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Ceramic Materials
Chapter 3: Bond Energy and Properties
HS 2007
Material Science I
Material Science I
Material Science I
Contents
potential well & bond energy for ionic bonding, the equilibrium distance
bond force as a function of the inter-ionic distance, max. force, inflexion
point.
melting temperature and hardness for ionic bonded compounds
limitation of the prediction by potential well (example of MgO / Al2O3)
-> introduction of covalency (of an ionic bond)
thermal expansion explained with the potential well
elastic modulus
theoretic strength of compounds
Material Science I
repelling
Sum
E repulsion
attracting
Ions Distance
r0
+
E attraction
r0 = equilibrium distance
B
Erep r n
r
z1 z2 e 2 B
Enet r
n
4 0 r r
Potential
Ebond
z1 z2 e2 1
1
4 0 r0 n
5
Material Science I
20
50
x2
-50
Force [nN]
Potential [eV]
100
-20
x1
-100
x1 x2
-40
-150
0
100
200
300
400
500
600
z1 z2 e2 B
Enet r
n
4 0 r r
Ceramics: Bond Energy and Properties, Chap 3
700
800 0
100
200
300
400
500
600
700
800
Fnet r
dEnet r
dr
8
Material Science I
NaCl
LiF
MgO
Potential [eV]
20
r0
Inter-Ionic Equilibrium
Distances
- NaCl r0=283 pm
- LiF r0= 209 pm
- MgO r0=212 pm
-20
Ebond
-40
0.5
1.5
z1 z2 e2 1
1
4 0 r0 n
2.5
3.5
Material Science I
MgO
NaCl
LiF
Crystal Structure
2852C
801C
848C
Rocksalt
10
Material Science I
z1=+1, z2=-1
inter-ionic distance
increasing due to anion
radius increasing
Melting
Temperature [C]
NaF
2.31
988
NaCl
2.81
801
NaBr
2.98
755
NaI
3.23
651
MgO
2.1
2800
CaO
2.4
2580
SrO
2.57
Comparable
BaO
2.76
!!!
LiF
2.01
824
NaF
2.311
988
KF
2.67
846
RbF
2.82
775
melting temperature
decreasing
z1=+2, z2=-2
inter-ionic distance
increasing due to cation
radius increasing
2430 decrease
1923
melting temperature
decreasing
!!!
z1=+1, z2=-1
inter-ionic distance
increasing due to cation
radius increasing
melting temperature
decreasing
The melting temperature increases as the ionic distance decreases within the lattice.
The melting temperature increases for increasing valency given about same ionic distance
Ceramics: Bond Energy and Properties, Chap 3
11
Material Science I
Hardness
as function of the inter-ionic distance and the ionic charge
Compound
Ionic Distance
[ ]
Hardness
[Mohs]
BeO
1.65
MgO
2.3
6.5
CaO
2.4
4.5
SrO
2.57
3.5
BaO
2.76
3.3
+F Na
NaF
2.01
3.2
2+O2Mg
MgO
2.3
6.5
3+N3ScN
Sc
2.67
7-8
4+C4TiC
Ti
2.82
8-9
z1=+2, z2=-2
inter-ionic distance
increasing due to cation
radius increasing
valency of ions
increasing & despite
inter-ionic distance
increasing
hardness
decreasing
hardness
increasing
The hardness increases with decreasing ionic distance, assuming constant ionic charges.
The hardness increases for increasing valency, despite ! increasing ionic distance.
Ceramics: Bond Energy and Properties, Chap 3
12
Material Science I
Al2O3: 2054 C
MgO: 2852 C
Criteria of Analysis:
Ionic Distance
Valency
Bond Energy
Lattice Energy
13
Material Science I
Al2O3: 2054 C
MgO: 2852 C
Criteria of Analysis:
Ionic Distance
Valency
Bond Energy
Lattice Energy
Al2O3
bond
Al2O3
Lattice
MgO
E bond 1.64
MgO
E Lattice 23.54
The analysis based on the potential well of an ionic bonded solid is often good and correct,
14
Material Science I
Al2O3: 2054 C
MgO: 2852 C
15
Material Science I
Tm = melting temp.
