PROJECT REPORT

SUBMITTED TO
MR. K. PANDA (P.R & H.R.D)

GUIDED BY
MR. RAJIV KUNDU (AGM-Technology)

SUBMITTED BY
ABINASH PRADHAN CERAMIC ENGINEERING N.I.T ROURKELA

CERTIFICATE
This is to certify that I, ABINASH PRADHAN bearing roll no: 110CR0611 branch CERAMIC ENGINEERING, NIT ROURKELA (6th semester completed) has prepared a project report at TRL KROSAKI REFRACTORIES LTD. Under the supervision of MR. RAJIV KUNDU (AGM-Technology). I further certify that this report has been completed by ABINASH PRADHAN for partial fulfilment of my analysis.

MR. RAJIV KUNDU (AGM-Technology)

ACKNOWLEDGEMENT
I take this opportunity to express my sincerity gratitude to Dr.Mihir Ranjan Nayak (Chief of PR&HRD) for allowing me to carry out my industrial training & project at TRL KROSAKI REFRACTORIES LTD., BELPAHAR. I am very thankful to Dr. S.ADAK (Vice president of technology) who gave me a chance to work in R&D. I am very thankful to MR. RAJIV KUNDU (Assist. General Manager Dolomite & Basic) who gave me a chance to work in his dept. I am sincerely thankful to MR. HARA PRASAD MURTY (Manager-Technology) & MR. (Manager-Technology) for giving me time from their busy schedule for guiding my vocational training. I am thankful to MR. K. PANDA (PR & HRD) for his support throughout my training and for his valuable guidance & co-operation in my work. I am thankful to all the employees who have helped me a lot in collecting the necessary information. There loving & caring word praise has really encouraged me.

YOURS FAITHFULLY ABINASH PRADHAN ROLL NO: 110CR0611 CERAMIC ENGINEERING (6th semester completed) NIT ROURKELA

INTRODUCTION
REFRACTORIES
Refractories, a key input for iron and steel making, assume ever increasing role due to high stress on production of high quality steels, which alone accounts for the consumption of nearly 70% of total refractories produced. Refractories in general, are the non-metallic materials that are difficult to melt at high temperature and have enough mechanical strength and heat resistance to withstand rapid temperature change, including repeated heating and cooling and resistance to molten slag and metals. They are those inorganic,non-metallic materials having those physical and chemical properties that make them applicable for structures or as components of those systems that are exposed to high temperature environments above 1000C. Refractories are porous, multi-component and heterogeneous materials composed of thermally stable mineral aggregates, a binder phase and additives. They are quasi brittle at low temperature and have a viscous behaviour at high temperature. They are characterized by high temperature creep or plastic deformation. Their brittleness and their high elastic modulus make them sensible to failure under thermal stress and shock .Generally refractories are classified into two categories i.e. (i) The shaped refractories, available in the form of different brick shape, and include the oxide and non-oxide systems. (ii) The unshaped refractories, which includes mortars, castables, plastics etc. Three types of refractory materials exist depending upon their chemical nature as given below:1) Acidic refractory: - It should not be allowed to come in contact with basic products to avoid the reaction. Examples Fire clay, Silica, Quartz, Ganister sand, Semi-silica etc. 2) Basic refractory: - Should not come in contact with acidic products. Examples Bauxite, lime, magnesia, dolomite, alumina, zirconia. 3) Neutral refractory: - Can be used in conjunction with acidic or basic products. Examples Chromite, graphite, carbon, carbide, mullite.

MAGNESIA REFRACTORIES
Magnesia refractory is defined by the American Society for Testing and Materials (ASTM) as a dead-burned refractory material consisting predominantly of crystalline magnesium oxide . Furthermore, ASTM defines dead-burned as the state of a basic refractory material resulting from a heat treatment that yields a product resistant to atmospheric hydration or recombination with carbon dioxide (2). The chemical formula for magnesium oxide is MgO. However, no dead-burned magnesium oxide contains 100 wt.% MgO. Chemical assays of any such refractory raw material show some level (generally less than 30 wt.% total) of silica, lime, iron oxide, alumina, and boron oxide, that, mineralogically, occur (1) in triple-point pockets and films between the MgO crystallites in the dead-burned magnesium oxide material as, for example, various calcium silicates, calcium magnesium silicates, calcium boron silicates, and calcium aluminates; (2) as lime and iron oxide solid-solutions in the magnesia crystallites; and (3) sometimes, as magnesioferrite exsolution intergrowths, within the magnesium oxide crystallites themselves. Magnesium oxide raw materials and products can be referred to interchangeably as one of four names or terms and, thereby lead to some confusion for people unfamiliar with commercial industry vernacular:(1) MgO; (2) magnesia; (3) periclase; and (4) magnesite. Technically, (1) MgO is the chemical formula for pure magnesium oxide; (2) magnesia is the chemical name applied to the oxide of magnesium; (3) periclase is the mineral name for magnesium oxide (this mineral is rarely found in nature, but is presently applied to high-grade [generally,less than 10 wt.%. impurities], deadburned magnesium oxide products produced synthetically from, for example, seawater or underground brines); and (4) magnesite is the mineral name for magnesium carbonate, MgCO3and is one of the original sources for magnesium oxide used in refractory products (magnesite has to be dead-burned to remove the carbon dioxide, but the name has carried over to the dead-burned product of the magnesium carbonatecurrent U.S. terminology is to use magnesite for deadburned magnesium oxide produced from naturally occurring magnesite, especially those raw materials with impurities greater than 5 wt. %, but its use secularly is not so differentiated). Some raw materials of refractory products can used directly, can be partially altered from naturally occurring mineral deposits, or are produced synthetically by various combinations of chemical processing and heat treatment. If the heat treatment is mild (~9001300C), the raw material is described as being calcined; if the heat treatment is more robust (~1500 2200C), the raw material is then described as being sintered (dead-burned materials are in this group); and if the heat treatment proceeds to a molten state (e.g., for MgO, in excess of 2800C), then

