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Chapter 5 -
Chapter 5: Diffusion in Solids
ISSUES TO ADDRESS...
• How does diffusion occur?
Chapter 5 - 2
Diffusion
Diffusion - Mass transport by atomic motion
Mechanisms
• Gases & Liquids – random (Brownian) motion
• Solids – vacancy diffusion or interstitial diffusion
Chapter 5 - 3
Diffusion
• Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially After some time
Adapted from
Figs. 5.1 and
5.2, Callister
7e.
Chapter 5 - 4
Diffusion
• Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms After some time
C
C
A D
A
D
B
B
Chapter 5 - 5
Diffusion Mechanisms
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
--number of vacancies
--activation energy to exchange.
• Simulation of
interdiffusion
across an interface:
• Rate of substitutional
diffusion depends on:
--vacancy concentration
--frequency of jumping.
Chapter 5 - 7
Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can
diffuse between atoms.
Chapter 5 - 9
Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip
silicon
2. Heat it.
3. Result: Doped light regions: Si atoms
semiconductor
regions.
M=
M l dM mass J slope
J diffused
At A dt
time
Chapter 5 - 11
Steady-State Diffusion
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx
dC
C2 C2 J D
dx
x1 x2
x
D diffusion coefficient
dC C C2 C1
if linear
dx x x2 x1
Chapter 5 - 12
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 = 110 x10-8 cm2/s
– surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
Chapter 5 - 13
Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C2 C1
tb
2 J -D D
paint
6D dx x2 x1
skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm
Chapter 5 - 14
Diffusion and Temperature
Qd
D Do exp
RT
Chapter 5 - 15
Diffusion and Temperature
D has exponential dependence on T
1500
1000
600
300
T(C)
10-8
10-20
0.5 1.0 1.5 1000 K/T
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.)
Chapter 5 - 16
Example: At 300ºC the diffusion coefficient and
activation energy for Cu in Si are
D(300ºC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350ºC?
D transform ln D
data
Temp = T 1/T
Qd 1 Q 1
lnD2 lnD0 and lnD1 lnD0 d
R T2 R T1
D2 Qd 1 1
lnD2 lnD1 ln
D1 R T2 T1
Chapter 5 - 17
Example (cont.)
Qd 1 1
D2 D1 exp
R T2 T1
Chapter 5 - 18
Non-steady State Diffusion
Chapter 5 - 19
Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms
Cs
Adapted from
Fig. 5.5,
Callister 7e.
B.C. at t = 0, C = Co for 0 x
at t > 0, C = CS for x = 0 (const. surf. conc.)
C = Co for x =
Chapter 5 - 20
Solution:
C x ,t Co x
1 erf
Cs Co 2 Dt
Chapter 5 - 21
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.
C( x, t ) Co x
• Solution: use Eqn. 5.5 1 erf
Cs Co 2 Dt
Chapter 5 - 22
C( x ,t ) Co x
Solution (cont.): 1 erf
Cs Co 2 Dt
– t = 49.5 h x = 4 x 10-3 m
– Cx = 0.35 wt% Cs = 1.0 wt%
– Co = 0.20 wt%
C( x, t ) Co 0.35 0.20 x
1 erf 1 erf ( z )
Cs Co 1.0 0.20 2 Dt
erf(z) = 0.8125
Chapter 5 - 23
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
x2 3 2
( 4 x 10 m) 1h
D 2.6 x 1011 m2 /s
4z 2t ( 4)(0.93)2 ( 49.5 h) 3600 s
Chapter 5 - 24
Solution (cont.):
• To solve for the temperature at Qd
T
which D has above value, we R(lnDo lnD )
use a rearranged form of
Equation (5.9a);
from Table 5.2, for diffusion of C in FCC Fe
Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol
148,000 J/mol
T
(8.314 J/mol - K)(ln 2.3x105 m2 /s ln 2.6x1011 m2 /s)
T = 1300 K = 1027°C
Chapter 5 - 25
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
breakthrough time (tb), i.e., how long could the gloves be used
before methylene chloride reaches the hand?
• Data (from Table 22.5)
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
Chapter 5 - 26
Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 2
tb Equation 22.24
paint skin 6D
remover
C2
x2 x1 0.04 cm
x1 x2
D = 110 x 10-8 cm2/s
(0.04 cm)2
tb 240 s 4 min
-8 2
(6)(110 x 10 cm /s)
Chapter 5 - 27
Summary
Diffusion FASTER for... Diffusion SLOWER for...
Chapter 5 - 28
ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:
Chapter 5 - 29