UNIVERSITI TUNKU ABDUL RAHMAN (UTAR)

Diffusion

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 Diffusion

• Introduction – Rate Reaction & Diffusion

• Diffusion Mechanisms
Vacancy diffusion
Interstitial diffusion

• Steady State diffusion – Fick’s 1st Law

• Non Steady State diffusion – Fick’s 2nd Law

• Factors that influence diffusion

Diffusion Species
Temperature

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 Rate Process in Solids
• Many processes concerned with the rate at which atoms move in the
solid state
• Reactions occur in solid state resulting in more stable atomic
arrangement.
• Reacting atoms must have sufficient energy to overcome activation
energy barrier.
• At a given temperature, not all atoms have activation energy E*. It
should be supplied to them.
E* Er = Energy of reactants
ΔE* E* = Activation Energy Level
Activation Energy ΔE* = Activation Energy
Ep = Energy of Products
Er
Reactants
Energy released
Due to reaction
EP
Products
Reaction Coordinate

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 Rate Process in Solids

• As temperature increases, more and more atoms

acquire activation energy level.
• Probability of finding an atom/molecule with energy E*
greater than average energy E of all atoms/ molecules
is given by

 ( E* E ) / KT
Probability  e
K = Boltzman’s Constant = 1.38 x 10-23 J/(atom K)

T = Temperature in Kelvin.

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 Diffusion

• Phenomenon of material (mass) transport by atomic

motion.

• Atomic movement within the atomic structure arrangement.

• Vary with temperature / kinetic energy. Phenomena of heat

treatment.

• Examples:
 Movement of smoke particles in air : Very fast.
 Movement of dye in water : Relatively slow.
 Solid state reactions : Very restricted movement due
to bonding.

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 Diffusion

Cu Ni

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 Types of Diffusion

Two types of diffusion

Self diffusion Impurity diffusion

(Interdiffusion)
Atomic migration in Diffusion of atoms of
pure metals or of the one metal into another.
same type.

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 Types of Diffusion

Self diffusion

• All atoms exchanging positions are of the same

type.

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 Types of Diffusion

Interdiffusion (Impurity Diffusion)

• There is a net drift or transport of atoms from

high to low concentration region.

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 Diffusion Mechanisms

Atomic diffusion must meet two conditions:

1.There must be an empty adjacent site

2.The atom must have sufficient energy to

break bonds with its neighbour atoms and then
cause some lattice distortion during the
displacement

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 Diffusion Mechanisms

Two Mechanisms

Vacancy diffusion Interstitial diffusion

Interchange of an Involves atoms that migrate

atom from a normal from an interstitial position
lattice position to an to a neighboring interstitial
adjacent vacancy. site that is empty.

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 Diffusion Mechanisms

Vacancy Diffusion (Substitutional Diffusion)

• Degree of diffusion depends on the number of

vacancies that are present.
• The motion of vacancies would be in the opposite
direction corresponds to the atomic diffusion.

increasing elapsed time

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 Diffusion mechanisms
Interstitial Diffusion

• More common with smaller size, such as hydrogen, carbon,

nitrogen and oxygen (small atom fits into interstitial sites)

• More rapidly and frequently than vacancy diffusion

* Interstitial atoms are smaller, more mobile
* More empty interstitial position than vacancies

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 Diffusion Flux
• Diffusion flux – mass M diffusing through and
perpendicular to a unit cross-sectional area of
material per unit time. (rate of mass transfer)
Differential form

M
J = ---- , 1 ----
dM
At J = ---
A dt
Where
A = cross section area which diffusion occur
t = diffusion time

• The units for J is kg/m2s or atoms/m2s

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 Steady-state Diffusion

Steady-state Diffusion (Fick’s First Law)

• Diffusion flux does not change with time.

• It is proportional to the concentration gradient.

dC ΔC CA - CB
• Concentration gradient = ---- = ---- = -----------
dx Δx xA - x B

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 Steady-state Diffusion
Rate of diffusion is independent of time; the diffusion flux does not
change with time.

The concentration profile shows the concentration (C) vs the position

within the solid (x); the slope at a particular point is the concentration
gradient.
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 Steady-state Diffusion

dC
J = – D(-----)
dx
Direction of diffusion
Where
D = diffusion coefficient (m2/s)
dC/dx = concentration gradient

• Concentration gradient is the diving force for the

diffusion reactions.

• The magnitude of D indicates the diffusion rate.

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 Nonsteady-state Diffusion
Nonsteady-state Diffusion
• The diffusion flux and the concentration gradient at some
particular point in a solid vary with time, with a net
accumulation or depletion of the diffusing species
resulting.

• Involves most practical

diffusion situations.

• The figure on the right

shows the concentration
profiles for nonsteady-
state diffusion taken at
three different time t1 , t2
and t3.

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 Nonsteady-state Diffusion

Nonsteady-state diffusion

• Fick’s second law: if the diffusion coefficient is

independent of composition, the time rate of
change of concentration is proportional to the
second derivative of concentration.

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 Nonsteady-state Diffusion

d 2C
dC
----- = D(------)
dt dx2

Where D is the diffusion coefficient (m2/s)

• Solution to the expression is possible for a semi-

infinite solid, in which none of the diffusing
atoms reaches the bar end during the time over
which diffusion takes place

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 Nonsteady-state Diffusion
For a semi-infinite solid :

• l > 10 √Dt , where l is the length of the bar.

• To obtain solution for the expression, the following assumptions

are made ;

1. Before diffusion, any of the diffusing solute atoms in the solid are
uniformly distributed with concentration of C0.

2. The value of x at the surface is zero and increases with distance

into the solid.

