Material Science I

Ceramic Materials

Chapter 3: Bond Energy and Properties

F. Filser & L.J. Gauckler

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

HS 2007

Ceramics: Bond Energy and Properties, Chap 3 1

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 2

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 ionic-
convalent bondings.

Ceramics: Bond Energy and Properties, Chap 3 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 4

Material Science I

The Bond Energy for Ionic Type of Bonding

Enet  Eatt  Erep
z1  z2  e 2
Sum Eatt  r  
4 0  r
repelling

B
E repulsion
Erep  r   n
r0 Ion’s Distance r
- +
z1  z2  e 2 B
Enet  r  
attracting

 n
4 0  r r
E attraction
r0 = equilibrium distance

Potential
z1  z2  e2  1 
Ebond  1  
4 0  r0  n 

Ceramics: Bond Energy and Properties, Chap 3 5

Material Science I
Potential and Force
as Function of Inter-Ionic Distance
150

40
100

20
Potential [eV]

50

Force [nN]
0 0
x2
-50
-20

x1
-100
x1 x2 -40

-150
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Inter-Ionic Distance r [pm] Inter-Ionic Distance r [pm]

Enet  r  
z1  z2  e2 B dEnet  r 
4 0  r r
 n Fnet  r  
dr
Ceramics: Bond Energy and Properties, Chap 3 8
Material Science I
Comparison of Potential – Inter-Ionic Distance Curves
for NaCl, MgO, LiF
• MgO potential well is
40
NaCl much deeper than for LiF
LiF
MgO and NaCl (ca 4x deeper)

20 • LiF potential well is a bit

deeper than for NaCl.
Potential [eV]

r0
0 • Same crystal structure
(Rocksalt)

-20 • Inter-Ionic Equilibrium

Distances
z1  z2  e2  1  - NaCl r0=283 pm
Ebond  1  
-40 4 0  r0  n  - LiF r0= 209 pm
- MgO r0=212 pm
0 0.5 1 1.5 2 2.5 3 3.5 4
• Valencies are different
Relative Inter-Ionic Distance r/r0 [-]

Ceramics: Bond Energy and Properties, Chap 3 9

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

2852°C 801°C 848°C Rocksalt

Ceramics: Bond Energy and Properties, Chap 3 10

Material Science I
Melting Temperature of some Compounds
Ionic Melting
z1=+1, z2=-1 Distance [Å] Temperature [°C]
NaF 2.31 988
inter-ionic distance
increasing due to anion NaCl 2.81 801 melting temperature
radius increasing decreasing
NaBr 2.98 755
NaI 3.23 651
z1=+2, z2=-2

MgO 2.1 2800

inter-ionic distance
increasing due to cation CaO 2.4 2580 melting temperature
radius increasing Comparable
decreasing
SrO 2.57 2430 decrease
BaO 2.76 !!! 1923 !!!
z1=+1, z2=-1

inter-ionic distance LiF 2.01 824

increasing due to cation NaF 2.311 988 melting temperature
radius increasing decreasing
KF 2.67 846
RbF 2.82 775

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
z1=+2, z2=-2 [Å ] [Mohs]
BeO 1.65 9
inter-ionic distance MgO 2.3 6.5
increasing due to cation hardness
radius increasing CaO 2.4 4.5 decreasing
SrO 2.57 3.5
BaO 2.76 3.3

Na+F -
NaF 2.01 3.2
valency of ions
Mg 2+O2- hardness
increasing & despite MgO 2.3 6.5
inter-ionic distance 3+N3-
increasing
ScN
Sc 2.67 7-8
increasing
TiC
Ti 4+C4- 2.82 8-9

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
The Melting Temperature of Al2O3 and MgO

Al2O3: 2054 °C Presumption: MgO has the lower melting temperature.

MgO: 2852 °C
} Why?

Criteria of Analysis:
• Ionic Distance

• Valency

• Bond Energy

• Lattice Energy

Ceramics: Bond Energy and Properties, Chap 3 13

Material Science I
The Melting Temperature of Al2O3 and MgO

Al2O3: 2054 °C Presumption: MgO has the lower melting temperature.

MgO: 2852 °C
} Why?

Criteria of Analysis:
• Ionic Distance -> r0Al2O3 = 193.5 pm, r0MgO = 212 pm

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

MgO
• Bond Energy E Al2O3
bond E bond  1.64
• Lattice Energy E Al2O3 MgO
E Lattice  23.54
Lattice

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 14
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 15

Material Science I

The Covalent Character of a Bond

TiO2 idealized Rutile CdI2 layer structure CO2 molecule lattice

Tm = 1857°C Tm = 387°C Tm = -57°C

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 16
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 polarized high amount of polarizing sufficient

(no polarization) pair of ions to form a covalent bond

Ceramics: Bond Energy and Properties, Chap 3 17

Material Science I

The Thermal Expansion Coefficient

1  l 
a  
l0  T  p
Potential Energy

rmin r0 rmax
max
ionic distance r

X maximum potential energy

energy level of the thermal vibration

= mean ion density (location) for increasing temperature

Ceramics: Bond Energy and Properties, Chap 3 18

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 19

Material Science I
Thermal Expansion Coefficient
in case of phase transformation

• a is a function of temp.
• Quartz shows one
Cristobalit
Cristobalite Quarz
transformation temperature.
Quartz
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.

