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Engineering materials

 The word ceramic comes from the Greek word


κεραμικός (keramikos) meaning pottery, which is said
to derive from the Indo-European word ker, meaning
heat.

 Non-metallic, Inorganic homogenous compounds

 Compounds between metallic and nonmetallic


elements (C, N, O, P, S)

 To be most frequently silicates, oxides, nitrides and


carbides.
Metals Vs ceramics
Metals Ceramics
 Ceramics is a multibillion dollar industry. worldwide sales
are about $100 billion per year; the U.S. market alone is over
$35 billion annually.

 The general distribution of industry sales is as follows:


 55% Glass

 17% Advanced ceramics

 10% Whiteware

 9% Porcelain enamel

 7% Refractories

 2% Structural clay
 Overall market distribution in the United States is as
follows:
 32% Flat glass

 18% Lighting

 17% Containers

 17% Fiber glass

 9% TV tubes, CRTs

 5% Consumer glassware

 1% Technical/laboratory

 1% Other
 Advanced ceramics form the second largest sector of the
industry.
 More than half of this sector is electrical and electronic
ceramics and ceramic packages:

 36% Capacitors/substrates/packages
 23% Other electrical/electronic ceramics
 13% Other
 12% Electrical porcelain
 8% Engineering ceramics
 8% Optical fibers
General properties
 The constituent atoms in a ceramic are held together by very strong
bonding forces which may be ionic, covalent or a mixture of the two.

 Most ceramics are brittle at room temperaturenot necessarily at elevated


temperatures.

 Their melting points are often very high, making them eminently suited for
use in energy-intensive systems such as industrial furnaces and gas turbines.
For instance, alumina primarily owes its importance as a furnace refractory
material to its melting point of 2050oC.
 The valence electrons are tied up in bonds, and are not free as they are
in metals. In metals it is the free electrons—the electron gas—that
determines many of their electrical and thermal properties.

 Diamond, which we classified as a ceramic has the highest thermal


conductivity of any known material. The conduction mechanism is due to
phonons, not electrons

 However, ion mobility becomes significant at temperatures above


500-6000C and they then become progressively more conductive. This
property can prove a problem in electric furnaces.
 Diamond is a good thermal conductor. But it is an excellent
electrical insulator. How?
Diamond crystal is a three-dimensional network of carbon atoms. All
carbon atoms in the network are strongly bonded by carbon-carbon
covalent bonds.
The diamond crystal has a highly symmetric cubic structure. The
carbon atoms in diamond are precisely aligned. Thus diamond is an
ideal crystal. Atoms in the crystal lattices in solids vibrate.

 These vibrations, called the atomic vibrations facilitate thermal


conduction (transport of heat) in solids. In an ideal crystal, the lattices
are so precisely aligned that they do not interact with each other.

Therefore an ideal crystal conducts better than a non-ideal crystal
resulting in ideal crystals having good thermal conductivity, which is a
measure of heat conduction. Diamond being an ideal crystal is thus a
good thermal conductor.
Mobile electrons facilitate electrical conduction - flow of current in
solids. There are no free mobile electrons in diamond crystal to
facilitate electrial conduction. Thus diamond is an excellent electrical
insulator.
 Answer
 In more simple terms, Diamond has a unique atomic structure. Each of
the Carbon atom's valence electrons is taken up in covalent bonding, so
each electron is localised. This means that no one electron is free to
pass an electric current through the Diamond - thus, Diamond cannot
carry an electrical current; there is nothing to pass the current through.
 Ceramics can also have high electrical conductivity:
 (1) the oxide ceramic, ReO3(Rhenium oxide ), has an
electrical conductivityat room temperature similar to that of Cu
 (2) the mixed oxide YBa2Cu3O7 is an HTSC; it has zero

resistivity below 92 K.
 Many ceramics are transparent because

they have a large Eg. Examples include sapphire watch


 The strength of ceramics under compressive stressing is excellent;
accordingly, designers of ceramic artefacts as different as arches in
buildings and metal cutting tool tips ensure that the forces during service
are essentially compressive.

 In contrast, the tensile strength of ceramics is not exceptional, sometimes


poor, largely because of the weakening effect of surface flaws. Thus, in
some cases, glazing with a thin vitreous layer can seal surface cracks and
improve the tensile strength.

 The strength of ceramics is commonly expressed as a modulus of rupture


(MoR) value, obtained from three-point bend tests, …. difficult to apply
with perfect uniaxiality; a slight misalignment of the machine grips will
induce unwanted bending stresses

 Ceramics are generally regarded as brittle, non-ductile materials, with little


or no plastic deformation of the microstructure either before or at fracture..
 The inherent lack of ductility implies that ceramics are likely to have a better
resistance to slow plastic deformation at very high temperatures (creep) than
metals

 The modulus of elasticity of ceramics can be exceptionally high. This


modulus expresses stiffness, or the amount of stress necessary to produce
unit elastic strain, and, like strength, is a primary design consideration.

 However, it is the combination of low density with this stiffness that makes
ceramics particularly attractive for structures in which weight reduction is a
prime consideration.

 In aircraft gas turbines, ceramic blades have long been an interesting


proposition because, apart from reducing the total mass that has to be
levitated, they are subject to lower centrifugal forces than metallic versions.
 It is therefore common practice to appraise competitor materials for
aircraft in terms of their specific moduli, in which the modulus of
elasticity is divided by density.

 Ceramics consist largely of elements of low atomic mass, hence their


bulk density is usually low, typically about 2000-4000 kg mm3.
Ceramics such as dense alumina accordingly tend to become pre-
eminent in listings of specific moduli

 The strong inter atomic bonding means that ceramics are hard as well
as strong. That is, they resist penetration by scratching or indentation
and are potentially suited for use as wear-resistant bearings and as
abrasive particles for metal removal
 Generally, impact conditions should be avoided. Interestingly, shape can
influence performance; thus, the curved edges of dinner plates are carefully
designed to maximize resistance to chipping.

 Although the strength and hardness of materials are often related in a


relatively simple manner, it is unwise to assume that a hard material,
whether metallic or ceramic, will necessarily prove to be wear-resistant.

 Grinding of ceramics is possible, albeit costly. Strength can be enhanced in


this way but great care is necessary as there is a risk that the machining
operation will damage, rather than improve, the critical surface texture.
 During the consolidation and densification of a 'green' powder compact in a
typical firing operation, sintering of the particles gradually reduces the
amount of pore space between contiguous grains.

 The final porosity, by volume, of the fired material ranges from 30% to
nearly zero.

 Together with grain size, it has a direct influence upon the modulus of
rupture; thus, bone china, because of its finer texture, is twice as strong as
fired earthenware.

 Pore spaces, particularly if interconnected, also lower the resistance of a


ceramic structure to penetration by a pervasive fluid such as molten slag.

 On the other hand, deliberate encouragement of porosity, say 25-30% by


volume, is used to lower the thermal conductivity of insulating refractories.
 Ceramics are often already in their highest state of oxidation. Not
surprisingly, they often exhibit low chemical reactivity when exposed to hot
oxidizing environments.

 Their refractoriness, or resistance to degradation and collapse during


service at high temperatures, stems from the strong interatomic bonding.

 However, operational temperatures are subject to sudden excursions and the


resulting steep gradients of temperature within the ceramic body can give
rise to stress imbalances.

 As the ceramic is essentially non-ductile, stresses are not relieved by plastic


deformation and cracking may occur in planes roughly perpendicular to the
temperature gradient, with portions of ceramic becoming detached from the
hottest face.
 The severity of this disintegration, known as spalling, depends mainly
upon thermal expansivity (a) and conductivity (k).

 Silica has a poor resistance to spalling whereas silicon nitride can


withstand being heated to a temperature of 1000oC and then quenched
in cold water
 Large refractory blocks cast from fused alumina are used to line
furnaces for melting glass. However, although alumina is a heat
resisting material with useful chemical stability, it is more sensitive to
thermal shock than silicon carbide and silicon nitride. A contributory
factor is its relatively high linear coefficient of thermal expansion (a).
 The exceptional insulating properties and range of alumina ceramics
have long been recognized in the electrical and electronics industries
(e.g. substrates for circuitry, sealed packaging for semiconductor
microcircuits).
 Unlike metals, there are no 'free' electrons available in the structure to
form a flow of current.
 The dielectric strength, which is a measure of the ability of a material
to withstand a gradient of electric potential without breakdown or
discharge, is very high. Even at temperatures approaching 1000oC,
when the atoms tend to become mobile and transport some electrical
charge, the resistivity is still significantly high.
 Electrical properties usually benefit when the purity of alumina is
improved.
 Many mass-produced engineering components take advantage of the
excellent compressive strength, hardness and wear resistance of alumina
 rotating seals in washing machines

 water pumps for automobile engines,

 machine jigs

 cutting tools

 Soil-penetrating coulters on agricultural equipment

 Shaft bearings in watches

 tape-recording machines

 guides for fast-moving fibres and yarns

 grinding abrasives

 Emery, the well-known abrasive, is an impure anhydrous form of


alumina which contains as much as 20% SiO2 + Fe2O3;
pretreatment is often unnecessary.)
 In glass-ceramics, a metastable glass of special composition is shaped while
in the viscous condition, then heat-treated in order to induce nucleation and
growth of a fine, completely crystalline structure.

 This glass-forming potential is an important aspect of ceramic science. The


property of transparency to light is normally associated with glasses, notably
with the varieties based upon silica. However, transparency is not confined to
glasses and single crystals. It is possible to produce some oxides, normally
regarded as opaque, in transparent, polycrystalline forms (e.g. hot-pressed
magnesia).
Properties of ceramics
Modulus
of Specific
Bulk density
elastic modulus
Material ity
(E/GN m-
2 (p/kg m-3) (E/p)
)
Alumina 345 3800 0.091
Glass (crown) 71 2600 0.027
Aluminium 71 2710 0.026
Steel (mild) 210 7860 0.027
Oak (with
12 650 0.019
grain)
Concrete 14 2400 0.006
Perspex 3 1190 0.003
 It is also not possible to define ceramics, or indeed any
class of material, in terms of specific properties.
 We cannot say “ceramics are brittle” because some can be
superplastically deformed and some metals can be more brittle: a
rubber hose or banana at 77 K shatters under a hammer.
 We cannot say “ceramics are insulators” unless we put a value on
the band gap (Eg) where a material is not a semiconductor.
 We cannot say “ceramics are poor conductors of heat” because
diamond has the highest thermal conductivity of any known
material.
 Traditionally, ceramics are moulded from silicate
minerals, such as clays, dried and fired at
temperatures of 1200-1800C to give a hard finish.
 Porcelain, brick, earthenware, etc
 Modern ceramics however, are often made by
processes that do not involve a kiln-firing step (e.g.
hot-pressing, reaction sintering, glass-
devitrification, etc.).
 High resistance to abrasion, excellent hot strength, chemical inertness,
high machining speeds (as tools) and dimensional stability

 Oxide Ceramics
 Oxidation resistant, chemically inert, electrically insulating,
generally low thermal conductivity, slightly complex
manufacturing and low cost for alumina, more complex
manufacturing and higher cost for zirconia.

