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
 Factors that Determine Crystal Structure
1. Relative sizes of ions – ________________________:
--maximize the # of ____________________________.
- - - - - -
+ + +
Adapted from Fig. 12.1,
Callister & Rethwisch 9e.
- - - - - -
________ ______ 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 9e.

0.155 - 0.225 3 _______ NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 12.2,
Callister & Rethwisch 9e.

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 9e.
Callister & Rethwisch 9e.
Chapter 12 - 5
 Computation of Minimum Cation-Anion
Radius Ratio
• Determine ________ rcation/ranion for an octahedral site
(C.N. = __)

_________
_
2ranion + 2rcation = 2 2ranion

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

rcation
= 2 - 1 = 0.414
ranion
Chapter 12 - 6
 Bond Hybridization
Bond Hybridization is possible when there is significant
____________ bonding
– ____________________________
– For example for SiC
• XSi = 1.8 and XC = 2.5

• ~ 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
Data from Table 12.3,
F- 0.133 Callister & Rethwisch 9e.

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 9e.

Chapter 12 - 9
 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 9e.

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:

 Since 0.732 < ____ < 1.0,

_____ sites preferred

Fig. 12.3, Callister & Rethwisch 9e.

So each Cs+ has __ neighbor Cl-

Chapter 12 - 11
 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 9e.

Chapter 12 - 12
 ABX3 Crystal Structures
• ___________ structure

Ex: complex oxide

_________

Fig. 12.6, Callister &

Rethwisch 9e.

Chapter 12 - 13
VMSE Screenshot – Zinc Blende Unit Cell

Chapter 12 - 14
Density Computations for Ceramics

Number of formula units/unit cell

__________ number
Volume of unit cell

= sum of atomic weights of ____________________

= sum of atomic weights of ____________________

Chapter 12 - 15
 Silicate Ceramics
Most common ___________________________

Si4+

O2-

Figs. 12.9 & 12.10, Callister &

Rethwisch 9e 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 9e.
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 9e.

Chapter 12 - 18
 Layered Silicates
• Layered ______ (e.g., clays, mica, talc)
– SiO4 ___________ 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 9e.

Chapter 12 - 19
 Layered Silicates (cont)
• Kaolinite clay _________ (Si2O5)2- layer with Al2(OH)42+
layer

Fig. 12.14, Callister &

Rethwisch 9e.

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 9e.
used for cutting tools,
medical devices, etc.

Chapter 12 - 21
Polymorphic Forms of Carbon (cont)
____________
– _________ structure – parallel ________ arrays of
carbon atoms

Fig. 12.17, Callister

& Rethwisch 9e.

– 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 9e.
(From W.G. Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, p.78. Copyright
©1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley and
Sons, Inc.)

Anion
Vacancy Chapter 12 - 23
 Point Defects in Ceramics (ii)
• Frenkel Defect
-- ____________________________________.
• Shottky Defect
-- ____________________________________.
Shottky
Defect: Fig. 12.19, Callister & Rethwisch 9e.
(From W.G. Moffatt, G.W. Pearsall, and J.
Wulff, The Structure and Properties of
Materials, Vol. 1, Structure, p.78. Copyright
©1964 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley and
Sons, Inc.)

Frenkel
Defect

• Equilibrium concentration of defects

Chapter 12 - 24
 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 9e.
[Adapted from B. Hallstedt,
“Thermodynamic Assessment
of the System MgO–Al2O3,” J.
Am. Ceram. Soc., 75[6], 1502
(1992). Reprinted by
 permission of the American
Ceramic Society.]

Chapter 12 - 26
 Mechanical Properties
___________ materials are more brittle than _________.
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
 Flexural Tests – Measurement of Elastic
Modulus
• Room T behavior is usually _______, with _______ failure.
• _____________________ often used.
-- tensile tests are difficult for ________ materials.
cross section F Adapted from Fig. 12.30,
L/2 L/2 Callister & Rethwisch 9e.
d R
b δ = midpoint
rect. circ.
deflection
• Determine ________________ according to:
F
x (rect. cross section)
F
slope =
δ
(circ. cross section)
δ
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 Adapted from Fig. 12.30,
Callister & Rethwisch 9e.
d R
b δ = midpoint
rect. circ.
deflection
location of max tension

• __________ strength: • Typical values:

Material σ fs (MPa) E(GPa)
(rect. ____________) Si nitride 250-1000 304
Si carbide 100-820 345
Al oxide 275-700 393
(circ. ____________) glass (soda-lime) 69 69
Data from Table 12.5, Callister & Rethwisch 9e.

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