Ceramics: Bond Energy and Properties, Chap 3 20

Material Science I

Anisotrope thermal Expansion Coefficients

b-Eucryptite (LiAlSiO4) = Glass Ceramic

kalt
cold heiss
hot

Ceramics: Bond Energy and Properties, Chap 3 21

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 22

Material Science I
Thermal Expansion and Melting Temperature
of chosen chemical Elements

Ceramics: Bond Energy and Properties, Chap 3 23

Material Science I
Thermal Expansion and Melting Temperature
of chosen chemical Elements

-40

-80

Potential [eV] -120

-160

-200

-240

0 100 200 300 400 500 600 700 800

Abstand [pm]

Ceramics: Bond Energy and Properties, Chap 3 24

Material Science I
Thermal Expansion and Melting Temperature
of chosen chemical Elements

0
• The higher the
melting temperature
-40
the deeper the
potential well.
-80
Potential [eV]

• The deeper the

-120 potential well the
more symmetric it
-160
appears.

• The more symmetric

-200
the less thermal
expansion
-240

0 100 200 300 400 500 600 700 800

Abstand [pm]
Ceramics: Bond Energy and Properties, Chap 3 25
Material Science I

The Elastic Modulus of Materials

150
Fmax
40
Hook’s
100
law

20
Potential [eV]

50

Force [nN]
r0
0 0

r0 rfail
-50
Epot -20

-100
-40

-150
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700 800
Ionic Distance r [pm] Ionic Distance r [pm]

z1  z2  e2 B dEnet z1  z2  e2 n  B
Enet   n Fnet    n 1
4 0  r r dr 4 0  r 2
r
Ceramics: Bond Energy and Properties, Chap 3 26
Material Science I

The Elastic Modulus of Materials

8
Kraft
6 Force
Fmax
F z1 z2 e 2 nB
4
F (r )  Enet / r  
2 Dx/Dy = elastic modulus, 4 0 r 2 r n1
linear elastic portion of
0 Hook’s law
Force
Kraft

-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 27
Material Science I

The Elastic Modulus of Materials

  E 
F  S0  (r  r0 )
 F 
S0   
 r r  r0
S0 1  F  1   2 Enet 
E E     2 
ro 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 28
Material Science I

The Elastic Modulus

Ceramics: Bond Energy and Properties, Chap 3 29

Material Science I
The Elastic Modulus

Ceramics: Bond Energy and Properties, Chap 3 30

Material Science I

Force-Distance-Curve

Ceramics: Bond Energy and Properties, Chap 3 31

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 32

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

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

E
 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

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 34

Material Science I

Summary
1.) the bond energy / force determines  many physical properties of a solid, i.e.
melting temperature Tm
thermal expansion a
elastic modulus E
theoretical strength 

2.) the deeper the potential well  the stronger the bonds
 the higher the melting temperature.
covalency in ionic bonds  stabilizes discrete structure elements
 lowers melting temperature lower.

3.) the thermal expansion  anharmonic potential well.

deeper potential well  smaller thermal expansion.
loose packed structures  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 35

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

z1  z2  e2  1 
Ebond  1  
4 0  r0  n 
Al2O3
 z1  z2 
Al2O3  r 
  0  MgO  1.64
Ebond
MgO
Ebond  z1  z2 
 r 
 0 

Al2O3: r0 = 193.5 pm, n = 7

MgO: r0 = 212 pm, n = 7

Ceramics: Bond Energy and Properties, Chap 3 37

Material Science I

Ratio of the Lattice Energy of Al2O3 to MgO

z1  z2  e 2
 1
ELattice  N Av  1  a
4 0  r0  n

E Al2O3
N Av  E Al2O3
a Al2O3
Lattice
 bond
 23.54
E MgO
Lattice N Av  E MgO
bond a MgO

Al2O3
Ebond Al2O3: aAl2O3 = 25.0312
 1.64
MgO
Ebond MgO: aMgO = 1.7475

Ceramics: Bond Energy and Properties, Chap 3 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
4 0  r0 2
r0
N Av  z1  z2  e 2  a r0 n 1
B 
4 0  r0 2
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 1  V 
• then we can calculate n     
V0  P T


 4 0  18r0
4

a  e   n  1
2

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

Ceramics: Bond Energy and Properties, Chap 3 40

Material Science I

Sample calculation for NaCl

 = 8.854×10-12 SI units
e = 1.602×10–19 coulombs
a = 1.74756 (NaCl structure)
d = 5.628×10-10 m giving r0 = 2.814×10–10 m
 = 4.18×10–11 SI

n is found by

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

Ceramics: Bond Energy and Properties, Chap 3 41