the raw material is said to be fused. The sintering of magnesite at a high temperature removes the possibility of shrinkage. Finally, a secondary source of magnesium oxide is from the mining and sintering of brucite deposits; this mineral is composed of magnesium hydroxide, Mg(OH)2, and has a theoretical MgO of about 70 wt. %. A major source of brucite was located in Nevada.

Production of Dead-Burnt Magnesia

Inspite of the remarkable developments in the field of sea-water magnesia, the natural mineral is still the principal source of raw material. To produce high-grade grains, moderate grinding followed by beneficiation techniques using froth flotation or heavy media is then required to remove gangue minerals before dead-burning in either rotary or shaft kilns. If the gangue minerals cant be removed sufficiently to produce high-grade magnesia, then fine grinding must be performed before beneficiation; consequently, high pressure briquetting is required for this fine-grained output in order to form a suitable pellet for deadburning. Preparation of magnesia for the manufacture of refractories involves dead burning of raw magnesite at about 1500-1700c to eliminate all the combined carbon dioxide and form magnesia of crystalline form, known as periclase(MgO). Natural magnesite is found in the form of MgCO3. MgCO3 on calcination at 900c gives rise to MgO. MgCO3 9000 C MgO + CO2

This MgO is prone to hydration and cant be used for refractory purpose. Hence calcined magnesite is again heated at 1650C-1700C to get dead burnt magnesite. Dead burnt magnesite can be produced directly for MgCO3 by heating it at 1650C- 1700C. MgCO3 1650-17000 C MgO + CO2

Refractories from periclase are stable and undergo very low shrinkages when reburnt and gives maximum slag resistance. Dead burning is carried out in shaft or rotary kilns.Dead burnt lumps obtained in sizes of 110-130mm are crushed to the desired fineness.Ground periclase with particles ranging in size upto 5mm max. is considered for manufacture of good quality bricks.

Dead-Burnt Magnesium Oxide Characteristics

MgO Content-The MgO content of dead-burned magnesium oxide is generally included in the grade and/or brand of the particular commercial product. Obviously, its overall purity plays an important role in determining what MgO content is suitable for a particular end use.

MgO Impurities-a chemical analysis of a sample of commercial MgO aggregate from naturally occurring sources will yield the following principal impurities: SiO2(silica); CaO(lime); Al2O3(alumina); Fe2O3(iron oxide); and B2O3(boric oxide). These impurities combine together from the MgO crystallites to form minerals that, under equilibrium conditions, can be predicted from phase equilibrium relationships in the MgOCaOSiO2Al2O3FeOFe2O3 system and generally confirmed by X-ray diffraction analyses.This fact is due to the impact that lime solubility has on altering the CaO/SiO2 wt. ratio determined by chemical assay and subsequent phase equilibrium assumptions; this ratio, in turn, controls the nature of the calcium silicate minerals that occur in the grains. The importance of the CaO/SiO2 wt. ratio can be appreciated from studying the MgOCaOSiO2 phase diagram; its representation is seen in Figure.

Figure 2 MgOCaOSiO2 phase diagram.

MgO Crystallite Size- Since chemical reactions, such as in refractory corrosion, are a function of available surface area, one would have to assume that the MgO crystallite size is important. The grain size of periclase crystals is of the order 20-40 and the true sp gr. is 3.58. periclase crystal melts at around 2800c. Prior average crystallite size of dead-burned magnesium oxide ranges from 25 to 100 mm; current synthetic, dead-burned magnesium oxide products are available with crystallites ranging from 100200 mm.

