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CERAMICS Introduction Forming processes Applications

Introduction
Ceramics are non-metallic, inorganic materials. Most of the ceramics are compounds of metallic and non-metallic elements for which interatomic bonds are either Ionic Bonds or Covalent bonds. Some times more predominantly ionic and having covalent characteristics. The term Ceramics is derived from a Greek word Keramikos, which means Burnt Stuff, indicating its characteristics of manufacturing as these are normally heat treated to high temperatures called as Firing. Up until past sixty to seventy years the most of the important materials in this class were termed as the traditional Ceramics as those primary raw materials were Clays; products considered to be china, porcelain, bricks, tiles and in addition glasses and high temperature ceramics. OF late the significance of these materials were studied and year by year the term ceramics got a broader sense of meaning in engineering application.

Classification:
Ceramics are classified on the bases of its characteristics of which behaves in Engineering application . Ceramics are classified as follows.

Ceramics

Glass

Clay Products

Refractories

Abrassives

Cements and Advanced Ceramics

1. Glasses 2. Glass Ceramics

1. Structural Clay Products 2. White Wares

1. Fireclay 2. Silica 3. Basic 4. Special

Fig: Classification of Ceramics on the basis of Applications.

GLASSES:
The glasses are Familiar group of ceramics; containers, lenses etc. As they are mentioned to be a non-crystalline silicates containing other oxides, notably CaO, Na2O, K2O and Al2O3, which influences he properties of glasses. A typical soda lime Glass consists of approximately 70 wt. % SiO2, the balance being mainly Na2O(Soda), and CaO (lime). The composition of several common glass materials are contained in the following Table with the consideration of prime aspects of optical transparency and ease of manufacture. Glasses type Composition (wt.%) SiO2 Na2O >99.5 CaO Al2O3 B2O3 other High melting Temp. Very low coeff. Of Expansion (thermally shock resistant) Thermally shock and chemically resistant Laboratory ware Thermally shock chemically inert oven ware Low melting temperature, Easily worked also durable Easily drawn in to fibers-glasss-resin composites High density and high index of refraction- optical lenses Easily fabricated, strong, resists thermal shocksovenware Characteristics and Applications

Fused silica

96% silica (vycor)

96

Borosilicate (Pyrex) Container (soda lime)

81

3.5

2.5

13

74

16

4MgO

Fiber Glass

55

16

15

10

4MgO

Optical Flint

54

37PbO, 8K2O

Glass -ceramics

43.5

14

30

5.5

6.5TiO2 0.5 As2O3

Table: composition and characteristics of some of the common commercial glass types

Crystalline structure of Glasses: Commercial glasses are based on silica. They are made of the same SiO4 tetrahedra on which the crystalline silicates are based, but they are arranged in a non-crystalline, or amorphous, way. The difference is shown schematically in Fig. In the glass, the tetrahedra link at the corners to give a random (rather than a periodic) network. Pure silica forms a glass with a high softening temperature (about 1200C). Its great strength and stability, and its low thermal expansion, suit it for certain special applications, but it is hard to work with because its viscosity is high.

Glass Ceramics
Most of the inorganic glasses are made to transform from a non-crystalline state to one that is crystalline state by the proper high temperature heat treatment. This process is called crystallization, and the product is fine grained polycrystalline material which s often called a Glass-ceramic. The formation of these small glass ceramic grains is in a sense a phase transformation, which involves nucleation and growth stages. As a consequence the kinetics (i.e., the rate) of crystallization may be described using the same principles that were applied to phase transformation for the metal systems. Dependence of degree of transformation on the temperature and the time may be expressed using isothermal transformations and the continuous cooling transformation. CASE STUDY: Continuous cooling phase transformation of Lunar Glass:

Fig: The Continuous cooling transformation diagram for the Crystallization of Lunar Glass (35.5 wt.% SiO2, 14.3 wt.% TiO2, 3.7 wt.% Al2O3, 23.5 wt.% FeO, 11.6 wt.% MgO, 11.1 wt.% CaO, and 0.2wt% Na2O). Also superimposed on this plot are two cooling curves 1 & 2.

