4.0 Imperfections in Solids: "Crystals Are Like People, It Is The Defects in Them Which Tend To Make Them Interesting!"

4.
0 IMPERFECTIONS IN SOLIDS
“Crystals are like people, it is the defects in them
which tend to make them interesting!” - Colin
Humphreys.
Defects in Solids
0D, Point defects

 vacancies
 interstitials
 impurities
1D, Dislocations
 edge
 screw
2D, Grain boundaries

 tilt
 twist
3D, Bulk or Volume defects

4.1 Introduction
Real crystals are never perfect, there are always
defects in them
Schematic drawing of a poly-crystal with many defects by

Helmut Föll, University of Kiel, Germany.
Defects have profound impact on the macroscopic
properties of materials
Eg. Sterling silver (92.5% Ag + 7.5% Cu) is much

harder and stronger than pure silver.
Defects may be classified into four categories
depending on their dimensions:
0D, Point defects: atoms missing or atoms in irregular

places in the lattice (vacancies, interstitials, impurities)
1D, Linear defects: groups of atoms in irregular

positions (e.g. screw and edge dislocations)
2D, Planar defects: the interfaces between

homogeneous regions of the material (grain boundaries,
external surfaces)
3D, Volume defects: extended defects (pores, cracks)

4.2 Point defects in Metals
- Vacancy: vacant atomic sites in a structure
Vacancy
distortion
of planes
- Self-interstitials: extra atoms positioned between

atomic sites.
self-
distortion interstitial
of planes
Equilibrium number of vacancies
Statistical thermodynamics predicts that the
equilibrium number of vacancies Nv of a material
depends on temperature according to
N = Total # of atomic sites

Qv = energy required for the formation of a vacancy
k = Boltzmann’s constant = 1.38 * 10-23 J/atom-K
= 8.62 * 10-5 eV/atom-K
T = temperature in kelvin
For a given material, N can be obtained from
NA = Avogadro’s number = 6.023 * 1023 atoms/mol

ρ = density of material, g/cm3
A = atomic weight, g/mol
Example 4.1
Calculate the equilibrium number of vacancies
per cubic meter for copper at 1000°C. The
energy for vacancy formation is 0.9 eV/atom;
the atomic weight and density (at 1000°C) for
copper are 63.5 g/mol and 8.40 g/cm3,
respectively.
Also, find the number of vacancies per every
10,000 atomic sites at this temperature.
Other point defects: Self-interstitial, impurity
4.3 Point defects in Ceramics
Both vacancies and interstitials are possible.
Ceramic materials contain ions of at least two kinds,
defects for each ion type may occur. Eg, in NaCl, Na
interstitials and vacancies and Cl interstitials and
vacancies may exist.
Defects occur in pairs to maintain electroneutrality
i.e. the state when there are equal # of +ve and –ve
charges from the ions.
1. A cation–vacancy and a cation– interstitial pair.

This is called a Frenkel defect.
Considered as being formed by a cation leaving its
normal position and moving into an interstitial site.
There is no change in charge because the cation

maintains the same positive charge as an interstitial.
2. A cation – vacancy and anion – vacancy pair.
This is known as a Schottky defect. The neutrality of
the crystal is maintained.
Stoichiometry
The ratio of cations to anions is not altered in the

formation of both Frenkel and Schottky defects. If this
ratio is equal to that of the chemical formula, the
material is said to be stoichiometric. A deviation from
this is said to be nonstoichiometric.
E.g of nonstoichiometric material is FeO.

4.4 Impurities
 Impurities - atoms which are different from the
host.
 All real solids are impure. Very pure metals
99.9999% - one impurity per 106 atoms
 May be intentional or unintentional
 Examples: carbon added in small amounts to

Iron makes steel, which is stronger than pure
iron. Boron added to silicon change its electrical
properties.
4.4.1 Solid with impurities – Solid solution
Solid solutions are made of a host (the solvent or matrix)
which dissolves the minor component (solute). The
ability to dissolve is called solubility.
Solvent: in an alloy, the element or compound present in

greater amount.
Solute: in an alloy, the element or compound present in

lesser amount.
Solid solutions are

homogeneous
able to maintain their crystal structure
Impurity point defects in solid solutions are
substitutional or interstitial.
Factors for high solubility
1. Atomic size factor - atoms need to “fit” ⇒ solute and

solvent atomic radii should be within ~15%
2. Crystal structures of solute and solvent should be

the same.
3. Electronegativities of solute and solvent should be

comparable (otherwise new inter-metallic phases are
encouraged)
4. Generally more solute goes into solution when the

solvent has higher valency.
4.5 Specification of composition/concentration
Composition can be expressed in

weight percent: useful when making the solution
atom percent: useful when trying to understand the
material at the atomic level
Weight percent (wt %): weight of a particular
element relative to the total alloy weight.
For two-component system, concentration of element
1 in wt. % is
Atom percent (at %): number of moles (atoms) of a
particular element relative to the total number of
moles (atoms) in alloy.
For two-component system, concentration of element

1 in atom % is
where nm1 = m’1/A1

m’1 is weight in grams of element 1,
A1 is atomic weight of element 1
Weight % to Atomic %
Atomic % to Weight %
4.6 Dislocation – linear defects
Dislocations are abrupt changes in the regular
ordering of atoms, along a line (dislocation line) in the
solid. The area in which these distortions occur is
dislocation core.
Dislocation are important in mechanical properties of
materials.
2 main types of dislocation are know

i. Edge dislocation
ii. Screw dislocation
Mixed dislocation: having both dislocations in a matter
4.6.1 Edge dislocation
Edge dislocations occur when an extra plane is
inserted. The dislocation line is at the end of the
plane.
4.6.2 Screw dislocation
Screw dislocations result when shear stresses are
applied to produce the distortion.
4.7 Grain Boundaries/Interfacial defects
Some of the defects include:

- External surfaces,
- Grain boundaries
- Twin boundaries
- Phase boundaries
Please read!!!!
4.8 Bulk or Volume defects
Pores - can greatly affect optical, thermal, and
mechanical properties
Cracks – can affect mechanical properties
Foreign inclusions - can greatly affect electrical,

mechanical, optical properties
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4.

0D, Point defects

2D, Grain boundaries

3D, Bulk or Volume defects

Schematic drawing of a poly-crystal with many defects by

Eg. Sterling silver (92.5% Ag + 7.5% Cu) is much

0D, Point defects: atoms missing or atoms in irregular

1D, Linear defects: groups of atoms in irregular

2D, Planar defects: the interfaces between

3D, Volume defects: extended defects (pores, cracks)

- Self-interstitials: extra atoms positioned between

N = Total # of atomic sites

NA = Avogadro’s number = 6.023 * 1023 atoms/mol

1. A cation–vacancy and a cation– interstitial pair.

There is no change in charge because the cation

The ratio of cations to anions is not altered in the

E.g of nonstoichiometric material is FeO.

 Examples: carbon added in small amounts to

Solvent: in an alloy, the element or compound present in

Solute: in an alloy, the element or compound present in

Solid solutions are

1. Atomic size factor - atoms need to “fit” ⇒ solute and

2. Crystal structures of solute and solvent should be

3. Electronegativities of solute and solvent should be

4. Generally more solute goes into solution when the

Composition can be expressed in

For two-component system, concentration of element

where nm1 = m’1/A1

2 main types of dislocation are know

Some of the defects include:

Foreign inclusions - can greatly affect electrical,

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