CERAMICS

Introduction
Ceramics can be defined as inorganic crystalline materials. They are the
compounds between metallic and nonmetallic elements. Basically they are the
most natural materials. Such traditional ceramics are used to make bricks,
sanitary ware, refractories, abrasives, etc. On the other hand, ceramics are also
used in most sophisticated applications such as computer chips, sensors, etc.
The word Ceramics is derived from Keramikos, which means burnt stuff in
Greek since desirable properties of ceramics are normally achieved through a
high temperature heat treatment process (firing). Oxides, nitrides, carbides of
metals/nonmetalsaresomeexamplesforceramicmaterials.Theatomicbonding
inceramicsismixed,ionicandcovalent,thedegreeofioniccharacterdependson
thedifferenceofelectronegativitybetweenthecations(+)andanions().
Commoncharacteristicsofceramicmaterialsarelistedhere:
Generallyceramicsarehard,brittleandpossesshighmeltingpoint.
Theyareelectricallyandthermallyinsulators.
Opticallytheycanbeopaque,semitransparent,ortransparent.
Theyareinertinmostoftheenvironments.
Theyaregenerallyporousandhencelight(lowdensity).
Mostoftheceramicsarestableevenathightemperatures.
Ceramicshaveexceptionalstrengthundercompression.
Thewearresistanceofceramicsishigh.
Ceramiccrystalstructures
The atomic bonding in ceramics is mixed type, i.e., a mixture of ionic and
covalent types. The degree of ionic character depends on the difference of
electronegativity between the cations (+) and anions (). For example, CaF2 has
about89%ionicbondswhereasSiChasonly12%ioniccharacter.Ionicradiiand
electrical neutrality are two important factors to be considered in order to
understandcrystalstructuresofionicallybondedsolids.Chargebalancedictates
chemicalformula(Ca
2+
andF

formCaF2).Relativesizesofthecationsandanions
are important since cations want maximum possible number of anion nearest
neighborsandviceversa.Thesetopicsarealreadydiscussed(duringthestudyof
crystalstructures).
Applicationofceramics
Ceramics are used in a wide range of technologies such as refractories, spark
plugs,capacitors,sensors,abrasives,magneticrecordingmedia,etc.Forexample,
the space shuttle makes use of ~25,000 reusable, lightweight, highly porous
ceramictilesthatprotectthealuminumframefromtheheatgeneratedduringre
entry into the Earths atmosphere. These tiles are made from highpurity silica
fibers and colloidal silica coated with borosilicate glass. Ceramics can appear in
nature as oxides. They are present even in human body (bones and teeth).
Ceramicsarealsousedascoatings(glazes,enamels,etc.).Aluminaandsilicaare
themostwidelyusedceramicmaterials.
Thecompressivestrengthistypicallytentimesthetensilestrength.Hence,in
structuralapplications,ceramicsareusedagainstcompressiveloads.
Thetransparencytolightofmanyceramicsenablesthemtouseinnumerous
opticalapplications(windows,photographiccameras,telescopes,etc).
Goodthermalinsulationenablesthemtouseinovens,theexteriortilesofthe
shuttleorbiter,etc.
Good electrical isolation enables them to use ceramics are used to support
conductorsinelectricalandelectronicapplications.
Good chemical inertness enables them to use applications in reactive
environments.
Ceramicsareoftenusedtoprovideprotectivecoatingstoothermaterials.
Thin films of many complex and multicomponent ceramics are used in
modernelectroniccomponents.
Fibers are produced from ceramic materials for several uses as
reinforcement in composite materials, for weaving into fabrics, for use in
fiberopticsystems,etc.
Ceramic oxides are used as magnetic and dielectric materials (ferrites and
ferroelectricmaterials).
The table given in the next page gives numerous applications of ceramic
materialsindiverseareas.
Classificationofceramics
In fact ceramics and glasses represent some of the earliest and most
environmentally durable materials for engineering. In addition they also
represent some of the most advanced materials developed for aerospace and
electronic industries. This diverse collection of engineering materials can be
studiedunderthreemaincategories,viz.,crystallineceramics,glassesandglass
ceramics.
Basically ceramics can be classified as natural (or traditional) ceramics and
advanced ceramics. Traditional ceramics are those based on clay (china, bricks,
tiles, porcelain), glasses where as advanced / new ceramics are modern day
materialsusedextensivelyinelectronic,computer,aerospaceindustries.Another
way of classifying the ceramics is on the class of chemical compounds such as
oxides,carbides,nitrides,sulfides,fluorides,etc.However,themostelegantway
istoclassifyceramicsbytheirfunction(referthetablegivenbelow).

