Diffusion in Solids
Prof. V. E. Buchanan
School of Engineering
1
Learning Outcomes
P Explain the meaning of diffusion.
P Explain the mechanisms of diffusion in
metals: self, vacancy and interstitial diffusion.
P State the factors that influence diffusion.
P State the difference between steady and
non-steady state diffusion.
P State Fick's laws of diffusion.
P Solve problems involving Fick’s laws.
P State typical applications of diffusion.
2
Content
P Diffusion mechanisms
< Self (Interchange) diffusion
< Vacancy (Substitutional) diffusion
< Interstitial diffusion
P Fick’s Laws of diffusion for steady and non-
steady
P Diffusion calculation for steady and non-
steady state
P Applications of diffusion
3
What is Diffusion?
P Diffusion is a mass transfer phenomenon that
causes the distribution of a chemical species to
become more uniform in space as time passes.
P Here, the chemical species migrate from regions of
high concentration to regions of low concentration,
down a concentration gradient until the two
concentrations are equal.
4
What is Diffusion, contd.
P Atomic diffusion is the principal mechanism in
solids, but is difficult due to bonding of atoms in
the lattice structures.
P Also, for diffusion to occur in solids:
< Adjacent sites need to be empty (vacancy or interstitial)
< Availability of sufficient energy to break bonds with
neighbours and overcome lattice distortion
– The energy is called the activation energy.
– A higher activation energy implies easier diffusion.
P Mechanisms by which atoms diffuse are:
< Self or Interchange Diffusion
< Vacancy or Substitutional Diffusion
< Interstitial Diffusion
5
Self Diffusion
P Atoms move from one lattice position to
another by exchanging positions.
P Occurs continually in all materials, but the
effect on the material’s behaviour is not
significant.
6
Vacancy (Substitutional) Diffusion
P Vacancy diffusion
occurs when atoms
move from one site
to another vacant
site.
P The rate of diffusion depends on the:
< Number of vacancies
< Activation energy to force the atom to its new
position (bonds at old position have to be broken)
< Temperature (more vacancies are created at higher
temperature)
< Melting point (As the melting point increases,
activation energy decreases)
< Crystal structure
7
Interstitial Diffusion
P Smaller atoms (H, He, C, O, N, etc.) than the
host atoms move between interstitial sites.
P Generally faster than vacancy diffusion as
< There are more interstitial sites
< Bonding of interstitials to the host atoms is weaker
< Less energy is required to move atoms
8
Diffusion Flux
P The diffusion flux, J, is the
amount of species (atoms,
molecules, etc.) passing through
a plane of unit area per unit time.
M 1 dM M (number of
Flux ( J ) or J
At A dt atoms/moles/mass)
2 2 2
Unit for J = g m s or atoms/m s or mol m s
P There are two laws governing diffusion in
materials.
< Fick’s first law for steady state diffusion, and
< Fick’s second law for non-steady state diffusion
9
Simulating Steady and Non-steady
State Diffusion
P In a finite vessel with no
supply of material, a
uniform, steady-state
concentration will be
attained.
P But in an infinite space
or in the presence of a
constant supply of
material, a uniform
concentration may not
be attained, i.e., non-
steady state. https://www.comsol.com/multi
physics/what-is-diffusion
10
Steady State Diffusion
P There is no change in concentration of the
diffusing species at different planes in a
system, over a period of time.
P The rate at which the species diffuse is
measured by the diffusion flux, J.
11
Fick’s First Law of Diffusion
P At steady state, the rate of diffusion is
independent of time, and the diffusion flux is
proportional to the concentration gradient.
dC dC C2 C1
J D where
dx dx x 2 x1
P D (m2/s) is the constant of
proportionality, and is called the
diffusion coefficient or diffusivity.
P The diffusion coefficient may be
interpreted as a measure of
mobility of diffusing species, that
is, a measure of the rate of the
diffusion process.
12
Fick’s First Law, contd.
P Fick’s first law may also be expressed
as a differential:
dC
J D
dx
1 dM dC
Also, J D
A dt dx
dM dC
DA
dt dx
13
Factors Influencing Diffusivity
P Diffusion mechanism - substitution or interstitial
P Temperature
< As the temperature increases diffusivity increases.
P Type of crystal structure of the host lattice
< BCC crystal has lower APF than FCC and, hence,
has higher diffusivity.
P Type of crystal imperfections
< Diffusion is faster along grain boundaries (greater
vacancy concentration) than elsewhere in the crystal
< Excess vacancies enhance diffusivity.
P Concentration/composition of diffusing species
< The greater the difference in concentration or
composition, the more rapid the diffusion.
