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 &
Rethwisch 8e.

Chapter 5 -
Chapter 5 - 2
 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 -
 Diffusion Mechanisms
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

Chapter 5 -
Chapter 5 - 5
 Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can
diffuse between atoms.

Adapted from Fig. 5.3(b), Callister & Rethwisch 8e.

More rapid than vacancy diffusion

Chapter 5 -
 Processing Using Diffusion
• Case Hardening:
-- Diffuse carbon atoms Adapted from
chapter-opening
into the host iron atoms photograph,
Chapter 5,
at the surface. Callister &
Rethwisch 8e.
-- Example of interstitial (Courtesy of
Surface Division,
diffusion is a case Midland-Ross.)

hardened gear.

• Result: The presence of C

atoms makes iron (steel) harder.

Chapter 5 -
 Diffusion
• How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

J  Flux   or
surface areatime  cm s m2s
2

• Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane

M=
M l dM mass J slope
J  diffused
At A dt
time

Chapter 5 -
 Steady-State Diffusion
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx

C1 C1 Fick’s first law of diffusion

dC
C2 J  D
C2
dx
x1 x2
x
D  diffusion coefficient
dC C C2  C1
if linear  
dx x x2  x1

Chapter 5 - 9
 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 - 10
 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
x 1 x2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

-8 2 (0.02 g/cm3  0.44 g/cm3 ) g

J   (110 x 10 cm /s)  1.16 x 10 -5
(0.04 cm) cm2s

Chapter 5 - 11
 Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D  Do exp 
 RT 

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

Chapter 5 - 12
 Diffusion and Temperature
D has exponential dependence on T
1500

1000
T(C)

600

300
10-8
C

D (m2/s)
in

Ci
n Dinterstitial >> Dsubstitutional
-

-Fe
Fe Fe i

C in -Fe Al in Al
Fe

10-14
C in -Fe Fe in -Fe
n
i

-

Al
n

Fe in -Fe
Fe

in
-Fe

Al

10-20
0.5 1.0 1.5 1000 K/T

Chapter 5 - 13
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 - 14
 Example (cont.)
 Qd  1 1 
D2  D1 exp   
 R  T2 T1 

T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K

11 2   41,500 J/mol  1 1 

D2  (7.8 x 10 m /s) exp   
 8.314 J/mol - K  623 K 573 K 

D2 = 15.7 x 10-11 m2/s

Chapter 5 - 15
 Non-steady State Diffusion
• The concentration of diffusing species is a function of both time and position C = C(x,t)
• In this case Fick’s Second Law is used

Fick’s Second Law C  2C

D 2
t x

Chapter 5 - 16
 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

B.C. at t = 0, C = Co for 0  x  
at t > 0, C = CS for x = 0 (constant surface conc.)
C = Co for x = 
Chapter 5 - 17
 Solution:
C x , t   Co  x 
 1  erf  
Cs  Co  2 Dt 

C(x,t) = Conc. at point x at CS

time t
erf (z) = error function
2 z
y 2 C(x,t)

  0
e dy
Co

Chapter 5 - 18
 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 - 19
 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 - 20
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) z  0.90 0.8125  0.7970


0.95  0.90 0.8209  0.7970
0.90 0.7970
z 0.8125 z  0.93
0.95 0.8209

Now solve for D x x2

z D
2 Dt 4 z 2t

 x2  ( 4 x 10 3
m) 2
1h
D      2.6 x 10 11 m2 /s
 4z 2t  ( 4)(0.93)2 ( 49.5 h) 3600 s
 
Chapter 5 - 21