ADVANCED CERAMIC OZELLKLER low density, high hardness, high mechanical strength, dimensional stability (specific stiffness), resistance

resistance to wear, resistance to corrosion (resistance to chemical attack), weathering resistance, high working temperature, low or high thermal conductivity, good electrical insulation and dielectric and ferroelectric properties

BAYER PROCESS 1)Digestion In order to remove the iron oxides and most of the silicon oxides present, the ore is first treated with sodium hydroxide. The digestion process takes advantage of the solubility of amphoteric aluminum oxides to form a solution of aluminate ions, whilst the basic iron oxides which form do not dissolve and are separated by filtration.

2)Clarification The alumina-bearing solution is separated from the insoluble impurities that were part of the original bauxite. With all solids removed, the pregnant liquor leaving the filter area, contains alumina in clear supersaturated solution. It is cooled by flash evaporation, the steam given off being used to heat spent liquor returning to digestion.

3)Precipitation The alumina is precipitated or crystallised from the solution as crystals of alumina trihydrate. The solution is mixed in tall vessels with recycled seed crystals. When completed the solid alumina hydrate is passed on to the next stage and the remaining liquor, which contains caustic soda and some alumina, goes back to the digesters. Dissolved alumina is recovered from the liquor by precipitation of crystals. Alumina precipitates as the trihydrate Al2O3 .3H2O in a reaction which is the reverse of the digestion of trihydrate 2NaAlO2 + 4H2O Al2O3.3H2O + 2 NaOH

4) Calcination In the final stage the alumina trihydrate is washed to remove any remaining caustic . It is heated to about 1050C in special calciners or kilns to drive off the water of crystallisation, leaving the alumina, which is a dry, white, sandy material. In the calcination process water is driven off to form alumina: 2Al(OH)3 ---> Al2O3 + 3H2O

CHEMICAL COMPOSITION IN ADVANCED CERAMICS SILICATE-CERAMICS

technical porcelain-The natural starting materials of technical porcelain are quartz, feldspar and kaolin. steatite -major component: soapstone, additives: clay and flux,

cordierite -These magnesium silicates occur during the sintering of soapstone with added clay, kaolin, corundium and mullite. mullite-ceramic OXIDE CERAMICS aluminium oxide-Al2O3 magnesium oxide-MgO zirconium oxide-ZrO2 aluminium titanate-Al2TiO5 or Al2O3.TiO2 piezo ceramic-lead zirconate to lead titanate NONOXIDE CERAMICS CARBIDES silicon carbide-SiC tungsten carbide-WC boron carbide-B4C titanium carbide-TiC NITRIDES silicon nitride-Si3N4 -3 Al2O3.2 SiO2

aluminium nitride-AlN boron nitride-BN SIALON Titanium nitride-TiN

Clay Minerals Mika llite Kaolen Montmorillonite

Two layers formation Kaolinite [ Al2(Si2O5)(OH)4 ] Dicite Nacrite Halloysite [Al2(Si2O5)(OH)4.2H2O] Prophillite [ Al2(Si2O5)(OH)2 ] Three layers formation Al2(Si4O10)(OH)2

Plasticity: When mixed with limited amounts of water, clays become plastic are able to be molded and formed easily. Example: Flour mixed with water =Easy form, Sand mixed with water=not plasticity Water have to add to clay to get plasticity, nothings give plasticity to clay except water.

Cohesion: This property proves the clay to keep its form when it dried. Since sand doesnt have this property, it changed its form when it dried.

Color: Since clays contain some mixed oxides in their body, they are naturally colored.

If the clay is pure, its color is white and is called as kaolin. Their color can be yellow, pink, reddish, blue-gray, green or black. Their colors give some information about their If the clay contains limonite, its color is dark. If it contains iron peroxide, its color is red. If it contains manganese oxide, its color is black. Organic materials change the clay color to violet.

However its color can change after firing due to change in color of oxides at high temperatures. Shrinkage: The dimensions of clay after forming with water reduce during drying . This volume shrinkage continues during the firing step of ceramic material processing. This shrinkage is related with plasticity of the clay.

PRODUCTION of SiC
H=132 kcal/mol

1.Acheson Process

The reaction within the furnace is complex but, in general, following the formula

A mixture of silica, carbon, sawdust and common salt (e.g. 50% silica, 40% coke, 7% sawdust and 3% common salt) is heated in an electric furnace. The heating is accomplished by a core of graphite and coke placed centrally in the furnace. The mixture of reactants is placed around this core. The mixture is then heated to reach a maximum o temperature of approximately 2700 C, after which the temperature is gradually lowered. Graphite electrode

SiO2 + 3 C SiC + 2 CO

Surrounded be silica and coke

Lely Process Lumps of SiC are packed between two concentric graphite tubes. The inner tube is thereafter withdrawn leaving a cylinder of SiC lumps inside the outer graphite tube called the crucible.

