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6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION 6.
ULUSLARARASI TOZ METALURJS KONFERANSI ve SERGS
6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION 6. ULUSLARARASI TOZ METALURJS KONFERANSI ve SERGS
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Development of PM in China
Authors: Michael Godin, Bahar Bayar, Fenling Han Abstract The continuous economic growth in China has an immense impact on the development of Chinese PM. Widely known advantages such as low production cost are complemented by the increasing quality of Chinese powders, PM parts and PM equipment. The international trend towards production localization in the automotive sector is accompanied by political pressure from Chinese government, which aims to have 50% local content in cars sold in China. 2009 Chinese car production reached 13 million, surpassing the US as the largest auto market in the world. Other industries such as medical, computer and telecommunication increasingly make use of Chinese PM. The development of Chinese PM raises concerns among western PM competitors, however most PM companies in China have a relatively low technological level and arent able to meet the highest standards of foreign customers. Therefore the interest to purchase foreign PM equipment and technologies offer various opportunities to foreign counterparts. Overview Abstract 1. History of PM in China 2. Automotive market in China 3. 3. PM in China - Market Data 4. 4. PM producers in China Changsha Xunda Powder Metallurgy NBTM New Materials Group Shanghai Automotive Powder Metallurgy 5. PM equipment Sintering Furnaces - Ningbo Dongfang Heating Equipment Compacting Presses - Nanjing Eastern Precision Machinery (EPM) Atomization - Changsha Easy Fashion Industry HIP & CIP - Beijing Isostatic Pressing Technology Engineering Center (IPTEC)
6. Iron and Copper Powder in China 7. MIM in China 8. PM education in China 9. Trends and Development of the Chinese PM industry 10. References 1. History of PM in China The PM industry in China started in the 1950s. One of the first enterprises to produce PM components such as bearings was the company Shanghai Automotive Powder Metallurgy Co., Ltd. After Chinas opening policy starting 1979 the development of PM in China accelerated due to the many opportunities
to supply PM components to emerging automotive, motorbike, electronics and furniture industries. As of the beginning of the 21st century, the automotive industry in China continues to develop at an accelerated speed, increasingly driving the growth of Chinas PM. Counting Powder, Mold, PM equipment and component manufactures in China, there are approximately 2000 PM enterprises in China. 2. Automotive Market in China The Chinese automotive market has been constantly growing for the last 20 years. In 2010 more than 18 264 700 vehicles were manufactured in China, making the Peoples Republic of China to the largest automotive producer in the world. 2010 the industry showed an increase of 32.44% compared to 2009. The output of passenger vehicles was 13 897 100. The quantity of automotive PM parts reached 18 456T in 2010, an increase of 9.8% compared to 2009. The amount of PM structural parts reached 116 835T, sinter parts were 12 509T. The PM industry in China is largely concentrated in eastern coastal regions, where most PM producers are located. However due to rising labor costs many enterprises have started to move further inland where labor costs are still much less. It can be predicted that China will continue to be a large and growing automotive market surpassing 20m cars in 2011. With an increasing amount of global automakers setting up their manufacturing plants further inland in China, the PM industry will certainty continue growth in the next years. Currently only 3% of Chinese population have a driving license. Therefore there is a tremendous potential for the automotive industry to further expand production and increase its sales in China. The PM industry in China will benefit from the current 5 years plan of the Chinese Communist Party, which oblige automotive producers to localize at least 50% of their automotive components. The governmental requirement forces automotive producers to source their PM components locally and refrain from importing them into China. Volkswagen and General Motors in China Currently the VW and GM Groups are the most successful automotive corporations in China. Combined the two companies have produced more than 3m vehicles in their manufacturing facilities across China in 2010. VW and GM both entered the Chinese market in the early 1980s and have established various joint ventures with local partners. Their business models allowed them to profit from the low production costs in China and substantially grow their business in cooperation with their partners. 3. PM in China - Market Data Total PM Sales in 2010 reached 300m USD. A growth of 42% compared to 2009. PM in China is not as closely related to the automotive market as it is in Europe or the US. Only 42% of all PM produced components in China are automotive components. Another 20% of PM parts components for the motorbike industry. More than 30% of all produced PM parts are supplied to non automotive related industries such as electronics, household, tools and others. Chinas PM total output surpassed Japan in 2009, reaching 137 146T in 2010. The output of the largest 12 PM producers in China was more than 83 000T in 2009. Chinas PM is currently Asias largest PM market. Largest PM producers in Mainland China (Sales): 1. Ningbo NBTM 2. Yanzhou Porite 3. Haian Yingqiu 4. Chongqing Huafu 5. Shanghai Automotive (SAIC) Chinas PM producers are not entirely focused on automotive products. Only five of the twelve largest PM producers have more than 75% of their components produced for the automotive industry in 2009. On average Chinese PM producers supplying 42% of its components to the automotive and 20% to the motorbike industry.
4. PM producers in China To show a general overview about the Chinese PM producers three PM producers will be presented. According to output in tons in 2009, the largest Chinese PM producer, Ningbo NBTM (#1 in China), Shanghai SAIC Group (#8 in China) Changshu Xunda (#20 in China) are briefly presented. NBTM New Materials Group Co., Ltd. NBTM is a first listed foreign-controlled company in China, which emerged from Ningbo Tongmuo Powder Metallurgy Co., Ltd. The company is registered with the capital of 30m USD. The Mutsumi Special Alloy Industry Co., Ltd. from Japan holds 33.34% of its shares. The Group has seven production sites all over China, employing more than 3000 people. The companies headquarter is in Ningbo, Zhejiang Province, approximately two hours south of Shanghai. Among others NBTM supplies to BorgWarner, ZF, Magna, GM, BYD. Only 42% of the companys production are automotive components. NBTM is the largest producer of sintered structural components in China. NBTMs annual production capacity is more than 40 000T. In 2010 the annual sales reached 170m USD. The sintered components manufactured by NBTM are used in automobile, motorcycle, refrigerator and air-conditioner compressors and power-tools. NTMB is exporting around 10% of its production to the US, Japan and Europe. Shanghai Automotive Powder Metallurgy Co., Ltd. (SAIC) SAIC is the oldest PM producer in China and is a completely government owned enterprise. The company has been manufacturing PM components since the 1960s and is currently the main PM supplier of GM and VW in Shanghai. Among others clients, the company is supplying KIA, FAW and a few foreign clients. With 5000T annual production capacity and 34m USD sales in 2010 the company belongs to largest PM producers in China. Changshu Xunda Powder Metallurgy Co., Ltd. Changshu Xunda is located 2 hours from Shanghai, in Changshu City, Jiangsu Province. The company was founded in 1992 and is privately owned. Xunda employs 250 people and has assets of 4m USD. The production facility covers an area of 20,000m2. Xunda was ISO9001- 2000 certificated in 2001 and TS16949 & ISO14001 certificated in 2008. Currently the production at Xunda, amounts 4m parts per month. The company produces products such as gears and clutches in quantities of 500 000 and more pcs per year. Xunda has a full equipment park, including more than 50 compacting presses ranging from 5T-500T, sizing presses, sintering furnaces, after treatment equipment, mold making and machining equipment. In addition, Xunda has a lab with all functions for 3D, precision air flow and strength testing. Xunda has also necessary equipment for metallographic, material flow and hardness testing. And the heat treatment workshop is equipped with an imported IPSEN furnace. 5. PM Equipment in China Currently foreign PM equipment has less than 10% of the total market share in China. The main reason is for the low market share is the high price of the foreign equipment and the long lead-times for spare parts. In general Chinese PM Equipment costs approximately 30% of what foreign PM equipment costs. In terms of quality, a difference remains between foreign and Chinese PM equipment, however there is a rapid increase of the quality of Chinese PM Machinery. In addition most of the PM components produced in China are rather simple and do not require highly sophisticated high precision equipment. Isostatic Pressing Technology & Engineering Center (IPTEC) IPTEC is the department of the China Iron & Steel Research Institute Group (CISRI) specialized in R&D and production of isostatic pressing equipment. IPTEC has begun its R&D work and production of cold isostatic presses (CIP) in 1956 and hot isostatic press (HIP) in 1972. In 1991, it developed its first sinter hot isostatic press furnace (Sinter-HIP or SIP). It has been provided nearly two hundred of CIP, HIP and Sinter-HIP furnaces for more than 100 customers in China and abroad. IPTECs equipments is widely used in the molding, sintering and densification of high-temperature, titanium-aluminum and carbide alloys, high performance ceramics, powder metallurgy and composite materials.
The company currently currently has 40 employees in its production site in Hebei, 2h from Bejing. The companies HQ is in Beijing, where 13 staff are involved in the companys operations and R&D. Annually IPTEC has the capacity to produce 20 Sintering HIP, 10 CIP and 5 HIP furnaces. The production time for a sintering HIP is around 18 months, the cycle for a SIP takes 10 months. Examples are: IPTECs Sintering HIP (exported to South Korea in 2010): Size: Temp: Max. Load: 5 MPa Argon: 620x460x1700 1520C 1500kg 1400 C 8 C
IPTECs HIP (Installed for a Chinese customer in 2009): Chamber size: Temp: Max. Load: 1 5 0 Mp a: 1250x2500mm 1400 C 10T Argon Gas
Nanjing East Precision Machinery Co., Ltd (EPM) EPM was established in 1995. EPM is a privately owned enterprise that specialized in the manufacturing & development of powder forming technology, forming equipment, tool adapters and peripheral equipment. It provided thousands of automatic dry powder compacting presses for magnetic materials, special ceramic, PM, hard metals and carbon production. Currently the Nanjing based company has 250 staff and produced 200 presses in 2010. Among its clients are Miba, Ames, Tigra and Porite. Ninbo Dongfang Heating Equipment Co., Ltd. Ningbo Dongfang is the largest producer of heating equipment in China. With over 150 employees the company has produced more than 100 sintering furnaces in 2010, reaching more than 10m USD in sales last year. Some of the companys clients are the Hawk Corp, FJ Automotive Denmark, Porite, SAIC and NBTM. The company is constantly expanding its product range and developed its first MIM batch furnace in 2010. One of its recently sold sintering furnaces for a US client was a 1150C furnace with only 2C of temperature difference at maximum operating temperature. With a production capacity of 240kg/hour the furnace was built for up to 500g automotive and magnet component production. Changsha Easy Fashion Equipment Co., Ltd. Easy Fashion is a Changsha based company specializes in atomization equipment, vacuum and smelting furnaces. With over 80 staff (6 R&D) the company manufactured 30 Vacuum and 6 atomization units for Chinese and foreign clients in 2010. 6. Powder Production in China Iron and Copper Powder Ferrous Powder production in China has been growing annually by 20% for the last 10 year, reaching 180 000T or approximately 85% of the US production in 2010. Copper powder in China has already surpassed the US production, reaching 30 000T in 2010.
The Chinese government has implemented a 25% export tariff on metal powder made in China. The current government restriction leads to market changes in China, making more high quality powder used in China. The tariff on powder exports leads to an increase of quality of finished components since good powder is being used domestically in China. Iron Powder Currently there are 28 ferrous powder producers in China, of which the seven largest have a market share of 63%. The total output of ferrous powder in China has reached 295 000T in 2010 (Water Atomized 105 000T & reduced powder 186 000T). Large Fe Atomized Powder producers in China 1. Laigang 2. Angang 3. Jiande Large Fe Reduced Powder Producers in China 1. Laigang 2. 2. Wugang 3. Beipiao 4. Magang Chinese powder is 50% cheaper than foreign powder. Therefore foreign powder is being replaced by many components manufacturers with domestic powder. Copper Powder In 1960 only 40T of electrolytic Cu powder was produced in China. In 2009 the production of electrolytic powder reached 20 500T. The total production of Cu powder in China has reached 40 500T. Largest Cu powder producers in China Beijing GRIPM Chongqing Huahao Hengshui Runze Cu powder produced in China: 50% Electrolytic 33% Atomized 10% Copper Coating, others 7% Reduced 7. Metal Injection Molding (MIM) in China Metal Injection Molding is a rather small industry in Chinese PM market, which started commercial application in the early 1990s. With increasing foreign direct investment into China, Chinese MIM experienced a high technological improvement and product innovation in recent years. MIM sales in China in 2010 reached 55m USD. Compared to the sales in Asia of 450m USD, the MIM market in China is still rather small, however continues to develop at an high speed pace. Currently there are 70 MIM producers in China, of which most are located around eastern Chinese manufacturing hubs such as Beijing, Shanghai and Guangzhou with most companies located in the provinces of Jiangsu, Zhejiang and Guangdong. Most commonly used materials in Chinese MIM are 17-4PH, 316L and FeNi alloys. MIM in China is strongly focused on computer and communication components and only few companies in China are manufacturing medical equipment and automotive components. Most of the 70 MIM producers in China are manufacturing their own feedstock and using predominantly domestic equipment.
Trends of MIM in China The MIM industry in China is growing rapidly where an increasing number of MIM and MIM powder newcomers can be seen. Due to high price foreign of MIM powder & feedstock foreign powder is being replaced with domestic Chinese one. An increasing use of cemented carbides, W & tool steels can be observed. Even though the MIM industry in China is already 20 years old, the domestic demand has not yet started and the majority of MIM enterprises highly depend on exports. However with an increasing awareness for the MIM technology, a demand for MIM products in China is expected shortly. Due to rapidly rising labor and material costs Chinese MIM is rapidly moving from very low automation to semi automated production, with an increasing number of robotics and computer programmed machines instead of manual labor. For that purpose Chinese MIM companies are heavily investing into the purchase or own development of MIM equipment. 8. PM education in China There are four leading universities with a PM core engineering major in China. The leading PM University is the Changsha Central South University. Other universities with a PM Major are Hefei Industrial, Beijing Tech and Guangzhou Industrial. There are six leading PM R&D institutes in China. Powder Metallurgical R&D institutes only accept PM master graduates. In 2010, there were over 500 graduates with a PM major in China. The PM graduates are the main drive force behind the rapid development of Chinas PM industry. 9. Trends in Chinese PM Industry Most Chinese PM factories use domestic equipment and do not export their production. However a quick quality improvement of Chinese equipment can be seen, since the producers are forced to meet the requirements of foreign PM end users who engage in manufacturing and assembling in China and require the highest component quality. An increasing number of PM factories in China start to import foreign equipment to replace domestic one. Regarding the powder, foreign powder is replaced with domestic one, mainly due to a much lower price comparable quality. Chinas PM has gained increasing competitiveness in the world. As a result, an increasing demand for training and education has become necessary.
THE PRACTICAL ANALYSIS OF FABRICATION OF A COPPER PART BY METAL INJECTION MOLDING

Asghar SAFARIAN*, Karen ABRINIA ** and Amir Hossein BEHRAVESH *** * Islamic Azad University, Maragheh Branch, Iran, asgharsafarian@iau-maragheh.ac.ir Tehran University, Faculty of Engineering, Department of Mechanical Engineering, Tehran, Iran, cabrinia@ut.ac.ir *** Tarbiat Modares University, Faculty of Engineering, Department of Mechanical Engineering, Tehran, Iran, amirhb@modares.ac.ir
**
ABSTRACT In the present work the application of MIM to metal matrix composites comprising of Copper powders is presented. The processing steps are discussed and a suitable set of powder loading, mixing procedure, molding condition and debinding/sintering schedule has been established. A defect-free cylindrical part was successfully produced and finally the effects of injection temperature, density and debinding/sintering atmosphere were studied. Also the possibility of manual mixing of powder/binder and direct injection of that mixture without having prepared granules has experimented. Keywords: Metal Matrix Composites, Copper Powders, Debinding, Sintering, Powder Loading. 1. INTRODUCTION The Metal Injection Molding (MIM) process is a combination of powder metallurgy and plastic injection molding technologies. The process has been developed from the injection molding approach used for manufacturing of plastic parts, but the technology for MIM is more complicated than that of plastic injection molding, which arises from the need to remove the binder and to strengthen the part. The MIM process comprises of four main steps: mixing, injection molding, debinding and sintering as illustrated in figure 1 [1].
Figure 1. Schematic diagram of MIM process.
In MIM process the most important thing is the technical information of these four steps which are different for various materials. Therefore for each material some experiments should be done to get technical and applicable data. That is what this study has tried to do for copper material which is very important in producing parts in different sectors such as telecommunication, electricity, etc. 2. EXPERIMENTAL PROCEDURE 2.1. Material Copper gas-atomized powders (code No. 19190, Ghatran Shimi Co., Iran) with spherical shape and average particle size smaller than 15 m have been used in order to prepare the feedstock. The binder used in this work is composite of 36% PP (fiber-free, Bandare Emam Petrochemical, IRAN), 60% paraffin wax (PW) and 4% stearic acid (SA). Powder loading for this work is 94 wt.% copper and 6 wt.% binder. In order to prepare the feedstock a manual mixing method has been used. For this purpose, at first step all PW was melted and copper powders were added step by step. After this step other components were added based on schedule shown in table 1. The heating equipment was a normal gas burner with a controllable gas dial in a way that feedstock temperature could be measured by a laser thermometer. In this step the used mixture was a fork shape manual one with rotation of 200 rpm. Table 1. Steps of feedstock manual mixing. Steps 1 2 3 4 5 Temperature 65 C 65 C 65 C 65 C Cooling until 24 C Time of Mixing .. 15 min 25 min 15 min 20 min Materials to be Added 100% PW 50% Copper Powder 50% Copper Powder 100% PP and SA ..
As the temperature was around the wax melting point, the only phenomenon happened in mixing step was powder wetting by melted wax and therefore having powder and polymer stuck to each other what made a homogenous physical feedstock not in granule form but in loose form of mixing which could easily fed into injection machine hopper. 2.2. Molding In this work a cylindrical part has been chosen as sample and one cavity mold with direct sprue has been designed and made based on dimensions shown in Figure 2 (all dimensions are in mm). The prepared feedstock was injected into the mold on a normal plastic injection machine (HAIDA HDX, 50 gr) with 7.5 MPa pressure and in two different temperatures, 165C and 185C of feedstock temperature which was again measured by laser gun thermometer. The injection process done in this situation and density measurement have proven that injection, with 165C results in homogenous and dense parts, while with 185C, parts with low density were fabricated which could not be debound and sintered to reach defect-free parts. The reason of this phenomenon will be discussed in following sections.
Figure 2. Geometry of sample.
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2.3. Debinding/Sintering Thermal debinding was used to extract the binder inside the green parts. In this step different green parts regarding their density from 5.5 to 7 g/cm3 were debound and so the effect of density on process and schedule of debinding was determined. These densities are measured simply by weighting green parts and dividing them by part volume ((20)24). Table 2 shows the debinding steps done in a tube furnace with -0.5 bar vaccum and circulatory system. Table 2. Debinding steps. Steps 1 2 3 Heating Rate (C/min) 0.5 1 2 Debinding Temperature (C) 100 250 500 Debinding Holding Time (min) 30 30 15
After debinding the same furnace was used to get the brown parts sintered and these parts get directly into sintering step from debinding. Sintering step was started from 500C and in fact it continued from the debinding step. Table 3 illustrates this step in detail. Table 3. Sintering steps. steps 1(debinding last step) 2 Heating Rate (C/min) 8 Sintering Temperature (C) 500 980 Sintering Holding Time (min) 60
The total time needed for debinding and sintering is 550 min and 120 min respectfully. After these steps defect-free parts were fabricated from brown parts and the best result was reached from the green parts with density near 7 g/ cm3. Figure 3 shows the whole diagram of debinding/sintering in one graph. Figure 4 illustrates the sintered defectfree part regarding the final part density, mechanical properties like hardness and tensile, with total volumetrical shrinkage of 13% which was measered by measuring the sintered part dimension and its weight. 3. RESULTS AND DISCUSSION 3.1. Influence of Injection Temperature As it was explained before injection process was carried out in two temperatures, 165C and 185C. In 185C because of high temperature, there is a low viscosity of feedstock mainly about binder, and therefore possibility of separation of binder/powder under injection pressure increases and so the percentage of defected parts with low density arises. Also separation phenomenon shown in Figure 5 is a concern that will definitely affect the debinding and sintering steps. This separation was happened during the experiments and because the pictures of these parts were not clear, this phenomenon is shown in schematic form. Differences among movements behavior of components in feedstock especially between powder and binder cause some problems in molding process and it gets worse when temperature gets high and viscosity drops dramatically.
Figure 3. The graph of debinding/sintering.
Figure 4. Sintered part.
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Therefore temperature should be near polymer melting point which causes optimum viscosity that makes the feedstock flow and get molded better and prevents the separation of powder and binder. In this study temperature of 165C near the melting point of PP is optimum injection temperature that results in homogenous parts. Another point to be considered is the difference between pure polymer and the present feedstock (powder/binder suspension). Because of having the powder as metallic particles inside the feedstock, the machine barrel transfers heat more easily and also there is interior friction that generates more heat inside the feedstock. Therefore the injection temperature of pure polymer and this feedstock could not be equal. Therefore it seems that the lower injection temperatures for this feedstock could have better injection results compared to pure PP.
Figure 5. Schematic shape showing the separation phenomenon in an injected part. 3.2. Influence of Green Part Density Although a considerable amount of research has been focused on the relationship between the density and the strength of sintered metal components [2-11], most of the investigations have not included both the low-density and the high-density powder compacts. In the present work samples with density of 5.5 to 7 g/cm3 were debound and sintered in order to study its effect on process. Low density samples have higher amount of binder and therefore there is not adequate compact of metallic particles. Consequently these samples will collapse in debinding stage and that is what happened for samples with density under 6.5 g/cm3. Although samples with higher density (around 6.5 g/ cm3) were debound without losing their shape, the result of sintering and strength of these parts was not satisfying (for example after sintering some parts with this density could crumbled easily). Figure 6 shows micrographs of these parts. As it is shown in figure 6 there are some gray places that show the presence of porosity. 3.3. Influence of Debinding/Sintering Atmosphere In this section the effect of furnace atmosphere were studied. Three different mediums were applied on samples in order not to get them oxidized:, vacuum, Nitrogen and Argon gases. The mechanical properties of sintered metals depend strongly on the porosity, inclusions, oxygen content and other metallurgical variables [12]. In this stage because of high temperature metallic samples could get oxidized easily. Therefore a -0.5 bar vacuum air atmosphere was applied on samples during debinding/sintering stage. However the result was not satisfying and all samples were oxidized which could be seen by color changes and very low strength that caused parts crumbling by hand pressure. The reason could be the low degree of vacuum, but because of lack of efficient vacuum equipment high degree of vacuum was not applied. Second medium was Nitrogen that was applied on samples. Nitrogen could not prevent samples oxidation completely and the sintered parts showed inappropriate mechanical properties which observed by some tests like tensile test. The reason was the degree of gas purity and its flow rate of 50 cc/min that was not enough for this experiment.
(a)
(b)
Figure 6. Micrographs of sintered parts (x1000), a) green part density: 6.5 g/cm3 and b) green part density: 7 g/cm3.
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Finally the last medium was studied and Argon was used with high purity and flow rate around 80 cc/min. Among all these atmospheres Argon had the best result and sintered parts in third atmosphere got to reach the desired mechanical properties compared to copper parts produced by other processes rather than MIM. It also should be mentioned that in order to get the best result samples were located on graphite powders which got oxidized rapidly and so could prevent metallic samples oxidation. Also it should be mentioned that the graphite powders were only used in the last medium. 3.4. Influence of Feedstock Direct injection instead of prepared Granules Making granules could expose some extra expense on metal injection molding. In this study an effort has been done to examine the possibility of direct injection of feedstock with manual mixing (explained in section 2.1) not in granule shape. The experiment has proven that in first stage of injection process, all injected parts (in this study first ten parts) have low density and are not homogenous. While after some injection it turns to get better with high quality. The reason could be the difference between movement behavior of binder and powder that makes them to separate. After this separation, under applied pressure by screw, binder flows easily and fills the mold. Therefore injected parts at first stage after starting point of injection have low density. However there is a slow flow for powders. In other words, powders have gradually flow forward and gathered in front zone of barrel and get ready to be injected to the cavity of mold. In this stage (after ten to fifteen parts) injected samples will have high density. This phenomenon could happen periodically and there will be a combination parts with low and high density which could heavily affect the production stability. As it mentioned before injection process have been done with normal plastic machine with its normal screw that definitely could affect all process specially injection of feedstock without granules. Although there is no absolute number of low density or high density parts based on which a injection parameters could be set. Changes and optimization in screw design could cause the process and have different results. 4. CONCLUSION After various experiments done in this study, finally a defect-free part with total volumetrically shrinkage of 13% was produced and all data needed for mixing, injection, debinding and sintering has determined. Also study of injection temperature pointed out that injection temperature should be near polymer melting point and the more temperature rises, the less samples density gets. With low density there is debinding and sintering problems. Even if there are some samples with density near ideal densities, the sintered part shows inappropriate mechanical properties. In this study the least density should be 7 g/cm3. Debinding and sintering stage have special concerns among which the medium could be very important if the material is sensitive to oxygen, especially in high temperatures. For copper samples debinding and sintering could be successful in Argon atmosphere with flow rate around 80cc/min. REFERENCES 1. B.O. Rhee, Processing Behavior of Powder/Binder Mixtures in Powder Injection Molding-Binder Separation and Quick Freezing, Doctor of Philosophy Thesis, Rensselaer Polytechnic Institute, School of Mechanical Engineering, Troy, NY, USA, 1992. 2. A. Salak, V. Miskovic, E. Dudrova, E. Rudnayova, Powder Metall. Int. 6 (3) (1974) 128. 3. N.A. Fleck, R.A. Smith, Powder Metall. 24 (1981) 121-125. 4. V.T. Troshchenko, Sov. Powder Metall. Met. Ceram. 2 (1963) 179-184. 5. H.E. Exner, D. Pohl, Powder Metall. Int. 10 (1978) 193-199. 6. A. Bose, JOM 47 (8) (1995) 24-30. 7. G.F. Bocchini, Int. J. Powder Metall. 22 (3) (1986) 185-202. 8. A. Bose, J.J. Valencia, J. Spirko, R. Schmees, Advances in powder Metallurgy and Particulate Materials, vol. 3, MIPIF, 1997, pp. 18099-18112. 9. G.F Bocchini, Int. J. Powder Metall. 22 (3) (1986) 185-202. 10. J.J. Valencia, T.J. McCabe, H. Dong, Advances in powder Metallurgy and Particulate Materials, vol. 2, MIPIF, 1995, pp. 6205-6214. 11. T.J. Griffiths, R. Davies, M.B. Bassett, Powder metal. 22 (1979) 119-123. 12. R. Haynes, The Mechanical Behavior of Sintered Metals, Freund Pub., London, 1981.
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THE PROCESSING OF Ni-RICH TiNi FOAMS WITH Mg SPACE HOLDER TECNIQUE AND IN-VIVO EVALUATION AS GRAFT MATERIAL
G.pek NAKA*, B.Bertan ARPAK**, akir BOR*** *Middle East Technical University, Department of Metallurgical and Materials Engineering, 06800, Ankara, Trkiye, inakas@metu.edu.tr ** Bakent University Faculty of Dentistry, Department of Oral and Maxillofacial Surgery, 06680, Ankara, Trkiye, bertanarpak@gmail.com ***Middle East Technical University, Department of Metallurgical and Materials Engineering, 06800, Ankara, Trkiye, bor@metu.edu.tr
ABSTRACT Porous TiNi alloys are very promising materials for the biomedical applications due to their superelastic properties and shape memory behavior in combination with the elastic module that are similar to that of bone. Surface roughness, which is a critical parameter to employ the material as a graft, can be achieved by the powder metallurgical processes. However, the close control of the pore size, geometry and orientation is still difficult to maintain. In this study, magnesium space holder technique is employed for manufacturing TiNi foams that consist of interconnected pores with homogeneous shape, size and distribution in addition to the surface quality necessary for bone growth. Porous TiNi alloys, which were processed from prealloyed nickel-rich (50.8 at.%Ni) TiNi powder via sintering at 1100 C for 1 hours under protective gas atmosphere, were placed into the created defects on the femur of rats for a period of 90 days to evaluate the bone healing process. Afterwards, processing technique was improved via increasing sintering temperature and time to 1200 C and 2 hours, respectively. The processed TiNi foams that have uniformly distributed and interconnected spherical pores within a size range of 250-600 m, were in fully austenitic state and the formation of secondary intermetallics as well as the oxidation, which is a major problem in dealing with titanium alloys, was prevented according to the X-ray Diffraction (XRD) and scanning electron microscope (SEM) analysis. Bone ingrowth was achieved in TiNi foams that have pore ratio in the range of 59-73 vol.%, and no infection was observed for these osseointegrated grafts according to the histopathological evaluation. Although no failure or bone resorption was observed for the grafted TiNi foams, the newly processed porous TiNi alloys were subjected to compression tests in order to evaluate the mechanical compatibility for biomedical applications. It was found that the mechanical properties could be adjusted by the alteration of the pore ratio and stress shielding problem could be eliminated. Keywords: TiNi, porous, graft, compression, biocompatibility, bone growth
1. INTRODUCTION Titanium and its alloys have been extensively studied and applied in the field of biomedical applications [1-3]. Among Ti alloys, TiNi has outstanding properties such as shape memory and superelasticity in addition to its elastic modulus that is similar to that of cortical bone [2, 4]. Processing the TiNi alloys in porous form further enhances the applicability of this alloy since the control of the mechanical response become possible via the adjustment of the pore characteristics. On the other hand, there has been a debate about the biocompatibility, especially in terms of possible toxic effects of Ni [5-8]. However, there are several inquiries indicating that Ni release will not occur since the implant will not be subjected to such a corrosive environment that is strong enough to reduce the passive TiO2 layer formed on TiNi [6-8].
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In addition to the mechanical and chemical, surface properties are also of vital importance in graft applications. The surface roughness required for the bone to have a good contact with the implant material, which can be artificially introduced to graft materials, is naturally present when the graft was processed via powder metallurgical methods. Among the several powder metallurgical techniques, sintering with space holder method has the advantage of the close control of pore shape, size and orientation. Therefore, Ni-rich TiNi foams, which were aimed to be used as graft materials, were processed by Mg space holder technique. The evaluation of the processed foams as graft materials were accomplished by the histopathological examination of the porous TiNi alloys after 90 days of implantation to the femur of rats. 2. EXPERIMENTAL PROCEDURE In this research, prealloyed Ni-rich TiNi powder (Ti-50.8at%Ni, 99.9% purity, supplied by Nanoval GmbH & Co. KG) were used as the raw material to overcome the formation of the secondary intermetallics such as Ti3Ni4, Ti2Ni3, which degrades the mechanical properties. Magnesium (99.82% purity, supplied by TangshanWeihao Magnesium Powder Co. Ltd.) was selected as the space holder since it prevents the oxidation of TiNi due to its higher oxygen affinity. Both powders, which were produced by gas atomization, were in spherical shape with average particle sizes of ~20 m and 356 m, respectively. The porosity ratio was adjusted with the amount of magnesium added. The powder mixture having predetermined ratios was blended with the addition of polyvinyl alcohol (PVA) solution (2.5 wt.% PVA + distilled water) that was used as binder. After compaction of the powder under 400 MPa pressure that is applied via hydraulic press, sintering were done at the atmosphere controlled furnaces. High purity (99.995%) Argon gas was used for the atmosphere control. The compacted powder mixtures with a diameter of 3 mm and height of 2 mm, which were processed for in-vivo evaluation, were sintered at 1100 C for 1 hour. Another set of TiNi foams having 10 mm diameter and aspect ratio of 1, were processed via sintering at 1200 C for 2 hours to evaluate the mechanical response of TiNi foams following the improvement obtained in processing technique. The heating rate was kept constant at 6.5 C/min for both of the processing techniques to assure sufficient sintering that would prevent the collapse of the compact upon melting and evaporation of magnesium. The porosity measurements were done according to the Archimedes principle by a precision balance equipped with a density measurement kit. Scanning electron microscope (SEM) (JSM 6400, Jeol LTD, Tokyo, Japan) and X-ray Diffraction (XRD) (Cu-Ka, Rigaku D/Max 2200/PC, Rigaku Corporation, Tokyo, Japan) analyses were employed to examine the pore structure and the phases present in the sintered porous alloys. Before the implantation of porous TiNi alloys, the residual MgO particles were eliminated with the nitric and hydrofluoric acid solutions treatment and NaOH solution was used for the neutralization procedure. In addition, TiNi graft materials were cleaned in ultrasonic bath with deionized water followed by the ethanol application for removing the possible oil residuals. Moreover, the grafts were autoclaved at 121oC for 30 minutes just before the implantation to the Sprague Dawley kind rats. TiNi foams with three different pore ratios in the range of 59 - 73 vol.% were selected as graft materials for the evaluation of bone growth. Accordingly, the rats were separated into 3 groups, each having 10 rats. The graft material was placed in the bone defect, which was created on the femur of the rat, with 3 mm diameter and 2 mm depth. Only one graft was implanted for each rat. The rats were continuously monitored for the infection or oedema formation as well as the change in general behavior. However, no detrimental effects of the placed grafts were observed in any of the rats during 90 days period of investigation. The grafts implanted were removed together with the femur for histopathologic examination after the sacrification of the rats. The histopathologic samples were prepared with the cutting-grinding method by the Sclerogenous Grinding Laboratory in the Dentistry Faculty of Hamburg University. On the other hand, TiNi foams processed by sintering at 1200 C for 2 hours were subjected to monotonic compression tests to evaluate the mechanical response since the implant materials are generally subjected to compressive loading. Compression tests were conducted with a constant crosshead speed of 0.1 mm/min by a 100 kN capacity screw driven mechanical tester (Instron 3367, Instron Co. LTD., Norwood, USA). 3. RESULTS AND DISCUSSION Porous TiNi alloys processed with three different amounts of Mg addition, namely 50, 60, and 70 vol.%, for both the evaluation of bone growth and mechanical characterization. However, the differences in the sintering regime have resulted in different porosity ratios measured at the end of processing as given in Table 1.
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Mg added (vol.%) 50 60 70 50 60 70
Porosity (vol.%) 59 66 73 49 58 64
Porosity (vol.%) 1h at 1100C 2h at 1200C
Table 1.The change of porosity with sintering regime and the amount of Mg addition. The amount of porosity measured for the samples sintered at 1100 C for 1 hour was found to be higher than the amount of Mg added while the pore ratio is lower than the added Mg for the TiNi foams sintered at 1200 C for 2 hours. The change in porosity with the sintering regime is believed to be due the change in the amount of microporosity. As the sintering temperature and time had increased, the diffusion rate of the atoms and so the extent of sintering was increased. Accordingly, the amount of microporosity that remained in between the powders after sintering was decreased. The change of the amount of microporosity with sintering regime was also revealed by SEM examination (Figure 1).
(a)
(b)
Figure 1. SEM micrographs indicating the microporosity for porous TiNi alloys sintered at (a) 1100 C for 1 hour and (b) 1200 C for 2 hours. On the other hand, all of the processed TiNi foams were found to be in austenitic (B2) state at room temperature according to the XRD analysis results. As it was given in Figure 2, extra peaks with low intesity were observed due to the presence of MgO residuals on the TiNi foams after processing. As mentioned above, these residuals were removed by acid treatment before implantation.
Figure 2. Representative XRD analysis result for the processed TiNi foams.
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Histopathologic examination showed that none of the grafts caused foreign body reaction or any inflammatory changes. Independent form the porosity, the bone growth was observed into all samples without forming a zone. The direct contact between the bone and the TiNi graft was observed indicating the low level of oxidation that was achieved via sintering with Mg space holder technique (Figure 3a). Moreover, the extent of osseointegration, which was achieved in 90 days of evaluation, was the evidence of the biocompatibility of TiNi foams processed (Figure 3b). Although not quantized, the extent of bone growth was observed to be increased with increasing porosity due to the increase in the interconnection between the macropores.
10 m Figure 3. The results of hystopathologic evaluation indicating: (a) the direct contact of the bone with the graft, (b) the extent of bone growth thorugh TiNi graft material. Although the mechanical properties of porous TiNi foams sintered at 1100 C for 1 hour were verified to be sufficient for implant applications, the mechanical reponse of the TiNi foams processed with the improved technique was also analyzed with uniaxial compression tests. The most important parameter among the mechanical properties is the elastic modulus due to the stress-shielding problem that is commonly encountered during use of implant materials. Stress-shielding is the resorption of the bone when all applied load is carried by the implant, which has higher elastic modulus than that of the bone. Therefore, the implant materials have to optimize high strength with low stiffness. As given in Table 2, porous TiNi graft materials display a range of elastic moduli varying with porosity, enabling the use of them as bone graft materials either for cancellous (< 3 GPa) or cortical bone (10-20 GPa) [4]. Porosity (vol.%) 49 58 64 E (GPa) 8.710.24 5.87 0.31 2.93 0.03 y (MPa) 147.93 12.10 91.50 8.50 44.12 7.65 max (MPa) 273.45 9.25 174.75 10.75 93.27 5.30
Table 2. The mechanical properties of TiNi foams sintered at 1200 C for 1 hour, where E is Youngs modulus, y is yield strength and max is ultimate compressive strength (The given data is the average of five tests for each level of porosity). When it was considered that the mechanical properties enhance with the extent of sintering, which can be achieved by raising the sintering temperature, even lower elastic moduli could have been achieved for the grafted TiNi foams. Therefore, TiNi foams processed at 1200 C are believed to be more prefereable for implant applications due to the high strength achieved in combination with low elastic modulus. CONCLUSIONS In this research, porous TiNi alloys with homogeneously distributed, interconnected, spherical pores were processed with Mg space holder technique. Two different sintering regimes were applied, one for processing the graft materials and the other at a higher temperature for the mechanical characterisation. The graft materials processed via sintering at 1100 C for 1 hour with three different porosity ratio in the range of 59-73 vol.% were implanted to the femur of the Sprague Dawley kind rats. The histopathological examination revealed that bone growth had occurred into all of the implanted TiNi foams at a rate
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proportional with the amount of porosity. Although none of the grafts sintered at 1100C was failed or no bone resorption was observed during 90 days of implantation, TiNi foams that were sintered at 1200 C for 2 hours were mechanically characterized to investigate the possible improvement in mechanical biocompatibility. It was observed that the elastic moduli varying in a broad range enable the use of the high temperature processed TiNi foams for a wide range of applications having different requirements. REFERENCES 1. Niinomi, M., Mechanical Properties of Biomedical Titanium Alloys, Materials Science and Engineering A, Vol. 243, pp. 231236, 1998. 2. Geetha, M., Singh, A.K., Asokamani, R., Gogia, A.K., Ti Based Biomaterials, The Ultimate Choice For Orthopaedic Implants A Review, Progress in Materials Science, Vol. 54, pp. 397425, 2009. 3. Tarnta,D., Tarnta, , , D. N., Bzdoaca, N., Mndrla, I., Vaslescu, M., Properties and Medical Applications of Shape Memory Alloys, Romanian Journal of Morphology and Embryology, Vol. 50, pp.1521, 2009. 4. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review, Acta Biomaterialia, Vol. 4, pp. 773782, 2008. 5. Eliades, T., Athanasiou, A.E., In Vivo Aging of Orthodontic Alloys: Implications for Corrosion Potential, Nickel Release, and Biocompatibility, Angle Orthodontist, Vol. 72, pp. 222-237, 2002. 6. Wever, D.J., Veldhuizen, A.G., Sanders, M.M., Schakenraad, J.M., Horn, J.R., Cytotoxic, allergic and genotoxic activity of a nickel-titanium alloy, Biomaterials, Vol. 18, pp. 1115-1120, 1997. 7. Assad,M., Chernyshov, A.V., Jarzem, P., Leroux, M.A., Coillard, C., Charette, S., Rivard, C.H., Porous Titanium-Nickel for Intervertebral Fusion in a Sheep Model: Part 2. Surface Analysis and Nickel Release Assessment, Journal of Biomedical Materials Research Part B: Applied Biomaterials, Vol. 64B, pp. 121129, 2003. 8. Shabalovskaya, S.A., Surface, Corrosion and Biocompatibility Aspects of Nitinol as an Implant Material, Bio-Medical Materials and Engineering, Vol. 12, pp. 69109, 2002.
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TOZ METALURJS YNTEMYLE RETLEN KPREBLR PREFORM MALZEMELERN TIG KAYNAI LE BRLETRLMES VE KPREBLRLNN ARATIRILMASI
Arif UZUN*, Hanifi NC**, Halil KARAKO** ve Mehmet TRKER** Kastamonu niversitesi, Cide Rfat Ilgaz MYO, Kaynak Teknolojisi Blm, Kastamonu, auzun@kastamonu.edu.tr ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, hcinici@gazi.edu. tr, mturker@gazi.edu.tr
*
zet Toz metalurjisi yntemi ile karmak ekilli ve yksek mekanik zelliklerde sahip metalik kpk retmek mmkndr. Ancak bu yntem ile ticari boyutlarda kullanlabilecek byk boyutlu metalik kpkleri retmek gtr. nk retim srecinde kullanlan cihaz ve donanmlar nihai rn ktsnn boyutlarn snrlandrmaktadr. Bundan dolay kprtme ncesi alminyum preform malzemeler TIG kayna ile farkl akmlarda (130 - 230 A) birletirilmi ve 710 o C scaklkta kprtme ilemine tabi tutulmutur. Elde edilen kpk numunelerde kaynak blgesi kaynak yaplmam ile gzenek morfolojisi ve lineer genleme asndan karlatrlmtr. Anahtar Kelimeler: Toz Metalurjisi, TIG Kayna, Alminyum Kpk.
jonng of foamable precursor materals, produced by powder metallurgy, BY TIG WELDING AND nvestgaton of ther foamablty
ABSTRACT It is possible to produce metallic foam, by powder metallurgy, with high mechanical properties and complex-shaped. However, it is difficult to produce metallic foams with a large commercial scale with this method. Because the device and equipment used in the production process limited to the size of the final product. Therefore, foamable aluminum precursor materials was joined by TIG welding with different currents (130 - 230 A) and then foamed at 710oC. The weld zone was compared in terms of pore morphology and linear expansion with the un-welded foamed samples. Keywords: Powder Metallurgy, TIG Welding, Aluminum Foam. 1. GR Teknolojinin geliimine paralel olarak hafif ve dayanm yksek malzemelere ihtiya gn getike artmaktadr. Aratrmaclar, yapsal ve fonksiyonel uygulamalarda bu zellikleri bir arada bulunduran malzemeleri elde etmek iin eitli araylar ierisine girmitir. Metalik kpkler bu olgu ierisinde nemli bir yere sahiptir. Bu malzemelerin retiminde dkm ve toz metalurjisi (TM) endstriyel boyutta en fazla kullanlan yntemleridir. Toz metalurjisi (TM) yntemi ile metalik kpk retimi ilk olarak Fraunhofer Malzeme Aratrma Enstits (IFAM) tarafndan gelitirilmitir [1]. Bu yntem de sandvi levha eklinde veya karmak ekilli homojen gzenek yaplara
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sahip kpk paralar kprebilir preform malzemelere uygulanan sl ilem ile retilmektedir [2]. Son zamanlarda TM ynteminin gelitirilmesine ve maliyetinin azaltlmasna ynelik aratrmalar yaplmaktadr. rnek olarak ok pahal olan atomize alminyum tozlar yerine, daha ucuz olan alminyum talalarnn kullanlmas, kprebilir preform malzemelerin stlmas ileminde geleneksel n stmal elektrikli frnlarn yerine ok gl gne enerjisi kaynaklarnn kullanlmas verilebilir [3,4]. Benzer amala toz metalurjisi yntemi ile retilmi kprebilir preform malzemelerin birletirilmesine ynelik almalarda yaplmtr [5-7]. Bu almada da kprebilir preform malzemeler TIG kayna ile birletirilmi ve kprtme ilemine tabi tutulmutur. 2.MALZEME RETM VE DENEYSEL YNTEM 2.1. Kprebilir Alminyum Preform Malzemelerin retimi Bu almada Al tozuna % 0,8 orannda TiH2 ve % 7 orannda Si tozlar eklenerek, boyutlu turbula da kartrlmtr. Karm tozlar kalp ierisinde 600 MPa basn altnda tek ynl sktrlarak ham younlukta silindirik blok numuneler retilmitir. Daha sonra blok numuneler 500 oC scaklkta ekstrzyon ve haddeleme ilemlerine tabi tutularak kprtme ncesi preform numuneler haline getirilmitir. 2.2. TIG Kayna ve Kprtme lemi Kaynak ilemi iin hazrlanan 5 mm kalnlndaki preform malzemeler yzeydeki oksit tabakasnn uzaklatrlmas amacyla tel fra ile mekanik olarak temizlenmi ve saf alkole batrlmtr. Hazrlanan paralar kt aln pozisyonda, ift tarafl tek pasoda ilave metal kullanlmadan birletirilmi ve atmosfer ortamnda soumaya braklmtr. Birletirme ilemi invertr tipi kaynak makinesi ile argon koruyucu atmosfer gaz altnda yaplmtr. Deney esnasnda kullanlan kaynak parametreleri izelge 1de verilmitir. Bu parametreler eliinde birletirilen numunelere ait makro yap fotoraflar ekil 1de verilmitir. izelge 1. Birletirme ileminde kullanlan parametreler Kaynak Parametreleri Kullanlan akm Gaz ak debisi Elektrod ap, Tipi Kaynak akm (A) Dolgu teli Alternatif 12 lt/dk 2,4 mm, Tungusten 130-170-190-230 Amper Kullanlmad
Birletirme sonras, preform numuneler 710 oC scaklkta kprtme ilemine tabi tutulmutur. Kprtme ilemi dorusal genlemeyi belirlemek iin st yzeyi ak bir kalp ierisinde yaplmtr. Daha sonra maksimum lineer genleme oranlar belirlendikten sonra btn yzeyleri kapal 25x25x16 mm boyutlarnda kprtme kalplar kullanlmtr.
ekil 1. Farkl akmlarda birletirilmi preform malzemeler
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3. DENEYSEL SONULAR VE TARTIMA Eitlik 1de TIG kayna ile birletirilmi numunelerin, birletirilmemi preform (referans) malzemelere kyasla gzeneklilik oranlarn hesaplamada kullanlan forml verilmitir. Burada kaynak ile birletirilmi malzemenin younluunu, s ise referans numunenin younluunu ifade etmektedir. Buna gre kaynak sonras TiH2 ieren numunelerin kaynak blgelerinde artan akm iddeti ile gzeneklilik orannn artt belirlenmitir. Bu oran 230 A akm iddetinde birletirilen numunelerde maksimum %10 oranndadr. Kaynak ilemi srasnda, yksek miktarda s girdisinden dolay kaynak blgesinde ksmi kprmeler meydana gelmitir. Bunun neticesinde numunelerin kaynak blgelerinde ve diki yzeylerinde gzenekler olumutur (ekil 1). Yap ierisindeki TiH2n 400-450oC gibi dk scaklklarda znerek gaz aa karmas kprme ncesi gzenek oluumunun nedeni olarak grlmektedir [8]. Bu durum kaynakl blgenin ana malzemeye nazaran daha farkl kprme davran sergilemesine neden olmutur. Gzeneklilik oran = (1/s) 100% (1) ekil 2de kalp ierisinde ve serbest olarak tek bir ynde kprtlen preform malzemelerin kpk yap resimleri gsterilmektedir. Serbest kprtme neticesinde kaynakl blgelerin ana malzemeye nazaran ok daha az kprd aka grlmektedir. Bu problemin nedeni kaynak ilemi esnasnda TiH2 kana engel olunamamasdr. Kprtc maddenin dk scaklklarda znerek gaz aa karmas ve bu gazn yap ierisinde muhafaza edilememesi serbest kprtme neticesinde kaynakl blge ile ana malzemenin dorusal genleme oranlarnda nemli lde farklla neden olmutur (ekil 3). rnein 130 A akm iddetinde yaplan birletirmelerde kaynak blgesi % 289 orannda genleme gsterirken, ana malzeme % 338 orannda genleme sergilemitir. Dolaysyla kaynak blgesi ile ana malzeme arasndaki dorusal genleme fark % 49dur. Bu oran 170 Ade % 86, 190 Ade % 102 ve 230 Ade % 133tr. Ayn zamanda ekil 2de kaynakla birletirilmi, birletirilmeden aln alna getirilmi ve yekpare preform malzemelerin kalpta kprtlmeleri neticesinde aldklar son ekil gsterilmektedir. Dikkat edildiinde yekpare numune hari dier numunelerin st ve yan yzeylerinde birletirme blgelerinin izleri grlmektedir. Ancak bu izlerin ara kesit boyunca srekli olmad, yalnzca yzeysel bir iz niteliinde olduu ekil 4te verilen arakesit fotoraflarndan anlalmaktadr. Kprme ilemi esnasnda numunelerin yzeylerinde oluan oksitlenmenin bu izlerin olumasna etki ettii dnlmektedir. Yzeyde oluan oksit katman kpn maruz kalaca scakl etkiledii gibi, geometrik eklini de deitirebilmektedir [9].
ekil 2. Kalp ierisinde ve serbest olarak kprtlen preform malzemelerin kpk yaplar
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ekil 3. Serbest olarak kprtlen numunelerin genleme oranlar ekil 4teki ara kesit resimlerine bakldnda serbest halde kprtme ilemi neticesinde kaynak ile birletirilmi numunelerin ara yzeylerinde ksmi birlemelerin olduu grlmektedir. Kalpta kprtme ileminde ise ara yzeydeki birlemelerin, yeterli lde olduu grlmektedir. Bunun nedeni kprtme ilemi esnasnda kalp ierisinde bulunan numuneler, nce serbest halde kprme davran sergilemekte ve sonrasnda st yzey kalp duvarlar genleme dorultusunu yanlara doru deitirmektedir. Dolaysyla serbest kprtme neticesinde birlemeyen d yzeyler, genleme dorultusu boyunca hareket ederek kalp boluunu doldurmaktadr. Ancak bu ilemler gerekletirilirken kalp ykseklii optimum deerde tutulmaldr. nk gereinden fazla ykseklie sahip olan kalplarda yaplan kprtme ilemlerinde dzgn geometrik ekilli kpk yaplar elde edilememektedir. Kalpta kprtlen numunelerin ara kesit yzeylerine bakldnda, birleme blgeleri ile ana malzemenin gzenek morfolojisinde nemli lde farkllk grlmemektedir. Ayrca bu durum, herhangi bir kaynak ilemine tabi tutulmadan aln alna getirilerek kprtlen alminyum kpklerde de gzlemlenmitir.
ekil 4. Kprtme ilemine tabi tutulmu numunelerin gzenek yaplar 4. SONULAR ve NERLER Yaplan deneysel almalar sonucu kprebilir alminyum malzemeler TIG kayna ile baarl bir ekilde birletirilmitir. Ancak kprtme ncesi kaynak blgesinde oluan gzenekler serbest kprtmede kprebilirlie olumsuz ynde etki ederken, kalp ierisinde kprtmede ise herhangi bir etki oluturmamtr. Ayrca kaynak ile birletiril-
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meden aln alna getirilerek kalpta kprtme ilemine tabi tutulan numuneler ile kaynakl numunelerin gzenek morfolojisinde nemli lde farkllk grlmemektedir. Toz metalurjisi yntemiyle retilecek byk boyutlu alminyum kpkler iin preform malzemelerin aln alna iyi sabitlenmesi gerekmektedir. Aksi halde kprtme ilemi olumsuz sonulanabilir. Bunun iin kaynakl birletirme alternatif bir yntem olarak dnlebilir. Ayrca tasarm aamasnda preform malzemelerin kprtme ncesi ekillendirilebilirlikleri nemlidir. Bunun iin kaynakla birletirilmi preform malzemelerin mekanik zellikleri belirlenebilir. KAYNAKLAR 1. Baumaster, J., US patent, 1992 2. Yu, C.J.,Eifert, H.H., Banhart, J., Baumeister, J., Metal foamingby a powdermetallurgymethod: Production, propertiesandapplications, Mat Res Innova, 2:181188, 1998 3. Hohlfeld, J., Hannemann, C., Vogel, R., Hipke, T., Neugebauer, R., Alternative starting materials for the production of aluminum foam by the powder metallurgical process, Prod. Eng. Res. Devel. 5:2530, 2011 4. Cambronero, L.E.G., Canadas, I., Martnez, D., Ruiz-Roman, J.M., Foaming of aluminiumsilicon alloy using concentrated solar energy, Solar Energy 84:879887, 2010 5. Kramer, I., Simancik, F., Florek, R., Nosko, M., Mllerov, K., Tobolka, P., Mishina, O., FrictionStirWelding of Foamable Materials and Foam Core Sandwiches, 11. Conference on Materials, Processes, Friction and Wear, Vela Luka, 347-352, 2006 6. Drfler, S., Otto, A., Merklein, M., Geiger, M., Processing of Aluminium Foam Sandwich Tailored Blanks, International Conference Advanced Metallc Materals, Smolenice, Slovakia,59-64, 2003 7. Horn H., FrictionStirWelding of AluminiumFoamMaterials In: Proceedings of the International Conference on Joining Technology of Dissimilar Materials and Structural Integrity Problems of so Jointed Structures. Ljubljana, 107-112, 2001 8. Lehmhus, D., Approaches to tailoring titanium hydride decomposition kinetics by annealing in various atmospheres, Adv. Eng. Mat, 2004 9. Solrzano, E., Garcia-Moreno, F., Babcsn, N., Banhart, J., Thermographic Monitoring of Aluminium Foaming Process, Nondestruct Eval, 28:141148, 2009
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WC-Co KESC U HURDALARINDAN PROMETALURJK YNTEMLE WC ve Co TOZLARININ GER KAZANIMI

Engin AHN, Kenan YILDIZ, Fatih STEL Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii, 54187 Sakarya, enginsahin48@gmail.com, kenyil@sakarya.edu.tr, ustel@sakarya.edu.tr ZET Gnmzde WC ve kobalt malzemesinin geri kazanmna ynelik yaklamlar sadece ekonomik faktrler ynnden deil evresel ve ekolojik faktrler nedeniyle de nem kazanmtr. Dnyada kesici ularn imalatnda kullanlan volfram karbrn (WC) te biri hurdalardan salanmaktadr. Son yllarda WC ve Co geri kazanmna ynelik gelitirilen bir teknikle, sert metal ularn hurdalar bir erimi metal (Zn) banyosunda zndrlerek geri kazanlmaya allmaktadr. Bu iki metalin ok farkl zellikleri olmasna karn, Zn-Co ikili denge diyagramna gre birbirleri iinde snrl znrlkleri vardr. Bu durum, sert metal ularnn asit ve uurma proseslerine alternatif bir ekilde daha ekonomik ve evreye duyarl olarak geri kazanmn mmkn klmaktadr. Bu almada WC-Co kesici u hurdas farkl scaklk ve srelerde erimi inko banyosunda tutulmu, inko buharlatrldktan sonra WC ve Co tozlar geri kazanlmtr. Anahtar Kelimeler: WC-Co hurdas, Geri kazanm, Pirometalurji
RECOVERY OF WC AND Co POWDERS FROM WC-Co CUTTING SCRAPS BY PYROMETALLURGICAL METHOD

ABSTRACT Nowadays, the approaches for recovering of WC and Co materials are not only becoming economically important but also, due to the environmental factors, it is ecologically significant. In the world, the one third of the consumption of WC in cutting tools is being produced from their scrap. In recent years, a new technique for recovering of WC and Co using molten zinc (Zn) bath has been developed from hard cutting tool scraps. Although very different properties of these two metals, there is a limited solubility one over another according to Zn and Co binary phase diagram. With this, hard cutting tool materials will be enabled to be recovered alternatively in contrast to acid leaching and evaporation methods. In this study, WC-Co cutting scrap was treated with molten zinc at different temperatures and durations, WC and Co powders were recovered after the evaporation of zinc. Keywords: WC-Co scrap, Recovery, Pyrometallurgy 1. GR Kesici ular, ncelikle talal imalat operasyonlarnda youn olarak kullanlmaktadr. Ayrca ucun karbrn oluturan volfram metali madencilik, elik sanayi, refrakter malzeme, uak uzay sanayi gibi kullanm alanlarna sahip olmakla birlikte volframn byk ounluu kesici takm ucu retiminde (WC olarak) kullanlmaktadr. Kesici u
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retiminde kullanlan semente karbrlerin kullanm sonras nispeten kolay toplanabiliyor olmalar ve hurda olarak yksek ekonomik deere sahip olmalar nedeniyle geri kazanmlar gerek ekonomik gerekse evresel nedenlerle nemlidir. Volframn pahal bir metal olduu dnldnde, geri dnm hayati bir nem arz etmektedir. Bu nedenle kesici ularn geri kazanmna ynelik bilimsel aratrmalar ve endstriyel lekteki almalar uzun yllardan beri devam etmektedir. Volfram karbr kesici ularn geri kazanmna ynelik almalar 3 ana grupta toplanmaktadr. Bunlar; (i) kesici ularn hidrometalurjik asit lii prosesleri (asetik, slfrik, nitrik ve hidroklorik asit), (ii) hidrotermal oksidasyon prosesi ve (iii) yksek scaklk oksidasyonu-redksiyon prosesi ile geri kazanmlar eklindedir. Ayrca daha snrl olarak elektrokimyasal zndrme ve hurda ularn toz haline getirildii mekanik tme proseslerine de bavurulduu grlmektedir. 1970li yllarda ortaya kan inko kazanm prosesi de geri dnm uygulamalarnda kullanlan farkl bir yntemdir [1,2]. Genel olarak kimyasal proseslerin btn hurda trlerini ileyebilme ve empriteleri uzaklatrabilme gibi avantajlar vardr. Fakat bu yntemler yksek maliyet, yksek zc ve enerji tketimi gereksinimi, daha dk verimlilik ve direkt metotlara gre daha fazla atk kmas gibi dezavantajlara sahiptir. Kimyasal geri dnm ile direkt geri dnm prosesleri arasndaki denge, volfram endstrisini geri dntrlen malzemelerdeki emprite seviyesini ve geri dnm maliyetlerini azaltmaya yneltmitir. Bu nedenle volfram bazl hurdalar ilemek iin birok metot ortaya kmtr [3]. Asidik li ilemleriyle geri dnm prosesleri, sert metal u ierisindeki balaycnn zeltiye alnmas ve metal karbr partikllerinin serbest hale gemesi dncesine gre yaplmaktadr. Balayc kobalt metalin zndrlmesine ynelik olarak birok asit bileenleri denenmitir. Her ne kadar kobalt birok asit iinde znse de, emisyon problemleri oluturmadan endstriyel bir proses ina etmek zordur. Slfrik, nitrik veya hidroklorik asit kullanan operasyonlarn evreye olumsuz etkileri bulunmaktadr ve kullanlan dk pH, asidin selektif li zelliine etki etmekte, oluan tungstik asit, li edilen blgelerdeki gzeneklere kerek li ilemini snrlayc etkiler meydana getirmektedir [4]. Bu durumu nlemek iin hurda birka yz mikron boyutuna paralanmakta, ancak bu boyut kltme ilemi maliyeti artrmakta ve demir kirlenmesi meydana geldiinden tercih edilmemektedir. Orijinal boyut ve ekildeki sert metal hurdalarn ekolojik adan li etmek iin asetik asit kullanlmaktadr. Bu yntemin avantajnn hurda boyut kltme ilemine gerek duyulmamas olduu ifade edilmektedir. Asetik asit, balayc kobalt selektif olarak zeltiye almaktadr [5]. Semente volfram karbr hurdalarnn deerlendirilmesinde kullanlan bir dier asidik li ilemi nitrik asitle yaplmtr. Hurda vibrasyonel bir deirmende tlm, akabinde nitrik asitle li edilmi ve balayc olan kobaltn znme verimleri incelenmitir [6]. Nitrik asidin yan sra hidroflorik (HF) asidin de kullanld bir baka almada WC-Co hurdalarnda hidrotermal oksidasyon ilemiyle WO3 tozlar elde edilmi, kobalt ise zeltiye gemitir. Sonu olarak WC-Co hurdalarndan W ve Co kazanmada bu yntemin tercih edilebilir yntemlerden biri olduu belirtilmitir [7]. Bir baka hidrometalurjik deerlendirme ynteminde ise WC-Co hurdalar HCl zeltisinde 110Cnin zerinde hidrotermal ileme tabi tutulmu ve Co balayc faz zndrlmeye allmtr. Kobaltn zndrlerek uzaklatrlmasndan sonra elde edilen WC tozlarnn olduka gevrek olduu ve kolaylkla pulverize edilebilecei de ifade edilmitir [8]. Asit liine benzer bir yntem olarak, kesici u hurdalarndan volfram karbrn ve kobaltn elektrolitik olarak kazanlmas hedeflenmi ve elektrolit olarak kullanlacak farkl asitlerin (HCl, H3PO4) kobalt zmlendirilmesine etkileri tespit edilmitir. Asit liinin uzun sreli olmas ve yksek enerji sarfiyat (1000 Amper) nedeniyle bu yntem kullanmnn ekonomik olmad ifade edilmitir [9]. Oksitleyici ekstraksiyon prosesinde geri dntrme ileminin ilk kademesi hurda, NaNO3 ve NaNO2 gibi oksitleyici bileenlerle kavrulmakta, elde edilen malzeme suyla muamele edilerek sodyum tungstat zndrlmekte, filtrasyon ve ktrme ilemleriyle empriteler uzaklatrlmaktadr. Sodyum iyonlarn ayrmak iin kerosen ve alkil benzen gibi organik zcde amin gibi znen bir maddeyle sodyum tungstat zeltisinde volfram paracklar ekstrakte edilmektedir. Amonyum polytungstat zeltisi elde etmek iin sulu amonyak zeltisi ile yeniden ekstrakte edilip, buharlatrma yntemiyle zeltiden amonyum paratungstat kristalize edilmektedir. Elde edilen amonyum paratungstat kalsine edilip akabinde hidrojenle redklenerek volfram metali elde edilmektedir [2]. Oksidasyon-Redksiyon prosesi de WC-Co sert metallerinin geri dnmnde kullanlan yntemlerden biridir. Bu yntemde WC-Co sert metali dner frnda CoWO4 ve WO3 oksit formlarna dnmekte, daha sonra bu oksit tozlar azot gaz ortamnda kat karbonla W ve Coa karbotermal olarak redklenmektedir [10].
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1970lerin sonunda ticarileen inko geri dntrme prosesinde, temizlenmi hurda asal bir gaz atmosferi altnda 650-800C scaklk aralndaki bir elektrikli frnda bulunan ergimi inko iine daldrlr. inko, balayc olan kobaltla reaksiyona girer ve karbr paracklar orijinal hacminin iki katndan daha fazla bir hacime ier. Optimum koullar Co ieriine ve inko/kobalt oranna baldr. inko vakum altnda 700-950C de destile edilir ve geri kazanlr. Karbr paracklar ince toz haline getirilmek zere pulverize edilir ve elenir. Partikllerin iinde halihazrda kobalt bulunur ve tane boyutu olarak orijinal sinterlenmi hurdadan bir farkllk gstermez [2,3]. inko banyosunda WC-Co sert metal bileiinin geri kazanm veriminin dier proseslere gre %95 daha verimli olduu ifade edilmektedir [11]. Geri dnm erevesinde semente karbrlerin tlerek yeniden retim srecine katlmas ekonomik zorunluluun bir gereidir. ABDde semente karbr hurdalarnn %35inin kimyasal proseslerin kullanmyla, %25inin inko banyosu prosesi ile geri kazanld ve %5 orannda hurdann ise deerlendirilmedii rapor edilmitir. inko prosesinin semente karbrlerin dnmnde kullanm son yllarda artmaktadr[12,13]. Bu alma 110M201 nolu TBTAK projesinin balang almalarn iermekte olup WC-Co kesici u hurdalar erimi inko banyosu iinde farkl scaklk ve srelerde tutularak WC ve Co partikllerinin geri kazanlmas amalanm ve elde edilen veriler sunulmutur.
2. DENEYSEL ALIMALAR 2.1. WC-Co Hurdasnn Karakterizasyonu Deneysel almalarda kullanlan WC-Co kesici u hurdasnn X-n difraksiyon analizi Rigaku Ultima X-In Difraktometresi ile Cu K-alfa kullanlarak yaplmtr. JEOL 6060 LV marka tarama elektron mikroskobu ile hurda malzemenin ve proses sonras elde edilen rnlerin SEM/EDS analizleri yaplmtr. 2.2. Pirometalurjik Geri Dnm Prosesi WC-Co kesici u hurdalarn erimi inko banyosunda zndrlmesi ve WC ile Co tozlarnn geri kazanmnn yapld ve deneysel almalarda kullanlan frn inko oksit retim tesislerinde kullanlan frnn bir kopyasdr. Frn, ayarlanabilir s rejimi ile maksimum 1100C ye kadar kabilmektedir. Frn ierisine, arzu edildii taktirde azot veya argon gaz, istenilen debi deerlerinde beslenebilmektedir. Yaplan deneysel almalar srecinde, inkonun eritilmesi ve buharlatrlmas srecinde ortama srekli olarak koruyucu gaz olarak argon gaz beslenmitir. Bu ekilde inkonun eritilmesinde, erime scakl yksek olan ZnO oluumu nlenmi olup banyo ortamnda metalik karakterde inko bulunmas salanmtr. Erimi inkonun iinde kobalt znmesinin salanmasnn akabinde inkonun buharlatrlmas amacyla frn 1000C ye karlm, bu esnada kullanlan koruyucu gaz, ortamdaki inko buharnn uzaklamasn da salamtr. ekil 1de kullanlan frn(a) ve frn iindeki grafit potann (b) grnts verilmitir. ekil 2de ise erimi inko banyosunda WC ve Co tozlarnn geri kazanm ematik olarak gsterilmitir. Frn alma scaklklar 700, 750 ve 800C olarak seilmi, bu scaklklarda bekletme sreleri ise 1, 2 ve 3 saat olarak kabul edilmitir.
(a)
(b)
ekil 1. Deneysel almalarda kullanlan frn (b) ve frn iindeki grafit pota (b)
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ekil 2. ematik erimi inko banyosunda geri kazanm prosesi Deneysel almalarda yaklak 28 g hurdaya karlk 300 g inko kullanlmtr. Erimi inko banyosunda hurdalar bekletilmi, hurdalardaki kobaltn znmesi salanmtr. inko buharlatrma kademesinde ise ortamda metalik olarak bulunan inko, frnn 1000C ye karlmasyla buharlatrlm, frn dnda bulunan toplama blgesinde kat inko oksit tozlar olarak elde edilmitir. 3. DENEYSEL SONULAR 3.1. Hurdann Karakterizasyonu ekil 3de kesici u hurdasnn X-n difraksiyon analizi, ekil 4de ise hurdann SEM analizleri ile EDS analizleri verilmitir. X-n difraksiyon analizinden grld gibi numunede ana madde volfram karbr (WC) olup kobalt (Co) ve az miktarda vanadyum oksitte (VO) bulunmaktadr.
ekil 3. WC-Co kesici u hurdasnn X-n analizi ekil 4de verilen SEM resimlerinde WC partiklleri belirgin ekilde grlmektedir (1 nolu blge). Partikller arasnda ise (2 nolu blge) kobalta zengin blgeler bulunmaktadr. ki farkl blgeden alnan EDS analizleri, kobalt orannn partikller arasnda daha fazla olduunu gstermektedir.
(1 nolu blge) ekil 4. WC-Co kesici u hurdasnn SEM grnts ve iki farkl blgedeki EDS analizi
(2 nolu blge)
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3.2. Pirometalurjik Yolla WC ve Co Geri Kazanm WC-Co kesici u hurdalar 700, 750 ve 800C de bulunan erimi inko banyosunda 1, 2 ve 3 saat bekletilmi, akabinde frn scakl 1000C ye karlarak inkonun ortamdan uzaklatrlmas salanmtr. Bu ilemler argon atmosferi altnda gerekletirilmitir. Elde edilen rnler tme ilemine tabi tutularak WC ve Co tozlar elde edilmitir. 700C scaklkta yaplan almalarda elde edilen rnlerin ince partikller haline getirilmesi iin yaplan tme ilemleri sonras homojen boyut dalml tozlar elde edilememitir. Bu scakln tam olarak yeterli gelmedii tespit edilmitir. Tm alma scaklklarnda 1 saatlik ilemler, uygun WC ve Co tozlarnn geri kazanmnda yeterli gelmedii de gzlenmitir. 750 ve 800C de inko banyosunda 3 saat sre beklenmesi sonrasnda elde edilen partikller ekil 3(a ve b)de grlmektedir. inkonun ortamdan uzaklatrlmasnda sonra elde edilen partikller sngerimsi yapda olup tme sonras kolaylkla toz haline gelmektedir. Scaklk arttka daha kolay tme ve levhasal ekilde daha kk boyutta tozlar elde edilmitir.
ekil 5. inko banyosunda (a) 750C de ve (b) 800C de 3 saat ilem sonras elde edilen tozlar ekil 5de grlen levhasal bir partikln 10000 bytme ile elde edilen SEM grnts ve burann alan analizi ekil 6da verilmitir. ekil 4den de grlecei zere, balayc olan kobaltn ayrlmas sonucu partikl yzeyinin sngerimsi bir grnmde olduu anlalmaktadr. 1 mden kk WC paracklarnn bulunduu bu tozlar, erimi inkoda geri dnm prosesi sayesinde elde edilmitir ve yaplan EDS analizlerinde kalnt inkoya rastlanmamtr. Geri kazanlan bu tozlar, daha ileriki aamalarda birok ama iin tekrar kullanlabilecek durumdadr. Mevcut alma devam etmekte olup elde edilen tozlarn daha detayl karakterizasyonu ve kaplama sektr gibi uygulamalarda kullanm da test edilecektir.
ekil 6. inko banyosunda 800C de 3 saat ilem sonras elde edilen WC partikl yzeyinin SEM ve EDS genel analizi 4. SONULAR WC-Co kesici u hurdalar erimi inko banyosunda farkl scaklk (700,750 ve 800C) ve farkl srelerde (1, 2 ve 3 saat) bekletilerek kobaltn znmesi salanm, ortamdaki inko uzaklatrldktan sonra WC ve Co tozlar geri kazanlmtr. Yaplan deneyler sonucunda 1 saat gibi ksa sreli ilemlerde yeterli kobalt znmesi salanamam, sre 3 saate ktka daha kk boyutta ve levhasal WC partiklleri elde edilmitir. Teekkr: 110M201 nolu proje kapsamnda yaplan bu almaya verdikleri maddi destekten dolay TBTAK kurumuna teekkr ederiz.
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KAYNAKLAR 1. Gotou, H., History of Igetalloy, SEI Technical Review, No.68, p.1-10, April 2009. 2. Sudarshan, T.S., Nano-sized WC-Co holds promise for the future, MPR, p.26-33, March 1998. 3. Shed, K.B., Tungsten recycling in the United States in 2000, USGS, Open-File Report 2005-1028, 2005. 4. Schiesser, R., Werstoff-Recycling wolframhaltiger sekundarrohstoffe, PhD Thesis, TU-Vienna, 2003. 5. Edtmaier, C., Schiesser, R., Meissl, C., Schubert, W.D., Bockb, A., Schoen, A., Zeiler, B., Selective removal of the cobalt binder in WC/Co based hardmetal scraps by acetic acid leaching, Hydrometallurgy, 76, p.6371, 2005. 6. Grmen, S., Recovery of nano-sized cobalt powder from cemented carbide scrap, Turkish J. Eng. Env. Sci., 29, p.343-350, 2005. 7. Sasai, R., Inagak, F., Itoh, H., Resource recovery from cemented carbide by subcritical hydrothermal treament, Journal of the Soc. of. Materials Science, Japan, Vol 55. No.3, pp. 254-257, 2006. 8. Kojima, T., Shimizu, T., Sasai, R., Itoh, H., Recycling process of WC-Co cermets by hydrothermal treatment, Journal of Material Science, 40, p.5167-5172, 2005. 9. Karayazgan, N., WC-Co esasl kesici ularn elektrolitik geri kazanm, Yksek Lisans Tezi, T Fen Bil. Ens., 2005. 10. Joost, R., Pirso, J., Viljus, M., Recycling of hardmetal scrap to WC-Co powder by oxidation-reduction process, 6th International DAAAM Baltic Conference, 24-26, Tallinn-Estonia, April 2008. 11. http://www.hmtg.de/ 12. Stjernberg, K., Johnson, J.JR., Recycling of cemented carbides, in 1998 Int. Con. on Powder Metallurgy & Particulate Materials, Las Vegas, Nev., May 31-June 4, 1998, Proceedings: Princeton, N.J., Metal Powder Industries Federation and APMI International, 1, 1998, p. 173-179. 13. Payne, M., U.S. Tungsten market update: International Tungsten Symposium-Outlook for Tungsten Production and Applications in the 21st Century, 9th, Pittsburgh, Pa., , Presentation, 19 p., September 30-October 4, 2002.
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SNTEST Toz metal paralarda atlak ve gzeneklilik tespiti iin gelitirilmi tahribatsz enstrman
A.ATAS1, A. Bulkai2, P. Tomek2, G. Tth2 1TOZMETAL Tic. Ve SAN. A.S. stanbul Cad.No:61 Grpnar, Bykekmece, stanbul, TRKYE www.tozmetal.com 2MFKK Invention and Research Centre Services Co. Ltd, 1119, Ttnyi t 93, Budapest, HUNGARY www.mfkk.hu ZET Geleneksel otomobil pazar ierisinde Toz Metal paralara olan talebin artaca ngrlmektedir, fakat sektrn gelecekteki gelimesi direkt olarak uzay ve ila endstrilerine sfr hatal para retebilme kabiliyetine baldr. Kalite gvence penceresinden bakldnda, yeterli kontrol sisteminin olmamas kontrol maliyetlerini, test iin harcanan zamanlar ve sarf edilen malzeme miktarn arttracandan olduka nemlidir. Son yllarda Eddy Current, bilgisayarl tomografi, X-Ray grntleme gibi birok tekniin Toz Metal paralarn kontrol iin uygulanabilirlii aratrlmtr. Fakat yaplan almalar gstermitir ki bu yntemlerin hepsin eksik olduu noktalar vardr ve bu durum onlar tam ve gvenilir bir atlak tespiti ya da younluk problemi tespiti iin geersiz klmaktadr. Avrupa Birlii Komisyonu fonlar kullanlarak, pulse echo ultrasonik teknolojinin robot teknolojisiyle birletirilmesiyle sinter paralarn global bir younluk haritasnn karlabildii yeni bir kontrol ekipman gelitirilmitir. Anahtar Kelimeler tahribatsz muayene, kalite kontrol, sinterlenmi paralar, kusur tespiti, younluk haritas, ultrasonik gzeneklilik tespiti, ultrason sinyal ileme
SINTEST - Non-InvasIve Instrument for determInIng the porosIty of powder metallurgy parts
Abstract The demand for P/M parts in its traditional automotive market is predicted to grow, but future sector expansion depends directly upon its capability to manufacture zerodefect parts for industries such as aerospace and medicine. The lack of adequate inspection systems has important implications from the view of quality assurance, since it increases the costs, time and wasted material. In recent years the applicability of several techniques for the inspection of P/M parts have been investigated, such as Eddy current testing, computer tomography or X-Ray imaging, but studies have revealed that all of them have deficiencies that make them unavailable for a complete and reliable flaw detection and density defect recognition. Using funding from the European Commission, a new inspection tool has been developed based on pulse echo ultrasonic technology combined with robotics, which makes it possible to provide a global density map of sintered parts. Keywords - non-destructive test, quality control, sintered parts, flaw detection, density mapping, porosity ultrasonic inspection, ultrasound signal processing 1. GR Toz metalurjisi (T/M) mekanik paralarn metal tozlar ve dier bileenlerden retilmesidir ve ok geni bir alanda endstriel sinter para retiminin temel retim rotasdr. Bugn otomotiv endstrisi T/M paralar iin en byk pa-
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zardr ve toplam pazarn %70ini oluturmaktadr. Bununla birlikte T/M paralar endstriyel eitlilik ierisinde dk maliyetleri ve fonksiyonel esneklilikleri sebebiyle dnya apnda olduka talep grmektedir. T/M firmalar, elektrikelektronik sektrne, ev gereleri sektrne, el aletleri retimine, hidrolik sektrne, motor ve manyetik malzeme retimine, savunma sanayine ve birok dier sektre mekanik paralar retmektedir. Dnya T/M pazarnn senelik sat 30 milyar Euroyu amaktadr. Sektrn gelecekteki genilemesi direk olarak uzay teknolojileri, tp sektr ve sfr hatal retim talep eden sektrler gibi alanlara ok daha karmak mekanik zelliklere sahip yksek kaliteli T/M para retebilmesine baldr. Bununla birlikte bu yksek standartlarda para retebilmek iin mevcut retim srelerinin optimize edilmesi uzun zaman alacaktr, nk paralarn iyaplarn test edebilmek iin gerekli, hzl ve sistematik ekipmanlar ya da test prosedrleri yoktur. Son yllarda Eddy Current, bilgisayarl tomografi, X-Ray grntleme gibi birok tekniin Toz Metal paralarn kontrol iin uygulanabilirlii aratrlmtr. Fakat yaplan almalar gstermitir ki bu yntemlerin hepsin eksik olduu noktalar vardr ve bu durum onlar tam ve gvenilir bir atlak tespiti ya da younluk problemi tespiti iin geersiz klmaktadr. Diren testi, gaz geirgenlik testi, manyetik partikl testi gibi geleneksel test yntemlerine ait yaynlarda da umut verici sonular elde edilememitir. Bir T/M parann blgesel gzenekliliinin tespitinde en gvenilir yntem parann sinterleme sonrasnda kesilip, parlatlp bu parlatlm yzey zerinde mikroskop altnda iyapsndaki hatalarn incelenebildii optik mikroskop yntemidir. Ne yazk ki bu yntemle ie yarayacak sonular elde edebilmek iin numunelerin ok zenle hazrlanmas gerekmektedir ve bu durum da yntemi hem yava hem de pahal yapmaktadr. Kalite gvence penceresinden bakldnda yeterli muayene ynteminin olmamasnn nemli etkileri vardr. Ne yazk ki bugn sinterlenmi paralarn iyapsn uygun bir ekilde ortaya karmaya ynelik bir test yntemi yoktur. T/M paralarn iyaplarndaki hatalar ya da younluk sapmalar gibi durumlara ait kolay eriilebilir ve gvenilir bilgiler elde edilememesi Toz Teknolojisinin yaygnlamasn engellemekte ve kullanmn standart para retimiyle snrlamaktadr. Bu gelimeler T/M paralarn hat zerinde daha etkin bir ekilde kontrol edilmesini salayan yeniliki, etkili ve dk maliyetli, ultrasonik teknoloji tabanl bir sistemi iaret etmektedir. Yeni kontrol ekipman pulse echo ultrasonik teknoloji tabanl gelitirilmitir ve bu da sinter paralarn global bir younluk haritas karlabilmesini mmkn klmaktadr. Bu sayede pazardaki rnn daha iyi bir ekilde kontrol salanabilecek, reticinin T/M para tedarii asndan gvenilirlii ve rekabet gc artacaktr. Ultrason teknolojisi hali hazrda kompak formlarda retim hattnn zerinde, ksmen ezamanl, volumetrik muayene sistemidir. 2. HEDEFLER Bu alma toz metalurjisi ile retilmi paralarn muayenesi alannda aratrma ve gelitirme yapmak amacyla mevcut teknolojinin zerine kurulmutur. Bununla birlikte sinter paralarn (bitmi rn) younluk haritasn elde etmek amacyla ultrason teknolojisine dayanan yeni bir yaklam kullanlacaktr. Ultrason tahribatszdr, X-ray gibi iyonize radyasyon eklinde deildir ve bu sebeple znde olduka gvenlidir. Ultrasonik sistemler uzun periyodlarda ksmen dk altrma maliyetleriyle kendi hallerinde alr halde braklabilirler. Bu alma T/M endstrisinin iki temel ihtiyacn yerine getirecektir: 1. Bitmi rnn performansn ciddi risk altna sokacak i yzeydeki atlaklarn hzl ve gvenilir ekilde tespit edilmesi ve bylece btn hatal paralarn retim hattnn sonunda ayrlabilmesi. Ultrason teknolojisi birok endstride hasar ve korozyon tespiti, kalnlk lm ve kaynak ve malzeme analizlerinde kullanlyor olduundan tahribatsz muayene iin uygun bir enstruman olduunu kantlamtr. Mevcut birok ticari hasar tespit enstruman metaller, plastikler ve kompositler gibi mhendislik malzemelerinde gizli iyap hatalarn tespit edebilirler. 2. Sinter paralarn iyap younluk haritalarnn karlarak muhtemel blgesel younluk hatalarn tespit edilmesi ve bu sayede parann alma esnasnda orta vadede yaratabilecei sorunlar ortadan kaldrlmas. Bu bilgi parann final kalite kontrol srasnda ok kullanl olabilecei gibi yeni paralara yeni kalplar tasarlamak iin gerekli zaman ve maliyetleri de azaltacaktr. 3. METODOLOJ SINTEST iki ana alana blnebilir. Sistemin kalbi, kendine zg bir bilgisayar yazlm ile kontrol edilen 6 eksenli bir robotik kol ile retim prosesine entegre edilebilen, pulse echo ultrason teknolojisidir.
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3.1 Ultrasonun Kullanm Sistem pulse-echo yaklamyla tek transduser kullanr. Ayn transduser ultrasonik dalgalar retir ve test edilen paradan geri dnen yanklar alglar. Hem transduser hem de test paras evrelerinde dolaan ultrasonik dalgalarn transmisyonunu kolaylatrmak amacyla bir svya daldrlrlar. Sistemin emasn ekil 1.de grebilirsiniz
ekil 1. Ultrason alt sisteminin emas Sistem bloktan olumaktadr. Ultrasonik transduser, ultrasonik verici ve ultrasonik alc. Ultrasonik verici ultrasonik transdusere elektrik voltaj demetleri gnderir. Ultrasonik transduser de bu demetlerden ultrasonik sinyaller retir. Sinyal tekrarlama frekans ise harici bir bilgisayar tarafndan kontrol edilir. Ultrasonik transduser tarafndan retilen elektrik sinyalleri alcya geldiklerinde genellikle ok zayflardr ve bilgisayara iletilip ilenmeden nce alc tarafndan ykseltilmesi gerekir. Birok alternatif denendikten sonra ticari olarak bulunabilen odakl daldrmal prob seilmitir. Transduserin ana parametreleri aadaki gibi zetlenebilir. retici: Panametrics-NDT Model: V324-SU Frekans: 25 MHz Nominal eleman bykl: 6 mm diameter Odak: 50,8 mm
Ultrasonik verici ultrasonik transdusere elektrik voltaj demetleri gnderir. Ultrasonik transduser de bu demetlerden ultrasonik sinyaller retir. Sinyal tekrarlama frekans ise harici bir bilgisayar tarafndan kontrol edilir. Verici aadaki spesifikasyonlar gerekletirir: Maksimum negatif voltaj demeti k: 300 Va kadar Sinyal tekrarlama frekans: 5 kHz (dardan kontroll) Ultrasonik transduser tarafndan retilen elektrik sinyalleri alcya geldiklerinde genellikle ok zayflardr ve bilgisayara iletilip ilenmeden nce alc tarafndan ykseltilmesi gerekir. Alc bir zaman ilerleme kontroll ykselticiden (Time Gain Controlled Amplifier, TGCA), bir voltaj rampa reticiden ve bir logaritmik ykselticiden olumaktadr. TGCA, ultra dk ses ykselticisi ve deiken alg ykseltici ieren Analog Devices marka AD8331 entegre devre temeline dayanmaktadr. TGCAnn alglad sinyaller bir voltaj rampa retici tarafndan control edilir ve dolam mesafesi ierisinde ultrasonik dalgalarn zayflamasn geen zaman ierisinde telafi ederek sinyalleri ykseltir. Logaritmik ykseltici Analog Devices marka AD8310 entegre devresi tabanldr. Alcnn spesifikasyonlar aadaki gibi zetlenebilir: Bant Genilii: 50 MHz Alg aral: 14 - 110 dB Giri empedans: 300 k empedans: 50
Elde edilen sinyaller sonularn yorumlanmasn kolaylatrmak amacyla grntlere dntrlerek ilenirler. Sonular B-scan ve C-scan grntleri eklinde sunulur. B-scan grntleri ardk noktalardan geri dnen sinyallerin yakalanp birletirilerek bir doru haline getirilmesiyle oluturulur. C-scande ise sinyalin yansyan enerjisi muayene edilen alann her bir noktasnda bir renkle temsil edilir. B-scan grntleri bir doru oluturacak ekilde ardk olarak test edilmi noktalardan elde edilen sinyal genliini (nceden artlandrlm) temsil edecek ekilde oluturulur. B-scan grntleri parann dikey bir kesiti eklindedir ve grntdeki renk deiiklikleri ya gzeneklilikle ya da atlaklardan kaynakl kesintilerle alakaldr. Dier taraftan C-scan grntleri bir alan oluturacak ekilde test edilen
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ardk noktalardan yansyan sinyalin enerjisini temsil edecek ekilde oluturulur. C-scan grntler test edilen parann yatay bir kesitini temsil eder ve sadece belirli bir derinlik aralndan elde edilen enerjinin birletirilmesiyle oluturulur. Bu sebeple bu tr bir grntde atlak olan bir yerden ok daha fazla enerji yansyacandan kolaylkla renk farkllklar grebiliriz. 3.2 Online Direkt Robot Kontrol Prototip srasnda probun manipulasyonu iin NX100 endstriyel robot kontrol tarafndan ynlendirilen bir Motoman HP6 ok kullanml robotu kullanlmtr. NX100 kontrolrnn RS232 ve Eternet gibi harici iletiim kanallar olduundan cihazla kiisel bilgisayarlarda Motoman tarafndan gelitirilmi iletiim protokol kullanlarak kolaylkla iletiim kurulabilmektedir. SINTEST projesinde pahal orijinal ktpane yerine robotun uzaktan kumandasn ve sistemin kontroln gvence altna alcak ekilde bilgi alveriini salayan kendi ktphanesi oluturulmutur.
ekil 2. NX100n iletiim protokol ekil 2.de grld gibi iletiim iki ana faza ayrlmtr; balatma ve iletiim. Balatma sadece bir kez program balangcnda yaplr. letiim basit bir UDP datagram zerinden komut ve mesajlar yaln tekst formatnda gndererek ve alarak yaplr. Komutlar basit bir yolla gnderilirken ve alnrken mesajlar zel balklar eklinde ksaltlrlar. Ayrca Microsoft Game Studio 3.1 ve NET Framework 3.5 ieren en yeni ve en stn 3D ( boyutlu) grntleme teknolojisi kullanlarak zel bir ok evreli GUI (Graphical User Interface, Grafiksel Kullanc Arayz) gelitirilmitir. Bu kendine zg aralar ilemci zamannn ounu veri analizine ayracak ekilde hesaplama gerekliliklerinin greceli olarak dk seviyelerde tutulmasna olanak vermitir. GUIde gerek ortamn bir dijital modeli oluturulmu ve robotu ve lmn yaplaca tezgah da ierecek ekilde kalibre edilmitir. Model ayrca bir alma alanna da aktarlabilir ve zel bir algoritma, ultrasonik sensrn hareket edecei yolu istenilen znrlkte otomatik olarak hesaplar. Hesaplama test edilecek parann ekline dayanr ve sonu olarak her nokta ilgili yzey noktasndan tam olarak eit mesafede olacak ekilde tespit edilir. ekil 3.te model ve prob hareketi hesaplamas grlebilir. Sanal bir ortama sahip olmas sebebiyle sistem lmn tamamn kendi kendine simle edebilir ve bu sayede sensrn sistemin dier bileenlerine arpp arpmayaca tespit edilebilir. Bu da sensr kafasnn korunmasn kolaylatrr. Bu zellik ayrca btn bir set parann taranmas iin gerekli zamann evirimd bir simulasyonda hesaplanmasna olanak verdiinden sre planlamasnn erken fazlarnda da kullanl olabilir. Aktr ki eer bilgisayara balanm bir robotunuz varsa onu direkt olarak istediiniz yrngede kontrol edebilirsiniz. ok zel durumlar iin bir hareket izleme sistemi de mevcuttur ve bu sistem birleme yerlerinin pozisyonlarn tanmlayarak ya da ekipmann pozisyon ve oryantasyonunu ileterek robot kolun direkt kontroln garanti altna alr.
ekil 3. SINTESTin grafiksel kullanc arayz
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4. SONULAR Ultrasonik sistemin tasarmnn uygunluunu onaylamak iin birok deneme gerekletirilmitir. Denemeler daha nce karakterize edilmi T/M paralardan seilmi rnekler zerinde gerekletirilmitir. Gzenekliliin deerlendirilmesi asndan sistemin performans ekil 4.te grlen ayn geometrili parann deiik basn altnda sktrlm ve bu sayede deiik younlukta elde edilmi rnekleri zerinde kantlanmtr.
ekil 4. Gzeneklilik/Younluk lmnde kullanlan rnek paralar Sonular B-scan grntleri olarak sunulmutur. ekil 5, 6 ve 7 incelenen numunenin ayn kesitindeki B-scan sonularn gstermektedir. ekiller kesitin sadece kk bir alann gstermektedir. Bu ekillerden de grlmektedir ki younluk ne kadar dkse o kadar deiken bir grnt elde edilmektedir. Bunun sebebi younluk dtke gzenekliliin artmas ve bu sebeple ultrasonik dalgalarn ok daha fazla yansmaya uramasdr. Bu grntler bir iso-genlikli hat tespit algoritmas vastasyla numuneler arasndaki farkllklar arttrmak iin ilenmitir.
ekil 5. rnek # 1in B-Scani (younluk 6.85 g/cm3)
ekil 6. rnek # 2nin B-Scani (younluk 6.07 g/cm3)
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ekil 7. rnek # 3n B-Scani (younluk 5.51 g/cm3) Ultrasonik sistem sinterlenmi numunelerde atlak tespiti iin de deerlendirilmitir. ekil 8.de lmlerde kullanlm T/M paray grebilirsiniz. Bu paralarda i kademe kenarnda ekil 8.de belirtilen blgede atlak olduu rapor edilmitir.
ekil 8. Numunelerdeki hasarl blgeler Numunedeki atlaklar ok ak ekilde B-scan grntlerde fark edilebilmektedir. atlak blgeden gelen yanklar yzeyin yaklak 2 mm. altnda, sv ve numune ara yzeyinden hemen sonradr. atlak tespiti ekil 9 ve 10daki hasarl ve hasarsz paralarn kyaslama grntlerinde ok daha ak yaplabilir.
ekil 9. Hasarsz rnein (stte) ve hasarl rnein (altta) radyal ynde B-Scan grntleri
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Ayrca hasarl paradaki atlaklar ok ak ekilde C-scan grntsnde de (krmz blgeler) fark edilebilmektedir. atlak tespiti ekil 11de de gsterildii ekilde hasarl ve hasarsz parann kyasland grntler zerinde ok daha kolaylkla yaplabilir.
ekil 10. Hasarsz rnein (solda) ve hasarl rnein (sada) D apa dik ynde B-scan grntleri
ekil 11. Hasarsz rnein (solda) ve hasarl rnein (sada) tm yzey C-scan grnts 5. DEERLENDRME Yaplan deneyler gstemitir ki ultrasonik dalgalar hatalarn ve hasarlarn ounlukla mevcut olduu derin blgelere ulaabilmektedirler. Ayrca deneyler gstermitir ki ultrason teknolojisi sinter paralarda younluk ve gzeneklilik farkllklarn, hasar ve atlak tespitini olanakl klmaktadr. Bu laboratuar testleri pulse echo ultrason teknolojisinin toz metalurjisi endstrisinde tahribatsz muayene iin ok uygun bir yntem olduunu kantlamtr. Sonular bu teknoloji kullanlarak hasarn ak grsel bir sunumunun elde edilebileceini gstermitir. Bu da hatalarn bykl ve yerinin tespitinde kullanlabilir. Bu sebeple teknoloji sadece grntleme/tespit amal olarak deil kalp tasarm ve retim srelerindeki parametrelerin iyiletirilmesine yardmc olacandan bir kalite gvence ekipman olarak ta deerlendirilmelidir. Sistemin bir dier ana avantaj ise maliyetidir. lmler iin tek bir prop kulland iin gerekli ekipman snrldr. Sistemin veri analizi dahil ultrasonik ksm ve robot kontrol bileenlerinin toplam maliyeti birka
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bin Eurolar civarndadr. Ve bu miktar dier T/M muayene ekipmanlarna kyasla olduka nemsizdir. Sistemin en pahal ksm endstriyel robottur fakat yazlm herhangi bir robota kolayca adapte edilebilecek ekilde gelitirilmitir. Bu esneklik kullancnn sistemi kendinde mevcut bir robota ya da ikinci el bir robota adapte etmesine olanak verir. Muayene iin gerekli hassasiyet greceli olarak dktr ve bu sebeple bu uygulama iin bir orta zellikli robot yeterli olacaktr. Bu durumlar gze alndnda SINTEST muayene ekipman nihai sat fiyat 25.000 Euroyu gemeyecektir ve bu da rekabet gcnn olduka yksek olacan gstermektedir. Teknoloji uygunluu laboratuar koullarnda yaplmtr ve endstriyel uygunluk iin ekipmann eksiksiz ve evrensel bir ekipman olduunu kantlamak amacyla denemeler ferritler dahil deiik T/M paralar zerinde devam edecektir. 6. TEEKKR SINTEST projesi Avrupa birlii Komisyonunun 7. ereve Program tarafndan deneklendirilmi ve MFKK firmas tarafndan koordine edilmitir. Proje bir konsorsiyum tarafndan yrtlmtr bu sebeple Tozmetal A.S, Sinterpress S.L, Danalco Wear & Welding Tech, TKI-Ferrit, M-iNG I&I, Ingenieurbro Gammatec, & Multitest Ltd. dahil btn partnerlere teekkrlerimizi sunarz.
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BORON
www.turkishpm.org
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HOLDING CONDITIONS ON MECHANICAL PROPERTIES OF CAST AL-B ALLOYS

Necip Fazl YILMAZ*, Mehmet ZTRK** *Gaziantep University, Faculty of Engineering, Department of Mechanical Engineering, 27310, Gaziantep, Turkey, nfyilmaz@gantep.edu.tr **Gaziantep University, Faculty of Engineering, Department of Mechanical Engineering, 27310, Gaziantep, Turkey, mehmetozturk@gantep.edu.tr ABSTRACT In this study, mechanical properties of Al-B alloys, prepared by the addition of borax to 99.70% pure commercial aluminum, were investigated. In this process, amount of borax, holding temperature and holding time were realized as affecting parameters. By considering these parameters three specimens were prepared for each condition and they were subjected to mechanical tests such as tensile and impact tests. As a result of tests, tensile strength of the alloy with the incorporation of borax was found 33% increase in comparison to pure aluminum while 21% increase in impact energy value. A substantial quantity of aluminum-boride flakes were observed in the microstructural investigation of the samples. Keywords: Al-B alloy, Mechanical Properties, Metal Alloys, Casting 1 INTRODUCTION In recent years, investigations in finding new materials superior than the conventional ones and improving the already existent materials properties have an increasing demand to respond the need in the use of light-weight functional material in emerging industrial applications. In this regard, stimulated intensive research activities have been observed on aluminum alloys [1-3]. The most important characteristics of Al alloys are low density, high strength-weight ratio and resistance to corrosion that have enabled them to be one of the dominant structural material families of the 21th century. Mechanical properties of Al can be greatly improved by incorporating with some chemical elements. Pure aluminum has a tensile strength of about 49 MPa and if it is formed into an alloy this value can be increased up to around 700 MPa [4]. Most of the chemical elements possessing metallic characteristics readily alloy with aluminum, but only a few are important major alloying ingredients in commercial aluminum-base alloys. The typical alloying elements are copper, magnesium, manganese, silicon, and zinc [5]. Al-B alloys are widely used commercially in the production of electrical conductive grade aluminum to scavenge transition metal impurities, such as titanium, vanadium, chromium and zirconium elements and have also great importance for its usage as grain refining agent for aluminum castings [7-10]. In this work, boron element was used as an alloying element to investigate a new generation aluminum alloy. This paper presents the experimental studies to determine the mechanical properties such as tensile and impact properties of the cast Al-B alloy. 2 EXPERIMENTAL PROCEDURE 2.1 Materials Materials used in this study were 99.70% pure commercial aluminum (AA1070) and borax powder (Na2B4O7.10H2O). Primary unalloyed aluminum ingots were obtained from Seydisehir Aluminum (Turkey) and borax was provided from Eti Mine Works (Turkey). The chemical composition of AA 1070 aluminum used in the present work is given in Table 1. Main impurities of AA 1070 aluminum are iron and silicon. In this study borax was used as a boron source to produce Aluminum-Boron alloy.
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Al 99.7
Cu 0.04
Table 1. Chemical Composition of AA 1070 (%) Fe Mg Mn Si Ti V Zn 0.25 0.03 0.03 0.2 0.03 0.05 0.04
Others 0.03
2.2 Manufacturing Conditions and Specimens During the experimentation, conventional casting method was used to produce aluminum-boron alloys. Some fabrication parameters were established to compare the effects of parameters on the mechanical properties of alloys [11]. All these parameters and mutual dependence are demonstrated in Figure 1.
Figure 1. Parameters Used in the Experiments Borax addition was performed within 5, 10, 15 and 20 weight percentage of pure aluminum and three temperatures, namely: 800, 1000 and 12000C were carried out during casting process. All samples were also hold 30, 45 and 60 minutes in the oven at elevated temperatures before casting into dies. The preparation steps of Al-B alloys were considered to consist of three distinct and consecutive steps (Figure 2).
Figure 2. Production Steps of Al-B alloys Fabrications of alloys were carried out on an about 400 gram batch scale. AA 1070 aluminum alloy ingots were placed into a graphite crucible with borax powder together and were brought to predetermined temperature using an electrical resistance furnace. The molten alloy thus obtained was held to establish a reaction between the aluminum and borax. During holding dross was generated on the surface and this dross provided an effective mechanism for protecting the molten alloy from the environmental effects. There was no stirring during holding to avoid excessive oxidation. Before casting into a permanent mold, dross was skimmed off from the surface and the melt was stirred thoroughly with graphite rods for 30 seconds to ensure homogeneity. As a last step, the melt was poured into a metal mold, made by cast iron, with a diameter of 20 mm and a height of 200 mm. Mechanical tests play a significant role in evaluating fundamental properties of materials. All samples were subjected to tensile and impact tests to observe the variations of mechanical properties. The tensile test was carried out on a cylindrical specimen with a gauge length of 75 mm and a diameter of 15 mm by using Shimadzu AGX universal testing device at RT. Impact test was performed on specimens with square cross section 10x10 mm and length of 55 mm by using Tinius Olsen charpy-type impact test equipment at RT. All impact test specimens have v type notch with the degree of 45 and 2 mm depth. Tensile and impact specimens are shown in Figure 3.
a) Tensle
B) Impact
Figure 3. Specimens for Tensile and Impact Testing
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3. RESULTS AND DISCUSSION Many experiments were carried out during this work but only 45 test results were emphasized in this paper. All test results were evaluated by averaging the results of 3 successive measurements in every sample. 3.1 Tensile Properties Tensile test results of samples as UTS values with and without incorporating borax are presented in Table 2. The data reveal that certain amount of borax addition increases ultimate tensile strength of pure aluminum. Table 2. Tensile Test Results (MPa) Pure %5 Borax 800 1000 1200 800 1000 1200 (0C) (0C) (0C) (0C) (0C) (0C) 30 min 52,2 54,7 49,1 62,0 64,6 59,7 45 min 58,7 59,7 51,1 63,6 79,5 72,6 60 min 55,9 53,1 50,9 67,0 73,5 70,5 %10 borax 800 1000 1200 (0C) (0C) (0C) 62,7 72,8 61,1 71,8 78,1 73,7 67,7 75,3 63,7 %15 Borax 800 1000 1200 (0C) (0C) (0C) 66,8 73,8 50,5 73,0 76,0 53,2 75,1 75,2 58,8 %20 borax 800 1000 1200 (0C) (0C) (0C) 71,2 66 52,3 70,6 68,5 56,4 67,7 63,5 54,7
The variations in the measured UTS value according to borax addition and holding times for varying holding temperature are respectively plotted in Figure 4. Highest UTS values were recorded at 5 and 10% borax addition as 79.5 and 78.1 MPa respectively. As shown in Figure 4, it is very clear that increasing holding temperature from 8000C to 10000C resulted in greater UTS values. Increasing holding temperature to 12000C has almost completely negated the UTS value of the samples almost in all conditions. When the effect of holding time on tensile test results are taken into consideration, holding time increasing up to 45 minutes improved UTS value almost in all cases. Holding for more than 45 minutes does not seem to offer any improvement in UTS values.
Figure 4. UTS variations of the samples
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3.2 Impact Properties Impact test results are depicted in Table 3. Data indicate that certain amount of borax addition to the pure aluminum yielded an improvement in impact resistance. Table 3. Impact Test Results (J) Pure %5 Borax %10 borax %15 Borax 800 1000 1200 800 1000 1200 800 1000 1200 800 1000 1200 (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) (0C) 4,7 4,9 1,1 6,0 6,2 1,8 5,9 6,6 1,1 6,2 6,1 1,3 5,0 5,7 1,2 6,6 6,9 2,1 6,2 6,8 1,2 6,7 6,7 1,0 4,5 4,1 0,9 6,2 6,5 3,3 5,5 6,7 1,1 6,6 6 0,9 %20 borax 800 1000 1200 (0C) (0C) (0C) 6,4 6,1 1,2 6,4 5,7 1,4 6,5 5,4 1,4
30 min 45 min 60 min
Variations of the impact energy value of the samples as a function of holding temperature for varying holding times and borax addition are displayed in Figure 5. The greatest impact energy values were obtained at 5 and 10% borax addition as 6.9 and 6.8 joule respectively. There is strong relationship between the holding temperature and impact energy as seen in Figure 5. Increasing holding temperature up to 10000C improved impact energy values. A significant point was observed that increasing holding temperature from 10000C to 12000C resulted in a dramatic reduction in impact resistance for both pure aluminum and alloyed samples in all conditions.
Figure 5. Impact Energy Variations of the sample Higher impact energy values were observed when the holding time increased from 30 to 45 minutes. However, further increasing holding time caused a reduction in impact energy values. Maximum results obtained from the tensile and impact tests and their fabrication conditions are summarized in Table 4.
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Table 4. Maximum Test Results Borax (%) Tensile strength (MPa) Impact Energy (kg.m) 3.3 Microstructure Standard metallographic procedures were employed to prepare the produced samples. In this work, specimens firstly were cut transversally in a band saw with a height of 20 mm then fixed into Weber mounting device. In order to obtain a highly reflective surface for microscopic examination that is free from scratches and damages, the specimens were carefully grinded and polished. All samples were gently grinded with 240, 400, 600, 800, 1000, and 2000 mesh SiC emery papers. Afterwards samples were roughly polished by 6 and 1 diamond solutions and then final polishing was performed by colloidal silica to obtain highly reflective surface. All grinding and polishing operations were made with Metkon Forcipol 2V grinding and polishing device. All samples were chemically etched with 0.5 ml hydrofluoric acid (HF) in 100 ml pure water for 45 seconds [6]. The microstructure examinations of the alloyed samples have been done by Nikon MA-100 optical microscope. 5 5 Holding Temperature (0C) 1000 1000 Holding Time (min) 45 45 Pure 59.7 5.7 Max. Value 79.5 6.9 Increment 33% 21%
(a)
(b)
(c)
Figure 6. Microstructure of produced Al-B alloy: a) 10X b) 50X c) 100X
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Figure 6 depicts the microstructure of the sample prepared by holding 45 minutes at 10000C with the addition of 5% borax, which has the highest UTS and impact energy value. The bright region represents the aluminum, the dark gray particles as aluminum-borides in micrographs. A substantial quantity of thick and long aluminum-boride flakes are observed in microstructure. 4. CONCLUSIONS A systematic experimental method has been achieved successfully in this work. The casted products have been machined according to the tests. It is possible to say that mechanical properties of AA 1070 aluminum can be enhanced by incorporating with borax by considering the experimental results and all about the data. By imposing various borax additions, holding temperatures and times on the samples, the following conclusions can be drawn from this study: The greatest mechanical test results obtained in %5-10 borax addition ranges. Optimum holding temperature was obtained at 10000C for tensile and impact properties of Al-B alloys. Optimum holding time for the highest mechanical properties has been described at 45 minutes. Increase in mechanical properties of the alloyed sample are: 33% for UTS value 21% for impact energy when comparing the maximum values with pure aluminum produced in the same conditions. Microscopic observations of alloyed samples reveal homogeneous distribution of aluminum boride particles and fewer porosity levels. Acknowledgement The authors would like to thank Scientific Research Projects Governing Unit of Gaziantep University for the financial support during the period of this research work. REFERENCES [1] Birol, Y., Production of Al-Ti-B grain refining master alloys from B2O3 and K2TiF6, Journal of Alloys and Compounds, Vol. 443, pp. 94-98, 2007. [2] Kerti, I., Toptan, F., Microstructural variations in cast B4C-reinforced aluminum matrix composites (AMCs), Materials Letters, Vol. 62, pp. 1215-1218, 2008. [3] Mohanty, R.M., Balasubramanian, K., Seshadri, S.K., Boron carbide-reinforced aluminum 1100 matrix composites: Fabrication and Properties, Materials Science and Engineering, Vol. A498, pp. 42-52, 2008. [4] Totten, G.E., MacKenzie, D.S., Handbook of aluminum, M. Dekker, New York, 2003. [5] American Society for Metals, Aluminum: Properties, physical metallurgy and phase diagrams, Ohio, Chapman & Hall Ltd, 1971. [6] Birol, Y., Production of Al-Ti-B grain refining master alloys from Na2B4O7 and K2TiF6, Journal of Alloys and Compounds, Vol. 458, pp. 271-276, 2008. [7] Wang, X., The formation of AlB2 in an Al-B master alloy, Journal of Alloys and Compounds, Vol. 403, pp. 283-287, 2005. [8] Hall, A.C., Economy, J., Preparing high and low aspect ratio AlB2 flakes from borax or boron oxide, Journal of the Minerals, Vol. 52(2), pp. 42-44, 2000. [9] Setzer, W.C., Boone, G.W., The Use of Aluminum/Boron Master Alloys to Improve Electrical Conductivity, Light Metals, pp. 837844, 1992. [10] Fjellstedt, J., Jarfors, A.E.W., Svendsen, L., Experimental analysis of the intermediary phases AlB2, AlB12 and TiB2 in the Al-B and Al-Ti-B systems, Journal of Alloys and Compounds, Vol. 283, pp. 192-197, 1999. [11] Ozturk, M., An Experimental Study on Mechanical Properties of Aluminum-Boron Compounds, MSc Thesis, Gaziantep University, Gaziantep, 2011.
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VIBRATION DAMPING CHARACTERISTICS OF BORON COMPOSITES

H. Ibrahim UNAL*, Ozlem EROL*, O. Yunus GUMUS**, Berrak CETIN*, Turgay ERGIN*** *Gazi University, Chemistry Department, Smart Materials Research Lab., Ankara, Turkey, iunal@gazi.edu.tr **Nevsehir University, Chemistry Department, Nevsehir, Turkey ***Hacettepe University, Department of Automotive, Ankara, Turkey ABSTRACT Electrorheological (ER) fluids can be classified as smart materials due to their controllable and reversible rheological characteristics under external electric fields. Most ER fluids consist of polarizable solid powders dispersed in insulating non-polar liquids. Recently, conducting polymers have gained interest in boron derivative containing conducting composites. Conducting polymer/boron derivative composites can be fabricated with controlled levels of conductivity and enhanced anti-sedimentation stability. In this study, vibration damping characteristics of borax and polyindene/colemanite composites were investigated. After characterizing these materials by various techniques, volume fraction series of dispersions were prepared in silicone oil (SO). Anti-sedimentation stabilities of these suspensions were determined. Flow rate measurements of these dispersions were measured at various electric field values; flow times and threshold energies were determined. Finally, vibration damping capacities of the materials were tested under external electric field, using an automobile shock absorber and were calculated as 68% and 27% for borax/SO and polyindene/colemanite/SO systems, respectively. Keywords: Conducting Polymer Composite, Electrorheological Fluids, Borax, Colemanite, Vibration Damping, Shock Absorber. 1. INTRODUCTION Electrorheological (ER) fluids are colloidal dispersions that commonly compose of polarizable powders dispersed in non-conducting liquids. ER fluids exhibit reversible changes (liquid-like to solid like and vice-versa) in their rheological properties as a function of the electric field strength (E). In the presence of sufficient electric field strength, the dispersed particles are polarized and aligned in the field direction to form a solid-like network of fibrillar structures and these structures cause to observe changes in rheological properties of dispersion. The solid powder comprises inorganic non-metallic, organic or polymeric semi-conductive materials [1]. Borax (Na2B4O7.5H2O) and colemanite (2CaO.3B2O3.5H2O) are important boron containing commercial borate minerals and can be candidates for being ER material. Also, preparing their composites with conducting polymer is another option since the interactions between organic and inorganic component of composite materials could enhance the desired properties. Because of the rapid and reversible changes in their rheological properties with the external applied E, ER fluids have been widely investigated for the purpose of various industrial applications such as shock absorbers, engine mounts, clutch/brakes and vibration dampers. ER shock absorbers are characterized by a valve containing a pair of electrodes between which the ER fluid flows [2]. The aim of this study was to investigate the vibration damping capacities of borax/SO and polyindene/colemanite composite/SO dispersion systems. Thus, borax was kindly ground milled and polyindene was polymerized in the presence of colemanite. The materials were dispersed in SO. Anti-sedimentation ratios of the dispersions were determined under constant temperature. Flow rates and threshold energies of the materials were investigated under various E. The effects of surfactant and polar additives on vibration damping capacities of the polyindene/ colemanite/SO were also examined. Results implied that all the systems perceive the applied electric field and try to act as a vibration damper.
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2. EXPERIMENTAL Borax and colemanite were kindly supplied by ETI Mining Co. (Turkey) and were ground milled. All the other chemicals were Aldrich products and used as received. Indene was used after distillation. Polyindene (PIn) was in-situ polymerized in the presence of colemanite using FeCl3 as oxidizing agent taking the monomer to initiator ratio as 2:1 in CHCl3. The prepared PIn/colemanite was ground-milled and subjected to particle size measurement using a Malvern Nano-ZS particle size analyzer. The obtained PIn/colemanite was subjected to various characterization techniques, namely: FTIR, particle size, density, conductivity, TGA, XRD and SEM. All the materials were subjected to solid pellet preparation (cylindrical in shape). Further, the apparent densities and conductivities (by a four probe technique) of the materials were measured. Dispersions of borax, colemanite and PIn/colemanite composite were prepared in SO at a series of volume fractions ( = 525%) and the anti-sedimentation stability of the dispersion systems were measured (T = 250.1C). The non-ionic surfactant examined was Triton-X (t-octylphenoxypolyethoxyethanol) and the concentration of TritonX in the colemanite and PIn/colemanite dispersions was 5 wt.%. To prepare the dispersions containing Triton-X, firstly, SO and surfactant were homogeneously mixed by using an ultrasonicator and then the materials, (colemanite and PIn/colemanite), were added and mixed again, with the volume fraction of 25%. These surfactant containing dispersions were coded as T-colemanite and T-PIn/colemanite. To enhance the ER activity of colemanite/SO and PIn/colemanite/SO dispersions, glycerol was added as 10 L/mL and the resultant dispersions were coded as Gcolemanite and G-PIn/colemanite. All the prepared dispersions were allowed to equilibrate for overnight before ER and vibration damping measurements. Flow rate measurements were carried out between two brass electrodes, which were connected to a high-voltage dc power supply. Oscillatory tests were carried out by a Termo-Haake RS600 parallel plate torque electrorheometer. Vibration damping experiments were carried out on an automobile shock absorber for Borax/SO ( =15%), under E = 0-0.3 kV/mm conditions on Therpa Hydraulic vibration damping test device. The hydraulic vibration test equipment contained a wheel (with a spring coefficient of 65400 N/m), an axle, a spring (with a coefficient of 13000 N/m), a shock absorber, an electrically operated drum to turn the wheel, a vibrating mass (60 kg), a non-vibrating mass (14 kg), control units and an external electric field generator (Fug Electronics). During the experiments, vibrations occurring on the body and on the axle were recorded by a recorder, which was operated at 400 V and 16 A. 250 mL of colemanite/SO, G-colemanite/SO, T-PIn/colemanite/SO and PIn/colemanite/SO dispersion systems were used with = 10% under the external electric field strength sweep of E = 0-170 V/mm and the experiments were carried out using Roehrig 20VS model shock absorber test equipment. During the experiments, a modified automobile shock absorber was placed to the vibration test device and a dc external electric field generator was connected to the inner and outer tubes of the shock absorber. The test parameters were set up using the Shock 6.3 shock absorber test program as following: Amplitude: 25.12 mm, test temperature: 25C, maximum test speed: 0.1 ms-1, frequency: 0.63 Hz, type of the input wave: sinusoidal. 3. RESULTS AND DISCUSSIONS The FTIR spectra proofed that the PIn/colemanite composite was successfully synthesized. SEM image of PIn/ colemanite composite reveals that porous structures of colemanite particles were homogeneously surrounded by close packed PIn chains, which supports the successful PIn/colemanite composite formation. The XRD pattern of PIn/colemanite composite showed sharp peaks at 2 = 15, 22 and 28 which indicates that colemanite was in the composite structure. The thermal stability of PIn/colemanite composite was observed to be higher than the thermal stabilities of colemanite and PIn [3]. The average particle size, apparent density, conductivity and anti-sedimentation ratios of the materials are given in Table 1. The conductivity values were decided to be in a suitable range for ER measurements. Table 1. Same physical properties of the samples. Sample Borax [4] Colemanite PIn/colemanite Average particle size (m) 6.35 1.2 2.2 Apparent Conductivity (Scmdensity (gcm-3) 1)x104 1.51 1.69 1.02 1.3 3.14 2.48 Anti-sedimentation ratios (%, at the end of 25 days, = 25%) 67 73 93
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Colloidal stability of the ER fluids against sedimentation is one of the important factors from industrial and application points of view. The ER fluids are supposed to be homogeneously dispersed before applying external electric field strength, and so that the stable fibrillar structures are formed under E between the upper and lower electrodes. At the end of 25 days of observation, 93% of PIn/colemanite composite particles were determined to remain unsettled. PIn/colemanite/SO dispersion system was significantly stable against gravitational sedimentation than colemanite/ SO and borax/SO systems. It can be concluded that in composite structure PIn chains surrounded the colemanite particles and formed steric hindrance that holds the particles in suspended positions against agglomeration. To observe the effect of dc electric field on the ER activity, flow rate measurements were carried out on all the dispersions. For this purpose, dispersions were prepared at a series of particle volume fractions ( = 525%) in SO and flow times were measured under E 0 kV/mm and E = 0 kV/mm conditions. During the flow time measurements, it was observed that electric field response time decreases with increasing volume fractions as a result of formation of fibrillar chain-like structures between the electrodes. On the other hand, a significant fibrillar structures between the electrodes was not observed for PIn/colemanite/SO system. The external frequency (f) is an important factor for characterizing the dynamic viscoelastic properties of ER fluids in vibration damping processes. Stress sweep was first carried out to determine the proper stress value to measure the storage modulus (G) in the linear viscoelastic regime. Figure 1 shows G as a function of frequency for borax/SO ( = 20%, E = 2 kV/mm), colemanite/SO, T-colemanite/SO, PIn/colemanite/SO and T-PIn/colemanite/SO dispersion systems ( = 25%, E = 1.5 kV/mm).
Figure 1. Change in storage modulus with frequency for all the dispersions. It was observed that Borax/SO system showed the highest G values and G values of all dispersions except PIn/ colemanite/SO were showed slight increments in the whole frequency sweep range and owing to not providing fully elastic solid-like structure in the dispersions, but they showed viscoelastic behavior. However, G values of PIn/colemanite/SO increased notably with increasing frequency. This suggests that fibrillar structure between the electrodes could not occur for PIn/colemanite [5].
Figure 2. Change in damping forces with piston velocity of shock absorber. Sample: T-PIn/colemanite/SO, = 10%. Figure 2 represents the damping forces (Fdamping) as a function of piston velocity of the modified automobile shock absorber for just T-PIn/colemanite/SO system under the constant conditions of T = 25C, = 10% and E = 0-170 V/mm. As the electric field increased, Fdamping of the ER damper, filled with T-PIn/colemanite/SO, also increased thereby requiring more force to move the piston. This was mainly attributed to the increment of the shear stress of
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the ER fluid with increasing applied E. The percentage increment of vibration damping of the samples was determined from the following equation: (1)
Vibration damping (%) of the materials calculated to change in the following order: T-PIn-colemanite (30%)>G-colemanite (28%)>PIn-colemanite (27%)>Colemanite (14%). The addition of Triton-X or glycerol caused to increase in the percentage of vibration damping of PIn/colemanite/SO and colemanite/SO. It was concluded that the presence of surfactant/promoter improved the performance of ER fluid. For Borax/SO system ( = 15%), positive body vibration amplitudes (recorded in the course of opening of the shock absorber) were observed to be bigger than the negative body vibration amplitudes (recorded in the course of closing of the shock absorber). Results showed that the amplitudes of body and axle, which are 10.2 and 12.6 mm, respectively, under non-electric field were reduced to 3.2 and 8.7 mm, respectively, by applying E = 300 V/mm external electric field. Thus, the vibration damping values were calculated as 68% on the body and 31% on the axle. These reductions on the amplitudes indicate that borax/SO system is able to perceive applied electric field strength and significantly increase the vibration damping capacity of the automobile shock absorber [6]. ACKNOWLEDGEMENTS The authors thank to Turkish Scientific and Technological Research Council for the financial support of this work (Project no: 107 T 711). REFERENCES 1. Hao, T., Electrorheological suspensions, Advances in Colloid and Interface Science, Vol. 97, pp. 1-35, 2002. 2. Wereley, N.M., Nondimensional HerschelBulkley Analysis of Magnetorheological and Electrorheological Dampers, Journal of Intelligent Material Systems and Structures, Vol. 19, pp. 257-268, 2008. 3. Cetin, B., Unal, H.I., Erol, O., Synthesis, Characterization and Electrokinetic Properties of Polyindene/ Colemanite Conducting Composite, Clay and Clay Minerals, submitted, 2011. 4. Gumus, O.Y., Unal, H.I., Erol, O., Sari, B., Synthesis, Characterization, and Colloidal Properties of Polythiophene/Borax Conducting Composite, Polymer Composites, Vol. 32, pp. 418-426, 2011. 5. Ramos-Tejada, M.M., Espin M.J., Perea, R., Delgado, A.V., Electrorheology of suspensions of elongated goethite particles, Journal of Non-Newtonian Fluid Mechanics, Vol. 159. pp. 34-40, 2009. 6. Gumus, O.Y., Erol, O., Unal, H.I., Polythiophene/Borax Conducting Composite II: Electrorheology and Industrial Applications, Polymer Composites, Vol. 32, pp. 756-765, 2011.
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Production of Al- B4C functionally graded material by powder metallurgy method

Aykut Canakci1, Temel Varol1, Ihsan Gokhan Zerin, Serdar zkaya
1
Department of Metallurgical and Materials Engineering, Karadeniz Technical University, Trabzon, Turkey aykut@ ktu.edu.tr, tvarol@ktu.edu.tr Abstract
The aim of this study is to examine the effects of the processing conditions on the final microstructure of Al-B4C functionally graded materials (FGMs). Al-B4C functionally graded material (FGM) having a compositional gradient from Al to B4C was obtained by powder metallurgy method with Al and B4C powders as starting materials. For this purpose laminar type of functionally graded Al-B4C with 1, 2 and 3 layers, which have different compositions, were produced. The functionally graded materials were analysed using a scanning electron microscopy (SEM). The microstructure, elemental distribution and microhardness variation of the sintered Al-B4C samples were investigated. The experimental results show that the distributions of structure properties strongly depend on the variation of microstructure. It is observed that hardness increases and ductility decreases with the increase of B4C, which is attributed to the variation of the matrix phase from the metal to the ceramic. Morever, The results showed that laminar type is an effective method for Al-B4C functionally graded materials production. Keywords: Functionally graded materials, Powder metallurgy, Boron carbide (B4C) 1. Introduction Functionally graded material (FGM) is a new concept in material design. FGMs with continuous changes of microstructures and properties across the material are expected to have low residual and thermal stresses and improved bonding strength between dissimilar materials and ceramic coatings. The unique characteristics in structure distribution makes FGM offer great promise in applications in many areas and the researches have been widely performed. It is well known that FGM performance depends mainly on the composition distribution. The composition distribution in FGMs can be tailored to specific requirements and properties of the constituent materials. For example, the structure of ceramic/metal FGMs is designed by considering the thermomechanical properties of the metal that has high mechanical strength and thermal conductivity of the ceramics that acts as a heat-resisting thermal shield. Therefore, ceramic/metal FGMs have received growing attention as prospective thermal barrier materials. A number of numerical analyses and experimental methods have been developed to evaluate the mechanical and thermal properties of FGMs [1-5]. Various techniques have been employed to the fabrication of FGM, including physical and chemical vapor deposition, sintering, plasma spraying, electroplating and combustion synthesis. Powder metallurgical processing is one of the most viable routes for FGM, because the composition and microstructure as well as shape forming of FGM can be easily controlled in a wide range [2,6,7]. The powder metallurgy (PM) or ceramic technology route for processing of materials and engineering parts includes powder production, powder processing, forming operations and sintering or pressure assisted hot consolidation. Powders of many metals, alloys, compounds and ceramic materials with particle sizes ranging from nanometers to several hundred micrometers are available from industrial sources or may be produced by the methods developed over decades in the field of PM or ceramics. Since the material used to form the sintered part is dispersed into very small portions of individual powder particles nearly ideal conditions exist to build-up graded materials with varying chemistry or microstructure by using the particles as building blocks. Practical considerations towards an efficient process design suggest the use of powder mixtures with changing average particle size or composition during deposition of the material prior to the forming operation. It depends on the method applied for powder deposition whether a smooth change or a stepwise variation is obtained in the
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green body. Since the consolidation of the green parts during sintering or hot pressing requires high temperatures at which diffusion processes are fast enough to enable densification, chemical reactions between particles of different compositions and the influence of particle size on the sintering behavior have to be taken into account for the final microstructure and dimensional control of the part. On the other hand thermodynamic factors acting during sintering may be used to create a gradient, e.g. during liquid-phase sintering [3,8]. The purpose of this research is to develop fundamental constitutional control technique of FGM by powder metallurgy, expecting to optimize FGM fabrication process and further improve its performance.The microstructure and the composition of the fabricated FGM by powder metallurgy were studied and the relative density and the Brinell hardness of each layer in the FGM were measured. The relationship between microstructure, composition, and some physical and mechanical properties were discussed. 2. Experimental procedures Aluminium powders and B4C particles were used as raw materials to fabricate the FGMs. An average particle size of B4C particles used as reinforcement material and Al powders (Etial 7) used as matrix materials were 102m and 113m, respectively. Fig. 1(a) and (b) shows the morphologies of the as received Al matrix powders and B4Cparticles [9].
(a)
(b)
Fig. 1. Morphology of as-received powders: (a) Al alloy and (b) Al2O3 particles. The Al matrix powders are ligamental in shape and the B4C particles are polygonal in shape. These powders are mechanically mixed and single-axis press, compressed raw samples produced at different pressures. The stacked layer were pressed at a pressure of 400 and 500 MPa. In ths work, experiments on single-layer, two-layer and three-layer of Al-B4C FGM, as shown in Fig. 2 and Table1, are conducted [9]. (a)
(b)
(c) Fig. 2. The composition distribution model of Al-B4C FGMs. (a) Single-layer samples, (b) Two-layer samples, (c) Three-layer samples
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Table 1.Configuration of FGMs. Coded Samples Alsingle(400) Alsingle(500) Al-5single (400) Al-5single (500) Al-10single(400) Al-10single (500) (Al+Al-5)two(400) (Al+Al-5)two(500) (Al+Al-10)two(400) (Al+Al-10)two(500) (Al+Al-5+Al-10)three(400) (Al+Al-5+Al-10)three(500) 100 wt.% Al 100 wt. % Al 95 wt.% Al + 5wt.% B4C 95 wt.% Al + 5wt.% B4C 90 wt.% Al + 10wt.% B4C 90 wt.% Al + 10wt.% B4C 100 wt. % Al and 95 wt.% Al + 5wt.% B4C 100 wt. % Al and 90 wt.% Al + 10wt.% B4C 100 wt. % Al and 90 wt.% Al + 10wt.% B4C 100 wt. % Al and 90 wt.% Al + 10wt.% B4C 100 wt. % Al , 95 wt.% Al + 5wt.% B4C and 90 wt.% Al + 10wt.% B4C 100 wt. % Al , 95 wt.% Al + 5wt.% B4C and 90 wt.% Al + 10wt.% B4C Composition Pressure (MPa) 400 500 400 500 400 500 400 500 400 500 400 500 Layer Single Single Single Single Single Single Two Two Two Two Three Three
The as-received Al alloy powder, the conventionally mixed (CM) powders were uniaxially cold pressed in a rectangular die with dimension of 30x30x20mm at 400 and 500MPa, with graphite as the die lubricant. The green compacts were sintered 600 oC for 3h under argon atmosphere. The sintered compacts were cooled to room temperature in the sintering furnace. The experimental density of the composite samples was measured using Archimedes method. In this technique, density is determined by measuring the difference between the samples weight in air and when it was suspended in distilled water at room temperature. The theoretical density was calculated using the mixture rule according to the volume fraction of the B4C particles. The porosities of FGMs were then evaluated from the difference between the expected and the observed density of each sample. To evaluate microstructure of produced composites the surface of samples were polished to achieve a rough surface of about 0.05m. The morphologies and distribution of the B4C particles and the microstructures of the conventionally both mixed and the milled Al-B4C FGMs were analyzed on a Zeiss Evo LS10 scanning electron microscope (SEM) and a stereo microscopy. The particle size distributions were determined using laser diffraction (Malvern, Model mastersizer Hydro 2000e), connected to a compute that models the volume size distribution, D10, D50, D90 calculation automatically; three measurements were carried out for each sample. The hardness of the samples was measured using Brinell hardness method under a load of 31.25 kg held for 20s. Reported hardness values were the average of five measurements. With the variation of composition, the Al-B4C uniform compacts undergo very different shrinkage during densifications as shown in Fig. 3. 3. Results and discussions
Fig. 3. Developing procedure of FGMs [9].
3.1. Microstructure distribution The optical and SEM images of the cross-section of the prepared FGM component are shown in Fig. 4 and Fig. 5, respectively.
(a)
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(b) Fig. 4. Optical micrographs of different Al-B4C FGM fabricated by powder metallurgy (pressed at 500MPa). (a) Single-layer samples, (b) Two-layer samples, and (c) Three-layer sample. (c)
(a)
(b)
(c) Fig. 5. Scanning electron microscopy micrographs at different positions in FGMs. (a) Single-layer samples (pressed at 500MPa), (b) Two-layer samples (pressed at 400MPa), and (c) Three-layer sample (pressed at 400MPa)
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It can be seen that the microstructure of the sample takes on a compositional gradient change along the thickness direction. The layer boundaries were observed clearly, which indicates that the structures of the FGMs were macroscopically heterogeneous due to the graded distribution of the composition. There arent delaminations or defects at the interlayer boundaries. In the images, it is noted that the light phase in the FGMs is Al and the dark phase is B4C, which is seen particularly clearly in the SEM image (Fig. 4). The microstructure of the sintered Al-B4C FGMs is presented in Fig. 5, where the gray and dark phases are Al and B4C, respectively. These images show a good gradual compositional variation in the FGMs. The obvious macroscopic interfaces are not observed even on the interfaces between different layers where the material composition jumps. Fig. 5 shows a typical variation of the microstructure in the FGMs. The varying microstructure is characterized by the gradual variation of the matrix phase from the metal to the ceramic with the increase of B4C. In the metal-rich side, the ceramic particles are dispersed in the metal matrix. With the increase of B4C, the clusters of the ceramic are formed and their further growths result in the formation of a network structure. Then, the network of the metal is gradually diminished and turns into the isolated metal particle dispersed in the ceramic matrix in the ceramic-rich side. 3.2. Some physical properties of FGMs The graded change of the chemical compositions and microstructure in FGM leads to a continuous distribution of the properties. As shown in Fig. 6, 7 and Table 2, the density of theoretical, green and sintered and porosities of the FGMs according to the weight fractions of B4C particles. Al-B4C system show various graded distributions corresponding to constitutional change. Fig. 6, 7 and Table 2 show that density of green and sintered samples decreases with increasing B4C content. The graphs of green and sintered densities of the FGMs according to the weight fractions of B4C particles are shown in Figs. 6 and 7, respectively. Table 2. Physical properties of FGMs [9]. Coded samples Alsingle(400) Alsingle(500) Al-5single (400) Al-5single (500) Al-10single(400) Al-10single (500) (Al+Al-5)two(400) (Al+Al-5)two(500) (Al+Al-10)two(400) (Al+Al-10)two(500) (Al+Al-5+Al-10)three(400) (Al+Al-5+Al-10)three(500) Theoretical density (g cm-3) 2.70 2.70 2.69 2.69 2.68 2.68 2.70 2.70 2.69 2.69 2.69 2.69 Green density (g cm-3) 2.52 2.60 2.51 2.59 2.49 2.57 2.52 2.59 2.51 2.59 2.50 2.59 Sintered density (g cm-3) 2.60 2.61 2.51 2.60 2.50 2.58 2.52 2.60 2.51 2.60 2.51 2.59 Green porosity (%) 6.54 3.70 6.74 3.82 7.12 4.27 6.63 3.75 6.88 3.84 7.09 4.20 Sintered porosity (%) 5.19 3.34 6.58 3.50 6.86 3.69 6.38 3.42 6.58 3.49 6.72 3.75
(a)
(b)
Fig. 6. The green densities of FGMs for different pressing pressure.(a) at 400MPa, (b) at 500MPa.
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(a)
(b)
Fig. 7. The sintered densities of FGMs for different pressing pressure. (a) at 400MPa, (b) at 500MPa. Table 3 shows that some theoretical density values of the FGMs decrease (as expected from the rule of mixtures). Although a decrease was also seen in the experimental densities (green and sintered density values), the value are lower than those theoretical ones. The density measurements showed that FGMs contain some porosity, and the amount of porosity in the green and sintered of FGMs increased with the increasing weight fraction of the particles (Fig. 8 and 9), as observed in the previous investigations [10-17].
(a)
(b)
Fig. 8. The green porosities of FGMs for different pressing pressure.(a) at 400MPa, (b) at 500MPa.
(a)
(b)
Fig. 9. The sintered porosities of FGMs for different pressing pressure.(a) at 400MPa, (b) at 500MPa. 3.3. Hardness of FGMs The influence of the varying microstructure on the hardness of the FGM sample is obvious, as shown in Fig. 10. As the content of B4C increases from 0% to 10%, the slope of the hardness curve changes and the hardness increases substantially. This is mainly caused by the gradual variation of the microstructure inthe FGMs. In these layers, the matrix phase varies from the softmetal to the hard ceramic, as shown in Fig. 4 and 5. The Brinell hardness of the FGMs and single-layers were given in Table 3. The relation between the B4C particle content and the hardness of the FGMs were plotted in Fig. 10. It was seen from Fig. 10 that the hardness of the FGMs increased with increasing particle weight fraction. As compared to the Alsingle matrix alloy, the hardness of the FGMs was found to be greater, and addition of B4C particles increase the hardness of the Al alloy [11,18].
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Table 3. The hardness properties of FGMs. Coded samples Alsingle(400) Alsingle(500) Al-5single (400) Al-5single (500) Al-10single(400) Al-10single (500) (Al+Al-5)two(400) (Al+Al-5)two(500) (Al+Al-10)two(400) (Al+Al-10)two(500) (Al+Al-5+Al-10)three(400) (Al+Al-5+Al-10)three(500) Brinell Hardness (BHN) 170 189 201 213 226 250 170-201 195-226 175-213 195-241 166-195-220 185-220-250
An increase in the hardness of the Al-B4C FGM with increasing weight fractions of B4C from the matrix to B4C graded regions, for both the FGM fabricated at 400 and 500MPa, respectively (Table 3, Fig. 10), as observed in the previous investigations [19,20].
(a)
(b)
(c) Fig. 10. The Brinell hardness of FGMs.(a) Single-layer samples, (b) Two-layer samples, (c) Three-layer sample.
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4. Conclusions Single, two and three staged Al-B4C FGMs had been successfully fabricated by powder metallurgy technique. The relative density of the FGM was more than 93%. The relative density of the three stage FGM (500Mpa) was more than 95%. Microstructure analysis showed that a good graded composition of FGM had been obtained. The B4C particles were well embedded into the matrix by solid state sintering. The present work provides a effective approach to fabricating ceramicmetal FGM by powder metallurgy technical for different applications. 1. Al-B4C functionally graded material (FGM) has been successfully developed by the powder metallurgical process 2. Green and sintered density values increases with increasing pressure. 3. Green and sintered density values decreases with increasing B4C content. 4. Hardness of FGMs increases with the increasing B4C content. Acknowledgement The authors are grateful to Karadeniz Technical University Research Fund for the financial supporting of this research work (No: 2007.112.10.2). References 1. Gang Jin, Makoto Takeuchi, Sawao Honda, Tadahiro Nishikawa, Hideo Awaji, Materials Chemistry and Physics 89 (2005) 238243 2. Jingchuan Zhua, Zhonghong Lai , Zhongda Yin, Jaeho Jeon, Sooyoung Lee, Materials Chemistry and Physics 68 (2001) 130135 3. B. Kieback, A. Neubrand , H. Riedel, Materials Science and Engineering A362 (2003) 81105 4. Xin Jin, LinzhiWu, Yuguo Sun, Licheng Guo, Materials Science and Engineering A 509 (2009) 6368 5. S. Lopez-Esteban, J.F. Bartolome , C. Pecharroman, J.S. Moya, Journal of the European Ceramic Society 22 (2002) 27992804 6. Zhang-Jian Zhou, Juan Du, Shu-Xiang Song, Zhi-Hong Zhong, Chang-Chun Ge, Journal of Alloys and Compounds 428 (2007) 146150 7. Zeming He, J. Ma, G.E.B. Tan, Journal of Alloys and Compounds 486 (2009) 815818 8. Li Sun, Basak Oguz, Patrick Kwon, Powder Technology 195 (2009) 227234. 9. I.G. Zerin, S. Ozkaya, Karadeniz Technical University, Department of Metallurgical and Materials Engineering, Trabzon, Turkey, Graduation Thesis, 38 pages, 2011. 10. Manumanth GS, Iron GA (1993) J Mater Sci 28:2459. doi: 10.1007/BFO1151680 11. Kk M (2005) J Mater Process Technol 161:381 12. Kk M (2006) Composites A 37:457 13. Ghost PK, Ray S (1988) AFS Trans 775782:88 14. Akhlaghi F, Lajervardi A, Maghanaki HM (2004) J Mater Process Technol 155156:1874 15. McCoy OW and Franklin EW (1988) In: Fishman SG, Dhingra AK (eds) Cast reinforced metal composites. Chicago, USA, p 77 16. Ray S (1988) In: Fishman SG, Dhingra AK (eds) Proceedings of the survey on fabrication methods of cast reinforced metal composites. ASM/TMS, p 77 17. Ccen U, nel K (1996) Mater Sci Eng A 221:187 18. Purazrang K, Abachi P, Kainer KU (1994) Composites A 25(4):296 19. Rao AG, Mohape M, Kathar VA, Gowtam DS, Deshmukh VP and Shah AK (2010) Materials and Manufacturing Processes, 25: 572576. 20. Lin CY, Bathias C, McShane HB and Rawlings RD (1999) Powder Metallurgy 42(1): 29-33.
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YKSEK ENERJL BLYEL TME YNTEM LE BOR NTRR NANO TP RETM

S. Hale GLER, Ertan EVN, mer GLER, Mustafa AKSOY Frat niversitesi, Metalurji ve Malzeme Mhendislii Blm, Elaz,Trkiye
ZET Bu almada tme ve tavlama metodu kullanlarak Bor Nitrr Nano Tpler (BNNT) sentezlenmitir. Balang tozu olarak amorf bor tozu kullanlm ve bu toz bir planeter bilyal deirmende (Fritsch Pulverisette 7) 20 ve 40 saat boyunca azot atmosferi altnda tlmtr. Yeterli tme salandktan sonra elde edilen tozlar bir tp frn ierisinde amonyak gaz altnda 1300 oC de 2 saat boyunca tavlanmtr. Sonu olarak bu teknik kullanlarak BNNTler retilmitir. retilen tpler X-n difraksyon analizi (XRD),yksek ayrma gl geirimli elektron mikrobu (HR-TEM) kullanlarak incelenmitir. Anahtar Kelimeler: Bor Nitrr, Nano tp, tme
PRODUCTION OF BORON NITRIDE NANOTUBES USING HIGH ENERGY BALL MILLING METHOD
S. Hale GLER, Ertan EVN, mer GLER, Mustafa AKSOY Firat University, Department of Metallurgical and Materials Engineering, Elazg,Turkey
ABSTRACT In this study , Boron Nitride Nanotubes (BNNTs) were synthesized using a ball-milling and annealing method. Starting powder was used as the amorphous boron powder and in a plenetary ball mill (FritschPulverisette 7) was ball milled for 20 and 40 hours under nitrogen atmosphere. After sufficent milling, to obtined powders were annealed under ammonia gas flow at 1300C for 2 hours in tube furnace. Consequently, the nanotube was produced by using this tecnique. Synthezed tubes were determined by using Xray diffraction analysis (XRD),high-resolution trasmission electron microscopy (HR-TEM) Keywords: Boron Nitride, Nanotubes, Ball milling 1. GR Bor nitrr nano tpler (BNNT) teorik olarak 1994 ylnda Rubio tarafndan kefedilmi [1] ve 1995 ylnda Chopra tarafndan Berkeley niversitesinde baaryla sentezlenmitir [2]. Karbon nano tplerde (KNT) olduu gibi BNNT lerinde tabakalar arasnda sp2 balar mevcuttur ve BNNT ler de tp eklindeki yaplarndan dolay iyi mekanik zelliklere sahiptirler. BNNT ler hegzegonal bor nitrr (hBN) tabakalarn, sarlarak silindir eklini almas ile olumulardr. hBN n tabakal yaps BNNT lerin anlalmas iin bir gayet nemlidir [3].
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KNT lerin elektronik cihazlarn yapsnda kullanlmas ile birlikte aratrmaclar nano lekte elektronik devreler iin yeni malzemeler aramaya balamlardr. BNNT lerin 5,5eV bant aralna sahip olduu saptanm ve yaltkan malzeme olarak kullanm ngrlmtr. Bu bant aral tp apna, tpn yapsna, duvar saysna bal olarak deimektedir [1]. BNNT ler KNT lerin uygun olmad, nano lekte elektronik ve foto elektronik yeni devrelerin retiminde kullanlabilirlii aratrlmaktadr. Yksek termal stabilitesi, iyi sl direnci, yaltkan zellii eitli korozif ortamlarda kimyasal direnci, bor nitrr nanotplerin iyi bilinen zelliklerindendir [3]. BNNT lerin retiminde KNT lerde olduu gibi farkl yntemler mevcuttur. Bu yntemler farkl apta, farkl saflkta ve farkl yapda tp sentezi salamaktadr. Bu amala kullanlan yntemler; ark boaltma, lazer biriktirme, kimyasal buhar biriktirme (CVD) ve mekanik alamlamadr. Mekanik alamlama iin konvansiyonel deirmenler ve yksek enerjili bilyeli deirmenler (YEBD) kullanlmaktadr. YEBD ler ilk olarak 1960 l yllarda Benjamin ve grubu tarafndan kullanlm ve konvansiyonel deirmenler yeterince enerji salamadndan dolay ODS alamlarn sentezlemek iin gelitirilmitir. YEBD lerde partikl krma ve boyut azaltma ilk aamada grlmekte ve bu nedenle YEBD lerde uzun tme zamanlarna gerek duyulmamaktadr. YEBD ler iin tme atmosferi ve tme iddetinin kontrol nem arz etmektedir. nk bu parametrelerin kontrol ile tme sresi boyunca kimyasal ve yap deiimleri gereklemektedir. YEBD lerin farkl tipleri mevcuttur. Bu deirmen tipleri; spex, planeter, atritr, vibrasyonludur. Nanotp sentezleme aratrmalar iin vibrasyonlu ve planeter bilyeli deirmenler kullanlmaktadr [4]. Bu almada nano tp retmek amac ile, tme ilemi sresince mekanik enerji yardmyla kimyasal dnm reaksiyonu (in-situ dnm) oda scaklnda gerekletirilmi ve sonraki tavlama ileminde dk scaklklarda tp oluumu salanmtr. 2. DENEYSEL ALIMA tme deneyleri bir planeter bilyeli deirmende (Fritsch Pulverisette 7) gerekletirilmitir. Balang malzemesi olarak Merck kGAA firmasndan temin edilen % 98 saflkta amorf bor tozu kullanlmtr. Deneylerde bilye/toz oran 32/1 olarak seilmi ve B tozu deirmende 20 ve 40 saat boyunca azot atmosferi altnda 400 devir/dak lk bir hzda tlmtr. tme ilemi oksidasyonu nlemek amac ile koruyucu atmosfer (N2) altnda gerekletirilmitir. tme ileminden nce, kaplar ierisindeki kalnt oksijeni uzaklatrlmas amacyla tme kaplar azot gaz ile birka kez temizlenmitir. Daha sonra tlen tozlar 1300C de 2 saat NH3 atmosferi altnda bir tp frn ierisinde tavlanmtr. NH3 gaznn debisi 500 ml/min olarak seilmitir. tlm ve tavlanm numuneler Frat niversitesi (F.) Metalurji ve Malzeme Mhendislii Blmnde Bruker D9 marka X-n difraksyon cihaznda (CuK radyasyonu vastasyla) veF. Fizik Blmmde yksek ayrma gl geirimli elektron mikrobu (JEOL JEM 2100F HR-TEM) kullanlarak incelenmitir. 3. SONU VE TARTIMA Bor tozunun tavlama esnasnda BNNT lere dnmesi iin ncelikle nano boyuta indirilmesi gereklidir. Bu amala amorf bor tozu bilyeli deirmende 20 ve 40 saat sreyle tlmtr. Ayrca tme esnasnda tme kaplar ierisinde bulunan tozlarn bir ksmnn N2 atmosferi ile reaksiyona girerek amorf yapl nano tozlara dnt XRD incelemeleri ile tespit edilmitir ekil 1.a-bde 20 ve 40 saat tlm numunelerden elde edilen XRD sonular verilmitir. ekilden de grld gibi 20 saat tmenin ardndan yaklak 44o de bir pik ortaya kmtr. Bu pik, BN ve FexBy pikleridir. 44o deki bu pikin 40 saat tme sonunda geniliinde artma meydana gelirken, iddeti nispeten azalmtr. Amorf bor tozunun azot atmosferinde tlmesinden dolay 20 saat tme sonunda yapda nano boyutlu BN partiklleri olumutur. Ayrca, tme ilemi srasnda tme kabnn ve bilyelerin anmas ile yapya karan Fe partiklleri tme sresinin artmas ile birlikte bor ile reaksiyona girerek FexBy ye dnmtr. ekil 1.cde grlen 40 saat tme ve 1300Cde 2 saat tavlama sonucunda elde edilen XRD analizinde yaklak 26o de ortaya kan (002) pikinin h-BN ilikili olduu tespit edilmitir ve baz almalarda bu pikin BNNT olduu belirtilmektedir [5]. tme ilemi srasnda 44o de ortaya kan pikin iddeti, sl ilemden sonra daha da azalmtr. Muhtemelen sl ilem ile beraber FexBy faznda ayrma meydana gelmitir. Pikteki azalmann sebebinin ise bu durum olduu dnlmektedir. Isl ilem ile beraber yapdaki demir partiklleri de amonyak ile reaksiyona girerek FexN eklinde demir nitrrlere dnmlerdir. Yapdaki demirin bir ksm ise sl ilem scaklnn etkisiyle bor ile reaksiyona girerek farkl formda FexBy e dnmtr. Yapda BN piklerinin tamam BN nanotpe ait pikler olmayp, farkl formlarda olumu BN de yapda bulunmaktadr.
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ekil 1. XRD sonular; (a) 20 saat tme sonunda,(b) 40 saat tme sonunda ve (c) 40 saat tme ve 1300Cde 2 saat tavlama sonucunda Bu sonular dahilinde tme sonucunda elde edilen metastabil amorf yapnn tpe dnt grlm ve baz aratrmaclar tarafndan da belirtilmitir [6]. Bu yksek miktarda hata ieren yap difzyon prosesini harekete geirmektedir. Partikl boyutunun nano boyuta dnmesi difzyon mesafesini azaltmaktadr. BN tpn oluabilmesi iin iki nemli gereksinim vardr. Bunlar; ekirdek alanlar ve serbest atom kaynaklardr. Nano katalizr partiklleri ve yzey difzyonunun etkisi ile bu zel yaplarn olutuu bilinmektedir [8]. Atomlarn, yzey ksmlarnda ok zayf balar kurmas ve yzey difzyonunun ortam gazlarnn adsorbsiyonundan byk lde etkilenmesinden dolay malzeme tanmnda yzey difzyonunun baskn mekanizma olduu dnlmektedir [7,8]. ekil 2de 20 saat (a-b) ve 40 saat (c-d-e) tme ileminden sonra tavlanan numunelerin TEM grntleri verilmitir. ekilde aka grld gibi matris iinde dalm nano Fe partikllerine rastlanmtr. Bu partikllerin yapya tme kabnn ve bilyelerin anmasndan tr getii sanlmaktadr. tme zamann artmas ile birlikte Fe partikl miktarnn dereceli olarak artt dnlmektedir [5]. Bu metal partikllerinin nanotp oluumu iin pozitif bir rol oynadklar ve ekirdekleme iin katalizr grevi yaptklar ekil 2.bde grlmektedir ve ekil 2.bde
ekil 2. 1300Cde 2 saat NH3 atmosferi altnda tavlanan numunelerin TEM resimleri
tpn u ksmndaki Fe partikl zerinden nanotp gelimektedir. Ayrca ayn ekilde nanotpn evresinde farkl boyutlarda Fe partiklleri mevcuttur. Bu partikllerin etrafnn dnmemi amorf yap ile kapl olduu grlmektedir. Elde edilen TEM grntlerine gre rnlerin bambu tipli nanotpler olduu aka grlmektedir. Bambu tipli nanotplerin oluum modeli ekil 3 de verilmitir.
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ekil 3. Bambu tipli BNNTlerin byme modeli [5]. Bu mekanizmaya gre tme kab ve bilyelerden tozlara geen metal partiklleri tme prosesi boyunca amorf yap ierisinde homojen olarak dalmtr. 1300Cde nano boyutlu Fe partikllerin hacim ve yzey difzyonu bor nitrr ve karbondan daha byk olduu varsaylmaktadr [8]. Ergime noktas 1535C olmasna ramen nano boyutlu olmas nedeniyle demir keltiler yava bir ak davran iine girerek yar kresel duruma gemektedir [8]. Bor atomlar nano Fe partikl iine difze olurken, azot atomlar nce Fe yzeyler zerinde amonyaktan ayrlmakta ve daha sonra nano Fe partikl iine difz etmektedir (ekil 3.a). Zaten, tavlama sonunda verilen XRD analizlerinde Fe4N in bulunmas bu mekanizmay destekler niteliktedir. B ve N yeterli miktara ulatnda ar doymu kat zelti oluturmakta ve bu zeltiden BN tabakalarn oluumu devam etmektedir (ekil 3.b). BNNTler BN kabuklar ve katalizr arasndaki ara yzeylerden olumaya balamaktadr. Bu byme aamasnda d kabuk partikln her iki tarafndan gerilip, ayrlrken i kabuk ise kavislenmektedir. Nano tpn klcal etkisinden dolay katalizr partikl tp iine emilmeye balamaktadr (ekil 3.c). Katalizr partiklnn yzey gerilimini artmasna neden olan bu reaksyonda bor ve azot arasndaki temas alannn azalmasndan dolay emilen katalizr partikl (ekil 3.d) bor ve azot kayna olarak grev yapmaktadr. Katalizr partikl geri itilip yar kresel ekle geri dndnde bir bambu yumru olumaktadr (ekil 3.e). Sonuta bu ilemin tekrarlanmas ile bambu tip nano tp byyebilir (ekil 3.f-g). Bu byme modeli KSK (Kat-Svi-Kat) mekanizmas olarak isimlendirilmektedir [5]. Deneyler sonunda elde edilen nanotplerin boylarnn 200 nm den birka mikrona kadar deitii ve aplarnn 20-100 nm arasnda deitii tespit edilmitir. 40 saat tlm numuneler 20 saat tlm numunelerle karlatrldnda, 40 saat tlen numunelerde tp miktarnn arttrd ve tplerin aplarnn azald tespit edilmitir. Bunun nedeni; tme sresinin artmas ile beraber azot gaznn absorbsyonun artmasna ve tozlarn partikl boyutunun daha da azalmasna balanmaktadr [5]. 4. GENEL SONULAR Bu yntem kullanlarak bambu tipli BNNTler baar ile retilmitir. Verilen byme modeline gre nanotplerin olutuu tespit edilmitir. 20 saat ve 40 saat tlen numuneler karlatrldnda, sl ilemden sonra 40 saatlik numunelerdeki rn miktarnn artt ve tp apnn azald tespit edilmitir. Bunun nedeni tme ile oluturulan ekirdek yap saysnn 40 saatte daha ideal olmasna ve tme sresinin artmasyla tlm tozun demir konsantrasyonunun artmasna balanmaktadr. 5. KAYNAKLAR Rubio, A., J. L. Corkill and M. L. Cohen, Theory of Graphitic Boron NitrideNanotubes, Physical Re1. view B, Vol. 49, pp. 5081-5084, 1994. Chopra, N. G.; Luyken, R. J.; Cherrey, K.; Crespi, V. H.; Cohen,M. L.; Louie, S. G.; Zettl, Boron-Nitride 2. Nanotubes A. Science , Vol. 36 269-966,1995 H. Zhang and Y. Chen Boron Nitride Nanotubes:Synthesis and Structure,Nanotubes and nanofibers, 3. pp 157-174, Australia,2006 Y. Chen and J. S. Williams Synthesis of Boron Nitride Nanotubes Using a Ball-Milling and Annealing 4. Method, Nanoengineering of Structural,Functional, and Smart Materials,pp 182-208, Australia,2006 Y. Chen, M. Conway, and J.S. Williams,Large-quantity production of high-yield boron nitride nanotubes, 5. J. Mater. Res., Vol. 17, No:8, Australia,2002 E.J.M. Hamilton, S.E. Dolan, C.M. Mann, H.O. Colijn, C.A.McDonald, S.G. Shore, Preparation of 6. Amorphous Boron Nitride from the Reaction of Haloborazines with Alkali Metals and Formation of a Novel Tubular Morphology by Thermal Annealing Chem. Mat.Science,Vol7, pp 11-117,1993. German R.M.,Sintering Theory and Practce, Joyn Wiley & Sons. Inc., USA,1996 7. 8. L. T. Chaddertona, Y. Chen A model for the growth of bamboo and skeletal nanotubes: catalytic capillarity, Physics Letter A, Vol. 263, pp 401-405,Australia,2001
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BOR KARBRL ELMASLI KESC SOKETLERN MKROYAPI VE MEKANK ZELLKLER

Serkan ISLAK*, Durmu KIR**, Halis ELK***, Erturul ELK****
*
Kastamonu niversitesi, Cide Rfat Ilgaz Meslek Yksekokulu, 37600 Kastamonu, sislak@kastamonu.edu.tr ** Kocaeli niversitesi, Gebze Meslek Yksekokulu, 41400 Kocaeli, durmuskir@gmail.com *** Frat niversitesi, Teknoloji Fakltesi, Metalurji ve Malzeme Mh. Blm, 23100 Elaz, durmuskir@gmail.com, hcelik@firat.edu.tr **** Tunceli niversitesi, Mhendislik Fakltesi, Makine Mh. Blm, 62000 Tunceli ecelik@tunceli.edu.tr ZET
Bu almada, doal ta kesme ilerinde kullanlan elmasl kesici soketlere bor karbr (B4C) ilavesinin mikroyap ve mekanik zellikleri zerine etkisi aratrlmtr. Bu amala, deneylerde B4C arlka % 2, 5 ve 10 oranlarnda kullanld. Tm deneylerde scak presleme ilemi 35 MPa basnta, 700 C scaklkta ve 3 dakika sreyle yaplmtr. Soketlerin mikroyap ve faz bileimi taramal elektron mikroskobu (SEM), X-n difraktogram (XRD), X n enerji dalm spektrometresi (EDS) ile belirlenmitir. Mikrosertlik ve eme dayanm deerleri ise srasyla sertlik ve noktal eme test cihazyla llmtr. Soketlerin sertlik ve eme dayanmlar bor karbrn oranna bal olarak deimitir. Anahtar Kelimeler: Elmasl soketler, bor karbr, scak presleme
MICROSTRUCTURE AND MECHANICAL PROPERTIES OF DIAMOND CUTTING SEGMENTS WITH BORON CARBIDE
ABSTRACT In this study, effect of boron carbide (B4C) addition on microstructure and mechanical properties of diamond cutting segments that are used in cutting works of natural stones were investigated. For this purpose, the boron carbide was changed as 2, 5 and 10 wt. % percents. In all of the experiments, hot pressing process was carried out at 35 MPa pressure, at 700 C temperature and 3 minutes sintering time. Microstructure and phase composition of segments were determined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analysis. Microhardness and bending strength values were measured by hardness and threepoint bending test devices, respectively. Hardness and bending strength values of segments changed depending on boron carbide rate. Keywords: Diamond segments, boron carbide, hot pressing 1. GR Sentetik elmasn kullanm alanlar arasnda, sert malzemelerin kesilmesi, talanmas, delinmesi ve parlatlmas ilerinde kullanlan elmasl takmlar en byk paya sahiptir. Elmasl takmlarn piyasada, dairesel testereler, karotlar, elmasl teller ve matkaplar gibi birok eidi mevcuttur [1]. Bu takmlar genellikle toz metalurjisi yntemleri ile retilmektedir. Toz metalurjisi yntemi ile retilecek paralarn preslenmesi genellikle oda scaklnda yaplmaktadr. Son yllarda oda scakl zerindeki ortamlarda da scak presleme ile para retimi salanmaktadr. Bu yntem
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kullanlarak daha az kalp-metal tozu ara yzey srtnmesi ile, daha dk presleme basnlarnda daha yksek younluun elde edildii grlmtr [2-5]. Scak presleme esnasnda, elmas tanecikleri fiziksel ve kimyasal etkileimler ile metal matrise balanr. Elmasl kesici takmn kesme performansn olumsuz ynde etkileyen, elmasn grafitlemesi, znmesi ve zarar grmesi gibi faktrlerden kanmak iin sinterleme parametrelerinin ok dikkatli seilmesi gerekir [6]. Elmasl kesici takmlarn kesme performans ve kullanm sresi birok faktr tarafndan etkilenmektedir. Bu temel faktrler; elmas ve matris zellikleri, soket retim metodu, kesme artlar (kesme hz, evresel hz ve kesme derinlii), kesme modu (ayn ve zt ynl kesim), doal tan minerolojik ve mekanik zellikleri, soutma etkisi, kesme makinesinin zellikleri ve operatrn becerisidir [7]. Elmasl kesici takmlardaki soketlerin retiminde kullanlan metalik matrislerin iki temel fonksiyonu vardr. Birincisi elmas skca tutmak, ikincisi ise elmas kayb ile uyumlu bir oranda optimum olarak anmaktr [8,9]. Bu ilikiyi en st dzeye getiren teknikler metal-elmas ara yzeyinde atomik balanma, mekanik dayankllk ve anma hznn kontroln kapsar. Elmas tanelerinin matrisin ar bir ekilde anmas sonucunda desteksiz bir ekilde matris yzeyinden ne fazla miktarda kmal ne de zamanndan nce matristen kopmaldr. Bunun iin matrisin anma direnci kesilecek malzemenin anabilirlik zellii ile uyumlu olmaldr [10,11]. Literatrde bir ok almada Fe, Co, Ni, Ti, W, Cu ve CuSn matris malzemesi olarak kullanlmtr. Nitkiewicz ve Swierzy [12], elmasl soketlerde kalayn kesme performans zerine etkisini incelemiler ve belirli miktarda ilavesinin kesme performansna olumlu etki yapt gzlenmi ve demirli matrislerle farkl takmlarda da kullanlabilecei ett edilmitir. Barbosa ve arkadalar [13], Fe-Cu-Co matrisli elmasl takmlar retmilerdir. En uygun matris bileiminin Fe-% 60 Cu-%20 Co olduunu yaplan noktal eme ve anma testleriyle gstermilerdir. Artan Cu miktar ile soketlerin younluu artm ve sertliklerinde de iyileme gzlenmitir. Metalik matrisin anma direncini arttrmak ve elmas ile matris ara yzeyinde ba glendirmek amacyla matrise karbrler ilave edilmektedir. Literatrde bu konuda kstl alma mevcuttur. Meszaros ve Vadasdi [14] Co-% 2 WC matrisli elmasl kesici takmlar retmilerdir. Yaplan almada WCn abrasyon ile matrisin ktle kaybn kontrol ettii ve bu ekilde anma direncini arttrd rapor edilmitir. Oliveira ve arkadalar [4], elmasl kesici takm iin matris olarak Fe-Cu-SiC tozlarn kullanmlardr. SiC ilavesi ile anma orann kontrol edici etkiye sahip olan sertlikte % 14 orannda bir art gzlenmitir. Ayrca ilave edilen SiCn tane boyutu arttka matrisin anma direncinde art meydana gelmitir. Son zamanlarda, yksek ergime noktas, yksek sertlii, dk younluu, yksek kimyasal kararllk ve mkemmel mekanik zelliklere sahip olan bor karbr (B4C) ileri teknoloji iin nemli bir malzemedir. Bor karbr elmas ve kbik bor nitrrden (cBN) sonra bilinen en sert malzemedir. Yksek sertliinden dolay anma direncinin iyiletirilmesi amacyla kullanlmaktadr. Yksek dayanm/younluk oran onu endstri iin ideal bir malzeme yapmaktadr [15-18]. Bu almada, doal ta kesme ilerinde kullanlan elmasl soketlere bor karbr (B4C) ilavesinin mikroyap ve mekanik zellikleri zerine etkisi aratrlmtr. Bu amala, deneylerde B4C arlka % 2, 5 ve 10 oranlarnda ilave edilmitir. Tm deneylerde scak presleme ilemi kullanld. Soketlerin mikroyap ve faz bileimi taramal elektron mikroskobu (SEM), X-n difraktogram (XRD), X n enerji dalm spektrometresi (EDS) ile belirlenmi; mikrosertlik ve eme dayanm deerleri ise srasyla sertlik ve noktal eme test cihazyla llmtr. 2. DENEYSEL ALIMALAR Deneysel almalarda matris olarak CuSn ve B4C tozlar kullanlmtr. Bor karbr tozu farkl yzde arlk oranlarnda matrise ilave edilmitir. Soket retiminde kullanlan matris gruplar Tablo 1de, kullanlan tozlarn zellikleri ise Tablo 2de verilmitir. ekil 1de soket retiminde kullanlan CuSn ve B4Cn SEM fotoraflar ve XRD grafikleri grlmektedir. Bronz tozu kresel ekilli ve bor karbr tozu ise keskin keli bir ekle sahiptir. Tablo 1. Soket retiminde kullanlan matris gruplar ve retim parametreleri Sinterleme Sinterleme Basn Matris (% a.) CuSn 100 98 95 90 B 4C 2 5 10 700 3 35 scakl (C) sresi (dak.) (MPa)
No S1 S2 S3 S4
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Tablo 2. Kullanlan Tozlarn zellikleri Tozlar CuSn B4 C zellik % 85 Cu, % 15 Sn, % 99.9 saflk % 79 B, % 20.5 C, % 99.9 saflk Tane boyutu (m) 45-50 ~20
ekil 1. Soket retiminde kullanlan tozlarn SEM fotoraflar ve XRD grafikleri: (a) CuSn tozu, (b) B4C Tablo 1de ki gibi hazrlanan matris gruplar mikserde 30 dakika sre ile 20 d/d hzda % 1 orannda parafin ya karma eklenerek krom kaplanm elik bilyeler ile birlikte kartrlmtr. elik bilye kullanmndaki ama karma katlan parafin yann topak oluturmasn engellemektir. Toz halindeki soketler 15 MPa basnla souk olarak preslendi. Biskvi eklindeki soketler grafit kalplarda scak presleme teknii kullanlarak nihai soket haline dntrld. Her bir soket 35 MPada 700 C scaklkta 3 dakika sinterleme sresinde elde edildi. ekil 2de soketlerin grafit kalba yerletirme dzeni ve sinterleme grafii grlmektedir.
ekil 2. (a) Soketlerin grafit kalba yerletirme dzeni ve (b) sinterleme grafii
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Scak presleme yntemi ile retilen soketlerin bal younluu, sertlii ve eme dayanm tespit edilmitir. Numunelerin bal younluk lm Archimedes prensibine gre yaplmtr. Sertlik lm iin Karl Frank marka sertlik lme cihaznda 62,5 kg yk ve 2.5 mm apnda bilye ile numunelerin sertlii Brinell cinsinden llmtr. Soketlerin eilme dayanmlar, 40 mm x 7 mm x 3.2 mm lsndeki numuneler kullanlarak noktal eme testi ile tespit edilmitir. Metalografik incelemeler iin numuneler, 3.2 mm x 7 mm x 10 mm llerinde kesilmitir. Elde edilen metalografi numuneleri 80-1200 meshlik zmpara kadna tutularak yzeyleri temizlenmitir. Daha sonra 1 ve 6 mlik elmas pasta ve inceltici yardmyla yan kesit yzeyleri parlatlmtr. Mikroyap incelemeleri iin numuneler 20 saniye sreyle 5 gr. FeCl3, 50 ml HCl ve 100 ml H2O zeltisinde dalanmtr. Soketlerin mikroyapsnn retim koullarna bal olarak nasl deitiini ve faz yaplarn tayin etmek iin ve krk yzeylerini incelemek iin taramal elektron mikroskobu (SEM), enerji dispersive spektograph (EDS), X- n difraksiyonu (XRD) ve spektral analizlerden yararlanlmtr. XRD analizleri 30 kV ve 15 mAde CuK radyasyonu kullanlarak Rigaku Geigerflex X-n difraktometresi ile elde edilmitir. 3. SONULAR VE TARTIMA CuSn ve CuSn-B4C matrisli soketler scak presleme yntemi ile 700 C scaklkta, 35 MPa basnta ve 3 dakika sinterleme sresinde baaryla retildi. CuSn matrisinin mikroyapsnda -Cu ve -bronzu (Cu3Sn) fazlar olumutur. Bu durum Cu-Sn ikili faz diyagram (ekil 3) ve ekil XRD grafii (ekil 4) ile de desteklenmektedir. Cu3Sn faz ekil 5deki SEM fotoraflarndan da grld gibi Cu partikllerinin tane snrlarnda kelmitir.
ekil 3. Cu-Sn ikili faz diyagram [19]
ekil 4. Soketlerin XRD grafii
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CuSn tozuna arlka % 2, 5 ve 10 oranlarnda B4C ilave edilerek CuSn-B4C kompoziti retilmitir. retilen CuSnB4C matrisinde B4C paracklar mikroyapda nispeten homojen olarak dalmtr ve CuSn tarafndan kuatlmtr (ekil 5). takviye partikllerin matris ierisinde homojen olarak dalmad durumlarda kompozitin mekanik ve fiziksel zellikleri olumsuz ynde etkilenmektedir [20]. Bu takviyeli matrislerin SEM fotoraflarnda koyu renkli ve keli partikller B4Clerdir. Bor karbr oran arttka, B4C partiklleri CuSnnin tane snrlarna doru yaylarak bir a oluturmutur (ekil 5b-c-d). Ayrca bor karbr ilave miktar arttka soketlerin XRD grafiklerindeki B4C piklerinin iddetleri artmaktadr. XRD grafikleri CuSn ve B4C arasnda herhangi bir kimyasal reaksiyonun olmadn da gstermektedir. CuSn-B4C soket matrislerinin mikroyapsnda gzenekler tane snrlarnda olumutur. Bor karbr oran arttka gzeneklilik miktar artmtr. Bu durum B4Cn sinterlenebilme zelliin dk olmasndan kaynaklanmaktadr. CuSn-B4C matrisli soketlerde B4C ilavesinin sktrlabilirlik zellikleri zerine belirlemek iin soketlerin deneysel younluklar lld. Matrislerin deneysel ve teorik younluklar kullanlarak bal younluklar belirlendi. ekil 6da bor karbr ilavesinin soketlerin deneysel ve bal younluklar zerine etkisi verilmitir.
ekil 5. Soket matrislerinin SEM fotoraflar: (a) CuSn, (b) CuSn-% 2 B4C, (c) CuSn-% 5 B4C ve (d) CuSn-% 10 B4C Tablo 3te ekil 5deki SEM fotoraflarnda belirlenen blgelerin EDS analizi verilmitir. 1 blgesinin EDS analizi tane kesinde oluan Cu3Sn ve B4C fazlarn iaret etmektedir. 2 nolu blge matris faz yani CuSnyi gstermektedir. 3 nolu blgenin analizi % 99.142 C ve % 0.858 Sndir. Bu bor karbr tanesi zerinden alnan analizdir. Fakat EDS analizinde B elementinin okunmamasnn sebebi karbon ve borun atom aplarnn ok kk ve birbirine yakn olmasdr. 4 nolu blge tane snrlarnda oluan Cu3Sn fazdr. Tablo 3. Soketlerde verilen blgelerin EDS analizi Blge 1 blgesi 2 blgesi 3 blgesi 4 blgesi Kimyasal bileim (% a.) B 0.000 0.000 0.000 0.000 C 13.425 0.000 99.142 0.000 Cu 53.142 85.461 0.000 62.281 Sn 33.433 14.539 0.858 37.719
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ekil 6. Bor karbr ilavesinin soket matrisinin deneysel ve bal younlua etkisi Artan bor karbr orannda younluklarda d meydana gelmitir. Bu durum bor karbrn younluunun (2,52 gr/ cm3) bronzun younluundan (8,68 gr/cm3) dk olmasyla ilgilidir. Yine artan bor karbr ilavesiyle bal younluklarda d meydana gelmitir. Bu durum artan bor karbr orannn sinterlenebilirlii olumsuz etkilemesiyle aklanabilir [21]. Dier bir sebep ise, matris ile takviye eleman yani bronz ile bor karbrn ergime noktalar arasndaki byk farkllk, sinterleme annda partikllerin tekrar dzenlenmesinde nleyici bir faktr olmasdr. Bor karbr ilaveli soketlerde en iyi younlama CuSn-% 2 B4C matrisinde yaklak % 93,01lik bal younluk ile olmutur (ekil 6). ekil 7de CuSn ierisine farkl oranlarda ilave edilen bor karbrn sertlik zerine etkisi grlmektedir. Her bir numune iin toplam alt adet lm yaplmtr. Deerlendirmede lmlerin ortalamas kullanlmtr. Bor karbr ilavesiyle elde edilen CuSn-B4C soket matrislerin sertliklerinde belirgin bir art olmutur. CuSn, CuSn-% 2 B4C, CuSn-% 5 B4C ve CuSn-% 10 B4C soketlerinin sertlikleri srasyla 78 HB, 87 HB, 109 HB ve 118 HB olarak llmtr. Bu sertlik artna bor karbrn dalm mukavemetlendirme etkisi sebep olmutur. Sertlik art ile soket matrisinin anma direnci arttrlmaya allmtr.
ekil 7. B4C ilavesinin soketlerin eme mukavemeti ve sertliine etkisi Krlma tokluunu belirlemek iin CuSn ve CuSn-B4C matris numunelerine 3-noktal eme testi uygulanmtr. Her bir matris iin noktal eme testi beer defa tekrarlanmtr. Elde edilen deerlerin ortalamas alnarak retim
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parametrelerinin etkisi tartlmaya allmtr. Eme mukavemeti zerine bor karbr ilavesinin etkisi yine ekil 7de grlmektedir. Bor karbr ilave miktar arttka soket matrislerin eme mukavemeti deerlerinde d gzlenmitir. CuSn, CuSn% 2 B4C, CuSn-% 5 B4C ve CuSn-% 10 B4C soket matrislerinin eme dayanmlar srasyla 477.40 MPa, 412.00 MPa, 372.42 MPa ve 244.48 MPa olarak llmtr. Eme mukavemeti deerlerinde bu dn sebebi yksek sertlie sahip bor karbrn artan miktarlarda soket matrisini gevrekletirmesidir. Ayrca takviye eleman ile snek matris arayzeyinde genleme katsays farkllndan dolay gerilim younlamas meydana gelir. Bu gerilim younlamas eme mukavemetinin dmesine yol amtr [22]. Ksaca bor karbr bronz matrisinin krlmasnda hata unsuru olmutur. Kompozit malzemelerde genel olarak krlma olay partikl krlmas, arayzeyde zayf balanma ve matris malzemesinin deformasyonu olmak zere hata mekanizmas ile oluur [23]. Bor karbr takviyesiz olan soket numunesinde matrisin plastik deformasyonu krlma olaynda hkim mekanizmadr (ekil 8a). Yine bu numunede boyun verme olay dier numunelere gre daha youn miktardadr. Bor karbr takviyeli soketlerin krlma yzeyinde ise bor karbr taneleri ile CuSn matrisi arasnda zayf balanmas sz konusudur. Bor karbr miktar arttka matris ile bor karbr taneleri arasndaki balanma daha da zayflamaktadr. Bu durum ekil 8b-c-dde ak bir ekilde grlmektedir. Bu zayf balanma olay sinterleme koullarnn yetersizliinden kaynaklanmaktadr. Daha yksek presleme basnc ve sinterleme scakl kullanlarak matris (CuSn) ile takviye eleman (B4C) ara yzeyindeki zayf balanmann stesinden gelinip eme dayanmnn arttrlaca dnlmektedir.
ekil 8. Soket matrislerinin krma yzeylerinin SEM fotoraflar: (a) CuSn, (b) CuSn-% 2 B4C, (c) CuSn-% 5 B4C ve (d) CuSn-% 10 B4C 3. GENEL SONULAR Scak presleme ile 700 C sinterleme scakl, 35 MPa presleme basnc ve 3 dakika sinterleme sresinde retilen CuSn-B4C matrisli soketlerde bor karbrn matris iinde nispeten homojen olarak dald SEM almalaryla gzlenmitir. Bor karbr taneleri bronzun tane snrlarnda olumu, bronz tarafndan kuatlmtr. Ayrca artan bor karbr ilavesinde gzenek miktarnda art gzlenmitir. Bor karbr ilavesiyle elde edilen CuSn-B4C soket matrislerin sertliklerinde belirgin bir art olmutur. En yksek sertlik deeri % 10 B4C ilavesinde 118 HB olarak llmtr. Bor karbr ilaveli soketlerde en iyi younlama CuSn-% 2 B4C matrisinde yaklak % 93,01lik bal younluk ile olmutur. Bor karbr ilave miktar arttka soket matrislerin eme mukavemeti deerlerinde d gzlenmitir. En dk toklua 244.48 MPa eme dayanm ile arlka % 10 B4C ieren numune sahiptir. Bor karbr ilavesiyle takviye ve matris ara yzeyinde zayf ara yzey balanmalar tespit edilmitir. Bu durum sinterleme koullarnn yetersizlii ile ilikilendirilmitir.
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4. TEEKKR Bu almann yrtlmesi ve sonulandrlmas ile ilgili konularda TEF.10.01 nolu proje ile maddi destek salayan Frat niversitesi Bilimsel Aratrmalar Projeleri Birimine (FBAP), teekkr ederiz. 5. KAYNAKLAR 1. Xu, X.P., Friction studies on the process in circular sawing of granite, Tribology Letters, Vol. 7, pp. 221-227, 1999. 2. Sun, J., Liu, C., Wang, R., Low pressure hot pressing of B4C matrix ceramic composites improved by Al2O3 and TiC additives, Materials Science and Engineering: A, Vol. 519, pp. 27-31, 2009 3. Kim, T.W., Determination of densification behavior of Al-SiC metal matrix composites during consolidation processes, Materials Science and Engineering: A, Vol. 483-484, pp. 648-651, 2008 4. Oliveira, L.J., Bobrovnitchii, G.S., Filgueira, M., Processing and characterization of impregnated diamond cutting tools using a ferrous metal matrix, International Journal of Refractory Metals and Hard Materials, Vol. 25, pp. 328-335, 2007. 5. zel, S., elik, E., Turhan, H., The investigation of microstructure and mechanical properties of Cu-Al/B4C composites produced by using hot press, e-Journal of New World Sciences Academy, Vol. 4 (1), pp. 106112, 2009. 6. Zeren, M., Karagz, ., Defect characterization in the diamond cutting tools, Materials Characterization, Vol. 57, pp. 111-114, 2006 7. Byksa, I.S., Effect of cutting mode on the sawability of granites using segmented circular diamond sawblade, Journal of Materials Processing Technology, Vol. 183, pp. 399-406, 2007 8. Konstanty, J., Production of Diamond Sawblades for Stone Sawing Applications, Key Engineering Materials, Vol. 250, pp. 1-12, 2003 9. Konstanty, J., Factors affecting diamond retention in stone sawblade segments, Key Engineering Materials, Vol. 250, pp. 13-20, 2003 10. Karagz, ., Zeren, M., The microstructural design of diamond cutting tools, Materials Characterization, Vol. 47, pp. 89-91, 2001 11. Konstanty, J., Powder Metallurgy Diamond Tools, Elsevier Ltd, The Metal Powders Technology Series, pp. 106-107, 2005 12. Nitkiewicz, Z., Swierzy, M., Tin influence on cutting behaviour of diamond sawblades for Stone cutting, 13th International Scientific Conference on Achievements in mechanical and materials Engineering, 16-18 May 2005, Gliwice-Wista, Poland, pp. 467-470, 2005 13. Barbosa, A.P., Bobrovnitchii, G.S., Skury, A.L.D., Guimares, R.S., Filgueira, M., Structure, microstructure and mechanical properties of PM FeCuCo alloys, Materials and Design, Vol. 31, pp. 522526, 2010 14. Meszaros, M., Vadasdi, K., Process and equipment for electrochemical etching of diamond-containing Co-Wc tools and recovery of diamond from used steel tools, International Journal of Refractory Metals and Hard Materials, Vol. 14, pp. 229-234, 1996 15. Pierson, H.O., Handbook of Refractory Carbides and Nitrides, William Andrew Pub., Noyes, 1996 16. Spohn, M.T., Boron Carbide, Minerals Review, Vol. 6, pp. 113-115, 1994 17. Jiang, T., Jin, Z., Yang, J., Qiao, G., Investigation on the preparation and machinability of the B4C/BN nanocomposites by hot-pressing process, Journal of Materials Processing Technology, Vol. 209, pp. 561-571, 2009 18. Ma, Q.C., Zhang, G.J., Kan, Y.M., Xia, Y.B., Wang, P.L., Effect of additives introduced by ball milling on sintering behavior and mechanical properties of hot-pressed B4C ceramics, Ceramics International, Vol. 36, pp. 167-171, 2010 19. Saunders, N., Miodownik, A.P., Cu-Sn (Copper-Tin), Binary Alloy Phase Diagrams, vol. 11, pp. 278-87, 1990. 20. Lee, D.W., Ha, G.H., Kim, B.K., Synthesis of Cu-Al2O3 nano composite powder, Scripta Materialia, Vol. 44, pp. 2137-2140, 2001 21. Rahimian, M., Ehsani, N., Parvin, N., Baharvandi, H.R., The effect of particle size, sintering temperature and sintering time on the properties of Al-Al2O3 composites, made by powder metallurgy, Journal of Materials Processing Technology, Vol. 209, pp. 5387-5393, 2009 22. Samuel, A.M., Gotmare, A., Samuel, F.H., Effect of solidification rate and metal feedability on porosity and SiC/Al2O3 particle distribution in an AlSiMg (359) alloy, Composites Science and Technology, Vol. 53, pp. 301315, 1995 23. Park, K.T., Mohamed, F.A., Creep strengthening in a discontinuous SiCAl composite, Metall. Mater. Trans. A, Vol. 26, pp. 31193129, 1995
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B4C TAKVYEL ALMNYUM KPKLERN KPRME ZELLKLERNN ARATIRILMASI

Uur GKMEN*, Halil KARAKO**, Arif UZUN***, Mehmet TRKER**
*
Gazi niversitesi, Atatrk MYO, Makine ve Metal Teknolojileri Blm, Teknikokullar, 06500, Ankara, ugokmen@gazi.edu.tr ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, halil.karakoc@hotmail.com, mturker@gazi.edu.tr *** Kastamonu niversitesi, Cide Rfat Ilgaz MYO, Kaynak Teknolojisi Blm, Kastamonu, a uzun@kastamonu.edu.tr ZET
Bu almada n alaml Alumix 231 tozu ierisine, % 1 orannda TiH2 ve farkl oranlarda (arlka % 3, 6, 9 ve 12) B4C tozu ilave edilerek kartrlmtr. Karm tozlar 600 MPa basn altnda tek ynl preste sktrlm ve 550 o Cde n stmaya tabi tutulmutur. Daha sonra numuneler sktrma ynnde deforme edilerek kprebilir kompozit preform malzemeler haline getirilmitir. Elde edilen preform numuneler 710C scaklkta kprtme ilemine tabi tutularak metal matrisli kompozit kpkler retilmitir. retilen metalik kpklerde B4C ilavesinin kprme davran zerine etkileri aratrlmtr. Anahtar Kelimeler : Alminyum Kpk, Alumix 231,B4C, Kprme Davran
INVESTIGATION OF THE FOAMING BEHAVIOUR OF B4C REINFORCED ALUMNUM FOAMS

ABSTRACT In this study, Alumix 231, 1% titanium hydrate (TiH2) and various amount of B4C (3%, 6%, 9% and 12 % by weight) powders were mixed, and then compacted at 600 MPa pressure by using a uniaxial action press and pre-heated to 550 oC in a furnace. Then the samples were deformed in the direction of compression to produce foamable composite precursor materials. Produced precursor samples were foamed at 710C in order to produced metal matrix composite foams. Effects of B4C addition on foamability behavior of metallic foams were invested. Keywords: Aluminum Foam, Alumix 231, B4C, Foaming Behaviour 1. GR Kapal gzenekli alminyum kpkler mekanik ve fiziksel zelliklerinden dolay yapsal ve fonksiyonel uygulamalar iin cazip hale gelmi malzemelerdir. Bu malzemelerin endustriel boyutta retiminde dkm ve toz metalurjisi (TM) en fazla kullanlan yntemlerdir. Ancak TM yntemi net ekilli paralarn dorudan retimine olanak salamas aratrmaclar bu yntem zerine daha da ok yneltmitir. TM yntemi ilk olarak Fraunhofer Malzeme Aratrma Enstits (IFAM) tarafndan gelitirilmitir [1]. Bu yntem de sandvi levha eklinde veya karmak ekilli homojen gzenek yaplara sahip kpk paralar kprebilir preform malzemelere uygulanan sl ilem ile retilmektedir [2]. lem sreci yksek younlukta preform malzeme retimi iin Al tozlar ile kprtc madde tozlarnn kombinasyonu ile balamaktadr. Daha sonra preform malzemelerin alminyumun ergime derecesinin biraz zerindeki bir
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scaklkta kprtlmesi ile ilem sreci tamamlanmaktadr. Bu srete ergiyik hale gelen alminyum ierisinde, kprtc madde znerek hidrojen gaz aa karmaktadr. Yap ierisinde giderek artan hidrojen gaz, gzenekli alminyum kpk oluumunu salamaktadr. Ancak ergiyik halde bulunan Al kpk, plato snrlar ve hcre duvarlar boyunca ergiyik drenaj ve artan yzey alan nedeniyle termodinamik ve kinetik adan kararl deildir [3,4]. Bu etkiler mekanik zellikleri dk, homojen olmayan kpk yaplarn oluumuna neden olmaktadr. Daha nce yaplan almalarda kpn kararlln ayarlayabilmek iin yap ierisine SiC, Al2O3, TiB ve TiC gibi seramik paracklar ilave edilmektedir [5-8]. lave edilen seramik paracklar ergiyik halde bulunan alminyumun viskozitesini artrarak, hcre duvar boyunca ergiyik akn drmekte, drenaj orann ve hcre duvar kntlerini azaltmaktadr. Fakat slatlabilirlii iyi olan paracklarla bu durum daha etkin hale gelebilmektedir. Bu almada ise B4C paracklarnn kprebilirlie etkisi aratrlmtr. 2. DENEYSEL ALIMALAR Deneysel almalar uygun miktarlarda hazrlanan n alaml Alumix 231 (2,5 Cu, 0,5 Mg, 14 Si - < 160 m), TiH2 (arlka % 1 - < 45 m) ve B4CP ( arlka % 3, 6, 9 ve 12 - < 10 m) tozlarnn karm ile balamtr. Karm boyutlu kartrcda (turbula) 30 dakika sreyle plastik bir kap ierisinde gerekletirilmitir. Daha sonra karm tozlar, kprebilir metal matrisli kompozit (MMK) preform malzemeler retmek amac ile elik kalp ierisinde tek ynl olarak 600 MPa basn altnda Preslenmitir ( ekil 1-a). Presleme sonras 550 Cde 4 saat bekletilen numuneler % 50 orannda deforme edilmitir (ekil 1-b). Daha sonra kprebilir kompozit preform malzemeler 710 C scaklkta, yaklak 10 dakika frn ierisinde bekletilerek kprtme ilemine tabi tutulmutur. Bu ilem sresince herhangi bir kprtme kalb kullanlmamtr. retilen kpk numunelerin younluklar ve hacimsel olarak genleme oranlar 0,1 mg hassasiyetteki terazi ve younluk kiti ile llmtr. Buna gre younluk hesab E.1de verilen Arimet prensibi esasna gre yaplmtr. Bu eitlikte, * kpn younluunu, mhava kpn havadaki arln ve msu kpn su ierisindeki arln ifade etmektedir.
*=mhava/(mhavamsu) (1)
Genleme oran ise E. 2de verilen formle gre hesaplanmtr. Bu formlde V* kpn hacmini, V ise kprtme ncesi numunenin ilk hacmini ifade etmektedir. Hacimsel Genleme ( HG ) = (V*/V-1) x 100 (2)
ekil 1. Souk preslenmi (a) ve % 50 deforme edilmi preform malzemeler (b) 3. DENEYSEL SONULAR ve TARTIMA ekil 1de % 1 orannda TiH2 ieren ve 710C scaklkta kprtme ilemine tabi tutulan numunelerde takviye elaman (B4C) miktarna bal olarak hacimsel genileme ve younlukta meydana gelen deiimler gsterilmitir. Grafie bakldnda parack ilavesinin hacimsel genlemeye azaltc, younlua ise artrc ynde etki ettii grlmektedir.
ekil 1. B4C miktarna bal hacimsel genileme ve younluk deiimi
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ekil 2de takviyeli ve takviyesiz alminyum kpklerin ara kesit fotoraflar verilmitir. Serbest kprtme neticesinde elde edilen numunelerde B4C ilavesinin kprme davranna ve gzenek morfolojisine olumsuz ynde etki ettii aka grlmektedir. Parack miktar % 6y getiinde numunelerde yeterli kprme meydana gelmemektedir. % 3 ve % 6 orannda parack ieren numunelerde ise gzenek boyut dalmnn, takviyesiz numuneye kyasla homojen olmad grlmektedir.
ekil 2. B4C miktarndaki arta bal olarak gzenek yaps ve younlukta meydana gelen deiim ekil 3te % 6 B4C ieren Almix 231 matrisli kompozit kpklerin SEM grnts verilmektedir. Bu grntlerde B4C paracklar net olarak tespitedilememitir. Ancak yaplan EDX analizlerinde 1 nolu blgede C elementine rastlanmtr. Paracn bu blgede matris ierisine gmlm olduu dnlmektedir. Bu durum parack-matris uyumunun iyi olduunu gsterebilir. Fakat baz aratrmalarda dkm yntemi ile retilen Al-B4C kompozitlerde 1100oCnin altnda alminyum ile bor karbr arasndaki slanmann dk olduu bilinmektdir. Bundan dolay ilave edilen parack ya kaplanmakta yada sl ileme tabi tutulmaktadr [9]. SEM grnts haritalandrldnda (FastMap) B ve C elementinin yap ierisinde homojen bir ekilde dald grlmektedir (ekil 4). Bundan dolay ilave edilen paracklarn hcre duvarlarnda homojen dalm sergiledii sylenebilir. Matris malzemesi olarak n alaml Alumix 231 kullanldndan alminyumdan sonra yapda en fazla Si elementine rastlanmaktadr. Silisyum, TM yntemi ile kpk retiminde matris ierisine ilave edilen en yaygn alam elementlerindendir [10]. Si, tektik noktay drdnden dk scaklklarda ergiyik hale gelen Al ile parack ara yzey uyumu artabilir.
ekil 3. % 6 B4C ieren Almix 231 matrisli kompozit kpklerin SEM grntleri
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ekil 4. % 6 B4C ieren Almix 231 matrisli kompozit kpklerin FastMap analiz yzeyi 4. SONULAR ve NERLER Bu almada toz metalurjisi yntemi ile retilmi metal matrisli kompozit kpklerde B4C ilavesinin kprme davran zerine etkisi incelenmi. Elde edilen verilere gre B4C oranndaki art younlukta ata, hacimsel genlemede ise azalmaya neden olmutur. Parack ilavesinde kritik deer % 6 olarak belirlenmitir. nk % 6dan sonra gzenek morfolojisinde ve kprme davrannda olumsuz ynde etkiler sz konusudur. Ayrca parack boyutunun (<10 m) kklnden dolay matris/parack ara yzey uyumu tam olarak gzlenememitir. Ancak hcre duvarlarnda homojen dalm sergiledii FasMap analizi ile belirlenmitir. Daha sonra yaplacak almalarda parack boyutunun etkisi ve mekanik zellikler belirlenebilir. Bu sayede daha ak sonulara ulalabilir. KAYNAKLAR 1. Baumaster, J., US patent, 1992 2. Yu, C.J.,Eifert, H.H., Banhart, J., Baumeister, J., Metal foamingby a powdermetallurgymethod: Production, propertiesandapplications, Mat Res Innova, 2:181188, 1998 3. Gergely V., Jones R.L. and Clyne T.W., The Effect of Capillarity-driven Melt Flow and Size of Particles in Cell Faces on Metal Foam Structure Evolution, Trans. JWRI, 30:371-376, 2001 4. Gergely V. and Clyne, T.W., Drainage in standing liquid metal foams: modelling and experimental observations. Acta Mater., 52(10): 3047-3058, 2004 5. Kennedy A.R. and Asavavisithchai S., Effect of ceramic particle additions on foam expansion and stability in compacted Al-TiH2 powder precursors, Adv. Eng. Mater., 6(6): 400-402, 2004 6. Guden M. and Yuksel S., SiC-particulate aluminum composite foams produced from powder compacts: foaming and compression behavior, J. Mater. Sci., 41(13): 4075-4084, 2006 7. Kennedy A.R. and Asavavisithchai S., Effects of TiB2 particle addition on the expansion, structure and mechanical properties of PM Al foams, Scr. Mater., 50(1): 115-119, 2004 8. Asavavisithchai, S., and Opa, A., Effect of TiC Particles on Foamability and Compressive Properties of Aluminium Foams, Chiang Mai J. Sci., 37(2) : 213-221, 2010 9. Kennedy, A.R., Bramton, B., The Reactive Wetting and Incorporation of B4C Prticles into Molten Aluminium, Scripta Materiala, 44:1077-1082, 2001 10. Esmaeelzadeh, S., Simchi, A., Foamability and compressive properties of AlSi73 vol.% SiC0.5 wt.% TiH2 powder compact, Materials Letters 62:15611564, 2008
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CHARACTERIZATION OF POWDER AND PARTS
www.turkishpm.org
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Transverse Rupture Strength Properties of Diamond Impregnated Metal Matrix

James D. Dwan Mechanical Engineering Dept. ITT Dublin, Tallaght, Dublin 24, Ireland Abstract The determination of mechanical properties of diamond impregnated metal matrices (DIMMs) is very important if proper understanding of the relationship between workpiece and the diamond tool is to be achieved. Transverse Rupture Strength (TRS) is a common mechanical test carried out on metal matrices as used in diamond tools. This is mainly because standard tensile testing is more problematic to carry out successfully due to the more brittle nature of the metal matrices used in diamond tools, especially cobalt matrix. Mechanical testing of DIMMs is rarely carried out mainly due to cost. This paper reports on TRS properties of diamond impregnated cobalt metal matrix (DICoMM). The effects of diamond size and concentration on the TRS of PM cobalt have been investigated. A measure of ductility called Displacement-at-Break derived from bend testing is also reported. The results presented and effect of the addition of diamond to the failure of DICoMM materials proposed. 1.0 Introduction Most research work carried out to-date into the mechanical properties of diamond impregnated metal matrix materials has concentrated solely on the metal matrix. However, some work has been conducted on mechanical property determination of DIMMs [1, 2, 3, 4, 5, 6, & 7]. However, their work was very limited in a number of areas [8, 9 & 10]. The optimum wear of the diamond impregnated metal matrix is paramount to the efficient operation and life of the diamond tool. However, the matching of the mechanical properties of the diamond tool to its workpiece in order to achieve this optimum is not very well understood. The purpose of this present paper into Transverse Rupture Strength (TRS) is only part of an overall investigative work into the wear-matching of the diamond tool and the workpiece. 2.0 Transverse Rupture Strength (TRS) Testing & PM/PMMC Type Materials As mentioned in previous papers by the author [1, 2, 3 & 5]. PM and particulate metal matrix composites (PMMCs) materials are related to DIMMs in their macro and microstructure. They are used by the author as reference materials in developing and understanding the mechanical properties of DIMMs. Particulates used in PMMCs can be regular or irregular in shape and can arranged in a random or with a preferred orientation. The PM process is a common method used for the fabrication of PMMCs and these will only be considered here [11, 12, 13, 14 & 15]. Transverse rupture testing of PM as well as PMMCs is a very common test. Regarding hardmetals, it is used as a characteristic of resistance to fracture [16]. Various versions of it are used, e.g. 3-point and 4-point, and standards e.g. ASTM B528-76, different sample preparations are carried out including the grinding & polishing of the surfaces, different specimen dimensions, crosshead speeds and spans e.g. 16-40mm, are used, and so one must take care in using such values unless all test parameters are mentioned [17, 16, 18]. TRS of PM-type PMMCs depends on structure and composition but is also especially sensitive to the degree of porosity both micro and macro-pores which act as internal flaws. In TRS testing, maximum tensile stress is experienced on the outer fibres of the loaded beam and so any flaws present on this outer surface will be potential crack initiators. Having measured the load to break the specimen, the Modulus-of-Rupture (MOR) or simply TRS which is valid if no plasticity is detected in the bend test is calculated. Also, depending whether it is three-point or four-point type test will influence the failure stress and the statistical probability of finding a critical flaw on the outer surface. So this high sensitivity to external flaws (stress concentrations) results in relatively high scatter of values. So for minimisation of scatter in results, sample preparation is paramount e.g. polished samples are often used.
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In PMMCs it is found that TRS is affected both by the size and type of the ceramic particles [17], some researchers found that the addition lowered TRS values [19], also that TRS increased with decreasing particle size and which also caused an increase in variability in TRS data. There was also an increased scatter in the bending strength data [20]. 3.0 Experimental Procedure Eurotungstene COUF ultrafine cobalt powder was used as the metal matrix in its granulated form (63-350m) with approx.1.3 % binder. Element 6 synthetic diamond SDA 85+ grade was used in the following US Mesh sizes: (25/30, 35/40, 45/50, 60/70 & 80/100). The diamond concentrations (DCs) used were 1, 10, 20, 30 & 40 for all the above sizes. The nominal specimen dimensions were 55mm x 5mm x 10mm. Specimens were hot pressed at 800oC with the preparation procedure and hot pressing profile as already described in [5]. 100% cobalt specimens were also hot pressed using the same temperature of 800oC. Replication was achieved by using four (4) specimens for each treatment of diamond size and concentration. Randomisation of the experimental testing was also practised to ensure good experimental protocol. In total, 121 samples were tested. Density was determined for all the specimens using the standard Archimedes Principle method. An Instron 8516 servohydraulic universal testing machine with Instron proprietary interface software SERIES-IX [21] was used. A 10kN load cell with a strain rate of 0.5mm/min was used. A three-point bend fixture with a span of 40mm was used with an external linear variable differential transducer (LVDT) to accurately measure the beam deflection, allowing the Displacement-at-Break to be determined (Figure 1).
Figure 1. Three-Point Bend Fixture Mark I showing TRS specimen & LVDT extensometer. A safety cage also allowed the recovery of broken specimens. Having measured the load to break the specimen, the TRS was calculated using the conventional formula, Equation 3.1, as found in the ASTM Standard B528-76: (3.1.) where P = break load (N), L = (span) distance between the supporting rollers (mm), (40mm), t = thickness of the test specimen (Specimen Depth or Height) (mm), w = width of the test specimen (mm). 4.0 Results & Discussion 4.1. TRS Specimens Results - % Theoretical Density (%TD) Figure 2 shows for the TRS type specimens the average %TD value for each DC. Included is the %TD for CoMM in red in the graph. As can be seen in Figure 2, the addition of diamond does cause a reduction in %TD when added to the cobalt matrix. The average %TD for CoMM is 95.6% whereas the average for all TRS DICoMM specimens is 93.9%.
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Figure 2.TRS Specimen Results: Figure shows the Average %TD achieved for CoMM and DICoMMs for each DC. The average values recorded on the graph are the overall average obtained for each DC. CoMM is included for comparison purposes. Figure 3 represents the %TD results for each individual specimen for each US Mesh size plotted against DC.
Figure 3. TRS Specimen Results: Figure shows %TD for each specimen achieved for CoMM and DICoMMs for each US Mesh size used plotted against DC. The graph shows the large spread found for each of the DCs. Another observation is that the increasing addition of diamond to the Co matrix seems to increase the amount of scatter in %TD as can be seen as DC increases. Standard Deviation of %TD for each US Mesh size plotted against DC does show increasing scatter for increasing DC can be seen in Figure 4.
Figure 4. TRS Specimen Results: Figure shows the Standard Deviation for %TD achieved for CoMM and DICoMMs for each US Mesh size within each DC. The results indicate that increasing diamond causes an increase in scatter in %TD.
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4.2. TRS Specimens Results - TRS Test Results Figure 5 shows the individual TRS failure stress achieved for CoMM and DICoMMs specimens for each DC, showing a large amount of scatter. Included in the graphs are the TRS results for the 100%Co matrix for comparison.
Figure 5. TRS Specimen Results: Figure shows the individual specimen TRS results for CoMMs (40mm Span) & DICoMMs (40mm spans) plotted against DC. The results are for each specimen for each US Mesh size and DC. CoMM specimen results shown in red. Averaging all the TRS results for 100% cobalt and the DICoMM specimens for each diamond concentration the graph in Figure 6 clearly shows that with increasing diamond concentration, failure stress decreases.
Figure 6. TRS Specimen Results: Average failure stress for each DC for specimens which were tested using 40mm span. CoMM average TRS result (40mm span) shown in red. What is not evident in Figures 5 & 6 is how failure stress behaves with increasing diamond concentration for each US Mesh size. As an example, Figure 7 shows the average failure stress for 60/70 US Mesh diamond DICoMM specimens showing that as diamond concentration increases the failure stress decreases. This effect is found for all the other US Mesh sizes with some showing it clearly while others not as strongly.
Figure 7. TRS Specimen Results: Figure shows the average failure stress for 60/70 US Mesh diamond DICoMM specimens showing that failure stress decreases as diamond concentration increases. CoMM average TRS result (40mm span) shown in red.
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Figure 8 shows clearly when diamond size decreases there is an increase in TRS failure stress. This effect is found for all DCs even though the effect is more pronounced in some in comparison to others the effect is still present. The effect is in keeping with that found in the literature. Another observation is that as diamond concentration increases there is a drop in TRS failure stress which was already pointed out previously.
Figure 8. TRS Specimen Results: All DC10 and DC30 TRS specimens tested using 40mm span, showing the effect of increasing failure stress with decreasing diamond size is still showing significance at different diamond concentrations.
Figure 9. TRS Specimen Results: Figure shows the Standard Deviation for Failure Stress achieved for CoMM and DICoMMs for each DC used. As can be seen in Figure 9, the standard deviation for each US Mesh size is plotted against DC. From the graph it can be seen that there is a decrease in the level of scatter with increasing DC. Within each DC, there is a slight increase in the range of scatter for DC1 and DC10 in comparison with the other DCs. Regarding the level of scatter with diamond size (US Mesh), in all DCs there is no significant increase or decrease in scatter as measured by standard deviation with diamond size discernable. Interestingly, the level of scatter for 100% cobalt is greater than any DC as seen in the figure. The ductility of bend specimens can be measured as the Displacement-at-Break. Hosking et al. [22] have found that for PMMCs the ductility is a function of volume-fraction but is independent of particle size. Regarding DICoMM materials, it is found that diamond concentration and particle size strongly influence ductility as measured by Displacement-at-Break, as can be seen in Figures 10 and 11 below. The results are just for the TRS tests carried out on DICoMM specimens using 40mm span. For diamond size, results for different DCs are plotted against diamond size and show a reasonable correlation, with correlation coefficients for DC1 of R = 0.41, DC20 of R = 0.40 & DC30 of R = 0.48.
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Figure 10. TRS Specimen Results: Graph of Displacement @ Break plotted against diamond size. The trendline showing a decreasing displacement with increasing diamond size, DC1, DC20 and DC30. R values for DC1 = 0.41, DC20 = 0.40 & DC30 = 0.48.
Figure 11. TRS Specimen Results: Graph of Displacement @ Break plotted against DC. The trendline showing a decreasing displacement with increasing DC, R = 0.40. In Figure 11 where Displacement-at-Break is plotted against diamond concentration shows with increasing diamond concentration Displacement-at-Break decreases with a correlation coefficient R equal to 0.40, in agreement with Hosking et al. [22]. From the results presented the author proposes that the addition of diamond introduces crack initiating flaws to the cobalt matrix, and with increasing DC and diamond size it increases the chance of finding a fatal flaw thus reducing the TRS and DICoMM ductility. Failure may occur from a defect within the test piece and not from the surface. The true fracture stress is then rather lower than that calculated. Failure may occur away from the loading point in three-point bending. Again, the true fracture stress is lower than that calculated, but this error can be corrected if the position of the failure relative to the loading point is noted. Further investigations into this will be carried out and findings will be published in due course. 4.5. Fractography - TRS Specimens This section is going to show a range of photomacrographs of the fracture surfaces of the DICoMM materials found during the TRS testing. Presented will be just a sample to indicate the typical variability found. Fracture surfaces chosen are ones that the author thinks will be interesting to the reader and that will also aid understanding the analysis of the results to be presented. Figure 12 shows the fracture surface of a specimen which was hot pressed using a 30/35US Mesh size and a diamond concentration DC40. The diamond present can be seen as yellow/green in colour and also areas of showing a strong reflection are pull-outs which are sockets where diamond has been pulled out of during the fracture process and would be present in the opposing fracture surface of the fractured specimen. Another interesting feature is the presence of clusters of diamonds which in high diamond concentrations and especially coarse sized US Mesh sizes are very common, however are detrimental to TRS fracture strength of the specimen.
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Figure 12. TRS specimen showing fracture surface of specimen 30/35 DC40 showing diamonds present on the fracture surface. Run 134/1, mag. x 10 TRS Type Specimens showing Fracture Surfaces.
Figure 13. TRS specimen showing fracture surface of specimen 25/30 DC40 showing large clustering of diamonds present on the fracture surface. Run 146/2, mag. x 10. Figure 13 shows a TRS fracture surface showing coarse diamonds of US Mesh size 25/30 and DC40, which have large areas of clustering present throughout the specimen. This clustering of diamond behaves as a great source of flaws to initiate fracture.
Figure 14. TRS specimen showing fracture surface of specimen 45/50 DC30 showing large clustering of diamonds present on the fracture surface. Run 179/2, mag. x 10. Figure 14 shows the fracture surface of the TRS specimen with 45/50 US Mesh diamond size and a diamond concentration of 30. It shows a good distribution of diamond throughout the fracture surface which would be expected because finer diamond generally gives better distribution than coarser diamond sizes. 5.0 Conclusions (1) The addition of diamond to cobalt matrix lowers the percent theoretical density achievable resulting increased in porosity level in diamond impregnated segments. (2) The TRS results for DICoMM materials show a large variability due to the addition of diamond. (3) The TRS of DICoMMs decreased with increasing diamond concentration. With increasing diamond concentration a shift downwards in TRS was found to occur. (4) Increasing diamond size at constant diamond concentration reduces the TRS strength of DICoMM materials. (5) It is proposed that the addition of diamond introduces a crack initiating flaw to the cobalt matrix, and with increasing DC and diamond size it increases the chance of finding a fatal flaw thus reducing DICoMM TRS. REFERENCES [1] James Dwan, Impact Properties of Diamond Impregnated Metal Matrices, Industrial Diamond Review, 2/2003. [2] James D Dwan, Fracture Toughness Determination of Diamond Impregnated PM Cobalt, EPMA Euro PM2006, 22-25 Oct 2006, Ghent Belgium [3] J. Dwan, Analysis of ASTM399 Fracture Toughness Testing of Diamond Impregnated Co Matrix, Euro PM 2009, Copenhagen Denmark, October. 2009. [4] D.OMahony, J. Dwan, Effect of Diamond on the Fatigue Properties of PM Cobalt, Euro PM 2006, Ghent, Belgium, 23-25 Oct. 2006. [5] James Dwan, Impact Properties of Diamond Impregnated Cobalt Metal Matrix, EURO PM 2002, European Conference on Hard Materials & Diamond Tooling, Lausanne, Switzerland October 7-9th, 2002. pp. 50-56.
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[6] James D. Dwan, WEAR properties of diamond impregnated Cobalt Metal, EURO PM2008, 29th Sept. 1st Oct. 2008, Mannheim Germany. [7] Y.Blake, J.Dwan, N. McClelland, M.J. Jackson, Investigation on wear process of diamond blade tools, Int. J. Manufacturing Technology and Management, Vol. 15, Number 2, pp.228-237, 2008. [8] Lin, Z., Queeney, R.A., Fracture Resistance of Diamond Reinforced Hot Pressed Cu/Ni Powders, Powder Metallurgy International, Vol 18, #12, 1986. [9] Yu-Zan Hsieh , Jing-Fure Chen, Shun-Tian Lin, Pressureless sintering of metal bonded diamond particle composite blocks, J., Materials Science , Vol. 35 (2000), pp. 5383 5387] ] [10] A. L.Majstrenko, The strength and fracture of composite diamond-bearing tool materials, Advances in Fracture Research (Fracture 84), Proc. 6th Intl. Conf. Fracture (ICF6), New Delhi, India, 4-10 Dec. 1984. [11] Ibrahim, F.A. Mohamed, E.J. Lavernia, Particulate reinforced metal matrix composites a review, J. Mater Science Vol.26, (1991) pp. 1137-1156. [12] Narula, P. Czubarow, D. Seyterth, Poly(borazinylamine): an excellent precursor for the preparation of low volume fraction metal-matrix composites containing metal borides and nitrides as ceramic phase, J. Mater. Sci. Vol. 33 (1998) pp. 1389-1397. [13] W. Frazier, Particulate Materials and Processes, a navy overview, Advanced Particulate Materials and Processes 1997, Proc. Fifth Intl Conf. On Advanced Particulate Materials and Processes (APMP). April 7-9, 1997, West Palm Beach .Florida. [14] K.I. Parashivamurthy, R.K. Kumar, S. Seetharamu, M.N. Chandrasekharaiah, Review on TiC reinforced steel composites, J. Mater. Sci. 36 (2001) pp. 4519-4530. [15] P. Yih, D.D. Chung, Titanium diboride copper-matrix composites, J. Mater Science, 32 (1997), pp. 17031709. [16] H. Reshetnyak, J. Kbarsepp, Resistance of hardmetals to fracture, Powder Metallurgy, 1998, Vol. 41. No.3 pp. 211-216. [17] M.M Oliveira, J.D. Bolton, Mechanical properties of high speed steel base composites containing TiC and TiN ceramic additions, ICCM/9, Madrid, 12-16th July, 1993, pp. 149-156. [18] A. Chakraborty, S.B. Bhaduri, J.J. Reddy, Y.R. Mahajan, The effect of processing parameters on the mechanical properties of Al2O3 /SiCw composites, PMI Vol. 23, No.3, 1991. pp. 169-173. [19] Manuela Oliveira, John D. Bolton, Effect of ceramic particles on the mechanical properties of M3/2 high Speed Steel, The International Journal of Powder Metallurgy, Vol. 32, No.1, 1996. pp. 37-48. [20] R. Vassen, M. Koldewitz, A. Ruder, Influence of binder content and particle size on green strength of WPP parts, Powder Metallurgy, 1995 Vol.38, No. 1, pp. 55-58. [21] SERIES-IX Software, Instron Corp., High Wycombe, UK. [22] F M Hosking, F. Folgar Portillo, R. Wunderlin, R. Mehrabian, Composition of aluminium alloys: fabrication and wear behaviour, J. Mater Sci. 17 91982) pp. 477-498.
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STUDY ON THE EFFECT OF TiB2 CONTENT ON MICROSTRUCTRE AND PROPERTIES OF Al-TiB2 NANOCOMPOSITE
Zohreh SADEGHIAN* and Behnam LOTFI** *Department of Materials Science and Engineering, Faculty of Engineering, Shahid Chamran University, Ahvaz, Iran, z.sadeghian@scu.ac.ir ** Department of Materials Science and Engineering, Faculty of Engineering, Shahid Chamran University, Ahvaz, Iran, behnaml@scu.ac.ir ABSTRACT Al-TiB2 nanocomposite was synthesized by mechanical alloying of elemental powders. A double step process was used to prevent the formation of undesirable phases. The resulting powders were consolidated by spark plasma sintering followed by hot extrusion. Microstructural characteristics of powder particles and consolidated samples were studied by X-ray diffractometry, scanning electron microscopy and transmission electron microscopy. The obtained powder showed a good thermal stability against grain growth and particle coarsening. Extruded Al-TiB2 exhibited improved mechanical properties with values higher than those reported for similar composites made by other processes. Decreasing TiB2 content to 10 wt.% caused no extreme reduction in mechanical properties. Keywords: Aluminum matrix nanocomposite, Mechanical alloying, In situ TiB2, Spark plasma sintering, Mechanical properties. 1. INTRODUCTION TiB2 is known as a suitable reinforcing phase for Al-base composites because of its thermodynamic stability, high modulus, excellent refractory properties and a high resistance to plastic deformation even at high temperatures [13]. In the last decade in situ metal matrix composites (MMCs) have been developed, in which the reinforcements are introduced in the metal matrix during fabrication, by a chemical reaction between the constituents. In comparison to traditionally fabricated materials, in situ MMCs undergo less degradation at high temperatures. This is because of their superior thermodynamic stability, stronger interface bonding resulting from the clean reinforcement-matrix interfaces and finer and more uniform distribution [4]. Several techniques including mechanical alloying have been developed to fabricate in situ MMCs [4-5]. MA has an advantage over other in situ fabrication routes as it is capable of producing nanostructured composite powder with high uniformity [5]. In previous investigations it has been reported that during the in situ synthesis of Al-TiB2 composites from different starting powder mixtures, Al3Ti intermetallic compound is also formed. This phase is brittle and has been reported to considerably reduce the fatigue life of composites [6-7]. Therefore it is of interest to eliminate the formation of Al3Ti intermetallic compound. A challenge in processing of nanostructured materials is that long time exposure at high temperature sintering, often results in severe grain growth. Several consolidation techniques such as hot-pressing, shock consolidation, sintering with the application of ac currents, pulsed electric current and spark plasma sintering (SPS) are introduced to overcome these difficulties [8]. SPS provides fast densification with minimal grain growth in a short sintering time. The aim of present study was to study the influence of second phase content at 10 and 20 wt.% on microstructure and properties of the material. Consolidation of the powder by SPS and hot extrusion was conducted to obtain bulk materials.
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2. EXPERIMENTAL PROCEDURE Elemental Al (63 m), Ti (40-60 m) and B (2 m) powders were used as starting materials. The aluminum powder with an average particle size of 63 m was supplied from ECKA Granulate, Velden. The titanium powder with a particle size of 40-60 m was obtained from GKN Sinter Metal Filters, Radevormwald, and the Merck boron powder had a particle size of about 2 m. Powder mixtures were milled by a Fritsch planetary ball mill with a rotating speed of 360 rpm. The ball to powder weight ratio was 10 and the diameter of the chromium steel balls was 15 mm. MA was done under argon and 1 wt. % zinc stearate was added to the mixture as a process control agent. A double step process was used to obtain an in situ Al-TiB2 metal matrix powder. In the first step Ti and B powders were milled with the composition of Al- 62.01 wt. % Ti-27.99 wt. % B. This powder was then milled with additional aluminum powder to achieve the tailored compositions of Al- 10 and 20 wt. % TiB2. Powders were sintered by FCT HP D 250 spark plasma sintering (SPS) equipment. Powder was placed into a graphite die with a diameter of 40 mm and compacted under argon atmosphere with an applied pressure of 35 MPa. The whole process lasted 600 sec and the maximum temperature was 550 C with the dwell time of 0 sec. The changes of the SPS parameters during the consolidation process are shown in Fig. 1.
Figure 1. An example curve showing the evolution of SPS conditions during the consolidation process. The density of the SPS materials was determined using Archimedes principle. The sintered samples were then hot extruded by direct and backward extrusion in order to obtain suitable rods of composites for mechanical tests. Investigation of the structural changes during mechanical alloying and after sintering was conducted by a SEIFERT 30033 PTS diffractometer employing monochromatic Cu K radiation (= 0.15406 nm). XRD scans were performed with a step size of 0.05 in 2 and a dwell time per step of 20 s. The microstructures of the powder particles and the sintered samples were studied by scanning electron microscope (SEM, LEO) and transmission electron microscopy experiments (TEM, FEI Tecnai G2 200 kV). The TEM samples were prepared by using focused ion beam (FIB) technique. Tensile behavior at high temperature was studied by MTS 30/HS testing machine with a strain rate of 0.008 mms-1. 3. RESULTS AND DISCUSSION Fig. 2 shows the X-ray diffraction patterns of the Al- 62 wt.% Ti- 28 wt.% B and Al with 10 and 20 wt.% TiB2 powders after different milling times. After 20 hours of milling (Fig. 2-b) no evidence of remaining titanium or formation of undesired phases could be detected on the XRD pattern. Milling of this powder with additional Al powder for 20 h yields Al- 20 wt.% TiB2 and/or Al- 10 wt.% TiB2 compositions (Fig. 2-c and d). Detailed structural changes during MA are presented elsewhere [10-11]. The grain size of the aluminum matrix and TiB2 was obtained from XRD analysis using WilliamsonHall (WH) equation [12]. The grain size of both TiB2 particles and aluminum matrix after double step MA was measured to be about 15 nm for Al- 20 wt.% TiB2.
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Figure 2. XRD patterns of Al-62 wt.% Ti-28 wt.% B powder mixture, (a)asreceived, (b) as-milled for 20 h, (c) final Al-20 wt.% TiB2 powder and d) final Al-10 wt.% TiB2 powder obtained from double step mechanical alloying. The cross-sectional SEM micrographs of final powder particles of both compositions are shown in Fig. 3. A fine and uniform distribution of TiB2 particles is observed in Al- 20 wt.% TiB2 (Fig.3-a). At higher magnification obtained from scanning transmission electron microcopy (STEM), the average TiB2 particle size was found to be about 90 nm with a distribution of 10 nm to 1 m (Fig. 3-b). The mean TiB2 particle size seems to be smaller than that of previous studies on in situ Al-TiB2 composite produced by MA [6]. As seen in Fig. 3-c in Al- 10 wt.% TiB2 the size of TiB2 particles yield a wider distribution from a few nanometers to about 3 m. this can be attributed to the effect of Al matrix as a ductile material to reduce TiB2 fragmentation during milling. Final powders obtained from the double step mechanical alloying were sintered using SPS technique. A typical XRD pattern obtained from SPSed Al-TiB2 samples is shown in Fig. 4-a. After SPS at 550 C no significant structural change occurred in the consolidated nanocomposites. It can be concluded that by the double stage synthesis process, the formation of undesirable compounds even after exposure to sintering temperature, is prevented. Lu et al. reported that during the high temperature exposure of as milled AlTiB powder mixture, Al3Ti phase was formed in the aluminum matrix along with TiB2 [7]. The grain size of Al matrix after sintering increased to 30 nm, indicating that Al matrix has a relatively good stability against grain growth.
Figure 3. Typical cross-sectional a) SEM, b) STEM images of Al- 20 wt.% TiB2 and c) SEM image of Al- 10 wt.% TiB2 powder particles.
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Final powders obtained from the double step mechanical alloying were sintered using SPS technique. A typical XRD pattern obtained from SPSed Al-TiB2 samples is shown in Fig. 4-a. After SPS at 550 C no significant structural change occurred in the consolidated nanocomposites. It can be concluded that by the double stage synthesis process, the formation of undesirable compounds even after exposure to sintering temperature, is prevented. Lu et al. reported that during the high temperature exposure of as milled AlTiB powder mixture, Al3Ti phase was formed in the aluminum matrix along with TiB2 [7]. The grain size of Al matrix after sintering increased to 30 nm, indicating that Al matrix has a relatively good stability against grain growth.
Figure 4. XRD pattern of the samples, a) SPSed Al-20 wt.% TiB2, b) extruded Al-20 wt.% TiB2 and extruded Al-10 wt.% TiB2. SPSed samples were hot extruded with a pre heating temperature of 400C and extrusion rate of 0.6 mm.s-1 to produce rods of Al-TiB2 nanocomposites. X-ray patterns of Al-20 wt. % TiB2 and Al-10 wt. % TiB2 nanocomposites after hot extrusion are shown in Fig. 4-b and c. No structural changes could be detected in the X-ray patterns. SEM observations revealed that the size of TiB2 particles in Al-20 wt. % TiB2 after extrusion ranged from 30 nm to 2 m (see Fig. 5). Therefore, the sample showed no considerable increase in particle size compared to that for SPS compact as well as milled powder. Also Al grain size increased only slightly to 35 nm after extrusion. In Al-10 wt. % TiB2 the maximum size of TiB2 particles was found to be about 3 m, which showed an acceptable stability against growth compared to the powder. Microhardness and hardness values of the samples at different stages are presented in Table 1. A significant decrease in the hardness values occurred after consolidation of the powders, which is caused by elimination of cold work effects during annealing at high temperatures. Hardness values of the samples were further reduced slightly after extrusion. Nevertheless even the hardness of Al-10 wt. % TiB2 is much higher than 84 VHN reported in the literature for the same material prepared by different route [6]. According to the Table 1 by reducing the amount of TiB2 in the composite from 20 to 10 % the hardness showed a small decrease of 3.8 %. This is in good agreement with the findings of previous studies on other nanocomposite systems such as Al-Al2O3 [13] and Ni-SiC [14].
Figure 5. SEM images of extruded nanocomposites, a) Al-20 wt. %TiB2 and b) Al-10 wt. %TiB2.
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Table 1. Hardness values of Al-20 wt. %TiB2 and Al-10 wt. %TiB2 nanocomposites at different processing stages. Extruded sample hardness, VHN 180 173 Sintered sample hardness, VHN 206 196 Powder microhardness, VHN 480 460 Sample Al-20 wt.%TiB2 Al-10wt.%TiB2
Table 2 presents the tensile properties of Al-20 wt. %TiB2 and Al-10 wt. %TiB2 nanocomposites at ambient temperature. Both compositions showed much higher yield and tensile strength than those reported for composites with similar compositions [1, 6]. The improved yield strength in the present study can be explained by Orowan strengthening, caused by the resistance of closely spaced fine, hard TiB2 particles for passing of dislocations. Al-TiB2 composites produced in this study showed a brittle behavior in tensile test. Decreasing the TiB2 content in this system caused only 5 % reduce in strength. Similar results have been reported for metal matrix nanocomposites, previously [13,14]. It is well known that particles smaller than 100 nm are responsible for the Orowan strengthening. When in a metal matrix nanocomposite the content of reinforcement at high values like 20 wt. % is reduced, this may cause a reduction in the number of larger particles. Despite the fact the matrix is still saturated with nano particles which are acting as Orowan resistors [15]. Fig. 6 shows the effect of temperature on tensile properties of bulk nanocomposites up to 400 C. In both compositions tensile strength did not decrease drastically up to 300 C. Hence, it can be concluded that even at high temperatures Orowan strengthening is the dominant mechanism. As presented in Fig. 7 Al-TiB2 nanocomposites produced in the present study showed higher tensile strength than those fabricated by other techniques at high temperatures. On the other hand the composites exhibited brittle behavior even at high temperature of 400 C. Table 2. Tensile properties of Al-20 wt. %TiB2 and Al-10 wt. %TiB2 nanocomposites at room temperature. Elongation, % 1.4 1.8 Tensile strength, MPa 543 514 Yield strength ,MPa 483 456 Sample Al-20 wt. % TiB2 Al-10 wt. % TiB2
Figure 7. A comparison between the tensile strength of Al-TiB2 nanocomposites prepared in this study and Al matrix composites presented in the literature.
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4. CONCLUSIONS Al TiB2 nanocomposite powder was synthesized by a double-step MA process of elemental powders. Microstructural observations showed formation of TiB2 particles with a relatively uniform distribution in the Al matrix after a total milling time of 40 h. No traces of undesirable phases such as titanium aluminides were observed even after consolidation of the powder by SPS. Al-TiB2 nanocomposite showed a tensile strength of 543 MPa with 20 wt. % and 514 MPa with 10 wt. % TiB2, which is much higher than those reported for similar composites made by other processes. Al-TiB2 nanocomposites showed a brittle behavior in tension. Al-TiB2 nanocomposites presented a good microstructural and mechanical stability at elevated temperatures. It was revealed by the results that reducing the TiB2 content frome 20 to 10 wt.% caused only a 5% reduction in tensile strength of the nanocomposite. REFERENCES 1. Tjong, S. C., Lau, K. C., Properties and abrasive wear of TiB2/Al-4%Cu composites produced by hot isostatic pressing, Composites Science and Technology, Vol. 59 , pp. 2005-2013,1999. 2. Chen, Z. Y., Chen, Y. Y., Shu, G. Y., Li, D., Liu, Y., Microstructure and properties of in situ Al/TiB2 composite fabricated by in-melt reaction method, Metallurgical and Materials Transactions A, Vol. 31A, pp. 1959-1964, 2000. 3. Yi, H., Ma, N., Li, X., Zhang, Y., Wang, H., High-temperature machanics properties of in situ TiB2p reinforced Al-Si alloy composites, Materials science and Engineering A, Vol. 419, pp. 12-17, 2006. 4. Tjong, S. C., . Ma, Z. Y, Microstructural and mechanical characteristics of in situ metal matrix composites, Materials Science and Engineering A, Vol. 29, pp. 49-113, 2000. 5. Suryanarayana C., Mechanical alloying and milling, Progress in Materials Science, Vol. 46, pp. 1-184, 2001. 6. L, L., Lai, M. O., Su, Y., Teo, H. L., Feng, C., F., In situ TiB2 reinforced Al alloy composite, Scripta Materialia, Vol. 45, pp. 1017-1023, 2001. 7. Lu, H. Lai M. O., Wang, Y., Synthesis of titanium diboride TiB2 and Ti-Al-B metal matrix composites, Journal of Materials Science, Vol. 35, pp. 241-248, 2000. 8. Viswanathan, V., Challenges and advances in nanocomposite processing techniques, Materials Science and Engineering R, 54, pp. 121-285, 2006. 9. Mamedov, V., Spark plasma sintering as advanced PM sintering method, Powder Metallurgy, Vol. 4 (45), pp. 322-328, 2002. 10. Sadeghian, Z., Enayati, M. H. Beiss, P., Characterization of in situ Al-TiB2 nanocomposite powder synthesized by mechanical alloying, Powder Metallurgy, Vol. 54, pp. 4649, 2011. 11. Sadeghian, Z., Enayati, M. H. Beiss, P., In situ production of AlTiB2 nanocomposite by double-step mechanical alloying, Journal of Materials Science, Vol. 44, pp. 2566-2572, 2009. 12. Suryanarayana, C., X-ray diffraction: a practical approach, Norton MG: Plenum Press, New York, USA, 1998. 13. Kang, Y. and Chan, S., Tensile properties of nanometric Al2O3 particulate-reinforced aluminum matrix composites, Materials Chemistry and Physics, Vol. 85, pp. 438-443, 2004. 14. Zimmerman, A.F., Palumbo, G., Aust, K. T., Erb, U., Mechanical properties of nickel silicon carbide nanocomposites, Materials Science and Engineering A, Vol. 328, pp. 137146, 2002. 15. Rabiei. A., Vendra. L. and Kishi. T.,Fracture behavior of particle reinforced metal matrix composites, Composites: Part A, Vol. 39, pp. 294300, 2008. 16. Vedani. M., Errico. F. D., Gariboldi. E., Mechanical and fracture behaviour of aluminium-based discontinuously reinforced composites at hot working temperatures, Composites Science and Technology, Vol. 66, pp. 343349, 2006.
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DRY SLIDING WEAR RESISTANCE AND DESIGN CRITERIA FOR POWDER METALLURGY STEELS
Ibrahim METINOZ*, Ilaria CRISTOFOLINI**, Alberto MOLINARI* *Department of Materials Engineering and Industrial Technologies, University of Trento, Trento (Italy), ibrahim.metinoz@ing.unitn.it, alberto.molinari@ing.unitn.it **Department of Mechanical and Structural Engineering, University of Trento, Trento (Italy), ilaria.cristofolini@ing.unitn.it ABSTRACT The wear coefficients of two diffusion bonded sintered steels was used as knowledge base to implement the model of the dry sliding wear. The difference in the wear resistance of the two steels has a noticeable influence on the working life of a component subject to this kind of wear. The effects of changing geometry or microhardness were compared. Keywords: Powder Metallurgy, Wear, Design Criteria 1. INTRODUCTION Many parts produced by Powder Metallurgy (PM) are subject to wear in application. Wear occurs by different mechanisms depending on the contact conditions (relative motion, load, environment) and on the materials involved. In the case of dry sliding contacts, wear occurs mainly by either adhesion or triboxidation [1]. Among the PM materials used in structural applications, the diffusion bonded Fe-Mo-Ni-Cu steels are widely utilized. They can be hardened by either through hardening or carburizing, but the final microstructure contains a Fe-Ni constituent which cannot be hardened by heat treatments. It may constitute a weak part of the microstructure, because of its lower microhardness in comparison to the martensitic areas formed in the Ni-free zones. Its effect on wear resistance of these steels has been demonstrated in previous works [2]. An alternative to this class of materials is represented by the diffusion bonded Ni-free Fe-Mo-Cu steels, which can be sinterhardened, obtaining a homogeneous martensitic microstructure just after sintering. In this case, post-sintering heat treatments can be avoided. In the present work, the results of dry sliding wear tests on these two types of sintered steels are elaborated to define some design guidelines for specific applications where this kind of wear may seriously damage the parts performance. The wear which is observed during tests is the so called low-sliding velocity oxidative wear proposed by Stott [3]. It occurs in the tribosystems characterized by a sliding velocity lower than 1 m/s [4]. Wear tests were carried out in a disk-on-disk apparatus, and tests were carried out at different loads. To generalize the results, the mean pressure was determined and the wear coefficient was calculated from the wear rate. A failure criterion was then defined with reference to the wear thickness, and the performance of the two steels was compared. Since the wear thickness depends on the hardness of the materials and on the geometry of the parts involved, the influence of these two parameters was evaluated. 2. EXPERIMENTAL PROCEDURE Table 1 shows the code and the nominal chemical compositions of the materials investigated; TH and SH mean through hardening and sinter hardening, respectively.
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Table 1. Chemical composition of the investigated materials Material Code TH SH Nominal Chemical Composition of the Steels (wt %) 93.4Fe-4Ni-0.5Mo-1.5Cu-0.6C 95.9Fe-1.5Mo-2Cu-0.6C
Discs 10 mm in height, with an external diameter of 40 mm and an internal hole of 16 mm diameter were compacted in a double action uniaxial press and sintered at 1120C in endogas; the as sintered density is 7.2 g/cm3. The production process was carried out in industrial plant. The microstructure of the materials was investigated at optical microscope after etching: it differs for the presence of the Ni-rich constituent in the TH material, in addition to martensite [2]. Hardness was measured on the compaction surface of the disks; it is 357 HV30 and 407 HV30 for TH and SH, respectively. 2.1 Dry Sliding Wear Test The dry sliding tests were carried out on an Amsler trybotester. The test configuration was disc on disc, with the PM disc rotating against the fixed counterface disc, made of a 100Cr6 steel hardened to 62 HRc. The loads during the tests were 200, 500 and 1000 N; the sliding speed was 0.314 m/s, which corresponds to 150 rev/min. Wear tests were interrupted each 15 minutes and the weight loss was measured after ultrasonic cleaning with acetone to remove wear debris entrapped into the pores. While measuring the weight loss of the discs, the width of the contact area was also measured. 3. RESULTS AND DISCUSSION 3.1 Wear Test The mean pressure during the wear tests is calculated from the equation (1) P0=F/A (1) where P0 [Pa] is the mean pressure, F [N] is the applied force and A [mm2] is the contact area given by A = lb where l is the contact length (10 mm) and b is the contact width, which was measured as described above.. At the beginning of the tests there is a line contact [1], and width is calculated from the theory of the elastic contact by equation (2) b= (4FR / lE )1/2 (2) where R [m] is the reduced radius of curvature of the two discs, R=(1/R1+1/R2)-1; E [Pa] is the reduced Youngs Modulus, E=(1/E1+1/E2)-1. The Youngs Modulus of the materials is 140 x 109 Pa for the PM specimens and 210 x 109 Pa for the counterface disc. The mean pressure P0 is calculated from equation (3) P0=0.78 Pmax (3) where Pmax is the maximum contact pressure given by the equation (4) Pmax= F/(bl) (4) Figure 1 shows the plot of the mean pressure P0 as a function of the sliding distance. The mean pressure is very high at the beginning due to the line contact and after a while decreases dramatically due to the enlargement of the contact area. It can be seen that the mean pressure can be considered as constant after a certain distance for each load.
Figure 1. The relation between mean pressure and sliding distance.
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The wear rate, calculated from the wear tests [5] can now be correlated to the mean pressure. Table 2 reports the data, which are also plotted in Figure 2.
Table 2. Wear Rate of the Materials
Figure 2. Wear Rate vs. Pressure On increasing the mean pressure wear rate increases in both materials. Moreover, SH has lower wear rate than TH under the same pressure; this was attributed to the effect of the Ni-rich constituent on the load bearing capacity of the surfaces [2]. The graph which illustrates the wear rate vs. mean pressure is shown in figure 2. From the Archard Law [6] the wear coefficient K was calculated by equation (5) K=WH/F (5) where W [mm3/m] is the wear rate, H [N/mm2] is hardness and F [N] is the applied force. The wear coefficient K as a function of mean pressure is shown in figure 3.
Figure 3. Wear Coefficient vs. Pressure Material SH still maintains a better wear resistance than TH. 3.2 Failure Criteria and Design Guidelines In the selection of wear model, wear thickness is the most convenient parameter [5]. Wear thickness is calculated from equation (6) h=(KFN)/(HL) (6) where h is the wear thickness, K is the dimensionless wear coefficient, F [N] is the applied force, H [N/mm2] is the hardness of the material, L [mm] is the length of the contact area and N is the number of cycles.
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As a failure criterion the maximum acceptable wear thickness has to be defined. The maximum acceptable wear thickness can be defined with reference to the tolerance required for the dimension perpendicular to the surface exposed to wear. In this way a maximum wear thickness hl is defined, to which the wear thickness calculated with equation (6) has to be related. The classes for dimensional tolerances are defined by the Internal Organization for Standardization, ISO. In the case of a Powder Metallurgy part having a diameter of 40 mm the ISO IT9, IT10 and IT11 classes may be considered and the relevant values are reported in table 3. Table 3. Classes of dimensional tolerance IT 9 0.031 mm IT 10 0.05 mm IT 11 0.08 mm
Given that the tolerance is applied to a diameter, the maximum acceptable wear thickness will be derived considering half of the values reported in Table 3. As an example, figure 4 shows the wear thickness as a function of the number of cycles N for the mean pressure of 3.67 MPa. The maximum acceptable wear thickness according to IT9, IT10 and IT11 requirements is reported as well.
Figure 4. Wear thickness vs. Number of Cycles at 3.67 Mpa It can be seen that material TH is not able to operate for 106 cycles in any acceptable range. On the other hand, material SH can operate 106 cycles if IT11 classes is required, whilst it operates up to 6.5x105 and 4x105 cycles if the IT10 and IT9 class are required, respectively. If the mean pressure on the tribosystem is increased from 3.67 up to 8.22 MPa the new trend for the wear thickness can be seen in figure 5.
Figure 5. Wear thickness vs. Number of Cycles at 8.22 MPa The increase in the pressure causes an increase in the wear thickness in both materials, then the maximum number of cycles to reach the acceptable wear thickness decreases. Both of materials cannot operate 106 cycles in all the cases; the material SH can operate 6x105 cycles if IT11 ISO class is required by the failure criterion.
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If the mean pressure of the tribosystem is increased to 13.71 MPa the wear thickness is shown in figure 6.
Figure 6. Wear thickness vs. Number of Cycles at 13.71 MPa Wear thickness further increases, and material SH operates 4x105 cycles if IT11 ISO class is required by the failure criterion. Equation (3) shows that the wear thickness depends on hardness of the material and on the length of the contact area L. The length of the contact area in Powder Metallurgy may be increased by increasing the height of the disk, by simply filling more powder without changing the die geometry and the compaction strategy significantly. An increase in L changes the mean pressure (decrease) and the wear coefficient, accordingly. For instance, figure 7 shows the wear thickness in the case of a 30% larger contact length: the wear coefficient in this new situation was extrapolated by the available data base.
Figure 7. h vs. N at 2.82 MPa (length of the contact area is increased of 30%) The comparison between figures 4 and 7 shows that the increase in the length of the parts results in a decrease of the wear thickness for both TH and SH. The material TH is still not able to operate for 106 cycles in any case. On the other hand, material SH can operate 106 if the IT11 is required by the failure criterion. As an alternative, hardness may be increased by increasing the carbon content of the material. For instance, an increase of 60 HV in hardness can be obtained by either increasing the carbon content up to 0.7-0.8% (in the case of TH the sintering temperature should be increased, as well, to enhance hardenability thanks to the homogenization of the Ni distribution). In this case, the wear thickness decreases, as shown by figure 8, relevant to the lowest pressure considered. Again, the material TH is still not able to operate for 106 cycles in any case. On the other hand, material SH can operate 106 even if the IT10 is required by the failure criterion. The increase in hardness is equivalent to the 30% increase in the height of the parts. The most attractive solution seems to be the increase in hardness. The increase in carbon content slightly decreases compressibility of the powder mix but, on the other side, the increase in height increases the part weight correspondingly. Even from the viewpoint of the cost effectiveness, the increase in the carbon content has to be preferred.
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Figure 7. h vs. N at 3.67 MPa (the hardness is increased by 60 HV) 4. CONCLUSION In this paper the wear coefficients of two different PM steels was used as knowledge base to implement the model of the dry sliding wear. The steels are both diffusion bonded: one contains Ni and was through hardened, the other one is Ni free and was sinter hardened. Due to the presence of the Ni rich areas which are softer than the martensitic matrix the former has a lower wear resistance than the latter. A failure criterion was defined based on the comparison between the wear thickness and the tolerance required on the dimension perpendicular on the wear surface. The difference in the wear resistance of the two steels has a noticeable influence on the working life of a component subjected to this kind of wear. By means of the same model the effects of changing geometry or microhardness were compared. REFERENCES 1. Straffelini G., Attrito e Usura, Metodologie di progettazione e controllo, ed. Tecniche nuove 2007, 2-7 2. Muterlle P. V., Straffelini G., Molinari A., and Pahl W., Microstructural effects in wear of hardened sintered steels produced by diffusion bonded and prealloyed powders, Powder Metallurgy 2010; 53(3):201-207 3. Stott FH. The Role of oxidation in the wear of materials. Tribol Int 1998; 31:61-71 4. Lim SC, Ashby MF. Wear mechanism maps. Acta Metall 1987; 35(1):1-24. 5. Cristofolini I., Molinari A., Straffelini G. and Muterlle P. V., A systematic approach to design against wear for Powder Metallurgy (PM) steel parts: The case of dry rolling-sliding wear, Materials and Design 2011; 32:2191-2198. 6. Archard JF. Contact and rubbing of flat surfaces. J Appl Phys 1953;24:981-8
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MICROSTRUCTURAL CHARACTERIZATION OF POWDER METALLURGICAL TOOL STEELS ETCHED BY DIFFERENT TECHNIQUES

. Hakan ATAPEK*, eyda POLAT*, Serap GM*, Ersoy ERR* and Gzde S. ALTU* Kocaeli University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 41380, Kocaeli, Turkey hatapek@kocaeli.edu.tr, seyda@kocaeli.edu.tr, sgumus@kocaeli.edu.tr, eerisir@kocaeli.edu.tr, gsultan.altug@gmail.com
*
ABSTRACT In this study, several commercial grades of powder metallurgical tool steels are investigated, in hardened and soft annealed conditions, to determine the types, morphologies and distributions of the carbides present. Prior to the microstructural characterization by scanning electron microscope, all samples are prepared using standard grinding and polishing steps and etched by using different techniques, including immersion into % 3 nital and Beraha solutions and also electroytic etching. The examinations reveal that the steels have fine, aligned or dispersed, carbides in their matrix with globular and facetted morphologies and in light/dark gray contrast. Microanalysis using energy dispersive x-ray spectrometer is carried out to determine carbide types and the results show that the globular carbides are typical W-Mo rich M6C and V-rich MC type carbides, as expected. Keywords: Tool Steels, Powder Metallurgy, Etching, Microstructure, Carbides. 1. INTRODUCTION It is well known that the processing technique has a strong influence on the properties and performance of materials. Engineers and researchers spend most of their time to develop new techniques for the materials that have high level functionality and can be produced by low cost. In the field of materials for tool applications, there are three processes that allow the processing of tool steels (e.g. cold work, hot work and high speed tool steels): conventional casting, powder metallurgy and spray forming [1-5]. The need for high-performance tool steels has grown dramatically because of the demand for high quality parts and low cost high performance tooling per part produced. In this concept, production of powder metallurgical tool steels gains importance. In traditionally melted tool steels, molten metal is poured into moulds and the resulting ingots are forged, rolled and then annealed. In this way, steel bars are formed. During the solidification of the ingot, carbide networks are formed and they weaken the cracking resistance of the matrix. T ype, morphology and also distribution of the carbide play an important role on the mechanical properties of a given tool steel and especially a change of morphology/distribution of the carbide is desired for many tooling applications. The extremely fine carbides and uniform microstructure of powder metallurgical tool steels greatly increase the mechanical properties (hardness, wear resistance, ductility etc.) in all directions. This is in contrast to conventionally produced steel where increased ductility can only be gained at the expense of reduced wear resistance/hardness [6-10]. In this study, the microstructural characterization of several commercial grades of powder metallurgical tool steels were carried out after etching, by using light microscope (LM), scanning electron microscope (SEM) and energy dispersive x-ray spectrometer (EDS) to determine the morphology, type and distribution of carbides in the their matrices.
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2. EXPERIMENTAL STUDY 2.1. Materials Several commercial grades of powder metallurgical tool steels, in hardened and soft annealed conditions were used for the characterization. Table 1 shows the chemical compositions of the steels used in this study. The steels were received from the supplier in soft annealed condition and then hardening heat treatments were carried out. The heat treatment parameters are given in Table 2. The steels used in the study are commonly treated at 1000-1200C for hardening. The sizes of the samples are 10 x 10 x 15mm and the duration for the solution treating was selected according to both sample size and also alloy content in the steel. As it is seen from Table 1, DIN 1.3207 tool steel includes higher W and Co content than DIN 1.3394 and DIN 1.3395 tool steels. Table 1. Chemical compositions of the experimental steels (wt.%). Materials DIN 1.3207 DIN 1.3395 DIN 1.3394 C 1.34 1.30 1.30 Si 0.30 Mn 0.21 Cr 3.36 4.20 4.20 Mo 3.17 5.00 5.00 V 2.50 3.10 3.10 W 9.66 6.40 6.40 Co 10.30 8.50 Fe balance balance balance
Table 2. Heat treatment conditions for the experimental steels. Materials DIN 1.3207 DIN 1.3395 DIN 1.3394 Austenization 1100C, 30 min. 1000C, 15 min. 1000C, 15 min. Quenching Water quenching Water quenching Water quenching
2.2. Metallographical preparations and microscopic examinations After standard metallographical preparations consisting of grinding and polishing, the steels were initially etched by using % 3 nital and Beraha solutions (100 ml H2O +20 ml HCl + 0.30.6 g of potassium metabisulfite). However, these solutions were not adequate to characterize the matrix phase that formed after hardening treatment. Thus, the steels were electrolytically etched by using AC2-I solution and applying 5V for 1 minute. The steels were characterized by using Zeiss Axiotech 100 model light microscope and Jeol JSM 6060 scanning electron microscope. 3. RESULTS AND DISCUSSION 3.1. Light microscope examinations The high-speed steel produced by powder metallurgy contains primary carbides that are rich in vanadium, tungsten and molybdenum. These carbides play an important role in the mechanical properties of the steel, including hardness, wear resistance and temperature resistance. Hence, the types, morphologies, distributions and also the amounts of these carbides must be determined [11]. Figures 1, 2 and 3 show the final microstructures of the investigated steels revealed by light microscope examinations. Hardened DIN 1.3207 high speed tool steel includes typically primary carbides within a martensitic matrix which is very hard and also brittle (Figure 1). In the etched steel, aligned primary carbides can be seen and there is no significant evidence of the austenite grain boundaries as seen in Figure 1a. Upon over etching with % 3 nital solution, the grain boundaries appear due to more anodic dissolution characteristic of the boundaries with chemical reactions. However, etching by nital is not adequate to determine the matrix phase. As-quenched martensite is described as having a tetragonal structure, but this is only true when the carbon content exceeds about 0.6 wt.%. Lower carbon martensites retain the body-centered cubic structure of ferrite. High-carbon martensites typically have lens-shaped martensite plates which contain fine-scale deformation twinning. Low-carbon martensites consist of laths, separated by low- or high-angle boundaries but also containing high densities of dislocations within them [12].
(a) (b) Figure 1. LM images of the microstructures of hardened DIN 1.3207 steel ; (a) as etched and (b) over etched by % 3 nital.
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In Figure 2, the microstructures of DIN 1.3395 steel are given to compare the etchant effect on the matrix for soft annealed and hardened conditions. A ferritic matrix including primary carbides takes place in soft annealed steel and the matrix consists of globular carbides (Figure 2a). In electrolytically etched case, the carbides and their morphologies appear clearly within the matrix and a very fine, homogenous distribution of the carbides can be seen (Figure 2b). Hardening treatment is applied to the steel to form martensitic/bainitic matrix for high mechanical requirements. Hardened microstructures in steels require the generation of the parent phase austenite, the formation of martensite crystals by diffusionless, shear-type martensitic transformation, and adjustment of final strength and toughness by tempering [13]. Figure 2c and 2d show the microstructures of hardened DIN 1.3395 steel. At first, the steel is etched by % 3 nital solution but a high level reaction between etchant and matrix phase cannot be attained. On the other hand, the matrix phase interacts with Beraha solution and it is possible to examine the steel in detail with scanning electron microscope at higher magnifications which will be discussed in the next section. A number of etchants have been reported in the literature to selectively outline, outline and color, or attack specific types of carbides in steels. These etchants have been developed during the first half of the 20th century but have not been studied since the development of modern analytical techniques. Although they are believed to be selective, that is qualitative in nature, their value for quantitative measurements of the carbides has not been determined [1417]. Figure 3 shows the microstructures of soft annealed and hardened DIN 1.3394 steel. As seen from Figure 3a, etching with % 3 nital solution results in low contrast to observe the type and morphology of the carbides and also the matrix phase and also grain boundaries in soft annealed steel. Electrolically etching provides more contrast in soft annealed matrix to evaluate the carbide features as shown in Figure 3b. On the other hand, etching with Beraha solution gives a detail, in hardened steel, for the matrix components. A network type carbide distribution within the matrix is observed (Figure 3c).
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(c) (d) Figure 2. LM images of the microstructures of DIN 1.3395 steel ; (a) soft annealed sample etched by % 3 nital solution (b) soft annealed sample as electrolytically etched , (c) hardened sample etched by % 3 nital solution, (d) hardened sample etched by Beraha solution. 3.2. SEM examinations After using various etchant and etching techniques followed by LM examinations, the steels were also characterized by SEM. Figure 4a shows the general matrix of hardened DIN 1.3207 tool steel. Similar to the light microscope examinations, aligned carbides are observed. At higher magnification, it is obvious that the matrix phase consists of typical plate type martensite with globular carbides mostly at the grain boundaries (Figure 4b).
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Etched microstructures of DIN 1.3395 tool steel are given in Figure 5. Soft annealed steel exhibits a homogeneous distribution of fine carbides within the ferritic matrix after electroytic etching (Figure 5a). In hardened steel, both globular and facetted carbides having different contrast, as bright and dark grey, are observed within the plate type martensitic matrix after etching with Beraha solution (Figure 5b). The type of carbide will be emphasized in the carbide analysis section. Plate type martensite phase is observed as acicular form due to the effect of electrolytical etching with high level anodic dissolution of ferrite (Figure 5c).
(a) (b) (c) Figure 3. LM images of the microstructures of DIN 1.3394 steel ; (a) soft annealed sample etched by % 3 nital solution (b) soft annealed sample as electrolytically etched, (c) hardened sample etched by Beraha solution.
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Figure 4. SEM images of the microstructures of DIN 1.3207 steel as electrolytically etched ; (a) aligned carbide distribution in martensitic matrix after hardening treatment, (b) carbides in the grains and also at the grain boundries.
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Figure 5. SEM images of the microstructures of etched DIN 1.3395 steel; (a) a homogeneous distribution of fine carbides within the matrix, in soft annealed sample, (b) globular and facetted type carbides within the matrix etched by Beraha solution, in hardened sample, (c) plates as acicular form of martensite phase after electrolytical etching in hardened sample. In tool steels, the improvement in the cutting performance with the addition of cobalt is indisputable. The more difficult the material is to machine, the more effective the addition of cobalt to the tool steel. Cobalt dissolves in iron (ferrite and austenite) and strengthens it at the same time imparting high temperature strength. During solution heat treatment to dissolve the carbides, cobalt helps the resist grain growth so that higher solution temperatures can
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be used to ensure the dissolution of higher percentage of carbides. Steels are quenched after solution annealing and a microstructure consisting of hard martensite with fine alloy carbides is obtained. Tempering will cause the precipitation of ultrafine carbides still in solution and maximum hardness will be attained. Here, cobalt plays another important role, in that it delays their coalescence. This is important as it means that during cutting, the structure is stable up to higher temperatures. Thus, cobalt-containing tool steels are capable of retaining strength at higher temperatures [18-20]. The microstructure given in Figure 6a explains the cobalt effect on the matrix with the comparison of DIN 1.3395 to 1.3394 steel. In electrolytically etched steel, carbides are observed in soft annealed matrix with skeleton morphology due to cobalt wetting. At higher magnification given in Figure 6b, both globular and also facetted carbides within the martensitic matrix, formed after hardening, appear in different sizes.
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Figure 6. SEM images of the microstructures of DIN 1.3394 steel as electrolytically etched; (a) carbides in the matrix with skeleton morphology, in soft annealed sample (b) plates of martensite phase and carbides in hardened sample. 3.3. Carbide analysis The microstructure of high speed tool steels, in annealed condition, consists of martensitic or ferritic matrix and blocky MxCy type carbides, called primary carbides, formed during casting. After heat treatment (annealing, quenching and tempering), this matrix is strengthened by secondary precipitation of extremely fine carbides. The function of the blocky carbides is to protect the matrix against wear and the secondary carbides help to provide high hot strength. Besides, the high speed steel requires high fracture toughness. It is very important to control the type of existing carbides. Hence, the size, distribution, type and fraction of the carbide phase to a large extent determine the properties of powder metallurgical tool steels. Thus, a large number of studies had been undertaken to find ideal tool steel microstructures. Depending on the steel composition several types of carbides (mainly MC, M2C, M6C) are precipitated in high speed steels. During hot working, the primary carbides, formed during solidification, change their as-cast structure to a more spherical one. They have an incoherent interface to the matrix and are a few micrometers in size. In the finished tool, the primary and also secondary carbides formed due to tempering effect are responsible for the high wear resistance, in addition to the high hardness of the matrix [21-25]. In DIN 1.3207 material there are globular carbides in bright contrast and facetted ones in gray contrast. Figure 7 and 8 show the typical carbides observed in DIN 1.3207 tool steel. The spot analysis was carried out to determine the elementel concentration of carbides and it was found that globular type carbides were typically M6C carbides which were W and Mo-rich (Figure 7), and facetted carbides were typically MC carbides in which vanadium was the major element (Figure 8). Both DIN 1.3395 and DIN 1.3394 steels have Cr, Mo, V and W which are strong carbide formers. The examinations revealed that the steels had similar carbide morphologies and types.
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Figure 7. Characterization of globular carbides in DIN 1.3207 tool steel; (a) SEM micrograph, (b) spot analysis giving the elementel spectrum of globular carbide marked in micrograph (a).
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Figure 8. Characterization of facetted carbides in DIN 1.3207 tool steel; (a) SEM micrograph, (b) spot analysis giving the elementel spectrum of facetted carbide marked in micrograph (a). 4. CONCLUSION In this study, the microstructures of hardened DIN 1.3207, soft annealed and also hardened DIN 1.3394, DIN 1.3395 powder metallurgical tool steels are investigated. In the first stage, % 3 nital and Beraha solutions were used to determine the matrix phase and the carbides present within the matrix. In the second stage, the steels were electrolytically etched due to the insufficiency of immersion technique to reveal matrix phase and also the interface of carbides. Aligned carbides are observed in DIN 1.3207 tool steel having martensitic matrix after hardening treatment. Fine dispersed carbides take place in both DIN 1.3395 and DIN 1.3394 tool steels having plate type martensitic matrix. In DIN 1.3207 tool steel, there are globular carbides in bright contrast and facetted ones in gray contrast. EDS analysis shows that globular type carbides are typically M6C carbides which are W and Mo-rich carbides, and facetted carbides are typically MC carbides in which vanadium is the major element. DIN 1.3395 and DIN 1.3394 steels have Cr, Mo, V and W which are strong carbide forming elements and their matrices also consist of typical M6C and MC carbides similar to DIN 1.3207 tool steel. References 1. German, R. M., Powder Metallurgy Science, MPIF, Princeton, NJ, USA, 1994. 2. Schatt, W., Wieter, K. P., Powder Metallurgy Processing and Materials, EMPA, Shewsbury, 1997. 3. Matula, G., Dobrzaski, L. A., Herranz, G., Vrez, A., Levenfeld, B., Torralba J. M., Structure and Properties of HS6-5-2 Type HSS Manufactured by Different P/M Methods, Journal of Achievements in Materials and Manufacturing Engineering, Vol. 24(2), pp. 71-74, 2007. [4] Mesquita, R. A., Barbosa, C. A., High Speed Steel Produced through Conventional Casting, Spray Forming and Powder Metallurgy, 6th International Tooling Conference, Karlstad-Sweden, pp. 387-402, 2002. 5. Schneider, R., Schulz, A., Bertrand, C., Kulmburg, A., Oldewurte, A., Uhlenwinkel, V., Viale, D., The Performance of Spray-Formed Tool Steels in Comparison to Conventional Route Material, 6th International Tooling Conference, Karlstad-Sweden, pp. 1111-1124, 2002. 6. Rosso, M., Ugues, D., Grande, M. A., The Challenge of PM Tool Steels for the Innovation, Journal of Achievements in Materials and Manufacturing Engineering, Vol. 18(1-2), pp. 175-178, 2006. 7. Nurthen, P., Bergman, O., Hauer, I., Carbide Design in Wear Resistant Powder Materials, PM2008 World Congress, Washington-USA, pp. 1-15, 2008. 8. Karaaslan, A., Aka, C., The Influence of Carbide Distribution on the Properties of Hot Work Tool Steels, METAL 2009, Hradec nad Moravic-Czech Republic, pp. 1-4, 2009. 9. Therkildsem, K. T., Dahl, C. V., Analysis of Carbide and Inclusion in High Speed Tool Steels, Report no : RisR-1360(EN), Ris National Laboratory, 2002. 10. Hetzner, D. W., Van Geertruyden, W., Crystallography and Metallography of Carbides in High Alloy Steels, Materials Characterization, Vol. 59, pp. 825-841, 2008. 11. Godec, M., Batic, B. ., Mandrino, D., Nagode, A., Leskovek, V., kapin, S. D., Jenko, M., Characterization of the Carbides and the Martensite Phase in Powder-Metallurgy High-Speed Steel, Materials Characterization, Vol. 61, pp. 452-458, 2010. 12. Hutchinson, B., Hagstrm, J., Karlsson, O., Lindell, D., Tornberg, M., Lindberg, F., Thuvander, M., Microstructures and Hardness of As-Quenched Martensites (0.1-0.5 %C), Acta Materialia, Vol. 59(14), pp. 5845-5858, 2011.
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13. Krauss, G., Martensite in Steel : Strength and Structure, Materials Science and Engineering A, Vol. 273-275, pp. 40-57, 1999. 14. Schumann, H., Metallographie, VEB Deutscher, Verlag fr Grundstoffindutrie, Leipzig, 1974. 15. Petzow, G., Metallographisches, Keramographisches, Plastographisches etzen, Editions Gebrder Borntraeger, Berlin, 1994. 16. Van der Voort, G. F., Manilova, E. P., Michael, J. R., Lucas, G. M., Study of Selective Etching of Carbides in Steel, Microscopy and Microanalysis, Vol. 10, pp. 76-77, 2004. 17. Van der Voort, G. F., Lucas, G. M., Manilova, E. P, Michael, J. R., Study of Selective Etching of Carbides in Steel, Praktische Metallographie, Vol. 36, pp. 255-262, 2004. 18. ASM Handbook, Machining, Vol. 16, pp. 51-59, ASM International, Ohio-USA, 1989. 19. Moiseev, V. F., Geller, Y. A., Effect of Cobalt on Structure and Properties of Fast-Cutting Steel, Metal Science and Heat Treatment, Vol. 7(4), pp. 245-249, 1965. 20. Gulyaev, A. P., Kupalova, I. K., Effect of Cobalt on the Structure and Properties of High-Speed Steels, Metal Science and Heat Treatment, Vol. 12(8), pp. 666-671, 1970. 21. Bochnowski, W., Leitner, H., Major, L., Ebner, R., Major, B., Primary and Secondary Carbides in High-Speed Steels after Conventional Heat Treatment and Laser Modification, Materials Chemistry and Physics, Vol. 81(2-3), pp. 503-506, 2003. 22. Karagz, ., Andren, H. O., Secondary Hardening in High Speed Steels, Zeitschrift fr Metallkunde, Vol. 83, pp. 386-394, 1992. 23. Fischmeister, H. F., Riedl, R., Karagz, ., Solidification of High Speed Tool Steels, Metallurgical Transactions A, Vol. 20, pp. 2133-2148, 1989. 24. Dobrzanski, L. A., Matula, G., Vrez, A., Levenfeld, B., Torralba,J. M., Fabrication Methods and Heat Treatment Conditions Effect on Tribological Properties of High Speed Steels, Journal of Materials Processing Technology, Vol. 157-158, pp. 324-330, 2004. 25. Trabadelo, V., Gimnez, S., Iturriza, I., Development of Powder Metallurgy T42 High Speed Steel for Structural Applications, Journal of Materials Processing Technology, Vol. 202(1-3), pp. 521-527, 2008.
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Foil 1: Topic Overview 1. 2. 3. 4. 5. 6. 7. 8. 9. Press Procedure Adapter Systems Press Tooling Filling Powder Transfer Pressing Pressure Relief Demolding Summary
1. Press Procedure Next to the withdrawal method (fixed bottom punch with movable die), the application of the ejection method (fixed die with movable top- and bottom punches) also becomes more established when using hydraulic presses. The withdrawal method is still predominantly applied with mechanical- and hybrid presses. The main advantage when using the withdrawal method lies in the simple applied load of the top punch during demolding of the press part, which will be discussed at a later point. Since the control technology has become considerably more efficient in the last few years, the ejection method is applied more frequently today with hydraulic presses. By synchronous ejection of the press part between top- and bottom punch, materials can also be pressed which tend to stockpile during the removal process. One of the advantages of the ejection process is that there is only one constant removal height, also if there are different bottom punch lengths. Another advantage is that the mass in the
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fill system is only moved in horizontal direction during the fill process which significantly decreases the segregation of the press mass. Furthermore, the programming during the ejection process is easier to understand, due to a similar course of movement of the top and bottom punch. All positions of the press axis relate to the fixed top edge of the die. Pressing processes like the pressing from both sides are easy to realise, whereas in the withdrawal process you have to work with relative movements between die and bottom punch. 2. Adapter Systems Besides taking up the press tooling, the adapter systems of modern high capacity powder presses also take over the precise guiding function of the tools. Present-day adapter systems with up to 8 and more press axes demand very high requirements towards precision and flexibility in regards to tool pick up and tool changing possibilities. When pressing complex component geometries, the press tools were often changed together with the tool adapter system. Simple press tools were already changed in the press because the change times were usually not above the adapter change times. Today, the possibilities of an easy and precise movement of hydraulic press axes make it possible to change even complex tooling within the presses. Especially the electrical handwheel is of advantage with which each individually selected press axis can be easily and accurately moved to any position. This kind of tool change offers specific benefits in regards to the withdrawal pressing since mostly hydraulic drives of the additional axes are here integrated in the adapter. An uncoupling of the hydraulic- and electric systems from the actual press is not applicable, which can often lead to leakages of the hydraulic connections after a few cycles. This is not necessary when pressing according to the ejection method because the hydraulic drives as well the measuring systems are part of the press and not of the adapter. Even presses without separate adapter are applied for the last few years and were integrated into the press. 3. Press Tooling Depending on the producible part geometry, the press tools are getting more and more complex with the increase of shape variations in the product. In order to achieve a widely even density distribution, it is necessary to also separate in cross section changes, press axes and tool axes. With some products it is possible that up to 8 and more press levels and therefore tool splittings are required. On one hand, this serves to produce the required filling spaces, on the other hand it enables the necessary powder transfer in the compaction start position before the actual densification begins. If these requirements can be met by the press tooling, only the forces that build up by the press travel and speed must be transferred from the tool to the press part during the densification process. Since the divided press tools can also be placed on different adapter levels, often only tool distance pieces can be used from each press level in the adapter to the press tools in order to construct the tools as short as possible. 4. Filling The filling process has an essential influence on the quality of the final product. Mistakes that are made in this process cannot be compensated during the subsequent pressing procedure. Therefore, the filling process is an essential task which has a critical influence on the final product quality. Hereby, especially with stepped tooling, fill density deviations caused by air can lead to density differences in the press part segments (Video). Through venting systems on the fill shoe, such fill density differences can be decreased and simultaneously shorten the fill times. Another important point that should be considered, especially during the compaction of higher density materials, is the decoupling of the supply storage (big bag) from the actual fill hopper. Here, a constant force of the powder mass should be reached; from the hopper via the hose and the fill shoe to the empty cavity. This prevents fill density deviations between full and depleting supply tanks. Any issues at the process start that should be taken into consideration during filling can already have a positive influence on the final product. 5. Powder Transfer Oftentimes it becomes necessary, especially with complex part geometries, to bring the press mass via the parted bottom punch in such a position before the densification that, at the later press process, the same density ratio
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exists in each part cross section. This shall prevent, that material displacements of higher density zones in lower density zones take place. It is also possible to transfer press mass out of the filled cavity to the top punches that are positioned above the die in order to press conical geometries upwards as well. 6. Pressing The compaction of the press mass occurs through the top- and bottom punch movement, or through the top punch and die movement (withdrawal principal) which moves relatively to the bottom punch. Thereby, the press mass is compressed with such forces that green parts are created according to the tool shape. This way, specific press forces of up to 100 kN/cm and more can act upon the press mass. Special attention should be paid to the even density gradient over the entire press part cross section to eliminate marginal powder shifting during the press process. This means that different single pair of punches must move with different speeds during the densification process so they reach their press position at the same time. The calculation and monitoring of such travel- and speed profiles is carried out automatically by the control elements of modern powder presses. 7. Pressure Relief After all press axes have reached their press position, a defined relief of the green part takes place. Here it is important, especially with stepped parts, that an even relief of all press axes occurs. Complex part geometries which require multiple top- and bottom punch levels have press punches of different length due to the adapter- and machine construction. Here, the springback forces of punch surface and punch length have a corresponding effect on the green part. With presses that work with fixed stops of the bottom punches, a punch relief downwards is not possible because these fix positions cannot be changed anymore. This results in different forces upon the green part during the relief of the top punch and oftentimes leads to cracks in the cross section variations of the component. At this point, an important advantage of the hydraulic hold of the press axes in press position comes in. Through a controlled relief of all punch axes top- and bottom punches, according to the punch compression, a crack formation can be specifically countered. 8. Demolding After the green part only shows forces in radial direction due to the prior described relieve process, it can be ejected by the bottom punch in overcoming the friction forces. Press mass (for example; ceramic mass) which tend to axial pile-up by pressed-in air, are weighed down during the removal process through application of programmable slight force of the top punch(es). This prevents a total axial relief and the green part can radially relax after demolding. 9. Summary Since the components produced by powder press technology become more and more complex, the demands on the press systems also increase steadily. Here, the production process of such components has to be considered in its entirety, as you can see in the above described procedural steps. KOMAGE took on the challenge to face these great demands and to successfully put them into practice by applying more than 100 years of experience in powder press construction as well as continuous innovative advancement in hydraulic, control technology and tool design make KOMAGE your qualified partner in the powder press technology.
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Prealloyed Molybdenum Low-Alloy Steel Powders and the Flexibility of Hybrid Alloys based on these Powders
W.B. James, Bruce Lindsley, Kalathur S. Narasimhan Hoeganaes Corporation Cinnaminson, NJ USA Abstract The introduction in 1990 of a water atomized low-alloy steel powder that used molybdenum as the principal alloy addition (Ancorsteel 85 HP) opened the doors to the development of numerous hybrid low-alloy steels based on the molybdenum-steel powder. Today, there are a number of water atomized prealloyed molybdenum-steel powders that contain different amounts of molybdenum; the appropriate one may be used depending on the hardenability needed for the intended application. The prealloyed molybdenum-steels are ideally suited for quench-hardening and tempering applications where their excellent compressibility and good hardenability may be utilized, along with their consistent dimensional change response. These molybdenum steel powders also form the basis for many hybrid low-alloy steels where the various molybdenum contents available provide great flexibility in alloy design. This paper will review the performance characteristics of these materials and illustrate their great flexibility. Keywords: low alloy, prealloyed powders, sinterhardening, Quench and Temper, heat treated 1. Introduction Water atomized prealloyed powders that use molybdenum as their principal alloy addition, were introduced commercially in 1990 [1]. They were developed via a design of experiments and the composition with 0.85% molybdenum was selected for commercialization because it offered excellent compressibility coupled with good hardenability. When mixed with graphite the material is well suited for applications that require quench-hardening and tempering. Because of its good compressibility, the powder was soon the base for hybrid alloys in which the base was combined with additions of nickel, copper, or both nickel and copper [2]. A powder with higher molybdenum content (1.5%) was introduced in Europe as both a prealloyed powder and the base for diffusion-alloyed powders [3]. The lower compressibility (see Figure 1) and higher cost of the 1.5% molybdenum powder (even at that time) resulted in little interest in the North American market but the diffusion alloys were used for some applications in Europe and Asia. In recent years, the considerably higher cost of molybdenum has led to the commercialization of prealloyed powders with lower molybdenum contents (both 0.5% and 0.3% Mo) and these powders now form the base for various hybrid alloys. Hybrid alloys based on 0.5% molybdenum are now standard materials in MPIF Standard 35 Materials Standards for PM Structural Parts [4]. These materials were first introduced in 1999 [5 and 6]. Subsequent developments based on prealloyed molybdenum steels
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Figure 1: Compressibility of some water atomized, prealloyed powders. (FL-4400 = 0.85% Mo; FL-4900 = 1.5% Mo; the others are Ni-Mo prealloys) include PM-Cr steels and PM-Mn steels [7-12]. This paper will provide an overview of the performance of these prealloyed powders that use molybdenum as their principal alloy addition. The flexibility of these materials will be highlighted along with the current trend towards materials that contain lower percentages of molybdenum. 2. Quench-Hardened and Tempered Properties Prealloyed powders that use molybdenum as their principal alloy addition are particularly well suited for applications where the PM parts need to be oil-quenched and tempered. The hardenability of the materials is a function of their molybdenum content Figure 2. Lindsley has shown that a 25 mm diameter compact, 25 mm high, made using a prealloyed powder with 0.3% molybdenum, through hardens at graphite addition levels as low as 0.6% [13] see Figure 3. At lower levels of graphite, the compacts no longer through harden but have a hardness profile with a high surface hardness (martensite) and a softer core (mixed martensite/bainite/unresolved pearlite). As the molybdenum content is increased, the graphite addition required to through harden the 25 mm diameter compacts is reduced Figure 4. The average microindentation hardness level for each molybdenum-graphite combination in these through hardened compacts is also listed in Figure 4. The decrease in microindentation hardness as the graphite addition decreases is apparent; martensite hardness is a function of its carbon content. The compact made from a base iron powder (0% Mo) did not through harden so the microindentation hardness of its case is shown. The samples in the referenced study were 25 mm in diameter. Part size should be kept in mind when determining the molybdenum content that is needed to through harden at a given carbon content. Smaller parts would not require the same molybdenum content for them to through harden. Larger parts would need greater hardenability and higher molybdenum content leads to increased hardenability - Figure 2.
Figure 2: The effect of molybdenum content on the Jominy end-quench hardenability for materials with 0.6% graphite.
Figure 3: Microindentation hardness profiles of oil quenched 25 mm diameter compacts with 0.3% molybdenum and various graphite additions.
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Figure 4: Minimum graphite contents required for through hardening oil quenched cylindrical compacts of 25 mm diameter made using various molybdenum prealloys. The average microindentation hardness is given for each Mo-graphite combination. * Note that the material with zero molybdenum did not through harden at 0.9% graphite and the microindentation hardness value listed is from the surface hardened case. There is little difference in the compressibility of the prealloys with 0.3, 0.5, and 0.85% Mo but the compressibility of the powder with 1.5% Mo decreases by about 0.08-0.1 g/cm3. Although copper steels are the workhorses of the powder metallurgy industry, they have limited hardenability and little ductility after heat treatment. When the microindentation hardness of a quenchhardened 25 mm diameter compact made from FC-0208 was compared with that for compacts made from a 0.3% Mo prealloyed powder the difference in hardenability is readily apparent [13] Figure 5. The FC-0208 compact has a hard case to a depth of less than 2 mm whereas the compacts made from the prealloyed powder through harden. Hanejko has shown that the dimensional change of the 0.3% Mo prealloyed material is less sensitive to density variation than FC-0208 [14]. Heat-treated PM gears made from FC-0208 showed greater scatter in dimensional change compared with the same gears made using a 0.3% prealloyed Mo steel powder.
Figure 5: Microindentation hardness profiles from the edge (distance = 0) toward the center of oil quenched, 25 mm diameter compacts with 0.9% graphite. 3. Hybrid Analogs of Diffusion Alloys Based on an Iron Powder Hybrid alloys based on 0.5% molybdenum were first introduced in 1999 [5 and 6]). They are now standard materials in MPIF Standard 35 Materials Standards for PM Structural Parts [4]. At the same sintered carbon content, these hybrid materials have higher tensile strength than the diffusion alloys based on an iron powder in the as-sintered condition Figure 6. While the materials have the same chemical composition, the hybrid alloys, made with a prealloyed powder base, have greater hardenability than their
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diffusion-alloyed analogs Figure 7 [4,15]. This makes them much better than the diffusion alloys based on an iron powder for applications where the PM parts need to be heat treated. In light of the good performance of the hybrid alloys based on a prealloyed powder with 0.5% molybdenum, it was decided to evaluate hybrid alloys with the same nickel and copper additions based on a prealloyed powder with 0.3% molybdenum. The samples were sintered at 1120 C for 13 minutes at temperature in a nitrogen:hydrogen atmosphere (90 v/o :10 v/o). No accelerated cooling was used. The oil-quenched and tempered specimens were tempered at 200 C for 1 h. The results are summarized in Figure 8 [15]. In the as-sintered condition, the yield strength of the hybrid alloy with 0.5% Mo exceeds that of the diffusion-alloyed material of similar chemical composition. This was expected
Figure 6: (a) As-sintered and (b) heat-treated tensile properties of diffusion-alloyed materials based on iron powder and their hybrid analogs based on a 0.5% Mo prealloy. from the data presented in Figure 6. It is interesting to note that each of the materials with 0.3% Mo has a similar yield strength to that of the comparable diffusion-alloyed material. This should be reflected in actual PM parts as the materials based on the prealloyed powder with 0.3% Mo have a hardenability that should be similar to that of the diffusion-alloyed materials.
Figure 7: Jominy hardenability comparison between diffusion-alloyed materials based on iron powder FD-0205 and FD-0405) and hybrid low-alloy powders based on a prealloyed powder with 0.5% Mo (FLN2C-4005 and FLN4C-4005) In general, the ultimate tensile strength of the quench-hardened and tempered lower nickel content materials is better than that of the materials with 4% nickel. This is due to higher amounts of retained austenite in the material with 4% nickel. The only reason for selecting the diffusion-alloyed material with 4% nickel would be for its better hardenability or slightly better impact energy. As the hardenability of the hybrid alloy with the lower nickel content is similar to that of the diffusion-alloyed material with 4% nickel, the hybrid alloy with the lower nickel content would be a more cost-effective choice.
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4. PM Chromium Steels Alloy additions such as chromium and manganese present difficulties when they are used in prealloyed water atomized powders due to their high affinity for oxygen. Once formed,
Figure 8: As-sintered [(a) and (b)] and heat-treated [(c) and (d)] tensile properties for hybrid and diffusionalloyed materials of the same chemical composition compared with the tensile properties of a hybrid low-alloy steel with the same nickel and copper additions but a lower prealloyed molybdenum content. All the materials had a 0.6% graphite addition and a density of 7.0 g/cm3. their oxides are extremely hard to reduce and if the alloy addition is not in solution it does not contribute to the hardenability of the material. A hybrid PM chromium steel alloy based on a 0.85% molybdenum prealloyed powder (Ancorsteel 4300) has been shown to have extremely good mechanical properties [7,8]. While the material may be sintered at | 1120 C in a 90 v/o: 10 v/o nitrogen:hydrogen atmosphere, a full 30 minutes are required at that temperature to develop optimum properties and it has been shown that high temperature sintering is more practical in light of the 10 to15 minutes more typically allowed at temperature during commercial sintering practice [13]. A key attribute of this PM chromium steel is the fact that it sinter hardens at conventional sintering furnace cooling rates (about 0.7 C/s) without the need for an addition of copper; something generally needed with many sinter-hardenable materials. The absence of copper improves the robustness of the material less sensitivity of the dimensional change of the material to density, carbon content, and cooling rate. The high cost of molybdenum in recent years led to the evaluation of hybrid PM chromium steels based on prealloyed powders with lower molybdenum contents and a lean version of the material has been developed based on a prealloyed powder that contains 0.3% molybdenum (Ancorsteel 4300L) [10]. While the hardenability of the hybrid PM chromium steels is lower that that of the hybrid sinter-hardenable
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alloys that contain copper additions, their hardenabilities are comparable to those of other commercial products Figure 9.
Figure 9: Jominy distance to 65 HRA for various PM materials The chemical composition of the hybrid PM chromium steel alloys is listed in Table 1, and the effect of cooling rate on the mechanical properties of both of the materials with a 0.6% graphite addition is summarized in Table 2 [10]. Table 1: Chemical composition of the hybrid PM chromium low-alloy steels Material Ancorsteel 4300 Ancorsteel 4300L Cr 1 1 Chemical Composition (mass %) Si Ni 0.6 1 0.6 1 Mo 0.8 0.3 Mn 0.1 0.1
Table 2: Mechanical properties of the hybrid PM chromium low-alloy steels as a function of cooling rate (cooling rate measured between 650 and 315 C) graphite addition of 0.6%. Material Ancorsteel 4300 Ancorsteel 4300L Cooling Rate (C/s) 0.7 1.6 2.2 0.7 1.6 2.2 Yield Strength (MPa) 752 896 1069 690 738 827 UTS (MPa) 1062 1172 1241 986 1020 1055 Total Elongation (% in 25 mm) 1.9 1.5 1.3 2.4 1.9 1.5 Impact Energy (J) 19 18 15 20 18 16 Apparent Hardness (HRA) 66 69 71 62 65 67
For the material that is based on a prealloyed powder with 0.85% molybdenum, increasing the cooling rate from 0.7 C/s to 2.2 C/s improved the yield strength by 42%. For the leaner alloy (0.3% Mo), the corresponding improvement in yield strength was 20% for the same change in cooling rate. The yield strength of the leaner alloy is about 80 to 90% that of the other material depending on the cooling rate. 5. PM Manganese Steels The ferrous PM industry continues to develop and expand its use of non-traditional PM alloying elements. Price, environmental, and recyclability concerns with Mo, Ni and Cu have driven this expansion. Manganese is a relatively inexpensive, yet effective, alloying element in wrought steels. Nevertheless,
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oxygen sensitivity has limited the use of manganese in PM steels in the past. The current nitrogenhydrogen sintering atmospheres with low partial pressures of oxygen now permit its use. The combination of Mn with a moderate level of Mo results in PM steel alloys with mechanical properties approaching those of FD-0405.
Figure 10: Microstructures of the two PM manganese steels. Conventional cooling rate (0.7 C/s) for (a) and (b) and accelerated cooling (1.6 C/s) for (c) and (d). ANCORBOND FLM-4005 = (a) and (c) ANCORBOND FLM-4405 = (b) and (d) Equally important, these alloys can be processed under typical, industrial sintering conditions. At higher carbon contents these manganese steels can be used as lean alloy, sinter-hardening grades as has been demonstrated by Lindsley and James [11, 12]. The microstructures of two PM manganese steels are presented in Figure 10. The ANCORBOND FLM-4405 material has a greater hardenability than the ANCORBOND FLM-4005 and this is reflected in the microstructures; there is a higher percentage of martensite present in the ANCORBOND FLM-4405 at both cooling rates. 6. Conclusions Since their introduction twenty years ago, prealloyed water atomized powders with molybdenum as their principal alloying element have become the widely used prealloyed low-alloy steel powders. They provide great flexibility in ferrous PM material design. They are used not only for their quench-hardened and tempered properties but also serve as the base for a wide range of hybrid low-alloy PM materials; analogs of the diffusion alloys that are based on iron, analogs of the diffusion alloys that are based on molybdenum prealloys, in PM chromium steels, and in PM manganese steels. 7. References 1. J.J. Fulmer and R.J. Causton, Tensile, Impact, and Fatigue Performance of a New Water Atomized Low-Alloy Powder Ancorsteel 85 HP, Advances in Powder Metallurgy,1990, Volume 2, compiled by E.R. Andreotti and Patrick J. McGeehan and published by MPIF, pp. 459. 2. Hoeganaes Corporation, Technical Data Sheet for Ancorsteel 85 HP, February 1991. 3. Hgans AB, Iron and Steel Powders for Sintered Components PM 94-2. 4. MPIF Standard 35, Material Standards for PM Structural Parts 2009 edition. 5. F.J. Semel, Ancorloy Premixes: Binder_Treated Analogs of the Diffusion-Alloyed Steels, Advanc-
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es in Powder Metallurgy & Particulate Materials, 1999, compiled by Charles L. Rose and Martin Thibodeau and published by MPIF, Princeton, NJ, Vol. 2, pp. 7-93. 6. W. Brian James, The Development of Engineered Binder-Treated Alternatives to Diffusion-Alloyed Powders, presented at 2nd International Latin American Conference on Powder Technology, November 10-12, 1999, Foz do Iguacu, Brazil. 7. Patrick King, Chromium Containing Materials for High Strength-High Fatigue Applications, Proceedings of the PM2004 World Congress, Vol. 3, published by EPMA, pp. 164-169. 8. Patrick King and Bruce Lindsley, A New Cr-Bearing Alloy for High Performance Applications, Advances in Powder Metallurgy & Particulate Materials 2005, compiled by Candido Ruas and Ted A. Tomlin, published by MPIF, Part 7, pp. 12-21. 9. Bruce Lindsley, Sintering of Chromium Containing PM Steels Processed to High Density, Advances in Powder Metallurgy & Particulate Materials 2008, compiled by Roger Lawcock, Alan Lawley, and Patrick J. McGeehan, published by MPIF, Part 5, pp. 150-160. 10. Patrick King and Bruce Lindsley, Chromium Steels for High Performance PM Applications, Advances in Powder Metallurgy & Particulate Materials 2007, compiled by John Engquist and Thomas F. Murphy, published by MPIF, Part 7, pp. 1-11. 11. Bruce Lindsley and W. Brian James, PM Steels that Contain Manganese, Advances in Powder Metallurgy & Particulate Materials 2010, compiled by Matthew Bulger and Blaine Stebick, published by MPIF, Part 10, pp. 36-49. 12. Bruce Lindsley and W. Brian James, PM Steels that Contain Manganese, proceedings of PM2010 Powder Metallurgy World Congress, Florence, Italy, October 2010, Volume 3, Sintered Steels, pp. 151-158. 13. Bruce Lindsley and Howard Rutz, Effect of Molybdenum Content in PM Steels, Advances in Powder Metallurgy & Particulate Materials 2008, compiled by Roger Lawcock, Alan Lawley, and Patrick J. McGeehan, published by MPIF, Part 7, pp.26-34. 14. Francis G. Hanejko, A Comparison of FC-0208 to a 0.3% Molybdenum Prealloyed Low-Alloy Powder with 0.8% Graphite, Advances in Powder Metallurgy & Particulate Materials 2009, compiled by Thomas J. Jesberger and Stephen J. Mashl, published by MPIF, Part7, pp. 59-72. 15. W. Brian James, Bruce Lindsley, Howard G. Rutz, and Kalathur S. Narasimhan, Lean Hybrid Low-Alloy PM Molybdenum Steels, proceedings of Euro PM2009, October 12-14, 2009, Copenhagen, Denmark, published by EPMA.
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COMPACTION AND MECHANICAL PROPERTIES
www.turkishpm.org
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HIZLI KATILATIRILMI MONEL 400 TOZUNUN PRESLENME DAVRANIININ NCELENMES

Sultan ZTRK*, Blent ZTRK*, Fatih ERDEMR* ve Yksel PALACI** Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080, Trabzon, suozturk@ktu.edu.tr ** Nide niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 51240, Nide, ypalaci@nigde.edu.tr
*
zet Bu almada su jeti soutmal dner disk atomizasyonu ile retilen Ni-Cu esasl Monel 400 tozlar kullanlarak, ortalama toz boyutu ve boyut dalmnn preslenen paralarn ham younluklarna etkileri incelenmitir. Bu amala 125/tava, -180/125, -250/180 ve -355/250 m elek aralklar ile bunlarn farkl oranlardaki katklaryla oluturulan sekiz farkl boyut dalmna sahip fraksiyonlar denenmitir. Ayrca, presleme basncnn ham younlua etkisini incelemek amacyla 150, 250, 350, 450 ve 600 MPa basnlar kullanlmtr. En yksek ham younluk 600 MPa presleme basncyla % 83 olarak elde edilmi ve artan presleme basncyla sertliin, tozlardaki plastik deformasyonun, paracklar aras temas alannn ve koordinasyon saysnn artt, porozitenin azald tespit edilmitir. Anahtar Kelimeler: Monel 400 Alam, Presleme, Ham Younluk.
INVESTIGATION OF PRESSING BEHAVIOUR OF RAPIDLY SOLIDIFIED MONEL 400 POWDER

ABSTRACT In this study, the effect of mean particle size and size distribution on the green strength of compacts produced by Monel 400 alloy powders which were obtained by water jet cooled rotating disc atomization have been investigated. Eight group samples were prepared by using sieve fractions of 125/pan, -180/125, -250/180 and -355/250 m, for this aim. Also, compacting pressures of 150, 250, 350, 450 and 600 MPa were used to investigate the effect of pressure on the green density. The experimental results showed that the highest green density of 83% was obtained with the compacting pressure of 600 MPa. The properties of hardness, plastic deformation of particles, the contact areas among the particles and the coordination number of particles increased and the porosity decreased with increasing compacting pressure. Key words: Monel 400 Alloy, Pressing, Green Density. 1.GR Tozlarn bir kalp ierisinde basnla deforme edilerek, aralarnda ba oluturma ilemine toz sktrma denir. Sktrma sonras elde edilen younlua ham younluk, mukavemete ise ham mukavemet denir. Sktrma ilemi ile parann tanabilecek kadar bir mukavemet kazanmas amalanr. Tam younluk ise sinterleme sonras elde edilir[1,2]. Eksenel sktrma; tozlarn sert bir metal kalpta tek eksende basn uygulayarak sktrlmasdr. Basncn tek bir zmbadan uygulanmas tek hareketli sktrma olarak ifade edilirken, basncn alt ve st zmbalarn her ikisinden ayn anda uygulanmas ilemi ift hareketli sktrma olarak adlandrlr. Ayn etki st zmbann basn
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uygulamas srasnda kalbn hareketli olmas ile de elde edilebilir. Sktrma genellikle souk olarak uygulanmakla birlikte, ham younluun artrlmas amacyla lk olarak da uygulanabilir. Sktrma ileminin balang aamasnda kalp ierisindeki toz grnr younluktadr ve her bir toz tanesi ortalama olarak 4-6 aras komu tane ile temastadr [3-5]. Presleme ileminin balangcndan sonuna kadar olan safhalar e ayrmak mmkndr. Presleme ileminin ilk aamasnda tozlar konumlarn deitirerek gevek durumdan sk paket durumuna gemeye balar. Bu aamada paracklarn elastik deformasyonu sz konusudur. kinci aamada younlamada ani bir art meydana gelir. Bu aamada tozlar birbiri zerinden kayarak yeniden konumlanrken, paracklar arasnda meydana gelen kenetlenme ile geri dn olmayan bir pozisyona girilmi olur. Kenetlenen paracklar plastik deformasyona uradklarnda son aama balam olur. Basn arttka tanecikler aras temas alan artar. Son aamada younlama komu paracklarn karlkl olarak bir araya gelmesiyle salanr. Balangta 4-6 olan parack koordinasyon says son aamada 10-12 gibi rakamlara ulaabilir. Sktrma ilemi devam ettike paracklar aras temas alan byyerek ham younlua ulalr. Son aamada paracklarn plastik deformasyonla sertlemelerinden dolay younlama hznda bir azalma grlr [6-8]. Preslemenin balang aamasnda tozlar grnr mukavemete sahiptir. Presleme sonunda elde edilen mukavemet ise ham mukavemettir. Bir sonraki aamada uygulanacak sinterleme ileminde maksimum mukavemete ulaabilmek iin sinterleme ncesi ham mukavemetin yksek olmas gerekir. Elde edilecek ham mukavemetin deeri, presleme basnc yannda esas itibariyle tozun birtakm zelliklerine baldr. Bunlar; tozun kimyasal bileimi, ortalama toz parack boyutu, boyut dalm, toz ekli ve tozlarn sertliidir. Presleme ileminde tozlar deformasyonla birlikte sertletikleri iin hesaplanandan daha fazla basnca gerek duyulur. Younlamaya sebep olan ortalama basn her zaman uygulanan basntan daha azdr ve toz para geometrisi, radyal basn dalm ve toz-kalp duvar srtnmesi deikenlerine baldr [9,10]. Yksek ham younluk ksa ve byk apl paralarda elde edilir. Toz boyutu ve ekli hem grnr younlua hem de preslenebilirlie etki eder. Kk ve kresel tozlarn grnr younluklar byk ve dzensiz tozlara gre daha yksektir. Kresel tozlarn grnr younluklar teorik younluun %60n bulurken, titreime tabi tutulduklarnda bu deer %64e kadar kabilmektedir. Bu her parack iin 6-7 temas noktas anlamna gelmektedir. Dzensiz ekilli tozlarda paketleme younluu teorik younluun %30u olurken, dzensiz ekilli ve sngerimsi tozlarda ok daha dk olmaktadr. Paracklar aras srtnme, biri dierini kayarak geen paracklarn sergiledii direnci ifade eder. Bu srtnme, nemli lde toz yzey alan, yzey przll ve yzeyin bileimi tarafndan belirlenir. Toz boyutu kldke (yzey alan arttka) paracklar aras srtnme artar. Dier taraftan, kresel tozlarn sktrlabilme kabiliyetleri, keli yapya sahip tozlarnkinden daha dk olmaktadr[11-13]. Bu almada ortalama toz boyutu, boyut dalm ve presleme basncnn preslenen paralarn ham younluuna etkisi incelenmitir. Bu amala, Monel 400 alamndan su jeti soutmal dner disk atomizasyonu yntemiyle retilmi farkl elek aralna ve ortalama boyuta sahip tozlar kullanlmtr. Presleme ilemi tek eksenli ve ift tesirli preste gerekletirilmi olup, presleme basncnn ham younlua etkisi 150, 270, 360, 480 ve 600 MPa basnlar kullanlarak incelenmitir. Ortalama toz boyutu ve boyut dalmnn ham younlua etkisi farkl elek aralndaki tozlarn 480 MPa sabit basnta preslenmesiyle aratrlmtr. 2. DENEYSEL ALIMALAR Bu almada, bileimi izelge 1de verilen Ni-Cu alamndan (Monel 400) su jeti soutmal dner disk atomizasyonu yntemiyle retilen tozlar kullanlm olup, retilen tozlar tek eksenli ift tesirli preste preslenerek; ortalama toz boyutu, boyut dalm ve presleme basncnn ham younlua etkileri incelenmitir. izelge1. Monel 400 alam kimyasal bileimi (% A.) Element Ni 66.8 Cu 31.45 Mn 1.33 Fe 0.97 Si 0.38 C 0.1 P 0.013 S 0.002
Monel 400 alamndan toz retimi KT Metalurji ve Malzeme Mhendislii Blmnde mevcut bulunan su jeti soutmal dner disk atomizasyon nitesinde gerekletirilmitir. ematik resmi ekil 1de verilen atomizasyon
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nitesinde, Monel 400 alam indksiyon stma sistemiyle grafit bir potada ergitilmi olup, potann dip ksmndaki delikten serbest dme ile yksek hzda dnmekte olan su jeti soutmal bakr disk zerine aktlarak atomize edilmitir. Buradan alnan tozlar eleme ilemine tabi tutulmu ve 355 m elek altna geen tozlar bu almada kullanlmtr. Atomizasyon nitesi dzgn dairesel st ksm ve konik dairesel alt ksmdan olumaktadr. Dzgn dairesel ksmn ap 2500 mm, ykseklii ise 600 mmdir. Alt ksm, tozlarn toz toplama blgesine kolaylkla ulaabilmesi iin konik olarak tasarlanmtr. Konik olan alt ksmn ykseklii ise 1500 mmdir. retilen tozlara herhangi bir kirliliin bulamamas iin atomizasyon nitesinin tamam AISI 304 paslanmaz elik sacdan imal edilmitir. Yaplan almalarda, disk malzemesi olarak s iletim katsays yksek olan elektrolitik bakr seilmi olup, disk ap 100 mm, et kalnl 0,5 mmdir. Ayrca, su ile soutmann yaplabilmesi iin disk, ters kap eklinde tasarlanmtr. Diskin kanatk says 4 olup kanatk profili dikdrtgen ekillidir (34 mm). Disk soutma suyunun sv alamla ve retilen tozlarla temasn engellemek iin metal sac koni kullanlmtr. Atomizasyon esnasnda sv metal disk merkezinden yaklak 35 mm uzaa aktlarak disk kenarndan maksimum hzla atomize olmas salanmtr. Disk dnme hz, kontrol nitesinden 0-24000 d/d aralnda istenen devir saysna ayarlanabilmektedir. Atomizasyon esnasnda disk zerine aktlan sv alam diskin kenarnda maksimum hza ulaarak atomize olmaktadr. Bu bakmdan, diskin evresel hz olarak en d apa (100 mm) karlk gelen hz alnmtr. Bu almada, toz retimi 14400 d/d disk devir saysnda yaplm olup, bu devir saysna karlk gelen disk evresel hz 75 m/sdir.
ekil 1. Su jeti soutmal dner disk atomizasyonu nitesi ematik resmi. 1- Atomizasyon odas, 2- atomizasyon diski motoru, 3- atomizasyon diski, 4- sac koni, 5- grafit pota, 6- seramik tka, 7- indksiyon bobini, 8- indksiyon stma sistemi, 9- pota ve tka motoru, 10- hidrolik piston-silindir, 11- disk soutma suyu girii, 12- disk soutma suyu k, 13- soygaz girii, 14- soygaz k, 15- toz toplama blm, 16- kontrol nitesi, 17- soutma nitesi. retilen tozlarn ortalama toz boyutu ve boyut dalmnn hesaplanmasnda Malvern Mastersizer 2000 model parack boyut analiz cihaz kullanlmtr. Yaplan analiz neticesinde tozlarn ortalama boyutu (d10), (d50 ) ve (d90) hesaplanm ve boyut dalm grafikleri izilmitir. Bu ilem iin her bir deneyde retilen tozlardan konilemedrtleme yntemiyle yaklak 5-7 g numune alnmtr. Ayrca, tozlarn boyutlarna gre snflandrlmas amacyla Retch marka titreimli eleme cihaz kullanlmtr. Tozlar 25, 36, 45, 63, 90, 125, 180 ve 250 mluk elek serisinde 20 dakika sreyle elenmitir. retilen Monel 400 alam tozlarn morfoloji ve mikroyaplar ile tozlardan presleme ile retilmi paralarn mikroyap incelemeleri Zeiss EVO LS10 marka taramal elektron mikroskobunda (SEM) yaplmtr. Monel 400 tozlarnn morfoloji incelemeleri ift tarafl yapkan karbon band kullanlarak gerekletirilmitir. Mikroyap incelemeleri iin tozlar, bir kalp ierisinde souk sertleen epoksi reine ile yataklandrlmtr. Dalama ilemi, taze hazrlanan 8 g FeCl3, 25 mL HCl , 100 ml H2Odan oluan dalama ayrac kullanlarak 20 s srede gerekletirilmitir. SEM incelemeleri ncesinde, reine kalba yataklanm tozlar iletkenlik salanmas amacyla altn kaplanmtr. Monel 400 alamndan toz retme ilemi esnasnda, tozlar yksek scaklkta olmalarndan dolay havada bulunan oksijenle tepkimeye girerek yzeyleri ince bir oksit tabakasyla kaplanmtr. Bu oksit tabaka hem ok sert hem de ergime scakl yksek bir bileiktir. Bu bileiin sert olmas, presleme ileminde tozlarn plastik deformasyona urayarak ekil deitirmesini, dier bir ifade ile tozlar arasnda mekanik kilitlemeyi engelleyerek presleme ile ham para elde edilmesine mani olur. Belirtilen bu olumsuzluktan dolay tozlardaki yzey oksit tabakasnn presleme ncesi indirgenmesi gerekir. ndirgeme ilemi atmosfer kontroll bir sinterleme frnnda gerekletirilmitir. Monel 400 alam tozlar PLC kontroll sinterleme frnnda 550 oCde, nce azot gaz ile frn ortam temizlenerek, sonra yksek saflkta (%99,999 saflkta) hidrojen gazyla 10 dak. sre ile indirgenmitir. ndirgeme ileminin tam olarak gerekleip gereklemedii XRD cihazyla yaplan faz analizi ile kontrol edilmitir.
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Hidrojen atmosferinde indirgenmi ve elemeye tabi tutularak tasnif edilmi tozlardan ham younlukta para retmek amacyla PLC kontroll, tek eksenli ve ift etkili 50 ton kapasiteli hidrolik toz kalplama presi kullanlmtr. Tozlar ASTM 8M04 standardnda ekme numunesi formunda bir kalpta preslenmi olup, kullanlan kalp tel erozyon yntemiyle hassas bir ekilde retilmitir. Presleme basncnn ham younlua etkisini incelemek amacyla 150, 270, 360, 480 ve 600 MPa basnlarda presleme yaplmtr. Tozlarla kalp yzeyi srtnmesini en aza indirmek amacyla presleme ncesi kalp ve zmba yzeyleri inko stearat ile yalanmtr. Kullanlan presin ematik resmi ekil 2de gsterilmitir.
ekil 2. ift tesirli tek eksenli presin ematik resmi. 1-Kauuk ayak, 2- kolonlar, 3-klavuz silindir, 4- st silindir piston, 5- alt silindir, 6- pres tablas, 7- alt zmba ve kalp boluu, 8- st zmba, 9- PLC kontrol nitesi, 10- hidrolik devre elemanlar, 11- motor, 12- pompa, 13- hidrolik ya tank.
3. DENEYSEL SONULAR VE TARTIMA Deiik elek aralklarna ait Monel 400 alam tozlarn SEM fotoraflar ekil 3te verilmitir. ekilden de grlebilecei gibi, tozlarn tamam kresel ekilli olup, toz boyutuna bal olarak toz ekli deimemitir. Genellikle 90 mdan byk boyutlu olan tozlarn yzeylerinde ekilme boluu olumutur. Toz boyutu bydke ekilme boluu miktarnn artt tespit edilmitir. ekilme boluklarnn nispeten byk apl tozlarda daha fazla olmas, toz boyutunun bymesiyle souma hznn azalmasna iaret etmektedir.
ekil 3 Monel 400 tozlarn morfolojisi. Elek aralklar: a) -25 m/tava, b) -45/25 m, c) -63/45 m, d) -90/63 m.
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Bu almada deiik elek aralklarna ait tozlar farkl oranlarda katlarak sekiz farkl rnek hazrlanmtr. Bylece, ortalama toz boyutu ve boyut dalmnn preslenmi numunenin ham younluuna etkisi aratrlm ve en optimum deerler ortaya konmutur. Bu amala, retilmi olan tozlar elenerek, -125/tava, -180/125, -250/180, -355/250 m elek aralklarndaki tozlar ayrlmtr. Deiik elek aralklarndan farkl oranlarda katlarak oluturulmu sekiz farkl rnek izelge 2de, bu rneklerin master sizer parack boyut cihaznda elde edilen toz boyut dalmlar ise ekil 4te gsterilmitir. izelge 2. Hazrlanan toz numunelerin elek aral oranlar ve ortalama toz boyutlar rnek kodu MN 1 MN 2 MN 3 MN 4 MN 5 MN 6 MN 7 MN 8 30 30 30 30 30 70 30 40 30 40 40 Elek aral (%) -125/tava (m) 100 100 100 100 -180/125 (m) -250/180 (m) -355/250 (m) d10 29,96 74,75 147,87 199,81 55,25 52,45 55,98 53,35 Ortalama toz boyutu (m) d50 69,72 128,605 209,99 305,99 97,97 110,79 152 107,61 d90 139,62 207,81 299,74 457,81 183,12 267,45 362 342,27
ekil 4. Farkl elek aral tozlardan oluturulmu rneklerin toz boyut dalmlar. Tozlardaki yzey oksit tabakas presleme ve sinterleme zelliklerini olumsuz etkilemenin yannda, grnr younluk ve ak hzn da olumsuz ynde etkiler. Grnr younluk ve ak hz preslemeye dorudan etki eden zelliklerdir. Bunlarn dk olmas, elde edilecek parann ham younluunun da dk olmasna sebep olur. Bu almada kullanlan Monel 400 alam tozlarnn oksit indirgeme ncesi ve sonras Hall ak aparatyla llen grnr younluk ve ak hz lm sonular izelge 3 ve izelge 4de verilmitir. izelgelerden de grlebilecei gibi, indirgeme sonrasnda grnr younlukta ve ak hznda nemli artlar meydana gelmitir. izelge 3. Monel 400 alam tozlarn indirgeme ncesi grnr younluk ve ak hz deerleri. rnek kodu Grnr younluk (g/ cm3) Ak sresi (s) MN 1 3,27 6,35 MN 2 3,01 6,39 MN 3 2,96 7,96 MN 4 2,90 8,3 MN 5 3,31 5,25 MN 6 3,34 5,77 MN 7 3,47 6,28 MN 8 3,43 5,88
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izelge 4. Monel 400 alam tozlarn hidrojen atmosferinde indirgeme sonras grnr younluk ve ak hz deerleri. rnek kodu Grnr younluk (g/cm3) Ak sresi (s) MN 1 3,46 5,03 MN 2 3,17 5,40 MN 3 3,14 6,10 MN 4 3,12 6,90 MN 5 3,34 4,90 MN 6 3,39 5,14 MN 7 3,49 5,40 MN 8 3,54 5,00
Ortalama toz boyutu ve boyut dalmnn ham younlua etkisini incelemek amacyla izelge 2de elek aralk oranlar verilen MN 1-8 kodlu toz numuneler 480 MPa sabit basnta preslenmitir. Elde edilen ham younluk deerleri izelge 5te gsterilmitir. izelge 5. Ortalama toz boyutu ve boyut dalmnn ham younlua etkisi. rnek kodu Ham younluk (%) MN 1 77 MN 2 80 MN 3 79 MN 4 79 MN 5 78 MN 6 79 MN 7 80 MN 8 77
Presleme basncnn ham parann younluuna ve sertliine etkisini incelemek amacyla MN 6 rnek kodlu Monel 400 alam tozlar 150, 270, 360, 480 ve 600 MPa basnlarda preslenmitir. Presleme ncesi, tozlarn homojen karmn salamak ve younluk gradyan oluumunu engellemek amacyla toz numuneler trbila tipi kartrcda 55 d/d dnme hznda 30 dak. sre ile kartrlmtr. Presleme basncnn ham younlukla deiimi ekil 5te verilmitir. Artan presleme basncyla para younluunun artt aka grlmektedir. Presleme balangcnda gevek halde olan tozlar, artan presleme basncyla birbiri zerinden kayarak yeniden konumlanrlar. Basn uygulamas devam ettike tozlar arasndaki boluklar azalr ve mekanik kilitlenme meydana gelir. Tozlarda plastik deformasyonun balad aama son aamadr. Bu aamada younluk art tozlarn deformasyonuyla salanr; ancak tozlar plastik deformasyona urarken ayn zamanda sertleerek mukavemet kazanrlar. Bu sebeple, son aamadaki younluk art hz balang ve ara aamalara gre daha yavatr. ekil 5deki veriler de bunu dorulamaktadr. Grnr younluklar teorik younluun %38i olan tozlar 150 MPa basnla preslendiklerinde, hzl bir younluk artyla ham younluk %60a ykselmektedir. 270 MPa presleme basncnda ham younluk %71e ulamaktadr. 270 MPa presleme basncndan sonra younluk art hznda bir yavalama ortaya kmaktadr. 360, 480 ve 600 MPa basnlarda yaplan presleme ilemleri sonucu elde edilen ham younluk deerleri srasyla %75, %79 ve %83tr. Bu durum, tozlarn plastik deformasyonla mukavemet kazandklarn gstermektedir. Preslenmi numunelerin presleme basncyla mikrosertliklerinin deiimi ekil 6da gsterilmitir. Mikrosertlik lme ilemi Struers Duramin mikrosertlik lme cihaznda, 10 g ykn 10 s sre ile tatbik edilmesiyle gerekletirilmitir. ekil 6dan da aka grld gibi, artan presleme basncyla Vickers sertlik deeri artmtr. Toz paracklarn artan presleme basncyla daha sk paketlenmelerinin sertlii artrd anlalmaktadr. 150, 270, 360, 480 ve 600 MPa basnlarda yaplan presleme ileminde elde edilen mikrosertlik deerleri srasyla 160, 180, 205, 255 ve 270 Vickersdir. Artan presleme basncnn tozlarn daha sk paketlenmesi salayarak sertlik artna sebep olmasnn yannda, tozlar plastik deformasyona uratarak sertliklerinin artmasn da salamaktadr.
ekil 5. Presleme basncyla ham younluun deiimi.
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ekil 6. Preslenmi ham parada presleme basncyla mikrosertliin deiimi Preslenmi ham haldeki paralarda, presleme basncna bal olarak porozite ve toz parack deformasyonu deiimi elektron mikroskobunda incelenmi olup, 270, 360, 480 ve 600 MPa presleme basnlar iin mikroyaplar ekil 7-10da gsterilmitir. ekillerin incelenmesinden, artan presleme basncyla porozitenin azald, tozlardaki plastik deformasyonun, paracklar aras temas alannn ve temasta olan parack saysnn artt aka grlmektedir.
ekil 7. Preslenmi ham paradaki porozite ve parack deformasyonu (presleme basnc 270 MPa).
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ekil 10. Preslenmi ham paradaki porozite ve parack deformasyonu (presleme basnc 600 MPa). 4. SONULAR Yaplan deneysel almalardan ve bulgularn deerlendirilmesinden elde edilen sonular aada verilmitir: 1. retilen Ni-Cu alam (Monel 400) alam tozlarn tamam kresel ekilli olup, toz boyutuna bal olarak toz ekli deimemitir. 90 mdan byk boyutlu tozlarn yzeylerinde ekilme boluu meydana gelmitir. Toz boyutu bydke ekilme boluklarnn artt tespit edilmitir. 2. Monel 400 alamndan retilen tozlarnn yzeylerindeki oksit tabakas yksek saflkta (%99,999 saflkta) hidrojen atmosferinde 550 0C scaklkta 10 dak. sre ierisinde indirgenmitir. 3. ndirgeme sonrasnda grnr younlukta ve ak hznda nemli artlar meydana gelmitir. 4. Artan presleme basncyla ham younluk artmtr ve en yksek ham younluk 600 MPa presleme basncyla %83 olarak elde edilmitir. 5. Artan presleme basncyla sertlik deerinin artt, porozitenin azald, tozlardaki plastik deformasyonun, paracklar aras temas alannn ve temasta olan parack saysnn artt tespit edilmitir. KAYNAKLAR 1. German, R.M., Toz Metalurjisi ve Parackl Malzeme lemleri eviri Editrleri: S. Sarta, M. Trker, N. Durlu, Trk Toz Metalurjisi Dernei Yaynlar:05, 2007,Ankara. 2. Gimenez, S., Vagnon, A., Bouvard, D., Biest, O. V., Influence of The Green Density on The Dewaxing Behaviour of Uniaxially Pressed Powder Compacts, Materials Science and Engineering A, 430, 277-284, 2006. 3. nl, N., avusoglu, L., Toz Metalurjisinin Yaygn Kullanm Alanlar, Metal Dnyas,Teknik Yaz, say:11-12, stanbul, 1995. 4. Rahman, M.M., Nor, S.S.M., An Experimental Investigation of Metal Powder Compaction at Elevated Temperature, Mechanics of Materials, 41, 553-560, 2009. 5. Fischmeister, H.F., Arzt, E., Densification of Powders by Particle Deformation, Powder Metallurgy, vol.26, n. 2, 1983. 6. Poquillon, D., Lemaitre, J., Carles, V., Tailhades, Ph., Lacaze J., Cold Compaction of Iron Powders-Relations Between Powder Morphology and Mechanical Properties Part I: Powder Preparation and Compaction, Powder Technology, 126, 65 74, 2002. 7. Ng, L.S, Loh, N.L., Boey, F.Y.C., Cold-Hot Isostatic Pressing of Mar M200 Superalloy Powders, Journal of Materials Processing Technology, 67, 143-149, 1997. 8. Al-Qureshi, H.A., Galiotto, A., Klein, A.N., On The Mechanics of Cold Die Compaction For Powder Metallurgy, Journal of Materials Processing Technology, 166, 135-143, 2005. 9. Park, S.J., Han, H.N., Oh, K.H., Lee, D.N., Model For Compaction of Metal Powders, International Journal of Mechanical Science, 41, 121-141, 1999. 10. Yamaguchi, K., Takakura, N., Imatani, S., Compaction and Sintering Characteristics of Composite Metal Powders, Journal of Materials Processing Technology, 63, 364-369, 1997. 11. Hyoung, S., K., Yield and Compaction Behavior of Rapidly Solidified AlSi Alloy Powders, Materials Science and Engineering A, 251, 100105, 1998. 12. Iveson, S.M., Page, N.W., Dynamic Strength of Liquid-Bound Granular Materials: The Effect of Particle Size and Shape, Powder Tecnology, 152, 79-89, 2005. 13. Smith, L.N., Midha, P.S., Graham, A.D., Simulation of Metal Powder Compaction, For The Development of a Knowledge Based Powder Metallurgy Process Advisor, Journal of Materials Processing Technology, 79, 94-100, 1997.
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COMPOSITES
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The effect of amount of methanol on the properties of Al-Al2O3 composite powders

