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ISSUES TO ADDRESS...
Structures of ceramic materials:
How do they differ from those of metals?
Point defects:
Ceramics
Chapter 12 - 1
How are they different from those in metals?
Impurities:
How are they accommodated in the lattice and how
do they affect properties?
Mechanical Properties:
What special provisions/tests are made for ceramic
materials?
Atomic bonding can be ionic or covalent, most have a
combination of the 2.
Most ceramics have both a metallic element and a non-
metallic one.
Oxides: SiO
2
, Al
2
O
3
Structure and Bonding
Chapter 12 - 2
Nitrides: Si
3
N
4
, AlN
Carbides: SiC
RecallthatelasticmodulusEisproportionaltointeratomic
bondforces(interatomicbondsarestretchedduringthe
elasticdeformation)
Typically:Eceramic>Emetals>Epolymers
Bonding:
-- Mostly ionic, some covalent.
-- % ionic character increases with difference in
electronegativity.
Large vs small ionic bond character:
Ceramic Bonding
CaF
2
: large
Chapter 12 - 3
Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University.
SiC: small
Ceramic Crystal Structures
Ifbondingisionic,atomscanbeconsideredascations and
anions.(e.g.NaCl Na
+
+Cl

).
Electroneutralitymustbemaintainedatalltimes.
Factorsthatdeterminecrystalstructure:
1) ElectricalChargeasions
2) l i i f i d i
Chapter 12 - 4
2) Relativesizeofcation andanion
Commonceramicstructures:
1) NaCl (RockSalt)
2) CaF
2
(Fluorite)
3) CsCl (CesiumChloride)
4) ZnS (ZincBlend)
5) BaTiO
3
(Perovskite)
Ionic Bonding & Structure
Size - Stable structures:
--maximize the # of nearest oppositel y charged neighbors.
- -
- -
+
unstable
- -
- -
+
stable
- -
- -
+
stable
Chapter 12 - 5
unstable
Charge Neutrality:
--Net charge in the
structure should
be zero.
--General form:
stable stable
CaF
2
:
Ca
2+
cation
F
-
F
-
anions
+
A
m
X
p
m, p determined by charge neutrality
Coordination # increases with
Coordination # and Ionic Radii
r
cation
r
anion
Coord
#
ZnS
(zincblende)
r
cation
r
anion
Issue: How many anions can you
arrange around a cation?
Chapter 12 - 6
2 < 0.155
0.155 - 0.225
0.225 - 0.414
0.414 - 0.732
0.732 - 1.0
3
4
6
8
linear
triangular
T
D
O
H
cubic
NaCl
(sodium
chloride)
CsCl
(cesium
chloride)
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On the basis of ionic radii, what crystal structure
would you predict for FeO?
Answer:
140 0
077 0
anion
cation
.
.
r
r
=
Example: Predicting Structure of FeO
Ionic radius (nm)
0.053
0.077
Cation
Al
3+
Fe
2+
3
Chapter 12 - 7
550 0. =
based on this ratio,
--coord # = 6
--structure = NaCl
0.069
0.100
0.140
0.181
0.133
Anion
Fe
3+
Ca
2+
O
2-
Cl
-
F
-
r
Na+
= 0.102 nm
r
Na+
/r
Cl-
= 0.564
r
Cl-
= 0.181 nm
2interpenetratingFCC
lattices.
1FCCwithanions(anda
cation@cubecenter)
1FCCwithcations(anda
anion@cubecenter
Coordination # for both
AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
Chapter 12 - 8
Coordination#forboth
cationandanion:6
2r
Cl- r
Na+
r
Na+
Howdoesa(interatomicdistance)relate
tor(radius):
a=2r
Cl
+2r
Na+
Whatisn?(#ofatomsperunitcell)
n=8=4Cl

+4Na
+
MgO and FeO
MgO and FeO also have the NaCl structure
O
2-
r
O
= 0.140 nm
Mg
2+
r
Mg
= 0.072 nm
Chapter 12 - 9
r
Mg
/r
O
= 0.514
So each oxygen has 6 neighboring Mg
2+
AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:
2simplecubiclatticesareinvolved;
onewithcationandonewithanion.
Coordination#forbothcationand
anion: 8
Chapter 12 - 10
939 . 0
181 . 0
170 . 0
Cl
Cs
= =

+
r
r
anion:8
Howdoesrrelatetoa?(Body
diagonal)
Whatisn?
n=2=1Cs
+
+1Cl

AX Crystal Structures
Zinc Blende structure
Forthiscrystalcrystalatomic
bondingisusuallyhighly
covalent.
FCCstructureforanions
Chapter 12 - 11
?? 529 . 0
140 . 0
074 . 0
2
2
O
Zn
H
O
r
r
= =

+
Ex: ZnO, ZnS, SiC
Coordination#forbothcation
andanion:4
n=8=4Zn
2+
+4S
2
AX
2
Crystal Structures
Fluorite structure
CalciumFluorite(CaF
2
):one
cationand2anions,sincethe
twohavedifferentcharge.
Oneunitcellhas8cubes.
Anionshavesimplecubic
Chapter 12 - 12
p
packingineachcube.
CN=8forcation,CN=4for
anion.
n=4Ca
2+
+8Cl