3. The time is taken to be zero the instant before the diffusion

process begins.

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 Nonsteady-state Diffusion
For a semi-infinite solid :

• The boundary conditions are stated as follows :

For t= 0, C = C0 at 0 ≤ x ≤∞
For t > 0, C = Cs (the constant surface concentration) at x = 0,
C = C0 at x = ∞

• Application of the boundary conditions to the expression yields

Where Cx represents the concentration at depth x after time t and erf()

is the Gaussian error function

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 Nonsteady-state Diffusion

Concentration, C Cs

Cs – Co
Cx
Cx – Co
Co

Distance from interface, x

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 Nonsteady-state Diffusion
For t= 0, For t > 0,
C = C0, C = Cs C = C0
at 0 ≤ x ≤∞ at x = 0, at x = ∞

Cs X=0

x
Co X

Co
X=∞
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 Nonsteady-state Diffusion

Concentration of diffusing species

t3 t1 < t 2 < t 3

t2
t1

Distance

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 Factors that Influence Diffusion

• The diffusing species as well as the host

material influence the diffusion rate
• Example : the diffusion coefficient at 500oC is greater in carbon- iron
interdiffusion (2.4 X 10-12 m2 /s) as compared to that of iron self-
diffusion (3.0 X 10-21 m2 /s)
• The self-diffusion of  iron occurs by a vacancy mechanism whereas
carbon diffusion in iron is interstitial

• The crystal structure of the host material

influence the diffusion rate of interdiffusion
• Example : the diffusion coefficient at 900o C is greater in
carbon- iron (BCC) interdiffusion ( 1.7 X 10-10 m2 /s) as compared to
that of carbon-  iron (FCC) interdiffusion ( 5.9 X 10-12 m 2/s)

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Factors that Influence Diffusion

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 Factors that Influence Diffusion

• Interstitial diffusion occurs more rapidly in

BCC crystal structure as compared to FCC
crystal structure since there are more
interstitial spaces in crystal structure with a
lower atomic packing factor.

• Type of crystal imperfection: More open

structures (grain boundaries) increases
diffusion.

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 Factors that Influence Diffusion
• Increase in temperature would cause an
increase in the diffusion coefficient and thus the
diffusion rate.

• Example : the self-diffusion of Fe in – Fe, the

diffusion coefficient increases from 3.0 X 10-21 to
1.8 X 10-15 m2 /s in rising temperature from 500o
C to 900o C.

• A large activation energy results in a small

diffusion coefficient.

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 Temperature and Diffusion Rate

Diffusion coefficient,

Where
D0 = a temperature-independent pre-exponential
(m2/s)
Qd = the activation energy, or the energy required to
produce the diffusive motion of one mol of
atoms (J/mol or eV/atom)
R = the gas constant , 8.31 J/mol.K
or 8.62 x 10-5 eV/atom.K
T = absolute temperature (K)
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 Case Hardening

• A technique by which both surface

hardness and fatigue life are
enhanced for steel alloys.

• Can be accomplished by increasing

the surface concentration of carbon via
diffusion in a process termed
carburizing.

• In carburizing, the steel piece is

exposed, at an elevated temperature,
to an atmosphere rich in a
hydrocarbon gas, such as methane
(CH4).
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 Case Hardening
A plate of iron is exposed to a carburizing (carbon-rich) atmosphere on one
side and a decarburizing (carbon-deficient) at mosphere on th other side at
700oC (1300oF). 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 (5 x 10-3 and 10-2 m) beneath the carburizing
surface are 1.2 and 0.8 kg/m3, respectively. Assume a diffusion coefficient of
3 x 10-11 m2/s at this temperature.

Solution

Fick’s first law is utilized to determine the diffusion flux.

CA - CB (1.2 – 0.8) kg/m3

J = – D(----------) = – (3 x 10 m /s) -----------------------
-11 2
xA - xB (5 x 10-3 – 10-2) m
= 2.4 x 10-9 kg/m2s

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 Case Hardening
For some applications, it is necessary to harden the surface of a steel (or iron-carbon alloy) above that of its
interior. One way this may be accomplished is by increasing the surface concentration of carbon in a
process termed carburizing: the steel piece is exposed, at an elevated temperature, to an atmosphere rich in
a hydrocarbon gas such as methane (CH4).

Consider one such alloy that initially has a uniform carbon concentration of 0.25 wt% and is to be treated at
950oC (1750oF). If the concentration of carbon at the surface is suddenly brought to ad 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 x 10-11 m2/s; assume that the steel piece
is semi-infinite.

Solution

Since this is a nonsteady-state diffusion problem in which the surface composition is held constant. Values
for all the parameters in this expression except time t are specified in the problem as follows :
Co = 0.25 wt% C
Cs = 1.20 wt% C
Cx = 0.80 wt% C
x = 0.50 mm = 5 x 10-4 m
D = 1.6 x 10-11 m2/s Cx - Co 0.80 – 0.25 5 x 10-4 m
---------- = -------------------- = 1 – erf (-------------------------------)
Thus Cs - Co 1.20 – 0.25 2√(1.6 x 10-11 m2/s)(t)

62.5 s½
0.4210 = erf (------------)
√t

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 Case Hardening
We must now determine the value of z for which the error function is 0.4210. An interpolation is
necessary, as
z erf (z)
0.35 0.3794
z 0.4210
0.40 0.4284

Z – 0.35 0.4210 – 0.3794

--------------- = -----------------------
0.40 – 0.35 0.4284 – 0.3794

Z = 0.392

62.5 s½
(------------) = 0.392
√t
62.5 s½
t = (------------)2
0.392

= 25,400s = 7.1h

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