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Aykut Canakci1, Temel Varol1, Cihad NAZK1 Department of Metallurgical and Materials Engineering, Karadeniz Technical University, Trabzon, Turkey aykut@ktu.edu.tr, tvarol@ktu.edu.tr
Abstract Mechanical alloying (MA) of elemental powder mixtures of Al- Al2O3 was performed in an argon atmosphere at various amount of methanol using a planetary ball mill. The effect of amount of methanol on production of Al-Al2O3 composite powder were evaluated. A process control agent (PCA) which the balance between cold welding and fracturing is controlled by the addition of a surface additive. Different amounts of methanol were used to study the effect of the process control agent on synthesis and properties of the Al-Al2O3 composite powders. The microstructural evolution of the milled powders was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results indicated that varition amount of PCA during milling process led to a significant change in morphology, particle-size distribution of milled powders. Morever, different microhardness values were obtained for different amount of PCA at same milling time. Keywords: Composite powders, mechanical alloying, Process control agent (PCA) 1. Introduction Mechanical alloying (MA) is a useful powder processing technique that can produce a variety of equilibrium and non-equilibrium alloy phase. The advantage of this process technology is that the powder can be produced in large quantities and the processing parameters can be easily controlled, thus it is a suitable method for commercial applications [1]. By using MA, it is possible to produce a fine and homogeneous distribution of hardening particles be difficult or even impossible with most molten material techniques. The amount that dispersoids strengthen the composite depends on particle type, size, morphology, volume fraction and distribution [2]. In this process, two essential processes are involded, namely, cold welding between particles under high energy collosion. Cold welding and fracturing enable powder particles to be always in contact with each other with atomically clean surfaces and with minimized diffusion distance. Without cold welding, the particles will not be bonded together for interdiffusion, while too much cold welding will lead to an increase in particle size and no formation of clean surfaces for diffusion. Therefore the balance between cold welding and fracturing is essential for a successful MA. The alloying process can only be continued if the rate of welding balances that of fracturing and the average particle size of the powders remains relatively coarse. However, for most material systems, the balance between cold welding and fracturing does not ocur naturally. The balance has to be controlled by the addition of a surface additive, in most cases, called a process control agent (PCA). Several PCAs, such as cyclohexane, hexane, stearic acid, methanol, ethyl acetate or polyethylene glycol are often used in MA [3-6]. To successful attain products with fine dispersion and good homogeneity; it is essential to establish a balance between cold welding and fracturing. However, for ductile systems, as in the milling of aluminum particles, this balance does not ocur naturally, resulting in non-uniform microstructures and properties. One of the effective methods to avoid excessive cold welding reported in the literature is the addition of surface-active substances, known as process control agents (PCAs). These surfactants are mostly organic compounds and are usually added to the powder charge in proportions that vary from 1 to 5wt.% [7]. In this work we have investigated the effect and the role of different amount of methanol on the morphology, particle size and microstructure of a Al-Al2O3 composite powder produced by MA.
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2. Experimental Procedure The initial materials used in this research work were Al powders and Al2O3 particles with a composition corresponding to Al-10wt.%Al2O3. The as-atomized Al alloy powders (Gndodu Exotherm Company, Turkey) with an average powder particle size of 127m and Al2O3 particles (99,7 % purity, Wacker Ceramic Company, Germany) with an average particle size of 13m are used as raw materials. The chemical composition of the as-atomized Al alloy (in wt. %) is 1.230Fe, 1.000Si, 1.000Pb, 0.710Cu, 0.530Zn, 0.116Mn, 0.071Ti, 0.050Mg and Al (balance). Fig. 1a and 1b show the morphologies of the as received Al alloy matrix powder and Al2O3 particles. The Al alloy matrix powder particles are ligamental shape and the Al2O3 particles are polygonal in shape. Methanol was used as the process control agent in varying amounts of 1, 2 and 3 wt% to study the effect of amount of methanol. The powders were milled in two vials of 80ml using a Fritsch Pulverisette 7, Premium line planetary ball mill at a rotation speed of 400rpm. The mixture of Al-Al2O3 powders was milled for 0.5, 1, 2, 4, 6, 8, 10h. The balls used were 10 mm in diameter and ball-to-powder weight ratio was 10:1. The morphology and microstructure of milled powders was analyzed by scanning electron microscopy (SEM). The size distribution of as-received and milled powders was quantified by a laser particle size analyzer (Malvern, model Mastersizer Hydro 2000). Apparent density of composite powders were measured using a Standard Hall Flowmeter. The microhardness of as-received and milled powders was measured by a microhardness tester (Struers microhardness tester) at 10gr load.
(a)
(b)
Fig. 1. Morphology of as-received powders: (a) Al alloy and (b) Al2O3 particles. Table 1. The amount of PCA (methanol) and coded process. Coded Process Process 1 Process 2 Process 3 3. Results and Discussions 3.1. Effect of the processes with amount of PCA on milling process Milling process is given in Table 2. Processes are summarized in the Table 2 for better understanding of the stages of milling. Table 2 shows the effect of the processes with amount of PCA on the mechanical alloyed Al-Al2O3 powders. Table 2. The shapes of milling during the mechanical alloying. Process 0.5 1 P1 Flake +irregular Flake P2 P3 Ligamental Ligamental Ligamental + Flake Ligamental 2 Irregular Flake+irregular Ligamental + Flake 4 6 Semi Equiaxial Equiaxial Flake+ Semi Equiaxial Flake Semi Equiaxial 8 Equiaxial Equiaxial 10 Equiaxial Equiaxial Semi Equiaxial Amount of PCA (wt.%) 1 2 3
Flake+ Flake+ Semi Semi Equiaxial Equiaxial
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3.2. Effect of the processes with amount of PCA on the powder morphology In order to understand the effect of methanol on the morphology of Al-Al2O3 powders during mechanical alloying, Al-10wt.%Al2O3 powder mixtures were milled with different amounts of methanol (1, 2, and 3 wt.%) for 10h. Figs. 2(a-k) show the SEM images of the powders milled for different times (0.5, 1 and 2h). Figs. 2(a-c) are SEM images with process 1 (1 wt. %), Figs. 2(d-f) are SEM images with process 2 (2 wt. %), and Figs. 2(g-k) are SEM images with process 3 (3 wt. %) for different times. The initial morphologies of both Al and Al2O3 powders are shown in Fig. 1a and 1b, respectively. As it is shown in these Figures, the Al2O3 particles are angular or poligonal in shape while Al powders has a distribution of ligament or irregular. It is clear that particle morphology changes with increasing milling time. After 0.5h of milling time (Fig. 2a), the particles were severely deformed plastically by MA and exhibited a shape changes from nearly ligament to flake in milling made by wt. %1 PCA (at process 1). In other words, plastic deformation of the soft matrix powder starts quickly in a short milling time which results in changing its morphology from ligamental to flattened shape. As shown Fig. 2d (at process 2), with increasing amount of methanol, particle deformation decreased and particle morphology showed little change. By increasing the amount of methanol significant changes werent observed in morphology of initial powders, as shown in Fig. 2g (at process 3). There is an important observation in milling made by 3 wt.% PCA. As can be seen Fig. 2g, alumina particles (Al2O3) were not embedded into the Al powders because of amount of excess methanol. In other words, excess amount of methanol decreases the effectiveness of ball-powder collisions. When the amount of methanol is less than 3 wt.% during milling time, such as 1 and 2 wt.%, work hardening becomes more dominant in the mechanical alloying process. As shown from SEM images of 2h of milling (Figs. 2c, 2f, 2g) fracturing effectiveness decreased with increasing amount of methanol. It can be easily observed that finer as-milled Al-Al2O3 powder particles are achieved with increasing milling time. If the critical PCA value is exceeded (3 wt.%), the particle morphology and particle size varies from less than other process (1 and 2 wt.%) with the increasing milling time. Fracturing process seems dominant in the powders using 1 wt.% methanol (Fig. 2c).
Fig. 2. Variation of the powder morphology with milling time at different process: (a-c) process 1, (d-f) process 2, and (g-k) process 3.
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When particle morphology was examined at the end of 4h of milling it can be seen, cold welding process is more than fracturing process for 1 wt.% methanol (Fig. 3a). In addition to particle morphology has started to convert into a equiaxial morphology. Morphology change for P2 process (2 wt.% methanol) are almost the same as P1 process (1 wt.% methanol). However, flake morphology was reached at the end of 4h of milling for P3 process (3 wt. % methanol) (Fig. 3g). At longer milling time, work hardening of powders causes them brittle and fracturing effectiveness becomes significant and the changing trend of particle morphology is observed.
Fig. 3. Variation of the powder morphology with milling time at different process: (a-c) P1 process , (d-f) P2 process, and (g-k) P3 process. Fig. 4 shows the powder morphologies after 10h of MA. The particle morphologies of P1 and P2 processes have semi equiaxed morphology and similar morphology but the particle size are different because of amount of methanol used in mechanical alloying process. Both cold welding and fracturing process were observed in P3 process.
Fig. 4. Variation of the powder morphology with different processes at 10h milling time: (a) P1 process, (b) P2 process, and (c) P3 process.
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3.3. Effect of the processes with amount of PCA on the apparent density When apparent densities were examined for P1, P2, and P3 processes, it can be seen, apparent density values increased at the beginning of milling process and then decreased but again towards the end of milling process increased. The change in values of apparent density closely related to powder morphology. When powder morphology compared with apparent densities values it can be seen easily, flake morphology increases the value apparent density. Flake morphology provides better packed. To the contrary, reduces the value of the apparent density with increases fracturing process because of deterioration from equiaxed morphology. In addition, it was observed that apparent density decreases with increasing amount of methanol because of increases the ability of powder agglomeration with increasing amount of methanol. The various stages of a ductile-brittle system during mechanical alloying are shown in Fig. 5.
Fig. 5. The various stages of a ductile-brittle system during mechanical alloying [8]. Table 3 and Fig. 6 are shown the effect of the processes with amount of PCA on the apparent density milled Al-Al2O3 powders. Table 3. Effect of PCA content on the apparent density. Milling time (h) 0 1.038 1.038 1.038 0.5 1.055 1.207 1.148 1 0.965 1.216 1.165 2 0.807 0.715 1.128 4 0.995 0.822 0.672 6 1.248 0,911 0.712 8 1.276 1,031 0.795 10 1.278 1.136 0.959
Apparent density (gr/cm3)
Amount of PCA (wt.%) 1 2 3
Fig. 6. Variation of the apparent density as a function of milling time at different processes for amount of PCA.
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3.4. Effect of the processes with amount of PCA on the particle size Table 4. The relationship between particle size and milling time at different processes for amount of PCA. Milling time (h) 0 Particle size (m) P1 P2 P3 127 127 127 0.5 132 121 126 1 130 116 124 2 65 60 133 4 33 38 116 6 103 33 42 8 112 35 45 10 115 28 37
Fig. 6. shows effect of PCA content and milling time on the average the particle size of ball milled powders. Al powders in their initial stage are predominantly irregular and ligamental in shape. During high energy milling, plastic deformation, cold welding and fracture are predominant factors, in which the deformation leads to a change in particle shape, cold welding leads to an increase in particle size and fracture leads to decrease in particle size. Table 4 presents average particle size values after 0h, 0.5h, 1h, 2h, 4h, 6h, 8h, 10h of milling times for all processes. The effect of milling time on the particle size of ductile powders has been studied separately by previous researches in the case of monolithic and composite powders [9,10-12]. In the all cases a similar trend was observed an increase in the particle size followed by a decrease and then steady state in the previous investigations [13-15]. However, the average particle size (d0.5) of the Al alloy-10 wt.% Al2O3 composite powders in this study decreased continously with the increasing milling time (Fig. 6). This can be attributed to the initially used Al alloy powders having ligamental shape. These powders can be easily deformed by high energy collisions of balls and they can be quickly fractured weakness regions. Unlike most of the work related to mechanical alloying [9,16,17], in this study, this particle morphology because of initial powders have ligamental shape. Powders are deformed due to high energy collisions of balls and they are fractured from fine regions. Flatten shape occurs after this fracturing process so particle size decreases unlike increasing at early stage of milling. With increasing milling time, work hardening of powders causes brittle of powders and fracturing process becomes effective process. It was observed that amount of PCA has a significant effect on the particle size of composite powders.
Fig. 6. Effect of milling time on the average particle size of composite powders 3.5. X-ray diffraction analysis of milled composite powders Al alloy powders underwent deformation and cold welding caused by continuous collision and split between balls and powders. As can be seen in Fig. 7, ball milling makes diffraction peaks become wide and the peaks intensities decrease. These observations were found in agreement with the reported for other Al alloy composites [11,14,18,19] (Abdoli et al., 2008; Razavi et al., 2006; Parvin et al., 2008; Abdoli et al., 2009). The concept of X-ray peak broadening related to the crystallite size is widely accepted in the study of mechanically alloyed powder particles. Fig. 7 shows the XRD patterns as a function of milling time. Due to the mechanical deformation introduced into the
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powder, crystallite refinement occurs and the lattice strain increases. The unmilled powder already presented a very refined crystallite since the high cooling rate imposed using the gas atomization method, and the milling process reduced its size. This result show that the mechanical alloying is an effectiveness process to produce nanostructure materials [20]. Fig. 7 shows the XRD patterns of composite powder that were mechanical alloyed with 1 and 3 wt.% methanol (2h and 4h) and initial Al alloy (0h) powders. Ball-impact energy of balls decreases because of increasing amount of PCA so work hardening of particles decreases and there is no significant change in peaks wide and the peaks intensities for P3 process which used 3 wt.% methanol. In other processes (1 wt.% methanol), Peaks wide and peaks intensities as well as particle size significantly changed due to deformation occurred at the end of 4h of milling. Increasing methanol content prevented particle deformation and reduced effectiveness of milling process.
Fig.7. XRD patterns of Al alloy and Al-Al2O3 composite powders for some milling times. 3.6. Microhardness The change of microhardness of milled powders as a function of milling time and PCA content is given in Fig. 8. Generally, increasing milling time increases the deformation and work hardening of powders. As can be seen in Fig. 8, there is a continuous increase in microhardness of all process with increasing milling time and increasing rate of microhardness values decreases with the increasing amount of PCA. As can be seen increasing milling time causes a raise in microhardness of particles. The main factor effecting the microhardness of powders is work hardening of powders. Up to 5h of milling the rate of increasing of microhardness, for P1 process (1 wt.% methanol) is more than P3 process (3 wt.% methanol) but this rate decreases with increaing milling time and microhardness values of P3 proces is more than these P1 process at the end of 10h in process (Fig. 8).
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Fig. 8. The change in microhardness of Al-Al2O3 composite powders with different amount of PCA and milling time. 4.Conclusion The effect of amount of methanol on production of Al-Al2O3 composite powder were investigated. It was observed that amount of PCA has a great effect on the powder characteristics. The increase of the amount of PCA reduced mechanical alloying process effectiveness up to 6h of milling and the steady-state time was delayed. Moreover, The process which used 2 wt.% methanol gave the best results within three process. Consequently, the results indicate that amount of PCA considerable effects on the particle size as well as on the structural behavior of the as milled powders. Acknowledgement The authors are grateful to Karadeniz Technical University Research Fund for the financial supporting of this research work (No: 2007.112.10.2). The researchers would also like to thank to Gundogdu Exotherm Service for providing Al 2024 powders. References 1. Shokrollahi H, Materials and Design 30 (2009) 3374-3387 2. Estrada-Guela I, Carreno-Gallardo C, Mendoza-Ruiz DC, Miki-Yoshida M, Rocha-Rangel E, Martnez-Snchez R, Journal of Alloys and Compounds 483 (2009) 173177 3. Lu L, Zhang YF, Journal of Alloys and Compounds 290 (1990) 279-283 4. Juarez R, Sunol JJ, Berlanga R, Bonastre J, Escoda L, Journal of Alloys and Compounds 434-435 (2007) 472476 5. Pilar M, Sunol JJ, Bonastre J, Escoda L, Journal of Non-Crystalline Solids 353 (2007) 848-850 6. Long BD, Zuhailawati H, Umemoto M, Todaka Y, Othman R, Journal of Alloys and Compounds 503 (2010) 228232 7. Gonalves VS, Rocha CJ, Leal Neto RM, Sixth International Latin-American Conference on Powder Technology, 2010, Rio de Janerio, Brazil 8. Fogagnolo JB, Velasco F, Robert MH, Torralba JM, Materials Science and Engineering A342 (2003) 131/143 9. Razavi Tousi SS, Yazdani Rad R, Salahi RE, Mobasherpour I, Razavi M, Powder Tech 192 (2009) 346351 10. El-Eskandarany MS (2000). Mechanical Alloying for Fabrication of Advanced Engineering Materials. William Andrew Publishing, New York. 11. Abdoli H, Farnoush H, Salahi E, Pourazrang K, Mater. Sci. and Eng. A (2008) 486: 580584. 12. Arik H, Turker M, Mater. and Design. (2007) 28: 140146. 13. Hashim J, Looney L, Hashmi MSJ, J. of Mater. Process. Tech. (1999) 92:1-7. 14. Razavi Hesabi Z, Simchi A, Seyed Reihani SM, Mater. Sci. Eng. A(2006) 428:159-168. 15. Adamiak M, J. Achiev. Mater. Manuf. Eng. (2008) 31(2): 191196. 16. Rodrigues JA, Gallardo JM, Herrera EJ, Journal of Materials Science 32 (1997) 3535-3539 17. Fuentes JJ, Rodriques JA, Herrera EJ, Materials Characterization 61 (2010) 386-395 18. Parvin N, Assadifarda R, Safarzadeha P, Sheibanib S, Marashi P, Mater. Sci. and Eng. A (2008) 492: 134140. 19. Abdoli H, Asgharzadeh H, Salahi E, J. of Alloys and Compounds (2009) 473: 116-122. 20. Fogagnolo JB, Amador D, Ruiz Navas EM, Torralba JM, Materials Science and Engineering A 433 (2006) 45-49
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Effect of The AlxNiy Phases On The Mechanical Properties Of The AlCuSiMg/SiC(Ni)p Composites
Judit PZMN*, Viktor MDAI**, Zoltn GCSI*, Alz MOLNR*, rpd KOVCS*
* University of Miskolc, Institute of Materials Science, 3515 Miskolc-Egyetemvros, Hungary; femjuju@uni-miskolc.hu; femtangz@uni-miskolc.hu; alizmolnar27@gmail.com; femkov@uni-miskolc.hu ** University of Miskolc, Department of Mineralogy and Petrology, 3515 Miskolc-Egyetemvros; askcesar@uni-miskolc.hu
Abstract In our research work AlCuSiMg/SiC(Ni)p composite was produced by powder metallurgy. The reinforcing phase (SiC) was surface coated by electroless nickel plating. The ceramic particles with inert surface had to be activated by acidic pre-treatment or surface oxidation or palladium chloride activation before surface coating. The quality of formed metal layer depends on the pre-treatment methods. The nickel layer of the silicon carbide particles and matrix react together during the sintering, and AlxNiy compound forms on the interface of AlCuSiMg-SiC. This compound effects on the mechanical properties of the composite. In our research work the compressive yield point, compressive strength and micro hardness were determined. The effect of the phase arrangement was studied on the mechanical properties. The microstructure of the samples was examined by SEM, optical microscopy and XRD. Keywords: Surface modification, Silicon carbide particles, Aluminium-nickel compounds, Powder Metallurgical Composite 1.Introduction To improve the interfacial bonding between the matrix and the reinforcing phase, the surface of the reinforcing phase is coated with different metal layers. Mostly the particles are surface treated with copper [1-3] or nickel [4-6]. These metal layers can improve not only the interfacial bonding but the properties of the matrix. These metal layers can be formed by different surface treating methods, for example by galvanization [7], mechanical alloying [8] or electroless plating [9]. The last method can be used simply in a laboratory conditions and it provides equal layer thickness, but the catalytic active surface is need to form the deposit. It is not simple to coat with metal the silicon carbide particles. The surface of the silicon carbide particles must be activated before surface coating. Different pre-treatment methods can be applied as a surface activation (Table 1), for example acidic pre-treatment, surface oxidation or palladium chloride activation [10-11]. Table 1 The main parameters of the pre-treatment methods Type of pre-treatment Acidic pre-treatment Chemical composition Sodium hypophosphite (NaH2PO2H2O) 30 g/l Lactic acid 98% (CH3CH(OH)COOH) 20ml/l In an air atmosphere in a heat-treatment furnace Applied parameters T=358K (85C), 35 min. At 1100C for 3h heat treatment, oxidation Mechanism The development of a thin hypophosphite layer can be expected on the surface. According to the Deal-Grove model, a continuous, compact oxide layer (SiO2) develops on the surface of ceramic particles.
Surface oxidation
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Sensitization
Stannous chloride 15g/l SnCl2 Hydrochloric acid HCl (cc. 37%) 55cm3/l PdCl2 0,5 g/l HCl (cc. 37%) 2ml/l
T= 298K (25C), t=10 min
Sn2+ ions adsorb on the surface of silicon carbide particles. The Sn2+ ions oxidize further into Sn4+ ions on the surface of sensitized particles, and the Pd2+ ions reduce to Pd0. Palladium nuclei form on the surface of SiC particles.
Activation
T=298K (25C), t=25 min
The applying of each pre-treatment method determines the quality of the developing deposit (Fig. 1). Particular surface activation can be realized by the acidic pre-treatment method. Consequently, only one part of the surface of the silicon carbide particles can be covered with metal layer. Mostly, nickel caps form on the edge of the ceramic particles after the electroless nickel plating. Coherent silicon oxide layer develop on the surface of the SiC particles after the surface oxidation. The oxide layer is able to activate the inert surface, so nickel nuclei with homogeneous arrangement form on the surface of the substrate after the electroless nickel plating. Elemental palladium nuclei can be created on the surface of the silicon carbide particles after the two steps activation process. These metal nuclei work as nucleus forming places and they give the possibility to form continuous metal layer.
Figure 1. The SEM photos of the electroless nickel plated SiC particles [9] a) Nickel cap formed on the edge of the SiC particles after the acidic pre-treatment and EN plating b) Nickel nuclei with homogenous arrangement on the SiC particles after the surface oxidation and EN plating (a) c) SiC particles electroless nickel plated (b) using palladium chloride activation (c) AlxNiy phases develop in the Al/SiCp composites using the surface treated reinforcing particles. In our research work the surface treated ceramic particles were used as a reinforcing phase in the powder metallurgical composite. This producing process is three steps. First the mixing of the powder (matrix and reinforcing phase), second the pressing of the power mixture and third is the sintering of the green product. The matrix and the nickel layer of the silicon carbide particles can react with each other due to the acceptable high temperature and long time of the sintering and AlxNiy phases form around the particles. The aim of our research work was to study aluminium-nickel phases and to determine the mechanical properties of Al/SiC(Ni)p composites. 2. Experimental 2.1. Starting materials The silicon carbide powder was chosen as a reinforcing phase. The powder was delivered by Saint Gobain Grains & Powders. Particle size distribution was established by computer image analysis (Fig. 2). Specific surface was determined by BET method. The powder is characterised by relatively low specific surface of SBET,77K=0.14 m2/g which is confirmed by SEM observations (Fig. 3). The X-ray diffraction spectrum (Fig. 4) clearly show that the used SiC powder is not homogenous in terms of phases content and its atomic stoichiometry (Mean atomic stoichiometry is 54,38 atom% C; 45,62 atom% Si). Aluminium based powder mixture signed as Alumix 123 was delivered by ECKA Granules. This powder was applied as a matrix in the production of the composite samples. Except aluminium the powder mixture contains 4.5-wt% Cu, 0.7-wt% Si, 0.5-wt% Mg and 1.5-wt% of Microwax C as a lubricant (Figure 5, a). The composition of the powder makes the sintered products heat-treatable (Figure 5, b).
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Figure 2. Particle size distribution of SiC powder
Figure 3. SEM photomicrograph of SiC particles
Figure 4. XRD spectrum of SiC powder 3. Results
Figure 5. XRD Spectrum of Ecka granulate a) before the sintering b) after the sintering
According to the Al-Ni binary phase diagram (Fig. 6.) different compounds (Al3Ni, Al3Ni2, AlNi and AlNi3) form during the reaction of the nickel layer of the silicon carbide particle and the aluminium alloy matrix. The chemical composition and arrangement of the AlxNiy phases have a connection with the quality of the pre-treatment and the arrangement of the pre-treatment layer. Namely, nickel deposit forms only such part of the particles, where the surface of the particles was activated. So the arrangement of the nickel coating determines the arrangement of the AlxNiy phases formed during the sintering (Fig. 7.). The hypophosphite layer sticking with weak adhesion covers the surface of the silicon carbide particles after the acidic pre-treatment. This pre-treatment layer is not compact. The electroless nickel deposit is situated only on the edge of the SiC particles. AlxNiy phases can form in two places in the electroless nickel plated SiC particles reinforced powder metallurgical composites (using acidic pre-treatment as a surface activation method). One part
Figure 6. Al-Ni binary diagram
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Figure 7. The arrangement of the AlxNiy phases in AlCuSiMg/SiC(Ni)p composites a) using the acidic pre-treatment (AP-MMC) b) using the surface oxidation (SO-MMC) c) using the palladium chloride activation (PCA-MMC) of the electroless nickel deposit is able to separate from the surface of the silicon carbide particles due to the weak adhesion during the mixing and pressing of the powder mixture. These separated coating parts react with the aluminium alloy and AlxNiy phases can be formed far from the SiC particles (Fig. 7. a). The shape of the AlxNiy phases is like a reservoir. Otherwise, the deposit part sticking to the particles react with the matrix, consequently AlxNiy phases develop around the reinforcing particles. At the sintering temperature (5755C) AlNi phase with 50% nickel concentration forms around the silicon carbide particles and AlNi3 with 75% nickel concentration far from the SiC particles [11]. Similar AlxNiy phases can be created by applying of the surface oxidized and electroless nickel plated SiC particles (SO-MMC). But the arrangement of AlxNiy phases in the SO-MMC is different in the acidic pre-treated and EN plated SiC reinforced composite (AP-MMC), because the compact oxide layer is situated on the full surface of the silicon carbide particles. So the activation of the surface is more successful in SO-MMC than the earlier acidic pre-treatment. The nickel nuclei formed on the surface of the SiC particles activated by surface oxidation do not separate, so the above-mentioned nickel reservoirs is not able to develop in the matrix. The AlxNiy phases are situated in an island shape around the ceramic particles (Fig. 7. b). The full nickel quantity can be found near the silicon carbide particles, so the AlNi3 phase with high nickel concentration surrounds the reinforcing particles. As the nickel concentration is different around the particles, so the thickness of the AlxNiy yard too. Mostly, Al3Ni2 phases with 40% nickel concentration can be formed by the reaction of the matrix and nickel layer of the silicon carbide particles [11]. The successful surface activation provides compact deposit in the case of the palladium chloride activation. When the silicon carbide particles EN plated after palladium chloride activation is used as a reinforcing phase in the production of the composites, the nickel concentration is equal around each particle. The nickel layer of the SiC particle reacts with the aluminium alloy matrix and AlNi3 and AlNi phases surround the ceramic particles (Fig. 7.c). 3.1 Mechanical properties of the AlxNiy phases Micro hardness (HV0.2) was measured on the AP-MMC composite samples (using the acidic pre-treatment for the surface activation). The micro hardness (HV0.2) of the above-mentioned aluminium-nickel reservoirs was determined. The results centre round two data, exactly 140 HV0.2 and 220 HV0.2. These hardness results advert to the AlxNiy phases with different nickel concentration. The X-ray diffraction phase detection demonstrates the different hardness data (Fig. 9.). The Al3Ni2 phase has less nickel concentration and lower hardness than AlNi and AlNi3 phases. If the hardness of the aluminium alloy is collated with the AlxNiy phases (Fig. 8), it can be seen that the compounds phase is very rigid. The AlxNiy phases show double higher hardness (152 HV0.2) than the matrix (82 HV0.2). The Standard Deviation (51 HV0.2) is three times higher than the matrix (17 HV0.2). 3.2 Compressive test of the AlCuSiMg/SiC(Ni)p composites The surface modified silicon carbide particles reFigure 8. Hardness of the matrix and AlxNiy phases inforced composite samples were studied by compressive test. The aim of the examination was to determine the effect of the rigid AlxNiy phases on the compressive properties of the composite. The composite samples
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Figure 9. X-ray diffraction spectrum of the AlCuSiMg/SiC(Ni)p composite (using palladium chloride activation) a) XRD specrtum of the composite b) XRD spectrum of the matrix powder mixture were pressed by quenched steel plates with 5 tonnes load. The results of the compressive test (Fig. 10.) show that the compressive properties of the composite are similar to the matrix, when the silicon carbide particles were pretreated by acidic pre-treatment (AP-MMC) or without the surface modification (10SiC-MMC). The SO-MMC and PCA-MMC samples have lower compressive properties than the AP-MMC samples. According to the results it can be said that the AlxNiy phases have the effect on the compressive properties in small extent. 4. Conclusion The electroless nickel plated SiC reinforced aluminium alloy matrix composite was produced by powder metallurgy. The electroless nickel layer of the particles and the matrix react with each other during the sintering, and AlxNiy phases form in the interface of the reinforcing phase and the matrix. The effect of the AlxNiy phases was determined on the compressive properties by compressive test. The results showed that the formed compounds phases have effect on the compressive strength in a small extent. 5. ACKNOwledgement This research was carried out as part of the TAMOP4.2.1.B-10/2/KONV-2010-0001 project with support by the European Union, co-financed by the European Social Fund.
Figure 10. Results of the compressive test in the case of AlCuSiMg/SiC(Ni) p composite
6. References [1] Sone, M., Kobayakawa, K., Saitou, M., & Sato, Y. (2004). Electroless copper plating using FeII as a reducing agent. Electrochimica Acta 49 , 233-238. [2] Tian, Q.-h., & Guo, X.-y. (2010). Electroless copper plating on microcellar poliurethane foam. Trans. Nonferrous Met. Soc. China 20 , 283-287. [3] Zhao, H., Huang, Z., & Cui, J. (2008). Electroless plating of copper on AZ31 magnesium alloy substrates. Microelectronic Engineering 85 , 253-258. [4] Kretz, F. a. (2004). The electroless deposition of nickel on SiC particles for aluminum matrix composites. Surface and CoatingsTechnology 180-181 , p575-579. [5] Li, L., & An, M. (2008). Electroless nickelphosphorus plating on SiCp/Al composite from acid bath with nickel activation. Journal of Alloys and Compounds , 8591. [6] Li, L., An, M., & Wu, G. (2006). A new electroless nickel deposition technique to metallise SiCp/Al composites. Surface & Coatings Technology , 5102 5112. [7] Socha, R., Nowak, P., Laajalehto, K., & Vyrynen, J. (2004 ). Particle-electrode surface interaction during nickel electrodeposition from suspensions containing SiC and SiO2 particles. Colloids and Surfaces A: Physicochem. Eng. Aspects , 45-55. [8] Arik, H. (2008). Effect of mechanical alloying process on mechanical properties of a-Si3N4 reinforced aluminum-based composite materials. Materials and Design 29 , 18561861. [8] Pzmn, J., Ferenczi, T., Trk, T., & Gcsi, Z. (2008). Metal Matrix Composite with Electroless Nickel Plated SiC. Euro PM2008 International Powder Metallurgy Congress & Exhibition, Conference Proceedings , 179184. [9] Pzmn, J., Ferenczi, T., Gcsi, Z., & Trk, T. (2008. oktber 8-12.). Improving the Interfacial Metal-Ceramics Bond of Metal Matrix Composites with Electroless Nickel Plating. Gcsi Zoltn, Ankara, 5th International Powder Metallurgy Conference , Trkorszg. [10] Pzmn, J., Mdai, V., Tth, J., & Gcsi, Z. (2009). Electroless Nickel Plating with Different Pre-treatments on Silicon Carbide Particles. Euro PM2009 International Powder Metallurgy Congress & Exhibition; Proceedings , 377-382. [11] Pzmn, J., Mdai, V., Tth, J., & Gcsi, Z. (2010). Effect of the interfacial phases on the mechanical properties of Al/SiC(Ni)p composites. World PM 2010 (Proceedings Volume 4, 87-94;). Florence, Italy: EPMA.
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PRODUCING OF STEEL CHIPS REINFORCED ALUMINUM COMPOSITES WITH POWDER METALLURGY

Rashad GULUZADE*, Ahmet AVCI** and M. Turan DEMRC*** *Selcuk University, Faculty of Engineering, Department of Mechanical Engineering, 42075, Konya, Turkey, rguluzade@hotmail.com ** Selcuk University, Faculty of Engineering, Department of Mechanical Engineering, 42075, Konya, Turkey, aavci@selcuk.edu.tr *** Selcuk University, Faculty of Technology, Department of Metallurgical and Materials Engineering, 42075, Konya, Turkey, turandemirci@selcuk.edu.tr ABSTRACT In this paper, recycling aluminum (Etial 65) and AISI 1040 steel chip composition were produced with powder method. Aluminum and steel chip size were determined as 1000 m. Steel chips were used as reinforcement into aluminum chip matrix. AISI 1040 reinforcement were added into 20, 30, 40% wt. ratios. The process was performed in following steps; granulation of chips (1000um screening apparatus used ), using zinc stearate as lubricating for press molding (under 200MPa pressure), sintering process at 650oC which contain new method for preventing oxidation without vacuum and shielding gas. Compression test, hardness measurement were applied to ascertain mechanical properties of composites. Compressive strength and hardness of the specimen with 40% of steel reinforcement is highest in 650oC sintering temperatures. Keywords: Recycling method, aluminum and steel chips, new sintering method 1. INTRODUCTION Manufacturing sintered products technology by powder metallurgy method has been developed gradually in recent years. Especially, when the recycling technologies for manufacturing have been progressed account of low material sources, the using of waste products in metal industries come into prominences [1-3]. In metal industries, waste and scrap metals that were manufactured end of metal products processes are chips and discards. These waste materials are reutilized by returning to smelters. However, during melting processes of materials for recycling, many metals are lost due to occurring oxidation and costs of labor, energy and environmental protection expenditures [4]. To overcome these disadvantages were mentioned on melting processes, there are different ways of recycling metal chips, consisting in the direct conversion of chips into compact metal. One of them contains granulation which gets from end of cutting process, then cold pressing and sintering processes. This type of recycling can be applied to iron, copper, aluminum, to some extent to cast metals and their alloys [5]. In aluminum and aluminum-alloys melting process for recycling aluminum waste and scrap, approximately 10% of it is burst and approximately 10% of it is lost on account of aluminum waste and scraps with the slag removed from surface of the ladle [4-6]. The reason of substantial losses of aluminum and aluminum alloys waste and scraps during conventional due to which it stays rather long on the surface of the molten aluminum and oxidizes intensively [1]. Therefore, powder methodology contains cold pressing and sintering process can be used to overcome all disadvantages of recycling of aluminum waste like chips were mentioned above. Aluminum chips especially were derived machining operation. For cold pressing and sintering chips size and irregular elongated spiral shapes make them unsuitable for is important to define the cold pressing conditions. For obtaining optimum size and shape of the chips, they must be broken into to small pieces by milling processes. Gronostajski et al. investigated new methods for the aluminum and aluminum alloy chips recycling and compared conventional and direct methods [1]. Chmura at al. studied the recycling of aluminum and aluminum-bronze chips
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as the use of bearing. Bearing composites were produced by the cold compaction and hot extrusion. End of production processes of composite bearing samples, mechanical and tribological properties were determined and found aluminum-based with aluminum bronze reinforcing phase have good frictional properties.[4-7]. Gronostajski et al. in other study, used direct the recycling method which contains cold press molding and hot extrusion. As aluminum alloys, they used Cu, Mg and W materials. As result of experiments, they determined that aluminum and its alloys can be recycled by direct conversion method which characterized by low energy-consumption and large material savings [2-3]. Gronostajski et al. investigated aluminum chips composites and used as a reinforcing phase the FeCr powder. The reinforcement of FeCr showed very good mechanical properties at room and elevated temperatures [5]. Gronostajki at al. in other study, they produced Al and ALMg2 alloy composites by using direct recycling method from chips [3]. Abdizadeh et al. studied on aluminum-zircon composites by powder metallurgy method. The cold pressed composites were sintered two different temperatures at 600 and 650oC. Then produced composites were carried out compressive and hardness tests. The best bonding temperature was obtained at 650oC [8]. They reached that adding zircon particulates increased mechanical properties of composites. Zhao et al. produced AlNi composites by powder metallurgy and examined their mechanical properties such as microhardness, ultimate tensile strength and elongation [9]. McKie et al. tried to find out mechanical properties of cubic boron nitride and aluminum composites which were produced by powder methodology. In this methodology, they applied to high pressure and high temperature sintering methods. End of experiments, they reached the important issues that the grain sizes effected the bonding of materials [10]. Showaiter and Youseffi examined the mechanical properties of 6061 Al and Pb, Ag and Sn added 6061 Al composites. They determined optimum sintering condition that was temperature of at 620oC and 1 h under pure nitrogen for compaction pressures of 340 and 510 MPa [11]. So far many researchers concentrated on studying powder materials such as Al, Cu etc and conventional sintering conditions. However, waste materials in order to use recycling methodology have received little attention. The aim of this work was to investigate the compaction, new sintering method and mechanical properties of composites produced by aluminum chips and reinforcement materials of steel chips attained from manufacturing processes. 2. EXPERIMENTAL PROCEDURE 2.1. Raw Materials Etial 65 Aluminum chips were used as matrix and AISI 1040 steel chips were used as reinforcing phase. Chemical properties of these chips were given in Table 1. At the beginning of study, size reduction processes by using a cutting device and sieve shaker were applied to aluminum and steel chips that are waste materials. Then sizes of chips were made smaller granular between 0.5 and 1 mm. Methyl alcohol was used to clean the chips from impurities and cutting oils used as lubricants and coolant. Aluminum chips mixed with 30, 40, 50 wt% ratios of reinforcing phase by mechanical stirrer for 15 min each (Table 2). Table 1. Chemical composition of Etial 65 aluminum and AISI 1040 steel chips Si (%) Fe(%) Cu(%) Mn(%) Mg(%) Al (%) C(%) 0.67 0.74 0.123 0.138 1.26 96.7 0.2 0.65 0.4 P(%) S(%) 0.04 0.2
Etial 65 AISI 1040
Table 2. Chips fraction used for this experiment. AISI 1040 (wt) 21 28 35 2.2 Compaction and sintering All mixture ratios given in Table 2 were pressed at 250 MPa by using cold press die which produced in accordance with ASTM-B557. Zinc stearate was used on the die wall and punches for lubrication before compaction to reduce die wall frictional effects. A single acting hydraulic press was used for compaction. Sintering characteristics were investigated in a laboratory furnace in 650oC and for 2 hours [8]. All composites were heated to sintering tempera% 30 40 50 Aluminum(wt) 49 42 35 % 70 60 50
Figure 1. Compaction die for producing compressive specimens.
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tures at the heating rate of 5oC/min and furnace cooled to room temperature. Instead of pure nitrogen atmosphere, sintering mold, molding sand and clay were used to prevent the oxidation of aluminum chips. In this new sintering method, cold pressed composites put in sintering mold firstly. Secondly molding sand filled in mold and clay were used to closed mold mouth finally. Molding sand provided to homogeneously heat to composites and prevented oxidations. Funnel seen in fig. 2 deposited the gases were released from composites.
Figure 2. Sintering mold for compressive specimens. Brinell hardness values of compressive specimens were measured on the polished surfaces of specimens using a ball 5 mm diameter under a load of 250 kgf by holding 30 second [2-7]. For each specimens three hardness tests on randomly selected regions were performed in order to eliminate the possible segregation effects and get a representative value of the matrix material hardness. The compressive strength test was conducted in air at room temperature according to ASTM-B557 and three specimens were tested each steel contents. 3. RESULTS Increasing the weight of 1040 steel chips causes an increase in the density of specimens. The differences of theoretical and sintered density of composites are very obvious, give in fig. 3. High sintering temperature provides to the easier diffusion of atoms which helps the better ability of sintering the composites. Therefore the density of composites reaches to a higher value [3-8].
Figure 3. Sintered density of composites. The hardness of specimens has been tested with Brinell measure method. The results were presented at fig 4. The hardness specimens increase by rising steel contents [8].
Figure 4. Hardness vs. steel contents.
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Figure 5. Compressive strength of composites. Compressive test were applied to three different composites and pure aluminum specimens and obtained measurement results give in fig. 6. According to tests results, the increasing of steel contents were enhanced the strength of composites. As it could be seen in the fig.6, compressive strength of the specimen with 40% of steel reinforcement is highest in 650oC sintering temperatures. This situation could be associated to the highest density of this specimen among the others. When reinforcement steel chips increases in composites, the distance between them decreases. Therefore movement of dislocations is harder because of providing more barriers and then, dislocations pile up occurs. These phenomena bring to an end of decreasing in elongation [4]. Fig 6. shows the elongation of composites.
Figure 6 Elongation of composites. While the steel contents are increased, the composites become denser (fig. 4.) as well as inflexible so that the elongations of composites are lower values [12]. 4. CONCLUSIONS In this study, compressive tests, density calculation and hardness test were performed according to ASTM. Conclusions from present study are given below; With increasing steel chips contents in composites, the hardness of specimens increases to a maximum value of 121 BHN. 650oC sintering temperatures provide to increase the sintered density. High temperatures under melting point for aluminum causes decrease in porosities of specimens and high temperatures cause better bonding between aluminum and steel chips, thus this improves the mechanical properties of composites. Compressive strength enhances with increasing steel chips wt % contents. The maximum of compressive strength is approximately 640 MPa which contains 40 wt% steel chips. In addition to all explanations, As know that the steel reinforcement is increase the compressive strength but to improve mechanical properties and decrease the porosity of composites, the cold pressing pressure can be increased and the different sintering temperatures can be carried out to investigate the effects of sintering temperatures to density, porosity and mechanical behavior. 5. ACKNOWLEDGEMENT The authors would like to thank The Onallar Agricultural Machine Company for technical supports.
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REFERENCES 1. Gronostajski J., Marciniak H., Matuszak A., New methods of aluminum-alloy chips recycling, Journal of Material Processing Technology, Vol:106, pp. 34-39, 2000. 2. Gronostajski J., Matuszak A., The recycling of metals by plastic deformation: an example of recycling of aluminum and its alloys chips, Journal of Materials Processing Technology, Vol: 92, pp. 35-41, 1999. 3. Gronostajski J, Z., Kaczmar J. W., Marciniak H., Matuszak A., Production of composites from Al and AlMg2 alloy chips, Journal of Materials Processing Technology, Vol: 77, pp. 37-41. 1998. 4. Gronostajski J., Chmura W., Gronostajski Z., Bearing materials obtained by recycling of aluminum and aluminum bronze chips, Journal of Materials Processing Technology, Vol: 125, pp. 483-490, 2002. 5. Gronostajski J.Z., Marciniak H., Matuszak A., Samuel M., Aluminium-ferro chromium produced by recycling of chips, Journal of Material Processing Technology, Vol: 119, pp. 251-256, 2001. 6. Gronostajski J., Kaczmar J. W., Marciniak H., Matuszak A., Direct recycling of aluminum chips into extruded products, Journal of Materials Processing Technology, Vol: 64, pp. 149-156, 1997. 7. Chmura W., Gronostajski Z., Bearing composites made from aluminum and aluminum bronze chips, Journal of Material Processing Technoloogy, Vol: 178, pp.188-193, 2006. 8. Abdizadeh H., Ashuri M., Moghadam P. T., Nouribahadory A., Baharvandi H. R., Improvement in physical and mechanical properties of aluminum/zircon composites fabricated by powder metallurgy method, Materials and Design, Vol: 32, pp. 4417-4423, 2007. 9. Zhao B., Zhu C., Ma X., Zhao W., Tang H., Cai S., Qiao Z., High strength Ni based composite reinforced by solid solution W(Al) obtained by powder metallurgy, Material Science and Engineering A, Vol: 456, pp. 337-343, 2007. 10. McKie A, Winzer J., Sigalas l., Hermann M., Weiler L., Rdel J., Can N., Mechanical properties of cBN-Al composite materials, Ceramic International, Vol: 37, pp. 1-8, 2011. 11. Showaiter N., Youseffi M., Compaction, sintering and mechanical properties of elemental 6061 Al powder with and without sintering aids, Material and Design, Vol: 29, 752-762, 2008. 12. Baron R. P., Wert J., Gerard A., Wawner F. E., The prosessing and characterization of sintered metal-reinforced aluminum matrix composites, Journal of Materials Science, Vol: 32, pp. 6435-6445, 1997.
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INVESTIGATING THE MICROSTRUCTURE OF HOT PRESSED SiC REINFORCED AlCu and AlSi ALLOY COMPOSITES BY ULTRASONIC TECHNIQUE
Evren TAN*, C. Hakan GR*, Andrea SIMON** and Zoltan GACSI** * Middle East Technical University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 06800, Ankara, Turkey etan@metu.edu.tr, chgur@metu.edu.tr ** Institute of Materials Sciences, Univ. of Miskolc, Miskolc-Egyetemvaros, Hungary femandi@uni-miskolc.hu, femtangz@uni-miskolc.hu ABSTRACT Al matrix composites are utilized in high-tech structural and functional applications including aerospace, defence, automotive industries. Among them particle reinforced ones are widely utilized since they show isotropic behaviour, and can be formed using the traditional metal working practices. Several challenges must be overcome in order to intensify their utilization such as parameters affecting the microstructural integrity including agglomerates need to be understood more thoroughly, and there is a need for developing simple, economical and portable non-destructive systems to control the product quality. This study aims to understand the microstructure-ultrasonic velocity relationship in SiCp reinforced Al-alloy matrix composites. Two specimen sets were fabricated by hot pressing of AlCu and AlSi powder mixtures containing various amounts of SiC particles. The microstructures of the specimens were characterized by microscopy, X-ray diffraction, hardness, and sound velocity measurements; and the results were correlated. Keywords: Aluminum alloy matrix composites, SiC reinforcement, Microstructure, Characterization, Ultrasonics 1. INTRODUCTION Metal matrix composites (MMCs) show an ability to blend high strength and high modulus with ductility and toughness, which leads to significant improvement in the performance of the composites over those of the metallic alloys. Due to relatively inexpensive reinforcements and the processes resulting in reproducible microstructures and properties, MMCs are being increasingly sought for a wide range of applications in the electronics, automotive and aerospace industries. Particle reinforced MMCs have been synthesized using a number of different techniques that include solid phase processes, liquid phase processes and two phase (solidliquid) processes [1]. In the case of powder metallurgy method, powdered metal is blended with reinforcement particles, and then, densified by die pressing, canning, and extrusion or canning and hipping. The rate of increase in strength with volume fraction decreases beyond approximately 3040 vol.% SiC. However, ductility, fracture toughness, formability, and machinability tend to decrease in value with increasing levels of reinforcement [2]. Strength clearly increases with reducing the particle size of the reinforcement. By reducing the reinforcement size, the ability to perform a secondary deformation and machinability was also enhanced. Reinforcement distribution is thought to be the major parameter influencing ductility and fracture toughness of the MMC, and hence indirectly strength. Mechanical properties and stressstrain behavior for several commercial Al-matrix composites, containing up to 40 vol.% discontinuous SiC whisker, nodule or particulate reinforcement were evaluated [3]. The particle size of SiC and Al material has an important role. If the particle size ratio is high, the particle size of them is very different and the smaller SiC particles can cluster among the bigger Al particles [4]. If the reinforcement distribution is not
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homogeneous, then clusters develop and pores appear among them. These clusters usually function as initial place for cracks. In the composites made via powder metallurgy route the reinforcement distribution homogeneity can be affected by the particle size ratio. To improve the homogeneity reinforcements with bigger particle size can be used. However, this leads to worse mechanical properties [5]. Propagation of ultrasonic waves is sensitive to the variations in the microstructure and mechanical properties. Therefore, establishment of the correlations between microstructure and nondestructive evaluations could be useful for process improvement and product quality control. It has been reported that the inhomogeneous distribution of SiC whiskers in 7090 Al, that significantly degrades tensile and fracture toughness, is detectable by ultrasonic measurement [6]. A theoretical model for the relationship between ultrasonic velocity and the microstructure has been established [7]. Multiple non-destructive techniques for determining the volume fractions of reinforcement in SiCp-reinforced 7091 Al-alloy matrix composites have been used [8]. Correlation of the ultrasonic velocity and specific surface area that occur as a result of sintering for several oxide powder systems has been studied [9]. It has been reported that the ultrasonic velocity increases with an increase in SiC content; however, it decreases owing to microporosity caused by the segregation of SiC particles [10]. MMCs provide a challenge for conventional non-destructive evaluation methods because of their complex microstructural characteristics. The primary objective of this research is to use a systematic approach directed towards microstructure characterization of various SiCp-reinforced Al matrix composites. 2. EXPERIMENTAL PROCEDURE The compositions of powders used were given in Table 1. A hot press system composed of furnace, control unit and a hydraulic press was used. Molykote P37 grease was applied on the die surfaces before placing the powder samples for easy removal of the product. Table 1. Chemical composition of the powders Matrix AlCu ECKA Alumix 123 AlSi ECKA Alumix 231 Element, wt% Cu 4.5 2.5 Si 0.7 14 Mg 0.5 0.5 Zn Lubricant 1.5 1.5 Al Bal. Bal. Mean size m 24 17
Reinforcement SiC
C 0.08
SiO2 0.15
Si 0.04
Fe2O3 0.015
Al2O3 0.004
CaO 0.003
SiC Bal. 14
Production sequence starts with powder mixing at 70 rpm in a 100 ml container with ZrO2 cylpeb balls for 1 h. The mixed powders were poured in the die cavity which was previously placed in the furnace. While the system was being heated, a pressure was applied on the die punch. Furnace and control unit was designed in such a manner that; the process temperature could be reached in 2 hours, and stay at that temperature within 5C variation. After 10 minutes under 25 MPa pressing pressure at 527oC for AlCu; 525oC for AlSi composites, the furnace was turned off and the die was removed. Sample densities were measured via Archimedes principle. To find the overall porosity; theoretical densities of the composites were calculated from rule of mixtures. Vickers HV30 indentation was performed on the sample surfaces, and average hardness values were calculated. X-Ray measurements were carried out to identify the intermetallic phases. Sound velocities were measured by establishing wave transmission through the thickness of samples produced. 0.5 MHz, 1 MHz, 2.25 MHz and 5 MHz longitudinal and transverse wave probes were used. 3. RESULTS Figure 1 shows the representative micrographs of the unreinforced and 30% SiC reinforced AlCu and AlSi alloy samples. Phases found in the X-ray diffraction analysis were Al2Cu in the AlCu composites, Al2Cu and Mg2Si in the AlSi composites. In none of the samples brittle Al4C3 was not detected.
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Figure 1. Selected SEM microstructures of the hot-pressed samples The porosities were detected between SiC particles/clusters (irregular shape); at the Al-SiC interface (elongated shape); and in the matrix (sphere-like/elongated shape). In AlCu samples no significant differences among the porosities were observed in the specimens containing 10 and 20% SiC. However, porosity content increased clearly in the sample with 30% SiC although it did not reach the quantity detectable in the matrix. The distribution of SiC seems to be the most uniform in the specimen containing 10% SiC; the SiC particles group in a greater extent at the Al-boundaries in the other two specimen. The pores are distributed randomly there is not any typical appearance. In the AlSi alloy specimens containing 10 and 20% SiC, porosity can be neglected. The extent of porosity increases significantly in the specimen containing 30% SiC. While the presence of porosity can mainly be due to the eutectic in the first two composites, it appears in the vicinity of SiC groups in the specimen containing a high quantity of SiC (it can be caused by the preparing of powders i.e. their improper mixing). Figure 2 shows that the hardness of the composite increases with increasing % SiC. Reinforcement is more effective for strengthening of AlSi composites than AlCu ones.
Figure 2. Macrohardness (HV30) of the samples
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Reinforcement content is an important factor controlling the strength of AlSiC composites. It is known that for a given matrix alloy and reinforcement, the yield and ultimate tensile strengths generally increase with increasing reinforcement content, and a similar increase is expected for the stiffness of the composite [2,3]. Sound velocity measurement results are tabulated in Table 3. Figure 3 shows the variation of longitudinal and transversal wave velocities with respect to the amount of SiC. The velocity of ultrasonic wave propagating in an inhomogeneous medium depends upon the overall effective stiffness and density of the medium. The SiC is much stiffer than the Al matrix while its density is comparable to that of the matrix. When SiC content increases, the stiffness and the elastic modulus increases. Thus, ultrasonic waves propagate faster in the SiC reinforced Al MMCs than in those without reinforcement, and the propagation rate of the wave increases with increasing amount of SiC reinforcement. Table 3. Velocities of longitudinal and transversal waves SiC theoretical measured VL (m/sec) VT (m/sec) (wt.%) 0 2,56 3819 2660 2,78 10 2,65 5147 2986 2,81 20 2,80 6788 3566 2,85 7246 3719 30 2,85 2,89 0 10 20 30 2,68 2,72 2,77 2,82 2,39 2,40 2,60 2,77 3268 3770 6443 7385 2185 2858 3605 4086
Set
AlCu
AlSi
Figure 3. Changes in the velocities of longitudinal and transverse waves with %SiC
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It has been observed that the velocity of longitudinal waves increases with increasing amount of SiCp with a corresponding increase in the density. Due to the inverse relation between velocity and density, the increase in the velocity of the longitudinal wave must be related to increasing elastic moduli rather than increasing density. However, the amount of the increase in both velocity and density is less than the theoretical values. It appears that the ultrasonic velocities, that are lower than the theoretical values, are probably due to the higher amount of residual pores. Microporosities in the specimens may affect the ultrasonic velocity. A relationship has been reported in the literature where the ultrasonic velocity varies as a function of pore volume fraction [11,12]. V L / V L,0 = 1 P where VL and VL,0 are the longitudinal ultrasonic velocity in porous and non-porous material, P is the pore volume fraction and is constant.
Figure 4. Changes in the longitudinal velocity with pore volume fraction (P) Figure 4 shows the variation of longitudinal wave velocities with respect to pore volume fraction. It was observed that for AlCu composites, effect of porosity on longitudinal ultrasonic sound velocity could be easily fit to the linear function with being 6.33. But for the AlSi composite case, a deviation from the linear function was found which shows that variation in the retained porosities was not enough to explain the change in ultrasonic sound velocity change. It was thought that for AlSi composites the density difference (16%) between reinforcement (3.21 g/cm3) and matrix (2.68 g/cm3) could be the another parameter that should be taken into account. 4. CONCLUSIONS This study aimed to understand the microstructure-ultrasonic velocity relationship in SiCp reinforced Al-alloy matrix composites. Two specimen sets were fabricated by hot pressing of AlCu and AlSi powder mixtures containing various amounts of SiC particles. The following conclusions can be drawn from the results of this study: Hardness increases with increasing SiC content. For a given particle size combination, the velocity of ultrasonic longitudinal waves increases with increasing reinforcement content. The propagation rate of the ultrasonic waves is affected by porosity in the matrix. Ultrasonic velocity measurement seems to be a promising technique for quality and process control purposes in the fabrication of SiCp-reinforced Al-alloy MMCs. Acknowledgements Financial support of Turkish-Hungarian project (TBTAK 106M328) is greatly acknowledged. Authors take this opportunity of thanking ECKA and Norton AS for providing Al and SiC powders. REFERENCES 1. Lloyd, D.J., Particle Reinforced Aluminum and Magnesium Matrix Composites, International Materials Review, Vol. 39, pp. 1-22, 1994. 2. Begg, A.R., Metal matrix composites by powder metallurgy, Powder Metallurgy, Vol. 36, pp.107-110, 1991.
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3. McDanels, D.L., Analysis of stress-strain, fracture and ductility behaviour of aluminium matrix composites containing discontinuous silicon carbide reinforcement, Metallurgical Transactions A, Vol. 16, pp. 11051115, 1985. 4. Bhanu Prasad, V.V., B. Bhat, V. R., Ramakrishnan, P., Mahajan Y.R., Clustering probability maps for private metal matrix composites, Scripta Materialia, Vol. 43, pp. 835-840, 2000. 5. Slipenyuk, A., Kuprin, V., Milman, Yu., Spowart, J.E., Miracle, D.B., The effect of matrix to reinforcement particle size ratio (PSR) on the microstructure and mechanical properties of a P/M processed AlCuMn/SiCp MMC, Material Science and Engineering A, Vol. 381, pp. 165-170, 2004. 6. Mott, G., Liaw, P.K., Correlation of Mechanical and Ultrasonic Properties of Al-SiC Metal Matrix Composite, Metallurgical Transactions A, Vol. 19, pp. 2233-2246, 1988. 7. Lu, Y., Liaw, P.K., Effects of Particle Orientation in SiC Particulate Reinforced Aluminium Matrix Composite Extrusions on Ultrasonic Velocity Measurement, Journal of Composite Materials, Vol. 29, pp.1096-1115, 1995. 8. Jeong, H., Multiple NDE Techniques for the Measurement of Constituent Volume Fractions in Metal Matrix Composites, Research in Non-Destructive Evaluation, Vol. 9, pp. 41-57, 1998. 9. Martin, L.P., Nagle, D., Rosen, M., Effect of Particle Size Distribution upon Specific Surface Area and Ultrasonic Velocity in Sintered Ceramic Powders, Material Science and Engineering A Vol. 246, pp. 151-160, 1998. 10. Gr, C.H., Investigation of MicrostructureUltrasonic Velocity Relationship in SiCp-reinforced Aluminium Metal Matrix Composites, Material Science and Engineering A, Vol. 361, pp. 29-35, 2003. 11. Mukhopadhyay A.K., Phani, K.K., An analysis of Microstructural Parameters in the Minimum Contact Area Model for Ultrasonic Velocity - Porosity Relation, Journal of European Ceramic Society, Vol. 20, pp. 29-38, 2000. 12. Kumar N., Panakkal, J.P., Analysis of Ultrasonic Velocity-Porosity Data in Polycrystalline Materials using Rotation-Iteration Technique, Journal of Materials Science, Vol. 34, pp. 4811-4814, 1999.
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THE EFFECT OF PROCESS PARAMETERS ON MECHANICAL AND DRY WEAR BEHAVIOUR OF ALUMINIUM COMPOSITE
Yusuf AHN*, Kerim Emre KSZ** * Gazi University, Faculty of Technology, Department of Manufacturing Engineering, Beevler-06500, Ankara, Turkey, ysahin@gazi.edu.tr ** Cumhuriyet University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 58140, Sivas, Turkey, emre.oksuz@cumhuriyet.edu.tr ABSTRACT Al2O3 particle-reinforced Aluminium composites were prepared by powder metallurgy (PM) method under different temperatures and times. Wear behaviour of Al-Al2O3 reinforced composites were tested under dry conditions using a pin-on-disc wear rig. Pure Al of average particle size of 45 m was reinforced with 10wt. %Al2O3 with average particle sizes of 20 and 3 m. SEM examination showed a nearly uniform distribution of the Al2O3 particles within the matrix. Improvements of hardness in comparison to matrix for 550C, 610C were achieved at about 44.52%, 50%, respectively. These improvements were reached up to 62.6% at 120 min sintering time. Moreover, the wear rate of the composites increased with increasing all applied loads, but wear rate decreased with increasing particle size. Keywords: Al matrix Al2O3 particle, metal matrix composite, powder metallurgy, wear 1. INTRODUCTION Metal matrix composites (MMCs) are relatively new class of advanced engineering materials characterized by higher stiffness and hardness, lighter weight and greater wear resistance than those of conventional materials [1]. The reinforcing particles in the MMCs protect the matrix surface against destructive action of abrasive wear. In producing MMCs; thus, C, SiC, TiC, B and Al2O3 in the form of continuous fibres, chopped fibres or whiskers and particulates have been used as reinforcement materials, whereas, aluminium, magnesium, titanium and their alloys have been used as matrix alloys [2]. The most commonly employed MMCs consists of aluminium alloy reinforced with hard ceramic particles, as stated above. The MMCs can be produced through a number of routes including casting and powder metallurgy (PM) including mechanical alloying (MA) [3-9, 10-13]. Some of the difficulties of producing the MMCs using conventional casting method is to obtain non-uniform microstructures and particle clustering [14, 15]. The PM routes like densification of mixtures of metal and ceramic powders or of composite powders made by mechanical processing, followed by pressure and sintering. The PM is simple method and exhibit excellent finished performance [16, 17]. MMCs, therefore, have been used for the automobile components such as engine piston, brake drums, cylinder blocks, drive shaft, but they are also used in structural applications such as helicopter parts, rotor vanes in compressors in aerospace industry [4, 18, and 19]. There have been a number of studies on the fabrication of Al matrix composites. However, there are a few reports on wear behaviour of Al2O3/Al composites with the effect of particle sizes at lower stress [2, 6, 15-16]. The purpose of the current study, therefore, is to produce MMCs with different particle sizes by PM method, evaluate the effect of particle sizes and load on the dry wear behaviour of MMCs. 2. EXPERIMENTAL PROCEDURE 2.1. Materials Pure aluminium (Al) was fabricated by powder metallurgy as an unreinforced material. In order to produce Al2O3Al based composites, commercial aluminium powders with an average particle size of 45 m with 99.5% purity and various particle sizes of Al2O3 powders have been provided from Akyol Turkish Company in Istanbul. For manufacturing MMCs, the average particle sizes of 22 m, 3 m was evaluated, hereafter denoted as 22 m- Al2O3/
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Al composite, 3 m-Al2O3/Al composite containing 10 weight fractions of Al2O3 particles. The mixtures of alloyed powders were uniaxially cold compacted using a cylindrical die of 6.5 mm diameter and 20 mm height at a pressure of 650 MPa. The compacts were then sintered in a pipe type of furnace under a control of argon gas. The mixed powders were sintered at 550C, 610C for 45 min and 120 min. A similar subsequent experiment was conducted for the development of Al powder specimens-only for comparison purposes. Hardnesss of composites and matrix were measured by Vickers hardness method by applying 30kgf load after polishing to a 3 m finish. Five samples were averaged at least. A pin-on-disc type of apparatus was employed to evaluate the wear characteristics of MMCs and matrix. The counter surface material,which was heat-treated to give a surface hardness of 59-63 HRC. The composite bars were in the form of cylindrical shapes. The pin was then mounted in a steel holder in the wear machine so that it was held firmly perpendicular to that of flat surface of the rotating counter disc when tested. The samples were loaded against the hardened steel disc with the help of a cantilever mechanism. In the tests; normal load on the pin was variable at a constant sliding speed of 1 m s-1. 3. RESULTS AND DISCUSSION 3.1 Microstructure Fig.1 shows the SEM micrographs of pure Al matrix and its composites reinforced with a 10 wt. % of Al2O3 composites with various particle sizes. Grain boundary can be seen in the pure Al matrix (Fig.1a). The darker region in the microstructure is essentially Al2O3 particles. The distributions of Al2O3 particles in these composites seem to be uniform. With the increment in the amount of particles, the size of -Al phase or grain boundary decreases progressively. There are no agglomerations and porosity in this micrograph because of increased the pressure (see Fig.1b). Grain growth during sintering changes the configuration of the grain boundaries relative to pores and thus may markedly influence the shrinkage rate. The addition of Al2O3 particles will increase the sintering rate if they increase diffusion rates, but they may also increase sintering rates by impeding grain-boundary movement. The grain growth might proceed via solid-state atomic diffusion. The relatively homogenous microstructure leads to the highest hardness in Fig.2.
a) C1 b) C3 Fig.1. Typical SEM micrographs of pure Aluminium matrix and its 10wt. % Al2O3 reinforced Al composite, sintered at 550oC for 45 min. a) Pure aluminium (C1), b) 20 m-10wt. % Al2O3/Al composite, indicating distributions of Al2O3 particles in the matrix (C3).
3.2 Hardness of The Composite Hardnesss of composites produced at different temperatures and times were measured by taking at least 5 samples. The results showed that hardness increased with increasing temperature, as shown in Fig.2. This 600C temperature promotes additional particle to particle bonding and more complete alloying because of higher diffusion rates. On the other hand, it is necessary to reduce the oxides of these elements in order to promote bonding of particles. However, sintering time is found to be more effective than that of the because of mechanism of neck formation and neck growth of powders (Table 1). Moreover, the hardness of the MMCs increased with increasing the size of particles (Fig.2). The achievement of wettability of these materials decreased for 3m-Al2O3 reinforced composite than that of the 20m-reinforced composite although the degree of liquid phase formation increases with temperature.
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Table 1. The results of hardness of metal matrix composite. Sintering times 45min Materials type Al matrix (C1) Al-3m-10wt.% Al2O3 reinforced MMCs (C2) Al-20m-10wt.% Al2O3 reinforced MMCs (C3) Hardness at 550C(HB1) 26.5 31.8 38.3 Hardness at 610C(HB1) 28 32.1 42 Hardness at 550C(HB1) 30 35.2 46 120min Hardness at 610C(HB1) 31.3 36.5 50.9
Fig.2. Variation of hardness as a function of type of materials for Al matrix and its 10wt. % Al2O3 reinforced Al composite. a) Sintering time of 45min, b) Sintering time of 120min a) (b) 3.3. Wear Behaviour The average volumetric wear rate of Al/Al2O3 reinforced composites are determined, and are illustrated graphically in Fig.3 as a function of different load. It is found that the wear loss of the composites increase sharply with all applied for both materials. The composite shows a lower wear rate than that of the matrix at lower loads due to increased hardness of the samples (see Table 1). This is a good agreement with previous studies on wear of metal matrix composite by Lim et al. [13], and Kumar et al. [17]. Furthermore, lower sizes of particles in the MMCs give the highest wear loss because small SiC particles in the composite are more easily pulled-out from the matrix, compare with higher sizes of particles. As the Al2O3 particles size increases from 3 m to 20 m in a fixed sliding distance, the composites wear rate tested at an average load decreases to 52%. On the worn surfaces, reddish-brown coloured transfer layers are observed by naked eye. This layer may be contained constituents from the counter face like Fe, Si and Cr, which is Fe rich layer. It acts as a solid lubricant and prevents direct contact between the composites and counter face during wear testing [23, 25]. However, there
Fig.3. Variation of average volumetric wear rate as a function of applied load for 10wt. % Al2O3 reinforced Al composite, sintered at 550C and 45 min.
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are more conflicting reports on these issues. For example, some researchers show that the wear resistance of Al2O3 or SiCp reinforced composites increases with increasing particle sizes and/or volume fraction of particles [21-24]. On the contrary, other people report that the smaller sizes of particles lead to the more wear resistant composites [26, 27]. 4. CONCLUSIONS The effects of particle size, applied load on the mechanical and dry wear behaviour of composites were investigated. 1. Aluminium composites containing various particle sizes with 10wt. % Al2O3 particles were produced successfully using PM method. SEM observation of the microstructure showed that homogenous distributions of Al2O3 particles in the pure matrix seemed to be dominant. 2. Hardness of the composite sintered at 550C increased with increasing the size of particle in the matrix, average hardness increased by approximately % 44.5 compared to unreinforced matrixes. 3. It was found that the composites wear rate decreased to 52% as the Al2O3 particle size increased from 3 m to 20 m in a fixed distance. REFERENCES 1. Das, S., Mondal, D.P, Dixit, G., Correlation of abrasive wear with microstructure and mechanical properties of pressure die-cast aluminium hard-particle composite, Metal. Mater. Transact., p. 633, 32A, 2001. 2. Zhang, Z.F., Zhang L.C., Mai, Y.W., Particle effects on friction and wear of aluminium matrix composites, J. Mater. Sci., p.1999, 30 A, 1995. 3. Singh, M., Jha, A.K., Das, S., Yegneswaran, A.H., Preparation and properties of cast aluminium alloy-granite particle composites, J. Mater. Sci., p.4421, 35, 2000. 4. Mandal, D.P., Das, S., High stress wear behaviour of aluminium hard particle composites effect of experimental parameters, particle size and volume fraction, Tribol. Inter., p.461, 39-6 2006. 5. Zhiqiang, S., Di, Z., Guobin, L., Evaluation of dry sliding wear behaviour of silicon particles reinforced aluminium matrix composites, Mater. Des. p.454, 26, 2005. 6. Bindumadhavan, P.N., Wah, H.K., Prabhakar, O., Dual particle size (DPS) composites effect on wear and mechanical properties of particulate metal matrix composites, Wear. , p.112, 248, 2001. 7. Sahin, Y., Preparation and some properties of SiCp reinforced composites, Mater.&Des., p.671, 24, 2003. 8. Mandal, D., Dutta, B.K., Panigrahi, S.C., Effect of wt.% reinforcement on microstructure and mechanical properties of Al-2Mg base short steel fiber composites, J.Mater. Process. Tech., p.195,198, 2008. 9. Venkataraman, B., Sundararajan, G., Correlation between the characteristics of the mechanically mixed layer and wear behaviour of aluminium, Al-7075 alloy and Al-MMCs, Wear. 22-38., p. 245, 2000. 10. Min, K.H., Lee, B.H., Chang, S.Y., Kim, Y.D., Mechanical properties of sintered 7xxx series Al/SiC composites, Mater. Lett., p.2544, 61, 2007, 11. Zebarjad, S.M., Sajjadi, S.A., Microstructure evaluation of Al-Al2O3 composites produced by mechanical alloying method, Mater. Des., p.684, 27,2006. 12. Zhang, J.T., Sheng, L., Liu, Zhai, P.C., Fu, Z.Y., Zhang, Q.J., Influence of heat treatment on interface of Cu/Al bimetal composite fabricated by cold Rolling, Mater.Lett., p.443, 62, 2008. 13. Lim, C.Y.H., Lim, S.C., Gupta, M., Wear behaviour of SiCp-reinforced magnesium matrix composites, Wear, p. 629-637, 255, 2003. 14. Wang, H., Zhang, R., Hu, X., Wang, C.A., Huang, Y., Characterization of a powder metallurgy SiC/Cu-Al composite, J. Mater. Procesess.Tech., p.43, 197, 2008. 15. Wan, D.T., Hu, C.F., Bao, Y.W., Zhou, Y.C., Effect of SiC particles on the friction and wear behavior of Ti 3 Si(Al) C 2 composites, Wear, p. 826, 262, 2007.
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16. Rahimian, M., Parvin, N., Ehsani, N., Investigation of particle size and amount of alumina on microstructure and mechanical properties of Al matrix composite made by powder metallurgy, Mater. Sci. Eng., p.1031, A527, (4-5), 2009. 17. Kumar, A., Mondal, Chandra Rao, B.S.S., Kumar, S., Wear behaviour of AE42+20% saffil Mg-MMC, Tribol. Inter., p.290, 40, 2007. 18. Shorowordi, K.M., Laoui, T., Haseeb, A.S.M.A., Celis, J.P., Froyen, L., Microstructure and interface characteristics of B4C, SiC and Al2O3 reinforced Al matrix composites a comparative study, J.Mater. Process. Tech., p.738, 142,2003. 19. Mondal, A., Murty, B.S., Chakraborty, M., Effect of TiB2 particles on sliding wear of composite, Wear, p. 865872, 266, 2009. 20. Kiourtsidis, G.E., Skolianos, S.M., Wear behavior of composites or of artificially aged AA2024/40 m SiCp composites in comparison with conventionally wear resistant ferrous materials, Wear, p. 946, 253, 2002. 21. Deuis, R.L., Subramanian, C., Yellup, J.M., Dry wear of composites, A review, Comp. Sci.Technol., p.413, 57, 1997. 22. Sharma, S.C., Girish, B.M., Somashekar, D.R., Satish, B.M., Kamath, R., The study process and wear behaviors in powder sintering 6061 Aluminum alloy composites, Wear, p.89, 224 1999. 23. Ahlatc, H., Koer, T., Candan, E., imenoglu, H., Wear behaviour of Al /(Al2O3p +SiCp ) hybrid composites, Tribol. Inter., p.213, 39, 2006. 24. Angers,R., Krisnadev, M.R., Tremblay, R., Corriveau, J.F., Dube, D., Characterization of SiCp/2024 aluminum alloy composites prepared by mechanical processing in a low energy ball mill, Mater.Sci.Eng., p.9, A262,1999. 25. Belmonte, M., Nieto, M.I., Osendi, M.I., Miranzo, P., Influence of the SiC grain size on the wear behaviour of Al2O3/SiC composites, J.European Soc., p.1273, 26, 2006. 26. Straffeline G., Experimental observations of subsurface damage and oxidative wear in Al-based metalmatrix composites, Wear, p.216, 245, 2000. 27. Sheu, S.Y., Lin, S.J., Particle size effect on the abrasion wear of 20 vol. % SiCp/7075 Al composites, Scr. Mater., p.1271,11, 1996.
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WEAR STUDIES ON DIAMOND-REINFORCED Fe-Co BASED METAL MATRIX COMPOSITES

Kerim Emre KSZ*, Mehmet MR* and Yusuf AHN ** * Cumhuriyet University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 58140, Sivas, Turkey, emre.oksuz@cumhuriyet.edu.tr * Cumhuriyet University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 58140, Sivas, Turkey, msimsir@cumhuriyet.edu.tr ** Gazi University, Faculty of Technology, Department of Manufacturing Engineering, Beevler-06500, Ankara, Turkey, ysahin@gazi.edu.tr ABSTRACT Abrasive wear behaviour of diamond-reinforced Fe-Co composites produced using hot pressing method was studied using a pin-on-disc wear rig where the samples slid against different SiC abrasives. Effects of wear parameters like, abrasive size, load, sliding time and hardness on weight loss were investigated. A plan of experiments in terms of Taguchi techniques was performed to acquire data in controlled way. An orthogonal array and analysis of variance were employed to investigate the influence of process parameters on the wear of composites. Furthermore, the confirmation of experiment was conducted to verify the optimal testing parameters. The experimental results showed that the hardness was the major parameter on the abrasive wear, followed by the applied load while the sliding time was found to have a neglecting effect. Key words: Fe-Co based matrix; Diamond; Powder metallurgy; Orthogonal Array; Taguchi method; Wear; Analysis of Variance 1. INTRODUCTION Diamond tools are widely used for sawing, drilling and grinding materials like stone, concrete and ceramics since the extreme hardness of diamond and strength of the diamond / matrix combinations [1]. The choice of the matrix material that bonds the diamond is vital to the eventual lifespan of these high performance tools. The matrix used in the most diamond tool is a cobalt alloy since it combines with diamond grits good chemical compatibility at the processing temperature. However, the price of Co is subjected to great variations [2, 3]. It is the main reason behind efforts to replace Co with other metals such as Co-bronze, Fe-bronze, Tin-Co, Fe-Co-Cu and Ni based materials [4-6]. In order to make sound products of the diamond reinforced alloy, it is needed to select the composition of the alloy matrix, its size, concentration of diamond grits, width and depth of ditches or diameter and depth of cell, location of ditches and cells in a product [7-12]. On the other hand, in any process, a trial-and-error approach is an expensive and time consuming way [13]. Therefore, several mathematical models based on statistical regression techniques have been constructed to select the proper cutting or testing conditions [14-18]. The Taguchis design can simplify by expending the application of the traditional experimental designs like full factorial or fractional factorial design to the use of orthogonal array [19-28]. The most of the study has been focused on processing and mechanical properties of hard and diamond materials [1, 3-12]. However, no works related to abrasive wear properties of diamond reinforced metal matrix composites by experimentally has been reported. The aim of the present study is, thus, to investigate the wear behaviour of diamond-reinforced composites based on the Taguchi method. Furthermore, the analysis of variance is employed to investigate the wear behaviour of metal matrix composites under different conditions.
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2. TAGUCHI TECHNIQUE Taguchi technique is a powerful tool for the design of the high quality system [18, 24]. To achieve desirable product quality by design, Taguchi recommends a three stage process such as system design, parametric design and tolerance design [25]. System design focuses on determining the suitable working levels of design factors. It includes designing and testing a system based on the engineers judgement of selected materials, parts and nominal process parameters. Parametric design seeks to determine the factor levels that produce the best performance of the product/process. The optimum condition is selected so that the influence of the uncontrolled factors (noises) causes minimum variation of the system performance. Tolerance design is used to fine tune the results of parameter design by tighting the tolerance of factors with significant influence on the product [26]. The most important stage in the plan of experiment is selection of factors. The data collected from all the experiments in the set are analyzed to determine the effect of various design parameters, which is accomplished with the aid of orthogonal arrays [19, 21]. Taguchi recommends the use of the criteria he call Signal-to-Noise (S/N)-ratios as performance statistics. The change in the quality characteristic of a product in response to a factor introduced in the experimental design is the signal of the desired effect. The effect of external factor (uncontrollable factors) on the outcome of the quality characteristic under the test is termed noise. The S/N ratio measures the sensitivity of the quality characteristic being investigated in a controlled manner. A high value of S/N implies that signal is much higher than the random effect of noise factors [26, 27]. 3. EXPERIMENTAL STUDY Fe-Co based diamond reinforced composites were produced by hot pressing method. Diamonds were used as reinforcement in the production of metal matrix composite while Co metal was a binder with a good wet ability. Fe is also used as a filling material because of its lower-cost. The concentration of diamond in the composite is kept constant as 20. The composites with various compositions [Fe-(15-3555wt. %Co)-bronze 10 wt. %-diamond 20 conc. with and without B4C powder (0.15 g)] were prepared. Polycrystalline diamond grits of 40/+50 mesh (LS4750+, LANDS), a carbonyl iron powder with an average particle less than 75 m (BaymetMetal Industry Inc.), a cobalt powder with an average particle size of 400 mesh (Umicore), a bronze powder with 85/15 mesh (Pometon), and a B4C (H.C.Starck) powder with average particle size less than 10m were selected as the starting materials for this study. In the production of composites, Fe-Co-bronze-diamond- was blended in T2 turbula mixture at about 45 min. The mixture per composition was put in carbon moulds 24X10X10 mm dimension were cold compacted, and then hot zone was evacuated to remove the air from the chamber atmosphere, and sintered by hot pressing of Fritsch DSP 510 type machine under nitrogen atmosphere. The sintering temperature was about 900 oC under a compression of 25 MPa. Total sintering time was about 15 min. Three types of samples were produced by this process, which is called as C1 (75Fe-15Co-10bronze-diamond), C3 (55Fe-35Co-10bronze-diamond), C5 (35Fe-55Co-10bronze-diamond) code. A typical micrograph of MMC including diamond particles was examined by SEM microscopy. Macro hardness tests, hardness Rockwell B, were carried out under 100 kgf in three samples for each composition and average of hardness values were calculated and presented. 3.1. Wear Tests A pin-on-disc type of apparatus was employed to evaluate the wear characteristics of MMCs (Fig.1). The counter surface material for the wear testing was a BS970 534A99 steel disc 160 mm diameter by 12 mm thick, which was heat-treated to give a surface hardness of 59-63 RC. The composite bars were produced in the form of square shapes. The wear pin specimens made from MMCs are approximately 10X10 mm in dimension and 24 mm in length, too short to fit into a standard wear machine. To form a pin necessary length the cylinders were bonded to a 60 mm long steel extension pin of the same diameter using an epoxy adhesive, with a brass sleeve fitted over the joint for extra strength. The samples were loaded against the hardened steel disc with the help of a cantilever mechanism. The specimens experienced to continuous motion in pre-determined time to complete the certain travel distances. Wear tests were carried out at room temperature without lubrication at different times. In wear tests; normal loads on the pin were 5, 15 and 25 N at a constant sliding speed of 1 m s-1. Each test was performed with a fresh SiC papers 400 grits and 180 grits, which is corresponds to ~18m and ~70 m,
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respectively. The track radius has been kept at 90 mm in length. The width of the wear track was 6.5 mm. The track radius was measured to be the distance between the centre of the disc and the central point of the track. A systematic view of the test procedure is shown in Fig. 1. The specimen surfaces were ground well prior to initiating the wear tests and subjected to few runs against the counter surface at different loads for establishing intimate contact between the two matting surfaces. All the samples and the disc surface were cleaned by acetone and then dried under ambient condition prior to and after tests. It was repeated for three times at least. Detail of the wear machine and wear process were given in previous study [14].
Fig.1. Schematic view of the pin-on-disc test procedure
3.2. Plan Experiments The experiment was carried out to analyze the influence of testing parameters on weight loss of metal matrix composites. In the present investigation, a standard Taguchi experimental plan with L18 (21X37) was chosen. The wear parameters chosen were abrasive size, materials hardness, load, sliding time and their levels, as indicated in Table 1. Experimental design is shown in Table 2. The first column in Table 2 was assigned to abrasive size (A), second column was hardness (B), third column was applied load (C) and forth column was assigned to sliding time (D) and the remaining columns were assigned to their wear results. The response to be studied was the wear with the objective as smaller, as the better. The experiments were conducted as per the orthogonal array with level of parameters given in each array row. The abrasive dry wear test results were subject to the analysis of variance to see which tests parameters are statistically significant. Table 1. Control factors and their levels for diamond reinforced MMCs. Levels 1 2 3 Abrasive size, m 18 m 70 m Hardness, BHN 88 93.4 97.2 Applied load, N 5 15 25 Sliding time, s 30 60 90
4. RESULTS AND DISCUSSION 4.1. Microstructure and Mechanical Test A typical micrograph of MMC reinforced by diamond particles is shown in Fig.2. It indicated that no evidence of the presence of cavities neither at interface nor in the matrix was observed using the SEM microscopy. The distribution of diamonds in the matrix could be seen in this micrograph. The diamond crystals were observed to be cube-octahedral in shape, but the diamond protrusions were also evidence. Fracture of different planes in diamonds was an indication of an enough bonding between the diamond and the matrix alloy. Macro hardness tests by hardness Rockwell B were carried out under 100 kgf in three samples for each composition and average of hardnesss values were presented (Table 1). The highest hardness was obtained for C5 samples because the hardness increased with increasing Co content (55%).
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Fig.2. Typical SEM micrograph of Fe-Co based MMC reinforced with only diamonds, showing cube-octahedral diamond crystals set and distributions of diamonds in the matrix. 4.2. Analysis of Control Factors Table 2 shows experimental design and results for weight loss of the composites and calculated S/N ratios. Analysis of the influence of each control factor on the weight loss was performed using a Minitab computer package. The control factor with the strongest influence is detected by differences values. The selected quality characteristic, weight loss, is a lower the better type and the S/N ratio for lower the better type of response is used as given below: (1)
Where y1,y2....yn are the response of quality characteristic for a trial condition repeated n times. The S/N ratio can be computed using Eq. (1) for each of the 18 trials and the values are reported in Table 2 along with the raw data. Table 2. Experimental design and results for weight loss of MMCs and their calculated S/N ratios. Expert no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Abrasive size, m (A) 18 18 18 18 18 18 18 18 18 70 70 70 70 70 70 70 70 70 Main factors Hardness, HB Load, (B) N (C) 88 5 88 88 93.4 93.4 93.4 97 97 97 88 88 88 93.4 93.4 93.4 97 97 97 15 25 5 15 25 5 15 25 5 15 25 5 15 25 5 15 25 Sliding time, s (D) 30 60 90 30 60 90 60 90 30 90 30 60 60 90 30 90 30 60 Diamond reinforced MMCs Weight loss S/N ratio (dB) in g 0.00370 48.6360 0.00550 0.01040 0.00160 0.00280 0.00740 0.00096 0.00290 0.00210 0.00890 0.01370 0.01730 0.00480 0.00860 0.00750 0.00400 0.00510 0.00720 45.1927 39.6593 55.9176 51.0568 42.6154 60.3546 50.7520 53.5556 41.0122 37.2656 35.2391 46.3752 41.3100 42.4988 47.9588 45.8486 42.8534
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12. Ko, Y.S., Tsurum, T., Fukunaga, Q., Yano, T., High pressure sintering of diamond-SiC composite, J.Mater. Sci., p. 469-475, 36, 2001. 13. Rabinowicz, E.D., Friction and wear of work hardening in the design of wear resistant materials, Wiley, New York, p.168, 1965. 14. ahin, Y., The prediction of wear resistance model for the metal matrix composites, Wear, p.17171722, 258, 2005. 15. Mondal, D.P., Das, S., Jha, A.K., Yegneswaran, A.H., Abrasive wear of Al alloy-Al2O3 particle composite, Wear, p. 131-138, 223, 1998. 16. Prasad, B.K., Das, S., Jha, A.K., Modi, O.P, Dasgupta, R., Yegnaswaran, A.H.,Wear of Al2O3 particle composite, Composites, p. 301-308, 28A, 1997. 17. ahin, Y., Tribological behavior of the metal matrix and its composites, Mater. Des., p.1348-1352, 28, 2007. 18. Basavarajappa, S., Arun, K.V., Paulo Davim, J., Effect of fillers on dry sliding wear behaviour of polymer matrix composites-A Taguchi approach, J.Miner.Mater. Charact.Eng. p. 375-391, 8, 2009. 19. Basavarajappa, S., Chandramohan, G., Paulo Davim, J., Application of Taguchi techniques to study dry sliding wear behaviour of metal matrix composites, Mater.Des., p.1393-1398, 28, 2007. 20. Fernandez, J.E., Fernandez, M.R., Diaz, R.V., Navarro, R.T., Abrasive wear analysis using factorial design, Wear, p.38-43, 255, 2003. 21. ahin, Y., Optimization of testing parameters on the wear behaviour of the metal matrix composites based on the Taguchi method, Mater. Sci.Eng. p.1717-1722, A408, 2005. 22. Basavarajappa, S., Chandramohan, G., Wear Studies on Metal Matrix Composites A Taguchi Approach, J. Mater. Sci. Technol., p. 845-852, 21(6), 2005. 23. ahin, Y., Comparison of tool life between ceramic and cubic boron nitride (CBN) cutting tools when machining hardened steels, J.Mater. Process. Technol. p.3478-3486, 209, 2009. 24. Yang, W.H., Tarn, Y.S., Design optimization of cutting parameters for turning operations based on the Taguchi method, J.Mater. Process. Technol. p.121-129, 84, 1998. 25. Roy, R.K., A Primer on the Taguchi method, Van Nostrand Reinhold, New York, 1993. 26. Phadke, M.S., Quality Engineering Using Robust Design, AT&T Bell Laboratories Report, Prentice-Hall International Editions, New Jersey, 1989. 27. Montgomery, D.C., Experimental Design Analysis, 4th Edition, John Wiley Sons, New York, 1997. 28. Rose, P. J., Taguchi Technique for Quality Engineering, McGraw-Hill, New York, 1988.
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THE EFFECT OF SINTERING AND NITRIDING PROCESSES ON DISTALOY AE POWDER MATERIALS

smail AKBULUT*, Abdul Kadir EK**, Durmu Ali BIRCAN**, Murat DILEK** and hsan EFEOLU*** * Turkish Petroleum Corporation, Batman, Turkey, ismailakbulut61@yahoo.com ** ukurova University, Mechanical Engineering Department, Adana Turkey, akeksi@cukurova.edu.tr, abircan@cukurova.edu.tr, mdilek@hotmail.de *** Atatrk University, Mechanical Engineering Department, Erzurum, Turkey, iefeoglu@atauni.edu.tr ABSTRACT In this work, Distaloy AE metal powders have been chosen for study due to widely used in industrial applications. First, Distaloy AE powders were pressed at 500 MPa pressure and room temperature. Then, pressed specimens were sintered at 1120 C for 30 minutes. In order to examine the effects of sintering operation on density, densities of each specimen have been measured separately. After sintering operation, nitriding was applied to a group of specimen at 520 C temperature during 16 hours. To investigate mechanical properties of sintered and nitrided Distaloy AE powders were performed. In addition, fractured specimens after tensile tests were used for microhardness tests. Key Words: Distaloy AE, Sintering, Nitriding, Fatigue 1. INTRODUCTION The Powder Metallurgy (PM) process is a near-net or net-shape manufacturing process that combines the features of shape-making technology for powder compaction with the development of final material and design properties (physical and mechanical) during subsequent densification or consolidation processes (e.g., sintering). It is critical to recognize this interrelationship at the outset of the design process because a subtle change in the manufacturing process can cause a significant change in material properties. Powder metallurgy has a wide range of applications ranging from automotive, building and contraction, hardware, heat treatment, medical and dental, to advanced aerospace components, etc. PM components have established themselves as an economic alternative to components made from other manufacturing processes as well as the only means to procedure some components which cannot be made other methods [1]. This process is a very suitable technique for manufacturing. Especially, this process contains blending or mixing, pressing or compacting, sintering and finishing. An important step is sintering for this process. Sintering reduces the porosity and enhances properties such as strength, translucency and thermal conductivity; yet, in other cases, it may be useful to increase its strength but keeping its gas absorbency constant. During the firing process and as it continues; grain size becomes smaller and more spherical [2, 3]. The most important thing after producing the material by using PM is to increase the mechanical and physical properties of the material. This especially can be done by nitriding. Nitriding is low temperature, low distortion thermochemical heat treatment carried out to enhance the surface properties of finished or near finished ferrous components. It is different in terms of suitable materials, processing conditions, the nature of the surface layers imparted and the property improvements conferred. Nitriding, conducted in gas (490C - 560C) or plasma (400C - 590C) for treatment times ranging up to 90 hours, involves the diffusion of nitrogen into the surface to produce a controlled depth of hard alloy-nitrides. Unlike the high-temperature, a case-hardening treatment, hardening is achieved without the need for quenching [4, 5].
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Nitriding process has some advantages to improve qualified for part properties. These are high torque, high wear resistance, abrasive wear resistance, corrosion resistance and high surface compressive strength. This paper presents the influence of sintering and nitriding process on Distaloy AE PM. The main aim of these processes is to improve physical and chemical characteristic of Distaloy AE. To do this, one should know the properties of the material well, adjust the temperature of the thermal process, choose a process increasing the surface quality and suitable for sample and perform a good fatigue design. 2. MATERIAL and METHOD 2.1. Material The Distaloy AE based on additions of Iron (Fe), Nickel (Ni), Copper (Cu), Molybdenum (Mo) and Carbon (C) is a high strength alloy. High Ni content and good compressibility makes it possible to produce materials with a sintered tensile strength increased. Distaloy AE exhibits good hardenability and dimensional stability. The chemical composition of Distaloy AE powder, from Hganas in Sweden, is given in Table 1. Table 1.Chemical composition of Distaloy AE powder Chemical Analysis of Distaloy AE % Iron (Fe) 94 2.2. Method Firstly, the components of Distaloy AE powder (4% Ni, 1.5% Cu , 0.5% Mo ,%0.01 C); which are approximately weight of 37 g are mixed to put into blanks which a die in sizes of 10x10x55 mm, together with lubricant, until a homogeneous mix is obtained under 500 MPa pressure at room temperature. Then, the specimens were sintered under 1120 C sintering temperature was selected the optimum temperature to produce the samples for tensile and fatigue tests since it resulted in high density. All specimens were sintered for 30 minutes at 1120 C temperature, respectively. Temperature was increased by 5 C/min until medium of furnace reached sintering temperature; and then specimens were kept for 1 hour. After, furnace was closed and temperature was decreased by 5 C/min, until medium of furnace was reached room temperature (RT, 22C). After this process, density of sintered and green Distaloy AE was evaluated by the Archimedes Principle. After, the sintered samples were conducted machining operations and polishing operations using Computerized Numerical Control (CNC) turning lathe and metal polishing machine, in turn, to achieve optimum results for fatigue and tensile test produced. After that, fatigue and tensile test samples and technical drawings are shown in Figure 1 and 2 separately. Nickel (Ni) 4 Copper (Cu) 1.5 Molybdenum (Mo) 0.5 Carbon 0.01
Figure 1. Fatigue and tensile test specimens; a) Fatigue test sample, b) Tensile test sample
Figure 2.Technical representation of fatigue and tensile test specimens; a) Finished product for fatigue test sample, b) Finished product for tensile test sample (Dimensions are in mm) In this study, nitriding was applied to increase fatigue life of material. To evaluate sintered and nitrited parts in respect to mechanical properties, 11 samples were sintered and other 11 samples are nitrited at 520 C temperature and 16 hours in % 50 H2 and % 50 N2 atmosphere. After this process, tensile and fatigue test samples were prepared [6].
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All the experiments of fatigue tests were conducted in the axial load control which is more severe than bending under fully reversed loading (stress or load) ratio R= min/ max=-1 which is sine (cyclic) waveforms using 11 specimens for the determination of each S-N (Whler) curve. The fatigue tests were performed at the constant frequency of f = 10Hz. One stress ratios (R = -1) were investigated on the unnotched (Kt=1 ) specimens. Sine (cyclic) waveforms are used. The cyclic group of waveforms all start at a setpoint, proceed to a peak amplitude, either negative or positive, before reversing direction, passing through the setpoint to the opposite peak amplitude. The signal will then return to the initial starting position, ready to commence the next cycle. The sine waveform follows a sinusoidal path, defined by the amplitude and frequency parameters. In the tensile test, experiment was taken v = 0, 5 mm/min as vertical movement and this velocity was kept constant during experiments [7]. Furthermore, the vickers hardness profile of fractured parts obtained as a result of static tests was measured at 14 different points and intervals of 3 mm on longitudinal section using a Vickers intender with a 25 g load for time of 10 s as shown in Figure 3.
Figure 3. Fractured sample during tensile test for vickers micro-hardness experiment 3. RESULT AND DISCUSSION In this study, green densities of Distaloy AE powders were determined as 7.19 g/cm under 500 MPa. The average densities of sintered and nitreded samples were found as 7.13 g/cm and 7.15. g/cm respectively. As can be seen, green density of samples was higher than sintered densities. So, the decrease in number of pores and becoming the internal structures more homogeneous. Hardness extremely increased after nitriding as can be easily and clearly understood from the graph shown Figure 4. The occurrence of a layer above the nitrited sample can be seen in Figure 5.
Figure 4. Compare hardness of sintered and nitrided specimens
Figure 5.Nitriding layer of samples
This layer provides the surface of the material gets more severe and as a result be resistant against impacts. The hardness increases by 163 percent on the surface and by 39 percent in the inner sides. The result of tensile test, sintered and nitreded specimens shown in Figure 6. Sintered sample ruptured 297 MPa of maximum tensile stress while the nitrided one had 318MPa tensile stress of maximum. Diffusion of nitride atoms through the sample plays an important role for making is stronger. Nitride atoms enter the gaps and pores of the sample and makes its tensile stress increase by 7 percent.
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Figure 6. Comparison sintered and nitreded specimens of tensile stress curves In fatigue experiments, 50-140 MPa as a stress value of average are used and graphs are generated. 2*106 value was accepted as a limit in the graph as previous ones and above this value was run-out period. After nitriding, nominal stress increased by 15-20 % and the lifetime of sample was better. 90 MPa stress, sintered sample ruptured after 379000 cycle while the nitrited one ruptured after 1513601. The main effect on this condition is the diffusion of nitrite atoms through the inner side of the sample and fill the gaps and pores. After that, the inner side of the sample is becoming more stable and homogenous, and so that the lifespan gets longer shown Figure 7.
Figure 7.Comparison of S-N curves for all sintered and nitreded specimens 4. CONCLUSION The density of Distaloy AE powder was measured in two different conditions and nitrited sample density (7, 12 at room temperature) was more than sintered one. After the Tensile test, the resistance of the sample increased more in nitriding, the Ultimate Tensile Strength was 8 percent more than sintering. Fatigue resistance is 50-120 MPa for sintered samples and 70-140 MPa for nitrided samples. At 100 MPa pressure, sintered sample ruptured 120000 rpm, nitrided sample ruptured at 150000 rpm. The increase in the density of the nitrided sample was simply because of the decrease in pore amount. 5. REFERENCES 1. 2. 3. 4. Angelo P.C. and Subramanian R., 2009, Powder Metallurgy Science, Technology and Applications. ASM Handbook, 1998, Powder Metal Technologies and Applications, Vol. 7, ASM International. German, R. M., 1997, Powder Metallurgy Science, Metal Powder Industries Federation, New Jersey, USA. Miura, H., 2002, Fatigue Fracture Behavior of PM and PIM Steels, 3rd International Powder Metallurgy Conference, September 4-8, 2002, Turkish Powder Metallurgy Association, Gazi University, Ankara, Turkey, pp. 47-55. 5. Molinari, A., Tesi, B., Bacci, T. and Marcu, T., 2001, Plasma Nitriding and Nitrocarburising of Sintered Fe-CrMo and Fe-Cr-Mo-C Alloys, Surface and Coatings Technology 140, pp. 251-255. 6. ASTM E8M, 2004, Standard Test Methods for Tension Testing of Metallic Materials (Metric). 7. ASTM E739, 2004, Standard Practice for Statistical Analysis of Linear or Linearized Stress-Life (S-N) and Strain-Life (-N) Fatigue Data at Room Temperature.
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BYOMEDKAL UYGULAMALAR N Ti-Mg KOMPOZTLERNN GELTRLMES

Ziya ESEN*, Arcan F. DERCOLU**, akir BOR*** ankaya niversitesi, Malzeme Bilimi ve Mhendislii Blm, 06530, Ankara, Trkiye, ziyaesen@cankaya.edu.tr ** Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mhendislii Blm, 06531, Ankara, Trkiye, arcan@metu.edu.tr *** Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mhendislii Blm, 06531, Ankara, Trkiye, bor@metu.edu.tr
*
ZET Biyomedikal uygulamalarda kullanlan metalik malzemeler genel olarak vcuda yerletirildikten belli bir sre sonra vcut svlaryla tepkimeye girmekte veya herhangi bir reaksiyona girmeden btnln korumaktadrlar. Son zamanlarda vcuda yerletirildiinde zamanla tepkimeye girerek vcutta yokolan ve herhangi bir yan etkiye neden olmayan magnezyum ve magnezyum alamlar zerine yaplan almalar artm ve genellikle aratrmalar bu alamlarn vcutta kontroll bir ekilde znmesi zerine younlamtr. Dier yandan, vcut svlaryla tepkimeye girmeyen titanyum ve titanyum alamlar gibi metalik malzemeler son derece yksek biyo uyumlulua ve korozyon direncine sahip olduklarndan dolay sklkla biyo-medikal uygulamalarda kullanlmaktadrlar. Bu almada, vcutta tepkimeye giren magnezyum ile herhangi bir reaksiyona girmeden btnln koruyan titanyumun bir arada kullanlmasyla yeni bir biyomedikal kompozit malzeme toz metalurji yntemi kullanlarak scak deformasyonla retilmitir. Hacimce % 50, 60, 70 ve 80 magnezyum tozu ieren Ti-Mg tozlar iki ucu kapatlm bakr borularn iinde 430oCde scak deforme edilen numunelerin apnda yaklak % 45 deiim gzlenmitir. Numuneler 600oCde 100 dak. sinterlendikten sonra basma ykleri altnda mekanik zellikleri karakterize edilmi ve kompozitlerin i yaplar optik ve elektron mikroskoplar ile incelenmitir. Anahtar Kelimeler: Kompozit, Biyo-malzeme, Toz Metalurjisi, Mekanik zellikler
DEVELOPMENT OF Ti-Mg COMPOSITES FOR BIOMEDICAL APPLICATIONS

ABSTRACT Metallic materials used in biomedical either interact with body fluids after a while or they preserve their integrity without any reaction. Nowadays, the research on magnesium, which dissolves in the human body after having been implanted without leaving harmfull remainders, has been inceased and the researches are focused on dissolving of magnesium in vivo in a controlled fashion. On the other hand, Ti and Ti-alloys are being used as bio-inert materials and preferred in biomedical applications as they exhibit superior biocompatibility and high corrosion resistance. In this study, new type of biomedical composite structures made up of biodegradable magnesium and bio-inert titanium powders have been manufactured by powder metallurgy using rotary hot swaging. Around 45% reduction in diameter has been observed in cans filled with Ti-Mg powder mixtures containing 50, 60, 70 and 80 % magnesium by volume as a result of deformation at 430oC. The samples were compression tested under quasi-static conditions after they had been homogenized by the application of annealing heat treatment at around 600oC. In addition, microstructure of mechanically tested samples were examined by optical and scanning electron microscopes. Keywords: Composite, Bio-material, Powder Metallurgy, Mechanical Properties
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1. GR Son zamanlarda medikal alanlardaki ilerlemelerle birlikte insanlarn ortalama mr ykselmi ve dolaysyla uzun mrl ve vucda uyumlu biyomedikal malzeme aratrmalar nceki yllara oranla byk bir art gstermitir. Biyomedikal malzemeler yapay kalp valflerinde, stentlerde ve di protezlerinde kullanlmakta, bunun yannda vcutta deiik yklere maruz kalan omuz, diz, kala ve dirsek gibi hareketli eklem blgelerinde de protez uygulamalar sklkla grlmekte ve zellikle diz ve kala blgelerindeki protez uygulamalarnda nmzdeki 20 yl iinde % 100n zerinde art gzlenmesi beklenmektedir [1]. Biyomedikal malzemeler vcuda yerletirildikten bir sre sonra anma, korozyon, yorulma, iltihap oluumu gibi nedenler ile vcut kemii ile mekanik zelliklerindeki uyumsuzluklarndan dolay ilevini yitirmekte ve bundan dolay ya yaplan operasyonlar tekrar edilmekte ya da vcut hcrelerinde geriye dnlemez hasarlar meydana gelebilmektedir. Bu nedenlerden dolay kullanlacak olan biyomedikal malzemelerin yksek derecede biyo uyumlulua, yksek korozyon direncine sahip olmas ve vuct kemiine benzer mekanik davranlar gstermesi beklenmektedir. zellikle eklem blgelerinde kemik ile biyomedikal malzemelerin elastik modlleri arasndaki farkllk kemik ve implant malzemenin deiik oranlarda yk tamasna neden olmakta bu da zamanla implanta temas eden blgelerdeki kemik hcre kaybn ve implantn yerinden kmasn beraberinde getirmektedir ve bundan dolay da implant ve kemik elastik modllerinin (katsaylarnn) benzerlik gstermesi implant malzemenin vcutta gvenli bir ekilde kullanlmas asndan nemlidir. Bunun yannda uzun bir implant mr iin biyomedikal malzemenin yksek anma direnci ile yorulma dayanmna sahip olmas da beklenmektedir. Gnmzde kullanlan biyomedikal malzemeler genellikle metalik, seramik ve polimerik malzemelerdir. rnein seramik malzeme olarak aluminyum oksit ve kalsiyum fosfat, polimerik malzeme olarak poli etilen malzeme kullanmlar grlmektedir. Bunlarn yannda seramik takviyeli polimerik kompozitler ile biyouyumluluu arttrmak iin eitli metalik malzemeler zerine seramik kaplama uygulamalarna da rastlanmaktadr [2]. Kullanlan biyomedikal malzemeler arasnda polimerik malzemeler dk mekanik dayanmlarndan, seramik malzemeler de dk krlma tokluuna bal olarak krlgan olmalarndan dolay yke maruz kalan blgelerde kullanlamamaktadr. Bu tr uygulamarda titanyum, titanyum alamlar, Co-Cr alamlar ve paslanmaz elik gibi metalik malzemeler tercih edilmektedir. Metalik malzemeler arasnda vcut kemiine benzer mekanik zellikleri, yksek biyouyumluluklar ve TiO2 pasif yzey oksit tabakasna bal yksek korozyon direnlerinden dolay titanyum ve titanyum alamlar biyomedikal uygulamalarda sklkla tercih edilmektedirler. Co-Cr alamlar ve paslanmaz elikler iin 240 ve 210 GPa olan elastik modl titanyum ve sklkla kullanlan Ti6Al4V alamlar iin srasyla 100 ve 112 GPa civarndadr [1]. Fakat bu malzemelerin elastik modl kemiin elastik modlne (3-20 GPa [3]) gre farkllk gstermesinden dolay nispeten kemiin mekanik zelliklerine daha fazla benzerlik gsteren NiTi alamlar ile Ti-Nb gibi beta tipi titanyum alamlar gelitirilmitir. Yine de kullanlan veya gelitirilen hacimli biyomedikal malzemeler tam olarak istenilen mekanik deerlere ulaamamaktadr. Son zamanlarda istenilen mekanik zelliklere sahip ve ayn zamanda kemik hcrelerinin bymesine olanak salayabilecek ekilde gzenekli titanyum ve titanyum alamlarnn sv veya kat faz retimi konusunda birok almalar yaplmtr [4-6]. Bu tr gzenekli malzemelerin retilmesiyle istenilen mekanik deerlere ulalmasna ramen gzeneklerin kemik hcreleriyle dolmas iin en az 3 ay gibi bir zaman gemektedir. Bu zaman aralnda implant malzemesinin kemie tam olarak tutanamamasndan dolay bu aamada sorunlara neden olmaktadr. Genel olarak hacimli veya gzenekli titanyum ve titanyum alamlar vcuda yerletirildikten sonra btnlklerini korumakta ve vcut svlaryla yok denecek kadar az reaksiyona girerek vcutta kalc implant vazifesi grmektedirler. Dier yandan son zamanlarda titanyum ve titanyum alamlarnn aksine vcut svlaryla tepkimeye girerek bir nevi kemik hcrelerinin bymesine yardmc olan magnezyum ve magnezyum alamlarnn kullanm artmtr. Fakat, yeni kemik hcrelerinin bymesinde uyarc bir etki gsteren ve mekanik zellikleri kemiin mekanik zellikleri ile kyaslanabilir olan magnezyum ve magnezyum alam implantlar kemik hcrelerinin kendini yenilemesi esnasnda sadece 12-18 hafta arasnda mekanik btnl korumakta ve sonrasnda yksek korozyon hzndan dolay btnln yitirmektedir [3]. Magnezyumun hzla korozyona uramas mekanik btnln bozulmasna ve ilevisini yitirmesine neden olmaktadr. Bu almada saf titanyum ve saf magnezyumun bir arada kullanlmasyla biyomedikal uygulamalarda kullanlmaya aday yeni bir kompozit malzemenin retimi ve karakterizasyonu aratrlmtr. Bu amala, toz metalurji yntemi kullanlarak scak dvme yoluyla kompozit retimi yaplm ve kompozit retimi esnasnda ve sonrasnda meydana gelen i yap deiikleri incelenmitir. Son olarak basma testleri ile de retilen kompozitlerin mekanik davranlar incelenerek kompozitlerin mekanik zellikleri vcut kemii ile karlatrlmtr. 2. DENEYSEL YNTEM Scak deformasyon yntemiyle Ti-Mg kompozit retiminde ASTM F1580-01 standartlarna uygun 55 m ortalama tane byklne sahip ekilsiz, yaklak % 99 saflkta titanyum tozlar (Phelly Materials) ile % 99.8 safla sahip
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ortalama tane boyutu 285 m olan kresel magnezyum tozlar (Tangshan Weihao Magnesium Powder Co. LTD) kullanlmtr. retimde ilk olarak homojen bir toz karm elde etmek amacyla hacimce miktar % 50-80 arasnda magnezyum tozu ieren Ti-Mg toz karmlar yarm saat sreyle bir kartrc vastasyla kartrlmlardr. Daha sonra hazrlanan toz karmlar bir ucu kapal bakr borunun iine yerletirilmi ve birka defa vakum altna alnp bakr borulara yksek saflkta argon doldurulmu ve bakr borular kapatlmtr. retimin bir sonraki aamasnda ise hazrlanan numuneler scak deformasyon yntemiyle 3 basamakta toplam % 45 orannda scak deforme edilmilerdir. Tozlarn sinterlenmesini hzlandrmak ve homojenlemeyi arttrmak amacyla numuneler hem deformasyon ncesinde hem de deformasyon basamaklar arasnda 450oCde 20er dakika bekletilmilerdir. Ayrca scak deformasyon sonras numunelerde olas gerilimleri azaltmak ve magnezyum tozlarnn sinterlenmesi daha da arttrmak amacyla 600oC scaklkta 90 dakika sreyle yksek saflktaki argon altnda tavlanma ilemi yaplm ve sonrasnda numuneler oda scaklna frnda soutulmutur. Son olarak kompozit malzemelerin yzeyindeki bakrlar ayrlm ve CNC torna yardmyla malzemeler ilenmitir. Numunelerde retim sonras younluk ve gzenek miktar Arimed prensibiyle younluk lm kitine sahip Sartorius marka hassas terazisi kullanlarak numunelerin ksilol zeltisine (CH3C6H4CH3) daldrlmasyla belirlenmitir. retimde kullanlan titanyum ve magnezyum tozlar ile retilen kompozit malzemelerin X-Ray krnm erileri Rigaku D/Max 2200/PC model X-Ray cihaz kullanlarak 40 kWta 30o-90o 2 alar arasnda belirlenmitir. Malzemelerin i yap incelemeleri hem parlatlm, hem de dalanm yzeyde gerekletirilmitir. Kompozitlerdeki magnezyumun i yap detaylarn ortaya karmak iin %5lik nital zeltisi, titanyum incelemesinde ise Krolls ayrac (3 ml HF+6 ml HNO3+100 ml H2O) kullanlmtr. yap incelemelerinde optik mikroskop ve Noran System 6 X-ray mikro analiz sistemine sahip Jeol JSM 6400 elektron mikroskobu kullanlmtr. Kompozitlerde kompozisyon deiimlerini belirlemek amacyla EDS izgi analizleri de ayrca kullanlmtr. Tane bykl gibi kantatif analizler Clemex Vision yazlm kullanlarak gerekletirilmitir. Kompozitlerin mekanik zellikleri biyomedikal malzemelerin vcutta sklkla maruz kald basma ykleri dnlerek basma testleri ile karakterize edilmitir. Bu maksatla ykseklik/ap oran yaklak 1.5 olan numuneler hazrlanm ve numuneler 0.5 mm/min hzyla video ekstansometreye sahip 100 kN kapasiteli Instron marka niversal ekme-basma cihazyla baslmlardr. 3. BULGULAR VE TARTIMA Bu almada younluu %100e yakn, magnezyum miktar hacimce % 50-80 arasnda deien biyomedikal uygulamalara aday Ti-Mg kompozit numuneleri retilmitir. Magnezyum oda scaklnda sadece (0001)<11-20> kayma sistemiyle deforme olabilmektedir ve yksek deformasyonlarda ise malzemeler kayma sistemlerinin snrl sayda olmasndan dolay krlmaktadr. Fakat, deformasyon scaklnn yaklak 200oCnin zerine kmasyla farkl kayma sistemleri iler hale gelmekte ve magnezyumun deformasyonu ok daha kolay olabilmektedir. retilen btn numunelerde titanyum tozlarnn arasndaki olas boluklar magnezyumun 450oC scaklkta deformasyona uramas ile doldurulmu ve younluu yksek, gzeneksiz bir yapnn eldesi salanmtr. ekil 1de rnek olarak Ti-80Mg kompozit numunesinin retim sonras deformasyona dik ve yatay kesitlerdeki parlatlm i yaps verilmektedir. ekilde koyu renkli blgeler magnezyumu, ak renkli blgeler ise titanyumu gstermektedir. Deformasyona dik olan kesitte magnezyum kreselliini korumasna ramen yatay kesitte magnezyum deformasyona urayarak deformasyon ynnde uzamtr. Biyomedikal uygulamalara aday olarak retilen Ti-Mg kompozitlerde titanyumun btnln korumas, dier yandan magnezyumun vcut svlaryla tepkimeye girerek korozyona urayp belli bir zaman sonra kaybolmas beklenmektedir. Dolaysyla retilen kompozitlerde magnezyum tozlarnn yap iinde birbiriyle balantl olup olmamas bu tr kompozitlerin korozyon davrann deitirecek ve numunelerin biyouyumluluklar farkl olacaktr. Magnezyum tozlarnn birbiriyle temas ettii kompozitlerde korozyonun hzl, magnezyum tozlarnn birbirlerinden titanyum tozlar ile tamamen izole edildii numunelerde ise yava bir korozyon hz beklenmektedir. Yaplan almada ise hacimce % 50 magnezyum ieren Ti-Mg kompozit numunelerinde magnezyumun izole olarak yapda durduu, dier numunelerde ise magnezyum tozlarnn yap iinde birbirine balantl olduu grlmtr. Dier taraftan magnezyum tozlarnn etrafnda yapda srekli olan titanyum tozlarnda retim sonrasnda yksek derecede younlama saland saptanmtr. Yaplan i yap incelemeleri ve mekanik testlerde titanyum tozlarnn birbirine ok iyi derecede mekanik olarak kilitlendii, fakat 600oCde uygulanan tavlama ileminin titanyum tozlarnn sinterlenmesinde etkili olamad grlmtr. Oda scaklnda titanyum ve magnezyum birbiri iinde yok denecek kadar az znmektedirler (yaklak arlka % 1.5) [7]. retilen kompozitlerde titanyum ve magnezyum tozlar ile arayzey boyunca yaplan EDS izgi analizlerinde ise herhangi bir kat zelti veya ikincil bir faza rastlanmam, eklenen titanyum ve magnezyum tozlarnn retim sonras yapda olduu gibi kald gzlenmitir.
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(a)
(b)
ekil 1. retilen Ti-%80Mg kompozitlerinin parlatlm i yaplar, a) deformasyona dik ara kesit, b) deformasyona paralel ara kesit. Ti-Mg kompozitlerde titanyum ve magnezyum tozlarnda retim esnasnda meydana gelecek deiiklikleri tayin edebilmek son rndeki i yapy ve dolaysyla rn fiziksel zelliklerini kontrol etme imkan salamaktadr. Yaplan deneylerde Ti-Mg kompozitlerde zellikle magnezyum tozlarnda mikro boyutta i yap deiimi saptanm ve bundan dolay magnezyum tozlarndaki deiimi daha iyi gzlemleyebilmek iin saf magnezyum numunelerinde retim esnasndaki deiimler incelenmitir (ekil 2 ve ekil 3). ekil 2 (a)da grld gibi kullanlan magnezyum tozlar retim ncesi irili ufakl dallantl bir yapya sahiptir. Tozlarn 450oCde 3 basamakta yaklak % 45 orannda deformasyona uradktan sonra bu dallantl yapnn belli ynlerde deforme olduu fakat tam olarak krlp yok olmad grlmtr (ekil 2 (b)). Scaklk ve deformasyonun ayn zamanda uyguland numunelerde belli scaklklarn stnde genellikle dinamik olarak yeniden ekirdeklenme ile e eksenli tane oluumu beklenmektedir. Deformasyonun scakla baskn olduu durumlarda yeni tanelerin olutuu, fakat scakln baskn olduu durumlarda ise dinamik olarak yeniden ekirdeklenmenin mmkn olmad bilinmektedir. Bu almada scak deforme edilen numunelerde yeniden ekirdeklenme ile oluan tanelerin grlememesi her bir basamaktaki deformasyon miktarnn (% 25) az olmasna balanm, scaklnn deformasyon miktarna baskn karak yeniden ekirdeklenmeyi engelledii dnlmtr. Numunelerin 600oCde tavlama sonras ise ok daha farkl bir i yap oluumu gzlenmi, dallantl yapnn tamamen kaybolduu tespit edilmitir. ekil 3te saf magnezyum numunelerinin scak deformasyon ve 600oCde tavlama sonras deformasyona dik ve paralel ynlerdeki i yaplar verilmitir. ekil 3te kaln siyah renkli izgiler magnezyum tozlarnn yzeyinden kaynakl MgO tabakalarn, ince siyah renkli blgeler ise 600oC scaklkta tavlama sonras oluan eeksenli tane snrlarn gstermektedir. Tozlar aras MgO faznn asitle yksek miktarda reaksiyona girmesi sonucu bu blgeler tane snrlarna gre daha kaln yapda grlmektedir. Grld gibi deformasyon sonras yapda bulunan dallantl yap tavlama ilemi sonras dik kesitte ortalama bykl 90 m olan e eksenli tanelere dnmtr. Magnezyum tozlarnda grlen bu eeksenli yapnn yeniden ekirdeklenmeye uramadan dallantl yapdan direk olarak byd grlmtr. Uygulanan tavlama scaklnn (600oC) magnezyumun erime scaklna (650oC) olduka yakn olmas bu direk bymenin nedeni olarak dnlmtr. Numuneleri homojenletirmek, magnezyum tozlarnn sinterlenmesini salamak amal yaplan tavlama ileminin scakln daha da arttrmak mmkndr. Fakat, 630oCde yaplan tavlama ilemlerinde scakln magnezyumun erime noktasnn (650oC) altnda olmasna ramen magnezyum toz yzeylerinde buharlama olduu saptanmtr. Erime noktasnda yaklak 3.5x10-3 atm olan magnezyumun buhar basncnn dk olmas erime noktasna ulalmadan magnezyumun ksmi olarak buharlamasna neden olmakta, bu da tavlama scakln kstlamaktadr. Dier yandan kalsiyum ve lityum gibi yksek derecede oksitlenme potensiyeline sahip olan magnezyum ve magnezyum ieren kompozitlerin yksek scaklklarda retimi de problem olmaktadr. Olas oksitlenme problemlerinden dolay bu almada tavlama scakl 600oCde snrlandrlmtr.
(a) (b) ekil 2. a) Kullanlan magnezyum tozlarnn retim ncesi i yaps, b) scak deformasyon sonras magnezyum numunelerinin deformasyona dik yndeki i yaps.
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ekil 3. 600oC tavlama sonras magnezyum numunelerinin i yaps, a) deformasyona dik kesit, b) deformasyona paralel kesit.
(a) (b) Titanyum ve magnezyumun mekanik zellikleri oksijen gibi arayer atomlarnn znrlnden ve buna ek olarak oluabilecek oksit fazlarndan yksek derecede etkilenmektedir. retilen kompozitlerde titanyum ve magnezyum toz blgelerinde yaplan EDS nokta analizlerinde titanyum ve magnezyum haricinde herhangi bir elemente rastlanmam, faz oluumlarn aratrmak amacyla da balang tozlar ile retilen kompozitlerde numune yzeylerinden tala kaldrldktan sonra deformasyona dik kesitlerde X-Ray analizleri yaplmtr (ekil 4). Grld gibi balang tozlar ile rnek olarak verilen Ti-80Mg kompozit numunesinde herhangi bir oksit ve dier ikincil faz oluumuna rastlanmamtr. retilen dier Ti-Mg kompozit numunelerinde de Ti-80Mg kompozit numunesine benzer krnm erileri gzlenmi fakat magnezyum ve titanyum tozlarnn miktarlarndaki farkllktan dolay magnezyum ve titanyum krnm iddetlerinde deiiklikler olduu gzlenmitir. Saf magnezyum ve Ti-Mg kompozit numunelerinin i blgelerinde oksit veya ikincil faz oluumu gzlenmemesine ramen numunelerin yzeye yakn blgelerinde durumun farkl olduu saptanmtr. Numunelerin yzeyinden tala kaldrlmadan nce yzeye yakn blgelerde yaplan i yap analizlerinde zellikle magnezyum tozlarnn arasnda kalnl 500 nmye ulaan MgO tabakasna rastlanmtr (ekil 5). Numunelerin i blgelerindeki magnezyum tozlarnn arasnda varolan birka nanometre mertebesindeki oksit tabakalar scakln etkisi ile tozlarn bakr ile temas eden yzeye yakn blgelerde bymtr. Bu yzden mekanik test ncesinde btn numunelerin yzeyinden yaklak 1 mm kalnlnda tala kaldrlmtr.
(a) (b) ekil 4. X-Ray krnm rgeleri, a) retim ncesi magnezyum ve titanyum tozlar, b) scak deformasyon ve 600oC tavlama sonras Ti-80% Mg kompozit
(a) (b) ekil 5. (a) Ti-80Mg kompozitlerde yzeye yakn blgelerin i yaps ve analiz alnan blge, (b) ekil 5(a)da gsterilen blgenin EDS izgi analizi.
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ekil 6da alma kapsamnda retilen saf magnezyum ile Ti-50Mg kompozit numunesinin basma ykleri altndaki mekanik davranlar sergilenmekte, Tablo 1de ise retilen btn numunelerin mekanik deerleri verilmektedir. ekil 6da grld gibi hem saf magnezyum, hem de Ti-Mg kompozit numuneleri basma ykleri altnda benzer davran sergilemekte ve gerilim-gerinim erileri elastik blge, gerinim sertleme blgesi ve tepe noktasndan sonra krlma blgesi olmak zere 3 blgeden olumaktadr. Grld gibi saf magnezyum numunesinde kompozitlerden farkl bir gerinim sertleme blgesi grlmtr. Bu blge kompozit numunelerde akma noktasndan maksimum yk noktasna kadar ayn ekilde art gstermesine ramen magnezyum numunelerinde gerilim sertleme derecesinde belli bir gerinim deerinden sonra art gzlenmitir. rnein ekil 6da verilen eride magnezyum, akma noktas ile 0.05 gerinim deeri ve maksimum yk noktas ile 0.05 gerinim deerleri arasnda farkl gerinim sertleme davranlar gstermektedir.
ekil 6. alma kapsamnda retilen baz numunelerin basma yk altndaki gerilim-gerinim erileri Basma testi srasnda gerilim-gerinim erilerinin tepe noktasna ulaldnda ise basma eksenine 45ode yzey atlaklar olumu ve daha sonra malzemeler belli bir gerinimden sonra krlmlardr (ekil 7(a)). Basma srasnda atlaklar hem titanyum toz blgelerinde, hem de titanyum magnezyum arayzeyinde meydana gelmitir. Magnezyum ve titanyum arasnda herhangi bir znrlk olmamasna ramen basma testi srasnda ilgin olarak magnezyum tozlar yapdan btnyle ayrlmam, atlak magnezyum toz taneleri boyunca ilerlemi ve magnezyum tozlar ekil 7(b)de grld gibi gevrek olarak krlmtr. Bu etki ekil 7(a)da da aka grlmekte, ak renkli olan magnezyum toz blgelerinde keskin, dzgn yzeyli basma ynne 45olik gevrek krlma saptanmtr. Daha nce de belirtildii gibi magnezyumun oda scaklnda kayma sistem says az olmakla birlikte, oda scaklnda plastik deformasyon sadece bazal yzeylerde olmaktadr.
(a)
(b)
ekil 7. Ti-80Mg kompozit numunesinde basma testi sonras krlma yzeyleri, a) basma eksenine 45ode oluan krlma, b) Magnezyum ve titanyum toz blgelerinde oluan krlma yzeyleri Bilindii gibi biyomedikal uygulamalarda, zellikle hareketli blgelerde bulunan kemik ve protezler arlkl olarak basma yklerine maruz kalmaktadrlar. Bu tr uygulamalarda kemik ve protez malzemesinin mekanik zelliklerinin birbirine benzerlik gstermesi uzun bir protez mrn garanti etmektedir ve mekanik zelliklerin farkllndan dolay kemik dokusunun anmas ile vcutta meydana gelebilecek hasarlar azaltmas bakmndan nemlidir. zellikle kemik ve protez malzemesinin elastik modllerinin benzerlik gstermesi gerekmekte ve bundan dolay da bu konuda yaplan almalarda implant malzemesinin elastik modlnn kemie benzerlik gstermesi zerine younlamtr. Vcut kemikleri genel olarak sngerimsi ve kortikal kemikler olarak iki ana grupta toplanmaktadr ve kemiklerin elastik modl 3-20 GPa arasnda, basma ykleri altnda akma dayanc ise 130-180 MPa arasnda deimektedir [3]. Tablo 1de grld gibi retilen hem saf magnezyum numunelerinin, hem de Ti-Mg kompozit numunelerin tmnn elastik modlleri vcut kemii elastik modl snrlar iinde kalmakta ve akma dayanlar da ayn ekilde vcut kemiine benzerlik gstermektedir. Grld gibi Ti-Mg kompozitlerde elastik modl, dayan ve akma dayanc magnezyum miktarnn art, dier bir deile titanyum miktarndaki azalma ile d gstermekte, te yandan kompozitlerde krlma noktasndaki uzama ise magnezyum miktarnn art ile artmakta ve saf magnezyum numunesinin uzama deerine (% 19.4 0.5) yaklamaktadr. retilen numunelerin mekanik zelliklerindeki ilgin
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olan nokta ise saf magnezyum ve Ti-Mg kompozit numunelerinin elastik modl deerleri arasnadaki farkllktr. Grld gibi saf magnezyumun elastik modl 20 GPa civarndadr. Magnezyuma titanyum eklendiinde elastik modl deerinde bir art beklenmesine ramen iinde hacimce % 50 titanyum ieren numunede bile elastik modl (12 GPa) saf magnezyumun altndadr. retilen kompozit numunelerde bilinen kompozitlerin aksine glendirici fazn (titanyum) yapda rastgele deil de magnezyum tozlarnn etrafnda dalmasna bal olarak deiik bir mekanik davrann ortaya kt dnlmtr. Bu konuda yaplan almalar devam etmektedir. Dier bir nokta ise retilen saf magnezyum numunelerinin olduka dk mekanik zelliklere sahip olmasdr. lenmi magnezyumlarda basma akma dayanc 130-180 MPa arasnda deimektedir [3]. Fakat bu almada ise retilen magnezyum nunumelerinin akma dayancnn 38 MPa civarnda deitii gzlenmitir. Genel olarak kumda dklen magnezyum numunelerinin akma dayancnn 20 MPa civarnda deitii ve bu deerin ekstrzyon ve scak haddeleme gibi ilemlerle arttrld bilinmektedir. Bu almada retilen saf magnezyum numunelerinin akma dayanc dkm yapsna sahip magnezyum numunelerine benzerlik gstermesine karn, krlma noktasndaki uzama miktar bakmndan ise farkllk gstermektedir. Dkm yaplarnda % 2-6 arasnda deien uzama miktar bu almada retilen magnezyum numunelerinde yaklak % 20ye kadar ulamtr. Numunelerin 450oCde deformasyon sonras 600oC gibi ok yksek scaklkta uygulanan tavlama ilemi taneleri bytm ve ayn zamanda malzemedeki retim kaynakl gerilimleri de yok etmitir. Tablo 1. alma kapsamnda retilen numunelerin mekanik zellikleri Elastik Modl, E Akma Dayanc, Dayan, UTS Krlma noktasndaki (GPa) 0.2 (MPa) (MPa) uzama, (%) 20.8 1.4 38.2 3.3 260.0 4.1 19.4 0.5 12.0 1.1 245.0 9.6 411.7 9.4 12.9 0.3 12.5 0.6 194.0 5.3 390.0 11.6 15.1 1.0 9.6 0.5 147.3 4.9 337.8 7.4 15.4 0.6 6.0 0.7 123.0 6.4 329.5 7.6 18.0 1.0
Numune Saf Magnezyum Ti-50%Mg Ti-60%Mg Ti-70%Mg Ti-80%Mg
4. SONULAR Bu almada gzeneksiz, biyomedikal uygulamalara aday saf magnezyum ve iinde hacimce % 50-80 arasnda deien oranlarda magnezyum ieren Ti-Mg kompozitleri scak deformasyon yntemiyle retilmitir. retim esnasnda uygulanan tavlama ilemi sonras Ti-Mg kompozitlerdeki magnezyum tozlarndaki grlen iri tanelerin dallantl yapdan direk olarak byd saptanmtr. Dier yandan 600oCde uygulanan tavlama ileminin ise titanyum tozlarnn sinterlenmesi iin yeterli olmad ve tozlarn yapda birbirine sadece mekanik olarak ok iyi derecede kilitlendii grlmtr. Ayrca retim sonras yaplan incelemelerde magnezyum tozlarnn arasndaki oksit tabakalarnn yzeye yaklatka kalnlat, numunelerin i blgelerinde ise sadece balang tozuna bal bir oksit tabakasnn olduu grlmtr. Yaplan basma testlerinde ise btn numunelerin gerinim-gerinim erilerinin elastik blge, gerinim sertlemesi ve krlma blgesi olmak zere 3 ana blgeden olutuu saptanm ve malzemelerin snekliinin olduka yksek olduu saptanmtr. Maksimum yk sonras kompozit numunelerde krlma basma ynne 45ode meydana gelmitir. Krlma titanyum toz blgelerinde, titanyum ve magnezyum toz arayzeyinde ve de magnezyum tozunun kendisinde meydan gelmitir. Magnezyumun oda scaklnda snrl sayda kayma sistemine sahip olmas magnezyumun gevrek ekilde krlmasna neden olmutur. Bunun yannda retilen saf magnezyum nunumelerinde sneklik olduka yksek olmasna ramen elastik modl ve akma dayancnn dkm yapsna sahip magnezyuma benzerlik gsterdii grlm, bunun nedeni de uygulanan tavlama ileminin scaklnn ok yksek olmasna balanmtr. retilen kompozitlerde elastik modl 6-12 GPa, akma dayanc da 123-245 MPa arasnda deimektedir. Vcut kemiinin elastik modl (3-20 GPa) ve akma dayancna (130-180 MPa) benzerlik gsteren Ti-Mg kompozitleri mekanik zellikler bakmndan biyomedikal uygulamalara olduka uygun olduu grlmtr. KAYNAKLAR 1. M. Geetha, A.K. Singh, R. Asokamani, A.K. Gogia, Ti based biomaterials, the ultimate choice for orthopedic implants- A review, Progress in Materials Science, 54, pp. 397- 425, 2009. 2. F. Barrre, T.A. Mahmood, K. De Groot, C.A. van Blitterswijk, Advanced biomaterials for skeletal tissue regeneration: Instructive and smart functions, Materials Science and Engineering R 59, pp. 38-71, 2008. 3. M. P. Staiger, Alexis M. Pietak, J. Huadmai, G. Dias, Magnesium and Alloys as orthopedic biomaterials: A review, Biomaterials, 27, pp. 1728-1734, 2006. 4. M. Bram, C. Stiller, H. P. Bunckremer, D. Stover, H. Baur, Titanium foams produced by solid state replication of NaCl powders, Adv. Eng. Mater., 2, pp. 196-199, 2000. 5. C. E. Wen, M. Mabuchi, Y. Yamada, K. Shimojima, Y. Chino and T. Asahina, Processing of biocompatible porous Ti and Mg, Scripta Mater., 45, pp. 1147-1153, 2001. 6. C. E. Wen, Y. Yamada, K. Shimojima, Y. Chino, H. Hosokawa, and M. Mabuchi, Novel titanium foam for bone tissue engineering, J. Mater. Res., 17(10), pp. 2633-2639, 2002. 7. Nayeb-Hashemi and J.B. Clark, Phase diagrams of magnesium alloys, ASM international, pp 324, 1988.
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Semente Bakr Matrisli- SiC Kompozitlerinin Toz Metalurjisi Yntemi ile retimi
G. Celebi Efe, . Altnsoy, T. Yener, M. Ipek, S. Zeytin, C. Bindal Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, Esentepe Kamps, 54187 Sakarya- Trkiye, E-mail:gcelebi@sakarya.edu.tr zet Bu almada elektriksel uygulamalar iin 5 ve 30m boyutunda ve arlka % 0, 1, 2, 3 ve 5 miktarda SiC ieren semente Cu matrisli SiC takviyeli kompozitlerin retimi amalanmtr. Semente bakr ve SiC tozlar mekanik olarak kartrlm ve 280 MPa basnta tek ynde preslenmitir. Preslenen kompaktlar 700Cde 2 saat ak atmosferli frnda sinterlenmitir. Kompozitteki Cu ve SiC bileenlerin varl XRD analiz teknii ile tespit edilmitir. Kompozitlerin nispi younluk ve elektrik iletkenlikleri, arlka artan SiC yzdesiyle azalrken artan SiC parack boyutuyla artmtr. Sonular, 30m parack boyutlu SiC ile takviye edilen Cu-SiC kompozitlerinin 5m parack boyutlu SiC ile takviye edilen Cu-SiC kompozitlerinden daha iyi zellikler sergilediini gstermitir. Maksimum nispi younluk (97%) ve elektrik iletkenlik deeri (%83.0 IACS: International Annealed Copper Standard) 30m luk SiC ile takviye edilen Cu-a.%1SiC kompoziti iin elde edilmitir. Anahtar Kelimeler: Cu-SiC, Sementasyon, Kompozit, Sertlik, Nispi Younluk, Elektrik letkenlii
The ProductIon of Cemented Cu MatrIx-SIC ComposItes By Powder Metallurgy Method

G. Celebi Efe, . Altnsoy, T. Yener, M. Ipek, S. Zeytin, C. Bindal Sakarya University, Engineering Faculty, Department of Metallurgy and Materials Engineering, Esentepe Campus, 54187 Sakarya-Turkey, E-mail:gcelebi@sakarya.edu.tr Abstract The present paper is aimed at the production of cemented Cu matrix-SiC composites with SiC having 5 and 30m particle size and at ratios of 0, 1, 2, 3 and 5% by weight for electrical applications. Cemented copper and SiC powders were mixed mechanically and pressed with an axial pressure of 280MPa. Pressed compacts were sintered at 700C in an open atmospheric furnace for 2 hours. The presence of Cu and SiC components in composites were verified by XRD analysis technique. While relative density and electrical conductivity of composites were decreasing with increasing the weight percentage of SiC, increased with increasing particle size of SiC particles. Hardness of the composites increased with both weight percentage and the particle size of SiC particles. The results indicate that Cu-SiC composite with 30m particle sized SiC has superior properties than the Cu-SiC composite with 5m particle sized SiC. The maximum relative density of 97% and electrical conductivity of 83.0%IACS (International Annealed Copper Standard) were obtained for Cu-1wt.%SiC with SiC particle size of 30m. Keywords: Cu-SiC, Cementation, Composite, Hardness, Relative density, Electrical conductivity. 1. GR Bakr, tm metaller arasnda gmten (6,21x107/.m) sonra elektrik iletkenlii en yksek metal (5,88x107/.m ) olup elektrik iletkenliinin ana talep olduu uygulama alanlarnda yaygn olarak kullanlmaktadr. Gm, yksek
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fiyat ve tedarikindeki glkler nedeni ile bu tr uygulama alanlarnda az kullanlmaktadr. Bakra bir rakip yine elektrik iletkenlii yksek olan alminyumdur, ancak onun hem iletkenlii (3,65x107/.m) hem de mukavemeti bakrnki kadar yksek deildir. Bakrn dier btn metaller ierisinde gmten sonra elektrii en iyi ileten metal olmas, elektrik iletkenliinin ana talep olduu uygulama alanlarnda yaygn olarak kullanmn salamaktadr [1, 2]. Bakrn yksek elektriksel iletkenlii (5,88x107/.m ), yksek sl iletkenlii (400 W/m.K), korozyon direnci, dekoratif rengi, orta derecedeki mukavemet ve kolay ekillendirilebilirlii onu tarih boyunca nemli klmtr ve [1, 3] eitli mhendislik uygulamalarnda en ok kullanlan yapsal ve ilevsel metallerden biri yapmtr [4- 6]. letkenler, elektrotlar, ama kapama kontaklar gibi elektrik iletkenliinin birinci derecede nemli olduu uygulama alanlarnda kullanlacak olan bakrlarda u temel zellikler aranr: Yksek elektrik iletkenlii, yksek oda scakl mukavemeti, mukavemetini yksek scaklklarda koruyabilme zellii (yksek scaklk mukavemeti). Saf bakr, ilk zellik asndan neredeyse rakipsiz bir malzemedir. Bu noktada oksijensiz yksek iletken bakr ok uygundur. Ancak, saf bakrn snrl bir mukavemeti vardr [3, 6- 8]. Bakrn dk mukavemeti ve zellikle yksek scaklklarda yumuamas yaygn kullanm alann kstlamaktadr [5, 9]. Bakr elektrik iletkenliinde nemli bir kayp olmakszn, sadece souk deformasyon ile sertletirilebilir. Bu ekilde mukavemetlendirilse bile, saf bakr 100oCye yaklaan scaklklarda, hzl bir ekilde yeniden kristalleir, sertlik ve mukavemetini kaybeder. Bakrn mukavemetini artrmann bir dier yolu alamlamadr. Alamlama sonucunda, bakr alamnn mukavemeti ya kat eriyik sertletirmesi veya kelti sertletirmesi ile artrlabilir. Ancak, elektrik iletkenliindeki kaybn yksek olmamas iin alam elementi ilavesinin snrl tutulmas gerekir. nk alam elementi ilavesi ile, mukavemetin artmasna karlk elektrik iletkenlii azalr. Bu bakmdan, iletken olarak kullanlacak bakr alamlarnda az miktarda alam elementi bulunur (genellikle a. %2 mertebesinde). Bilindii gibi, yalandrlm alamlar yalandrma scaklnn zerinde kullanlmamaldr, aksi halde hzla yumuarlar. Dolaysyla, az alaml bakrlarn mukavemet performanslar ykselen scaklklarda deimektedir [10]. Bakrn yksek scaklklarda azalan zelliklerini kazanmann bir yoluda, bakr matris ierisinde seramik paracklarinin dispersiyonu ile kompozit oluturmaktr. Bu amala bakr matrise ilave edilen seramiklere rnek olarak Al2O3, SiC, TiC, WC, B4C ve TiB2 saylabilir [5]. Bunlardan, SiC yksek elastik modl ve aluminadan ok daha yksek sl iletkenlii ile dikkat ekmektedir. Cu- SiC kompozitleri, bakrn iyi sneklii ve tokluu ile SiC paracklar takviyelerinin yksek mukavemeti ve elastik modllerinin her ikisini birletirir [11]. Bu kompozitler diren kaynak elektrotlar, klavuz ereveleri, elektrik klemensleri, rleler, iletkenler, kondaktrler, elektrik anahtarlar, akm devresi kesicileri, elektronik paketleme uygulamalarnda elektrik temas malzemeleri olarak kullanlabilirler [11- 13]. Bu almada sementasyon yntemiyle retilen bakr tozunun farkl parack boyut ve bileimdeki seramik karakterli SiC tozu ile takviye edilerek yksek iletken Cu-SiC kompozit retimi hedeflenmitir. Sonular mekanik, mikroskobik ve elektriksel olarak karakterize edilmitir. 2. DENEYSEL ALIMALAR almalarda balang malzemeleri olarak semente bakr (%99.5 safiyette, 0.1-0.5 m) ve SiC (% 99.5 safiyette, 5 ve 30 m, Struers) tozlar kullanlmtr. Balang tozlar bilyeli deirmende 2 saat sre ile kartrlarak, semente Cu-SiC (5 m) ve semente Cu-SiC (30 m) eklinde, srasyla a. % 1, 2, 3 ve 5 SiC takviyeli toz karmlar hazrlanm ve sz konusu karmlar tek eksenli kalp ierisinde pres yardmyla 280 MPa basnla kompaklanmtr. Kompaktlanan numuneler grafite gml halde ak atmosferli elektrikli frnda, 700oCde 2 saat sinterlenmitir. Sinterlenen numunelerin nispi younluklar Arimed Prensibi ne gre hesaplanm, sertlik ve elektriksel iletkenlikleri srasyla Vickers indentasyon teknii ve DC elektrik iletkenlik lm cihaz kullanlarak llmtr. Numunelerin mikroyaplar SEM mikroskobu ile incelenmi ve kompozitlerin ierisindeki fazlar XRD analizi ile belirlenmi, SEM incelemelerindeki baz bulgular ve XRD analizi SEM-EDS yardmyla teyit edilmitir. 3. DENEYSEL SONULAR ve TARTIMA Sinterlenmi semente Cu-SiC (5 ve 30 m) kompozit numunelerine ait SEM mikroyaplar ekil 1ve 2de gsterilmitir. Mikroyaplar incelendiinde, gri, geni alanlarn Cu, siyah ve keli paracklarn ise SiC olduu grlmektedir. Takviye miktar artka SiC paracklerinin matriks ierisindeki miktar artmakta ve paracklar aras mesafe ksalmaktadr. Her iki SiC parack boyutuna sahip numunelerde de, takviye faz matriks ierisinde Cu taneleri etrafnda homojen olarak dalmaktadr (ekil 1-2). Sz konusu homojen dalm daha kk (5 m) SiC patiklleriyle takviye edilmi numunelerde daha belirgin gzkmektedir. SiC parack boyutu arttka SiC dalm daha uzun mesafeli hale gelmektedir (ekil 2). Mikroyaplarda grlen kk beyaz kresel paracklar ise parlatma malzemesi olan Al2O3 n matriks yzeyine gmlmesinden kaynaklanmaktadr.
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ekil 1. Sinterlenmi semente Cu-SiC (5 m) kompozit numunelerine ait SEM mikroyaplar.
ekil 2. Sinterlenmi semente Cu-SiC (30 m) kompozit numunelerine ait SEM mikroyaplar. Kompozit numuneler ierisinde balang bileenleri dnda, proses srelerine bal olarak hangi fazlarn bulunduu XRD analizleriyle incelenmi ve analiz sonular grafiksel olarak ekil 3 ve 4 te verilmitir. (XRD patternlerinde C1Ss eklindeki ksaltmalarda C: bakr, rakam: takviye miktarn ve S: SiC, s: semente matriks tozu kullanldn sembolize etmektedir.) XRD analizlerinde SiC ve Cu dnda bir faza rastlanlmamtr (ekil 3-4). SiC piklerinin SiC miktarndaki arta bal olarak belirginlememesi ise takviye miktarlarnn XRD cihaznn deteksiyon limitlerine yakn olmasndan kaynaklanabilmektedir.
ekil 3. 700 Cde sinterlenen 5m tane boyutunda SiC ieren Cu (semente)-SiC kompozitlerinin XRD paternleri.
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ekil 4. 700 Cde sinterlenen 30m tane boyutunda SiC ieren Cu (semente)-SiC kompozitlerinin XRD paternleri. XRD ile tespit edilen hakim fazlar ve yapdaki bilenler SEM- EDS nokta analizleri desteklenmitir. 700Cde sinterlenmi 5 ve 30mluk SiC ile takviye edilmi Cu-SiC kompozitlerine ait SEM-EDS analizleri ekil 5, 6 da verilmitir. Analizlerde koyu gri ve keskin keli fazlar SiC ak gri alanlar Cu matriksi, serbest beyaz alanlar muhtemelen parlatmadan kaynaklanan alminay gstermektedir. ekil 6 da matriste serbest gri renkte adacklarn bulunduu grlmtr. Bu blgelerden biri olan 3 noktasndan alnan SEM-EDS analizlerinde Fe ve O2 tespit edilmitir. Fe sementasyon prosesinden kaynaklanmaktadr ve muhtemelen sinterleme scaklnda oksitlenmitir.
ekil 5. 700Cde sinterlenmi 5 mluk SiC ile takviye edilmi C5Ss numunesinin EDS analizi.
ekil 6. 700Cde sinterlenmi 30 mluk SiC ile takviye edilmi C2Ss numunesinin EDS analizi.
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700Cde sinterlenmi numunelerin Archimedes prensibi ile llen nispi younluklarnn SiC ieriine ve boyutuna bal olarak deiimi ekil 7 de stun grafii olarak verilmitir. Semente bakr tozuna SiC takviyesi ile nispi younluklar azalmaktadr. SiC parack takviyeli numunelerde younluk, SiC parack boyutu art ile artmaktadr. Kompozit numunelerde dk SiC hacim oranlarnda Cu-SiC arayzeyi daha azdr ve bakr atomlar iin daha az difzyon bariyeri sz konusudur. Bakr atomlarnn kolaylkla difze olmas ve SiC paracklar arasndaki boluklar doldurabilmesi kompozitte younluk artna neden olur [14]. SiC parack boyutu arttka yzey alan ve Cu-SiC arayzeyleri azalmakta, buna bal olarak ta daha youn bir yap ortaya kmaktadr. Kompozitlerin nispi younluklar SiC parack boyutunun artyla art sergilemitir ve en iyi younluk deerleri 30 mluk SiC parack takviyeleri ile elde edilmitir. SiCn artan parack boyutu ile birlikte, daha fazla bakr-bakr taneleri birbirleri ile temas etmekte ve sinterleme sonrasnda daha youn bir yap ortaya kmaktadr.
ekil 7. 700C de Sinterlenmi kompozitlerin % nispi younluklarnn SiC ieriine ve boyutuna bal olarak deiimi. Kompozit numunelerde sertlik lm Cu ve SiC tanelerini homojen olarak kapsayacak ekilde iz oluturulmasna dikkat edilerek yaplmtr. Cu ve 5mluk SiC takviyeli Cu-SiC kompozitlerinin sertlik lmlerinde 50gr yk, 30mluk SiC takviyeli Cu-SiC kompozitlerinin sertlik lmlerinde ise, sertlik izinin Cu ve SiCn her ikisinide kapsamas iin 100gr yk kullanlmtr. Kompozitlerin sertliinin SiC ieriine ve parack boyutuna bal olarak deiimi ekil 8de stun grafiinde verilmitir.
ekil 8. 700C de Sinterlenmi kompozitlerin sertliklerinin SiC ieriine ve boyutuna bal olarak deiimi. SiC ierii arttka kompozitlerin sertlik deerleri artmtr. Snek bakr matrisin sertlii sert disperse faz ilavesiyle artmaktadr [15, 16]. Kompozit numunelerin mikrosertlik deerlerinin SiC parack boyutunun artmasyla daha da artmasnn nedeni, indenterin sert takviye bileenine temas alannn artmas olabilir. Cu ve Cu-SiC kompozitlerinin elektrik iletkenliklerinin SiC boyut ve ieine gre deiimi ekil 9 da verilmitir. Nispi younluk sonularna benzer ekilde kompozititn elektrik iletkenlii artan SiC miktar ile artmaktadr. Matris ierisinde dalan SiC paracklar elektron hareketine engel olarak elektrik iletkenliini drmektedir. SiC tane boyutu arttka birim alana den SiC parack says azaldndan elektrik iletkenlii artmtr.
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ekil 9. 700C de Sinterlenmi kompozitlerin sertliklerinin SiC ieriine ve boyutuna bal olarak deiimi. 4. SONULAR Gerekletirilen amada aadaki sonular elde edilmitir: 1. Cu-SiC kompozitleri, sementasyon yntemiyle retilen bakr tozuna farkl ierik ve boyutta SiC paracklar takviye edilerek, Toz Metalurjisi yntemiyle baaryla retilmitir. 2. Kompozillerdeki hakim fazlar Cu ve SiC, XRD ve SEM- EDS nokta analizleri ile tespit edilmi ve yapda herhangi bir oksit pikine rastlanlmamtr. 3. Takviye bileeni olan SiC paracklar matriks ierisinde homojen olarak dalmtr. 4. 700C de 2 saat sinterlenmi kompozilerin nispi younluklar ve elektrik iletkenlikleri, artan SiC miktar ile birlikte azalrken, artan SiC parack boyutuyla art gstermitir. 5. Kompozitlerin mikrosertlikleri artan SiC miktar ve parack boyutu ile artmtr. TEEKKR Yazarlar Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm teknikeri Ersan DEMIRe, SEM, XRD incelemelerini gerekletiren uzman Fuat KAYIa, Federal Elektrik A..ye, TBTAKa teekkkr ederler. KAYNAKLAR 1. www.bpc.edu/mathscience/chemistry/electrical_conductivity.html 2. http://en.wikipedia.org /wiki/Copper 3. www.cda.org.uk 4. Zhu, J., Liu, L., Zhao, H., Shen, B., Hu, W., Microstructure And Performance of Electroformed Cu/Nano-Sic Composite, Materials & Design, Vol. 28, pp. 1958-1962, 2007. 5. Xu, Q., Zhang, X., Han, J., He, X., Kvanin, V.L., Combustion Synthesis and Densification of Titanium Diboride-Copper Matrix Composite, Materials Letters, Vol. 57, pp. 4439-4444, 2003. 6. Dobrzanski, L.A., Significance of Materials Science for The Future Development of Societies, Journal of Materials Processing Technology, Vol. 175, pp.133-148, 2006. 7. Zhan, Y., Zhang, G., The Effect of Interfacial Modifying on The Mechanical and Wear Properties of Sicp/Cu Composites, Materials Letters, Vol. 57, pp.4583-4591, 2003. 8. http://www.matweb.com/reference/copper-alloys.aspx 9. Ahmed, R. N., Ramesh, C.S., Tribological Properties of Cast Copper-Sic-Graphite Hybrid Composites, International Symposium of Research on Materials Science and Engineering, Chennai India, December 20-22, 2004. 10. Salam, ., Cu-Cr-Zr Alamnda Yalandrma Isl leminin, Elektrik letkenlii ve Anma Davranlar zerine Etkisinin ncelenmesi, Bilim Uzmanl Tezi, Karabk niversitesi, Fen Bilimleri Enstits, Makine Eitimi Anabilim Dal, Ocak, 2008. 11. Zhang, R., Gao, L., Guo, J., Effect Of Cu2O on The Fabrication of Sicp/Cu Nanocomposites Using Coated Particles and Conventional Sintering, Composites, Vol. 35, pp. 1301-1305, 2004. 12. Motta, M.S., Jena, P.K., Brocch, E.A., Solorzano, I.G., Characterization of Cu-Al2O3 Nano-Scale Composites Synthesized By In Situ Reduction, Materials Science and Engineering C, Vol. 15, pp. 175-177, 2001. 13. Zhang, R., Gao, L., Guo, J., Temperature-Sensitivity of Coating Copper on Sub-Micron Silicon Carbide Particles by Electroless Deposition in A Rotation Flask, Surface and Coatings Technology, Vol. 166, pp. 67-71, 2003. 14. Efe, C.G., Altinsoy, I., Ipek, M., Zeytin, S., Bindal, C., Some Properties of Cu-Sic Composites Produced by Powder Metallurgy Method, Kovove Metallic, Vol. 49, No.2, pp. 131- 136, 2011. 15. Efe, C.G., Altnsoy, ., Ipek, M., Zeytin, S., Bindal, C., Investigation of Some Properties of Sic Particle Reinforced Copper Composites, 5. Uluslararas Toz Metalurjisi Konferans, Ankara, 8-12 Ekim 2008. 16. Celebi Efe, G., Altinsoy, I., Yener, T., Ipek, M., Zeytin, S., Bindal, C., Characterization of Cemented Cu-SiC Composites, Vacuum, Vol. 85, pp. 643-647, 2010.
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FERROUS POWDER METALURGY
www.turkishpm.org
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THE MICROSTRUCTURE AND PROPERTIES OF LOW CARBON PM Mn STEELS SINTERED UNDER DIFFERENT CONDITIONS
Maciej SULOWSKI*, Andrzej CIAS*, Tadeusz PIECZONKA* *AGH University of Science and Technology, Faculty of Metals Engineering and Industrial Computer Science, Physical and Powder Metallurgy Research Unit, PL 30-059 Krakw, Poland, Al. Mickiewicza 30, sulek@agh.edu.pl ABSTRACT The paper presents the effect of sintering conditions on the microstructure and properties of low-carbon Mn-Cr-Mo PM steels. It was proved there is no effect of tempering temperature on the mechanical properties of Astaloy CrLbase steels, sintered at 1250C in 5H2-95N2 mixture as compared with the properties of those sintered at 1120C. The properties of Astaloy CrM-base steels, sintered at 1250C in air were comparable or higher on the contrary to Astaloy CrL-base steels. The addition of lump ferromanganese was not sufficient for metal oxides reduction. The structure investigation confirmed the Mn-Cr-Mo PM steels have predominantly bainitic microstructure. Keywords: Structural PM Materials, PM Mn Steels, Sintering Process, Sintering Atmosphere, Microstructure, Mechanical Properties. 1. INTRODUCTION Manganese and chromium are two important elements in steels, which show effective strengthening. The issue of sintering low alloy steels containing these metals having high affinity for oxygen is one of the most important topics in powder metallurgy (PM), as testified by the number papers on this subject that have taken place over the last few years [1-6]. The question of the role of micro-atmosphere in the development of microstructure is fundamental to our understanding of sintering process, especially the relationship of microstructure evolution to mechanical properties evolution. The thermodynamics bonds concerning carbon equilibrium during sintering were discussed and possible interactions between steel and various controlled atmosphere were examined [7-10]. Therefore it is anticipated that this topic would generate a great deal of interest among powder metallurgy specialists. The PM industry needs economical ways of producing components with higher densities in order to effect the stepwise improvement in dynamic mechanical properties necessary to compete with highly loaded wrought and machined components. This paper aims to determine the processing conditions necessary for standard and high temperature sintering in nitrogen rich, non-flammable atmospheres of PM ferrous structural parts, which contain the easily oxidisable chromium and manganese in addition to carbon and molybdenum. These components are to possess high fatigue strength, good dimensional accuracy, be fully recyclable and of lower cost than equivalent wrought and machined parts. Recyclability is achieved by substitution of the normal (for PM) alloying elements of copper and phosphorus by chromium and manganese. Recyclable components are of paramount importance to automotive manufacturers due to increasingly stringent legislation that now sees the manufacturers responsible for the whole life cycle of vehicles, i.e. birth to grave. Another element often used in PM is the expensive and potentially carcinogenic nickel. Its exclusion as an alloying element can only make for a safer workplace. Also the issue has a high profile in public awareness because of a series of magazine articles. To research a potentially economical route for production of components made of Fe- Mn-Cr-Mo-C structural steels, ways of maximising mechanical properties were investigated. The slow cooling of large masses in semi-closed containers in the sintering furnace favours bainite formation. Correct sinter-hardening of these steels should lead to a tough, potentially bainitic, core with a hard wear resistant surface. The new processing conditions aim to make use of carbothermic reduction of metal oxides by promotion of a local micro-climate or micro-atmosphere around the sintered components, with
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low oxygen potential and high CO/CO ratio. It is well known, from iron and steel-making processes, that at tem2 peratures >900C carbon monoxide is a more efficient reducing gas than pure dry hydrogen. Also CO is efficiently 2 reduced to CO by solid carbon by means of the Boudouard reaction at temperatures >927C. It was proposed to model theoretically the metal-metal oxide-carbon reactions to predict the generation of CO and CO versus tem2 perature and the projected efficiency for gaseous-metal oxide reduction. These analyses were used to corroborate the theoretical modelling and also to help with design improvements of semi-closed container systems. The use of semi-closed containers is envisaged in order to produce and maintain an efficient reducing atmosphere around the components being sintered. Various semi- closed container designs have been used previously in [1116] during authors work on the understanding and development of sintering parameters for manganese and chromium containing PM alloys. The relatively small volume of reducing gas (CO/CO ) in these containers ensures that 2 the process is more eco-friendly than when either flowing endogas (unacceptable due to its wetness) or cracked ammonia (or other nitrogen-hydrogen, minimum 10%, mixture) plus methane addition is employed, as currently in industry. The use of carbon and/or manganese vapour producing getter systems will be investigated for the purposes of increased CO/CO2 generation and drying of the micro-climate, thus ensuring low oxygen potential and best possible reducing conditions. Avoidance of formation of deleterious manganese and chromium oxides and chromium nitrides has already been demonstrated. 2. EXPERIMENTAL PROCEDURE The pre-alloyed Hgans Astaloy CrL and Astaloy CrM powders were used as the base materials. 3% of manganese, in the form of low-carbon (1.3% C) ferromanganese (77% Mn), and 0.15% ultra fine graphite powder were added to the base powders in order to prepare two mixtures Fe-3%Mn-1.5%Cr-0.2%Mo-0.15%C and Fe-3%Mn-3%Cr0.5%Mo-0.15%C, based on Astaloy CrL and Astaloy CrM, respectively (Fig. 1).
Figure 1. Micrographs of base powders: a) pre-alloyed Astaloy CrL powder, b) pre-alloyed Astaloy CrM powder, c) ferromanganese Elkem powder, d) graphite powder grade C-UF. The powders were mixed in a Turbula mixer for 30 min, and compacted in steel dies with zinc stearate lubricated walls. Two types of compacts were prepared: 55x10x5 mm TRS specimens and ISO 2740 dog-bone tensile test bars. The green and as-sintered densities of compacts, d0 and d1, respectively, are summarised in Table 1. Before sintering process, green compacts of each mixture were numbered from 1 to 40. The scheme of sintering is presented in Table 2. Isothermal sintering was carried out: in dry (10 ppm moisture) 5% H2-95% N2 (the flow rate of atmosphere was approximately 1 ml/min) atmosphere in the laboratory horizontal tube furnace, in presence of Mn vapours (a lump of the ferromanganese was placed in the boat), at 1120C and 1250C for 60 minutes, employing convective (65Cmin-1) cooling. To improve the local dew point of microatmosphere and to minimise the loss of manganese due to volatilisation, sintering was carried out in a semi-closed stainless steel container.
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The mass of lump of FeMn was 52 g and it was added per 489,5 g of compacts, both rectangular and ISO 2740. The total number of compacts during single sintering process was 20 - 10 rectangular and ISO 2740. Samples based both on Astaloy CrL and Astaloy CrM pre-alloyed powders, numbered 6-10, 16-20, 26-30 and 36-40 were subsequently tempered at 200C for 60 minutes in air. Table 1. Green densities, d0, and as-sintered densities, d1, of Fe-Mn-Cr-Mo-C PM steels - mean values for 40 (green compacts) and 20 (as-sintered materials) measurements.
Table 2. The scheme of sintering compacts.
3. RESULTS The mechanical properties of investigated PM steels are summarised in Table 3 and in Figures 2-9. LECO instruments were employed to check the chemical composition of Fe-Mn-Cr-Mo-C PM steels. After mechanical tests, the structure of sintered Mn-Cr-Mo steels was examined using light optical microscopy (LOM) technique. Table 3. Mechanical properties of Fe-3Mn-Cr-Mo-C steels based on Astaloy CrL prealloyed powder- mean values and standard deviation.
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Figure 2. Representative tensile curves for Astaloy CrL-based 3%Mn + 0.15%C PM steels sintered at 1120C in 5% H2 / 95% N2 mixture; not tempered (right) and after tempering (left).
Figure 3. Representative tensile curves for Astaloy CrL-based 3%Mn + 0.15%C PM steels sintered at 1120C in air + 52g FeMn (added in the form of a lump); not tempered (right) and after tempering (left).
Figure 4. Representative tensile curves for Astaloy CrL-based 3%Mn + 0.15%C PM steels sintered at 1250C in 5% H2 / 95% N2 mixture; not tempered (right) and after tempering (left).
Figure 5. Representative tensile curves for Astaloy CrL-based 3%Mn + 0.15%C PM steels sintered at 1250C in air + 52g FeMn (added in the form of a lump); not tempered (right) and after tempering (left).
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Figure 6. Representative tensile curves for Astaloy CrM-based 3%Mn + 0.15%C PM steels sintered at 1120C in 5% H2 / 95% N2 mixture; not tempered (right) and after tempering (left).
Figure 7. Representative tensile curves for Astaloy CrM-based 3%Mn + 0.15%C PM steels sintered at 1120C in air + 52g FeMn (added in the form of a lump); not tempered (right) and after tempering (left).
Figure 8. Representative tensile curves for Astaloy CrM-based 3%Mn + 0.15%C PM steels sintered at 1250C in 5% H2 / 95% N2 mixture; not tempered (right) and after tempering (left).
Figure 9. Representative tensile curves for Astaloy CrM-based 3%Mn + 0.15%C PM steels sintered at 1250C in air + 52g FeMn (added in the form of a lump); not tempered (right) and after tempering (left).
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Following the results of chemical analysis presented in Table 4, higher sintering temperature contributes the decarburization effect in investigated steels. This effect is connected with carbothermic reaction between C and O2 which can be possible during the whole heating and sintering steps. This phenomenon was widely reported by Cias et al [11]. Also the lower oxygen content in PM steel after sintering at 1250C suggests the carbon oxygen reactions. It has to be also pointed out that sintering in air with additions of FeMn, irrespective to sintering temperature, contributes to decreasing decarburization effect due to the shortage of hydrogen. Higher nitrogen level in investigated steels can be explained by nitrogen-rich atmosphere; also porosity which is seen in Figs. 10-11 play important role in nitriding Mn-Cr-Mo PM steels. Table 4. Chemical composition of investigated not tempered 3Mn-Cr-Mo-0.15C PM
Figure 10. The microstructure of Astaloy CrL-based not tempered steel sintered at 1120C (left) and 1250C (right).
Figure 11. The microstructure of Astaloy CrM-based not tempered steel sintered at 1120C (left) and 1250C (right). The heterogeneous microstructure of investigated PM steels observed in bright field (Figs. 10 and 11) mainly consists of martensite or martensite+bainite (lower and upper); also a lot of upper bainitic islands, homogeneous arranged, were observed. 4. DISCUSSION The strength properties of PM Mn-Cr-Mo-C steels obtained during investigations indicate that these steels can be classified as medium-to-high strength wrought steels. As was shown in Tables 1, compacts based on Astaloy CrL pre-alloyed powder are characterised by a little bit higher densities than those based on Astaloy CrM powder. It can be connected with better compressibility of powder mixture containing less chromium and molybdenum. Mechanical properties of investigated PM steels were summarised in Tables 3 and in Figures 2-9. High temperature sintering of steels based on Astaloy CrL powder in 5%H2-95% N2 mixture and their tempering doesnt influence on strength properties of investigated steels. UTS and TRS strengths and R0,2 yield offset are comparable
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for tempered and not tempered samples; toughness and hardness values recorded for not tempered samples increased by 4.8% and 25% than those obtained for as-tempered steels. There are some materials e.g. gray cast iron or porous steels for which the initial elastic portion of the stress-strain curve is not linear; hence, it is not possible to determine a modulus of elasticity as for wrought steel. For this nonlinear behaviour, either tangent or secant modulus is used. Tangent modulus is taken as the slope of the stressstrain curve at some specified level of stress, while secant modulus represents the slope of a secant drawn from the origin to some given point of the stress-strain curve. For the investigated specimens the proportional limit stress was ~160MPa and Young modulus at this limit (measured either as secant or tangent modulus) was 150GPa (146160GPa measured using ultrasonic technique). The mechanical properties of both group of steels (Astaloy CrL and Astaloy CrM-based materials) are comparable, irrespective of sintering atmosphere. Not tempered steels, sintered in air with addition of 52g of FeMn obtained higher mechanical properties. After sintering at 1120C in 5%H2-95% N2 mixture, irrespective of heat treatment, the comparable mechanical properties of investigated PM steels were obtained. Mechanical properties of steels based on Astaloy CrM prealloyed powder, sintered at 1250C in air with addition of 52g of FeMn were higher or comparable to properties of low- chromium, low-molybdenum steels sintered at the same temperature in 5%H2-95% N2 atmosphere. A specific characteristic of manganese in relation to sintering mechanisms is its vapour pressure, the highest of all the alloying elements in PM structural steels. Its significance was first recognised by Salak [17, 18], who reported that manganese sublimation and evaporation plays a significant part in such phenomena as homogenisation and self-gettering action of Mn vapour. The observed rapid alloying of iron particles in Mn steels can only be accounted for by transport of manganese via gaseous phase. High manganese vapour pressure make possible manganizing of the sintered alloy, a process the diffusion of manganese into the surface of a metal, particularly the steel compacted powder particles, and improve its mechanical properties. This may be achieved by sintering the compacts (open-porous material) at 1100-1250C in a sealed boat packed with compacts and ferromanganese lumps and with an inert gas/manganese vapour atmosphere. Additionally manganese and carbon loss is lowered. The effect low temperature sintering (at 1120C) and the use tempering on increasing the strength properties, irrespective of chemical composition of sintering atmosphere, in Astaloy CrL based steel was observed. When tempering wasnt carried out, the higher properties were recorded for steel sintered in air with addition of 52 g of FeMn. Chemical analysis has showed (Table 4), that reduction of oxides is more advanced in 5%H2-95% N2 atmosphere. It can be pointed out that the addition of 52 grams of ferromanganese is not sufficient to oxide reduction presented in sintered steels. Higher amount of nitrogen in compacts can be explained by nitriding in nitrogen-rich atmosphere. The highest decarburization was observed for Astaloy CrL-based steels sintered at 1250C in the presence of hydrogen. This phenomenon was also recorded in Astaloy CrM-based steels sintered in air with addition of 52g FeMn. 5. CONCLUSIONS Assuming present work, the following conclusions can be drawn: 1. The effect of heat treatment on the mechanical properties of Astaloy CrL-based steels sintered at 1250C in 5% H2 / 95% N2 mixture was not observed. 2. Mechanical properties of Astaloy CrM-based steels sintered at 1250C in air + FeMn were comparable or higher than those recorded for low-chromium, low- molybdenum PM steels. 3. Low temperature sintering (1120C) and the use of tempering, irrespective of sintering atmosphere, allow increasing strength properties of low-chromium, low- molybdenum PM steels. 4. Not tempered, low-chromium, low-molybdenum PM steels sintered in air + 52 g FeMn obtained higher mechanical properties than those sintered in nitrogen/hydrogen mixture. 5. The addition of lump of ferromanganese in amount of 52 g is not sufficient for oxides reduction. 6. Both higher sintering temperature and the presence of hydrogen in sintering atmosphere are favourable for decarburization effect in sintered steels. 7. The heterogeneous microstructure of investigated PM steels mainly consists of martensite or martensite+bainite (lower and upper).
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ACKNOWLEDGEMENTS The financial support of the Ministry of Science and Higher Education under the contract no N N507 477237 (AGH no 18.18.110.961) is gratefully acknowledged. REFERENCES 1. Cias, A., Development and Properties of Fe-Mn-(Mo)-(Cr)-C Sintered Steels, Ed. AGH-UST, Krakow, Poland, 2004. 2. Youseffi, M., Mitchell, S.C., Wronski, A.S., Cias, A., Sintering, Microstructure, and Mechanical Properties of PM Manganese-Molybdenum Steels, Powder Metallurgy, Vol. 43, No. 4, pp. 353-358, 2000. 3. Cias, A., Mitchell, S.C., Wronski, A.S., Microstructure and Properties of PM 0.6%C Manganese Steels, Proc. of the 1998 Powder Metallurgy World Congress, EPMA, Granada, Spain, Vol. 3, pp. 179-184, 1998. 4. Cias, A., Mitchell, S.C., Watts, A., Wronski, A.S., Microstructure and Mechanical Properties of Sintered (2-4)Mn(0.6-0.8)C Steels, Powder Metallurgy, Vol. 42, No. 3, pp. 227-233, 1999. 5. Mitchell, S.C, Wronski, A.S., Cias, A., Stoytchev, M., Microstructure and Mechanical Properties of Mn-Cr-Mo-C Steels Sintered at >1140C, Advances in Powder Metallurgy and Particulate Materials, Vol .2, part 7, MPIF, pp. 129 to 144, 1999. 6. Mitchell, S.C., Becker, B.S., Wronski, A.S., Further Alloying Additions to PM Fe- Mn-C Steels, Proc. of the 2000 PM World Congress, Kyoto, Japan, The Japan Soc. Of Powder and Powder Metallurgy, Vol. II, pp. 923-926, 2001. 7. Slesar, M., Danninger, H., Sulleiova, K., Microstructure Formation and Fracture Processes in Fe-C Systems Sintered in Nitrogen, Powder Metallurgy Progress, Vol. 2, No 4, pp. 199-210, 2002. 8. Kremel, S., Danninger, H., Yu, Y., Effect of Sintering Conditions on Particle Contacts and Mechanical Properties of PM Steels Prepared from 3%Cr Prealloyed Powder, Powder Metallurgy Progress, 2, pp. 211-221, 2002. 9. Mitchell, S. C., Cias, A., Carbothermic Reduction of Oxides During Nitrogen Sintering of Manganese and Chromium Steels, Powder Metallurgy Progress, Vol. 4, No 3, pp. 132-142, 2004. 10. Bocchini G. F., Influence of Controlled Atmospheres on the Proper Sintering of Carbon Steels, Powder Metallurgy Progress, Vol. 4, No 1, pp. 1-34, 2004. 11. Cias, A., Mitchell, S. C., Pilch, K., Cias, H., Sulowski, M., Wronski A.S., Tensile Properties of Fe-3Mn-0.6/0.7C Steels Sintered in Semi-closed Containers in Dry Hydrogen, Nitrogen and Mixtures Thereof, Powder Metallurgy, Vol. 46, No 2, pp. 165-170, 2003. 12. Cias, A., Mitchell, S. C., Sulowski, M., Wronski, A. S., Sinter-hardening of Fe- Mn-C Steels, Proc. of Euro PM2001, EPMA, Nice, France, Vol. 4, pp. 246-251, 2001. 13. Cias, A., Mitchell, S.C., Wronski, A. S., Mechanical Properties of Chromium PM Steel Sintered in Technical Nitrogen, Proc. of PM 2004 World Congress & Exhibition, EPMA, Vienna, Austria, Vol. 2, pp. 7-12, 2004. 14. Cias, A., Wronski, A.S., Mechanical Properties Distributions of PM Manganese Steels Analysed by Gaussian and Weibull Statistics, Powder Metallurgy, Vol. 53, No 4, pp. 328-335, 2010. 15. Salak, A., Seleck, M., Bures, R., Manganese in Ferrous Powder Metallurgy, Powder Metallurgy Progress, Vol. 1, No 1, pp. 41-58, 2001. 16. Hryha E., ajkova E., Dudrov E., Study of Reduction/Oxidation Processes in Cr- Mo Prealloyed Steels During Sintering by Continuous Atmosphere Monitoring, Powder Metallurgy Progress, Vol. 7, No 4, pp. 181-197, 2007. 17. Salak, A., Effect of Extreme Sintering Condition upon Properties of Sintered Manganese Steels, Powder Metallurgy International, Vol. 16, No. 6, pp. 260- 263, 1984. 18. Salak, A., Selecka M., Bures, R., Manganese in Ferrous Powder Metallurgy, Powder Metallurgy Progress, Vol. 1, no 1, pp. 41-58, 2001.
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HGANAS NEW LEAN ALLOYS FOR PM PARTS

Philippe SZABO*, Eda YILMAZTRK YKSEKDA** *Hganas AB, France Office, 1117 Avenue Edouard Herriot, B.P. 117, F 69654, Villefranche sur Saone Cedex, France, philippe.szabo@hoganas.com **Hganas AB, Turkey Agency Office, Eksper Endustriyel Hammadde ve Dis Ticaret Ltd Sti, Sipahioglu Caddesi, Salkim Apartmani, No:11 D:13, 34149, Yesilyurt, Istanbul, Turkey, eda@eksperdisticaret.com ABSTRACT In order to cut costs and to be less sensitive to price versatility of raw materials, Hgans AB recently developed and put in mass production 2 new promising materials. Presented paper will cherry pick among examples of typical results which can be achieved with these 2 products: The so called Distaloy AQ, is part of the famous Hgans ABs family line of Distaloy (pre-diffusion - alloyed powders). Distaloy AQ is specifically designed to get very interesting mechanical properties after standard heat treatments & tempering. It could also allow high compressibility and very easy machinability after standard sintering. The so called Astaloy CrA, is part of the Hgans ABs family line of pre-alloyed Cr content powders. - Due to Cr content process routine shall use N2 + H2 for furnace atmosphere. Astaloy CrA is designed to get very nice global properties with standard sintering conditions. These properties will be emphasized a lot within sinterhardening conditions and small addition of Copper or Ni. Key Words: Distaloy AQ, Astaloy CrA, Alloyed Iron Powders, Mechanical Properties of PM Parts. 1. BACKGROUND FOR STRUCTURAL PARTS IN PM It is well known that traditional materials for PM parts often include copper, nickel, or molybdenum in quantities of totally 2-6%. Due to recent cost increases & cost versatility for these alloying elements, these materials are becoming less competitive compared to solid steel process routes. (Figure 1.) With a low alloy route, the sensitivity to price fluctuations can be reduced, and a robust product from an economical point of view can be ensured. Figure 1. Price changes for metals in max. and min. levels during 5 years and 1 year periods. 1.1. Hgans Routes To Be Less Sensitive To Versatile Material Costs In order to reduce the amount of alloying elements and/or change the nature of alloying elements, Hgans decided to work on LEAN ALLOYS way. Constraints being to use standard PM process routines and obviously to get good level of properties for the PM parts. This presentation is done in order to present 2 new alloys designed by Hgans, called DISTALOY AQ and ASTALOY CrA . 1.2 eminder Of Hgans Standard Grades Hgans is working for PM structural parts for a very long time. Its portfolio is very large and it is covering Sponge Powders, Atomized powders and famous brand names as Distaloys and Astaloys. All these root materials able to be mixed in Premix, Starmix and Densmix ways. (Figure 2.)
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Figure 2. Key elements of powders portfolio and Lean Alloys in green. 2. DISTALOY AQ CHEMICAL COMPOSITION : Fe base + 0.5% Mo + 0.5% Ni. The Iron Base powder is the high purity atomized ASC100.29. Mo and Ni elements are diffusion- alloyed elements (Figure 3.)
Figure 3. Sketch of a pre-diffusion alloyed particle. The diffusion-alloying process allows for high compressibility together with good consistency of properties on the PM components. The key process routine is defined as: COMPACTION + STANDARD SINTERING + CONVENTIONAL HEAT TREATMENT
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2.1 Properties 2.1.1 Green and Sintered Density Figure 4. Green density levels, in different compaction levels and in different lubricants additions.
Figure 5. Sintered density levels, in different compaction levels, in different lubricant additions and in different sintering temperatures. Compaction and sintering conditions are within, 600 and 700 MPa/70C compaction, 0.6% Lube E used as lubricant, sintering done at 1120C for 30 minutes and at 1250C for 1h, with 90/10 N2/H2atmosphere, no forced cooling was applied. 2.1.2 Sintered Properties and Typical Microstructures
Figure 6. Dimensional Change after sintering at the same sintering conditions, due to added graphite content before sintering.(Green Line: 700 MPa compaction to 7,25 g/cm3 density, Blue Line: 600 MPa compaction to 7,10 g/cm3 density)
Figure 7. Hardness variation after sintering at the same sintering conditions, due to the added graphite content before sintering.
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Figure 8. Tensile strength variation after sintering at the same sintering conditions, due to the added graphite content before sintering.
Figure 9. Microstructure of Distaloy AQ + 0.46%C 2.1.3 Heat Treated Properties
Figure 10. Microstructure of Distaloy AQ + 0.78%C
Compaction + Sintering + Heat Treatment conditions are within 20 min, 920C, C-neutral, oil quench, tempering 200C 1h in air.
Figure 11. Tensile Strength variation after Q&T heat treatment at the same heat treatment conditions due to the graphite content in the part.
Figure 12. Hardness variation after Q&T heat treatment at the same heat treatment conditions due to the graphite content in the part.
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Figure 13. Elongation variation after Q&T heat treatment at the same heat treatment conditions due to the graphite content in the part. 2.1.4 Typical Performances
Figure 14. Impact Energy variation after Q&T heat treatment at the same heat treatment conditions due to the graphite content in the part.
Figure 15. Tensile Strength comparison of different grades, after the same sintering conditions.
Figure 16. Yield Strength comparison of different grades, after the same compaction and sintering conditions
Figure 17. Hardness comparison of different grades, after the same sintering conditions. 3. ASTALOY CrA
Figure 18. Elongation comparison of different grades, after the same compaction and sintering conditions.
CHEMICAL COMPOSITION: Fe base + 1.8% Cr, Fully Pre-Alloyed
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Figure 19. Sketch of a pre-alloyed particle. The key process routine is defined as: COMPACTION + STANDARD SINTERING or SINTERHARDENING in N2+H2 Atmosphere.
3.1 Properties 3.1.1 Green Density
Figure 20. Green Density variation of Astaloy CrA depending on different compaction pressures and different lubrication systems. 3.1.2 Sintered and Sinterhardened Properties
Figure 21. Sintered and Sinter Hardened Properties of Astaloy CrA according to different process parameters. 3.1.3 Typical Microstructures In this section, different examples of microstructures depending on Carbon content, sinter-hardening conditions and different Copper or Nickel additions are displayed.
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Standard Sintering
Figure 22. Microstructure of Astaloy CrA with %0,4 sintered carbon content shows Pearlitic structure with around %5 ferrite inside.
Figure 23. Microstructure of Astaloy CrA with %0,6 sintered carbon content shows totally Pearlitic structure.
Figure 24. Microstructure of Astaloy CrA with %0,8 sintered carbon content shows totally Pearlitic structure. Astaloy CrA is basically a pearlitic material regardless of treatment under normal un-alloyed conditions. Sinter-Hardening at Cooling Rate 3 4 C/sec
Figure 25. Microstructure of Astaloy CrA with %0,4 sintered carbon content shows Pearlitic structure with around %5 ferrite inside.
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In sinterhardened conditions, the pearlite will be finer and some islands of martensite will form. Astaloy CrA is basically a perlitic material regardless of treatment under normal un-alloyed conditions. Ni or Cu Admixing (Sinterhardened Microstructures, cooling rate 3-4C/s)
Figure 28. Microstructure of Astaloy CrA + %2 Ni with %0,6 sintered carbon, shows Martensitic structure with %20 pearlit as well. 4. CONCLUSIONS
Figure 29. Microstructure of Astaloy CrA + %1 Cu with %0,6 sintered carbon, shows Martensitic structure with around %10 pearlite and some Bainite.
Distaloy AQ, is a newly developed diffusion-alloyed low Mo & Ni containing powder, suitable for manufacturing of high performance PM components after sintering at 1120C + conventional heat treatment . The optimum carbon content for this lean alloyed steel is between 0.5% and 0.6%. Tensile strengths of 800 ~1300 MPa can be achieved with the density level from 6.8 to 7.25 g/cm3 Astaloy CrA , is a newly developed pre-alloyed Cr containing powder, suitable for manufacturing of high performance PM components, after sintering at 1120C . Depending on carbon content, tensile strength levels from 500 MPa to 700 MPa can be obtained after conventional sintering at 1120 C. By adding Cu or Ni to Astaloy CrA; materials that possess good hardenability and thereby give excellent response to sinter hardening operations can be obtained. Martensitic structures can be achieved already at cooling rates of 2.0 C/s at a density of 7.0 g/cm3 . At a sintered carbon content of 0.5-0.6% Tensile Strength around1000 MPa is obtained with 1% Cu addition and around 1100 MPa can be obtained by a Ni addition of 2%. Hardness levels in the range of 300-400HV10 and elongation in the range 0.5 to 0.8 % can be obtained for both alloyed materials after sinter hardening. All results and figures thank to Ulf Engstrm and team from Hgans AB
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AN EXAMINATION OF COBALT EFFECT ON HEAT TREATED POWDER METALLURGICAL TOOL STEELS

. Hakan ATAPEK*, eyda POLAT*, Serap GM*, Ersoy ERR* and Gzde S. ALTU*
* Kocaeli University, Faculty of Engineering, Department of Metallurgical and Materials Engineering, 41380, Kocaeli, hatapek@kocaeli.edu.tr, seyda@kocaeli. edu.tr, sgumus@kocaeli.edu.tr, eerisir@kocaeli.edu.tr, gsultan.altug@gmail.com
ABSTRACT In this study, two commercial grades of powder metallurgical tool steels (DIN 1.3394 and 1.3395) are investigated to determine cobalt effect on the matrix, carbide distribution and hardness in soft annealed and hardened conditions. The steels have a similar composition of 1.30C, 4.20Cr, 6.40W, 5.00Mo and 3.10V, with the exception that DIN 1.3394 steel has 8.50Co as well. In order to investigate the primary carbides, soft annealing and solution annealing heat treatments were carried out. The specimens were heated stepwise (650 C, 850 C and solution annealing temperature) and hardened at 1000 C, 1100 C and 1200 C for 15 min followed by water quenching. In the first step, all samples are prepared by grinding and then ground surfaces are polished. Nital and Beraha solutions are used as etchants. Electrolytic etching is then carried out with AC2-I solution to characterize the matrix phase (martensite) after hardening. In the second step, all samples are examined using scanning electron microscope and energy dispersive x-ray spectrometer to investigate the carbide type in the matrix. In the third step, hardness values of the steels are determined in Vickers scale. The microstructural characterization reveals that DIN 1.3395 steel exhibits dispersed M6C and MC type carbides and carbides have poor interfaces with the matrix. On the other hand, DIN 1.3394 steel has M6C and MC carbides in the matrix, with skeleton morphology, due to cobalt wetting. Vickers hardness measurements show that DIN 1.3394 steel has a higher hardness value than DIN 1.3395 steel due to strengthening effect of cobalt in ferrite. Keywords: Tool steels, Powder Metallurgy, Microstructure, Carbides, Cobalt Wetting. 1. INTRODUCTION Proper heat treatment of tool steels is essential for their properties. Powder metallurgical (PM) tool steels have similar heat treatment routes as conventional tool steels, but they respond more rapidly to heat treatments due to their more uniform microstructure and finer carbides [1, 2]. PM tool steels may include cobalt as alloying element. Costly addition of cobalt increases solidus temperatures, thus permitting the use of higher solution temperatures. Furthermore, cobalt enhances hot hardness and temper resistance by promoting a finer carbide size, without entering the carbide lattice [1, 3]. The properties of tool steels are determined by the type, distribution and morphology of the primary carbides. The secondary carbides, precipitated during tempering, determine the hot hardness of the material [4]. Depending on the chemical composition of PM tool steels and on the cooling rate, following types of primary carbides appear in the alloyed steels after solidification: MC, M2C and M6C. Other carbides are of a minor importance [5]. During high temperature annealing, unstable M2C carbides decompose into M6C and MC carbides [5-7]. In tool steels, the improvement in the cutting performance with the addition of cobalt is indisputable. The more difficult the material is to machine, the more effective the addition of cobalt to the tool steel. Cobalt dissolves in iron (ferrite and austenite) and strengthens it at the same time imparting high temperature strength. During solution heat treatment to dissolve the carbides, cobalt helps the resist grain growth so that higher solution temperatures can be used to ensure the dissolution of higher percentage of carbides. Steels are quenched after solution annealing and a microstructure consisting of hard martensite with fine alloy carbides is obtained. Tempering will cause the precipitation of ultrafine carbides still in solution and maximum hardness will be attained. Here, cobalt plays another
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important role, in that it delays their coalescence. This is important as it means that during cutting, the structure is stable up to higher temperatures. Thus, cobalt-containing tool steels are capable of retaining strength at higher temperatures [8-10]. In the present study, cobalt effect on the matrix of a soft annealed powder metallurgical tool steel was investigated. DIN 1.3394 and DIN 1.3395 powder metallurgical steels in soft annealed and hardened conditions were examined using light microscope (LM), scanning electron microscope (SEM) and energy dispersive x-ray spectrometer (EDS). M6C and MC type carbides were found. Cobalt alloying resulted in a skeleton morphology of carbides due to wetting. 2. EXPERIMENTAL STUDY 2.1. Materials Two commercial grades of powder metallurgical tool steels, DIN 1.3394 and DIN 1.3395, were used in the experimental studies. The chemical compositions of the experimental steels are listed in Table 1. The soft annealing and solution annealing heat treatments were carried out in order to investigate the primary carbides. The specimen size of 10mm x 10mm x 15mm was used. The specimens were heated stepwise (650 C, 850 C and solution annealing temperature) and hardened at 1000 C, 1100 C and 1200 C for 15 min followed by water quenching. Hardness values of the steels for soft annealed condition were measured in Vickers scale. After three measurements, a mean value of hardness was determined as 204.7 HV10 for DIN 1.3395 and 285.2 HV10 for DIN 1.3394. As can be seen from the hardness measurements, Co-free steel has a lower hardness value than the one having 8.50Co (wt. %). Table 1. Chemical compositions of the experimental steels (wt.%). Materials DIN 1.3395 DIN 1.3394 C 1.30 1.30 Cr 4.20 4.20 Mo 5.00 5.00 V 3.10 3.10 W 6.40 6.40 Co 8.50 Fe balance balance
2.2. Metallographical preparations and microscopic examinations The specimens were metallographically prepared. After grinding, they were polished using diamond pastes with particle sizes of 3 m. Beraha II (100 ml H2O +20 ml HCl + 0.30.6 g of potassium metabisulfite) and % 3 nital solutions were used as etching agents. Electrolytic etching was then carried out with AC2-I solution to characterize the matrix phase (martensite) after hardening. Zeis Axitotech 100 model light microscope, Jeol JSM 6060 model scanning electron microscope and energy dispersive x-ray spectrometer were used to observe the morphology of carbides and to analyze their chemical compositions. 3. RESULTS AND DISCUSSION 3.1. Microstructural characterization in soft annealed condition The microstructures of DIN 1.3395 and DIN 1.3394 grade tool steels in soft annealed condition are given in Figure1. Cobalt free DIN 1.3395 tool steel has random distributed carbides in matrix phase (Figure 1a). As shown in Figure 1b, cobalt affects the distribution of carbides. A skeleton structure of carbides is seen after soft annealing.
Figure 1. SEM micrographs of tool steels in soft annealed condition, electrolytic etching; (a) DIN 1.3395 and (b) DIN 1.3394.
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3.2. Microstructural characterization in solution annealing condition In order to reveal the primary carbides in martensitic matrix, electrolytic etching was carried out using AC2-I solution. Figure 2 shows a SEM micrograph of DIN 1.3395 steel after solution annealing at 1000C for 15 min. Micrometer sized MC (grey) and sub-micrometer sized M6C (white) primary carbides exist in the microstructure. It should also be mentioned that deep etching reveals also martensitic plates of the matrix phase.
Figure 2. SEM micrograph of DIN 1.3395 after solution annealing at 1000 C for 15 min., electrolytic etching. The carbides (MC and M6C) and the matrix could be differentiated in this sample by using secondary electron (SE) imaging and backscattered electron (BSE) imaging (Figure 3). Since the carbides vary strongly in composition, W/ Mo (higher atomic number than Fe in the matrix) rich M6C carbides appear in white contrast. On the other hand, MC carbides rich in V (atomic number close to Fe in the matrix) appear in gray and cannot be distinguished from the matrix in Figure 3b.
Figure 3. SEM micrographs of DIN 1.3395 after solution annealing at 1000 C for 15 min., etched by Beraha; (a) SE mode and (b) BSE mode. In order to determine the chemical compositions of the primary carbides, microanalysis was carried out using EDS (Figure 4 and 5). The spot analyses (Figure 4b and 5b) revealed two types of primary carbides, tungsten and molybdenum being present in both. According to the EDS peaks, M6C carbides include mainly W and Mo (Figure 4b), whereas in primary MC carbides V exists as well and is dominant (Figure 5b). As it is seen, there is no cobalt content in both carbides. Cobalt takes place in iron lattice to strengthen the matrix phase.
Figure 4. (a) SEM micrograph and (b) EDS analysis of M6C carbides.
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Figure 5. (a) SEM micrograph and (b) EDS analysis of MC carbides. The microstructure of primary carbides in 8.5% cobalt alloyed PM steel (DIN 1.3394), after solution annealing at 1000 C for 15 min. is given in Figure 6. Similar primary carbides appear in DIN 1.3394 steel as well, however their distribution in matrix phase is markedly different than DIN 1.3395 case. The wetting effect of cobalt results in orientation of carbides rather than random distribution.
Figure 6. SEM micrograph of DIN 1.3394 after solution annealing at 1000 C for 15 min., electrolytic etching. The microstructures observed in solution annealed samples, etched by nital and Beraha solutions, are presented in Figures 7-12. The steel (DIN 1.3395), heated up to 1000C and then quenched, has random distributed carbides in the matrix (Figure 7). However, as the hardening temperature increases the amount of the carbides in the matrix decreases (Figures 8 and 9). This indicates that temperature promotes the dissolubility of the alloying element in iron lattice. In Figure 9, the mobility of grain boundaries is clearly seen in DIN 1.3395 tool steel heated up to 1200C. Effect of cobalt on wetting is seen in the matrix as given in Figures 10-12. The matrix of DIN 1.3394 tool steel heated up to 1000C exhibits fine and homogeneous carbides and it is obvious that there is no significant effect on the dissolubility of the carbides due to heating (Figure 10). As the heating temperature increases, the tendency of austenite grain size to be coarsened increases (Figures 11 and 12). Both steels showed grain coarsening with increasing annealing temperature.
Figure 7. Micrograph of DIN 1.3395 tool steel. Solution annealing temperature : 1000C, etched by nital + Beraha II solution.
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Figure 9. Micrograph of DIN 1.3395 tool steel. Solution annealing temperature : 1200C, etched by nital + eraha II solution.
Figure 12. Micrograph of DIN 1.3394 tool steel. Solution annealing temperature : 1200C, etched by nital + Beraha II solution. 4. CONCLUSION Powder metallurgical high-speed steels were soft annealed and hardened. Primary carbides observed in the matrix were analyzed using scanning electron microscope and energy dispersive spectrometer. The following preliminary results were obtained: (i) Soft annealing revealed that cobalt had a significant effect on the carbide distribution in matrix phase. A skeleton structure of carbides was seen in DIN 1.3394 steel.
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(ii) After solution annealing, SEM investigations and EDS analyses indicated that the primary carbides were of M6C and MC type. (iii) Comparison of hardened steel with soft annealed condition revealed that the secondary carbides remained undissolved after solution annealing at 1000C. When the micrographs are considered, as temperature of solution annealing increases the amount of carbides within the matrix decreases due to dissolutions. (iv) In solution annealed samples, grain coarsening was observed for both steels as annealing temperature increased. References 1. Davis, J. R., ASM Specialty Handbook: Tool Materials, ASM International, Materials Park, OH-USA, 1995. 2. Roberts, G., Krauss, G., Kennedy, R., Tool Steels, ASM International, Materials Park, OH-USA, 1998. 3. Fischmeister, H. F., Karagz, ., Andrn, H. O., An Atom Probe Study of Secondary Hardening in High Speed Steels, Acta Metall, Vol. 36, pp. 817-825, 1988. 4. Riedl, R., Karagz, ., Fischmeister, H. F., Jeglitsch, F., Developments in High Speed Tool Steels, Steel Research, Vol. 58, pp. 339-352, 1987. 5. Pippel, E., Woltersdorf, J., Pckl, G., Lichtenegger, G., Microstructure and Nanochemistry of Carbide Precipitates in High-Speed Steel S 6-5-2-5, Materials Characterization, Vol. 43, pp. 41-44, 1999. 6. Lee, E. S., Park, W. J., Baik, K. H., Ahn, S., Different Carbide Types and Their Effect on Bend Properties of a Spray-Formed High Speed Steel, Scripta Materialia, Vol. 39(8), pp. 1133-1138, 1998. 7. Zhou, X., Fang, F., Li, G., Jiang, J., Morphology and Properties of M2C Eutectic Carbides in AISI M2 Steel, ISIJ International, Vol. 50(8), pp. 1151-1157, 2010. 8. ASM Handbook, Machining, Vol. 16, pp. 51-59, ASM International, Ohio-USA, 1989. 9. Moiseev, V. F., Geller, Y. A., Effect of Cobalt on Structure and Properties of Fast-Cutting Steel, Metal Science and Heat Treatment, Vol. 7(4), pp. 245-249, 1965. 10. Gulyaev, A. P., Kupalova, I. K., Effect of Cobalt on the Structure and Properties of High-Speed Steels, Metal Science and Heat Treatment, Vol. 12(8), pp. 666-671, 1970.
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FORMING PROCESSES
www.turkishpm.org
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NI 625 Speralamlarnn Toz Enjeksiyon Kalplama Yntemiyle retilmesi

zgr ZGN*, H. zkan GLSOY**, Fehim FINDIK***, Ramazan YILMAZ**** Bingl niversitesi, Teknik Bilimler Meslek Yksekokulu, Bingl, Trkiye, oozgun@bingol.edu.tr ** Marmara niversitesi, Teknoloji Fakltesi, Gztepe, stanbul, 34722, Trkiye ** TBTAK MAM, Malzeme Enstits, Gebze - Kocaeli, 41470, Trkiye, ogulsoy@marmara.edu.tr *** International University of Sarajevo, Faculty of Engineering and Natural Sciences Department of Mechanical Engineering, 71000 Sarajevo, Bosnia-Herzegovina, ffindik@ius.edu.ba **** Sakarya niversitesi, Teknoloji Fakltesi, Esentepe Kamps, 54187, Sakarya, Trkiye, ryilmaz@sakarya.edu.tr
*
ZET Toz Enjeksiyon Kalplama (TEK) metalik ve metalik olmayan eitli boyutlardaki karmak ekilli paralarn retiminde yksek katma deere sahip ve gelimekte olan bir teknolojidir. Speralamlarn otomotiv, havaclk, medikal ve endstriyel uygulamalardaki stn zellikleri nedeniyle demir, krom ve/veya kobalt ieren nikel esasl speralamlarn gelitirilmesi zerine aratrmalar younlatrlmtr. Bu almada nikel esasl speralamlarn TEK yntemi ile retilmesi ve optimum retim parametrelerinin incelenmesi gerekletirilmitir. Deneysel almalar iin nikel esasl speralam gruplar ierisinde nemli bir yere sahip olan NI 625 tipi speralam tozlar, parafin mum (PM), polipropilen (PP), brezilya mumu (BM) ve stearik asit (SA) ieren ok bileenli bir balayc sistemi ile kartrlmtr. Elde edilen karm granl haline getirildikten sonra enjeksiyonla kalplanarak standart ekme ubuu formu kazandrlmtr. Kalplama sonrasnda NI 625 numunelerinin polimerik malzemelerden arndrlmas amacyla solvent ve termal balayc giderme ilemleri uygulanmtr. Balaycs giderilen numuneler DSC ve dilatometre analizlerine tabi tutularak, farkl scaklklarda ve yksek vakum altnda sinterlenmitir. retilen numunelerin younluk lmleri ve optik mikroskop incelemeleri yaplmtr. Sinterleme scakl artna bal olarak younluk deerleri art gstermi ve en yksek younluk deerine 1300oCde sinterlenen numunelerin sahip olduu gzlenmitir. Anahtar Kelimeler: Toz Enjeksiyon Kalplama, Speralam, NI 625, Sinterleme.
ProductIon of NI 625 Superalloys BY Powder InjectIon MouldIng Method

ABSTRACT Powder injection molding (PIM) is a maturing technology which is highly useful for the production of complex metallic and non-metallic parts of various sizes. Considering the advantageous properties of superalloys in automotive, aerospace, medical, and industrial applications, the development of nickel based superalloys containing iron, chromium and/or cobalt have become of great interest in recent years. In this work we present our effort made on developing nickel based superalloys by PIM process. A multiple component binder system consisting of paraffin wax (PA), polypropylene (PP), carnauba wax (CW), and stearic acid (SA) were mixed with metal powder (62.5 vol.%). NI 625 was prepared and injection molded as standard tensile bars. Solvent and thermal debinding process was employed to remove the polymeric materials. An optimized sintering cycle derived from differential scanning calorimetry (DSC) was used to sinter the specimens at different temperatures and in a high vacuum furnace. After production, a number of density measurements and light microscopes examinations were conducted. Density values of the materials increases depending on increasing of the sintering temperature and the highest density value was obtained for the sample sintered at 1300oC. Key words: Powder Injection Moulding, superalloy, NI 625, sintering
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1. Giri Enjeksiyon kalplama yksek boyutsal hassasiyete sahip rnleri kusursuz, ince taneli yapda ve mekanik zellikleri anizotropik olmayacak bir ekilde retmeyi mmkn klmakla birlikte; %95in zerinde verim salayan, para retimindeki iilii 3 kat veya daha da aa dren ve ilk yatrm maliyeti dk olan bir retim yntemidir. Enjeksiyon kalplamayla tek aamada kalplanan ve sinterlenen paralarn younluu geleneksel yntemlerle preslenerek sinterlenen paralardan daha yksek olup mukavemetleri dkm ve haddeleme ile retilenlere yakndr [1]. Nikel esasl speralamlar gaz trbinleri, uak motoru bileenleri, jet motorlar iin kritik paralar, roket motorlar, nkleer paralar takm malzemeleri ve metaller iin scak ilem kalplarnda en sk kullanlan malzemelerdir [2]. NI 625 ve NI 718 mhendislik uygulamalarnda en baarl uygulanm speralamlar arasnda yer almaktadrlar [3]. Nikel esasl bir speralam olan NI 625 alam mukavemet ve korozyon dayanmnn mkemmel bir kombinasyonunu sergilemektedir. Cr, Mo ve Nb gibi temel alam elementlerini ieren bu malzeme kat zelti ile mukavemetlenen bir alam olarak snflandrlmtr [4,5]. Mikroyapsal kararllndan dolay servis scakl kriyojenik scaklklar ile 1000oC arasnda olabilmektedir [6]. Gnmzde bu alamdan dvme yntemiyle retilen paralar endstride byk kabul grmesine ramen, karmak ekle sahip ou parann talal ilem gerektirmesi retim maliyetinin ok yksek olmasna yol amaktadr [7]. Geleneksel dkm yntemiyle retimde kimyasal segregasyonun neden olduu malzeme zelliklerindeki ktleme homojen iyap ve ince tane yaps salayan toz metalurjisi ile retime ynelmeye neden olmutur. Son gnlerde speralamlardan gaz trbin motorlar iin eitli paralarn retiminde metal enjeksiyon kalplama byk ilgi grmektedir [812]. Bu almada yksek ekme mukavemeti, srnme dayanm, kopma mukavemeti ve korozyon direnci gibi zellikleri beraber sergilediinden dolay olduka geni kullanm alan bulan NI 625 alamnn [4,5] toz enjeksiyon kalplama yntemiyle ekillendirilerek farkl scaklklarda sinterlenmesi sonucu mikroyapsal zelliklerinin karakterize edilerek belirlenmesi ve bu sayede genellikle dkm ve dvme yntemleriyle retilmekte olan bu denli geni kullanm alanna sahip bir malzeme iin alternatif bir retim yntemi olan TEK metodu iin optimum retim parametrelerinin tespit edilmesi amalanmaktadr. 2. Deneysel almalar Bu almada Osprey Co. (UK) firmasndan temin edilen NI 625 speralam tozlar kullanlmtr. Deneylerde kullanlan NI 625 speralam tozunun kimyasal bileimi Tablo 1de verilmitir. Kullanlan tozun parack ekli hakknda bilgi edinmek amacyla SEM grnts alnm, boyut dalm hakknda bilgi edinmek zere Malvern Mastersizer cihaz ile boyut dalm analizi gerekletirilmitir. Tablo 2de tane boyutu dalm analizine ait sonular da ieren balang tozuna ait baz zellikler verilmitir. Tablo 1. NI 625 speralam tozlarnn kimyasal bileimleri NI 625 Ni 64,043 Cr 20,9 Fe 2,600 Nb 3,2 Mo 8,4 % arlk Al 0,01 Ti 0,01 Co 0,01 C 0,029 Si 0,31 Mn 0,39
Tablo 2. NI 625 speralam tozlarnn zellikleri zellik retici retim yntemi Toz ekli Vurgu younluu (g.cm3) Teorik younluk (g. cm3) Partikl boyutu (m) D10 D50 D90 NI 625 Osprey Gaz atomizasyonu Kresel 5,3 8,58 3,7 11,1 26,7
Polipropilen, parafin mum, brezilya mumu ve stearik asidin farkl oranlarda kartrlmas ile elde edilen ok bileenli bir sistem halindeki balayc ile NI 625 tozu hacimce %60 ana toz%40 balayc olacak ekilde vakum altnda ve 170oC scaklkta 30 dk kartrlarak besleme stou hazrlanmtr. Besleme stou souduktan sonra el ile granle edilerek enjeksiyon cihaznda 12,5 MPa basn ve 20 saniye tutma sresi uygulanarak MPIF 50 standardna uygun olarak hazrlanm kalp kullanlarak ekme numuneleri kalplanmtr.
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ekillendirilen numunelerin balayc giderme ilemi iki aamada gerekletirilmitir. lk aama solvent balayc giderme ilemi olup, 70oCye stlan heptan ierisinde numunelerin 6 saat bekletilmesi eklinde gerekletirilmitir. Bu ilem sonucunda stearik asit, brezilya mumu ve parafin mumun numuneleri terk edip heptana gemesiyle yap ierisindeki balayclarn byk bir ksm uzaklatrlmtr. Balayc gidermenin ikinci aamas sl balayc giderme aamas olup, numunelerin almina altlk zerinde ve vakum ortamnda ekil 1de verilen sl evrime maruz braklmasyla gerekletirilmitir.
ekil 1. Isl balayc giderme ilemi evrimi TEK ile ekillendirilmi ve balaycs giderilmi numunelerin sinterleme davranlarnn belirlenmesi iin DSC ve dilatometrik testler uygulanmtr. DSC analizi Setaram marka DSC131 model cihazla (Fransa) 108,6 mg arlndaki numunenin 10oC/dk stma hzyla 1350oCye kadar 100 ml/dk debili yksek saflktaki Ar gaz atmosferi altnda stlmas ile gerekletirilmitir. Referans malzeme olarak Al2O3 kullanlmtr. Scaklk deiimine bal olarak malzemede meydana gelen genleme veya bzlmenin tespit edilebilmesini salayan dilatometre analizi iin ilk l boyu 3,47 mm olan numune kullanlmtr. Analiz, Unitherm Model 1161H cihaz (USA) kullanlarak numunenin H2 atmosferi altnda 10oC/dk stma hz ile 1313oCye kadar stldktan sonra 10oC /dk ile oda scaklna soutulmas eklinde gerekletirilmitir. NI 625 numuneleri 12601320oC arasnda farkl scaklklarda sinterlenmilerdir. Tm sinterleme ilemleri vakum ortamnda 10oC/dk stma ve soutma hzlaryla sinterleme scaklnda 1 saat tutma sresiyle gerekletirilmi olup frnn soumas srasnda 150oCye kadar vakum ak braklmtr. ekil 2de NI 625 tozundan retilmi ekme numunelerinin kalplama sonras ve sinterleme sonras grntleri verilmitir. ekme numunelerinin balayc giderme ilemine de bal olarak sinterleme sonras boyutsal olarak %1618 orannda ekme gsterdii grlmektedir. Sinterleme ileminin yksek vakum deerlerine klarak yaplmasna bal olarak numune yzeyinde herhangi bir oksitlenme olmad grlmtr.
ekil 2. NI 625 tozundan TEK ile retilen ekme numunelerinin kalplama sonras ve sinterleme sonras grntleri Sinterleme sonras Arimet prensibine gre numunelerin younluklar llmtr. Zmparalama ve parlatma gibi metalografik hazrlklardan sonra ve uygun dalayclarla dalandktan sonra numunelerin mikroyapsal geliimi incelenmitir. 3. Sonular ve Tartma Balang tozunun tane ekli hakknda bilgi edinmek amacyla alnm ekil 3teki SEM grntsnden de grlecei gibi tozlar kresel ekle sahiptirler. Toz enjeksiyon kalplamada kullanlan tozlarn partikl boyutu 20 mnin
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altndadr [8]. ekil 4teki tane boyutu analizine ait eriden tane boyut dalmnn toz enjeksiyon kalplamada kullanlmaya uygun aralkta olduu grlmektedir.
ekil 3. NI 625 tozunun SEM grnts
ekil 4. Ni625 tozuna ait tane boyut dalm erisi TEK ile ekillendirilen numuneler iin uygun sinterleme scakl aralnn belirlenebilmesi amacyla gerekletirilen DSC ve dilatometre analizlerine ait eriler srasyla ekil 5 ve ekil 6da verilmitir. DSC erisine gre 1170oCde faz dnm olabilecei dnlen bir endotermik pik olumutur. NI 625 numuneleri iin ergimenin yaklak 1298oCde balad ve 1331oCye kadar devam ettii grlmektedir. ekil 6da grlen dilatometre erisine gre bzlmenin 1190oCde balayp 1305oCye kadar devam ettii, en yksek bzlmenin 1300oC civarndaki scaklkta meydana geldii grlmektedir. Kimyasal bileimi bu almada kullanlan NI 625 tozuna ok yakn olan tozlarn kullanlmasyla gerekletirilmi olan bir baka almada yaplm olan dilatometre analizi sonucunda maksimum bzlmenin 1294oCde meydan geldii bildirilmitir [7].
ekil 5. NI 625 numunelerine ait DSC erisi
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ekil 6. NI 625 numunelerine ait dilatometre erisi DSC ve dilatometrik analiz sonular esas alnarak, farkl scaklklarda ve birer saatlik sreyle gerekletirilen sinterleme ilemleri sonras numunelerde ulalabilen grnr younluk deerleri ekil 7.ada, bal younluk deerleri ekil 7.bde verilmitir. En yksek younluk deerine 1300oCde yaplm olan sinterleme ilemiyle ulald grlmektedir. 1300oCnin zerindeki scaklklarda gerekletirilen sinterleme ilemlerinin younluun daha ok artmasna herhangi bir katk salamad, aksine de yol at grlmtr. 1320oC ve zerindeki sinterleme scaklklarnda numunelerde ksmi ergimelerin olduu ve buna bal olarak numune ekillerinin bozulduu gzlemlenmi; sinterleme ileminin 1320oCden yksek scaklklarda yaplamayaca tespit edilmitir.
ekil 7. Sinterleme scaklna bal olarak a) elde edilen grnr younluk deerleri, b) ulalabilen bal younluk deerleri
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Sinterlenen numunelerin gzenek miktar hakknda bilgi edinmek amacyla numunelerden parlatma ilemi sonrasnda alnm olan optik grntler ekil 8de verilmitir. Toz enjeksiyon kalplama yntemiyle retilen paralar geleneksel toz metalurjisi ile retilenlerden daha youndurlar. Para iinde kalan az miktardaki gzenekler de kk ve kresel ekilli olup birbirleriyle balantl deillerdir [13]. Grntler incelendiinde yukardaki aklamaya uygun olarak gzenek yapsnn kresel olduu ve gzeneklerin birbirleriyle balantl olmadklar grlmektedir.
ekil 8. a) 1260oCde, b) 1280oCde, c) 1300oCde, d) 1320oCde bir saat sreyle sinterlenen numunelerin parlatma sonras, dalama ncesi optik grntleri Farkl scaklklarda sinterlenmi numunelerin tane yaplarnn anlalabilmesi amacyla dalama ilemi sonrasnda alnm olan optik grntleri ekil 9da verilmitir. Gzeneklerin ounlukla tane ilerinde hapsolmu durumda bulunduu fakat ksmen tane snrlarnda da gzeneklere rastland ve bu gzeneklerin tane ierisindeki gzeneklerden daha iri olduu sylenebilir. 1260oCde sinterlenen numunenin optik grntsnden sadece toz partiklleri arasnda boyun oluumunun gerekletii, dolaysyla bu scakln sinterleme iin yetersiz olduu anlalmaktadr. Elde edilen younluk deerlerine uygun olarak en az gzenek miktarnn 1300oCde sinterlenen numunenin grntsnde olduu ve bu numunedeki gzeneklerin dierlerine kyasla daha kk boyutlu olduu gzlenmitir. Tane boyutunun artan sinterleme scakl ve sresi ile birlikte artt bilinen bir gerektir [14,15]. Grntler incelendiinde artan sinterleme scaklyla beraber tane boyutunun da iriletii grlmektedir. En yksek younluu salayan 1300oCde sinterlenmi numunenin ortalama tane boyutunun 100 m civarnda olduu grlmektedir. 1320oCde yaplan sinterleme sonucu malzemede gzeneklerin iriletii ve buna bal olarak dk younluk deeri elde edildii grlmtr. Bu durumun yksek miktarda sv faz oluumundan kaynaklanm olabilecei dnlmektedir.
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ekil 9. a) 1260oCde, b) 1280oCde, c) 1300oCde, d) 1320oCde bir saat sreyle sinterlenen numunelerin dalama sonras optik grntleri Yaplm olan bir almada 8,5 m boyutunda NI 625 tozu kullanlarak hidrojen atmosferi altnda, 1288-1298oC scaklk aralnda ve 2460 dakika tutma sreleriyle gerekletirilen sinterleme sonucu % 99un zerinde bal younlua ulalabildii rapor edilmitir [12]. Bir baka almada ortalama tane boyutu 9,7 m olan NI 625 tozundan retilen ham paralarn hidrojen atmosferi kullanlarak 1290oCde 0,5 saat sinterlenmesi sonucu 8,4 g.cm-3 younluk deeri (%99,5 bal younluk) elde edildii bildirilmektedir. Yine bu almada daha yksek younluk deerleri elde edilebilmesi iin sinterleme artlar zerinde yaplacak almalarn gerekliliine de vurgu yaplmaktadr [16]. Bu almada biraz daha dk younluk deerleri elde edilmi olmasnn, kullanlan balang tozunun ortalama tane boyutunun daha byk olmasndan ve balang tozlar arasndaki kimyasal bileim farkllklarndan kaynaklanm olabilecei dnlmektedir. Sinterleme ileminde itici g yzey enerjisindeki azalmadr. Daha kk boyutlu toz partiklleri daha yksek yzey enerjisi salar ve bu sayede daha ksa srede daha yksek younluk deerleri elde edilebilir [14]. Bu almada zellikle 1260oCde 1 saat sre ile sinterlenen numunenin optik grnts incelendiinde kk boyutlu tozlarn olduu ksmlarda younlamann daha ok olduu, iri partikllerin evresinde ise balanmann daha az ve gzeneklerin daha iri olduu grlmektedir. Bu durum bu tr malzemeler iin daha kk boyutlu tozlar kullanlarak daha yksek younluk deerlerine klabileceini dndrmektedir. 4. Sonular Bu almada Toz Enjeksiyon Kalplama yntemiyle NI 625 tipi nikel esasl speralam tozlarndan para retimi yaplm; yaplan deneysel almalardan aadaki sonular karlmtr. 1. ok bileenli bir balayc sistemi kullanlarak NI 625 speralam tozundan baarl bir ekilde para retimi gerekletirilmitir. 2. Yaplan boyut dalm analizi sonularna gre toz partikl boyutunun 3,7 ila 26,7m arasnda olduu, bu toz partikllerinin %50sinin 11,1 m boyutunda olduu tespit edilmitir. 3. Balayclar sisteme baarl bir ekilde dhil edilmi ve uygulanan bir dizi ilem sonrasnda sistemden baarl bir ekilde uzaklatrlmtr. 4. Balaycs giderilen malzemeler DSC, TGA ve Dilatometre analizlerine tabi tutulmulardr. DSC analizine gre malzemenin 1298oC civarnda ergimeye balad grlmtr. Dilatometre testinden elde edilen eriye gre 1190oC civarnda malzemede bzlmenin balad ve bu durumun 1300oCnin biraz zerine kadar devam ettii tespit edilmitir. 5. Farkl scaklklarda gerekletirilen sinterleme ilemlerinde 1300oCye kadar scaklk artna paralel olarak younluk deerleri artm ve en yksek younluk deeri 8,415 g.cm-3 olarak bu scaklkta elde edilmitir. Bu scakln zerindeki sinterlemelerle younlukta d olduu grlmtr. Artan sinterleme scaklnn malzemenin tane yapsnn irilemesine yol at gzlenmitir. TEEKKR NI 625 tozlarnn temini konusundaki desteklerinden dolay Osprey Co. (UK) Firmasna teekkr ederiz.
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KAYNAKLAR 1. V. M. Kryachek, Injection Moulding (Review), Powder Metallurgy and Metal Ceramics, cilt: 43, sayfa: 78, 2004. 2. Z. Zhong, K. Ramesh, S. H. Yeo, Grinding of nickel-based super-alloys and advanced ceramics, Mater Manuf Process 16 (2), sayfa:195207, 2001. 3. M. J. Cieslak, The solidification behavior of an alloy 625/718 variant, Proceedings of the International Symposium on the Metallurgy and Applications of Superalloys 718, 625 and Various Derivatives, Pittsburgh, Pennsylvania sayfa: 7180, 1991. 4. H. K. Kohl, Thermal stability of the superalloys Inconel 625 and Nimonic 86, Journal of Nuclear Materials, cilt: 101, sayfa: 243250, 1981. 5. V. L. Tellkamp, M. L. Lau, A. Fabel, and E. J. Lavernia, Thermal spraying of nanocrystalline inconel 718, Nanostructured Materials, cilt: 9, sayfa: 489492, 1997. 6. Kyung H. Chung, Jongsang Lee, Rodolfo Rodriguez, and Enrique J. Lavernia, Grain Growth Behavior of Cryomilled Inconel 625 Powder During Isothermal Heat Treatment, Metallurgical and Materials Transactions A, cilt: 33A, sayfa: 125134, 2002. 7. A. SIMCHI, Densification and Microstructural Evolution during Co-sintering of Ni-Base Superalloy Powders, Metallurgical and Materials Transactions A, cilt: 37A, sayfa: 2549, 2006. 8. J.J. Valencia, J. Spirko, and R. Schmees, Sintering Effect on the Microstructure and Mechanical Properties of Alloy 718 Processed by Powder Injection Molding, Superalloys 718, 625, 706 and Various Derivates, E.A. Loria, ed., TMS, Warrendale, PA, sayfa: 753762, 1997. 9. J.J. Conway, M.S. Sperber, and F.J. Rizzo: Advances in Powder Metallurgy and Particular Materials, MPIF, Princeton, NJ, blm 8, sayfa: 123137, 2002. 10. H. Wohlfromm, A. Ribbens, J. Maat, and M. Blomacher, Proc. Eur. PM2003 Congr. Exhib., Powder Injection Moulding, European Powder Metallurgy Association (EPMA), Shrewsbury, U.K., sayfa: 20715, 2003. 11. A. Bose, J. J. Valencia, J. Spirko, and R. Schmees Powder Injection Molding of Inconel 718, Advances in Powder Metallurgy and Particulate Materials, (MPIF, Princeton, NJ, sayfa: 1809918112, 1997). 12. K.F. Hens, J.A. Grohowski, R.M. German, J.J. Valencia, and T. McCabe, Processing of Superalloys via Powder Injection Molding, Advances in Powder Metallurgy and Particular Materials, (MPIF, Princeton, NJ, sayfa: 137148, 1994). 13. P. J. VERVOORT, R. VETTER and J. DUSZCZYK, Overview of Powder Injection Molding, Advanced Performance Materials 3, sayfa: 121151, 1996. 14. R. M, GERMAN, Sintering Theory and Practice, Wiley-Interscience, 1996, Newyork, USA. 15. R. M. GERMAN, Powder Metallurgy and Particulate Materials Processing, 2005, USA. 16. John L. Johnson, Lye King Tan, Pavan Suri and Randall M. German, Mechanical Properties and Corrosion Resistance of MIM Ni-Based Superalloys. presented at PM2Tec2004, Chicago, IL (June 1417, 2004).
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BLYEL TME YARDIMIYLA LE KARBON NANOTP RETM

mer GLER, Ertan EVN, Mustafa AKSOY Frat niversitesi Metalurji ve Malzeme Mhendislii Blm, Elaz zet Bu almada tme ilemi yardm ile karbon nanotp (KNT) retilmitir. Bu amala ncelikle katalizr olarak kullanmak zere nano boyutlu demir tozu retilmitir. kincil adm olarak ise saf grafit tozlar 5 saat yksek enerjili tme ilemine tabi tutularak nano karbon tozu elde edilmitir. Bu ilemlerden elde edilen tozlar belirli oranlarda kartrldktan sonra 1400 oC de argon atmosferi altnda tavlanmtr. Elde edilen numuneler zerinde XRD ve HR-TEM incelemeleri yaplmtr. ncelemeler sonucunda aplar 15-30 nm arasnda deien karbon nanotpler tespit edilmitir. Anahtar Kelimeler: Karbon nanotp, Bilyeli tme
CARBON NANOTUBE PRODUCTION ASSISTED BY BALL MILLING

mer GLER, Ertan EVN, Mustafa AKSOY Frat University, Metallurgy and Materials Engineering Department, Elaz Abstract In this study, carbon nanotubes were produced assisted by ball milling process. For this aim, firstly nano-sized iron powder was produced as a catalyst. Secondly, pure graphite powders were ball milled in a high energy ball mill for 5 h to attain nano carbon powders. These powders obtained from the process were mixed at the different proportions then annealed at 1400 oC in Ar gas. Then, samples were investigated by X-Ray diffraction (XRD) and High Resolution Transmission Electron Microscopy (HR-TEM). As a result of the investigations, carbon nanotubes with diameter varying from 15 to 30 nm were determined. Keyword: Carbon nanotube, Ball Milling 1.GR Karbon nanotpler (KNT) ilk kez Iijima tarafndan kefedilmitir ve o tarihten itibaren pek ok aratrmac KNT in zelliklerini anlamak ve yksek kalitede nanotpler retebilmek iin saysz aratrmalar yapmtr [1]. Elektrik ark boalm, kimyasal buhar ktrme (CVD), sol-jel gibi pek ok yntem kullanlarak KNT in retimi baar ile gerekletirilmitir [2]. Y.Chen ve arkadalar ise yaptklar almalarda KNT in tlm grafit tozlarnn tavlanmas ile retilebileceini ortaya koymulardr [3]. KNT in bymesini kontrol etmek ve yksek kalitede KNT retebilmek iin artlarn optimize edilmesi gerekir ve bu durum oluum mekanizmasnn anlalabilmesi iin gayet nemli bir husustur. CVD veya elektrik ark boalm gibi KNT retiminde ok kullanlan metotlardaki temel oluum mekanizmas; karbon atomlarnn uygun artlar altnda tek tek dizilmesi ile nanotp oluturmas esasna dayanr. Y. Chen
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ve arkadalar mekano-termal yntem ile KNT retiminde oluum mekanizmasn; 150 saat tme ilemine tabi tutulmu ve tme ilemi sonunda eilmi-kvrlm grafit tabakalarnn 1000-1500 oC gibi bir scaklkta tavlanmas sonucunda KNT e dnt eklinde belirtmektedirler. Ayn aratrmaclar 1000 oC in altnda ise kristallemenin ok az olmas sebebiyle hi nanotp olumadn belirtmektedirler [3-4]. X.H. Chen ve arkadalar ise yaptklar almada grafitin 150 saat tlmesi ve 1400 oC scaklkta tavlanmas sonucu eitli alarda eilmi, kvrlm grafit tabakalar gibi eitli nano yaplarn ortaya ktn rapor etmilerdir [5]. Daha nceki almalarmzdan, 5. ulusal nanobilim ve nanoteknoloji kongresinde sunulan almamzda mekanotermal yntem ile karbon nanotp retimi aratrlm ve 5 saat tme ilemi sonunda karbon naotpler sentezlenmitir [6]. Belirtilen almada sentezlenen tplerin aplar 50-200 nm arasnda deimektedir. Bu almada ise elde edilen karbon nanotplerin aplar 15-30 nm ye kadar drlmtr. 2.DENEY ALIMALARI Daha nceki almamzda deneyler sonucu kaln nanotpler elde edildii giri ksmnda belirtilmiti. Bu almada ise elde edilen nanotplerin aplarn kltmek amacyla nano boyutlu katalizr kullanlmasna karar verilmitir. Bu sebeple yaplan deneyler iki admda gerekletirilmitir. lk adm; nano boyutlu demir tozu retimi, ikinci adm ise karbon nanotp retimidir. Katalizr retimi iin, % 99,9 saflkta ve 30 m boyutundaki demir tozlar Fritsch Pulverisette 7 cihazda 3 saat tlmtr. Nano boyuta inen demir tozu 200 oC de 30 dakika tavlama ilemine tabi tutulmutur. Elde edilen tozdaki yapsal deiimleri tespit etmek iin CuK mas yapan Bruker Advanced D8 marka X-n difraktometresi kullanlmtr. Ayrca demir tozu Jeol Jem 2100F marka yksek znrlkl geirmeli elektron mikroskobu (HR-TEM) ile incelenmitir. Deneyin ikinci aamasn karbon nanotp retimi kapsamaktadr. Bu amala; grafit tozlar (Merck kGAA, 99.5%, <50 m) yksek enerjili bir deirmende tlmtr. Deneylerde kullanlan deirmen Fritsch Pulverisette 7 olup, kullanlan kap ve bilyeler sertletirilmi sade karbonlu elikten imal edilmitir. tme deneylerinde bilye/toz oran 32/1 olarak seilmi ve deneyler 850 devirde gerekletirilmitir. Grafit tozlar 1/4, 2, 3, 4, 5 saat tme ilemine tabi tutulmulardr. Ardndan, tlen numunelerdeki yapsal deiimleri tespit etmek iin X-n analizi alnmtr. Bylece grafitin tamamen amorf hale geldii tme sresi tespit edilmitir. Tamamen amorflamann 5 saat tme ilemi sonunda gerekletii tespit edilmitir. deal tme sresinin tespit edilmesinin ardndan, homojen bir karm salayabilmek iin 5 saatlik tme ileminin bitmesine 30 dakika kala almann ilk admnda retilen nano boyutlu demir tozu kaba ilave edilmi ve tme ilemi 5 saate tamamlanmtr. tme ileminin ardndan, tozlar bir tp frn ierisinde 5.10-2 l/min lk argon gaz ak altnda 1400 oC de 4 saat tavlama ilemine tabi tutulmulardr. Elde edilen numuneler Jeol Jem 2100F marka yksek znrlkl geirmeli elektron mikroskobu (HR-TEM) ile incelenmitir. 3.SONULAR Daha nceki almalarmz nda [6], nanotp retiminde katalizr olarak nano boyutlu saf demire ihtiya olduuna karar verilmitir, bu sebeple bu almann ilk admnda nano boyutlu demir tozu retilmitir. 3 saat sreyle demir tozu tme ilemine tabi tutulmutur. Nano boyutlu demirin yeniden kristalleme scaklnda bir sre tavlandktan sonra aktif karbona katlmasna karar verilmitir. Bu sebeple elde edilen nano demir tozlar 200 oC de 30 dakika tavlama ilemine tabi tutulmutur. Bu ilemden sonra elde edilen tozun XRD analizi ekil.1 de verilmitir. Debye-Scherrer (1) forml kullanlarak elde edilen demirin ortalama parack boyutunun 17 nm civarnda olduu hesaplanmtr. (1) Ps parack boyutu, dalga boyu, FWHM full width at half-maximum, 1 ise krnm asdr. XRD analizinde verilen demirin karakteristik pikleri incelendiinde bu piklerin ilem grmemi demir piklerine gre geniliklerinin artt sylenebilir. Bu durum ise toz parack boyutunun azaldn ve kristal rgdeki i gerilmelerin arttn tarif etmektedir.
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ekil 1.tme ilemiyle retilen nano boyutlu demirin XRD analizi ekil.2 de, retilen nano boyutlu demirden alnan HR-TEM grnts verilmitir. ekilde de grld gibi farkl boyutlarda pek ok partikl bulunmaktadr. HR-TEM incelemelerinden tespit edildii kadaryla yapda ortalama aplar birka nm den 20 nm kadar demir partiklleri bulunmaktadr.
ekil 2. tme ilemiyle retilen nano boyutlu demirden alnan HR-TEM grnts Nano boyutlu demir retiminin ardndan grafit tozlarnn tlmesi ilemlerine geilmitir. tme ilemi uygulanm tozlar XRD incelemelerine tabi tutulmulardr. ekil 3. de 1/4, 2, 3, 4, 5 saat tme ilemlerine tabi tutulmu grafit tozlarndaki deiim verilmitir. 1/4 saat tme sonunda grafitin (002) pikinde ciddi bir azalma meydana gelmitir. Ayrca, tmenin ilk 4 saatine kadar kristal rgye sahip grafit tozlarnn miktar artan sre ile azalmakta bu sreden sonra ise kristal rgye sahip grafit tozlarnn miktar ihmal edilecek kadar kk miktarlara dmektedir. Tozlarda meydana gelen deformasyonlarn artmas zaman ierisinde, nce grafit levhalar arasndaki zayf balarn kopmasna, sonra her bir grafit levhasnda karbon atomlar arasndaki balarn krlmasna sebep olmakta ve sonu yap amorf bir hal almaktadr.
ekil 3. tme sresinin artmasyla grafit tozunda meydana gelen XRD deiimi.
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ekil 3 de grlecei zere 5 saat tme sonunda yapda demir karbr olumutur. tme ilemi sresince bilye ve kaplardan kopan demir paracklar tme sresinin artmas ile beraber demir karbre dnmlerdir. Bilyeler vastas ile tozlara yklenen enerji, tozlarn krlm ba saysn ve dolaysyla i enerjisini arttrmtr. Bu tozlar i enerjilerini minimuma indirerek kararl hale gemek iin fazladan enerjiye ihtiya duymaktadrlar. Bu enerji sl ilem sayesinde tozlara kazandrlmaktadr. 5 saat tme yaplm ve 1400 oC de 4 saat sl ilem grm tozlar incelendiinde yapda aplar 15-30 nm arasnda olan nanotplerin olutuu grlmektedir (ekil.4.a ve b). Oluan bu tplerin ok cidarl nanotpler olduu kolaylkla sylenebilir. Karbon nanotplerde boy/ap oran nemli bir parametredir. ap kk boyu uzun nanotpler daha ok tercih sebebidir. ekil 4.a. incelendiinde boylar 0,5-1 m arasnda deien tpler grlmektedir. Oluan nanotplerin bir ksm karbon ktlenin alt ksmnda kalmtr.
ekil 4a,b: 5 saat tme yaplm ve 1400 oC de 4 saat sl ilem grm tozlarn HR-TEM grnts. ekilde 4.b de grlen sa taraftaki koyu renkli blge karbon ktle olup, sol taraftaki ak renkli ubuk eklindeki yap ise ok duvarl karbon nanotptr. Grlen nanotpn ap yaklak olarak 20 nm dir. Tpn dier ucu karbon ktlenin altnda kaldndan dolay boyu konusunda kesin bir ey sylemek mmkn deildir. Karbon nanotpn grlen ksmnn uzunluu ise yaklak 300 nm dir. Nanotpn u ksmnda ise demir katalizr grlmektedir. Oluan nanotpn bu katalizr zerinde gelitii aktr. Katalizr amal kullanlmak zere retilen nano demir tozlarnn katlmad daha nceki deneylerden, aplar 50-200 nm arasnda olan karbon nanotpler elde edilmitir [6]. retilen katalizrn tlen toza katlmas sayesinde karbon nanotplerin aplar 20 nm civarna indirilebilmitir. Nanotpler genellikle katalizr etkisi gsteren gei elementleri zerinde olumaktadrlar. ekil 4a ve b de grlen nanotplerin oluumunda da bu katalizr etkinin sz konusu olduu dnlmektedir. zellikle mekano-termal (tme ve sonrasnda sl ilem) yntemde demirin katalizr etkisi meydana getirdii hususunda literatrde rapor edilmi almalar bulunmaktadr [8]. Bu dnceyi irdelemek amacyla bu ekirdek yaplar zerinden TEM teknikleri kullanlarak EDS analizi alnm ve bu sonular ekil 5 de verilmitir.
ekil 5: Karbon nanotpn zerinde gelitii ekirdekten alnan EDS analizi. Elde edilen sonuca gre karbon nano tpn ucunda bulunan metal paracnn Fe olduunu sylemek mmkndr. Analizde tespit edilen dier elementlerden Cu nun TEM incelemesi iin kullanlan karbon elekten dolay, C nin metal paracn yzeyi karbonla kapl olduundan dolay pikler verdikleri eklinde dnlmektedir. Si nin ise sl ilem frnnda kullanlan almina tpn kapan izole etmekte kullandmz silikon contadan dolay ortaya ktklar dnlmektedir.
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Literatrde tme yoluyla karbon nanotplerin nasl olutuu konusunda kesin bir fikir olmamakla birlikte, bu yntemle retim konusunda Avustralya Ulusal niversitesinden (ANU) Y.Chen, SLS ksaltmasyla tanmlad bir oluum mekanizmasndan bahsetmektedir [4].
ekil 6. Kat halde karbon nanotp oluumunun ematik gsterimi [4].
Bu mekanizmaya gre uygulanan sl ilem scaklnn karbonun bilinen yaplarnn dnm scaklnn altnda olmasndan dolay bu scaklkta karbonun kat halde demirin ise sv fazda bulunmas sz konusudur. Bu yzden, bu model Solid-Liquid-Solid (SLS) oluumu zerine oturtulmutur. Yksek miktarda kusurlar ihtiva eden eilmi bklm grafenler ve amorf haldeki karbon tme ilemi ile ortaya kar ve bu yaplar kararsz yaplardr. Bu yaplar sl ilem esnasnda yksek hareketlilik sebebiyle nanotpler gibi daha kararl olan ekle ve geometriye dnmek isteyeceklerdir. Nano boyutta hatalar ihtiva eden ve dzensiz yapda olan zincirler ve halkalar nanotplerin geliimi iin bir kaynak grevi grmektedir. Bu esnada sv fazda bulunan demir ise ideal bir ekirdek grevi grerek nanotplerin geliimini salamaktr. Bu modelle ilgili olarak yazarn sunduu ematik resim ekil 6. da verilmitir. ekilde M, metal nano parac temsil etmekte olup, nano hatalar ihtiva eden nano karbon tozlar tpn geliimi iin bir kaynak oluturmaktadr. Bu modele gre amorf karbonla temas halinde bulunan Fe, sv evreye geerek ierisinde znm halde bulunan karbonu yzey ksmna doru itmekte ve Fe paracnn yzeyinde oluan karbon filmi ise amorf karbondan beslenerek nanotp oluturmaktadr. 4.GENEL SONULAR Nano boyutlu demir tozu retebilmek iin demir yksek enerjili deirmende 3 sat tlmtr. Sonuta - ortalama boyutu 17 nm olan demir tozu elde edilmitir. Grafitin 1/4, 2, 3, 4, 5 saat tme ilemine tabi tutulmutur. 5 saat tmenin ardndan yapnn tamamen amorflat grlm, (002) piki tamamen kaybolmutur. 5 saatlik tme ileminin son yarm saatinde, daha nce retilen nano boyutlu demir tozlar kaba eklenmitir. Elde edilen tozun 1400 oC de 4 saat tavlama ilemine tabi tutulmasyla yapda karbon nanotpler olumutur. Oluan tplerin aplar 15-30 nm civarndadr. Tplerin ularnda ise 10-15 nm civarnda demir partiklleri mevcuttur. 5.KAYNAKLAR Iijima S. Helical microtubules of graphitic carbon. Nature 1991; 354:56-8. 1. 2. Terrones M, Hsu WK, Kroto HW, Walton DRM. Nanotubes: A revolution in materials science and electronics. Top Curr Chem, 199:189-34, 1999 Chen Y, Conway MJ, Fitz Gerald JD, Williams JS, Chadderton LT. The nucleation and growth of carbon 3. nanotubes in a mechano-thermal Process. Carbon; 42:1543-48, 2004 Chen Y. Solid-state formation of carbon nanotubes. In: L. Dai, editor. Carbon Nanotechnology, 4. UK;Elsevier; 53-58, 2006 Chen XH, Yang HS, Wu GT. Generation of curved or closed-shell Carbon nanostructures by ball-milling 5. of graphite. J Cryst Growth 2000; 218:57-61. Evin,E., Gler,.,Aksoy,M.Carbon Nano Tube Formation by Mechano-Thermal Process, 5th Nanosci6. ence and Nanothecnology Conference, p.19, June 8-12, Eskiehir, 2009 Geng Y., Wang S.J., Kim K.J., Preparation of graphite nanoplatelets and graphene sheets, Journal of 7. Colloid and nterface Science, vol.336, pp. 592-598, 2009 Chen Y, Conway M.J., Fitz Gerald J.D., Carbon nanotubes formed in graphite after mechanical grin8. ding and thermal annealing, Applied Physics A, vol. 76, pp. 633-636, 2003 Surov D.V., Lomovsk O.I., Boldyrev V.V., Low- Temperature Crystallization of Mechanically Amorphi9. zed Graphite Inorganic Material, vol. 42, pp.116-120, 2006
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SNTERLEME PARAMETRELERNN MONEL 400 ALAIMI TOZUNDAN RETLM PARALARIN MEKANK ZELLKLERNE ETKS
Sultan ZTRK*, Blent ZTRK*, Fatih ERDEMR* ve Yksel PALACI** Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080, Trabzon, suozturk@ktu.edu.tr ** Nide niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 51240, Nide, ypalaci@nigde.edu.tr
*
zet Bu almada, sinterleme scaklnn ve sresinin 69 m ortalama boyuta sahip Monel 400 alam tozlardan retilmi paralarn mekanik zelliklerine etkisi incelenmitir. Yksek saflkta hidrojen gaz atmosferinde gerekletirilen sinterleme ileminde, sinterleme scaklnn etkisini incelemek amacyla 1100, 1140, 1180 ve 1200 oC scaklklar ve sinterleme sresinin etkisi iin 60, 75, 90 ve 105 dak. sreler kullanlmtr. Sinterleme ncesi Monel 400 alam tozlarn yzey oksitleri hidrojen gaz atmosferinde indirgenmi ve sonrasnda tek eksenli ift etkili preste 600 MPa sabit basnta preslenerek ham para haline getirilmitir. Deneysel sonular en optimum mekanik zelliklerin 1200 o C scaklkta ve 90 dak. sinterleme sresinde elde edildiini ortaya koymutur. Anahtar Kelimeler: Monel 400 Alam, Sinterleme Scakl, Sinterleme Sresi, Mekanik zellikler.
EFFECT OF SINTERING PARAMETERS ON THE MECHANICAL PROPERTIES OF SINTERED PARTS PRODUCED BY MONEL 400 ALLOY POWDERS
ABSTRACT In this study, the effects of sintering parameters such as temperature and time on the mechanical properties of compacts produced by Monel 400 alloy powders which have mean particle size of 69 m have been investigated. The sintering process was carried out in high purity hydrogen atmosphere by using temperatures of 1100, 1140, 1180 and 1200 oC and times of 60, 75, 90 and 105 minutes. The surface oxides of Monel 400 alloy powders were reduced in hydrogen atmosphere before sintering and then the powders were pressed as green compacts with pressure of 600 MPa by using a uniaxial and double action pres. The experimental results showed that the optimal mechanical properties were obtained with sintering temperature of 1200 oC and sintering time of 90 minutes. Key words: Monel 400 Alloy, Sintering Temperature, Sintering Time, Mechanical Properties. 1.GR Sinterleme, preslenmi ham haldeki paralarda birbirine temas eden tozlarn aralarnda ba oluturmas amacyla yksek scaklkta uygulanan stma ilemidir. Sinterleme ile gzenekli yapdaki ham paradan gzeneksiz veya ok dk oranda gzenekli para elde edilir. Sinterleme ilemi sonrasnda paralarn mukavemet deerlerinde nemli artlar meydana gelir. Sinterleme ileminde tozlar arasnda balanma kat halde, ergime scaklnn altnda atomik difzyon mekanizmasyla gerekleir. Kat hal sinterlemesi metal veya alamn ergime noktas altnda bir scaklkta yaplan sinterleme ilemidir. Bu ilem, birbirine temas eden paracklarn yksek scaklklarda birbirine balanmasn salar. Bu balanma, ergime scaklnn altnda kat halde atom hareketleriyle oluabilir. Baz durumlarda sv faz oluumu ile de gerekleebilir. Mikroyap leinde balanma, temas eden paracklar arasnda boyun oluumu ile gerekleir [1-4]. Sinterleme ilemi difzyonla gerekleen bir ktle transferi olaydr. Uygun scaklk ve srede atomlarn yaynm ile ktle transferi geekleir ve tozlar arasnda ba oluur. Bu adan sinterleme scakl ve sresi en nemli ilem
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deikenleridir. Kullanlan tozun bileimine ve ortalama boyutuna bal olarak bu deikenler belirlenir. Kk paracklar yksek yzey enerjisine sahip olduklarndan, yksek scaklkta atomlarn yaynm ve kk paracklarn yzey enerjilerinin azalmasyla sinterleme gerekleir. Tozlarda yzey enerjisi toz boyutuyla ters orantldr. Kk boyutlu tozlar, byk boyutlu olanlara nazaran daha yksek yzey enerjisine sahiptirler ve daha hzl sinterlenirler. Byk boyutlu tozlarn sinterlenmesinde difzyon mesafesinin uzamasndan dolay tam younlua ulamak iin daha uzun sre sinterlemek gerekir [5,6]. Sinterleme balangcnda tozlar birbirleriyle noktasal temas halindedirler. Sinterleme ilemi ilerledike birbirine temas eden paracklar arasndaki ba byr ve birleir. ki paracn tamamen birlemesiyle, ap balang apnn 1,26 kat olan tek parack oluur. Kresel tozlarn temas noktalarna boyun ad verilir. Boyun blgelerinin bymesi ile morfolojik deiimler balar. Boyun bymesi, birbiriyle temas eden tozlardan boyun blgesine doru atomlarn difzyonu ile gerekleir. Tane snrlar ktle transferinin saland yerlerdir [1,3,7]. Sinterlemede ba oluumu, yzey difzyonu, tane snr difzyonu ve tane ii hacim difzyonu mekanizmalaryla gerekleir. Yksek scaklklarda atomlar komularyla balarn koparp yeni yerlerine gidecek dzeyde enerjiye sahip olurlar. Atomlarn hareket edebilmesi iin gerekli olan en dk enerjiye aktivasyon enerjisi denir. Kat hal sinterlemesinin ilk aamasnda birbirinden bamsz olarak boyun bymesi grlr. Sktrlmam tozlarda temas kk noktalar ile balar. Balangta gzenekler dzensiz ve keli ekillidir. Optimum sinterlemede gzenekler kk ve yuvarlak biimde olmaldr. Tane snr difzyonu mekanizmas geliirken gzenekler tane snrlarnda younlar. Tane snrlarna yerleen gzenekler tane bymesini engeller. Sinterlemenin ara aamasnda boyunlar birbiri ile etkileerek byrler. Gzenekler yuvarlak ve dzgn hale gelmeye balarlar. Sinterlemenin ilerleyen aamalarnda taneler byr, gzenekler klr. Tane snr alanlarn azaltan gzenekler nedeniyle sistem enerjisinde bir azalma olur. Tane snrlarndan daha yava hareket eden gzenekler tane bymesi esnasnda tane snrlar tarafndan ya srklenir ya da yok edilirler [8,9]. Bu almada, sinterleme scaklnn ve sresinin Monel 400 alam tozlardan retilmi paralarn mekanik zelliklerine etkisi incelenmitir. Sinterleme ilemi yksek saflkta hidrojen gaz atmosferinde gerekletirilmitir. Frn atmosferi bileimindeki hidrojen gaz oran %100 olarak alnmtr. Sinterleme scaklnn etkisini incelemek amacyla 1100, 1140, 1180 ve 1200 oC scaklklarda sinterleme gerekletirilmi olup, sinterleme sresi olarak 60, 75, 90 ve 105 dak. sreler kullanlmtr. Sinterleme ileminde Monel 400 alamndan su jeti soutmal dner disk atomizasyonu yntemiyle retilmi ortalama boyutu 69 m olan 125 m elek alt tozlar kullanlmtr. Bu tozlar sinterleme ncesi tek eksenli ift etkili preste 600 MPa sabit basnta preslenerek ham para haline getirilmitir. 2. DENEYSEL ALIMALAR Bu almada, bileimi izelge 1de verilen Ni-Cu alam (Monel 400) kullanlm olup, bu alamdan su jeti soutmal dner disk atomizasyonu yntemiyle toz retimi yaplm, retilen tozlar tek eksenli ift tesirli preste preslenerek; ortalama toz boyutu, boyut dalm ve presleme basncnn ham younlua etkileri incelenmitir. izelge 1. Monel 400 alam kimyasal bileimi (% A.) Element Ni 66.8 Cu 31.45 Mn 1.33 Fe 0.97 Si 0.38 C 0.1 P 0.013 S 0.002
Monel 400 alamndan toz retimi KT Metalurji ve Malzeme Mhendislii Blmnde mevcut bulunan su jeti soutmal dner disk atomizasyon nitesinde gerekletirilmitir. retilen 125 m elek alt Monel 400 alam tozlarnn ortalama boyutunun (d10), (d50 ) ve (d90) belirlenmesinde Malvern Mastersizer 2000 model parack boyut analiz cihaz kullanlmtr. retilen paralarda younluk gradyannn olumamas iin presleme ncesi toz numuneler Trbila tr bir kartrcda 30 dak. sre ile 55 d/d devir saysnda kartrlarak homojen bir dalm salanmtr. Tozlarn presleme ncesi yzey oksitlerinin indirgenmesi ve preslenen paralarn sinterlenmesi amacyla 1300 C maksimum alma scaklna sahip atmosfer kontroll sinterleme frn kullanlmtr. Oksit indirgeme ve sinterleme ileminde %100 orannda yksek saflkta (%99,999 saflkta) hidrojen gaz kullanlmtr. Ortama hidrojen gaz gndermeden nce azot gazyla sprme ilemi gerekletirilmitir. Yaplan ilemlerin tamam frn zerinde bulunan PLC kontrol nitesi zerinde gerekletirilmitir. Tozlardaki yzey oksitleri 550 oC scaklkta 10 dak. sre ile indirgeme ile temizlenmitir. ndirgeme ileminin tam olarak gerekleip gereklemedii XRD cihazyla yaplan faz
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analizi ile kontrol edilmitir. Sinterleme scaklnn etkisini incelemek amacyla 1100, 1140, 1180 ve 1200 oC scaklklarda sinterleme gerekletirilmi olup, sinterleme sresi olarak 60, 75, 90 ve 105 dak. sreler kullanlmtr. Hidrojen atmosferinde indirgenmi tozlardan ham younlukta para retmek amacyla PLC kontroll, tek eksenli ve ift etkili 50 ton kapasiteli hidrolik toz kalplama presi kullanlmtr (ekil 1). Monel 400 tozlar ASTM 8M04 standardnda tel erozyon yntemiyle hazrlanm olan ekme numunesi kalbnda preslenmilerdir. Presleme basnc 600 MPa olarak sabit tutulmutur. Tozlarla kalp yzeyi srtnmesini en aza indirmek amacyla presleme ncesi kalp ve zmba yzeyleri inko stearat ile yalanmtr. retilen Monel 400 alam tozlarn morfoloji ve mikroyaplar ile tozlardan presleme ve sinterleme ile retilmi paralarn mikroyap incelemeleri Zeiss EVO LS10 marka taramal elektron mikroskobunda (SEM) yaplmtr. Monel 400 tozlarnn morfoloji incelemeleri ift tarafl yapkan karbon band kullanlarak gerekletirilmitir. Yine ayn tozlarn mikroyap incelemeleri iin tozlar, bir kalp ierisinde souk sertleen epoksi reine ile yataklandrlmtr. Dalama ilemi, taze hazrlanan 8 g FeCl3, 25 mL HCl , 100 ml H2Odan oluan dalama ayrac kullanlarak 20 s srede gerekletirilmitir. SEM incelemeleri ncesinde, reine kalba yataklanm tozlar iletkenlik salanmas amacyla altn kaplanmtr. Preslenmi ve sinterlenmi numunelerin sertlik, akma dayanm, ekme dayanm ve yzde uzama gibi mekanik zellikler incelenmitir. ekme zellikleri Instron marka ekme cihaznda 0,01 mm/s hzda ekme deneyleri yaplarak belirlenmitir. Mikro sertlik lmleri Struers Duramin marka cihazda en az 10 farkl noktadan 98,12 mN yk 10 s sreyle uygulanarak gerekletirilmitir. Makro sertlik lmleri Rockwell sertlik lm cihaznda 1/16 in bilya ile 10 kg n yk ve 60 kg esas yk artlarnda sertlik lmleri gereklemitir.
ekil 1. ift tesirli tek eksenli presin ematik resmi. 1-Kauuk ayak, 2- kolonlar, 3- klavuz silindir, 4- st silindir piston, 5- alt silindir, 6- pres tablas, 7- alt zmba ve kalp boluu, 8- st zmba, 9- PLC kontrol nitesi, 10- hidrolik devre elemanlar, 11- motor, 12- pompa, 13- hidrolik ya tank. 3. DENEYSEL SONULAR VE TARTIMA Bu almada sinterleme scaklnn ve sresinin etkisini incelemek amacyla, su jeti soutmal dner disk atomizasyonu yntemiyle retilen, 69 m ortalama boyuta sahip 125 m elek alt Ni-Cu alam (Monel 400) tozlar kullanlmtr. retilen numunelerin tamam 600 MPa sabit basnta preslenmitir. Kullanlan Monel 400 tozlardan
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deiik elek aralklarna ait SEM fotoraflar ekil 2de verilmitir. ekilden de grlebilecei gibi, tozlarn tamam kresel ekilli olup, toz boyutuna bal olarak toz ekli deimemitir. Genellikle 90 mdan byk boyutlu olan tozlarda yzeylerde ekilme boluu olumutur. Toz boyutu bydke ekilme boluu miktarnn artt tespit edilmitir. ekilme boluklarnn nispeten byk apl tozlarda daha fazla olmas, toz boyutunun bymesiyle souma hznn azalmasna iaret etmektedir.
(a) (b) ekil 2. Monel 400 tozlar morfolojisi. a) -36/25 m elek aral, b) -125/90 m elek aral. Sinterleme sresinin sinter younluuna etkisi, 1180 ve 1200 C scaklklar iin ekil 3te verilmitir. Artan sinterleme sresi ve scaklk artlarnda sinter younluunun artt gzlenmitir. Ham younluu %80 olan para iin 1180 Cde 60, 75, 90 ve 105 dak. sinterleme sreleri sonunda elde edilen younluk deerleri srasyla %84, %87, %91 ve %91 olarak elde edilmitir. Ayn srelerde 1200 C de sinterlenen %80 ham younluktaki numunelerin sinterleme younluklar srasyla %88, %91, %94 ve %93 olarak bulunmutur. Artan sinterleme sresiyle atomik difzyona daha fazla zaman tannmakta ve younluk art meydana gelmektedir. Ancak, sinterleme sresi snrsz deildir. Belli bir aamadan sonra ok uzatlan sinterleme sresinin younluk artrc etkisi grlmemektedir. Son aamada gerekleen bu olayda tane snr enerjisinin azalmasndan dolay sinterleme ilemi yavalar. Baz durumlarda tane bymesi gibi gzenek bymesi de oluabilir. Bu durumda gzenek says azalrken ortalama gzenek boyutu artar. Bu yzden gereinden uzun tutulan sinterleme srelerinde kayda deer bir younluk art meydana gelmez. 1180 Cde 90 ve 105 dak srelerde yaplan sinterlemede elde edilen younluklar srasyla %91 ve %91 olarak elde edilirken, 1200 C sinterleme scaklnda 90 ve 105 dak. sinterleme srelerinde elde edilen younluklar ise srasyla %94 ve %93tr. Yukarda belirtilen sebeplerden dolay artan sre ile birlikte younlukta bir miktar azalma meydana gelmitir.
ekil 3. Sinterleme sresinin sinter younluuna etkisi (presleme basnc 600 MPa). Sinterleme sresinin sertlie etkisi, 1180 ve 1200 C scaklklar iin ekil 4de gsterilmitir. 1180 oC scaklkta 60, 75, 90 ve 105 dak. sinterlenen numuneler iin makro sertlik deerleri srasyla 61, 67, 72 ve 74 HRF olarak elde edilmitir. 1200 Cde ayn srelerde yaplan sinterlemede elde edilen sertlikler srasyla 73, 75, 79 ve 76 HRFdir. Artan sinterleme sresiyle sertliin artt aka grlmektedir.
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ekil 5de sinterleme sresi ile ekme mukavemetinin deiimi grlmektedir. Buna gre; 1180 C scaklkta 60, 75, 90 ve 105 dak. sinterleme sreleri iin ekme mukavemeti deerleri srasyla 167, 202, 234 ve 258 MPa olarak elde edilmitir. Ayn sinterleme srelerinde 1200 Cde sinterlenen numunelerin ekme mukavemeti deerleri ise srasyla 211, 248, 259 ve 244 MPa olarak bulunmutur. Artan sinterleme sresiyle difzyona daha fazla zaman salandndan tozlar arasnda daha gl ba oluumu salanm, gzenek saylar ve boyutlar azalmtr. Dier taraftan, gereinden fazla sinterleme sresinin gzenek bymesine yol ap mekanik zellikleri olumsuz etkilemesi burada da ortaya kmtr. 1200 Cde 90 dakikalk sinterlemede 259 MPa ekme mukavemeti elde edilirken, 105 dak. sinterlemede ise bu deer 244 MPa olmutur. Sinterleme sresine bal olarak elde edilen mekanik zelliklerin tamam izelge 2de verilmitir. Sinterleme sresiyle ekme mukavemeti ve kopma uzamasndaki deiim, 1180 C ve 1200 C sinterleme scaklklar iin ekil 6 ve ekil 7de verilmitir.
ekil 4. Sinterleme sresi ile sertliin deiimi (presleme basnc 600 MPa).
ekil 5. Sinterleme sresi ile ekme mukavemeti deiimi.
ekil 6. Sinterleme sresiyle ekme mukavemeti ve kopma uzamasnn deiimi (sinterleme scakl 1180 C).
ekil 7. Sinterleme sresiyle ekme mukavemeti ve kopma uzamasnn deiimi (sinterleme scakl 1200 C).
izelge 2. Sinterleme sresine bal olarak mekanik zelliklerin deiimi. Sinter. sresi (dk.) 60 75 90 105 Sinterleme younluu(%) 1180 C 84 87 91 91 1200 C 88 91 94 93 Akma mukavameti (MPa) 1180 C 74 89 92 108 1200 C 102 90 92 71 ekme mukavameti (MPa) 1180 C 167 202 234 258 1200 C 211 248 259 244 Uzama (%) 1180 C 5,7 7,2 9,3 9,4 1200 C 6,0 11,3 11,7 13,2
Sinterleme scaklyla sinter younluunun deiimi, 60 dakikalk sinterleme sresi iin ekil 8de verilmitir. 1100, 1140, 1180 ve 1200 C scaklklarda 60 dak. sinterlenen numuneler iin sinter younluklar srasyla %82, %83, %84 ve %88 olmutur. ekil 9da sinterleme scaklyla sertliin deiimi, 60 dakikalk sinterleme sresi iin verilmitir. 1100, 1140, 1180 ve 1200 C scaklklarda 60 dak. sreyle yaplan sinterlemede sertlikler srasyla 55, 58, 61 ve 73
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HRF olarak gereklemitir. Artan sinterleme sresiyle sinter younluunda olan artla birlikte sertliin de artt aka grlmektedir.
ekil 8. Sinterleme scaklyla younluunun deiimi (sinterleme sresi 60 dakika).
ekil 9. Sinterleme scaklyla sertliin deiimi (sinterleme sresi 60 dakika).
Sinterleme scaklyla ekme mukavemetinin deiimi, 60 dakikalk sinterleme sresi iin ekil 10da verilmitir. 1100, 1140, 1180 ve 1200 C scaklklarda yaplan sinterlemelerde ekme mukavemeti deerleri srasyla 126, 138, 167 ve 211 MPa olarak bulunmutur.
ekil 10. Sinterleme scaklyla ekme mukavemetinin deiimi. Sinterlenmi numunelerde, sinterleme sresine bal olarak i yap deiimi, 1200 C sabit sinterleme scaklnda, 60, 75, 90 ve 105 dak. sreler iin, ekil 11-14de sunulmutur. ekillerden de grlebilecei gibi, 60 dakikalk sinterlemede i yapda gzenek says yksek olup, sinterleme sresinin yetersizliinden dolay toz paracklar arasndaki snr belirgin durumdadr. Srenin 75 dak. kartlmasyla gzenek miktarnda grlr bir azalma ve toz tanecikleri arasndaki snr, tam olarak yok olmasa da, ok byk oranda azalm durumdadr. 90 ve 105 dak. sinterleme srelerinde elde edilen i yaplarda ise tane snrlarnn tamamen ortadan kalkt, gzeneklerin ise kreselletii grlmektedir. 90 dak. sinterlenen paradaki gzenek miktar 105 dak. sinterlenen paraya gre daha fazla iken, 105 dak. sinterlenen numunedeki gzeneklerin, nispeten uzun olan sinterleme sresinden dolay birleerek byd anlalmaktadr.
ekil 11. 1200 oC scaklkta sinterlenen numunede sinterleme sresi ile i yapnn deiimi (sinterleme sresi 60 dakika).
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ekil 13. 1200 oC scaklkta sinterlenen numunede sinterleme sresi ile i yapnn deiimi (sinterleme sresi 90 dakika). 4. SONULAR
Yaplan deneysel almalardan ve elde edilen bulgularn deerlendirilmesinden elde edilen sonular aada verilmitir: 1. retilen Ni-Cu alam (Monel 400) alam tozlarn tamam kresel ekilli olup toz boyutuna bal olarak toz ekli deimemitir. 90 mdan byk boyutlu tozlarda yzeylerde ekilme boluu olutuu gzlenmitir. Toz boyutu bydke ekilme boluu miktarnn artt tespit edilmitir. 2. Monel 400 alamndan retilen tozlarnn yzeylerindeki ince oksit film tabakasnn yksek saflkta (%99,999 saflkta) hidrojen atmosferinde 550 0C scaklkta 10 dak. sre ierisinde indirgendii anlalmtr. 3. Artan sinterleme sresi ve scaklk artlarnda sinter younluunun artt gzlenmitir. 1180 C sinterleme scaklnda optimum sinterleme sresi 105 dakika olurken, 1200 C iin bu sre 90 dakika olarak tespit edilmitir. 4. Artan sinterleme sresiyle sertlik ve ekme mukavemeti deerlerinde artlar gzlenmitir. Sertlik ve ekme mukavemetinin sinter younluuyla doru orantl olarak deitii tespit edilmitir. 5. 90 ve 105 dakika sinterlenen numunelerden elde edilen i yaplarda tane snrlar tamamen ortadan kalkt, gzeneklerin ise kreselletii tespit edilmitir. Gzeneklerin, 105 dakikalk sinterlemede nispeten uzun olan sinterleme sresinden dolay birleerek byd gzlenmitir. KAYNAKLAR 1. German, R.M., Toz Metalurjisi ve Parackl Malzeme lemleri eviri Editrleri: S. Sarta, M. Trker, N. Durlu, Trk Toz Metalurjisi Dernei Yaynlar:05, 2007,Ankara. 2. Yamaguchi, K., Takakura, N., Imatani, S., Compaction and Sintering Characteristics of Composite Metal Powders, Journal of Materials Processing Technology, 63, 364-369, 1997. 3. German, R.M. Sintering Theory and Practice, Wiley-Interscience Publications, New York, 1996. 4. Narasimhan, K.S., Sintering of Powder Mixtures and The Growth of Ferrous Powder Metallurgy, Materials Chemistry and Physics, 67, 56-65, 2001. 5. Missiaen, J.M., Solid-State Spreading and Sintering of Multiphase Materials, Materials Science and Engineering A, 475, 2-11, 2008. 6. Liu, S., Zhang, H., Hu, J., Effect of Carbusintering on Densification Behavior and Mechanical Properties of Fe2%Ni-x%Cu Alloys, Materials Design, 32, 3686-3691, 2011. 7. Okuyama, K., Sintering, Hiroshima University, Higashi-Hiroshima, Japan,2007. 8. Wang ,Y.,U., Computer Modeling and Simulation of Solid-State Sintering: A Phase Field Approach, Acta Materialia, 54, 953961, 2006. 9. Ji, C.H., Loh, N.H., Khor, K.A., Tor, S.,B., Sintering Study of 316L Stainless Steel Metal Injection Molding Parts Using Taguchi Method: Final Density, Materials Science and Engineering A, 311, 7482, 2001.
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RENE TR VE ELYAF UZUNLUUNUN FREN BALATALARININ MEKANK VE TRBOLOJK ZELLKLERNE ETKS

Blent ZTRK* ve Sultan ZTRK*
*
Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080, Trabzon, bozturk@ktu.edu.tr zet
Bu almada, reine tr ve elyaf uzunluunun otomotiv fren balatalarnn mekanik ve tribolojik zelliklerine etkileri incelenmitir. Srtnme deneyleri, Chase tipi srtnme-anma deney dzeneinde yaplmtr. Elde edilen sonulardan hem reine trnn hem de elyaf uzunluunun balata malzemelerinin mekanik ve tribolojik zellikler zerinde etkisi olduu grlmtr. Reine tr dikkate alndnda MR ve SR kodlu numuneler srasyla en dk ve en yksek srtnme katsays gsterirken CR ve MR kodlu numuneler en dk ve en yksek anma direnci gstermitir. Ayrca artan elyaf uzunluuyla da numunelerin srtnme katsaylar derken anma dayanmlar artmtr. almada balata malzemelerinin anma yzeyleri ve anma paracklar da incelenmitir. Anahtar Kelimeler: Balata, Srtnme, Anma, Reine Tr, Elyaf Uzunluu.
EFFECTS OF RESIN TYPE AND FIBER LENGTH ON THE MECHANICAL AND TRIBOLOGICAL PROPERTIES OF BRAKE FRICTION MATERIALS
ABSTRACT In this study, the effects of resin type and fiber length on mechanical properties and friction characteristics of automotive brake materials were studied. The friction tests were performed using a Chase type friction tester. The results showed that both resin type and fiber length played an important role on the mechanical and tribological properties of the friction materials. The highest and the lowest friction coefficient for resin types were recorded for series SR and series MR composites, respectively, while the series MR and CR composites showed the highest and the lowest wear resistance, respectively. For the fiber length considered, increasing the fiber length increased the wear resistance of the composites. The morphological features of worn surfaces and wear debris of the composites were analyzed. Keywords: Brake Pad, Friction, Wear, Resin Type, Fiber Length. 1. GR Srtnme malzemelerinin (balata) balca uygulama alanlar debriyaj ve fren balatalardr. Bu malzemeler ok bileenli kompozit malzemeler olup deien scaklk, hz, basn ve evre artlarnda kararl bir srtnme katsaysna, dk anma, yeterli dzeyde mukavemete ve alma esnasnda grlt ve titreim oluturmama gibi zelliklere sahip olmas istenir [1-5]. Bu nedenle balatalarn performanslar kendilerini oluturan bileenlerin zelliklerine baldr. Gnmzde balatalarda kullanlan bileen says 700
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n zerinde olmasna ramen bu bileenler 4 ana grupta toplanr. Bunlar balayclar, elyaflar, dolgu malzemeleri ve srtnme dzenleyicilerdir [6-8]. Balayc malzemeler veya balayclar, balata bileenlerini bir arada tutan malzemelerdir [7]. Elyaflar, balataya mukavemet, tokluk ve sl kararllk salarlar. Dolgu malzemeleri, balatann maliyeti drmek amacyla katlr ve balatann hacmini arttrmak zere kullanlrlar. Srtnme dzenleyici malzemeler ise balatann srtnme-anma davrann deitirmek zere kullanlrlar. Balatay oluturan bileenlerin birletirilmesi ve bu bileenlerin ortaya koyduklar sinerjik etki, balatann performansn nasl etkileyeceini tam olarak bilmek olduka zordur [9]. Modifiye edilmi ve edilmemi fenolik reineler, balatay oluturan bileenleri iyi slatmas ve maliyetinin de dk olmas nedeniyle genellikle fren malzemelerinde balayc olarak kullanlrlar. Ancak fenolik reine neme ve scakla kar duyarldr. Yksek sl kararlla ve oksitlenme direncine sahip reine seimi balatann feyd (artan scaklkla birlikte srtnme katsaysnda dme) dayanmn etkiler [7, 10]. Fenolik reine dndaki reineler maliyetlerinin nispeten yksek olmas nedeniyle balata retiminde genellikle tercih edilmemektedirler [7]. Fren balata malzemelerin retiminde farkl elyaflar kullanlmaktadr. Bu elyaflarn tr ve oranlar balatann srtnme performans ve anma miktar zerine olduka etkilidir. zellikle volkanik kayalardan elde edilen Lapinus elyaf, dier balata bileenleriyle birlikte kullanldklarnda balatann feyd dayanm arttrmtr. Aramid elyaf, ta yn ve cam elyafla birlikte balatalarda kullanldnda balatann yksek scaklklardaki srtnme performansn gelitirmi ve daha karal srtnme katsays ortaya koymutur [1]. Son yllarda yaplan almalarda, balatann performansna elyaf hacim orannn, elyaf ynlenmesinin ve elyaf trnn etkileri incelenmi ancak elyaf uzunluunun etkisi tam olarak ortaya konmamtr [11]. Bu nedenle bu almann amac hem reine trnn hem de elyaf uzunluunun balatann performansna etkisini incelemektir. Srtnme performans deneyleri Chase tipi srtnme test dzeneinde SAE J661 standardna uygun olarak yaplmtr. 2. DENEYSEL ALIMALAR 2.1. Numune retimi almada incelen numuneler asbest iermeyen organik trde (NAO) olup reine, elyaf, yalayc, andrc, dolgu malzemesi ve srtnme dzenleyici iermektedir. Her bir numune grubunda matris malzemesi olarak farkl tr reine (dz fenolik reine, kaju fst kabuu svs (CNSL) ile modifiye edilmi fenolik reine ve melamin reine) kullanlmtr. Takviye edici malzeme olarak kullanlan elyaflarn kodlar ve uzunluklar ise srasyla RB215, RB260, RB280 ve 15025 m, 30050 m, 650150 m dir. Elyaf ap yaklak 9 m dir. Balata retiminde kullanlan bileenler ve bu bileenlerin arlk oranlar izelge 1 de verilmitir. Balata numuneleri seri (SR, CR ve MR) halinde retilmitir. Numune retiminde hem reine tr hem de elyaf uzunluu deiken olarak alnm, balata bileenleri ise btn numunelerde ayn oranda sabit tutulmutur. Balatay oluturan bileenler 0,1 mg hassasiyetle tartldktan sonra bir kartrc ierisinde 3-4 dakika sreyle kartrld. Karm daha sonra 150 oC scaklk, 15 MPa basnca sahip bir kalpta 15 dakika sreyle tutularak sertletirildi. Sertlemenin tamamlanmas iin numuneler 180 oC scakla sahip frnda 4 saat sreyle tutuldu. retilen numuneler daha sonra talal ileme tabi tutularak deneylere hazr hale getirildi. izelge 1. Numune bileenleri ve oranlar.
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almada kullanlan reinelerin sl analizleri Seiko II Exstar 6000 termal analiz cihaznda azot atmosferinde ve 20 oC/dak stma orannda yaplmtr. ekil 1(a-c), reinelerin TG ve DTG erilerini gstermektedir. ekilden grld zere dz fenolik reine (SR), CNSL modifiyeli reine (CR) ve melamin reinenin (MR) ekzotermik reaksiyonlar srasyla 154, 159 ve 152 oC dir. Ayrca bu reinelerin ayrma scaklklar da srasyla yaklak olarak 550, 431 ve 408 oC de meydana gelmitir.
(a)
(b)
(c) ekil 1. Reinelerin TG ve DTG erileri: (a) dz fenolik reine; (b) CNSL modifiyeli fenolik reine; ve (c) melamin reine. 2.2. Fiziksel ve Mekanik zelliklerin llmesi Numunelerin fiziksel (younluk) ve mekanik zellikleri (sertlik, eilme, kesme ve darbe mukavemetleri) ilgili standartlara gre tespit edildi. Numune sertlikleri ASTM D785-03 standardna uygun olarak Rockwell sertlik test makinesinde ve M skalasnda tespit edildi. Eilme, kesme ve darbe mukavemet deerleri srasyla ASTM D790, ASTM D732 ve ASTM D256 standartlarna gre gerekletirildi. Btn deneyler oda scaklnda yapld. Eilme ve kesme mukavemet deerleri Instron marka niversal test makinesinde yapld. Darbe deneylerinde kullanlan ekicin arl ise 15 J dr. 2.3. Test Cihaz ve Test artlar Srtnme performans deneyleri SAE J661 standardna uygun olarak Chase tipi test cihaznda gerekletirildi. Test cihaz ekil 2 de verilmitir. Cihaz numune tutucu, tambur ve kontrol nitesi olmak zere 3 ana ksmdan olumaktadr. Srtnme deneylerinde kullanlan numune boyutu 25x25x7 mm dir. Srtnme performans deneyleri izelge 2 de verilen test artlarnda yaplmtr.
ekil 2. Srtnme test dzenei (Chase tipi).
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izelge 2. Test artlar.
Srtnme deneyleri yanma, dzenleme, birinci altrma, birinci yorma, birinci toparlama, anma, ikinci yorma, ikinci toparlama ve ikinci altrma ksmlarndan olumaktadr. zgl anma miktar, birim srtnme ii bana anan balata hacmi olup aadaki formlle bulunmutur [11]. (1)
Burada; m numune arlk kayb (anma deneyinden nce ve sonra numunedeki arlk kayb), L kat edilen toplam yol, numune younluu, Fn ise uygulanan yktr. Numune anma yzeyleri ve anma paracklar ZEISS marka taramal elektron mikroskobunda, anma parack boyutu ise Malvern Mastersizer 2000 cihaz kullanarak tespit edildi. 3. SONULAR VE TARTIMA 3.1. Fiziksel ve Mekanik zellikler Balata numunelerinin younluk, sertlik, eilme, kesme ve darbe mukavemet deerleri izelge 3 de verilmitir. izelge 3. Numunelerin fiziksel ve mekanik zellikleri.
izelge 3 den grld zere numunelerin sertlik deerleri artan elyaf uzunluuyla birlikte dmtr. Maksimum sertlik deerleri hem reine tr hem de elyaf uzunluu gz nne alndnda CR kodlu numunelerde elde edilmitir. Eilme mukavemeti genellikle artan elyaf uzunluuyla artmtr. Literatrde yaplan almalar incelendiinde ksa elyaf takviyeli kompozitlerin eilme mukavemet deerleri artan elyaf uzunluuyla artt grlr [11, 12]. En yksek ve en dk eilme mukavemet deerleri srasyla CR ve MR kodlu numunelerde elde edilmitir. Bununla birlikte CR kodlu numuneler maksimum kesme mukavemet deeri gsterir. Numunelerin kesme mukavemetleri genellikle hem SR kodlu hem de CR kodlu numunelerde artan elyaf uzunluuyla artarken, bu iliki MR kodlu numunelerde grlmemitir. Ayn elyaf uzunluklar dikkate alndnda en yksek darbe mukavemet deeri SR kodlu numunelerde elde edilirken, CR ve MR kodlu numunelerde bu deerler yaklak olarak ayndr. 3.2. Srtnme Performans Numunelerin srtnme katsaylarnn artan scaklkla (II-yorma) deiimi ekil 3 (a-c) de verilmitir. SR1, SR2, SR3 kodlu numunelerin deney balangcndaki srtnme katsaylar 0,45, 0,44, 0,45, CR1, CR2, CR3 kodlu numunelerin 0,44, 0,45, 0,43 ve MR1, MR2, MR3 kodlu numunelerin 0,43, 0,42 ve 0,39 dur. Deney sonucunda bu deerler srasyla SR1, SR2, SR3 kodlu numuneler iin 0,49, 0,47, 0,47, CR1, CR2, CR3 kodlu numuneler iin 0,48, 0,47, 0,45 ve MR1, MR2, MR3 kodlu numuneler iin 0,41, 0,41 ve 0,40 olarak elde edilmitir.
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(a)
(b)
c ekil 3. Numunelerin srtnme katsaylarnn scaklkla deiimi: (a) SR; (b) CR; ve (c) CR. ekil 3 (a-c) de grld gibi, numunelerin srtnme katsaylar deneyin balamasyla birlikte artan scaklkla kayma ara yzeyindeki gerek temas alanndaki deiimler nedeniyle artmtr. Numunelerin srtnme katsaylar, deneyin balamasyla birlikte artmasnn nedeni birincil temas platolarnn oluumu ve buna bal olarak da gerek temas alanlarnn artmasdr. Platolar, disk ile temas alanlar olup birincil ve ikincil platolar olmak zere iki ksmdan oluur. Birincil platolar balatann daha yksek anma dayanmna sahip, mekanik olarak kararl ve anmaya direnli bileenlerinden oluur. kinci safhada ise bu bileenler ikincil platolarn olumas ve bymesi iin ekirdeklenme yeri olutururlar. Anma paracklar yer yer birincil platolarn arkasna skarak birikir ve ikincil platolar olutururlar [13, 14]. Deney balangcndaki srtnme, matris-disk eklinde olurken artan deney sresi ve scaklkla birlikte matrisin giderek anmasyla elyaf paracklar yzeye kmakta, srtnme arlkl olarak elyaf-disk ekline dnmektedir. SR ve CR kodlu numunelerin srtnme katsaylarnda deney sresinin art ile birlikte yaklak 345 C disk scaklna kadar nemli bir dme olmad iin bu numunelerin yksek scaklk feyd dayanmlar olduka iyidir. Ancak MR kodlu numunelerin srtnme katsaylar, artan deney sresi ile birlikte 275 oC disk scaklna kadar artmakta ancak bu scakln zerinde keskin bir ekilde dmektedir. Bu numunelerin feyd dayanmlar ktdr. Bu melamin reinenin bozunma scaklnn dk olmas nedeniyledir.
o
SR, CR ve MR kodlu numunelerin ortalama srtnme katsaylar ekil 4 (a-c) de verilmitir. Ortalama srtnme katsays, farkl ilem basamaklarndan alnan 10 srtnme katsays deerinin ortalamasdr. Bu deerler srasyla birinci toparlama esnasnda 204 ve 149 oC, ikinci yorma esnasnda 232, 260, 288, 316 ve 343 oC ve ikinci toparlama esnasnda 260, 204 ve 149 oC dir.
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(a)
(b)
c ekil 4. Numunelerin ortalama srtnme katsaylarndaki deiim: (a) SR; (b) CR; ve (c) MR. SR ve CR kodlu numunelerin ortalama srtnme katsays deerleri artan elyaf uzunluuyla dmtr. Ancak MR kodlu numunelerde ise belirli bir deiim elde edilmemitir. Ayn elyaf uzunluklar dikkate alndnda maksimum ve minimum ortalama srtnme katsays srasyla SR ve MR kodlu numunelerde elde edilmitir. 150 m elyaf uzunluunda ortalama srtnme katsaylar SR1 ve MR1 kodlu numunelerde srasyla 0,494 ve 0,468 olarak bulunmutur. Bu deerler 300 m elyaf uzunluklarnda SR2 ve MR2 kodlu numunelerde 0,481 ve 0,441 ve 650 m elyaf uzunluklarnda ise SR3 ve MR3 kodlu numunelerde 0,472 ve 0,444 olarak elde edilmitir. Elyaf takviyeli kompozitlerde eer elyaf kompozit malzemeyi yeteri kadar desteklemez ve mukavemet kazandrmazsa, matris malzemesi kar yzey zerinde mevcut przler tarafndan mikro kazma ve mikro kesme ilemine tabi tutulur. Bunun sonucunda matris malzemesinde daha fazla anma olur. Matris grevini yapamazsa kayma esnasnda oluan srtnme kuvveti numunedeki elyaflar krmadan direkt olarak onlar yapdan kopartr. Kopan bu elyaflar ara yzeyde andrc ve kazyc olarak hareket eder bu ise muhtemelen hem srtnme katsaysn hem de zgl anma miktarn arttrr. (ekil 5a). Nispeten daha uzun elyaflarda anma daha zor meydana gelir. Balangta elyaflar yapdan kopmadan yava yava anmaya balar ve elyaflarda incelmeyle birlikte kopmalar meydana gelir. Kopan elyaflarn bir ksm anma yzeyinden ayrlrken geri kalan ksm ise belirli bir sre ikincil platolar oluturarak kompozit malzemeyi desteklemeye devam eder. Belirli bir zaman sonra mevcut elyaf btnyle kopar ve andrc olarak ilevini yapar. Ancak bu andrclk, ksa elyafla karlatrldnda nispeten daha dk oranda meydana gelir. (ekil 5b) [11, 15].
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(a) (b) ekil 5. Numunelerin anma yzeylerin SEM grntleri: (a) CR1; ve (b) CR3.
Numunelerin srtnme katsaylarnn frenleme saysyla deiimi ekil 6 (a-c) de verilmitir. ekil 6a da grld gibi, SR kodlu numunelerin srtnme katsaylar beinci frenlemeye kadar artmtr. Srtnme katsays otuzuncu frenlemeye kadar dm ve bu deerin zerinde yaklak olarak sabit kalmtr. ekil 6b de ise CR kodlu numunelerin srtnme katsaylar onuncu frenlemeye kadar artmtr. Bu deerden sonra yaklak otuzuncu frenlemeye kadar benzer ekilde dm ve bu deerden sonra yaklak olarak sabit kalmtr. MR kodlu numunelerde ise MR1 kodlu numune hari hem MR2 hem de MR3 kodlu numunelerde artan frenleme ile birlikte srtnme katsaylar yaklak olarak sabit kalmtr. MR1 kodlu numune ise deneyin balangcndan yirminci frenlemeye kadar srtnme katsays dmekte, bunun zerindeki frenleme saysnda srtnme katsays sabit olmaktadr (ekil 6c).
(a)
(b)
c ekil 6. Srtnme katsaysnn frenleme says ile deiimi: (a) SR; (b) CR; ve (c) MR.
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3.3. Anma Oran Anma genellikle scaklk, hz, basn, evre artlar ve numune-kar yzey arasndaki etkileim gibi faktrlere baldr. Balatalarn anmasna, balatada oluturan reine, elyaf ve srtnme dzenleyiciler gibi bileenler etki ederler [6, 16]. Numune gruplarnn zgl anma oranlar ekil 7 (a-c) da verilmitir. ekilde grld zere, reine tr dikkate alndnda CR kodlu numune grubu en yksek zgl anma oranna sahiptir. SR kodlu numune grubu ise zgl anmas CR kodlu numunelere gre nispeten daha dk, MR kodlu numuneler ise en dk zgl anma oranna sahiptir.
(a)
(b)
ekil 7. Numunelerin zgl anma miktarlar: (a) SR; (b) CR; ve (c) MR.
c Elyaf uzunluklar gz nne alndnda artan elyaf uzunluu ile birlikte numunelerin genellikle zgl anma miktarlar azalmtr. Bunun nedeni ise ksa elyaflarn kayma esnasnda matristen daha kolay ayrlmasdr. 3.4. Anma Yzeylerin ve Anma Paracklarnn SEM Analizi SR1, CR1 ve MR1 kodlu numunelerin anma yzeylerinin grntleri ekil 8-10 da verilmitir. ekil 8 (a-b) de grld gibi, SR1 numunesi birincil ve ikincil platolara ilaveten anma yzeyinde toz anma paracklar mevcuttur. Ayrca numune anma yzeyinde anm fakat kopmam elyaflar da bulunmaktadr.
(a) (b) ekil 8. SR1 kodlu numunenin anma yzeyinin SEM grnts: (a) X500; ve (b) X2000.
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ekil 9 (a-b), CR1 kodlu numunenin anma yzeyini gstermektedir. SR1 kodlu numuneyle kyaslandnda CR1 kodlu numunenin anma yzeyinde daha fazla oranda krlm ve kopmu elyaflar, daha fazla elyaf-matris ayrlmas mevcuttur. Krlm ve yzeyden ayrlm olan elyaflar kar yzey przlln artrmakta bunun sonucunda artan kar yzey przll ise kazma etkisiyle zgl anma miktarn artrmaktadr [17].
(a) (b) ekil 9. CR1 kodlu numunenin anma yzeyinin SEM grnts: (a) X500; ve (b) X1000. MR kodlu numunelerin mekanik zellikleri, dier numunelere gre daha dk olmasna ramen en dk zgl anma deeri gstermitir. ekil 10 (a-b) de grld gibi numune anma yzeyi, daha byk boyutta ikincil temas platosuna sahiptir. Ayrca, SR1 ve CR1 kodlu numunelerle kyaslandnda MR1 kodlu numunenin anma yzeyinde az oranda krlm ve yzeyden ayrlm elyaflar mevcuttur.
(a) (b) ekil 10. MR1 kodlu numunenin anma yzeyinin SEM grnts: (a) X500; ve (b) X500. Anma deneyi srasnda olumu anma paracklar ve bu paracklarn boyut dalm ekil 11-13 de verilmitir. Bu paracklarn incelenmesi de anma mekanizmalarnn ortaya konmas ve yzey etkileimi asndan nemlidir [18].
(a) (b) ekil 11. SR1 kodlu numunenin (a) anma paracklarnn SEM grnts; (b)Parack boyut dalm.
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(a) (b) ekil 12. CR1 kodlu numunenin (a) anma paracklarnn SEM grnts; (b)Parack boyut dalm.
(a) (b) ekil 13. MR1 kodlu numunenin (a) anma paracklarnn SEM grnts; (b)Parack boyut dalm. Anma paracklar genellikle krlm ve daha sonra yzeyden kopmu elyaf paracklarndan, numune yzeyindeki tabakalardan ve kar yzeyden kopan anma paracklarndan oluur. Bu paracklar, kar yzeyin numune yzeyine temas etmesiyle hemen yzeyden ayrlabilir veya tabaka eklinde bir sre yzeyde kalabilir. Dk anma direnci gsteren SR1 ve CR1 kodlu numunelerin anma parack ekilleri, MR1 kodlu numuneye gre olduka kresel ve birka plaka eklindedir. Yksek anma direnci gsteren MR1 kodlu numunenin anma paracklarnn ekli ise genellikle plaka ve az da olsa kreseldir. SR1, CR1 ve MR1 kodlu numunelerin ortalama anma parack boyutlar srasyla 2,609 m, 2,521 m ve 4.822 m dir. 4. SONULAR almada reine tr ve elyaf uzunluunun fren balatalarnn mekanik ve tribolojik zelliklerine etkisi incelenmitir. Srtnme performans deneyleri Chase tipi srtnme test dzeneinde gerekletirilmitir. Yaplan mekanik ve tribolojik deneylerden aadaki sonular elde edilmitir. 1. Numunelerin mekanik ve tribolojik zellikleri arasnda direkt bir iliki yoktur. Numunelerin anma oranlar srtnme katsaylaryla ilikilidir. 2. En dk ve en yksek srtnme katsays MR ve SR kodlu numunelerde elde edilirken, MR ve CR kodlu numuneler en yksek ve en dk anma direnci sergilemitir. 3. Numunelerin srtnme katsaylar ve zgl anma oranlar genellikle artan elyaf boyuyla azalmtr. 4. Uzun elyaf takviyeli numunelerin mekanik zellikleri genellikle ksa elyaf takviyeli numunelerden daha fazladr. TEEKKR Bu alma, Karadeniz Teknik niversitesi BAP Birimi 2007.112.010.1 kodlu proje kapsamnda yaplmtr. Proje desteklerinden dolay Karadeniz Teknik niversitesine teekkr ederiz.
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KAYNAKLAR 1. Satapathy, B.K., Bijwe, J., Fade and Recovery of Non-Asbestos Organic (NAO) Composite Friction Materials Based on Combinations of Rock Fibers and Organic Fibers, Journal of Reinforced Plastics and Composites, Vol. 24, pp. 563-576, 2005. 2. Kim, S.J., Cho, M.H., Lim, D.S., Jang, H., Synergistic Effects of Aramid Pulp and Potassium Titanate Whiskers in the Automotive Friction Material, Wear, Vol. 251, pp. 1484-1491, 2001. 3. Kim, S.J., Lee, J.Y., Jang, H., Effect of Humidity on Friction Characteristics of Automotive Friction Materials, KSTL International Journal, Vol. 2, pp. 150-153, 2001. 4. Ertan, R., Yavuz, N., An Experimental Study on the Effects of Manufacturing Parameters on the Tribological Properties of Brake Lining Materials, Wear, Vol. 268, pp. 1524-1532, 2010. 5. Satapathy, B.K., Bijwe, J., Composite Friction Materials Based on Organic Fibers: Sensitivity of Friction and Wear Operating Variables, Composites Part: A, Vol. 37, pp. 1557-1567, 2006. 6. Kim, S.J., Jang, H., Friction and Wear of Friction Materials Containing Two Different Phenolic Resins Reinforced with Aramid Pulp, Tribology International, Vol. 33, pp. 477-484, 2000. 7. Gurunath, P.V., Bijwe, J., Friction and Wear Studies on Brake-Pad Materials Based on Newly Developed Resin, Wear, Vol. 263, pp. 1212-1219, 2007. 8. Kumar, M., Bijwe, J., Role of Different Metallic Fillers in Non-Asbestos Organic (NAO) Friction Composites for Controlling Sensitivity of Coefficient of Friction to Load and Speed, Tribology International, Vol. 43, pp. 965-974, 2010. 9. Gopal, P., Dharani, L.R., Blum, F.D., Fade and Wear Characteristics of A Glass-Fiber-Reinforced Phenolic Friction Material, Wear, Vol. 174, pp. 119-127, 1994. 10. Bijwe, J., Nidhi, Satapathy, B.K., Influence of Amount of Resin on Fade and Recovery Behaviour of Non-Asbestos Organic (NAO) Friction Materials, Transaction of the Indian Institute of Metals, Vol. 57, pp. 335-344, 2004. 11. Zhang, H., Zhang, Z., Friedrich, K., Effect of Fiber Length on the Wear Resistance of Short Carbon Fiber Reinforced Epoxy Composites, Composites Science and Technology, Vol. 67, pp. 222230, 2007. 12. Subramaniam, N., Sinha, B.R., Blum, F.D., Chen, Y.R., Dharani, L.R., Glass Fiber Based Friction Materials, International Journal of Polymeric Materials, Vol. 15, pp. 93-102, 1991. 13. Eriksson, M., Jacobson, S., Tribological Surfaces of Organic Brake Pads, Tribology International, Vol. 33, pp. 817-827, 2000. 14. Nidhi, Bijwe, J., Mazumdar, N., Influence of Amount and Modification of Resin on Fade and Recovery Behavior of Non-Asbestos Organic (NAO) Friction Materials, Tribology Letters, Vol. 23, pp. 215-222, 2006. 15. ztrk, B., ztrk, S., Effects of Resin Type and Fiber Length on the Mechanical and Tribological Properties of Brake Friction Materials, Tribology Letters, Vol. 42, pp. 339-350, 2011. 16. ztrk, B., Arslan, F., ztrk, S., Hot Wear Properties of Ceramic and Basalt Fiber Reinforced Hybrid Friction Materials, Tribology International, Vol. 40, pp. 37-48, 2007. 17. Vishwanath, B., Verma, A.P., Rao C.V.S.K., Friction and Wear of A Glass Woven Roving/Modified Phenolic Composite, Composites, Vol. 21, pp. 531-536, 1990. 18. Mosleh, M., Blau, P.J., Dumitrescu, D., Characteristics and Morphology of Wear Particles from Laboratory Testing of Disk Brake Materials, Wear, Vol. 256, pp. 1128-1134, 2004.
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MECHANICAL ALLOYING
www.turkishpm.org
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The effect of reinforcement ratio on hardness of Al-Al2O3 composites fabricated by mechanical alloying technique
Aykut Canakci1, Temel Varol1, Saban Ertok1
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Department of Metallurgical and Materials Engineering, Karadeniz Technical University, Trabzon, Turkey aykut@ktu.edu.tr, tvarol@ktu.edu.tr Abstract
In this work, mechanical alloying technique was used to produce aluminum (Al) matrix composite reinforced with alumina (Al2O3). A mixture of Al and 5, 10, 15 vol. % Al2O3 powders were milled in a high energy milling process. The powder mixtures were milled in a planetary ball mill for different milling times of 0.5, 2, 5 and, 7 h. Ball mill velocity was 400 rpm and ball to powder weight ratio was 10: 1. Methanol was used as process control agent (PCA). Mechanic alloyed composite powders were consolidated as compacts and sintering (under argon). Mechanical alloying was followed by SEM, particle size and hardness. The results show that increase in volume fraction of reinforcement particles increases the work hardening, affecting structural evolution and hardness of the composites. Moreover, The results show that physical properties of Al-Al2O3 composites depend strongly on milling time so that increasing milling time causes to change the values of properties of composites. Keywords: Mechanical alloying (MA); Aluminium-based metal matrix composites (Al-MMCs); Alumina (Al2O3) 1. Introduction In recent years, alumium alloy based metal matrix composites are interested their importance for endustries like automative and aerospace due to their engineered properties. Aluminum matrix composites (AMCs) are widely used for light weight, unique mechanical properties [1,2]. MMCs can be formed from solid and molten states into forging, extrusions, sheet and plate and casting. Conventional techniques like casting, spraying and forging have problems like reinforcement segregation,unwanted interfacial chemical reactions, higher porosity and poor interfacial bonding. Due to the presence of alumina particles with high melting point, conventional melting and casting is not suitable for producing dispersion-strengthened Al composites [3,4]. Alternatively, powder metallurgy ensures the fine alumina dispersoid is well distributed within the Al matrix, which eventually gives good final mechanical properties to the composite with sufficient physical properties. Mechanical alloying has also been employed to synthesize AMC. This method is relatively easy to produce composite powders with fine microstructure [5]. Mechanical alloying (MA) that is a ball milling process where the powder particles are subjected to high energy impact have been recently used in the production of aluminum base matrix composite. MA enables a uniform distribution of the reinforcement particles into the aluminum matrix, the refining of the metal matrix and the fracturing of the hard reinforcement particles [6]. The purpose of this study was to prepare Al-Al2O3 composite powder by mechanical alloying and to investigate the influence of the milling time and the effect of reinforcement volume fraction on composite hardness and the structural evolution during MA. 2. Experimental Procedure 2.1. Materials The as-atomized Al alloy powders (Gndodu Exotherm Company, Turkey) with an average particle size of 377 m, Al2O3 powders (99,7 % purity, Wacker Ceramic Company, Germany) with an average particle size of 13 m
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which varies between 5 m and 25 m and the density of 3.95 g/cm3 are used as raw materials. The chemical composition of the as-atomized Al alloy (in wt. %) is 1.230Fe, 1.000Si, 1.000Pb, 0.710Cu, 0.530Zn, 0.116Mn, 0.071Ti, 0.050Mg and Al (balance). Fig 1(a) and (b) shows the morphologies of the as received Al alloy matrix powder and Al2O3 particles.
Fig. 1. Morphology of as-received powders: (a) Al alloy and (b) Al2O3 particles. 2.2. Milling Composites powders of Al alloy matrix reinforced with different amount of Al2O3 (in vol. %5, %10 and %15) by highenergy ball milling for 0.5 h, 2 h, 5 h, and 7 h. The milling process was carried out in a planetary ball-mill (Fritshc Gmbh, model Pulverisette Premium Line 7) at room temperature using tungsten carbide bowl and high argon atmosphere. The milling medium was tungsten carbide balls, 10 mm in diameter. The ball-to-powder weight ratio (BPR) and rotational speed were 10:1 and 400 rpm, respectively. A total of 1.75 wt. % of methanol (Merck) was added to the ball-mill as process control agent (PCA). The milling atmosphere was argon which was purged into the bowl before milling. To prevent over heating, ball milling experiments were stopped (every 0.5 h) and then resumed when the temperature of the bowl decreased to the room temperature. Powders samples were withdrawn at time intervals of 0.5, 2, and 5 h for morhological, microstructural and structural analyses. 2.3. Powder characterization The size distribution of as-received and milled powders was quantified by a laser particle size analyzer (Malvern, model Mastersizer Hydro 2000). The morphology and microstructure of raw and milled powders were investigated by scanning electron microscopy (SEM) using Zeiss LS10. The microhardness of as-received and milled powders was measured by a microhardness tester (struers microhardness tester) at 10 gr load. 2.4. Powder compaction The as-received Al alloy powder, the conventionally mixed (CM) and the mechanically alloyed powders were uniaxially cold pressed in a cylindrical die at 500 and 700 MPa to block specimen with dimension of 30x20 mm, with graphite as the die lubricant. The green compacts were sintered 600 oC for 3 h under high argon atmosphere. The sintered compacts were cooled to room temperature in the sintering furnace. 2.5. Microscopic evaluation To evaluate microstructure of produced composites the surface of samples were polished to achieve a rough surface of about 0.05 m. The microstructures of the conventially mixed and the milled Al alloy-Al2O3 composites were examined by Zeiss scanning electron microscope. 3. Result and discussion 3.1. Particle size evaluation of milled powder The effect of milling time on the particle size of ductile-ductile and ductile-brittle powders has been studied separately by previous authors [7-12]. The effect of milling time on the average particle size of monolithic Al alloy and Al alloy-Al2O3 composite powders was shown in Fig. 2. Unlike most of the work related to mechanical alloying [13-16], in this study, the particle size decreases continuously. This can be attributed to the initially used Al alloy powders having ligamental shape. These powders can be easily deformed by high energy collisions at balls and they can be
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easily fractured weakness regions. It should be noted that initial powder morphology is an important factor affecting the change of the particle size. The average particle size (d0.5) of the monolithic Al alloy and Al-Al2O3 composites powders were decreased same trend with increasing milling time (Fig. 2).
Fig. 2. The change of particle size of Al alloy and composite powders with milling time The average particle size of the Al alloy-Al2O3 composite powders was lower than that of the Al alloy powders it was reduced by increasing the reinforcement content. Indeed, the presence of the ceramic phase accelerates the rate at which the milling process reaches completion. The presence of alumina particles increases local deformation which improves the particle welding process. Beside this, the higher local deformation imposed by reinforcement particles increases the deformation hardening, which helps the fracture process. The small hard brittle particles in the matrix act as small milling agents, and thus the steady state the milling time is reduced. A similar behavior was observed the ball milling of Al20 wt. % Al2O3 system [11] and Al-AlN system [9,10,17,18]. 3.2. Milled powder characteristics The as-received aluminum alloy matrix powders were irregular and ligamental shape (Fig. 1a). By continuing milling process, these powders are deformed and transmitted to flatten and flake shapes and weld to each other. Then these changes followed by fracture and rewelding, repeatedly [11]. After 0.5 h milling, the Al alloy powders deform into a flake like shape (Fig. 3a). Due to ductile nature of the Al alloy powder, welding seems to be the dominating mechanism over this stage of milling [7,10,11], and thus the 0.5 h milled particles have large size and flattened shape (Fig. 3a). The large size and flatten shape like Al alloy powders are work hardened after 2 h milling, hence fracture mechanism is activated (Fig. 3b).
Fig. 3. Morphology of the milled Al alloy powders for: (a) 0.5 h, (b) 2 h, (c) 7 h. SEM micrographs of milled Al alloy powders showed that after 5 h milling, the morhology of Al alloy powders were not completely equiaxed, which is the characteristic of Al alloy powders at steady state. Further milling up to 7 h has no effect on the morphology (Fig. 3c); indeed at milling times longer than 5 h the steady state predominates. The variation of Al alloy-Al2O3 powder shape during high energy ball milling as the function of milling time up to 7 h is shown in Fig. 4(ac). During the MA process, powders are subjected to high energy collision, which caused severe plastic deformation, cold welding and fracturing of the powders. Plastic deformation and cold welding were predominant during initial stage of high-energy ball milling, in which the deformation led to a change in particle shape and cold welding led to an increase in average particle size. The addition of hard reinforcement particles would accelerate the fracture process of the matrix powders, which was reported elsewhere [13]. The increased
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fracturing tendency for high reinforcement was due to more collision with balls and more support from hard ceramic particles [14]. In order to understand the effect of reinforcement ratio on the mechanical alloying process and composite properties, Al powders were milled with different amounts of Al2O3 (0, 5, 10, and 15 vol. %) for 0.5, 2, 5, and 7 h. If the presence of reinforcement results in a high deformation of the metallic matrix and advances the mechanic alloying process, a higher reinforcement fraction will result in a still greater deformation of the metallic particles and will accelerate the process even more. The reinforcement particles embedding into the Al powders during milling lead to their fracture toughness reduction enhancing their fracture.
Fig. 4. Morphologies evolution of the Al alloy reinforced with different amount of Al2O3 (in vol. %5, %10 and %15) by high-energy ball milling for 0.5 h, 2 h, 5 h, and 7 h: (a) 0.5 h, (b) 2 h, and (c) 7 h. 3.3. Microstructure Fig. 5 shows the evolution of distribution of the Al2O3 particulates reaching milling time in the Al alloy matrix for Al-Al2O3 composites. Fig. 5. A schematic view of the evolution of distribution of the Al2O3 particulates reaching milling time in the Al matrix [19].
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The main process which takes place in a mill during the MA method to produce quality powders with controlled microstructure is the repeated welding, fracturing, and rewelding of a mixture of powders. The morphology of the initial powders is modified when they are subjected to ball collisions [15]. Initial stages of MA, welding process too much dominant than fracture because of that powders are exposed to high cold deformation. The presence of reinforcement particles between the particles during welding increases local deformation in the around of the reinforcement particle. An increase the local deformation improves the particle welding process and also increment of reinforcement lead to improvement of fracture mechanism on continuous process. In other words, small hard brittle particles in the mix act as small milling agents, with an improvement of the energy of the system. Therefore, reducing the milling time necessary to achieve uniform dispersing of reinforcement particles. The effect of milling time on the distribution of Al2O3 powders is investigated by SEM. Figs. 6-8 show the distribution of reinforcement powders (5, 10, and 15 vol. % Al2O3) milled with different milling time (0.5, 2, and 7 h). SEM images show that most of the reinforcement powders dispersed inside the Al matrix at the end of a long milling time while Al2O3 powders werent showed a homogeneous distribution within the matrix in short milling time. In other words, the homogeneous distribution of the reinforcement powders provided with increasing milling time.
Fig. 6. Distribution of alumina particles of Al alloy-5 vol. % Al2O3 composites in the Al alloy matrix with milling time after (a) 0 h, (b) 0.5 h, (c) 2 h, and (d) 7 h.
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Fig. 7. Distribution of alumina particles of Al alloy-10 vol. % Al2O3 composites in the Al alloy matrix with milling time after (a) 0 h, (b) 0.5 h, (c) 2 h, and (d) 7 h.
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Fig. 8. Distribution of alumina particles of Al alloy-15 vol. % Al2O3 composites in the Al alloy matrix with milling time after (a) 0 h, (b) 0.5 h, (c) 2 h,and (d) 7 h.
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The particle distribution was not uniform at initial milling time (0 h, 0.5 h) and the distance between alumina particles was too much. However, increasing milling time caused to fracture the brittle alumina powders and to embed them into ductile Al powders. The distance between reinforcement particles decreases with increasing milling time (Figs. 6-8). 3.4. Hardness The result of micro and macro-hardness for different milling time and different compact pressure is shown in Figs. 9-10. Micro and macro hardness values increases with increasing milling time and with the reinforcement content. MA assists a high degree of deformation and reduces the grain size to finer level. As can be seen from figures, increasing milling time fractures coarse powder particles into fine particles due to cold welding and plastic deformation. The rate of an increase in micro-hardness is high and becomes even greater after reaching 5h of milling. The increase in hardness values can be explained more homogeneous distribution of reinforcement particles, increasing work hardening decreasing grain size [10, 20-22]. In addition, as shown in the Figures; hardness values increases with increasing compact pressure because of decreasing porosity. When particle morphology, particle size and composite hardness examined it was observed that measurements done at the end of 5 and 7 h of milling were close to each other. Based on this, it can be expressed mechanical alloying process reached virtually steadystate at the end of 5 h of milling.
Fig. 9. Micro-hardness of the Al alloy and composites versus milling time at different compact pressure (a) 500 MPa and (b) 700 MPa. The Brinell hardness of the composites and matrix alloy was given in Fig. 10. It was seen from Fig. 10 that the hardness of the composites increased with increasing particle volume fraction. As compared to the Al matrix alloy, the hardness of the MMCs was found to be greater, and addition of Al2O3 particles increase the hardness of the Al alloy [23-25].
Fig.10. Macro-hardness of the Al alloy and composites versus milling time at different compact pressure (a) 500 MPa and (b) 700 MPa.
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4. Conclusion In this work, Al2O3 reinforced Al alloy base composites were synthesized by mechanical alloying process. The milling time was varied from 0.5 h to 7 h while volume fraction was varied from 0% to 15%. Mechanical alloying appears to be an ideal technique to produce composites in a variety of systems. The most impressive advantage of the mechanical alloying method is that a uniform dispersion can be succeed by optimizing the process parameters. It was observed that higher hardness is obtained when volume fraction (reinforcement ratio) was increased. The results of the macro-hardness measurements for Al-Al2O3 composites show a important increase in hardness as compared to the unreinforced sample. Moreover, the average particle size, powder morhology, and hardness of properties of the monolithic Al alloy matrix and the composites were reached virtually a steady state value at the end of 5 h of milling tim by mechanical alloying process. Acknowledgement The authors are grateful to Karadeniz Technical University Research Fund for the financial supporting of this research work (No: 2007.112.10.2 ). The researchers would also like to thank to Gundogdu Exotherm Service for providing Al-alloy powders. 5. References 1. C. Padmavathi., Anish. Upadhyaya., Science of Sintering (2010) 42 363-382 2. C. Suryanarayana, Journal of Alloys and Compounds 529 (2010) 229-234 3. B. Prabhu, C. Suryanarayana, L. An, R. Vaidyanathan , Mater Sci Eng A (2006) 425:192-200 4-. G. ODonell, L. Looney, Mater Sci Eng A (2001) 303: 292301 5. S.M. Zebarjad, S.A. Sajjadi, Materials and Design 28 (2007) 2113-2120. 6. Grazziani Maia Candido, Vanessa Guido, Gilbert Silva, Ktia Regina Cardoso, Materials Science Forum Vols. 660-661 (2010) 317-324 7. Rodiguez A, Gallardo JM, Herrera EJ (1997) J of Mater Sci 32: 35353539 8. El-Eskandarany MS (2000) William Andrew Publishing, New York 9. Fogognolo JB, Velasco F, Robert MH, Torralba JM (2003) Mater Sci Eng A 342: 131143 10. Razavi Tousi SS, Yazdani Rad R, Salahi E, Mobasherpour, I Razavi M (2009) Powder Tech 192: 346351 11. Abdoli H, Salahi E, Farnoush H, Pourazrang K (2008) J of Alloys and Compounds 461: 166-172 12. Arik H, Turker M (2007) Mater and Design 28: 140146 13. Razavi Hesabi Z, Simchi A, Seyed Reihani SM (2006) Mater Sci Eng A, 428:159-168 14. Sivasankaran S, Sivaprasad K, Narayanasamy R, Vijay Kumar Iyer (2010) Powder Tech 201: 7082 15. Adamiak M (2008) J Achiev Mater Manuf Eng 31(2): 191196 16. Hashim J, Looney L, Hashmi MSJ (1999) J of Mater Process Tech 92:1 17. Fogognolo JB, Robert MH, Torralba JM (2006) Mater Sci Eng A 426: 8594 18. Fogognolo JB, Ruiz-Navas Elisa M, Robert MH, Torralba JM (2003) Mater Sci Eng A 355: 5055 19. L, Lu, M.O. Lai, C.W. Ng, Materials Science and Engineering A252 (1998) 203-211 20. I. Estrada-Guel, C. Carreno-Gallardo, D.C. Mendoza-Ruiz, M. Miki-Yoshida, E. Rocha-Rangel, R. MartinezSanchez, Journal of Alloys and Compounds 483 (2009) 173-177, 21. H. Arik, Materials and Design 25 (2004) 31-40, 22. E.M. Ruis-Navas, J.B. Fogagnolo, F. Valesco, J. M. Ruiz-Prieto, L. Froyen, Composites: Part A 37 (2006) 21142120, 23. Kok M (2005) J Mater Process Technol 161:381. 24. Purazrang K, Abachi P, Kainer KU (1994) Composites A 25(4):296. 25. A. Canakci, J Mater Sci (2011) 46:28052813.
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PRODUCTION OF Al-[Al-Al3Ti] NANOCOMPOSITE BY MECHANICAL ALLOYING AND TWO-STEP HOT PRESSING