Bulk Density of MgO Grains- The true specific gravity of periclase is 3.58. Therefore, the closer the bulk density of a sample of a MgO aggregate is to that value, the lower its total porosity (open and closed pores). In refractory technology, generally, the densest body offers the best resistance to corrosion by slags and is the strongest to resist abrasion. Desired commercial MgO grains for products destined for basic oxygen furnaces and steel ladles should have bulk density greater than 3400 kg/m. Thermal Expansion of MgO- The coefficient of thermal expansion of an essentially pure MgO refractory is very high; for example, at 1425C, the linear expansion of a fused MgO or isostatically pressed and fired MgO of 99 wt.% minimum purity with a minimum bulk density of 3180 kg/m is about 2%. Of course, incorporating other refractory raw materials with magnesia in a refractory body will alter this value. Care is required in using these materials to account for this property in an engineering sense. Chemical composition and bulk density for a number of selected commercial dead-burnt magnesia from naturally occurring sources. Brand Kumas96A MagnesitasM30 QM9090 Radex S.L. QMAG 1 Country Turkey Brazil China Austria Australia MgO (wt.%) 96.5 96.5 92.5 90.0 96.5 CaO (wt.%) 2.2 1.0 1.3 3.0 2.0 SiO2 Fe2O3 (wt.%) (wt.%) 1.0 0.95 3.5 1.0 0.5 0.2 0.7 1.0 5.0 0.1 Al2O3 B2O3 BD (wt.%) (wt.%) (kg/m) 0.02 <0.01 3400 0.1 <0.01 3350 1.5 <0.01 3250 1.0 <0.01 3350 0.15 <0.01 3400

Typical magnesite characteristics Resist the action of slags rich in iron oxide and lime High electrical and thermal conductivity Low iron magnesia bricks have a better resistance to thermal spalling than
high iron magnesia bricks Corrosion resistance High melting point Higher thermal expansion and lower thermal shock resistance

ZIRCONIA REFARCTORIES
Zirconia refractories are usually classed as neutral refractories but they are not quite resistant to acid slags and hence are on the border line between neutral and basic refractories. Zirconia exhibits three well-defined polymorphs, the monoclinic, tetragonal and cubic phases. The monoclinic phase is stable upto about 1170C where it transforms to the tetragonal phase, which is stable up-to 2370C, when the cubic phase exists up-to the melting point of 2680C. Monoclinic, tetragonal and cubic zirconia are generally prepared by addition of stabilizing oxides such as MgO, CaO, Y2O3, Scandia and CeO2 in zirconia powders and subjecting the material to appropriate processing parameters. Zirconia is mostly available in beach sand. Both zirconia and zircon have a high melting point. Zirconia melts at a temperature of

2720C,but this is subject to the nature and amount of impurities which bring down the melting point. Interest in zirconia-based ceramics is attributed to their unique set of properties. The very high melting temperature of zirconia makes it a prime candidate for refractory applications. Zirconia is a candidate material for components that are subjected to high thermal shock resistance, high temperature and corrosive environments. Zirconia has been utilized in seals, engines, cutting tools, sensors, and thermal barrier coatings. Pure zirconia undergoes a number of reversible phase transitions during heat treatment. The most destructive is the transformation of tetragonal to monoclinic phase resulting in 4% volume change. The best method to exploit the properties of zirconia is improvement of sinterability by stabilization of the high temperature phases to room temperature. Control over the stability is achieved by doping zirconia with one or more of the fluorite stabilizer oxides CaO, MgO,Y2O3, and CeO2 are used to achieve either fully or partially stabilized zirconia. Calcia and magnesia are the most extensively used oxides to stabilize zirconia at their high temperature polymorphs because of their cheap precursors and refractory potential. However, CaO and MgO stabilized zirconia show poor stability due to the extensive tetragonal to monoclinic phase transformation resulting in extensive cracking in certain applications. The controlled, stress induced volume expansion of the tetragonal to monoclinic inversion is used to produce very high strength, hard, tough varieties of zirconia available for mechanical and structural applications. There are several different mechanisms that lead to strengthening and toughness in zirconias that contain tetragonal grains. This is a complex subject matter. Simplistically, these depend on the grain sizes, the thermal history and the kind and amount of stabilizing additive in the body. These variations lead to two strong, commercially available partially stabilized zirconia (PSZ) microstructures identified as TTZ (tetragonally toughened zirconia) and TZP (tetragonal zirconia polycrystal) ceramics. The TTZ is an MgO partially stabilized zirconia often designated as MgPSZ consisting of uniformly dispersed tetragonal precipitates in larger cubic phase crystals. The secondary thermal aging process requiring tight manufacturing controls for proper microstructural development has limited the supplier base for the tetragonally toughened zirconias. The second variety, TZP, is a pure tetragonal phase, very fine grain material stabilized with rare earth oxides, primarily yttria and less commonly ceria. They are often designated YTZP for the yttria stabilized product and CeTZP for the ceria stabilized product. The TZP material has found uses in cutting and wear resistant applications due to its reliable and outstanding hardness and toughness. TZP properties degrade rapidly when the material is exposed to water vapor at 200 to 300C, so controlled use conditions are important for good performance. All of the toughened zirconias show a degrading of properties with increasing temperature, and this class of high strength, tough materials is generally limited to use temperatures below 800C. Calcia(CaO) addition is preferred over other oxides due to stability of cubic phase at all temperatures. Whereas the magnesia or yttria-stabilization revert to the monoclinic structure at low temperature. While using calcia and magnesia as stabilizer in zirconia, the toughening of the material increases, by the mechanism known as transformation toughening. A significant limiting factor with these

toughening properties increases with increasing temperature of the material serves to stabilize the tetragonal phase thus reducing the propensity for the precipitates to undergo a stress-induced transformation to the monoclinic phase.

