Ceramic Bonding

Chapter 13:
Structure & Properties of Ceramic
Materials

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

Issues to address...

Large vs small ionic bond character:

CaF2: large

Structures of ceramic materials

SiC: small

How do they differ from metals?

H
2.1
Li
1.0

Point Defects
How do they differ from metals?

Impurities
How are they accommodated in the lattice?

Mechanical Properties
How are they measured?

He
-

C
2.5
Si
1.8

Be
1.5

CaF2:

Ca2+ +
cation

Fanions
F-

General form: AmXp

m, p determined by charge neutrality

Stable structures
maximize the # of nearest oppositely charged neighbors

unstable

stable

Cl
3.0

Ar
-

Br
2.8

Kr
-

Mg
1.2

K
0.8

Ca
1.0

Rb
0.8

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

Fe
1.8

Ni
1.8

As
2.0

Zn
1.8

Table of Electronegativities
Anderson 205- 13-2

Coordination Number and Ionic Radii

Ionic Bonding and Structure

Net charge in the
structure should be zero.

Ne
-

Na
0.9

Anderson 205- 13-1

Charge Neutrality

F
4.0

stable
Anderson 205- 13-3

r
Coordination # increases with cation
Issue: How many anions
can you arrange around a cation?
rcation
Coord #
ranion
< .155

ZnS
(zincblende)

.155-.225

.225-.414

.414-.732

.732-1.0

ranion

8
Table 13.2, Callister

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

AmXp Structures

Example
On the basis of ionic radii, what crystal structure
would you predict for FeO?
Ionic Radius (nm)
Cation
Al3+
Fe2+
Fe3+
Ca2+

Example: CaF2

0.053
0.077
0.069
0.100

rcation 0.077
=
ranion 0.140

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

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

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

= 0.550
coord # = 6

Anion
O2ClF-

NaCl structure

0.140
0.181
0.133

Table 13.3, Callister

Anderson 205- 13-5

Defects in Ceramic Structures

Frenkel Defect:

Figure 13.5, Callister

Impurities

Impurites must also satisfy charge balance

Ex: NaCl Na+
Cl Substitutional cation impurity

a cation is out of place

Shottky Defect:

Na+

Shottky
Defect:
Figure 13.20, Callister

D /kT

cation
vacancy

Ca2+

a paired set of cation and anion vacancies

# defects e

Anderson 205- 13-6

Frenkel
Defect
Anderson 205- 13-7

Na+
initial geometry

Ca2+ impurity

Substitutional Anion impurity

O2-

initial geometry

ClCl2O impurity

Ca2+
resulting geometry
anion vacancy

resulting geometry
Anderson 205- 13-8

Mechanical Properties-I

Mechanical Properties-II

Room T: Elastic and brittle

3-point Bend Test

Room T test to failure

cross section

-standard tension tests are difficult here!

cross section
d
b
rect.

b
rect.

L/2

L/2

= midpoint

circ.

= midpoint

circ.

x
slope =

L3

4bd3
rect.
cross
section

L3

deflection

Material

circ.
cross
section

silicon nitride700-1000
silicon carbide 550-860
aluminum oxide 275-550
soda-lime glass 69

Anderson 205- 13-9

Mechanical Properties-III
Elevated T (T > 0.4Tmelt) Tensile Test

creep test
x

slope = ss = steady-state creep rate

time
. ceramics

Generally, ss

. metals

< ss

Anderson 205- 13-11

Flexural strength (fs)= m(at failure) =

12R 4

linear-elastic behavior

deflection

location of max tension

Elastic modulus, E =
F

L/2

L/2

fs(MPa)

E(GPa)
300
430
390
69

selected values,
Table 13.5, Callister

1.5FmaxL
bd2
rect. cross
section
Fmax

F
L
= max
3
R

circ. cross
section

x
max

Anderson 205- 13-10

Taxonomy of Ceramics

Chapter 14:
Applications and Processing of
Ceramics

Glasses

Issues to address...

Clay Refractories Abrasives Cements Advanced

products
ceramics

optical
whiteware bricks for
high T
reinforcement bricks
(furnaces)
containers/
household

How do we classify ceramics?

How is processing different than for metals?

sandpaper composites engine

cutting
structural
-rotors
polishing
-valves
-bearings

Properties

-sensors

Tmelt: Moderate for glasses, large for other ceramics.