The crucible is closed with a graphite or SiC lid and placed inside an oven. The crucible is heated to approximately 2500o C in an atmosphere of argon at atmospheric pressure

The Modified Lely Process

SiC powder or lumps of SiC are placed inside a cylindrical graphite crucible. The crucible is closed with a graphite lid onto which a seed crystal is attached. The crucible is heated to approximately 2200o C normally in an argon atmosphere at a pressure below atmospheric pressure. A temperature gradient is applied over the length of the crucible in such a way that the SiC powder at the bottom of the crucible is at a higher temperature than the seed crystal.

In this way boules of SiC may be grown, which may be further processed into wafers. HSC FURNACE The feed to the furnace is a mixture of silica sand and petroleum coke, the same low-cost material used in the conventional Acheson furnace, which is used for almost the entire world production of silicon carbide. The HSC silicon carbide furnace product is removed from the bottom of the furnace. Feed and discharge are continuous. The fluidizing nitrogen enters through a gas distributor at the base of the furnace. The application of the fluidization method for the production of silicon carbide enables the charge- resistor feature (which has served so well in the Acheson furnace) to be updated and used in a fully continuous, steady state process. The furnace product is highly porous silicon carbide agglomerate with some residual carbon that is removed in subsequent processing. The HSC furnace operates at 18501900C, significantly

lower than the temperatures reached in the Acheson furnace. Because of the lower temperature and the manner

of the silicon carbide formation, the HSC product has a microcrystalline beta (cubic) structure silicon carbide with entirely different morphology and different properties than the more conventional alpha (hexagonal) crystal structure. The main product is a submicron silicon ceramic grade

sinterable powder for advanced ceramic applications.

Carboreduction of silica:

SiO2 + 3 C SiC + 2 CO As the same reaction formula as in the Acheson process, -SiC is synthesized by heating a mixture of fine particles of both silica and carbon in the inert atmosphere of a furnace. It is necessary, however the control the reaction temperature to keep it in a lower zone (1500 to 1700C) to avoid formation of the form of SiC

Silicification of Carbon

Si + C SiC Powdered silicon and a carbon source such as carbon black are made to react directly at a comparatively low temperature. This reaction is slightly exothermic so that it is self sustaining ones initiated and SiC can be formed by combustion synthesis. Typically, very fine Si powder and C black are mixed with a binder, pressed and inductively heated in graphite to 1200C. Once ignition occurs the reaction wavefront proceeds at about 0.1 cm/s down the sample mass and temperatures of 2250C can occure in the sample center. This energy-saving and rapid method enables stoichiometric -SiC powders of relatively uniform particle size (0.2-0.5 m) to be obtained. The powders are highly puresince, impurities are volatilized and oxide film reduced during SHS.

Gas-phase Reaction, Gas Phase Pyrolysis, Chemical Vapour Deposition: Gases such as SiCl4 or SiH4 are made to react with hydrocarbons, or gases such as CH3SiCl3 or (CH3)4Si are made to undergo pyrolysis, yielding a fine powder. The heat sources used include plasmas and lasers. SiCl4(g) + CH4(g) SiC(s) + 4HCl(g) SiH4(g) + C2H4(g) 2SiC(s) + 6H2(g) Vapour phase techniques produce pure, homogenous and fine powderes with a crystallite size in the 10-20 nm range although formed into large aggregates.

The high cost and volatility of the starting materials The difficulty of separeting the powders from the large quantitaties of exit gas limit their commericial exploitation. Silicon carbide is also produced on a small scale by the decomposition in an inert atmosphere of gaseous or volatile compounds of silicon and carbon, allowing the reaction products to deposit the carbide on a suitable hot substrate. An example of this process, known as chemical vapor deposition (CVD): CH3SiCI3(g) SiC(s) + 3HCl (g)

Raw Materials Selection Criteria A)PURITY Purity strongly influences high-temperature properties such as strength, stress rupture life, and oxidation resistance of ceramic materials. For instance, Ca severely decreases the creep resistance of Si3N4 hot-pressed with MgO as a densification (sintering) aid, but appears to have little effect on Si3N4 hot-pressed with Y203 as the densification aid. Impurities present as inclusions do not appreciably affect properties such as creep or oxidation, but do act as flaws that can concentrate stress and decrease component tensile strength. The effect on strength is dependent on the size of the inclusion compared to the grain size of the ceramic and on the relative thermal expansion and elastic properties of the matrix and inclusion. Tungsten carbide inclusions in Si3N4 have little effect on the strength; Fe and Si have a large effect. The effects of impurities are important for mechanical properties, but may be even more important for electrical, magnetic, and optical properties. Electrical, magnetic, and optical properties are usually carefully tailored for a specific application, often by closely controlled addition of a dopant. Slight variations in the concentration or distribution of the dopant severely alter the properties.

B) Particle Size and Reactivity Particle size distribution is important, depending on which consolidation or shaping technique is to be used. In most cases the objective of the consolidation step is to achieve maximum particle packing and uniformity, so that minimum shrinkage and retained porosity will result during densification. A single particle size does not produce good packing. Optimum packing for particles all the same size results in over 30% void space.

Adding particles of a size equivalent to the largest voids reduces the void content to 26%.

