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Material Science I

Ceramic Materials
Chapter 3: Bond Energy and Properties

F. Filser & L.J. Gauckler


ETH-Zrich, Departement Materials
frank.filser@mat.ethz.ch

HS 2007

Ceramics: Bond Energy and Properties, Chap 3

Material Science I

Goal of this Chapter is

to develop semiquantitative relationships between


the properties of a ceramic material and
the depth and shape of the energy well

Ceramics: Bond Energy and Properties, Chap 3

Material Science I

The Bond Energy and the Physical Properties

Bond forces / energy between ions or atoms composing a


solid determine a lot of its physical properties
Hence we can use the bond energy as a means to predict
physical properties
Examples: melting temperature, modulus of elasticity,
strength, hardness

This prediction works in a lot of cases but not in all.


Refinement is required for crystallized solids, i.e. effect of
Madelung, and for solids made up of mixed ionicconvalent bondings.

Ceramics: Bond Energy and Properties, Chap 3

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

Ceramics: Bond Energy and Properties, Chap 3

Material Science I

The Bond Energy for Ionic Type of Bonding


Enet Eatt Erep
z1 z2 e 2
Eatt r
4 0 r

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

Ceramics: Bond Energy and Properties, Chap 3

z1 z2 e2 1

1
4 0 r0 n
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Material Science I

Potential and Force


as Function of Inter-Ionic Distance
150
40

20

50

x2
-50

Force [nN]

Potential [eV]

100

-20

x1

-100

x1 x2

-40

-150
0

100

200

300

400

500

600

Inter-Ionic Distance r [pm]

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

Inter-Ionic Distance r [pm]

Fnet r

dEnet r
dr
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Material Science I

Comparison of Potential Inter-Ionic Distance Curves


for NaCl, MgO, LiF
40

MgO potential well is


much deeper than for LiF
and NaCl (ca 4x deeper)

NaCl
LiF
MgO

LiF potential well is a bit


deeper than for NaCl.

Potential [eV]

20

r0

Same crystal structure


(Rocksalt)

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

Relative Inter-Ionic Distance r/r0 [-]

Ceramics: Bond Energy and Properties, Chap 3

Valencies are different


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Material Science I

The Melting Temperature


The Bond strength Ebond
-> depends strongly on the valency and the ionic radii/distance (lattice distance).
The bond strength Ebond of ionic bonded compounds is directly proportional the
multiplication of its ionic charges z1 and z2 and inverse proportional the
equilibrium ionic distance r0.
The higher the valency the stronger the bond strength.
The compounds MgO, NaCl and LiF crystallize in same lattice (fcc lattice),
and ionic character of the bond is prevailing (>60 %).

MgO

NaCl

LiF

Crystal Structure

2852C

801C

848C

Rocksalt

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Melting Temperature of some Compounds


Ionic
Distance []

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

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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

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Material Science I

The Melting Temperature of Al2O3 and MgO

Al2O3: 2054 C
MgO: 2852 C

Presumption: MgO has the lower melting temperature.


Why?

Criteria of Analysis:
Ionic Distance
Valency

Bond Energy
Lattice Energy

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Melting Temperature of Al2O3 and MgO

Al2O3: 2054 C
MgO: 2852 C

Presumption: MgO has the lower melting temperature.


Why?

Criteria of Analysis:
Ionic Distance

-> r0Al2O3 = 193.5 pm, r0MgO = 212 pm

Valency

-> (z1 x z2)Al2O3= -6, (z1 x z2)MgO= -4

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,

however not all the time!!!


Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Melting Temperature of Al2O3 and MgO

Al2O3: 2054 C
MgO: 2852 C

We need other and better criteria !!!

Further Criterium of Analysis:


-> Type of Bond: amount of covalency in the bonds for Al2O3 is higher
than for MgO.
A measure for covalency is, for example, the difference in
electronegativity of the ions. DENAl2O3 = 1.83, DENMgO = 2.13

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Covalent Character of a Bond

TiO2 idealized Rutile


Tm = 1857C

CdI2 layer structure


Tm = 387C

CO2 molecule lattice


Tm = -57C

MX2 stoichiom., DEN = 1.9

MX2 stoichiom., DEN = 0.97

MX2 stoichiom., DEN = 0.89

Tm = melting temp.

The covalent character of a bond increases from the left to right.


The network structure of the bonds changes: from a 3D structure of TiO2 (Rutile), to a
layered structure of CdI2, to a molecule lattice of CO2. The melting temperature
decrease in this direction, too.
Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

What issues influence the amount of covalency


in an ionic bond?
MgO vs Al2O3

Polarizing power of the cation

fAl3+ = 60 1/nm; fMg2+ = 31 1/nm

Polarizibility of the anion

aeO2- equal for both cases

Elektron configuration of the cation

no d-electrons in both cases

ideal pair of ions


(no polarization)

Ceramics: Bond Energy and Properties, Chap 3

polarized
pair of ions

high amount of polarizing sufficient


to form a covalent bond

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Material Science I

The Thermal Expansion Coefficient


1 l

l0 T p

Potential Energy

rmin r0

rmax
max

ionic distance r

maximum potential energy


energy level of the thermal vibration

= mean ion density (location) for increasing temperature

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Thermal Expansion of Chosen Ceramic Materials

Metals possess a higher thermal


expansion than ceramic materials
a is a function of the temperature
The higher T the higher a

Loosely packed, non-dense structures


(higher amount of bond covalency) may
have very small a changement of
angle of the the bonds

Temperature C
Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Thermal Expansion Coefficient


in case of phase transformation

Cristobalit
Cristobalite

Ceramics: Bond Energy and Properties, Chap 3

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.

