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CERAMICS

Ceramics comesfromKeramikos. Keramikosmeansaburntmaterial Atomicbondingisionic tocovalent DependsonElectronegativity

( X A X B )2 x ( 100 %) 4 1 e

%ioniccharacter =

whereXA &XB areElectronegativities

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Ionic character of ceramics

CERAMICBONDING
Bonding: --Mostly ionic, some covalent. --% ionic character increases with difference in electronegativity.
Large vs small ionic bond character:

H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7

CaF2: large
Be 1.5 Mg 1.2

He -

SiC: small
Ti 1.5 Cr 1.6 Fe 1.8 Ni 1.8 Zn 1.8

Ca 1.0
Sr 1.0 Ba 0.9 Ra 0.9

C 2.5 Si 1.8
As 2.0

F 4.0
Cl 3.0 Br 2.8 I 2.5 At 2.2

Ne Ar Kr Xe Rn 2

Table of Electronegativities

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CERAMICS
Comprising of Metallic and non-metallic elements Metallic elements +ve Charge CATION Non-metallic elements -ve Charge ANION

Characteristics influence Ceramic Structure

1) Charge Neutrality: Charge in the structure Should be neutral

Generalform:

CaF2:

Ca2+ + cation

Fanions F-

2) Stability :--Size (or) Radius ratio

Cation size (rc ) < Anion Size (ra) rcation ranion < 1 Stabile structure is form when anions surrounds the cation has in contact (or) touch.

+ stable

+ stable

unstable

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Coordinate number : Number of anions nearest to cation

Coordinate number depends on radius ratio Size of the ion depends on : 1) Coordinate number 2) Charge on ion

Determineminimumrcation/ranion forC.N.=6
2ranion + 2rcation = 2a

CationSiteSize

a = 2ranion

2ranion + 2rcation = 2 2ranion

ranion + rcation = 2ranion

rcation = ( 2 1)ranion

rcation = 0 .414 ranion

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ForCN=8

Ceramic Systems => Are equal Crystal Structure

NaCl R. Ratio = 0.563 (0.414 to 0.732) CN = 6 Octahedral FCC (Interpenetrating)

Nacl or Rock salt structure

Other Eg: MgO, MnS, LiF, FeO

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CsCl R. Ratio = 0.9392 (0.732 to 1 ) CN = 8 Not BCC : Cubic

Cesium Chloride structure

ZnS R. Ratio = 0.4021 (0.225 to .414) CN = 4 Tetrahedral FCC anion Tetrahedron cationes Zink Blend or Sphalerite

Other Ceramics : SiC, ZnTe

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COORDINATIONANDIONICRADII
rcation ranion < .155 .155-.225 .225-.414 .414-.732 .732-1.0 Coord # 2 3 4 6 8 NaCl (sodium chloride) CsCl (cesium chloride) ZnS (zincblende)

If Charge on iones are not same

Crystal Structure

AX2 = CaF2 R. Ratio = 0.75 (0.732 to 1) CN = 8 Anion (F) corners Cation (Ca) cube center Similar to CsCl Fluorite Structure Other Ceramics : ZrO2, UO2, PuO2, ThO2

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Crystal Structure More than 1 Cation BaTiO3

Perovskite Structure ABX3

Other Ceramics : CuFeS2

CommonCeramiccrystalstructures
Structure Name Sodium Chloride Cesium Chloride Zink Blend (Sphalerite) Fluorite Structure Perovskite Structure Type AX AX AX AX2 ABX3 Anion Packing FCC Simple Cubic FCC Simple Cubic FCC Co-ordination Anion Example no: Cation 6 8 4 8 12(A) , 6(B) 6 8 4 4 6 Nacl, MgO,Feo CsCl ZnS, SiC CaF2, ZnS BaTiO3

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(111) Plane in FCC- NaCl

Each anion share 1 Octahedral 2 tetrahedral Positions

On the basis of ionic radii, what crystal structure

would you predict for FeO?

EX:PREDICTINGSTRUCTUREOFFeO
Answer:

Cation Ionic radius (nm) 0.053 Al3+ 0.077 Fe2+ 0.069 Fe3+ 0.100 Ca2+ Anion O2ClF-

r cation 0.077 = r anion 0.140 = 0.550

(0.414 to 0.732) based on this ratio, --coord # = 6 --structure = NaCl

0.140 0.181 0.133

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4.35]inBeOBe2+ =0.035nma)InterstitialsiteBeoccupies? b)FractionofsitesoccupiedbyBe?

Note : Each onion spear having one octahedral and 2 Tetrahedral sites exists in crystal.

CeramicDensityComputation
Number of formula units/unit cell

n( AC + AA ) VC N A
Volume of unit cell

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4.38)CalculatetheoreticalDensityofNiOifitis arocksaltstructure

4.32

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CarbonForms
Polymorphic form and amorphous form Not fall any type

Carbon Phase diagram

CarbonForms Graphite
layerstructure aromaticlayers

weakvanderWaalsforcesbetweenlayers planesslideeasily,goodlubricant

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Layered Structure Unit cell

Electrodes in Electric Furnaces. Rocket Nozzles. Refractories.

Diamond
tetrahedralcarbon
hard nogoodslipplanes brittle cancutit

largediamonds jewelry smalldiamonds

oftenmanmade usedfor cuttingtoolsandpolishing

diamondfilms
hardsurfacecoat tools,medical devices,etc.

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Synthetic diamond
HTHP Chemical Vapor Deposition (CVD)

Large & Natural Diamonds

Rough Diamonds

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Precession Diamond

CarbonForms Fullerenes,Nanotubes,Graphene
Fullerenesorcarbonnanotubesorgraphene
wrapthegraphitecurvingintoballortubeorsheets Buckminister fullerenes
LikeasoccerballC60

Fullerenes BuckyBall 0D

C Nanotubes 1D

Graphene 2D

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