KC22203 Material Technology

Chapter 10

Ceramic Materials

1
WHY STUDY Structures and Properties of Ceramics?

Some of the properties of ceramics may be

explained by their structures.
affirmation
For example:
hard
(a) The optical transparency of inorganic glass materials is due, in
part, to their noncrystallinity;
(b) the hydroplasticity of clays (i.e., development of plasticity upon the
addition of water) is related to interactions between water molecules
and the clay structures, and
(c) the permanent magnetic and ferroelectric behaviors of some
ceramic materials are explained by their crystal structures.

2
 Learning objectives
 After this lesson you should be able to do the following:
1. Sketch/describe unit cells for sodium chloride, cesium chloride, zinc blende, diamond cubic, fluorite, and
perovskite crystal structures. Do likewise for the atomic structures of graphite and a silica glass.
2. Given the chemical formula for a ceramic compound, calculate the ionic radii of its component ions,
3. Predict the crystal structure. How
many
4. Calculate the theoretical density of a compound given that it has a crystal structure.
5. Name and describe two different ionic point defects that are found in ceramic compounds.
6. Briefly explain why there is normally significant scatter in the fracture strength for identical specimens of
the same ceramic material.
7. Compute the flexural strength of ceramic rod specimens that have been bent to fracture in three-point
loading.
8. On the basis of slip considerations, explain why crystalline ceramic materials are normally brittle.
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 and
Ceramic Bonding plastic
polymer
covalent
• Bonding:
-- Mostly ionic, some covalent.
-- % ionic character increases with difference in
electronegativity.
• Large vs small ionic bond character:
CaF2: large
SiC: small

electronegativity
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 4
Cornell University.
 Ionic Bonding & Structure
1. Size - Stable structures:
--maximize the # of nearest oppositely charged neighbors.
- - - - - -
+ + +
Adapted from Fig. 12.1,
Callister 7e.
- - - - - -
unstable stable stable
• Charge Neutrality:
--Net charge in the F-
structure should CaF 2 : Ca 2+ +
cation anions
be zero.
F-
--General form: A m Xp
m, p determined by charge neutrality 5
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Coordination # and Ionic Radii mayhem
r cation
• Coordination # increases with r
anion

Zinc
r cation ZnS
r anion
Coord struiture (zincblende)
#
Adapted from Fig.
< 0.155 2 linear 12.4, Callister 7e.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 TD chloride)

IF
Adapted from Fig.
12.2, Callister 7e.

0.414 - 0.732 6 OH CsCl

(cesium
0.732 - 1.0 8 cubic chloride)
Adapted from Fig.
Adapted from Table 12.2, 12.3, Callister 7e.
Callister 7e. 6
 Example 1: Predicting Structure of FeO
• On the basis of ionic radii, what crystal structure
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 # = 6
Anion
--structure = NaCl
O2- 0.140
Cl - 0.181
F-
Data from Table 12.3,
0.133 Callister 7e. 7
 Rock Salt Structure
Same concepts can be applied to ionic solids in
general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

 cations prefer OH sites

Adapted from Fig.

12.2, Callister 7e.

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

Cesium Chloride structure:

rCs  0.170
  0.939
rCl 0.181

 cubic sites preferred

Adapted from Fig. So each Cs+ has 8 neighboring Cl-

12.3, Callister 7e.
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Crystal structure

10
 Ceramic Density Computation
Number of formula units/unit cell

n(AC  AA )

VC N A

mass / unitcell

volume / unitcell

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 Example 1

 Calculate the theoretical density of NiO given

that it has the rock salt crystal structure.

12
 Silicate Ceramics
Most common elements on earth are Si & O

Si4+

O2-

Adapted from Figs.

12.9-10, Callister 7e.
crystobalite
 SiO2 (silica) structures are quartz, crystobalite, & tridymite
 The strong Si-O bond leads to a strong, high melting
material (1710ºC)
 quite stable, therefore unreactive -makes good catalyst
support
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 Silicate Ceramics
Silica
 Silica gels - amorphous SiO2
 Si4+ and O2- not in well-ordered
lattice
 SiO2 is quite stable, therefore
unreactive
 makes good catalyst support

Adapted from Fig.

12.11, Callister 7e.