Armin VAHID MOHAMMADI*, Hamid Reza MADAAH HOSSEINI** * Department of Materials Science and Engineering, Sharif University of Technology, Tehran, Iran, arminvm@ gmail.com ** Department of Materials Science and Engineering, Sharif University of Technology, Tehran, Iran, madaah@ sharif.edu ABSTRACT Pure Al powder was mixed with 20 wt.% pure Ti powder to produce Al-Al3Ti composite powder by Mechanical Alloying (MA) for 12 hours. The produced composite powder was mixed with pure Al powder in 10, 15 and 20 wt.%. Two-Step hot pressing was performed to produce Al-[Al-Al3Ti] bulk nanocomposites. The results show that effective temperature range for first and second step of hot pressing was between 620 - 625 C and 570 - 585 C, respectively. Furthermore the highest density was achieved in the sample with 20 wt.% of pure Al. Keywords: Al-Al3Ti, Nanocomposite, Hot Pressing, Mechanical Alloying 1. INTRODUCTION Recent advances in producing nanostructured materials with novel material properties have stimulated research to create multi-functional macroscopic engineering materials by designing structures at the nanometer scale. Motivated by the recent enthusiasm in nanotechnology, development of nanocomposites is one of the rapidly evolving areas of composites research [1]. According to this, recently most researches have focused on production of composites and nanocomposites by using different sintering processes such as Hot Pressing, hot extrusion, and hot isostatic pressing (HIP) [2]. Hot pressing is widely used in the manufacturing process of high strength materials such as Al and Ti alloy and stainless steel [2-3]. However, grain growth occurs readily during the high temperature consolidation of nanocrystalline materials [4,5], because nanocrystalline materials are thermally unstable. Thus, the full benefit of nanocrystalline materials may only be preserved if the consolidated specimen maintains its nanosized grains. Two-Step Hot Pressing is a technique that in comparison to Single-Step hot pressing enables reaching higher densities while controlling grain size [6,7]. Aluminum composites reinforced with trialuminide particles (Al3Ni, Al3Fe, Al3Ti, Al3Zr, etc.) possess high specific strength, high specific modulus, and excellent properties both at ambient and elevated temperatures [7]. In comparison to most other aluminum-rich intermetallics, Al3Ti with higher melting point (~1623 K), relatively low density (3.4 g/cm3) and high Youngs modulus (217 GPa; which are comparable with the properties of SiC) is the most considerable tri-aluminide for Al matrix composites [2,7,8]. Therefore, the presence of Al3Ti intermetallic phase is very effective in increasing the strength and stiffness of aluminum composite and nanocomposites. The major strengthening mechanisms, which contribute to the high strength of AlAl3Ti alloys, have been suggested to include Orowan strengthening mechanism, grain size strengthening, and load-shearing effects of Al3Ti particles [7-13]. In this research Mechanical Alloying was used to mix the Al and Ti powders and form the Al-Al3Ti composite nanopowder. Pure Al powder was added to the produced composite powder as a modification parameter to achieve a fully dense structure. Furthermore, Two-Step hot pressing was performed to produce Al-[Al-Al3Ti] bulk nanocomposites and effect of different parameters of hot pressing on the density of produced samples was investigated
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2. EXPERIMENTAL PROCEDURE Aluminum fine powder Merck (average particle size of 45-150 m) with 99.9% purity were mixed with 20 wt.% Titanium Powder Merck (average particle size of 10 m) with 99.9% purity by using mechanical alloying (High-energy vibrating mill) for 12 hours. The produced Al-Al3Ti composite powder with average particle size of 100 nm was degassed using a tunnel furnace in a vacuum atmosphere and again mixed with Pure Al powder in 10, 15 and 20 wt.%. Sample 1 consisted of 10% pure Al powder (9 g Al-Al3Ti + 1 g Al), Sample 2 had 15% pure Al powder (8.5 g Al-Al3Ti + 1.5 g Al) and sample 3 had 20% pure Al (4 g Al-Al3Ti + 1 g Al). Two-step hot pressing was performed for manufacturing the bulk nanocomposite by in situ reaction. In table 1 hot pressing conditions for test samples have been shown. Hot press temperatures were chosen according to AlTi binary phase diagrams, which would cause the formation of intermetallic phase Al3Ti [2]. Three different pressures (110, 130, and 150 KN) at three different durations for first and second steps (10-30, 5-45, and 10-45 min) were applied at the mentioned temperature. The pressing was performed by Gotech Testing Machines Inc. U60 with pressure rate of 3 mm.min-1. Apparent density measurement was performed according to ISO 3923-1:2008 standard using Archimedes method and Theoretical density measerments was performed according to ASTM D854-92e1 standard using pycnometery method. SEM and EDS analysis were done by TESCAN VEGA scanning electron microscopy and image analyzing was performed on SEM images. Table 1. Two-Step Hot Pressing Conditions for samples. Temperature (C) Sample 1 Sample 2 Sample 3 First Step Second Step First Step Second Step First Step Second Step 625 585 620 570 620 570 Time (min) 10 30 5 45 10 45 Pressure (MPa)/(KN) 339.5/110 462.9/150 401.2/130
3. RESULTS AND DISCUSSION Morphology changes of Al-Al3Ti composite powder is shown in fig. 1. SEM images taken in 1.5 and 12 hrs of mechanical alloying showed that by increasing MAs time the morphology of composite powder changed from a palette shape to a homogenous structure, while its size decreased. EDS data which are shown in fig. 2 proved the formation of Al3Ti inter-metallic phase after 12 hrs of MA. Furthermore, Image analyzing on SEM images showed an increase in volume fraction of this inter-metallic phase by increasing MA time.
Fig. 1. Morphological changes of composite powder. (a) after 1.5 hr of MA (b) after 12 hr of MA.
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Fig. 2. EDS data of composite powder after 12 hrs of MA which proves the formation of Al-Al3Ti intermetallic phase. In the following, effect of different parameters of Two-Step hot pressing on the density of the produced nanacomposites has been discussed. 3.1 Time and Temperature of First and Second Step of Hot Pressing Table 2 shows the theoretical density and real density of produced samples. In the first step of two-step hot pressing due to higher temperature and more grain growth, decreasing time to a limit helps to produce a more dense structure while keeping grain size in nano scale. Indeed in the first step the temperature range is near the melting point of Al, so the growth rate of particles due to increasing of diffusion is very fast and decreasing time is a key parameter to control the grain size of produced naonocomposite. In this research in the first step of hot pressing, temperature (T1) range between 620 and 625 C in time period between 5 and 10 min was effective for achieving higher densities while maintaining grain size in nano scale. Table 2. Theoretical density and real density of produced samples. Theoretical Density (g/cm3) Sample 1 Sample 2 Sample 3 3.0230 3.0050 2.9870 Real Density (g/cm3) 2.9287 2.8452 2.9006 Density Percentage 96.68 % 94.68 % 97.1 %
In the second step of hot pressing, due to lower temperatures and slower grain growth, hot pressing duration should be longer. In fact, according to Wang et al [6], second step temperature should be restricted within a range, called the kinetic window, here the grain boundary or the volume diffusion operates while the grain boundary motion is frozen. It is worthy to remark that the choice of temperature T2 is very important because the grain growth may be generated when the setting T2 is too high; in contrary the densification is exhausted due to the suppression of atomic diffusion and results in an incomplete densification. Therefore in this study effective temperature (T2) range for the second step was obtained between 570 and 585 C in duration of 30 to 45 min. 3.3 Hot Pressing Pressure Both steps of hot pressing were performed at a constant pressure to minimize the probable sudden changes in samples. In fig. 3 density percentage changes of samples vs. hot Pressing pressure is shown. As given in table 2 we see a few increase in the density of sample 3 which was hot pressed at 130 MPa compared to sample 1 that hot pressed at 110 MPa. Meanwhile by increasing the pressure to 150 MPa in sample 2, we see a noticeable decrease in the density. Although this decrease could be due to the other different factors, such as wt.% of secondary added pure Al powder or sample weight (because of single-action hot pressing performed in this research) which are discussed in the following sections, it was concluded that the pressure had a effective range between 110 - 130 MPa and increasing it more than an upper limit which was obtained 150 MPa would cause a less densification.
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Fig. 3. Density percentage changes of samples to Hot Pressing pressure. 3.4 Secondary Added Pure Al Powder Wt.% As indicated secondary added pure Al powder was used as a modification factor for reaching higher densities and producing fully-dense Al-[Al-Al3Ti] bulk nanocomposite. The results given in table 2. with regard to samples hot pressing conditions given in table 1. indicated that by increasing the amount of pure Al powder from 10 wt.% in sample 1 to 15 wt.% in sample 2 the density decreased. However, by increasing it from 15 wt.% to 20 wt.% in sample 3, we see a increase in density which could be because of lower sample weight and also lower pressure. 3.5 Sample Weight Due to single-action pressing used in this research, sample weight had very critical effect on the density of the produced samples. As given in table 2 we see an increase in the density of sample 3 while decreasing sample weight from 10 g for sample 1 and 2 to 5 g for sample 3. This increase has happened in spite of decreasing the pressure and increasing pure Al powder wt%, which means because of using single-action pressing, the decrease in the total sample weight has caused this increase in the density despite of increased negative factors on the density. This also proves the mentioned behaviors in the section 3.3 and 3.4. 3.5 Scanning Electron Microscopy (SEM) Analysis Fig 4. shows the SEM images of sample 1. White phases in this SEM images represents Ti and dark gray phase is Al. Also light gray phase which is mostly formed around Ti phase represents Al-Al3Ti intermetallic phase. In fig. 5. and 6. SEM images of sample 2 and 3 are shown. Also EDS analyses were performed to prove the formation of Al-Al3Ti intermetallic phase in light gray regions. Fig. 7 shows the EDS dates of sample 3, analyzed point is marked on the SEM image of sample 3 in fig. 6.
Fig 4. SEM images of sample 1. (a) Scale of 100 m (b) Scale of 20 m.
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Fig. 7. EDS data of Sample 3 which proves the formation of Al-Al3Ti intermetallic phase in light gray regions. 4. CONCLUSION The influence of time, temperature and pressure of tow-step hot pressing on density of Al-[Al-Al3Ti] nanocomposite was investigated. SEM was utilized to study the morphology and structure of the different phases and EDS analysis was performed to prove the formation of Al3Ti intermetallic phase. The conclusions derived from the results are as follows. Density measurements for samples revealed that for the first step of hot pressing, duration of 5 - 10 min at a temperature range between 620 - 625 C was effective for production of the bulk nanocomposite with a high density. Also for the second step, duration of 30 - 45 min at a temperature range between 570 - 585 C proved to be a ideal condition for maintaining the grain size at nano scale while reaching higher densities.
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Furthermore, by increasing the hot pressing pressure from 110 to 130 MPa at different durations, the density gently increased. Also for sample at 150 MPa, a considerable reduction was seen. The highest density achieved in sample with 20 wt.% of secondary added pure Al. Moreover due to single action pressing, by decreasing sample weight despite of an increase in the other negative factors, the density increased. SEM images and EDS analysis proved the formation of Al3Ti intermetallic phase mostly around the Ti phase in the bulk nanocomposites. 5. ACKNOLEDGEMENTS The authors gratefully acknowledge Miss Sogol Palaseyed, RAZI research center and Ceramic laboratory of Sharif University of Technology for their help and support of this research. 6. REFRENCES 1. Erik T. Thostenson, Chunyu Li, Tsu-Wei Chou, Nanocomposites in context, Composites Science and Technology, 65 (2005) 491516. 2. M. Nofar, H.R. Madaah Hosseini, N. Kolagar-Daroonkolaie, Fabrication of high wear resistant Al/Al3Ti metal matrix composite by in situ hot press method, Materials and Design, 30 (2009) 280286. 3. K.T. Kim, H.C. Yang, Densification behavior of titanium alloy powder during hot pressing, Materials Science and Engineering, A313 (2001) 4652. 4. H. Hahn, J. Logas, R.S. Averback, J. Mater. Res. 5 (1990) 609. 5. Kyoung Il Moon, Hee Sub Park, Kyung Sub Lee, Study of the microstructure of nanocrystalline Al5 at.% Ti compacts prepared by reactive ball milling and ultra-high-pressure hot pressing, Journal of Alloys and Compounds, 325 (2001) 236244. 6. Chih-Jen Wang, Chi-Yuen Huang, Yu-Chun Wu, Two-step sintering of fine aluminazirconia ceramics, Ceramics International, 35 (2009) 14671472. 7. Karel Maca, Vaclav Pouchly, Pavel Zalud, Two-Step Sintering of oxide ceramics with various crystal structures, Journal of the European Ceramic Society, 30 (2010) 583589. 8. S.S. Nayaka, S.K. Pabi, B.S. Murty, Al(L12)Al3Ti nanocomposites prepared by mechanical alloying: Synthesis and mechanical properties, Journal of Alloys and Compounds, 492 (2010) 128133. 9. Nikitin VI, Wanqi JIE, Kandalova EG, Makarenko AG, Yong L., Preparation of AlTiB grain refiner by SHS technology. Scripta Mater, 2000;42:5616. 10. C.J. Hsu, C.Y. Chang, P.W. Kao, N.J. Ho, C.P. Chang, AlAl3Ti nanocomposites produced in situ by friction stir processing, Acta Materialia, 54 (2006) 52415249. 11. Feng CF, Froyen L. Acta Mater 1999;47:4571. 12. Wu JM, Zheng SL, Li ZZ. Mater Sci Eng A 2000;289:246. 13. Kwang-Min L, In-Hyung M. High temperature performance of dispersion-strengthened Al-Ti alloys prepared by mechanical alloying. Materials Science and Engineering A, 1994, 185:165171.
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THE EFFECT OF RARE-EARTH CATIONS ON THE STRUCTURAL PROPERTIES OF BaFe12O19 HARD MAGNETS
Glten SADULLAHOLU*, Burcu ERTU*, Hasan GKE*, Baki ALTUNCEVAHR**, A. M. Ltfi VEOLU* and Okan ADDEMR* Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak, Istanbul, Turkey, sadullahoglu@itu.edu.tr * Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak, Istanbul, Turkey, ertug@gmail.com * Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak, Istanbul, Turkey, gokceh@itu.edu.tr ** Istanbul Technical University, Physics Engineering, 34469 Maslak, Istanbul, Turkey, altuncevahir@itu.edu.tr * Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak, Istanbul, Turkey, ovecoglu@itu.edu.tr * Istanbul Technical University, Metallugical and Materials Engineering,, 34469 Maslak, Istanbul, Turkey, addemir@itu.edu.tr
*
ABSTRACT The samples of Ba0.85R0.15Fe12O19 (where R= Nd3+, Sm3+ and La3+ ions) were prepared by the solid state sintering using stoichiometric proportions of pure BaCO3, Fe2O3 and of R2O3 added compositions. The mixed powders were milled for 10 h in toluen medium by using SPEX8000D with 1200 rpm. The pressed samples were sintered at 1000oC for 1h and 5h and at 1250oC for 1 h under air. In the DTA analysis the onset temperature to form the BaFe12O19 phase increased by inducing rare earths in barium hexaferrite composition. For the undoped sample reaction peak temperature is 985C and onset temperature is 800C corresponding to the formation of the BaFe12O19 phase. For the Sm, Nd and La substituted samples the onset temperatures are 880C, 850C and 900C respectively which are above that of the undoped composition. Keywords: Barium hexaferrite, rare earth substitutions, mechanical alloying. 1. INTRODUCTION Barium ferrite has a hexagonal crystal structure and fairly large uniaxial crystal anisotropy. There are five iron sublatices which are three octahedral (2a, 12k and 2b) and two tetrahedral (4f1 and 4f2) are coupled by superexchange interactions through oxygen to form ferromagnetic structure [1,2]. The hexagonal c axis is the easy axis and the crystal anisotropy constant K is 3.3x106 erg/cm3 or 330kJ/m3. The Ms is low, 380 emu/cm3 or or 72 emu/gr at room temperature. The Curie point is 450oC. The hexagonal unit cell of barium ferrite contains 64 atoms, the Ba2+ and O2- ions both are nonmagnetic, the only magnetic Fe3+ ions, each will a moment of 5 B. Of the 24 Fe3+ ions, 16 are in one direction, 8 are arranged in the opposite direction, therefore, (16-8)(5)=40 B per cell or 20 B per formula. This quantity corresponds to 100 emu/g and agrees axactly with the measured value of the saturation magnetization at 0 Kelvin [3,4]. Many researches have been performed to improve magnetic properties of MFe12O19 (M=Sr, Ba) ferrites by introducing di-tri- and tetravalent metal ions (Al, Mn, Co, Ti, Sn, e.c.) substituting to Fe3+ ions. Furthermore, in the early investigations the occupation of the sublattice in the structure by trivelent RE ions (Nd3+, Sm3+, La3 or Pr3+) in stead of Ba2+ or Sr2+ ions causes the valans change of Fe3+ to Fe2 on the 2a crystallografic sites where the strong Fe2 anisotropy leads to an increase in magnetocrystalline anisotropy or coercivity depending on the molar ratio of the substitutional rare earth ion [5-13].
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In order to extend these investigations the effects of RE cations (Nd3+, Sm3+ and La3+) were studied on the formation temperature of BaFe12O19 phase associated with the solubility properties of the substitutional additions in the structure. 2. EXPERIMENTAL A series of Ba0.85RE0.15Fe12O19 (RE=Nd,La and Sm) samples was prepared by mechanically alloying of the BaCO3, RE2O3 , and Fe2O3 powders followed by heat treatment. The amounts of the prepared powder batches weighed in a XB320M (PrecisaTM, Dietikon, Switzerland) sensitive balance were 56 g. MA experiments were carried out in a vibrating ball mill SpexTM 8000 D Mixer/Mill,NewJersey,USA) with a speed of 1200 rpm in a hardened steel vial (50 ml capacity) and hardened stainles steel balls with a diameter of 6.35mm (1/4 in.) with a ball-to-powder weight ratio (BPR) of 10:1. Mechanical alloying duration was chosen 10 h. Toluene was used as the milling media to inhibit agglomeration. At the end of the milling process, the wet powders were unloaded and toluene was vapourized in the furnace at 200oC for 12 h under air. The dry powders were cold pressed into pellets with a diameter of 12 mm. Cold pressed samples were annealed for 1 h and 5 h at 1000oC, and for 1 h at 1250oC under air. Exothermic and endothermic reactions were determined by DTA analysis by heating the as-blended and milled powders up to 1200C with the heating rate of 10/min in air. The phase compositions of the milled powders and the sintered samples were performed by X-ray diffraction (XRD) technique using a D8 Advanced Series Powder Diffractometer (BrukerTM, Karlsruhe, Germany) with Cu-K (1.54060 A) radiation in the 2 range of 2080 with 0.02o steps at a rate of 2/min. International Centre for Diffraction Data (ICDD) powder diffraction files were utilized for the identification of crystalline phases. 3. RESULTS AND DICSUSSION Thermal Differential Analyses (DTA) of the stociometric MAd powders for 10 h are presented in Fig.1 The initial exothermic peak was observed for the milled powders at about 250oC. This can be attributed the release of the cold work energy in the system stored during the mechanical alloying process at low temperatures.
Figure 1. DTA patterns of the MAd Fe2O3 and BaCO3 powders for 10 h with and without La, Sm or Nd substitutions.
In the DTA thermograph of Fig.1, the curve belonging to the as-milled samples show an endothermic peak at pertaining to the decomposition temperature of the precursors into the hexaferrite phase. For the undoped sample endothermic peak temperature is 985C and onset temperature is 800C corresponding to the formation of the BaFe12O19 phase. However, the other samples substituted with Sm, Nd and La the onset temperatures are 880C, 850C and 900C respectively which are above that of the undoped composition. Table 1. Reaction onset temperature of the Fe2O3 and BaCO3 powders for 10 h with and without La, Sm or Nd substitutions. Composition BaFe12O19 Ba0.85La0.15Fe12O19 Ba0.85Nd0.15Fe12O19 Ba0.85Sm0.15Fe12O19 Reaction onset temperature (C) 800 900 850 880
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3.1. Effects of the substitutions on the structure Figure 2 shows the XRD patterns of a series of Ba0.85RE0.15Fe12O19 (RE=Nd, La and Sm) samples and pure barium hexaferrite revealing the peaks belonging to the Fe2O3 phase (Bravais lattice : Rhombohedral, space group : Rc; a = b = 0.542 nm, c = 1.371 nm) and BaFe12O19 phase (Bravais lattice: simple hexagonal; space group: P63/mmc; a = b = 0.586 nm, c = 2.309 nm). For all samples, the formation of the magnetic BaFe12O19 hard ferrite phase was not completed after the heat treatment at 1000C for 1h. In the rare earth doped samples diffraction patterns show lower intensities of peaks reflected from the BaFe12O19 phase. This can be attributed to the increase in the reaction onset temperature of the rare earth added powders to form hexaferrite phase.
Figure 2. XRD patterns for the samples with Sm (a), Nd (b), La (c) substitutions and undoped Ba-hexaferrite (d) sintered at 1000C for 1 h. In Figure 3, diffraction peaks of the patterns reflected from BaFe12O19 hard ferrite and hematite (Fe2O3) phases are more intense than those of the powders sintered at the same temperature for 1 h because of the grain growth. But the hematite phase still exists in the structure of all the substances. Figure 3 shows the XRD patterns of these samples substituted with Nd, Sm, La and pure Ba hexaferrite.
Figure 3. XRD patterns for the samples with Sm (a), Nd (b), La (c) substitutions and pure Ba-hexaferrite (d) sintered at 1000C for 5 h.
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Figure 4. XRD patterns for the samples with Sm (a), Nd (b), La (c) substitutions and pure Ba-hexaferrite (d) sintered at 1250C for 1 h. Figure 4 shows that after sintering at 1250C, a single BaM-type phase was obtained for all compositions. For the pure barium hexaferrite, the diffraction peaks are more intense than those of the rare earth substituted samples. The XRD patterns of the samples are in accordance with the DTA analysis, since the crystallization of the barium hexaferrite phase starts at the lowest temperature of 800C and grain growth occurs for the undoped samples. Therefore, the peak intensities are stronger than those of the rare earth added powders barium hexaferrite phase which forms at the higher temperatures. 4. CONCLUSIONS The effects of RE cations (Nd3+, Sm3+ and La3+) were studied on the formation temperature of BaFe12O19 phase by using mechanical alloying method. The onset temperature to start the formation of the BaFe12O19 phase increases by inducing rare earth additions in barium hexaferrite composition. For the undoped sample endothermic peak temperature is 985C and onset temperature is 800C corresponding to the formation of the BaFe12O19 phase. However, the other samples substituted with Sm, Nd and La the onset temperatures are 880C, 850C and 900C respectively which are above that of the undoped composition. The heat treatment of 1000C is not sufficient to form pure BaFe12O19 hard ferrite phase for all the samples. In the XRD analysis, it was observed that for the rare earth doped samples diffraction patterns show lower intensities of peaks reflected from the BaFe12O19 phase. This can be attributed to the increase in the reaction onset temperature of the rare earth added powders to form hexaferrite phase. After sintering at 1250C, a single BaM-type phase was obtained for all the compositions and it was observed that the XRD patterns of the samples are in accordance with the DTA analysis. Since the crystallization of the barium hexaferrite phase starts at the lowest onset temperature 800C and grain growth is expected in the undoped samples while for the rare earth added powders barium hexaferrite phase forms at the higher temperatures. REFERENCES 1. Z.F. Zi , Y.P.Sun, X.B.Zhu, Z.R.Yang, J.M.dai, W.H.Song, Structural and magnetic properties of SrFe12O19 hexaferrite synthesized by a modified chemical co-precipitation method, Journal of Magnetism and Magneric Materials, Vol. 320, pp. 2746-2751, 2008 2. R. Smomski and J.M.D. Coey, Permanent Magnetism, p.261, Bookcraft, UK, 1999 3. A. Goldman, Modern Ferrite Technology, p.104, 2nd edition, New York, USA, 2006
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4. B. D. Cullity, C. D. Graham, Introduction to Magnetic Matreials, p.190,191,487 , John Wiley&Sons, New Jersey, USA, 2009 5. H. Yamamoto, M. Nagakura, H. Terada, Magnetic properties of anisotropid Sr-La system ferrite magnets, IEEE Transactions on Magnetics, Vol. 26 (3), pp.1144-1148, 1990 6. A. Gonzales-Angeles, G. Mendoza-Suarez, A.Gruskova, R. Dosoudil, R. Ortega-Zempoalteca, Magnetic Studies of Sn2+ - Sn4+ substituted barium hexaferrites synthesized by mechanical alloying, Materials Letters, Vol. 58, pp.2906-2910, 2004 7. G.K. Thompson, B.J. Evans, Order-Disorder and Magnetic Exchange Interactions in Subsitututed Strontium Hexaferrites SrAxFe12-xO10 (A=Ga, In), Journal of Applied Pyhsics, Vol.75, pp. 6643, 1994 8. G.Turilii, F.Licci, A.Paoluzi, NiTi substituted hexaferrites for magnetic recording, IEEE Transactions on Magnetics, Vol.24 (4), pp. 2146-2149, 1988 9. G.Turilii, F.Licci, Anisotropy field measurement and magnetization reversal in (Co-Ti) substituted hexaferrites, IEEE Transactions on Magnetics, Vol.24 (6), pp. 2865-2867, 1988 10. H.Yamamoto, M.Isono and T. Kobayashi, Magnetic properties of BaNdCo system M-type ferrite fine particles prepared by controlling the chemical coprecipitation method, Journal of Magnetism and Magneric Materials, Vol.295, pp.51, 2005 11. P. Sharma, R.A.Rocha, S.N.medeiros, B.Hallouche, A.Paesano Jr., Structural and magnetic studies on barium hexaferrites prepared by mechanical alloying and conventional route, Journal of Magnetism and Magnetic Materials, Vol.316 (2007) 29-33 12. S. Ounnunkad, Improving magnetic properties of barium hexaferrites by La or Pr substitution, Solid State Communications, Vol.138, pp. 472-475, 2006 13. L. Lechevallier, J.M.Le Breton, A.Morel and P.Tenaud, On the solubility of rare earths in M-type SrFe12O19 hexaferrite compounds, Journal of Physics; Condensed Matterials, Vol.20, pp.175203, 2008
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METALLIC FOAM
www.turkishpm.org
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TM YNTEMYLE BYK YZEY ALANLI METALK KPK RETMNDE KPREBLRLK PROBLEMLER

Ersin BAHEC*, Yusuf ZATALBA** ve Mehmet TRKER** * Kastamonu niversitesi, Cide Rfat Ilgaz M.Y.O. Kaynak Teknolojisi Blm, 37600, Kastamonu, ebahceci@kastamonu.edu.tr ** Gazi niversitesi, Teknoloji Fakltesi, Metalurji ve Malzeme Mhendislii, 06500, Ankara, yusufoz@gazi.edu.tr, mturker@gazi.edu.tr ZET Bu almada, byk kesit alanl (7500 mm2) kapal hcreli metalik kpk levhalarn toz metalurjisi yntemiyle retimi gerekletirilmitir. retim srecinde oluan problemler gzlenmi ve giderme areleri aratrlmtr. Al, %4 Si ve % 1,2 TiH2 tozlar kartrlarak souk presleme, sinterleme, scak ekstrzyon ve scak/lk haddeleme ilemleri uygulanarak kprtmeye hazr preform malzemeler retilmitir. Metalik kpk retiminde kullanlan byk boyutlu preform levhalarn, frnda kprtme ilemi srecindeki etkileri incelenmi ve kprtme hatalar kategorize edilerek sebepleri tartlmtr. Levha eklinde (250x250x30mm3) retilen metalik kplerin gzenek yaps ve gzenek oluumlar belirlenerek kprebilirlikleri kyaslanmtr. Kprtme srecindeki olumsuzluklar mimize etmek iin gelitirilen Yksek Enerji Metodu-X (YEM-X) ile endstriyel boyutlarda levha metalik kpk retimi gerekletirilmitir. Anahtar kelimeler: Metalik kpk, Al kpk, Kapal hcreli, Kprebilirlik, Isl etki
Foamablity problems encountered during the production of large surfaceD METALLIC FOAM by pm route
ABSTRACT In this study large surfaced (7500 mm2) close cell metallic foams were produced by using PM route. The problems encountered during production of such surfaced metallic foam were specified and tried to be solved. Al 4% Si, 1.2% TiH2 powders were mixed, cold pressed, sintered, extruded and then hot/warm rolled to produce foamable precursor. During the foaming process, effect of large surfaced foams on the foamability behavior was instigated and foaming problems were categorized and the reasons of problems were discussed. Pore formation and pore structure of plate like foams (250x250x30 mm3) were determined and foamability behaviors were compared. In order to minimize the problem encountered during the production of large surfaced industrial sized metallic foam High Energy Method-X (HEM-X) was used and foams was produced successfully. Keywords: Metalic Foam, Al Foam, Closed Cell, Foamability, Thermal Effect 1. GR Metalik kpkler, iyi enerji absorbe zellii, yksek basma dayanm, dk zgl arlk ve yksek rijitlik gibi mekanik ve fiziksel zellikleri ile bilinir [1]. eitli mhendislik uygulamalarnda kullanm alan bulabilen malzemeler olarak son yllarda olduka ilgi ekmektedir. zellikle Al esasl metalik kpkler, kapal hcre yaps ve ok hafif olmas ile gze arpmaktadr. Al kpkler, darbe enerjisini plastik enerjiye dntrebilir ve birok metalden daha fazla enerji absorbe edebilir [2, 3]. Bundan dolay ses ve enerjinin snmlenmesin de alminyum kpkleri fonksi-
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yonel olarak kullanlmaktadr. Kullanm alanlar arasnda, hafifliin ve mukavemetin bir arada bulunmas gereken otomotiv, uzay sanayi, demiryolu tamacl ve asansr gibi alanlar bulunmaktadr [4, 5]. Metalik levha kpkler ayn zamanda atee dayankl yaplar olarak da retilebilmektedir. Plaka tr kpk snfnda olan metalik kpkler yksek scaklklara kar yaltm malzemesi olarak kullanlmaktadr [6]. Bu zelliklerinden dolay savunma sanayisinde balistik ve/veya integral koruyucu zrh malzemeleri olarak kullanlmaktadr. Toz Metalurjisi (TM) yntemi metalik kpklerin retimi iin en yaygn kullanlan yntemlerden biridir. Homojen bir yap elde etmek iin gelitirilen bir yntemdir [7-9]. Bu yntem metal tozlarnn ve kprtc malzeme tozlarnn kartrlmas ve preslenmesi ile kprebilir yar maml (preform) malzeme haline getirme ilemine dayanr. Bu ilemlerle birlikte scak presleme, ekstrzyon, toz haddeleme, vb. metodlar ile preform haline getirilebilir. Preform ergitme scaklnn zerinde bir scakla getirilerek kprtme ilemi gerekletirilir [10, 11]. Sv ynteme gre homojen gzenekli kpk retebilme avantajnn yannda, byk kesitli preform malzemeden kprme ilemleri srasnda karlalan zorluklarda mevcuttur. zellikle kprtme srecinde preformun d yzeylerinde ve kalpla temas yzeylerinde balayan ve kprme reaksiyonu ile oluan gaz dolu hcrelerin, s iletiminde homojensizlie sebep olmas byk kesitli metalik kpklerin retimini gletirmektedir. Bu durumda kprtme srecinin kontrol nemlidir ve kprtme ilemi srasnda kontrol edilmesi zor deikenler devreye girmektedir. Bunlardan iki tanesi deien gzenek boyutlar ve ona bal deien sl iletkenliktir. Oluan malzemenin younluu ve gzeneklilii arasnda aadaki gibi bir eitlik bulunmaktadr [12]. (1) Burada p gzeneklilik, V kpk hacmini, ve * preform malzeme ve kpk malzeme younluunu temsil etmektedir. Preform (kat) younluu ve gaz faz younluu kprme esnasnda kpn younluunu deitirmektedir. Bu deiim sl iletimi deitirerek kprme karakteristiini belirlemektedir. Byk kesitli metalik kpk retimlerinde bunun daha nemli bir parametre olduu tespit edilmitir. Termal iletkenlik ve gzenek boyutu arasnda birka yaklam bulunmaktadr. Bu yaklamlardan bir tanesi Eitlik 2, 3 ve 4te gsterilmektedir. Yaklama gre gaz-kat, kat - sv veya sv-gaz gibi iki fazl sistemlerde s transferinin gerekleme durumlar gsterilerek formlize edilmitir (ekil 1.1) [13].
ekil 1.1. ki fazl sistemlerde ak ve s iletiminin paralel ve seri yaplandrma yaklam [13]. (2)
(3)
Burada gaz, kat gaz ve kat termal iletkenlii sembolize etmektedir [12-14]. 1. ve 2. Eitliklerdeki hem seri hemde paralel durum iki fazl yaplarda dnldnde 3 nolu bant oluturulmutur. = p gaz + (1-p) kat (4)
Her iki eitlik (1. ve 4.) birbiri ile dnldnde kprme esnasnda ierde oluan hcre boyutlar deitike hcre duvarlarndaki sl iletkenliin de deitii dnlebilir [12-14]. Eitlik 2ye gre dnlecek olursa gzeneklilik (p) arttka gazn termal iletkenlii kat ve/veya sv hcre duvarlarn iletkenliine gre daha belirgin rol oynamaktadr. zellikle byk kesitlere sahip preformlardaki btn kesit ya da hacim boyunca s iletim fark ve homojensizlik kprme srecinin de heterojenliine sebep olmaktadr. lk s girdisinin olduu preformun kenar, alt ve st yzey blgeleri ile orta blgelerinin kprme sreleri deiir. lk sl girdinin preformun kenar ve yzeylerinde balatt kprme reaksiyonu ile oluan ii hidrojen gaz dolu gzeneklerin ve hcre duvarlarnn Eitlik 4te belirtilen sl ilet-
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kenliine bal olarak kprme reaksiyonu i blgelere yaylr. Is iletiminde yukarda belirtilen etkenlerin meydana getirdii homojensizlik, homojen kprtme ve kpk retme ilemine engel olur. Bu nedenle kaln kesitlerde retilen kpk malzemelerde, kalnlk arttka homojen kprme problemleri ortaya kar. Kprme srecindeki s iletimini kalbn ekli, boyutu, sl iletkenlii ve preformun iletkenliinin belirledii tespit edilmitir [15]. Bu parametreler ve frn ii scaklk dalm dikkate alndnda byk kesitlerde homojen kpk oluumu iin mmkn olduunca e zamanl reaksiyon salanabilmelidir. Bu amala, Yksek Enerji Metodu-X (YEM-X) ile kprtme teknii gelitirilmitir. Bu metot ile preformun tm kesitinde kprmenin yaklak ezamanl balamas salanmtr. s iletimini Bu almada toz metalurjisi yntemiyle byk kesit alanl, AlSi alam kapal hcreli levha kpklerin kprme srecinde meydana gelen problemler ve giderme yntemleri aratrlm ve tartlmtr. 2. DENEYSEL ALIMALAR 2.1. Malzeme ve Metot1 % 99,9 saflkta ve 160 m alt tane boyutundaki Al tozu, % 4 Si ve kprtc madde % 1,2 TiH2 tozu 3 eksenli kartrma cihaznda (Turbola) kartrlp karm tozlar hazrlanmtr. Karm tozlar oda scaklnda preslenerek 80 mm apnda silindirik blok numuneler retilmitir. Blok numunelerin 1 saat sre ile sinterlenmesi ardndan 4:1 orannda scak ekstrzyon ilemi uygulanmtr (ekil 2.1-a). Ekstrze malzeme kademeli olarak scak/lk haddelenerek ekillendirilmi ve levha biimli 250x250x10 mm boyutlarnda preform levhalar retilmitir (ekil 2.1-b).
ekil 2.1. a) Ekstrzyon rn preform b) Haddelenmi preform levha 2.2. Kprtme lemi ekil 2.2de imal edilen kpk retme ve ekillendirme kalbnn resmi verilmektedir. Kprtme ilemleri, zel tasarlanan ve imal edilen mufel tipi 600x600x300mm3 kamara hacminde, alt tablas srgl hareket edebilen 13 kW gcndeki frnda yaplmtr.
ekil 2.2. Kprtme kalb

1
Bu alma konusunun ticari deeri sebebiyle sre, scaklk, basn vb. baz parametrelerin deerleri belirtilmemitir.
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Preform levha malzemeler kalp ierisine yerletirildikten sonra kprtme scaklndaki (680-780C) frna yerletirilmitir. Kprtme scaklnda belirli sre bekletildikten sonra kalp boluunu dolduran metalik kpk, kalpla birlikte frndan kartlarak sirklsyonlu havada soumaya braklmtr. Katlama tamamlandktan sonra metalik kpk malzeme kalptan kartlmtr. 3. SONULAR ve TARTIMA 3.1. Kprtme Kusurlar 3.1.1. Tm Kesitte Kprme Tamamlanmadan kme Kalp ierisinde ilk s iletimi salayan blgeler yzey alanlarnn kk olmasndan dolay kalp kenarlardr. ekil 3.1de kprtme ilemine tabi tutulmu olan levha eklindeki kpk malzeme gsterilmitir. Kprme srecinde ilk kpren blgelerin kalp kenarlarna yakn olan blgeler olduu kenar tarma deliklerinden gzlenmitir. Is iletiminin zamana bal ilerlemesi (ekil 3.1de A oklarnn yn) ile kprme, orta blgelerde de balamtr. Fakat orta blgeler kprme srecine girene kadar A oklar ile gsterilen blgeler ar kprme srecine girmitir. En son kprme blgesinin orta ksm olduu gzlenmitir. Bu sre tamamlanana kadar B oklar ile gsterilen blgelerde kme gzlenmitir. Is iletiminin preform zerinden salanmas, kenar blgelerde hcre oluumu ile azalmtr (Eitlik 4). Fakat kalp alt yzeyinden orta ksmdaki prefom malzemeye s transferi salandnda orta ksmda da kprme gereklemitir.
ekil 3.1. Homojen olmayan kprme ile oluan levha kpk 3.1.2. Yaynm ve Ylma ile Katmanlama ekil 3.2-Ide gsterilen levhada tam kprmeme ve ylma problemleri belirlenmitir. Kalp ierisinde kprtme srecinde kalb dolduran kpk malzemenin kenarlardan merkeze doru ilerledii gzlenmitir (ekil 3.2-III). Bu srete, yar kat durumda olan orta ksmdaki kprmemi malzeme, kprerek genleen ktle tarafndan yukar itilmi ve dzlemsellikten sapmasna neden olmutur. Bu deiiklik ile preformun kalp alt yzeyi ile temasn kestii gzlenmitir (ekil 3.2-IV). Bu srete s iletimi arlkl olarak kpren ksm olan blgeden gereklemektedir. Gzenek oluumuyla azalan s iletimi, kenar blgelerin kprerek ilerleme ve genleme hzn artrmtr. Bunun sonucunda orta ksmlar henz kprme srecine girmez iken kpren kenar blgelerin dzensiz gzeneklerle kalb doldurduu gzlenmitir. Ortam ve buna bal kalp scaklnn artmasyla kpren blgelerin drenaj azalmtr. Bununla birlikte kpk hacimsel genleme artacandan kalp doldurma sresi ksalacaktr [10, 16]. ekil 3.2-IIIte gsterilen kenar blgelerde gzenek boyutlar orta ksmlara gre daha byk ve hcrelerin birbiri ile birletii gzlenmitir. C oklaryla gsterilen ynde orta ksmlarda kprme sreci tamamlanmam malzeme zerine kpren malzemenin hareketi ile katmanlama gzlenmitir (ekil 3.2-II).
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ekil 3.2. I) Homojen kprmeyen levha kpk, II) st ksmda katmanlama III) Levha kpk kesiti, IV) Levhann alt yzeyi ekil 3.3te gsterilen kpk levha orta ksmda kprmeme problemi gzlenmitir. ekil 3.2de gsterilen levha kpe benzer durum sergilemitir. Fakat dier numune kprtme ileminden farkl olarak tarma deliklerinden kpk gelse dahi kprme srecine devam edilmitir. Bu bekleme kalp ierisini kpk doldurma ilemini artrmtr. Fakat orta ksmda kprme sreci tamamlanmamtr (ekil 3.3-b). Kprtme srecinin uzatlmasyla kalp st yzeyi arasna yaylan kprm malzemenin orta tarma deliklerinden tat gzlenmitir. Bu yaylma D oklarnn gsterildii ynde gereklemitir. ekil 3.3-bde de F oklaryla bu srnme etkisinin gzenek hcre ekillerini ve boyutlarn dzensizletirdii grlmektedir. E okuyla gsterilen ksmlarda ar kprme gzlenmi olup hcre duvarlarnn birbiri zerine kt belirlenmitir.
ekil 3.3. a) Levha kpn genel grnm, b) Levha kpk kesiti
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3.1.3. Kelerde kme ekil 3.4te gsterilen kpk levha ke ksmlarnda kme problemi gzlenmitir. Bu levha kpk retiminde kullanlan parametreler sabit olmakla birlikte, kalp st kapann kprme srecinde kapatlmas denenmitir. Kprme sreci tamamlanrken tavlanm kalp kapa vastasyla basn uygulanarak, kalp iindeki kpn scak deformasyonuyla kalp boluunu doldurmas salanmtr. Bu ilemlerin sreci ok ksa tutulmutur. G oklaryla gsterilen blgelerde, kpk hcrelerinin ekil deitirme esnasnda patlamas, birlemeleri ve skan hidrojen gaznn kamasyla levha kelerinde ar kpk kmeleri ve malzeme ylmalar gzlenmitir. ekil 3.4-IIde levha kpn kesit grnts verilmitir. ekil deiiklii ile levhann genelinde basn uygulanan yne dik ynde hcreler deformasyona urayarak elipstik ekil almlardr. Bu ekilde oluan morfolojik dzensizlikler, hcre elipslii, homojen olmayan hcre duvar kalnl ve hcre boyut dalmnn plato blgesi gerilmesini azatl belirlenmitir [17]. H oklaryla gsterilen blgelerde istenmeyen bu hcre yaplar belirtilmitir.
ekil 3.4. I) Levha kpn genel grnm ve ylma kesinin grnts, II) Levha kpk kesit grnts. ekil 3.5te Yksek Enerji Metodu-X (YEM-X) ile retilen metalik levha kpk gsterilmitir. retilen kpk levhada ayn kesit alanl nceki levhalara gre daha homojen ve e eksenli hcreler elde edilebilmitir. Levha kpn tm kesiti ayn boyutlarda, ayn homojen hcre yapsnda ve dzgn geometrik yzeylere sahiptir. Kprme srecinde preform malzemenin tm yzeylerinde salanan daha homojen ve hzl s iletimi ile e zamanl balatlan kprme reaksiyonu, dzenli hcreli levha kpk retimini gerekletirmitir. Preform malzeme retim srecinde homojen olmayan Si ve TiH2 dalm, kprme srecinde de baz homojen olmayan gzenek dalmna da sebep olmaktadr. Bu nedenle G oklaryla gsterilen birka hcrede, kprme srecinde hcrelerin balant duvarlarnn kaybolmas ve birbiriyle birlemesi ile byk gzenekli hcreler olumutur.
ekil 3.5. YEM-X yntemi ile retilen metalik levha kpk
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4. SONULAR Bu almada, geni yzey alanl veya byk kesitli metalik kpklerin retimi srecinde meydana gelen metalik kpk levhalardaki hatalar kategorize edilmi ve nedenleri tartlarak giderilme areleri aratrlmtr. Bu almann sonular olarak aada hususlar belirtilmitir; 1) Preform (kat) younluu ve gaz faz younluu kprme esnasnda kpk malzemenin younluunu deitirmitir. Bu deiim preformun s iletimini deitirerek kprme karakteristiini belirler. Toz metalurjisi teknii ile levha boyutlarndaki byk kesitli metalik kpk retimlerinde s iletimindeki bu deikenlik nemli problemler meydana getirir. 2) Byk kesitli levha kpk retim srecindeki oluan problemler;
- Kalp ierisinde tm kesitte kprmenin tamamlanmas srecinde erken kprme oluan blgelerde kme problemi meydana gelir. - Kalp ierisinde tm kesitte tam kprmeme ve yaylma problemleri meydana gelir. Kprtme srecinde kalb dolduran kpk malzemenin kenarlardan merkeze doru yaylmasyla, kprmeyen preformun dzlemsellii bozularak kalp alt yzeyi ile temas keser. Kprerek yaylan malzeme prefom malzemenin zerine doru ilerleyerek katmanlama meydana getirir. Bu durumda, retilen kpk levhann orta ksmlarnda hcre oluumu tamamlanmazken kenar ksmlarda byk ve homojen olmayan gzenekli yap meydana gelir. - Kprme srecinde basn oluturarak kalp boluunun doldurulmas ilemlerinde, kalp kelerine malzemenin yaylmas srasnda hcrelerin deformasyonla patlamas, kapanmas, kme problemlerini oluturur. Kpk malzemenin scak deformasyonu ise, uygulanan basma ykne dik dorultuda hcrelerin deformasyonuna ve geometrisinin bozulmasna sebep olmaktadr. - Yukarda belirtilen problemlerin giderilmesi iin gelitirilen Yksek Enerji Metodu-Xin uygulanmas bu problemlerin bir ounu elimine etmitir. Kprme srecinde preform malzemenin tm yzeylerinde salanan yksek enerjili homojen s iletimi sayesinde yaklak e zamanl balatlan kprme reaksiyonu, dzenli hcreli levha kpk retimini gerekletirmitir. Levha kpn tm kesiti ayn boyutlarda, dier kpklere kyasla daha homojen ve e eksenli hcre yapsnda ve dzgn geometrik yzeylere sahiptir.
TEEKKR Yazarlar, Bilimsel Aratrma Projesi ( No: 107A016) kapsamnda bu almaya destek salayan TBTAKa teekkr eder. KAYNAKLAR 1. Seitzberger, M., Rammerstorger, F.G., Degischer, H.P.,Crushing of axially compressed steel tubes filled with aluminium foam, Acta Mechanica, 125: 95-103, 1997. 2. Hanssen A.G., Langseth, M., Happerstad, O.S., Static and dynamic crushing of circular aluminium extrusions with aluminium foam filler, Int. J. of Impact Eng., 24 (5): 475-507, 2000. 3. Elbir, S., Ylmaz, S., Gden, M.,Kapal hcre alminyum kpk metallerin retim metodlar ve mekanik zellikleri, TMMO Metalurji Dergisi, 23 (120): 35-42, 1999. 4. Davies, G.J., Zhan, S., Review metallic foams, their production, properties and applications, J. Mat. Sci., 18: 1899-1911, 1983. 5. Simancik, F., Rajner, W., Laag, R., Alulight - Aluminum Foam for Lightweight Construction, SAE 2000 World Congress, 2000-01-0337, pp. 1-7, Detroit, Michigan, 2000. 6. P. Schaeffler, W. Rajner, D. Claar, T. Trendelenburg, and H. Nishimura., Production, Properties and Applications of Alulight Closed-Cell Aluminum Foams, The Fifth International Workshop on Advanced Manufacturing Technologies, pp. 1-6, London, Canada, 2005. 7. John Banhart, Manufacturing Routes for Metallic Foams, Journal of the Minerals, pp. 22-27, 2000. 8. Chin-Jye Yu, Harald H. Eifert, John Banhart and Joachim Baumeister, Metal Foaming by A Powder Metallurgy Method: Production, Properties and Applications, Innovations in Materials Conference, vol:2, pp. 181188, 1998. 9. Mehmet TRKER, Toz Metalurjisi Yntemi ile Alminyum Kpk retimi, 5. Uluslararas leri Teknolojiler Sempozyumu (IATS09), s.1-6, Karabk, 2009. 10. I. Duarte and J. Banhart, A Study of Aluminium Foam Formation Kinetics and Microstructure, Acta Materialia, 48, pp. 2349-2362, 2000. 11. By Frank Baumgrtner, Isabel Duarte and John Banhart, Industrialization of Powder Compact Foaming Process, Advanced Engineering Materials, 2, No:4, pp. 168-174, 2000. 12. Hegman, N. and Babcsan, N., Specific Feature of Thermal and Electrical Transport In Cellular Media, Anyagok Vilaga Materials World, 6:1, 2005.
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13. Singh, R., Kasana, H.S., Computational aspects of effective thermal conductivity of highly porous metal foams, Applied Thermal Engineering, 24, 18411849, 2004. 14. Sullins, A.,D. And Daryabeigi, K., Effective Thermal Conductivity of High Porosity Open Cell Nickel Foam, 35th AIAA Thermophysics Conference, AIAA 2001-2819, 3-5, 2001. 15. Hans-Peter Degischer and Brigitte Kriszt, Handbook of Cellular Metals: Production, Processing, Applications, Wiley- VCH, pp. 33-338, 2002. 16. S. Asavavisithchai, A.R. Kennedy, Effect of powder oxide content on the expansion and stability of PM-route Al foams, Journal of Colloid and Interface Science, 297, 715723, 2006. 17. Elbir, S., Kapal Gzenekli Alminyum Kompozit Kpklerin Hazrlanmas ve karakterizasyonu, zmir Teknoloji Enstits, Yksek Lisans Tezi, 28-79, 2001.
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TiCN Takviyeli 316L Paslanmaz elik Kpklerin retimi ve zellikleri

Halil . BAKAN1 ve Kemal KORKMAZ2
2
TBTAK MAM Malzeme Enstits Pk 21 Gebze 41470 - KOCAEL Gebze Yksek Teknoloji Enstits, Malzeme Bil. ve Mh. Bl. Gebze 41400 - KOCAEL
1
ZET Arlka %5 TiCN ieren stenitik paslanmaz elik esasl metalik kpkler replikasyon ve toz metalurjisi yntemleri ile retildi. Bunun iin 316L tozlar ile balaycdan oluan sv karm, poliretan sngere emdirildi. Yzeyleri metal tozlar ile kaplanm olan sngerlere srasyla kurutma ve bunu takip eden piroliz ilemi uygulanarak, snger ve balayclarn ortamdan uzaklatrlmas saland. Bu ekilde poliretan sngerin ak gzenekli iskelet yaps ak gzenekli metalik iskelet yapya dntrld. 1350 oC scaklkta gerekletirilen sinterleme ileminden sonra ak gzenekli hcresel paslanmaz elik esasl metalik kpkler elde edildi. Sinterleme sonras elde edilen kpk metalik malzemelerin gzenek dokusu optik mikroskop ve SEM ile incelendi. EDX ve XRD analizleri ile numunelerin faz yaps karakterize edilmitir. Ayrca numuneler zerinde gerekletirilen basma deneyleri ile elde edilen kpk metalin mekanik zellikleri irdelenmitir. Anahtar Kelimeler: Metalik Kpkler, , Paslanmaz elik, Toz Metalurjisi,
Manufacturing and Properties of 316L Stainless Steels Foams Reinforced with TiCN
ABSTRACT Austenitic stainless steel based metal foams with 5 wt % TiCN were manufactured by using replication and powder metallurgy techniques. Therefore, a polyurethane sponge, impregnated with stainless steel slurry prepared from 316L powders and binders, was subjected to drying and pyrolyzing to remove the polyurethane sponge and binders. Thus, the complete transformation of open network of the polyurethane sponge to the metal network was carried out. After sintering process at temperature of 1350 oC, open cellular 316L based metal foams were produced. The porous structure of metallic foam materials obtained after sintering was investigated by using optical microscopy and SEM. The phase structures of samples were characterized by XRD and EDX analysis. In addition, mechanical properties were investigated by compression tests performed on the samples. Keywords: Metal Foams, , Stainless Steel, Powder Metallurgy 1. GR Metalik kpk malzeme tanm; hacimce % 50 - % 99 arasnda hava boluu ieren gzenekli ya da hcresel ekilli bir yapya sahip metalik malzemelere verilen genel bir isimdir. erdikleri hava boluu sayesinde ok farkl fiziksel zellikleri ayn anda gsterebilmektedirler. Bu malzemelerin en belirgin zellikleri ise ok dk younlua sahip olmalar, basma ve eme dayanmlarnn ok yksek olmas, darbe ve titreim snmleme zelliklerinin yksek olmas, s ve elektrik iletim zelliklerinin de dk olmasdr. Bu zellikleri nedeniyle yeni bir malzeme snfn oluturmaktadrlar. erdikleri hava boluunun oran, hava boluunu meydana getiren gzeneklerin ekli
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ve bu gzeneklerin birbirleri ile olan balantsna bal olarak gsterdikleri fiziksel zellikler ve potansiyel kullanm alanlar deimektedir. Sahip olduklar bu zgn zellikler nedeniyle 21. yzylda uzay teknolojisinden otomotiv teknolojisine, inaat teknolojisinden salk teknolojisine kadar ok deiik alanlarda kulanm potansiyelleri olduu ngrlmektedir. Paslanmaz elik esasl kpk metallerin, alminyum esasl kpk malzemelere gre daha yksek mekanik zelliklere sahip olmalar ve yksek scaklklarda uygulamalarnda kullanlma imkanlarnn bulunmas, elik esasl metalik kpk malzemelere olan ilgiyi arttrmaktadr [1-5]. Ak gzenekli hcresel ekilli metalik kpklerin retimi replikasyon teknii ve toz metalurjisi yntemi ile gerekletirilmektedir. Metalik kpklerin ak gzenekli hcresel yaps, ayn ekle sahip olan ve balang malzemesi olarak kullanlan polimerik sngerler sayesinde elde edilebilmektedir. Replikasyon (kopyalama) ileminin gerekletirilebilmesi iin ncelikle metal tozlarnn uygun organik malzemeler ile kartrlarak bir sv karmn elde edilmesi gerekir. Daha sonra bu sv karmn polimerik sngere emdirilmesi gerekletirilmektedir. Daha sonra uygulanan piroliz ilemi ile polimerik snger ve organik malzemeler buharlatrlarak ortamdan uzaklatrlmaktadr. Bu ilem srasnda, balang polimerik sngerin ak gzenekli hcresel yapsnn bir kopyas olan metal iskelet yapnn elde edilmesi gereklemektedir. Bu ilemden sonra uygulanan sinterleme ile de ak gzenekli hcresel metalik kpkler retilmi olmaktadr [1-5]. Polimerik snger yzeylerinin metal tozlar ile kaplanmas bu prosesin ilk ve en nemli aamasn oluturmaktadr. Metal tozlarnn organik malzemelerle kartrlmasyla hazrlanm olan sv karmn mmkn olan en fazla oranda metal tozu iermesi ve snger yzeylerine mmkn olan en fazla miktarda metal tozlarn yaptrabilme zelliine sahip olmas gerekir. Bunun sonucunda; sinterlemenin daha iyi gereklemesi ve daha yksek sinterleme younluklarnn elde edilmesi mmkn olabilir. Buna karn, sv karmn gereinden fazla metal tozu iermesi de polimerik snger yzeylerinin metal tozlar ile tam olarak kaplanamamasna neden olur. Bu nedenle sv karmdaki metal toz miktarnn optimum bir deerde olmas gerekir. Paslanmaz elik tozlarnn yzeyinde bulunan ince bir krom oksit tabakas, bu malzemelerde normal kat hal sinterleme koullarnda yksek sinterleme younluk deerlerinin elde edilmesini imkansz hale getirmektedir. Buna karn sv faz sinterlenmesi ilemi ile bu malzemelerde yzde yz teorik younlua ulalmas mmkn olabilmektedir. Younluk artyla birlikte mekanik zelliklerde de nemli artlar gerekleebilmektedir [6] Fakat tamamen ak gzenekli metalik kpk malzemelerin retiminde sv faz sinterlenmesinin uygulanmas mmkn deildir. nk sv faz oluumu ile birlikte metalik iskelet yapda yer yer kmeler ve ekil bozukluklar olumaktadr. Bu nedenle bu malzemelerin retiminde kat hal sinterlemesi kanlmazdr. Bununla birlikte metalik kpk malzemenin mekanik zelliklerini arttrmak iin deiik oranlarda karbr esasl katklar paslanmaz elik tozlarna ilave edilebilir. Bu sayede ana yap ierisinde homojen olarak datlm sert karbr faz ya da oksit fazlar sayesinde, mekanik zellikler nemli artlar salanabilir. Literatrde zellikle TiC, NbC, SiC, TiCN, Al2O3 ve Y2O3 katklar ile ilgili almalar bulunmaktadr [7-9]. Bununla birlikte TiCN takviyeli paslanmaz elik malzemeler ile ilgili almalar olduka yenidir [10] Bu nedenle daha stn mekanik zellilere sahip metalik kpkler retebilmek iin; mevcut almada arlka % 5 orannda TiCN ieren 316L paslanmaz elik tozlar kullanlarak, replikasyon ve toz metalurjisi yntemiyle hcresel ekilli metalik kpklerin retimi gerekletirilmitir. retilen metalik kpk malzemenin mekanik zellikleri basma deneyleri ile belirlenmi. Ayrca retilen kpk malzemenin mikroyap zellikleri optik ve taramal elektron mikroskobuyla (SEM) ve faz yaps da XRD ve EDX analizleri ile incelenmitir. 2. DENEYSEL ALIMALAR Bu almada gaz atomizasyon yntemiyle retilmi ve ortalama tane boyutu 25 m olan kresel ekilli 316L stenitik paslanmaz elik tozlar ve ortama tane boyutu 1 m olan dzensiz ekilli TiCN tozlar kullanlmtr. Kullanlan 316L tozlarn kimyasal bileimi arlka % Fe -16.96 Cr, 10.8 Ni, 2.04 Mo, 1.38 Mn, 0.4 Si, 0.03 C, 0.03 P, 0.003 S dr. Arlka % 5 TiCN ieren homojen bir toz karmn elde edilebilmesi iin toz karm, aseton ieren bir kabn ierisine konularak, Turbula tipi kartrc da saatlik bir kartrma ilemi uyguland. Daha sonra etvde uygulanan kurutma ilemiyle aseton toz karmndan uzaklatrld ve kullanma hazr 316L+ % 5 TiCN toz karm elde edildi. Arlka % 5 TiCN ieren 316L paslanmaz elik esasl metalik kpk retimi replikasyon ve toz metalurjisi yntemiyle gerekletirildi (ekil 1).
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ekil 1: Hcresel ekilli paslanmaz elik kpk malzemenin retim emas
Ak gzenekli hcresel ekilli kpk metalin elde edilebilmesi iin balang malzemesi olarak ierdii gzenek miktar 10 ppi (pores per inch) poliretan sngerler kullanld. Metal tozlarnn poliretan sngere emdirilebilmesi ve snger yzeylerinin metal tozlar ile kaplanabilmesi iin deiik molekler arlktaki Polietilen Glikol (PEG) ve Karboksimetil selloz (Carboxy Methyl Cellulose, CMC) zeltisinden oluan balayc sistemi kullanld. ncelikle Karboksimetil selloz zeltisine metal tozlar (arlka % 5 TiCN ieren 316L paslanmaz elik tozlar) azar azar ilave edilerek bir saatlik kartrma ilemi uyguland. Daha sonra elde edilen karmn scakl oda scaklndan 75C scakla kartld ve deiik molekler arlktaki PEG (PEG600, PEG1500 ve PEG8000) karma eklendi. lave edilen PEGler bu scaklkta tamamen ergitildikten sonra, balayc+metal tozundan oluan sv karm saat daha kartrlarak homojen bir sv bir karm elde edildi. Elde edilen sv karmn iermesi gereken ideal metal toz miktarn ve reolojik zelliinin belirlenmesi iin ayn artlarda hazrlanm ve ierdii metal toz miktar hacimce % 45, % 50 ve % 55 arasnda deien karmlarn viskozite lmleri yapld. Viskozite lmleri srasnda ortam scakl 75C olarak sabit tutuldu. Sv karmn iermesi gereken optimum metal tozu miktar belirlendikten sonra poliretan sngerler sv karma daldrlarak, snger yzeylerinin metal tozlar ile kaplanmas gerekletirildi. Yzeyleri metal tozlar ile kaplanm olan sngerler daha sonra iki merdane arasndan geirilerek, fazlalk metal tozlarnn sngerden uzaklatrlmas ve ak gzenekli yapnn korunmas saland. Bu ilemden sonra numuneler belirli bir nem oranna sahip kabin ierisinde ve oda scaklnda iki gn kurutulmaya brakld. Numuneler kurutulduktan sonra poliretan snger ve organik balayclar 450C scaklnda ve Ar - H2 atmosferinde otuz dakika ierisinde buharlatrlarak numunelerden uzaklatrld. Hidrojen ortamnda ve 1350Cde gerekletirilen saatlik sinterlemeyle ak gzenekli hcresel yapda 316L + %5 TiCN esasl metalik kpkler retildi. Elde edilen metalik kpklerin mikro yaps ve yzey zellikleri optik mikroskop ve taramal elektron mikroskop (SEM) kullanlarak aratrld. Numunelerin faz yaplar XRD ve EDX analizleri ile incelendi. Gerekletirilen basma deneyleri ile de mekanik zellikler belirlendi. 3. DENEYSEL SONULAR VE RDELEME Deiik oranlarda metal tozu ieren sv karmn 75C scaklkta gerekletirilen viskozite lm sonular ekil 2de grlmektedir. Metal tozlarnn polimerik yzeylere daha kolay yapmasnn salanabilmesi iin sv karma yksek kayma hz uygulandnda karmn viskozite deerinin dk olmas arzu edilir. Fakat kayma hz dk olduunda ise sv karmn viskozitesinin de yksek olmas gerekir. Bu durum metal tozlarnn polimerik snger yzeylerine kolay ve daha iyi yapmasn salar. ekil 2 de grld gibi hacimce %45 metal tozu ieren sv karmn viskozite deeri kayma hznn artmasyla belirgin bir ekilde azalmakta ve kayma dk olduu durumda 45 Pa.s olan viskozite deeri kayma hznn artmasyla birlikte dier karmlara gre ok daha hzl olarak dmekte ve 2 Pa.s gibi ok dk bir deere ulamaktadr. Dolaysyla hacimce %45 metal tozu ieren sv karm daha ideal reolojik zellikler sahiptir.
ekil 2: Deiik oranlarda (%45-55) metal tozu ieren sv karmn 75Cdeki viskozite deerlerinin kayma hzna gre deiimi
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Hacimce %45 metal tozu ieren (316L+%5 TiCN) sv karm PEG + CMC ekilde 1de grld gibi replikasyon ve toz metalurjisi yntemleri ile arlka %5 TiCN ieren 316L paslanmaz elik esasl metalik kpkler baarl bir ekilde retilmitir. Elde edilen gzeneklerin ekil ve yaplar balangta malzemesi olarak kullanlan poliretan sngerin gzenek ve yapsnn birer kopyas gibidir. Ancak 316L paslanmaz eliklerin 1350C de gerekletirilen kat hal sinterlenmesinin doal bir sonucu olarak mikroyapda mikro gzenekler bulunmaktadr (ekil 3). nk paslanmaz elik tozlarnn yzeyinde doal olarak oluan ince oksit tabakas, kat hal sinterlenmesinde tam younlamann salanabilmesini engellemekte ve yapda mikro gzeneklerin olumasna neden olmaktadr. retilen TiCN katkl 316L paslanmaz elik malzemenin younluu 0,70 g/cm3 ve TiCN katks iermeyen 316L paslanmaz elik kpk malzemenin younluu ise 0.75 g/cm3 olarak llmtr (ekil 3a). Bu deerler retilen metal kpk malzememizin ne kadar hafif bir malzeme olduunun ak bir gstergesidir. Younluktaki azalma yalnzca daha hafif olan TiCN katksndan kaynaklanmad, ayn zamanda TiCN katks ile mikro yapda ilave olarak bir miktar daha istem d meydana gelen mikro gzenek oluumu aklanabilmektedir. Bu durum mikroyap fotoraflarnda da grlmektedir (ekil 3a-3b,). Buna karn TiCN katks sonucu kpk malzemenin sertlik deerinde bariz bir art grlm ve 316L paslanmaz elik kpk malzemenin sertlik deerinin % 5lik TiCN katks ile 220 HV den 355 HV ye ykseldii tespit edilmitir. Elde edilen kpk malzemenin sertlik deerindeki artn, mikroyapda homojen bir dalm gsteren sert bir TiCN takviyesinin doal bir sonucu olduu grlmektedir.
ekil 3a) retilen TiCN katkl 316L metalik kpklerin deiik grnmleri
ekil 3b): retilen ak gzenekli hcresel 316L paslanmaz elik kpklerin SEM de ekilmi mikro yap grnts retilen hcresel 316L paslanmaz elik kpklerin ve TiCN katkl 316L paslanmaz elik kpklerin basma dayanm ekil deitirme erisi tipik bir basma dayanm ekil deitirme erisi eklindedir (ekil 4). Her iki metalik kpk malzemenin basma erisi blmden olumaktadr. Birinci blmde ekil deiimi ile dorusal olarak deien bir gerilim sz konusudur. Elastik blge olarak isimlendirilen bu blgede hcre duvarlar eilmektedir. Elastik blgeyi takiben ikinci blge ise gerilimin deimedii, buna karn uzun ve kalc bir ekil deiiminin olduu bir plastik deformasyon blgesini gstermektedir. Bu blgede hcre duvarlarnn plastik ekil deitirmesi ile birlikte gzenekler kapanmaktadr. Erinin nc ve son blgesinde ise boluksuz, bulk bir malzemedeki gibi kesit alannn giderek artmasna bal olarak gerilmede hzl bir art grlmektedir. 316L paslanmaz elik kpk malzemenin basma dayanmnn % 5lik TiCN katks ile 30,56 MPa dan 45 MPa a artt grlmektedir. Bu artn mikroyapda homojen olarak dalm olan sert TiCN fazndan kaynakland aktr.
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ekil 4: retilen ak gzenekli hcresel 316L paslanmaz elik kpklerin basma erisi Elde edilen %5 TiCN katkl 316L paslanmaz elik kpk malzemenin SEM de yaplan EDX analizi ekil 5 de grlmektedir. Kpk malzemenin stenitik paslanmaz elik (316L) esasl olmasndan dolay Fe, Cr, Ni ve Mo elementlerinin, %5 TiCN katkdan dolay da Ti elementinin tespit edildii aikardr. N elementinin tespit edilemeyecek kadar az olmasna karn C elementinin hem stenitik paslanmaz elik ve hem de %5 TiCN iinde mevcut olmasndan dolay tespit edilebildii dnlmektedir.
ekil 5: % 5 TiCN katkl 316L paslanmaz elik esasl metal kpk malzemenin SEM de elementel (EDX) analiz sonular.
ekil 6: 316L paslanmaz elik esasl ve % 5 TiCN katkl metal kpk numunelerde XRD analiz sonular. ekil 6 da ise %5 TiCN katkl ve katksz 316L paslanmaz elik kpk numunelerin, 2 = 20o ile 90o arasnda dakikada 2o tarama hz ile llen XRD analiz sonular verilmektedir. Her iki analizde de paslanmaz elie ait olduu dnlen Fe- stenitik fazn (111), (200) ve (220) yansma dzlemlerinden elde edilen en belirgin pikleri grlebilmektedir. %5 TiCN katkl numunenin analizinde ise Fe- stenitik fazlarn yan sra titanyum karbonitrr (TiC0.7N0.3) fazna ait olduu dnlen ve en iddetlileri (111), (200), (220) yansma dzlemlerinden elde edilen pikler olmakla beraber (311) ve (222) deki piklerde ayrt edilebilmektedir.
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4. SONULAR Mevcut almada replikasyon (kopyalama) teknii ve toz metalurjisi yntemleri kullanlarak arlka %5 TiCN katkl ve katksz olmak zere 316L paslanmaz elik esasl, ak gzenekli ve hcresel ekilli kpk malzemeler baarl bir ekilde elde edilebilmitir. Elde edilen kpk malzeme elik esasl olmasna karn sudan daha hafiftir ve gzenek ekli ve yaps asndan balang malzemesi olarak kullanlan ve 10 ppi gzenek miktarna sahip poliretan sngerin bir kopyas eklindedir. retilen TiCN katkl 316L paslanmaz elik malzemenin daha dk younlua sahip olmasna ramen daha iyi mekanik zellikler sergiledii grlmtr. 316L paslanmaz elik kpk malzemenin sertlik deerinin % 5lik TiCN katks ile 220 HV den 355 HV ye ve basma dayanmnn da 30,56 MPa dan 45 MPa a ykseldii tespit edilmitir. Elde edilen kpk malzemenin mekanik zelliklerindeki artn sebebinin TiCN katksnn meydana getirdii ve mikroyapda homojen bir dalm gsteren titanyum karbonitrr gibi sert bir faz oluumu sonucu olduu dnlmektedir. KAYNAKLAR [1] J. Banhart, Progress in Materials Science, Vol.46, pp.559-632, 2001 [2] L. J. Gibson and M.F. Ashby, Cellular Solids: Structure and Properties, Second Edition, Cambridge University Press, Cambridge, 1997. [3] C. Park and S.R. Nutt, Materials. Science . and Engineering. A vol 288 , pp. 118-118, 2000 [4] L. P. Lefebvre, M. Gauther and M. Patry, International . Journal of. Powder Metalllurgy. vol,42, 3, 49-57, 2006 [5] S.V. Raj, L. J. Ghosn, B.A. Lerch, M. Hebsur, L. M. Cosgriff and J. Fedor, Materials. Science . and Engineering. A vol 456,1-2, pp.305-316, 2007 [6] H.I. Bakan, D. Heaney , R.M German, Powder Metallurgy, vol. 44-3 , pp. 235-241, 2001 [7] J.D Bolton. and A.J. Gant , International . Journal of. Powder Metalllurgy., vol 36, pp. 267-274,1993 [8] S.Lal and G.S.Upadhyaya., Powder Metalllurgy International vol.20,3 pp. 35-38, 1988 [9] S.K.Mukherjee., A.Kumar, and G.S.Upadhyaya. Powder Metalllurgy International vol 20,3 pp. 35-38, 1988 [10] H.. Glsoy. Powder Metalllurgy, vol.24, 2, pp 14841490, 2008
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TOZ METALURJS YNTEMYLE RETLM TiNi KPKLERDE YALANDIRMA ISIL LEMNN ETKLER
Tark AYDOMU* ve akir BOR** Yznc Yl niversitesi, Mhendislik Mimarlk Fakltesi, Makina Mhendislii Blm, 65080, Van, aydogmus@yyu.edu.tr ** Orta Dou Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 06531, Ankara, bor@metu.edu.tr
*
ZET Bu almada yalandrma sl ileminin farkl miktarda gzenek ieren TiNi kpklerin dnm scaklklar ve mekanik zellikleri zerindeki etkisi incelenmitir. Ti-50.6 at. %Ni alam tozu ve boluk yapc olarak magnezyum tozunun 400 MPa basn altnda basldktan sonra 1100 Cde 1 saat sinterlenmesiyle retilen tek fazl (stenit) TiNi kpkler 400 Cde 1 saat sreyle yalandrma sl ilemine tabi tutulmulardr. Bu ilem sonrasnda kelen Ti3Ni4 faznn TiNi ana fazndaki nikel miktarn azaltarak dnm scaklklarn nemli lde arttrd grlmtr. Yalandrma sl ilemi sonras mekanik zelliklerde belirgin bir deiiklik gzlenmemitir. Yalandrlm btn TiNi kpkler ksmi sperelastisite sergilemi, tam sperelastisite ancak dngsel ykleme-boaltma sonucu elde edilebilmitir. Bu sayede % 5e varan gerinim kazanmlar mmkn olmutur. Anahtar kelimeler: TiNi Kpkler, Yalandrma, Sperelastisite, Faz Dnm Scaklklar, Mekanik zellikler.
EFFECTS OF AGING HEAT TREATMENT ON TiNi FOAMS PRODUCED BY POWDER METALLURGY METHOD
ABSTRACT In the present study, effects of aging heat treatment on transformation temperatures and mechanical properties of TiNi foams have been studied. Single phase (austenite) TiNi foams, which were produced by sintering Ti-50.6 at. %Ni powder and magnesium spacer particle mixtures at 1100 C for 1 hour subsequent to compaction under 400 MPa, were subjected to aging heat treatment at 400 C for 1 hour. It has been observed that, Ti3Ni4 precipitates formed increased the transformation temperatures significantly by decreasing the nickel content of TiNi matrix phase. Aging was not effective notably on mechanical properties. Partial superelasticity was observed for all aged TiNi foams. Complete superelasticity of samples strained up to 5% was observed only upon employing cyclic loading and unloading. Keywords: TiNi Foams, Aging, Superelasticity, Phase Transformation Temperatures, Mechanical Properties.
1. GR Diilik ve ortopedi gibi biyomedikal uygulamalar iin gelecek vaat eden TiNi kpklerle [1] ilgili aratrmalar son 10 sene ierisinde nemli bir hz kazanmtr. Biyouyumlu [2,3] olduklar kantlanan bu kpkleri biyomedikal uygula-
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malarn gerektirdii zelliklerde retilebilmek amacyla pek ok alma yaplmtr [4-23]. Her ne kadar gzenekli metalik malzemeler kat hal ilemleri (toz metalurjisi), sv hal ilemleri (dkm), elektrolitik ilemler veya gaz fazndan biriktirme yntemlerinden biriyle retilebilseler [24] de hem daha pratik hem de kolay olan toz metalurjisi teknikleri TiNi kpklerin retilmesinde kullanlan esas yntemler olmutur. Zaten ikinci nemli alternatif retim yntemi olan dkm, daha ok ergime scakl dk ve ergitilmesi kolay, reaktif olmayan metaller iin uygundur. TiNi kpk retiminde bugne kadar kullanlan yntemlerin ortak problemleri istenmeyen, krlgan intermetaliklerin olumas, homojen olmayan gzenek ekli ve dalm, bunlarn sonucu olarak dk mekanik zellikler ve yetersiz sperelastisite davran sergilemesi ve gzenek miktar ile boyutlarnn ayarlanmasnn zorluu olmutur. Bu problemlerin hemen hepsi daha nceki almalarmzda [4,9,15,16] incelenmi ve eitli zmler nerilmitir. Bu almada ise nceki almalarmzdaki gibi magnezyum (Mg) boluk yapc ve TiNi alam tozu kullanarak rettiimiz TiNi kpklerinde yalandrma sl ileminin pratik uygulamalar asndan son derece nemli olan faz dnm scaklklar ve mekanik zellikler zerindeki etkisini ortaya koymaya altk. TiNi alamlarna sklkla uygulanan sl ilemlerin banda souk ilem sonras ekil bellek zelliini kazandrmak iin yaplan tavlama ilemleri gelmektedir. Bu sl ilem zellikle eit atomlu ve titanyumca zengin TiNi alamlar iin uygundur [25,26]. nk artan nikel miktaryla souk deformasyon zorlamaktadr. Nikelce zengin TiNi alamlar iin ise (Ni miktar 50.5 at. %) [25,26] ok daha uygun olan, yalandrma sl ilemiyle mekanik zelliklerin ve dnm scaklklarnn kontrol edilmesidir. Literatrde yer alan, TiNi kpklerin yalandrma sl ilemi [19, 2737] sonucunda zelliklerinde meydana gelen deiimlere ilikin almalarda, sl ilem ncesi kpklerde byk miktarda bulunan ikincil fazlarn zeltiye alma ilemi srasnda zndrlememesi nedeniyle tutarszlklar bulunmaktadr. Bu almada tek fazl TiNi kpkler kullanlarak sl ilemler gerekletirilmi ve daha tutarl sonulara ulalmaya allmtr.
2. DENEYSEL YNTEM 2.1. Kullanlan Tozlar ve retim Yntemi TiNi kpkleri retmek iin balang tozlar olarak nikelce zengin, Ti-50.6 at. %Ni alam tozlar kullanlmtr. Boluk yapc olarak ise kresel magnezyum (Mg) tozlar tercih edilmitir. Mg boluk yapc miktar hacimce % 20-50 aralnda olacak ekilde ayarlanmtr. Kullanlan tozlar ve retim yntemine ait geni bilgi nceki almalarmzda [4,9,15,16] bulunabilir. % 50 Mgden daha az Mg ieren kompaktlar sinterleme esnasnda toplam Mg miktar % 50 olacak ekilde ekstra Mg, koruyucu olarak, ilave edildikten sonra sinterlenmitir. Sinterleme scaklna (1100 C) stma hz 10 C/dak olarak sabit tutulurken, sinterleme sresi (1 saat) sonrasnda pota frnn souk blgesine ekilerek, yaklak 60-75 C/dak bir hzda numunelerin oda scaklna soutulmalar salanmtr. retilen farkl miktarda gzeneklilie sahip TiNi kpklerin sl ilem ncesi grnts ekil 1de verilmitir.
ekil 1. Farkl miktarda gzenek ieren sinterlenmi TiNi kpkler.
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2.2. Yalandrma Isl lemi Sinterleme sonras farkl gzeneklerde retilen tek fazl (B2 stenit), (ekil 2) TiNi kpkler, koruyucu argon atmosferi altnda 400 C scaklkta 1 saat sreyle yalandrma sl ilemine tabi tutulmulardr. zeltiye alma ilemi yaplmamtr nk sinterleme sonras numuneler ekil 2den de grld zere zaten sadece istenilen stenit fazn iermekteydiler. Yalandrma scakl ve sresi ayn kompozisyondaki hacimli (gzenek iermeyen) TiNi alamlarnda sperelastisite asndan en iyi sonularn elde edildii scaklk ve sre olarak seilmitir. Yalandrma esnasnda olas oksitlenmeyi minimize etmek iin numuneler bir pota ierisindeki Mg tozu iine gmlerek sl ilem gerekletirilmitir. Frnn souk blgesinde bekletilen numuneler scakln 400 Cye ulamas ve kararl hale gelmesiyle birlikte scak blgeye indirilmitir. Yalandrma sresinin tamamlanmasyla birlikte pota tekrar souk blgeye ekilerek 3 dakika sreyle soumaya braklmtr. Daha sonra hemen frndan alnarak zerine alkol pskrtmek suretiyle oda scaklna soutulmalar salanmtr. Bu yntemle toplam soutma sresi 4 dakikadan daha az olarak gereklemitir. Su verme ilemi nemli derecede oksitlenmeye neden olduu iin tercih edilmemitir.
ekil 2. (a) TiNi toz ve (b) % 38, (c) % 43, (d) % 51, (e) % 59 gzenekli TiNi kpe ait XRD patternleri. 2.3. Karakterizasyon Sinterlenen numunelerin younluk ve gzenek miktar Arimet metoduyla llmtr. yapda oluan fazlar Rigaku D/Max 2200/PC model X n difraktometresi (XRD) yardmyla belirlenmitir. TiNi kpklerin dnm scaklklar Perkin Elmer Diamond diferansiyel taramal kalorimetresi (DSC) ile 10 C /dak stma ve soutma hzlar kullanlarak belirlenmitir. Basma ve sperelastisite testleri 10X10 mmlik silindirik numuneler kullanlarak 30 kN kapasiteli, stma haznesi olan Instron 3367 mekanik test cihaz yardmyla 0.1 mm/dak basma hzyla gerekletirilmitir. Elastik modl deerleri gerilim-gerinim diyagramnn dorusal ksmndan hesaplanrken, stenit-martensit dnm gerilimi % 0.2-offset metodu ile hesaplanmtr. Sperelastisite testleri 0-250 MPa aralnda dngsel ykleme ve boaltmalarla oda scakl (25 C), vcut scakl (37 C) ve stenit biti (Af) scaklnn 10-20 C zerindeki bir scaklkta yaplmtr.
3. BULGULAR VE DEERLENDRME 3.1. Faz Dnm Scaklklar Balang TiNi alam tozu, sinterleme sonras, ve akabinde yalandrma sl ilemine tabi tutulan kpklere ait DSC erileri ekil 3de gsterilmektedir. Bu erilerden elde edilen [38] dnm scaklklarnn gzeneklilikle ilikisi ise ekil 4de verilmitir. Yalandrlm numunelerde soutma esnasnda tek bir pik grnrken stma srasnda iki ayr pik gzlenmitir. ekil 4den aka grld zere gzenekliliin dnm scaklklar zerinde ok fazla bir etkisi bulunmazken, zellikle martensitik dnm scaklklarnn (martensit balang, Ms, ve martensit biti, Mf) yalandrma sonras nemli lde ykseldii anlalmaktadr. Ms ve Mf scaklklarndaki art 41-65 C arasndayken (ortalama 46 C Ms iin ve 53 C Mf iin) Af scaklndaki art ortalama 23 C olarak gereklemitir. stenit balang, As, scakl ise belirgin bir deiim gstermemi ve buna bal olarak martensitik dnm ile ters reaksiyon arasndaki histeresis azalmtr.
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Istma srasnda gzlemlenen iki ayr pikin varl kpklerin kimyasal olarak homojen olmamasna atfedilmitir. Yalandrma ilemi sonucu iyapda kelen Ti3Ni4 faz bu homojensizlie neden olmaktadr. Ti3Ni4 keltileri oluurken daha fazla Ni atomu tketildiinden TiNi matrix iindeki Ni miktar azalmaktadr. Ni miktarnn azalmas da dnm scaklklarndaki art beraberinde getirmektedir. Ti3Ni4 keltileri 50.6 at.% Ni gibi grece az Ni ieren TiNi alamlarnda homojen olmayan bir ekilde, sadece tane snrlar ve civarnda olumaktadrlar [39]. Bu kelme davran neden As scaklnn yalandrma sl ilemi sonrasnda ayn kaldn aklamaktadr. keltilerin olumad tanelerin i ksm Nice daha zengindir ve stma srasnda daha nce stenite dnmeye balarlar. Bu da piklerin genilemesine neden olmaktadr. Benzer durum soutma srasnda da grlr. Dikkat edilirse (ekil 3 (c)) bu piklerin de olduka geni olduu grlmektedir. Tek fark belirgin iki pikin olmamasdr. Ayrca kullanlan TiNi tozu ve sinterlenen numunelerde de (ekil 3 (a) ve (b)) zellikle soutma esnasnda keskin pikler elde edilememitir. Bunun yerine olduka geni ve yayvan piklerin gzlenmesi numunelerin iyapsnda Ni dalmnn homojen olmamasna balanmtr.
ekil 3. (a) ve (b) Sinterleme sonras, (c) ve (d) 400 Cde 1 saat sreyle yalandrlan TiNi kpklere ait DSC erileri. (i) Istma ve (ii) Soutma erisi.
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ekil 4. Gzenek miktarnn dnm scaklklar zerindeki etkisi. Ti3Ni4 keltileri soutma srasnda R faznn olumasna neden olabilirler [39-41]. Bu durum DSC erilerinden iki farkl pikin grlmesiyle anlalr. R faznn olumas sistemin enerjisini drebilir nk B2 stenitten R fazna dnm latis gerinimini ok az artrmaktadr. te yandan B2den B19 martensite dnm 10 kat daha fazla latis gerinimi yaratmaktadr. Koherent Ti3Ni4 keltilerinin gerinim alanlar martensit faznn ekirdeklenmesini kolaylatrmaktadr. Fakat ayn zamanda oluan martensitlerin bymesi iin engel tekil etmektedirler. Bu da tamamlanamam dnmlerle sonulanmaktadr. izelge 1den grld zere, bu kompozisyondaki tam bir dnm iin 23 J/g civarnda olan [42], dnm ss (latent heat of transformation) deerleri olduka dktr. Bu yzden ekil 5deki XRD diyagramnda (25 Cde elde edilmi) esas olarak martensit faz grlmesi gerekirken stenit faz daha fazla miktarda bulunmutur. DSC sonularna gre ise Ms ve Mf scaklklar srasyla 65 ve 25 Cdir. R faznn oluup olumadnn kesin tespiti iin TEM almalarnn yaplmas gerekmektedir. Bu faz termal analiz srasnda oluuyor oabilir ama DSC erisi zerinde iki pik rttnden gzlemlenmeyebilir. Ayrca uygulanan ksa yalandrma sresi ve de inhomojen dalm kelti younluunun yetersiz olmasna dolaysyla TiNi matrixin yeterince glendirilememesine neden olabilir. Bylelikle B2den B19a direkt dnm gerekleebilir. 100 nm [43] ve daha byk boyutlarda olan Ti3Ni4 keltilerinin R faz oluumunu tetikledikleri bilinmektedir. Bu almada uygulanan yalandrma sl ilemi ayn kompozisyondaki hacimli TiNi alamlarnda 30 nmden [25] daha kk keltilerin olumasyla sonulanmtr. Gzeneklerin kelti oluumuna etki edecei dnlmemektedir dolaysyla benzer boyutta keltilerin kpklerde de oluaca dnlrse R faznn olumad sonucu karlabilinir. izelge 1. Yalandrlm TiNi kpklere ait martensitik ve ters dnmlerin slar. Gzeneklilik (%) Latent heat of transformation, Dnm ss (H, J/g) -Hileri 38 43 51 59 5.3 2.1 4.1 4.3 Hgeri 8.6 4.4 7.5 8.5
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ekil 5. % 51 gzenekli yalandrlm TiNi kpe ait XRD diagram. 3.2. Mekanik ve Sperelastisite zellikleri Ayn miktarda gzenee sahip (% 38) TiNi kpklerin iki farkl durumda, sinterleme ve yalandrma sonras, oda scaklndaki gerilim-gerinim davranlar ekil 6da grlmektedir. Yalandrma sl ilemine maruz braklan kpkler oda scaklnda daha kt sperelastisite davran gsterdiklerinden farkl gzeneklilikteki dier yalandrlm numuneler 80 Cde dngsel basma testine tabi tutulmulardr. Bu scaklk numunelerin Af scaklklarndan 10-15 C daha fazladr ve normal koullarda tam sperelastisite davran beklenmektedir. Dnm scaklklarnn ykselmesi nedeniyle oda scaklnda, yalandrlm TiNi kpklerin i yaps martensit ve stenit fazlarndan olumaktadr. Bu scaklkta basma testi yapldnda mevcut martensit faz yeniden ikizlenme mekanizmas ile deforme olurken stenit faz da gerekli kritik gerilme deerine ulaldnda martensit fazna dnmektedir. Yeniden ikizlenen martensitler ancak Af scaklnn zerine stlarak tekrar stenit fazna dntrlebilinir. Sabit scaklkta (oda scakl) yaplan test sonucunda stenit fazna dnemediklerinden ekil kazanmna katklar olmamaktadr. ekil kazanm ykn uzaklatrlmasyla yeniden stenite dnen gerilimle oluturulmu martensitlerden dolaydr. Bu yzden yalandrlm numuneler oda scaklnda daha kt sperelastisite zellii gstermektedirler. Ayn zamanda daha dk mukavemetlidirler. Gerilim nedeniyle stenitten dnm ile oluan martensitlerin bir ksm da yalandrlm numunelerin dnm scaklklarnn yksek olmas nedeniyle kararl hale geebilir ve yk uzaklatrldnda tekrar stenite dnmeyebilir. Bu da geri kazanlamayan gerinim miktarlarnda arta neden olur.
ekil 6. % 38 gzenekli TiNi kpn sinterleme ve yalandrma sonras oda scaklndaki gerilim-gerinim davran. Farkl miktarda gzenekli yalandrlm TiNi kpklerinin 80 Cdeki gerilim-gerinim davranlar ekil 7den takip edilebilir. Oda scaklndaki ile karlatrlrsa daha yksek ekil kazanmnn (% 5 civarnda, ekil 7 (a)) olduu grlecektir. Her ne kadar burada verilmese de, ayn miktarda gzeneklilie sahip ve sinterleme sonras oda ve vcut scaklnda (37 C ) yaplan testlerden de daha iyi bir sperelastisite ve ekil kazanm salanmtr. Fa-
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kat ayn gzeneklilikte, sinterlenmi ve baka ilem grmemi numuneler 60 C gibi Af scaklklarndan 10-15 C daha yksek scaklklarda test edildiinde sinterleme sonras yalandrma ilemine tabi tutulmu ve 80 Cde test edilmi numuneler ile ok benzer mekanik davran sergilemilerdir, ekil 7 (c). Koherent Ti3Ni4 keltileri mevcut almadaki kompozisyonda sadece tane snrlar ve yakn evresinde olutuu iin TiNi matrixi yeterince glendirememi ve bunun sonucunda da nemli bir mukavemet artn salayamamtr. Bu keltilerin sperelastisite zelliini iyiletirmeleri matrixdeki Ni ieriini azaltmalar ve arayzeyde gerilim alanlar oluturarak martensit faznn olumasn kolaylatrmalar ile aklanmaktadr. Ayn zamanda TiNi matrixi glendirerek dislokasyon hareketini zorlatrmaktadrlar. Bylelikle deformasyon srasnda kayma mekanizmasnn aktiflemesini engelleyerek tamamen gerilim ile oluturulan martensit mekanizmas ile deformasyonun olmasn salamaktadrlar. Hacimli TiNi alamlarnda basma yk altnda % 6ya [26] kadar olan gerinimler geri kazanlabilmektedir. Ne yazk ki gzenekli TiNi alamlarnda farkl boyutlarda sinterleme boyunlarnn ve hcre duvarlarnn olumas nedeniyle % 3.5 gibi dk bir gerinim deeri bile tamamen geri kazanlamaktadr, ekil 7(d). ekil 8de gsterildii zere kararl hale gelen ve geri dnmeyen martensitler buna neden olmaktadrlar. Isl ilemin daha iyi sonu vermesi iin gerilim altnda yaplmas ve bu sayede homojen olarak (tane snr ve ilerinde) koherent Ti3Ni4 keltilerinin oluturulmas salanabilir.
ekil 7. Yalandrlm TiNi kpklerin 80 Cde gerilim-gerinim erileri, (a) % 38, (b) % 43, (c) % 51, (d) % 59 gzenekli.
ekil 8. % 43 gzenee sahip TiNi kpn % 7 gerinime yklenip boaltldktan sonra SEMde grntlenen mikroyaps: stenitik TiNi taneleri iinde beyaz renkli kk martensitler yer almaktadr.
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ekil 9 sinterlenmi ve yalandrlm numunelerde elastik modl-gzeneklilik-scaklk ilikisini gstermektedir. Elastik modl deerleri artan gzeneklilik ile dorusal bir ekilde azalrken hacimli TiNi alamlarnda olduu gibi artan scaklkla artmaktadr. Yalandrlm kpkler daha dk elastik modle sahiptirler. Koherent keltiler her ne kadar homojen olarak dalmasa da yine de kritik gerilimi drerek martensitin olumasn kolaylatrmtr. Bu almada % 10-15 aralnda sneklik deerleri elde edilmitir. Zhang ve arkadalarnn almasnda [20] amonyum bikarbonat boluk yapc olarak kullanlm ve % 61 gzenekli TiNi alam retilmitir. Bu kpk % 3 gerinime kadar (15 MPa) dngsel olarak yklenildiinde ilk dngde krlmtr. Bu almadaki % 59 gzenekli TiNi kpk ise 80 MPa sabit gerilime (ilk dngde % 6 gerinim) dngsel olarak 20 kez maruz braklm ve herhangi bir atlak oluumu tespit edilmemitir. Dier btn retim yntemlerinde krlgan, mekanik ve korozyon dayancn dren ikincil intermetaliklerin, oksitlerin ve/veya karbonitratlarn olumas kanlmazdr. Ayn zamanda bu almadaki gibi lokal gerilim konsantrasyonlarn minimize edecek en uygun gzenek ekli olan kre, dier almalarda elde edilememitir. Sabit basnta scak presleme ileminde mikro-gzenekler nerdeyse sfrlanmakta iken yine de mukavemet deerlerinin [6,19,44] bu almadakiler ile ayn seviyede olmas gzeneklerin yap ierisinde homojen olarak dalmamas ve oksitlenme gibi kirlenmeler ile aklanabilir. Dier yntemlerle bu almadaki sneklik deerlerine ulalmas ikincil fazlarn ve kirlenmenin olmas nedeniyle mmkn grlmemektedir.
ekil 9. Young modlnn scaklk, gzeneklilik ve yalandrma sl ilemi ile deiimi.
4. SONULAR 1. Yalandrma sl ilemi TiNi kpklerin dnm scaklklarn As dnda ok nemli oranda artrmaktadr. Ayn zamanda, yalandrlm TiNi kpklerde faz dnmleri ksmi olmaktadr. 2. Yalandrma sl ilemine maruz kalm TiNi kpklerde Ms scakl, As scaklndan daha yksektir. 3. TiNi kpklerin basma ve sperelastisite davran hacimli TiNi alamlarnnkinden farkldr. Dorusal sperelastisite gsteren kpklerde elastik modl, dayan ve martensit oluturmak iin gereken gerilim deeri artan gzeneklilikle azalmaktadr. 4. Btn kpklerde ksmi sperelastisite gzlenmi olup, yalandrma ve dngsel ykleme-boaltma sonras % 5e varan gerinimler tamamen geri kazanlabilmitir. Kalnt gerilmelerin nedeni test scakl ya da farkl geometrik yapda olan hcre duvarlar ve sinter boyunlarnn farkl gerilmelere maruz kalmas sonucu meydana gelen martensit stabilizasyonuna balanmtr. 5. Yalandrma sl ilemi martensitik dnm iin gereken gerilim deerini drerek elastik modln de azalmasna neden olmaktadr.
TEEKKR Bu alma Trkiye Bilimsel ve Teknolojik Aratrma Kurumu (TBTAK, Proje no: 108M118) tarafndan desteklenmitir.
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MODELING, SIMULTATION AND CHARACTERIZATION
www.turkishpm.org
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FARKLI GEOMETRLERE SAHP GAZ ATOMZASYONU NOZUL PERFORMANSLARININ HESAPLAMALI AKIKANLAR DNAM (CFD) LE KARILATIRILMASI
Mustafa GLEEN*, Rahmi NAL** ve Melih C. KUHAN*
*
Eskiehir Osmangazi niversitesi, Mhendislik ve Mimarlk Fakltesi, Makine Mhendislii Blm, 26030, Eskiehir, mgulesen@ogu.edu.tr, mckushan@ogu.edu.tr ** Dumlupnar niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 43020, Ktahya, runal@dpu.edu.tr,
ZET Bu almada nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri deitirilerek nozul veriminin daha yksek olabilecei en uygun tasarm CFD zm yntemiyle bulunmaya allmtr. Bu amala 3 farkl yeni tasarm yaplarak daha yksek verimli nozul tespit edilmeye allmtr. CFD sonularna gre en uygun tasarmn Model 3 adl tasarm olduu anlalmtr. Bu tasarm metal ak borusu ucunda en yksek emme basncn oluturmakla birlikte en yksek hz deerlerine dk basnlarda dahi ulamaktadr. Ayrca gaz tketimi de bu tasarm iin en dk deerdedir. Btn bunlardan dolay model 3 adl tasarm mevcut nozul performansna gre daha yksek performansa sahiptir. Bu sonular ile CFD zmlerinin nozul tasarmnda kullanlabilecei ortaya konmutur. Bylece daha dk maliyet ve ksa srede daha yksek verimli nozul geometrisi gelitirmek mmkn olabilecektir. Anahtar Kelimeler: Gaz atomizasyonu, Nozul tasarm, CFD
COMPARISON of DIFFERENT GEOMETRICAL GAS ATOMIZATION NOZZLE PERFORMANCES BY COMPUTATIONAL FLUID DYNAMICS (CFD)
ABCTRACT This study is important in the design of the nozzle geometry and gas output may be higher than the yield of field variables by changing the nozzle design the most appropriate method of CFD model with the best solution. For this purpose, a new design made of 3 different nozzle tried to determine a more highly efficient. According to the results of the CFD model 3s design proved to be the most appropriate design. This design tip of the metal flow tube with creating the highest suction pressure reaches the highest velocity values , even at low pressures. In addition, gas consumption is also low for this design value. Because of this design available at Model 3 has higher performance than the performance of the nozzle. These results suggest that the CFD solutions were used in the design of the nozzle. Thus, lower cost and shorter time will be possible to develop highly efficient nozzle geometry. Keywords: Gas atomization, Nozzle design, CFD (computational fluid dynamics) 1.GR Gaz atomizasyon yntemi ok sayda atomizasyon deikenlerine sahiptir (sv metal debisi, gaz debisi, gaz basnc ve nozul geometrisi). Bu deikenlerden en nemlisi nozul geometrisidir [1]. Nozul en basit kelime anlamyla simetri ekseni boyunca hareket eden akkann hzn artrrken basncn dren geometrik yapya verilen isimdir. Gaz atomizasyonunda kullanlan nozullar farkl geometrilere sahiptirler. Genel olarak kullanlan nozullar, sonik (daralan) veya spersonik (daralan-genileyen) geometriye sahiptirler. Atomizasyon ileminde nozul, gazn kinetik enerjisini sv metale aktarr. Yaplan almalar sonucu elde edilen bilgilere gre spersonik geometrili nozullar,
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sonik geometrili nozullara gre daha iyi gaz genleme davran gsterirler. Bylelikle spersonik nozullarda daha ince boyutta toz retimi gerekletirilir. Yksek verimli nozullar mmkn olduu kadar dk atomizasyon basnlarnda daha kk apta toz retimine imkan salarlar. Yakndan elemeli sistem ile toz retimi fiziksel olarak olduka karmak bir ilemdir. Yakndan elemeli sistemlerde gaz dolam blgesi ve bu blgenin atomizasyona olan etkisinin aratrma konusu olmutur. Gaz ak dinamii konularnda yaplan aratrmalar sonucu daha ince toz boyut dalmna sahip tozlar retilmi ve atomizasyon ileminin verimi artrlmtr [2-7] Akn olduu mhendislik sistemlerinin tasarm ve analizinde iki temel yaklam vardr: deney yapma ve hesaplama. Gnmz aratrmaclar hem deneysel analizi hem de CFD (hesaplamal akkanlar dinamii) analizini uygularlar ve bu ikisi bir birini tamamlar. Hesaplamal akkanlar dinamii (CFD) ile laminer aklar kolayca zmlenebilirken, uygulamadaki trblansl aklar trblans modellerini kullanmakszn zmek imkanszdr. Ne yazk ki genel bir trblans modeli yoktur ve bir trblansl CFD zm, sadece trblans modelinin uygunluu kadar iyidir. Bu snrlamaya ramen, standart trblans modelleri uygulamadaki ou mhendislik problemlerinde makul zmler verir. Saysal ve deneysel olarak bulunan genel byklklerin karlatrlmas yoluyla CFD zmlerini dorulamak iin ounlukla deneysel veriler kullanlr. CFD, daha sonra, dikkatlice kontrol edilen parametrik incelemeler yoluyla, gerekli deneysel test saysn drerek tasarm srecini ksaltmak iin kullanlr [8]. Gaz atomizasyon ileminde nozul ak blgesinde atomizasyon gaznn scakl, hz ve basnc ergiyik metalin ak zerine aktarlmas, kinetik enerjiyi ve soutma etkisini belirler ve dolaysyla retimi nemli lde etkiledii gibi balang boyutu, ekli, damlacn uu yn ve radyal dalm etkiler. Nozula yakn blgede gaz ak analizi, saysal simlasyon/modelleme hesaplamal akkanlar dinamii (CFD) kodlar yardmyla yaplabilir. Bu kodlar genellikle sktrlamaz ve/veya sktrlabilir aklar zer ve trblans modelleri kullanlr. Nozula yakn blgede atomize gazn ak ve hz blgelerinin modellenmesi atomizasyon parametrelerinin optimizasyonu iin temel kurallar salar. Bu durumda modelleme sonular farkl atomizasyon ilemlerinin modellenmesinde balang koullar salar [9]. Bu almada Aydn ve naln [ 1,10-11] yaptklar almalar farkl geometrilere sahip atomizasyon ilemlerinin modellenmesinde balang koullarn salamtr. CFD modelin deneysel verilere yaklam en iyi olacak ekilde model zerinde eitli parametrelerin etkileri incelenmitir. Nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri deitirilerek nozul veriminin daha yksek olabilecei en uygun tasarm bulunmaya allmtr. Yeni tasarmlar yaplarak daha yksek verimli nozul elde edilmeye allmtr. 2. FZKSEL MODELN TANIMI Model geometrilerinin oluturulmasndan nce DPU Makine Mhendislii laboratuarndaki gaz atomizasyon nitesinde kullanlan mevcut nozulun geometrisi ekil 1de gsterilmitir. Burada nozul as, A knt mesafesi ve R boaz akl olarak tanmlanmtr. Nozul yksek basnl tpe bal orta bir giri ile tek bir manifoldu vardr. Atomizasyon gaz olarak azot kullanlmtr. Nozul 0.2 mm boaz akl, 5 mm knt mesafesine ve 260 lik nozul asna sahiptir. Oluturulan geometrilerde, boaz akl, knt mesafesi ve nozul as deerleri deitirilerek 3 farkl nozul geometrisi oluturulmutur (ekil 2).
ekil 1. Nozulun ematik gsterimi.
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ekil 2. Farkl geometrilere sahip nozullar. Mevcut nozul geometrisine gre Model 1de nozul as () 260 sabit tutulmu, boaz akl (R) 0.3 mm karlm ve knt mesafesi (A) 6 mm olarak arttrld grlmektedir. Model 2de boaz ksmanda gazn kat edecei mesafe arttrlm boaz akl 0.2 mm, nozul as 160 ve knt mesafesi mevcut nozuldaki gibi 5 mm alnmtr. Model 3te daralan-genileyen ksmlarn alar mevcut nozulla ayndr. Fakat daralan ksmda gazn kat edecei mesafe arttrlm boaz akl 0,2 mm ve knt mesafesi 6.84 mmye karlmtr. Atomizasyon gaz ak modeli olutururken aadaki kabuller alnmtr. Gaz ak srekli bir rejimdir. Atomizasyon nozul sisteminin simetrik ekle sahip olduu iin hesaplama iki boyutlu eksenel simetrik olarak zlmtr. Gaz ak izentropik sktrlabilir ve ideal gaz yasas kanunu kabul edilmitir. Gaz ak trblansl ak ve ak katmanlar arasnda momentum ve enerji transferi vardr. Yerekimi ihmal edilmitir. 3. SAYISAL MODELLEME VE HESAPLAMA METODU 3.1 Temel Denklemler Atomizasyon sistemin sadece gaz akn simle edilmesi ile atomizasyon gaz basncnn etkileri zerine modelleme almas, CFD yazlmnn paket program FLUENT 6.3 kullanlarak yerine getirilmitir. FLUENT 6.3 program seilen denklemlerin zmnde sonlu hacim yaklamn kullanr. CFD gibi byle nmerik modelleme teknikleri ak ve s transferi problemlerini simule etmek iin gl bir aratr. Ktlenin korunumu veya sreklilik denklemi, momentumun korunumu veya NavierStokes transport denklemi ve enerjinin korunumu denklemi nmerik olarak zlebilir. ki boyutlu eksenel simetrik geometriler iin sreklilik denklemi; [12] (1)
Burada gaz younluu, x eksenel koordinat, r radyal koordinat, vx eksenel hz, and vr radyal hzdr. Sm kaynak terimi ise ayrlm ikinci fazdan (sv damlacklarnn buharlamas nedeniyle gibi) srekli faza ilave edilen ktle ve herhangi bir kullanc tarafndan tanmlanm kaynaktr. Denklem (1) sktrlabilir ve sktrlamaz aklar iin kullanlan ktlenin korunumu denkleminin genel formudur. ki boyutlu eksenel simetrik geometriler iin eksenel ve radyal momentum korunum denklemleri aada verilmitir.
(2)
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ve
(3)
Burada;
ve
(4) srasyla yerekimi kuvveti ve d kuvvettir (ayrk ve trblans yitim hz denklemleri aada veril(5)
Burada p statik basn, gerilim tens, vz swirl hz, faz ile etkileimden ykselme gibi).
Reynolds stress model (RSM) gre trblans kinetik enerji mitir.
ve (6) Burada; = 0:82, = 1, = 1:44, fonksiyonu olarak llm deerler ve and = 1:92, Yerekimi vektrle alakal lokal ak ynnn bir kaynak terimlerdir.
Sktrlabilirlik etkilerine yksek hzlardaki gaz aklarnda ve/veya byk basn deiimlerinde karlalr. Ak hz gazn ses hzna yaklat ya da at zaman veya sistemde basn deiimi (p=p) byk olduu zaman basnla gaz younluunun deiimi ak hz basnc ve scakl zerinde nemli bir etkiye sahiptir. Sktrlabilir aklar iin, ideal gaz kanunu aadaki formda yazlr; (7)
Burada pop iletme basnc (operating conditions panelinde tanmlanr), p iletme basncna gre bal lokal statik basn, R niversal gaz sabiti, ve Mw molekler arlktr. Scaklk T enerjinin korunum denkleminden hesaplanabilecektir. 3.2 A Yapsn Oluturma Nozul iki boyutlu ve eksenel simetri olmak zere GAMBIT 2.4.6 programnda izilmi ve a yaps (meshleme) oluturulmutur (ekil 3). ki boyutlu eksenel simetrik geometrili zm, iki boyutlu ve boyutlu geometrilere gre hassasiyet asndan bakldnda daha avantajldr. nk grid saysnn azl zaman tasarrufu salayaca gibi, alan bana den grid miktar dierlerine gre olduka yksektir. ekil 4te nozulun yaknsak-raksak blgesinin grid yaps ve hesaplanan alan gsterilmitir. Nozulun en dar blgesi (boaz) 0.2 mm. Ak daha iyi analiz edebilmek iin nozul blgesi ince meshlenmitir. Bu almada incelenen tm durumlar iin, gen a yaps tercih edilmitir. Oluturulan a yaps ak zelliklerini ve ak tahminleri, sktrlabilir ak teorileri ve literatrle tutarl bir ekilde yakalamak mmkndr [13].
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ekil 3. Mesh yaps ve snr artlar.
ekil 4. Kritik blgelerdeki ve cidarlardaki mesh yaplar. 3.3 Snr artlar CFD simlasyonlar basnca dayal, kararl durum ayrlm tam zc kullanlarak yapld. Ak trblansl, viskoz model olarak Reynolds stres model (RSM) kullanlarak simlasyon yapld. Model sabitleri default deerler uyguland. Programn zc tipi seiminde seilenler ise pressure based, implicit yaklam, standart duvar fonksiyonu ve steady (kararl) zmdr. Akkan olarak azot gaz, younluk iin ideal gaz kanunu ile sktrabilir gaz gibi modellendi ve NIST verilerine gre gaz sabitleri Tablo 1 de verilmitir[14]. NIST verilerine gre azot gaznn sktrabilirlik faktr 11 Atmosfer basncnda ve 300 K scaklkta 0,998 dir. Bu durumda ideal gaz kanunu bu simlasyon kullanmak makuldr. Snr artlar ekil 3te gsterilmitir. Atomizasyon basnc 0.8, 1.0, 1.3 ve 1.7 MPa deerler CFD modelleme esnasnda gaz giri basnc olarak kullanld. Gaz giriindeki scaklk 300 K alnd. Gaz kn CFD modelde basn k olarak belirtildi ve atmosfer basn deeri alnd. Tm duvar scaklklar 300 K alnd. Sutherland vizkosite kanunu ideal gazlarn kinetik kuram ve idealize edilmi bir molekller aras kuvvet potansiyeline dayanmaktadr. Bu forml iki veya katmanldr. Bu almada katmanl Sutherland kanunu kullanlmtr. katmanl Sutherland kanunu; (8) Burada viskozite (kg/ms), T statik scaklk (K), 0 bir referans deer (kg/ms), T0 bir referans scaklk (K), ve S ise gazn karakteristii olan Sutherland sabiti olarak isimlendirilen bir efektif scaklk (K). Scaklk ve basncn orta deerlerinde hava iin, 0= 1.7894x0-5 kg/ms, T0 = 273.11 K, and S = 106.67 K [15].
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Tablo 1 Saysal simlasyon iin azot gaznn zellikleri Fiziksel zellikler Younluk (kg/m3) C (J/(kg.K)) Termal iletkenlik (W/(m.K)) Referans viskosite (kg/(m.s)) Referans scaklk (K) Efektif scaklk (K) Molekler arl (kg/(kg.mol)) Standart hal entropisi (J/(kg.mol.K)) Deer 1.138 1040.67 0.0242 1.663 10-5 273.11 106.67 28.0134 191494.8
3.4 zm Metodu zme balama aamasnda programn kullanc kitabndan olduka yararlanlmtr. Yksek basnl almalarda zme balamada nerilen yollarn kullanlmas nem arz etmektedir. Aksi takdirde zme ulalamamaktadr. Bunun iin zellikle 200 iterasyonda kararl bir yaknsama salanmas iin enerji denklemleri seilmemitir. Balang deeri iin hz deeri programn hesaplad deerden daha dk girilmitir. Ayrca rahatlatma faktrleride (under-relaxation factor) basn iin 0.4, momentum iin 0.3, younluk iin 0.3, enerji iin 0.9 seilmitir ve dierleri default deerleri olarak ayn kalmtr. Yaknsama da kararl bir grnt salandktan sonra (200 iterasyon sonra) enerji denklemi almtr. zm iin 1.dereceden denklemler (first order upwind) seilmitir. RSM ayrklatrma zmnde 2. dereceden denklemler (second order upwind) altnda simlasyonun yaknsamas olduka zordur[14]. Yaknsama kriteri olarak ise enerji denkleminin 10-6 hata oran esas alnmtr. Ayrca giri ve k arasndaki ktlesel debiler arasndaki farknda 10-6 orannda bir farka ulamas yaknsama kriteri olarak gz nne alnmtr. 4. BULGULAR ve DEERLENDRME Bu almada simlasyonun doruluu naln deneysel verilerinden yararlanlmtr [1,17-18]. Aydn ve nal yaptklar almada saysal zmlemeleri ile deneysel verilere bakldnda nozul gaz basnlar arasndaki fark tm basnlarda ayn olduu, deneysel verilerde nozul u basnc daha az olmakla birlikte, Realizable model sonular ile arasndaki fark %11-15 arasnda deitiini tespit etmilerdir [11]. Reynolds stres model ile deneysel verileri kyaslandnda %3-11 arasnda deiirken, %11 fark sadece 1.0 MPa basn altnda elde edilmitir. 1.3, 1.7, 2.2 ve 2.7 MPa basnlarda deneysel verilere yaknl %3-5 arasndadr (ekil 6). Bu sonuca gre Reynolds stres model deneysel verilere en yakn sonucu vermitir. Elde edilen bu sonuca gre tasarlanan modeller de Reynolds stres modele (RSM) gre zm yaplmtr. zm sonular Tablo 2de verilmitir.
ekil 5. Nozul u basncnn CFD ve deneysel veriler ile karlatrlmas[11].
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Atomizasyon basncna gre metal ak borusu u basn deerlerinin karlatrlmas ekil 6da verilmitir. Model 3 adl nozulun dierlerine gre belirgin bir ekilde daha yksek negatif basn oluturduu grlmektedir. Bu basn sv metalin nozula ekilmesini salayarak atomizasyon ileminin yerekimi etkisiyle yaplabileceini gstermektedir. Eer u basn pozitif olursa sv metalin yerekimi etkisiyle ak mmkn olmadndan ergitme odasnn kapal olarak yaplmas ve st basn uygulamak gerekecektir. Gaz basncna gre gaz debisinin deiimi ekil 7de verilmitir. Bu deerlerin incelenmesi sonucu model 2 ve model 3 adl tasarmlarn debi asndan da en uygun tasarmlar olduu grlmektedir. Gaz debisinin daha az olmas gaz tketimini azaltacandan dolay dierlerine gre daha verimli bir nozul tasarm olduu sylenebilir. Tablo 2. Nozullarn CFD zm deerleri Nozul Nozul As Boaz akl (mm) Boaz Alan (mm2) knt Mesafesi (mm) alma Basnc (bar) 8 Mevcut Nozul [9] 26 0,2 8,5 5 10 13 17 8 Model 1 26 0,3 12,7 6 10 13 17 8 Model 2 16 0,2 11 5 10 13 17 8 Model 3 26 0,2 11 6,84 10 13 17 Gaz Hz (m/s) 597 613 622 626 580 592 608 624 590 605 629 647 594 623 636 646 Mach Says 2,61 2,77 2,88 2,94 2,51 2,58 2,69 2,81 2,57 2,72 2,96 3,21 2,84 2,88 3,05 3,23 Gaz Debisi (kg/dak) 1,06 1,72 2,24 2,95 1,74 2,14 2,84 3,54 1,13 1,42 1,84 2,46 1,08 1,61 1,94 2,64 U Basnc (mbar) 1002 1023 1070 1166 965 1007 1086 1176 1009 1027 1061 1144 956 971 974 1023
ekil 6. Atomizasyon basncna gre nozullarn u basn deiimi.
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ekil 7. Atomizasyon basncna gre nozullarn gaz debisi deiimi. Gaz basncna gre Mach saysnn deiimi ekil 8de verilmitir. Mach saysnn en yksek olduu tasarm Model 3 adl tasarmdr. Bu tasarmda Mach saysnn dk basnlarda dahi daha yksek olduu grlmektedir. Mach saysnn yksek olmas bu tasarmda gazn daha iyi hzlandn ve dolaysyla daha yksek bir kinetik enerjiye sahip olduu anlamna gelmektedir. Bu da daha yksek verimli bir atomizasyon ileminin gereklemesini salayacaktr. Sonuta dk basnlarda daha kk toz retmek mmkn olabilecektir.
ekil 8. Atomizasyon basncna gre nozullarn Mach says deiimi. Gaz basncna gre gaz hznn deiimi ekil 9da verilmitir. Burada da model 3 adl tasarm baz basnlarda en yksek gaz hzna sahip olmakla birlikte dier tasarmlar ile arasndaki fark ok belirgin deildir. Ancak basnca gre deiimi daha azdr. Model 3 adl tasramda 1.3 MPa basnta dahi 636 m/s gibi yksek hza ulamas tasarmn dierlerine gre stnln gstermektedir. Atomizasyon basncna gre Mach/gaz debisi orannn deiimi ekil 10da verilmitir. Model 2 ve Model 3 dier tasarmlara gre daha stn gzkmektedir. Dk gaz debisinde yksek hzn elde edilmesi nozulun verimini arttracaktr.
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ekil 9. Atomizasyon basncna gre nozullarn hz deiimi.
ekil 10. Atomizasyon basncna gre nozullarn Mach says/gaz debisi orannn deiimi. Daha az gaz debisi ile yksek hzn elde edilmesi tketimin az olmasna karn kinetik enerjinin yksek olmas anlamna gelmektedir. Buda daha kk tozun retilebilmesine imkan verir. Btn karlatrmalar dikkate alndnda en iyi tasarmn Model 3 adl tasarm olduu grlmektedir. Mevcut nozul 1.0 MPa basnta 613 m/s hz, 2,77 Mach says, 1,72 kg/dak debi ve 1023 mbar u basn deerlerine sahip iken model 3 adl tasarm 1.0 MPa basnta 623 m/s hz, 2,88 Mach says, 1,61 kg/dak debi ve 971 mbar u basn deerine sahiptir. 5. SONULAR Bu almada farkl geometrilere sahip nozullarn performanslar CFD yntemi ile incelenerek en uygun tasarmn bulunmas hedeflenmitir. Bu amala 3 farkl geometri karlatrlarak en uygun tasarm belirlenmitir. CFD sonularna gre en uygun tasarmn Model 3 adl tasarm olduu anlalmtr. Bu tasarm metal ak borusu ucunda en yksek emme basncn oluturmakla birlikte en yksek hz deerlerine dk basnlarda dahi ulamaktadr. Ayrca gaz tketimi de bu tasarm iin en dk deerdedir. Btn bunlardan dolay model 3 adl tasarm mevcut nozul performansna gre daha yksek performansa sahiptir. Bu sonular ile CFD zmlerinin nozul tasarmnda kullanlabilecei ortaya konmutur. Bylece daha dk maliyet ve ksa srede daha yksek verimli nozul geometrisi gelitirmek mmkn olabilecektir.
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KAYNAKLAR 1. Unal R. Improvements to close coupled gas atomization nozzle for fine powder production Powder Metallurgy, 50(1): 66-71, 2007. 2. LE T., and Henein, H., , Effect of nozzle geometry and position on gas atomization, The international journal of powder metallurgy, Volume 32, No 4, 353-363, 1996. 3. http://www.cstl.nist.gov/div836/836.01/PDFs/1998/EPMA_US.pdf 4. Ting J, Peretti M W, Eisen W B. The effect of wake-closure phenomenon on gas atomization performance, Mater Sci Eng A, 326(1): 110121 2002. 5. Mates, S. P., and Settles, G. S., A flow visualization study of the gas dynamics of liquid metal atomization nozzles, Proceedings of the 1995 International Conference on Powder Metallurgy and Particulate Materials, Seattle, May 14-17, 1995. 6. Ting J, Anderson IE, A computational fluid dynamics (CFD) investigation of the wake closure phenomenon, Materials Science and Engineering A, 379: 264-276, 2004. 7. Strauss, J.T., Hotter gas atomization increases atomization efficiency, Metal Powder Report, Volume 54, Issue 11, 24-28, 1999. 8. engel Y A., Cimbala J M., Akkanlar Mekanii Temelleri ve Uygulamalar, Birinci baskdan eviri, 2008. 9. Liu H., Science and engineering of droplets Fundamentals and applications, Noyes publications, New Jersey, USA, 2000. 10. nal, R., Investigation of the Metal Powder Production Efficiency of a New Convergent-Divergent Nozzle in Close-Coupled Gas Atomisation, Powder Metallurgy, Vol.50, No.4,p.302-306, 2007. 11. Aydn O., Unal R., Experimental and numerical modeling of the gas atomization nozzle for gas flow behavior, Computers and Fluids, 42, 37-43, 2011. 12. Fluent 6.1 Users Guide, Fluent Inc., Centerra Resource Park, 10 Cavendish Court, Lebanon, NH 03766, USA, 2003. 13. White F.M., Fluid Mechanics, McGraw-Hill Book Co. 2nd Ed., 1988. 14. NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP) version 7.0, National Institute of Standards and Technology, Boulder, CO 80305-3328, USA. 15. Fluent Inc., GAMBIT Users Guide, Fluent Inc., Lebanon, 2002. 16. Gimbun, J., at all, The influence of temperature and inlet velocity on cyclone pressure drop; a CFD study Chemical Engineering and Processing 44 7 12, 2005. 17. Aksoy A, nal R. Effects of gas pressure and protrusion length of melt delivery tube on powder size and powder morphology of nitrogen gas atomized tin powders Powder Metall, 49(4): 349354, 2006. 18. Unal R. The influence of the pressure formation at the tip of the melt delivery tube on tin powder size and gas/ melt ratio in gas atomization method Journal of Materials Processing Technology, 180: 291-295, 2006. 19. Gleen M., nal R., Aydn ., Gaz atomizasyonu nozulunun hesaplamal akkanlar dinamii (CFD) ile nmerik modellenmesi, 6th International Powder Metallurgy Conference, 2011
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Hesaplamal Akkanlar Dinamii (CFD) Yntemi ile Gaz Atomizasyon Nozul Geometrisinin yiletirilmesi
zer Aydn and Rahmi nal Dumlupinar University, Engineering Faculty, Mechanical Eng. Dept., 43100 Kutahya-Turkey ozaydin@dpu.edu.tr, runal@dpu.edu.tr ZET alma kapsamnda Fluent program kullanlarak CFD yaklam ile metal tozu retiminde kullanlan gaz atomizasyon nozulunun teorik modellemesi yaplmtr. ncelikle, TBTAK 105M033 nolu projede gelitirilen ve toz retiminde kullanlan nozulun deneysel verileri ile modellemenin doruluu tespit edilmeye allmtr. Deneysel verilerde nozul u basnc daha az olmakla birlikte CFD sonular ile arasndaki fark %11-15 arasnda deimektedir. CFD ile modellenen nozulda elde edilen veriler ile deneysel verilerin karlatrlmas sonucunda CFD yaklamnn nozul tasarm iyiletirilmesinde kullanlabilecei ortaya konmutur. Daha sonra nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri deitirilerek nozul veriminin daha yksek olabilecei en uygun tasarm bulunmaya allmtr. Keywords: Gaz atomizasyonu, nozul tasarm, CFD ABSTRACT In this study, gas atomisation nozzle for metal powder production was modelled with a CFD approach by using Fluent programm. First of all, the powder production data of the nozzle designed and used for metal powder production in the project of TUBTAK with the number of 105M033 was compared with the CFD modelling data to confirm the theoretical modell. CFD modell was improved by changing the modelling parameters. The difference between the experimental data and the CFD modell data for the nozzle melt tip base pressure varies about 11-15%. With comparison of the experimental data and the theoretical data obtained from the CFD study of the nozzle it was concluded that this CFD modell can be used for the design of the nozzle. Then, the geometry and the nozzle throat gap were changed and the effect of these parameters were determined to find out the best efficient nozzle design parameters. Key Words: Gas Atomization, Nozzle Design, CFD. 1. GR Metal tozu retimi iin farkl yntemler kullanlmaktadr. Bu yntemlerden en geni ve ticari olarak kullanma sahip olan atomizasyon yntemidir. Atomizasyon ile retilmi tozlar dier retim yntemleri (mekanik yntemler, elektroliz, kimyasal yntemler) ile elde edilemeyecek zelliklere ve avantajlara sahiptir. Atomizasyon, sv metal demetinin basnl akkanlar ile veya mekanik olarak paralanmasyla oluan damlacklarn katlama davran gstererek metal tozu haline gelmesidir. Basnl akkan olarak gazn kullanld atomizasyon trne gaz atomizasyonu, suyun kullanld atomizasyon trne su atomizasyonu denir. Gaz atomizasyonu sistemleri genel olarak serbest dmeli ve yakndan elemeli olmak zere ikiye ayrlr. Yakndan elemeli atomizasyon sistemleri daha iyi kinetik enerji transferi salad iin serbest dme ynteminden daha stndr [1-3]. Yakndan elemeli sistemlerde daha ince boyutlarda ve daha dar dalma sahip tozlar retmek mmkndr.
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Gaz atomizasyon yntemi ok sayda atomizasyon deikenlerine sahiptir (sv metal debisi, gaz debisi, gaz basnc ve nozul geometrisi). Bu deikenlerden en nemlisi nozul geometrisidir. Nozul en basit kelime anlamyla simetri ekseni boyunca hareket eden akkann hzn artrrken basncn dren geometrik yapya verilen isimdir. Gaz atomizasyonunda kullanlan nozullar farkl geometrilere sahiptirler. Genel olarak kullanlan nozullar, sonik (daralan) veya spersonik (daralan-genileyen) geometriye sahiptirler. Atomizasyon ileminde nozul, gazn kinetik enerjisini sv metale aktarr. Gazn hz, basnc, scakl ve younluu gibi zellikleri nozulun yapsna, tasarmna ve verimliliine baldr. Yaplan almalar sonucu elde edilen bilgilere gre spersonik geometrili nozullar, sonik geometrili nozullara gre daha iyi gaz genleme davran gsterirler [4-7]. Bylelikle spersonik nozullarda daha ince boyutta toz retimi gerekletirilir. Yksek verimli nozullar mmkn olduu kadar dk atomizasyon basnlarnda daha kk apta toz retimine imkan salarlar. Yakndan elemeli sistem ile toz retimi fiziksel olarak olduka karmak bir ilemdir. Paralanma mekanizmasnn karmaklndan dolay bu ilem bugne kadar tam olarak anlalm deildir. Bu nedenle, toz retim kabiliyetinin gelitirilmi nozul tasarm ile iyiletirilme konusunda byk bir potansiyel vardr ve gnmzde almalar bu ynde devam etmektedir [8-11]. Bu alma kapsamnda Fluent program kullanlarak CFD yaklam ile nozulun teorik modellemesi yaplmtr. ncelikle daha nce blmmz laboratuarnda gerekletirilen toz retim almalarnda kullanlan nozulun deneysel verileri ile modellemenin doruluu tespit edilmeye allmtr. CFD modelinin deneysel verilere yaklam en iyi olacak ekilde model zerinde eitli parametrelerin etkileri incelenmitir. Daha sonra nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri deitirilerek nozul veriminin daha yksek olabilecei en uygun tasarm bulunmaya allmtr. 2. YNTEM 2.1. Deneysel alma Atomizasyon ileminin kararl bir ekilde gerekleebilmesi iin nozul ierisine yerletirilen sv metal ak borusu u noktasnda meydana gelen basn nemlidir ve bu basncn bilinmesi gerekir. Sv metalin atomizasyonu srasnda bu basncn lm mmkn olmadndan dolay genellikle sadece atomizasyon gaz verilerek u basn lmleri yaplr. Bu amala kurulmu dzenek ekil 1de gsterilmitir.
ekil 1. Spersonik geometrili nozulun ematik gsterimi ve metal ak borusu u basncnn lm sistemi. Burada metal ak borusunun st tarafna yerletirilen bir basn alglaycsndan (pressure transmitter) alnan sinyaller sinyal alc tarafndan mbar deerine evrilerek okunmaktadr. Farkl atomizasyon basnlarnda llen deerler kaydedilerek u basn grafikleri izilmitir. Gaz atomizasyonu ileminde ekonomiklilik nemli bir parametredir. Bu parametre retilen toz iin tketilen gazn debisini ifade eder. Yaplan deneylerde spersonik nozul iin farkl atomizasyon basnlarndaki gaz debisi deerleri llmtr. lmler SIEMENS marka Strans F C Massflo Mass 2100 tipi ktlesel debi lm cihaz ile gerekletirilmitir.
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2.2. Model Geometrisinin Oluturulmas Nozulun modellenmesi saysal akkanlar dinamii alannda (Computational Fluid Dynamics - CFD) bir paket program olan FLUENT 6.3.26 ile yaplmtr [FLUENT INC., 2003]. Nozul iki boyutlu ve eksenel simetrik olmak zere GAMBIT 2.4.6 programnda izilmitir. Model geometrisinin oluturulmasnda daha nce toz retiminde kullanlan nozul lleri esas alnmtr. ncelikle iki boyutlu, iki boyutlu eksenel simetrik ve boyutlu geometriler (yarm ve eyrek geometrilerde dahil) oluturulmutur. ki boyutlu eksenel simetrik geometri zm hassasiyeti asndan bakldnda dierlerine gre daha avantajldr. nk dier geometrilere gre grid saysnn azl zaman tasarrufu salayacaktr. Ayrca dier geometrilere gre alan bana den daha fazla grid saysna ulalmasna olanak salamaktadr. Bylece zmn grid saysndan bamsz olduu optimum grid saysnn tespit edilmesi bu geometrik yap ile daha uygun tespit edilmi olacaktr. ekil 2de iki boyutlu eksenel simetrik geometri ve snr blgeleri gsterilmitir.
ekil 2. CFD Model geometrisi ve snr blgeleri. 2.2.1. Model Geometrisinde A Yapsnn Oluturulmas (Meshleme) Model geometrisinde saysal zme olanak veren a yapsnn oluturulmas (meshleme) aamasnda farkl mesh saylar oluturulmutur. Burada ama optimum mesh saysn tespit etmektir. Yani saysal zmn belli bir mesh saysndan sonra deimeyecei ispatlanmaldr. Bu amala farkl mesh yaplar oluturulmutur. Farkl mesh yaplar ile yaplan zmlerde nozul u basncnn deneysel deerlere olan yaknlna baklmtr. Geometride mesh yaplrken dikkat edilecek dier bir hususta geometrinin en dar blgesi olan nozul blgesinin meshlenmesidir. Bu alanda yaplacak yetersiz meshleme zmn hassasiyetini ok etkileyecektir. Ayrca yine zmn hassasiyetini etkileyecek dier bir noktada cidarlarn meshlenmesidir. Bu nedenle cidarlara yakn blgeler daha sk meshlenmelidir. Sk meshlenmesi iyi olacak dier bir blge ise akn olduu blgedir. Gelime raporunda da belirtildii gibi 344196 mesh sayl bir zmn deneysel sonulara yakn olduu belirtilmitir. Fakat bu mesh saysnda yksek basnlarda (17, 22 ve 27 bar) elde edilen zmler deneysel deerlerle rtmemektedir. Bu nedenle 2 090 381 mesh saysna kadar klmtr (ekil 3). Ayrca nozul cidarlar ve burun blgesi cidarlar daha da sk meshlenmitir (ekil 4).
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ekil 4. Kritik blgelerdeki ve cidarlardaki mesh yaplar 2.2.2. Saysal zm Snr artlar : Giri blgesi pressure inlet snr art olarak tanmlanmtr. Buradan azot gaz girmektedir. Deneysel verilerle kyaslanmak zere deneylerdeki farkl giri basn deerleri iin (10, 13, 17, 22 ve 27 bar) model almalarnn da ayn basn deerleri ile yaplmas gerekecektir. Bu yzden FLUENT programnda giri art olarak bu basn deerleri tanmlanmtr. nce 10 bar basn deerinde almaya balanlmtr. Gaz girii iin Pressure inlet snr art seilerek gauge total pressure 10 bar (106 Pa), turbulent viscosity ratio ve intensity 10 olarak tanmlanmtr. k iin pressure outlet snr art seilmitir. Deer olarak bu blgeler atmosfere ald iin atmosfer basnc (101.325 Pa) girilmitir. k iin dier deerler programdaki default deerler kullanlmtr. Orta eksen izgisi eksen olarak tanmlanmtr. Bu snr blgesi dndaki tm blgeler cidar olarak tanmlanmtr. Bu blgeler iin FLUENT programnda scaklk art olarak 300 K alnmtr. Seilen Modeller: eilen tm modellerde almamza yakn uluslararas makalelerdeki seilen modeller gz nnde bulundurulmutur. Bu aamada programn kullanm kitaplarndan problemimizle ilgili rnekler ve seilen modeller incelenmitir. Bu incelemelerin nda problemimize uygun modellerin seilmesine zen gsterilerek aada belirtilen modeller seilmitir. Oluturulan geometri iin programda 2D eksenel simetrik zm (2D Axisymmetric) seilmelidir. Programn zc tipi seiminde seilenler ise pressure based, implicit yaklam ve steady (kararl) zmdr. Akkan olarak azot gaz seilmi ve ideal gaz olarak tanmlanmtr. Viskozite panelinde ise sutherland law tanmlanmtr. Ayrca ak modelleri iinde programn iindeki mevcut ak modellerinden k epsilon modeli seilmitir. zme Balama: Bu aamada programn kullanc kitabndan olduka yararlanlmtr. Yksek basnl almalarda zme balamada nerilen yollarn kullanlmas nem arz etmektedir. Aksi takdirde zme ulalamamaktadr. Bunun iin zellikle 100 iterasyonda kararl bir yaknsama salanmas iin enerji denklemleri seilmemitir. Balang deeri iin hz deeri programn hesaplad deerden daha dk girilmitir. Ayrca rahatlatma faktrleride (under-relaxation factor) basn iin 0.4, momentum iin 0.3, younluk iin 0.3, enerji iin 0.9 seilmitir ve dierleri default deerleri olarak ayn kalmtr. Yaknsama da kararl bir grnt salandktan sonra (100-200 iterasyon sonra) enerji denklemi almtr ve basn iin rahatlatma faktr 0.7 olarak deitirilmitir. zm iin ncelikle 1.dereceden denklemler (first order upwind) seilmitir ve yaknsama kriteri olarak ise enerji denkleminin 10-6 hata oran esas alnmtr. Ayrca giri ve k arasndaki ktlesel debiler arasndaki farknda 10-6 orannda bir farka ulamas yaknsama kriteri olarak gz nne alnmtr. Bu aamadan sonra ise second order denklemleri seilerek eski zm zerinden tekrar iterasyon yaptrlarak son zm salanmtr.
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2.2.3. Saysal zm Teorisi Fluent program seilen denklemlerin zmnde sonlu hacim yaklamn kullanr. CFD gibi byle nmerik modelleme teknikleri ak ve s transferi problemlerini simule etmek iin gl bir aratr. Ktlenin korunumu veya sreklilik denklemi, momentumun korunumu veya NavierStokes transport denklemi ve enerjinin korunumu denklemi nmerik olarak zlebilir. Ktlenin korunumu ya da sreklilik denklemi aada gibi yazlabilir [FLUENT INC., 2003]. 1 Burada gaz younluu, v gaz hzn ifade eder. Sm kaynak terimi ise ayrlm ikinci fazdan (sv damlacklarnn buharlamas nedeniyle gibi) srekli faza ilave edilen ktle ve herhangi bir kullanc tarafndan tanmlanm kaynaktr. 1 numaral denklem ktle korunum denkleminin genel formudur ve sktrlabilir aklarda olduu kadar sktrlamaz aklarda da geerlidir. ki boyutlu eksenel simetrik geometriler iin sreklilik denklemi; 2 Burada x eksenel koordinat, r radyal koordinat, vx eksenel hz, and vr radyal hzdr. Bir atalet (ivmelenme olmakszn) referans erevesinde momentumun korunumu; 3 Burada p statik basn, gerilim tens (aada tanmland), ve ve srasyla yerekimi kuvveti ve d kuvvettir (ayrk faz ile etkileimden ykselme gibi). daima poroz ortam ve kullanc tanml kaynaklar gibi baka model baml kaynak terimler ierir. Gerilim tensr aadaki gibi ifade edilir. 4 Burada molekler viskozite, I birim tensr, ve sa taraftaki ikinci terim hacim genileme etkisidir.
ki boyutlu eksenel simetrik geometriler iin eksenel ve radyal momentum korunum denklemleri aada verilmitir.
ve
Burada; 7 ve vz swirl hzdr.
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Sktrlabilirlik etkilerine ile yksek hzlardaki gaz aklarnda ve/veya byk basn deiimlerinde karlalr. Ak hz gazn ses hzna yaklat ya da at zaman veya sistemde basn deiimi (p=p) byk olduu zaman basnla gaz younluunun deiimi ak hz basnc ve scakl zerinde nemli bir etkiye sahiptir. Sktrlabilir aklar iin, ideal gaz kanunu aadaki formda yazlr; 8 Burada pop iletme basnc (operating conditions panelinde tanmlanr), p iletme basncna gre bal lokal statik basn, R niversal gaz sabiti, ve Mw molekler arlktr. Scaklk T enerjinin korunum denkleminden hesaplanabilecektir. Enerjinin korunum denklemin aadaki gibi yazlabilir; 9 Burada E toplam enerji, H entalpi ve s aks vektr. Sktrlabilir aklar tipik olarak akn toplam basn p0, toplam scaklk T0 tarafnca karakterize edilir. deal gaz iin bu byklkler aada verildii gibi statik basn ve scaklkla ilikilendirilebilir:
10
Cp iin; 11
12 Hz (Mach says) isentropik artlar altnda deiirken ak iindeki statik basn ve scakln deiimini bu bantlar tanmlar. Sktrlabilir aklar Mach saysnn deeri ile karakterize edilebilir : 13 Burada, c gaz iindeki ses hz: 14 ve zgl slarn orandr. (cp/cv).
Sutherland viskozite kanunu iki ya da katsayl kullanmyla belirtilir. ki katsayl Sutherland kanunu; 15 Burada viskozite (kg/m-s), T statik scaklk (K), ve C1 ve C2 katsaylardr. Scaklk ve basncn orta deerlerinde hava iin C1 = 1.458x10-6 kg/msK1/2, and C2 = 110.4 K.
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katsayl Sutherland kanunu; 16 Burada viskozite (kg/ms), T statik scaklk (K), 0 bir referans deer (kg/ms), T0 bir referans scaklk (K), ve S ise gazn karakteristii olan Sutherland sabiti olarak isimlendirilen bir efektif scaklk (K). Scaklk ve basncn orta deerlerinde hava iin, 0= 1.7894x0-5 kg/ms, T0 = 273.11 K, and S = 106.67 K [FLUENT 6.1.22, Users Guide, 2003]. 3. Sonular ve Deerlendirme 3.1 CFD Sonular ile deneysel verilerin karlatrlmas Bir problemin CFD yardmyla zlmesinde seilen modellerin uygunluunun tespiti iin CFD sonularnn deneysel verilerle kyaslanmas gerekir. CFD sonularnn deneysel verilere yaknlk derecesi ve deneysel verilerle ayn karakteristik zelliklerine sahip olup olmad incelenir. Gaz atomizasyonu almalarnda teorik zm ile deneysel almann karlatrlmas nozul ucunda yaplan u basn lmleriyle yaplabilmektedir. nk nozul ucunda meydana gelen u basn gaz atomizasyonunda olduka nemli bir etkiye sahiptir. CFD zmde nozul u basnc; nozulun u blgesinden balayarak aralklar 1 mm olan lm izgisi zerindeki deerlerin ortalamas alnarak elde edilmitir. Deneysel lmde boru i ap 3mm olduundan dolay her lm izgisi radyal ynde 1.5 mm uzunluuna sahip olup bu uzunluk zerinde 10 lm noktas seilmitir. Bu adet lm izgisi zerinde elde edilen deerlerin ortalamas deneysel verilerle kyaslama iin nozul u basn deeri olarak alnmtr. ekil 5de nozul u basncnn CFD ve deneysel kyaslanmas verilmitir. Giri basncna bal olarak nozul u basncndaki deiim deneysel verilerle ayn karakteristik zellii tamaktadr. CFD ile deneysel verilere bakldnda nozul gaz basnlar arasndaki fark tm basnlarda ayndr. Deneysel verilerde nozul u basnc daha az olmakla birlikte CFD sonular ile arasndaki fark %11-15 arasnda deimektedir. Espina ve Piomelli yaptklar almalarnda saysal zmlemeleri ile deneysel verilere genellikle %10-20 arasnda yaknlk elde etmilerdir [Espina 1998]. Bu nedenle bu simlasyonlar deneysel verilerle Espina ve Piomelli tarafndan yaplan daha nceki almalardan daha iyi rtmektedir. Bu sonu nozul u basncnn belirlenmesinde CFD modelin kullanlabileceini gstermektedir [12]. ekil 6 da gaz ktlesel debisinin CFD ve deneysel veriler ile kyaslamas verilmitir. Deneysel veriler ile CFD sonular arasndaki fark hemen hemen sabit olup %30 civarndadr. Bu fark nozulun yzey zelliklerinden ve gerek boaz kesit alan ile nozulun tasarmndaki boaz kesit alan arasndaki farktan kaynaklanm olabilir. Yine bu konuda Anderson ve Terpstra [Anderson 2002] yaptklar almada teorik debi ile deneysel debi arasnda basncn artmasyla birlikte giderek artan bir fark tespit etmiler ve teorik debi deerleri ile deneysel debi deerleri arasnda ok byk fark bulmulardr. Anderson ve Terpstra bu farkn nedenini aklayamamlardr. Bu almada elde edilen deerler arasnda hemen hemen sabit bir farkn olmas yaplan hesaplamann deneysel veriler ile rttn gstermektedir. Ayrca CFD almasnda gaz scakl sabit tutulmutur. Deneysel almada ak esnasndaki gaz scakl zamanla azalmaktadr. Bu durum nozulan geen gazn gerek ktlesel debisini de etkileyebilir.
ekil 5. Nozul u basncnn CFD ve deneysel veriler ile karlatrlmas
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ekil 6. Gaz ktlesel debisinin CFD ve deneysel veriler ile karlatrlmas. 3.2 Nozul Tasarmn yiletirme almalar nceki blmde akland zere CFD modelinin deneysel veriler ile uyum ierisinde olduunun tespit edilmesinden sonra mevcut nozul tasarmnn iyiletirilmesi amacyla farkl artlarda nozul davran incelenmitir. Bu amala yaplan almalarda nemli tasarm kriteri olarak nozul u basnc, gaz hz, gaz debisi ve gazn enerjisi esas alnmtr. 3.2.1. Nozul Geometrisinin Etkisi Burada mevcut nozulun as ve boaz k alan deitirilerek nozul davranndaki deiim tespit edilmitir. Elde edilen deerler Tablo 1de verilmitir. Tablo 1. Farkl nozul alar ve darboaz aklnda gaz hz ve u basn deerleri. Nozul as 10 10 10 13 13 13 16 16 16 7 Darboaz akl (mm) 0,2 0,3 0,4 0,2 0,3 0,4 0,2 0,3 0,4 0,4 alma Basnc (bar) 13 13 13 13 13 13 13 13 13 13 Gaz Hz (m/s) 616,3 598,7 588,0 633,4 622,1 612,7 643,6 631,7 620,8 600,9 Mach Says 2,78 2,59 2,48 2,99 2,85 2,74 3,13 2,96 2,83 2,61 Gaz debisi (kg/dak) 2,099 2,821 3,533 2,259 2,942 3,668 2,435 3,172 3,876 3,441 U Basnc (bar) 0,896 0,901 0,988 0,939 0,961 1,178 1,078 1,159 1,372 1,037 Dzeltilmi U basn (bar) 0,784 0,788 0,865 0,822 0,841 1,031 0,943 1,014 1,201 0,907
ekil 7de nozul boaz aklna ve farkl nozul alarna gre gaz hznn deiimi 1.3 MPa atomizasyon basn deeri iin grafik halinde verilmitir. En yksek gaz hz 16 al ve 0,2 mm darbogaz aklnda elde edilmitir. Bu artlarda nozul ucunda az da olsa negatif basn oluumu gzlenmitir. Fakat 16 al nozulda meydana gelen u basn deerleri 0,3 ve 0,4 mm darboaz aklnda pozitif
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kmtr. Dolaysyla bu nozullarda metalin ak mmkn olmayacaktr. Bu nedenle bu nozullarn 0,3 ve 0,4 mm darboaz aklnda kullanm mmkn olamayacaktr.
ekil 7. Nozul boaz aklna gre gaz hznn 1.3 MPa basnta farkl nozul alarna gre deiimi. ekil 8de 1.3 MPa gaz basncnda farkl nozul boaz akl ve farkl nozul asna gre Mach saysndaki deiim verilmitir. 10, 13, 16 derece al nozullarda Mach says srasyla 2,78, 2,99 ve 3,13 olarak tespit edilmitir. 16 derece al nozulda en yksek deer elde edilmitir. ekil 9da ayn artlarda gaz debisindeki deiim verilmitir. Nozul boaz aklnda art olduu zaman hzdaki deiim ok fazla olmamtr. 16 derece al nozulda 02, 03 ve 0,4 mm darboaz aklnda srasyla gaz hzlar 643.6, 630.7 ve 620.8 m/s iken gaz debileri 2.435, 3.172 ve 3.876 kg/dak olarak hesaplanmtr. Bu karlatrma gstermektedir ki boaz aklnn art ile gaz hznda ok nemli bir azalma olmaz iken gaz debisi daha fazla miktarda art gstermektedir. rnein 16 derece al nozulda 0,2 mm darboaz aklk deeri 0,4 mmye karlrsa gaz hz yaklak %4 azalrken gaz debisi %59 orannda artmtr. Bu karlatrma ile aka grlmektedir ki nozul geometrisine gre boaz aklk deeri olduka kritik bir neme sahiptir.
ekil 8. Darboaz aklk deerine gre Mach saysndaki deiim (nozul alar 10, 13, 16).
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ekil 9. Darboaz aklk deerine gre gaz debisindeki deiim (nozul alar 10, 13, 16) Gaz atomizasyon ilemi gaz enerjisinin sv metale aktarlmas sonucu sv metalin ok kk damlacklar halinde paralanmas olaydr. Paralanma mekanizmas Weber saysna (we) gre deiiklik gstermektedir. ekil 10da We saysna gre sv metalin paralanmas farkl ekilde meydana gelmektedir.
ekil 9. Weber saysna gre paralanma mekanizmalar Weber says eitlik 17de verilmitir. 17 Burada, dpart sv metal demeti ap, ve sv metalin younluu ve yzey gerilmesi deeridir, urel ise gazn sv metale arpt andaki hzdr. Buradan grld gibi hzn karesi alndndan gaz hz ok byk bir neme sahiptir. Dolaysyla ayn artlarda en yksek gaz hzna ulaan nozul tasarm daha baarl sonu verecektir. Bylece nozul verimlilii artacaktr. Bu nedenlerle nozul tasarmnda boaz aklnn fazla olmas durumunda gaz kullanm artacaktr, fakat toz boyutunda nemli bir klme gzlenmeyecektir. Tablo 1de verilen nozul deerleri yukarda yaplan deerlendirmeler nda incelendiinde en iyi artlar 10 dereceli ve 0,2 mm akla sahip nozul salayabilecektir. nk hem nozul ucunda iyi bir emme basnc olumakta hem de atomizasyon gaz 613 m/s ile olduka makul bir debide akmaktadr.
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4. SONULAR Proje kapsamnda Fluent program kullanlarak CFD yaklam ile nozulun teorik modellemesi yaplmtr. ncelikle daha nce blmmz laboratuarnda gerekletirilen toz retim almalarnda kullanlan nozulun deneysel verileri ile modellemenin doruluu tespit edilmeye allmtr. CFD modelinin deneysel verilere yaklam en iyi olacak ekilde model zerinde eitli parametrelerin etkileri incelenmitir. Daha sonra nozul tasarmnda nemli olan geometri ve gaz k alan deikenleri deitirilerek nozul veriminin daha yksek olabilecei en uygun tasarm bulunmaya allmtr. Yaplan deerlendirmeler sonucunda elde edilen sonular aada maddeler halinde verilmitir; Deneysel verilerde nozul u basnc daha az olmakla birlikte CFD sonular ile arasndaki fark %1115 arasnda deimektedir. Elde edilen teorik ve deneysel deerler arasnda hemen hemen sabit bir farkn olmas yaplan hesaplamann deneysel veriler ile rttn gstermektedir. Nozul boaz aklnn artmas ile nozul hznda ok nemli bir deiiklik meydana gelmemektedir. Ancak gaz debisi ok yksek oranda artmaktadr. 16 dereceli eski tasarmda 0,2 mm boaz aklk deeri 0,4 mmye karlrsa gaz hz yaklak %4 azalrken gaz debisi %59 orannda artmtr. Bu almada elde edilen veriler mevcut nozul tasarmlarnn CFD ile iyiletirilebileceini ortaya koymutur.. Teekkr Bu alma TUBITAK tarafndan 107M189 nolu proje ile desteklenmitir. KAYNAKLAR 1. A.M. Mullis, N.J. Adkins et al., High frame rate analysis of the spray cone geometry during closecoupled gas atomization, PM 2007, 2. J. Mller, Flow field Simulation of a High Pressure Gas Atomization using CFD, 3. I.E. Anderson, R.S. Figliola & H. Morton, Mater. Sci. Eng. A, 1991, vol. 148, pp. 101-114. 4. I.E. Anderson & R.L. Terpstra, Mater. Sci. Eng. A, 2002, vol. 326, pp. 101-109. 5. nal R., Aksoy A., Effects of Gas Pressure and Protrusion Length of Melt Delivery Tube on Powder Size and Powder Morphology of Nitrogen Gas Atomised Tin Powders, Powder Metallurgy, Vol.49, No.4, pp. 349-354, 2006. 6. nal R., Improvements to a close-coupled gas atomisation nozzle for fine powder production, Powder Metallurgy, Vol.50, No.1, pp 66-71 , 2007. 7. nal R., The Influence of The Pressure Formation at The Tip of The Melt Delivery Tube On Tin Powder Size And Gas/Melt Ratio In Gas Atomization Method, Journal of Materials Processing Technology, Vol.180, No.1-3, pp. 291-195, 2006. 8. NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP) version 7.0, National Institute of Standards and Technology, Boulder, CO 80305-3328, USA. 9. N. Zeoli, S. Gu, Numerical modelling of droplet break-up for gas atomisation, Computational Materials Science 38 (2006) 282292. 10. P.I. Espina and U. Piomelli, numercal smulaton of the gas flow n gas-metal atomzers, Proceedings of FEDSM98, 1998 ASME Fluids Engineering Division Summer Meeting, June 21-25, 1998, Washington, DC, USA. 11. Espina, P. I., and Piomelli, U., A Validation of the NPARC Code in Supersonic Base Flows, AIAA Paper, 97-0032, 1997. 12. Aydn . and nal R., Experimental and numerical modeling of the gas atomization nozzle for gas flow behavior , Computers and Fluids, Volume 42, Issue 1, March 2011, Pages 37-43.(2011).
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AA 2014 ALAIMININ MKROYAPISAL KARAKTERZASYONU VE AINMA DAVRANIINA ETKS

Sedat TOMRUK*, Hakan GKMEE** ve Blent BOSTAN*** Milli Eitim Bakanl, Mehmet Rfat Breki lkretim Okulu, Mamak, 06320, Ankara, sedat tomruk@yahoo.com ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, hakangokmese@gazi.edu.tr *** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, bbostan@gazi.edu.tr
*
ZET Bu almada ticari AA 2014 alminyum alamna ait, ortalama toz boyutu 95 m olan alam tozlar kullanlmtr. Bu tozlardan 650 MPa presleme basncnda, tek ynl souk pres de anma numuneleri retilmitir. Preslenen numuneler 550 C de, 224 saat aralnda sl ileme tabi tutulmutur. Daha sonra numunelerin sertlik deerleri llmtr. Ayrca 600 C sinterleme scaklnda 268 gn sl ilem yaplarak numunelerin anma davranlar incelenmitir. Isl ilem sresinin artmas ile birlikte sertlik deerlerinde de art olduu belirlenmitir. Anma kayma mesafesine bal olarak, 400 mnin zerinde en az anma kayb 6 gn sl ilem grm numunelerde gereklemitir. Anahtar Kelimeler: AA 2014, Karakterizasyon, Anma
MICROSTRUCTURAL CHARACTERIZATION OF AA 2014 ALLOY AND EFFECT ON WEAR BEHAVIOR

ABSTRACT In this study, It has been used alloy powders belonging to AA 2014 commercial alloy which avarege powder dimensions are 95mm. These powders have been pressed at 650 Mpa pressure and has been produced wear experiment samples. Pressed samples has been carry out to heat treatment at 550C between 2 and 24 hours. Later, Hardness values of the samples have been measured. It has been investigated hardness value as dependent on increasing of heat treatment time. In addition, It has been investigated wear behaviors of samples which to process heat treatment 2-6-8 day at 600C. It has been confirmed that hardness value has also increaesed after inreasing heat treatment time Depending on wear sliding distance, minimum wear lose has evuntuate samples that has been applied 6 day heat treatment. Key Words: AA 2014, characterization, wear 1. GR Malzemelerin mekanik, kimyasal ve fiziksel zelliklerini iyiletirmede; kimyasal modifikasyon, sl ilemler, mekanik ve termomekanik ilemler kullanlmaktadr. Gelien teknoloji ile ihtiyalarda farkllamtr. Toz Metalurjisi (TM) gibi yeni retim tekniklerinin kullanmlar yaygnlamaya balamtr. TM yntemiyle retilmi malzemelerin yksek kullanm zelliklerini geleneksel metotlarla retmek neredeyse imknszdr [1]. Toz Metalrjisi metal tozu ve ondan ktlesel gereler ve ekillendirilmi paralar retme teknoloji ve sanatdr [2]. TM paralarn en yaygn olarak kullanld alan otomotiv sanayidir. Otomatik vites paralar, hareket dilileri, yalama pompa dilileri, debriyaj bask plakalar yllardr T/M teknolojisi ile retilmektedir [3]. Toz metalurjisi yntemi son
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yllarda daha nemli bir hale gelmitir [4]. Son yirmi ylda yksek performansl toz metal alminyum alamlar (Al alamlar) iin talep giderek artmtr [5]. Alminyum alamlarnn toz metalurjisi ticari olarak birka alam zerine younlamtr. Kartrma esnasndaki potansiyel risklere kar, reticiler tarafndan nceden kartrlm, baz yalayclar katlm alminyum alamlar retilmektedir. Alminyum alamlar, nispeten dk basnlarda (400480 MPa) preslenir. Alminyum esasl ticari alamlar yksek sktrlabilirlik gsterir ve yaklak 350 MPa basn kullanlarak % 9095 arasnda teorik younlua ulalabilir [6] Al alamlarnn anma oran hava ortamnda yksek olup, vakum ortamnda ise dktr. Al alamlar korozyon ortamlarnda kullanlr ve Si ierenlerinin anma direnci dierlerinden fazladr [7,8]. Endstriyel uygulamalarda anmaya dayankl malzemeler yaygn kullanm alanna sahip olup bu malzemelerin hafif olmalar ve evre artlarndan daha az etkilenmeleri beklenmektedir [9]. Makine paralarnn alma mrleri, anmaya kar direnci yksek olan malzemelerin retilebilmesiyle arttrlabilmektedir. Makine hasarlarnn analizi, paralarn bozulmalarnn % 75 inin srtnen yzeylerin anmas sonucu olduunu gstermektedir. Yzeylerin mrlerinin uzamas iin, malzemelerin anmaya kar direncinin arttrlmas gerekmektedir. Anma zorlamasnn yksek olduu ve yalamann yeterli olmad durumlarda anmaya kar direnli ve srtnme katsays dk malzeme seilir [10]. Bu amala AA 2014 malzemesinin mikro yapsal karakterizasyonu ve anma davranlarnn belirlenmesi hususunda almalar yrtlmtr. 2. DENEYSEL ALIMALAR Bu almada Gazi niversitesi Teknik Eitim Fakltesi Dkm A.B.D.de bulunan gaz atomizasyon nitesinde retilmi olan, ortalama toz boyutu 95 m olan tozlar kullanlmtr. Kullanlan tozlarn boyut analizleri Gazi niversitesi Mimarlk Mhendislik Fakltesi Makine Mhendislii Blmndeki Malvern Mastersizer E Version 1,2 b, boyut analizi cihaznda yaplmtr. Taramal Elektron Mikroskobu (SEM) grntleri ile de, boyut analizi cihaznda karlalabilecek boyutsal sorunlarn olup olmad aratrlmtr. retilen tozun kimyasal bileimi izelge 1de verilmitir.
izelge 1. AA 2014 Alminyum alamnn kimyasal bileimi Toz boyutu ortalama 95m olan karmdan 1gr toz kullanlarak 10 mm apnda tek ynl pres altnda farkl presleme basnlar denenerek uygun presleme basncna ulalmtr. Presleme sonras deney numunelerinin sl ilemleri atmosfer kontroll frnda 550C de 2, 4, 8, 12 ve 24 saat olmak zere farkl srelerde gerekletirilmitir. Tane yaps ve gzenek oluumuna sl ilem sresinin etkileri tespit edilmeye allmtr. Isl ilem scakl ve sresi temel alnarak, sl ilem ncesi ve sonrasndaki younluklar hesaplanm ve uygun sl ilem sresi tespit edilmeye allmtr. Numunelerin metalografik olarak incelenebilmeleri iin, Optik mikroskop ve SEM (Joel JSM - 6060 LV) cihazlarndan yararlanlmtr. Yaplan almalar dorultusunda sertlik sonularnn sl ilem scakl ve sresine bal olarak nasl deitii hususunda sertlik zerine etkileri incelenmitir. Sertlik lmleri SHIMADZU marka mikro sertlik cihaznda yaplmtr ve kullanlan yk ise HV 0,1kg olarak belirlenmitir. Deney numunelerine uygulanan presleme ve sl ilemler sonras, Karabk niversitesi Teknik Eitim Fakltesi Dkm Eitimi Anabilim Dalnda bulunan anma cihaz kullanlarak kuru srtnme anma davranlar pin-on-disk tipi anma cihaznda yaplmtr. Anma deneyleri kuru ortamda yaplmtr. Isl ilem uygulanm numunelere 15 N yk uygulanmtr. Bu ykler altnda numuneler 400, 800 ve 1200 m kayma mesafelerinde srtnme ve arlka kayplar hesaplanarak sonulara ulalmtr. Anma yzeylerine ait grntleme ilemleri 1200 m ardndan yaplmtr. 600C scaklkta, 2, 6, 8 gn uygulanan sl ilemlerin ardndan elde edilen anma kayplar grafiklere dntrlmtr. Anma kayplar ve kayma mesafesi ilikileri deneyler sonras irdelenmitir. 3. ARATIRMA BULGULARI VE DEERLENDRLMES AA 2014 malzemesinin presleme basncnn belirlenmesi amal farkl presleme basnlar test edilmitir. Younlukpresleme basnc ilikisi asndan optimum deer olarak 650Mpa bulunmutur. Tm dier deneyler bu presleme basncnda retilen numuneler kullanlarak gerekletirilmitir.
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izelge 2. Isl ilem ncesi ve sonras younluk deiimleri Numune Kodu Numune 1 Numune 2 Numune 3 Numune 4 Numune 5 Isl lem Scakl (C) 550 550 550 550 550 Isl ilem Sresi (saat) 2h 4h 8h 12h 24h Isl lem ncesi Younluk (g/cm3) 2,77 2,76 2,75 2,74 2,73 Isl lem Sonras Younluk (g/cm3) 2,62 2,62 2,66 2,7 2,69
izelge 2de sl ilem ncesindeki ve sonrasndaki younluklar gsterilmitir. izelge 2 ve ekil 1de gzlemlendii gibi 550 C de farkl srelerde sl ilem uygulanan numunelerin, sl ilem sresinin art ile younluklarnda da belli bir art tespit edilmitir.
ekil 1. 550C de sl ilem sonras younluk deiimi 12 saat sl ilem sonrasnda younluk artnda nemli bir deiim meydana gelmemitir. Toz metalrjisi yntemleri ile tam youn para retimi ikincil ilemler veya sv faz sinterleme ile mmkndr. Bu balamda kullanm olduumuz AA 2014 malzemesinin teorik younluunun 2,75 g/cm3 civarnda olduunu gz nne aldmzda younluun % 98 civarna kadar kt grlmektedir. Bu da ikincil ilemler olmakszn younluk asndan olduka yksek bir deerdir. Isl ilem scakl ve sresi temel alnarak, sl ilem ncesi ve sonrasndaki younluklar hesaplanm ve uygun sl ilem sresi tespit edilmeye allmtr.
ekil 2. 550C de farkl srelerde sl ilem yaplm numunelerin optik mikroskop grntleri; a) 4 saat, b) 8 saat, c) 12 saat, d) 24 saat
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Isl ilem ile birlikte numunelerde oluan faz deiimlerinin kontrol iin (2 saatten 24 saate kadar olan srelerdeki) optik mikroskop grntleri incelenmitir. nceleme sonrasnda 4 saat sl ilem uygulanan numunelerde gzeneklerin tane snrlarnn bulunduu nadiren de tane ilerinde bulunduu gzlemlenmitir (ekil 2a). Srenin artmasyla birlikte tane snrlar ve ierisindeki gzenekliliklerin birlemeye balad ve genel itibariyle tane snrlarnda younlat gzlemlenmitir (ekil 2d). ekil 2d de grld gibi sl ilem sresinin 24 saat gibi yksek srelere kmasyla birlikte daha ncesinde yaplan dk srelerdeki sl ilem uygulamalarna gre gzeneklerin tamam tane snrlarna doru yneldii ve resim incelendiinde sinterleme teorisine gre sl ilemin bu sre iin yeterli olduu sylenebilir. Farkl srelerde sl ilem grm numunelerin, farkl bytmelerdeki ekilmi olan SEM grntleri incelendiinde (ekil 3), artan sl ilem sresinin etkileri aka grlmektedir. Ayn etkinin daha ksa srelerde gereklemesi iin sl ilem scaklnn artnn etkili olaca sylenilebilir.
ekil 3. 550 C de farkl srelerde sl ilem grm numunelerin, farkl bytmelerdeki SEM grntleri; a) ve b) 4 saat, c) ve d) 24 saat ekil 4de 550C de 2, 4, 8, 12 ve 24 saat gibi farkl srelerde sl ilem grm numunelere ait sertlik deerleri gsterilmitir. Isl ilem sresinin artmas ile birlikte sertlikte de bir art gzlemlenmektedir. 12 saatin zerindeki sl ilem srelerinde sertlik deerinde ciddi bir deiikliin olmad grlmektedir. lk sl ilem srelerinde (2,4 saat) sertlikte bir deiim olmamtr. Bunun nedeni balangta uygulanan enerjinin tozlarda ve toplam ktlede meydana gelen toparlanma sreci gibi dnebiliriz. 4,8 ve 12 saatlerde ise sertlikteki art makro ve mikro gzeneklerin kapanmas ile izah edilebilir.
ekil 4. Farkl sl ilem srelerindeki sertlik deerleri
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ekil 5 de 600 C de 2, 6, 8 gn sl ilem uygulanm numunelerin anma kayma mesafesine bal olarak anma kayplar verilmitir. lk 400 m kayma mesafesine kadar, bu numunelerin anma kayplarnn sl ilem zamannn artmasyla daha az olduu grlebilir. Bunun muhtemel nedeni sl ilem zamannn artmasyla numunelerdeki younlamann artmas ve buna bal olarak da sertliin artmas gsterilebilir.
ekil 5. 600 C de 2, 6, 8 gn sl ilem uygulanm numunelerin anma kayma mesafesine bal olarak anma kayplar grafii Bu numunelerde 400 m kayma mesafesinden sonra en az anma oran 6 gn sl ilem uygulanm numunede olduu grlmektedir. Oysaki 400 m kayma mesafesi ncesinde en az anma oran en uzun sl ilem sresi uygulanan numunede gereklemiti. Bu numunede anma kaybnn daha az kmasna muhtemel nedenler ya kuru srtnmeden dolay numune yzeyindeki oksitlenmeye (Al2O3 filmi) bal olarak ya da Al alamlar gibi baz yumuak ve YMK yapl malzemelerde anma yk altnda iken plastik deformasyona bal olarak sertliin yzeyde blgesel olarak artmas gsterilebilir. ekil 6 da 600 C de 2, 6, 8 gn sl ilem uygulanm numunelerin 1200 m kayma mesafesi sonras anma yzeyleri srasyla verilmitir. 2 gn sl ilem uygulanm numunenin anma yzeyi incelendiinde ktle kayplarnn ok daha fazla olduu derin anma izlerinden aka grlebilir. Bu numunede ktle kayplar adhesiv anma mekanizmasna bal olduu anma izlerindeki snek yrtlmalardan anlalmaktadr.
ekil 6. 600 C de farkl srelerde sl ilem uygulanm numunenin anma yzeyi; a) 2 gn, b) 6 gn, c) 8 gn 6 gn sl ilem uygulanm numunenin anma yzeyi incelendiinde ise ktle kayplarnn ok az olduu anlalmaktadr. Anma yzeyindeki anma izleri daha dz ve ok derin olmad grlmektedir. Ayn zamanda zellikle toz metalurjisi yntemiyle retilen malzemelerde yzeye ak gzeneklerin anma esnasnda kopan ok kk paracklarn yzeye ak gzenekler tarafndan tutulmas da anma kayplarnn daha az olmasna neden olabilir. 8 gn sl ilem uygulanm numunenin anma yzeyi incelendiinde 6 gn sl ilem uygulanm numunenin anma yzeyine gre daha fazla 2 gn sl ilem uygulanm numunenin anma yzeyine gre daha az olduu grlmektedir. Isl ilem sresinin artmasna ramen anma kayplarnn yeniden artmasna neden olarak anma esnasnda kopan byk boyutlu paralarn yzeye daha derin hasar verdii dnlebilir.
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4. SONULAR Bu alma kapsamnda TM gaz atomizasyon yntemiyle retimi gerekletirilen AA 2014 malzemesine ait deney numunelerinin sl ilem scakl, sresi, sertlik ve anma deneyleri sonrasnda elde edilen sonular u ekilde zetlenebilir; Isl ilem sresinin artyla birlikte gzenek-yap etkileimi asndan 550 C deki uygun sl ilem sresi 24 saat olarak belirlenmitir. Sabit scaklkta yaplan (550 C) sl ilem sresinin artmas ile birlikte sertlik deerlerinin de nemli derecede art olduu belirlenmitir. 600 C de 2, 6, 8 gn sl ilem uygulanm numunelerin anma kayma mesafesine bal olarak anma kayplar ilk 400 m kayma mesafesine kadar sl ilem zamannn artmasyla daha az olduu tespit edilmitir. 400 mnin zerinde en az anma kayb 6 gn sl ilem grm numunelerde gereklemitir. Numunelerin anma deneylerinde sklkla karlalan scaklk artna bal oksit oluumunun, anma kayplarn etkiledii tespit edilmitir. Benzer ekilde artan anma mesafelerine bal olarak gereklemesi muhtemel olan anma kayplar mesafe arttka dorusal bir art gstermemitir. Artan sl ilem scakl ve zaman toz numunelerin gzenek miktarn etkiledii bilinen bir sonutur. Anmada bu etki mesafeye bal olarak aa kan gzeneklerin anan paracklar tutarak sanki anma miktarnda bir d varmasna bir etki yapt gzlemlenmitir. TEEKKR Bu almada kullanlan tozlarn retimi ve yaplan deneysel almalar, Gazi niversitesi Bilimsel Aratrma Projeler Birimi, 41/2010 04 nolu proje kapsamnda gerekletirilerek, desteklerinden dolay Gazi niversitesine teekkr ederiz. KAYNAKLAR 1. Aksz, S., Al4C3 Faznn Karbon ve AA2014 Tozlarndan Kat Faz Reaksiyon Teknii le Oluturulmas ve Yalanmaya Etkisi, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara,1-2, 2009. 2. Sarta, S., Toz Metalurjisi, TMMOB, Cilt:36, Say: 421, ubat, 1995. 3. Baaran, A., Toz Metal Paralara Isl ve Mekanik Yzey lemlerin Birlikte Uygulanabilirliinin Aratrlmas, Doktora Tezi, Sleyman Demirel niversitesi Fen Bilimleri Enstits, Isparta, 29-32, 2007. 4. Sonoda, T., Watazu, A., Zhu, J., Sh, W., Kamiya, A., Kato, A., Asahina, T., Deposton Of Titanium Onto Alumnum Powder Ints Self-Convectve Moton By Dc Sputterng, 3rd International Powder Metallurgy Conference, September 4-8, Turkish Powder Metallurgy Association Gazi University, Ankara, TURKEY, pp.756-759, 2002. 5. Eki A., K., ,Bircan D., A., Sonsino, C., M., Alumix 431 Tozunun (Al7xxx) Souk ve Ilk Preslenmesi zerine Bir alma, Gazi niv. Mh. Mim. Fak. Der., Cilt: 22, No: 2, 337-345, Ankara, 2007. 6. Gke, A., Yapsal Uygulamalar in Alminyum Esasl Malzemelerin Toz Metalurjisi Kullanlarak Gelitirilmesi, Yksek Lisans Tezi , Sakarya niversitesi Fen Bilimleri Enstits, Sakarya, 26-31, 2007. 7. nl, B., S., ahin, S., Akgn, S., Dkm ve T/M Yntemiyle retilmi Al2O3-SiC Takviyeli Al Kompozitlerinin Anma zelliklerinin ncelenmesi, 4th International Powder Metallurgy Conference, May 18-22, Turkish Powder Metallurgy Association Sakarya University, Sakarya, TURKEY, pp. 615-621, 2005. 8. Bostan, B., Gaz Atomizasyon Yntemi le AA 2014 Alam Tozlarnn retilmesi ve Karakterizasyonu, 5. Ulusal Toz Metalurjisi Konferans, TOBB, Ankara, 1-8, 2008. 9. Ylmaz, R., Kurt, A., O., Seramik Kaplamalarn Anma Davranlarnn ncelenmesi, 4th International Powder Metallurgy Conference, May 18-22, Turkish Powder Metallurgy Association Sakarya University, Sakarya, TURKEY, pp. 649-663, 2005. 10. Kksal, F., Al-Cu-SiC ve Al-Cu-B4C Kompozitlerin Scak Presleme Yntemi le retimi ve Anma zelliklerinin Aratrlmas, Yksek Lisans Tezi Sleyman Demirel niversitesi Fen Bilimleri Enstits, Isparta, 1-5, 2004.
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MKRO YAPIDA BOYUTLU YZEYLERN GZENEKLLK VE MKROSERTLNE RETM PARAMETRELERNN ETKS

Blent ZTRK1,2, mer Necati CORA2,3 ve Muammer KO 2,4
1
Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080, Trabzon, bozturk@ktu.edu.tr 2 NSF I/UCR Center for Precision Forming, Richmond, VA, USA 3 Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 61080, Trabzon, oncora@ktu.edu.tr 4 stanbul ehir niversitesi, stanbul, mkoc@sehir.edu.tr zet
Gzenekli metalik yzeyler, s eanjrleri, yakt hcreleri ve biyomedikal implant malzemeleri gibi alanlarda s ve ktle transferi asndan geni uygulama alanna sahiptirler. Yaplan bu almada toz presleme ynteminde sktrma scakl, sktrma basnc, toz boyutu ve sinterleme scaklnn retilen 3 boyutlu gzenekli numuneler zerindeki gzeneklilik ve mikrosertlik zerine etkileri incelenmitir. almada iki tabakal fonksiyonel gzenekli yzeylerin retimi baarl bir ekilde gerekletirilmitir. Elde edilen sonulardan; gzenekliliin genellikle artan toz boyutu, azalan sktrma basnc ve scaklyla artt grlmtr. Ayrca, sinterleme scaklnn azalmasyla da gzeneklilik deeri artmtr. Mikrosertlik deerlerinde ise retim parametrelerine bal olarak belirgin bir deiim elde edilememitir. Anahtar Kelimeler: Gzenekli Yzeyler, Mikro retim, Bakr Tozu.
EFFECTS OF MANUFACTURING PARAMETERS ON THE POROSITY AND MICROHARDNESS OF MICRO-SCALE 3-D POROUS GRADIENT SURFACES
ABSTRACT Porous metallic surface structures are used in wide range of applications including heat exchangers, fuel cells, and biomedical implants for heat and mass transfer purposes. In this study, the effects of the compaction temperature, pressure, powder size and sintering temperature were investigated on porosity and microhardness during powder forming process. Tests proved successful implementation of two-layered porous gradient surface. The results showed that porosity increased with increasing powder size, decreasing compaction temperature and pressure. Also, porosity increased with decreasing sintering temperature. Analyses showed that microhardness values did not change significantly depending on the manufacturing parameters. Keywords: Porous Surfaces, Micro Manufacturing, Copper Powders. 1. GR Gzeneklilik (porozite), gzenekli malzeme tasarmnda en etkin faktrlerden biridir. Gzenekli yzeyler, ok deiik amalar iin farkl uygulama alan bulurlar. Bu yzeylere, gelimi s transfer uygulamalarndaki yzey alan arttrlm alanlar, kemik byme ve hcre oalmasn salayan biyouyumlu implantlar, madde filtrasyonu vb. r-
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nek olarak verilebilir. Mikro lekteki gzenekli yzeylerin, zellikle, s transferini gelitirdii ve iyiletirdii yaplan almalarda ortaya konulmutur [1-3]. Litter ve Kaviany mikro-lekte, kresel bakr tozlar kullanarak rettikleri gzenekli yzeylerdeki s transfer orann %300 deerinde arttrmlardr [4]. Benzer almalar yazarlar tarafndan da yaplm olup, bu almalarda bakr alt tabaka zerine yksek scaklkta bakr tozlar preslenmi ve retim parametrelerinin etkileri incelenmitir [1-3, 5]. Bu alma, hem gelimi s transferi hem de kat oksit yakt hcresi (solid oxide fuel cell, SOFC) gibi enerji dntrme sistemlerinde kullanlabilecek mikro yapda gzenekli yzeylerin retimini amalamaktadr. nerilen yntem, kresel tozlar metal bir alt tabakaya presleyip kompakt hale getirerek farkl gzeneklilik deerlerine sahip numuneler retmektir. Metal alt tabakaya bitiik alt yzeyin, madde transferini engellemek maksadyla sfra yakn gzeneklilikle retilmesi istenirken, st yzeyin ise gaz difzyonunu iyiletirmek (SOFC durumunda) veya s transferini gelitirmek (s eanjrlerindeki buharlama) amacyla yksek gzeneklilik deerlerinde (~%40) retilmesi amalanmtr. Alt tabaka malzemesi, uygulama alan ve kullanm amacna bal olarak bakr veya paslanmaz elik olabilir. almada farkl aplara sahip kresel bakr tozlar gzenekli yzey retmek iin bakr alt tabaka zerine farkl sktrma scaklklar ve basnlar kullanlarak sktrlm ve kompakt hale getirilmitir. Kompakt hale getirilmi olan numuneler farkl iki scaklkta sinterlenerek gzeneklilik ve mikrosertlikleri incelenmitir. 2. DENEYSEL ALIMALAR 2.1. Numune retimi Numune retiminde kullanlan bakr tozlar Acupowder International LLC (Union, NJ, ABD) firmasndan temin edilmitir. Tozlarn younluu, safl ve toz boyut dalm izelge 1de verilmitir. Numunelerin iki tabakal blge eklinde retilmesi amalandndan st yzey blgesi iin nispeten byk toz boyutlu tozlar (-106+90 m), alt yzey ve vadi blgesi iin srasyla farkl toz boyut aralna sahip tozlar (-63+45 m, -45+25 m ve -25+0 m) kullanlmtr. lk ksmda bahsedilen fonksiyonel gzenekli yzeyler retmek amacyla (a) niversal MTS ekme-basma makinesi (Instron SATEC 5596-400HVL), (b) toz sktrma kalp seti (alt kalp/zmba, st kalp ve tayc, (c) stma elemanlar, (d) kontrol ve veri toplama sistemi kullanlmtr. Alt kalbn yzeyinde 100 adet delik (10x10) mevcut olup her bir delik 0,5 mm derinliinde ve 1 mm apndadr. ekil 1de toz sktrma kalp seti verilmitir. izelge 1. almada kullanlan tozlarn zellikleri. Derece 83 103 155 Younluk (g/cc) 5.1 5.16 4.98 %Cu min 99.82 99.78 99.83 +80 2 max +100 20-50 2 max +150 50- 75 Bal Elek Analizi-Mesh- % +200 +325 10 max Tr 50-80 0.5 max 20-50 Bal -325 10 max 95 min
ekil 1. almada kullanlan kalp seti.
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Numune retiminde balangta -106+90 m toz boyut aralndaki tozlar st yzey blgesini retmek iin alt kalbn zerine delikleri dolduracak ekilde serbest olarak yerletirilmitir. Daha sonra toz boyutunun etkisini incelemek amacyla srasyla farkl toz boyut aralklarndaki tozlar (45-63 m, 25-45 m ve 0-25 m) benzer ekilde alt kalp zerine dklerek 200 m kalnlndaki bakr alt tabaka (substrate), tozlarn zerine yerletirilmitir. Kalp, istenen scaklkla bal olarak (350, 425 ve 500C) stlmtr. Bu scaklklara ulaldktan sonra tozlar, farkl toz sktrma basn deerinde (20, 35 ve 50 MPa) ayr ayr sktrlarak kompakt hale getirilmitir. almada numune retim artlarn minimuma indirmek iin MINITAB paket programndan istatistik deney tasarm (DOE: Design of Experiments) yaklam kullanlmtr. Tozlarn birbirine balanmasn ve mukavemet artn salamak amacyla kompakt hale getirilmi numuneler, bir tp frn ierisinde ve kontroll atmosfer ortamnda (%5 hidrojen + %95 azot) 1 saat sreyle srasyla iki farkl sinterleme scaklnda (600 ve 900 C) sinterlenmi ve numune retimi tamamlanmtr. retilen numunelerin ematik grnm ekil 2de, optik ve taramal elektron mikroskop (SEM) grntleri ise ekil 3 (a-d)de verilmitir.
ekil 2. boyutlu gzenekli yzeyin ematik gsterimi.
ekil 3. retilen numunenin: (a) optik mikroskop; (b) A-A kesitinin; (c) stten ve (d) perspektif SEM grnts (sinterleme scakl 900 oC, sktrma basnc: 50 MPa). 2.2. Gzeneklilik lmleri Numune retiminde kullanlan tozlar farkl byklkte olduklarndan st yzey, alt yzey ve vadi blgeleri iin farkl gzeneklilik deerleri llmtr. Gzeneklilik lmlerinde numuneler iki paraya ayrlm ve paralardan bir tanesi kalp ierisine alnmtr. Kalplanan numuneler daha sonra zmparalama ve parlatma ilemine tabi tutulmutur. Zmparalama ilemi 240, 400, 800 ve 1200 nolu zmparalar kullanlarak yaplmtr. Daha sonra, numune yzeyleri 6 ve 1 m luk elmas pastalar yardmyla parlatlmtr. Parlatlm numunelerin yzey grntleri k mikroskobunda incelenmi ve fotoraflar ekilmitir. Bu resimler Image J ve Motic programlar vastasyla ilenerek numunelerin gzeneklilik deerleri tespit edilmitir. Bu amala gzeneklilik lmleri iin alnan resimler ilk olarak siyah ve beyaz alanlara dntrlm (binarization) daha sonra st yzey, alt yzey ve vadi blgeleri seilerek, bu blgelerdeki
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her bir siyah ve beyaz alanlarn toplam, toplam alana oran tespit edilmitir. Numunelerin gzeneklilik deerleri 10 blgedeki farkl gzeneklilik deerinin ortalamas alnarak belirlenmitir. ekil 4 (a-f), farkl toz boyut aralna (0-25 m, 25-45 m ve 45-63 m) sahip tozlar kullanlarak retilmi numunelerin st yzey, alt yzey ve vadi blgelerin optik mikroskop ve siyah ve beyaz alanlara dntrlm grntlerini gstermektedir.
ekil 4. st yzey, alt yzey ve vadi blgelerin optik mikroskop ve siyah ve beyaz alanlara dntrlm grntleri: ((a), (b); toz boyut aral 0-25 m (c), (d); toz boyut aral 25-45 m ve (e), (f); toz boyut aral 45-63 m).
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2.3. Mikrosertlik lmleri Yzeyi parlatlm olan numunelerin Vickers mikrosertlikleri Duramin 4 mikrosertlik test cihaznda (Struers Co, Cleveland, OH, ABD) llmtr. Numunelere uygulanan yk 50 gram olup bekleme sresi 10 saniye olarak seilmitir. st yzey, alt yzey ve vadi blgelerinden alnan sertlik lm yerleri ekil 5de gsterilmitir.
ekil 5. Vickers mikrosertlik lm noktalar. 3. SONULAR VE TARTIMA 3.1. Gzeneklilik ekil 6 (a-f), farkl toz boyutu, sktrma scakl ve basncnn gzeneklilik zerindeki etkisini gstermektedir. Sinterleme scaklklar srasyla ekil 6 (a,c,e)de 600C, ekil 6 (b,d,f) de ise 900 C dir. Numunelerin st yzey, alt yzey ve vadi blgelerindeki gzeneklilik deerleri, sktrma basncnn 20 MPadan 50 MPaa artmas durumunda dmtr. 20 MPa sktrma basnc, 0-25 m toz boyutu, 425 C sktrma scakl ve 600 C sinterleme scaklnda st yzey blgesi iin elde edilen gzeneklilik deeri yaklak %30 iken; bu deer ayn artlarda 50 MPa sktrma basnc iin %24 olarak elde edilmitir. Ayn artlarda sadece toz boyutu deitirildiinde (45-63 m) st yzey blgesi iin gzeneklilik deerleri 20MPa ve 50MPa sktrma basnlarnda srasyla %32 ve %28 olarak bulunmutur. Sinterleme scakl 900 oC ye arttrldnda ise 20 MPa ve 50 MPa sktrma basnlarnda, 0-25 m toz boyutu ve 425 oC sktrma scaklnda st yzey blgesi iin elde edilen gzeneklilik deerleri srasyla %18 ve %10 dur. 45-63 m toz boyut aralnda ise bu deerlerin benzer ekilde yaklak %25 ve %20 olduu grlmtr. Tozlarn bir kalp ierisinde sktrlmas esnasnda, balangta tozlar 4-6 komusu ile temasta (koordinasyon says) bulunur. Artan basnla birlikte tozlar kalba daha iyi yerleir ve uygulanan basncn deerine gre de ekil deitirebilirler. Artan basnla birlikte gzenekliliin azalmasnn nedeni toz paracklarndaki deformasyonun artmas ve bunun sonucunda da tozlar arasndaki mevcut boluklarn azalmasdr [6, 7]. Gzenekliliin sktrma scaklnn artmasyla genel olarak azald gzlemlenmitir. 600 oC sinterleme scakl, 20 MPa sktrma basnc, 25-45 m toz boyut aral iin; sktrma scaklnn 350 oC den 500 oC ye artmasyla st yzey blgesi iin elde edilen gzeneklilik deerleri srasyla %32 ve %27 olarak elde edilmitir. Sktrma basncnn 35 MPa olmas durumunda 0-25 m toz boyut aral iin gzeneklilik deerleri %30 ve %21; 45-63 m toz boyutunda ise bu deerler %36 ve %26 dr. 900 oC sinterleme scakl, 20 MPa sktrma basnc ve 25-45 m toz boyutunda sktrma scaklnn 350 oC den 500 oC ye arttrlmasyla elde edilen gzeneklilik deerleri srasyla %23 ve %19; ayn artlarda basncn 50 MPa artmasyla ayn toz boyutunda gzeneklilik deerleri %21 ve %15 olarak bulunmutur. (ekil 6 a-f). Artan scaklkla birlikte gzeneklilik deerlerinin azalmasnn nedeni tozlarn ve kat alt yzeyin yumuayarak snek hale gemesi, basnla birlikte tozlarn temas alanlarnn artmasyla paracklar arasndaki boluklarn azalmasdr [1,8].
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ekil 6. Gzenekliliin retim parametrelerine bal olarak deiimi: (a, c, e sinterleme scakl 600C; b, d, f sinterleme scakl: 900C). 600 oC ve 900 C sinterleme scaklklarnda sinterleme ile boyun verme (necking-growth) oluumunun taramal elektron mikroskopu (SEM) grnts ekil 7 (a-b) de verilmitir. 600 C sinterleme scaklklarnda boyun oluumu gzlenmezken, 900 C sinterleme scaklnda kresel tozlar arasnda kat halde boyun oluumu grlmektedir. Bu tr boyunlama, mukavemetin ham mukavemete oranla artmasn salar.
ekil 7. Sinterleme ile boyun oluumunun SEM grnts (sol taraf dk bytme sa taraf yksek bytme): a) sinterleme scakl 600 C ve b) sinterleme scakl 900 C.
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Farkl sktrma scakl ve basncnn numunelerin st yzey gzenekliliine etkisi boyutlu olarak ekil 8de verilmitir. 600 C sinterleme scaklnda sktrma scakl ve basncna bal olarak daha yksek gzeneklilik seviyeleri ve deiimleri elde edilirken 900 oC sinterleme scaklnda gzeneklilik seviyeleri daha dk olmutur.
ekil 8. st yzey blgesi iin sktrma scakl ve basncnn gzeneklilik zerine etkisi: (a) sinterleme scakl 600 C ve (b) sinterleme scakl 900 C. 3.2. Mikrosertlik ekil 9 (a-f), farkl toz boyutu ve sktrma scaklnn st yzey, alt yzey ve vadi blgelerinin mikrosertlik zerindeki etkisini gstermektedir. ekil 9 (a-f)de grld zere, st yzey alan iin elde edilen mikrosertlik deerlerinde sinterleme scaklnn 600 oCden 900 oCye arttrlmasyla, hem sktrma scaklnn hem de sktrma basncnn arttrlmasyla belirgin bir deiim elde edilememitir. st yzey blgesi iin mikrosertlik deerleri 85-100 (Hv0,05) olarak tespit edilmitir. Ancak, alt yzey ve vadi blgelerinin mikrosertlikleri hem sktrma scaklnn ve basncn artrlmasyla hem de sinterleme scaklnn arttrlmasyla artmtr.
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ekil 9. Mikrosertliin retim parametrelerine bal olarak deiim; (a, c, e sinterleme scakl 600C; b, d, f sinterleme scakl: 900C). Farkl sktrma scakl ve basncnn numunelerin st yzey mikrosertlik zerindeki etkisi boyutlu yzey alan olarak ekil 10da gsterilmitir.
ekil 10. st yzey blgesi iin sktrma scakl ve basncnn mikrosertlik zerine etkisi (a) sinterleme scakl 600 C ve (b) sinterleme scakl 900 C. 4. SONULAR Bu almada toz metalurjisi yntemiyle farkl toz boyutu aralklarnda bakr tozlar kullanarak boyutlu, gzenekli yzeyler, farkl retim parametrelerine bal olarak retilmi ve retim parametrelerinin yzeylerin gzeneklilik ve mikrosertlik zerindeki etkisi incelenmitir. almada gzenekli yzeyler, iki farkl toz boyutu aralna sahip olacak ekilde tozlar kullanlarak retilmitir. Elde edilen sonulardan gzenekliliin hem st yzey ve alt yzey hem de vadi blgeleri iin artan toz boyutu, azalan sktrma scakl, basnc ve azalan sinterleme scakl ile artt grlmtr. Ancak, numunelerin st yzey blgesi iin, mikro sertlik deerlerinde retim parametrelerine bal nemli bir deiim gzlemlenmemitir. Ancak, alt yzey ve vadi blgeleri iin mikrosertlik deerleri, artan sinterleme scakl, sktrma scakl ve basncyla artmtr. TEEKKR Bu alma, Amerikan Ulusal Bilim Konseyi (NSF) tarafndan desteklenen ENG/CMMI 0638522 nolu proje kapsamnda yaplmtr. Proje desteklerinden dolay Ulusal Bilim Konseyine teekkr ederiz. KAYNAKLAR 1. Cora, .N., Usta, Y., and Ko, M., Micro-Manufacturing of Micro-Scale Porous Surface Structures for Enhanced Heat Transfer Applications An Experimental Process Optimization Study, Journal of Micromechanics and Microengineering, Vol. 19, pp. 1-12, 2009. 2. Min, D.H., Hwang, G.S., Usta, Y., Cora, O.N., Ko, M., and Kaviany, M., 2-D and 3-D Modulated Porous Coatings for Enhanced Pool Boiling, International Journal of Heat and Mass Transfer, Vol. 52, pp. 2607-2613, 2009.
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3. Cora, .N., Min, D., and Ko, M., Kaviany, M., Micro-scale Modulated Porous Surface Coatings-Fabrication and Pool Boiling Heat Transfer Experiments, Journal of Micromechanics and Microengineering, Vol. 20, pp. 1-12, 2010. 4. Liter, S.C, and Kaviany, M., Pool-boiling CHF Enhancement by Modulated Porous-Layer Coating: Theory and Experiment, International Journal of Heat and Mass Transfer, Vol. 44, pp. 4287-4311, 2001. 5. Ko, M., Usta, Y., and Karako, A., Investigations on Thermo-Mechanical Fabrication of Micro-Scale Porous Surface Features Journal of Power Sources, Vol. 179, pp. 592602, 2007. 6. Gupta, M., Tay, A.A.O., Vaidyanathan, K., Srivatsan, T.S., An Investigation of the Synthesis and Characterization of Copper Samples for Use in Interconnect Applications, Materials Science and Engineering: A, Vol. 454-455, pp. 690-694, 2007. 7. German, R.M., Toz Metalurjisi ve Parackl Malzeme lemleri Editrler: Sarta, S., Trker, M., Durlu, N., Trk Toz Metalurjisi Dernei Yaynlar: 05, Ankara, 2007. 8. Ahmed, Y.M.Z, Riad, M.I., Sayed, A.S., Ahlam, M.K., Shalabi. M.E.H., Correlation between Factors Controlling Preparation of Porous Copper via Sintering Technique using Experimental Design, Powder Technology, Vol. 175, pp. 48-54, 2007.
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POROUS MATERIALS
www.turkishpm.org
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TOZ METALURJS YNTEM LE RETLEN KRESEL EKLL ALMNYUM KPKTE KPRTME SICAKLIININ VE TiH2 ERNN KPRME DAVRANII ZERNE ETKS
Arif UZUN*, Mehmet TRKER** Kastamonu niversitesi, Cide Rfat Ilgaz MYO, Kaynak Teknolojisi Blm, Kastamonu, auzun@kastamonu.edu.tr ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, mturker@gazi.edu.tr
*
zet Bu almada toz metalurjisi yntemi ile retilen kresel ekilli alminyum kpk paralarda kprtme scakl ve kprtc madde (TiH2) miktarnn, kprme davran zerine etkileri aratrlmtr. Buna gre Alumix 231 tozuna deiik oranlarda (% 0,5-0,75-1 ve 1,5) TiH2 tozu ilave edilerek kartrlm ve tek ynl preste 600 MPa basn uygulanarak preslenmitir. Bunun sonucu 30x50x10 mm llerinde elde edilen taslak numuneler frn ierisinde 550oC scaklkta 180 dakika bekletilmi ve % 70 orannda deforme edilmitir. Elde edilen preform numuneler kare eklinde kesilerek, 650oC ile 710oC scaklklar arasnda kprtme ilemine tabi tutulmutur. Burada kprtme scaklna ve TiH2 ieriine bal olarak kresel ekilli Al kpn hacimsel genleme oranlar, younluk ve gzenek morfolojisi deiimleri belirlenmitir. Anahtar Kelimeler: Kresel ekilli Al Kpk, Kprtme Scakl, TiH2
THE EFFECT OF TiH2 CONTENT AND FOAMING TEMPERATURE ON THE FOAMING BEHAVIOUR OF SPHERICAL ALUMINUM FOAM PRODUCED BY POWDER METALLURGY ROUTE
ABSTRACT The effect of production parameters such as foaming duration and the amount on the foaming behavior of sphericalshaped aluminum foam parts was studied. Alumix 231 and various amount of foaming agent (0,5-0,75-1 and 1,5% TiH2) were mixed, and then compacted at 600 MPa pressure by using a uniaxial action press to produce blanks with 50x30x10 mm dimensions. These blanks were pre-heated at 550C in a furnace for 180 min and then deformed by 70% by using an eccentric press. They were cut into square shape and foamed at temperatures between 650oC and 710oC. It was determined that the linear expansion, density and pore morphology chances of spherical-shaped aluminum foam depending on the foaming temperature and TiH2 content. Keywords: Spherical-Shaped Al Foam, Foaming Temperature, TiH2 1.GR Metalik kpkler mekaniksel, fiziksel ve akustik zellikleri son derece iyi olan ve retim yntemleri hzla gelitirilen yeni bir malzeme grubudur [1]. Bu zelliklerinin kombinasyonundan dolay yapsal ve fonksiyonel uygulamalarda
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sklkla kullanlmaya balanm ve bunun zerine birok aratrma yaplmtr [1-3]. Bu aratrmalara konu olan ve metalik kpkler arasnda yeni saylabilecek malzeme trlerinden bir tanesi de kresel ekilli alminyum kpklerdir. Almanyada IFAM tarafndan gelitirilen kresel ekilli metalik kpk paralar ileri gzenek morfolojisi (APM) teknii ile retilmektedir. Bu yntem esasen toz metalurjisi yntemindeki kpn genleme ve ekillenme ilemlerini birbirinden ayrmaktadr. Bu iki aama, farkl zamanlarda ve farkl yerlerde retici firmalar tarafndan ayr ayr gerekletirilebilmektedir. Gerek IFAM, gerekse dier ticari firmalar tarafndan retilecek kresel ekilli alminyum kpk paralar tketiciye maliyet ve iilik asndan nemli lde tasarruf salamaktadr. Bu teknikte kprtme ilemi esnasnda kalp kullanlmamaktadr. retilen paralar genelde 1 cm3ten daha kk hacimlere sahiptir. Bu malzemeler aralarn n takmlarndaki darbe dayanmn artrmak iin elik profillerin ierisine doldurularak kullanlabildikleri gibi basit yaptrma teknikleri ile birlikte kullanlmas, kullanclar iin maksimum ynde esneklik salamaktadr [4, 5]. 2. DENEYSEL ALIMALAR 2.1. Malzemeler Deneysel almalarda kresel ekilli alminyum kpk retimi iin matris malzemesi olarak % 99 saflkta ve <200 m parack ebadna sahip Alumix 231 tozlar (Al-%2,5Cu-%0,5Mg-%14Si) ve kprtc madde olarak da <45 m, % 98 saflktaki TiH2 tozlar kullanlmtr. 2.2. Numune Hazrlama ve Kprtme lemi almann ilk aamas preform malzeme retimi ile balamaktadr. Bu amala deiik oranlarda (% 0,5-0,75-1 ve 1,5) TiH2 tozlar, matrisi oluturan alminyum tozlarna ilave edilerek, boyutlu kartrcda 30 dakika sreyle kartrlmtr. Daha sonra karm tozlar kalp ierisinde tek ynl preste 600 MPa basn uygulanarak preslenmi ve 30x50x10 mm llerinde taslak numuneler haline getirilmitir. Elde edilen bu numuneler frn ierisinde 550oC scaklkta, 180 dakika bekletilerek n stmaya tabii tutulmutur. Akabinde numuneler % 70 oranda deforme edilmi ve 6x6 mm boyutlarda kare eklinde kesilerek kprmeye hazr hale getirilmitir. kinci aamada ise kprtme ilemi gerekletirilmitir. Bunun iin kprmeye hazr hale gelen preform numuneler frn ierisinde 650oC, 670oC, 690oC ve 710oC scaklklarda 2 ile 5 dakika arasnda 30 saniye aralklarla bekletilerek kprtme ilemine tabii tutulmutur. Bu ilem srasnda herhangi bir kalp kullanlmadan serbest halde kprtme yaplmtr. Bu sayede frn ierisindeki s, kalp duvarlar tarafndan engellenmeden preform malzeme ierisine dorudan nfus etmi ve yar ergiyik hale gelen alminyumun, yzey gerilmesi neticesinde kresele yakn bir ekil almtr. ekil 1de kresel ekilli kpn retimi esnasnda sahip olduu geometrik yapya benzeyen metalik kpn radyoskobik X-ray grnts verilmektedir.
ekil 1. Kresel ekilli kpn retimi esnasnda sahip olduu geometrik yapya benzeyen metalik kpn radyoskobik X-ray grnts [6] 2.3. Karakterizasyon retilen kpk numunelerin younluklar ve hacimsel olarak genleme oranlar 0,1 mg hassasiyetteki terazi ve younluk kiti ile llmtr. Buna gre younluk hesab E.1de verilen Arimet prensibi esasna gre yaplmtr. Bu eitlikte, * kpn younluunu, mhava kpn havadaki arln ve msu kpn su ierisindeki arln ifade etmektedir.
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(1)
Genleme oran ise E. 2de verilen formle gre hesaplanmtr. Bu formlde V* kpn hacmini, V ise kprtme ncesi numunenin ilk hacmini ifade etmektedir. Gzeneklilik oran ise E.3te verilen formle gre hesaplanmtr. Burada , gzenek duvarlarn oluturan ana malzemenin younluunu belirtmektedir. Hacimsel Genleme ( HG ) = (V*/V-1) x 100 (2)
Gzeneklilik (G)= (1 */) 100
(3)
Younluklar ve hacimsel genleme oranlar hesaplanan numuneler daha sonra makro boyutta gzenek yaplar incelenmek amacyla 240lk zmpara ile su altnda andrlmtr. Daha sonra elde edilen alminyum kpklerin gzenek ekli, gzenek boyutu ve gzenek dalm incelenmek amacyla dijital kamera ile makro yap fotoraflar ekilmitir. Bylelikle kprtc madde miktarnn ve kprtme scaklnn kresel ekilli alminyum kpk retimine etkileri incelenmitir. 3. DENEY SONULARI VE TARTIMA Tablo 1de kpk retim aamalarnda kullanlan deiken parametreler verilmitir. Bu parametreler birbirleriyle kombine edilerek her trl deney art deerlendirilmitir. Bylece deneylerde kullanlan deiken parametrelerin, kresel ekilli kpn younluk, hacimsel genleme, gzenek morfolojisi gibi zelliklere ne tr etkisi olduu belirlenmitir. Tablo 1. Kresel ekilli alminyum kpk retiminde kullanlan deiken retim parametreleri TiH2 miktar (%) 0,5 0,75 1 1,5 3.1. Liner Genleme, Kresellik ve Younluk Deiimleri ekil 2de farkl scaklklarda kprtme ilemine tabii tutulan numunelerin kprtc madde miktar ve kprtme srelerine bal hacimsel genleme oranlar verilmitir. Buna gre, grafiklere bakldnda 650oC scaklkta numunelerde maksimum hacimsel genleme orannn % 400 at grlmektedir. Ancak bu noktaya ulatklar sreler birbirinden farkldr. erisinde %1,5 TiH2 ieren numuneler, dierlerine oranla daha ksa srede ve % 431 ile maksimum oranda hacimsel genleme sergilemitir. Bu oran % 0,5 TiH2 ieren numunelerde % 422, % 0,75 TiH2 ieren numunelerde % 434 ve %1 TiH2 ieren numunelerde % 449dur. 670 oCde kprtme ilemine tabii tutulan numuneler arasnda en fazla hacimsel genlemenin % 523 ile ierisinde %1 orannda TiH2 ieren numunelerde meydana geldii grlmektedir. Bu scaklkta en dk maksimum hacimsel genleme ise % 400 ile ierisinde % 1,5 TiH2 bulunduran numunelerde elde edilmitir. Benzer ekilde 690 oCde kprtme ilemine tabii tutulan numuneler arasnda da en fazla hacimsel genlemenin % 556 ile ierisinde %1 TiH2 ieren numunelerde meydana geldii grlmektedir. Bu scaklkta en dk hacimsel genleme ise % 356 ile yine ierisinde % 1,5 TiH2 bulunduran numunelerde elde edilmitir. Burada dikkat ekici husus, % 1,5 TiH2 ieren numuneler 650 oCde maksimum hacimsel genleme oranna sahipken, 670 oC ve 690 oC scaklklarda en dk hacimsel genleme oranlarna sahiptir. Bu fark hacimsel genlemeye yalnzca kprtc madde miktarn deil, ayn zamanda scaklnda etkisi olduunu gstermektedir. Literatrde genleme orann sadece kprtc madde miktarna bal olmad, ayn zamanda ergiyik viskozitesine de bal olduu belirtilmitir [7-9]. Bu dorultuda scaklktaki artn, kprme ilemi srasnda ergiyik halde bulunan numunenin viskozitesini drd, bylelikle yap ierisinde bulunan hidrojen gaznn daha rahat genleme gsterdii anlalmaktadr. Ancak bu genlemenin devam etmesi, kpk yapda hcre zarnn incelmesine ve zarn yrtlmasna neden olmaktadr. Dolaysyla yap ierisinde hapsedilmi hidrojen gaznn bu blgelerden rahatlkla uzaklat ve kntlerin balad grlmtr (ekil 3) [6]. Bunun sonucu olarak 710 oCde kprtme ilemine tabii tutulan numunelerin hacimsel genleme oranlarnda azalmalar ve yapda dzensizlikler meydana gelmitir. 70 Deformasyon oran (%) Kprtme scakl (oC) 650 670 690 710 Kprtme sresi (dak.) 2-2,5 3-3,5 4-4,5 5
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ekil 2. Farkl scaklklarda kprtme ilemine tabii tutulan numunelerin kprtc madde miktarna ve kprtme srelerine bal hacimsel genleme oranlar
ekil 3. Kprtme ilemi srasnda yapda meydana gelen yrtlma ekil 4te ierisinde deiik miktarlarda kprtc madde bulunan ve farkl scaklklarda kprtme ilemine tabii tutulan numunelerin maksimum oranda hacimsel genlemeleri sonucu elde edilen kpk yaplar verilmektedir. Bu resimler zerinden yaplan alansal ve evresel lmler elde edilen numunelerin teoride kresellik deerleri hakknda bilgi vermitir. Bunun iin aadaki eitlikten faydalanlarak hesaplamalar yaplmtr. Burada fkresel ekil faktr, A alan ve P evre uzunluunu belirtmektedir. f kresel = (4A)/P2x100 (4)
Elde edilen verilere gre 650 oC, 670 oC ve 690 oC scaklklarda maksimum hacimsel genleme sergileyen numunelerde % 90 ile % 95 arasnda deien kresellik deerlerleri mevcuttur. Ancak 710 oCde kpk yaplardaki dzensizlikler rahatlkla fark edilmekte ve kresellik oranlar dierlerine oranla ok daha dk olduu grlmektedir. Dz bir zemin zerinde kprtlen numuneler yer ekimi etkisiyle tam bir kresellie sahip olmadndan geometrik ekilleri elipse benzemektedir [10].
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Maksimum oranda genleme sergileyen numunelerin younluklar karlatrldnda ise en dk younluk ierisinde % 1 TiH2 ieren ve 690 oCde kprtlen numunelerde elde edilmitir. Younluk, numunelerin hacmi ile ters orantl olduundan hacimsel genleme oran maksimum olan bu numunelerde younlukta en dk seviyededir. Kresel ekle yakn olan numunelerde younluk deiimi 0,41 - 0,52 g/cm3 arasndadr.
ekil 4. Farkl scaklklarda kprtme ilemine tabii tutulan numunelerin maksimum oranda hacimsel genlemeleri sonucu elde edilen kpk yaplar 3.2. Gzenek Morfolojisi Deiimi ekil 5te maksimum oranda hacimsel genleme sergileyen numunelerin gzeneklilik oranlar verilmitir. Gzeneklilik oran numune ierisindeki gaz boluklarn ifade etmektedir. Bu orann gzenek says ile kartrlmamas gerekmektedir. Grafie bakldnda 650 oC, 670 oC ve 690 oC scaklklarda % 1e kadar TiH2 art gzeneklilik orannda arta neden olurken, 710 oCde srekli azalan ynde etki etmitir. Benzer scaklklarda % 1,5 TiH2 ieren numunelerde ise gzeneklilik orannda belirgin bir dn meydana geldii grlmektedir. Bunun sebebi, artan scaklk ve kprtc madde miktar, kprtme ilemi srasnda gzeneklerin birlemesine ve yer yer hidrojen ka ile kntlere neden olmasdr. Maksimum oranda gzeneklilik % 85 ile 690 oC scaklkta % 1 orannda TiH2 ieren numunelerde elde edilmitir. En dk gzeneklilik ise 710 oC scaklkta % 1,5 orannda TiH2 ieren numunelerde % 75 orannda elde edilmitir.
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ekil 5. Maksimum oranda hacimsel genleme sergileyen numunelerin gzeneklilik oranlar ekil 6da maksimum oranda hacimsel genleme sergileyen numunelerin ara kesit resimleri verilmitir. Numunelerin gzenek yaplar makro boyutta incelendiinde gzenek boyutu ve saysnda farkllklarn olduu aka grlmektedir. 650oC, 670oC ve 690oC scaklklarda kprtc madde miktar %1,5e ulatnda gzenek boyutlarnda dierlerine kyasla belirgin bir art mevcuttur. Bu durum kprtme ilemi srasnda preform ierisinde youn halde bulunan TiH2n znmesi sonucu aa kan gaz baloncuklarnn birlemesi ile olumutur. Ayrca artan scaklkla birlikte yap ierisindeki hidrojen gaz basncndaki art bu durumu daha etkin hale getirmektedir. Sz konu etkenler ald zaman ise 710 oCde kprtme ilemine tabi tutulan numunelerde olduu gibi kmeler meydana gelmektedir. Gzenek boyutu dalm asndan ierisinde % 0,5 ile % 1 arasnda TiH2 ieren ve 690oCde kprtlen numuneleri daha homojen olduu grlmektedir. Alminyum kpk retiminde TiH2 miktar genellikle % 0,6 ile % 1 arasnda seilmektedir.
ekil 6. 650oCde kprtme ilemine tabii tutulmu numunelerin gzenek yaplar
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4. SONULAR Bu almada toz metalurjisi yntemi ile retilen kresel ekilli alminyum kpk paralarda kprtme scaklnn ve kprtc madde miktarnn, kprme davran zerine etkileri aratrlmtr. Elde edilen verilere gre kresel ekilli alminyum kpklerdeki hacimsel genlemenin yalnzca kprtc madde miktarna bal olmad, ayn zamanda scaklk ile ilikili olduu belirlenmitir. nk alminyum kpklerde artan scaklk ile birlikte ergiyik viskozitesi dmektedir. Bundan dolay hem scaklk, hem de kprtc madde miktarndaki art yap ierisindeki hidrojen gaz basncn artrmakta ve yapda daha rahat genleme salamaktadr. Ancak bu genleme belirli bir noktadan sonra hcre zarnda incelmelere ve yrtlmalara neden olarak kresel ekilli alminyum kpn kmesine ve yapsal dzensizliklerin olumasna neden olmaktadr. Bu durumum 710oC scaklkta daha etkin olduu belirlenmitir. Dolaysyla scaklk ve kprtc madde miktarndaki art ile kresel ekilli alminyum kpk retim sreci kontrolnn azald aktr. 650oC, 670oC ve 690oC scaklklarda maksimum oranda genleme sergileyen numunelerde teorik olarak % 90nn zerinde kresellik elde edilmitir. Fakat 710 oCde kresellik bu orann altndadr. Kresel ekle yakn olan numunelerde younluk deiimi 0,41 - 0,52 g/cm3 arasndadr. 650 oC, 670 oC ve 690 o C scaklklarda % 1e kadar TiH2 art gzeneklilik orannda arta neden olmutur. 710 oCde ise srekli azalan ynde etki etmitir. Benzer scaklklarda % 1,5 TiH2 ieren numunelerde ise gzeneklilik orannda belirgin bir d meydana gelmitir. Bunun sebebi, artan scaklk ve kprtc madde miktar, kprtme ilemi srasnda gzeneklerin birlemesine ve yer yer hidrojen ka ile kntlere neden olmasdr. Maksimum oranda gzeneklilik % 85 ile 690 oC scaklkta % 1 orannda TiH2 ieren numunelerde elde edilmitir. KAYNAKLAR 1. Ashby, M. F., Evans, A., Fleck, N. A., Gibson, L. J, Hutchinson J. W., Wadley, H. N. G.,Metal foams: a design guide, Oxford, Butterworth, Heinmann, 2000. 2. Banhart, J., Manufacture, characterisation and application of cellular metals and metal foams, Progress in Materials Science, 46:559-632, 2001 3. Degischer, H.P.; Kriszt, B., Handbook of Cellular Metals, Wiley- VCH, Weinheim, pp. 1521, 2002 4. Rausch, G., K. Stobener, Improving Structural Crashworthiness Using Metallic and Organic Foams, Porous Metals and Metal Foaming Technology Conference Proceedings, Kyoto (Japan), JIMIC, 2005 5. Stbener, K., Baumeister, J., Rausch, G., Rausch, M., Forming metal foams by simpler methods for cheaper solutions, Metal Powder Report, 60:12-16, 2005 6. Dudka, A., Garcia-Moreno, F., Wanderka, N., Banhart, J., Structure and distribution of oxides in aluminium foam, Acta Materialia, 56:39904001, 2008 7. Yang, C.C., Nakae, H., Foaming characteristics control during production of aluminum alloy foam, Journal of Alloys and Compounds, 313:188191, 2000. 8. Uzun, A., inici, H., Trker, M., Effect of deformation rate and foaming duration on the properties of spherical aluminum foam produced by powder metallurgy, 5th International Powder Metallurgy Conference, Ankara, 801-807, 2008 9. Duarte, I., Banhart, J., A study of alumnum foam formaton knetcs and mcrostructure, Acta mater., 48:23492362, 2000. 10. Stbener, K., Baumeister, J., Rausch, G., Busse, M.,Metal Foams with Advanced Pore Morphology (APM), Fraunhofer IFAM, 26:231-237, 2007
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YKSEK ORANDA GZENEK EREN DEMR ESASLI KOMPAKTLARIN KARBON ERNN BASMA DAVRANIINA ETKS
Nuray BEKZ*, Enver OKTAY* *stanbul niversitesi Metalurji ve Malzeme Mhendislii Blm, Avclar,stanbul. e-mail : nbekoz@istanbul.edu.tr, oktay@istanbul.edu.tr ZET Bu almada; %48-70 arasnda deien oranlarda gzenek ieren demir esasl kompaktlar; n alaml Distaloy AE demir tozuna a. %0,3, 0,6 ve 0,8 orannda karbon katlarak toz metalurjisindeki boluk yapc teknii kullanlarak retilmilerdir. Boluk yapc olarak 0,71-1,00 mm boyut aralna sahip dzensiz ekilli karbamit, karbon katkl Distaloy AE tozuyla kaplanm ve 200 MPa basn altnda tek ynl preslenerek boy/ap oran yaklak 1,5 olan ham kompaktlar elde edilmitir. Ham kompaktlar ierisindeki karbamitin oda scaklnda suda zndrlmesi ile oluturulan gzenekli yaplar; hidrojen atmosferi altnda 1200 Cde 60 dakika sinterlenmitir. Karbon ilavesi kompaktlarn basma dayanmlarn arttrmtr. Artan gzenek miktar ile kompaktlarn basma dayanmlar ve elastisite modlleri azalmtr. Basma testi sonular, mikroyap karakterizasyon bulgular altnda tartlmtr. Anahtar kelimeler: Gzenekli malzemeler, n alaml demir tozu, sinterleme, basma testi.
EFFECT OF CARBON CONTENT OF HIGHLY POROUS IRON BASED COMPACTS ON THE COMPRESSION BEHAVIOUR
ABSTRACT In this study; iron based compacts having porosities in the range 48-70% were produced from 0.3, 0.6 and 0.8 wt.% carbon added pre-alloyed Distaloy AE powders by the space holder technique in powder metallurgy. For this purpose irregular shaped carbamide particles with the size distribution of 0.71-1.00 mm were covered by carbon added prealloyed iron based Distaloy AE powder and pressed uniaxially at 200 MPa to produce cylindrical green compact with length to diameter ratio of about 1.5. Highly porous structures were obtained by removal of the carbamide in a water bath at room temperature and sintered under hydrogen atmosphere at 1200 C for 60 minutes. Carbon additions increased the compressive strength values of the compacts. Compressive strength and the modulus of elasticity values of the compacts decreased with increasing porosity. Results obtained by compression test were discussed in light of the findings obtained by microstructure characterization. Keywords: Porous materials, pre-alloyed iron powder, sintering, compression test. 1. GR Toz metalrjisi yntemiyle retilen demir esasl malzemelerin mukavemetini arttrmak iin, demir tozlarna eitli alam elementleri ilave edilir. Karbon katks elastiklik zelliin aranmad durumda yk-
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sek mukavemete sahip para retimini ekonomik olarak mmkn klmaktadr. Bu, parann her yerinde demiri karbonla alamlandrarak elde edilir. Bu tip bir malzeme retiminin en yaygn yntemi demir tozuyla grafiti kartrmaktr. Yaplan almalar, sinterleme srasnda stenit ierisine geen karbonun souma esnasnda perlitik ve beynitik yapy oluturduunu ortaya koymutur [1-6]. Chawla ve dierleri [7], Distaloy AB tozuna benzer bileimdeki alaml demir tozuna farkl oranlarda karbon ilave ederek rettikleri youn numunelerde mikroyapnn perlit, beynit, martensit, nikelce zengin blge ve gzeneklerden olutuunu tespit etmilerdir. Boluk yapc kullanarak toz metalurjisi yntemiyle yksek oranda gzenek ieren metal (kpks metal) retimi; gzenek zelliklerinin, malzeme eklinin ve mekanik zelliklerin kontrolnde dier yntemlere gre salad birok stnlkten dolay son yllarda kullanlan bir yntem olarak karmza kmaktadr. Kullanlacak boluk yapc, malzemenin ierisinde kalnt brakmadan kolayca atlabilmeli ve metalle reaksiyona girmemelidir. Karbamit, hem termal hem de suda zndrlerek yapdan uzaklatrlabildiinden; alminyum, titanyum, paslanmaz elik, nikel ve bunlarn alamlarndan yksek oranda gzenek ieren metal retiminde son yllarda baarl olarak kullanlmaktadr [8-11]. Mo ieren n alaml demir tozlarndan retilen yksek oranda gzenek ieren malzemeler; yksek scakla ve sl oklara kar dayanma sahip olmasndan dolay s kalkan olarak s yaltm ve soutma sistemlerinde, yanma motorlarnn yksek scakla maruz kalan k yerlerinde kullanm potansiyeline sahiptir [12-13]. Literatrde; Distaloy AE tozundan hareketle boluk oluturucu kullanlarak toz metalurjisi yntemiyle kpks metal retimine ynelik bir alma bulunmamaktadr. Bu almada, boluk yapc kullanarak toz metalurjisi yntemiyle Distaloy AE tozundan yksek oranda gzenek ieren numuneler retilerek; karbon katksnn basma davran zerine etkisi mikroyap karakterizasyon bulgular altnda deerlendirilmitir. 2. MALZEME VE YNTEM Deneysel almada; Hgans firmas tarafndan atomizasyon yntemi ile retilmi ortalama tane boyutu 90 m olan dzensiz ekilli n alaml Distaloy AE demir tozu kullanlmtr. Karbon ilavesinin sinterleme sonras zelliklere etkisini incelemek iin Hgans firmas tarafndan retilmi sertletirici ve yalayc zelliklere sahip ticari ismi UF4 olan grafit tozu kullanlmtr. Ham mukavemeti arttrmak amacyla balayc olarak kullanlan parafin Merck firmasndan temin edilmi olup 46-48 C arasnda erime scaklna sahiptir. Boluk yapc olarak; +710-1000 m boyut aralna sahip dzensi3z ekilli teknik safiyette karbamit kullanlmtr. Karbamitin younluu; 1,34 g/cm , erime scakl 133 C ve 20 C scaklktaki suda znrl 108 g/mLdir. Deneysel almada kullanlan tozlarn kimyasal bileimleri Tablo 1de verilmektedir. Tablo 1 : Tozlarn kimyasal bileimleri, % [3].
ekil 1-(a)da atomizasyon yntemiyle retilmi n alaml Distaloy AE tozunun, (b)de dzensiz ekilli karbamitin Taramal Elektron Mikroskobu (SEM) grntleri verilmitir.
ekil 1 : Deneysel almada kullanlan (a) Distaloy AE tozunun ve (b) karbamitin SEM grnts
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Deneysel almada kullanlan toz metalurjisi yntemi ile kpks metal retiminin temel ilem admlar ekil 2de verilmitir.
ekil 2 : Toz metalurjisi yntemi ile kpks metal retiminin temel ilem admlar Numunelerin retimi aamasnda ilk olarak; Distaloy AE tozuna a.%0,3, %0,6 ve %0,8 oranlarnda karbon ilavesi yaplarak farkl karbon ieriklerinde demir esasl toz gruplar oluturulmutur. lave edilen karbonun karm ierisinde homojen olarak dalmas iin tozlar, 30 kg kapasiteli 30 devir/dakika hza sahip Apex marka laboratuar tipi kartrc ierisinde 30 dakika sreyle kartrlmtr. Ham numunelerin mukavemetinin arttrlmas amacyla balayc olarak a.%3 orannda hazrlanan parafin zeltisi, n alaml demir tozuna hac.%2 orannda katlarak oda scaklnda 30 dakika kartrlmtr. Karma; hac.%50 ile %80 arasnda deien oranlarda karbamit ilave edilip turbula tipi kartrcda 1 saat sre ile kartrma sonucu, karbamit paracklar demir tozlar ile kaplanmlardr. Demir tozlaryla kaplanm karbamitin elik bir kalp ierisinde tek ynl preslenmesiyle 12 mm apnda ve yaklak 18 mm yksekliinde silindirik numuneler elde edilmitir. Optimum presleme basncn belirlemek amacyla 100-400 MPa arasnda basnlar uygulanmtr. Preslenen numuneler ierisindeki karbamitin zndrlerek numunelerden uzaklatrlmas oda scaklnda saf su banyosunda yaplmtr. 200 MPa altnda basnlar uygulanarak retilen ve yksek oranda karbamit ieren numunelerdeki karbamitin zndrlerek uzaklatrlmas esnasnda yapnn kt; 200 MPa zerinde basnlar uygulanarak retilen daha dk oranlarda karbamit ieren numunelerde ise; karbamit uzaklatrldktan sonra kurutma esnasnda numunelerin atlad grlmtr. Bu nedenlerden dolay tm numuneler 200 MPa basn uygulanarak preslenmitir. zndrme sresi; hacimce %80, %70, %60 ve %50 karbamit ieren numuneler iin srasyla; 3, 5, 8 ve 12 saat olarak gereklemitir. Numunelerin ierisinde kalan az miktardaki karbamit ile balayc olarak kullanlan parafinin termal olarak giderilmesi ve sinterleme ilemi Lenton marka frnda yaplmtr. Seramik boru ierisine yerletirilen numuneler; ortamdan N2 gaz geirilerek nce 5 C/ dak stma hzyla 400 Cye stlm ve bu scaklkta 30 dakika tutulmu daha sonra ortamdan yksek safiyette H2 gaz geirilerek 10 C/dakika stma hzyla 1200 Cde 1 saat sinterlenmitir. Sinterlenmi numunelerin younluklar, ak ve kapal gzenek oranlar Arimed Yntemine gre belirlenmitir. Sinterleme sonras karbon katkl ve katksz numunelerdeki karbon ieriklerinin tayini; Leco CS-600 marka C/S analiz cihaznda gerekletirilmitir. Numunelerin grnt analizleri Jeol JSM-5600 Taramal Elektron Mikroskobunda yaplmtr. Metalografik inceleme iin sinterlenmi numuneler Struers Epvac marka vakumlu kalplama cihaznda epoksi reine ile kalba alnp Nikon FDX kamera balants olan Olympus marka PME3 model k metal mikroskobunda incelenmitir. Sinterlenmi numunelerde gzeneklerin kresel ap ve kresellik dalmlar; Clemex Vision PE-4.0 grnt analiz program kullanlarak SEM resimleri zerinde belirlenmitir. Basma testleri, ZWICK marka Z 050 PROLINE model mekanik test cihaznda oda scaklnda 0,5 mm/dak. basma hzyla gerekletirilmitir. Gerilme- %ekil deiim grafikleri ve hesaplamalar, Test-Xpert programnn V11-02 versiyonu kullanlarak elde edilmitir. 3. SONULAR VE DEERLEND RME Karbamitin oda scaklndaki su banyosunda numunelerden uzaklatrlmas ile oluturulan yksek oranda gzeneklilie sahip numuneler sinterleme sonrasnda da yaplarn korumulardr. retilen sinterlenmi numunelerin younluklar 2,32-4,08 g/cm3, toplam gzenek oranlar %.47,7-70,3, ak gzenek oranlar %.33,5-62,8 ve kapal gzenek oranlar %7,5-14,2 arasnda deimitir. Artan gzenek miktar ile numunelerdeki ak gzenek oran artmtr. Bu art gzeneklerin birbirleriyle balant kurmasndan kaynaklanmtr. Gzenek miktar azaldka elde edilen gzenekler birbirinden izole olarak kapal gzenekli yaplar elde edilmektedir. Karbamit miktar arttka sinterleme sonras numunelerin gzenek oranlar da artmtr. Ancak ilave edilen karbamit miktarna gre sinterleme sonras beklenen gzenek ieriklerinde azalma meydana gelmitir. Bu azalma hacimce %70 ve %80 karbamit ilave edilmesi durumunda daha fazla gereklemitir. Sinterleme esnasndaki ekme ham younlukla ters orantl olduundan daha yksek miktarda karba-
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mit kullanlarak retilen numuneler daha dk ham younlua sahip olup sinterleme sonucu nispeten daha ok younlamlardr. Sinterleme sonras numunelerde meydana gelen hacimsel ekme %4,3 ile %6,7 arasnda gereklemitir. Sinterleme sonras gzenek oran %48in zerinde olan numunelerde karbon katksnn hacim deiimi zerine nemli bir etkisi olmamtr. %48 gzenek orannda ise tm numunelerde gzenek duvarlarnn kaln olmasndan dolay artan karbon miktaryla bir miktar ekme gereklemitir. %0,8 karbon katksnda hacimsel ekme daha belirginlemitir. Sinterleme esnasnda meydana gelen boyutsal klme gzenek duvarlarnda sinterleme esnasnda meydana gelen ekmeden kaynaklanmaktadr. Sinterleme sonras karbon katkl numunelerin belirlenen karbon ierikleri Tablo 2de verilmitir. Karbon katksz sinterlenmi numunelerin karbon ierii %0,025 olarak bulunmutur. Tablo 2 : Karbon katkl numunelerin sinterleme sonras karbon ierikleri
ekil 3de farkl miktarlarda karbamit ilave edilerek retilmi ve 1200 Cde 1 saat sinterleme sonras yaklak (a) %49,0, (b) %54,2, (c) %61,4 ve (d) %70,1 gzenek ieren karbon katksz Distaloy AE numunelerin yzeylerinden alnan SEM fotoraflar verilmitir.
ekil 3 : (a) %49,0, (b) %54,2, (c) %61,4 ve (d) %70,1 gzenek ieren numunelerin yzeylerinin SEM grntleri ekil 3de verilen SEM grntlerinde belirgin bir ekilde kpks yapnn olutuu grlmektedir. Balangta ilave edilen karbamit miktarna bal olarak sinterleme sonras numunelerin gzenek miktarlar deimektedir. Gzenekler birbirlerinden hcre duvarlaryla ayrlmlardr. Yaplarda atlak oluumlarna rastlanmam ancak mikro gzenekler tespit edilmitir. Gzenek morfolojisinin karmak olmas kullanlan karbamitin dzensiz ekilli olmasndan ileri gelmektedir. Farkl oranlarda gzenek ieren karbon
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katksz Distaloy AE numunelerindeki gzeneklerin kresel ap ve kresellik deerleri Tablo 3de verilmitir. Tablo 3 : Karbon katksz numunelerdeki gzeneklerin kresel ap ve kresellik deerleri
Karbon katkl Distaloy AE tozundan elde edilen yksek oranda gzenek ieren numunelerin kresel ap ve kresellik deerleri Tablo 3de verilen deerlere ok yakn bulunmutur. Gzenek miktarnn azalmasyla; maksimum ve ortalama kresel aplar azalm, kresellik artmtr. Dk gzenek miktarlarna doru ortalama kresel aplarn giderek azalmasnn nedeni gzenek duvarlarnda sinterlenmeden kaynaklanan ekmenin baskn olmasdr. Yksek miktarlarda gzenek ieren numunelerde ortalama gzenek boyutundaki art ve maksimum gzenek boyutunun kullanlan karbamitin boyutundan byk olmas gzeneklerin birbirleriyle balant kurmas sonucudur. ekil 4-(a) karbon katksz, (b) %0,3, (c) %0,6 ve (d) %0,8 karbon katkl Distaloy AE tozundan elde edilen farkl gzeneklilie sahip numunelerin gerilme-%ekil deiim erileri verilmitir.
ekil 4 : (a) karbon katksz, (b) %0,3, (c) %0,6 ve (d) %0,8 karbon katkl farkl gzeneklilie sahip numunelere ait basma erileri Bu eriler kpks metallerin tipik basma davrann yanstmaktadr. Her bir eri elastik bir blgeye, uzun bir plato blgesine ve gerilmenin hzla artt younlama blgesine sahiptir. Gzenek miktarnn artmasyla; plato blgesinin uzunluu ve younlamann balad ekil deiimi artmaktadr. Numunelerin maksimum basma gerilmeleri (st akma gerilmeleri) ve plato gerilmeleri artan gzenek miktar
326
ile azalmaktadr. Elastik blgeden sonra numunelerde meydana gelen youn gzenek duvar krlmas nedeniyle gerilmede ani dler gereklemitir. Yaklak ayn gzeneklilie sahip numunelerde, maksimum basma mukavemetleri ve plato gerilmeleri artan karbon miktaryla bir miktar artmtr. Gzenek orannn azalmasyla karbon katksnn mukavemet zerine etkisi daha da belirginlemektedir. Ancak karbon katksnn plato blgesinin uzunluu ve younlamann balad ekil deiimi zerine belirgin bir etkisi olmamtr. ekil 5de karbon katksz, %0,3, %0,6 ve %0,8 oranlarnda karbon katkl Distaloy AE tozundan elde edilen farkl gzeneklilie sahip numunelerin maksimum basma mukavemetlerinin numunelerin ierdii gzenek miktarna gre deiimi verilmektedir.
ekil 5 : Farkl gzeneklilie sahip numunelerde karbon katksnn maksimum basma mukavemetine etkisi Numunelerin maksimum basma mukavemetleri ve elastisite modlleri srasyla; 23-133 MPa ve 0,703,43 GPa arasnda deimitir. Tm numunelerin maksimum basma mukavemetleri artan gzenek miktaryla azalmtr. Gzenek miktarnn artmasyla; maksimum ve ortalama kresel aplar artm, kresellik deerleri azalmtr. Ayn gzenek miktarlarnda numunelerin maksimum basma mukavemetleri artan karbon miktaryla bir miktar artmtr. Azalan gzenek miktaryla; karbon katksnn maksimum basma mukavemeti zerine daha belirgin etkisi olmaktadr. Yaklak %48 gzeneklilie sahip numunelerde %0,8 karbon katks maksimum basma mukavemetini %10,8 arttrmaktadr. Yaklak ayn gzeneklilie sahip numunelerin elastisite modllerinde artan karbon ieriine bal olarak nemli bir deiim gereklememitir. Ancak artan gzenek miktarna bal olarak elastisite modlleri azalmtr. lave edilen karbon miktarnn yksek oranda gzenek ieren numunelerin maksimum basma mukavemeti zerine etkisini aklayabilmek iin mikroyap incelemeleri yaplmtr. Mikroyaplardaki fazlar toz metalurji yntemi ile retilmi youn Distaloy AE kompaktlar iin literatrde verilen standart mikroyap grntleri ile karlatrlarak teyit edilmitir [4]. ekil 6da yaklak %48 gzeneklilie sahip karbon katksz ve farkl oranlarda karbon katkl Distaloy AE tozundan elde edilen farkl gzeneklilie sahip numunelerin mikroyap fotoraflar verilmektedir. Mikroyap grntlerinde; Ferrit F, Perlit P, Beynit B ve mikro gzenek G ile ifade edilmitir.
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ekil 6 : (a) karbon katksz, (b) %0,3, (c) %0,6 ve (d) %0,8 karbon katkl numunelerin mikroyap grntleri Literatrde yksek oranda gzenek ieren n alaml demir esasl kompaklarda karbonun etkisinin aratrld bir alma bulunmamaktadr. Yksek oranda gzenek ieren Distaloy AE numunelerinde; youn kompaktlarda olduu gibi [4-6], karbon miktarnn artmasyla yapy oluturan gzenek duvarlarnda ferritik yapdan perlitik ve beynitik yapya gei olduu grlmtr. Ancak bu almada sinterleme evriminin soutma aamas kontroll olarak yava yapldndan; mikroyapda beynit oluumu az gereklemi, martensit oluumuna ise rastlanmamtr. Gzenek orannn azalmasyla karbon katksnn mukavemet zerine etkisi daha da belirginlemektedir. Sonular yksek oranda gzenek ieren Distaloy AE numunelerinde yapda beynit ve martensit oluumlarnn artmasyla daha yksek mukavemet deerleri elde edilebileceine iaret etmektedir. Teekkr Bu alma T-1431 proje numarasyla stanbul niversitesi Bilimsel Aratrma Projeleri Birimi tarafndan desteklenmitir. KAYNAKLAR 1. HGANS HANDBOOK-2, Production of Sintered Components, Sweden, 2004. 2. HGANS HANDBOOK-4, Compacting of Metal Powders, Sweden, 2004. 3. HGANS-A.B., Hgans Iron and Steel Powders for Sintered Components, Sweden, 1996. 4. HGANS A.B, Hgans Handbook for Sintered Component- Metallography, Sweden, 2007. 5. CHAGNON, F., TRUDEL, Y., Designing Low, Alloy Steel Powders for Sinterhardening Applications, Metallurgy and Particulate Materials, 1-10, 1999. 6. KHORSAND, H., HABIBI, S.M., YOOZBASHIZADEA, H., JANGHORBAN K., REIHANI, S.M.S., SERAJI, H.R., ASHTARI, M., The Role of Heat Treatment on Wear Behaviors of Powder Metallurgy Low Alloy Steels, Materials and Design, 23, 667-670, 2002. 7. CHAWLA, N., DENG, X., Microstructure and Mechanical Behavior of Porous Sintered Steels, Materials Science and Engineering A, 390, 98-112, 2005. 8. MICHAILIDIS, N., STERGIOUDI, F., TSOUKNIDAS, A., PAVLIDOU, E., Compressive Response of Al-foam Produced via a Powder Sintering Process Based on a Leachable Space-holder Material, Materials Science and Engineering, 528, 1662-1667, 2011. 9. BAKAN, H.I., A Novel Water Leaching and Sintering Process for Manufacturing Highly Porous Stainless Steel, Scripta Materialia, 55, 203-206, 2006. 10. KOTAN, G., BOR. A.S., Production and Characterization of High Porosity Ti- 6Al-4V Foam by Space Holder Technique in Powder Metallurgy, Turkish J. Eng. Env. Sci, 31, 149-156, 2007. 11. GULSOY, H.O., GERMAN, R.M., Sintered Foams from Precipitation Hardened Stainless Steel Powder, Powder Metallurgy, 51(4), 350-353, 2008. 12. KREMER, K., LISZKIEWICZ, A., ADKINS, J., Development of Steel Foam Material and Structures, Technology Roadmap Program 9913 Final Report, The United States Department of Energy and American Iron and Steel Institute, 2004. 13. ALY, S.M., High Temperature Mechanical Properties of Cast as well as Powder Metallurgical Manufactured Metallic Foams, Doctorate Thesis, Stipendiat am Institut fr Eisenhttenkunde, Aachen, Deutschland, 2004.
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YAKIT HCRELERNDE KULLANILACAK GZENEKL PASLANMAZ ELK TOZ METAL PARALARIN RETM PARAMETRELERNN ARATIRILMASI
Adem KYL* ve Yusuf USTA** **Arazi,naat ve Kamulatrma Daire Bakanl, Boru Hatlaryla Petrol Tama A.. Bilkent Plaza BOTA Bilkent / Ankara, adamvillager@hotmail.com *Makina Mhendislii Blm, Mhendislik Fakltesi Gazi niversitesi 06570 Maltepe / Ankara, uyusuf@gazi.edu.tr ZET Bu almada yakt hcrelerindeki s deitiricilerinde de kullanlabilmesi dncesi ile SS316L kresel paslanmaz elik tozlarndan, bir altlk zerinde tutundurulmu gzenekli yzeye sahip paralar retilmitir. Bunun iin minimum basn-scaklk deerleri ile tozlar ve altlk arasndaki iliki incelenmitir. Ayrca; tozlarn altla balanmas iin, altln yzey przlln arttrlmas yntemi uygulanmtr. Bu amala yzey andrma teknikleri aratrlm, en dk yzey przll deeri belirlenmitir. almalar yaplrken prosesin endstrideki uygulanabilirlii gzetilmitir. Bunun yannda scaklk ve basncn, ak gzeneklilik zerindeki etkisi aratrlmtr. Yaplan deney ve testler 200 MPa presleme basnc, 500C presleme scakl, Ra=1,7 m altlk yzey przll ile gzeneklilik yzdesinin %29,6 deerlerinin yeterli balang koullar olduunu gstermitir. Anahtar Kelimeler: Yakt hcresi, gzenek, paslanmaz elik, sinterleme, przllk, toz metalurjisi.
INVESTIGATION OF PRODUCTION PARAMETERS OF POROUS STAINLESS STEEL SURFACES USED ON FUEL CELLS
ABSTRACT In this study, parts that have porous surface of SS316L spherical stainless steel powder have been produced to be used for heat exchangers of the fuel cells by designing and producing die and special punches. Minimum pressures and temperatures for compacting have been examined to have bonding between powders and a substrate. Moreover, surface roughness of the substrate has been increased in order to bond substrate and the powders. Surface etching techniques have been investigated and minimum surface roughness has been defined. Besides, the effects of temperature and pressure on open porosity have been investigated. The experiments and the tests showed that 200 MPa compacting pressure, 500C temperature and Ra=1,7 m roughness, on the substrate are enough as the initial conditions. Under these circumstances 29,6% porosity has been obtained. Keywords: Fuel cell, pore, stainless steel, sintering, surface roughness, powder metallurgy 1.GR Is deitiricilerde yzey alannn artrlmas, aktarlacak s miktarn dorudan etkilediinden, dar hacimler nedeni ile daha byk yzeyli s deitiricisi kullanm zorunluluu giderek artmaktadr. Is deitiricisinde gzenekli yzeyler kullanmak veya yzeyinde kntlar oluturmak yzey alann arttrmak iin balca yntemlerdir. Hem kntl hem de gzenekli yzeyin ayn anda imalat ise iki baarl uygulamann birletirilmesidir. Bu yzey alann nemli llerde artrmakla birlikte klcal etki (capillary effect) yardm ile iki fazl soutma (nucleate boiling) da mmkn olmakta ve s deitiricisinin verimi %300 mertebelerinde artmaktadr. Bu tr bir uygulama bakr tozlar kullanlarak yaplm, teorik snrlarn yannda bu snrlarn endstrideki uygulanabilirlii aratrlmtr. Bugn, gelien yakt
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hcreleri ve membran teknolojileri kk hacimde daha byk s aa karmaktadrlar. Yksek scaklk ve yaktn oluturduu korozif ortam bu alandaki nitelikli malzeme ihtiyacn aka gstermektedir. Mhendislik uygulamalarnn en nemli ve en ok karlalan ilemlerinden birisi, farkl scaklklardaki iki veya daha fazla akkan arasndaki s deiimidir. Is deitiricilerinin konstrksiyonunda yumuak elikler, alaml elikler, zellikle bakr gibi dier alamlar, seramikler veya zel maksatlar iin de grafit gibi malzemeler kullanlr. Bu malzemelerin seiminde korozif, scak, basnl, asitli veya bazik ortam alma koullarna dayanakllnn yan sra, zellikle metal malzemelerde imalat kolaylnn (bilhassa kaynak kabiliyeti), s iletim katsays, younluk, s yaynm katsays gibi fiziksel zellikler, pratikte standart ap ve boyutlarda imal edilebilme ve fiyat gibi etkenler gz nnde tutulmaldr [1]. Paslanmaz elik endstriyel tesislerde, korozyon dayanm gereken yerlerde ska kullanlr. Paslanmaz elikten mamul s deitiricileri yakt hcreleri alanndaki malzeme gereksinimini, zellikle korozyona olan direnci nedeniyle karlamaktadr. Bilindii gibi yakt hcrelerinde (yakt pillerinde); elektrokimyasal tepkime sonucu aa kan sy uzaklatrmak, bu teknolojinin verimli olarak kullanlabilirliini etkilemektedir. Yakt hcreleri yaplar gerei kk ve karmak geometriye sahip olduundan oluan sy atabilmek iin gerekli mekanizmann boyutlar snrlanmaktadr. Buna karn, yakt hcresinin gc arttka aa kan s da doal olarak artacak ve daha byk kapasiteli s deitirici kullanm zorunlu hale gelecektir. Liter ve Kaviany [2] yaptklar almalarnda, gzenekli yzeylere sahip s deitiricileri ile klcal etkisiyle (capillary effect) ift fazl s transferi (sv ve gaz) ve ayn zamanda artrlm yzey alan elde etmiler ve bylece dz bir plakaya gre %300 gibi bir artla s transferi kapasitesine ulalabileceini gstermilerdir. Ulalan bu sonu, yakt hcresi ve elektronik cihazlarn soutucularnda gzenekli yzeylere sahip s deitiricilerinin kullanlabilecei ynnde bir motivasyon oluturmutur. Literatr incelendiinde, gzenekli yzeylerin oluturulabilmesi iin zellikle bata kimyasal olmak zere eitli yntemler olduu grlmektedir [3-6]. Ancak, kontrol edilebilir ve ak gzeneklilie sahip paralar iin toz metalurjisi yntemi nemli bir zmdr. Bunun yan sra iki farkl sv arasnda szdrmazl salamak amacyla bir plaka zerinde gzenekli yapy oluturmak iin de yine T/M yntemi nemli bir alternatif olacaktr. Tipik T/M paralarn yapsal teorik younluu %85-%99,9 aralnda deiirken, gzenekli yap iin kullanlan teknik ve sinterlemeyle %25 ile %85 aras teorik younluklu paralar retilebilmektedir. Filtreler, kendi kendini yalayabilen yataklar, bataryalarn elektrotlar, ak kontrol cihazlar, ak snrlandrclar, darbe emiciler ile kpks yaplar bu paralara rnek olarak verilebilir [7]. Gzeneklilik basn altnda dmekte younluk st snrna yaklamaktadr. Yksek gzeneklilie sahip olabilmek iin dk basnta presleme gerekirken, tozlarn bir altla tutunabilmesi iin sktrma basncnn artrlmas gerekmektedir. Bakr ile yaplan almalarda; minimum basn seviyesinin 15MPa civarnda olabilecei, ancak tutunma iin scaklk altnda preslemenin yaplmas gerektii ve bunun da minimum 350C olmas gerektii belirtilmektedir [8]. Bakr tozlarndan baar ile retilen gzenekli yzeylerin [8], yakt hcrelerinin s deitiricilerinde anlan zellikleri nedeniyle paslanmaz elikten retilmesi fikri bu almann kaynan oluturmaktadr. Tozlar ve yzey arasnda gl bir ba salamak amacyla, lk, hatta scak presleme zorunluluu vardr. Ko, M. arkadalar yaptklar almada, sinterlemenin gerekli olaca, oksidasyonu engellemek iin sktrmann ve sinterlemenin korumal atmosferde yaplmasnn gerekecei, yksek basn ve scaklk deerleri her ne kadar gl ve kompakt bir yap iin gerekse de gzeneklilii snrlad, tutarl gzeneklilik seviyeleri iin uygun toz boyutunun salanmas gerektii sonucuna varmlardr [9]. Is deitiricisi olarak kullanabilmek iin, sv ile ekillendirme (hydroforming) yntemi kullanlarak, 0,05 mm kalnlndaki SS304 levha ile 0,5x0,5 mm ok ince ak kanall bipolar levhalar retilmitir. Bu kanallar ile s transferi svs iin ak yollar oluturulmutur [10]. Benzer bir almada, dorudan metal lazer sinterleme kullanlarak, sinterlenmi gzenekli 316L paslanmaz elik bileenlerin ileme koullar ve mikro yapsal zellikler incelenmitir. Sinterlenmi rneklerde genellikle %2155 gzeneklilik elde edilmitir [11]. Yakt hcreleri oluan kimyasal olaylar nedeniyle korozif bir ortam oluturmaktadr. stenitik 316L malzeme ile 500C scaklkta iletilen bir hcrede deneyler yaplarak, hava oksidasyonunun yksek olduu 500C st scaklklarda paslanmaz elik kullanmann uygun olmayaca belirlemitir [12]. 300 saat sonra 800Cdeki yakt hcresinde hava oksidasyonundan dolay paslanmaz elik balang ktlesinin %5 orannda azald grlmtr [12]. Yakt hcrelerinin; dk emisyon ve grlt seviyeleri ile H2nin temel enerji kayna olmas durumundaki yksek verimlilikleri nedeniyle yakn gelecekte nemli rol oynayaca tahmin edilmektedir [13]. Zamanla fosil yaktlarn azalmasndan duyulan endie sonras iten yanmal motorlara gre pahal bir yntem olan yakt hcreleriyle elektrik retme, yksek verimlilii ve emisyonsuz olmas sayesinde tekrar aratrlmaya ve gelitirilmeye balamtr [14].
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Bugne kadar olan yakt hcrelerinin ksaca karlatrlmas Tablo 1de verilmitir [15]. ekil 1de yaps verilen yakt pilinde katot tarafndaki ak kanalndan hava geerken, anot tarafndaki ak kanalndan hidrojen (yakt) gemektedir. Anot tarafndaki gzenekli tabakadan katalizr tabakaya geen hidrojen, platin katalizr sayesinde elektronlarn brakr [16].
ekil 1. Yakt hcresi (PEM) ve tabannda gzenekli tabaka bulunan kanaldaki ak. Tablo 1. Yakt hcrelerinin ksaca karlatrlmas. alma Yakt Avantajlar Dezavantajlar Aral Dk scaklk yksek <1W enerji younluu, hafif, ok saf H2, Pahal H2 200kW hzl ilk alma, Kat katalizr Elektrolit 1W 250kW H2, CO2, CH4 Yksek verim, yakt eitlilii, ucuz katalizr, hzl ilk alma, Kat Elektrolit Katottaki aktivasyon kayb dk, sv elektrolit, yksek temas Safl dk hidrojen kullanlabilir, sv elektrolit, yksek temas Yksek verim, yakt eitlilii, ucuz katalizr, Yksek Scaklk, Sv Elektrolit, yksek Korozyon temas Dk verim, metanoln zehirli bir yakt olmas Yaktn elde edilmesi zor Yksek Scaklk, Korozyon, Hcre retimi zor ve pahal ok saf H2, Pahal katalizr
Yakt Hcresi Tr Proton geirgen zarl yakt hcresi (PEMFC)
alma Scakl 20-100C
Uygulama Alanlar Portatif Sistemler, Jeneratr, Askeri sistemler Elektrik santralleri, Orta lekli iletmeler iin s ve elektrik, Portatif Sistemler Uzay aralar Elektrik santralleri, Orta lekli iletmeler iin s ve elektrik
Kat oksit yakt hcresi (SOFC)
5001000C
Alkaline (bazik) yakt hcresi (AFC) Fosforik Asit yakt hcresi (PAFC)
50-100C
200W 10kW
H2
190220C
10kW 1MW
H2
Eriyik Karbonat yakt hcresi (MCFC) Dorudan Metanol (veya Etanol) yakt hcresi (DMFC veya DEFC) Dorudan Bor hidrr yakt hcresi (DBFC) Dorudan Glikoz yakt hcresi (Biyolojik yakt hcreleri) (DGFC)
600650C
200kW 10MW
H2,CO
Elektrik santralleri
50-100C
<1W 200W
CH3OH, Ucuz Yakt, Kolay (C2H5OH) depolanan sv yakt
Portatif Sistemler
20-100C
1W 200W
BH4-1
Alternatif yakt, yksek ak u gerilimi
Deneme aamasnda
10-50C
1W 20W
C6H12O6
Yakt vcutta bol miktarda bulunmakta, Glikozdan bakterisiz olarak akm retimi
Dk g younluu
Kalp pili, la pompas, sensr
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2. DENEYSEL ALIMALAR almada 55 mm apl metal toz sktrma kalbnn tm paralarnn imalat yaplm, imalatlar tamamlanarak montajlar yaplan sktrma kalbnn mekanik ksmlarnn yan sra elektriksel ksmlarnn hesap ve analizleri yaplmtr. Modellemede PHONEICS yazlm kullanlm, kalbn oda scaklndan 500Clik bir scakla ulamas iin gereken zaman 2250 saniye (~37,5 dk) olarak bulunmutur (ekil 2).
ekil 2. Toz sktrma kalbnn kat modeli ve stma sresi sonunda kalpta oluan scaklk dalm. Temin edilen 150 m apnda kresel paslanmaz elik tozu ierisinde bulunan daha kk apta tozlar ortamdan ak gzeneklilii etkileyeceinden, 75 m alt tozlar birbirinden ayrlmtr. Deneylerde 100 m kalnlnda SS316L paslanmaz elik levhalar altlk olarak kullanlmtr. 2.1. Toz Presleme Deney Dzenei ve Deneyinin Yapl Tozlarn preslenmesi iin, mekanik laboratuarnda bulunan DARTEC marka niversal ekme-basma cihaz kullanlmtr (ekil 3). Cihazn kontrol nitesi kullanlarak basma yk profili oluturulmutur.
ekil 3. Metal toz presleme deney dzenei. ncelikle, dz yzeyli numuneler oluturulmaya allmtr. Bu maksatla 55 mm apnda kesilen altlklarn, tozlara dorudan temas edecek yzeyleri zmparalanarak hazrlanmtr.75 m elek alt tozlar, yaklak 2 mm kalnlkta bir katman oluturacak ekilde alt kalba koyulmutur. Bu tozlarn zerine altlklar yerletirilmitir. Daha sonra st zmba yerletirilerek izolasyonlar sarlm ve kalp stlmtr. nceden ayarlanm basn deerine 10 saniyede ulalacak ekilde rampa girii uygulanm ve bu basn altnda 60 s beklenmitir. Bu sre bitiminde pres st enesi
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kalp st zmbasndan ayrlm, izolasyon ceketleri karlarak kalbn soumas beklenmitir. ekil 4te kalptan kan numuneler grlmektedir.
ekil 4. a) Presleme, b) Numunenin karlmas, c) 450C scaklk ve 100 MPa basn altnda tozlarn altla tutunmam ancak kendi aralarnda tutunmu hali, d) 490C presleme scakl ve 150 MPa basn altnda altla blgesel tutunmu bir numune. Tozlarn kendi aralarnda tutunmas ancak altla tutunmamalar, altlklara ait przllk deerlerinin yeterli olmadn ortaya koymutur. Yzey przll artrma ilemi ncelikle kaba zmparalarla gereklemi, ancak yine sonu alnamamtr. Bu durumda daha etkin bir yntem kullanlarak daha yksek yzey przllk deerlerine ulalmas gerekmektedir. 2.2. Kimyasal Yntemle Yzey Przllnn Artrlmas Elektrolitik bir ortam ierisinde bekleyen metal ierisinde aktiflikleri farkl blgeler ve mikro yaplar arasnda reaksiyon balar. Bu reaksiyon neticesinde kimyasal korozyon balar. Kimyasal korozyon metalin ierisinde bulunduu ortamdaki dier bir elementle dorudan elektron alveriinin sz konusu olduu bir reaksiyondur. Elektrokimyasal korozyonda konum olarak ounlukla farkl yerlerde oluan iki ksmi reaksiyon vardr. Genel btn metallerde ve zellikle paslanmaz eliklerde elektrokimyasal korozyon hasarlarna daha ok rastlanmaktadr. almada altlk olarak kullanlan SS316L levha (100 m kalnlnda) anot olarak kullanlmtr. Katot olarak yine ayn levhadan oluturulmu levha kullanlmtr. Elektrolitik sv ierisinde elektrot balants olmayacak ekilde katot balant ucu karlmtr Anot levhasnn tek taraf (pitting korozyonunun istendii yzey) 80 mesh zmpara ile przlendirilmitir. Anodun bu przlendirilmi yzeyi katot tarafna doru konumlandrlmtr. Przllk deneyleri nce farkl zeltilerde oda scaklnda yaplm ancak belirgin bir przllk art gzlenmemitir. Gzlemlenen NaCl ierisinde scaklk art olduunda korozyonun hzla arttdr. Bu gzlem, zelti kab ierisindeki FeCl2 floklar oluumunun hzlanmas ve belirginlemesidir (ekil 5).
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ekil 5. Farkl scaklklardaki denemeler ve NaCl zeltisinde FeCl2 bloklar. Bunun zerine, 70C zerinde bir scakla sahip %(w/w)20 NaCl zeltisi (ktlece %20 NaCl zeltisi: 1000g NaCl zeltisinde 200 g kat NaCl bulunduunu ifade etmektedir), ekil 6da grld gibi akm verilip, zeltide reaksiyon balatlmtr.
ekil 6. Altlklar iin hazrlanan hzlandrlm deney dzenei.
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Deney dzenei iin kullanlan g kayna, 32V-2A DC g kaynadr. Bekleme sresi 8 dakika olarak belirlenmitir. lk yksek przllk deerine sahip yzeyler elde edilip, olumlu sonular alnmasndan sonra artlar birbiriyle ayn sekiz adet altlk hazrlanmtr. Bu artlara uygun olarak balayan elektro-kimyasal reaksiyonda; zelti ierisindeki klor iyonlar, anottan gelen demir katyonlar ile birleerek, belirli bir sre ierisinde oyuklanma korozyonu gereklemektedir. Deney srasnda zaman ilerledike g kaynandan okunan besleme geriliminde bir art gzlemlenmitir (balangtaki gerilim 3,8V-4V arasndadr). Gerilimdeki artn nedeni zeltinin iletkenliindeki azalmadr. zelti iletkenliinin azalmas, serbest Cl- iyonlarnn azalmasn gstermektedir. Bu durum, reaksiyonunun gereklemekte olduunun gstergesidir. letkenliin azalmasyla meydana gelen zelti i direncinin art gerilimde ykselme olarak kendini gstermektedir. Bu artn 8 dakika ierisindeki deiimi ekil 7de grlmektedir. Scakln art reaksiyon hzn artrdndan sre ksalmtr. Deneyin oda scaklna yaplmas durumunda reaksiyon hz dm, pitting korozyonu sresi artmtr.
ekil 7. Elektrolitik zelti direnci. Elde edilen sekiz adet altln przllk deerleri Taylor Hubson SURTRONIC 3+ przllk lm cihaz ile llmtr. lmler sonucunda elde edilen ortalama yzey przllk deeri (Ra) ve profildeki tepe-ukur ykseklikleri (Rz) przllk deerleri ekil 8deki grafikte verilmitir. Ra ortalama deeri 1,7 m civarnda iken Rz deerleri 8,5818,93 m arasnda deimektedir. Ortalama Rz deeri 14,4 m civarndadr. Bu fark uniform bir yzey dalm olmadn gstermektedir. Uniform kabul edilebilir bir yzeyin Rz/Ra=4 oranna sahip olmas gerekir [19, 20].
ekil 8. Altlk numunelerine ait Ra ve Rz deerleri. Przllk deerlerinin llmesinden sonra, saysal ortama grnt aktarabilen OLYMPUS GX71 optik mikroskopta numunelerin yzey morfolojileri incelenmitir. Elde edilen en dk ve en yksek przl yzeyler ekil 9da grlmektedir.
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Ra=0,77 m, Rz=8,58 m (Dk Przllk deerine sahip altlk)
Ra=2,30 m, Rz=17,48 m (Yksek Przllk deerine sahip altlk)
ekil 9. En dk ve en yksek przl numunelere ait yzey grntleri (50x). Bu artlarda; przllk deerleri Ra=0,77 m, Rz=8,58 m olarak llm olan dk przlk deerine sahip altlk kullanlarak T=500C ve P=150 MPa artlarnda preslenmi, ancak altla tutunma gereklememitir. Tozlar geri kalan przlendirilmi altlklara T=500C ve P=200 MPa artlarnda preslenmi, hepsinde hem tozlar hem de altlk arasnda tutunma salanmtr. Altla tutunan bu numuneler, 1150C scaklkta 30 dakika beklenmek suretiyle korumal atmosferde sinterlenmitir. Koruyucu gaz olarak %95 Argon %5 Hidrojen karm kullanlmtr. Sinterleme ilemi PROTHERM marka PTF 12/38/250 model tp frnda gerekletirilmitir (ekil 10).
ekil 10. Sinterleme frn ve uygulanan scaklk profili. Bu artlarda sinterlenen malzeme zerinde grnr renk deiimleri meydana gelmitir. Yani numunede sinterleme srasnda oksijenle reaksiyon gereklemitir. Buna gereke olarak koruyucu gaz atmosferinin yetersiz kald dnlebilir. Bu durum koruyucu gaz karm oranndan veya frna giren koruyucu gaz karmnn debisinden olabilecei gibi, tp frnn giriinde ve knda dardan havann girii tamamen engellenememi de olabilir. Bunun yannda, disk eklinde giren malzemede ekil deiiklikleri meydana gelmitir. Altln tutunduu yzeyde meydana gelen bombenin derinlii 3mm civarndadr (ekil 11).
ekil 11.Sinterleme frnndan kan numunelerin geometrilerindeki deiim.
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Gzeneklilik deerlerinin belirlenmesi iin numuneler incelemeye alnacak ekilde yzeyleri parlatlarak OLYMPUS GX71 optik mikroskopta incelenmitir. Grntler dzenlendikten sonra Image-JTM grnt analiz yazlm yardmyla binary modunda (ikili renk modu) gzeneklilik lm yaplmtr (ekil 12). Her numunenin farkl blgelerinden 7 adet grnt analiz edilmi ve numunelerin gzeneklilik oran %29,6 olarak tespit edilmitir.
ekil 12. Gzeneklilik analizi iin alnan resim ve siyah-beyaza dntrlm grnts. Gzeneklilik deerleri ierisinde en byk deer %35,6 en kk gzeneklilik deeri ise %23,3tr. 3. SONULAR VE NERLER almada; farkl geometrilere sahip zmbalarla scaklk, basn ve toz boyutu parametrelerinin aratrlmas hedeflenmitir. Ancak; 500C scaklk ve 50 MPa basn altnda tozlar birbiri arasnda tutunurken altla yapma salanamamtr. Basn deeri 200 MPa deerine kadar testler yaplmtr. Bu nedenle gzeneklilik testlerinden nce altlk przllnn artrlmas konusuna younlalmtr. Bylece, farkl yzey geometrileri (farkl zmba kullanm) yerine sadece dz yzeyli numuneler elde edilmitir (tek tip zmba kullanlmtr). Gerek kalptaki olumsuz deformasyonu nlemek ve gerekse uygulanabilirlik bakmndan maksimum deerler olarak, 200 MPa basn ve 530C scaklk kullanlm ancak, numunelerde snrl ve blgesel olarak altla tutunma gzlenmitir. Altlk malzemesinin yzeyine herhangi bir ilem yaplmakszn, tozlarla altlk arasnda tutunma salanamamtr. Bunun zerine 80, 150 ve 240 meshlik zmparalar ile altlk yzeyi przlendirilmi ancak yeterli bir tutunma yine salanamamtr. Altln tutunmasn glendirecek kimyasal bir przllk artrma almas yaplarak, mekanik tutunma iin minimum przllk deerleri belirlenmeye allmtr. Kullanlan kimyasal zeltilerin farkl deriimlerinde przll artracak olan korozyon gzlemlenmitir. NaCl, HCl ve Fe3Cl zeltileri kullanlarak przlendirme almalar yaplm, en byk oyuklanma (przllk) NaCl zeltisi ierisinde gereklemitir. Bu durum literatrdeki dier almalarla [3,17] paralellik gstermektedir. Elde edilen ortalama przllk deeri Ra=1,7 m, ortalama Rz deeri ise 14,4 m civarndadr. Rz/Ra orannn yaklak 8 belirlenmesi, przlln uniform dalmadn gstermektedir. Altlklarda meydana gelen pitting korozyonu deliklerinin akm, zaman, konsantrasyon ve levha kalnl parametreleri ile farkllatrlabilecei grlmektedir. Altlk numunesi zerindeki korozyon, alt ve st blgede farkllk gstermektedir. Mikroskopta anot altln, akm giri ve k taraflar incelendiinde, anot akm k tarafnda belirgin bir korozyon olduu grlmektedir. Kimyasal yntemle przlendirme almas yaplrken, her taraftan eit ekilde przlenmi, daha uniform przl yzeyin artlar aratrlmaldr. Yaplan almalarda, zellikle sinterleme ileminde, artlarnn yeterince salanamad anlalmaktadr. Gelecekte yaplacak almalardan salkl sonularn alnabilmesi iin laboratuvar artlarnn (sinterleme ilemi) iyiletirilmesi nerilmektedir. alma srasnda dz yzeylere sahip numuneler elde edilmitir. Altla tutunmann baar ile salanmasnn ardndan, yzey alann artrmak amacyla mikro kanallarn bulunduu numuneler elde edilmeli ve bunlarn gzeneklilikleri aratrlmaldr. Kimyasal yntemden farkl olarak elektroerezyon yntemi, daha kontrol edilebilir yzey przlendirme imkan sunabilir. Bu sebeple, yzey przlendirmede elektroerezyonla przllk artrma ynteminin kullanlmas nerilmektedir. Analiz neticesinde, minimum artlarda, tutunmay salayacak gzeneklilik oran %29,6 olarak tespit edilmitir. Przlln artrlmas ile tutunmay salayan snr gzeneklilik deerlerinin deiebilecei grlmtr.
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TEEKKR Bu alma Gazi niversitesi Bilimsel Aratrma Projeleri tarafndan 06/2010-56 kodlu proje olarak desteklenmitir. Teekkr bir bor biliriz. KAYNAKLAR 1. nternet: Trk Toz Metalurjisi Dernei Toz Metalurjisi retim Teknikleri http://www.turktoz.gazi.edu.tr/ttmd_ tr.htm (2009). 2. Liter S.G., Kaviany M., Pool-boiling CHF enhancement by modulated porous-layer coating: theory and experiment, International Journal of Heat and Mass Transfer, 44: 42874311 (2001). 3. Qiao, Y.X., Zheng, Y.G., Okafor, P.C., Ke, W., Electrochemical behaviour of high nitrogen bearing stainless steelin acidic cloride solution: Effect of oxygen, acid concentration and surface roughness, Electrochimica Acta., 54: 22982304 (2009). 4. Sato, S., Enoeda, M., Kuroda, T., Oharo, Y., Mohri, K., Cardella, A., Characteristic evaluation of HIP bonded SS/DSCu joints for surface roughness, Fusion Engineering and Design, 58-59: 749754 (2001). 5. Torikai, Y., Penzhorn, R.D., Matsuyama, M., Watanabe, K., Tritium uptake by SS316 and its decontamination, Journal of Nuclear Materials, 329-333: 16241628 (2004). 6. Wang, Y., Northwood, D.O., An investigation into polypyrrole-coated 316L stainless steel as a bipolar plate material for PEM fuel cells, Journal of Power Sources., 163: 500508 (2006). 7. Neikov O., Naboychenko S., Mourachova I., Gopienko V.,Frishberg I., Handbook Nonferrous Metal Powders: Technologies and Applications, Elsevier, Amsterdam, 212-213 (2009). 8. Cora . N., Usta Y., Ko Y., Micro-manufacturing of micro-scale porous surface structures for enhanced heat transfer applications: an experimental process optimization study Journal Of Micromechanics And Microengineering, 1-19 (2009) . 9. Ko, M, Usta, Y., Karako, A., Investigations on thermo-mechanical fabrication of micro-scale porous surface features, Journal of Power Sources., 179: 592602 (2008). 10. Mahabunphachai, S., Ko, M., Ni, J., Development of a novel process for manufacturing of fuel cell bipolar plates: internal pressure assisted embossing of microchannels with in-die mechanical joining, 2006 ASME International Conference on Manufacturing Science and Engineering, MSEC2006-21034, Ypsilanti, 1-5 (2006). 11. Gu, D., Shen, Y., Processing conditions and microstructural features of porous 316L stainless steel components by DMLS-mechanical fabrication of micro-scale porous surface features, Applied Surface Science, 255: 18801887 (2008). 12. Molin, S., Gazda, M., Kusz, B., Jasinski, P., Evaluation of 316 L porous stainless steel for SOFC support, Journal of the European Ceramic Society, 29: 757762 (2009). 13. nternet: Hacettepe niversitesi Yakt Hcrelerinin Tarihesi http://yunus.hacettepe.edu.tr/~yilser/yakitpili. htm (2010). 14. nternet: University of Denver The Telegraph Line: Batteries http://mysite.du.edu/~jcalvert/ (2010). 15. nternet: The Hebrew University of Jerusalem The Institute of Chemistry Origin of the Electric Current: Galvanic Batteries http://chem.ch.huji.ac.il/history/ grove.htm (2010). 16. F. Barbir, PEM Fuel Cells : Theory and Practice, Elsevier, (2005). 17. Dndar F. , PEM tipi yakt hcrelerinde kullanlan katalizrlerde farkl karbon destei kullanlarak yzey alannn arttrlmas ve kinetik zelliklerinin gelitirilmesi, Yksek Lisans Tezi, Gebze Yksek Teknoloji Enstits Mhendislik ve Fen Bilimleri Enstits, Gebze, 4-10 (2006). 18. Berning, T., Djilali, N., Transport Phenomena in a PEM Fuel Cell: A Parametric Study Using a Three-Dimensional Computational Model Transport phenomena in a PEM fuel cell, 11th Canadian Hydrogen Conference, Victoria, 699-707 (2001). 19. nternet: TMMOB naat Mhendisleri Odas imento Tipinin Donat Korozyonuna Etkisi http://www.e-kutuphane.imo.org.tr/pdf/3157.pdf (2010). 20. nternet: TMMOB Metalurji Mhendisleri Odas AISI 316L Tipi stenitik Paslanmaz eliklerin Taneler Aras Korozyona Duyarllnn Elektrokimyasal Polarizasyon Yntemiyle Belirlenmesi http://www.metalurji.org.tr/dergi/ dergi140/ d140_5061.pdf, (2010). 21. EN ISO 1302:2002, Geometrical Product Specifications (GPS) - Indication of surface texture in technical product documentation, International Standard ISO, 90-93 (2002). 22. TS 2040 EN ISO 1302, Geometrik mamul zellikleri (GM) Teknik mamul dokmantasyonunda yzey durumlarnn gsterilii, Trk Standard, (2005).
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TOZ METAL Al MALZEMELERDE GZENEKLLK ORANININ ELEKTRK LETKENLNE ETKS

Adem Kurt, Ahmet Ayata ve Fatih Iss Gazi niversitesi, Teknik Eitim Fakltesi,06500 Ankara-Trkiye ademkurt@gazi.edu.tr, ahmetayata42@gmail.com ZET Toz metal alminyum malzemelerin kullanm alan gn getike artmaktadr. Kullanm alanlarnn genilemesinde toz metal malzemelerin zelliklerinin belirlenmesi byk neme sahiptir. Her belirlenen zellik yeni kullanm alanlar oluturmaktadr. Bu amala bu almada toz metal Al malzemelerin gzeneklilik oranna bal elektrik iletkenlikleri aratrlmtr. Bu amala 200, 250 ve 300 MPa sktrma basnlarnda toz metal numuneler preslenerek, ham ve sinterlenmi younluklar belirlenmi, gzenek dalmlar ve gzenek ekilleri mikro yap incelemesi ile tespit edilmitir. Sonrada bu numunelerin elektrik iletkenlikleri llerek gzeneklilik oranna gre iletkenlik deiimleri belirlenmitir. alma sonunda artan gzeneklilik oranna bal olarak elektrik iletkenliinde azalma olduu grlmtr. Anahtar kelimeler: Toz metal Al malzemeler, gzeneklilik, elektrik iletkenlii
THE EFFECT OF POROSITY RATE ON ELECTRICAL CONDUCTUVITY OF Al POWDER MATERIALS

ABSTRACT Use of Al powder materials increases recently. Defining of a property of the Al powder has an important role to implement of the powder in another area. Every new property of a material defines a new application area. As the purpose of this study, electrical conductivity of Al powder materials, were investigated in term of porosity. For this purpose, 200, 250 and 300 MPa compression pressures were used and the green and sintered densities were determined, the pore distribution and pore shapes have been detected by micro-structural analysis. Then the electrical conductivity of the samples were determined by measuring changes in conductivity according to the amount of the porosity. Decrease in electrical conductivity was observed with the increasing porosity 1.GR Toz metalurjisi; elementel veya alam tozlarn birbirleriyle kartrlarak retimi yaplacak para kalbnn ierisinde sktrlp sonra da atmosfer kontroll bir frn ierisinde sinterlenerek partikller arasnda metalurjik bir ba oluuncaya kadar tutulmas sreleri ieren bir imalat yntemidir. Toz metalurjisi karmak ekilli paralarn son boyutta retilmesinde ok ekonomik bir yntemdir. Bunun dnda u avantajlar da iermektedir [1] . Karmak ekilli ve basit paralarn retiminde son derece uygun maliyetli bir yntemdir, hurda kayb yoktur ve daha az ikincil ilemler gerektirir, bileenlerin fiziksel ve mekanik zelliklerine yakn paralar retilir, retilecek paralarn younluk kontrol mmkndr, ikincil ilemler uygulayarak deiik zellikleri iyiletirilebilir. Alminyum toz metalurjisi sreci drt temel admdan oluur bunlar; Kontroll saflk ve boyuttaki Al tozlar alamlanacak metal tozlar ile kartrlrlar. Genellikle partikllerin birbirleriyle ve kalp duvar ile souk kaynak yapmamalar iin toz yalayclar ilave edilir.
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n kartrma yaplm tozlar zel yaplm metal kalp ierisinde ham mukavemet kazandrmak iin preslenirler. n kartrlm Al tozlar dk basnlarda veya enjeksiyonla yksek younluklara karlrlar. 180 MPada % 90 ve 375 MPada % 95 younlua ulaabilirler. Ham younlukla, ham mukavemet 22 MPa ile 150 MPa arasna kabilmektedir. Ham mukavemet kazanm paralar atmosfer kontroll bir frnda ergime scaklnn altnda bir scaklkta sinterlenirler. Bu srete paracklar arasnda metalurjik ba geliir ve istenilen fiziksel ve mekanik zellikler bir araya getirilmi olur. Alminyumda oksit olumas sinterlemeyi zorlatrr. Bunun iin sinterleme hidrojen, azot ieren ortamlarda yaplmaldr. Birok Al alamlar 535585 oC scaklklarda 720 dakika srelerde sinterlenirler [2]. Azot atmosferi tavsiye edilir. Al T/M malzemelerin zellikleri retim ekline gre deiebilmektedir. Mekanik zellikler younlua bal olarak 110 MPa ile 345 MPa arasnda deiebilmektedir. Sinterleme scakl, sresi ve atmosferi bunlar etkileyebilmektedir. Toz metal Al malzemeler bu zelliklerinin dnda elektrik ve termal iletkenliin ve korozyon direncinin yksek olmas gibi zellikleri nedeniyle bu alanlarda da kullanlmaktadr. Bu sebeple bu almada farkl gzeneklilie sahip Al toz metal paralarn elektrik iletkenlikleri llerek gzenekliliin elektrik iletkenliine etkisi aratrlmtr. 2. DENEYSEL ALIMALAR Bu almada ortalama 51 m boyutunda elementsel Al tozlar kullanlmtr. Al tozlar 200, 250 ve 300 MPa sktrma basnlarnda preslenerek, 6,35 x 12,7 x 31,7 mm boyutlarnda toz metal Al numuneler retilmi, bu numunelerin ham ve sinterlenmi younluklar belirlenmitir. Ayrca younlua bal gzenek dalmlar ve gzenek ekilleri mikro yap incelemesi ile tespit edilmitir. Sonrada bu numunelerin elektrik iletkenlikleri llerek gzeneklilik oranna gre iletkenlik deiimleri belirlenmitir. Bu almada kullanlan Al tozlarn boyut analiz sonular aada ekil 1de verilmitir.
ekil1. Deneylerde kullanlan Al tozlarn boyut dalm
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Farkl basnlarda preslenen numunelerin ham younluklar belirlenerek daha sonra 500, 540 ve 580oCde 45 dakika sreyle argon atmosferinde sinterlenmilerdir. Tablo 1de numunelere ait ham ve sinterlenmi younluklar verilmitir. Tablo 1. Toz metal Al numunelerin ham ve sinterlenmi younluklar Sinterlenmi Younluk (%) Basn 200 MPa 250 MPa 300 MPa Ham Younluk (%) 89 91,5 94 500 C 91 92,6 94,4 540C 91,5 93 95,2 580 C 91,7 93,3 95,5
ekil 2. T/M Al numunelerin sinterleme scaklna bal younluk deiimleri Sinterlenmi numunelere daha sonra elektrik iletkenlik testleri uygulanmtr. 3.SONULAR VE TARTIMA 3.1 Younlama Bu almada farkl basnlarda preslenen ve farkl scaklkta sinterlenmi numunelerin basnca ve scakla bal younluk deiimleri Tablo 1de verilmitir. Tablodan grlecei gibi 200, 250 ve 300 MPa presleme basnlarnda younluk deiimi % 89, % 91.5 ve % 94 olarak elde edilmitir. Artan presleme basncyla kalp iindeki tozlar birbirleri zerinden kayarak younlama davran gstermilerdir. Artan presleme basncyla toz partikllerin bir araya gelme oran artm bunun sonucu olarak younluk art elde edilmitir. Presleme ile ham mukavemet kazandrlan numuneler sinterleme ilemi ile partikller ve toz taneleri arasnda metalurjik bir ba oluturularak mukavemetlerinin art salanmtr. ekil 2 de verildii gibi sinterleme scakl 500oCde en dk presleme basnc olan 200 MPada younluk %89dan %91e, 540oCde %91.5 ve 580oCde %91.7 younluklara ulalmtr. Artan sinterleme scakl ham younlua gre bir younluk artna sebep olmakla birlikte sinterleme scaklnn sinterlenmi younluk artna etkisi artan presleme basncyla dt grlmektedir. rnein 200 MPa presleme basncnda %89 ham younluktan 580oC sinterleme scaklnda younluk %91.7 ye karak %2.7lik bir at gsterirken 250 MPada %1.8, 300 MPa da %1.5lik bir art gstermektedir. Ham younluk arttka partikller aras temasn artmas, bzlme orann drerek younlama orannn da azalmasna sebep olduu dnlmektedir.
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3.2 Elektriksel zellikler Toz metal Al malzemelerin gzeneklilie bal olarak elektrik iletkenliklerinin belirlenmesi amacyla yaplan bu almada %8.3, %6.7 ve %4.5 orannda gzeneklilie sahip numuneler kullanlarak ve bunlara 10 Ae kadar akm verilerek gzeneklilie bal gerilimleri llm ve gzenek miktarnn elektrik iletkenliine etkisi belirlenmitir. ekil 3de presleme basncna bal oluan gzenek durumuna gre toz metal numunenin akm-gerilim ilikisi verilmitir.
ekil 3. Presleme basncnn elektrik iletkenliine etkisi ekil 3 de grld gibi 200 MPa dk presleme basncnda % 8.3 gzeneklilikte 1 volt gerilimde 8 A akm geerken %6.5 ve %4.5 gzenekli numunelerde 1 volt gerilimde 9.5 A akm gemektedir. Bilindii gibi tam youn bir katya bir elektriksel alan uygulanrsa, serbest elektronlar hzlanrlar ve kafes atomlaryla arparak kinetik enerjilerini azaltr veya kaybederler. Meydana gelen akm, uygulanan elektriksel alann iddeti ve arpma frekans ile belirlenen ortalama elektron hz ile orantldr. deal bir kristalde elektronlar direnle karlamadan hareket ederler. Fakat gerek kristallerde elektronlar fononlar, dislokasyonlar, boluklar yabanc katk atomlar ve herhangi kafes kusurlaryla arprlar [3]. Bunlarda elektronlarn hareketini snrlandrrlar. Toz metal malzemelerde gzenekler boluklar oluturduundan elektronlar bu boluklara arparak kinetik enerjilerini azaltmaktalar ve dolaysyla boluklar elektronlarn hareketini snrlandrdndan iletkenlik deerlerinin dmesine neden olmaktadrlar. Ayrca toz metal malzemelerde gerek sinterleme ncesi toz partikl yzeylerinde oluan oksitler, gerekse sinterleme srasnda sinter atmosferine bal oluabilecek oksitlerin toz metal numunelerde elektrik iletkenliini drd yaplan almalarda belirtilmitir [4].
ekil 4. Sinterleme scaklnn elektrik iletkenliine etkisi
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ekil 4de sinterleme scaklnn toz metal Al numunelerde elektrik iletkenliine etkisi grlmektedir.Burada da gzeneklilie benzer bir iletkenlik davran grlmektedir. Dk sinterleme scaklnda gzenek kapanma oran azaldndan baka bir ifadeyle daha fazla gzeneklili yap elde edildiinden dk basnlarda preslenmi numunenin elektrik iletkenliine benzer bir iletkenlik erisi elde edilmitir. 540 ve 580Clerde sinterlenmi numunelerde gzenek oran azaldndan elektrik iletkenliinin artt grlmtr. 3.3 Mikroyaplar
ekil 5. Preslenme basncnn gzeneklilie etkisi, a) 200 MPa, b) 250 MPa, c) 300 MPa Toz metal malzemelerde gzeneklilik oran presleme basncyla deimektedir. ekil 5te grlecei gibi presleme basnc 200 MPa da %11 gzenekli bir yap olumutur. Gzenekler toz metal partikllerin presleme ile bir araya gelip oluturduklar tanelerin kelerinde boluklar halinde siyah noktalar olarak grlmektedir. Presleme basnc 250 MPaa karldnda gzenek miktarnn azald ekil 5bde grlmektedir ekil 5cde ise 300 MPada preslenmi numunenin mikroyaps grlmektedir. 300 MPada gzenek miktar ve boyutunun iyice azald bariz bir ekilde grlmektedir. Gzenek miktarnn ve boyutunun deimesinde ve azalmasnda presleme basnc etkili olduu gibi sinterleme scakl da etkili olmaktadr. ekil 5de mikroyaps verilen numuneler 500Cde sinterlenmilerdir. Sinterleme scaklnn gzenek deiimine etkisi ekil 6da verilmitir.
ekil 6. Sinterleme scaklnn gzeneklilie etkisi a) 500 C, b) 540 C c) 580 C ekil 6da 250 MPa presleme basncnda 500, 540 ve 580Cde sinterlenmi numunelerin mikro yap fotoraflar verilmitir. 500 ve 540Clerde sinterlenmi numunelerde gzenek miktar birbirine yakn gzkmekle birlikte 580Cde gzenek miktarnn yok denecek kadar azald kalan gzeneklerin boyutlarnn kld grlmektedir. Sinterleme srasnda gzenek klmesinin nedeni partikller aras boyun blgesinin olumas, oluan boyun blgesinin byyerek partikllerin eksenleri arasndaki mesafeyi azaltarak partikllerin bir btn tane ekline dnmeleridir. Partikller taneye dnrken gzenekler yok olmakta, boyu byk olup da yok olamayan gzenekler de boyutlar klerek tane kelerinde bulunmaktadrlar. 4.SONULAR Toz metal Al malzemelerde gzenek miktarnn elektrik iletkenliine etkisinin belirlenmesi amacyla yaplan bu almada aadaki sonular elde edilmitir. 1. Toz metal malzemelerde younluk artnda presleme basnc nemli bir etken olup, presleme basncn artmas ile ham numunelerin gzenek miktar da azalmaktadr. 2. Gzenek miktarnn azalmasn etkileyen bir dier faktr sinterleme scakldr. Bu almada kullanlan Al malzeme iin 500, 540 ve 580C sinterleme scaklklar kullanlmtr. Artan sinterleme scakl younluu artrrken gzenek miktarn azaltmaktadr. 3. Presleme basncyla artan younluk art toz metal numunelerin elektrik iletkenliinde de arta sebep olmaktadr. 1 volt gerilimde 200 MPa da preslenmi numunede 8 Amper akm geerken, 250 MPa da preslenmi numune de 9.4, 300 MPada preslenmi numunede 9.6 Amper akm iletilmektedir.
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4. Sinterleme scakl younluu artrdndan elektrik iletkenliinde de arta neden olmaktadr. 500Cde sinterlenmi numune yaklak 8 A akm iletirken, 540 ve 580Cde sinterlenmi numuneler 9.8 A akm iletmektedir. KAYNAKLAR 1. Randall M.German Powder Metallurgy and Particulate Materials Processing Editrler. S.Sarta,M.Trker,N. Durlu 2007 Ankara 2. http://www.aluminum.org/Content/NavigationMenu/TheIndustry/PowderandPaste/PowderMetallurgy.PDF 3. R.M.Rose, L.A.Shepard,J.Wulff, evirenler Kaif Onaran, Sabri Altnta, Malzemelerin Yap ve zellikleri Elekronik zellikler,1986 4. Ye.P. Mamunya, H. Zois, L. Apekis,, E.V. Lebedev, Influence of pressure on the electrical conductivity of metal powders used as fillers in polymer composites, Powder Technology 140 (2004) 49 55
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POWDER COMPACTION AND APPLICATIONS
www.turkishpm.org
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New Press Type EP with Electrical servo drive system

