1

Chapter 5: Diffusion in Solids

ISSUES TO ADDRESS...
How does diffusion occur?
Why is it an important part of processing?
How can the rate of diffusion be predicted for
some simple cases?
How does diffusion depend on structure
and temperature?
Types of Diffusion
2
Interdiffusion: In an alloy, atoms tend to migrate from regions
of high conc. to regions of low conc.
Initially
Adapted from
Figs. 5.1 and
5.2, Callister
7e.
After some time
Types of Diffusion
3
Self-diffusion: In an elemental solid, atoms also migrate.
Label some atoms After some time
A
B
C
D
A
B
C
D
Diffusion Mechanisms
4
Vacancy Diffusion
atoms exchange with vacancies
applies to substitutional impurities atoms and self-diffusion
rate depends on:
--number of vacancies
--activation energy to exchange.
increasing elapsed time
Diffusion Mechanisms
5
Interstitial diffusion smaller atoms can diffuse
between atoms.
More rapid than vacancy diffusion
Adapted from Fig. 5.3 (b), Callister 7e.
Processing Using Diffusion
6
Adapted from
chapter-opening
photograph,
Chapter 5,
Callister 7e.
(Courtesy of
Surface Division,
Midland-Ross.)
Case Hardening:
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.
Processing Using Diffusion
7
Doping silicon with phosphorus
for n-type semiconductors:
Process:
magnified image of a computer chip
0.5 mm
light regions: Si atoms
light regions: Al atoms
3. Doped semiconductor regions.
silicon
2. Heat it.
1. Deposit P rich
layers on surface.
silicon
Adapted from chapter-opening photograph,
Chapter 18, Callister 7e.
8
How do we quantify the
amount or rate of diffusion?
9
( )( )
s m
kg
or
s cm
mol
time area surface
diffusing mass) (or moles
Flux
2 2
= J
Steady-State Diffusion
10
dx
dC
dx
dC
D J =
Ficks first law of diffusion
C
1

C
2

x
C
1

C
2

x
1
x
2

D diffusion coefficient
Rate of diffusion independent of time
Flux proportional to concentration gradient =
1 2
1 2
linear if
x x
C C
x
C
dx
dC

=
A
A
~
11
Example: Chemical Protective Clothing (CPC)
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.
Example: Chemical Protective Clothing (CPC)
12
If butyl rubber gloves (0.04 cm thick) are used, what is the
diffusion flux of methylene chloride through the glove?
Data:
diffusion coefficient in butyl rubber:
D = 110 x10
-8
cm
2
/s
surface concentrations:

C
2
= 0.02 g/cm
3
C
1
= 0.44 g/cm
3
s cm
g
10 x 16 . 1
cm) 04 . 0 (
) g/cm 44 . 0 g/cm 02 . 0 (
/s) cm 10 x 110 (
2
5 -
3 3
2 8 -
=

= J
Factors that influence Diffusion
Temperature
Diffusing Species
13
Diffusion and Temperature
14
Diffusion coefficient increases with increasing T.
D
=
D
o
exp
|
\

|
.
|

Q
d

R T
= pre-exponential [m
2
/s]
= diffusion coefficient [m
2
/s]
= activation energy [J/mol or eV/atom]
= gas constant [8.314 J/mol-K]
= absolute temperature [K]
D
D
o
Q
d
R
T
Diffusion and Temperature
15
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.)
D has exponential
dependence on T
D
interstitial
>> D
substitutional
C in o-Fe
C in -Fe
Al in Al
Fe in o-Fe
Fe in -Fe
1000 K/T
D (m
2
/s)
0.5 1.0 1.5
10
-20

10
-14

10
-8

T(C)
1
5
0
0

1
0
0
0

6
0
0

3
0
0

16
Example: At 300C the diffusion coefficient and activation
energy for Cu in Si are

D(300C) = 7.8 x 10
-11
m
2
/s
Q
d
= 41.5 kJ/mol

What is the diffusion coefficient at 350C?
|
|
.
|

\
|
=
|
|
.
|

\
|
=
1
0 1
2
0 2
1
ln ln and
1
ln ln
T R
Q
D D
T R
Q
D D
d d
|
|
.
|

\
|
= =
1 2 1
2
1 2
1 1
ln ln ln
T T R
Q
D
D
D D
d
D
2
= 15.7 x 10
-11
m
2
/s
Non-steady State Diffusion
17
The concentration of diffusing species is a
function of both time and position C = C(x,t)
In this case Ficks Second Law is used


2
2
x
C
D
t
C
c
c
=
c
c
Ficks Second Law
Non-steady State Diffusion
18
Copper diffuses into a bar of aluminum.
pre-existing conc., C
o
of copper atoms
Surface conc.,
C of Cu atoms
bar
s
C(x,t) = Conc. at point x at time t
erf (z) = error function



erf(z) values are given in Table 6.1
( )
|
.
|

\
|
=

Dt
x
C C
C t x C
o s
o
2
erf 1
,
dy e
y
z
2
0
2

}
t
=
Non-steady State Diffusion
19
Sample Problem: An FCC iron-carbon alloy initially containing
0.20 wt% C is carburized at an elevated temperature and in
an atmosphere that gives a surface carbon concentration
constant at 1.0 wt%. If after 49.5 h the concentration of
carbon is 0.35 wt% at a position 4.0 mm below the surface,
determine the temperature at which the treatment was carried
out.

Solution: use Eqn. 5.5
( ) z erf 1
C C
C t) C(x,
o s
o
=

erf(z) = 0.8125
20
since erf(z) = 0.8125
Solution (cont.):
21
through interpolation
z erf(z)
0.90 0.7970
z 0.8125
0.95 0.8209
7970 . 0 8209 . 0
7970 . 0 8125 . 0
90 . 0 95 . 0
90 . 0

z
z = 0.93
Now solve for D
Dt
x
z
2
=
t z
x
D
2
2
4
=
/s m 10 x 6 . 2
s 3600
h 1
h) 5 . 49 ( ) 93 . 0 ( ) 4 (
m) 10 x 4 (
4
2 11
2
2 3
2
2

= =
|
|
.
|

\
|
=
t z
x
D
22
) ln ln ( D D R
Q
T
o
d

=
from Table 5.2, for diffusion of C in FCC Fe

D
o
= 2.3 x 10
-5
m
2
/s Q
d
= 148,000 J/mol
/s) m 10 x 6 . 2 ln /s m 10 x 3 . 2 K)(ln - J/mol 314 . 8 (
J/mol 000 , 148
2 11 2 5

= T
Solution (cont.):
T = 1300 K = 1027C
Seatwork 2
23
1.
2.