 Non-Oxide Ceramics
 Low oxidation resistance, extreme hardness, chemically inert,
high thermal conductivity, and electrically conducting,
difficult energy dependent manufacturing and high cost.
Classification

 Pottery
 Heavy clay products(bricks, earthenware pipes, etc.)
 Refractories (firebricks,silica, alumina, basic, neutral), cement and
concrete, glasses and vitreous enamels

 Engineering(technical,fine) ceramics
 Very high strength

 Hardness

 Exceptional chemical stability

 Manufactured to very close dimensional tolerances


 1. Oxides — alumina, Al2O3 (spark plug insulators,grinding wheel grits),
magnesia, MgO (refractory linings of furnaces, crucibles), zirconia,ZrO2
(piston caps, refractory lining of glass tank furnaces), zirconia/alumina
(grinding media),spinels, M2+O.M3+O3 (ferrites, magnets,
transistors,recording tape), 'fused' silica glass (laboratory ware),
 2. Carbides — silicon carbide, SiC (chemical plant,crucibles, ceramic
armour), silicon nitride, Si3N4(spouts for molten aluminium, high-
temperature bearings), boron nitride, BN (crucibles, grinding wheels for
high-strength steels).
 3. Silicates —porcelain (electrical components), steatites (insulators),
mullite (refractories).
 4. Sialons — based on Si-Al-O-N and M-Si-Al-O-N where M = Li, Be, Mg,
Ca, Sc, Y, rare earths(tool inserts for high-speed cutting, extrusion
dies,turbine blades).
 5. Glass-ceramics — Pyroceram, Cercor, Pyrosil (recuperator discs for
heat exchangers).
1. Single crystals of appreciable size (e.g. ruby laser crystal)
2. Glass (non-crystalline) of appreciable size (e.g.sheets of 'float' glass)
3. Crystalline or glassy filaments (e.g. E-glass for glass-reinforced polymers,
single-crystal 'whiskers',silica glass in Space Shuttle tiles)
4. Polycrystalline aggregates bonded by a glassymatrix (e.g. porcelain
pottery, silica refractories,hot-pressed silicon nitride)
5. Glass-free polycrystalline aggregates (e.g. ultrapure,fine-grained, 'zero-
porosity' forms of alumina,magnesia and beryllia)
6. Polycrystalline aggregates produced by heat treating glasses of special
composition (e.g. glassceramics)
7. Composites (e.g. silicon carbide or carbon filaments in a matrix of glass or
glass-ceramic, magnesia graphite refractories, concrete).
Oxide ceramic processing

 High purity starting materials (powders) are prepared using mineral


processing techniques

 These powders are generally ground to an extremely fine or “ultimate”


crystal size to assist ceramic reactivity.

 Plasticisers and binders are blended with these powders to suit the
preferred method of forming (pressing, extrusion, slip casting, etc.) to
produce the “raw” material.

 Both high and low-pressure forming techniques are used. The raw
material is formed into the required “green” shape or precursor
(machined or turned to shape if required) and fired to high
temperatures in air or a slightly reducing atmosphere to produce a
dense product.
Non-Oxide Ceramics processing

 The production of non-oxide ceramics is usually a three


stage process involving:

 First the preparation of precursors or starting


powders,
 Secondly the mixing of these precursors to create the
desired compounds (Ti + 2B, Si + C, etc.)
 Thirdly the forming and sintering of the final
component.

 The formation of starting materials and firing for this group,


require carefully controlled furnace
 This group of materials generally requires quite high
temperatures to effect sintering.

 Similar to oxide ceramics, carefully controlled purities and


crystalline characteristics are needed to achieve the desired
final ceramic properties
Firing
 In general these materials are fired to temperatures well
above metals, and typically in the range of 1500°C to
2400°C and even higher

 . These temperatures require very specialised furnaces and


furnace linings to attain these high temperatures.

 Some materials require special gas environments such as


nitrogen or controlled furnace conditions such as vacuum.

 Others require extremely high pressures to achieve


densification (HIPs). Thus these furnaces are quite diverse
both in design and concept.
 The typical methods of heating in these furnaces are gases
(gas plus oxygen, gas plus heated air), resistance heating
(metallic, carbon and ceramic heaters) or inductance
heating (R.F., microwave).
Finishing

 Finishing techniques can include:


 laser,

 Water jet

 Diamond cutting

 Diamond grinding

 Drilling

 However if the ceramic is electrically conductive

techniques such as EDM (electrical discharge


machining) can be used.
Crystal Structures
 Because ceramics are composed of at least two elements, and often more, their
crystal structures are generally more complex than those for metals.

 The atomic bonding in these materials ranges from purely ionic to totally
covalent; many ceramics exhibit a combination of these two bonding types

 For those ceramic materials for which the atomic bonding is predominantly
ionic, the crystal structures may be thought of as being composed of
electrically charged ions instead of atoms.

 The metallic ions, or cations, are positively charged, because they have given
up their valence electrons to the nonmetallic ions, or anions, which are
negatively charged.
AX-Type Crystal Structures
 Some of the common ceramic materials are those
in which there are equal numbers of cations and
anions. These are often referred to as AX
compounds, where
A denotes the cation and X the anion.

 Some of the common ceramic materials that form


with this crystal structure are NaCl, MgO, MnS,
LiF, and FeO.
AmXp-Type Crystal
tructures
 If the charges on the cations and anions are not the same, a compound
can exist
 with the chemical formula AmXp , where m and/or p ≠ 1. An example
would be AX2 , for which a common crystal structure is found in
fluorite (CaF2).
 Other compounds that have this crystal structure include UO2 , PuO2 ,
and ThO2 .
AmBnXp-Type Crystal tructures

 It is also possible for ceramic compounds to have more than one type of
cation;for two types of cations (represented by A and B), their chemical
formula may be designated as AmBnXp .

 Barium titanate (BaTiO3), having both Ba 2+ and Ti 4+ cations, falls into this
classification. This material has a perovskite crystal structure
Structural ceramics
 Include silicon nitride (Si3N4), silicon carbide (SiC), zirconia (ZrO2),
boron carbide (B4C), and alumina (Al2O3).
 They are used in applications such as cutting tools, wear components,
heat exchangers, and engine parts.
 Their relevant properties are high hardness, low density, high-
temperature mechanical strength, creep resistance, corrosion resistance,
and chemical inertness.
 There are three key issues to solve in order to expand the use of
structural ceramics:
 Reducing cost of the final product

 Improving reliability

 Improving reproducibility
Electronic ceramics
 Include barium titanate (BaTiO3), zinc oxide (ZnO), lead
zirconate titanate [Pb(ZrxTi1−x)O3], aluminum nitride
(AlN), and HTSCs.
 They are used in applications as diverse as capacitor
dielectrics, varistors, microelectromechanical systems
(MEMS), substrates, and packages for integrated circuits.
 There are many challenges for the future:
 Integrating with existing semiconductor technology

 Improving processing

 Enhancing compatibility with other materials


Nanoceramics
 can be either well established or at an early stage
in their development. They are widely used in
cosmetic products such as sunscreens, and we
know they are critical in many applications of
catalysis, but their use in fuel cells, coatings, and
devices, for example, is often quite new. There are
three main challenges:
 Making them
 Integrating them into devices
 Ensuring that they do not have a negative impact on society
Composites
 Composites may use ceramics as the matrix phase and/or the
reinforcing phase. The purpose of a composite is to display a
combination of the preferred characteristics of each of the components.
 In CMCs one of the principal goals has been to increase fracture
toughness through reinforcement with whiskers or fibers. When
ceramics are the reinforcement phase in, for example, metal matrix
 composites the result is usually an increase in strength, enhanced creep
resistance, and greater wear resistance.
 Three issues must be solved:
 Reducing processing costs
 Developing compatible combinations of materials (e.g., matching coefficients
of thermal expansion)
 Understanding interfaces
Coatings
 Coatings and fi lms are generally used to modify the surface properties of a
material, for example, a bioactive coating deposited onto the surface of a
bioinert implant.
 They may also be used for economic reasons; we may want to apply a coating
of an expensive material to a lower cost substrate rather than make the
component entirely from the more expensive material.
 An example of this situation would be applying a diamond coating on a
cutting tool. In some cases we use films or coatings simply because the
material performs better in this form. An example is the transport properties of
thin films of HTSCs, which are improved over those of the material in bulk
form. Some issues need to be addressed:
 Understanding film deposition and growth
 Improving film/substrate adhesion
 Increasing reproducibility
Bioceramics
 used in the human body.
 The response of these materials varies from nearly inert to
bioactive toresorbable. Nearly inert bioceramics include
alumina (Al2O3) and zirconia (ZrO2). Bioactive ceramics
include hydroxyapatite and some special glass and glass–
ceramic formulations. Tricalcium phosphate is an example
of a resorbable bioceramic; it dissolves in the body.
 Three issues will determine future progress:
 Matching mechanical properties to human tissues
 Increasing reliability
 Improving processing methods
Production of ceramic
powders

 A fine powder is usually the starting material, or precursor;


advanced ceramics are mainly produced from powders with a
size range of 1-10 um

 The three principal routes for producing high-grade powders


 Solid-state reactions

 Solution

 Vaporization
Types Of Powders
Primary particles are the smallest clearly identifiable unit in the powder. Primary
particles may be crystalline or amorphous and cannot easily be broken down into
smaller units.

Agglomerates are clusters of bonded primary particles. Soft agglomerates are easily
broken up; hard agglomerates, because of the stronger interparticle bonds, are more
difficult to break up. Hard agglomerates should be avoided in ceramic powder
processing as much as possible.

Particles is a general term applied to both primary particles and agglomerates


 Granules are large agglomerates, usually 0.1–1 mm in diameter, that are formed
by the addition of a granulating agent (e.g., a polymer binder). The mixture is
tumbled, producing large, nearly spherical granules that flow freely and can be
used to fill complex molds and in automated processes.

 Flocs are clusters of particles in a liquid suspension held together


electrostatically.

 Colloids are very fine particles (they can be as small as 1 nm in diameter) held in
fluid suspension by Brownian motion. consequently, colloidal particles will
settle very slowly.

 Aggregates are coarse constituents, >1 mm, in a mixture. The important example
is the addition of gravel to cement to make concrete. In early concrete structures
MECHANICAL MILLING
Solid-state reaction
 Involves high temperatures.

 It is used in more refined forms for the production of other


carbides (TiC, WC), super-conductive oxides and silicon
nitride.

 An aggregate is produced and the necessary size reduction


(comminution) introduces the risk of contamination.

 Furthermore, as has long been known in mineral-dressing


industries, fine grinding is energy-intensive and costly
Solution-treatment method
 Solution-treatment method: The Bayer process - bauxite into
alumina

 Aluminium hydroxide is precipitated from a caustic solution and then


converted to alumina by heating.

 Unfortunately, this calcination has a sintering effect and fine grinding


of the resultant agglomerate is necessary.