Toughness, ductility: Small

What are some typical applications?

Applications
High T, wear resistant, novel uses from charge neutrality.

Fabrication
Anderson 205- 14-1

Some glasses: forming possible

Other ceramics: cannot form or cast!

Glass Properties

Silicate Glasses
Glass Structure:
Amorphous (noncrystalline)
Na+
Si4+
O2-

4Basic unit: Si04 tetrahedron

Si4+
O2-

Compare to crystalline
Impurity elements

Anderson 205- 14-2

Check: Is
this
charge
balanced?

Na+, Mg2+, Ca2+, Al3+

-bonds Si04 tetrahedra together
-often lowers working T
-complicates structure: makes amorphous easier to obtain.
-must achieve charge neutrality
Anderson 205- 14-3

Specific volume

Specific volume (1/)

vs temperature (T)

Supercooled
Liquid

Liquid
(disordered)

Glasses:
-do not crystallize
Glass
-spec. vol. varies smoothly (amorphous solid)
-Tg: glass transition T
Crystalline
Crystals are different:
(i.e., ordered) solid
-spec. vol changes
T
Tg Tm
abruptly at Tm
dv
Viscosity (): =
units of : [Pa s]
dy

glass

dy dv
dv

dy

velocity gradient
Anderson 205- 14-4

Types of Glass Forming

Glass viscosity vs T, impurity content

Viscosity decreases with T
Impurities lower Tdeform

1014

Pressing:

annealing range

both operations
are used to
make jars,
bottles

Blowing:

1010

Tdeform: soft enough

to deform or work

106
102
1
200

Fiber
Drawing:
wind up

600 1000 1400 1800 T(C)

Anderson 205- 14-5

Anderson 205- 14-6

Clay Products

Tempered Glass
Puts surface into compression
Suppresses growth of surface cracks
before cooling

surface cooling

Clay is inexpensive

further cooled
compression
tension
compression

Surface crack growth is stopped

weak van
der Waals
bonding

Slip casting:
pour slip absorb water
into mold into mold green
ceramic

show
Prince
Ruperts
drops

charge
neutral

Add water to clay:

-allows material to shear easily
-extrusion, slip casting possible

pour slip
into mold

drain
mold

green
ceramic

charge
neutral

Sheet structure of kaolinite

clay
show slip demo

Anderson 205- 14-7

Anderson 205- 14-8

Drying and Firing

Drying: layer size and spacing decreases

wet slip

partially dry

green ceramic

Sintering Powders
Grind to produce ceramic and/or glass particles
Inject into mold
Sinter (i.e., press at elevated T to reduce pore size)

Aluminum oxide powder

Firing:
-T raised to (900-1400C)
-glass forms from clay and flows between Si02 particles
Si02 particle
(quartz)
glass formed
around
the particle

micrograph of
porcelain

70m

1800
1600

a crystalline 1400
material made 0
up of SiO2
tetrahedra

mullite
+ crystobalite

20

Particles are...
held together w/ glass or polymer resin
(ex: sandpaper or grinding wheels)
used in abrasive slurry
(ex: wire saws, polishing)

resin

alumina + L
mullite
+L

crystobalite
+L

3Al2O3-2SiO2

mullite

Liquid
(L)

Anderson 205- 14-10

Abrasives

High T phases (e.g., furnaces)

ex: silica(Si02)-alumina(Al203) system

2000

at 1700C for 6
minutes

Anderson 205- 14-9

Refractories

2200
T(C)

sintered at 1700C
for 2.5 minutes

40

60

alumina
+
mullite

80

100

Composition (wt% alumina)

Anderson 205- 14-11

Diamond-based
abrasive manufactured
by GE Superabrasives,
Worthington, OH
http://www.ge.com/superabrasives/

1.9mm

particles
-silicon carbide
-tungsten carbide
-aluminum oxide
-silica sand

Anderson 205- 14-12

Sensors
Principle: Make diffusion of ions fast
Oxygen sensor: ZrO2
Ca impurity
-increases O2- vacancies
-increases O2- diffusion

Ca2+

sensor

a Ca2+ ion removes a

Zr4+ and a O2- ion.

reference
gas with an
unknown, higher O2- gas at fixed
oxygen content diffu oxygen content

sion
+
voltage difference produced!

You can
also
make an
oxygen pump!
Anderson 205- 14-13