ATOMIC BONDING IN

CERAMIC

Chapter 12 - 1

Chapter 12 - 2

Figure 1.7 Periodic table with ceramic compounds indicated by a combination of one or more
metallic elements (in light color) with one or more nonmetallic elements (in dark color). Note
that elements silicon (Si) and germanium (Ge) are included with the metals in this figure but
were not included in the periodic table shown in Figure 1.4. They are included here because,
in elemental form, Si and Ge behave as semiconductors (Figure 1.16). Elemental tin (Sn) can
be either a metal or a semiconductor, depending on its crystalline structure.
Metallic Elements

Nonmetallic ceramic forming

elements

Ceramics are usually oxides. However, silicon nitride (Si3N4) is an important nonoxide ceramic
used in a variety of structural applications. Some ceramics are chemical compounds made up
of one of the five nonmetallic materials, C, N, O, P or S, shaded with dark blue color in figure
1.7. Very many variety of ceramic materials can be formed.
(C, N, P, S are forming none-oxide ceramics with metallic elements.)
12 (Now, Si and Ge are included as metallic elements in this classification, because they formChapter
ceramics.)

Atomic Bonding in Ceramics

Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.

Degree of ionic character may be large or small:

CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (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
Chapter 12 - 4
Cornell University.)

IONIC BONDING

Occurs between + and - ions.

Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl

Chapter 12 - 8

Characteristics of Ionic Bonding

1. medium high melting point (600 2000 C)
2. medium high boiling points
3. hard and brittle
4. nonconductor of electricity
5. poor conductor of heat

Chapter 12 -

EXAMPLES: IONIC BONDING

Predominant bonding in Ceramics

NaCl
MgO
CaF2
CsCl

H
2.1
Li
1.0

Be
1.5

Na
0.9

Mg
1.2

K
0.8

Ca
1.0

Rb
0.8

He
O
F
3.5 4.0

Ne
-

Cl
3.0

Ar
-

Br
2.8

Kr
-

Sr
1.0

I
2.5

Xe
-

Cs
0.7

Ba
0.9

At
2.2

Rn
-

Fr
0.7

Ra
0.9

Ti
1.5

Cr
1.6

Give up electrons

Fe
1.8

Ni
1.8

Zn
1.8

As
2.0

Acquire electrons

Adapted from Fig. 2.7, Callister 6e. (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.
Chapter 12 - 9

COVALENT BONDING
Requires shared electrons
Example: CH4

C: has 4 valence e,
needs 4 more
H: has 1 valence e,
needs 1 more
Electronegativities
are comparable.
Adapted from Fig. 2.10, Callister 6e.

Chapter 12 - 10

Characteristics of Covalent Bonding

1. very low melting point (-370 to 300

C)
2. very low boiling point
3. soft
4. nonconductor of electricity
5. poor conductor of heat

Chapter 12 -

EXAMPLES: COVALENT BONDING

H2
H
2.1
Li
1.0

Be
1.5

Na
0.9
K
0.8

Mg
1.2
Ca
1.0

Rb
0.8

Sr
1.0

Cs
0.7

Ba
0.9

Fr
0.7

Ra
0.9

column IVA

H2O

C(diamond)

SiC
Ti
1.5

Cr
1.6

Fe
1.8

F2
He
-

O
2.0

C
2.5

Ni
1.8

Zn
1.8

Ga
1.6

Si
1.8
Ge
1.8

As
2.0

Sn
1.8
Pb
1.8

F
4.0

Ne
-

Cl
3.0
Br
2.8

Ar
Kr
-

I
2.5

Xe
-

At
2.2

Rn
-

Cl2

GaAs

Adapted from Fig. 2.7, Callister 6e. (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.

Molecules with nonmetals

Molecules with metals and nonmetals
Elemental solids (RHS of Periodic Table)
Compound solids (about column IVA)

Chapter 12 - 11

Ceramic Phase Diagrams

MgO-Al2O3 diagram:

Adapted from Fig.

12.25, Callister &
Rethwisch 8e.

Chapter 12 - 11

fig_12_26

Chapter 12 - 12

CERAMIC CRYSTAL STRUCTURES

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13

Ceramic Crystal Structures

Oxide structures
oxygen anions larger than metal cations
close packed oxygen in a lattice (usually FCC)
cations fit into interstitial sites among oxygen ions

Chapter 12 - 14

Factors that Determine Crystal Structure

1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors.

unstable
2. Maintenance of
Charge Neutrality :

stable

--Net charge in ceramic

should be zero.
--Reflected in chemical
formula:

CaF 2 :

Adapted from Fig. 12.1,

Callister & Rethwisch 8e.