A glass is an inorganic nonmetallic material that does not have a crystalline

structure.Suchmaterialsaresaidtobeamorphous.Thesearethenoncrystalline
solids with compositions comparable to the crystalline solids. Examples of
glasses range from the sodalime silicate glass in soda bottles to the extremely
high purity silica glass in optical fibers. Glassceramics are the crystalline
ceramicsthatareinitiallyformedasglassesandthencrystallizedinacontrolled
manner.
Someoftheimportantandmostwidelyusedceramicmaterialsaresummarized
here:
Silica(SiO2):Oneofthemostwidelyusedceramicmaterialwhichisessential
ingredient in glasses, refractories, abrasives, etc. Many of the traditional
ceramics fall into the category of silicates. In the form of long continuous
fibers, it is used to make optical fibers. Powders of silica are used in tyres,
paints, etc. Silica shows polymorphisms with three hexagonal and one fcc
polymorphs. These are known as low quartz (up to 573C, hexagonal), high
quartz(between573and867C,hexagonal),hightridymite(between873and
1470C, hexagonal) and high cristobalite (between 1470 and melting point
1723C,fcc).
Alumina (Al2O3): It is also a widely used ceramic and used in variety of
applicationsrangingfromrefractoriestoelectronicpackages.Itpossesseslow
thermal conductivity, high hardness and chemical stability. It has a good
strengthevenathightemperatures.Itisusedasinsulatorsinsparkplugs.
Zirconia(ZrO2):Itisanimportantoxideceramic.Therearethreepolymorphs
of zirconia Monoclinic zirconia (stable up to 1150C), tetragonal (1150
2300C) and cubic (above 2300C). The tetragonalmonoclinic phase
transformation is accompanied with 4% volume change. If this
transformation is allowed in an uncontrolled manner during service,
spontaneousfailureofzirconiaceramiccanoccur.Thisproblemiscountered
bydopingthezirconiawithoxidesofcalcium,yttriumormagnesium,which
stabilizesthestructure(partiallystabilizedzirconia)
Barium titanate (BaTiO3): Most widely used electronic ceramic. It is a
ferroelectricmaterial.Highdielectricconstantofbariumtitanatemadeitideal
materialforcapacitors.
Boron carbide (B4C): Very hard but light weight and hence used in
applicationswheregoodabrasionresistanceisrequired.Itisusedinnuclear
shielding,bulletproofarmourplate,etc.
Cordierite (2MgO.2Al2O3.5SiO2): Used to make honeycomb structure in
catalyticconverterstocarryadispersionofnanosizedmetalparticles.
Lead zirconium titanate (PZT, PbxZr1xTiO3):Mostwidelyusedpiezoelectric
material,findingapplicationingasigniters,ultrasoundimagingdevices,etc.
Silicon carbide (SiC): Exhibits excellent oxidation resistance (even at
temperatures>1200C).Henceitisusedascoatingformetals,carboncarbon
composites and other ceramicsto protectinextremetemperatureconditions.
Itisalsousedasabrasiveingrindingwheelsandheatingelementinfurnaces.
Zincoxide(ZnO):Usedasanacceleratorinthevulcanizationofrubbers.Itis
alsousedinpaints,skinointments,etc.
Magneticoxides:Magneticceramicsarecomplexoxidesthatbelongtooneof
the categories spinels (cubic ferrites), garnets (RE ferrites) or hexagonal
ferrites.
Yttrium Aluminium Garnet (YAG, Y3Al5O12): These crystals are used for
makingNdYAGlasers.
Chinaclay(Kaolinite,Al2O3.2SiO2.2H2O):Atraditionalceramic.
Mica(K2O.3Al2O3.6SiO2.2H2O):Awidelyusedinsulationmaterial.
Asbestos(3MgO.2SiO2.2H2O):Anotherceramicusedinnumberofindustrial
appliocations.
123 superconductors: Someofthe oxideceramicsarefinding applications as
high (critical) temperature superconductors. YBa2Cu3O7x or 123
superconductorisatypicalexampleforthisclassofceramics.
MagCarb (Magnesium carbonate, MgCO3): A ceramic mineral, popularly
known as magnesite. It contains about 43% MgO. It is commonly used in
pottery bodies, glazes, glass, etc. and also as reinforcing agent translucent
filler in rubber and plastic compounds. It also acts as flame retardant in
plastics.Beingarefractory,itisusedtomakebricksforthecementandmetal
industries.However,itdecomposesat900CandlosesitsCO2.
Carbon: It is not a ceramic. Carbon exists in various polymorphic forms: sp
3