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 Silicate Ceramics
Silica Glass
 Noncrystalline solid, having a high degree of atomic
randomness
 Eg: Containers, Windows
 Silica glass added with other Oxides such as CaO and Na2O
 Cations are incorporated within and modify the SiO44-
 Borosilicate glass is the pyrex glass used in labs
 better temperature stability & less brittle than
sodium glass

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Silicate Ceramics
The Silicates-simple silicates
 Combine SiO44- tetrahedra by having them share
corners, edges, or faces

Adapted from Fig.

12.12, Callister 7e.
Mg2SiO4 Ca2MgSi2O7

 Cations such as Ca2+, Mg2+, & Al3+ act to neutralize

& provide ionic bonding
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 Silicate Ceramics
The Silicates-Layered Silicates
 Layered silicates (clay silicates)
 SiO4 tetrahedra connected
together to form 2-D plane

 Repeating unit formula: (Si2O5)2-

Adapted from Fig.
 So need cations to balance 12.13, Callister 7e.
charge =
 Eg: talc, micas, kaolinite clay 17
 The Silicates-Layered Silicates
 Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+ layer

Al2 (Si2O5)(OH)4

Adapted from Fig.

12.14, Callister 7e.

Note: these sheets loosely bound by van der Waal’s forces 18

 Carbon Forms
 Diamond
 tetrahedral carbon
 hard

 brittle

 large diamonds – jewelry

 small diamonds
 often man made - used for

cutting tools and polishing

 diamond films
 hard surface coat – tools,

medical devices, etc. Adapted from Fig.

12.15, Callister 7e.

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 Carbon Forms - Graphite
 layer structure – aromatic layers

Adapted from Fig.

12.17, Callister 7e.

 weak van der Waal’s forces between layers

 planes slide easily, good lubricant
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 Defects in Ceramic Structures
• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect: 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.)
Frenkel
Defect

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 Impurities
• Impurities must also satisfy charge balance = Electroneutrality
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
initial geometry Ca 2+ impurity resulting geometry

• Substitutional anion impurity anion vacancy

O2-

Cl - Cl -
initial geometry O2- impurity resulting geometry 22
 Ceramic Phase Diagrams
MgO-Al2O3 diagram:

Adapted from Fig.

12.25, Callister 7e.

23
 Mechanical Properties
We know that ceramics are more brittle than
metals. Why?
 Consider method of deformation
 slippage along slip planes
 in ionic solids this slippage is very difficult
 too much energy needed to move one anion
past another anion

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 Measuring Elastic Modulus
• Room T behavior is usually elastic, with brittle failure.
• 3-Point Bend Testing often used.
--tensile tests are difficult for brittle materials.
cross section F
L/2 L/2 Adapted from Fig. 12.32,
Callister 7e.
d R
b d = midpoint
rect. circ.
deflection
• Determine elastic modulus according to:
F F L3 F L3
x E= =
F d 4bd 3 d 12 p R4
slope =
d rect. circ.
cross cross
d section section
linear-elastic behavior 25
 Measuring Strength
• 3-point bend test to measure room T strength.
cross section F
L/2 L/2 Adapted from Fig. 12.32,
Callister 7e.
d R
b d = midpoint
rect. circ.
deflection
location of max tension

• Flexural strength: • Typ. values:

Material sfs (MPa) E(GPa)
1.5Ff L Ff L
s fs   Si nitride 250-1000 304
bd 2 pR3 Si carbide 100-820 345
F rect. Al oxide 275-700 393
Ff x glass (soda) 69 69
Data from Table 12.5, Callister 7e.

d 26
dfs
Measuring Strength

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 Application-Classification of Ceramics

Glasses Clay Refractories Abrasives Cements Advanced

products ceramics
-optical -whiteware -bricks for -sandpaper -composites engine
-composite -bricks high T -cutting -structural -rotors
reinforce (furnaces) -polishing -valves
-containers/ Adapted from Fig. 13.1 and discussion in
-bearings
household Section 13.2-6, Callister 7e.
-sensors

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 Group activities

Fabrication and Processing of

Ceramics

Fabrication and Fabrication and Powder Pressing

Processing of Processing of
Glasses Clay Products

Tape Casting

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 Group activities
1. Describe the process that is used to produce glass–ceramics.

2. Name the two types of clay products, and then give two examples of each.

3. Cite two important requirements that normally must be met by refractory

ceramics and abrasive ceramics.

4. Name and briefly describe four forming methods that are used to fabricate
glass pieces.

6. Briefly describe and explain the procedure by which glass pieces are
thermally tempered.

7. Briefly describe processes that occur during the drying and firing of clay-
based ceramic ware.

8. Briefly describe/diagram the sintering process of powder particle

aggregates.

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