1 Diffusion

Diffusion in Solids!
Phenomenon!
put one drop of ink in a glass of
water: you will see ink diffusing
away and eventually
indistinguishable (the water
becomes slightly blue)!
pickled vegetable: salt applied
on the surface diffusing into the
inside!
case hardening of steel: put a
steel component in a high
temperature furnace with a
carbonising or nitrogenising
atmosphere, and C or N atoms
will diffuse from the surface into
the component causing
hardening of the surface!
Definition!
transport of atoms from place to
place within a solid material!
Effect!
causing microstructure change
during service (often
damaging)!
causing phase transformation
during heat treatment!
Quantitative description!
Fick's first law!
Fick's second law!
temperature dependence!
What is the mechanism?!
vacancy!
interstitial!
Reading: Chapter 5 (5th and 6th ed)

MCEN90014: Materials
!Dr. K. Xia!
!1!
!2!
at a sufficiently
high
temperature

for a period of
time

Interdiffusion: one
type of atoms
diffusing into
another type, most
likely driven by
composition
difference

t
!Dr. K. Xia!
at a sufficiently
high
temperature

for a period of
time

Self-diffusion:
same type of
atoms diffusing
among
themselves, for
example driven
by stress as in
diffusional creep

!Dr. K. Xia!
!3!
Diffusion in Solids - Mechanisms!
Vacancy diffusion

Interstitial diffusion

!Dr. K. Xia!
!4!
for diffusion in a single direction

(e.g. x) and observed at a
particular moment!
dC
J = D
d x t=to
Diffusion Rate!
Measurement of how fast a
diffusion takes place!
diffusion flux: mass transported
per unit area per unit time!
J=
M
At
M: mass (kg or number of

atoms)!
A: cross section area (diffusion
takes place perpendicular to
the cross section) (m2)!
t: time (s)!
Fick's law: diffusion flux is

proportional to the concentration
gradient of the diffusing atoms!
when concentration difference is driving diffusion

C: concentration (kg/m3 or g/
cm3)!
x: position (dx in m or cm)!
D: diffusion coefficient (m2/s
or cm2/s)!
t = to

x
J

when dC is
plus, J is
negative (in
the opposite
direction of x
axis)

!Dr. K. Xia!
when dC is
minus, J is
positive (in
the direction
C + dC
of x axis), as
shown here

x x + dx
C

!5!
Example 5.1!
Steady state diffusion!
CA = 1.2 kg/m3!
Steady state: concentration profile
CB = 0.8 kg/m3!
(concentration as a function of
D = 3 x 10-11 m2/s!
location) does not change with
time, i.e. C = C(x)!

Fick's first law!
J = D
dC
dx
J may change
with x but not t

A
CA

dC
C CA
= D B
dx
xB xA
0.8 1.2
= 3 10 11
= 2.4 10 9 kg/m 2 s
5 10 3
J = D
Concentration
profile

CA

C
CB

This can be realised if CA
and CB are kept constant

Concentration
profile of C at
steady state

5 mm

x
!
T = 700C

!Dr. K. Xia!
CB

plate of Fe

!
x
!
!6!
Steady state flow of water

Water levels do not change with time

Water in

Water out

Direction of water flow

Flow rate is constant

!Dr. K. Xia!
!7!
!8!
Non-steady state diffusion!

In general, concentration profile
does change with time, i.e. C =
C(x, t)!
Fick's second law!
C
2C
=D 2
t
x
this is a partial differential

equation!
analytical solutions may be
found for some boundary
conditions!
increasingly, numerical
solutions are obtained by finite
element analysis using
computer!
!Dr. K. Xia!
Non-steady state diffusion!

Analytical solution to Fick's
second law equation for a semiinfinite plate with a constant
surface concentration with the
following initial and boundary
conditions!
t = 0, C = Co at 0 x !
for t > 0, C = Cs at x = 0 and
C = Co at x = !
Cs

t = 0

Co

# x &
C x Co
= 1 erf %
(
$ 2 Dt '
C s Co
t = to > 0

erf: Gaussian error function!
Cx

See table 5.1 for

selected values of erf

Surface

!Dr. K. Xia!
!9!
Diffusion in Solids - Example!
Example 5.2!
From table 5.1 using
interpolation

Known!
Co = 0.25 wt%!
Cs = 1.20 wt%!
D = 1.6 x 10-11 m2/s!
Require!
Cx = 0.8 wt% at x = 0.5 mm!
How long will it take (i.e. t = ?)!
Solution!
Using equation on the previous page!
Cs

Cs = 1.20 wt% C

T = 950C

CH4
gas at
surface
to keep
Cs

t = 0

Co = 0.25 wt% C

Co

t = ?