 In the more recent spray drying and spray-roasting techniques, which


are widely used to produce oxide powders, sprayed droplets of
concentrated solutions of appropriate salts are rapidly heated by a
stream of hot gas. Again, there is a risk of agglomeration and grinding
is often necessary.
Sol-gel
The three key stages

1. Production of a colloidal suspension or solution (sol) (e.g.


concentrated solution of metallic salt in dilute acid)

2. Adjustment of pH, addition of a gelling agent, evaporation of liquid


to produce a gel

3. Carefully controlled calcination to produce fine particles of ceramic.


 Sol-gel methods are applicable to both ceramics and glasses and are
capable of producing filaments as well as powders.

 The hydroxide particles precipitated from the sol are spherical, uniform
in shape and sub-micron sized.

 Sintering does not drastically change these desirable characteristics.


 Although costs tend to be high and processing times are
lengthy, sol-gel methods offer an attractive way to produce
oxide powders, such as alumina, zirconia and titania, that will
flow, form and sinter readily and give a product with superior
properties.

 Individual ceramic particles are commonly brittle and non-


deformable; consequently, manufacturing routes usually avoid
plastic deformation and there is a greater inherent risk that
flaws will survive processing without becoming visible or
causing actual disintegration.
 It can produce powders with a high surface area, which allows sintering to
nearly full density at much lower temperatures than are normally required
when the particles have been made by other techniques.
 In most sol-gel processes the reactants are solutions of metal alkoxy
compounds.
 Alkoxides result from the reaction of metals (Me) with alcohols. The general
reaction is
 nROH + Me → (RO)nMe + (n/2)H2

 where R is an organic group.

 For ethanol, R is the ethoxy group C2H5


 Catalysts are often necessary to increase reaction rates. For example,
aluminum will react with isopropanol at 80°C in the presence of a
small amount of HgCl2. In this case the catalyst breaks down the
protective oxide layer that forms on the aluminum.

 A number of metal alkoxides are commercially available in high purity


form. To make metal oxide powders from these organometallic
precursors we start with a solution (a “sol”) of the metal alkoxide in
alcohol. (The alcohol is usually the same one that was used for
alkoxide formation.)
 Water is added to the alcohol solution.

 Two reactions then occur, which, using aluminum


isopropoxide as an example, may be written as follows:

 Reaction 1: Hydrolysis
 (C3H7O) 2–Al–OC3H7 + HOH →(C3H7O) 2–Al–OH +
C3H7OH
 Reaction 2: Condensation
 (C3H7O) 2–Al–OH + C3H7O–Al–(C3H7O)2 → (C3H7O)

2–Al–O–Me–(O C3H7) 2 + C3H7OH


 There are several variables in the sol-gel process:

 Rates of hydrolysis and condensation (relative differences in the rates can


be used to modify the microstructure of the powder)
 Type of alkoxide (mixing of the alkoxides in the solution is achieved at a
molecular level giving the powders a high degree of chemical homogeneity)
 Reaction temperature (affects the degree of polymerization of the gel)
 Amount of water added (affects the degree of polymerization of the gel)
 Solution pH (rates of hydrolysis and condensation can be increased by the
addition of acids or bases, respectively)
 Gelation times vary from seconds to several days.
 When the gel forms it may contain only about 5 vol% of the oxide.
 The dried gel is calcined to completely convert it to oxide. Powders
produced by the sol-gel method are amorphous. A crystallization step
is required to produce crystalline bodies, which is often performed
after sintering.
Powders By Precipitation
 To cause precipitation it is necessary to produce a supersaturated
solution

 At a supersaturation that exceeds the concentration threshold for


homogeneous nucleation, a large number of nuclei form suddenly.
Their formation lowers the solution concentration below the
concentration at which nucleation occurs, but enough excess solute
remains for the existing nuclei to grow.

 If the solution is kept uniform, growth of all the particles proceeds at


the same rate, producing powders with extremely uniform size
distribution.
 Precipitation of mixed oxides is possible.
 For example, in the fabrication of nickel ferrite (a
magnetic ceramic used for memories) a mixed aqueous
solution of iron and nickel sulfates is used.
 The solution is kept at about 80°C and precipitation occurs
when the pH is increased to around 11 with ammonium
hydroxide.
 A mixed hydroxide precipitates, which is washed to
remove the residual sulfate and dried to a powder with a
particle size between 50 nm and 1μm.
 It is possible to produce submicron particles of α-Si3N4 by reacting silicon
tetrachloride, a liquid at room temperature, and ammonia.

 The reaction involves the formation of silicon diimide [Si(NH)2] as an


intermediate phase.
 3Si(NH)2 → Si3N4 + 2NH3

 This process is used commercially by Ube Industries in Japan to produce


Si3N4.

 The particle morphology is controlled by the calcination time and temperature:


 Fine-grained equiaxed powders form at low temperatures
 Needle-like and coarse-grained hexagonal particles form at
temperatures >1500°C.
 Another example of a liquid-phase reaction used to produce precursors
for nonoxide powders involves reductive dechlorination of halide
solutions.

 An example is the reaction between silicon tetrachloride, carbon


tetrachloride, and sodium in heptane at ∼300°C:
 SiCl4 + CCl4 + 8Na → “SiC” + 8NaCl

 The amorphous precursor can be crysyallized by heating between 1400


and 1800°C in 5% H2/Ar. This process has also been used to produce
powders of TiB2 and B4C.
Vaporization
 Non oxides , nano sized powders
 Vapor phase processes are relatively expensive, but there are
several good reasons for using them to prepare powders,
particularly when we want
 High purity

 Discrete and nonaggregated particles

 Nanoparticles with narrow size distributions

 Versatility in producing powders of oxides and nonoxides


Shaping and forming
 1. Powder compaction: dry pressing, hot pressing, cold
isostatic pressing, etc.
 2. Casting: using a mold with the ceramic as, or containing,
a liquid or slurry
 BINDERS
 Poly (vinyl alcohol) (PVA) and poly (ethylene glycol)
(PEG) are the two of the most popular binders for drypressing
ceramics:
 PVA provides a high green strength.
 PEG provide a high green density.
 3. Plastic forming: extrusion, injection molding, etc.—
using pressure to shape the green ceramic
Alumina

 Amongst the oxide ceramics, alumina, Al2O3, is the most commonly used ceramic

 High hardness
 Wear resistance
 High modulus
 Inertness
 Refractoriness
 chemical resistance,
 smooth surface
 reasonable strength
 moderate thermal conductivity

 Low electrical conductivity insulators- spark plugs in automotive and aircraft engines
during World War II
 Alumina ceramics are the most widely used oxide-type ceramic, chiefly
because alumina is plentiful, relatively low-cost, and equal to or better than
most oxides in mechanical properties.
 Density can be varied over a wide range, as can purity—down to about 90%
alumina— to meet specific application requirements. Alumina ceramics are
the hardest, strongest, and stiffest of the oxides.
 They are also outstanding in electrical resistivity and dielectric strength, are
resistant to a wide variety of chemicals, and are unaffected by air, water
vapor, and sulfurous atmospheres.
 However, with a melting point of only 3700°F (2037°C), they are relatively
low in refractoriness, and at 2500°F (1371°C), retain only about 10% of
room-temperature strength.
 In addition to alumina’s wide use as electrical insulators and in chemical
Units Property/ Material Alumina

% Alumina 85 90 92 96 97 I 98 99.5

1000psi Tensile 18 26 28 30 30 30 32

1000psi Flexural 45 52 55 55 55 55 60

1000psi Compressive 250 265 280 300 300 300 330

g/cc Density 3.40 3.64 3.65 3.67 3.72 3.80 3.85

- Porosity 0 0 0 0 0 0 0

- Color White Black White White White White White

Moh's Scale Hardness 9 9 9 9 9 9 9

Thermal
g.cal/cm-sec-ºC 0.042 0.044 0.045 0.049 0.050 0.052 0.055
Conductivity

in/inºCx10-7 C.T.E. 67 70 71 75 76 77 78

ºC Max. Working Temp. 1350 1400 1500 1600 1650 1650 1700

D.C.Volts/Mil. @ 0.100"
Dielectric Strength 190 210 210 230 230 240 250
thick

Ohm/cm3x 1012 Volume Resistivity 0.02 0.5 1.0 2.0 3.1 3.2 3.5

- Dielectric Constant 7.6 8.1 8.6 9.0 9.4 9.6 9.7

- Dissipation Factor 0.0006 0.0004 0.0003 0.0003 0.0002 0.0001 0.0001

- Loss Factor 0.006 0.004 0.003 0.0028 0.0013 0.0011 0.0009

http://www.gbcmaterials.com/mat_alumina.htm
Properties Condition Units 960P 975P 998P 96S IP-95 IP-99

Mechanical

Al2O3 Minimum - % 96.0 97.6 99.8 96.0 99.5 95.0


Bulk Density 20°C g/cm3 3.67 3.72 3.96 3.77 3.65 3.85
Tensile Strength 20°C MPa 205 205 220 nd 160 240
Flexural (Bending) Strength 20°C MPa 375 375 410 295 300 350
Elastic Modulo 20°C GPa 300 355 375 nd 300 350
Hardness 20°C MPa 10 12 14 nd nd nd
Fracture Toughness 20°C MPa-m1/2 4-5 4-5 4-5 nd nd nd
Porosity 20°C % 0 0 0 0 0 0
Thermal
- °C 1600 1650 1700 na 1500 1700
Max. Working temperature
25-300°C 10-6 /°C 7.1 7.2 7.8 6.7 7.1 7.8
Coef. Thermal Expansion
25-1000°C 10-6 /°C 7.4 7.7 8.1 7.4 8.1 8.0
Thermal Conductivity 20°C W/m°K 24 26 28 28.6 20 25
Electrical
Dielectric Strength 2.5mm tk ac-kv/mm 9.2 9.2 10 30 20 20
Dielectric Constant 1 MHz - 9.0 9.4 9.7 9.8 9.0 9.2
20°C Ohm-cm >1014 >1014 >1014 >1014 >1014 >1015
Volume Resistivity 300°C Ohm-cm 109 109 1010 1012 nd nd
1000°C Ohm-cm 106 106 106 107 nd nd
Loss Tangent 1 MHz - 0.028 0.012 0.009 0.0015 0.0003 0.0002
Dissipation Factor 1 MHz - 0.0003 0.0002 0.0001 - - -
Electrical IP,DP,CIM,SC,EX TC IP
IP= Isopress DP= Dry press SC= Slip cast CIM= Ceramic injection molding TC= Tape cast EX= Extrusion
 Alumina-based refractories - slabs, shapes and bricks for furnace
construction- high melting point (20500C) and its heat resistance, or
refractoriness

 Aluminosilicate refractories (based upon clays) to be replaced by more


costly high-alumina materials and high-purity alumina.

 Interatomic bonding forces, partly ionic and partly covalent, are extremely
strong and the crystal structure of alumina is physically stable up to
temperatures of 1500-17000C.