diamondand amorphous carbon,sp

2
graphiteand fullerenes/nanotubes,one
dimensionalspcarbon.Carbon(Diamond)hasdiamondcubicstructure.Itis
one of the strongest/hardest materials known. It has high thermal
conductivity (unlike ceramics). It is transparent in the visible and infrared,
withhighindexofrefraction.Itcanbedopedtomakeelectronicdevices.Itis
ametastablematerial(transformstocarbonwhenheated).Ontheotherhand,
Carbon (Graphite) has a layered structure with strong bonding within the
planar layers and weak, van der Waals bonding between layers. Easy
interplanarcleavagepropertyofgraphitefindsapplicationsasalubricantand
for writing (pencils). It is a good electrical conductor and chemically stable
even at high temperatures. The prime applications include furnaces, rocket
nozzles,weldingelectrodes,etc.

Processingofceramics
Ceramics melt at relatively higher temperatures and exhibit brittle behaviour
undertension.Therefore,theycannotbeprocessedbyusingconventionalroutes
suchascasting,thermomechanicalforming,etc.Generallyceramicmaterialsare
processed using powder metallurgy route. The basic steps involved in the
processingofceramicsareschematicallypresentedinthefiguregiveninthenext
page.
Apowderisacollectionoffineparticles.Crushingandgrindingareconductedto
reduce the particle size of the minerals. Ball milling further reduces the size of
particles and blends different powder ingredients. In this, a cylindrical vessel
containing grinding media (steel/alumina/zirconia spheres) is fed with powder
ingredients and it is rotated. Collisions between the grinding media and the
ceramicpowderingredientsleadtosizereductionandefficientblending.Solgel
process is a chemical technique that is used to produce large quantities of high
purityceramicpowders.Asolisadispersionofcolloidalmatter.Itisconverted
intoagelandultimatelyintoausefulproduct(suchasthinfilms,powders,etc.).
Calcination refers to the heating of a mineral/intermediate product in order to
decompose or to remove moisture. In leaching, acids and alkalies are used to
dissolveamineral.

Forming/shapingof
powders
Thermaltreatment/
sintering
Secondaryprocessing
Finalproduct
Powderpreparation
Ceramic powders prepared by using various techniques are shaped using
different methods depending on the requirement. The figure given in the next
pageshowsfewsuchtechniques.

When the ceramic powders are needed in the form of soft agglomerates, a
techniqueknownas spray dryingisused.Inthis,aslurryofceramicpowderis
sprayedthroughanozzleintoachamberinthepresenceofhotair.
Compaction and sintering form the most common methodology in the
formation of ceramic products. Compaction is nothing but application of force
(uniaxial/isostatic) to compact the ceramic powders (into the required shape) to
form green ceramic. Very large pieces are produced by using cold isostatic
pressing (CIP) where pressure is applied using oil. Sintering involves different
masstransportmechanismsthatresultintodensification.
In some cases, parts are produced under conditions in which sintering is
conductedusingappliedpressure(hotpressing).Inhotisostaticpressing(HIP),
pressureisappliedisostaticallyusingoil.
A technique known as tape casting is used for the production of thin ceramic
tapes. In this, a slurry containing ceramic particles, solvent, plasticizers and
bindersismadetoflowunderandontoaplasticsubstrate.Thetapeisthendried.
Slipcastingisanothertechniquethatusesanaqueousslurryofceramicpowder
(knownasslip).ItispouredintoplasterofParis(PoPCaSo4.2H2O)mould.As
the water from the slurry begins to move out by capillary action, a thick mass
builds along the mould wall. After sufficient thickness is built, excess slip is
drained and casting is removed after partial drying. This green ceramic is then
sintered at high temperature. Figure given below shows the various steps
involvedinslipcasting.