Preparation Zircon is a naturally occurring material, ZrSiO4 and is found in heavy mineral deposits such as illimanite,rutile,monazite and garnet as river or beach sands. In addition to high melting point it has very low thermal expansion and good resistance to abrasion. At high temperatures the following reaction takes place: the dissociation of zircon starts at 1400C and at about 1600C a complete reaction takes place forming a stable product of zirconia and mullite. Zirconia occurs naturally as Baddeleyite (which is the chief source of zircoinia), or is prepared from zircon.

Zirconia occurs in 3 systems. The monoclinic low temperature phase converts above approx. 1100C to the tetragonal and cubic high temperature phase respectively. The conversion is reversible. The monoclinic low temperature phase has a larger volume than both of high temperature phases. This effects an approx 5% by volume contraction or expansion when exceeding or falling below the conversion temperature.This means there would be intensive crack formation if a brick would consist of only ZrO2. If MgO is present then ZrO2 of the silicate is transformed into the cubic form. This does not undergo any transformations on cooling. It is the stable form. We see that ZrO2 undergoes many polymorphous transformations and these changes form monoclinic form to tetragonal form are accompanied with large volume changes which are reversible. On cooling the expansion takes place more rapidly than contraction on heating .So, ZrO2 has to be stabilized so that it does not undergoes these changes. It is possible to stabilize zirconia by adding MgO. Addition of MgO and heating the mixture to 1700C results in the formation of cubic solid solution and stabilization of ZrO2 where it shows uniform expansion. Additives of MgO,CaO,Y2O3 or other rare earths keep the high temperature phases metastable until room temperature.is reached. These additives also minimise the abnormal thermal expansion.One speaks of partially stabilized or completely stabilized zirconia depending on the amount of additives or stabilizers. Concerning partially stabilized zirconia,the abnormal thermal expansion is more or less intense depending on the monoclinic phases present. The completely stabilized materials have linear expansion. Stabilized zirconia is used as a grinding media and engineering ceramics due to its increased hardness and high thermal shock resistivity. 1. Unstabilized (Pure) Zirconia Pure zirconia is an important component of lead-zirconia-titanate electronic ceramics. Pure zirconia can be used as an additive to enhance the properties of other oxide refractories. It is particularly advantageous when added to high-fired magnesia and alumina bodies. It promotes sinterability and with alumina, contributes to abrasive characteristics. Pure zirconia is monoclinic at room temperature and

changes to the denser tetragonal form at about 1000 C, which involves a large volume change and creates cracks within its structures. Due to the inversion, pure zirconia has low thermalshock resistivity. 2. Partially Stabilized Zirconia (PSZ)
Partially stabilized Zirconia is a mixture of zirconia polymorphs, because insufficient cubic phase-forming oxide (Stabilized) has been added and a cubic plus metastable tetragonal ZrO2 mixture is obtained. This material is most commonly stabilized by MgO or CaO. A smaller addition of stabilizer to the pure zirconia will bring its structure into a tetragonal phase at a temperature higher than 1,000C, and a mixture of cubic phase and monoclinic (or tetragonal)-phase at a lower temperature. Therefore, the partially stabilized zirconia is also called as tetragonal zirconia polycrystal (TZP). PSZ is a transformation-toughened material. Microcrack and induced stress may be two explanations for the toughening in partially stabilized zirconia. Toughening results when the tetragonal precipitates

transform to the stable monoclinic phase at the crack tip as the crack propagates through the material. The Microcrack explanation depends upon difference in the thermal
expansion between the cubic phase particle and monoclinic (or tetragonal)-phase particles in the PSZ. Coefficient of thermal expansion (CTE) for the monoclinic form is 6.5 -6/ C up to 1200 C, 10.5-6/ C for cubic form. This deference creates microcracks that dissipate the energy of propagating cracks. The induced stress explanation depends upon the tetragonalto-monoclinic transformation, once the application temperature over pass the transformation temperature at about 1000 C. Stress energies from propagating cracks cause the transition from the metastable tetragonal to the stable monoclinic zirconia. The energy used by this transformation is sufficient to slow or stop propagation of the cracks. Partially Stabilized Zirconia has been used where extremely high temperatures are required. The low thermal conductivity (about 8 Btu/ft2/in/ F at 1800 F) ensures low heat losses, and the high melting point permits stabilized zirconia refractories to be used continuously or intermittently at temperatures of 2,200C in neutral or oxidizing atmospheres. Above 1,650C in contact with carbon, zirconia is converted in to zirconium carbide. Zirconia is not wetted by many metals and is therefore an excellent crucible material when slag is absent. It has been used very successfully for melting alloy steels and the noble metals. PSZ refractories are rapidly finding application as setter plates for ferrite and titillate manufacture, and as matrix elements and wing tunnel liners for the aerospace industry. PSZ is also used experimentally as heat engine components, such as cylinder liners, piston caps and valve seats.