 It is used for protective sheaths for temperature-measuring thermocouples


and for filters which remove foreign particles and oxide dross from fast-
moving streams of molten aluminium prior to casting.
 The constituent atoms in alumina, aluminium and oxygen, are of relatively
low mass and the correspondingly low density (3800 kg m-3)

 Alumina is brittle and should not be subjected to either impact blows or


excessive tensile stresses during service.

 The principal raw material for alumina production is bauxite Al2O(OH)4,


an abundant hydrated rock.

 In the Bayer process, prepared bauxitic ore is digested under pressure in a


hot aqueous solution of sodium hydroxide and then 'seeded' to induce
precipitation of Al(OH)3 crystals, usually referred to by the mineral term
'gibbsite'.
 The conditions of time, temperature, agitation, etc. during this stage
greatly influence the quality of the Bayer product.

 Gibbsite is chemically decomposed by heating (calcined) at a


temperature of 1200oC.

 Bayer calcine, which consists of a-alumina (>99% Al2O3), is graded


according to the nature and amount of impurities.

 Sodium oxide, Na2O, ranges up to 0.6% (affects sintering behaviour


and electrical resistance)

 The calcine consists of agglomerates of a-alumina crystallites which


can be varied in average size from 0.5 to 100 mm by careful selection
of calcining conditions.
 Bayer calcine is commonly used by manufacturers to produce high-
purity alumina components as well as numerous varieties of lower-
grade components containing 85-95% Al2O3.

 Additions of oxides such as SiO2, CaO and MgO which act as fluxes,
forming a fluid glassy phase between the grains of a-alumina during
sintering.

 The chosen grade of alumina+ additives, is ground in wet ball-mills to


a specified size range.

 Water is removed by spraying the aqueous suspension into a flow of


hot gas (spray-drying) and separating the alumina in a cyclone unit.
 The free-flowing powder can be shaped by a variety of methods
 Dry, isostatic-or hot-pressing

 Sip- or tape-casting

 Roll-forming

 Extrusion

 Injection moulding

 In some processes, binders are incorporated with the powder; for instance, a
thermoplastic can be hot-mixed with alumina powder to facilitate injection-
moulding and later burned off.

 In tape-casting, which produces thin substrates for microelectronic circuits,


alumina powder is suspended in an organic liquid.
 Densification by sintering :The fragile and porous 'green' shapes are finally
fired in kilns (continuous or intermittent).

 Firing is a costly process

 Faster rates of cooling after 'soaking‘ at the maximum temperature have


been found to give a finer, more desirable grain structure.

 For instance, roasted kaolinite can be leached in concentrated hydrochloric


or sulphuric acid, then precipitated as an aluminium salt which is calcined to
form alumina.

 Fluxing oxides are added to lower-grade aluminas in order to form an


intergranular phase(s).
 Although this fluid inter-granular material facilitates densification during
firing, its presence in the final product can have a detrimental effect upon
strength and resistance to chemical attack.

 In general, an increase in alumina content from 88% to 99.8% requires a


corresponding increase in firing temperature from 1450oC to 1750oC.

 The liquid phase sintering of alumina is a widely used process.

 It is more significant phenomenon than the solid state sintering of this


material .
 Many different additives are used to produce liquid phase with the aim
to promote liquid phase sintering and perhaps also the desired
microstructure development.

 The matter of our attention were additives from the CaO-MgO-SiO2 and
CaO-SiO2 system, which should assure coarse grain ceramics with high
dielectric strength

 Viscosity of the liquid phase is a very important characteristic, which


can influence densification in these stages.

 Viscosity depends on the temperature and also on the chemical


composition of the liquid phase.
 E. Kosti´c showed that for a good densification, the most suitable were
additives forming an equilibrium liquid phase at sintering temperature, but
not entering in the chemical reactions .

 The viscosity increase is caused by formation of the reaction products


between Al2O3 and liquid phase. This can be avoided if CaO/SiO2 ratio is
kept within a fixed range (0.47-1.23)

 'Harder' firing incurs heavier energy costs and has led to the development of
reactive alumina which has an extremely small particle size (1 um) and a
large specific surface.

 'Softer' firing temperatures became possible with this grade of alumina and
the need to debase the alumina with relatively large amounts of additives
was challenged.
 Investigations indicated an influence of additive composition on
microstructure development. An effect of addition of small amounts of
MgO on alumina microstructure is well known.

 A fine microstructure is caused by MgO precipitation on grain


boundaries. A slower grain growth and also appearance of large spinel
(MgAl2O4) grains is caused at larger MgO concentration (about
20wt.%) in the additive composition.
 Shrinkage is the most apparent physical change to take place when a
'green' ceramic compact is fired. The linear shrinkage of alumina is about
20% and dimensions may vary by up to +or-l%.

 Diamond machining is used when greater precision is needed but requires


care as it may damage the surface and introduce weakening flaws.

 Currently, there is great interest in vapour phase methods that enable


powders with a particle size as small as 10-20 nm to be produced (e.g.
oxides, carbides, nitrides, silicides, borides). The high-energy input
required for vaporization is provided by electric arcs, plasma jets or laser
beams.

 The powder is condensed within a carrier gas and then separated from the
gas stream by impingement filters or electrostatic precipitators. Sometimes,
in a chemical vapour deposition process (CVD), a thin film is condensed
directly upon a substrate.
 Alumina has low fracture toughness but it can be considerably improved by
making a composite in which fine particles of zirconia (ZrO2) are uniformly
dispersed .

 Zirconia dispersed in alumina (or other ceramic matrices) acts as a smart


material in that just as a crack starts propagating in alumina, it transforms
itself crystallographically and expands. The result is that a compressive or
crack closure stress is produced which slows down or stops the crack.

 The toughness of alumina can be easily increased by a factor of 2 and can be


even increased to as high as nearly four times with simultaneous increase in
strength by a factor of more than 2.
 A major concern in the processing of the Al2O3-ZrO2 composites is to
achieve a uniform dispersion of fine zirconia in Al2 O3 matrix.

 The conventional method of mixing the powders in a ball mill or other


device usually leads to formation of clusters (called "agglomerates") of
ZrO2 , which do not retain the tetragonal structure after processing and are
not effective in enhancing the mechanical properties.

 To achieve a uniform dispersion of ZrO2 in the Al2 O3, several techniques


can be used
 Hybrid sol-gel process is being used in which alumina powder +
zirconium alkoxide. Proper processing leads to a microstructure in
which nanosized zirconia particles are uniformly dispersed in
alumina. The size of zirconia particles can be increased by
controlling the sintering cycle. Excellent strength and toughness are
obtained
 Auminum (Al) / aluminum oxide (Al2 O3) and Al / aluminum
nitride (AlN) composites are being produced by oxidizing or
nitriding liquid aluminum melts.
 Used for ceramics, refractories, pigments, and catalyst carriers, and in
chemicals.

 Aluminum oxide crystals are normally hexagonal and are minute.

 For abrasives, the grain sizes are usually from 100 to 600 mesh.

 The larger grain sizes are made up of many crystals, unlike the
singlecrystal large grains of silicon carbide.
 Type A is alpha alumina with hexagonal crystals of particle size 11.8
in (0.3 m), specific gravity 4.0, and Mohs hardness 9.

 Type B is gamma alumina with cubic crystals of particle size less


than 3.94 in (0.1 m), specific gravity of 3.6, and hardness 8.

 Type A cuts faster, but Type B gives a finer finish.

 At high temperatures, gamma alumina transforms to the alpha crystal.

 The aluminum oxide most frequently used for refractories is beta


alumina in hexagonal crystals heat stabilized with sodium.

 The aluminum oxide abrasives in all forms are sold under trade names.
Alundum, of Saint-Gobain Industrial Ceramics, formerly Norton
Materials; Aloxite, of Carborundum Co; and Lionite, of General
Abrasives are aluminum oxides
 Alumina ceramics are finding increasing use in applications such as pump
seals, wear plates for industrial components, sand blast nozzles, extrusion
dies, etc.

 Alumina is also being widely used as a bio-inert material in various


orthopedic devices such as hip joint prosthesis, knee joint, etc
Silicon Carbide
 Silicon carbide is the most widely used nonoxide ceramic for heating
elements for high-temperature furnaces.

 SiC heating elements can be used up to 1500°C in air because of the


formation of a protective oxide layer.

 At temperatures in the range 1500–1600°C SiC decomposes:


 SiC(s) + O2(g) → SiO(g) + CO(g)

 Its major application is in abrasives because of its hardness (surpassed


only by diamond, cubic boron nitride, and boron carbide).
 It is more expensive than alumina and has lower toughness than silicon nit
ride, so it is not the optimum material for all corrosion or wear applications
.

 But where it can be used, it normally provides superior wear resistance an


d long life

 Like silicon nitride, silicon carbide is a family of materials each with its sp
ecial characteristics. Most of the silicon carbide materials have very high h
ardness (harder than alumina and silicon nitride) and thus have superior we
ar resistance.

 Most have unusually high thermal conductivity for a ceramic, low thermal
expansion compared to metals, and very high temperature capability.

 Some actually increase in strength at elevated temperature Relatively pure


SiC also has excellent resistance to corrosion in the presence of hot acids a
nd base
 Silicon carbide does not occur in nature and therefore must be
synthesized.

 It occurs in two crystalline forms: the cubic β phase, which is formed


in the range 1400–1800oC, and the hexagonal α phase, formed
at >2000oC.

 The world’s largest producer of SiC is China


 There are three main methods used to produce SiC heating elements:

 In situ reaction
 Reaction bonding
 Sintering
In situ reaction
 In the first method a carbon tube is heated to about 1900°C in a bed of
sand (SiO2) and coke (C).

 The tube may be directly resistance heated or heated indirectly by a


sacrificial tube of smaller diameter. Silicon monoxide is generated
from reaction and infiltrates the carbon tube transforming it to SiC.

 The SiC tube is then removed and the residual carbon is burnt out. The
tube has a porosity of about 30% and a large internal surface area.

 To prevent internal oxidation during use, the outer surfaces of the tube
are coated with a thin layer of a calcium aluminosilicate glass and are
then fired at about 1450°C.
Reaction bonding
 In the second method a mix of SiC and carbon powders and a polymer
binder is extruded to a rod. The “green” form is then brought in contact
with molten silicon.

 The liquid penetrates the pores reacting with the carbon to form silicon
carbide and bonding the grains together.

 The resulting ceramic has low porosity and, consequently, along


service life.
Sintering
 In the third method, SiC powder is mixed with a polymer binder and
extruded.

 The rod is then sintered in a carbon furnace at approximately 2300°C.

 To give the rod low-resistance terminations, the ends are dipped into
molten silicon, which is allowed to infiltrate along a predetermined
length.

 In all cases the ends of the elements are coated with aluminum to make
electrical contacts.

 The main disadvantage of silicon carbide heating elements is that they


are extremely brittle and must be handled carefully, especially when
being installed and wired.
Silicon Nitride
 It is strong, hard and has excellent resistance to wear,
thermal shock
 high strength over a broad temperature range, high
hardness,
 Moderate thermal conductivity,
 low coefficient of thermal expansion,
 Moderately high elastic modulus,
 Resistance to attack by many destructive fluids (molten
salts, slags, aluminium, lead, tin, zinc, etc.).
 Unusually high fracture toughness for a ceramic
 Although extensive testing has been conducted, silicon nitride has not yet
reached a significant level of production for turbine engines.