Extrusionisapopulartechniqueusedformakingfurnacetubes,bricks,tilesand
insulators. A viscousmixture ofceramic powders, binder and other additives is
fed to an extruder to get a continuous green product which is cut, dried and
sintered. In injection moulding, ceramic powder is mixed with a thermoplastic
plasticizerandotheradditivesandinjectedintoadie.Thepolymercontainedin
the green ceramic is burnt off and rest of the ceramic body is sintered at high
temperature.
Sinteringcommonlyreferstotheprocessesinvolvedinthethermaltreatmentof
powderceramiccompactscarriedoutatelevatedtemperatures(>0.5TM).
Refractories
A group of ceramic materials capable of withstanding high temperatures for
prolonged periods of time are common called as ceramic refractories. There are
threetypesbasedontheirchemicalbehaviourasindicatedbelow:
AcidicRefractoriesCommonacidicrefractoriesincludesilica,alumina,and
fireclay(animpurekaolinite).
Basic Refractories These are the refractories based on MgO (magnesia, or
periclase).Thesearemoreexpensivethantheacidrefractories.
Neutral Refractories These refractories, which include chromite and
chromitemagnesite, can be used to separate acidic and basic refractories,
preventingthemfromattackingoneanother.
Otherrefractorymaterialssuchasgraphite,zirconia(ZrO2),zircon(ZrO2SiO2),
andavarietyofnitrides,carbides,andboridesareknownasspecialrefractories.
Thetablegivenhereliststhecompositionsofcommonrefractoryceramics.

Mechanicalbehaviourandplasticdeformationofceramics
Ceramicsarebrittle.(Forbrittlefracturestressconcentratorsareveryimportant).
Measuredfracturestrengthsaresignificantlysmallerthantheoreticalpredictions
forperfectmaterialsduetothestressrisers.Fracturestrengthofceramicmaybe
greatly enhanced by creating compressive stresses in the surface region (similar
toshotpeening,casehardeninginmetals).Thecompressivestrengthistypically
ten times the tensile strength. This makes ceramics good structural materials
under compression (e.g., bricks in houses, stone blocks in the pyramids). In
crystallineceramicsslip(dislocationmotion)isverydifficult.Thisisbecauseions
of like charge have to be brought into close proximity of each other. Therefore
thereisalargebarrierfordislocationmotion.Inceramicswithcovalentbonding
slip is not easy as well (covalent bonds are strong). But in noncrystalline
ceramics, there is no regular crystalline structure and hence no dislocations.
Therefore, materials deform by viscous flow, i.e. by breaking and reforming
atomicbonds,allowingions/atomstoslidepasteachother(likeinaliquid).
Glasses
Glass is a noncrystalline inorganic material having composition similar to
manyceramics(mainlymadeupofsilicates).Itisametastablematerialthathas
hardened without crystallizing. Solidification of glass from molten state is
gradual, through a viscous stage (viscosity is increasing with decreasing
temperature),withoutaclearmeltingtemperature.Thespecificvolumedoesnot
have an abrupt transition at a fixed temperature but rather shows a change in
slopeattheglasstransitiontemperature(seethefiguregivenbelow).
Important properties of glass are: transparency, hardness, insulation, chemical
inertness, corrosion resistance and high brittleness. Due to these attractive
propertiestheyareusedinnumberofstructuralandspecialapplications.

Silicate glasses are the most widely usedcategory of glasses. Fused silica (pure
SiO2)hasahighmeltingpointandundergoessmalldimensionalchangesduring
cooling.However,commercialglassescontainnumberofotheroxideswithSiO2.
Theoxidesusedintheglassesaregenerallyfallintothreecategoriesasgivenin
thefollowingtable:
Category Characteristics Examples
Glassformers/
networkformers
Theoxidesthatformglassby
themselves.
SiO2,B2O3,GeO2,P2O5,
V2O3
Intermediates
Theoxidesthatdonotformglassby
themselvesbutsubstitutetheglass
formerinthenetworkstructure.
TiO2,ZnO,PbO2,BeO,
Al2O3
Modiefiers
Theoxidesthatbreakupthe
networkstructureandtherebycause
theglasstodevitrify.
Na2O,MgO,CaO,
PbO,Y2O3