Christian Mller, DORST Technologies GmbH & Co. KG, Mittenwalder Str. 61, 82431 Kochel am See/Germany Abstract In this new press type the rigidness of a mechanical press meets the high precision and convenience of a closed loop controlled hydraulic press. The flexibility is assured by easy programming, due to the powerful electronic control system, proven with hydraulic presses since years. The well known IPG has been adapted to the new task and guarantees quick setting of tools. The machine is designed to accept existing TPA die-sets, or optional quick clamping system for new tool concepts. The positioning accuracy of the punches is within 0,001 mm, thus fulfilling demand for minimized tolerances. Also future environmental requirements, such as minimum energy consumption, low noise emission or absence of hydraulic oil and lubricants are implemented in the new design. The paper presents the new type in detail and compares the performance to existing press systems. Keyworks: Powder Metallurgy, Compacting Press, Servo electrical press 1. Introduction The standard drives for powder presses are nowadays mechanical drives, hydraulic drives or the so-called hybrid drives. All these technologies have proven to be successful during many years of extensive use in the production process and under various conditions. The range of application of the different press types varies: Mechanical presses are mainly used as standard machines with pressing forces of up to about 4500 kN for the production of simple parts in long production runs. These machines have a fixed sequence of operations, all individual movements are interdependent of each other and the upper punch determines the pressing cycle. This press type is especially characterized by reliability and low energy demand and combines a high production rate with consistent part quality. Operation of the press requires well-trained and highly qualified technicians with extensive knowledge of the functions and operational steps of the machines. The actual setting process and the adjustment of the cycle are complex and time-consuming. The application of hydraulic presses ranges from small pressing forces up to maximum pressing forces. All movements can be carried out independently of each other and that is the reason why this technology is predestinated for multi- platen systems. The machines are usually equipped with programmable control systems, which are complemented by measuring systems on the machine axes. Thanks to this, it is possible to record and compensate deviations, which occur during the pressing process. Hydraulic presses are used for the production of complex and multi-level parts with close tolerances. The closedloop control ensures stabilized results, even under varying external conditions. The setting process is reduced to a minimum thanks to advanced electronic control systems, supporting software and technical experts. The hydraulic drive requires high energy input and thorough maintenance to ensure reliability during continuous operation.
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As a leading manufacturer of axial powder pressing technology, DORST Technologies is always striving for new approaches and solutions to optimize the production step of shaping. The mentioned drive technologies are fully developed nowadays. For pressing forces of up to 1600kN there is now an alternative drive technology, which incorporates the various advantages of both existing systems: 2. The Electrical Servo Drive System 2.1. Fundamental Principles Of The Electrical Servo Drive With the new EP press series the movements of the punches are generated by means of servo-motors and a backlash-free spindle drive. They provide for dynamic movements with accurate positioning and, as a result, for high stroke rates and precise compacts. In order to use all the positive characteristics of servo-motors to their full extent for the powder pressing technology, DORST Technologies did not integrate the new drive type into an existing press type but has developed a new press series for this purpose. The motors are of compact design and do not require any intermediate elements such as a transmission or coupling, but activate the spindles directly. That is why this drive technology has an extremely high rigidity. Each drive motor is equipped with its own measuring system the closed-loop control is carried out individually and directly on the active axis. Thus, inaccuracies resulting from indirect measuring are eliminated. In addition, the press is equipped with length measuring systems. Joint processing of both signals leads to a very high positioning and repeat accuracy of the axes. As a result there is a significant increase of speed, since the normal time-consuming adjustments, e.g. through hydraulic lines and hydraulic valves, are eliminated and the correction is carried out directly on the axis! All axes for compaction on a standard press, which are the upper punch, the die and the core rod, are driven by their own servo-motor. All movements can be carried out independently of each other. The maximum torque and thus the force are at disposal at any rotational speed and in any position. Thanks to this, movements can be carried out at the highest speeds up to the pressing position. 2.2. Implementation Of The Technology In The Machine The EP press type is equipped with a pre-stressed frame with four columns. The frame is of high rigidity and at the same time ensures easy access to the press area, respectively the tool, from all sides. The new press series comprises pressing forces from 150kN up to 1600kN and operates according to the die withdrawal process. It is designed for the application of quick-action clamping systems as well as for the installation of die sets. Thanks to the resulting flexibility, tools from existing presses can easily be integrated into the new machines. The new development is based on the modular design of DORST Technologies: Besides the new frame, DORST Technologies uses parts and complete subassemblies, which have been successfully used in production on other press types for years and have proven their reliability. For instance: Guidance of the axes is carried out in backlash-free linear guides, which provide a favorable length to supporting difference ratio within the frame. These guides have been successfully used in powder presses of the type TPA-HS for more than 10 years. The EP press series is designed in compliance with well-proven and reliable technology, which fulfills all requirements for the operation in daily production. The compact design of the drive motors allows for space-saving installation compared to conventional plants. The floor space of an EP50 press requires for instance only about 70% of the floor space of a comparable mechanical
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press for 500kN. Furthermore, there is the electrical installation, which requires a separate switch cabinet for the drive motors. However, the switch cabinet can be installed independently of the press and thus further away and in a space-saving manner, e.g. on a powder platform. The operating level is not very high for the most types of the EP press series, so that a pit is usually not required. The positioning and repeating accuracy of the press axes amount to 0,001 mm and therefore easily meet todays requirements for tolerances of compacts. These accuracies are achieved during each stroke by the extremely high consistency of the rotational speed, which is higher by a factor of 10 compared to conventional plants as well as by the measuring systems installed in each servo motor. Closed-loop control is carried out by means of the sophisticated control system DVS/DCS, which has been used worldwide in hydraulic presses for years and has been adapted to the specific requirements of the electrical drive. Thanks to the quick reaction of the purely electrical closed-loop control system and the dynamics of the servomotors, all movements with consistently high precision can be carried out with maximum speed and thus be used to increase the number of strokes. The time required by a motor to run up from standstill to the maximum speed is approximately 100 ms. Thus, the electrically driven EP presses achieve speeds of mechanical high speed presses. However, for the new press type there is no need of taking early decisions during the investment regarding the press design. The flexibility of electrical presses allows for production optimization to be carried out only as a function of part geometry and powder flow behavior. This means that when high parts or complex geometries are to be pressed, the press is being operated with a lower number of strokes and auxiliary movements of the filler to ensure adequate filling, but with pressing of flat parts the same press may be operated at a significantly higher speed optimized number of strokes and thus maximum productivity in accordance with the pressing requirements are the result. The maximum torque and thus the force are at disposal at any rotational speed and in any position. As a result, the high efficiency factor of the servo motors is being transmitted to the machine as a whole. The energy required for the operation of a powder press with a nominal pressing force of 500 kN amounts to an average amount of about 4 kW (operated at a pressing force of approx. 400 kN and 50 strokes/min). Even a mechanical press requires under the same conditions approx. 6,5 kW and the energy demand of a hydraulic press is about three times as much. For the purpose of meeting different requirements regarding press technology, all axes can be controlled according to position. The upper punch can alternatively be controlled according to the pressing force and can therefore produce precise compacts with constant height or density. 2.3. Control System DVS/DCS and IPG Complete monitoring and programming are carried out by means of the control system DVS/DCS, which has proven to be successful for many years on hydraulic presses. With this control system all hardware-related and software-related possibilities required for the control of the electrically driven EP press are available. The control system DVS/DCS (Dorst Visualisation System/Dorst Control System) ensures completely free programming in due consideration of the technological requirements of the press. Depending on the individual part to be pressed, its geometry and the desired tolerances, the technological optimum flow chart for the press will be programmed. It is not a requirement to take into consideration any fixed operational sequences of the machine (mechanical upper punch and/or die) nor it is necessary to adjust the speeds accordingly. The software tool Intelligent Program Generator IPG is an integral part of the control system. On the basis of some input data on geometry of the part to be pressed, the IPG calculates the complete pressing process and generates the appropriate machine program. The machine program is exactly adapted to the respective press type and, therefore, represents the perfect cycle. The required adaptations for the optimization of density, height and weight can quickly and easily be carried out by means of the screen masks which were especially designed for this purpose. Due to the simple design and clear structure of the windows for programming, manual entries regarding operational machine sequences can easily be carried out.
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Access to all functions is as usually provided by the well-known user interface and each operator, who has already experience with the control system of e.g. a hydraulic press, will be able to cope with it without any difficulties. 2.4. Advantages Compared To Previous Press Types Due to the design and behavior of the servo motors, there are a number of advantages, which prove to be beneficial for the press technology: The compact design allows for little floor space of the press. This is a significant advantage of the EP press series taking into account that it is not easy to enlarge the space in existing buildings. The direct drive without intermediate components leads to a significant decrease of effort regarding maintenance and servicing, due to the fewer number of subassemblies. The provision of spare parts can be limited to a minimum. The machines of the EP press series do not require any auxiliary fluids and lubricants. Hydraulic oil is not required and therefore there is no need of oil change. In addition to resulting cost savings, this also means that there are no environmental hazards due to leakage of such fluids. The installation place of the machine does not have to be equipped with an oil pan or a leak proof pit. The motors have a very low noise emission: Typically these emissions amount to less than 65 dB(A). This means that, without taking any noise-absorbing measures, the noise level in the pressing plant falls significantly below todays admissible values. The low energy demand decreases the operating costs for a long term and for the entire lifetime of the machine. Furthermore, there is the possibility of using the energy supply cabinet of the first electrically driven press for further machines: Up to four powder presses can be operated simultaneously with only one supply cabinet. This ensures a reduction in costs for the second and further machine investment! 3. Upshot The introduction of the Servo Motor Drive Press EP represents a milestone in the development of compacting presses for the PM industry. Environmental friendliness, low energy consumption and logistic advantages are combined with yet unknown opportunities for press movements and directly controlled adjustments.
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MAGNESIUM BASED GRANULES AND POWDERS A TOOL FOR SOLVING THE CHALLENGES OF OUR MODERN WORLD
Wolfgang GITTERLE ALMAMET GmbH ABSTRACT Beside the typical use of magnesium in die casting there are manifold uses of magnesium in our modern world. To reach the requirements magnesium ingots are processed into granules, powders and raspings. These products are then used for the production of chemical substances and metals, for pyrotechnic applications and also for the refining of high quality steels. Other applications are the use for increasing the performance of refractory materials in high temperature areas and for the production of computer casings. Without magnesium based products some of our technical improvements would not have been possible. The presentation will show the chemical properties of the used magnesium, the mechanism of production and the chemical and metallurgical explications for the use of magnesium in these special application fields. Keywords: Magnesium, raspings, granules, powders, chemicals, desulfurization 1. INTRODUCTION Magnesium is a light metal with manifold applications. Beside the use for automotive parts,- one of the most famous application was the use in engine parts of the Volkswagen Beetle-, magnesium is also a very important alloying metal for aluminium alloys. According to figure 1 the world wide consumption of magnesium has become almost 800.000 tons per year [1]. The most important producer of magnesium is by far China with an yearly production of more than 650.000 tons. The sales of magnesium raspings, granules and powders with chinese origin has reached 85.000 tons in 2010, which is a bit more than 10% of the world wide use of magnesium; this shows that the use of magnesium for applications beside alloying and diecasting is still a niche market.
Figure 1. Worldwide use of magnesium [1].
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Almamet as a producer of magnesium based raspings, granules and powders, is one of the most important players in this market; although the quantities of material are not that high compared to the quantities in the steel industry, nevertheless this is a field with a wide range of challenges and opportunities. 2. PROPERTIES OF MAGNESIUM The atomic number of magnesium is 12, the atomic weight is 24,3050 g/mole. Magnesium has a density of 1,738 g/cm, a characteristic light metal with excellent properties for the use in automotive parts. The crystal lattice is hexagonal which brings some difficulties in forging of magnesium parts. Aluminium- magnesium alloys with 50% Mg and 50% Al are brittle and cannot be sawed with cutting machines. Magnesium has a low melting point, it melts at 650C and has a vapour point of 1090C; the low melting point limits the use of this light metal in some technical applications. The normal potential of magnesium is -2,372 V, which indicates that magnesium has a high affinity to react with oxygen. Especially for the use of magnesium based parts at higher temperature it is necessary to protect them against oxidation. Therefore the use of coatings is a convenient way of protection. 3. PRODUCTION OF MAGNESIUM FINES Magnesium is a very reactive material and a lot of safety issues have to be considered. Magnesium fines are dangerous products which need to be transported and stored under consideration of strong safety regulations. The problem of oxidation is always present during the production process of magnesium parts. Drilling can only be done with special emulsions, based on oils or any other non- flammable liquids, which are able to reduce the process temperature and avoid the oxidation and burning of magnesium. The production of fine magnesium products can be done in two different ways. The conventional production route is the sawing of ingots (figure 2), followed by the grinding of the produced rasping and, as last step, the classification of the produced fines. According to the size of the products the materials are classified in raspings, granules and powders. Typical granules of this production route are shown in figure 3.
Figure 2. Raw material for the production of magnesium fines
Figure 3. Magnesium granules Mg99,95, produced from ingots
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Another possibility to produce magnesium fines is the spraying of liquid magnesium metal through a nozzle under an inert atmosphere. This production route is cost intense and mainly preserved for the production of magnesium powders for military applications. While the output of the conventional route is approximately 50.000 tons per year, the production of atomized powders by spraying of magnesium metal is only a small part of this amount. Especially for the use in hot metal desulfurization the use of magnesium granules made from secondary magnesium alloys has become an important production route. For this use the requirements are not so strong as for other applications, this is why a significant amount of magnesium scrap is used for the production of desulfurizing reagent [2]. 4. APPLICATION OF MAGNESIUM FINES The main application of ground magnesium is the use as desulfurizing agent for the production of steel. Magnesium granules in a size of 0,2- 1,0 mm are injected into molten iron, react there with sulphur and form a slag which can be rather easily removed. This is by far the most important application of magnesium fines. The raw material for magnesium granules is mainly pure magnesium with 99,95% Mg content. Another source for magnesium granules is secondary magnesium, consisting mainly of magnesium alloys AZ91 and AM50 and AM 60. These materials have brought very good results when desulfurizing at temperatures above 1500C. The strength of these raw materials limits the shape of the granules; it is much more difficult to get globular products compared to the results when processing pure magnesium. Magnesium granules are a very efficient reagent for removing the sulfur from hot metal. The efficiency is about seven times higher than that of calcium carbide; a typical steelplant with initial sulfur contents of approx. 800ppm in the hot metal before desulfurization and final sulfur contents of about 50ppm is using approximately 0,6-0,7 kg magnesium granules per ton of hot metal [3]. Conventional steelplants using the typical route with blast furnace and BOF converters are producing about 5 million tons of hot metal. This means that a mid sized steelplant has a consumption of almost 3.500 tons of magnesium granules per year. Another important application of magnesium granules is the use in semi- solid casting processes. Magnesium granules are transported with a screw conveyor; friction leads to an increase of temperature and the granules start to melt at the surface. This pulp of partly molten magnesium flows into the mould and fills it. With this process it is possible to produce high quality computer casing boxes and automotive parts. Due to the high production costs of the rasping this process is reserved only for high- end products. The advantages of this production route are low thermal shrinkages and high quality surfaces of the products. With this production route it is possible to produce thin- wall parts like notebook housings. The raw materials for this application are mainly magnesium alloys, based on AZ91 or AM60 since it is necessary to reach high standards regarding the strength of the produced parts. Another advantage of this process is the short production schedule; the period from designing to mass production of the consumer part is very short, compared to other production processes [4]. The production of cored wires filled with magnesium granules and ferroalloys is another special application in the steel production. In this case magnesium helps to provide good conditions for alloying and helps to reach special structures of inclusions in the casted steel, which is important to reach the high demands on modern steels. A big quantity of magnesium raspings is used in chemical processes. Magnesium is filled into catalytic reactors; together with organic substances chemical reactions will start and organometallic compounds are generated. These so called Grignard- reactions, running at different temperature levels and with different organic reagents, are used for the production of different intermediates for the production of plastics or vitamins. The magnesium raspings are in a size of 1 50mm length, depending on the process; generally it can be said that all raspings used in Grignard reactions, are tailor made according to the requirements of the customers. Due to the special application the used magnesium has to be high purity material; even a small number of impurities can lead to outliers and wastage of the whole charge. The yearly amount of magnesium used in this application is less than 10.000 tons. Only a small amount of magnesium fines is used as powders. Magnesium powders are sensitive against oxidization and have to be carefully protected against humidity and open fires. The main use of magnesium powders is in processes where a high level of energy is required. Magnesium has a high affinity to oxygen; in combination with the high specific surface of powders this type of magnesium product is a proper reagent for the reduction of metallic oxydes, e.g. tungsten from WO3. For this applications the used magnesium has to be pure with a magnesium content of not less than 99,95% to avoid any impurities which might disturb the properties of the produced metal.
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Another important application of magnesium powders is the use in pyrotechnics as an energy source. The magnesium contains a lot of energy to start the specific reactions of the added metal oxydes with the result of sophisticated colouring effects. The magnesium powders also burn with a bright flame, which is also used to bring a decorative effect in fireworks. For the use in fireworks mainly magnesium-aluminium alloys with 50% Al and 50% Mg are used. This material is brittle and can be crushed. The production of these powders is therefore done with crushers, it is almost impossible to cut these alloys with saws. The powders are globular, which allows constant properties in all dimensions; cutted magnesium powders have different dimensions in length and wideness, therefore these powders will have a different appearance when burning, they tend to make sparks in all directions. Magnesium based powders are also used for military applications. In this field magnesium flares are in use to irritate thermal controlled weapons; In case if an airplane starts or lands in a dangerous area, in which it might be attacked by thermal controlled weapons, a cloud of burning magnesium flares is generated which helps to irritate any weapons which would have the engines of the plane as their target. A very interesting application for magnesium based powders is the use in refractory bricks. Mainly powders based on aluminium- magnesium- alloy 50/50 are used for increasing the performance of magnesia and carbon based, resin bonded, refractory bricks. Additions of small amounts of Al-Mg- powders in a size of 0-500 microns have a significant influence on the life time of the refractories. During the use of these bricks in converters or blast furnaces the added alloy powder gets oxidized and forms Al2O3 and MgO. This phase has very good properties regarding strength, supports the structure of the bricks and also prevents the carbon of the refractory bricks from oxygen. Even as theses powders have an influence on the price of the refractory bricks, the use is justified by an increased life time of the refractory material. For this special application Almamet is selling some hundred tons per year. All powders are tailor made; every customer has his own special requirements. Beside the pure alloy powders some customers need to be supplied with premixes of alloy powders with magnesia to decrease the hazardous potential of these fine materials. It has been detected that the addition of 30% magnesia tremendously reduces the explosivity of these magnesium powders. In addition to this fact the dosage of the powder is much easier and helps the producer of the refractory bricks to save time and brings big increases of the quality. Some research activities were recently made with magnesium powders used for the storage of hydrogen [5]. The hydrogen is stored as MgH2. The production of MgH2 is done with magnesium powder and pressurized hydrogen at temperatures between 250C and 400C. The production parameters for the typical reaction can be seen in figure 4. The MgH2 is a solid material which can be stored then in cartridges as a fuel for hydrogen driven cars. The hydrogen is released then in the hydrolysis reaction between water and MgH2. This new application for magnesium powder could be a solution for the storage of hydrogen for transport means in the future. The production process is patented and the first commercial production should have been started [6].
Figure 4. Production parameters for MgH2 [4]. 5. CONCLUSION Magnesium raspings, granules and powders are positioned in a niche market. Although the materials are not known well, they play an important role in our modern life. Magnesium fines are used in manifold production routes. The modern production of steel, plastics and even nutritials would not be possible without magnesium fines. Since the requirements of modern construction materials continue to increase, magnesium fines are getting even more important to fulfil the ambitious needs of our modern society.
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6. REFERENCES 1. M. Shukun, W. Xiuming, X. Jinxiang, China Magnesium Development Report in 2010, 68th Annual World Magnesium Conference, Prague, 2011, p.51ff 2. A. Ditze, C. Schrf, Utilising magnesium scrap in other sectors, Recycling of Magnesium, p. 141ff 3. R. Schwarzenbrunner, F. Landerl, R. Apfolterer, The Pig Iron Desulphurization as an Important Procedural Step of the Steel Production, The X. International Symposium for Desulphurization of Hot Metal and Steel, 2008, Lisbon, p.40ff 4. I. Nakatsugawa, T. Tsukeda, K. Kitamura, Latest Developments in Magnesium Use for Thixomolding in Asia, 59th Annual World Magnesium Conference, Montreal, 2002, p. 11ff 5. H. Uesugi, T. Sugiyama, I. Nakatsugawa, T. Ito, Production of Hydrogen Storage Material MgH2 and its Applications, 67th Annual World Magnesium Conference, Hong Kong, 2010, p. 49ff 6. M. Jehan, Safe Clean and Efficient Solutions for Energy Storage, 66th Annual World Magnesium Conference, San Francisco, 2009, p. 171ff
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APPLICATION OF CENTRAL COMPOSITE DESIGN TO INVESTIGATE THE EFFECTS OF REINFORCEMENT VOLUME FRACTION AND MATRIX-REINFORCEMENT PARTICLE SIZE RATIO ON WEAR CHARACTERISTICS OF Al-SiCp METAL MATRIX COMPOSITES
Ege Anl Diler , Rasim pek and hret M. Erolu
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Department of Mechanical Engineering, Ege University, 35100, Bornova, Izmir, Turkey, Ege. anil.diler@ege.edu.tr, rasim.ipek@ege.edu.tr, sohret.eroglu@ege.edu.tr ABSTRACT
In this study, the effects of reinforcement volume fraction, matrix-reinforcement particle size ratio and their interactions on the wear characteristics of Al-SiC metal matrix composites have been investigated by using central experimental composite design (CCD). To optimize the required number of experiments central composite design with three factors and five levels was used. The fabricated composites were reinforced with SiC particles of 4.09, 7.5, 12.5, 17.5 and 20.91 volume fractions. The particle sizes of 68, 86, 112, 138 and 156 m were selected for both matrix and reinforcement particles. All these values were determined according to CCD. The wear behavior of these Al-SiCp metal matrix composites have been investigated under dry adhesive wear condition. Main factors and their interactions were effective on wear behavior of Al-SiCp composites. The best combination of factors to obtain the highest wear resistance was achieved when matrix-reinforcement size ratio equaled to one or was a little higher than one for high volume fraction. Keywords: Powder metallurgy; Al-SiCp; Metal matrix composites; Central composite design; wear. 1. Introduction Metal matrix composites (MMCs) have been extensively used because of high strength, light weight, improved wear resistance. These materials are preferred in several applications; for instance, brake pads which have been made of Al-SiC composites have been used in railway or automotive applications [1,2]. Ceramic phases like SiC improve the wear resistance of materials. These phases are found as particle or whisker forms in the Al-SiC composites. Although the study of Aiguo and Rack [3] showed that whisker reinforcement is more influential than particle reinforcement in enhancing wear resistance of a composite, Miyajima and Iwai [4] presented composite with particle was more beneficial than ones with whisker and fiber. There are many factors affecting the wear behavior of Al-SiC composites. These factors are reinforcement size and volume fraction, abrasive size, load, speed, sliding distance, temperature, etc. The effect of matrix powder size hasnt been taken into account in the studies which all other factors were investigated [3-13]. However, matrix powder size is one of the important factors in Al-SiCp composites which are manufactured by powder metallurgy method. Because, matrix-reinforcement size ratio determines the distribution of reinforcement particles in the microstructure. In addition to matrix-reinforcement size ratio, reinforcement volume fraction also affects particle distribution. Due to volume fraction and matrix-reinforcement size ratio, particle clustering may occur, which raises probability of particle clustering [14]. A reinforcement particle in a particle cluster can be easily pulled out from the material surface contacting against the counterface material during the wear test. Hence, the wear resistance of the composites
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reinforced with high reinforcement volume fraction can be lower than that of unreinforced materials. As a result of aforementioned reasons, the matrix-reinforcement particle sizes and reinforcement particle volume fraction have a strong impact on the wear behavior of the composites. As the number of the factors and their levels increases, the number of experiment also increases. Therefore, many experimental design methods have been used to investigate the wear behavior of Al-SiCp composites. Most of the researchers used Taguchi method [15-18] while ahin [19] applied factorial design method in his study. Another experimental design method for statistical analysis is central composite design (CCD) method. CCD method has been preferred by some researchers [20-21] because the number of experiment is decreased with the help of this method. Unfortunately, the effect of matrix powder size on the wear behavior of composites has not been investigated in all the studies mentioned above. The aim of this study is to investigate the effect of the matrix powder size besides reinforcement particle size and volume fraction and their interactions on the wear behavior of Al-SiCp composites under adhesive wear condition by using CCD statistical analysis. 2. ExperImental 2.1 Materials SiC particle reinforced aluminum matrix composite specimens were manufactured from elemental powders by powder metallurgy. According to CCD experimental method, the fabricated composites were reinforced with SiC particles of 4.09, 7.5, 12.5, 17.5 and 20.91 volume fractions, and the particle sizes of 68, 86, 112, 138 and 156 m were selected for both matrix and reinforcement particles. The powders were blended for 1 h in triaxial mixer to provide homogeneous dispersion. Then powder mixture was cold compacted under a pressure of 450MPa. The green compacts were then sintered at 600 C for 6 h. 2.2 Wear test The wear tests were performed under dry sliding conditions using a ball-on-disc type testing machine. A hardness of 62 HRC and 6 mm diameter bearing ball was loaded against the specimens. The track diameter was 10 mm. Wear tests were applied under the normal load of 5 N and at a constant sliding velocity of 0.416 m/s and a sliding distance of 500 m. Before and after the wear test all specimens were cleaned with alcohol to remove accumulated debris on the wear track and weighed before and after the wear tests using an electronic balance with a resolution of 0.0001 g. 2.3 Experimental design The experiments were designed according to CCD method. Each variable was studied at two different levels (-1, +1), two axial points (-1.68179, +1.68179) and a center point (0) which is the midpoint of each factor range. The minimum and maximum range of variables investigated and the full experimental plan with respect to their actual and coded values are listed in Table 1. Table 1. Experimental range of the variables studied using CCD in the terms of actual and coded factors.
Experimental results were analyzed using the Minitab 15 software. The polynomial equations for the response were validated by ANOVA (analysis of variance) to determine the significance of each term in the equations and also to estimate the goodness of fit in each case. Response surfaces were drawn for the experimental results obtained for the effect of the different variables on the wear loss of the MMCs after the wear test in order to determine the main, interaction and quadratic effects of these variables.
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Table 2. Central composite design plan and experimental results. 3. Results and discussion The microstructures of Al-SiCp composites with different volume fraction, matrix and reinforcement size are shown in Fig.1. Reinforcement particles were uniformly distributed in Al-SiCp composites with low volume fraction (Fig.1 a and b) while they clustered in case high volume fraction of reinforcement was high level and matrix size was higher than that of reinforcement particles (Fig.1 c and d).
Fig. 1. Optical micrographs of Al-SiCp composites at 100X magnification: (a) 7.5% Al(86m)-SiCp(138m); (b) 7.5% Al(138m)-SiCp(86m); (c) 17.5% Al(86m)- SiCp(138m); (d) 17.5% Al(138m)-SiCp(86m).
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Table 3, Analysis of variance (ANOVA) of CCD model.
Table 3 shows the ANOVA of CCD model. The coefficient determination (R2) was 0.9790. It means that the statistical model can explain 97.90 % variability in the response. When the value of P is less than 0.05, the terms (main factors, interactions and quadratic effects of factors) of the model are significant. As seen from Table 3, P values of the main factors were less than 0.05 values; therefore, volume fraction, matrix and reinforcement sizes had significant effects on the wear rate. Interactions of volume fraction*matrix size (A*B) and volume fraction*reinforcement size (A*C) was also significant while interaction between matrix size and reinforcement size was insignificant on the model. Except for volume fraction, quadratic terms of matrix and reinforcement size was insignificant. To calculate the % contribution of the significant factors, the sum of squares of a factor divides the total sum of squares. As seen from the Table 4, the factor of volume fraction of reinforcement particles had the highest contribution on the response of the model.
Table 4. Contribution of significant main factors, their interactions and quadratic effects of factors.
Table 4. Response surface regression including only significant terms. Eq. (1), the regression equation including coefficients of significant terms and coded values of factors, is given below: W = 0.003651 - 0.005698 (A) + 0.001244 (B) - 0.002316 (C) + 0.002881 (A2) - 0.000967 (AB) + 0.001750 (AC) (1) where W is the response (wear loss) and A, B and C are the coded values of factors, volume fraction, matrix size and reinforcement size, respectively.
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Fig. 2. Main effects plot for wear of Al-SiC composites. Fig. 2 shows the individual main effect of matrix size on wear. Total surface area of matrix powder increases as their size decreases, which results in an increase in hardness of composite due to an increase in number of obstacles against movement of dislocations. Hence, wear loss of MMCs increased as matrix size increased in present study. Individual main effects plot of reinforcement particle size showed that wear loss decreased as reinforcement particle size increased (Fig. 2). The reason is that large sized particles have higher load bearing capacity than smaller one [10]. Another reason is that matrix-reinforcement interfacial area is wider for MMCs reinforced with small sized particles, which causes to reinforcement particles easily pull out from the matrix [21]. Large sized particles tightly embedded in the matrix; therefore, they protect the matrix until they fracture into smaller particles. As a result of two reasons mentioned above, wear resistance of MMCs increases as size of reinforcement particle increases. As for individual main effect of volume fraction on wear, wear loss decreases as volume fraction increased. In fact, an increase in volume fraction negatively affects the mechanical behavior of MMCs because particle clustering occurs as volume fraction increases. Particle clustering in MMCs weakens the mechanical strength such as tensile strength [22]. From the point of view of wear, particle clustering depending on high volume fraction had positive influence on wear resistance of MMCs in present study. This was only true when matrix- reinforcement size ratio was high at high volume fractions. Because; for high volume fractions, wear resistance increased as matrixreinforcement size ratio increased. Reinforcement particles which are located in cluster region are not bonded to each other due to low sintering temperature. These particles are more easily debonded from the cluster region or pulled out from the matrix during wear. Debonded or pulled out particles cause three-body abrasive wear [23], which results in an increase in wear due to the fact that hard reinforcement particles tend to abrade both MMC and counterface surfaces. These particles form a hard and stable MML at a later stage of wear. Wear loss reduces in these stages, called as mild wear, which is attributed to existence of a hard and stable MML resulting in better wear resistance [24]. In this case, it is easy to form a thinner, harder and more stable MML for MMC reinforced with small sized particle compared to big sized particle one. Although the individual main effect of reinforcement size increases wear resistance, coarse particle size at high level of volume fraction has negative influence on wear resistance. It is also important to note that since the stress on the debonded or pulled out particles is excessive and the probability of having defects of coarse particles is high, these particles will begin to become smaller and smaller by fracturing. This situation increases the wear resistance of MMCs in that the ability of these particles to plough or to scratch decreases. Actually, probability of particle clustering increases as matrix-reinforcement size ratio increases. Although particle clustering has a strong effect on the mechanical properties of MMCs reinforced with particles, Table 3 shows that interaction between matrix size (B) and reinforcement size (C) had insignificant effect on wear because its P value is greater than 0.05.
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Fig. 3. 3D response surface plot of the effect of volume fraction and matrix size and their interaction on wear. Fig. 3 shows the interaction effect of volume fraction and matrix size on the wear of Al- SiCp composite while reinforcement size is constant kept at coded value of 0. This response surface plot indicates that wear loss increased at low level of volume fraction and high level of matrix size and also that the volume fraction had a dominant effect over the matrix size (Table 4).
Fig. 4. 3D response surface plot of the effect of volume fraction and reinforcement size and their interaction on wear. The interaction effect of volume fraction and reinforcement size on the wear of Al-SiCp composite while matrix size was constant kept at coded value of 0 is shown in Fig. 4. As aforementioned above, this response surface plot indicates that wear loss of Al-SiCp composites decreased at the high level of volume fraction and at the low level of reinforcement size or at high matrix-reinforcement size ratio. Consequently, for highest wear resistance the best combination of factors is achieved when matrix-reinforcement size ratio equals to one or is a little higher than one for high volume fraction although both high volume fraction and high matrix-reinforcement size ratio result in particle clustering. 4. Conclusions In this study, the effect of reinforcement volume fraction, matrix and reinforcement size on wear of Al-SiCp composites was investigated using CCD, and the following results were obtained: (1) Reinforcement volume fraction, matrix and reinforcement sizes as individual main factors and their interactions except matrix size*reinforcement size interaction affect wear behavior of Al-SiCp composites. (2) Individual main effect plots of volume fraction and reinforcement size indicate that wear loss decreases as values of these factors increases while matrix size has contradictory effect. In interaction between volume fraction and matrix size, the effect of volume fraction dominates that of matrix size.
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(3) Although both volume fraction and reinforcement size as individual main factors decrease wear loss, interaction between volume fraction and reinforcement size plays a negative role on the wear resistance at high volume fraction and reinforcement size. (4) The best combination of factors to obtain the highest wear resistance can be achieved when matrix-reinforcement size ratio equals to one or is a little higher than one for high volume fraction. References [1] Laden K., Guerin J.D., Watremez M. and Bricout J.P., Frictional characteristics of AlSiC composite brake discs, Tribology Letters, 8, 2000, 237-247. [2] Vencl A., Rac A., Bobic I., Tribological behaviour of Al-based MMCs and their application in automotive industry, Tribology in industry, 26, 3-4, 2004, 31-38. [3] Wang Aiguo and Rack H.J., Abrasive wear of silicon carbide particulate-and whisker- reinforced 7091 aluminum matrix composites, Wear, 146, 2, 1991, 337-348. [4] Miyajima T. and Iwai Y., Effects of reinforcements on sliding wear behavior of aluminum matrix composites, Wear, 255, 2003, 606-616. [5] Veeresh Kumar G.B., Rao C.S.P., Selvaraj N., Mechanical and tribological behavior of particulate reinforced aluminum metal matrix composites - a review, Journal of Minerals & Materials Characterization & Engineering, 10, 1, 2011, 59-91. [6] Daoud A., Abou El-khair M.T., Wear and friction behavior of sand cast brake rotor made of A359-20vol%SiC particle composites sliding against automobile friction material, Tribology International, 43, 2010, 544-553. [7] Deuis R.L., Subramanian C., Yellup J.M., Dry sliding wear of aluminium scomposites-a review, Composites Science and Technology, 57, 1997, 415-435. [8] Alpas A.T. and Zhang J., Effect of SiC particulate reinforcement on the dry sliding wear of aluminium-silicon alloys (A356), Wear, 155, 1, 1991, 83-104. [9] pek R., Adhesive wear behavior of B4C and SiC reinforced 4147Al matrix composites (Al/B4C-Al/SiC), Journal of Materials Processing Technology, 162-163, 2005, 71-75. [10] Bindumadhavan P.N., Heng Keng Wah, Prabhakar O., Dual particle size (DPS) composites: effect on wear and mechanical properties of particulate metal matrix composites, Wear, 248, 2001, 112-120. [11] Gl F. and Acilar M., Effect of the reinforcement volume fraction on the dry sliding wear behavior of Al10Si/SiCp composites produced by vacuum infiltration technique, Composites Science and Technology, 64, 2004, 1959-1970. [12] Sun Zhiqiang, Zhang Di, Li Guobin, Evaluation of dry sliding wear behavior of silicon particles reinforced aluminum matrix composites, Materials and Design, 26, 2005, 454- 458. [13] Mondal D.P., Das S., High stress abrasive wear behavior of aluminium hard particle composites: Effect of experimental parameters, particle size and volume fraction Tribology International, 39, 2006, 470-478. [14] Bhanu Prasad V.V., Bhat B.V.R., Ramakrishnan P., Mahajan Y.R., Clustering probability maps for private metal matrix composites, Scripta Materialia, 43, 2000, 835- 840. [15] Basavarajappa S., Chandramohan G., Paulo Davim J., Application of Taguchi techniques to study dry sliding wear behavior of metal matrix composites, Materials and Design, 28, 2007, 1393-1398. [16] Kk M., Computational investigation of testing parameter effects on abrasive wear behavior of AL2O3 particlereinforced MMCs using statistical analysis, International Journal of Advanced Manufacturing Technology, 52, 2011, 207-215. [17] Venkat Prasat S., Subramanian R., Radhika N., Anandavel B., Arun L., Praveen N., Influence of parameters on the dry sliding wear behaviour of aluminium/fly ash/graphite hybrid metal matrix composites, European Journal of Scientific Research, 53, 2, 2011, 280-290. [18] Sahin Y., The prediction of wear resistance model for the metal matrix composites, Wear, 258, 2005, 1717-1722. [19] Sahin Y., Wear behavior of aluminium alloy and its composites reinforced by SiN particles using statistical analysis, Materials and Design, 24, 2003, 95-103. [20] Anoop S., Natarajan S., Kumaresh Babu S.P., Analysis of factors influencing dry sliding wear behaviour of Al/SiC brake pad tribosystem, Materials and Design, 30, 2009, 3831-3838. [21] Kumar S., Balasubramanian V., Developing a mathematical model to evaluate wear rate of AA7075/SiCp powder metallurgy composites, Wear, 264, 2008, 1026-1034. [22] Liu Z.Y., Wang Q.Z., Xiao B.L., Ma Z.Y., Clustering model on the tensile strength of PM processed SiCp/Al composites, Composites: PartA 41, 2010, 1686-1692. [23] Bindumadhavan P.N., Chia T.K., Chandrasekaran M., Heng Keng Wah , Loh Nee Lam, Prabhakar O., Effect of particle-porosity clusters on tribological behavior of cast aluminum alloy A356-SiCp metal matrix composites, Materials Science and Engineering A 315, 2001, 217-226. [24] Venkataraman B., Sundararajan G., Correlation between the characteristics of the mechanically mixed layer and wear behavior of aluminium, Al-7075 alloy and Al- MMCs, Wear, 245, 2000, 22-38.
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HGANAS NEW MACHINABILITY ENHANCING MATERIALS

Philippe SZABO*, Eda YILMAZTRK YKSEKDA** *Hganas AB, France Office, 1117 Avenue Edouard Herriot, B.P. 117, F 69654, Villefranche sur Saone Cedex, France, philippe.szabo@hoganas.com **Hganas AB, Turkey Agency Office, Eksper Endustriyel Hammadde ve Dis Ticaret Ltd Sti, Sipahioglu Caddesi, Salkim Apartmani, No:11 D:13, 34149, Yesilyurt, Istanbul, Turkey, eda@eksperdisticaret.com ABSTRACT This Hgans presentation is done in order to show how it can be find improvement for machining processes, through material selection. A straightforward way to improve the process is to use a material with enhanced machinability. By adding small portions of machinability enhancing materials to the powder mix for component production, it can be got significantly increased tool life (or productivity) and improved surface finish of the components. Hgans provides four different additives to choose from: totally new MnM and SM3, and the traditional MnX, MnS. The optimal choice is dependent on the machinability process, indeed. Main benefits to target are: higher productivity increased tool life improved surface finish Key Words: MnX, MnS, PM Enhancing Materials, Machinability of PM Parts. 1. INTRODUCTION Powder Metallurgy (PM) is well known for producing complex parts to very close tolerance. Yet, machining is still important for some applications: - Further demands on tolerances - Undercuts - Further demands on surface quality 2. MACHINABILITY Assumed that machining operation can be defined as a chip removing operation. Therefore, we can consider machinability as a general property, strongly influenced by machining process. When determination to do as questioning Is it easy to machine the material? or How to characterize machinability? , we can summarize this topic through measurement of tool wear and life (the real action between tool edge and material) and then, surface quality of the machined part - cutting forces and torques shape of chip. 3. OBJECTIVE Carry out Drilling & Turning tests on three different PM steels. Investigate how drill tool grades and additives will influence machinability. 3.1 Experimental - Materials and Specimens for Machinability Experiments Materials and Specimens:
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Figure 1. Chemical composition of different powder mixes to be used in experimental application. Additives: 0.3% MnS, 0.15% test additive MnM, SM3 in order to achieve variants in powder mix (Our new MnM & SM3 are additives free from sulphur). Compacted specimens: All specimens with GD = 7.0 g/cm Sintering/Sinter Hardening:
Figure 2. Sintering and Sinter Hardening conditions of powder mixes to be used in experimental application. Heat Treatment: After sinter hardening - tempering at 200C in air for 60 minutes. Microstructures:
Figure 3. Microstructure of part produced by AHC powder mix at the end of processes, resulted typically with 83 HRB hardness level.
Figure 4. Microstructure of part produced by DAE powder mix at the end of processes, resulted typically with 92 HRB hardness level.
Figure 5. Microstructure of part produced by CRM powder mix at the end of processes, resulted typically with 35 HRC hardness level.
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3.2 Experimental Drilling and Turning Process for Experiments
Figure 6. Drilling machine to be used in process Mazak Lathe Quick turn Nexus 200-II MY.
Figure 7. 100/42 mm ring specimen to be used in drilling process (full pattern is equal to 302 holes). Test Method: To drill as many holes as possible before break down. (More than eight drill per test used to establish statistic values). Cutting Parameters & Drills:
Figure 8. Types and properties of drills to be used in experimental applications. 3.3 Experimental Results of Drilling and Turning Experiments Drilling Machinability of AHC / DAE / CrM :
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Figure 9. Affect of different type of enhancing materials on tool life and production efficiency. (Test held on part produced by AHC based powder mix.)
Figure 10. Affect of different type of enhancing materials on tool life and production efficiency. (Test held on part produced by DAE based powder mix.)
Figure 11. Affect of different type of enhancing materials on tool life and production efficiency. (Test held on part produced by CrM based powder mix.)
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Turning Machinability of AHC / DAE / CrM :
Figure 12. Affect of different type of enhancing materials on tool life and production efficiency. (Test held on part produced by AHC based powder mix.)
Figure 13. Affect of different type of enhancing materials on tool life and production efficiency. ( Test held on part produced by DAE based powder mix.) 4. HGANAS SOURCING GRID To facilitate the powder mix selection, Hgans has developed its internal Machinability Sourcing Grid. The tool is based on a comprehensive range of tests under selected different process conditions with a representative selection of materials combined with Hgans four additives.
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Figure 14. Illustration of the tool, by playing on the targeted results. 5. CONCLUSIONS Hgans is proposing Machinability Enhancing Materials, in order to get main benefits at your production as ; - higher productivity - increased tool life - improved surface finish By improving your machining processes through material selection, you can get a straightforward way to improve the process using a material with enhanced machinability. By adding small portions of machinability enhancing materials to the powder mix for component production, you can increase tool life (or productivity) significantly and improve the surface finish of the components. For this aim, Hgans provides four different additives to choose from: MnM, MnX, MnS and SM3. The optimal choice is dependent on the machinability process. All results thank to Olof Andersson + Mats Larsson + Bo-Hu + Nandivana Nagarjuna and team / Hgans AB
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POWDER PROCESSES & CHARACTERIZATION OF METAL POWDER AND PM PARTS
www.turkishpm.org
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YAPAY YALANDIRMANIN SiC VE 7075 ALMNYUM ALAIMI EREN BR LEVSEL DERECEL MALZEMENN SERTL ZERNE ETKS
Bertan SARIKAN*, M. Kemal ZTA**, Erhan BALCI*, Mustafa BEYL***, Necip CAMUU*, mer KELE** TOBB Ekonomi ve Teknoloji niversitesi, Makine Mhendislii Stz Caddesi No: 43 06530 Ankara TRKYE ** Gazi niversitesi, Mhendislik Fakltesi, Makine Mhendislii 06570 Maltepe, Ankara TRKYE *** Osmaniye Korkut Ata niversitesiMhendislik Fakltesi, Makine Mhendislii Karacaolan Yerlekesi, 80000 Osmaniye TRKYE e-posta: bsarikan@etu.edu.tr
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ZET Bu almada, scak presleme ve sv faz sinterleme yntemiyle, katmanl bir ilevsel dereceli malzeme (DM) retilmitir. retilen malzemenin alt katman 7075 alminyum alam, orta katman %10 veya %20 SiC takviyeli kompozit, st katman ise %20 veya %40 SiC takviyeli kompozitten olumaktadr. DMlere daha sonra yapay yalandrma ilemi uygulanmtr. Bu ilem zeltiye alma ileminden sonra, 120C scaklkta ve 78 saate kadar yaplmtr. Numuneler zerinde belirli zaman aralklarnda sertlik deerleri llmtr. Farkl yalandrma zamanlarnn numunelerin sertlik deerlerine etkisi aratrlmtr. almann sonunda, 65 saatlik yapay yalandrma ilemi sonunda en yksek sertlik deerlerine ulald gzlemlenmitir. Anahtar kelimeler: levsel dereceli malzeme, yalandrma, scak presleme.
EFFECT OF ARTIFICIAL AGING ON THE HARDNESS OF A FUNCTIONALLY GRADED MATERIAL CONSISTING OF SiC AND ALUMINIUM 7075 ALLOY
ABSTRACT In this study, a three-layer functionally graded material (FGM) was produced by hot pressing and liquid phase sintering methods. The top, middle and bottom layers of this material consist of 20% or 40% SiC reinforced composite, 10% or 20% SiC reinforced composite and 7075 aluminum alloy, respectively. Then, artificial aging process was applied to the materials. This was done at 120C and up to 78 hours. Hardness measurements were taken at certain time intervals. The effect of duration of the artificial aging process on the hardness of the materials was investigated. In conclusion, it was observed that the highest hardness values were obtained at the end of 65 hours of artificial ageing process. Keywords: Functionally graded material, aging process, hot pressing 1.GR Her geen gn artan toplum ihtiyalarnn karlanmas gereklilii, tasarmclar yeni malzemeler gelitirmeye ynlendirmektedir. Bu kapsamda kompozit malzemeler geleneksel metal malzemelere gre daha dk younlua ve
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istenilen mekanik zelliklere sahip olmalar nedeniyle tercih edilmektedir [1]. Kompozit malzemelerde anayapya ilave edilen takviye malzemesi dk younluk, yksek sneklik ve toklua sahip olan sisteme, yksek dayanm, rijitlik ve sertlik zellikleri kazandrarak stn mekanik zelliklere sahip bir malzemenin ortaya kmasn salamaktadr. Parack takviyeli kompozit sistemlerde takviye malzemesi olarak; silisyum karbr, bor karbr ve almina yaygn olarak kullanlmaktadr [2]. Malzemede yne bal olarak istenen mekanik zelliklerin elde edilmesi amacyla kompozit malzemelerin bir tr olan ilevsel dereceli malzemeler (DMler) ortaya kmtr. DMler heterojen bir yapya sahip olup, istenilen malzeme performansn salamak amacyla, kompozit malzeme ierisindeki yap, bileimi oluturan malzemelerin hacim oranlarn ve mikroyapsal zelliklerini deitirerek ayarlanabilmektedir [3]. DMlerin retiminde; toz metalurjisi, plazma pskrtme, kimyasal buhar keltme, lazer kaplama en yaygn kullanlan yntemlerdir. Bu yntemler arasnda toz metalurjisi, dk maliyet, dk enerji tketimi ve ilem sresinin ksa olmas gibi zellikleri nedeniyle tercih edilen yntemler arasnda en nemlisi olarak gsterilebilir [4]. Farkl ekillerdeki takviye malzemelerine kyasla parack takviyeli kompozit malzemeler izotropik mekanik zellikler elde edilmesi asndan daha elverilidir. Metal ve seramik toz paracklarnn sinterlenmesinde parack boyutu ve dalm kompozit malzemelerin mekanik zelliklerini nemli lde etkilemektedir [5]. SiC takviyeli Al alamlaryla ilgili literatrde yaplan almalarda; takviye paracklarn boyutu azaldka mekanik zelliklerin artt fakat bunun yannda takviye boyutu azaldka ve anayap ierisindeki takviye miktar arttka, toz karm esnasnda takviye paracklar arasnda topaklanmann daha fazla meydana geldii grlmtr [6]. stn mekanik zellikler elde edilmesi asndan anayap ve takviye malzemesinin iyi ba yapabilme zelliine sahip olmas gerekmektedir [7]. Anayapdaki toz boyut dalmnn geni bir aralkta olmas yksek paketlenme younluklar salarken, sinterleme ilemi sonucunda daha yksek mekanik zelliklerin elde edilmesine neden olmaktadr [7,8]. SiC parack takviyeli Al kompozitlerinin yalandrlmas ile ilgili yaplan almalarda, Mg atomlarnn Al ve SiC ara yzeylerinde MgO paracklar eklinde bulunmas ve anayapda MgSi2 bileii olumasna bal olarak yalandrma ileminin yavalad grlmtr [9]. Bir baka almada ise Al ve SiCnin iyi ba yapt gzlemlenmitir [10]. 7xxx serisi alminyum alamlar yalandrlabilir alamlar olup, yalandrma scaklk ve sresine bal olarak dayanmlarnn artrlabildii bilinmektedir [11]. AA 7075 iin kelti dizisi karmak olmasna ramen genel kabul gren kelti dizisi aadaki gibidir [12]: Ar doymu kat zelti GP blgeleri -MgZn2
Yalandrma ilemi sonucu ulalan en yksek sertlik deerlerinin kararl faz yerine, yar kararl faznn oluumundan sonra elde edildii dnlmektedir. GP blgeleri ve yar kararl faz kelmenin ilk aamalarnda olumaktadr. Oluan zeltilerin boyutu ve younluu istenilen zelliklerin elde edilmesinde nemli bir ldr. Ayrca oluan faznn tabakal yapsnn sertlii belirgin derecede artrd ve en yksek sertliin elde edilmesinde byk miktarda rol oynad bilinmektedir [11,13]. Bu almada, SiC parack takviyesi ve alminyum alam (AA) 7075 (%5,1-6,1 Zn, %2,1-2,9 Mg, %1,2-2,0 Cu, %0,5 Fe, %0,4 Si ve %0,18-0,28 Cr) ieren katmanl ilevsel dereceli malzemeler retilmitir. Daha sonra bu malzemelere yapay yalandrma sl ilemi uygulanarak malzeme sertliinin zamanla deiimi aratrlmtr.
2. DENEYSEL YNTEM Bu almada; %99.9 saflkta ve 45 m alt metal ve seramik tozlar kullanlarak iki farkl bileime sahip ve katmandan oluan DMler retilmitir. Lazer parack boyutu lm yntemiyle almada kullanlan toz boyutlar belirlenmitir. retilen kompozit malzemelerde anayap olarak AA 7075, takviye malzemesi olarak SiC seramik paracklar kullanlmtr. ki farkl bileimdeki DMlerden ilkinde alt katman AA 7075, orta katman %10 ve st katman %20 SiC takviyeli; dierinde alt katman AA 7075, orta katman %20 ve st katman %40 SiC takviyeli olmak zere iki farkl bileimde DM retilmitir. Hacimce yzde bileimi hazrlanan tozlar deirmen tipi kartrcda 2 saat sreyle kartrlmtr. Elde edilen karmlar, srasyla alt katmandan balanarak ortalama 13 MPa basn altnda n sktrma ilemine tabi tutulmutur. Yaplan bu ilem sonras 70x70 mm boyutlarndaki malzemelere 13 MPa basn altnda ve 575Cde 30 dakika sreyle sktrma ve sinterleme ilemleri e zamanl olarak uygulanmtr.
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Daha sonra retilen iki farkl bileimdeki malzemenin k mikroskobu grntleri alnmtr. n sktrma ve ardndan gerekletirilen sinterleme ilemi 11 kW gcnde ve 15 ton sktrma kapasiteli scak presleme cihaznda gerekletirilmitir. retilen DMlere 470Cde 1 saat sreyle zeltiye alma ve ardndan su verme ilemi uygulanmtr. Su verilmi malzeme, ya banyosunda 120C scaklkta 78 saate kadar farkl srelerde yapay yalandrma ilemine tabi tutulmutur. Malzemelerin belli aralklarda sertlik lmleri gerekletirilmitir. Brinell sertlik lmleri 2,5 mm bilye ap ile 187,5 kg yk altnda gerekletirilmitir. lmler sonunda yalandrma sresinin DMlerin sertlii zerine etkisi belirlenmitir.
3. DEERLENDRME 3.1 Yap ncelemeleri retim sonras alnan kesit grntlerinde, 3 katmanl DMlerin baarl bir ekilde retilebildii grlmtr. ekil 1de %40 ve %20 hacimsel takviye oranlarna sahip DMnin kesit grnts rnek olarak verilmitir.
ekil 1. retilen DMlere ait kesit grnts. Parack takviyeli kompozit malzemelerde toz boyut ve dalm sinterlenme davran zerinde nemli bir etkiye sahiptir. Toz boyut lmleri sonucunda belirlenen ortalama toz boyutlar izelge 1de verilmitir. izelge 1. almada kullanlan tozlarn ortalama boyutlar Malzeme Al Zn Mg Cu Fe Cr Si SiC Ortalama Toz Boyutu (m) 10,22 6,66 45,08 19,17 6,66 33,42 3,53 32,67
Takviye paracklarnn bykl, takviye malzemesinin anayap ierisinde homojen dalm asndan olduka nemlidir. Takviye malzemesi olarak kullanlan SiC paracklar ve anayapnn nemli bir ksmn oluturan Al tozlar arasndaki boyutsal oran, tozlarn nemli miktarda homojen dalmn salamtr. Elde edilen homojen dalm, retilen DMnin hacimce %20 takviyeli blgesinden alnan ve ekil 2de verilmi olan k mikroskobu grntsnde aka grlebilmektedir. Homojen toz dalm 3 farkl katman ierisinde, malzeme zelliklerinin blgesel olarak farklln byk lde ortadan kaldrarak, izotropik mekanik zelliklerin elde edilmesini salamtr. Takviye miktarnn art ekil 3te verilen ve hacimce %40 takviyeli katmana ait olan k mikroskobu grntsnde gzlemlendii gibi, takviye paracklarn anayap ierisinde homojen dalm gsterdii fakat takviye miktarnn artna bal olarak yap iinde bir miktar topaklanma meydana geldii gzlemlenmitir.
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ekil 2. Hacimce %20 parack takviyeli katmana ait k mikroskobu grnts.
ekil 3. %40 parack takviyeli katmana ait k mikroskobu grnts.
ekil 3te grld gibi takviye miktarnn %40 olduu katmanda, takviye miktarnn nemli miktarda artmasna ramen, anayap ierisinde mmkn olduunca homojen parack dalm elde edilebilmitir. Bu durum retilen DMnin her katmannda izotropik mekanik zellik elde edilebildiinin bir gstergesidir. Anayapy oluturan Al 7075 alam ierisinde byk oranda bulunan Al, Zn ve Mg elementleri yap ierisinde MgZn2nin bulunmasn, yap ierisindeki MgO ve SiC paracklarnn bulunmas ise MgSi2 bileiklerinin bulunma ihtimalini glendirmektedir [8-9]. 3.2 Sertlik Davran ki farkl bileimde retilen DMlere 120Cde yapay yalandrma ilemi uygulanm, numunelerin belirli sre aralklarnda sertlik deiimleri belirlenmi ve ulalan en yksek sertlik deerleri tespit edilmitir. %20-10 takviye oranna sahip DMye 120Cde uygulanan yapay yalandrma ilemi sonucunda DMyi oluturan katmana ait sertlik deiimleri ekil 4de verilmitir.
ekil 4. Hacimce %20 ve %10 takviyeli katmanlara sahip DMnin yapay yalanma davran
Hacimce %20 ve %10 takviyeli katmanlara sahip DMye uygulanan ve 120Cde 78 saate kadar gerekletirilen yalandrma ilemi sonucunda, beklendii gibi en yksek sertlik deeri en fazla takviye miktarna sahip katmanda elde edilmitir. zeltiye alma ve su verme ilemlerinden sonra gerekletirilen yalandrma ileminin ilk saatlerinde sertlik deerlerinde belirgin biimde art grlrken, ilerleyen yalandrma srelerinde farkl katman iin sertlik deerlerinde bir miktar d olduu ve daha sonra belirgin bir deiimin olmad gzlemlenmitir. Her
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katmanda sertlik deiiminin genel olarak ayn ynelime sahip olduu grlmektedir. Anayapya ilave edilen takviye malzemesinin, anayapnn yalanma karakteristiine etkisi olmad anlalmaktadr. Hacimce %40 ve %20 takviyeli katmanlara sahip DMnin 120Cde 78 saat boyunca gerekletirilen yalandrma ilemi sonucu elde edilen sertlik deiimi ekil 5te verilmitir.
ekil 5. Hacimce %40 ve %20 takviyeli katmanlara sahip DMnin yapay yalanma davran. Uygulanan yapay yalandrma ilemi sonucunda hacimce %40 takviye oranna sahip katmanda en yksek sertlik deeri elde edilmitir. Artan takviye oranlarnn sertlik deiim eiliminde genel olarak bir deiime yol amad, takviyesiz alt katman ve takviyeli katmanlar arasnda sertlik deiiminin ayn ynelime sahip olduu grlmtr. retilen her iki eit DMde de 65 saatlik bir yalandrma sonunda en yksek sertlik deerine eriildii gzlemlenmitir. GP blgelerinden sonra yar badak keltilerinin oluumu bu sre boyunca gereklemektedir. 65 saatlik srenin devamnda ise sertlik deerlerinde dme balamaktadr. SiC ilavesinin anayapnn sertlik deiimi eilimine etki etmedii, sadece takviyenin hacimsel oranna bal olarak sertlikte arta neden olduu tespit edilmitir. 4. SONULAR En yksek sertlik deeri 120Cde 65 saate kadar yaplan yapay yalandrma ilemi sonucu %40 SiC parack takviyeli katmanda elde edilmitir. Daha yksek yalandrma srelerinde sertlik deerlerinin azalmaya balad gzlemlenmitir. Anayapya ilave edilen takviye malzemesi orannn ulalan sertlik seviyesini etkiledii fakat ana yapnn yalanma karakteristiini deitirmedii belirlenmitir.
TEEKKR Bu alma, TBTAK 110M034 projesi kapsamnda gerekletirilmitir. Verdii destekten dolay TBTAKa teekkr ederiz. 5. KAYNAKA [1]. Kainer, K. U., Metal Matrix Composites: Custom-made Materials for Automotive and Aerospace Engineering, Wiley, Weinheim, 2006. [2]. Kalkanl, A., Ylmaz, S., Synthesis and characterization of aluminum alloy 7075 reinforced with silicon carbide particulates, Materials and Design, 29, 775-780, 2008. [3]. Goupee, A. J., Vel, S. S., Transient multiscale thermoelastic analysis of functionally graded materials, Composite Structures, 92, 1372-1390, 2010. [4]. Ruiz-Navas, E. S., Gordo, E., Garcia, R., Development and Characterization of 430L Matrix Composites Gradient Materials, Materials Research, Vol. 8, No. 1, 1-4, 2005.
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[5]. Chao, S., Song, M., Wang, Z., He, Y., Effect of Particle Size on the Microstructures and Mechanical Properties of SiC-Reinforced Pure Aluminum Composites, JMEPEG_ASM International, DOI: 10.1007/s11665010-9801-3, 2011. [6]. Wang, Z., Song, M., Sun, C., He, Y., Effects of particle size and distribution on the mechanical properties of SiC reinforced AlCu alloy composites, Material Science and Engineering, A 528, 1131-1137, 2011. [7]. German, R. M., Toz Metalurjisi ve Parackl Malzeme lemleri, Tercme: Sarta, S.,Trker, M., Durlu, N.,Trk Toz Metalurjisi Dernei Yaynlar: 05, Ankara, 15-500, 2007. [8]. Aycan, M.F., Yalandrma ileminin Al2O3 ve SiC takviyeli aluminyum alam esasl kompozitlerin mekanik zelliklerine etkisi, Yksek Lisans Tezi, TOBB ET F.B.E., 2010. [9]. Wenchuan, M., Jialin, G., Yong, Z., Mingmei, W., Effect of SiC Particles on ageing behaviour of SiCp/7075 Composites, Journal of Materials Science Letters, 16, 1867-1869, 1997. [10]. Dasgupta, R., Meenai, H., SiC particulate dispersed composites of an AlZnMgCu alloy: Property comparison with parent alloy, Materials Characterization, 54, 438-445, 2005. [11]. Chen, J., Zhen, L., Yang, S., Shao, W., D, S., Investigation of precipitation behavior and related hardening in AA 7075 aluminium alloy, Materials Science and Engineering, A 500, 34-42, 2009. [12]. Lloyd, D. J., Chatuverdi, M. C., A calorimetric study of aluminum alloy AA-7075, Journal of Materials Science, 17, 1819-1824, 1982. [13]. Sha, G., Cerezo, A., Early-stage precipitation in Al-Zn-Mg-Cu alloy (7050), Acta Materialia 52, 4503-4516, 2004.
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SICAK PRES YNTEM LE ATOMZE Al-SiC KOMPOZT TOZLARININ YOUNLATIRILMASI

Rdvan YAMANOLU, Erdem KARAKULAK, Muzaffer ZEREN Kocaeli niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 41380, Kocaeli, ryamanoglu@kocaeli.edu.tr, mzeren@kocaeli.edu.tr
ZET Bu almada, Kocaeli niversitesi Metalurji ve Malzeme Mhendislii Blmnde retimi gerekletirilen Al-SiC kompozit tozlarnn sinterleme davranlar incelenmitir. Sinterleme iin vakum destekli scak presleme teknii seilmitir. retilen tozlar farkl scaklk, sre ve basn altnda sinterlenmi ve proses parametrelerinin sinterleme karakteristii zerine etkileri saptanmtr. Elde edilen kompaktlarn younluklar, mikroyapsal karakteristikleri ve sertlikleri incelenerek sonular deerlendirilmitir. Sinterlenmi numuneler dendritik yap sergilemi ve sertlikleri 79 ile 117 kg/mm2 arasnda deiim gstermitir. Anahtar Kelimeler: Al-SiC, Dnel Elektrot Yntemi, Vakum Destekli Scak Presleme
CONSOLIDATION OF ATOMIZED Al-SiC COMPOSITE POWDERS BY HOT PRESSING

ABSTRACT In this study, sintering behaviour of Al-SiC composite powders fabricated at Kocaeli University Department of Metallurgical and Materials Engineering was investigated. A vacuum hot pressing technique was selected for sintering of produced powders. The powders were consolidated under various temperature, holding time and pressure conditions. The effect of process parameters on the sintering characteristic was revealed. Hot pressed samples were examined in terms of relative density, microstructure and hardness. Sintered samples showed dendritic structure and their vickers hardnesses are in the range of 79-117 kg/mm2. Keywords: Al-SiC, Rotating Electrode Process, Vacuum Hot Pressing 1. GR zellikle otomotiv, uzay, denizcilik ve spor malzemeleri gibi endstriyel alanlarn ounda kompozit malzemeler sahip olduklar stn zelliklerinden dolay geleneksel malzemelerin yerine tercih edilmektedirler [1-2]. Sz konusu metal matrisli kompozit olduunda en yaygn kullanlan takviye malzemelerinden biri olan SiC, yksek scaklk mukavemeti ve modlne, dk younlua, iyi oksidasyon direncine ve yksek sertlie sahiptir [3-4]. Matris malzemesi olarak ise hafiflikleri, stn korozyon direnleri ve uygun mekanik zelliklerinden dolay aluminyum alamlar dikkati ekmektedir. Matris ile takviye malzemesi arasndaki arayzeyin doas kompozitin zellikleri asndan olduka nemlidir [5]. Dolaysyla SiC partiklleri ve aluminyum matris arasndaki fiziksel ve kimyasal uyum SiC/Al kompozitlerin hazrlanmas srasnda kritik unsurlardr [6,7].
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Al-SiC MMK (Metal Matrisli Kompozit) malzeme retimi iin farkl metodlar uygulanmaktadr. Bunlardan yaygn olarak kullanlanlardan bazlar, dkm, infiltrasyon, sprey teknii ve toz metalurjisidir. Standart dkm tekniinde SiC takviye faz ile matris alam ergitme srasnda kartrlarak homojenlik salanr ve katlatrlr. nfiltrasyon tekniinde gzenekli yap olarak elde edilen SiC ktle iine sv halde matris malzeme infiltre edilir. Sprey teknii ise atomize edilen matris malzemesi ierisine katlama tamamlanmadan partikllerin enjekte edilmesine dayanr. Alternatif olarak kullanlan toz metalurjisi ile Al-SiC MMK retimi, aluminyum tozlar ile SiC partikllerinin kartrlmas, preslenmesi ve sinterlenmesine dayanr [8]. Bu almada da farkl olarak kompozit tozlar santrifuj atomizasyonu ile retilmi ve ardndan scak pres ile sinterlenmitir. Scak preslemede ilk younlama paracklarn yeniden dzenlenmesi ve partikllerin temas noktalarndaki plastik ak ile gerekleir. Dier basnl yntemlere nazaran scak presleme dngs daha yavatr. Sinterlenecek ktle arttka sreler ok uzayabilir. Maksimum basn deeri 50 MPadr. Kirlenmeleri ve oksidasyonu nlemek iin genellikle vakum ortamnda allr. Pahal bir yntem olmasna ramen sert ve youn malzemelerin zellikle de elmas kesici takmlarn retiminde yaygn bir ekilde kullanlmaktadr [9].
2. DENEYSEL ALIMA Deneysel almada matris malzemesi olarak Etial-24 (DIN AlCu4Mg1) normunda Al-Cu alam kullanlmtr. Kullanlan alamn kimyasal bileimi izelge 1de verilmitir. Bu alama dkm srasnda yaklak 650 nm (ekil 1) boyuta sahip, ktlece % 4 SiC partiklleri ilave edilmitir. Ergiyen alam silindirik kalplara dklerek katlamaya braklmtr. Dkm yntemiyle retilen MMK malzeme scak ekstrzyon yntemiyle ekillendirilmitir. Scak ekstrzyon ilemi SiC partikllerinin yap iinde homojen dalm salamak ve uygulanacak atomizayon ilemine uygun boyutlu ubuk elde etmek iin gerekletirilmitir. ekil 2de SiC partikllerinin homojen dalmlarnn salanmas iin kartrld srada ekilmi bir grnt sunulmutur. izelge 1. Bu almada kullanlan matriks alamnn kimyasal bileimi. Etial-24 % Si 0,5 % Fe 0,5 % Cu 4,3 % Mn 0,6 % Mg 1,5 % Cr 0,1 % Zn 0,25 % Ti 0,15
ekil 1. almada kullanlan SiC partikllerinin SEM grntleri
ekil 2. Pota ierisindeki dkm alam
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Dkm ubuklar daha sonra plazma destekli dnel elektrot yntemi ile toz haline getirilmitir. Farkl boyutlarda toz eldesi iin deiik devir saylarnda allmtr. Toz boyut dalmlarnn belirlenmesinin ardndan iki farkl grup toz (150-250 ve 300-500 m) Diex marka vakum destekli scak pres (ekil 3) ile sinterlenmitir. Grafit kalplar arasna konan tozlar farkl scaklk, basn ve srede younlatrlmtr.
ekil 3. Diex marka scak pres cihaz Sinterlenen kompaktlarn younluklar arimet yntemi ile, sertlikleri Fisherskop marka Vikers sertlik cihaz ile belirlenmitir. Numunelerin mikroyapsal karakterizasyonlar iin Zeiss Axiotech k mikroskobu ve Jeol 6060 tarama elektron mikroskobu kullanlmtr. 3. SONULAR ekil 4de Kocaeli niversitesi Metalurji ve Malzeme Mhendislii Blmnde retilen ve bu almada kullanlan kompozit partikllerin grntleri verilmitir. Devir saysna bal olarak elde edilen partikllerin morfolojileri deimektedir. Artan devir says ile tozlar kresellemektedir. Ayn ekilde dk devir saysnda ise kreselleme iin yeterli zamann bulunmamas nedeniyle karmak ekilli partikller olumaktadr.
ekil 4. Al-SiC kompozit tozlarnn tarama elektron mikroskobu grntleri 150-250 ve 300-500 m boyut aralna sahip tozlar scak preste younlatrlmtr. izelge 2de plazma destekli dnel elektrot yntemi ile retilen Al-SiC MMK tozlarnn vakum destekli scak pres ile sinterlenmesi srasnda kullanlan parametreler ve sonular sunulmutur.
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izelge 2. Al-SiC MMK tozlarnn scak presleme parametreleri Numune kodu A1 A8 A9 A2 A3 A6 A10 A11 A4 A5 A7 A12 Scaklk (oC) 530 530 530 550 550 550 550 550 560 560 560 560 Basn (MPa) 20 20 20 20 20 23 20 20 20 20 25 20 Sre (Dakika) 10 25 25 5 10 7 25 25 15 30 20 25 Younluk (%) 88,80 93,60 96,00 95,50 96,20 98,20 97,00 98,60 97,80 97,90 99,00 99,20 Toz boyutu (m) 150-250 150-250 300-500 150-250 150-250 150-250 150-250 300-500 150-250 150-250 150-250 300-500
10 dakika bekleme sresi ve 20 MPa basn altnda elde edilen (A1) % 88,8lik gibi nispeten dk younluk deerinden sonra ilk olarak scaklk 20 oC arttrlm sre ise 5 dakikaya drlmtr. Sredeki azalmaya ramen scaklktaki 20 oClik art ile yaklak % 7lik bir ykselme salanarak (A2) % 95,5 younluk elde edilmitir. Tam younlua ulamak iin bu aamadan sonra scaklk deitirilmeden sre tekrar 10 dakikaya karlmtr. Scaklk etkisinin aksine bekleme sresi ok az da olsa younlua % 0,7lik (A3) bir katk salamtr. ok uzun bekleme sresinden kanmak iin scaklk bir 10 oC daha arttrlm ve ilave olarak bekleme sresi 15 dakikaya ykseltilmitir. Bu iki katk ile younluk (A4) % 1,60 artmtr. Ayn scaklkta bekleme sresi iki kat arttrlarak 30 dakikaya karlm (A5) ve daha nceki sonulardan da grld gibi bekleme sresinin etkisinin ok az olduu sonucuna varlmtr. Tm bu denemelerden sonra sinterleme davranna etki eden en nemli parametrelerden olan basn etkisini grmek asndan yine ok ksa bir bekleme sresi ve 550 oC de sadece 3 MPalk bir basn art ile (A6) % 98,2 gibi olduka yksek bir younluk elde edilmitir. Bu aamada grlen etkili basn desteinin ardndan scaklk tekrar 560 oC ye, basn deeri 25 MPaa ve bekleme sreside 20 dakikaya karldnda (A7) % 99luk bir younlua ulalmtr. Tm bu parametrelere ilave olarak toz boyutu arttrldnda malzemelerin younluunda art grlmtr. A1 (% 88) ve A7 (% 99) numunelerine ait k mikroskop grntleri ekil 5a ve 5bde verilmitir. En yksek gzeneklilie sahip bu numunede tozlarn temas blgelerinde byk boyutlu boluklar grlmektedir. Yksek younlua sahip numunede ise gzenekler neredeyse tamamen kapanmtr.
ekil 5. Sinterlenen numunelerin parlatlm konumda k mikroskobu grntleri, a) % 88 younluklu, b) % 99 younluklu numune
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ekil 6da bu kez A1 ve A7 numunelerinin dalanm konumdaki k mikroskobu grntleri sunulmutur. Dendritik katlama sergileyen bu numunelerde kimyasal kompozisyona bal olarak yer yer tektik blgelerde dikkati ekmektedir.
ekil 6. Sinterlenen numunelerde dalanm konumda k mikroskobu grntleri Optik incelemelerin yannda krlma yzeyleri de incelenerek yine ayn ekilde en dk ve en yksek younluklu numuneler iin grntler ekil 7de verilmitir. Dk younluklu numunede partikller aras balant zayfken yksek younluklu numunenin sahip olduu kuvvetli balant net bir ekilde grlmektedir. Yksek younlua sahip numunede artan basnca bal olarak youn deformasyon grlmektedir.
a)
b)
ekil 7. Krlma yzeylerinin SEM grntleri, a) % 88, b) % 99 younluklu numune
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Mikroyapsal karakterizasyonlarn ardndan karlatrma amacyla farkl yntemler ile retilen malzemelerin sertlikleri llmtr. izelge 3de SiC iermeyen dkm alam, SiC katkl dkm alam ve scak preslenmi numuneler iin sertlik deerleri verilmitir. SiC ierii ve yalanma ile sertlikte art meydana gelmitir. izelge 3. Farkl yntemlerle retilen alamlarn sertlik deerleri Malzeme AlCuMg (Dkm) AlCuMg (Dkm, yalanm; 220 Cde 6 saat)
o
Sertlik (HV10) kg/mm2 90 129 110 139 117

o
Al-SiC (Dkm) Al-SiC (Dkm, yalanm; 220 oCde 6 saat) Al-SiC (Scak pres) Al-SiC (Scak pres yalanm: 220 Cde 6 saat)
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Farkl parametrelere bal olarak elde edilen deiik younluk deerleri iin sertlik lldnde ise ekil 8deki diyagram elde edilmitir. Artan younluk ile sertlikteki art net bir ekilde grlebilmektedir.
ekil 8. Sertlik ile younluk arasndaki iliki Bu alma ilk olarak kompozit tozu retimi temeline oturtulmutur. Kompozit tozlar baarl bir ekilde retildikten sonra sinterleme davranlarnn belirlenmesi iin scak pres ile younlatrlmlardr. Farkl parametrelerin sinterleme zerine etkileri saptanarak % 99 terorik younlua ulalmtr. Elde edilen malzemelerin mikroyapsal karakterizasyonlarnn ardndan sertlikleri llm ve dier yntemlerden daha yksek deerler elde edilmitir.
TEEKKR Bu almaya Atomizasyon Teknikleri ile Toz retimi isimli proje kapsamnda verdii destekten dolay Kocaeli niversitesi, Bilimsel Aratrma Projeleri Komisyon Bakanlna teekkrlerimizi sunarz.
KAYNAKLAR [1] Thnemann, M., Beffort, O., Kleiner, S., Vogt, U., Aluminum matrix composites based on preceramic-polymerbonded SiC preforms, Composites Sciences and Technology, 67, 2377-2383, 2007.
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[2] Mondal, D. P., Das, S., Suresh, K. S., Ramakrishnan, N., Compressive deformation behaviour of coarse SiC particle reinforced composite: effect of age-hardening and SiC content, Materials Science and Engineering A, 460-461, 550-560, 2007. [3] He, X., Hang, X., Zhang, C., Zhou, X., Zhou, A., Microstryuctures and mechanical properties of Cf/SiC composites by precursor pyrollysis-hot pressing, Materials Science and Engineering A, 284, 211-218, 2000. [4] Niklas, A., Froyen, I., Delaey, I., Comparative evaluation of extrusion and hot isostatic pressing as fabrication techniques for Al-SiC composites, Materials Science and Engineering A, 135, 225-229, 1991. [5] algl, U., Dikba, H. ve Takn, M., Scak presleme yntemiyle imal edilmi SiCp takviyeli aluminyum esasl kompozitlerin dfuzyon kaynanda srenin birleme zerindeki etkisinin incelenmesi, Frat niv., Fen ve Mh. Bil. Dergisi, 18 (3), 437-443, 2006. [6] Wang, R. M., Surappa, M. K., Tao, C. H., Li, C. Z. and Yan, M. G., Microstructure and interface structure studies of SiCp-reinforced Al (6061) metal-matrix composites, Materials Science and Engineering: A, Volume 254, Number 1, 219-226, 1998. [7] Ma, T., Yamaura, H., Koss, A. D. and Voigt R. C., Dry sliding wear behavior of cast SiC-reinforced Al MMCs, Materials Science and Engineering: A 360, 116-125, 2003. [8] Eslamian, M., Rak, J., Ashgriz, N., Preparation of aluminum/silicon carbide metal matrix composites using centrifugal atomization, Powder Technloogy, 184, 11-20, 2008. [9] German, R. M., Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Dernei Yaynlar, 2007.
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WO3N H2CH4 GAZ KARIIMIYLA REAKSYONU YOLUYLA TEK ADIMDA WC TOZ SENTEZ
enol ETNKAYA, erafettin EROLU stanbul niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mh. Blm Avclar Kamps, 34320 Avclar / stanbul senol-c@istanbul.edu.tr seref@istanbul.edu.tr ZET Bu almada WO3 tozu Ar atmosferinde stlm ve akabinde H2CH4 (% 10) gaz karmlaryla 9001300 Kde 60 dk ve 120 dk srelerde reaksiyona sokulmutur. Deiik reaksiyon kademelerindeki rnlerin karakterizasyonu iin XRD ve SEM teknikleri kullanlmtr. Partikl boyutu 0.21.5 m ve kristal boyutu ~50 nm olan tek faz WC tozu, 1300 Kde 120 dk iinde elde edilmitir. Gibbs serbest enerji minimizasyon yntemiyle yaplan termodinamik analiz sonular, WC oluumu iin deneysel artlar tahmin etmede ve sentez prosesini anlamada klavuz olarak kullanlmtr. Termodinamik analiz, 1300 Kde WC oluumunun artan reaktan gazlar ile WO3 WO2 W WC eklinde olduunu ngrmektedir. Anahtar Kelimeler: WC toz sentezi, kat-gaz reaksiyonu, X-n difraksiyonu, morfoloji, termodinamik analiz.
ONE-STEP SYNTHESIS OF WC POWDERS BY REACTION OF WO3 WITH H2CH4 GAS MIXTURE

ABSTRACT In this study, WO3 powder was heated in Ar atmosphere and were subsequently reacted with H2CH4 (% 10) gas mixtures at 9001300 K for 60 min and 120 min. XRD and SEM techniques were used to characterize the products at various stages of the reactions. It was found that single phase WC powders with particle size of 0.21.5 m and crystallite size of ~50 nm were obtained at 1300 K within 120 min. Equilibrium thermodynamic analysis by the method of minimization of Gibbs free energy was used as a guide to predict the experimental conditions for the formation of WC and to understand the synthesis process. Thermodynamic analysis at 1300 K reveals that WC formation follows the path WO3 WO2 W WC with increasing amount of reactant gases. Keywords: WC powder synthesis, solid-gas reaction, X-ray diffraction, morphology, thermodynamic analysis. 1. GR Tungsten karbr (WC), sertlik, elastisite modl, ergime scakl ve korozyon direnci gibi fiziksel ve kimyasal zellikleri yksek olan refrakter bir malzemedir. Bu stn zelliklerinden dolay WC, anma direnli paralarda ana bileen olarak kullanlmaktadr [13]. WC tozlar, deiik balang malzemeleri kullanlarak birok metotla retilmektedir. Klasik yntemle WC retimi, W tozunun kat karbon siyah ile yksek scaklklarda (16002000 K) karbrizasyonu sonucu gerekletirilmektedir
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[4]. Bu yntem, kat reaktanlar arasndaki reaksiyon hznn dk olmas nedeniyle uzun karbrizasyon sreleri gerektirmektedir. Sentez sonras elde edilen kaba partikllerin boyutlar mekanik tme yoluyla drlmektedir. Bu ilem, prosese ilave bir zaman ve klfet getirmektedir. Ayrca nihai rn, kat karbondan ve tcden kaynaklanan Ca, Si, Fe, S, P gibi empriteler ile kirlenmektedir [5]. Mikronalt WC partiklleri sentezlemek iin, hzl karbotermal indirgeme [5], yksek enerjili tme [6], kimyasal buhar biriktirme [7], termokimyasal proses [810], kat-gaz reaksiyonlar [1114] gibi eitli yntemler gelitirilmitir. Bu yntemlerde karbrizasyon scakl ve/veya sresi klasik ynteme gre daha dktr. Kat-gaz reaksiyonu (gaz faz karbrizasyonu), gaz fazndaki karbon molekllerinin tungsten ieren partikllerle yakn temas sonucu dk scaklklarda bile karbrizasyon hzn arttrmaktadr. Bu nedenle bahsi geen yntem byk ilgi grmtr. Giraudon ve dierleri [14], WO3in H2 / CH4 gaz karm ile e zamanl indirgenmesi ve karbrizasyonunu incelemilerdir. Oksit esasl balang malzemesi kullanldnda, W2C, W ve C gibi dier fazlar olmadan WC sentezlemek iin indirgeme ve karbrizasyon arasnda hassas bir denge olduunu ifade etmilerdir. Davidson ve dierleri [15], mikrokristal W tozlarnn H2 / CH4 gaz karm ile karbrizasyonunun 1073 Kde baladn, fakat yksek scaklklarda (11731323 K) reaksiyonun ok daha etkili olduunu belirtmilerdir. Bu almada, WC sentezi iin ncelikle Gibbs Serbest Enerji Minimizasyon yntemi kullanlarak WO3H2CH4 sisteminde 9001300 K aralnda termodinamik analiz yaplmtr. Deneysel almalarda ise WO3 tozunun 9001300 Kde H2CH4 (% 10) gaz karmlaryla reaksiyon davran incelenmitir. Sentezlenen rnlerin karakterizasyonu iin XRD ve SEM teknikleri kullanlmtr. Ayrca prosesin termokimyasnn akla kavuturulmas amacyla 1300 Kde kat ve gaz fazndaki deiimler termodinamik analizler yardmyla hesaplanm ve olas reaksiyon mekanizmas ortaya konmutur.
2. TERMODNAMK ANALZ Termodinamik analiz, istenilen fazlarn sentezlenmesi iin gerekli proses parametrelerini tahmin etmek ve prosesin termokimyasn anlamak iin kullanlan yararl bir yntemdir [16]. Bu amala yaplan termodinamik analizlerde, Gibbs Serbest Enerji Minimizasyon ynteminden [17] yararlanlmtr. Termodinamik hesaplar iin, Eriksson tarafndan hazrlanan Solgas-Mix adl bilgisayar programnn Besmann tarafndan gelitirilmi versiyonu kullanlmtr [18]. Bu yntemle sabit scaklk ve basnta, verilen girdi kompozisyonu iin denge halindeki (sistemin enerjisinin minimum olduu durumdaki) gaz ve youn faz bileimleri hesaplanmaktadr. Hesaplarn yaplabilmesi iin ilgili scaklk aralndaki mevcut olan tm element ve bileiklerin termodinamik verilerinin (Gof, bileenlere ait standart serbest oluum enerjilerinin) bilinmesi gerekmektedir. Bu almada kullanlan termodinamik veriler, termokimyasal tablolardan [19, 20] temin edilmitir. Hesaplamalarda reaktan (girdi) bileimi ve scaklk deitirilmi, basn (1 atm) ise sabit tutulmutur. Hesaplama sonular, scaklk ve girdi bileimine bal olarak kararl durumdaki kat fazlar gsteren hal diyagramlar eklinde gsterilmitir. Ayrca, proses termokimyasnn aklanmas amacyla kat faz ve gaz faz bileimlerindeki deiimler de grafik halinde gsterilmitir.
3. DENEYSEL ALIMALAR Deney dzenei temel olarak Ar (% 99,999), H2 (% 99,99) ve CH4 (% 99,5) gazlarn ieren gaz silindirlerinden, bu gazlarn ak hzlarn hassas bir ekilde belirlemek iin ak lerlerden (Dwyer) ve ierisinde sentez reaksiyonlarnn gerekletirilecei kuvars tp (i ap: 20 mm) bulunan frn sisteminden (Strhlein) olumaktadr. Sentez almalar iin gerekletirilen her bir deneyde ~10-3 mol (~0,2319 g) WO3 tozu (SigmaAldrich) kullanlmtr. Tm deneyler ncesinde, oksit tozunun bnyesinde bulanabilecek olan nemin giderilmesi amacyla ~373 Kdeki etvde 10 dakikalk bekletme yaplm ve tartmlar 10-4 g hassasiyete sahip analitik terazide (Sartorius BP110S) gerekletirilmitir. Tartlan WO3 tozu, almina kaykk ierisinde tp frnn merkezine yerletirilmi ve ~25 K/dk stma hzyla Ar atmosferinde (85 cm3/dk) 900, 1000, 1100, 1200 ve 1300 Ke stlmtr. stenilen s-
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cakla ulaldktan sonra Ar gaz ak kesilerek 60 ve 120 dklk srelerde H2CH4 gaz karm ile reaksiyonlar gerekletirilmitir. H2 ve CH4 gaz ak hzlar srasyla reaksiyon sresi 60 dk iin 370 cm3/dk ve 40 cm3/dk; 120 dk iin ise 185 cm3/dk ve 20 cm3/dk olacak ekilde sabit tutulmutur. Bu ekilde sisteme verilen toplam reaktif gaz miktarnn ayn olmas salanmtr. Tm deneylerde frn oda scaklna soutuluncaya kadar 85 cm3/dk ak hznda Ar gaz sistemden geirilmitir. Sentezlenen rnlerinin faz analizleri, Rigaku D/Max2200/PC marka XInlar Difraksiyon (XRD) cihaznda; morfoloji incelemeleri ise, Jeol 6335 marka Taramal Elektron Mikroskoplarnda (SEM) gerekletirilmitir. Reaksiyon rnlerinin kristal byklkleri, (1) nolu eitlikte verilen Scherrer forml kullanlarak hesaplanmtr. (1) Eitlik (1)de gsterilen , Cu K radyasyonunun dalga boyunu (0,15418 nm); , difraksiyon asn; t, kristal boyutunu ve , yar ykseklikteki pik geniliini (FWHM) ifade etmektedir. FWHM deerleri belirlenirken ~0,2lik cihazdan kaynaklanan pik genilemesi de dikkate alnmtr.
4. BULGULAR ve DEERLENDRME 4.1. Termodinamik Analiz Sonular WC sentezi amacyla WO3H2CH4 sisteminde 9001300 K aralnda yaplan termodinamik analizde, gaz faznda 9001000 K iin 76 bileen; 11001300 K iin 46 bileen dikkate alnmtr. Bunlar arasnda H2, CH4, CH3, C2H4, C3H6, CH2O, H2O, CO, CO2 ve H2WO4 bulunmaktadr. Denge durumundaki youn fazlar ise WO3, WO2, H2WO4 (sadece 9001000 K iin), W, W2C, WC ve Cdan olumaktadr. Tm hesaplamalarda WO3 miktar 0.001 mol ve H2/CH4 mol oran 9.25 olarak sabit tutulmutur. Hesaplama sonular, ekil 1de scaklk ve CH4 mol kesri [noCH4/ (noCH4+noWO3)] ile kararl kat faz alanlarndaki deiimi gsteren denge diyagram olarak gsterilmektedir.
ekil 1. WO3 H2 CH4 sistemi iin denge durumundaki kararl kat faz alanlarnn CH4 mol kesri ve scaklkla deiimi (noWO3 = 0.001 mol; noH2 / noCH4 = 9.25) ekil 1den 9001300 K aralnda kararl durumdaki kat faz alanlarnn WO3+WO2, WO2, WO2+WC, WO2+W+WC, WO2+W, W, W+WC, WC ve WC+C olduu grlmektedir. Dk CH4 mol kesirlerinde (0.08) WO3ten WO2 olumakta daha sonra tek faz WO2 blgesi kararl faz alan olarak gze arpmaktadr. Dk scaklklarda (9001000 K), artan CH4 mol kesri ile WO2ten WC faz direkt olarak olumaktadr. Yksek scaklklarda (11001300 K), artan CH4 mol kesri ile WO2 nce We indirgenmekte ve daha sonra Win karbrizasyonu sonucunda WC olumaktadr. Daha da yksek CH4 mol kesirlerinde ise WC faznn yannda serbest C ortaya kmaktadr. Ara scaklk kademesinde (10001100 K) ise WC, hem WO2ten hem de Wden olumaktadr. Ayrca, tek faz WC blgesinin artan scaklkla darald grlmektedir. rnein tek faz WC blgesi, 900 Kde 0.54 CH4 mol kesirlerinde, 1300 Kde ise 0.780.81 CH4 mol kesri aralnda olumaktadr. Yaplan termodinamik analiz sonucunda WO3in H2CH4 gaz karmyla reaksiyonu sonucu tek faz WC sentezinin mmkn olduu belirlenmitir.
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4.2. XRD Analiz Sonular ekil 2de 9001300 K aralnda yaplan 60 ve 120 dklk deneyler sonras elde edilen rnlerin XRD paternleri grlmektedir. Reaksiyon sresi 60 dk (ekil 2a) iin 900 Kdeki rnde ana faz olarak W ve az miktarda W2C saptanmtr. Scaklk 1000 Ke karldnda, rnn W, W2C ve WC fazlarndan olutuu anlalmtr. 1100 Kdeki rnde W2C pikleri gzkmezken 1000 Kdeki rne gre We ait pik iddetlerinin zayflad ve WC pik iddetlerinin artt tespit edilmitir. 1200 ve 1300 Kdeki rnlerin ana faz WCn yannda ok dk miktarda W ierdii saptanmtr. Bu sonular, 9001300 K scaklk aralnda kullanlan reaktif gaz bileiminde 60 dk reaksiyon sresinde saf WC elde edilemedii anlamna gelmektedir. Sisteme verilen toplam reaktif gaz miktar ayn kalmak artyla 120 dk srede yaplan deneyler sonras elde edilen rnlerin XRD paternleri de (ekil 2b) benzer davran sergilemektedir. Fakat, 60 dklk deneylere kyasla 9001200 K aralnda 120 dkda sentezlenen rnlerde W pik iddetlerinin dt (daha az miktarda W ierdii) ve 1300 Kde tek faz WC elde edildii ilgili paternlerden anlalmaktadr.
ekil 2. 9001300 K aralnda sentezlenen rnlerin XRD paternleri (a: 60 dk, b: 120 dk) ekil 3te XRD paternlerindeki her fazn ana pik iddetinin, fazlarn ana pik iddetlerinin toplamna oranlanmas sonucu hesaplanm faz bileimlerinden tespit edilen tahmini karbrizasyon oranlar (C/W) verilmektedir. Karbrizasyon oran grafikleri, deney sonularn genel olarak zetlemektedir. ekilden, her iki srede sentezlenen rnlerde, ykselen scaklkla karbrizasyonun artt anlalmaktadr. Toplam reaktif gaz miktar her iki srede yaplan deneyler iin ayn olsa bile 60 dklk rnlerin karbrizasyon oranlarnn 120 dklk rnlerden her zaman daha dk olduu ve tek faz WC sentezinin ancak 1300 Kde 120 dklk reaksiyon sonucu salanabildii belirlenmitir. Karbrizasyonun uzun sreli deneylerde daha etkili olmas, reaktif gazlarn tp ierisinde kal sresinin daha fazla olmas (daha yava gaz ak) nedeniyle daha fazla CH4 gaznn paralanmasna, dolaysyla daha fazla C oluumuna iaret etmektedir.
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ekil 3. Scaklk ve sreye bal olarak tahmini karbrizasyon oranlarndaki (C / W) deiim XRD paternlerindeki piklerin yar ykseklikteki genilikleri belirlenerek balang tozu WO3in ve reaksiyon rnlerinin kristal boyutlar (1) nolu eitlik yardmyla hesaplanmtr. Tm rnlerde mikrodeformasyon deerlerinin ihmal edilebilir dzeyde olduu saptanmtr. WO3 tozunun kristal boyutu ~50 nm iken; 900 Kde 60 ve 120 dk srelerde sentezlenen rnlerdeki Win kristal boyutlar srasyla 32 ve 40 nm olarak hesap edilmitir. 1000, 1100 ve 1200 Kde sentezlenen WCn kristal boyutlarnn ise 60 ve 120 dklk srelerde srasyla 2026 ve 3034 nm aralnda olduu bulunmutur. 1300 Kde yaplan deneyler sonras her iki sre iin de sentezlenen rnlerin kristal boyutlarnn ~50 nm olduu belirlenmitir. 4.3. Morfoloji ncelemeleri ekil 4te 9001300 K aralnda 60 ve 120 dklk srelerde sentezlenen rnlerin morfolojileri grlmektedir. SEM grntlerinden, artan scaklk ve sre ile partikl boyutlarnda byme meydana geldii anlalmaktadr. Tek faz WCn elde edildii 1300 K 120 dk deneysel arttaki rnde partikl boyutunun 0.21.5 m arasnda olduu saptanmtr. XRD piklerinden hesaplanm olan kristal boyutlarnn SEM lmlerinden elde edilmi olan boyutlardan daha dk olmas yapnn polikristal olduuna iaret etmektedir.
ekil 4. H2CH4 gaz karmyla 9001300 Kde sentezlenen rnlerin SEM grntleri (a), (c), (e) iin H2 : 370 cm3/dk, CH4 : 40 cm3/dk (b), (d), (f) iin H2 : 185 cm3/dk, CH4 : 20 cm3/dk
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4.4. WC Oluumu in Reaksiyon Mekanizmasnn Termodinamik Modellenmesi WO3H2CH4 sisteminde yaplan termodinamik analiz (ekil 1), 9001300 Kde tek faz WC sentezinin mmkn olduunu gstermitir. Deneysel almalarda ise, WO3in sadece 1300 Kde H2CH4 gaz karm ile 120 dklk reaksiyonu sonrasnda saf WC sentezlendii tespit edilmitir. allan artlarda daha dk scaklklarda CH4 gaznn paralanma kinetiinin ve C difzyonunun yava olmas nedeniyle tek faz WC sentezi mmkn olmamtr. ekil 1den 1300 Kde artan CH4 mol kesriyle WO3+WO2, WO2, WO2+W, W, W+WC, WC ve WC+C faz alanlarnn olutuu grlmtr. 1300 Kdeki WC sentezinin kimyasal reaksiyon mekanizmasnn anlalmas iin CH4 mol kesri ile denge durumundaki kat ve gaz bileimlerinin deiimi incelenmi ve sonular ekil 5a-bde grafikler halinde verilmitir.
ekil 5. CH4 mol kesri ile (a) kat ve (b) gaz fazlarnn bileimlerindeki deiim (T = 1300 K; noH2 / noCH4 = 9.25; noWO3 = 0.001 mol) ekil 5adan artan mol kesriyle ikili faz alanlarnda ortaya kan yeni fazn miktarnn artt anlalmaktadr. rnein, W+WC faz alannda (0.7120.776 mol kesir aralnda) artan CH4 miktar ile W %si azalrken WC %si artmaktadr. 1300 Kde H2CH4 atmosferinde WO3ten WC sentezinin srasyla WO3 WO2 W WC admlarndan getii ekil 5adan belirlenmitir. Bu sonular, WO3H2CH4 sisteminde WC sentezi zerine yaplan literatrdeki deneysel almalar [14, 2123] ile de uyum ierisindedir. ekil 5bden grlecei zere tm CH4 mol kesirlerinde gaz fazndaki rnlerin ana bileenlerinin H2O, CO ve CO2 olduu anlalmaktadr. Bu sonular da literatrdeki WC sentezi iin WO3H2CH4 sisteminde yaplm deneysel almalarda tespit edilen gaz trleri [14, 2123] ile de uyumludur. Ayrca termodinamik analiz sonucunda gaz faznda dk mol kesirlerinde az miktarda H2WO4, yksek mol kesirlerinde de dk miktarda C2H4, CH3 ve H gazlar tespit edilmitir. ekil 5bden WO3+WO2 faz blgesinde gaz fazndaki ana bileenlerin H2O, CO2, CO ve H2WO4 olduu ve bu gazlarn miktarlarnn WO3ten WO2e dnmn tamamland mol kesri olan 0.081 mol kesrine kadar artt anlalmaktadr. 0.081 mol kesrinin altnda H2 ve CH4 gazlarnn giren miktardan daha az kt grlmektedir. Bu da H2 ve CH4 gazlarnn reaksiyona girdiine iaret etmektedir. Bu sonular, (2) (7) nolu reaksiyonlar ile ifade edilebilir. (G0R = 18 400 J) (2) WO3 (k) + H2 (g) WO2 (k) + H2O (g) (3) 4WO3 (k) + CH4 (g) 4WO2 (k) + 2H2O (g) + CO2 (g) (G0R = 170 856 J) 5WO3 (k) + H2 (g) + CH4 (g) 5WO2 (k) + 3H2O (g) + CO2 (g) (G0R = 189 256 J) (4)
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3WO3 (k) + CH4 (g) 3WO2 (k) + 2H2O (g) + CO (g) (G0R = 158 561 J) (5) 4WO3 (k) + H2 (g) + CH4 (g) 4WO2 (k) + 3H2O (g) + CO (g) (G0R = 176 961 J) (6) (7) 5WO3 (k) + CH4 (g) 3WO2 (k) + 2H2WO4 (g) + CO (g) (G0R = 24 795 J) Tek faz WO2 blgesinde H2O, CO2 ve H2WO4 miktarlarnda hafif bir azalma gzlenirken CO ieriinde ise belirgin bir art gzlenmektedir. Sisteme verilen H2 ve CH4 miktarlarnn fazla olmas nedeniyle bu gazlarn miktarlar artan CH4 mol kesri ile birlikte art gstermektedir. Muhtemel CO oluum reaksiyonlar aadaki gibi olabilir. (G0R = 103 361 J) (8) CH4 (g) + H2O (g) CO (g) + 3H2 (g) (G0R = 109 466 J) (9) CH4 (g) + CO2 (g) 2CO (g) + 2H2 (g) (G0R = 6 105 J) (10) H2 (g) + CO2 (g) CO (g) + H2O (g) (11) 2CH4 (g) + H2WO4 (g) WO2 (k) + 2CO (g) + 5H2 (g) (G0R = 292 005 J) WO2+W blgesinde ise H2O, CO, CO2 ve H2WO4 ieriklerinde art olduu grlmektedir. ekil 5adan artan CH4 mol kesri ile birlikte WO2 ierii azalrken W ieriinin artt anlalmaktadr. Bu sonular nda WO2ten W oluumu iin aadaki reaksiyonlar yazlabilir. 3WO2 (k) + CH4 (g) 2W (k) + H2WO4 (g) + H2O (g) + CO (g) (12) (G0R = 9 384 J) 0 (13) 2WO2 (k) + H2 (g) + CH4 (g) 2W(k) + 3H2O (g) + CO (g) (G R = 94 667 J) (G0R = 88 562 J) (14) 2WO2 (k) + CH4 (g) 2W (k) + 2H2O (g) + CO2 (g) Tek faz W blgesinde gaz fazndaki rnlerden H2O, CO2 ve H2WO4 azalmakta iken CO miktar ise belirgin bir ekilde artmaktadr. Bu sonular ise (8), (9) ve (15) nolu reaksiyonlar ile ifade edilebilir. (G0R = 184 297 J) (15) CH4 (g) + H2WO4 (g) W (k) + 3H2O (g) + CO (g) W+WC blgesinde ise H2O ve CO deerlerinde belirgin bir deiim olmazken CO2 miktarnda ise azalma olduu grlmektedir. ekil 5adan grlecei zere artan CH4 mol kesri ile birlikte W ierii azalrken WC ierii artmaktadr. Bu sonular nda Wden WC oluumu srasnda gereklemesi muhtemel reaksiyonlar, (9), (10), (16) ve (17) nolu reaksiyonlardr. (G0R = 87 686 J) (16) W (k) + CH4 (g) WC (k) + 2H2 (g) (G0R = 49 214 J) (17) W (k) + 3CH4 (g) WC (k) + C2H4 (g) + 4H2 (g) Tek faz WC blgesinde gaz fazndaki rnlerden H2O ve CO2 azalmakta iken CO miktar ise artmaktadr. Bu sonular ise (8) ve (9) nolu reaksiyonlar ile ifade edilebilir. WC dnm tamamlandktan sonra serbest C aa kmaktadr. Bu blgedeki muhtemel reaksiyonlar ise (9) ve (18) nolu reaksiyonlar ile gsterilebilir. (G0R = 52 626 J) (18) CH4 (g) C (k) + 2H2 (g) Bu bilgiler nda WO3in H2CH4 gaz karm ile 1300 Kdeki karbrizasyonu temel kademe iermektedir. Bunlar; (a) WO3in H2CH4 gaz karm ile WO2e indirgenmesi, (b) ksmi indirgenmi rnn H2CH4 gaz karm ile redksiyonun devam neticesinde W eldesi ve (c) Wden WC sentezi eklindedir. Bu sonular, WO3ten WC oluumu iin birok toplam reaksiyona iaret etmektedir. nerilen net reaksiyonlar ise aada gsterilmektedir. (G0R = 101 739 J) (19) WO3 (k) + H2 (g) + CH4 (g) WC (k) + 3H2O (g) 4WO3 (k) + H2 (g) + 5CH4 (g) 4WC (k) + 11H2O (g) + CO (g) (G0R = 510 317 J) (20) 7WO3 (k) + 3H2 (g) + 8CH4 (g) 7WC (k) + 19H2O (g) + CO2 (g) (G0R = 809 429 J) (21) 4WO3 (k) + 2H2 (g) + 6CH4 (g) 4WC (k) + 12H2O (g) + C2H4 (g) (G0R = 368 484 J) (22) 4WO3 (k) + 3H2 (g) + 6CH4 (g) 4WC (k) + 12H2O (g) + 2CH3 (g) (23) (G0R = 178 642 J) 5. SONULAR WC sentezi amacyla WO3 tozunun Ar atmosferinde stlmas akabinde H2CH4 (% 10) gaz karmlaryla 9001300 Kde 60 dk ve 120 dk srelerde reaksiyonlar gerekletirilmitir. Tek faz WC allan artlarda ancak WO3in 1300 Ke Ar atmosferinde stlmas sonras H2CH4 gaz karm ile 120 dklk reaksiyonu sonucunda elde edilmitir. Bu artta elde edilen WC tozunun 0.21.5 m partikl ve ~50 nm kristal boyutlarna sahip olduu belirlenmitir. Gibbs serbest enerji minimizasyon yntemiyle yaplan termodinamik analiz, WC oluumunun artan reaktan gazlar ile WO3 WO2 W WC eklinde olduunu ngrmektedir. Ayrca, bu dnmler iin muhtemel reaksiyonlar da saptanmtr.
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TEEKKR Bu alma, stanbul niversitesi Bilimsel Aratrma Projeleri Koordinasyon Birimince desteklenmitir. Proje numaras: 1453. KAYNAKLAR 1. German, R.M., Liquid-Phase Sintering, Plenum Press, New York, USA, 1985. 2. Matejka, D., Benko, B., Plasma Spraying of Metallic and Ceramic Materials, John Wiley & Sons, New York, USA, 1989. 3. Eroglu, S., Ekren, H., Baykara, T., Surface Hardening of Tungsten Heavy Alloys, Scripta Materialia, Vol. 38, pp. 131136, 1998. 4. Schwarzkopf, P., Kieffer, R., Refractory Hard Metals, The Macmillan Company, New York, USA, 1953. 5. Lassner, E., Schubert, W.D., Tungsten: Properties, Chemistry, Technology of the Elements, Alloys and Compounds, Kluwer Academic / Plenum Publishers, New York, USA, 1998. 6. Bolokang, S., Banganayi, C., Phasha, M., Effect of C and Milling Parameters on the Synthesis of WC Powders by Mechanical Alloying, International Journal of Refractory Metals & Hard Materials, Vol. 28, pp. 211216, 2010. 7. Tang, X., Haubner, R., Lux, B., Kieffer, B., Preparation of Ultrafine CVD WC Powders Deposited from WCl6 Gas-Mixtures, Journal de Physique IV, Vol. 5, pp. 10131020, 1995. 8. Koc, R., Kodambaka, S.K., Tungsten Carbide (WC) Synthesis from Novel Precursors, Journal of the European Ceramic Society, Vol. 20, pp. 18591869, 2000. 9. Reddy, K.M., Rao, T.N., Radha, K., Joardar, J., Nanostructured Tungsten Carbides by Thermochemical Processing, Journal of Alloys and Compounds, Vol. 494, pp. 404409, 2010. 10. Lei, M., Zhao, H.Z., Yang, H., Song, B., Tang, W.H., Synthesis of Transition Metal Carbide Nanoparticles through Melamine and Metal Oxides, Journal of the European Ceramic Society, Vol. 28, pp. 16711677, 2008. 11. De Medeiros, F.F.P., De Oliveira, S.A., De Souza, C.P., Da Silva, A.G.P., Gomes, U.U., De Souza, J.F., Synthesis of Tungsten Carbide through Gas-Solid Reaction at Low Temperatures, Materials Science and Engineering A, Vol. 315, pp. 5862, 2001. 12. De Medeiros, F.F.P., Da Silva, A.G.P., De Souza, C.P., Gomes, U.U., Carburization of Ammonium Paratungstate by Methane: the Influence of Reaction Parameters, International Journal of Refractory Metals & Hard Materials, Vol. 27, pp. 4347, 2009. 13. McCandlish, L.E., Kear, B.H., Kim, B.K., Chemical Processing of Nanophase WC-Co Composite Powders, Materials Science and Technology, Vol. 6, pp. 953957, 1990. 14. Giraudon, J.M., Devassine, P., Lamonier, J.F., Delannoy, L., Leclercq, L., Leclercq, G., Synthesis of Tungsten Carbides by Temperature-Programmed Reaction with CH4-H2 Mixtures: Influence of the CH4 and Hydrogen Content in the Carburizing Mixture, Journal of Solid State Chemistry, Vol. 154, pp. 412426, 2000. 15. Davidson, C.F., Alexander, G.B., Wadsworth, M.E., Initial Kinetics of Tungsten Carburization by Methane, Metallurgic Transactions B, Vol. 9, pp. 553557, 1978. 16. Eroglu, S., Zhang, S.C., Messing, G.L., Synthesis of Nanocrystalline Ni-Fe Alloy Powders by Spray Pyrolysis, Journal of Materials Research, Vol. 11, pp. 21312134, 1996. 17. Eriksson, G., Thermodynamic Studies of High Temperature Equilibria, Chemica Scripta, Vol. 8, pp. 100103, 1975. 18. Besmann, T.M., SOLGASMIX-PV, a computer program to calculate equilibrium relationships in complex chemical systems, Report No: ORNL/TM-5775, Oak Ridge National Laboratory, 1977. 19. Chase, M.W., Davies, C.A., Downey, J.R., Frurip, D.J., Mcdonald, R.A., Syverud A.N., JANAF thermochemical tables, 3rd ed., J. Phys. Chem. Ref. Data 14 (Suppl. l), 1985. 20. Barin, I., Thermochemical Data of Pure Substances, VCH Verlagsgesellschaft, WeinHeim, Germany, 1993. 21. Lfberg, A., Frennet, A., Leclercq, G., Leclercq, L., Giraudon, J.M., Mechanism of WO3 Reduction and Carburization in CH4/H2 Mixtures Leading to Bulk Tungsten Carbide Powder Catalysts, Journal of Catalysis, Vol. 189, pp. 170183, 2000. 22. Leclercq, G., Kamal, M., Giraudon, J.M., Devassine, P., Feigenbaum, L., Leclercq, L., Frennet, A., Bastin, J.M., Lfberg, A., Decker, S., Dufour, M., Study of the Preparation of Bulk Powder Tungsten Carbides by Temperature Programmed Reaction With CH4 + H2 Mixtures, Journal of Catalysis, Vol. 158, pp. 142169, 1996. 23. Decker, S., Lfberg, A.,. Bastn, J.M., Frennet A., Study of the Preparation of Bulk Tungsten Carbide Catalysts with C2H6/H2 and C2H4/H2 Carburizing Mixtures, Catalysis Letters, Vol. 44, pp. 229239, 1997.
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2014 ALMNYUM - KARBON SSTEMNDE Al4C3 FAZININ SENTEZLENMES VE SONRASI YALANMA LEMNE ETKS
Sinan AKSZ, A. Tamer ZDEMR Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, sinanaksoz@hotmail.com, tozdemir@gazi.edu.tr ZET 2014 Al alam tozlar ve %2 grafit, koruyucu saf Ar atmosferi altnda 7 s mekanik alamlanma ilemine tbi tutulmulardr. Elde edilen karm, 800 MPa basn altnda souk preslenmi ve malzemeler 5500C de, ayn koruyucu ortamda uzun sre sinterlenmitir. Yaplan analizler, beklenen Al4C3 faz paracklarnn ancak sinterleme srasnda olutuklarn gstermektedir. Son olarak, 5200C de 2 saat zeltiye alma ileminden sonra su verilen malzemeler, 1500C de 36 saatte kadar belli srelerde yalandrma ilemine tbi tutulmulardr. Mekanik alamlama yaplmadan preslenip, sinterlenen 2. grup numuneler, yine ayn artlarda yalandrlmlardr. Bu iki farkl malzeme grubunun yalanma zamanna bal sertlik deiimleri karlatrldnda, mekanik alamlanm malzemelerin dayanmlarnn dikkat ekici biimde artt ve 1500C de ok uzun tavlanmalarna ramen ar yalanma belirtileri gstermedikleri belirlenmitir. Anahtar Szckler: 2014 Al alam, Mekanik Alamlama, Yalanma, Al4C3 faz.
SYNTHESIS OF Al4C3 PHASE IN 2014 ALUMINUM CARBON SYSTEM AND ITS EFECT ON SUBSEQUENT AGEING TREATMENT
ABSTRACT 2014 aluminum alloy powders and 2% graphite dust by weight were mechanically alloyed under the protective atmosphere of purified argon gas for about 7 h. Blended powders were later cold pressed at 800 MPa and then long term sintered at 5500C under the same gas tight conditions. The expected Al4C3 phase could only be formed during the process of sintering. Later, samples were solution treated at 5200C for 2 h, then water quenched and finally aged at 1500C for several time intervals up to 36 h. Another batch without the preliminary process of mechanical alloying, were similarly pressed, sintered and finally aged hardened. When the change in hardness with respect to ageing time for each group were compared, it was found that mechanically alloyed samples substantially reach to high strength values. However, softening due to over-ageing could not be detected during the period of prolonged annealing at 1500C. Key words: 2014 Al alloy, Mechanical Alloying, Ageing, Al4C3 phase. 1. GR Gnmzde, Toz Metalurjisi (TM) ileri malzeme retiminde yaygn olarak kullanlan yntemlerden biridir [1, 2]. Mekanik Alamlama (MA) ise, normalde termodinamik olarak birbirleriyle karm oluturmayan maddeleri kat reaksiyon teknii ile hzl ve etkin bir ekilde bir araya getirerek, eitli kompozit malzemeleri oluturabilmede temel yntemlerdendir.
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MA ileminde, nce tozlar en doru oranlarda kartrlr ve sonra toz haznesinde tc bilyalarla uygun grlen sre ierisinde hzl bir ekil birbirlerine yerdirilirler [3]. Bylece, birbirlerine adeta atomik boyutta kattrlm yeni ve farkl kombinasyonlarda alam tozlar oluturulur [4]. MA ile, ana malzemeye parack takviyesi olarak eitli karbrler ve dier kat paracklar yedirilerek stn zellikte ve yksek performansta eitli kompozit malzemeleri tasarlayp, retebilmek mmkn olabilmektedir. zellikle alminyumda, eitli karbr paracklar takviye elaman olarak kullanlmaktadr. Alminyum karbr (Al4C3) ierii alminyum metal teknolojisinde nemli bir bileen ve elmas bal seramiklerin (Al2O3Al4C3AlN) retimi balangcnda ilk kullanlan malzemelerden olup, bu yap oda scaklnda yksek termal iletkenlikle birlikte yksek elektrik direncine sahiptir. Ayrca, Al4C3 ilavesi metal kompozit ve alamlarnn mukavemetlemesini arttrmaktadr (AlAl4C3, AlSiCAl4C3, AlAl3TiAl4C3, v.b.) [5]. Bilindii gibi, 2xxx ve 7xxx serisi alminyum alamlar neredeyse havaclk tarihi kadar uzun bir sredir hava aralarnda etkin olarak tercih edilmekte ve arlkl olarak uak kanatlarnda, gvde ve d yzey kaplamalarnda, perinlerde vs kullanlmaktadrlar. Yeni nesil 2014 alminyum alam, bu sektrde geleneksel olarak tercih edilen 2024 alamnn yerini alm bir malzemedir. Bu alam zellikle scak ekstrzyon ve scak haddeleme ilemleriyle retilmektedir. Genellikle ieriinde bulunan bakr, magnezyum, manganez oranlar daha rafine edilmitir. Ayrca, retimden gelen dier kalnt elementlerin azaltlm olmas, sonraki kat hal ilemleri ve buna bal yapsal tasarm kabiliyetini arttrmaktadr [6]. 2014 alminyum alamnn genel dayanm zellikleriyle korozyon davran 2024 alamna gre daha gelikindir. Bu almada, gaz atomizasyon yntemi ile retilmi 2014 tozlar, %2 karbon (C) tozlaryla beraber MA ilemine tbi tutulmu, presleme ve sinterleme sonras elde edilen malzeme son olarak yalandrlmtr.
2. DENEYSEL ALIMALAR 15 bar basnl saf argon gaz ile atomize edilen 2014 Al alam tozlarnn dalm aral 20-180 m, ortalama boyu ise 95 m dir. Bu tozlar, %2 grafit ile harmanlanp, yksek enerjili dikey Atritrde saf Ar gaz atnda MA ilemine tbi tutulmulardr. Bir nceki almada olduu gibi ilem, 500 dev. / dak. ve 20: 1 bilye toz orannda gerekletirilmitir [7]. Ancak, grafit tozuna ilave olarak % 0.5 inko stearat alam sistemine katlm ve en uygun MA sresi olarak tespit edilen 7 saat sre sonuna kadar ilem sorunsuz olarak tamamlanmtr. lem sonunda elde edilen kompozit tozlarnn ortalama tane boyutu 54,50 m ve toz boyut aral 1,60-331 m arasnda deimektedir. Balangta yaklak 125 HV olan sertlik 7 saatin sonunda 228 HV ye kmaktadr. MA sonras tozlar, 800 MPa basn altnda preslenmiler ve daha sonra, 550 Cde 4, 8 ve 24 saat sre ile sinterlenmilerdir. Son olarak, malzeme, 5200C de 2 saat zndrldkten sonra su verilmi ve srasyla 1500C de 4, 8, 12, 16, 20 ve 24 saat yalandrlmlardr. Yalanma ncesi mikro-yapda oluturulmu olan Al4C3 paracklarnn yalanm malzemenin dayanmna olan etkilerini net olarak grebilmek iin; 2ci grup bir malzeme, 2014 tozlarnn MA yaplmadan dorudan benzeri koullarda preslenmesi, sinterlenmesi ve ardndan yalandrlmasyla elde edilmitir. Malzeme yapsndaki deiiklikleri tespit edebilmek iin srasyla: Malvern Mastersizer E toz boyutu analiz cihaz, Cuk =1.5406 ve 2/dakika tarama hznda Bruker D8 XRD analiz cihaz kullanlmtr. Mikro yap incelemeleri Joel JSM-5600 taramal elektron mikroskobunda, sertlik lmleri ise, Shimadzu Mikro Sertlik cihaznda 100g yk kullanlarak gerekletirilmitir. 3. BULGULAR VE TARTIMA 7 saat MA sonunda elde edilen tozlarn XRD analizi incelendiinde beklenen Al4C3 faznn halen olumad anlalmtr (ekil 1). Bu bulgu dier baz almalarda elde edilen sonulara benzerlik gstermektedir [8-11]. Buna karn, MA sonras elde edilen tozlar, preslendikten ve 550Cde uzun sreler tavlanarak, sinterlendikten sonra XRD analizleri tekrarlandnda, yapda ok yava bir hzda Al4C3 faznn olumaya balad ve Al2Cu faz krnm tepeleri arasnda zamana bal olarak yavaa ykseldii grlmtr (ekil 2).
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ekil 1. 7 saat MA ileminden sonra tozlarn XRD analizleri.
ekil.2. MA ve preslenme sonras 550 Cde 24 saat sinterlenmi malzemenin XRD analizi.
Dier yandan, 5500C de yaplan l ilem sv faz sinterlemesi iin yeterli olduundan, ilem sonras yava souma sonucu tane snrlarnda youn olarak Al2Cu faznn olutuu grlebilmektedir [12, 13]. ekil 3de, 4 saat sinterlenmi numune mikro-yaps ve element dalm analizi (EDS) grlmektedir. Buna gre, resimde bulunan parlak blgeler bakrca zengin (Al2Cu) alanlardr ve tane snrlarnda toplanmlardr.
ekil 3. 550 Cde 4 saat sinterlenmi yapda blgelere gre EDS sonular. Homojenletirme (zndrme) ilemi ile birlikte, tane snrlarndaki Al2Cu zamanla erimekte, su vermenin ardndan yalandrma ilemiyle, Al2Cu faz mikro-yap ierisinde daha homojen dalmaktadr. te bu yzden, rnein, 550 Cde 24 saat sinterleme sonrasnda 46 saat yalandrlan numunenin Al2Cu oluumuna ait XRD krnmlarnn nispi olarak alald ekil 4te rahatlkla grlebilmektedir. Ksaca, yalandrma ile birlikte belli blgelerde biriken Al2Cu miktar azalmaktadr.
ekil 4. MA ve preslenme sonras 550 Cde 24 saat sinterlenmi malzemenin 46 saat yalandrma sonras XRD analizi.
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MAnn yalanma zerine olan etkisi ise ekil 5de aka grlmektedir. MA ilemi yaplmam malzemenin balangtan gelen sertlik deerleri dktr. Su verme ve tavlama sonras bilinen yalanma mekanizmalaryla belli bir deere kan dayanm, ksa bir zaman sonra azalmaya balamaktadr. te yandan, MA ilemiyle zaten peklemi olan alam tozlar, preslendikten sonra sinterleme srecinde youn bir yap olutururken, Al4C3 faznn oluumuyla ile malzeme yaps kararl hale gelmektedir. Bu yzden, homojenletirme ve su verme sonras ara malzemenin sertlii, MA ilemi uygulanmam malzemenin yalanma ilemi ncesi sertliinden daha yksektir. Yalanma srecinde ise, balangta MA yaplm malzemede, dayanm ciddi miktarda giderek daha da artmakta ve sertlik deerleri belli bir platoya eritikten sonra, dayanmda herhangi bir azalma olumamaktadr.
ekil 5. MA sonras 550 Cde 24 saat sinterlenmi yapnn yalanma sresine bal sertlik deiimi ile MA yaplmam ve ayn artlarda yalandrlm yapnn sertlik deiimiyle karlatrlmas.
4. SONULAR Yapda Al4C3 paracklarnn youn olarak bulunmas malzemenin dayanmn artrrken, yalanma sresini de nemli lde uzatmaktadr. Nano boyda, ok sk dalml ve kararl paracklar [7], MA ile elde edilen souk deformasyon alt yap oluumlarnn zerinde oturduu, onlar hareketsiz kld (veya kararl hale getirdii) ve bylece toparlanma safhasn bastrd veya teledii bilinmektedir [14-16]. Yalanma ile mikro-yapya ilave edilen Al2Cu paracklar mikro-yapy daha fazla takviye ederken, daha kararl ve sabit hale getirerek dayanm yksek seviyelere kartabilmektedir. yle ki, malzeme 5500C de uzun sre tavlanmasna ramen mikro-yapda sertlik dne sebep olabilecek hibir deiim (toparlanma veya yeniden kristalleme) belirtisi grlmemektedir. Ksaca, retilen bu yeni ve nc malzemenin yapsal zellikleri, yksek scaklk uygulamalarna olduka uygun bir malzeme olabileceini gstermektedir. KAYNAKLAR 1. Suryanarayana C., Mechanical Alloying and Milling, Progress in Mater. Sci., 46 (2001) 1-184. 2. German R.M., ed. Sarta S., Trker M., Durlu N., Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Dernei , Ankara, (2007). 3. Suryanarayana C., Mechanical Alloying, Pergamon Mater. Series, 2 (1999) 49-85. 4. Ruiz-Navas E.M., Fogagnolo J.B., Vlasco F., Ruiz-Prieto J.M., Froyen L., One Step Production of Aluminium Matrix Composite Powders by Mechanical Alloying, Progress in Composites, 37 (2006) 2114-2120. 5. Solozhenko V.L., Kurakevych O.O., Equation of State of Aluminum Carbide Al4C3, Progress in Solid State Communications, 133 (2005) 385-388. 6. Kaar H., Atik E., Meri C., The Effect of Precipitation-Hardening Conditions on Wear Behaviours at 2024 Aluminium Wrought Alloy Progress in Mater. Processing Tech., 142 (2003) 762-766. 7. Bostan, B., zdemir A.T., Kalkanl A., Microstructure characteristics in Al-C system after mechanical alloying and high temperature treatment, Powder Metallurgy, 47:1 (2004) 37-42. 8. Arslan G., Kara F., Turan S., Quantitative X-ray Diffraction Analysis of Reactive Infiltrated Boron CarbideAluminium Composites J. European Ceramic Society, 23 (2003) 12431255. 9. Wu, N. Q., Wu, J. M., Wang, G.X., Li, Z. Z., Amorphization in the Al-C System by Mechanical Alloying, J. of All. And Comp. 260 (1997) 121-126. 10. Besterci, M., Preperation Microstructure and Properties of Al-Al4C3 System Produced by Mechanical Allying, Materials and Design, 27 (2006) 416-421. 11. Zhou, Y., Li Z.Q., Structural Characterization of a Mechanical Alloyed Al-C Mixture, J. Alloys and Comp.,414 (2006) 107-122. 12. imir, M., Gngr, ., gel, B., Al-Cu ve Al-Cu-Mg Toz Karmlarnn Azot Atmosferi Altnda Scak Presleme almalar, 10. Uluslararas Metalurji ve Malzeme Kongresi Bildiriler Kitab Cilt III, 24-28 Mays, stanbul, 1781-1788 (2000). 13. Zhou, J., Duszczyk, J., 1999. Liquid Phase Sintering of an AA2014-Based Composite Prepared from an Elemental Powder Mixture. J. Mater. Sci. 34, (2008) 545550. 14. Doherty R.D., The Deformed State and Nucleation of Recrystallization, Metal Sci., 8 (1974) 132-142. 15. Higgins G.T., Grain Boundary Migration and Grain Growth, Metal Sci., 8 (1974) 143-150. 16. Hoyt J.J., On the Coarsening of Precipitates Located on Grain Boundaries and Dislocations, Acta Metall. Mater., 39 (1991) 2091-2098.
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POWDER PRODUCTION AND NANO MATERIALS
www.turkishpm.org
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EFFECT OF PROCESSING DURATION ON MECHANICAL PROPERTIES OF MG-BASED NANOCOMPOSITES REINFORCED BY MULTI WALLED CARBON NANO TUBES (MWCNT)
Sardar S Iqbal*, Mustafa Aydin**, Saikat Talapatra***, Peter Filip*, Rait Ko**** Center for Advanced Friction Studies, Mechanical Engineering & Energy Processes, Southern Illinois University Carbondale, IL sarwatiq@yahoo.com, filip@siu.edu ** Dumlupinar University, Department of Mechanical Engineering, Main campus, 43100, Kutahya, TURKEY, m_aydin@dpu.edu.tr *** Department of Physics, Southern Illinois University Carbondale, IL stalapatra@physics.siu.edu **** Mechanical Engineering & Energy Processes, Southern Illinois University Carbondale, IL, kocr@ siu.edu
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ABSTRACT Mechanical properties of Mg-based nanocomposites reinforced with non-heat treated virgin/pristine multi walled carbon nanotubes (CNT) and prepared by powder metallurgy method, were investigated. Microstructure was characterized by scanning electron microscopy. The flexural load, Youngs modulus and failure strain were determined for processing time of 5, 30 and 60-minutes in comparison to pure Mg. Mechanical strength was found to be dependent on processing time. The maximum load bearing capability increased by 11% and 6% for nanocomposites prepared for 30 min and 60 min, respectively, and Youngs modulus increased for 30-minutes processed nanocomposites in comparison to Pure Mg. However, failure strain of pure Mg was the highest followed by nanocomposites processed for 60-min due to apparent accommodation of dislocations in pure Mg. SEM of nanocomposites processed for 30-min showed a good bonding of CNT with the matrix, a better dispersion of CNT, with rest of the nanocomposites exhibiting poor bonding. Mechanical strength and microstructure development showed a strong dependence on dispersion of CNT and processing time. Keywords: Magnesium, Carbon Nano Tubes, Composite Materials, Mechanical Properties
1. INTRODUCTION Magnesium (Mg) based composites are more interested due to their potential applications in aerospace, automotive and sports equipment industries [1]. Mg and its alloys are increasingly used in engineering structures due to their higher specific strength [2]. Carbon nanotubes (CNTs) have recently emerged as materials with exceptional properties exceeding those of any conventional material [3-6]. Efforts are being made to incorporate CNT as reinforcement into Mg matrix. Mechanical properties make CNTs ideal candidates as reinforcements in composite materials to increase both stiffness and strength while also contributing to weight savings. Carbon nanotubes have emerged as new reinforcements for a number of material systems including polymeric [7,8], metallic [911] and ceramic [12] matrices. Numerous research groups have added carbon nanotubes to polymer matrices with the aim of producing conductive and high strength polymers. However, no significant improvement in mechanical properties has been reported. The challenges faced were many, including nanotube agglomeration, and the lack of control over alignment. Few research groups have investigated either metal or ceramic matrices. A successful procedure was recently reported MWCNT were incorporated in both aluminum (Al) and magnesium (Mg) matrices by powder metallurgy (PM) techniques [10,13]. Low-energy ball milling in a Turbula mixer is used to homogenize the mix followed by compaction into a disc shape, and sintered. The samples tested exhibited a ductile behavior, but the expected improvement in Youngs modulus was
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only slightly achieved. The powder metallurgy technique is promising over other techniques such as pressureless infiltration technique, mechanical alloying and by a powder can rolling technique [2, 14]. Various inadequacies in mechanical properties can be attributed, among several factors such as on the difficulty of dispersion of CNT and subsequent agglomeration, use of limited amount of CNT, poor bonding between matrix and CNTs, and the difficulty in the alignment of CNTs in the desired direction in the matrix [9-11, 14,]. Although such issues have not yet been resolved, extensive efforts are underway to overcome them. Present study discusses the impact of mixing duration of CNTs in Mg matrix on the mechanical properties. 2. EXPERIMENTAL PROCEDURES In the present study, powder metallurgy method was used for the preparation of a CNT within Mg powders by ball milling mixing machine. Pure magnesium powder (99.9% pure, -325 mesh in size) from Alfa Aesar was used as metal matrix. The multi wall carbon nano tubes (MWCNTs) produced by chemical vapor deposition (CVD) process were used as reinforcements for the fabrication of nanocomposites. Mg-nanocomposites were prepared by mixing CNTs at ratio of 1 % by weight. The mixing was performed by high energy ball milling machine (Turbola spex 8000). The mixing duration was 5, 30, and 60 minutes. The mixture of Mg and CNTs was cold pressed at 700 MPa. Mg-nanocomposites were sintered at 620 oC under argon atmosphere for 2 hours in tube furnace. The density was measured by mineral spirit method using Archimedes principle by taking average of three readings. The flexural tests were carried out in Instron 4202 Universal testing machine at cross head speed of 0.2mm/min. The microstructure of fractured surfaces of the nanocomposites was studied and analyzed using scanning electron microscopy Hitachi S-570. 3. RESULTS AND DISCUSSIONS Figure 1 shows the density and porosity of pure Mg and Mg-nanocomposites. It is apparent that the density of pure Mg is the highest, and reduced significantly after incorporating 1% CNT by weight. On the other hand, pure Mg shows minimum level of porosity, whereas Mg-nanocomposites show progressive increase in the porosity with increasing CNTs. Since the steady decrease in density and an increase in porosity is due to the increase in the ratio of CNTs. This indicates that although, the decrease in density has occurred due to CNT reinforcements, yet an appreciable increase in porosity is observed, and indicates the less effective homogeneous distribution of the CNTs in Mg-matrix, as the clustering of the CNTs is unavoidable due to the sheer size of the CNTs at the nano levels. Goh et al. [15] also reported on the decrease in the density of nanocomposites with increasing CNTs. Goh et al. [16] reported a similar case, and attribute it to the addition of lighter weight CNTs or the increase in porosity in the Mg matrix. Esawi et al. [14] attributed the lower densification to the CNT clustering present in the material.
Figure. 1 Density and porosity of Pure Mg and Mg-nanocomposites. Goh et al. [16] reported a decrease in ductility with increasing CNT contents, and attributed it to agglomeration of CNT becoming cluster which prevent the bonding between Mg and CNTs. Ultimately, the nanocomposites are inherently prone with pre-existing cracks. These cracks are nucleation sites for
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instability, and leads to the failure of the material. Goh, Lee and Gupta [15] reported that the increase in porosity affects the integrity of the material, and attributed the existence of porosity to the clustering of CNTs. Figure 2 shows specific mechanical strength of the Mg-nanocomposites mixed for 0, 5, 30, and 60 minutes. It is apparent that the Mg-nanocomposites mixed for 30-minutes exhibit highest modulus closely followed by Mg-nanocomposites mixed for 5-minutes. The lowest modulus was exhibited by Mg-nanocomposites mixed for 60-minutes. The specific strength of Mg-nanocomposites mixed for 30-minutes was the highest followed by Mg-nanocomposites mixed for 60-minutes. The specific strength of pure Mg was the lowest. Pure Mg exhibited the highest failure than the Mg-nanocomposites, which was followed by Mg-nanocomposites mixed for 60-minutes. The Mg-nanocomposites mixed for 5-minutes exhibited the lowest failure, and was followed by Mg-nanocomposites mixed for 30-minutes. Pure Mg showed highest fracture energy followed by Mg-nanocomposites mixed for 60-minutes, and could be attributed to higher failure strain. The lowest fracture energy is exhibited by Mg-nanocomposites mixed for 5-minutes, and was followed by Mg-nanocomposites mixed for 30-minutes.
Figure.2 Specific strength of Mg-nanocomposites for different mixing duration. Li et al. [17] reported that the compression mechanical properties of the MWNT/Mg composites. The compression at failure, the compressive yield strength and ultimate compressive strength reportedly improved significantly up to 36% by only adding 0.1wt% MWNTs to the Mg alloy. Multiwall carbon nanotube/pure magnesium composites by a powder metallurgical method were produced, and found out that the Youngs modulus increased 9% in comparison to pure Mg by adding 2 wt% CNTs [13, 18]. Shimizi et al. [19] fabricated 1 wt% of short and straight carbon nanotubes reinforced Mg alloy composites by a vacuum hot pressure method followed by extrusion. The yield strength, the tensile strength and the Youngs modulus of the CNT/Mg composites reportedly improved by 23%. It is known that the CNTs have high aspect ratio, which makes it possible to acquire smaller interparticle spacing in the matrix at very low concentrations compared to other traditional reinforcements in powder form. Therefore, CNTs can act as obstacles to dislocation movement in metals. Plastic deformation occurs if the dislocations circumvent the obstacle or shear the nanotube. Due to CNTs smaller diameter , shear appears to be the most likely mechanism. It would mean that dislocations are held up at and around the CNT, and the stress concentration at the head of the pile-up group of dislocations causes the CNT to yield by deformation or fracture. Additionally, CNT are able to bridge the crack opening and crack bridging at the submicron and nano levels. In the case of obstacles with high aspect ratio, dislocations cannot easily climb to circumvent the obstacle, so an improvements of flow stress and toughness can be expected.
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Figure. 3 Mechanical strength and failure of nanocomposites mixed for different time.
Figure 3 shows the strength and failure displacement of nanocomposites. It is apparent that the introduction of CNT increased the load bearing capability of Mg metal by incorporating 1% CNT by weight. The load bearing capability progressively increased with increasing mixing time, and maximum load bearing capability is shown by Mg-nanocomposites mixed for 30-minutes. Subsequently, further mixing time reduced the load bearing capability of Mg-nanocomposites mixed for 60-minutes. On the other hand, Pure Mg showed higher failure resistance than the nanocomposites. The failure resistance of nanocomposites, progressively increased with increasing mixing time, which shows that nanocompsoites are losing characteristics of pseudo fiber reinforce composite and are readily becoming homogenized mixture of comparative particle size of Mg and CNT due to extensive crushing of CNT into progressively finer bits and particles. Figure 4 shows the SEM micrographs of fracture surfaces of Mg-nanocomposites for 30, and 60 minutes mixing. It is apparent that Mg-nanocomposites mixed for 30-minutes show CNTs (in insert of SEM image, a) which are longer. However, Mg-nanocomposites mixed for 60-minutes show negligible traces of CNTs of longer lengths, which indicates that the crushing of the CNTs occurred extensively, and changed the CNT into a finer particle form and, therefore, losing the characteristics of CNT as fiber reinforcement when compared with the Mg-nanocomposites mixed for 30-minutes. This also explains the ductile behavior of the Mg-nanocomposites mixed for 60-minutes as the dislocations are easily accommodated due to comparative sizes of the constituents. It can be seen that the nanocomposite mixed for 30-minutes have more agglomerated areas whereas Mg-nancomposite mixed for 60-minutes shows no such behavior. The, CNTs can act as obstacles to dislocation movement in metals, however, unlike Shimizi et al. [19], no significant plastic deformation is observed in the current Mg-nanocomposites.
Figure.4. The SEM images of the Mg-CNT composites mixed at different duration (a) 30 min; (b) 60min. The micron bar in insert in (a) is 800nm; and in (b) micron bar is 100nm.
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4. CONCLUSIONS 1) Mg nanocomposites exhibited a lower density after incorporating CNT in comparison to pure Mg. The porosity increase could be attributed to clustering of CNTs. SEM images of nanocomposites mixed for 30-minutes exhibited longer CNTs, whereas nanocomposites mixed for 60-minutes showed negligible CNTs. 2) Mg-nanocomposites mixed for 30-minutes exhibited higher mechanical strength and modulus among Mg-nanocomposites and pure Mg. The lowest strength was shown by pure Mg. 3) Mg-nanocomposites prepared by powder metallurgy showed that mixing duration impacts the overall mechanical and microstructural properties of the composites. ACKNOWLEDGEMENTS The authors would like to TUBITAK (The Science and Technological Research Council of Turkey) for financial support during the post doctoral programmed at the Southern Illinois University,USA. References 1. C. S. Goh, J. Wei, L. C. Lee and M. Gupta1. Development of novel carbon nanotubes reinforced magnesium nanocomposites using powder metallurgy technique SIMTech technical reports (STR_V9_N3_04_JTG) Volume 9 Number 3 Jul-Sep 2008. 2. Naing Naing Aung, Wei Zhou, Chwee Sim Goh, Sharon Mui Ling Nai, Jun Wei. Effect of carbon nanotubes on corrosion of MgCNT. Composites. Corrosion Science 52 (2010) 15511553. 3. De Heer W. Nanotubes and the pursuit of applications. MRS Bull 2004:281. 4 Demczyk BG, Wang YM, Cumings J, Hetman M, Han W, Zettl A, et al. Direct mechanical measurement of the tensile strength and elastic modulus of multiwalled carbon nanotubes. Mater Sci Eng A 2002;334:1738. 5. PJF Harris. Carbon nanotubes and related structures: new materials for the twenty-first century. Cambridge University Press; 2001. 6. RS Ruoff, D Qian, WK Liu. Mechanical properties of carbon nanotubes: theoretical predictions and experimental measurements. CR Phys 2003;4:9931008.]. 7 ET Thostenson, C Li, Chou Tsu-Wei. Nanocomposites in context. Compos Sci Technol 2005; 65:491516. 8. Thostenson ET, Ren Z, Chou T. Advances in the science and technology of carbon nanotubes and their composites: a review. Compos Sci Technol 2001;61:1899912. 9. Laha T, Agarwal A, McKechnie T, Seal S. Synthesis and Characterization of plasma spray formed carbon nanotube reinforced aluminium composites. Mater Sci Eng A 2004;381:24958. 10. Carreno-Morelli E, Yang J, Schaller R, Bonjour C. Carbon nanotube reinforced metal matrix composites. In: Proceedings of EURO PM 2003, October 2022, 2003, Valence, Spain. 11. Zhong R, Cong H, Hou P. Fabrication of nano-Al based composites reinforced by single-walled carbon nanotubes. Carbon 2003;41:CO1-851. 12 . Peigney A, Laurent Ch, Flahaut E, Rousset A. Carbon nanotubes in novel ceramic matrix composites. Ceramics Int 2000; 26: 67783. 13. Carreno-Morelli E, Yang J, Couteau E, Hernadi K, Seo JW, Bonjour C, et al. Carbon-nanotube/magnesium composites. Phys Stat Sol 2004; 201(8):R535. 14. Amal M.K. Esawi , Mostafa A. El Borady. Carbon nanotube-reinforced aluminium strips. Composites Sci. & Technology 68; 2008: 486-92. 15. C.S. Goh, J. Wei, L.C. Lee, M. Gupta. Simultaneous enhancement in strength and ductility by reinforcing magnesium with carbon nanotubes. Materials Science and Engineering A 423 (2006) 153156. 16. CS Goh, J Wei, LC Lee, M Gupta,. Development of novel carbon nanotube reinforced magnesium nanocomposites using the powder metallurgy technique. 2006 Nanotechnology, doi:10.1088/09574484/17/1/002. 17. Qiangqian Li, Andreas Vierecki, Christian A Rottmair, Robert F. Singer. Improved processing of CNT/ Mg alloy composites, Composites Science & Technology 69(7-8); 2009: 1193-99. 18. Song Hai-Yang and Zha Xin-Wei,. The effects of boron doping and boron grafts on the mechanical properties of single-walled carbon nanotubes 2009 J. Phys. D: Appl. Phys.42 225402 doi:10.1088/0022-3727/42/22/225402 19. Shimizu Y. Multi-walled carbon nanotube-reinforced magnesium alloy composites Scripta. Mater. 2008: 58; 26770.
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Production of In-situ Cu/TiO2 Nano-composites & Evaluation of Physical and Mechanical Properties
Amir Hossein MOGHANIAN*,Kazem PURAZRANG* , Parvin ABACHI* and Fahimeh SHOJAEEPOUR* Dept. of Materials Sci. and Eng., Sharif Uni. of Tech., Azadi Ave., Tehran, Iran, abachi@sharif.edu, f.shojaeepour@gmail.com, abapar1390@yahoo.com, purazrang@sharif.edu
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Abstract Copper matrix composites reinforced with TiO2 particles, because of good electrical and thermal conductivity and strength at high temperature, are suitable for contact materials. At present work, Cu/TiO2 nano-composites, containing different amounts of TiO2, were produced by in-situ oxidation of Cu-Ti pre alloyed powders. The morphology of milled powders and microstructure of nano-composite specimens were studied using SEM. To evaluate mechanical alloying progress of Cu and Ti powders mixture and internal oxidation after Cu2O addition, XRD analysis were carried out. Physical and mechanical properties results of nano-composite specimens indicate the density, specific electrical resistivity, hardness and wear rate values alternation with amount of TiO2 in Cu matrix . Keywords: Copper matrix nano-composite; TiO2 particles; Internal oxidation; Specific electrical resistivity, Wear rate. 1. Introduction Oxide dispersion strengthened (ODS) copper matrix composites are known as highly thermal and electrical conductive materials with high strength at room and elevated temperatures [1].It has been realised that the performance of moving electrical contacts is greatly governed with friction and wear of the contact surfaces, so that, their motion in operation leads to formation of wear particles and contamination on contact spots and current passage breakdown [2]. Therefore, evaluation of tribological behaviour of contact materials and improvement of contact quality, reliability and durability is necessary. Referring to other works, wear resistivity of copper base composites containing fine particles as reinforcement is noticeably higher than pure copper [3]. Internal oxidation, as in-situ production route of ODS materials, has been the subject of numerous investigations during the past decade. This process has two major benefits, firstly, it can prevent the formation of external oxide scale and secondly, internal oxidation provides a method of introducing second phase particles into an alloy which can affect the mechanical and other properties of alloys [4]. The Cu/Al2O3 as a representative of these composites owing almost identical electrical and thermal conductivity like as copper, represent higher strength in comparison to pure copper [5]. Cu/Al2O3 nano-composites are proper in use as contact materials but the duration of internal oxidation, during internal oxidation of Cu (Al) solid solution is too long and the complete oxidation and therefore perfect elimination of Al from Cu lattice is difficult to achieve [6]. The remained solute Al in Cu will lead to decrease in electrical conductivity of the composite [7]. Referring to the equilibrium phase diagram of Cu-Ti, solubility of Ti in Cu is limited and less than 6 weight percent at 1143K and very negligible at room temperature. Additionally; due to solubility limitation curve, extraction of remained titanium from copper lattice with subsequent heat treatment is possible. Moreover, oxidation rate of Ti is more than Al. Due to limited works on Cu/TiO2 composite as materials used in electrical contacts, the present work concentrates on this system. Cu/TiO2 nano-composites has been produced by in-situ internal oxidation of Cu-Ti alloyed powder. In order to investigate the effect of various amounts of TiO2 particles on the density, electrical conductivity, hardness and wear rate of Cu/TiO2 nano-composites, the Ti values was selected at the range of 1-3 wt.%.
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2. Experimental Procedure The elemental Cu (ME-1.12097.0500), Ti (purity of 99%, d<10m) powders and Cu2O powder (AC-19742.0500) served as starting materials. At the initial stage, elemental Cu and Ti powders were mechanically alloyed for 60h in argon atmosphere in Fritsch6 planetary ball. The stainless steel balls to powder weight ratios (BPR) and mill rotation speed were selected as 20:1, 10:1 and 250 rpm, respectively. Considering the Ti content in the range of 1-3 wt.% in Cu-Ti powder composition, the amounts of reaction products and X values were calculated according to stochiometric oxidation reaction of Ti according to following reaction: The theoretical values of TiO2 are presented in table 1. To specify pressed and sintered specimens, in continue the capitals P and S will be added, respectively. Referring to Murty and et.al [8], the large lattice strain generation due to Ti solution in Cu, some amounts of Ti can remain insoluble. Apparently, the insoluble Ti in Cu lattice can lead to formation of coarse TiO2 particles. Table 1. Theoretical values of TiO2 in Cu/TiO2 nano-composites according to different quantity of Ti in Cu-Ti alloyed powders Ti, wt.% 1 2 3 TiO2, wt.% (vol.%) 1.66 (3.45) 3.33 (6.80) 5 (10.03) Specimen Designation C1 C2 C3
Following mechanical alloying, the Cu-Ti alloyed powder and Cu2O were milled for 10h under Argon atmosphere. To prevent oxidation of very fine powder particles, compacting was firstly conducted in a hot press under 30MPa applied pressure at 400C in glove box. For more densification of specimens, a cold press was performed at 400MPa. Internal oxidation completion was carried out during sintering at 800C for 1h. The heating rate was considered as 5C/min. The specimens were cooled down in the furnace. X-ray diffraction analysis was used to determine progress of mechanical alloying process during milling and to detect TiO2 formation after sintering. The density value of specimens was specified by usual Archimedes method using precise balance model CP324S-Sartorius with an accuracy of 0.1mg. The electrical resistivity was measured by micro-ohmmeter LOM-D500 working based on Kelvin Bridge. The specific electrical resistance were then determined considering specimens dimensions. The Vickers hardness was measured under applied load of 5 N. Dry sliding wear tests were carried out according to ASTM G-99 standard using pin-on-disk equipment. The pins having a diameter of 5 mm and a length of 10 mm slide against the steel counter-face with 67HRC hardness. The sliding speed and normal load were 0.25 m/s and 20 N, respectively. The sliding distances were selected as 1000, 2000 and 3000 m. The weight loss was measured using a precise electronic balance and converted to volume loss knowing the density values of specimens. The wear rate was given as volume loss per unit sliding distance. To study the wear mechanisms of the specimens, worn surfaces of the pins were investigated using SEM and EDS analysis. 3. Results and discussion In order to determine the proper mechanical alloying time and BPR values with less contamination and efficient alloying, milling process were performed in different times. Finally, the work was concentrated on two milling times of 40 and 60hrs and BPR of 10:1 and 20:1. Figure 1 shows SEM micrographs of Cu-2wt.% Ti powder milled at different conditions. In fact, flat like powder particles in figure 1a and 1b, indicate that more time is required to reach a proper state between cold welding and fracturing of powder particles. Milling in almost 60 hours with BPR 20:1 not only decreases average particle size but also makes particles morphology relatively equi-axed. A decrease in powder particle size and formation of thin layers between different particles make the atoms diffusion path shorter and therefore facilitates formation of alloys. As shown in figure 1c, particle size of powders milled for 60hr with BPR 20:1 is less than the others. Additionally, the particles morphology indicate that an equilibrium state between cold welding and fracture of powder particles has been achieved. However, to confirm suitability of selected milling time and ball to powder weight ratio (BPR) for mechanical alloying of Cu-Ti system, X-ray diffraction was also applied to the Cu-Ti alloyed powders after 60 hours with BPR 20:1. The XRD results of Cu-2wt.% Ti powder after mechanical milling in different conditions are shown in figure 2.
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Figure 1. Morphology of Cu-2wt.%Ti powder after mechanical milling of (a) 60 hrs with BPR 10:1, (b) 40 hrs with BPR 20:1, (c) 60 hrs with BPR 20:1.
Figure 2. XRD analysis of Cu-2wt.%Ti powder after mechanical milling of 60 hrs with BPR 10:1 and 20:1 The intensity of the peaks decreases with increasing of BPR. This can be related to grains refinement, increase of lattice strain along with increasing of dissolved Ti in Cu. Determination of crystallite size and lattice strain from the XRD data and using the Williamson-Hall equation [9], confirms this comment. During milling of elemental Cu and Ti powders, Ti dissolves in Cu, progressively. Since, atomic radius of Ti (2.93A) is larger than Cu (2.56A), the lattice parameter of Cu should be increased. Therefore, according to Braggs law and considering direct dependence of lattice parameter to lattice planes distances, XRD peaks of alloyed Cu should be shifted to lower values. However, due to low difference in atomic radius of Cu and Ti, the displacement of peaks is very negligible. In addition, dissolving of limited amounts of oxygen atoms and their placement on interstitial sites of copper lattice would lead to strong decrease of lattice parameter due to large difference in the atomic radii [10]. It should be noted that, the solution of Fe atoms originated from milling jar and balls has the same effect. Another possibility for unexpected values is formation of stacking faults during intense milling of copper having low stacking fault energy. Consequently, these faults may cause a peak shift opposite to that caused by the dissolved atoms with atomic size of more than that of Cu [11]. Referring to XRD analysis, it can be concluded that following the particles refinement and formation of thin layers of Cu and Ti, after milling 60 hrs with BPR 20:1, Cu-Ti solid solution can be mainly formed. The XRD results of pressed and sintered specimens of C1P and C1S, are shown in figure 3. It seems that, after sintering, due to extraction of Ti atoms from Cu lattice and internal oxidation, diffraction peaks move to that of pure
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Cu peaks again. The intensity increment of the peaks is also sensible. However, due to very low amount of TiO2 (max. 3.45 vol.%) and small particle size, the diffraction peaks of TiO2 are not appeared for this specimen. Referring to SEM micrograph of Cu/TiO2 nano-composite in figure 4, average grain size is near 50 nm. The TiO2 particles as light regions, are smaller than 100 nm. However, the insoluble Ti in Cu lattice can lead to formation of coarser TiO2 particles, with a size which depends on Ti particle size.
Figure 3. XRD results of Cu-Ti -Cu2O powders after pressing and sintering (C1P and C1S specimens)
Figure 4. SEM micrograph of Cu/TiO2 nano-composite ( C1S) The specified physical and mechanical properties values of pressed and sintered specimens are presented in tables 2 and 3. As it can be seen, due to presence of Ti in Cu lattice and formation of solid solution, remained porosity, presence of Cu2O and probably some TiO2 particles, specific electrical resistivity of pressed specimens increases with increasing Ti content. In general, the values are higher than that of the of pure Cu which is equal to 1.7241. cm. The specific electrical resistivity of Cu/TiO2 composites increases also with increasing the amount of TiO2 particles. Two important strengthening and hardening mechanisms can be considered in the Cu/TiO2 nano-composite produced by in-situ oxidation: the oxide dispersion strengthening according to Orowan mechanism and refined grains strengthening according to Hall-Petch relation [12]. Table 2. Properties of pressed specimens Specimen Designation C1P C2P C3P Density (g/cm3) 7.2 7.05 6.83 Table 3. Properties of sintered specimens Specimen Designation C1S C2S C3S Density (g/cm3) 7.74 7.31 7.11 Specific electrical resistivity (.cm) 1.95 2.79 7.19 Hardness (HV) 75.3 87.8 96.5 Specific electrical resistivity (.cm) 3.34 5.92 7.22
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To investigate wear behaviour of Cu/TiO2 nano-composites dry sliding wear tests were carried out according to ASTM G-99 standard using pin-on-disk equipment. As shown in figure 5 a, by increasing the sliding distance, the amount of the specimens volume loss increases. As the reinforcement particles, TiO2, increases, the volume loss decreases. Figure 5 b shows the wear rate of Cu/TiO2 nano-composite versus TiO2 particles. The lowest wear rate belongs to C3S specimen.
(a) (b) Figure 5. (a) Wear volume loss dependence to sliding distance and (b) Wear rate of sintered specimens containing different amounts of TiO2 particles Figure 6 shows worn surfaces of C2S nano-composite after sliding of different distances. Sliding speed and normal load are constant and equal to 0.25 m/s and 20 N, respectively. Grooves and channels parallel to the wear direction in figure 6a indicate an abrasive wear. Increasing the sliding distance causes the formation of some cracks perpendicular to the wear direction in the specimen surface which is indicative of the delamination dominance in high distances. In addition, as the sliding distance increases to 2000 m, the depth and width of the grooves increases. The EDS results in table 4 confirm an increase in oxygen content in the wear surfaces with increasing the sliding distance from 1000 to 3000m. Due to friction between composite pin and counter-face disk surfaces, the temperature of surfaces increases to the level in which an oxide phase forms. As indicated in table 4c, the oxidation wear mechanism can be more effective after 3000 m sliding.
Figure 6. SEM images of worn surfaces of C2S specimen after sliding distances of (a) 1000, (b) 2000, (c) 3000 m,
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Table. 4. EDS analysis of worn surface of C2S specimen after sliding of (a) 1000, (b) 2000, (c) 3000 m
4. Conclusions A study on the effect of milling condition and Ti content on the formation of in-situ TiO2 particles in Cu matrix composites and evaluation of some physical and mechanical properties reveal the followings : 1- Formation of TiO2 particles can be proceed by mechanical milling and subsequent sintering of Cu(Ti)-Cu2O powders mixture. 2- The density of Cu/TiO2 nano-composites decreases with increasing TiO2 particles content having lower density in comparison to Cu matrix. 3- Specific electrical resistivity and hardness of Cu/TiO2 nano-composites increases with increasing oxide particles content. 4- Increasing the sliding distance causes an increase in the rate of wear volume loss, especially in the case of specimens with low content of particles correspoding lower wear resistance. 5- At low sliding distance, the dominant wear mechanism is abrasive, whereas, at higher sliding distance the delamination and oxidation mechanisms can perform greater role.
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REFERENCES [1] J.Y. Cheng, M.P. Wang, Nano scale Al2O3 dispersion-strengthened copper alloy produced by internal oxidation, China-EU Forum on Nanosized Technology, pp. 93-101, 2002. [2] M. Braunovic, V.V. Kochits and N.K. Myshkin, , Electrical contacts : fundamental, applications and technology, pp. 373-376, 2007, NY., CRC Press. [3] P.K. Deshpande, R.Y. Lin, Wear resistance of WC particle reinforced copper matrix composite and the effect of porosity, Material Science and Engineering A, Vol. 418, pp. 137-145, 2006. [4] S.Wood, D. Adamonos,Internal oxidation of dilute Cu-Ti alloys, Metallurgical Transaction, Vol. 6, pp. 17931794, 1975. [5] Z. Shi, M. Yan, The preparation of Al2O3- Cu composite by internal oxidation, Applied Surface Science, Vol. 134, pp. 103106, 1999. [6] S. H. Liang, L. Fang, Z. K. Fan., Effect of powder characteristics on Cr internal oxidation for preparation of Cr2O3/ Cu composite, Materials Science and Technology, Vol. 20,pp. 800-803, 2004. [7] S.H. Liang, L. Fang, Internal oxidation of Cr in Cu-Cr/Cu2O composite powder prepared by mechanical activation Material Science and Engineering A, Vol. 437, pp. 27-33, 2004. [8] B.S. Murty, M. Mohan Rao and S. Ranganthan,Nanocrystalline phase formation of solid solubility by mechanical alloying Nanostrutured materials, Vol.3. pp.459-467, 1993. [9] G.K. Williamson, W.H. Hall, Acta Metall, vol. 1, pp. 2231, 1953. [10] E. Botcharova, M. Heilmaier, J. Freudenberger, G. Drew, D. Kudashow, U. Martin, Supersaturated solid solution of niobium in copper by mechanical alloying, jourmal of Alloys and Compounds, Vol. 351.pp. 119-125, 2003. [11] C. Suryanaryana., Mechanical alloying and milling, Prog. Mater. Sci., Vol. 46, pp. 1-184, 2001. [12] S.J. Hwang, J.H. Lee, Mechanochemical synthesis of Cu-Al2O3 nano-composites, Material Science and Engineering A, Vol. 405, pp. 140-146, 2005.
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Researches regarding the obtaining of cermet type mixtures from TiC-WC-(Ni,Co)-Al2O3 and TiC-(Ni,Co)-Al2O3 systems
Emilia Maria Coman (Ciovica)*, Irina CARCEANU**
*
VALAHIA University of Targoviste, 2nd Carol I Street, code 130024, Targoviste, Dambovita Romania, emilia_ciovica@yahoo.com ** Metallurgical Research Institute of Bucharest, 39 Mehadia Street, code 060543, 6 County, Bucharest Romania, irina_carceanu@yahoo.co.uk, ABSTRACT
The paper presents the results of experiments effectuated to obtain some intimate mixtures based on cermets with a high level of TiC, special alumina Al2O3 and different concentrations of metal binder Ni/Co. We present the physical-chemical characteristics of sinterized benchmarks made of hard composites of Cermet type. Keywords: cermets; intimate mixtures, cutting plates. 1. INTRODUCTION The technological evolution in the field of powder metallurgy is related in the last decade by the appearance and development of some new methods to obtain composite materials with hi-tech characteristics, methods allowing the creation of new materials with superior mechanical properties to the existing ones obtained either by modifications of the chemical composition or by modifications in terms of the obtaining method. The use stresses specific to the more and more complex mechanical processing by chip removal as well as the emphasis on the increase of productivity have led to the elaboration of new materials obtained by the application and development of some advanced technologies that may allow the obtaining of some products with hi tech characteristics; they must simultaneously have high values of the triplet hardness (wear resistance) tenacity (bending resistance) chip removing speed as well as properties of mechanical shock resistance, corrosion and oxidization at high temperatures appearing during their use. Regardless of the appearance, development and implementation in industry of some advanced technological processes, the mechanical processing, especially the chip removal, still occupies a dominating position. The variety of processed materials and the processing conditions on plants in full diversification, the complexity of the tribo-technical processes during chip removal as well as the numerous factors influencing the operation characteristics of the cutting tool have triggered worldwide, among the famous manufacturers in the field of processing the hard alloy powders, preoccupations focusing on a series of aspects such as: Obtaining the optimal geometry of the cutting plates depending on the characteristics of the cutting process; Extending their field of use while restraining the range of powders used; Design of some materials that might make possible the mechanical processing at higher and higher speeds in absence of vibrations. Cermet is a term used for a wide range of materials and, in accordance with the definition from Metals Handbook cermet is a product of powder metallurgy made of ceramic particles bound in a metal matrix (see [1]). Cermets are materials made of heterogeneous compositions of one of several ceramic phases wit metals or alloys having a set of properties resulted from the combination of qualitative characteristics of the initial constituents and also new properties that may no be encountered in the latter ones. Cermets have a set of physical-mechanical properties allowing their use in different technical fields for heavy duty work as materials resistant to high temperatures, materials with a special refractoriness, materials resistant to oxidization at high temperatures, materials resistant to corrosion in acid environments, materials resistant to wear [2].
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Depending on the basic component, cermets fall into: oxydic cermets (oxide-metal) and non-oxydic cermets such as those based on carbides (carbide-metal), nitride-based cermets (nitride-metal) or boride-based cermets (boridemetal). Carbide-metal cermets represent the largest class of composite materials being discovered since 1922. This important invention consisting in the making of a combination between a hard component, namely wolfram carbide (WC hexagonally compactly crystallized) with a ductile phase as binder - cobalt (Co), was the reason for the setting up of WIDIA company in Germany [3] After a couple of years, they started the development of the titanium and nickel carbide-based materials, (TiC-Ni) under the clear denomination of cermets. In current practice for the composites used in the processing of metals by chip removing, the term cermet is used to define the tool materials based on titanium carbonitride (TiCN) bound with nickel (Ni) and/or cobalt (Co), with the possibility to add some different carbides [4]. This terminology will apparently help to tell these types of materials for cutting tools from the conventional ones based on wolfram carbide (WC), though titanium carbonitride is not at all more ceramic than wolfram carbide[5]. At the same time, the complexity of the increasing processing operations has led to the appearance of some problems in terms of chi removing after the processing by chip removing of very small depth and high speed; the cutting tools executed from such materials need sharp cutting edges that may be executed at a high qualitative level from cermets as compared to those executed from conventional hard alloys with or without cover layers [6]. 2. EXPERIMENTAL CONDITIONS To execute the cutting plates, we tried to obtain some composition recipes of CERMET type CERMET with a high content of TiC (superior to 25 %), different concentrations of metal binder Ni/Co and special alumina Al2O3. The chemical composition of the powder mixtures was: TiC = 75 %; WC = 10 %; Co = 5 %; Ni = 5 %; Al2O3 = 5 % - for system (TiC - WC - (Ni, Co) - Al2O3) and: TiC = 75 %; Co = 5 %; Ni = 5 %; Al2O3 = 15 % - for system (TiC - (Ni, Co) - Al2O3). The binder temporarily used to obtain some powder homogenous mixtures was transparent A type paraffin [7]. The experimental works for the execution of the compositional systems of the type (TiC WC - (Ni, Co) - Al2O3 ) and (TiC - (Ni, Co ) - Al2O3) consisted in: choosing the raw materials; characterization of the elementary powders and processed powders according to the standards in force; obtaining the experimental powdery mixtures used to obtain cermets; To obtain the basic mixtures based on cermets, we used the following powders: wolfram carbide powder WC (from PLANSEE company AUSTRIA); cobalt powder Co (from TIZIT company AUSTRIA); nickel powder Ni (from TIZIT company AUSTRIA); special calcinated alumina powder Al2O3 (ICEM Bucharest). The properties of the powders used within the experimental works to obtain the mixtures used in the obtaining of cermets are given in table 1a [4] and their supplementary characterization was made according to the international standards in force being presented in table 1b. Table 1a. Properties of powders used in the execution of the cermet-based mixtures Vickers hardness [HV50] 2200 3000 1800 < 100 < 100 Crystallographic structure hexagonal cubic cubic Cubic / hexagonal cubic Melting temperature [C] 2800 3100 3800 1495 1455 Specific density Elasticity module [g/cm3] [Gpa] 15.63 4.94 14.50 8.9 8.9 696 451 285 207 207
Material WC TiC TaC Co Ni
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Table 1b. Characteristics of the powders used in the execution of cermet-based mixtures Powder type WC TiC TaC Co Ni Al2O3 Average particle diameter, Fischer [m] 1.50 2.00 1.95 1.00 1.50 Initial: 4-5; After : 2.0 Flow rate [sec/100g] 37 33 31 it doesnt flow 35 it doesnt flow Apparent freely poured density [g/cm3] 7.83 2.28 6.55 3.46 2.30 3.70
In table 2, we present the physical-chemical characteristics of the special alumina used[7]. Special alumina used has a content of 1% Cr2O3 having the same role with that of Cr3C2 in case of metal carbide powders, namely an inhibitor of granulation increase in sinterized structure. Table 2. Physical-chemical characteristics of calcinated alumina powder Material Special alumina Al2O3 [%] cca. 99,5 Fe2O3 [%] max. 0,20 Alkalis [%] max. 0,15 Humidity [%] max. 0,5 SiO2 [%] max. 0,15 Al2O3 [%] cca. 98 Specific density [g/ cm3] 3,70
The special alumina powder having an average diameter of particles of 4-5 m was subjected to grinding for 16 hours to obtain a granulation as close as possible to the metal carbide powders used. Thus, following the grinding operation executed in Attritor, the average diameter of the alumina particles was 2 m. Attritor mills are made of a cylindrical vertical tank where the grinding ball load is activated by means of a vertical stem and a set of horizontal arms. These arms are arranged perpendicularly on the vertical stem and they carry along the balls by the rotation movement. Balls will move at first together with the stem arms, then they will be carried along in a falling movement triggering the collision among them and with the processed material. Collision may occur among balls, between balls and the tank walls and between balls, the stirring arm and arms. Grinding occurs due to collisions and frictions. The mills of this type are produced in a wide range of capacities (1-1000 dm3), they may have variable speeds, they may be cooled or may work in controlled atmospheres. The Attritor type installations have a simple design, they are easy to operate and allow the continuous execution of the process. Following fragmentation, we obtain a much more dimensionally uniform powder in a much shorter time as compared to the time necessary for the ball mills. For the experimental works, we prepared two mixtures having different compositions, according to table 3, so as to obtain cermets. Table 3. Compositions of experimental cermet-based mixtures Material / Mixture coding (TiC WC - (Ni, Co) - Al2O3) / A1 (TiC - (Ni, Co) - Al2O3) / A2 TiC [%] 75 75 WC [%] 10 Co [%] 5 5 Ni [%] 5 5 Al2O3 [%] 5 15
The execution of mixtures in reduced quantities (about 300 g) took place as follows: the component powders were dosed by weighing on the analytic balance; the powders were mechanically homogenized for 12 h, in cylindrical airtight containers 75 mm wide and 95 mm long, fitted on a rotating device with rotation n = 60 rpm. The aspect of the mixtures obtained following this operation was uniform without inhomogeneities visible by the naked eye. The powder mixtures were then bound with paraffin (4%), sieved in semidry state by a sieve having the size of meshes of 0.4 mm and then dried finally obtaining an adequate granulation of the powder mixtures characteristic to the ready for pressing mixtures. The binder used - A type paraffin has the following characteristics: density: = 0.90 g/cm3; melting type: Tt = 50 - 54 oC. In table 4, we give the characteristics of the cermet type mixtures obtained - (TiC WC - (Ni, Co) - Al2O3) / A1; (TiC - (Ni, Co) - Al2O3) / A2 [2].
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Table 4. Physical-technological characteristics of experimental mixtures Material / Mixture coding Powdery mixture obtained (TiC-WC-(Ni, Co) - Al2O3) / A1 (TiC- Ni, Co ) - Al2O ) / A2 Flow rate [sec/100] 55 62 Physical-technological characteristics Fischer average Apparent freely poured diameter FSSS unsettled density [g/cm3] [m] 4.56 4.23 1.95 1.80
The values obtained while determining the flow rate allow the use of these mixtures in making automatic presses with volumetric filling. To know the compaction aptitude, it was necessary to determine the optimal specific pressing pressure. The specific pressure ranges between 200 - 300 MPa depending on the nature and composition of powders used, the geometry and sizes of the part, the type and quality of matrix. The pressing was executed bilaterally on a steel matrix with circular section having the surface of 1 cm2, and a steel matrix having a rectangular section (6.26 x 43) mm2 to make the transversal rupture strength specimens, at specific pressures of 2000 N/mm2 for the powdery mixtures of the type A1 and A2 (v.[7]). From the cermet type powder mixtures obtained this way we pressed at least 15 cylindrical compressed items and 10 A type specimens from every composition, and we obtained the average densities of the compressed items given in table 5. Table 5. Average densities of the compressed items in uncured state from experimental cermet type mixtures Powder class TiC-WC-(Ni, Co) - Al2O3) / A1 (TiC- Ni, Co ) - Al2O ) / A2 Density in uncured state [g/ cm3] 4.975 4.889
All compressed items were measured (to subsequently determine the dimensional variation) and weighed (to determine the mass loss after the debinding pre-sinterization operation). As we expected, the smallest density in uncured state may be noticed for mixture A2 where the alumina content (having a smaller density as compared to the other constituents) is in a larger proportion (15 %) and does not contain wolfram carbide powder (with the highest density of all composing powders). In the process for the obtaining of conventional hard sinterized alloys, especially of cermets, to facilitate the pressing operation, we frequently use paraffin, as we mentioned above. Once the pressing process ended, the lubricant must be eliminated since its presence might cause certain drawbacks during the sinterization operation, such as: - carburization or oxidization of parts; - degradation of part surface (on the surface of parts might appear pinches caused by the exaggerated pressure of the gases resulted from the cracking of the lubricant or its fast volatilization). In general, lubricants melt at temperatures below 200oC and boil at temperatures below 350oC. Consequently, heating the parts must be slow by 30oC/min at most, up to 500-600oC, where they are kept for 30-45 minutes so as not to appear physical-chemical modifications in the deparaffined parts. In case of paraffin, this must be extracted slowly and controllably (depending on the size and surface specific to the parts) so as not to destroy the surface of the part and paraffin should not decompose forming free carbon. Deparaffining shall be executed in depressurized hydrogen current, in a static oven, the determination of the optimal work temperature being obtained experimentally. Thus, up to 400oC, the heating speed must be very slow, at 400oC paraffin cracks and forms inferior paraffinic hydrocarbons and free carbon. Its evaporation takes place depending on the surface of the compressed item exposed to the thermal flow that must ensure the volatilization of the lubricant without restrictions, the volatilizing quantity being replaced by another diffusing from the inside to the surface. Once paraffin has been transferred to the gas current, this must be removed from the reaction area as soon as possible; the parts must be put in such a manner that the maximum surface should be exposed in the atmosphere of the oven without creating areas of agglomeration or areas from where paraffin may not be removed in order to avoid its depositing on certain areas of the oven and its subsequent cracking. The pressed benchmarks were submitted to debinding in Siemens-Plania oven, in hydrogen atmosphere, using as a packing agent the alumina calcinated beforehand at 1450oC, for 5 hours, to ensure the thermal stability. The parameters of the debinding pre-sinterization process were:
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atmosphere- hydrogen; pre-sinterization temperature was in the temperature interval (800-900)oC; maintaining at pre-sinterization temperature: 30 min.; total time of the debinding pre-sinterization cycle: 8h 30 min;
Following the debinding pre-sinterization operation, we noticed that the established parameters allowed a uniform elimination of the binder without the appearance of cracks. The pressed benchmarks were submitted to the sinterization operation to obtain the complex of properties imposed to the material. The sinterization operation was executed in a vacuum induction heating furnace of Balzers type, with currents of average frequency and the parameters of the sinterization operation were the following: values of the sinterization temperature were in the interval 1400oC 1450oC; soaking time at sinterization temperature: 60 min.; total time of the cycle: 8 h. For the characterization of the sinterized benchmarks, we determined the following physical-mechanical properties: Vickers hardness HV50; density (g/cm3); transversal rupture resistance (daN/cm2); contraction to sinterization. In table 6, we present the characteristics of sinterized benchmarks made of the analysed compositions. The structural compositions were analysed by electronic microscopy SEM by means of an electron scan microscope CX 100-JEOL-TEMSCAN, at 100 kV, the magnification being 300,000 times, equipped with an energy dispersive analysis system (EDS) and wave length (WDX); Table 6. Characteristics of sinterized benchmarks Number of batch Batch A1/ (TiC-WC)-(Ni,Co) - Al2O3) Batch A2/(TiC- Ni, Co) - Al2O3 ) Density [g/cm3] 4.775 4.376 Rupture resistance [N/mm2 ] 525 350 HV50 1400 1450 Contraction on the direction of application of the pressing force Ch [ % ] 3.375 2.430
We may notice that the densities obtained have values typical to the cermet type hard alloys and fall in the interval 4.37-4.77 g/cm3, the smaller value of the density of mixture A 2 (4.376 g/cm3) as compared to the one corresponding to the powdery mixture A1 (4.775 g/cm3) is due to the fact that WC powder is missing from the structure of one of these mixtures (case of mixture A2) having the highest density among the carbides present in the four mixtures and to the fact that this class - class TiC - (Ni, Co) - Al2O3 mostly containing titanium carbide. The values of resistance to transversal rupture determined by parallelipipedic sinterized specimens indicate that batch A1/ (TiC-WC-(Ni,Co) - Al2O3) registers a clearly superior value to class TiC - (Ni, Co) - Al2O3 due to the presence of wolfram carbide. The value of the triplet density rupture resistance hardness obtained this way indicate that the sinterization parameters established for these mixtures allowed a high level of densification of the sinterized structures. The sinterized benchmarks were prepared for metallographic examination in order to determine microstructure. Microstructural analysis was executed by gradually highlighting the phases by Murakami attack. Murakami attack specific for the highlighting of the phases present in cermets and hard alloys is a mixture made of 10 gr K3Fe(CN)6, 10 gr. KOH and 100 ml distilled water. The samples for analysis were analysed under the electronic microscope with a magnification of X 1000, in attacked state (see figures no. 1-2). Figure 1 presents the morphology of particles from the structure of class type A1/TiC-WC-( Ni, Co) - Al2O3; we may notice fine granulation powders but also the fact that the phases existing in the sinterized structures are somehow non-uniformly distributed; the structure presented is an angular structure characteristic to the sinterized hard alloys (a possible explanation might be that this class of powder has the highest content of WC; structural non-homogeneity might be due to the insufficient humectation of the carbide phase WC by the binder phase Ni/Co).
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Attack: Murakami
X1000
Attack: Murakami
X1000
Figure 1. Microstructural aspect of cermet type mixture A1/ TiC-WC - (Ni, Co) - Al2O3)
Figure 2 Microstructural aspect of cermet type mixture A1/ TiC-WC - (Ni,Co) - Al2O3)
In figure 2, we present the morphology of the particles from the structure of class type A2/(TiC-(Ni, Co) - Al2O3 ); we may notice fine granulation powders, a relatively uniform distribution of components (relatively rounded shape of particles allows a high level of enveloping of particles). The structure presented is a structure typical to a cermet a structure of the type nucleus-cellular edge, the ceramic-metallic particles having rounded, annular shapes. 3. CONCLUSIONS We may obtain cermet-based mixtures with a high content of TiC (superior to 25%), different concentration of metal binder Ni/Co and special alumina Al2O3 by using techniques specific to the powder metallurgy; The systems of ceramic-metallic materials selected were characterized from the physical-mechanical and structural viewpoint in accordance with the norms specific to the powder metallurgy; The experiments effectuated allowed us to establish the factors with a significant influence on the characteristics of the materials of Cermet type under study, namely formation parameters, composition of gaseous environments as well as thermal and temporal parameters of the thermal treatment processes; The cermet type powdery mixtures obtained experimentally are recommended to be used in the making of cutting plates utilized on automatic machines, at very high chip removing speeds and in conditions of dry processing. 4. REFERENCES 1. C. Collin, 13-th International Plansee Seminar,Comparative study of the properties of WC-Co Cermet, vol. II, Reute, 1993, 505-522; 2. C. Collin, 1993, Processing of composition gradient WC-Co Cermet, 13-th International Plansee Seminar, Vol 2, Reutte, 522-537 3. N. Cherradi, 1996, Matriaux a gradient: exploatation du concept et tecniques de production par mtallurgie du poudres, La Revue de Mtallurgie CIT/Science et Genie des Matriaux, 185-196; 4. M. Sjostrand, 2001, Advances in coating technology for metal cutting tools, Metal Powder Report, No. 4, 2430; 5. A.F. Lisovsky, 1987 On the inhibition of metal melt by sintered carbides, Powder Metallurgy Intternational, No. 5, 18-21; 6. C. Ciocardia, E. Dragulanescu, I. Dragulanescu, 1985, Aliaje dure sinterizate din carburi metalice, Ed. Tehnic , Bucureti; 7. Raport de Cercetare ICEM-C156/2004, Faza II/2004; Researches regarding the obtaining of cermet type mixtures from TiC-WC-(Ni,Co)-Al2O3 and TiC-(Ni,Co)-Al2O3 systems
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SINTERING AND SINTERING ATMOSPHERES
www.turkishpm.org
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atmosphere effect on Sintering behaviour of Astaloy CrM and Astaloy Crl Hgans powders with manganese and carbon additions
Tadeusz PIECZONKA*, Maciej SULOWSKI*, Andrzej CIAS* *AGH University of Science and Technology, Faculty of Metals Engineering and Industrial Computer Science, Physical and Powder Metallurgy Research Unit, PL 30-059 Krakw, Poland, Al. Mickiewicza 30, pieczonk@agh.edu.pl Abstract Dilatometric data for Astaloy CrM (3% Cr-0.5% Mo) and Astaloy CrL (1.5% Cr-0.2% Mo) powders with additions of 0.3% carbon and 3.0% manganese during sintering cycles up to 1120 and 1250C in different atmospheres are reported. For comparison, also Astaloy CrM and Astaloy CrLpowders were investigated. Starting with green densities of approx. 6.8 g/cm3, the final density of sintered compacts was influenced mainly by the sintering temperature, while the results showed the only minor effect of the sintering atmosphere on the final dimensional changes. However, the sintering atmosphere influences the sintering behaviour and a final chemical composition of sintered compacts. In sintered and cooled in the dilatometer Mn-Cr-Mo-C steels predominantly bainitic structures were obtained / observed. Keywords: Pre-alloyed Iron Based Powders, Sintering, Dimensional Control, Dilatometry 1. INTRODUCTION Chromium and manganese are potentially important alloying elements in sintered steels. When correctly employed, they can improve mechanical properties, hardenability and nitridability [1-6]. For these reasons Cr and Mn are the elements, which are widely used in many structural wrought steels. However, up to date, these elements have seen little exploitation in the powder metallurgy (PM) industry due to their extremely high affinity for oxygen [7-16]. One of the recent (1998) industrially available means of incorporating chromium into structural PM parts production is use of the water atomised pre-alloyed Astaloy CrM (Fe-3%Cr-0.5%Mo) powder developed by Hgans AB [17]. This producer delivers also (since 2002) a modified powder grade AstaloyCrL (Fe-1.5%Cr-0.2%Mo) [18]. Sintered compacts made of these powders alloyed with carbon indicate attractive mechanical properties, including sinter hardening effect [19-24]. The limited use of both powders in PM industry is associated with the processing requirements of very low dew point/oxygen potential of the sintering atmosphere at normal link-belt sintering temperatures. The atmosphere requirements are relaxed by the use of elevated sintering temperatures (above 1200C) [1]. There has been, however, a reluctance on the part of manufacturers to use this technique in, for example, walking beam or pusher furnaces on the grounds of cost and availability. This situation is changing with the introduction of modern, more cost efficient furnaces. Because high temperature sintering (HTS) promotes oxide reduction, it is an especially very useful PM route for steels containing elements which have a high affinity for oxygen, particularly if they are added in elemental form. HTS further promotes homogenisation of the microstructure and pore rounding, which can lead to the improvement in the mechanical properties of PM steels [4]. Additionally, the hardenability of Astaloy CrM and Astaloy CrL steels can be further increased by manganese addition to the starting powder, and e.g. Mitchell et al [1-4] have reported or obtaining martensite, including by air hardening, and presented initial sinter hardening data. It is well known in PM industry that the dimensional changes occurring during the whole PM cycle have to be carefully controlled to produce high precise parts and to keep required tolerances. There are many parameters influencing the dimensional behaviour of the compact during sintering. Main of them is the sinterability of the material subjected to the specific
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external conditions, which includes chemical homogenisation and material sintering atmosphere interactions. Thus, in this paper a study of the temperature and atmosphere effect on dimensional changes of Mn and C containing compacts based on Astaloy CrM and Astaloy CrL Hgans grade powders is shown. 2. EXPERIMENTAL PROCEDURE The following starting powders were used: commercial pre-alloyed Fe-3%Cr-0.5%Mo Hgans Astaloy CrM grade powder, commercial pre-alloyed Fe-1.5%Cr-0.2%Mo Hgans Astaloy CrL grade powder, smaller than 40 m fraction (distribution centred around 10 m) of low carbon ELKEM ferromanganese powder supplied by Elkem Ferromanganese Sauda, Norway, containing 77.0 wt% Mn, 1.3 wt% C, 0.2 wt% O2, 0.02 wt% N2 and Fe bal., commercial C-UF Hgans fine graphite powder. The lubricant was not added. The starting powders were mixed in Turbula mixer for 30 minutes to prepare the following mixtures: Astaloy CrM + 0.30 wt% C + 3.0 wt% Mn, Astaloy CrM + 0.33 wt% C + 3.0 wt% Mn, Astaloy CrL + 0.30 wt% C + 3.0 wt % Mn, Astaloy CrL + 0.33 wt% C + 3.0 wt% Mn. For comparison, the compacts based on as-received Astaloy CrM and Astaloy CrL powders were also used. Mixtures were carefully handled to minimise any segregation of the constituents. The mixtures were compacted into rectangular specimens of size 4x4x15 mm3, using uniaxial pressing at 600 MPa. This resulted in green densities of about 6.8 g/cm3. The sintering experiments were carried out in a horizontal push rod dilatometer NETZSCH 402E. The measuring direction (length of the specimen) was chosen perpendicular to the pressing direction of the compacts. The gases used as the sintering atmospheres were: nitrogen, purity 5.0 95 vol.% nitrogen + 5 vol.% hydrogen mixture prepared from 5.0 purity gases, and argon, purity 4.5. The dew point measured at the inlet to the dilatometer was at least 55C. The flow rate was 50 ml/min at the internal tube diameter of 38 mm. Samples were heated at 10 C/min to the isothermal sintering temperature of either 1120C or 1250C. Isothermal sintering was then carried out for 60 minutes. It should be noted that the dilatometer used could not maintain the constant cooling rate during the whole cooling period. Thus, the cooling rate within the linear range (from isothermal temperature down to about 380C) was 20C/min (0.33C/s). Below 380C the cooling rate was decreasing continuously as it is seen on T-curves (e.g. in Figure 1). The temperature control was accurate to 1C. The changes in slope of the dilatometric traces were examined in detail. Sintered compacts were used to prepare metallographic specimens. 2% nital was used for etching. The microstructures of sintered compacts were observed by light microscopy. 3. RESULTS AND DISCUSSION Figures 1-4 show the complete dilatometric plots obtained during the current investigations. In the case of unmodified Astaloy CrL and Astaloy CrM powders, used as standard materials, initially the thermal expansion is observed, transformation begun at ~888C and ~878C, respectively, and finished at then the shrinkage due to ~918C for both powders, being ~ 0.20% with minor effect of the atmosphere. The isothermal dimensional changes of pure Astaloy CrL and Astaloy CrM compacts are strongly influenced by the temperature. During sintering at 1120C, the changes are negligible, irrespective of the sintering atmosphere, while at 1250C the effect of the sintering atmosphere is significant: the ~0.45% shrinkage is observed for both powders but only in hydrogen containing atmosphere (95%N2/5%H2). This behaviour can be explained by the extending oxides reduction at higher transformation starting earlier (i.e. at higher temtemperature [22]. Cooling period is characterised by the perature) in argon than in other atmospheres. Astaloy CrL specimens cooled from 1120C began to expand due to the transformation at ~870C in argon and at ~850C in nitrogen and nitrogen/hydrogen mixture. In case of Astaloy CrM the respective temperatures are: ~880C and ~830C. Compacts cooled after sintering at 1250C start to transform at ~880C in argon (irrespective of the powder grade) while at ~840C for Astaloy CrL and only at ~820C for Astaloy CrM in other atmospheres.
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Figure 1. Dilatometric curves for sintering cycles at 1120C under different furnace atmospheres. The details are given in individual figures.
Figure 2. Dilatometric curves for sintering cycles at 1250C under different furnace atmospheres. The details are given in individual figures.
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Specimens containing manganese and graphite heated from room temperature initially expand thermally, till ~ transformation in other atmospheres, which are: ~ 680C in argon atmosphere and till the beginning of 780C for Astaloy CrL-base composition and ~ 815C for Astaloy CrM-base one. Similarly to the not modified powders, the dimensional behaviour of Mn and C alloyed mixtures in argon differs from those in nitrogen and nitrogen/ hydrogen mixture. The expansion rate starts to decrease slightly only in argon at by ~ 130C (Astaloy CrL base transformation, powder) or even by ~ 160C (Astaloy CrM) lower temperature than that of the initiation of the which is better visible in Figure 5. Generally, Mn and C lower the temperature at which this transformation starts. This is important since it has been demonstrated by Mitchell et al [1, 4] that alpha phase sintering in Astaloy CrMbase alloys is to be avoided. Except argon, there were only minor effects due to the composition of the sintering transformation. It is, however, worthy of note that the thermal conductivity of the sinteratmosphere on the ing atmosphere was anticipated to be of more importance during cooling, especially when sinter hardening effects were expected. transformation the specimens expand until the sintering plateau, due to thermal After completion of the expansion and possibly also alloying and other sintering processes. The slopes of the dilatometric curves in this increasing temperature region depend on composition of the mixtures, being steeper for those based on Astaloy CrL powder, implying that homogenisation processes continue to take place. All the specimens sintered at 1120C expanded continuously during heating at almost constant rate, independently of the atmosphere (Figure 1), whereas those heated to 1250C reached their maximal length admittedly at that temperature, but starting at about 1200C at significantly lower expansion rate, which indicates that sintering shrinkage begins to dominate thermal expansion, starting just at 1200C. There was observed only a minor effect of the sintering atmosphere on isothermal shrinkage. At 1120C both mixtures shrank by ~0.6%, while at 1250C by ~1.3% in case of Astaloy CrL based composition and by ~1.4% for Astaloy CrM based one. The influence of sintering atmosphere on dimensional changes is more clearly illustrated in Figures 3 and 4. Interestingly, the argon produces the highest final shrinkage.
Figure 3. The influence of the sintering atmosphere on dimensional changes for specimens sintered at 1120C.
Figure 4. The influence of the sintering atmosphere on dimensional changes for specimens sintered at 1250C.
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Figure 5. Detailed dilatometric heating segments. The addition of carbon and ferromanganese to the Astaloy CrL and Astaloy CrM powders, which enhances sinter hardening effects, can be related to the cooling segments of the dilatometric curves (Figures 6 and 7). In the con transformation is not detected now. Because of the advanced trary to the unmodified base powders the homogenisation the sintered alloys show increased hardenability. Thus the approximate bainite start temperatures appear to be ~470C for Astaloy CrL + 0.3% C + 3% Mn and ~460C for Astaloy CrM + 0.3% C +3% Mn, respectively for compacts sintered at 1120C. The sintering temperature of 1250C increases the bainite start temperature (Bs) by about 40C. Independently of the composition and isothermal sintering temperature, Bs temperature is by about 20C higher in argon than in other atmospheres.
Figure 6. Detailed dilatometric cooling segments for compacts sintered at 1120C.
Figure 7. Detailed dilatometric cooling segments for compacts sintered at 1250C.
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The higher heat conductivity of the 95% N2 / 5% H2 atmosphere during cooling made only a negligible difference in heat transfer when the non-linear region of cooling rate was reached, probably due to the small thermal mass of the dilatometric sample. Thus sinter hardening was not significantly influenced by the high heat conductive hydrogen. It is well known in PM steel that carbon not only changes the transformations behaviour but also acts as a reducing agent. The last role is connected with some lost of this element during sintering. Therefore, the LECO analysis has been performed on the sintered compacts to control the final carbon content. The results showed the large decrease of carbon concentration: from ~25% up to ~75% as compared with that in green compacts. At higher sintering temperatures the higher carbon reduction was recorded. Thermodynamics indicates favourable conditions for carbothermic reduction of Cr and Mn oxides at conventional sintering temperatures. For reduction of Cr2O3 and MnO by solid carbon thermodynamic calculations for atmosphere predominantly of nitrogen were carried out by Cias and Mitchell [24, 25]. Comparison of calculated ratio of partial pressures p(CO)/p(CO2) and maximum allowed partial pressure of O2 and H2O in the 90% N2 / 10% H2 atmosphere with the experimentally obtained one, by continuous atmosphere monitoring during the sintering of Astaloy CrM + 0.5% C, clearly shows favourable conditions for carbothermic reduction of the chromium oxides during isothermal sintering at 1120C or higher [26]. The effect of the sintering atmosphere is not unambiguous. The relatively low carbon concentration in sintered steels seems to be responsible for their rather limited sinter hardenability. The examples of sintered microstructures are shown in Figures 8 and 9.
Figure 8. Microstructure of Astaloy CrL + 0.3 wt% C + 3 wt% Mn sintered at 1250C: left in N2/H2=95/5, right in argon.
Figure 9. Microstructure of Astaloy CrM + 0.3 wt% C + 3 wt% Mn sintered at 1250C: left in N2/H2=95/5, right in argon. Generally for both base powders, sintering in nitrogen and in 95% N2 / 5% H2 gas mixture produces homogeneous bainitic microstructure with rounded pores, whereas the microstructure of compacts sintered in argon is characterised by bainitic matrix containing one phase bright grains. The identification of the phase and the role of argon in its appearance require further investigations.
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4. CONCLUSION REMARKS The relatively small shrinkages observed at the sintering temperatures probably resulted from solid state sintering of the compacts with a relatively low green density of approx. 6.8 g/cm3. In accordance with the theoretical phase diagrams, for the Fe-3%Cr-0.5%Mo-C and Fe-1%Cr-3%Mn-0.5%Mo-C systems [27], to obtain a liquid phase for the alloys investigated temperatures of the order of 1400C are required. Therefore to increase densification at chosen isothermal temperatures this sintering period should be elongated. Based on isothermal shrinkage rate shown in Figures 1 and 2 it can be stated that there is still a potential for further shrinkage at these temperatures. Why argon modifies the sintering behaviour and microstructure of materials investigated is not completely clear. Probably it can be explained, at least partly, by the low heat conductivity of this gas. The further investigations in this field, including mechanical properties of in argon sintered compacts, are under way. ACKNOWLEDGEMENTS The financial support of the Ministry of Science and Higher Education under the contract no N N507 477237 (AGH no 18.18.110.961) is gratefully acknowledged. REFERENCES 1. Mitchell, S.C, Wronski, A.S., Cias, A., Stoytchev, M., Microstructure and Mechanical Properties of Mn-Cr-Mo-C Steels Sintered at >1140C, Advances in Powder Metallurgy and Particulate Materials, Vol .2, MPIF, pp.7129 to 7-144, 1999. 2. Wronski, A.S., Becker, B.S., Wright, C. S., Mitchell, S.C., Alloy Design for Improved Mechanical Properties and Robust Processing, Proc. DFPM99, ed. L. Parilak and H. Danninger, Vol. 1, pp.1/155 to 1/166, 1999. 3. Mitchell, S.C., The Development of Powder Metallurgy Manganese Containing Low-Alloy Steels, Ph.D. thesis, University of Bradford, 2000. 4. Wronski, A.S., Cias, A., Barczy, P., Stoytchev, M., et al, Tough Fatigue and Wear Resistant Sintered Gear Wheels, Final Report on EU Copernicus Contract No. ERB CIPA CT-94-0108, European Commission, 1998. 5. Lindsley, B., James, B. PM Steels That Contain Manganese, Advances in Powder Metallurgy & Particulate Materials, MPIF, Hollywood, Vol. 10, pp. 36-49, 2010. 6. Hryha, E., Dudrova, E., Nyborg, L., Critical Aspects of Alloying of Sintered Steels with Manganese, Metallurgical and Materials Transactions A-Physical Metallurgy and Materials Science, 41A (11), pp. 2880-2897. 7. Navara, E., Sintering of Iron Powder with an Addition of Ferromanganese, Sintering85, compiled by G.C. Kuczynski et al., Plenum Press, pp. 343-356, 1985. 8. Klein, A.N., Oberacker, R., Thmmler, F., High Strength Si-Mn- Alloyed Sintered Steels. Microstructure and Mechanical Properties, Powder Metallurgy International, Vol. 17, No. 1, pp. 13-16, 1985. 9. Klein, A.N., Oberacker, R., Thmmler, F., High Strength Si-Mn- Alloyed Sintered Steels. Sinterability and Homogenization, Powder Metallurgy International, Vol. 17, No. 2, pp. 71-74, 1985. 10. Salak, A., Effect of Extreme Sintering Condition upon Properties of Sintered Manganese Steels, Powder Metallurgy International, Vol. 16, No. 6, pp. 260-263, 1984. 11. Salak, A., Manganese Sublimation and Carbon Ferromanganese Liquid Phase Formation During Sintering of Premixed Manganese Steels, International Journal of Powder Metallurgy, Vol. 16, No. 4, pp. 369-379, 1980. 12. Danninger, H., Pttschacher, R., Jangg, G., Seyrkammer, J., Salak, A., Manganese Alloyed Sintered Steels Prepared from Elemental Powders, Proc. PM94 World Congress, EPMA, Paris, Vol.1, pp. 879-882, 1994. 13. Danninger, H., Gierl, C., New Alloying Systems for Ferrous Powder Metallurgy Precision Parts, Science of Sintering, 40, pp. 33-46, 2008. 14. Selecka, M., Salak, A., Pieczonka, T., Stoytchev, M., Solid Phase Sintering and Alloying of Powder Fe-Mn Steels Observed by Dilatometry, Proc. Int. Powder Metallurgy Congress and Exhibition EURO PM2007, Vol. 1, pp. 47-50, 2007. 15. Selecka, M., Salak, A., Pieczonka, T., Solid Phase - Gas Phase Sintering and Alloying of Powder Fe-Mn Steels Analysed by Dilatometry, Steel Grips, Vol. 6, No. 5, pp. 355-358, 2008. 16. Hryha, E., Nyborg, L., Dudrova, E., Bengtsson, S., Microstructure Development During Sintering of Manganese Alloyed PM Steels, Proc. EURO PM2009 (CD), Copenhagen, Denmark, 2009. 17. Lindberg, C., Mechanical Properties of Water Atomised Fe-Cr-Mo Powder and How to Sinter It, Advances in Powder Metallurgy and Particulate Materials, Vol. 2, MPIF, pp. 7-229 to 7-244, 1999. 18. Engstrom, U., Klekovkin, A., Berg, S., Edwards, B., Frayman, L., Hinzmann, G., Whitehouse, D., Efficient LowAlloy Steels for High Performance Structural Applications, Advances in Powder Metallurgy & Particulate Materials, MPIF Las Vegas, USA, Vol. 7, pp. 68-79, 2003. 19. Molinari, A., Straffelini, G., Campestrini, P., Influence of Microstructure on Impact and Wear Behaviour of Sintered Cr and Mo Steel, Powder Metallurgy, Vol. 42, No. 3, pp. 235-241, 1999.
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20. Engstrm, U., Evaluation of Sinter Hardening of Different PM Materials, Advances in Powder Metallurgy & Particulate Materials, Vol. 5, MPIF, pp. 5147 to 5-157, 2000. 21. Lindberg, C., Johansson, B., Maroli, B., Mechanical Properties of Warm Compacted Astaloy CrM, Advances in Powder Metallurgy & Particulate Materials, Vol. 6, MPIF, pp. 681 to 6-92, 2000. 22. Castro, F., Ortiz, P., Study of Gas Solid Interactions During Sintering of Cr-Containing PM Steels, Proc. of EURO PM2003, Valencia, Spain, Vol. 1, pp. 243-249, 2003. 23. Bergman, O., Nyborg, L., Evaluation of Sintered Properties of PM Steels Based on Cr and Cr-Mn Prealloyed Steel Powders, Powder Metallurgy Progress, Vol.10, No.1, pp. 1-19, 2010. 24. Cias A., Development and properties of Fe-Mn-(Mo)-(Cr)-C sintered steels, Ed. AGH UST, Krakw, 2004. 25. Mitchell S. C., Cias A., Carbothermic reduction of oxides during nitrogen sintering of manganese and chromium steels, Powder Metallurgy Progress, Vol. 4, No 3, pp. 132-142, 2004. 26. Hryha E., ajkova E., Dudrov E., Study of reduction/oxidation processes in Cr-Mo prealloyed steels during sintering by continuous atmosphere monitoring, Powder Metallurgy Progress, Vol. 7, No 4, pp. 181-197, 2007. 27. Pieczonka, T., Mitchell, S.C., Stoytchev, M., Kowalczyk, M. Liquid Phase Sintering of Fe-3Cr-1Mn-0.5Mo High Carbon Steels, Proc. of the 2002 Int. Conf. on Powder Metallurgy & Particulate Materials, Orlando, USA, Vol. 11, pp. 1428, 2002.
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CARBON, OXYGEN AND NITROGEN VARIATIONS DURING SINTERING OF Mo PREALLOYED AND Ni-Cu-Mo DIFFUSION BONDED STEELS
Mohammad MOMENI*, Herbert DANNINGER** and Christian GIERL*** Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164, A-1060 Wien/Vienna, Austria *mmomeni@mail.tuwien.ac.at, **hdanning@mail.tuwien.ac.at, ***cgierl@mail.tuwien.ac.at ABSTRACT In this research, Mo prealloyed and Ni-Cu-Mo diffusion bonded steels were produced, sintering was conducted from 700 to 1300C temperature in nitrogen atmosphere, and interstitial elements; i.e. carbon, oxygen and nitrogen contents were determined by carrier gas hot extraction method (Leco). In both steels, the major part of the oxides are reduced up to 1000C, with resulting loss of carbon, but above this temperature only about 0.01% oxygen is removed. Nitrogen pickup was measured in both materials by less than 0.03% up 1000C; this confirms once more that nitrogen can be used as neutral atmosphere except for soft magnetic materials. Keywords: Sintered steel, Interstitial contents, Mo prealloyed, Cu-Ni-Mo diffusion bonded, Powder metallurgy. 1. INTRODUCTION Sintering not only means formation and growth of interparticle contacts and lowering or in some cases, eliminating the porosity, but it also brings about changes of the specimen chemistry [1]. Therefore, investigation of the reduction of surface oxides, carbon dissolution, formation of sintered contacts and phase transformation during the thermal cycle is a necessity to understand the sintering procedure in an appropriate manner. Standard alloying elements for PM-steels such as Cu, Ni and Mo, having significantly less affinity to oxygen than Cr, require O2 partial pressures better than 10-13 bar and thus can be easily sintered in standard atmospheres [2]. Thus industrial sintering is feasible in N2/H2 atmospheres containing tolerably low fractions of oxygen and/or oxidizing species including H2O and CO2. During sintering in an inert atmosphere such as dry nitrogen, carbon acts as an agent for reduction of oxidic surfaces of metal powders. Thus, the transport via gas phase is a parallel process to the direct solid state diffusion of carbon in the iron matrix [3], but Dautzenberg et al [4] stated that the solution of carbon into premixed sintered steel during sintering is not depending as usually assumed - on a conversion of the graphite into CO but appears to be a direct solid state diffusion. Sintering atmospheres based on nitrogen/hydrogen combinations are widely used for processing high performance and close dimensional tolerance steel components. In practice, a relatively low dew point is required which is of no concern as the commercially available industrial gases of today are of good quality. The low dew point of the nitrogen ( -70C) helps prevent decarburization and increase reducing potential [5,6]. Generally, nitrogen by itself does an effective job of keeping oxygen out of the furnace [7], and sintering in nitrogen results in faster dissolution of carbon relative to hydrogen [3,8]. Carbon can act as reducing agent both as element and in CO, the latter one is known as indirect carbothermic reaction and the former as direct oxide reduction [9]. For plain carbon steels, investigations showed that there are three temperature ranges within which gas formation, associated with weight loss, preferentially takes place. The first interval, ranging between 50 and about 500C, is mostly associated with desorption of water or decomposition of hydroxides, mass 18-H2O being preferentially detected in two maxima at 150 and 450C, respectively. In the same
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temperature range also mass 44-CO2 can be detected, with a pronounced maximum at 350-400C, which shows carbothermic reduction reactions. The second temperature interval is rather narrow, between 680 and 750C, but here a very pronounced mass loss occurs, indicates CO formation. The second peak occurs at slightly higher temperatures in Fe-Mo-C than for Fe-C at about 750C, i.e., apparently following the shifting of the ferrite to austenite transformation [10,11]. A third, rather less pronounced peak which, however, in total results in larger mass loss than the other peaks is found in the temperature range 950-1100C and also consists mostly of CO [12]. The only reasonable explanation was that the oxygen originated from different sources, i.e., the reduction at about 700C involves the surface oxygen and the process at higher temperatures the oxygen present within the powder particles. In this work, two different alloyed steels, i.e. Mo prealloyed and Ni-Cu-Mo diffusion bonded steels, were produced. They were compacted at 600 MPa and sintering was done between 700 and 1300C in N2 atmosphere. With relatively wide range of sintering temperature, the sintering procedure can be studied from initial stages up to high temperature levels. Oxygen, carbon and nitrogen contents were measured by carrier gas hot extraction method (Leco). Oxygen content is helpful in order to evaluate reduction of oxides and estimate progress in sintering procedure. Carbon is consumed during carbothermic reduction; therefore the carbon loss should be compensated, and the nitrogen pick up can also be evaluated by nitrogen measurement. 2. EXPERIMENTAL PROCEDURE Mo prealloyed powder Fe-1.5% Mo (Hgans Astaloy Mo) and 4%Ni-1.5%Cu-0.5%Mo diffusion bonded grade (Hgans Distaloy AE) were used for this experiment. Natural graphite UF4 was used as an additive and 0.5% HWC as a lubricant, and two chemical compositions were produced, i.e. Astaloy Mo- 0.5% C and Distaloy AE- 0.5% C. Powders were mixed in a tumbling mixer for 60 min. Charpy test bars (ISO 5754) were prepared by compacting at 600 MPa. The specimens were first dewaxed at 600C for 30 min in flowing high purity N2 in a small tube furnace. After that they were sintered in N2 at widely varying temperatures, between 700 and 1300C with 100C interval, in a large pusher furnace with gas tight superalloy retort, isothermal sintering time was 60 minutes. The cooling rate was approx. 0.5C/s average. Sintered densities were measured using the Archimedes method (DIN ISO 3369). Dimensions were measured with precision of 0.01 mm for each sample, and the dimensional change during sintering was calculated. Then the oxygen and nitrogen contents of the specimens were measured using carrier gas hot extraction (Leco TC400). Carbon content was measured after sintering using combustion analysis (Leco CS230). The measured carbon, oxygen and nitrogen content of base powders is presented in Table 1. Mass change was calculated from difference of mass between green and sintered parts. Mass spectrometry investigations have been conducted in a Netzsch STA 402C pushrod dilatometer with alumina measuring system. Before each test run, the system was evacuated and flooded with high purity helium for 3 times. Then the runs were performed by heating at 10 K.min1 up to 1300 C, soaking for 1 h, and then cooling at 10 K.min1. N2 (99.999%) with flow rates of 10 ml.min1 was used as protective gas (only running through the balance system) and with 50 ml. min1 as working atmosphere (in contact with the specimen). For identifying the degassing processes occurring during sintering, recorded intensities of m44 (CO2), m12 (C) and m16 (O) were evaluated. 3. RESULTS AND DISCUSSION 3.1. Density and dimensional change Sintered densities and dimensional changes of both steels as function of sintering temperature are presented in Figure 1. The results show only marginal changes of sintered density for both diffusion bonded and prealloyed steels below 900 and 1000C respectively; increasing by only about 0.02 g.cm-3 for the former and without any significant increment for the latter. In diffusion bonded powder compacts, contacts between particles are originated not only from compacting pressure but also from powder particles itself, therefore with slight oxide reduction and the subsequently carbon dissolution at initial stages of sintering, sintered density slightly improved. The reason is due to the characteristics of diffusion powder particles; on surfaces with highest content of metallic alloying elements the sintering contacts can be formed and improved already by slight carbon dissolution, while for plain carbon steel compacts higher carbon dissolution is necessary to enhance the Ac or load bearing cross section.
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Dimensional changes of course show an opposite trend to sintered density. The observed expansion between 700 and 900C for prealloyed steel shows that sintering contacts is not formed properly at these temperature intervals, the reason is due to the carbon dissolution and formation of austenite. As already reported, sintering is in progress in both ferritic and austenitic areas and the sintering bridges are improved up to 900C but the significant sintering contacts are formed in Mo containing prealloyed material at higher temperature levels [13]. Table 1. Measured carbon, oxygen and nitrogen content of different base powders. Material Astaloy Mo Distaloy AE Carbon (wt%) 0,0082 0,0089 Oxygen (wt%) 0,0842 0,1220 Nitrogen (wt%) 0,00056 0,00081
Figure 1. Dimensional properties as a function of sintering temperature, compacted at 600 MPa, sintered 60 min in N2, A: sintered density, B: dimensional change. 3.2. Interstitial elements Table 2 shows the measured carbon, oxygen and nitrogen contents for both steels sintered from 700 to 1300C with an interval 100C, and the graphs of interstitial elements as function of sintering temperature are represented in Figure 2 and Figure 3. In order to eliminate the effect of different atomic weight, carbon and oxygen contents are presented in atomic percentage in Table 3 with their accumulated reductions at different temperature intervals (for calculating the atomic percent out of weight percent, only main alloying elements i.e. Fe, Mo, Ni, Cu, C, O and N were considered). As stated in Table 1, the oxygen content in the diffusion bonded material is about 50% higher than in the prealloyed grade. Oxygen content in AstaloyMo and DistaloyAE was reduced from 0.08 to 0.006 wt% (0.28 to 0.02 at%) and from 0.09 to 0.007 wt% (0.33 to 0.03 at%) respectively when the sintering temperature increased from 700 to 1300C. Figure 2 shows that in both steels the major part of oxygen content was reduced up to 1000C, and above 1000C only about 0.01% oxygen is removed. While below 1100C the diffusion bonded grade shows more oxygen content than AstaloyMo, above 1000C the oxygen contents in both steels are relatively similar. It is obvious that in a neutral atmosphere such as nitrogen, and in presence of admixed graphite in powder compacts, oxygen is reduced through carbothermic reaction which means by carbon consumption. Carbon decreased from 0.64 to 0.55 wt% (2.9 to 2.5 at%) for Mo containing material while it decreased from 0.54 to 0.47 wt% (2.5 to 2.2 at%) for diffusion bonded grade. For Mo containing material terminating carbon consumption up to 1300C is visible while for DistaloyAE oxide reduction yields relatively similar carbon level in the range of 1100 to 1300C. Higher level of oxygen content in DistaloyAE compared with AstaloyMo below 1100C should be reduced with higher level of carbon consumption at lower sintering temperatures. The relative ratio of carbon consumption to
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oxygen reduction (as stated in Table 3) at 800C is about 1.5 and 2 for Mo containing and diffusion bonded material. The reason can be in part due to the slightly finer particles of the latter and also its bonded structure that yields smaller diffusion path to reduce oxides especially at initial stages of sintering. Table 2. Carbon, oxygen and nitrogen contents with their standard deviations for both steels sintered in a wide temperature range. Material Compaction pressure (MPa) Sintering Carbon C Oxygen O temperature content standard content standard (C) (Wt%) deviation (Wt%) deviation 700 800 900 1000 1100 1200 600 DistaloyAE-0.5%C (AE) 1300 700 800 900 1000 1100 1200 1300 0,6382 0,6212 0,5971 0,5828 0,5731 0,5671 0,5504 0,5433 0,5125 0,4995 0,4816 0,4739 0,4766 0,4726 0,0042 0,0071 0,0015 0,0050 0,0018 0,0113 0,0061 0,0042 0,0035 0,0081 0,0043 0,0071 0,0021 0,0070 0,0815 0,0670 0,0422 0,0178 0,0088 0,0087 0,0058 0,0948 0,0756 0,0513 0,0213 0,0118 0,0088 0,0073 0,0016 0,0017 0,0013 0,0004 0,0002 0,0003 0,0001 0,0035 0,0006 0,0011 0,0004 0,0010 0,0012 0,0003 Nitrogen content (Wt%) 0,0059 0,0104 0,0231 0,0262 0,0239 0,0226 0,0217 0,0098 0,0077 0,0119 0,0197 0,0189 0,0178 0,0175 N standard deviation 0,0002 0,0004 0,0002 0,0002 0,0002 0,0002 0,0001 0,0007 0,0002 0,0009 0,0001 0,0001 0,0001 0,0001
Figure 2. Interstitial elements as a function of the sintering temperature, compacted at 600 MPa, sintered in N2 atmosphere, A: Carbon and B: Oxygen. Figure 3 shows the nitrogen uptake from the atmosphere during sintering. Sintering in N2 base atmosphere enhances the probability to pick up the nitrogen in the sintered part. High purity N2 by itself is usually thought to be an inert gas in sintering of ferrous compacts, but the chemical analysis shows that there is a small amount of nitrogen pickup, less than 0.03% up to 1000C, and at higher sintering temperatures nitrogen contents tend to level off. Therefore the amount of N introduced is rather low and, except for soft magnetic materials, pure nitrogen can be used as neutral atmosphere. It is also reported that even the higher N content in Cr-Mo prealloyed steel, present as nitrides, is not dangerous for the mechanical properties of the material because the nitrides are distributed in the matrix and not concentrated at the grain boundaries [14].
AstaloyMo-0.6%C (Mo)
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Table 3. Carbon and oxygen contents, their reductions (at %) and ratio carbon consumption to oxygen reduction at different temperature intervals for both steels. Material Compaction pressure (MPa) Sintering temperature (C) 700 AstaloyMo-0.6%C (Mo) 800 900 1000 1100 1200 600 DistaloyAE-0.5%C (AE) 1300 700 800 900 1000 1100 1200 1300 Carbon content (at %) 2,91 2,84 2,73 2,67 2,62 2,60 2,52 2,49 2,35 2,29 2,21 2,18 2,19 2,17 Oxygen content (at %) 0,28 0,23 0,14 0,06 0,03 0,03 0,02 0,33 0,26 0,18 0,07 0,04 0,03 0,03 Reduction of carbon (at %)* NA 0,07 0,18 0,24 0,29 0,31 0,39 NA 0,14 0,20 0,28 0,31 0,30 0,32 Reduction of oxygen (at %)* NA 0,05 0,14 0,22 0,25 0,25 0,26 NA 0,07 0,15 0,26 0,29 0,30 0,30 Ccons/Ored ratio* NA 1,46 1,34 1,11 1,15 1,25 1,49 NA 2,03 1,30 1,08 1,08 1,00 1,04
*Oxygen reduction and carbon consumption were calculated with respect to the sintered part at 700C.
Figure 3. Nitrogen content as a function of the sintering temperature, compacted at 600 MPa, sintered in N2 atmosphere. 3.3. Mass spectrometry Comparative intensities for mass 44 (CO2), m12 (C) and m16 (O) recorded by mass spectrometry in the dilatometer are shown in Figure 4 and Figure 5. Figure 4 shows carbothermic reduction by CO forming CO2 which is more intense at lower temperature according to Boudouard equation. Mass 12 can be used to derive an indirect indication of the formed CO [11,15] as recording m28 during sintering in nitrogen atmosphere is not effective because of interference of the m28 signals for the two chemical compounds with the same mass, i.e., CO and N2, and m16 shows the spectra for atomic oxygen.
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Figure 4. Comparative gas intensities for mass 44 (CO2), compacted at 600 MPa, sintering at 1300C in N2 atmosphere, heating-cooling rate: 10K/min. DistaloyAE shows the tallest and widest peak for all three mass intensities during reduction of surface and internal oxides, therefore more surface and internal oxides are removed by formation of CO2 and CO. Observing almost the same level of intensity for mass 16 or atomic oxygen above 1150C certifies that for both steels the same amount of oxygen should be reduced above that temperature. While the oxygen contents were measured ex situ from the specimens sintered at different temperatures for 60 min isothermally in a laboratory furnace, the mass intensity was in situ recorded by mass spectrometry during the sintering procedure, but it seems that the results of these two different analytic methods can be reliably correlated.
Figure 5. Comparative gas intensities for mass 12 (C) and mass 16 (O), compacted at 600 MPa, sintering at 1300C in N2 atmosphere, heating-cooling rate: 10K/min. Figure 6 shows the carbon consumption as a function of oxygen reduction. This graph is helpful to predict one of them if the other has been measured. The relations between C consumption and O reduction show that the majority of oxygen removal in all alloys takes place by formation of CO and not CO2, i.e. by direct reduction.
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Figure 6. Carbon consumption as a function of oxygen reduction for both sintered steels; compacted at 600 MPa, sintering at 700-1300C in N2 atmosphere. 4. CONCLUSION The chemical analysis shows that for both steels the major part of oxides is reduced up to 1000C; yielding an oxygen content of about 0.02 wt%, and with using higher sintering temperatures oxygen is reduced to less than 0.01 wt% for both steels and then tends to level off. The content of carbon, as reducing agent, shows its continuous decrease in Mo prealloyed steel from 700 to 1300C but for diffusion bonded material there is not any significant reduction above 1100C. The higher ratio of carbon consumption to oxygen reduction at 800C for diffusion bonded steel in comparison with Mo prealloyed grade indicates more carbon loss in the former material at initial stages of sintering. Nitrogen pickup was measured in both materials to be less than 0.03% up to 1000C; this confirms once more that nitrogen can be used as neutral atmosphere except for soft magnetic materials. 5. REFERENCES 1- Xu, C., Blanco, L., Campos, M., Torralba, J.M., Effect of High Density Levels on Degassing of High Strength PM Steel Compacts, Euro PM2004, Vol.2, Sintering, Vienna, Austria, p.19-24, 2004. 2- Hatami, S., Hryha, E., Nyborg, L., Nilsson, D., Modelling of Sintering Atmosphere and Microstructure Development of Chromium Alloyed Steel, Powder Metallurgy Progress, Vol.8, No.2, pp.115-120, 2008. 3- Simchi, A., Danninger, H., Gierl, C., Electrical Conductivity and Microstructure of Sintered Ferrous Materials: IronGraphite Compacts, Powder Metallurgy, vol.44, No.2, pp.148-156, 2001. 4- Dautzenberg, N., Hewing, J., Beitrag zur Kinetik der Graphitaufloesung beim Sintern von Kohlenstoffstaehlen, Proceedings Powder Metallurgy Symposium Grenoble 7 pages, 1974. 5- Wilyman, P.R., Sintering With Nitrogen Based Atmospheres, Powder Metallurgy, Vol.28, No.2, pp. 85- 89, 1985. 6- Lindqvist, B., Kanno, K., Considerations When Sintering Oxidation-Sensitive PM Steels, Powder Metallurgy and Particulate Materials, MPIF, Part 13, 16-21 June, Orlando, USA, pp.278-290, 2002. 7- Philips, T., Dwyer, J.J., Zurecki, Z., Controlling Properties of Sintered Steel Powder Metal Components Using Atmosphere Composition As a Variable, Air Products and Chemicals, Inc., 8 p., 2006. 8- Danninger, H., Wolfsgruber, E., Ratzi, R., Sintering of Different PM Ferrous Materials at Moderate Temperatures, 1998 PM World Congress, Sintering, Spain, File PDF No. 589, pp.290-295, 1998. 9- Ortiz, P., Castro, F., Thermodynamic and Experimental Study of Role of Sintering Atmospheres and Graphite Additions on Oxide Reduction in Astaloy CrM Powder Compacts, Powder Metallurgy, Vol.47, No.3, pp.291-298, 2004. 10- Danninger, H., Gierl, C., New Alloying Systems for Ferrous Powder Metallurgy Precision Parts, Science of Sintering, Vol.40, pp.33-46, 2008. 11- Danninger, H., Gierl, C., Kremel, S., Leitner, G., Roessler, K.J., Yu, Y., Degassing and Deoxidation Processes During Sintering of Unalloyed and Alloyed PM Steels, Powder Metallurgy Progress, vol.2, No.3, pp.125- 140, 2002. 12- Danninger, H., Gierl, C., Processes In PM Steel Compacts During The Initial Stages of Sintering, Materials Chemistry and Physics, Vol.67, pp.4955, 2001. 13- Momeni, M., Gierl, Ch., Danninger, H., Ratio Tensile Strength-Vickers Hardness in Sintered Steels as a Function of The Sintering Temperatures, Powder Metallurgy Progress, Vol.8, No.3, pp.183-189, 2008. 14- Dlapka, M., Gierl, C., Danninger, H., Bengtsson, S., Dudrova, E., Nitrogen Pickup During Sintering and Subsequent Cooling of Chromium Alloyed PM Steels, PM2010 Powder Metallurgy World Congress & Exhibition, Florence, 10-14 Oct, Florence, Italy, Vol.2, pp.13-20. 15- Momeni, M., Gierl, C., Danninger, H., Study of the Oxide Reduction and Interstitial Contents during Sintering of Different Plain Carbon Steels by In Situ Mass Spectrometry in Nitrogen Atmosphere, Materials Chemistry and Physics, Vol.129, Issues 1-2, pp.209-216, 2011.
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SINTER HARDENING A TIME / COST EFFICIENT PRODUCTION LINE

Peter JOHANSSON*, Eda YILMAZTRK YKSEKDA** *Hganas AB, SE-263 83, Hganas, Sweden, peter.johansson@hoganas.com **Hganas AB, Turkey Agency Office, Eksper Endustriyel Hammadde ve Dis Ticaret Ltd Sti, Sipahioglu Caddesi, Salkim Apartmani, No:11 D:13, 34149, Yesilyurt, Istanbul, Turkey, eda@eksperdisticaret.com ABSTRACT In order to cut costs and increase production capacity; sinter hardening could be the process route to choose. By implementation of the sinter hardening process in the production line, it will be possible to have hardened components directly after the sintering operation. Instead of an additional heat treatment operation in-house or by subcontractor, the components can move on directly to secondary operations or in some cases directly for packaging and shipment to end user. As with traditional heat treatment a tempering operation is mandatory for stress relief of the material in order to increase tensile strength and elongation properties. To have successful results, it is necessary to do proper set up of the furnace and also perform enough trials to understand and optimize the end result. On the market, there are several powder alloys suitable for sinter hardening operations. Many of the alloys could be sintered in all traditional atmospheres such as endogas, cracked ammonia and nitrogen based atmospheres but some of the high perfomance materials for sinter hardening require nitrogen based atmospheres. Key Words: Sinter Hardening, Cost Reduction on Sintering, Astaloy85Mo, Distaloy DH, Astaloy CrA, Astaloy CrM. 1. INTRODUCTION TO SINTER HARDENING To continue to expand the PM market into new applications, there is a need for materials with increased performance manufactured in a cost effective way. This can be achieved by different means. Sinter hardening, which utilizes high performance materials in combination with accelerated post sintering cooling rates, is one example of such means. As this is a one step process, it combines good manufacturing economy with the ability to achieve a unique combination of mechanical properties. Alloying elements such as copper, nickel, molybdenum and chromium all promote hardenability and these are therefore utilized for sinter hardened PM applications. However, during the last years there have been dramatic increases and fluctuations in raw material costs of especially nickel and molybdenum. Therefore there is a continuously growing interest to utilize more cost effective and less volatile alloy systems that enable enhanced mechanical properties after sinter hardening. In this paper cost effective low alloy steel powders and their properties achieved after sinter hardening will be presented. The hardenability of a material is characterized as the ability to transform austenite into martensite. In PM, the hardenability of a material is dependent on the content of alloying elements, alloying method and processing. Carbon content also plays an important role in hardenability. Alloying increases the hardenability of a material and allows for more martensite transformation at a given cooling rate, which increases the mechanical properties. Elements such as nickel, copper, and molybdenum were among the first alloying elements to be used in PM to increase strength and hardenability.
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Although elements such as chromium and manganese increase hardenability more than nickel and copper, they were not used in PM alloys due to oxygen sensitivity. Advances in sintering & powder production technology have made it possible to successfully utilize chromium and manganese and take advantage of their attributes. Heat treatment of PM components can be performed using a variety of methods. The traditional austenitize, quench & tempering methods are widely used throughout the PM industry. If a component manufacturer does not want a secondary heat treatment operation, sinterhardening can be used. Sinter hardening; combines sintering and heat treatment in one single step in order to produce high strength and wear resistance of the material and minimizing the number of processing steps. Both conventional quench & tempering and sinter hardening modify the microstructure of a material system through increased cooling rates. Sinter hardening is a process step that can be fully integrated in the normal sintering operation. The sintering furnace is equipped with a rapid cooling device (gas quenching) between the sintering zone and cooling zone circled in figure 1.
Figure 1. Belt furnace equipped with rapid cooling device. The sintering atmosphere is cooled by circulation of gas through heat exchangers as shown in Figure 2.
Figure 2. Rapid cooling device. Normal cooling rates achieved in production lines are 2 to 5C/s depending upon furnace load, i.e. mass and geometry. After sintering zone (or carbon restoration zone if the furnace is equipped with this section), the rapid cooling occurs. Figure 3 displays a typical temperature profile where rapid cooling starts directly after the sintering zone.
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Materials for sinter hardening are tailor made in order harden at slightly higher cooling speeds than for normal sintering operations with cooling speeds between 0.5 to 1.0C/s. If insufficient hardening was obtained, as in Figure 4a, with too low amount of martensite, the alloying elements could be modified. In Figure 4b alloying elements have been increased and the pearlite and bainite nose have been shifted to the right, leading to that hardening occur at lower cooling rates resulting in more martensite. In both cases the cooling rate was the same. In Figure 4c the original composition of alloying elements was maintained, but the cooling rate was increased resulting in similar hardening effects as for example in Figure 4b.
Figure 4a. Insufficient hardening.
Figure 4b. Increase of alloying elements.
Figure 4c. Increase of cooling rate.
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As with traditional heat treatment a tempering operation is necessary in order to reduce internal stresses in the sinter hardened components, i.e. to temper the brittle martensite obtained during the rapid cooling. The influence on mechanical properties with/without tempering for Distaloy DH + 0.7%C sintered in 90%N2 / 10%H2 at 1120C for 30 minutes with a cooling rate between 3 to 4C/s is shown in Figure 5. The hardness properties decreases but tensile, yield and elongation properties increase. 200C for 60 minutes proved to be the better temperature and time for the tempering process for all the materials tested. Tempering at 300C decreases the elongation due to tempering embrittlement.
Figure 5. Effects of tempering. The tempering operation could be carried out in a separate line (furnace constructed for lower temperatures without any additional gas consumption) or be built into the furnace system as shown in Figure 6. With a system like this, the components can go directly from the furnace to the secondary operations or perhaps even directly to packing and shipping to the end user after quality control.
Figure 6. Built-in tempering zone, in sintering furnace. 2. COST COMPASRISON BETWEEN SINTER HARDENING AND HEAT TREATMENT The investment cost for a separate heat treatment furnace is approx. 4 times higher than the costs for the rapid cooling device that is assembled onto the sintering furnace. Many of the PM producers use a subcontractor for heat treatment of their components. This means that no investments for a HT furnace are necessary. However, the service has to be bought with additional costs of transportation + longer lead times before the components could be sent to the end user. Multiple quality controls will be necessary in this case; one after sintering and a second one after the components arrive from subcontractor. According to recent calculations carried out by Hgans AB and a furnace supplier, the cost for external heat treatment + tempering was approx. 70 to 80% of the total cost of a component. These figures were obtained during calculations of setting up 2000+ ton/year production line in western parts of Europe including a new large capacity sintering furnace with depreciation costs, operator costs, maintenance costs and energy costs etc. The actual sintering cost was 0.2 /kg and 0.8 /kg for the external heat treatment and tempering. To perform traditional heat treatment in-house, requires 4 times higher investment costs with higher processing costs due increased gas consumption and energy costs. With the sinter hardening process line, a continuous operation results in a through hardened PM component when leaving the sintering furnace.
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Figure 7. Comparison of HT and Sinter hardening main highlights. 3. SINTER HARDENING MATERIALS GRADES FROM HGANAS AB From Hgans AB there are many different grades designed for sinter hardening, three of them are displayed in Figure 8. Traditional Hgans materials such as Distaloy AE work excellent for sinter hardening but the amount of alloying elements in the material is high. *Cr materials are sensitive for oxidization which means that endogas is not suitable as sintering atmosphere. The recommended atmosphere is nitrogen based with additions of hydrogen. Syntetic DA (75%H2 / 25%N2) atmosphere can be used, but requires carbon control. The Distaloy DH (Direct Hardening) grade is based on pre-alloyed Astaloy Mo with diffusion bonded Cu. A leaner version is possible for sinter hardening applications with Astaloy 85Mo + Cu powders. Both grades are used for sinter hardened synchronizer hubs around the world. The Distaloy LH grade is based on pre-alloyed Astaloy LH with diffusion bonded Cu. Distaloy DH, leaner version (Astaloy 85Mo + Cu) and Distaloy LH can be processed in endogas, nitrogen based atmospheres and DA atmospheres.
Figure 8. Three sinter hardening grades from Hganas AB. In Figure 9, Astaloy CrM + 0.4%C with two different cooling rates are compared.
Figure 9. Astaloy CrM with two different cooling rates are compared.
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In Figure 10, Distaloy DH + 0.55%C with two different cooling rates are compared.
Figure 10. Distaloy DH + 0,55%C with two different cooling rates are compared. 4. DISCUSSIONS With a cost effective lean alloyed material and increasing the cooling rate with 2C/s in a sinter hardening furnace, results in a fully martensitic structure compared to a bainitic structure with conventional sintering of the materials, which leads to higher hardness and tensile strength of the components. It is important that a material with high enough hardenability is used for the process and there are several cost effective lean alloyed materials available that are suitable for sinter hardening. The structure of these materials after sinter hardening are similar and the properties are on the same levels as conventional heat treated materials, but produced in one process step without any subcontractors. Reducing the processing steps results in that the total production costs of a hardened component can be lowered and the properties are on the same level if a material with high hardenability is used. 5. CONCLUSION In order to cut production costs, it might be possible that sinter hardening could do a successful job. By implementing rapid cooling device to the sintering furnace, it is possible to have through hardened components leaving the furnace. Time and costs could be reduced due to less logistics and lower production costs. Thank to Ingo Cremer at Cremer GmbH, Sigurd Berg at Hgans AB
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SINTERING ACTIVATION AND MASS TRANSFER IN Ni-ALLOYED PM STEELS WITH ADDITION OF PRE-NITRIDED POWDER
Diyan M. DIMITROV*, Penka ZLATEVA** *Technical University of Varna, Faculty of Shipbuilding, Department of Mechanical Engineering, 9010, Varna, Bulgaria, dimitrov.diyan@gmail.com Technical University of Varna, Faculty of Shipbuilding, Department of Heat Engineering, 9010, Varna, Bulgaria, pzlateva1@abv.bg ABSTRACT In the present article sintering activation and mass transfer during microstructure formation, in compacts prepared from AstaloyCrL and DistaloySA powders with Ni, graphite and pre-nitrided powder addition were discussed. Prenitrided fine grade ASC powder with about 1%N as a sintering activator was used. Rectangular (5x5x15) compacts were pressed to density of about 6.0-6.2g/cm3. Sintering was done in an industrial mesh belt furnace at 1120oC under flowing 90%N2+10%H2 atmosphere. Dimensional changes after sintering were controlled. In compacts with prenitrided powder the sintering shrinkage is higher, especially in AstaloyCrL compacts. The observed microstructures of AstaloyCrL compacts were different. The addition of pre-nitrided powder gives higher percent lower bainite and martensite phases. The microstructures of DistaloySA compacts were similar. It seems that pre-nitrided Fe-powder is a better sintering activator for Cr prealloyed powders than Cu, Ni, Mo diffusion alloyed ones. Keywords: Powder Metallurgy, Sintering, Microstructure, Nitriding, Mass Transfer
**
1. INTRODUCTION The use of thermal instability of iron nitrides as a possible way of sintering activation in Fe-based systems is topic of several papers in the last 20 years [1-9]. An iron nitride phase was incorporated by both using pre-nitrided iron powders in the composition or nitriding of green compacts. Since nitriding potential of the most common N2+H2 sintering atmospheres is very low iron nitrides are instable and disappear during heating, resulting in in situ active surface. As a consequence such compositions exhibit enhanced sinterability (high sintering shrinkage). Sintering shrinkage depends on the protective atmosphere and the amount of nitrogen. In hydrogen rich atmospheres iron nitrides decompose rapidly at lower temperatures, resulting in higher sintering shrinkage [2]. In [3] it was demonstrated that main contribution to sintering shrinkage has the shrinkage in high temperature austenite region. The denitriding process also favors carbon dissolution into iron matrix and, again, accelerates sintering shrinkage [4]. These theoretical studies dont take into account the isothermal holding for delubrication in industrial sintering process. Investigations at temperature of 650oC (delubrication zone average temperature) show that in nitrogen rich (<10%H2) atmospheres, there is no sufficient nitrogen loss, but nitrogen diffusion is activated [3, 5]. Taking into account the inhomogeneous N distribution (N is concentrated in nitrided particles) the diffusion process from nitrided to pure powder particles begins, resulting in nitrogen redistribution into the whole volume i.e. the whole volume of the compact is activated. On the other side is the compressibility of such powder mixtures. Nitriding increases hardness of the powder particles, especially Cr prealloyed grades, thus drastically reducing the compressibility of powder mixtures. To solve this problem in [3,5] short time nitrided fine fraction (<53m) atomized iron ASC100.29 powder with approximately 1wt%N and microhardness 100-120HV0.05, as a sintering activator was proposed. It is shown that mixtures with 25% of such powder have similar green density as the mixture without an addition. It is reasonable to assume that, since nitride powder in this case is only a nitrogen donor, its quantity can be limited to 10% or even 5% and the sintering activation to be considered not only as a sintering shrinkage, but the phase composition has also to be taken into account.
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The main objective of this paper is to discuss the influence of nitrided powder addition on the alloying behavior of one of the mostly used alloying elements - Ni. Despite its high price fluctuations and some environmental issues, Ni is still an attractive alloying element in high performance low alloy PM steels [10-16]. Since Ni increases the ferrite hardness, thus decreasing the compressibility of powders, usually Ni is added as diffusion bonded or admixed to keep high compressibility. It is known that due to the slow Fe-Ni interdiffusion and the strong repulsion between Ni and C Ni-rich C-lean and/or areas form in sintering process [12,15]. These Ni rich areas are soft and prone to fracture during mechanical loading [15]. The alloying mechanism is reported in [13]. First fast particle and grain boundary diffusion of Ni was observed, followed by a slow volume Fe-Ni interdiffusion process with preferential atomic flow from Fe into Ni. As a result, depending on the Fe-Ni concentration profile, the carbon quantity and the cooling rate, , or (martensitic) phases can form. One possibility to diminish these Ni-rich areas is using a ultrafine (<0.5m) Ni particles [12,16]. Chromium alloying can diminish the repulsion effect between Ni and C, thus eliminating Ni-rich soft ferrite and austenite [14]. It is assumed that activated surface due to denitriding process (with a lot of vacancies defects) will increase atomic diffusion flow from Ni into Fe and will improve Ni alloying. 2. EXPERIMENTAL PROCEDURE As a base Fe material the prealloyed AstaloyCrL (Fe-1.5%Cr-0.2%Mo) and the diffusion bonded DistaloySA (Fe-1.75%Ni-2%Cu-0.5%Mo) powder grades have been used. Fine fraction (<53m) from atomised Fe powder ASC100.29, short time gas nitrided at 560oC with nitrogen content about 1wt%N (controled by LECO analyzer), as an activation substance was added to some of the mixtures. Artificial graphite grade (TIMCAL F10), fine (20m) electrolytic Ni powder, and 0.6%Kenolube as a lubricant was also used. Powder mixtures with composition given in Table 1 were prepared by tumbling 30min in a turbula mixer. From the powder mixtures, rectangular compacts (5x5x15 mm3) were formed. Sintering was carried out in an industrial mesh belt furnace under flowing N2+10%H2 atmosphere for 30min at 1120oC. The temperature of the delubrication zone of the furnace is about 650oC, the average cooling rate is about 0.75Ks-1. Table 1. Composition and green density of compacted samples. Code A1_N A2 D1_N D2 Powder mixture composition AstaloyCrL(Fe-1.5%Cr-0.2%Mo)+10%ASC(nitrided) +0.6%Ni+0.6%C AstaloyCrL(Fe-1.5%Cr-0.2%Mo)+0.6%Ni+0.6%C DistaloySA (Fe-1.75%Ni-2%Cu-0.5%Mo)+ +10%ASC(nitrided)+0.45%C DistaloySA (Fe-1.75%Ni-2%Cu-0.5%Mo)+0.45%C Green density, g/cm3 6.35 6.26 6.17 6.05
3. RESULTS AND DISCUSSION Calculated sintering shrinkage/swelling of samples was shown on Fig.1. On activated samples (A1_N, D1_N) higher shrinkage was measured. It is clearly seen that activated CrL powder (A1_N) shows higher percent shrinkage compared to non-activated (A2). For Distaloy powder probably Cu inhibits higher shrinkage, dissolving at the activated grain boundaries. For significant activation of this powder higher percent nitride powder addition is needed.
Figure 1. Shrinkage/swelling of sintered samples. A-astaloyCrL; D-distaloySA ; 1_N-with nitrided powder; 2 without nitrided powder;
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Data for measured apparent hardness of sintered samples is collected in Table 2. Again the same tendency is observed. Activated samples have slightly higher hardness and in Cr prealloyed samples hardness improvment is higher. Table 2. Apparent hardness of sintered samples. Code A1_N A2 D1_N D2 Hardness, HV10 130-165 124 -133 101-117 95-101
Observed microstructures of sintered AstaloyCrL based samples are shown on Fig.2. On pictures mainly coarse (upper) and fine (lower) bainite were registered. The measured mirohardness of coarse bainite is in the range of 167-204HV0.05. Most of the lower values are measured in A2 sample. Fine bainite have microhardness 279427HV0.05. In both samples Ni-rich areas are visible. Their microhardnesses are 205-268HV0.05 for A1_N activated and 101-120HV0.05 for A2 sample. Traces of Ni grain boundary diffusion (red arrows) can be seen on low magnification picture (upper row). Additionally little Ni-rich martensite was found. Finally, when nitrided activator was added the microstructures was improved. More, fine bainite formed at the expense of upper bainite. This result was due to better Fe-Ni alloying. On Fig.3 the observed microstructures of sintered DistaloySA based samples are shown. The microstructures of both samples look similar and consist of pearlite, ferrite, bainite and Ni-rich areas. It seems that the activation of this sample is not linked with a significant microstructure improvement.
Figure 2. Microstructures of sintered AstaloyCrL based samples; A1_N -left side ; A2 right side.
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Figure 3. Microstructures of sintered DistaloySA based samples; D1_N -left ; 4. CONCLUSION
D2 right.
For Cr prealloyed PM steels with added Ni, the addition of 10% pre-nitrided powder as a sintering activator, seem to be a promising way to improve their microstructure. More fine bainite forms, resulting in increased apparent hardness. For diffusion bonded samples no significant microstructure improvement was found. Probably Cu diffuses faster into the activated particles, resulting in its inhomogeneous distribution and altering Ni-diffusion. 5. ACKNOWLEDGEMENTS Authors wish to thank Gamasinter Ltd Varna, Bulgaria for sintering of investigated samples REFERENCES 1. T. Pieczonka, S. Harizanova, R. Rusev, E. Ruseva, Dialtometric Analysis of Sintering during Heating Stage of Nitrided Fe-2 wt.-% Ti Powder Mixtures Proceedings of 2000 Powder Metallurgy World Congress, Kyoto, 2000, p. 785 788 2. Harizanova S., .Russev R, Ruseva E., Petkova R., Pieczonka T., Povedenie na probi ot jelqzo-titanovi prahovi smesi pri spichane v H2 i bogata na N2 gazova sreda, II International Science- Technical Congress Mechanical Engineering99, Varna, 1999 , p. 61 66 (in bulgarian) 3. Dimitrov, D.M., Structure and Properties of alloyed PM steels on a base of AstaloyCrl powder grade, after sintering and surface heat treatment, PhD Thesis, Technical University of Varna , Varna, 2010. 4. Dimitrov, D.M., T. Pieczonka, S.D. Harizanova. Sintering Behaviour of AstaloyCrL Based Powder Mixtures, Containing Nitrided AstaloyCrL and Graphite Additions, Proceedings of 5th International Powder Metallutgy Converence, 08-12.10.2008, Ankara, Turkey, 2008, pp. 1387-1397 5. Dimitrov, D.M., P.N. Zlateva, S.D. Harizanova, S. Gyurov. Structure Forming and Chemical iteractions during Sintering of Low Alloyed Chromium PMsteels with Addition of Nitrided Powders. Proceedings of Material Science and New Materials, 04-05.12.2008, Sofia, BAS, 2008,pp.128-132 6. S. Harizanova, T. Pieczonka, E. Ruseva, M. Stoytchev, R. Rusev, Sintering Behaviour of nitrided mixtures of ASC100.29 Hoganas Grade and Sponge Titanium Powder, Proceedings of Deformation and Fracture in Structural PM Materials International PM Conference, Piestany .99,IMR SAS Kosice, vol. 2, p. 26 29 7. T. Pieczonka, S. Harizanova, R. Rusev, E. Ruseva, Dialtometric Analysis of Sintering during Heating Stage of Nitrided Fe-2 wt.-% Ti Powder Mixtures Proceedings of 2000 Powder Metallurgy World Congress, Kyoto, 2000, p. 785 788 8. Harizanova S., Pieczonka T., Ruseva E., Rusev R., Decheva D., Stoytchev M., Thermal Stability of Nitride Phases in Fe-2Ti sintered Alloys, Proceedings of the PM Congress Valensia, 2003., v.1, . 435 440 9. Pieczonka T., Harizanova S., Decheva D. Sintering of low-temperature gas carbonitrided iron-base materials containing 2wt.-% Ti Sacaria Powder Metallurgy Conference proceedings, Turkey, 2006
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10. F. Castro, S. Sainz, Influence of Ni on hardenability of PM steels, Advances in Powder Metallurgy and Particulate Materials, Lauderdale, Florida, USA, 2010. 11. Hwang et al. Comparison of mechanical properties of Fe175Ni05Mo15Cu04C steels made from PIM and press and sinter processes, Powder Metallurgy 2002 Vol. 45 No. 2, pp160-166 12. W. Garca, P. Uranga, F. Castro, Influence of Nickel and Cooling Rate on the Microstructural Development of Mo-Containing PM Steels, Euro PM2008-Sintered Steels, Mannheim, Germany. Vol. 2, pp. 153-158. 13. S. Sainz, W. Garca, A. Karuppannagounder, F. Castro, Microstructural development during sintering of PM steels with admixed Nickel, Powder Metallurgy Progress, Vol.7 (2007), No 3, pp121-127 14. Wu M.W., K. S. Hwang and K. H. Chuang Improved distribution of Ni and C in sintered steels through addition of Cr and Mo, Powder Metallurgy 2008 VOL 51 No 2, pp160-165 15. Wu, M.-W. Hwang, K.-S., The Mechanisms of the Formation and Elimination of Weak Ni-Rich Areas in PM Steels, Advances In Powder Metallurgy And Particulate Materials, 2007, NUMB 2, pages 07-12-07-23 16. T. F. Stephenson, S. T. Campbell, T. Singh, Properties of Prealloyed Mo Steels Admixed with Extra-Fine Ni Powder, Procs. of EuroPM2003, , Valencia, Spain 2003. Vol.1, pp. 269-275
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Production Of MWCNT Reinforced Bronze Matrix Composite By Current Activated Sintering

Ramazan KARSLIOLU, Mehmet UYSAL, mer Faruk YAZICI, Hatem AKBULUT Sakarya University Engineering Faculty, Department of Metallurgical and Materials Engineering, rkarslioglu@sakarya.edu.tr Abstract In this study, bronze matrix (90 wt. % Cu + 10 wt. % Sn) was reinforced with multi walled carbon nanotubes (MWCNTs) using mechanical alloying and then produced by subsequent rapid current sintering technique. The mechanically ball milled bronze matrix powders was reinforced with various amounts of MWCNT (1.0 wt. %, 3.0 wt. % and 5.0 wt. %). The composites were cold compacted under a constant pressure of 200 MPa. The compacted structures were sintered at atmospheric conditions almost to the full density within 10 minutes at 1000 A using current sintering, in which the powders were heated by a low voltage and high amperage current and compressed simultaneously. Microhardness testing, and scanning electron microscopy (SEM) studies were carried out for the characterization of the composite. Optimal microstructure was targeted to determine the properties for the resultant composites. Key words: Rapid current activated sintering, CNT, Bronze, composite. 1. Introduction Copper and copper matrix composites have been known as excellent engineering materials for application where good mechanical and thermal properties are desired [1-2]. Cu-matrix particle MMCs may even be more suitable for use in brakes and other severe frictional applications because of (1) the higher thermal conductivity of these MMCs, which makes them better than Al-SiC MMCs at conducting frictional heat away from the sliding interface; (2) the much higher melting and softening temperatures of copper; and (3) the superior corrosion resistance of copper and its alloys in chloride environments [3]. Dispersed particles such as oxides, carbides, and borides, which are insoluble in the copper matrix and thermally stable at the high temperatures, are being increasingly used as the reinforcement phase. Various methods have been used for making MMCs such as liquid metal infiltration, squeeze casting, diffusion bonding, electrodeposition, and PM [4]. The relatively high melting point and poor wettability of the reinforcement phase by the copper make powder metallurgy suitable for production of copper-based composites [5]. Interest for using multiwall carbon nanotubes (MWCNTs) to reinforce polymers, ceramics and metals has grown tremendously over the last decade because of their attractive mechanical and thermal properties [6]. Many researchers have reported on mechanical properties of carbon nanotubes that exceed those of any previously existing materials. Although there are varying reports in the literature on the exact properties of carbon nanotubes, theoretical and experimental results have shown extremely high elastic modulus, greater than 1 TPa (the elastic modulus of diamond is 1.2 TPa) and reported strengths 10100 times higher than the strongest steel at a fraction of the weight. Indeed, if the reported mechanical properties are accurate, carbon nanotubes may result in an entire new class of advanced materials [7]. Also CNTs have very high thermal conductivity (30006000 W (m K)-1) along the tube direction. Excellent mechanical and thermal properties combined with their low-density make CNTs as an ideal reinforcement to fabricate high-performance composites for various engineering applications [6]. However, limited research has been done in preparation, structural, physical and mechanical properties of metalCNT
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nanocomposites. Poor wetting behaviour or weak interfacial bonding to matrix materials, agglomeration among themselves with Van-der-Waals force, inhomogeneous distribution of CNTs in the matrices and degraded thermal stability at high processing temperature are the prime drawbacks to use carbon nanotubes as reinforcements of metal matrix composites. For instance, Kuzumaki et al. [8] reported very little improvement in tensile strength of CNT reinforced Al nanocomposites prepared by conventional powder mixing, hot-pressing followed by hot extrusion due to inhomogeneous dispersion of CNTs in the metal matrix. For any case, the homogeneous dispersion of nanotubes in metal matrices is the prime requirement before fabricating carbon nanotube based metal matrix nanocomposites. Early studies carried out by Uddin et al. [9] showed that, high energy mechanical alloying involved continuous impact, welding, fracturing and re-welding of powders to disperse nanotubes in the metal powders. The objective of the present investigation is to prepare bronze-matrix composite reinforced with five different ratios (1.0, 3.0 and 5 wt. %) MWCNT by using a rapid current activated sintering technique. Effect of the different ratio MWCNT on the bronze matrix MMCs were investigated. In this contribution, we report on the successful preparation of MWCNT reinforced bronze composites by mechanical mixing of nanotubes and metal powders followed by current activated sintering. A new approach was taken into account to obtain rapid and cost effective sintering to improve hardness of MWCNT reinforced bronze matrix. 2. Experimental Three different ratios MWCNTs reinforced bronze metal matrix composites were produced by rapid current activated sintering technique. The matrix material was a 10 wt. % Sn bronze alloy in the powder state and has an average particle size of 80 m. The average particle sizes of the MWCNT were 80 nm in diameter and 8 m in length. The blended and mechanically planetary ball milled bronze matrix powders and MWCNTs were then cold compacted, which was a disk form in 25 mm diameter, under a pressure of 300 MPa to obtain nanocomposite. The cold compacted nanocomposite mixture structure was then sintered at atmospheric conditions to nearly a full density within 10 minutes under an applied pressure of 10 MPa. The compaction processes were accomplished in a single process. The sintering was carried out at high-current levels as high as 1200-1500 Amperes and constant voltages (2.5 V). The current activated sintering system setup is shown in Fig. 1. After sintering treatment the samples were left the air for cooling, and the samples were cut from the disks and prepared to use standard metallographic techniques. Polished and lightly etched specimens were examined using for microhadness test. The matrix microhardness measurements were carried out on polished samples using 50 g load for 10 sec. Also the composites were prepared to investigate fracture surfaces for scanning electron microscope (SEM) and Energy dispersive X-ray analysis investigation (EDS). A complete fracture surface microstructural characterization was carried out via SEM and EDS (JEOL 6060LV).
Fig 1. a) Schematic presentation of the current activated sintering system and b) an example of sintering process application [1].
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3. Results and Discussion In an early contribution[21] S.M. Uddin, T. Mahmud, C. Wolf, C. Glanz, I. Kolaric and M. Hulman et al., Thermal expansion coefficient of nanotube-metal composites, Phys Status Solidi B 246 (1112) (2009), pp. 28362839. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (2), it was shown that the planetary ball mill employed a strong centrifugal force to develop high energy milling action inside the vial, which in fact involved continuous impact, welding, fracturing and re-welding of MWCNTmetal powders[9]. Milling for time 3 h did not show good embedment of MWCNTs in the matrix materials and (b) prolonged milling promoted cold-welding of metal powders producing very large metal particles. (a)
Fig. 2. SEM microphotograph of mechanically alloyed bronze and MWCNT (a)low magnification (b) high magnification In the current activated sintering process was aimed to produce of the nanocomposite. Fig. 3-4 show the microstructure of the composites that produced by using different voltage applications. In Fig. 3-4 both the fracture surface microstructures in low magnification and high magnification are presented. In Fig 3 and 4 the MWCNT distribution is also shown. The fracture microstructure reveals a good bonding is provided and no de-attachment was observed with low porosity among the grains and MWCNT. All the nanocomposites produced by current sintering show uniform distribution of particles through the matrix. EDS analysis was given in Fig. 5. EDS analysis shows Cu-Sn elements and also C traces, which belongs to the carbon nanotubes.
Fig.3. Low magnification fracture surface micrographs of the composite produced with different applied voltages; a) 2 V, b) 2,5V and c) 3 V
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Fig.4. High magnification fracture surface micrographs of the composite produced with different applied voltages; a) 2 V, b) 2,5V and c) 3 V The hardness of the MWCNT/bronze nanocomposites as well as the unreinforced bronze alloy was measured by Vickers hardness test. Fig. 6 shows the effect of the MVCNTs weight fraction on the hardness of the prepared MWCNT/Bronze nanocomposites. Micro hardness of unreinforced bronze alloys is 98 Hv. The microhardness of the nanocomposites dramatically increases with reinforced MWCNTs. Hardness of 1 wt. % MWCNT reinforced bronze alloys is obtained as 158 Hv. However over the 1 wt. % MWCNTs, The hardness of the composites decreases with increasing MWCNTs. The improvement in the hardness of bronze based nanocomposite matrix is related to the second phase hardening effect caused by MWCNT in the nanocomposite matrix, which obstructs the shift of dislocation in nanocomposite. Two reasons are suggested to be responsible for the increase in hardness; particle-strengthening and grain refining. Particle-strengthening is related to the incorporation of MWCNT and amount fractions above 1 wt. %. In this case, the load is carried by both the matrix, and the particles and strengthening is achieved because the particles restrain the matrix deformation. The second mechanism is related to the nucleation of small grains on the surface of the incorporated particles, resulting in a general structural refinement. In this case, the presence of smaller grains impedes dislocation motion resulting in an increase in microhardness. Also; MWCNTs resulted to obtain a hardness value as high as 158 Hv whereas, unreinforced bronze showed only 98 Hv. This corresponds to 61 % hardness increment.
Fig. 5. EDX analysis of nano composite
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Fig. 6. Matrix microhardness variation of composite depending volume fraction of MWCNT. 4. Conclusions Bronze alloys and MWCNTs reinforced bronze metal matrix composites were successfully produced by rapid current activated sintering technique. SEM photographs show uniform distribution of MWCNT through the matrix. EDS analysis shows Cu-Sn elements and also C traces which belongs to the carbon nanotubes. The microhardness of the nanocomposites dramatically increases with reinforced MWCNT. Introducing MWCNT resulted to obtain a hardness value as high as 158 Hv whereas, unreinforced bronze showed only 98 Hv. This corresponds to 61 % hardness increment. The microhardness of the bronze matrix was increased as the increasing applied voltage. References 1. Karslioglu R., Uysal M., Alp A., Akbulut H., Wear Behavior of Bronze Hybrid MMCs Coatings Produced by Current Sintering on Steel Substrates Tribology Transactions, Vol. 53 pp 779-785, 2010 2. Sornakumar, T., and Senthil Kumar, A. Machinability of BronzeAlumina CompositeWith Tungsten Carbide Cutting Tool Insert, Journal of Materials Processing Technology, Vol. 202, pp 402-405. 2008, 3. Kennedy, F. E., Balbahadur, A. C., and Lashmore, D. S.), The Friction And Wear of Cu-Based Silicon Carbide Particulate Metal Matrix Composites for Brake Applications, Wear, Vol. 203/204, pp 715-721. 1997 4.Distribution in Al/Al2O3 Composites Obtained from Composite Powder, Materials Characterization, Vol. 46, pp 189-195. 5. Sapate, S. G., Uttarwar, A., Rathod, R. C., and Paretkar, R. K. (2009), Analyzing Dry Sliding Wear Behaviour of Copper Matrix Composites Reinforced with Pre-Coated SiCp Particles, Materials and Design, 30, pp 376386. 6. Bhata A., Balla V. K., Bysakh S., Basu D., Bose S., Bandyopadhyay A., Carbon nanotube reinforced Cu10Sn alloy composites:Mechanical and thermal properties Materials Science and Engineering A Vol. 528 6727 6732. 2011 7. Erik T. Thostenson, Zhifeng Ren, Tsu-Wei Chou, Advances in the science and technology of carbon nanotubes and their composites: a review Composites Science and Technology Vol. 61 18991912 2001 8. Kuzumaki T, Miyazawa K, Ichinose H, Ito K. Processing of carbon nanotube reinforced aluminium composite. J Mater Res Vol. 13: 24452454. 1998 9. Uddin SM, Mahmud T, Wolf C, Glanz C, Kolaric I, Hulman M, et al. Thermal expansion coefficient of nanotube-metal composites. Phys Status Solidi B; Vol 246(1112):28362845. 2009
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Al+%5MgO KOMPOZT MALZEMENN ZELLKLERNE SNTERLEME SICAKLII VE SNTERLEME SRESNN ETKLER

Yusuf KARAMAN*, Hanifi NC**, Recep ALIN*** *Krkkale niversitesi, Makine Mhendislii Blm, Krkkale **Gazi niversitesi, Metal Eitimi Blm, Ankara ***Krkkale niversitesi, Malzeme ve Metalurji Mhendislii Blm, Krkkale ZET Toz Metalurjisi (T/M) yntemiyle metal matrisli kompozit (MMK) retimi iin, saf alminyum (Al) matris malzemesi olarak seilmi ve %5 arlk orannda MgO takviye malzemesi olarak belirlenmitir. Hazrlanan toz karmlar 500 MPa basn altnda tek ynl sktrma ilemine tabi tutulmulardr. Arlka %5 takviye oran ieren ham numuneler 570-600-630 C scaklklarda argon (Ar) gaz atmosferinde 1,2 ve 4 saat sreyle sinterleme ilemi uygulanmtr. Elde edilen numuneler optik mikroskop ve SEM grntleri alnp mikroyaplar incelenerek younluk, sertlik ve apraz krlma mukavemetleri llmtr. Yaplan alma sonucunda sinterleme scakl ve sinterleme sresinin artmasna bal olarak younluk, sertlik ve apraz krlma dayanmlarnn artt grlmtr. Deerler incelendiinde en iyi sonularn 630 Cde 4 saat sinterlemede elde edildii tespit edilmitir. ABSTRACT In this study, weight percent of 5% MgO reinforcement aluminum (Al) matrix composites were produced by powder metallurgy (P/M) method. Prepared powder mixes had been mixed for 60 minutes by Turbula. Powders were compacted at 500MPa pressure by single action press. Weight percent of 5% MgO reinforced composite specimens had been sintered at 570; 600 and 630C for 1-2-4 hours in argon atmosphere. After having the results of density, hardness and transverse rupture strength (TRS) tests, the best results were obtained on sintering process at 630C for 4 hours. The increasing sintering temperature and time made the porosity decrease and made the mechanical properties improve. Specimens surface inspections were applied by optical microscopy (OM) and scanning electron microscopy (SEM). Key Words: MgO, TRS, Transverse Rupture Strength, Sintering Temperature, Sintering Time 1.GR Farkl zellikteki malzemelere olan ihtiya yeni retim tekniklerinin gelitirilmesini salamtr. Tek bir bileenden oluan malzemeler genellikle ihtiyalar karlayamamaktadr. Bu sebepten dolay kompozit malzemelerin bir grubu olan metal matrisli kompozitler (MMK) gelitirilmektedir [1,2]. MMK malzemeler yksek mekanik zellikleri ve anma direnleri sayesinde endstride geni kullanm alan bulmaktadrlar. Alminyum matrisli kompozitler dk younluklar, yksek tokluklar ve yksek korozyon direnleri sayesinde endstride geni kullanm alan bulmaktadrlar. Havaclk ve uzay sanayisi, otomotiv, savunma ve elektronik sanayileri bu alanlarn nde gelenleridir. Alminyum saf halde yksek mekanik zelliklere sahip deildir. Ancak Al2O3, SiC, TiC, B4C ve MgO gibi seramik malzemelerin takviye eleman olarak kullanlmas sonucunda elde edilen alminyum matrisli kompozitlerin mekanik zellikleri yksektir [3-7]. Toz metalurjisi (T/M) en yaygn kompozit retim yntemlerinden biridir. Dkm yntemine gre en byk avantaj homojen takviye eleman dalm sayesinde mikroyapnn kontrol edilebilmesidir [4]. T/Mnin dier bir avantaj da kat hal sinterlemesi sonucunda matris ve takviye eleman arayzeyinde istenmeyen fazlarn oluumunu en dk seviyede tutulmas sonucunda arayzeyde kuvvetli bir ba oluumunu salamasdr [3,8]. Bu almada T/M yntemiyle retilen Al-MgO kompozitlerinin mekanik zelliklerine sinterleme scaklnn ve sinterleme sresinin etkileri aratrlmtr.
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2.DENEYSEL YNTEM Bu almada gaz atomizasyonu yntemiyle retilmi %99,7 saflk orannda 76,39 m ortalama toz tane boyutundaki Al tozlar matris malzemesi olarak kullanlmtr. 29,53 m ortalama toz tane boyutuna sahip saf MgO tozlar takviye eleman olarak kullanlmtr. Arlka %5 MgO oran ieren Al-MgO toz karmlar Turbula cihaznda 60 dakika kartrldktan sonra tek etkili preste 500 MPa basn altnda sktrlarak ASTM standartlarndaki 6,35x12,70x31,75mm boyutlarnda apraz krlma numuneleri elde edilmitir. Elde edilen test numuneleri argon (Ar) gaz ortamnda yatay tpl frnda 570; 600 ve 630C scaklkta 1; 2 ve 4 saat srelerde sinterlenmilerdir. Arimet prensibine gre younluklar llen numunelerin gerekli yzey ilemlerinden sonra Vickers yntemi ile sertlikleri llm ve ASTM standartlarna gre apraz krlma mukavemetleri (KM) llmtr. Numunelerin mikroyap incelemeleri taramal elektron mikroskobunda (SEM) yaplmtr. 3.DENEYSEL BULGULAR VE TARTIMA 3.1. Younluk sonularnn incelenmesi Farkl sinterleme scaklk ve srelerinde elde edilen younluk sonular ekil 1de verilmitir. ekil 1 incelendiinde artan sinterleme scakl ve artan sinterleme sresi sonucunda elde edilen younluk deerlerinin ykseldii grlmektedir. Bu art Eitlik 1de yer alan Arrhenius denklemi [9,10] ile aklanabilir. (1) Burada DV hacim difzyonu katsays, D0 malzeme sabiti, Q aktivasyon enerjisi, R gaz sabiti ve T mutlak scaklktr. Denklemin sa tarafndaki T deerinin artmasyla DV deerinin de artaca ak bir ekilde grlmektedir.
ekil 1. %5 MgO takviye oranl kompozitlerin sinterleme sresi ve sinterleme scaklna gre younluk deiimleri.
Ergime scaklna yakn scaklklarda daha fazla atom komular ile balarn kopartp yeni yerlere gitmek iin daha yksek enerjiye sahiptir [10]. Artan scaklk ile Al paracklar arasnda daha fazla difzyon gerekletii ve gzeneklerin birleerek daha dk enerji konumuna getii deerlendirilmitir. Sonu olarak scakln artmas ile sinterlenebilirlik artm [11] ve sinterlenebilirliin artmas younluk deerlerini arttrarak teorik younlua yakn deerler elde edilmitir.
ekil 2. 630Cde 1 saat (a), 2 saat (b) ve 4 saat (c) sinterlenmi numune yzeylerinin SEM grntleri. Sinterleme sresinin artmasyla paracklar arasndaki boyunlamann gelitii, gzeneklerin azald [12] artan sre ile paracklar aras difzyonunda artmas sonucu yksek younluk deerleri elde edilmitir.
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ekil 3. 4 saat sreyle 570Cde (a) ve 600Cde (b) sinterlenmi numune yzeylerinin SEM grntleri. ekil 2 ve ekil 3 incelendiinde takviye elemannn kompozit ierisinde homojen dald grlmektedir. Younluk sonular birbirine yakn olduu iin gzeneklilik oranlar grsel olarak ayrt edilememektedir. Gzeneklerin Al tane snrlarnda ve Al-MgO arayzeylerinde olduu grlmektedir. 3.2. Sertlik sonularnn incelenmesi ekil 4de sinterleme scakl ve sinterleme sresinin Al-MgO kompozitlerin sertliklerine olan etkileri verilmitir. ekil 4 incelendiinde artan sinterleme scakl ile numunelerin sertlik deerlerinin artt grlmektedir.
ekil 4. %5 MgO takviye oranl kompozitlerin sinterleme sresi ve sinterleme scaklna gre sertlik deiimleri.
Buradaki sertlik artnn artan sinterleme scakl ile teorik younlua daha yakn sonular elde edilmesinden veya dier bir deyile gzenekliliin dmesinden kaynakland [4] deerlendirilmitir. Gzeneklilik oran dk yaplarda sertlik lme cihaznn batc ucunun gzenek zerine gelme olaslnn dk olmas da sebepler arasnda saylabilir. 3.3. apraz krlma mukavemetlerinin incelenmesi ekil 5. incelendiinde artan sinterleme scakl ve sinterleme sresi ile KM deerlerinin art grlmektedir. Yksek scaklklarda alminyumun yzey gerilmesi der, slatma kabiliyeti artar ve daha kuvvetli arayzey balar oluur [8]. Buradan yola karak KM artnn sebebi; artan sinterleme scakl ve sresiyle paracklar arasnda oluan boyun apnn (X) toz apna (D) olan oran (X/D) artmasyla [13] olumu olan kuvvetli ba sayesinde paracklar arasndaki yk transferinin daha kolay gereklemesi olarak deerlendirilmitir.
ekil 5. %5 MgO takviye oranl kompozitlerin sinterleme sresi ve sinterleme scaklna gre KM deiimleri.
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ekil 6 incelendiinde krlmalarn Al-MgO arayzeyindeki zayf slatma [14] sonucu tane snrlarndan gerekletii grlmektedir. Tane snrlarnda yer alan gzeneklerin entik etkisi yaparak krlmay kolaylatrd deerlendirilmi ve KM deerlerini drd sonucuna varlmtr. MgO-Al arayzeyinde slatma kabiliyetinin iyi olmay da [13] sebepler arasnda yer almaktadr.
ekil 6. 630Cde 1 saat (a), 2 saat (b) ve 4 saat (c) sinterlenmi numunelerin krk yzeylerinin SEM grntleri. 4.SONULAR Sinterleme sresindeki art ile beraber Al-MgO kompozitlerin younluk, sertlik ve KM deerlerinin artt tespit edilmitir. Sinterleme scaklnn artmas ile den gzeneklilik sayesinde younluk ve sertlik deerlerinde ykselme gzlenmitir. Artan scaklk ile gerekleen kuvvetli arayzey balar sayesinde daha yksek KM deerleri elde edilmitir. Artan gzeneklilik ise mikro atlak etkisini artrd iin kompozitlerin KM deerlerini drmtr. Krk yzeylerin SEM grntleri incelendiinde krlmann arayzeylerde ve matris tane snrlarnda gerekletii grlmtr. Gzeneklerin takviye eleman etrafnda ve tane snrlarnda yer ald SEM grntleri ile tespit edilmitir. 5.KAYNAKLAR [1] aln R., tak R., Effect of Mg Content of Matrix on Infiltration Height in Producing MgO Reinforced Al Matrix Composite By Vacuum Infiltration Method. Material Science Forum Vols.546-549, s.611-614, 2007. [2] aln R., tak R., Effect of Powder Size on Infiltration Height in Producing MgO Reinforced Al Matrix Composite By Vacuum Infiltration Method. Materials Science Forum Vols., 534-536, s.797-800, 2007. [3] Rahimian, M., Parvin, N., Ehsani, N., Investigation of particle size and amount of alumina on microstructure and mechanical properties of Al matrix composite made by powder metallurgy. Material Science and Engineering, Vol 527, s.1031-1038, 2010. [4] Rahimian, M., Ehsani, N., Parvin, N., Baharvandi, H.Z., The effect of particle size, sintering temperature and sintering time on the properties of Al-AlO composites, made by powder metallurgy. Journal of Materi als Processing Technology, Vol 209, s.5387-5393, 2009. [5] Topu, ., Glsoy, H.O., Kadolu, N., Gllolu, A.N., Processing and mechanical properties of BC reinforced Al matrix composites. Journal of Alloys and Compounds, Vol 482, s.516-521, 2009. [6] Tatar, C., zdemir, N., Investigation of thermal conductivity and microstructure of the -Al2O3 particulate reinforced Al composites (Al/Al2O3-MMC) by powder metallugy method. Physica B 405, s.896- 899, 2010. [7] ahin, Y., Kompozit Malzemelere Giri. Gazi Kitabevi, Ankara, 2000. [8] Wang, H., Zhang, R., Hu, X., Wang, C.A., Huang, Y., Characterization of a powder metallurgy SiC/Cu-Al composite. Journal of Material Processing Technology 197, s.43-48, 2008. [9] German, R.M., Park, S.J., Mathematical Relations in Particulate Material Processing. John Wiley & Sons Inc. Publication, USA, 2008. [10] German, R.M., Toz Metalurjisi ve Parackl Malzeme lemleri. Trk Toz Metalurjisi Dernei Yaynlar, Ankara, 2007. [11] Min, K.H., Kang, S.P.,Kim, D.G., Kim, Y.D., Sintering Characteristic of AlO-reinforced 2xxx Series Al Composite Powders. Journal of Alloys and Compounds, Vol 400, s.150-153, 2005. [12] Kim, T.W., Determination of Densification Behavior of Al-SiC Metal Martix Composite During Consolidation Processes. Materials Science and Engineering A 483-484, s.648-651, 2008. [13] Xu, X., Lu, P., German, R.M., Densification and strength evolution in solid-state sintering. Journal of Materials Science, Vol 37, s.117-126, 72002. [14] aln R., tak R., Effect of Vacuum on Infiltration Height in Producing MgO Reinforced Al Matrix Composite By Vacuum Infiltration Method. ICIT-MPT International Conference on Industrial Tools and Materials, Bled, Slovenya,11-14 Eyll 2007.
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Toz Metal Paralarn ndksiyonla Sinterlenmesinin NMERK ANALZ

M. Bahattin AKGL*, Gksan AKPINAR*, Can V*, Enver ATK* *Celal Bayar niversitesi Mhendislik Fakltesi, Makine Mhendislii Blm, 45140, Manisa,mehmet.akgul@ bayar.edu.tr, goksanakpinar105@hotmail.com, can.civi@hotmail.com, enver.atik@bayar.edu.tr ZET Toz metal paralarn retiminde sinterleme nemli bir yer tutmaktadr. Bu ilem sinterleme frnlarnda gerekletirilmektedir. Bu sinterleme yntemine alternatif olmak zere toz metal paralarn indksiyonla sinterlenmesi almalar yaplmaktadr. Bu almada 20 kHz frekansta toz metal paralarn indksiyonla sinterleme ileminin nmerik analizleri yaplmtr. Bobin tasarmnn s oluumuna etkileri tartlarak optimum bobin tasarm belirlenmeye allmtr. Bu analizlerle toz metal paralarn indksiyonla sinterlenmesinde, sinterleme parametreleri optimize edilebilmektedir. Anahtar Kelimeler: Toz Metalurjisi, Sinterleme, ndksiyon, Nmerik Analiz.
NUMERICAL ANALYZING OF INDUCTION SINTERING OF POWDER METALIC COMPONENT

ABSTRACT Sintering is taken important part for production of powder metallic component. This operation is practiced in sintering furnace. Alternatively this sintering method it is studied that induction sintering process. In this study, it is done that numeric analyzing of powder metallic component for 20 kHz induction sintering. It is discussed that coil design effect to heat production and it is practiced to find optimum coil design. Induction sintering parameters of powder metal components is optimized with this analyzing. Key Words: Powder Metallurgy, Sintering, Induction, Numeric analyzing. 1. GR: Toz metalurjisi ynteminde, uygun bileime sahip toz karmlar ilk aama olarak kalp ierisinde preslenmektedir. Presleme basncna ve etki ekline bal olarak parann younluu da deimektedir. Bu ilk ilem, elde edilecek parann mekanik ve fiziksel zelliklerini de etkilemektedir. Toz metalurjisi ile elde edilecek paralarda ikinci aama sinterlemedir. Sinterleme, ergime scaklnn altnda ve genellikle koruyucu atmosferde gerekletirilir. Bu aamada para, stlm ve korozyondan korumak amacyla atmosferle ilgisi kesilmi frn ierisinde nce yalayclardan temizlenmek zere n stmaya tabi tutulur. Oksit indirgenmesinin ardndan frnn scak blgesinde sinterleme ilemi gerekletirilir ve frndan kan para soumaya braklr [1]. Sinterleme, toz metalurjisinin en karmak konusudur. Sinterleme, ham malzemelerin yksek younluklu paralara dntrld kilit kademelerin banda gelmektedir [2]. Sinterleme srasnda polimer/yalayc yaklmas, paracklar aras balanma, boyut deiimi ve mikroyapnn irilemesi gibi birok olay gerekleir. Sinterleme uygulamasnda hedeflenen mhendislik amalar iin evrim, ekipman ve gerekli ortamn uygun parametrelerin kullanlmas gerekir. Sinterlenen parann istenilen zelliklere sahip olmas kadar parann istenilen boyutlarda olmas da bir zorunluluktur.
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ndksiyonla stma prosesi; scak ekillendirme, yzey sertletirme, sl ilem, indksiyonla ergitme, indksiyon kayna, birletirme, lehimleme, yaptrma, sk geme, srtnme kayna vb. uygulamalarda ve otomotiv endstrisi, gda ve kimya endstrisi gibi birok teknolojik uygulamalarda kullanlmaktadr. ndksiyonla stma enerji younluu, i parasndaki scaklk alannn kontrol ve temassz enerji transferinden dolay son derece etkilidir. Ancak, indksiyonla stmadaki yksek potansiyel sadece nmerik simlasyon baz alnarak tamamen anlalabilir. ndksiyonla stma elektromanyetik ve termal fizii kapsamaktadr. Oluacak s i parasnn malzemesine bal olduu iin bunlar birbiriyle dorudan ilikilidir [3, 4]. ndksiyonla sinterleme, deiken akm tayan iletken bobin ile salanr. Bobinde oluan akm, toz metal malzeme iinde girdap akma neden olan manyetik alan oluturur. Bobin genellikle bakrdan meydana gelir. erisinden soutma suyu geer. ndksiyonla sinterleme ynteminde kullanlan frekans 50 Hz ile 50 kHz arasnda olabilir. ndksiyon sisteminin frekansna gre penetrasyon derinlii deiir. Demir gibi ok iletken malzemeler ksa srede snr. Yksek scaklkta veya yksek frekansta penetrasyon derinlii azalr (ekil 1.). Oda scaklnda 100 mmye kadar penetrasyon derinlii gerekleebilir ama scaklk artarsa penatrasyon derinliinde azalma meydana gelir.
ekil 1. ndksiyonla sinterlenmi Cu-15Al TM numunenin scaklk ve frekansa gre penetrasyon derinlii [5]. Scaklk avantaj olduu halde indksiyon, sinterlemede ok az kullanlr. Genellikle indksiyon akmn dzelten grafit ile birlikte yava admlarla stlacak scak presleme ilemlerinde kullanlmaktadr. ndksiyonla sinterlemede parann tamamnda homojen bir s oluumu hedeflenmelidir. Toz metal paralarn indksiyonla sinterlenmesinde frekans kadar bobin tasarm nemli etkenlerden biridir. 2. MATERYAL VE METOT: Bu almada, sinterlenecek numuneler ortalama 75 m boyutunda demir tozlarnn 600 MPa basnta tek eksenli hidrolik presle baslmasyla retilmitir. Numunelerin boyutu 10x10x55 mmdir. Numuneler demir esasl olup arlka %2 Cu, %0,8 grafit ve yalayc olarak %1 inko stearat kullanlarak retilmitir. Bu toz metal numunelerin indksiyon bobini ierisinde sinterlenmesi, numunelerin bobin ierisinde sabit hzla ilerlemesi srasnda gerekletirilmitir. Ancak deneysel almalarda malzeme zerinden geen manyetik ak tam olarak llemedii iin nmerik modelleme ile optimum bobin tasarm gelitirilmeye allmtr. Bylece bu boyutlardaki toz metal numunelerin sinterlenmesinde n stma, sinterleme ve soutma blgesini elde etmek iin en uygun bobin tasarm elde edilmeye allmtr. 3. NMERK ALIMALAR: ndksiyonla sinterleme parametrelerinden biri olan optimum bobin tasarmn belirlemek amacyla yaplan nmerik almalarda Comsol Multiphysics 3.5 program kullanlmtr. Bu modellemede toz metal numuneler, 7 sarml 20 mm apnda bobin kullanlarak 20 kHz frekansta ve 3,5 kA akm iddetinde indksiyonla stma ilemine tabi tutulmutur. Nmerik almada, sadece bobin sarm ekilleri deitirilerek numuneler arasnda scaklk dalm ve sreleri bakmndan karlatrlmalar yaplmtr. lgili kurucu denklem aadaki ekildedir; (1) (2)
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Bu formlde younluk, Cp spesifik s kapasitesi, k termal iletkenlik, Q indktif sy temsil etmektedir. Demirin elektirk iletkenlii, , aadaki eitlikte verilmitir. Burada 0: referans scaklktaki (T0= 293 Kelvin) dire, : direncin scaklk katsays ve T: anlk scakl ifade etmektedir. ndktif snn bir periyodundaki ortalama zaman aadaki denklemde verilmitir: (3)
(4)
Modellemede 2 boyutlu eksenel simetri, AC/DC modl, yar statik manyetik, Azimuthal indksiyon akm, vektr potansiyel, zaman uyumlu analiz olarak seilmitir. Sabitler izelge 1.de verilmitir. izelge 1. Sabitler izelgesi. Parametreler Akm Bobin ap Yzey Akm Younluu Referans Scaklk T=T0 daki Diren Scaklk Katsays Havann Younluu Havann Is Kapasitesi Havann Is letkenlii Demirin Younluu Demirin Is Kapasitesi Demirin Is letkenlii Deer ve Birimi 3,5 (kA) 0,02 (m) 15915,494309 (A/m) 293 (K) 17,54 e-7 (.m) 0,0039 (1/K) 1,293 (Kg/m) 1010 [J/(Kg.K)] 0,026 [W/(m.K)] 7892 (Kg/ m) 452 [J/(Kg.K)] 72 [W/(m.K)]
Para zerinden geen indksiyon akm younluu ve manyetik ak izgilerine bal olarak oluan optimum s transferini hesaplayabilmek iin 3 adet numune, hava ve 7 sarml bobin meshlenmitir. 3 adet numune soldan saa doru ilerleyerek bobine girecek, bylece n stma, sinterleme, souma ilemi gerekleecektir (ekil 2).
ekil 2. 3 Adet Temas Halinde Numune, 7 Sarml Bobinin n ve Yan Grn
ekil 3. Meshlenmi 3 adet numune, 7 sarml bobin ve hava ortamnn grn.
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Bu almada, indksiyonla toz metal paralarn sinterlenmesinde indksiyon bobinlerinin sarm biimleri optimize edilerek klasik sinterleme frnlarnda elde edilen n stma, sinterleme ve yava souma aamalarndaki gibi (ekil 4) numune scakl erisinin elde edilmesi amalanmtr.
ekil 4. Klasik sinterleme frnndaki ilemler zinciri ve zaman-scaklk profili [6]. 3.1. ndksiyonla Sinterlemede Nmerik Bulgular: Toz metal numunelerin indksiyonla sinterlenmesinde bobin-numune konumlandrmas, bobin ekline gre numunelerde oluan scaklk deiimleri Kelvin olarak model zerinde numerik olarak belirlenmitir. Ayrca numunelerin yatay eksen zerinde (z-ekseni) oluan scaklk dalm grafik olarak verilmitir. Farkl sarm ekilli numuneler demir esasl malzemeler iin yaklak olarak sinterleme scakl olan 1393 K scakla kncaya kadar sinterlenmi olup, daha sonra bu scakla kabildikleri sreler esas alnarak karlatrlmtr.
ekil 5. Silindirik sarml ortalanm bobin ekline ve konumuna gre 108,3 saniyede 3 adet numune zerinde oluan scaklk dalm.
ekil 6. Silindirik sarml ortalanm bobin ekline gre 108,3 saniyede 3 adet numune zerinde oluan scaklkkonum grafii.
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ekil 7. Silindirik sarml sola dayal bobin ekline gre 87,2 saniyede 3 adet numune zerinde oluan scaklk dalm.
ekil 8. Silindirik sarml sola dayal bobin ekline gre 87,2 saniyede 3 adet numune zerinde oluan scaklk-konum grafii.
ekil 9. Konik sarml bobin ekline gre 114,7 saniyede 3 adet numune zerinde oluan scaklk dalm
ekil 10. Konik sarml bobin ekline gre 114,7 saniyede 3 adet numune zerinde oluan scaklk-konum grafii
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ekil 11. Konkav sarml bobin ekline gre 126,6 saniyede 3 adet numune zerinde oluan scaklk dalm.
ekil 12. Konkav sarml bobin ekline gre 126,6 saniyede 3 adet numune zerinde oluan scaklk-konum grafii.
ekil 13. Konveks sarml bobin ekline gre 115,4 saniyede 3 adet numune zerinde oluan scaklk dalm.
ekil 14. Konveks sarml bobin ekline gre 115,4 saniyede 3 adet numune zerinde oluan scaklk-konum grafii.
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5. SONULAR: Sinterlemede n stma, sinterleme daha sonrada yava souma koullar istenmektedir. Bu amala 7 sarml bobin iine sabit bir hzla gnderilen numune olarak modellenen sistemde, soldan saa doru ilerleyen numunenin herhangi bir noktas izlenirse n stma, sinterleme ve yava soumas aamalar gerekleir. Modellemede sadece bobin sarm ekilleri deitirilerek numuneler zerinde oluturulan scaklk dalmlarnn etkisi aratrlmtr. Modellenen modifiye edilmi bobin tasarmlar incelenecek olursa sinterleme scakl asndan aadaki sonular elde edilmitir: Silindirik sarml bobinde 1120C (1413 K) scakla 87,2 saniyede ulalmaktadr (ekil 7.). Klasik sinterleme frnnda elde edilen n stma, sinterleme ve soutma para scakl erisini salayan indksiyon bobini ekil 13te verilen i bkey (konveks) sarml bobindir. Numune dorultusunda al ve d bkey (konkav) indksiyon bobinleri, sinterleme srasndaki ilem zinciri scaklklarna uygun deildir. Optimum sinterleme parametrelerini belirlemek amacyla yaplan nmerik almalarda numuneler demir esasl malzeme olarak tanmlanmtr ve demirin termofiziksel zellikleri baz alnarak nmerik model oluturulmutur. Deneysel almalarda ise toz metal paralar retmek iin yalayc malzemeler ve baka tozlar ilave edilmektedir. Bunlar demir esasl toz metal paralarn termofiziksel (zellikle elektrik zdiren) zellikleri etkilemektedir. Daha sonraki almalarmzda, nmerik almalardaki sonularn deneysel almalarla rtp rtmedii belirlenecektir. Sinterleme esnasnda termal kamera, infrared termometreler kullanlarak numunelerin farkl noktalarndan scaklk lmleri yaplarak deneysel sonularla nmerik sonular karlatrlacaktr. 6. KAYNAKLAR : 1. Randall M.G., Editrler; Sarta, S. Trker, M., Durlu, N., Toz Metalurjisi ve Parackl Malzeme lemleri, p.p. 2-9, 143, 233-273, 279-296, TMMD, Ankara/Trkiye, 2007. 2. German, R.M., Powder Metallurgy of iron and steel, Pennsylvania, A willey interscience publication, Jon Wiley & Sons, INC., USA, pp. 181-209, 232-260, 1998. 3. S. Galunin, M. Zlobina, K. Blinov, A. Nikanorov, T. Zedler, B. Nacke, Numerical analysis of coupled physics for induction heating of movable workpieces International Scientific Colloquium Modelling for Electromagnetic Processing Hannover, October 27-29, 2008. 4. enol SERT Yksek Lisans Tezi ndksiyon Isl Ykleme le Bir atlak Etrafnda Olusan Gerilmelerin ModellenmesiSakarya niversitesi Fen Bilimleri Enstitis, Eyll 2008. 5. German, R.M., Sintering theory and practice The Pennsylvania State Universty Park, Pennsylvania, A willey interscience publication, Jon Wiley & Sons, INC., USA, pp. 313-362, 373-400, 403-420, 1996. 6. Zinn, S., Semiatin, S.L., Coil design and fabrication, Part 2, specialty coils, 1988.
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N KARITIRILMI VE SICAK PRESLENM Al-Cu ALAIMI TOZ METAL PARALARDA KIRKENDALL ETKS VE FZKSEL ZELLKLERN ARATIRILMASI
Ergn EKC*, Mahmut GLESN ** ve Yusuf ZATALBA***
*
Dzce niversitesi, Cumayeri Meslek Yksekokulu, Makine Blm, 81700, Dzce, ergunekici@duzce.edu.tr ** Gazi niversitesi Teknik Eitim Fakltesi, Makine Eitimi Blm, Teknikokullar, 06500, Ankara, gulesin@gazi.edu.tr *** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, yusufoz@gazi.edu.tr zet
Bu almada, arlka % 4,5 Cu ve kalan Al tozlar olmak zere bir saat sreyle turbulada n kartrmaya tabi tutulmutur. Karm tozlar scak presleme yntemiyle 570 Cde 200 MPa basnta 20 dakika sreyle preslenmitir. Scak preslenmi blok numuneler 550C scaklkta 2, 4, 6, 8, 10 saat sreyle difzyon tavlamasna tabi tutulmutur. Toz Metalurjisi (TM) yntemiyle retilen bu numunelerin metalografik incelemeleri ve elektron mikroskop almalar yaplarak Al-Cu difzyon sreci aratrlmtr. ki saatlik tavlama srecinde nemli miktarda bakr tozunun Al matriste difzyonla znd ancak Kirkendall etkisiyle Cu tozlarnn yerini boluklarn ald belirlenmitir. Bu durum ise TM paralarn fiziksel zelliklerini olumsuz etkilemitir. Anahtar Kelimeler: Al-Cu, Toz Metalurjisi, nkartrma, Kirkendall Etkisi.
Investigation of Kirkendall Effect and Physical Properties in Premixed and Hot Pressed PM Parts with Al-Cu Alloy
ABSTRACT In this study, the alloy consisting of 4,5% Cu and 95.5% Al powder was exposed to premixing in turbula for an hour. Then the mixture was pressed for twenty minutes in 570 C under 200 MPa pressure with hot pressing method. The samples of hot pressed blocks were exposed to diffusion annealing in 550 C for 2, 4, 6, 8, 10 hours. Diffusion process of the samples produced with powder metallurgy method was investigated by metallographic examination and electron microscopic study. It was determined that during the two-hour annealing process, great amount of Cu powder was decomposed with diffusion at Al matrix, but with the effect of Kirkendall, the Cu powder was replaced with gaps. This affected the physical properties of powder metallurgy pieces negatively. Keywords: Al-Cu, Powder Metallurgy, Premixing, Kirkendall Effect. 1. GR Toz metalurjisi teknii n alaml tozlarn ve takviye elemannn vakum kontrol altnda kartrlmas ve kaynaklanmas gibi karmak bir dizi operasyonu gerektirmektedir [1]. Alminyum alamlarna mikro (<0,5) veya makro (% 1-20) arasnda deien miktarlarda Cu, Si, Mg ve Li gibi alam elementlerinin ilavesi ile mekanik zellikleri gelitirilebilir[2,3]. Metal tozlarnn scak preslenmesiyle reaktif sinterleme (HPRS) younlama ve malzemenin kimyasal reaksiyonun her ikisinin birden tek admda gerekletii bir tekniktir. Nispeten dk sinterleme scakl, tozlarn dk maliyetinden ve younlama iin herhangi bir takviye elemanna ihtiya duyulmamasndan dolaysyla bu teknik ekonomik olabilir[4,5]. Toz Metalrjisi (TM) yntemi ile retilen paralarn mekanik zellikleri ile anma ve
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korozyon direnlerini artrmak amacyla sinterleme sonras farkl mekanik ve sl ilemler uygulanmaktadr [6]. Tane snrlarnn dalm/bileimi ve gzeneklerin dalm/bykl gibi zellikleri mikro yapnn performans zerinde etkilidir[7]. Konsantrasyon fark olan ikili bir alamda temas eden yzeylerin difzyon farkndan dolay bir ak meydana gelir[8]. Kirkendall etkisi, birleme ara yzeyinden metal iftlerine doru atomik aknn farkl olmasndan kaynaklanmaktadr [9]. Gke ve arkadalar elementel yntemle AlCuMg tozlarnn retilmesinde mikroyap zelliklerini incelemilerdir[10]. Schaffer ve arkadalar elementel yntemle retilen AlCuMgSi alamlarnda azot ve kalayn sv faz sinterleme zerindeki etkilerini aratrmlardr[11]. Fogagnolo ve arkadalar mekanik alamlama ile retilen Al-4.5 Cu kat zeltisinin MA sresi ve scakla bal olarak mikroyapsal deiimleri ve yapdaki bakrn durumunu incelemilerdir. Bakr XRD ve SEM incelemelerinde saptayamamalar nedeniyle ok kk boyutta ikinci bir faz olarak kalan aluminyum ierisinde dalm olabileceini belirtmilerdir. Baka bir olasla gre ise bakrn yap ierisinde ksm olarak znm olabilecei veya nano boyutta dalm ikinci bir fazn paras olabileceini belirtmilerdir[12]. Bu almada, scak presleme (SP) yntemiyle Al-Cu alam TM para retilmesi ve retim srecinde Cunun difzyon mekanizmas ile gzenek oluumu ve fiziksel zelliklere etkisi incelenmitir. 2. MATERYAL VE METOT almada %99 saflkta 100 m alt Al tozlar ile % 99 saflkta 44 m alt Cu tozlar kullanlmtr. % 4.5 Cu-Al karm 1 saat sreyle turbulada kartrlmtr. Kartrlan tozlar kalp ierisine alnarak n ekillendirilme iin 200 MPa souk olarak preslenmi ve devamnda 570 Cde 200 MPa basn altnda 20 dakika sre ile scak olarak preslenmitir. Bu sayede 60x60 mm kare kesitli yaklak 10mm kalnlklarnda blok numuneler retilmitir. Scak preslenmi blok numuneler 550C scaklkta 2, 4, 6, 8, 10 saat sreyle difzyon tavlamas yaplmtr. Tavlama ncesi ve sonras optik ve taramal elektron mikroskopta (TEM) mikroyap incelemeleri yaplmtr. Karm tozun gerek para younluk lmleri Sartorius marka 0,1 mg hassasiyetteki terazide younluk kitiyle yaplmtr. Vickers mikro sertlik lmleri 100 g yk 10 sn sre uygulanarak gerekletirilmitir. 3. SONULAR VE TARTIMA 3.1 Difzyon (Yaynm) ve Alamlama 200 MPa basn altnda 20 dakika sre ile scak presleme sonrasnda retilen numunelerin mikroyaplar incelendiinde, bakr tozlarnn Al matris ierisinde homojen olarak dald, gzenek orannn ok dk olduu (ekil 1a) ve Al matris ile Cu paracklar arasnda dzenli bir arayzey olutuu (ekil 1b) grlmektedir.
ekil 1. Scak presleme sonrasnda retilen numunelerin mikroyaps. Matris ierisindeki bir Cu parac etrafnda oluan difzyon gradyanlar ve elementsel mikro analizi ekil 2de verilmitir.. Scak presleme ilemi srecinde Al-Cu ikilisinin karlkl ktlesel difzyonu balam fakat tamamlanmamtr. ekil 2ada 1 nolu hat boyunca XRF/EDS analizi yapldnda 2bde verilen grafik elde edilmitir. Herhangi bir dalayc kullanmakszn dahi Cu parac etrafnda akca grlen ve farkl Al-Cu atomik younluklarna sahip difzyon gradyanlarnda paracktan uzaklatka Cu oran azalmaktadr. Burada, gradyanlarn merkezine yaklarken Cu miktarnn artt ve merkezde maksimum olduu grlmektedir. Tersine, en dtaki gradyandan balamak zere merkeze yaklatka ise Al miktar azalmtr. Merkezde bulunan Cu parac ile Al matris arayzeyinde ise bakrn ktlesel difzyonu sebebiyle oluan halka eklinde boluk grlmektedir (ekil 2ada okla gsterilmitir). Dier bir boluk ise, ekil 2ada gsterilen resmin sol alt kesinde bulunan Cu taneciinin merkezindedir. Muhtemel bu noktadaki Cu tanecii ok kk hacim ve boyutta idi (yaklak 6 m) ve scak piresleme srecindeki ktlesel difzyonla Cu tanecii byk oranda Al iine difzyon gereklemitir.
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ekil 2. Scak preslenmi Al-Cu ikilisinde bileim gradyanlar ve XRF analiz sonular. Difsyon gradyanlarnn zerindeki farkl noktalardan alnan XRF/EDS sonular ekil 3de verilmitir.
ekil 3. Difzyon gradyanlar zerinde farkl noktalardan alnan mikro analiz sonular. Bu sonular da akca gstermektedir ki 1 nolu analiz blgesinde Cu iine Al difzyonu yok denecek kadar azdr (%0.57). Ancak 2nolu blgede maksimum (%66.2) olmak zere 3 ve 4nolu blgelerde Al iine Cu difzyonunun giderek azald grlmektedir. Difzyon mekanizmasnda atomlar yksek konsantrasyonda bulunduklar bir blgeden konsantrasyonlarnn daha dk olduu bir blgeye g ederler[13]. Atomlar yalnzca yksek scaklkta ara yzeyin bir kenarndan dier kenarna difze olabilirler bunun iin gerekli olan scaklk genellikle (0.6-0.8Tm) dir. Tm buradaki ergime scakln gstermektedir[14]. Al-Cu ikili denge diyagramna gre Alminyum blgesinde bakrn znrl scakla bal deimekle birlikte 548 Cde maksimum arlka %5.65 oranndadr[15]. Bu orandan sonra Cu orannn artmas ekil 3de 4. blgede gsterildii gibi Al matris iinde AlCu2 intermetalii olan faznn oluumuna, artan Cu oranyla ile birlikte 2. ve 3. gradyan blgelerinde ise Al faz kaybolarak +2 fazlarnn olutuu sylenebilir. Btn bunlarla birlikte Cu taneciinden farkl konstrasyonlarda Al matris iine yaynan Cu atomlarnn, Cu iine yaynan Al atomlarndan ok daha fazla olduu ve yaynmann Cu dan Al matrise doru olduu aka grlmtr. Bunun nedeni olarak Cu atomlarnn aplarnn (2.556 ), Al atom aplarndan (2.886 ) daha kk olmas, ve kk apl atomlarn yaynm hzlarnn byk atomlardan daha hzl olmas sylenebilir[16]. Bu durum sebebiyle Al iinde Cun yaynm blgesi bymektedir. Bakr tarafnda ise gei blgesinin dar olmasna neden olmaktadr[17]. Bu mekanizmalarn meydana getirdii Al iinde Cun hzl ktlesel yaynm ekil 2de okla gsterilen Cu taneciinin evresindeki ktle kaybn ve ayn zamanda scak preslenen bu numunelerin 2, 4, 6 ve 10 saatlik difzyon/sinterleme tavlamas srecinde Cun byk oranda Al iine ktlesel yaynm sebebiyle oluan gzenekleri meydana getirmitir. ekil 4de aka grlen ve Cu taneciklerinin neredeyse tamamen yaynmyla meydana gelen gzeneklerin varl Kirkendall etkisiyle aklanr[18]. Yukarda bahsedilen yaynm etkileriyle oluan Kirkendall etkisiyle ve artan difzyon/sinter tavlamas ile birlikte Cu paracklarnn boyutlarna yakn (<50m) boluklar belirlenmitir. ekil 4de 2 saat difzyon tavna tabi tutulan numunede bu durum aka grlmektedir. Ayrca, halen tamamen yaynmam, boluk iinde kalm Cuca zengin kalntlar ve hi yaynmam Cu paracklar grlebilmektedir.
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ekil 4. 2 saat difzyon/sinter tavlamas sonrasnda oluan boluklar. 3.2 Younluk Deiimleri retilen numunelerin tavlama ncesi ve sonras llen younluk deerleri ekil 5de verilmitir. Scak presleme ile retilmi numunelerin younluu %99 civarndadr. Ancak artan difzyon/sinter tav sresiyle birlikte numunelerin younluk oranlarnda azalma belirlenmitir. zellikle 2 saat tavlama sonundaki younluk d nemli miktardadr. Kirkendall etkisinin zellikle tavlama srecinde belirginletii yukarda aklanmtr. Bu srete, Al matris iinde yaynan Cu atomlarnn yaklak toplam hacin %95ini oluturan Al matris hacmini arttraca, bununla birlikte % 4.5 oranndaki Cu partikllerin oluturduu boluklarda ise bzlme olaca literatrde belirtilmektedir[19-20]. Numunelerin ktlelerinin sabit olmasna ramen, tavlanm numunelerde belirgin oranda oluan Kirkendal etkisinin meydana getirdii bu hacimsel artn younluk azalmasna sebep olduu dnlmektedir.
ekil 5. Difzyon/sinter tav sresine bal younluk deiimi. 3.3 Sertlik Deiimleri Scak presleme sonrasnda retilen numunelerin tavlama ncesinde elde edilen mikrosertlik deerleri ekil 6da verilmitir. Bakr paracn merkezinde sertlik maksimum (249 HV) iken difzyon gradyanlar zerinde merkezden uzaklatka sertlik deeri Al miktarnn artmas ile azalmaktadr.
ekil 6. SP sonras mikrosertlik.
ekil 7. Difzyon/Sinter tavlar sonras sertlik.
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Farkl srelerde difzyon tav uygulanan numunelerin sertlik deiimleri ekil 7de verilmitir. Genel olarak tavlama sresinin artmas ile sertlik deerinin artt net olarak grlmektedir. Scak preslenmi numunenin sertlii 38 HV iken artan tavlama sresi ile 78 HV sertlie kadar art meydana gelmitir. zellikle 4 saate kadar tavlama sresindeki artla artan boluk/gzenek oranna ramen Al matris iinde daha dk konsantrasyon fark oluturarak znen Cu miktarnn art genel olarak numunenin sertliini de arttrd sylenebilir. Bu sreden sonraki numune sertliinin 10-15HV aralndaki sapma ile sabit kald, bu sapmaya ise tavlama sresiyle artan boluk oranndaki artn sebep olduu dnlmektedir. 4. SONULAR Al+%4,5 Cu n kartrlm tozlarn scak preslenmesi ve devamnda farkl srelerde tavlanmas ile oluturulan Al-Cu alam tozmetal paralardaki difzyon srecinin ve fiziksel zelliklerin aratrld bu almada aadaki sonular sylenebilir. 1. n kartrlm Al-Cu tozlarnn 200 MPa basn altnda 570 C scaklkta 20 dakika sre ile preslenmesi sonunda yaklak %99 younlukta TM para retimi gerekletirilmitir. Ancak bu sre iinde Al-Cu difzyonunun tam olarak gereklemedii ve Cu paracnn evresinde (Al matris iinde) eitli younluklarda Cu ieren difzyon gradyanlarnn olutuu grlmtr. Bu gradyanlarn Cu younluu bakr tanecikten uzaklatka azalmaktadr. 2. Scak presleme srecinde Cun alminyum matrise ktlesel difzyonu, Kirkendall etkisiyle Cu taneciin evresinde boluk oluturmutur. Devamnda, Cun Al iinde tamamen yaynmasn salamak iin yaplan tavlama srecinde Cu taneciklerinin yerini tamamen boluklar almtr. 3. Tavlama ilemiyle artan Kirkendall etkisi, retilen TM numunelerin younluklarnn dmesine sebep olmutur. 4. Genel olarak artan difzyon tav ile birlikte TM numunelerin sertlii de artmtr. KAYNAKLAR 1. Bedir, F., Characteristic Properties of AlCuSiC and AlCuB4C Composites Produced by Hot Pressing Method Under Nitrogen Atmosphere, Materials and Design, Vol. 28, pp. 12381244, 2007. 2. Hirosawa, S., Sato, T., Kamio, A., Flower, HM., Classification of the role of microalloying elements in phase decomposition of Al based alloys, Acta Mater, Vol. 48, pp. 1797806, 2000. 3. Bishop, DP., Cahoon, JR., Chaturvedi, MC., Kipouros, GJ., Caley, WF., On enhancing the mechanical properties of aluminium P/M alloys, Mater Sci Eng, A290, pp. 1624, 2000. 4. Veljovic, D., Jokic, B., Petrovic, R., Palcevskis, E., Dindune, A., Mihailescu, I.N., Janackovic, D., Processing of dense nanostructured HAP ceramics by sintering and hot pressing, Ceramics International, Vol. 35, pp. 14071413, 2009. 5. Huang, L.J., Geng, L., Li, A.B., Yang, F.Y., Peng, H.X., In situ TiBw/Ti6Al 4V composites with novel reinforcement architecture fabricated by reaction hot pressing, Scripta Materialia, Vol. 60, pp. 996999, 2009. 6. Boylu, K.S., Varol, R., Pek, M.A., Tam Youn Ve T/M eliklerde Karbon Miktarnn Borr Tabakas Kalnlna Etkisi TMMOB Makina Mhendisleri Odas Konya ubesi H- Makina .Tasarm ve malat Teknolojileri Kongresi 26-27 Eyll 2003 7. Rong, L., Hongqiang, R., Kai, G., Di, T.,Research on Preparation of Zr( OH)JB4 C Composite Powder by Different Processes, Journal of Rare Earths Vo1. 25, p.340, 2007. 8. Shewmon, P.G., Diffusion in Solids, Mc Grow Hill Book Company, 1964. 9. Adda, Y., Philibert, J., La diffusion dans les solides. Bibliothque des Sciences et Techniques Nuclaires, Presses Universitaire de France, Paris, pp. 810853, 1996. 10. Gke, A., Fndk, F., Kurt, A.O., Microstructural examination and properties of premixed AlCuMg powder metallurgy alloy, Materials Characterization, Vol. 62, pp. 730735, 2011. 11. Schaffer, G.B., Yao, J.Y., Bonner, S.J., Crossin, E., Pas, S.J., Hill, A.J., The effect of tin and nitrogen on liquid phase sintering of AlCuMgSi alloys, Acta Materialia, Vol. 56, pp. 26152624, 2008. 12. Fogagnolo, J.B., Amador, D., Ruiz-Navas, E.M., Torralba, J.M., Solid solution in Al4.5 wt% Cu produced by mechanical alloying, Materials Science and Engineering, A 433, pp. 4549, 2006. 13. Ouz, B., Demir D Metaller Kayna, Oerlikon Yayn, stanbul, 468-469 1990. 14. Chen, S., Ke, F., Zhou, M., Bai, Y., Atomistic investigation of the effects of temperature and surface roughness on diffusion bonding between Cu and Al Acta Materialia, Vol. 55, pp. 31693175, 2007. 15. Willamson, J.R., Superplastic Forming Diffusion Bonding of Titanium, Proc. The Ist. Int. Cant. Materials in Areospace. 2.Konf. No. 10817, pp. 373394, 1986. 16. Richmond, O., Morrison, H.L., Devenpeck, M.L.,. Sphere indentation with application to the Brinell hardness test, Int. J. Mech. Sci, Vol. 16, pp. 7582, 1974. 17. Callistar, W.D., Materials Science and Engineering an ntroduction Diffusion Mechanism, 5th Edition, The Universty of Utah Johnwilley, 94-111, 2000. 18. Strandlund, H., Larsson, H., Prediction of Kirkendall shift and porosity in binary and ternary diffusion couples, Acta Materialia, Vol. 52, pp. 46954703, 2004. 19. Srinivasan, D., Subramanian, P.R., Kirkendall porosity during thermal treatment of MoCu nanomultilayers, Materials Science and Engineering, Vol. 459, pp. 145150, 2007. 20. Hermans, M.J.M., Biglari, M.H., Void formation by Kirkendall effect in solder joints, Netherlands, December 2006.
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MANYETK NKEL DEMR ALAIMLARININ MKRODALGA SNTERLEME YNTEMYLE RETLMES