 However, silicon nitride ceramics have reached large-scale production for


 Cutting tools,

 Bearings,

 Turbocharger rotors,

 Diesel cam follower rollers, and diesel prechambers


 Moderate levels of production for other applications such a
s
 Thermocouple protection tubes,

 Grit-blast nozzle liners,

 Wire-forming rolls and guides,

 Paper making dewatering foil segments,

 Check valve balls,

 Down hole oil well parts,

 Aluminum die-casting tooling,

 and a variety of custom wear parts


 A more recent application for silicon nitride that is having major
impact on many industries is bearings

 Silicon nitride was first demonstrated as a superior bearing


material

 Although silicon nitride bearings are still 2–5 times more expensive than the
best bearing steel, their superior performance and life
have resulted in rapid escalation in their use.
 One of the most important applications of silicon nitride bearings is
tool spindles Because of their light weight (60% lighter than steel),
silicon nitride bearings can be operated at much higher speed than metal beari
ngs without generating a critical level of centrifugal stress.
 Because of their low thermal expansion (one-fifth that of steel) and high elastic
modulus, the silicon nitride bearings can operate to much closer tolerances t
han metal bearings, which enables machines
with higher precision and lower vibration.

 Because of their high hardness and smoother surface, the silicon nitride bearin
gs run smoother and wear at about one-seventh the rate
of the best metal bearings.
 All of these factors together result in 3–10 times the life of metal
bearings, up to 80% higher speed capability, about 80% lower
friction, higher operating temperature, and 15–20% reduction in
energy consumption.
 In addition to cutting tool inserts, bearings and check
valves, silicon nitride is being vigorously evaluated for

 Diesel and auto engine valves,


 Valve guides,
 Stator vanes and rotors for turbines,
 Wear parts,
 Forging dies for aluminum
Reaction-bonded silicon nitride
(RBSN)

 The properties available from existing materials were variable and


specific service requirements, such as good resistance to thermal shock and
attack by molten metal and/or slag, could not be met. The development of
silicon nitride minimized these problems

 Cutting tools, bearings, heat engines, foundry equipment, furnace parts,


welding jigs, metal-working dies, etc.

 Silicon nitride exists in two crystalline forms (a, b): both belong to the
hexagonal system.

 Bonding is predominantly covalent.


 Silicon nitride was first produced by an innovative form of pressureless
sintering.

 First, a fragile pre-form of silicon powder (mainly a-Si3N4) is prepared,


using one of a wide variety of forming methods

 Die-pressing
 Isostatic-pressing
 Slip-casting
 Flame-spraying
 Polymer-assisted injection-moulding
 Extrusion
 In the first stage of a reaction-bonding process, this pre-form is heated in a
nitrogen atmosphere and the following chemical reaction takes place

 3Si + 2N2 = Si3N4

 A reticular network of reaction product forms throughout the mass, bonding


the particles together without liquefaction.

 Single crystal 'whiskers' of a-silicon nitride also nucleate and grow into pore
space.

 Reaction is strongly exothermic and close temperature control is necessary in


order to prevent degradation of the silicon.

 The resultant nitrided compact is strong enough to withstand conventional


machining.
 In the second and final stage of nitridation, the component is heated in
nitrogen at a temperature of 14000C, forming more silicon nitride in situ and
producing a slight additional change in dimensions of less than 1%. (Alumina
articles can change by nearly 10% during firing.)

 The final microstructure consists of a-Si3N4 (60-90%), b-Si3N4


(10-40%), unreacted silicon and porosity (15-30%)

 As with most ceramics, firing is the most costly stage of production.

 The final product, reaction-bonded silicon nitride (RBSN),


has a bulk density of 2400-2600 kg m-3.
Hot-pressed forms of silicon nitride
(HPSN, HIPSN)

 Silicon nitride powder, which cannot be


consolidated by solid-state sintering alone, is
mixed with one or more fluxing oxides (magnesia,
yttria, alumina) and compressed at a pressure of
23 MN m-2 within radio-frequency induction-
heated graphite dies at temperatures up to 18500C
for about 1 h.
 The thin film of silica that is usually present on
silicon nitride particles combines with the
additive(s) and forms a molten phase.
 Densification and mass transport then take place
 As this intergranular phase cools, it forms a siliceous glass which can be
encouraged to crystallize (devitrify) by slow cooling or by separate heat-
treatment.

 Produces a limited amount of second phase (up to 3% v/v) as a means of


bonding the refractory particles; however, this bonding phase has different
properties to silicon nitride and can have a weakening effect, particularly if
service temperatures are high.

 Thus, with 3-5% added magnesia, at temperatures below the softening


point of the residual glassy phase, say 1000oC, silicon nitride behaves as a
brittle and stiff material; at higher temperatures, there is a fairly abrupt loss
in strength, as expressed by modulus of rupture (MoR) values, and slow
deformation under stress (creep) becomes evident.

 For these reasons, controlled modification of the structure of the inter-


granular residual phase is of particular scientific concern
 Yttria- an alternative densifier to magnesia. Its
general effect is to raise the softening point of
intergranular phase significantly.
 More specifically, it yields crystalline
oxynitrides (e.g. Y2Si3O3N4) which dissolve
impurities (e.g. CaO) and form refractory solid
solutions ('mixed crystals').
 Unfortunately, at high temperatures, yttria-
containing silicon nitride has a tendency to
oxidize in a catastrophic and disruptive manner.
 Although the use of dies places a restriction upon
component shape, hot-pressing increases the bulk
density and improves strength and corrosion
resistance.
 The combination of strength and a low
 In a later phase of development, other
researchers used hot isostatic-pressing
(HIPing) to increase density further and to
produce much more consistent properties.
 Silicon nitride powder, again used as the
starting material, together with a relatively
small amount of the oxide additive(s) that
promote liquid-phase sintering, is formed
into a compact.
 This compact is encapsulated in glass (silica
or borosilicate). The capsule is evacuated at
 Finally, the glass envelope is removed from the isotropic HIPSN
component by sand-blasting.

 Like HPSN, its microstructure consists of b-Si3N4 (>90%) and a small


amount of intergranular residue (mainly siliceous glass).

 Production routes involving deformation at very high temperatures and


pressures, as used for HPSN and HIPSN, bring about a desirable
closure of pores but inevitably cause
a very substantial amount of shrinkage (20-30%).

 (In contrast to HPSN and HIPSN, RBSN undergoes negligible


shrinkage during sintering at the lower process temperature of 14000C
and accordingly contains much weakening porosity, say 15-30% v/v.)
 By the early 1970s, considerable progress had been made in producing
silicon nitride by reaction-bonding,hot-pressing and other routes.

 However, by then it had become evident that further significant


improvements in the quality and capabilities of silicon nitride were
unlikely. At this juncture, attention shifted to the sialons.
Sialons
 As alloys of Si3N4, sialons exist in three basic forms.

 Each form is isostructural with one of the two common forms of Si3N4,
beta (β) and alpha (α) and with silicon oxynitride.

 In the case of sialon, there is substitution for Si by Al with corresponding


atomic replacement of N by O, to satisfy valency requirements. The
resulting 'solution' (sialon) has superior properties to the original pure
solvent (silicon nitride).

 The fundamental structural unit of Si3N4 is the SiN4 tetrahedron, which is


analogous to the SiO4 structural units in silicates.

 The tetrahedra are linked together into a rigid three dimensional framework
by sharing corners. The Si-N bonds are short and they are very strong. This
strong, rigid, compact structure is responsible for many of the important
properties of Si3N4.
β-Sialon

 β-sialon is based upon the atomic arrangement existing in β-Si3N4

 In this material, Si is substituted by Al with corresponding replacement


of N by O. In this way up to two-thirds of the silicon in β-Si3N4 can
be replaced by Al without causing a change in structure.

 The chemical replacement is one of changing Si-N bonds for Al-O


bonds. The bond lengths are about the same for the two cases but the
Al-O bond strength is significantly higher than that of Si-N.

 In sialon the Al is co-ordinated as AlO4 and not as AlO6 as in


alumina (Al2O3). Therefore, in β-sialons the Al-O bond strength is
50% stronger than in Al2O3. Thus sialons intrinsically have better
properties than both Si3N4 and Al2O3.
 b-sialon is produced using yttria (Y2O3) as a sintering aid and marketed
under the trade name Syalon 101.

 During sintering at temperatures above 1400°C, the oxides react to form an


yttrium-silicon-aluminium-oxynitride liquid which is neccessary for
ensification. This then forms an intergranular glass on cooling.

 Syalon 101 is a fully dense ceramic characterised by high strength and


thoughness.
 As a solid solution, the vapour pressure of β-sialon is lower than that of
Si3N4 and as a result the sialon will form more liquid at a lower
temperature with Y2O3. Sialon is, thus more easily densified using
normal sintering techniques.

 Furthermore, it should be noted that the lower vapour pressure of sialon


reduces decomposition at high temperatures so that the sialon is
thermodynamically more stable than Si3N4. The second form of Si3N4
with which sialon is isostructural is α-Si3N4.

 The stacking structure in α-Si3N4 is different from β-Si3N4 in that the


long 'channels' which run through the β structure are blocked at intervals.
This gives rise to a series of intersticial holes.

 In α-sialons, Si in the tetrahedral structure is replaced by Al with limited


substitution of N by O. Valency requirements are satisfied by modifying
cations occupying the intersticial holes. In this way cations of yttrium (Y),
calcium (Ca), lithium (Li) and neodymium (Nd) for example can be
incorporated into the structure.
α-Sialon

 Syalon 050. α-sialons are intrinsically hard materials.

 Hardness can be simplistically related to bond energy density, which


for α-sialons is high, giving extreme hardness.

 In addition, during sintering and subsequent heat treatment of α-


sialons such as Syalon 050, the intergranular phase is taken up into the
structure resulting in a dense, hard ceramic which is almost free of a
grain boundary phase.

 This results in the materials properties being retained at upto 1400°C,


with improved oxidation resistance.
O-Sialon
 The final form of sialon, O-sialon, is iso-structural with silicon
oxynitride (Si2N2O). The structure of Si2N2O consists of layers of
Si3N4 rings joined by Si-O-Si bonds.

 In O-sialon, Al and O replace some Si and N atoms.

 They have good refractory properties, they are low in strength and
toughness and therefore are not bracketed as advanced ceramics.

 They are effectively a refractory with no benefits over β-sialon for


example, other than cost, although the much superior properties of α-
and β-sialon provide much greater service life, thus offsetting any
supposed cost benefits.
O'-SIALON
 O’-Sialon is a unique class of non-oxide ceramic which incorporates
grains of silicon carbide held by a matrix of O’-Sialon.

 This results in a product that exhibits high strength at both room


temperature and working temperature.

