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Ceramic Structures PDF
Ceramic Structures PDF
Bonding in Ceramics
CERAMIC STRUCTURES
Dipole moment
The measure of net polarity of a bond is
called dipole moment, ()
Mathematically,
=
Q = Charge
r= distance between charges
Units: debye
1 D = 3.336 x 10-30 C.m
Formation of ions
Removal of electron gives Cation (+vely
charged ions), has more number of
protons than electrons (All metals form
cations)
Addition of electron gives anion (-vely
charged), has more electrons than protons
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Second Criteria
Each Cation prefers to have as many nearest
neighbours anions as possible and likewise.
Stable ceramic structures form when anions
surrounding a cation are in contact with that cation.
Size or ionic radii of the cations and anions is
important
Cation ion radius (rc) and anion radius (rA)
Cations are smaller than anions, the relative size is
quantified by the radius ratio ()
= < 1
UNSTABLE
STABLE
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Tetrahedron
Octahedron
Cube
X-ray d100 a
Ionic radius =
2
4
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1 2 2
+
40
Repulsive energy
Attractive energy
Homework problems
Lattice Energy
Amount of Energy released on the formation of bonds (-ve)
Indicator of bond strength
Book
Principles of Materials Science and Engineering by W. F. Smith
3rd Edition
08-Nov-13
Bond Length
NaCl
LiF
Structure
Melting
point
2852 C
801 C
848 C
Rocksalt
Inter-ionic
equilibrium
distance
212 pm
283 pm
209 pm
Rocksalt
Comparison of Potential-interatomic
distance curves
NaCl
LiF
Structure
Melting
point
2852 C
801 C
848 C
Rocksalt
Inter-ionic
equilibrium
distance
212 pm
283 pm
209 pm
Rocksalt
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% Ionic Character vs EN
1
4
)(100%)
Where, XA = EN of atom A
XB = EN of atom B
Polarisation
Polarization
Cations tend to attract outer electrons of the anion and at the same time it tends to
repel the positively charged nucleus of the anions. This result in distortion of the
anion (anion is polarised). The effect is called polarising effect.
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Crystal Structures
Simple Cubic structure
Packing of spheres in a simple cubic array
Interstitial site
surrounded by eight
atoms
CN = 8
Octahedral
site (Type 2)
Tetrahedral
Sites (Type 1)
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Type 1 are
now covered
But type 2 are
still left vacant
Interstitial site 3
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FCC lattice
Octahedral hole
Tetrahedral hole
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For CN = 8
+ = 1.732
dA = 1
Then
dC = 0.732
1 (arbitrary)
Cation will rattle if Relative
Radius goes below 0.732
1 (arbitrary)
For CN = 6
= = 0.732
+ = 2
dA = 1
Then
dC = 0.414
= = 0.414
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Cl
Cl-1
Cs
1 1 1
( , , )
2 2 2
Position of Cs
cation in unit
cell
Cs+1
Lattice of CsCl
Hard sphere model to represent
unit cell of CsCl
Example 10.3
Calculate the ionic packing factor for CsCl. Ionic radii are
Cs+ = 0.170 nm and Cl-= 0.181 nm
Ionic packing factor =
3 = 2 + 2
= 0.405
AlNi
AgMg
LiMg
4
3
3
4
3
1 + 3 (1 )
3
0.68
-Cu-Zn
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Formation of Octahedrons
Eight
In FCC unit cell, there are 13 octahedral sites, and octahedrons can
be formed
Rocksalt Structure
ClNa+
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The octahedral sites are located at the centre of the unit cell (1/2, 1/2, 1/2)
as well as at the edges of the unit cell (1/2, 0, 0), etc.
Calculate the planar density of Ca+2 and O-2 ions in ions/nm2 on the
(111) plane of CaO.
FCC
( , , )
(, , )
FCC
BCC
12 Sites available for BCC unit cell
BCC
In FCC unit cell, 8 tetrahedral sites are positioned within the cell, at the general
fractional Coordinates (n/4,n/4,n/4) where n = 1 or 3, e.g., (,, , ) or (, , )
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rZn/RS=0.60/1.84=0.32 (tetrahedral)
S-2
Zn+2
4 tetrahedral
sites are
occupied per unit
cell to maintain
charge neutrality
Bonding is
typically covalent
Diamond
Example 3.16
Calculating the Theoretical Density of GaAs
The lattice constant of gallium arsenide (GaAs) is 5.65 . Show that
the theoretical density of GaAs is 5.33 g/cm3.
For the Zinc blende GaAs unit cell, there are four Ga
and four As atoms per unit cell.
Each mole (6.023 1023 atoms) of Ga has a mass of
69.7 g. Therefore, the mass of four Ga atoms will be (4
* 69.7/6.023 1023) g.
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density
mass
4(69.7 74.9) / 6.023 10
8
3
volume
(5.65 10 cm)
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If the charges on the cations and anions are not same, a compound can
exist with the chemical formula AmXp ,where m and/or p 1
AX2 type compounds
Examples CaF2 (fluorite), UO2, PuO2, ThO2, BaF2, PbMg2
rca+2/RF- = 0.8
CN = 8 for
Ca+2
8 tetrahedral
sites are
occupied by Fions to maintain
charge neutrality
Many octahedral
sites are vacant.