+
-

stable

Ca 2+ +
cation

Fanions
F-

A m Xp
m, p values to achieve charge neutrality
Chapter 12 - 15

Coordination # and Ionic Radii

r cation
Coordination # increases with r
anion

To form a stable structure, how many anions can

surround around a cation?
r cation
r anion
< 0.155

Coord
#
linear
2
triangular

0.155 - 0.225

0.225 - 0.414

4 tetrahedral

0.414 - 0.732

6 octahedral

0.732 - 1.0

Adapted from Table 12.2,

Callister & Rethwisch 8e.

cubic

ZnS
(zinc blende)
Adapted from Fig. 12.4,
Callister & Rethwisch 8e.

NaCl
(sodium
chloride)

Adapted from Fig. 12.2,

Callister & Rethwisch 8e.

CsCl
(cesium
chloride)
Adapted from Fig. 12.3,
Callister & Rethwisch 8e.
Chapter 12 - 16

Chapter 12 - 17

Computation of Minimum Cation-Anion

Radius Ratio
Determine minimum rcation/ranion for an octahedral site
(C.N. = 6)
2ranion 2rcation = 2a

a = 2ranion

2ranion 2rcation = 2 2ranion

ranion rcation = 2ranion

rcation = ( 2 1)ranion

rcation
= 2 1 = 0.414
ranion
Chapter 12 - 18

Chapter 12 - 19

Chapter 12 - 20

Bond Hybridization
Bond Hybridization is possible when there is significant
covalent bonding
hybrid electron orbitals form
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% covalent bonding
Both Si and C prefer sp3 hybridization
Therefore, for SiC, Si atoms occupy tetrahedral sites

Chapter 12 - 21

Example Problem: Predicting the Crystal

Structure of FeO
On the basis of ionic radii, what crystal structure
would you predict for FeO?
Cation Ionic radius (nm)
Al 3+
0.053
Fe 2+
0.077
Fe 3+
0.069
Ca 2+
0.100
Anion
O2Cl F-

Answer:

rcation 0.077
=
ranion 0.140
= 0.550
based on this ratio,
-- coord # = 6 because

0.140
0.181
0.133

0.414 < 0.550 < 0.732

-- crystal structure is NaCl
Data from Table 12.3,
Callister & Rethwisch 8e.
Chapter 12 - 22

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 (Na+) prefer octahedral sites

Adapted from Fig. 12.2,

Callister & Rethwisch 8e.

Chapter 12 - 23

MgO and FeO

MgO and FeO also have the NaCl structure
O2-

rO = 0.140 nm

Mg2+

rMg = 0.072 nm

rMg/rO = 0.514
cations prefer octahedral sites
Adapted from Fig. 12.2,
Callister & Rethwisch 8e.

So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms

Chapter 12 - 24

EXAMPLE OF CRYSTAL STRUCTURE

Rock salt structure(AX)(NaCl )

Fluorite structure(AX2)(CaF2)

Perovskite structure(ABX3)(BaTiO3) Spinel structure(AB2X4)(MgAl2O4)

http://www.eng.uwo.ca/es021/ES021b_2007/Lecture%20Notes/Chap%2012-13%20SN%20-%20Ceramics.pdf

16.03.2015

25

EXAMPLE OF CRYSTAL STRUCTURE

16.03.2015

AX Crystal Structures
AXType Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:

rCs
rCl

0.170
= 0.939
0.181

Since 0.732 < 0.939 < 1.0,

cubic sites preferred
Adapted from Fig. 12.3,
Callister & Rethwisch 8e.

So each Cs+ has 8 neighbor Cl-

Chapter 12 - 27

AX2 Crystal Structures

Fluorite structure
Calcium Fluorite (CaF2)
Cations in cubic sites
UO2, ThO2, ZrO2, CeO2
Antifluorite structure
positions of cations and
anions reversed
Adapted from Fig. 12.5,
Callister & Rethwisch 8e.
Chapter 12 - 28

ABX3 Crystal Structures

Perovskite structure
Ex: complex oxide
BaTiO3

Adapted from Fig. 12.6,

Callister & Rethwisch 8e.