%
(
0.80 0.25
5 10 4
= 1 erf '
*
11
1.20 0.25
& 2 1.6 10 t )
" 62.5 %
62.5
= 0.392
0.4210 = erf $
'
# t &
t
" 62.5 %2
t =$
' = 25400 s = 7.1 h
# 0.392 &
Surface

!Dr. K. Xia!
Fe-0.25 C
steel

C0.5 mm = 0.80 wt% C

0.5 mm

!
!10!
z = ?

0.4210

z 0.35
0.4210 0.3794
=
0.40 0.35 0.4284 0.3794
z = 0.392
!Dr. K. Xia!
!11!
Diffusion coefficient!
J = D
log D = log D0
log D

D determines how fast a

diffusion takes place!
dC
dx
the higher D is, the larger J

for the same driving force
(dC/dx)!
Expression for D!
# Q &
!
D = Do exp% d ( Arrhenius
$ RT ' equation

!
Do: constant for a certain type
and
of diffusion (m2/s)!host
diffusing species

Qd: activation energy for
diffusion (J/mol)!
R: gas constant = 8.31 J/mol-K!
T: absolute temperature (K)!
Qd # 1 &
% (
2.3R $ T '
the slope

1/T

Do (the up and down position) and Qd (the slope)
dependent on the diffusion system (NOT T!)

Temperature has very significant influence on D

!Dr. K. Xia!
IMSE: !Diffusion coefficients

!
!12!
The diffusing
atom can jump in
any direction that
is available

An activation energy is needed for the

diffusing atom to "squeeze" through to
the vacancy next door

There are more vacancies and the atoms have more
energy (vibrational) at a higher temperature
diffusion is faster with increasing temperature

!Dr. K. Xia!
!13!
!14!
Diffusion system

!Dr. K. Xia!
Example 5.5!
Known: log D vs 1/T curve!
Qd and Do = ?!
Solution!
Pick up any two points from the
curve (e.g. {D1,T1} & {D2,T2})!
Qd = 2.3R Slope!
log D

Diffusion in Solids - Example!

Cu diffusion in Au

(D1, T1)

Qd/2.3R

1
#
&
% log D log D (
1
2
(
Qd = 2.3R%
1 1
%%
((
T1 T2
$
'
# 12.40 (15.45) &
= 2.3 8.31%
(
1/T x 1000

$ 0.8 10 3 1.110 3 '
= 194000 J /mol = 194 kJ /mol
Q "1%
194000
log Do = log D + d $ ' = 12.40 +
0.8 10 3 = 4.28
2.3R # T &
2.3 8.31
(D2, T2)

Do = 10 4.28 = 5.25 10 5 m 2 /s
!Dr. K. Xia!
!15!
!16!
Diffusion in Solids - Summary!
Phenomenon!
mass transport in solids!
Mechanism!
vacancy!
interstitial!
Quantitative description!
Fick's first law!
Fick's second law!
their applications!
Diffusion coefficient!
D!
effect of T!
Qd and Do!
how to determine them!
!Dr. K. Xia!

1 Diffusion

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1 Diffusion

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Diffusion in Solids!

Diffusion in Solids - Mechanisms!

for diffusion in a single direction

M: mass (kg or number of

Fick's law: diffusion flux is

when concentration difference is driving diffusion

time, i.e. C = C(x)!

Steady state flow of water

Direction of water flow

Non-steady state diffusion!

this is a partial differential

Non-steady state diffusion!

erf: Gaussian error function!

See table 5.1 for

Diffusion in Solids - Example!

C0.5 mm = 0.80 wt% C

D determines how fast a

the higher D is, the larger J

IMSE: !Diffusion coefficients

An activation energy is needed for the

Diffusion in Solids - Example!

Diffusion in Solids - Summary!

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