 It also gives longer life meaning less change-overs and consequently


less down time. No expensive and time consuming coatings are
required because O’-Sialon is non-wetting to molten aluminium and its
alloys.
 ADVANTAGES:
 Excellent oxidation resistance
 Non-wetting to aluminium and its
 alloys
 Good thermal shock
 Good abrasion resistance
 Chemically inert
 APPLICATIONS:
 Dosing tubes
 Riser tubes
 Heater protection tubes
 Thermocouple Protection tubes
 AVAILABILITY:
 Cast, isostatically pressed,
 extruded and hydraulically pressed
 shapes
 b-sialon ceramics have lower thermal conductivities than b-Si3N4 ceramics
 the substitution of aluminium and oxygen into silicon and nitrogen sites in the
t3-Si~N4 structure decreases the'thermal conductivity.
 New types of solid solution which have the a-Si3N4 structure have been
developed recently.
 The general formula for the solid solution, a-sialon, is Mx(Si, A1)I2(O, N)16
where M = Li, Mg, Ca, Y or the lanthanide metals except lanthanum and
cerium
 The metals dissolved into interstitial sites and stabilized the structure . The a-
sialon ceramics had comparable bending strengths and were promising for
engineering applications
 There was no report on thermal conductivity of a-sialon ceramics.
 The starting powders for the fabrication of a-sialon ceramics are Si3N4,
A1N and MgO, or CaCO3 or Y 203
 The powders were mixed in restricted ratios The ratios were x = 0.8 for Mg-
a-sialon and Ca-a-sialon and x = 0.4 in Y-a-sialon in the general formula.
 The mixture was hot-pressed in a graphite die, with an inside diameter of 10
ram, under a pressure of 14.7 MPa at 1973 K for 1 h. The mixture was
reacted and sintered simultaneously to form a-sialon ceramics.
 It was shown that most of the added calcium and yttrium were
dissolved into a-sialon grains during heating .
 A crystalline impurity in the materials was a small amount of a-quartz.
There were unreacted b-Si3N4 and A1N in the sintered a-sialon
containing magnesium.
 The amount of dissolved magnesium in the grains is supposed to be
smaller than for calcium or yttrium
Zirconia
Structural properties
 Zirconium is a polycrystalline ceramic without any glass component. The
transformation toughened Zirconia has unique properties such as high
fracture toughness and strength.
 It is a polymorph that occurs in three forms,
 Monoclinic (M),
 Cubic (C)
 Tetragonal (T).
 Pure Zirconia at room temperature is monoclinic and stable till 1170 °C.
Above this temperature it transforms itself into tetragonal and then further
into cubic phase at 2370 °C.
 During cooling, a T-M transformation takes place at the temperature range
of about 100 °C below 1070 °C. The phase transformation, which takes
place during cooling, is associated with volume expansion of
approximately 3–4%. This means that components made of pure zirconium
oxide would burst due to volume increase of grains and tension.
 Magnesia Partially Stabilized Zirconia(Mg-PSZ) and Yttria Tetragonal
Zirconia Polycrystal, Y-TZP structural ceramic zirconia materials provide
 excellent erosion

 corrosion

 abrasion resistance along with temperature resistance

 fracture toughness and strength.

 These ceramic alloy components are used in extreme service applications


that take advantage of their superior wear and corrosion resistance.
 Numerous applications for these materials are in the chemical and
petrochemical industry providing economic payback in the way of reduced
maintenance and down time
 Valve components, pump liners, plugs, sleeves, pistons, precision ceramic
balls, spools, press tooling, dental blanks, extrusion tooling and wear plates.
Other specialty products include a range of porous ceramic filters, diffusers
and adsorbent filter/drier cores for refrigeration applications, dispersion parts,
vacuum chucks, inkpads and gas probes.
 Zirconia is also becoming the material of choice for components in healthcare and
dental applications.
 Pure Zirconia (Zirconium dioxide) has a high melting point (2,700° C) and a low
thermal conductivity.
 Its polymorphism, however, restricts its widespread use in ceramic industry. During a
heating process, zirconia will undergo a phase transformation process. The change in
volume associated with this transformation makes the usage of pure zirconia in many
applications impossible.
 Addition of some oxides, such as CaO, MgO, and Y2O3, into the zirconia structure in a
certain degree results in a solid solution, which is a cubic form and has no phase
transformation during heating and cooling. This solid solution material is termed as
stabilized zirconia, a valuable refractory.

 Stabilized zirconia is used as a grinding media and engineering ceramics due to its
increased hardness and high thermal shock resistivity.

 Stabilized zirconia is also used in applications such as oxygen sensors and solid oxide
fuel cells due to its high oxygen ion conductivity.
Unstabilized (Pure) Zirconia

 Pure zirconia is an important constituent of ceramic colors and 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 1,000° C, which involves a large
volume change and creates cracks within its structures. Due to the
inversion, pure zirconia has low thermal shock resistivity.
Partially Stabilized Zirconia (PSZ)
 Partially stabilized Zirconia is a mixture of zirconia polymorphs, because
insufficient cubic phase-forming oxide (Stabilizer) are added and a cubic
plus metastable tetragonal ZrO2 mixture is obtained.
 A smaller addition of stabilizer to the pure zirconia will bring its structure
into a tetragonal phase at a temperature higher than 1,000 ° C, 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).
 Usually such PSZ consists of larger than 8 mol% (2.77 wt%) of MgO, 8
mol% (3.81 wt%) of CaO, or 3-4 mol% (5.4-7.1 wt%) of Y2O3.
 PSZ is a transformation-toughened material.
 Microcrack and induced stress may be two explanations for the toughening
in partially stabilized zirconia. 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 is. This deference
creates microcracks that dissipate the energy of propagating cracks.

 The induced stress explanation depends upon the tetragonal-to-


monoclinic transformation, once the application temperature over pass
the transformation temperature at about 1000° C.

 The pure zirconia particles in PSZ can metastabily retain the high-
temperature tetragonal phase.

 The cubic matrix provides a compressive force that maintains the


tetragonal phase. 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 2,200 °C (4000° F) in neutral or
oxidizing atmospheres.
 Above 1,650°C (3000 ° F), 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.
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.
Preparation of Pure Zirconia
Powders
 Zirconia is usually produced from the zircon, ZrSiO4. To
produce zirconia from zircon, the first step is to convert
zircon to zirconyl chloride
 There are two methods are used to make zirconia from the zirconyl
chloride:
 Thermal decomposition
 Precipitation.
 A. Once the zircornyl chloride (ZrOCl2 8H2O) is heated to 200° C, it
starts dehydration and becomes dehydrated ZrOCl2.On next step,
ZrOCl2 decomposes into chlorine gas and becomes zirconia at a
much higher temperature. Zirconia lumps obtained from the
calcination then undergo a size reduction process, such as ball
milling, into the particle size range needed, usually up to-325 mesh.
 This method is associates with low production cost. However, it is
not easy to produce zirconia powders with high purity and fine
particle size by the method.
 B. Precipitation method, on other hand, uses chemical reactions to
obtain the zirconia hydroxides as an intermediate
 By this method, the grain size, particle shape, agglomerate size, and
specific surface area can be modified within certain degree by
controlling the precipitation and calcination conditions.

 Furthermore, its purity is also easier to be controlled. For the


applications of zirconia in the slip casting, tape casting, mold injection
and so forth, particle size and specific surface are important
characteristics.

 Well-controlled precipitated zirconia powder can be fairly uniform and


fine. Particle size can be made less than 1 µm.
Preparation of Stabilized
Zirconia Powders
 In order to achieve the requirement of the presence of cubic and
tetragonal phases in their microstructure, stabilizers (magnesia, calcia,
or yttria) must to be introduced into pure zirconia powders prior to
sintering.
 Stabilized zirconia can be formed during a process called in-situ
stabilizing. Before the forming processes, such as molding, pressing or
casting, fine particles of stabilizer and monoclinic zirconia are well
mixed.
 Then the mixture is used for forming of green body. The phase
conversion is accomplished by sintering the doped zirconia at 1700° C.
During the firing (sintering), the phase conversion takes place.
 High quality stabilized zirconia powder is made by co-precipitation
process. Stabilizers are introduced during chemical processing, before
zirconium hydroxide's precipitation. (See following flow chart):
 A cubic (or tetragonal) phase zirconia is formed during calcination of
chemically precipitated intermediates.
 These powders have chemically higher uniformity than in-situ
stabilizing powder and can be used in applications such as refractories,
engineering ceramics and thermal barrier coatings.
Considerations on Preparation of
Precipitated Zirconia and PSZ powders.
 Small particle, large specific surface area, desired particle size distribution will
greatly enhance the sintering kinetics, such as shorter sintering time, lower sintering
temperature and denser specific gravity of sintered body.
 However, the physical properties of powders also depend upon individual
application. Forming processes such as tape casting and extrusion sometimes need a
smaller specific surface area to enhance dispersion of the powders when mixed with
solvents. Special efforts during the preparation of powders are needed to control
initial particle size distribution, agglomeration, and calcination
 A. Particle size: Particle size is mostly determined by the agglomerate's size that are
formed in the early stages of powder preparation and during the precipitation. There
is no or little effect on the particle size during drying or calcination stage, even
calcinated at different temperature or for different time periods.
 B. Crystallite Size: Crystallite size is determined during Calcination due to the
crystal growth. The calcination temperature has more significant effect on final
crystal size than calcination time.
 C. Specific Surface Area: As crystallite size, the specific surface area is strongly
influenced by the calcination parameters, especially by calcination temperatures.
Forming and Sintering of Yttria Stabilized Zirconia Powder
Grade: PSZ-5.2YB-NB

 Sintering:
Room Temperature ® 900° C 2° C/min.
900° C ® 1300° C 1° C/min.
1300° C ® 1540° C 2° C/min.
1540° C Keep 2 hours
1540° C ® 1000° C 2° C/min.
1000° C ® Room Temperature Stop heating and keep in furnace.
 The properties of fired PSZ:
Density: 5.95-6.05 g/cm3
HRA: 89 Sore D
Flexural Strength: 940 MPa
 In late 1929, Ruff and co-workers demonstrated the possibility of
stabilization of C-phase at room temp by adding small amount of
CaO. The addition of stabilizing oxides, like CaO, MgO, CeO2, and
Y2O3, to pure Zirconia allows generating multi phase materials
known as Partially Stabilized Zirconia (PSZ).
 T-M phase transformation in partially stabilized Zirconium (PSZ)
and in the process improves the mechanical and physical properties
of the material.
 Tetragonal (T) phase of PSZ is in metastable state at room
temperature. The state is metastable because the transformation from
T to M phase can be induced by external influence like tension or
temperature.
 On PSZ, when tensile stresses acting at the crack tip induces
transformation of metastable T phase to M phase. This
transformation is associated with local increase of 3 % to 5 % in
volume.
 This increase in volume results in localized compressive stresses
being generated around and at the crack tip. Thereby squeezing the
crack. This physical property is known as transformation toughening.
Transformation-toughened Zirconia

 Transformation-toughened zirconium oxide (TTZ) is another family of


important high-strength, high-toughness ceramics that have been devel
oped during the last 20–25 years [13, 14].
 TTZ materials have fracture toughness values ranging from about 6–15
MPa ?m1/2, compared to conventional ceramics with TRANSFORM
ATION-TOUGHENED ZIRCONIA 75 fracture toughness of about 2–
3 MPa ?m1/2.
 The mechanism of toughening in TTZ materials involves a volume inc
rease due to a polymorphic transformation that is triggered when an ap
plied stress causes a crack to form in the TTZ [15].
 The volume increase only occurs for material adjacent to the crack and
presses against the crack to keep it from propagating through the TTZ.
Some forms of steel have a similar mechanism of toughening, so TTZ
has sometimes been called ceramic steel.
 Figure 2.7 shows the microstructure of one type of TTZ called partially s
tabilized zirconia (PSZ). It consists of lenticular-shaped precipitates of th
e tetragonal form of zirconia distributed throughout larger grains of the c
ubic phase of zirconia.