UO
2,
ThO
2
,ZrO
2
,CeO
2
Antifluorite structure
cations and
anions reversed
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ABX
3
Crystal Structures
Perovskite
Ex: complex oxide
BaTiO
3
Chapter 12 - 13
Adapted from Fig.
12.6, Callister 7e.
Ceramic Density Computation
A
A C
N V
) A A ( n
C
E + E '
=
Number of formula units/unit cell
Chapter 12 - 14
Volume of unit cell
Carbon Forms
Carbonispolymorphic
Diamond
tetrahedralcarbon
hard nogoodslipplanes
brittle cancutit
bondingindiamond(sp3)istotally
Chapter 12 - 15
g ( p ) y
covalent,verystronginteratomic
bonds.
Applications:
oftenmanmade usedfor
cuttingtoolsandpolishing
hardsurfacecoating tools,
medicaldevices,etc.
Carbon Forms
layerstructure
covalentbonding(sp
2
)in
plane
k d W l
- Graphite
Chapter 12 - 16
weakvanderWaals
forcesbetweenlayers
planesslideeasily,good
lubricant
Carbon Forms Graphitic derivatives
Chapter 12 -
A.K.Geim,Novoselov,K.S.NatureMater.2007, 6,183191.
17
Fullerenes CarbonNanotubes Graphenes
Ceramics are ionic crystalsit has two or more species of
anions and cations
Usually anion size > cation size
cations (metal ions: e.g. Ca
2+
, Al
3+
, Si
4+
etc.)
anions (O2-, Cl- etc.)
Defects in Ceramic Structures
Chapter 12 - 18
anions (O2 , Cl etc.)
Both vacancies and interstitial defects are possible
But electro-neutrality must be maintained at all times.
equal # of + and - charge from ions.
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Frenkel Defect
-- vacancy and interstitial pair, typically only occurs for cations.
Schottky Defect
--a paired set of cation and anion vacancies.
Defects in Ceramic Structures
Schottky
Chapter 12 - 19
Equilibrium concentration of defects
kT / Q
D
e ~

Adapted from Fig. 12.21, Callister
7e. (Fig. 12.21 is from W.G.
Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and
Properties of Materials, Vol. 1,
Structure, John Wiley and Sons,
Inc., p. 78.)
Schottky
Defect:
Frenkel
Defect
What if cation and anion have different charges
Defects in Ceramic Structures
Defect:Mgvacancy:Lossof2+charges
Electroneutrality must be maintained:
Example: MgCl
2
(Mg
2+
, Cl
-
)
Chapter 12 - 20
Electro neutralitymustbemaintained:
Possibilities:
(1)Mg
2+
interstitial
(2)2Cl

vacancies
In case of Fe, cation can change valence
Defects in Ceramic Structures
Defect:Fe
2+
vacancy(lossof2(+)charge)
Fe
2+
can change to Fe
3+
Example: FeO (O
2-
, Fe
3+
, Fe
2+
)
Chapter 12 - 21
Fe canchangetoFe
Tomaintainchargeneutrality,
twoneighbouring Fe
2+
changetoFe
3+
Create:Fe
1X
O
Resultsinelectricalconductivity,electron
hoppingbetweenatoms.
Impurities must also satisfy charge balance = Electroneutrality
Ex: NaCl
Substitutional cation impurity
Impurities
Na
+
Cl
-
Ca
2+
Na
+
cation
vacancy
Chapter 12 - 22
initial geometry Ca
2+
impurity resulting geometry
Na
+
Ca
2+
Substitutional anion impurity
initial geometry O
2-
impurity
O
2-
Cl
-
anion vacancy
Cl
-
resulting geometry
Impurities must also satisfy charge balance = Electroneutrality
Ex: Na
2
O added as impurity to FeO (host)
Impurities
Na
+
substituteforFe
2+
(lossof+1charge)
Tomaintainchargeneutrality,
Possibilities:
Chapter 12 - 23
(1) For2substitutions,createaO
2
vacancy()
(2) For2substitutions,createaFe
2+
interstitial
(3) For1substitution,addNa
+
interstitial
(4) For1substitution,oneFe
2+
becomesFe
3+
()
Impurities must also satisfy charge balance = Electroneutrality
Ex: Al
2
O
3
added as impurity to MgO (host)
Impurities
Al
3+
substituteforMg
2+
(createexcessof+1charge)
Tomaintainchargeneutrality,
Possibilities:
Chapter 12 - 24
Possibilities:
(1) For2substitutions,createaO
2
interstitial
(2) For2substitutions,createaMg
2+
vacancy()
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Ceramic materials have covalent & ionic bonding.
Structures are based on:
-- charge neutrality
-- maximizing # of nearest oppositely charged neighbors.
Structures may be predicted based on:
Summary
Chapter 12 - 25
Structures may be predicted based on:
-- ratio of the cation and anion radii.
Defects
-- must preserve charge neutrality
-- have a concentration that varies exponentially w/T.
Silicate Ceramics
Most common elements on earth are Si & O
TetrahedronwithSi
(4+)
in
thecenter.
SiObondmostlycovalent.
Basic Unit:
SiO
4
tetrahedron
4-
Si
4+
O
2-
Chapter 12 - 26
Silica(SiO
2
)canbeamorphousorcrystalline,SiO
2
is
polymorphic.
(SiO
4
)isthebasicunit(orbuildingblock)ofsilica
(amorphousorcrystalline).
Combine SiO
4
4-
tetrahedra by having them share
corners, edges, or faces
Silicates
Chapter 12 - 27
Crystalline Silica
Thereislongrangeorder,
atomsformregulararray,
atomsaregenerallymore
closelypackedthan
amorphoussilica.
D i 2 65 /
3
Chapter 12 - 28
SiO
2
(silica)structuresarequartz,crystobalite,&tridymite
ThestrongSiObondleadstoastrong,highmelting
material(1710C)
crystobalite
Density2.65g/cm
3
.
Amorphous Silica
Silicagels amorphousSiO
2
Si
4+
andO
2
notinwellorderedlattice
Nolongrangeorder.(Density
2.2g/cm
3
)
Charge balanced by H
+
(to form
Chapter 12 - 29
ChargebalancedbyH (toform
OH

