Chapter 12: Structures & Properties of Ceramics

Chapter 12: Structures & Properties of

Ceramics

ISSUES TO ADDRESS...
• How do the crystal structures of ceramic materials
differ from those for metals?
• How do point defects in ceramics differ from those
defects found in metals?
• How are impurities accommodated in the ceramic lattice?
• In what ways are ceramic phase diagrams different from
phase diagrams for metals?
• How are the mechanical properties of ceramics
measured, and how do they differ from those for metals?

Chapter 12 - 1

Atomic Bonding in Ceramics

• Bonding:
-- ______________________________________.
-- % ionic character __________ with difference in
electronegativity of atoms.
• Degree of ionic character may be large or small:
CaF2: large
SiC: small

Chapter 12 - 2

Ceramic Crystal Structures

Oxide structures
–  oxygen anions ________ than metal cations
–  close _______ oxygen in a _______ (usually ____)
–  cations fit into _______ sites among ________ ions

Chapter 12 - 3

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Chapter 12: Structures & Properties of Ceramics

Factors that Determine Crystal Structure

1. Relative sizes of ions – _________________________:
--maximize the # of ______________________________.
- - - - - -
+ + +
Adapted from Fig. 12.1,
Callister & Rethwisch 10e.
- - - - - -
________ ______ stable
2. Maintenance of
Charge Neutrality : F-
--_________________ CaF 2 : Ca 2+ +
cation anions
should be zero.
--Reflected in chemical F-
formula:
A m Xp
m, p values to achieve
charge neutrality Chapter 12 - 4

Coordination Number and Ionic Radii

r cation
• ___________ Number increases with r
anion
To form a ______ structure, how many anions can
surround around a cation?
r cation Coord. ZnS
r anion Number (zinc blende)
Adapted from Fig. 12.4,
< 0.155 2 linear Callister & Rethwisch 10e.

0.155 - 0.225 3 ________ NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 12.2,
Callister & Rethwisch 10e.

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 _____ Adapted from Fig. 12.3,
Adapted from Table 12.2, Callister & Rethwisch 10e.
Callister & Rethwisch 10e.
Chapter 12 - 5

Computation of Minimum Cation-Anion

Radius Ratio
•  Determine ________ rcation/ranion for an octahedral site
(C.N. = __)
2ranion + 2rcation = 2a

_________
2ranion + 2rcation = 2 2ranion

ranion + rcation = 2ranion rcation = ( 2 −1)ranion

rcation
= 2 −1= 0.414
ranion
Chapter 12 - 6

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Chapter 12: Structures & Properties of Ceramics

Bond Hybridization
Bond Hybridization is possible when there is significant
__________ bonding
–  ___________________________
–  For example for SiC
•  XSi = 1.8 and XC = 2.5

% ionic character = 100 {1-exp[-0.25(X Si − X C )2 ]} = 11.5%

•  ~ 89% __________ bonding
•  Both Si and C prefer sp3 hybridization
•  Therefore, for SiC, Si atoms occupy ______________ sites

Chapter 12 - 7

Example Problem: Predicting the Crystal

Structure of FeO
• On the basis of ionic radii, what _________________
would you predict for FeO?
Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069 = 0.550
Ca 2+ 0.100
based on this ratio,
-- coord # = __ because
Anion
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is ____
Cl - 0.181
F-
Data from Table 12.3,
0.133 Callister & Rethwisch 10e.

Chapter 12 - 8

Rock Salt Structure

Same concepts can be applied to ______ solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm

rCl = ______ nm

rNa/rCl = _________

∴  cations (Na+) prefer __________ sites

Adapted from Fig. 12.2,

Callister & Rethwisch 10e.

Chapter 12 - 9

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Chapter 12: Structures & Properties of Ceramics

MgO and FeO

MgO and FeO also have the NaCl structure
O2- rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = _________

∴  _________ prefer octahedral sites

Adapted from Fig. 12.2,

Callister & Rethwisch 10e.