Abriefsummarycommercialglassesispresentedhere:
Fused / vitreous silica: It is a high purity silica ( 99% SiO2). It has high
melting point and can withstand high temperatures up to 1000C. It is used
forapplicationslikefurnacewindows,crucibles,etc.
Sodalimeglass:Majorshareoftheglassindustryisinvolvedwithsodalime
glass.Thetypicalcompositionis:SiO27173%,Na2O1214%andCaO1012%.
It has lower melting range (softening point: 800 1500C). It is inexpensive
and hence very common glass in use. However, it has poor resistance to
chemical attack and thermal stresses. It is used in application such as
windows,containers,etc.
Borosilicate glass: It is also known as Pyrex glass. Typical composition is:
SiO2 81%, B2O3 12%, Na2O 5%, Al2O3 2%. It possesses good formability, low
expansion, good thermal shock resistance and excellent chemical stability.
Hence,itisusedtomakelabwares,cookingwares,etc.
Leadglass:Thisglasscontainssignificantquantityofleadoxideandusedfor
decorative applications, lenses and radiation windows. The composition of
thisglassisSiO263%,PbO20%,Na2O8%andK2O6%.
Eglass:Itisalsoknownasfiberglass.Itcontainsabout55%SiO2,15%Al2O3,
20%CaO,10%B2O3andasmallquantityofNa2O(<1%).Itisinsulativeand
corrosionresistant.Itisthemostcommonlyusedglassfiberincomposites.
Thecharacteristictemperaturesintheprocessingofglassesaredefinedinterms
ofviscosityasshowninthefollowingfigure:

Melting point: viscosity = 100 Poise, above this temperature (below this
viscosity)glassisliquid.
Workingpoint:viscosity=10
4
Poise,glassiseasilydeformed.
Softening point: viscosity = 4x10
7
Poise, maximum T at which a glass piece
maintainsshapeforalongtime.
Annealingpoint:viscosity=10
13
Poise,relaxinternalstresses(diffusion).
Strain point: viscosity = 3x10
14
Poise, above this viscosity, fracture occurs
beforeplasticdeformation.
Glass forming operations are generally carried out between softening and
workingpoints.
On the basis of above characteristic points, three ranges are identified for the
processing of glasses, viz., liquid range (< 100 poise viscosity), working range
(150010
7
poise)andannealingrange(10
13
10
15
poise).
Liquidrange:Sheetandplateglassesaregenerallymanufacturedwhenthey
are molten state. Rolling the molten glass through water cooled rolls
produces glass sheets. Floatglass process produces a glass sheet with very
smooth surface finish. In this technique, the molten glass is made to float
throughabathofmoltentin.Castinglargepartsanddrawingofglassfibers
are also done in the liquid range. Figure given below shows the techniques
formanufacturingsheetandplateglass.
(a)Rollingtheglassand(b)floatingtheglassonmoltentin

Working range: Containers, bulbs are formed in this range by using the
processes such as pressing/drawing/blowing. In the working range, glass is
formablebutnotrunny.
Annealing range: In this range, glass parts are annealed to reduce the
residualstressesintroducedduringforming.
Tougheningofglasses
Glasses are generally brittle. However, toughness of glass can be increased by
introducing residual compressive stresses in the surface. This is known as
tempering.Temperedglassiscapableofwithstandinghighertensilestressesand
impactthantheordinaryglass.Itisusedinhomewindows,refrigeratorshelving,
ovens, furniture and many other applications where safety is important. On the
other hand, annealed glasses are stressfree and used to make the laminated
glass (a polymer is sandwiched between two annealed glass pieces) which is
usedinautomobilewindshields.
Glasstemperingcanbedoneintwoways,viz.,thermalandchemicalmeans.In
thermal tempering, glass is heated above the glass transition temperature but
belowthesofteningpointandthenquenchedinanairjetoroilbath.Theinterior,
whichcoolsslowerthantheoutside,triestocontractwhileinaplasticstateafter
the exterior has already become rigid. This causes residual compressive stresses
on the surface and tensile stresses inside. In fracture, a crack has first to
overcome the residual compressive stress, making tempered glass less
susceptible to fracture. The alternate technique, known as chemical tempering,
involves chemical exchange of larger ions (K
+
) for the surface Na
+
ions. The
compressivestressingofthesilicatenetworkproduceschemicallystrengthened
glass.
Glassceramics
These are the crystalline materials derived from amorphous glasses. Hence, the
combinethepropertiesofcrystallineceramicsandnoncrystallineglasses.These
materials have very good mechanical strength, toughness, low thermal
expansion coefficient and high temperature corrosion resistance. In addition,
they have the formability and density of glasses. Glassceramics are used for
makingcookingutensils,ceramictopsforstoves,andalsoinadvancedfieldslike
communications, computers and optical applications. The production/heat
treatmentscheduleforatypicalglassceramicsystem(Li2OAl2O3SiO2)isshown
below.

Thecompositionoftheaboveglassceramicis:
Li2O4%,Al2O316%,SiO274%andTiO2(nucleatingagent)6%.