CHAPTER 5

5.1 CRYSTAL DEFECTS

C R YSTAL DEF ECTS

In a perfect crystal, atoms would exist only on lattice sites

and every lattice site would be occupied by an atom.

A ND DIF F US ION
5.1

A crystal defect or imperfection is an irregularity in the

crystal lattice, a departure from the perfect crystal. Defects

CRYSTAL DEFECTS

affect material properties, but not necessarily adversely.

5.1.1 Thermal Vibration of Atoms

5.1.2 Vacancies
5.2

Point defects are zero dimensional imperfections that

involve only a few atoms at most. These include: vacancies

DIFFUSION

(Sec. 5.1.2)

5.2.1 Vacancy Diffusion

5.2.2 Interstitial Diffusion

Linear defects are one-dimensional imperfections where

5.2.3 Concentration and Flux

5.3

and impurities (Sec. 6.3.2).

local faults in the atomic arrangement lie along a straight

FACTORS AFFECTING RATE OF DIFFUSION

line, curve or loop through the crystal. Linear defects are

5.3.1 Temperature

collectively known as dislocations (Sec. 6.2).

5.3.2 Diffusion Mechanism

Planar defects are two-dimensional imperfections that

5.3.3 Atomic Bonding

serve as boundaries between regions having different

5.3.4 Crystal Structure

5 . 3 . 5 Crystal Defects (Short Circuit Diffusion)

crystal structures and/or crystallographic orientations.

Grain boundaries (Sec. 4.7) are one class of planar defects.
Volume defects are macroscopic (large-scale) defects that
represent inhomogeneities in a solid. Among these are:
inclusions (unwanted foreign particles), precipitates
6.3.3),

5-1

(Sec.

cracks (Chp. 7) and voids.

5-2

5.1.1

Thermal Vibration of Atoms

At temperatures above absolute zero (0 Kelvin), atoms

Fig. 5.1-2 Illustration

showing how an atom must
overcome an activation
energy, Q, to move from
one stable position to a
similar adjacent position.

possess kinetic energy and vibrate about their equilibrium

lattice positions (see also Sec. 3.7).
At any given temperature, the average kinetic energy of a
material is fixed; however, the kinetic energy of an
individual atom at any time is not constant but randomly
distributed over a wide range (Fig. 5.1-1).

The number of atoms that possess enough kinetic energy

to overcome the activation energy barrier (i.e. E ! Q) and
make successful jumps may be found from the kinetic
energy distribution of atoms.

Fig. 5.1-1 Distribution of

kinetic energy of atoms
changing with temperature.
N(E) represents the number
of atoms that possess E
amount of kinetic energy.

The rate at which atoms make successful jumps must be

proportional to number of such atoms (with enough E).
This rate is described by the Arrhenius equation:

Sometimes an atom in a solid may possess high enough

kinetic energy to enable it to break its bonds with its

Rate = C exp %" Q (

neighbours and jump away from its original lattice position

to another site.

&

RT '

where

C = material constant
Q = activation energy
R = gas constant
T = absolute temperature

The amount of energy required for breaking atomic bonds

and making a jump is known as the activation energy, Q
(Fig. 5.1-2).
5-3

The Arrhenius equation implies that a low activation

energy and/or a high temperature will result in faster rates.
5-4

5.1.2

Vacancies

5.2 DIFFUSION

A vacancy is a vacant lattice site from which an atom is

missing

(Fig. 5.1-3).

Diffusion is the spontaneous movement of atoms within a

Vacancies are defects that occur naturally

material as a result of atomic vibrations. The manufacture

as a result of atomic vibrations; they may also be

of many materials (e.g. surface hardening, microchips) and

introduced during processing, or arise from radiation

most changes in microstructure (and therefore, properties)

damage.

are accomplished through diffusion.

There is an equilibrium number of vacancies, Nv, at any

temperature, T:

Self-diffusion is the constant, random, movement of

atoms of the same type within pure materials.

Nv = N exp %" Q (
#

&

RT '

where

It occurs in the absence of a concentration gradient; there

N = total no. of lattice sites

is no net flow of atoms.

Qv = energy required to form a

vacancy (J/mol)

The effects on material properties are insignificant.

R = gas constant (J/mol.K)

Interdiffusion is the movement of atoms from one

T = absolute temperature (K)

material into another unlike material.

Fig. 5.1-3 A vacancy.

It occurs in the presence of a concentration gradient; there

A crystal will always contain vacancies at any temperature

is a net flow of atoms from high to low concentration.

above absolute zero (0 K). The equilibrium number of

Interdiffusion affects material properties.

vacancies, Nv, increases with temperature.

Vacancies are the basis of an important mechanism for the
movement

of

atoms

(diffusion)

within

metals

and

This type of diffusion is also known as impurity diffusion

or heterogeneous diffusion.

ceramics.
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5-6

5.2.1

Vacancy Diffusion

5.2.2

In vacancy diffusion, the diffusing atom moves from its

normal lattice position to an adjacent vacancy. (Fig. 5.2-1)

Interstitial Diffusion

In interstitial diffusion, the diffusing atom moves from

one interstitial site to an adjacent empty interstitial site.

(Fig.

5.2-3)

The interstitial diffusion mechanism is limited to small

solute atoms such as H, C, N, O, which are small enough
to squeeze into the interstitial sites between lattice atoms.

Fig. 5.2-1 Schematic representation of vacancy diffusion.

Vacancy diffusion is the mechanism for self-diffusion, as

well as interdiffusion, when the diffusing atoms and host
atoms are of comparable size.

Fig. 5.2-3 Schematic representation of interstitial diffusion.