The continuous cooling transformation diagram for the crystallization of a lunar glass is presented as in figure the begin and end on transformation curves on this plot have the same general shapes is in iron carbon alloy of eutectoid composition. Also included are two continuous cooling curves are represented as 1 & 2.bthe cooling rate represented by the curve 2 is much greater than that for the curve 1. As also noted on this plot, for the continuous cooling path represented by the curve 1 crystallization begins at this intersection with the upper curve and progresses as the time increases and the temperature decreases continuously; upon crossing the lower curve as the original glass has crystallized. The other cooling curve just misses the nose of the crystallization start curve. It represents that minimum cooling rate less than this some Glasses ceramic is 100C/min. A nucleating agent (frequently Titanium Dioxide) is often used to the glasses to promote the crystallization. The presence of the nucleating agent shifts the begin and end transformation curves to short times.

PROPERTIES: Glass materials have been damaged to have the following characteristcs 1. High mechanical strength 2. Low coefficient of thermal expansion to avoid thermal shocks 3. Relatively high temperature capabilities 4. Good dielectric properties for electron packaging application 5. Good biological compatibility 6. good optical characteristics 7. good bondage resistance in fibres of glass in composites 8. good corrosion resistance 9. ease of sand-witching properties with high cohesion 10. good electrical insulating APPLICATION: some common application of glasses and glasses ceramics Some commercial names of glass manufacturing under common names as follows 1. Pyroceram 2. Corning wares 3. Cercor 4. Vision Applications: 1. Ovenware 2. Table ware 3. Oven windows 4. Rangetops 5. Electrical insulation 6. Substrates for printed circuits boards 7. Architectural cladding 8. For heat exchangers and regenerators.

CLAY PRODUCTS (VIREOUS PRODUCTS):


One of the most widely used ceramic raw materials is clay. This inexpensive ingredient, found naturally in great abundance, often is used as mined without any upgrading of quality. Another reason for its popularity lies in the ease with which clay form a plastic mass that is very amenable to shaping. The formed piece is dried to remove some of the moisture. After which it is fired at an elevated temperature to improve its mechanical strength. Potters have been respected members of society since ancient times. Their products have survived the ravages of time better than any other; the pottery of an era or civilization often gives the clearest picture of its state of development and its customs. Modern pottery, porcelain, tiles, and structural and refractory bricks are made by processes which, though automated, differ very little from those of 2000 years ago. All are made from clays, which are formed in the wet, plastic state and then dried and fired. After firing, they consist of crystalline phases (mostly silicates) held together by a glassy phase based, as always, on silica (SiO2). The glassy phase forms and melts when the clay is fired, and spreads around the surface of the

inert, but strong, crystalline phases, bonding them together. The important information is summarized in table

Most of the clay-based products fall within two broad classifications; the structural clay products and the white-wares. Structural clay products include building bricks, tiles, and sewer pipes. White wares ceramics become white after the high temperature firing. The white -wares are porcelain, pottery, table ware, china and plumbing fixtures (sanitary ware). In additions to clay, many of these products also contain nonplastic ingredient, which influence he the changes that take place during the drying and firing processes.

REFRACTORIES:
Another important class of ceramics that are utilized in large tonnages is the Refractories Ceramics. The salient properties of these materials include 1. Withstand high temperatures without decaying 2. Zero Decomposition of any change in environmental parameters 3. Very high melting points 4. Capacity to remain unreactive 5. Inert to many chemicals 6. Inert when exposed to many changes in environments 7. Thermal insulation POROSITY: porosity is the one microstructural variable that must be controlled to produce a suitable
refractory brick. Strength, load carrying capacity and resistance to attack by corrosive materials all increase with reduction of porosity. At the same time thermal insulation characteristics and resistance to thermal shock are diminished.