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Material Science I

Anisotrope thermal Expansion Coefficients


b-Eucryptite (LiAlSiO4) = Glass Ceramic
cold
kalt

heiss
hot

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Glass ceramics: Zerodur

Astro Space: Mirrors of future x-ray satelites


Micro lithography: Zerodur components are used as movable elements in wafer-stepper and wafer-scanners.
Metrology: Because of its very low thermal expansion and its long-term stability, components made of Zerodur will show
excellent precision in measurements instruments and metroloy.
Mechanic: Excellent machinability of Zerodur in combination with the modern high-tech manufacturing technologies enables
complex shapes.
Further Applications: Zerodur has good transmission properties in visible and infrared spectrum and a very good optical
homogeneity. Because of these properties Zerodur is often used in optical systems.
http://www.schott.com/optics_devices/german/products/zerodur/?c=mL

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Thermal Expansion and Melting Temperature


of chosen chemical Elements

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Thermal Expansion and Melting Temperature


of chosen chemical Elements
0

Potential [eV]

-40

-80

-120

-160

-200

-240

100

200

300

400

500

600

700

800

Abstand [pm]

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Thermal Expansion and Melting Temperature


of chosen chemical Elements
0

The higher the


melting temperature
the deeper the
potential well.

Potential [eV]

-40

-80

The deeper the


potential well the
more symmetric it
appears.

-120

-160

The more symmetric


the less thermal
expansion

-200

-240

100

200

300

400

500

600

700

800

Abstand [pm]

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Elastic Modulus of Materials


150

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

Ionic Distance r [pm]

Enet

z1 z2 e2 B

n
4 0 r r

Ceramics: Bond Energy and Properties, Chap 3

700

800 0

100

200

300

400

500

600

700

800

Ionic Distance r [pm]

dEnet z1 z2 e2 n B
Fnet

n 1
2
dr
4 0 r
r
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Material Science I

The Elastic Modulus of Materials


8

Kraft

Fmax
F

Force

F (r ) Enet / r

Dx/Dy = elastic modulus,


linear elastic portion of
Hooks law

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

The force inter-ionic distance curve.


In the equilibrium point r0 a tangential line exists which in a first approximation describes
good the linear elastic behaviour of a solid under tensile force.
Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Elastic Modulus of Materials

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

This result is important:


1. the stiffness (elastic modulus) of a solid is directly related to the curvature of its potential
ionic distance curve. The curvature is inverse of the curvature radius.
2. compounds with stronger bonds have a higher elastic modulus (stiffness) than weak bonded
compounds, and
3. compounds with a high melting temperature, i.e. ceramic materials, (deep potential well) are
very stiff solids.
Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Elastic Modulus

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Elastic Modulus

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Force-Distance-Curve

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Theoretic Strength of Solids


- simple approximation assuming that generally bonds in solids fail at 25% elongation,
which calculates to 1.25 x r0.

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.

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

The Theoretic Strength of Solids


- more sophisticated approximation generalized form of the potential distance function
with n > m and max Fmax/(r0)2
E

typical values for n and m, in case of ionic bonds (n = 9, m = 1) leads to

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

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Material Science I

The Theoretic Strength of Solids


simple approximation:

more sophisticated approximation:

Examples:

Al2O3: bend = 330 MPa, E = 300 GPa (/ 910) (http://www.accuratus.com/)


SiC: bend = 550 MPa, E = 410 GPa (/ 745)
BN: bend = 75.8 MPa, E = 46.9 GPa (/ 620)

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

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Material Science I

Summary
1.) the bond energy / force determines

2.) the deeper the potential well


covalency in ionic bonds

3.) the thermal expansion


deeper potential well
loose packed structures

many physical properties of a solid, i.e.


melting temperature Tm
thermal expansion a
elastic modulus E
theoretical strength

the stronger the bonds


the higher the melting temperature.
stabilizes discrete structure elements
lowers melting temperature lower.
anharmonic potential well.
smaller thermal expansion.
smaller thermal expansion.

4.) stiffness / elastic modulus


proportional to the curvature of the potential
Solids with stronger bonds are stiffer than solids with weaker bonds.
5.) theoretical strength should be
~1/10 of the elastic modulus E.
However, experimentally measured strength values are about 1/100 to 1/1000 of this value.

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Additional Slides

Ceramics: Bond Energy and Properties, Chap 3

36

Material Science I

Ratio of the Bond Energy of Al2O3 to MgO

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

Al2O3: r0 = 193.5 pm, n = 7


MgO: r0 = 212 pm, n = 7
Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Ratio of the Lattice Energy of Al2O3 to MgO

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
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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

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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

Examples: NaCl 4.18 x 10-11 1/Pa -> n = 7.7

Ceramics: Bond Energy and Properties, Chap 3

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Material Science I

Sample calculation for NaCl


= 8.85410-12 SI units
e = 1.6021019 coulombs
a = 1.74756 (NaCl structure)
d = 5.62810-10 m giving r0 = 2.8141010 m
= 4.181011 SI
n is found by

This compares to 769.4 kJ/mole experimental (2.4% error)


Ceramics: Bond Energy and Properties, Chap 3

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