Chapter 13: Structure & Properties of Ceramic Materials

Issues to address... • Structures of ceramic materials
How do they differ from metals?

Ceramic Bonding
• Bonding
Mostly ionic, some covalent %ionic character ↑ as difference in electronegativities ↑

• Large vs small ionic bond character:
CaF2: large SiC: small
H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7 He Be 1.5 Mg 1.2

• Point Defects
How do they differ from metals?

• Impurities
How are they accommodated in the lattice?

C 2.5 Si 1.8
Ti 1.5 Cr 1.6 Fe 1.8 Ni 1.8 Zn 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 -

Ca 1.0
Sr 1.0 Ba 0.9 Ra 0.9

• Mechanical Properties
How are they measured?
Anderson 205- 13-1

Table of Electronegativities
Anderson 205- 13-2

Ionic Bonding and Structure
• Charge Neutrality
Net charge in the structure should be zero. General form: AmXp m, p determined by charge neutrality

Coordination Number and Ionic Radii
Fanions Fr • Coordination # increases with cation Issue: How many anions can you arrange around a cation? rcation Coord # ranion < .155 .155-.225 .225-.414 .414-.732 .732-1.0 8
Table 13.2, Callister

CaF2:

Ca2+ + cation

ranion

ZnS (zincblende)

2 3 4 6 NaCl (sodium chloride) CsCl (cesium chloride)
Anderson 205- 13-4

• Stable structures
maximize the # of nearest oppositely charged neighbors

-

+

-

-

+

-

-

+ -

unstable

stable

stable
Anderson 205- 13-3

Example
• On the basis of ionic radii, what crystal structure would you predict for FeO?
Ionic Radius (nm) Cation Al3+ Fe2+ Fe3+ Ca2+ Anion O2ClF0.053 0.077 0.069 0.100

AmXp Structures
Example: CaF2

• •

# Ca2+ ions = 1/2 # F- ions

rcation 0.100 = ≈ 0.8 ⇒ coord # = 8 ⇒CsCl structure ranion 0.133

rcation 0.077 = ranion 0.140 = 0.550
⇒ coord # = 6 ⇒ NaCl structure

Result: CsCl structure w/only 1/2 cation sites occupied

0.140 0.181 0.133

Table 13.3, Callister

Anderson 205- 13-5

Figure 13.5, Callister

Anderson 205- 13-6

Defects in Ceramic Structures
• Frenkel Defect:
a cation is out of place

• Impurites must also satisfy charge balance • Ex: NaCl Na+ Cl• Substitutional cation impurity
Ca2+ Na+ Na+ initial geometry Ca2+ impurity O2Ca2+ resulting geometry
anion vacancy cation vacancy

Impurities

• Shottky Defect:
a paired set of cation and anion vacancies

Shottky Defect:
Figure 13.20, Callister

• Substitutional Anion impurity

• # defects ∝ e

−Q

D /kT

Frenkel Defect
Anderson 205- 13-7

initial geometry

ClCl2- impurity O

resulting geometry
Anderson 205- 13-8

Mechanical Properties-I
• Room T: Elastic and brittle • 3-point Bend Test
-standard tension tests are difficult here! cross section d b rect. R circ. L/2 cross section d b rect. R circ.

Mechanical Properties-II
• Room T test to failure
L/2

F

L/2

F

L/2

δ= midpoint σm
location of max tension

δ= midpoint
F L3 δ 4bd3
rect. cross section

σm

deflection

• Elastic modulus, E = F
x
slope =

=

F

L3

deflection

• Flexural strength (σfs)= σm(at failure) =
Material σfs(MPa) E(GPa)
300 430 390 69 silicon nitride700-1000 silicon carbide 550-860 aluminum oxide 275-550 soda-lime glass 69

1.5FmaxL bd2
rect. cross section Fmax

δ 12πR 4
circ. cross section

F L = max 3 πR

circ. cross section

F δ

F

x
δmax

linear-elastic behavior

δ

Anderson 205- 13-9

selected values, Table 13.5, Callister

δ

Anderson 205- 13-10

Mechanical Properties-III
• Elevated T (T > 0.4Tmelt) Tensile Test creep test σ
x

ε

σ

slope = εss = steady-state creep rate

.

time
• Generally, εss
. ceramics

< εss

. metals

Anderson 205- 13-11

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