The performance of a refractory ceramic to a large degree, depends on its composition. On this basis there are several classifications but namely 1. Fireclay refractories 2. Silica refractories 3. Basic refractories 4. Special refractories Some five common refractories and its composition are given in following table Refractory types Al2O3 25-45 90-50 0.2 1.0 9.0 SiO2 70-50 10-45 96.3 3.0 5.0 Composition (wt. %) MgO 0-1 0-1 0.6 90.0 73.0 Cr2O3 Fe2O3 0-1 0-1 CaO 0-1 0-1 2.2 2.5 2.2 TiO2 1-2 1-4 Apparent porosity % 10-25 18-25 25 22 21

Fire clay High Alumina fireclay Silica Periclase Periclase Chrome ore

0.3 8.2

3.0 2.0

FIRE CLAY REFRACTORIES: Main ingredients silica and alumina mixtures Silica in the form of cristobalite about wt. % of 70 to 50 alumina in the form of Mullite about the wt.% 25 to 45 for this composition operating temperature is 1587C, for hich the formation is possible without liquid phase above 1587C liquid phase present will be depending upo the compostion Upgrading alumina content will increase the maximum service temperature allowing formation of small amount of liquid. Thermal Resistance is not only the criteria of these refractories but also the dimensional stabilities higher temperatures. Application Principally used in furnace constructions Furnace inside liners and bricks Thermal insulators where the high temperature exposures SILICA REFRACTORIES: It consists of small concentrations of alumina by the wt.% of 0.2-0.1%, and the silica by the wt.% of 95-97%. The oprating temperature of this eutectic composition of alumina is 7.7% is very near to silica extremity is 1600C. Application: High temperature & high load bearing capacity applications Roofing of steel and glass making furnaces Used as containments where the high resistant to Acidic Slags formations.

BASIC REFRACTORIES: Ingredients of these refractories are Perclase or Magnesia( MgO) They may also contain calcium, chromium, iron compounds Application: Basic refractories are highly used where the basic slag formations is more such as Steel making process in Open Hearth Furnaces. Some high heating chambers of sintering process. SPECIAL REFRACTORIES: These are yet other ceramics materials which include high purity of oxides which may contain little porosity. They may include Alumina, silica, magnesia, beryllia, zirconia, mullite and some carbide compounds Applications : Crucibles of steel industry Carbide inclusion may be used in electrical resistance heating furnaces.

ABRASIVES:
Abrasives are another form of ceramics which is having following characteristics high wear resistance, high hardness toughness to shock loads to take care of abrasive particles dont fracture high grindablity high temperature resistance due to frictional load. Refractorness is also essential Common abrasives are made of powder metallurgy process Common abrasives are diamond(natural & synthetic), silicon carbide, tungsten carbide,aluminium oxide or corundum and silica sand Abrasives are used inseveral forms as bonded to griding wheels, coated abrasives or as loose grains

CEMENTS:
Cements are also a type of ceramics which include lime or calcium substrates which upon affinity towards water, becomes paste then a gel form which formed is then settled for setting then become hard solid structure with strong bods by Cohesive forces, which is known property of ceramic. Some of common cement is ortland cement which include the major contents like tri calcium silicate or dicalcium silicate. Which is when hydrated then becomes a srong cementinous gell which then setting done upon which it becomes more solid.

ADVANCED CERAMICS:
Some of advanced ceramics are made for the unusual properties Dielectric property Piezoelectric ceramics High refractive indices Some applications are MEMS, Optical fibers, Ceramic Ball bearings, etc

