Paper Ref: S0311_P0278 3rd International Conference on Integrity, Reliability and Failure, Porto/Portugal, 20-24 July 2009

ALUMINIUM-BASE NANOCOMPOSITE OBTAINED BY MELTSPINNING TECHNIQUE

S. Valdez1*, S. R. Casolco2 and L. Martnez1, J.M. Gmez de Salazar3 Instituto de Ciencias Fsicas-Universidad Nacional Autnoma de Mxico, Av. Universidad S/N, Col. Chamilpa, C.P. 062210, Cuernavaca, Morelos, Mxico. 2 Instituto Tecnolgico y de Estudios Superiores de Monterrey, Campus Puebla, Va Atlixcyotl 2301, C.P. 2800. Puebla, Pue. Mxico. 3 Depto. de Ciencia de Materiales e Ingeniera Metalrgica. Facultad de CC. Qumicas. Universidad Complutense de Madrid. Avd. Complutense s/n 28040. Madrid Espaa. Email: svaldez@fis.unam.mx
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ABSTRACT A new nanocomposite Al-base has been manufactured by melt-spinning technique. This technique allows obtaining a material with small size grain by cooling rate control and high undercooling temperature, basically. In this study the nanocomposite ribbon obtained by the melt-spinning technique has been formed by nano sized grains of 90 nm. The composite material has been prepared with the Al-Mg matrix alloy added with 10vol%SiC particulates mixed into the steel tubes at 1500 rpm. In addition, the mechanical properties such as microhardness and strength have been determined and they were compared with AlMg ribbon. A mechanical property has been improved when the AlMg alloy was added with SiCp and was improved yet when the composite AlMgSiCp has been manufactured on to nanocomposite ribbon. INTRODUCTION The great interest to use low oil has been conduced to development a better design and very high strength aluminum alloys. Al-base alloys, has been studied by many researchers, due to their excellent castability, corrosion resistance and high specific strength [Goehler, 1998]. The AlMg alloys (5XXX), are the most frequently aluminum alloys used in car body panels [Gaffar, 2007].The usage of these Al-alloys for automotive applications has increased steadily in the recent years. The Aluminum and its alloys, combine their mechanical properties like ductility, conformability and low densidad with the properties of the reinforcement ceramic particles, such as hardness, chemical and thermal stability, in order to get a composite material with better properties. One of the combinations (metal + ceramic particles) more studied is the Al/SiCp system, whch has been characterized by a good resistance to the wearing down and high thermal conductivity [Mahagundappa, 2006]. Compared with metallic alloys, the reinforced compounds of metallic matrix with ceramic particles (MMCs) display major mechanical resistance, better thermal properties (elevated thermal conductivity) and major dimensional stability [Valdez, 2008]. The compounds of metallic matrix are considered like excellent candidates in structural applications, and aeronautical-aerospace uses, or in the automotive industry.

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Mechanical properties such as strength and hardness are mainly depended on its microstructure, much effort has been devoted to refining the grains of the alloys in order to improve them [Zhang, 2007]. High cooling rates generate a fine and homogeneous microstructure. The cooling rate has an important role on the microstructure, which has a significant effect on the mechanical and electrochemical properties [Garca, 2008]. Effects of time and cooling rate are very important. By varying the cooling rate, amorphous and metastable phases can often be formed which are not predicted by phase diagrams. In addition, with the combination of high subcooling and high cooling rates, is possible to obtain a fine microstructure until nanosize with improved hardness and mechanical resistence relationship. The microstructures formed during the solidification of an alloy play an enormous role in the properties of solid material. In metals, alloys and composite materials with nanosize structure, the hardness and strength increases, enhanced ductility, toughness and formability [Xu, 2006]. During recent decades, great efforts have been devoted to the research of rapid solidification (RS) technique. The level of undercooling achievable at high cooling rates refines the microstructure and improves the mechanical properties. Rapid solidification controls the microstructure through grain refinement and ultra-fine second phase precipitation. The rapid solidification is applied on different ferrous and nonferrous materials[Benyounis, 2009] including alloy steels, tool steels, cast irons, titanium alloys and aluminum alloys. Rapid Solidification process was carry out by the melt spinning technique, used to produce Al-Mg metallic ribbons with dissolved SiC refiner particles. With the rapid solidification process was possible to get high cooling rates and a nanocrystalline AlMgSiCp composite. Ribbons of 35 m thickness was obtained by ejected the AlMgSiCp melt overheated at 100 C onto a copper wheel (0.25m diameter) rotating at 40m/s. The melt-spun AlMgSiCpcomposite structure consisted of nanometric grains of 90 0.2 nm. The nanostructured aluminum alloys and composites, are in the top ten materiales due to their remarkable properties, are comparable to highstrength steels having the weight of only one third of steel parts.
Table 1 Chemical composition (% wt.) for AlMg matrix, AlMgSiCp casting/ribbon composite, obtained by ICP.

Element Mg Fe Mn Si Casting matrix 9.95 0.30 0.19 0.21 Casting composite 9.85 0.33 0.22 0.28 Ribbon composite 9.73 0.40 0.20 0.26 Material EXPERIMENTAL DETAILS

Al Bal Bal. Bal.

Others 0.2116 0.1121 0.1014

Cast ingots of the Al-Mg matrix alloys were prepared by the melt stirring technique with stoichiometrically mixing pieces from Al and Mg (99.98% commercial purity) alloying elements.