14
Effect of Temperature on Diffusivity
P Diffusion coefficient increases with increasing
temperature.
Q
D Do exp
RT
D = Diffusion coefficient, m2/s
Do = pre-exponential, m2/s
Q = Activation energy, J/mol or eV/atom
R = Gas constant, 8.314 J/mol.K
T = Absolute temperature, K
The pre-exponential and the activation energy
depends on factors such as size of the
interstitial atoms, elastic modulus, melting
point, and crystal structure.
15
Example 1
A plate of iron is exposed to a carburizing
(carbon-rich) atmosphere on one side and a
decarburizing (carbon-deficient)
atmosphere on the other side at 700 oC. If a
condition of steady state is achieved,
calculate the diffusion flux of carbon
through the plate if the concentrations of
carbon at positions of 5 and 10 mm beneath
the carburizing surface are 1.2 and 0.8
kg/m3, respectively. Assume a diffusion
coefficient of 3 × 10-11 m2/s at 700 oC.
Callister, 2007
dC C 2 C1
J D D 11 2
3 10 m / s
0.8 1.2 kg/ m
3
9
2.4 10 kg/ m s
2
dx x 2 x1 0.010 0.005 m
16
Example 2
There is one carbon atom per 10 unit cells at the
surface of FCC iron. There is one carbon atom per
30 unit cells 1 mm beneath the surface. At 900 oC,
how many carbon atoms diffuse down the gradient
per second through each cm2? At 900 oC, radius of
FCC iron = 0.129 nm and diffusion coefficient = 1 ×
10-7 cm2/s.
Solution:
First, the unit for concentration is atom or mass
or mole per unit volume. Therefore, we must
convert cells to volume.
17
Solution 2, contd.
a FCC iron 2 2 R 2 2 0129
. nm 0.3648 10 7 cm
1 atom 1 atom
C1 2.060 10 21 atoms / cm 3
10 a
3 3
10 0.3648 10 7 cm
1 atom 1 atom
C2 6.866 10 20 atoms / cm 3
30 a
3 3
30 0.3648 10 7 cm
dC C2 C1
J D D
dx x 2 x1
1 10 7
cm 2
/ s
6.866 10 20
2.060 10 21 atoms / cm 3
0.1 0 cm
1.37 1015 atoms / cm 2 .s
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Non-steady State Diffusion
P Concentration of diffusing species at any
point in the material changes with time.
P This is the most common situation.
Change of concentration of solute
atoms with change in time in different
planes
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Fick’s Second Law
P The first law does not consider the fact that the
gradient and local concentration of the
impurities in a material decreases with an
increase in time.
P This aspect of time dependence is important to
most diffusion processes.
P Under conditions of non-steady state diffusion,
Fick’s second law is used. The law states:
< The change in concentration with time in a particular
region is proportional to the rate of change in the
concentration gradient with distance at that region in
the system. Mathematically, dC d dC
D
dt dx dx
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Fick’s Second Law, contd.
Solution depends on the boundary conditions for a
particular situation. One such solution is:
Cs C x x
erf
Cs Co 2 Dt
P Cs is the constant
concentration of the
diffusing atoms at the
surface of the material.
P Co is the initial uniform concentration of the diffusing
atoms in the material.
P Cx is the concentration of the diffusing atom at a
distance x below the surface after time t1.
P erf is a mathematical function called error function.
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Error Function Values
22
Analysis of Fick’s Second Law
Cs C x x
erf
Cs Co 2 Dt
If the boundary conditions (Cs, Cx, and Co) do not
change, then:
x
constant K
2 Dt
x 2K D t K' t
x t constant concentrations and diffusivity
and x Dt constant concentrations
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Example 3
A 1020 steel gear is to be gas carburized at 927
o
C. Calculate the carbon content at 0.5 mm
beneath the surface of the gear after 5 hours of
carburizing time. Assume that the carbon content
of the surface of the gear is 0.9 wt% and that the
steel has a nominal carbon content of 0.2 wt%.
Given D for steel at 927 oC = 1.28 × 10-11 m2/s.
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Cs C x x
Cs Co
erf
2 Dt
Solution 3
0.9 C x 5 10 4
m
erf
0.9 0.2 2 1.28 10 11m 2 / s 5 3600 s
0.9 C x Z erf(z)
erf 0.5208 0.5000 0.5205
0.7 0.5208 X
0.5500 0.5633
x - 0.5205 0.5208 - 0.5000
0.5633 0.5205 0.5500 - 0.5000
x - 0.5205 0.0208
0.4160
0.0428 0.05
x 0.0428 0.4160 0.5205 0.5383
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Solution 3, contd.