CERAMICS FORMING PROCESSES


The surface area of fine powders is enormous. A cupful of alumina powder with a particle size of 1_m has a surface area of about 103 m2. If the surface energy of alumina is 1 Jm2, the surface energy of the cupful of powder is 1 kJ. This energy drives sintering. When the powder is packed together and heated to a temperature at which diffusion becomes very rapid (generally, to around 2/3Tm), the particles sinter, that is, they bond together to form small necks which then grow, reducing the surface area, and causing the powder to densify. Full density is not reached by this sort of sintering, but the residual porosity is in the form of small, rounded holes which have only a small effect on mechanical strength. Figure shows, at a microscopic level, what is going on. Atoms diffuse from the grain boundary which must form at each neck (since the particles which meet there have different orientations), and deposit in the pore, ending to fill it up. The atoms move by grain boundary diffusion (helped a little by lattice diffusion, which tends to be slower). The reduction in surface area drives the process, and the rate of diffusion controls its rate. This immediately tells us the two most important things we need to know about solid state sintering: Fine particles sinter much faster than coarse ones because the surface area (and thus the driving force) is higher, and because the diffusion distances are smaller. The rate of sintering varies with temperature in exactly the same way as the diffusion coefficient. Thus the rate of densification is given by:

Here is the density, a is the particle size, C and n are constants, Q is the activation energy for sintering, R is the gas constant and T is the absolute temperature. n is typically about 3.

The very specific character of ceramics high temperature stability makes conventional fabrication routes unsuitable for ceramic processing.

Inorganic glasses though make use of lower melting temperatures. Most other ceramic products are manufactured through powder processing Typical ceramic processing route: powder synthesisgreen component (casting, extrusion, compaction) sintering/firing

Figure: Flow route of powder synthesis

Processing ceramics Glasses


Most of them are silica-soda-lime variety. Raw materials are heated to an elevated temperature where melting occurs. Glass melt is processed by different route to form different products: Pressing to form shapes like plates table wares and dishes Blowingused to produce objects like jars, bottles, light bulbs. Drawingto form lengthier objects like tubes, rods, whiskers, etc.

Ceramic powder processing


Ceramic powder processing route: synthesis of powder, followed by fabrication of green product which is then consolidated to obtain the final product. Synthesis of powder involves crushing, grinding, separating impurities, blending different powders. Green component can be manufactured in different ways: tape casting, slip casting, extrusion, injection molding and cold-/hot-compaction. Green component is then fired/sintered to get final product.

Ceramic powder processing -Casting Slurry of ceramic powder is processed via casting routes Tape casting, and slip casting. Tape casting also known as doctor blade process used for making thin ceramic tapes. In this slurry of ceramic powder + binders + plasticizers is spread

over plastic substrate. Tape is then dried using hot air. Later tape is subjected to binder burn out and sintering. Slip castinghere aqueous slurry of ceramic powder is poured into plaster of Paris mold. As water begins to move out due to capillary action, thick mass builds along mold wall. It is possible to form solid piece by pouring more slurry. Ceramic powder processing Extrusion & Injection molding Extrusionviscous mixture of ceramic particles, binder and other additives is fed through an extruder where continuous shape of green ceramic is produced. Then the product is dried and sintered. Injection moldingit is similar to the process used for polymer processing. Mixture of ceramic powder, plasticizer, thermoplastic polymer, and additives is injected into die with use of a extruder. Then polymer is burnt off, before sintering rest of the ceramic shape. It is suitable for producing complex shapes. Extrusion and Injection molding are used to make ceramic tubes, bricks, and tiles. Ceramic powder processing Compaction Ceramic powder is compacted to form green shapes of sufficient strength to handle and to machine. Basis for compaction application of external pressure from all directions. In cold iso- static pressing (CIP), pressure is applied using oil/fluid, then green product is subjected to sintering. In hot iso static pressing (HIP), pressure is applied at high temperatures thus compaction and sintering occurs simultaneously. It is expensive but has certain advantages.

Figure: normal ceramics forming processes by powder metallurgy technique

Figure: Typical Cemented Carbide Forming Technique through powder metallurgy.

Figure: Composite Ceramic Liners of Steel Melting Hearth of Furnace

Figure:

Ceramic liners inside the steel furnace crucible

Figure: ceramic hexa bricks inside the furnace

Hot tuyeres liners Rubber composite ceramics arrangements for the hoppers. bricks

Blast Furnace roofing

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