3. Fully Stabilized Zirconia Generally, addition of more than 16 mol% of CaO (7.9 wt%), 16 mol% MgO (5.86 wt%), or 8 mol% of Y2O3 (13.75 wt%), into zirconia structure is needed to form a fully stabilized zirconia. Its structure becomes cubic solid solution. Its structure becomes cubic solid solution, which has no phase transformation from room temperature up to 2,500 C. As a good ceramic ion conducting materials, fully yttria stabilized Zirconia (YSZ) has been used in oxygen sensor and solid oxide full cell (SOFC) applications. The SOFC applications have recently been attracting more worldwide attention, due to their high energy transfer efficient and environment concerns.

Fig. Phase equilibrium representation of lime stabilized zirconia.

One broad class of materials, transformation-toughened zirconias (TTZ), has been extensively examined . This particular class of materials possesses a very low thermal conductivity and an unusual combination of high strength and fracture toughness at room temperature. The material's unusual mechanical properties stem from a stress-assisted "martensitic" phase transformation of a metastable tetragonal (t) phase to the stable monoclinic (m) phase; hence the name "transformation toughening. The mechanisms of this toughening are believed to include one or more of the following: deflection of the crack tip microcracking which leads to crack branching and an increase in the energy required for continued crack growth absorption of the crack tip energy by the phase transformation (tm) In order to achieve some degree of transformation toughening, a stabilizer (typically CaO,MgO, Y203, or CeO2) must be added. The addition of one of these stabilizers lowers the tm chemical driving force and thus the tm transformation temperature, enabling then t-phase to be retained in a metastable state upon cooling to room temperature. With these additions, new phases have also been identified. These include a high pressure orthorhombic phase, (which has been identified in CaO-stabilized cubic zirconia), a rhombohedral phase, and a non transformable t'-phase' (in Y203-stabilized zirconia).

The addition of various stabilizers results in one of two types of TTZs: a) partially stabilized zirconia (PSZ) or b) tetragonal zirconia polycrystalline (TZP) materials. Although both PSZ and TZP are, in fact, "partially stabilized," their microstructure and stabilizers are quite different. .

Zirconium Dioxide (ZrO2) Properties

Zirconia is best known among ceramics as being both hard and fracture-tough at room temperature. Additionally, its fine (sub-micron) grain size enables excellent surface finishes and the ability to hold a sharp edge. Although it retains many properties including corrosion resistance at extremely high temperatures, Zirconia does exhibit structural changes that may limit its use to perhaps only 500C. Superb corrosion resistance is characteristic of ZrO2.The reason is the very slight tendency of ZrO2 to enter compounds with other oxides. Zirconia has a low thermal conductivity particularly at high temperatures and therefore serves as a good insulator. Pure zirconia shows high volume change on heating,about 9% contractionat 10001100C,giving rise to poor thermal shock resistance. Zirconia bricks are resistant to the action of basic and acid slags.Their specific gravity is 4.47 and apparent porosity is 2025%.They are extremely resistant to corrosive action of such materials as molten glass and fused silica. Zirconia being susceptible to temperature changes on heating, has a low spalling resistance and therefore is not used where fluctuating temperature conditions exist. Zirconia is used as an addition to magnesite brick mixture to improve the thermal shock resistance of the bricks. More extensive applications of these refractories is hindered due to the fact that they are costly and heavy, each 9 brick weighing more than 12 lbs.It is possible to optimize thermal shock resistance by specially influencing phase changes and resulting thermal expansion.

Stabilized ZrO2 is very resistant to molten metals but is attacked a little by titanium and strong acid slags.Inspite of its several advantages it has some disadvantages or drawbacks. They are:

i. ii.

Zirconia bricks are costly and they have tendency of changing their crystal structure upon heating. Stabilized zirconia is prone to thermally age i.e. stabilizer tends to migrate out of the structure when material exposed to long term temperatures.

The fundamental properties of zirconia which are of interest to the engineer or designer are:

 high strength, high fracture toughness, high hardness, wear resistance, good frictional behaviour, non-magnetic, electrical insulation, low thermal conductivity, corrosion resistance in acids and alkalis, modulus of elasticity similar to steel, coefficient of thermal expansion similar to iron.

APPLICATIONS
Zirconia bricks are very expensive and are used only where the temperature is very high as in high frequency electric furaces. Zirconia finds applications in ZrO2-Al2O3 abrasives, erosion & corrosion resistant refractories for Glass furnace & special Cast refractories,, insulating materials, kiln furniture, crucibles, Saggers Nozzles, Applications requiring an inert material with high melting point and low thermal conductivity. Nozzles used in continuous casting steel plants are made of zirconia. zirconia is also used for lining high temperature ceramic kilns, barrier coatings for jet engines and furnaces used for melting precious metals,glazes,special glasses etc. It is electrically conductive above 600C and is used in oxygen sensor cells and as the susceptor (heater) in high temperature induction furnaces.

