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
MCEN90014: Materials Dr. K. Xia 1

Diffusion in Solids

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
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 Diffusion in Solids

at a sufficiently
high
temperature
s
s

for a period of
time

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

MCEN90014: Materials Dr. K. Xia 3

Diffusion in Solids - Mechanisms

Vacancy diffusion

Interstitial diffusion

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2
 Diffusion in Solids
Diffusion Rate – for diffusion in a single direction
(e.g. x) and observed at a
• Measurement of how fast a
diffusion takes place particular moment
dC
– diffusion flux: mass transported J = −D
per unit area per unit time d x t=to
M C: concentration (kg/m3 or
J= g/cm3)
At
• M: mass (kg or number of € x: position (dx in m or cm)
atoms) D: diffusion coefficient (m2/s
• A: cross section area (diffusion or cm2/s)
€ takes place perpendicular to t = to
the cross section) (m2)
• t: time (s) x
J
• Fick's law: diffusion flux is
proportional to the concentration when dC is when dC is
gradient of the diffusing atoms plus, J is x x + dx minus, J is
negative (in positive (in
the opposite C the direction
direction of x C + dC of x axis), as
when concentration difference is driving diffusion axis) shown here
MCEN90014: Materials Dr. K. Xia 5

Diffusion in Solids
Steady state diffusion • Example 5.1
CA = 1.2 kg/m3
• Steady state: concentration profile
(concentration as a function of CB = 0.8 kg/m3
location) does not change with D = 3 x 10-11 m2/s
time, i.e. C = C(x) dC C − CA
J = −D = −D B
• Fick's first law dx xB − xA
dC J may change 0.8 −1.2
J = −D = −3 ×10 −11 ⋅ = 2.4 ×10 −9 kg/m 2 ⋅ s
dx with x but not t 5 ×10 −3

A B A B
Concentration
CA € CA profile of C at
€ Concentration steady state
profile
C
C

CB 5 mm CB
This can be realised if CA
x T = 700°C plate of Fe
and CB are kept constant x
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3
 Diffusion in Solids

Steady state flow of water

Water levels do not change with time

Water in

Water out
Direction of water flow
Flow rate is constant

MCEN90014: Materials Dr. K. Xia 7

Diffusion in Solids
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

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4
 Diffusion in Solids
Non-steady state diffusion Cs
• Analytical solution to Fick's
t=0
second law equation for a semi-
infinite plate with a constant
surface concentration with the
following initial and boundary
conditions
– t = 0, C = Co at 0 ≤ x ≤ ∞ Co

– for t > 0, C = Cs at x = 0 and

C = Co at x = ∞
C x − Co # x & t = to > 0
= 1− erf % (
C s − Co $ 2 Dt '
erf: Gaussian error function
See table 5.1 for selected values of erf
Cx

Surface
MCEN90014: Materials Dr. K. Xia 9

Diffusion in Solids - Example

Example 5.2 Cs
From table 5.1 using Cs = 1.20 wt% C
• Known interpolation

Co = 0.25 wt% CH4 T = 950°C

Cs = 1.20 wt% gas at t=0
Fe-0.25 C
surface
D = 1.6 x 10-11 m2/s steel
to keep
• Require Cs
Co = 0.25 wt% C
Cx = 0.8 wt% at x = 0.5 mm Co
• How long will it take (i.e. t = ?)
Solution
Using equation on the previous page t=?
0.80 − 0.25 % 5 ×10 −4 (
= 1− erf ' −11 * C0.5 mm = 0.80 wt% C
1.20 − 0.25 & 2 1.6 ×10 ⋅ t )
" 62.5 % 62.5
0.4210 = erf $ ' = 0.392
# t & t
€ " 62.5 %2
t =$ ' = 25400 s = 7.1 h
# 0.392 & Surface 0.5 mm
€ €
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5
 Diffusion in Solids

z=? 0.4210

z − 0.35 0.4210 − 0.3794

= z = 0.392
0.40 − 0.35 0.4284 − 0.3794

MCEN90014: Materials Dr. K. Xia 11

€
€

Diffusion in Solids
Diffusion coefficient
• D determines how fast a Qd # 1 &
diffusion takes place log D = log D0 − % (
2.3R $ T '
log D

dC
J = −D
dx the slope

– the higher D is, the larger J

for the same driving force €
(dC/dx)
€
• Expression for D
# Q & Arrhenius
D = Do exp%− d ( equation
$ RT '
Do: constant for a certain type
of diffusion (m2/s) host and
diffusing species

€ Qd: activation energy for 1/T

diffusion (J/mol)
R: gas constant = 8.31 J/mol-K
T: absolute temperature (K)
MCEN90014: Materials
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

6
 Diffusion in Solids
The diffusing
atom can jump in
any direction that
is available
1 2

E 2
3 1 3
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
MCEN90014: Materials Dr. K. Xia 13

Diffusion in Solids
Diffusion system

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7
 Diffusion in Solids - Example
Example 5.5

log D
Cu diffusion in Au
• Known: log D vs 1/T curve (D1, T1)

• Qd and Do = ?
Solution
Pick up any two points from the
Qd/2.3R
curve (e.g. {D1,T1} & {D2,T2})
Qd = –2.3R ·Slope 1 (D2, T2)
# &
% log D − log D (
1 2
Qd = −2.3R% (
%% 1 1 ((
−
$ T1 T2 '
# −12.40 − (−15.45) &
= −2.3 × 8.31% (
$ 0.8 ×10 −3 −1.1×10 −3 ' 1/T x 1000

= 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
€ Do = 10 −4.28 = 5.25 ×10 −5 m 2 /s
MCEN90014: Materials Dr. K. Xia 15
€
€

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
MCEN90014: Materials Dr. K. Xia 16