Structure of Materials

Dr. Kazi Hanium Maria

Course teacher
PH-407
 Ceramic
➢ The word ceramic is derived from the Greek term keramos, which
means “potter’s clay” and keramikos means “clay products”. Till 1950s,
the most important types of ceramics were traditional clays, made into
pottery, bricks, tiles etc.
➢ Ceramic materials are inorganic, nonmetallic materials that consist of
metallic and nonmetallic elements bonded together primarily by ionic
and/or covalent bonds.

Properties of ceramic materials:

most ceramic materials are hard and brittle with low toughness and
ductility but good electrical and thermal insulating properties. Also,
ceramic materials typically have high melting temperatures and high
chemical stability.
 Classifications of Ceramic
Ceramic Materials

Glasses Clay Refractories Abrasives Cements Advanced

products ceramics

-optical -whiteware -bricks for -sandpaper -composites -engine

-composite -structural high T -cutting -structural rotors
reinforce (furnaces) -polishing valves
-containers/ bearings
household -sensors

• Oxides: Alumina, zirconia

• Non-oxides: Carbides, borides, nitrides, silicides
• Composites: Particulate reinforced, combinations of oxides and
non-oxides
Classifications of Ceramic
 Ceramic
Distinguish between traditional and engineering ceramic materials:
➢ Traditional ceramic materials are typically made from three
components – clay, feldspar, and silica –. In contrast, engineering
ceramics consist of pure or nearly pure compounds such as aluminum
oxide ( Al2O3 ), silicon carbide (SiC), and silicon nitride ( Si3N4 ).
➢ Examples of traditional ceramics include bricks, tiles, and electrical
porcelain. In contrast, applications of engineering ceramics include
silicon carbide parts for high-temperature gas turbine engine
components, zirconium dioxide crucibles for melting superalloys, and
high-performance ball bearings and races made of titanium and
carbon nitride.
 Ceramic Crystal Structures
1. Tetrahedral: Geometric structure
where one atom or sphere is
surrounded by 4 nearest neighbours.

2. Octahedral: Geometric structure

where one atom or sphere is surrounded
by 6 nearest neighbours. It looks like
double pyramid.
 Ceramic Crystal Structures
3. Triangular: Geometric structure
where one atom or sphere is
surrounded by 3 nearest neighbours.

4. Linear: Geometric structure where

one atom or sphere is surrounded by
2 nearest neighbours.
Pauling’s Rules: Factors that Determine Crystal Structure
Pauling’s rules are based on the geometric stability of packing for ions of
different sizes, combined with simple electrostatic stability arguments.

Rule 1 Pauling’s first rule states that each cation will be coordinated by a
polyhedron of anions, the number of ions is determined by the relative sizes
of the cation and anion.

Pauling’s model treats the anions and cations of a crystal as if they were hard
spheres packed so tightly together that the spheres are touching. The arrangement of
anions in crystals is expected for a cubic or hexagonal closest-packed arrangement
of spheres, which suggests that the hard-sphere model is a good first approximation.
The number of large spheres (anions) that can fit around a small sphere (cation) is
called the anion coordination number and depends on the relative sizes of the small
and large spheres (the radius ratio).

Stable and unstable coordination configurations

Pauling’s Rules: Factors that Determine Crystal Structure
Rule 2 An ionic structure will be stable to the extent that the sum of the strengths
of the 2 electrostatic bonds that reach an anion equals the charge on that anion.

The electrostatic bond strength of an ionic bond may be defined as the charge on
the cation divided by the coordination number of the cation. In effect, the charge
on a cation is “shared” equally among all the nearest neighbor anions. The
electrostatic attraction of the cation to one anion is reduced if another anion is
attracting the cation in another direction. For example, the electrostatic bond
strength for the Si-O bond is 1 (+4/4) whereas the Al/O bond has a strength of 3
/4 (+3/4) or 1 /2 (+3/6). In most cases, the sum of the bond strengths for all the
bonds to a single oxygen anion is 2. In other words, the -2 charge on the oxygen
anion is balanced by a total charge of +2.

Pauling’s Rule #2 is also called the

principle of local charge balance.
Pauling’s Rules: Factors that Determine Crystal Structure
Rule 3 The sharing of edges and particularly faces by two anion polyhedra
decreases the stability of an ionic structure.
Cations strongly repel one another. When the bonding in a crystal is largely ionic,
the crystal is likely to have a structure that keeps the cations as far apart as
possible. However, because anions commonly have more than one cation bonded
to them, cations are never far apart. Cations will be farthest apart if they share only
one anion, i.e. their coordination polyhedra share only corners. If two anions are
shared, the coordination polyhedra have an edge in common and the cations are
closer together. If three anions are held in common, the coordination polyhedra of
the two cations share faces and the cations are “unreasonably close.”

Coordination polyhedra prefer

linkages where they share corners
rather than edges, and edges rather
than faces. This rule is simply based
on the fact that cations prefer to
maximize their distance from other
cations to minimize electrostatic
repulsion.
Pauling’s Rules: Factors that Determine Crystal Structure
Rule 4 In a crystal containing different cations, those of high valency and small
coordination numbers tend not to share polyhedron elements with one another.
If a cation has a high valency (charge) and a small coordination number, the electrostatic
bond strength for bonds between this cation and its coordinating anions will be relatively
large. If the bond strength is more than half the charge on the anion, it is unlikely that that
anion will have more than one bond to the same cation with the same coordination
number (see Rule 2). For example, bonds between phosphorus (with a charge of +5) and
oxygen (in four coordination) would have a strength of 5 /4. Two such bonds to an oxygen
anion would “overload” its -2 charge with a positive charge of +2.5.

