TOPIC 2: Diffusion in Solids
Why diffusion is important?
Heat treatment (phase transformation from
solid to solid)
ISSUES TO ADDRESS...
How does diffusion occur?
Solidification (liquid to solid)
Why is it an important part of processing?
Surface hardening of steel
(carburising, nitriding, etc)
How can the rate of diffusion be predicted for
some simple cases?
Coatings
How does diffusion depend on structure
and temperature?
sintering of ceramics
1
Diffusion
Diffusion in solid materials
Diffusion - Mass transport by atomic motion in
{G
GG
GG
GG
G
GG
G
materials (solids, liquids or gases)
Mechanisms
Gases & Liquids random (Brownian) motion
Solids vacancy diffusion or interstitial diffusion
oGaGGGG
}GGaGGG
tGGGGGG
GGG
Diffusion
Two types of diffusion in crystalline solids:
Self-diffusion: In an elemental solid, atoms
also migrate.
OXP GGG
vGGGGGG
GGGGGG
OGGGP
OYPGzT
vGGGG
GOGGGG
P
Label some atoms
C
A
D
B
After some time
A
B
Diffusion
Diffusion Simulation
Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially
Simulation of
interdiffusion
across an interface:
After some time
Adapted from
Figs. 5.1 and
5.2, Callister
7e.
Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.
(Courtesy P.M. Anderson)
Diffusion Mechanisms
Diffusion mechanism
Interstitial diffusion smaller atoms can
diffuse between atoms.
Atoms are constantly in motion and
vibrating
Change of atomic position requires:
}G
lGGG
{GGGG
a
}GGGG
pG
Adapted from Fig. 5.3 (b), Callister 7e.
Diffusion Mechanisms
More rapid than vacancy diffusion because the interstitial
atoms are smaller, thus more mobile. Also, there are more
11
empty interstitial positions than vacancies.
INTERSTITIAL SIMULATION
Vacancy Diffusion:
atoms exchange with vacancies
applies to substitutional impurities atoms
Both self diffusion and interdiffusion occur by this mechanism
rate depends on:
--number of vacancies
--activation energy to exchange.
Applies to interstitial
impurities.
More rapid than
vacancy diffusion.
Simulation:
--shows the jumping of a
smaller atom (gray) from
one interstitial site to
another in a BCC
structure. The
interstitial sites
considered here are
at midpoints along the
unit cell edges.
10
(Courtesy P.M. Anderson)
12
Example: Chemical Protective
Clothing (CPC)
Processing Using Diffusion
Case Hardening:
Adapted from
chapter-opening
photograph,
Chapter 5,
Callister 7e.
(Courtesy of
Surface Division,
Midland-Ross.)
--Diffuse carbon atoms
into the host iron atoms
at the surface.
--Example of interstitial
diffusion is a case
hardened gear.
Result: The presence of C
atoms makes iron (steel) harder.
Methylene chloride is a common ingredient of paint
removers. Besides being an irritant, it also may be
absorbed through skin. When using this paint
remover, protective gloves should be worn.
If butyl rubber gloves (0.04 cm thick) are used, what
is the diffusive flux of methylene chloride through the
glove?
Data:
diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
13
15
Steady-State Diffusion
Example (cont).
Rate of diffusion independent of time (no change in
concentration of solute atoms with time)
dC
Flux proportional to concentration gradient = dx
C1 C1
glove
C1
Ficks first law of diffusion
C2
x1
if linear
Solution assuming linear conc. gradient
C2
J D
paint
remover
tb
"2
6D
skin
C2
dC
dx
J -D
x1 x 2
dC
C C1
D 2
dx
x2 x1
Data:
D = 110 x 10-8 cm2/s
C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 x1 = 0.04 cm
x2
dC C C2 C1
dx x
x2 x1
D diffusion coefficient
14
J (110 x 10-8 cm2 /s)
(0.02 g/cm3 0.44 g/cm3 )
g
1.16 x 10-5
(0.04 cm)
cm2s
16
Example: At 300C the diffusion coefficient and
activation energy for Cu in Si are
Diffusion and Temperature
D(300C) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
Diffusion coefficient increases with increasing T.
Arrhenius equation:
What is the diffusion coefficient at 350C?
Qd
D Do exp
RT
transform
data
D = diffusion coefficient [m2/s]
Do = pre-exponential [m2/s]
Temp = T
Qd = activation energy [J/mol or eV/atom]
T = absolute temperature [K]
17
Q
D2 D1 exp d
R
D has exponential dependence on T
300
600
1000
Qd
R
1
T1
19
Example (cont.)
Diffusion and Temperature
1500
1/T
1
Q
and lnD1 lnD0 d
R
T2
Q 1 1
D
lnD2 lnD1 ln 2 d
D1
R T2 T1
lnD2 lnD0
R = gas constant [8.314 J/mol-K]
10-8
ln D
T(C)
1 1
T2 T1
T1 = 273 + 300 = 573K
D (m2/s)
Dinterstitial >> Dsubstitutional
C in -Fe
C in -Fe
10-14
10-20
0.5
1.0
1.5
Al in Al
Fe in -Fe
Fe in -Fe
T2 = 273 + 350 = 623K
41,500 J/mol 1
1
D2 (7.8 x 1011 m2 /s) exp
8.314 J/mol - K 623 K 573 K
1000 K/T
D2 = 15.7 x 10-11 m2/s
Adapted from Fig. 5.7, Callister 7e. (Date for Fig. 5.7 taken from E.A.
Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th
ed., Butterworth-Heinemann, Oxford, 1992.)
18
20
Non-steady State Diffusion
The concentration of diffusing species is a function of
both time and position C = C(x,t).
In most cases non-steady state diffusion is occurs,
where the concentration of solute atoms at any point
in the materials changes with time.
e.g. If carbon is being diffused in the surface of a steel
camshaft to harden its surface, the concentration of
carbon under the surface at any point will change
with time as the diffusion process progresses.
In this case Ficks Second Law is used
C
2C
Ficks Second Law
D 2
t
x
21
Summary
Diffusion FASTER for...
Diffusion SLOWER for...
open crystal structures
close-packed structures
smaller diffusing atoms
larger diffusing atoms
lower density materials
higher density materials
22