Derya Erdem, Arcan F. Dericiolu Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mh. Bl deryae@metu.edu.tr, arcan@metu.edu.tr ZET Mikrodalga sinterleme yntemi, ncelikli olarak seramik paralarn retiminde hzl ve niform stma salamas, malzemelerin teorik younluuna daha yakn deerlerde ve daha iyi mikroyaplarda elde edilebilmesi sebebiyle kullanlmtr. Ancak, hacimli metalik paralarn mikrodalgalar yanstc zellikleri sebebiyle, uygulama alan seramik retim sreleriyle snrl kalmtr. Ancak, toz metalurjik paralarn; ounlukla mikroldaga etkileim kalnl ile orantl byklklerde tozlardan olumasndan tr, mikrodalgalar ile verimli bir ekilde etkileerek mikrodalga enerjisini sourabildikleri ve mikrodalgalarla hacimsel olarak stlabildikleri grlmtr. Bunun yansra, mikrodalga enerjisi ile sinterlenerek retilen toz metalurjik paralarn, konvansiyonel yntemle sinterlenen kartlarndan daha az enerji kullanlarak, daha dk sinterleme scaklk ve srelerinde, iyiletirilmi mekanik zellikler ve gzenek morfolojileriyle retilmesinin mmkn olduu anlalmtr. Bu almada, manyetik zelliklere sahip toz metalurjik Ni-Fe (Nikel-Demir) alamlar hem mikrodalga sinterleme yntemiyle hem de konvansiyonel yntemle retilmi ve retilen alamlar oluan fazlar ile mikroyapsal ve manyetik zellikler bakmndan karakterize edilerek konvansiyonel ynteme kyasla incelenmitir. Literatrde bulunan pek ok almadan farkl olarak, bu alma kapsamnda mikrodalga sinterleme ynteminin toz metalurjik numunelerin mikroyapsal ve mekanik zelliklerinin yansra, yumuak manyetik zelliklerine etkisi de incelenmitir. Anahtar Kelimeler: Mikrodalga sinterleme, nikel-demir alamlar, mekanik zellikler, manyetik zellikler. ABSTRACT In this study, soft magnetic Ni-Fe permalloy compacts were consolidated through microwave and conventional sintering routes at combinations of various sintering temperatures and compaction pressures. Sintered alloys were characterized in terms of their densification, microstructural evolution as well as magnetic and machanical properties. The effect of sintering method in terms of the applied sintering parameters on the final properties of the compacts were investigated in a comparative manner. It was determined that microwave sintered permalloys are superior compared to their conventionally sintered counterparts in densification response, microstructural characteristics such as pore shape and distribution as well as mechanical properties. However, permeabilities of the microwave sintered permalloys were inferior to their conventionallty sintered counterparts possibly due to microstructural refinement associated with microwave sintering route. Keywords: microwave sintering, nickel-iron alloys, mechanical properties, magnetic properties 1.GR Yumuak manyetik malzemeler, transformatr ekirdekleri, manyetik kayt cihazlar vb gibi elektrik ve telekominikasyon endstrilerinde geni bir uygulama alanna sahiptir [1]. Yumuak manyetik malzemeler ierisinde, ktlece %80 Nikel ieren Nikel-Demir (Ni-Fe) alamlar, yksek manyetik geirgenlikleri nedeniyle byk bir nem arzetmektedir. Hacimli Ni-Fe alamlar, 2kHze kadar olan frekanslara kadar olan uygulamalarda tercih edilirken; daha yksek frekanslardaki uygulamalarda eddy akmlarndan kaynaklanan AC kayplarn azaltmak iin toz metalurjik Ni-Fe alamlar kullanlmaktadr [1]. Toz metalurjik yntem, AC kayplarnn azaltlmasnn yansra, kompleks geometrilerde paralarn azalan gzeneklilik yzdesi, homojen ve kk boyuttaki tanelerden oluan mikroyaplarda elde edilmesi olanaklarn
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da salamaktadr. Ayrca, sinterleme aamasnn kontrol araclyla, toz metalurjik paralar son ekillerine yakn halde minimal ekinti ile retilebilirler [2-3]. Toz metalurjik paralarn sinterlenmesi yaygn olarak elektrikli konvansiyonel frnlarda gerekletirilmektedir. Is enerjisinin frnn stc elemanlarndan numunelerin yzeyine radyasyon ve konveksiyon meaknizmalar ile iletimi esasna dayanan bu yntemde, sl gerilmeleri ve atlamalar nlemek araclyla, olduka dk stma hzlar ve ara duraklamalar tercih edilmektedir. Bu nedenle, hem ilem sreleri ve enerji sayfiyatlar artmakta, hem de numunelerin yksek scaklklara daha uzun sreler maruz kalmas sebebiyle, mikroyapsal irileme ve tane boyutunda art meydana gelmektedir. Toz metalurjik alamlarn, hacimli kartlarndan farkl olarak, mikrodalgalar ile verimli bir ekilde etkileebilmeleri ve hacimsel olarak stlabilmeleri sayesinde, toz metalurjik alamlar mikrodalga sinterleme yntemiyle konvansiyonel ynteme kyasla azalan ilem sreleri ve enerji sayfiyatlar ile, artan sinterlenmi younluklarda, azalan gzeneklilik yzdeleri ve tane boyutlar ile iyiletirilmi mekanik zelliklerde, artan korozyon ve anma dayanlar ile retilebilmektedir [4-12]. Bu almada, yumuak manyetik zellikler gsteren toz meta metalurjik Ni-Fe alamlar hem mikrodalga sinterleme hem de konvansiyonel yntemle deien sinterleme scaklklarnda retilmi, deien sinterleme sre parametrelerinin ve sinterleme ynteminin numunelerin younlam, mikroyapsal ve manyetik zelliklerine etkisi de incelenmitir. Ayrca, bu almada, literatrde bulunan nceki almalara ek olarak, mikrodalga sinterleme ynteminin toz metalurjik alamlarn yumuak manyetik zelliklerine de etkisi incelenmitir. 2. DENEYSEL YNTEM 2.1. Pelet Hazrlama Ni ve Fe tozlar (Ni: %99,99 saflk, 7-10 parack boyutu, ekil 1a, Fe: %99,99 saflk, 10 mden kk parack boyutu, ekil 1b) ktlece 4:1 orannda olacak ekilde tartlm ve istenilen oranda homojen bir karm elde etmek amacyla izopropilalkol (IPA) ortamnda elde kartrlmtr. Karmn kurumasn takiben, tozlar iki eksenli souk sktrma yntemiyle 200 MPa sktrma basnc kullanlarak ekillendirilmi ve daha sonra maksimum preslenmi younlua ulaabilmek amacyla, souk izostatik presleme yntemiyle 1500 bar altnda sktrlmtr. Sktrma ilemi sonras, disk eklindeki geometriye sahip 15 mm apl ve ortalama 4,5 mm ykseklikli peletler, %71 sinterleme ncesi younlukla elde edilmitir.
ekil 1a. almada kullanlan Ni tozunun taramal elektron mikroskobu grnts.
ekil 1b. almada kullanlan Fe tozunun taramal elektron mikroskobu grnts.
2.2. Sinterleme retilen peletler, mukavemet art ve pekleme salamak amacyla sinterleme srecine tabi tutulmutur. Sinterleme ilemi, Ni-Fe alamlar korozyona grece dayankl olduklarndan herhangi bir koruyucu atmosfer kullanmna gerek duyulmakszn 1200, 1225 ve 12500C scaklklarda 45 dakika sreyle 4,8 kW gcndeki mikrodalga frn (MKH-4.8???, Linn High Therm GmbH, Eschenfelden, Germany) kullanlarak gerekletirilmitir. Toz metalurjik numunelerin oda scaklnda mikrodalgalar ile verimli bir ekilde etkileememelerinden dolay, verimli etkileim scaklklarna n stma salamak amacyla 63mlik -SiC tozu kullanlmtr. SiC yksek kayp tanjant sebebiyle oda scaklndan itibaren elektromanyetik dalgalar ile etkin olarak etkileerek snmakta ve n stma amacyla susceptor malzeme olarak sklkla kullanlmaktadr. Mikrodalga sinterleme srasnda, s kayplarn engellemek amacyla tasarlanan almina fiber-bord yaltm malzemeleri ve almina krozelerden oluan izolasyon kafesi, ekil 2a ve 2bde gsterilmektedir. Mikrodalga sinterleme yntemiyle retilen numunelerin karakterizasyonu esnasnda kyaslama yapabilmek amacyla, ayn koullarda hazrlanan peletler konvansiyonel sinterleme yntemiyle de ayn sinterleme parametreleri kullanlarak retilmitir.
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ekil 2a. Mikrodalga sinterleme izolasyon kafesi.izolasyon kafesi. 2.3. Malzeme Karakterizasyonu
ekil 2b. Mikrodalga sinterleme dzeneginin x-x kesiti
Younluk lm: Sinterleme sreci sonrasnda elde edilen numuneler, yzeylerinde bulunan oksit tabakasnn giderilmesi amacyla kaba zmparalandktan sonra, 24 saat sreyle ksilende bekletilmi ve daha sonra Arimet Yntemi kullanlarak deneysel younluklar llmtr. Elde edilen sonularn allmakta olan Ni-Fe alamnn teorik younluuna (hacimli nikel ve demir metallerinin younluklarnn ktlece yzdelerine gre oranlanmasyla elde edilen younluk deeri) oranlanmasyla ulalan %younlam deerleri belirlenmitir. Faz Analizi: Sinterlenen alamlar X nlar krnm (XRD) yntemiyle10-90 aralnda 2/dak. tarama hzyla oluan fazlar bakmndan incelenmitir. Mikroyap Analizi: Mikrodalga ve konvansiyonel sinterleme sreleriyle retilen alamlarn metalografik olarak parlatlm ancak dalanmam yzeyleri gzeneklilik yzdeleri ve gzenek morfolojilerinin incelenebilmesi amacyla, Taramal Elektron Mikroskobu kullanlarak incelenmitir. Elde edilen mikroyaplar yardmyla mikrodalga ve konvansiyonel sinterleme yntemlerinin %gzeneklilik ve gzenek morfolojileri zerindeki etkileri karlatrlmtr. Manyetik Karakterizasyon: Titreimli rnek Manyetometresi (VSM) (EasyVSM EV10, ADE Electronics, Wisconsin, USA) kullanlarak, alamlarn manyetik zellikleri llm ve mikrodalga sinterleme ynteminin manyetik zelliklere etkisi konvansiyonel ynteme kyasla incelenmitir.
3. Bulgular ve Tartma Mikrodalga enerjisi ve SiC tozlarnn salad stma sayesinde, mikrodalga sinterleme sreci esnasnda 300C/dky geen stma hzlar ile numuneler sinterleme scaklklarna stlabilirken, konvansiyonel yntemde stma hz 100C/ dky geememitir. Bu balamda, mikrodalga sinterleme yntemiyle, konvansiyonel ynteme kyasla toz metalurjik numuneler azalan ilem sreleri ve maliyetleri ile retilebilmitir. ekil 2de mikrodalga (MW) ve konvansiyonel (C) sinterleme yntemi ile retilen numunelerin sinterleme sonras younluk sinterleme scakl erileri incelendiinde; ayn koullarda mikrodalga sinterleme yntemiyle retilen numunelerin konvansiyonel kartlarndan daha yksek younluklara eritii grlmektedir. Bunun yansra, konvansiyonel sinterleme yntemiyle retilen numunelerin sinterlenmi younluklarnn, 12500Cde optimize olduu, ve artan sinterleme scaklklar ile d gsterdii saptanmtr. Bu durumun, tane bymesi, gzeneklerin birlemesi ve tane snrlarnn oksitlenmesinden ileri geldii dnlmektedir. Mikrodalga sinterleme yntemiyle retilen numunelerde ise, sinterlenmi younluklarn sinterleme scaklklar ile artt grlmtr. ki yntem arasnda gzlemlenen bu farklln, mikrodalga sinterleme yntemiyle salanan hzl ve hacimsel stmadan kaynakland dnlmektedir. Mikrodalga sinterleme yntemiyle olduka hzl olarak sinterleme scaklna stlan numuneler, konvansiyonel ynteme kyasla azalan tane boyutuna sahip olduklarndan, sinterleme esnasnda atomlarn kolaylkla difzyon yapabilecei daha fazla yzey alan bulunmakta ve mikrodalga sinterleme yntemi ile ayn koullarda konvansiyonel ynteme kyasla daha yksek younluklara eriilebilmektedir. Ayrca, sinterleme sreci mikrodalga sinterleme yntemi ile daha ksa olduundan, tane snrlarnn oksitlenmesinin konvansiyonel ynteme kyasla daha az miktarda gerekletii dnlmektedir.
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ekil 2. Mikrodalga (MW) ve konvansiyonel (C) sinterleme yntemiyle 1200, 1250 ve 1300C scaklklarda retilen numunelerin sinterlenmi younluk sinterleme scakl grafii Numunelerin taramal elektron mikroskobu ve optik mikroskop aracl ile mikroyapsal zellikleri incelendiinde ise, mikrodalga sinterleme yntemi ile retilen numunelerin, konvansiyonel kartlarna kyasla azalan gzeneklilik yzdesi ve tane boyutu ile yuvarlaklam gzenek morfolojileri ile elde edilebildikleri grlmtr (ekil 3, Tablo 1). Ayrca, her iki yntemle retilen numunelerde; sinterlenmenin iyi bir derecede gerekletiini gsteren tavlama iftleri bulunmaktadr. Tablo 1. Mikrodalga (M) ve konvansiyonel (K) sinterleme yntemleriyle 1200, 1250, 1300C scaklklarda retilen numunelerin ortalama tane boyutu deerleri. Sinterleme Scakl (C) 1200 1250 1300 Ortalama Tane Boyutu (m) M K 96 106 110 109 135 150
ekil 3. Mikrodalga sinterleme yntemiyle 1200 (a), 1250 (c) and 1300 C (e) ve konvansiyonel sinterleme yntemiyle1200 (b) and 1250 (d) and 1300 C (f) scaklkarda retilen numunelerin taramal electron mikroskobu grntleri
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Numunelerin mekanik zelliklerinin mikrosertlik deerleri zerinden karakterizasyonu gerekletirildiinde ise (ekil 4), her iki yntemle retilen numunelerin optimum sertlik deerlerine maximum younlama denk gelen sinterleme scaklklarnda ulatklar grlmektedir. Bu durum, sinterleme sonras younluklarn toz metalurjik numunelerin fiziksel zelliklerini belirleyen nemli parametrelerden biri olmas sebebiyle, beklenen bir durumdur.
ekil 4. Mikrodalga (M) ve konvansiyonel (K) sinterleme yntemleri ile 1200, 1250 ve 1300C scaklklarda retilen numunelerin ortalama mikrosertlik deerleri Diferansiyel manyetik geirgenlik erileri zerinden numunelerin manyetik zellikleri incelendiinde ise (ekil 5 a-b), her iki metodlar retilen numunelerin, daha dk scaklklarda retildiklerinde daha yksek manyetik geirgenlik deerlerine ulatklar grlmektedir. Dk scaklklarda toz metalurjik alamlarn ulatklar sinterlenmi younluk deerleri dk olmasna ramen, bu scaklklarda bile 100mye yaklaan ortalama tane boyu deerleri sayesinde, yksek scaklklarda etkin olan tane snr oksitlenmesi nedeniyle, dk scaklklarda daha yksek manyetik geirgenlik deerlerine ulalabilmitir. Ayrca, mikrodalga sinterleme yntemiyle retilen numunelerin, konvansiyonel sinterleme yntemiyle retilen kartlarna kyasla daha dk manyetik geirgenlik deerlerine sahip olduklar tespit edilmitir. Bu durumun, konvansiyonel sinterleme yntemi srasnda mikroyapsal irileme ve ortalama tane boyutundaki artdan kaynakland dnlmektedir.
ekil 5. Mikrodalga (a) ve konvansiyonel (b) yntemle 1200, 1250, 1300C scaklklarda retilen numunelerin diferansiyel geirgenlik deerlerinin uygulanan manyetik alanla (H) deiimi 4.Sonu Bu alma kapsamnda elde edilen bulgular, mikrodalga sinterleme yntemiyle toz metalurjik yumuak manyetik Ni-Fe alamlarnn konvansiyonel yntemel kyasla azalan ilem sreleri ve enerji safiyatlar ile, daha yksek
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sinterlenmi younluklarda, azalan gzeneklilik yzdesi ve tane boyutu, iyiletirilmi mekanik zellikler ile retilebildiklerini gstermitir. Diferansiyel geirgenlik erileri zerinden numunelerin manyetik karakterizasyonu yapldnda ise, sinterleme sonras ok daha byk ortalama tane boyutu deerlerine sahip olan konvansiyonel yntemle retilmi numunelerin, mikrodalga sinterleme yntemiyle retilmi numunelerden daha iyi yumuak manyetik zellikler gsterdii tespit edilmitir. Ancak, sinterleme sonras manyetik numunelere tatbik edilecek olan tane iriletirme tavlamas ilemi nedeniyle, mikrodalga sinterleme yntemi ile retilen numunelerin de tane boyutu artrlacandan, yumuak manyetik toz metalurjik Ni-Fe numunelerin, azalan ilem sreleri ve artan sinterlenmi younluk deerleri ile mikrodalga sinterleme yntemiyle avantajl bir ekilde retilebilecei dnlmektedir. KAYNAKA [1] W.F.T. Gale, Terry C, in: Smithells Metals Reference Book, pp. 9-12. [2] F. Fausto, in: Measurement and characterization of magnetic materials, Elsevier Academic Press, 2004, pp. 62-65. [3] R.M. German, Powder Metallurgy Science, Metal Powder Industries Federation, 1989. [4] R.M. Anklekar, K. Bauer, D. Agrawal, R. Roy, Powder Metallurgy, 48 (2005) 39-46. [5] V.D. Buchelnikov, D.V. Louzguine-Luzgin, A.P. Anzulevich, I.V. Bychkov, N. Yoshikawa, M. Sato, A. Inoue, Physica B: Condensed Matter, 403 (2008) 4053-4058. [6] M. Celuch, W. Gwarek, M. Soltysiak, in: 2008 International Conference of Recent Advances in Microwave Theory and Applications, MICROWAVE 2008, 2008, pp. 404-405. [7] P. Chhillar, D. Agrawal, J.H. Adair, Powder Metallurgy, 51 (2008) 182-187. [8] S. Das, A.K. Mukhopadhyay, S. Datta, D. Basu, Bulletin of Materials Science, 31 (2008) 943-956. [9] H. Katsuki, S. Komarneni, Funtai Oyobi Fummatsu Yakin/Journal of the Japan Society of Powder and Powder Metallurgy, 50 (2003) 745-750. [10] C. Leonelli, P. Veronesi, L. Denti, A. Gatto, L. Iuliano, Journal of Materials Processing Technology, 205 (2008) 489-496. [11] K. Saitou, Scripta Materialia, 54 (2006) 875-879. [12] S. Takayama, G. Link, M. Sato, M. Thumm, in: Conference Digest of the 2004 Joint 29th International Conference on Infrared and Millimeter Waves and 12th International Conference on Terahertz Electronics, 2004, pp. 729-730.
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Akm Destekli Sinterleme Yntemi le retilen Al2O3 Takviyeli Bronz Matriksli MMKin Karakterizasyonu
Mehmet UYSAL Ramazan KARSLIOLU, Ahmet ALP Hatem AKBULUT, Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm 54187 Adapazar/SAKARYA mehmetu@sakarya.edu.tr zet Bu almada bronz (% 90 Cu - %10 Sn) matriks ierisine 80 m boyutlarnda hacimce %10, 20 ve 30 takviyeli almina (Al2O3) ilave edilerek metal matrisli kompozit malzeme (MMK) retimi amalanmtr. stenen bileimdeki tozlar bilyal deirmende homojen bir ekilde kartrlp basn altnda souk olarak ekillendirilmitir. Oluturulan mukavemetsiz malzeme yaps, yksek akm ve dk voltaj kullanlarak hzl bir ekilde sinterlenmitir. retilen numunelerin mikro yap, mikro setlik zellikleri ile oluan fazlar ve matriks yap iersindeki partikl dalmlar Taramal Elektron Mikroskobu (SEM) kullanlarak incelenmitir. Anahtar Kelimeler: Akm destekli sinterleme, Bronz, SiC, MMK Abstract In this study, a bronze matrix (90 wt. % Cu + 10 wt. % Sn) was reinforced with Al2O3 particles using mechanical alloying and then produced by subsequent rapid current sintering technique. The mechanically ball milled bronze powders were reinforced with electroless Ni coated 80 m Al2O3 particles with different volume fractions of 10 vol. % 20 vol. % 30 vol. % Microstructure of the bronze / Al2O3 composite produced by these techniques have been investigated by means of SEM. Keywords: current sintering, bronze, Al2O3, MMC 1.Giri MMKlerin retim ve kullanmlar son 20 ylda teknolojik gelimelerle birlikte, havaclk, uzay, savunma, otomotiv, spor ve denizcilik gibi uygulamalarda art gstermitir Gnmzde zellikle otomotiv, uzay, denizcilik, demiryolu tamacl ve spor malzemeleri gibi endstriyel sanayi alanlarnn birounda, kompozit malzemelerin geleneksel malzemelerin yerine kullanmlar gn getike artarak devam etmektedir [1, 2]. Bunun nedeni olarak, kompozit malzemelerin zellikle yksek spesifik mukavemet (/E), spesifik modl (/E) ve dk younluk zellikleri gsterilebilir. Kompozit malzemeler ayrca metaller gibi geleneksel malzemelere gre daha dk younluklar, artan korozyon ve scaklk gibi zellikleriyle birtakm avantajlar sunmaktadr [3]. Partikl takviyeli kompozitler, matriks malzemesinin ierisine takviye malzemesi olarak partikllerin ilave edilmesi ile oluur. Partikller farkl boyutlarda olabilen, tahmin edilebilir izotropik zellikler salayan malzemelerdir. Ayrca birok partikl takviyeli kompozit malzeme iyi mekanik, termal ve tribolojik zellikleri sebebiyle ilgi ekmekte, ok eitli endstriyel uygulamada kullanlmaktadr. Yaygn olarak kullanlan partikller SiC ve Al2O3 olmakla birlikte, TiB2, B4C, SiO2, TiC, WC, BN, ZrO2 gibi partikl takviyeler zerine birok alma yaplmaktadr [4]. Metal matriksli kompozit malzemelerin retiminde karlalan en temel problem, seramik fazn slatlamamas ve buna bal olarak iyi bir ba oluturulamamasdr. Bu problem kompozit malzemelerin ara yzey zelliklerini nemli lde etkiler. Ara yzeyin yaps kompozit malzemenin zellikleri zerinde nemli bir etkiye sahiptir. Takviye faz ile malzemenin zelliklerinin glendirilmesi, matriks ve takviye
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faz arasndaki ara yzey bann gcne baldr. Gl bir ara yzey ba, ykn matriksden takviye fazna doru transferine izin verir. Bununla beraber malzemenin sertlik, krlma tokluu, sl genleme, s iletkenlii srtnme katsays da ara yzeyin yapsyla etkilenir. Ara yzey ba dayanmn artrabilmek iin kompozit retim ileminden nce genel olarak farkl n ilem; -Seramik partikllere metalik kaplamalarn uygulanmas, -Reaktif metallerle metal matrisin alamlandrlmas, -Seramik partikllere sl ilem uygulanmas, suretiyle salanr [5, 6]. Dk termal genleme katsays, yksek sertlik, yksek elastik modl, iyi elektriksel iletkenlik, yksek termal iletkenlik, iyi anma dayanm gibi zelliklerinden dolay bakr esasl kompozitler, yksek hibrid modll malzemelerin, elektronik rlelerin, elektrikli yaylarn, birok elektrik/elektronik paralarn, frenlerin, srtnmeye direnli malzemelerin retimi gibi amalar iin kullanlmaktadr [7, 8]. Bu almada bronz matriks iersine farkl hacim oranlarnda Al2O3 tozlar ilave edilerek, akm destekli sinterleme yntemiyle kompozit malzeme retilmitir. Akm sinterleme ynteminin seilme nedeni, ksa srelerde youn ve dk maliyetli kompozitlerin elde edilmesidir. retim prosesi uygulanmadan nce Al2O3 seramik partikllerinin matriks yapya daha kolay girmesini kolaylatracak slatma artlarn salamak amacyla yzeyleri akmsz yntemle nikel ile kaplanmtr. retilen kompozit malzemelerin mikroyap ve sertlik zellikleri incelenmitir. 2. Deneysel almalar 2.1. Malzemeler MMK malzeme retiminde matriks malzemesi olarak bronz (%90bakr-%10 kalay), takviye malzemesi olarak hacimce % 10, 20 ve 30 oranlarnda, ortalama 80 m boyutunda Al2O3 seramik partiklleri kullanlmtr. 2.2. Seramik Tozlarn Akmsz Yntemle Nikel Kaplanmas Kompozit malzeme retiminde, metal/seramik partikl ara yzeyi byk sorun oluturmaktadr. Bu ara yzey sorununu ortadan kaldrabilmek ve metal ile seramik arasndaki slatabilirlii artrmak iin, seramik partikllerin yzeyi metal ile kaplanmaktadr. Bu amala yaplan almalarda alkali zeltiler kullanlm olup, Al2O3 seramik partikllerinin yzeyleri Ni ile akmsz artlarda kaplanmtr. ekil 1 de kullanlan akm destekli sinterleme ynteminin grnts verilmitir.
ekil 1. Akm sinterleme deney dzeneinin grnts [9] 2.2.1. Kaplama ncesi Uygulanan n Yzey lemleri Seramik Tozlarnn Temizlenmesi: Kaplama yaplacak Al2O3 seramik tozlarnn yzey zellikleri kaplamann verimlilii asndan ok nemlidir. Bu yzden seramik tozlarn kaplama ncesi yzeyleri ultrasonik temizleme cihaznda aseton zeltisi iinde yaplarak, kaplamaya engel olabilecek eitli kirlilikler giderilmeye allmtr. Hassaslatrlma lemi: Bu ilemden ama toz yzeylerinde kalay iyonlarnn adsorbsiyonudur. Seramik tozlar aseton ile temizlendikten sonra SnCl2 zeltisinde belirli srelerde tutulmak suretiyle
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hassaslatrma denilen bu ilemin uygulanmas suretiyle yzeyde adsorbe olmu +2 deerlikli kalay iyon tabakasnn oluturulmasdr. Aktivasyon lemi: Bu ilem genellikle hassaslatrma ilemi akabinde uygulanmaktadr. Bu ilem srasnda tozlar aktivasyon amacyla PdCl2 zeltisinde belirli bir sre bekletilmektedir. Bu esnada toz yzeylerindeki kalayn ykseltgenmesi srasnda aa kan elektronlar alarak indirgenen Pd, ok ince bir tabaka oluturmaktadr. Tozlar daha sonra 90 oCde etvde kurutularak kaplamaya hazr hale getirilmitir. 2.2.2.Seramik Tozlarnn Nikel le Kaplanmas lemleri Al2O3 seramik tozlarnn kaplanmasnda kullanlan akmsz nikel kaplama banyosu bileimi ve parametreleri Tablo 1de verilmitir. Kaplamalar, pH 8 olan alkali zeltide ve 70 0C scaklkta gerekletirilmitir. Tablo 1. Akmsz nikel kaplama banyosu ierii ve parametreleri Banyo bileenleri ve parametreleri Datalar NiCl2 (45.0 g/l) Na-citrate (C6H5Na3O7. 2H2O) (100.0 g/l) NH4Cl (50.0 g/l) sodium hypophosphite 8.0 g/l) pH 8 Scaklk 70oC Sre Partikl miktar 2.3. Kompozit Malzeme retimi Bronz matrisli kompozit malzeme retimi iin ncelikle akmsz nikel ile kaplanm Al2O3 seramik ve bronz tozlar kartrma ilemine tabi tutulmutur. Al2O3 tozlar hacimce % 10, 20 ve 30 olacak ekilde bronz matriks iersine ilave edildikten sonra gezegensel bilyal deirmende kartrma ilemi 2 saat sreyle gerekletirilmitir. Kartrma ileminde numune/bilya arlka oran 1/15 orannda olacak ekilde WC bilyeler kullanlmtr. Bu ilemden sonra tozlar 300 kg/cm2lik basn altnda 10 dakika sreyle souk izostatik preslenerek ham numuneler elde edilmitir. Akabinde akm destekli sinterleme yntemi ile bronz matrisli, hacimce % 10, 20 ve 30 Al2O3 takviyeli kompozit malzemeler elde edilmitir. ekil 1 deki dzenee yerletirilen numune 10 dk sreyle 2,0 V altnda ortalama 1200 A akm etkisinde braklm, malzemenin akma kar gsterdii diren sonucu aa kan syla hzla ykselen scaklklarda sinterleme ilemi gerekletirilmitir. 2.4. Kompozit Malzemelerin Karakterizasyonu retilen bronz matrisli kompozit malzemeler metalografik numune hazrlama teknikleri ile srasyla 600, 800, 1200 lk elmas zmpara kullanlarak kaba ve ince olarak zmparalanmtr. Daha sonra elmas pastalar yardmyla kaba ve ince parlatma ilemlerine tabi tutulmutur. Metalografik olarak hazrlanan yzeyler daha sonra etanol ile temizlenmi ve yzeydeki kirlilikler giderildikten sonra tozlarn dalm ve morfolojisinin belirlenmesi iin JEOL JSM 6060LV marka taramal elektron mikroskobu (SEM) ile geri salml elektron dedektr kullanlarak incelenmitir. Matristeki zellik deiimlerinin tespiti amacyla retilen kompozit numunelerin mikrosertlikleri incelenmitir. Leica VMHT MOT Mikro sertlik cihaznda her bir numune iin en az 5 alandan vickers setlik lmleri yaplm ve 5 lmn ortalamas alnmtr. lmler 15 saniye sre ile 50 gr yk altnda gerekletirilmitir. 3. Deneysel Sonular 3.1. Mikroyap almalar 3.1.1. Akmsz Nikel Kaplanm Numuneler Kompozit malzeme retiminden nce Al2O3 seramik toz yzeyleri akmsz yntem ile nikel ile kaplanmtr. ekil 2 de Al2O3 seramik tozlarnn nikel kaplanm ve kaplanmam fotoraflar grlmektedir. ekil 10 dak 10 g/l
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2a da kaplanmam Al2O3 tozlarnn temiz yzeyleri, homojen nikel kapl Al2O3 seramik tozlarnn SEM resimleri ise ekil 2b de grlmektedir. SEM resimlerinden grld gibi Al2O3 seramik tozlarnn zeri nikel ile baarl bir ekilde kaplanmtr. Nikel partiklleri seramik tozlarnn yzeyini homojen ekilde kaplam ve tozlarn keskin kelerinde youn olarak birikmitir. ekil 2c deki EDS analizinde ise Al2O3 seramik tozlarnn zerinin Ni-P ile kapland ak bir ekilde grlmektedir.
ekil 2. a)Kaplanmam Al2O3 seramik tozlar, b)Ni kaplanm Al2O3 seramik tozlar, c) Ni kaplanm Al2O3 seramik tozlarn EDS analizi. 3.1.2. Kompozit Malzemeler Bronz matrisli kompozit malzemeler, bronz iersine hacimce %10 % 20 ve %30 oranlarnda Al2O3 takviyesi yaplmak suretiyle ve akm destekli sinterleme yntemi kullanlarak retilmitir. Sinterleme ilemi btn malzemeler iin 1200 A akm altnda ve 10 dak. sre ile gerekletirilmitir. Farkl hacim oranlarnda Al2O3 ile takviye edilmi kompozit malzemelerin SEM grntleri ekil 3de verilmitir. Bronz matrisli kompozit malzemelerin mikroyap almalarnda Al2O3 seramik partikllerinin bronz matris ierisine homojen olarak daldklar grlmektedir. Al2O3 seramik partikllerin matris iersine homojen dalmn, Al2O3 partiklleri ile matris malzemesi arasnda arayzey bann iyi olmas ve alam tarafndan Al2O3 partikllerinin iyi slatabilirlilii salamtr. Seramik partiklleri ile matris arasndaki arayzeyin grnmnn de ok iyi olduu sylenebilir. Ayrca artan partikl hacim oranyla yapya daha byk partikl girmesine ramen matris partikl faz uyumunun bozulmad, partikl dalm ve homojenliinin saland da grlmektedir.
ekil 3. Bronz matrisli kompozit malzemelerin SEM grnts:a) %10 Al2O3, b) %20 Al2O3, c) %30 Al2O3
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3.2. Sertlik lmleri Numunelerin sertlik lmleri mikro-sertlik cihaznda Vickers sertlik yntemi kullanlarak yaplmtr. Sertlik deerleri, metalografik olarak hazrlanm numunelerden 50 gr yk altnda 15 sn sreyle ve 5 farkl lmn aritmetik ortalamas alnarak yaplmtr. ncelenen kompozitlerin sertlik deerleri ekil 4 de verilmitir. Takviye edilen Al2O3 seramik tozlarn hacm oranlar sonucu yapya giren partikl miktar arttka kompozit malzemenin sertliinde art grlmektedir. Kompozit malzemelerde en yksek sertlik, % 30 hacimce Al2O3 ilave edilen malzemede elde edilmitir. Bunun sebebi bronz matrisin iindeki sert Al2O3 seramik partikllerinin bulunmasndan dolay matris takviye faz arayzeyinde dislokasyon younluunun artmas ve partiklerin dispersiyon sertlemesi etkisi yapmasdr. Bylece partikller ana metal fazna gre daha sert malzemeler olarak kompozit yapnn sertliine direkt olarak takviye yapmaktadr.
ekil 4. Bronza Al2O3 ilavesiyle sertlikte meydana gelen deiim 4.Sonular Akm destekli sinterleme yntemi kullanlarak Al2O3 takviyeli kompozitler ksa srede baarl bir ekilde retilmitir. Takviye faz ile matris arasndaki ara yzeyi iyiletirmek iin Al2O3 seramik tozlarn yzeyleri akmsz nikel ile homojen bir ekilde kaplanmtr. Bronz matris iersine 80 m boyutunda hacimce %10, %20 ve %30 oranlarnda Al2O3 takviye faz ilave edilerek akmla sinterleme yntemiyle kompozit malzemeler retilmitir. Al2O3 partiklleri matris iersine homojen olarak dalarak baarl bir kompozit retilmitir. Matris iersine ilave edilen Al2O3 partikllerinin miktar arttka kompozit malzemenin sertliinde art meydana gelmitir. Kaynaklar 1. Altnsoy Almina Takviyeli Bakr Kompozitlerin retimi Ve Karakterizasyonu Yksek Lisans Tezi, , Sakarya niversitesi, Fen Bilimleri Enstits, 2009 2.Kl F. Elektrolitik Nano Sic Partikl Takviyeli Nikel Kompozitlerinin zellikleri Yksek Lisans Tezi, , Sakarya niversitesi, Fen Bilimleri Enstits, 2008 3.Sur, G., Sahin, Y., Gkkaya, H., Ergimis Metal Karstrma ve Basnl Dkm Yntemi ile Alminyum Esasl Tanecik Takviyeli Kompozitlerin retimi, J. Fac. Eng. Arch. Gazi Univ.,Vol.20, 2, 233-238, 2005 4.Gltekin, D., Metal matrisli kompozit fren diski balatas retimi ve karakterizasyonu, Yksek Lisans Tezi, , Sakarya niversitesi, Fen Bilimleri Enstits, 2007 5. Yng, D. Y., Zhang, D.L., Processing of Cu-Al2O3 metal matrix nanocomposite materials by using high energy ball milling, Materials Science & Engineering A, Vol. 286, pp. 152-156, 2000 6.Aslan, S., SiC ve Grafit takviyeli inko alminyum hibrit kompozit malzemelerin asnma davranslarnn incelenmesi, Doktora Tezi, Sakarya niversitesi, Fen Bilimleri Enstits, 2005 7.Tjong S.C. Lau K.C. Tribological behaviour of SiC particle-reinforced copper matrix composites Materials Letters Vol. 43 pp 274280 2000 8.Ramesh C.S. , Noor Ahmed R. , Mujeebu M.A. , Abdullah M.Z. Development and performance analysis of novel cast copperSiCGr hybrid composites Materials and Design Vol.30 pp 19571965(2009) 9. Karsliolu R., Uysal M., Alp A., Akbulut H., Current Actvated Snterng Of Bronze Hybrd Mmcs Coatngs On Steel Substrates 5th International Powder Metallurgy Conference October 8-12, 2008 Ankara TURKEY
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Cu + % 5 Al/ Cr3C2 TOZU LE KAPLANAN TABAKALARIN YAPIMA MUKAVEMET VE YZEY PRZLLNN NCELENMES
Serkan ZEL* ve Hseyin TURHAN** *Bitlis Eren niversitesi, Mhendislik ve Mimarlk Fakltesi, Makina Mhendislii Blm, 13000, Bitlis, sozel@beu.edu.tr ** Frat niversitesi, Teknik Eitim Fakltesi, Metal Eitimi Blm, 23119, Elaz, hturhan@firat.edu.tr ZET Bu almada, Cu + 5 % Al toz karm ierisine farkl yzdelerde ilave edilen Cr3C2 tozlar, atmosferik plazma pskrtme teknii kullanlarak Cu alam yzeyine kaplanmtr. Cu + 5 % Al ierisine % 5, % 10 ve % 20 Cr3C2 oranlar kullanlarak yaplan kaplamalarda Cr3C2n yzeye yapma mukavemeti ve yzey przllne olan etkisi incelenmitir. Bu amala, kaplanan tabakalara ekme deneyi uygulanm ve yzey przllk deerleri llmtr. Deney sonular incelendiinde, Cu + 5 % Al/ Cr3C2 tozlar ile kaplanan tabakalarn yapma mukavemetleri arayzey balanmasnn az olmasndan dolay dk seviyelerde kmtr. Cr3C2 ilavesine bal olarak yzey przll deerinin artt tespit edilmitir. Anahtar Szckler: Plazma Pskrtme, Cr3C2 tozu, Yapma mukavemeti, Przllk.
THE INVESTIGATION OF BONDING STRENGHT AND SURFACE ROUGHNESS OF COATNG LAYERS WITH Cu + 5 % Al/ Cr3C2 POWDERS
ABSTRACT In this study, the Cr3C2 added at different concentrations (5, 10 and 20 wt.%) to the Cu + 5 % Al content powders were coated on the surface of Cu alloy by using the atmospheric plasma spraying (APS) method. The effect of Cr3C2 on bonding strenght and surface roughness was examined in four different coatings. For this aim, bonding strenght and surface roughness values were measured. The results showed that the bonding strenght of coating layer with Cu + 5% Al / Cr3C2 powders are low because of the low interfacial adhesion. The surface roughness values were increased depending on the addition of Cr3C2. Keywords: Plasma Spraying, Cr3C2 powder, Bonding strenght, Roughness. 1. GR Gelien teknoloji ile metal ve alamlarnn yzeyleri, yksek scaklk, anma ve korozyon dayanmn arttrmak amac ile eitli kaplama ilemlerine tabi tutulmaktadr. Isl pskrtme kaplama teknikleri, tel veya toz halindeki kaplama malzemelerinin bir pskrtme tabancasnda tayc, yanc ve yakc gazlarn eliinde pskrtlerek altlk zerinde biriktirilmesi ve koruyucu tabakann elde edilmesi esasna dayanan ilemlerdir [1]. Toz pskrtmede, ince toz paracklar yksek s kaynann iinden geerek ergimi ya da yar ergimi duruma gelirler. Ergiyen kaplama malzemesi kaplanacak olan parann souk olan yzeyine pskrtlr. Yzeye darbe etkisiyle arpan tanecikler, dzlemekte ve esas metale olan s transferi ile souyarak katlamaktadr. Birbirleri ile temas haline gelen bu tanecikler malzeme yzeyinde kaplama tabakasn meydana getirmektedirler [2]. Metallerden ve oksitlerden, oksit seramik ve
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cams metallere kadar geni bir dalm aralndaki malzemeleri ieren sl pskrtme kaplamalar, ana malzemenin beklenilmeyen ve gereksiz olan hasarndan dolay bata reticiler olmak zere herkesin dikkatini ekmektedir. Paray tamamen yenilemek iin gerekli olan masrafn az bir ksm ile ve eitli sl pskrtme yntemleri ile uygulanan yeni yzey malzemesi, bu tr paralara ilave mr kazandrmaktadr [3]. Plazma pskrtme yntemi, sl pskrtme tekniklerinin ierisindeki kaplama yntemlerinden bir tanesidir. Plazma pskrtme yntemi ile sl bariyer, anma direnci, korozyon direnci gelitirilmi ve biomedikal amal zel kaplamalar yaplabilmektedir [4, 5, 6]. Sert krom kaplamalar, mhendislik uygulamalarnda (havaclk, otomotiv, denizcilik vb.) kullanlan valf, piston, ubuklar ve birok dier paralar gibi kritik mekanik bileenlerin yzey zelliklerini gelitirmede yaygn olarak kullanlmaktadr [2]. Krom karbr, son derece sert olan refrakter bir seramik malzemedir. Krom karbr, metal malzemelerin yzeylerinin sert olmasnn, korozyona ve anmaya kar dayankl olmasnn istenedii yerlerde sl pskrtme malzemesi olarak kullanlmaktadr [7,8, 9]. Bu almada, Cu alam yzeyine Cu + 5 % Al/ Cr3C2 tozlar plazma pskrtme yntemi ile kaplanmtr. Kaplama deneyleri sonunda numunelerde, kaplama tabakasnn yzeye yapma mukavemeti ve kaplama sonras yzey przllk deerlerine farkl oranlarda ilave edilen Cr3C2n etkisi aratrlmtr. 2. DENEYSEL ALIMALAR Alt malzeme olarak kullanlan Cu alam, % 5 Al, % 2 Fe ve % 2 Ni katk oranlarnn bakr ierisine katlmasyla meydana gelmitir. 100 x 20 x 5 mm llerinde hazrlanan bakr alam numuneler, yzey przllnn salanmas amac ile 60 PSIlik basn altnda Al2O3 kullanlarak yzey przlendirme ilemine tabi tutulmutur. Yzey przlendirme ilemine tabi tutulan numunelerin yzeylerine, Cu + %5 Al ierisine farkl yzdelerde ilave edilen Cr3C2 tozlar ile elde edilen toz karmlar kaplanmtr. Bu toz karmlarna ait karm yzdeleri Tablo 2de verilmitir. Kaplama tabakasna ilave edilen Cr3C2 + 7 % (Ni20Cr) tozun SEM fotoraf ekil 1de grlmektedir. Tablo 1. Cu + % 5 Al tozu ve Cr3C2 tozunun (%) karm oranlar. Numuneler A1 A2 A3 A4 Kaplama Tozlar (%) Karm Oranlar Cu + % 5 Al 100 95 90 80 *Cr3C2 0 5 10 20
* Cr3C2 tozu METCO 430NS kodu ve Cr3C2 + 7 % (Ni20Cr) bileimi ile standart bir tozdur.
ekil 1. Cr3C2 + % 7 (NiCr) tozunun SEM fotoraf. Plazma pskrtme kaplama ilemleri atmosferik plazma pskrtme kaplama nitesindeki 3 MB tabancasnn elle kullanlarak uygulanmas ile gerekletirilmitir. Plazma pskrtme ynteminin ematik grn ekil 2de verilmitir. Kaplamada kullanlan plazma pskrtme parametreleri Tablo 2de verilmitir.
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ekil 2. Plazma pskrtme kaplama sisteminin ematik grn. Tablo 2. Cu + Al + % Cr3C2 karbr karm tozlarna ait kaplama parametreleri. Parametreler Akm Gerilim Sprey Mesafesi Plazma Gaz Tayc Gaz Nozul ap Toz Besleme Oran Cu + Al + Cr3C2 Tozu 400 A 70 V 100 mm 145 l/dk Ar 10 l/dk H2 37 l/dk Ar 7,6 mm 53 g/dk.
Kaplama sonras, kaplama tabakalarnn st yzeylerinden yzey przllk lmleri Mitutoyo Surftest-211 marka cihazda ayn yzeyin farkl blgelerinden lmler tekrarlanp aritmetik ortalamas hesaplanarak tespit edilmitir. Kaplama tabakalarnn ba mukavemet deerleri, ASTM C-633 standartna uygun olarak hazrlanan numuneler ile ekme deneyine tabi tutularak tespit edilmitir. ekme deneyi iin 25,4 mm apnda dairesel test kuponlar kullanlmtr (ekil 3-a). Ayn parametrelerle kaplama ilemine tabi tutulan ekme deney test kuponlar, zel epoksi yaptrclar ile ekme deney balklarna yaptrlm ve 2 saat sre ile 200 C scaklkta bekletilerek kurutma ilemine tabi tutulmutur (ekil 3-b). Kurutma ilemi sonrasnda ekme deney balklar, ekil 4te verilen ekme deney cihaz ile yapma mukavemeti testine tabi tutularak kaplama tabakas ile altlk malzeme arasndaki yapma mukavemet deerleri tespit edilmitir.
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ekil 3. a) Kaplanacak numuneler ve ekme deneyinde kullanlacak test kuponlar, b) ekme testi deney balklar ve test numunesi.
ekil 4. Dillon marka ekme deney cihaz. 3. DENEYSEL SONULARIN NCELENMES 3.1. Kaplamalarn Yapma Mukavemet Deerleri Kaplanm numunelere ekme deneyi sonras tespit edilen yapma mukavemetlerine ait grafik ekil 5te verilmitir. Numunelerin yapma mukavemet deerleri incelendiinde, plazma pskrtme kaplamalar iin n grlen mukavemet deerlerinin (34-69 MPa aras) [10] altndaki seviyelerde olduu grlmtr. Yapma mukavemeti deerlerindeki bu dklk, arayzeyle ilgili olarak Yeildal ve Gney [11] tarafndan belirtilen, kaplama tabakas ile bakr alamndan oluan alt malzeme arasnda oksit tabakas oluumlarnn varlndan ileri gelmektedir (ekil 6). Plazma pskrtme yntemi ile gerekletirilen kaplamalarda, kaplama esnasnda alt malzemenin snmas sz konusudur. Cu alam alt malzememizin yzeyinin genelinde bu snmadan dolay bir oksit film tabakas olumaktadr. Cu + % 5 Al + Cr3C2 ile kaplanan numunelerde kaplama tabakas alt malzemeye, yzeydeki oksit tabakasna bal olarak oluan gzenekten dolay tam olarak balanamamtr. Ara yzeyde gzenekli bir yap elde edilmitir. Arayzeyde oluan bu gzenekler, kaplama tabakas ile alt malzemenin yapma mukavemetini drmtr. Yapma mukavemeti en dk seviyede 7,96 MPa deeri ile Cu + % 5 Al tozu ile kaplanan A1 numunesinde tespit edilmitir. Cu + % 5 Al toz ierisine ilave edilen Cr3C2 tozu ile yapma mukavemet deeri artmtr. Ara yzeydeki tutunmaya bal olarak en yksek yapma mukavemeti 19,16 MPa deeri ile % 10 Cr3C2 ilaveli A3 numunesinde tespit edilmitir.
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ekil 5. A grubu numunelere ait yapma mukavemeti deerleri.
ekil 6. A grubu numunelerde ara yzeydeki oksite bal olarak oluan gzenekler. 3.2. Kaplamalarn Yzey Przll Deerleri Kaplama ileminde numunelerin, kaplama ncesi, yzey przlendirme ilemi sonras ve kaplama sonras yzey przllk deerleri llmtr (ekil 7). lmlerde; hehangi bir ilem uygulanmam numunede 3,824 m ve yzeyi sadece przlendirilmi numunede de 5,125 m yzey przllk deerleri tespit edilmitir. Numune yzeyine yaplan kaplamalar ile A1, A2, A3 ve A4 numunelerinde farkl yzey przllk deerleri tespit edilmitir. Yzeye Cu + % 5 Al tozu kaplanan A1 numunesinde 5,28 m przllk deeri elde edilmitir. % 5 Cr3C2 tozu ilaveli A2 numunesinde yzey przll 8,75 m llrken; % 10 Cr3C2 tozu ilaveli A3 numunesinde 8,43 m ve % 20 Cr3C2 tozu ilaveli A4 numunesinde de 8,13 m yzey przllk deerleri tespit edilmitir. ekil 6da grld gibi Cu + % 5 Al tozu ile kaplanan A1 numunesinde; A2, A3 ve A4 numunelerine gre daha iyi bir yzey kalitesi olumutur. lave edilen Cr3C2 ile kaplama tabakasnn ergime scakl olaanst ykselmekte, taneciklerin birbiriyle olan sinterlemesi ktlemekte ve bu da yzey przllnn bir miktar ykselmesine neden olmaktadr. A1 numunesinde yzey przllnn en dk olmas bu numunenin tamamyla istenen kalitede olduunu gstermez. Cu + % 5 Al tozu ierisine ilave edilen Cr3C2 ile yzey przllk deeri artmtr, fakat ilave edilen Cr3C2 miktarnn artmas ile yzey przllk deeri derek yzey kalitesi ksmen iyilemitir.
ekil 7. A grubu numunelere ait alt malzeme ve kaplanan numunelerin yzey przllk deerleri.
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4. Sonular Plazma pskrtme yntemi ile Cu alam yzeyine Cr3C2 tozlarnn kaplanmas gerekletirilmitir. Kaplama ilemi sonrasnda numunelere uygulanan yapma mukavemeti testi sonucunda, alt malzemenin kaplama esnasnda oksitlenmesi ve buna bal olarak ara yzeyde gzenek oluumunun meydana geldii tespit edilmitir. Bu nedenle kaplama tabakalarnn tmnde standart deerlerin altnda bir yapma mukavemeti deeri llmtr. En yksek yapma mukavemeti A3 nolu numunede 19,16 MPa deeri ile tespit edilmitir. Numunelere uygulanan yzey przllk testinde, ilave edilen Cr3C2 ile yzey przllk deerinin artt ve en dk yzey przllnn A1 nolu numunede 5,28 m deeri ile olutuu grlmtr. Teekkr Bu alma, FBAP-1471 nolu proje ile maddi olarak desteklenen bir doktora tez almasdr. Bu proje ile maddi destek salayan Frat niversitesi Bilimsel Aratrma Projeler (FBAP) Birimine, kaplamalarn yaplmasnda ve ekme deneyinde yardmc olan THY Teknik A.. ve alanlarna sonsuz kranlarmz sunarz. KAYNAKLAR 1. . Ylmaz, E. Ercenk, C. Bindal, AISI 316L elii zerine Plazma Sprey Yntemi le Kaplanm Al2O3 ve Al2O3 - % 13 TiO2 Kaplamalarn zelliklerine Ba Tabakann ve Al Katksnn Etkisi, 13. Uluslararas Metalurji Ve Malzeme Kongresi, s. 690-696, stanbul, 2006. 2. S. zel, Alminyum alam ve bronzu yzeyine oksit ve karbr bileiklerinin plazma sprey yntemiyle kaplanmasnn aratrlmas, Doktora Tezi, Frat niversitesi Fen Bil. Ens., 2009. 3. N. Y. Sar, E. Kalu, K. Tlbenti, Alevle Isl Pskrtme Uygulanarak 1050 (C45 E) eliinin Abrazif + Erozif Anma Davrannn yiletirilmesi, Kaynak Teknolojisi II. Ulusal Kongresi, s. 177-185, Ankara, 1999. 4. S.B. Mishra, K. Chandra, S. Prakash, B. Venkataraman, Characterisation and erosion behaviour of a plasma sprayed Ni3Al coating on a Fe-based superalloy, Materials Letters, Vol. 59, pp. 3694 3698, 2005. 5. G. Bolelli, V. Cannillo, L. Lusvarghi, T. Manfredini, Glass-alumina composite coatings by plasma spraying. Part I: Microstructural and mechanical characterization, Surface & Coatings Technology, Vol. 201, pp. 458473, 2006. 6. S. zel, H. Turhan, F. Sarslmaz, AA2024 Alminyum Alam Yzeyine Al2O3/Al2O3+TiO2 Tozunun Plazma Sprey Yntemiyle Kaplanmas, Frat niversitesi Fen ve Mhendislik Bilimleri Dergisi, 20 (3), s. 503-508, 2008. 7. J.M. Guilemany, N. Espallargas, P.H. Suegama and A.V. Benedetti, Comparative study of Cr3C2 NiCr coatings obtained by HVOF and hard chromium coatings, Corrosion Science, Vol. 48, 10, pp. 2998-3013, 2006. 8. G. C. Ji, C. J. Li, Y. Y. Wang and W.Y. Li, Microstructural characterization and abrasive wear performance of HVOF sprayed Cr3C2NiCr coating, Surface and Coatings Technology, Vol. 200, 24, pp. 6749-6757, 2006. 9. N. Espallargas, J. Berget, J.M. Guilemany, A.V. Benedetti and P.H. Suegama, Cr3C2NiCr and WCNi thermal spray coatings as alternatives to hard chromium for erosioncorrosion resistance, Surface and Coatings Technology, Vol. 202, 8, pp. 1405-1417, 2008. 10. R. C. Tucker, Thermal Spray Coatings, Vol. 5: Surface Engineering, ASM Handbook, ISBN: 0-87170-384-2, Ohio, pp. 499-509, 1994. 11. R. Yeildal, Y.Z. Gnay, Plazma sprey yntemi ile kaplama ve sprey karakteristiklerinin incelenmesi, DE Mhendislik Fakltesi Fen ve Mhendislik Dergisi, 9, 1, s. 59-76, 2007.
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MAGNEZYUM BOLUK YAPICI KULLANILARAK RETLEN TiNi KPKLERNDE BASMA VE SPERELASTSTE DAVRANII
*
ZET Bu almada boluk yapc olarak magnezyum kullanlarak retilen, % 38-59 gzenee sahip Ti-50.6 at %Ni kpklerinin basma ve sperelastisite davranlar incelenmitir. Kresel gzeneklere sahip stenitik TiNi kpkleri farkl scaklklarda dngsel olarak basma yklemesine ve boaltmaya tabi tutulmutur. Mukavemet, Young modl ve martensit oluturmak iin gereken kritik gerilmenin artan gzenek miktar ile ters orantl olduu bulunmutur. Kpklerin ksmi sperelastisite gsterdikleri gzlemlenmi, geri kazanlamayan gerinme miktarlarnn artan test scakl ile azald grlmtr. Dngsel ykleme-boaltma sonras % 5e kadar gerinimin tamamyla geri kazanld tespit edilmitir. % 38-51 gzeneklilikteki TiNi alamlarnn kemik implantasyonu gibi biyomedikal uygulamalarn gerektirdii mekanik zellikleri karlad sonucuna varlmtr. Anahtar kelimeler: TiNi Kpkler, Martensitik Dnmler, Sperelastisite, Biyomedikal Uygulamalar, Dngsel Basma.
COMPRESSION AND SUPERELASTICITY BEHAVIOR IN TiNi FOAMS PRODUCED USING MAGNESIUM SPACERS
ABSTRACT In the present study, compression and superelasticity behavior of Ti-50.6 at %Ni foams with porosities in the range 38-59% and produced by use of magnesium powders as space holders were investigated. Austenitic TiNi foams with spherical pores were subjected to loading-unloading cycles under compression at different temperatures. It has been found that strength, elastic moduli and critical stress for inducing martensite were inversely correlated with increasing porosity. Partial superelasticity was observed for all the foams and unrecovered strain was found to decrease with increasing test temperature. Strains up to 5% were recovered fully after cyclic loading-unloading. TiNi foams produced with porosities in the range of 38-51% meet the main requirements of biomaterials in terms of mechanical properties for use as bone implant. Keywords: TiNi Foams, Martensitic Transformations, Superelasticity, Biomedical Applications, Cyclic Compression. 1. GR Metalik kpkler, polimer ya da seramik gibi dier malzemelerden retilmi kpklere benzer ekilde srad fiziksel ve mekanik zellikler gsterirler. Dk younluklarna ramen yksek rijitlik, yksek gaz geirgenlii ile yksek
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termal iletkenlik gsterirler. Bu birbirine zt zellikleri birarada iermeleri nedeniyle otomotiv, havaclk, demiryolu, ve inaat endstrilerinde yapsal amal kullanmlarnn yansra, susturucu, pil elektrodlar, sv depolama ve transferi aygtlar gibi fonksiyonel uygulamalarda da ska kullanlmaktadrlar [1]. Metalik kpkler iin dier nemli bir uygulama alann biyomalzeme sektr oluturmaktadr. Bu uygulamalarn byk bir blmnde kpn hem yapsal hem de fonksiyonel zelliklerinden yararlanlmaktadr. ekil bellek etkisi ve sperelastisite gibi iki srad fonksiyonel zellik gsteren TiNi kpkler biyomedikal uygulamalarda ne kan alamlar olmutur. Bu zellikler sayesinde TiNi kpkler implant yaplacak blgeye kolaylkla yerletirilebilmekte ve vcut dokularyla ok iyi bir temas salanabilmektedir [2]. Vcut iinde yer alan canl dokular ve kemiklerin % 2 civarndaki gerinimleri tamamyla geri kazanabildikleri tespit edilmitir [3]. Bu davrana benzer bir mekanik davran gsteren sperelastik TiNi alamlar bu adan da dier kpklere gre nemli bir avantaja sahiptir. Biyouyumluluu kantlanm olan [4,5] TiNi kpklerin implant malzemesi olarak kullanlabilmeleri iin yeterli gzenek miktar, uygun gzenek boyutu ve gerekli mekanik zellikleri salamas zorunludur. Bu almada magnezyum (Mg) boluk yapc tozlar kullanlarak retilen tek fazl, kresel gzenekli TiNi kpklerin yapsal ve fonksiyonel zellikleri tespit edilerek implant malzemesi olarak kullanlmalarnn uygun olup olmad belirlenmeye allmtr. zellikle mekanik basma ve sperelastisite davranlar sistematik deneylerle aratrlm, bu zelliklerin gzeneklilik, scaklk ve dngsel ykleme-boaltmayla olan deiimleri ortaya konulmutur.
2. DENEYSEL YNTEM 2.1. Kullanlan Tozlar ve retim Yntemi TiNi kpkleri retmek iin balang tozlar olarak nikelce zengin (Ti-50.6 at. %Ni, % 99.9 saflkta, Nanoval GmbH & Co. KGdan temin edilmi), ortalama ap 21 m olan, inrt gaz atmosferi altnda atomizasyon yntemiyle retilmi, kresel TiNi alam tozlar kullanlmtr. Boluk yapc olarak ise 100-600 m aralnda elenen ve eleme sonras ortalama 450 m apnda olan, yine inrt gaz altnda atomize etmek suretiyle retilmi, kresel Mg tozlar (% 99.82 saflkta, Tangshan Weihao Magnesium Powder Co. LTDden satn alnm) kullanlmtr. TiNi tozlarnn i yaps sadece B2 stenit fazndan olumaktadr [6-7]. retim yntemi daha nceki almalarmzda optimum hale getirdiimiz ve uyguladmz [7-9] yntemin aynsdr. Mg boluk yapc miktar uygun mekanik zellikleri elde edebilmek iin bu almada hacimce % 20-50 aralnda ayarlanmtr. Balayc yardmyla kartrlan tozlar, 400 MPa basn altnda ift ynl presleme sonras 1100 C scaklkta, koruyucu argon atmosferi altnda 1 saat sreyle sinterlenmilerdir. % 50 Mgden daha az Mg ieren kompaktlar sinterleme esnasnda toplam Mg miktar % 50 olacak ekilde ekstra Mg, koruyucu olarak, ilave edildikten sonra sinterlenmitir. Frn stma hz 10 C/dak olarak sabit tutulurken, sinterleme sonrasnda pota frnn souk blgesine ekilerek yaklak 60-75 C/ dak bir hzda numunelerin oda scaklna soutulmalar salanmtr. 2.2. Karakterizasyon Sinterlenen numunelerin younluk ve gzenek miktar Arimet yntemi kullanlarak llmtr. Gzenek boyutlar ve dalm, Noran System 6 enerji dispersiv spektrometresine sahip Jeol JSM 6400 taramal elektron mikroskobunda (SEM) kk bytmelerde (10X, 20X) alnan grntlerin Clemex Vision, professional edition, version 3.5.020 grnt analiz programnda deerlendirilmesiyle tespit edilmitir, (ekil 1). TiNi kpklerin dnm scaklklar Perkin Elmer Diamond diferansiyel taramal kalorimetresi (DSC) ile 10 C /dak stma ve soutma hzlar kullanlarak belirlenmitir. Basma ve sperelastisite testleri 10X10 mmlik silindirik numuneler kullanlarak 30 kN kapasiteli, stma haznesi olan Instron 3367 mekanik test cihaz yardmyla 0.1 mm/dak basma hzyla gerekletirilmitir. Elastik modl deerleri gerilim-gerinim diyagramnn dorusal ksmndan hesaplanrken, stenit-martensit dnm gerilimi % 0.2-offset metodu ile hesaplanmtr. Sperelastisite testleri 0-250 MPa aralnda dngsel ykleme ve boaltmalarla farkl scaklkta yaplmtr: oda scakl (25 C), vcut scakl (37 C) ve stenit biti (Af) scaklnn 10-20 C zerindeki bir scaklk. Uygulanan maksimum gerilim deeri yksek gzenekli numuneler iin dk tutulurken azalan gzenek miktar ile birlikte artrlmtr.
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ekil 1. Clemex Vision grnt analiz programnda % 59 gzenekli TiNi kpn gzenek boyutlarnn ve dalmnn belirlenmesi. 3. BULGULAR VE DEERLENDRME 3.1. Gzeneklilik, Gzenek Boyutu ve Dalm ekil 2den grld gibi artan Mg miktaryla younluun dorusal olarak derken gzenek miktarnn dorusal olarak ykseldii gzlenmitir. retilen tm numunelerde toplam gzenekliliin eklenen Mg miktarndan fazla olduu grlmektedir. Bunun nedeni TiNi tozlarn iinde atomizasyon srasnda oluan boluklar ve TiNi tozlar arasnda yer alan ksmi sinterlemeden kaynaklanan mikro-boluklardr. % 20 Mg eklenmi kpkteki gzenek miktar % 38 iken, % 50 Mg eklenmi kpkteki gzenek miktar % 59 olmutur. Karmdaki Mg miktar artarken TiNi tozu miktar azalmaktadr bu yzden de TiNi tozlar arasnda oluan mikro-boluklarn says da azalmaktadr. Dolaysyla eklenen Mg miktar arttka toplam gzeneklilikteki art daha az olmaktadr. Eklenen Mg miktarndan bamsz olarak makro-gzenek boyutu 380 130 m olarak belirlenmitir. ekil 3 % 20 ve % 50 Mg boluk yapc ilave edilerek sinterlenen dolaysyla farkl miktarda gzenek ieren iki farkl numunedeki makro-gzeneklerin boyut dalm erisini vermektedir. Her iki kmlatif eri incelendiinde gzeneklerin % 90dan fazla bir ksmnn 130-650 m aralnda olduu grlmektedir. Gzenekler Mgun buharlamasyla olutuu iin gzenek boyutu dalm da kullanlan Mg tozun dalm ile bir paralellik gstermektedir. Mevcut almada retilen tm kpklerde ak gzeneklilik oran % 95 ve zeri olarak belirlenmitir. Dk gzenek miktarlarnda dahi bu orann yakalanmas mikro-gzeneklerin varl ile aklanabilir.
ekil 2. Younluk ve gzenekliliin eklenen Mg miktar ile deiimi.
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Biyomedikal uygulamalarda kemik dokunun implant malzemesi iinde geliimi iin 100-600 m arasnda deien gzenek boyutlar istenilmektedir [10]. Bunun yannda yapay kemik deiimi uygulamalar iin gzenek miktar % 30-90 aralnda olmaldr [2]. Ayrca kemik bymesi ve vcut svlarnn tanm iin gzenekler ak tipte ve birbirleriyle balantl olmaldr. Bu bilgilerin nda, retilen TiNi kpklerin btn gzenek miktarlarnda yapay kemik implant olarak istenilen tm yapsal artlar salad grlmektedir. 3.2. Mikroyap ve Dnm Scaklklar retilen btn kpklerin mikroyaps balangta kullanlan TiNi tozlarnn mikroyaps ile ayndr. Tm kpkler yalnzca B2 stenit fazn iermektedirler. Mikroyap ile ilgili detayl bilgiler daha nceki almalarmzda [7-9] verilmitir. DSC erilerinden elde edilen ve izelge 1de verilen dnm scaklklarndan grld zere Af scaklklar vcut scakl civarndayken martensit balama (Ms) scaklklar oda scaklnn altndadr. Bu sonular da XRD verilerini (burada verilmemitir) desteklemektedir, yani tm kpkler oda scaklnda sadece stenitten olumaktadrlar.
ekil 3. (a) % 20 (b) % 50 Mg ilave edilerek retilen numunelerde sinterleme sonras gzenek dalm. izelge 1. TiNi kpklerin dnm scaklklar. Gzeneklilik (%) Ms 38 43 51 59 17 6 15 5 Dnm scaklklar (C) Mf -28 -34 -37 -40 As 12 21 15 8 Af 42 36 40 33
3.3. Mekanik Basma ve Sperelastisite ekil 4 farkl gzenek oranlarna sahip TiNi alamlarnn oda scaklndaki gerilim-gerinim diyagramlarn vermektedir. Gzenekli TiNi kpkler retim sonras herhangi bir termomekanik ileme tabi tutulmamlardr. ekilden de grld zere mukavemet, elastik modl ve martensit oluturmak iin gereken kritik gerilim artan gzenek miktaryla azalmaktadr. Sperelastisite mekanizmasyla geri kazanlabilen gerinim miktar da gzenek miktarnn azalmasyla art gstermektedir. rnek olarak % 38 gzenekli TiNi alamnda % 7.7 lik bir gerinim uygulandktan sonra sadece % 2.7lik bir kalnt gerinim kalmaktadr. te yandan daha yksek gzenee sahip (% 51) numune ise benzer bir gerinime kadar deforme edildiinde (% 7.2) geri dnemeyen kalc gerinim miktar % 3.75 dzeyindedir.
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ekil 4. Farkl gzeneklilikteki TiNi kpklerin oda scaklndaki gerilim-gerinim erileri. Sperelastik gerinim kazanmnn tam olmamas da ekil 4ten aka gzlenmektedir. Bunun nedeni test scaklnn Af scaklndan daha dk olmas veya geri dnm mmkn olmayan plastik deformasyonun martensitik dnme elik etmesi olabilir. Her iki etki ayn anda da grlebilir. Tam bir sperelastik dngnn gerekleebilmesi iin iki temel unsurun karlanmas gerekmektedir. lk olarak deformasyon yalnzca martensitik dnmle gereklemeli dislokasyon hareketi ile meydana gelen kayma mekanizmas aktif olmamaldr. Bunun salanabilmesi iin kayma iin gereken kritik gerilimin martensitik dnmn mmkn hale gelmesini salayan kritik gerilimden daha yksek olmas gerekmektedir. kinci olarak test scakl malzemenin Af scakl deerinden daha yksek olmaldr. Bu art salanmazsa oluan martensit faz test scaklnda stabil olacandan ykn kaldrlmasyla birlikte stenit fazna dnmeyecektir. Deformasyon srasnda dnm scaklklarnn artmas da bilinen bir gerektir. Bu scaklk artn telafi etmek iin genellikle sperelastisite testleri Af scaklnn 10-20 C zerindeki bir scaklkta yaplrlar [11] ve en iyi ekil geri kazanm (tam bir sperelastik dng) bu scaklklarda salanr. Md diye tanmlanan ve hemen altnda gerilim ile martensit oluturulabilen maksimum bir scaklk vardr. Her ne kadar bu scakla kadar sperelastisite mmkn olsa da tam bir sperelastik dng dar bir scaklk aralnda elde edilebilir. nk artan scaklkla birlikte martensitik dnm iin gereken gerilim artmakta iken kayma iin gereken gerilim azalmaktadr.
ekil 5. % 51 gzenekli TiNi kpn gerilim-gerinim erilerinin ve sperelastisite davrannn scaklkla deiimi. ekil 5 farkl scaklklarda % 51 gzenee sahip TiNi alamlarnn gerilim-gerinim erilerini gstermektedir. Dayan, Young moduli ve martensit oluturacak kritik gerilme artan scaklkla birlikte art gstermektedir. izelge 2 ayn numunelerde ve % 59 gzenekli TiNi kpklerde geri kazanlamayan gerinim miktarlarn zetlemektedir. Artan scaklkla birlikte kalnt gerinimlerin miktarndaki dme aka grlmektedir. ekil 5 ve izelge 2 ayn anda analiz edilirse geri kazanlamayan gerinimlerin nedeninin deformasyonun sadece martensitik dnmle deil ayn zamanda kayma mekanizmasyla gereklemesi olduu grlecektir. Af scaklnn zerindeki scaklklarda yaplan testlerde bile kalnt gerinimlerin olmas bu sonucu desteklemektedir. Oda scakl ya da vcut scaklnda test
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edilen numuneler daha sonra Af scaklklarnn zerine stldklarnda bir miktar gerinimi daha kazandklar tespit edilmitir. Yine de mutlak bir miktar gerinim her zaman kalmtr. rnein % 51 gzenekli numunede oda scaklndaki ykleme-boaltma admlarndan sonra kalan % 3.75lik gerinim Af scaklnn zerine stldnda % 1.8e dmtr. Buradan martensitik dnmle birlikte kayma mekanizmasnn da altn syleyebiliriz. izelge 2. ki farkl gzenee sahip gzenkli TiNi alamlarnn farkl scaklklarda testi sonucu kazanlmayan gerinim miktarlar. Geri kazanlmayan gerinim (%) Gzeneklilik (%) Oda scakl 51 59 42 51 Vcut scakl 32 31 T>Af (60 C) 22 26
ekil 6 oda scaklnda sabit gerilim altnda yaplan dngsel ykleme ve boaltma testlerinin sperelastisite zerindeki etkilerini gstermektedir. Kalnt gerinim miktarnda artan dng saysyla birlikte bir d gzlenmitir ve 5. dng sonunda ekil 6 (b) den de grlecei zere kalnt gerinim miktar sfra inmitir. Bu tespit farkl gzeneklere sahip TiNi alamlarnn hepsi iin geerlidir. 4 ya da 5. dngnn sonunda geri kazanlamayan gerinim hemen hemen olmamtr.
ekil 6. Sabit gerilimde yaplan dngsel ykleme ve boaltmalarn TiNi kpklerin sperelastisite zellikleri zerindeki etkisini gsteren gerilim-gerinim erileri (a) ve (b) % 51 gzenekli, 10 dng 125 MPada, (c) % 43 gzenekli, artan gerilimlerde dngler.
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ekil 6 (c) % 43 gzenee sahip TiNi kpn tipik gerilimgerinim erisini gstermektedir. Testler 6 farkl gerilim deerinde ilkinde 10 dng sonrakilerde 5 dng olmak zere yaplmtr. lk dngden sonra yaplan ikinci ykleme esnasnda dorusal bir deformasyon davran gzlenmektedir. Gerilim miktar artrldnda da deformasyonun bir nce uygulanan gerilim miktarna kadar dorusal ilerledii daha sonra dorusallktan saparak klasik bir ekilde devam ettii grlmektedir. TiNi kpklerin basma ve sperelastisite davran hacimli (gzenek iermeyen) TiNi alamlarnnkinden bariz bir ekilde farkllk gstermektedir. Hacimli TiNi alamlar optimum artlarda retilip gerekli termomekanik ilemler uygulandnda belirli gerilim deerlerinde tam bir sperelastik dng davran sergilerler. Fakat ekme esnasnda hem ileri (stenitten martensite) hem de geri (martensitten stenite) ynde olan dnmler neredeyse sabit ya da ok az eimli gerilimlerde vuku bulurken basma durumunda bu eim artmaktadr. Gzenekli malzemelerde uygulanan yk hcre duvarlar tamaktadr. Bu almadaki gibi ksmi sinterleme ile retilen ve makro-gzeneklerin yannda mikro-gzenekler de ieren alamlarda uygulanan yk byk bir ounlukla sinterleme boyunlar tarafndan tanmaktadr. Yap ierisinde rastgele olumu farkl boyut, ekil ve farkl ynlenmelerde bir ok sinterleme boynu mevcuttur. Uygulanan yk her ne kadar ayn olsa da sinterleme boyunlar kanlmaz olarak farkl gerilimlere maruz kalacaktr. Sonu olarak da her bir boyun farkl zamanlarda martensitik ya da stenitik dnme urayacaklardr. Ayn ekilde farkl zamanlarda plastik deformasyona da urayabilirler. Bu yzden deformasyon sabit bir gerilim seviyesinde ilerlemek yerine gittike artan gerilimlerde gereklemektedir. Bu da sabit ya da az eimli gerilimlerin TiNi kpklerin basma testi srasnda neden gzlemlenemediini aklamaktadr. Ykleme esnasnda martensitik dnmlerin balamas iin gereken kritik gerilim de ayn ekilde sabit olamaz. Aslnda sabittir ama herbir boyun bu gerilime fakl zamanlarda ya da dier bir deyile farkl uygulanan gerilim deerlerinde ular. Bu yzden elastik deformasyon blgesinde dahi martensitik dnmler ya da plastik deformasyon meydana gelebilir. Sperelastik TiNi kpklerin elastik modllerinin dk olmasnn nedeni byle aklanabilir. Gzlenebilen ya da % 0.2 off-set metoduyla bulunabilecek kritik gerilime ulaldnda ilk yklemede dorusallktan sapma grlmektedir. Bu gerilimden itibaren plastik deformasyonun ciddi bir biimde arttn sylemek mmkn grnmektedir. Ayn gerilim deerine yeniden ykleme yapldnda yeni dislokasyon hareketleri olmayacaktr ve deformasyon sadece elastik deformasyon ve martensitik dnmler yolu ile gerekleecektir. Bu ykleme esnasnda neredeyse tamam ile dorusal bir gerilim-gerinim davrannn grnmesi plastik deformasyonun ilk yklemedeki dorusallktan sapmann balad gerilimden itibaren gerekletii tezini dorulamaktadr. Bylelikle ikinci ykleme sonrasnda gerinimin tamam geri kazanlacaktr. Elbette test scaklnn Af scaklndan uygun miktarda yksek olmas ve martensit stabilizasyonunun (ar deformasyon nedeniyle) olumamas artyla. Biyoimplantasyon amacyla kullanlabilecek TiNi kpklerinin mekanik zellikler asndan yksek dayan (en az 100 MPa % 2 gerinimde) ve % 8lik gerinime yklendikten sonra % 2den daha fazla gerinimi geri kazanmas gibi temel nartlar yerine getirmeleri zorunluluu vardr [2]. Gerinim kazanm miktar koulunu retilen btn numuneler hibir ilem yapmadan yerine getirebilmektedirler. Fakat yksek dayan koulunu oda scakl testlerinde en youn numunenin (% 38 gzenekli) dahi salayamad grlmektedir. Vcut scaklnda ve daha yksek scaklklarda ise bu kpn ve % 43 gzenee sahip TiNi alamnn bu dayanc salad gzlenmitir. Dngsel yklemeboaltma yapldnda ise % 38 ve % 43 gzenee sahip alamlar btn scaklklarda gerekli koulu salarken % 51 gzenekli kpk ise ancak Af scaklnn zerindeki scaklklarda bu zorunluluu yerine getirebilmektedir. % 59 gzenekli numunenin ise zaten maksimum dayanc 90 MPa civarndadr. TiNi kpklerin dngsel ykleme-boaltma ilemine tabi tutulmas sperelastisite zelliklerinin iyiletirilmesi asndan yalandrmaya alternatif ucuz ve basit bir yntem olarak kullanlabilir. Bu ilem sonucu iyi bir dorusal sperelastisite elde edilebilmektedir. % 43 gzenee sahip numune 150 MPada 5 dng ile yklenip boaltldnda son dngde % 3.8 olan gerinimin tamamn kazanabilmitir. Dngsel ykleme-boaltma sonras dorusal sperelastisitenin elde edilmesi istenilen geri kazanm miktarnn hangi gerilimde elde edilebileceinin de kolaylkla hesaplanabilmesini salamaktadr. Elastik moduli deerlerinde dngsel ykleme-boaltma sonras belirgin bir farkn olmad ilk bakta anlalmaktadr. nk hemen hemen btn ykleme ve boaltma erileri birbirine paraleldirler. ekil 7 dngsel ykleme-boaltmann mukavemet ve sneklie olan etkisini sunmaktadr. Maksimum basma dayanc az bir miktar derken krlma gerinimindeki dme yar yaryadr. Bu ileme maruz braklmayan numunede % 15 gerinimde ilk atlak oluurken, 150 MPada 20 dng sonras 21. dngde krlan numunede ilk atlak % 7 ye yakn bir gerinimde ortaya kmtr. Test edilen numunenin gzeneklilik oran % 51 dir.
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ekil 7. Dngsel ykleme-boaltmann basma mukavemeti ve krlma gerinimi zerindeki etkisi. ekil 8 farkl gzenekteki numunelerin farkl scaklktaki elastik moduli deerlerini vermektedir. Artan gzenek miktaryla elastik modln dorusal olarak azald gzlemlenmitir ve beklenildii gibi artan scaklklarla elastik modlde de bir art kaydedilmitir. Daha nce de belirtildii zere martensit dnmn mmkn hale getiren kritik gerilme scaklkla dorusal olarak artmaktadr ve bu gerilme martensit Ms scaklnn hemen zerinde minimumdur. Yani Ms scaklndan uzaklatka gereken gerilme miktar da artacaktr. Bu da martensitik dnm zorlatracandan elastik modlde artmaya neden olacaktr. Youn kemiin elastik modl 10-20 GPa arasnda deiirken gzenekli kemiinki 3 GPadan kktr [12-13]. % 38 ve % 43 gzenee sahip TiNi alamlarnn elastik modl deerleri vcut scaklnda youn kemiinki ile ayn aralkta yer almaktadr. % 51 gzenekli TiNi alam da 60 Cde bu arala girmekte daha dk scaklklarda da fazla dk olmamaktadr. Btn bu mekanik zellikler birlikte deerlendirildiinde % 38-51 arasnda gzenek ieren TiNi kpklerin yapay kemik olarak kullanlmalarnda mekanik adan da bir sorun tekil etmedikleri grlmtr. Daha yksek sinterleme scaklklar ve nikelce zengin alam tozlar kullanlarak mekanik zellikler daha da gelitirilebilir ve bylelikle % 51den daha fazla gzenek ieren TiNi kpklerin de mekanik zellikleri yapay kemiinkiyle ayn seviyelere getirilebilir.
ekil 8. Elastik modl deerlerinin gzenek miktar ve scaklkla deiimi. 4. SONULAR
1. Mg boluk yapc kullanlarak retilen TiNi kpklerin gzenek yaps, miktar ve boyutlar kemik implantasyonu 2. TiNi kpklerin basma ve sperelastisite davran hacimli TiNi alamlarnnkinden farkldr. Dorusal spereuygulamalar iin uygundur. lastisite gsteren kpklerde elastik modl, dayan ve martensit oluturmak iin gereken gerilim deeri artan gzeneklilikle azalmaktadr.
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3. Btn kpklerde ksmi sperelastisite gzlenmi olup, geri kazanlamayan gerinme miktarlarnn artan test
scakl ile azald grlmtr. Dngsel ykleme-boaltma sonras % 5e varan gerinimler tamamen geri kazanlabilmitir. Kalnt gerilmelerin nedeni test scakl ya da farkl geometrik yapda olan hcre duvarlar ve sinter boyunlarnn farkl gerilmelere maruz kalmas sonucu meydana gelen martensit stabilizasyonuna balanmtr. 4. % 38-51 gzeneklilikteki TiNi alamlarnn kemik implantasyonu gibi biyomedikal uygulamalarn gerektirdii mekanik zellikleri karlad tespit edilmitir.
TEEKKR Bu alma Trkiye Bilimsel ve Teknolojik Aratrma Kurumu (TBTAK, Proje no: 108M118) tarafndan desteklenmitir. KAYNAKLAR
1. Banhart, J., Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress in 2. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review, Acta Bio3. Gjunter, V.E., Sysoliatin, P., Temerkhamor, T., Superelastic Shape Memory Implants in Maxillofacial Surmaterialia, Vol. 4, pp. 773-782, 2008. gery, Traumatology, Orthopaedics, and Neurosurgery, Tomsk University Publishing House, Tomsk, Russia, 1995. 4. Shabalovskaya, S., On the Nature of Biocompatibility and Medical Applications of Shape Memory and Superelastic NiTi-Based Alloys, Bio-Medical Materials and Engineering, Vol. 6,pp. 267-289, 1996. 5. Pelton, A.R., Stoeckel, D., Duerig, T.W., Medical Uses of Nitinol, Materials Science Forum, Vol. 327-328, pp. 63-70, 2000. 6. Aydomu, T., Bor, A.., Production and Characterization of Porous TiNi Shape Memory Alloys, Turkish Journal of Engineering and Environmental Sciences, Vol. 35, pp. 69-82, 2011. 7. Aydomu, T., Bor, ., Gzenekli TiNi ekil Bellekli Alamlarnn retilmesi ve Karakterizasyonu, 15. Uluslararas Metalurji ve Malzeme Kongresi, Dzenleyen: TMMOB Metalurji Mhendisleri Odas, s. 665-675, stanbul, 2010. 8. Aydomu, T., Bor, ., Processing of Porous TiNi Alloys Using Magnesium as Space Holder, Journal of Alloys and Compounds, Vol. 478, pp. 705-710, 2009. 9. Aydomu, T., Tarhan Bor, E., Bor, ., Phase Transformation Behavior of Porous TiNi Alloys Produced by Powder Metallurgy Using Magnesium as a Space Holder, Metallurgical and Materials Transactions A, in press, DOI: 10.1007/s11661-011-0714-z. 10. Itin, V., Gyunter, V., Shabalovskaya, S., Sachdeva, R., Mechanical Properties and Shape Memory of Porous Nitinol, Materials Characterization, Vol. 32, pp. 179-187, 1994. 11. Liu, D.Y., Galvin, S.P., Criteria for Pseudoelasticity in Near-equiatomic NiTi Shape Memory Alloys, Acta Materialia, Vol. 45, pp. 4431-4439, 1997. 12. Rho, J.Y., Ashman, R.B., Turner, C.H., Youngs Modulus of Trabecular and Cortical Bone Material: Ultrasonic and Microtensile Measurements, Journal of Biomechanics, Vol. 26, pp. 111-119, 1993. 13. Suchanek, W., Yoshimura, M., Processing and Properties of Hydroxyapatite-based Biomaterials for Use as Hard Tissue Replacement Implants, Journal of Materials Research, Vol. 13, pp. 94-117, 1998. Materials Science, Vol. 46, pp. 559-632, 2001.
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TiNi KPKLERDE EKL BELLEK DAVRANII VE FAZ DNM SICAKLIKLARININ NCELENMES

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ZET Mevcut almada Ti-50.4 at. %Ni alam tozu kullanlarak boluk yapc toz metalurjisi yntemiyle retilen % 5373 gzeneklilie sahip TiNi kpklerinde gzenek miktarnn serbest ekil kazanm ve faz dnm scaklklar zerindeki etkisi incelenmitir. Boluk yapc olarak kresel magnezyum tozlar kullanlmtr. ekil bellek etkisiyle kazanlan gerinim miktarnn artan gzeneklilik ile % 95lerden % 78e kadar azald gzlenmitir. Uygulanan gerinim miktarnn artmasyla grece dk gzenekli kpklerde (% 53-59) ekil kazanm fazla etkilenmezken yksek gzenekli kpklerde % 20ye varan azalmalar meydana gelmitir. Faz dnm scaklklarnn gzeneklilikten nemli lde etkilenmedii artan gzenek miktar ile yavaa ykseldii tespit edilmitir. te yandan kullanlan alam tozu ile kpklerin dnm scaklklar karlatrldnda 25 C ye varan artlar belirlenmitir. Bu artn nedeni boluk yapc olarak kullanlan magnezyumun proses esnasnda oksitlenmeyi nlemesiyle aklanmtr. Anahtar kelimeler: ekil Bellek Etkisi, Gzeneklilik, Faz Dnm Scaklklar, Martensitik Dnmler, TiNi Alamlar.
INVESTIGATION OF SHAPE MEMORY BEHAVIOR AND PHASE TRANSFORMATION TEMPERATURES IN TiNi FOAMS
ABSTRACT In the present study, effect of porosity on free shape recovery and phase transformation temperatures of porous TiNi alloys with porosities in the range of 53-73% which were produced using Ti-50.4 at. %Ni alloy powders and space holder technique has been investigated. Spherical magnesium powders were used as space holder material. It has been observed that strain recoveries by shape memory mechanism decreased from 95% to 78% with increasing porosity. While shape recovery in 53% and 59% porosity samples, relatively low porosity, was not dependent on the amount of applied strain considerably, in higher porosity samples shape recovery exhibited up to 20% decrease with increasing strain. It has also been found that phase transformation temperatures has not affected much from porosity content; just a slight increase was observed with increasing porosity. On the contrary, increase in the transformation temperatures of the foams produced compared to that of the starting prealloyed powders reached up to 25 C. This has been explained by the deoxidation of TiNi alloy by the magnesium used as space holder during processing. Keywords: Shape Memory Effect, Porosity, Phase Transformation Temperatures, Martensitic Transformations, TiNi Alloys.
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1. GR ekil bellekli alamlar (hafzal ya da akll alamlar olarak da bilinirler), termomekanik yklerin uygulanmasyla termoelastik martensitik dnm gsteren ve belirli bir scakln zerine stldklarnda kalc ekil deiimlerini geri kazanabilme yeteneine sahip metalik alamlar olarak tanmlanrlar. Fakat ekil bellek etkisi ayn zamanda baz seramik ve polimerik malzemelerde de grlmektedir. [1]. Atomik olarak % 50 titanyum ve % 50 nikelden oluan TiNi alamnda benzersiz ekil bellek etkisi ilk olarak 1963 ylnda Buehler ve arkadalar tarafndan tesadfen farkedildi [2]. Her ne kadar ayn etki baka alamlarda daha nceden bulunmu olsa da aratrmaclarn fazla dikkatini ekmemitir. Buna karlk TiNi alam bulunuundan hemen sonra olduka popler hale geldi. Bunda alamn bulunduu Naval Ordinance Laboratory tarafndan dnya apnda yaplan yaynlar ve birok uygulama iin gerekli olan stn mekanik zellikleri salamas ile ekil bellek etkisi gsteren dier alamlar iinde en iyi performans gstermesi etken olan faktrler olarak sralanabilir [3]. ekil bellek etkisi gsteren eitli alamlardan sadece TiNi ve bakr bazl olanlar ticari uygulama alan bulmutur. Yapay sert doku nakillerinde metaller ve alamlar en ok kullanlan malzemelerdir. Biyomalzeme endstrisinin dnya apnda pazar paynn 2013de 140 milyar dolara ulamas beklenmektedir [4] ve bunun nemli bir ksmn sert doku onarm ve nakilleri oluturmaktadr. Bu malzemelere olan ihtiya gn getike artmaktadr ve bu artn nmzdeki yllarda ok daha hzl olaca ngrlmektedir. u anda kullanlan geleneksel biyomalzemeler, nakil malzemesinin ve kemiin uyum sorunlar nedeniyle deiik problemler yaratmaktadr. Fizikokimyasal ve mekanik zellikleri ne olursa olsun herhangi bir implant, vcut dokularyla iyi ve kalc bir temas salayamad mddete, vcut tarafndan kabul grmez. Olduka basit grnen ancak vida, yaptrc, dolgu malzemesi, plastik ya da karmak mekanik sistemlerin kullanlmasyla tatmin edici bir ekilde zlemeyen bu sorunun TiNi ekil bellekli alamdan yaplm, snger kemiinkine benzeyen bir yap ieren gzenekli implant paralar kullanlarak baaryla zlebilme olasl ok yksektir. TiNi alamnn biyouyumluluu 316L paslanmaz eliininkiyle ayn seviyededir [5]. Malzemenin yzeyinde oluan ve biyouyumluluu salyan TiO2 tabakas ayn zamanda alam iindeki nikel ve dier elementlerin znmesini ve vcuda yaylmasn engellemektedir. Bunun yannda TiNi alamlar mkemmel mekanik zellikler, iyi korozyon dayanc ve stn ekil bellek etkisi gibi ekici zellikleri bir arada iermektedir. mplant uygulamalarnda, gzenekler iine kemik bymesine, vcut svlarnn serbeste dolamna izin verir, nakil parann vcutla btnlemesini salayarak implant ve dokular arasnda muntazam uyumlu bir ban olumasn mmkn klar. Vcut iinde yer alan canl dokular ve kemikler ekme ykleri altnda yksek geri kazanlabilir gerinimlere sahiptir ( > % 2) [6]. Olduka iyi bir elastikiyet gerektiren bu davrana benzer bir davran ancak ekil bellekli alamlar gsterebilmektedir. Gzenekli TiNi alamlarnn elastik modlleri kemiin elastik modl seviyelerine gzenek miktar ve boyutunun ayarlanmasyla kolaylkla indirilebilmektedir. Bu yzden gzenekli TiNi alamlar kala ve eklem bozukluklarnn tedavisinde, travmatolojide, kemik ve sert doku nakillerinde ve diilikte implant malzemesi olarak kullanlma potansiyeli yksek malzemelerdir [7-9]. Yakn zamanda yaplan almalarda gzenekli TiNi alamlarnda da bir dereceye kadar ekil bellek etkisi gzlenmitir [10,11]. Pratik uygulamalar iin ok nemli olan bu zelliin ve dnm scaklklarnn belirlenmesi son derece gerekli bir almadr. Literatrde gzenekli TiNi alam retme yntemleri ile ilgili ok sayda yayn [12-27] varken bu malzemelerin ekil bellek etkisi [10,11] ve dnm scaklklarn gzenek miktar ile ilikilendirerek inceleyen makale [28-30] says olduka azdr. Bu almada magnezyum boluk yapc kullanlarak retilen TiNi alamlarnda gzenek miktarnn ekil bellek etkisi ve martensitik dnm scaklklar zerindeki etkileri sistematik bir ekilde ortaya konulmutur.
2. DENEYSEL YNTEM 2.1. Kullanlan Tozlar ve retim Yntemi Metalik kpk retiminde balang tozlar olarak hafif nikelce zengin (Ti-50.4 at. %Ni, % 99.9 saflkta, Special Metals Corp.dan temin edilmi) TiNi tozlar kullanlmtr. Gaussian (log-normal) dalm gsteren TiNi alam tozunun ortalama ap 40 m (ekil 1(a)) iken boluk yapc kresel Mg tozunun (%99.82 saflkta, Tangshan Weihao Magnesium Powder Co. LTDden satn alnm) ap ortalama 450 m (ekil 1(b)) olarak belirlenmitir. Her iki tozda inrt argon gaz altnda atomize edilmek suretiyle retilmitir. TiNi alam tozlarnn ekli, sinterleme esnasnda kirlenmeye ve istenmeyen Ti-Ni bileiklerinin oluumuna yol aabilecek oksitlenme vb. reaksiyonlar minimuma
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indirmek iin yzey alan en dk olan kre (ekil 2(a)) olarak seilmitir. ekil 2(b)den grlecei zere oda scaklnda (25 C) elde edilen X n difraksiyon (XRD) sonularna gre TiNi tozun iyapsnda B2 stenit ve B19 martensit fazlar bulunmaktadr. Diferansiyel taramal kalorimetre (DSC) ile llen dnm scaklklar da bu sonu ile uyum iindedir. Martensit balama (Ms) ve martensit biti (Mf) scaklklar srasyla 28 ve 10 C olarak belirlenmitir. stenit balama (As) ve stenit biti (Af) scaklklar ise 36 ve 58 C olarak bulunmutur.
ekil 1. (a) TiNi, (b) Mg tozuna ait parack boyut dalmn gsteren histogramlar. Gzenekli TiNi alam retiminde kullanlan boluk yapc yntem daha nceki almalarmzda [7,8,23] ayrntl olarak aklanmtr. zetle hacimce % 40-70 aralnda Mg ieren TiNi ve Mg karmlar % 5 polivinil alkol (PVA) zeltisi (% 2.5 PVA + su) ilavesiyle hazrlanmtr. Elde edilen karmlar souk olarak basma kalplar iinde 400 MPa basn altnda ift ynl olarak baslmlardr. Presleme sonras kalplardan karlan yaklak 10 mm apnda ve 12 mm yksekliindeki numuneler 1100 C scaklkta, koruyucu argon atmosferi altnda 2 saat sreyle sinterlenmilerdir. % 40 Mg ieren kompakt sinterleme esnasnda toplam Mg miktar % 50 olacak ekilde ekstra Mg koruyucu olarak ilave edildikten sonra sinterlenmitir. Oda scaklndan 1100 Cye stma hz 10 C/dak olarak sabit tutulmutur. Sinterleme sonrasnda pota frnn souk blgesine ekilerek yaklak 60-75 C/dak bir hzda numunelerin oda scaklna soutulmalar salanmtr.
ekil 2. TiNi tozuna ait (a) SEM grnts ve (b) XRD paterni. 2.2. Karakterizasyon Tozlarn parack boyut dalmlar Malvern Mastersizer 2000 cihaz ile belirlenmitir. TiNi tozda ve sinterlenmi gzenekli TiNi alamlarnn i yapsnda oluan fazlar belirlemek iin Rigaku D/Max 2200/PC model XRD cihaz kullanlmtr. Toz morfolojileri ve mikroyap incelemeleri Noran System 6 enerji dispersiv spektrometresine sahip Jeol JSM 6400 taramal elektron mikroskobu (SEM) kullanlarak gerekletirilmitir. TiNi kpklerin gzeneklilikleri Arimet yntemiyle belirlenmitir.
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ekil bellek davran 10X10 mmlik silindirik numuneler kullanlarak 30 kN kapasiteli Instron 3367 mekanik test cihaz ve bu cihaza ait ekstensometre yardmyla belirlenmitir. Sv azotta 5 dak bekletilen farkl gzenek miktarna sahip numuneler (% 100 martensit elde etmek iin) daha sonra oda scaklnda % 2 gerinime kadar basma yklemesine maruz braklmtr. Yk boaltldktan sonra numuneler yaklak 100 Cde kaynamakta olan saf su ierisinde martensit-stenit dnmn salamak iin 5 dak sreyle tutulmutur. Serbest ekil kazanm numunelerin yksekliinin soutma ve stma sonras llmesiyle hesaplanmtr. Bu lmler 1m hassasiyetli bir mikrometre ile yaplmtr. Ayn prosedr ayn numuneler kullanlarak % 4, 6 ve 8lik gerinimler iin de tekrarlanmtr. retilen TiNi kpklerin ve balang TiNi alam tozunun dnm scaklklar Perkin Elmer Diamond model DSC kullanlarak +150 C ile -60 C scaklk aralnda yaplan 10 C/daklk stma ve soutma dnglerinden tesbit edilmitir. Referans malzeme olarak indiyum kullanlmtr. Numuneler sl dengenin salanmas iin stma ve soutma esnasnda, limit scaklklar olan 150 ve -60 Cde srasyla 2 ve 5 dak bekletilmitir. Faz dnm scaklklar, ikinci stma ve soutma erilerine ASTM F2004-05 standardnda [31] verilen prosedr uygulanarak tespit edilmitir.
3. BULGULAR VE DEERLENDRME 3.1. Mikroyap ekil 3de sinterlenmi % 53 gzenekli TiNi kpn XRD diyagram ve SEM grnts verilmitir. retilen numunelerin oda scaklnda martensit ve stenit fazlarndan olutuklar bulunmutur. Sinterleme sonras kullanlan tozlarla kyaslama yapldnda i yaplarn deimedii ve ayn kald gzlenmitir. Ayrca istenmeyen ikincil fazlarn, oksit ya da karbon bileiklerinin olumad da gze arpmaktadr.
ekil 3. Sinterlenmi % 53 gzenekli TiNi kpe ait (a) XRD paterni, (b) SEM grnts. 3.2. Serbest ekil Geri Kazanm % 53 gzenekli TiNi kpn oda scaklnda elde edilen gerilim-gerinim erileri ekil 4te verilmektedir. Uygulanan btn gerinim miktarlarnda farkl gzenek oranlarna sahip dier kpklerin davran da benzer olmutur. lk etapta elastik deformasyon gsteren kpkler gerinimin artmasyla birlikte ikizlenmeye maruz kalarak dorusala yakn bir dnm gstermilerdir. Ykn boaltlmasyla birlikte uygulanan gerinimin ok az bir ksmnn geri kazanld ekil 4ten net bir ekilde grlmektedir. Maksimum basma dayanlar % 53 gzenekli kpk iin 55 MPa iken % 59 gzenekli kpk iin 30 MPa civarndadr. Daha yksek gzenekli kpklerin dayancysa olduka dk olmutur. Elastik modl deerleri de ok dk olan kpklerde en dk gzenekli kpk iin bu deer 1 GPa olarak hesaplanmtr. Mekanik zelliklerin olduka dk olmasnn nedeni ksmi sinterleme sonras yapda kalan mikro-gzeneklerin varl, balang tozlarnn byk boyutlu olmas ve kompaktlarn sinterleme scaklna stlrken ekil geri kazanm gstermeleri ile aklanabilir. TiNi kpkler dk mekanik zellikler gsterse de olduka iyi ekil bellek etkisi sergilemilerdir. Martensit faznda iken uygulanan gerinim sonras stenit biti scaklnn zerine stlarak salanan gerinim kazanm miktarlar % olarak ekil 5de gsterilmitir. % 53 ve % 59 gzenekli kpklerde uygulanan gerinimin yaklak % 90 ve fazlas geri kazanlrken daha yksek gzenekli numunelerde bu deer % 78e kadar azalmtr. Dk gzenekli nu-
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munelerdeki gerinim kazanm miktar uygulanan gerinime daha az bal iken gzenekliliin artmasyla birlikte bu bamllk daha duyarl bir hale gelmi ve % 73 gzenekli numunelerde uygulanan gerinimin artmasyla birlikte ekil geri kazanmnda ciddi bir azalma gzlenmitir.
ekil 4. % 53 gzenekli TiNi kpn oda scaklndaki gerilim-gerinim erileri. 3.3. Martensitik Dnm Scaklklar
ekil 5. Geri kazanlan gerinimin uygulanan maksimum gerinim ve gzeneklilikle deiimi.
ekil 6da TiNi tozun ve gzenek miktar % 53-73 arasnda deien TiNi kpklerin DSC erileri sunulmaktadr. Dnm scaklklarnn en yksek gzenekli numune dnda artan gzenek miktaryla daha yksek scaklklara doru kayma eilimi gsterdikleri btn numunelerin stma-soutma erilerinden aka grlmektedir. Balang tozlaryla kyaslandnda, gzenekli malzemelerde sz edilen bu kayma miktarlarnn Ms scakl iin 12-19 C ve Af scakl iin 15-25 C olduu belirlenmitir. Pik dnm scaklklarnn da benzer bir kayma eilimi gsterdii yine ayn ekilden ve izelge 1den izlenebilmektedir. Dnm slar TiNi kpklerde hacimli TiNi alamlaryla benzerlik gstermektedir. retilen TiNi kpks malzemeler kimyasal homojenlie sahip olduundan, yani Ti-Ni ikili sistemindeki ikincil intermetalik fazlar bulunmadndan, dnm scaklklarndaki artn kkeni gzenek miktarna, Ti3Ni4 faznn kelmesine ya da proses esnasndaki olas oksitlenmeye atfedilebilinir. Fakat bu bileimdeki TiNi alamlarnda Ti3Ni4 faz oluumu grlmemektedir [1,3], kald ki bu faz XRD sonularnda da grlmemitir. Bu almada retilen TiNi alam ierisindeki gzenekler kresel ekilde olduklarndan lokal gerilmeler yaratmayaca iin gzenekliliin de dnm scaklklar zerinde etkisi olmamas gerekir. Geriye sinterleme esnasnda numunelerin oksitlenme derecelerinin farkl olmas nedeniyle dnm scaklklarnn deimesi seenei kalmaktadr. Bilindii gibi TiNi alamlarnda oksijen miktarnda % 1 oranndaki bir art dnm scaklklarnda 100 C de yol amaktadr [1].
ekil 6. Farkl gzeneklere sahip TiNi alamlarnn DSC erileri.
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Bu almada, gzenekli malzemelerin retiminde boluk yapc olarak kullanlan magnezyum, sinterleme srasnda indirgeyici bir atmosfer yarattndan, balang tozlarnn kompozisyonuna bal olarak sinterleme sonras mikro yap yine stenit ve martensit fazlar karmndan olumaktadr. TiNi alamlarnda oksijenin znrl dk scaklklarda 0.045 at.% [1] olduundan yksek oksijen konsantrasyonlar Ti4Ni2O faz oluumuyla sonlanr. Bu oluum srasnda ana fazdaki titanyum atomlar nikel atomlarna kyasla iki kat daha fazla kullanldklarndan oksijenin varlnda nikelce zenginlemi ana fazda TiNi3 faz belirir. zetle, ok az oksijenli ortamlarda bile TiNi alamlarnn tek faz olarak retilmeleri mmkn olamamaktadr. Termodinamik hesaplamalar gstermitir ki oksijen ksmi basncnn 1100 Cde 5 10-25 atmden az olmas durumunda TiO2 oluumu engellenebilmektedir. Dier taraftan ayn scaklkta MgO oluumu iin gerekli oksijen ksmi basnc 10-34 atmdir. Oksijen ekicilii bakmndan yaklaldnda, magnezyum Elingam erisinde kalsiyumun ardndan gelen ikinci elementtir ve titanyumun oksitlerini etkin bir ekilde indirgeyebilir. TiNi sinterleme atmosferi olarak yksek saflkta argon gaz kullanmak veya vakum artlar oluturmak oksijen ksmi basncn ancak 10-8 atmosfere kadar drebilir ki hala ok yksek bir deerdir. Titanyum alamlarnn sinterlenmesinde olas oksijen kaynaklar, koruyucu atmosfer olarak kullanlan gazlar ve balang tozlarndan gelen yzey oksit katmanlardr. Bu almada sinterleme atmosferindeki oksijenin ortamdan uzaklatrlmas oksijen giderici olarak kullanlan kk boyutlu snger titanyumla yaplmaktadr. Snger boyutlarnn kk tutulmas olayn kinetiini hzlandrmaktadr, argon gaz ak ise minimumda tutulmaktadr. Balang tozlarnn yzeyindeki oksijeni indirgemede ise magnezyumun ok etkili olduu gzlenmitir. Alnan bu nlemler sonucunda alamlarda ikincil faz olumad belirlenmitir. Titanyum alamlar karbrleme ve nitrrlemeye de eilimlidirler ancak titanyum ve magnezyumun karbon ya da azota olan yksek afiniteleri argon gaznn bu safszlklardan da arndrlmasn salamaktadr. Ayrca magnezyumun hidrojene kar yksek ekicilii sebebiyle TiNi alamlarnn olas hidrojenlenmesi engellenmektedir. Dier retim yntemlerinde titanyum ya da magnezyum gibi ortamn ksmi oksijen basncn dren malzemeler kullanmadklarndan alam tozu dahi kullanldnda oksitlenme ve/veya ikincil intermetalik fazlarn oluumu kanlmazdr. Ek olarak, elemental tozlar kullanldnda homojen olmayan kartrmalar difzyon mesafelerinin artmasna ve sonu olarak titanyum ya da nikelce zengin blgeler olumasna yol aar. zetle, TiNi alamlarnn koruyucu magnezyum atmosferi altinda sinterlenmesi kirlenmelerden arndrlm olmalarn garanti eder. izelge 1. Sinterlenmi numunelere ait dnm scaklklar ve entalpileri. Gzeneklilik (%) Ms TiNi toz 53 59 66 73 28 40 43 47 46 Mp 20 31 31 34 27 Dnm scaklklar (C) Mf 10 20 21 21 13 As 36 49 50 48 42 Ap 50 62 62 68 66 Af 58 73 75 80 83 Dnm entalpileri (H, J/g) -Hforw 18.3 23.6 22.5 24.2 27.5 Hrev 18.3 23.1 22.7 24.8 24.7
Bunun yannda magnezyumun dnm scaklklarna etkisi, zerinde durulmas gereken nemli bir konudur. Gzenekler eklenen magnezyumlar ile oluturulduundan magnezyum miktarnn ve gzeneklerin dnm scaklklarna etkisi ayndr. Bunun dorulanmas % 40 ve % 50 magnezyum eklenerek retilen % 53 ve 59 gzenekli alamlarn dnm scaklarnn karlatrlmasyla yaplabilir. Bunlarn dnm scaklklar nerdeyse ayndr nk sinterleme srasnda ayn miktarda magnezyum kullanlmtr. % 40 Mg eklenerek retilen numunelerin kenarna ekstra Mg ilave edilerek pota ierisinde toplamda % 50 Mg olmas salanmtr. Daha nce de belirtildii zere TiNi alamlarnda oksijen miktarnda % 1 oranndaki bir art dnm scaklklarnda 100 C de yol amaktadr. Magnezyumun balang TiNi tozlarndaki oksijeni indirgemesi nedeniyle dnm scaklklarnda bir artma grlmtr. Ayn ekilde eklenen magnezyum miktarnn artmasyla dnm scaklklar grece ykselmitir ta ki % 73 gibi ok yksek bir gzenek oranna ulalncaya kadar. Gzenekliliin ak fazla artmasyla magnezyum buhar potay daha abuk terketmekte ve bunun sonucunda da dnm scaklklarnda az da olsa bir azalma meydana gelmektedir. 4. SONULAR ekil bellek etkisiyle TiNi kpklerde kazanlan gerinim miktarnn artan gzeneklilik ve gerinim ile % 100lerden % 78e kadar azald gzlenmitir. Gzenek miktarnn ayn zamanda geri kazanlan gerinimin uygulanan gerinime
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duyarll da artrd gzlenmitir. Mg boluk oluturucu yntemiyle retilen gzenekli TiNi ekil bellek alamlarnn gzenek miktarlarnn, dnm scaklklar zerinde dorudan bir etkiye sahip olmad grlmtr. Artan gzeneklilikle birlikte dnm scaklklarnda grlen artn, eklenen Mg orannn artmasyla birlikte sinterleme srasnda oluan sv veya gaz magnezyumun gzenekli TiNi alamndan oksijen giderme etkisinin artmasna bal olduu tespit edilmitir. Gzenekli TiNi alamlarnn neredeyse tam dnm gsterdii grlmtr.
TEEKKR Bu alma Trkiye Bilimsel ve Teknolojik Aratrma Kurumu (TBTAK, Proje no: 108M118) tarafndan desteklenmitir.
KAYNAKLAR Otsuka, K., Wayman, C.M., Shape Memory Materials, Cambridge University Press, Cambridge, UK, 1998. Buehler, W.J., Gilfrich, J.W., Wiley, R.C., Effect of Low-Temperature Phase Changes on the Mechanical Properties of Alloys near Composition TiNi Journal of Applied Physics, Vol. 34, pp. 1475-1477, 1963. 3. Otsuka, K., Ren, X., Physical Metallurgy of Ti-Ni-based Shape Memory Alloys, Progress in Material Science, Vol. 50, pp. 511-678, 2005. 4. http://www.biyomalzeme.org.tr/haberler.html, Eriim Tarihi: 25.06.2011. 5. Shabalovskaya, S., On the Nature of Biocompatibility and Medical Applications of Shape Memory and Superelastic NiTi-Based Alloys, Bio-Medical Materials and Engineering, Vol. 6,pp. 267-289, 1996. 6. Gjunter, V.E., Sysoliatin, P., Temerkhamor, T., Superelastic Shape Memory Implants in Maxillofacial Surgery, Traumatology, Orthopaedics, and Neurosurgery, Tomsk University Publishing House, Tomsk, Russia, 1995. 7. Aydomu, T., Bor, ., Gzenekli TiNi ekil Bellekli Alamlarnn retilmesi ve Karakterizasyonu, 15. Uluslararas Metalurji ve Malzeme Kongresi, Dzenleyen: TMMOB Metalurji Mhendisleri Odas, s. 665-675, stanbul, 2010. 8. Aydomu, T., Tarhan Bor, E., Bor, ., Phase Transformation Behavior of Porous TiNi Alloys Produced by Powder Metallurgy Using Magnesium as a Space Holder, Metallurgical and Materials Transactions A, in press, DOI: 10.1007/s11661-011-0714-z. 9. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review, Acta Biomaterialia, Vol. 4, pp. 773-782, 2008. 10. Bansiddhi, A., Dunand, D.C., Shape-Memory NiTi Foams Produced by Solid-State Replication with NaF, Intermetallics, Vol. 15, pp. 1612-1622, 2007. 11. Bansiddhi, A., Dunand, D.C., Shape-Memory NiTi Foams Produced by Replication of NaCl Space-Holders, Acta Biomaterialia, Vol. 4, pp. 1996-2007, 2008. 12. Itin, V., Gyunter, V., Shabalovskaya, S., Sachdeva, R., Mechanical Properties and Shape Memory of Porous Nitinol, Materials Characterization, Vol. 32, pp. 179-187, 1994. 13. Li, B.Y., Rong, L.J., Li, Y.Y., Gjunter, V.E., Synthesis of Porous Ni-Ti Shape-Memory Alloys by Self-Propagating High-Temperature Synthesis: Reaction Mechanism and Anisotropy in Pore Structure, Acta Materialia, Vol. 48, pp. 3895-3904, 2000. 14. Yuan, B., Zhang, X.P., Chung, C.Y., Zeng, M.Q., Zhu, M., A Comparative Study of the Porous TiNi ShapeMemory Alloys Fabricated by Three Different Processes, Metallurgical and Materials Transactions, Vol. 37A, pp. 755-761, 2006. 15. Kaya, M., Orhan, N., Kurt, B., Khan, T.I., The Effect of Solution Treatment under Loading on the Microstructure and Phase Transformation Behavior of Porous NiTi Shape Memory Alloy Fabricated by SHS, Journal of Alloys and Compounds, Vol. 475, pp. 378-382, 2009. 16. Tosun, G., Ozler, L., Kaya, M., Orhan, N., A Study on Microstructure and Porosity of NiTi Alloy Implants Produced by SHS, Journal of Alloys and Compounds, Vol. 487, pp. 605-611, 2009. 17. Aydomu, T., Bor, A.., Production and Characterization of Porous TiNi Shape Memory Alloys, Turkish Journal of Engineering and Environmental Sciences, Vol. 35, pp. 69-82, 2011. 18. Li, B., Rong, L.J., Li, Y.Y., Porous NiTi Alloy Prepared from Elemental Powder Sintering, Journal of Materials Research, Vol. 13, pp. 2847-2851, 1998. 19. Zhu, S.L., Yang, X.J., Fu, D.H., Zhang, L.Y., Li, C.Y., Cui, Z.D., Stress-Strain Behavior of Porous NiTi Alloys Prepared by Powders Sintering, Materials Science and Engineering A, Vol. 408, pp. 264-268, 2005.
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20. Greiner, C., Oppenheimer, S.M., Dunand, D.C., High Strength, Low Stiffness, Porous NiTi with Superelastic 21. Lagoudas, D.C., Vandygriff, E.L., Processing and Characterization of NiTi Porous SMA by Elevated Pressure 22. Zhao, Y., Taya, M., Kang, Y.S., Kawasaki, A., Compression Behavior of Porous NiTi Shape Memory Alloy, 23. Aydomu, T., Bor, ., Processing of Porous TiNi Alloys Using Magnesium as Space Holder, Journal of 24. Zhang, Y.P., Li, D.S., Zhang, X.P., Gradient Porosity and Large Pore Size NiTi Shape Memory Alloys, Scripta 25. Grummon, D.S., Shaw, J.A., Gremillet, A., Low-Density Open-Cell Foams in the NiTi System, Applied Phy26. Guoxin, H., Lixiang, Z., Yunliang, F., Yanhong, L., Fabrication of High Porous NiTi Shape Memory Alloy by 27. Bertheville, B., Porous Single-phase NiTi Processed under Ca Reducing Vapor for Use as a Bone Graft Su28. Wu, S., Chung, C.Y., Liu, X., Chu, P.K., Ho, J.P.Y., Chu, C.L., Chan, Y.L., Yeung, K.W.K., Lu, W.W., Cheung,
bstitute, Biomaterials, Vol. 27, pp. 1246-1250, 2006. K.M.C., Luk, K.D.K., Pore Formation Mechanism and Characterization of Porous NiTi Shape Memory Alloys Synthesized by Capsule-Free Hot Isostatic Pressing, Acta Materialia, Vol. 55, pp. 3437-3451, 2007. 29. Yuan, B., Zhang, X.P., Chung, C.Y., Zhu, M., The Effect of Porosity on Phase Transformation Behavior of Porous Ti-50.8 at.% Ni Shape Memory Alloys Prepared by Capsule-free Hot Isostatic Pressing, Material Science and Engineering A, Vol. 438-440, pp. 585-588, 2006. 30. Li, H., Yuan, B., Gao, Y., Chung, C.Y., Zhu, M., High-porosity NiTi Superelastic Alloys Fabricated by Lowpressure Sintering Using Titanium Hydride as Pore-forming Agent, Journal of Materials Science, Vol. 44, pp. 875-881, 2009. 31. ASTM F 2004-05, Standard Test Method for Transformation Temperature of Nickel-Titanium Alloys by Thermal Analysis, ASTM, Philadelphia, PA, 2010. Metal Injection Molding, Journal of Materials Processing and Technology, Vol. 206, pp. 395-399, 2008. sics Letters, Vol. 82, pp. 2727-2729, 2003. Materialia, Vol. 57, pp. 1020-1023, 2007. Alloys and Compounds, Vol. 478, pp. 705-710, 2009. Acta Materialia, Vol. 53, pp. 337-343, 2005. Sintering, Journal of Intelligent Materials Systems and Structures, Vol. 13, pp. 837-850, 2002. Properties, Acta Biomaterialia, Vol. 1, pp. 705-716, 2005.
494
Akm Destekli Sinterleme Yntemi le retilen SiCp Takviyeli Bronz Matriksli MMKin Karakterizasyonu
Mehmet UYSAL Ramazan KARSLIOLU, Ahmet ALP Hatem AKBULUT, Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm 54187 Adapazar/SAKARYA mehmetu@sakarya.edu.tr zet Bu almada bronz (% 90 Cu - %10 Sn) matriks ierisine farkl boyutlarda(65-52-45 ve 37 m) hacimce %20 takviyeli silisyum karbr (SiC) ilave edilerek metal matrisli kompozit malzeme (MMK) retilmesi amalanmtr. stenilen bileimdeki tozlar, bilyal deirmen kullanlarak homojen ekilde kartrlp souk olarak basn altnda ekillendirilmitir. ekillendirilen bu yap yksek akm ve dk voltaj kullanlarak hzl bir ekilde sinterlenmitir. retilen numunelerin mikro yap, mikro setlik zellikleri ile oluan fazlar ve matriks faz iersindeki partikl dalm Taramal Elektron Mikroskobu (SEM) kullanlarak incelenmitir. Anahtar Kelimeler: Akm destekli sinterleme, Bronz, SiC, MMK Abstract In this study, a bronze matrix (90 wt. % Cu + 10 wt. % Sn) was reinforced with SiC particles using mechanical alloying and then produced by subsequent rapid current sintering technique. The mechanically ball milled bronze powders were reinforced with electroless Ni coated 20 vol. % SiC particles with four different particle sizes of 65, 52, 45 and 37m. Microstructure of the bronze /SiC composite produced by these techniques have been investigated by means of SEM. Keywords current sintering, bronze, SiC, MMC 1.Giri Kompozit malzemeler; sergiledikleri mkemmel dayanm zellikleri, farkl birlesim ve geometrilerde retilebilmeleri, yorulma, tokluk, yksek scaklk, oksitlenme ve asnma dayanmlarnn yksek olmas nedeniyle, endstriyel alanlarda gn getike daha fazla kullanlmaktadr Yksek elastik modl, yksek mukavemet ve yksek anma direnci gibi zellikleri salamak zere metal alamlarna yaplan ilaveler, partikl eklinde SiC, TiC, B4C ve Al2O3 gibi seramik takviyeler olabilmektedir [1-3]. Gnmzde metal matris kompozit malzeme retiminde sv yntemler, partikl takviyeli metal matris kompozit sistemlerinde olduka tercih edilen retim prosesleridir. Genel olarak stn dkm kalitesi ve yksek retim kapasitesine sahip olmas ve son ekle yakn retim imkan salamas gibi avantajlar nedeniyle sktrma dkm prosesi nemli retim tekniklerinden birisidir.[4] Dk termal genleme katsays, yksek sertlik, yksek elastik modl, iyi elektriksel iletkenlik, yksek termal iletkenlik, iyi anma dayanm gibi zelliklerinden dolay bakr esasl kompozitler, yksek hibrid modll malzemelerin, elektronik rlelerin, elektrikli yaylarn, birok elektrik/elektronik paralarn, frenlerin, srtnmeye direnli malzemelerin retimi gibi amalar iin kullanlmaktadr [5,6]. Bu almada kompozit malzemeler, bronz matriks iersine farkl boyutlarda hacimce %20 SiC tozlar ilave edilerek, akm destekli sinterleme yntemi kullanlarak retilmitir. Akm sinterleme ynteminin seilme nedeni, ksa sre-
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lerde youn ve ekonomik kompozitlerin elde edilmesidir. Yntem ayn zamanda sinterlenen kompozitlerin istenildiinde bir altlk zerine kaplanmasna imkan verebilecek esneklikte olmasndan dolay da tercih edilmitir. retim prosesi uygulanmadan nce SiC seramik partikllerinin matriks yapya daha kolay girmesini salayacak slatma artlarn salamak amacyla da akmsz yntemle nikel kaplanmtr. retilen kompozit malzemelerin fiziksel ve yapsal zelliklerinin tespiti amacyla mikroyap, sertlik ve anma zellikleri incelenmitir. 2.DENEYSEL ALIMALAR 2.1. Malzemeler MMK malzeme retiminde matriks malzemesi olarak bronz (%90bakr-%10 kalay), takviye malzemesi olarak % 20 hacimce orannda 65, 52, 45 ve 37 m boyutlarnda SiC seramik partiklleri kullanlmtr. 2.2. Seramik Tozlarn Akmsz Yntemle Nikel Kaplanmas Kompozit malzeme retiminde, metal ile seramik partikller arasndaki arayzey byk sorun oluturmaktadr. Bu ara yzey sorununu ortadan kaldrabilmek iin metal ile seramik arasndaki slatabilirlii arttrmak gerekmektedir. Metal ile seramik partiklleri arasndaki slatabilirlii gelitirmek iin birka yol vardr. Seramik partikllerin zerini metal ile kaplamak bunlardan biridir. Yaplan bu almada bazik zeltide ve akmsz kaplama artlarnda SiC seramik partikllerinin yzeyleri Ni kaplanmtr.
ekil 1. Akm sinterleme deney dzeneinin grnts [4] 2.2.1. Kaplama ncesi Uygulanan n Yzey lemleri Seramik Tozlarnn Temizlenmesi: Kaplama yaplacak SiC seramik tozlarnn yzey zellikleri kaplamann verimlilii asndan ok nemlidir. Bu yzden seramik tozlarn kaplama ncesi yzeyleri ultrasonik temizleme cihaznda aseton zeltisi iinde yaplmtr. Hassaslatrlma lemi: Bu ilemden ama toz yzeylerinde kalay iyonlarnn adsorbsiyonudur. Seramik tozlar aseton ile temizlendikten sonra SnCl2 zeltisinde belirli srelerde tutulmak suretiyle hassaslatrma ilemi uygulanmtr. Aktivasyon lemi: Bu ilem genellikle hassaslatrma ilemi akabinde uygulanmaktadr. Bu ilem srasnda tozlar aktivasyon amacyla PdCl2 zeltisinde belirli bir sre bekletilmektedir. Bu esnada toz yzeylerinde kalayn ykseltgenmesi srasnda indirgenen Pd, ok ince bir tabaka oluturmaktadr. Tozlar daha sonra 90 oCde etvde kurutula-
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rak kaplamaya hazr hale getirilmitir. 2.2.2.Seramik Tozlarnn Kaplanmas lemleri SiC seramik tozlarnn kaplanmasnda kullanlan akmsz nikel kaplama banyosu bileimi ve parametreleri Tablo 1de verilmitir. Kaplamalar, pH 8 olan alkali zeltide ve 70 0C scaklkta gerekletirilmitir. Tablo 1 Aksz kaplama parametreleri Banyo bileenleri ve parametreleri NiCl2 Na-citrate (C6H5Na3O7. 2H2O) NH4Cl sodium hypophosphite pH Scaklk Sre Partikl miktar Datalar (45.0 g/l) (100.0 g/l) (50.0 g/l) 8.0 g/l) 8 70oC 10 dak 10 g/l
2.3. Kompozit Malzeme retimi Bronz matrisli kompozit malzeme retimi iin ilk nce, akmsz nikel ile kaplanm SiC seramik tozlar ile bronz tozlar, kartrma ilemine tabi tutulmutur. Farkl boyutlardaki SiC tozlar hacimce % 20 olacak ekilde bronz matriks iersine ilave edildikten sonra gezegensel deirmende kartrma ilemi gerekletirilmitir. Kartrma ilemi numune/bilya arlka oran 1/15 orannda olacak ekilde WC bilyeler kullanlarak 1 saat sreyle gerekletirilmitir. Bu ilemden sonra tozlar 300 kg/cm2lik basn altnda 10 dakika sreyle souk izostatik preslenerek ham numuneler elde edilmitir. Akabinde akm destekli sinterleme yntemi ile bronz matrisli, hacimce %20 SiC takviyeli kompozit malzemeler elde edilmitir. ekil 1 de akm destekli sinterleme ynteminin grnts verilmitir. Dzenee yerletirilen numune 10 dk sreyle 2,0 V altnda ortalama 1000 A akm etkisinde braklarak hzla yksek scakla karlm ve sinterleme ilemi gerekletirilmitir. 2.4. Kompozit Malzemelerin Karakterizasyonu retilen bronz alam ve kompozit malzemeler metalografik numune hazrlama teknikleri ile srasyla 600, 800, 1200 lk elmas zmpara kullanlarak kaba ve ince olarak zmparalanmtr. Daha sonra elmas pastalar yardmyla kaba ve ince parlatma ilemlerine tabi tutulmutur. Metalografik olarak hazrlanan yzeyler daha sonra etanol ile temizlenmi ve yzeydeki kirlilikler giderildikten sonra tozlarn dalm ve morfolojisinin belirlenmesi iin JEOL JSM 6060LV marka taramal elektron mikroskobu (SEM) ile geri salml elektron dedektr kullanlarak incelenmitir. Matriksteki zellik deiimlerinin tespiti amacyla retilen kompozitlerin mikrosertlikleri incelenmitir. Leica VMHT MOT Mikro sertlik cihaznda her bir numune iin en az 5 alandan vickers setlik lmleri yaplm ve 5 lmn ortalamas alnmtr. lmler 15 saniye sre ile 50 gr yk altnda gerekletirilmitir. 3. Deneysel Sonular 3.1. Mikroyap almalar 3.1.1. Akmsz Nikel Kaplama Numuneleri Kompozit malzeme retiminden nce SiC seramik tozlarna akmsz yntem ile nikel kaplama yaplmtr. ekil 2de nikel kaplama yaplmam ve nikel kaplama uygulanm SiC seramik tozlarnn SEM yaplar grlmektedir. SEM resimlerinden grld gibi SiC seramik tozlarnn zeri nikel ile baarl bir ekilde kaplanmtr. Nikel partiklleri
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a)
b)
c seramik tozlarnn yzeyini homojen ekilde kaplam ve tozlarn keskin kelerinde youn olarak birikmitir.
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ekil 2 a) a) Kaplanmam SiC seramik tozlar b)Ni kaplanm SiC seramik tozlar c) Ni kaplanm SiC seramik tozlarn EDS analizi 3.1.2. Kompozit Malzemeler Bronz matrisli kompozit malzemeler, bronz iersine farkl boyutlarda ve %20 orannda SiC takviyesi yaplmak suretiyle ve akm destekli sinterleme yntemi kullanlarak retilmitir. Sinterleme ilemi btn malzemeler iin 1000 A akm altnda ve 10 dak. sre ile gerekletirilmitir. Farkl boyutlarda SiC ile takviye edilmi kompozit malzemelerin SEM grntleri ekil 3de verilmitir. Bronz matrisli kompozit malzemelerin mikroyapsal almalarnda SiC seramik partikllerinin bronz matris ierisine homojen olarak daldklar grlmektedir. SiC seramik partikllerin matris iersine homojen dalmn, SiC partiklleri ile matris malzemesi arasnda arayzey bann iyi olmas ve alam tarafndan SiC partikllerinin iyi slatabilirlilii salamtr. Ayrca n ilem safhasnda uygulanan, gezegensel deirmen ortamnda yaplan kartrma ileminin etkin ve ideal artlarda yaplm olmas da bu sonu zerinde ciddi etki dourmutur. Seramik partiklleri ile matris arasndaki arayzeyin grnmnn de ok iyi olduu sylenebilir. ekil 3 Bronz SiC kompozit malzemelerim SEM grnts a) 65m b) 52 m c) 45 m d) 37 m 3.2. Sertlik lmleri Numunelerin sertlik lmleri mikro-sertlik cihaznda Vickers sertlik yntemi kullanlarak yaplmtr. Sertlik deerleri, metalografik olarak hazrlanm numunelerden 50 gr yk altnda 15 sn sreyle ve 5 farkl lmn aritmetik ortalamas alnarak yaplmtr. ncelenen kompozitlerin sertlik deerleri ekil 4 de verilmitir. Takviye edilen SiC seramik tozlarn boyutlar dtke kompozit malzemenin sertliinde art grlmektedir. Kompozit malzemelerde en yksek sertlik, 37 m partikl boyutuna sahip SiC seramik tozlarn ilavesiyle elde edilmitir. Bunun sebebi bronz matrisin iindeki sert SiC seramik partikllerinin bulunmasndan dolay matris takviye faz arayzeyinde dislokasyon younluunun artmas ve partiklerin dispersiyon sertlemesi etkisi yapmasdr. Ayrca SiC seramik partikllerinin boyutlarnn dk olmas, daha fazla yzey alannn olumasna ve sertliin daha da ykselmesine neden olmutur.
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ekil 4. Bronza SiC ilavesiyle sertlikte meydana gelen deiim 4.Sonular Akm destekli sinterleme yntemi kullanlarak SiC takviyeli kompozitler ksa srede baarl bir ekilde retilmitir. Takviye faz ile matris arasndaki ara yzeyi iyiletirmek iin SiC seramik tozlar akmsz yntem ile nikel kaplanmtr. SiC seramik tozlarnn yzeyi homojen bir ekilde kaplanmtr. Bronz matris iersine 65-52-45-37 m boyutlarnda hacimce %20 orann SiC takviye faz ilave edilerek akmla sinterleme yntemiyle kompozit malzemeler retilmitir. SiC partiklleri matris iersine homojen olarak dalarak baarl bir kompozit retilmitir. Matris iersine ilave edilen SiC partikllerinin boyutlar dtke kompozit malzemenin sertliinde art meydana gelmitir. Kaynaklar 1.Ramesh, C.S. , Noor Ahmed R. , Mujeebu M.A., Abdullah M.Z. Development and performance analysis of novel cast copperSiCGr hybrid composites Materials and Design Vol. 30, pp 19571965 2009 2. Pul M, aln R., Seker U. nfiltrasyon Yntem ile retilmi Al Matrisli MgO Takviyeli Yel_ Kompozitlerin lenebilirliin Asl Kesme Kuvvetleri Asndan Degerlendirilmesi 2. Ulusal Tasarm _malat ve Analiz Kongresi 1112 Kasm 2010 - Balkesir 3. Mindivan H., Kayali E.S SiC takviyeli 2618 Al matrisli kompozitlerin anma davran itdergisi mhendislik Cilt:6, Say:2, 63-70 Nisan 2007 4. Karsliolu R., Uysal M., Alp A., Akbulut H., Current Actvated Snterng Of Bronze Hybrd Mmcs Coatngs On Steel Substrates 5th International Powder Metallurgy Conference October 8-12, 2008 Ankara TURKEY 5. Sapate S.G., Uttarwar A., Rathod R.C., Paretkar R.K. Analyzing dry sliding wear behaviour of copper matrix composites reinforced with pre-coated SiCp particlesMaterials and Design Vol.30 pp 376386 2009 6. Tjong S.C., Lau K.C. Tribological behaviour of SiC particle-reinforced copper matrix Composites Materials Letters Vol. pp 43. 274280 2000 7. Jianhua Z., Lei L., Bin S., Wenbin Hu Mechanical properties of Cu/SiCp composites fabricated by composite electroformingMaterials Letters Vol. pp 61 28042809 2007
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Demir esasl toz alamnda SNTERLEME iLE SERTLETRMe ileminin mekanik zelliklere ETKS
Hakan HAFIZOLU*, Nuri DURLU*, Ayta ATA**, Hsn ZDURAL** *TOBB Ekonomi ve Teknoloji niversitesi, Makine Mhendislii Blm, Stz Caddesi No:43, Ankara, **Toz Metal Ticaret ve Sanayi A.. stanbul Caddesi No:75 Grpnar, Bykekmece, stanbul ZET Sinterleme ile sertletirme ilemi ikincil bir sl ileme gerek kalmakszn yksek mekanik zellikler veren dk maliyetli ve tek aamal bir imalat ilemidir. Bu almada Fe-1,5Cu-0.62C toz alamnda sinterleme ile sertletirme ileminin mekanik zelliklere etkisi incelenmitir. Numuneler 600 MPa basn altnda preslendikten sonra 1120 Cde sanayi lekli frnda metan gaz ortamnda 20 dakika sre ile sinterlenmitir. Sinterleme ileminden sonra numuneler iki farkl soutma hznda soutularak, sertletirilmitir. Sinterlenmi numunelerin bir blmne ikincil bir sl ilem uygulanmtr. Sinterlenmi, sinterleme ile sertletirilmi, sinterlenmi ve ikincil sl ilem uygulanm numunelerde yaplan mekanik testler ile makro sertlik deerleri, apraz krlma dayanm deerleri belirlenmi ve numunelerin mikroyaplar incelenmitir. alma, Fe-1,5Cu-0,62C alam iin sinterleme ile sertletirme ileminde kullanlan soutma hzlarnn yeterli olmadn ve sinterleme ile sertletirme ileminin ikincil sl ileme kyasla daha dk sertlik deerlerine yol atn gstermitir. Anahtar Kelimeler: Toz metalrjisi, sinterleme ile sertletirme, sl ilem, demir esasl tozlar
EFFECT OF SINTER HARDENING ON MECHANICAL PROPERTIES OF AN IRON BASED POWDER ALLOY

ABSTRACT Sinter hardening is a low cost one step manufacturing process which gives high enough mechanical properties without the need of a secondary heat treatment. In this study, the effect of sinter hardening on the mechanical properties of Fe-1,5Cu-0,62C powder alloy was investigated. Samples were pressed under 600 MPa and sintered at 1120C under methane for 20 minutes. After sintering, sinter hardening was done under two different cooling rates. Some of the sintered samples were heat treated as a secondary operation. The macrohardness and transverse rupture strength values of the sintered, sinter hardened, sintered and heat treated samples were determined. Microstructural analysis of the samples were done with optical and scanning electron microscopy. The study show that for the alloy with the composition Fe-1,5Cu-0,62C with the cooling rates utilized one step sinter hardening process did not improve the hardness of the samples in comparison to the sintered and heat treated samples. Key Words : Powder metallurgy, sinter hardening, heat treatment, iron based powders 1. GR Sinterleme ile sertletirme ilemi son zamanlarda nemi artan, dk maliyetli ve yksek performansl para imalatnda kullanlan bir imalat tekniidir [1]. Sinterleme ile sertletirme ileminin geleneksel sinterleme ve sonrasnda yaplan ikincil sl ileme kyasla eitli avantajlar bulunmaktadr. Bunlardan ilki, sinterleme ile sertletirme ilemi uygulanan paralarda ikincil bir sl ileme gerek kalmamas nedeni ile retim maliyetlerinin dmesidir. lemin
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dier bir avantaj, sinterleme ile sertletirilen paralarda su verme ilemi ile sertletirilen paralara kyasla daha az boyutsal deiimin gzlenmesi ve imalat ileminin kolaylamasdr [2]. Geleneksel sinterleme ve ikincil sl ilemde paralar ya banyosunda soutulmaktadr. Sinterlenmi paralarn gzenekli olmas, soutma ilemi srasnda yan gzeneklere szmasna neden olmaktadr. Yan gzeneklerde birikmesi ve sonrasnda belirli bir scaklkta uzaklatrlmamas mekanik zellikleri olumsuz etkilemektedir. Sinterleme ile sertletirme ileminde soutma ileminin sinterleme frn iinde yaplmas bu tr sorunlarn oluumunu engellemekte ve dk maliyetli yksek performansl para retimine yol amaktadr. Sinterleme ileminden sonra yaplan zellik artrc sl ilemlerde para yzeyinde veya tm para kesiti boyunca menevilenmi martensitli mikroyaplarn elde edilmesi esas amatr [2]. Sinterleme ile sertletirme ileminde martensitli mikroyaplar oluturmak iin sinterleme ilemi sonrasnda srasnda soutma hznn ayarlanmas gerekmektedir. Soutma hznn martensit oluumu iin gerekli dzeyde olmas, i parasnn kimyasal bileimi ve ktlesi ile ilgili olup, bu hz 900-425 C aralnda genellikle 1-10C/sn olarak belirtilmitir [1]. Sinterleme ile sertletirme ileminde soutma hzn etkileyen eitli unsurlar bulunmaktadr. Para geometrisi, frn tasarm, soutucu akkann s kapasitesi, paradaki gzeneklilik miktar gibi unsurlar soutma hzn etkilemektedir. Sinterleme ile sertletirme ileminde, soutma hz dnda alamlama elementlerinin paralarn sertleebilirliini artrmas asndan nemi byktr. Alam elementleri, srekli souma dnm diyagramlarnda (CCT) martensitli dnm iin gerekli soutma sresini artrarak, daha uzun bir srede martensit oluumu salamaktadr [3]. Sertleebilirlii artrmak iin kullanlan alam elementleri Mn, Cr, Si, Mo, Ni, C, Cu olarak gsterilebilir. Ni, Mo, Cu elementlerinin oksijen ile tepkimeye girme eilimleri az olduu iin sertleebilirlii arttrmas asndan en yaygn kullanlan alamlama elementleridir. Karbon, sertleebilirlii dier alam elementlerine kyasla daha dk oranda artrmaktadr. Alam elementi olarak karbon kullanld taktirde bu element sadece oluan martensitin sertliini artrmaktadr. Alam elementlerinin yksek miktarda kullanlmas tozun sktrlabilirliini azaltrken ilemdeki maliyetlerin artmasna neden olur [4]. Bu nedenle, son zamanlarda soutma yaplacak paralar ile soutucu akkan arasndaki s iletiminin artrlmas amalanmtr. Daha hzl soutma, parada istenilen zelliklerin olumas iin gerekli koullardan biridir. Yksek hzda soutma ilemi, endstriyel frnlarda bandn daha hzl almasn ve retimin artmasn salar. Sertleebilirlii etkileyen bir dier unsur da stenit tane boyutudur. stenit tane boyutu arttka tane snr azalacandan, tane snrlarnda oluan prlit oluumu zorlaacaktr. Sertlii dk olan prlitin olumamas parann sertleebilirliini olumlu bir ekilde etkilemektedir. Toz metalurjisiyle retilmi paralarda, gzeneklilik mekanik zellikleri etkilemektedir [5]. En nemli deiken toplam gzeneklilik miktardr ve parann nihai younluu gzeneklilik hakknda fikir vermektedir. Bir dier deiken ise gzeneklerin geometrisidir. Geni ve dzensiz gzenekler mekanik zellikleri olumsuz etkilemektedir. Bu almann amac, Fe-1,5Cu-0,62C toz alamnda sinterleme ile sertletirme ileminin ve sinterleme ileminden sonra yaplan ikincil sl ilemin mekanik zelliklere etkisinin incelenmesidir. 2. DENEYSEL YNTEM Bu almada, Hganas firmasnn su atomizasyon yntemiyle rettii saf demir tozu (ASC100.29) kullanlmtr. Tozun tane boyutu 50-150 mikron arasnda deimektedir. Saf demir tozuna arlka %1,5 orannda bakr (toz boyutu 149 mikron) ve %0,62 orannda grafit tozu ilave edilmitir. almada kullanlan toz bileimi ve zellikleri izelge 1 de verilmitir. Demir esasl tozlarda bakr sinterlenmi paradaki boyutsal deiimi en aza indirmek iin kullanlr [6] . Grafit ise hem sertlii arttrmak hem de yalayc etkisi yaratmak iin kullanlan bir alam elementidir. Toz karmna yalayc olarak %0,5 MnS ve balayc olarak %0,9 amide mumu eklenmitir. izelge 1. Fe-1,5Cu-0,62C tozunun bileimi ve zellikleri. Miktar % arlk Grafit 0,62 Cu 1,5 Fe kalan Grnr younluk 3,00 g/cm
3
Akkanlk 35 s/50 g
Numuneler 600 MPa basn altnda 60 tonluk Instron marka ekme-basma cihaznda tek ynl preslenmitir. Presleme ileminden sonra numunelerin ham younluklar 7,07 g/cm3 olarak llmtr. Deneysel almalarda iki farkl geometride numune preslenmitir. Bu numuneler; nokta eme deneylerinde kullanlmak zere preslenen ubuk numuneler ve makro sertlik, mikro sertlik ve mikroyap almalar iin kontrol numunesi olarak preslenen
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pelet numunelerdir. 16 mm apl pelet numunelerde 8 gr toz kullanlrken ubuk numunelerde yaklak olarak 17 gr toz kullanlmtr. Pelet numunelerden er tane, ubuk numunelerden TS 4222 EN ISO 3325 standartlarna uygun olarak beer tane hazrlanmtr. Preslenen numunelerin sinterleme ilemleri ve sinterleme ile sertletirme ilemleri Tozmetal firmasndaki frnda gerekletirilmitir. Sinterleme ilemlerinde sinterleme ortam olarak metan gaz kullanlmtr. Frnda; ilk olarak 700C de yalayc ve balayc giderme ilemi yaplm, daha sonra numuneler 1000Cye, 1050Cye ve 1120Cye kademeli olarak stlarak sinterleme ilemi gerekletirilmitir. Numuneler 1120Cde 20 dakika sre ile sinterlenmilerdir. Sinterleme ileminden sonra yava soutma koullar 5 Hz olarak ayarlanm, sinterleme ile sertletirme ilemleri ise orta hzda soutmada 15 Hz ve hzl soutmada ise 35 Hz olarak gerekletirilmitir. Frnn bant hz 200 mm/dak. olup her bir evrim 1 saat 20 dakikada tamamlanmtr. Sinterleme ilemlerinden sonra numunelerin apraz krlma dayanmlar, makrosertlik ve mikrosertlik deerleri belirlenmitir. apraz krlma dayanm deerleri 5 tonluk Instron ekme-basma cihaznda TS 4222 EN ISO 3325 standartlarna uygun olarak gerekletirilmitir. Basma hz olarak 1 mm/dak. seilmi, numune boyutlar; 31,8x12,8x6 mm olarak belirlenmitir. Makro sertlik lmleri Wilson-Wolpert cihaznda Brinell yntemi ile (HB), mikrosertlik lmleri Buehler cihaznda Vickers yntemi ile (HV0,1) yaplmtr. Mikroyap almalarnda dalayc zeltisi olarak %3lk nital zeltisi kullanlmtr. Sinterlenmi numunelerin bir blm karbonitrrleme ikincil sl ilemine tabi tutulmutur. Karbonitrrleme ilemi 850Cde, C miktarnn 0,65 ve NH3 miktarnn 0,5 olduu durumda 120 dakika sre ile gerekletirilmi, sonraki aamada scaklk 810C ye drlm ve numunelere 30 dakika sre ile karbon ve amonyak nfuz ettirilmitir. Son aamada, numuneler 100Cde bulunan ya banyosunda soutulmu ve 85C de ykama ilemi gerekletirilerek ilem tamamlanmtr. 3.DENEYSEL SONULAR ve TARTIMA 3.1.Mekanik zellikler Sinterlenmi, sinterleme ile sertletirilmi, ve ikincil sl ilem uygulanm numunelerin mekanik zellikleri izelge 2 de verilmitir. Sinterlenmi numunelerin sertlik deeri 144 HB olarak llmtr. Sinterleme ileminden sonra iki farkl soutma hznda yaplan sinterleme ile sertletirme ilemi sertlik deerlerinde az bir arta yol am ve numunelerin sertlik deerleri orta hzda yaplan soutma ilemi iin 160 HB, yksek hzda yaplan soutma ilemi iin 167 HB olarak llmtr. Orta ve yksek hzda yaplan sinterleme ile sertletirme ileminde sertlik deerindeki artn az olmas Fe-1,5Cu-0,62C alam iin soutma hznn yeterli olmadn ve buna bal olarak martensit faz oluumunun gereklemediini gstermektedir. Sinterleme ileminden sonra yaplan ikincil sl ilem ile (karbonitrrleme), numunenin sertlii artm ve sertlik deeri 246 HB olarak llmtr. Sertlik deerindeki artn nedeni karbonitrrleme ilemi srasnda numune yzeyinde meydana gelen bileim deiimi ve su verme ilemi sonrasnda numune kesiti boyunca oluan martensit fazdr. kincil sl ilem uygulanm numunenin kesit boyunca mikrosertlik deiimi ekil 1de verilmitir. izelge 2. Sinterlenmi ve sinterleme ile sertletirilmi numunelerin mekanik zellikleri. Numune (Fe-%2Cu-%1,5Mo-%0,7C) Sinterleme (1120C, 20dak.) Sinterleme (1120C, 20dak.) ve orta hzda soutma Sinterleme (1120C, 20dak.) ve yksek hzda soutma Sinterleme (1120C, 20dak.) + ikincil sl ilem Makrosertlik (HB) 1443 1604 1673 24658 apraz Krlma Dayanm (MPa) 94326 91838 97832 93236
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Kenar blgelerde soutma hznn yksek olmasna ve martensit faznn oluumuna bal olarak yksek sertlik deerleri (700 HV0,1) elde edilirken, orta blgede sertleebilirliin dk olmasna bal olarak dk sertlik deerleri (350 HV0,1) elde edilmitir.
ekil 1. Sinterleme sonras ikinci sl ilem uygulanm numunenin kesiti boyunca mikro sertlik deiimi. Numunelerin apraz krlma dayanm deerlerinin 920-980 MPa arasnda deitii gzlenmitir (izelge 2). Fe-Cu alamlar zerine yaplan bir almada, 1150Cde amonyak gaz altnda 60 dakika sre ile sinterlenen Fe-2Cu alamnn sinterlenmi dayanm deeri 420 MPa olarak llmtr [7]. Fe-2Cu-0,6P alam zerine yaplan bir almada numuneler 1120Cde endogaz altnda sinterlenmi ve numunelerin apraz krlma dayanm deerleri 689 MPa olarak llmtr [8]. Bu tr alamlar zerine yaplan dier bir almada Fe-3Cu-0,3C-0,28P alamnn sinterlenmi dayanm deeri 880 MPa olarak llm ve C miktarnn artna bal olarak dayanm deerinin artt belirlenmitir [9]. 3.2.Mikroyap ncelemeleri ekil 2de sinterlenmi numunenin optik mikroskop ve taramal elektron mikroskop grntleri verilmitir. Mikroyap tektoid ncesi oluan ferrit fazndan (ak faz) ve ince perlitten olumaktadr. Sinterleme ileminden sonra yksek hzda soutulan numunenin optik ve taramal elektron mikroskop grntleri ekil 3te verilmitir. Mikroyap yava ve orta hzda soutulan numune mikroyaplarna benzer ekilde ferrit (ak faz) ve ince perlitten olumaktadr. Mikroyapda soutma hznn artmasna bal olarak ferrit miktar azald, ince perlit miktarnn ise artt gzlenmitir.
ekil 2. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve yava soutulan numunenin ferrit ve perlit ieren mikroyaplar.
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ekil 3. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve yksek hzda soutulan numunenin ferrit ve perlit ieren mikroyaplar.(a) 100x, (b) 3000x Sinterleme ileminden sonra yaplan ikincil sl ilem numunenin sertlik deerinde arta yol amtr. Bunun nedeni karbonitrrleme ilemi ile numunenin yzey blgesinde salanan bileim deiimi ve karbonitrrleme ileminden sonra yaplan hzl soutma ilemine bal olarak martensit faznn oluumudur. Numunenin dalanm mikroyapsndan elde edilen mikroyap grntleri ekil 4te verilmitir. ekil 4.ada verilen optik grnts sl ilem sonrasnda karbonitrrleme ilemi ile oluturulan sertletirme derinliini, ekil 4.bde verilen optik mikroskop grnts martensit mikroyapsn gstermektedir.
ekil 4. 1120C de 20 dakika sinterlendikten sonra sl ilem uygulanm numunelerin mikroyap grntleri. (a) 100x , (b) 1000x 4.SONULAR Bu almada demir esasl Fe-%1,5Cu-%0,62C toz alamnda sinterleme ile sertletirme ileminin mekanik zelliklere etkisi incelenmitir. ki farkl soutma hznda yaplan sinterleme ile sertletirme ileminin, sinterleme sonrasnda yaplan ikincil sl ileme kyasla istenilen dzeyde sertlik artna yol amad belirlenmitir. TEEKKR Bu alma TOBB Ekonomi ve Teknoloji niversitesi ve Tozmetal A. firmasnn katklar ile gerekletirilmitir. Taramal elektron mikroskop almasndaki katklarndan tr Cengiz Tan ve Serkan Ylmaza teekkr ederiz. 5.KAYNAKLAR [1] Hatami S., Malakizadi A., Nyborg L., Wallin D., Critical aspect of sinter-hardening of prealloyed Cr-Mo steel, Journal of Materials Processing Technology 2010 1180-1189.
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[2] James W. B., What is Sinter Hardening, International Conference on Powder Metallurgy & Particulate Materials, May 31-June 4, 1998, Las Vegas, Nevada, USA. [3] Rutz H.G., Graham A.H., Davala A.B., Sinter-Hardening P/M Steels, International Conference on Powder Metallurgy & Particulate Materials, June 29-July 2, 1997, Chicago, IL USA. [4] Blais C., Serafini Jr. R. E., LEsperance G., Effect of Hydrojen Concentration in Cooling Zone on Sinter Hardening, International Journal of Powder Metallurgy, Volume:41, No::4, pp. 33-41, 2005. [5] Staffelini G., Fontanari V., Hafez A., Benedetti M., Tensile and Fatigue Behaviour of Sinter Hardened Fe-1.5Mo2Cu-0.6C Steels, Powder Metallurgy, Volume:52, No:4, pp. 298-303, 2009. [6] etinkaya ., Karbon Katkl Alaml Demir Tozu Peletlerinin Sinterleme Sonras zellikleri, Yksek Lisans Tezi, stanbul niversitesi F.B.E., 2005. [7] Phadke B., Relationship Between Transverse Rupture Strength and Hardness of P/M Fe-Cu Alloys, The International Journal of Powder Metallurgy and Powder Technology, Volume: 17, No:1, pp.37-43, 1981. [8] Avar E., Durlu N., Ata A., Bozac C., zdural H., Demir Esasl Toz Metal Paralarn Sinterleme ile Birletirilmesi, Gazi niversitesi Mhendislik-Mimarlk Fakltesi Dergisi, Volume:25, No:4, 713-718, 2010. [9] Kohno T., Koczak M.J., Rajagopalan V., Nishino Y., Sintering Improvements in Strength and Dimensional Control Utilizing Eutectic Phosphide Additions in Iron-Copper-Carbon Alloys, Modern Developments in Powder Metallurgy, Volume 15, pp 521-540, 1985.
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CH4 ATMOSFERNDE NANOKRSTAL NKEL OKST TOZUNUN ZOTERMAL NDRGENMES

Melek CUMBUL ALTAY, erafettin EROLU stanbul niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 34320, Avclar, stanbul, mcumbul@istanbul.edu.tr, seref@istanbul.edu.tr ZET Nanokristal nikel oksit tozunun reaksiyon davran farkl scaklk (1000-1300 K) ve sre iin saf metan altnda allmtr. Nikel oksit toz ieriinin tanmlanmasnda DTA/DSC-TG, FTIR ve XRD tekniklerinden yararlanlmtr. Nikel oksit tozunun sadece NiO fazn ierdii XRD analiz ile ortaya konulmutur. Enstrmantal analiz, az miktarda Ni(OH)2xH2O faznn da orijinal nikel oksit tozda mevcut olduunu gstermitir. Arlk lmleri, Ni:O orannn 2:3 olduunu belirtmitir. Oksit tozu 1200 K de 5 dak iinde saf metan tarafndan Ni e indirgenmektedir. Artan scaklk ve sreyle serbest C da olumaktadr. Bu sonular, yksek scaklklarda (1100-1300 K) termodinamik analiz sonularyla kalitatif olarak uyum iinde bulunmutur. Anahtar Kelimeler: Nanokristal toz, Nikel oksit, Metan, ndirgenme
ISOTHERMAL REDUCTION OF NANOCRYSTALLINE NICKEL OXIDE POWDER UNDER CH4 ATMOSPHERE

ABSTRACT Reaction behavior of nanocrystalline nickel oxide powder was studied under pure CH4 atmosphere at different temperatures (1000-1300 K) and time. DTA/DSC-TG, FTIR and XRD techniques were employed for the determination of contents of nickel oxide powder. Nickel oxide powder consisted of only NiO phase as revealed by XRD. Instrumental analysis showed that a small amount of Ni(OH)2xH2O phase is also present in the original powder. Weight measurements indicated that the ratio of Ni to O is 2:3. Oxide powder was reduced to Ni at 1200 K within 5 min under pure CH4 atmosphere. Free C was also observed with increasing temperature and time. These results were found to be qualitatively in agreement with those of thermodynamic analysis at high temperatures (1100-1300 K). Keywords: Nanocrystalline powder, Nickel oxide, Methane, Reduction 1. GR Nano malzemeler, yeni malzemelerin bir tr olarak, geleneksel bulk (yn) malzemelere gre boyut etkisi nedeniyle stn fiziksel ve kimyasal zellikler sergilemekte ve birok alanda geni potansiyel uygulama alanna sahip olmaktadr. 1990 lardan beri nano lekli bilim ve teknoloji, kimyasal g kaynaklar alanna artan bir ilgiyle odaklanmtr [1]. Gei metal oksiti olan nikel oksit (NiO) ise NaCl tipi antiferromanyetik yar iletken zellie sahip olmasndan dolay birok aratrmann konusu olmutur. NiO in dikkat eken zellikleri; yksek dayankllk ve elektrokimyasal kararllk, dk malzeme maliyeti, periyodik karallk ve geni yaylma optik younluu asndan umut verici iyon depolama malzeme olmas ve eitli retim tekniklerine olanak salamasdr. NiO, solar termal emici, fotoelektroliz ve elektrokromik cihazlarda katalizr olarak potansiyel kullanm alanna sahiptir [2]. Ayrca NiO, karbon nanotp (KNT) sentezinde katalizr hammaddesi olarak da kullanlmaktadr [3]. KNT sentezi iin ark dearj, lazer kazma ve kimyasal buhar biriktirme (KBB) yntemleri en sk kullanlan yntemlerdir [4]. Ark dearj ve lazer kazma yntemleri, yksek scaklklarda kat karbon kaynaklarnn buharlamasyla
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oluan karbon atomlarnn younlamas, KBB yntemi ise genellikle hidrokarbon gazn (C2H2, CH4, C2H4 vs.) katalizr partikllerin yzeyinde paralanaca reaksiyon odasna tanmas temeline dayanmaktadr [5, 6]. KNT morfolojilerinin sentez srasnda katalizr boyutu ve ekliyle ilikili olduu rapor edilmitir. Katalizr olarak Fe, Co ve Ni gibi gei metal elementleri KNT lerin bymesinde nemli rol oynamaktadr [6]. KNT sentezinde katalizr olarak kullanlan gei metal oksit tozunun karbon bytlmesindeki katalitik etkisinin belirlenmesinde hidrokarbon gaz atmosferi altndaki indirgenme davrannn anlalmas byk nem tamaktadr. Bu almada nanokristal nikel oksit tozunun reaksiyon davran farkl scaklk ve sre iin saf metan altnda izotermal artlarda incelenmitir. Nikel oksit toz ieriinin tanmlanmasnda birok farkl malzeme karakterizasyon tekniklerinden yararlanlmtr. Ayrca oksit tozun reaksiyon davrannn daha iyi anlalmasna ve indirgenme artlarnn ngrlmesine yardmc olmas iin NiO-CH4 sisteminde termodinamik analiz de yaplmtr. 2. MALZEME VE YNTEM Mevcut almada kullanlan deney dzenei (ekil 1) esas olarak SiC stc elementli scak cidarl frn, kuvars tp (20 mm apnda) ve gaz ak lerlerden olumaktadr. Deneysel almada katalizr hammaddesi olarak 10-20 nm boyutlarnda % 99,8 safiyette nikel oksit tozu kullanlmtr. Deney ncesi oksit tozu, nem gidermek amacyla 373 K de 15 dak sreyle etvde tutulmutur. zotermal artlarda indirgeme almalar iin ~0,3728 g nikel oksit tozu almina kaykk ierisinde frnn scak blgesine yerletirilmitir. Daha sonra frn Ar (%99,999) atmosferi altnda reaksiyon scaklna stlmtr. stenilen scakla eriildiinde saf CH4 (% 99,5) belirlenen gaz ak hz3nda ve srede sistemden geirilmitir. Reaksiyon sonrasnda tm numuneler, 42,5 cm /dak lk Ar ak debisinde oda scaklna soutulmutur.. Reaksiyon sonras elde edilen rnn arl llmtr. Reaksiyonlarn geliimini anlamak iin rn/giren (balang) arlk oranlar hesaplanarak grafik eklinde gsterilmitir. Arlk lmleri, 0.0001 g hassasiyetli elektronik hassas teraziyle (Sartorius) yaplmtr. ndirgenme deneyleri 1000-1300 K scaklk aralnda, deiik sre (0-45 dak) ve metan gaz ak (0-70 cm3/dak) artlarnda allmtr.
ekil 1. Kimyasal buhar biriktirme reaktrnn ematik grnm. almada kullanlan balang tozu, X nlar difraksiyon analizi (Rigaku D/Max- 2200/PC), Fourier dnml kzltesi spektrometresi (FTIR; Bruker IFS 66/S), termal analiz (DSC/DTA-TG; TA SDT Q600) ve Yksek znrlkl Geirim Elektron Mikroskobu (HR-TEM; Jeol 2100) kullanlarak karakterize edilmitir. HR-TEM analizinde elektron difraksiyon paterni ekilmitir. Patern difraksiyon halka oranlar kullanlarak zlmtr. Balang tozunun kristal boyutu elde edilen XRD paterninden Denklem 1 de verilmi olan Scherrrer forml ile hesaplanmtr. (1) Burada, t = ortalama kristal boyutu, = dalga boyu (0,15418 nm), = yar ykseklikteki pik genilii, = difraksiyon asdr.
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Deneysel almalar neticesinde elde edilen rnlerin faz analizleri XRD yntemiyle, morfolojik incelemeler ise Taramal Elektron Mikroskobu (SEM Jeol 5600, FEG-SEM Jeol 6335F) kullanlarak gerekletirilmitir. Ayrca, NiO-CH4 sisteminde termodinamik hesaplamalar serbest enerji minimizasyon yntemiyle [7] 700-1300 K scaklk aralnda yaplmtr. 700-1000 K iin 71 ve 1100-1300 K iin ise 41 gaz faz bileeni hesaplamalarda kullanlmtr. Bu sistemde en nemli gaz bileenleri CO, CO2, CH4 ve H2 dir. Kat faz iin 700, 800 ve 900-1300 K de srasyla 6 (C, Ni, Ni3C, NiO, NiCO3, Ni(CO)4), 4 (C, Ni, Ni3C, NiO) ve 3 (C, Ni, NiO) bileen gz nne alnmtr. 3. BULGULAR 3.1. Oksit tozun karakterizasyonu Nikel oksit tozunun HR-TEM grnts, elektron difraksiyon paterni ve XRD paterni ekil 2 (a-c) de gsterilmektedir.
ekil 2. Balang oksit tozuna ait a) HR-TEM grnts, b) elektron difraksiyon ve c) XRD paternleri. Toz, genellikle kresele yakn bir morfolojiye sahip olup llen partikl boyutu ortalama 126 nm dir. Halka eklindeki difraksiyon paterni, tozun ok kristalli karakterini yanstmaktadr. ekil 2 b de, srasyla merkezden darya doru halkalarn (111), (200) ve (220) dzlemlerine ait olduu tespit edilmitir. Bu sonu NiO in YMK yapda olduunu gstermektedir. ekil 2 c de verilen tozun XRD paterni YMK yapy teyit etmektedir. Paternden grld zere difraksiyon piklerinin iddetleri ve difraksiyon alar, NiO in yaynlanm izgileriyle uyum iindedir. Ayrca toza ait iddetli piklerin yar ykseklikteki genilikleri kullanlarak kristal (tane) boyutu Denklem 1 ile 18 nm olarak hesaplanmtr. Bu deer retici firma tarafndan rapor edilen ve HR-TEM ile llen deerlere yakndr. Dolaysyla, partikllerin tek (mono) kristal yapda olduu anlalmtr. Nikel oksit tozuna ait argon atmosferi altnda elde edilen DSC/DTA-TG diyagramlar ile FTIR analiz sonular ekil 3 (a-c) de verilmitir. ekil 3a da verilen diyagramdan ~380 K de tozun bnyesinden nemin tamamen ayrld endotermik DTA ve DSC piklerinden anlalmaktadr. TG erisinden tozun yaklak olarak % 2,5 nem ierdii belirlenmitir. Artan scaklkla 520 K ve 576 K de iki endotermik pik gzlenmektedir. Literatr aratrmas, bu piklerin Ni(OH)2xH2O bileii ile ilikili olduunu gstermektedir [8-11]. Deneysel almada kullanlan tozun az miktarda bu faz ierdii tahmin edilmektedir. ki endotermik pikten birincisinin bileikte bulunan yapsal suyun uzaklamasyla, ikincisinin ise bileiin Ni(OH)2 nin NiO e dnmesiyle ortaya kt sonucuna varlmtr. Ayrca, 710 K de grlen kk ekzotermik pikin yapda olmas muhtemel amorf yapnn kristallemesiyle ortaya ktna inanlmaktadr. 1150 K de DSC erisinde daha belirgin grlen geni endotermik pik, NiO in Ar atmosferi altnda ok az miktarda Ni e dnmesiyle aklanmaktadr. Bu duruma tekabl eden TGA erisinde dk oranda artan scaklkla arlkta azalma olmakta olup eriilen nihai arlk deiimi % 88,5 tir. lerideki blmde gsterilecei zere arlk kayb ve XRD analizleri-1bu sonucu desteklemektedir. ekil 3 b de verilen orta-IR spektrumunda 3670-3330 cm da-l1ga saylar arasndaki geni bandn suya ve Ni(OH)2 e [1,2,8,12-15], ve 1976 cm deki kk keskin bandlarn ise ATR kr-istaline (elmas) [16] ait olduu tespit edilmitir. Ayrca, 1612 [1,2,8,14] ve 660 cm 1 deki bandlarn su ve Ni(OH)2 den [12-14] kayn-akland tahmin edilmektedir. Dier Ni(OH)2 bandlarnn 1432, 1360 [14] ve 560 cm 1 [11,13,17,18] dalga saylarnda bulunduu tespit edilmitir. Orta-IR spektrumunda 460 cm- de ortaya kan bandn NiO e ait olduu b1elirlenmitir [1,2,8,13,19,20]. ekil 3 c de verilen uzak IR spektrumunda ise 395 cm- deki geni band, nano kristal NiO ten kaynaklanmaktadr [17,18].
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ekil 3. a) Nikel oksit tozuna ait Ar atmosferi altnda elde edilen DSC/DTA-TG diyagramlar b)orta IR ve c) uzak IR blgesinde ekilen FTIR diyagramlar. 3.2. CH4 atmosferlerinde oksit tozunun izotermal indirgenmesinde scaklk ve srenin toz arlk oranlarna etkisi Sabit CH4 gaz ak hznda (13,4 cm3/dak) izotermal artlarda 1000-1300 K scaklk aralnda yaplan deneyler sonucu elde edilen toz arlk oranlarnn reaksiyon sresiyle deiimi ile 1000 ve 1200 K iin srasyla 15 ve 7,5 dak reaksiyon sresinde CH4 gaz ak hznn arlk oranlarna etkisi ekil 4 (a-b) de verilmitir. ekil 4 a da grld zere 1000 K de arlk zamanla azalmakta ve 45 dak iinde % 71 deerindeki yatay izgiye yaklamaktadr. 1100 K de arlk kayb daha ksa srede gereklemekte ve yaklak 17,5 dak sonra ok az arlk kazanc grlmektedir. 1200 ve 1300 K de ise arlk oran-zaman erileri arlkta azalmay takip eden art olduunu gstermektedir. Ancak, 1300 K de arlk oranlar 1200 K e kyasla daha dk seviyelerde bulunmaktadr. Bu scaklklarda (1200-1300 K) arlk kayb dk scaklklara kyasla daha hzl olmaktadr. ekil 4 b de grld zere 1000 K de arlk hemen hemen dorusal bir ekilde CH4 ak hzyla azalmaktadr. 1200 K de ise arlktaki azalmay art izlemektedir.
ekil 4. a) 1000-1300 K scaklk aralnda reaksiyon sresinin toz arlk oranlarna etkisi, b) CH4 ak hznn 1 000 K de 15 dak ve 1200 K de 7,5 dak sresi sonunda arlk oranna etkisi. 3.3. rnlerin X-nlar difraksiyonu ile faz analizi ekil 5 (a-d), oksitin deiik srelerde CH4 ile izotermal reaksiyonu sonucu elde edilen rnlere ait XRD paternlerini srasyla 1000, 1100, 1200 ve 1300 K iin gstermektedir.
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ekil 5. 13,4 cm3/dak CH4 ak hznda, deiik reaksiyon srelerinde; a) 1000 K, b) 1100 K, c) 1200 K ve d) 1300 K de elde edilen rnlerin XRD paternleri. 1000 K deki paternlerden balangta numunenin NiO ve eser miktarda Ni fazlarn ierdii, artan reaksiyon sresiyle Ni pik iddetlerinin ykseldii ve NiO e ait olanlarn ise azald grlmektedir. Ayrca, 45 dak sonunda Ni in yannda az miktarda oksit faz bulunmaktadr. 1100 K de ise 20 dak sonunda oksit tamamen Ni e indirgenerek tek faz olumaktadr. 1200 K de daha ksa srede (7,5 dak) indirgenme tamamlanmaktadr. Daha yksek scaklkta (1300 K) 5 dak sonra Ni ve NiO fazlar yannda eser miktarda C faz (ekilde gsterilen paternde belirgin deil) grlmektedir. 12,5 dak sonra ise oksit tamamen Ni fazna dnmektedir. Sre arttka C (002) pik iddeti de artmaktadr. ekil 6, 1200 K de, 13,4 ve 70 cm3/dak CH4 gaz ak hzlarnda, 7,5 dak reaksiyon sresinde elde edilen rnlere ait XRD paternlerini gstermektedir. Dk gaz ak hznda sadece Ni in, yksek CH4 gaz aknda ise Ni in yannda serbest C un bulunduu paternlerden grlmektedir.
ekil 6. Deiik CH4 ak hznda elde e3dilen rnlere ait XRD paternleri. artlar: a) 13,4 cm3/dak, b) 70 cm /dak CH4, 1200 K, 7,5 dak. 3.4. rnlerin morfolojlerinin incelenmesi CH4 atmosferinde (13,4 cm3/dak) 20 dak lk reaksiyon sonunda 1000 ve 1200 K de elde edilen numunelerin SEM grntleri srasyla ekil 7 (a-b) de gsterilmektedir. 1000 K de morfoloji, ortalama boyutu 6015 nm olan partikllerden olumaktadr. 1200 K de ise partikl boyutunda biraz art olmakta (ortalama boyut 7916 nm) ve top eklinde yaplar bulunmaktadr.
ekil 7. SEM grntleri. 13,4 cm3/dak CH4 gaz ak hz, 20 dak srede, a) 1000 K, b) 1200 K de elde edilen rnlere ait morfolojiler.
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3.5. Termodinamik analiz Ar altnda stma sonrasnda rnn esas itibaryla NiO ten olutuu tespit edilmitir. CH4 gaz sisteme verilmeden nce Ar altnda stma yapldndan termodinamik hesaplamalarda Ni:O oran 1:1 alnmtr. NiO-CH4 sistemi iin yaplan termodinamik hesaplamalar sonucunda elde edilen denge kat hal diyagram, denge durumunda oluan rnlerin (kat ve gaz) miktarlar scaklk (700-1300 K) ve CH4 mol kesrine (nCH4/(nNiO+nCH4) bal olarak ifade ekil 8 (a-c) de grafikler halinde verilmektedir. ekil 8 a dan da grld zere 700 ile 1300 K aralnda NiO+Ni, Ni, Ni+C olmak zere 3 faz alan mevcuttur. NiO+Ni faz alan, allan scaklklarda 0-0,2 CH4 mol kesri aralnda bulunmaktadr. CH4 mol kesri 0,2 den yksek olduunda, Ni tek faz blgesinin olutuu ve artan scaklkla Ni blgesinin geniledii ekilden grlmektedir. rnein, 700 ve 1300 K iin tek faz Ni blgesinin snrlar srasyla 0,2- 0,3 ve 0,2-0,5 CH4 mol kesir aralklarndadr. Bu snrlarn stnde Ni ile beraber serbest C da oluarak Ni+C faz alan ortaya kmaktadr. Bu alan, 1000 K in altndaki scaklklarda genilemektedir. ekil 8 b den grld zere allan scaklk aralnda artan CH4 mol miktar ile NiO miktar azalmakta, 0,2 mol kesrinde Ni ierii % 100 e ulamaktadr. Ni+C faz alannda tm scaklklarda CH4 mol kesri arttka Ni miktar azalmakta ve serbest C miktar artmaktadr. Ancak, 700 K de C faz 1300 K e kyasla daha dk CH4 mol kesrinde (0,3) ortaya kmaktadr. ekil 8 c de 700-1300 K de, H2O, CO2, H2, CO ve CH4 sistemde bulunan nemli gaz bileenleri olup ksm basnlarnn nCH4/(nNiO+nCH4) ile deiimi gsterilmitir. Grafikte gsterilmemi olan miktar az (<10-5 atm) olan gaz bileenler arasnda CH2O2, Ni(OH)2, HO, H, H2CO, CH4O, C2H4 ve C2H6 bulunmaktadr.
ekil 8. a) Scaklk ve CH4 mol kesrine bal olarak denge kat hal diyagram, b) CH4 mol kesrinin kat rn % mol miktarlarna etkisi, c) rnlerin ksm basnlarnn CH4 mol kesri ile deiimi rnlerin oluumu iin olas reaksiyonlar kat ve gaz faz bileimlerindeki deiimin incelenmesiyle aklanabilir. Dk CH4 mol kesirlerinde, Ni+NiO faz alannda, H2O ve CO2 ksmi basnlar H2 ve CO te kyasla daha yksek olup artan CH4 mol kesriyle miktarlar kademeli bir ekilde azalmaktadr. Buna karlk H2 ve CO ksm basnlar artmaktadr. Bu durumda oluabilecek nemli reaksiyonlar srasyla dk ve yksek CH4 mol kesirleri iin Denklem 2 ve 3 ile verilebilir. (2) (3)
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Bu reaksiyonlara ilaveten Denklem 4, 5 ve 6 da verilmi olan reaksiyonlarn ortaya kmas muhtemeldir. CH4 ile H2O ve CO2 arasndaki reaksiyonlar (Denklem 5 ve 6) CO ve H2 miktarlarnn artmasna yol aabilir. (4) (5) (6) C oluumu iin reaksiyonlar Denklem 4 (CH4 n paralanmas) ve 7 ile ifade edilebilir. Denklem 7 ile verilen Boudouard reaksiyonu 1000 K in altndaki scaklklarda C oluumuna neden olmaktadr. 1000 K zerinde ise reaksiyon tersine dnerek (CO2, C la reaksiyona girerek) CO oluumuna yol amaktadr. Bunun sonucu olarak kat hal diyagramnda Ni+C faz alan artan scaklkla daralmakta, yksek scaklklarda ( 1000 K) serbest C sadece CH4 n sl paralanmasyla olumaktadr. (7) Yukarda verilen bilgiler nda NiO-CH4 sisteminde Ni+C oluumu iin genel reaksiyonlar Denklem 8 ve 9 ile ifade edilebilir. (8) Termodinamik analiz, artan CH4 mol kesriyle NiONiNi+C dnmnn olacan ngrmektedir. 4. TARTIMA CH4 atmosferi altnda izortermal artlarda oksit tozunda gerekleen arlk deiimleri, esas itibaryla balang tozunun tamamnda Ni:O orann 1:1 olmadn, NiO faz yannda Ni2O3, Ni(OH)2 gibi dier fazlar da ierebileceini gstermitir. Bahsedilen ilave fazlar X-n difraksiyonunda deiik nedenlerden (amorf yap, faz miktarnn az olmas) tr tespit edilememitir. Ayrca, Ar atmosferinde balangta siyah renkte olan orijinal tozun, arlk orannn ~% 90 olduunda, ak yeile (NiO in tipik rengine) dnmesi bileimde deiimin (oksijen miktarnn azalmas) olduunun iaretidir. Teorik olarak Ni:O orannn 2:3 ten 1:1 e dt toz arlk oran (% 91,3) grafiklerinde yatay referans izgisi olarak gsterilmitir. Deneysel sonucun bu deere yakn olmas, balang tozunun oksijence daha zengin olduunu gstermektedir. Bu gzlemler balang tozunda Ni:O orannn 2:3 olduuna iaret etmektedir. Ayrca, DTA-DSC-TG ve FTIR analizleri bu sonucu desteklemektedir. Deneysel artlar, kat hal denge diyagramnda tm scaklklar iin yksek CH4 mol kesirlerine (1 e yakn) tekabl etmektedir. Diyagrama gre denge durumunda rnlerin Ni+C fazlarndan olumas gerekirken deneysel sonular, 1200 K in altndaki scaklklarda serbest C un olumadn gstermektedir. Bu durum, dk scaklklarda CH4 n yeteri kadar paralanmadn, dolaysyla serbest C olumadn gstermektedir. Bu scaklklarda kinetik faktrler nemli rol oynamaktadr. 1200 ve 1300 K de ise CH4 n paralanma derecesi artarak rnlerde Ni yannda serbest C da grlmektedir. Yksek scaklklarda kinetik faktrler nemini yitirmekte ve sistem termodinamik dengeye yaklamaktadr. Termodinamik ngrler, artan CH4 miktaryla NiO tozundaki deiimleri srasyla NiONiNi+C eklinde olduunu gstermekte olup 1200-1300 K deki deneysel sonularla kalitatif olarak uyum iindedir. XRD analiz sonular, arlk oran verilerini dorulamaktadr. rnein, 1300 K de zamanla NiO faz Ni e kademeli olarak dnmekte, artan reaksiyon sresiyle Ni faznn yannda bulunan serbest C a ait (002) pikinin iddeti (C miktar) artmaktadr. 5. SONU Nanokristal nikel oksit tozunun reaksiyon davran farkl scaklk (1000-1300 K) ve sre iin saf metan altnda incelenmitir. CH4, atmosferi altnda scaklk ve sreye bal olarak arlk oranlarndaki deiimler oksit tozunun oksijence daha zengin olduunu (Ni:O=1:1 oranndan daha yksek), muhtemelen bu orann 2:3 olduunu gstermitir. FTIR ve DTA/DSC-TG analizleri bu sonucu desteklemekte olup yapda NiO in yannda az miktarda Ni(OH)2xH2O faznn bulunduu tahmin edilmektedir. Termodinamik ngrler, artan CH4 miktaryla NiO tozundaki deiimleri srasyla NiONiNi+C eklinde olduunu gstermekte olup 1200-1300 K deki XRD ve arlk oran verileriyle kalitatif olarak uyum iindedir. NiO-CH4 sisteminde nemli reaksiyonun; NiO(k)+2CH4 Ni(k)+C(k)+CO+4H2 eklinde olduu ngrlmektedir. (9)
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TEEKKR Bu alma, ..Aratrma Projeleri Birimi tarafndan 1459 numaras ile desteklenen proje ile M. C. Altay n doktora tezinin bir blmdr. KAYNAKLAR 1. Xiao-Yan, G., Jian-Cheng, D., Preparation and Electrochemical Performance of Nano-Scale Nickel Hydroxide with Different Shapes, Materials Letters, 61, 621-625, 2007. 2. Patil, P. S., Kadam, L. D., Preparation and Characterization of Spray Pyrolyzed Nickel Oxide (NiO) Thin Films, Applied Surface Science, 199, 211-221, 2002. 3. Bououdina, M., Grant, D., Walker, G., Effect Of Processing Conditions On Unsupported Ni-Based Catalysts For Graphitic-Nanofibre Formation, Carbon, 43 1286-1292, 2005. 4.Kuchibhatla, S. V. N. T., Karakoti, A. S., Bera, D., Seal, S., One Dimensional Nanostructured Materials, Progress in Materials Science, 52, 699-913, 2007. 5. Yang, P., The Chemistry of Nanostructured Materials, World scientific publishing, New Jersey, U.S.A., 2003.
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SNEK METALLERN TLMESNDE EEKSENL AISAL PRESLEME KULLANIMI LE NCE TOZ RETM
Glhan AKMAK ve Tayfur ZTRK Orta Dou Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 06800, Ankara ozturk@metu.edu.tr zet Snek metallerde ince toz retimi kuru tmede topaklama nedeni ile ou kez mmkn olmamaktadr. Her ne kadar dk scaklklarda tme ve/veya slak tme belirli oranlarda baarl olsa da snek metal ve alamlardan ince toz retimi skntl bir sretir. Bu alma Mg tozlarnn tlmesini konu almakta ve etkin inceltme amal olarak iki yntemi deerlendirmektedir. Bu yntemler MgH2 ilavesi ile tme ve e kanall asal preslemeyi takiben tmedir. alma her iki yntemin de baarl sonular verdiini gstermekle beraber e kanall asal presleme tm snek tozlara uygulanabilir olmas nitelii ile n plana kmaktadr. nerilen yntem snek tozlarn e kanall asal prese beslenmesi ve birka paso preslemeyi takiben sertlemi metalin mekanik olarak tlmesidir. Anahtar Kelimeler: Mekanik tme, Katkl tme, E Kanall Asal Presleme, Parack Boyutu, Hcre Bykl.
equal channel angular PRESSING AS an a ad n the mllng of ductle powders

ABSTRACT Mechanical milling of ductile metals and alloys into fine powders are difficult to achieve due to particle agglomeration. Even though cyrogenic milling and/or wet milling can lead to substantial reduction of particle size, the production of fine powders from ductile metals is a difficult process. The current study deals with the milling of Mg powder and examines processing methods that would yield an efficient size reduction. Two methods were investigated i.e. milling with MgH2 addition, and milling the powders pre-deformed via equal channel angular pressing(ECAP). The study shows that both methods are successful in imparting a substantial size reduction but preprocessing of powders via equal channel angular pressing has more applicability. In this method, metal powders may be subjected to several passes of equal channel angular pressing followed by mechanical milling. Keywords: Mechanical Milling, Milling with Additives, Equal Channel Angular Pressing(ECAP), Particle Size, Coherently Diffracting Volume, 1. GR Toz boyutlar her ne kadar toz retim aamasnda ilgili parametrelerin kontrol ile denetim altna alnabilse de, elde edilen boyutlar ou uygulama iin iri kalmakta, bu da retim sonras parack inceltme srelerini gerekli klmaktadr. nceltme, genellikle mekanik tme ile gerekletirilmektedir. Bu ilem, seramik ve intermetalikler gibi krlgan tozlarda baarl sonular vermekte ve -kuru halde gerekletirilmeleri halinde bile- mikron alt tozlarn eldesi mmkn olabilmektedir. Bu durum snek tozlarda farkllk gstermekte, sneklik nedeni ile paracklar ufalanma yerine arpma srasnda yer yer yapmakta ve aglomere olmaktadr[1]. Bu nedenle snek tozlar ou kez sv
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bir ortam iinde tlmektedir[2]. Sv ortamn kullanm her uygulama iin uygun dmemekte, bu durum alternatif yntemlerin kullanmn gerekli klmaktadr. Bu yntemler malzeme snekliliini azaltma amal olup, bunun nispeten yaygn uygulamas tmenin dk scaklklarda yaplmasdr[3]. Hidrr oluturan metallerde tmenin hidrojen atmosferi altnda yaplmas gene yaygn bir uygulamadr[4]. Bavurulabilecek dier bir yntem tozlara uygun katklar yaplarak snekliinin azaltlmasdr. Oksit[5], karbr[6] veya florrler[7] bu ama iin yaygnca kullanlan ilavelerdir. nce toz eldesi Mg ve Mg esasl alamlarda nem arz eden bir husustur. Bu durum zellikle hidrojen depolama asndan bir gereklilik olmakta ve sorunun nitelii gerei ilemin kuru olarak gerekletirilmesi gerekmektedir. Bu almada magnezyumun tlmesinde iki yeni yntem deerlendirilmitir. Bunlar, katk maddesi olarak MgH2 ilavesi ile tme ve e kanall asal preslemeyi takiben tme eklindedir. 2. DENEYSEL YNTEM Bu almada kullanlan Mg tozu (Alfa Aesar) % 99,8 saflkta ve parack bykl ortalama 45,7 m dir. Yaplan almada ou deney saf Mg tozu ile gerekletirilmitir. Katkl karmlar Mgye MgH2(Goldschmidt) ilavesi ile hazrlanmtr. tme ilemleri gezegensel deirmende (Fritsch-Pulverisette 7 Premium Line) argon gaz altnda yaplmtr. tme ilemleri paslanmaz elik hazne ierisinde 15 mm apnda paslanmaz elik toplar kullanlmak sureti ile gerekletirilmitir. Top/toz oran 10:1 olarak seilmi ve cihaz 700 rpm hzda altrlmtr. tme her yarm saatte yarm saatlik srelerle durdurulmu ve bu ekilde ortamn snmas kontrol altnda tutulmutur. E kanall asal pres ilemi iin kullanlan kalp ematik olarak ekil 1 de verilmektedir. Tozlarn kalp boluuna beslenebilmesi iin tozlar nce bakr bir blok ierisine yerletirilmitir. Bu amala 14x14 mm boyutlarndaki bloun orta ekseni 8 mm apnda delinmi ve bu delik toz konduktan sonra bakr bir tpa yardmyla kapatlmtr. Verilen geometride kalp ke as =90 (d ke =20) olup numunenin kalptan geirilii gerek gerinme olarak =1 e denk gelmektedir[8]. Her bir gei sonras numune dikey ekseni boyunca 90 evirilerek kanala tekrar beslenmitir.
ekil 1. E kanall asal pres kalbnn ematik grnm (=90 ve =20) lem gren tozlarda parack boyutu, tarama elektron mikroskop grntleri zerinde lm almak veya lazer parack boyut lm ile tespit edilmitir. Mgnin su ile reaksiyona girmesi nedeni ile lazer ile lmde tozlar etanol iinde datlmtr. Paracklarda, uyumlu krnm salayan hacim dier bir ifade ile hcre bykl X-nlar krnm ile tespit edilmitir. Bu amala veri, CuK kullanlmak sureti ile 20<2<90 aralnda toplanmtr. Veriler adml tarama modunda 0.02 lik aralklarla 3 s sre ile toplanmtr.
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ekil 2. MgH2 ilaveli tme ile Mg de elde edilen toz yaps (a)Mg (b)Mg-%5 MgH2 (c) Mg-%10 MgH2 (d) Mg-%30 MgH2 3. BULGU VE DEERLENDRME Bu blmde nce MgH2 ilaveli tme ele alnacak, takibende e kanall asal presleme sonras tme deerlendirilecektir. MgH2 ilavesi ile tme MgH2 ilaveli tme iin Mg tozlarna hacimce % 5, % 10 ve % 30 MgH2 ilave edilmitir. Her bir deney iin toplam 10 gr toz kullanlm ve tme argon atmosferi altnda gerekletirilmitir. 3 saat tme sonras elde edilen toz byklkleri ekil 2 de verilmektedir. Tespit edilen SEM grntleri zerinde yaplan lmler sonucu elde edilen parack byklkleri izelge 1 de verilmektedir. Grlecei zere MgH2 ilaveli tme ilavesiz tmeye oranla daha kk deerler vermektedir. lavesiz tme ile elde edilen parack bykl ortalama 80 m iken bu deer % 5-10 MgH2 ilavesi ile 20 civarna dmekte ilave miktarnn % 30 a kartlmas ile ortalama byklk 11 m e dmektedir. X nlar krnm yntemi ile tespit edilen hcre byklkleri izelge 1 e dahil edilmitir. Benzer ekilde, artan MgH2 ilavesi ile parac oluturan hcreler klmekte, ancak bu klme parack boyutuna gre daha tedrici kalmaktadr. izelge 1. MgH2 katks ile tlen Mg de parack boyutu ve hcre bykl Numune Parack bykl (m) Mg 79,43 Mg-5% MgH2 26.85 42.33 Mg-10% MgH2 22.16 30.36 Mg-30% MgH2 11.19 24.57
Hcre bykl (nm) 79.7
E kanall asal presleme kullanm ile tme Bakr blok iersine yerletirilen Mg tozlar ekil 1de gsterilen kalp kullanlmak sureti ile 4 kez kalptan geirilmitir. Mg tozlarnda bu ilem sonras tespit edilen SEM grntleri ekil 3de verilmektedir. Grlecei zere bu ilem sonucu tozlar konsolide olmakta ve yekparelemektedir. Drt paso sonras yekpare halde bakr bloktan kartlan numune havanda krlm ve takiben tme ilemine tabi tutulmutur.
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ekil 3. E kanall asal presleme yntemi ile deforme edilmi Mg tozlarnda yap. a) balang mikroyaps (b) Presleme sonras yap (kayma dzlemi kesidi) Presleme sonras tlen tozlarn yaps ekil 4de verilmektedir. Grlecei zere tme ile elde edilen yaplar magnezyumun dorudan tlmesi ile elde edilen yapdan -baknz ekil 2(a)- bir hayli incedir. Tozlar artan tme sresi ile tedrici bir incelme gstermektedirler. ki saat sonras ortalama 40 m olan toz boyutu 5 saatlik sre sonunda 26 m e inmektedir. Yukarda verilen sonular magnezyumun gerek MgH2 ilavesi gerekse e kanall asal presleme ile daha etkin tarzda tlebileceini gstermektedir. Nitekim tek bana kuru olarak tlen Mg, 5 saat sonunda yaklak 70 m lik paracklar verirken MgH2 ilaveli tme % 5-10 mertebelik ilavelerde 20-30 m lik paracklar (%30 lk ilavede 11 m), e kanall asal preslemede ise benzer srede 26 m lik paracklar vermektedir.Burada belirtilmesi gereken bir husus katknn MgH2 olmas nedeni ile burada bir hacim kaybnn olmaddr. Tozlarn dehidrrlenmesi ile tm yap Mgye dnecektir. Bu durum hidrr oluturan metallerin katkl tme ile baarl tarzda tlebileceini gstermektedir.
ekil 4. E kanall asal presleme sonras tlen Mg tozlarnda mikroyap. (a) 0,5 s (b) 1 s (c)2 s (d) 5 s tme. E kanall asal presleme ile tme, metal hidrr katkl tmeden farkl olarak tm metallere ve alamlara uygulanabilir bir sretir. Bu nedenle ayr bir neme sahiptir. Bu ilem sonras elde edilen etkin incelme byk bir ihtimalle ilemin sebep olduu gerinme sertlemesinden dier bir ifade ile sneklik azalmasndan kaynaklanmakta-
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dr. E kanall asal presleme ile malzemelerin hzla sertletii ve bu sertlemenin byk oranda ilk paso srasnda gerekletii bilinmektedir[9]. E kanall asal preslemenin dier bir stnl tmenin aksine malzeme yzey alannda artn bu ilemde snrl kalmasdr. Bu durum atmosferden etkilenen tozlarn ilenmesinde bir stnlk salamakta, tozlar atmosfer kontrolsz ortamda ilenebilmektedir. Bu koullarda nerilen yaklam tozlarn atmosfer kontrolsz olarak e kanall asal kalpta birka paso preslenmesi ve takiben atmosfer kontroll bir ortamda ksa srelerle tlmesidir[10]. 3. SONU Mg tozlarnn inceltilmesini konu alan bu almada MgH2 ilavesi ile tme ve e kanall asal preslemeyi takiben tme yntemleri deerlendirilmitir. alma her iki yntemin de baarl sonular verdiini gstermi ve 1- MgH2 nin 1/3 hacim oranlk ilavesi ile yaplan 3 saatlik tme sonunda parack byklnn 11,2 m indirilebildiini 2- Ekanall asal presleme ile tozlarn deforme edilmesi durumunda tozlarn nce yekpareletii, takiben yaplan tmede ise etkin bir incelme gsterdii tespit edilmitir. Magnezyumun dorudan tlmesi durumunda elde edilen parack byklnn 5 saat sonunda 70 m olduu dikkate alndnda yukarda verilen deerler tozlarda ciddi bir incelmeye iaret etmektedir. MgH2 katk miktarnn yksek olmas katkl tmenin ancak hidrr oluturan metaller iin uygulanabilir bir yntem olduu anlamndadr. Bu durum ekanall asal preselemeyi yntem olarak nplana kartmaktadr. KAYNAKLAR 1. Suryanarayana, C. Mechanical alloying and milling, Progress in Materials Science , Vol.46,1,2001 2. Arias, A.,The Role of Chemical Reactions in the Mechanism of Comminution of Ductile Metals into Ultrafine Powders by Grinding NASA technical Note, 1968 3. Song, M. Y., Kwon, S. N., Bobet, J-L,Park, H. R. Enhancement of hydrogen-storage properties of Mg by reactive mechanical grinding with oxide, metallic element(s), and hydride-forming element Ceramics International, vol. 37, 897-902, 2011 4. Bobet, J.-L., Akiba, E., Darriet, B., Study of Mg-M(M=Co,Ni, and Fe) mixture elaborated by reactive mechanical alloying: hydrogen sorption properties International Journal of Hydrogen Energy, Vol. 26, . 493-501, 2001 5. Friedrichs, O., Klassen, T., Sanchez-Lopez, J.C., Bormann, R., Fernandez, A. Hydrogen sorption improvement of nanocrystalline MgH2 by Nb2O5 nanoparticles Scripta Materialia 54/7, 473,2006 6. Gvendiren, M., Baybr, E., ztrk, T., Effects of additives on mechanical milling and hydrogenation of magnesium powders International Journal of Hydrogen Energy, vol. 29, 491, 2004 7. Deledd, S., Borissov, A., Poinsignon C., Bott W.J., Dornheim, M., Klassen, T., H-sorption in MgH2 nanocomposites containing Fe or Ni with uorin , Journal of Alloys and Compounds , vol. 404/406, 409412, 2005 8. Valiev, R., Islamgaliev, R.K., Alexandrov, I.V., Bulk nanostructured materials from severe plastic deformation, Progress in Materials Science , vol. 45, 103-189,2000 9. Valiev, R., Langdon, T.G., Principles of equal channel angular pressing as a processing tool for grain refinement, Progress in Materilas Science ,vol. 51, 881, 2006, 10. akmak, G., ztrk, T., ECAP processing and mechanical milling of Mg and MgTi powders: a comparative study, Journal of Materials Science , vol. 46, 5559-5567, 2011
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Sv Fazl sinterlenen W-Ni-Cu alamlarnda soutma hznn mekanik zelliklere etkisi

N. Kaan ALIKAN*, Nuri DURLU**, A. akir BOR*** *TBTAK-SAGE, Metal ve Seramik Malzemeler Birimi, PK 16, Mamak, Ankara, ** TOBB, Ekonomi ve Teknoloji niversitesi, Makina Mh Bl., 06560, Ankara, ***Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mh. Bl., Ankara ZET Tungsten ar alamlar sv fazl sinterleme teknikleri kullanlarak retilen iki fazl kompozit malzemelerdir. Bu almada sv fazl sinterlenen 90W-7Ni-3Cu ve 90W-3Ni-7Cu alamlarnda sinterleme ileminden sonra yaplan soutma ilemi hznn mekanik zelliklere etkisi incelenmitir. Numuneler souk izostatik presleme ile 300 MPa basn altnda preslenmi ve 1430Cde hidrojen ve argon altnda 30 dakika sre ile sinterlenmitir. Sinterleme ileminden sonra numuneler iki farkl soutma hznda soutulmutur. Numunelerin mikroyaplar ve mekanik zellikleri incelenmitir. Sv fazl sinterlenen 90W-7Ni-3Cu alamnn ekme dayanmnn ve % uzamasnn 90W-3Ni-7Cu alamna kyasla daha iyi olduu belirlenmitir. 90W-7Ni-3Cu alamnda sinterleme sonrasndaki soutma hznn yava olmasna bal olarak ekme dayanmnn ve % uzamann artt, 90W-3Ni-7Cu alamnda ise yava soutma koullarnda ekme dayanmnn dt ve snekliin artt belirlenmitir. Anahtar Kelimeler: Tungsten ar alamlar, sv fazl sinterleme, W-Ni-Cu, mekanik zellikler, soutma hz
EFFECT OF coolng rate ON The MECHANICAL PROPERTIES OF lqud phase sntered W-N-cu Alloys
ABSTRACT Tungsten based alloys are two phase composite materials manufactured by liquid phase sintering technique. In this study, the effect of cooling rate after liquid phase sintering was investigated in 90W-7Ni-3Cu and 90W-3Ni7Cu alloys. Samples were cold isostatically pressed under 300 MPa and sintered at 1430C for 30 minutes under hydrogen and argon. After liquid phase sintering the samples were cooled at two different cooling rates. The mechanical properties of the samples were determined, and the microstructures were investigated. The mechanical properties of the 90W-7Ni-3Cu alloy was found to be better than the 90W-3Ni-7Cu alloy. In the 90W-7Ni-3Cu alloy, with the slower cooling rate after sintering, an increase in tensile strength and % elongation was observed. On the other hand, in the 90W-3Ni-7Cu alloy, slower cooling rate led to a decrease in tensile strength and an increase in % elongation. Key Words : Tungsten heavy alloys, liquid phase sintering, W-Ni-Cu, mechanical properties, cooling rates
1. GR Tungsten ar alamlar sv fazl sinterleme teknii ile retilen iki fazl metal matriks kompozitleridir. Tungsten ar alamlarnn sahip olduklar yksek younluk, yksek ekme dayanm, yksek sneklik ve iyi korozyon zellikleri, bu tr alamlarn zellikle savunma sanayisine ynelik uygulamalarda yaygn kullanmna yol amtr. Tungsten ar alamlarnda en youn olarak kullanlan l alam sistemleri W-Ni-Fe ve W-Ni-Cudr. Yaklak ola-
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rak %90-%98 arlk oranlarndaki Wnin, belirli oranlardaki Ni-Fe veya Ni-Cu balayc faz bileimleri ile birlikte 1410C1500C aralndaki scaklklarda koruyucu ortam altnda sv fazl sinterlenmesi, yksek younlua ve mekanik zelliklere sahip alamlarn retimini salamaktadr. Sinterleme sonras oluan iki fazl mikroyapda yksek oranda hacim merkez kp kristal yapl W faz, ve balayc faz (veya matriks) olarak kullanlan yzey merkez kp kristal yapl Ni-Fe-W veya Ni-Cu-W kat zelti faz bulunmaktadr. Tungsten ar alamlarnn sv fazl sinterlenmesi ile ilgili ilk alma 1930lu yllarda W-Ni-Cu l alam sisteminde yaplmtr [1]. Ancak W-Ni-Cu alam sisteminin istenilen mekanik zellikleri salayamamas nedeni ile, 1950li yllarda daha iyi mekanik zellikler salayan W-Ni-Fe sistemi yaygn bir ekilde kullanlmaya balanmtr. Gnmzde W-Ni-Cu l alam sistemindeki tungsten ar alamlar manyetik geirgenliinin dk olmas nedeni ile manyetik alan etkilenmeyen uygulamalarda yaygn olarak kullanlmaktadr [2]. W-Ni-Cu ve W-Ni-Fe sistemlerindeki ar alamlarn mekanik zelliklerinin incelendii almalarda, 90W-6Ni-4Cu alamnn ekme dayanm 600 MPa, uzama ise %3 olarak [3], 90W-7Ni-3Cu alamnn ekme dayanmnn ise 770 MPa ve uzamann ise %0,5 ile %6 arasnda deitii gzlenmitir [4]. 90W-6Ni-4Cu alamnn sv fazl sinterleme ilemi 1425Cde 1 saat sre ile hidrojen altnda yaplm ve daha sonra numuneler hzl bir ekilde oda scaklna soutulmu [3], 90W-7Ni-3Cu alamnda ise sv fazl sinterleme ilemi 1410Cde hidrojen altnda yapldktan sonra numuneler frnda soutulmutur [4]. 90W-7Ni-3Cu alamnda yaplan detayl mikroyap incelemelerinde herhangi bir intermetalik faz oluumuna rastlanmam, ancak Auger elektron spektroskopisi ile yaplan incelemelerde tungsten ile matriks arayzeyinde gzlenen P ve S birikintilerinin gevreklemeye yol aarak dk % uzama deerlerine yol at ifade edilmitir [4]. Hidrojen altnda 1420Cde 1 saat sre ile sinterlenen ve frnda soutulan 90,4W-7,2Ni-2,4Cu alamnda yaplan detayl transmisyon elektron mikroskop almalarnda frnda soutulan numunelerde herhangi bir intermetalik faz oluumuna rastlanmam, ancak 1350Cde bir saat tavlandktan sonra su verilen numunelerde tungsten ve matriks arasndaki snrlarda intermetalik faz oluumlar gzlenmitir [5]. Transmisyon elektron mikroskop almalar fazlar arasnda ince bir film olarak oluan bu fazn Ni4W faz olduunu gstermitir. W-Ni-Cu l sisteminde balayc faz bileimindeki Ni:Cu orannn 7:3 olarak, ve balayc faz miktarnn %5 ile %25 arasnda seildii bir almada, 1300C ve 1350Cde yaplan sv fazl sinterleme ilemi sonrasnda, balayc faz miktarndaki arta ve sinterleme sresindeki arta bal olarak W paracklarnn byklnn ve bitiikliin azald gzlenmitir [6]. W-Ni-Cu l sisteminde daha yksek oranlarda W ( > %92,5) ve balayc faz iindeki Ni:Cu orann yksek olduu (>2,5) ar alamlarda yaplan almalarda, numunelerin ekme dayanmlarnn 660 ile 701 MPa arasnda, % uzamalarnn ise 3 ile 6 arasnda olduu gzlenmitir [7,8]. W-Ni-Cu sistemindeki ar alamlarnn performans toz zelliklerinden, alam iindeki tungsten miktar ve balayc faz bileiminden, sv fazl sinterleme ortam ve sresinden, ve sinterleme ilemi sonrasndaki soutma hzna bal olarak oluan mikroyapdan etkilenmektedir. Bu almada sv fazl sinterlenen 90W-7Ni-3Cu ve 90W-3Ni7Cu alamlarnda, sinterleme sonras iki farkl hzda yaplan soutma ileminin mekanik zelliklere etkisi incelenmitir. 2. DENEYSEL YNTEM Deneysel almalarda kullanlan Cu, Ni ve W metal tozlarnn zellikleri izelge 1de verilmitir. Tozlarn ortalama tane byklkleri lazer tane bykl analiz cihaz (Model: Malvern Mastersizer 2000) ile llmtr. Tozlarn parack ekli taramal elektron mikroskop ile incelenmi ve ekil 1de verilmitir. izelge 1. almada kullanlan metal tozlarn zellikleri. Toz retici Saflk Toz ekli D10(m) D50(m) D90(m) Cu AEE 99.9+ Kresel 3.1 6.5 12.3 Ni AEE 99.9+ Kresel 5.2 9.1 16.1 W Eurotungstene 99.9+ Poligonal 1.7 4.2 10.3
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Elementel metal tozlarndan yaklak olarak 3 kg olarak hazrlanan 90W-7Ni-3Cu ve 90W-3Ni-7Cu toz karmlar Turbula kartrcda (Model: T2F Glenn Mills) dakikada 67 devir ile 45 dakika sre ile kartrlmlardr. Toz karmlarnn ekillendirilmesinde polimerik kalplar kullanlm ve numuneler souk izostatik presleme cihaznda (Model: Flow Autoclave Engineers CIP 42260) yaklak 15 saniye boyunca 300 MPa basn altnda sktrlarak ekillendirilmilerdir. ekillendirilen W-Ni-Cu alamlarn ya numunelerinin yaklak %65 teorik younlua ulatklar belirlenmitir.
ekil 1. almada kullanlan Cu, Ni ve W metal tozlarnn taramal elektron mikroskop grntleri. Sinterleme almalar yksek saflkta hidrojen gaz altnda (ilenme noktas = - 60C), 1430Cde atmosfer kontroll frn (Linn HT-1800) kullanlarak gerekletirilmitir. Sinterleme dngs u ekilde uygulanmtr : 9C/dakika stma hz ile 1000Cye stma, saf H2 altnda 1000Cde 30 dakika oksit indirgeme, 3C/dakika stma hz ile 1430Cye stma, 1430Cde 20 dakika sre ile H2 altnda ve 10 dakika sre ile argon altnda sinterlemenin ardndan iki farkl hzda soutma. Yava olarak yaplan soutma ileminde numuneler 1430Cden 1130Cye kadar 2,6C/ dak. hznda soutulduktan sonra frnda soutulmaya braklm, daha hzl olarak yaplan soutma ileminde ise numuneler 1430Cden 1330Cye 2,8C/dak. hznda soutulduktan sonra frnda soutulmaya braklmtr. Sinterlenen numunelerin mekanik zelliklerini belirleme almalarnda kullanlmak zere ekme testi ubuu ve sertlik, younluk lm ve iyap incelemeleri iin ise kk numune retimi yaplmtr. ekme deneyinde kullanlan numuneler uluslararas standarda uygun ekilde (ISO 6892) hazrlanmtr. ekme testi (Model: 3369 Instron) 0.5mm/dakika ekme hznda gerekletirilmitir. ekme testi sonular 3 adet numunenin ortalamas alnarak verilmitir. Alam numunelerinin iyaps geleneksel metalografi yntemleri ile incelenmitir. yap incelemeleri iin hazrlanan numuneler literatrde nerilen Murakami zeltisi (10 g K3Fe(CN)6, 10g NaOH, ve 100 ml saf H2O) ile dalanmtr. Numunelerin iyap incelemeleri nokta sayma yntemi kullanlarak optik mikroskop grntleri zerinden gerekletirilmitir. Fazlarn hacimce miktarnn belirleme almalar ASTM E562 standardnn uygulanmas ile gerekletirilmitir. Tungsten bitiiklik deeri ise optik mikroskop grntleri zerine 10x10cmlik ve 1cm aralkl matrislerin izilmesiyle her bir izgiye den W-W balantsnn saylmasyla gerekletirilmitir. Bitiiklik deerinin hesaplanmasnda kullanlan basit denklem u ekildedir [9].
NWW = izgi bana den W-W balant says NWM = izgi bana den W-balayc faz balant says Sinterlenmi numunelerin younluk lmleri hassas terazi kullanlarak Arimet prensibi ile gerekletirilmitir. Younluk lmlerinde sv olarak ksilen (younluk 0.86g/cm3) kullanlmtr. W-Ni-Cu alamlarndaki faz dnm scaklklar DSC cihaz (Model: Setaram Setsys Evolution) kullanlarak belirlenmitir. DSC cihaznda argon atmosferi altnda yaplan lmlerde stma ve soutma hz olarak 10C/dakika kullanlmtr. 3. DENEYSEL SONULAR ve TARTIMA Sv fazl sinterlenmi ve farkl hzlarda soutulmu numunelerin optik mikroskop grntleri ekil 2de verilmitir. Alamlarn mikroyaplar, kresel W tanelerinden, ve Ni-Cu-W balayc fazndan (veya matriks faz) olumaktadr. Parlatlm numune yzeylerinde yaplan optik mikroskop incelemelerinde gzenek miktarnn ok az (<%1) olduu ve younluk lmlerinde de btn numunelerin younluunun %99 teorik younluk civarnda olduu belirlenmitir.
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ekil 2. Sv fazl sinterlenmi numunelerin optik mikroskop grntleri. (a) 90W-7Ni-3Cu, yava soutma, (b) 90W-7Ni-3Cu, hzl soutma (c) 90W-3Ni-7Cu, yava soutma, (d) 90W-3Ni-7Cu, hzl soutma. ekil 2de verilen optik mikroskop grntlerinde sv fazl sinterlenmi 90W-7Ni-3Cu alamndaki W tanelerinin, 90W-3Ni-7Cu numunelerindeki W tanelerine kyasla daha byk olduu grlmektedir. Optik mikroskop grntleri zerinde yaplan W tane bykl lmlerinde, ortalama W tane byklkleri yava ve hzl soutulmu 90W-7Ni-3Cu alamlar iin 22,55 mikron ve 214 mikron, yava ve hzl soutulmu 90W-3Ni-7Cu alamlar iin ise 163 mikron ve 164 mikron olarak llm ve soutma hznn mikroyapdaki ortalama W tane byklne nemli bir etkisinin olmad belirlenmitir. Optik mikroskop grntlerinden, grnt yazlm ile yaplan mikroyap incelemelerinde, sinterlenmi numunelerdeki toplam balayc faz miktarnn 90W-7Ni-3Cu alamnda yaklak olarak %18, 90W-3Ni-7Cu alamnda ise %10 olduu belirlenmi ve soutma hznn balayc faz miktarnda nemli bir deiime yol amad gzlenmitir. Balayc faz iindeki Ni:Cu orannn artmasna bal olarak W tane bykl ve balayc faz miktar artmtr. Bu artlarn nedeni Wnin 7Ni-3Cu balayc faz iindeki znrllnn, 3Ni-7Cu balayc faz iindeki W znrlne kyasla daha fazla olmasdr [10]. Sv fazl sinterleme ileminin baar ile gereklemesi iin yksek miktarda kat fazn sv faz ierisinde znmesi gerekmektedir. Kat fazn sv faz ierisindeki znrlnn artmas ile sv faz miktar artmakta, slatma as dmekte ve znme-yeniden kelme aamasnn ok hzl gereklemesi nedeni ile son iyapdaki kat fazn bykl artmaktadr [9]. DSC almalar ile sv fazl sinterlenmi ve farkl soutma hzlarnda soutulmu numunelerin faz dnm scaklklar belirlenmitir. Yaplan DSC deneylerinin stma erilerinden balayc faz iindeki Ni:Cu orannn 7:3 olduu numunede katgen scakl yaklak olarak 1387C svgen scakl ise 1426C olarak belirlenmitir. Balayc faz iindeki Ni:Cu orannn 3:7 olduu durumda ise, katgen scakl 1188C, svgen scakl ise 1262C olarak llmtr. Bakr-nikel ikili faz diyagram incelendiinde, Ni:Cu orannn 7:3 olduu durumda svgen scakl 1375C, Ni-Cu orannn 3:7 olduu durumda ise svgen scakl 1245Cdir [11]. 90W-7Ni-3Cu numunesinde gzlenen svgen scakl 1426Cdir ve bu bileimdeki 7Ni-3Cu alamnn svgen scaklndan yaklak olarak 51C zerindedir. 90W-3Ni-7Cu alamnda ise Ni-Cu-W kat zeltisinin svgen scakl ile 3Ni-7Cu ikili alamn svgen scaklklar arasnda yaklak olarak 17Clik bir fark bulunmaktadr. Her iki alamda da Wnin balayc faz iinde znmesi, svgen erilerinde arta yol amtr. Ancak 90W-7Ni-3Cu alamnda balayc faz iindeki W znrl, 90W-3Ni-7Cu alamndaki balayc faza gre daha fazla olduu iin, l alamn svgen scaklndaki art daha fazla olmutur [10]. Sv fazl sinterlenen ve farkl soutma hzlarnda soutulan 90W-7Ni-3Cu ve 90W-3Ni-7Cu ar alamlarnn optik mikroskop grntleri zerinden yaplan mikroyap incelemeleri ile bitiiklik deerleri belirlenmitir. 90W-7Ni-3Cu alamndaki bitiiklik deerleri yava soutmada 0,37 ve hzl soutma da 0,46 olarak, 90W-3Ni-7Cu alamnda ise bitiiklik deeri yava soutmada 0,64 hzl soutmada ise 0,67 olarak llmtr. W-Ni-Cu alamlarnda llen bitiiklik deerleri mekanik zellikler asndan 90W-7Ni-3Cu alamnn 90W-3Ni-7Cu numunesine gre daha
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iyi mekanik zelliklere sahip olabileceini ve bu alamlarda yava soutma hzlarnn daha iyi mekanik zellikler vereceini gstermektedir. Sv fazl sinterlendikten sonra farkl hzlarda soutulmu numunelerin mekanik zellikleri izelge 2de verilmitir. Sinterlenmi numuneler arasnda en yksek ekme dayanm (776 MPa) ve uzama deeri (%9,2) yava soutulmu 90W-7Ni-3Cu numunesinde gzlenmitir. Bu numunede soutma hznn artrlmas ekme dayanm deerinde ve % uzama deerinde dmeye yol amtr. 90W-7Ni-3Cu numunesinde izelge 2. Sv fazl sinterlenmi ve farkl soutma hzlarnda soutulmu 90W-7Ni-3Cu ve 90W-3Ni-7Cu alamlarnn mekanik zellikleri. Numune 90W-7Ni-3Cu a 90W-7Ni-3Cu b 90W-3Ni-7Cu a 90W-3Ni-7Cu b
a
ekme Dayanm (MPa) 77614 74312 6811 7136
Uzama (%) 9.21.8 7.51.5 4.80.4 3.80.5
1430Cden 1100Cye argon altnda 2,6C/dak. hznda soutmann ardndan frnda soutma b1430Cden 1365Cye argon altnda 2,6C/dak. hznda soutmann ardndan frnda soutmafarkl soutma hzlarnda elde edilen ekme dayanm deerleri Edmonds ve Jones tarafndan ayn alam sistemi iin yaplan bir almadaki deerler ile benzerlik gstermektedir [4]. Ancak almamzda bu alam iin iki farkl soutma hznda daha yksek % uzama deerleri elde edilmitir. ki farkl hzda soutulmu 90W-3Ni-7Cu alamlarnn ekme dayanm ve % uzama deerleri 90W-7Ni-3Cu alamlarna kyasla daha dktr. Bunun nedeni dk Ni:Cu oranlarnda, Wnin balayc faz iindeki znrlnn dk olmas ve buna bal olarak balayc faz dayanmnn azalmasdr. Bu etkinin yansra, 90W-3Ni-7Cu alamnda bulunan balayc faz miktarnn daha az olmas (yaklak olarak %10) yksek bitiiklik deerlerine yol amakta ve bu alam sisteminde ekme dayanmnn ve % uzamann dmesine yol amaktadr. 4.SONULAR Bu almada 1430Cde hidrojen ve argon altnda yarm saat sre ile sv fazl sinterlenen ve yksek younlua ulalan 90W-7Ni-3Cu ve 90W-Ni3-Cu7 ar alamlarnda sinterleme ileminden sonra iki farkl hzda yaplan soutma ileminin mikroyapya ve mekanik zelliklere etkisi incelenmitir. alma sonucunda 90W-7Ni-3Cu alamnn ekme dayanmnn ve % uzamasnn 90W-3Ni-7Cu alamna gre daha yksek olduu belirlenmitir. 90W7Ni-3Cu alamnda sinterleme sonrasndaki soutma hznn yava olmasna bal olarak ekme dayanmnn ve % uzamann artt, 90W-3Ni-7Cu alamnda ise yava soutma koullarnda ekme dayanmnn dt ve % uzamann artt belirlenmitir.
5.KAYNAKLAR [1] Price G.H.S., Smithells C.J. ve Williams S.V., Sintered Alloys. Part . CopperNickel-Tungsten Alloys Sintered with a Liquid Phase Present, Journal Institute Metals, Vol. 62, pp. 239-264, 1938. [2] Caldwell S.G., Heat Treatment of Tungsten Heavy Alloys, International Journal of Powder Metallurgy, Vol. 39, No:7, pp. 43-51, 2003. [3] Kuzmick J.F., Development of Ductile Tunsten-Base Heavy-Metal Alloys, Modern Developments in Powder Metallurgy, Vol.3, pp.166-171, 1966. [4] Edmonds D.V., Jones P.N., Interfacial Embrittlement in Liquid-Phase Sintered Tungsten Heavy Alloys, Metall. Trans. A, Vol. 10A, No:3, pp. 289-295, 1979. [5] Muddle B.C., Interphase Boundary Precipitation in Liquid Phase Sintered W-Ni-Fe and W-Ni-Cu Alloys, Metall. Trans. A, Vol. 15A, No:6, pp. 1089-1098, 1984. [6] Ramakrishnan K.N., Upadhyaya G.S., Effect of composition and sintering on the densification and microstructure of tungsten heavy alloys containing copper and nickel, J. Materials Science Letters, Vol.9, pp. 450-459, 1990. [7] Das J., Kiran U.R., Chakraborty A., Prasad N.E., Hardness and tensile properties of tungsten based heavy alloys prepared by liquid phase sintering technique, Int. J. Ref. Metals and Hard Materials, Vol.27, pp. 577583, 2009. [8] Das J., Rao G.A., Pabi S.K., Microstructure and mechanical properties of tungsten heavy alloys, Materials Science and Eng. A, Vol.527, pp.7841-7847, 2010. [9] German R.M., Sintering Theory and Practice, John Wiley, Kanada, 1996. [10] alkan N.K., Durlu N., Bor A.., Tungsten Esasl Ar Alamlarda Ni/Cu Orann Mekanik zelliklere Etkisi yaynlanmak zere gnderildi, 2010. [11 Okamoto H., Subramaniam P.R., Kacprzak L., Binary Phase Diagrams, Cilt 2, ASM International, Materials Park, OH, 1990.
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TOZ ENJEKSYON YNTEMYLE KALIPLANMI MgO TAKVYEL ALMNANIN MEKANK ZELLKLERNN ARATIRILMASI
Ouz ERDEM*, brahim USLAN * Gazi niversitesi Mhendislik Fakltesi, Makine Mhendislii Blm, Ankara oguz_erd@yahoo.com, iuslan@gazi.edu.tr ZET Bu almada MgO takviyeli ve takviyesiz almina tozlar toz enjeksiyon yntemiyle kalplanmtr. Balayc olarak arlka %65 PEG8000 (polietilenglikol)+%30 PP (polipropilen)+%5 SA (stearik asit) kullanlmtr. Balangta drt farkl oranda besleme stounun reolojik zellikleri incelenerek en iyi toz-balayc oran hacimce %53/%47 olarak bulunmutur. Bu karmdan oluan (MgO ilavesiz (takviyesiz) ve arlka %0,5, %1, %1,5 oranlarnda MgO ieren) besleme stoklarnn reolojik zellikleri incelenmitir. Bu orana gre hazrlanan besleme stoklar granl hale getirilmitir. Enjeksiyonda ekme ve eme numuneleri kalplanmtr. Kalplanan numunelere zc ve sl balayc giderme (n sinterleme) ilemleri uygulanmtr. Yaplan sinterleme almalar sonucunda 1775 C scaklk ve 8 saat sinterlenen numunelerde mekanik zellikler ktlemitir. 1775 C scaklk ve 6 saat sre optimum sinterleme parametreleri olarak bulunmutur. En iyi mukavemet ve younluk deerleri ktlece %1 MgO takviyeli almina besleme stoklarnda elde edilmitir. SEM ile yaplan incelemelerde ktlece %1 MgO takviyeli numuneler daha az gzenekli ve dzgn sinterlenmi grnm sergilemitir. Anahtar Kelimeler: Toz enjeksiyon kalplama, Reoloji, Almina, Sinterleme.
INVESTIGATION OF MECHANICAL PROPERTIES OF POWDER INJECTION MOULDED ALUMINA BY ADDING MgO

ABSTRACT In this study, MgO added alumina and pure alumina powders were molded by powder injection molding method. %65 PEG8000 (polyethyleneglycol)+%30 PP (polypropylene) + %5 SA (stearik asit) in weight was used as the binder. First, the rheological properties of four different feedstocks were examined and the optimum powder/binder ratio was determined as 53%/47% in volume. Rheological properties of feedstocks (pure and in weight for 0,5%, 1%, 1,5% MgO added alumina) which contain 53% alumina+ 47% binder in volume, were investigated. The feedstocks prepared using this ratio, were granulated and then tensile and bending samples were molded by injection method. Solvent and thermal (pre-sintering) debinding of these molded samples were carried out. As a result of sintering investigations, the samples sintered in 1775 C for 8 hours had inferior mechanical properties. The temperature of 1775 C and 6 hours of the holding time were determined as the optimum sintering parameters. The highest strength and density values were obtained for 1% (wt.) MgO added alumina feedstocks. SEM analysis showed that 1% (wt.) MgO added alumina feedstock samples have less pore and those have good sintering. Keywords: Powder injection moulding, Rheology, Alumina, Sintering. 1. GR Toz Enjeksiyon Kalplama (TEK), ok ince taneli metal ve seramik tozlarn, termoplastik balayclarla kartrlmas ve bu karma plastik enjeksiyon makinelerinde preslenerek ekil verme teknolojisidir. lem aamalar; kartrma, granlleme, enjeksiyon kalplama, balayc ayrtrma ve sinterlemeden oluur [1]. kinci Dnya Savandan sonra gelien teknolojilerin younluu dk, fiziksel ve kimyasal ortamlarda dayankl, y-
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ksek scaklklarda da kullanlabilecek malzemelere olan ihtiyac aa karmasna bal olarak, metallerden daha yksek scaklklarda kullanlabilen, sertlik ve anma direnci yksek seramik malzemeler ne kmtr [2]. Bugn dnyada byk bir kullanm alanna sahip olan ileri mhendislik seramik malzemelerin banda mekanik, sl, optik, elektrik, kimyasal ve nkleer zelliklerinden dolay almina ve almina bazl seramik malzemeler gelmektedir [3]. Alminann ekillendirilmesinde MgO ilavesinin alminadaki tane snr bymesini engelledii bilinmesine karn, bugn halen birok aratrmac, MgO ilavesinin alminann tane bymesini yavalatmadaki roln ve tane yaps zerindeki eitli mekanizmalar (ikinci faz, kat znme v.b) aratrmaktadr [4]. Alminann toz enjeksiyonla kalplamasna ynelik almalar literatrde yaygn olmakla birlikte [5-20], MgO takviyeli alminann TEK yntemiyle yaplm almalar snrldr [21-23]. Hwang ve arkadalar, aluminann enjeksiyon ile kalplanmasnda kullanlan balayc sistemine Mg bileikleri katldnda sinterleme sonras %96 teorik younlua ulaldn ve Mg-stearatn homojen bir MgO dalm saladn bildirmitir [21]. Vielma ve arkadalar polimer-mum esasl balayc sistemiyle gerekletirdikleri alminann toz enjeksiyon yntemiyle kalplanmas almasnda en yksek younluk deerine (%99,6) 1600 Cde 2 saat sinterleme sonucu ulamlardr [22]. Ycel, herhangi bir ilave toz kullanmakszn %55 almina+%45 balayc sisteminden oluan besleme stou ile rettii numunelerde en iyi mekanik zellikleri 1800 C sinterleme scaklnda elde ettiini bildirmitir [12]. 2. DENEYSEL ALIMA 2.1. Malzemeler Deneylerde kullanlan almina tozu Treibacher Schleifmittel firmas tarafndan retilen ALODUR WSK F500 fused almina olup, %99,6 saflkta, 3,96 g/cm3 younlukta, 101,961 g/mol molekl arlnda ve 3,37 m ortalama boyuttadr. Deneylerde takviye malzemesi olarak kullanlan magnezyum oksit tozu3 Merck Co. firmas tarafndan retilmitir. Kullanlan MgOnun younluu 3,58 g/cm , molekl arl 40,30 g/mol, erime scakl 2800 C, kaynama scakl 3600 C ve ortalama boyutu 6,37 m dir. Balayc sistemi; enjeksiyon kalplama yaplacak MgO takviyeli ve takviyesiz almina tozlarn sinterleme aamasna kadar bir arada tutacak olan iskelet balayc polipropilen (PP), kalplama esnasnda ak kolaylatracak olan ana balayc PEG8000 ve toz-kalp aras yalayc (nemlendirici, kayganlatrc) etkis3i olan stearik asit (SA)dan olumaktadr. Kullanlan PEG8000in younluu 1,204 g/cm ve erime scakl 60 C, PPnin younluu 0,85 g/cm3 ve erime scakl 189 C, SAnn younluu 0,94 g/cm3 ve erime scakl 68 Cdir. 2.2. Klcal Reometre Deneyleri Klcal reometre deneyleri iin drt farkl besleme stou oluturulmutur. Bunlar: hacimce %51 almina+%49 balayc, %53 almina+%47 balayc, %56 almina+%44 balayc ve %59 almina+%41 balaycdr. Besleme stoundaki balayc sistemi arlka %65 PEG8000, %30 PP ve %5 SAdan olumaktadr. Deneylerde srasyla hacim olarak %51, 53, 56, 59 almina tozu oranl drt farkl besleme stounun 170, 180, 190, 200, 210 C scaklklarda 0,6 MPa ve 1 MPa basnlarda ASTM D1238 ve TS 1675 standartlarna gre reoloji deneyleri yaplmtr. 2.3. Granlleme Granlleme ilemi ift vidal Kraus-Maffei marka ekstrder ile yaplmtr. Ekstrderin silindir scakl 165 Cde ve 50 devir/dakda tm besleme stoklar granl edilmitir. 2.4. Toz Enjeksiyon Kalplama Kalplama ilemi Gazi niversitesi Makina Mhendislii Blmnde bulunan ARBURG Allrounder 220S marka enjeksiyon makinesinde gerekletirilmitir. Enjeksiyonda iki farkl tip (byk, kk) ekme numunesi ile tek tip eme numunesi kalplanmtr. Bu numunelerin geometrileri ekil 1de, ham younluktaki boyut lleri ise izelge 1de grlmektedir. 2.5. Balayc Giderme Bu almada kullanlan balayc sisteminden (%65 PEG8000, %30 PP, %5 SA) dolay iki aamada gerekletirilmitir. lk aamada ana balayc PEG8000in suda znmesi, iskelet balayc PPnin ve yalayc SAnn suda znmemesinden faydalanarak PEG8000 uzaklatrlmtr. kinci aamada ise numuneleri sinterleme aamasna kadar tayacak olan PP ve yalayc SA sinterlemenin ilk aamasnda s ile uzaklatrlmtr.
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ekil 1. ekme ve nokta eme numunelerinin geometrileri izelge 1. ekme ve eme numunelerinin ham younluktaki boyutlar
2.6. Sinterleme Sinterleme ilemi Carbolite marka frnda gerekletirilmitir. Isl balayc giderme ileminden sonra frn 600 Cye ulamtr. Sonra 10 C/dak ile 1200 Cye klm ve bu scaklkta 15 dak beklenmi daha sonra 15 C/dak ile farkl numunelerde (1650-1700-1720- 1740-1750-1775 C)ye klm ve burada 2-14 saat sre ile sinterleme ilemleri yaplmtr. 2.7. Sinterlenmi Paralarn % Bzlme ve Younluklarnn Tayini ekme ve eme numunelerinin younluk ve % bzlme oranlar, TS 2305 ve TS EN 623-2 standartlarna uygun olarak yaplmtr. 2.8. ekme ve Nokta Eme Deneyleri ekme ve nokta eme deneyleri 5 kN kapasiteli bilgisayar kontroll Schimadzu marka ekme cihaz kullanlarak gerekletirilmitir. ekme deneyleri TS ISO 15490 standart, eme deneyleri ise TS ENV 12789 standartlar esas alnarak yaplmtr. 2.9. Taramal Elektron Mikroskop almalar JEOL marka JSM-6060LV Taramal Elektron Mikroskobu (SEM) kullanlarak numunelerin sinterleme ncesi ve sonras yapsal durumlar incelenmitir. 3. DENEY SONULARI VE TARTIMA 3.1. Klcal Reometre Sonular Oluturulan drt farkl besleme stounun (hacimce %51 almina+ %49 balayc, %53 almina+%47 balayc, %56 almina+%44 balayc ve %59 almina+%41 balayc) 0,6 MPa ve 1 MPa basn deerleri iin viskozitescaklk ve viskozite-kayma hz grafikleri deerlendirilerek besleme stoklarnn TEK ilemi iin uygunluu aratrlmtr (ekil 2-5). Besleme stoklarnn reolojik zellikleri incelendiinde; hacimce %51 almina+%49 balayc karmnn reolojik zellikleri ilk bakta TEK ilemi iin uygun grnmektedir. Fakat bu karmn kayma
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hz deerleri, dier karmlarn kayma hz deerlerine nazaran yksek olduundan; zellikle yksek kalplama basnlarnda dk younluklu balaycya gre daha youn almina tozlarnn balaycdan ayrmasna neden olabilecei, tam dolmama sorununa yol aabilecei dnlmtr. Ayrca TEK ilemi ile retilmi paralarda tam younlua ulaabilmek iin mmkn olan azami kat ykleme oranna yaklalmaldr. Bu balamda hacimce %51 almina+%49 balayc karm tercih edilmemitir.
ekil 2. 0,6 MPa basnta karmlarn scaklk-viskozite grafii
ekil 3. 1 MPa basnta karmlarn scaklk-viskozite grafii
ekil 4. 0,6 MPa basnta karmlarn kayma hz-viskozite grafii
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ekil 5. 1 MPa basnta karmlarn kayma hz-viskozite grafii Besleme stoklarnn reoloji deneylerinde hacimce %56 almina+%44 balayc karmnn 170 Cde akmad ve bundan sonraki scaklk deerlerindeki viskozite deerlerinin de TEK ilemi iin uygun olmad grlmtr. Buna gre; bu karm iin kritik toz yk hacimsel olarak %56 alminadr. Dolaysyla besleme stoklarn olutururken bu orann altndaki deerlerde oluturmann sorunsuz bir TEK ilemi iin gerekli olduu tespit edilmitir. Drt farkl besleme stounun reolojik zellikleri incelendiinde TEK iin en uygun karmn hacimce %53 almina+%47 balayc olduuna karar verilmi ve MgO takviyesi bu orandaki karmlara yaplmtr. Burada almina ve MgOnun younluk deerlerinin birbirine ok yakn olmas nedeniyle yaplacak MgO takviyesinin alminann reolojik zelliklerini TEK ileminde sorun tekil edecek ekilde deitirmeyecei ngrlmtr. Bir baka deyile, takviyesiz almina karm iin geerli olan en uygun orann, takviyeli almina karmlar iin de geerli olaca kabul edilmitir. Hacimce %53 almina+ %47 balaycdan oluan farkl MgO takviyeli besleme stoklarnn 0,6 MPa ve 1 MPa basn deerleri iin viskozite-scaklk ve viskozite-kayma hz grafikleri incelenerek TEK ilemi iin uygunluu aratrlmtr (ekil 6-9).
ekil 6. 0,6 MPa basnta MgO takviyeli karmlarn scaklk-viskozite grafii
ekil 7. 1 MPa basnta MgO takviyeli karmlarn scaklk-viskozite grafii
ekil 8. 0,6 MPa basnta MgO takviyeli karmlarn kayma hz-viskozite grafii
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Hacimce %53 almina+%47 balaycdan oluan takviyesiz, ktlece %0,5, %1 ve %1,5 MgO takviyeli besleme stoklarnn, 0,6 ve 1 MPa basnlardaki scaklk-viskozite grafikleri incelendiinde viskozite deerlerinin tm besleme stoklarnda 1000 Pa.snn altnda olduu ve TEK ilemi iin uygun olduklar rahatlkla grlebilir. Beslemestoklarnn birbirlerine benzer ak zellii gstermesiyle, MgO takviyesinin reolojik zellikleri ok deitirmeyecei n grs dorulanmtr.
ekil 9. 1 MPa basnta MgO takviyeli karmlarn kayma hz-viskozite grafii 3.2. Enjeksiyon Makinesinde Kalplama Farkl enjeksiyon parametreleri sonucunda elde edilen baz numunelerde basn, scaklk, debi ve mal alma miktarna bal olarak eksik dolum, apaklanma ve kme gzlenmitir. TEKde eksik dolum, apaklanma ve kme istenmeyen durumlardandr. TEKde standart numune oluturma ancak uzun sren deneme-yanlmalar ile mmkn klnmtr (izelge 2). izelge 2. %53 almina+ %47 balayc ieren besleme stounun TEK ile kalplanmas
3.3. Balayc Giderme Yaplan zcde balayc giderme denemelerinde en iyi sonu 60 C scaklktaki suda 24 saat bekleme sresinde elde edilmitir. ekme ve eme numunelerine bu artlarda balayc giderme ilemi uygulanm sonra 50 Cde 5 saat kurutulmutur. Bu ilem sonunda PEG8000in, ekme numunelerinden ktlece %84, eme numunelerinden ise ktlece %89u uzaklatrlmtr. Isl balayc giderme ilemi, sinterleme ileminin balangcnda gerekletirilmitir. Isl balayc giderme ilemi ilk nce 210 Cye kadar 3 C/dak stma hzyla kma ve bu scaklkta 30 dak bekleme, sonra 4 C/dak stma hzyla 480 Cye kma ve bu scaklkta 30 dak bekleme, daha sonra 5 C/dak stma hzyla 600 Cye kma ve bu scaklkta 15 dak bekleme olarak gerekletirilmitir. Bylece tamamlanan sl balayc giderme ileminin (n sinterleme) ardndan numuneler frn iinden karlmadan sinterleme ilemine devam edilmitir. Sinterlemenin balang aamas olarak planlanp uygulanan sl balayc giderme ileminde her hangi bir soruna rastlanlmam ve sinterleme ilemi sonunda numuneler gayet dzgn kmtr. 3.4. Sinterleme ncelikle optimum sinterleme parametrelerinin aratrlm daha sonra mevcut tane boyutu ve almina eiti iin en uygun sinterleme artlar belirlendikten sonra bir defada ok sayda numune sinterlenmitir. Optimum sinterleme parametreleri belirlenirken ktlece %1 MgO takviyeli byk ve kk ekme numuneleri kullanlm ve sinterleme ilemi sonunda numunelerin ekme mukavemetleri belirlenerek yorumlanmtr. Ktlece %1 MgO takviyeli numunelerin kullanlmasnn sebebi, literatrde yaplm benzer bir almada [21] alminaya yaplan ktlece %1 MgO takviyesinin en iyi mekanik zellikleri gsterdii sonucudur. Optimum scaklk olarak 1775 Cnin tespitinden sonra optimum sinterleme sresinin bulunmas iin bu scaklkta 2, 4, 6, 8 ve 10 saatlik sinterleme sreleri denenmitir. Sonulara bakldnda 8 saat sinterleme sonras kk ekme numunelerinde ciddi derece arplma gzlemlenmi ancak byk ekme numunelerinde bu sorunla karlalmamtr. 10 saatlik sinterleme ilemi sonras her iki tip numunede de arplma gzlemlenmitir. 1775 Cde 6 saatte sinterlenmi byk ekme numunesinin mukavemet deeri ile ayn scaklkta 8 saatte sinterlenmi byk ekme numunesinin mukavemet deerleri karlatrldnda, 8 saatlik
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sinterleme ilemi sonras ekme mukavemetinde azalma grlmtr. Bunun nedenin yksek scaklklarda uzun sren sinterleme ilemi, tane bymesine yol amas olarak dnlmtr. Alminadaki anormal tane snr bymesinde MgO ilavesinin etkilerinin aratrld C. Park ve D. Yoonun almasnda [22] benzer sonular bulunmutur. Sonu olarak en iyi deerler 1775 Cde 6 saatte sinterlenmi numunelerde elde edilmitir. 3.5. Mekanik Testler Kk ve byk ekme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerinde yaplan sinterleme ilemi sonucunda deien ortalama mukavemet deerlerinin grafiksel gsterimleri ekil 10 ve 11de verilmitir. Eme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerinde yaplan sinterleme ilemi sonucunda deien ortalama mukavemet deerlerin grafiksel gsterimleri ekil 12de verilmitir.
ekil 10. Kk ekme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerindeki sinterleme ilemine gre ortalama ekme mukavemetleri
ekil 11. Byk ekme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerindeki sinterleme ilemine gre ortalama ekme mukavemetleri
ekil 12. Eme numunelerinin 1775 C scaklkta 6 ve 8 saat bekleme srelerindeki sinterleme ilemine gre ortalama ekme mukavemetleri
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3.6. Sinterlenmi Paralarn % Bzlme ve Younluklar Kk ekme numunelerinde en yksek younluk deeri ktlece %1 MgO takviyeli besleme stounda elde edilmitir. Maksimum younluk deeri 3,44 g/cm3 ve %86,8 teorik younluk deeri elde edilmitir. Benzer durum byk ekme numunelerinin younluk deerlerinde de grlmektedir. En yksek younluk deeri ktlece %1 MgO takviyeli besleme stounda elde edilmitir. Maksimum younluk deeri 2,84 g/cm3 ve %71,7 teorik younluk deeri elde edilmitir. Eme numunelerinde %1 MgO takviyeli besleme stounda 3,49 g/cm3 en yksek younluk ve %88,1 teorik younluk deeri elde edilmitir. Alminaya ktlece %0,5 MgO takviyesi younluk deerini artrmakta, MgO takviye miktar ktlece %1 olduunda ise younluk deerleri maksimum olmaktadr. Ancak MgO takviye miktar ktlece %1,5 olduunda younluk deerlerinde d grlmektedir. Kk ekme numunelerinde %17,8 bzlme deeri, byk ekme numunesinde %18,5 bzlme deeri ve eme numunelerinde %16,2 bzlme deeri elde edilmitir. Bu almada toplam tip numune kullanlmtr. Bunlar byk ekme, kk ekme ve eme numuneleridir. Ham numuneden balaycs giderilmi numuneye ve daha sonra sinterlenmi numuneye geii ile sinterlenmi numunelerdeki boyutsal daralma ekil 13de grlmektedir.
ekil 13. Numunelerdeki boyutsal daralma 3.7. Mikroskobik ncelemeler Ham ve balaycs giderilmi takviyesiz alminaya ait ekme ve eme numunelerinin SEM grntleri ekil 14de grlmektedir.
ekil 14. Ham ve balaycs giderilmi numuneler (a) Ham ekme numunesi (b) Balaycs giderilmi ekme numunesi (c) Ham eme numunesi (d) Balaycs giderilmi eme numunesi
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ekil 14 (a) ve (c)de grlecei zere ham numunelerde balayclar beyaz renkli blgelerde youn olarak grlmektedir. ekil 14 (b) ve (d)de ise balaycs giderilmi numunelerde beyaz blgelerin ciddi oranda azald grlmektedir. 3.7.1. ekme numuneleri Drt farkl besleme stoundan hazrlanp 1775 Cde 6 saat sinterlenmi ekme numunelerinin krlma yzeylerine ait SEM grntleri ekil 15de verilmitir.
ekil 15. %53 almina+ %47 balaycya sahip ekme numunesi krlma %5 yzeyleri (a) Takviyesiz numune: 48 MPa (b) %0,5 MgO takviyeli numune: 50,4 MPa (c) %1 MgO takviyeli numune: 69 MPa (d) %1,5 MgO takviyeli numune: 54,2 MPa ekme numunelerinin SEM grntlerinden de grld gibi (ekil 15) almina tozlarnn en youn olduu, baka bir ifadeyle gzeneklerin en az olduu %1 MgO takviyeli numune (ekil 15.c), ekme mukavemetinin yksek olduu numunedir. 3.7.2. Eme numuneleri Drt farkl besleme stoundan hazrlanp 1775 Cde 6 saat sinterlenmi eme numunelerinin SEM grntleri ekil 16da verilmitir.
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ekil 16. %53 almina+ %47 balaycya sahip eme numunesi krlma % yzeyleri (a) Takviyesiz numune: 88,2 MPa (b) %0,5 MgO takviyeli numune: 110 MPa (c) %1 MgO takviyeli numune: 158 MPa (d) %1,5 MgO takviyeli numune: 144,1 MPa Eme numunelerinin SEM grntlerinden de grld gibi (ekil 16) almina tozlarnn en youn olduu, baka bir ifadeyle gzeneklerin en az olduu %1 MgO takviyeli numune (ekil 16.c.), ekme mukavemetinin yksek olduu numunedir. 4. SONULAR 1. Kritik toz yk %56 almina olarak bulunmu ve en iyi toz-balayc oran hacimce %53 almina+ %47 balayc olduu tespit edilmitir. 2. Granl haline getirilen besleme stoklaryla dzgn kalplama iin enjeksiyon parametreleri belirlenmitir. ekme numuneleri iin 1150 bar enjeksiyon basnc, 17 cm3/s debi, 16 cm3 mal alma miktar ve 195 C ortalama scaklkla kusursuz numuneler kalplanmtr. Eme numuneleri iin 900 bar enjeksiyon basnc, 17 cm3/s debi, 13,5 cm mal alma miktar ve 190 C ortalama scaklkla kusursuz numuneler kalplanmtr. 3. En iyi sinterleme parametreleri mukavemet deerleri esas alnarak: 1775 C sinterleme scakl ve 6 saat bekleme sresi olarak belirlenmitir. 4. Takviyesiz alminadan retilmi ekme numunelerinde, maksimum ekme mukavemeti 48 MPa iken ktlece %1 MgO takviyeli alminadan retilmi numunelerin maksimum ekme mukavemeti 69 MPadr. Ayrca bu almada ktlece %1 MgO takviyeli alminadan retilmi kk ekme numunelerinin ortalama ekme mukavemeti 65,5 MPa iken Ycelin [12] almasnda ayn almina tozu ile 1800 Cde 10 dak sinterlenmi kk ekme numunelerin ortalama ekme mukavemeti 56,51 MPadr. Bu sonulara gre alminaya ktlece %1 MgO takviyesi yaplarak Ycelin [12] almasndaki ortalama ekme mukavemet deeri geilmitir. 5. Takviyesiz alminadan retilmi numunelerde, ortalama eme mukavemeti 86,8 MPa iken ktlece %1 MgO takviyeli alminadan retilmi numunelerde ortalama eme mukavemeti 155,8 MPadr. Ycelin [12] almasnda alminadan retilmi eme numunelerinin ortalama eme mukavemeti 91,4 MPadr. Bu sonulara gre alminaya ktlece %1 MgO takviyesi yaplarak Ycelin [12] almasndaki maksimum eme mukavemet deeri geilmitir. 6. Alminaya ktlece %0,5 MgO takviyesi hem ekme hem de eme mukavemetdeerlerini artrmakta, MgO takviye miktar ktlece %1 olduunda ise mukavemet deerleri maksimum olmakta, ancak MgO takviye miktar ktlece %1,5 olduunda mukavemet deerlerinde d grlmektedir. 7. Takviyesiz alminadan retilmi ekme numunelerinde, maksimum younluk deeri 3,11 g/cm3 ve %78 teorik younluk elde edilmitir. Ktlece %1 MgO takvi3yeli alminadan retilmi ekme numunelerinde maksimum younluk deeri 3,44 g/cm ve %86,8 teorik younluk elde edilmitir. Takviyes3iz alminadan retilmi eme numunelerinde, ortalama younluk deeri 3,12 g/cm ve %78,7 teorik younluk elde edilmitir. Ktlece %1 MgO takviyeli alminadan retilmi eme numunelerinde ortalama younluk deeri 3,45 g/cm3 ve %87,1 teorik younluk elde edilmitir. 8. Alminaya ktlece %0,5 MgO takviyesi younluk deerini artrmakta, MgO takviye miktar ktlece %1 olduunda ise younluk deerleri maksimum olmakta, ancak MgO takviye miktar ktlece %1,5 olduunda younluk deerlerinde d grlmektedir. 9. 1775 C scaklkta 6 saatte yaplan sinterleme ilemi sonucunda: byk ekme numunelerinde %17,80, kk ekme numunelerinde %18,52 ve eme numunelerinde %16,20 bzlme gereklemitir. 10. SEM ile yaplan mikro yap incelemelerinde ktlece %1 MgO takviyeli numuneler daha az gzenekli ve dzgn sinterlenmi grnm sergilemektedir.
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Teekkr Bu alma, Gazi niversitesi Bilimsel Aratrma Projeleri tarafndan desteklenmitir. KAYNAKLAR 1. Karata, ., Sarta, S., Toz Enjeksiyon Kalplama: Bir Yksek ve Teknoloji malat Metodu, Gazi niversitesi Mhendislik Mimarlk Fakltesi Dergisi, Ankara, 13 (2): 193-228, (1998). 2. ztrk, M., SiC laveli Almina Seramik Kompozitler, Yksek Lisans Tezi, Sakarya niversitesi Fen Bilimleri Enstits, Sakarya, 1-83 (2007). .ran, M., Alminann Ekstrzyonla ekillendirilmesi, Yksek Lisans Tezi, Afyon Kocatepe niversitesi Fen Bilimleri Enstits, Afyon, 1- 4 (2006). 4.Byung-Ki, K., Seong-Hyeon, H., Sang-Ho, L., Alternative explanation for the role of magnesia in the sintering of alumina containing small amounts of a liquid phase, Seoul National University, Korea, 634-635 (2003). 5.Hwang, K.S., Hsieh, C.C., Injection-Molded Alumina Prepared with MgContaining Binders, The American Ceramic Society, USA, 2349-2359 (2005). 6.Vielma, P.T., Cervera A., Levenfeld, B., Varez, A., Production of alumina parts by powder injection molding with a binder system based on high density polyethylene, Universidad Carlos III de Madrid, Spain, 763-771 (2008). 7. Yang, W.W., Yang, K.Y., Hon, M.H., Effects of PEG molecular weights on rheological behavior of alumina injection molding feedstocks, National Cheng Kung University, Taiwan, 416-424 (2002). 8. Oliveira, R.V.B., Soldi, V., Fredel, M.C., Pires, A.T.N., Ceramic injection moulding: influence of specimen dimensions and temperature on solvent debinding kinetics, Universidade Federal de Santa Catarina, Brazil, 213-220 (2005). 9. Wei, W.C.J., Wu, R.Y., Ho, S.J., Effects of pressure parameters on alumina made by powder injection moulding, National Taiwan University, Taiwan, 1301-1310 (2000). 10. Loebbecke, B., Knitter, R., Hauelt, J., Rheological properties of alumina feedstocks for the low-pressure injection moulding process, Institute for Materials Research III, Germany, 1595-1602 (2009). 11.Bakan, H.I., Gne, M., Development of Water Soluble Binder Systems for Low Pressure Injection Molding of Alumina, TUBITAK-MRC Materials and Chemical Technologies Research Institute, Turkey, 313-316 (2004). 12. Ycel, ., Toz enjeksiyon kalplanm alminann mekanik zellikleri, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara, 1-117 (2007). 13. Trunec, M., Cihlar, J., Thermal Debinding of Injection Moulded Ceramics, Technical University of Brno, Czech Republic, 203-209 (1997). 14. Krauss, V.A., Oliveira, A.A.M., Klein, A.N., Al-Qureshi, H.A., Fredel, M.C., A model for PEG removal from alumina injection moulded parts by solvent debinding, Federal University of Santa Catarina, Brazil, 268-273 (2007). 15. Yang, W.W., Yang, K.Y., Wang, M.C., Hon, M.H., Solvent debinding mechanism for alumina injection molded compacts with water-soluble binders, National Cheng Kung University, Taiwan, 745-756 (2003). 16. Wong, T.L., Li, R.K.Y., Wu, C.M.L., Injection Moulding of SiC / Al2O3 Composites, City University of Hong Kong, Hong Kong, 399-404 (1997). 17. Mannschatz, A., Hhn, S., Moritz, T., Powder-binder separation in injection moulded green parts, Fraunhofer Inst. for Ceramic Tech. and Systems, Germany, 1-6 (2010). 18. Trunec, M., Cihlar, J., Thermal removal of multicomponent binder from ceramic injection mouldings, Technical University of Brno, Czech Rep., 2231-2241 (2002). 19. Wei, W.C., Tsai, S.J., Hsub, K.C., Effects of mixing sequence on alumina prepared by injection molding, Nationai Taiwan University, Taiwan, 1445-1451 (1998). 20. Say, C.A., Earl, D.A., Thompson, M.J., Optimization of the sintered density of aluminum oxide compacts, New York State College of Ceramics at Alfred University, USA, 262-267 (2002). 21. Heraiz, M., Merrouche, A., Saheb, N., Effect of MgO addition and sintering parameters on mullite formation through reaction sintering kaolin and alumina, International Islamic University Malaysia, Malaysia, 285-290 (2006). 22. Park, C.W., Yoon, D.Y., Abnormal grain growth in alumina with anorthite liquid and the effect of MgO addition, Korea Advanced Institute of Science and Technology, Korea, 1585-1593 (2002). 23. Erdem, O., Toz enjeksiyon yntemiyle kalplanm MgO takviyeli alminann mekanik zelliklerini aratrlmas, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara, 1-117 (2010).
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MAGNEZYUMUN LAVESNN Al4Cu TM ALAIMININ YALANMA DAVRANIINA ETKLER

Azim GKE*, Fehim FINDIK**, Ali Osman KURT***
* **
Sakarya niversitesi Teknik Eitim Fakltesi Metal Eitimi Blm,54187, Sakarya, azimg@sakarya.edu.tr Uluslararas Sarajevo niversitesi, Mhendislik ve Fen Bilimleri Fakltesi, Mmakine Mhendislii Blm, 71000, Saraybosna, Bosna-Hersek, ffindik@ius.edu.ba *** Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 54187, Sakarya, aokurt@sakarya.edu.tr zet
Bu almada elementel olarak hazrlanm % 4 bakr ieren alminyum alamna farkl oranlarda magnezyum katks yaplm, alamn yapay yalanma davran mikroyap ve sertlik sonularyla incelenmitir. Magnezyum ilavesi Al4Cu toz metal ana malzemesinin yalandrma ile sertlik kazanma kabiliyetini artrmaktadr. Magnezyum ilavesiz numunede sertlikte 6 saatlik yalandrma ile yaklak % 40lk bir art salanrken, ayn numuneye % 0,5 magnezyum ilavesi ile 6 saatlik bir yalandrma sonras sertlik art yaklak % 95 olmaktadr. almada en yksek sertlie (117 HB) % 2 magnezyum ieren alamn 24 saat yapay yalandrlmas sonucu ulalmtr. Anahtar Kelimeler: Al Toz Metal, Mikro Alamlama, Sinterleme, Toz Metal Isl lemleri.
EFFECTS OF THE MAGNESIUM ADDITION ON THE AGING BEHAVIOR OF Al4Cu PM ALLOY

ABSTRACT In this study, various levels of magnesium added into pre-mixed Al4Cu powder metallurgy alloy and aging behavior of the alloy was investigated. The addition of Mg resulted in an increase in age hardening ability of the onto the main Al4Cu PM alloy. The alloy without Mg addition has only 40 % increase in hardness after 6 hours ageing whereas with an 0,5 wt% Mg addition on to the same alloy resulted in an 95 % increase in hardness after 6 hours ageing. In the study, the highest hardness value was obtained with an alloy (Al4Cu2Mg) of 2 % Mg addition after 12 hour ageing. Keywords: Al Powder Metallurgy, Micro-Alloying, Sintering, Powder Metallurgy Heat Treatments. 1. GR Alminyum alamlarnn dk zgl arlk, yksek korozyon direnci, geri dnm gibi zellikleri toz metalurjisi ynteminin avantajlar ile birlemesiyle tozmetal alminyum alamlar son yllarda giderek artan bir oranda endstriyel ve teknolojik rnlerde kullanm alan bulmaktadr. Alminyum tozlarndan retilen alamlar ilenmi alminyum alamlar ile byk oranda benzer bileimdedir. Alminyum tozlarnn sktrlma zellii, genel olarak toz morfolojisine ve boyut dalmna bal olmakla beraber, 350 MPa basn altnda teorik younluunun %90na kadar ulalabilmektedir. Demir esasl tozlara nispeten alminyum tozmetal malzemelerin sinterlenmesi iin ok daha dk scaklklar yeterli olmaktadr. Bu ise zamandan ve enerjiden byk tasarruf salamaktadr [1].
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Alminyumun toz metalurjisinde kullanmndaki byk sorunlardan biri yzey oksididir. Alminyum zerindeki oksidin kalnl ortam scakl, alminyum tozunun retiminde kullanlan sre, sakland ortamdaki nem gibi deikenlere baldr. Oda scaklnda ktle alminyum yzeyindeki oksidin kalnl yaklak 10 20 dur. Atomize alminyum zerindeki oksit kalnl ise 50-150 arasndadr. Alminyum zerindeki oksit genellikle amorf ve emilen su tabakas nedeniyle hidrolize olmu durumdadr. 350 oC zerindeki scaklklarda tavlama srecinde oksit tabakas g-Al2O3 halinde kristalize olur. Oksit tabakas dk ergime dereceli metallerde kat faz sinterlemeyi engelleyici bir faktrdr. Bu yzde alminyum alamlarnn sinterlenmesinde sv faz daha ok tercih edilir bir yntemdir. Baz metallerin alam sistemine katlmas sinterleme srasnda oksit tabakasn elimine edici etki yapabilir. Magnezyum katksnn yzeyde oluan oksit tabakasn krmak sratiyle alminyum alamlarnn sinterlenmesinde olumlu katk yapt bilinmektedir[2,3,4,5]. Sisteme magnezyum katlmas durumunda; oluan reaksiyon aadaki gibidir[6]. 3Mg + 4Al2O3 3MgAl2O4 + 2Al (1)
Scheaffer[6] yapt TEM almalar ve mikroyapsal analizler ile Al 2xxx serisine yaplan Mg katksyla Spinel fazn olutuunu gstermitir. Sinter esnasnda magnezyumun alminyum matris iine nfuz etmektedir Sonrasnda yukardaki reaksiyon sonucu oksit film tabakas zerinde hacimce deiim meydana gelmekte ve bundan dolay oluan kesme gerilmesi oksit tabakasnn krlmasna sebep olmaktadr. Bylelikle yaynm (difzyon), slatma sonucunda sinterlemenin daha iyi olmasn salamaktadr. Dolaysyla, oksit tabakas bir problem olmaktan kmaktadr. Alminyum bakr alamlarnn mukavemetinin artrlmas iin sl ilem uygulanmas pratikte sklkla kullanlan bir yntemdir. Bu yntem zeltiye alma, su verme ve yalandrma olarak basamaktan olumaktadr[7]. Bu almada elementel tozlarla hazrlanm Al4Cu ana alamna eitli miktarlarda (% 0,5 2) magnezyum ilavesinin mikroyapya ve yalandrma sonucunda ana malzemenin sertliine olan etkileri incelenmitir. 2. DENEYSEL ALIMALAR 2.1 Hammadde ve Kompozisyon Hazrlama almada kullanlan tozlarn zellikleri Tablo 1de verilmitir. Tablo 2`de ise almada retilen alamlarn bileimleri grlmektedir. Tablo1. Deneysel almalarda kullanlan tozlarn zellikleri Toz Alminyum Bakr Magnezyum Tedariki Grel Makine A.. Grel Makine A.. Magnezyum Metal A.. Safiyet (%) 99,60 99,60 99,95 ,00 Toz Boyutu ( m) -53 -53 -53
Tablo 2. retilen alamlarn bileimleri Alam Kodu Alam Kodu Al4Cu Al4Cu0.5Mg Al4Cu0.5Mg1Mg Al4Cu0.5Mg2Mg Al 96,00 95,50 95,00 94,00 Alam Elementi (% a.) Cu 4,00 4,00 4,00 4,00 Mg -0,50 1,00 2,00
Alamn bileimine uygun olacak ekilde tozlar 0,0001 gr hassasiyetli Precisa hassas terazide tartlm sonrasnda taban 35 mm apnda 80 mm yksekliinde geni azl silindirik HDPE ielere konmutur. Kartrma ileminin daha etkili olmas asndan 5mm apnda ZrO2 bilyeler kullanl olup, ielerin hacimce 1/3 karm toz, 1/3 ZrO2 bilye ile doldurulmu 1/3lk ksm ise bo braklmtr. Kartrma ilemlerinde Turbula-T2F Mixer kullanlm olup kartrma sresi 3 saat olarak belirlenmitir.
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2.2. ekillendirme lemleri Kompaktlarn retilmesinde 14 Ton kapasiteli manel hidrolik bask cihaz kullanlmtr. Numune retiminde kullanlan basn 400 MPadr. retilen silindirik ham paralarn ap 16 mm ykseklii ise 4 mm olacak ekilde ayarlanmtr. Ham paralarn sinter ncesi younluklar ktlelerinin hesaplanm olan hacimlerine blnmesi ile bulunmutur. Kalp anmasnn engellenmesi iin her bir ekillendirme ilemi ncesi kalp boluu ve kalp zmbalar inko stearat ile yalanmtr. inko stearattn yzeye dalm yksek safiyetli alkol ile gerekletirilmitir. 2.3. Sinterleme lemleri Sinterleme ilemlerinde Honeywell DC2500 kontrol nitesi ile programlanabilen silindirik yatay tp frn kullanmtr. Frnn reaktr tp 316 L paslanmaz elikten zel olarak imal edilmitir. zeltiye alma ilemlerinde de ayn frn ve tp kullanlmtr. Numuneler frna Al2O3 altlklar zerinde yerletirilmitir. Sinterleme ilemlerinde yksek safiyette azot gaz kullanlmtr. Gaz iindeki olas ok dk oksijen safszlnn nne geilmesi amacyla tpten kan gaz frna girmeden nce silika jel ile doldurulmu gaz ykama iesinden geirilmitir. Gaz ak hz sinter esnasnda 1 lt/dk olarak belirlenmitir. Sinterleme scakl 615 C olup bu scakla 15 oC/dk hzla klmtr. Kontrolsz olarak frn ierisinin bu scaklklarn zerine almasn engellemek amal 600 C`nin zerinde frn stma hz 1 oC/dk olarak gerekletirilmitir (ekil 1). oCoCzeltiye alma ve yalandrma scaklklar her 3 grup numune iin de ayndr. zeltiye alma ilemi sonrasnda ar doymu yap elde edilmesi amacyla frndan kartlan numuneler oda scaklndaki su ierisine drlmtr. Isl ilem sreci olarak dkm alminyum alamlarna uygulanan T6 sl ilemine benzer bir sre olan T51 sreci seilmitir (ekil 1). Bu srece gre sinter sonrasnda numuneler oda scaklna dmeden zeltiye alma scaklna kontroll olarak soutulmaktadr. Yalandrma ilemleri Protherm-PFL-130/6 kl frnda yaplm olup yalandrma sresi 6, 12, 24 ve 48 saat olarak seilmitir. 2.4. Sinter Sonras lemler Sinterlenen numunelerin younluklar Arimet Prensibine gre belirlenmitir. Younluk belirleme ilemleri karm hazrlamada kullanlan hassas teraziye balanan younluk lm kiti ile yaplmtr. Younluk lm sonrasnda numuneler hassas kesme cihaz ile ortadan kesilip herhangi bir kontrolsz yalanmann engellenmesi iin souk olarak reineye alnmtr. Mikroyapsal inceleme iin numuneler geleneksel metalografik ilemlerden geirilmi nihai parlatmada 0,3 mlik almina sspansiyon kullanlmtr. Optik mikroskop olarak Clemex Image Analysis yazlm ile senkronize alan Nicon Eclipse L150A metal mikroskobu, elektron mikroskobu olarak Jeol JSM 6060LV taramal elektron mikroskobu kullanlmtr. Sertlik lmlerinde BMS 200 RB sertlik lm cihaz kullanlm olup seilen yk 62,5 kg ve yk uygulama sresi 10 saniyedir. Her bir numuneden 5 lm alnm ortalama deer o numunenin sertlik deeri olarak kabul edilmitir.
ekil 1. Sinterleme almalarnda kullanlan scaklk-zaman grafii.
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3. DENEYSEL SONULAR ve TARTIMA Deneysel almalarda kullanlan tozlarn morfolojik zelliklerinin incelenmesi amacyla ekilmi olan elektron mikroskobu grntleri ekil 2de verilmitir.
ekil 2. Kullanlan tozlarn SEM grntleri a)Al b)Cu c)Mg (. l izgisi a, b ve c iin 100 mdir). ve d iin ise 50 m`dir. l izgisleri daha da belirginletirilecek Literatrde alminyum-bakr alamlarnn sinterlenmesi ile ilgili almalarda sinterlemenin 580-620 oC scaklklar arasnda yapld grlmtr[6,8,9,10]. Sinterleme scaklnn belirlenmesinde bakr oran arttka sinterleme scakl dmektedir. Alminyum bakr denge diyagramna gre (ekil 3) % 4 bakr katks ile tektik sv faza gei scakl yaklak olarak 590 Cdir. Bu scaklk zerinde yaplan sinterleme ilemi sv faz olarak adlandrlr. Oluan tektik sv fazn kapiler basn etkisiyle paracklarn arasn doldurmas ile daha youn bir yap elde edilmesini salar. Daha nce yaplan bir alma[3] magnezyum katks ile birlikte sv faz oluma scaklnn dtn gstermitir. Bu yzden almada kullanlan sinter scakl olan 615 Cde oluan tektik fazn diyagramda belirlenenden daha fazla olduu dnlmektedir. zeltiye alma scakl olan 550 Cde bakrn tamam yapya girerken oda scaklnda alminyum iinde bakrn ok az bir ksm znebilmektedir. Bu durumda ani soutma ile ar doymu bir yap elde edilmektedir.
ekil 3. Al-Cu faz diyagramnn alminyumca zengin ksm. ekil 4de sinterlenmi Al4Cu ve Al4Cu2Mg alamlarna ait mikroyaplar grlmektedir. Magnezyum ilavesi ile birlikte yapda tane bymesi grlrken tane snrlar da magnezyum ilavesiz numuneye gre daha belirgindir. Magnezyum ilavesi ayn zamanda mikroyapda tespit edilebilir belirgin ekilde porozitede arta sebep olmutur (ekil 5). Magnezyumun spinel faz oluturarak alminyum yzeyindeki oksit tabakasn krmas dolaysyla sv faz oluumunu kolaylatrmas ve tane snrlarndaki sv faz miktar artyla beraber daha kaln tane snrlar olutuu dnlmektedir.
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ekil 4. Sinterleme ilemi sonrasnda a)Al4Cu b) Al4Cu2Mg alam.
ekil 5. retilen alamlarn sinter sonras % teorik younluk deerleri. Al4Cu numunesine ait zeltiye alma sonucunda oluan optik mikroyap grnts ekil 6-ada; taramal elektron mikroskobu grnts ise ekil 6-bde verilmitir. ekil 6-a genel yapnn grlmesi amacyla en dk bytmede (50X) ekilirken ekil 6-b keltilerin ve gzenek byklnn daha iyi incelenmesi amacyla yksek bytmede alnmtr. ekil 6-ada verilen numunede makro porozite grlmemektedir.
ekil 6. zeltiye alma ilemi sonucu Al4Cu numunenin a) optik b) SEM grnts ekil 6-bde belirtilen noktalara ait EDS analiz sonular Tablo 3de sunulmutur. Yapda grlen beyaz blgelerin demir ve bakrca zengin blgeler olduu grlmekle beraber zellikle demirce zengin blgeler inemsi yapda keltiler oluturmutur. Al4Cu numunesinin zeltiye alma sonras ekilmi XRD grafiinde (ekil 7) yapda Al-Cu-Fe intermetalik faznn olutuunu tespit edilmitir.
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Tablo 3. ekil 6-bde belirtilen noktalarn EDS analiz sonular. Nokta 1 2 3 4 Al 69,874 95,131 98,836 97,879 Element (% a.) Cu 21,952 4,869 1,164 1,762 Fe 8,174 --0,359
ekil 7. Al4Cu numunenin zeltiye alma sonras XRD grafii. (-Al7Cu2Fe, -Al) Yapda grlen demir tozlarn retim safhasnda ve safszlk olarak gelmektedir. Demir faz iinde znerek Al7Cu2Fe fazn oluturmaktadr. Bu faz mikroyapda inemsi/ubuksu formda yer almaktadr (ekil 6-b). Al4Cu2Mg numunenin zeltiye alma ilemi sonucu mikroyaps ekil 8de verilmitir. Magnezyum ilavesi ile birlikte ilavesiz numuneye oranla en byk fark olarak magnezyumun btn mikroyapda dalmas ve analiz yaplan noktalarda bulunan oksijen dikkat ekmektedir (Tablo 4). Matris olarak ifade edilebilecek 1 numaral nokta da dahil olmak zere analiz yaplan her noktada oksijen bulunmasnn nedeni, yapy oluturan elementlerin oksijene ilgisinin yksek olmasndandr. Bakr ieriinin yksek olduu 3 ve 4 numaral noktalarda demir ieriinin de yksek olmas XRD sonularn (ekil 7) dorular niteliktedir.
ekil 8. Al4Cu2Mg numunenin zeltiye alma ilemi sonucu mikroyap grnts Tablo 4. ekil 8de belirtilen noktalara ait EDS elementel analiz sonular. Nokta 1 2 3 4 Al 84,133 92,121 43,621 43,617 Element (% a.) Cu 1,342 1,366 17,346 17,539 Mg 2,714 1,725 3,440 3,091 O 11,811 4,788 32,280 28,664 Fe --3,311 7,088
Al4Cu2Mg numunesinin 24 saat yalandrma sonucu mikroyap grnts ekil 9da verilmitir. Mikroyap grntlerine gre tane snrlar belirgin olmakla beraber kimi noktalarda ikincil fazn daha belirgin olduu dikkat ekmektedir. zeltiye alma ilemi sonrasnda zeltiye alnamayan Al-Cu-Fe intermetaliinin (ekil 7) mikroyapda
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farkl renkte grnd tespit edilmi olup tane snrlarnda youn olarak biriken bu fazn sertlik zerinde olumlu bir etkisi olsa da mekanik zellikler zerinde olumsuz bir etkisinin olaca dnlmektedir. Bu fazn bakrca zengin blgelerde daha youn bulunduu EDS analizi ile tespit edilmi olup matris olarak ifade edilecek 1 ve 4 numaral noktalarda demir tespit edilmemesi bu faz zeltiye alnamad kantlar niteliktedir.
ekil 9. Al4Cu2Mg numunenin 24 saat yalandrma sonucu grnts. Tablo 5. ekil 9da belirtilen noktalarn EDS analiz sonular Nokta 1 2 3 4 Al 96,667 43,917 96,242 91,216 Cu 1,865 39,113 1,481 1,293 Element (% a.) Mg 1,468 1,976 2,277 1,566 O -11,201 -5,925 Fe -3,792 ---
retilen alamlara ait sertlik deerleri Tablo 6a verilmitir. Sonulara gre en yksek sertlik deeri 24 saat yalandrlan Al4Cu2Mg numunesinde elde edilmitir. % 2 magnezyum ilavesi, alam sertliinde hibir sl ilem olmadan % 50 art salamaktadr. Magnezyumun sinter kolaylatrc etkisi ve yapda ince bir ekilde dalmas bunun balca sebebidir. Ayrca magnezyum katks arttka yalanma iin gerekli sre ksalmtr. Elde edilen sertlik deerleri literatrdeki benzer almalardan daha yksektir[11,12,13]. Tablo 6. retilen alamlarn sertlik deerleri Sertlik (HRB) Alam Al4Cu Al4Cu0.5Mg Al4Cu1Mg Al4Cu2Mg 4. SONULAR zetle bu almada aadaki sonulara ulalmtr. Hammadde olarak kullanlan tozlardan safszlk olarak gelen demir Al-Cu ile birleerek Al7Cu2Fe intermetalii oluturmaktadr ve bu intermetalik zeltiye alma sl ilemi ile yapda zlememektedir. Al-Cu-Mg alamna eklenen mikro dzeyde magnezyum ile sertlikte yaklak %50 art elde edilmitir. Magnezyum ilavesi yalandrma ile sertlik kazanma kabiliyetini artrmaktadr. Magnezyum ilavesiz numunenin sertlii 6 saatlik yalandrma ile yaklak % 40lk bir sertlik art salanrken, ayn numuneye % 0,5 magnezyum ilavesi ile 6 saatlik bir yalandrma ile salanan sertlik art yaklak % 95dir. En yksek sertlik 118,2 HB ile k elde edilebilirkenen yksek sertlik deerine te ulalmtr. en % 2`lik magnezyum katks yaplan numunelerin 24 saat yalandrlmas ile elde edilmitir. Alamlandrma ve sl ilem ile Al4Cu alamnn sertlii % 179 artrlabilmektedir. Silisyum ilavesinin % 1`e karlmas ile en yksek sertlie 6 saatte klabilmektedir. Sinter 42,2 44,0 53,6 62,2 zeltiye alma 50,5 53,8 78,8 97,7 6 saat 59,2 86,2 92,4 111,1 Yapay Yalandrma 12 saat 24 saat 62,3 73,6 81,6 92,4 89,2 105,2 110,5 118,12 48 saat 72,2 94,3 96,6 101,8
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TEEKKR Bu alma Sakarya niversitesi Bilimsel Aratrma Projeleri Komisyonunca desteklenmitir (SA-BAPK 200950-02-020). Yazarlar, tozlarn teminindeki desteinden dolay Grel Makina A.. ve Magnezyum Metale teekkr eder. KAYNAKLAR 1. nternet Sitesi - European Powder Metallurgy Association- http://www.epma.com/New_non_members/structural_parts.htm 2. Lumley, RN., Sercombe, TB., Schaffer, GB., Surface Oxide and the Role of Magnesium During the Sintering of Aluminum, Metallurgical and Materials Transactions A, Vol. 30A, pp. 457-463, 1999. 3. Kondoh, K., Kimura, A.,Watanabe, R., Effect of Mg on Sintering Phenomenon of Aluminium Alloy Powder Particle, Powder Metallurgy, Vol. 44, pp. 161-164, 2001. 4. Gke, A., Fndk, F., Kurt, AO., Microstructural Examination and Properties of Premixed Al-Cu-Mg Powder Metallurgy Alloy, Materials Characterization, Vol. 62, pp. 730-735, 2011. 5. MacAskill, IA., Hexemer Jr, RL., Donaldson, IW., Bishop, DP, Effects of Magnesium, Tin and Nitrogen on the Sintering Response of Aluminum Powder, Journal of Materials Processing Technology, Vol. 210, pp. 22522260, 2010. 6. Schaffer, GB., Sercombe, TB., Lumley, RN.,Liquid Phase Sintering of Aluminium Alloys, Materials Chemistry and Physics,Vol. 67,pp. 8591, 2001. 7. Smith, WF., Mhendislik Alamlarnn Yap ve zellikleri, eviri:Dr.Mehmet Erdoan, Nobel Yaynlar, Ankara, 2001. 8. Kyung, HM., Kang, SP., Lee, BH., Lee, JK., Kim, YD., Liquid Phase Sintering of the Commercial 2xxx Series Al Blended Powder, Journal of Alloys and Compounds, Vol. 419(1-2), pp. 290-293,2006. 9. Hall, BJ., Schaffer, GB., Statistical Experimental Design of Al-Cu-Mg-Si P/M Alloys, Journal of Light Metals, Vol. 2(4),pp. 229-238, 2002. 10. Lefebvre, LP., Thomas, Y.,White, B., Effects of Lubricants and Compacting Pressure on the Processability and Properties of Aluminum P/M Parts, Journal of Light Metals, Vol. 2(4), pp. 239-246, 2002. 11. Kent, D., Schaffer, GB., Drennan, J., Age Hardening of a Sintered Al-Cu-Mg-Si-(Sn) Alloy, Materials Science and Engineering: A, Vol. 405(1-2), pp. 65-73, 2005. 12. Delgado, ML., Ruiz-Navas, EM., Gordo, E., Torralba, JM., Enhancement of Liquid Phase Sintering Through Al-Si Additions to Al-Cu Systems, Journal of Materials Processing Technology, Vol. 162-163, pp. 280-285, 2005. 13. ...c. T Durmus HK., Meric C., Age-hardening Behavior of Powder Metallurgy AA2014 Alloy, Materials and Design, Vol. 28(3), pp. 982-986, 2007.
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W-Ni-Fe alamlarnda balayc faz bileiminin mekanik zelliklere etkisi

N. Kaan ALIKAN*, Nuri DURLU**, nder M. SOYER*, akir BOR*** *TBTAK-SAGE, Metal ve Seramik Malzemeler Birimi, PK 16, Mamak, Ankara, ** TOBB, Ekonomi ve Teknoloji niversitesi, Makina Mh Bl., 06560, Ankara, ***Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mh. Bl., Ankara
ZET Tungsten ar alamlar sv fazl sinterleme teknikleri kullanlarak retilmekte ve balayc faz olarak genellikle NiFe alam kullanlmaktadr. Bu almada %97 arlk orannda W ieren ar alamda, balayc faz iindeki Ni:Fe orannn (2, 3, ve 4) mekanik zelliklere etkisi incelenmitir. Numuneler souk izostatik presleme ile 300 MPa basn altnda preslenmi ve 1480Cde hidrojen ve argon altnda 30 dakika sre ile sinterlenmitir. Sv fazl sinterlenmi numunelerin mekanik zellikleri belirlenmi ve mikroyaplar optik mikroskop ve taramal elektron mikroskop ile incelenmitir. Balayc faz iindeki Ni:Fe orannn artmasna bal olarak ekme dayanmnn ve snekliin azald gzlenmi ve bu deiimin sinterlenmi numuneler iinde bulunan tungsten ve balayc fazn dnda oluan nc bir faz ile ilgili olduu belirlenmitir. Anahtar Kelimeler: Tungsten ar alamlar, sv fazl sinterleme, W-Ni-Fe, mekanik zellikler
EFFECT OF BINDER PHASE COMPOSITION ON The MECHANICAL PROPERTIES OF W-N-Fe Alloys

ABSTRACT Tungsten based alloys are produced by liquid phase sintering technique. Ni-Fe alloys are the most commonly used binder phase in the manufacturing of tungsten alloys. This study investigates the effect of Ni:Fe ratio (2,3 and 4) on the mechanical properties of tungsten based alloys with 97 wt.% tungsten. Samples were cold isostatically pressed under 300 MPa and sintered at 1480C for 30 minutes under hydrogen and argon. The mechanical properties of the liquid phase sintered samples were determined, and the microstructures were investigated with optical and scanning electron microcopy. The study show that increase in Ni:Fe ratio of the binder phase decreases the tensile strength and % elongation of the samples. The decrease in the mechanical properties of the heavy alloys is related to the formation of a third phase in these alloys. Key Words : Tungsten heavy alloys, liquid phase sintering, W-Ni-Fe, mechanical properties
1. GR Tungsten ar alamlar sv fazl sinterleme ile retilen, yksek younluk ve yksek mekanik zelliklere sahip iki fazl metal matriks kompozitleridir. Bu tr alamlarda ana faz yaklak olarak %90-%98 arlk oranlarnda kullanlan ve dayanm yksek olan hacim merkez kbik kristal yapl W, ikinci faz ise (matriks veya balayc faz) sv fazl sinterleme ilemi srasnda bir miktar Wnin znd yzey merkez kbik kristal yapl ve sneklii yksek olan Ni-Fe-W ve Ni-Cu-W kat zeltileri oluturmaktadr. Balayc faz bileiminde Nie ek olarak Fe veya Cu kullanm,
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Wnin Ni iindeki znrln azaltarak zellikle krlganla yol aan nc fazlarn oluumunu engellemekte ve mekanik zelliklerde arta yol amaktadr. Tungsten ar alamlarnn retiminde en yaygn olarak kullanlan l sistem W-Ni-Fe sistemidir. Bu l sistemde balayc faz bileimindeki Ni:Fe orannn 7:3 olduu durumda intermetalik faz oluumlarnn engellenerek sinterlenmi durumdaki en iyi mekanik zellikleri verdii ifade edilmitir [1]. zellikle W miktarnn %90-%98 arlk orannda ve balayc faz bileimindeki Ni:Fe orannn 7:3 olduu alamlarda salanan yksek dayanm (850-1000 MPa) ve yksek sneklik (%12-%30 uzama) deerleri, bu tr alamlarn savunma sanayisinde yaygn olarak kullanmna yol amtr. Sv fazl sinterlenmi tungsten ar alamlarnn mekanik zellikleri zerine yaplan bir almada, balayc faz bileimindeki Ni:Fe orannn 7:3 olduu ve W arlk oranlarnn %80 ile %92 arasnda deitii W-Ni-Fe kompozit malzemelerinde, mekanik zelliklerin sadece tungsten paracklarna bal olduu ve balayc faz miktarndan etkilenmedii bulunmutur [2]. Balayc faz bileimindeki Ni:Fe orannn ayn olduu ancak tungsten arlk oranlarnn %88 ile %97 arasnda deitii W-Ni-Fe kompozitlerinin mekanik zellikleri zerine yaplan bir almada, 1480Cde 30 dakika sre ile hidrojen ve argon altnda sinterlenen numunelerde, 888-986 MPa arasnda ekme dayanm deerleri ve %12 ile %35 arasnda sneklik deerleri elde edilmitir [3]. almada en yksek dayanm deeri 93W-4,9Ni-2,1Fe alamnda, en dk sneklik ve dayanm deeri ise balayc faz miktarndaki azalmaya bal olarak 97W-2.1Ni-0,9Fe alamnda gzlenmitir. Tungsten miktarnn %93 arlk oranndan fazla olduu numunelerin (%95W ve %97W) boyun vermeden krld, ve krlmalarn nemli lde tane snrlar boyunca olduu, tungsten miktarnn daha fazla olduu numunelerde ise (%88W, %90W ve %93W) numunelerin boyun vererek krld gzlenmitir. Dayanmn en yksek olduu 93W-4,9Ni-2,1Fe numunelerinde yaplan krk yzey incelemelerinde krlmalarn nemli lde W tanelerinden olduu gzlenmitir [3]. Tungsten ar alamlarn mekanik zellikleri toz zelliklerinden, alam bileiminden, retim srelerinden ve sinterleme ilemi sonrasnda oluan mikroyapdan etkilenmektedir. zellikle sv fazl sinterleme ilemi srasnda oluan gzenekler, sv fazl sinterleme ilemi sonrasnda balayc faz bileimine ve soutma koullarna bal olarak oluan intermetalik fazlar, sv fazl sinterleme ileminin yapld hidrojen ortam ve tozlarn iinde bulunan safszlk atomlarnn yol at gevreklemeler mekanik zellikleri olumsuz etkilemekte [4-10], ve istenilen mekanik zelliklerde para imalat iin btn srecin iyi bir ekilde kontrol edilmesi gerekmektedir. W-Ni-Fe sisteminde retilen ar alamlarn nemli bir blmnde salad iyi mekanik zellikler nedeni ile balayc faz bileiminde Ni:Fe oran 7:3 olarak kullanlmaktadr. Bunun nedeni bu faz bileiminin krlganla yol aabilecek intermetalik bileiklerin oluumunu engellemesi ve buna bal olarak yksek dayanm ve yksek sneklik deerlerinin salanabilmesidir. Ancak, baz almalarda sinterlenmi durumda bulunan numunelerde balayc faz bileimindeki Ni:Fe orannn 2 ile 4 arasnda olduu durumlarda en iyi mekanik zelliklerin salanabilecei ifade edilmitir [12]. almamzn amac, %97 arlk orannda W ieren W-Ni-Fe alamlarnda, nemli bir deiken olan balayc faz iindeki Ni:Fe orannn (2, 3, ve 4) mekanik zelliklere etkisinin incelenmesidir 2. DENEYSEL YNTEM Deneysel almalarda kullanlan Fe, Ni ve W metal tozlarnn zellikleri izelge 1de verilmitir. Tozlarn ortalama tane byklkleri lazer tane bykl analiz cihaz (Model: Malvern Mastersizer 2000) ile llmtr. Tozlarn parack ekli taramal elektron mikroskop ile incelenmi ve ekil 1de verilmitir. izelge 1. almada kullanlan metal tozlarn zellikleri. Toz retici Saflk Toz ekli D10(m) D50(m) D90(m) Fe W. Rowland Ltd. 99.5+ Kresel 3.6 7.8 27.3 Ni AEE 99.9+ Kresel 5.2 9.1 16.1 W Eurotungstene 99.9+ Poligonal 1.7 4.2 10.3
Elementel metal tozlarndan yaklak olarak 3 kg olarak hazrlanan 97W-2Ni-1Fe, 97W-2,25Ni-0,75Fe ve 97W2,4Ni-0,6Fe toz karmlar Turbula kartrcda (Model: T2F Glenn Mills) dakikada 67 devir ile 45 dakika sre ile
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kartrlmlardr. Toz karmlarnn ekillendirilmesinde polimerik kalplar kullanlm ve numuneler souk izostatik presleme cihaznda (Model: Flow Autoclave Engineers CIP 42260) yaklak 15 saniye boyunca 300 MPa basn altnda sktrlarak ekillendirilmilerdir. ekillendirilen W-Ni-Fe alamlarn ya numunelerinin yaklak %65 teorik younlua ulatklar belirlenmitir. Sinterleme almalar yksek saflkta hidrojen gaz altnda (ilenme noktas = - 60C), 1480Cde atmosfer kontroll frn (Linn HT-1800) kullanlarak gerekletirilmitir. Sinterleme dngs u ekilde uygulanmtr : 9C/ dakika stma hz ile 1000Cye stma, saf H2 altnda 1000Cde 30 dakika oksit indirgeme, 3C/dakika stma hz ile 1480Cye stma, 1480Cde 20 dakika sre ile H2 altnda ve 10 dakika sre ile argon altnda sinterlemenin ardndan frnda soutma. Sinterlenen numunelerin mekanik zelliklerini belirleme almalarnda kullanlmak zere ekme testi ubuu ve sertlik, younluk lm ve iyap incelemeleri iin ise kk numune retimi yaplmtr. ekme deneyinde kullanlan numuneler uluslararas standarda uygun ekilde (ISO 6892) hazrlanmtr. ekme testi (Model: 3369 Instron) 0.5mm/dakika ekme hznda gerekletirilmitir. ekme testi sonular 3 adet numunenin ortalamas alnarak verilmitir.
ekil 1. almada kullanlan Fe, Ni ve W metal tozlarnn taramal elektron mikroskop grntleri. Alam numunelerinin iyaps geleneksel metalografi yntemleri ile incelenmitir. yap incelemeleri iin hazrlanan numuneler literatrde nerilen Murakami zeltisi (10 g K3Fe(CN)6, 10g NaOH, ve 100 ml saf H2O) ile dalanmtr. Numunelerin iyap incelemeleri nokta sayma yntemi kullanlarak optik ve elektron mikroskop grntleri zerinden gerekletirilmitir. Fazlarn hacimce miktarnn belirleme almalar ASTM E562 standardnn uygulanmas ile gerekletirilmitir. Tungsten bitiiklik deeri ise optik mikroskop ve elektron mikroskop grntleri zerine 10x10cmlik ve 1cm aralkl matrislerin izilmesiyle her bir izgiye den W-W balantsnn saylmasyla gerekletirilmitir. Bitiiklik deerinin hesaplanmasnda kullanlan basit denklem u ekildedir [12].
NWW = izgi bana den W-W balant says NWM = izgi bana den W-balayc faz balant says Sinterlenmi numunelerin younluk lmleri hassas terazi kullanlarak Arimet prensibi ile gerekletirilmitir. Younluk lmlerinde sv olarak ksilen (younluk 0.86g/cm3) kullanlmtr. W-Ni-Fe alamlarndaki faz dnm scaklklar ise DSC cihaz (Model: Setaram Setsys Evolution) kullanlarak belirlenmitir. DSC cihaznda argon atmosferi altnda yaplan lmlerde stma ve soutma hz olarak 10C/dakika kullanlmtr.
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3. DENEYSEL SONULAR ve TARTIMA Sinterlenmi numunelerin taramal elektron mikroskop grntleri ekil 2de verilmitir. Mikroyap, ortalama tane bykl 20-25 mikron olan kresel W tanelerinden (ak faz) ve balayc fazndan (siyah faz) olumaktadr. Younluk lmlerinde sinterlenmi numunelerin younluklarnn %99 teorik younluun zerinde olduu gzlenmitir. Optik mikroskop ile parlatlm yzeylerde yaplan mikroyap incelemelerinde sv fazl sinterlemenin tamam ile younlam 2 fazl bir mikroyapya yol at ve mikroyapda ok az miktarda (<%1) gzenek olduu belirlenmitir.
(a)
(b)
ekil 2. Sinterlenmi numunelerin taramal elektron mikroskop grntleri. (a) 97W-2Ni-1Fe, (b) 97W-2,25Ni-0,75Fe, (c) 97W-2.4Ni-0,6Fe Taramal elektron mikroskop grntlerinden, grnt yazlm ile yaplan incelemelerde sinterlenmi numunelerdeki toplam balayc faz miktarnn %5,5 ile %6,75 arasnda deitii, balayc faz iindeki Ni:Fe oran arttka, balayc faz miktarnn azald gzlenmitir. Numunelerin taramal elektron mikroskop grntlerinden bitiiklik lmleri yaplm ve bitiiklik deerlerinin Ni:Fe oranndaki arta bal olarak 0,52 ile 0,66 arasnda deitii belirlenmitir. Bitiiklik, W-W temas alannn toplam yzey alanna oran olarak tanmlanr. Bitiiklik ar alam iindeki W miktarna ve iki dzlemli aya kat-kat-sv l noktasndaki a baldr [12]. Bitiiklik deerinin artmas, W-W temas alann artracandan numunelerin snekliinde azalmaya yol aar. Sinterlenmi numunelerin mekanik zellikleri izelge 2de verilmitir. Sinterlenmi numuneler arasnda en yksek ekme dayanm (921 MPa) ve uzama deeri (%13) 97W-2Ni-1Fe numunesinde gzlenmitir. Rabin ve German tarafndan W-Ni-Fe alamlar zerine yaplan bir almada [3], alam bileiminin 97W-2,1Ni-0,9Fe olduu sinterlenmi ve sl ilem grm bir numunede ekme dayanm 888 MPa, uzama ise %12,4 olarak llmtr. almamzda 97W-2Ni-1Fe numunesinde elde edilen ekme dayanm ve uzama deerleri Rabin ve German tarafndan yaplan alma ile [3] benzerlik gstermektedir. Ancak almamzda elde edilen mekanik zellik deerleri balayc faz iindeki Ni:Fe orannn daha dk olduu durumda (Ni:Fe = 2) elde edilmitir. Bu sonu W-Ni-Fe sistemindeki ar alamlarda kullanlan balayc faz iindeki Ni:Fe orannn 7:3 gibi bir sabit deerde en yksek mekanik zellikleri vermediini, ve daha dk Ni:Fe oranlarnnda yksek mekanik zellikler salayabileceini gstermektedir.
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izelge 2. 1480Cde hidrojen ve argon altnda 30 dakika sre ile sinterlenmi ve frnda soutulmu numunelerin mekanik zellikleri. Numune 97W-2Ni-1Fe 97W-2,25Ni-0,75Fe 97W-2,4Ni-0,6Fe Balayc Faz Ni:Fe Oran 2 3 4 ekme Dayanm (MPa) 921 18 769 27 750 11 Uzama (% ) 13 1,2 3,3 0,6 2,6 0,7
Balayc faz iindeki Ni:Fe orannn artmasna bal olarak, 97W-2,25Ni-0,75Fe ve 97W-2,4Ni-0,6Fe numunelerinin ekme dayanmnda ve % uzama deerlerinde nemli azalmalar gzlenmitir (izelge 2). Bu iki numunenin, zellikle uzama deerlerindeki yksek orandaki dn, balayc faz iindeki Ni miktarnn artmasna bal olarak sinterleme ilemi srasnda ve/veya sonrasnda oluan intermetalik faz veya karbrlerden kaynakland dnlmtr. Edmonds ve Jones tarafndan W-Ni-Fe ve W-Ni-Cu sistemlerindeki tungsten alamlarnn gevreklii zerine yaplan bir almada sinterleme ileminden sonra yaplan frnda soutma ileminin tungsten ile balayc faz ara yzeyinde intermetalik faz oluumuna yol at ve buna bal olarak alamlarn gevrek davran gsterdii ifade edilmitir [5]. Sv fazl sinterlenmi 90W-7Ni-3Fe ve 90W-5Ni-5Fe alamlarnda yaplan analitik transmisyon elektron mikroskop almasnda tungsten-balayc faz arayzeyinde oluan fazn W(Ni,Fe) intermetalik bileii olduu ifade edilmitir [5]. Muddle tarafndan 90W-4,5Ni-4,5Fe alamnda, Posthill ve Edmonds tarafndan 90W-5Ni-5Fe alamnda yaplan transmisyon elektron mikroskop ve Auger spektroskopisi almalarnda [7,8], arayzeyde oluan 3. fazn W(Ni,Fe) intermetalik bileii yerine sinterleme ortamndaki Ca bal olarak oluan (Ni,Fe)6W6C veya (Ni,Fe)3W3C l karbr olabilecei ifade edilmitir. Balayc faz iindeki Ni:Fe orannn yksek olduu numunelerde yaplan X-n krnm almalarnda ana faz tungsten ve balayc faz Ni-Fe-W kat zeltisinin dnda nc bir faz gzlenmemitir. Bunun olas nedeni mekanik zelliklerde azalmaya neden olan intermetalik faz ve/veya karbr faznn miktarnn dk olmasdr. Taramal elektron mikroskop ile dalanm numune yzeylerinden yaplan mikroyap incelemelerinde nc bir faz tespit edilememitir. Ancak Ni:Fe oranndaki arta bal olarak zellikle uzama deerlerinde meydana gelen nemli ldeki azalmann bu alamlardaki nc bir faz oluumu ile ilgili olabileceini gstermektedir. Sinterlenmi numunelerde yaplan DSC almalarnda faz dnm scaklklar belirlenmitir. Numunelerin stma erilerinden yaplan incelemelerde 97W-2Ni-1Fe numunesinde balayc faz olarak bulunun Ni-Fe-W kat zeltisinin katgen scaklnn 1443C ve svgen scaklnn da 1467C olduu belirlenmitir. Balayc faz iindeki Ni miktarnn artna bal olarak 97W-2.25Ni-0,75Fe ve 97W-2.4Ni-0,6Fe numunelerinin katgen scaklklar 1441C ve 1409C, svgen scaklklar ise 1471C ve 1483C olarak llmtr. Balayc faz bileiminin deiimine bal olarak katgen ve svgen scaklklarndaki deiimin, balayc faz iindeki W znrllnn farkl olmas ve de zellikle Ni:Fe orannn 3 ve 4 olduu numunelerdeki olas 3. faz ile ilgili olduu dnlmtr. Balayc faz bileimindeki Ni:Fe orannn 3 ve 4 olduu numunelerin DSC stma erilerinde, katgen scaklnn zerinde 2. bir faz dnmne karlk gelen deiimler gzlenmitir. kinci faz dnmne karlk gelen scaklklar 97W-2.25Ni-0,75Fe numunesi iin yaklak olarak 1465C, 97W-2.4Ni-0,6Fe numunesi iin ise yaklak olarak 1472C olarak belirlenmitir. 97W-2.25Ni-0,75Fe ve 97W-2.4Ni-0,6Fe alamlarnn DSC stma erilerinde gzlenen 2. faz dnmnn, bu alamlar iinde W faz ve Ni-Fe-W kat zeltisinden ayr olarak bulunan 3. bir faz ile ilgili olduu dnlmtr. W-Ni-Fe sistemindeki ar alamlar zerinde yaplan almalar [7,8], 3. fazn sinterleme ileminden sonra soutma srasnda oluan (Ni,Fe)6W6C veya (Ni,Fe)3W3C faz olabileceini gstermektedir. Balayc faz iindeki Ni:Fe orannn yksek olduu durumda, olumas olas olan dier bir fazda Ni-W ikili sisteminde bulunan Ni4W intermetalik fazdr. Bu numunelerdeki mikroyap almalar devam etmektedir. Yaplacak olan detayl tramsmiyon elektron mikroskop almalar ile 3. faz bileimi ve kristal yaps belirlenecektir.
4.SONULAR Bu almada 1480Cde hidrojen ve argon altnda yarm saat sre ile sv fazl sinterlenen ve yksek younlua ulalan 97W-2Ni-1Fe, 97W-2,25Ni-0,75Fe, 97W-2,4Ni-0,6Fe alamlarnda, balayc faz iindeki Ni:Fe orannn (2, 3, ve 4) mekanik zelliklere etkisi incelenmitir. allan tungsten ar alamlarnda, balayc faz iindeki
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Ni:Fe orannn artmasna bal olarak ekme dayanmnn ve sneklik deerlerinin azald ve bunun tungsten ve balayc fazn dndaki nc bir faz ile balantl olduu belirlenmitir. TEEKKR Taramal elektron mikroskop almasndaki katklarndan tr Orta Dou Teknik niversitesi, Metalurji ve Malzeme Mhendislii Blmnden Cengiz Tan ve Serkan Ylmaza teekkr ederiz. 5.KAYNAKLAR [1] German R.M., Bourguignon L.L., Rabin B.H., Microstructure Limitations of High Tungsten Content Heavy Alloys, Journal of Metals, Vol. 37, No : 8, pp. 36-39, 1985. [2] Krock R.H., Sheppard L.A., Mechanical Behavior of the Two-Phase Composite, Tungsten-Nickel-Iron, Transactions AIME, Vol. 227, No:11, 1127-1134, 1963. [3] Rabin B.H., German R.M., Microstructure Effects on Tensile Properties of Tungsten-Nickel-Iron Composites, Metall. Trans. A, Vol.19A, No:6, 1988 [4] Churn K.S., Yoon D.N., Pore formation and its effect on mechanical properties in W-Ni-Fe heavy alloy, Powder Metallurgy, Vol. 2, No:4, pp. 175-179, 1979. [5] Edmonds D.V., Jones P.N., Interfacial Embrittlement in Liquid-Phase Sintered Tungsten Heavy Alloys, Metall. Trans. A, Vol. 10A, No:3, pp. 289-295, 1979. [6] German R.M., Churn K.S., Sintering Atmosphere Effects on the Ductility of W-Ni-Fe Heavy Metals, Metall. Trans. A, Vol. 15A, No:4, pp. 747-754, 1984. . [7] Muddle B.C., Interphase Boundary Precipitation in Liquid Phase Sintered W-Ni-Fe and W-Ni-Cu Alloys, Metall. Trans. A, Vol. 15A, No:6, pp. 1089-1098, 1984. [8] Posthill J.B., Edmonds D.V., Matrix and Interfacial Precipitation in the W-Ni-Fe System, Metall. Trans. A, Vol. 17A, No:11, pp. 1921-1934, 1986. [9] Yoon H.K., Lee S.H., Kang S.J.L.,Yoon D.N., Effect of vacuum-treatment on mechanical properties of W-Ni-Fe alloy, J. Mater. Sci., Vol. 18, pp. 1374-1380, 1983. [10] Edmonds D.V., Structure/Property Relationships in Sintered Heavy Alloys, Refractory Metals and Hard Materials, Vol. 10, pp. 15-26, 1991. [11] Caldwell S.G., Heat Treatment of Tungsten Heavy Alloys, International Journal of Powder Metallurgy, Vol. 39, No:7, pp. 43-51, 2003. [12] German R.M., Sintering Theory and Practice, John Wiley, Kanada, 1996.
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Bakr ve Grafit Katkl N Alamlanm Astaloy mO Toz Karmnda SNTERLEME ile sertletirme
Ahmet Murat GE*, Nuri DURLU*, Ayta ATA**, Hsn ZDURAL** *TOBB Ekonomi ve Teknoloji niversitesi, Makine Mhendislii Blm, Stz Caddesi No:43, Ankara, **Tozmetal Ticaret ve Sanayi A.. stanbul Caddesi No:75 Grpnar, Bykekmece, stanbul ZET Sinterleme ile sertletirme ilemi, ikincil bir sl ileme gerek kalmakszn toz metal paralarn retiminde kullanlan tek aamal ve dk maliyetli bir imalat ilemidir. Bu almada, %2Cu ve %0.7C ieren n alamlanm Astaloy Mo (Fe-1,5Mo) toz karmnda sinterleme ile sertletirme ilemi incelenmitir. Deneylerde presleme basnc olarak 600 MPa kullanlm, sinterleme ilemleri ve sinterleme ile sertletirme ilemleri sanayi lekli frnda 1120Cde metan gaz ortamnda yaplmtr. Sinterleme ile sertletirme ileminin mekanik zelliklere etkisinin belirlenmesi iin sinterlenmi numunelerin bir blmne ikincil bir sl ilem uygulanmtr. Sinterlenmi, sinterleme ile sertletirilmi, sinterlenmi ve ikincil sl ilem uygulanm numunelerin makrosertlik deerleri, apraz krlma dayanm deerleri belirlenmi ve mikroyaplar incelenmitir. alma uygun soutma koullar salanabildiinde, tek aamal sinterleme ile sertletirme ileminin ikincil bir sl ileme gerek kalmakszn istenilen mekanik zellikleri salayabileceini gstermitir. Anahtar Kelimeler: Toz metalurjisi, sl ilem, sinterleme ile sertletirme, n alaml tozlar, alamlama, sertleebilirlik.
SINTER HARDENING IN PREALLOYED ASTALOY MO ADMIXED WITH COPPER AND GRAPHITE

ABSTRACT Sinter hardening is a low cost one step process which eliminates secondary heat treatment in the manufacturing of powder metallurgy components. In this study sinter hardening behavior of prealloyed Astaloy Mo (Fe-1,5Mo) powder with %2Cu and %0,7C additions was examined. Samples were pressed at 600 MPa, sintered at 1120C under methane atmosphere in an industrial furnace. After sintering the samples were sinter hardened at two different cooling rates. In order to understand the sinter hardening behavior, a secondary heat treatment was done with the sintered samples. The macrohardness and transverse rupture strength of the sintered, sinter hardened, and sintered and heat treated samples were measured. Microstructure of the samples were examined with optical and scanning electron microscopy. The study show that, under favorable cooling conditions, sinter hardening can give comparable properties in comparison to sintered and heat treated samples. Key Words : Powder metallurgy, heat treatment, sinter hardening, prealloyed powders, alloying, hardenability 1.GR Demir esasl toz metal alamlarn mekanik zellikleri temel olarak sinterleme sonras younluk ve buna bal olarak para gzenekliliine baldr.[1]. Demir esasl toz metal alamlar genellikle sinterleme ilemi sonrasnda, martensitli bir yap elde edilebilmesi, ve daha yksek sertlik ve dayanm deerleri iin, ikincil sl ilemlere tabi tutulmaktadr. retilen paralarda mekanik zelliklerin arttrlmas iin gerekletirilen ikincil sl ilemler retim sra-
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snda maliyet artna neden olmaktadr [2]. Bu nedenle, sinterleme ile sertletirme ilemi ikincil sl ilemi ortadan kaldrabilmek iin, gn getike nemini arttran bir ilem haline gelmitir [3]. Sinterleme ile sertletirme ilemi temel olarak sinterlenme tamamlandktan sonra, retilen paralarn sinterleme scaklndan hzl soutmaya tabi tutularak sertlik artnn salanmasdr. Bu nedenle sinterlemenin gerekletirildii frnda, soutma hz ayarlanabilir bir soutma nitesi olmas gerekir. [4] Soutma ilemi frnda, sinterleme evrimi tamamlandktan sonra, soutma nitesinde yksek hzl hava akm oluturularak gereklemektedir. Bu sayede sinterleme ilemi sonras yaplacak olan ikincil sertletirme ilemlerine gereksinim duyulmakszn martensitli bir yap elde edilebilir. Bunun yannda geleneksel su verme ilemleri olduu gibi, malzeme ya veya su ile temasa sokulmadan hzl soutma ilemi gerekletirilmektedir [3]. Sonu olarak, su verme ilemi srasnda oluabilecek korosif etkiler de engellenmi olacaktr. Sinterleme ile sertletirme ilemi srasnda, ok yksek olmayan soutma hzlar sayesinde, geleneksel ikincil su verme ilemlerine oranla daha iyi boyut kontrol salanabilmektedir [3]. Sinterleme ile sertletirme ileminin baar ile gerekletirilebilmesi iin, sinterleme ileminden sonra yaplan soutma ileminin i parasnda beynitli ya da martensitli mikroyap oluumuna yol amas gerekir [5]. Hava akm ile soutma ilemi yeterli soutma hzlarna ulaamyor ise, malzeme sistemine eklenecek alam elementleri ile malzemenin sertleebilirlikleri arttrlarak, parann mekanik zelliklerinde azalmaya neden olmakszn, martensitli veya beynitli mikroyap oluumu salanabilmektedir. Molibden, nikel, krom ve bakr gibi alam elementleri demir esasl paralarn sertleebilirliini artrarak sinterleme ile sertletirme ileminin istenilen mekanik zelliklere ulamasn salar [6-8]. Sertleebilirliin artmasnda rol oynayan bir dier faktr ise stenit tane boyutudur. ri stenit taneleri, mikroyapda bulunacak tane snr miktarn azaltaca iin, tane snrlarndan balayan prlit dnm azalacaktr ve sonu olarak malzemenin sertleebilirlii artacaktr [9]. Bu nedenle sinterleme sresi ve sinterleme scakl sinterleme ile sertletirme ileminde nemli deikenlerdir [2]. Bunlarn yan sra, sinterleme ilemi gerekletirilecek parann bykl, sinterleme ile sertletirme ileminin sonucunu etkiler. Daha byk paralarda, gerekletirilecek olan s transferi daha yksek olaca iin, soutma hz ya da malzemenin sertleebilirlii daha yksek olmaldr [4]. Para boyutunun yannda, sinterleme ile sertletirme ileminde, toz metal paralarla alld iin, younluk nemli bir deikendir. zellikle para gzeneklilii, para boyunca oluacak s transferini etkilemektedir, bu nedenle Engstrm ve dierlerinin yapt bir almada, gzenekliliin sinterleme ile sertletirme ilemine etkisi allmtr [9]. Molibdenum, nikel, krom ieren n alamlanm Astaloy tozu sinterleme ile sertletirme ileminde yaygn olarak kullanlmaktadr. Warga ve Lindberg tarafndan Cu, Ni ve deiik oranlarda C eklenmi n alamlanm Astaloy Mo tozunda yaplan bir almada 1120Cde 30 dakika sre ile yaplan sinterleme ileminden sonra 1-8C/s arasndaki hzl soutma hzlarnda sinterleme ile sertletirilmi numunelerin mekanik zellikleri belirlenmitir [10]. almalar sonucunda Astaloy Mo tozuna eklenen %2 Cu veya %2Ni ve %0,4-%0,6Cnun sertleebilirlii ve mekanik zellikleri nemli lde artrd gzlenmitir. Maroli ve dierleri tarafndan yaplan bir dier almada Mo, Ni, Cr ve Mn ieren n alamlanm Astaloy tozlarnda soutma hznn mekanik zelliklere ve mikroyapya etkisi incelenmitir [11]. Bileimi Fe-2Ni-1,5Mo-0,5C olan alamdan hazrlanan numuneler 1120 Cde 30 dakika sre ile sinterlendikten sonra 0,1-8 C/saniye soutma hzlarnda sinterleme ile sertletirilmi, ve mikroyapda beynit ve martensit gzlenmitir Soutma hznn 8 C/ saniyeden hzl olduu durumlarda mikroyapda byk oranda martensit olduu ve az miktarda da kalnt stenit olutuu belirlenmitir. n alamlanm Astaloy Mo (Fe-1,5Mo) tozuna %2Cu ve %0,65C (veya %0,8C) eklenmesi ile oluturulan iki alam sisteminde ayn artlarda yaplan sinterleme ileminden sonra soutma hzndaki deiime bal olarak yava soutma hzlarnda (1-1,5 C/saniye) beynit ve martensit, hzl soutma hzlarnda ise (5-6 C/ saniye) martensit oluumu gzlenmitir [11]. . Bu almann amac %2Cu ve %0,7C eklenen n alamlanm Astaloy Mo (Fe-%1,5Mo) toz karmnda sinterleme ile sertletirme ileminin incelenmesi, sinterleme ileminden sonra ikincil sl ilemin sinterleme ile sertletirme ilemiyle karlatrlmasdr.
2.DENEYSEL YNTEM Bu almada, Hganas firmasnn su atomizasyon yntemiyle rettii n alamlanm Astaloy Mo tozu kullanlmtr. Tozun tane boyutu 50-150 mikron arasnda deimektedir. almalarda kullanlan tozun bileimi ve zellikleri izelge 1 de verilmitir. n alamlanm Astaloy Mo tozunun iine %2Cu ve %0,7C eklenmitir. Toz metalurjisi ile retilen paralarda Mo sertleebilirlii ve sktrlabilirlii artrmak iin, Cu sinterlenen paradaki boyutsal deiimi
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en aza indirmek iin, C (Grafit UF4) ise hem sertlii arttrmak hem de yalayc etkisi yaratmak iin kullanlan bir alam elementidir. Tozlarda yalayc olarak inko stearat kullanlmtr. izelge 1. almada kullanlan toz bileimi ve toz zellikleri.
Miktar % arlk
Grafit 0,7
Cu 2
Mo 1,5
Fe Kalan
Grnr younluk 3,32 g/cm3
Akkanlk 33 s/50 g
Numunelerin preslenmesi 600 MPa basn altnda 60 tonluk Instron marka ekme-basma cihaznda tek ynl basma yaplarak gerekletirilmitir. Presleme ileminden sonra numunelerde 7,04 g/cm3lk ham younluk elde edilmitir. Bu ilemde iki farkl geometride numune preslenmitir. Bu numuneler; nokta eme deneylerinde kullanlmak zere preslenen ubuk numuneler ve makro sertlik, mikro sertlik ve mikroyap almalar iin kontrol numunesi olarak preslenen pelet numunelerdir. 16 mm apl pelet numunelerde 8,5 g toz kullanlrken ubuk numunelerde 17 g toz kullanlmtr. ubuk numuneler TS 4222 EN ISO 3325 standartlarna uygun, apraz krlma testlerinde kullanlmak zere hazrlanmtr. Sinterleme ilemi ve sinterleme ile sertletirme ilemleri, Tozmetal firmasndaki endstriyel lekli frnda gerekletirilmitir. Sinterleme ilemleri sresince koruyucu atmosfer olarak metan kullanlmtr. Frnda yaplan ilemler sras ile; 700Cde yalayc ve balayc giderme ilemi, 1120Cye kadar kademeli olarak stma ve 20 dakika sre ile sinterleme. Normal soutma koullar 5 Hz olarak ayarlanmtr. Sinterleme ile sertletirme ilemi iki ayr soutma hzyla gerekletirilmitir. Bu soutma hzlar kullanlan frnn kapasitesine gre dk hzl soutma (15 Hz) ve yksek hzl soutma (30 Hz) olarak gerekletirilmitir. Frnn bant hz 200 mm/dk olup ve bir sinterleme evrimi 80 dakikada tamamlanmaktadr. Sinterleme ileminden sonra numunelere ikincil bir sl ilem uygulanmtr. kincil sl ilem, 0,5 NH3 ortamnda, 150 dakika boyunca 890C scaklkta 0,4 C ortamnda karbonitrrleme ilemini, ortam scaklnn 850Cye indirilmesinden sonra 1 dakika sre ile 1,0 C ve 0,5 NH3 ortamnda bekletmeden sonra, ayn scaklkta 30 dakika sreyle 0,75 C ve 0,5 NH3 ortamnda bekletme ve 70Cye ya banyosu iinde hzl su verme, ve 85Cde ykama ilemlerini iermektedir. Mikroyap almalar, makro ve mikro sertlik lmleri pelet numunelerin kesitinden yaplmtr. Yaplan metalografik yzey hazrlama almalar sonrasnda numunelerin gzenek yaps incelenmi, daha sonra %3 nital zeltisi kullanlarak dalanm yzeylerde mikroyap incelemesi yaplmtr. Makro sertlik lmleri HRC leinde a Wilson-Wolpert marka sertlik cihaznda, mikro sertlik lmleri HV0,1 leinde Buehler marka sertlik cihaznda gerekletirilmitir. Sertlik lmleri radyal ve dikey eksende alnmtr. Her bir numuneden 10 adet sertlik lm alnmtr. Mikro sertlik deneylerinde lmler radyal eksende 2 mm ve dikey eksende ise 1,25 mm aralklarla gerekletirilmitir. apraz krlma deneyleri standartlara uygun olarak (TS4222 EN ISO 3325) hazrlanm ubuk numunelerle gerekletirilmitir. Deneyler 5 tonluk Instron marka cihaznda standartlara uygun ekilde hazrlanm nokta basma deney dzenei ile 1mm/dakika basma hznda gerekletirilmitir. 3.DENEYSEL SONULAR ve TARTIMA 3.1.Mekanik zellikler Sinterlenmi, sinterleme ile sertletirilmi, ve ikincil sl ilem uygulanm numunelerin llen mekanik zellikleri izelge 2 de verilmitir. izelge 2. Sinterlenmi, sinterleme ile sertletirilmi, sinterlendikten sonra ikinci sl ilem uygulanm numunelerin makrosertlik ve apraz krlma dayanm deerleri. Numune (Fe-%2Cu-%1,5Mo-%0,7C) Sinterleme (1120C, 20dak.) Sinterleme (1120C, 20dak.) ve orta hzda soutma Sinterleme (1120C, 20dak.) ve yksek hzda soutma Sinterleme (1120C, 20dak.) ve ikincil sl ilem Makrosertlik (HRC) 391 441 451 482 apraz Krlma Dayanm (MPa) 88926 70260 73331 91868
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Sinterlenmi ve yava soutulmu numunelerin sertlik deeri 39 HRC olarak llmtr. Sinterleme ileminden sonra iki farkl soutma hznda yaplan sinterleme ile sertletirme ilemi sertlik deerlerinde yaklak olarak %12%15 civarnda bir art salam, ve sertlik deerleri 44 HRC ve 45 HRC olarak llmtr. Maroli ve dierlerinin yapt bir almada %2Cu ve %0,6C (veya % 0,8C) eklenen n alamlanm Astaloy Mo tozunda, azot ve hidrojen gaz karm ortamnda 1120Cde laboratuar lekli frnda yaplan sinterleme ileminden sonra sinterleme ile sertletirme ileminde soutma hznn 1-1,5 C/s olduu durumda sertlik deeri %0,6C iin 315 HV10, %0,8C iin ise 340 HV10 olduu gzlenmitir [11]. Sinterleme ile sertletirme ilemindeki soutma hznn artrlmas ile (2-3C/s ve 5-6C/s) sertlik deerlerinin %0.6C ieren numuneler iin 360 HV10 ve 430 HV10, %0,8 C ieren numuneler iin ise 375 HV10 ve 455 HV10 deerlerine ulat gzlenmitir [11]. almamzda sinterleme sonrasnda yava soutma koullarnda elde edilen sertlik deeri (39HRC) ve orta ve yksek hzda yaplan sinterleme ile sertletirme ilemi sonrasnda elde edilen sertlik deerleri (44 HRC ve 45 HRC) Maroli ve dierleri i[11] tarafndan yaplan almada orta ve yksek soutma hzlarnda elde edilen sertlik deerlerine benzerlik gstermektedir. Sinterleme ileminden sonra yaplan ikincil sl ilem sonrasnda numunelerin sertlik deerlerinde %25e yakn bir art gzlenmi ve sertlik deeri 48 HRC olarak llmtr. Sertlik deerindeki artn nedeni 800 C zerinde yaplan karbonitrrleme ilemine bal olarak azot ve karbonun numune yzeyine yaynarak yzey bileimini deimesi ve daha sonra yaplan yada suverme ilemi ile martensit faznn oluturulmasdr. Sinterlendikten sonra ikincil sl ilem yaplm numunelerde kesit boyunca mikrosertlik lmleri yaplm ve sonular ekil 1de verilmitir. Kenar blgelerde karbonitrrleme ilemine ve soutma hznn yksek olmas ile martensit faznn oluumuna bal olarak yksek sertlik deerleri (835 HV0,1) elde edilirken, orta blgede soutma hznn dk olmasna bal olarak dk sertlik deerleri (580 HV0,1) elde edilmitir. Sinterlenmi, sinterleme ile sertletirilmi, ve sinterleme sonras ikincil sl ilem uygulanm numunelerin apraz krlma dayanm deerlerinin 702 ile 918 MPa ararsnda deitii belirlenmitir. Sinterleme ilemi sonrasnda yava soutulmu numunenin apraz krlma dayanm deeri 889 MPa olarak llm, sinterleme sonras orta ve yksek hzda yaplan sinterleme ile sertletirme ilemi sonrasnda apraz krlma dayanm deerleri 702 MPa ve 733 MPa olarak belirlenmitir. En yksek apraz krlma dayanm deeri (918 MPa) sinterlendikten sonra ikincil sl ilem grm numunede gzlenmitir. Sinterleme ile sertletirme ilemi sinterleme ilemine kyasla sertlik deerlerinde art salarken apraz krlma dayanm deerlerinde azalmaya yol amtr. Bunun nedeni, sinterleme ile sertletirme ilemi sonrasnda, soutma hzndaki arta bal olarak numunelerin sertlik deerlerinin 44 HRC ve 45 HRCye ykselmesi ve buna bal olarak numune iinde bulunan gzeneklerin atlak etkisi gstererek gevrek krlmaya yol amasdr [12].
ekil 1. Sinterleme sonras sl ilem grm numunenin kesiti boyunca sertlik deiimi. 3.2. Mikroyap ncelemeleri ekil 2de sinterlenmi numunenin parlatlm yzeyden ve dalanm yzeyden elde edilen optik mikroskop grntleri verilmitir. Sinterlenmi mikroyap kk ve byk gzeneklerden olumaktadr (ekil 2.a). Sinterleme
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sonras yaplan younluk lmlerinde numune younluu yaklak olarak 7.1 g/cm3 olarak bulunmutur. Dalama ilemi sonrasnda mikroyapda beynit (koyu faz) ve martensitten (ince inemsi faz) oluan iki fazl bir mikroyap gzlenmitir. Sinterlenmi ve yava soutulmu numunede yaplan detayl mikrosertlik incelemeleri ile beynit faznn mikrosertlik deeri 422 HV0,1, martensit faznn mikrosertlik deeri ise 729 HV0,1 olarak belirlenmitir
ekil 2. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve yava soutulan numunenin mikroyaplar. (a) Parlatlm yzey, 100X, (b) Dalanm yzey, 1000X Sinterleme ileminden sonra orta hzda ve yksek hzda yaplan sinterleme ile sertletirme ileminden sonra optik mikroskopta elde edilen dalanm mikroyap grntleri ekil 3te verilmitir. Orta ve yksek hzda yaplan sinterleme ile sertletirme ilemi, soutma hznn artmasna bal olarak numunelerdeki martensit miktarn artrm ve beynit miktarn azaltmtr. Sinterleme ile sertletirme ilemi sonrasnda yaplan makrosertlik lmleri sinterlenmi numuneye kyasla sertlik artnn %15 civarnda olduunu gstermitir (izelge 2). Numuneler zerinde yaplan detayl mikroyap incelemeleri, sinterleme ile sertletirme ilemi srasnda, martensit ve beynitin yansra ok az miktarda kalnt stenit oluumu olduunu da gstermitir (ekil 2.b, ak beyaz yuvarlak faz).
ekil 3. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve orta ve yksek hzda sinterleme ile sertletirilen numunelerin dalanm mikroyaplar. (a) Orta hz, 100OX, (b) Yksek hz, 1000X. Sinterleme ileminden sonra yaplan ikincil sl ilem numunenin sertlik deerinde yaklak olarak %25 civarnda bir arta yol amtr (Tablo 1). Bunun nedeni karbonitrrleme ilemi srasnda numunenin yzeyinde azot ve karbon yaynmna bal olarak yzey bileiminin deiimi ve karbonitrrleme ileminden sonra yaplan hzl soutma ilemine bal olarak martensit faznn oluumudur. Karbonitrrleme ilemi sonrasnda numunenin yzey blgesinde oluan martensit mikroyaps optik mikroskop grnts ekil 4.ada, taramal elektron mikroskop grnts ekil 4.bde verilmitir.
ekil 3. 1120C de metan gaz ortamnda 20 dakika sinterlenen ve ikincil sl ilem uygulanan numunelerin mikroyap grntleri (a) Kenar blge, optik mikroskop 100OX, (b) Kenar blge, taramal elektron mikroskop, 3000X.
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4. SONULAR Fe-%2Cu-%1,5Mo-%0,7C toz alamnda 1120Cde 20 dakika sre ile yaplan sinterleme ilemi 39 HRC sertlik deerine, sinterleme sonrasnda iki farkl soutma hznda yaplan sinterleme ile sertletirme ilemi 45 HRC sertlik deerine, sinterleme ileminden sonra yaplan ikinci sl ilem ise yaklak olarak 48 HRC sertlik deerine yol amtr. Sinterlenmi ve sinterleme ile sertletirilmi numunelerde yaplan mikroyap incelemelerinde, mikroyaplarn martensit ve beynitten olutuu ve numunelerde ok az miktarda kalnt stenit bulunduu belirlenmitir. TEEKKR Bu alma TOBB Ekonomi ve Teknoloji niversitesi ve Tozmetal A. firmasnn katklar ile gerekletirilmitir. Taramal elektron mikroskop almasndaki katklarndan tr Cengiz Tan ve Serkan Ylmaza teekkr ederiz. 5.KAYNAKLAR [1] Bocchini G.F., Rivolta B., Silva G., Poggio E., Pinasco M.R., Ienco M.G., Microstructural and Mechanical Characterisation of some Sinter Hardening Alloys and Comparisons with Heat Treated PM Steels, Powder Metallurgy, Vol. 47 No. 4, 343-351, 2004 [2] James W. B., What is Sinter Hardening, International Conference on Powder Metallurgy & Particulate Materials, May 31-June 4, 1998, Las Vegas, Nevada, USA. [3] Hatami S., Malakizadi A., Nyborg L., Wallin D., Critical aspect of sinter-hardening of prealloyed Cr-Mo steel, Journal of Materials Processing Technology 2010 1180-1189. [4] Maroli B., Berg S., Larsson M., Hauer I., Performance of Sinter-Hardened P/M Steels, EUROMAT ITALY, 2001 [5] Blais C., Serafini R.E.Jr., LEsprance G., Effect of Hydrogen Concentration in Cooling Zone on Sinter Hardening, International Journal of Powder Metallurgy Volume 41, Issue 4, 33-41, 2005 [6] Rutz H. G., Graham A. H., Davala A. B., Sinter-Hardening P/M Steels, nternational Conference on Powder Metallurgy & Particulate Materials, June 29-July 2, 1997, Chicago, IL USA. [7] Causron R.J., Fulmer J.J., Sinter Hardening Low-Alloy Steels, Powder Metallurgy World Congress San Francisco, CA, June 21-26, 1992. [8] Engstrm U., Frykholm R., Milligan D., Warzel R., Cost Effective Materials for Sinter Hardening Applications, PM2008 Washington, USA, June 11, 2008. [9] Krauss G., Steels: Processing, Structure, and Performance, ASM International, 316-317, 2005 [10] Warga D., Lindberg C., Efficient Sintering and Hardening in the Conveyor Belt Sintering Furnace, 1993, Powder Metallurgy World Congress, Kyoto, Japan, pp.983. [11] Maroli B., Berg S., Larsson M., Hauer I., Performance of Sinter-Hardened P/M Steels, Euromat, Italy, 2001. [12] Straffelini G., Fontanari V., Hafez A., Benedetti M., Tensile and Fatigue Behavior of Sinter Hardened Fe-15Mo0.6C Steels, Powder Metallurgy, Volume 41, Issue 4, 298-303, 2009.
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CHARACTERIZATION OF POWDER AND PARTS
www.turkishpm.org
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Abrasive wear behaviour of PMD 23 and M2 cold work tool steels