 The tetragonal grains are the ones that transform adjacent to a crack.

 Another TTZ is made up completely of tiny grains of the tetragonal phas


e and is referred to as tetragonal zirconia polycrystal (TZP). Both types a
re mentioned because they each have different properties, and one may b
e preferable for a specific application.

 Transformation toughening was a breakthrough in achieving high-strengt


h, high-toughness ceramic materials. For the first time in history a cerami
c material was now available with an internal mechanism for actually inh
ibiting crack propagation.

 A crack in a normal ceramic travels all the way through the ceramic with
little inhibition, resulting in immediate fracture. TTZ has fracture toughn
ess (resistance to crack propagation) three to six times higher than norma
l zirconia and most other ceramics. It is tougher than cast-iron and comparabl
e in toughness to some compositions of WC–Co cermet.
 Table 2.5 lists some of the applications where TTZ has been s
uccessful.

 TTZ ceramics typically cost around four times as much as stee


l and two times as much as WC–Co for a part such as an extr
usion die.

 In spite of the higher cost, though,TTZ often can provide suffi


cient increased life to justify its use on a life-cycle cost basis.

 The suppliers can provide information on life-cycle cost for ex


isting applications and can probably estimate for similar appli
cations
 Since the tetragonal phase is unstable, but shows the greatest
mechanical strength of the three phases, Y-TZP was used for the
surgical grade zirconia ceramics.
Porous Ceramics

 Porous ceramics have traditionally been used for thermal insulation


purposes and as building materials.

 Applications such as filters, catalyst supports and membranes are


currently rapidly growing markets owing to among other things
environmental aspects.

 Porous ceramics are produced within a wide range of porosities and


pore sizes depending on the application intended.

 Filters for molten metals often have pore sizes of 300–800 μm,
whereas membranes for reverse osmosis have pore sizes of a few
tenths of a nanometre.
 Different techniques for creating porous bodies. The choice of technique
depends on the desired structure and pore size. One of the techniques is based
on the foaming of a powder/protein suspension. Porosities between 50 and
80% with pore sizes in the range 10–500 μm have been obtained.
 The addition of a fugitive agent is another method of providing porosity in a
ceramic material. The total porosity and pore size distribution can be carefully
controlled by the choice of fugitive agent and the amount added. This method
results in both open and closed pores depending on the total porosity.
 Laminated structures with, e.g. alternating dense and porous layers or a
gradient structure with increasing pore sizes can easily be created using the
technique of adding a fugitive resin. Porosity can also be created by controlling
the particle interaction.
 The choice of powder, particle size, packing technique and sintering procedure
determine the final structure. All of the above mentioned techniques allow the
forming of complex shapes.
 As an example it can be mentioned that porous materials with more
than 90 vol% porosity for thermal insulation has been developed with
extremely low thermal conductivity (< 0.08 W/m K).
 Ultrafiltration membranes built up of three layers are another result of
our efforts in the field of porous structures.
 The ultrafiltration membrane top layer has pore sizes as small as 6 nm.
The characterisation of porosity and pore sizes by water intrusion,
mercury intrusion and scanning electron microscopy are services
frequently used in the development of porous structures.
Laminated intermediate layer and support sintered at 1200 oC
with a dip-coated top layer.
Glass ceramic
 There are materials that are hybrids between glasses and ceramics.

 Glass ceramics are a family of fine-grained crystalline materials achieved


through controlled crystallization of glasses.

 They are nonporous and are either opaque or transparent. Their optical
transparency arises from the fact that the crystals are smaller than the
wavelength of visible light such that the light waves are transmitted without
significant scattering.

 Like glasses, glass ceramics have excellent corrosion and oxidation resistance,
but have improved impact strength and dimensional stability over both glasses
and ceramics.
 Glass ceramics are commonly made of compositions in the MgO–
Al2O3–SiO2, and Li2O–Al2O3–SiO2 systems, with the main crystal
phases being cordierite (Mg2Al4Si5O18) and β-quartz and β-
spudomene (Li2O.Al2O3 .4SiO2) solid solutions.
 The residual glass phase is usually 1–10% by volume.

 The desired crystalline microstructure is achieved through the addition


of nucleating agents, often titanium dioxide, to the glass prior to heat
treating.

 The glass is heated to an appropriate nucleating temperature that allows


the maximum number of crystal nuclei to form, followed by heat
treatment at a higher temperature to grow the crystals

 The result is a highly crystalline material with tiny crystallites, on the


order of a few nanometers.

 Glass ceramics are used as ovenware and tableware, electrical


insulators, substrates for circuit boards, architectural cladding, and for
heat exchangers and regenerators.
Controlled devitrification of a glass

 The basic principle of glass-ceramic production is that


certain compositions of glass respond to controlled heat-
treatment and can be converted, without distortion and
with little dimensional change, from a readily-shaped glass
into a fine-grained crystalline ceramic possessing useful
engineering properties.

 The key to this structural transformation, which takes place


throughout the bulk of the glass (volume crystallization),is
the presence of a nucleating agent, or catalyst, in the
original formulation.
 Controlled devitrification of a special glass involves two or more stages of
heat-treatment.

 In the first stage, which can begin while the glass is cooling from the
forming and shaping operation, holding at a specific temperature for a
definite time period causes the catalyst to initiate the precipitation of large
numbers of nuclei throughout the glassy matrix.

 When these seed regions reach a certain size, different species of crystals
may begin to grow upon them.

 Finally, in the second stage of heat-treatment the structure is heated to a


different temperature in order to induce further crystallization, crystal
growth, crystal transitions and a gradual, almost complete, disappearance
of the glassy matrix
 Control of time and temperature
is essential during the production
by heat-treatment of a
glassceramic.

 Curve N represents the rate of


homogeneous nucleation; that is,
the number of nuclei forming per
second in each unit volume of
glass.

 Curve G represents the rate of


crystal growth (micron/second).
Each curve has a peak value; for
viscous glass-forming melts, these
maxima are not very pronounced.
 Glass-ceramic, it is of prime importance to select a temperature which is
close to the peak of the nucleation curve and then, in the second stage of
heat-treatment, a temperature which does not encourage excessive grain
growth. Usually the temperature chosen for the second stage is higher than
that used for the first.

 A careful balance of conditions during heat-treatment will favour the


production of the desired ultra-fine grain structure. Thus the rate of
nucleation should be high, nuclei should be uniformly dispersed and the
rate of crystal growth should not be excessive. Crystals are one micron or
less in size; interlocking of these crystals will enhance the mechanical
strength.

 However, although spinodal decomposition is sometimes possible, it is


usually regarded as a nucleation and growth process.
 Although the exact nature of the early stages of nucleation is highly
debatable, the nuclei, once formed, enable heterogeneous nucleation
of the major crystalline phases to take place.

 Metastable phases may form during heat-treatment; such phases do


not feature in phase (equilibrium) diagrams. Well-known crystalline
phases may appear at unexpected temperatures.

 Nominally metastable phases may prove to be quite stable under


service conditions. Furthermore, successful compositions are usually
multi-component in character and modifying oxides, particularly the
catalyst, can have a significant effect upon the types of crystal
produced and upon their transformation processes.

 For a given catalyst, a change in the heat-treatment process can


result in a change in the major crystalline phase(s).
 Nucleation in glasses which use an oxide as catalyst often appears to
be preceded by a process of separation into two solid glassy phases
(metastable immiscibility).

 These microphases differ in chemical composition and are therefore


believed to have a desirable effect upon the ultimate grain size by
favouring a high nucleation density and reducing the growth rate of
crystals.

 Phase separation may occur during either cooling of the melt or


reheating and it is logical to presume that it is more likely to take place
when two network-formers are present in the glass formulation. The
production of Vycor, a SiO2-B2O3-Na2O glass, also takes advantage of
phase separation.
Development of glass-ceramics

 Metals, such as copper, silver or gold, act as nucleating agents for


limited crystallization. It was fortuitously discovered that higher heat-
treatment temperatures could induce complete crystallization.

 Certain oxides could also act as effective nucleating agents and led to
development of the first glass-ceramics, which were based on the SiO2-
Al2O3-LiO2system.

 Conveniently, these materials do not require prior irradiation.


 Oxides which promote crystallization include titania, zirconia and
phosphorus pentoxide.

 As a general rule, the temperatures of melting and refining should not


exceed 1400-1500oC.
 Fortunately, some nucleating agents, such as titania, have a strong fluxing
action on silica.

 In addition, melt viscosity is important; alumina increases viscosity and


will tend to slow down melting and refining operations.

 As composition control is a vital feature of glass ceramics, it is essential to


maintain melt composition reproducibly from batch to batch.

 Volatilization and interaction between the melt and the refractory lining of
the melting furnace can make this difficult.

 For instance, high proportions of lithium oxide in the melt will increase
attack on the lining.
 Although conventional glasses have a useful
'long‘ range of temperature over which they can be
worked, the composition of potential glass-
ceramics restricts ('shortens') this range,
particularly when aluminium oxide is present.

 As a consequence, the choice of shaping process


may be restricted to gravity or centrifugal casting.
 As metastability is an essential feature of a glassceramic, it is not
surprising to find that certain compositions tend to devitrify
prematurely during working.

 Oxides of aluminium, phosphorus and the alkali metals sodium and


potassium inhibit devitrification in SiO2-LiO2 glasses. On the other
hand, the glass should recrystallise neither too quickly (during cooling
of the melt) nor too slowly (during heat-treatment).

 These tendencies can be eliminated by adding oxides which have a


specific effect upon the strength of the glass network structure.

 For instance, lithium oxide introduces non-bridging oxygen ions into a


network of SiO4 tetrahedra and, by weakening it, favours
crystallization.
 The versatility and potential for development of glassceramics quickly led
to their adoption in heat engines, chemical plant, electronic circuits, seals,
cladding for buildings, aerospace equipment, nuclear engineering, etc.
They can offer a remarkable combination of properties.

 For instance, glass-ceramic hob plates for electric cookers are strong,
smooth and easy to clean, stable over long periods of heating, transparent
to infrared radiation from the tungsten halogen lamp, relatively opaque to
visible light (reducing glare) and resistant to thermal shock. The last
property originates primarily from the low thermal coefficient of thermal
expansion (a) of this particular glass-ceramic.