So each Mg2+ (or Fe2+) _______ neighbor oxygen atoms

Chapter 12 - 10

AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende

Cesium Chloride structure:

r 0.170
Cs+
= = ______
r 0.181
Cl−

∴ Since 0.732 < ______ < 1.0,

______ sites preferred

Fig. 12.3, Callister & Rethwisch 10e.

So each Cs+ has ___ neighbor Cl-

Chapter 12 - 11

VMSE Screenshot – Zinc Blende Unit Cell

Chapter 12 - 12

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Chapter 12: Structures & Properties of Ceramics

AX2 Crystal Structures

Fluorite structure

•  Calcium _________ (CaF2)

•  Cations in _________ sites

•  UO2, ThO2, ZrO2, CeO2

•  _____________ structure –
positions of cations and
anions reversed

Fig. 12.5, Callister & Rethwisch 10e.

Chapter 12 - 13

ABX3 Crystal Structures

•  _________ structure

Ex: complex oxide

___________

Fig. 12.6, Callister &

Rethwisch 10e.

Chapter 12 - 14

Density Computations for Ceramics

Number of formula units/unit cell

nʹ(ΣAC + ΣAA )
ρ=
VC N A
___________ number
Volume of unit cell

ΣAC = sum of atomic weights of _______________________

ΣAA = sum of atomic weights of _______________________

Chapter 12 - 15

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Chapter 12: Structures & Properties of Ceramics

Silicate Ceramics
Most common _____________________________

Si4+

O2-

Figs. 12.9 & 12.10, Callister &

Rethwisch 10e crystobalite

•  SiO2 (silica) __________________ forms are quartz,

crystobalite, & tridymite
•  The strong Si-O bonds lead to a high ____________
temperature (1710ºC) for this material

Chapter 12 - 16

Silicates
Bonding of adjacent SiO44- accomplished by the
sharing of common _________________________

Adapted from Fig.

12.12, Callister &
Rethwisch 10e.
Mg2SiO4 Ca2MgSi2O7

Presence of cations such as Ca2+, Mg2+, & Al3+

1. maintain charge ______________, and
2. __________ bond SiO44- to one another
Chapter 12 - 17

Glass Structure
• Basic Unit: Glass is ___________ (__________)
4- • ____________ is SiO2 to which no
Si0 4 tetrahedron impurities have been added
Si 4+ • Other common _________ contain
O2 - impurity ions such as Na+, Ca2+,
Al3+, and B3+

• Quartz is _____________
Na +
SiO2:
Si 4+
O2 -

(soda glass)
Adapted from Fig. 12.11,
Callister & Rethwisch 10e.

Chapter 12 - 18

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Chapter 12: Structures & Properties of Ceramics

Layered Silicates
•  Layered ________ (e.g., clays, mica, talc)
–  SiO4 tetrahedra connected
together to form 2-D plane

•  A net negative charge is associated with

each (Si2O5)2- unit

•  Negative charge balanced by

_________ plane rich in positively
charged _________

Fig. 12.13, Callister

& Rethwisch 10e.

Chapter 12 - 19

Layered Silicates (cont)

•  Kaolinite clay _________ (Si2O5)2- layer with Al2(OH)42+
layer

Fig. 12.14, Callister &

Rethwisch 10e.

Note: Adjacent sheets of this type _________ bound to one

another by __________________________.
Chapter 12 - 20

Polymorphic Forms of Carbon

Diamond
–  tetrahedral bonding of
carbon
•  _____________________
•  _____________________
conductivity
–  large single crystals –
gem stones
–  small ________ – used to
grind/cut other materials
–  ____________ thin films
Fig. 12.16, Callister &
•  hard surface coatings – Rethwisch 10e.
used for cutting tools,
medical devices, etc.

Chapter 12 - 21

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Chapter 12: Structures & Properties of Ceramics

Polymorphic Forms of Carbon (cont)

____________
–  _______ structure – parallel __________ arrays of
carbon atoms

Fig. 12.17, Callister

& Rethwisch 10e.