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The Al (660 C) and Mg (650 C) elements were put inside of alumina crucible with an inner diameter of 120 mm and placed inside a resistance furnace previously preheated at 300C for 15 minutes. A mixture of flux salts (KCl + NaCl in relation 1:1) was used to avoid the contact between the molten alloy and the atmosphere in order to dimmish the elements oxidation. During the SiCp addition, the molten Al-Mg matrix temperature was maintained at 71010 C. The silicon carbide particulates in 10% vol. (SiCp) were previously heated at 1000 C, and then were incorporated by the Vrtex Method to the Al-Mg molten matrix via refractory feeder tip directly into the steel crucible at 1150 rpm. Al-Mg-SiCp molten composite was stirring for up to 15 minutes in order to get a better homogenization, after that was degassed with pure argon when the crucible was inside the furnace, after that the drag was eliminated mechanically. The melt composite was superheat above the liquidus temperature and was poured by two differente ways. One of them was by conventionally cast alloys, in where the melt composite was poured into metallic steel molds at 710 C. The other way, was by the meltspinning technique ribbons, in this case the melt composite was stirring until their was poured in cuarze crucible with 1.0 mm diameter orifice, the crucible was inductively preheated at 700C in an atmosphere of 200 mbar argon, and then was ejected onto a copper wheel with 0.25m diameter and with a peripheral velocity of 40m/s. Their nominal chemical composition of AlMgSiCp composite ingot and ribbon was obtained by ICP and are given in Table 1. The mechanical properties of casting and ribbon composite were determined by microhardness measurements. Vickers hardness measurementes were made using a Vicker pyramidal indenter using a digital Instron microdurometer. Each hardness value corresponds to the averages of at least ten identations with load 980.70 mN (HVO.1). Before to carry out the vickers measurements, the samples surfaces were prepared by the standard technique of grinding with SiC up to # 1000 emery paper and mechanical polishing with Al2O3 suspension solution. After that, the casting and ribbon samples were cleaned by ultrasound machine, degreased in acetone, washed thoroughly in distilled water and dried with hot air. RESULTS With the melt-spinning technique, was possible to obtain ribbons without effect of the remelting process. The composite ribbon had typical width 2 mm and thickness 40 m (Figure 1), giving an estimated cooling rate of 105 to106 K s1, this value is much higher than the cooling rates applied for conventional solidification processes, which is about 102 K/s or less[Karakose, 2009]. For that reason, our values of cooling rate are considered for the rapid solidification. This process occurs at rates fast enough yields compositions and phases or microstructures not normally achieved by the conventional casting solidification rates[Abd, 2009]. The melt spinning technique is the most important one commonly employed to produce long and continuous ribbons[Yan Wang, 2006], suitable for investigating the mechanical properties.

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Figure 1. Representative samples of a) AlMg matrix alloy, b) AlMgSiCp casting composite and c) AlMgSiCp ribbon obtained by rapid solidification. Table 2, reports the microhardness results for the casting matrix AlMg, the casting composite AlMgSiCp and the ribbon composite. An increase of the microhardness value is observed when SiCp addition and increase too with the rapid solidification. This is because, the high cooling rate for rapid solidification process suggest refinement of microstructure. Similar effect was found previously by Benyounis et al. Is well known, that the process of rapid solidification improves the mechanical properties such as hardness, strength and ductility, when the grain size is reduced to the nanometer scale[Milligan, 2009]. In addition, leads to the formation of new intermediate phases, amorphous and refined microstructure, increased structural and chemical homogeneity, extended solubility and anomalous vacancy concentrations[Green, 1994 and Inokuti, 1979].

Material Casting matrix Casting composite Ribbon composite

Microdureza Grain size 74 2.5 126 3.3 284 3.1 0.38mm 0.25mm 90nm

The microhardness increase 1.7 times when the SiCp has been added, due to the SiC particles can be considdered as an effective grain refining. These particulates (impurity and SiC) has been identified as nucleating substrate, because particulates acts like nucleation sites, interferes in the growth of grains providing a greater number of surfaces and then eliminate the barrier energetics of the subcooling and increasing, the number of nucleation sites. It is also known that controlling the impurity levels affects the grain size of alloys, where Al alloys have a significantly finer grain size than commercial purity alloys [Easton , 2006]. In addition when the composite was rapid solidified their microvickers hardness increase 3.84 and 2.25 times with respect to the casting matrix and casting composite respectively. This means that particulates addition and ultra high cooling rate controls the grain refinement. Which should be considered, that the increase in the cooling rate decrease subcooling during the nucleation. This phenomenon originates an increase in the temperature of nucleation, consequently the solidification rate increases, due to the presence of a greater

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number of nuclei and agglomerates of atoms that tends to grow simultaneously, diminishing then the size of grains. The equation 1 shows the relationship between the grain refinement and particle addition with solidification conditions.

d=

1 (bTn ) + 11 / 3 (a ) Cs %p

(1) (2)

Cs = m i C o ,i (k i 1)
i

where %P is the particle addition rate in weight %, Tn is the nucleation undercooling and Cs is the solute content, m is the liquidus gradient, C0, i is the the initial alloy composition of each element i and k is the partition coefficient. The equation shows that the gradient is related to the nucleant potent and the intercept to the number of substrates available for nucleation, thereby the mechanism causing changes in grain size. Similar study was done previously in Mg alloys by Easton et al., adding silicon carbide particles, and decreasing Tn was lead to a decrease in the grain size.
CONCLUSIONS

Rapid solidification provides a ribbon with nanostructure grains of 90 nm. With the melt-spinning technique, was possible to obtain ribbons without effect of the remelting process and casting defects. The ribbon shows an improve grain refninement and microhardness. The silicon carbide particles content in the melt Al-Mg alloy has a beneffical effect on grain refinement and the in the microvickers hardness.
ACKNOWLEDGMENT

The authors would like to express their gratitude to DGAPA-PAPIIT and CONACyT, Grants No IN105708 and 89981 for their financial support of this research project.
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