MAGNESIA-ZIRCONIA REFRACTORIES
Magnesia zirconia refractories are fired basic products which mineralogically consist of mainly periclase and zirconia. Secondary chemical constituents are CaO, SiO2, Al2O3, and Fe2O3. Graded sintered or fused magnesia are raw material base. ZrO2 is added to the raw material batch in the form of natural minerals zircon (ZrO2.SiO2) and baddeleyite(monoclinic-prismatic form of ZrO2) or technically produced zirconia(ZrO2 not stabilized or stabilized) and as calcium zirconate(CaO.ZrO2). These bricks are manufactured on the basis of sintered or fused magnesia and zirconia. Mineralogically they consist of periclase, stabilized ZrO2 or CaO.ZrO2 and small amounts of silicate phases. ZrO2 has uniform distribution in the brick structure and improves thermal shock resistance as a result of micro crack propagation. Diffusion processes during the partial or total stabilization of ZrO2 effect direct bonds between MgO and ZrO2. This gives the Mag-ZrO2 bricks increased hot properties when subjected to mechanical stress. Magnesia-zirconia products are distinguished by high corrosion resistance against alkali oxides and alkaline earth oxides as well as against highly basic slags. They posses superb thermal shock resistance and high endurance strength.

Prime features: Very high mechanical strength Excellent abrasion resistance Excellent corrosion resistance High impact resistance and toughness High resistance to thermal shock Very low thermal conductivity

AIM OF THE PROJECT

To develop toughened magnesia brick with addition of zirconia for vertical shaft lime kiln application.

LIME KILN
Two types of kilns are primarily used to calcine limestone and dolomite in todays lime industry: Rotary kilns, and Vertical shaft kilns Rotary kilns, with or without preheater, usually process grain sizes between 6 and 50 mm. The heat balance of this type of kilns is characterised by rather high losses with the off-gases and through the kiln shell. Typical figures for off-gas losses are in the range of 20 to 25% and for kiln shell losses 15 to 20% of the total heat requirement. Only approx. 60% of the fuel energy introduced into preheater type kilns is used for the calcining process itself. For all types of vertical single shaft kilns there is an imbalance between the heat available from the burning zone and the heat required in the preheating zone. Even with an ideal calcinations process (having an excess air factor of 1.0) a waste gas tempe-rature of 100C may only be achieved with limestone containing less than 88% CaCO3. However, lime produced from such low quality limestone has only a restricted field of application. In practice limestones with much higher carbonate content are processed resulting in higher waste gas temperature which is the consequence of excess available heat in the preheating zone. The question now is: How can the surplus heat available in the calcining zone of the kiln be utilised to minimise heat consumption and how do the modern kiln types match this aspect. An almost perfect solution for this problem is offered by the Maerz Parallel Flow Regenerative Lime Kiln (PFR-Kiln).

The PFR-Kiln
Two main types of vertical shaft kilns exist. The single shaft counter flow heating kiln and the multiple shaft parallel flow heating kiln. The standard PFR-Kiln is a two-shaft kiln defined by alternating burning and non-burning shaft operation. There are two key characteristics of the PFR-Kiln: 1) the parallel flow of hot gases and stone in the burning zone, and 2) the regenerative preheating of all combustion air in the process. The kiln is ideally suited to produce soft-burnt, high reactive lime and dolomitic lime because of the conditions created by the parallel flow of the stone and the combustion gases in the burning shaft. Additionally, the regenerative process provides the lowest heat consumption of all modern kilns available today. In parallel flow kilns the fuel is introduced at the upper end of the burning zone and the combustion gases travel parallel to the material. Fig. 1b shows a typical temperature profile where the green line represents the material, the blue line in the preheating zone the combustion air, the blue line in the cooling zone the cooling air and the red line the combustion gas and kiln off-gas. As the fuel is injected at the upper end of the burning zone where the material can absorb most of the heat released by the fuel the temperature in the burning zone is typically 950C in average. Because of this, parallel flow heating is the best solution for the production of softburnt, reactive lime and dolomitic lime. The second important characteristic of the PFR-Kiln is the regenerative preheating a part of the combustion air. In kilns with counter flow heating, the combustion air is preheated in the cooling zone by the

sensible heat contained in the calcined lime. The amount of preheating is limited, however, by the enthalpy of the lime. In the counter flow heating process there is a surplus of usable sensible heat contained in the off-gas that is not recovered prior to being exhausted. Some single shaft kiln designs therefore have incorporated recuperators in an effort to recover this waste heat, but such heat exchangers are susceptible to disruptions caused by dust contained in the hot off-gases.