 In the versatile SiO2-Al2O3-LiO2 class of glass-ceramics, the a-value can


be 'tailored' from zero to 12 x 10-6 oC-1 by controlling structure. Thus, in
types containing about 10% alumina, crystals of lithium disilicate and
quartz (or cristobalite) form to give a relatively high expansion coefficient.
 Increasing the alumina to about 20% favours the formation of two types of
lithium aluminium silicate crystals, b-spodumene and b-eucryptite. Over the
temperature range 20-100O0C, the a-values for these two compounds are 0.9 x10-
6 oC-1 and -6. 4 x 10-60C-1, respectively.

 Careful balancing of their relative amounts against the residual glass content can
reduce the overall expansion coefficient towards zero.
This capability is ideal for the large mirror blanks used for telescopes where dime
nsional stability is essential.

 In heat engines such as lorry gas turbines, a low expansion coefficient is required
for the regenerative heat exchanger which is alternately heated and cooled by exh
aust gases and combustion air. In glass/glass and metal/glass seals, precise matchi
ng of expansion characteristics is possible.

 In the mass production of colour television tubes, devitrifiable solder glass-ceram


ics based upon the PbO-ZnO-B2O3 system have a fairly high a value and have be
en used to seal the glass cone to the glass face plate at a relatively low temperatur
e without risk of distortion. The seal is subsequently heated to form the glass-cera
mic.
 A fine-grained structure of interlocking crystals favours mechanical
strength; modulus of rupture values are comparable to those for dense
alumina.

 In a machinable variety of glass-ceramic, interlocking crystals of platey


mica deflect or blunt forming cracks and make it possible for complex
machinable components to be designed. Chemical stability, as well as wear-
resistance, is essential when service involves contact with fluids (e.g. valves,
pumps, vessel linings).

 It is well-known that the fluxing oxides of sodium and potassium lower the
chemical resistance of silica glass to aqueous solutions; in glass-ceramics,
this susceptibility is countered by stabilizing any residual glass phase with
boric oxide.

 Attempts are being made to extend their use to much higher temperatures
(e.g. 1300-170O0C) by exploiting refractory systems, such as SiO2-Al2O3-
BaO, which can provide a liquidus temperature above 175O0C but such
glasses are very difficult to melt.
 Conversion from glass to crystals causes mobile ions to disappear from
the structure and become 'bound‘ to crystals, consequently the electrical
resistivity and dielectric breakdown strength of glass-ceramics are high,
even at temperatures up to 500-70O0C. The dielectric loss is low.

 Utilization of plentiful and cheap waste byproducts from industry for the
bulk production of glass-ceramics has stimulated much interest.

 Although the chemical complexity of materials such as metallurgical


slagsmakes it difficult to control and complete crystallization, strong and
wear-resistant products for architecture and road surfacing have been
produced (e.g. Slagceram, Slagsitall) have a strong fluxing action on silica.
In addition, melt viscosity is important; alumina increases viscosity and
will tend to slow down melting and refining operations.

 As composition control is a vital feature of glassceramics, it is essential to


maintain melt composition reproducibly from batch to batch.
 Volatilization and interaction between the melt and the refractory lining of
the melting furnace can make this difficult. For instance, high proportions
of lithium oxide in the melt will increase attack on the lining. The melt
leaving the melting furnace has a temperature-dependent viscosity of 1013
poise and the cooling mass can be worked and shaped until its viscosity
falls to about 108 poise.

 Although conventional glasses have a useful 'long'range of temperature


over which they can be worked, the composition of potential glass-
ceramics restricts ('shortens') this range, particularly when aluminium oxide
is present. As a consequence, the choice of shaping process may be
restricted to gravity or centrifugal casting.
Ceramic Structures
 Ceramics are a little more complex than metallic structures,
 A ceramic has traditionally been defined as “an inorganic, nonmetallic
solid that is prepared from powdered materials and is fabricated into
products through the application of heat. Most ceramics are made up of two
or more elements. This is called a compound. For example, alumina
(Al2O3) is a compound made up of aluminum atoms and oxygen atoms.

 The two most common chemical bonds for ceramic materials are covalent
and ionic. The bonding of atoms together is much stronger in covalent and
ionic bonding than in metallic.

 This is why ceramics generally have the following properties: high


hardness, high compressive strength, and chemical inertness. This strong
bonding also accounts for the less attractive properties of ceramics, such as
low ductility and low tensile strength. The absence of free electrons is
responsible for making most ceramics poor conductors of electricity and
heat.
 However, it should be noted that the crystal structures of ceramics are
many and varied and this results in a very wide range of properties. For
example, while ceramics are perceived as electrical and thermal
insulators, ceramic oxide (initially based on Y-Ba-Cu-O) is the basis
for high temperature superconductivity. Diamond and silicon carbide
have a higher thermal conductivity than aluminum or copper. Control
of the microstructure can overcome inherent stiffness to allow the
production of ceramic springs, and ceramic composites which have
been produced with a fracture toughness about half that of steel. Also,
the atomic structures are often of low symmetry that gives some
ceramics interesting electromechanical properties like piezoelectricity,
which is used in sensors and transducers.

 The structure of most ceramics varies from
relatively simple to very complex. The
microstructure can be entirely glassy (glasses
only); entirely crystalline; or a combination of
crystalline and glassy. In the latter case, the glassy
phase usually surrounds small crystals, bonding
them together. The main compositional classes of
engineering ceramics are the oxides, nitrides and
carbides.
Advanced ceramics

 Structural (wear parts, bioceramics, cutting tools, and engine


components)
 Electrical (capacitors, insulators, substrates, integrated circuit packages,
piezoelectrics, magnets and superconductors)
 Coatings (engine components, cutting tools, and industrial wear parts)
 Chemical and environmental (filters, membranes, catalysts, and
catalyst supports)
Sol-Gel Glasses
 Sol-gel processing uses solutions prepared at low temperature rather
than high temperature powder processing to make materials with
controlled properties. A precursor sol-gel solution (sol) is either poured
into a mold and allowed to gel or is diluted and applied to a substrate
by spinning, dipping, spraying, electrophoresis, inkjet printing or roll
coating.
 Controlled drying of the wet gel results in either a ceramic or glass
bulk part or a thin film on a glass, plastic, ceramic or metal substrate.
Sol-gel derived materials have diverse applications in optics,
electronics, energy, space, sensors and separation technology
 highly porous bulk and thin film aerogels using a sol-gel process.
 These novel materials have unique properties
 (>90% porosity, ultra-low density, low hermal conductivity) that lead to
applications as acoustic insulation, highly efficient inorganic insulation, low
K dielectrics and as inert porous matrices for sensors or optics.
Capabilities
 Formulate and produce single and multicomponent glass and ceramic
materials with controlled porosity (templated or non-templated) by low
temperature solution chemical polymerization (sol-gel techniques) Deposit
sol-gel thin films by spinning, dipping, spraying, electrophoresis, ink jet
printing orroll coating for reflection control, planarization, protection,
dielectric barriers, enhanced surface conductivity, inert porous matrix for
sensors or surface modification
 • Produce ultra-low density (<150 mg/cc) bulk aerogel glass by either CO2
solvent exchange and supercritical solvent removal or low temperature/
pressure (LTP) processing. Thin aerogel films can be deposited on
substrates by the LTP process • Entrain particles, optically active
compounds and chemically selective reagents into sol-gel films or
controlled porosity bulk sol-gels (aerogels or xerogels) • Perform process
development and scale-up of laboratory research processes
Tape casting

The top schematic drawing illustrates tape casting. The bottom sketch shows
the different stages during the processing: the slip consisting of water, ceramic
particles and binder; the cast, dried green sheet; and, finally, the microstructure
of the sintered material.
 Tape Casting
 This process involves the casting of a slurry onto a flat moving carrier
surface. The slurry usually consists of a ceramic powder with the
appropriate additions of solvents plasticisers and binders.

 Doctor Blade on Tape Cast Strip "As-Cast" Strip

 The slurry passes beneath the knife edge as the carrier surface
advances along a supporting table. The solvents evaporate to leave a
relatively dense flexible sheet that may be stored on rolls or stripped
from the carrier in a continuous process.
 "As-Cast" Tape Cast Strip

 Tape casting is a forming technique for producing thin, flat ceramics. The
method was originally deve-loped for producing electronic ceramics
(insulating substrates and packages and multilayer capacitors) and is still
mainly used for this. Structural laminates, knives, membranes and solid
oxide fuel cells are examples of other applications for thin ceramics formed
by tape casting. The tape thickness that can be achieved is generally in the
range of 25 μm up to 1 mm but it is possible to produce tapes down to 5 μm.
 The Swedish Ceramic Institute (SCI) has focused its research and
development within this area on water-based tape casting. An aqueous
system has the advantages of reducing health and environmental hazards
coupled with lower cost and a more manageable process. Among the
disadvantages of water-based tape casting we can mention slower drying,
higher crack sensitivity and, for some ceramics, reactions with water.
Studies have been made, in which the SlipGreen TapeSintered
MaterialTape CastingBurn-out,SinteringCast TapeCasting BladeSlipCarrier
Film entire process chain has been evaluated with regard to rheological
properties, drying, binder removal, sintering and, finally, microstructure.
 Acrylic latex-type binders have been identified as the best type of binder
owing to their low viscosity at high polymeric content and their internal
plasticization, which makes additional plasticizer superfluous. Furthermore,
lamination is possible at room temperature. Green tapes are obtained that are
insensitive to air humidity, at the same time as they have a high quality with
regard to surface smoothness, flexibility and green density. The longer drying
times of water-based systems are overcome by the fact that higher solids
loading is possible in aqueous systems than in organic, solvent-based systems,
coupled with effective heating during drying. Important characteristics of the
latex relevant to the processing are the latex particle size, the stabilisation
type of the latex and the type of polymer.
 So far, SCI has tape cast the following materials: Al2O3, ZrO2, cordierite,
mullite, alu minium titanate, PZT, SiC, Si3N4 and particulate composite
materials: Al2O3-ZrO2, cordierite-ZrO2 and Si3N4-TiN. Laminated
structures such as Al2O3 membranes, SiC/C laminates and PZT-actuators
have been made of these materials. SCI’s tape caster (TC 155 from AEM Inc.)
is a continuous machine with a stationary casting head. The machine is
designed for making thin tapes with a thickness range 4–400 μm. For thicker
com ponents (0.5 mm up to 7 mm) lamina tion of green tapes is possible.
 Diamond Grinding
 High levels of accuracy and surface finish can be achieved
by diamond grinding. Tolerances of a few microns are
commonplace. However, diamond grinding is a relatively
expensive micro-machining process, consequently, if a
design can be produced to "as-fired" tolerances, the overall
cost of the component is reduced. Precision Machining
(Diamond Grinding) of Engineering Ceramics



Source “ Manufacturing Processes for Engineering Materials”, 4th edition, Kalpakjian, Schmid,
Prentice Hall 2003
Figure from: “ Manufacturing Processes for Engineering Materials”, 4th edition,
Kalpakjian, Schmid, Prentice Hall 2003