Ferhat GL1, Melik ETN2
1
Gazi University, Technology Faculty, Metallurgical and Materials Engineering, Teknikokullar, Ankara, Turkey 2 Karabuk University, Technical Education Faculty, Division of Metal Casting, Karabuk, Turkey 1fgul@gazi.edu.tr, 2mcetin@karabuk.edu.tr ABSTRACT
In this study, abrasive wear behaviour of PMD 23 and M2 cold work tool steel produced through two different methods (powder metallurgy and conventional ) was investigated. The wear tests were carried out at sliding velocities of 0.1 m s-1 and under 10 N, 20 N, and 30 N variable loads. The sliding distance was 10 m for all the tests and by rubbing the specimens to abrasive Al2O3 grains with 38, 65 and 150 m. Abrasive wear tests revealed that, abrasive wear loss increased with increasing abrasive particle size. The wear loses of PMD 23 steel was found to be lower than that of the M2 cold work tool steel under the same test conditions. Keywords: Wear, tool steel, abrasive grain size. 1. Introduction The utilize of powder metallurgy (PM) processes to manufacture near-net-shape steel components has increased quickly in current years, mainly because PM processes are capable of producing material compositions that are impractical to obtain by conventional casting processes[1,2]. Materials produced by PM processes acquire outstanding structural homogeneity and fine microstructure. Also these days, many high alloyed cold-working tool steels are developed by advanced powder metallurgy (PM) methods, such as hot isostatic pressing (HIP), powder injection moulding and spray forming and so on. On the consideration of their fine and homogeneous microstructure, high alloyed PM cold-working tool steels with excellent strength and good wear resistance are presently employed for stamping forming dies, industrial knives, slitters, plastic mold inserts and wear parts[3-6]. PM high alloyed coldworking tool steels are commonly strengthened by tempered martensite and high volume fraction of carbides [2]. PMD 23 is a new cold work-tool steel developed by Drrenberg Edelstahl, Germany. It is an development over the familiar cold work-tool steel. PMD23 is a new tool steel, little information is available in literature related to its wear behaviour. Therefore, in this study, the effect of microstructure on the hardness and abrasive wear behaviour of PMD 23 and M2 cold work tool steel produced through two different methods (powder metallurgy and conventional) conditions were determined. 2.Experimental procedure Experimental study was performed on a PMD 23 and M2 cold work tool steel. The chemical composition of PMD 23 is 1.30C4.20Cr5.00Mo3.10V6.40W-Fe(wt.%), which was produced by Drrenberg Edelstahl, Germany. M2 cold work tool steel chemical composition is 0.90C4.10Cr5.00Mo1.90V6.40W-Fe(wt.%), and it was made by conventional method. The samples subjected to wear tests were wire cutted from the forged-and-soft annealed master blocks. Then they were austenitized at 1180oC for 30 min in vacuum with uniform N2 gas quenching and than they were tempered at 550oC for 3 h, the details of each step being illustrated in Fig. 1. Specimens for metallographic observations were prepared by grinding down to 1200 grit abrasive papers followed by polishing with 0.3 m diamond paste. The microstructure of the specimens was investigated by means of the optical microscopy. The
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Vickers hardness of the PMD 23 and M2 cold work tool steel were determined using Instron Wolpert Testor DIA Testor 7551 using a load of 1 kg and each hardness value is an average of 10 measurements. The hardness of the tempered PMD 23 and M2 cold work tool steel are about 860HV1, 840 HV1, respectively. Abrasive tests of the PMD 23 and M2 cold work tool steels were carried out on the two-body pin on disc apparatus shown in Fig. 2 under the loads of 10 N, 20 N, and 30 N at the speed of 0.1 m s-1, by rubbing the specimens having 6,25 mm diameter and 50 mm length, on bonded abrasive Al2O3 abrasive. During the wear tests, specimens that were rubbing on the abrasives were moving perpendicular to the sliding direction so that they always passed over fresh abrasives. Six different particle sizes (38, 65 and 150 m) of abrasive Al2O3 abrasives were used to test each specimen. Total sliding distance of the specimens on the abrasives were 10 m. Specimens were weighed, before and after the test, using an electronic scale with a resolution of 104 g in order to determine wear losses as weight loss. The abrasion tests were performed three times for each sample and the results were calculated using the mean values.
Fig. 1. Schematically representation of heat treatments
Fig. 2.A schematic pin-on-disc wear test configuration 3. Result and discussion Fig. 1(a) and (b) show the typical microstructure of the PMD 23 and M2 cold work tool steel after austenitized and tempered, respectively. For typical austenitization temperature at 1180oC, the equilibrium phase situate consists of the austenitic matrix and carbides. Microscopic examinations revealed that light coloured needle like vanadium carbides and they are regularly distributed in the tempered martensitic matrix. Previously, vanadium carbides in microstructure of cold work tool steel after austenitized and tempered have also been reported [4, 7]. The carbides in the martensitic matrix produce an natural wear resistance [7].
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Fig. 3: Microstructure of the specimens (a) PMD 23 cold work tool steel (b) M2 cold work tool steel centrifugally casting Results of abrasive wear tests on the PMD 23 cold work tool steel and M2 cold work tool steel after austenitized and tempered, are shown in Fig. 4 and Fig. 5, respectively. The weight loss of the PMD 23 and M2 cold work tool steels increased with increasing the applied load, and abrasive particle size. PMD 23 cold work tool steels (high vanadium steels) exhibit low weight loss than M2 cold work tool steel under the loads of 10-30N for all the abrasive particle sizes (Fig. 4 and Fig. 5). They are excellent candidates for replacing sintered carbides and other materials that are highly resistance to wear in machinery. The most important result of the abrasive wear test is that abrasive Al2O3 grain size and applied load have an important effect on the wear lose of the investigated PMD 23 and M2 cold work tool steels Fig. 4 and Fig 5 obviously shows that, abrasive wear lose of PMD 23 and M2 cold work tool steels increased with increasing abrasive grain size in accord with the work of Cetin and Gul [8] and Shue and Lin [9].
Fig. 4: The effect of the size of abrasive Al2O3 grain and loads on the wear loss of the PMD23 cold work tool steel
Fig. 5: The effect of the size of abrasive Al2O3 grain and loads on the wear loss of the M2cold work tool steel
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Conclusion An experimental study of wear behaviour of PMD23 and M2 cold work tool steel used in this investigation at different load and the size of abrasive Al2O3 grains value reveals the following conclusion: 1. The microstructure of the PMD23 cold work tool steel had finer grains than M2cold work tool steel. Decreasing grain size led to increase in hardness 2. Wear lose values increased with the increment of load and abrasive Al2O3 grain size 3. The wear lose of PMD23 steel was found to be lower than that of the M2 cold work tool steel under the same test conditions. Acknowledgement The authors are thankful to Saglam Metal (Istanbul-TR) and and Mr. Fatih YALAVA for providing PMD23 cold work tool steel. References 1. 2. 3. 4. 5. 6. 7. 8. 9. R.M. German, Powder Metalurgy of Iron and Steel, John Willey and Sons, U.S.A. K. S. Narasimhan, Materials Chemistry and Physics, Volume 67, Issues 1-3,2001, Pages 56-65 H.K. Moon, K.B. Lee, H.Kwon, Materials Science and Engineering A 474 (2008) 328334 S. Weber, W. Theisen, F. Castro, A. Pyzalla, Materials Science and Engineering: A, Volume 515, Issues 1-2, 25 July 2009, Pages 175-182 J. Richter, Materials Characterization, Volume 50, Issues 4-5, June 2003, Pages 339-347 J. Yao, X.H. Qu*, X.B. He, L. Zhang, Materials Science and Engineering A 528 (2011) 41804186 R.M. Muoz Riofano, L.C. Casteletti, L.C.F. Canale, G.E. Totten, Wear, Volume 265, Issues 1-2, 25 (2008) 57-64. M.etin and F.Gul, TEKNOLOJ, Cilt 11(2), 137-144, (2008). C-Y. Sheu, S.-J. Lin, Scripta Materialia, Volume 35, Issue 11, 1 December 1996, Pages 1271-1276
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SOME PROPERTIES OF CLINOPTILOLITE AFTER LONG-TERM HOT ACID LEACHING

Osman AN*, Remzi GREN*, Cem ZGR*, Muhterem KO**, Tuba ERGLER*, Ali MARETL*
* Dumlupnar University, Department of Ceramic Engineering, Ktahya, 43100, Turkey, osmansan@dumlupinar.edu.tr, rgoren@dumlupinar.edu.tr, cozgur@dumlupinar.edu.tr, tubaerguler@gmail.com, imaretli@gmail.com ** Celal Bayar University, Turgutlu Vocational School, Department of Industrial Glass and Ceramic, Manisa, 45400, Turkey, muhterem.koc@bayar.edu.tr
ABSTRACT This study presents an investigation on the purification of a natural zeolite (clinoptilolite) by acid leaching conducted in hot solution (75C and 5 M HCl) for the period up to 72 h and examines some properties of the powder samples such as change in chemical compositions, specific surface areas, X-ray detected phases and size of the particles. The treatment increased the specific surface area from 47.87 m2/g to 154.3 m2/g, with the SiO2 content being 97.5 wt.%. The reduction of aluminum, potassium, iron and calcium oxides was significant. The longer time leaching removed the clinoptilolite phase but did not remove the impurity phases such as cristoballite, quartz and tridimite. The leaching process significantly decreased the size of particles. The material may potential be used as high silica ceramic powder. Keywords: Zeolite powders, chemical preparation, silicate 1. Introduction Abundant deposits of zeolitic tuffs have been discovered in many countries. Among them, clinoptilolite is the most common and industrially important natural zeolite. It is a natural zeolite mineral from the tectosilicates group. Its typical unit cell formula is Na6[(AlO2)6(SiO2)30] 24H2O [1]. The most important property of clinoptilolite is its high cation exchange capability which makes it a potential candidate in the removal of inorganic contaminants from water and wastewater [2-5]. In addition, it is also possible to remove nonionic organic contaminants in liquids by a modified clinoptilolite through adsorption of cationic surfactants [6]. In addition, clinoptilolite is abundant and inexpensive, making this zeolite an attractive alternative to use of a ceramic powder. Fusibility of the clinoptilolite at relatively low temperatures has great importance since they are used in the ceramic industry as sintering aids [7-8]. Recently, a natural zeolite was used as a phase-transforming agent for quartz to cristobalite [9]; the zeolite was melted at a low temperature (around 800C), and further heating provided good dispersion of the liquid phase through the quartz particles. The chemical modification of zeolites by acid can increase both porosity and the capacity of adsorption. However, not only adsorption capacity of the material is altered, but acid treatment could also alter the secondary porosity and the crystalline network of the zeolite [10]. It is necessary to investigate the chemical changes produced by the acidic treatment of zeolites in order to verify that the desired improvements occur without altering properties of interest for the final application. In this study, the clinoptilolite was investigated as high silica- containing ceramic powder. For this purpose, the clinoptilolite powder was leached for long-term treatment. 2. Materials and Methods Natural zeolite (clinoptilolite) was obtained from a mine located at Manisa-Grdes in Turkey (Enni Mining). The sample was wet ground in attrition mill for 1 h using alumina balls. The slurry was dried at 105oC for 24 h, and then
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leached in 5 M HCl solution at 75oC. The treatment duration was selected as 72 h [11]. During leaching, 10 g of clinoptilolite sample was weighed and poured into 200 ml of solution, the solution was then stirred continuously at 500 rpm using a magnetic stirrer and a thermostat was used to keep the reaction medium at constant temperature. After a predetermined period of time, the solid product was filtered and washed with distilled water. The study of the samples included: (i) chemical composition measurement by X-ray fluorescence (Spectro X-LAB 200), (ii) crystalline phase identification by X-ray analysis (Rigaku Miniflex powder diffractometer employing CuK radiation in 2 = 10-65o at a ganiometer rate of 2 = 2o/min.), (iii) particle-size determination by zeta sizer (MalvernNano S) and (iv) determination of specific surface areas by BET (Quantachrome-Nova 2200e). 3. Results 3.1. Dissolution during leaching The raw clinoptilolite powder was treated in hot-acid solutions of 5M HCl at 75 C to remove impurities such as, alkaline earth and alkali metal compounds as well as the alumina. The amount of total dissolving components from the powder sample was determined as 25 wt.% for the long-term processing (72 h). 3.2. Analysis of the crystal structure 3.2.1. The as-received clinoptilolite The X-ray diffraction analysis of the raw clinoptilolite powder is given in Fig. 1. It shows an essentially clinoptilolite phase with crystalline phases which are cristobalite, quartz and tridymite.
Figure 1. XRD pattern of as-received clinoptilolite powder. 3.2.2. The leached clinoptilolite After leaching, the clinoptilolite phases of the sample undergo and the other crystalline phases such as cristobalite, quartz and tridimite could not be removed. The long-term leaching showed that during stirring the presence of hard constituents in the solvent medium tended to facilitate the break-down of coarse clinoptilolite particles. This phenomenon induced a more amorphous structure and the shapes of amorphous peaks became broader. 3.3. Influence of leaching time on chemical composition Changes in the chemical compositions of the as-received clinoptilolite after leaching for 72 h are given in Table 1. The de-alumination of the powder material was succeeded and the iron contamination was significantly reduced. The leached powder samples exhibit less crystalline structure (see Fig. 2) and being a high-grade silica material, having more than 97 wt.%SiO2.
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Figure 2. XRD pattern of leached clinoptilolite powder. Table 1. Chemical composition of the as-received and leached clinoptilolite (wt.%). Oxides As-received Leached SiO2 83.88 97.50 Al2O3 8.27 1.00 K2O 3.67 1.10 Fe2O3 1.77 0.48 CaO 1.81 0.084 Na2O 0.26 0.02 MgO 0.64 0.31 TiO2 0.10 0.07 MnO 0.04 0.01 P2O5 0.02 0.02 SO3 0.02 0,02
3.4. Influence of leaching times on particle size and distribution The size distributions of the untreated and leached clinoptilolite powders were investigated by zeta sizer (MalvernNano S). Fig. 3 presents the plot of cumulative mass percent finer versus particle size. After leaching the particle size of the sample became finer due to fracture of the large particles and the sample acquired a monomial and narrow size distribution.
Figure 3. Size distributions of raw and leached clinoptilolite powders. 3.5. Influence of leaching on the specific surface area The BET surface area values of the raw and leached powders are given in Table 2. As evident from the table, the surface area of clinoptilolite greatly increased after the leaching. The reason for the increase in the specific surface area could mainly be due to the breakdown and/or very intensive erosion of the larger particles through the longterm processing. Table 2. Specific surface area of the clinoptilolite with and without leaching. Samples Raw clinoptilolite Leached clinoptilolite Specific surface area, m2/g 47.87 154.30
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4. Discussion Motivation of the present study was the previous finding that a high silica-containing ceramic powder has been investigated from diatomite where a low-grade diatomite having 68.08 wt. % SiO2 was leached through long-term (240 h) and a high silica-containing material containing 98 wt. % SiO2 was obtained. Phase analysis of the sample indicated a highly amorphous structure and the remaining phase was only a small quantity of quartz [11]. The powder was used for the fabrication of beta-cristobalite ceramic material for filtration application in harsh thermal environments. The small amount of impurities had no significant influence on the thermal behavior of the ceramic material and the thermal expansion coefficient was found as 11.42 x 10-6C-1 [12]. The present study indicated that the leached clinoptilolite for 72 h has great potential for the production of betacristobalite ceramic material with high silica-content which could be obtained after a shorter time treatment (72 h) and the resulting impurities would be quite low. 5. Conclusion These following salient conclusions related to the leaching treatment can be made: 1. High SiO2 ceramic powders having 97 wt.% SiO2 can be successfully prepared from impure raw zeolite (clinoptilolite) after a prolonged time (72 h) of hot-acid (75C and 5 M HCl) leaching. 2. When the raw zeolite powder is treated with hot acid solution (5 M HCl) for the longer time (72 h), the surface area of powder increases from 47 to 154 m2/g. 3. The leaching process provides a decrease in average particle size significantly from 825 nm to 100 nm. 4. Also, the leaching process makes possible the production of ceramic powders containing high-silica with several ratios by adjusting the leaching conditions. REFERENCES [1] T. Armbruster, Studies in surface science and catalysis, in: A. Galarnau, F. Di Renzo, F. Faujula, J. Vedrine (Eds.), yqq1, vol. 135, Elsevier, Amsterdam, 2001. [2] D.W. Breck, in: Zeolite Molecular Sieves, John Wiley, New York, 1974, pp. 529588. [3] N.A. Hernndez-Beltrn, M.T. Olgun, Elemental composition variability of clinoptilolite-rich tuff after the treatment with acid phosphate solutions, Hydrometallurgy 89 (2007) 374378. [4] J. Hlavay, G. Vigh, V. Olaszi, J. Inczedy, Ammonia and iron removal from drinking water with clinoptilolite tuff, Zeolites 3 (1983) 188-190. [5] G. Blanchard, M. Maunaye, G. Martin, Removal of heavy metals from waters by means of natural zeolites,Water Res. 18 (1984) 1501-1507. [6] B. Ersoy, Adsorption mechanisms of cationic surfactants onto clinoptilolite and removal of non-ionic organic contaminants by modified clinoptilolite , Ph.D. Thesis, Istanbul Technical University, Istanbul, 2000, p. 212. [7] F. Andreola, T. Manfredini, E. Passaglia, G.C. Pellacani, P. Pozzi and M. Romagnoli, Utilization of an Italian Zeolite in ceramic bodies, Materials Engineering, 5 (1994) 299-312. [8] R. de Gennaro, P. Cappelletti, G. Cerri, M. de Gennaro, M. Dondi, G. Guarini, A. Langella and D. Naimo, Influence of zeolites on the sintering and technological properties of porcelain stoneware tiles, Journal of the European Ceramic Society 23 (2003) 2237-2245. [9] O. an, S. Abal and . Hoten, Fabrication of microporous ceramics from ceramic powders of quartz-natural zeolite mixtures, Ceramic International, 29 (2003) 927-931. [10] N.A. Hernndez-Beltrn, M.T. Olgun, Elemental composition variability of clinoptilolite-rich tuff after the treatment with acid phosphate solutions, Hydrometallurgy, 89 (2007) 374378. [11] O. an, R. Gren, C. zgr, Purification of diatomite powder by acid leaching for use in fabrication of porous ceramics, Internal Journal of Mineral Processing, 93 (2009) 6-10. [12] O. an, C. zgr, Preparation of a stabilized cristobalite ceramic from diatomite, Journal of Alloys and Compounds, 484 (2009) 920-923
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Investigation on the Use of Natural Zeolite for Ceramic Pigment

Eda Tasci1, Mustafa Tuncer1 and Ismail Ozden Alp2
1
Dumlupnar University, Ceramic Engineering Department, Kutahya, TURKEY 2 Altn Ceramic Company, Kutahya, TURKEY Abstract
Pigments for ceramic glaze were obtained by treating clinoptilolite type-natural zeolite with aqueous solution of FeCl3. The powders calcined at different temperature were characterized using X-ray diffraction, chemical analysis. Coloring properties of pigment powders tested in transparent floor tile glaze was analysized using LAB instrument. The results showed that the whiteness value (+L) of pigments decreased while redness value (+a) increase with increasing calcination temperature from 1000 to 1200 oC. It can be started that natural zeolite with ion exchange are expected to be useful for ceramic pigment. Keywords: Pigment, clinoptilolite, ion exchange. 1. Introduction The term pigments is applied to black, white and colored organic or inorganic powders that are insoluble in the substrate in which they are incorporated not chemically and physically altered by it [1]. Ceramic pigments were synthesized by solid-state reactions and the color developed in a suitable ceramic glaze was investigated in comparison with the color developed by the pigments prepared from pure SiO2. Raw materials which are mostly metallic oxides or salts of the desired metals with industrial chemical purity are used for pigment production [2]. Some minerals are employed as host materials for colorant ions because of specific crystal structure. One of these is naturally occurring zeolites. They are microporous aluminosilicate materials with wide use in catalysis, molecular sieving, animal nourishment and slow release fertilizers [3]. These applications are related to their structure with cages and channels of molecular size ranging from about 2- 15 in size. The replacement of Si+4 by Al+3 creates negative charge in zeolite framework. This charge is compensated by cations positioned in the structure. These cations can easily be inserted into framework, leading to new ceramic phase. So the new materials can be development [4]. The aim of present study was to produce ceramic pigments based on zeolite previously exchanged with colorant ions. FeCl3 was chosen as colorant agent. 2. Experimental Procedure Industrial quality clinoptilonite-type zeolites have been used as starting raw materials for the pigment preparation. Firstly, zeolite was leached to eliminate cations such as sodium, potassium and calcium that are in the pores of zeolite and then ion exchange procedure was conducted as follow. In a 300 cc glass bottle, FeCl3.6H2O (5.5 g) was dissolved in 200 cc of deionized water and mixed until to get clear solution. The leached zeolite (5.2 g) was dispersed in Fe-solution. The bottle was sealed and kept at 70 oC for 2 days. This procedure was repeated three times. The powders were filtered, subsequently washed for twice with 50 ml distilled water. It was centrifuged at 9000 rpm for 5 min, dried at 90 oC overnight and finally gentle crushed in agate mortar. The obtained mixture has been calcined in a closed porcelain crucibles at different temperatures (1100, 1175 and 1200 oC) for 60 min of soaking time and then dry milled. The phase content of powders were identified by X-ray diffractometer (Rigaku, Miniflex) using Cu K radiation over the range of 2080o at a rate of 2o/min. the oxide content were determined by X-ray fluorescence
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(Spectra). The morphology and microstructure of the powders have been examined by Scanning Electron Microscopy (SEM, Zeiss Supra 50 VP ) The obtained powders have been tested as pigments for glaze coloring. A ceramic glaze, having a typical composition for porcelainized stoneware, has been used for pigment application. The pigments, added to the composition at 3 wt%, have been wet mixed with the ceramic frit for 30 min in a blender-mixer and then dried. The dried powders have been pressed at 40 MPa to produce wires (40mm diameter) that have been fired in an industrial high-speed roller kiln using a typical industrial cycle of 40 min. Color measurements have been performed on both pigments and glazes by UVvis spectroscopy (model Lambda 19, Perkin Elmer) using the CIElab method in order to obtain L*, a* and b* values. 3. Results and Discussion Table 1 reports the chemical analysis of clinoptilolite type zeolite. Regarding the loss of ignitions the elemental analysis defines that the hydrogen content is 0.15 wt %, the nitrogen content is 0.16 wt % while the carbon content is 11 wt % in accordance with light green color of the zeolite. The chemical analysis, thus, confirms that the as received clinoptilolite type zeolite, though with 11 wt% of loss of ignition, is a waste that contains a 67 wt% of very pure silica. Other oxides are all lower than 3 wt%; the chromofore oxides, in particular Fe2O3 and TiO2, that can influence the color developed by the pigment in a ceramic matrix, are present only as traces. After the exchange process, the amount of iron oxide in zeolite was increased from 1.79 to 3.55. Table 1. Oxide composition of raw and exchanged zeolite Oxides (%) Raw Zeolite Exchanged Zeolite SiO2 67,1 84,71 Al2O3 11,8 6,11 Fe2O3 1,79 3,55 CaO 3,87 0,63 MgO 1,21 1,04 K 2O 2,29 1,09 Na2O 0,3 2,86 TiO2 0,11 LOI**. 11,49 Total 100 99,99
Fig. 1 shows XRD pattern of raw zeolite. Clearly, it had clinoptilolite phase with minor silica.
Fig. 1. XRD patterns of raw zeolite (Q: Kuvars, C: Klinoptilolit, P: Olajioklas). Fig.2. shows XRD patterns of ion exchanged-clinoptilolite calcined at different temperature. The XRD results showed cristobalite was main phase. Fe-exchanged clinoptilolite was transformed to new ceramic phase, which is cristobalite. This new phase acted as host crystal for Fe ion.
Fig.2. XRD analysis of Fe-exchanged zeolite calcined at different temperature (C: cristobalite).
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The successful formation of the cristobalite based pigments has been also confirmed by colorimetric analysis. In fact, the b* parameter, indicating the predominance of the yellow color (+b*) on the blue color (b*), increases with the calcination temperature, irrespective of the silica precursor used. The color developed by the two precursor is quite the same and reach the higher yellowness at 1200 oC. For this reason only the pigments calcined at 1100 oC have been used to verify their chemical stability in a ceramic glaze. The color developed by these pigments added both at 3 wt% in an industrial glaze for high temperature is reported in Table 2. The table shows that Table 1. L*a*b* values for the sintered pigments and the applications (glazes 3 wt% of pigment). The obtained pigments developed a good yellow color, irrespective of the raw materials used, indicating the chemical and thermal stability of the synthesized powders. Table 2. CIElab values of the obtained glazes. Colour parameters Thermal Treatment (C) 1100 1175 1200 4. Conclusion Fe-exchanged zeolite was successfully produced using ion exchange procedure. The Cristobalite type structure formed after heat treatment. The obtained pigments were stable and develop an intense pink color that is very similar to the colored by the pigments obtained starting from pure quartz. The result showed that the clinoptilolite type zeolite can be used as host material for coloring. Acknowledgements The authors would like to thanks Ceramic Engineer Mehmet Akkas for XRF Analysis. References 1. P. A. Lewis, Pigment Handbook, (1988), Vol. I, 2nd Ed., John Wiley & Sons, New York, USA 945 pp. 2. Federica Bondioli, Fernanda Andreola, Luisa Barbieri, Tiziano Manfredini and Anna Maria Ferrari, Effect of rice husk ash (RHA) in the synthesis of (Pr,Zr)SiO4 ceramic pigment, Journal of the European Ceramic Society 27 (2007), p.34833488. 3. V. M. PogrebenkovandM. B. Sedelnikova, Ceramic Pigments Based on Natural Minerals, Glass and Ceramics, Volume 59, Numbers 11-12,396-399. 4. V. M. Pogrebenkov, M. B. Sedelnikovaand V. I. Vereshchagin, Zeolites: Raw material for ceramic pigments, Glass and Ceramics, Volume 55, Numbers 1-2,55-56. L 89,32 81,75 77,43 a 0,49 6,38 9,99 b 4,72 16,89 23,6
Hue Light pink Middle pink Pink
569
FUNCTIONAL GRADED HARD METALS PREPARED BY POWDER METALLURGY

Irina CARCEANU*, Emilia Maria COMAN (CIOVICA)** Metallurgical Research Institute of Bucharest, 39 Mehadia Street, code 060543, 6 County, Bucharest Romania, irina_carceanu@yahoo.co.uk, ** VALAHIA University of Targoviste, 2nd Carol I Street, code 130024, Targoviste, Dambovita Romania, emilia_ciovica@yahoo.com
*
Abstract WC-Co cemented carbides are widely used as machining tools, mining tools and wear resistant parts. Multilayer graded structures with Co/Ni content from 10 to 30 wt% from one side of the structure to the other, have been prepared by using either solid-state or liquid - phase sintering. This paper presents briefly the experimental works performed for manufacturing parts from functional graded hard metals with designed structure aiming at the wear resistance increase. Keywords: Functional graded hard metals; Multilayer graded structures; Mining inserts; INTRODUCTION The necessity to improve continuously the working performances of the parts equipping mining tools requires new materials with mechanical properties superior to those of the existent ones, these new materials being obtained as well by changing the chemical composition as the method of material making. The obtaining of materials with designed structure based on sintered hard metals, by using powder metallurgy technologies, which determine changes just during the processing, were considered from the beginning as an attractive alternative to the current manufacturing methods. The advantages of this technology concern both economic aspects and practically unlimited possibilities of using specific methods for pulverous materials processing in order to obtain various functional combinations. EXPERIMENTAL TECHNIQUE In the case of obtaining WC-Co materials with designed structure, a world-wide accepted method presented in the paper consists in creating the property gradient in one stage of the technological stream, i.e. during the stage of powder compaction by an adequate pressing method, followed by liquid phase sintering.[1] Experiments, which are furtheron briefly emphasized, had in view to realize those tungsten and cobalt carbide compositions in optimal alloys, which confer as well resistance to abrasion as to shocks and determine an optimal behaviour of the parts used for percussive rotary drilling under extreme conditions imposed by their efficient using[2]. Taking into account the above mentioned considerations, the selected hard metals systems are the following: WCCo hard metals system (G 20 grade);WC-(Ta, Nb) C - Co hard metals system (K 45 grade). The pressing, binder removal-presintering and sintering operations were the targets of the experimental works, in order to analyse the repeatability of the main technological parameters specific to powder metallurgy, having in view the obtaining of inserts with performant physico-mechanical and structural properties. The standardized profiles of the grades for core bits, G 115 code, are presented in figure 1. The tips of G 115 type equipping the removable heads of the tools for percussive rotary drilling are used for rocks excavation in the underground exploitations.
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Figure 1 The shape of G115 mining inserts RESULTS AND DISCUSSIONS Having in view the above presented, the aim was the creation of this tip type from sintered hard metals with Co structural gradient, the working part of which has to be realised from an alloy, which is harder than the sublayer, but of comparable toughness. After the die manufacturing, the compacts were obtained by cold pressing on an self-acting press with mechanical driving and volume filling. Table 1 presents the pressing characteristics of the double-layer compacts obtained by successive batching of the powder into the die, the batching being calculated so that the upper part should contain the whole working part of the piece and lie minimum 3 mm under the cap boundary line. Table 1. Pressing characteristics of the G 115 tip obtained from a double-layer material Double-layer G 115 grade K 45 / G 20 Upper layer [g] 21,5 Mass Bottom layer [g] 63 Specific Pressure [ daN/cm2 ] 1455
The parts formed by cold pressing at the above mentioned specific pressure were submitted to binder removal-presintering in a periodic electrically heated furnace with Kanthal resistances in reducing flow (hydrogen at 220 l/h) at a temperature of 800 C with two holding levels at 380 C and 450 C of approx. 30 minutes each. The intermediary holding levels of 380 C and 450 C are necessary, because they provide the temperature equalization in the charge mass and paraffin is completely removed before it is decomposed on pieces or furnace walls. After pressing and binder removal-presintering the parts were submitted to sintering in order to obtain the set of properties, required by the working conditions: TRS = min. 2400 N/mm2 and HV 30 = min. 1300. The sintering operation was performed in a BALZERS type vacuum induction furnace showing following operation parameters: sintering temperature: 1370 C; sintering atmosphere: vacuum; the holding time at sintering temperature: 40 min.; total cycle time: 8 h. The obtained density values are presented in table 2. Table 2. Apparent density values determined on the lot parts. Mean values [g/cm3] 14.25 14.21 14.18 Average density [ g/cm3 ] 14.21
Table 3 presents the values of the bending breaking strength determined on sintered specimens with parallelepipedic shape from the heat containing also parts from the testing lot. Table 3. Values of the bending breaking strength determined on sintered specimens. Average values [ N/mm2 ] 2420 2480 2460 Transverse rupture strength [ N/mm2 ] 2454
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In order to emphasise the structural gradient created during the processing, the the cobalt content variation was studied at the interfaces of the double-layer parts, on a cross section, by electron microscopy with an ELECTROSCAN Philips microscope equipped with EDAX system for the quantitative analysis of elements, by passing over the piece from the point 1 to the point 7 and maintaining a x 1250 magnification - figure 2.
Figure 2. EDAX quantitative analysis on K 45 - G 20 system. One used a window of 25 x 20 m size , i.e. with a surface of 500 m2, representative for each analysed zone. Figures 3 and 4 shows the microstructure of the interface zone.
Figure 3-4. Microstructures of the G20/K45 separation interface Murakami etching 2000X
On the basis of performed experimental works it was established and finalized the technology for manufacturing mining inserts of G115 type from materials with structural gradient and thus, the testing lot was obtained. The physico-mechanical and dimensional characteristics of the parts of the testing lot are presented in table 4. Table 4. Physico-mechanical and dimensional characteristics of the G115 parts corresponding to the manufactured testing lot. Average density [ g/cm ] 14.18
3
Transverse rupture strength [ N/mm2 ] 2460
Hardness HV 30 [ N/mm2 ] 12811314
Shrinkage [%] 18,2
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ConclusIons The results of the performed experiments and tests, which are presented shortly in this paper, allowed the following conclusions: The sintered hard metals with structural gradient are obtained on powder metallurgy base, by successive batching in the stage of bilateral pressing, followed by liquid phase sintering, at the end of which the material structure is finalized. The mass transfer phenomena taking place during the liquid phase sintering, which characterizes the WC-Co systems, allowed the obtaining of a Co structural gradient depending on the Co concentrations of the contact layers.[3] One obtained in the pressing stage, by powder successive batching, multi-layer compacts with a stationary Co gradient, the Co content for each layer being the following: - in the upper layer, corresponding to the working cutting part of the insert, the Co content amounts to 15% and in the bottom part 12%. [2] The Co structural gradient finalized in the heat treatment stage, emphasised and quantized by electron microscopy, varies at the end of the sintering stage from the upper part to the bottom from 13,76 to 12,18% Co. [2] The structural gradient determined on one hand a hardness variation, so that in the working zone the hardness was the expected one and the assemble toughness - of minimum 2400 N/mm2. [2] All analysed specimens of the testing lot showed the presence of an admissible remanent porosity, A 01, without free carbon, thus highlighting the fact that heat treatment regimes are adequate and characteristics repeatability is guaranteed. References 1. K. Dreyer, D. Kassel, Functionally Graded Hardmetals and Cermets Preparation, Performance and Production Scale Up, 15-th International Plansee Seminar, Vol 2, Reutte, 2001. 2 C.Coman & others Multilayer hard alloy designed for hard rock dislocation, Matnantech Project C 81, (20012002). 3 C. Colin Processing of composition gradient WC-Co Cermet, 13-th International Plansee Seminar, Vol 1, Reutte, 1993, pag. 522-537.
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Yalandrma ISIL leminin tOZ ENJEKSYON KALIPLAMA METODU LE RETLM Speralamlarn Anma Davranna Etkisi
zgr ZGN*, H. zkan GLSOY**, Ramazan YILMAZ***, Fehim FINDIK**** *Bingl niversitesi, Teknik Bilimler Meslek Yksekokulu, Bingl, Trkiye, oozgun@bingol.edu.tr ** Marmara niversitesi, Teknolojoji Fakltesi, Gztepe, stanbul, 34722, Trkiye ** TBTAK MAM, Malzeme Enstits, Gebze - Kocaeli, 41470, Trkiye, ozkan.gulsoy@mam.gov.tr *** Sakarya niversitesi, Teknik Eitim Fakltesi, Metal Eitimi Blm, Esentepe Kamps, 54187, Sakarya, Trkiye, ryilmaz@sakarya.edu.tr **** International University of Sarajevo, Faculty of Engineering and Natural Sciences Department of Mechanical Engineering, 71000 Sarajevo, Bosnia-Herzegovina, ffindik@ius.edu.ba ZET NI 718 speralam, oda scaklnda sahip olduu yksek mukavemet deerlerini yksek scaklklarda da muhafaza edebilmesinin yannda stn korozyon direncine de sahip olmasndan dolay zellikle havaclk ve otomotiv sektrlerinde yaygn uygulama alan bulmaktadr. Bu almada, NI 718 numuneleri karmak geometrilere sahip paralarn hassas llerde, ince taneli, homojen iyapl ve stn mekanik zelliklere sahip olmasn salayabilen Toz Enjeksiyon Kalplama (TEK) metodu kullanlarak retilmilerdir. Optimum younluk salayan scaklk ve srede retilen paralara yalandrma sl ilemi uygulanmtr. Isl ilemlerin malzemenin anma davranlarna etkisi aratrlmtr. Uygulanan yalandrma ileminin malzemenin anma direncine olumlu etki yapt ve ama deneylerinde uygulanan yk ve kayma hznn artna paralel olarak anma kaybnda iddetli art meydana geldii tespit edilmitir. Anahtar Kelimeler: Toz Enjeksiyon Kalplama (TEK), speralam, NI 718, anma,
The Effect of Aging Treatment On Wear Behavior of pOWDER INJECTION MOLDED Superalloys
ABSTRACT NI 718 superalloys are widely used especially in aerospace and automotive sectors due to having higher strength at both room temperature and elevated temperatures, and also superior corrosion resistance. In this study the samples of NI 718 superalloys were produced by Powder Injection Moulding (PIM) process, which provides fine grained homogeneous microstructure of the materials with the net shape size of complex shaped of the pieces with the superiors mechanical properties. Age treatments were applied on those superalloys produced by using suitable sintering temperature and duration at which optimum density was provided. The effects of age treatments on the wear behaviours were investigated. The aging has positive effectives on the hardness and wear resistance of the materials. On the other hand, the load and sliding speeds has great influences on the wear behaviour of the materials. Wear loses increases by parallel increasing of the loads and sliding speeds applied during wear tests. Key words: Powder Injection Moulding (PIM), superalloy, NI 718, wear 1. GR Bir toz metalurjisi ilemi olmasna ramen geleneksel kalpla presleme ile retilen paralardan daha yksek younluk ve dolaysyla daha stn mekanik zellikler elde edilmesini salayan Toz Enjeksiyon Kalplama (TEK)
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teknolojisi, gerek talal imalat gerekse de dkm yntemlerine nazaran daha karmak ekilli paralarn yksek yzey kalitesine sahip olacak ekilde yksek l hassasiyetiyle retilebilmesine olanak tanmakla kalmaz; bunun yannda ince tane yapsna sahip ve kimyasal bileimi her yerinde homojen olan paralarn ekonomik olarak retilmesini de salar [1]. Yksek scakla dayankl bir alam snf olan speralamlar nikel, nikel-demir veya kobalt esasl olabilmektedirler. Speralamlar hem kriyojenik scaklklarda hem de yksek scaklklarda mukavemet ve yzey kararllnn mkemmel bir kombinasyonunu sergilemektedirler [2]. NI 718 bugn dnyada en ok kullanlan speralamdr [3]. NI 718 kelme ile sertletirilebilen nikeldemir esasl bir speralam olup, iyi korozyon direnci ve yksek mukavemet ile stn kaynak edilebilirlik ve yksek scaklklarda (~650oC) mikroyapsal kararllk gibi zelliklerin belirgin bir kombinasyonuna sahip olmasndan dolay gaz trbinlerinde, roket motorlarnda, uzay aralarnda, nkleer reaktrlerde, pompalarda ve takmlarda yaygn olarak kullanlmaktadr. NI 718de mukavemet artrma mekanizmasn temel olarak kbik veya kresel ekilli nano llerdeki Ni3Al ve lens gibi disk ekilli Ni3Nb keltileri oluturmaktadr [48]. 718 alam ounlukla geleneksel dkm yntemi ile retilmektedir. Fakat elementel segregasyon ve arzu edilmeyen fazlarn olumas byk boyutlu ingotlarn retiminde karlalan ciddi problemlerdir [9]. NI 718 alamndan bu dkm hatalarnn elimine edilmesi zaman alc ve pahal olan bir sre gerektirmektedir [10]. Uygulanan sl ilemlerle malzemelerin daha mukavemetli ve daha yksek anma direncine sahip olmalar umut edilmektedir. Paralara uygulanan sl ilemlerin anma davranlarna etkisi ile sertlik davranlarnn karakterize edilmesi bu tr malzemelerin zelliklerinin gelitirilmesi bakmndan ilgin olacaktr. Bu nedenlerden dolay bu almada gaz atomizasyonu ile retilmi n alaml NI 718 tozlar TEK teknii ile ekillendirilmi ve daha sonra optimum scaklk ve srede sinterlenerek retilmitir. retilen paralara yalandrma sl ilemi uygulanmtr. Bylece uygulanan sl ilemin bu tr malzemelerin sertliine ve anma davranlarna etkisi aratrlmtr. 2. DENEYSEL ALIMALAR Deneylerde Osprey firmas tarafndan gaz atomizasyonu yntemi ile retilmi n alaml NI 718 tozu kullanlm olup bu tozun kimyasal bileimi Tablo 1de verilmitir. Tozun tane boyut dalmnn belirlenmesi amacyla Malvern Mastersizer marka cihazla gerekletirilen analize ait eri ekil 1de, toz eklinin belirlenmesi amacyla ekilmi olan SEM grnts ekil 2de verilmitir. Tablo 2de toza ait baz zellikler gsterilmitir. Tablo 1. Kullanlan NI 718 speralam tozunun kimyasal kompozisyonu % arlk NI 718 Ni 52,300 Cr 18,7 Fe 19,306 Nb 5,0 Mo 3,1 Al 0,33 Ti 0,71 C 0,011 Si 0,29 Mn 0,24
ekil 1. Deneylerde kullanlan NI 718 tozuna ait tane boyut dalm erisi Hacimce % 60 ana toz ve %40 balayc ierecek ekilde tasarlanan besleme stou, NI 718 tozu ile parafin mum, brezilya mumu, polipropilen ve stearik asitten oluan ok bileenli balayc sisteminin zel olarak tasarmlanm bir kartrcda 170oCde ve vakum altnda 30 dk kartrlmasyla oluturulmutur. Oluturulan besleme stou granle edilerek 12,5 MPa basn ve 20 saniye tutma sresi ile standartlara uygun olacak ekilde kalplandktan sonra
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balayc giderme ilemine tabi tutulmulardr. Balayc giderme ilemi 70oCye karlm heptan ierisinde 6 saat bekletilen numunelerin almina altlk stnde ve vakum ortamnda 2oC/dk stma hz ile stlrken 200, 400, 500 ve 600oC scaklklarda 2er saat bekletildikten sonra yine 2oC/dk hzla 900oCye stlp burada bir n sinterlenme meydana gelecek ekilde 1 saat bekletilmesi eklinde tasarlanan sl evrime maruz braklmasyla iki aamada gerekletirilmitir. Ayn zamanda toz paracklarn balayan balaycnn uzaklatrlmas nedeniyle parada ekil kayb meydana gelmemesini salamak amacyla balayc gidermenin termal aamasnda 900oCye klp 1 saat beklemeyle bir n sinterleme salanmtr. Tablo 2. Kullanlan NI 718 speralam tozuna ait baz zellikler zellik retici retim yntemi Toz ekli Vurgu younluu (g/cm3) Teorik younluk (g/cm )
3
NI 718 Osprey Gaz atomizasyonu Kresel 4,9 8,323 4,5 11,9 26,2
Partikl boyutu (m) D10 D50 D90
ekil 2. NI 718 tozuna ait SEM grnts Sinterlenen numunelerin Arimet prensibine gre younluklar llm, NIKON LP 1200 ELIPSE marka optik mikroskop ile grntleri alnm ve Shimadzu (Japan) marka cihaz ile 100 g ykn 10 saniye uygulanmas suretiyle mikrosertlik lmleri gerekletirilmitir. Yaplan bu incelemeler sonucunda en iyi sonucun alnd numuneler, standatlarda bu malzeme iin belirlenmi 980oCde 1 saat bekletme [11] eklinde zeltiye alma ilemi sonrasnda farkl srelerde yalandrlmlardr. Yalandrma ilemi sonrasnda tekrar sertlik lm yaplarak optimum sonucu veren numuneler anma testine tabi tutulmulardr. Anma testleri Pin-on disk yntemiyle yaplmtr. Andrc olarak 62 HRc sertlie sahip 100Cr6 rulman eliinden hazrlanm disk kullanlmtr. Deneyler sinterlenmi durumdaki ve yalandrlm durumdaki numunelerin andrc disk zerinde 10N ve 20Nluk ykler altnda 1 ms1 ve 2ms2 hzlar ile 5000 m kaymas eklinde gerekletirilmitir. 3. SONULAR VE TARTIMA Farkl scaklklarda ve farkl srelerde gerekletirilen sinterleme ilemleri sonucunda en yksek bal younluk deerine (%95,84) 1300oCde 3 saat sren sinterleme ilemiyle ulald grlmtr. Fakat bu sinterleme parametrelerinde numunelerde ksmi ergimeler sonucu ekil kayb olduu gzlenmitir. 1290oCde 3 saat sreyle yaplm olan sinterleme ilemi sonucunda da yaklak olarak ayn bal younluk deeri elde edilmi ve numunelerde ekil kayb olmad grlmtr. 1290oCnin altnda yaplan sinterleme ilemlerinde yeterli younlua ulalamamtr. Bu nedenle yalandrma ilemlerinde ve anma testlerinde kullanlacak olan numuneler 1290oCde 3 saat sre ile sinterlenmilerdir. ekil 3de 1290oCde 3 saat sre ile sinterlenen ve bal younluu %95,81 olan numuneye ait optik grnt verilmitir.
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ekil 3. 1290oCde 3 saat sinterlenen numunenin optik mikroyap grnts. ekil 4te sinterleme sonras farkl tutma sreleriyle gerekletirilen yalandrma sl ilemleri sonras numunelerden llen sertlik deerleri verilmitir. Standartlara uygun olarak 980oCde 1 saat zeltiye alnarak [11] suda soutulan numuneden llen sertlik deeri 227 HV0,1 olmutur. Yalandrma sonucu en iyi sertlik artnn 720oCde 9 saat bekletildikten sonra frndan karlmadan frn scakl 620oCye drlp 8 saat bekleme sonucu suda soutulan numunede 454 HV0,1 olarak elde edildii gzlenmitir. Yalandrma ilemiyle meydana gelen bu sertlik art istenilen kelti fazlarnn olutuunu dndrmektedir. Bu srenin zerinde gerekletirilen yalandrmalar sonucu sertlikte d olmas ar yalanma olduunu dndrmektedir. Elde edilen bu sertlik deeri literatrde [12] bu malzeme iin belirtilen ve takriben 360 Hv sertliine denk gelen 36 HRc sertlik deerinden olduka yksektir. Sertlik deerinin literatrde belirtilen sertlik deerinden olduka yksek olmas toz enjeksiyon kalplama yntemiyle retilmi olan bu malzemelerin ince taneli oluuna balanmaktadr.
ekil 4. 720oCde farkl srelerde bekletildikten sonra 620oCde 8 saat bekletilen numunelerde ulalan sertlik deerleri Yalandrma ileminden nce ve sonra numuneler anma testlerine tabi tutulmutur. 10N ve 20N ykler altnda 5000 m yolu 1ms1 ve 2ms2 hzlarla kayan numunelerde meydana gelen arlk kayplar ekil 5.a ve ekil 5.bde verilmitir. Farkl yk ve hzlarla gerekletirilen anma testleri sonucunda hem sinterlenmi numunelerde hem de yalandrlm numunelerde arlk kaybnn ykten ok hzn artmasyla artt grlmtr. Dier bir ifadeyle bu tr malzemelerin anmasnda hzn uygulanan ykten daha etkili olduu grlmtr. Yalandrlm numunelerde sinterlenmi durumdaki numunelerden daha az anma kayb grlmekte olup, bu durumun yalandrma ilemiyle malzeme iinde meydana gelen kelti fazlarnn salad sertlik artndan kaynakland dnlmektedir.
(a)
(b)
ekil 5. Anma testine tabi tutulan numunelerden, a) 1ms1 hzla, b) 2ms1 hzla kayan numunelerde meydana gelen arlk kayplar (SS-Sinter Sonras, YS-Yalanma Sonras).
577
ekil 6da 10N ve 20N ykler altnda 5000 m yolu 1ms1 ve 2ms2 hzlarla kayan numuneler iin, anan malzeme hacminin yola blnmesi eklinde hesaplanan anma oranlar verilmitir. Anmayla meydana gelen arlk kaybna paralel bir ekilde yalandrlm malzemelerin anma orannn sinterlenmi durumdaki malzemelerden daha dk olduu, bu tr malzemelerde uygulanan yk ve anma hz arttka anma orannn da artt, fakat hzn anma oranndaki etkisinin ykten daha ok olduu grlmtr.
(a)
(b)
ekil 6. Anma testine tabi tutulan numunelerden, a) 1ms1 hzla, b) 2ms1 hzla kayan numunelerde meydana gelen anma oranlar (SS-Sinter Sonras, YS-Yalanma Sonras). Nikel esasl speralamlarn dk termal iletkenliklerinden dolay talal ilem esnasnda takm malzemesi ile temas eden blgede scaklk artnn meydana geldii belirtilmektedir [13]. Anma testleri esnasnda yukardaki aklamaya uygun olarak hem sinterlenmi hem de yalandrlm numunelerde ve andrc diskte scakln ok ykseldii gzlenmitir. ekil 7.ada sinterlenmi durumdaki numunenin 20N yk altnda 2ms1 hzla andrldktan sonra yzeyinden alnan SEM grnts verilmitir. Bu tr malzemelerin pin-on disk yntemiyle andrlmasnda, anma olaynn daha ok adhesiv anma eklinde gerekletii grlmektedir. Ezugwu ve arkadalar tarafndan yaplan bir almada [14], nikel esasl speralamlarn ilenmesinde kesme hznn artna paralel olarak ara yzeyde oluan scakln da artt, takm tala ara yzeyinde ok yksek kesme hz aralklarnda speralamlarn ergime scaklna ulaan scaklklarn meydana geldii bildirilmitir. Ayn almada nikel esasl speralamlarn uzun sre yksek hzl kesme artlarnda ilenmesinin yeni oluturulmu yzeylerin yumuamas ile sonuland ve i paras malzemesinin takma adhezyonu ile birlikte takmda anma olumaya balad belirtilmitir [14]. Benzer durum bu almada elde edilen anma yzeyinin SEM grntsnde de grlmektedir (ekil 7a). Scaklk ykselmesine bal olarak malzemede baz ksmlarn atlad, yumuayan ve zayflayan ksmlarn kopmu olduu gzlenmekte, kopan malzemelerin andrma diskine yapm olduu dnlmektedir. Benzer durum, yaplm baka bir almada yine yksek kesme hzyla ilemede seramik kesici takm zerine Inconel 718 i parasnn yapmas eklinde gzlenmitir [15]. Elde edilen sonu bu almada elde edilen sonularla uyumaktadr. Inconel 718 speralamnn seramik takm ile ilenmesi zerine yaplan bir almada abrasif anma, adhezyon anmas, mikro krlmalar ve talalanma etkin anma mekanizmas ve tipleri olarak grlmtr [16]. ekil 7. bde yalanm numunenin anma sonras grnts verilmi olup, sinterleme sonras andrlan numuneye gre anmaya kar direncin daha fazla olduu grlmektedir.
(a)
(b)
ekil 7. a) Sinter sonras 20N yk altnda 2m/s hzla anan, b) yalanma sonras 10N yk altnda anan numunenin SEM grnts (KY, kayma yn) TEK rn malzemelerin anma davranlarn etkileyen en nemli parametre yap ierisindeki gzenek miktar ve dalmdr. Gzenek miktarnn %7nin altnda olmas durumunda anma kayplar gz nne alnmayacak deerlerdedir ve dikkate alnmaz [17,18]. Gerekletirilen deneysel almalarda ise gzenek miktar %4 seviyesinde olup, sl ilemli ve sl ilemsiz numuneler iin ayn seviyededir. Bu durumda anma kayplarndaki nemli farklarn sadece sl ilem artlarna bal olarak gerekleen sertlik artlar ile dorudan ilikisi vardr. zellikle ekil 7.ada grld zere anma yzeylerinde kayma yn dorultusunda nemli bir delaminasyon grlmektedir. ekil 7.bde ise, sertlik artna bal olarak kayma ynne bal olarak anma yzeylerindeki delaminasyon azalmaktadr [1719].
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4. Sonular Bu almada n alaml NI 718 tozundan TEK metodu ile para retimi yaplm, retilen paralar sl ilem ve anma testlerine maruz braklmlardr. Yaplan deneysel almalardan aadaki sonular karlmtr. 1. Balang tozuna yaplan boyut dalm analizi, tozlarn %50sinin 11,9 m boyutunda olduunu ve TEK iin kullanlmaya uygun aralkta olduunu gstermitir. 2. ok bileenli bir balayc sisteminin kullanlmasyla ekillendirilen paralarn eklini muhafaza edebilmesi bakmndan kullanlabilecek en yksek sinterleme scaklnn 1290oC olduu tespit edilmi, bu scaklkta 3 saat sreyle gerekletirilen sinterleme ilemi sonucunda %95,81 bal younlua ulalmtr. 3. 980oCde 1 saat zeltiye alma sonrasnda gerekletirilen farkl srelerdeki yalandrma ilemelerinde, en yksek sertlik art 720oCde 9 saat+620oCde 8 saat bekleme sreleriyle elde edilmi olup, bu deer 454 HV0,1dir. 4. Hem sinterlenmi durumda hem de yalandrlm durumda 5000 m yolu 10N ve 20N ykler altnda, 1ms1 ve 2ms1 hzlarla kayan numunelerde yk ve hzn artmasyla arlk kayplar ve anma oranlar da artmtr. Bu tr malzemelerde anma kayplar zerinde hzn uygulanan ykten daha etkili olduu grlmtr. 5. Anma deneylerine tabi tutulan numunelerden sinterleme sonras sl ileme tabi tutulan numunelerin olutuu dnlen intermetalik keltilerin salad sertlik artna bal olarak sinterlenmi durumdaki numunelere nazaran anmaya kar daha direnli olduklar tespit edilmitir. TEEKKR NI 718 tozlarnn temini konusundaki desteklerinden dolay Osprey Co. (UK) firmasna teekkr ederiz. KAYNAKLAR 1. R. M. German, Powder Injection Molding, ASM Handbook, Volume 7, Powder Metal Technologies and Applications, sayfa: 843848, 1998. 2. ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys, compiled by J.R. Davis, ASM International, Materials Park, OH., 2000. 3. R. E. Schafrik, D.D.Ward, J.R. Groh, in: E.A. Loria (Ed.), Application of Alloy 718 in GE Aircraft Engines: Past, Present and Next Five Years, Superalloys 718, 625, 706 and Various Derivatives, TMS, sayfa: 111, 2001. 4. D. F. Paulonis, J. M. Oblak, and D. S. Duvall, Precipitation in nickel-base alloy 718, Trans. ASM, cilt: 62, no: 3, sayfa: 611622, 1969. 5. R. Cozar and A. Pineau, Morphology of and precipitates and thermal stability of inconel 718 type alloys, Metallurgical Transactions, cilt: 4, no: 1, sayfa: 4759, 1973. 6. I. Kirman and D. H. Warrington, Precipitation in Nickel-Based Alloys Containing both Niobium and Titanium, Institute of Metals, cilt: 99, sayfa:197- 199, 1971. 7. W. E. Quist, R. Taggart and D. H. Polonis, The Influence of Iron and Aluminium on the precipitation of metastable Ni3Nb Phases in the Ni-Nb System, Metallurgical and Materials Transactions, no:3, cilt: 2, sayfa: 825832, 1971. 8. M. C. Chaturvedi and Ya-fang Han, Strengthening Mechanisms in Inconel 718 Superalloy, Metal Science, cilt: 17, sayfa:145149, 1983. 9. S. T. Wlodek and R. D. Field, Freckles in Cast and Wrought Products, Superalloys 718, 625, 706 and Various Derivatives, ed. E. A. Loria, (TMS, Warrendale, PA), sayfa:167176, 1994. 10. A. R. Braun and J. F. Radavich, Microstructnral and Mechanical Properties Comparison of P/M 718 and P/M TA 718, Superalloy 718 - Metallurgy and Applications (Warrendale PA, E.A.Loria, Metals and Materials Society), sayfa: 623629, 1989. 11. Donald J. Tillack, James M. Manning, and J. R. Hensley, Heat Treating of Nickel and Nickel Alloys, ASM Handbook, Volume 4, Heat Treating, sayfa: 2042, 1991. 12. W.L. Mankins and S. Lamb, Nickel and Nickel Alloys, ASM Handbook, Volume 2, Properties and Selection: Non Ferrous Alloys and Special-Purpose Materials, sayfa: 1387, 1990. 13. D. A. Axinte, P. Andrews, W. Li, N. Gindy and P. J. Withers, Turning of advanced Ni based alloys obtained via powder metallurgy route, Annals of the CIRP, 55/1 2006. 14. E. O. Ezugwu, J. Bonney, Y. Yamane, An overview of the machinability of aeroengine alloys, Journal of Materials Processing Technology, cilt: 134, sayfa: 233253, 2003. 15. A. R. MOTORCU, Nikel Esasl Speralasmlarn ve Titanyum Alamlarnn lenebilirlii, II. Blm: Seramik Kesici Takmlarn Performanslarnn Deerlendirilmesi, Makine Teknolojileri Elektronik Dergisi, cilt: 7, No: 2, sayfa: 117, 2010. 16. L. Li, N. He, M. Wang, Z. G. Wang, High speed cutting of Inconel 718 with coated carbide and ceramic inserts, Journal of Processing Technology, cilt:129, sayfa: 127130, 2002. 17. N. P. Suh, An overview of The Delamination Theory of Wear, Wear, cilt: 44, sayfa: 116, 1997. 18. K.V. Sudhakar, P. Sampathkumaran, E.S. Dwarakadasa, Dry Sliding Wear High Density Fe2%Ni Based P/M Alloy, Wear, cilt: 242, sayfa: 207, 2000. 19. H.O. Gulsoy, Dry Sliding Wear in Injection Molded 174 PH Stainless Steel Powder With Nickel Boride Additions, Wear, cilt: 262, sayfa: 491497, 2007.
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MAGNEZYUMUN LAVESNN Al4Cu TM ALAIMININ YALANMA DAVRANIINA ETKLER

Azim GKE*, Fehim FINDIK**, Ali Osman KURT***
* **
Sakarya niversitesi Teknik Eitim Fakltesi Metal Eitimi Blm,54187, Sakarya, azimg@sakarya.edu.tr Uluslararas Sarajevo niversitesi, Mhendislik ve Fen Bilimleri Fakltesi, Mmakine Mhendislii Blm, 71000, Saraybosna, Bosna-Hersek, ffindik@ius.edu.ba *** Sakarya niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 54187, Sakarya, aokurt@sakarya.edu.tr zet
Bu almada elementel olarak hazrlanm % 4 bakr ieren alminyum alamna farkl oranlarda magnezyum katks yaplm, alamn yapay yalanma davran mikroyap ve sertlik sonularyla incelenmitir. Magnezyum ilavesi Al4Cu toz metal ana malzemesinin yalandrma ile sertlik kazanma kabiliyetini artrmaktadr. Magnezyum ilavesiz numunede sertlikte 6 saatlik yalandrma ile yaklak % 40lk bir art salanrken, ayn numuneye % 0,5 magnezyum ilavesi ile 6 saatlik bir yalandrma sonras sertlik art yaklak % 95 olmaktadr. almada en yksek sertlie (117 HB) % 2 magnezyum ieren alamn 24 saat yapay yalandrlmas sonucu ulalmtr. Anahtar Kelimeler: Al Toz Metal, Mikro Alamlama, Sinterleme, Toz Metal Isl lemleri.
EFFECTS OF THE MAGNESIUM ADDITION ON THE AGING BEHAVIOR OF Al4Cu PM ALLOY

ABSTRACT In this study, various levels of magnesium added into pre-mixed Al4Cu powder metallurgy alloy and aging behavior of the alloy was investigated. The addition of Mg resulted in an increase in age hardening ability of the onto the main Al4Cu PM alloy. The alloy without Mg addition has only 40 % increase in hardness after 6 hours ageing whereas with an 0,5 wt% Mg addition on to the same alloy resulted in an 95 % increase in hardness after 6 hours ageing. In the study, the highest hardness value was obtained with an alloy (Al4Cu2Mg) of 2 % Mg addition after 12 hour ageing. Keywords: Al Powder Metallurgy, Micro-Alloying, Sintering, Powder Metallurgy Heat Treatments. 1. GR Alminyum alamlarnn dk zgl arlk, yksek korozyon direnci, geri dnm gibi zellikleri toz metalurjisi ynteminin avantajlar ile birlemesiyle tozmetal alminyum alamlar son yllarda giderek artan bir oranda endstriyel ve teknolojik rnlerde kullanm alan bulmaktadr. Alminyum tozlarndan retilen alamlar ilenmi alminyum alamlar ile byk oranda benzer bileimdedir. Alminyum tozlarnn sktrlma zellii, genel olarak toz morfolojisine ve boyut dalmna bal olmakla beraber, 350 MPa basn altnda teorik younluunun %90na kadar ulalabilmektedir. Demir esasl tozlara nispeten alminyum tozmetal malzemelerin sinterlenmesi iin ok daha dk scaklklar yeterli olmaktadr. Bu ise zamandan ve enerjiden byk tasarruf salamaktadr [1].
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Alminyumun toz metalurjisinde kullanmndaki byk sorunlardan biri yzey oksididir. Alminyum zerindeki oksidin kalnl ortam scakl, alminyum tozunun retiminde kullanlan sre, sakland ortamdaki nem gibi deikenlere baldr. Oda scaklnda ktle alminyum yzeyindeki oksidin kalnl yaklak 10 20 dur. Atomize alminyum zerindeki oksit kalnl ise 50-150 arasndadr. Alminyum zerindeki oksit genellikle amorf ve emilen su tabakas nedeniyle hidrolize olmu durumdadr. 350 oC zerindeki scaklklarda tavlama srecinde oksit tabakas g-Al2O3 halinde kristalize olur. Oksit tabakas dk ergime dereceli metallerde kat faz sinterlemeyi engelleyici bir faktrdr. Bu yzde alminyum alamlarnn sinterlenmesinde sv faz daha ok tercih edilir bir yntemdir. Baz metallerin alam sistemine katlmas sinterleme srasnda oksit tabakasn elimine edici etki yapabilir. Magnezyum katksnn yzeyde oluan oksit tabakasn krmak sratiyle alminyum alamlarnn sinterlenmesinde olumlu katk yapt bilinmektedir[2,3,4,5]. Sisteme magnezyum katlmas durumunda; oluan reaksiyon aadaki gibidir[6]. 3Mg + 4Al2O3 3MgAl2O4 + 2Al (1)
Scheaffer[6] yapt TEM almalar ve mikroyapsal analizler ile Al 2xxx serisine yaplan Mg katksyla Spinel fazn olutuunu gstermitir. Sinter esnasnda magnezyumun alminyum matris iine nfuz etmektedir Sonrasnda yukardaki reaksiyon sonucu oksit film tabakas zerinde hacimce deiim meydana gelmekte ve bundan dolay oluan kesme gerilmesi oksit tabakasnn krlmasna sebep olmaktadr. Bylelikle yaynm (difzyon), slatma sonucunda sinterlemenin daha iyi olmasn salamaktadr. Dolaysyla, oksit tabakas bir problem olmaktan kmaktadr. Alminyum bakr alamlarnn mukavemetinin artrlmas iin sl ilem uygulanmas pratikte sklkla kullanlan bir yntemdir. Bu yntem zeltiye alma, su verme ve yalandrma olarak basamaktan olumaktadr[7]. Bu almada elementel tozlarla hazrlanm Al4Cu ana alamna eitli miktarlarda (% 0,5 2) magnezyum ilavesinin mikroyapya ve yalandrma sonucunda ana malzemenin sertliine olan etkileri incelenmitir. 2. DENEYSEL ALIMALAR 2.1 Hammadde ve Kompozisyon Hazrlama almada kullanlan tozlarn zellikleri Tablo 1de verilmitir. Tablo 2`de ise almada retilen alamlarn bileimleri grlmektedir. Tablo1. Deneysel almalarda kullanlan tozlarn zellikleri Toz Alminyum Bakr Magnezyum Tedariki Grel Makine A.. Grel Makine A.. Magnezyum Metal A.. Safiyet (%) 99,60 99,60 99,95 ,00 Toz Boyutu ( m) -53 -53 -53
Tablo 2. retilen alamlarn bileimleri Alam Kodu Alam Kodu Al4Cu Al4Cu0.5Mg Al4Cu0.5Mg1Mg Al4Cu0.5Mg2Mg Al 96,00 95,50 95,00 94,00 Alam Elementi (% a.) Cu 4,00 4,00 4,00 4,00 Mg -0,50 1,00 2,00
Alamn bileimine uygun olacak ekilde tozlar 0,0001 gr hassasiyetli Precisa hassas terazide tartlm sonrasnda taban 35 mm apnda 80 mm yksekliinde geni azl silindirik HDPE ielere konmutur. Kartrma ileminin daha etkili olmas asndan 5mm apnda ZrO2 bilyeler kullanl olup, ielerin hacimce 1/3 karm toz, 1/3 ZrO2 bilye ile doldurulmu 1/3lk ksm ise bo braklmtr. Kartrma ilemlerinde Turbula-T2F Mixer kullanlm olup kartrma sresi 3 saat olarak belirlenmitir.
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2.2. ekillendirme lemleri Kompaktlarn retilmesinde 14 Ton kapasiteli manel hidrolik bask cihaz kullanlmtr. Numune retiminde kullanlan basn 400 MPadr. retilen silindirik ham paralarn ap 16 mm ykseklii ise 4 mm olacak ekilde ayarlanmtr. Ham paralarn sinter ncesi younluklar ktlelerinin hesaplanm olan hacimlerine blnmesi ile bulunmutur. Kalp anmasnn engellenmesi iin her bir ekillendirme ilemi ncesi kalp boluu ve kalp zmbalar inko stearat ile yalanmtr. inko stearattn yzeye dalm yksek safiyetli alkol ile gerekletirilmitir. 2.3. Sinterleme lemleri Sinterleme ilemlerinde Honeywell DC2500 kontrol nitesi ile programlanabilen silindirik yatay tp frn kullanmtr. Frnn reaktr tp 316 L paslanmaz elikten zel olarak imal edilmitir. zeltiye alma ilemlerinde de ayn frn ve tp kullanlmtr. Numuneler frna Al2O3 altlklar zerinde yerletirilmitir. Sinterleme ilemlerinde yksek safiyette azot gaz kullanlmtr. Gaz iindeki olas ok dk oksijen safszlnn nne geilmesi amacyla tpten kan gaz frna girmeden nce silika jel ile doldurulmu gaz ykama iesinden geirilmitir. Gaz ak hz sinter esnasnda 1 lt/dk olarak belirlenmitir. Sinterleme scakl 615 C olup bu scakla 15 oC/dk hzla klmtr. Kontrolsz olarak frn ierisinin bu scaklklarn zerine almasn engellemek amal 600 C`nin zerinde frn stma hz 1 oC/dk olarak gerekletirilmitir (ekil 1). oCoCzeltiye alma ve yalandrma scaklklar her 3 grup numune iin de ayndr. zeltiye alma ilemi sonrasnda ar doymu yap elde edilmesi amacyla frndan kartlan numuneler oda scaklndaki su ierisine drlmtr. Isl ilem sreci olarak dkm alminyum alamlarna uygulanan T6 sl ilemine benzer bir sre olan T51 sreci seilmitir (ekil 1). Bu srece gre sinter sonrasnda numuneler oda scaklna dmeden zeltiye alma scaklna kontroll olarak soutulmaktadr. Yalandrma ilemleri Protherm-PFL-130/6 kl frnda yaplm olup yalandrma sresi 6, 12, 24 ve 48 saat olarak seilmitir. 2.4. Sinter Sonras lemler Sinterlenen numunelerin younluklar Arimet Prensibine gre belirlenmitir. Younluk belirleme ilemleri karm hazrlamada kullanlan hassas teraziye balanan younluk lm kiti ile yaplmtr. Younluk lm sonrasnda numuneler hassas kesme cihaz ile ortadan kesilip herhangi bir kontrolsz yalanmann engellenmesi iin souk olarak reineye alnmtr. Mikroyapsal inceleme iin numuneler geleneksel metalografik ilemlerden geirilmi nihai parlatmada 0,3 mlik almina sspansiyon kullanlmtr. Optik mikroskop olarak Clemex Image Analysis yazlm ile senkronize alan Nicon Eclipse L150A metal mikroskobu, elektron mikroskobu olarak Jeol JSM 6060LV taramal elektron mikroskobu kullanlmtr. Sertlik lmlerinde BMS 200 RB sertlik lm cihaz kullanlm olup seilen yk 62,5 kg ve yk uygulama sresi 10 saniyedir. Her bir numuneden 5 lm alnm ortalama deer o numunenin sertlik deeri olarak kabul edilmitir.
ekil 1. Sinterleme almalarnda kullanlan scaklk-zaman grafii.
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3. DENEYSEL SONULAR ve TARTIMA Deneysel almalarda kullanlan tozlarn morfolojik zelliklerinin incelenmesi amacyla ekilmi olan elektron mikroskobu grntleri ekil 2de verilmitir.
ekil 2. Kullanlan tozlarn SEM grntleri a)Al b)Cu c)Mg (. l izgisi a, b ve c iin 100 mdir). ve d iin ise 50 m`dir. l izgisleri daha da belirginletirilecek Literatrde alminyum-bakr alamlarnn sinterlenmesi ile ilgili almalarda sinterlemenin 580-620 oC scaklklar arasnda yapld grlmtr[6,8,9,10]. Sinterleme scaklnn belirlenmesinde bakr oran arttka sinterleme scakl dmektedir. Alminyum bakr denge diyagramna gre (ekil 3) % 4 bakr katks ile tektik sv faza gei scakl yaklak olarak 590 Cdir. Bu scaklk zerinde yaplan sinterleme ilemi sv faz olarak adlandrlr. Oluan tektik sv fazn kapiler basn etkisiyle paracklarn arasn doldurmas ile daha youn bir yap elde edilmesini salar. Daha nce yaplan bir alma[3] magnezyum katks ile birlikte sv faz oluma scaklnn dtn gstermitir. Bu yzden almada kullanlan sinter scakl olan 615 Cde oluan tektik fazn diyagramda belirlenenden daha fazla olduu dnlmektedir. zeltiye alma scakl olan 550 Cde bakrn tamam yapya girerken oda scaklnda alminyum iinde bakrn ok az bir ksm znebilmektedir. Bu durumda ani soutma ile ar doymu bir yap elde edilmektedir.
ekil 3. Al-Cu faz diyagramnn alminyumca zengin ksm. ekil 4de sinterlenmi Al4Cu ve Al4Cu2Mg alamlarna ait mikroyaplar grlmektedir. Magnezyum ilavesi ile birlikte yapda tane bymesi grlrken tane snrlar da magnezyum ilavesiz numuneye gre daha belirgindir. Magnezyum ilavesi ayn zamanda mikroyapda tespit edilebilir belirgin ekilde porozitede arta sebep olmutur (ekil 5). Magnezyumun spinel faz oluturarak alminyum yzeyindeki oksit tabakasn krmas dolaysyla sv faz oluumunu kolaylatrmas ve tane snrlarndaki sv faz miktar artyla beraber daha kaln tane snrlar olutuu dnlmektedir.
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ekil 4. Sinterleme ilemi sonrasnda a)Al4Cu b) Al4Cu2Mg alam.
ekil 5. retilen alamlarn sinter sonras % teorik younluk deerleri. Al4Cu numunesine ait zeltiye alma sonucunda oluan optik mikroyap grnts ekil 6-ada; taramal elektron mikroskobu grnts ise ekil 6-bde verilmitir. ekil 6-a genel yapnn grlmesi amacyla en dk bytmede (50X) ekilirken ekil 6-b keltilerin ve gzenek byklnn daha iyi incelenmesi amacyla yksek bytmede alnmtr. ekil 6-ada verilen numunede makro porozite grlmemektedir.
ekil 6. zeltiye alma ilemi sonucu Al4Cu numunenin a) optik b) SEM grnts ekil 6-bde belirtilen noktalara ait EDS analiz sonular Tablo 3de sunulmutur. Yapda grlen beyaz blgelerin demir ve bakrca zengin blgeler olduu grlmekle beraber zellikle demirce zengin blgeler inemsi yapda keltiler oluturmutur. Al4Cu numunesinin zeltiye alma sonras ekilmi XRD grafiinde (ekil 7) yapda Al-Cu-Fe intermetalik faznn olutuunu tespit edilmitir.
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Tablo 3. ekil 6-bde belirtilen noktalarn EDS analiz sonular. Nokta 1 2 3 4 Al 69,874 95,131 98,836 97,879 Element (% a.) Cu 21,952 4,869 1,164 1,762 Fe 8,174 --0,359
ekil 7. Al4Cu numunenin zeltiye alma sonras XRD grafii. (-Al7Cu2Fe, -Al) Yapda grlen demir tozlarn retim safhasnda ve safszlk olarak gelmektedir. Demir faz iinde znerek Al7Cu2Fe fazn oluturmaktadr. Bu faz mikroyapda inemsi/ubuksu formda yer almaktadr (ekil 6-b). Al4Cu2Mg numunenin zeltiye alma ilemi sonucu mikroyaps ekil 8de verilmitir. Magnezyum ilavesi ile birlikte ilavesiz numuneye oranla en byk fark olarak magnezyumun btn mikroyapda dalmas ve analiz yaplan noktalarda bulunan oksijen dikkat ekmektedir (Tablo 4). Matris olarak ifade edilebilecek 1 numaral nokta da dahil olmak zere analiz yaplan her noktada oksijen bulunmasnn nedeni, yapy oluturan elementlerin oksijene ilgisinin yksek olmasndandr. Bakr ieriinin yksek olduu 3 ve 4 numaral noktalarda demir ieriinin de yksek olmas XRD sonularn (ekil 7) dorular niteliktedir.
ekil 8. Al4Cu2Mg numunenin zeltiye alma ilemi sonucu mikroyap grnts Tablo 4. ekil 8de belirtilen noktalara ait EDS elementel analiz sonular. Nokta 1 2 3 4 Al 84,133 92,121 43,621 43,617 Element (% a.) Cu 1,342 1,366 17,346 17,539 Mg 2,714 1,725 3,440 3,091 O 11,811 4,788 32,280 28,664 Fe --3,311 7,088
Al4Cu2Mg numunesinin 24 saat yalandrma sonucu mikroyap grnts ekil 9da verilmitir. Mikroyap grntlerine gre tane snrlar belirgin olmakla beraber kimi noktalarda ikincil fazn daha belirgin olduu dikkat ekmektedir. zeltiye alma ilemi sonrasnda zeltiye alnamayan Al-Cu-Fe intermetaliinin (ekil 7) mikroyapda
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farkl renkte grnd tespit edilmi olup tane snrlarnda youn olarak biriken bu fazn sertlik zerinde olumlu bir etkisi olsa da mekanik zellikler zerinde olumsuz bir etkisinin olaca dnlmektedir. Bu fazn bakrca zengin blgelerde daha youn bulunduu EDS analizi ile tespit edilmi olup matris olarak ifade edilecek 1 ve 4 numaral noktalarda demir tespit edilmemesi bu faz zeltiye alnamad kantlar niteliktedir.
ekil 9. Al4Cu2Mg numunenin 24 saat yalandrma sonucu grnts. Tablo 5. ekil 9da belirtilen noktalarn EDS analiz sonular Nokta 1 2 3 4 Al 96,667 43,917 96,242 91,216 Cu 1,865 39,113 1,481 1,293 Element (% a.) Mg 1,468 1,976 2,277 1,566 O -11,201 -5,925 Fe -3,792 ---
retilen alamlara ait sertlik deerleri Tablo 6a verilmitir. Sonulara gre en yksek sertlik deeri 24 saat yalandrlan Al4Cu2Mg numunesinde elde edilmitir. % 2 magnezyum ilavesi, alam sertliinde hibir sl ilem olmadan % 50 art salamaktadr. Magnezyumun sinter kolaylatrc etkisi ve yapda ince bir ekilde dalmas bunun balca sebebidir. Ayrca magnezyum katks arttka yalanma iin gerekli sre ksalmtr. Elde edilen sertlik deerleri literatrdeki benzer almalardan daha yksektir[11,12,13]. Tablo 6. retilen alamlarn sertlik deerleri Sertlik (HRB) Alam Al4Cu Al4Cu0.5Mg Al4Cu1Mg Al4Cu2Mg 4. SONULAR zetle bu almada aadaki sonulara ulalmtr. Hammadde olarak kullanlan tozlardan safszlk olarak gelen demir Al-Cu ile birleerek Al7Cu2Fe intermetalii oluturmaktadr ve bu intermetalik zeltiye alma sl ilemi ile yapda zlememektedir. Al-Cu-Mg alamna eklenen mikro dzeyde magnezyum ile sertlikte yaklak %50 art elde edilmitir. Magnezyum ilavesi yalandrma ile sertlik kazanma kabiliyetini artrmaktadr. Magnezyum ilavesiz numunenin sertlii 6 saatlik yalandrma ile yaklak % 40lk bir sertlik art salanrken, ayn numuneye % 0,5 magnezyum ilavesi ile 6 saatlik bir yalandrma ile salanan sertlik art yaklak % 95dir. En yksek sertlik 118,2 HB ile k elde edilebilirkenen yksek sertlik deerine te ulalmtr. en % 2`lik magnezyum katks yaplan numunelerin 24 saat yalandrlmas ile elde edilmitir. Alamlandrma ve sl ilem ile Al4Cu alamnn sertlii % 179 artrlabilmektedir. Silisyum ilavesinin % 1`e karlmas ile en yksek sertlie 6 saatte klabilmektedir. Sinter 42,2 44,0 53,6 62,2 zeltiye alma 50,5 53,8 78,8 97,7 6 saat 59,2 86,2 92,4 111,1 Yapay Yalandrma 12 saat 24 saat 62,3 73,6 81,6 92,4 89,2 105,2 110,5 118,12 48 saat 72,2 94,3 96,6 101,8
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TEEKKR Bu alma Sakarya niversitesi Bilimsel Aratrma Projeleri Komisyonunca desteklenmitir (SA-BAPK 200950-02-020). Yazarlar, tozlarn teminindeki desteinden dolay Grel Makina A.. ve Magnezyum Metale teekkr eder. KAYNAKLAR 1. nternet Sitesi - European Powder Metallurgy Association- http://www.epma.com/New_non_members/structural_parts.htm 2. Lumley, RN., Sercombe, TB., Schaffer, GB., Surface Oxide and the Role of Magnesium During the Sintering of Aluminum, Metallurgical and Materials Transactions A, Vol. 30A, pp. 457-463, 1999. 3. Kondoh, K., Kimura, A.,Watanabe, R., Effect of Mg on Sintering Phenomenon of Aluminium Alloy Powder Particle, Powder Metallurgy, Vol. 44, pp. 161-164, 2001. 4. Gke, A., Fndk, F., Kurt, AO., Microstructural Examination and Properties of Premixed Al-Cu-Mg Powder Metallurgy Alloy, Materials Characterization, Vol. 62, pp. 730-735, 2011. 5. MacAskill, IA., Hexemer Jr, RL., Donaldson, IW., Bishop, DP, Effects of Magnesium, Tin and Nitrogen on the Sintering Response of Aluminum Powder, Journal of Materials Processing Technology, Vol. 210, pp. 22522260, 2010. 6. Schaffer, GB., Sercombe, TB., Lumley, RN.,Liquid Phase Sintering of Aluminium Alloys, Materials Chemistry and Physics,Vol. 67,pp. 8591, 2001. 7. Smith, WF., Mhendislik Alamlarnn Yap ve zellikleri, eviri:Dr.Mehmet Erdoan, Nobel Yaynlar, Ankara, 2001. 8. Kyung, HM., Kang, SP., Lee, BH., Lee, JK., Kim, YD., Liquid Phase Sintering of the Commercial 2xxx Series Al Blended Powder, Journal of Alloys and Compounds, Vol. 419(1-2), pp. 290-293,2006. 9. Hall, BJ., Schaffer, GB., Statistical Experimental Design of Al-Cu-Mg-Si P/M Alloys, Journal of Light Metals, Vol. 2(4),pp. 229-238, 2002. 10. Lefebvre, LP., Thomas, Y.,White, B., Effects of Lubricants and Compacting Pressure on the Processability and Properties of Aluminum P/M Parts, Journal of Light Metals, Vol. 2(4), pp. 239-246, 2002. 11. Kent, D., Schaffer, GB., Drennan, J., Age Hardening of a Sintered Al-Cu-Mg-Si-(Sn) Alloy, Materials Science and Engineering: A, Vol. 405(1-2), pp. 65-73, 2005. 12. Delgado, ML., Ruiz-Navas, EM., Gordo, E., Torralba, JM., Enhancement of Liquid Phase Sintering Through Al-Si Additions to Al-Cu Systems, Journal of Materials Processing Technology, Vol. 162-163, pp. 280-285, 2005. 13. ...c. T Durmus HK., Meric C., Age-hardening Behavior of Powder Metallurgy AA2014 Alloy, Materials and Design, Vol. 28(3), pp. 982-986, 2007.
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TOZ METALURJS YNTEMYLE RETLEN ve MERMER (DOAL TA) KESMEDE KULLANILAN KESC ULARA B4C LAVESNN ETKLERNN NCELENMES
Kerim Emre KSZ *, Mehmet MR *, Yusuf AHN ** Cumhuriyet niversitesi, Metalurji ve Malzeme Mhendislii Blm, 58140, Sivas, Trkiye. Cumhuriyet niversitesi, Metalurji ve Malzeme Mhendislii Blm, 58140, Sivas, Trkiye. ** Gazi niversitesi, Makine Eitimi Blm, Teknik Eitim Fakltesi, Teknikokullar, 06500 Ankara/Trkiye
* *
ZET Kesici takm malzemelerinde beklenen ortak zellikler; anma dayanm, tokluk (en nemli takm malzemesi zelliidir ve anma direnci-tokluk ilikisi takm kalitesini belirler) ve ekonomikliktir. Bu deneysel almada elmas emdirilmi Fe-Co matrisli kompozitler toz metalurjisi yntemiyle scak presleme teknii kullanlarak retilmitir. B4C takviyeli ve takviyesiz 2 farkl kompozisyona (farkl Fe/Co oran) sahip numuneler hazrlanm, 25 MPa basn altnda ve 900 C derece scaklkta sinterlenerek, B4C ve Fe takviyesinin etkisi aratrlmtr. Kompozitlerin mekanik zelliklerinin tespiti iin sertlik lm yaplm ve anma deneyleri de farkl yk artlarnda pim-disk tr anma deneyi cihaz aracl ile yaplmtr. Deneysel sonular; Fe ilavesi ile matrisin sertliinin biraz azaldn gstermitir. Fakat B4C takviye elemannn katlmasyla matrisin sertliinde art grlmtr. Kompozitlerin, (TEM) ve (EDS) teknikleri ile karakterizasyon almalar gerekletirilmitir. Anahtar kelimeler: Toz Metalrjisi, Bor Karbr, Kompozit, Anma. 1. GR Kesici takmlarnn mikro yapsn belirleyen iki ana evre olan matris ile elmas ara yzeyinde sinterleme koullarnda kimyasal bir reaksiyon olumas istenir ve bu reaksiyon, elmasl kesici takmn mrn byk lde belirler [1]. Bu ba reaksiyonun oluumu metal tozlarnn bileimine, parack boyutuna ve dalmna, gaz ortamnn koruyucu etkisine, sinterleme scaklna, suresine ve basncna baldr. Bu ekilde mekanik bir ban yan sra kimyasal bir ba da oluturulmaya allr [2]. Elmasl kesici takmn baarl bir ekilde retilmesindeki en nemli parametrelerinden biri metalurjik slatmayla matrise kuvvetlice balanan elmaslarn, oturma yzeyinden koparak uzaklamaya kar direnli olmasdr. Elmas takmlarda kullanlan matris toz karmlarnn elmaslar salam bir ekilde tutmas gerekir [3]. Kesici takmn mr asndan elmaslar tamamen kaybolmadan veya elmaslarda hasar oluturmadan metalik matris optimum bir hz ile anmaldr. ok kolay bir ekilde anan matris, elmaslarn ar bir ekilde zayflayarak kaybolmasna yol aabilmekte, ok sert bir matris ise yzeydeki elmaslarn bir sure sonra kesme yzeylerini yitirmeleri ve alttan da yeni kesici yzeylerin kmamas neticesinde kesme ileminin kesintiye uramasna neden olabilmektedir. Kesilmesi amalanan doal tan ncelikle sertlii dorultusunda matris bileiminin ayarlanmas gerekmektedir [4]. lkemizin mermer rezervleri asndan zengin bir lke olmas dnldnde mermer lkemiz sanayisi iin nemli bir sektr haline gelmitir. Bu nedenle mermerin ve doal talarn daha kaliteli ve daha ucuz bir ekilde ilenmesi bu sektr asndan olduka nemlidir [56]. Dnyada mermer ve doal talarn kesimi su jeti ve lazer kullanmak suretiyle ve daha birok yntemle yaplrken, lkemizde en yaygn kullanlan yntem dairesel elmas testereler ile kesimdir. Testerenin imalat, testerenin gvdesini tekil eden dairesel elik levhayla beraber kesme ilemini yapan elmas soketlerin imalatndan oluur [7].Yaplan bu deneysel almada toz metalurjisi yntemi ile kesici u retilmesi, retilen kesici ularn mekanik zelliklerinin belirlenmesi, mikro yap kontrol ve endstride uygulanabilirliinin aratrlmas hedeflenmitir.
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2. DENEYSEL ALIMA 2.1 Numune Hazrlama Elmas ve B4C katkl MMCler toz metalurjisi yntemi kullanlarak metal tozlarnn belirli oranlarda kartrlmas ile retilmitir. Matris dizaynnda elmaslar bir arada tutan bir balant evresinden ve sinterleme koullarnda gzenekleri kapatmaya yarayan ve kesme koullarnda hzla anarak tala akma kanallarn oluturan bir dolgu evresinden yararlanlr. Balant evresi iin iyi slatan kobalt ve nikel veya ucuz olmas nedeniyle demir gibi elementler ve bu elementlerin kombinasyonlarndan faydalanlr [8-9]. Dolgu evresi iin genelde sinterleme koullarnda ergiyen bronz veya pirin kullanlr. Doal ta iin standart matris dizayn Co, Ni ve Cu-Sn tozlar zerinden yaplmaktadr. Co ve Ni tozlar -iyi slatma zellikleri dorultusunda- elmas balayc evre olarak kullanlmaktadr. Cu-Sn katks hem Cu ve Sn tozlarnn karm halinde veya saf bronz tozu halinde olabilmektedir [8]. Yaplan bu almada, 40/+50 mesh elmas tozlar, 75 mden kk karbonil demir tozu, 85/15 mesh bronz tozu ve 10 mden kk B4C tozu kullanlmtr. retilen kompozitlerin matris kompozisyonu, elmas konsantrasyon deeri ve B4C miktarlar Tablo 1de verilmitir. Tablo 1. retilen Kompozitlerin zellikleri. Kompozit Kodlamalar C2 C4 C2-B4C C4-B4C Fe 65 45 65 45 Matris Kompozisyonu, a. % Co 25 45 25 45 Bronz 10 10 10 10 Elmas Konsantrasyonu 20 konsantrasyon 20 konsantrasyon 20 konsantrasyon 20 konsantrasyon B4C (g) 0,15 0,15
B4C ilaveli kompozitler
B4C ilaveli ve ilavesiz kompozitler 2 farkl kompozisyonlarda 24 x 10 x 10 mm boyutlarnda (farkl Fe/Co oran) retilmitir. LS4750 kodlu endstriyel elmas tozu her bir sokette 20 konsantrasyon olacak ekilde kullanlmtr. (4,4 konsantrasyon/cm3 younluundaki elmas tozlar 100 konsantrasyon olarak ifade edilir). Fe - (2545) a. % Co, elmas ve B4C tozlar (bor karbrsz) 2 farkl grup olarak kartrma ilemine tabi tutulmutur. Kartrma ilemi 45 derece eimli Turbula Mixer kartrc ile 45 dakika yaplmtr. Tozlarn karmasn kolaylatrmak amacyla, karmn homojen olmas ve akkanln ideal biimde olmas iin % 2 glialkol (C2H5OH) (% 25 gliserin + % 75 alkol) eklenmitir. Homojen bir ekilde kartrlan metal tozlar nceden hazrlanm grafit kalplara tartlarak yerletirilmitir. Grafit kalplara koyulan tozlar yksek akm sayesinde, grafitte oluan snn etkisiyle scak presleme yntemiyle 900 Cde azot kontroll atmosfer altnda sinterlenmitir. (Dr. Fritsch DSP 510 scak sinterleme presi). Kompozit numuneler 25 MPa basn altnda sinterleme scakl olan 900 Cye stllarak sinterlenmitir. ekil 1 uygulanan sinterleme rejim grafiini gstermektedir.
ekil 1. Kompozit numunelere uygulanan sinterleme rejim grafii. 2.2 Mekanik Testler retilen her bir kompozit malzeme iin 5 ayr noktadan 100 kgf kuvvet altnda Brinell sertlik deerleri llm ve ortalama sertlik deerleri belirlenmitir. Elmas katkl soketlerin anma deneyleri pim-disk tr cihaz ile kuru ortamda gerekletirilmitir. Numuneler, disk yzeyine dik bir biimde cihaza monte edilmitir. Abrasiv anma deneylerinde numuneler ilk nce talama makinesinde apaklarndan arndrlm ve temizlenmitir. Daha sonra abrasiv anma deneyleri tane boyut aral 8874 mikron olan 180 numara silisyum karbr zmpara kullanlarak yaplmtr. Anma
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deneyleri; 8, 16 ve 24 N yk altnda 48 m kayma mesafesinde, 1 m/s sabit hzda, oda scaklnda gerekletirilmitir. retilen kompozit numuneler anma miktarlar; 0,0001 gr lme hassasiyetine sahip hassas bir teraziyle, deney ncesi llen arlklarndan deney sonras tespit edilen arlklarnn karlmas ile bulunmutur. 3. SONULAR VE TARTIMA 3.1 Sertlik Doal ta kesimleri iin sertlik elmas emdirilmi kompozit malzemelerin kalitesini belirlemek iin en sk kullanlan parametrelerdendir. Bu sebeple sertlik testleri sinterlenmi kompozit malzemelere uygulanmtr. Tablo 2de kompozit numuneler iin llen Brinell sertlik deerleri gsterilmitir. Deneysel sonular; Fe ilavesi ile matris sertliinin azaldn gstermitir. Fakat B4C takviye elemannn katlmas matrisin sertliini artrmtr. Maksimum sertlik deeri B4C ilaveli ve ilavesi C4 kompozisyonuna sahip numunelerde llmtr. Bu sonular Co-Fe metalleri arasnda kat ergimenin gerekletiini ve bununda sertlik artna neden olduunu gstermektedir [810]. Tablo 2. retilen Kompozitlerin Sertlik (HBN) Deerleri Kompozitler C2 65wt%Fe+25wt%Co+10wt%bronze, 20 konsantrasyon C4 - 45wt%Fe+45wt%Co+10wt%bronze, 20 konsantrasyon C2-B4C -65wt%Fe+25wt%Co+10wt%bronze, 20 konsant, 0.15 g B4C C4-B4C - 45wt%Fe+45wt%Co+10wt%bronze, 20 konsant, 0.15 g B4C HBN (ort.) 90 93 97 99
3.2 Anma Testi Scak presleme teknii ile retilen B4C katkl ve katksz kompozit malzemelerin anma testi sonunda anma kayplar ekil 2de gsterilmitir. B4C katksz kompozit numuneler iin ilk tespit edilen, her bir numune iin uygulanan yk arttka anma kaybnn arttdr. kinci olarak tespit edilen kompozitlerdeki Fe miktar artka anma kaybnn arttdr. 24 N yk uygulandnda C4 kompozisyonuna sahip numunedeki anma miktar 0,01535 gramdr. Bu deer 1,27 kat C2 kompozisyonuna sahip numunedekinden daha azdr. Benzer tespitler B4C katkl kompozit numuneler iinde tespit edilmitir. Sonuta B4C katksz kompozit numunelerde dier B4C katkl tm kompozit numunelere gre daha fazla anma kayb olduu gzlemlenmitir. B4C malzemesi yksek sertliinden tr retilen kompozit malzemelerin anma direncine arttrma ynnde katk salamtr.
ekil 2. Anma testi sonundaki anma kayplar. 3.3 Mikro yap Optik mikroskop kullanlarak retilen kompozitlerin mikro yaplar belirlenmitir. Zmparalama ve parlatma ilemlerine tabi tutulan kompozit numuneler daha sonra amonyum perslfat ( 10 g (NH4)2S2O3 + 90 ml damtk su ) zeltisi ile dalanmtr. ekil 3a matrisin mikro yapsn gstermektedir. B4Cnin mikro yaps B4C konsantrasyonu ok az miktarda ve parack boyutu ok kk (<10 m) olduundan tr mikroskop altnda net bir ekilde seilememektedir. Fakat yaplan EDS analizlerinde boronun pik yapt tespit edilmitir. ekil 3b C4-B4C kompozit numunesinin EDS analizini gstermektedir.
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(a) (b) ekil 3. (a) Kompozit numunelerin mikro yaps C4-B4C (400X). (b) Kompozit numunelerin EDX analizi C4-B4C. 4. SONULAR Yaplan bu deneysel almada Co matriksli kompozitlere Fe ve B4C ilavesinin etkileri aratrlmtr. Elmas emdirilmi Fe-Co matriks kompozitler (soket ) scak presleme teknii kullanlarak toz metalurjisi ile retilmitir. C4 ve C4-B4C tip kompozitler kesilecek olan doal tanda zelliine de bal olarak ta kesiminde kullanlabilir.. retilen kompozitlere, Fe ilavesinin matriksteki sertlii drd fakat B4C ile glendirilmi kompozitlerin sertliinin dierlerine gre artt grlmtr. B4C ilaveli Fe-Co matriks kompozitlerin anma kayplarnn ilavesizlere daha az olduu gzlemlenmitir. KAYNAKLAR 1. Karagoz, S., Zeren, M., Characterisation of Hot Pressing Behaviour of Diamond Cutting Tools, Int. PM Conf., Granada-spanya, 4, 208-212, 1998. 2. Karagoz S, Zeren M.,The Property Optimization of Diamond Cutting Tools with the Help of Microstructural Characterisation, 3rd European Conference on Advances in Hard Materials Production, EUROPM, Turintalya, 399-405,1999. 3. Bailey M.W. and Bullen G.J., The de Beers sda Series of Diamond Abrasives and its Stability for the Stone Industry, Eskenazi Semineri, 1-33, stanbul, 1987. 4. Karagoz S, Zeren M.,Srekli Disk Tipi Elmasl Kesici Takmlarda HataKarakterizasyonu, 9. Uluslararas Metalurji ve Malzeme Konf. Bildiriler Kitab, T.M.M.O.B. stanbul, 517-525, 1997. 5. Gray, A.E., Elmas Soketlerin Toz Metalurjisi ile retiminde Kobalt-Bronz Orannn Soket zelliklerine Etkisinin ncelenmesi, Yksek Lisans Tezi, Dumlupnar niversitesi F.B.E., 2005. 6. Karagz, ., Zeren., M., Doal Ta Kesiminde Kullanlan Elmas Kesici Takmlarn Anma Karakteristii, Uluslararas Katlml 4. Ulusal Toz Metalurjisi Konferans, Dzenleyen: Trk Toz Metalurjisi Dernei, Ankara, 2002. 7. Zeren, M., Elmas Kesici Takmlarda Mikroyapsal Karakterizasyon zerinden zelliklerin Optimizasyonu, Doktora Tezi, Kocaeli niversitesi F.B.E., 2005. 8. Ucun , Aslantas K, Byksag S, Tagetiren S, An Investigation on the Effect of Diamond Concentration and Matrix Material Composition in the Circular Sawing Process of Granites, Proceedings of the Institution of Mechanical Engineers, Part C : Journal of Mechanical Engineering Science,1,1-11, 2010. 9. Barbosa, A., Bobrovnitchii, G., Skury, A., Guimaraes, R., Filgueira, M., Structure, Microstructure and Mechanical Properties of PM Fe-Cu-Co Alloys, Materials and Design, 31,522-526,2010. 10. imir, M., ksz, K.E., ahin, Y., Investigation of the Wear behavior of B4C Reinforced Fe/Co Matrix Composites Produced by Hot Pres, International Conference on the Mechanical Behavior of Materials, Como Lake, Italy, 5-9 June, 2011.
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Mo, Ni ve Cu KATKILI Fe ESASLI T/M ALAIMINDA AINMA DRENCN ETKLEYEN PARAMETRELERN DENEYSEL VE STATSTKSEL YNTEMLERLE NCELENMES
Serkan ZEL*, Nusret BOZKURT** ve lyas SOMUNKIRAN*** *Bitlis Eren niversitesi, Mhendislik ve Mimarlk Fakltesi, Makina Mhendislii Blm, 13000, Bitlis, sozel@beu.edu.tr **Bitlis Eren niversitesi, Mhendislik ve Mimarlk Fakltesi, naat Mhendislii Blm, 13000, Bitlis, nbozkurt@beu.edu.tr ***Frat niversitesi, Teknik Eitim Fakltesi, Metal Eitimi Blm, 23119, Elaz, ilyass@firat.edu.tr
ZET Bu almada, Toz Metalurjisi (T/M) yntemiyle retilen Mo, Ni ve Cu katkl Fe esasl toz alam zerinde anma deneyi uygulanm ve anma direncine etkili olan deneysel parametreler Taguchi yntemi kullanarak incelenmitir. Argon gaz atmosferinde Fe esasl toz alam preslemeden sonra 30 dk sre ile 1000, 1050, 1100, 1150 ve 1200 o C gibi farkl scaklklarda sinterlenmitir. Farkl sinterleme scaklklarna sahip numuneler 20 N yk altnda adhasif anma deneyine tabi tutulmutur. almada L25 (52) Taguchi ortogonal dizi ile deney tasarm gerekletirilmitir. Deneysel parametrelerin (sinterleme scakl, kayma mesafesi) anma direnci zerindeki nem seviyesini belirleyebilmek iin istatistiksel metotlardan ANOVA ve F-test uygulanmtr. statistiksel analiz sonular deneysel alma sonularn destekleyerek, Fe esasl toz alamnda artan sinterleme scaklnn anma direncini arttrd belirlenmitir. Anahtar kelimeler: T/M, Sinterleme, Anma, Taguchi, ANOVA.
THE INVESTIGATION WITH EXPERIMENTAL AND STATISTICAL METHODS OF PARAMETERS AFFECTING WEAR RESISTANCE OF Fe BASED P/M ALLOY ADDED Mo, Ni ve Cu
ABSTRACT In this study, wear test was carried out on dust alloy based Fe containing Mo, Ni and Cu additives produced with Powder Metallurgy (P/M) method, and experimental parameters affecting on wear resistance were investigated using Taguchi method. In the argon gas atmosphere, Fe based dust alloy was sintered in different temperatures of 1000, 1050, 1100, 1150 and 1200C with duration of 30 mins after pressed. The samples having different sintering temperatures were subjected to adhesive wear tests under 20 N load. In the study, experimental design is made up with L25 (52) of Taguchi orthogonal series. ANOVA and F-test of the statistical analysis methods were used in order to determine the importance level of the experimental study parameters (sintering temperature and wear distance) on wear. Statistical analysis results supported the experimental study data and showed that the abrasion resistance increased with the increasing of the sintering temperature in the powder alloy including Fe. Keywords: P/M, Sintering, Wear, Taguchi, ANOVA.
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1. GR Toz Metalurjisi (T/M) yntemi, hassas metal paralarnn retiminde kullanlan ok gelimi bir yntemdir. Bu yntemin temel admlar, elementel tozlarn kartrlmas, sktrlmas ve sktrma sonras toz partikllerinin birlemesi iin sinterleme ileminin uygulanmasdr. Gnmzde T/M yntemiyle para retimi ok yaygn olarak kullanlmakta ve giderek bilinen retim yntemlerine alternatif olmaktadr. leri bir imalat yntemi olan T/M, teknolojik malzemelerin retilmesine ok uygun, kk paralarn ok sayda ve ekonomik retimini salayan bir yntemdir. Toz metalurjisinin amac, metal ve metal alamlarn tozlarn ergitmeden, basn ve scaklk yardmyla, dayankl cisimler haline getirmektir. Sinterleme ise ergitmenin yerini tutmakta ve kullanlan metal tozunun ergitme scaklnn altndaki bir scaklkta yaplan bir sl ilemdir [1, 2, 3]. T/M yntemi, otomotiv endstrisinde kullanlan zellikle yapsal paralar, dili, piston, balant ubuklar gibi ar para uygulamalarnda nemli rol oynamaktadr. Son yllarda, T/M elik paralara retim maliyetinin azalmas nedeniyle talep artmtr. Buna bal olarak, otomotiv endstrilerinde kullanlan byk paralar, toz metalurjisi ile retilmektedir [4] Toz metalurjisi yntemi kullanlarak retilen demir esasl molibden, nikel, bakr ve karbon ilaveli toz alamlar yksek mukavemet ve tokluk salanmas amacyla gelitirilmitir. Demir esasl toz metal malzemeler yksek anma dayanml motor ve anzman sisteminde, otomotiv endstrisinde geni uygulama alan bulmutur [5, 6]. Fe esasl toz alamlarnda, Mo ilavesi kat zelti yaparak mukavemeti, dolaysyla bu alamlarda sertleebilirlii arttrmaktadr. Dier yandan Mo elementi, karbon elementi ierisinde zndnde, malzemenin sertleebilirliini arttrmaktadr. Ayn zamanda Ni elementi ile birlikte bulunduunda anma dayanmn da arttrmaktadr [7]. T/M ile retilen elik malzemelerin sinterlenmesinde sv faz ve sertlik arttrc olarak Cu tozu ilave edilmektedir. % 1-2 bakr ilaveli alamlar byk boyuttaki paralarn retiminde kullanlr. Ni ilavesi ile bakrn oluturduu boyutsal deimeleri azaltlabilmektedir. % 2,5 Ni tozu ilavesi ise ekme dayanm artrmaktadr [8]. Mhendislik bilimlerinde deneysel alma sonularnn istatistiksel metotlarla analizinin yaplarak doruluunun teyit edilmesi ya da sonularn optimize edilmesi almalar yaygn olarak yaplmaktadr. Sakarya ve Glolu [9] almalarnda, Taguchi yntemini kullanarak cep ilemede kullanlan takm yolu hareketlerinin ve kesme parametrelerinin yzey przll zerindeki etkilerini aratrmlardr. Tosun ve Cogun [10], kablo kaplama zerine yaptklar almada istatistiksel metodlardan ANOVAy kullanmlardr. Bozkurt ve Yazcolu [11], hafif beton tasarm zerine yaptklar almada kullanlan katk tipinin ve uygulanan farkl kr srelerinin beton zellikleri zerindeki etkilerini deneysel ve istatistiksel yntemler ile aratrmlardr. Bu almada, T/M yntemiyle retilen Mo, Ni ve Cu katkl Fe esasl toz alamna farkl sinterleme scaklklar uygulanm ve elde edilen numunelere anma deneyi yaplarak anma direncine etkili olan deneysel parametreler Taguchi yntemi ile incelenmitir.
2. DENEYSEL ALIMALAR Bu almada kullanlan Fe esasl Mo, Ni, Cu toz alam, toz atomizasyon yntemiyle retilmitir. Tablo 1de bu toz alamna ait kimyasal analiz sonular grlmektedir. Tablo 1. Fe esasl Mo, Ni, Cu toz alamnn kimyasal analizi Mo Ni Cu C Fe % 0.50 % 4.04 % 1.50 % 0.01 Kalan Fe esasl Mo, Ni, Cu toz alam, 600 MPa basn altnda tek eksenli preste basma kuvveti ile preslenmitir. Preslenen numuneler argon gaz ortamnda 1000 oC, 1050 oC, 1100 oC, 1150 oC ve 1200 oC scaklklarda 30 dakikalk srelerde sinterlenmitir. Mikroyap incelemeleri iin numunelerin yzeyleri metalografik numune hazrlama aamalarndan geirilmitir. Numunelere uygulanan block on ring tip adhesif anma deneyi, andc olarak 32 mm apndaki yzeyi honlanm AISI 9840 elii kullanlarak, 20Nluk ykte, 100-500 m. kayma mesafesinde, 0,15 m/ sn kayma hznda farkl srelerde gerekletirilmitir. Anma miktarlar tespitinde, anma ncesi ve sonras 10-5 gr. arla duyarl Scaltec marka elektronik terazi kullanlarak, ktle kayb belirlenmitir. 2.1. statistiksel Analiz Bu almada, deney parametrelerinin sonular zerindeki nem derecelerini istatistiksel olarak grebilmek iin L25 (52) Taguchi ortogonal dizi tasarm kullanlm ve ANOVA ile F-test metotlar uygulanmtr. Hesaplanan F deeri-
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nin byk olmas deney parametrelerindeki deikenliin performans karakteristikleri zerinde byk bir deiime neden olduu anlamna gelmektedir [10, 12, 13]. ANOVA metodunda deneysel deerler ile arzu edilen deerler arasndaki sapmay hesaplayabilmek iin bir kayp fonksiyon kullanlmtr. Bu kayp fonksiyon daha sonra bir sinyal-grlt (S/G) oranna dntrlmtr. Karakteristik tipine bal olarak retilen farkl sinyal-grlt oranlar vardr [13]. Toz alamnn yksek performansa sahip olmas, mekanik ve fiziksel baz karakteristik zelliklerinin yksek olmas ile belirlenebilir. Bu almada fiziksel anlamda daha az anma kayb daha iyi karakteristie sahip malzemeyi iaret ettii iin Daha Kk Daha yidir (Smaller is Better:SB) kayp fonksiyonu kullanlmtr. Bu kayp fonksiyona ve sinyal-grlt oranna ilikin formller aada verilmitir: S/Gij=-10log (Lij) (1) (2)
Burada Lij, j.deneydeki i. performans karakteristiinin kayp fonksiyonu ve S/G ise sinyal-grlt orandr. n denemedeki testlerin saysn, y ise k. test j. denemedeki i. performans karakteristiinin deneysel deerini ifade etmektedir. Sinyal-grlt oranlarnn hesaplanmas iin kullanlan deney kontrol parametreleri ve bunlara ilikin seviyeler Tablo 2de verilmitir. Tablo 2. Kontrol faktrleri ve seviyeleri Scaklk (C) Kayma Mesafesi (m) 3. SONULAR VE TARTIMA Presleme sonras farkl scaklklarda sinterleme ilemine tabi tutulan numunelerin ekil 1de verilen SEM fotoraflar incelendiinde, bakrn ergime derecesine bal olarak 1000 oC scaklkta sv faz sinterlemesinin meydana gelmedii, artan scaklkla beraber (1150 oC ve 1200 oC) numune iin gerekli olan sv faz sinterlemenin gerekletii grlmektedir. Bakr sv faza geerek tane snrlarna doru ilerlemitir. Seviye 1 1000 100 Seviye 2 1050 200 Seviye 3 1100 300 Seviye 4 1150 400 Seviye 5 1200 500
(a)
(b)
(c)
(d)
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(e) ekil 1. Farkl sinterleme scaklklar sonras numunelerin SEM mikroyap resimleri a)1000 oC b) 1050 oC c) 1100 oC d) 1150 oC e)1200 oC 3.1. Deneysel Anma Deerlerinin rdelenmesi 20 N yk altnda yaplan anma deneyi sonucunda elde edilen deerler ekil 2deki grafikte verilmitir. Grafik incelendiinde en fazla anma kaybnn, en az sinterleme scaklna sahip numunede gerekletii grlmektedir. Anma miktar sinterleme scaklnn artmas ile dmtr. Sv faz sinterlemesinin gerekletii 1150 ve 1200 oC sinterleme scaklna sahip numunelerde anma miktar dmtr. Sv fazn olumas ile eriyen bakrn taneler arasnda sv faz oluturmas, Cun balayclk grevi grmesi ve tane ilerine doru difzyonu ile taneler aras ba glendirmesiyle, yksek performansta para retimi salanabilmektedir.
ekil 2. Farkl scaklklarda sinterlenen numunelerin 20N yk altndaki arlk kayb-mesafe ilikisini veren anma grafii.
(a) (b) ekil 3. a)1000 oC scaklkta sinterlenen, b) 1200 oC scaklkta 30 dk. srede sinterlenen numunelerin anma yzey fotoraflar. Anma yzey fotoraflarna bakldnda (ekil 3-a) 1000 oCde sinterlenen numunenin anma izlerinin derin olduu grlmektedir. ekil 3-bde grlen ve 1200 oC scaklkta sinterlenen numuneye ait anma yzey fotorafnda ise anma izlerini 1000 oCdeki numuneye gre daha az derinlie sahip olduu grlmektedir. Buda bize anma grafiinde verilen en az anma deerinin 1200 oCdeki numuneye ait olduunu desteklemektedir.
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3.2. statistiksel Sonularn rdelenmesi Blm 2de belirtilen deney kontrol parametreleri iin hesaplanan S/G oranlar Tablo 3de verilmitir. Bu tabloda deney parametrelerinin etkisinde sonular maksimum yapan seviyeler iaretlenmitir. Ayrca sonularn daha iyi yorumlanmas iin bu deerler kullanlarak ekil 4te toz alamnn anma kayb zelliine ilikin etki grafii verilmitir. S/G oranlar temel alnarak oluturulan ekil 4 ve varyans analizi tablosundan (Tablo 4) toz alamnn karakteristik zelliklerinin farkl sinterlenme scaklklarndan ve kat edilen kayma mesafelerinden etkilenmi olduu istatistiksel olarak ortaya konularak deneysel alma bulgular dorulanmtr. Kat edilen kayma mesafesinin art (100 mden 500 mye artmas) ile anma kaybnda art grlmesi beklenen bir sonutur. Bunun yannda bu istatistiksel alma ile sinterlenme scakllnda farklln olmas, anma kaybnda deney sonularn etkileyen nemli bir deiken parametre olduu ortaya konulmutur. ANOVA tablosu incelendiinde sinterlenme scaklnn farkllk gstermesi ile bu etkinin toz alamnn karakteristik zellii zerinde kayma mesafesi kadar olmasa da neme sahip olduu grlr. Tablo 3. Faktr seviyelerinin S/G oranlar Anma Kayb Seviye 1 Seviye 2 Seviye 3 Seviye 4 41,57 43,00 45,58 46,24 57,92* 45,58 41,39 39,98 *Deney sonularn maksimum yapan seviyeler Seviye 5 47,72* 39,25
Scaklk Mesafe
Kontrol parametreleri ve seviyeleri ekil 4. Anma kayb iin deneysel parametrelerin S/G oran grafii. ekil 4 incelendiinde, scakln artmas ile eimin artt, mesafenin artmas ile ise eimin azald grlmektedir. Hesaplanan S/G oran deerlerine gre oluturulan bu etki grafii, sinterlenme scaklnn artmas ile toz alamnn bir karakteristik zellii olan anma kaybnda minimizasyonun; kat edilen mesafenin artmas ile bu karakteristik zellikte maksimizasyonun (anma kayb artnn) olduunu ortaya koymaktadr. Tablo 4. Anma kayb iin varyans analizi (ANOVA) tablosu Kontrol Faktr Scaklk Kayma Mesafesi Hata Toplam Serbestlik Derecesi 4 4 16 24 Kareler Toplam 127 1191 125 1443 Varyans 31,2 297,8 F 3,9 37,6 P 0,021 0,000 -
Tablo 4 varyans analizi sonularn ve buna bal olarak hesaplanan F-test ve P-deeri (nem-anlamllk deeri) sonularn gstermektedir. Anma deneylerinde kayma mesafesinin arlk kaybna olan etkisi bilinmektedir. Anma kayb zerinde deney parametrelerinden kayma mesafenin, 297.8 varyans deeri, 37.6 F-test deeri ve 0 P-deeri ile en byk etkiye sahip olduu istatistiksel analiz sonucunda da ortaya koyulmutur. Scaklk parametresinin ise varyans analizi deeri ve F-test deerinin zerinde anlaml bir etkiye sahip olduu P-deerinin 0.5 limitinden dk olmas sonucundan anlalmaktadr.
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4. SONULAR - Farkl sinterleme scaklklarna sahip numunelerin mikroyaplarnda deiiklikler gzlenmitir. - 1150 oC ve 1200 oC scaklklarda sinterlenen numunelerde sv faz sinterlenmesi gereklemitir. - Anma miktar en fazla 1000 oCde sinterlenen numunede, ez az anma miktar ise 1200 oCde sinterlenen numunede gereklemitir. - Deneysel alma sonular ile istatistiksel alma sonular birbirini destekler nitelikte elde edilmitir. - statistiksel alma sonucunda kayma mesafesinin artmas ile anma kaybnn artt, sinterlenme scaklnn arttrlmas ile anma kaybnda azalma olduu grlmtr. KAYNAKLAR 1. Narayanasamy R., Ramesh T., Pandey K.S., Workability studies on cold upsetting of AlAl2O3 composite material, Materials and Design, Vol. 27, 7, pp. 566-575, 2006. 2. Ouz ., ztrk Z., Uzun E., Kurt A., Boz M., Gaz Atomizasyonu Yntemi le Kalay Tozu retiminde Gaz Basncnn Toz Boyutu ve ekline Etkisi, 6th International Advanced Technologies Symposium (IATS11), s. 565-568, Elaz, 2011. 3. Somunkran ., Baln A., Scak Presleme Tekniiyle retilen Co Esasl Co-Cr-Mo Toz Alamnda Presleme Scaklnn Mikroyap zerine Etkisi, 6th International Advanced Technologies Symposium (IATS11), s. 223-228, Elaz, 2011. 4. H.Khorsand, S.M.Habibi, H.Y oozbashizadea, K.Janghorban, S.M.S.Reihani, H.Rahmani Serajib, M.Ashtari, The role of heat treatment on wear behavior of powder metallurgy low alloy steels, Materials and Design, Vol. 23, pp. 667670, 2002. 5. Somunkran ., zel S., Fe Esas Toz Alamnda Sinterleme Scaklnn Anma Direncine Etkisi, 10. Uluslararas Malzeme Sempozyumu, s. 153-157, Denizli, 2006. 6. Fujiki A., Present State and Futureprospects of Powder Metallurgy Parts For Automotive Applications, Materials Chemistry and Physics, Vol. 67, pp. 298-306, 2001. 7. zgn ., Toz Metalurjisi le retilen Alaml eliklerin Mikroyapi ve Mekanik zellikleri, Sakarya niversitesi Fen Bilimleri Enstits, Yksek Lisans Tezi, 2007. 8. Salak A., Ferrous Powder Metallurgy, ISBN:1898326O37, Cambridge International Science Publishing, England, 1995. 9. Sakarya N. ve Glolu C., Taguchi Yntemi ile Cep lemede Kullanlan Takm Yolu Hareketlerinin ve Kesme Parametrelerinin Yzey Przllne Etkilerinin Belirlenmesi, Gazi niv. Mh. Mim. Fak. Der., 21, 4, s. 603-611, 2005. 10. Tosun N., Cogun, C., An investigation on wire wear in WEDM, Journal of Materials Processing Technology, Vol. 134, pp. 273-278, 2003. 11. Bozkurt N. ve Yazcolu S., Srdrlebilir Tayc Hafif Beton Tasarm ve Mekanik zelliklerinin Aratrlmas, Uluslararas Srdrlebilir Yaplar Sempozyumu (ISBS), Ankara, 2010. 12. Tosun N. and Ozler, L.,Optimisation for Hot Turning Operations with Multiple Performance Characteristics, The International Journal of Advanced Manufacturing Technology, No 23, pp. 777-782, 2004. 13. Ross P.J.,Taquchi Tecniques for Quality Engineering, McGraw-Hill, 2nd Edition, New York, 1996.
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COMPACTION
www.turkishpm.org
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ON THE SEVERE PLASTIC DEFORMATION OF SINTERED STRUCTURAL STEELS BY CONSTRAINED GROOVE PRESSING
Viorica CHERTES, Radu L. ORBAN, Ioan VIDA-SIMITI, Liviu BRNDUAN Technical University of Cluj-Napoca, 103-105 Muncii Blv., Romania, chertes@gmail.com ABSTRACT The possibilities of Severe Plastic Deformation (SPD) application to improve mechanical properties of sintered structural steels are investigated. Among the known SPD variants, Constrained Groove Pressing (CGP), was selected as it keeps the part shape and precision. It consists in part repressing in a die of similar cavity but a little larger cross section, producing both compression and shear stresses with pore closing and microstructure refining. The effects of compacting and sintering parameters and of re-pressing pressure, on the final density, microstructure and hardness of sintered parts processed from Distaloy AE powder by cold die compaction/sintering is presented. Keywords: Powder Metallurgy, Severe Plastic Deformation, Mechanical Properties. 1. INTRODUCTION The extending of Powder Metallurgy (PM) application, as a clean, productive and cost-effective technology to a wider range of structural parts fabrication is still limited by its known drawback of the inherent porosity, which diminishes mechanical properties in comparison with those of their wrought counterparts with the same chemical composition [1]. An intensive research activity is worldwide performed to overcome this drawback. Powders with improved compressibility, more efficient compaction lubricants, die wall lubrication, new compaction technologies like warm and high velocity compaction, more efficient sintering and post sintering treatment technologies like high temperature sintering and sinter-quenching have been developed [2]. Even though all these have brought a notable progress, it is not yet at the expectations and, consequently, intensive researches are still underway [3]. A method of a high potential to notable reduce porosity of sintered parts and even to refine their microstructure, improving on these ways mechanical properties, is Severe Plastic Deformation (SPD) [4]. In spite of its proved potential to lead to the obtaining of sub-micron or even nanocrystalline structures in bulk metallic materials and, implicitly, to improved mechanical properties, there is a very little information on the SPD application to sintered structural materials, most of them referring to the green compact advanced consolidation by the most investigated SPD variant - Equal Channel Angular Pressing (ECAP). So, K. Xia et al. [5] revealed that significantly increased density, while N. Harrison et al. [6] that also smaller grain sizes and improved hardness values can be achieved by this method. However, although it is expected that ECAP can be also applied to sintered materials, being, in fact, an extrusion process, can not be applied to the near-net shape part obtaining. For this purpose, J. Asami et al. investigated die compaction at 2000 MPa for sintered structural parts [7], proving the possibility of SPD application to the near-net shape green part obtaining, of which sintering leads to mechanical strength equivalent to that of full dense compacts. So, they have established that higher green densities, up to 7.6 g/cm3 and a fine-grain microstructure can be achieved on this way. Furthermore, these properties can be controlled without difficulty, by selecting the SPD degree of deformation and applied pressure. But, it was not found any published information concerning SPD application directly to the obtaining of near-net shape sintered parts. Consequently, this possibility has been considered in the present research with reference to the most used materials in sintered structural part fabrication - low alloy steels. By analyzing the known SPD variants {Equal Channel Pressing (ECAP), Constrained Groove Pressing (CGP), Differential Speed Rolling (DSR) etc.}[4], one was established that the most appropriate for sintered parts is CGP, as it keeps the part shape and assures the obtaining of the required precision. It consists in part repressing in a die of a similar shape cavity but of a little higher cross section, producing both compression
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and shear stresses with pore closing and microstructure refining. Consequently, it was adopted in this research. The effects of cold die compacting and sintering parameters in Endo-gas and of re-pressing pressure, on the final microstructure, density, hardness, ultimate tensile strength and elongation of structural parts obtained from Distaloy AE powder were investigated and are presented. 2. EXPERIMENTAL PROCEDURE Hgans Distaloy AE powder low alloyed with Cu, Ni and Mo [8] has been uniaxially compacted at different compacting pressures (200, 400, 500, 600 and 700 MPa) to cylindrical samples of a diameter of 9,24 mm (cross section area, S0 = 67.06 mm2) and a height of 8 mm, in a pressing tool with floating die, with die wall lubrication. Beside these cylindrical samples for density determination, three tensile test samples (ISO 2740:2009) have been realized but only at a compacting pressure of 700 MPa. All these green samples were sintered in industrial conditions, in a belt sintering furnace, at 1120 0C, in endogas with a dew point of -40 0C for 40 min, followed by cooling in the waterjacket cooling zone of the sintering furnace (cooling rate ~30 0C/min). In agreement to the selected CGP variant of SPD, the die re-pressing with transverse deformation of material (Fig. 1) [1] has been adopted in the experimental researches.
Figure 1. Principle of die compaction with transverse deformation of material [1]. According to the Theory of Plastic Deformation of Metallic Materials [9], even to a compression applied stress, shear stresses also appear in the transverse directions, leading to material deformation both by compression and by shear. In the case of porous materials, this results in the pore flattening and can lead to their wall cold welding under the applied pressure. Therefore, after their density and hardness determination by the Archimedes method (ISO 2738:1999/ASTM B962) and Rockwell B method (ISO 6508-1:2005/ASTM E18 respectively, all the cylindrical samples were re-pressed in a rigid die of the same shape as the initial sintered compacts but having a higher area of the cross section, i.e. diameter of 11,28 mm (cross section area, S1 = 100 mm2), respectively with a degree of transversal deformation, tr 33 % with pressures of 1400 1600 and 1800 MPa and die wall lubrication using the same lubricant as to the initial pressing, without annealing between the initial pressing and re-pressing. To avoid the die crack, it has been consolidated with a 205Cr115 high strength steel (ASTM A-120) clamping ring. Three cylindrical samples were realized in the above mentioned conditions for each compacting pressure, respectively adopted re-pressing pressure (i.e. a total of 36 samples). However, as the construction of a die of a higher cross section than of the standard one and also its consolidation was more difficult, for the test samples re-pressing was adopted the same die as for their compaction and only one re-pressing pressure, respectively 1200 MPa. To accomplish the condition of sample transversal deformation during re-pressing in the same die as for compaction, beside their cross section reduction by shrinkage at sintering, a supplementary reduction has been realized by uniform grinding along to contour with a cutting depth of 0.86 mm, to assure a transverse deformation degree as that adopted for cylindrical samples ~33%). The re-pressed cylindrical samples were characterized by density and hardness determination in the same way as before re-pressing, and also by their microstructure optical examination, after etching with Nital 3%, on an Olympus 50x 1000x inverted metallurgical metallographic microscope with USB digital JPG image camera, while both assintered and re-pressed tensile samples were subjected to tensile test at room temperature, in conditions of the above mentioned ISO 2740:2009 with a loading speed 1 mm/min, on universal testing machine Sun 5, with stress strain diagram recording. 3. RESULTS AND DISCUSSION Metallographic investigation was performed for revealing the correlation between microstructure compacting and re-pressing pressures. As can be seen in Figure 2, presenting, for the lack of space, only typical microstructure of
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the re-pressed samples, a dense microstructure with fine grains, oriented toward the main direction of plastic deformation (by shearing) have been formed, while porosity has been almost totally eliminated, being much lower than of the sintered samples without re-pressing. Certainly, it depends upon the re-pressing pressure, but also upon the initial density and, intricately, by the compacting pressure.
Figure 2. Typical microstructure of the re-pressed at 1800 MPa sample, initially compacted at 700 MPa. Etching: Nital 3%. The correlation between density, D compacting pressure and re-pressing pressure, P, for the same degree of transversal deformation is graphically presented in Figure 3. For better reflecting the effect of re-pressing pressure on the densification process, on the right Y axis of the graph has been represented the Compactness, C, i.e.
Figure 3. Effect of re-pressing pressure on the density, D and compactness, C of sintered compacts for the used compacting pressures. Relative density values - established in respect to the theoretical density of Distaloy AE material, calculated taking into consideration its composition {(Cu 1.5%, Ni 4.0%, Mo 0.5 %, Fe balance (94.0 %)}[8] and density of components respectively. As can be seen, by the common PM route of cold compaction and sintering (0 value of re-pressing pressure on diagram), the obtained density values are in the limits provided by the Distaloy AE powder producer, Hgans AB co. [8], proving that these operations occurred normally. Instead, as expected, a notable increasing of density, respectively of compactness, occurred by re-pressing. Certainly, the highest density (points filled with the same color)/compactness (points filled in yellow) values have been obtained for the highest repressing pressure (1800 MPa) and for the highest compaction pressure used in the green compact preparation (700 MPa), but well above 90 % relative densities have been also obtained for the re-pressing pressure of 1600 MPa and even of 1400 MPa and for the compacting pressures of 600 MPa and even of 400 MPa.
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Figure 4. Effect of re-pressing pressure on the compactness of sintered compacts increasing for the used compacting pressures. All these findings prove that the method can be applied at the industrial scale as 1600 and 1400 MPa re-pressing pressures can be easier adopted than 1800 or, certainly, than 2000 MPa above mentioned as adopted by J. Asami et al. in their research [7], while 600 and 400 MPa compacting pressures are more often used than 700 MPa in the sintered structural part fabrication to prevent excessive wear of tools [1]. To evaluate repressing behavior and the work hardening introduced by the re-pressing of sintered samples without their intermediate annealing advantageous from the cost point of view the compactness increasing as a function of the re-pressing pressure has been calculated and also the main mechanical properties were determined. So, in Figure 4 is presented the compactness increasing as a function of re-pressing pressure for all the used compacting pressures. Certainly, the increasing of this characteristic by re-pressing is as high as re-pressing pressure is higher. However, on the first view, it appears somewhat surprising that the maximum compactness increasing doesnt occur for the maximum used compacting pressure (700 MPa), but, on the contrary, it has the smallest values. This is an indubitable proof that, at re-pressing, densification occurs mostly by the pore elimination as a result of the above-mentioned shear and cold welding processes and samples compacted with 700 MPa already have the smallest porosity (< 10 %, see Fig.3) among all the samples. Hardness and tensile rupture strength of the re-pressed samples are sensitive properties which can portray the amount of pore closing and of cold hardening during re-pressing without an intermediate annealing process. For the lack of space, in Figure 5 is presented hardness variation with re-pressing pressure only for samples compacted with 700 MPa.
Figure 5. Hardness of the re-pressed compacts variation with the re-pressing pressure for the compacting pressure of 700 MPa. Surprisingly, it abruptly increases, with 42.69%, by re-pressing up to the re-pressing pressure of 1400 MPa (from 71.48 HRB to 102 HRB), remaining quite the same for its higher values (medium values of 102.66 for 1600 MPa and of 104.12 for 1800 MPa) in spite of the above presented results of density increasing. This proves that hardness of sintered samples increasing at re-pressing is determined to a higher extent by the material cold hardening than by the sample densification and there are not significant differences between the material cold hardening at
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re-pressing with re-pressing pressures higher than 1400 MPa. The most appropriate trend-line, fitting on the best extent the experimental variation curve (smallest value of R2), the logarithmic one (see Fig. 5) shows a tendency of asymptotic increase of hardness as the re-pressing pressure increases, which appears more normal. However, tensile test at room temperature seems to lead to a similar result. So the recorded stress-strain curves for the re-pressed samples with only 1200 MPa, a re-pressing pressure smaller even to that to which the hardness increases 1400 MPa (see Fig. 5), and of as-sintered sample (repressing pressure equal to zero), not included hire for the lack of space, indicates a value of ultimate tensile strength of the re-pressed sample (UTS1200 = 473.18 MPa) with 24.34 % higher than of the as-sintered sample (UTS0 = 380.56 MPa). But, an unexpected increase of the elongation at rupture, from Er0 = 7.43 % for the as-sintered sample to Er1200 = 7.64 % for the re-pressed with 1200 MPa, i.e. with ~2.8 % has been also observed. This cannot be explained by the material cold hardening, as on the contrary, by cold hardening plasticity and, implicitly, elongation at rupture in tension decrease. So, it can be attributed in exclusivity to densification. Consequently, one can be resumed that hardness of sintered parts increase at re-pressing is determined mostly by the material cold hardening, while tensile properties (ultimate tensile strength and elongation) by the sample densification. 3. CONCLUSIONS The above presented results prove that severe plastic deformation can be successfully applied to sintered low alloyed steels - the most used in the sintered structural parts fabrication for their both density and mechanical properties. In the CGP variant, i.e. by the sintered compact further die compaction with transverse deformation of material, it can be applied to parts of a high complexity, keeping their geometrical shape and precision. For the common industrial used compacting pressures (400-600 MPa), an increase in density of about 5 -12 [%], in hardness of over 30 %, in UTS of 20-25 % and in elongation of 2.5-3.5 % can be achieved in quite simple and safe conditions, replacing the classical calibration operation with severe plastic deformation. REFERENCES 1. * * * ASM Handbook, Vol. 7, Powder Metal Technologies and Applications, ASMI, 1998, ISBN 978-0-87170-3873, 1238 p. 2. T. Sawayama, M. Sato, Y. Seki, T. Tsuchida and H. Yaguchi, High Performance P/M Materials by High Density Process, Proceedings of 2000 Powder Metallurgy World Congress, The Japan Society of Powder and Powder Metallurgy Ed., Tokyo, 2000, Part 1, p. 540-542, ISBN 4-9900214-8-7. 3. J. M. Torralba, R. De Oro and M. Campos, From Sintered Iron to High Performance PM Steels, Materials Science Forum, Ed. Trans Tech Publications Ltd, Switzerland, Vol. 672, pp. 3 11, 2011. 4. A. Azushima et al., Severe plastic deformation (SPD) processes for metals, CIRP Annals - Manufacturing Technology 57(2), 716 (2008). 5. K. Xia and X. Wu, Back pressure equal channel angular consolidation of pure Al particles, Scripta Materialia, Vol. 53, Issue 11, 2005, p. 1225. (2005). 6. Harrison & I. T. H. Chang, Consolidation of Elemental Aluminium Powders Using Equal Channel Angular Pressing (ECAP), Proceedings of the PM 2010 World Congress, Vol.1, p. 565-572. 7. J. Asami, N. Hirose and T. Kohno, Die Compaction at 2000 MPa for Sintered Structural Parts, Proceedings of 2000 Powder Metallurgy World Congress, The Japan Society of Powder and Powder Metallurgy Ed., Tokyo, 2000, Part 1, p. 570-573, ISBN 4-9900214-8-7. 8. *** Hgans Iron and Steel Powders for Sintered Components, Copyright Hgans AB, 2002, 393 p. 9. K.M. Ralls et. al., An Introduction to Materials Science and Engineering, John Wiley& Sons Ed. 1976.
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COMPOSITES
www.turkishpm.org
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AN EVALUATION OF SiC PARTICLE REINFORCED CEMENTED COPPER COMPOSITES

Gozde F. CELEBI EFE, Ibrahim ALTINSOY, Mediha IPEK, Sakin ZEYTIN, Cuma BINDAL Sakarya University, Engineering Faculty, Department of Metallurgy and Materials Engineering, Esentepe Campus, 54187 Sakarya-Turkey, E-mail:gcelebi@sakarya.edu.tr ABSTRACT In this study, copper powder was produced by cementation method. For comparison, cemented and commercial copper powders were reinforced with SiC particles of 1 m size and at ratios of 0, 1, 2, 3 and 5% by weight. Powder mixtures were pressed with an axial pressure of 280 MPa and embedded in graphite powder for obviating the oxidation. Sintering process was performed in an open atmospheric furnace at 700C for 2h. The morphology and phases of composites were analyzed by Scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. Optical and SEM studies showed that SiC particles were located around the copper grains. Commercial Cu-SiC composites have more homogenous microstructure than the cemented Cu-SiC composites due to the agglomeration of cemented copper powders. Relative densities and electrical conductivities were decreased with increasing weight percentage of SiC particles. The highest electrical conductivity of 79% IACS (International annealed copper standard) for cemented Cu-SiC composites and 86% IACS for commercial Cu-SiC composites was obtained for Cu-1wt.% SiC composites. The microhardness of test materials increased as amount of reinforcing materials increased. Keywords: Cu-SiC, Composite, Cementation, Relative density, Electrical conductivity. 1. INTRODUCTION Copper is a mostly used industrial and functional metal for various thermal and electronic applications, i.e. electronic packaging, electrical contacts and resistance welding electrodes. This is because of good thermal and electrical conductivity, high Plasticity, softness, formability and excellent resistance to corrosion and oxidation. Although pure copper is mostly used in electrical applications, it has a key role to play in energy efficiency and provides durable maintenance free structures that are naturally good looking, long lasting and fully recyclable. Nevertheless, low mechanical strength and undesirable wear resistance limit its applications [1,2]. The room temperature mechanical strength can be improved dramatically by addition of small amount of elements such as Cr, Zr, Ag or Fe, etc. to form precipitation- hardened alloys. However, these copper alloys lose their high strength at higher temperature (usually 500 oC) generally related to the structural instability caused by the coarsening of precipitation particles. Furthermore, low wear resistance and conductivity are the other two limitations of these alloys. In this respect, dispersion-strengthened copper has the ability to retain most of its properties on exposure to high temperatures. Through adding inert, second phase particulate materials (such as oxides, carbides, borides) in copper matrix, it can not only keep coppers excellent electrical and thermal conductivity, but also make copper achieve appreciable strength. The dispersion-strengthened copper alloys generally can be classified as the copper-based matrix composites. In addition, copper-based composites physical and mechanical properties can be varied from the second phase content. In recent years, Cu/SiC composites have received considerable attention to meet the challenges of thermal management in the rapidly increased power of advanced electronics. They offered a great potential for uses in electrical sliding contacts such as those in homopolar machine and railway overhead current collection system, where high thermal electrical/thermal conductivity and good wear resistant properties are needed, high-temperature structural applications and electronic packing due to the superior heatconductive, electric conductive and heat-releasing natures [3-6]. Methods for the production of dispersion-strengthened copper matrix composites involve ingot casting and powder metallurgy PM. processes. The PM route consists
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of several processes like blending, compacting, and sintering. Blending is one of the crucial processes in PM where the metallic powders are mixed with the ceramic reinforced particles. Good blending produces no agglomeration of both the metallic and ceramic particle powders. Conventional melting and casting has distinct limitations due to the poor wettability between ceramic particles and molten copper, leading to agglomeration of dispersoids. Moreover, the difference in the densities and the reinforcements can also cause segregation in the melts. Therefore, the PM route is ideal to prepare copper matrix composites because of its efficient dispersion of fine particles [4]. In this study, the influences of the amount of the SiC on the properties of the both cemented and commercial copper composites were investigated and studied what sort of differences exist between commercial or cemented copper-SiC composites. 2. EXPERIMENTAL DETAILS Copper powder was precipitated from the CuSO4 solution by cementation method. 2-6m cemented copper powder and 10m commercial copper powder was mixed with 1m SiC particles at weight percentage of 1, 2, 3 and 5. Powder mixtures were cold pressed in metal die of 15 mm in diameter under an axial pressure of 280 MPa. Compacted samples were embedded into the graphite powder and sintered at 700C in an electrical furnace. After sintering samples were immediately pressed with a load of 850 MPa in order to increase the relative density and electrical conductivity. The microstructures of specimens were examined by Optic and SEM microscopy. The presence of phases formed within the sintered samples was determined by x-ray diffraction using CuK radiation with a wavelength of 1.5418 A over a 2 range of 10 to 80o. In order to detect the Cu, SiC and any oxide of Cu and SiC particles EDS analyses were performed. Relative densities of samples were determined according to Archimedes method. Microhardness of both pure copper and composites were determined using a Leica WMHT- Mod model Vickers hardness instrument under an applied load of 50g. Electrical conductivity of polished samples was determined by GE model electric resistivity measurement instrument. 3. RESULTS AND DISCUSSIONS SEM images of initial copper powders, obtained commercially and precipitated by cementation method, were given in Fig.1. Commercial copper powders are in spherical morphology and 10m particle size. It can be seen from the Fig.1b that there is a significant agglomeration in cemented copper powders. Size of these agglomerates is approximately 5-7m but real size of the cemented copper grains is submicron.
(a) (b) Fig.1. SEM micrographs of a) commercial and b) cemented copper powder. Optic microstructures of commercial and cemented Cu-3wt.%SiC composites sintered at 700C for 2 hours were shown in Fig.2. Dark grey and cornered particles indicate SiC particles and light grey regions show Cu matrix. It is seen from the Fig.2 that SiC particles dispersed in copper matrix homogenously. For commercial Cu-SiC composites, it can be said that SiC particles located at the joining points of copper grains but for cemented Cu-SiC composites more complex microstructure is said. This is related with the agglomerated grain structure of cemented copper.
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(a)
(b)
Fig.2. Optic micrographs of a) commercial and b) cemented Cu-3wt.%SiC composites sintered at 700C for 2 hours. XRD patterns of cemented and commercial copper matrix-SiC composites, including 1 and 5wt.%SiC, are shown in Fig. 3 and consist of Cu and SiC dominantly. In the XRD analysis of cemented Cu-SiC composites slight amount of iron-oxide (Fe3O4) was detected and it probably results from the cementation process of copper powder. For both Cu-SiC composites SiC peaks become clear with increasing weight percentage of SiC. Dominant phases of Cu and SiC in composites were confirmed by EDS analysis. In EDS analysis, while dark and relatively cornered components indicate SiC, grey components indicate Cu matrix (Fig. 4). In the analysis taken from the SiC particles in commercial Cu-SiC composite, slight oxygen was detected together with Si and C. This probably arises from surfaces of the SiC particles. In Fig. 4b iron reach areas seems as light grey and it probably results from cementation process and oxidized at sintering temperature. Fig. 5 reveals that the density of composites using Archimedes principle tends to decrease with increasing SiC content. This is due to the density of SiC particles being much smaller than that of copper [7]. Relative densities of commercial Cu and Cu-SiC composites are higher than cemented ones. This may be related with the morphology and agglomeration of cemented copper grains. Commercial copper grains are more spherical shape and so can be compacted easily. Hardness variation of Cu and Cu-SiC composites with increasing SiC content was given in Fig. 6. Hardness of sintered pure copper was determined as 133HVN for commercial copper and 127HVN for cemented copper. These values are too high from the literature value of 37 HVN for copper and this may be related with hot pressing applied after sintering. It can be seen from the Fig. 6 that hardness values of composites increased with increasing weight percentage of SiC particles. Hardness of ductile copper generally improves with addition of hard disperse phase [8, 9]. It is thought that the higher the amount of the ceramic particles in the matrix, the higher the density of the dislocation, and as a result, the higher the hardness of the composite [10, 11]. The results of electrical conductivity values measured on the polished samples were given in the Figure 7. Electrical conductivity of cemented and commercial coppers were measured as 95.6 % IACS (International Annealed Copper Standard) and 91.7 % IACS respectively and the addition of SiC contents decreased the electrical conductivity of Cu-SiC composites as expected. It is possible to claim that there is a linear relationship between SiC content and electrical conductivity and electrical conductivity values of composites are coherent with relative density and hardness values of composites. Irregular dispersion of SiC particles in cemented copper matrix probably caused lower electrical conductivity than commercial copper matrix composites, because of the agglomerated grain structure of cemented copper powder.
(a)
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(b) Fig. 3. XRD patterns of a) cemented, b) commercial copper matrix-SiC composites including 1 and 5wt.%SiC.
Fig. 4. SEM-EDS analysis of a) commercial Cu-2wt.% SiC and b) cemented Cu-2wt.% SiC composites sintered at 700C for 2h.
Fig. 5. Relative density variation of cemented and commercial Cu and Cu-SiC composites depending on SiC weight percentage.
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Fig. 6. Hardness variation of cemented and commercial Cu and Cu-SiC composites depending on SiC weight percentage.
Fig. 7. Electrical conductivity variation of cemented and commercial Cu and Cu-SiC composites depending on SiC weight percentage. 4. CONCLUSIONS In conclusion Cu powders were produced by chemical precipitation method from CuSO4 salts and commercially used for comparison. Cu-SiC composites with high electrical conductivity were produced by reinforcing cemented and commercial copper with ceramics based SiC at different ratios by the PM method at 700C in the present work. XRD patterns of commercial and cemented Cu-SiC composites are similar to each other and consist of Cu and SiC peak dominantly. SiC peaks become clear with increasing of SiC content. It was found that SiC particles distributed homogeneously in Cu matrix and generally they are concentrated at grain boundaries of Cu grains for commercial Cu-SiC composites. For cemented Cu-SiC composites more complex microstructure was observed related with the agglomerated grain structure of cemented copper. Related with this slightly higher relative density, electrical conductivity and hardness were achieved for commercial Cu-SiC composites. For both cemented and commercial Cu-SiC composites relative density and electrical conductivity was decreased and hardness increased with increasing weight percentage of SiC particles. It can be said that cemented copper matrix can replace instead of commercial copper matrix.
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Acknowledgement The authors thank to experts Fuat Kayis for performing XRD and SEM-EDS studies and special appreciation are extended to technician Ersan Demir of Sakarya University for assisting with experimental studies. This work was conducted a project supported by TUBITAK with contract number of 106M118. REFERENCES 1. Barmouz, M., Givi, M. K. B., Seyfi, J., On The Role of Processing Parameters in Producing Cu/SiC Metal Matrix Composites via Friction Stir Processing: Investigating Microstructure, Microhardness, Wear and Tensile Behavior, Materials Characterization, Vol. 62, pp. 108-117, 2011. 2. Barmouz, M., Asadi, P., Givi, M. K. B., Taherishargh, M., Investigation of Mechanical Properties of Cu/Sic Composite Fabricated By FSP: Effect of Sic Particles size and Volume Fraction, Materials Science and Engineering A, Vol. 528, pp. 1740-1749, 2011. 3. Zhan, Y., Zhang, G., The Effect of Interfacial Modifying on The Mechanical and Wear Properties of Sicp/Cu Composites, Materials Letters, Vol. 57, pp. 4583-4591, 2003. 4. Tjong, S. C., Lau, K. C., Tribological Behaviour of SiC Particle-Reinforced Copper Matrix Composites, Materials Letters, Vol. 43, pp. 274-280, 2000. 5. Zhu, J., Liu, L., Hu, G., Shen, B., Hu, W., Ding, W., Study on Composite Electroforming of Cu/Sicp Composites, Materials Letters, Vol. 58, pp. 1634-1637, 2004. 6. Zang, R., Gao, L., Guo, J., Preparation and Characterization of Coated Nanoscale Cu/Sicp Composite Particles, Ceramics International, Vol. 30, pp. 401-404, 2004. 7. Tjong, S.C., Lau, K.C., Tribological Behaviour of SiC Particle-Reinforced Copper Matrix Composites, Materials Letters, 43, pp. 274-280, 2000. 8. Efe, C.G., Altinsoy, I., Ipek, M., Zeytin, S., Bindal, C., Investigation of Some Properties of SiC Particle Reinforced Copper Composites, 5th International Powder Metallurgy Conference, Ankara-Turkey, October 08-12, 2008. 9. Efe, C. G., Altinsoy, I., Yener, T., Ipek, M., Zeytin, S., Bindal, C., Characterization of Cemented Cu-SiC Composites, Vacuum, Vol. 85, pp. 643-647, 2010. 10. Shu, K-M., Tu, G.C., The Microstructure and the Thermal Expansion Characteristics of Cu/SiCp Composites, Materials Science & Engineering, Vol. 349, pp. 236-247, 2003. 11. Efe, C.G., Altinsoy, I., Ipek, M., Zeytin, S., Bindal, C., Some properties of Cu-SiC composites produced by powder metallurgy method, Kovove Metallic Materials, Vol. 49, No.2, pp. 131- 136, 2011.
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AN INVESTIGATION ON Cu-Al2O3 COMPOSITES PRODUCED BY PM METHOD

brahim ALTINSOY, Gzde F. elebi EFE, Tuba YENER, Mediha PEK, Sakin ZEYTN, Cuma BNDAL Sakarya University, Engineering Faculty, Metallurgy and Materials Engineering Department, Esentepe Campus 54187, Serdivan-Sakarya, E-Mail: ialtinsoy@sakarya.edu.tr ABSTRACT This study reports on characterization of copper (40 m) composite reinforced with alumina (0.3 m) particle at ratios of 5 and 7% by weight. Sintering was performed at 925C for 2h in graphite powder. The relative densities of sintered samples are 98.8 and 97 % for reinforcements amount of 5 and 7 wt%, respectively. Optical and SEM studies revealed that alumina particles were located homogenously around Cu grains. The presence of alumina and copper were confirmed by EDS and XRD analysis. Depending on the amount of alumina, the electrical conductivity of test samples ranged from 58.6 to 44.8 %IACS. There is a little change in the microhardness of test materials with increment in the amount of reinforcement ratios. Key Words: Sintering, Alumina, Copper, Conductivity, Composite. 1. INTRODUCTION Although, Copper is widely used as an electrical conductor because of its high electrical and thermal conductivity, but it has low tensile and yield strength. To solve this problem, copper has been strengthened by several different ways. Conventional methods such as cold working and precipitation hardening as well as solid solution hardening, which lower thermal conductivity, are not suitable for high-temperature applications. Metal matrix composite materials can be utilized at higher service temperatures than their base metal counterparts. There, the primary attention is in dispersion strengthening (DS) of copper, i.e. in copper based metallic matrix composites and, oxide dispersion strengthened Cu matrix composites (ODSC) present superior advantages and have been successfully used in a good many aspects of industry such as automobile and wiring industries (MMC) [1-3]. Studies on the synthesis and characterization of nanoscale alumina dispersed copper metal matrix composites have been attracting scientific interest in recent years, since nanostructured-type materials are expected to have special physical and mechanical properties. Owing to the presence of uniformly-dispersed fine Al2O3 particles, which are hard and thermally stable at the elevated temperatures near the melting point of the copper matrix, the alumina-dispersion strengthened copper-based composites afford high strength at elevated temperatures as well as at room temperature. A unique combination of high strength and electrical conductivity at elevated temperatures enables the Al2O3/Cu composites to be the best candidates for high-temperature electric material and the most attractive material of the international thermonuclear experimental reactor (ITER) high-heat flux components, such as, electrodes, lead wires, connectors, diverters and first wall [4,5]. In order to achieve high fracture toughness and low processing cost, the Al2O3 phase in the microstructure should be in particulate form, and the particle size should be as small as possible. The particulate reinforced CuAl2O3 MMCs can be synthesized by using several routes which include mixing of Cu melt and Al2O3 powder followed by casting, such as the Comalco process, and internal oxidation of CuAl alloy powders. The casting process has the limitation that the Al2O3 size has to be large enough to allow effective mixing. Alternatively, powder metallurgy is fabrication method with its advantage of homogeneous mixing of constituent materials which eventually gives good final mechanical properties to the composite with sufficient physical properties.[5-7]. The present paper aims to investigate the effect of high reinforcement amounts on the properties of copper-alumina composites.
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2. EXPERIMENTAL DETAILS During this study, commercial Cu powder (99.9% puridity) as a matrix material and commercial Al2O3 powder as a reinforcement agent (99% puridity) were used. At first, powders were mixed and then were compacted by unaxial press. After compaction, the green body sintered at 925 C for 2 hours in an electrical furnace. Following sintering, samples were hot pressed as fast as possible and finally, composites characterized by using optical microscope, SEM, SEM-EDS, XRD, Vickers Indentation Technique, DC electrical conductivity instrument and by measuring density using Archimeds principle. The preparation and characterization procedures of the samples were given schematically in Fig. 1.
Fig.1. The schematical presentation of experimental procedure. 3. RESULTS and DISCUSSIONS 3.1. Optical-SEM Micrographs It can be claimed that the reinforcement materials distributed homogenously into the matrix and they located among the Cu grains. This phenomena results from the poor wettability between Cu and Al2O3. Dark grey regions indicate Al2O3 particles, when bigger gray areas point out the Cu matrix (Fig. 2).
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(a) (b) Fig.2. Optical micrographs of composites sintered at 925 oC for 2h. reinforced with: a) Al2O3 wt.5% b) Al2O3 wt. 7% (Magnification: 500X) SEM microstructures of the samples are similar to optical micrographs according to distribution and location of the reinforcing agent. Same gray grains indicate the Cu, while white, small zones seen as Al2O3. Besides, there was no remarkable grain grow in the Cu matrix after the sintering. This probably resulted from reinforcement agent formed a barrier for possible grain growth (Fig. 3).
(a) (b) Fig.3. SEM microstructures of composites sintered at 925 oC for 2h. reinforced with: a) Al2O3 wt.5% b) Al2O3 wt. 7% 3.2. XRD Analysis XRD analyses revealed that the dominant phases in the composite bodies were Cu and Al2O3. Peak intensities of the reinforcement material was shown very few contrast to Cu, because the ratio of them to matrix phase are very little. Also, there was a little amount of copper-oxide (Cu2O) in both Cu- Al2O3 wt. 5% and 7% samples, but the change in the amount of copper-oxides was no remarkable by increment in the ratio of reinforcement material (Fig. 4 and 5).
Fig. 4. XRD analysis of the Cu- Al2O3 wt.5% composite sintered at 925 oC
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Fig. 5. XRD analysis of the Cu- Al2O3 wt.7% composite sintered at 925 oC 3.3. SEM-EDS Results
Fig. 6. SEM-EDS analyses of the Cu-Al2O3 wt. 5% and 7% samples. The results of the SEM-spot EDS analyses were confirmed the optical, SEM examinations and XRD analyses. The spots taken from the larger grey areas (spot #1 in Cu- Al203 wt. 5% and 7 %) indicated Cu matrix, while black regions (spot #2,3 in Cu- Al203 wt. 5%; spot #2,3,4 in Cu- Al203 wt. 7%) between the copper regions pointed out reinforcement agent in both composites samples. This clarifies why the reinforcements existed among the matrix grains. Further-
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more, the oxygen element mostly resulted from the Al2O3. There is no oxygen evidence on the surface of copper grains as well as detecting a little at the spots taken from the Cu-Al2O3 interface. This was probably resulted from the both oxidation of starting Cu powder and oxidation during the sintering process. 3.4. Relative Density-Microhardness-Electrical Conductivity The results of relative density, microhardness and electrical conductivity measurements were given in Table 1. Microhardness measurements conducted by taking care of the indenter incorporates both matrix and reinforcement phases, homogenously. Table 1. The relative density, microhardness and electrical conductivities of the composite samples sintered at 925 oC. Al2O3 wt. % Relative Density (%) 5 7 98.78 97.04 Sample Cu (40)-Al2O3 (0.3 m) Microhardness (HV) 156 159.4 Electrical Conductivity (%IACS) 58.62 44.83
From the Table 1, it can be seen that the relative densities and electrical conductivities of the composites decreased by increasing of the reinforcement ratio, but this diminution was remarkable in the electrical conductivities other than the relative density. This could result from the post compaction process eliminated the pores in the body. On the other hand, the microhardness values increased slightly with the increment in the ratios of Al2O3. Due to the small and uniformly distributed hard Al2O3 particles act as reinforcing phases and become obstacles to the movement of dislocations [1], the microhardness increased. Furthermore, post compaction (hot pressing) after sintering, provides increment in the number of dislocations in the matrix and this contributed to the hardness increment. According to Mathiessen Rules, electrical conductivity is affected by resistivity due to impurities, since alumina is an insulator and act as impurities in copper matrix and plastic deformation, the composites achieves lower electrical conductivity [7]. 4. CONCLUSIONS Cu (40 m)-Al2O3 (0.3 m) composites were produced by PM method and the distribution of the reinforcements was homogenously in the matrix. The reinforcements agent, Al2O3 located between the copper grains and this confirmed by SEM-EDS results. The dominant phases were detected as Cu and Al2O3 and a little amount of copper-oxide existed in the composites by the XRD results. In the XRD results, the few amount of copper-oxides probably resulted from the oxidation of starting Cu powder and/or oxidation during sintering process. SEM-EDS analyses confirmed the XRD results and evidences as mentioned in optical, SEM micrographs. The microhardness of the composites increased slightly by increasing of the amount of Al2O3, while the electrical conductivities and relative densities of them decreased. In this paper, since the amounts of reinforcing agents are at some high levels for this type of composites, the values of electrical conductivities are not enough in the applications which electrical conductivity has primary importance. However, this composites possessed high microhardness values and reinforced with fine particle size of reinforcement and thus, this samples (especially Cu-Al2O3 wt.5%) can be suitable for applications which high hardness and high temperature resistance as well as certain electrical conductivity are required. REFERENCES 1. Ritasalo, R., Liu, X. W., Sderberg, O., Keski-Honkola, A., Pitknen, V., Hannula, S-P., The Microstructural Effects on the Mechanical and Thermal Properties of Pulsed Electric Current Sintered Cu-Al2O3 Composites, Procedia Engineering, Vol: 10, pp: 124-129, 2011. 2. Efe, G. C., Yener, T., Altinsoy, I., Ipek, M., Zeytin, S., Bindal, C., The Effect of Sintering Temperature on Some Properties of CuSiC Composite, Journal of Alloys and Compounds, Vol: 509, pp: 6036-6042, 2011. 3. Wang, Q. Z., Cui, C. X., Lu, D. M., Bu, S. J., Fabrication and Properties of A Novel ZnO/Cu Composite, Journal of Materials Processing Technology, Vol: 210, pp: 497-503, 2010. 4. Motta, M. S., Jena, P. K., Brocchi, E. A., Solorzano I. G., Characterization of CuAl2O3 Nano-Scale Composites Synthesized by In Situ Reduction, Materials Science and Engineering C, Vol: 15, pp:175-177, 2001. 5. Ruihua, L., Kexing, S., Shuguo, J., Xiaofeng, X., Jianxin, G., Xiuhua, G., Morphology and Frictional Characteristics Under Electrical Currents of Al2O3/Cu Composites Prepared by Internal Oxidation, Chinese Journal of Aeronautics, Vol: 21, pp: 281-288, 2008. 6. Ying, D. Y., Zhang, D. L., Processing of CuAl2O3 Metal Matrix Nanocomposite Materials by Using High Energy Ball Milling, Materials Science and Engineering A, Vol: 286, pp: 152-156, 2000. 7. Hussain, Z., Keong, K. H., Studies on Alumina Dispersion-Strengthened Copper Composites Through Ball Milling and Mechanical Alloying Method, Jurnal Teknologi, Universiti Teknologi Malaysia, Vol: 43(A), pp: 1-10, 2005.
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DOAL VE YAPAY YALANDIRMANIN ALMNA TAKVYEL ALMNYUM ALAIMI ESASLI KOMPOZT MALZEMELERN SERTLNE ETKS
M. Fatih AYCAN*, Mustafa BEYL** * Gazi niversitesi, Mhendislik Fakltesi, Makine Mhendislii Maltepe-Ankara, Trkiye ** Osmaniye Korkut Ata niversitesi, Mhendislik Fakltesi, Makine Mhendislii Karacaolan Yerlekesi, Osmaniye, Trkiye ZET Bu almada, toz metalurjisi yntemlerinden scak presleme yntemi kullanlarak Al2O3 takviyeli Al-5Zn-3,5Cu2,5Mg alam esasl kompozitlerin retimi yaplmtr. retilen numunelere doal ve yapay olmak zere iki farkl yalandrma ilemi uygulanmtr. Yalandrma ilemleri sresince numunelerin sertlik deiimleri belirlenmitir. almann sonunda, doal yalandrma ileminde yalandrma sresine bal olarak sertlik deerlerinin balangta ykseldii fakat daha sonra byk lde kararl davran sergiledii grlrken, yapay yalandrma ilemlerinde farkl yalandrma scaklklarnda benzer sertlik deiim erileri elde edilmitir. Anahtar kelimeler: Kompozit malzemeler, yalandrma ilemleri, sertlik
EFFECT OF NATURAL AND ARTIFICIAL AGING ON THE HARDNESS OF ALUMINA REINFORCED ALUMINIUM ALLOY COMPOSITES
ABSTRACT In this study, Al2O3 reinforced Al-5Zn-3.5Cu-2.5Mg alloy composites were produced using hot pressing method which is one of the powder metallurgy methods. Natural and artificial aging processes were carried out to the samples produced. During the aging processes, the hardness behaviors of the composites were investigated in each aging condition. According to the experimental results, it was determined that the hardness values increased at the beginning of the process then they were stable substantially in natural aging, on the other hand similar hardness behaviors were determined for all conditions in artificial aging processes. Key words: Composite materials, aging process, hardness 1.GR Uzun yllar mhendislik uygulamalarnda yaygn olarak kullanlan demir-elik malzemeler yerine, daha dk arlkta daha iyi mukavemet zelliklerine sahip olan metal esasl kompozit malzemeler tercih edilmeye balanmtr [1]. Metal esasl kompozitler sahip olduklar dk younluk ve genleme katsays, yksek dayanm, anma direnci ve rijitlik gibi zellikleri ile n plana kmaktadr. Bu zelliklerin tek bir yapda birleimi mevcut geleneksel malzemeler tarafndan karlanmas mmkn olmamaktadr. lerleyen teknolojiye paralel olarak gelitirilen kompozit malzemeler; gnmzde uzay-havaclk, otomotiv ve savunma sanayinde yaygn olarak kullanlmaktadr [2-4]. Kompozitlerde ana yap ve takviye eleman olarak kullanlacak malzemelerin doru seilmeleri, kullanmlar esnasnda beklenen baarmn elde edilebilmesi iin son derece nemlidir. Ana yapnn sneklik ve tokluk deerlerinin iyi olmasnn yannda slatabilirlii ve takviye eleman ile kimyasal ba oluturma kabiliyetinin yksek olmas istenir-
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ken, takviye elemannn ise ana yap ierisinde znmeyecek ve ana yap ile uyumlu ara yzey oluturabilecek btncl bir yap oluturabilmesi istenir [5]. Hafif metaller olarak nitelendirilen alminyumun ana yap, oksit grubu seramiklerinden Al2O3 seramiinin takviye eleman olarak kullanld metal esasl kompozitler endstride yaygn kullanm alan bulmaktadr. Ayrca, gemi dnemlerde yaplan bilimsel almalar incelendiinde; Al2O3 takviyeli alminyum esasl kompozitlerin iyi ara yzey baarmna ve slatabilirlie sahip olduklar grlmektedir [6]. Seramik takviyeli alminyum esasl kompozitler, zellikle anma dayanm ve dk arlk gibi zelliklerin gerekli olduu uygulamalarda tercih edilmektedir. Parack takviyeli metal esasl kompozitlerin retimlerinde toz metalurjisi, basnl dkm, ekstrzyon ve yar kat kartrma yntemleri kullanlmaktadr [7]. Toz metalrjisi yntemi, ergimi metalin kullanld retim yntemlerine gre ksmen daha maliyetli olmasna ramen dk ilem scaklklarnda retime olanak vermesi nedeniyle endstride geni kullanm alan bulmaktadr [2]. Kompozitlerde; retim ynteminin eidi de ana yap ve takviye elemannn tr ve retim sonrasnda uygulanan sl ilemler gibi mekanik zelliklerin farkllk kazanmasnda etkili olmaktadr. Bu almada 7xxx serisi alminyum alam esasl seramik takviyeli kompozit malzemelerin sertlik deerlerinin uygulanan fakl sl ilemler ile deiimleri incelenmitir. Al2O3 takviyeli kompozit numuneler scak presleme yntemi kullanlarak retilip farkl scaklklarda yalandrma ilemi uygulandktan sonra numunelerin sertlik deiimleri belirlenmitir.
2.MALZEME VE DENEYSEL YNTEM Bu almada %99,9 saflkta ve 20 m alt boyutlarda metal ve seramik tozlar kullanlmtr. Ana yap olarak arlka Al, %5 Zn, %3,5 Cu ve %2,5 Mg oranlarna sahip 7xxx serisi Al alam, takviye eleman olarak parack eklinde Al2O3 seramik tr kullanlmtr. Takviye oran etkisinin incelenebilmesi iin takviyesiz olarak hazrlanan alam ve %5, %10 ve %15 gibi farkl takviye oranlarnda hazrlanan numuneler ile birlikte toplamda drt eit numune hazrlanmtr. stenilen karm oranlarnda hazrlanan tozlar, deirmen tipi kartrcda 2 saat sreyle kartrma ilemine tabi tutulmulardr. almada; sktrma ve sinterleme ilemleri, 15 ton sktrma kapasitesi ve 11 kW stma gcne sahip scak presleme cihaz kullanlarak gerekletirilmitir. Hazrlanan toz karmlarna 50x70 mm ebatlarndaki scak pres kalbna konularak, ortalama 25 MPa basn altnda 535Cde 30 dakika sktrma ve sinterleme ilemleri uygulanmtr. Sonra numunelere kl frnnda 500C scaklkta 30 dakika sreyle zeltiye alma ilemi uygulanm hemen ardndan oda scaklnda su verme ilemi gerekletirilmitir. Daha sonra ise numunelere doal ve yapay olmak zere birbirinden bamsz olarak iki farkl yalandrma ilemi uygulanmtr. Doal yalandrma ilemi 60 gn sreyle 25C oda scaklnda, yapay yalandrma ilemleri ise 120C, 150C, 180C ve 200C scaklklarda 300 dakika sreyle ya banyosu kullanlarak gerekletirilmitir. Yapay yalandrma ilemleri sonunda numunelere oda scaklnda su verme ilemleri uygulanmtr. Yalandrma ileminden sonra numunelerin iyaplar incelenmitir. Numunelerin yalandrma ilemleri boyunca sergiledikleri sertlik deiimleri ise belirli zaman dilimlerinde alnan sertlik lmleri ile belirlenmitir. Sertlik deneyleri; ASTM E10-84 [8] standardna gre 187,5 kg yk ve 2,5 mm bilye ap ile Brinell sertlik yntemi kullanlarak gerekletirilmitir. Doal yalandrma ilemlerinde gnde bir, yapay yalandrma ilemlerinde ise yarm saatte bir alnan er sertlik lm ile numunelerin zamana bal yalanma davranlar elde edilmitir.
3.DEERLENDRME 3.1. Yap ncelemeleri almada kullanlan metal ve seramik tozlarnn ortalama boyutlar toz boyut lm ilemleri ile belirlenmitir. Yaplan lm ilemleri sonucunda belirlenen ortalama ap lleri izelge 1de verilmitir. Toz boyutu, tozlarn ak hzlar ve paketlenmeleri zerinde etkili olmasna bal olarak sinterleme sonrasnda retilen paralarn mekanik zelliklerini byk lde deitirirken, daha yksek paketlenme zellikleri iin kk ve iri toz tanelerinden oluan farkl toz bileimleri hazrlanmaktadr [9]. Ana yapy oluturan element tozlarnn farkl boyutlarda olmas daha iyi zelliklerin elde edilmesinde yararl olduu dnlmektedir.
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izelge 1 Kullanlan tozlarn ortalama boyutlar Malzeme Al Mg Cu Zn Al2O3 Ortalama Toz Boyutu (m) 3,41 14,75 15,55 2,45 12,24
almada takviye eleman olarak parack ekilli seramiklerin kullanlmasna bal olarak numuneler izotropik zellik sergilemektedir. Ana yap ierisinde takviye elemanlarnn dalmlar numunelerin mekanik zellikleri zerinde dorudan etkilidir. Bu nedenle takviye elemanlarnn yap ierisinde homojen dalmalar daha iyi mekanik zelliklerin elde edilebilmesi iin istenen bir durumdur. ekil 1de verilen k mikroskobu grntsnde; %15 Al2O3 takviyeli numunede seramik paracklarnn ana yap ierisinde byk lde homojen dalm sergiledikleri grlmektedir. Bu sebeple numunelerde yne bal zellik farknn gzlemlenmemesi beklenmektedir.
ekil 1 Parack ekilli takviye elemannn ana yap ierisindeki dalm 3.2.Sertlik Davran Alam ve farkl takviye orannda olmak zere toplamda drt farkl bileimde hazrlanan numuneler, doal ve yapay olmak zere farkl yalandrma koullarnda yalandrlm ve her bir koulda numunelerin sergiledikleri sertlik deiimleri ve ulalan en yksek sertlik deerleri belirlenmitir. Oda scaklnda altm gn sreyle yaplan doal yalandrma ilemi sonucunda elde edilen sertlik deiimleri ekil 2de verilmitir.
ekil 2 Numunelerin doal yalanma davran Doal yalandrma ilemlerinde numunelerin benzer davrana sahip olmalarnn yannda farkl sertlik seviyelerine sahip olduklar grlmektedir. Numunelerin farkl takviye oranlarnda benzer davran sergilemeleri, takviye ora-
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nnn numunelerde doal yalanma karakterini etkilemediini, yalnzca ulalan sertlik seviyesini etkilediini gstermektedir. Bu durum, yalandrma ileminin oda scaklnda gereklemesine bal olarak ana yap ile takviye elemanlar ara yzeylerinde kimyasal tepkimelerin gerekleme olaslnn dk olmas ile aklanabilir. Eriler incelendiinde zeltiye alma ve su verme ileminden sonra alnan sertlik deerlerinin, yalandrma ileminin balang safhasnda alnan sertlik deerlerine oranla daha yksek olmasnn sebebi olarak malzemedeki kafes rahatlamas gsterilebilir. Numunelere, doal yalandrma ileminden sonra 120C, 150C, 180C ve 200C olmak zere drt farkl scaklkta yapay yalandrma ilemi uygulanmtr. Her bir numune iin zeltiye alma ve su verme ilemlerinden sonra elde edilen sertlik deerleri doal yalandrma ilemleri sonunda ulalan en yksek sertlik seviyesi ile birlikte ekil 3 ve 4de verilmitir. Yapay yalandrma ilemlerinde; artan yalandrma scaklna bal olarak art gsteren ana yapnn sertlik deerleri, doal yalandrma ilemi sonunda elde edilen en yksek sertlik seviyesine gre daha yksek seviyelere ulamtr.
ekil 3 Yapay yalandrma ilemleri sonunda alam numunenin sertlik davran Artan yalandrma scaklklar ile birlikte sertlik deerlerinde azalma grlrken, yksek scaklklarda tane irilemesinin fazla olmasna bal olarak yksek scaklklardaki sertlik deerlerinin daha dk olduu belirlenmitir [10]. Ana yap zerinde takviye elemannn etkisi olmakszn farkl scaklklarda gerekletirilen yalandrma ilemlerinde ana yapnn yalanma karakteristii belirlenmeye allmtr. Alam numunenin yalanma karakteristiine takviye elemannn etkisi ise ekil 4de verilen erilerde grlmektedir. 300 dakika sreyle yaplan yalandrma ilemleri sonunda elde edilen sertlik davranlar irdelendiinde; genel olarak artan yalandrma scaklklar ile birlikte sertlik deiimlerinde azalma eilimi olduu ve doal yalandrma ilemi sonunda elde edilen en yksek sertlik seviyesine hibir koulda ulalamad grlmektedir. zeltiye alma ve su verme ilemlerinden sonra belirgin biimde artan sertlik deerlerinin, ilerleyen yalandrma sresine bal olarak azalma gsterdii ve bir sre sonra ise deimedii belirlenmitir. Numunelerin yapay yalandrma ilemleri sonunda elde edilen sertlik davranlar karlatrldnda; takviye elamannn ana yapnn ve yalandrma scaklklarnn yalanma karakteristiini belirgin biimde etkiledii grlmektedir.
(a)
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(b)
(c) ekil 4 Yapay yalandrma ilemleri sonunda farkl takviye oranlarnda elde edilen sertlik deiimleri; (a) %5, (b) %10, (c) %15 lem scaklnn, malzeme iinde yalanmaya bal oluan keltilerin yaps zerinde etkili olduu dnlmektedir [11]. Buna ek olarak sl genlemeye bal oluan dislokasyonlar ve yapda bulunan magnezyumun takviye eleman olarak yapya katlan almina ile etkileimine bal olarak oluacak kelti yapsn etkilemesi, alam numune ile takviyeli numunelerin sertlik davranlar arasndaki farkllklarn nedenini aklamaktadr [12]. Numunelerin scak presleme yntemiyle retilmeleri ile zeltiye alma ve su verme ilemlerinden sonra elde edilen ve uygulanan yapay yalandrma ilemleri esnasnda ulalan en yksek sertlik deerleri ekil 5de verilmitir.
ekil 5 Farkl koullarda elde edilen sertlik deerleri
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Ham olarak ifade edilen retim sonras sertlik deerleri, beklendii gibi en dk seviyede iken zeltiye alma ve su verme ilemlerinden sonra art gstermitir. Artan yalandrma scaklklar ile ulalan sertlik seviyelerinde azalma eilimi sz konusuyken, genel olarak btn numunelerin benzer sertlik davranna sahip olduklar grlmektedir. 4. SONULAR Doal ve yapay yalandrma ilemleri karlatrldnda alam numune iin yapay yalandrma ilemlerinde daha yksek sertlik deerlerine ulalrken, takviyeli numunelerde ise doal yalandrma ilemlerinde daha yksek deerlere ulalmtr. Artan yalandrma scaklklar, numunelerin sertlik deerlerinde azalmaya neden olmutur. Takviye orannn ana yapnn yalanma karakteristiini etkilemedii, yalnzca ulalan sertlik seviyesini etkiledii belirlenmitir. 5. KAYNAKA 1. Akbulut, Hatem, Otomotiv fren diski ve balatalarn metal matriksli kompozitlerden retimi, DPT Proje No: 2003K120970. 2. Wu, Yan-Lin and Chao, Chuen-Guang, Deformation and fracture of Al2O3/Al-Zn-Mg-Cu metal matrix composites at room and elevated temperatures, Materials Science and Engineering, A282, 193-202, 2000. 3. Rahimian, M et al, The effect of sintering temperature and the amount of reinforcement on the properties of Al/ Al2O3 composites, Materials and Design, 30, 3333-3337, 2009. 4, Shorowordi, K.M. et al, microstructure and nterface characteristics of B4C, SiC and Al2O3 reinforced Al matrix composites: A Comparative Study, Journal of Materials Processing Technology, 142, 738743, 2003. 5, Kiourtsidis, Grigoris E. et al, Aging response of aluminium alloy 2024/silicon carbide particles (SiCp) composites, Materials Science and Engineering A, 382, 351361, 2004. 6 S.Y. Oh, J.A. Cornie, K.C. Russel, Wetting of ceramic particulates with liquid aluminium alloys. Part II. Study of wettability, Metall.Trans. A 20, 533541, 1989. 7 ahin, Y, Preparation and some properties of SiC particle reinforced aluminium alloy composites, Materials and Design, 24, 671-679, 2003. 8 ASTM Standarts, Designation E10-84, Standard Test Method for Brinell Hardness of Metallic Materials, 1984. 9 German, R. M., Toz Metalurjisi ve Parackl Malzeme lemleri, Sarta, S.,Trker, M., Durlu, N.,Trk Toz Metalurjisi Dernei Yaynlar: 05, Ankara, 15-500, 2007. 10 Aye, Shwe Wut Hmon et al, The effect of ageing treatment of aluminum alloys for fuselage structure-light aircraft, Proceedngs of World Academy of Science, Engineering and Technology, Volume 36, ISSN 2070-3740, 2008. 11 Sheu, Cha-Yuan, Ln, Su-Jen, Ageing behaviour of SiCp-reinforced AA 7075 composites, Journal of Materals Scence, 32, 1741-1747, 1997. 12. Gomez de Salazar, J.M., Barrena, M.I., Role Of Al2O3 Particulate Reinforcements on Precipitation in 7005 AlMatrix Composites, Scripta Mater.,44, 24892495, 2001.
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Al-SiC-Grafit kompozitinin Tribolojik Davran

Hlya DURMU*, Salim AHN**, R. Onur Uzun***, Nilay Yksel** Celal Bayar niversitesi, Turgutlu MYO, Makine ve Metal Teknolojileri Blm, Turgutlu-Manisa. hulya.kacar@ bayar.edu.tr ** Celal Bayar niversitesi, Mhendislik Fakltesi, Malzeme Mhendislii Blm, Muradiye-Manisa. Salim.sahin@ bayar.edu.tr, nilay.yuksel@bayar.edu.tr *** Celal Bayar niversitesi, Fen Bilimleri Enstits, Muradiye-Manisa. receponur@gmail.com
*
zet Bu almada, toz metalrjisi (TM) yntemi ile retilen %96 saflktaki alminyum-SiC Grafit numunelerin anma davran incelenmitir. Tribolojik zellikleri pin-on-disk anma cihaz ile belirlenmitir. Kar eleman olarak seramik bilya kullanlmtr. 150 m, 300 m ve 450 m de anma kayplar llmtr. Anma srasnda numunelere 1, 2, 3, 4 ve 5 N yk uygulanmtr. Kayma hz 10 cm/s ve kayma mesafesi 450 m olarak belirlenmitir. Yaplan anma deneyleri sonucunda grafitin, kayma hz ve ykn anma davranlarna etkisi byk olduu grlmtr. Anma mekanizmas daha ok adheziv olduu grlmtr. Anahtar kelimeler: Alminyum tozu, SiC, anma, grafit, mikroyap.
TRIBOLOGICAL BEHAVIOR OF Al-SiC-GRAPHITE COMPOSITE

Abstract In this study, wear behavior of Aluminium at %96 grade-SiC-Graphite samples produced by powder metallurgy (PM) method has been investigated. Tribological properties have been determined by pin-on-disc test machine. Ceramic ball has been used as counter element. Wear loss has been measured at 150m, 300m and 450m. 1, 2, 3, 4 and 5 N loads have been applied on samples during wear test. Sliding speed and distance have been determined respectively 10 cm/s and 450 m. As a result of wear tests, it has been seen that graphite, sliding speed and load have significant effect on wear behavior. It has been observed that, the mechanism of wear was mainly adhesive. Keywords: Aluminium powder, SiC, wear, graphite, microstructure 1.GR Kompozit, srekli bir faz (matris) ierisinde yaylm ayrk bileenlerden oluan ve ayrt edici zelliklerini bileenlerinin zelliklerinden, geometri ve yapsndan ve ayrca farkl bileenler arasndaki arayzlerin zelliklerinden alan malzemelerdir. Alminyum matrisli kompozitler temelde birden fazla trde takviye iermektedir. Grafit parackl alminyum matrisli kompozitler genellikle toz metalurjisi, karma dkm, sktrmal dkm, UPAL yntemi ve topak yntemlerinden biriyle retilir [1]. Toz metalrjisi ok kk partiklleri birbirine balayarak para haline getirme ilemidir. Daha geni bir ifade ile toz metalrjisi, toz eklindeki malzemelerin preslenmesi ve takiben yksek scaklkta sinterlenmesi ile para imalatn kapsamaktadr. nce partikl eklindeki saf metaller, alamlar, karbon, seramik ve plastik malzemeler birbirleriyle kartrlarak basn altnda ekillendirilirler. Daha sonra bu paralar ana bileenin ergime scaklnn altnda bir scaklkta sinterlenerek partikllerinin temas yzeyleri arasnda kuvvetli bir ba oluturulur ve bylece istenilen zellikler elde edilir. Toz metalrjisi kk, karmak ve boyutsal hassasiyeti yksek paralarn seri imalatna son derece uygundur. Malzeme kayb ok azdr, belirli derece porozite (gzenek) ve geirgenlik elde edilir [2].
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Alminyum-grafit takviyeli kompozitler pistonlarda, silindirlerde, trbin rotorlarnda ve yatak burlarnda kullanlmaktadr. Grafitin ilavesi anma direncinin, ilenebilirliinin, snmleme kapasitesinin artmasn ve sl genleme kapasitesinin dmesini salamaktadr. Ancak grafit partikl takviyesinin artmas kompozitin dayanmn drmektedir [3, 4, 5]. Srtnerek alan btn makine elemanlarnda kanlmaz olan kompleks bir sistem zellii gsteren anma, sanayide bir ok tribolojik sistemlerde grlen korozyonun ve yorulmann yan sra nc byk problemdir. Bu nedenden gnmz teknik sistemlerindeki aratrmalar srtnmeyi ve anmay azaltma ve kontrol etme almalar eklinde younlamtr. Srtnmenin ve anmann azaltlmasyla malzeme kayb nlenerek boyut hassasiyeti salanrken enerji israf da nlenmi olur [6]. Kompozit malzemelerde anmay azaltmak iin en sk kullanlan yalayclardan biri grafittir. Birok alma alminyum/grafit kompozitlerinin uygulamalarna odaklanmtr [5]. zellikle deniz tatlarnn dizel motorlarnda kullanlan yataklarda Al-Grafit kompozitlerin kullanm ile srtnme kayplar ve anmay azaltt grlmtr [7]. SiC ilavesi ile kompozitlerin dayanm ve anma direnci artmaktadr [8, 5]. SiC n dezavantaj ilenebilirlii zorlatrmasdr. Dier taraftan grafitin ilavesi ilenebilirlii arttrmakta ve anmay azalmaktadr [9]. Bu almada, Al-SiC-Grafit kompozitleri toz metalurjisi yntemiyle retilmitir. Anma dayanmna grafit miktarnn etkisi incelenmitir. 2.DENEYSEL ALIMALAR 2.1. T/M Para retimi T/M numuneler Alminyum, SiC ve grafit kompozitidir. Tozlar 53 m-75 m arasndadr. Numuneler %90 Al-%10 SiC, %89.5 Al-%10 SiC0.5 Gr, %89 Al-%10 SiC%1 Gr, %88.5 Al - %10 SiC- %1.5 Gr eklinde hazrlanmtr. ncelikle sktrlacak toz karmlar 5 saat kartrlmtr. apraz krlma testi iin retilen numuneler 60x10x10 mm boyutlarndadr. Anma testleri iin ise numunelerin boyutlar 20x10 mm dir. 400 MPa basnta preslenmitir. Daha sonra hazrlanan numuneler 6200 C scaklkta 1 saat boyunca sinterlenmitir. 2.2. Younluk Testi Numunelerin sinterleme ncesi ve sonras younluklar ekil 1de gsterilmitir. Ayrca sinterleme ncesi ve sonras llen boyutlar izelge 1de belirtilmitir. izelge 1 . Sinterleme ncesi ve sonras T/M numunelerin boyutlar Boyut lm %0 Gr %0.5 Gr %1 Gr %1.5 Gr Sinterlemeden nce 10 mm ykseklik 20 mm ap 10 mm ykseklik 20.1 mm ap 10.4 mm ykseklik 20.1mm ap 10 mm ykseklik 20.1 mm ap Sinterleme Sonras 10.6 mm ykseklik 20.1 mm ap 10.2 mm ykseklik 20.15 mm ap 10.4 mm ykseklik 20.3 mm ap 10 mm ykseklik 20.2 mm ap
ekil 1. Sinterleme ncesi ve sonras numunelerin younluklar
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2.3. apraz Krlma Deneyi Krlma Deneyi TS 4222 EN ISO 3325 e gre gerekletirilmitir. Elde edilen dayanm deerleri ekil 2de verilmitir. Grafit miktar arttka dayanm azalmtr (%90 Al-%10 SiC (1), %89.5 Al-%10 SiC0.5 Gr (2), %89 Al-%10 SiC%1 Gr (3), %88.5 Al - %10 SiC- %1.5 Gr (4)). Ted Guo ve Tsaonun almasnda test edilen malzemelerin mekanik karakteristikleri (sertlik, sl genleme katsays ve krlma tokluu), grafit katksnn artyla azalmtr. Bu almada da grafit miktar arttka apraz krlma dayanm azalmtr [1, 5].
ekil 2. Numunelerin apraz krlma dayanm sonular. 2.4. Anma Testi Anma srtnen yzeylerde malzeme kayb olarak tanmlanr. Anma miktar malzemenin trne, srtnen yzeylerin biimine, srtnme koullarna ve evrenin kimyasal etkilerine baldr. Anma testlerinde anma yk 1, 2, 3, 4, 5 N olarak seilmitir (izelge 2). Andrc bilya olarak seramik bilya kullanlmtr. izelge 2. Anma test parametreleri. Al % 90 89,5 89 88,5 90 89,5 89 88,5 90 89,5 89 88,5 90 89,5 89 88,5 90 89,5 89 88,5 Al-SiC-Gr kompozit SiC % Gr % 10 0 10 0,5 10 1 10 1,5 10 0 10 0,5 10 1 10 1,5 10 0 10 0,5 10 1 10 1,5 10 0 10 0,5 10 1 10 1,5 10 0 10 0,5 10 1 10 1,5 Anma Yk 1N 1N 1N 1N 2N 2N 2N 2N 3N 3N 3N 3N 4N 4N 4N 4N 5N 5N 5N 5N
5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
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ekil 3. Anma deneyi sonras numune arlklarndaki deiim
ekil 4. Anma deneyi sonras bilya arlndaki deiim 2.5. Mikroyap ncelemesi Numunelerin mikroyaplar incelenmitir (ekil 5-8)
ekil 5. %0 grafit ieren numune (40x)
ekil 6. %0,5 grafit ieren numune (40x)
ekil 7. % 1 grafit ieren numune (40x)
ekil 8. %1,5 grafit ieren numune (40x)
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3.SONULAR 1. En yksek younluk %1 Gr ieren numunelerde elde edilmitir. 2. Anma deneylerinde yk 4 ve 5 N kullanldnda grafit miktar arttka anma kayb artmtr. 1, 2 ve 3 N kullanldnda ise anma kayb grafit miktar deiimlerinden fazla etkilenmemitir. 3. En dk anma kayb tm ykler iin % 0.5 grafit ieren numunelerde elde edilmitir. Grafit miktarnn artmas mekanik zellikleri dreceinden dolay bu oran en uygun grafit orandr. 4. Kar eleman zerinde anma mesafesi arttka ok az kompozitten yapma olmutur. Kar elemann anma kayb ok az olmutur. 5. Grafit miktar arttnda apraz krlma dayanmnda azalma meydana gelmitir. 4.Kaynaklar 1. A. Marinkovi , A. Vencl, Influence of the Solid Lubricant Particles Reinforcement on Composites Tribological Properties, 11th International Conference on Tribology, 2009 2. S. Akgn Kayral, Plazma Pskrtme Yntemi ile BN, B4C ve SiC Takviyeli Alminyum Kaplamalarn retimi, Karakterizasyonu ve Anma Davrannn ncelenmesi, Celal Bayar niversitesi Fen Bilimleri Enstits, 2011. Y.B. Liu, J.D. Hu, Z.Y. Cao, P.K. Rohatgi, Wear resistance of laser processed Al-Si-graphite composites, wear, 206, 1997, 83-86. 3. G. Rajaram, S. Kumaran, T. Srinivasa Rao, M. Kamaraj, Studies on high temperature wear and its mechanism of Al-Si/graphite composite under dry sliding conditions, Tribology International, 43, 2010, 2152-2158. 4. Karam, M.B., Odaba, D., tektoid alt eliklerin kayma srtnmesinde adhesiv anma katsaysnn aratrlmas, 3. Ulusal Makine Tasarm Ve malat Kongresi, Ankara, 155-163, (1988). 5. Ted Guo ML, Tsao CYA., Tribological behavior of self-lubricating aluminium/ SiC/graphite hybrid composites synthesized by the semi-solid powder densification method, Composites Science and Technology 2000;60:6574. 6. H. Hocheng, S.B. Yen, T. Ishihara, B.K. Yen, Fundamental turning characteristics of a tribology-favored graphite/aluminum alloy composite material, Composites Part A, 28A, 1997, 883-890. 7. S.Suresha, B.K. Sridhara, Effect of addition of graphite particulates on the wear behaviour in aluminium-silicon carbide- graphite composites, Materials and Design, 31, 2010, 1804-1812. 8. S. Suresha, B.K. Sridhara, Wear characteristics of hybrid aluminium matrix composites reinforced with graptite and and silicon carbide particulates, Composites Science and Technology, 70, 2010, 1652-1659.
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The effect of milling speed on particle morphology and particle size of Al 2024 powders prepared by using high energy ball milling
Aykut Canakci1, Temel Varol1, Recep Sen, Sinan Yildiz
1
In the present work, the effect of milling speed on particle morphology and particle size of Al 2024 powders, prepared by high-energy ball milling, was investigated. The powder mixtures were milled in a planetary ball mill for different milling times of 0.5, 1, 2, 4, 6, 8 and 10h. Milling speed was 250rpm and 350rpm and ball to powder weight ratio was 10:1. Because of excessive cold welding for soft material such as Al, process control agent was used to decrease the tendency of cold welding. Methanol was used as process control agent (PCA). Scanning electron microscopy (SEM) was used to evaluate the morphological and microstructural evolution of the powder synthesized by high energy milling. Particle size and powder morphology as a function of milling time were determined. The results show that the increasing milling speed increases the work hardening and fracture occurrence in Al 2024 powder during the milling process, affecting the structural evolution of the powder. 1. Introduction High-Energy ball milling was also known that metal powder particles could be fractured when subjected to heavy plastic deformation. However, if ductile metal powder particles are used, cold welding among them would prevent fragmentation of the particles. Hence, at same stage cold welding could be as rapid as fracturing. This welding could be avoided or minimized by employing special chemicals that act as surfactants, such as stearic acid, methanol. Consequently, cold fracturing take place more easily and effectively to produce finer particles [1]. Mechanical alloying (MA) or high-energy ball milling (HEBM) is solid-state powder processing involving repeated welding, fracturing and rewelding of powder particles in a high-energy ball mill. Process variables in this method such as milling time, milling speed, ball to powder weight ratio and process control agent have effects on the final structure and morphology of the powders [2-5]. High-energy ball milling (mechanical alloying) induces high energy impacts on the charged powder by collision between balls and particles causing severe plastic deformation, repeated fracturing and cold welding of the particles leading to nano crystalline materials [6-9]. The main aim of this study is to investigate the effect of different milling speeds on the morphology and particle size of Al2024 powders. 2. Experimental procedures The as-atomized Al2024 powders (Gndodu Exotherm Company, Turkey) with an average particle size of 111m which varies between 90 m and 125 m was used as raw materials. The chemical composition of as-atomized Al2024 alloy (in wt.%) was 4.85 Cu, 1.78 Mg, 0.385 Si, 0.374 Fe, 0.312Mn, 0.138Zn, 0.042Cr, 0.005Ti and Al (balance). Fig.1 shows the morphology of as received Al2024 alloy powder. The Al2024 alloy powders are ligamental like shape. Powders samples were withdrawn at time of 0.5, 1, 2, 4, 6, 8 and 10h with two different milling speeds of 250 and 350 rpm for morphological and microstructural analyses. The milling process was carried out in a planetary ball mill (Fritsch Gmb, model Pulverisette Premium Line 7) at room temperature using tungsten carbide container. The milling medium component was tungsten carbide balls with 10mm in diameter. The ball-to-powder weight ra-
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tio (BPR) was selected as 10:1. A total of 2 wt % of methanol was added to the ball-mill as process control agent (PCA). To prevent over heating, ball milling experiments were stopped for every 0.5h and then resumed when the temperature of the container decreased to the room temperature. The particle size distribution of as-received and milled powders was quantified by using a laser particle size analyser. The morphology evolution of the powders during milling was investigated by SEM. Apparent density of powder samples were measured using a standard Hall Flowmeter. The microhardness of as-received and milled powders was measured by a microhardness tester (struers microhardness tester) by applying 10g load [10].
Fig.1. Morphology of as-received powders. 3. Results and discussions 3.1 Effect of milling speed on milling process Fig. 2 shows the used milling medium components (ball and vial) and Al2024 powders before and after milling. As it can be seen, the Al2024 powders are little cold-welded to balls due to applied normal force between ball-ball and ball-mill. In fact this phenomenon is due to locally increasing of temperature [11]. Vial and ball surfaces in Fig. 2c are very much cold welded than vial and ball surfaces in Fig.2b due to high efficiency of ball-powder-vial collision. As can be seen in Fig. 2, the Al2024 powders are very much cold-welded to balls and vials surfaces at milling speed of 350rpm (Fig. 2c) than at milling speed of 250rpm (Fig. 2b) due to high efficiency of ball-powders-vial collision. The powder yield could also be lower if the powder gets stuck to vial and ball surfaces due to increase in cold welding caused by the higher degree of plastic deformation [1]. However, morphology and particle size of Al2024 were changed with different milling speeds of 250 rpm and 350 rpm (Fig. 2a, 2b, 2c). It is easy to realize that the faster the mill rotates the higher will be the energy input into the powder. This is because the kinetic energy of the milling medium is impacted to the powder being milled. Therefore, the kinetic energy supplied to the powder is higher at higher relative velocities of the milling medium [1]. Particle size of Al 2024 powders at high milling speed of 350rpm was smaller than at low milling speed at 250rpm due to high efficiency of ball-powder collision.
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(c) Fig.2. Used milling medium components (balls and vial) and Al2024 powders before and after milling. (a) Before milling (b) At 250rpm, after milling (c) At 350rpm, after milling.
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3.2. Powder morphology The main process which takes place in a mill during the MA method to produce quality powders with controlled microstructure is the repeated welding, fracturing, and rewelding of a mixture of powders. The morphology of the initial powders is modified when they are subjected to ball collisions. It is worth noting that the effects of collisions on the milled powders depend on the type of the constituent particles. It has been shown that the initial ball-powder-ball collision causes the ductile metal powders to flatten and work harder when they are cold welded and heavily mechanically deformed. They are brought into intimate contact, forming layered structure of composite particles consisting of various combinations of the starting ingredients, as schematically shown in Fig. 3. Further milling results in cold welding and deformation of the layered particles and a refined microstructure is obtained. Due to the initially low hardness of the starting elemental powders, the lamellar spacing of the agglomerated particles is quickly reduced upon further milling. Increasing the MA time increases the hardness and this leads to fracturing of the agglomerated powders into smaller particles. In the following stage, the welding predominates, causing the equiaxed particle formation. Then welding and fracture mechanism reach equilibrium and the formation of particles with randomly oriented interfacial boundaries. The final stage is characterized by the steady state process, in which the microstructural refinement can continue, but the particle size and size distribution remain approximately the same [12].
Fig. 3. Evolution of different stages of mechanical alloying of a ductile-ductile system according to [12]. The changes of in morphology of particles at 250rpm and 350rpm are showed in Fig. 4 and Fig. 5. It can be observed that different morphologies occurred during high energy milling. During high-energy milling, plastic deformation, cold-welding and fracture are predominant factors, in which the deformation leads to a change in particle shape, cold-welding leads to an increase in particle size and fracture leads to decrease in particle size [13, 14]. Fracture is very low at the beginning of milling for both milling speed due to the lack of enough particles to deform. Fig. 4b shows Al 2024 powder morphology after 0.5h of milling and Al 2024 particles have a flake like shape at this stage. After this stage, until at end of 2h of milling, there is very little change in morphology (Fig. 4c). However, some particles were fractured with increasing milling time particles get work hardened and after 2h of milling, the tendency to fracture predominates over cold welding (Fig. 4d). In other words, work hardening of the deformed particles reached a critical value which led to the activation of the fracture process [2]. Fig. 4e shows the morphology of the powders fractured at the end of 4h of milling. Milled powders exhibited a shape changes from flake-like to nearly spherical or angular shape. As can be seen, Fig. 4d, 4e, after this stage, powder morphology almost unchanged but the fracture continued until the end of 8h of milling. As can be seen Fig. 4f, at the end of 10h of milling, powders agglomerate seriously. There are various reasons for this situation. The most important of these reasons is the low milling speed of vial. Therefore, methanol (PCA) could not be absorbed by the surfaces and powders were agglomerated to each other [10]. In addition, decreasing particle size is one other factor affecting agglomeration [9].
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(a)
(b)
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(d) (e) (f) Fig. 4. Morphologies of Al 2024 powders after different milling time at vial milling speed of 250rpm: (a) 0.5h, (b) 1h, (c)2h, (d) 4h, (e) 8h, and (f)10h [10].
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Fig. 5. Morphologies of Al 2024 powders at milling speed of 350rpm: (a) 0.5h, (b) 1h, (c) 2h, (d) 4h, (e) 8h, and (f)10h. Fig. 5 shows the morphology of the powders of milled at 350 rpm. Similar morphologies are seen with Fig. 4 but fracture is much more than previous procedure (250rpm). Milled powders exhibited a shape changes from flake-like to nearly spherical or angular shape in a short time. Kinetic energy per collosion increases by increase of milling speed from 250 to 350rpm and therefore, particles get more work hardened. Moreover, agglomeration is less than the previous processes. This observation shows fracture is more than previous processes (250rpm). 3.3. Particle size Fig. 6 shows the measurement of particle sizes of the Al 2024 powders for different milling speed and different milling time. The measurment shows that a light difference in particle size can be observed up to 1h of milling. With
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increase in milling time, particle size show a significant change and particle size gradually decreased. As it can be seen, the average particle size of both the process is almost the same at the end of 10h of milling. Meanwhile, there is a significant difference between two different milling speeds (250 and 350rpm). It was reached steady state in first speed of 250rpm but fracture is still continues in second speed of 350rpm at the end of 8h of milling. In other words, ball-impact energy of balls increases because of increasing milling speed so work hardening of particles increases and thus increasing the amount of fractured particles [12].
Fig. 6. The change of particle size with milling speed and milling time. 3.4. Particle microhardness The change of microhardness of milled powders as a function of milling time is shown in Fig.7. In general, increasing the milling time increases the deformation and work hardening of milled powders. In this study, there is a continuous increase in hardness of powders with increasing milling time. Moreover, increasing milling speed increases microhardness of powders due to increasing work hardening.
Fig.7. The change of microhardness with milling speed and milling time. 3.5. Apparent density The first point observed in the high-energy process is the dependence of milling speed and time on apparent density. Fig. 9 shows this dependence for the Al 2024 powders. The predominantly ligamental or irregular morphology of the initial (as received) powders causes bad powder packing, which results in the low initial apparent density values. The ligamental morphology of the shorter-time mechanically milled powders brings good powder packing due to convert into semi-spherical from ligamental powder, and consequently increases in the apparent density values. Then, the laminar morphology of the shorter-time mechanically milled powders brings poorer powder packing, and consequently decreases in the apparent density. After longer milling, the apparent density of the Al 2024 powders reaches a steady value [12].
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Fig. 8. Apparent density changes versus time of mechanical alloying for Al 2024 powders. 4. Conclusion The results indicate that milling speed occurs considerable effects on the milling process, powder morphology and particle size as well as on the structural behaviour of the as milled powder. 1. The Al 2024 powder particles submitted to high energy ball milling are in good agreement with the model description proposed for ductile-ductile systems. 2. Fracture effectiveness of high energy ball milling increases with increasing milling speed. 3. Particle size distribution of Al 2024 powders was homogenous after 8h of milling process and particle size reduction increases with increasing milling speed. 4. Apparent density of Al2024 were changed with different milling speeds and apparent density of 350rpm speed was higher than 250rpm speed for milled Al2024 powders. 5. Microhardness measurements of milled powders indicate their increase in comparison to the initial values of Al 2024 powders for the two different milling speeds and microhardness of 350rpm speed was higher than 250rpm speed for milled Al2024 powders. Acknowledgement The authors are grateful to Karadeniz Technical University Research Fund for the financial supporting of this research work (No: 2007.112.10.2). The researchers would also like to thank to Gundogdu Exotherm Service for providing Al 2024 powders. References 1. C. Suryanarayana, Mechanical alloying and milling, Marcel Dekker, New York, 2004 2. Kh. Gheisari, S. Javadpour, J.T. Oh, M. Ghaffari, Journal of Alloys and Compounds 472 (2009) 416420. 3. I. Estrada-Guel, C. Carreno-Gallardo, D.C. Mendoza-Ruiz, M.Miki-Yoshida, E.Rocha-Rangel, R. MartinezSanchez, Journal of Alloys and Compounds 483 (2009 173177). 4. J.B. Fogagnolo, D. Amador, E.M. Ruiz-Navas, J.M Torralba, Materials Science and Engineering A 433 (2006) 45-49. 5. Syed Nasimul Alam, Materials Science and Engineering A 433 (2006) 161-168. 6. M.M. Rajath Hedge, A.O. Surendranathan, Front. Mater. Sci. China 4(1) (2009) 310-318. 7. R. Daly, M. Khitouni and N. Njeh, Physics Procedia 2 (2009) 685-691. 8. Hafeez Ahamed, V. Senthilkumar, Journal of Alloys and Compounds 505 (2010) 772782 9. L. Lu, M.O. Lai, S. Zhang, journal of Materials Processing Technology 67 (1997) 100-104 10. R. Sen, S. Yildiz, Karadeniz Technical University, Department of Metallurgical and Materials Engineering, Trabzon, Turkey, Graduation Thesis, 41 pages, 2011. 11. S.M. Zebarjad, S.A. Sajjadi, Materials & Design 27 (2006) 684-688. 12. M. Adamiak, Journal of A Achievements in Materials and Manufacturing Engineering, 31(2008) 191-196. 13. C. Suryanarayana, Prog. Mater. Sci., 46 (2001) 1-184. 14. Li. Lu, Y.F. Zhang, Journal of Alloys and Compounds 290 (1999) 279-283.
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The effects of parameters on the synthesis and the piezoelectric properties of PLZT ceramics by sol-gel and mechanical milling methods
Shahab Khameneh Asl *, Shahin Kh. Asl Department of materials science and engineering, Faculty of Mechanical Eng., University of Tabriz, Tabriz, IRAN
Abstract PLZT ceramic powders were successfully prepared from the mixture of zirconium (IV) propoxide, titanium (IV)isopropoxide and lead and lanthanum acetate trihydrate by modified sol-gel synthesis and ZrO2, PbO, TiO2 and La2O3 by high energy mechanical alloying under different conditions. The formation of perovskite phase in the calcined PLZT powder has been investigated by X-ray diffraction (XRD) techniques. The morphology evolution was determined by scanning electron microscopy (SEM) technique. The PZT powders with nanometer grain size were synthesized at a temperature lower than that required in the conventional process. In the present work, PLZT samples were prepared by a sol-gel and mechanical activation methods at a temperature as low as 700C with the particle size in the range of 20-30 nm. Fully dense PZT ceramics with 98% of the theoretical density have been achieved from powders at a sintering temperature of 1200C for 2 h. The good dielectric and ferroelectric properties of the sintered PLZT ceramic were measured for both methods. Keywords: A. PLZT powder, B. sol-gel, C. mechanical activation, D.electrical properties Introduction Lead zirconate titanate PZT with morphotropic phase boundary is one of the most widely used piezoelectric materials with the perovskite structure [1-2]. Other oxides can be added to improved PZTs properties. Substituting the Asites of Pb2+ with La2+ leads to a considerable improvement in the electrical properties of PZT. As the electric valence of the added cations is larger than the electric valence of the original cations, the crystal cell contains a vacancy in the A-site (Pb2+) , As an average , the substitution of two A-site Pb2+ ions with two aliovalent La3+ ions will result in one valance of an Asite in the crystal lattice, This substitution change the material properties, such as dielectric constant, dielectric loss, elastic modulus, etc [3]. PLZT powders traditionally prepared by solid-state reaction processing oxides as the starting materials [4] the conventional method requires a high sintering temperature. This leads to poor microstructure and properties of piezoelectric. One of efforts to avoid this problem is to use ultra fine PLZT powder. This powder can be synthesized by wet-chemical process [5] sol-gel process [6] and hydrothermal reaction [7] and mechanical milling [8]. Reaction sintering is a promising fabrication technique for PZT ceramics in which reaction between constituent phase, take place during sintering process at high temperatures. It is simple process procedure and enhanced densification progress. Shrout et al [9] found that reactive sintering process occurred during the final stages of perovskite formation. Preparation of PZT ceramics via a reactive sintering from their chemically coprecipiated precursors were reported by Xue and Wang [10]. In the present work, ultrafine PLZT powders via sol-gel and mechanical activation processes were synthesized and these mixtures showed a very high sinterability from which the PZT ceramics could be derived at temperatures from 1100oC to 1200oC.
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EXPERIMENTAL PROCEDURE The starting materials were commercially available PbO(99.9%, Merck), ZrO2 (99.9%,Merck), TiO2(99.9%,Merck), La2O3 for solid state methods and Trihydrated lead acetate [Pb(CH3COO)2-3H2O]( analytical grade, Merck), zirconium n-propoxide [Zr(OCH(CH3)2)4](assay 70% in propanol, Fluka), hydrated Lantanium acetate and titanium iso-propoxide [Ti(OCH(CH3)2)4] (for synthesis, Merck )for sol gel method. According to chemical formula Pb1.1(Zr0.53_sLasTi0.47)O3; x = 0.010.05, approximate amounts. of starting materials were weighed. In solid state methods, oxides mixed in an alumina jar for 24 h in ethanol and for activation further milled in planetary ball mill. Milling conditions were the following: stainless steel jar and balls, ball to powder weigh ratio was 20:1, powder quantity was 20 g, air atmosphere, rotation speed of discs was 350 min-1, and milling time was 900 min. In the sol gel method, lead acetate trihydrate and hydrated lanthanum acetate were dissolved in heated acetic acid. The solution was dehydrated at 105C for 2 h and after cooling to 80C it was mixed with the acetate solution of zirconium and titanium propoxide in the required ratio of compounds. By polycondensation of the orange lead zirconyl titanyl acetate after adding a hydrolyzing agent [ethylene glycol, H2O and NH3(aq)] with the temperature of 80C, an yellow sol was formed, which was converted to a gel at the given temperature11. Polycondensation took place in closed flasks. After polycondensation (12 h), it was dried at 100C in 8 h. All powders calcinated in optimum calcinations conditions for the manufacture of perovskite PZT powder. Calcinated powders were subsequently examined by room temperature X-ray diffraction (XRD; SIEMENS D500), using CuK radiation, to identify phase formation. Crystal size and phase formation were analyzed by Sheruder low [12] and standard JCPDS files. The mixtures were pressed in to grain pellets and sintered at 1100C- 1300oC for 2h. The density of PZT ceramics was measured by using Acheron method. The dielectric property of the sintered samples was measured by using impedance analyzer. The ferroelectric properties of the PLZT powders were measured using an RT 66A ferroelectric tester. RESULTS AND DISCUSSION Fig.1 illustrates the XRD patterns of calcined PLZT prepared by mixed oxides and mechanical activation, and solgel methods at 850, 650, 600oC respectively. The patterns for the calcined powder suggest that the phase is mainly perovskite. However, there exist some extra peaks for conventional powders and the broaden peaks with small tail and low crystallinity appeared at 2 at 45 for other methods. After sintering all compositions have the single perovskite phase. It illustrated that there is no secondary phase against La contents will. PLZT derived by sol gel and mechanical activation formed completely in lower temperature than conventional method.
Fig. 1. XRD patterns of calcined (a) mixed oxides 850 C, (b) sol gel600 C, (c) mechanical actived 650 C PLZT at suitable temperatures for 2 h (xxx: PZT, p:PbO, precursors).
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The theoretical density of sintered PZT (52:48) doped with 1.0 5.0% La varied from 8.07 to 7.78 g/cm3 and it slightly deceases with increasing La content for all methods. As illustrated in Table1, The bulk density of samples that ultra fine powders have a good sinterablity than conventional powders at lower temperature. The density of mechanical powders is rapidly increased in low temperature because of its stored stress that can be change to chemical force and its high grain surface that can be released by sintering. The loss of PbO had another effect that caused the decrease in density at high temperatures.
Table 1. Some physical properties of PLZT sintered at various conditions Table 2 summarizes the dielectric constants and some piezoelectric parameters of the ceramics. It was observed that the dielectric constant remarkably increased with increasing sintering temperature initially. It can be found that the dielectric constant of PLZT increases with increasing density but with increasing grain size at high temperature reduces its rate.
Table 2. Dielectric and piezoelectric of PLZT (1%La) Results imply that control of La content and sintering temperature for each process to minimize grain size increases dielectric constant. The value of kp for all conditions reached the maximum (0.47) at 1.00 mol% La before declining steadily for higher La concentration. The value of kp tends to increase with increasing sintering temperature. In contrast, the values of Qm dramatically declined from 225 to 96, and increased slightly for higher La content. Moreover, the Qm tended to decrease with decreasing average grain size for PLZT. The mechanical quality factor, Qm is reduced because of a reduction in the concentration of domain stability. Scanning electron micrographs of the surface morphology of PLZT samples sintered at 1100OC to 1300OC at various compositions are shown in Fig.4. In general, sol gel and mechanical PLZT samples show dense and homogeneous microstructures, it can be seen from Fig. 3 that the grain size significantly decreases when La content is increased from1.0 to 3.0 mol%, and relatively small changes occur for a higher La concentration. SEM images show that an increase in La content and using the sol gel and mechanical methods decease grain size and porosity of samples.
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Fig.4. SEM microstructure of sol-gel PLZT ceramics by 1.00 mol%La sintered for 2 h (a) 1100 (b) 1200 (c) 1300OC CONCLUSION In this study, lanthanum-doped lead zirconate titanates (PLZT) in the area around the morphotropic phase boundary (MPB) have been investigated. The microstructure showed dense grains which tended to become smaller when either increasing La3+ content, or using the activation methods to decreasing sintering temperature. The dielectric constant tended to increase with the activation methods, giving the maximum value of 2000 for 3.0 mol percent La3+ sintered at 1200OC. As the average grain size decreased, the dielectric constant increased. The value of planar coupling factor (kp) was fluctuated and reached the maximum of 0.47 at 1.00 mol% La3+. In addition, the mechanical coupling factor (Qm) of the doped ceramics showed a significant decrease in all cases. The overall results showed that PLZT prepared by sol gel method with 1.0 mol% La sintered at 1200OC have the best properties. REFERENCES [1] B. Jaffe, W.R. Cook Jr., H. Jaffe Piezoelectric Ceramics Academic Press, New York, 1971. [2] Moulson A.J., Herbert J.M. Electroceramics Second Ed.,Wiley Press, 2003. [3] Yang Wein-Duo PZT/PLZT ceramics prepared by hydrolysis and condensation of cetate precursors Ceramic International, 27 (2001) 373-384. [4]. Satter N.,Colla E.L. Ferroelectric Ceramics. Tutorial reviews, theory, Processing, and applications Birkhauser Verlag Basel, 1993 [5] R.N. Das, A. Pathak, P. Pramanik, Low-temperature preparation of nanocrystalline lead zirconate titanate and lead lanthanum zirconate titanate powders using triethanolamine J. Am. Ceram. Soc. 81 12 1998 3357 3360. [6] N. Okada, K. Ishikawa, T. Nomaru Low hysteresis actuator of alkoxide-prepared Pb0.96Sr0.04(Zr0.51Ti0.49) O3 Jpn. J. Appl. Phys. 30 (1991) 22672270. [7] T.R.N. Kutty, R. Balachandan, Direct preparation of lead zirconate titanate by the hydrothermal method Mater. Res. Bull. 19 1984 14791488. [8] Kong L.B., Ma J. PZT ceramics formed directly from oxides via reactive sintering Materials Letters 51(2001), 95100. [9] T. R. Shrout, P. Patant, S. Kim, G.S. Lee conventionally prepared submicrometer Lead- Based provskite powders by reactive calcinations J. Am. Ceram. Soc. 73 (7) (1990) 1862- 1867. [10] J. Xue, J. Wang Lead zrconate titanate via reactive sintering of hydroxide precursors J. Mater. Res. 14 (4) (1990) 1503- 1509. [11] T. Tunkasiri Properties of PZT ceramics prepared from aqueous solution Smart. Mater. Sci. 3 (1994) 243 247. [12] Suryanarayana c.,Mechanical Alloying and Milling, Progress in Materials Sci. USA, 46(2001)1-184.
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THE IMPLEMENTATION OF RESPONSE SURFACE METHODOLOGY FOR THE OPTIMIZATION OF MILLING PARAMETERS IN THE SYNTHESIS OF Cu-Al2O3 POWDER
Ali DORYAB*, Nader PARVIN** and Davoud HAGHSHENAS FATMEHSARI*** * Department of Mining and Metallurgical Engineering, Amirkabir University of Technology, Tehran, Iran, doryab.aut@gmail.com ** Department of Mining and Metallurgical Engineering, Amirkabir University of Technology, Tehran, Iran, nparvin@aut.ac.ir *** Department of Mining and Metallurgical Engineering, Amirkabir University of Technology, Tehran, Iran, davoudhaghshenas@gmail.com ABSTRACT In the present work copper-alumina powder has been successfully produced by mechanical milling. Response Surface Methodology (RSM) was employed to study and optimize the effect of four factors, namely as aluminum solubility in copper, milling time, ball powder ratio (BPR) and milling speed (RPM). The response of the system was the difference in lattice parameter of copper after milling process. Results demonstrated that among all the four factors, only rpm had statistically minor effect on the difference in lattice parameter of copper. The most statistically significant interactions were found to be BPR, solubility of aluminum in copper, and milling time respectively. The proposed model predicted that the maximum value of lattice parameter is 0.356 where solubility of aluminum in copper, BPR, and RPM are 1.1, 10.2, and 1.1 h respectively. X-ray diffraction patterns, verified the RSM values. Keywords: copper-alumina powder, mechanical alloying (MA), response surface methodology (RSM), optimization 1. INTRUCUCTION Mechanical alloying (MA) is a solid-state powder processing technique involving repeated welding, fracturing, and rewelding of powder particles in a high-energy ball mill. Mechanical alloying is a complex process and hence involves optimization of a number of variables to achieve the desired product phase and/or microstructure.For many applications such as electronic packaging or manufacturing of electrodes and contact materials [1], it is required that the materials must have a good combination of electrical conductivity, wear resistance, and resistance to erosion and welding [2]. Mechanical attrition of copper powders with ceramic particles has allowed the uniform introduction of small strengthening phases and also promotes a microstructural grain refinement [3]. Copper-alumina metal matrix composites (MMCs) combine the high electrical and thermal conductivity of the copper phase and high strength and high thermal and chemical stability of the alumina phase. Thus copper-alumina MMCs have the potential to offer both high strength and high electrical conductivity. In order to achieve high fracture toughness and low processing cost, the Alumina phase in the microstructure should be in particulate form, and the particle size should be small. Several techniques can be used to synthesize copperalumina MMCs. Casting is one of the options [4] which has its own problems such as low toughness. This limitation can be avoided by using the powder metallurgy (PM) process. As a way to improve the mechanical properties at low temperatures, the matrix must be strengthened with particles, which have a low diffusivity in the [5-6]. Type of mill, milling container, milling speed, milling time, type, size, and size distribution of the grinding medium, Ball-to-powder weight ratio, extent of filling the vial, milling atmosphere, process control agent (PCA) and temperature of milling [7]. All these process variables are not completely independent.Distribution of reinforcing particles during ball milling is not only dependent on ball milling parameters but also on initial particle sizes [8, 9]. The optimum milling time depends on
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the type of mill, size of the grinding medium, temperature of milling, ball-to-powder ratio and desired phase formation [10]. Another technique is a combination of oxidation and mechanical alloying Cu-Al alloy powder is milled under an oxidizing atmosphere to produce the composite powder.[11] With this technique, Cu powder is first partially oxidized, and then the partially oxidized powder is mechanically alloyed with Al powder to facilitate reactions between CuO (or Cu2O) and Al, forming Al2O3 particles. Also we can use in situ process; the Al2O3 particles were also produced in-situ by the reaction between CuO and Al [12]. Identification of the correct optimum value of the effective parameters in mechanical alloying system is a prerequisite for their successful exploitation. Different parameters identified in previous research as significantly influencing the mechanical alloying system are Al %, time, BPR and RPM [6, 7, 8 and 12]. There are extensive literatures on mechanical alloying systems but an answer to the question of what is the optimum level of processing parameters cannot be reliably found from these studies. This is because in previous studies one-factor-at-a-time methodology has been used to optimize the abovementioned parameters. This methodology is very inefficient and furthermore gives absolutely no information about interactions between parameters in a process. The only methodology capable of providing an answer to this question is factorial design of experiments (DOE). The use of techniques such as Response Surface Methodology (RSM) - is able to simultaneously consider several factors at different levels, and give a suitable model for the relationship between the various factors and the response [13]. The aim of the present work is to evaluate and quantify interaction between important parameters in a mechanical alloying system by using an appropriate methodology, namely RSM. A half fractional factorial central composite design, was chosen as the design matrix since it allows reliable identification of first order interaction between factors and provides a second order polynomial model which can be used to predict optimum level of these parameters [13]. 2. EXPERIMENTAL PROCEDURE 2.1. Materials The materials used in the experiments were Cu powder, purity 99.5%, average particle size 63m), Al (purity 99.5%, average particle size 45 m) and CuO (purity 99%, particle size 63m) powders. 2.2. Experimental Methods Table 1 presents the lists of 28 combinations of factor levels. Hardened steel vial containing tungsten carbide (WC) balls, Ethanol 96 as PCA and the powders were sealed in a glove box filled with high purity Argon. The ball milling was performed in a planetary ball mill. The Cu-Al powder mixture was milled for up to 8 h. In the stage two, CuO powder was added to the optimized Cu(Al) solid solution for up to 8h and mechanically alloyed with ball to powder weight ratio of 4:1. Samples (28 samples) were taken out from the vial and the amount of difference in lattice parameters were studied by X-ray diffraction which was performed in a Philips PW1800 X-ray diffractometer with Cu K Ni filtered radiation. Experiment Number Al % 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Table1. Central composite design arrangement and response Factors 1.0 10.0 1.0 10.0 1.0 10.0 1.0 10.0 1.0 10.0 1.0 10.0 1.0 10.0 time 1.0 1.0 8.0 8.0 1.0 1.0 8.0 8.0 1.0 1.0 8.0 8.0 1.0 1.0 BPR 4 4 4 4 16 16 16 16 4 4 4 4 16 16 rpm 50 50 50 50 50 50 50 50 250 250 250 250 250 250 Response(A) 0.261 0.168 0.210 0.210 0.279 0.279 0.169 0.279 0.298 0.150 0.279 0.184 0.298 0.279
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15 16 17 18 19 20 21 22 23 24 25 26 27 28
1.0 10.0 1.0 10.0 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5
8.0 8.0 4.5 4.5 1.0 8.0 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5
16 16 10 10 10 10 4 16 10 10 10 10 10 10
250 250 150 150 150 150 150 150 50 250 150 150 150 150
0.216 0.245 0.253 0.215 0.295 0.257 0.122 0.174 0.300 0.297 0.245 0.295 0.250 0.260
2.3. Experimental Design for RSM A central composite design (CCD) was adopted to study four factors at three levels. Twenty eight experimental runs consisting of 8 star points (star distance was 0) and 4 center points were generated with 4 factors and 3 levels by the principle of RSM using MINITAB Release 15. The levels employed for the different factors, according to CCD design, are listed in Table 1. The quadratic polynomial regression model (Equation 1) was used for predicting the response variable in terms of the four independent variables: (1) Y is the response variable lattice parameter, b0, bi, bii, and bij are the coefficients of the intercept, linear, quadratic and interaction terms, respectively, and Xi and Xj represent the four independent variables (Al %, time. BPR and RPM).The experiments were carried out with two replicates and conducted in a randomized order to avoid systematic bias. The statistical significance of the full quadratic models predicted was evaluated by the analysis of variance (ANOVA). The significance and the magnitude of the effects estimates for each variable and all their possible linear and quadratic interactions were also determined. . Unless otherwise stated, the significance level employed in the analyses was 5% (p<0.05). Finally, the model was used to predict the optimum value of the factors which result in maximum or fairly high lattice parameter (a). 2.4. Measurements and Analysis Samples were analyzed by X-ray diffraction. Three major peeks were selected and from the Braggs law (Equation 2) and using the least square root method, the lattice parameter of the samples was calculated. Braggs law (2)
The difference between lattice parameter of samples (secondary) and lattice parameter of copper (primary) determined. If the amount of this difference was positive that means aluminum had diffused into copper under these condition and a solid solution of Cu( Al) was formed.. 3. Results and Discussions 3.1. Model Fitting In the design of experiments for estimating statistical models, optimal designs allow parameters to be estimated without bias and with minimum-variance. A non-optimal design requires a greater number of experimental runs to estimate the parameters with the same precision as an optimal design. In practical terms, optimal experiments can reduce the costs of experimentation. RSM, reduces the costs of experimentation by allowing statistical models to be estimated with fewer experimental runs. The following discussion shows how the response surface methodology helps in this regard. Table 1 lists the values of difference of lattice parameters at each of the 28 combination of Factor levels with the values ranging
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from 0.122 A to 0.300 A. The values of the regression coefficients are presented in Table 2. The linear terms, except RPM, as well as the second order terms of the independent parameters, apart from Al %, are significant. The statistical analysis of the interaction terms showed that, at 5% significance level, there are significant interactions between Al %, time and BPR. Based on the calculated values of the regression coefficients (Table 2) a polynomial regression model equation that fitted 88.8% of the variation in the data is proposed as follows (coded values): Response = 0.256 - 0.0141 Al% - 0.0143 time + 0.0188 BPR + 0.053 time time - 0.075 BPR BPR + 0.019 Al% time + 0.0.285 Al% BPR - 0.0145 time BPR (3)
The low values of P determined for the regression (P < 0.001), as well as the fact that the lack of fit of the model was not significant (P > 0.05), revealed the suitability of the model (Table 3). Table 2. Values of calculated regression coefficients (coded values).
Table 3.ANOVA table
3.2. Study of Interactions In the cases where interaction between factors is statistically significant, surface plots give more complete information regarding the effect of a factor on the response. Examination of the surface plot is presented in Figure 1.
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Figure 1 Surface plots for difference of lattice parameter (a) respect to BPR and Al solubility in Copper (%wt) (a), time and Al solubility in Copper (%wt) (b), BPR and time (h) (c) (other parameters are fixed at their middle values). According to the results presented in Table 2,. BPR is the most effective parameter compared to the amount of Al and time, due to higher regression coefficient. Figure 2 illustrates the contour plots of difference of lattice parameter versus the variation of the three significant parameters (Al %, BPR and time). It can be observed that the highest value of response, occurs at a BPR of around 10(dark green regions in Figures 2 a and b).
Figure 2.Contour plots for difference lattice parameter with respect to BPR and Al solubility in Copper (%wt) (a) and BPR and time(h) (b)(Other parameters are fixed at their middle values)
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Also, by increasing of Al% or time, response (difference of lattice parameter) was declined. In red region response is in lowest value where Al% and time are at their highest level and the level of time and Al% should be around 1. The rapid decrease in lattice parameter occured at the very beginning of the milling process, then the change in lattice parameter decreases slowly with the prolonged milling. The decrease in lattice parameter is assumed to be due to the oxidation of dissolved aluminium, which forms as alumina dispersoids. High diffusion rate of oxygen through the deformed copper matrix accelerated the process of oxidation during milling. This result is in agreement with a previous research that investigated the relationship between Cu-3.5 wt. % Al [7]. Lattice parameter and milling time relationship is shown in Figure 3.
Fig. 3. Lattice parameter vs. milling time for Cu-3.5 wt.% Al powder. The BPR has a significant effect on the time required to achieve a particular phase in the powder being milled. The higher the BPR, the shorter is the time required. At a high BPR, the number of collisions per unit time increases and consequently more energy is transferred to the powder particles and so alloying takes place faster. 3.3. Optimization of parameters in the mechanical alloying Initially, optimization of the factors for achieving maximum response was carried out using the proposed second order polynomial model (Equation 3). This exercise The following conditions: Al % = 1.1(%wt), BPR = 10.2, time = 1.1h. To confirm this prediction, and therefore the applicability of the proposed second order model for further optimization exercises, confirmation runs (i.e. runs at the predicted optimum level of the factors) were carried out in triplicate. The 90% confidence interval for deference lattice parameter under optimized conditions was obtained as 0.335 A. (Fig.4)Since the value predicted by the model is within this interval, this can be taken as the confirmation of the suitability of the regression model for predictive purposes [12].
Figure 4. XRD pattern of the Copper-Aluminum powder (optimized variable parameters)
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4. Conclusions It was investigated that Response Surface Methodology has been successfully optimized mechanical milling factors and to examine the effect of four most effective parameters namely as aluminum solubility of copper, time, ball powder ratio and rpm in the mechanical milling of copper-alumina powder. It was shown that BPR is the most effective parameter in compared other variable and It was also found that RPM had statistically insignificant effect on the difference of lattice parameter. A polynomial regression model equation is proposed as follows: Response = 0.256 - 0.0141 Al% - 0.0143 time + 0.0188 BPR + 0.053 time time - 0.075 BPR BPR + 0.019 Al% time + 0.0.285 Al% BPR - 0.0145 time BPR This exercise predicted that the maximum deference of lattice parameter is 0.356 which Aluminum solubility in Copper, BPR, and time were obtained 1.1(%wt), 10.2, and 1.1 h respectively. Acknowledgements The authors would like to thank Sahand Mirzaei, Reza Bahrami for their assistance in the experimental work. References 1. ASM Handbook, Powder Metal Technologies and Applications, vol. 7. ASM, USA, pp. 1020-1030. 1997 2. Chen, W., Kang, Z., Shen, H., Ding, B., Arc erosion behavior of a nanocomposite W-Cu electrical contact material. Rare Met. 25, 37.2006 3. Lopez, M., Jimenez, J.A., Corredor, D., Precipitationcstrengthened high strength- conductivity copper alloysccontaining ZrC ceramics. Composite: Part A 38, 272- 279.2007. 4. M.J. Couper, K. Xia, in: N. Hansen, D. Jnul Jensen, T. Leffers, Proceedings of 12th Ris Symposium on Metal Matrix Composite, Ris National laboratory, Roskilde, Denmark, p. 291.1991 5. Lopez, M., Corredor, D., Camurri, C., Vergara, V., Jimenez, J., 2005.Performance and characterization of dispersion strengthened Cu-Tib2 composite for electrical use. Mater. Charact. 55, pp.252262.2005 6. Omer G uler, The investigation of contact performance of oxide reinforced copper composite via mechanical alloying, journal of materials processing technology, 209,pp.1286-1290,2009. 7. Viseslava Rajkovic, Properties of copper matrix reinforced with nano- and micro-sized Al2O3 particles, Journal of Alloys and Compounds 459,177-184, 2008 8. Suryanarayana, C., Mechanical alloying and milling. Progr. Mater. Sci. 46, 1-184.2001 9. J. Corrochano, The effect of ball milling on the microstructure of powder metallurgy aluminium matrix composites reinforced with MoSi2 intermetallic particles, Composites: Part A, 2011. 10. Ovecoglu, M.L., Ozkal, B., Mechanochemical synthesis of WC powders by mechanical alloying. Key Eng. Mater.pp. 264-268,89-92.2004. 11. E. Bobrova, M. Besterci, Powder Metall. Sci. Tech. 6 (1994) 7 12. D.Y. Ying, Processing of Cu-Al2O3 metal matrix nanocomposite materials by using high energy ball milling, Materials Science and Engineering A286, 152-156, 2000. 13. John Wiley & Sons, Montgomery, D.C. Design and Analysis of Experiments (6th Edition), 2006.
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EFFECT OF MANUFACTURING PARAMETERS ON PHASE GROWTH AND HOMOGENIZATION OF A PM Al/Ni3AL COMPOSITE

Maziyar AZADBEH*, Maryam ABBASI* *Department of Materials Engineering, Sahand University of Technology, P.O. Box 51335-1996, Tabriz, Iran, Corresponding author. Tel.:+98 412 3459446; fax: +98 412 3444333, azadbeh@sut.ac.ir Maryamabbasi86@gmail.com ABSTRACT Aluminum reinforced with intermetallics present a special behavior due to the reaction between matrix and reinforcement. This reaction forms interphases that influence the physical and mechanical properties of Al composites. In this work an approach was made to study of produced interphases in a PM Al/Ni3AL composite, under varying time of mechanical alloying and sintering conditions. To obtain different types of interphases and more homogenization, aluminum powder was mixed with 5 wt.% Ni3Al particles (Intermetallics were obtained by mechanical alloying) followed by uniaxial compacting of a preform, and subsequent sintering at different temperatures (580, 625 and 650C) accomplished. A microstructural study, quantitative and qualitative analysis were carried out by SEM and XRD, showing the chemical gradient formed at the interphase between Al matrix and intermetallic particles under different manufacturing parameters. As well as raising sintering temperature and time of mechanical alloying for producing Ni3Al particles increased diffusion of Ni through intermetallic particles to matrix. At higher temperatures, dissolution of Ni3Al particles occurred with formation of concentric layers of Al3Ni and Al3Ni2 phases. Keywords: PM Al composite, intermetallic Ni3Al, mechanical alloying, manufacturing parameters, homogenization. 1. INTRODUCTION Intermetallics of the Ni-A1 system would be excellent candidates for reinforcement of Al-base because they exhibit a high level of hardness and melting temperature. However, aluminum intermetallic compounds are so brittle that it alone cannot serve as a structural material. Attempts have been made to compensate the brittleness by embedding it in a ductile matrix material. These metal matrix composites (MMCs) are currently being investigated because of their superior properties as compared to those of most conventional materials [1, 2, 3, 4]. The interfacial characteristics in metal matrix composites play an important role in determining the resultant composite properties. This is because superior material properties in MMCs are attributed to the efficiency of the load transfer from the matrix to the reinforcements through the matrixreinforcement interface [5]. The degree of property enhancement depends also on morphological factors such as volume fraction, size and spatial distribution of the reinforcement phase arising from manufacturing parameters. The major obstacle to the application of such materials is chemical reaction and interfacial bonding at reinforcement/ matrix interfaces during materials processing [6], that affecting mechanical properties and corrosion resistance. In order to solve this problem, some special techniques, such as adjustment of the chemical composition of the matrix and manufacturing parameters such as sintering temperature in PM route are used therefore optimum sintering temperature in PM route can be the main key in attaining improved properties.
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However deleterious reaction products at intermetallic/matrix interfaces may form during sintering or solid solution treatments giving rise to brittle interphases and modifications in matrix composition, which result in the worsening of mechanical properties. In some cases such as Al/NiAl, better bonding of the reinforcement to matrix gives better mechanical behavior of composite, while the produced reinforcement is more brittle [7,8]. As well as the mechanical alloying process changes dramatically the powder characteristics, the more refined microstructure improved dispersion of the reinforcement particles and improved mechanical properties can be achieved with this process route. The aim of this study was investigation on the effect of manufacturing parameters such as different sintering temperatures and MA exposure time on characterization of the microstructure of aluminum matrix/Ni3Al interface in Al/ Ni3Al composite where aluminides have been formed as the effect of diffusion and interaction between Ni and Al. Depend on type and amount of created intermetallics at reinforcement/matrix interfaces, varying physical and mechanical properties will be achieved. Therefore main role of manufacturing parameters on obtained properties of composite should be considered. 2. EXPERIMENTAL PROCEDURE Aluminum matrix composites were produced employing pure aluminum as metal matrix when nanostructure Ni3Al intermetallic particles were used as reinforcement. Aluminum powder from Merck Co. (Germany) was used as a matrix material. Reinforcement particles used were the nanostructure Ni3Al Nickel aluminide (particles size less than 100 nm) produced in mechanical alloying process with the conditions given in Table 1. To investigate the effect of starting intermetallic reinforcement size on interfacial bonding and more homogenization two different sizes of reinforcement were produced by selecting two appropriate mechanical alloying times (15 and 55 h). The powders of Aluminum and Ni3Al were mixed to give the nominal composition Al5wt.%Ni3Al. The obtained mixed powders were cold compacted uniaxially in the cylindrical matrix 14mm in diameter with floating die and oil graphite die wall lubricated. The compacting pressure was chosen equal to 400 MPa for 300 second. To investigate the effect of sintering temperature on homogenization and interphase reaction, the compacted samples were sintered at 580, 625, 650C in a vacuum furnace for 30 min followed by furnace cooling. Densities of the sintered parts were determined using Archimedes principle (DIN ISO 3369). Microstructural observations were made by optical microscopy (OM) and scanning electron microscopy (SEM). The produced layers through diffusion of Ni at matrix/reinforcement interfaces were identified by energy-dispersive X-ray (EDX) analysis. As well as the produced interphases under different sintering temperatures were obtained by XRD examinations. To determine macro-microhardness values, Vickers tests were performed in the carefully sectioned and polished specimens. Vickers macro-microhardness values were the average of at least 10 indentations by applying 30 kg and 25 g load for 15 s respectively. Table1. Parameters of mechanical alloying for producing Ni3Al
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3. RESULTS AND DISCUTION In order to evaluate the effect of mechanical alloying on the reinforcement grain size, XRD analysis was performed (see Figure 1).
Figure 1- X-ray diffraction pattern of elemental mixture powders and after 15 h and 55 h mechanical alloying for the composition Ni75Al25, used as nanostructure reinforcement in fabrication of Aluminum matrix composite Peak line broadening represented a decrease in the crystalline size of nanostructure Ni3Al and accumulation of lattice strain with increasing time of mechanical alloying. The analysis of the XRD peaks was performed via the WilliamsonHall method. The evolution of matrixreinforcement interface and spatial distribution of the reinforcement in the matrix in Al/5 wt% Ni3Al composite during sintering at three different sintering temperatures (580, 625 and 650C) was followed by optical microscopy and SEM observations on specimens prepared by embedding the sintered samples in epoxy resin followed by conventional metallographic polishing.
Sintering Temperature=580C
Figure 2. Microstructure of sintered Aluminium matrix composite particle reinforced with 5 wt.% Ni3Al particles after 15 h of mechanical alloying Figure 2 shows low sintering temperature (e.g. 580C) can not eliminate the void around intermetallic that originated at particle matrix interface and generated primarily by decohesion of the matrix-particle interface. Therefore the bonding between the matrix and intermetallic particles is not strong and thickness of diffusion layer around the intermellic is negligible. Microstructure of the composite sintered at 580 shows that Ni3Al particle reinforcements remain approximately intact. With increasing sintering temperature diffusive layers will be extended and reaction phases improve the bonding. An analysis of the chemical composition by the energy dispersive X-ray (EDX) method in vicinity of the interface with the matrix of sintered composite at 625C, has shown the following contents: 24.37 at.% of Al and 75.63 at.% of
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Ni in the inner layer of reinforcement, 60.11 at.% of Al and 39.89 at.% of Ni in the middle layer of reinforcement and 75.22 at.% of Al and 24.78 at.% of Ni in the outer layer of interface (Figure 3). The EDX results and XRD patterns of sintered composite at different sintering temperatures (Figure 4), confirm OM and SEM observations of the formation of a multilayer at matrixreinforcement interface in Al/Ni3Al composite, sintered at 625C for 30 min.
Figure 3. EDX measurements in the diffusion zone around interface for Al+ 5wt.%Ni3Al, sintered at 625C for 30 min As it can be seen in Figure 2, higher sintering temperatures help more the diffusion of elements at matrix-reinforcement interfacial. The spatial distribution of the reinforcement phase in matrix arising from sintering at 650C is larger than it created at 625C. As well as pores in the microstructure of sintered composite at 650C are more rounded with respect to other samples that sintered at lower temperatures. Exothermic reaction due to the formation of Ni-Al intermetallic compound [9] during sintering of Al/5 wt.%Ni3Al composite at 650C causes heat flow through the Aluminum matrix that contribute to eliminate pores and make them round. Comparison of the microstructure in Figure 2 shows that the thickness of interfacial layer increases with rising sintering temperature. Comparing the microstructure of sintered composite at different temperatures in Figure 2 shows that the new phases at interface also have the effect of increasing volume locally, compressing the matrix around the intermetallic particles, which is due to the different densities of the three Ni-aluminides [10] (7.45, 4.75 and 3.95 g/cm3 respectively for Ni3Al, Al3Ni2 and Al3Ni). The Obtained microstructures under different manufacturing parameters are in a good coordination with measured sintered density. Density was determined by Archimedes principle (DIN ISO 3369) since this method is more precise than calculating the density from the dimensions. The sintered density values for Al/ 5 wt.%Ni3Al composite sintered at 580, 625 and 650C are 2.79, 2.88 and 2.89 g/cm3, respectively.
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Figure 4. X-ray diffraction pattern of Al/Nickel aluminide composite as green and assintered at different temperatures. The peaks are labeled accordingly It can be concluded that at higher sintering temperature (625 and 650C) dissolution of the Ni3Al intermetallic in Al/5wt.%Ni3Al composite occurs with formation of concentric layers of Al3Ni and Al3Ni2 reaction products according to the following sequence: Firstly the Al3Ni phase nucleates and grows enveloping the dissolving Ni3Al nucleus. This can be attributed to solidstate inter-diffusion that occurs between aluminum and nickel at temperatures below the eutectic temperature and form predominantly aluminum-rich compounds. Then the Al3Ni2 phase nucleates and grows between the remaining Ni3Al nucleus and the growing Al3Ni layer. These phase transformation are exothermic which subsequently heat the compact and thus triggering a reaction as well as it can be act as a driving force for diffusion of Ni and Al. Finally, the Ni3Al and Al3Ni2 phases completely dissolve and the equilibrium Al3Ni phase remains. Constituent phases of interfacial layer created in Al/Ni3Al that sintered at 625C for 30 min were studied by microhardness measurements. The results of these measurements on the inner, middle, outer layer of diffusion bond and matrix are shown in Figure 5. The microhardness of the produced intermetallic in the inner, middle and outer layers and Aluminum matrix are of about 922, 1100, 770 and 59 HV0.025 respectively
Figure 5. Microhardness values (HV 0.025) of constituent phases at matrix reinforcement interface in Al + 5 wt.% Ni3Al, sintered at 625C for 30 min The results of macrohardness measurements with a load of 30 kg (HV 30) for sintered samples are graphically depicted in Figure 6. With increasing sintering temperature, the hardness of sintered samples increases. This behavior is a consequence of the formation of diffusion reaction phases and better bonding of the reinforcement to matrix at higher sintering temperature that affects the hardness of composite
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Figure 6. Macrohardness of sintered Al + 5 wt.% Ni3Al particles (15 h MA) at different temperatures In order to investigate the effect of time of mechanical alloying process on interfacial bonding at reinforcement/ matrix interfaces, sticking reinforcement to matrix and more homogenization, Ni3Al particles that produced after 15 and 55 h mechanical alloying were used as reinforcement component in aluminum matrix composite (Figure 7). To reveal the effect of reinforcement grain size on thickness of diffusion layer, specimens were sintered at 625C for 30 min. At this sintering temperature, multilayer interface is seen obviously in the microstructure (see Figure 2 and Figure 3). Figure 7a shows Ni3Al particles (15 h MA) that surrounding by diffusion layers and Ni-Aluminide components have been created. In the meanwhile it is seen in Figure 7b that Ni3Al particles (55 h MA) change to Al3Ni, due to diffusion Ni to the Aluminum matrix and Aluminum to reinforcement particle and more dissolution of Ni3Al occurs. Increasing time of mechanical alloying generate more defects such as vacancy besides more stored strain energy in the powders due to large plastic deformation. The stored elastic energy, small volume to surface ratio are the main parameters in creating the condition which led to the increase of reaction rate by providing short circuit diffusion path. The numerous interfaces provide a high density of short-circuit diffusion paths hence very enhanced diffusion rates are expected for Ni3Al particles after 55 h of mechanical alloying in comparison with particles proceed after 15 h of mechanical alloying. This enhanced diffusivity can have significant effect on spreading intermetallic phases at interfacial. The increased diffusivity leads to increased sinterability and sticking reinforcement to matrix. As well as the formation of Al3Ni leads to swelling of the compact and Kirkendall porosity due to unbalanced diffusivities of nickel and aluminum. This phenomenon is more obvious in the case of composite with fine intermetallic reinforcement because of rapid reaction between intermetallic and Aluminum matrix.
Figure 7. Microstructure of sintered Aluminium matrix composite particle reinforced with 5 wt.% Ni3Al particles after 15 h and 55 h of mechanical alloying, sintered at 625C for 30 min
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4. CONCLUSION 1. Sintering temperature is one of the critical parameters in manufacturing of PM composite, which influence interfacial characteristics in metal matrix composites, sintered density and obtained physical and mechanical properties. 2. At higher sintering temperature (625 and 650C) dissolution of the Ni3Al intermetallic in Al/5 wt.%Ni3Al composite occurs with formation of concentric layers of Al3Ni. The Al3Ni phase nucleates and grows enveloping the dissolving Ni3Al nucleus. Then the Al3Ni2 phase nucleates and grows between the remaining Ni3Al nucleus and the growing Al3Ni layer; finally the Ni3Al and Al3Ni2 phases completely dissolve and the equilibrium Al3Ni phase remains. 3. The fine Ni3Al reinforcements produced from prolonged mechanical alloying procedure promote the diffusion process owing to large deformation of powder particles and hence more stored strain energy. Consequently, thicker diffusive layers formed around the fine reinforcements during sintering and produce a composite with decreased porosity percentage in comparison with the coarse intermetallic reinforcements at the same sintering temperature. 4. Powder metallurgy is the most suitable method for processing Aluminum matrix composite reinforced with intermetallic particles, because of its capacity to control reactions between matrix and reinforcement by proper selecting of sintering temperature, exposure time in sintering process, size of intermetallic particles in other words mechanical milling time and other manufacturing parameters applied to production procedure of starting powder and other sequences of composite synthesis. Therefore importance of manufacturing parameters on achieved properties of composite should take into account. 5. REFERENCES 1. - C. Di.Az, J.L. Gonzalez-Carrasco, G. Caruana, and M. Lieblich, Ni3AI Intermetallic Particles As Wear-Resistant Reinforcement for AI-Base Composites Processed by Powder Metallurgy, Metallurgical and Materials Transactions A, Vol. 27A, OCTOBER 1996, 3259-3266. 2 - W.H. Xu, X.K. Meng, C.S. Yuan, A.H.W. Ngan, K.L. Wang, Z.G. Liu, The Synthesis and Mechanical Property Evaluation of Ni/Ni3Al Microlaminates, Materials Letters, 46 (2000) 303308. 3 - L. DAngelo, G. Gonzalez, J. Ochoa, Phase Transformations Study on Ni75Al25 and Ni50Al50 During Mechanical Alloying and Sintering, Journal of Alloys and Compounds, 434435 (2007) 348353. 4 - M. Krasnowski, A. Antolak, T. Kulik, Nanocrystalline Ni3Al Alloy Produced by Mechanical Alloying of Nickel Aluminides and Hot-Pressing Consolidation, Journal of Alloys and Compounds, 434435 (2007) 344347. 5 - I.G. Waston, P.D. Lee, R.J. Dashwood, and P. Young, Simulation of the Mechanical Properties of an Aluminum Matrix Composite using X-ray Microtomography, Metallurgical and Materials Transactions A, Vol. 37A, March 2006551. 6 - M. Adamiaka, J.B. Fogagnolo, E.M. Ruiz-Navas, L.A. Dobrzaski, J.M. Torralba, Mechanically Milled AA6061/(Ti3Al)P MMC Reinforced with Intermetallics The Structure and Properties, Journal of Materials Processing Technology, 155156 (2004) 20022006. 7 - Hiroshi Okada, Yasuyoshi Fukui, Ryoichi Sako, Noriyoshi Kumazawa, Numerical Analysis on Near Net Shape Forming of AlAl3Ni Functionally Graded Material, Composites, Part A 34 (2003) 371382. 8 - H.A. Pour, M. Lieblich, A.J. Lopez, J. Rams, M.T. Salehi, S.G. Shabestari, Assessment of Tensile Behaviour of an AlMg Alloy Composite Reinforced with NiAl and Oxidized NiAl Powder Particles Helped by Nanoindentation, Composites, Part A 38 (2007) 25362540. 9 - L. Lu, M. O. Lai and S. Zhang, Thermodynamic Properties of Mechanically Alloyed Nickel and Aluminum Powders, Materials Research Bulletin , Vol. 29, No. 8, 1994, 889-894. 10 - H.A. Pour, M. Lieblich, A.J. Lopez, J. Rams, M.T. Salehi, S.G. Shabestari, Assessment of Tensile Behaviour of an AlMg Alloy Composite Reinforced with NiAl and Oxidized NiAl Powder Particles Helped by Nanoindentation, Composites, Part A 38 (2007) 25362540.
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TOZ METAL PSKRTME YNTEM LE BORU YZEYLERNN KAPLANMASI VE KARAKTERZASYONU

Erdal KARADENZ*, smail CEYLAN**, Uur ZSARA***, Azim GKE***
*
Sakarya niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, Sakarya ** PETKM, Aliaa, zmir *** Sakarya niversitesi, Teknik Eitim Fakltesi, Metal Eitimi Blm, Sakarya ZET
Bu almada, 4, 6 ve 10 ASTM A106 Grade A dikisiz elik borularn i yzeyleri bronz tozlar ile toz alev pskrtme yntemiyle kaplanmtr. Deneysel almalarda, toz pskrtme mesafesi ve hava basnc, deiken kaplama parametreleri olarak alnmtr. Pskrtme mesafesi olarak 50 mm, 100 mm ve 150 mm mesafe ve hava basnc olarak da 0, 0.5, 1 ve 2 bar deerleri kullanlmtr. Standartlarda 150 mm- 250 mm aras toz pskrtme mesafesi tavsiye edilmektedir. Daha kk apl yataklarn i yzeylerinin kaplanmas iin, pskrtme mesafesi azal ile kaplamann gerekletirilebilirlii aratrlmtr. Bunun iin pskrtme hava basnc deerleri deitirilerek allmtr. Deneylerde elde edilen numunelerin ara yzeyleri, mikrosertlik deerleri, yzey przllkleri ve balanma mukavemetleri incelenerek deiken parametrelerin bunlara olan etkileri tespit edilmitir. Anahtar kelimeler: Toz metal, Bronz, Alev pskrtme, Dikisiz boru
INVESTIGATION AND CHARACTERIZATION OF INNER SURFACES OF PIPES COATED BY POWDER SPRAY PROCESS
ABSTRACT In this study, 4, 6 and 10 ASTM A106 GRADE A-seamless steel pipes inner surfaces were coated with bronze metal powders by powder flame spraying method. Spray distance and air pressure were chosen as variable parameters. Spray distances were chosen as 50, 100 and 150 mm and air pressures were chosen as 0, 0,5, 1 and 2 bar. The recommended powder spray distance is 150-250 mm in standards, so the investigation of the coating of smaller diameter pipe inner surfaces was aimed. Therefore, spray air pressure values were changed variously. The interval surface images, micro hardness measurements, surface roughness and bonding strengths of specimens were investigated to see how they were affected by these parameters. Keywords: Surface Coating, Thermal Spray, Flame Spray, Compressed air pressure, Spray distance 1. GR Ar evre artlarnda alacak gerekli dayanklla sahip ana metalleri, bu artlarn zararl etkilerinden korumak iin ok daha ucuz bir yntem olan, dayankl ana metalin yzeyini evre artlarndan etkilenmeyen zellie sahip malzemelerle kaplama teknolojisi gelitirilmi ve yzey kaplama teknolojisi olarak isimlendirilmitir. Burada kaplanan yzeyler genellikle metal olmakla beraber, nadir durumlarda baz metal olmayan yzeylerin kaplanmas da olasdr. Nispeten ucuz olan ve asl yk tayan ana malzemeler, uygun kaplama malzemeleri ile kaplanarak anmaya, korozyona ve sya dayankl hale getirilebilir [1]. letmelerde karlalan en byk sorunlardan biri de anan veya krlan makine paralardr. Krlan makine paralar eitli kaynak yntemleriyle tamir edilebilir. Anma nedeniyle isletme toleranslarnn dna km paralar ise eitli kaplama yntemleriyle kaplanarak tekrar orijinal l deerlerine getirilebilir. alma ortamndaki artlardan dolay ortaya kan bu problemin nne gemek iin
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anan makine paralarnn yzeylerinin neden andnn doru olarak belirlenmesi ve bu anma faktrne dayankl bir malzeme ile kaplama yaplarak parann alma mrn uzatlmas mmkndr [2]. Metaller zerine uygulanan kaplamalar, iki temel prensibe gre yaplmaktadr: (i) Kaplama ile metal arasnda bir difzyon ba oluturarak ve (ii) Kaplama ile metal arasnda herhangi bir difzyon ba olmakszn metal-kaplama arasndaki mekanik yapma ile balanmas. Difzyonlu kaplamalarda, metal ile kaplama arasndaki ban zellikleri, malzeme bileimleriyle dorudan ilikilidir (rnein; galvaniz kaplama). Toz pskrtme gibi difzyonsuz kaplamalarda ise, kaplama ve metal arasndaki mekanik yapma tamamen kaplama prosesi artlarna baldr [3]. Difzyonsuz kaplama yntemlerinden Termal sprey genel bir ifadeyle benzer prosesler vastas ile metalik ve metalik olmayan kaplamalarn uygulanmas iin yaygn olarak kullanlan bir gurup prosesi ifade etmektedir. ok sayda termal sprey ilemi mevcut olmakla birlikte ticari olarak kullanlan drt temel metot: 1- Alev Pskrme (Toz alev pskrtme ve tel alev pskrtme), 2- Ark Pskrtme, 3- Detanasyon Alev Pskrtme ve 4- Plazma Pskrtmedir. Bu teknikler ile yumuak metallerden son derece sert seramiklere kadar ok geni bir aralktaki malzemeler ile hemen hemen tm altlk malzemelerin kaplanmas mmkn olmaktadr. Ayrca bir malzemenin yzeyine ince bir tabakann spreylenmesi anmaya, korozyona ve sya kars direnci artrmakta ve ayrca altlk malzemenin zelliklerini etkilememektedir [4]. Bu almada ASTM A106 Karbon elik boru malzemesinin i yzeyine toz alev pskrtme yntemi kullanlarak bronz kaplama tozu pskrtlm ve malzeme yzeyi souk pskrtme yntemiyle kaplanmtr. 2. DENEYSEL ALIMALAR 2.1. Materyal ve Yntem Toz Alev Pskrtme ynteminde toz halindeki ilave metal bir sevk gaz ve sevk dzenei ile iletildii oksi-asetilen alevi iinde eritilir ve asetilen-oksijen karmnn yanmas ile oluan genleme yardmyla hzlandrlr (kinetik enerji) ve kaplanacak para yzeye pskrtlr. Sekil 1,1de toz alev pskrtme yntemi ematik olarak grlmektedir.
ekil 1. Toz alev pskrtme ynteminin gsterimi [5]. Deneysel almalar iin 4, 6 ve 10 aplarnda izelge 1de kimyasal kompozisyonu verilen ASTM A106 GRADE A dikisiz karbon elik borularn i yzeyleri toz pskrtme yntemiyle Castolin firmasna ait Xuper Frixtec 19850 Bakr-Alminyum alaml toz ile kaplanmtr. Borularn i aplarndaki farkllk nedeniyle pskrtme mesafesi 4 borularda 50 mm, 6 borularda 100 mm ve 10 borularda 150 mm olarak tasarlanmtr. izelge 1. Altlk olarak kullanlan elik boru malzemenin kimyasal kompozisyonu. Element % 2.2. Hazrlk Drt adet 4, adet 6 ve iki adet 10 boru tornada 100 mm boylarnda kesilerek hazrlanmtr. Daha sonra borularn i yzeylerinden ve d yzeylerinden korozyonlu tabakalar tornada alnmtr. 4 borularn i ap 90mmye, 6 borularn i ap 143 mm.ye, 10 borularn i ap 247 mmye islenmitir. Malzeme ieriindeki nemden C 0,25 Mn 0,61 Si 0,09 P 0,025 S 0,32 Cu 0,32 Ni 0,31 Cr 0,28 Mo 0,11 V 0,07
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arndrlmak iin 60 C ye kadar n tavlamaya tabii tutulmutur. Kaplama ilemi esnasnda malzeme scakl Raytek PM Plus Model RAYPM30L2ISG termal tabanca ile kontrol edilmitir (ekil 2).
ekil 2. Termal tabanca ile scaklk kontrol.
ekil 3. Kaplama ncesi iine di alm boru
n tavlamadan sonra borunun iine tornada 0,75 mm adma sahip di almtr (ekil 3). Ardndan hemen kaplama ilemine balanmtr. 2.3. Toz Metal Pskrtme ile Kaplama lemi Kaplama ilemi PETKM A.S. Merkez Bakm Atlyesinde yaplmtr. Kaplamalar Castolin firmasna ait ROTOTEC 80 Toz pskrtme tabancas ile yaplmtr. Borunun i yzeyine kaplama yapld iin kaplama uzatma nozulu kullanlarak yaplmtr. (ekil 4).
ekil 4. Toz pskrtme tabancas i ap kaplama ( uzatma ) nozulu. Aada ekil 5te gsterildii gibi asetilen ve oksijen deerleri Castolin firmasnn verdii deerlere gre ayarlanm ve ntr alev kullanlmtr. Asetilen basnc 0,7 bar, oksijen basnc 4 bar olarak ayarlanmtr. ROTOTEC 80 cihaznn zelliinden dolay toz besleme debisi sabittir. Tm kaplamalarda ayn toz debisi ile kaplama yaplmtr. Malzemeye M 0,75 di aldktan sonra balayc toz olarak Xuper Ultrabond 51000 tozu ile 0,1 mm kalnlnda astar kaplama yaplmtr. Btn kaplamalarda astar kaplama esnasnda 0 bar basncnda hava kullanlmtr. 4 borularda 50 mm uzaklktan pskrtme yaplarak, hava basnlar 0, 0,5, 1 ve 2 bar olacak ekilde 4 adet boru i yzeyine 1,5 mm kalnlnda kaplama ilemi yaplmtr. 6 borularda 100 mm uzaklktan pskrtme yaplarak, hava basnlar 0, 1 ve 2 bar olacak ekilde 3 adet boru i yzeyine 1,5 mm kaplama ilemi yaplmtr. 10 borularda 150 mm uzaklktan pskrtme yaplarak, hava basnlar 1 ve 2 bar olacak ekilde 2 adet boru i yzeyine 1,5 mm kaplama ilemi yaplmtr (ekil 6). Kaplamalar esnasnda malzeme scakl termal pirometre ile kontrol edilerek malzeme scaklnn 260 Cyi gememesi salanmtr. Malzeme bu scakla ulatnda bir mddet soumaya braklm sonra tekrar devam edilmitir. Kaplama yaplan numuneler ak havada soumaya braklmtr. Souyan malzemelerin i aplarndan 0,5 mm tala alnarak kaplama kalnlklar 1 mm ye drlmtr.
ekil 5. Toz pskrtme tabancas ve gaz ayarlar.
ekil 6. Alev toz pskrtme yntemiyle kaplama.
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3. DENEYSEL SONULAR Yaplan kaplamalarda deiken parametreler olarak hava basnc ve pskrtme mesafesi kullanlmtr. Dier parametreler tm kaplamalarda ayn tutulmutur. Deiken parametrelere gre numunelere verilen kodlar izelge 2de verilmitir. izelge 2. Kaplamalar iin pskrtme parametreleri Numune Kodu A1 A2 A3 A4 B1 B3 B4 C3 C4 Hava Basnc (bar) 0 0,5 1 2 0 1 2 1 2 Pskrtme Mesafesi (mm) 50 50 50 50 100 100 100 150 150
3.1. Mikroyap Ara Yzey Mikroyaplarnn ncelenmesi optik mikroskopta yaplm, elde edilen mikroyaplar aadaki ekillerde verilmitir. Btn mikroyap grntleri 50x bytmede ekilmitir.
ekil 7. A1 kaplamas optik mikroskop grnts.
Yukarda ekil7 deki A1 kaplamas incelendiinde kaplama ara yzeyinde astar tabakas ak renkte grnmektedir. Ortalama 0,1 mm kalnlnda ince bir astar tabaka varl sz konusudur. Kaplama tabakasnda ba tabakas ile st kaplama arasndaki ara yzeydeki siyahlklar boluklar temsil etmektedir. Bu grnt iki tabakann birbirine iyi tutunmadn gstermektedir. Kaplamann grnts, dalgal klasik termal sprey grntsdr. Fakat homojen byklkte olmayan porozite varl gze arpmaktadr. Byklkleri ok farkllk gstermektedir. Sekil 8de 50 mm pskrtme mesafeli 0,5 bar pskrtme basnl A2 numunesinden elde edilen mikroyap fotoraf grlmektedir. A2 numunesi mikroyap fotoraflar incelendiinde, basncn arttrlmas kaplamada A1 numunesine gre daha youn bir yap olumasna sebep olmu grlmektedir. Fakat porozite dalm ve bykl hala homojen deildir. Yapma mukavemetine ynelik, ara yzeyde esas metal-ba tabakas ve st katman balants gayet iyi grnmektedir.
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Sekil 9da 50 mm pskrtme mesafeli ve 1 bar pskrtme basnl A3 numunesinden elde edilen mikroyap fotoraflar grlmektedir. Basncn 1 bara karlmas porozite dalmnn daha homojen olmasna yol am grnmektedir. Ara ba ile altlk ve st katman aras balanmann iyi olduu grlmektedir. Mikroyapda dikkati eken nokta, kaplama iinde yuvarlak formda ergimemi partikllerin varldr. Bu durum basncn yksek olmasndan dolay tozlarn ergimek iin alev ierisinde fazla kalamadn gstermektedir. Sekil 10da 50 mm pskrtme mesafeli ve 2 bar pskrtme basnl A4 numunesinden elde edilen mikroyap fotoraflar grlmektedir. Basncn 2 bara arttrlmas, porozitenin arttn gstermektedir. Ayrca tozlar ergimeden mikro yap bnyesine girmitir. Byk boluklar sz konusudur ve bu boluklar iin porozite tabiri dahi yetersiz kalmaktadr.
ekil 11. B1 kaplamas optik mikroskop grnts.
ekil 12. B3 kaplamas optik mikroskop grnts.
Yukarda Sekil 11de 100 mm pskrtme mesafeli ve 0 bar pskrtme basnl B1 numunesinden elde edilen mikroyap fotoraflar grlmektedir. B1 numunesi mikroyap fotoraflarnda porozite miktar daha az ve genel olarak iyi bir kaplama yaps grlmektedir. Pskrtme mesafesinin 100 mmye karlmas kaplama yapsna olumlu yansm durumdadr. 50 mmden pskrtme yaplan A-grubu kaplamalar ile kyaslandnda, pskrtme mesafesinin 100 mmye karlmasnn kaplama yapsna olumlu yansd grlmektedir. Seki 12de 100 mm pskrtme mesafeli ve 1 bar pskrtme basnl B3 numunesinden elde edilen mikroyap fotoraflar grlmektedir. B3 numunesi mikroyap fotoraflarnda baz ergimemi partikllerin varl gze arpmaktadr. Yapsal olarak normale yakn bir kaplama yaps gze arpmaktadr. Ba tabakas burada daha ince grnmektedir. Sekil 13de 100 mm pskrtme mesafeli ve 2 bar pskrtme basnl B4 numunesinden elde edilen mikroyap fotoraflar grlmektedir. B4 numunesi mikroyap fotoraflarnda, dier B-grubu kaplamalarna gre daha poroziteli bir kaplama yaps grnmektedir. Hava basncnn artrlmasnn poroziteye sebep olduu gzlemlenmektedir. Dier B-grubu kaplamalarna nazaran daha az erimemi partikl olduu gze arpmaktadr.
ekil 14. C3 kaplamas optik mikroskop grnts.
ekil 15. C4 kaplamas optik mikroskop grnts.
Yukarda ekil 14te 150 mm pskrtme mesafeli ve 1 bar pskrtme basnl C3 numunesinden elde edilen mikroyap fotoraflar grlmektedir. C3 numunesi mikroyap fotoraflarndaki kaplama grntleri incelendiinde, klasik alev pskrtmenin mikroyap grnts ( baloncuksu yap ) elde edilmitir. Ba tabakasnn altlk malzemeye ve kaplamaya nfuziyeti gayet iyi grnmektedir. Porozite homojen olarak dalm grnmektedir. Baz ergimemi partikller sz konusudur. Pskrtme mesafesinin 150 mm ye karlmasnn kaplama yapsna olumlu etkileri ak bir ekilde grlmektedir. Sekil 15te 150 mm pskrtme mesafeli ve 2 bar pskrtme basnl C4 numunesinden elde edilen mikroyap fotoraflar grlmektedir. C4 numunesinde pskrtme mesafesinin 150 mmye karlmasnn kaplama yapsna olumlu etkileri grlmektedir. Homojen dalm bir porozite sz konusudur. C3 numunesinden farkl olarak bir miktar erimemi partikl gze arpmaktadr.
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3.2. Mikrosertlik Btn numunelerin mikrosertlik deerleri, arayzeyden itibaren 0,15 mm aralklarla llm, sonra her bir numune iin ortalama deer alnarak aadaki ekil 16daki grafik oluturulmutur.
ekil 16. Numunelerin ortalama sertlikleri.
ekil 17. Hava basncna bal sertlik deiimi (50 mm)
ekil 18. Hava basncna bal sertlik deiimi (100 mm) Yukardaki ekil 17 ve ekil 18de ise mikrosertlik deerinin 50 mm ve 100 mm toz metal pskrtme mesafelerinde hava basncna gre deiimi grafikleri verilmitir. Elde edilen deney sonular incelendiinde genelde hava basnc artrldnda sertliin de artt grnmektedir. Dk pskrtme mesafelerinde hava basnc ok artrldnda bu kural tersine dnebilmektedir. Burada dk pskrtme mesafelerinde hava basnc artnca kaplamada oluan yksek poroziteden dolay mikro sertlik lmlerinde salkl deerler elde edememi olmamz olasdr. Pskrtme mesafesi olarak optimum deerler ierisinde kabul edilen 150 mm deeriyle kaplanm C numunelerinde, kullanlan tozun literatrdeki sertlik deerine yakn deerler elde edilmitir. Burada da hava basnc artrldnda sertlikte artma tespit edilmitir. 3.3. Yzey Przll Deerleri
ekil 19. Yzey przll sonular.
ekil 20. Hava basnc- yzey przll ilikisi(50mm)
ekil 21. Hava basnc- yzey przll ilikisi(100mm).
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Yzey przll lmlerinde optik mikroskop grntlerinde elde edilen grntlerle paralellik gsteren deerler elde edilmitir. Syle ki; yakn mesafeden pskrtme yaplan A1 ve A2 numunelerinde optik mikroskopta grlen heterojen porozite bykl yzey przllne de yansm ve daha homojen byklkte poroziteye sahip A3 numunesinden daha przl bir yzey elde edilmitir. Basncn artrlmasyla oluan A4 numunesindeki byk boluklar ok daha yksek bir yzey przll oluturmutur. B1 numunesinde kullanlan sfr hava basnc tozun hzn ok drdnden yzeye ge gelen toz bu sre zarfnda souyarak yzeyde erimemi partikllere sebep olmu ve B3 ve B4 numunelerine nazaran daha przl bir yzey olumasna sebep vermitir. C numunelerinde ise yksek hava basnc kullanlan C4 numunesinde C3 numunesine nazaran ok daha fazla przl bir yzey elde edilmitir. Buradan su sonucu karmak mmkndr ki; hava basncnn ok dk olmas da ok yksek olmas da yzey przlln artrmaktadr. Her pskrtme mesafesinde de 1 barlk hava basnc en dzgn yzey przlln vermektedir. Bu deerin altndaki basnlar tozun yzeye yava gelmesine ve bu sre zarfnda souyarak yzeyde erimemi partikller olumasna sebep olmaktadr. Bu deerin stndeki basnlar da tozun yzeye ok hzl arpmasna ve yzeyde dalgal bir grnt oluturmasna sebep olmaktadr. 3.4. Kaplama Ba Mukavemeti Kaplamalarda ba mukavemeti ASTM C633 Isl Pskrtme Kaplamalar Yapma Mukavemeti lm Standardna gre llr [13]. 25 mm apndaki test ubuunun u yzeyine kaplama yaplr. Ayn aptaki dier bir test ubuuna epoksi srlerek kaplama yaplm ubua yaptrlr. Kullanlan epoksinin sertleme sresi dolunca bu ubuklar ekme deney cihazna balanarak ekme kuvveti uygulanr. ekme sonucu kaplamann koptuu gerilme deeri kaydedilir ve bu deer yaplan kaplamann ba mukavemeti olarak nitelendirilir. Bu almadaki kaplama numuneleri boru malzemesinden yapldndan dolay, yapm olduumuz ekme deneyi ASTM C633 standardna bire bir uygun yaplamamtr. Kaplama yaplm halkalardan kesilen 10 mm x 10 mm kare kesitli test paralarnn kaplama yaplm yzeyleri, yine 10 mm x 10 mm kare kesitli ekme deney ubuklarnn ucuna yaptrlm ve kaplamalara ekme deney cihazyla ekme kuvveti uygulanmtr. Kaplamalarn esas metalden ayrld gerilme deerleri kaydedilmi ve bu deerler kaplamalarn birbirleriyle mukayese edilmesi iin kullanlacak ba mukavemeti olarak deerlendirilmitir. Bu deerler yaplan kaplamann gerek ba mukavemeti olarak deerlendirilmemelidir. Bu deneyde btn numunelere ayn artlar altnda (fakat ASTM C633 standardna tam uygun deil) ekme deneyi uygulanm ve bulduumuz kopma deerleri birbirleri arasnda mukayese amacyla kullanlmtr. Kaplama prosesi sonras malzemede iki tr ba kuvveti olumaktadr. Esas metal ile kaplama malzemesi arasnda oluan Adhezyon Balar ve kaplama malzemesinin kendi moleklleri arasnda oluan Kohezyon Balardr. ekil 22de numunelere uygulanm ekme deneyleri sonucu elde edilen ba mukavemetleri verilmitir.
ekil 22. Numunelerin ba mukavemetleri.
ekil 23. Hava basnc-ba mukavemeti ilikisi (50 mm).
ekil 24. Hava basnc-ba mukavemeti ilikisi (100 mm). Ba mukavemetleri deerlendirildiinde yakn mesafeden yaplan pskrtmenin ba mukavemetine olumsuz etkisi grlmektedir. Yakn mesafeden pskrtme esnasnda hava basncnn sfra indirilmesi adhezyon ba kuvvetini olumsuz etkilemekte ve kaplama esas metale yapmamaktadr. 0,5 bar hava basncnn kullanld A2 numunesinde ise adhezyon ve kohezyon ba kuvvetlerinin optimum pskrtme mesafesi olan 150 mm den yaplan pskrtme sonucu elde edilen ba kuvvetleri kadar iyi olduu grlmektedir. Basn 1 bar ve 2 bar seklinde artrldnda
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daha dk kohezyon ba deerleri elde edilmektedir. 100 mm ve 150 mm pskrtme mesafeli B ve C numunelerinde de hava basncnn 2 bara karlmas ba mukavemetinde zayflamaya sebep olmaktadr. 4. TARTIMA Toz alev pskrtme yntemi ile ASTM A106 karbon elik boru i yzeylerinin Xuper FrixTec 19850 tozu ile kaplanmas deneylerinden elde edilen sonulara gre; 1- Kaplamada kullanlan farkl pskrtme mesafeleri ierisinden en optimum deer 150 mm bulunmutur. 2- Optimum pskrtme mesafesinde yaplacak kaplamlarn sertlii artrlmak istendiinde hava basnc biraz artrlabilir. 3- 4 ve 6 borularn i aplarnn bu deerden daha kk olmas gibi yakndan pskrtme yapmak zorunda kalnd durumlarda, kaplamada oluacak poroziteyi azaltmak iin dk deerlerde hava basnc seilmelidir. 4- Yzeyde erimemi partikllerin grnmesi halinde, hava basnc artrlarak tozun ivmesinin artrlmas ve tabancadan ktnda erimi halde olan tozun daha ksa srede yzeye ulamas salanmaldr. Aksi takdirde alev pskrtme ynteminin dk pskrtme hzndan dolay kaplama tozunun yzeye ulasana kadar ergimi formdan bir miktar kat forma dnt grlmektedir. 5- Pskrtme mesafesi ile hava basnc arasnda ba mukavemeti asndan dorusal bir iliki bulunmamakta, basn ok drldnde de, ok ykseltildiinde de ba mukavemeti zayflamaktadr. 50 mm pskrtme mesafesi iin 0,5 bar, 100 ve 150 mm pskrtme mesafesi iin 1 bar hava basnc ba mukavemeti asndan optimum deer olarak grlmektedir. Dolaysyla ksa mesafeden pskrtme yapma zorunluluunun olduu durumlarda hava basncnn optimum basn deeri olan 2 barn daha altlarnda bir deer seilmelidir. KAYNAKLAR [1] TRKES, ., Metal Makine Paralarnda Yzey Kaplama Teknolojisi, Petkim Petrokimya Holding A.S., Yayn No: 93-MB-002. [2] NURSOY, M., NER, C., CAN, ., Wear behavior of a crankshaft journal bearing manufactured by powder spraying, Materials and Design 29 (2008), 20472051. [3] STEL, F., Plazma Sprey Kaplama Teknolojisi, Yksek Lisans Tezi, T Fen Bilimleri Enstits, stanbul, 1995. [4] PAMUK, U., Plazma Spreylenmi Cr3C2-NiCr ve Al2O3-TiO2 Kaplamalarn Abraziv Anma Davranlarnn ncelenmesi, Yksek Lisans Tezi, T Fen Bilimleri Enstits, stanbul, 1996. [5] http://www.twi.co.uk/j32k/protected/band_3/ksrdh001.html.
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TME ZAMANININ PERLT TOZ TANE BOYUTUNA ETKS

Yusuf KILIN* *Seluk niversitesi Ereli Kemal Akman Meslek Yksek Okulu, 42320, Konya, ykilinc@selcuk.edu.tr ZET Bu almada 500, 700 ve 900 dev/dak dnme hzlarnda olmak zere farkl hzda alabilen; 3/2, 2 ve 3 litre deiebilir tme tank kapasiteli, titreimli yatay bir atritr tasarlanm ve imal edilmitir. Bu atritrle mikronize perlit malzeme 9.52 mm apl elik bilyelerle 1:5 ,1:10,1:20 toz/bilye arlk oranlarnda 6,9 ve 12 saat srelerle tlmlerdir. tme zaman arttka toz tane boyutunun azald grlmtr. Anahtar Kelimeler: Atritr, Perlit, Deirmen, tme, Toz Boyutu.
THE EFFECT OF MILLING TIME ON THE GRAIN SIZE OF PERLIT POWDERS