)atdanglingbonds
veryhighsurfacearea>200m
2
/g
SiO
2
isquitestable,therefore
unreactive
makesgoodcatalystsupport
Glassisamorphous
Amorphousstructure
occursbyaddingimpurities
(Na
+
,Mg
2+
,Ca
2+
,Al
3+
)
Impurities:
(soda glass)
Si
4+
Na
+
O
2-
Silica Glass
Denseformofamorphoussilica
Chapter 13 - 30
Modifiers:e.g.Na
2
O,CaO,MgO,
PbO,whoseeffectistobreakup
the(SiO4)network.
(Note:networkformers:e.g.
Al
2
O
3
,B
2
O
3
)
(soda glass)
Macroscopiceffectofaddingmodifiers:1)Lowerviscosity;
2)lowermeltingtemperature,andthereforemakeglass
processingeasier.
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Glass Properties: Viscosity
Crystallinematerials,plasticdeformationoccursby
themotionofdislocation.
Amorphousmaterials,plasticdeformationdoesnot
occurbydislocationmotionasthereisnoregularatomic
structures.Thesematerialsdeformbyviscousflow.
Viscosityisameasureofnoncrystallinematerials
Chapter 13 - 31
Viscosity, q: relates shear stress and velocity gradient:
q has units of (Pa-s)
y
v
d
d
q = t
velocity gradient
dv
dy
t
t
glass dv
dy
resistancetodeformation
ViscositydecreaseswithT
ImpuritieslowerTdeform
Glass Viscosity vs. T and Impurities

s
]
10
14
strain point
fused silica: > 99.5 wt% SiO
2
soda-lime glass: 70% SiO
2
balance Na
2
O (soda) & CaO (lime)
Vycor: 96% SiO
2
, 4% B
2
O
3
borosilicate (Pyrex):
13% B
2
O
3
, 3.5% Na
2
O, 2.5% Al
2
O
3
Chapter 13 - 32
V
i
s
c
o
s
i
t
y

[
P
a

1
10
2
10
6
10
10
10
200 600 1000 1400 1800 T(C)
T
deform
: soft enough
to deform or work
annealing range
T
melt
strain point
Annealing:
--removes internal stress caused by uneven cooling.
Tempering:
--puts surface of glass part into compression
--suppresses growth of cracks from surface scratches.
--sequence:
Heat Treating Glass
further cooled
compression
before cooling
h t
surface cooling
cooler
Chapter 13 - 33
tension
compression
hot hot
cooler
--Result: surface crack growth is suppressed.
Specific volume (1/) vs Temperature (T):
Crystallinematerials:
crystallizeatmeltingtemp,Tm
haveabruptchange(discontinuity)in
spec.vol.atTm
Glass Properties
Specific volume
Supercooled
Liquid
Liquid
(disordered)
Chapter 13 - 34
Glasses(amorphous):
donotcrystallize
changeinslopeinspec.vol.curveat
glasstransitiontemperature,Tg
AtTg,materialtransformfromsoft
rubberystatetorigid,brittlestate.
Adapted from Fig. 13.6, Callister, 7e.
T
solid
T
m
Crystalline
(i.e., ordered)
T
g
Glass
(amorphous solid)
Glassesareamorphous:
nolongrangeorderedatomicarrangement
deformthroughviscousflow,butnotdislocationmotion
experiencedifferentspecificvolumevstemperaturebehaviour
comparedtocrystallinematerials
ImpuritiesinglasseslowerstheTm,Tg,Tdeform.
Summary
Chapter 12 - 35
p g , g,
Heattreating:Usedto
alleviateresidualstressfromcooling,
producefractureresistantcomponentsbyputting
surfaceintocompression.(temperedglass)