Ceramics

(keramikos - burnt stuff - desirable props are achieved by firing)

Traditional Silicate Ceramics Combinations of clay, feldspar and silica (cheap)1

Advanced/Engineering Ceramics Nearly pure compounds of o ides, carbides or nitrides (e pensive)

Non-silicate oxide ceramics -!l"#$ !lumina -'r(" 'irconia Structural Clay Products -brick -tile -se)er pipe -cement
1

Non-oxide ceramics -%i$N& %ilicon nitride -%iC %ilicon carbide

Whitewares more carefully controlled compositions -pottery -porcelain -sanitary )are

*clay * ! hydrated !luminum silicates )ith other o ides+ ,rovides )orkability before firing hardens it+ (eg !l "($ "%i#$ "-"()

elds!ar * ! naturally occurring, industrial important, net)ork silicate )ith a lo) melting temperature+ .t becomes glass upon firing and bonds the refractory components together+ %ome %i /& ions are replaced )ith !l/$ in substitional positions and some Na/, 0/, Ca/, 1a/ ions are in interstitial positions+ (eg 0"( !l"#$ 2%i#") silica * (aka flint or 3uart4) %i(" is a polymorphic compound+ (3uart4, tridymite and cristobalite are some of its forms+) .t acts as the refractory component of traditional ceramics+

Ceramics
.norganic nonmetallic materials )hich consist of electropositive5electronegative compounds that are bonded primarily by ionic bonds, sometimes )ith covalent character+ Ceramic crystal structures can be relatively simple to very comple + Ceramics can range from the more traditional 6 ine pensive to the advanced 6 highly sophisticated+ 7he fabrication of ceramics and glasses must be different than for metals because of their high melting temperatures, (hence, difficult to cast) and lo) ductility, (hence, difficult to form)+ 8ost are formed from po)ders (or particulate collections) and then dried and fired+

A!!lications" insulators capacitors semiconductors abrasives refractory ferroelectrics pie4oelectrics nuclear fuels

Processing Techni#ues" fusion slip casting sintering hot isostatic pressing(-.,) sol-gel biomimetic %-% (self-propagating high-temp synthesis)

$eneral !ro!erties" hard and strong brittle (lo) ductility) lo) toughness 6 fracture toughness lo) impact resistance lo) electrical and thermal conductivity high melting temperatures high chemical stability high compressive and tensile strengths (C%9997% by :-1# ) fatigue life is rare

Ceramics %0eramikos- burnt stuff -desirable props are achieved by firing)

Traditional Silicate Ceramics Combinations of clay, feldspar and silica (cheap)" Advanced/Engineering Ceramics Nearly pure compounds of o ides, carbides or nitrides (e pensive)

Non-silicate oxide ceramics -!l"#$ !lumina -'r(" 'irconia Structural Clay Products brick
"

Non-oxide ceramics -%i$N& %ilicon nitride -%iC %ilicon carbide

Whitewares more carefully controlled compositions

*clay * ! hydrated !luminum silicates )ith other o ides+ ,rovides )orkability before firing hardens it+ (eg !l "($ "%i#$ "-"()

elds!ar * ! naturally occurring, industrial important, net)ork silicate )ith a lo) melting temperature+ .t becomes glass upon firing and bonds the refractory components together+ %ome %i/& ions are replaced )ith !l/$ in substitional positions and some Na/, 0/, Ca/, 1a/ ions are in interstitial positions+ (eg 0"( !l"#$ 2%i#") silica * (aka flint or 3uart4) %i(" is a polymorphic compound+ (3uart4, tridymite and cristobalite are some of its forms+) .t acts as the refractory component of traditional ceramics+

-tile -se)er pipe -cement

-pottery -porcelain -sanitary )are

Clays !luminosilicates (!l"($ and %i(" and chemically bound -"() 1road range of compositions, structures, impurities ;sually the structure is layered )ith )ater bet)een the sheets making it plastic (hydroplasticity) Can be mi ed )ith )ater and easily formed and then dried and fired to increase strength

Whitewares and Structural Clay Products 8ade from clay, flint and feldspar <lint is finely ground 3uart4, a filler that is hard and chemically unreactive )ith a high melting temperature+ <eldspar is an aluminosilicate mineral that contains 0/, Na/ and Ca/+ .t acts as a flu ing agent+ (i+e+ it spreads out heat and helps things to flo)+) &e ractories 8aterials that are able to )ithstand high temperatures )ithout melting or decomposing+ 7hey are able to maintain insulative properties at high temperatures+ 7hey remain inert and unreactive at high temperatures+ 7he four main categories= fireclay, silica (acid), basic and special+ ! decrease in the porosity of refractories )ill increase strength increase corrosion resistance increase load-bearing capacity decrease insulativeness resistance to thermal shock A'rasives > tremely hard materials used for cutting, grinding, and polishing other materials+ ?ue to high heat generated during the process, these materials also must have some refractory properties+ > amples are diamond, %iC, @C, Corundum, and silica sand+ Cements materials that form a paste )hen mi ed )ith )ater and then hardened by e amples include cement, plaster of paris and lime