Refractory Lining
The preheating and cooling zones of the kiln are lined with an abrasion resistant wear lining backed by insulating firebricks. The wear lining in the burning zone is made of high quality magnesite bricks with an insulating secondary lining. The working lining has a thickness of 250 mm and is backed by an insulating lining made from light fireclay bricks and calcium silicate boards. The arrangement of the brickwork is simple. There are no burner bridges or other devices in the shafts that would hinder the free flow of stone and calcined product as it passes through the kiln. In the case of rectangular shafts, standard brick shapes can be used to a large extent with a minimal number of special shapes required. This provides low cost lining and a simple inventory of spare bricks for repairs. Circular shafts are not as simple and require somewhat more special shapes. However, due to the static nature of the kiln and the constantly improving refractory materials, a long life with minimal maintenance can be expected. The lime kilns, whether they are vertical type or horizontal rotary type can be divided into 3 zones. They are:I. Pre-heating zone II. Burning zone III. Cooling zone In the first or pre-heating zone,the temperature is about 900C. The lower part of the hotter portion of this zone may have the temperature of about 950C. These refractories therefore need not have high refractoriness. The main resistance the refractories have to offer is to the abrasion by the stones. Therefore, the bricks should be hard and compact and perhaps have to be resistant to thermal shock as cold air may enter the kiln. Some lime kiln begins to react with the refractories at the hotter part,hence the refractories should be basic or high alumina in composition. These bricks do not have to encounter any slag attack or any fluctuations of temperature. The bricks should have a low porosity to stop the carbon dioxide from entering the pores. The burning zone which is the main zone where real calcinations of lime takes place Has a temperature between 1100C-1500C. Here the CaO becomes reactive and at that high temperature forms silicates or aluminates with the material of the bricks. Impurities in the limestone fuse and tend to form slag. The bricks should be aluminous or basic in character to resist this chemical attack. They should be hard,compact,well burned and should have a low pororsity to resist not only the chemical attack but also the mechanical abrasion caused by the falling stones. This abrasion is not so strong in the pre-heating zone but still it is present to a great extent. The joints should be tight. In the cooling zone the bricks should be resistant to spalling and abrasion.

Raw Materials: Q-Mag Kumas Binders Used: Dextrin Molasses Additives Used:

Process Flow Sheet

RAW MATERIALS

CRUSHING & GRINDING

STORAGE IN SILOS

BATCHING

MIXING PRESSING DRYING

FIRING (BURNT)

SORTING

INSPECTION

Crushing & Grinding:

The desirable fractions required for Green mix are as follows: Coarse: 1-4 mm. Fine: 0-1 mm Dust: < 0.09 mm. (obtained from air filter & Ball Mill) Following are the grinding equipment used for this purpose: A. Jaw Crusher B. Impeller Breaker C. Maxecon Mill D. Ball Mill

Granulometry of silo material:

(1-4) mm (0-1) mm Dust : : : (-4+1) mm -0.09 mm <0.09 mm 80.0% min. 10-26% 80.0% min.

Composition (wt %) of MAGNESIA-ZIRCONIA brick Weight percentage Component Standard Composition

38 39.5 20 2.5 2 1.5

Trial 1
38 39.5 20 2.5 2 2.5

Trial 2
38 39.5 20 2.5 2 1.5

Trial 3
38 39.5 20 2.5 2 1.5

Trial 4
38 39.5 20 2.5 2 1.5

QMAG (1-4) mm - do - (0-1) mm - do - dust K M Extra (1-4) mm - do - (0-1) mm - do - dust Monoclinic ZrO2 dust Partially Stabilized ZrO2 (0.5-1) mm Molasses Dextrin

Mixing:
Any type of mixer machine can be used for mixing the raw materials.

Mixing sequence:
COARESE RAW MATERIAL
2 min mixing

MOLASSES ADDED
5 min mixing

FINE AND DUST ADDED

10 min mixing

DEXTRIN ADDED
3 min mixing

Total Mixing Time 20 min

BATCHING AND MIXING

Pressing:
After mixing of raw materials, they are given required shape by pressing at nominal pressures. The materials were pressed in FSP (friction screw) at a pressure of 1000 ton. It is manually operated with hydraulic ejection. After pressing, the bricks are checked for, Green B.D, lamination, cracks, front back B.D. variation, segregation, corner breakage, etc. Green B.D. (gm/cc) :3.05 - 3.15

Drying:
Drying is very important to reduce moisture content of the brick to avoid crack. The pressed bricks are kept for floor drying for atleast 5 days.

Firing:
The dried bricks are then fired in HTK (High temperature kiln) between 16801700C. PRC (Pushing rate of car) :- 60 mins per 1/2 car with 240 min soaking

time.

Sorting:
After firing, the bricks are unloaded & transported to the sorting area where the visual inspection is done. Here the final product size (375*225*78/65) is measured. Defects usually present are warpage, physical defects like iron spot, melt holes, oversize etc. Defects like warpage and oversize can be removed by surface grinding. Good bricks are sorted out.

Photograph:

Trial-1

Trial-2

Trial-3

Trial-4

Inspection (Testing):
The properties that are checked in the R&D laboratory are: Apparent Porosity, Bulk Density, Apparent Specific Gravity, Cold Crushing Strength, Hot Modulus of Rupture & Cold Modulus Of Rupture Wet Chemical Analysis, Refractoriness Under Load, Reversible Thermal Expansion, Thermal Conductivity, Microstructure, Thermal Spalling Resistance, etc.

