Chapter 5 - 3

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?
Chapter 5: Diffusion
Chapter 5 - 4
Diffusion
Diffusion - Mass transport by atomic motion
Mechanisms
Gases & Liquids random (Brownian) motion
Solids vacancy diffusion or interstitial diffusion
Chapter 5 - 5
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 &
Rethwisch 8e.
Diffusion
After some time
Chapter 5 - 6
Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms
Diffusion
A
B
C
D
After some time
A
B
C
D
Chapter 5 - 7
Diffusion Mechanisms
Vacancy Diffusion:
atoms exchange with vacancies
applies to substitutional impurities atoms
rate depends on:
-- number of vacancies
-- activation energy to exchange
(frequency of jumping).
increasing elapsed time
Chapter 5 - 8
Diffusion Mechanisms
Interstitial diffusion smaller atoms can
diffuse between atoms.
Adapted from Fig. 5.3(b), Callister & Rethwisch 8e.
Chapter 5 - 9
Adapted from
chapter-opening
photograph,
Chapter 5,
Callister &
Rethwisch 8e.
(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
Chapter 5 - 10
Doping silicon with phosphorus for n-type semiconductors:
Process:
3. Result: Doped
semiconductor
regions.
silicon
Processing Using Diffusion
magnified image of a computer chip
0.5mm
light regions: Si atoms
light regions: Al atoms
2. Heat it.
1. Deposit P rich
layers on surface.
silicon
Chapter 5 - 11
Diffusion
How do we quantify the amount or rate of diffusion?
( )( )
s m
kg
or
s cm
mol
time area surface
diffusing mass) (or moles
Flux
2 2
= J
J slope
dt
dM
A
J
1
=
M =
mass
diffused
time
Measured empirically
Make thin film (membrane) of known surface area
Impose concentration gradient
Measure how fast atoms or molecules diffuse through the
membrane
Chapter 5 - 12
Steady-State Diffusion
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
Negative sign indicates that
the direction is down the
concentration gradient
Rate of diffusion independent of time
Flux proportional to concentration gradient =
dx
dC
1 2
1 2
linear if
x x
C C
x
C
dx
dC

=
A
A
~
Chapter 5 - 13
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.
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 = 110x10
-8
cm
2
/s
surface concentrations:
C
2
= 0.02 g/cm
3
C
1
= 0.44 g/cm
3
Chapter 5 - 14
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
Example (cont).
1 2
1 2
-
x x
C C
D
dx
dC
D J

~ =
D
t
b
6
2

=
glove
C
1
C
2
skin
paint
remover
x
1
x
2
Solution assuming linear conc. gradient
D = 110x10
-8
cm
2
/s
C
2
= 0.02 g/cm
3
C
1
= 0.44 g/cm
3
x
2
x
1
= 0.04 cm
Data:
Chapter 5 - 15
Diffusion and Temperature
Diffusion coefficient increases with increasing T.
D = D
o
exp
|
\

|
.
|

Q
d
RT
= 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
Chapter 5 - 16
Diffusion and Temperature
Adapted from Fig. 5.7, Callister & Rethwisch 8e. (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
1000K/T
D (m
2
/s) C
in
o
-
F
e
C
i
n

-
F
e
A
l
i
n
A
l
F
e
i
n
o
-
F
e
F
e
i
n

-
F
e
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
Chapter 5 - 17
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
transform
data
D
Temp = T
ln D
1/T
Chapter 5 - 18
Example (cont.)
(

|
.
|

\
|

=

K 573
1
K 623
1
K - J/mol 314 . 8
J/mol 500 , 41
exp /s) m 10 x 8 . 7 (
2 11
2
D
(

|
|
.
|

\
|
=
1 2
1 2
1 1
exp
T T R
Q
D D
d
T
1
= 273 + 300 = 573K
T
2
= 273 + 350 = 623K
D
2
= 15.7 x 10
-11
m
2
/s
Chapter 5 - 19
Non-steady State Diffusion
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
1. If then has a local maximum at .
2. If then has a local minimum at .
3. If , the second derivative test says nothing about the point , a possible
inflection point.
Mathematic considerations:
Chapter 5 - 20
Non-steady State Diffusion
Adapted from
Fig. 5.5,
Callister &
Rethwisch 8e.
B.C. at t = 0, C = C
o
for 0 s x s
at t > 0, C = C
S
for x = 0 (constant surface conc.)
C = C
o
for x =
Copper diffuses into a bar of aluminum.
pre-existing conc., C
o
of copper atoms
Surface conc.,
C of Cu atoms
bar
s
C
s
Chapter 5 - 21
Solution:
C(x,t) = Conc. at point x at
time t
erf (z) = error function
erf(z) values are given in
Table
C
S
C
o
C(x,t)
( )
|
.
|

\
|
=

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

}
t
=
Adapted from Fig. 5.5,
Callister & Rethwisch 8e.
Chapter 5 - 22
Chapter 5 - 23
Non-steady State Diffusion
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
|
.
|

\
|
=

Dt
x
C C
C t x C
o s
o
2
erf 1
) , (
Chapter 5 - 24
Solution (cont.):
t = 49.5 h x = 4 x 10
-3
m
C
x
= 0.35 wt% C
s
= 1.0 wt%
C
o
= 0.20 wt%
|
.
|

\
|
=

Dt
x
C C
C ) t , x ( C
o s
o
2
erf 1
) ( erf 1
2
erf 1
20 . 0 0 . 1
20 . 0 35 . 0 ) , (
z
Dt
x
C C
C t x C
o s
o
= |
.
|

\
|
=

erf(z) = 0.8125
Chapter 5 - 25
Solution (cont.):
We must now determine from Table 5.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows
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
Chapter 5 - 26
To solve for the temperature at
which D has the above value,
we use a rearranged form of
Equation (5.9a);
) 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
Chapter 5 - 27
Chapter 5 - 28
Chapter 5 - 29
Diffusion FASTER for...
open crystal structures
materials w/secondary
bonding
smaller diffusing atoms
lower density materials
Diffusion SLOWER for...
close-packed structures
materials w/covalent
bonding
larger diffusing atoms
higher density materials
Summary
Chapter 5 -
Concept check
30
Rank the magnitudes of the diffusion coefficients from greatest to least for
the following systems:
N in Fe at 700C
Cr in Fe at 700C
N in Fe at 900C
Cr in Fe at 900C .
Note: Both Fe and Cr have the BCC crystal structure, and the atomic radii for Fe, Cr,
and N are 0.124, 0.125, and 0.065 nm, respectively.
Chapter 5 - 31
Question: Consider the self-diffusion of two hypothetical
metals A and B. On a schematic graph of ln D versus 1/T,
plot (and label) lines for both metals given that D0(A) >
D0(B) and also that Qd(A) > Qd(B).
D = D
o
exp
|
\

|
.
|

Q
d
RT
ln ln
|
|
.
|

\
|
=
T R
Q
D D
d
1
0