Lecture – 19

Diffusion in solids

Md. Fakhrul Islam

 Diffusion

Diffusion - Mass transport by atomic motion

Mechanisms
• Gases & Liquids – random (Brownian) motion
• Solids – vacancy diffusion or interstitial diffusion

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Diffusion in liquids
 Diffusion in solids
• 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.

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 Diffusion
• Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms After some time
C
C
A D
A
D
B
B

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

increasing elapsed time

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

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

More rapid than vacancy diffusion

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Processing Using Diffusion
 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 & 10
Rethwisch 8e.
 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

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 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
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 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:
C = 0.44 g/cm3
1

C2 = 0.02 g/cm3
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 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

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 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 C( x, t )  Co  x 

1  erf  
Cs  Co  2 Dt 

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 C ( x , t )  Co  x 
Solution (cont.):C  C 1  erf  
s o  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

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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  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
 
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 Solution (cont.):
• To solve for the temperature at Qd
T 
which D has the 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 2.3 x10  5 m2 /s  ln 2.6 x10  11 m2 /s)

T = 1300 K = 1027ºC
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 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

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 CPC Example (cont.)
• Solution – assuming linear conc. gradient
glove Breakthrough time = tb
C1
2 Equation from online CPC
Case Study 5 at the Student
paint skin tb  Companion Site for Callister &
remover 6D Rethwisch 8e (www.wiley.com/
college/callister)
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

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 Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

æ Qd ö
D = Do expç - 
è RT ø

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]

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 Diffusion and Temperature

D has exponential dependence on T

1500

1000

600

300
T(C)
10-8
C

D (m2/s)
in

Ci
na Dinterstitial >> Dsubstitutional
g-

-Fe
Fe Fe i

C in a-Fe Al in Al
Fe

10 -14
C in g-Fe Fe in a-Fe
n
i
ng

a-

Al

Fe in g-Fe
Fe

in
-Fe

Al

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.)
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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 
lnD2 lnD0    and lnD1 lnD0   
R  T2  R  T1 
D2 Qd  1 1 
 lnD2  lnD1 ln    
D1 R  T2 T1 
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 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

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 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

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Thanks