Chapter 5: Diffusion

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 - 1
 Diffusion
Diffusion - Mass transport by atomic motion
Mechanisms (How do atoms move through solids?)
• Gases & Liquids – random (Brownian) motion
• Solids – vacancy diffusion or interstitial diffusion,
impurities
The mathematics of diffusion
• Steady-state diffusion (Fick’s first law)
• Nonsteady-state diffusion (Fick’s second law)
Factors that influence diffusion
• Diffusing species
• Host solid
• Temperature
• Microstructure
Chapter 5 - 2
 Diffusion
• Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc. (impurity dif.)
Initially After some time

Adapted from
Figs. 5.1 and
5.2, Callister &
Rethwisch 8e.

Diffusion couple (Cu, Ni) is heated for an extended period at elevated temperature
Chapter 5 - 3
 Diffusion

Inhomogeneous materials can become homogeneous by diffusion.

For an active diffusion to occur, the temperature should be high
enough to overcome energy barriers to atomic motion. 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

Exchanging the positions of atoms

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 (to break the bonds with
neighbours)

increasing elapsed time

Chapter 5 - 6
 Diffusion Simulation

• Simulation of
interdiffusion
across an interface:

• Rate of substitutional
diffusion depends on:
-- vacancy concentration
-- frequency of jumping.

(Courtesy P.M. Anderson)

Chapter 5 - 7
 Diffusion Mechanisms
• Interstitial diffusion – smaller atoms (e.g.
C, H, O) can diffuse between atoms.

Adapted from Fig. 5.3(b),

Callister & Rethwisch 8e.

More rapid than vacancy diffusion

(bonding of interstitials to the surrounding atoms is normally
weaker and there are many more interstitial sites than vacancy
Chapter 5 - 8
sites to jump to
 Processing Using Diffusion
• Case Hardening:
Adapted from
-- Diffuse carbon atoms 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 - 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.

light regions: Al atoms

silicon
Adapted from Figure 18.27, Callister &
Rethwisch 8e. Chapter 5 - 10
 Diffusion
• How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

J  Flux   or
surface area time  2
cm s m 2 s
• 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
Where M is the mass of atoms diffusing through the area A during time t
Chapter 5 - 11
 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 C2 J  D
dx
x1 x2
x
D  diffusion coefficient
dC C C2  C1
if linear  
dx x x 2  x1

Chapter 5 - 12
Steady-State Diffusion

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 = 110 x10-8 cm2/s
– surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3

Chapter 5 - 14
 Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C 2  C1
tb 
2 J  -D  D
paint
6D dx x 2  x1
skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x 2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

-8 2 (0.02 g/cm 3  0.44 g/cm 3 ) g

J   (110 x 10 cm /s)  1.16 x 10 - 5
(0.04 cm) cm 2 s

Chapter 5 - 15
 Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D  Do exp 
 RT 

D = diffusion coefficient [m2/s]

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

For example, for the self diffusion of Fe in α-Fe, D increases

apx. six orders of mag. (from 3.0x10e-21 to 1.8x10e-15) in rising
T from 500 to 900 °C. Chapter 5 - 16
 Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300
T(C)
10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in a-Fe Al in Al
10-14 C in g-Fe Fe in a-Fe
Fe in g-Fe

10-20
0.5 1.0 1.5 1000 K/T

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.)

Chapter 5 - 17
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 Qd 1
ln D2  ln D0    and ln D1  ln D0   
R  T2  R  T1 
D Q  1 1
 ln D2  ln D1  ln 2   d   
D1 R  T2 T1 
Chapter 5 - 18
 Example (cont.)
 Qd  1 1 
D2  D1 exp      
 R  T2 T1  

T1 = 273 + 300 = 573K

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 - 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 Fick’s Second Law is used

Fick’s Second Law C  2C

D 2
t x

Solution of this equation is concentration profile as

function of time, C(x,t)

Chapter 5 - 20
 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 & Rethwisch 8e.

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 - 21
 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 C(x,t)

y 2
 e dy
 0
Co
erf(z) values are given in
Table 5.1
Adapted from Fig. 5.5,
Callister & Rethwisch 8e.

Chapter 5 - 22
 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 )  C o  x 
• Solution: use Eqn. 5.5  1  erf  
Cs  Co  2 Dt 

Chapter 5 - 23
 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 - 24
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  0 .90 0 .8125  0 .7970

z erf(z) 
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  3 2
( 4 x 10 m) 1h
D     2.6 x 10 11 m 2 /s
 4 z 2t  ( 4 )(0.93 )2 ( 49 .5 h) 3600 s
 
Chapter 5 - 25
 Solution (cont.):
• To solve for the temperature at Qd
T 
which D has the above value, R (ln Do  ln D )
we 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 2.3 x10  5 m 2 /s  ln 2.6 x10 11 m 2 /s)

T = 1300 K = 1027ºC

Chapter 5 - 26
 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
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s

Chapter 5 - 27
 CPC Example (cont.)
• Solution – assuming linear conc. gradient
glove Breakthrough time = tb
C1
2
Equation from online CPC

tb 
Case Study 5 at the Student
paint skin Companion Site for Callister &
remover 6D Rethwisch 8e (www.wiley.com/
college/callister)
C2
  x 2  x1  0.04 cm
x1 x 2
D = 110 x 10-8 cm2/s

(0.04 cm) 2
tb   240 s  4 min
-8 2
( 6 )(110 x 10 cm /s)

Time required for breakthrough ca. 4 min

Chapter 5 - 28
 Summary
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

Chapter 5 - 29