Chapter 12 - 29

VMSE: Ceramic Crystal Structures

Chapter 12 - 30

Density Computations for Ceramics

Number of formula units/unit cell

n(AC AA )
=
VC N A

Avogadros number

Volume of unit cell

AC = sum of atomic weights of all cations in formula unit

AA = sum of atomic weights of all anions in formula unit

Chapter 12 - 31

Chapter 12 - 32

Chapter 12 - 33

Silicate Ceramics
Most common elements on earth are Si & O

Si4+
O2Adapted from Figs.
12.9-10, Callister &
Rethwisch 8e

crystobalite

SiO2 (silica) polymorphic forms are quartz,

crystobalite, & tridymite
The strong Si-O bonds lead to a high melting
temperature (1710C) for this material
Chapter 12 - 34

Silicates
Bonding of adjacent SiO44- accomplished by the
sharing of common corners, edges, or faces

Mg2SiO4

Ca2MgSi2O7

Adapted from Fig.

12.12, Callister &
Rethwisch 8e.

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

1. maintain charge neutrality, and
2. ionically bond SiO44- to one another
Chapter 12 - 35

Chapter 12 - 36

Glass Structure
Basic Unit:
4Si0 4 tetrahedron
Si 4+
O2 -

Quartz is crystalline
SiO2:

Glass is noncrystalline (amorphous)

Fused silica is SiO2 to which no
impurities have been added
Other common glasses contain
impurity ions such as Na+, Ca2+,
Al3+, and B3+
Na +
Si 4+
O2 -

(soda glass)
Adapted from Fig. 12.11,
Callister & Rethwisch 8e.
Chapter 12 - 37

Layered Silicates
Layered silicates (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
adjacent plane rich in positively
charged cations

Adapted from Fig.

12.13, Callister &
Rethwisch 8e.
Chapter 12 - 38

Layered Silicates (cont.)

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

Adapted from Fig. 12.14,

Callister & Rethwisch 8e.

Note: Adjacent sheets of this type are loosely bound to

one another by van der Waals forces.

Chapter 12 - 39

Polymorphic Forms of Carbon

Diamond
tetrahedral bonding of
carbon
hardest material known
very high thermal
conductivity

large single crystals

gem stones
small crystals used to
grind/cut other materials
diamond thin films
hard surface coatings
used for cutting tools,
medical devices, etc.

Adapted from Fig. 12.15,

Callister & Rethwisch 8e.

Chapter 12 - 40

Polymorphic Forms of Carbon (cont)

Graphite
layered structure parallel hexagonal arrays of
carbon atoms

Adapted from Fig.

12.17, Callister &
Rethwisch 8e.

weak van der Waals forces between layers

planes slide easily over one another -- good
lubricant
Chapter 12 - 41

Polymorphic Forms of Carbon (cont)

Fullerenes and Nanotubes
Fullerenes spherical cluster of 60 carbon atoms, C60
Like a soccer ball
Carbon nanotubes sheet of graphite rolled into a tube
Ends capped with fullerene hemispheres

Adapted from Figs.

12.18 & 12.19, Callister
& Rethwisch 8e.

Chapter 12 - 42

Imperfections in Ceramics
Electroneutrality (charge balance) must be maintained

when impurities are present

Cl Ex: NaCl Na +
Substitutional cation impurity

cation
vacancy

Ca 2+
Na +
Na +
without impurity

Ca 2+ impurity

Substitutional anion impurity

Ca 2+
with impurity
an ion vacancy

O2-

without impurity

Cl Cl O2- impurity

with impurity

Chapter 12 - 43

Point Defects in Ceramics (i)

Vacancies
-- vacancies exist in ceramics for both cations and anions
Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites

Cation
Interstitial
Cation
Vacancy

Anion
Vacancy

Adapted from Fig. 12.20, Callister

& Rethwisch 8e. (Fig. 12.20 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.)
Chapter 12 - 44

Point Defects in Ceramics (ii)

Frenkel Defect
-- a cation vacancy-cation interstitial pair.
Shottky Defect
-- a paired set of cation and anion vacancies.
Shottky
Defect:

Adapted from Fig.12.21, Callister

& Rethwisch 8e. (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

Equilibrium concentration of defects

e QD /kT
Chapter 12 - 45

Chapter 12 - 46

Chapter 12 - 47

Chapter 12 - 48

Chapter 12 - 49