ABSTRACT . In this study, 500, 700 and 900 rpm rotational speeds to operate the mill was designed and manufactured. With this mill 500,700 and 900 rpm rotational speeds to operate in three different speed. In this grinding mill the micronized perlite material grinded by 9 mm diameter steel ball used at 1:5,1:10,1:20 powder/ball weight ratio. Three different grinding time was used which6,9 and 12 hours. Powder particle size decreased with increasing grinding time Keywords: Attritor, perlit, grinding, milling, particle size 1.GR Toz metalrjisi teknolojileri paracklarn bir araya gelmesiyle oluan tozlarla balar. Younlatrma ileminde nemli bir girdi olmas nedeniyle tozun iyi anlalmas gerekir. Parack, tozun blnemeyen en kk birimi olarak tanmlanr. Toz ileme teknikleri genellikle dumandan daha byk (0,01-1m), fakat kumdan daha kk (0,1-3mm) paracklarla ilgilenir. Kullanlan tozlarn ou insan sa lsndedir(25-200m). Toz metalrjisi ve parack malzemelerde en yksek retim hacimleri elektronik, mikro elektronik ve elektrik alanlarndadr. Elektrik temas elemanlar byk lde preslenmi ve sinterlenmi W-Cu veya W-Ag tozlar kullanlarak retilmektedir. Ylda 150-200 milyon kiisel bilgisayar retilmekte ve bunlarn her biri sinterleme ile retilmi eitli kilitler, disk src balanslar, balantlar ve yataklar ierirler. Uzay mekii zerindeki sl koruma sistemi silikadan (SiO2) sulu amur dkm ve sinterleme teknikleri ile retilir.[1] Bir metal tozu retim teknii olmakla birlikte, dier tekniklerle retilmi ancak kmelemi tozlarn krlmas iinde kullanlan tme, en ok bilyal deirmenlerde yaplmaktadr[2]. Perlit malzemesi tarm. naat, sanayi, gda, filtre retimi, tekstil ve kriyojenik perlit olarak hemen hemen btn sektrlerde farkl boyutlarda kullanlmaktadr. Tarmda perlit, %92nin zerindeki toplam gzeneklilii ve %68 do-
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layndaki havalandrma gzeneklilii ile topran havalanmasn salar, drenajn ykseltir. naat uygulamalarnda perlit, izolasyon malzemesi olarak kullanlr. Sanayi sektrnde, gda, ila ve kimya sanayi katk maddesi olarak, s yaltmnda, metalurji, cam ve seramik retiminde youn olarak kullanlmaktadr. Tekstik sektrnde kuma retiminde perlit ieren polyester iplik retimi ve perlikt kullanmnn kuma performans zelliklerine etkisi zerine bilimsel almalar yaplmaktadr [3]. Bu almada 500, 700 ve 900 dev/dak dnme hzlarnda olmak zere farkl hzda alabilen; 3/2, 2 ve 3 litre deiebilir tme tank kapasiteli, titreimli yatay bir Atritr tasarlanm ve imal edilmitir. Bu atritrle, Uluda niversitesi Tekstil Blmnden temin edilen mikronize edilmi perlit malzeme 9.52 mm apl elik bilyelerle 1:5,1:10 ve 1:20 toz/bilye arlk oranlarnda 6,9 ve 12 saat srelerle tlmtr. Atritrn perlit tme davran, farkl tme sreleri ve toz/bilye oranlar iin aratrlmtr. Bu deirmenle Perlit tozlar farkl deneylerle farkl toz/bilye oranlarnda ve zaman aralklarnda tlmlerdir. Tozlarn orijinal boyutlarnn tme sreleriyle deime sreci takip edilmitir. Optimum tme artlarnda elde edilen toz boyutlarnn lm yaplarak minimum toz boyutu elde edilmeye allmtr. Atritr altrldnda yksek enerji ile bilyeler birbirine arpar ve arpmann etkisi ile arada kalan tozlar ezilir. Bu ilem devam ettike tozlarda pekleme, krlma ve kaynama devam eder. ok ksa srede dahi karm elde edilir, ancak ok homojen deildir. Saf tozlarn tlmesinde ise tme devam ettike toz boyutlar klmeye devam eder. 2.TOZ TME TEKNKLER 2.1 Toz tme mekanizmas Bir metal tozu retim teknii olmakla birlikte, dier tekniklerle retilmi ancak kmelemi tozlarn krlmas iin de kullanlan tme, en ok bilyeli deirmenlerde yaplmaktadr. tlecek metal, iinde byk apl, sert ve anmaya kar dayankl bilyelerin bulunduu kaba yerletirilir. Kap dndrlerek veya titretirilerek bilyeler harekete geirilir (ekil. 2.1). Eer tlen paracklar gevrek ise, bilyelerle arpma neticesinde ok kk tozlara blnr. Snek paracklar ise, arpma sonucunda ekil deitirerek yasslarlar (ekil 2.3) ve ancak ar i sertlemesi neticesinde gevrekleerek kk tozlara blnebilirler [4].
ekil 2.1 Toz tme Mekanizmas ekil 2.2 Bilyeli Atritr
ekil 2.3 tmede arpmann Etkisi [3]
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tmenin su, alkol ve heptan gibi bir hidrokarbon sv iinde yaplmas hem tme sresini ksaltr, hem de ince tozlar retilmesini salar. Bir tcnn verimliliini tme ortamnn arpma hz ve tc iindeki malzemenin hareketlilii belirler. tmenin ok yava bir dn hz ile yaplmas, bilyelerin kabn zerinde yuvarlanmasna; ok yksek bir dn hz ise merkezka kuvvetinin etkisiyle bilyelerin kap yzeyinde dmeden durmalarna sebep olur. Ayrca bilyelerin hacmi kap hacminin yaklak yars ve tlecek metal miktar kap hacminin yaklak %25i olmaldr. Silindirik deirmenler metal tozlarnn tlme sinde yaygn olarak kullanlmakla birlikte, dk hzlarda altklarndan tme sresi uzundur. Bu sreyi ksaltmak iin titreimli deirmenler ve atritrler (ekil 2.2) gelitirilmitir. Atritrler dier tclere gre daha ksa zamanda kartrma-tme zelliine sahip, yksek enerjili ve en verimli tclerdir. Silindirik deirmenlerde optimum bir dnme hz sz konusu iken, atritrlerde kartrc kollarn hz ne kadar yksek ise tme verimlilii de o kadar yksek olmaktadr. Bu almada, titreimli yatay tip bir atritrn tasarm ve imalat yaplarak almina ve perlit tozlarn tme davran incelenmitir. Toz tme deirmenleri ok eitli modellerde ve serilerde retilmektedir. Union Process Firmas tarafndan retilen tipik aratrma ve laboratuar almalarnda kullanlan tipik atritr ekil 2,4.de verilmitir. Szeguari marka krc tc deirmenleri yksek enerji ile alan bilyeli deirmenlerdir. Bunlarda bilyelerin ve tozun yklenmesi sabit, dik konumda, su soutmaldr. Dnen bir merkez aft ile malzemeler kartrlr. Spex shaker deirmenleri az miktardaki tozu (10 gdan az) toz tmek iin kullanlan titreimli deirmenlerdir. Aslnda spektrografik rnekleri arptrarak toz retme amacyla gelitirilen Spex deirmeni (55.10-3 m3 ) lk kk bir tme kabn dik yne yaklak 20 Hz (1190 dev/dak) ile sallayarak alr. Merkez yatay bir aksn yrngesinde dnen geleneksel top deirmenleri, 1mden byk apl ve yksek enerjilidirler. Bu deirmenler toplar i duvarlara yaptracak ve toz ykne bal top yknn arln drecek olan kritik hzn altnda altrmay gerektirir. Toz tmede genellikle 5000 den fazla AISI E 52100 standart tc bilyeler kullanlr.
ekil 2.4 Ticari Olarak retilen Toz tme Deirmeni (Atritr) ekil. 2.5 ve ekil 2.6da grlen Titreimli Yatay Atritr tasarmlanm ve imalat yaplmtr[5]. Sistem 0.75 kw gcnde 1800 d/d motor mili dnme hznda bir elektrik motoru ile tahrik edilen 700, 900, 1400 d/d dnme hzlarna ayarlanabilen kademeli V kay kasnakl olarak almaktadr. Atritrn iskeletini muhtelif kebent, kare profil sa malzemeler oluturmaktadr. Deneyler iin 3/2 , 2 ve 3 litrelik paslanmaz elik tanklar ile tankn evresinde soutma suyunun dolamas iin elik borudan imal kazan kullanlmtr. Kartrc kollar ve merkez aft paslanmaz elik malzemeden yaplm ve kollar gvdeye TIG kayna ile kaynatlmtr. Kollar motor supaplarndan imal edilmitir. Bilyelerin ve tozlarn kartrc kol yzeylerinde anma ve oyuk oluturmalar sert dolgu kayna ile giderilmitir. malat yaplan titreimli yatay atritr ekil.2.5te gsterilmitir. Atritr, bir elektrik motorundan kay-kasnak sistemi ile tahrik edilmektedir. Motor mili 1800 dev/dak hza sahiptir. Bu hz, kademeli kasnaklar ile 700,900 ve1400 dev/ dak hzlara ayarlanabilmek tedir. tmenin yapld tank, drt adet bask yay zerine oturtulmutur. Yay sabitleri Probat-Werke marka cihazda llmtr. Serbest boy Lo = 61,5 mm, L = 51 mm (4,95 kg ykleme), L2=41 mm (9,75 kg ykleme) ve Lmin = 25 mm (16 kg ykleme) lm deerleridir. Elektrik motoru mili, atritr miline ift akuple bir kardan kavramas ile irtibatlandrlmtr. Motor alt anda serbest dnen mil esnek hareketle atritr yaylar zerinde titretirmektedir. Bylece tc tank, elik bilyeler ve toz malzeme ok eksenli olarak titremektedir. Atritrde tme, 3/2, 2 ve 3 litre hacimli Cr-Ni paslanmaz i elik tanklarda yaplmaktadr. ekme dikisiz borudan d tank yaplmtr. tanklar deitirilebilmektedir. Her iki tank arasnda soutma suyu dolaa bilmektedir. Kartrc kollar Cr-Ni paslanmaz elikten yaplmtr. Atritrn almas srasnda meydana gelebilecek snmadan kaynaklana bilecek reaksi yonlarn nlenmesi iin,tme tank ile d tank arasnda soutma sistemi mevcuttur. Sistemin montaj ve demontaj kolaylkla yaplabilmektedir.
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ekil 2.5 Yatay Titreimli Artritr ematik Resmi
ekil 2.6 Tasarm Yaplan ve mal Edilen Yatay ve Titreimli Toz tme Deirmeni 3.DENEYLER 3.1 almann amac Bu almada ama, mikronize Perlitin atritrde tlerek tane boyutunun kltlmesi ve tme parametrelerinin toz boyutlarnn kltlmesinde etkilerinin incelenmesidir. Boyutlar 14 mikron civarnda olan mikronize toz perlit,1 mikron seviyesine indirilmesi amacyla muhtelif deneyler yaplmtr. Minimum toz boyutunun elde edilebilecei alma parametrelerinin belirlenmesi ve atritrn verimlilii zerinde yaklamlar sergilenmitir. 3.2 almann nemi Mikronize edilmi tozlarn ticari kullanmlar ok nemlidir. Mikronize perlit ham perlitin tlerek ticari kullanmlar iin en kk boyuta getirilmi eklidir. Perlitin mevcut uygulamalar iin 10 mikron civarnda boyutlar yeterli olmaktadr.Ancak bu almadan elde edilecek daha kk boyutlu perlit tozlarna da ihtiya duyulmaktadr.Yatay
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Titreimli olarak tasarlanan Atritrn perlit tme performans bir dizi deneyle llecek ve sonu olarak tasarm asndan makine deerlendirilecektir. 3.3 Deney Malzemeleri Deneylerde Uluda niversitesinden elde edilen mikronize Perlit farkl parametrelerde tlmlerdir. Perlit tozlar ortalama toz boyutu: 14.04 mdur. 3.4 Perlit tme deneyleri Deneyde Uluda niversitesi Tekstil Blmnden temin edilen ve ortalama toz boyutu d(0.5) 14.04 d(0.1)3.44 d(0,9) 44.09 mikron olan mikronize perlit kullanlmtr. elik bilyeler 9.52 mm apndadr ve ORS (Ortadou Rulman Sanayi)den temin edilmitir. alma devri 900 d/d olarak ayarlanmtr. Deneyler 6, 9 ve12 saat srelerle 1:5,1:10,1:20 toz/bilye oranlarnda ayr ayr yaplmtr.Deneyler kuru tme ortam ve sulu ortamda yaplmtr. tme tank kapasitesi 2 litre hacimli seilmitir. tlen perlit tozlarnn boyut analizleri Gazi niversitesi Mhendislik Mimarlk Fakltesi Makine Mhen dislii Blm Toz Metalrjisi Laboratuarnda bulunan Malvern Mastersizer E lazerli toz boyutu lme cihaznda yaplmtr. Yaplan tme ilemlerine ait deney artlar ve tme neticesinde elde edilen tozlarn boyut analizlerine ait d(0,5), d(0,1) ve d(0,9) deerleri izelge 3.1de gsterilmitir. 3.5 Perlit Boyut lm izelge 3.1. Farkl tme artlarnda Elde Edilen Perlit Tozu Boyutlar Deney no 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Toz/Bilye Oran 1:5 1:5 1:5 1:10 1:10 1:10 1:20 1:20 1:20 1:5 1:5 1:5 1:10 1:10 1:10 1:20 1:20 1:20 tme sresi(saat) 6 9 12 6 9 12 6 9 12 6 9 12 6 9 12 6 9 12 tme Ortam Kuru Kuru Kuru Kuru Kuru Kuru Kuru Kuru Kuru Sulu Sulu Sulu Sulu Sulu Sulu Sulu Sulu Sulu d(0,5)m 4.66 5.62 7.52 8.02 9.72 14.72 8.89 11.10 7.63 3.60 3.28 3.14 3.51 3.52 3.39 4.78 4.99 5.20 d(0,1)m 0.75 0.88 1.09 1.10 1.02 1.37 1.09 1.19 0.99 1.07 1.04 0.94 1.00 0.90 0.84 1.00 0.95 0.97 d(0,9)m 43.73 33.39 39.42 37.38 95.84 166.41 36.18 70.43 39.79 11.38 9.72 18.72 10.85 19.58 17.48 17.00 23.75 27.26
Orijinal veriler verilmeli 3.6 Perlit tme Sonular Mikronize perlit tme ncesi ortalama boyutu (14,04 ) dr Ancak ayn perlitlerin boyutlar arasndaki azda olsa fark olabilmektedir. Ham perlitten mikronize perlit elde edilirken homojen boyutlar elde edilemedii biliniyor. Deneylerde kullanlan mikronize perlitin iinde deien boyutlarda perlit tanecikleri var. Gazi niversitesinde yaplan boyut lm sonularndan da bu grlebiliyor. Farkl zamanlarda yaplan ortalama lm sonular arasndaki fark perlit retimi srasnda olumaktadr. Sonulardan izelge 3.1de kuru ortamda 1:5 ve 1:10 ve su ortamnda 1:20 ile yaplan tmelerde ilgin bir ekilde tme sresi artka ortalama perlit boyutunun artt grlyor. Beklenen sonu tme sresi arttka toz
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boyutunun dmesidir. Toz boyutunun, su ortamnda 1:5 ve 1:10 ile yaplan tmelerde dt grlyor. O da kk deiimlerle. Kuru ortamda 1:20 ile yaplan almada ise baka ilgin bir durum sz konusu: 6 saatten 9 saate knca boyut artarken 12 saatte boyut byk oranda klm. Bu farkn sebebi zerinde dnmek gerekecektir. Perlitin ilk tme sresince topaklanarak katmerlemesi beklenilmelidir. Daha sonraki tme srecinde yeniden krlmalar ve ufalanmalar toz boyutunu kltecektir.12 saatlik srede beklenen olmutur. Kuru ortamlarda yaplan tmeler iin tozlarn kaynaklamas ve zamanla tekrar ufalanmas daha da olas bir durum olarak gzlemlenmitir. izelge 3.1de deney 9 daki durumu hari tutarak ayn alma srelerinde toz/bilye orannn boyut zerine etkisi dikkate alndnda; en kk orandan (1:5) en yksek orana (1:20) kldka ortalama perlit boyutunun artt grlyor.Tm toz/bilye oranlar ve alma sreleri dikkate alndnda; su ortamnda almann kuru ortama gre ok daha kk boyutlarda tme salad grlyor. Tm tme oranlar iin 12 saat su ya da alkol benzeri sv ortamlarda tme yapmak daha kk boyutlara ulamak asndan faydal olacaktr. 4. SONULAR Tasarm ve imalat yaplan Yatay Titreimli ATRTR yukarda belirtilen toz tme mekanizmasna uygun tasarmlanmtr. Atritrden beklenen, tme ortamnda herhangi bir kimyasal reaksiyona meydan vermeden tozlar istenen boyutlara kadar tmesidir. Bu nedenle atritr laboratuar iin tasarmlanm ve kk kapasiteli tutulmutur. Elektrik motoru yeterli gte seilmitir. Titreim iin Atritr drt adet yay zerine oturtulmu. tme tank ayrca mafsall bir mil ile de salnmakta ok ynl hareket edebilmektedir. 4.1 tme Zaman - Toz tme sresi Toz Boyutu likisi Perlit tme ilemlerinde tme ortam olarak kuru ve sulu ortam tercih edilmitir. Perlit yumuak bir malzeme olup tme mekanizmasna anma bakmndan herhangi bir zarar vermemektedir. Kuru ortamlarda perlit toz boyutu tme sresinin artmas ile bymektedir. Bu durum istenmeyen bir sonutur. Kanaatimize gre kuru ortamlarda tozlar ezilerek katmerlemekteler. izelge 3.1 de 1:20 tme orannda bu durum farkl kmtr. Deneyin tekrar ve ya toz boyutunun yeniden llmesi gerekebilir. Perlit tozunun sulu ortamda 1:5 toz/bilye orannda 12 saatlik sre sonunda 3.14 mikron deerine ulat grlmektedir. Bu durum beklenen bir sonutur. 4.2 neriler Tm deneylerde sabit tutulacak olan alma devri yeniden seilebilir. tme tank kapasitesini deitirmek mmkndr. Perlit iin 9,52 mm bilye ap seildi. Kk apl bilye kullanmann tme zerine daha olumlu etkisi olaca dnlebilir ve bilye ap olarak 6,35 mm perlit iin yeniden denenebilir. Yaptmz almalar gsteriyor ki; Perlit iin almay tamamen alkol ortamnda yapmak deney saysn 27ye karacaktr. Byle bir almann daha doyurucu olmas mmkndr. Perlit iin su ortam yerine alkol ortam da seilebilir. Kuru ortamda tmenin zellikle kalmasn tercih edilmelidir. nk alkoll tme sonrasnda alkoln perlitten uzaklatrlmas iin ek ilem gerekmektedir. Bu nedenle perlit iinde yukarda belirtilen farkl seviye 1:5,1:10 ve 1:20 (toz/bilye oran) yeterli olacaktr. alma sresi olarak 6,9 ve 12 saatler allmtr. 12 saatten sonra yaplacak bir dizi almada toz boyutlarnn kltme salanaca dnlmektedir. 5. KAYNAKLAR 1. German, R.M., Powder Metallurgy Science, MPIF, Princeton, NJ, USA, 1994 2. Sarta, S., Toz Metalrjisi, Makine Mhendislii El Kitab, MMO, 1994 3.Karaca, E., Perlit eren Poliester plik retimi ve Kullanmnn Kuma Performans zelliklerine Etkilerinin Aratrlmas TBTAK aratrma projesi, 109M269, 2009 4. Da Silva, A.G.P., Da Silva, N.F. and Gomes, U.U., Efects of Milling Technique on the Dispersion, Sintering and Hardness of WC-Co Hard Metals Int. J. Powder Metallurgy, Vol.37, no.6, pp57-66,2001 5.Kln, Y.,Speralam retimi in Yatay ve Titreimli Mekanik Alamlama Deirmeni (Atritr) Tarsarm, malat ve Denenmesi, S. Bilimsel Aratrma Projeleri, 2009
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2014 ALMNYUM ALAIM TOZU LE %2 GRAFT TOZUNUN HIZLI DERMENDE LENMES VE PRESLEME SONRASI UZUN TAVLAMA SRECNDE MKRO-YAPISAL GELMELER
Sinan AKSZ, A. Tamer ZDEMR, B. BOSTAN Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Beevler, 06500, Ankara, sinanaksoz@hotmail.com, tozdemir@gazi.edu.tr , bostan@gazi.edu.tr ZET 2014 alminyum alam tozu ve %2 grafit, koruyucu argon atmosferi altnda 7 s sre ile mekanik alamlama (MA) ilemine tbi tutulmutur. Elde edilen harmanlanm karm 600 MPa basn altnda souk preslenmitir. Numuneler, Ar gaz altnda srasyla 5500C ve 6000C de uzun sre tavlanmlardr. Elde edilen malzemeler incelendiinde; tavlama srasnda taneler irileirken, gzenekliliin nce artt, daha sonra ise azald tespit edilmitir. Gzeneklilikteki bu deikenliin sebebinin, yapdaki atomik magnezyumun scakln etkisiyle hzla tane snrlarnda kmeleirken, ardnda boluklar brakmas olduu dnlmektedir. Bakr ise daha sonra bu boluklar kapatmaktadr. 6000Cde, 196 s tavlanan numunelerde ise ksmi yeniden kristalleme tespit edilmitir. Bu bulgu, yapda youn olarak ince dalml Al4C3 paracklarnn olduunu ve yeniden kristallemeyi bastrdn iaret etmektedir. Anahtar Szckler: 2014 Al alam, MA, uzun sreli tavlama, gzeneklilik, yeniden kristalleme.
HIGH SPEED MILLING OF 2014 ALUMINUM POWDERS TOGETHER WITH 2% GRAPHITE AND PROGRESS IN MICRO-STRUCTURE DURING LONG TERM ANNEALING AFTER COLD COMPACTION
ABSTRACT 2014 Al alloy powders and 2% graphite by weight were mechanically alloyed (MA) about 7 h under gas tight conditions of argon athmosphere. Blended powders were later cold pressed at 600 MPa and then long term annealed at 5500C and 6000C, respectively under the same controlled atmosphere. It was deduced that, during annealing, while grains were slowly coarsening, porosity of the samples first decreased but later increased progressively. For this, Mg atoms primarily diffuse towards grain boundaries and then evaporate, leaving pores behind. Atomic copper later occupies these openings. Particularly, at about 196 h of annealing at 6000C, an evidence of the onset of recrystallization was observed at several areas within the microstructure. This result in fact confirms a dense formation of fine Al4C3 precipitates, which are very effective depressing the recrystalization of the micro-structure. Key words: 2014 Al alloy, MA, long term annealing, porosity, Recrystallization. 1. GR Yap malzemelerini srekli gelitirebilmek iin mhendislik alannda almalar duraksamadan devam etmektedir. Kimyasal, mekanik ve fiziksel zelliklerin geliiminde, kimyasal yap ve termo-mekanik ilem metotlar srekli olarak gzden geirilip, yenilenmektedir. Bu yeni ilemlerle, yap malzemelerinin tasarm ve geliiminde eitli zelliklerle beraber, dayanma karn hafiflik artmakta ve geleneksel metotlarla retilen malzemelerden daha stn nitelikte yeni malzemeler gelitirilmektedir [1]. Toz Metalurjisi (TM) de, yaygn olarak ileri malzeme ve teknolojileri gelitirmede en fazla rabet gren sahalardan biridir [2]. TM ile retilen tozlarn zelliklerini artrmak iin eitli mekanik yntemler de uygulanmaktadr. Bunlardan en nemlisi ve etkin olan, MA tekniidir. MA ilemi birbirinden ok farkl tozlarn birlikte tlmesi ilemidir. MA ilemi
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nce tozlarn doru oranlarda kartrlmas ile balar ve sonra toz karmnn tme haznesine elik bilyalarla birlikte yerletirilmesiyle devam eder. Bu karm daha sonra kararl bir duruma ulaana kadar uygun grlen srede tlr. MA ilemindeki tme sreci bileimdeki toz parack boyutlarnn eitlenmesi ve balangtaki toz boyutlarna ulalmasna kadar devam edilir [3]. Tozlarn son mikro yaplar atomizasyon yntemi ile elde edilen tozlardan ve ayn tane boyutuna sahip hzl katlama ilemine tbi tutulmu tanelerden genelde daha iyidir. Ayrca, toz paracklarnn devaml olarak bilyelerin ve bilye hazne arasnda sktrlp, paralanmas nedeniyle mikro yapsal gerilmeler artmakta, buna bal olarak, sonuta mekanik zellikleri gelimi, adeta birbirlerine yedirilmi, farkl kombinasyonlu yeni alam tozlarnn olumas gereklemektedir [4]. eitli karbr ve dier kat paracklarn ilavesi ile malzemelerin zellikle mekanik zellikleri ve buna bal performanslarnda ciddi artlar kaydedilmitir. Bilhassa, karbrler alminyumda yaygn olarak kullanlmaktadr. Al karbr (Al4C3) ierii Al metal teknolojisinde nemli bir bileen ve elmas bal seramiklerin (Al2O3Al4C3AlN) retimi balangcnda ilk kullanlan malzemelerden olup, bu yap oda scaklnda yksek termal iletkenlikle birlikte yksek elektrik direncine sahiptir. Ayrca, Al4C3 ilavesi metal kompozit ve alamlarnn mukavemetlemesini arttrmaktadr (AlAl4C3, AlSiCAl4C3, AlAl3TiAl4C3, v.b.) [5]. 2xxx serisi alamlar uzun zamandr havaclk sektrnde rabet gren malzemelerdir ve arlkl olarak uak yzeylerinde, perinlerde ve ekme aralarnda kullanlmaktadrlar. Yeni nesil 2014 Al alam, havaclk sektrnde geleneksel olarak tercih edilen 2024 alamnn yerini alm bir alamdr. Bu alam zellikle scak ekstrzyon ve scak haddeleme sonras elde edilmektedir. Genellikle ieriinde bulunan Cu, Mg ve Mn oranlar daha rafine edilmitir. Ayrca, retimden gelen dier kalnt elementlerin azaltlm olmas, sonraki kat hal ilemleri ve buna bal yapsal tasarm kabiliyetini artrmaktadr [6]. 2014 alminyum alamnn elastikiyet modl ve dayanm 2024 alamnnkine gre daha yksektir. Bu almada gaz atomizasyon yntemi ile retilmi 2014 tozlar, Grafit (C) tozlar MA ilemine tbi tutulmu, hem MA hem de MA sonras ilemlerle yapsal gelimeler incelenmitir. 2. DENEYSEL ALIMALAR: 2.1. Mekanik Alamlama: 2014 alam tozlar, yksek saflktaki Ar gazyla 15 bar basn altnda gaz atomizasyon yntemi ile retilmitir. Daha sonra, elek analizi ve parack boyut analiz cihazlarnda ayrtrlan tozlarn ortalama boyu 95 m dir. Alam tozlar, (20-180 m boyut aralnda) %2 grafit tozlaryla harmanlandktan sonra, yksek enerjili dikey Atritrde MA ilemine tbi tutulmulardr. Atritr ierisinden yksek saflkta Ar gaz geirilerek toz karmnn oksitlenmesi engellenmeye allmtr. Bir nceki almada, MA ilemi bir kimyasal kullanmadan saf Al ve C tozlar ile gerekletirilmi ve ilemin 2 s sonunda baaryla tamamland belirlenmiti [7]. Benzer ekilde, bu almada da MA iin bir yalayc kullanmadan AA2014 tozlar ve %2 C, 500 dev. / dak. ve 20: 1 bilye toz orannda tlmek istenmitir. Ancak, sistemin kilitlendiinin fark edilince, ilave yalayc olarak % 0,5 inko sterat katlm ve sorun almtr. Daha sonra, deneylerle uygun MA sresinin en fazla 7 s olabilecei tespit edilmitir. Bu sre sonucu elde edilen kompozit tozlarnn ortalama tane boyutu 54, 50 m ve toz boyut aral 1,60-331 m arasnda deimektedir. ekil 1de, MA sresine bal olarak ortalama toz boyutu ve buna bal olarak sertlik deerleri verilmitir. Alamlanm toz boyutun yaklak 5 s kadar artt ve bundan sonra tekrar azald grlmektedir.
ekil 1. MA ilemi srasnda, ortalama toz boyu ve sertlik deiimleri.
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eitli srelerde MA yaplan tozlar XRD ile incelenmi ve ilemin sonunda beklenen Al4C3 faznn olumad anlalmtr (ekil 1). Benzer sonular, dier baz almalarda da grlmtr [7-11].
ekil 2. 7 s MA ilemi gren tozlarn XRD analizi. 2.2. Presleme ve Sinterleme: MA sonras tozlar, 600 MPa altnda izo-statik presleme ile sktrlarak tablet haline getirilmitir. Daha sonra tabletler, 550 Cde 2-24 s arasnda, 600 Cde 2-196 s olarak belirli zaman aralklarnda uzun sreli sinterleme ilemlerine tbi tutulmutur. Bu sre ierisinde, gerek MA sonras tozlar, gerekse sinterleme sonras elde edilen kompozit malzeme yaplar eitli karakterizasyon ilemlerine tbi tutulmulardr. Srasyla: toz boyutu analizlari iin; Malvern Mastersizer E cihaz, XRD analizleri iin; Cuk =1.5406 ve 2/dakika tarama hznda Bruker D8 cihaz kullanlmtr. Ayrca, mikro yap incelemeleri Joel JSM-5600 taramal elektron mikroskobunda (SEM), sertlik lmleri ise, Shimadzu Mikro Sertlik cihaznda 100g yk kullanlarak gerekletirilmitir. 3. BULGULAR VE TARTIMA MA sonras preslenen kompozit tozlar, preslenip tablet haline getirildikten sonra, 550 Cde uzun sreler tavlanarak, sinterlenmitir. Tavlamann balangcnda (4 s), tane yaps kk ve gzeneklilik azalma eilimi gsterirken, zamann artmasyla (12 s) tanelerin iriletii, buna karn gzenek saysnda bir art grlmtr (Resim 3).
ekil 3. 550 Cde uzun sre tavlanma sonras mikro yaplar. a) 4 s (X 1500) b) 12 s (X 1500) 5500C de, 4 s tavlanan numunelerde element dalm taramas (EDS) yaplarak, mikro yap iersindeki alam elementleri ve miktarlar belirlenmitir. Resim 4 te iaretlenen 3 ayr blgede EDS analizi yaplmtr. lk 2 analiz, ana matris zerinden alnm, bu iki farkl blgenin sl ilem sonras element dalm farkllklar belirlenmitir. 3. analiz ise parlak renkli blgeden alnmtr. 1. blgenin analizi gre; Alminyum %93,2, Cu %0,85 ve Oksidin %5,94 olduu, 2. blgede, Cu %1,59 olarak artarken, O deerinin %1,69 oranna dt tespit edilmitir. 3. blgede ise, Cu %4,6 deerlerine ularken, O deerinin % 3 civarnda olduu tespit edilmitir.
ekil 4. 550 Cde 4 s tavlama sonras mikro-yap ve EDS iin seilen blgeler (X 1500).
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Ksaca, yap ierisinde element dalmlarnn homojen olmad, blgesel farkllklarn baskn olduu anlalmaktadr. ekil 4te, 3. noktadan alnan analiz sonularnda, parlak yerlerin Cu bakmndan zengin alanlar (Al2Cu) olduu anlalmaktadr. te yandan, ekil 5teki genel EDS sonucu incelendiinde, yaplan uzun sreli tavlamalar sonras mikro yapda oksitlenme olmadn gstermektedir. Ayrca, genel Cu dalm seviyesinin beklenen miktardan (%5) daha dk (%2,56) kmaktadr. Bu sonuca gre, Cu belli blgelerde ar younlaarak, kmelenmektedir. Sv faznda sinterlemenin etkin olduu bu durumda, tane snrlarnda kelen Al2Cu faz, tane iinde azalan Cu miktarnn sebebini aklamaktadr.
ekil 5. 550 Cde 4 s tavlama sonras genel EDS sonular. 550C de yaplan uzun tavlama srasnda zamana bal olarak nce gzeneklilikte bir artn olduu, bunun tersi olarak ta younlukta bir azalma meydana geldii grlmektedir. Tavlamann 24 s zerine kmasyla, olayn terse dnd ve younluun artmaya balad fark edilmitir. Ksaca, 24 s dnm noktas olduu ve etken mekanizmann zayflad veya terse dndn anlalmaktadr. Genelde, Al alamlarnda bulunan Cu elementinin malzemenin younluunda bir azalmaya sebep olduu bildirilmektedir [2,12,13]. Esasen, hem Cu, hem de Mg, Al ierisinde hzla yaynabilmekte ve bylece, kk tane veya toz ara-yzeylerine hzla kabilmektedirler. zellikle Mg, scakln etkisiyle Cua gre yaklak 5 kat daha hzl yaynp, buharlaarak ardnda boluk brakmaktadr [14]. Daha yava ilerleyen Cu ise daha sonra ara-yzeylere gelip, younlaarak Al2Cu fazn oluturmakta ve sv haldeki bu faz zamanla tm ara-yzeyi kaplama eilimi gsterdii iin gzeneklilikte bir azalma balamaktadr. Bu yzden yaplan element analizlerinde, mikro yaplarda Mg elementine rastlanamamtr [14].
ekil 6. 600 Cde 196 s tavlama sonras mikro yaplar. a) (X 1000) b) (X 1500) 6000Cde yaplan uzun sinterleme ilemlerinde, mikro-yaplarda az da olsa ksmi olarak yeniden kristalleme (YK) balanglar grlmektedir (Resim 6). Saf Al istif hatas enerjisi (HE) yksektir ve bu yzden yaklak 300-3500C gibi scaklklarda, Al hzl toparlanma ve YK eilimindedir [15]. Ancak bu almada, YKnn, 6000C de ok uzun sren tavlama sonrasnda belli belirsiz olumaya balamas, alam elementlerinin etkisinden daha ok, yapda youn olarak ince dalml Al4C3 paracklarnn bulunduunu ve YK balangcn nemli lde telediini gstermektedir. Tavlama srasnda oluan bu nano boyda, ok sk dalml ve kararl paracklar, MA sonras souk deformasyondan gelen alt yap taneleri vs zerinde yerleerek, onlarn geliimini engellerken, toparlanma srecini ar derecede geciktirmektedirler [14-18].
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4. SONULAR Sonu olarak, yap ierisinde youn dalma sahip Al4C3 faz YK balangcn nemli lde etkilemektedir. YK baz belli blgelerde ok zor ve yava olarak geliim gsterme eilimindedir. nceki almalardan, Al4C3 paracklarnn youn olarak yapda olutuu ve yaplarda hibir YK oluumunun gzlenmedii bilinmektedir [7]. Bu almada ise, eldeki malzemenin YKya kar gsterdii ar diren, zellikle yksek scaklk dayanmnn iyi olabileceini iaret etmektedir. retilen bu kompozit malzemede, hem MA sonras sinterleme ve hem de yalandrma ilemleriyle yksek dayanml bir mikro-yap elde edilmitir. Malzeme, uzun sre yksek scaklklara maruz kalmasna ramen, mekanik olarak eritii dayanmdan bir ey kaybetmemekte ve bylece yksek scaklk uygulamalarnda srnme dayanm yksek malzemeler arasnda yer bulma potansiyeline kazanmaktadr. KAYNAKLAR 1. Suryanarayana C., Mechanical Alloying and Milling, Progress in Materials Science, 46 (2001) 1-184. 2. German R.M., ed. Sarta S., Trker M., Durlu N., Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Dernei , Ankara, (2007). 3. Suryanarayana C., Mechanical Alloying, Pergamon Materials Series, 2 (1999) 49-85. 4. Ruiz-Navas E.M., Fogagnolo J.B., Vlasco F., Ruiz-Prieto J.M., Froyen L., One Step Production of Aluminium Matrix Composite Powders by Mechanical Alloying, Progress in Composites, 37 (2006) 2114-2120. 5. Solozhenko V.L., Kurakevych O.O., Equation of State of Aluminum Carbide Al4C3, Progress in Solid State Communications, 133 (2005) 385-388. 6. Kaar H., Atik E., Meri C., The Effect of Precipitation-Hardening Conditions on Wear Behaviours at 2024 Aluminium Wrought Alloy Progress in Materials Processing Technology, 142 (2003) 762-766. 7. Bostan, B., zdemir A.T., Kalkanl A., Microstructure characteristics in Al-C system after mechanical alloying and high temperature treatment, Powder Metallurgy, 47:1 (2004) 37-42. 8. Arslan G., Kara F., Turan S., Quantitative X-ray Diffraction Analysis of Reactive Infiltrated Boron CarbideAluminium Composites Journal of the European Ceramic Society 23 (2003) 12431255. 9. Wu, N. Q., Wu, J. M., Wang, G.X., Li, Z. Z., Amorphozation in the Al-C System by Mechanical Alloying, J. of All. And Comp. 260 (1997) 121-126. 10. Besterci, M., Preperation Microstructure and Properties of Al-Al4C3 System Produced by Mechanical Allying, Materials and Design, 27 (2006) 416-421. 11. Zhou, Y., Li Z.Q., Structural Characterization of a Mechanical Alloyed Al-C Mixture, J. Alloys and Comp.,414 (2006) 107-122. 12. K.S. Dunnett, R.M. Mueller, D.P. Bishop, Development of AlNiMg(Cu) Aluminum P/M Alloys, Journal of materials processing technology 198 (2008) 3140. 13. Zhou, J., Duszczyk, J., 1999. Liquid Phase Sintering of an AA2014-Based Composite Prepared from an Elemental Powder Mixture. J. Mater. Sci. 34, (2008) 545550. 14. imir, M., Gngr, ., gel, B., Al-Cu ve Al-Cu-Mg Toz Karmlarnn Azot Atmosferi Altnda Scak Presleme almalar, 10. Uluslararas Metalurji ve Malzeme Kongresi Bildiriler Kitab Cilt III, 24-28 Mays, stanbul, 1781-1788 (2000). 15. Cotterill P., Mould P.R., Recrystallization and Grain Growth in Metals, Surrey University Press, London, UK, (1976). 16. Doherty R.D., The Deformed State and Nucleation of Recrystallization, Metal Science, 8 (1974) 132-142. 17. Higgins G.T., Grain Boundary Migration and Grain Growth, Metal Science, 8 (1974) 143-150. 18. Hoyt J.J., On the Coarsening of Precipitates Located on Grain Boundaries and Dislocations, Acta Metall. Mater., 39 (1991) 2091-2098.
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Serkan BIYIK1 , Fazl ARSLAN2 1 Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080, Trabzon, e-mail: serkanbiyik@ktu.edu.tr 2 Karadeniz Teknik niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 61080, Trabzon, e-mail: farslan@ktu.edu.tr zet Bu almada TM yntemiyle retilen Ag-B2O3 esasl kontak malzemelerinin zelliklerine B2O3 orannn etkisi incelenmitir. Gm ve bor oksit tozlar retildikten sonra homojen bir ekilde kartrlp 1000 MPada preslenmitir. Preslenen numuneler 800Cde sinterlenmitir. Bor oksit % 0 ile % 15 orannda ilave edilmitir. Sabit ve hareketli kontak iftlerinin malzemeleri ayn trden seilmitir. Numunelerin belirli evrim saylar sonunda arlklar llm ve yzeyleri metal mikroskobu ve SEMde incelenmitir. Deneyler 220 V, 50 Hz ve 5 A alternatif akm altnda yaplmtr. evrim says dakikada 60 ama-kapama olacak ekilde seilmitir. Ama-kapama says 40.000 evrime kadar kartlarak, evrim says ile arlk kayb arasndaki ilikiler aratrlmtr. Belirli evrim saylarnda kontaklarn yzeylerinde yaplan incelemelerde ark etkili blge, gei blgesi ve ark etkisiz blge olmak zere farkl blgenin olutuu gzlenmitir. Ark etkili blgeler evrim saysnn artmasyla genilemitir. Saf gm ve B2O3 orannn dk olduu kontak malzemelerinde ark etkili blge yzeyinde ergime sonucu nispeten kaba girinti ve kntlar oluurken, artan B2O3 oranyla ark etkili blgede belirgin ergime izleri azalmtr. B2O3 orannn yaklak % 8 kadar artmasyla arlk kaybnda azalmalar tespit edilmitir. Bu azalma zellikle % 10 orannda B2O3 ieren kontaklarda olduka belirgindir. Anahtar Kelimeler: Elektrik Kontak Malzemeleri, Ag Esasl Kontak Malzemesi, Ark Erozyonu, Bor Oksit
TOZ METALURJS YNTEMYLE Ag-B2O3 ESASLI KONTAK MALZEMES RETM VE ZELLKLERNN NCELENMES
InvestIgatIon of PropertIes of SIlver - BorIc OxIde Based Contact MaterIals Produced by Powder Metallurgy
ABSTRACT In this study, the effects of boric oxide content on the properties of Ag-B2O3 based contact materials which were produced by PM were investigated. Silver and boric oxide powders were uniformly mixed and pressed at 1000 MPa. Compacts were sintered at 800C. The boric oxide content was changed between 0 % and 15 %. Both the fixed and the movable contacts were selected from the same material. The contact surfaces and the weight losses were examined after certain cycles. Arc erosion experiments were carried out at 220 V, 50 Hz, 5 A AC and cycled at 60 operations per minute. The number of cycles were increased up to 40.000 and the relationship between weight loss and cycle number were investigated. It was observed that all the samples were loosing weights rapidly up to 20.000 cycles and after that point, the weight losses were slow up to 40.000 cycles. The effects of B2O3 was not significant at low contents of B2O3 but reached to minimum weight loss at about 8 % contents of B2O3. Examinations of contact surfaces using metal microscope and SEM after certain cycles showed that the arc affected zones enlarged with increasing number of cycles. Arc affected zone was almost diminished in 10 % B2O3 containing materials, this was attributed to cooling effect of B2O3 particles which was melted at 450C. Key Words: Electrical Contact Materials, Silver-Based Contacts, Arc Erosion, Boric Oxide
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1. Giri Kontaklar, elektrik uygulamalarnn ounda kullanlan ve bir ya da daha fazla saydaki devrenin elektrik akmn ap kapamak suretiyle ayn anda bu devreleri kumanda edebilen kontaktr ve rle gibi elektromanyetik anahtarlarn en nemli elemanlarndan birisidir. Karlkl olarak alan, akm tama ve akm kesme grevlerini stlenen kontaklar, alp-kapanma srasnda oluan ark ile ar ekilde snmakta ve hem ergime hem de buharlama yolu ile nemli miktarlarda malzeme kaybna uramaktadrlar. Buna ek olarak kontaklarn yzeyleri bozulmakta ve bir kontaktan dierine malzeme transferinin meydana gelmesiyle kontaklar alamaz hale gelmektedirler. Bu olumsuz durumlar en aza indirerek kontaklarn mrlerini uzatmak iin seilecek kontak malzemelerinin, akmn geii srasnda oluan yksek sy ileterek kontaklarn ar snmasn nleyecek yksek elektriksel iletkenlie, ortaya kan ark ssn iletecek yksek sl iletkenlie, kontaklarn yzeylerinde birikerek yaltkanla sebep olan oksit, slfit ve dier bileiklere kar yksek reaksiyon direncine, ark erozyonunu, malzeme transferini ve kaynak olmay (yapmay) snrlayacak yksek ergime noktasna ve dk buhar basncna, iyi bir anma direnci iin yksek sertlie sahip olmas gerekir. Fakat hibir malzeme sralanan btn bu zelliklere tek bana sahip olmadndan emniyet, elde edilebilirlik, mr ve maliyet gz nne alnarak belirlenen her uygulama iin uygun bir malzeme seimi yaplmal ve farkl zelliklere sahip malzemeler bir araya getirilmelidir. Kontak malzemelerinin seiminde, elektrik devresinin karakteristikleri (akm, gerilim v.b.), ykn eidi, kapasite, kontaklara uygulanan kuvvet, kontaklarn alp-kapanma says, alp-kapanmann skl ve gvenilirlik gz nne alnmas gereken faktrlerin balcalardr [1-4]. Kontaklardan geen akmn alternatif ya da doru akm, yksek ya da dk deerli, ykn indktif, kapasitif, diren ya da bir motor yk olmas da malzeme seiminde nemlidir. Metallerin mrn nemli oranda azaltan atmosfer etkisi, kirlilikler, gazlar, tozlar, nem ve organik buharlar gibi evresel faktrler de kontak malzemesinin seiminde nemli rol oynamaktadr. Saf gmn dier metaller iinde en yksek sl ve elektrik iletkenliine sahip olmas, kontak malzemesi olarak kullanmn cazip klmasna karn, ark erozyonuna kar mukavemeti arttrmak, kaynama veya yapmay en aza indirmek; oksit ierikli birok malzeme ile birletirilmesini gerekli klmtr. Dkm yolu ile retilemeyen bu malzemeler, toz metalurjisi ve i oksidasyon yntemleri ile elde edilmektedir. oksidasyon iin gerekli zamann ok uzun olmas, oksit dalmnn, byklnn, eklinin dzensiz olmas ve oksit ieriinin snrl oranda olmas, toz metalurjisi tekniinin i oksidasyona tercih edilmesinin balca sebeplerini oluturmaktadr. Toz metalurjisi yntemi kullanlarak istenilen zelliklerde rnlerin elde edilebilmesi, aadaki proses deikenlerinin doru olarak seilmesine ve kontrolne baldr [5]: Toz zellikleri, Tozun hazrlan yntemi, Sktrmann nasl uyguland, Sktrmann yapld kalp ve aletlerin tasarm, Sinterleme frnnn tipi, Sinterleme atmosferinin bileimi, Sinterleme scakl ve zaman da dahil olmak zere retim ak, kincil uygulamalar ve sl ilem. Kontaklardan beklenen yararl kullanm mrleri, fzelerde birka operasyondan, otomobil titretiricilerinde yz milyon evrime (ama-kapama) ve telefon rlelerinde krk yla kadar deimektedir. Bu almann amac yeni kontak malzemeleri bulmak ve gelitirmektir. Bu amala K.T.. Fen Bilimleri Enstits Metalurji ve Malzeme Mhendislii Anabilim Dal Toz Metalurjisi Laboratuarnda toz metalurjisi yntemiyle deiik oranlarda B2O3 ieren gm esasl kontak malzemeleri retilmi ve ark erozyon deneylerine tabi tutulmutur. Ark erozyon davranlar incelenen kontak malzemelerinde B2O3 in ark erozyonuna ve arkn kontaklarda oluturduu yzey bozunumuna etkileri incelenmitir. 2. DENEYSEL ALIMALAR Bu almada hacimsel olarak %5, %10 ve %15 B2O3 (bor oksit) ieren Ag (gm) esasl elektrik kontak malzemeleri toz metalurjisi yntemi kullanlarak retilmitir. retilen bu kontaklar tasarm ve imalat yaplan deney dzeneinde ark erozyon testlerine tabi tutulmulardr. Deneylerde kontaklarn 10.000, 20.000, 30.000 ve 40.000 kez alp-kapanmas (evrim) sonunda, kontak yzeylerinde meydana gelen ark bozunumlar incelenmitir. Her evrim aral sonunda sabit ve hareketli kontaklarn arlklar llerek, ark erozyonu ile kontak iftleri arasndaki malzeme transferleri deerlendirilmitir. Elde edilen bulgular ile de, test edilen drt deiik kontak arasnda karlatrmalar yaplarak B2O3 orannn kontak erozyonuna etkisi incelenmitir.
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2.1. Kullanlan Malzemeler ve Toz retimi Kontaklar retmek iin gerekli olan gm tozu, ticari saflktaki gm (%99,7) bir parann mekanik eelenmesiyle elde edilmitir. B2O3 ise Etibank tesislerinde retilmi olup, piyasadan toz halinde alnmtr. retilen tozlar 250 mlik elekten elenerek, elek alt tozlar kontak malzemesi imalinde kullanlmtr. Deneyde kullanlan tozlarn SEM grntleri aada verilmitir (ekil 1 ve ekil 2).
ekil 1. Gm tozu
ekil 2. Bor oksit tozu 2.2. Toz Metalurjisi Yntemiyle Ag B2O3 Kontak Malzemesi retimi lk olarak Ag ve B2O3 tozlar srasyla %5, %10 ve %15 olmak zere, belirli hacim oranlarnda kartrlmtr. Karmn homojen olabilmesi iin kartrlma esnasnda tozlara etil alkol pskrtlmtr. Elde edilen bu toz karm ekil 3 ve ekil 4de grnleri verilen kalpta sktrlmtr. Sktrma ilemi 15 ton kapasiteli hidrolik bir pres ile yaplmtr. Sktrma basnc 1000 MPa olarak alnmtr.
ekil 3. Ag B2O3 tozlarnn preslenmesinde kullanlan kalbn grn
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ekil 4. Ag B2O3 tozlarnn presleme kalbnn teknik resmi Sktrlan toz karm, baka bir ifadeyle ham kompaktlar sinterlenmek zere ii odun kmr ile doldurulmu olan bir elik tp iine (ular kapal) yerletirilmitir. Bu suretle indirgeyici atmosfer oluturularak oksitlenme nlenmitir. Sinterleme ilemi sinter frnnda 800Cde 1 saat sre ile gerekletirilmitir. Sinterlenmi olan bu paralar biri sabit kontak, dieri de hareketli kontak olacak ekilde bakr levhalara lehimlenmilerdir. Lehimleme ileminin ardndan kontak yzeyleri ilenip en son 800 numaral zmpara ile zmparalama ilemi yaplmtr. Elde edilen kontaklarn ykseklii yaklak 2.50 mm olarak llmtr. Hem alt hem de st kontaklarn aplar 5 mmdir. Btn lmler dijital kumpas kullanlarak yaplmtr. st kontaklar hareketli, alt kontaklar ise sabit olarak kullanlmtr. Kontaklar iin kullanlan retim metodunun i ak diyagram ekil 5de gsterilmitir. ekildeki ak diyagramna gre imal edilip son ekline getirilen Ag - %5 B2O3, Ag - %10 B2O3, Ag - % 15 B2O3 ve ayrca saf gm kontaklar ark erozyon testlerine tabi tutulmutur. Testlerden sonra numunelerin yzeyleri metal mikroskobunda ve SEMde incelenerek fotoraflar ekilmitir.
ekil 5. Kontak malzemesi retiminde izlenen i ak diyagram
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2.3. Deney Dzenei Elektrik Devresi Ag B2O3 kontaklarnn test edilmesinde kullanlan deney dzenei ekil 6da grld gibidir.
ekil 6. Kontaklarn test edilmesinde kullanlan deney dzenei Deney dzenei elemanlar rle, ift ayarl flr, reosta, varyak ve doru akm kaynandan olumaktadr. Rlenin bobini 24 voltluk doru akm ile almaktadr. Bobin ilevi, akm getiinde mknatslanarak hareketli konta kendine doru ekmesi ve akm kesildiinde ise konta brakmas eklindedir. Bu ekilde hareketli kontan sabit kontak zerine kapanp almas salanmtr. Kontaklarn belirli frekanslarda alp kapanmalarn salamak iin ift ayarl flr kullanlmtr. Bylelikle kontaklarn ne sklkla alp kapanaca ve evrim sonras bekleme sresi kolaylkla ayarlanabilmitir. Devreden geen akm artrmak veya azaltmak iin dzenee varyak dahil edilmitir. Rlenin kontaklar 220 V gerilim ve 50 Hz frekans deerindeki alternatif akm ebekesine balanmtr. Ayrca kontaklar zerinden 5 A lik akmn ekilmesi iin de devreye reosta eklenmitir. Kontaklar retilip bakr levhalara lehimlendikten sonra kontak sistemine monte edilmilerdir. Kontak sistemi ekil 7de grld gibidir. 2.4. Deneylerin Yapl Gm ve bor oksit tozlar elek sisteminden geirilmi ve 250 mlik elek alt tozlar kontaklarn retiminde tercih edilmitir. Ortalama parack boyutu arttka, sinterleme ilemi kt ynde etkilenecektir [6]. Bu nedenle 250 mlik elek alt tozlar presleme ve sinterleme asndan uygun grlmtr. Hacimsel olarak %5, %10 ve %15 orannda B2O3 ieren Ag B2O3 kompozitleri daha nce bahsedilen ak emasna uygun olarak imal edilmilerdir. ekil 6da gsterilen deney dzeneindeki devreye monte edilen sabit ve hareketli kontaklar belirli ama kapama saylarnda alnarak arlklar llm ve daha sonra da yzeyleri metal mikroskobu altnda incelenmitir.
ekil 7. Kontak sistemi
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Deneylerden nce ortamn scakl ve nemi higrometreyle (nem ler) llmtr. Deneylerde nem orannn % 41 RH % 60 RH arasnda olduu grlmtr. Sistemin almas esnasndaki scaklk artlar ise kzltesi termometre araclyla belirlenmitir. Yzeylerin incelenmesinde ise metal mikroskobu kullanlmtr. ift ayarl flr ile kontaklarn saniyede bir kez alp-kapanmas salanmtr. Aratrmaclarn yapt almalarda da deneylerin salkl olmas asndan ama-kapama says dakikada 60 olarak alnmtr [7]. Kontaklardan 220 V gerilim, 50 Hz frekans deerlerinde 5 Alik alternatif akm geirilerek deneyler yaplmtr. Yaplan incelemelerde her kontak malzemesi ifti iin ark erozyonu ve yzeyde ark ile ortaya kan deiiklikler karlatrmal olarak incelenerek B2O3 orannn etkisi deerlendirilmitir. 3. SONULAR 1. Alternatif akm artlarnda (220V, 50 Hz, 5 A) yaplan deneyler sonucu yaklak 20.000 ama-kapamada her drt eit kontak iftindeki toplam arlk kaybnda nispeten hzl bir art grlm ve bu evrimden sonra arlk kaybndaki azalma yavalamtr (ekil 8).
ekil 8. Drt farkl malzemeden yaplm kontak iftlerine ait toplam arlk kayplarnn ama-kapama says ile deiimi 2. Gme % 5 B2O3 katlmasyla retilen kontak iftindeki toplam arlk kayb, saf gm kontaktakine yakn seyrederken, zellikle % 10 B2O3 ieren Ag - B2O3 kontak iftlerinde arlk kaybnda saf gme gre nemli lde d grlmtr. Kontak malzemesindeki B2O3 oran arttka (yaklak % 10 B2O3 oranna kadar) arlk kaybnda azalma gzlenmitir (ekil 8 ve ekil 9).
ekil 9. Deiik ama-kapama saylar iin kontak iftlerine ait toplam arlk kayplarnn bor oksit oranyla deiimi
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3. Sabit kontaklarda saf gm ile % 5 B2O3 ieren kontak malzemeleri benzer davran sergilerken, % 10 B2O3 ieren kontak malzemelerindeki arlk kayb nemli lde d gstermitir (ekil 10). Hareketli kontaklarda ise, saf gm ile % 15 B2O3 ieren malzemelerde daha yksek arlk kayb grlmtr (ekil 11).
ekil 10. Drt
farkl malzemeden yaplm sabit kontaklarn arlk kayplarnn ama-kapama says ile deiimi
ekil 11. Drt farkl malzemeden yaplm hareketli kontaklarn arlk kayplarnn ama-kapama says ile deiimi 4. zerlerinden akm geen kontak iftlerinin alp-kapanmalar srasnda oluan ark nedeniyle kontak yzeylerinde yapsal deiiklikler olmutur. Genel olarak nispeten fazla arlk kayb gsteren numunelerde arkn etkin olduu blgenin nispeten daha belirgin ve daha geni olduu gzlenmitir (ekil 12 ve ekil 13).
ekil 12. % 15 B2O3 ieren kontaklarda meydana gelen ark etkili blgelerin grnm
ekil 13. % 15 B2O3 ieren kontaklarda meydana gelen ark etkili blgelerin dier bir grnm
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5. Saf gm kontaklarn yzeylerinde oluan ark etkili blge homojen olmayan bir deiim gsterirken, B2O3 ieren Ag - B2O3 kontak yzeylerinde % 10 B2O3 oranna kadar artan B2O3 oranyla daha homojen bir grnm sergilemitir (ekil 14 ve ekil 15).
ekil 14. % 10 B2O3 ieren kontaklarda meydana gelen homojen ark etkili blge
ekil 15. % 10 B2O3 ieren kontaklarda meydana gelen homojen ark etkili blgenin dier bir grnm
6. Sabit kontaklarn yzeylerindeki ark etkili blgelerde genellikle ergime sonucu malzeme kntlar ve ark noktalar oluurken, hareketli kontaklarda daha geni alana dalm ukurcuklar ve nispeten kk kntlarn olutuu grlmtr. 4. KAYNAKLAR 1. Akarsu, F., Dalay, N., Dlen, E., Erdoan, F., Gnsel, E., Kan, B., Savat, G., Sevindik, A. ve Soytrk, E., Nasl alr, Cilt I, Marshall Cavendish Ltd., Londra ve Geliim Basm Yaym A.., stanbul, 1980. 2. Askeland, D.R., The Science and Engineering of Materials, University of Nostrand Reinhold (International), Missouri, Rolla, 1988. 3. Onaran, K. ve Altnta, S., Malzemelerin Yap ve zellikleri, Elektronik zellikler, 4. Cilt, Birinci Bask, .T.. Ktphanesi, Say: 1332, Gmsuyu, stanbul, 1986. 4. Ayar, H., Elektrik Kontak Malzemeleri, Bitirme almas, K.T.., Mhendislik Mimarlk Fakltesi, Makine Mhendislii Blm, Trabzon, 1986. 5. Anonim, Metals Handbook, Properties and Selection: Irons, Steels and High Performance Alloys, A.S.M., 1993. 6. Sarta, S., Trker, M. ve Durlu, N., Toz Metalurjisi ve Parackl Malzeme lemleri, Ankara, Temmuz 2007. 7. Wingert, P.C. ve Horn, G., The Effects of CdO on the Static Gap Arc Erosion of Silver Based Contacts, IEEE Transactions on Components, Hybrids and Manufacturing Technology, 16, 2 (1993)
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AIRLIKA %10 SiC PARACIK TAKVYEL AL MATRSL KOMPOZT RETMNDE, RETM YNTEMNN KOMPOZT ZELLKLERNE ETKS
Hasan KARABULUT*, Ramazan ITAK**
*
Ankara Altnda Siteler Mesleki Eitim Merkezi, Metal Teknolojisi retmeni, Siteler, 06500, Ankara, karabulut.hasan@hotmail.com ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, rcitak@gazi.edu.tr zet
Arlka % 10 SiC parack takviyesi ieren Al matrisli kompozitler turbulada kartrma (TK) ve Mekanik alamlama (MA) yntemi ile retildi. TK ilemi homojen bir karm salamak amacyla 1 saat sreyle yaplm olup, MA ilemi 10 saat sreyle gerekletirildi. TK ve MA yaplm numunelerin toz boyutu, parack dalm, sertlik, younluk, gzeneklilik gibi karakteristik zellikleri ve abrasif anma direnleri incelenerek kyaslamalar yapld. Yaplan deney ve analiz sonularnda MA yaplm numunelerin TK numunelerine gre daha homojen bir parack dalmna sahip olduu belirlenmitir. TK numunelerinin younluunun daha fazla, dolaysyla daha az gzenek deerine ve daha yksek abrasif anma direncine sahip olduu; MA uygulanm numunelerin ise, toz boyutunun daha kk, sertlik deerinin daha yksek olduu belirlenmitir. Anahtar Kelimeler: Kompozit, mekanik alamlama, SiC, abrasif anma direnci, sertlik.
EFFECT OF PRODUCTION METHODS ON COMPOSTE PROPERTIES FOR %10 (BY WEIGHT) SiC PARTICLE REINFORCED AL MATRIX COMPOSITES
ABSTRACT Al matrix composites containing 10 % (by weight) SiC particle reinforcement was produced by turbulent mixing (TK) and mechanical alloying (MA). Mixing process in order to ensure a homogeneous mixture was carried out in a three dimensional turbula device for one hour. MA process was performed for 10 hours. Particle size, reinforcement distribution, hardness, density, porosity and abrasive wear resistances of composites were investigated and compared. It was determined that MA samples had more homogeneous reinforcement distribution than TK samples. TK samples had high density and less porosity and higher abrasive wear resistance. It has also been determined that MA samples had smaller particle size and higher hardness. Keywords: Composite, mechanical alloying, SiC, abrassive wear, hardness. 1. GR Yeni malzeme gelitirme almalar srekli devam etmekte olup, kompozit malzemeler iin yaplan almalarda ok hzl bir ekilde ilerlemektedir. Kompozit malzemeler, kimyasal bileimi ve zellikleri farkl olan iki veya daha fazla malzemenin makro dzeyde birletirilmesiyle elde edilen malzemeler olarak tanmlanmaktadr [1]. Kompoziti oluturan malzemeler ara yzeylerle birbirlerinden ayrlr ve yap iinde kendi zelliklerini korurlar. Ancak kompozit malzemenin zellikleri, kendisini oluturan malzemelerin zelliklerinden stndr [2]. Kompozit malzemelerin ou takviye elemanlar ve bunun etrafn evreleyen matris malzemesinden olumaktadr. Takviye elemanlarnn temel fonksiyonu gelen yk tamak, matrisin rijitlik ve dayanmn arttrmaktr. Kompozit malzemelerin retiminde uygun
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artlar oluturulursa hafif alamlarn darbe ve anma dayanm arttrlabilir, yksek scaklklarda alabilecek zellikler kazandrlabilir ve younluklarn drmekte mmkn olabilir [3]. Bu sebeple dk younluklu alminyuma yaplan seramik takviyesi ile yksek mekanik zelliklere sahip kompozitler retilebilir. Alminyum ve alamlarnn dayanmlarn artrmak ve dier zelliklerini de iyiletirmek iin sert takviye elemanlaryla (fiber, whisker, parack gibi) alminyum matrisli kompozitler retilmektedir [4]. Kompozit malzemeler, eitli dkm ya da toz metalurjisi teknikleriyle retilebilir. Bu tekniklerden bir tanesi de bir kat hal ilem teknii olan mekanik alamlama yntemidir. Mekanik alamlama ilemi ile dkm ynteminde karlalan homojenlik, slatlabilirlik, birbiri ierisinde karmama vb. problemler ortadan kaldrlabilmektedir [5]. Bu almada, Al matrisli ve arlka %10 SiC parack takviyeli kompozitler kartrma ve mekanik alamlama yntemiyle retilmitir. Mikroyap, tane boyutu, younluk, gzeneklilik ve sertlik gibi zelliklerin yannda abrasif anma direnlerinin de incelenmesi amalanmtr. 2. DENEYSEL ALIMALAR Matris malzemesi olarak kullanlan alminyum tozlar % 99,7 saflkta olup 72 m ortalama toz boyutundadr. Takviye eleman olarak SiC seramik tozlar ise; 12 m ortalama toz boyutundadr. Kartrma ilemi homojen bir karm elde etmek amacyla 1 saat sreyle boyutlu kartrma yapabilen turbula cihaznda bilyesiz olarak yapld. Mekanik alamlama ilemi ise; szegvari modeli dikey bir atritr ierisinde 10/1 bilye/toz orannda 10 mm apnda elik bilye ve 0,75 g yalayc ile birlikte yapld. MA ilemi 350 rpm hzda, akan argon atmosferinde 10 saat srede uygulanmtr. MA srasnda snmay nlemek iin silindir, akan souk su ile srekli soutuldu. TK ve MA ileminin toz boyutuna etkisini belirlemek iin toz boyut analizi yaplmtr. Ardndan kompozitlerin mikroyap, younluk, gzeneklilik, sertlik ve abrasif anma direnlerini belirlemek amacyla 12 x 15 mm boyutlarnda blok numuneler 700 MPa presleme basncnda tek ynl olarak preslendi. Preslenen numuneler 600 C scaklkta akan argon atmosferinde 1 saat sreyle sinterlendi. Sinterleme ncesi ve sonras younluk lmleri yaplarak gzenek deerleri belirlenmitir. Sinterlenen numunelerdeki sinterlemeyi ve faz dalmn grebilmek iin, ncelikle numuneler uygun zmparalama, parlatma ve dalamann ardndan Optik Mikroskop ve Taramal Elektron Mikroskobu ile incelendi. Sertlik lmleri Brinell sertlik lm cihaznda 2,5 mm bilye u ve 31,25 kgf yk uygulanarak gerekletirildi. Her numune iin 6ar adet lm yapld ve bu deerlerin ortalamas alnd. Anma deneyleri 1200 meshlik SiC abrasif andrc zmparalar ile 7,5 m mesafede kuru ve yasz kayma koullar altnda gerekletirildi. Anma deney ncesi ve sonrasnda hassas terazi ile arlklar lld ve deney sonras arlk kayplar belirlendi. Resim 1de anma deneylerinin gerekletirildii deney cihaz grlmektedir.
Resim 1. Anma deney dzenei [a) SiC zmpara, b) Numune tutucu (mandren), c) Dner disk] 3. DENEYSEL SONULAR 3.1 Toz Boyutu lmleri ekil 2de grld gibi, MA uygulanm numunelerde toz boyutlar 45 m lara kadar derken, TK ilemi yaplm numunelerde karmn ortalama toz boyutu 67 m olarak llmtr. Bunun sebebi MA uygulanm numunelerde tozlarn 10 saat sreyle yksek enerjili deirmen ierisinde deformasyona maruz kalmas ve dolaysyla ortaya kan peklemenin sonucunda krlma mekanizmasnn etkili olmasdr. Karabulut ve tak benzer artlarda Al Mat-
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risli ve Al2O3 parack takviyeli kompozit retmiler ve 10 saat MA ileminin sonucunda parack boyutunun 27 m mertebesine kadar dtn bulmutur [6]. Benzer ekilde Ark ve Trker MA yntemi ile rettikleri Fe-Fe3C kompozitlerde alamlama sresinin artmasyla toz boyutunda azalmalar olduunu tespit etmitir [7]. Her iki almada da ortaya kan sonular bu almay destekleyici niteliktedir.
ekil 2. Toz boyut analiz sonular Resim 2de TK ve MA yaplm toz numunelerin SEM fotoraflar verilmitir. Resimlerde de grld gibi MA yaplm numunelerde tme artlarndan kaynakl deformasyonun etkisi ile oluan tane klmesi ve pullama belirgindir, ancak turbula cihaznda bilyesiz olarak kartrma yaplm toz numunelerde herhangi bir deformasyon etkisi grlmemektedir.
Resim 2. TK ve 10 saat MA yaplm tozlarn SEM grnts 3.2 Younluk ve Gzeneklilik Deerleri ekil 3te blok numunelerin sinterleme ncesi/sonras younluk ve gzeneklilik deerleri verilmitir. Bu sonulara gre turbulada kartrma yaplm numunelerin daha yksek younlua ve daha az gzeneklilik deerine sahip olduu grlmektedir. TK ilemi yaplm numunelerin ham younluklar % 96 iken; MA yaplm numunelerin ham younluklar % 94 olarak belirlenmitir. Sinterleme sonras ise numunelerin younluk deerleri bir miktar artmtr. Mekanik alamlanm numunelerin TK numunelerine gore younluklarnn dk olmasnn sebebinin MA srasnda yksek deformasyonun etkisiyle tozlarda oluan peklemenin numunelerin presleme esnasnda sktrlabilirliini olumsuz etkilemesinden kaynakland sanlmaktadr. Karabulut ve taknda ayn artlarda rettikleri Al Matrisli ve Al2O3 ve SiC parack takviyeli kompozitlerde bulduklar benzer sonular bu almay desteklemektedir [6, 8]. Ayrca bu durum MA yaplm numunelerin toz boyutunun turbulada kartrma yaplm numunelere gre daha dk olmasndan da kaynaklanabilir. nk, kk tozlarn sktrmaya diren gsterdii ve bundan dolay zellikle nano boyutlu tozlarn sktrlabilirliinin ok zor olduu belirtilmektedir [9].
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ekil 3. Turbulada kartrma ve MA yaplm numunelerinin sinterleme ncesi ve sonras younluklar ve gzeneklilik deeri retilen blok numunelere ait optik mikroskop fotoraflar Resim 3de verilmitir. MA uygulanm numunelerin TK numunelerine nispeten daha homojen bir dalm sergiledii grlmektedir. Dier yandan MA ilemi uygulanan numunelerde TK numunelerine gre gzeneklilik orannn artt belirgindir. Her ne kadar MA ilemleri koruyucu gaz atmosferi altnda yaplsa da, uzun sreli MA ilemlerinde % 100 denge artlarnn salanmas zordur. Bu sebeple uzun sureli MA ilemlerinde toz yzeylerinde oluabilecek oksitlenmeler presleme ve sinterleme esnasnda olumsuz etkilere neden olabilir. Doal olarak numunelerin younluklar derken, gzeneklilik deeride bir miktar artmaktadr.
Resim 3. TK ve 10 saat MA yaplm blok numunelerin optik Mikroskop resimleri 3.3 Sertlik lmleri Sadece matris malzemesi olarak kullanlan alminyum tozlarndan ayn artlarda retilen blok numunelerin sertlik sonular 26 HB sertlik deerinde elde edilmiken, doal olarak parack takviyeli kompozitlerin sertlikleri hem TK ilemi, hem de MA ilemi sonucunda daha yksek kmtr. ekil 4te grld gibi MA yaplm numunelerin brinell sertlik deerleri, turbulada kartrma yaplm numunelerin sertlik deerine oranla neredeyse iki katna yakndr. Bu artn, MA srasnda oluan tane klmesinden kaynakland dnlmektedir. Ark, MA ile rettii kompozitlerde sertlik iin en nemli faktrlerden birinin MA sresi olduunu belirtmitir [10].
ekil 4. Sertlik sonular
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3.4 Anma Direnleri Tm numunelere anma deneylerinde 10, 20 ve 30 N yk uygulanmtr. Doal olarak yk miktarnn artmasyla anma miktarlar da artmtr. Saf alminyumda, retilen kompozit malzemelere gre daha kolay deformasyon olumu, izik oluumu ve srklenme sebebiyle anma daha kolay balamtr (Resim 4). Yumuak malzemelerin sert malzemelere gre daha abuk deformasyona urayaca ve dolaysyla malzemenin ekil deiimine uramasnn daha kolay olaca belirtilmitir [11]. Anma deneyleri ierisinde beklendii gibi en fazla anma miktar saf Al malzemede tespit edilmitir. Saf alminyumda abrasif anmada mikro kesmeyle birlikte yksek deformasyon sonucunda takozlama (srklenme) mekanizmas olumu ve buna bal olarak srekli geni izgiler meydana gelmitir. Hasrc ve Glde yaptklar almada benzer sonular bulmutur [11].
(a) (b) Resim 4. 30 N yk altnda anm numune SEM resimleri (a) Saf alminyum (b) TK ilemi yaplm kompozit (c) MA ilemi yaplm kompozit
(c)
TK ve MA tekniiyle retilen kompozitler de beklendii gibi anma miktarlar saf Al malzemeye kyasla daha azdr. Bu durum retilen kompozitlerde sert seramik parack takviyesinin etkisinden kaynaklanmaktadr.
ekil 5. Saf alminyum ve kompozitlerin arlk kayb miktarlar Genel olarak tm kompozitlerin anma miktarlar incelendiinde (ekil 5), TK ile retilmi olan numunelerin MA ile retilmi olan numunelere gre daha az andn grlmektedir. Bu durumun TK numunelerinin daha youn ve bu numunelerde sinterlemenin daha iyi olmasndan kaynakland sanlmaktadr. Benzer ekilde Kurt yapt almada, Al-Al2O3 takviyeli kompozitleri, 4er saat sreyle turbulada bilyesiz olarak kartrma, MA ve dner deirmende olmak zere farkl yntemle retmitir. retilen blok numunelerde en iyi anma performansnn turbula cihaznda retilen kompozitlerde olduunu tespit etmitir [12]. 1. SONULAR
MA ilemi ile uygulanm numunelerin toz boyutu nemli oranda klmtr. Sinterleme sonras tm numunelerin younluk deeri artmtr. TK numunelerinde sinterleme sonras younluk art daha fazladr, dolaysyla bu numunelerde sinterlemenin daha iyi olduu grlmtr. TK numunelerinin younluk deerleri MA numunelerine gre daha yksek ve dolaysyla gzenek deerleri de daha dktr. MA ile retilmi kompozitler TK ile retilmi kompozitlere gre daha serttir. MA numunelerinin abrasive anma direnleri TK numunelerine gre daha dktr.
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TEEKKR Gazi niversitesi BAP Birimine 07/2010-58 nolu proje kapsamnda yapt katklardan dolay teekkr ederiz. KAYNAKLAR 1. Kaw, A.K., Mechanics of Composite Materials, Crc Press, Washington, 3: 61-65 (1997). 2. Hull, D. ve Clyne, T.W., An Introduction to Composite Materials, 2nd Edition, Cambridge University Press, Cambridge, (1996). 3. Sahin, Y., Kompozit Malzemelere Giris, Gazi Kitabevi, Ankara, 65-69 (2000). 4. Jun D., Liu, Y.-H., Yu, S.-R., Li, W.-F. Dry sliding friction and wear properties of Al2O3 and carbon short fibres reinforced Al-12Si alloy hybrid composites, Wear, 257: 930-940 (2004). 5. Suryanarayana, C., Mechanichal alloying and milling, Progress in Materials Science, 46: 1-184 (2001). 6. Karabulut, H., tak, R., Al matrisli ve Al2O3 parack takviyeli kompozitler iin retim ynteminin kompozit zelliklerine etkisi 6th International Advanced Technologies Symposium (IATS11), 503-506, Elaz, 2011. 7. Ark, H., Trker, M., Production and characterization of in situ Fe-Fe3C composite produced by mechanical alloying, Materials & Design, 28: 140-146 (2005). 8. Karabulut, H., tak, R., Al matrisli ve SiC parack takviyeli kompozitlerin farkl mekanik alamlama srelerinde retilmesi ve karakterize edilmesi 6th International Advanced Technologies Symposium (IATS11), 527-530, Elaz, 2011. 9. Sarta, S., Trker, M, Durlu, N,.Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Yaynlar: 05, Ankara, 2-9, 15-34, 206, 237, 379-387, 404-410, (2007). 10. Ark, H., Production and characterization of in situ Al4C3 reinforced aluminum based composite produced by mechanical alloying technique, Materials and Design, 25: 1-4, (2004). 11. Hasrc, H., Gl, F., B4C /Al kompozitlerin takviye hacim oranna bal olarak abrasif anma davranlarnn incelenmesi, SDU International Journal of Technologic Sciences, Vol 2, PP 15-21, 2010. 12. Kurt, H., Alminyum Almina Kompozit Malzeme retiminde Kartrma Tekniinin Kompozitin Anma Davran zerine Etkilerinin Aratrlmas, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara, 33-48 (2010).
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YKSEK ORANDA GZENEK EREN DEMR ESASLI KOMPAKTLARDA RETM SREC ESNASINDA MEYDANA GELEN HACMSEL DEMLER
Nuray BEKZ*, Enver OKTAY* * stanbul niversitesi Metalurji ve Malzeme Mhendislii Blm, Avclar, stanbul. e-mail : nbekoz@istanbul.edu.tr, oktay@istanbul.edu.tr ZET Bu almada; toz metalurjisindeki boluk yapc teknii kullanlarak yksek oranlarda gzenek ieren demir esasl kompaktlarda retim sreci esnasnda meydana gelen hacimsel deiimler incelenmitir. Farkl ekil ve partikl boyutlarna sahip karbamit, Astaloy Mo tozlaryla kaplandktan sonra 200 MPa basn altnda preslenerek boy/ap oran yaklak 1,5 olan silindirik ham kompaktlar retilmitir. Ham kompaktlar ierisindeki karbamitin suda zndrlerek uzaklatrlmasyla elde edilen gzenekli yaplar hidrojen atmosferinde 1200 Cde 60 dakika sinterlenmitir. zndrme sonras ham kompaktlarda hacimsel byme meydana gelmi, artan karbamit miktar ve azalan karbamit boyutuyla hacimsel byme azalmtr. Sinterleme sonras numunelerde; gzenek miktar, ekli ve boyutuna bal olarak hacimsel ekme gereklemitir. Anahtar kelimeler: Gzenekli malzemeler, karbamit, sinterleme, hacimsel deiimler.
DIMENSIONAL CHANGES IN HIGHLY POROUS IRON BASED COMPACTS OCCURRED DURING MANUFACTURING PROCESS
ABSTRACT In this study; volume changes that occurred during manufacturing process of highly porous iron based compacts using the space holder technique in powder metallurgy were investigated. Different amount of space holder (carbmide) having different particle sizes and shapes were covered with pre-alloyed Astaloy Mo powder and then compacted at 200 MPa to produced green compacts having length to diameter ratio of about 1.5. Carbamide in the green compacts was removed by water leaching and then the highly porous green compacts were sintered at 1200 C for 60 minutes under hydrogen atmosphere. Volume expansion in the green compact occurred after water leaching. An increase in carbamide content and a decrease in carbamide particle size lead to lower volume expansions. Sintering caused volumetric shrinkage in the compacts. The extent of volumetric shrinkage after sintering was dependent on volume, shape and sizes of the pores. Keywords: Porous materials, carbamide, sintering, volumetric changes. 1. GR Yksek oranda gzenek ieren malzemeler; yksek mekanik enerji emebilme kapasitesi ve ok dk zgl arla sahip olduklar iin yapsal ve ilevsel amalarla kullanlmaktadr. Kpks metallerin gsterdii zellikler; ierdikleri gzeneklerin ekline, dalmna ve gzeneklerin birbirleriyle olan balantsna bal olarak deimekte ve ok farkl potansiyel kullanm alanlar gstermektedir. Kpks malzemeler ierdikleri gzenek tiplerine gre; ak, kapal ve kark gzenekli malzemeler olarak ayrlabilir. Gzenek tipi gzenek yapsn belirlediinden ayn zamanda kpks malzemenin pek ok zelliini de ortaya koymaktadr. Gzenein yaps; kpks malzemenin s iletkenliini, ses absorbsiyonunu, hava geirgenliini, mukavemetini, rijitliini etkilemektedir. Kapal gzenekli malzemeler, ak gzenekli olanlara nispeten daha yksek mukavemet, rijitlik ve darbe dayanmna sahiptir. Deformasyon mekanizmasnda gzenek duvar esnemesi ve bzlmesi de nemli bir rol oynadndan bu tip gzenek
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yapsna sahip malzemelerde gzenek duvarlar yapy rijitletirir. Bu bakmdan kapal gzenekli malzemeler, srekli titreime maruz kalan makine paralarnda esneklik vermek amacyla kullanlmaktadr. Ak gzenek yaps ise malzemenin rijitliini drmesine karn yksek s tanmn mmkn klan zelliinden dolay yksek g reten cihazlarda etkili bir soutucu mekanizma olarak kullanm alan bulmaktadr [1-2]. Boluk yapc kullanlarak toz metalurjisi yntemiyle gzenekli malzeme retimi; gzenek zelliklerinin, malzeme eklinin ve mekanik zelliklerinin kontrolnde dier yntemlere gre salad birok stnlkten dolay son yllarda kullanlan bir yntem olarak karmza kmaktadr [3-7]. Yaplan almalarda boluk yapc olarak; organik malzemeler, karbonatlar, metalik tozlar, seramik paracklar, polimerik tozlar, ii bo kresel tozlar veya tuz kullanlmtr. Boluk yapcnn ana yapdan uzaklatrlmas; boluk yapcnn uygun bir organik zcde veya suda zndrlmesi ve termal olarak ayrtrma ile yaplabilir. Organik zc ile boluk yapcnn giderilmesi evreye zararl atklar oluturabilir, termal olarak gidermede boluk yapcnn bozunmas sonucu ortaya kan gazn numuneyi paralama riski vardr bu durum ok dk sinterleme hzlarnda giderilebilir ancak uzun sre gerektirir ve bozunma esnasnda aa kan gazlar metalle reaksiyona girebilir. Boluk yapcnn suda zndrlerek giderilmesi evreye zarar olmayan olduka basit ve ucuz bir yntemdir. Toz metalurjisi ile retilecek bir parann dizaynnda gz nne alnmas gereken en nemli unsur paraya uygulanacak srelerdir. Parann sktrma kalb tasarmndan daha sonra uygulanacak btn sreler ve bu srelerden kaynaklanan boyutsal deiimler gz nnde bulundurularak kalp dizayn yaplmaldr [8-10]. Bundan dolay yksek oranda gzenek ieren demir esasl malzemelerin boluk yapc-toz metalurjisi yntemiyle retim srecinde numunelerde meydana gelen boyutsal deiimlerin belirlenmesi nem tamaktadr. Literatrde boluk yapc yntemiyle gzenekli malzeme retiminde; boluk yapc miktar, ekli ve boyutunun hacimsel deiimler zerine etkisinin aratrld bir almaya rastlanmamtr. Bu almada, toz metalurjisi yntemiyle Astaloy Mo tozundan yksek oranda gzenek ieren numuneler retilerek boluk yapc olarak kullanlan karbamitin miktar, ekli ve boyutuna gre; zndrme sonras numunelerde meydana gelen hacimsel deiimler karbamit miktarna gre; sinterleme sonras numunelerde meydana gelen hacimsel deiimler sinterleme sonras gzenek miktarna gre belirlenmitir. 2. MALZEME VE YNTEM Bu almada; Hgans firmas tarafndan atomizasyon yntemi ile retilmi ortalama tane boyutu 109 m olan dzensiz ekilli n alaml Astaloy Mo demir tozu kullanlmtr. Astaloy Mo tozu Fe-%1,5 Mo ve %0,8 Zn-Stearate PM isimli organik bazl yalayc iermektedir. Ham mukavemeti arttrmak amacyla balayc olarak kullanlan parafin Merck firmasndan temin edilmi olup 46-48 C arasnda erime scaklna sahiptir. Boluk yapc olarak, Merck firmas tarafndan temin edilen teknik safiyette karbamit (re) kullanlmtr. Karbamitin younluu; 1,34 g/cm , erime scakl 133 C ve 20 C scaklktaki suda znrl 108 g/mLdir. ekli kresel olan karbamitten eleme yaplarak +1000-1400 m boyut aralna sahip kresel ekilli; agat havanda tlp ardndan eleme yaplarak da +500-710 m, +710-1000 m ve +1000-1400 m boyut aralklarna sahip dzensiz ekilli karbamit elde edilmitir. ekil 1de atomizasyon yntemiyle retilmi n alaml Astaloy Mo tozunun Taramal Elektron Mikroskobu (SEM) grnts, ekil 2-(a), (b) ve (c)de srasyla; +500-710 m, +710-1000 m ve +1000-1400 m boyut aralklarna sahip dzensiz ekilli; (d)de +1000-1400 m boyut aralna sahip kresel ekilli karbamitlerin stereo mikroskop grntleri verilmitir.
ekil 1 : Deneysel almada kullanlan Astaloy Mo tozunun SEM grnts
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ekil 2 : (a) +500-710 m, (b) +710-1000 m ve (c) +1000-1400 m boyut aralklarna sahip dzensiz ekilli; (d) +1000-1400 m boyut aralna sahip kresel ekilli karbamitlerin morfolojisi Ham numunelerin mukavemetinin arttrlmas amacyla balayc olarak a.%3 orannda hazrlanan parafin zeltisi, n alaml demir tozuna hac.%2 orannda katlarak oda scaklnda 30 dakika kartrlmtr. Karma; hac.%50 ile %80 arasnda deien oranlarda farkl partikl boyut ve ekline sahip karbamit ilave edilip turbula tipi kartrcda 1 saat sre ile kartrma sonucu, karbamit paracklar demir tozlar ile kaplanmlardr. Optimum basn karbamit eklinin korunmas iin mmkn olduu kadar dk, retimin tamamlanabilmesi iin yeterli olacak kadar byk olmas amalanarak belirlenmitir. Tm numuneler iin optimum presleme basnc 200 MPa olarak belirlenmitir. Demir tozlaryla kaplanm karbamitin elik bir kalp ierisinde 200 MPa basn uygulanarak tek ynl preslenmesiyle 12 mm apnda ve yaklak 18 mm yksekliinde silindirik numuneler elde edilmitir. Ham numunelerdeki karbamitin byk blm saf su banyosunda zndrlerek giderilmitir. Numunelerin ierdii karbamit oranna gre suda zndrme sreleri 3-12 saat arasnda deimitir. Numunelerden zndrlen karbamit miktarlar, Jenco marka 6350 PH/COND/TEM model Kondktometre cihaz kullanlarak tespit edilmitir. Hacimce %70-80 orannda karbamit ieren numunelerdeki karbamitin yaklak %91-98i, hac.%50-60 orannda karbamit ieren numunelerdeki karbamitin ise yaklak %73-85i zndrlerek uzaklatrlmtr. Numunelerin ierisinde kalan az miktardaki karbamit ile balayc olarak kullanlan parafinin termal olarak giderilmesi ve sinterleme ilemi Lenton marka frnda yaplmtr. Seramik boru ierisine yerletirilen numuneler; ortamdan N2 gaz geirilerek nce 5 C/dak stma hzyla 400 Cye stlm ve bu scaklkta 30 dakika tutulmu daha sonra ortamdan yksek safiyette H2 gaz geirilerek 10 C/dakika stma hzyla 1200 Cde 1 saat sinterlenmitir. Presleme ncesi; demir tozlarnn, farkl partikl boyut ve ekilli karbamitin ve yzeyi demir tozuyla kaplanm farkl 3 partikl boyut ve ekilli karbamitin grnr younluklarn belirlemek iin 2 cm lk Arnold metre kullanlmtr. Ham numunelerin zndrmeden nce ve zndrmeden sonra younluklar ktle/hacim ilikisinden belirlenmitir. Numunelerdeki karbamitin zndrlerek uzaklatrlmas sonras boyut lmleri, zndrme ncesi boyut lmleriyle deerlendirilerek; farkl miktar, partikl boyut ve ekline sahip karbamit ieren ham numunelerde meydana gelen hacim deiimleri karbamit miktarna gre belirlenmitir. Sinterlenmi numunelerin younluklar, ak ve kapal gzenek oranlar Arimed Yntemine gre belirlenmitir. Ak ve kapal gzenek oranlarn belirlemek iin numuneler 150 Cde kaynayan parafin ierisinde 1,5 saat bekletilerek parafinin gzeneklere emdirilmesi salandktan sonra numunelerin arlk lmleri gerekletirilmitir. Farkl miktar, partikl boyut ve ekline sahip karbamit kullanlarak retilen numunelerin sinterleme sonras boyut lmleri, sinterleme ncesi (zndrmeden sonra) boyut lmleriyle deerlendirilerek; numunelerde meydana gelen hacim deiimleri sinterleme sonras numunelerin gzenek miktarna gre belirlenmitir. lmler 5 numune zerinde yaplarak ortalamalar alnmtr. 3. SONULAR VE DEERLENDRME Kalp ierisindeki metal tozuyla kaplanm boluk yapcnn grnr younluu sktrlabilirliinde belirleyici rol oynamaktadr. Demir tozuyla kaplanm farkl boyut ve ekilli karbamitlerin grnr younluklar; demir tozunun ve karbamitin grnr younluklar ve hacimsel oranlar kullanlarak karm kuralna gre hesaplanan grnr younluklar ve Arnold metre kullanlarak belirlenen grnr younluklar srasyla; (h) ve (b) ile ifade edilerek Tablo 1de verilmitir.
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Tablo 1 : Karm kuralyla hesaplanan ve Arnold metre ile belirlenen grnr younluklar
Artan karbamit oranyla grnr younluklar beklendii gibi azalmtr. Arnold metre kullanarak belirlenen grnr younluk deerleri, karm kuralna gre hesaplanan grnr younluk deerlerinden kk kmtr. Karbamitin balayc ile kartrlm demir tozlaryla kaplamas iin nemlendirilmesi, nihai karm sonras dk karbamit oranlarnda artan demir tozu veya yksek karbamit oranlarnda tam kaplanmam karbamitler buna neden olmutur. Demir tozuyla kaplanm farkl boyut aralklarna sahip dzensiz ekilli karbamitlerin grnr younluu artan karbamit boyutuna bal olarak bir miktar artmtr. Demir tozuyla kaplanm kresel ekilli karbamitin grnr younluu, ayn boyut aralna sahip dzensiz ekilli karbamitin grnr younluundan bir miktar yksek bulunmutur. Demir tozuyla kaplanm daha byk boyutlu ve kresel ekilli karbamitler ak esnasnda daha az srtnme direnci gsterdiklerinden grnr younluklar artmtr. Artan grnr younlukla birlikte demir tozuyla kaplanm karbamitlerin kalp ierisine ak davranlar ve preslenebilirlikleri daha iyi olmaktadr. Ham numunelerin zndrmeden nce ve zndrmeden sonraki younluklar, karbamitin miktar, boyut aral ve ekline gre Tablo 2de verilmitir. Tabloda numunelerin zndrmeden nceki ham younluklar .. ve zndrmeden sonraki ham younluklar .s. ile ifade edilmitir. zndrme sonras numunelerde bulunan karbamitin giderilmesi sonucu numunelerin younluklar azalmtr. Tablo 2 : zndrme ncesi ve sonras numunelerin ham younluklar
ekil 3de; farkl miktar, partikl boyut ve ekline sahip karbamit ilave edilerek retilmi ham numunelerde zndrme sonucu gerekleen hacim deiimleri karbamit miktarna gre verilmitir.
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ekil 3 : Farkl miktar, partikl ekli ve boyutuna sahip karbamit ieren ham numunelerde zndrme sonucu karbamit miktarna bal olarak meydana gelen hacim deiimleri
zndrme sonras tm numunelerde hacimsel byme meydana gelmi ve artan karbamit miktaryla hacim deiimi azalmtr. Metal tozuyla kaplanm karbamitlerin grnr younluklar artan karbamit miktaryla azalmtr. Grnr younluun azalmasyla preslemede sktrma orann artmas, daha yksek oranda karbamit ilavesiyle retilen numunelerin biraz daha mukavemetli olmasn saladndan bu numuneler zndrme sonucu daha az hacimsel byme gstermilerdir. Kresel ekilli karbamit kullanlarak retilen numunelerin hacim deiimleri dzensiz ekilli karbamit kullanlarak retilen numunelere gre daha fazla bulunmutur. +500-710 m, +710-1000 m ve +1000-1400 m boyut aralklarna sahip dzensiz ekilli ve +1000- 1400 m boyut aralna sahip kresel ekilli karbamitin hac.%80 orannda ilavesiyle retilen numunelerde zndrme sonras hacimsel bymeler srasyla; %1,32, 1,45, 1,56 ve 1,89 olarak tespit edilmitir. Demir tozuyla kaplanm kresel ekilli karbamitin grnr younluu yksek olduundan preslemede sktrma orannn dk olmas nedeniyle ham numunelerde hacimsel deiim daha fazla gereklemitir. Sonular; demir esasl ham numunelerden karbamitin zndrlerek uzaklatrlmas sonras meydana gelen hacimsel deiimler zerine en nemli etkiyi karbamit miktar ve eklinin yaptn, boyutun etkisinin ise daha az olduunu gstermektedir. Karbamitin uzaklatrlmas ve 1200 Cde 1 saat sinterleme sonras farkl oranlarda gzenek ieren numunelerin resimleri ekil 4de grlmektedir.
ekil 4 : (a) %47,5, (b) %56,0, (c) %60,5 ve d) %70,8 gzenek ieren numunelerin resimleri
Sinterleme sonras numunele3rin gzenek miktar, boyutu ve ekline bal olarak younluklar 2,25-4,09 g/cm , toplam gzenek oranlar %.48,4-71,1 ak gzenek oranlar %.23,8-68,4 ve kapal gzenek oranlar %2,6-27,1 arasnda deimitir. Azalan gzenek miktaryla ak gzenek oran azalrken kapal gzenek oran artmtr. Kresel ekilli karbamit kullanlarak retilen numunelerde kapal gzenek oran; gzeneklerin birbirinden izole olmasndan dolay daha yksektir. ekil 5de farkl miktar, partikl boyut ve ekline sahip karbamit kullanlarak retilen ve 1200 Cde 1 saat sinterlenmi numunelerde sinterleme sonras gzenek oranna gre gerekleen hacim deiimleri verilmitir.
ekil 5 : Farkl miktar, partikl ekli ve boyutuna sahip karbamit kullanlarak retilen ve 1200 oCde 1 saat sinterlenmi numunelerde gzenek miktarna bal olarak meydana gelen hacim deiimleri
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Sinterleme ncesi daha az gzenek ieren numunelerin ham younluklar dierlerine gre fazla olduundan bu numuneler sinterleme sonucu daha az hacimsel ekme gstermilerdir. Literatrde toz metalurjisi yntemiyle malzeme retiminde; Astaloy Mo tozlarndan retilen ham kompaktlarn 1120 Cde 30 dakika sinterlenmesiyle retilen 6,7 g/cm3 younluundaki kompaktlarda yaklak %0,2 orannda hacimsel ekme tespit edilmitir [11]. Karbamit ilave edilerek toz metalurjisi yntemi ile yksek oranda gzenekli malzeme retiminde; uygulanan dk presleme basnc ve retilen ham numunelerden karbamitin uzaklatrlmas sonucu younluklarnn dk olmas sinterleme sonras daha fazla hacimsel ekmeye neden olmaktadr. Ayn boyut aralna sahip kresel ekilli karbamit kullanlarak retilen numuneler dzensiz ekilli karbamit kullanlarak retilen numunelere gre daha fazla hacimsel ekme gstermilerdir. +1000-1400 m boyut aralna sahip dzensiz ve kresel ekilli karbamitin hac.%80 orannda ilavesiyle retilen numunelerin sinterlenmesi sonucu hacimsel ekmeleri srasyla; %6,88 ve %7,24 olarak tespit edilmitir. Kresel ekilli karbamit kullanmnda ham numunelerde metal-metal toz temasnn artmasndan dolay sinterleme sonras daha fazla hacimsel ekme gereklemektedir. Farkl boyutlarda dzensiz ekilli karbamit kullanlarak retilen numunelerde artan karbamit partikl boyutuyla hacimsel ekme artmtr. +500-710 m, +710-1000 m ve +1000-1400 m boyut aralklarna sahip dzensiz ekilli karbamitlerin hac.%80 orannda ilavesiyle retilen numunelerin sinterlenmesi sonucu hacimsel ekmeleri srasyla; %6,36, %6,57 ve %6,88 olarak tespit edilmitir. Kullanlan dzensiz ekilli karbamitin boyutu arttka ham numunelerde metal-metal temas noktalar artacandan sinterleme sonras daha fazla hacimsel ekme meydana gelecektir. zndrme sonras ham numunelerde karbamit miktar, partikl boyutu ve ekline bal olarak %1,38-3,29 arasnda hacimsel byme; sinterleme sonras numunelerde gzenek miktar, ekli ve boyutuna bal olarak %4,31-7,25 arasnda hacimsel ekme meydana gelmitir. Yksek oranda gzenek ieren Astaloy Mo numunelerin younluklar ve gzenek yapsnn; balangta kullanlan karbamit miktar, ekli ve boyutu ile kontrol edilebilecei saptanmtr. Teekkr Bu alma T-1431 proje numarasyla stanbul niversitesi Bilimsel Aratrma Projeleri Birimi tarafndan desteklenmitir. KAYNAKLAR 1. BANHART, J., Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress in Materials Science, 46, 559-632, 2001. 2. KREMER, K., LISZKIEWICZ, A., ADKINS, J., Development of Steel Foam Material and Structures, Technology Roadmap Program 9913 Final Report, The United States Department of Energy and American Iron and Steel Institute, 2004. 3. KOTAN, G., Production and Characterization of Porous Titanium and Ti-6Al-4V, Master Thesis, Middle East Technical University, Department of Engineering Science, 2006. 4. CONDE, Y., DESPOIS, J.F., GOODALL, R., MARMOTTANT, A., SALVO, L., MARCHI, C.S., MORTENSEN, A., Replication Processing of Highly Porous Materials, Advanced Engineering Materials, 8 (9), 795-803, 2006. 5. BAKAN, H.I., A Novel Water Leaching and Sintering Process for Manufacturing Highly Porous Stainless Steel, Scripta Materialia, 55, 203-206, 2006. 6. SURACE, R., FILIPPIS, C.D., LUDOVICO, A.D., BOGHETICH, G., Influence of Processing Parameters on Aluminium Foam Produced by Space Holder Technique, Materials and Design, 30, 1878-1885, 2009. 7. TUNCER, N., ARSLAN, G., Designing Compressive Properties of Titanium Foams, Journal of Materials Science, 44, 1477-1484, 2009. 8. GERMAN, R.M., Powder Metallurgy Science, The Pennsylvania State University, MPIF, Princeton, New Jersey, 1-878954-42-3, 1994. 9. KANG, S.L., Sintering, Densification, Grain Growth and Microstructure, Elsevier Butterworth-Heinemann, Linacre House, Jordan Hill, Oxford, 0-750663-855, 2005. 10. ORBAN, R.L., New Research Directions in Powder Metallurgy, Romania Report in Physics, 56(3), 505-516, 2004. 11. HGANS HANDBOOK-1, Material and Powder Properties, Sweden, 2004.
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PSKRTMEL EKLLENDRME LEMNN GZENEKLLE ETKLER

Shaker M. ASWAD ve Yusuf USTA* Makina Mhendislii Blm, Mhendislik Fakltesi, Gazi niversitesi, 06570, Maltepe-Ankara, *uyusuf@gazi.edu.tr ZET Bu almada, tasarmlar ve imalatlar yaplm olan yakndan elemeli nozullar ve gaz atomizasyon nitesinde, alminyum tozu kullanarak pskrtme ekillendirme (P) ile silindir zerinde bir kaplama tabakas oluturulmutur. Mekanik zellikleri dorudan etkilemesi nedeniyle, ekillendirme parametrelerinin gzeneklilie etkileri aratrlmtr. almann gerekletirilmesi iin kendi ekseni etrafnda dnen bir silindir atomizasyon dorultusuna dik olarak konumlandrlmtr. Deneyler srasnda atomize edilen tozlarn henz sv iken, sz konusu dnen silindire tutunmas salanmtr. Deney parametreleri olarak pskrtme mesafesi, atomizasyon basnc ve yakndan elemeli nozulun u ksmnn knt mesafesi seilmitir. Her bir parametre iin ayr deer (pskrtme mesafesi: 135, 165, 200 mm; atomizasyon basnc: 5, 10, 15 bar ve knt mesafesi: 4, 6, 8 mm) eitli denemeler sonucunda belirlenmi ve her bir art kez tekrarlanarak kaplamalar gerekletirilmitir. Yaplan deneylerin sonunda elde edilen kaplamalarn kenar ve orta ksmlarndan numuneler alnarak gzeneklilik, taneler aras balant, tane bykl ve tane ekli optik mikroskop altnda incelenmitir. Anahtar Kelimeler: Pskrtme ekillendirme, yzey kaplama, gaz atomizasyonu, alminyum boru
EFFECT OF PARAMETERS OF SPRAY FORMING ON POROSITY

ABSTRACT In this study, a coating layer has been formed on a cylinder with spray forming technique by using aluminum powders which has atomized by close coupled nozzles which have been designed and produced before. Since porosity has a major effect on the mechanical properties of spray formed parts, effect of the parameters on the porosity have been investigated in order to have higher mechanical properties. n the experimental step, a spinning cylindrical tube has been located straight forward to the atomization direction. During the experiments, the atomized aluminum powder has been sprayed with the help of nozzles when they were yet in the liquid form. The cylindrical tube rotates at different speed and the coating has been applied from 3 different distances as being 135, 165 and 200 mm. Therefore, a coating layer has been deposited on the surface of cylinder. n the study, the protrusion of 4, 6 and 8 mm at nozzle tip and 5, 10 and 15 bar pressure have been used besides of the spray distance. Each experimental condition has been repeated 3 times. Samples have been taken from the center and side of the each coated parts in order to examine their porosity, bonding with powders and substrate, powder sizes and powder shapes under an optical microscope. Keywords: Spray forming, surface coating, gas atomization, aluminum pipe
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1. GR Toz metalurjisi endstriyel olarak kullanlan imal usullerinden olmakla birlikte en farkl imalat yoludur. Toz metalurjisi, metalrjinin, metalik toz veya bu tozlarn ekillendirilip sinterlenmesiyle yaplan rnlerin imalat ile ilgili bir blmdr [1]. Toz metalurjisinin (T/M) amac metal ve metal alamlarnn tozlarn ergitmeden, basn ve scaklk yardmyla dayankl malzemeler haline sokmaktr. Dier metal ileme yntemlerine gre daha farkl bir uygulama olan T/Mnin stnlkleri; paralarn yksek kalitede, karmak yapda, kk toleranslarla ve daha ucuz olarak retilebilmesidir [2]. T/M kk, karmak ve boyutsal hassasiyeti yksek paralarn seri imalatna son derece uygundur. Belirli derecede gzenek (porozite) ve geirgenlik elde edilir. T/M ile retilen paralarn byk bir ksmnda elde edilen boyutsal hassasiyet ve yzey kalitesi talal ilem gibi ekstra operasyonlara olan gereksinimleri ortadan kaldrmas ve malzeme kaybnn ok az olmas T/M ynteminin ekonomik bir retim yntemi olduunun gstergesidir [3]. Tane boyutu ve gzenek miktar gibi zellikler malzemelerin mekanik zelliklerini nemli lde etkiler. Mekanik zelliklerin yksek olmasnn istendii durumlarda, tane yapsnn kk olmas ve gzeneklerin en az seviyede olmas gerekmektedir [4]. Metal pskrtmede esas prensip, zel olarak hazrlanm metalik yzeylere, ergitilmi sv metalin basnl gazlarn kinetik hz (itmesi) ile pskrtlmesidir. Bunlarn gnmz teknolojisinde kullanlan deiik usulleri olduu gibi daha yeni usuller de denenmekte ve kullanlmaktadr [5]. P ilemi, para retmek iin, atomizasyon ve birletirme/pekitirme olaylarnn srayla gereklemesi prensibine dayanr. lemin ana ekiciliklerinden biri yksek malzeme biriktirme orandr (0,2-2 kg/s) [6]. Ergimi metali hava, azot, argon veya helyum gazlar kullanarak paralamak suretiyle toz elde etme ilemine gaz atomizasyonu denir. Sv metal akkan nozuldan kan yksek hzl gazn genlemesi suretiyle paralanarak kk tanelere ayrlr. Gaz atomizasyonu; kresel yapl yksek younlukta, iyi akclkta ve yksek kalitede olan tozlarn retilmesinde yaygn bir ilemdir. Ayn zamanda gaz atomizasyonu ile yksek saflkta az oksijen ieren metal tozu retimi mmkndr. Byle tozlarn, pskrtme kaplama, pskrtme balama, kimya endstrisi, tp teknolojisi gibi geni bir kulanm alan vardr. Gaz atomizasyonu, sper alamlar ile yksek alaml metallerde de ok baarl sonular vermektedir. Bu yntemde gaz cinsi, gaz basnc, gaz ve sv metal ak debileri ile nozul geometrisi gibi retim parametreleri tozlarn fiziksel ve kimyasal zelliklerini etkilemektedir [7]. Yaygn bir toz retim teknii, metal tozlarnn yaklak olarak %80i bu yntemle retilmektedir [8]. Pskrtme ekillendirme ynteminin iki nemli avantaj vardr. Bunlardan birincisi eriyikten direk olarak tek bir operasyonla net ekillendirilmi rn elde etme imkandr. P ynteminin ikinci avantaj metalurjik ve mekanik zelliklerde nemli lde iyilemenin salanmasdr [9].Biriktirilen damlacklarn yaps malzemedeki en belirgin zelliktir. nk son rnn mekanik zellikleri tamamen bu yapya baldr[10]. Bu paralar diske ulamadan katlam ve toz haline gelmilerdir. Pskrtlen sv younluu az ise bu tabakalar arasnda kalnt gzenekler oluur. Genellikle gzenek miktar %3 ile %15 arasnda deiir. Bununla beraber vurgulanmas gereken dier bir nokta ise, bu ekilde retilen paralarn mukavemetinin sinterlenmemi T/M rnlerine gre ok daha yksek olmasdr. Parann yaps disk dzleminde genellikle izotropik, normal ynde ise anizotropiktir. Snrl miktarda yaplan scak ekillendirme veya souk ekillendirme ileminden sonra bu gibi yaplar genellikle izotropisini korurlar. Bu durum ise, genellikle faydaldr (derin ekme srasnda kulakk verme, baak verme olayn azaltr) [11]. Bu almada, tasarmlar ve imalatlar daha nceden yaplm olan yakndan elemeli nozullar kullanlarak gaz atomizasyon nitesinde, alminyum tozu kullanlarak silindir zerinde homojen bir kaplama tabakas oluturulmutur ve gzenekliliin mekanik zellikleri dorudan etkilemesi nedeniyle parametrelerin buna etkileri aratrlmtr.
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2. DENEYSEL YNTEM 2.1. Atomizasyon almalar Gaz atomizasyonu almalarnda, tasarm ve imalat yaplm olan yakndan elemeli laval tipi nozul kullanlmtr. knt aparat olarak farkl uzunluklara sahip adet para, tozu retilecek metal olarak alminyum, atomizasyon gaz olarak ise hava kullanlmtr. Alminyum ergime scakl 660Cdir. Yaplan atomizasyon almalarnda ergimi alminyum 725 Cye kadar stlmtr. Ergimi alminyum, elik potann altndan atomizasyon gazyla buluma noktasna doru seramik tpn iinden akarken sv metalin scaklnn deimemesi iin ak memesi ierisindeki seramik tpn etrafna, iki ucu voltaj deitiriciye bal olan diren teli sarlmtr. Metal ergitmeye baland andan itibaren voltaj deitirici 25 Va ykseltilmitir ve atomizasyon ilemi boyunca bu deerde sabit tutulmutur. 6x4x145 mm boyundaki seramik tpn etrafna 0,7 mm apnda 1200 Wlk diren teli sarlm, seramik tp ak memesinin iine yerletirilmitir. Seramik tpn dier ucuna knt aparat yerletirilmi ve ak memesi ile knt aparat birbirine balanmtr. Seramik tpn iki ucundaki diren telleri 700Cye kadar dayankl yanmaz kablo ile kaplanarak ak memesi zerindeki delikten dar karlm ve telin iki ucu voltaj deitiriciye balanmtr. Ergitilecek olan alminyum pota ierisine atlmtr. Yaplan almalarda yaklak olarak her deney iin 250 g alminyum kullanlmtr. Alminyum scakl 725Cye ulatnda ama-kapama mekanizmas zerindeki ubuun kaldrlarak, sv metalin atomizasyon ilemi gerekletirilmitir. alma esnasnda Pyi etkileyen parametrelerden nozul ucundaki knt mesafesi, gaz basnc ve pskrtme mesafesinin (pozisyon) etkilerini grmek amacyla baz n testeler uygulanarak parametrelerin balang deerleri belirlenmi ve sonularn etkilerini boyutlu grafiklerde yzey cevaplar eklinde grebilmek iin bir deney program yaplmtr. Bunun iin MINITABTM yazlmndan yararlanlmtr. Her bir parametre iin deiik deer ve her bir artta tekrar esas alnarak Box-Behnken tipi deney program oluturulmu, bylece normalde 81 adet olmas gereken deney says baz u deerlerin tekrarlarnn azaltlmas suretiyle 42 olarak bulunmutur. Bu deney program esas alnarak kaplamalar yaplmtr. 2.2. Pskrtme ekillendirme Deneyleri Atomizasyon ilemiyle elde edilen damlacklarn st ste ylarak biriktirebilmesi iin, gaz atomizasyon nitesinde, nozul altna denk gelecek ve nozul ile mesafesi ayarlanabilecek bir mil tasarm ve imalat yaplmtr (ekil 1). Bu milin belli bir hzla dnmesini salayabilmek iin 0,37 kW ve 200 dev/dk nominal hza sahip tahrik motoru (redktr) ve AC motor srcs kullanlmtr (ekil 2). 50x40x250 mm boyutlarnda alminyum boru milin zerine yerletirilmitir (ekil 3).
ekil 1. Deney dzeneinin ematik grnts
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ekil 2. Deney dzenei
ekil 3. Nozul altna yerletirilen mil ve boru montaj Bundan sonraki aamada alminyum boru yzeyine nozullar vastasyla deney programna uygun srayla pskrtme ilemi uygulanp alminyum borunun yzeyi kaplanmtr (ekil 4).
(a) 5 bar, 4 mm knt uzunluu ve 135 mm pskrtme mesafesi
(b) 10 bar, 6 mm knt uzunluu ve 165 mm pskrtme mesafesi
(c) 15 bar, 6 mm knt uzunluu ve 200 mm pskrtme mesafesi ekil 4. Kaplanm numunelerden rnek resimler
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3. DENEYSEL BULGULAR VE TARTIMA 3.1. Testler in n Hazrlklar Yaplan deneyler sonucu elde edilen kaplamalarn, nozulun tam altna gelen orta ksmlarndan ve kenar ksmlardan birer numune alarak bakalite gmme ilemi yaplm ve parlatma ilemi yaplmtr. Elde edilen parlatlm numunelerin OLYMPUS GX71 optik mikroskopta yzey morfolojileri incelenmi ve her yzeye farkl yerlerden 5 adet fotoraf ekilmitir. Bu fotoraflar Image-J programnda (ekil 5) analiz edilerek % cinsinden gzeneklilik miktarlar hesaplanmtr. Bu ilem iin nce fotoraflar ikili (binary) koda dntrlm ardndan da siyah ksmlarn beyaz ksmlar oran bulunmutur. Elde edilen saysal deerler Minitab yazlmnda kullanlarak 3 boyutlu yzey cevaplar elde edilmi ve bu grafikler zerine yorumlar yaplmtr. Numunelere ait mikroskoptan alnan rnek yzey grntleri ekil 6da grlmektedir.
ekil 5. Image-J yazlmnda ikili koda dnm ve bulunan % gzeneklilik
(a) 5 bar, 8mm knt uzunluu, kenar ksm, 135 mm pskrtme mesafesi
(b) 10 bar, 6mm knt uzunluu, orta ksm, 165 mm pskrtme mesafesi
15 bar, 6mm knt uzunluu, orta ksm, 200 mm pskrtme mesafesi ekil 6. Kaplama ile elde edilmi numunelerin rnek mikroskop grntleri (x400)
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3.2. Gzeneklilik Testi Kaplamalarn orta ksmlarndan alnan rnekler incelendiinde, 135 mm mesafeden yaplan pskrtme deneylerinde beklendii gibi gzenek miktarnn orta blgede (%8) kenar ksmlardan daha az olduu gzlenmitir (%11) (ekil 7). Pskrme mesafesinin artmasyla birlikte katlamann daha fazla olaca bylece tanelerin kaplanan yzeye ylmas srasnda ekil deitirme kabiliyetinin azalmas nedeniyle daha fazla gzeneklilik beklenmekte olup ekil 7 incelediinde artan pskrtme mesafesiyle birlikte gzenekliliin de art gsterdii grlmektedir. Dier taraftan ekil incelendiinde, tane boyutunu etkilemesi dnlen nozul ucundaki knt mesafesinin deitirilmesinin gzeneklilik zerinde dikkate deer bir etkisinin olmad grlmektedir. ekil 7den kartlan bir dier sonu ise btn artlar iin geerli olmak zere gzenekliliin kenar blgelerde biraz daha yksek olduudur.
ekil 7. Kaplamalardaki gzeneklilie pskrtme mesafesi ve kntnn etkileri Yaplan deneylerde atomizasyon basncnn etkileri incelendiinde, gerek kenar ve gerekse orta ksmlarndan artan basncn gzeneklilii etkili bir ekilde ve neredeyse lineer olarak azaltt grlmektedir (ekil 8). Bu durum artan basnla birlikte toz boyutunun klmesi ve silindir zerine giderken daha yksek hza sahip olmalar, bylece tozlarn daha yksek hzlarda arpmalar eklinde aklanabilir. Yine beklendii gibi, basncn artmasnn orta ve kenar blgedeki gzenekliliklerde etkisinin olmad, yani kenar blgelerde atomizasyon basnc artrlm olsa bile orta ksmlara gre daima daha yksek gzenekliliin olutuu gzlemlenmitir.
ekil 8. Atomizasyon basnc ve knt uzunluunun gzeneklilie etkileri 3.3. Taneler Aras Balant, Tane Bykl ve Tane ekli Testleri Tane eklinin, boyutunun ve mikro yapsnn incelenmesi iin numunelere dalama yaplmtr. Dalama ilemi KELLER zeltisi kullanarak yaplmtr (2.5ml HNO3+1.5ml HCL+1ml HF +95ml saf su). Dalama ilemi yaplmadan nce tane ekli ve bykl grnmemektedir (ekil 9).
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ekil 9. Dalama ilemi yaplmadan nceki optik mikroskobu altnda yzey grnts (x400). Dalama ilemi hem kle alminyuma ve kaplama numunelerine uygulanmtr. Yaplan dalama ilemi sonrasnda elde edilen grntler ekil 10da kle alminyum ve ekil 11de ise pskrtme sonras elde edilen kaplamaya ait olacak ekilde verilmitir. Grlecei zere, atomizasyon ilemi P ile elde edilen parann mikroyapsn nemli lde kltm, yass ve iri mikroyapy ortadan kaldrp, gittike kreselleen ve en nemlisi kk ve homojen bir mikroyapsn ortaya karmtr. Atomizasyon basncnn 5 bar olduu numune incelendiinde, tane boyutunun olduka byk ve karmak geometrili (kimi tanelerin ubuumsu kimisinin yamuk geometrili) olduu grlmektedir. Basn arttrlp 10 bara ykseltildiinde tanelerin kld ayn zamanda da kreselletii gzlemlenmitir. Basn 15 bara ykseltildiinde ise tane boyutunun beklendii gibi daha da kld ve neredeyse tamamnn kresel geometriye brnd grlmektedir.
Resim 10. Dalama ilemi yaplan alminyum ktk numunesinin tane ekli ve bykl (x400)
ekil 11. Orta ksm alnm bir numunede tane ekli ve bykl (x400)
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Her ne kadar tanelerin yar kat bir ekilde arpt ve taneler arasndaki snrlarn ok net olarak grlmesi beklenmese de, elde edilen dalanm numunelerin mikroskop grntlerinden tozlarn tane boyutlar llmeye allmtr. Tane boyutunu lmek iin mikroskopta daha nce numune fotoraflar iin kullanlan ayn piksel ayarlarnda gerek kalnl 0,100 mikron olan sac malzemenin fotoraf ekilmi, buna gre tane boyutlarnn gerek lsn bulmak iin karlatrma yaplmtr. En az 7 adet rnein tane boyutu ortalamas alnmtr. Bunun sonucunda, 5 barda yaplan kaplamalarn tane boyutlarnn ortalamas = 22,3 m iken bu byklk 10 bar iin 10,5 m ve 15 bar iin de 4,8 m olarak llmtr (ekil 12).
Resim 12. Image-J program ile tane boyutu lme 4. SONULAR Bu almada, nceden yaplm yakndan elemeli laval tipi nozul kullanlarak, gaz atomizasyonu yntemiyle hava atomize alminyum tozu retilmesi ile birlikte eitli mesafelerde dnen bir silindirin yzeyinde pskrtme ekillendirme ile alminyum kaplamas yaplmtr. almadan elde edilen sonular aada verilmitir: 1. Kaplamalarn orta ksmlarndaki gzenekliliklerin, kenar ksmlardan daha az olduu gzlenmitir. 2. Pskrtme mesafesi arttka gzenek miktar artt tespit edilmitir. En az gzenek miktar 135mm pskrtme mesafesinde elde edilmitir. Dolaysyla, yksek younluk iin pskrtme mesafesinin mmkn olduunca ksa tutulmas gerekmektedir. 3. Artan atomizasyon basncyla gzenek miktarnn da dzenli olarak azald grlmtr. 4. Mikroyaplar incelendii zaman, beklendii gibi normal bir dkme gre olduka ince ve homojen bir yap elde edilmitir. Daha nceki almalardan anlalaca gibi, ince taneli mikroyapnn mekanik zellikleri arttraca beklenmektedir. Bu alma sonucunda elde edilen avantajlardan biri, pskrtme ekillendirme yntemi ile tozlarn ylmas yapldndan, ok ince bir tane yaps, dolaysyla mekanik zelliklerde belirgin art olarak zetlenebilir.
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TEEKKR Bu alma Gazi niversitesi Bilimsel Aratrma Projeleri tarafndan 06/2010-58 kodlu proje olarak desteklenmitir. Teekkr bir bor biliriz. KAYNAKLAR 1. Bozkurt, ., nal, R., Gaz atomizasyon yntemi ile metal tozu retiminde gaz ak modelleri, I. Ulusal Metalurji Ve Malzeme Gnleri Bildiri Kitab, Osmangazi niversitesi, Eskiehir, 099, 2004. 2. German, R., M., Powder Metallurgy Science 2nd edition, Metal Powder Industries Federation, USA, 16-20, 76-90, 1984. 3. nternet:http://mf.dumlupinar.edu.tr/~runal/toz/powdermet.html 4. Yldz, E., S., Gaz atomizasyonu ile metal tozu retiminde, nozul geometrisinin toz boyutuna etkisinin aratrlmas, Yksek Lisans Tezi, Dumlupnar niversitesi Fen Bilimleri Enstits, Ktahya, 2007. 5. nternet:http://mf.dpu.edu.tr/~runal/toz/sprayforming.pdf 6. Bozda, V., Yakndan elemeli laval nozul kullanlarak yaplan pskrtme ekillendirmenin mekanik zelliklere etkisinin aratrlmas, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara, 2008. 7. Uslan, ., Kkarslan, S., Kalay tozu retimine gaz atomizasyonu parametrelerinin etkisinin incelenmesi, Gazi niversitesi Mhendislik Mimarlk Fakltesi Dergisi, 25(1): 1-8 2010. 8. Uslan, ., Toz Metalurji retim Teknikleri, Gazi niversitesi, Mh. Fak. Yksek Lisans Ders Notlar, 2009. 9. Odaba, A., Altmolu, S., A., Eruslu, N., Toz metalurjisine alternatif: Osprey prosesi, I. Ulusal Metalurji ve Malzeme Gnleri Bildiri Kitab, Osmangazi niversitesi, Eskiehir, 099, 2004. 10. Cai., W., D., Smugeresky, J., Lavernia, E., J., Low-Pressure Spray Forming of 2024 Aluminum Alloy, Material Science and Engineering A, 241 (1-2): 60-71 1998. 11. Ekici, A., Ekstrzyonla tam younlatrlm pskrtme ekillendirme alminyumun mekanik zelliklerinin deneysel olarak aratrlmas, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara, 2005.
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MECHANICAL ALLOYING
www.turkishpm.org
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The effect of gradual process control agent technique on the morphology of Al powders fabricated by high energy ball milling
Aykut Canakci1, Temel Varol1
1
In this work, a new method was developed in relation to process control agent. This new method was called as gradual PCA technique. The morphology and the microstructure of the milled powder were evaluated using SEM and XRD techniques, respectively. Also the relationship among the stages of milling was examined. For determining relationship between particle hardness and amount of PCA was measured the microhardness of the particle. In addition, the particle size change with milling time and the amount of PCA was investigated. It was observed that the effectiveness of milling increase by the gradual PCA technique. In other words, this method increases the efficiency of milling balls at the beginning of the process. Hence, it is observed that the amount of PCA up to 2h of milling time has a significant effect on particle microhardness and particle size. As a result, a new technique which increases the efficiency of milling process were carried out using a planetary ball mill. Keywords: Process control agent (PCA), Gradual PCA technique, Mechanical alloying (MA), High energy milling 1. Introduction Mechanical alloying or high energy milling (HEM) is a solid-state powder processing involving repeated welding, fracturing, and rewelding of powder particles in a high-energy ball mill and this process has the advantages of the synthesis of nanostructure materials with high purity at large quantities at room temperature [1-4]. Besides mechanical alloying or high-energy ball milling can produce a fine and homogeneous distribution of the hardening particles [5-10]. The high energy involved in the MA process fragments and cold rewelds powder particles that form the initial mix. The microstructure of final powders is usually finer than of powders obtained by atomization and has grain size levels similar to those obtained using rapid solidification techniques [11]. Process variables in MA technique or HEM process such as milling time, milling speed, ball-to-powder weight ratio and process control agent have effects on the final structure and morphology of the powders [12]. In high energy milling process, process control agents (PCAS) play a significant role in controlling the particle size and degree of cold welding during ball milling. A process agent is a surface additive used in the milling process in order to control the balance between the fracturing and cold welding of particles. The application of PCA to MAed powder enables to reduce cold welding and promote fracturing [13-16]. PCAs adsorb on the surface of the powder particles and minimize cold welding among powder particles, thereby inhibiting agglomeration. A wide range of PCAs has been used in practice at a level of about 1-5wt% of the total powder charge. The most important PCAs include stearic asit, hexane, methanol and ethanol [17]. PCA must be used in milling process for most material systems because of the balance between cold welding and fracturing doesnt occur naturally. Many researches [18-20] have used PCA to prevent excessive cold welding of particles during milling but so far, any researchers has not used gradual PCA technique. All of PCA is usually emptied to vial at the beginning of the process. However There are important differences between the two processes in of results.
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The present work aims to investigate of the gradual PCA technique on the characteristics of mechanical alloyed powders. 2. Experimental procedure Gas atomized Al powders with average particle size of 377m (Gndodu Exotherm Company, Turkey) were used as raw materials. Fig 1 shows the morphology of the as received Al powders. The chemical composition of the as-atomized Al alloy (in wt. %) is 1.230Fe, 1.000Si, 1.000Pb, 0.710Cu, 0.530Zn, 0.116Mn, 0.071Ti, 0.050Mg and Al (balance).
Fig. 1. Morphology of the as received Al powder. The initial powders have ligamental shape and which were milled by a high-energy ball milling up to 7h. The milling process was carried out in a planetary ball-mill (Fritshc Gmbh, model Pulverisette 7 premium line) at room temperature using tungsten carbide bowl and high argon atmosphere. Tungsten carbide ball with a diameter of 10mm were used to milling process. The ball-to-powder weight ratio (BPR) and rotational speed were 10:1 and 400rpm, respectively. Methanol (Merck) was used as PCA. In order to investigate the effect of gradual PCA technique were used wt.% beginning of PCA 0, 0.25, 0.5, 0.75, 1 and 2, respectively. This process is given in Table 1. In order to avoid the formation of some intermetallic fractions and the heating by milling, process was stopped every 30 minutes than resumed when the temperature of the bowl decreased to the room temperature. Table 1. Gradual PCA application process. Milling Time (h) Process 1 2 3 4 5 6 Code P1 P2 P3 P4 P5 P6 0 0 0.25 0.5 0.75 1 2 1 0 0.25 0.214 0.179 0.143 0 2 0 0.25 0.214 0.179 0.143 0 3 0 0.25 0.214 0.179 0.143 0 4 0 0.25 0.214 0.179 0.143 0 5 0 0.25 0.214 0.179 0.143 0 6 0 0.25 0.214 0.179 0.143 0 7 0 0.25 0.214 0.179 0.143 0 Total of PCA (wt.%) 0 2 2 2 2 2
The size distribution of as-received and milled powders was quantified by a laser particle size analyzer (Malvern, model Mastersizer Hydro 2000). The phase analysis of milled products was evaluated by X-ray diffraction (XRD) (Rigaku Corporation, Japan) using CuK radiation (1,54059 Ao) operating at 30mA and 40 kV. The XRD patterns were recorded in the 2 range of 20-100 o (step size 0.02o and time per step 1s). Crystallite size in the milled powders were calculated from the XRD line broadening using the Scherrer equation. For this purpose, some Al powders were annealed to minimize the strain field in lattice of the powder particles. After annealing, x-ray diffraction patterns of annealed powders and the full width at half maximum intensity of the peak were measured to eliminate instrumental broadening effect. After that the full width at half maximum intensity of the peak was recorded from x-ray diffraction patterns of milled powders. Scherrer equation can be written as follow:
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(1)
(2)
where, B is the modified peak full width, is the Bragg angle, is the wavelength of the x-radiation used, d is the crystallite size, Bm is the peak full width at half the maximum intensity of x-ray diffraction patterns of milled powders, and Ba is the peak full width at half the maximum intensity of x-ray diffraction patterns of annealed powders. The morphology of powders particles was investigated by scanning electron microscopy using Zeiss LS10. Morever the microhardness of Al powders have been measured using a vickers microhardness tester (Struers microhardness tester) at an load of 98.7mN for 10s. 3. Results and discussion 3.1. Effect of gradual PCA technique on milling process Milling process is given in Table 2. Process is summarized in the Table 2 for better understanding of the stages of milling. Table 2 shows the effect of the gradual PCA process on the mechanical alloyed Al powders. Table 2. The shapes of milling during the mechanical alloying. Milling Time (h) Process P1 P2 P3 0.5 1 Cold welding Fracture and flattened shape A little fracture and a little flattened shape A little fracture and a little flattened shape Little fracture and little flattened shape Little fracture and little flattened shape 2 Cold welding Fracture Fracture and flattened shape Fracture and flattened shape Little fracture and little flattened shape Little fracture and little flattened shape 5 Cold welding Fracture Fracture 7 Cold welding Fracture continues Fracture continues Fracture continues Fracture continues Fracture continues
Fracture and cold welding Fracture and cold welding Little fracture
P4
A little fracture
Fracture
P5
No fracture
Fracture
P6
No fracture
Fracture
Fig. 2 shows the used milling medium component (bowl and balls) and Al powders before and after milling. Fracture and cold welding occured between particles up to 0.5h of milling. Cold welding process is effective up to from 0.5 h to 7h and particle size is increasing continuously. The average particle size is 1600 m at the end of 7h. It can be observed that cold welding lead to be little cold welded to bowl surfaces after milling time of 7h (Fig. 2b). One of the remarkable events of this process, sticking of Al powders on the surface of the bowl is very little. However, Fig. 2c gives another example of Al powders being serious cold welded to a milling ball. As it can be seen in Fig 2b and 2c, the sticking of Al powders on the surface of bowl and balls increases with increasing milling time so impact energy of balls decreases. As a result, the milling of ductile metal powders is not possible without PCA. This result is a negative result for milling process but this process may be considered as a new surface coating method [21,22].
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(a)
(b)
(c) Fig. 2. Used milling medium components (bowl and balls) and Al powders before and after milling for P1 . (a) Bowl and balls before milling, (b) Bowl after milling (7h), (c) Al powders and ball surfaces after milling (7h). Compared to applications by looking at process images of the P1 and P2, the addition a small amount of PCA can easily see the effect on milling process. With the addition of 0.25 wt. %PCA, powders were fractured and flatten shape after 0.5h of milling. This result is an evidence showing that a high level of efficiency of the P2 process. As shown in the process images (Fig. 3a), At the end of milling, balls and bowl surfaces for P2, P3, P4, P5, and P6 processes have light freckles (Fig. 3). Bowl after milling Al powders and ball surfaces after milling
(a)
(b)
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(c)
(d)
(e) Fig. 3. Used milling medium components (bowl and balls) and Al powders after milling for gradual PCA processes: (a) P2, (b) P3, (c) P4, (d) P5, and (e) P6. 3.2. Effect of gradual PCA technique on the powder morphology The particle morphology of milled powders for gradual PCA processes are showed in Fig. 4. It can be observed that different powder morphologies were obtained for different amounts of PCA and different milling times. Initial Al powders particles have ligamental shape. When particle morphologies was examined at the end of 0.5h of milling it was observed; ligamental morphology was completely disappeared and an abnormal growth of particle size due to the cold welding in the P1 process. Moreover, powders morphology have spherical and flatten shape and particle size is constantly growing for all milling times. Eventually, the cold welding process becomes almost dominant on the powder which was milled without PCA. Ligamental powders were fractured and which change into flatten shape in P2 process during 0.5h of milling process (Fig. 4a). After that 0.5h, fracture process is active process. There is no significant change in particle morphology up to 2h of milling, but the particle size slightly decreased. After this stage up to 7h, the tendency to fracture dominates over cold welding. Particle morphology exhibited a morphology which has similar spherical morphology after 2 h of milling. The amount of PCA is above the critical value for the P3 process so fracture process efficiency is little up to 0.5h (Fig. 4b). After this stage up to 7h, the tendency to fracture dominates over cold welding and particle size decreases with increasing milling time. A similar behaviour was observed with previous studies [23-26] in all the cases. Moreover, the amount of reduction in particle size decreases with increasing the amount of PCA. Flatten particle morphology can not be reached at the end of 1h milling in P4 process (Fig. 4c). As can be seen from SEM images (Fig. 4c and Fig. 4d), the effectiveness of fracture decreases with increasing the amount of PCA. P4, P5, and P6 processes are similar to the processes in terms of change of particle morphology but changes in particle size are slightly different.
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Fig. 4. Morphologies of Al powders at after different milling times for gradual PCA processes: (a) P2, (b) P3, (c) P5, and (d) P6. 3.3. Effect of gradual PCA technique on the particle size During high energy milling, plastic deformation, cold welding and fracture are predominant mechanisms, in which the deformation leads to a change in particle shape, cold welding leads to an increase in particle size and fracture leads to decrease in particle size. Fig. 5 shows the particle size distribution of Al powders for P2 process after the milling times of 0.5, 1, 2, 5, 7h, respectively. Table 3 presents average particle size values after 0h, 0.5h, 1h, 2h, 5h, 7h of milling times for all processes. As can be seen from Table 3, except for P1 process, particle size decreases with increasing milling time for all processes. However, the particle size of P2 decreases to be the highest in gradual
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processes. This result is another evidence showing that a high level of efficiency milling of the P2 process. Unlike most of the work related to mechanical alloying [10,27-33], in this study, this particle size decreases continuously because of initial powders have ligamental shape. Powders are deformed due to high energy collisions of balls and they are fractured from fine regions. Flatten shape occurs after this fracturing process so particle size decreases unlike increasing at early stage of milling. With increasing milling time, work hardening of powders causes brittle of powders and fracturing process becomes effective process. Table 3. Particle size of Al powders at after differents milling times for gradual PCA processes. Process P1 P2 P3 P4 P5 P6 Particle size (m) Milling time (h) 0 377 377 377 377 377 377 0.5 500 269 337 344 360 367 1 790 200 242 327 340 361 2 950 120 150 186 269 332 5 1200 40 58 63 68 71 7 1600 18 34 40 43 45
Fig. 5. The change of particle size of Al powders with milling time and gradual PCA process. The most effective gradual proces was found to be P2 process. The average particle size in this process was decreased from 377m to 18m, as seen in Table 3. Ball-impact energy of balls decreases because of increasing the beginning amount of PCA so work hardening of particles decreases and there was no significant change in particle size. Significant reduction of particle size in P3, P4, P5, P6 processes occur during milling from 2h to 7h. It should be noted that almost no change in particle size up to 2h of milling in P6 process because of the beginning amount of PCA is higher than the beginning amount of critical PCA. 4. X-ray Diffraction analysis of milled powders Crystallite size determination is one of the most important applications in powder diffractometry for materials characterization. XRD pattern of milled powders for P2 process are illustrated in Fig. 6. Al powders underwent deformation and cold welding caused by continuous collision and split between balls and powders. As can be seen in Fig. 6, ball milling makes diffraction peaks become wide and the peaks intensities decrease.
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Fig. 6. The change of XRD patterns of milled Al powders at different milling times for P2 process. The effect of milling time on the crystallite size for Al powders are shown in Fig. 7. A rapid decrease in crystallite size of Al powders from 0h to 0.5h of milling time but after 0.5h of milling only a slight further decrease in crystallite size occurs as confirmed by other studies [15,16,34]. This result indicates that P2 process is highly effective in reducing crystallite size by increasing milling time.
Fig. 7. Variation in crystallite size for as a function of milling time. 5. Effect of gradual PCA technique on the particle microhardness The change of microhardness of milled powders as a function of milling time and gradual PCA is given in Table 4. Generally, increasing milling time increases the deformation and work hardening of powders. As can be seen in Table 4 and Fig. 8, there is a continuous increase in microhardness of all process with increasing milling time and there is a continuous decreases in microhardness with increasing the beginning amount of PCA up to 2h of milling. The initial amount of PCA begins to approach for all processes after 2h of milling so the microhardness values are almost the same for 5h and 7h.
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Table 4. Milled powder of microhardness at different milling time for gradual PCA processes. Process P1 P2 P3 P4 P5 P6 Microhardness (Hv) Milling time (h) 0 33 33 33 33 33 33 0.5 101 89 68 67 66 65 1 117 106 88 87 75 74 2 124 123 115 113 93 88 5 125 126 123 121 120 110 7 125 128 124 122 121 120
Fig. 8 shows variation of microhardness of powders versus milling time for P2, P4 and P6 processes. As can be seen increasing milling time causes a raise in microhardness of particles. The main factor effecting the microhardness of powders is work hardening of powders. At the beginnig of milling the rate of increasing of microhardness is so much but this rate decreases as milling time increases gradually.
Fig. 8. The change of microhardness at different milling time for gradual PCA processes. 6. Conclusions The effect of gradual process control agent on high energy milling process was examined. Stages of the process, powder morphology and particle size for All process were investigated. The results showed that the P2 process is the most efficient process so crystallite size of P2 process was investigated. Morever, change of microhardness of powders as a function of milling time for all process were examined. The results are remarked as below: 1. Gradual process control agent technique reduces the size of Al powders rapidly because of increasing the fficiency of milling balls at the beginning of high energy milling process. Consequently, the researchers working on high energy milling or mechanical alloying, avoiding the use of PCA more than critical amount of PCA may increase the efficiency of milling process. 2. The optimal amount of PCA for Al powders (10:1 ball-powder weight ratio) is 2 % by weight. 3.Particle microhardness decreases with increasing amount of PCA during 2h of milling. 4. Particle microhardness increases wiht increasing milling time. 5. It was seen, milling process which is applicated without PCA can be used as a novel surface coating technique.
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Acknowledgement The authors are grateful to Karadeniz Technical University Research Fund for the financial supporting of this research work (No: 2007.112.10.2). The researchers would also like to thank to Gundogdu Exotherm Service for providing Al powders. References 1. I. Estrada-Guela, C. Carreno-Gallardo, D.C. Mendoza-Ruiz, M. Miki-Yoshida, E. Rocha-Rangel, R. MartinezSanchez, Journal of Alloys and Compounds 483 (2009) 173177 2. S.Gomari, S.Sharafi, Journal of Alloys and Compounds 490 (2010) 2630 3. Li Lu, Y.F. Zhang, Journal of Alloys and Compounds 290 (1999) 279-283 4. B.D. Long, H. Zuhailawati, M. Umemoto, Y. Todaka, R. Othman, Journal of Alloys and Compounds 503 (2010) 228-232 5. B. Prabhu, C. Suryanarayana, L. An, R.Vaidyanathan, Mater Sci Eng A 425 (2006) 425:192. 6. MS. El-Eskandarany, Journal of Alloys and Compounds 279 (1998) 26327. 7. H. Arik Materials & Design 25 (2004) 31:40. 8. Naiquin Zhao, Philip Nash, Xianjin Yang, Journal of Materials Processing Technology 170 (2005) 586-592. 9. Yusuf Ozcatalbas, Composites Science and Technology 63 (2003) 53-61. 10. SS. Razavi Tousi, R. Yazdani Rad, E. Salahi, I. Mobasherpour, M. Razavi Powder Tech 192 (2009) 346351. 11. E.M. Ruiz-Navas, J.B. Fogagnolo, F. Velasco, J.M. Ruis-Prieto, L. Froyen, Composite: Part A 37(2006) 21142120. 12. Kh. Gheisari, S. Javadpour, J.T. Oh, M.Ghaffari Journal of Alloys and Compounds 472 (2009) 416-420. 13. Keke Gan, Mingyuan Gu, Journal of Materilas Processing Technolgy 199 (2008) 173-177. 14. M. A. Shaikh, M. Iqbal, J. I. Akhter, M. Ahmad, Q. Zaman, M. Akhtar, M.J. Moughal, Z. Ahmed, M. Farooque, Materials Letters 57 (2003) 3681-3685. 15. L. Shaw, M. Zawrah J. Vllegas, H. Luo, D. Mracle, Metallurgical and Materials Transactions A 34A (2003) 159-170. 16. M. Pilar, J.J. Sunol, J. Bonastre, L. Escoda, Journal of Non-Crystallne Solids 353 (2007) 848-850. 17. C. Suryanarayana, Mechanical Alloying and Milling, New York, 2004. 18. Lu, Li., Zhang, Y.F., Influence of process control agent on interdiffusion between Al and Mg during mechanical alloying, Journal of Alloys and Compound, vol. 290, 1999, pp. 279-283. 19. Pilar, M., Suol, J.J., Bonastre, J., Escoda, L., Influence of process control agents in the development of a metastable FeZr based alloy, Journal of Non-Crystalline Solids, vol. 353, 2007, pp. 848-850. 20. Long, B.D., Zuhailawati, H., Umemoto, M., Todaka, Y., Othman, R., Effect of ethanol on the formation and properties of a CuNbC composite, Journal of Alloys and Compound, vol. 503, 2010, pp.228-232. 21. Iman Farahbakhsh, Alireza Zakeri, Palavesamuthu Manikandan, Kazuyuki Hokamoto, Applied Surface Science 257 (2011) 28302837. 22. S. Romankov, W. Sha, S.D. Kaloshkin, K. Kaevitser, Surface & Coatings Technology 201 (2006) 32353245. 23. M. Azimi, G.H. Akbari, Journal of Alloy and Compounds 509 (2011) 27-32. 24. Hafeez Ahamed, V. Senthilkumar, Journal of Alloy and Compounds 505 (2010) 772-782. 25. S.M. Zebarjad, S.A. Sajjadi, Materials and Design 27 (2006) 684-688. 26. JB. Fogognolo, F. Velasco, MH. Robert, JM. Torralba, Mater Sci Eng A 342 (2003) 131143. 27. J. A. Rodrigues, J. M. Gallardo, E. J. Herrera, Journal of Materials Science 32 (1997) 3535-3539. 28. H. Abdoli, H. Asgharzadeh, E. Salahi, Journal of Alloys and Compounds 473 (2009) 116-122. 29. J.J. Fuentes, J.A. Rodriques, E.J. Herrera, Materials Characterization 61 (2010) 386-395. 30. Yan J-w, Lu Y, Peng A-f, Lu Q-g, Trans. Nonferrous Met. Soc. China 19 (2009) 711-717. 31. G. Pozo Lopez, S.P. Silvetti, Physica B 354 (2004) 141-144. 32. J.B. Fogagnolo, D. Amador, E.M. Ruiz-Navas, J.M. Torralba, Materials Science and Engineering A 433 (2006) 45-49. 33. Xuren Liu, Yongbing Liu, Xu Ran, Jian An, Zhanyi Cao, Materials Characterization 58 (2007) 504-508. 34. H. Zuhailawati, Y. Mahani, Journals of Alloys and Compounds 476 (2009) 142-146.
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MEKANK ALAIMLAMA LEMNDE UYGULANAN DK ENERJL KESME GERLMLER YARDIMIYLA KARBON NANO UBUKLARIN RETM
mer GLER, Ertan EVN Frat niversitesi Metalurji ve Malzeme Mhendislii Blm, Elaz oguler@firat.edu.tr zet Bu almada, mekanik alamlama ilemi esnasnda grafit tozlarna dk enerjili kayma gerilimleri uygulanmtr. Alamlama ilemi 250 saatte tamamlanm ve ardndan elde edilen tozlar argon atmosferi altnda 1600 Cde 4 saat sre ile tavlanmtr. Alamlanan numuneler, X-n difraksiyon analizi (XRD), Alan etkili taramal elektron mikroskobu (FE-SEM) kullanlarak incelenmitir. ncelemeler sonucunda karbon nano ubuk yaplar tespit edilmitir. Anahtar Kelimeler: Karbon Nano ubuk, Mekanik Alamlama
THE PRODUCTION OF CARBON NANOROD THE HELP OF LOW ENERGY SHEAR STRESSES APPLIED AT THE MECHANICAL ALLOYING PROCESS
Abstract In this study, low energy shear stresses were applied to graphite powders during mechanical alloying process. Mechanical alloying process was performed for 250 hours and subsequently, milled powders were annealed at 1600 C under argon atmosphere during 4 hours. Samples were investigated by using X-ray diffraction analysis (XRD), field emission scanning electron microcopy (FE-SEM). Carbon nano-rods were determined by investigations. Keyword: Carbon Nano-Rod, Mechanical Alloying
1. GR Grafit, hegzagonal kristal yapnn yksek anizotropisinden dolay pek ok farkl zellikler sergileyen ve bu sebeple zerinde youn almalar yrtlen bir malzemedir. Grafit nano-partikller ve nano-tabakalar, arj edilebilir lityum bataryalarda elektrot olarak, yksek scaklk uygulamalar iin conta olarak, nano-kompozit malzemelerde takviye eleman olarak kullanlmas gibi pekok teknolojik uygulamada kullanm asndan byk potansiyele sahiptirler [1]. Bu malzemeler kimyasal veya mekanik olarak retilebilirler. Mekanik deformasyon ile karbon nano yaplarn elde edilmesi uzun yllardr allan bir konudur [2-3]. Yaplan almalar sonucunda, plastik deformasyonun grafitte yapsal deiimlere sebep olduu ve farkl trden hatalar ortaya kt grlmtr. Mekanik deformasyon iin en ok kullanlan deneysel metot, bir deirmen ierisinde grafitin tlmesi ilemidir. Mekanik alamlama ilemi sresince partikl boyutunda klme ve mikro yapsal deiim meydana gelir. Bu durum, bilyeler tarafndan uygulanan gerilme trne gre deiir. Uygulanan gerilme tr darbe veya kayma eklinde olabilir. Grafite kayma trnden gerilmeler uygulanmas durumunda nispeten kristal yapsn muhafaza etmi yksek anizotropik partikller meydana gelirken [1], darbe trnden gerilmeler uygulanmas durumunda amorf veya nano poroz karbon yaplar meydana gelir [4].
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Bu almada grafit tozlar mekanik alamlama (MA) ilemine tabi tutulmu ve mekanik alamlama (MA) srasnda kayma trnden gerilmeler uygulanmtr. Mekanik alamlama ileminden hemen sonra tozlara yksek scaklkta sl ilem uygulanarak tozlarda meydana gelen deiimler incelenmitir.
2. DENEY ALIMALARI Grafit tozlar (Merck kGAA, 99.5%, <50 m) Planeter tipteki Fritsch Pulverisette P7 cihaz ile 19 mm apnda tek bilye kullanlarak (Bilye/toz oran 8/1) 50 saatten balayarak 250 saate kadar MA ilemine tabi tutulmutur. MA ilemi 15 dakika MA ve 30 dakika souma iin bekleme eklinde yaplmtr. MA deneyleri ncesinde kaplar ve bilyeler alkolle temizlenmitir. alma devri olarak 400 devir/dak seilmitir. 250 saat MA yaplm tozlara 1600 oC de 4 saat sl ilem uygulanmtr. Numuneler koruyucu ortam ierisinde argon atmosferi altnda hazrlanm, sl ilemler ise 0,1L/dak debideki akkan argon yatak altnda yaplmtr. MA ilemi sonras tozlar CuK (1,5406 ) mas altnda XRD incelemelerine tabi tutulmutur. Isl ilem sonrasnda toz numuneler zerinde Fei Nova Nanosem 600 markal cihazla FE-SEM incelemeleri yaplmtr.
3. SONULAR ekil 1. de 400 devirde tek bilye ile 50, 100, 150, 200 ve 250 saat MA yaplm tozlarn XRD deiimi verilmitir.
ekil 1: 50, 100, 150, 200 ve 250 saat MA yaplan tozlarn XRD deiimi. 26o civarnda grlen karbonun (002) pikinin 250 saat MA sonunda iddetinde azalma meydana gelmitir ve artan MA sresiyle birlikte tozlarda bir miktar amorf yap ortaya kmtr. 50 saat MA ile 250 saat MA sonunda elde edilen piklerin iddetleri oran () 2,6dr. Yaplan TEM incelemeleri sonucu ve Debye-Scherrer forml (1) kullanlarak yaplan hesaplamalar sonucu 50 saat MA sonras ortalama toz boyutunun 230 nm olduu ve artan MA sresiyle birlikte toz parack boyutunun azald ve 250 saat MA sonunda ise 160 nm ye kadar dt tespit edilmitir. (1)
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Ps parack boyutu, dalga boyu, FWHM full width at half-maximum, 1 ise krnm asdr. 50 saatten balayarak 250 saate kadar olan MA srecinde kap ve bilyelerden anarak kopan Fe nin sementite (FexC) dnt tespit edilmitir. MA srasnda tozlara uygulanan deformasyon enerjisi FexC nin (x=2 ve 3) dk scaklkta olumasna sebep olmaktadr. MA ileminin balangcndan 24 saat sonra, tme kaplarnn scakl bir sl ift ile llm ve 32 oC olduu grlmtr. Literatrde molar oranlarda kartrlan Fe ve C tozlarnn MA ilemi ile 5 saat sonunda Fe3C ye dntkleri (in-situ dnm) hususunda bilgiler bulunmaktadr [5]. FexC tozlarnn parack boyutunun ise (1) denklemi kullanlarak 240 nm den balayp 170 nm ye kadar indii hesaplanmtr. Grafite kayma trnde gerilmelerin uyguland almalar incelendiinde bu almalarn tamamnda kayma gerilmesinin darbe tipi gerilmelere gre daha az kristal kusuru oluturduu belirtilmektedir [1,6,7]. Kayma gerilmeleri ksa bir sre iin uygulandnda yapda pek bir deiim gzlenmemi ve tlmemi grafitin yapsna yakn yaplar tespit edilmitir. Artan MA sresiyle beraber grafit tabakalarnda pul pul dklmelerin olduu ve kristal yaplarn koruyan nano tabakalarn olutuu rapor edilmitir [1]. Yaplan FE-SEM incelemeleri sonucu, 250 saat MA ilemine tabi tutulmu 1600 oC de 4 saat tavlanm numunelerde kalnl 15 nm in altnda olan hegzagonal yapl kaln tabakalara rastlanmtr (ekil.2de ok ile gsterilmitir). Bu kaln tabakalarn, yukardaki ksmda da belirtildii gibi, grafit tabakalarnn mekanik alamlama ilemi sresince boyutu klm ve pul pul dklmesi sonucu olumu ince grafit tabakalarnn tavlama ilemi sayesinde st ste gelerek olutuu dnlmektedir.
ekil 2. 250 saat MA sonras 1600 oC de 4 saat sl ilem uygulanm numunede oluan grafit nano tabakalarn FE-SEM grnts. Isl ilem scaklnn veya sresinin yetersiz olmasndan dolay bu tabakalarn tam olarak byyemedii dnlmektedir. Bu yaplarn tam anlamyla bymesi durumunda nano ubuk yaplara dnmesi mmkndr. 250 saat MA ilemine tabi tutulmu 1600 oC de 4 saat tavlanm numunenin baz blgelerinde karbon nano ubuk (karbon nanorod) yaplar grlmtr. Bu nano ubuk yaplar ekil 3.a ve b de gsterilmitir. ekil 3.a da grld gibi yapda kalnl 50 nm civarnda olan grafit nano tabakalar bulunmasna karn, tabakalarn st ste gelerek byd, u ksm gittike sivrileen ve boyu yaklak 10 m civarnda olan karbon nano ubuk yap grlmekte-
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dir. ekil 3.b de ise yaklak 100 nm kalnlnda ve 400 nm geniliinde nano ubuk yap grlmektedir. Bu yap sl ilem srasnda yeterli derecede byyememitir. ekil 3.bdeki bu yap ekil 2 de belirtilen karbon tabakalara benzemektedir. Aradaki fark, ekil 3.bdeki yap scakln etkisiyle daha fazla oranda bym dolaysyla kalnl daha fazla olan karbon nano ubuk yapdr. ekil 2. deki yaplar ise, yeteri kadar byyememi ve bu sebeple ubuk formu kazanamam nispeten kaln karbon nano tabakalardr. ekil 3.b. deki yap iki paradan olumutur. Paralardan biri daha kaln olan ve yzeyini grdmz ksmdr. Dier para ise, yzeyi resimde grlemeyen ve kalnl nispeten daha az olan ksmdr. Kalnl daha az olan para ksmen hegzagonalliini yitirmitir (okla gsterilmitir). Hegzagonal yzeydeki bu hasar muhtemelen mekanik alamlama ilemi srasnda bilye darbeleri sebebiyle meydana gelmitir.
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ekil 3: a) ve b) 250 saat MA sonras 1600 oC de 4 saat sl ilem uygulanm numunenin FE-SEM grnts, c) karbon nano ubuklarn bymesinin ematik olarak gsterilmesi [8] Grafitin tlmesi sonucu karbon nano ubuklarn oluma sebebinin tme trnden kaynakland sanlmaktadr. MA ilemi srasnda bilyelerin tozlara kayma trnde gerilmeler uygulamas grafit tabakalar arasndaki zayf balarn krlmasna sebep olmutur ve uygulanan gerilmeler grafit tabakasna, baka bir deyile bazal dzleme zarar vermemi, hegzagonal yaplarn muhafaza etmelerine imkan tanmtr. MA ilemi sonunda uygulanan tavlama ilemi ise hegzagonal yapdaki grafen tabakalarnn st ste gelerek [0001] ynnde bymesine sebep olmutur ve bylece nano ubuk yaplar ortaya kmtr [8]. Nano ubuklarn oluumu ematik olarak ekil 3.c. de gsterilmitir. Baz blgelerde ise byme gereklememi ve tabakalar bymeden olduu gibi kalmtr. Karbon nano ubuk yaplarn MA srasnda tozlara darbe trnden gerilmeler uygulandnda olumad rapor edilmektedir [7]. Uygulanan gerilme trne gre grafitin kristal yapsnda meydana gelen deiimler ekil.4 de ematik olarak verilmitir. Grld gibi, darbe trnden gerilmeler uygulanmas durumunda sadece grafit tabakalar arasndaki ba deil ayn zamanda tabaka ierisindeki gl C-C balar da krlarak yap tamamen amorf hale gelmektedir. Fakat kayma trnden gerilmeler uyguland zaman bilyelerin toza uyguladklar gerilme miktar nispeten dn olmasndan dolay sadece tabakalar arasndaki balarda krlmalar meydana gelirken, tabaka iindeki balar krlmadan kalmaktadr. Bu almada kayma trnden gerilmeler uygulandndan tr MA ilemi sonunda pek ok grafit tabakas kristal yaps bozulmam halde kalmtr. MA ilemi sonunda elde edilen toza uygulanan sl ilem bu tabakalarda bir etkiye sebebiyet vermemitir. Sadece tabakalarn st ste gelerek dizilmesine baka bir deyile nano ubuk tipi yaplarn olumasna sebep olmutur.
ekil 4: MA ilemi srasnda grafit tozlarna uygulanan gerilme trne gre tozun kristal yapsnda meydana gelen deiimlerin ematik grnts [6]
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ekil 3.a da karbon nano ubuklar, kristal yapsn muhafaza etmi grafitik tabakalarn yannda nano topak haldeki amorf karbon da bulunmaktadr. Planeter bir deirmende belli bir hzda tek bir bilye ile yaplan MA ilemi srasnda bilyenin toza uygulad gerilmeler kayma gerilmeleri eklindedir ve kapta ok bilye olmad iin tozlara uygulanan darbe trndeki gerilmeler minimum dzeydedir. Fakat tek bilye ile yaplan deneylerde tozlarn kesinlikle darbe gerilmelerine maruz kalmayacaklarn sylemek mmkn deildir. Tek bilye ile yaplan MA ileminde ortaya kan darbe gerilmeleri, bilye ile kabn arasndaki arpmalardan tr meydana gelmektedir. Bu dk enerjili arpmalar darbe gerilmeleri yaratmakta ve MA sresinin artmasyla bir ksm tozlarn amorflamasna, bir ksm tozlarda ise grafitik tabakalarn bklmesine sebep olmaktadr. 4. GENEL SONULAR Grafite uygulanan kayma trnden gerilmeler kristal yap bozulmakszn nano boyutlu grafit tabakalarnn olumasn salamaktadr. MA sresi 250 saat olmasna karn (002) piki tamamen kaybolmamtr. Tozun baz blgelerinde ksmen amorflama mevcuttur ve bu amorf yaplar sl ilem sonunda yeniden kristalleememilerdir. Yaplan sl ilem sonunda nano boyutlu grafit tabakalar st ste gelerek karbon nano ubuklar oluturmutur. 5. KAYNAKLAR
1. Antisari M.V., Montone A., Jovic N., Piscopiello E., Alvani C., Pilloni L., Low Energy pure shear milling: A 2. Huang J.Y., Yusuda H., Mori H., Highly Curved Carbon Nanostructures Proced by ball-milling, Chem. Phys. 3. Chen Y, Conway M.J., Fitz Gerald J.D., Carbon nanotubes formed in graphite after mechanical grinding and 4. Chen Y. Solid-state formation of carbon nanotubes. In: L. Dai, editor. Carbon Nanotechnology, UK;Elsevier; 5. Gosh, B., Pradhan, S.K., Microstructure characterization of nanocrystalline Fe3C synthesized by high energy 6. Disma F.S., Tarascon J.M, Clinard C., Rouzaud J.N., Transmission Elektron microscopy studies on carbon 7. Gler ., Mekano-Termal Yntem le Karbon Nano Tp retimi Ve Karakterizasyonu, Doktora Tezi, Frat 8. J.S. Lee, K. Park, M.I. Kang, I.W. Park, S.W. Kim, W.K. Cho, H.S. Han, S. Kim, ZnO nanomaterials synthesized
from thermal evaporation of ball-milled ZnO powders, J. Crystal Growth, 254, 428, 2003 niversitesi F.B.E., 2011 materials prepared by mechanical milling, Carbon vol.37, pp.1941-1959, 1999 ball milling, J. Of Alloys and Compounds, 477, pp 127-132, 2009 53-8, 2006 thermal annealing, Applied Physics A, vol. 76, pp. 633-636, 2003 Lett. Vol.303, pp. 130, 1999 method fort he preparation of graphite nano-sheets, Scripta Materialia vol.55, pp.1047-1050, 2006
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FARKLI SRELERDE MEKANK ALAIMLANAN NKEL ESASLI SPERALAIM TOZUN KARAKTERZASYONU

nn . Mh. Fak. Makine Mh. Blm, Malatya, mehmet.erdem@inonu.edu.tr *Gazi ., Tekn. Fak., Metalrji ve Malz. Mh. Blm, Ankara, mturker@gazi.edu.tr ZET Bu almada, Ni esasl speralam toz karm (%75 Ni, %20 Cr, %4 Al2O3, %0.6 Ti, %0.4 Y2O3), seramik bir kazanda farkl srelerde (-24 saat) ve 450 rpm sabit hzda mekanik olarak alamland. Farkl mekanik alamlama srelerinin speralam toz boyutuna, ekline ve mikro sertliine etkisi tespit edildi. Mekanik alamlanan tozlarn karakterizasyonu iin toz boyut analizi, mikro sertlik lm ve elektron mikroskop (SEM) almas yapld. Bu analizlerde; artan mekanik alamlama sresi ile speralam toz boyutunun mikron alt boyutlara kadar kld, souk kaynak sonucu lamelli yapnn olutuu ve lameller aras mesafenin zamanla darald ve toz mikro sertliinin art tespit edildi. Ayrca, 4-8-12-16-24 saat mekanik alamlanan speralam tozlarn X-RD (X-Ray Diffraction) analizleri yapld ve herhangi bir metaller aras bileiin olumad belirlendi. Anahtar Kelimeler: Ni esasl speralam, Mekanik alamlama sresi, Mikroyap karakterizasyonu
CHARACTERIZATON OF Ni BASED SUPERALLOY POWDER MECHANICAL ALLOYED FOR VARIOUS DURATIONS

ABSTRACT In this study the Ni based superalloy powder mixture (75% Ni, 20 % Cr, 4% Al2O3, 0.6% Ti) were alloyed in a ceramic container under different durations (-24 hours) and 450 rpm constant speed. It has been determined the effect of different mechanic alloying durations for superalloying powder dimensions, forms and micro hardness. The powder dimension analyze, micro hardness measurement end SEM has been carried out for characterization of the mechanically alloyed powder. In this analyses; it has been determined that the superalloy powder dimension were diminished to sub-micron dimensions, lamellae structure got finer and the distance between the lamellaes got closer and the micro hardness of powder were increased with increasing the milling time. Moreover the X-RD (X-Ray Diffraction) analyses of mechanical superalloyed powder for 4-8-12-16-24 hours were carried out and there has been determined that a inter-metallic compound was not formed. Keywords: Ni based superalloy, mechanical alloying duration, microstructural characterization 1. GR Mekanik alamlama (MA) son derece homojen ve ince mikro yaplar elde etmek amacyla kuru, ya, yksek enerjili, bilyeli ve/veya ubuklu tme teknii olarak tanmlanmtr [1-3]. MA mekanizmas ayr aamadan meydana geldii kabul edilmektedir. Birinci aamada, tme srecindeki bilye-bilye, bilye-cidar ve kartrclar-cidar arpmasyla arada kalan tozlara bir miktar darbe enerjisi yklenir. Bu darbe enerjisi yumuak tozlarda ekil deiimine, sert tozlarda ise krlmaya neden olur. Deformasyon ve krlmayla
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oluan yeni yzeyler ilemin devam etmesiyle birbirleriyle kaynaklanr. Bylece, alamlamann ilk aamasnda toz parack boyutu artar. Bu aamada parack boyutu byyerek balang parack boyutunun 3 katna kadar ulaabilir [4]. kinci aamada, artan MA sresi ve deformasyon ile tozlarda ki deformasyon peklemesi ve sertlik artar [5]. Bu sertlik etkisiyle toz paracklarnda krlma balar ve bu aamada krlma souk kaynaktan daha etkindir. nc aamada ise her bir toz parac ierisinde bulunan alam tabakalar arasndaki boluklar azalrken, ayn zamanda bu alam tabakalarnn says artar. Parack iindeki katmanlar aras mesafe azalrken, katman says da artar. Belli bir sre tmenin ardndan, ortalama parack boyutunu artran kaynaklanma ve ortalama toz partikl boyutunu azaltan krlma, miktarlar arasnda bir denge yakalandnda kararl hal dengesine ulalr. Salkl bir mekanik alamlama ileminin gerekletirilebilmesi iin ilem zerinde olduka fazla etkileri olan deirmen tipi, tme kazan, tme hz, zaman, tme malzemesi (bilye), bilye-toz arlk oran, kazan doldurma miktar, tme atmosferi, scakl, ilem kontrol kimyasal gibi parametrenin doru bir ekilde seilmi olmas gerekir. Bunlar tlecek tozun miktarn, boyutunu, kirlenme orann, tme enerjisini ve toz kaybn etkileyen en nemli parametrelerdir. MA da, tcden elde edilen enerjinin verimli kullanlmas ve tozun kimyasal yapsnn deimesine kazan tipi etki eder. MA ilemi srasnda tc bilyelerin tme tanknn i cidarna uyguladklar darbeler nedeniyle kap malzemesinin bir ksm yzeyden koparak toza karabilir. Bu durum tozun kimyasal yapsnn deimesine veya paracklarn kalkt blgelere tlen tozun yapmasna neden olur. Buda, toz kaybna ve toz kirliliine neden olur. Bu konu ile ilgili yaplan bir almada [6], bakr kap iinde Cu-In-Ga-Se toz karm tlm ve toz iindeki bakr miktarnn balang toz karmna gre daha yksek olduu tespit edilmitir. tme kabndan kopan bakr paralarnn toza karmas neden olarak belirtilmitir. Byle durumlarda tozun kimyasal bileiminin deimemesi iin uygun tme kab seilerek gerekli nlemler alnmaldr. tc maddenin younluu, toz zerine yeterli darbe enerjisi oluturabilecek byklkte olmaldr. rnein elik bilye yerine WC bilyeler kullanlarak yaplan bir almada daha yksek darbe enerjisi elde edilmitir [7]. Ayn zamanda tc madde boyutu da tme verimini dorudan etkiler. Genelde byk boyutlu bilyeler toz paracklar zerine daha fazla darbe enerjisi transfer ederler. Ancak gereinden byk bilyeler toz boyutunun klmesini engelleyebilirler. tc madde boyutunun tozun final yaps zerinde etkili olduu tespit edilmitir. Bu konuyla ilgili yaplm bir almada, titanyum alminyum toz karm 5 ve 8 mm apnda ki bilyeler kullanlarak tldnde amorf fazn olutuu 12 mm apndaki bilyeler kullanldnda ise amorf fazn olumad gzlemlenmitir [8]. Pd-Si sisteminde de benzer ekilde amorf fazn olumas iin kk boyutlu bilyelerin tercih edildii bildirilmitir ve kk bilyelerin gl srtnme hareketi rettii ve bununda amorf faz oluumunu hzlandrd belirtilmitir [9]. Toz paracklarn kararl hal dengesine ulamasnda en nemli parametrelerden biride MA sresidir. Normal artlarda sre, toz paracklar arasndaki krlma ve souk kaynaklama kararl hale gelecek kadar seilmelidir [10]. zellikle titanyum ve zirkonyum gibi reaktif elementlerin bulunduu tozlar eer gereinden fazla tlrlerse, kirlenmeleri ve istenmeyen fazlarn olumas kanlmaz olur [11]. Bu nedenle tozlar sadece gerekli olan sre kadar tlmelidir. Toz paracklarnn kararl hale gelmesi iin, yksek enerjiyle ksa sreli ve dk enerjiyle de uzun sreli tme yapmak genel olarak kabul edilen bir kuraldr. Yani, yksek bilye-toz orannda az sre, dk bilye-toz orannda ise daha fazla sre kullanlmaldr. MA iin gerekli sre tme hzna, tc tipine, tme younluuna, tme scaklna ve bilye-toz arlk oranna bal olarak deiiklik gsterir. Bu parametreler, her bir toz kombinasyonu iin ayr ayr belirlenmelidir [12]. Bu almada, nikel esasl sper alam toz karmna MA sresinin etkisi aratrlmtr. Bu amala farkl srelerde mekanik alamlanan tozlar toz boyut analizi, mikro sertlik lm, taramal elektron mikroskop (SEM) almas ve XRD analizleri ile karakterize edilmitir. 2. MALZEME VE METOD Deneylerde kullanlan toz komposizyonu Tablo 1de, SEM ve EDAX analizleri de Resim 1-5de verilmitir. Deneylerde kullanlan Ni tozunun ortalama toz boyutu 10,38 m, Cr tozunun 87,90 m, Al2O3 tozunun 3 m, Y2O3 tozunun 3 m ve Ti tozunun ise 2-50 m gibi geni bir aralkta deitii grlmektedir. MA ilemi esnasnda yalayc olarak %2 toz Zn-stearat kullanlmtr. Ancak, 16 ve 24 saat MA esnasnda tozlarn, kartrc kollara, bilyelere ve kazan i yzeyine svanmas nedeni ile atritrn zorland grlm ve Zn-stearat miktar %3e kartlmtr. Mekanik alamlama ilemi Unionprocess firmas tarafndan imal edilen 2 litrelik tme tankna sahip dnme hz dijital olarak ayarlanabilen SZEGVARI modelli bir atritrde 450 dev/dak hzda ve 10/1 bilye-toz arlk oran kullanlarak yaplmtr. Deneylerde 50 gram toz karm 10 mm apnda elik bilyeler kullanlarak tlmtr. Mekanik alamlama esnasnda koruyucu atmosfer olarak yksek saflktaki (%99,999 orannda) argon gaz kullanlmtr. Argon gaz iindeki nemi kurutmak ve bulunmas muhtemel oksijeni yapdan uzaklatrmak iin gaz, boru ierisine doldurulmu 650oCdeki bakr talalarnn ierisinden geirilmitir.
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Optimum mekanik alamlama sresini tespit etmek amacyla seramik kazanda sekiz farkl sre (, 1, 2, 4, 8, 12, 16, ve 24 saat) kullanld. Deneyler esnasnda alamlama tank srekli olarak su sirklasyonu ile soutuldu. Deiik srelerde yaplan mekanik alamlama deneyleri sonras elde edilen tozlar rnga ile vakumlanan kk plastik kutulara konularak muhafaza edildi. Farkl srelerde mekanik olarak alamlanan tozlarn karekterizasyonu iin toz boyut analizi Malvern Mastersizer E ver 1.2 b cihaznda, mikro sertlik lmleri 10 g yk altnda SHIMADZU HMV-2 cihaznda, SEM ve EDX analizleri J0EOL JSM-6060 LV markal elektron mikroskobunda ve XRD analizleri de Bruker D 8 Advance markal cihazda oda scaklnda yaplmtr. Mikro yap almalarnda Marbel dalaycs kullanlmtr. Tablo 1. MA deneylerinde kullanlan toz kompozisyonu (% arlk). Element % Arlk Ni kalan Cr 20 Al2O3 4 Ti 0.6 Y2O3 0.4
Resim 1. Nikel tozu ve tozun EDAX analizi
Resim 2. Krom tozu ve tozun EDAX analizi
Resim 3. Al2O3 tozu ve tozun EDAX analizi
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Resim 4. Y2O3 tozu ve tozun EDAX analizi
Resim 5. Titanyum tozu ve tozun EDAX analizi 3. DENEY SONULARI VE TARTIMA 3.1. SEM Sonular saat mekanik alamlama sonunda elde edilen tozlara ait SEM grnts Resim 6-ada verilmitir. Mekanik alamlamann bu aamasnda, sert tozlarda krlma, yumuak tozlarda ise deformasyon nedeni ile azda olsa katmans yap oluumunun balad grlmektedir. ekil 6-bde 1 Saat MA sonunda elde edilen tozlarn mikro yaplar verilmitir. Bu aamada sert toz tanelerinin krlma ile inceldii ve yumuak toz tanelerinin ise souk kaynak ve deformasyonla uzad grlmektedir. ekil 6-cde 2 saat sreyle MA ilemine tabi tutulan tozlarda, heterojen bir boyut dalm dikkat ekmektedir. Tozlarn, e eksenli tane yaplarnn souk kaynaklanma nedeniyle zaman zaman bozularak tozlarn boy/en orannn artt grlmektedir. Resim 6-dde 4 saat mekanik alamlanm toz paracklar deformasyonun etkisi ile inceldii ve boy/en oranlarnn artt grlmektedir. Ayrca kaynaklama sonucu oluan katmanl (lamelli) yaplarn artt grlmektedir. ekil 6-ede 8 Saat mekanik alamlanm tozlarn SEM grntsnde tamamen lamelli yapnn hakim olduu ve lameller aras mesafenin 1 m dan fazla olduu ak bir ekilde grlmektedir. Alamlanm toz tanelerinin her biri, balang kompozisyon oranlarna sahip olup, tm balang bileenlerini ierdii sylenebilir. Resim 6-fde 12 saat MA ilemi sonras tozlarn SEM grnts verilmitir. Resimde, tozlarn kresel ve e eksenli tane yapsnda olduklar grlmtr. Lamel boy/en oran yaklak 10/1, lameller aras mesafenin ise yaklak 1 m civarnda olduu tespit edilmitir. 16 saat MA sonrasnda tozlar homojen grnml ve tane boy/en oranlar yaklak 1/1 civarnda kresel bir boyut dalmna sahip olduklar grlmektedir (Resim 6-g). Lamel boy/en oran yaklak 10/1 ve lameller aras mesafenin bir nceki aamaya gre (12 saat MA) zaman zaman kapand zaman zamanda 0,5 m civar olduu grlmtr. 24 saat MA ilemi sonunda elde edilen tozlarda ise (Resim 6-h) souk kaynak sonucu oluan lameller aras mesafenin nerdeyse tamamen kapand ve tozlarn kresel yapy koruduklar dikkat ekmektedir. Lameller, 12 ve 16 saat tlm toz yapsndaki lamellere gre daha ince olduklar grlmektedir. Lamel boy/en orannn yaklak 10/1 civarnda olduu tespit edilmitir.
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Resim 6. Farkl srelerde mekanik alamlanm tozlarn SEM grntleri. a- saat, b- 1 saat, c-2 saat, d- 4 saat, e- 8 saat, f- 12 saat, g- 16 saat, h- 24 saat
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3.2. Mekanik Alamlama Sresine Bal Toz Boyutu Deiimi MA sresine bal toz boyut deiimi ekil 1de grafik olarak verilmitir. Bu grafie gre saat alamlanan tozlar 11,43 m olup genelde elemental halde ve souk kaynaklamann etkin olmamas nedeni ile toz paracklarnn irilemedii grlmtr. 1 saatlik alamlama sonunda, toz paracklar arasnda zaman zaman meydana gelen kaynaklamalar toz boyutunun artmasna (16,09 m) neden olmutur. 2 saatlik mekanik alamlama sonunda tozlarda kaynaklamann hakim olmasyla birlikte toz boyutunda gzle grlen bir art (24,14 m) tespit edilmitir. 4 saatlik MA sonunda, kaynaklaan tozlar da deformasyon peklemesine bal sertlik art nedeni ile krlmann (22,55 m) balad tespit edilmitir. 8 saat MA uygulanm tozlarda krlmann daha etkin olmas sonucu boyutlarnda gzle grlen bir azalma (16,11 m) tespit edilmitir. 12 saat sonunda, pekleme sonucu toz sertliindeki arta bal krlmann devam etmesiyle toz boyutlarnn 10,96 m olduu tespit edilmitir. 16 saat MA ilemi sonunda da tozlardaki krlmann dzenli olarak devam ettii grlmtr (6,51 m). 24 saat MA ilemi uygulanm tozlardaki krlmann devam ettii ve nceki aamalara gre daha az oranda olduu grlmtr (4,95 m).
ekil 1. Mekanik alamlama sresine bal toz boyutu deiimi. Bu sonulara gre MA ileminin ilk aamas olan souk kaynaa bal parack boyutlarndaki art 2 saat MA sonrasnda gereklemi ve parack boyutu 24,14 mna ykselmitir. 4 saat tlen tozlardaki krlma ve kaynaklamann belli bir dengede devam ettii ve peklemeye bal krlma aamasnn henz balad grlmtr. nk, 2 saat sonunda 24,14 m olan toz parack boyutu, 4 saat sonunda 22,55 ma dm ve toz parack boyutunda gzle grlr bir azalma olmamtr. 8 saat MA sonunda peklemeye bal krlmann daha hakim olmas ile toz parack boyutu 16,11 mna dmtr. MA ileminin ikinci aamas 4 saat sonunda balam ve 8 saatte
ekil 2. MA sresine bal lameller aras mesafe deiimi
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kadar youn bir ekilde devam etmitir. Ayn zamanda MA ileminde nc aama olan kararl hal aamasnn da 8 saat MA sonunda balad ve 12-16 ve 24 saat MA ileminde de belli oranda devam ettii sylenebilir. nk 8 saat MA sonunda tozlarda lamelli yapnn hakim olduu grlmektedir (Resim 6-e). Artan MA sresi lamelli parack boyutunu kltrken, lameller aras mesafenin de kapanmasn salamtr. 8 saat sonunda lameller aras mesafenin yaklak 2 m ve lamel boy/en oran 15/1 olduu tespit edilmitir. 12 saat sonunda lameller aras mesafe (1 m) ve lamel boy/en orannn azald (10/1) grlmtr. 16 saat sonunda, tozlarn kresel yapy koruduklar, lameller aras mesafenin kapanmaya devam ettii (0,5 m) ve lamel boy en orannn 10/1 civarnda olduu grlmtr. 24 saat sonunda da tozlar kresel yapda olup, lameller aras mesafenin neredeyse tamamen kapand ve lamel boy en orannn 10/1 civarnda olduu grlmtr. ekil 2de artan MA sresine bal lameller aras mesafe deiimi verilmitir. Bu konu ile ilgili yaplan almalarda, artan tme sresine bal olarak lamelli yapnn inceldii ve lameller aras mesafenin azald belirtilmitir [13]. Bu konu ile ilgili elik kazanda yaplan benzer bir almada Ni esasl speralam tozlar farkl srelerde (-1-2-4-7 ve 8 saat) mekanik alamlanm ve toz boyutlar saatlik alamlama sonunda 9,42m, 1 saatlik alamlama sonunda 11,03m, 2 saatlik mekanik alamlama sonunda 8,67m, 4 saatlik mekanik alamlama sonunda 20,87m, 7 saatlik mekanik alamlama sonunda 11,34m ve 8 saatlik mekanik alamlama sonunda da ise 10,38 m olarak tespit edilmitir. Bu almada mekanik alamlamann ilk aamasna 4 saat MA sonunda, ikinci aamasna 7 saat MA sonunda ve nc aamasna da 8 saat MA sonunda ulald belirtilmitir [3]. Nikel esasl bir speralam zerinde yaplan baka bir almada da, dnme hz 710 dev/dak olan bir atritrde, farkl bilye aplar ile farkl srelerde MA ilemi denenmitir [14]. 10 mm apnda elik bilye ve kazan ile 2, 5 ve 10 saat MA ilemi sonunda ortalama toz boyutu sras ile 18,84 m, 27,52 m ve 23,20 m olduu belirtilmitir. Demir esasl bir speralam zerinde yaplan baka bir almada ise dnme hz 1200 dev/dak olan bir atritrde, ap olan bilyelerle farkl srelerde MA ilemi denenmitir [15]. mm apnda elik bilye ve kazan ile 1 saat MA ilemi sonunda ortalama toz boyutu 72,63 m, 2 saat MA ilemi sonunda ortalama toz boyutu 62,84 m, 10 saat MA ilemi sonunda ortalama toz boyutu 12,54 m, 24 saat MA ilemi sonunda ortalama toz boyutu 6,18 m ve 48 saat MA ilemi sonunda ise ortalama toz boyutu 12,05 m olduu belirtilmitir. 3.3. Mekanik Alamlama Sresine Bal Mikro Sertlik Deiimi Mekanik alamlama sresine bal toz mikro sertlik deerleri grafik halinde ekil 2de verilmitir. saat MA ilemine tabi tutulmu tozlar genelde elemental halde olup sertlikleri 143 HV olarak llmtr. 1 saat MA ilemi sonunda tozlardaki deformasyon miktarnn artmasyla sertlik 173 HV ye kmtr. 2 saat MA ilemi sonunda hakim olan souk kaynaklama nedeniyle toz parack boyutu artarken serlikleri de 189 HV ye kmtr. 4 saatlik MA ilemi sonunda artan deformasyon peklemesi nedeni ile toz parack boyutlarnda azalma, sertliklerinde ise artma tespit edilmitir (210 HV). 8 saat MA ilemi sonunda tozlarda lameli yap hakim olup, sertlik deeri 239 HV olarak tespit edilmitir. Tozlardaki lamelli yapnn artmas, artan MA srelerinde toz sertlik lmlerini zorlatrmtr. nk, sertlik cihaznn batc ucu lameller arasna geldiinde sertlik deerlerinin dk kmasna neden olmutur. Bu nedenle sertlik lmleri titizlikle yaplmtr. 12 saatin sonunda tozlardaki krlma ve sertlik artnn devam ettii tespit edilmitir (276 HV). 16 saat MA ilemi sonunda, souk kaynak sonucu oluan toz paracklarndaki lameller aras mesafenin ve parack boyutlarndaki azalmann devam ettii grlm ve artan deformasyon peklemesi nedeniyle sertlik 301 HV olarak tespit edilmitir. 24 saat MA ilemi sonunda toz paracklarnn krlmaya devam etmesi ve zaman zaman da mikron alt seviyelerde olmalar nedeniyle mikro sertlik lmleri yaplamamtr. Bu konu ile ilgili elik kazanda yaplan benzer bir almada Ni esasl speralam tozlar farkl srelerde mekanik alamlanm ve mikro sertlikleri 2 saat MA ilemi sonunda 102 HV, 4 saat MA sonunda 128 HV, 7 saat MA sonunda sertlik 212 HV, ve 8 saat MA sonunda ise 218 HV olarak bulunmutur [3]. Ayn almada toz parack sertliinin 8 saat MA sonunda kararl hale geldii ifade edilmitir. Baka bir almada demir esasl sper alam tozlar dikey bir atritrde deiik srelerde (1-2-10-24 ve 48) saat) tlm ve artan MA sresi ile toz mikro sertliklerinin artt belirtilmitir. 1 saat MA ilemi sonunda tozlarn mikro sertlii 292 HV, 2 saat sonunda 313 HV, 10 saat sonunda 323 HV, 24 saat sonunda 382 HV ve 48 saat sonunda ise 525 HV olduu tespit edilmitir [15]. Bu konu ile ilgili yaplan baka bir almada da, nikel esasl sper alam tozlar deiik aptaki (6-5/6 ve 10 mm) bilyelerle deiik srelerde (510-15 ve 24 saat) dikey bir atritrde tlm ve artan MA sresi ile toz mikro sertliklerinin de artt belirtilmitir [14]. Botcharova E., ve arkadalar bakr ierisine deiik oranlarda niobyum ilave etmiler ve farkl srelerde bilyeli tcde tmlerdir. Artan MA sresi ile beraber tozlarn mikro sertliklerinin arttn ve toz parack boyutunun da kldn tespit etmilerdir[16]. Adabavazeh Z. ve arkadalar %50 Fe, %25 Ni ve %25 Al tozlarna oda scaklnda farkl srelerde(5-20-40-80 saat) 20mm apndaki bilyelerle (bilye toz oran 10/1) mekanik alamlama ilemi yapmlar ve artan MA sresine bal olarak tozlarn mikro sertliinde art tespit etmilerdir[17].
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ekil 3. Mekanik alamlama sresine bal mikro sertlik deiimi. 3.4. Tozlarn X-RD analizleri tme esnasnda tozlar arasnda meydana gelebilecek muhtemel bileikleri tespit etmek amacyla seramik kazanda, farkl srelerde (4, 8, 12, 16, 24 saat) tme ilemi uygulanan tozlarn X-RD analizleri yaplmtr. X-RD analizinde Cu K n (k = 0.1542 nm) kullanlmtr. .Elde edilen sonular ekil 4-8de sras ile verilmitir. X-RD analizleri, 4, 8, 12, 16 ve 24 saat sonunda toz yaplarnda farkl bir bileik yada amorf yapnn henz olumadn gstermitir. Bu konu ile ilgili yaplan bir almada, n alamlanm iki farkl toz bileimi, (Ni-%13,3Al- %2,1 Y2O3 ve Ni-%50Al- %2,1 Y2O3) titreimli bilyeli tcde 50 saat tlm ve XRD analizleri yaplmtr. MA esnasnda tozlarn tamamen B2-NiAl bileiine dnt tespit edilmitir [18]. PM 1000 ile benzer bileim ve mikro yapya sahip olan MA 754 alamnda saf Y2O3in yerine yitrium alminann var olduu belirtilmitir [19]. Bu bileiklerin alamn retimi esnasnda, Y2O3 paracklarnn bir ou Al ile kat zelti ierisinde reaksiyona girmeleri ile olutuu belirtilmitir [20].
ekil 4. 4 Saat MA sonras tozlarn X-RD analizi
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4. BULGULAR VE NERLER Seramik kazanda elik bilye kullanlarak yaplan MA ileminde MA sresinin Ni esasl speralam toz boyutu, ekli ve sertliine etkisi incelenmi ve aadaki sonular elde edilmitir. 1. Yaplan MA ileminde toz paracklarnn souk kaynak sonucu irilemesi aamas olan birinci aamaya 2 saat MA sonunda, deformasyon peklemesi nedeniyle toz paracklarnn krlma aamas olan ikinci aamaya 4 saat MA sonunda ve kaynaklama ve krlmann dengede olduu kararl hal aamas olan nc aamaya da 8 saat MA sonunda ulalmtr. Ayrca 8 saat MA sonrasnda tozlarda lamelli yaplarn hakim olduu grlmtr. 2. 8 saat MA sonras ulalan kararl hal aamasnn 12-16 ve 24 saat MA sonrasnda da devam ettii tespit edilmitir. 8 saat MA sonrasnda itibaren toz paracklarnn ortalama toz boyutunun klmesiyle lamel boy/en oranlarnn 15/1den 10/1 seviyelerine dt, toz paracklarndaki lamel saysnn artt ve lameller aras mesafenin azald tespit edilmitir . 3. Artan MA sresine bal olarak parack boyutlarnn kld 24 saat MA sonunda zaman zaman mikron alt byklklere ulald grlmtr. Ayrca artan MA sresi ile toz paracklarnn deformasyon peklemesine bal olarak mikro sertliklerinin de artt tespit edilmitir. 4. Tozlara 4, 8, 12, 16, 24 saat MA ileminden sonra uygulanan X-RD analizlerinde farkl bir bileik yada amorf yapnn henz olumad grlmtr. Uzun sreli ( 50 saat ve zeri) yaplacak tme ilemlerinde, Ni-Al- Y2O3 alam sistemlerine ait bileiklerin oluabilecei dnlmektedir. 5. Farkl aplarda tc biyelerle ve farkl tme hzlarnda uzun sreli (50 saat ve zeri) MA ilemi yaplabilir ve olumas muhtemel bileik yada amorf yaplarn analizleri yaplabilir. 5. KAYNAKA
1.
Schelleng, R.D., and Donachie, S.J., Mechanical alloyed aluminum, Metal Powder Report, 38:357-359, 1983. 2. El-Eskandarany, M. S., Aoki, K., Suziki, K. J. Less Common Metals 167:113-118, 1990. 3. Erdem. M., Trker, M., Farkl srelerde mekanik alamlanan nikel esasl speralam tozun karakterizasyonu, 13th International Metalurgy & Materials congress, stanbul, 930-936, November 09-11, 2006. 4. Suryanarayanan, C., Ivanov, E., Boldyrev, V. V., The Science and Technology of Mechanic Alloying, Mater. Sci. Eng. A304-306:151-158, 2001. 5. Trker, M., zdemir, A.T., el, B. ve Yavuz, A., Al-SiC tozlarnn alamlama deirmeninde tme zamannn kompozit toz yapsna etkisinin aratrlmas, 2. Ulusal Toz Metalurjisi Konferans, 425-431, 15-17 Eyll ODD, Ankara, 1999. 6. Suryanarayana, C., Ivanov, E., Noufi, R., Contreras, M.A., Moore, J. J., Phase selection in a mechanically alloyed Cu-In-Ga-Se powder mixture J. Mater. Res., 14: 377-383 (1999). 7. Gonzales, G., Sagarzazu, A., Villalba, R., Ochoa, J., DOnofrio, L., Effect of the milling media on the phases obtained in mechanically alloyed equiatomic Fe-Co, Mater. Sci. For., 360-362:355-360 (2001). 8. Park, Y.-H., Hashimoto, H., Watanabe, R., Morphological evolution and amorphization of Ti/Cu and Ti/Al powders mixtures during vibratory ball milling Mater. Sci For., 88-90: 59-66 (1992). 9. Padella, F., Paradiso, E., Burgio, N., Magini, M., Martelli, S., Guo, W., Iasonna, A., Mechanical alloying of the Pd,Si system in controlled conditions of energy transfer, J. Less Common Metals 175: 79-90 (1991). 10. Suryanarayana, C., Internalt. Mater. Rev., 40:41-64, 1995. 11. Schaffer, G.B.,McCormick, P.G., Metal Transaction A, 22:2789, 1990. 12. Bostan, B., Synthesis of Al-C by MA Process, Ph.D. Thesis., G.U. Enst. Of Sci. And Techn., Ankara, (2003). 13. Suryanarayana, C., Mechanical alloying and milling, Marcel Dekker, New York, 1-466 (2004). 14. Evin, E., Nikel Esasl Bir Sper Alamn Mekanik Alamlama Yntemi le retilmesi Ve Mikroyap-Oksitlenme zelliklerinin Aratrlmas, Doktora Tezi, Frat ., Fen. Bil. Enst., 2003. 15. Kln,Y., Demir bazl speralamlarn mekanik alamlama metodu ile retilmesi ve zelliklerinin aratrlmas, Doktora tezi, G..Fen Bil.Enst., Ocak 1999. 16. Botcharova E., Heilmaier M., Freudenberger J., Drew G., Kudashow D., Martin U., Schultz L., Supersaturated solid solution of niobium in copper by mechanical alloying Journal of Alloys and Compounds 351 (2003) 119125 17. Adabavazeh Z., Karimzadeh F., Enayati M.H., Synthesis and structural characterization of nanocrystalline (Ni, Fe)3Al intermetallic compound prepared by mechanical alloyin, Advanced Powder Technology xxx (2011) xxxxxx (article in press). 18. Grahle, P., and Arzt, E., Microstructural development in dispersion strengthened NiAl produced by mechanical alloying and secondary recrystallition, Acta Mater., 45(1): 201-211(1997). 19. Howson, T. E., Stulga, J.E., Tien, J.K., Creep and stres rupture of a mechanically alloyed oxide dispersion and precipitation strengthened nicel-base superalloy, Metall. Trans., 11A: 1599 (1980). 20. Sha, W., Bhadeshia, H. K. D. H., Characterization of mechanically alloyed oxide dispersion-strengthened nicel-based superalloy MA760, Matall. Trans., 25A: 705-714 (1994).
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AL MATRSL VE Al2O3 PARACIK TAKVYEL KOMPOZTLERN FARKLI MEKANK ALAIMLAMA SRELERNDE RETLMES VE KARAKTERZE EDLMES
Hasan KARABULUT*, Ramazan ITAK**
*
Ankara Altnda Siteler Mesleki Eitim Merkezi, Metal Teknolojisi retmeni, Siteler, 06500, Ankara, karabulut.hasan@hotmail.com ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, rcitak@gazi.edu.tr ZET
Al matrisli Al2O3 parack takviyeli kompozitler farkl srelerde mekanik alamlanm ve mekanik alamlama sresinin alamlanm tozlarda, parack dalm, toz boyutu, sertlik, younluk ve gzeneklilik gibi karakteristik zelliklere etkisi incelenmitir. Mekanik alamlama sonras numunelerde homojen bir parack dalm elde edilmitir. Alamlama sresinin artmasyla toz boyutu klrken, sertlik artmtr. Ayrca artan alamlama sresi ile younluk azalm, gzenek oran da artmtr. Anahtar Kelimeler: Kompozit, Al2O3, Mekanik alamlama, Sertlik.
PRODUCTION AND CHARACTERIZATION OF AL MATRIX AND Al2O3 PARTICLE-REINFORCED COMPOSITES FOR DIFFERENT MECHANICAL ALLOYING DURATIONS
ABSTRACT Composite materials with Al2O3 particle reinforcement and Al matrix were produced by using mechanical alloying methods for different periods of time. Effect of time on particle distribution, particle size, hardness, density and porosity ratio were investigated. A homogeneous particle distribution was obtained in samples mechanical alloyed. While particle size was decreasing with alloying time hardness was increased. In addition, the density decreased with alloying time and porosity increased. Key Words: Composite, Al2O3, Mechanical alloying, Hardness. 1. GR Gelien teknoloji ile tm mhendislik dallarnn ve insan ihtiyalarnn da deimesi metalurji ve malzeme alanndaki aratrmaclarn yeni malzeme retme almalarnn nemini artrmaktadr. Kompozit malzemeler ve zellikle metal matrisli kompozit malzeme retimi bu almalardan sadece bir tanesidir. Kompozit malzemeler, kimyasal bileimi ve zellikleri bakmndan farkl olan birden daha fazla sayda malzemenin makro dzeyde birletirilmesi ile bir araya getirilen malzemelerdir [1]. Kompozit malzeme ierisindeki bileenler ara yzeylerle birbirinden ayrlr ve yap ierisinde kendine has zelliklerini muhafaza ederler [2]. Kompozit malzemeler bir ok yntemle retilebilir. Bu yntemlerden bir tanesi de Mekanik alamlamadr (MA). MA yntemi, yksek enerjili bir deirmen ierisinde toz ve paracklarn kartrlmas esnasnda kaynaklanmas, paralanmas ve yeniden kaynaklanmasn ieren bir kat hal ile tekniidir [3]. Mekanik alamlama ilemi ile dkm ynteminde karlalan homojenlik, slatlabilirlik, birbiri ierisinde karmama vb. problemler ortadan kaldrlabilir [1-7].
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Bu almada, Al matrisli Al2O3 seramik parack takviyeli kompozitler mekanik alamlama yntemiyle retilmitir. Farkl alamlama srelerinde, mikroyap dalm, tane boyutundaki deiimler, younluk, gzeneklilik ve sertlik gibi zelliklerin incelenmesi amalanmtr. 2. DENEYSEL ALIMALAR Matris malzemesi olarak, gaz atomizasyon yntemi ile retilmi, % 99,7 saflkta, 72,24 m ortalama toz boyutunda alminyum toz kullanld. Takviye eleman olarak ise 15,40 m ortalama toz boyutunda Al2O3, seramik tozlar kullanld. MA ilemi, szegvari modeli dikey bir atritr ierisinde 10/1 bilye/toz orannda, 10 mm apnda elik bilye ve % 1,5 yalayc ilave edilerek yapld. MA ilemi 350 rpm hzda akan argon atmosferinde 2, 6 ve 10 saat srelerde uyguland. MA srasnda snmay nlemek iin silindir akan souk su ile srekli soutuldu. MA sresinin toz boyutu zerindeki etkisini belirlemek iin toz boyut analizi yapld. Mekanik alamlanan tozlar 700 MPa basn altnda 12 x 15 mm boyutlarnda blok paralar oluturacak ekilde tek ynl olarak preslendi. Blok paralar 600 C scaklkta akan argon atmosferinde 1 saat sreyle sinterlendi. Sinterleme ncesi ve sonras younluk lmleri yaplarak gzenek deerleri belirlendi. Sinterlenen numunelerdeki sinterleme kalitesini ve faz dalmn grebilmek iin, uygun numuneler alnarak, zmparalama, parlatma ve dalama ilemleri uyguland. retilen kompozitlerin mikro yaplar Optik Mikroskop ve Taramal Elektron Mikroskobu ile incelendi. Brinell sertlik deerleri 2,5 mm bilye ve 31,25 kgf yk uygulanarak gerekletirildi. Her numune iin 6 sertlik lm uygulanarak ortalamas alnd. 3. DENEYSEL SONULAR 3.1. Tane Boyut Analizi Matris olarak kullanlan saf alminyum tozlarn ve takviye eleman olarak kullanlan Al2O3 tozlarnn SEM fotoraflar Resim 1de verilmitir. Bu resimlerden Al matris malzemesinin ounlukla dzensiz ekilli olduu, ancak keskin kelerin olmad, Al2O3 tozlarnn da dzensiz bir geometride ve keskin keli olduklar grlmektedir.
Resim 1. (a) Saf Al tozunun ve (b) Al2O3 tozunun SEM grnts Ortalama toz boyut analiz sonular ekil 1.de verilmitir. MA uygulanmam, ancak bilyesiz olarak eksenli turbula cihaznda homojen karm yaplm (TK) kompozitlere gre, 2 saat MA ilemi uygulanan numunelerde toz boyut oran ksmen artmaktadr. Ancak MA sresinin 6 ve 10 saate kmasyla toz boyut oran srekli olarak klmektedir. zellikle MA sresi 10 saate kartlmasyla toz boyutundaki klme oran daha da fazlalamtr. Bunun sebebi artan deformasyon ve peklemenin sonucunda krlma mekanizmasnn etkili olmasdr. Benzer ekilde, Ark ve Trker MA yntemi ile rettikleri Fe-Fe3C kompozitlerde alamlama sresinin artmasyla toz boyutunda azalmalar tespit etmilerdir [10, 11]. Gemite yaplan baz almalarda aratrmaclar, kk paralarn byk paralarla kaynaklama eiliminde olduklarn ve MA sresinin artmasyla tekrar tane klmesinin olutuunu tespit etmilerdir [12, 13].
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ekil 1. MA sresine gre toz boyutu deiimi Resim 2.de verilen SEM fotoraflar da MA sresinin artmasyla tane boyutunda oluan klmeyi ak bir ekilde ifade etmektedir. Ayrca bu resimlerde TK numunesinde herhangi bir deformasyon etkisi grlmezken, MA ilemi uygulanan tozlarda oluan deformasyon belirgin olarak grlmektedir
Resim 2. (a) TK, (b) 2 saat MA, (c) 6 saat MA, (d) 10 saat MA ilemi uygulanm tozlarn SEM resimleri
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3.2. Mikro Yap zellikleri Resim 3te kompozitlere ait mikro yap resimleri verilmitir. Bu resimlerde grld gibi tm numunelerin parack dalm homojene yakndr. TK numunesinde gzeneklerin neredeyse tamamen kapand sylenebilir. 2 saat MA yaplm numunede tane snrlar neredeyse kaybolmuken, dier numunelerde ksmen tane snrlar belirgindir. 2 ve 6 saat sreyle MA ilemi yaplm numunelerde tane snrlarna yakn yerlerde ksmen kk topaklamalar mevcuttur. Tm numuneler iin ounlukla takviye elemanlar matris ierisinde gmlm olmakla birlikte, ksmen tane snrlarnda kk birikmelerin olduu da grlmektedir. zellikle 10 saat MA yaplm numunelerde gzenek miktarlarndaki art belirgindir.
Resim 3. Kompozitlerin Optik Mikroskop resimleri (a) TK ilemi yaplm, (b) 2 saat, (c) 6 saat ve (d) 10 saat MA ilemi yaplm. Bunun yannda 10 saat MA yaplm numunelerde mikro yapda grlen karartlarn kirlenmeler olabilecei dnlerek bu numunelerin SEM ve EDS analizleri alnmtr (Resim 4). 10 saat MA yaplm kompozitin optik mikroskop resimlerinde kirlenme varm gibi grnen yzeylerin aslnda klm seramik paracklar ve gzeneklerden ibaret olduu kompozitlerden alnan SEM ve EDS analizleriyle tespit edilmitir. Bu analizlerde kompozitin yapsnda herhangi bir reaksiyon rn element ya da faz olumad belirlenmitir.
(a) SEM grnts (b) Genel EDS analizi Resim 4. 10 saat MA yaplm Al+%10 Al2O3 kompozit numuneler iin SEM resmi ve EDS analizi
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3.3. Younluk ve Gzeneklilik Younluk ve gzeneklilik deerleri ekil 2de verilmitir. Beklendii gibi tm deneylerde sinterleme sonras llen younluk deerleri ham younluk deerlerine oranla artmtr. MA uygulanmam, ancak bilyesiz olarak eksenli turbula cihaznda homojen karm yaplm kompozit numunelerin sinterleme ncesi ve sinterleme sonras younluk deerleri, MA yaplm kompozit numunelere gre daha yksektir ve gzenek deeri de daha dktr. MA sresinin artmasyla numunelerin younluk deerleri derken, gzenek miktarlar da ksmen artmtr. MA sresinin artmasyla oluan souk deformasyon ve pekleme, tane boyutunu klterek malzemelerin sktrlabilirliini olumsuz etkilemitir. Dolaysyla bu durum, MA sresinin artmasyla younluun dmesine ve gzenekliliinde ksmen artmasna neden olmutur. Sarta ve arkadalarda, kk tozlarn sktrmaya diren gsterdiini ve bundan dolay zellikle nano boyutlu tozlarn sktrlabilirliinin ok zor olduunu belirtmitir [9].
ekil 2. Al+%10 Al2O3 blok numuneler iin younluk ve gzeneklilik deerler 3.4. Sertlik Brinell sertlik deerleri ekil 3te verilmitir. Beklendii gibi saf alminyumun sertlik deeri 28 BSD iken MA ile numunelerin sertlik deerleri doal olarak ykselmitir. MA sresinin artmasyla genel olarak tm numunelerin sertliklerinde bir art olduu grlmektedir. Bu artn, MA srasnda yksek deformasyonun etkisiyle oluan tane klmesinden kaynakland dnlmektedir. Benzer ekilde Ark, MA ile rettii kompozitlerde sertlik iin en nemli faktrlerden birinin MA sresi olduunu belirtmitir. Ancak, yksek sinterleme scaklnn ve sresinin de sertlii etkiledii belirtilmitir. 10 saate kadar MA ilemlerinde 650 C de 20 saat sinterlenen numunelerin sertlik deerinde dzenli bir art grlrken, 10 saat MA ileminden sonra keskin bir art gzlemi ve bu artn kompozit yapsnda oluan Al4C3 varlndan kaynaklandn belirtmitir [10]. Ayrca gzenekliliin mekanik zellikleri olumsuz etkiledii bilinmektedir. Resim 3.(c)de grld gibi MA sresinin artmasyla gzeneklilik bir miktar artsa da, gzeneklerin ok kk olmas ve dzgn dalmas sebebiyle kompozitlerin mekanik zelliklerinde olumsuz bir etki olumamtr. Gzeneklerin ok kk ve kresel ekilli olmas tercih edilmektedir. Baz seramik malzemelerde gzenek deeri % 45lere kadar ksa bile, gzenekler ok kkse tam youn dayanma yakn deerler elde edilebileceini belirtilmitir [9].
ekil 3. Sertlik (BSD) lm sonular
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4. SONULAR MA sresinin artmasyla toz boyutu klmtr. retilen blok numunelerde homojen bir parack dalm olumaktadr. MA sresinin artmasyla younluk azalrken, gzeneklilik artmaktadr. MA sresinin artmasyla sertlikte srekli bir art meydana gelmektedir.
TEEKKR Gazi niversitesi BAP Birimine 07/2010-58 nolu proje kapsamnda yapt katklardan dolay teekkr ederiz. Kaynaklar 1. Kaw, A.K., Mechanics of Composite Materials, Crc Press, Washington, 1997. 2. Hull, D. ve Clyne, T.W., An Introduction to Composite Materials, 2nd Edition, Cambridge University Press, Cambridge, 1996. 3. Suryanarayana, C., Mechanichal alloying and milling, Progress in Materials Science, 46: 1-184 (2001). 4. Ylmaz, O. and Buytoz, S., Abrasive wear of Al2O3 reinforced aluminum based MMCs, Composites Science and Technology, 61: 2381-2392, 2001. 5. Abenojar, J., Velasco, F. and Martinez, M. A., Optimization of processing parameters for the Al + 10 % B4C system obtained by mechanical alloying, Journal of Materials Processing Technology, 18, 441-446, 2007. 6. Kennedy, A. R. and Brampton, B., The reactive wetting and incorporation of B4C particles into molten aluminum, Scripta Materialia, 44, 1077-1082, 2001. 7. Toptan, F. ve Kerti, I., B4C ile takviye edilen Alminyum matrisli kompozitlerin dkm yntemi ile retimi, 12. Uluslar aras Metalurji-Malzeme Kongresi, 808-812, stanbul, Kasm-2006. 8. Akn, G., Mindivan, H., imenolu, H. ve Kayal, E. S., Toz metalurjisi yntemiyle retilen Alminyum matrisli bor karbr takviyeli kompozitlerin anma davrannn incelenmesi, 12. Uluslar aras Metalurji-Malzeme Kongresi, 735-740, stanbul, Kasm-2006. 9. Sarta, S, Trker, M, Durlu, N,.Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Yaynlar: 05, Ankara, 2-9, 15-34, 206, 237, 379-387, 404-410, 2007. 10. Ark, H., Production and characterization of in situ Al4C3 reinforced aluminum based composite produced by mechanical alloying technique, Materials and Design 25, 1-4, 2004. 11. Ark, H., Trker, M., Production and characterization of in situ Fe-Fe3C composite produced by mechanical alloying, Materials & Design, 28: 140-146 (2005). 12. Lee, W., Kwun, S. I., The effects of process control agents on mechanical alloying mechanisms in the Ti---Al system, Journal of Alloys and Compounds, 240: 193-199, South Korea, (1996). 13. Lu, M.O. Lai, C.W. Ng, Enhanced mechanical properties of an Al based metal matrix composite prepared using mechanical alloying, Materials Science and Engineering A252: 203211, Singapur, (1998).
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MECHANICAL PROPERTIES
www.turkishpm.org
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Production of Ni3Al-Fe Composite and Investigation of Mechanical Properties

1
Ayhan Erol, 1smail Yldz, 2Ahmet Yonetken
1 2
Afyon Kocatepe University, Technology Faculty, 03200, Afyonkarahisar/ Turkey Afyon Kocatepe University, Engineering Faculty, 03200, Afyonkarahisar/ Turkey aerol@aku.edu.tr, iyildiz@aku.edu.tr, yonetken@aku.edu.tr ABSTRACT
In intermetallics high resistance to creep and oxidation, high strenght, low density are desired properties. Sintering process was used in this study by adding different amounts of Fe powder to Ni-Al powder mixture. When the properties of the sample after sintering were examined 40% weight Fe added composition was found as the most suitable ratio in terms of mechanical properties. Analyses were conducted metallographically on the samples after sintering, the densities were calculated, hardness and shear strengths were determined. According to the data 40% Fe added composition had 5,82 gr/cm3 of density, 92,8 HB hardness values and displayed 221 MPa shear strength. Keywords: Sintering, intermetallic, powder, composition 1. ntroducton The intermetallic compound, Ni3A1, has many advantages such as high melting point, low densities, high strength, as well as good corrosion and oxidation resistance, which make it an attractive candidate for high-temperature structural use [1-4]. Furthermore, the high strength and work hardening ability of these alloys mean that they can perform well in a variety of wear environments [5]. Because of the potential use of nickel aluminides at high temperatures, it is imperative to understand and study their oxidation behaviour [6]. However, low ductility, brittle fracture and processing problems seriously handicapped its application [7]. Its indicated that high temperature alloys should resist to corrosive affect of service atmosphere, should have enough strength in addition should protect its microstructure at elevated temperatures and stay durable [8]. AlFeNi alloys have been employed as the basis of the Ni-Al-Co permanent magnets because of their good magnetic properties and as high-temperature materials due to high melting points and excellent oxidation resistance [9-11]. Due to their good magnetic properties, Ni-Al-Fe alloys have been employed as the basis of the Alnico permanent magnets. Later on, they were improved by major additions of Co and minor additions of Cu, Ti and traces of other elements [12,13].
Figure 1. Ni-Al-Fe ternary phase diagram [13].
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The purpose of this study is to obtain Ni3Al-Fe composite by heat threatening at 600 C. It is known that the intermetallics obtained with addition of Fe have low density, high hardness, and high shear strength. In the light of this information the mechanic properties of obtained Ni3Al-Fe will be investigated. 2. expermental method In this study properties of raw materials are; the nickel is in 99.8% purity and has particle size lower than 40 , the aluminum is in 99.95% purity and has particle size lower than 75 and Fe is in 99.9% purity and has particle size lower than 150. For obtaining 11 gr rectangle sample according to the formula (NixAly)(Fe)100-(x+y) (x+y= %80, 70, 60 weight) Al and Fe as well as Ni material were mixed homogenously for 24 hours in certain proportions in order to produce a Ni based intermetallic. For this process the raw material powders mixed in mixer has single phased electric motor. This mixer is a mixer that circular motion. The mixture was shaped by one axis cold hydraulic pressing in a suitable container. In shaping process the pressing pressure was 300 bar. Pressed samples have undergone sintering for 2 hours at 600 C in a tube oven within Argon gas atmosphere. They were left to free cooling after sintering, their hardness, density and shear strengths were measured. Also XRD and SEM were applied to samples after sintering. The XRD analyses carried out in Shimadzu XRD-6000 the radiation chosen is Cu k-alfa the scan range is 2 teta and scanning rate is 2degree/minute. The SEM microanalyses performed in Leo 1430 VP secondary electron detector and the W used as filament of electron gun. 3. EMPIRIC RESULTS 3.1. Density: The densities of the samples obtained after sintering were calculated by using (d=m/V) calculation formula (Figure 2). Here m is the mass of sintered sample; v is the volume of sintered sample, calculated geometrically. When Figure 2 is examined highest density is in 40% Fe added mixture as 5.82 gr/cm3 and the lowest density has 5.57 gr/cm3 values in 20% Fe added mixture.
Figure 2. Density graphic of Ni3Al-Fe composite materials 3.2. Hardness: Hardness values of samples which were obtained in connection with sintering effect were measured as Brinell (Figure 3). In Brinell hardness measurement method 10 mm spherical ball tip used. The approximate data has taken that performed any 3 places on rectangle sample. The reason is obtaining the exact hardness data. When Figure 3 is examined while the highest hardness was obtained in 40% Fe added mixture as 92.8 HB, the lowest hardness was obtained in 20% Fe added mixture as 86.2 HB.
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Figure 3. Hardness graphic of Ni3Al-Fe composite materials 3.3. Volumetric Change: The volumetric changes of Ni3Al-Fe composite material after sintering were calculated by using (d=m/V) calculation formula (Figure 4). The volume of pre-sintered and post-sintered samples was measured with Archimedes principle that volume changing in liquid.
Figure 4. Volumetric change graphic of Ni3Al-Fe composite materials When Figure 4 is examined it can be seen that decreases in volumetric changes of composite materials occur inversely proportional to increases in density values when compared to pre-sintering. While the highest volumetric change was obtained in 40% Fe added mixture with 1.75 cm3, the lowest volumetric change was 2.06 cm3 in 20% Fe added mixture. The increasing in density is changing diametrically with decreasing in volume change. This situation shows that the desired sintering occurred. 3.4 Shear Strength: Shear strength values (Figure 5) for the samples obtained after sintering were measured by Shimadzu AG-IS 100KN device. Shear strength performed via connecting shear apparatus to jaw of tensile testing device and the rectangle samples placed in this apparatus and testing performed.
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Figure 5. Shear strength graphic of Ni3Al-Co composite materials While the highest shear strength value was obtained as 221 MPa in 40% Fe added mixture, the lowest shear strength value was 133 MPa in 20% Fe added mixture. 3.5 Xrd Analysis: After sintering, XRD analysis was performed upon the samples (Figure 6 and Figure 7). When the analysis results were examined, the highest peak value was observed in Ni3Fe phase among the sintered composite materials. Following this phase, FeAl phase has the second highest peak value. It is anticipated that Ni3AlFe peak value indicates the reaction of Ni with Al within the composite material.
Figure 6. XRD graphic of Ni-Al-20% Fe composite material The XRD analysis result of 40% Fe added mixture is seen in Figure 7. As it is seen in the Figure as well, Ni3Fe phase has the highest peak value. It is anticipated that this case indicates that Ni element may be formed within the composite material.
Figure 7. XRD graphic of Ni-Al-40% Fe composite material When Figure 6 and 7 are examined it is seen that intermetallic phase formed in Ni3Al-Fe composition after sintering is Ni3Al, Ni3AlFe, Ni3Fe, NiAl, FeAl, Ni, FeNi.
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3.6 Sem Analysis: SEM analysis of the composite materials obtained depending upon sintering effect was performed (Figure 8). When SEM images were examined, it is observed that more homogenous and less porous structure 20, 30 and 40% Fe added materials. The reason of obtaining less-porous structure is more sintering. It is thought that this situation indicates that Fe material in the composite material could increase the sintering temperature by reacting with other materials.
Figure 8. SEM images of Ni3Al-Fe composite materials, a) SEM image of Ni-Al-20% Fe added composite material, b) SEM image of Ni-Al-30% Fe added composite material, c) SEM image of Ni-Al-40% Fe added composite material 4. RESULTS AND DISCUSSION The following results were obtained from the experimental findings; The highest density value was calculated in 40% Fe added composite material as 5.82gr/cm3 (Figure 2). The highest hardness value was measured as 92.8 HB hardness in 40% Fe added composite material among the sintered composite materials. The highest shear strength was measured in 40% Fe added composite material as 221MPa. When SEM analysis were examined, it was seen that 20, 30 and 40% Fe added composite material has a more spaceless and homogenous structure. While the flow charted followed in empiric studies is similar to the one used by Yonetken et al. in their studies, there are some differences in the values [14]. Decreasing in volume change is changing diametrically with the increasing in density, by the way the desired sintering quality occurred. 5. Acknowledgement: It was supported by Afyon Kocatepe University SRPC Project no 10.TEF.01. We would like to thank to Scientific Research Project Commission for their support. REFERENCES [1] Morsi, K., Review: Reaction synthesis processing of NiAl intermetallic materials, Mater Sci Eng A; vol. 299, pp.115, 2001. [2] Sikka, V. K., Deevi, S. C., Viswanathan, S., Swindeman, R. W., Santella, M. L., Advances in processing of Ni3Al-based intermetallics and applications, Intermetallics, vol.8, pp. 132937, 2000.
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[3] Li, S., Feng, D., Luo, H., Microstructure and abrasive wear performance of chromium carbide reinforced Ni3Al matrix composite coating, Surface & Coatings Technology, vol. 201, pp. 45424546, 2007. [4] Peng, L. M., Fabrication and mechanical properties of microalloyed and ceramic particulate reinforced NiAlbased alloys, Journal of Alloys and Compounds, vol. 440, pp. 150153, 2007. [5] Li, S. P., Luo, H. L., Feng, D., Cao, X., Zhang, X. E., Abrasive Performance of Chromium Carbide Reinforced Ni3Al Matrix Composite Cladding, Journal of Iron and Steel Research, vol. 16(5), pp. 87-91, 2009. [6] Moussa, S. O., Morsi, K., High-temperature oxidation of reactively processed nickel aluminide intermetallics, Journal of Alloys and Compounds, vol. 426, pp. 136143, 2006. [7] Deevi, S. C., Sikka, V. K., Nickel and iron aluminides: an overview on properties, processing, and applications, Intermetallics, vol. 4, pp. 35775, 1996. [8] Akdoan, A., Superalloys, Access: www.yildiz.edu.tr/~akdogan/lessons/malzeme2/Super_Alasimlar.pdf., 2010. [9] Zhang, L., Du, Y., Xu, H. etc., Phase equilibria of the AlFeNi system at 850 C and 627 C, Journal of Alloys and Compounds, vol. 454, pp. 129-135, 2008. [10] Marcon, G., Lay, S., Ann. Chim. Sci. Mater. vol. 25, pp. 2140, 2000. [11] Bitterlich, H., Loeser, W., Schultz, L., J. Phase. Equilib. vol. 23, pp. 301304, 2002. [12] Eleno, L., Frisk, K., Schneider, A., Assessment of the Fe-Ni-Al system, Intermetallics, vol. 14, pp. 12761290, 2006. [13] Raghavan, V., Al-Fe-Ni (Aluminum-Iron-Nickel), Section II: Phase Diagram Evaluations, vol. 29, pp. 180184, 2008. [14] Yonetken, A., Erol, A., Talas, S., Microwave Sintering of Electroless Ni Plated SiC Powders, Material Science and Engineering Conference, 1-4 September 2008, Nunberg, Germany.
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TOZ METALURJS LE RETLEN Fe-26Al ve Fe-50Al TOZ KARIIMLARININ ISIL LEM SONRASI MKROYAPI VE MEKANK ZELLKLERNN ARATIRILMASI
Mehmet AKMAKKAYA* ve kr TALA**
** * AK, Teknoloji Fakltesi, Otomotiv Mhendislii Blm, 03030, Afyonkarahisar, cakmakkaya@aku.edu.tr AK, Teknoloji Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 03030, Afyonkarahisar, stalas@aku.edu.tr
ZET Bu almada, Fe, Al tozlar atomik % oranlarda Fe-26Al ve Fe-50Al kompozisyonlar oluturularak tek eksenli presle preslenmitir. Numuneler 550, 600, 650, 700, 750, 800 C de mikrodalga frnda argon gaz atmosferlerinde 0,5, 1 ve 1,5 saat srede sinterlenmitir. Sinterleme ileminden sonra konvansiyonel frn kullanlarak atmosfer artlarnda 450 0Cde 5,10, 15, 30 saat sreyle sl ilem uygulanmtr. Yaplan sl ilem kesme mukavemet deerini artrrken artan sl ilem sresine bal olarak kesme mukavemetinde azalma olduu grlmtr. Bununla birlikte artan alminyum oran da kesme mukavemetini aa ekmektedir. En yksek kesme mukavemet deeri 5 saat sl ilem yaplan numunelerde llmtr. Sinterleme scaklnn 650 C nin zerinde seilmesi durumunda numunelerde hacimsel genleme gzlenmitir. SEM sonularna gre; matris faz Al oluturmakta ve Fe,Ti tozlarnn sinterlenmi olarak dalm grlmtr. Sinterlenmi numunelerin XRD sonularnda FeTi, AlTi, Ti3Al, Fe3Al, FeAl intermetalik bileiklere rastlanmtr. Anahtar Kelimeler: Toz Metalurjisi, Sinterleme, Mekanik zellikler.
PRODUCED BY POWDER METALLURGY POWDER MIXTURES Fe-26Al and Fe-50Al Microstructure AFTER HEAT TREATMENT AND MECHANICAL PROPERTIES OF INVESTIGATION
ABSTRACT In this study, Fe, Al powders atomic% Fe-26Al and Fe-50Al composition rates by creating pressed under uniaxial presses. Samples 550, 600, 650, 700, 750, 800 C in a microwave oven atmosphere of argon gas, 0.5, 1 and 1.5 hours, sintered time. After sintering, atmospheric conditions using a conventional oven 5, 10, 15, and 30 hour 450 C heat treatment were applied. Increasing the heat treatment increased the shear strength shear strength, depending on the duration of heat treatment were reduced. However, the increasing rate of shear strength of aluminum draws down. The highest shear strength value of the samples were measured 5 h heat treatment. Sintering temperatures at around 650 C, if you select on the volumetric expansion observed in the samples. According to the results of SEM, the matrix phase of the Al and Fe to create, as the distribution of Ti powders were sintered. XRD results of samples sintered Fe3Al, FeAl Intermetallics compounds were found Keywords: Powder Metallurgy, Sintering, Mechanical Properties 1.Giri Toz metalrjisi parack boyutu 0,1 ila 200 m aralnda deien metal esasl tozlar paralarn ekil ve boyutlarna uygun olarak presleyip, (0.750.86)Tm scaklnda vakum veya koruyucu gaz atmosferinde sinterleyerek tipik
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mhendislik paracklarndan (metaller, seramikler ve plastikler) son ekle yakn para imal etme yntemidir[1, 2]. Toz metalrjisi metal, seramik tozlarnn retimi ve bu tozlarn mekanik ve termik etkilerle birletirilerek kullanl mhendislik paralara dntrlmesini amalayan bir imalat srecidir[3]. retilen paralarda son ilemden sonra %1030 arasnda gzenek mevcutsa gzenekli, %13 arasnda gzenek varsa bu rne kompakt malzeme denilir[4, 5]. Karm tozlar oluturmak iin paracklar homojen bir ekilde kartrma, toz tanelerinin birbiriyle ba oluturmalar iin kalpta presleme ve atmosfer kontroll sinterleme ilemi basamaklarn ierir[6]. Sktrlm toz paralar arasndaki ba, yapma, mekanik kilitleme ve benzeri trden zayf balar olup kristal kafes ierisindeki ba dayanmna gre ok zayftr. Sktrlm tozlar bir birleriyle temas etseler bile bir birlerinden bamsdrlar. Sinterlemede scakln etkisi ile bu tozlar arasndaki temas noktalar artrlmakta, atom ve iyonlar arasnda bir ba oluturulmaktadr. Tek bileenli sistemlerde sinterleme tamamen kat fazda gerekleir. ok bileenli sistemlerde sinterleme ilemi sktrlm parann kat formunu (iskeletini) koruyacak ekilde kat veya sv fazda gerekleir[7]. Gerekte sinterleme ilemi de bir scak basn kayna ilemi olup, tozlarn birbirleriyle birlemesi difzyon mekanizmasyla olmaktadr. Toz metalrjisi, ana imalat yntemleri olan dkm, plastik ekil verme, talal imalat ve kaynakl imalata (ergitme kayna) gre daha farkl bir imalat yntemidir ve bu yntemin kendine has zellikleri vardr. Bunlar, retimi zor olan alamlarn daha kolay retilebilmesi, karmak ekilli paralarn imalatnn kolayl, younluk kontrolnn yaplabilmesi ve ekonomiklik gibi zelliklerdir. Toz metalrjisi genelde kalite ve maliyet asndan dier yntemlerle retilemeyen paralarn imalatnda yaygn olarak kullanlr[8]. Toz metalrjisi ile elde edilmesi dnlen bir parann malzemesi ve elde edilecek para, kalite ve maliyet asndan dier yntemlerdekilerle karlatrlmal ve elde edilen sonuca gre toz metalrjisinin uygulanp, uygulanmamasna karar verilmelidir. Toz metalrjisi teknolojisi, makine ve elemanlarnn yapmnda istifade edilen nceki teknolojilerden farkldr. En nemli farkll, istenilen zellik ve ekle sahip rnlerin elde edilmesine imkn vermesidir. Kaliteli ve karmak paralarn ekonomik olarak retilebilmesi toz metalurjisini daha da cazip klmaktadr[9, 10]. Toz metalurjisi malzemeleri ierisinde demir esasl toz metal malzemeler nemli bir yere sahiptirler. Bu malzemelerin eidini arttrmak ve uygulama alann geniletmek iin eitli yntemler vardr. Bu yntemlerden en nemlisi eitli alam elementlerinin ilavesi ile malzemelerin alamlandrlmasdr[11, 12]. Daha karmak ekillere ve zelliklere sahip olan paralarn retimi, toz metalrjisinin presleme, piirme (sinterleme) ve sl ilem operasyonlarndan baka ek ilemlerin yaplmasn zorunlu klar. Bu paralarn malzemelerinin fiziksel, mekanik ve dier zelliklerinin iyiletirilmesi iin malzeme younluunun uygun ekilde ayarlanmas, yeterli alamlamann ve sl ilemin yaplmas gereklidir. Bununla birlikte, ergime scakl dk olan metaller sayesinde retilecek paralarn gzeneklerinin yeterli derecede doldurulmas da salanmaldr. Karmak ekle sahip bir rnn elde edilmesi, bazen byk boyutlardaki hammaddeden dier imalat yntemleri kullanlarak, bazen de toz metalrjisi yntemi kullanlarak yaplr. Toz metalrjisi ynteminde presleme, piirme (sinterleme) ve az sayda talal imalat gerekebilir. Parann btn olarak hazrlanmas gerekli zaman arttrmakta, daha byk boyutlu preslere ve pres kalplarna ihtiya gerektirmekte ve bunlarn yannda bir ok teknik ve ekonomik zorluklara neden olmaktadr[13]. Gnmzn vazgeilmez bir paras olan TM rnleri hayatmzn birok yerinde karmza kmaktadr. TM teknolojisi yntemiyle mhendislik malzemelerinin kullanm sresini artrmak, maliyetini drmek ve mukavemetlerini artrmak iin birok alma yaplmaktadr[1](German 2007). Toz metalrjisi prosesleri kullanlarak retilen tm yapsal paralarda %100 teo rik younluklara eriilmek istenir. stenilen bu deerlere ulamak balang toz zellik lerine, kullanlan proses parametrelerine ve en ok da kullanlan sinterleme koullarna baldr. Tm koullar ne kadar ideal olursa olsun uygun seilmeyen sinterleme para metreleri dk teorik younluklu paralar sunar. Yksek teorik younluklu paralarn elde edilmesinde en ok kullanlan sinterleme teknii sv faz sinterleme tekniidir. Bu teknikte yksek teorik younluklu ve buna bal olarak stn mhendislik zelliklere ulaan paralar elde edilebilir. Balang tozlar ierisine katlan dk miktardaki ilave ler, sinterleme esnasnda yap ierisinde sv faz oluturarak sinterleme mekanizmasn hzlandrrlar. Oluan sv faz yapy daha sk hale getirerek younluk deerlerinin art masna sebep olur. Yap ierisinde oluan sv faz sadece younluk deerlerini arttrmaz ayn zamanda sv fazn karakteristiine bal olarak parann mhendislik zelliklerini deitirir[14]. Hui-Zhen Kang ve arkadalar Fe Al toz karmlarnn tepkisel davranlarn aratrmlardr. Sinterleme ileminde toz bileenleri glenir ve daha mukavemetli yaplar oluur. Fakat ime problemi serbest katlaabilen demir alminyum tozlarnda grlr. %29 Fe ieren Fe3Al intermetaliinde serbest boluklar katlarken Fe2Al5 bileiindeki gibi katlar. %71 demir ieren Fe2Al5 dk scaklkta katlamas srasnda gzenekli mikro yaplarda art olur. nk bu scaklkta FeAlun ekzotermik reaksiyonun sonucu hzl ve iddetli sveren bir yapda olmasndan kaynaklanmaktadr[15]. Demir alminat ailesini ieren stratejik elementlerin dnm salanm ve malzemelerin maliyeti ve scaklk uygulamalar aratrlm, dikkatli bir ekilde gelien yapsal malzemelerin ucuz olduu bir snf oluturulmutur. almalarda 600 C scaklklarda elikten daha hafif ve daha mukavetli, bununla beraber evresel korozyondan korunabilen oksidasyon direnci yksek yap malzemesi retilmitir. Bu yzden Fe3Al alamlar termal uygulamalarda kullanlabilen potansiyel bir malzemedir[16]. Maziasz, McKaamey ve arkadalar FeAl komposizyonlarn B2 D03 yapsal dnmlerdeki etkiyi aratrmlar. Bu almalarnda Fe-28Al alm 530670 C scaklkta B2 D03e dnm salad belirlenmitir. ntermetalik tozlarn demir alminyum ksmn Godlewska ve arkadalar almtr. Burada demir alminyum malzemeleri %40 alminyum ieren metal tozlar, 25 40 m tane boyutuna sahip tozlarn belirli oralarda karmlar salanarak mekanik alamlama allmtr. Fe Al toz karmlar alminyumun ergime scaklna yakn 660 C de argon ve hidrojen karm gaz atmosferinde sinterlenmi, bylelikle oda scaklnda dayankl ve snek intermetalik malzeme retilmitir[17].
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2. Deneysel almalar Sinterleme malzemelerin performanslarn artrmak iin termal enerji kullanlarak yaplan bir ilemdir. ekil 1de malzeme bilimcilerinin malzeme zerimde urat drt temel grlmektedir. Bu temel prensipleri istenilen ynde deitirmek iin kullanlan yntemlerden birisi de sinterleme ilemidir. Sinterleme ileminde takip edilen genel aamalar ekil 2de verilmitir.
ekil 1. Malzeme bilimi ve mhendisliin drt temel esas
ekil 2. retim ynteminde sinterleme blmlerinin basamaklar. Sinterleme, birbirine temas eden paracklarn yksek scaklklarda birbirine balanmasn salar. Bu balanma, ergime scaklnn altnda kat halde atom hareketleriyle oluabilir. Fakat pek ok durumda, sv faz oluumu ile birlikte gerekleir[1]. Sinterleme, toz halindeki malzemenin erime scakl altndaki bir scakla belli bir sre maruz braklarak tozlarn birbirlerine dedikleri noktalardan balayarak kaynamasna denir. Baka bir ifadeyle teknik terminolojide sinterleme terimi, metalik veya metalik olmayan anorganik tozlardan oluan kat rnlerin ergime scaklklarnn veya ne kadar stlmalar anlamna gelmektedir. Bu ilem esnasnda taneler farkl difzyon mekanizmalar ile bir araya gelirler. Zamanla yap iindeki boluklar kapanr ve bu nedenle parada ekmeler oluur. Sonuta youn bir yap elde edilir[18]. Sinterleme, yksek scaklkta atomlarn yaynm ve kk paracklarn yzey enerjisinin azalmasyla gerekleir. Kristal yapl katlarda, hemen hemen btn parack temas noktalar snrlar enerjisine sahip olan tane snrlarn oluturur. Sinterleme esas olarak itici gler, mekanizmalar ve aamalar asndan incelenir: Sinterlemenin itici gleri balanmaya neden olan mikroskobik erilikleri tanmlar. Sinterleme mekanizmalar itici glere tepki olarak oluan atom hareketlerinin yolunu tanmlar. Sinterleme aamalar atom hareketleri sonucu oluan geometrik geliimi tanmlar. Bu aamalar da dier taraftan itici gleri deitirir. tici gler veya sinterleme gerilmeleri mikroyapdaki eriliklerden kaynaklanr. Sinterleme mekanizmalar genellikle yzey, tane snr veya kristal kafesinde oluan yaynm ilemleridir. Sinterleme aamalar etkin itici gcn ve kinetiin aklanmasna yardmc olur ve ilemin matematik modellenmesinde kullanlr[1]. Tm toz metal ve seramik paralar mukavemet kazandrmak amacyla yksek scaklklarda sinterlemeye tabi tutulurlar. Sinterleme ile preslenmi toz paralarda younluk artna neden olan boyutsal (veya hacimsel) klme meydana gelir. Sktrlm toz paralar arasndaki balant yapma, mekanik kilitleme ve benzeri trden zayf balar olup kristal kafes ierisindeki ba dayanmna kyasla ok zayf kalmaktadr. Sktrlm toz yaplar ierindeki partikller bir biri ile temas
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ediyor olsa da her bir partikl dierinden bamszdr. Sinterleme ile partikl temas noktalar artmakta ve atomlar ve iyonlar arasnda fiziksel bir ba olumaktadr. Bu trden ba oluumu kristal kafes sistemi ierisindeki yksek dayanml atomsal balanma ile benzetir. Tek fazl sistemlerde (saf toz kullanmnda) sinterleme tamamen kat fazda gerekleir. ok fazl sistemlerde (birden fazla trde toz bir arada kullanlmas durumunda veya toz ierisinde bulunan safszlklar) sinterleme ilemi sktrlm parann kat formunu (iskeletini) koruyacak ekilde sv fazda gerekleebilir. Bu durum zellikle ok ince taneli tozlarda daha fazla grlr[7]. Kat durum sinterlemesi, kompakt hale getirilen tozlarn btnln bozmayan scaklkta kat bir durumda meydana gelir, sv faz sinterlemesi, kompakt tozlar sv faz scaklna gei durumunda yaplan sinterlemedir. Bu iki olay ekil 3de gsterilmektedir[19].
ekil 3. Sinterleme trleri [19]. 3. Fe26Al Bileiin XRD Analizleri Deneysel almalar sonucunda oluan mikroyaplarn XRD analizleri yaplmtr. Bu almada seilen 1 saatlik sinterleme sresine daha ok nem verilmitir ve dier mikrodalga sreleri iin yaplan XRD krnm desenleri iin snrl XRD ve hesaplama yaplmtr. Bu analizlerde farkl sinterleme scaklk deerleri, sinterleme sresi ve toz bileimlerine gre oluturulan numunelerin sonular deerlendirilmitir. XRD pikleri aada ekil 4 de verilen tipik XRD deseninde gsterilmitir. Burada f ana pikleri temsil etmektedir ve dier pikler ise alamda grlen sperlatis pikleridir. Fe26Al kompakt numunelerin 550 C 1, mikrodalga frn Argon atmosferinde sinterleme ilemlerinden sonra 450 C tp frn argon atmosferinde 5, 10, 15, ve 30 saat srelerde sl ilem yaplarak oluan yaplarn XRD analizleri grlmektedir(ekil 5). almalarda tek eksenli presleme yaplarak sinterlenmi numunelerin XRD sonularnda D03, B2, FeAl, Fe(110), Fe(200), Al(200), Al(220) fazlar tespit edilmitir. Ayn ekilde Robin ve arkadalar bu fazlar scak presleme reaksiyonlarnda da elde edilmitir[20]. Krnm deseninde verilen kutucuklarda sadece DO3 (Fe3Al) ve B2 (FeAl) alamlarnda grlen pik pozisyonlar verilmitir(ekil 4). Pik dzlemleri bilinmeyen durumlarda hesaplanabilirken genellikle XRD krnm veri tabanndan piklere karlk gelen deerler bulunabilir. Sktrlan tozlarn yaplan sl ilemleri sonucu elde edilen XRD krnm desenlerinde sinterleme srasnda ortaya kabilecek DO3 ve veya B2 fazlarnn tespit edilmesi, DO3 faz iin, krnm desenlerinde uzun mesafeli dzen(UMD) yaps aadaki formlle ifade edilebilir: SD03 = (I111/I220)obs / (I111/I220)calc and SB2 = (I200/I220)obs/(I200/I220)calc
3. 1
S, UMD parametresi, Iobs ve Ical ise normalize edilmi srasyla llen ve hesaplanm pik iddetleridir. (111)DO3 sperlatis ve (220)DO3 ana piklerine ait iddetlerin hesaplanmas Ihkl = |F| 2 mhkl Lp(), forml ile gerekletirilmitir. Burada, F is yap faktr ve mhkl ise ilgilenilen dzleme ait pikin arpm faktrdr ve son olarak Lp is Lorentz polarizasyon faktr olarak bilinmektedir. Bu hesaplamalardaki scaklk faktr deney yaplan (XRD) scakln btn deney numuneleri iin ayn olmas nedeniyle dikkate alnmamtr. UMD sonular Fe ve Al elementleri iin Sinterlenmemi ve 0,5, 1 ve 1,5 saat deiik srelerde sinterlenmi numuneler iin hesaplanmtr. rnein Fe ve Al iin atomik fraksiyonlar XFe ve XAl (XTi ) olarak ifade edilsin ve dolaysyla bu terimlerin toplam sistemdeki toplam fraksiyon orann yan 1 i verecektir. Yani, XFe+XAl+XTi+XCu=1. Tam olarak UMD yapsna sahip olan Fe3Al sisteminde, kristal yaps drt ana sperlatise ayrlabilir: a, b, c ve d; ayrca bu sperlatislerin toplam fraksiyonlar ise Ya+Yb+Yc+Yd=1. c ve d sperlatisleri sekiz Fe atomlar tarafndan tamamen doldurulur ve b sperlatisi ise drt Fe atomu tarafndan ksmen doldurulur geri kalan d sperlatisi ise Al tarafndan doldurulur. Dolaysyla, sperlatis pik yansmas iin b sperlatisi yap faktrlerinin hesaplanmasnda nemli bir kstas olacaktr. nk bu sperlatiste Al ve Fe tarafndan paylalmaktadr.
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Fe3Al latisinde, yani, b sperlatisinde ortalama yap faktrleri D03 ve B2 speryaplar iin srasyla FDO3= 4(fa-fb) ve FB2 = 4(2fc-fb-fa) olarak verilir ve ayrca ortala sapma faktrleri ise fb = (qfFe -zfAl) ile temsil edilir. Burada q ve z (0 veya 1 arasnda bir say ile ifade edilebilen molar fraksiyonlara gre dzeltilmi yer igal arpm fraksiyonudur (rnein b sperlatisindeki durumda q 0,5 ve Al da 0,5 ile ifade edilir)ve fa fb ve fc ise her bir pik dzlemine ait hesaplanan sapma faktrleridir. Bu formllerle UMD faktrleri hesaplanmaktadr(izelge 1). Bu almada (111)/(400) piklerinin oran DO3(Fe3Al faznn) kristal yapsnn ve (200)/(400) oran ise B2 (FeAl) faznn kristal yapsnn dzen oranlarn vermektedir. (200)/(400) oran paylalan latiste Fe/Al oran 0,5 olduu iin, en yksek B2 dzen oran 0,5 olacaktr buna karn DO3 kristal yapsnn ise 1 olabilir[21] Bu bilgiler nda aada izelge 1 verilen UMD sonular deerlendirildiinde sinterleme srelerinde 1 saatlik bir sinterlemenin yeterli olduu grlmektedir ancak en iyi sinterleme performans UMD deerleri dikkate alndnda 2 saatlik bir sinterlemenin verdiini grmekteyiz. Ancak 2 saatlik bir sinterleme fizibil olmamaktadr ve maliyeti artrmaktadr. lave olarak sl ilemler dikkate alndnda ise istisnasz olarak 5 saatlik bir sl ilemin yeterli olduu grlmektedir. izelge 1 Fe-26Al karm iin deiik sinterleme zaman ve takip eden sl ilem sreleri iin UMD deerleri 1/2 saatlik Mikrodalga Sinterleme Sinter. Sr.(Saat) 0 0,5 30 DO3 0 0,01 0,01 B2 0 0,03 0,07 1,5 saatlik Mikrodalga Sinterleme Sinter. Sr.(Saat) 0 1 5 10 1 saatlik Mikrodalga Sinterleme Sinter. Sr.(Saat) 0 1 5 10 15 30 DO3 0 0,01 0,01 0,01 0,03 0,04 B2 0 0,09 0,11 0,06 0,08 0,11 2 saatlik Mikrodalga sinterleme Sinter. Sr.(Saat) 2 5 10 DO3 0,06 0,24 0,09 B2 0,14 0,32 0,04 15 30 DO3 0 0,06 0,08 0,01 0,01 0,01 B2 0 0,14 0,19 0,01 0,01 0,02
Artan sl ilem sreleri ile beraber ksmen Fe3Al faznda art oluturmaktadr ancak genel olarak sonulara ok fazla bir etkisi olmamaktadr. Isl ilemle belirlenen UMD deerlerinde deiim iin deiik mekanizmalar nerilebilir. Sinterleme ardndan yaplan sl ilemler 450 C de yapld iin daha ok DO3 yapsn glendirilmesi amalanmaktadr ancak ilk sinterleme scakl ise B2 yapsnn baskn olduu 550 C yaplmtr. Genel olarak B2 kristal yapsnn daha fazla bulunmas aslnda fiziksel olarak Fe ve Al arayzeylerinin daha fazla temas halinde olmasndan kaynaklanmaktadr[22]. Dybkova gre Fe ve Al un reaksiyonu sonucu ilk oluacak fazn Al ve Fein faz diyagramndan anlalaca gibi doyum limitlerine yakn olan Fe2Al5 bileii ile balayacan ve artan sre ile beraber Fe3Al ve daha sonra ise FeAl ikili bileie dnecei belirtilmektedir. Bununla birlikte Jozwiak ve ark ise yaptklar DSC(Differential Scanning Calorimetry) almalarnda ise sralamann FeAl3Fe2Al5FeAl2FeAl eklinde olutuunu gstermilerdir[23]. Ancak bu almada Fe2Al5 bileiine ait herhangi bir pik tespit edilememitir buna karn Fe3Al faza ait piklerin az olmas Dybkovun nerdii mekanizmann bu durumda scakla ar baml olduunu nermektedir. Gerekten Dybkov deneylerini olduka yksek scaklklarda (700 C ve zeri) scaklklarda yapt iin bu almada yaplan deneylerin sonular iin nerilebilecek uygun bir mekanizma olmad grlmektedir. Buna karn, Turmezey elektron mikroskopi almalarnda FeAl ve Fe3Al bileiklerinin ayn anda bulunabileceini tespit etmi ve souma hzna bal olarak Fe3Al faznn daha az bir byme hzna sahip olduu iin FeAl oluumunun daha ok sistem tarafndan tercih edildiini ispatlamtr[24].
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ekil 4. Tipik Fe26Al alamnda grlen ana ve sperlatis pikleri
ekil 5. 550 Cde 1 saat n Sinterleme yaplm ve 5, 10, 15 ve 30 saat sl ilem uygulanm numunelerin XRD analizleri verilmitir 4. Fe26Al ve Fe50Al ntermetaliklerin Kesme Mukavemeti nsinterleme zerine yaplan btn sl ilemler sinter dayanmn artrma ynnde almtr ancak sinter sresi arttka dayanm deerlerindeki d olduka bariz olarak karmza kmaktadr. Artan sinter sresi, toz boyut dalmn ve temas yzey orann deitirecektir ve genel olarak dayanmdaki dme ise reaksiyon rnlerinin eitliliine balanmaktadr[25, 26]. Gerekten de, en iyi sonular XRD krnm deseni ile elde edilen sonularda 1 saat nsinterleme ile elde edilmi ve dier srelerin etkisinin ok az olduu gzlemlenmitir. izelge 1de verilen deerler dikkate alnrsa B2 piklerinde meydana gelen deiimin aslnda FeAl faznn artmas ile sonuland ve dolaysyla daha krlgan bir faz olan FeAlun genel dayanm artan sl ilem scakl ile drd nerilebilir. ekil 9, 10da Fe26Al ve ekil 11de ise Fe50Al numuneler 550 Cde 1saat Mikrodalga sinterleme yapldktan sonra ayn numunelere mikroyapda intermetalik oranlarndaki ve mekanik zelliklerinde oluabilecek deiimin aratrlmas amacyla 450 C de 5-10-15 ve 30saat sl ilem uygulanmtr. Sinterleme ileminde sinterleme sresinin kesme mukavemetine etkisinin fazla olmad llmtr. Fakat sl ilem sresindeki artlarda kesme mukavemetinde azalma olduu belirlenmitir. En yksek kesme mukavemet deeri 1saat n sinterleme ve 5 saat sl ilem grm Fe26Al oranna sahip numunelerde llmtr. Toz karmda Alminyum oran arttka kesme mukavemet deerlerinde belirgin azalma olumaktadr(ekil 5).
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ekil 6. 550 Cde n Sinterleme Sonras Isl lem Sresine Bal Fe26Al Kesme Mukavemeti
ekil 7. 550 Cde n Sinterleme Sonras Isl lem Sresine Bal Fe50Al Kesme Mukavemeti 5. Fe26Al ve Fe50Al Numunelerinde Isl lem artlarnn Etkisi Numunelerde sinterleme ileminden sonra mikroyapda intermetalik orannn deerlendirilmesi ve mekanik zeliklerdeki deiimin aratrlmas amacyla nceki almada belirlenen ideal sinterleme scaklk ve sresi seilerek numuneler retilmitir. Bu almada Fe26Al ve Fe50Al numuneleri Mikrodalga frn argon atmosferinde 550 Cde 1, 1,5 ve 2 saat sinterleme yaplmtr. Sinterlenmi bu numuneler tp frn atmosferinde 450 Cde 5101530 saat bekletilerek frn iinde oda scaklna kadar soutularak mikroyap deiimleri aratrlmtr. Sinterleme ileminden sonra numunelerde nceden oluan intermetalik oranlardaki deiim 10 saat 450 Cde bekletilen numunelerin analizlerinde grlmektedir(ekil 5).
ekil 8. Fe-26Al 550 C de mikrodalga 1saat sinterleme ve 10saat 450 C de sl ilem, a) SEM ve b)EDX elementel haritalama grnts analizi
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ekil 9. Fe-26Al 550 C de 1 saat sinterleme ve 15 saat 450 C de sl ilem SEM grnts
ekil 10 Fe-26Al 550 C de mikrodalga 1 saat sinterleme ve 30saat 450 C de sl ilem SEM grnts
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ekil 11. Fe50Al, 550 C de 1 saat sinterleme ve 450 C de 15 saat sl ilem mikroyap SEM ve EDX spektrometre analizleri. KAYNAKLAR 1. Rveall M.German, Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Dernei Yaynlar, 1.basm, Ankara, 2007. 2. krov R.., Metalnaslq. Bak: aolu Yaynevi, 2002. 3. Kang, Hui-Zhen., Hu, Chen-Ti., Swelling behavior in reactive sintering of Fe-Al mixtures, Materials Chemistry ve Physics 88, s. 264 272, 2004. 4. Avc A.U., Toz metalrjisi ders notlar. Yldz Teknik niversitesi, stanbul, 1993. 5. Bishop D.P., Diffusion-based micro alloying via reaction sintering. Ph.D. Thesis, Dalhousie University, 1998. 6. Schneibel, H.J., Devi, S.C., Processing ve mechanical Properties of iron Aluminides composites containing oxide particles, Materials Science ve Engineering A364, s.166-170, 2002. 7. Kurt A.O., Toz retim yntemleri ve sinterleme. Sakarya niversitesi, Mhendislik Fakltesi, Metalrji ve Malzeme Mhendislii Blm Ders Notlar, s. 19-20. Sakarya, 2005. 8. Babayev Y., Karadeniz S. ve Memmedov A., FeCu karm toz malzemenin tribolojik zelliklerinin incelenmesi. 3. Makina Tasarm ve malat Teknolojileri Kongresi, 16-17 Eyll, s. 127-130, 2005. 9. Federenko .M. ve Pugina L.., Kompoziionne speenne antifrikionne material. Kiev: Nauk, 1980. 10. Radomselskiy .D., Porokove konstrukionne detali. Sovremennoe sostoyane, perespektne razvitiya. Porokovaya Metallurgiya, (10), s. 37-41, 1985. 11. Skoroxod V.V., Sostoyane i perispektiv razvitiya naunx osnav porokovoy metallurgii. Porokovaya Metallurgiya, (10), s. 20-24, 1995. 12. Zavolotny L.V., evuk Y.F., Begun K.., Kolinienko A.F. ve Varenko V.T., Porokove antifrukionne material na osnove matallokonentrata iz lifovalnx lamov. Porokovaya Metallurgiya, (7/8), s. 89-92, 1995. 13. Ordenko V.B., Proizvodstvo i primeneniya izdeliy iz metallieskix poroikov. Kiev, 1987. 14. Al-Qureshi, H.A., Galiotto, A., Klein, A.N., On the Mechanics of the Cold Die Compaction for Powder Metallurgy, Journal of Materials Processing Technology, 166, 135-143, 2005. 15. Kang, Hui-Zhen., Hu, Chen-Ti., Swelling behavior in reactive sintering of Fe-Al mixtures, Materials Chemistry ve Physics 88, s. 264 272, 2004.
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16. Hui-Zhen Kang, and Chen-Ti Hu., Materials Science and Engineering Material Chemistry and Physics, 88(2-3), pp.264-272, 2004. 17. Godlewska, E., Szczepanik, S., Mania, R., Krawiatz, J., Kozinski, S., FeAl Materials from Intermetallic powders, Intermetallics11, pp.307 312, 2003. 18. . Burke J.E. ve Rosolowski J.H., Sintering J. Eur. Ceram. Soc. 08, 758-769, 2000. 19. Suk-Joong L. Kang Sintering Densification, Grain Growth, and Microstructure Butterworth-Heinemann Publication Date: 2005-01-19. 20. B. H. Rabin and R. N. Wringht, Micrustructure and tensile Properties of Fe3Al Produced By compustion Synthesis/ hot Isostatic Presing Metallurgical and Materials Transsctions A Volume 23, Number 1, 35-40, 1991 21. Yang ZR, Wang SQ (Wang, Shu Qi)1, Cui XH (Cui, Xiang H.)2, Zhao YT (Zhao, Yu T.)1, Gao MJ (Gao, Ming J.)1, Wei MX (Wei, Min X.)1 Formation of Al3Ti/Mg composite by powder metallurgy of Mg-Al-Ti system Scence And Technology Of Advanced MateralsVolume: 9Issue: 3Article Number: 035005Published: SEP 2008 22. Dybkov, VI, Reacton Dffuson And Sold State Chemcal Knetcs, The IPMS Publications, Kyiv, 2002 23. Stanislaw Jzwiak, Krzysztof Karczewski and Zbigniew Bojar., Kinetics of reactions in FeAl synthesis studied by the DTA technique and JMA model ., ntermetallics. , Volume18, Issue 7, P. 1332-1337, July 2010. 24. Turmezey, T, AlFe and AlFeSi intermetallic phases in Al alloys, Materials Science Forum, Vol 13/14, pages 121131 ttp publications, London, NY., 1987. 25. Pease L.F. III, West W.G., Fundamentals of powder metallurgy, Metal Powder Industries Federation, Princeton, USA, 2002 26. Randall M. German., Sintering Theory and Practice, pp. 568. ISBN 0-471-05786-X. Wiley-VCH , January 1996.
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TOZ METAL MALZEMELERN MEKANK ZELLKLERNE YOUNLUK VE BAKIRIN ETKS

Nihat YILMAZ*, Remzi VAROL** * Sleyman Demirel niversitesi, Teknik Eitim Fakltesi Makine Eitimi Blm, 32260, Isparta, nihatyilmaz@sdu.edu.tr ** Sleyman Demirel niversitesi, Mh.-Mim. Fakltesi, Makine Mhendislii Blm, 32260, Isparta, remzivarol@sdu.edu.tr
ZET TM paralarn mekanik zellikleri, dvme ve dkm malzemelerde olduu gibi kimyasal kompozisyondan olduka fazla etkilenmektedir. Bunun yannda TM paralarda younluk, parack boyutu ve dalm ile dier TM proses parametreleri de mekanik zellikleri etkilemektedir. Bu almada demir esasl TM alamlarnn mekanik zellikleri zerine younluk deiimi ve bakr ilavesinin etkisi deneysel olarak incelenmitir. lk olarak ASTM standardna gre Fe-C ikili alamdan 210, 350 ve 700 MPa basnta 3 farkl younlukta (6.0,-6,5-7,1g/cm3) numuneler hazrlanm, daha sonra bu karmlara %2 bakr ilave edilmitir. Hazrlanan numunelere standart eme deneyi ve krk yzey SEM analizi, mikrosertlik lm ve mikroyap incelemesi yaplmtr. Bylece farkl younluun mekanik zellikler zerine etkisi incelenmi, daha sonra da bakr ilave edilmi numunelerle karlatrlmtr. Sonular gstermitir ki, Fe-C ikili alamlarnda younluk arttka eme mukavemeti ve mikrosertlik artm, %2 bakr ilavesi de eme mukavemeti ve sertlik deerlerindeki art daha st mertebeye tamtr. Anahtar kelimeler: TM malzeme, younluk, bakr ilavesi, mekanik zellikler
EFFECT OF DENSITY AND COPPER ON MECHANICAL PROPERTIES OF P/M MATERIALS

ABSTRACT Identically to wrought and cast metals, the chemical composition of PM parts strongly influences the mechanical properties. In PM parts, however, properties are dependent on additional factors such as density; particle size; pore size, shape, and distribution; and other PM process parameters. In this study, Effect of density variety and copper (Cu) addition on mechanical properties of ferrous PM alloys was experimentally investigated. Firstly, the samples prepared that three different density (6.0-6.5-7.11 g/cm3) Fe-C binary alloys. Later, Cu was addition to these alloys. Some standard tests carry out to the samples such as traverse rupture test and SEM analyze of crack surfaces, microhardness measurement, and microstructure investigations. Thus, effect of different density on mechanical properties and Cu addition has been investigated. Results showed that bending strength and microhardness increased with increasing density and addition of w%2 Cu at Fe-C binary alloys, Keywords: PM material, density, Cu addition, mechanical properties 1. GR Sinterlenmi paralarn karakteristik zellii olan porozite, geleneksel ergitme prosesiyle retilen malzemelerin aksine, TM malzemelerde eitli malzeme zelliklerini kimyasal kompozisyon ve yapdan daha fazla etkiler. Bu
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nedenle, sinterleme ve sktrmayla elde edilen younlama derecesinin belirlenmesi, sinterlenmi malzemelerin test edilmesinde nemli bir unsurdur. Younlamann miktar kompaktlanm veya sinterlenmi parann gzenek (gzenek hacmi) veya younluu olarak belirtilir. Porozite boyutu ve ekli ile bnye ierisinde heterojen dalma sahip olmas, younluk veya porozitenin deerlendirilmesinde gz nne alnmaldr [1]. TM malzemelerin porozitesi, Arimet yntemiyle belirlenen younlua gre hesaplanr. Younluun malzeme zellikleri zerine etkileri genel olarak bilinmektedir. rnein, younluk azaldka (porozite arttka), mekanik zellikler der, sl iletkenlik azalr, sertlik der, elektrik ve manyetik zellikler olumsuz etkilenir. Ancak bunlarn hangi seviyede etkiledii, her bir malzeme iin, TM proses deikenlerine (tozla ilgili parametreler, sktrma- sinterleme parametreleri v.b.) gre ayr ayr belirlenmesi iin daha detayl almalarn yaplmas gerekmektedir. Bu almann ana temasn da belirlenen bir malzeme grubunun baz mekanik zelliklerine, farkl younluk seviyesinin ve bakr ilavesinin etkilerinin detayl olarak incelenmesi oluturmaktadr. Bu konuda literatrde, baz kimyasal ilavelerin mekanik zelliklere etkisini inceleyen almalar vardr ve bunlarn zellikle son on ylda yaplanlar ilenebilirlik ilaveleri zerine younlamaktadr. Ayrca younluun mekanik zellikler zerine etkisini inceleyen olduka eski almalara rastlanrken, bunlarn gnmz teknolojisiyle retilen TM paralar iin detayl incelemesini ieren almalar olduka azdr. Bu konuda yaplan baz almalar yledir. Sulowski ve Cias (2011) yaptklar almada, Fe-3%Mn-(Cr)-(Mo)-0.3%C TM eliklerinin younluk, mekanik zellikler ve mikroyaps zerine, kimyasal kompozisyon, sinterleme atmosferi ve soutma hznn etkisini incelemilerdir. almada n alaml Astaloy CrM ve CrL ile ferromanganez ve grafit tozlar kullanlarak karm hazrlanm ve preslendikten sonra 1120 ve 1250 C scaklkta, farkl oranlardaki H2/N2 sinterleme ortamnda 60 dakika sinterlemilerdir. Ayrca iki farkl soutma hznda (frnda 1,4 C/dak., cebri soutma ile 65 C/dak.) soutma ve 200 C de temperleme yapmlardr. Tm numunelere ekme, TRS, darbe tokluu, grnr yzey sertlii yaplm ve mikroyapsal inceleme gerekletirilmitir. alma sonucunda daha yksek sinterleme scaklnda ve %Cr orannn artmasyla zelliklerin iyiletii ifade edilmitir [2]. Lindsley ve Rutz (2008) demir-esasl TM malzemelere molibden ilavesinin etkilerini inceledikleri almasnda, olduka yaygn kullanlan Mo ilavesinin TM malzemelerde sktrlabilirlii ok az etkiledii, oksijen duyarllnn olmadn ve zellikle eliklerin sertleebilirliini arttrdn ifade etmilerdir. almada % 0-1,5 aralnda n alaml Mo ilavesinin etkileri incelenmi ve genel olarak Mo ilavesinin TM eliklerde mukavemet ve sertlik art saladn ifade etmilerdir. almada sonu olarak, % 0,5 Mo alamlarnn sinter sertlemesinin hem Cu hem Ni ilavesiyle mmkn olmasna ramen, tavsiye edilen Ni ve Cu ilavesiyle beraber minimum % 0,85 Mo ilavesi nerilmitir. Isl ilem paralar iin % 0,3 kadar az bir Mo orannn bile paralarn sl ilem tepkilerini iyiletirecei belirtilmi ve Fc-20x serisi alamlara yakn maliyetteki alamlarda, nalaml % 0,3 Mo ilavesinin yalnzca daha iyi sl ilem tepkisi salamad ayn zamanda boyutsal hassasiyeti de iyiletirdii ifade edilmitir. Yksek Mo ve dk karbon ieriinin karburizasyon iin olduka uygun olduu belirtilmitir [3]. Chawla ve Deng (2005) almalarnda sinterlenmi Fe-0,85Mo-Ni eliklerinin mekanik zellikleri ve mikroyapsn younluun bir fonksiyonu olarak incelemilerdir. Sonu olarak ekme mukavemeti, Young modl, krlmaya kadar gerinme ve yorulma zelliklerinin porozitenin azalmasyla arttn tespit etmilerdir. Ayrca 2-boyutlu sonlu elemanlar tabanl mikroyap modeli gstermitir ki, daha youn parann iyiletirilmi ekme ve yorulma davranlar, daha homojen, kk ve daha kresel poroziteye ve malzemedeki azalm gerinme lokalizasyonuna dayandrlabilir [4]. Bergmark ve Bengstsson (2001) ise Cu-C ilaveli TM eliklerin yorulma zellikleri zerine iki farkl younluk (%7,157,4 g/cm3), karbon (% 0,2-0,8) ve bakr orannn (% 0-2) etkisini inceledikleri almada, en yksek yorulma performansnn yksek bakr (%2) yksek C (%0,8) ve yksek younluktaki (%7,4) numunelerde elde etmilerdir [5]. Chagnon ve Trudel (1998) almalarnda sinter sertletirilmi dk alaml (% 2Cu ve %0,65 ve 0,8 kombine Ca ilave olarak % 0,45 Mn- %0,45 Cr-% 0,90 Ni-% 1,0 Mo ieren) elik alamndan % 6,8-7,0-7,15 ve dvme ile tam youn olmak zere 4 farkl younlukta numuneler hazrlamlar ve 1120 Cda 25 dakika sinterlemilerdir. Numuneler zerinde yaplan testler gstermitir ki, grnr sertlik her iki karbon oran iin younluun artmasyla lineer olarak artm ancak art oran % 0,65 C orannda daha fazla olmutur. Younluun etkisinin, tam youn olarak benzer sertlie sahip %0,65 C oranndaki malzemede daha belirgin olduu, ayrca maksimum ve ekme mukavemetlerinin de her iki karbon orannda, younluun artmasyla lineer olarak artt belirtilmitir. Sonu olarak % 0,65 C orannn daha yksek mukavemet deerleri verdii vurgulanmtr [6]. Literatrdeki almalar incelendiinde younluun ve bakrn genel olarak mekanik zelliklerde iyileme salad ancak bu iyilemenin dier alam elementlerinden zellikle de C oranndan etkilendii grlmektedir. Ayrca bakr ve younluun etkisinin birlikte incelendii bir almaya da rastlanmamtr. Bu almada iki grup TM yapsal demir-esasl malzeme grubunda numuneler hazrlanmtr. lk grupta Fe-C ikili alamndan oluan ve MPIF TM yapsal para standardna [7] gre F-0005 ile gsterilen %0,6 C ieren alam 3 farkl younlukta numuneler
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retilmi daha sonra bunlara %2 Cu ilave edilerek 3 farkl younlukta ikinci grup numuneler hazrlanmtr. Numuneler zerinde, sertlik lm, apraz krlma testi (transverse rupture strength-TRS) yaplm, ayrca krk yzey analiz ve makroyap incelemesi yaplmtr. Bylece iki grup numune ile yalnzca younluk deiiminin etkisiyle bakr ilavesinin etkisi detayl olarak incelenmitir. 2. DENEYSEL ALIMALAR 2.1. Malzeme ve Metot Deneysel almalar iin elementel demir, grafit, bakr tozlar ile yalayc olarak inko-stearat tozu kullanlmtr. Numuneler her bir karmn younluuna gre ayr ayr hassas terazi ile tartlarak ift konili kartrc ierisinde % 60 doluluk salanacak ekilde, torna tezghnda en dk devir olan 22,4 devir/dakika dnme hznda 20 dakika kartrlmtr. almada demir esasl 6 farkl karm elde edilmitir. Kullanlan karmlarn tmnde yalayc olarak inko-stearat kullanlm ve ilave miktar % 0,8 orannda sabit tutulmutur. almada ilk grup numune ASTM standardna gre Fe-C ikili alamlardan F-0005 standart karmna uygun ve farkl younlukta hazrlanmtr. Bu ilk grup A1, A2, ve A3 ile gsterilmitir. Bylece A grubu karmlarda (A1-A2-A3) kimyasal bir farkllk olmayp (Fe+%0,6C) yalnzca younluk farll vardr. kinci grup numunede B grubu olarak kodlanmtr. B grubu karmlarda (B1B2-B3) A grubundan farkl olarak tmne % 2 orannda elementel bakr ilave edilmi (Fe+%0,6C+%2Cu) ve yine 3 farkl younluk elde edilmitir. Numunelerin ierikleri aadaki izelge 1de verilmitir. izelge 1. Toz Karmlarna Ait Kodlamalar ve Karm Oranlar (Arlka-%) Karm A1 A2 A3 B1 B2 B3 0,6 C Cu 2 2 2 0,8 Kalan Zn-stearat Fe
Belirlenen oranlarda kartrlan tozlardan numune elde edilmesi iin hazrlanan kalp ile tozlarn blok numune haline getirilmesi gerekletirilmitir. Btn numuneler ekil 1.ada verilen kalp sistemiyle hidrolik preste tek etkili olarak sktrlarak elde edilmitir. Numunelerin geometrisi ve boyutlar, standart eme test numuneleri gz nne alnarak belirlenmitir. Deneylerde kullanlan numunelerin geometrisi ve boyutlar ekil 1.bde verilmektedir.
ekil 1. a) Toz sktrma kalp konstrksiyonu b) Numune geometrisi Preslemede 3 farkl younluk iin, 210 MPa, 350 MPa ve 700 MPa olmak zere 3 farkl basn uygulanmtr. Presleme sonras blok numuneler ayr ayr kodlanm ve numune kodu olarak toz karmlarda kullanlan kodlamalar esas alnmtr. izelge 2de numunelere uygulanan sktrma basn deerleri ve younluk lmlerinden elde edilen sonular ortalama deer olarak Tablo 1de verilmitir. Toz numunelerin sinterlenmemi younluk lmleri TS 2305 standardna uygun olarak Arimet prensibine gre yaplmtr.
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izelge 2. Numune gruplarna uygulanan basn deerleri ve elde edilen younluklar KARIIM Sk. Basnc (MPa) Younluk (g/cm3) A1 210 6.0 A2 350 6.50 A3 700 7.1 B1 210 6.0 B2 350 6.50 B3 700 7.1
Sinterleme ilemi elektrik stmal, otomatik atmosfer kontroll MAHLER marka endstriyel srekli bant frnda, doalgaz (Metan) kullanlarak endotermik atmosferde yaplmtr. Sinterleme esnasnda metan gaz paralanarak (C ve H2 olarak)redkleyici bir atmosfer oluturulmakta ve sktrlm toz kompakt bnyesindeki oksidi alnp, CO2 ve H2O eklinde dar atlmaktadr.Sinterleme ilemi 1120 Cde 20-30 dakika srede gerekletirilmitir Parann frnda kalma sresi ise (n stma, sinterleme ve soutma toplam) 1,5 saat mertebesindedir. 2.2. Bulgular ve Tartma retilen demir esasl TM kompaktlar sinterlendikten sonra malzeme karakterizasyonu iin sertlik ve apraz krlma testleri uygulanm, ayrca krk yzey analizi yaplmtr. T/M numunelerinin presleme ynnde ve buna dik ynde toplam drt yzeyinden Vickers sertlik lmleri alnmtr (ekil 2.). Sertlik lmleri bu drt yzeyde enine ve boyuna olarak ayr ayr alnmtr. izelge 3de gsterildii gibi, presleme ynne dik A ve A yzeylerinin enine ve boyuna sertlik lmleri ayr ayr verilirken, presleme ynne paralel B ve B (yan) yzeylerdeki lm sonular enine ve boyuna lmlerin aritmetik ortalamas (AO) olarak verilmitir.
ekil 2.a) Sertlik lmnn gsterimi b) apraz krlma numunelerinin hazrlanmas izelge 3. Numune yzeylerindeki mikrosertlik sonular (HV10) A1 A2 A3 B1 B2 B3 AE 110-200 145-250 210-283 210-265 215-260 270-340 AB 120-220 131-248 225-255 210-265 215-290 265-340 A'E 120-170 150-205 182-230 210-242 202-255 240-315 A'B 110-170 140-200 165-220 204-245 204-240 240-285 Bort 130-205 139-231 170-215 230-290 265-320 240-290 B'ort 130-170 160-186 175-220 240-285 270-300 250-315 ORT 120-200 144-220 187-240 220-265 230-280 250-315 AO 160 182 215 243 255 282
ekil 3. Mikrosetlik sonular a) grafik gsterimi b) Younlua ve bakr oranna bal
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izelge 3 ve ekil 3 incelendiinde genel olarak u sylenebilir; Yalnz A younluk grubunda %76-91 arasndaki bal younluun artmasyla sertlik % 25 orannda artmtr. B bakr ve younluk grubunda bakr ilavesi genel olarak sertlii A grubunun ayn younluk dzeyine gre %25-40 arasnda bir art salam, ancak bakr ilaveli B grubun kendi iinde %76-91 younluk deiiminin sertlie etkisi, yalnz karbon ieren A grubundan daha az olmu ve % 13 seviyesinde kalmtr. apraz krlma (TRS) deneyi MPIF 35/41 standardna gre yaplmtr. Bu standartta (MPIF 35/41) apraz krlma iin standart numune geometrisi ve boyutlar kalnlk 6,35mm x uzunluk 31,7mm x genilik 12,7mm verilmitir. apraz krlma deney numuneleri ekil 2.b.de grld gibi kompaktn tel erozyon tezghnda boyuna kesilmesiyle elde edilmitir. Bylece bir kompakttan 2 adet apraz krlma numunesi elde edilmitir. Ayn malzemeden retilen bu iki numune iin uygulanan apraz krlma test sonular ortalamas alnarak ekil 2de toplu olarak verilmitir.
ekil 4. apraz Krlma sonular ve grafik gsterimi apraz krlma test sonularna genel olarak bakldnda, TM malzemelerin younluu arttka hem apraz krlma mukavemeti (TRS) hem de sneklii artmaktadr. Bu sonu apraz krlma deneyi esnasnda yk-sehim grafiinden bakldnda A younluk grubunda younluun artmasyla TRS ve sneklii artmaktadr. A Younluk grubunun en dk younlua sahip A1, A younluk grubunun en gevrek malzemesi olarak belirlenmitir. Ayn ekilde B younluk ve Bakr Grubunda da benzer eilim grlmektedir. Yani younluun artmasyla TRS ve sneklik artmaktadr. Bu sonular genel literatr yorumlaryla uyumludur [8];[9]. Bu sonular SEM krk yzey analizleriyle ilikilendirildiinde, A Younluk grubunda en dk younlua sahip A1 ile ayn grupta daha youn A3n krk yzey SEM grntleri ekil 5.a ve bda verilmitir.
ekil 5.a) 6.0 g/cm3 younluklu A1 (Fe+%0,6C) numunesinin krk yzey SEM grnts b) 7.1 g/cm3 younlua sahip A3 (Fe+%0,6C) numunesinin krk Yzey SEM grnts ekil 5.a ve 5.bden grld gibi sar izgilerle belirtilen blgeler partikller aras balarn olutuu ve partikller aras krlmalarn grld blgelerdir. Daha dk younluktaki A1 numunesinde nispeten ba oluumunun daha az ve kk temas alanlarnda, dolaysyla daha gevrek bir yapda olduu, daha youn A3 numunesinde ise daha youn partikller aras boyun olutuu ve bu boyun blgelerinin okluu grlmektedir. Literatrde dk younluklarda mukavemetin partikller aras boyun oluumuyla snrl olduu belirtilmitir [10]. Partikl temas alanlarnn daha byk olmas, apraz krlma srasnda hem TRS deerini arttrd hem de A1e gre deforme olana kadar daha fazla plastik ekil deitirmeye msaade ettii anlalmaktadr.
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ekil 6.a) 6.0 g/cm3 younluklu B1 (Fe+%0,6C+%2Cu) numunesinin krk yzey SEM grnts b) 7.1 g/cm3 younlua sahip B3 (Fe+%0,6C+%2Cu) numunesinin krk Yzey SEM grnts Ayn ekilde B (younluk + bakr) grubunun (Fe+0.6C+0.2Cu) en dk ve en yksek younlua sahip B1 ve B3 numunelerinin ekil 6.a ve bde gsterilen TRS krk yzey SEM analizlerinin karlatrlmas gstermektedir ki, partikller aras temas alanlarnn says ve temas alannn genilii younluun artmasyla artmaktadr. Yine B1 ve B3 arasndaki younluk fark da ekillerden grlmektedir. nk ekil 6.ada partikller arasndaki boluk alanlar daha fazla, ekil 6.bde ise nisbeten daha azdr. Ayrca bu grupta A younluk grubundan farkl olarak bakrn ilave edilmi olmas da yapda partikller arasndaki balarn oluumuna ve kuvvetlenmesine katkda bulunmu ve TRS deerlerini artrmtr [11]. Bakr ilavesiyle TM malzemelerdeki sertlik ve apraz krlma mukavemetinin artmasnn nedeni; bakrn ferritte maksimum zlebilirlii % 1.5-2 Cu oranna kadardr, bu orandan fazla bakr ilavesi tipik olarak tane snrlar ve kk gzeneklerde kelir. Bunun sonucunda partikller arasndaki boyun blgesinde gerilme konsantrasyonunu azaltan ve atlak balangcn geciktiren kresel gzenek oluumu ile sertlik ve mukavemet deerleri artmtr [12]. 3. SONULAR
i.
T/M malzemelerin younluu ve bakr oran, sertlik ve apraz krlma mukavemeti, zerine nemli bir etkiye sahiptir. ii. Younluun artmas apraz krlma mukavemeti ve sertlii arttrr. Bal younluun % 76-91 aralnda artmasyla, Fe-C ikili sisteminde sertlik art % 25 ve apraz krlma mukavemeti %40 artarken, ayn bal younluk aralnda, Fe-C-Cu l sisteminde sertlik %13 apraz krlma mukavemeti % 115 orannda artmtr. Bylece ayn oranlardaki younluk artnn sertlie etkisi yalnzca Fe-C ikili alamna (A grubuna) etkisi Fe-C-Cu l sisteminden oluan B grubuna etkisinden daha fazladr. Yani bakr ilavesi younluk artnn sertlie etkisi azaltmtr iii. Krk yzey SEM grntleri gstermitir ki, daha yksek basnla sktrlan numunelerde, partikller arasndaki temas blgeleri artm ve bu blgeler sinterleme sonras boyun oluumunu artrmtr. Younluk arttka partikller arasnda boyun oluumu artm bylece yap bileenleri arasndaki ba glenerek mekanik zelliklerin artmasna neden olmutur. 4. KAYNAKLAR 1. Schatt, W., Wieters, K.P., Powder Metallurgy: Processing and Materials, European Powder Metallurgy Association (EPMA), Germany, 1997. 2. Sulowski, M., Cias, A., Microstructure and Mechanical Properties of Cr-Mn Structural PM Steels, Archives of Metallurgy of Materials, Vol. 56, Issue 2, 2011. 3. Lindsley, B., Rutz, H., Effect Of Molybdenum Content In Pm Steels, PM 2008, Washington, DC, 2008. 4. Chawla, N and Deng, X., Microstructure And Mechanical Behavior Of Porous Sintered Steels, Materials Science and Engineering A Volume 390, Issues 1-2, 15 January 2005, Pages 98-112, 2005. 5. Bergmark, A., Bengtsson, S., Fatigue Properties of Cu-C alloyed PM Steel at two density levels, EURO PM2001, in Nice, France, 2001. 6. Chagnon,F., Trudel,Y., Effect of Density on Mechanical Properties of Sinter Hardened P/M Materials, PMTEC 98, May31-June4, Las Vegas, Nevada, USA, 1998. 7. MPIF Standart35, Materials Standards for P/M Structural Parts, MPIF, USA, 2000. 8. alak, A., Ferrous Powder Metallurgy, Cambridge International Science Publishing, 450, England, 1995. 9. Hgans AB, Design and Mechanical Properties Volume 3:. Hgans Handbook for Sintered Components, Sweden, 2004a. 10. German, R.M., Powder Metallurgy Science, MPIF, Princeton, NJ, USA, 1994. 11. Hgans AB, Machining Guidelines Volume 5. Hgans Handbook for Sintered Components, Sweden, 2004b. 12. Brnduan, L., 2004. Researches Regarding the Influence of Cu Content on Static and Dynamic Properties of Sintered Steels. Leonardo Electronic Journal of Practices and Technologies, ISSN 1583-1078, Issue 4, January-June, 30-37.
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DOAL TA KESME LERNDE KULLANILAN ALTERNATF KBK BOR NTRRL KESC TAKIMLARIN MKROYAPI VE MEKANK ZELLKLER
Durmu KIR *, Serkan ISLAK **, Halis ELK*, Erturul ELK*** Frat niversitesi, Teknoloji Fakltesi, Metalurji ve Malzeme Mh. Blm, 23100 Elaz, durmuskir@gmail.com, hcelik@firat.edu.tr ** Kastamonu niversitesi, Cide Rfat Ilgaz Meslek Yksekokulu, 37600 Kastamonu sislak@kastamonu.edu.tr *** Tunceli niversitesi, Mhendislik Fakltesi, Makine Mh. Blm, 62000 Tunceli ecelik@tunceli.edu.tr
*
ZET Bu almada, doal ta kesme ilerinde kullanlan elmasl kesici takmlarda elmasn yerine alternatif olarak kbik bor nitrrn (cBN) kullanlabilirlii aratrlmtr. Bu amala soketlere farkl oranlarda kbik bor nitrr ilave edildi. Tm soketler 35 MPa basn altnda, 600 C scaklkta ve 3 dakika sinterleme sresinde scak preste retildi. Soketlerin mikroyap ve faz bileimi taramal elektron mikroskobu (SEM), X-n difraktogram (XRD), X n enerji dalm spektrometresi (EDS) ile belirlenmitir. Soketlerin mekanik zellikleri noktal eme testi kullanlarak tespit edilmitir. Eme testi sonular kbik bor nitrrl soketlerin eme mukavemetlerinin elmasl soketlerinkinden daha yksek ktn gstermitir. Anahtar Kelimeler: Kbik bor nitrr, scak presleme, noktal eme testi
MICROSTRUCTURE AND MECHANICAL PROPERTIES OF ALTERNATIVE CUBIC BORON NITRIDE CUTTING TOOLS USED CUTTING NATURAL STONE
ABSTRACT In this study, the usability of cubic boron nitride (cBN) as an alternative in stead of diamond in cutting tools used to cut natural stones was investigated. For this purpose, cBN with different proportions was added into the segments. All the segments were manufactured under 35 MPa pressure at 600 C with a 3 minutes sintering time. Microstructure and phase composition of segments were determined by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analysis. The mechanical properties of segments were determined using three-point bending test. The results of the bending test demonstrated that the bending strength of the segments with cBN were higher than that of the segments with diamond. Keywords: Cubic boron nitride, hot pressing, three-point bending test 1. GR Kbik bor nitrr (cBN), elmastan sonra en sert malzemedir. Bu iki malzemeyi oluturan elementler periyodik cetvelde birbirine yakn olduundan elmas ile kbik bor nitrrn kristal yaplar benzerdir [1]. Kbik Bor Nitrr, 2597 C scaklk ve 7,7 GPa basn altnda 60 saniye ierisinde gBN (Grafit Bor Nitrr) malzemeden dorudan hBNcBN dnmyle retilen yeniden kristallemi malzemedir. Younluu 3,47-3,48 gr/cm3 dr [2]. Elmas yksek scaklklardaki almalarda grafitlemeye sebep olur. Bylece performansnda d meydana gelir. Fakat cBNnin yksek kimyasal kararllk, yksek sl iletkenlik ve mkemmel anma direnci gibi zelliklerinden
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tr elmasl takmlardaki grafitleme probleminin nne geilmi olur [3-5]. Ayrca cBN, elmasa gre daha ekonomiktir. Sentetik elmas, yksek basn ve scaklk altnda ok ksa srede yumuak olan grafitin ok sert kristal yapl karbon atomuna dnmesi ile elde edilir. Grafit, karbonun kristal formundan birisi olup; dierleri elmas ve ergiyik halidir. Grafit normalde 2500 C scakla kadar dayanr. Sentetik elmas retiminde alternatif bir yntem olarak yksek scaklk ve dk basn (CVD) yntemi de kullanlr. Grafit, karbonun dk younluklu allotropu olup; genellikle yumuak ve siyah renklidir. Sentetik elmaslar bakrdan be kat daha fazla termal iletkenlie sahiptirler. Kbik Bor Nitrr (cBN) de elmasa benzer ekilde retilir. cBN, gnmzde daha ok demir esasl metallerin ilenmesinde yaygn olarak kullanlan polikristalli bor nitrrl (PCBN) takmlarn retiminde kullanlr [6]. Elmas ve cBNin kristal yaplar benzer olup; yapda bulunan her bir atom dier drt atom ile 10928 a yaparak mkemmel bir tetrahedral dzen olutururlar. Elmasta, her bir karbon atomu dier drt karbon atomu ile saf kovalent ba yapar. cBNde ise kovalent ba hkim olmakla birlikte bor ve azotun farkl atomlar olmalar nedeniyle az miktarda iyonik bada bulunmaktadr. cBNde her bir azot atomu drt bor atomu ile balanrken, her bir bor atomuda drt azot atomu ile balanarak tetrahedral karakter gsterir [7]. Soketler, kesici diskin apna ve kesme artlarna bal olarak deiik geometri ve zelliklerde imal edilirler. Soket zelliklerinin belirlenmesinde kesme parametreleri ile kesilecek olan doal tan mineral yaps ve mekanik zelliklerinin bilinmesi gerekir. Soketlere ait matris karmnn hazrlanmas srasnda metal tozlarna ilave olarak 50-500 m tane boyutunda elmas yada cBN tozlar da matrise kartrlarak soket retimi yaplr. Doal ta kesme ileminde arlkl olarak dikdrtgen kesitli elmasl soketler tercih edilmektedir. Soketler, matris ve elmas ya da cBN tozlar olmak zere iki paradan olumaktadr. Matris, elmas ya da cBN taneciklerini matriste tutma ilevini yerine getirirken; elmas ya da cBN ise kesme ilevini yerine getirir [8,9]. Baarl bir elmas soket tasarm iin nitelikli metal tozlarnn kullanlmas gerekmektedir. Matriste elmas yada cBN tanelerini tutmas iin Co, Ni, Cu, Fe veya bunlarn kombinasyonlarndan yararlanlr. Dolgu evresi iin genellikle Cu-Sn kullanlr [10,11]. Kesilecek doal tan zelliklerine, kesme parametrelerine ve kesme koullarna bal olarak ana ve balayc fazlarn oluturulmas deimektedir. Bu gne kadar doal ta kesici takmlar ile ilgili yaplan almalar, genellikle mevcut elmasl soketlerin anmas, kesme performans ve kesme srasnda oluan kuvvetler, kesici soketteki hasar durumlar, matris karakterizasyonu, analitik/nmerik modellemeler ile elmasl kesici disklerin dinamik davranlarnn incelenmesi ve elmas kesici tellere ait alsmalar zerine younlam bulunmaktadr. Literatrde doal ta kesici takmlarda elmas yerine kbik bor nitrr de dhil olmak zere alternatif bir andrc kullanldna dair bir almaya henz rastlanlmamtr. Yaplan bu almada, doal ta kesici takmlarda kbik bor nitrrn alternatif andrc olarak kullanlmasnn aratrlmas amaland. Bu amala soketlere kesici tanenin arlka % 0-100 arasndaki orann cBN ilave edildi. Soket matrisinin brinel cinsinden sertlii ve sktrlabilirlik zellikleri iin younluu lld. Soketin mikroyaps ve krk yzeyinin incelenmesinde taramal elektron mikroskobu (SEM), enerji dispersive spektograph (EDS) faz eitleri iin X-n difraktometresi (XRD) kullanld. Soketlerin eme mukavemeti deerleri noktal eme testi ile tespit edildi. 2. DENEYSEL ALIMALAR Doal ta kesici takmn retiminde matris olarak -325 mesh tane boyutuna ve % 99.9 safla sahip Cu-15Sn tozu kullanlmtr. Kesici olarak 40/50 ve 50/60 mesh tane boyutuna sahip MBD.6 ticari sentetik elmas ve yine ayn tane boyutuna sahip kbik bor nitrr matrise ilave edildi. Her iki tane boyutu eit miktarda kullanld. ki farkl tane boyutuna sahip kesici taneciin kullanlmasnn sebebi takmn kesme performansn arttrmaktr. Kullanlan kesici konsantrasyonu her bir numune iin toplam olarak 30 olarak seildi. Elmasl/cBNli soketlerin retiminde kullanlan numune gruplar ve retim parametreleri Tablo 1de verilmitir. ekil 1de soket retiminde kullanlan elmas, cBN ve CuSn tozunun ve SEM fotoraflar grlmektedir. Tablo 1. Soket retiminde kullanlan matris gruplar ve retim parametreleri
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ekil 1. Soket retiminde kullanlan tozlarn SEM fotoraf: (a) elmas, (b) cBN ve (c) CuSn tozu Tablo 1de ki gibi hazrlanan matris/elmas/cBN karm mikserde 30 dakika sre ile 20 d/d hzda % 1 orannda parafin ya eklenerek krom kaplanm elik bilyeler ile birlikte kartrlmtr. elik bilye kullanmndaki ama karma katlan parafin yann topak oluturmasn engellemektir. Toz halindeki soketler 15 MPa basnla souk olarak preslendi. Biskvi eklindeki soketler grafit kalplarda scak presleme teknii kullanlarak preslendi. Her bir soket 35 MPada 600 C scaklkta 3 dakika sinterleme sresinde elde edildi. ekil 2de sinterleme grafii verilmitir.
ekil 2. Sinterleme grafii Scak presleme yntemi ile retilen soket matrisin sertlii BAHA marka sertlik lme cihaznda 62,5 kg yk ve 2.5 mm apnda bilye ile Brinell cinsinden llmtr. Soketlerin eilme dayanmlar, 40 mm x 7 mm x 3.2 mm lsndeki numuneler kullanlarak noktal eme testi ile tespit edilmitir. noktal eme testi sonras elde edi-
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len krlma numunelerinin mikroyap zellikleri taramal elektron mikroskobu (SEM-JEOL Ltd., JEM-2100F model), enerji dispersive spektograph (EDS), X- n difraksiyonu (XRD- Bruker AXS Inc., D8 Advance model) ve spektral analizleri ile deerlendirilmitir. XRD analizleri 30 kV ve 15 mAde CuK radyasyonu kullanlarak Rigaku Geigerflex X-n difraktometresi ile elde edilmitir. 3. SONULAR VE TARTIMA Sktrlabilirlik ve younlama hususunda bir fikir vermesi asndan soket numunelerinin younluk lmleri yaplmtr. Yaplan lmler sonucunda 600 C sinterleme scakl iin soket younluunun 8,5866 gr/cm3 olduu tespit edilmitir. Teorik ve deneysel younluk kullanlarak elde edilen bal younluk ise % 98.855dir. Karl Frank marka sertlik lme cihaz ile 62.5 kg yk ve 2.5 mm apl bilya kullanlarak elde edilen matris sertlik deeri ortalama 75.46 HB olarak lld. 600 Cde retilen soket matrisinin mikroyapsnda tane snrlarnda XRD analizleri (ekil 4) ile de tespit edildii gibi Cu3Sn gevrek fazn olutuu tahmin edilmektedir (ekil 3). Matris % 85.461 Cu ve % 14.539 Snden olumaktadr (EDS analizine gre). Mikroyapdan soket matrisinde sinterleme koullarnn yeterli olmayndan dolay gzeneklerin olutuu tespit edilmitir.
ekil 3. CuSn matrisin SEM fotoraf ve EDS analizi ekil 4de soketlerden alnan XRD grafikleri verilmitir. XRD analizleri sonucunda, soketlerde cBN, elmas, -Cu, Cu3Sn bronzu fazlar tespit edilmitir. Matrikse katlan cBN miktarnn artmas ile cBN piklerinin iddetlerinde artlar meydana geldii gzlenmitir.
ekil 4. cBN/elmasl soketlerin XRD grafii Her bir soket grubuna ait numunelerin eilme mukavemetleri, noktal eme deneyi yaplarak llmtr. Yaplan deneylerde ASTM B 528-83a standardna gre imal edilen zel olarak yaplm aparatlar kullanlmtr. Instron marka ekme deney makinesinde yaplan deneylere ait sonular ekil 5de grlmektedir.
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ekil 5. Arlka % cBN miktarnn eme mukavemetine etkisi ekil 5de verilen grafik incelendiinde, cBN katkl numunelerin eilme mukavemetlerinin elmas katkl numuneye gre daha yksek olduu grlmektedir. Arlka % 0, 20, 40, 60, 80 ve 100 cBN ilavelerinde srasyla eme mukavemetleri 222 MPa, 305 MPa, 280 MPa, 260 MPa, 294 MPa ve 297 MPa olarak belirlendi. % 100 cBN katkl numunenin eilme mukavemetinin, % 100 elmas katkl numuneye gre yaklak % 30 daha byk olduu grlmektedir. Genel olarak tm cBN katkl numunelerin eilme mukavemetlerinin % 100 elmas katkl numuneye gre daha yksek olduu grlmektedir. Bunun sebebi olarak elmasa nazaran cBNin 85/15 bronz malzeme ile iyi bir ba yapt sylenebilir. ekil 6daki krma yzeylerinin SEM fotoraflar incelendiinde matris ile cBN arasndaki arayzey balantsnn, matris ile elmas tanesi arayzey balantsndan daha kuvvetlii olduu grlmektedir. Tm krk fotoraflarndan matris ile kesici tanecik arasnda sz konusu balanmann arzu edilenden daha zayf olduu anlalmaktadr. Ayrca krk yzeylerde matristeki gzeneklerde dikkat ekmektedir. Bu durum sinterleme scaklnn ve presleme basncnn dk olmas ve matrisin elmas bu scaklkta slatma kabiliyetinin dk olduu dnlmektedir.
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ekil 6. noktal eme testi sonras oluan krk yzeylerin SEM fotoraflar: (a) % 0 cBN, (b) % 20 cBN, (c) % 40 cBN, (d) % 60 cBN, (e) % 80 cBN, (f) % 100 cBN 4. GENEL SONULAR CuSn matrisine farkl oranlarda elmas/cBN ilave edilerek 600 C sinterleme scaklnda, 35 MPa presleme basncnda ve 3 dakika sinterleme sresinde doal ta kesici soketler retildi. Soket matrisinin nispeten gzenekli olduu SEM fotoraflarndan belirlendi. Bu durum sinterleme scaklnn dk olduunu gstermektedir. Ayrca soketlerin XRD analizlerine gre mikroyapda -Cu, Cu3Sn, elmas ve cBN fazlar olutu. noktal eme testi ile en yksek eme mukavemeti deerine % 100 cBNli soketin sahip olduu tespit edildi. Bunun sebebi olarak elmasa nazaran cBNin matris ile iyi bir ba oluturduu dnlmektedir. 5. TEEKKR Bu almann yrtlmesi ve sonulandrlmas ile ilgili konularda FBAP-2020 nolu proje ile maddi destek salayan Frat niversitesi Bilimsel Aratrmalar Projeleri Birimine (FBAP), teekkr ederiz. 6. KAYNAKLAR 1. Brookes, C.A., The mechanical properties of cubic boron nitride a perspective view, Inst Phys Conf. Ser., Vol. 75, pp. 20720, 1986 2. Petrusha, I.A., 2000, Features of a cBN-to-graphite-like BN phase transformation under pressure, Diamond and Related Materials, Vol. 9, pp. 1487-1493, 2000 3. Wentorf, R.H., De Vries, R.C., Bundy, F.P., Sintered superhard materials, Science, Vol. 208, pp. 87380, 1980 4. Tomlinson, P.N., Wedlake, R.J., The current status of diamond and cubic boron nitride composites, Proceedings of the international conference on recent developments in specialty steels and hard materials, Oxford: Pergamon; pp. 17384, 1983 5. Brook, B., Principles of diamond tool technology for sawing rock, International Journal of Rock mechanics and Mining Sciences, Vol. 39, pp. 41-58, 2002 6. ifti, ., Trker, M., eker U., CBN cutting tools wear during machining of particulate reinforced MMCs, Wear, Vol. 257, pp. 1041-1046, 2004 7. Pierson, H.O., Handbook of Refractory Carbides and Nitrides, William Andrew Pub., Noyes, 1996 8. Konstanty, J., Production of Diamond Sawblades for Stone Sawing Applications, Key Engineering Materials, Vol. 250, pp. 1-12, 2003 9. Konstanty, J., Powder Metallurgy Diamond Tools, Elsevier Ltd, The Metal Powders Technology Series, pp. 106-107, 2005 10. Karagz, ., Zeren, M., The microstructural design of diamond cutting tools, Materials Characterization, Vol. 47, pp. 89-91, 2001 11. Zeren, M., Karagz, ., Defect characterization in the diamond cutting tools, Materials Characterization, Vol. 57, pp. 111-114, 2006
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TM ALUMIX 231 VE %5 SiCp KOMPOZTE UYGULANAN EKSTRZYON VE YKSEK BASINLI BURULMA LEMLERNN MEKANK ZELLKLERE ETKS
Ceren GDE*, smail ZDEMR**, Hasan ALLIOLU*** ve Hakan YILMAZER****
*
Pamukkale niversitesi, Denizli Meslek Yksekokulu, Metal ve Makine Teknolojileri Blm, 20070, Denizli, cgode@pau.edu.tr ** Bartn niversitesi Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 06500, Bartn, iozdemir@bartin.edu.tr *** Pamukkale niversitesi Mhendislik Fakltesi, Makine Mhendislii Blm, Denizli, 20070, hcallioglu@pau.edu.tr **** Tohoku niversitesi Mhendislik Enstits, Malzeme Bilimi Blm, 9808577 Japonya, hakan@imr.tohoku.ac.ip zet
Toz metalurjisi souk presleme (SP) yntemiyle retilmi Alumix 231 ve %5 SiCp takviyeli kompozitlere uygulanan ekstrzyon (EKST) ve yksek basnl burulma (HPT) ilemlerinin mekanik zelliklere etkisi incelenmitir. retilen numunelerin mikro sertlik ve mekanik zelliklerindeki deiimler aratrlmtr. ekme deneyi uygulanm ve mikro sertlik deerleri llmtr. TM malzemelerin optik ve SEM incelemeleri de yaplmtr. Sonularda, SP numunelerine gre EKST ve HPT numunelerinde ekme dayanm ve sertlik deerleri art gstermitir. Alumix 231 ierisindeki %5 SiCp ilavesi ile ekme dayanm azalm, sertlik deerleri ise bir miktar art gstermitir. ekme deneyi grafikleri ve krlma yzeyleri incelendiinde HPT ve EKST numunelerinde SP numunelerine gre daha snek krlma olutuu grlmtr. Anahtar Kelimeler: Toz metalurjisi, souk presleme, ekstrzyon, yksek basnl burulma, mekanik zellikler.
THE EFFECTS OF EXTRUSION AND HIGH PRESSURE TORSION ON THE MECHANICAL PROPERTIES OF PM ALUMIX 231 AND 5% SiCp COMPOSITE
ABSTRACT The effect of extrusion (EXTR) and high pressure torsion (HPT) on the mechanical properties of cold pressed (CP) Alumix 231 and 5% SiC reinforced composites, produced by PM route, were examined. The changes on micro hardness and mechanical properties of the specimens were investigated. For this purpose tensile and micro hardness tests were carried out. SEM and optical analysis of powder metallurgy materials were also examined. The results showed that tensile strength and hardness values in extrusion and high pressure torsion samples increased compared to cold pressed samples. The addition of 5%SiC reinforcement into Alumix 231 resulted in a decrease in tensile strength whereas increased the hardness values. When examining the tensile test graphics and fracture surfaces, it was seen that HPT and EXTR samples exhibited more ductile behavior than CP samples. Keywords: Powder metallurgy, cold pressing, extrusion, high pressure torsion, mechanical properties. 1. GR Teknolojinin hzl deiimi ve buna paralel olarak malzeme teknolojisinin srekli gelimesi karsnda aratrmaclar yeni malzemeler aratrmaya ve mevcut malzemeleri de gelitirmeye ynelmilerdir. Son zamanlardaki gelimelere
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bal olarak stn zelliklere sahip kompozit malzemelerin ileri mhendislik uygulamalarnn kullanld gnmzde nemi giderek artmakta ve bu alanda birok almalar yaplmaktadr [1,2]. Alminyum matrisli kompozitler (AMK), tedarik kolayl gibi stn zellikleri ile gelitirebilmekte ve dk arlklar, yksek mukavemetleri, stn anma dayanmlar sayesinde birok mhendislik uygulamas iin potansiyel bir malzeme haline gelmitir [3]. Aratrmalar sonucunda ticari Al alamlar ile kyaslandnda, alminyum matrisli parack takviyeli kompozitlerde artan sertlik, anma direnci, mukavemet, titreim azaltc ve dk sl yaynm katsays gibi zellikleri olduunu ortaya kmtr. Ksa fiber, srekli fiber ve klcal kristal takviyeli alminyum matrisli kompozitlerin retiminde zorluklar yaanmaktadr. Son yllarda parack takviyeli alminyum matrisli kompozitlerin kullanmnda bir art grlrken, iletme giderleri ve ilenebilirliklerindeki zorluklarla kyaslandnda bu kompozit paralarn uygulama alanlar kstlanmtr [4,5]. Kompozit malzemeler, yaygn olarak otomotiv, uak ve elektronik sanayilerinde, uzay endstrisinde ve talal imalat sektrnde anma direnci, yksek scaklk zellii ve hafiflik istenen durumlarda tercih edilmektedir. Toz metalurjisi (TM) rnlerinin en yaygn kullanld alan otomotiv endstrisidir [6]. zellikle dnyadaki petrol fiyatlarnn artmas ile daha fazla yakt ekonomisi yaratmak otomotiv reticileri zerinde artan bir bask yaratmtr. Ara arln azaltarak yakt tketimini en alt seviyelere indirmek iin gnmzde pek ok aratrma yaplmaktadr. Otomotiv uygulamalarnda TM yntemiyle retilen yksek performansl, dk younluklu paralarn hazrlanmasnda en ideal malzemelerin banda alminyum gelir. Ancak kalpta presleme ve sinterleme sreci sonunda %9095 teorik younlukta numuneler elde edilirken geride kalan gzenek miktar dikkat ekmektedir. Bu gzenek miktarn drmek ve daha mukavemetli paralar elde etmek iin TM yntemleri dnda numunelere ikincil ilemlerin uygulanmas ihtiyac duyulmutur. Parack takviyeli AMKde, seramik paracklar metalik alamn mekanik zelliklerini gelitirmede son zamanlarda oka kullanlmaktadr. Bu almada, toz metalurjisi yntemiyle retilmi Alumix231 ve %5 SiCp takviyeli kompozitlere uygulanan ekstrzyon (EKST) ve yksek basnl burulma (HPT) ilemlerinin ekme deneyi ile mekanik zellikleri ve mikro sertlik lmleri ile sertlik deiimleri incelenmitir. Burada SiC ilaveli numunelerde ekme dayanm deeri azalmaktadr. Mikroyap, SEM ve TEM incelemelerinde yapda SiC ilaveli numunede gzeneklerin dierlerine gre daha fazla olduu ve en az gzeneklilik orannn HPT numunelerine ait olduu tespit edilmitir. Gzenekliliin ve parack boyutunun azalmas ile HPT numuneleri en yksek mekanik zellikleri tad belirlenmitir 2. DENEYSEL ALIMALAR Bu almada ECKA Granulate Velden GmbH, Germany firmasndan temin edilen Alumix 231 (2,5 Cu, 0,5 Mg, 14 Si) tozu (<157 m) kullanlmtr. Toz ierisinde %1,5 orannda Amide-wax (Ethyle bisstearamide) yalayc mevcuttur. Alumix 231 tozuna % 5 oranlarnda (% arlk olarak) SiC (< 53 m ) tozu (Aldrich) ilave edilerek 30 dakika sreyle 60 dev/dkda boyutlu turbula ierisinde kartrlmtr. Tozlar daha sonra kalp ierisinde 600 MPa basn altnda 1 dk sreyle preslenerek ekme numuneleri ve 200 MPa basn altnda 1 dk sreyle preslenerek 100 mm apnda silindir eklinde ktk numuneler elde edilmitir. Souk presleme (SP) yntemi ile retilen ekme numuneleri tp frnda ncelikle 410 C scaklkta 50 dakika sreyle yalayc uurma sonras 565 C scaklkta 90 dakika sreyle stma ilemine tabi tutulmulardr. SP sonras ekstrzyon (EKST) ilemi iin kullanlan ktk numuneler, ayn stma artlar sonras pres zerinde 565 Cye kadar stlan kalp ierisinde 4:1 orannda ekstrze edilmitir. EKST sonras elde edilen blok numuneler ekme numunesi eklinde ve yksek basnl burulma ileminde (HPT) kullanlmas iin 0,80 mm kalnlnda ve 20 mm boyutlarnda para biiminde kesilmitir. Kesilen EKST numuneleri Tablo 1de verilen deney artlarnda HPT ilemine tabi tutulmutur. HPT ilemine ait hidrolik pres ve kalplar ekil 1de verilmektedir. HPT ilemi; uygulanan basn yardmyla, presleme ilemiyle malzemenin burulma srasnda ayrlmasn nlemek amac ile alt ve st olmak zere iki takoz arasnda kuvvet uygulanarak gerekletirilmektedir. HPT cihazna yksek basn altnda malzemeye burma ilemini gerekletirmek amacyla alt ve st kalplar taklr. Bu kalplarn malzeme ile temas halindeki yzeyleri przlendirilmitir. Para eklindeki malzeme alt kalptaki yerine yerletirildikten sonra kalbn d ksmna karbon yalayc srlr. Yalaycnn ilem srasnda numuneye temas etmeyecek ekilde srlmesine dikkat edilir. Daha sonra alt takoz tarafndan, kapal sistem ierisindeki iki kalp arasnda bulunan numuneye alt takoz vastasyla burulma ilemi uygulanr. HPT cihazyla burulma ilemi, bir panel yardmyla uygulanacak basn ve burulma hz kontrol edilerek gerekletirilmektedir.
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ekil 1: HPT ileminde kullanlan hidrolik pres ve kalp Tablo 1. Yksek basnl burulma numunelerin deneysel deerleri Numune Alumix 231 %5 SiC Balang Presleme Deeri (GPa) 5 5 Burulma Hz (dev/dk, Derece) 0,5/180 0,2/72 Burulma Deeri 5 tam tur 5 tam tur
Elde edilen numunelerin younluk, sertlik ve ekme dayanm deerleri llmtr. Ayrca, SiC ilavesinin etkileri aratrlmtr. Younluk lm: Numunelerinin gerek younluk deerleri ayn dijital terazi ve younluk lm kiti kullanlarak Arshimet prensibine gre yaplmtr Her bir kompozit iin teorik ve deneysel (gerek) younluk arasndaki farklar alnarak gzenek miktarlar (1)de verilen eitlikle hesaplanmtr. lm sonular Tablo 2de verilmektedir. (1)
ekme Deneyi: SP ve EKST ilemlerinden elde edilen ekme deneyi numuneleri MPFI10, 1998 standartlarnda olup, HPT ilemi sonucunda elde edilen ekme numuneleri boyutlar ve ekme aparat ekil 2de verilmektedir. ekme hz 0,5 mm/dk olarak deney uygulanmtr. Her bir grup numune iin maksimum ekme dayanm deerleri elde edilmi ve ortalama ekme deneyi sonular Tablo 3de verilmitir.
ekil 2. ekme numunesi boyutu ve ekme cihazna yerletirilen ekme aparat
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Mikrosertlik lm: Shimadzu mikro sertlik cihaznda iz alan temel alnarak lm yaplan Vickers sertlik yntemine gre numunelerden sertlik lmleri alnmtr. Mikro sertlik iin, 2000 gf kuvvet 10 s uygulanm, mikro sertlik lmleri ortalama sonular Tablo 4de verilmitir. 3. DENEYSEL SONULAR VE TARTIM 3.1 Younluk lm Tablo 2. Numunelerin gzenek miktar Malzeme Alumix 231 % 5 SiC SP Gzenek Miktar (%) 3,93 4,31 EKST Gzenek Miktar (%) 0,59 0,67 HPT Gzenek Miktar (%) 0,43 0,58
Numunelerinin gzenek miktar SiC ilavesi ile art grlmtr Bunun nedeni SiC parack younluunun Alumix 231 tozun younluundan yksek olmasdr. SiC paracklarnn sertliinden dolay karm tozun skmaya daha direnli hale gelmesiyle preslenebilirliin ktlemesi, parack takviye miktarnn artmasna paralel olarak da artan matris/takviye ara yzey alannn artmas ve bunun da gzeneklilii arttrmas gsterilebilir [7]. Tablo 2 incelendiinde numunelerde ulalan en dk gzenek miktar %0,43 ile HPT numunelerine aittir. Burada SP numunelerine ikincil ilem olarak uygulanan EKST ve HPT ilemleri gzeneklilii en alt dzeye indirerek mekanik zellikler asndan nemli bir avantaj salamtr. 3.2 ekme Deneyi Tablo 3. Numunelerin ortalama ekme dayanm deerleri (MPa) Malzeme Alumix 231 % 5 SiC SP ekme Dayanm (MPa) 92 69 EKST ekme Dayanm (MPa) 253 212 HPT ekme Dayanm (MPa) 537 418
Malzeme ierisinde SiC ilavesinin ekme dayanm deerlerini azaltt grlmtr. Dn sebebi, takviye hacim oran art ile ekme dayanm der. Toz paracklarnn retimi srasnda presleme sonrasndaki oluan gzenekler ve matris/ara yzey ba iyi olmad durumda ara yzey alan artna bal olarak SiC tozlarn birleememesiyle artan ara yzey alannn kopmay kolaylatrmas gibi faktrler bu azalmada etkili olduu dnlmektedir. EKST ve HPT ikincil ilemleri de uygulansa takviye maddesi ilavesi matris katk maddesi toz ara yzey etkileimin yetersiz kalmasna ve ara yzeylerden ayrlma krlmasnn gelimesine ve hzla enine kesitte ilerleyerek erken kopmaya neden olmaktadr. Burada ikincil ilemler ekme dayanmmda EKTS ilemi SPye gre %400 art salarken HPT ilemi EKTS ilemine gre %200 art salamtr. Burada HPT tekniinin temeli; malzemenin ilem srasnda hacmi deimeden malzemeye deforme etme amacna dayanr. Bu ekilde malzeme de tane yaps mikron seviyeden nano seviyeye indirilerek nano seviyede bir yap elde edilir (ekil 46). retilen malzemeler mikron seviyedeki ayn malzemeye gre daha iyi zellikler gsterir. Bu da bu ilemin ok iyi olduunu gstermektedir [8,9]. 3.3 Mikro sertlik lmleri Tablo 4. Numunelerin ortalama sertlik deerleri (HV0.2) Malzeme Alumix 231 % 5 SiC SP Sertlik Deeri 33 37 EKST Sertlik Deeri 76 77 HPT Sertlik Deeri 239 258
Burada, HPT uygulanm numunelerdeki sertlik deerlerinin EKST ilemine gre yaklak 3 kat artt grlmektedir. Bunun nedeni HPT ileminin paracklarn klmesi ve Si dalmnn artmasyla tane snrlarnn oalmas olarak gsterilebilir. Kullanm koullarna bal olarak sertlik istenilmesi durumunda TM malzemelerdeki bu sertlik art nemli olabilir.
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ekil 3. Alumix 231 ve %5 SiC HPT numunelerinin sertlik deerlerinin merkeze olan uzakla gre deiimi ekil 3te grld gibi numunenin merkezinden kenara gidildike homojen bir sertlik dalm olmad gzlemlenmektedir. Bunun nedeni, kenar blgelerde gerinim artndan dolay tane klmesinin daha fazla yaanmasyla aklanabilir. Tane klmesine sebep olan gerilme, alma sertlemesine, hz da sertlik artna sebep olmaktadr. Farkl almalarda da belirtildii gibi ilemin etkisi merkezden kenar blgeye doru gidildike daha fazladr [10]. Dikkat edilirse %5 SiC ilavesi sertlikte ciddi art oluturmamtr ve sertlik deiimi merkezden uzaklatka ilavesiz matris malzemeye paralel gitmektedir. 3.4 Mikroyap ncelemeleri EKTS ve HPT Alumix 231 matris malzemeye ait numunelerin yzeylerinden alnan XRD grnt analizi ekil 4de verilmitir.
ekil 4. Alumix 231 EKST ve HPT numunesine ait XRD grafiinde Si pikleri Grafikten de grld gibi 56. pikte Si paracklarnn HPT sonras kld hatta baz piklerde kaybolduu tespit edilmitir. Alumix 231 alamnn EKST ve HPT (P=5GPa ve N=5) numunelerine ait SEM grntleri ve SEM fotoraflarndan llerek (Clemex image analysis) belirlenen silisyum fazlarn boyut dalm ekil 5te gsterilmektedir.
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ekil 5. Alumix231 iin (a) EKST ve (b) HPT numunesine ait Si dalm grafii ve SEM grntleri Toz halindeki ilem grmemi Alumix231 matriste tektik alt ikincil silikon fazlar ~2030 m boyutlarndadr [11]. Alam, EKST alama gre HPT sonras daha modller ve kk tektik silisyum fazlar bulunmaktadr. Ayrca silisyum fazlar HPT sonras Al metal matris ierisine daha homojen dalma gstermektedir. Hem EKTS hem de HPT sonraki alam, ~0,33,8 m arasnda deien silisyum fazlarn boyut dalmna sahiptir. Fakat EKTS sonras alam farkl boyut gruplarnda faz dalm gsterirken, HPT sonrasnda daha homojen ve kk boyutta silisyum faz dalm gstermektedir. Bir mikron altnda (1,0 m) silikon faz oran HPT sonras %89,5 iken EKTS sonras 70,4 %tir. Yine 0,5 mikron altnda ( 0,5) silikon faz 58,6 % iken EKTS sonrasndaki 30,9 % oranndadr.
ekil 6. %5 parack takviyeli numunelerin SiC paracklarn SEM grntleri HPT ileminde takviye faz zerinde ok fazla klerek EKST ilemindeki gibi matris ierisinde dalmnda farkllk salanmamtr. Ayrca, parack baznda ekil 6.(d)de grld gibi parack evresinde az miktarda krlmalara sebep olsa da SiCn matris malzemeden sert olmas nedeniyle takviye elemann klmesi ve daha homojen dalm sz konusu olmamtr. Bu durum farkl almalarla da desteklenmektedir [12]. Burada ekil 6. (b) ve (d) incelendiinde ikincil faz olan Si paracklar HPT ncesinde uzun ve yaygn iken sonrasnda daha yuvarlak ve dzgn hale gelmitir [13].ekme deneyi sonras krlma yzeylerinden alnan SEM grntleri ekil 7de verilmitir.
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ekil 7. %5 parack takviyeli numunelerin mikroyap grntleri Krlma yzeylerinin SEM grntleri incelendiinde, SiC ile ana malzeme arasnda SP numunelerinde yeterli slatma gereklemedii grlmektedir. Buna bal olarak matris takviye malzemesi arasnda oluan birlemenin yeterli olmad ve krlmann daha dk kuvvetlerle gerekletii dnlmektedir. EKST ve HPT numunelerinin Alumix 231 ve %5 SiC parack numunelerinde snek krlma gzlenmitir. Mekanik zelliklere bakldnda HPT numunelerinin ekme mukavemetinin olduka ykseldii grlmektedir. Tahmin edildii gibi uygulanan burulma ileminin, numunelerin mekanik zelliklerini iyiletirdii ynnde bilgi vermektedir [8]. SP numunelerine direk HPT ilemi yapldnda baarsz olunmutur. SP numuneleri HPT ilemi balangcnda gerekli sneklii tamad iin uygulama balangcnda numuneler krlmtr. Dolaysyla SP numunelerinde direk HPT ilemi uygulanmamtr. 4. SONULAR - - - kincil ilemler ekme dayanmmda EKST ilemi SPye gre %400 art salarken HPT ilemi EKST ilemine gre %200 art salamtr. Alumix231 ierisindeki %5 SiCp ilavesi ile, ekme dayanm azalm, sertlik deerleri ise bir miktar art gstermitir. HPT ve EKST numunelerinde TM numunelerine gre daha snek krlma olutuu grlmtr.
5. TEEKKR Bu alma, Pamukkale niversitesi Bilimsel Aratrma Projeleri Komisyonu tarafndan, BAP 2009/032 nolu projesi ile desteklenmitir. Prof. Dr. Mehmet TRKERe laboratuar imknlarn salad iin teekkrlerimizi sunuyoruz. KAYNAKLAR 1. Akbulut, H., Almina Fiber Takviyeli Metal Matrisli Kompozitlerin retimi ve Mikroyap-zellik likilerinin ncelenmesi, Doktora Tezi, T Fen Bilimleri Enstits (yaymlanmam), stanbul, 1995. 2. gel, B. Kompozit Malzemelerde Son Gelimeler ve leriye Dnk Beklentiler, 9. Uluslararas Metalurji ve Malzeme Kongresi, stanbul, Vol. 33, pp. 639650, 1997. 3. Toptan, F., Alminyum Matrisli B4C Takviyeli Kompozitlerin Dkm Yntemiyle retilmesi, Yksek Lisans Tezi, YT Fen Bilimleri Enstits, stanbul, 2006. 4. ODonnell, G., Looney, L., Production of Aluminium Matrix Composite Components Using Conventional PM Technology, Materials Science and Engineering, Vol. A303, pp. 292 301, 2001. 5. Wlodarczyk-Flger A., Dobrzansk L.A., Kremzer M., Adamak M., Manufacturing of aluminium matrix composite materials reinforced by Al2O3 particles, Journal of Achievements in Materials and Manufacturing Engineering, Vol. 27, pp. 99-102, 2008.
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6. ahin, S., Akgn, S., Uzkut, M., Kksal, N.S., T/M Yntemi ile retilmi Al Esasl SiC, Al2O3, SiC + Al2O3 Takviyeli Kompozitlerin Anma Davrannn ncelenmesi, 10. Denizli Malzeme Sempozyumu ve Sergisi, Denizli, pp.442 449, 2004. 7. German, R.M., Powder Metallurgy Science, MPIF, Princeton, NJ, USA, 1994. 8. Cepeda-Jimnez, C.M., Garca-Infanta, J.M., Zhilyaev, A.P., Ruano, O.A., Carreno, F., Influence of the Thermal Treatment on the Deformation-induced Precipitation of a Hypoeutectic Al7 wt% Si Casting Alloy Deformed by High-pressure torsion, Journal of Alloys and Compounds, Vol. 509, pp. 636643, 2011. 9. Rajinikanth, V., Venkateswarlu, K., Sen, M. K., Das, M., Alhajeri, S.N. and Langdon, T.G., Influence of scandium on an Al2% Si alloy processed by high-pressure torsion, Materials Science and Engineering A, Vol. 528, 17021706, 2011. 10. Edalati, K. and Horita, Z., Universal Plot for Hardness Variation in Pure Metals Processed by High-Pressure Torsion, Materials Transactions, Vol. 51, pp. 1051-1054, 2010. 11. Heard, D.W., Donaldson, I.W. and Bishop, D.P., Metallurgical Assessment of A Hypereutectic AluminumSilicon P/M Alloy, Journal of Materials Processing Technology, Vol. 209, pp. 5902-5911, 2009. 12. Sabirov, I., Kolednik, O. and Pippan, R., Homogenization of Metal Matrix Composites by High-Pressure Torsion, Metallurgical and Materials Transactions A, Vol. 36A, pp. 2005-2861, 2005. 13. Edalati, K. and Horita, Z., Application of high-pressure torsion for consolidation of ceramic powders, Scripta Materialia, Vol. 63, pp. 174177, 2010.
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METALLIC FOAM
www.turkishpm.org
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ALSi7, ALSi14 VE ALSi14CU4,5 KARIIM TOZLARDAN ALMNYUM SANDV KPK RETLEBLRLNN ARATIRILMASI
Hseyin DEMRTA * ve Mehmet TRKER**
*
Karabk niversitesi Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 78050, Karabk, hdemirtas@karabuk.edu.tr ** Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, mturker@gazi.edu.tr zet
Bu almada toz metalurjisi yntemi ile dk ergime derecesine sahip farkl Al alamnn sandvi kpk retimi aratrlmtr. Kullanlacak malzemelerin kimyasal bileimi AlSi7, AlSi14 ve AlSi14Cu4,5 olarak belirlenmitir. Deneyler sonucunda alamn da saf alminyumdan olduka dk scaklklarda kprd ve sandvi retimi iin uygun olduu belirlenmitir. Anahtar Kelimeler: Toz metalurjisi, alminyum sandvi kpk. INVESTIGATION OF THE REPRODUCTIBILITY OF ALUMINIUM SANDWICH FOAM FROM ALSi7, ALSi14 AND ALSi14CU4,5 PREMXED POWDERS ABSTRACT In this study, reproducibility of sandwich foam by using three different Al alloys, which have low melting points, have been investigated. The chemical compositions of the powder were chosen as AlSi7, AlSi14 and AlSi14Cu4.5. Experimental results has show that each three alloys foaming lower temperature than pure aluminum and detected as suitable for sandwich production. Keywords: Powder metallurgy, aluminum sandwich foam 1. GR Sandvi yaplar kemiklerde ve yetikin aa dallarnda grld gibi tabiatta var olan bir malzeme trdr. Bu noktada tabiatn mkemmelliini gz nne alrsak sandvi yaplarn gerekliliini ve nemini daha iyi anlarz. Bu yaplar genel olarak hafif ekirdek malzemesinin sert iki d tabaka arasna yerletirilmesi ile retilir ve ayn llerdeki yekpare malzemeye gre zgl mukavemeti daha yksektir. zgl mukavemetinin salad arlk kazancnn yan sra ses ve s yaltm, titreim emme, darbe absorbsiyonu ve daha uzun yorulma mr gibi zelliklerin bir ksmn veya hepsini ihtiva edebilir [1,2]. Genel olarak baktmzda bu tr yaplarda minimum malzeme kullanlarak maksimum performans, yapsal optimizasyon prensibi grlmektedir [3]. Sandvi yaplarn i ksmlarnda kullanlan ekirdek malzemesi olarak genelde polimer, metal, aa ve bunlarn eitli ekiller verilmi trevleri kullanlmaktadr. Fakat bu malzemelerden dolay sandvi yaplarn olumsuz ynleri genel olarak; neme duyarl olmalar, yanma direnlerinin dk olmas ve burulma riskinin klasik malzemelerden daha yksek olmas eklinde sralanmaktadr [4]. Bahsedilen olumsuzluklar gelitirilen yeni malzeme trleri ile almaya allmaktadr. Bu konuda iyi bir alternatif olarak baklan metal kpkler akademik olarak youn bir ekilde aratrlan, ksmen sanayi uygulamalar olan ve umut vadeden bir malzeme snfdr.
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Metal kpkler inko, kurun, titanyum, elik gibi eitli metal ve alamlar ile retilebilmekle birlikte dk younluk, yksek korozyon direnci, uygun maliyet ve dier metallere gre kolay retilebilirlik gibi birok stn avantajlar sebebi ile alminyum ve alamlar daha fazla tercih edilmektedir [5,6]. Alminyum kpkler ksaca zetlenecek olursa; tam olarak karakterize edilmemi, dk younluklu ve allmn dnda mekanik, termal, elektrik, akustik zellikler barndran bir malzeme snfdr. Bu malzemeler, enerji absorbsiyonu, s kontrol, yaltm, hafif yaplar gibi eitli alanlarda kullanm potansiyeline sahiptir. Ayrca geri dnml olmalar ve toksik zellik iermemelerinden dolay evreye zararlar yoktur [5,7,8]. Bunlarn yan sra dier malzemelerin kpk yaplar ile mukayese edildiinde; mekanik dayanm, sertlii ve enerji absorbsiyonu polimer kpklerden daha yksektir. Termal ve elektrik iletkenlikleri vardr ve mekanik zelliklerini polimer kpklere gre daha yksek scaklklara kadar srdrebilirler. Ayrca zorlu artlarda polimer kpklere gre daha kararldr. Seramik kpklerin aksine plastik deforme olabilir ve bylece enerji absorbe edebilirler [9]. Alminyum kpk kullanarak sandvi yap retiminde yzey levhalar kpe eitli yntemlerle balanabilmektedir. Bu yntemler kpn trne ve retim yntemine gre deimektedir. Farkl alamlardaki alminyum kpk ve alminyum levha kullanarak sandvi yap retimi, balanma mekanizmalar ynnden temel olarak kprtme esnasnda oluturulan doal balanma (in-situ bonding) ve kprtme sonras ilave balayclar yardm ile yapay balanma (ex-situ bonding) olarak ikiye ayrlabilir [10,11]. Bu yntemlerden ilave arlk iermeme, sya duyarl olmama, kolay geri dnm gibi birok sebeple doal balanma ynteminin kullanlmas daha avantajldr. 2. DENEYSEL ALIMALAR Bahsedilen doal balanma ile alminyum sandvi kpk (AFS) retiminde d tabaka ve kpren malzeme e zamanl stlmaya tabi tutulmaktadr. Bu sebeple alminyum levha ergimeden kprmenin gerekletirilmesi gerekmektedir. Bunun iin izlenen yol kprtlecek alminyumun alamlandrlarak ergime scaklnn drlmesidir. Yaplan almalarda genelde silisyum ve bakr kullanlarak alminyumun alamlar oluturulmaktadr [10-12]. Bu almada saf alminyuma silisyum arlka %7, %14 ve AlSi14e %4,5 bakr ilave edilmi farkl toz karmnn kprtlebilirlii incelenmitir. Ayrca btn alamlara kprtc madde olarak arlka % 0,6 TiH2 katlmtr. Deneylerde toz olarak ECKA firmasndan temin edilen %99,9 saflktaki AS 91/S kodlu alminyum tozu kullanlmtr. Ayrca alminyumu alamlandrmak iin ortalama 63m boyutunda bakr tozu ve 10m boyutunda, %99,9 saflkta silisyum (AEE SI 102) tozu kullanlmtr. Kprtc madde olarak, Aldrich firmasndan salanan - 325 mesh boyutunda ve %98 saflkta TiH2 tozu kullanlmtr. Sandvi yap retimi iin, yzey tabakas olarak piyasada yaygn olarak bulunan ticari saflktaki alminyum plakalar tercih edilmitir. lem basamaklar alttaki resimde (ekil 1) gsterilmektedir.
Sekil 1. Uygulama islem basamaklar
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ekil 1deki ilem basamaklarnda grld gibi numune hazrlama ileminde, nce 1/10000 g hassasiyetinde hassas terazi kullanlarak belirli oranlarda hazrlanan tozlar (a) Turbula marka T2 F tipi eksenli kartrc ile homojen bir dalm elde etmek amacyla kartrlmtr (b). Karm tozlar blok haline getirebilmek iin elik kalplar kullanlarak tek eksenli preslenmi ve 30x50x10 mm boyutlarnda numuneler retilmitir (c). Presleme esnasnda yalayc olarak inko stearat (Zn-55) kullanlm ve pres basnc olarak 600 MPa uygulanmtr. Blok haline getirilmi numunelere 450C de saatlik ksmi sinterleme uygulanmtr (d). Ksmi sinterleme sonras son ilem olarak blok malzemeler 450C de %50 orannda deformasyona uratlmtr (e). Deformasyon sonras bloklar ikiye blnerek yaklak 30x30x5 mm boyutunda kprtlmeye hazr numuneler elde edilmitir. Kprtlmeye hazr numuneler atmosfer ortamnda eitli scaklklarda kprtlmtr. Elde edilen kpk numunelerin 0,0001g hassasiyetindeki younluk lme cihaz kullanlarak Arimet prensibine gre younluklar belirlenmitir. Kpn gzeneklilii (p) aada verilen forml ile kpk younluunun (*) kpn hcre duvarlarn oluturan malzemenin younluuna (s) oranlayarak elde edilmitir [13]. Son karakterizasyon ilemi olarak kpkler kprme dorultularnda kesilmi ve yzeyi klasik metalografik tekniklerle hazrlanan numunelerin, bilgisayar destekli Leica marka mikroskopta ortalama hcre duvar kalnlklar belirlenmitir. 3. DENEYSEL SONULAR Kprmeye hazr numuneler 590C - 710C arasnda eitli scaklklarda en fazla 50 dakika sre ile kprtme ilemine tabi tutulmutur. Kprtme ilemi, frn camndan gzlemlenerek kprmenin ilk safhalar ve kmelerini iine alan, eitli srelerde yaplmtr. Bu kprtme sreleri ierisinde numunelerden elde edilen en dk younluklar aadaki grafikte verilmitir
ekil 2. Farkl alamlarda kprtme scaklnn younlua etkisi Grafikte grld gibi en dk scaklk olan 590C de sadece bakr ilaveli olan karm 50 dakikalk bekleme sonras verilen younluk deerine kadar kprme gstermitir. Ayn scaklkta dier karmlar 50 dakikalk sre ierisinde yeterli kprme gstermemi ve daha fazla bekletilmemitir. AlSi14 alamnda 630C den sonra artan scaklk ile younlukta belirli bir deiimin olmad dier iki alamda ise artan scaklk ile younluun ksmen dt ve sonra tekrar ykseldii grlmektedir. Kpklerin viskoziteleri artan scaklk ile dmektedir ve buda kpn kararlln olumsuz ynde etkilemektedir. Ayrca yine artan scaklk ile kprtme sresindeki bir dakikalk deiiklik kp bariz ekilde etkilemektedir. Yaplan deneylerde ise en fazla bir dakikalk farklar gzlemlenmitir. Sonuta artan scaklk ile younluk deiimleri anlk gzlemlenmedii iin yksek scaklklarda sonularn ksmen yanltc olabilecei ngrlmtr. En dk younluk ise 690C de 9 dakikalk kprtme sonras AlSi7 alamnda grlmtr. Dier alamlarda ise sras ile AlSi14Cu4,5; 670C de 11 dakikada ve AlSi14; 630C de 20 dakikada en dk younluklar elde edilmitir. Sonuta genel olarak grafie baktmzda AlSi7 alaml kpklerde her scaklkta en dk younluun elde edildii grlmektedir. Aadaki ekilde farkl alamn en dk younluklar ve bu younluklara ait makro grntleri verilmitir.
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ekil 3. Farkl alamlardaki kpklerin en dk younluk deerleri ve optik grntleri
ekildeki grntlere baktmzda genel olarak homojen bir gzenek dalm grlmekte birlikte AlSi14 alam dierlerine gre daha dzensiz bir yap sergilemitir. AlSi7 alamnda ise kpn kenarlarnda kk gzenekler olumakla birlikte genelde iyi gzenek dalmna sahiptir. Bakr ilaveli alam ise yaklak her scaklkta iyi bir gzenek morfolojisi gstermitir. Kpklerin greceli younluklarna baktmzda hcre duvarn oluturan malzemenin teorik younluunu belirlemek iin; kp oluturan malzemenin younluu (dk), karm oluturan malzemelerin ktleleri toplamnn (m1+m2+mn) hacimleri (v1+v2+vn) toplamna blnmesi ile elde edilir. Daha sonra greceli younluk ( = */s) ve yzde gzeneklilik [(1- )x100] belirlenir: s = (m1 + m2) / (v1 + v2) d(AlSi7) = 93 + 7 / [(93 / 2,698) + (7 / 2,33)] = 2,66 g/cm3 (AlSi7) = 0,389 / 2,66 = 0,146 Gzeneklilik = % 85,4 d(AlSi14) = 86+14 / [(86/2,698) + (14/2,33)] = 2,64 g/cm3 (AlSi14) = 0,512 / 2,64 = 0,194 Gzeneklilik = % 80,6 d(AlSi14Cu4,5) = 81,5+14+4,5 / [(81,5 / 2,698) + (14 / 2,33) + (4,5/8,92)] = 2,724 g/cm3 (AlSi14Cu4,5) = 0,442 / 2,724 = 0,162 Gzeneklilik = % 83,8 Hesaplamalarda grlecei gibi kpklerin gzeneklilikleri younluklarna paralel olarak deimektedir. Fakat kp oluturan bileenlerin younluklar hesaba katld iin ar bakr tozlar ieren karmn gzeneklilii beklenenden daha yksek kmaktadr. Yani bakr alaml kpk dier numuneler kadar, hatta daha fazla gzeneklilie sahip olsa dahi younluu daha fazla kabilir. Buda younluu yksek alam katklarnn dezavantajdr. Ayrca alminyuma katlan Cu, Si elementine gre tektik scakl daha fazla drmektedir. Fakat tektik noktaya ulamak iin olduka fazla bakr ilavesi gerekmekte (% 33 Cu, 548,2 C) ve bakrn bahsedilen olumsuzluu sebebiyle bu alam cazip olmamaktadr [14]. Son olarak elde edilen kpklerin duvar kalnlklarna bakldnda ise mikroskop altnda hcre duvarlarnn dzgn boyutlu olmamalarndan dolay ortalama duvarlarn ince ve kaln ksmlar ayr olarak llerek verilmitir. Aadaki fotorafta AlSi14 alaml kpn hcre duvarnn mikroskop altndaki grnts verilmitir.
ekil 4. AlSi14 alaml kpn hcre duvarnn mikroskop grnts
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Yaplan lmler neticesinde AlSi7 alaml kpn hcre duvarlar kaln blgelerde 82m, ince blgelerde 57m, AlSi14 alamnda kaln blgelerde 145m ve ince blgelerde 84m ve son olarak AlSi14Cu4,5 alamnda ise kaln ksmlarda 295m, ince ksmlarda ise 125m ve olarak belirlenmitir. Eit arlkl numuneler iin artan hcre duvar kalnlnn azalan hcre duvar miktarn ve bu da artan gzenek boyutunu gstermektedir. Yani ortalama gzenek boyutlar kkten bye; AlSi7, AlSi14 ve AlSi14Cu4,5 olarak sralanabilir. Yaplan dier akademik almalar da bu sonucu dorulamaktadr [15]. 4. SONU ve NERLER Yaplan almalar neticesinde farkl alamn da 630C civarnda yeterli kprme gsterdii gzlemlenmitir. Bu da her alamn alminyum levha kullanarak kprtme esnasnda sandvi kpk retiminde kullanlabilecek yeterlilikte olduunu gstermektedir. En dk kprme scakln ve en iyi gzenek morfolojisini AiSi14Cu4,5 alam gstermitir. AlSi7 alam da olduka iyi sonular vermi ve en dk younluk bu alamdan elde edilmitir ki zaten birok akademik almada bu alam tercih edilmitir [10,11,16]. AlSi14 alaml kpk ise ok iyi sonular vermemekle birlikte kullanlabilecek niteliktedir. KAYNAKLAR 1. K.P. Jackson, J.M. Allwood, M. Landert, Incremental forming of sandwich panels, Journal of Materials Processing Technology, 114 2008. 2. Sandwich Data Sheet, Alulight international GmbH., Ranshofen, 2007. 3. S. Herrmann, P. C. Zahlen, and I. Zuardy, Sandwich Structures 7, Netherlands, Airbus Deutschland GmbH, 1326, 2005. 4. D. Gay, S. V. Hoa, S. W. Tsai, Composite Materials Design And Applications, United States of America, CRC Press, 2003. 5. M.F. Ashby, A.G. Evans, N.A. Fleck, L.J. Gibson, J.W. Hutchinson and H.N.G. Wadley, Metal Foams: A Design Guide, Boston, Butterworth-Heinemann 1, 2000. 6. J. Banhart, J. Baumeister, M. Weber, Powder Metallurgical Technology for the Production of Metallic Foams, in Conf. Rec. 1995 European Conference on Advanced PM Materials, 201208. 7. R. Montanini, Measurement of strain rate sensitivity of aluminium foams for energy dissipation, International Journal of Mechanical Sciences, 47: 2642, 2005. 8. J. Vogel, J. Keller, A. Sviridov, H.J. Feige, K. Kreyssig, J. Auersperg, P. Plass, H. Walter, Characterization of Strength Behavior of Aluminium Foam Sandwiches Under Static Load, Strain, 19, 2009. 9. L. P. Lefebvre, J. Banhart, D.C. Dunand, Porous Metals and Metallic Foams: Current Status and Recent Developments, Advanced Engineering Materials 10 (9): 775787, 2008. 10. J. Banhart, H. Seeliger, Aluminium foam sandwich panels: manufacture, metallurgy and applications, Advanced Engineering Materials, 9: 793802 2008. 11. J. Banhart, H. Stanzick, L. Helfen, T. Baumbach, K. Nijhof, Real-time Xray Investigation of Aluminum Foam Sandwich Production, Advanced Engineering Materials, 6: 407411 2001. 12. D. Schwingel, H.W. Seeliger, C. Vecchionacci, D. Alwes, J. Dittrich, Aluminium foam sandwich structures for space applications, Acta Astronautica, 61: 326330 2007. 13. Y. Mu, G. Yao, H. Luo, Anisotropic damping behavior of closed-cell aluminum foam, Materials and Design, 31: 610612 2010. 14. H. Baker, ASM Handbook Volume 3, USA, ASM International, 3. Ed. 2.44, 2.51 1999. 15. H. Demirta, Toz metalurjisi yntemi ile alminyum esasl kpk sandvi yap retimi, Yksek Lisans Tezi, Gazi niversitesi Fen Bilimleri Enstits, Ankara, 2010. 16. H. Yu, G. Yao, X. Wang, Y. Liu, H. Li, Sound insulation property of AlSi closed-cell aluminum foam sandwich panels, Applied Acoustics, 68: 15021510 2007.
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MEKANK ALAIMLANMI Al2O3 TAKVYEL AlSi7Mg0,6 ESASLI TOZLARDAN METALK KPK RETM VE ZELLKLERNN NCELENMES
Yasin PELT*, Mehmet TRKER**
** * Gazi niversitesi, Fen Bilimleri Enstits, Metal Eitimi Blm Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, mturker@gazi.edu.tr
ZET Bu almada Al2O3 takviyeli Al esasl metalik kpk retimi iin Al, Si, Mg ve TiH2 tozlar 30 dakika sreyle eksenli kartrma yapabilen turbula cihaznda kartrlmtr. Daha sonra Szegvari tip mekanik alamlama cihaznda, 1/10 toz bilye orannda ve argon atmosferi altnda, 350 dev/dk hzda, 15, 30, 60, 120 dakika srelerde MA yaplmtr. MA yaplm tozlar 400 MPa basn altnda kalp ierisinde tek ynl olarak sktrlmtr. Sktrlan numuneler 550C scaklkta ekstrzyon ileminden geirilmitir. Daha sonra 500C de haddelenerek kprmeye hazr levha eklinde numuneler elde edilmitir. Bu numuneler 690 C ve 7 dk sreyle kprtme ilemine tabi tutulmutur. Kpk malzemeler mikro ve makro boyutta incelemeler yaplm ve MA sresine bal olarak kpk malzemelerin younluunda artma, 15 ve 60 dk MA yaplm tozlardan elde edilen kpk malzemesinin gzenek morfolojisinde daha homojen bir dalm gsterdii grlmtr. Anahtar Kelimeler: Mekanik Alamlama, Al Kpkler, Toz Metalurjisi
Production of metallic foam from mechanically alloyed Al2O3 reinforced AlSi7Mg0.6 powders and investigation of its properties
Abstract In order to produce Al2O3 reinforced Al based metallic foam Al, Si, Mg and TiH2 powders were mixed in a three dimensional turbula for 30 min and then mechanically alloyed in a Szegvari type attritor for 15, 30, 60, 120 minutes with the powder ball ratio of 1/10 at 350 rev/min in Ar atmosphere. Powders were compacted in a steel die by using a uniaxial press at 400 MPa pressure. Compacted powders were extruded at 550C and then hot rolled at 500C to produce foamable precursor sheet. Sheets were then subjected to foaming process at 690 C for 7 min. Macro and micro examinations were carried out on the foamed materials. It was found that higher mechanical alloying duration resulted in the formation of denser foam material however, foam produced from 30 and 60 minutes mechanically alloyed powders showed more homogeneous pore morphology. 1. GR Teknolojinin ilerlemesi ile birlikte malzeme biliminde nemli gelimeler yaanmaktadr. Malzeme biliminin son gelimeleri arasnda metalik kpkler nemli bir yer tutmaktadr. Metalik kpkler, gzenekli yapya sahiptir ve bu yap retim esnasnda baz ilemler uygulandktan sonra ortaya kar. Doal kpk ile hibir ilgisi olmamasna ramen grnm ve baz zelliklerinden dolay metalik kpk diye adlandrlr [1].
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Toz metalurjisi (TM) yntemiyle Al esasl metalik kpk retimi toz haldeki Al, kprtc madde (genellikle TiH2) ve dier alam elementlerinin preslenmesiyle elde edilen kompakt yapnn ergime scaklnn zerinde bir scakla kadar stlmasyla devam eder. Sv metal ierisinde TiH2in ayrmasyla gzenek ekirdekleri olumaya balar ve zamana bal olarak hcresel yaplar oluturur [2]. Hcresel malzemeler arasnda seramik, metalik ve polimer gibi malzemeler saylabilir. Metalik kpkler, mekanik zelliklerin iyi olmasndan dolay gnmzde artan neme sahip malzemelerdir [3]. Metalik hcreli malzemelerin yapsal kullanm alanlar arasnda otomotiv, demiryolu ve inaat endstrileri, uzay aralar, gemi ve spor malzemeleri yapm ve biyomedikal uygulamalar; ilevsel kullanm alanlar arasnda ise filtreleme ve ayrma, s dntrc, soutma sistemleri, elektrokimyasal uygulamalar, su artma, sv muhafaza ve iletimi gibi uygulamalar saylabilir [4]. Fark zelliklere sahip malzemelerin iyi zelliklerini bir araya getirerek stn zelliklere sahip kompozit malzemeler retilir. retimdeki bu eitlilik retim yntemlerine de yansmaktadr. Mekanik alamlama (MA) yntemi ile metalik kpk retimi bu konuya rnek olarak verilebilir. MA bir kat toz retim metodu olup, genellikle yksek enerjili deirmenler kullanlarak yaplr. MA deirmenine genellikle biri kolay sekilenebilen (snek) metal tozlar ve dierleri krlgan, metal veya seramik tozlar konularak alamlama/tme ilemi yaplr. Atritr tipi MA deirmenleri genellikle su soutmaldr ve tme srasnda oksitlenmeyi minimuma indirmek iin Ar, H veya N gaz kullanlr [5]. Bu almada MA yntemiyle homojen yapda Al2O3 takviyeli alminyum esasl metalik kpk retimi gerekletirilip MA sresinin kpk malzemenin gzenek yapsna etkisi incelenmitir. 2. DENEYSEL ALIMA 2.1. Malzeme ve Yntem Bu almada alminyum kpk malzeme retmek iin %99,7 saflkta Al, %7 Si, %0,6 Mg, %2 Al2O3, %0,8 TiH2 tozlar kullanlmtr. Tozlar turbola cihaznda homojen bir karm elde etmek amacyla 30 dakika sreyle kartrlmtr. Daha sonra Szegvari tip atritrde 1/10 toz bilye orannda ve Ar atmosferi altnda, 350 dev/dk hzda 15, 30, 60, 120 dk srelerde MA ilemine tabi tutulmutur. Tozlar daha sonra kalp ierinde 400 MPa basn altnda tek ynl olarak sktrlmtr. Sktrlan numuneler 550 Cde 1/3 orannda ekstrzyona tabi tutulmu ve 500 Cde haddelenerek levha halinde kprtlmeye hazr numuneler elde edilmitir. Bu numunelerin kprtme ilemi 690 Cde ve 7 dk sreyle gerekletirilmitir. Elde edilen kpk malzemelerin makro ve mikro yap incelemeleri yaplmtr. Yaplan almalar sonucunda 15 dk MA yaplm malzemenin gzenek yapsnn dierlerine gre daha homojen dalm sergiledii belirlenmitir.
3. DENEY SONULARI VE TARTIMA 3.1. MA Sresinin Lineer Genilemeye Etkisi MA sreleri ve buna bal olarak kpk malzemelerin lineer genilemesi ekil 1de grlmektedir. 15 dk MA yaplm numune %226 lineer genleme oranyla en fazla lineer genlemeye sahip kpk malzemesi olduu grlmektedir. Karm tozlar 30 dk MA yapldnda ise kpk malzemenin lineer genilemesi belirgin bir ekilde azalarak %132 ye geriledii grlmektedir. MA sresi artrlp 60 dk ya karldnda ise kpk malzemenin lineer genilemesi %193e kt grlmektedir. 120 dk MA yaplm tozlardan elde edilen kpk malzemenin lineer genilemesinde tekrar bir d olduu ve %165 e geriledii grlmektedir. Bunun muhtemel sebebinin MA sresine bal olarak deien toz tane boyutu olduu dnlmektedir. Ark ve arkadalar yaptklar almada MA iin kullandklar Al ve Al4C3 tozlarn 0.5, 1, 2.5, ve 7.5 saat elik bilye ortamnda MA yapmlar ve 0,5 saatlik MA da ortalama toz boyutunun 150 m den 82 m ye dtn, 1 saatlik MA da ise ortamn ssndan kaynaklanarak toz boyutunda hzl byme gstererek 172mye ktn ve 2.5 saatlik MAda ise toz boyutunun 53 mye dtn belirtmilerdir [6]. Deien toz boyutlar presleme sonras elde edilen blok numunenin gzeneklilik orann etkileyecektir. Numunelerdeki gzeneklilik oran, kprme esnasnda kprtc maddeden ayran hidrojen gaznn kamasna neden olacaktr. Dolaysyla MA sresine bal olarak deien toz boyutunun lineer genilemeyi etkiledii dnlmektedir. Sarta ve arkadalar btn mekanik toz retim tekniklerinde olduu gibi mekanik alamlamada da kirlilik sorunu oluabileceini belirtmilerdir [7]. MA sresinin artmasna bal olarak kpk malzemelerin lineer genilemesinde greceli bir azalma olduu ekil 1 de grlmektedir. Burada lineer genilemedeki azalmann malzemedeki kirlenmelerden kaynaklanm olabilecei dnlmektedir.
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ekil 1. Kpk numunelerde zamana bal % lineer genileme oran 3.2. MA Sresinin Younlua Etkisi MA sresinin younluk zerindeki etkisi ekil 2de grlmektedir. 15 dk MA yaplm tozlara ait kpk malzemenin younluunun 0,818 g/cm3 lk deerle en dk younlua sahip malzeme olduu grlmektedir. 30 dk MA ile retilmi kpk malzemenin younluu 1,144 g/cm3 lk deere kt ekil 2de grlmektedir. Buradaki ani younluk artnn MA esnasnda kirlenmeler ve TiH2deki ayrmalar olabilecei dnlmektedir. 60 dk MA ile retilmi tozlara ait kpk malzemenin younluu ise 0,914 g/cm3e dt grlmektedir (ekil 2). 120 dklk MA ile retilmi tozlara ait kpk malzemenin younluu ise 1,014 g/cm3 olduu grlmektedir. Kpk malzemelerdeki younluk ve lineer genilemedeki deiimlerin aklanmasnda toz malzemelerin MA esnasndaki zamana bal olarak etki eden baz kuvvetleri dikkate almak gereklidir. Suryanarayana, MA esnasnda oksit ve karbrlerle glendirilmi alamlarn yksek enerjili deirmen ierisinde, srekli bir deformasyon, krlma, souk kaynak, tekrar krlma ve ardndan kaynaklanma aamalarn ieren homojen dalml, kimyasal ya da sl ilem gerektirmeyen kat hal reaksiyonu olduunu belirtmitir (8). MA esnasnda meydana gelen bu deiimlerin, kpk malzeme zerinde gsterdii younluk ve lineer genilemedeki dalgalanmalarn bu ekilde olmas yadrganamaz.
ekil 2. MA sresine bal younluk deiimi 3.3. Kpk Malzemelerin Makro Yap ncelemeleri 15 dk, 30 dk, 60 dk, 120 dk MA yaplm takviye elemanl tozlara ait kpk malzemelerin makro gzenek yaps ekil 3te grlmektedir. ekil 3.aya bakldnda, kpk malzemenin gzenekleri ksmen iri ve hcre duvarlarnn ise kaln olduu grlmektedir. Bu da gzenekler yap zerinde homojen bir dalm sergilediini gstermektedir. ekil 3.b ye bakldnda malzemenin gzenek yapsnda homojen dalm olmad, gzeneklerin iri, gzeneklerde bir ynlenme ve hcre duvarlarnda girinti ve kntlarn hakim olduu grlmektedir. Malzemedeki bu hzl deiimin nedeni MA esnasndaki toz tane boyutundaki deiimler, kirlenmeler, TiH2 tozlarndaki znmelerin ve
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belirli bir ksmnn ise atritr eperine yapmas etkili olduu dnlmektedir. 60 dk lk MA yaplm tozlardan elde edilen kpk yap ekil 3.cde grlmektedir. Burada malzemenin gzenek saysnda greceli olarak bir art, gzeneklerinde klmeler ve hcre duvarnda incelme olduu grlmektedir. Asavavisithchai ve arkadalar kompakt malzeme stlmaya baladnda TiH2 deki ayrmalar ilk nce ekirdek gzenekleri ve bu ekirdek gzenekleri birleerek hcresel yapy oluturduunu belirtmitir [2]. Burada gzeneklerin ksmen kk ve ok sayda olmas yzey gerilim kuvvetlerinin ve Al2O3 takviye elemannn hcre ekirdeklerin byyerek birletirmesinde snrlayc kuvvet olarak etki ettii dnlmektedir. ekil 3.dye bakacak olursak kpk malzemelerde istenen homojen dalml hcre morfolojisinden uzaklat grlmektedir. Gzenekler baz blgelerde iri yapda, baz blgelerde ise kk olduu grlmektedir.
ekil 3. MA yaplm numunelere ait makro gzenek yaplar. a) 15 dk MA, b) 30 dk MA, c) 60 dk MA, d) 120 dk MA
3.4. Mikro Yap ncelemesi MA yaplm tozlardan elde edilen kpk malzemelerin SEM grntleri ekil 4te grlmektedir. ekil 4.ada 15 dk MA yaplm tozlardan elde edilen kpe ait hrce duvar grlmektedir. Hcre duvarnn kaln olmas nedeniyle hcre duvar zerinde kk gzeneklemelerin olduu grlmektedir. MA sresi 30 dkya ulatnda ise kpk malzemenin hcre duvarnda girinti ve kntlarn hakim olduu ve homojen bir gzenek yapdan uzaklald ekil 4.bde grlmektedir. MA esnasnda toz malzemelere zamana bal olarak plastik deformasyon, krlma ve souk kaynak kuvvetlerinin etki ettii bilinmektedir. Burada ise malzemeler henz plastik deformasyon aamasnda olduu ve bu etkinin kpk malzemenin homojen gzenek yapsndan uzaklatrd dnlmektedir. 60 dk MA yaplm tozlardan elde kpn hcre duvar grnts ekil 4.cde grlmektedir. Burada hcre duvarnda belirgin bir ekilde incelme olduu grlmektedir. ekil 4.d de ise 120 dk MA yaplm tozlardan elde edilen kpk malzemenin hcre yaps grlmektedir. Burada hcre duvar zerinde gzeneklemelerin olduu ve hcrelerin irili ufakl olduu grlmektedir. Hcre duvarnda gene bir incelme olduu ve girinti kntlarn hakim olduu grlmektedir. Bu duruma malzemenin kprme esnasnda yzey gerilimi kuvvetlerinin dengesiz bir etki ettii dnlmektedir.
ekil 4. Farkl srelerde MA yaplm tozlardan elde edilen kpk malzemelerin SEM grnts, a) 15 dk, b) 30 dk, c) 60 dk, d) 120 dk
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3.5. Sonular Bu almada %2 Al2O3, takviyeli Al esasl Al-Mg-Si tozlarna %0,8 orannda TiH2 tozlar kartrlarak nce turbolada daha sonra farkl srelerde yksek enerjili atritrde MA ilemine tabi tutulmutur. Tozlar daha sonra presleme, sinterleme, ekstrzyon ve scak haddelemenin ardndan kprtme ilemine tabi tutulmu ve aadaki sonular elde edilmitir. MA sresinin kpk malzemenin younluu, gzenek dalm ve gzenek duvar kalnlna etki ettii grlmtr. MA sresi arttka younlukta greceli olarak bir d olduu ve 30 dakikalk alamlamann daha etkili olduu grlmtr. Kpk malzemenin gzenek boyutu ve gzenek duvarna bakldnda ise MA sresi arttka gzeneklerin kld ve gzenek duvarnn inceldii tespit edilmitir. Bu durum 60 ve 120 dk MA ilemine tabi tutulmu numunelerde daha belirgin olarak ortaya kmtr. KAYNAKLAR 1. Yavuz, .,Metalik Kpk Malzemeler ve Uygulama Alanlar, Tat Teknolojileri Elektronik Dergisi (TATED), Cilt: 2, No: 1, (49-58) 2010 2. S., Asavavisithchai, A.R. Kennedy., The effect Of Mg Addition On The Stability Of AlAl2O3 Foams Made By A Powder Metallurgy Route, Scripta Materialia, 54 13311334 (2006) 3. Pelit, Y., Ayata, A., Kurt, A., Trker, M., Toz Metal Al Kpk Malzemelerin Kprtme ncesi Saplama Kayna ile Birletirilmesi 6. Uluslar Aras Teknolojiler Sempozyumu, Elaz, 2011 4. Baspnar, M. S., Yurtcu, S., Metalik Kpk Malzemelerin Mekanik zelliklerini Belirlemede Kullanlan Matematiksel Modeller, Makine Teknolojileri Elektronik Dergisi, Cilt: 8, No: 1, 2011 (69-78) 5. Kaya, H., Spex Tip Mekani Alasmlama Cihaznn Tasarm, malat Ve gtme Kabiliyetinin incelenmesi, 5. Uluslararas leri Teknolojiler Sempozyumu (IATS09), 13-15 Mays 2009, Karabk, Trkiye 6. Ark, H., Trker, M., Sarta, S., Mekanik Alamlama le Alminyum Matrisli Alminyum Karbr (Al4C3) Kompozit Malzeme retimi 2. Ulusal Toz Metalurjisi Konferans, Ankara, 1999 7. Sarta. S., Trker, M., Durlu, N., Toz Metalurjisi Ve Parackl Malzeme lemleri, Trk Toz Metalurjisi Yaynlar, 05, Ankara, (2007) 8. Suryanarayana, C., Mechanichal Alloying And Milling, Progress in Materials Science, 46, (2001)
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ALMNYUM TOZ TANE BOYUTUNUN KPK oluumuna ETKSNN NCELENMES