CHARACTERIZATION: Bulk Density: A useful property for refractories is bulk density, which defines the material present in a given volume. The bulk densities of the sintered samples were determined by Archimedes principle using the mass in air and the mass when immersed in water. For Dry Weight the sample is weighed in air. Then the sample is kept in a beaker filled with water and vacuumed for about 1 hour so that all the pores present in it are filled with distilled water and when no more air bubbles evolve the vacuum pump is turned off. Then measurements for suspended weight is done using apparatus in which sample is suspended in water. After taking suspended weight, soaked weight is taken by wiping off the excess water present on its surface using a wet cloth. Once the dry weight, soaked weight and suspended weight were measured, bulk density and apparent porosity were calculated by the formula: B.D. = Dry weight/ (Soaked weight Suspended weight) x Liquid density Apparent Porosity: The apparent porosity is a measure of the volume of the volume of the open pores into which a liquid can penetrate, as a percentage of the total volume. This is an important property in case where the refractory is in contact with molten charge and slag. A low apparent porosity is desirable since it would prevent easy penetration. A large number of small pores have an important influence on the refractory behavior. However, a measure of the true porosity, which also takes into account the volume of closed pores, gives a reasonable idea of the texture of the material as well as sintering characteristics. In fact, porosity, bulk density and apparent solid density have been termed as Vital Statistics of refractory shapes. It is measured from the soaked weight, suspended weight determined as explained earlier. It can be expressed as: A.P. (%) = [(Soaked weight Dry weight)/(soaked weight suspended weight)]100

Apparent Specific Gravity Cold crushing strength

Cold crushing strength of refractories is carried out by placing a suitable refractory specimen on a flat surface followed by application of a uniform load to it through a bearing block in a standard mechanical or hydraulic compression testing machine. The size of the bearing block has a plane bearing surface of size equal to or more thanthe size of the test specimen surface that it comes in contact with. CCS of the cubic samples has been measured with universal testing machine. The maximum load has been recorded from the load deflection curve for each sample. The load at which cracks appear in the refractory specimen represents the CCS of the specimen.60mm cube refractory specimens are used for this test. The stronger a material is the greater is its resistance to abrasion. CCS value of the specimen has been calculated from the formula CCS = load/ cross-sectional area Hot Modulus of Rupture & Cold Modulus of Rupture
The cold modulus of rupture of a refractory material indicates the flexural strength and its suitability for use in construction. It is indicative of the strength of the bonding system of the refractory product. Since the test is done at room temperature, it can only show its suitability and its use in construction. It provides no indication of how the refractory will behave at elevated temperatures. The hot modulus of rupture provides the indication of a refractory material about its flexural strength at elevated temperatures. Since refractories are used at elevated temperatures, the hot modulus of rupture is the true indicator of the suitability and performance of a refractory at high temperatures. Hence, in recent years, the hot modulus of rupture has been prescribed and required by users as the most important test criterion for selection and use of refractories. Strengths of refractories are usually reported in terms of the three-point bend strength or the flexural strength, frequently called the modulus of rupture (MOR). When the strength of refractories is measured by the three-point bend test and done so as a function of temperature, then the bend or flexural strength invariably exhibits a maximum that is associated with the softening of the silicate bonds. This strength maximum is usually not a very large one. It is usually observed between 6008C and 14008C, depending on the particular refractory type, its silicate content, and the specific chemistry of that silicate. At more elevated temperatures, above this strength maximum, the strength of the refractory rapidly decreases to only a few MPa and exhibits distinctly nonlinear load-displacement curves. Thus, although refractories are never very strong, they become even weaker at highly elevated temperatures, but they are noticeably less brittle as well. In addition, the loading rate dependence of strength at elevated temperatures becomes quite complicated.
The MOR test is a measure of the flexure (transverse ) breaking strength of the refractory at a very high temperature. The test specimen, again a standard 9 straight, is placed on two bearing with top & bottom(9x4.5)faces oriented horizontally. The specimen is broken at

mid-span in flexure at a standard loading rate. The modulus of rupture is calculated by following equation:MOR = 3pl / 2bd2 Where, MOR=modulus of rupture(N/mm2) p=load at rupture (N) l=span b/w support (mm) b=breadth/width of sample (mm) d=depth/thickness of sample (mm)

Wet Chemical Analysis Refractoriness Under Load Reversible Thermal Expansion Thermal Conductivity
Thermal conductivity is a measure of the refractory regarding its ability to conduct heat from the hot to the cold face when it is exposed to high temperatures. There are three different methods of determining thermal conductivity of refractory materials. ASTM C-210 is the standard method for determining thermal conductivity of refractories; ASTM C-202 is the standard method for determining thermal conductivity of refractory brick; and ASTM C-1113 is the standard method for determining thermal conductivity of refractories by hot wire. The thermal conductivity tests are particularly important for insulating refractories where the thermal gradients from the hot face to the cold face dictate the use of a refractory material for the specific uses.

Microstructure Thermal Spalling Resistance

This is measure of the refractory property when the refractory is exposed to alternate heating and cooling. It is an important property for a refractory material. Most high-temperature processes experience heating and cooling. Both refractory grains and the bonding system expand while being heated and contract during cooling. Having similar grains in the structure, the thermal shock resistance depends on the matrix bonding the grains. Thus, refractories having structures with built-in microcracks of defects show better thermal shock resistance than with rigid systems. In some refractories, the bonding system, by nature, possesses microstructural defects or cracks that provide better thermal shock resistance.