The slides are based in:

“Materials Science and Engineering. An

Introduction” William D. Callister Jr., David G.
Rethwish, John Wiley and Sons, 2018
Chapter 12:
Structures and Properties of Ceramics

“Introduction to Materials Science for Engineers”

James F. Shackelford, Prentice Hall, 2015
Chapter 3: Crystalline Structure – Perfection
Ceramic structures
 Fluorite Structure (AX2)
Ionic radii ratio in Fluorite
(CaF2) is:

RC/RA =

0.100/0.133 =

= 0.75

Therefore C.N. = 8

Would this be the unit cell ? NO !

 Fluorite Structure
We need in
the unit cell
the same
number of +
and –
charges.

That is, we
need twice as
many F- as
Ca2+ ions
 Fluorite Structure
We need in
the unit cell
the same
number of +
and –
charges.

That is, we
need twice as
many F- as
Ca2+ ions
Out class problem
•a) calculate the atomic packing factor of fluorite

•b) calculate the density of fluorite

Perovskite Structure
Typical Perovskite:
calcium titanium oxide (CaTiO3)

See unit cell:

- 8 x (1/8) Ca cations = 1 cation (2+)

- 1 x 1 Ti cation (4+)

- 6 x (1/2) O anions = 3 anions (2-)

Titanium

Calcium Compounds used as Perovskite = mineral first found

sensors, catalysts,
electrodes in fuel cells,
piezoelectric and memory
devices
WHY ?
in Ural mountains in 1839 and
named after Russian
mineralogist, Count Lev von
Perovski (1792-1856)
Perovskite Structure
Draw these two planes
(at scale). Do you see
any problems?

Titanium

Calcium

R(O=) = 0.14 nm
R(Ca2+) = 0.10 nm
R(Ti4+) = 0.068 nm a = 2 R(O=) + 2 R(Ti4+)
a = 0.28 + 0.136 = 0.416 nm
Perovskite Structure

√2
a

Titanium

Calcium
a

√2a = √2 x 0.416 nm = 0.588 nm

R(O ) =
=
0.14 nm a = 2 R(O=) + 2 R(Ca2+) = 0.48 nm
R(Ca2+) = 0.10 nm
R(Ti4+) = 0.068 nm
Cation mobility
Perovskite Structure
Piezoelectricity

Titanium

Calcium
 Cubic-to-Tetragonal/Triclinical Transformation

Above Curie temperature the material loses its spontaneous

polarization and piezoelectricity
 Piezoelectric Effect:
Force-to-Voltage

Road
sensors

Fancy
OTHER USES ? Shoes
Silicate Ceramics
Si and O are the two most abundant elements
on Earth’s crust:

•rocks
•sand
•clays

Instead of unit cell, building block of

silicates:
SiO44- tetrahedron
 SiO44- tetrahedron
What is the charge for this structure? -4

Inosilicates - chain silicates

https://cdn.britannica.com/42/2642-050-AC18536C/silicon-tetrahedron-silicate-minerals-atom-corner-oxygen.jpg
Inosilicates

Pyroxene
Mg[SiO3]
[Si2O6]4-

[Si4O11]6-

Amphibole
Mg7[Si8O22](OH)2
 Neso-, Soro-, and Cyclosilicates
Nesosilicates
[SiO4] 4-
Si 4+
Olivine [Si6O18]12-
(Mg,Fe)2 [SiO4 ]
O 2-
O1-
Cyclosilicates
Sorosilicates
Beryl
Si
Be3Al2[Si6O18]
[Si2O7]6- O0
[SiO3]2-
 Layer Silicates

Phyllosilicates (from the Tectosilicates, or

Greek phyllon, leaf), or "framework silicates"
“sheet silicates”
• Quartz
• Kaolinite - Al2Si2O5(OH)4
• Tridymite
• Mica
• Cristobalite
 Phyllosilicates
2:1 Phlogopite KMg3 [AlSi3O10](OH)2
1:1 Kaolinite Al4 [Si4O10](OH)8

TL
OL 2:1
[Si2O5]2- TL
Interstitial
 Tectosilicates
[SiO2]
High Cristobalite SiO2

Si
Si
Silica
Some forms of silica:
quartz
cristobalite

Silicas are not

closely packed
so they have
low densities.

cristobalite
Silica Glasses
Called fused silica or vitreous silica, silica glasses
have a high degree of atomic randomness

Beyond the SiO44- tetrahedron

structure, very little order exists.
 Zeolites / Molecular sieves
Open 3-D Framework
of TO4 tetrahedra
(T=Si, Al, P, .....)
Chabasite (CHA)
Secondary
Building Units
3D 8-rings

Large cages 1D
or channels 12-rings
(1, 2 3-D) AlPO4-5 (AFI)
accessible to
molecules
Zeolites
Morphological diversity
3

4
3
3
4
4
1
3
4
1 4 3
4 2 4
4 32 3
3 2 3
3 2
4 2
3 1 3 3
3 2 4 41 4
1
4 3 14
4
3
3 3
3
4
4
1
3 4 1
2
4
1
2 1 4 4 3
4 3 3 342 3 3 4
3 3 2
42 4 4

LTA
4 2 1
1

ANA
3 4 4 3

4 3 3 4

2 2
1 1 3
3 4 4
3 1 4 3
3 4 4 3 4 4 1
2 2 3
3 4 3 3 1
1 2 3 4
2
3
3
4
4 4
4
3
3 2 4
3
3 2
3 2 3 1
2 4 4 3
4 1 4
1 4
4 1 3 1 4
3 4 3
4 4 1
2 4
3
3
2
4
4
3
3
4

NAT LTL

MOR TON
 Please read:

“Materials Science and Engineering. An

Introduction” William D. Callister Jr., David G.
Rethwish, John Wiley and Sons, 2018
Chapter 4: Imperfections in Solids
Chapter 7: Dislocations and Strengthening
Mechanisms

“Introduction to Materials Science for Engineers”

James F. Shackelford, Prentice Hall, 2015
Chapter 3: Crystalline Structure – Perfection
Ceramic structures