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?

Chapter 5 - 1
 Diffusion
• Mass transport by atomic motion?

• Gases & Liquids – random (Brownian) motion

• Solids – vacancy diffusion or interstitial diffusion

Diffusion - Mass transport by atomic motion.

Due to concentration difference.

Chapter 5 - 2
 Diffusion
• Interdiffusion: Atoms of the metals diffuse into one another.

Diffusion couple
Initially After some time

3
Chapter 5 -
 Diffusion
Example: Diffusion of Cu & Ni in one another at elevated
temperature.

Alloy region

Chapter 5 -
 Diffusion
• Self-diffusion: In an elemental solid, atoms also migrate.
Label some atoms After some time

C
C

A
A
D D
B
B
• In pure metals, all atoms exchanging positions are of same
type.
• No compositional changes observed. Chapter 5 - 5
 Diffusion Mechanisms
Vacancy Diffusion: atoms exchange with vacancies.
• rate depends on
-number of vacancies
-activation energy to exchange.
-Temperature

increasing elapsed time

• Vacancies and atoms transport in opposite direction.

Chapter 5 - 6
 Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can diffuse
between atoms.

• In alloys, interstitial diffusion occurs more rapid

than vacancy diffusion.
Chapter 5 - 7
 Processing Using Diffusion

• Practical Example of interstitial

diffusion is a case hardened gear.

Case Hardening
-Diffuse carbon atoms into the
host iron atoms at the surface.

• Result: The presence of C atoms makes iron (steel)

harder.
Chapter 5 - 8
 Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process:
1. Deposit P rich
layers on surface.

0.5 mm
silicon
2. Heat it.
3. Result: Doped
semiconductor
regions.
magnified image of a computer chip

silicon
Chapter 5 - 9
 Diffusion
• How fast does mass transport?

moles (or mass) diffusing mol kg

J  Flux   or
surface area time  cm2s m2s

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

• Time dependent/ transient diffusion

Chapter 5 - 10
 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 x2  x1

• Why negative sign? Chapter 5 - 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.
• 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 - 12
 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

-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 - 13
 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 - 14
 Diffusion and Temperature
D has exponential dependence on T
1500

1000
T(C)

600

300
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

Chapter 5 - 15
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 - 16
 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 - 17
 Non-steady State Diffusion
• The concentration of diffusing species is a function of
both time and position C = C(x,t)

• Most practical

• What type of derivative?

C  C 2
D
t x 2

Fick’s Second Law

Chapter 5 - 18
 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 (const. surf. conc.)
C = Co for x =  Chapter 5 - 19
 Solution:

C x, t   Co  x 
 1  erf  
Cs  Co  2 Dt 
C(x,t) = Conc. at point x at
time t CS
erf (z) = error function

x
 erf ( ) C(x,t)
2 Dt
Co
erf(z) values are given in Table

Chapter 5 - 20
Table

Chapter 5 -
 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  1  erf  
Cs  Co  2 Dt 

Co = 0.20 wt% Cs = 1.0 wt% Cx = 0.35 wt%

t = 49.5 h x = 4 x 10-3 m 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

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 4z 2t

 x2  3 2
( 4 x 10 m) 1h
D      2.6 x 10 11 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(ln Do  ln D )
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 2.3x10 5 m2 /s  ln 2.6x10 11 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)

Time required for breakthrough ca. 4 min

Chapter 5 - 27
 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 - 28