Since vacancies must first be

No vacancies are required for interstitial diffusion to occur.

available for atoms to move

into

(Fig.

diffusion

5.2-2),

is

the rate of

limited

by

At lower temperatures, interstitial diffusion is generally

the

faster than vacancy diffusion, since interstitial sites are far

number of vacancies.

more abundant than vacancies. Furthermore, interstitial

Fig. 5.2-2 A mechanical analogy of
vacancy diffusion using a puzzle in a
frame, showing how a vacancy must first
exist before an atom can move into it.
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atoms are smaller and more mobile.

5-8

5.2.3

Concentration and Flux

The plot of concentration, C, against distance (along x, y

or z axis), is called the concentration profile. The slope,

When

there

is

difference

in

concentration

"C , at a particular point on the concentration profile is the

"x

(i.e.

composition), random atomic jumps will result in a net

flow of atoms from high to low concentration, until the
diffusing

atoms

are

uniformly

distributed

and

the

concentration gradient is zero (Fig. 5.2-4).

Concentration profile
of copper

concentration gradient. These can change with time.

!

Diffusion problems in solids often involve finding out how

fast diffusion occurs. This rate of mass transfer is measured

Concentration profile
of nickel

by the diffusion flux, J, defined as the mass (or

equivalently, the number of atoms) passing through a unit
cross-sectional area of the solid per unit time (Fig. 5.2-5).
The flux at any position along a diffusion path is related to
the instantaneous concentration gradient at that point:
J = -D "C
"x

where D is the diffusion coefficient or diffusivity (m2/s)

!

Fig. 5.2-4 Interdiffusion of copper atoms into nickel and vice versa.

Fig. 5.2-5 Illustration of diffusion flux. The units of J are kg/m2.s or atoms/m2.s
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5-10

5 . 3 F ACTORS A FFECTING R ATE OF D IFFUSION

The flux of atoms is proportional to the concentration
gradient, with the constant of proportionality being the
diffusion coefficient, D. The magnitude of D is indicative of
the rate at which atoms diffuse.
D is directly related to the frequency at which atoms jump
from site to site within a solid. Jumps can only occur when
atoms possess high enough kinetic energy to overcome
the activation energy barrier. D is thus described by the
Arrhenius equation:
D = Doexp %" Q (
#

&

RT '

where Do = material constant (m2/s)

Q = activation energy (J/mol)

R = gas constant (J/mol.K)
T = absolute temperature (K)

5.3.1

Temperature

With higher temperatures, the number of atoms with

Fig. 5.3-1 Arrhenius plot of logarithm of diffusion coefficient D as a function of

the reciprocal of absolute temperature of some metals and ceramics.
A rise in T (i.e. lower T1 ) increases D.

kinetic energy high enough to overcome the activation

energy barrier increases, so the jump frequency of the

atoms rises. Therefore, the higher T is, the larger D

becomes, and the faster the rate of diffusion (Fig.5.3-1).
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5-12

5.3.2

Diffusion Mechanism

The activation energy, Q, depends on the diffusion

mechanism (vacancy or interstitial). When Q is high, few
atoms possess the kinetic energy required to overcome Q
and make a jump, so D is low and diffusion is slow.
In vacancy diffusion, a vacancy must first be created before
an atom can jump from an adjacent lattice site. Q then
consists of the energy required for vacancy formation plus
the energy required for an atom to jump.
In interstitial diffusion, interstitial spaces are always
available, so Q is simply the energy an atom requires to
jump into an adjacent interstitial site.
In general, Qvacancy > Qinterstitial. (Fig. 5.3-2 & Table 5.3-1)

Fig. 5.3-2
Qvacancy > Qinterstitial.

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5.3.3

Atomic Bonding

5.3.4

The activation energy, Q, also depends on the atomic

bond strength. Q is high for materials with strong atomic
bonds (reflected in the high melting points)

(Table 5.3-2),

because an atom in such a material requires high kinetic

energy in order to break its bonds with its neighbours and
make a jump.

Crystal Structure

The influence of atomic packing within the crystal structure

is reflected in Q and Do. It is more difficult for atoms to
squeeze through regions that are densely packed; in
general, Q is higher and/or Do is smaller in close-packed
structures (e.g. FCC), resulting in lower D and slower
diffusion. (Fig. 5.3-3 & Table 5.3-3)

Table 5.3-2 Typical Activation Energies for Self-Diffusion, Q

Fig. 5.3-3 Arrhenius plots

showing approximate ranges
of D for vacancy diffusion in
BCC and FCC alloys. TM is the
melting point of the alloy.

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5.3.5

Crystal Defects (Short Circuit Diffusion)

In nanocrystalline materials, which have a large proportion

of

grain

boundaries,

grain

boundary

diffusion

can

Crystal defects such as dislocations (Sec. 6.2), grain boundaries

dominate. Similarly, in fine powders with large surface area,

and surfaces provide open, disordered regions

surface diffusion can dominate; e.g. sintering of powders in

(Sec. 4.7)

through which atoms can move easily. Q for diffusion along

powder metallurgy or manufacture of ceramics (Fig. 5.3-5).

such short circuits is much lower than through the bulk of

the crystal (Fig. 5.3-4), so D is higher and diffusion faster.
Since the cross-sectional areas of these easy diffusion paths
are usually small, volume diffusion is still dominant under
most temperatures. Only at low temperatures does short
circuit diffusion become significant.

Fig. 5.3-5 Surface diffusion is significant in the sintering of powders.

Short circuit diffusion in microelectronic devices is a

reliability issue due to the comparable dimensions of the
electronic circuits and crystal defects.

Fig. 5.3-4 Arrhenius plots showing D for diffusion along various different paths.
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