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Material Science I
polarized
pair of ions
17
Material Science I
l0 T p
Potential Energy
rmin r0
rmax
max
ionic distance r
18
Material Science I
Temperature C
Ceramics: Bond Energy and Properties, Chap 3
19
Material Science I
Cristobalit
Cristobalite
Quarz
Quartz
a is a function of temp.
Quartz shows one
transformation temperature.
Q. is a single crystal - the
other materials are
polycrystals.
a of b-quartz has a negative
slope, i.e. increasing temp.
leads to smaller a(see also
ZrO2)
Quartz has a lower a than
cristobalite because quartz
bonding can change angles,
and cristobalite bond angles
are already more straight
SiO2 vit. : bond angles change
in all spatial directions.
20
Material Science I
heiss
hot
21
Material Science I
22
Material Science I
23
Material Science I
Potential [eV]
-40
-80
-120
-160
-200
-240
100
200
300
400
500
600
700
800
Abstand [pm]
24
Material Science I
Potential [eV]
-40
-80
-120
-160
-200
-240
100
200
300
400
500
600
700
800
Abstand [pm]
25
Material Science I
Fmax
100
20
50
r0
r0
Force [nN]
Potential [eV]
40
Hooks
law
rfail
-50
Epot
-20
-100
-40
-150
0
100
200
300
400
500
600
Enet
z1 z2 e2 B
n
4 0 r r
700
800 0
100
200
300
400
500
600
700
800
dEnet z1 z2 e2 n B
Fnet
n 1
2
dr
4 0 r
r
26
Material Science I
Kraft
Fmax
F
Force
F (r ) Enet / r
Kraft
Force
2
0
z1 z2 e 2
4 0 r 2
nB
r n1
-2
-4
-6
-8
-10
0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8
r00
Abstand
Distance
27
Material Science I
E
F S0 (r r0 )
F
S0
r r0
S0
E
ro
1 F
1 2 Enet
E
2
r0 r r r0 r0 r r r
0
28
Material Science I
29
Material Science I
30
Material Science I
Force-Distance-Curve
31
Material Science I
2 Fmax
2 Fmax
S0
rBruch r0 1.25r0 r0
The (tensile) strength of an ionic bonded solid should be ~ 1/8 of the elastic modulus.
32
Material Science I
max
15
The (tensile) strength of an ionic bonded solid should be ~ 1/15 of the elastic modulus.
Ceramics: Bond Energy and Properties, Chap 3
33
Material Science I
Examples:
The tensile strength of ionic bonded solids should be about ~ 1/10 of the elastic modulus E.
However, we find experimentally that the strength of these materials is about
1/100 to 1/1000 x E. That is much less than our approach using the potential well predicts !!!
There must be other issues determining the low strength than the potential well!
Ceramics: Bond Energy and Properties, Chap 3
34
Material Science I
Summary
1.) the bond energy / force determines
35
Material Science I
Additional Slides
36
Material Science I
Ebond
z1 z2 e2 1
1
4 0 r0 n
Al2O3
Al2O3
Ebond
MgO
Ebond
z1 z2
r
0 MgO 1.64
z1 z2
r
0
37
Material Science I
z1 z2 e
N Av
4 0 r0
ELattice
Al2O3
Lattice
MgO
Lattice
E
E
N Av E
N Av E
Al2O3
Ebond
1.64
MgO
Ebond
Ceramics: Bond Energy and Properties, Chap 3
Al2O3
bond
MgO
bond
Al2O3:
MgO:
1
1 a
n
a
23.54
MgO
a
Al2O3
aAl2O3 = 25.0312
aMgO = 1.7475
38
Material Science I
Determination of
B (Born Constant) and n Born Exponent
at equilibrium
Elattice
0
r r r0
r0 can be measured
N Av z1 z2 e 2 a n B
n 1 0
2
4 0 r0
r0
N Av z1 z2 e 2 a r0 n 1
B
2
4 0 r0
n
N Av z1 z2 e 2 a r0 n 2
B
4 0 n
n is still unknown!
To find n, we need to move away from equilibrium, i.e. compress the solid and
measure its compressibility
Ceramics: Bond Energy and Properties, Chap 3
39
Material Science I
Compressibility
compressiblity is measured
then we can calculate n
1 V
V0 P T
4
4
18
r
0
0
2
a e n 1
40
Material Science I
41