In UO2 this
allows to
accommodate
fission products
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3
+
= 4 + 2
4
Structure of Li2O
g/cm3
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Octahedral
sites
Example:
Silicon with a valence of 4 has tetrahedral coordiantion (CN=4) ,
the bond strength is 4/4 = 1
Al+3 ions in octahedral coordiantion (CN=6) , the bond strength
is 3/6 = 1/2
A2X3 structures
Hexagonal closed pack structures
Coordination number of cation is 6 and anion is 4
2/3 octahedral sites are filled
Structure name is Corundum
Examples
Al2O3, Fe2O3, Cr2O3, Ti2O3, V2O3, Ga2O, Rh2O3
O-2
Al+3
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Perovskite structures
ABO3 type structures (have two types of cations)
A is a divalent cation (La, Ba, Sr, Ca, etc)
B is tetravalent cation (Fe, Co, Ni, Mn, Ti, etc)
O is oxide anion
Examples BaTiO3, CaTiO3, LaMnO3, etc.
Perovskite structures
2 Ti+4 , 4 Ca+2
Total bond strength of Ti-O bond = 2(2/3) = 4/3
And Total bond strength of Ca-O bond = 4(1/6)
a = (rO+rA)
a = 2(rO+rB)
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If A ion is smaller than ideal then t will be smaller than ideal value.
Problem
Calculate GoldShmidts tolerance factor for SrTiO3? Ionic radii for Sr+2 =
0.144 nm ,Ti+4 = 0.0605 nm ,O-2 = 0.140 nm
For ideal cubic pervoskite t= 1, such as SrTiO3
Higher or lower values than ideal value (1) changes the
structure symmetry
In SrFeO2.875 , there will be some Fe+3 and the other Fe+4 ions. Oxygen
vacancies ordered so that FeO5 square pyramids formed.
Oxygen vacancies
provide oxide ion
conductivity to the
pervoskites, hence
used in Solid oxide
fuel cells
Barium titanate
Perovskite Superconductor
High temperature superconductor (YBa2Cu3O6.96) is superstructure
of pervoskite.
Perovskite structure
Piezoelectricity
High dielectric strength
Ferroelectricity (exhibition of spontaneous
polarisation and re-orientation of polarisation)
Curie temperature (120 C). It is tetragonal below 120
C (ferroelectric) but above 120 C it is cubic a perfect
pervoskite (paraelectric)
Uses:
Ultrasonic equipment, capacitors, piezoelectric devices,
doped titanate have applications in semiconductors.
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Ferroelectricity in BaTiO3
Ferroelectricity in BaTiO3
Ferroelectricity in BaTiO3
Ferroelectricity in BaTiO3
Ferroelectricity in BaTiO3
Ferroelectricity in BaTiO3
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10.2.5-10.2.24
AII is divalent cation e.g, Fe, Cr, Mn, Mg, Co, Ni, Cu, Zn, Cd, Sn
BIII is trivalent cation e.g, Al, Ga, In, Ti, V, Cr, Mn, Fe, Co, Ni
X is O, S, Se
Named after the mineral spinel (MgAl2O4)
Spinel structure
Spinel structure is a cubic structure which is considered as
combination of the rock salt and zinc blende structures.
Spinel structure
Example :
MO.Fe2O3 (M is a divalent
metal ion)
Inverse Spinel
Most common structure
The A+2 ions and half B+3 ions
are on octahedral sites, the
other half of B+3 are on
tetrahedral sites.
Examples
Ferrites (these have magnetic
properties) e.g.,
Fe3O4, FeMgFeO4, FeTiFeO4,
ZnSnZnO4, etc.
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Pauling rules
Pauling rules
First Rule
Second Rule
In a stable structure the total strength of the bonds reaching an anion from all
surrounding cations should be equal to the charge of the anion.
Linus Pauling
Pauling rules
Second Rule
The electrostatic valency (E.V) principle
E.V = charge on cation/C.N
Charge is exactly balanced on anion and cation , this is called isodesmic bond
and the bond strength are equal from all directions.
Pauling rules
Third Rule
Sharing corners will put the cations at the greatest distance from each other.
In the stable structures, corners and faces of the coordination polyhedra tend
to be shared.
E.V = 4/4= 1
SiO4-4 a building block of silicate minerals
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Pauling rules
Pauling rules
Fourth Rule
Third Rule
Cations with high valency and low coordination numbers tend to not
share their coordinating polyhedra.
Paulings fourth rule says that highly charged cations will tend to be as far
apart as possible to minimize electrostatic repulsion.
Fifth Rule
The number of different kinds of constituents in a structure tends to be
small.
Stability decreases
There are only few different kinds of anions and cations sites in a crystal.
There are only octahedral, tetrahedral and cubic sites, most crystal will be
formed by occupying these small number of sites.
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