chemical reactions

Note= Concrete is a composite material made up of cement, large aggregates (gravel), and small aggregates (sand)+ 7he cement in concrete is similar to the glassy phase in ceramics+ .t bonds the other phases together+ Portland cement (ne of the most commonly used cements+ 8ade by follo)ing process= () calcination= grinding and mi ing clay and lime-bearing minerals *) heating to obtain a material called clinker +) grind this to a po)der ,) add gypsum (Ca%(&-"-"() to retard setting process ,rinciple constituents are tricalcium silicate ($Ca(-%i(") and dicalcium silicate ("Ca(-%i(")+ 7here can be many different compositions+ -ardening occurs by comple hydration reactions that form comple gels or crystalline substances+ 7his process is kno)n as curing+ .f there )ere no )ater the reactions could not proceed and drying )ould occur+ ?rying is bad+ Curing is good+ (,ortland cement is a hydraulic cement because )ater is involved in the reactions+ Aime is a nonhydraulic cement because other compounds (C( ") are involved in the hardening reactions+)

Ceramic Crystalline Structures

Crystal structures of ionic compounds tend to ma imi4e packing efficiency+ (7his lo)ers the overall energy+) 7he limitations to dense packing are the radius ratio and the need to maintain charge neutrality+ 7he radius ratio can help to predict the CN (and hence the crystal structure+) .f the bonding has some covalent character, then the packing )ill be less efficient+ Bou can determine the amount of ionic character in a bond by kno)ing the electronegativities, C! 6 C1, of the elements in the bond and the follo)ing e3uation= D ionic character E F1 * e -15&(C!-C1)G 1##D ! tetrahedral position is an interstitial site that if occupied, )ould have & neighbors+ !n octahedral position is an interstitial site that if occupied, )ould have 2 neighbors+ @here are the octahedral and tetrahedral sites in the fcc crystal structureH @here are the octahedral and tetrahedral sites in the hcp crystal structureH

Some relatively sim!le ceramic structures"

%odium Chloride structure (NaCl) Cesium Chloride structure (CsCl) 'inc 1lende structure ('n% and Compound %emiconductors) <luorite structure (Ca<") ,erovskite structure (Ca7i($) ?iamond Cubic structure (Carbon and >lemental %emiconductors) Iraphite (Carbon) <ullerenes (Carbon) Cristobalite structure (%i(") Corundum %tructure (!l"($) %pinel %tructure (8g!l"(&)5.nverse %pinel H

Silicate Structures
Silica (%i(") has half ionic and half covalent character+ (7he percent of ionic character is about :#D as calculated from the above e3uation+) ! CN of & is predicted for the radius ratio of #+"J for ionic compounds+ ! bond angle of 1#:o is predicted for covalent bonding+ %ilica is allotropic )ith at least five different crystalline forms depending on temperature and pressure conditions+ -o)ever, each form has every corner of an %i( & tetrahedra (every o ygen atom) shared+ 7he sharing of o ygen atoms bet)een the tetrahedra give the overall formula of %i( "+ 7he structures are not dense and have high melting temperatures+ Silicates (or silicate ceramics) are %ilica (%i(") based ceramic clays that contain %i(&&- tetrahedra in various arrangements+ 8any naturally occurring minerals such as clays, feldspars and micas are silicates+ 8any ceramic materials contain silicate structures+ 7hey include glass, cement, brick, electrical insulative materials, etc+ 7he general nature of silicate structures is the connection of the %i( &&- tetrahedra+ !dditional o ides tend to break up the continuity of these tetrahedra+ 7he remaining connectedness may be in the form of islands, chains or sheets= Networ- silicate structures * these structures connect all & corners of the %i( &&- tetrahedra to form a network+ 7he ( ygen atoms are shared )hich accounts for the overall chemical formula of %i( " not %i(&+ .sland silicate structures * )hen positive ions bond )ith the o ygens of the %i( &&- tetrahedra Chain or ring silicate structures * )hen " corners of each %i(&&- tetrahedra are bonded )ith corners of other tetrahedra )ith unit chemical formula %i($-"+ Sheet silicate structures * )hen $ corners in the same plane of a silicate tetrahedron are bonded to the corners of $ other silicate tetrahedra )ith chemical unit %i"(:-"+