Salim ahin*, Hlya DURMU**, Nilay YKSEL*
*
Celal Bayar niversitesi, Mhendislik Fakltesi, Malzeme Mhendislii Blm, Muradiye-Manisa. salim.sahin@bayar.edu.tr, nilay.yuksel@bayar.edu.tr ** Celal Bayar niversitesi, Turgutlu MYO, Makine ve Metal Teknolojileri Blm, Turgutlu-Manisa. hulya.kacar@bayar.edu.tr ZET
Bu almada, farkl boyutlara sahip alminyum tozlar kullanlmtr. Toz metalurjisi yntemi ile %98,23 saflkta alminyum tozuna %1, 5 ve 10 SiC takviye eleman ve kprtc madde olarak ise TiH2 tozu %0.5, 1, 1.5, 2 oranlarnda eklenerek kpk numuneler retilmitir. Alminyum tozu, takviye elaman ve kprtc madde tozlar 3 saat sreyle kartrlm ve daha sonra sktrma, n stma, deformasyon ve kprtme ilemlerine tabi tutulmutur. retilen kpkte alminyum tozu tane boyutuna bal olarak uygun kprtme sresi, kprme miktar, younluk ve gzenek dalm aratrlmtr. Anahtar Kelimeler : Al Kpk, SiC, TiH2, Al toz tane boyutu.
INVESTIGATION OF THE EFFECT OF ALUMINIUM POWDER PARTICLE SZE ON FOAM FORMATION

Abstract In this study, aluminium powders in different sizes have been used. Foam samples have been produced by powder metallurgy method adding 1,5% and 10% SiC reinforcing member and TiH2 as foaming agent at the rate of 0,5, 1, 1,5, 2 % in aluminium powder at 98,23 % grade. Aluminium powder, reinforcing member and foaming agent powders have been mixed for 3 hours and then subjected to pressing, pre-heating, deformation and foaming processes. On produced foam, adequate foaming time, foaming gauge, density and pore distribution depending on granule size of aluminium powder have been investigated. Keywords: Al Foam, SiC, TiH2, Al powder particle size 1.Giri Metalik kpkler, mekanik zelliklerinin iyi olmasndan dolay gnmzde byk bir neme sahiptir. zellikleri arasnda, enerji emebilme kabiliyetinin yksek olmas, dk arlk, sl izolasyon, titreim azaltma ve kimyasal szme saylabilir [1]. Daha ok alminyum esasl metalik kpkler, eitli mhendislik uygulamalarnda kullanm alan bulabilen malzemeler olarak son yllarda olduka ilgi ekmektedir. Alminyum kpkler, darbe enerjisini plastik enerjiye dntrebilirler ve birok metalden daha fazla enerji absorbe edebilirler. Tpler ierisine dolgu malzemesi olarak konulduklarnda emilen toplam enerji hafifliin ve mukavemetin bir arada bulunmas gereken otomotiv, uzay sanayi, demiryolu tamacl ve asansr gibi alanlarda kullanlmaktadr [2]. zellikle alminyum kpkler, kapal hcre yaps ve ok hafif olmas ile gze arpmaktadr. Bundan dolay ses ve enerjinin absorbesinde alminyum kpkleri fonksiyonel olarak kullanlmaktadr [3]. retim yntemleri arasnda ergiyik ierisine gaz enjekte edilmesi, ergiyik ierisine kprtc madde ilavesi ve toz metalurjisi yntemleri saylabilir. Toz Metalurjisi (TM) yntemi, metal kpklerin retimi iin en yaygn kullanlan
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yntemlerden biridir ve bu alanda youn almalar yaplmaktadr. TM yntemiyle, bilinen basit kpk retiminin yan sra sandvi kpk, kresel kpk, ii bo kalp veya profil ierisinde kprtme yaplabilmektedir [4]. TM ynteminde metal tozlar, kprtc madde (genellikle TiH2) ile kartrlr ve preslenir. Kprtme ilemi srasnda scakln artmasyla yap ierisindeki kprtc madde ayrr ve gaz kna neden olur. Ayrma ilemi esnasnda yksek scaklktaki metalde genleme yani kprme meydana gelir [5]. Alminyum iin TiH2 tozu genellikle % 0.6-1 arasnda kullanlmaktadr [6]. Bu almada, alminyum kpk retiminde kullanlan alminyum tozunun tane boyutunun kpklemeye olan etkisi incelenmitir. 2. DENEYSEL MALZEME VE METOD 2. 1. Malzeme Bu almada, 53 m, 100 m ve 200 m altndaki boyutlarda %98.23 saflktaki alminyum tozlar (izelge 1), 53 mluk SiC (izelge 2) ve kprtc madde olarak TiH2 tozlar kullanlmtr. izelge 1. Alminyum Tozunun Bileimi (%). Al 98.23 Fe 0.0056 MgO 1.52
izelge 2. SiC Bileimi (%). SiC 97.80 2.2. Deneysel Metot 2.2.1. Eleme, kartrma ve presleme Alminyum tozlar elenerek 0-53 m, 53-100 m, 100-200 mluk, SiC tozlar elenerek 0-53 mluk tozlar elde edilmitir. Al, SiC ve TiH2 den oluan 20 deneme ve 36 esas olmak zere 56 karm (izelge 3) 1/1000 g hassasiyetindeki bir teraziyle (ekil 1) tartlarak homojen bir dalmn oluturulmas iin 3 saat sreyle kartrlmtr. Hazrlanan karmlar 10 mm apl silindir kalba aktarlm, 600 MPa basn altnda sktrlarak 10x10 mm silindirik numuneler (ekil 2) elde edilmitir. Si 0.65 SiO2 0.59 Fe 0.12 C 0.29 Dierleri 0.55
ekil 1. Karm hazrlama
ekil 2. Sktrlm numuneler
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izelge 3. Karmlar ve miktarlar. Alminyum Tane Boyutu Karm Miktarlar 0-53 m 53-100 m 100-200 m Al (%) SiC (%) TiH2 (%) A2 B2 C2 98.5 1 0.5 A4 B4 C4 94.5 5 0.5 A5 B5 C5 89.5 10 0.5 A8 B8 C8 98 1 1 A10 B10 C10 94 5 1 A11 B11 C11 89 10 1 A14 B14 C14 97.5 1 1.5 A16 B16 C16 93.5 5 1.5 A17 B17 C17 88.5 10 1.5 A20 B20 C20 97 1 2 A22 B22 C22 93 5 2 A23 B23 C23 88 10 2 2.2.2. n Istma ve Deformasyon lemi Elde edilen silindirik numuneler 550 oC scaklkta 3 saat sreyle n stma ilemine tabi tutulmutur (ekil 3). Ardndan %50 orannda preste sktrlarak deforme edilmitir (ekil 4).
ekil 3. n stma uygulanmas
ekil 4. Deformasyon uygulanmas 2.2.3. Kpkletirme lemi Sktrlarak %50 deforme edilmi olan numunelerden, deneme numuneleri en iyi kprme sresinin belirlenebilmesi iin 700 oC de 90 dakikaya kadar bir n teste tabi tutulmutur. 20 numune (ekil 5) belli periyotlarla frndan alnmtr. kan sonular dorultusunda 36 numune 700 oC de 35 dakika bekletilmi ve frndan alnarak havada soutulmutur.
ekil 5. Deneme numuneleri
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3. DENEY SONULARI VE TARTIMA Toz metalurjisi ile alminyum kpk retiminde TiH2 kprtc madde miktar (%0.5, 1, 1.5, 2), SiC oran (%1, 5, 10) ve alminyum tane boyutu (0-53 m, 53-100 m, 100-200 m) gibi farkl parametre kullanlmtr. n stma scakl 550 oC, toz presleme basnc 600 MPa, deformasyon miktar %50, kprtme scakl 700 oC ve kprme sresi 35 dakika olarak sabit tutulmutur. 3.1. Deneme Numunelerinde Kpkleme ve Gzenek Dalm Sonular %98.23 Al, %2 SiC ve %1 TiH2 den oluan deneme numuneleri kprme sresinin tayin edilebilmesi amacyla kullanlmtr. 20 numune 700 oC de, 2.5 dk, 5 dk, 7.5 dk, 10 dk, 15 dk, 20 dk, 25 dk, 30 dk, 35 dk, 40 dk, 45 dk, 50 dk, 55 dk, 60 dk, 65 dk, 70 dk, 75 dk, 80 dk, 85 dk ve 90 dk da frndan alnarak kpklemeleri incelenmitir. En iyi gzenek yapsnn ve en dk younluun 35. dakikadaki numunede olduu belirlenmitir (ekil 6-7). Daha az ve fazla srelerde numunelerde kpkleme az yada dzensiz olmutur. Artan sre ile numunelerde kabarma olmu ama daha sonra kmeler gereklemitir.
ekil 6. Deneme numunelerinin gzenek dalm
ekil 7. Deneme numunelerinin younluk grafii 3.2. Kpk Numunelerin Kpklemeleri ve Gzenek Dalm Sonular Hazrlanan numuneler 700 oC de 35 dakika kprmeye tabi tutulup gzenek dalmlar incelenmitir (ekil 8-11).
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ekil 8. 35 dk kpren numuneler
ekil 9. A numunelerinin gzenek dalmlar
ekil 10. B numunelerinin gzenek dalmlar
ekil 11. C numunelerinin gzenek dalmlar
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Arimed prensibine gre yaplan younluk lmnde, artan kprtc madde miktaryla younluun azald tespit edilmitir. Bunun sebebinin TiH2 miktarnn artmasyla gzenek miktar artm, younluk azalmtr. Alminyum toz tane boyutu kk olduunda, daha dk younluklar elde edilmitir. SiC miktarnn artmasyla younluklar artmtr (ekil 12).
(a)
(b)
(c)
ekil 12. Alminyum toz tane boyutuna gre Al kpklerin younluk grafikleri (a) 0-53 m (b) 53-100 m (c) 100-200 m. 4. SONULAR 1. Alminyum toz tane boyutu arttka kpkleme azalm, younluk artmtr. Alminyum toz tane boyutunun artmasyla younluklar birbirine yakn elde edilmitir. En dk younluk 53 um altndaki boyuta sahip alminyum tozunda %2 TiH2 eklenmi numunede elde edilmitir. Alminyum toz tane boyutu arttka younluklarda ok az bir artma meydana gelmitir. 2. %50 deformasyon uygulamas ile numunelerde atlak olumadan ekil deiimi salanmtr. 3. En uygun kprme sresi 35 dk olarak bulunmutur. Gzenek dalm homojene yakndr. Kre formunda elde edilmi tek numunedir. 4. Kpklemenin fazla olduu numunelerde younluk dktr. TiH2 miktar arttka younluk azalmtr. 5. SiC ve TiH2 oran %1 olan numunelerde uygun kpkleme yaps elde edilmitir. Gzenek dalmnn en iyi olduu numune TiH2 oran %1 olan numunedir. KAYNAKLAR 1. Seitzberger, M., Rammerstorger, F.G., Degischer, H.P., Crushing of axially compressed steel tubes filled with aluminium foam, Acta Mechanica, 125: 95-103, (1997). 2. Davies, G.J., Zhan, S., Review metallic foams, their production, properties and applications, J.Mat. Sci., 18: 1899-1911, (1983). 3. Banhart, J., Manufacturing Routes for Metallic Foams, Journals of Materials 52(12): 22-27, (2001). 4. Trker, M., Toz Metalurjisi Yntemi le Alminyum Kpk retimi, 5. Uluslararas leri Teknolojiler Sempozyumu (IATS09), 13-15 Mays 2009, Karabk, Trkiye. 5. Yavuz ., Bapnar M. S., Bayrakeken H., Metalik Kpk Malzemelerin Tatlarda Kullanm, Tat Teknolojileri Elektronik Dergisi (TATED), (3), 43-51, 2009. 6. Kennedy, A.R., The Effect of TiH2 Heat Treatment on Gas Release and Foaming Al-TiH2 Preforms, Scripta Materilia, 47: 763-767, (2002).
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SiC LAVESNN ALUMIX 231 ESASLI METALK KPN KPRME ZELLKLERNE ETKLER
Uur GKMEN, Halil KARAKO, Hanifi NC, Mehmet TRKER Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar 06500 Ankara, mturker@gazi.edu.tr; Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar 06500 Ankara, ugurgokmen@gazi.edu.tr ZET Bu almada, TM yntemi ile n alaml Alumix 231 (Al-Cu %2,5-Mg %0,5Si %14 ) tozu ierisine %1 orannda TiH2 ve farkl oranlarda (% 3-6-9-12 ) SiC tozu ilave edilerek 3 boyutlu turbula marka kartrc ile 30 dakika kartrlmtr. Karm tozlar kalp ierisinde tek ynl basn altnda preslenerek toz metal blok numuneler haline getirilmitir. Elde edilen blok numuneler 690C scaklkta kprtme ilemine tabi tutulmutur. Kprtme ileminden sonra elde edilen metal matrisli kompozit kpkler atmosfer ortamnda soumaya braklmtr. retilen SiC takviyeli metal matrisli kompozit kpe takviye elemann miktarnn etkisi aratrlmtr. Elde edilen SiC takviyeli metalik kpklerin gzenek yaplar ve dalm, lineer genileme oranlar, younluu ve gzenek duvar kalnlklar incelenmitir. Yaplan alma sonucunda parack miktarnn artna bal olarak younlukta art ve lineer genilemede azalma gzlenmitir. Anahtar Kelimeler : Metalik Kpkler, Alumix 231, SiC
EFFECT OF THE SiC REINFORCE ADDITION ON THE FOAMABILITY BEHAVIOUR OF ALUMIX 231 BASED METALLIC FOAM
ABSTRACT In this study, %1 TiH2 and various amount of SiC (3, 6, 9 and 12%) particles were added into prealloyed Alumix 231 (Al-Cu 2,5%-Mg 0,5%Si 14% ) powders and mixed in a turbula for 30 minutes. Mixed powders were compacted at unidirectional press to produce blanks. These blanks were foamed at 690C in a furnace and then cooled to room temperature outside the furnace. Effect of reinforcing amount on the behavior of metallic foam was investigated. Pore morphology, pore distribution, linear expansion, density and cell thickness of the SiC reinforced foam was investigated. It was found that high amount of reinforcing element resulted in an increase in density of the foam however, reduced the linear expansion rate. Keywords: Metallic Foams, Alumix 231, SiC 1.GR Metalik kpkler, zellikle alminyum ve alminyum alaml kpkler son yllar da youn olarak ilgilenilen yaplardr. Uygulama alanlar arasnda en nemli olanlar ultra hafif olmalarndan dolay tpler ierisinde ve sandvi yaplar arasnda dolgu malzemesi olarak kullanlmalardr [1-6]. Gzenekli metal malzemelerin yapsal kullanm alanlar arasnda otomotiv, demiryolu ve inaat endstrileri, uzay aralar, gemi ve spor malzemeleri yapm ve biyomedikal uygulamalar; ilevsel kullanm alanlar arasnda ise filtreleme ve ayrma, s dntrc, soutma sistemleri, elektrokimyasal uygulamalar, su artma, sv muhafaza
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ve iletimi gibi uygulamalar sylenebilir [7]. Alminyum kpkler zellikle arpma olaylarnda yksek enerji snmleme zellii, yksek basma dayanm ve yksek rijitlik gibi mekanik zellikleri bir arada bulundurmas ile bilinirler [8]. ok hafif olmalar nedeniyle zellikle uak, uzay arac ve gemiler gibi kritik yaplarn uygulamalarnda ekici hale gelmilerdir [9]. Kpk malzemenin mekanik zelliklerini artrmak amacyla parack takviyeli kpk retimi yaplmaktadr. Ergiyik ierisine seramik paracklarn ilave edilmesi, sv metalin viskozitesini ve kpn yzey gerilmesini deitirmektedir. Bu balamda ergiyik haldeki kpn kararllnn bu zelliklere bal olarak gelitirilebildii bilinmektedir [10]. Kpn kararln artrmak ve gzenek yapsn dzenlemek amacyla ierisine SiC, Al2O3 gibi eitli paracklar katld bilinmektedir [11]. Yaplan almada, toz metalurjisi yntemiyle, n alaml Alumix 231 esasl deiik oranlarda (% 3-6-9-12) SiC takviyeli kompozit kpk retimi gerekletirilmitir. lave edilen takviye elemann kpk yapnn gzenek morfolojisine, lineer genilemeye ve younlua etkisi aratrlmtr. SEM yardmyla gzenek parack yzey ilikisi incelenmitir. 2. MATERYAL VE METOT Deneysel almalarda % 99,9 saflkta Alumix 231 (2,5 Cu, 0,5 Mg, 14 Si) tozu ierisine arlka % 3, 6, 9 ve 12 oranlarnda takviye elaman (SiC) ve % 1 TiH2 kprtc madde katlarak 30 dakika sreyle boyutlu turbola ierisinde kartrlmtr. Elde edilen karm tozlar kalp ierisinde tek ynl basn altnda souk izostatik preslenerek numuneler elde edilmitir. Numuneler koruyucu gaz uygulanmadan frn ierisinde 550 Cde 4 saat bekletilmitir. Daha sonra frn ierisinden alnan numuneler tamamen souma olmadan yaklak % 55 orannda deforme edilerek 690 C kprtme scaklnda yaklak 10 dakika sreyle kprtme ilemine tabi tutulmutur. Kprtlm metal matrisli kompozit rnler frn ierisinden karlarak atmosfer ortamnda soumaya braklmtr. Kprtc madde miktar (%1 TiH2) ve kprtme scakl (690C) sabit tutularak deiik oranlarda takviye eleman (% 3, 6, 9, 12 SiC) ilave edilerek n alaml Alumix 231 esasl metalik kpkler retilmitir. retilen metal matrisli kompozit kpklerde takviye elemann (SiC) miktarnn gzenek boyutuna, gzenek yapsna, younlua, lineer genileme oranlarna etkileri aratrlm ve SEM yardmyla gzenek duvarlar zerinde bulunan takviye elemann durumu incelenmitir. Kpk numunelerin lineer genileme oranlar aadaki eitlik ile hesaplanmtr; Ls - Li Lineer Genileme Oran = -----------Li Kullanlan eitlikte Li kprtme ncesi, Ls kprtme sonras numune yksekliini gstermektedir [12]. retilen Alumix 231 esasl metal matrisli kompozit kpklerin younluk hesab Arimet prensibine gre yaplmtr [12]. m d=
y s Yukardaki eitlikte, d younluk, m arlk, Vy ya arlk, Vs ise su ierisindeki arl ifade etmektedir.
V -V
3. DENEYSEL SONULAR ve TARTIMA retilen metal matrisli kompozit kpklerde presleme ve deformasyon ynnde genileme gzlenmitir. ekil 1de %1 orannda TiH2 ieren ve 690C scaklkta kprtme ilemine tabi tutulan numunelerde artan takviye elamann (SiC) miktarna bal olarak younlukta meydana gelen deiimler gsterilmitir. Elde edilen grafiklerde grld gibi en yksek younluk arlka %12 orannda SiC ieren numunelerde elde edilmitir. 690C kprtme scaklnda % 1 TiH2 ieren metalik kpklerde en dk younluk deerleri ise arlka %3 orannda SiC ieren numunelerde elde edilmitir. Yap ierisinde %3 orannda takviye eleman bulunan numuneler ile ierisinde takviye eleman bulunmayan numunelerin younluk deerlerinin bir birine yakn kt tespit edilmitir. Buna paralel olarak %3 orannda SiC ilavesinin Alumix 231 esasl kpklerde kprme ve younlukta dikkate deer bir deiiklie neden olmad sylenebilir. %12 orannda takviye eleman ieren numunelerde ise younluk 0,88 g/cm3 olarak elde edilmitir ve bu deer %12 orannda SiC ilave edilerek retilen metal matrisli kompozit kpklerin ortalamas alnarak belirlenmitir. Yaplan almalar ile retilen kompozit kpklerde elde edilen en yksek younluk deeri 0,88 g/cm3 tr ve elde edilen bu deerin 1 g/cm3n altnda olmasndan dolay kpk numunelerin suyun zerinde batmadan durabilecei sylenebilir. SiC parack takviyesi ile metal matrisli kompozit kpn lineer genileme oranna paralel olarak younluunda meydana gelen azalma daha nce yaplan benzer almalar [13] ile rtmektedir.
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ekil 1. Alumix 231 ierisine ilave edilen SiC tozlarnn younlua etkisi ekil 2de arlka %3, 6, 9, 12 oranlarnda takviye eleman ieren, kprtc madde (TiH2) miktar %1 olarak sabit tutulan ve 690Cde kprtlen numunelerde parack takviyesindeki arta bal olarak lineer genileme orannda meydana gelen deiimler gsterilmektedir. Kprme ilemi srasnda meydana gelen lineer genileme orannn sadece ergiyik metalin viskozitesine bal olmayp ayn zamanda ayran kprtc madde miktarna da bal olduu literatrde belirtilmitir [14]. ekil 2de grld zere sabit kprtme scaklnda ve kprtc madde miktarnda artan takviye eleman miktarna bal olarak lineer genilemede bir azalma gzlenmitir. %3 parack takviyeli numunelerde maksimum lineer genilemeye 690 C kprtme scaklnda %1 TiH2 orannda ulalmtr. Ayn kprtme scakl ve kprtme sresinde ierisinde takviye eleman bulunmayan numuneler ile %3 orannda takviye eleman ieren numunelerde llen lineer genileme oranlarnda yaklak deerler hesaplanmtr. En dk lineer genileme oran arlka %12 orannda SiC ieren numunelerde hesaplanmtr. Artan takviye eleman miktarna bal olarak lineer genileme orannda bir azalma vardr fakat takviye eleman iermeyen, %3 ve %6 oranlarnda parack takviyesi ieren numunelerde lineer genileme oranlar ksmen birbirlerine yakn deerler olarak hesaplanmtr. Literatrde yaplan benzer almalarda farkl kprtme scaklklarnda SiC miktarndaki arta bal olarak lineer genilemede azalma tespit edilmitir [15]. Takviye elemann miktarndaki arta paralel olarak lineer genilemede meydana gelen azalmann sebebi gzenek duvarlarnn oluumu srasnda ergiyik metal ierisinde var olan paracklarn drenaj etkisini artrd ve genlemeyi azaltt olarak belirtilmitir [15].
ekil 2. Alumix 231 ierisine ilave edilen SiC tozlarnn lineer genilemeye etkisi ekil 3te 690C scaklkta kprtlm numunelerin gzenek yaplarna ait resimler gsterilmitir. 690C kprtme scaklnda ve %1 TiH2 ilave edilerek elde edilen metal matrisli kompozit kpklerde ideale yakn gzenek dalm ve gzenek duvar kalnlna ulald sylenebilir. Takviye eleman iermeyen, arlka %3 ve %6 orannda takviye eleman ieren numunelerde gzenek yaplar, gzenek dalmlar ve boyutlar ksmen benzerlik sergilemektedir. Gzenek morfolojisinde grlen benzer yaplar lineer genileme ve younluk lmleriyle elde edilen deerler ile uyumaktadr. Artan takviye eleman miktarna paralel olarak gzenek duvarlarnda kalnlama gzenek miktarnda azalma tespit edilmitir. Paracklar ksmen ergiyik metalin viskozitesini artrrken ksmen de metal/gaz
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ara yzeyinde yzey etken maddesi olarak davranarak gzeneklerin ergiyik ierisinde hareket etmesine ve birbirleri ile birlemelerine engel olmaktadr [16, 17]. %9 - 12 takviye eleman (SiC) ve %1 kprtc madde katlarak kprtlen numunelerde deiik oranlarda ve deiik boyutlarda gzenek elde edilmitir. Takviye eleman ilavesinin gzenek duvarlarn dzenleyici ve mekanik zellikleri iyiletirici etki yapt bilinmektedir [18]. SiC ilavesinin gzenek duvarlarnda dayanm art meydana getirdii dnlmektedir. Dayanm artna bal olarak kprme srasnda ayran hidrojen gaznn genlemeyi salamak zere gzenek duvarlarnda oluturduu basncn dk geldii ve kprmeyi engelledii sylenebilir. Kullanlan kprtme scakl yapya ilave edilen takviye elemannn ergime derecesinden daha dktr ve bu nedenle seramik paracklarn gzenek duvarlarnda hibir reaksiyona girmeden kald dnlmektedir.
ekil 3. SiC miktarndaki arta bal olarak deien gzenek yaps %1 TiH2 ve deiik oranlarda SiC takviye edilerek retilen Alumix 231 esasl kompozit kpklerin JEOL JSM 6060LV marka SEM cihaznda ekilen SEM grntleri ekil 4de grlmektedir. SiC paracklar gzenek duvar ierisinde yerlemi durumdadr. ekil 4a da SiC ieren Alumix 231 matrisli kompozit kpklerin gzenek yaps genel grnts verilmitir. ekil 4b ve c de gzenek duvar ve gzenek duvar zerinde bulunan SiC paracn grnts incelenmitir. ekil 4c zerinde grlen 1 numaral noktadan EDX analizi yaplarak SiC parack olup olmad netletirilmitir. EDX analiz deerleri ekil 5 de verilmitir. Elde edilen SEM grntlerine gre SiC ile Alumix 231 matris arasnda uyum olduu sylenebilir. SiC paracklar matris malzeme ierisine iyice girmi bir grnt sergilemektedir.
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ekil 4. SiC ieren Alumix 231 matrisli kompozit kpklerin SEM grntleri Gzenek yaps genel grnts b) Gzenek duvar c) Matris malzeme parack ara yzeyi ve EDX analizi yzeyi
ekil 5. SiC ieren Almix 231 matrisli kompozit kpklerin EDX analiz deerleri
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4. SONU Yaplan deneysel almalar sonucunda homojen dalm ve ideal gzenek duvar kalnlklarnda Alumix 231 matrisli kompozit kpk retimi iin %1 TiH2 orannda 690 C kprtme scaklnn uygun olduu sylenebilir. Deneysel almalar sonrasnda yap ierisinde deiik oranlarda (%3,6,9,12 SiC) bulunan takviye elemannn metal matrisli kompozit kpklerde, kprmeye ve buna paralel olarak da gzenek yaplarna nemli etkilerinin olduu tespit edilmitir. Parack miktarndaki arta bal olarak gzenek duvarlarnda kalnlama, gzenek saysnda azalma olduu ve rnlerin baz blgelerinde kprme olmad gzlenmitir. EDX analiz sonular ile gzenek duvarlar zerinde bulunan SiC paracklar tespit edilmitir. SEM grntlerine ve EDX analiz sonularna baklarak matris malzeme ve parack ara yzeyi arasnda bir uyum olduu sylenebilir. KAYNAKLAR 1. Seitzberger, M., Rammerstorfer, F.G., Degischer, H.P,, Gradinger, R. Crushing of axially compressed steel tubes filled with aluminium foam, Acta Mechanica:93,14, 1997. 2. Santosa, S.P., Wierzbicki, T., Hanssen, A.G., Langseth, M. Experimental and numerical studies of foam-filled sections, International Journal of Impact Engineering ;24, 509-517, 2000. 3. Chen, W.G., Experimental and numerical study on bending collapse of aluminum foam-filled hat profiles, International Journal of Solids and Structures, ,38,7919, 2001. 4. Hanssen, A.G., Langseth, M., Hopperstad, O.S., Optimum design for energy absorption of square aluminium columns with aluminium foam filler, International Journal of Mechanical Sciences, 43,153-158, 2001. 5. Song, H.W., Fan, Z.H., Yu, G., Wang, Q.C., Partition energy absorption of axially crushed aluminum foam-filled hat sections, International Journal of Solids and Structures, 42, 2575 2583, 2005. 6. Crupi, V., Montanini, R., Aluminium foam sandwiches collapse modes under static and dynamic three-point bending, International Journal of Impact Engineering, 34, 509-517, 2007. 7. Banhart, J., Aluminium foams for lighter vehicles, Int. J. Vehicle Design, 37: 114125 (2005). 8. Song, H., He, Q., Xie, J., Tobota, A., Fracture mechanisms and size effects of brittle metallic foams: In situ compression tests inside SEM Composites Science and Technology, 68, 24412450, 2008. 9. Hua Qin, Q., Wang, T.J. An analytical solution for the large deflections of a slender sandwich beam with a metallic foam core under transverse loading by a flat punch Composite Structures :88, 509518, 2009 10. J. Banhart, Manufacturing routes for metallic foams, Journal of Material science: 52, 2227, (2000) 11. Esmaeelzadeh, E., Simci, A., Lehmhus, D., Effact of ceramic particle addition on the foaming behaviour, cell structure and mechanical properties of P/M AlSi7 foam, Materials Sci&Engineering A, 424, 290-299, (2006) 12. H. inici, M.Trker, TM Yntemi le retilen Alminyum Esasl Metalik Kpe deformasyon Miktarnn Etkilerinin Aratrlmas, 13. Uluslar aras Metalrji ve Malzeme Kongresi, 854-860, Trkiye, (2006). 13. Yu, S., Luo, Y., Liu, J., Effects of strain rate and SiC particle on the compressive property of SiCp/AlSi9Mg composite foams, Materials Science and Engineering A 487, 394399, 2008. 14. L. Ma, Z. Song, Cellular structure control of aluminium foams during foaming process of aluminium melt, Scripta Mater., 39,1523-1528, (1998) 15. Esmaeelzadeh, S., Simchi, A., Lehmhus, D., Effect of ceramic particle addition on the foaming behavior, cell structure and mechanical properties of P/M AlSi7 foam Materials Science and Engineering A 424, 290299, 2006. 16. Prakash, G.O., Sang, H., Embury, J. D., Structure and properties of Al-Si foam, Mater. Sci. Eng., A 199: 195-203, (1995). 17. Gergely, V., Clyne, T.W., The Formgrip process: Foaming of reinforced metals by gas release in precursors, Adv. Eng. Materials 2:4, 175-178, (2000). 18. Li,Y.C., Xiong, J.Y., Lin,J.G., Forrest,M., Hodgson, P.D., Wen, C.E., Mechancal Propertes and Energy Absorpton of Ceramc Partculate and Resn-Impregnaton Renforced Alumnum Foams ,Materals Forum, 31, 52-56, 2007.
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VIBRATION DAMPING CHARACTERISTICS OF BORON COMPOSITES

H. Ibrahim UNAL*, Ozlem EROL*, O. Yunus GUMUS**, Berrak CETIN*, Turgay ERGIN*** *Gazi University, Chemistry Department, Smart Materials Research Lab., Ankara, Turkey, hiunal@gazi.edu.tr **Nevsehir University, Chemistry Department, Nevsehir, Turkey ***Hacettepe University, Department of Automotive, Ankara, Turkey ABSTRACT Electrorheological (ER) fluids can be classified as smart materials due to their controllable and reversible rheological characteristics under external electric fields. Most ER fluids consist of polarizable solid powders dispersed in insulating non-polar liquids. Recently, conducting polymers have gained interest in boron derivative containing conducting composites. Conducting polymer/boron derivative composites can be fabricated with controlled levels of conductivity and enhanced anti-sedimentation stability. In this study, vibration damping characteristics of borax and polyindene/colemanite composites were investigated. After characterizing these materials by various techniques, volume fraction series of dispersions were prepared in silicone oil (SO). Anti-sedimentation stabilities of these suspensions were determined. Flow rate measurements of these dispersions were measured at various electric field values; flow times and threshold energies were determined. Finally, vibration damping capacities of the materials were tested under external electric field, using an automobile shock absorber and were calculated as 68% and 27% for borax/SO and polyindene/colemanite/SO systems, respectively. Keywords: Conducting Polymer Composite, Electrorheological Fluids, Borax, Colemanite, Vibration Damping, Shock Absorber. 1. INTRODUCTION Electrorheological (ER) fluids are colloidal dispersions that commonly compose of polarizable powders dispersed in non-conducting liquids. ER fluids exhibit reversible changes (liquid-like to solid like and vice-versa) in their rheological properties as a function of the electric field strength (E). In the presence of sufficient electric field strength, the dispersed particles are polarized and aligned in the field direction to form a solid-like network of fibrillar structures and these structures cause to observe changes in rheological properties of dispersion. The solid powder comprises inorganic non-metallic, organic or polymeric semi-conductive materials [1]. Borax (Na2B4O7.5H2O) and colemanite (2CaO.3B2O3.5H2O) are important boron containing commercial borate minerals and can be candidates for being ER material. Also, preparing their composites with conducting polymer is another option since the interactions between organic and inorganic component of composite materials could enhance the desired properties. Because of the rapid and reversible changes in their rheological properties with the external applied E, ER fluids have been widely investigated for the purpose of various industrial applications such as shock absorbers, engine mounts, clutch/brakes and vibration dampers. ER shock absorbers are characterized by a valve containing a pair of electrodes between which the ER fluid flows [2]. The aim of this study was to investigate the vibration damping capacities of borax/SO and polyindene/colemanite composite/SO dispersion systems. Thus, borax was kindly ground milled and polyindene was polymerized in the presence of colemanite. The materials were dispersed in SO. Anti-sedimentation ratios of the dispersions were determined under constant temperature. Flow rates and threshold energies of the materials were investigated under various E. The effects of surfactant and polar additives on vibration damping capacities of the polyindene/ colemanite/SO were also examined. Results implied that all the systems perceive the applied electric field and try to act as a vibration damper.
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2. EXPERIMENTAL Borax and colemanite were kindly supplied by ETI Mining Co. (Turkey) and were ground milled. All the other chemicals were Aldrich products and used as received. Indene was used after distillation. Polyindene (PIn) was in-situ polymerized in the presence of colemanite using FeCl3 as oxidizing agent taking the monomer to initiator ratio as 2:1 in CHCl3. The prepared PIn/colemanite was ground-milled and subjected to particle size measurement using a Malvern Nano-ZS particle size analyzer. The obtained PIn/colemanite was subjected to various characterization techniques, namely: FTIR, particle size, density, conductivity, TGA, XRD and SEM. All the materials were subjected to solid pellet preparation (cylindrical in shape). Further, the apparent densities and conductivities (by a four probe technique) of the materials were measured. Dispersions of borax, colemanite and PIn/colemanite composite were prepared in SO at a series of volume fractions ( = 525%) and the anti-sedimentation stability of the dispersion systems were measured (T = 250.1C). The non-ionic surfactant examined was Triton-X (t-octylphenoxypolyethoxyethanol) and the concentration of TritonX in the colemanite and PIn/colemanite dispersions was 5 wt.%. To prepare the dispersions containing Triton-X, firstly, SO and surfactant were homogeneously mixed by using an ultrasonicator and then the materials, (colemanite and PIn/colemanite), were added and mixed again, with the volume fraction of 25%. These surfactant containing dispersions were coded as T-colemanite and T-PIn/colemanite. To enhance the ER activity of colemanite/SO and PIn/colemanite/SO dispersions, glycerol was added as 10 L/mL and the resultant dispersions were coded as Gcolemanite and G-PIn/colemanite. All the prepared dispersions were allowed to equilibrate for overnight before ER and vibration damping measurements. Flow rate measurements were carried out between two brass electrodes, which were connected to a high-voltage dc power supply. Oscillatory tests were carried out by a Termo-Haake RS600 parallel plate torque electrorheometer. Vibration damping experiments were carried out on an automobile shock absorber for Borax/SO ( =15%), under E = 0-0.3 kV/mm conditions on Therpa Hydraulic vibration damping test device. The hydraulic vibration test equipment contained a wheel (with a spring coefficient of 65400 N/m), an axle, a spring (with a coefficient of 13000 N/m), a shock absorber, an electrically operated drum to turn the wheel, a vibrating mass (60 kg), a non-vibrating mass (14 kg), control units and an external electric field generator (Fug Electronics). During the experiments, vibrations occurring on the body and on the axle were recorded by a recorder, which was operated at 400 V and 16 A. 250 mL of colemanite/SO, G-colemanite/SO, T-PIn/colemanite/SO and PIn/colemanite/SO dispersion systems were used with = 10% under the external electric field strength sweep of E = 0-170 V/mm and the experiments were carried out using Roehrig 20VS model shock absorber test equipment. During the experiments, a modified automobile shock absorber was placed to the vibration test device and a dc external electric field generator was connected to the inner and outer tubes of the shock absorber. The test parameters were set up using the Shock 6.3 shock absorber test program as following: Amplitude: 25.12 mm, test temperature: 25C, maximum test speed: 0.1 ms-1, frequency: 0.63 Hz, type of the input wave: sinusoidal. 3. RESULTS AND DISCUSSIONS The FTIR spectra proofed that the PIn/colemanite composite was successfully synthesized. SEM image of PIn/ colemanite composite reveals that porous structures of colemanite particles were homogeneously surrounded by close packed PIn chains, which supports the successful PIn/colemanite composite formation. The XRD pattern of PIn/colemanite composite showed sharp peaks at 2 = 15, 22 and 28 which indicates that colemanite was in the composite structure. The thermal stability of PIn/colemanite composite was observed to be higher than the thermal stabilities of colemanite and PIn [3]. The average particle size, apparent density, conductivity and anti-sedimentation ratios of the materials are given in Table 1. The conductivity values were decided to be in a suitable range for ER measurements. Table 1. Same physical properties of the samples. Sample Borax [4] Colemanite PIn/colemanite Average particle size (m) 6.35 1.2 2.2 Apparent Conductivity density (gcm-3) (Scm-1)x104 1.51 1.69 1.02 1.3 3.14 2.48 Anti-sedimentation ratios (%, at the end of 25 days, = 25%) 67 73 93
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Colloidal stability of the ER fluids against sedimentation is one of the important factors from industrial and application points of view. The ER fluids are supposed to be homogeneously dispersed before applying external electric field strength, and so that the stable fibrillar structures are formed under E between the upper and lower electrodes. At the end of 25 days of observation, 93% of PIn/colemanite composite particles were determined to remain unsettled. PIn/colemanite/SO dispersion system was significantly stable against gravitational sedimentation than colemanite/ SO and borax/SO systems. It can be concluded that in composite structure PIn chains surrounded the colemanite particles and formed steric hindrance that holds the particles in suspended positions against agglomeration. To observe the effect of dc electric field on the ER activity, flow rate measurements were carried out on all the dispersions. For this purpose, dispersions were prepared at a series of particle volume fractions ( = 525%) in SO and flow times were measured under E 0 kV/mm and E = 0 kV/mm conditions. During the flow time measurements, it was observed that electric field response time decreases with increasing volume fractions as a result of formation of fibrillar chain-like structures between the electrodes. On the other hand, a significant fibrillar structures between the electrodes was not observed for PIn/colemanite/SO system. The external frequency (f) is an important factor for characterizing the dynamic viscoelastic properties of ER fluids in vibration damping processes. Stress sweep was first carried out to determine the proper stress value to measure the storage modulus (G) in the linear viscoelastic regime. Figure 1 shows G as a function of frequency for borax/SO ( = 20%, E = 2 kV/mm), colemanite/SO, T-colemanite/SO, PIn/colemanite/SO and T-PIn/colemanite/SO dispersion systems ( = 25%, E = 1.5 kV/mm).
Figure 1. Change in storage modulus with frequency for all the dispersions. It was observed that Borax/SO system showed the highest G values and G values of all dispersions except PIn/ colemanite/SO were showed slight increments in the whole frequency sweep range and owing to not providing fully elastic solid-like structure in the dispersions, but they showed viscoelastic behavior. However, G values of PIn/colemanite/SO increased notably with increasing frequency. This suggests that fibrillar structure between the electrodes could not occur for PIn/colemanite [5].
Figure 2. Change in damping forces with piston velocity of shock absorber. Sample: T-PIn/colemanite/SO, = 10%. Figure 2 represents the damping forces (Fdamping) as a function of piston velocity of the modified automobile shock absorber for just T-PIn/colemanite/SO system under the constant conditions of T = 25C, = 10% and E = 0-170 V/mm. As the electric field increased, Fdamping of the ER damper, filled with T-PIn/colemanite/SO, also increased thereby requiring more force to move the piston. This was mainly attributed to the increment of the shear stress of the ER fluid with increasing applied E. The percentage increment of vibration damping of the samples was determined from the following equation:
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(1)
Vibration damping (%) of the materials calculated to change in the following order: T-PIn-colemanite (30%)>G-colemanite (28%)>PIn-colemanite (27%)>Colemanite (14%). The addition of Triton-X or glycerol caused to increase in the percentage of vibration damping of PIn/colemanite/SO and colemanite/SO. It was concluded that the presence of surfactant/promoter improved the performance of ER fluid. For Borax/SO system ( = 15%), positive body vibration amplitudes (recorded in the course of opening of the shock absorber) were observed to be bigger than the negative body vibration amplitudes (recorded in the course of closing of the shock absorber). Results showed that the amplitudes of body and axle, which are 10.2 and 12.6 mm, respectively, under non-electric field were reduced to 3.2 and 8.7 mm, respectively, by applying E = 300 V/mm external electric field. Thus, the vibration damping values were calculated as 68% on the body and 31% on the axle. These reductions on the amplitudes indicate that borax/SO system is able to perceive applied electric field strength and significantly increase the vibration damping capacity of the automobile shock absorber [6]. ACKNOWLEDGEMENTS The authors thank to Turkish Scientific and Technological Research Council for the financial support of this work (Project no: 107 T 711). REFERENCES 1. Hao, T., Electrorheological suspensions, Advances in Colloid and Interface Science, Vol. 97, pp. 1-35, 2002. 2. Wereley, N.M., Nondimensional HerschelBulkley Analysis of Magnetorheological and Electrorheological Dampers, Journal of Intelligent Material Systems and Structures, Vol. 19, pp. 257-268, 2008. 3. Cetin, B., Unal, H.I., Erol, O., Synthesis, Characterization and Electrokinetic Properties of Polyindene/ Colemanite Conducting Composite, Clay and Clay Minerals, submitted, 2011. 4. Gumus, O.Y., Unal, H.I., Erol, O., Sari, B., Synthesis, Characterization, and Colloidal Properties of Polythiophene/Borax Conducting Composite, Polymer Composites, Vol. 32, pp. 418-426, 2011. 5. Ramos-Tejada, M.M., Espin M.J., Perea, R., Delgado, A.V., Electrorheology of suspensions of elongated goethite particles, Journal of Non-Newtonian Fluid Mechanics, Vol. 159. pp. 34-40, 2009. 6. Gumus, O.Y., Erol, O., Unal, H.I., Polythiophene/Borax Conducting Composite II: Electrorheology and Industrial Applications, Polymer Composites, Vol. 32, pp. 756-765, 2011.
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TM YNTEMYLE AlSiMg ALAIMI METALK KPK RETM N GELTRLEN PREFORM MALZEME RETM SRECNN KAREKTERZASYONU
Ersin BAHEC*, Yusuf ZATALBA** ve Mehmet TRKER** * Kastamonu niv., Cide Rfat Ilgaz M.Y.O, 37600, ebahceci@kastamonu.edu.tr ** Gazi niversitesi, Teknoloji Fakltesi, Metalurji ve Malzeme Mhendislii, 06500, Ankara, yusufoz@gazi.edu.tr, mturker@gazi.edu.tr ZET Bu almada, toz metalurjisi yntemiyle AlSiMg alam kapal hcreli metalik kpk imalatnda kullanlan preform (nc) malzeme retimi ve retim srecindeki ilemlerin mikroyapya etkileri aratrlmtr. Arlka %8 Si, %0,8 Mg, %0,8 TiH2 ve kalan Al tozlar olmak zere Turbola cihaz ile 45 dakika sreyle kartrlmtr. Karm tozlar oda scaklnda preslenmi, sinterlemi ve ardndan scak ekstrzyon ilemi uygulanmtr. Ekstrze numuneler %20, %30, %40 ve %50 oranlarnda scak/lk haddelenerek levha numuneler retilmitir. retim srecindeki her bir ilem sonrasnda numunelerin mikroyaplar optik ve taramal elektron mikroskop vastasyla incelenmitir. Her bir sl ve deformasyon ilemleri sonrasnda retilen preform younluunda art gzlenmitir. Sinterleme sonras matristeki Si dalmnn homojen olduu ancak ekstrzyon sonunda deformasyon dorultusunda Si partikllerinde ynlenme olduu ve haddeleme sonras bu etkinin artt belirlenmitir. Ayrca, deformasyon ilemlerinin TiH2 n homojen dalmna etkisi olmazken, Mg partikllerinin deformasyon etkisi ile kmeletii belirlenmitir. Anahtar kelimeler: Metalik Kpk, Preform (nc) malzeme, Al Alam, Mikroyap
THE CHARACTERIZATION OF PRODUCTION PROCESS OF PREFORMS DEVELOPED FOR THE PRODUCTION OF AlSiMg ALLOY METALLIC FOAMS BY PM ROUTE
ABSTRACT In this study, production of precursor material for the production of AlSiMg alloyed closed cell metallic foam by PM techniques and the effect of production route on the properties of microstructure was investigated. Al, 8% Si, 0.8% Mg and 0.8% TiH2 powders were mixed in a three dimensional turbula for 45 min. Mixed powders were compacted at room temperature and sintered before hot extrusion. In order to produce sheet materials samples were hot/warm rolled by the reduction rates of 20% to 50%. Microstructures after every production stages were investigated by using optical and electron microscopes. A density increase has been observed after all heat treatment and deformation stages. The distribution of Si particles was found to be homogeneous after sintering whereas they exhibited orientation towards the deformation direction after extrusion which was more severe with rolling. The rate of deformation did not affect the distribution of TiH2 whereas which result in the agglomeration of Mg particles. Keywords: Metallic Foam, Al Alloy, Preform, Microstructure
1. GR Kpk malzemeler retim yntemleri asndan farkllklar gstermektedir. retim ilemlerine gre kat, sv ve gaz veya iyonize olarak snflandrlmaktadr. Sv retim yntemlerinde sv metal ierisine gaz enjektesi ile gerekle-
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tirilmektedir. Gaz veya iyonize retim yntemlerinde elektro-biriktirme veya metal buhar biriktirme ile ok gzenekli metalik yaplar elde edilir. Kat hal retim yntemlerinde ise tozlarn kprtc madde tozlar ile kartrlarak, sinterlenmesi ve ekstrzyon ilemi ile yar mamul elde edilir [1]. Toz Metalurjisi (TM) yntemi metal kpklerin retimi iin en yaygn kullanlan yntemlerden biridir. Bu yntem homojen bir yap elde etmek iin gelitirilen bir yntemdir [2,3] ve bu alanda youn almalara devam edilmektedir [2,4]. Kapal gzenekli kpk retimi yllardr TM yntemiyle gelitirilmektedir. Bu yntemde metal tozlarnn ve kprtc malzeme tozlarnn kartrlmas ve preslenmesi ile kprebilir yar mamul (preform/nc) malzeme haline getirme ilemine dayanr. Bu ilemlerle birlikte scak presleme, ekstrzyon, toz haddeleme, vb. metotlar ile preform retimi gerekletirilebilir. Preform malzeme ergime scaklnn zerinde bir scakla getirilerek kprtme ilemi gerekletirilir [5, 6]. TM yntemiyle retilen kpk malzemelerde Si ilavesi nemli bir parametreyi tekil etmektedir. Kpk hcreleri ve hcre ekilleri e eksenli yap grntsne benzer homojen ve yakn hcre boyutlu kpkler retilebilmektedir [7]. Bunun yannda % 8 Si alamnn seilmesi kprme iin gerekli olan en uygun lineer genleme ve daha dk younluklu kpk retebilmek iin kullanlmaktadr [8]. Otomobil paralarnn ksa srede retimi iin tozlardan metalik kpk retimi cazip hale gelmektedir. Scak ekstrzyon ile retilen preformlar istenildii gibi ekillendirilerek veya birletirilerek kprtlebilirler [9]. Karmak ekilli paralarn uygun ekilli preformlarn hazrlanarak kprtlebilmesine imkn vermektedir. Bu almada TM yntemiyle AlSiMg alam kapal hcreli metalik kpk elde etmek iin retilen preform malzemenin retim srecindeki ilemleri karakterize edilmitir. 2. DENEYSEL ALIMALAR 2.1. Malzeme ve Metot1 % 99,9 saflkta 160 m alt Al tozu ve 10 m alt Si tozlar kullanlmtr. Mg tozlar ise % 99,95 saflkta 149 m alt boyutunda tercih edilmitir. Arlka % 8 Si, % 0,8 Mg tozlar, % 0,8 TiH2 kprtc ajan tozu ve kalan alminyum tozu olmak zere 3 eksenli kartrma cihaznda (Turbola) 45 dakika sre ile kartrlmtr. Karm tozlar oda scaklnda preslenerek 60 mm apnda silindirik blok numuneler retilmitir. Blok numunelerin sinterlenmesi ilemi ardndan yaklak 8:1 ekstrzyon orannda scak ekstrzyon ilemi uygulanmtr (ekil 2.1-a). Ekstrze numune kademeli olarak scak/lk ilem scaklklarnda %20, %30, %40 ve %50 oranlarnda haddelenerek levha biimli numuneler retilmitir (ekil 2.1-b).
( a) (b) ekil 2.1. a)Ekstrze edilmi ve b) Haddelenmi numuneler 2.2. Sertlik ve younluk lmleri Malzemelerin sertlik lmleri, vickers yntemi ile Instron-Wolpert marka Diatestor 7551 model sertlik lm cihaz kullanlarak yaplmtr. Ayn numune iin 10 deiik noktadan llen sertlik deerlerinin ortalamas alnmtr. Younluk lmleri Arimet yntemiyle llmtr. retilen numunelerin younluklar, havadaki arlklar, daras alnm sudaki arlklar ile blnerek hesaplanmtr. llen younluk deerleri () ile retilen numunelerin teorik younluunun (teorik) oranlanmasyla ((/teorik) x 100) yzde younluk deerleri bulunmutur.
1
alma konusunun ticari deeri sebebiyle scaklk, sre, basn vb. baz parametrelerin deerleri bildiri metninde belirtilmemitir.
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teorik = %A x A + %B x B + %C x C + ..+ %N x N = 100 2.3. Mikroyap analizleri
g/cm3
(1)
Mikroyap grntlenmesinde Leica DFC 320 dijital kamera balantl Leica DM 4000 M marka optik mikroskop kullanlmtr. Numunelerin retim aamalarnda mikro yaplar incelenmitir. Preslenmi blok numune, sinterleme sonras, ekstrzyon sonras ve haddelemedeki deformasyon oranlarna (%20, %30, %40 ve %50) gre numunelerin mikroyaplar belirlenmitir. (ekil 3.2). Mikroyap karekterizasyonu ve grnt almlar Jeol JSM-6060 LV marka TEM (Tarama Elektron Mikroskobu) ile salanm, elementsel mikro analizler EDS/XRF sistemi ile gerekletirilmitir.
3. DENEYSEL SONULAR ve TARTIMA 3.1. Preform Malzeme Mikroyaps ekil 3.1de Ekstrze edilmi AlSiMg nkarml malzemenin TEM grnts ve XRF analiz sonular verilmitir. Ana TEM fotorafnda 1 numara ile XRF kodlamas yaplan ak gri renkli paracn arlka %78 orannda Ti ierdii ve bu paracklarn TiH2 paracklar olduu belirlenmitir. Kmelemi blgenin byltlm fotorafnda verilen 3 nolu koyu gri renkli paracklar ise Si paracklardr. Kmelemi blge iinde tanmlanan bir alann ise youn olarak Mg ierdii grlmektedir.
ekil 3.1. a) Ekstrze numune SEM grnts ve XRF analizleri ekil 3.2de sinterlenmi ve ekstrze edilmi numunelerin mikroyaplar grlmektedir. Sinterleme sonras mikroyapda Si ve Mg partikllerinin Al matris ierisinde genel olarak homojen dalml olduu sylenebilir (ekil 3.1a). Ancak, Al tozlarna nazaran ince toz boyutunda olan Mg paracklarnn matris iinde homojen dalmyla birlikte yer yer Si paracklar etrafnda kk kmeler meydana getirdii grlmektedir. Bu mikroyapda belirgin bir gzeneklilik mevcut deildir. Scak ekstrzyon ilemi sonras mikroyapya bakldnda Si partiklleri ve Mg kmelerinin ekstrzyon dorultusunda ynlendii belirlenmitir.
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ekil 3.2. a) Sinterlenmi numune, b) Ekstrze edilmi numune mikroyaps. ekil 3.3de haddeleme sonras mikroyap resimleri grlmektedir. Ekstrzyon sonras haddeleme miktar artka hadde ynnde Si partikllerinin ve Mg kmelemesinin de artt belirlenmitir.
ekil 3.3. %20 ve %50 haddelenmi numunelerde Si ve Mg dalmlar Toz metalurjisi yntemiyle retilen ve ekstrze edilen numune SEM grnts ekil 3.4te verilmitir. Beyaz renkte grnen paracklar TiH2yi gstermektedir. Baz blgelerde Mg kmelemeleri mevcuttur. Genel olarak Mg, Al matris yap ierisinde ok kk boyutlu taneler eklinde yayld grlmektedir (Siyah renkte). Yaylma ile Mg ilavesinin sinter kalitesi arttrma eilimi bu numunelerde de grlmtr [10]. Deformasyon ilemlerinin TiH2 n homojen dalmna etkisi olmad belirlenmitir. TiH2 hem Al matris hem de Mg, Si partikllerinin evresinde homojen olarak dald gzlenmitir.
ekil 3.4. Ekstrze preform malzemede genel parack dalmlar 3.2. Sertlik ve younluk Sinterleme sonras blok malzemelerin teorik younluu 2,679 g/cm3 olarak hesaplanm, Arimet yntemiyle llen younluk 2,60 g/cm3 ve % 97 oranndadr. Sinterlenen malzemeye uygulanan scak ekstrzyon sonras 2,65 g/cm3 ve % 99 a artmtr. Haddeleme sonras numunelerin younluklarndaki art maksimum 2,66 g/cm3 llmtr. ekil 3.5te ilem basamaklarna gre sertlik ve younluk deerlerini ieren grafik gsterilmitir. Ekstrzyon ileminden sonra younluk oranlarnda nemli bir deiiklik gzlenmez iken ilem basamaklarnda srasyla sertlik deerleri artt gzlenmitir. Ekstrzyon ileminden sonra yaplan scak/lk haddeleme ilemlerinde peklemenin etkisiyle sertlikte bir miktar art tespit edilmitir. Sinterlenmi numune ile % 50 deforme numune arasnda yaklak % 100luk sertlik art gzlenmitir.
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ekil 3.5. lem trne gre younluk ve sertlikteki deiim grafii. 4. SONULAR Kapal hcreli metalik kpk retmek iin toz metalurjisi yntemiyle gelitirilen Al, %8Si ve %0.8 TiH2 ieren nkarml malzemeye uygulanan sinterleme ve eitli deformasyon ilemleriyle retilen preform malzemenin sonularyla ilgili aadakiler sylenebilir; Sinterleme sonrasnda ekstrzyon ile salanan deformasyon ilemleri sonunda younluk % 97den arttrlarak % 99 younlua ulalmtr. Ekstrzyon sonras uygulanan scak/lk haddeleme ilemlerinin younlua nemli bir etkisi olmad belirlenmitir. Ekstrzyon ncesi sinterlenmi malzemede Si ve TiH2 paracklarnn genel olarak Al matris iinde homojen dalm gsterdii, ancak Mg paracklarnn yer yer kk kmecikler oluturduu belirlenmitir. Sinterlenmi malzemeye uygulanan 8:1 oranndaki scak ekstrzyon ilemi sonunda Si paraclarnn ekstrzyon dorultusunda youn olarak ynlendii, ayrca Mg kmlerinin ise, ksmen deformasyon etkisi gstererek ekstrzyon dorultusuna paralel ynlendii belirlenmitir. Ekstrze malzemelere scak/lk haddeleme ile salanan ve %50 varan deformasyon ilemlerinde ise, ekstrzyonla ynlenmi Si partiklleri ve Mg kmelerinin sklat grlmtr. lem basamaklarnda srasyla sinter, ekstrzyon ve haddeleme ilemlerinden sonra sertlik art grlmtr. Sinterlenmi numune ile % 50 deforme numune arasnda sinter numune sertliinin yaklak iki kat sertlik art gzlenmitir. KAYNAKLAR 1. John Banhart, Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress in Materials Science, 46, pp. 559632, 2001. 2. John Banhart, Manufacturing Routes for Metallic Foams, Journal of the Minerals, pp. 22-27, 2000. 3. Chin-Jye Yu, Harald H. Eifert, John Banhart and Joachim Baumeister, Metal Foaming by A Powder Metallurgy Method: Production, Properties and Applications, Innovations in Materials Conference, vol:2, pp. 181188, 1998. 4. Mehmet TRKER, Toz Metalurjisi Yntemi ile Alminyum Kpk retimi, 5. Uluslararas leri Teknolojiler Sempozyumu (IATS09), s.1-6, Karabk, 2009. 5. I. Duarte and J. Banhart, A Study of Aluminium Foam Formation Kinetics and Microstructure, Acta Materialia, 48, pp. 2349-2362, 2000. 6. By Frank Baumgrtner, Isabel Duarte and John Banhart, Industrialization of Powder Compact Foaming Process, Advanced Engineering Materials, 2, No:4, pp. 168-174, 2000. 7. Koza, E., Leonowicz, M., Wojciechowski, S. and Simancik, F., Compressive Strenght of Aluminium Foams, Materials Letters, 58, pp. 132-135, 2003. 8. Uzun, A., Gmen, U. ve Trker, M., Toz Metalurjisi Yntemi le retilen Alminyum Esasl Metalik Kpkte Si lavesinin Kprmeye Etkisi, 5. Uluslararas Ileri Teknolojiler Sempozyumu (IATS09), Karabk, s. 1-4, 2009. 9. M. Shiomi, S. Imagama, K. Osakada and R. Matsumoto, Fabrication of Aluminium Foams From Powder by Hot Extrusion and Foaming, Journal of Materials Processing Technology, 210, pp. 12031208, 2010. 10. I.A. MacAskill, R.L. Hexemer Jr., I.W. Donaldson and D.P. Bishop, Effects of Magnesium, Tin and Nitrogen On The Sintering Response of Aluminum Powder, Journal of Materials Processing Technology, 210, pp. 22522260, 2010.
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MODELING AND SIMULATION
www.turkishpm.org
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MODELING OF HEAT TRANSFER PROCESSES IN POROUS STEELS

Penka ZLATEVA*,Diyan DIMITROV**, Marin STOYTCHEV***and Daniela CHAKYROVA* * Technical University of Varna, Faculty of Shipbuilding, Department of Heat Engineering, 9010, Varna, Bulgaria, pzlateva1@abv.bg ** Technical University of Varna, Faculty of Shipbuilding, Department of Mechanical Engineering, 9010, Varna, Bulgaria, dimitrov.diyan@gmail.com *** Institute of Metal Science -BAS, 1000, Sofia, Bulgaria, m.stoytchev@ims.bas.bg ABSTRACT In the present article questions about heat transfer in sintered PM steels are discussed. Modeling of heat transfer in porous media can help for optimizing sintering and secondary heat treatment processes. On a base of experimentally obtained heat properties (heat capacity, thermal conductivity) of steel samples different with different porosity levels (6,11,20%), a numerical model of heat transfer was created. It seems that low porosity levels decreases thermal diffusivity, but at high porosity levels deeper penetration of cooling media into the open pores increases it. Keywords: Powder Metallurgy, Sintering, FEM-modeling 1. INTRODUCTION Increasing demands of PM components required detailed knowledge of the capabilities of sintering technology, the correct selection of the modes of ongoing processes in a wide variety of metal compositions. Knowledge of thermal characteristics of PM products with different porosity is necessary to maximize the impact of the process [1-2]. Cooling of PM parts is set by temperature curve representing the relationship between the body temperature (model) and environment (furnace) and cooling time. Upon realization of this non-stationary temperature field of the body significant amount of heat is released. This heat flux can be most accurately determined by modeling of unsteady heat transfer from PM body to the furnace, reflecting its real geometry and heat properties [3,6]. 2. EXPERIMENTAL In present paper object of study is simulation modeling of cooling process of PM sintered bodies with different porosity. For this purpose, microstructure images of iron besed sintered samples with different porosity level were used. Sintering was carried out at 1120C in industrial conveyor belt furnace with isothermal holding time 30 min and non-forced cooling to room temperature. The porosity of samples after sintering is 6, 11, 16%, based on the metallographic analyses. The metallographic analysis of the samples was made, using microscope Neofot-32, equipped with a digital camera. To form geometry of the model microstructure non-etched JPEG image is converted into black and white image. Contours are obtained in the binary version of black and white image. The next step of modeling is to extract the geometry using the AutoCAD software. B&W image contains many small art and distortion effects that must be filtered. Filtering of the image must be done very carefully because in this process most of details can be lost. The main idea is to draw points on the border between binary 1 and 0 areas, which correspond to the contours of the pores.
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The geometry of the pores is also made in AutoCAD. The boundaries are defined by different functions of curvature. For example, the points are spent in the channels to form boundary curves pores. Extracting the coordinates of pores and channels of receipt was done with the help of built into AutoCAD functions Fig.1.
Figure 1. Example of porous body geometry drawn. Creating the finite elements network is limited by two factors. The number of elements should not be too large and the size of the elements must be small enough to reflect the existing physical processes. Based on these limitations in FEM-software finite element network with approximate size of 3m was generated. Shape of finite element rectangular tetrahedron was chosen. 3. RESULTS AND DISCUSION Numerical model is built under the following conditions: Heat is given by the radiation of heat from the plate type body, to the furnace environment. The body is heterogeneous and consists of a metal matrix and pores. 3.1 Mathematical models of transient analysis temperature flow in the plate Transient heat transfer in plate body can be described by heat transfer equation (1) and conditions of unity to solve it, adequate to the real thermal behavior of the body in cooling mode. (1)
3.2 Geometry of the model Because of the thermal and geometric symmetry, geometric model is presented in the following way. Separate a small amount of microstructure picture after treatment in the above software is presented as a plate with the following characteristics: - Model 1 6% porosity has dimensions of 0.552 x 0.414 x 0,001 mm; - Model 2 11% porosity has dimensions of 0.594 x 0.446 x 0,001 mm; - Model 3 20% porosity has dimensions of 0.571 x 0.429 x 0,001 mm. 3.3. Initial and boundary conditions The temperature in the plate at the end of sintering process (1120C) is taken as a starting temperature of the cooling process. Initial uniform temperature distribution of 1120C was set. To all outside faces radiation with a degree of emissivity = 0.97 was set. Radiant energy exchange between neighboring surfaces of a region or between a region and its surroundings can produce large effects in the overall heat transfer problem. Though the radiation effects generally enter the heat transfer problem only through the boundary conditions, the coupling is especially strong due to nonlinear dependence of radiation on surface temperature. Extending the Stefan-Boltzmann Law for a system of N enclosures, the energy balance for each surface in the enclosure for a gray diffuse body is given by Siegal and Howell [5], which relates the energy losses to the surface temperatures:
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(2)
For a system of two surfaces radiating to each other, Equation2 can be simplified to give the heat transfer rate between surfaces i and j as see Chapman:
where: If Aj is much greater than Ai, Equation3 reduces to: where:
(3)
(4)
(5)
3.4. Physical conditions After check [3] of the thermal properties of materials for metal matrix (Fe-0.3%C) and the pores (nitrogen) are composed the following relations: C = C (T) and K = K (T) Table 1. These dependencies are used in solving equation (1). Table 1. Thermal properties.
3.5. Post processing results The formulated mathematical model is solved, using Ansys 13 FEM-software. The duration of cooling is discretisated in equal (1s) time steps. The results of simulation studies for model 1,2 and 3 are shown on Figure 2,3 and 4. Figures shows the distribution of thermal field in the metal parts and pores in a model. From Fig. 2 can be seen that for a time 0,3477s, plate size of around 500m is cooled to aproximatelly 89,145C. Cooling curve is shown in the bottom of the figure. From Fig. 3 can be seen that for a time 0,3477 s, plate with 11% porosity (mostly elongated pores) size of around 500m is cooled to aproximatelly the same temperatue as a 6% porosity sample 89,088C. Cooling curve is shown in the bottom of the figure.
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Figure 2.Temperature field distribution in 6% pores model. Bottom cooling curve From Fig. 4 can be seen that for a time 0,3477s, plate with 20% porosity and size of around 500m is cooled to aproximatelly 84,895C. Cooling curve is shown in the bottom of the figure. The analysis of results Fig.2,3,4 shows that at the same time and temperature, simulations show varying degrees of cooling, due to the different percentage of pores. As a rule thermal difusivity have to decrease with porosity increasing [3]. It is interestinng to mention that at higher porosity level (20%) faster cooling speed (lower
Figure 3.Temperature field distribution in 11% pores model. Bottom cooling curve
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Figure 4.Temperature field distribution in 20% pores model. Bottom cooling curve thermal diffusivity) was registred. The presence of open high percent open pores is a key factor here [4,7] since cooling media can penetrate in open pores. 4. CONCLUDING REMARK The proposed in this paper simulation model of the cooling of metal matrix and pores can be used in the design and verification tasks associated with the cooling process of PM products in belt furnaces. 5. NOMENCLATURE C specific heat capacity, J/(kg.K) K - thermal conductivity, W/(m.K) density, kg/m3 N = number of radiating surfaces ji = Kronecker delta i = effective emissivity (input on EMIS or MP command) of surface i Fji = radiation view factors Ai = area of surface i Qi = energy loss of surface i = Stefan-Boltzmann constant (input on STEF or R command) Ti, Tj = absolute temperature at surface i and j, respectively REFERENCES
1. German, R.M., Powder Metallurgy Science, MPIF, Princeton, NJ, USA, 1994. 2. German, R.M. Sintering Theory and Practice, Willie&Sons, NY, 1996 3. Rusev D.and etc, Heat Transfer, TU Varna, 2002 4. Bocchini G. F., A. Baggioli, B. Rivolta, G. Silva, P. Piccardo, E. Poggio, Influence Of Density And Surface/Vol-
ume Ratio On The Cooling Rate Of Sinter-Hardening Materials, Powder Metallurgy Progress, Vol.4 (2004), No 2 5. Sundelf Erik: Modelling of Reactive Gas Transport, ISBN 91-7283-511-7 TRITA-NA-0309 Licentiate Thesis, Universitetsservice US AB, Stockholm 2003 6. Ansys Modeling and Meshing Guide Ansys Release 13.0
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GAZ ATOMZASYONU NOZULUNUN HESAPLAMALI AKIKANLAR DNAM (CFD) LE NMERK MODELLENMES

Mustafa GLEEN*, Rahmi NAL** ve zer AYDIN**
*
Eskiehir Osmangazi niversitesi, Mhendislik ve Mimarlk Fakltesi, Makine Mhendislii Blm, 26030, Eskiehir, mgulesen@ogu.edu.tr ** Dumlupnar niversitesi, Mhendislik Fakltesi, Makine Mhendislii Blm, 43020, Ktahya, runal@dpu.edu.tr, ozaydin@dpu.edu.tr ZET
Bu almada, yakndan elemeli spersonik gaz atomizasyonu nozulu CFD simlasyonu kullanlarak Reynold Stress Modeli ile modellenmitir. Nozulun k blgesindeki gazn davran ve metal ak borusu ucundaki etkisi incelenmitir. zellikle metal ak borusu ucunda meydana gelen u basn deerlerini belirlemek amacyla CFD simlasyon modelinin sonular ile deneysel sonular kyaslanmtr. CFD zmnde elde edilen gaz atomizasyonu nozulunun metal ak borusu u basn deerleri deneysel veriler ile olduka yakn bulunmutur. Ortalama %3-5 daha byk deerler elde edilmi ve gaz basncna gre deiim erisi benzer bir davran gstermitir. Bu sonulara gre Reynold Stress model olduka baarl bir zm ortaya koymutur. Anahtar Kelimeler: Gaz atomizasyonu, CFD, gaz ak blgesi
NUMERICAL MODELING OF THE GAS ATOMIZATION NOZZLE BY CFD

ABSTRACT In this study, close coupled gas atomisation nozzle was modelled by CFD using Reynold Stress Modell. Gas behaviour at the nozzle exit and effect of the gas on the melt delivery tube tip were investigated. The pressure observed at the melt delivery tube was especially compared with the experimental melt tip pressure data. The difference between the CFD solution and experimental data was found to be very small. About %3-5 higher tip pressure value is observed at the CFD solution. The deviation between the numeric solution and experimental data is similar in shape. This results show that the Reynold Stress model offer very good results for the gas atomisation nozzle. Keywords: Gas atomization, CFD, gas flow field. 1.GR nce metal ve alam tozu retiminde kullanlan etkili yntem yksek basnl gaz atomizasyon yntemidir. Yakndan elemeli nozulun kullanld sv metalin gaz atomizasyonunda retilen metal tozunun homojen ve kresel olmas, dier toz retim teknikleri ile elde edilememektedir. Bu yntem ince metal tozu retiminde, iyi ak karakteristii ve paketleme zellii gereken uygulamalarda kullanlr. Kimyasal tekniklerle retilemeyen alam tozlar gaz atomizasyon yntemi ile kolayca retilir. Gaz atomizasyon ynteminde ama yksek hzda genleen gazn kinetik enerjisini sv metale aktararak metali kk damlacklara ayrmaktr. Dzenli ve yksek verimli bir atomizasyon ileminin gereklemesi gaz kinetik
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enerjisinin yksek olmas ve metal ak borusu ucunda negatif basn oluumu ile salanr. Gaz atomizasyonu ileminde, atomizasyon gaz basnc partikl boyutu ve yzey morfolojisini belirlemede nemli bir rol oynar. Aksoy ve ark. yaptklar almada azot gaz ile atomize edilmi kalay tozunun toz boyutu ve morfolojisi zerine knt mesafesinin ve gaz basncnn etkisini incelemilerdir [1-4]. Artan atomizasyon gaz basnc ile ortalama toz boyut dalmn azaldn bulmulardr. Toz karakteristiinin belirlenmesinde atomizasyon gaz basncnn fiziksel etkisini birka aratrmac grup anlamak iin almlardr [5-10]. Ting ve ark. HPGA (yksek basnl gaz atomizasyon) nozulda atomizasyon gaz basnc deiimi ile open wake ve closed wake durumunu aratrmtr [5]. Mi ve ark. Hesaplamal akkanlar dinamii yazlm PHOENICS kullanm ile HPGA (yksek basnl gaz atomizasyon) gaz ak blgesinde metal ak borusu mesafesinin ve atomizasyon gaz basncnn etkisini simle etmilerdir [6-7]. Zeoli ve ark. sv metale maximum kinetik enerji transfer edildii ve ok dalgalarnn azaltld bir izentropik meme nozul (IPN) tasarlamtr. IPN nin performans gaz ak dinamiini, damlack paralanma mekanizmasn ve parack boyutunu ieren nmerik bir model kullanlarak zmlemitir. Bu modeli oluturulmasnda CFD yazlm olan FLUENT kullanmlar. Trblans model olarak Reynolds-stress modeli kullanlm. Nedeni olarak da bu modelin akta hzl deiimlerin olmas ramen ak yakalamadaki stnl neden ile tercih etmitir [8]. Allimant ve ark. De laval nozul ile sv metalin gaz atomizasyon yntemi ile ilenmesi balkl makalesinde De laval nozul iin gaz ak blgesinde basn ve ergiyik debi etkisini incelemitir. Sv metal atomizasyonunda De laval nozul kullanlarak hem deneysel hemde modelsel yaklamlar allmtr. Bu iki yaklam ile atomizasyon basncna etkisi ve toz boyutuna etkileri karlatrmtr [9]. Deneysel olarak gzlemlenen eilimler yalnz gaz ak zerinde CFD modelleme almas ile aklanabilir olduunu tespit etmitir [10]. Bunun iin atomizasyon modeli oluturulmasnda CFD yazlm olan FLUENT kullanarak yapmlardr. deal gaz olarak argon, trblans model olarakta k- trblans modeli kullanmtr. Hesaplamann yaknsamasn giren ve kan debi arasndaki fark tarafndan deerlendirmitir. Basn artmas gaz hznda bir arta yol atn, bunun ergiyii daha iyi keserek paralayp ve bylece daha ince toz retildiini belirlemitir [9]. Bu almada, yakndan elemeli spersonik gaz atomizasyonu nozulu CFD simlasyonu kullanlarak Reynold Stress Modeli ile modellenmitir. Nozulun k blgesindeki gazn davran ve metal ak borusu ucundaki etkisi incelenmitir. zellikle metal ak borusu ucunda meydana gelen u basn deerlerini belirlemek amacyla iki farkl CFD simlasyon modelinin sonular ile deneysel sonular kyaslanmtr. 2. MODELLER VE SAYISAL FORMLASYONU CFD yazlmnn paket program FLUENT 6.3 kullanlarak atomizasyon nozulunun gaz ak simle edilmi ve atomizasyon gaz basncnn etkileri zerine modelleme almas yaplmtr. FLUENT 6.3 program seilen denklemlerin zmnde sonlu hacim yaklamn kullanr. CFD gibi byle nmerik modelleme teknikleri ak ve s transferi problemlerini simule etmek iin gl bir aratr. Ktlenin korunumu veya sreklilik denklemi, momentumun korunumu veya NavierStokes transport denklemi ve enerjinin korunumu denklemi nmerik olarak zlebilir. ki boyutlu eksenel simetrik geometriler iin sreklilik denklemi; [17] (1) Burada gaz younluu, x eksenel koordinat, r radyal koordinat, vx eksenel hz, and vr radyal hzdr. Sm kaynak terimi ise ayrlm ikinci fazdan (sv damlacklarnn buharlamas nedeniyle gibi) srekli faza ilave edilen ktle ve herhangi bir kullanc tarafndan tanmlanm kaynaktr. Denklem (1) sktrlabilir ve sktrlamaz aklar iin kullanlan ktlenin korunumu denkleminin genel formudur. ki boyutlu eksenel simetrik geometriler iin eksenel ve radyal momentum korunum denklemleri aada verilmitir.
(2) ve (3)
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Burada;
ve
(4) srasyla yerekimi kuvveti ve d kuvvettir (ayrk ve trblans yitim hz denklemleri aada (5)
Burada p statik basn, gerilim tens, vz swirl hz, faz ile etkileimden ykselme gibi).
Reynolds stress model (RSM) gre trblans kinetik enerji verilmitir.
ve (6) = 0:82, = 1, = 1:44, Burada; and fonksiyonu olarak llm deerler ve = 1:92, Yerekimi vektrle alakal lokal ak ynnn bir kaynak terimlerdir.
Sktrlabilirlik etkilerine yksek hzlardaki gaz aklarnda ve/veya byk basn deiimlerinde karlalr. Ak hz gazn ses hzna yaklat ya da at zaman veya sistemde basn deiimi (p=p) byk olduu zaman basnla gaz younluunun deiimi ak hz basnc ve scakl zerinde nemli bir etkiye sahiptir. Sktrlabilir aklar iin, ideal gaz kanunu aadaki formda yazlr; (7) Burada pop iletme basnc (operating conditions panelinde tanmlanr), p iletme basncna gre bal lokal statik basn, R niversal gaz sabiti, ve Mw molekler arlktr. Scaklk T enerjinin korunum denkleminden hesaplanabilecektir. Sutherland vizkosite kanunu ideal gazlarn kinetik kuram ve idealize edilmi bir molekller aras kuvvet potansiyeline dayanmaktadr. Bu forml iki veya katmanldr. Bu almada katmanl Sutherland kanunu kullanlmtr. katmanl Sutherland kanunu; (8) Burada viskozite (kg/ms), T statik scaklk (K), 0 bir referans deer (kg/ms), T0 bir referans scaklk (K), ve S ise gazn karakteristii olan Sutherland sabiti olarak isimlendirilen bir efektif scaklk (K). Scaklk ve basncn orta deerlerinde hava iin, 0= 1.7894x0-5 kg/ms, T0 = 273.11 K, and S = 106.67 K [18]. 3. DENEYSEL YNTEM ve SAYISAL MODEL 3.1. Deneysel alma Atomizasyon ileminin kararl bir ekilde gerekleebilmesi iin nozul ierisine yerletirilen sv metal ak borusu u noktasnda meydana gelen basn nemlidir ve bu basncn bilinmesi gerekir. Sv metalin atomizasyonu srasnda bu basncn lm mmkn olmadndan dolay genellikle sadece atomizasyon gaz verilerek u basn lmleri yaplr. Bu amala kurulmu dzenek ekil 1de gsterilmitir. ekil 1. Spersonik geometrili nozulun ematik gsterimi ve metal ak borusu u basncnn lm sistemi.
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Burada metal ak borusunun st tarafna yerletirilen bir basn alglaycsndan (pressure transmitter) alnan sinyaller sinyal alc tarafndan mbar deerine evrilerek okunmaktadr. Farkl atomizasyon basnlarnda llen deerler kaydedilerek u basn grafikleri izilmitir. Gaz atomizasyonu ileminde ekonomiklilik nemli bir parametredir. Bu parametre retilen toz iin tketilen gazn debisini ifade eder. Yaplan deneylerde spersonik nozul iin farkl atomizasyon basnlarndaki gaz debisi deerleri llmtr. lmler SIEMENS marka Strans F C Massflo Mass 2100 tipi ktlesel debi lm cihaz ile gerekletirilmitir. Nozul 8.5 mm2 boaz alanna, 5 mm knt mesafesine ve 260 lik nozul asna sahiptir. Atomizasyon nozul sisteminin simetrik ekle sahip olduu iin hesaplama iki boyutlu eksenel simetrik olarak zlmtr. 3.2. CFD Model Oluturulmas Atomizasyon nozul sisteminin simetrik ekle sahip olduu iin hesaplama iki boyutlu eksenel simetrik olarak zlmtr. Model geometrisinin oluturulmasnda daha nce toz retiminde kullanlan nozulun lleri esas alnmtr. Nozul iki boyutlu ve eksenel simetri olmak zere GAMBIT 2.4.6 programnda izilmi ve a yaps (meshleme) oluturulmutur(ekil 2). ki boyutlu eksenel simetrik geometrili zm, iki boyutlu ve boyutlu geometrilere gre hassasiyet asndan bakldnda daha avantajldr. nk grid saysnn azl zaman tasarrufu salayaca gibi, alan bana den grid miktar dierlerine gre olduka yksektir. ekil 3 de nozulun yaknsak-raksak blgesinin grid yaps ve hesaplanan alan gsterilmitir. Nozulun u basncn lmek iin ekil 4te gsterildii gibi nozulun ucundan itibaren bir mm ara ile satr kullanld ve her bir hat 1,5 mm uzunluundadr. Her bir hat zerine 10 adet lm noktas konulmutur. lm noktalarndan elde edilen tm basn verilerinin ortalamas nozul u basnc olarak kabul edilmitir. Metal ak borusunun i ap 3 mm olduundan dolay Simlasyon basn deerleri elde etmek iin hat uzunluklar y-ekseni ynnde 1,5 mm alnmtr. Simlasyonda elde edilen basn deerlerinin doruluunu artrmak iin basn hatt birbirinden 1 mm aralkla yerletirilmitir. Tm noktalarn basn deerlerinin ortalamas alnarak belirlenen metal ak borusu u basn deeri, deneylerde elde edilen deerler ile kyaslanmtr. Nozulun en dar blgesi (boaz) 0.2 mm. Ak daha iyi analiz edebilmek iin nozul blgesi ince meshlenmitir. Simlasyon balangcnda hcre says 47196 (mesh 1) olan kaba meshleme yaplm, daha sonra rafine ederek 334917 (mesh 2) mesh den bamszln kantlamak iin ayn geometriyi hcre says 1464200 (mesh 3) olan a yaplarnda ak simle edilmitir (ekil 5). Buradan da anlald zere mesh 2 daha ince a yapsna sahip mesh 3 den daha avantajldr. Elde edilen modelin meshden bamszln kantlam olduumuz gibi mesh 2 ile sonu daha ksa srede ve mesh 3 e benzer deerleri elde ettii tespit edilmitir. Bu almada incelenen tm durumlar iin, gen a yaps tercih edilmitir.
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ekil 3. Kritik blgelerdeki ve cidarlardaki mesh yaplar.
ekil 4. CFD modellemede nozul u basn deerlerini alnmasnda kullanlan hatlarn pozisyonu.
ekil 5. Farkl mesh saysna sahip CFD modellerdeki veriler ile deneysel verilerin kyaslanmas.
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CFD simlasyonlar basnca dayal, kararl durum ayrlm tam zc kullanlarak yaplmtr. Ak trblansl, viskoz model olarak Reynolds stres model (RSM) kullanlarak zlmtr. Model sabitleri default deerler uygulanmtr. Programn zc tipi seiminde seilenler ise pressure based, implicit yaklam, standart duvar fonksiyonu ve steady (kararl) zmdr. Akkan olarak azot gaz, younluk iin ideal gaz kanunu ile sktrabilir gaz kabul edilmi ve NIST verilerine gre gaz sabitleri Tablo 1 de verilmitir [20]. NIST verilerine gre azot gaznn sktrabilirlik faktr 11 Atmosfer basncnda ve 300 K scaklkta 0,998 dir. Bu durumda ideal gaz kanunu bu simlasyon kullanmak makuldr. Snr artlar ekil 2de gsterilmitir. Atomizasyon basnc 1.0, 1.3, 1.7, 2.2 ve 2.7 MPa deerler CFD modelleme esnasnda gaz giri basnc olarak kullanlmtr. Gaz giriindeki scaklk 300 K kabul edilmitir. Gaz k CFD modelde basn k olarak belirtilmi ve atmosfer basn deeri alnmtr. Tm duvar scaklklar 300 K kabul edilmitir. zme balama aamasnda programn kullanc kitabndan olduka yararlanlmtr. Yksek basnl almalarda zme balamada nerilen yollarn kullanlmas nem arz etmektedir. Aksi takdirde zme ulalamamaktadr. Bunun iin zellikle 200 iterasyonda kararl bir yaknsama salanmas iin enerji denklemleri seilmemitir. Balang deeri iin hz deeri programn hesaplad deerden daha dk girilmitir. Ayrca rahatlatma faktrleride (under-relaxation factor) basn iin 0.4, momentum iin 0.3, younluk iin 0.3, enerji iin 0.9 seilmitir ve dierleri default deerleri olarak ayn kalmtr. Yaknsama da kararl bir grnt salandktan sonra (200 iterasyon sonra) enerji denklemi almtr. zm iin 1.dereceden denklemler (first order upwind) seilmitir. RSM ayrklatrma zmnde 2. dereceden denklemler (second order upwind) altnda simlasyonun yaknsamas olduka zordur [21] ve yaknsama kriteri olarak ise enerji denkleminin 10-6 hata oran esas alnmtr. Ayrca giri ve k arasndaki ktlesel debiler arasndaki farknda 10-6 orannda bir farka ulamas yaknsama kriteri olarak gz nne alnmtr. Tablo 1 Saysal zmleme iin azot gaznn zellikleri Fiziksel zellikler Younluk (kg/m3) (J/(kg.K)) Termal iletkenlik (W/(m.K)) Referans viskosite (kg/(m.s)) Referans scaklk (K) Efektif scaklk (K) Molekler arl (kg/(kg.mol)) Standart hal entropisi (J/(kg.mol.K)) Deer 1.138 1040.67 0.0242 1.66310-5 273.11 106.67 28.0134 191494.8
4. BULGULAR ve DEERLENDRME Bir problemin CFD yardmyla zlmesinde seilen modellerin uygunluunun tespiti iin CFD sonularnn deneysel verilerle kyaslanmas gerekir. CFD sonularnn deneysel verilere yaknlk derecesi ve deneysel verilerle ayn karakteristik zelliklerine sahip olup olmad incelenir. Bu almada simlasyonun doruluunu kontrol etmek iin naln deneysel verilerinden yararlanlmtr [1, 22, 23]. Aydn ve nal yaptklar almada saysal zmlemeleri ile deneysel verilere bakldnda nozul gaz basnlar arasndaki fark tm basnlarda ayn olduu, deneysel verilerde nozul u basnc daha az olmakla birlikte, Realizable model sonular ile arasndaki fark %1115 arasnda deitiini tespit etmilerdir [25]. Reynolds stres model ile deneysel verileri kyaslandnda %3-11 arasnda deiirken, %11 fark sadece 1.0 MPa basn altnda elde edilmitir. 1.3, 1.7, 2.2 ve 2.7 MPa basnlarda deneysel verilere yaknl %3-5 arasndadr (ekil 6). Bu sonuca gre Reynolds stres model basn deerleri demodele gre daha yakn sonular vermitir. Espina ve Piomelli yaptklar neysel veriler ile kyaslandnda almalarnda saysal zmlemeleri ile deneysel verilere genellikle %10-20 arasnda yaknlk elde etmilerdir [24]. Bu nedenle bu simlasyonlar deneysel verilerle Espina ve Piomelli tarafndan yaplan daha nceki almalardan daha iyi rtmektedir. Bu sonu nozul u basncnn belirlenmesinde Reynolds stres modelin kullanlabileceini gstermektedir. ekil 7de gaz ktlesel debisinin CFD simlasyonlar ve deneysel veriler ile kyaslamas verilmitir. Deneysel veriler ile CFD sonular arasndaki fark hemen hemen sabit olup %30 civarndadr. Bu fark nozulun y-
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zey zelliklerinden ve gerek darboaz kesit alan ile nozulun tasarmndaki darboaz kesit alan arasndaki farktan kaynaklanm olabilir. Yine bu konuda Anderson ve Terpstra [3] yaptklar almada teorik debi ile deneysel debi arasnda basncn artmasyla birlikte giderek artan bir fark tespit etmiler ve teorik debi deerleri ile deneysel debi deerleri arasnda ok byk fark bulmulardr. Anderson ve Terpstra bu farkn nedenini aklayamamlardr. Bu almada elde edilen deerler arasnda hemen hemen sabit bir farkn olmas yaplan hesaplamann deneysel veriler ile rttn gstermektedir. Ayrca CFD almasnda gaz scakl sabit tutulmutur. Deneysel almada ak esnasndaki gaz scakl zamanla azalmaktadr. Bu durum nozula geen gazn gerek ktlesel debisini de etkileyebilir.
ekil 6. Nozul u basncnn CFD ve deneysel veriler ile karlatrlmas.
ekil 7. Gaz ktlesel debisinin CFD ve deneysel veriler ile karlatrlmas Nozul blgesinde Reynolds stress zmde elde edilen gaz hzlar ekil 8de verilmitir. Gaz hz maksimum deerine (663 m/s) 2.7 MPa gaz giri basncnda, minimum deerine (631m/sn) ise 1.0 MPa gaz giri basncnda erimektedir. Bu sonular gaz hznn basn art ile nemli lde artmadn gstermektedir. Bu nedenle verimli bir gaz atomizasyon ilemi iin nozul geometrisinin daha nemli olduunu gstermektedir. Bir nozulda ayn ktlesel gaz debisinde daha yksek gaz hz elde edilebilirse nozulun verimi daha yksek olacaktr. Bundan dolay bir gaz atomizasyon nozulunun verimi ekseriyetle nozulun geometrisine bal olduu sylenebilir.
ekil 8. Reynolds stres modelin farkl basntaki hz deerleri.
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5. SONULAR Bu alma kapsamnda gaz atomizasyonu nozulunun Reynold Stress model ile CFD zm yaplmtr. Elde edilen sonular deneysel veriler ile kyaslanarak modelin doruluu incelenmitir. almann sonular aada maddeler halinde verilmitir: CFD zmnde elde edilen gaz atomizasyonu nozulunun metal ak borusu u basn deerleri deneysel veriler ile olduka yakn bulunmutur. Ortalama %3-5 daha byk deerler elde edilmi ve gaz basncna gre deiim erisi benzer bir davran gstermitir. Bu sonulara gre Reynold Stress model olduka baarl bir zm ortaya koymutur. Gaz debisi deerleri deneysel debi deerleri ile karlatrldnda sabit olmak zere %30 fark elde edilmitir. Boaz akl 0,2 mm olarak teorik hesaplamalar yaplmtr. Debi deerleri arasndaki farkn nedeni nozulun imalatndaki boyutsal sapmadan ve scaklk deiimlerinden kaynaklanabilir. Gazn ak dorultusunda bir izgi boyunca gaz hz deerleri karlatrldnda gaz basncna gre ok nemli fark olmad grlmtr. zellikle gazn sv metal ile buluma noktas olan blgede yksek basncn gaz hzn ok nemli oranda arttrmad, 1.7, 2.2 ve 2.7 MPa basnlarda gaz hznn birbirine olduka yakn olduu grlmtr. KAYNAKLAR 1. Aksoy A, nal R. Effects of gas pressure and protrusion length of melt delivery tube on powder size and powder morphology of nitrogen gas atomized tin powders Powder Metall, 49(4): 349-354, 2006. 2. Singh D D, Dangwal S. Effects of process parameters on surface morphology of metal powders produced by free fall gas atomizationJ Mater Sci, 41(12): 3853-3860, 2006. 3. Anderson I E, Terpstra R L. Progress toward gas atomization processing with increased uniformity and control Mater Sci Eng A, 326(1): 101-109, 2002. 4. Srivastava V C, Ojha S N. Effect of aspiration and gas-melt configuration in close coupled nozzle on powder productivity Powder Metall, 49(3): 213-218, 2006. 5. Ting J, Peretti M W, Eisen W B. The effect of wake-closure phenomenon on gas atomization performance, Mater Sci Eng A, 326(1): 110-121 2002. 6. Mi J, Figliola R S, Anderson I E. A numerical simulation of gas flow field effects on high pressure gas atomization due to operating pressure variation, Mater Sci Eng A, 208(1): 20-29, 1996. 7. Mi J, Figliola R S, Anderson I E. A numerical investigation of gas flow effects on high-pressure gas atomization due to melt tip geometry variation, Metall Mater Trans B, 28(5): 935-941 8. Zeoli N, Gu S. Computational simulation of metal droplet break-up, cooling and solidification during gas atomisation Comp Mater Sci, 43(2): 268-278, 2008. 9. Allimant A, Planche M P, Dembinski L, et al. Progress in gas atomization of liquid metals by means of a de Laval nozzle. Powder Technol, 190(1-2): 79-83, 2009. 10. XinMing Z., et al. Effect of atomization gas pressure variation on gas flow field in supersonic gas atomization, Sci. China Ser E-Tech Sci, 52 (10):3046 3053, 2009. 11. Tinoco J, Widell B, Fredriksson H, Fuchs L. Modeling the in-flight events during metal spray forming Materials Science and Engineering A ,365: 302-310, 2004. 12. Ting J, Anderson IE, A computational fluid dynamics (CFD) investigation of the wake closure phenomenon, Materials Science and Engineering A, 379: 264-276, 2004. 13. Zeoli N, Gu S, Kamnis S. Numerical modelling of metal droplet cooling and solidification, International Journal of Heat and Mass Transfer 51, 4121-4131 2008. 14. Zeoli N, Gu S. Numerical modelling of droplet break-up for gas atomization, Computational Materials Science, 38, 282-292, 2006. 15. Tong M, Browne DJ. Direct numerical simulation of meltgas hydrodynamic interactions during the early stage of atomization of liquid intermetallic, Journal of Materials Processing Technology , 202: 419427 2008. 16. Tong M, Browne DJ. Modelling compressible gas flow near the nozzle of a gas atomiser using a new unified model. Computers & Fluids, 38: 11831190, 2009. 17. Fluent 6.1 Users Guide, Fluent Inc., Centerra Resource Park, 10 Cavendish Court, Lebanon, NH 03766, USA, 2003. 18. Fluent Inc., GAMBIT Users Guide, Fluent Inc., Lebanon, 2002. 19. White F.M., Fluid Mechanics, McGraw-Hill Book Co. 2nd Ed., 1988. 20. NIST Reference Fluid Thermodynamic and Transport Properties Database (REFPROP) version 7.0, National Institute of Standards and Technology, Boulder, CO 80305-3328, USA. 21. Gimbun, J., at all, The influence of temperature and inlet velocity on cyclone pressure drop; a CFD study Chemical Engineering and Processing 44 (2005) 7 12, 2005. 22. Unal R. The influence of the pressure formation at the tip of the melt delivery tube on tin powder size and gas/melt ratio in gas atomization method Journal of Materials Processing Technology, 180: 291-295, 2006. 23. Unal R. Improvements to close coupled gas atomization nozzle for fine powder production Powder Metallurgy, 50(1): 66-71, 2007. 24. Espina PI, Piomelli U. Numerical simulation of the gas flow in gas-metal atomizers. Proceedings of FEDSM98, 1998 ASME Fluids Engineering, Division Summer Meeting, June 21-25, Washington, DC, USA, 1998. 25. Aydn O., Unal R., Experimental and numerical modeling of the gas atomization nozzle for gas flow behavior, Computers and Fluids, 42, 37-43, 2011.
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GELENEKSEL TOZ METALURJS YNTEMYLE GZENEKL TiNi ALAIMLARIN RETM VE KARAKTERZASYONU

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ZET % 21-26 arasnda gzeneklilie sahip TiNi alamlar (Ti-50.6 at. %Ni) geleneksel toz metalurjisi yntemiyle retilmitir. Sinterleme srasnda oksitlenmeyi engellemek ve koruyucu bir atmosfer oluturmak amacyla titanyum paracklar ve magnezyum tozlar kullanlmtr. retilen gzenekli TiNi numunelerin sadece stenit fazn ierdikleri, bunun dnda istenmeyen krlgan Ti-Ni bileikleri ya da oksit gibi herhangi bir ikincil faz iermedikleri grlmtr. Her ne kadar geleneksel sinterleme metoduyla retilen gzenekli TiNi alamlar yetersiz gzenek miktar ve kk gzenek boyutu (uygulanan presleme basncna bal olarak, ortalama 4-65 m) nedeniyle yapay kemik uygulamalar iin uygun olmasa da gzeneklerin birbirleriyle balantl olmas nedeniyle filtre malzemesi olarak kullanlmaya son derece uygundur. Anahtar kelimeler: Gzenekli TiNi Alamlar, Biyomalzemeler, Mekanik zellikler, Oksitlenme, Toz Metalurjisi.
PROCESSING OF POROUS TiNi ALLOYS VIA CONVENTIONAL POWDER METALLURGY TECHNOLOGY AND THEIR CHARACTERIZATION
ABSTRACT Porous TiNi alloys (Ti-50.6 at. %Ni) with porosities in the range of 21-26% were produced using the conventional powder metallurgy technique. Titanium sponge and magnesium powders were used to prevent oxidation by providing a protective atmosphere during sintering. It has been observed that porous TiNi samples produced consisted of only single austenite phase without any secondary phase such as brittle undesired Ti-Ni intermetallics and oxides. Although porous TiNi alloys produced by conventional sintering have not been found to be applicable for bone replacements due to their low porosity and small pore size (4-65 m on average, depending on compaction pressure), they are appropriate for filtering applications due to their highly interconnected pore structures. Keywords: Porous TiNi Alloys, Biomaterials, Mechanical Properties, Oxidation, Powder Metallurgy. 1. GR TiNi alamlar sergiledikleri stn ekil bellek ve sperelastisite zellikleri ile bilinirler. Bu zellikler TiNi alamlarnn % 8e [1] varan oranlarda elastik ekil deiimlerini tamamen geri kazanmalarna imkan vermektedir. Bu srad termoelastik davran TiNi alamlarnn endstride pek ok kullanm alan bulmasn salamtr. TiNi alamlar gnmze kadar yaygn bir ekilde aktatr ya da tahrik dzenei, kavrama ve balant eleman, sensr, cep telefonu anteni, gzlk erevesi, ortodontik tel ve stent imalatnda [1-3] en ok tercih edilen malzemeler olmutur. Biyomedikal malzeme olarak kullanlmalarn sahip olduklar yksek biyo-uyumlulua borludurlar [4].
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ekil bellek ve sperelastisite zelliklerini gzenekli halde de ksmen koruyan TiNi alamlar son 20 ylda gzenekli olarak retilmeye balanm ve yeni uygulama alanlar nerilmitir [5]. Gzenekli TiNi alamlar, iyi korozyon direnci gstermeleri nedeniyle zellikle kimya ve polimer endstrisinde kullanlan gzenekli filtre retiminde ve iyi derecede biyo-uyumlulua sahip olmalar ve vcut kemiinin mekanik zelliklerine benzer zellikte mekanik davran sergilemeleri nedeniyle de diilikte ve vcut kemik deiimlerinde implant malzemesi olarak kullanlabilirler. Bugne kadar gzenekli TiNi alam retmek iin pek ok toz metalurjisi yntemi uygulanmtr. TiNi alamnn yksek ergime scakl, 1310 C, oksijen, karbon, azot ve hidrojene olan yksek afinitesi ve pota malzemeleri ile reaksiyona girmesi gibi nedenlerle sv halde gzenekli metal retme yntemleri pek tercih edilmemi [6], eitli toz metalurjisi teknikleri esas retim metodu olarak benimsenmitir. Reaktif sinterleme [7-10], geleneksel sinterleme [11-13], sabit basnta scak presleme [14,15], elektro plazma sinterleme [16], boluk oluturucu yntem [17-22] ve toz enjeksiyon kalplama [23,24] teknikleri sklkla kullanlmtr. Bu yntemlerde reaktif sinterleme dnda elementel titanyum ve nikel ya da alam (TiNi) tozlar kullanlabilmektedir. Her yntemin kendine zg avantaj ve dezavantajlar bulunmakla beraber gerek elementel gerekse alamlanm toz kullanlarak sz konusu yntemlerle retilen gzenekli TiNi alamlarnda grlen ortak ve en nemli sorun istenmeyen TiNi3, Ti4Ni2O ve Ti2Ni gibi titanyumca ya da nikelce zengin ikincil fazlara rastlanlm olmasdr. Bu fazlar TiNi yap iinde, zellikle tane snrlarnda, byk boyutlu olarak olumakta ve malzemenin krlganlamasna sebep olarak mekanik zelliklerini olumsuz ynde etkilemektedirler. Bunun yan sra malzemenin ekil bellek ve sperelastisite zelliklerini azaltmakta ve malzemenin korozyon direncinde de bir de neden olmaktadrlar [25,26]. Ayrca hemen hemen tm yntemlerde zellikle elementel titanyum ve nikel toz kullanldnda reaksiyona girmeden yapda kalan saf titanyum ve nikel fazna da ska rastlanlmaktadr. Titanyum faz malzemenin mekanik zelliklerinde bir zayflamaya neden olurken, nikel faz bilinen toksik ve alerjik zellikleri nedeniyle malzemenin biyouyumluluunu olumsuz ynde etkilemektedir [25]. TiNi dnda oluacak tm fazlar yapnn bileimini deitireceinden kompozisyona ok duyarl olan ekil bellek ve sperelastisite davranlar da bu deiimden etkilenecektir. Tm bunlarn yan sra oksijen, hidrojen ve azot gibi gazlarn 200 C scakln stnde TiNi alamlarndaki yksek znrlklerinden dolay gzenekli metal retiminde eitli zorluklarla karlalmakta ve retilen gzenekli metalik malzemelerin mekanik zelliklerinin bu elemetlerin znmelerinden olumsuz etkilendii grlmektedir. rnein, oksijenin TiNi iinde znmesi sonucu TiO, TiO2, Ti2O3 ve Ti3O5 gibi erime scakl ok yksek oksit bileikleri olumaktadr. Titanyumun seici oksitlenmesi sonucu aa kan nikel atomlar da TiNi3 faznn oluumuna yol amaktadr [1]. Bu yzden TiNi alamlarnn sinterleme srasnda oksitlenmemesi iin sinterleme atmosferindeki oksijen ksm basncnn ok dk deerlere indirilmesi (rnein 1100 C sinterleme scaklnda Ellingham Diyagramna gre 5 10-25 atm) arttr [17,18]. Ayn ekilde hidrojen elementinin de TiNi alamlar iindeki znrl yksektir. Dk scaklk ve basnlarda TiNiH1.4 oluurken daha fazla hidrojen konsantrasyonu, yksek scaklk ve basnlarda TiH2 ve TiNi3 olumaktadr. Hidrojen miktar 1809 ppme ulatnda ekil bellek ve sperelastisite zelliinin tamamen ortadan kalkt rapor edilmitir [27]. Benzer ekilde azotun da TiNi alamlar iinde znmesi sonucu TiN olumaktadr. Bunlarn dnda karbon da TiNi iinde znrl az da olsa titanyum atomlar ile reaksiyona girerek TiC oluturmaktadr. Bu almada, elementel tozlarn kullanlmas durumunda varlklar kanlmaz olan istenmeyen ikincil fazlarn oluumunu, alam TiNi tozlarn koruyucu magnezyum buhar altnda sinterleyerek engellemenin mmkn olduu gsterilmitir. Magnezyum, Ellingham diyagramnda kalsiyumun hemen zerinde yer alan, oksijen alabilirlii (afinitesi) son derece yksek olan ok iyi bir indirgeyici elementtir. Bu yzden sinterleme scaklna stma, bekleme ve soutma aamalarnda (sv ve gaz haldeyken) TiNi alamlarnn olas oksitlenmesini tamamen engelleyebilmektedir. Buna ilaveten retilen tek fazl TiNi alamlarnn yapsal ve mekanik zellikleri ortaya konulmutur. 2. DENEYSEL YNTEM 2.1. Kullanlan tozlar retim ynteminde daha nceki almalarmzda [6,11,17,18] detayl olarak analiz edilmi, alamlanm nikelce zengin, stenitik, kresel TiNi tozlar (Ti-50.6 at. %Ni, % 99.9 saflkta, Nanoval GmbH & Co. KG) kullanlmtr. Gaussian (log-normal) dalm gsteren TiNi alam tozunun ortalama ap 21 m iken koruyucu atmosfer yaratmak
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iin kullanlan kresel Mg tozunun (% 99.82 saflkta, Tangshan Weihao Magnesium Powder Co. LTD) ap ortalama 450 m olarak belirlenmitir. 2.2. retim Yntemi TiNi tozu sktrma ncesi balayc olarak kullanlan % 5 polivinil alkol (PVA) zeltisi (% 2.5 PVA + su) ile homojen bir karm elde etmek zere 30 dakika sreyle kartrlmtr. Elde edilen karm, souk hidrolik preste, sertletirilmi elikden yaplm basma kalplar iinde, n deneylerle belirlenmi olan 770 MPa optimum basn altnda ift ynl olarak baslmtr. Presleme sonras kalplardan karlan yaklak 10 mm apnda ve 12 mm yksekliindeki numuneler 1100 C scaklkta, sngerimsi titanyum paracklarla temizlenmi koruyucu argon atmosferi altnda 1 saat sreyle sinterlenmilerdir. Sinterleme ilemi ncesi potaya TiNi kompaktn arlnn % 12si miktarnda magnezyum konulmutur. Oda scaklndan 1100 Cye stma hz 10 C/dak olarak sabit tutulmutur. 1090 Cye ulaldnda, 650 Cde eriyerek sv hale geen magnezyumun tamam buharlaarak pota iinde TiNi iin indirgeyici bir atmosfer oluturmaktadr. Bu sebeple argon gei hz frn ierisinde bir miktar i basn oluturmaya yetecek kadar yavalatlmtr. Oksitlenmeye kar ek bir nlem olarak sngerimsi titanyum paracklar TiNi kompakt zerine temas etmeyecek ekilde yerletirilmitir. Sinterleme sonrasnda pota frnn souk blgesine ekilerek yaklak 60-75 C/dak bir hzda numunelerin oda scaklna soutulmalar salanmtr. 2.3. Karakterizasyon Younluk ve gzenek miktar Arimet yntemi kullanlarak llmtr. Gzenek boyutlar Quantachrome PoreMaster 60 cival gzenek ler cihaz kullanlarak llmtr. TiNi tozda ve retilen gzenekli TiNi alamnda bulunan fazlar belirlemek iin Rigaku D/Max 2200/PC model X-In Difraktometresi (XRD) kullanlmtr. yap incelemeleri Noran System 6 enerji dispersiv spektrometresine sahip Jeol JSM 6400 taramal elektron mikroskobu (SEM) kullanlarak gerekletirilmitir. Tek eksenli basma testleri 10X10 mmlik silindirik numuneler kullanlarak 30 kN kapasiteli Instron 3367 mekanik test cihaz yardmyla oda scaklnda (25 C) 0.1 mm/dak basma hzyla gerekletirilmitir. Elastik modul deerleri gerilim-gerinim diyagramnn dorusal ksmndan hesaplanrken stenit-martensit dnm gerilimi % 0.2-offset metodu ile belirlenmitir. 3. BULGULAR VE DEERLENDRME 3.1. Younluk ve Gzeneklilik Ya younluk ve gzenekliliin presleme basnc ile deiimi ekil 1de gsterilmitir. TiNi tozlarn grnr younluu 4.195 g/cm3 olarak llmtr ve buna karlk gelen gzeneklilik miktar % 34.96dr. Beklendii gibi uygulanan basncn artrlmas younlukta bir art ve gzeneklilikde bir azalmaya yol amtr ve elde edilen maksimum ya younluk, 1150 MPa maksimum basn altnda yaplan sktrmasktrma sonras % 22lik bir gzenek oranna karlk gelen 5.07 g/cm3 olmutur. ekil 1den TiNi tozlarn sktrma davrannn dier alam tozlarnkine benzer olduu aktr. Sktrma ilemi tozlarn yeniden dzenlenmesi ile balar. Bu aamada tozlarn yzey alan, yzey morfolojisi ve yzey przll tarafndan kontrol edilen partikller aras srtnme etkin olan mekanizmadr. Bu almada kullanlan TiNi tozlar (ortalama 21 m) ok kk olduundan, yzey alanlar son derece byktr. Geni yzey alan genel olarak daha yksek srtnme ve daha dk paketlenme, hem de yetersiz dzenlenme anlamna gelir. Basncn uygulanmasna devam edilmesiyle tozlarn yeniden dzenlenmesini takiben, toz temas blgelerinde lokal deformasyon gerekleir. Basncn daha fazla artrlmasyla plastik deformasyon geiren her paracn bal hacminde bir art gerekleir ve gzeneklerin miktarnda azalma meydana gelirken yeni temaslarn oluumu artar ve nihayet btn kompakt homojen deformasyona maruz kalr. Plastik deformasyon ile birlikte deformasyon sertlemesi kanlmaz olur ve bunun sonucunda yksek younluk dzeyleri daha yksek d enerji gerektirir.
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ekil 1. Sinterleme ncesi younluk ve gzenekliliin sktrma basnc ile deiimi.
ekil 2. Farkl basnlarda baslm TiNi kompaktlara ait XRD diyagramlar.
TiNi tozlarn baslabilirliinin, geleneksel tozlarnkine gre daha dk olduu tespit edilmitir. Dayankl, atlak iermeyen kompakt retimi basma srasnda gzlenen sperelastik davran nedeniyle ok daha zordur. stenitik iyapya sahip olan balang TiNi alam tozlar sktrma esnasnda uygulanan basnla birlikte % 7-8 kadarlk deformasyonu martensitik dnm ile gerekletirmektedir. Daha fazla deformasyon uygulandnda tozlar klasik dislokasyon hareketi yoluyla plastik ekil deitirmektedirler. Bilindii zere sperelastik davran gsteren malzemelerde ykn boaltlmasyla birlikte malzeme ters dnm (martensitstenit) nedeniyle ilk ekline geri dnmektedir. Fakat yapda dislokasyonlar da oluturulduu zaman bu ekil geri kazanm ksmi olmaktadr. ekil 2deki XRD patternlerinden farkl sktrma basnlar ile preslenen TiNi kompaktlarn bu ilem sonras hangi fazlar ierdikleri grlmektedir. Dk sktrma basnlar uygulandnda, oluan martensit faznn basncn sfrlanmasyla birlikte tamamen stenite geri dnt gzlenmitir. te yandan daha yksek presleme basnlar kullanldnda, rnein 575 MPa, iyapda meydana gelen dislokasyonlar gerilimle oluturulan martensitlerin kararl hale gelmesine yol amtr. Dislokasyonlar normalde hareketli olan stenit/martensit ara yzeylerinin hareketini engelleyerek ters dnmn gereklemesini ve dolaysyla ekil geri kazanmn ksmen engellerler. ekil geri kazanm artan basnla birlikte daha da azalr. Normal artlar altnda istenmeyen bir fenomen olan martensit stabilizasyonu sperelastik TiNi tozlarnn baslabilmesi iin gerekli bir koul haline dnr. Aslnda presleme basnc 10 mm apnda ve 3 mm yksekliinde disk eklindeki numunelerin retiminde kritik bir parametre deildir. Ancak, basma deneyleri iin gereken ve 10 mm ap ve 12 mm boyunda numunelerin sadece 770 MPa civarnda bir basn ile retilebilecei tespit edilmitir. 1150 MPa gibi daha yksek basnlarda ise her ne kadar ya mukavemeti daha yksek ve gzenek miktar daha az numuneler retilebilse de, bu kompaktlarn kalp ierisinden karlmas inko stearat gibi bir yalayc kullanlmasna ramen ok daha zor olmutur. Kald ki bu almada ama zaten dk gzenekli malzeme retmek deildir. ekil 3 presleme basncnn sinterleme sonras younluk ve gzeneklilik zerindeki etkisini gstermektedir. Sinterleme ilemi sonucu gzeneklilikte % 0.8-3.7 aralnda bir d meydana gelmitir. Sinterleme sonucu oluan aptaki bzlme miktar retilen tm numunelerde % 2den daha dk iken numune boylarnda yaklak % 2lik bir ime (swelling) gzlenmitir. Fakat bu ime, elementel tozlar kullanlarak sinterlenen TiNi alamlarnda gzlenen klasik ime deildir. Daha ziyade sinterleme ncesi stma srasnda ekil bellek etkisi mekanizmas ile geri kazanlan elastik gerinimlerden kaynaklanan bir imedir. Farkl basnlarda preslendikten sonra sinterlenmi TiNi alamlarna ait gzeneklilik dalm ekil 4de verilmektedir. Gzenek byklnn artan sktrma basnc ile azald grlebilir. Ortalama gzenek boyutu (% 50 kmla-
ekil 3. Sinterleme sonras younluk ve gzenekliliin sktrma basnc ile ilikisi.
ekil 4. Sinterlenmi TiNi alamlarnda sktrma basncna bal olarak gzenek dalmnn deiimi.
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tife karlk gelen), en dk basn iin, 190 MPa, 65 m iken maksimum basn olan 1.150 MPa iin yaklak 4 m olarak tespit edilmitir. Gzlenen en byk gzenek boyutu 200 m civarndadr. Biyomedikal uygulamalar kemik dokunun implant malzemesi iinde geliimi iin 100-600 m arasnda deien gzenek boyutlar gerektirmektedir [3]. Bu nedenle, gzenek boyutlar 100 mdan byk olan gzenek ierii nemli bir parametredir. 190 MPalk bir presleme basnc toplam porozitenin % 40nn boyutlarnn 100 mdan daha byk olduu gvencesini verirken bu oran 380 ve 575 MPa iin % 20 seviyelerine dmtr. Daha yksek basnlarda ise sadece % 5-6 civarndadr. Ancak, bu tr byk gzenek boyutlar (100 m ve daha yksek), SEM analizi srasnda gzlenmemitir. Geleneksel sinterleme yntemiyle retilen gzenekli TiNi alamlarnda belirli bir gzenek eklinin olmad ekil 5den aka grlmektedir. Genel olarak, gzenekli bir malzeme veya kpkte gzenekli numunenin d yzeyine bal gzenekler ak gzenekler, d yzeye bal olmayan gzeneklerse kapal ya da izole gzenekler olarak snflandrlabilir. Geleneksel toz metalurjisi yntemiyle retilen gzenekli TiNi alamlarnda gzeneklerin byk bir ounluunun balang tozlarn dk paketlenme, dk sktrma basnc ve basnsz ksmi sinterleme sonucu birbirine bal ve ak tip olduu bulunmutur. Yine de bir miktar izole veya kapal gzenek de ekil 5den grld zere SEM incelemeleri srasnda gzlenmitir. Bu gzeneklerin byk bir ksm tozlarn atomizasyonu srasnda olumutur. Ancak sinterleme esnasnda da baz kapal gzeneklerin olumu olmas muhtemeldir. Ak gzenek oran, retilen btn numunelerde % 90dan daha fazladr.
ekil 5. % 23 gzenekli TiNi alamnn SEM grnts. Genel gzeneklilik (yani toplam porozite), ak gzenek oran ve gzenek boyutu zellikle kemik implantasyonu gibi biyomedikal uygulamalar iin ok nemli faktrlerdir. Yksek bir ak gzeneklilik oran ile yeterli gzenek miktar ve gzenek boyutu implant malzemesi iinde doal kemik bymesini garanti eder. Yapay kemik deiimi uygulamalar iin gzenek miktar % 30-90 aralnda olmaldr [5]. Kemik bymesi ve vcut svlarnn tanm iin gzenekler ak tipte ve birbirleriyle balantl olmaldr. Bu gereksinimlerin nda klasik souk presleme ve sinterleme yntemi ile retilen gzenekli TiNi alamlarnn yapay kemik implant olarak kullanlmalar uygun deildir. te yandan, birbirine yksek oranda bal gzenek yaplar (mkemmel geirgenlik) nedeniyle pek ok uygulamada filtre olarak kullanlmalar mmkndr. 3.2. Makro ve Mikroyap ekil 6da verilen SEM grnts sinterlenmi gzenekli TiNi alamnn makro grnmn gstermektedir. 5 m boyutlarna varan beyaz renkli magnezyum oksitler (MgO) aka grlmektedir. Bu oksitlerin TiNi kompakta dorudan temas eden magnezyumun ortamdaki oksijenle reaksiyona girmesi sonucu olutuu anlalmaktadr. Buna karlk, balangta magnezyum tozu ile dorudan temas halinde olmayan yzeylerde magnezyum ya da MgOe hemen hemen rastlanlmamtr.
(a) (b) ekil 6. Sinterleme srasnda TiNi kompakt yzeyinde oluan beyaz renkli MgOlar gsteren SEM grntleri, (a) kk bytme, (b) yksek bytme.
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Magnezyum 650 Cde erir ve artan scaklkla buhar basnc sv haldeyken byk lde artmaya balar. Scaklk art ayn zamanda magnezyumun oksidasyon reaksiyonunu da hzlandrr. Sv magnezyum TiNi kompakt yzeyini slatr ve TiNi tozlarn oksitlerini indirgerken pota iinde bulunan frn atmosferindeki kalnt oksijen ile de reaksiyona girer. Sonu olarak, sinterleme ncesi magnezyum tozu ile dorudan temas blgelerinde youn olarak MgO paracklar oluturur ve bu oksitler kompakt zerinde yapr kalr. Ayn zamanda sv magnezyum ekil 6 (b)de belirgin bir ekilde grld zere bir dereceye kadar kompakt yzeyini andrmaktadr. Balangta direk temasn olmad blgelerde MgOnun olmama ya da ok ok az olmasnn nedeni bu blgelerin sadece magnezyum buharna maruz kalmalarndandr. Bu blgelerde erozyon izine de rastlanlmamtr. blgelerin ise tamamen magnezyum ve MgO paracklardan muaf olduu tespit edilmitir. Sv magnezyum ile TiNi kompakt erozyonunu nlemek ve yzey zerinde kalan MgO paracklarn en aza indirmek iin kompakt sinterleme ncesi uzun MgO pelet zerine yerletirilmitir ve magnezyum tozu bu peletin zerine ve yanlarna ilave edilmitir. Bylece kompaktn hibir blmnn magnezyum tozu ile temas halinde olmamas garanti altna alnmtr. Bu tasarm kalnt MgO paracklarn minimize etmitir. ekil 7 gelitirilmi tasarm kullanlarak retilmi bir numuneyi gstermektedir.
ekil 7. Sinterlenmi ve nerdeyse hi kalnt MgO iermeyen TiNi alamnn makro grnts. Farkl basnlarda preslenmi ve daha sonra ayn artlarda sinterlenmi gzenekli TiNi numunelere ait XRD desenleri ekil 8de gsterilmitir. Grld zere ne istenmeyen ikincil Ti-Ni intermetalikler ne de oksit, karbr gibi bileikler tespit edilememitir. Btn numunelerde i yap sadece B2 stenit fazndan olumaktadr. Daha nce de belirtildii zere 1100 C sinterleme scaklnda TiNi alamnn oksitlenmesini nlemek iin ksmi oksijen basncnn 5 10-25 atmden daha dk bir deerde olmas gerekir. Ayn scaklkta, oksijen giderici olarak kullanlan titanyum 510-27 ve magnezyum 10-34 atmlik ksmi oksijen basnc seviyelerine inmeyi olanakl klmaktadr. Her ne kadar bu teorik deerlere ulalmas ok mmkn olmasa da pratikte salanan oksijen ksmi basnc TiNi alam oksitleyecek ve ikincil faz oluturacak seviyelere ulamamtr. Bu konuda daha detayl aklamalar [6 ve 8] numaral referanslarda bulunabilir.
ekil 8. Farkl basnlarda baslm TiNi kompaktlarn sinterleme sonras XRD patternleri.
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3.3. Mekanik zellikler % 23 gzenee sahip TiNi alamna ait basma gerilim-gerinim erisi ekil 9da verilmitir. Bu eriden elde edilen mekanik zellikler de izelge 1de verilmitir. Dngsel yklemeyle birlikte dayan artarken geri kazanlamayan gerinim miktarnda zellikle ilk dng sonrasnda nemli bir azalma sz konusudur, elastik modl ise ayn kalmaktadr. lk dngde % 6ya yakn bir gerinim uygulandktan sonra geri kazanlamayan gerinim miktar % 1.7 civarnda gereklemitir. Gzenekli TiNi alamlarnda hacimli olanlardakinin (sabit gerilimde dnm) tersine dorusal sperelastisite davran gzlenmitir. Bu davrann ve geri kazanlamayan gerinimlerin iki nedeni vardr: test scaklnn (25 C) stenit biti scaklndan (41 C) dk olmas ve ekilsiz, homojen olmayan gzenek yapsnn yaratt lokal gerilmelerdir. Geleneksel sinterleme metoduyla retilen gzenekli TiNi alamlarnn yetersiz olan gzenek boyutu ve gzenek miktar nedeniyle kemik deiimi uygulamalar iin uygun olmad belirlenmesine ramen, mekanik zellikleri bakmndan hibir sorun tespit edilmemitir. Bir implant malzemesinden beklenen yksek mukavemet, dk elastik modl ve gerinim kazanma yeteneini baaryla yerine getirmektedirler. Bu anlamda kolayca, derece derece deien gzenekli implant uygulamalar iin gereken metalik malzemelerin retiminde kullanlabilir. rnein, implantn youn ekirdek ksm olarak sert doku nakil malzemesi retiminde kullanlabilir. Yksek gzenekli d yzeyler doku bymesine izin verirken i ksmda yer alan daha dk gzenekli ksm gerekli dayanc salayacaktr. Kk gzenekler ayn zamanda vcut svlarnn tanmna imkan verirken dk elastik modl sayesinde de gerilim perdeleme etkisi minimize edilebilecektir.
ekil 9. % 23 gzenekli TiNi alamnn gerilim-gerinim erisi. izelge 1. % 23 gzenekli TiNi alamnn mekanik zellikleri. Young modl, E (GPa) 13.2 Martensit oluum gerilimi, (MPa) 140
cr
% 2 gerinimde basma gerilimi, (MPa) lk dng 135 kinci dng 186 nc dng 188
4. SONULAR zellikle filtre malzemesi olarak kullanlmaya uygun TiNi malzemeler alam tozu kullanlarak magnezyum buhar altnda sinterleme suretiyle % 21-26 aralnda gzenekli olarak retilmilerdir. Magnezyumun TiNi alamn sinterleme esnasnda oksitlenme v.b. eitli kirlenmelerden ve buna bal istenmeyen ikincil Ti-Ni faz oluumundan koruduu grlmtr. retilen gzenekli malzemelerin gzenek miktar ve boyutu asndan yetersiz iken mekanik zellikler asndan olduka baarl olduu bulunmutur. Gzenekli TiNi alamlarnn dorusal sperelastisite davran sergiledikleri ve dngsel ykleme-boaltma ile byk miktarda gerinimleri tamamen geri kazanabildii belirlenmitir. TEEKKR Bu alma Trkiye Bilimsel ve Teknolojik Aratrma Kurumu (TBTAK, Proje no: 108M118) tarafndan desteklenmitir.
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KAYNAKLAR 1. Otsuka, K., Wayman, C.M., Shape Memory Materials, Cambridge University Press, Cambridge, UK, 1998. 2. Pelton, A.R., Stoeckel, D., Duerig, T.W., Medical Uses of Nitinol, Materials Science Forum, Vol. 327-328, pp. 63-70, 2000. 3. Itin, V., Gyunter, V., Shabalovskaya, S., Sachdeva, R., Mechanical Properties and Shape Memory of Porous Nitinol, Materials Characterization, Vol. 32, pp. 179-187, 1994. 4. Shabalovskaya, S., On the Nature of Biocompatibility and Medical Applications of Shape Memory and Superelastic NiTi-Based Alloys, Bio-Medical Materials and Engineering, Vol. 6,pp. 267-289, 1996. 5. Bansiddhi, A., Sargeant, T.D., Stupp, S.I., Dunand, D.C., Porous NiTi for Bone Implants: A Review, Acta Biomaterialia, Vol. 4, pp. 773-782, 2008. 6. Aydomu, T., Bor, ., Gzenekli TiNi ekil Bellekli Alamlarnn retilmesi ve Karakterizasyonu, 15. Uluslararas Metalurji ve Malzeme Kongresi, Dzenleyen: TMMOB Metalurji Mhendisleri Odas, s. 665-675, stanbul, 2010. 7. Li, B.Y., Rong, L.J., Li, Y.Y., Gjunter, V.E., Synthesis of Porous Ni-Ti Shape-Memory Alloys by Self-Propagating High-Temperature Synthesis: Reaction Mechanism and Anisotropy in Pore Structure, Acta Materialia, Vol. 48, pp. 3895-3904, 2000. 8. Yuan, B., Zhang, X.P., Chung, C.Y., Zeng, M.Q., Zhu, M., A Comparative Study of the Porous TiNi ShapeMemory Alloys Fabricated by Three Different Processes, Metallurgical and Materials Transactions, Vol. 37A, pp. 755-761, 2006. 9. Kaya, M., Orhan, N., Kurt, B., Khan, T.I., The Effect of Solution Treatment under Loading on the Microstructure and Phase Transformation Behavior of Porous NiTi Shape Memory Alloy Fabricated by SHS, Journal of Alloys and Compounds, Vol. 475, pp. 378-382, 2009. 10. Tosun, G., Ozler, L., Kaya, M., Orhan, N., A Study on Microstructure and Porosity of NiTi Alloy Implants Produced by SHS, Journal of Alloys and Compounds, Vol. 487, pp. 605-611, 2009. 11. Aydomu, T., Bor, A.., Production and Characterization of Porous TiNi Shape Memory Alloys, Turkish Journal of Engineering and Environmental Sciences, Vol. 35, pp. 69-82, 2011. 12. Li, B., Rong, L.J., Li, Y.Y., Porous NiTi Alloy Prepared from Elemental Powder Sintering, Journal of Materials Research, Vol. 13, pp. 2847-2851, 1998. 13. Zhu, S.L., Yang, X.J., Fu, D.H., Zhang, L.Y., Li, C.Y., Cui, Z.D., Stress-Strain Behavior of Porous NiTi Alloys Prepared by Powders Sintering, Materials Science and Engineering A, Vol. 408, pp. 264-268, 2005. 14. Greiner, C., Oppenheimer, S.M., Dunand, D.C., High Strength, Low Stiffness, Porous NiTi with Superelastic Properties, Acta Biomaterialia, Vol. 1, pp. 705-716, 2005. 15. Lagoudas, D.C., Vandygriff, E.L., Processing and Characterization of NiTi Porous SMA by Elevated Pressure Sintering, Journal of Intelligent Materials Systems and Structures, Vol. 13, pp. 837-850, 2002. 16. Zhao, Y., Taya, M., Kang, Y.S., Kawasaki, A., Compression Behavior of Porous NiTi Shape Memory Alloy, Acta Materialia, Vol. 53, pp. 337-343, 2005. 17. Aydomu, T., Bor, ., Processing of Porous TiNi Alloys Using Magnesium as Space Holder, Journal of Alloys and Compounds, Vol. 478, pp. 705-710, 2009. 18. Aydomu, T., Tarhan Bor, E., Bor, ., Phase Transformation Behavior of Porous TiNi Alloys Produced by Powder Metallurgy Using Magnesium as a Space Holder, Metallurgical and Materials Transactions A, in press, DOI: 10.1007/s11661-011-0714-z. 19. Bansiddhi, A., Dunand, D.C., Shape-Memory NiTi Foams Produced by Solid-State Replication with NaF, Intermetallics, Vol. 15, pp. 1612-1622, 2007. 20. Bansiddhi, A., Dunand, D.C., Shape-Memory NiTi Foams Produced by Replication of NaCl Space-Holders, Acta Biomaterialia, Vol. 4, pp. 1996-2007, 2008. 21. Wu, S., Chung, C.Y., Liu, X., Chu, P.K., Ho, J.P.Y., Chu, C.L., Chan, Y.L., Yeung, K.W.K., Lu, W.W., Cheung, K.M.C., Luk, K.D.K., Pore Formation Mechanism and Characterization of Porous NiTi Shape Memory Alloys Synthesized by Capsule-Free Hot Isostatic Pressing, Acta Materialia, Vol. 55, pp. 3437-3451, 2007. 22. Zhang, Y.P., Li, D.S., Zhang, X.P., Gradient Porosity and Large Pore Size NiTi Shape Memory Alloys, Scripta Materialia, Vol. 57, pp. 1020-1023, 2007. 23. Grummon, D.S., Shaw, J.A., Gremillet, A., Low-Density Open-Cell Foams in the NiTi System, Applied Physics Letters, Vol. 82, pp. 2727-2729, 2003. 24. Guoxin, H., Lixiang, Z., Yunliang, F., Yanhong, L., Fabrication of High Porous NiTi Shape Memory Alloy by Metal Injection Molding, Journal of Materials Processing and Technology, Vol. 206, pp. 395-399, 2008. 25. Bertheville, B., Porous Single-phase NiTi Processed under Ca Reducing Vapor for Use as a Bone Graft Substitute, Biomaterials, Vol. 27, pp. 1246-1250, 2006. 26. Dutta, R.S., Madangopal, K., Gadiyar, H.S. Banerjee, S., Biocompatibility of NiTi Shape Memory Alloy, Br. Corros. J. Vol. 28, pp. 217-221, 1993. 27. Pelton, A., Trepanier, C., Gong, X.Y., Wick, A., Chen, K.C., Structural and Diffusional Effects of Hydrogen in TiNi, SMST 2003, Organizer: SMST, pp. 33-42 Monterey, CA, 2004.
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POWDER PRODUCTION
www.turkishpm.org
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AA 2014 ALMNYUM ALAIM TOZLARINDA MA VE SPEX YNTEMLER KULLANILARAK KARBON LAVES ve ZELLKLERNN ARATIRILMASI
Sinan AKSZ, A. Tamer ZDEMR, B. BOSTAN Gazi niversitesi Teknik Eitim Fakltesi, Metal Eitimi Blm, Teknikokullar, 06500, Ankara, sinanaksoz@hotmail.com, tozdemir@gazi.edu.tr , bostan@gazi.edu.tr ZET Bu almada argon atmosferinde ve 790 C alma scaklnda gaz atomizasyon yntemi kullanlarak retilen AA 2014 alam tozlar kullanlmtr. Elde edilen tozlar daha sonra dikey atritrde ierisine karbon tozlar ilave edilerek tme ilemine tabi tutulmutur. tme ileminde spex ile tlen tozlar ile atritrdeki tozlar arasnda karlatrma yaplmtr. Atritrde yaplan tme ileminde yalayc olarak kullanlan inko stearatrn etkisi aratrlmtr. tme sresinin toz boyutuna olan etkisi tespit edilmeye allmtr. Yaplan deneysel almalar neticesinde spex ile tmede 45 dakika gibi ksa srelerde nihai rn elde edilebilirken atritrde bunu elde edebilmek iin 7 saat zerindeki srelere ihtiya duyulabilmektedir ve yalayc kullanlmadan yaplan tme ileminde gereklemesi gereken evrelerin olumad belirlenmitir. Anahtar Kelimeler: AA2014 Alminyum Alam, Mekanik Alamlama, Metal Matris Kompozit .
RESEARCH ON CARBON ADDITING IN AA2014 ALUMINIUM ALLOY AND FEATURES OF THE PRODUCTS AFTER MECHANICAL MILLING AND SPEX
ABSTRACT In this study, fine AA 2014 alloy powders manufactured by the method of gas atomization were used. Processing was accomplished under argon gas atmospheric conditions at 7900C. Then, some powders were mixed with graphite and attrition milled in a horizontal attritor where, rest of the powders was processed by using spex. There after, products of these different processes were compared in details. Thus, together with the effect of the addition of zinc stearate as a lubricant, the effect of processing time on mean powder sizes was investigated. It was found that, processing with spex was fast and the desired composite powder could only be achieved after 45 minutes. Where as, for the same product, the required attrition time was about 7 hours. It was concluded that, lubrication during processing was essential and without it, quality of milling was insufficient. Key words: AA 2014, Mechancal Alloying, Metal Matrix Composite. 1.GR Mekanik Alamlama (MA) yntemi bir hazne ierisindeki tozlara yksek enerjili bilyalar ile tekrarl olarak devam eden kaynaklanma, krlma ve yeniden kaynaklanmann meydana getirildii bir kat hal reaksiyonudur. lk olarak nikel ve elik bazl sper alamlarda uak endstrisi uygulamalarnda kullanlmak iin oksit dalmyla glendirilerek retilmitir. SPEX ileminde ise bir kerede 10 ile 20 g arasnda toz ilave edilebilen hazneye sahip olup ounlukla laboratuar artlarnda kullanlan bir cihazdr. MA sonras mikro yap gaz atomizasyon yntemi ile retilen tozlardan daha iyidir ve tane boyutu oranlar hzl katlatrma teknikleri kullanlarak elde edilen yntemlerle ayndr. lk aamada MA ilemi oksit dalm ile glendirme ilemleri ve Ni bazl sper alamlar iin gelitirilse de bu gnlerde alminyum ve bakr alamlarnn uygulamalarnda ve zellikle intermetalik yaplarda kullanlmaktadr
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[1-2]. TM yntemi ile retilen paralar gnmzde yaygn olarak kullanlmakta ve kullanm alanlar da giderek artmaktadr [3]. Mekanik retim sonras boyut aral tme esnasnda bilyelerin oluturduu enerji, bilye toz aarlk oran ve tme ilemi esnasnda oluan toplam scaklk ile belirlenebilir. Yaplan aratrmalarda SPEX ile yaplan tme ilemi ile dier dk enerjili tme ilemlerine gre daha hzl bir tme gereklemektedir. Yaplan deneysel almalarda SPEX ile 20 nm gibi dk tane boyutlarna ksa srelerde ulalabilirken dier yntemlerde bu boyuta ulamak iin uzun srelere ihtiya duyulmakta baz retim yntemlerinde ulalamamaktadr (ekil 1). Pulverisette isimli SPEX ile 32 saat tme sresinde 90 d/d hzda 40 nm, 180d/d hzda 31 nmve 360 d/d hzda ise 20 nm tane boyutuna ulalabilmektedir [4]. Suryanarayana ve arkadalarnn yapt alma ile ticari olarak kullanlan MA ileminin kullanm ve kullanm alanlar giderek artmaktadr [5].
ekil 1. Demir tozlar iin farkl tme trlerinde zamana bal olarak ortalama toz boyutu [4]. tme sonras tozlar birok taneden meydana gelecek ve tane boyutunun azalmas ile Hall Petch eitliine gre (=0 + kd1/2)mekanik zelliklerde bir artma meydana gelecektir [6]. ekil 2 incelendiinde tme sresine bal olarak numunelerin sertliklerinin giderek artt gzlemlenmektedir. Bu sertlik artna da yukardaki ekil 1 incelendiinde tme sresinin artmas ile tanelerin boyutunun artmasna neden olmakta ve tane boyutundaki azalma ise malzemede mukavemetlemeye neden olmaktadr.
ekil 2. tme sresine bal olarak saf ve glendirilmi Al alamnn sertlik grafikleri [6].
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2. DENEYSEL ALIMALAR 2.1. tme lemi Kullanlan AA 2014 tozlar, Dey tip gaz atomizasyon nitesinde 15 bar basn altnda yksek saflktaki inert tip argon gaz ile retilmitir. Tozlar atomizasyon nitesinde retildikten sonra elek analizi ile boyut dalm gerekletirilmi ve 100 m altndaki tozlar alnarak boyut dalm cihaz ile ortalama boyutu 95 m olarak tespit edilmitir. Boyutlandrma ilemi esnasnda, yaklak 5 kere ilem tekrarlanm ve btn sonular ortalama 95 m deerinde kmtr. Daha nce yaplan almalarda herhangi bir yalayc kullanlmad taktirde (Saf Al ierisine % 2 C) 2 saatte istenilen toz boyutuna ulalmtr [7]. Bu almada da nceki almaya paralel olarak yalaycsz olarak AA 2014 ierisine %2 C ve %2 C + % 0,5 orannda yalayc (inko stearat) ilave edilerek MA ilemine yalaycnn ve karbonun etkisi incelenmitir. Ayrca MA ile SPEX arasnda karlatrmalar yaplarak, her iki nitenin tme srelerinin tane yaplarna etkileri tespit edilmeye allmtr. tme sresinin; toz boyutuna, ekline ve sertlie olan etkileri belirlenmeye allmtr. Bu kapsamda MA ilemine tabi tutulan tozlarn tme sresine bal olarak sertlikleri ve mikro yaplar incelenmitir. MA ilemi sonrasnda karbonun sistem ierisinde karbr oluturma eilimi tespit edilmeye allmtr. Bu amala XRD analizleri yaplarak Al4C3 iin gerekli piklerin oluup olumad belirlenmeye allmtr. tme ilemleri sonrasnda numunelerin SEM ve XRF incelemeleri yaplarak meydana gelen deiimler ve kirlenme oluumlar tespit edilmeye allmtr. Tozlarn karakterizasyonu ve grntlenmesi esnasnda bir ok deneysel ekipmandan yararlanlmtr. Bu cihazlar sralamak gerekirse G.. Mhendislik Fakltesindeki Malvern Mastersizer E toz boyutu analiz cihaz, Atom Enerjisindeki Bruker D8 XRD analiz cihaz ile Cuk =1.5406 ve 2/dakika tarama hznda deneyler yaplmtr. Mikro yap incelemeleri G.. Teknoloji Fakltesi Metal Eitimi Blmndeki Joel JSM-5600 taramal elektron mikroskobunda, sertlik lmleri ise, Shimadzu Mikro Sertlik cihaznda 100g yk kullanlarak gerekletirilmitir. 3. SONULAR VE TARTIMA Tozlarn boyut analizleri esnasnda yaplan boyutlandrmalarda yaklak 5 adet boyutlandrmann da ayn boyut aralnda kmas, tozlarn retiminin uygun artlarda gerekletirildiini gstermektedir. Tozlarn SEM ile yaplan boyutlandrlmas ve mikro yap incelemelerinde kresel ve kresele yakn bir mikro-yapya sahip olduu gzlemlenmektedir (ekil 3).
ekil 3. MA ileminde kullanlan tozlar Sistemde kullanlan AA2014 tozlarna yalayc olarak kullanlan grafitin MA sresine bal olarak etkileri incelendiinde, normal artlarda tanelerde plakalama olmas beklenirken tozlar direk olarak krlp birlemektedir. Kullanlan grafitin AA 2014 tozlar iin yalayclk grevi stlenmedii tespit edilmi ve yalayc olarak alam tozlar iin inko stearat kullanmna geilmitir. 6064 malzemesinde ise yalayc olarak grafit kullanlm ve yksek tme srelerine ulalmtr. Yalaycnn kullanld artlarda ise tozlar MA srecinde izlemesi gereken nce tabaklama ve sonrasnda yksek sertlik ve peklemeyle birlikte krlma gzlenmitir [1, 8]. Krlma sonras ise tozlar tekrar mekanik birleme sonras nihai yapsn oluturmaktadr. Yalayc ilavesi yaplmadan almalarda en fazla 240 dakika MA sresine ulalrken (ekil 4 a) ve bu sre yalayc kullanlan sistemlerde ise krlmann yeni balad noktalara tekabl etmektedir (ekil 4 b). MA ileminin tamamland sre ise 420 dakika olarak belirlenmitir (ekil 4 c). 420 dakika allan Atritr kitlenmeye ve sorunlar oluturmaya balamaktadr. Bu sebeplerden dolay MA sresi olarak, en fazla 420 dakika kullanlmtr.
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ekil 4. MA a) Yalayc kullanlmadan 240 dak. b) Yalayc kullanlarak 240 dak c) Yalayc kullanlarak 420 dak. Yaklak 45 dak. sren SPEX ile tme almalarnda elde edilen toz yapsna (ekil 5) , MA ileminde yalayc da kullanlarak ancak 420 dakikada ulalabilmitir. Bu sonu ise SPEX ile yaplan tme performansnn MAya gre daha iyi olduu gstermektedir. Ancak MA ileminde yksek oranlarda toz malzeme kullanlabilirken, SPEX ile tme ileminde 10 gram gibi ok dk deerlerde toz tlebilmektedir [9].
ekil 5. SPEX ile 45 dak. tme a) X 100 b) X 200 Karbon ilavesi ile yaplan MA ilemindeki tozlarda XRD incelemeleri sonras karbr yapsna rastlanlamamtr (ekil 6). XRF incelemelerinde de, karbon miktarnn tme sresine bal olarak deimemesi XRD verilerini dorular niteliktedir. Bylece MA sresinin karbr oluumuna etkisinin olmad belirlenmitir. Bu konu hakk nda yaplan dier almalarda da benzer sonular elde edilmitir [7,10-13].
ekil 6. 7 saat MA ilemi gren tozlarn XRD analizi. MA sresinin artmasyla birlikte doal olarak tozlarn sertliklerinde de bir art meydana gelmektedir (ekil 7). Buradaki sertlik art azalan tane boyutlarndan (Hall Petch bants) ve uygulanan deformasyon neticesinde deformasyon sertlemesinden kaynaklanmaktadr. Tane boyutlarnn klmesi ile meydana gelen sertlik art ile birlikte tanelerin presleme basnlarnda da benzer artlar meydana gelmektedir. [6,14].
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ekil 7. Farkl srelerde MA ilemine tabi tutulmu tozlarn sertlik sonular KAYNAKLAR REFERENCES
1. Suryanarayana C., Mechanical alloying and milling, Progress in Materials Science, 46: 1-184 (2001). 2. Ruiz-Navas E.M., Fogagnolo J.B., Velasco F., Ruiz-Prieto J.M., Froyen L., One step production of aluminium 3. German R.M., ed. Sarta S., Trker M., Durlu N., Toz Metalurjisi ve Parackl Malzeme lemleri, Trk Toz 4. Claudio L. De Castro, Brian S. Mitchell., Nanoparticles from Mechanical Attrition, Department of Chemical 5. Suryanarayana C., Ivanov E., Boldyrev V.V., The science and technology of mechanical alloying, Materials 6. Razavi Tousi S.S.*, Yazdani Rad R., Salahi E., Mobasherpour I., Razavi M. , Production of Al20 wt.% Al2O3 7. Bostan, B., zdemir A.T., Kalkanl A., Microstructure characteristics in Al-C system after mechanical alloying 8. Son H.T., Kim T.S., Suryanarayana C., Chun B.S., Homogenous Dispersion of Graphite in a 6061 Aluminium 9. Suryanarayana C, Mechanical Alloying, Pergamon Materials Series, Volume 2, Pages 49-85, (1999). 10. Arslan G., Kara F., Turan S., Quantitative X-ray Diffraction Analysis of Reactive Infiltrated Boron CarbideAlu11. Wu, N. Q., Wu, J. M., Wang, G.X., Li, Z. Z., Amorphozation in the Al-C System by Mechanical Alloying, J. of 12. Besterci, M., Preperation Microstructure and Properties of Al-Al4C3 System Produced by Mechanical Allying, 13. Zhou, Y., Li Z.Q., Structural Characterization of a Mechanical Alloyed Al-C Mixture, J. Alloys and Comp.,414 14. Sivasankaran, S., Sivaprasad K., Narayanasamy R., Vijay Kumar Iyer, An investigation on flowability and
compressibility of AA 6061100x-x wt.% TiO2 micro and nanocomposite powder prepared by blending and mechanical alloying, Powder Technology 201 (2010) 7082. (2006) 107-122. Materials and Design, 27 (2006) 416-421. All. And Comp. 260 (1997) 121-126. minium Composites Journal of the European Ceramic Society 23, 12431255, (2003). Alloy by Ball Milling, Materials Science & Engineering, 163-169, (2002). and high temperature treatment, Powder Metallurgy, 47:1 (2004) 37-42. composite powder using high energy milling , Powder Technology, 192 (2009) 346351. Science and Engineering A304306 : 151158, (2001). Engineering, Tulane University,New Orleans, Louisiana, USA, syf.6. Metalurjisi Dernei , Ankara, (2007). matrix composite powders by mechanical alloying Composites: Part A 37 :21142120 (2006)
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BOR OKSTTEN ELEMENTEL BOR TOZU RETM PARAMETRELERNN ARATIRILMASI

Bahadr GNEY ve brahim USLAN Gazi niversitesi, Makina Mhendislii Blm, Maltepe, Ankara, bahadirguney@gmail.com, iuslan@gazi.edu.tr ZET Bu almada elementel bor tozu oda scaklnda, mekanik tme tekniiyle retilmitir. Bu amala magnezyum (Mg) ve bor oksit (B2O3) tozlar spekste farkl parametreler kullanlarak tlmtr. Tepkimenin gereklemesi ile elementel bor (B) ve magnezyum oksit (MgO) rn olarak elde edilmitir. Farkl parametrelerde tlm olan numuneler XRDde analiz edilmi ve elde edilen pik deerleri patern deerleri ile karlatrlarak yorumlanmtr. Elementel bor tozu tayini yapmak iin iki numune ICP- OESde analiz edilerek 100 mglk numunede 11,7 mg elementel bor tozu tespit edilmitir. alma neticesinde magnezyum ve bor oksitin mekanik tlmesi ile bor oksit iindeki bor indirgenerek % 77lere varan oranlarda elementel bor tozu retilmitir. Anahtar Kelimeler: Bor Oksit, Elementel Bor, tme, Speks. INVESTIGATION OF PRODUCTION PARAMETERS OF ELEMENTAL BORON FROM BORON OXIDE ABSTRACT In this study, elemental boron powder was produced by mechanical milling technique at room temperature. With this purpose, magnesium (Mg) and boron oxide (B2O3) powders were milled in a spex by using different parameters. Elemental boron (B) and magnesium oxide (MgO) were obtained as a product after the reaction. The milled samples by different parameters were analyzed using XRD unit and interpreted by comparing values of peak and pattern. By analyzing of the samples using ICP-OES unit 11,7 mg of elemental boron powder was determined in the sample which is 100 mg. As a result of this study, magnesium and boron oxide were milled mechanically and with this process, boron which was in the boron oxide was reduced and finally obtained with the yield of 77%. Keywords: Boron oxide, elemental boron, milling, spex. 1.GR Bor madenleri iindeki B2O3 oranna gre deerlendirilir ve ticari deer kazanr. lkemizde Emet, Bigadi ve Kesdelekde bulunan kolemanit (Ca2B6O11.5H2O), %50,8 oran ile en yksek B2O3 ieriine sahip bor minerallerinden biridir. Yksek saflkta B2O3, borik asitin iki aamada dehidrasyonu yntemiyle retilmektedir [1-4]. Mekanik enerji sayesinde kimyasal reaksiyonlarn ve faz deiimlerinin gerekletii mekanik- kimyasal sentez yntemi ile indirgeme reaksiyonlar, oksitleme reaksiyonlar ve elementel toz retimi gerekle-
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tirilebilmektedir. Literatrde bunlarla ilgili almalar mevcuttur [5-17]. Mekanik-kimyasal sentez uygulamalar genellikle atritr ve speks tipi tclerde yaplmaktadr [11]. Atritrler ve speksler, mekanik tme ve mekanik alamlama almalarnda kullanlan yksek enerjili ve verimli tclerdir. Koruyucu gaz atmosferinde de allabilen atritrlerde iinde tmenin yapld kap sabittir/dnmez. Atritrlerin verimliliinde en etkin parametre kartrc kollarn hzdr. Spekste ise, iinde tmenin/ mekanik alamlamann gerekletii reaktr dnme ve titreim hareketleri birlikte yapldndan alamlama etkinlii daha yksektir. Spekste mekanik tme yaparak; Bolarin ve arkadalar [6], Mn2O3 ve La2O3 bileik tozlarndan lantanyum magnatit (LaMnO3) bileiini, Garcia ve arkadalar [7] de elementel Co ve Ni tozlarndan Ni-Co alamn elde etmilerdir. Ricceri ve Matteazzi [12] ise Mg ve B2O3 tozlarn spekste terek elementel bor tozunu rettiklerini bildirmilerdir. Bununla ilgili deerlendirme, tartma blmnde verilmitir. 2. DENEYSEL ALIMA 2.1. Malzeme Deneylerde kullanlan Mg tozlar piyasadan, B2O3 ise Eti Maden letmeleri Bandrma Bor Oksit Fabrikasndan temin edilmitir. Mg tozlar, Gazi niversitesi Fizik Blmnde bulunan XRD cihaznda analiz edilerek dorulanmtr. Amorf yapdaki bor oksitin XRD analizinden ise sonu alnamamtr. 2.2. Speks Uygulamalar Speks uygulamalar Gazi niversitesi Kimya Mhendislii Blm Laboratuvarnda bulunan Spex 8000M cihaz ile yaplmtr. Speks almalarnda kullanlan parametreler izelge 1de verilmitir. tme ilemlerinde drt adet paslanmaz elik bilya kullanlmtr. Bu bilyalardan bir tanesi 16 mm apnda dier ise 4,8 mm apndadr. Bu bilyalarn toplam arl 17,51 gramdr. Speks uygulamasnda tepkimeye girecek toz miktarnn arlka %48,83nn Mg, %51,17sinin ise B2O3 tozlar olduu hesaplanmtr. Bu deerlere gre, izelge 1de verilen toz/bilya oranlar iin Mg ve B2O3 miktarlar bulunmutur. Spekste tmenin gerekleecei reaktr iine Mg, B2O3 ve bilyalar kontroll atmosfer nitesinde (glove-box) koyulmu ve reaktr kapa skca kapatlp hava girii engellenmitir. Daha sonra reaktr speks cihazna yerletirilip tme ilemi yaplmtr. 2.2. XRD, ICP-OES ve SEM Analizleri tme sonras elde edilen toz karmlarn tm Eti Maden letmeleri Ar-Ge Laboratuvarnda bulunan Rigaku D-max 2200 model XRD cihaznda analiz edilmitir. Ayrca elementel bor analizi iin ODT Merkez Laboratuvarnda bulunan Perkin Elmer Optima 4300DV ICP-OES (Endktif Elemi Plazma Optik Emisyon Spektrometresi) cihazndan yararlanlmtr. Bu cihazla, yetmi civarnda kimyasal elementin eser, minr ve major konsantrasyon dzeylerinde ve ayn anda analizi mmkndr. ICPOES analizleri 5 ve 9 nolu deney numuneleri iin gerekletirilmitir. Bu analizler iin 0,1 g rnek alnp kral suyu (3 hacim HCI ve 1 hacim HNO3) iinde zlmtr. nce stlan zelti daha sonra 100 mlye saf su ile seyreltilmitir. Oluan zeltiden 1 ml alnp 50 mlye saf su ile tamamlanmtr. Analiz sonucu cihazdan okunan deerden 0,1 glk toz karm iindeki elementel bor miktar hesaplanmtr. Mg ve B2O3 tozlar ile 5 ve 9 nolu deney numunelerinin taramal elektron mikroskop almalar ise Gazi niversitesi Metal Eitimi Blmnde bulunan JEOL JSM 6060 LV model SEM cihaznda gerekletirilmitir.
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3. DENEYSEL BULGULARLAR VE TARTIMA Deneysel almalarda Mg ve B2O3 tozlar speks tipi deirmende tlm ve denklem (1)de verilen reaksiyon ile elementel bor tozunun retilmesi amalanmtr: B2O3 + 3Mg 2B + 3MgO (1) Deneylerde kullanlan Mg ve B2O3 tozlarnn SEM grntleri ekil 1de verilmitir.
(a) (b) ekil 1. (a) Mg, (b) B2O3 tozlarnn SEM grntleri 1/27 toz/bilya oran ve 20 dakika sreyle yaplan tme almalarndan elde edilen toz numunelerinin XRD analizinden elde edilen grafikteki zirve deerleri XRD cihazndaki desenlerle karlatrlm ve grafikteki zirvelerin tamamnn magnezyuma ait olduu, hedeflenen tepkimenin bu deney parametreleri iin gereklemedii grlmtr (ekil 2). Karm oran 1/27 alnarak yaplan tme ileminden beklenen sonu alnamamas zerine yeni parametreler belirlenmitir. Yaplacak uygulamalarda bilya says sabit tutulurken, farkl karm oranlar (toz/bilya) ve sreler kullanlmtr (Deney 2-4). Olas farkllklar grebilmek iin birbirine uzak karm oranlar alnmtr. 1/48 karm orannda 90 dak. sreyle yaplan Deney 2 iin hem Mg hem de MgO pikleri grlm
ekil 2. Deney 1 iin XRD analizi. Toz/bilya oran: 1/27, sre: 20 dak.
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ekil 3. Deney 2 iin XRD analizi. Toz/bilya oran: 1/48, sre: 90 dak. (ekil 3); reaksiyonun gereklemeye balad fakat srenin tozlarn tamamnn tepkimeye girmesine yetecek kadar uzun olmad anlalmtr. MgOe ait desen deerlerinde yer alan 42,917de oluan %100lk pik grafikte net olarak grlmektedir. Ayrca grafikte yer alan ikinci en yksek iddetli pik ise hem magnezyumun 36,620deki pikine uyarken, hem de MgOe ait 36,937deki pike uymaktadr. Dolaysyla bu pikin tam olarak hangisine ait olduu bilinmemektedir. Fakat magnezyumun %100lk pikine uymas, ona ait olma olasln artrmaktadr. Ayn karm orannda 180 dak. sreyle yaplan Deney 3 iin tepkime tamamen gereklemitir (ekil 4). Burada magnezyuma ait pikler yok olarak, yerine MgO pikleri olumutur. Grafikte bir de demire ait bir pik ortaya kmtr. Bu pikin uzun sreli tmeye bal arpmalar neticesinde, bilyalardan veya reaktr eperlerinden kaynakland dnlmektedir. Bir nemli nokta ise, her iki reaksiyon sonucunda olumas beklenen bir dier rn olan elementel bor grlmemitir. 1/8 karm orannda 300 dak. sreyle yaplan Deney 4e ait numunelerin analizinden elde edilen grafik (ekil 5) incelendiinde, oluan piklerin magnezyuma ait olduu grlmektedir. Ayrca 42-44 deerleri arasnda MgOe ait olabilecek kk bir pik grlmektedir. Dier iki almaya gre uzun sren bir tme olmasna ramen beklenen reaksiyon gereklememitir. Bu da toz/bilya karm orannn tepkimenin gereklemesinde ok etkin bir rol olduunu gstermektedir.
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1/48 karm oran iin 90 dakikada balayan tepkimenin 180 dakikada tamamland grldnden, bu karm oran sabit tutulup, zaman aral daraltlarak tepkimenin yaklak olarak ne zaman tamamland yeni deneylerle belirlenmeye allmtr (Deney 5-6). Ayrca yeni karm oran (1/36) ve srelerle (120, 150, 180 dak.) farkl uygulamalar yaplmtr (Deney 7-9). Deney 5-9un hepsinde reaksiyonun tamamen gerekletii Mg pikinin olumad, sadece MgOe ait piklerin olutuu grlmektedir. Bunlara ait rnek bir XRD kts Deney 7 iin ekil 6de verilmitir. Buradan hem bir 1/36lk hem de 1/48lik karm oranlarnda yaklak
ekil 6. Deney 7 iin XRD analizi. Toz/bilya oran: 1/36, sre: 120 dak. 120 dakikalk tme sresinin reaksiyonun gereklemesi iin yeterli olduu anlalmtr. Yaplan bu be uygulamann sonularnn ortak zelliinden biri de, hepsinde demire ait pik grlrken, beklenen rn olan elementel bora ait herhangi bir pik grlmemitir. Deney 5 ve Deney 9 numuneleri iin ICP-OES cihaznda yaplan elementel bor tayini almalarndan elde edilen dalga boyu-konsantrasyon erisi ekil 7de verilmitir. Cihazdan okunan deerlere bal yaplan hesaplamalardan 0,1 glk toz karm iinde, Deney 5 iin 11,35 mg, Deney 9 iin ise 11,7 mg elementel bor tozu bulunduu tespit elikidir.
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ekil 7. ICP-OES dalga boyu-konsantrasyon erisi. Deney 5: 1/48, 120 dak., Deney 9: 1/36, 180 dak. ekil 8. Ricceri ve Matteazziye ait makalede verilen XRD grafikleri [12]. a) tme ncesi B2O3 ve Mg karm, b) Karm oran 1/27, sre 10 dak. olan karm (reaksiyon tamamlanm), c) bdeki parametrelerle tlm ve kimyasal ayrtrlm, d) Karm oran 1/8, sre 300 dak. olan karm (kimyasal ayrtrlm). Not: Mg (x), MgO (o), B (+). edilmitir. Stokiyometrik hesaplara gre bu miktarn 15,17 mg olmas gerekmektedir. Speks uygulamasyla elementel bor tozu retimi iin buna gre bir karlatrma yapldnda; Deney 5 iin %75lik, Deney 9 iin ise %77lik bir baar elde edildii grlmtr. Bu almada elde edilen sonular Ricceri ve Matteazzinin almasyla [12] karlatrldnda, dikkat ekici farkllklar ortaya kmtr. Ricceri ve Matteazzi [12], 8 adet 8 mmbapnda bilya kullanm ve optimum artlar 1/27 karm orannda 9 dakika olarak bulmular; tme ncesi ve sonras XRD grafiklerini sunmulardr (ekil 8). Buradaki grafikler incelendiinde, ilgili makale ieriiyle elikiler tespit edilmitir. ekil 8.adaki grafiin B2O3 ve Mg iin olduu belirtilmi, ancak * ile gsterilen piklerin neyi temsil ettii belirtilmemitir. Bu pikler, desenlerle karlatrldnda hibir eye uymamtr. Fakat piklerin dizilii ve tipik grntsnn magnezyuma benzemesi nedeniyle, bu grafik kaydrldnda magnezyuma ait piklere uyduu grlmtr. ekil 8.bdeki pikler Mg olarak tanmlanm, fakat Mg desenleri incelendiinde bu piklerin magnezyuma ait olmad grlmtr. Ayrca reaksiyonun tamamland belirtilen bu grafikte, olumas gereken MgO ve elementel B pikleri yerine Mg piklerinin grlmesi nemli bir elikidir. XRD analizi ncesi kimyasal ayrtrma ile Mg, Fe ve tepkimeye girmeyen Mg tozlarnn ortamdan uzaklatrld, ortamda sadece elementel bor tozu kald ifade edilen ekil 8.cde verilen grafik iin; tm piklerin MgO olmas da ayr bir Ayrca literatrdeki MgOe ait desenlerde sadece on noktada pik oluurken, ekil 8.cde birok noktada pik olumaktadr. Benzer ekilde ekil 8.dde de, kimyasal ayrtrmaya karn hem MgO, hem de elementel bor pikleri iaretlenmitir. Ricceri ve Matteazzi [12] XRD analizlerini Co K kullanarak yapmlardr. Bir element veya bileie ait XRD grafiinde ilk olumas gereken pik noktas %100lk noktadr. Co K iin elementel bora ait %100lk zirve yaklak 20,3te olumaldr. Fakat ekil 8.dde grld gibi, grafik 20den balamakta ve MgO ve elementel B pikleri, desenlere uymamaktadr. Bir dier husus da, ekil 8.dde olduu gibi eer XRDde elementel B analizi mmknse, buna ait piklerin ekil 8.cde niin grlmediidir. XRD analizlerindeki bu hatal yorumlardan dolay, bu alma kapsamndaki sonularn Ricceri ve Matteazzinin verileriyle [12] uyum gstermedii kanaatine varlmtr. 4. SONULAR Drt bilyann kullanld spekste tme uygulamalarnda, 1/8 karm oran ile 300 dakika tme sresiyle bile mekanik-kimyasal sentezleme gereklememi iken, 1/48 karm oran iin 90 dakikalk bir tme sresiyle sentezlemenin balad tespit edilmitir.
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Reaksiyonun en ksa zamanda gereklemesi ve yksek oranlarda elementel bor tozu elde etmek iin magnezyum ve bor oksit tozlarnn toz/bilya karm orannn 1/36 veya 1/48 alnarak en az 120 dakika sreyle spekste tlmesi gerektii belirlenmitir. Bu tme ilemleri sonunda bor oksitin indirgenerek %77ye varan miktarlarda elementel bor elde edilmitir. Bu miktar artrmak iin bilya says ve boyutunun deitirilmesinin veya reaksiyon hzn artrmak iin katalizr kullanlabilecei dnlmektedir. almalar sonunda elementel borun XRDde tespit edilemedii grlmtr. Borun teyiti ve miktar olarak analizi ICP-OESde yaplabilmitir. Bunun dnda elementel bor tespiti iin kimyasal tayin yntemleri aratrlabilir. tme ilemi ile elementel bor tozu retiminde hem kullanlan hemde elde edilen rnlerin miktarlar dktr. Endstriyel olarak yksek miktarlarda elementel bor tozu retmek iin atritr, silindirik deirmen veya byk hacimli kaba sahip speks kullanlm aratrlmaldr. Ricceri ve Matteazzinin almasnda [12] verilen XRD analizlerine ait grafiklerin yorumlarnda elikiler sz konusudur. KAYNAKLAR 1. Ulusal Bor Aratrma Enstits (BOREN), www.boren.gov.tr/borhk.htm. 2. DPT 8. Be Yllk Kalknma Plan Madencilik zel htisas Komisyonu Raporu,Endstriyel Hammaddeler Alt Komisyonu, Kimya Sanayi Hammaddeleri, DPT:2608-K:619 2: 5-40, 2001. 3. alk A., Trkiyenin Bor Madenleri Ve zellikleri, Mhendis Ve MakineDergisi, Say 508, Mays 2002. 4. Ylmaz A., Her Derde Deva Hazinemiz Bor, Bilim ve Teknik Dergisi, say 414,38-48, Mays 2002. 5. Gennari F.C., Castro F.J., Gamboa J.J.A., Synthesis of Mg2FeH6 by Reactive Mechanical Alloying: Formation and Decomposition Properties, Journal ofAlloys and Compounds, 339, 261267, 2002. 6. Bolarin A.M., Sanchez F., Ponce A., Martinez E.E., Mechanosynthesis ofLanthanum Manganite, Materials Science and Engineering A, 454455, 6974, 2007. 7. Garcia-Contreras M.A., Fernandez-Valverde S.M., Vargas-Garcia J.R., Oxygen Reduction Reaction On CobaltNickel Alloys Prepared By Mechanical Alloying,Journal of Alloys and Compounds, 434435, 522524, 2007. 8. Choi C.J., Preparation Of Ultrafine Tic-Ni Cermet Powders By Mechanical Alloying, Journal of Materials Processing Technology, 104, 127-132, 2000. 9. Valderruten J.F., Perez Alcazar G.A., Greneche J.M., Study Of FeNi Alloys Produced By Mechanical Alloying, Physica B, 384, 316318, 2006. 10. Birajdar B., Gruner W., Herrmann M., Perner O., MgB2 Bulk And Tapes Prepared By Mechanical Alloying: Influence Of The Boron Precursor Powder, Supercond. Sci. Technol., 19, 512520, 2006. 11. Suryanarayana C., Mechanical Alloying and Milling, Marcel Dekker, New York, 359, 2004. 12. Ricceri R., Matteazzi P., Mechanochemical Synthesis Of Elemental Boron, International Journal of Powder Metallurgy, 39(3), 48-52, 2003. 13. Boldyrev V., Boldyreva E., Mechanochemical of Interfaces, Materials ScienceForum, 88-90, 711714, 1992. 14. Tokumitsu K., Mechanochemical Reaction Between Metals and Hydrocarbons-Formation of Metal Hybrides, Materials Science Forum, 88-90, 715-722, 1992. 15. Hida M., et al., Mechanochemical Reaction in Various Systems Involving Ionic and Hydrogen Bond Crystals, Materials Science Forum, 88-90, 729-736, 1992. 16. Popovich A.A, et al., Mechanochemical Technology of Synthesis of Refractory Compounds and Alloys Based Upon Them, Materials Science Forum, 88-90, 737-744, 1992. 17. Gney, B., Bor Oksitten Elementel Bor Tozu retim Parametrelerinin Aratrlmas, Yksek Lisans Tezi, Gazi niv. Fen Bil. Enst., Ankara, 2007.
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Fe2O3N ZOTERMAL NDRGENMES AKABNDE SAF CH4 LE REAKSYONUYLA Fe3C TOZ SENTEZ
enol ETNKAYA, erafettin EROLU stanbul niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mh. Blm Avclar Kamps, 34320 Avclar / stanbul senol-c@istanbul.edu.tr seref@istanbul.edu.tr ZET Tek fazl Fe3C tozu, 800 Kde H2 atmosferinde Fe2O3in izotermal indirgenmesini takiben indirgenmi rnn saf CH4 ile reaksiyonu yoluyla sentezlenmitir. lk olarak Fe2O3in H2 atmosferinde farkl srelerdeki indirgenme davran incelenmitir. Daha sonra farkl indirgeme sresi (2.5 dk, 5 dk ve 10 dk) akabinde saf CH4 gaz ile deiik srelerde karbrizasyon reaksiyonlar gerekletirilmitir. Arlk deiim lmleri ve XRD analizleri, tek faz Fe3C tozunun yksek oranda indirgenmi ( 5 dk) tozun saf CH4 (15 dk) ile reaksiyonu sonucu elde edildiini gstermitir. Sentezlenen rnlerde morfoloji almalar SEM kullanlarak yaplmtr. Sentezlenen Fe3C tozunun partikl ve kristal boyutlar srasyla 0.30.9 m ve 40130 nm olarak llmtr. Anahtar Kelimeler: Fe3C toz sentezi, kat-gaz reaksiyonu, X-n difraksiyonu, morfoloji.
SYNTHESIS OF Fe3C POWDER BY ISOTHERMAL REDUCTION OF Fe2O3 AND SUBSEQUENT REACTION WITH PURE CH4
ABSTRACT Single phase Fe3C powder was synthesized by isothermal reduction of Fe2O3 in H2 atmosphere followed by reaction of reduced product with pure CH4 at 800 K. Firstly, reduction behavior of Fe2O3 was investigated in H2 atmosphere at various times. Then, carburization reactions were subsequently carried out after three different reduction times (2.5 min, 5 min and 10 min). Weight change measurements and XRD analysis showed that single phase Fe3C powder was obtained by reaction of highly reduced ( 5 min) powder with pure CH4 ( 15 min). Morphological analysis on the products was carried out by SEM. The particle and crystallite sizes of the synthesized Fe3C powder were measured to be 0.30.9 m and 40130 nm, respectively. Keywords: Fe3C powder synthesis, solid-gas reaction, X-ray diffraction, morphology. 1. GR Fe3C (demir karbr / sementit), elik ve demir alamlarnn mekanik zelliklerini gelitirmesi ve CO2/H2 gazlarndan hidrokarbon retiminde katalizr olarak kullanlmas nedeniyle byk bir teknolojik neme sahiptir. Genellikle elik matriks ierisinde bulunduundan tek faz olarak elde edilmesi olduka gtr. Manyetik zellik gsterdii iin Fe3C tozlarnn manyetik uygulamalar da vardr. Son zamanlarda nanoboyutlu Fe3C, karbon fiber, nanotp ve nanopartikllerin sentezinde katalizr olarak tercih edilmektedir [1]. imdiye kadar Fe3C sentezi iin pek ok yntem rapor edilmitir. Nikitenko ve dierleri [2], Fe-Fe3C nanokristal partikllerini sonokimyasal metotla retmilerdir. Nelson ve Wagner [3], alkali redksiyon; Morjan ve dierleri [1],
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lazer piroliz; Lee ve dierleri [4] ise kimyasal buhar biriktirme (CVD) yntemleriyle nanokristal Fe3C tozu sentezlemilerdir. Tm bu sentez teknikleri yksek scaklk, pahal hammadde veya karmak tehizat gerektirmektedir. Reaktan olarak nanopartikl Fe ve hidrokarbon gazlar kullanldnda [5, 6] ise Fe3C nispeten daha dk scaklklarda olumaktadr. Bu ynteme ait baz detaylar aada verilmektedir. Arabczyk ve dierleri [5], az miktarda K2O, Al2O3 ve CaO gibi oksitler ieren Fe3O4i H2 ieren atmosferde 853 Ke stma srasnda nce Fee redklemilerdir. Daha sonra nanokristal Fe katalist tozunun CH4, CH4/N2 veya CH4/H2 gazlar ile 773853 K aralnda karbrizasyon kinetiini incelemiler ve Fe3C oluum artlarn aratrmlardr. Sentezlenen rnlerin Fe3Cn yannda karbrlenmemi Fe ve serbest C ierdiini rapor etmilerdir. Karbrizasyon prosesinin paralanm CH4 gaznn demir yzeyindeki adsorbsiyonu ile kontrol edildiini vurgulamlardr. Narkiewcz ve dierleri [6], yukarda bahsedilen yntemle [5] sentezlenen Fe3Cde ayrntl karakterizasyon almalar yapmlardr. Aratrmaclar, sentezlenen rnlerin ortalama kristal (tane) boyutlarnn 4167 nm arasnda olduunu ve nihai rnlerin arlka % 7.816.8 arasnda serbest C ierdiini rapor etmilerdir. Bu almada ise Fe3C sentezi, Fe2O3 tozlarnn 800 Kde H2 atmosferinde izotermal indirgenmesi akabinde saf CH4 gaz ile reaksiyonu sonucu gerekletirilmitir. Sentezlenen rnlerin karakterizasyonu iin arlk deiim grafikleri ile XRD ve SEM teknikleri kullanlmtr.
2. DENEYSEL ALIMALAR Deney dzenei temel olarak Ar (% 99,999), H2 (% 99,99) ve CH4 (% 99,5) gazlarn ieren gaz silindirlerinden, bu gazlarn ak hzlarn hassas bir ekilde belirlemek iin ak lerlerden (Dwyer) ve ierisinde sentez reaksiyonlarnn gerekletirilecei kuvars tp (i ap: 20 mm) bulunan frn sisteminden (Strhlein) olumaktadr. Sentez almalar iin gerekletirilen her bir deneyde ~10-3 mol (~0,1597 g) Fe2O3 tozu (SigmaAldrich) kullanlmtr. Tm deneyler ncesinde, oksit tozunun bnyesinde bulanabilecek olan nemin giderilmesi amacyla ~373 Kdeki etvde 10 dakikalk bekletme yaplm ve tartmlar 10-4 g hassasiyete sahip analitik terazide (Sartorius BP110S) gerekletirilmitir. Tartlan Fe2O3 tozu almina kaykk ierisinde tp frnn merkezine yerletirilmitir. Yaklak 25 K/dk stma hzyla 800 Ke klncaya kadar 85 cm3/dk ak hznda Ar gaz sisteme beslenerek stma yaplmtr. Frn istenilen scakla ulatktan sonra oksit tozunun H2 gazyla (110 cm3/dk) deiik sreler iin indirgenmesi incelenmitir. Daha sonra farkl indirgeme srelerinin (2.5, 5 ve 10 dk) akabinde 40 cm3/dk ak hzndaki saf CH4 gaz ile deiik srelerde deneyler gerekletirilmitir. Tm deneylerde frn oda scaklna soutuluncaya kadar 85 cm3/dk ak hznda Ar gaz sistemden geirilmi ve akabinde sentezlenen rnlerin arlklar tespit edilmitir. Sentezlenen rnlerinin faz analizleri, Rigaku D/Max2200/PC marka XInlar Difraksiyon (XRD) cihaznda; morfoloji incelemeleri ise, Jeol 5600 ve Jeol 6335 marka Taramal Elektron Mikroskoplarnda (SEM) gerekletirilmitir. Reaksiyon rnlerinin kristal byklkleri ise, (1) nolu eitlikte verilen Scherrer forml kullanlarak hesaplanmtr. (1)
Eitlik (1)de gsterilen , Cu K radyasyonunun dalga boyunu (0,15418 nm); , difraksiyon asn; t, kristal boyutunu ve , yar ykseklikteki pik geniliini (FWHM) ifade etmektedir. FWHM deerleri belirlenirken ~0,2lik cihazdan kaynaklanan pik genilemesi de dikkate alnmtr. 3. BULGULAR ve DEERLENDRME 3.1. Fe2O3in H2 Atmosferinde zotermal ndirgenmesi 3.1.1. Fe2O3in ndirgenme Kinetii ekil 1de 800 Kde Fe2O3in H2 atmosferinde indirgenmesi srasnda reaksiyon sresinin oksit tozundaki arlk deiimine etkisi grlmektedir. ekildeki yatay kesikli izgiler, Fe2O3ten Fe3O4, FeO ve Fe dnmleri iin hesaplanm teorik arlk deiimlerini ifade etmektedir. Arlk deiimi grafiinden, 800 Kde 10 dk iinde % 100e yakn bir indirgemenin gerekletii anlalmaktadr.
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ekil 1. H2 atmosferinde reaksiyon sresinin Fe2O3in arlk deiimine etkisi (T = 800 K) 3.1.2. XRD Analiz Bulgular ekil 2de balang tozuna (Fe2O3) ve indirgeme almalar sonras elde edilen reaksiyon rnlerine ait X-nlar difraksiyon paternleri grlmektedir. XRD paternleri, 2.5 dklk indirgeme sresinin yeterli olmadn ve oluan Fein yannda yapda hala demir oksitler (Fe2O3, Fe3O4 ve FeO) bulunduunu; 5 ve 10 dklk indirgeme sonras ise rnlerin sadece Fe ierdiini gstermektedir. Bu bulgular, arlk deiimleri ile kalitatif olarak uyumaktadr.
ekil 2. Balang tozunun (Fe2O3) ve bu tozun 800 Kde H2 atmosferinde deiik srelerdeki indirgenme almalarna ait X-nlar difraksiyon paternleri
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Kristal boyutlar, yar ykseklikteki pik geniliklerinden (1) nolu eitlik kullanlarak belirlenmitir. Balang malzemesi olan Fe2O3 tozunun kristal boyutunun ~75 nm, 2.5, 5 ve 10 dklk indirgeme sonras elde edilen rnlerin kristal boyutlarnn ise >200 nm olduu hesaplanmtr. 3.1.3. Morfoloji ncelemeleri Fe2O3 tozunun ve 800 Kde H2 atmosferinde indirgenmi rnlerin SEM grntleri ekil 3te verilmektedir. Fe2O3 tozu, kk kresel partikllerden (ap: 2080 nm); rnler ise kaba partikllerden olumaktadr. Reaksiyon sresi 2.5 dk olan rn morfolojisinin 5 ve 10 dklk numunelere kyasla farkl olduu (daha kk partikl boyutuna sahip partiklleri de bnyesinde bulundurduu) SEM grntlerinden grlmektedir. XRD sonularna gre bu rnde hala oksitler bulunduundan, morfolojideki kk partikllerin demir oksitler olduu anlalmaktadr. 5 ve 10 dklk indirgeme sonras rn morfolojilerin birbirine benzedii ve partikl boyutlarnn 0.20.8 m arasnda deitii belirlenmitir. Ayrca, indirgeme srasnda oluan ve birbirleri ile temas halindeki demir tozlarnn sinterletii grlmektedir.
ekil 3. (a) Fe2O3 tozu ve 800 Kde H2 atmosferinde (b) 2.5 dk, (c) 5 dk, (d) 10 dk indirgeme sonras elde edilen reaksiyon rnlerinin SEM grntleri 3.2. H2 Atmosferinde Elde Edilmi rnlerin Saf CH4 Gazyla zotermal Reaksiyonu 3.2.1. Farkl Oranlarda ndirgenmi rnlerin Karbrizasyon Kinetii Karbr sentezi almalar srasnda sinterlemeyi dk tutabilmek iin farkl indirgenme oranlarna sahip tozlarda karbrizasyon almalar yaplmtr. ekil 4te 800 Kde karbrizasyon sresinin arlk deiimine etkisi grlmektedir. Arlk deiimlerinden, tam indirgeme sonras (10 dklk indirgeme sonras) yaplan karbrizasyon almalarnda, 15 dklk reaksiyon sresinin Fe3C oluumu iin yeterli olduu grlmektedir. 5 dk indirgenmi numuneye ait eriden, CH4 gaznn balangta yapda kalan az miktardaki oksitleri indirgedii ve 15 dkda karbrizasyonun tamamland anlalmaktadr. Daha dk indirgeme orannda (2.5 dklk indirgeme sonras) ise tek faz Fe3C sentezinin allan artlarda mmkn olmad grlmektedir.
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ekil 4. 800 Kde 2.5, 5 ve 10 dk indirgenmi numunelerde karbrizasyon sresinin arlk deiimine etkisi 3.2.2. XRD Analiz Sonular ekil 5te farkl indirgenme oranlar iin yaplan karbrizasyon almalar sonras elde edilen rnlere ait X-nlar difraksiyon paternleri verilmektedir. XRD paternlerinden, 2.5 dklk indirgeme sonras yaplan karbrizasyon almalar neticesinde CH4 gaznn hem indirgeme hem de karbrleme iin yeterli olmad anlalmtr. Bu rnde 30 dk CH4 gaz ile reaksiyon sonrasnda dahi fazlarn deimedii (Fe, Fe2O3, Fe3O4 ve FeO) ilgili paternden grlmektedir. Ancak, arlk deiimleri az miktarda arlk kazanm olduunu gstermektedir. Arlktaki art, muhtemelen Fe3C oluumu nedeniyle olmaktadr. Bu faz, miktarnn az veya kristalleme derecesinin dk olmas nedeniyle XRD ile saptanamamtr. H2 atmosferinde 5 ve 10 dk indirgenmi tozlarn 15 ve 30 dklk CH4 gaz ile reaksiyonuyla elde edilen rnlerin esas itibaryla Fe3Cden olutuu ilgili paternlerden grlmektedir. Ayrca, sentezlenen Fe3C tozlarnn kristal boyutlarnn 40130 nm arasnda olduu XRD paternlerindeki pik geniliklerinden tespit edilmitir.
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ekil 5. Fe2O3in (a) 2.5 dk, (b) 5 dk ve (c) 10 dk H2 atmosferinde indirgenmesi sonras saf CH4 gaz (40 cm3/dk) ile yaplan karbrizasyon almalarna ait rnlerin XRD paternleri 3.2.3. Morfoloji ncelemeleri ekil 6da farkl indirgenme oranlar iin yaplan 15 ve 30 dklk karbrizasyon almalar sonras elde edilen rnlere ait SEM grntleri verilmitir.
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ekil 6. Karbrizasyon almalar sonras elde edilen rnlere ait SEM grntleri. H2 atmosferinde indirgeme sresi: (a), (b) 2,5 dk; (c), (d) 5 dk ve (e), (f) 10 dk Saf CH4 gazyla reaksiyon sresi : (a), (c) ve (e) 15 dk; (b), (d) ve (f) 30 dk SEM grtlerinden 2.5 dk indirgenmi numunenin karbrizasyonu sonras rn morfolojisinde belirgin bir deiim olmad (kk demir oksit partiklleri hala mevcut) grlmektedir. 5 ve 10 dklk H2 atmosferinde indirgeme akabinde saf CH4 gazyla yaplan karbrizasyon almalar sonrasnda elde edilen Fe3Cn morfolojilerinin indirgenmi rn morfolojileri (ekil 3) ile benzerlik gsterdii saptanmtr. SEM grntlerinden karbrizasyon sonras elde edilen reaksiyon rn partikl boyutlarnn 0.30.9 m arasnda deitii belirlenmitir. 3.3. Deneysel Sonularn Literatrle Karlatrlmas Literatrde [5, 6] nanokristal Fein 773853 Kde saf CH4 gaz ile reaksiyonu sonucu elde edilen rnlerin Fe3C, Fe ve C [5] veya Fe3C ve C [6] ierdii rapor edilmitir. Bu almalarda [5, 6] rnlerde serbest karbon grlmesi, balang Fe3O4 tozunda bulunan K2O, Al2O3 ve CaO gibi yapsal oksitlerle ilikilidir. Bu oksitler, H2 atmosferinde indirgeme srasnda sinterlemeyi byk oranda engelleyerek nanoboyutlu Fe olumasn salamaktadr. Nanoboyutlu partikller karbrizasyon srasnda katalitik etki gstermekte ve CH4n daha fazla paralanmasn salamaktadr. Dolaysyla literatrde [5, 6] rapor edilen nihai rnlerde serbest C bulunmaktadr. Mevcut almada ise Fe partikllerinin indirgenme srasnda sinterlemesi nedeniyle CH4n katalitik olarak paralanmas mmkn grlmemitir. 4. SONULAR Fe2O3in Ar atmosferinde stldktan sonra 800 Kde H2 gazyla izotermal indirgenmesi (5 dk) sonucu 0.20.8 m aralnda deien partikl boyutuna ve >200 nm kristal boyutuna sahip Fe tozu elde edilmitir. Bu ilemin akabinde yaplan saf CH4 gaz ile reaksiyonlar (15 dk) sonras partikl boyutu 0.30.9 m, kristal boyutu 40130 nm arasnda deien Fe3C tozlar sentezlenmitir. Arlk deiim lmleri ve XRD analizleri, sentezlenen Fe3C tozlarnn olduka saf olduunu ve serbest C iermediini de gstermemitir. TEEKKR Bu alma, stanbul niversitesi Bilimsel Aratrma Projeleri Koordinasyon Birimince desteklenmitir. Proje numaras: 1453. KAYNAKLAR 1. Morjan, I., Alexandrescu, R., Scarisoreanu, M., Fleaca, C., Dumitrache, F., Soare, I., Popovici, E., Gavril, L., Vasile, E., Ciupina, V., Popa, N.C., Controlled Manufacturing of Nanoparticles by the Laser Pyrolysis: Application to Cementite Iron Carbide, Applied Surface Science, Vol. 255, pp. 96389642, 2009.
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2. Nikitenko, S.I., Koltypin, Y., Felner, L., Yeshurun, I., Shames, A.I., Jiang, J.Z., Markovich, V., Gorodetsky, G., Gedanken, A., Tailoring the Properties of Fe-Fe3C Nanocrystalline Particles Prepared by Sonochemistry, Journal of Physical Chemistry B, Vol. 108, pp. 76207626, 2004. 3. Nelson, J.A., Wagner, M.J., High Surface Area Nanoparticulate Transition Metal Carbides Prepared by Alkalide Reduction, Chemistry of Materials, Vol. 14, pp. 44604463, 2002. 4. Lee, D.W., Yu, J.H., Km, B.K., Jang, T.S., Fabrication of Ferromagnetic Iron Carbide Nanoparticles by a Chemical Vapor Condensation Process, Journal of Alloys and Compounds, Vol. 449, pp. 6064, 2008. 5. Arabczyk W., Konicki W., Narkiewicz U., Jasinska I., Kalucki K., Kinetics of the Iron Carbide Formation in the Reaction of Methane with Nanocrystalline Iron Catalyst, Applied Catalysis A: General, Vol. 266, pp. 135145, 2004. 6. Narkiewcz, U., Guskos, N., Arabezyk, W., Typek, J., Bodzion, T., Konicki, W., Gasiorek, G., Kucharewcz, I., Anagnostakis, E.A., XRD, TEM and Magnetic Resonance Studies of Iron Carbide Nanoparticle Agglomerates in a Carbon Matrix, Carbon, Vol. 42, pp. 11271132, 2004.
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KMYASAL BUHAR BRKTRME YNTEMYLE Fe2O3 TOZU VE METAN KULLANILARAK KARBON NANOTP BYTLMES
Melek CUMBUL ALTAY, erafettin EROLU stanbul niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 34320, Avclar, stanbul, mcumbul@istanbul.edu.tr, seref@istanbul.edu.tr ZET Karbon nanotpler, <100> ynne sahip silisyum altlk zerinde Fe2O3 tozu ve metan gaz kullanlarak kimyasal buhar biriktirme tekniiyle bytlmtr. C nanotp sentezinde iki yol kullanlmtr. Birinci yolda, 1200 byme scaklnda C nanotp altlk zerinde sentezlenmitir. kinci yolda ise bytme, n stlm CH4 frnn scak zonundan (1200 K) geirildikten sonra daha dk scaklklarda (10501150 K) gerekletirilmitir. Tp apnn artan scaklk ve sreyle artt gzlenmitir. Ayrca HR-TEM grntleri, birbirine ve tp eksenine paralel olarak bym ok sayda grafit tabakalarndan oluan tpleri gstermitir. Fe2O3-CH4 sistemi iin yaplan termodinamik analiz, artan CH4 miktaryla Fe oksitFeFe3CFe3C+C dnmlerinin olabileceini ortaya koymutur. Anahtar Kelimeler: Karbon nanotp, Kimyasal buhar biriktirme, Fe2O3, Metan
GROWTH OF CARBON NANOTUBE BY CHEMICAL VAPOR DEPOSITION USING Fe2O3 POWDER AND METHANE
ABSTRACT Carbon nanotubes were grown on a silicon substrate with a <100> orientation by chemical vapor deposition technique using Fe2O3 powder and methane gas. Two routes were used for C nanotube synthesis experiments. In the first route, C nanotube was synthesized on the substrate at a growth temperature of 1200 K. In the second route, growth was carried out at lower temperatures (1050-1150 K) after preheating CH4 gas by flowing it through the hot zone of the furnace (1200 K). It was observed that tube diameter increased with increasing time and temperature. Also, HR-TEM images showed that the tubes consisted of multi graphite layers grown parallel to each other and to the tube axis. Thermodynamic analyses carried out in the system of Fe2O3-CH4 revealed that Fe oxideFeFe3CFe3C+C transformations take place with increasing CH4 amount. Keywords: Carbon nanotube, Chemical vapor deposition, Fe2O3, Methane 1. GR Nano yapl karbon malzemeler bilim dnyasnda olaanst elektronik, termal, mekanik, optik ve kimyasal zellikleri nedeniyle nem arz etmekte ve dikkat ekmektedir. Nanoyapl karbon malzemeler, kimyasal sensr, alan emisyon malzemeleri, katalizr tayc, elektronik ve enerji depolama alanlarnda potensiyel kullanm alanlarna sahiptir [1,2]. Karbon nano tpler (KNT) temel olarak ark dearj, lazer kazma ve kimyasal buhar biriktirme (KBB) yntemleriyle sentezlenmektedir [3]. KBB, ok daha dk scaklklarda karbon nano tp bymesine olanak salamasndan dolay daha ekonomik bir yntemdir. Bu yntemde, karbon ieren gazlarn, yksek scaklktaki altlk yzeyinde bulunan metal katalizr partikllerle etkileimiyle gerekleen yzey reaksiyonlar (heterojen biriktirme reaksiyonlar) ile birlikte
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karmak gaz faz reaksiyonlar (homojen piroliz reaksiyonlar) sonucu altlk zerinde kat karbon biriktirilmektedir [4]. Metal katalizr olarak Fe, Co ve Ni gibi gei elementleri KNT lerin bymesinde nemli rol oynamaktadr. C kayna olarak genellikle seyreltilmi hidrokarbon (CH4, C2H2, C2H4) ve CO gazlar kullanlmaktadr [5,6]. KNT morfolojilerinin sentez srasnda katalizr boyutu ve ekliyle ilikili olduu rapor edilmitir [6]. Farkl bileim ve formlarda katalizrler ile C ieren deiik gaz bileimlerinin karbon nanotp sentezine etkileri zerine aratrmalar devam etmektedir. Demir esasl katalizr kullanlarak deiik gaz ve karmlar altnda karbon bymesine etkileri incelenmitir [7-12]. Mccaldin ve dierleri, Fe(NO3)3 tan elde edilen Fe2O3 katalizr, C2H4/H2 gaz karmlar kullanarak 773- 1073 K scaklk aralnda 2 saat srede hem nano fiber yapda hem de nano tp yapda karbon sentezlediklerini rapor etmilerdir. Ayrca, % 20 C2H4 - % 80 H2 gaz karmnda 773 K de elde ettikleri balk kl yapsnn artan reaksiyon scaklyla ok cidarl nano tp morfolojisine dntn belirlemilerdir [7]. Schnitzler ve Zarbin, KNT sentezi hava atmosferinde ferrosenin ssal bozunmasyla gzenekli silika cam zerinde ince film eklinde Fe2O3 katalizr hammaddesini biriktirmilerdir. Benzen ieren gaz karmn katalizr zerinden geirmek suretiyle 1173 K de 30 dak lk reaksiyon sresinde, 50-250 nm apnda ok cidarl KNT ler elde etmilerdir [8]. Kong ve dierleri, n ilemlerle hazrlam olduklar almina ve silika nano partikl destekli Fe2O3 katalizr tozuyla 1273 K de CH4 gaz kullanarak tek duvarl KNT ler sentezlemiler ve nano tp byme mekanizmasnn kk byme mekanizmasna gre gerekletiini rapor etmilerdir [12]. Katalizr tozu olarak n ilem grmemi Fe2O3 ve saf metan gaz kullanlarak KBB yntemiyle KNT sentezi konusunda literatrde bir almaya rastlanmadndan mevcut alma yrtlmtr. Bu almada Si altlk zerinde saf metan gaz ile n stmal ve n stmasz artlarda scaklk ve byme sresine bal olarak KNT sentez almalar gerekletirilerek optimum sentez koullar belirlenmitir. Ayrca sentez prosesinin daha iyi anlalmasna ve C oluum artlarnn ngrlmesine yardmc olmas iin termodinamik analiz yaplm, Fe2O3-CH4 sistemi iin muhtemel genel reaksiyon belirlenmitir. 2. MALZEME VE YNTEM Mevcut almada kullanlan deney dzenei (ekil 1) esas olarak SiC stc elementli scak cidarl frn, kuvars tp (20 mm apnda) ve gaz ak lerlerden olumaktadr. Deneysel almada katalizr olarak <50 nm boyutlarnda Fe2O3 tozu kullanlmtr. Katalizr partikller, etanol/katalizr sspansiyonuna daldrlmak suretiyle ultrason yardmyla <100> ynne sahip Si altlk zerinde datlmtr. Sentez almas iin karbon kayna olarak metan (%99,5), reaksiyon ncesi ve sonrasnda inert atmosfer salamak amacyla yksek safiyette argon (%99,999) kullanlmtr.
ekil 1. Kimyasal buhar biriktirme reaktrnn ematik grnm. Bu almada, n stlmam ve n stlm metan gaz kullanlarak iki seri sentez almalar gerekletirilmitir. lk seride, n stmasz almada, altlk 1200 K frn merkez scaklna yerletirilmitir. kinci seri, n stmal deneylerde, 1200 K de frn merkezinden metan gaz geirilerek reaktr tpnn k tarafna yerletirilmi olan daha dk scaklklardaki altlk zerinde karbon bytme yaplmtr. Bu deneylerde altlk (reaksiyon) scaklk aral 1050-1150 K olarak seilmitir. Her iki seride sabit CH4 gaz ak hznda (13,4 cm3/dak) scakla ve sreye (15-60 dak) bal olarak karbon bytme deneyleri yaplmtr. C sentez almalar iin TMerkez/TBytme/CH4 gaz ak hz/sre eklinde ksaltmalar kullanlarak optimum deneysel artlar ifade edilmitir.
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Deneysel almalar sonucunda elde edilen rnlerin morfolojileri Taramal Elektron Mikroskobu (SEM Jeol 5600, FEG-SEM Jeol 6335F) ve Yksek znrlkl Geirim Elektron Mikroskobunda (HR-TEM Jeol 2100) incelenmitir. Termodinamik hesaplamalar Fe2O3-CH4 sisteminde serbest enerji minimizasyon yntemiyle [13] 1000- 1300 K scaklk aralnda yaplmtr. Hesaplamalarda 40 gaz faz (r. CH4, CH3, C2H6) ve 6 kat faz (C, Fe, Fe3C, FeO, Fe2O3 ve Fe3O4) bileenleri gz nne alnmtr. 3. BULGULAR 3.1. n stlmam metan gaz ile sentez almas n stlmam metan gaz kullanlarak 1200 K de 30 dakika bytme sresinde elde edilen numuneye ait ekil 2 (a-c) de verilen HR-TEM resimleri rn morfolojisinin tps yapda olduunu gstermektedir. ekil 2 (a) dan baz tplerin ularnn ak (ekilde A ile gsterilmi), bazlarnn ise kapal (B) olduu anlalmaktadr. Ayrca, katalizrn, tp ierisinde belirli bir yere kademeli olarak ilerledii (C) ve yer yer tp ierisindeki partikller arasnda boluk olduu grlmektedir. Koyu renkli keli alanlar (D) sinterlenme sonucu kabalam partiklleri temsil etmektedir. ekil 2 (b) de baz tplerde boumlar (E) grlmektedir. ekil 2 (c), ucu kapal bir tpn HRTEM grntsn sergilemektedir. Grnt, tpn tek cidarl deil ok cidarl olduunu (birden fazla grafit katman ierdiini) aka ortaya koymaktadr.
ekil 2. . n stlmam metan gaz kullanlarak 1200 K de 30 dak bytme sonrasnda elde edilen rnn HR-TEM grntleri. ekil 3 (a-c), 1200 K frn merkez scaklnda, 15, 30 ve 60 dak bytme srelerinde sentezlenen numunelerin altlk zerindeki SEM grntlerini gstermektedir. ekilden grld zere rn morfolojileri i ie giren yumak eklinde uzun (r. 20 m) nanotplerden olumaktadr. Bu yaplarn aplar sreye bal olarak artmaktadr (ekil 3 c). Ortalama tp aplarnn 15 ve 30 dak lk bytme srelerinde 100 nm nin altnda, 60 dak sonra ise ~250 nm civarnda olduu tespit edilmitir.
ekil 3. n stlmam metan gaz kullanlarak 1200 K de a) 15 dak, b) 30 dak, c) 60 dak da elde edilen rnlerin SEM grntleri ve d) rnlerin tp ap boyutuna bytme sresinin etkisi.
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3.2. n stlm metan gaz ile sentez almas 1200 K deki frn merkezinden geirilen CH4 n frnn daha dk scaklk blgelerine (1050, 1100 ve 1150 K) yerletirilmi olan altlk zerindeki katalizrle reaksiyona girmesi sonucu elde edilen rnlerin FEG-SEM resimleri ekil 4 (a-) de verilmitir. n stlmam metan gaz kullanlarak elde edilen rnlerde gzlenen morfolojilere benzer oluumlarn n stlm artlarda da ortaya kt tespit edilmitir. Ayrca yer yer dall fiberler morfolojide yer almaktadr (rnein ekil 4 () da A ile iaretlenmi alan). ekil 5 te deiik sreler iin bytme scaklnn rn ap boyutuna etkisi grafik halinde verilmitir.
ekil 4. n stlm (1200 K) metan gaz kullanlarak 1050 K (a-c), 1100 K (d-f), 1150 K (g-) bytme scaklnda 15 dak (a,d,g), 30 dak (b,e,h) ve 60 dak (c,f,) bytme sonras elde edilen numunelere ait FEG-SEM grntleri.
ekil 5. n stlm (1200 K) metan gaz kullanarak deiik bytme sreleri iin bytme scaklklarnn tp ap boyutuna etkisi.
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Grafikten grld zere, artan bytme scakl ve srelerinde tp aplarnda art gereklemitir. allan scaklklarda 15 ve 30 dak sre sonunda tp aplar 100 nm nin altndadr. Bu srelerde sentezlenen rnlerin artan bytme scaklna bal olarak tp aplarndaki art hemen hemen ayn seviyededir. Ancak, aptaki byme 60 dak iin daha fazla olup 1050 K bytme scaklnda ortalama tp ap ~ 70 nm iken 1150 K de ise ~ 200 nm dir. 3.3. Termodinamik analiz Fe2O3-CH4 sistemi iin yaplan termodinamik hesaplamalar sonucunda elde edilen denge kat hal diyagram, denge durumunda oluan rnlerin (kat ve gaz) miktarlar scaklk (1000-1300 K) ve C mol kesrine (nC/(nFe+nC) bal olarak ifade ekil 6(a-c) de grafikler halinde verilmektedir
ekil 6. a) Scaklk ve C mol kesrine bal olarak denge kat hal diyagram, b) C mol kesrinin kat rn % mol miktarlarna etkisi, c) rnlerin ksm basnlarnn C mol kesri ile deiimi. ekil 6 a da verilmi olan denge kat hal diyagramndan grld zere, tm scaklklar iin, yaklak 0,25 C mol kesrine kadar artan CH4 ile srasyla Fe2O3+Fe3O4, Fe3O4, Fe3O4+FeO ve FeO bulunmaktadr. Bu faz alanlarndan sonra 1005-1300 K scaklk aralnda artan CH4 miktaryla birlikte FeO+Fe, Fe, Fe+Fe3C, Fe3C ve Fe3C+C faz alanlar grlmektedir. Ayrca, 1000 K de dier scaklklarda bulunan faz alanlarna ek olarak FeO+Fe3C ikili faz ile FeO+Fe3C+Fe l faz alanlar olumaktadr. ekil 6 b, denge durumunda sistemde oluan kat rn % mol miktarlarna C mol kesrinin etkisini gstermektedir. Grafikten, CH4 miktar arttka ikili veya l faz blgelerinde ortaya kan yeni fazlarn miktar artt, mevcut olann miktarnn ise azald grlmektedir. Tek faz blgelerinde ise ilgili bileenin miktar % 100 olmaktadr. rnein, Fe3C+C blgesinde Fe3C faz miktar azalrken, ortaya kan C un miktar artmaktadr. Scakln mol miktarlarna etkisi yaklak 0,74 C mol kesrine kadar grlmektedir. Ancak, bu deerden sonra esas itibaryla etkisi olmamaktadr. ekil
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6 c verilen grafik ise Fe2O3-CH4 sisteminde 1000-1300 K aralnda bulunan 10-5 atm den byk olan rnlerin ksmi basnlarnn C mol kesri ile deiimini gstermektedir. Bu grafikten elde edilen nemli sonular sistem iin yle zetlenebilir: H2O, CO2, H2, CO ve CH4 gaz faznn bileenleridir. C mol kesri arttka, H2O ve CO2 in ksmi basnlar azalmakta, buna karlk H2 ve CH4 ksmi basnlar ykselmektedir. Yaklak 0,15 C mol kesri civarnda CO ve H2 e ait ksm basn erileri CO2 ve H2O erilerini kesmektedir. Daha yksek C mol kesirlerinde H2 ve CO ksm basnlar dier iki gaz bileenine kyasla daha fazladr. Sabit C mol miktar iin scaklk arttka, CO2, H2O ve CH4 ksm basnlar azalmaktadr. Ayrca, dk ksmi basnlara sahip tali gaz bileenleri de (C2H4, H2CO, CH3, Fe(OH)2, H, HCO, HO) sistemde bulunmaktadr. Oluan rnlerin miktarlar gz nne alnarak olas kimyasal reaksiyonlar Fe2O3-CH4 sistemi iin belirlenmitir. Fe2O3+Fe3O4 faz alannda gaz faznda CO2 ve H2O ana gaz bileeni olarak yer almakta ve artan CH4 miktaryla Fe3O4 miktar artmakta ve Fe2O3 miktar azalmaktadr. Buna gre Fe2O3+CH4 sisteminde Fe3O4, CO2 ve H2O oluumu iin ana reaksiyon Denklem 1 ile ifade edilebilir. 6Fe2O3(k) + 1/2CH4 4Fe3O4(k) + H2O+ 1/2CO2 (1000-1300 K iin Gr<0) 2Fe3O4(k) + 1/2CH4 6FeO(k)+ H2O + 1/2CO2 (1000-1300 K iin Gr<0) (1)
Artan CH4 ile Fe3O4 ten FeO e dnm iin muhtemel ana reaksiyon Denklem 2 de verilmitir. (2)
FeO+Fe faz alannda CO miktar CO2 ten daha yksek olduu ekil 11 den grlmektedir. Dolaysyla FeO ten Fe e dnm reaksiyonu Denklem 3 ile gsterilebilir. 3FeO(k) + CH4 3Fe(k) + 2H2O + CO (1100-1300K iin Gr<0) (3)
Ayrca, Fe ieren faz alanlarnda, artan CH4 miktar ile CO ve H2 nin ksmi basnlar artmakta, buna karlk CO2 ve H2O in ksmi basnlar dmektedir (ekil 5.5). Bu durum CH4 n Denklem 3 te ortaya kan H2O ve CO2 in CH4 ile gaz faznda reaksiyona girebileceine iaret etmektedir (Denklem 4-5). CH4 + H2O CO + 3H2 (1000-1300 K iin Gr<0) CH4 + CO2 2CO + 2H2 (1100-1300 K iin Gr<0) (4) (5)
Ayrca, metann paralanmas (Denklem 6) sonucu oluan kat C un, CO2 ile reaksiyona girerek (Boudouard reaksiyonu, Denklem 7) CO oluumuna katkda bulunaca dnlmektedir. CH4 C(k) + 2H2 (1000-1300 K iin Gr<0) CO2 + C(k) 2CO (1000-1300 K iin Gr<0) (6) (7)
Fe3C ise yksek metan miktarlarnda Denklem 8 de verilmi olan reaksiyon uyarnca olumaktadr: 3Fe+C(k) Fe3C (1000-1300 K iin Gr<0) (8)
Oluan C un stokiometrik orandan fazla olduu durumda ise Fe3C yannda serbest C da olumaktadr. Fe2O3-CH4 sisteminde Fe3C+C oluumu iin nemli genel reaksiyon Denklem 9 ile ifade edilebilir. 3Fe2O3(k) + 12CH4 2Fe3C(k) + C(k) + 9CO + 24H2 (1000-1300 K, Gr<0) (9) 4. TARTIMA Karbon nanotp bymesi metan gaznn katalizr partikl zerinde muhtemelen uygun kristallografik yzeylerde paralanmas sonucu C oluumu, C atomlarnn partikl iinde yaynm ve nanopartikln belirli yzeylerinde birikerek bymesi eklinde aklanmaktadr [14]. Si altlk zerinde katalizrlerin bulunmad blgelerde C birikiminin gzlemlenmemesi KNT yaplarn katalizr etkisiyle CH4 n paralanmas sonucu bydn ortaya koymaktadr. KNTlerin sentezi iin katalizr seimi yannda CH4 gaznn paralanma derecesi veya sentez scakl nemli bir rol oynamaktadr. Bu nedenle CH4 gaz-
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nn paralanma derecesini artrmak iin gaz 1200 K de n stma ilemine tabi tutulduktan sonra daha dk scaklklarda (1050-1150 K) altlk zerinde C bytme ilemleri yaplmtr. n stlm CH4 gaz kullanlarak gerekletirilen almalarda, rn morfolojisinin n stlmam artlardaki morfolojiyle ayn olduu belirlenmitir. Artan sentezleme srelerinde ise elde edilen rnlerin morfolojik zellikleri deimemi, sadece nceden oluan tp zerinde pirokarbon birikmesi nedeniyle tp aplarnda zamana bal olarak art meydana gelmitir. Ancak, bu artlarda (n stlm), n stlmam artlara gre daha dk ortalama aplara sahip tpler sentezlenmitir. Bu durum nispeten dk bytme scaklndan kaynaklanmaktadr. HR-TEM analizi, sentezlenen tplerin ok cidarl olduunu sergilemitir. Cidar says katalizr partiklnn boyutlaryla ilikilendirilmektedir [15]. Mevcut almada kullanlan Fe2O3 tozunun ortalama partikl boyutunun ~38 nm olmas nedeniyle ok cidarl nanotpler elde edilmitir. Metal katalizr - altk etkileimlerinin, byme mekanizmasnda nemli rol oynad rapor edilmitir [6]. Katalizr-altlk etkileimi gl olduunda karbon nano tp, katalizr partikl tabanda kalacak ekilde (kk byme modeli) bymektedir. Altlk - katalizr etkileimi zayf olduunda ise katalizr partikl, oluan karbon tp tarafndan altlktan koparlarak tpn ucunda bymeyi tevik etmektedir (u byme modeli) [15]. Mevcut almada elde edilen morfoloji grntlerinden bahsi geen tp byme modellerinden genel olarak karbon nanotplerin kk modeline gre byd dnlmektedir. Fe2O3-CH4 sisteminde 1000-1300 K scaklk aralnda atmosferik basn altnda yaplan termodinamik hesaplar, Fe2O3 in saf CH4 atmosferi altnda Fe e indirgendiini ve artan CH4 miktaryla serbest C un da olutuunu gstermektedir. Termodinamik analiz, CH4 miktar arttka kat fazdaki kimyasal deiimlerin Fe2O3 Fe3O4 FeO Fe Fe3C Fe3C+C, ekilde olduunu ngrmektedir. Deneysel almalar, serbest C un olduu alan iinde kalacak ekilde (diyagramlarda sa alt blgede) gerekletirilmi olup allan scaklklarda katalitik etkiyle metann paralandn deneysel almalarda teyit etmitir. 5. SONU Fe2O3 tozu kullanlarak ok cidarl C tpler deiik srelerde sentezlenmitir. Deneysel bulgular, scaklk ve sre arttka tp apnn bydn1 gstermitir. Nano tp sentezi iin optim3um -artlarn 1200 K/1200 K/13,4 cm3.dak- /15-330 da1k, 1200 K/1050- 1150 K/13,4 cm .dak 1/15-30 dak ve 1200 K/1050 K/13,4 cm .dak- /60 dak olduu tespit edilmitir. HR-TEM analizi, sentezlenen tplerin ekseni boyunca birbirine paralel grafit tabakalardan olutuunu sergilemitir. Nanotplerin muhtemel byme mekanizmalarnn elde edilen HR-TEM ve SEM grntlerinden genel olarak kk byme mekanizmasna gre gerekletii sonucuna varlmtr. Fe2O3-CH4 sisteminde yaplan termodinamik analiz, artan CH4 miktaryla Fe oksitFeFe3CFe3C+C dnmlerinin olduunu gstermektedir. Ayrca, denge halindeki kat ve gaz fazlardaki CH4 miktarna bal olarak ortaya kan bileim deiimlerinden Fe2O3-CH4 sistemindeki muhtemel genel reaksiyon 3Fe2O3(k) + 12CH4 2Fe3C(k) + C(k) + 9CO + 24H2 olarak belirlenmitir. TEEKKR Bu alma, ..Aratrma Projeleri Birimi tarafndan 1459 numaras ile desteklenen proje ile M. C. Altay n doktora tezinin bir blmdr. KAYNAKLAR 1. Mamalis, A. G., Vogtlnder, L. O. G., Markopoulos, A., Nanotechnology and Nanostructured Materials: Trends in Carbon Nanotubes, Precision Engineering, 28, 16-30, 2004. 2. Paradise, M., Goswami, T., Carbon Nanotubes - Production and Industrial Applications, Materials & Design, 28, 1477-1489, 2007. 3. Kuchibhatla, S. V. N. T., Karakoti, A. S., Bera, D., Seal, S., One Dimensional Nanostructured Materials, Progress in Materials Science, 52, 699-913, 2007. 4. Delhas, P., Fibers and Composites, Taylor & Francis, London, U.K., 2003. 5. Yang, P., The Chemistry of Nanostructured Materials, World scientific publishing, New Jersey, U.S.A., 2003. 6. Dupuis, A. - C., The Catalyst in the CCVD of Carbon Nanotubes - A Review, Progress in Materials Science, 50, 8, 929-961, 2005. 7. Mccaldin, S., Bououdina, M., Grant, D.M., Walker, G.S., The Effect of Processing Conditions on Carbon Nanostructures Formed on An Iron-Based Catalyst, Carbon, 44, 2273-2280, 2006.
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8. Schnitzler, M. C., Zarbin, A. J. G., Utilization of Iron Oxide Film Obtained by CVD Process as Catalyst to Carbon Nanotubes Growth, Journal of Solid State Chemistry, 182, 2867-2872, 2009. 9. Singjai, P., Thongtem, T., Kumfu, S., Thongtem, S., Synthesis of CNTs via Ethanol Decomposition Over Ball-Milled Fe2O3 Coated Copper Sheets, Inorganic Materials, 43, 2, 143-147, 2007. 10. Homma, Y., Kobayashi Y., Ogino, T., Takagi, D., Ito, R., Joon Jung, Y., Ajayan, P., M., Role of Transition Metal Catalysts in Single-Walled Carbon Nanotube Growth in Chemical Vapor Deposition, The Journal of Physical Chemistry B, 107, 12161- 12164, 2003. 11. Narkiewicz, U., Podsladyy, M., Jedrzejewski, R. J, Pelech, I., Catalytic Decomposition of Hydrocarbons on Cobalt, Nickel and Iron Catalysts to Obtain Carbon Nanomaterials, Applied Catalysis A: General, 384 , 27-35, 2010. 12. Kong, J., Cassell, A. M., Dai, H., Chemical Vapor Deposition Of Methane for Single-Walled Carbon Nanotubes, Chemical Physics Letters, 292, 567-574, 1998. 13. Erolu, S., Bakan, H., Chemical Vapor Reaction, Mo2C Powder Synthesis, Thermodynamic Analysis, Key Engineering Materials, 264-268, 121-124, 2004. 14. Yoon, S., Lim, S., Hong, S., Qiao, W., Whitehurst, D. D., Mochida, I., An, B., Yokogawa, K., A Conceptual Model for the Structure of Catalytically Grown Carbon Nano-Fibers, Carbon, 43, 1828-1838, 2005 15. Ando, Y., Zhao, X., Sugai, T., Kumar, M., Growing Carbon Nanotubes, Materials Today, 7, 10, 22-29, 2004.
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SINTERING and SINTERING ATMOSPHERES
www.turkishpm.org
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INVESTIGATION OF POWDER INJECTION MOLDING STEATITE: RHEOLOGY, DEBINDING AND SINTERING PARAMETERS
Levent URTEKN *, brahim USLAN ** and Bedri TU ** * Dumlupinar University, Department of Mechanical Engineering,Kutahya, TURKEY, lurtekin@dpu.edu.tr ** Gazi University, Faculty of Technology, Department of Materials Technology, 06500, Ankara, Turkey, iuslan@gazi.edu.tr , btunc@gazi.edu.tr ABSTRACT Steatite ceramics have been produced by dry pressing, extrusion, slip casting, wet pressing and injection moulding methods. In this study, steatite samples were produced by powder injection moulding (PIM) using a feedstock based on a polyethylene glycol (PEG), polypropylene (PP) and stearic acid (SA) formulation. Rheological experiments are performed using a capillary rheometer on mixtures with 50-60 vol.% powder. A volume fraction of 58 vol.% shows the best properties and is used for injection moulding. Two procedures were used for debinding the injection moulded samples, solvent and thermal methods. The solvent debinding is carried out at 60 0C in water. Thermal debinding parameters are deduced from thermogavimetric (TGA) analysis. Sintering is performed at 12001300 0C for 2-4 hours in air. The theoretical densities of 98-99% are realized. Furthermore, the porosity associated with density changes was observed by electron microscopy. Keywords: Powder Injection Molding, Rheolghy, Debinding 1. INTRODUCTION There are many shaping method of ceramics such as slip casting, dry pressing, wet pressing, hot pressing, isostatic pressing and injection molding. Powder injection molding is a method in which production of inorganic powder engineering components is performed using injection molding equipments and debinding processes. If the used powder is metallic, it is known as metal injection molding (MIM). On the other hand, if it is ceramic, it is named ceramic injection molding (CIM) [1]. The application area of this method is fairly large. For examples, these areas are complex shape, machine parts, small clock parts, robot arms, medicine equipment parts, tooth prosthesis, office equipments, laboratory parts, engine parts of air space vehicle, printing circuits, automotive parts, hand equipments, cutting tools, electric and electronic parts, gun parts, high temperature ceramics can be given as examples of PIM application [2-3]. In 1999 the estimated market value of PIM system was found to be 664 million US dollars [4]. In 2003 value of PIM process market was 1 billion US dollars. It is estimated that PIM market will be 2 billion dollars until 2010 [5]. Today PIM process finds large application areas in USA, European countries, Israel, China and Indian. Lately, PIM has been used in micro processing like as 400 nm alumina grains and 5 m big parts. These dimensions of PIM processing are useful for micro electromechanical systems (MEMs) and micro systems technologies (MST). Both have a market value in the world with 68 billion US dollars [6]. Steatite is a natural mineral. Its formula is (Mg(Si4O10)(OH)2), magnesium silicate. Steatite ceramics can be produced by dry pressing, extrusion, casting and semi wet pressing. Steatite, which has very good mechanical and electrical properties, can show high densities when it is sintered. By these properties, steatite can be used as a good electric insulator in the electrical equipment industry. Steatite has applications such as socket, control units, insulating bed, low voltage power protection and plates. [7-8]. Karatas et al. [9] studied on rheology of prepared feedstock produced using steatite powder and polyethylene based binders. Loebbecke et al. [10] this work focuses on the flow behaviour of alumina feedstocks with high solids
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content, based on two different binder systems and two different alumina powders. By varying particle size, organic binder system, and solids content, the rheological properties of the feedstocks were modified significantly. Vielma at al [11]; in this experimental work, injection molding of alumina parts was performed with a developed binder system based on high density polyethylene (HDPE), paraffin wax (PW) and stearic acid. Rheological character was determined by torque rheometer and performed with alumina by 50-60 % in volume. The flow type was pseudo-plastic and optimum flow occurred at 58 % alumina powder load by volume. 99 % therotica1 density was obtained by sintering at 600 0C for 2 hours. Soykan [12]; used 80-90 wt % talc, 10 wt % clay and 5-10 wt % flux mixture by adding TiN and barium carbonate to this mixture. Clay provided mass formation, barium carbonate affected liquid flow during sintering. Sotomayor at al [13] have studied rheological properties of binding system consisting of HDPE and paraffin wax, and stainless steel powders produced with gas atomization method by using capillary rheometer. The effects of powder loading and different powder distributions on rheological parameters were studied. In a study by Ahn at al. [14], they have examined the combination of different binding systems under four main bases, First of these is the rheological action of stainless steel with binders, the second is the feeding stock characteristics which can be listed as shear speed, viscosity and injection pressure. The third is the relationship of powder-binder and the fourth basis is carrying out the control of speed and powder-binder mixture depending on the shear speed. In this study capillary rheometer trials were carried out for binding mixture that contains 50-60 % steatite powder by volume for a temperature range of 170-220 0C. The homogeneity of the mixture and optimum powder loading were determined empirically. After performing injection molding debinding was carried out by two means solvent and thermal. Selecting a multi-system binder, i.e. preferring binding system which consists of PEG/PP/SA, was due to avoiding deformations that may occur during debinding. Debinding speed and temperature were determined by TGA. Sintering was carried out 99% theoretical density was obtained for optimum sintering temperature of 1300 0C at 4 hours of waiting period. The rest of the paper is organized as follows: in Section 2, we will present experimental model under study. In Section 3, we gave the experimental results. The conclusions of the research are summarized in Section 4. 2. EXPERIMENTAL METHOD Material: The used steatite powder was provided from Kale Chemical Co. Its composition is given in Table 1. Steatite C221; optimum dielectrically property according to European Electro Technical Standard Institution (CENELEC) norm as CEI 672-1. Sockets, insulating beds and low voltage power fuse are some usage areas of steatite. Table 2 shows some of their physical and mechanical properties. The particle size distribution is as follows: d10=0.74, d50=3,96 and d90=15.92m. Table 1. Composition of Steatite, wt.% SiO 60 MgO 30 Al2O3 2.5 CaO 1 Fe2O3 1.5 Na2O3 + K2O 0.5 tempering losses 4.5
Table 2. Properties of Steatite porosity (%) density, g/cm3 hardness, Mohs modulus of elasticity, MPa tensile strength, MPa * bending strength, MPa compression strength, MPa 0 2.7 7-8 110 50-51 124-140 900
Feedstock: The evaluation of the feedstock rheological properties is based on the viscosity and its shear sensitivity and temperature sensitivity [3]. Water based binder of composition (wt.%) 65% PEG 8000, 30% polypropylene (PP) and 5% stearic acid (SA) were used to prepare feedstocks. Density of the binder mixture was 1.084 g/cm3.
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Rheology: Rheological evaluation serves as a quality control tool in a PIM operation. Maximum useful viscosity for the mixture is 103 Pa.s at the molding temperature. [3].The rheological properties of the feedstocks were analysed capillary rheometer. Then rheological properties of feedstock were measured at four temperatures from 170 C to 220 C. Molding: The feedstock was molded Arburg Allrounder 220S injection molding machine in the PM Laboratory of Gazi University. The molding parameters are shown in Table 3. Tensile and bending samples were produced under the PIM parameters. Table 3. PIM operation parameters Feedstock Holding Barrel temperature, flow rate, pressure, bar C cm3/s 600 600 35-185-190-195-200 35-190-195-200-205 15 17-25
Molding pressure, bar Bending samples Tensile samples 1000-1250 1350
Mold temperature, C 20 20
Green density (%) 70 72
Debinding: Debinding was performed into two ways. For PEG8000, distilled water was used as a solvent PP and SA were debound using thermal method during the sintering. Moulded parts were immersed into distilled water at 60C for 24h. The samples were oven dried at 50C for 5h and weighed. Thermal analysis methods are widely used in the ceramic industry for research and quality control purposes. Thermal behavior and removal of the binders from the PIM feedstocks prepared were studied by TGA analysis. Heating rate was 1 C/min until 400 C and holding time was 30 min. at this temperature for thermal debinding (pre-sintering). Heating up rate was same to 550 C, but the holding time was changed as 60 minutes at this temperature. Fig. 1 gives TGA analysis of the feedstock.
Fig. 1. Thermo-gravimetric analysis (TGA) of the feedstock Sintering: Sintering process was carried out for different temperatures between 1200-1300 C and different holding times between 2-4 hours. Heating rate to sintering temperature and cooling rate to room temperature were same as 5 C/min. Fig. 2 shows thermal debinding and sintering procedures.
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Fig. 2. Pre-sintering and sintering processes 3. EXPERIMENTAL RESULTS Powder additions to the binder raise the viscosity. Viscosity got over 103 Pa.s rapidly after 58 vol. % steatite loading and critical solid loading was 60 vol. % as seen in Fig. 3. At 160-170 C, the viscosity values were over 103 Pa.s for all feedstocks. The viscosity must be evaluated over the range of temperatures and shear rates expected during molding.
Fig. 3. (a) Viscosity versus temperature (b) viscosity versus shear rate (pressure :1.36 MPa) The melt volume index (MVI), defined as the extruded volume over 10 min., also illustrates that the critical solid loading is 60 vol. % steatite. The mixture is not flowing above this loading ratio. Spiral and direct flow was observed at 55-58 vol. % steatite loading. Loaded mass kept constant, the addition of steatite powder to the binder formulations caused a decrease at the MFV values, as a result, increased the temperature required to achieve a good capillary flow. Burning was observed in feedstocks after 230 0C (Fig 3.a). Shear rate increased when decreasing viscosity (Fig 3.b). This is known as pseudo plastic behavior. 102-105s-1 intervals are desired values for feedstocks. Viscosity increased when the solid loading was increased. Viscosity was 800 Pa.s at 58 vol % solid loading. Capillary rheo-
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logical tests were not achieved for 60 vol % solid loading because of high viscosity (Fig. 4.a) Melt volume index was also higher at high temperatures than lower ones (Fig. 4.b).
Fig. 4. (a) Viscosity versus steatite loading (b) the melt volume index versus steatite loading (pressure: 1.36 MPa ) About 90% of binder was successfully extracted by solvent debinding. Debinding rations of PEG in water by solvent debinding process were approximately 90.7 %, 91.7 % and 92.17 % for bending, graded and tensile samples. The remaining amount of binder (skeleton binder, PP, and lubricant, SA) was also burned by thermal debinding process (pre-sintering). Fig. 5 shows debinding ratios in water by time for three different samples.
Fig. 5. Weight loss of steatite compact immersed in water for various extractive times Densities of the bending and tensile samples were the lowest at 1200 C and increased when the temperature was increased (Fig. 6). Increasing has continued obviously until 1275 C for different holding times. Any significant change has not observed at temperatures above 1275 C for 4h. Theoretical densities were 97 % and 98 % under sintering conditions of 1250 C for 4h and 1275 C for 2h respectively. Maximum density values of the samples were obtained at 1300 C for 4h. After waiting for 4h at 1300 C, the porosities were found close and density was found maximum. Similar results were obtained for tensile samples.
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Fig. 6. Theorical densities of (a) three point and (b) tensile samples versus holding time at different sintering temperatures For 1300 C for 4 h, maximum linear shrinkages of tensile and bending samples were 18.17 % and 18.18 %, respectively (Fig. 7).
Fig. 7. Linear shrinkages of (a) three point (b) tensile samples versus sintering time for different holding times Images obtained by SEM analyses are illustrated in Fig. 9. Sintered samples have open porosity at 1200 C (Fig. 8.a). If sintering temperature was increased to 1300 C, most of porosities were close and samples were near full density (Fig. 8.b).
b) surface contact (1300 0C) a) interconnected porosity (1200 0C) Fig. 8. Pore structure in sintering samples (SEM and Optic images)
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Graded and bending samples of green part, debinding and sintering are shown in Fig. 9.a and Figure 9.b, respectively. Figure 9.c shows sintered tensile sample.
Fig. 9. Green, debinding and sintered samples 4. CONCLUSIONS Critical steatite solid loading with the PEG-based binder is 60 vol. %. Temperature ranges 170 to 200 C are suitable for molding of PEG-based feedstocks with steatite solid loadings 50, 55, 56 and 58 vol. %. The rheological behavior of feedstock flow was found to be pseudo-plastic. In this behavior by increasing shear rate viscosity is decreasing. This behavior is known the desired property. 90.7 % PEG for bending sample, 91.7% PEG for stepped sample and 92.17% PEG for tensile sample were removed easily from system. When debinding, the possibility of distortion was decreased. The removal of binder was different for each sample. The reason of this behavior was related with the dimensions and package efficiency of samples. At 400 0C, all binder was completely debinding for PEG/PP/SA with TGA method. Thermal debinding rate was kept very small such as 1 0C/min. The maximum shrinkage was found to be 18.18%. After injection molding green density was found 70-72%. The highest density (99 %) values were obtained by sintering this steatite powder at 1300 C. ACKNOWLEDGEMENTS The authors are grateful to Prof. Dr. Suleyman SARITAS. The authors acknowledge the support of Gazi University (DPT Projects No: 2001K120590 and 2003K120470) labs for facilitating the experimental studies. REFERENCES 1. R.M. German, (in Turkish) editors: S. Sartas, et al., Powder Mettalurgy, First Press, 2007, Uyum Agency, Ankara. 2. C. Karatas, Rheology for feedstocks used powder injection moulding, 1997, Ph.D. Thesis, Gazi University, Ankara. 3. R.M. German, A. Bose, Injection Molding of Metals and Ceramics, 1997, Metal Powder Industries Federation, New Jersey.
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4. P.A. Hauck, Powder Injection Molding: Current and long term outlook, Int. J. Powder Metallurgy, 2000, vol. 36, no. 3, pp. 29-30. 5. C. Karatas and S. Sartas, Powder Injection Molding: A high technology manufacturing process, Journal of The Faculty Engineering And Architecture of Gazi University, 1998, vol.13, no. 2, pp. 193. 6. R. Zauner, Micro Powder Injection Moulding, Microelectronic Engineering, 2006, vol. 83, pp. 1442-1444. 7. L. Urtekin Investigation of the effect of molding and sintering parameters on properties of powder injection molded steatite ceramics, 2008, Ph.D. Thesis, Gazi University, Ankara. 8. L. Urtekin, I. Uslan, and B. Tuc Investigation of Properties of Powder Injection-Molded Steatites, Journal of Materials Engineering and Performance, DOI: 10.1007/s11665-011-9901-8. 9. C. Karatas, A. Kocer, H.I. Unal, S.Sartas, Rheological Properties of Feedstocks Prepared with Steatite Powder and Polyethylene-Based Thermoplastic Binders, J. Materials Processing Technology, 2004, vol. 152, no. 1, pp. 77-83. 10. B. Loebbecke, R. Knitter, J. Hauelt, Rheological properties of alumina feedstocks for the low-pressure injection moulding process Journal of the European Ceramic Society, 2009, vol. 29, no. 9, pp 1595-1602. 11. P. T. Vielma, A. Cervera, B. Levenfeld, A. Vrez, Production of alumina parts by powder injection molding with a binder system based on high densitypolyethylene, Journal of the European Ceramic Society, 2008,vol. 28, no. 4, pp 763-771. 12. H.S. Soykan, Low-temperature fabrication of steatite ceramics with boron oxide addition, Ceramics International, 2007, vol. 33, pp. 911-914. 13. M.E. Sotomayor, A. Vrez, B. Levenfeld, Influence of powder particle size distribution on rheological properties of 316L powder injection moulding feedstocks Powder Technology, 2010, vol. 200, no. 1-2, pp. 30-36. 14. S Ahn, S. J. Park, S. Lee, S. V. Atre, R. M. German Effect of powders and binders on material properties and molding parameters in iron and stainless steel powder injection molding process Powder Technology, 2009, vol. 193, no. 2, pp 162-169 15. B.C. Mutsuddy and R.G. Ford, Ceramic Injection Molding, 1995, U.S.A.
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SNTERLEME SICAKLII VE SRESNN YKSEK ORANDA GZENEK EREN DEMR ESASLI KOMPAKTLARIN BASMA MUKAVEMETNE ETKS
Nuray BEKZ*, Enver OKTAY* * stanbul niversitesi Metalurji ve Malzeme Mhendislii Blm, Avclar, stanbul. e-mail : nbekoz@istanbul.edu.tr, oktay@istanbul.edu.tr ZET Bu almada; toz metalurjisindeki boluk yapc teknii kullanlarak yksek oranda gzenek ieren demir esasl kompaktlar retilmitir. Boluk yapc malzeme olarak 0,71-1,00 mm partikl boyut aralna sahip dzensiz ekilli karbamit, n alaml Distaloy AB demir tozuyla kaplanm ve 200 MPa basn altnda tek ynl preslenerek ap 12 mm ykseklii yaklak 18 mm olan ham kompaktlar elde edilmitir. Ham kompaktlar ierisindeki karbamitin %95i oda scaklnda suda zndrlerek uzaklatrlmtr. Ham kompaktlar hidrojen atmosferi altnda 1150 C ile 1200 C de 60 dakika ve 1200 C de 120 dakika sinterlenmilerdir. 60 dakika sinterleme sresi iin sinterleme scaklnn 1150 Cden 1200 Cye karlmas kompaktlarn maksimum basma mukavemetini %41 orannda arttrmtr. Fakat 1200 Cde 120 dakika sinterlemenin yksek oranda gzenek ieren demir esasl kompaktlarn basma mukavemeti zerine az bir etkisi olmutur. Bulgular sinterlenmi kompaktlardaki gzeneklerin kresel ap ve kresellik deerleri altnda tartlmtr. Anahtar kelimeler: Gzenekli malzemeler, boluk yapc, sinterleme, basma mukavemeti, kresellik, kresel ap.
EFFECT OF SINTERING TEMPERATURE AND TIME ON THE COMPRESSIVE STRENGTH OF HIGHLY POROUS IRON BASED COMPACTS
ABSTRACT In this study; highly porous iron based compacts were manufactured using the space holder technique in powder metallurgy. Carbamide which had a particle size distribution in the range 0.71-1.00 mm with an irregular shape were covered with prealloyed Distaloy AB iron powder and pressed uniaxially at 200 MPa to obtain cylindrical compacts having a diameter of 12 mm and height of about 18 mm. About 95% of the carbamide was removed from the compacts by water leaching at room temperature. The compacts were sintered at 1150 C and 1200 C for 60 minutes and at 1200 C for 120 minutes under hydrogen atmosphere. For 60 minute sintering time, raising the sintering temperature from 1150 C to 1200 C increased the compressive strength values of the compacts about 41%. But, sintering at 1200 C for 120 minutes made a small contribution to compressive strength values of the compacts. The findings were discussed in light of spherical diameter and sphericity values of the pores. Keywords: Porous materials, space holder, sintering, compressive strength, sphericity, spherical diameter. 1. GR Srekli gelien ve deien teknolojinin bir sonucu olarak kullanlan malzeme trlerinde ve zelliklerinde de ilerlemeler kaydedilmektedir. Gzenekli malzemelerin ortaya k hem hafif hem de mukavemetli malzemelere duyulan ihtiyacn artmasna dayanmaktadr. Yeni bir mhendislik malzeme snf olan kpks metaller; dk younlua, bklmeye kar dirence, yksek enerji snmleme kabiliyetine, sesi emme zelliine, dk s ve elektrik iletkenliine sahiptirler. Enerji tketiminin azalmasna olanak veren hafif yaplar ayn zamanda evreye duyarl yeni bir malzeme grubu olarak da dikkat ekmektedir [1-3]. Kpks metaller; sv hal kpklendirmesi, gaz hapsetme, amur
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kpklendirme, metalik bo kre kullanarak kpklendirme, dkm, ktrme- kaplama, gaz-tektik dnm ve toz metalurjisi yntemleri ile retilmektedir. Boluk yapc kullanlarak toz metalurjisi yntemiyle gzenekli malzeme retimi; gzenek zelliklerinin, malzeme eklinin ve mekanik zelliklerinin kontrolnde dier yntemlere gre salad birok stnlkten dolay son yllarda kullanlan bir yntem olarak karmza kmaktadr. Kullanlacak boluk yapc, malzemenin ierisinde kalnt brakmadan kolayca atlabilmeli ve metalle reaksiyona girmemelidir. Karbamit, hem termal hem de suda zndrlerek yapdan uzaklatrlabildiinden; alminyum, titanyum, paslanmaz elik, nikel ve bunlarn alamlarndan metalik kpk retiminde son yllarda baarl olarak kullanlmaktadr [4-6]. Sinterleme scakl ne kadar yksek olursa ham kompakt ierisindeki toz partikllerin de arzu edilen derece bir balanma elde etmek iin gereken sre o kadar ksa olur. malat asndan ksa sinterleme sreleri daha ok tercih edilir. Ancak yksek sinterleme scaklklar sinter frn bakm maliyetleri asndan ekonomik deildir. Demir esasl alamlar iin en yaygn sinterleme koullar 1120-1150 Cdir. Uygulamaya bal olarak sinterleme sresi 15-60 dakika arasnda deiir [7]. Ancak toz metalurjisi yntemiyle yksek oranda gzenek ieren malzeme retiminde dk presleme basncndan kaynaklanan ksmi sinterleme yksek sinterleme scakl ve sresiyle iyiletirilebilir [8-12]. Ak gzenek yaps malzemenin dayanmn drmesine karn yksek oranda s tanmn mmkn klan zelliinden dolay yksek g reten cihazlarda etkili bir soutucu mekanizma olarak, yksek hzda ve titreim frekansnda alan makine paralarnda akustik sourma salamak amacyla ve kimyasal reaktrlerde katalizr tayc olarak kullanm alan bulmaktadr. Mo ile n alamlandrlm demir tozlarndan retilen gzenekli malzemeler; yksek scakla ve sl oklara kar dayanma sahip olmasndan dolay s kalkan olarak s yaltm ve soutma sistemlerinde, yanma motorlarnn yksek scakla maruz kalan k yerlerinde kullanm potansiyeline sahiptir [1-3, 13]. Literatrde; Distaloy AB tozundan hareketle boluk oluturucu kullanlarak toz metalurjisi yntemiyle kpks metal retimine ynelik bir alma bulunmamaktadr. Bu almada, toz metalurjisi yntemiyle Distaloy AB tozundan yksek oranda gzenek ieren numuneler retilerek; farkl sinterleme scakl ve sresinin basma davran zerine etkisi gzeneklerin kresel ap ve kresellik deerleri altnda tartlmtr. 2. MALZEME VE YNTEM Deneylerde; Hgans firmas tarafndan atomizasyon yntemi ile retilmi ortalama tane boyutu 112 m olan dzensiz ekilli n alaml Distaloy AB demir tozu kullanlmtr. Ham mukavemeti arttrmak amacyla balayc olarak kullanlan parafin Merck firmasndan temin edilmi olup 46-48 C arasnda erime scaklna sahiptir. Boluk yapc olarak; +710-1000 m boyut aralna sahip dzensiz ekilli teknik safiyette karbamit kullanlmtr. Karbamitin younluu; 1,34 g/cm3, erime scakl 133 C ve 20 C scaklktaki suda znrl 108 g/mLdir. Deneysel almada kullanlan n alaml demir tozunun kimyasal bileimi Tablo 1de verilmektedir. Tablo 1 : n alaml demir tozunun kimyasal bileimi [14].
ekil 1-(a)da atomizasyon yntemiyle retilmi n alaml Distaloy AB tozunun ekil 1-(b)de dzensiz ekilli karbamitin Taramal Elektron Mikroskobu (SEM) grntleri verilmitir.
ekil 1 : Deneysel almada kullanlan (a) Distaloy AB tozunun ve (b) karbamitin SEM grnts
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Toz metalurjisi yntemi ile kpks metal retiminin temel ilem admlar; metal tozunun balayc ile kartrlmas, karbamit yzeyinin metal tozuyla kaplanmas, presleme, ham numunelerden karbamitin uzaklatrlmas ve sinterlemedir. Ham numunelerin mukavemetinin arttrlmas amacyla balayc olarak a.%3 orannda hazrlanan parafin zeltisi, n alaml demir tozuna hac.%2 orannda katlarak oda scaklnda 30 dakika kartrlmtr. Karma; hac.%80 orannda karbamit ilave edilip turbula tipi kartrcda 1 saat sre ile kartrma sonucu, karbamit paracklar demir tozlar ile kaplanmlardr. Demir tozlaryla kaplanm karbamitin elik bir kalp ierisinde 200 MPa basn altnda tek ynl preslenmesiyle 12 mm apnda ve yaklak 18 mm yksekliinde silindirik numuneler elde edilmitir. Ham numunelerdeki karbamitin yaklak %98i saf su banyosunda 3 saatte gider3ilmitir. retilen ham numunelerin younluklar ktle/hacim ilikisinden 2,20 g/cm olarak belirlenmitir. Numuneler ierisinde kalan az miktardaki karbamit ile balayc olarak kullanlan parafinin termal olarak giderilmesi ve sinterleme ilemi seramik bir boruya sahip Lenton marka frnda yaplmtr. Numuneler; ortamdan N2 gaz geirilerek nce 5 C/dak. stma hzyla 400 Cye stlm ve bu scaklkta 30 dakika tutulmu daha sonra ortamdan yksek safiyette H2 gaz geirilerek 10 C/dak. stma hzyla; 1150 C ile 1200 C de 60 dakika ve 1200 C de 120 dakika sinterlenmilerdir. Sinterlenmi numunelerin younluklar, ak ve kapal gzenek oranlar Arimed Yntemine gre belirlenmitir. Ak ve kapal gzenek oranlarn belirlemek iin numuneler 150 Cde kaynayan parafin ierisinde 1,5 saat bekletilerek parafinin gzeneklere emdirilmesi salandktan sonra numunelerin arlk lmleri gerekletirilmitir. Numunelerin grnt analizleri Jeol JSM-5600 Taramal Elektron Mikroskobunda yaplmtr. Sinterlenmi numunelerdeki gzeneklerin kresel ap ve kresellik dalmlar; Clemex Vision PE-4.0 grnt analiz program kullanlarak SEM resimleri zerinde belirlenmitir. Basma testleri, boy/ap oran 1,5 olan numuneler zerinde, ZWICK marka Z 050 PROLINE model mekanik test cihaznda oda scaklnda 0,5 mm/dak. basma hzyla gerekletirilmitir. Gerilme-%ekil deiim grafikleri ve hesaplamalar, Test-Xpert programnn V11-02 versiyonu kullanlarak elde edilmitir. 3. SONULAR VE DEERLENDRME 2,20 g/cm3 ham younluktaki numunelerin; 1150 Cde 60 dakika, 1200 Cde 60 dakika ve 1200 Cde 120 dakika sinterlenmesi sonucu hacimsel ekmeleri srasyla; %6,41, %6,62 ve %6,68 olarak gereklemitir. Artan sinterleme scakl ve sresi tm numunelerde hacimsel ekmeyi arttrmtr. Sinterleme scaklnn hacimsel ekme zerine etkisinin sinterleme sresinden daha fazla olduu belirlenmitir. Sinterlenmi numunelerin Arimed Yntemine gre belirlenen younluklar, toplam, ak ve kapal gzenek oranlar sinterleme scakl ve srelerine gre Tablo 2de verilmitir. Tablo 2 : Arimed Yntemine gre belirlenen younluk, toplam, ak ve kapal gzenek oranlar
Sinterlenmi numunelerin toplam gzenek oran hedeflenen gzenek oranndan (hac.%80) dk kmtr. Artan sinterleme scakl ve sresi ile kapal gzenek oran bir miktar artmtr. Azalan sinterleme scakl ksmi sinterlemeden dolay ak gzenek orann bir miktar arttrmtr. ekil 2-(a)da 1150 Cde 60 dakika, (b)de 1200 Cde 60 dakika ve (c)de 1200 Cde 120 dakika sinterlenen numunelerin SEM fotoraflar verilmitir.
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ekil 2 : (a) 1150 Cde 60 dakika, (b) 1200 Cde 60 dakika ve (c) 1200 Cde 120 dakika sinterlenen numunelerin SEM grntleri ekil 2de verilen SEM fotoraflarnda belirgin bir ekilde kpks yapnn olutuu grlmektedir. Gzenekler birbirlerinden hcre duvarlaryla ayrlmlardr. Yaplarda atlak oluumlarna rastlanmam ancak mikro gzenekler bulunmaktadr. Gzenek morfolojisinin karmak olmas kullanlan karbamitin dzensiz ekilli olmasndan ileri gelmektedir. ekil 3de; farkl scaklk ve srelerde sinterlenmi numunelerdeki gzeneklerin kresel ap ve kresellik dalmlar verilmitir. ekil 3 : (a) ve (b) 1150 Cde 60 dakika, (c) ve (d) 1200 Cde 60 dakika ve (e) ve (f) 1200 Cde 120 dakika sinterleme sonras numunelerdeki gzeneklerin kresel ap ve kresellik dalmlar Kresel ap ve kresellik dalmlar; numunelerin farkl scaklk ve srede sinterlenmesine gre deiiklik gstermektedir. Sinterleme scaklnn 1150 Cden 1200 Cye ykselmesi ile gzeneklerin maksimum ve ortalama kresel aplar srasyla; 1026,2 mden 991,2 mye ve 608,7 mden 586,5 mye azalm, kresellii 0,54den 0,56ya artmtr. Ancak artan sinterleme sresiyle ortalama gzenek boyutlar ve kresellik deerlerinde kayda deer farkllklar olmamtr. 1150 Cde 60 dakika sinterleme ile retilen numunelerdeki gzeneklerin %50si 400-800 m boyut aralna sahipken, 1200 Cde 60 ve 120 dakika sinterleme ile retilen numunelerdeki gzeneklerin yaklak %60 400-800 m boyut aralna sahiptir. Boluk yapc olarak kullanlan karbamitin balangta maksimum ve ortalama kresel aplar ve kresellik deerleri srasyla; 996,7 m, 812,6 m ve 0,66dr. Balangta kullanlan karbamite gre tm numunelerde sinterleme sonras gzeneklerin oratalama kresel aplar ve kresellikleri azalmtr. Bu durum, sinterlemeden dolay gzenek duvarlarnda ekmenin baskn olmasndan kaynaklanmaktadr. Maksimum gzenek boyutunun kullanlan karbamitin boyutundan byk olmas gzeneklerin birbirleriyle balant kurmasndan kaynaklanmaktadr. ekil 4de farkl sinterleme scakl ve sresinde sinterlenmi numunelerin gerilme- %ekil deiim erileri verilmitir.
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ekil 4 : Farkl sinterleme scakl ve sresinde sinterlenmi ve yaklak %70 gzenek ieren numunelere ait basma erileri Bu eriler kpks metallerin tipik basma davrann yanstmaktadr. Her bir eri elastik bir blgeye, uzun bir plato blgesine ve gerilmenin hzla artt younlama blgesine sahiptir. Elastik blgeden sonra numunelerde meydana gelen youn gzenek duvar krlmas nedeniyle; gerilmede ani dler gereklemitir. 1150 Cde 60 dakika, 1200 Cde 60 dakika ve 1200 Cde 120 dakika sinterleme sonras numunelerin maksimum basma mukavemeti srasyla; 17 MPa, 24 MPa ve 25 MPa olarak belirlenmitir. Artan sinterleme scakl maksimum basma mukavemetini bir miktar arttrm ancak artan sinterleme sresi maksimum basma mukavemetinde az bir arta neden olmutur. 60 dakika sinterleme sresi iin sinterleme scaklnn 1150 Cden 1200 Cye karlmas kompaktlarn maksimum basma mukavemetini %41 orannda arttrrken; 1200 C sinterleme scaklnda sinterleme sresinin 60 dakikadan 120 dakikaya karlmas kompaktlarn maksimum basma mukavemetini %4 orannda arttrmtr. 1150 Cde 60 dakika, 1200 Cde 60 dakika ve 1200 Cde 120 dakika sinterleme sonras numunelerin elastisite modlleri srasyla; 0,47 GPa, 0,68 GPa ve 0,71 GPa olarak belirlenmitir. Artan sinterleme scakl ve sresiyle elastisite modlleri bir miktar artmtr. Sinterleme scakl ve sresinin artmasnn younlamann balad ekil deiimi zerine belirgin bir etkisi olmamtr. Aly yapt almada [13], ticari isimleri Distaloy SA ve Astaloy Mo olan n alaml demir tozlarna amur kpklendirme prosesi uygulam ve rettii3 ham numuneleri 1170 Cde 90 dakika sinterlemidir. Younluklar 1,3 ile 2,0 g/cm arasnda olan kpks metallerin maksimum basma mukavemetini 5-15 MPa arasnda, younlamann balad ekil deiimlerini %50-60 arasnda bulmutur. Bu yntemin dezavantaj yapda atlak oluumunun ska gereklemesidir. Bram ve dierleri [8], Park ve Nutt [9], Tuncer ve Arslan [10] ile Ahmed ve dierleri [11] toz metalurjisi yntemiyle boluk yapc kullanarak yksek oranda gzenek ieren metal retiminde; gzenek miktar, i yap ve basma davran gibi zelliklerin boluk yapc miktar ve ekli ile balang toz boyutunun yan sra sinterleme scakl ve sresi gibi parametrelerle kontrol edilebileceini belirtmilerdir. Jiang ve dierleri [12], artan sintreleme scakl ile tozlar arasnda balanmann iyileerek basma mukavemetini arttrdn tespit etmilerdir. Artan sinterleme scakl, yksek oranda gzenek ieren Distaloy AB numunelerinde daha fazla hacimsel ekme ve younlamaya neden olmaktadr. 1200 Cde 60 dakika sinterleme yerine 120 dakika sinterlemenin hacimsel ekme ve younlama zerine nemli bir etkisi olmamaktadr. Sinterleme scaklnn artmasyla numunelerdeki gzeneklerin kresellik deerleri artm, ortalama gzenek boyutlar azalmtr. Ancak artan sinterleme sresi ile gzenek boyutlar ve kreselliklerde ok az deiiklik meydana gelmitir. Numunelerin maksimum basma mukavemetlerinde meydana gelen art; gzenek duvarlarndaki ksmi sinterlemenin yol at mikro gzeneklerin azalmas sonucu gzeneklerin kresel aplarnn azalmas ve kreselliklerinin artmasyla mmkn olmutur. Teekkr Bu alma T-1431 proje numarasyla stanbul niversitesi Bilimsel Aratrma Projeleri Birimi tarafndan desteklenmitir. KAYNAKLAR 1. BANHART, J., Manufacture, Characterisation and Application of Cellular Metals and Metal Foams, Progress in Materials Science, 46, 559-632, 2001. 2. KREMER, K., LISZKIEWICZ, A., ADKINS, J., Development of Steel Foam Material and Structures, Technology Roadmap Program 9913 Final Report, The United States Department of Energy and American Iron and
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Steel Institute, 2004. 3. BANHART, J., Properties and Applications of Cast Aluminium Sponges, Advanced Engineering Materials, 4:188-191, 2000. 4. BAKAN, H.I., A Novel Water Leaching and Sintering Process for Manufacturing Highly Porous Stainless Steel, Scripta Materialia, 55, 203-206, 2006. 5. WEN, C.E., MABUCHI, M., YAMADA, Y., SHIMOJIMA, K., CHINO, Y., ASAHINA, T., Processing of Biocompatible Porous Ti and Mg, Scripta Materialia, 45, 1447-1153, 2001. 6. ZHAO, Y.Y., SUN, D.X., A Novel Sintering-Dissolution Process for Manufacturing Al Foams, Scripta Materialia, 44, 105-110, 2001. 7. HGANS HANDBOOK-6, Sintering, Sweden, 2004. 8. BRAM, M., STILLER, C., BUCHKREMER, H.P., STOVER, D., BAUR, H., High Porosity Titanium, Stainless Steel and Superalloy Parts, Advanced Engineering Materials, 2, 196-199, 2000. 9. PARK, C., NUTT, S.R., PM Synthesis and Properties of Steel Foams, Materials Science and Engineering, A288, 11-18, 2000. 10. TUNCER, N., Metalik Kpk Malzemelerin retimi ve Karakterizasyonu, Yksek Lisans Tezi, Anadolu niversitesi Fen Bilimleri Enstits, 2006. 11. AHMED, Y.M.Z, RIAD, M.I., SAYED, A.S., AHLAM, M.K., SHALABI, M.E.H., 2006, Correlation Between Factors Controlling Preparation of Porous Copper via Sintering Technique Using Experimental Design, La-Metallurgia Italiana, 41-46, 2006. 12. JIANG, B., ZHAO, N.Q., SHI, C.S., LI, J.J, Processing of Open Cell Aluminum Foams with Tailored Porous Morphology, Scripta Materialia, 53, 781-785, 2005. 13. ALY, S.M., High Temperature Mechanical Properties of Cast as well as Powder Metallurgical Manufactured Metallic Foams, Doctorate Thesis, Stipendiat am Institut fr Eisenhttenkunde, Aachen, Deutschland, 2004. 14. HGANS-A.B., Hgans Iron and Steel Powders for Sintered Components, Sweden, 1996.
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42CrMo4 ELNN KIVILCIM PLAZMA SNTERLEME YNTEM LE YOUNLATIRILMASI

Rdvan YAMANOLU*, William BRADBURY**, Eugene OLEVSKY**, Randall M. GERMAN** *Kocaeli niversitesi, Mhendislik Fakltesi, Metalurji ve Malzeme Mhendislii Blm, 41380, Kocaeli, ryamanoglu@kocaeli.edu.tr **San Diego State niversitesi, Makine Mhendislii Blm, 92182-1323, San Diego, California, USA, wbradbur@gmail.com, eolevsky@mail.sdsu.edu, rgerman@mail.sdsu.edu ZET Bu almada, 42CrMo4 eliinin kvlcm plazma sinterleme (SPS, Spark Plasma Sintering) yntemi ile younlatrlmas incelenmitir. retilen tozlar farkl scaklk, sre ve zellikle etkili stma hz deiimleri altnda sinterlenmi ve proses parametrelerinin sinterleme karakteristii zerine etkileri saptanmtr. Elde edilen kompaktlarn younluklar, mikroyapsal karakteristikleri ve sertlikleri incelenerek sonular deerlendirilmitir. Mikroyapsal zelliklerin tayininde optik ve taramal elektron mikroskobu kullanlmtr. 42CrMo4 elii iin elde edilen en yksek younluk deerine ( % 99,2) 1000 oCde 7 dakika bekleme sresi ve dakikada 200 oC stma hz ile ulalmtr. Keywords: Kvlcm Plazma Sinterleme, 42CrMo4 elii, Mikroyapsal Karakterizasyon
CONSOLIDATION OF 42CrMo4 STEEL BY SPARK PLASMA SINTERING

ABSTRACT In the current study, a 42CrMo4 steel powder was consolidated by spark plasma sintering. The effect of processing parameters on the sintering characteristics was determined through variation of temperature, holding time and particularly heating rate conditions. Sintered samples were characterized in terms of relative density, microstructure and hardness. Optical and scanning electron microscopy was used to examine the microstructural characteristics. The 42CrMo4 steel powders were successfully sintered to 99.2 % density at 1000oC for 7 minutes using 200 oC/ min. heating rate. Keywords: Spark Plasma Sintering, 42CrMo4 Steel, Microstructural Characterization 1. GR eliklerin sinterlenmesi zerine bir ok alma yaplmaktadr. zellikle Cr ierikli eliklerin sinterlenmesinde kromun oksidasyona yatknl nedeniyle oluan oksit tabakas sebebiyle sinterleme olduka zor olmaktadr. Bu nedenle sinterlenemenin atmosfer kontroll bir ortamda yaplmas gerekmektedir [1]. Bu almada da kvlcm plazma sinterleme yntemi yoluyla vakum altnda Cr ierikli 42CrMo4 elii younlatrlmtr. 42CrMo4 elii orta karbonlu dk alaml elikler gruba girer. Isl ileme olduka yatkn olan bu elik zellikle yksek mukavemet gerektiren uygulamalarda tercih edilir [2]. Krom ve molibden ierii srasyla % 0.030-1.20 ve % 0.08-0.35 arasnda deiir. Krom oksidasyon ve korozyon direncini, sertleebilirlii ve yksek scaklk mukavemetini arttrr. Ayn ekilde molibdende mukavemeti artrr, sertleebilirlii kontrol eder ve temper krlganlna yatknl azaltr. % 0.40 karbon ieren 42CrMo4 elii en yaygn kullanlan eliklerden birisidir ve olduka yksek ekme mukavemet deerlerine sahiptir [3-4].
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Kvlcm plazma sinterleme teknii prensip olarak genellikle bir grafit kalp ve zmbalar ierisinde bulunan metal veya seramik tozunun, yksek akm younluundaki doru akm ile stlmas esasna dayanr. st ve alt zmbalardan kalp boyunca akan akm (tipik olarak birka 1000 A ve birka V) eer sinterlenecek toz malzemede iletken ise malzemenin iinden de akarak devre tamamlanm ve SPS prosesi ile toz partiklleri arasndaki boluklarda yksek enerji ak retilmi olur. Bu yntem sahip olduu yksek stma hzlar nedeniyle olduka fazla avantaja sahiptir. [5-9].
2. DENEYSEL ALIMA Kocaeli niversitesi Metalurji ve Malzeme Mhendislii Blmnde plazma destekli dnel elektrot yntemi (PREP, Plasma Rotating Electrode Process) ile retilen 42CrMo4 elii tozlarnn kimyasal bileimi izelge 1de, tarama elektron mikroskobu grnts ise ekil 1de verilmitir. Tozlar retim ynteminin doas gerei uular srasnda yeterli sreyi bulup kreselleerek katlamalarn tamamlamlardr. Ayn tozlarn dalanm halde kesit mikroyaplarnn grntleri ekil 2de verilmitir. Geleneksel dkm teknikleri ile retimin aksine toz metalurjik yntemle retilen tozlar yksek souma hzlar sayesinde martenzitik dnme uramlardr. izelge 1. Bu almada kullanlan matriks alamnn kimyasal bileimi. 42CrMo4 %C 0,42 % Si 0,23 % Mn 0,62 %P 0,02 %S 0,027 % Cr 0,99 % Mo 0,17
ekil 1. almada kullanlan 42CrMo4 elii tozlarnn SEM grntleri
ekil 2. Tozlarn kesit grntleri, a) SEM, b) optik mikroskop. retilen bu tozlarn 150-250 m aralna sahip olanlar elek analizi ile gruplandrlarak kvlcm plazma sinterleme teknii ile younlatrlmtr. Sinterleme iin San Diego State niversitesinde bulunan Dr. Sinter Lab 515S SPS (SPS Syntex, Co., Japonya) cihaz kullanlmtr. PREP yntemi ile retilen 42CrMo4 elii tozlarnn kvlcm sinterleme yntemi ile younlatrlmasnda 3 farkl sinterleme deikeni kullanlmtr: 800 ile 1000 oC arasnda deien scaklk, 5 dakika ile 8 dakika arasnda deien tutma sresi ve 100 ile 225 oC/dak. arasnda deien stma sreleri kullanlmtr. Sinterlenen kompaktlarn younluklar arimet yntemi ile, sertlikleri Fisherskop marka vickers sertlik cihaz ile belirlenmitir. Numunelerin mikroyapsal karakterizasyonlar iin Zeiss Axiotech k mikroskobu ve Jeol 6060 tarama elektron mikroskobu kullanlmtr.
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3. SONULAR izelge 2de 42CrMo4 elii tozlarnn kvlcm sinterleme ile younlatrlmas srasnda kullanlan parametreler ve sonular sunulmutur. izelge 2. 42CrMo4 elii iin SPS parametreleri ve younluk deerleri Numune Kodu T1 T2 T3 T4 T5 T6 T7 T8 T9 Scaklk (oC) 800 900 1000 800 900 1000 800 900 1000 Sre (dakika) 5 5 5 5 5 5 8 8 7 Istma Hz (oC/dakika) 100 100 100 200 225 200 200 225 200 Younluk (%) 83,6 93,3 98,4 85,3 94,2 98,5 86,6 95,2 99,2
Scaklk younluk zerinde en etkili parametre olmutur. 800, 900 ve 1000 oCde uygulanan ilemlerde younluk scaklkla birlikte etkili bir ekilde artmtr. Scaklk etkisinin daha net grlebilmesi iin elde edilen deerler diyagramlar zerinde gsterilmitir. ekil 3de ayn bekleme sresi ve 100 oC/dak. stma hzlarnda 800 ve 1000 oCde yaplan sinterleme iin scaklk ve younluk diyagramlar verilmitir. Scaklk hari tm parametrelerin ayn olduu bu iki farkl deneyde diyagramlardan da grld gibi artan scaklk ile younluk ok etkili bir ekilde art gstermitir. 800 oCde younluk % 83,6 iken,a) 1000 oCde % 98,4e ykselmitir.
b)
ekil 3. Younluk zerine scakln etkisi, a) 800 oC, b) 1000 oC
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Yaplan deneylerde scaklk kadar olmasa da stma hznn da younlama zerine etkisi olduu grlmtr. 100 oC/dak. stma hznda younluk % 83,6 iken stma hz 200 oC/dak. olduunda % 85,3e kmtr. 800 oCde yaplan almada elde edilen younluk art % 1,7 iken artan scaklk ile stma hznn etkisi younluk zerinde neredeyse kalmamtr. 900 oC ve 1000 oCde yaplan deneylerde artan stma hz ile elde edilen younluk art srasyla % 0,9 ve 0,1 olarak bulunmutur. Burada yksek stma hzlarnda partikller arasnda oluan plazma younluk artnda etkili olmutur. Yaplan SEM incelemeleri de partikller arasnda oluan etkileimin artan stma hz ile arttn gstermitir. Scaklk ile karlatrldnda stma sresi ile daha etkisiz bir ekilde deien younluk, bekleme sresinin uzamas ile artmtr. 800 oCde yaplan iki deneyde stma hz ile artan younluk, yaplan nc bir deneyde bekleme sresi sadece 3 dakika arttrldnda belirgin ekilde ykselmitir. Bekleme sresi etkisi stma hznn aksine btn scaklk deerlerinde grlmtr. 800 oCde 200 oC/dak. stma hznda bekleme sresi arttrldnda younluktaki art % 1,3, 900 oC iin % 1 ve 1000 oC iin % 0,7 olarak belirlenmitir. Tm parametre etkileri incelendiinde en uygun koullarda younluk % 99,2 olarak elde edilmitir. Dolaysyla 1000 o Cye 200 oC/dakika stma ile ulalp 7 dakika beklendiinde maksimum younluk kazanlmtr. Parametrelerin etkilerinin daha ak bir ekilde incelenebilmesi iin ekil 4de bekleme sresi, scaklk, younluk ile ekil 5de stma hz, scaklk ve younluk ilikileri verilmitir.
ekil 4. 42CrMo4 elii iin bekleme sresinin scaklk ve younluk ile ilikisi
ekil 5. 42CrMo4 elii iin stma hznn scaklk ve younluk ile ilikisi
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Elde edilen sinterlenmi kompakt malzemelerin parlatlm konumda k mikroskobu grntleri ekil 6da gsterilmitir. ekil 6ada % 83,6 younlua sahip numunenin olduka fazla gzenekli yaps grlmektedir. ekil 6bde ise en yksek younlua (% 99,2) sahip numunenin ayn bytmedeki optik mikroskop grnts verilmitir. ekil 6. Sinterlenmi numunelerin parlatlm konumda k mikroskobu grntleri, a) % 83,6 younluklu, b) % 99,2 younluklu numune. Yaplan sertlik lmlerinde % 83,6 younluklu numunenin sertlii 140 HV, % 99,2 younluklu numunenin ise 380 HV olarak llmtr. Sinterlemenin grafit kalpta yaplmas nedeniyle yzeyden karbon difzyonu olmu ve zellikle yzeylerde sert sementit ve martenzit fazlar grlmtr. ekil 7de % 99,2 younluklu numuneye ait sertlik profili verilmitir. Karbon difuzyonu ve buna bal olarak deien mikroyapsal karakteristik nedeniyle farkl sertlie sahip blgeler tespit edilmi ve bu yaplar incelenmitir (ekil 8). Malzemenin genel sertliini yanstan sertlik deeri yaklak 350400 HV arasnda deimektedir. Yzeyde meydana gelen kalnt stenit nedeniyle sertikte nce azalma daha sonra ise martenzit nedenli bir ykseli grlmektedir.
ekil 7. T9 nolu numunede sertlik dalm
ekil 8. % 99,2 younluklu numunede yzey ile merkez arasndaki mikroyap fark
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42CrMo4 eliinin SPS yntemi ile younlatrlmasnn ardndan, ayn tozlar karlatrma amac ile geleneksel scak presleme ile de sinterlenmitir. SPS deneylerinde en yksek younluun elde edildii 1000 oC scaklk ve 50 MPa basn deeri altnda tozlar 20 dakika sre ile sinterlenmelerine ramen % 90,5 gibi SPS yntemine gre olduka dk bir deer elde edilmitir. Numuneler kvlcm sinterleme yntemi ile younlatrldktan sonra gevrek krlm ve elektron mikroskobunda krlma yzeyleri incelenmitir. ekil 9da en dk (T1) ve en yksek younlua sahip (T9) numunelerin SEM grntleri verilmitir. Younluk fark net bir ekilde dikkati ekmektedir. T1 numunesinde dk younluk nedenli partikller arasndaki zayf balantlar (taneleraras krlma), T8 numunesinde ise kuvvetli balantlar (yer yer tane ii krlma) grlmektedir.
a) b) ekil 9. En dk ve en yksek younlua sahip numunelerin SEM grntleri, a) T1, b) T9 SPS ile sinterlenen numunlerde kullanlan farkl parametrelerin etkileri daha nce aklanmt. Ayn scaklk, basn ve bekleme sresine sahip fakat farkl stma hzlarndaki numunlerin (T1 T4) krlma yzeyleri ekil 10da verilmitir.
a)
b)
c)
d)
ekil 10. Farkl stma hzlarnda T1 ve T4 numunelerinin SEM grntleri Srasyla % 83,6 ve 85,3 younlua sahip bu numunelerin krlma yzeylerinden yksek stma hzna sahip numunedeki partikller arasndaki balantnn daha etkili olduu anlalmaktadr. ekil 10dde T4 numunesinde dekohezyon etkisi net bir ekilde grlmektedir.
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Bu almada PREP ile retilmi olan demir esasl DIN 42CrMo4 (AISI 4140) eliinin son yllarda olduka fazla ilgi eken ve zerinde ok fazla aratrmann yapld kvlcm sinterleme teknii ile younlatrlmas zerinde durulmutur. Bu malzemeye ounlukla boyut olarak byk paralarda ihtiya duyulmaktadr. Fakat mekanik zelliklerden dn verilemeyecek hassas paralarn kk boyutlu ve karmak ekilde retilme ihtiyac nedeniyle bu tarz malzemelerin de toz metalurjisi ile retimi zerinde durulmaya balanmtr. Sadece otomotiv deil silah paralar gibi farkl bir ok uygulamada yksek mukavemetli paralarn retimi nem arzeder hale gelmitir. PREP ile baarl bir ekilde retilen 42CrMo4 elii basn destekli sinterleme yntemi ile younlatrlmtr. Geleneksel basnl sinterlemeye gre aradaki fark, stma hzlarnn ok yksek olmasdr. Kvlcm sinterleme sayesinde PREP ile retilen 42CrMo4 eliinde % 99,2 teorik younlua ulalmtr. Ayn malzeme ayn koullar altnda geleneksel basnl sinterleme ile younlatrldnda ise % 90,5 gibi olduka dk bir younluk elde edilmitir. TEEKKR Bu almaya Atomizasyon Teknikleri ile Toz retimi isimli proje kapsamnda verdii destekten dolay Kocaeli niversitesi, Bilimsel Aratrma Projeleri Komisyon Bakanlna teekkrlerimizi sunarz. KAYNAKA [1] Campos, M., Sanchez, D., Torralba, J. M., Sintering behaviour improvement of a low Cr-Mo prealloyed powder steel through Mn additions and others liquid phase promoters, Journal of Materials Processing Technology, 143-144, 464-469, 2003. [2] Bayrak, M., ztrk, F., Demirezen, M., Evis, Z., Analysis of tempering treatment on material properties of DIN 41Cr4 and DIN 42CrMo4 steels, Journal of Materials Engineering and Performance, 16, 597-600, 2007. [3] Brady, G. S., Clauser, H. R., Vaccari, J. A., Materials Handbook, Fifteenth Edition, McGraw-Hill, New York, 2002. [4] Chuang, J. H., Tsayt, L. W., Chen, C., Crack growth behaviour of heat-treated 4140 steel in air and gaseous hydrogen, International Journal of Fatigue, 20, 531-536, 1998. [5] Orru, R., Licheri, R., Locci, A. M., Cincotti, A., Cao, G., Consolidation /synthesis of materials by electric current activated/assisted sintering, Materials Science and Engineering R, 63, 127-287, 2009. [6] Menapace, C., Lonardelli, I., Molinari, A., Phase transformation in a nanostructured M300 maraging steel obtained by SPS of mechanically alloyed powders, Journal of Thermal Analysis and Calorimetry, 101, 815-821, 2010. [7] Skiba, T., Hausild, P., Karlik, M., Vanmeensel, K., Vleugels, J.,Mechanical properties of spark plasma sintered FeAl intermetalics, Intermetallics, 18, 1410-1414, 2010. [8] Yanagisawa, O., Kuramoto, H., Matsugi, K., Komatsu, M., Observation of particle behavior in copper powder compact during pulsed electric discharge, Materials Science and Engineering A, 350, 184-189, 2003. [9] Bernard-Granger, G., Addad, A., Fantozzi, G., Bonnefont, G., Guizard, C., Vernat, D., Spark plasma sintering of a commercially available granulated zirconia powder: Comparison with hot-pressing, Acta Materialia, 58, 3390-3399, 2010.
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SiCp Takviyeli Zn-Al Matriksli Metal Matriksli Kompozit Malzemeleri Akm Sinterleme Yntemiyle retilmesi
Ramazan KARSLIOLU, Mehmet UYSAL, Hatem AKBULUT Sakarya University Engineering Faculty, Department of Metallurgical and Materials Engineering, rkarslioglu@sakarya.edu.tr zet Bu deneysel almada Zn-Al matriks ierisine hacimce farkl oranlarda(%0, %10, %20, %30) SiC takviyelenmitir. stenilen bileimdeki numuneler toz metalurjisi yntemi kullanlarak hazrlanmtr. SiC takviyeli Zn-Al alamlar akm destekli sinterleme yntemiyle 200 A akm altnda 10 dk sreyle sinterlenmitir. sinterlenen numuneler taramal elektron mikroskobu(SEM), Optik mikroskop, mikro setlik cihazlar kullanlarak analiz edilmitir. Akm sinterleme yntemi ile Zn-Al alamlarnn rtilebilirlii ve SiC orann etkisi incelenmitir. Anahtar Kelimeler: Zn-Al alam, Toz Metalurjisi (T/M), kompozit, akm destekli sinterleme Abstract In this study, Zn-Al matrix was reinforced with different ratio SiC(0 vol%, 10 vol%, 20 vol%, 30 vol%). Intended compositions of samples were prepared by Powder Metallurgy. SiC reinforced Zn-Al alloys were produced by current activated sintering under 200 A with 10 min. Sintered samples were characterized by optic microscope, Scanning Electron Microscope (SEM) and Microhardnes. Reproducibility of Zn-Al alloys by current activated sintering and effect of SiC ratio were investigated Keywords: Zn-Al alloys, Composite, Powder metallurgy, current activated sintering, 1.Giri Metal matriksli kompozit malzemeler, tek bileenli yaplarla baarlamayan, gerekli ve istenen zellikleri salamak zere en az biri metal veya alam dieri takviye malzemesi (srekli fiber, wisker ve partikl eklinde genel olarak metaller aras bileik, oksit, karbr veya nitrr bileikleri gibi) olan iki veya daha fazla farkl sistemin birleimi ile elde edilen malzeme grubudur. Yksek elastik modl, yksek mukavemet ve yksek anma direnci gibi zellikleri salamak zere metal alamlarna yaplan ilaveler, partikl eklinde SiC, TiC, B4C ve Al2O3 gibi seramik takviyeler olabilmektedir [1]. inko alminyum alamlar son yllarda srekli gelien ve sk kullanm alanlar bulan alamlar haline gelmitir. Gnmzde ZA alam ailesi olarak bilinen ZA-8, ZA-12 ve ZN-AL alamlar, deiik alanlarda yaygn olarak kullanlan ZAMAK alamlarnn uygulama alanlarn daha da genileterek, birok endstriyel uygulamalarda (konstrksiyon, otomotiv, madencilik vs.) yer almaktadr [2]. inko-alminyum alamlar mukavemetli, korozyon ve anma direnci iyi, ayn zamanda kolay dklebilirlie sahip alamlardr. Ancak younluklarnn yksek olmas ve scaklk art ile mukavemetlerini nemli oranda kaybetmeleri gibi dezavantajlar vardr [3]. stn tribolojik zelliklere sahip olan inko alminyum esasl alamlar, pek ok uygulamada beyaz metal, bronz, pirin ve dkme demir gibi geleneksel yatak malzemelerinin yerini almaktadr [4-5]. Toz metalurjisi yntemi ile retilen inko-Alminyum alamlarnn sinterlenmesinde byk problemler yaanmaktadr. Bunun nedeni sinterleme esnasnda inkonun buharlaarak yapdan uzaklamasdr. Bu nedenle son yllarda
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ilgi eken akm sinterleme yntemi inko-Alminyum alamlar iin de uygulanabilir gzkmektedir. Bu yntemde inko tozlar buharlamaya vakit bulamadan Alminyum tozlar ile etkileime girerek birbiri ierisine difze olurlar. stenilen bileimi ve yapy ok ksa srede oluturabilirler. Bu almada, olduka iyi anma direnci, mkemmel sertlik zellikleri ve yksek mukavemete sahip SiC partiklleri kullanlarak, Zn-Al alamnn anma zelliklerinin gelitirilmesi amalanmtr. Zn-Al alamnn ve MMK malzemelerin retimi akm destekli sinterleme yntemiyle gerekletirilmitir. Takviyesiz Zn-Al ve hacimce % 10, % 20 ve % 30 SiC partiklleri takviye edilerek kompozit malzemeler retilmitir. Alam ve kompozitlerde mikroyap incelemesi ve sertlik lmleri yaplmtr. 2.Deneysel almalar MMK malzeme retiminde kullanlan mariks malzemesi Zn-Al alamdr. Alam arlka %73 Zn %27 Al bileimindedir. inko ve alminyum tozlarnn boyutlar 45-90 m arasnda olup GTV Verschleiss-Schutz GmbH ticari marka tozlar kullanlmtr. Matriks alam %10, %20 ve %30 orannda SiC ile takviye edilmitir. Kullanlan SiC tozlarnn partikl boyutu ~55mdir. Numuneler geleneksel toz metalurjisi yntemi kullanlarak hazrlanmtr. inko, Alminyum ve SiC tozlar etil alkol ierisinde bilyeli deirmen kullanlarak 4 saat boyunca kartrlmtr. Kartrlan tozlar n ekillendirme ile 20 MPalk basn altnda elik kalp kullanlarak numuneler hazrlanmtr. Numuneler bakr elektrotlar arasnda ve elik kalp ierisine yerletirilerek 200 A akm altnda 10 dk sre ile 5 barlk basn altnda sinterlenmitir. Sinterleme esnasnda elik kalbn scakl lazer termocouple kullanlarak 400 oC olarak llmtr. Deney dzenei ekil. 1de gsterilmitir. retilen numuneler metalografik yzey hazrlama yntemi ile hazrlanp fazlarn optik mikroskopla grnebilmesi iin dalama yaplmtr. Metalografik olarak hazrlanan alam ve kompozitler NIKON ECLIPSE L150A optik mikroskobu ile incelenmi ve partikl dalmlar aratrlmtr. Daha sonra alam ve kompozit numuneler Future Leica VMHT MOT Mikro sertlik cihaz yardm ile 50 gr 15 saniye sreyle uygulanarak mikrosertlik lmleri yaplmtr. Sertlik lmleri mariks fazndan alnmtr. lmn salkl olabilmesi iin her numuneden beer adet lm alnarak ortalamalar kaydedilmitir. Taramal elektron mikroskobu (SEM) incelemeleri ve EDS analizleri Jeol JSM 6060 LV marka cihazla yaplmtr.
ekil 1. Deney dzeneinin a)ematik gsterimi b)Deney esnasndaki grnm[6] 3. Deneysel Sonular 3.1. Optik Mikroskop Sonular Zn-Al alamlarnn sinterlenmesinde gnmzde teknolojik glkler yaanmaktadr. inkonun ergimeden buharlama davranndan dolay geleneksel sinterleme ilemlerinde kontroll atmosferde yaplan sinterleme ilemlerinde bile nihai rnde ok nemli poroziteler ortaya kmakta ve bu da mekanik ve fiziksel zellikleri ok olumsuz etkilemektedir. Benzer ekilde Cu-Zn ve bronzlarda da sinterleme hatalar ile karlalmaktadr. Bu hatalar zellik-
877
lerin d yannda ou zaman sinterleme sonrasnda malzemelerde boyutsal art (ime) ortaya karmaktadr. Yaplan optik mikroskop incelemelerinden elde edilen grntler ekil 2-5 te grlmektedir. Alamn mikro yaps incelendiinde, alamn lamelli tektik yap hakim bir yap gsterdii anlalmaktadr. Bu tr mikroyap klasik dkm yntemleri ile retilen Zn-%27 Al alamndan farkldr. Lamelli tektik yapnn zellikle SiC partiklleri etrafnda ekirdeklenme eilimi gsterdikleri ortaya kmaktadr. Kompozit mikro yaplarnn incelenmesinden SiC partikllerinin Zn-Al mariksi iinde olduka homojen daldklar, segregasyon gstermedikleri gzlenmitir. Saf Zn-Al alamnn sinterlenmesi Zn-Al nin birbirlerinin iine difzyonu iin deneysel parametrelerin yeterli olduu grlmektedir. ekil 1 den de anlalaca zere toz metalurjisi ytemi ile retimi zor olan Zn-Al alamlar baarl bir ekilde retilmitir. ekil 3 deki %10 SiC takviyeli Zn-Al alam incelendiinde SiC partiklerle matriks malzemesi arasnda iyi bir birleme olduu yksek bytmeli fotoraftan da dorulanmtr. SiC oran oran % 20 ye ktnda yapda poroziteler grlmtr (ekil 4). % 30 SiC takviyeli yapy incelediimizde ise yap ierisindeki porozite miktarn ve boyutlarnn artt grlmektedir (ekil 5). Bunun muhtemel nedeni SiC miktarnn art Zn ve Al arasnda difzyonu engellemesi ve dolaysyla daha yksek scaklklar veya srelerde retimin yaplmasna ihtiya duyulmasdr. Metal ve alamlarna ilave edilen sert seramik esasl fazlarn yksek scaklkta kullanlma imkanlarn arttrmas da difzyonun engellenmesinden kaynaklanmaktadr. zellikle yksek miktarda SiC takviyeli alamlarn retilmesinde engellenen difzyon neticesinde klasik Zn-%27 Al mikroyaps elde edilememektedir. Elde edilen lamelli yaplar daha ok Zn-%5 veya Zn-%12 Al bileimlerini andrmaktadr. Dier taraftan matriks alamna ilave edilen SiC partikllerinin faz dnm iin heterojen ekirdekletirici olarak davrandklar da mikroyaplardan anlalmaktadr. tektik dnm genelde SiC seramik partiklleri zerinde olumaya balamaktadrlar.
ekil 2. Zn-Al alamn mikro yaps
ekil 3. Zn-Al+%10 SiC kompozit yapnn optik grnts
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3.2. SEM ve EDX incelemeleri
ekil 6 SEM Fotoraf ve EDX analizi sonular ekil 6 da geri salm dedektr kullanlarak elde edilen yksek bytmeli SEM mikroyap fotoraf verilmitir. Mikro yap incelendiinde SiC ve matriks malzemesi olan Zn-Al alam arasndaki ban salanabildii buradan da anlalmaktadr. Ayn zamanda alam yaps da ayrntl olarak gzkmektedir. EDX analizileri yardmyla SiC ve Zn-Al yaplar mikro yap zerinde gsterilmitir. 3.3. Mikro Sertlik Sonular retilen mariks (Zn-Al) ve deiik oranlarda SiC takviyeli kompozitlerin akm altnda sinterlenmesi sonrasnda matrikste ortaya kan mikro sertlik sonular ekil 7da verilmitir. SiC miktar arttka beklenildii gibi sertliin artt gzlenmitir. SiC ierii fazla olan kompozitin sertlii en yksek deerde iken alamn sertliinin kompozitlere gre daha dk kald grlmtr. retilen kompozit malzemeler arasndaki bu farkn nedeninin MMK malzemelerde, takviye malzemelerinin yksek sertlik deerlerine sahip olmasdr. Bunun yannda yksek takviye orannda fazla yk transferi ve bu malzemelerin souma srasnda kendisi ve mariks malzemesi arasndaki yksek termal genleme katsays farknn bir sonucu olarak ortaya kan dislokasyon younluunun etkili olduu dnlmektedir.
ekil 7. Elde edilen kompozitlerin sertlik deerleri 3. Sonular Klasik sinterleme yntem ile sinterlemesi mmkn olmayan Zn-Al alam akm sinterleme yntemi ile baarl bir ekilde retilmitir.Akm sinterleme ytemi kullanlarak ksa srede SiC takviyeli Zn-Al mariksli MMK malzemeler baarl bir ekilde retilmitir. SiC partiklleri matrikste homojen dalmlardr. Artan partikl miktar mikroporozitenin artna yol amtr. Zn-Al ierisindeki SiC miktarnn art matriks sertliini artrd grlmtr. Kaynaklar 1. Sornakumara T. , Senthil Kumarb A. journal of materials processing technology Vol. 202 pp 402405 2008 2. Smith W., Structure and Properties of Engineering AlIoys, 2nd Edn, p. 561. McGraw-Hill, New York 1993. 3. Lee P. P., Savaskan T. and E. Laufer, Wear Vol 117, pp 79 1987. [4] Seah K. H. W., Sharma S. C. and Girish B. M., Mater. Des. in press (1996). [5] Seah K. H. W.,_ Sharmas F S. C. and Grshs B. M. Corrosion Science, Vol. 39, No. 1, pp. 1-7, 1997 [6] Karslioglu R.,Uysal M.,Alp A.,Akbulut H., Tribology Transactions, Vol. 53, Issue 5 pp 779 - 785 2010
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6th INTERNATIONAL POWDER METALLURGY CONFERENCE & EXHIBITION 6.

ULUSLARARASI TOZ METALURJS KONFERANSI ve SERGS

THE PRACTICAL ANALYSIS OF FABRICATION OF A COPPER PART BY METAL INJECTION MOLDING

Figure 1. Schematic diagram of MIM process.

Figure 2. Geometry of sample.

Figure 3. The graph of debinding/sintering.

Figure 4. Sintered part.

Porosity (vol.%) 1h at 1100C 2h at 1200C

ekil 1. Farkl akmlarda birletirilmi preform malzemeler

WC-Co KESC U HURDALARINDAN PROMETALURJK YNTEMLE WC ve Co TOZLARININ GER KAZANIMI

RECOVERY OF WC AND Co POWDERS FROM WC-Co CUTTING SCRAPS BY PYROMETALLURGICAL METHOD

ekil 3. SINTESTin grafiksel kullanc arayz

ekil 5. rnek # 1in B-Scani (younluk 6.85 g/cm3)

ekil 6. rnek # 2nin B-Scani (younluk 6.07 g/cm3)

HOLDING CONDITIONS ON MECHANICAL PROPERTIES OF CAST AL-B ALLOYS

Figure 3. Specimens for Tensile and Impact Testing

Figure 4. UTS variations of the samples

30 min 45 min 60 min

Figure 6. Microstructure of produced Al-B alloy: a) 10X b) 50X c) 100X

VIBRATION DAMPING CHARACTERISTICS OF BORON COMPOSITES

Production of Al- B4C functionally graded material by powder metallurgy method

Fig. 3. Developing procedure of FGMs [9].

YKSEK ENERJL BLYEL TME YNTEM LE BOR NTRR NANO TP RETM

BOR KARBRL ELMASLI KESC SOKETLERN MKROYAPI VE MEKANK ZELLKLER

ekil 3. Cu-Sn ikili faz diyagram [19]

ekil 4. Soketlerin XRD grafii

B4C TAKVYEL ALMNYUM KPKLERN KPRME ZELLKLERNN ARATIRILMASI

INVESTIGATION OF THE FOAMING BEHAVIOUR OF B4C REINFORCED ALUMNUM FOAMS

ekil 1. B4C miktarna bal hacimsel genileme ve younluk deiimi

CHARACTERIZATION OF POWDER AND PARTS

Transverse Rupture Strength Properties of Diamond Impregnated Metal Matrix

Figure 1. The relation between mean pressure and sliding distance.

Table 2. Wear Rate of the Materials

MICROSTRUCTURAL CHARACTERIZATION OF POWDER METALLURGICAL TOOL STEELS ETCHED BY DIFFERENT TECHNIQUES

COMPACTION AND MECHANICAL PROPERTIES

HIZLI KATILATIRILMI MONEL 400 TOZUNUN PRESLENME DAVRANIININ NCELENMES

INVESTIGATION OF PRESSING BEHAVIOUR OF RAPIDLY SOLIDIFIED MONEL 400 POWDER

ekil 5. Presleme basncyla ham younluun deiimi.

The effect of amount of methanol on the properties of Al-Al2O3 composite powders

Flake+ Flake+ Semi Semi Equiaxial Equiaxial

Apparent density (gr/cm3)

Amount of PCA (wt.%) 1 2 3

T= 298K (25C), t=10 min

T=298K (25C), t=25 min

Figure 2. Particle size distribution of SiC powder

Figure 3. SEM photomicrograph of SiC particles

Figure 4. XRD spectrum of SiC powder 3. Results

Figure 6. Al-Ni binary diagram

PRODUCING OF STEEL CHIPS REINFORCED ALUMINUM COMPOSITES WITH POWDER METALLURGY

Etial 65 AISI 1040

Figure 1. Compaction die for producing compressive specimens.

Figure 4. Hardness vs. steel contents.

Figure 2. Macrohardness (HV30) of the samples

WEAR STUDIES ON DIAMOND-REINFORCED Fe-Co BASED METAL MATRIX COMPOSITES

Fig.1. Schematic view of the pin-on-disc test procedure

THE EFFECT OF SINTERING AND NITRIDING PROCESSES ON DISTALOY AE POWDER MATERIALS

Figure 4. Compare hardness of sintered and nitrided specimens

Figure 5.Nitriding layer of samples

BYOMEDKAL UYGULAMALAR N Ti-Mg KOMPOZTLERNN GELTRLMES

DEVELOPMENT OF Ti-Mg COMPOSITES FOR BIOMEDICAL APPLICATIONS

Numune Saf Magnezyum Ti-50%Mg Ti-60%Mg Ti-70%Mg Ti-80%Mg

The ProductIon of Cemented Cu MatrIx-SIC ComposItes By Powder Metallurgy Method