–  weak van der Waal’s forces between layers

–  planes slide easily over one another -- good
lubricant
Chapter 12 - 22

Point Defects in Ceramics (i)

• Vacancies
-- vacancies exist in ___________ for both _____________________
• Interstitials
-- interstitials exist for ______________
-- interstitials are not normally observed for ___________________
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy
Fig. 12.18, Callister & Rethwisch 10e.
(From W.G. Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, John Wiley &
Sons, 1964. Reproduced with permission of
Janet M. Moffatt.)

Anion
Vacancy Chapter 12 - 23

Point Defects in Ceramics (ii)

• Frenkel Defect
-- ____________________________________.
• Shottky Defect
-- ____________________________________.

Shottky
Defect: Fig. 12.19, Callister & Rethwisch 10e.
(From W.G. Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, John Wiley &
Sons, 1964. Reproduced with permission of
Janet M. Moffatt.)

Frenkel
Defect

−QD / kT
• Equilibrium concentration of defects ∝e

Chapter 12 - 24

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Chapter 12: Structures & Properties of Ceramics

Imperfections in Ceramics
• ______________ (charge _________) must be maintained
when impurities are present
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
without impurity Ca 2+ impurity with impurity
• Substitutional anion impurity an ion vacancy
O2-

Cl - Cl -
without impurity O2- impurity with impurity
Chapter 12 - 25

Ceramic Phase Diagrams

MgO-Al2O3 diagram:

Fig. 12.23, Callister &

Rethwisch 10e.
[Adapted from B. Hallstedt,
“Thermodynamic Assessment
of the System MgO–Al2O3,” J.
Am. Ceram. Soc., 75[6], 1992,
p.1502. Reprinted by
° permission of the American
Ceramic Society.]

Chapter 12 - 26

Mechanical Properties
__________ materials are more ___________________.
Why is this so?
•  Consider ________________________________
–  In crystalline, by __________ motion
–  In highly ionic solids, dislocation motion is difficult
•  few ______________
•  resistance to motion of ions of like charge (e.g., anions)
past one another

Chapter 12 - 27

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Chapter 12: Structures & Properties of Ceramics

Flexural Tests – Measurement of Elastic

Modulus
• Room T behavior is usually ________, with _______ failure.
• ____________________ often used.
-- tensile tests are difficult for ________ materials.
cross section F
L/2 L/2 Adapted from Fig. 12.30,
Callister & Rethwisch 10e.
d R
b δ = midpoint
rect. circ.
deflection
• Determine ________________ according to:
F F L3
x E= (rect. cross section)
F δ 4bd 3
slope =
δ F L3
E= (circ. cross section)
δ δ 12π R 4
linear-elastic behavior
Chapter 12 - 28

Flexural Tests – Measurement of _________

Strength
• _____________ test to measure room-T flexural strength.
cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
location of max tension

• ___________ strength: • Typical values:

Material σ fs (MPa) E(GPa)
3Ff L
σ fs = (rect. _____________) Si nitride 250-1000 304
2bd 2 Si carbide 100-820 345
Al oxide 275-700 393
Ff L
σ fs = (circ. _____________) glass (soda-lime) 69 69
π R3 Data from Table 12.5, Callister & Rethwisch 10e.

Chapter 12 - 29

SUMMARY
• Interatomic bonding in ceramics is ionic and/or covalent.
• Ceramic crystal structures are based on:
-- maintaining charge neutrality
-- cation-anion radii ratios.
• Imperfections
-- Atomic point: vacancy, interstitial (cation), Frenkel, Schottky
-- Impurities: substitutional, interstitial
-- Maintenance of charge neutrality
• Room-temperature mechanical behavior – flexural tests
-- linear-elastic; measurement of elastic modulus
-- brittle fracture; measurement of flexural modulus

Chapter 12 - 30

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