Electrical Pro!erties o Ceramics

Ceramics are used in many electrical applications as= .nsulators Capacitors %emiconductors <erroelectrics ,ie4oelectrics .nsulators prevents the flo) of charge or heat+ Ceramics make good insulators because the ionic and covalent bonding restricts electron and ion mobility+ Ca!acitors store electrical energy by virtue of separating oppositely charged plates )ith an insulator (also called a dielectric) in bet)een+ !n e ample of a ceramic material used as the dielectric for a capacitor is 1arium 7itanate, 1a "7i($ %ome material properties of insulators (also called dielectrics)= Capacitance (actually this is a property of a device, not the material) ?ielectric constant ?ielectric breakdo)n strength ?ielectric loss factor %ome e amples of ceramic insulators are >lectrical ,orcelain (:#D clay, ":D silica, ":Dfeldspar) %teatite (J#D talc, 1#D clay) <osterite (8g"%i(&) !lumina (!l"($ crystals in a glassy matri of clay, talc, alkaline earth flu es) Semiconductors have an intermediate value of electrical conductivity+ 7he most commonly used ceramic semiconducting materials are sintered o ides of 8n, Ni, <e, Co, and Cu+ 1y varying the amounts of these o ides in the material the desired value of the electrical conductivity can be obtained+ 7hese are used for N7C thermistors+ ! Negative Temperature Coefficient 7hermistor is a device that measures temperature by a change in the resistance of the material+ !s temperature increases, resistance decreases+ /erroelectrics have behavior similar to a ferromagnetic material+ 7he relationship bet)een the electric dipole moment density (,olari4ation, ,) and the electric field strength (>) looks e actly like the relationship bet)een magnetic dipole moment density (8agneti4ation, 8) and magnetic field strength (-)+ Pie0oelectrics have the distinct property )hereby an applied stress induces an electrical voltage+ 7he reverse pie4oelectric effect is the phenomena )hereby an applied voltage across the material results in a dimensional change+ 1a7i( $

1echanical Pro!erties o Ceramic 1aterials

Ceramics are strong -o)ever, their principle dra)back is a disposition to catastrophic fracture in a brittle mode+ -ence, the effort in research of these materials is to make them tougher) !n e ample of an advancement in this area is the transformation toughening of partially stabili4ed 'irconia (,%')+ /ine grain si0e ceramics are stronger than coarse grain si0e ceramics 7he reason is different than for metals= .f fracture does not initiate at a crack, fla), pore or inclusion, it )ill originate at a fla) in a grain boundary+ <iner grain si4e ceramics )ill have smaller fla) at the grain boundaries+ -ence, the finer grain ceramics )ill be stronger+ The /lexural Strength is an alternate !ro!erty to Tensile Strength or ceramics 7he fle ural strength (or modulus of rupture, fracture strength, bend strength) is the (calculated) tensile stress at failure of a specimen subKected to a three or four point load+ 7his is an easier test to carry out for brittle materials than the traditional standard 7ensile 7est+ Ceramics are 'rittle Ceramics have very lo) toughness values and also fracture toughness values+ Lecall that brittle fracture consists of formation and propagation of cracks through the cross section in a direction perpendicular to the applied load+ ;sually the crack gro)th is transgranular and along specific crystallographic directions+ 7he reasons that ceramics are so brittle= 1+ Ceramic materials inherently have cracks, fla)s, pores and inclusions+ 7hese act as stress risers and failure initiates at one of these and propagates 3uickly (because there is no energy absorbing mechanism as there is in metals,) causing brittle fracture+ "+ 7he covalent bond is directional and electrons are shared+ -ence, bonds )ill not reform easily and so brittle fracture )ill occur+ $+ %ince the crystal structures tend to be comple , there are limited slip systems and large 1urgers vectors+ (called comple dislocation structures) &+ ,otential slip planes may involve like charges moving over each other )hich )ill cause separation and so brittle fracture )ill occur+ Ceramics are much stronger in com!ression than in tension) @hyH Some ceramics are su'2ect to Static /atigue or 3elayed /racture 7his is )hen ceramics fail by slo) crack propagation under a static load+ 7he mechanism is a stress-corrosion process at a crack tip+ Ceramics rarely have any sort o atigue ailure 7his is due to the lack of plasticity in ceramicsM ho)ever, there have been recent advances in compressivecompressive stress cycling of polycrystalline alumina+ Ceramics have high hardness values 7his makes them e cellent abrasive materials used for cutting, grinding and polishing+ !lumnia (aluminum o ide, !l"($) and silicon carbide, %iC are t)o of the most commonly used manufactured ceramic abrasives+ .mprovements on these are made by combining 4irconium o ide )ith aluminum o ide+ !nother important ceramic abrasive is cubic boron nitride (1orta4on)+ Ceramics have high melting tem!eratures 7his makes them e cellent materials to be used for high temperature applications+ 8aterials used at high temperatures are call refractory materials or refractories+ -o)ever, creep )ill occur at these temperatures and so one must be a)are of the materialNs creep behavior+ Porosity has an adverse a ect on a ceramic4s !ro!erties) 7he modulus of elasticity and the fle ural strength )ill both decrease )ith porosity+ There is much scatter in the data measuring the !ro!erties o ceramic materials

7he reason is because much of the data depends on fla) density and si4e+ 7his, in turn, )ill depend on fabrication techni3ue, processing and si4e of the specimen+ -ence, the scatter+