Olivine (M2SiO4) is one of Pauling's

examples, where M is a mixture of Mg2+
at some sites and Fe2+ at others. The
structure contains distinct SiO4 tetrahedra
which do not share any oxygens (at
corners, edges or faces) with each other.
The lower-valence Mg2+ and Fe2+ cations
are surrounded by polyhedra which do
share oxygens.
Pauling’s Rules: Factors that Determine Crystal Structure
Rule 5 The number of essentially different kinds of constituents in a crystal
tends to be small.

Simple structures are usually preferred over more complicated

arrangements. For example, when several cations of similar size and
identical valence are incorporated into a lattice, they frequently occupy the
same site but are distributed at random, forming a solid solution or “alloy. ” As
the cations become increasingly dissimilar, a tendency to form an ordered
arrangement or “superlattice ” may occur. Finally, when the cations are
sufficiently different, they may each take on entirely different coordination
increasing the complexity of the structure.
Pauling’s Rules: Factors that Determine Crystal Structure
Stability of ionic crystal structures Stability of ionic crystal structure

How can we apply Pauling’s rules to deduce the unknown structure of an

ionic compound?
1. If the cation is smaller than the anion, as is often the case, we can deduce
that FCC or HCP close-packing of the anions will occur.
2. The cation/anion radius ratio helps us to decide which interstitial sites will be
occupied, and by far the most common are octahedral and tetrahedral sites.
3. Then if the ratio of interstitial sites to atoms in the FCC and HCP structures,
we examine the stoichiometry of the compound. For example, a binary metal
oxide MO has a 1:1 cation to anion ratio, so if octahedral coordination (CN=6)
is preferable, we can deduce that all of the octahedral sites will be filled since
the ratio of octahedral sites to atoms is 1:1. If tetrahedral coordination (CN=4)
is preferred, then only one-half of the tetrahedral sites need be filled since the
ratio of tetrahedral sites to atoms is 2:1.
4. These sites will tend to be filled in a way that maximizes the cation
separation, according to Pauling’s third and fourth rules.
Coordination number and Ionic Radii
r
• Coordination increases with cation
r anion UNIT CELL- ATOM
To form a stable structure, how many anions can RATIO
surround around a cation?
r cation Coord ZnS
ION LOCATIONS
r anion # (zinc blende)
Adapted from Fig. 12.4,
< 0.155 2 linear Callister & Rethwisch 8e.

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
Adapted from Fig. 12.2,
Callister & Rethwisch 8e.

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic Adapted from Fig. 12.3,
Callister & Rethwisch 8e.
 Coordination number and Ionic Radii
Determine minimum rcation/ranion for an octahedral site (C.N. = 6)

2ranion + 2rcation = 2a

a = 2ranion

2ranion + 2rcation = 2 2ranion

ranion + rcation = 2ranion rcation = ( 2 −1)ranion

rcation
= 2 − 1 = 0.414
 ranion 
 Pauling Equation and % ionic character of covalent bond
Electronegativity: The tendency of an atom in a molecule to attract the shared pair
of electrons towards itself is known as electronegativity. It indicates the net result
of the tendencies of atoms in different elements to attract the bond-forming electron
pairs. Linus Pauling designed the most commonly used scale.

Percentage Of Iconic Characters: The percentage of ionic character in a compound

having covalent character, can also be calculated by the following equation.
𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑑𝑖𝑝𝑜𝑙𝑒 𝑚𝑜𝑚𝑒𝑛𝑡
% 𝑖𝑜𝑛𝑖𝑐 𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟 =
𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑑𝑖𝑝𝑜𝑙𝑒 𝑚𝑜𝑚𝑒𝑛𝑡 𝑎𝑠𝑠𝑢𝑚𝑖𝑛𝑔 100% 𝑖𝑜𝑛𝑖𝑐 𝑏𝑜𝑛𝑑

Consider, HF. The % ionic character is nearly 43.25%, so the % covalent character
is (100 – 43.25) = 56.75%. But from the octet rule, HF should have been a purely
covalent compound but actually, it has some amount of ionic character in it which
is due to the electronegativity difference of H and F. Similarly knowing the bond
length and observed dipole moment of HCl, the % ionic character can be known. It
was found that HCl has 17% ionic character. Thus it can be seen that although we
call HCl and HF covalent compounds it has got appreciable amount of ionic
character. So from now onwards we should call a compound having more ionic
less covalent and vice versa rather than fully ionic or covalent.
 % ionic character of covalent bond

Bond Hybridization is possible when there is significant

covalent bonding
– hybrid electron orbitals form
– For example for SiC
• XSi = 1.8 and XC = 2.5
• ~ 89% covalent bonding
• Both Si and C prefer sp3 hybridization
• Therefore, for SiC, Si atoms occupy tetrahedral
sites
% ionic character = 100 {1- exp[-0.25(X Si − X C )2 ]} = 11.5%
Example Problem: Predicting the Crystal Structure of FeO

• On the basis of ionic radii, what crystal structure would you predict for FeO?

• Answer:
Cation Ionic radius (nm)
Al 3+ rcation 0.077
0.053
=
Fe 2 + 0.077 ranion 0.140
Fe 3+ 0.069 = 0.550
Ca 2+ 0.100
based on this ratio,
-- coord # = 6 because
Anion
0.414 < 0.550 < 0.732
O 2- 0.140
-- crystal structure is NaCl
Cl - 0.181
F- 0.133