0.9 C x
erf 0.5208
0.7
Substituting
0.9 C x
0.5383
0.7
0.9 C x 0.7 0.5383 = 0.3768
C x 0.9 - 0.3768 = 0.52 wt%
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Example 4
An alloy initially has a uniform carbon
concentration of 0.25 wt% and is to be treated at
950 oC. If the concentration of carbon at the
surface is suddenly brought to and maintained at
1.20 wt%, how long will it take to achieve a
carbon content of 0.80 wt% at a position 0.5 mm
below the surface? The diffusion coefficient for
carbon in iron at this temperature is 1.6 × 10-11
2
m /s. Assume that the steel piece is semi-infinite.
Callister, 2007
27
Co = 0.25 wt% C
Solution 4 Cs = 1.20 wt% C
Cs C x x Cx = 0.80 wt% C
erf -4
Cs Co 2 Dt x = 0.50 mm = 5 × 10 m
D = 1.6 × 10-11 m2/s
1.20 0.80 5 10 4 m
erf
1.20 0.25 2 1.6 10 m / s t
11 2
62.5s 0.5
0.4210 erf
t
62.5s 0.5
0.392
t
2
62.5s 0.5
t
0.392
25 421 s 7.1 hr
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nd
Applications of Fick’s 2 Law
P Several cases in which diffusion is important
are:
P Case hardening (Carburising, Nitriding,
Carbonitriding)
P Galvanising
P Annealing (Recrystalisation and grain growth)
P Diffusion Bonding
P Sintering
P Doping silicon with phosphorus for n-type
semiconductors
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Case Hardening
P This is a process in which one
element is diffused into
another (a solid), the diffusion
being limited to a small region
near the surface.
P The diffused region becomes harder, but the
core remains ductile.
P Case hardening of steel components like
gears is done by:
< Carburising - diffusing Carbon into the surface of
mild steel
< Nitriding - diffusing Nitrogen into the surface of
mild steel
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Grain Growth
P A material composed of many grains
contains a large number of grain
boundaries, which increase vacancies.
P Grain growth involves the movement of
grain boundaries, permitting some
grains to grow at the expense of other.
< Reduce excessive vacancies and
dislocations formed during working
P Therefore, diffusion of atoms across the grain
boundary is required.
P High temperatures or low activation energies
increase the size of the grains, i.e, for the
growth of the grains.
31
Diffusion Bonding
P Diffusion bonding is a method of creating a joint
between similar or dissimilar materials.
P The surface of two materials are heated and
pressed together (typically in a vacuum) for a
specific holding time, causing atoms to diffuse
along grain boundaries to the remaining voids.
P Bonding temperature
< Typically 50% - 70% of the melting temperature
of the most fusible metal in the composition
< Raising the temperature aids in the interdiffusion
of atoms across the face of the joint.
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Advantages of Diffusion Bonding
P Properties of parent materials are generally
unchanged
P Diffusion bonding can bond similar or dissimilar
metals and nonmetals.
P The joints formed by diffusion bonding are
generally of very high quality.
P The process naturally lends itself to automation.
P Does not produce harmful gases, ultraviolet
radiation, metal spatter or fine dusts.
P Does not require expensive solders, special
grades of wires or electrodes, fluxes or shielding
gases.
33
Sintering
P Sintering is the high-temperature treatment that
causes particles to join together and gradually
reduces the volume of pore space between them
< Atoms diffuse to points in contact, creating bridges and
reducing the pore size
P Sintering is a frequent step in the manufacture of
ceramic components, as well as in the production of
metallic parts by powder metallurgy.
P A variety of
composite
materials are
produced
using the
technique.
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Other practical applications are:
P How much oxygen gets into the blood stream
from the lungs.
P How capillaries take gases in/out from an
interstitial fluid.
P How things pass across membranes.
P How to get the caffeine out of coffee beans.
P Interpreting MRI of the brain.
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Summary
P Diffusion FASTER P Diffusion SLOWER
for... for...
< open crystal < close-packed
structures structures
< materials with < materials with
secondary bonding covalent bonding
< smaller diffusing < larger diffusing
atoms atoms
< lower density < higher density
materials materials
< High-temperature < Low temperature
conditions conditions
< Cations < Anions
36
Bibliography/Reference
P Smith, William F. Principles of Materials
Science and Engineering., Third Edition
P William D. McCallister, Jr., Materials Science
and Engineering – An Introduction, 8th ed.,
John Wiley & Sons, Inc., New York, 2010
P http://www.slideshare.net/luiscobaya/diffusion
-in-materials
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