Adding a third, still smaller particle size can reduce the pore volume to 23%. Therefore, to achieve maximum particle packing, a range of particle sizes is required Low porosity and fine grain size are beneficial to achieve a ceramic with high strength.

However, there are many applications where strength is not the primary criterion. Refractories are a good example. Most refractories contain either large particles or high porosity as an important constituent in achieving the desired properties such as low thermal conductivity and high thermal shock resistance. Another important aspect of the starting powder is reactivity. The primary driving force for densification of a compacted powder at high temperature is the change in surface free energy. Very small particles with high surface area have high surface free energy and thus have a strong thermodynamic drive to decrease their surface area by bonding together.

Very small particles, approximately 1 m or less, can be compacted into a porous shape and sintered at a high temperature to near-theoretical density

Particle size distribution and reactivity are also important in determining the temperature and the time at temperature necessary to achieve sintering. Typically, the finer the powder and the greater its surface area, the lower are the temperature and time at temperature for densification. This can have an important effect on strength. Long times at temperature result in increased grain growth and lower strength. To optimize strength, a powder that can be densified quickly with minimal grain growth is desired.

Sintering Sintering commonly refers to processes involved in the heat treatment of powder compacts at elevated temperatures, usually at T > 0.5Tm [K], in the temperature range where diffusional mass transport is appreciable. Successful sintering usually results in a dense polycrystalline solid. Volume diffusion, whether along grain boundaries or through lattice dislocations, does result in shrinkage.

1st Stage (initial) Rearrangement Neck Formation 2 nd Stage (intermediate) Neck Growth Grain growth High shrinkage Pore phase continuous 3 rd Stage (final) Much grain growth Discontinuous pore phase Grain boundary pores eliminated

1. Traditional ceramic raw materials; Derived from common, naturally occurring raw materials such as clay minerals and quartz sand. Used for traditional ceramics such as wall and floor tiles, sanitary ware, white ware, refractories, bricks. 2. Advanced ceramic raw materials; Mostly derived from synthetic(not naturally occurred) powders obtained by special synthesis processes. High purity materials and precise methods of production must be employed to ensure that the desired properties of these advanced materials are achieved in the final product. Used for special purpose such as space shuttle tile, engine components, artificial bones and teeth, computers and other electronic components, and cutting tools, . SILICATE-CERAMICS technical porcelain-The natural starting materials of technical porcelain are quartz, and kaolin. steatite cordierite soapstone with mullite-ceramic OXIDE CERAMICS aluminium oxide-Al2O3 magnesium oxide-MgO zirconium oxide-ZrO2 aluminium titanate-Al2TiO5 or Al2O3.TiO2 piezo ceramic-lead zirconate to lead titanate NONOXIDE CERAMICS CARBIDES silicon carbide-SiC tungsten carbide-WC boron carbide-B4C titanium carbide-TiC NITRIDES silicon nitride-Si3N4 boron nitride-BN SIALON aluminium nitride-AlN Titanium nitride-TiN -major component: soapstone, additives: clay and flux, -These magnesium silicates occur during the sintering of added clay, kaolin, corundium and mullite. -3 Al2O3.2 SiO2

feldspar

Isostatic Pressing: Uniaxial pressing has some limitation which can be overcome by applying pressure from all directions instead of only one or two directions. This is referred to as isostatic pressing or cold isostatic pressing(CIP). Greather uniformity of compaction ncreased shape capability

Wet bag

Dry Bag

Tape Casting

Some applications such as substrates and packages for electronics and dielectrics for capacitors require thin sheets of ceramics. Tape casting has been developed to fabricate these thin sheets in large quantity and at low cost. It is similar to slip casting, except that the slip is spread onto a flat surface rather than being poured into a shaped mold. 1. Doctor Blade Process 2. Waterfall technique 3. Paper-casting process PLASTlC FORMING 1.Injection Molding 2.Extrusion

Extrusion: The extrusion process consists of forcing a highly viscous, doughlike plastic mixture of ceramic powder plus additives through a shaped die.

Injenction: The feed material for injection molding generally consists of a mixture of the ceramic powder with a thermoplastic polymer plus a plasticizer, wetting agent, and antifoam agent. The mixture is preheated in the "barrel" of the injection-molding machine to a temperature at which the polymer has a low-enough viscosity to allow flow if pressure is applied. A ram or plunger is pressed against the heated material in the barrel by either a hydraulic, pneumatic, or screw mechanism. The viscous material is forced through an orifice into a narrow passageway that leads to the shaped tool cavity. This helps compact the feed material and remove porosity. At the end of the passageway the strand of viscous material passes through another orifice into the tool cavity. The mixture is much more fluid at this point than an extrusion mix and could not form a selfsupporting shape. The strand piles on itself until the cavity is full and the material has knit or fused together under the pressure and temperature to produce a homogeneous part. The shaped tool is cooler than the injection-molding mix such that the mix becomes rigid in the tool cavity. The part can be removed from the tool as soon as it is rigid enough to handIe without deformation. Cycle times can be rapid providing the potential for injection molding to be a high-volume, low-cost process for fabrication of ceramics into complex shapes.