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Diffusion in Materials
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MaterialsTJand MetallurgyTJ(ME-209) TJ

TJ TJ TJ TJ TJ
Dr. Tariq Jamil
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E-mail: [email protected]
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Office: DICE Energy Lab, MED, NEDUET

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 Materials and Metallurgy (ME-209)
(According to Course Outline)
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Diffusion in materials: Diffusion theory, equilibrium and non-equilibrium diffusion

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mechanisms, effect of diffusion TJ
on material properties TJ TJ

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 Books / Resource Material
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• Text book: “Materials Science and Engineering: An Introduction” by

David G. Rethwisch, 7th Edition
TJ William D. Callister and TJ TJ TJ TJ
• Chapter # 5 “Diffusion”

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• Reference book: Principles of Material Sciences & Engineering by
William F. Smith, rd
TJ TJ3 Edition TJ TJ TJ

• Online resources (Lectures and resource material on Google

TJ classroom, YouTube, Wikipedia)
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 Outline
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• How does diffusion occur?

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• Why is it an important part of processing?
• How can the rate of diffusion be predicted for some simple cases?
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• How does diffusion depend on structure and temperature?
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 Diffusion
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Diffusion - Mass transport by atomic motion

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Mechanisms
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• Gases & Liquids – random (Brownian) motionTJ TJ

TJ • Solids – vacancy
TJ diffusion or interstitial
TJ diffusion TJ TJ

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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.

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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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 Diffusion Mechanism
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For an atom to make such a move, two conditions must be met:

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(1) there must be an empty adjacent site, and

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(2) the atom must have sufficient energy to break bonds with its neighbor
TJ atoms andTJthen cause some lattice
TJ distortion duringTJthe displacement. TJ

This energy is vibrational in nature

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At a specific temperature some small fraction of the total number of atoms is

capableTJof diffusive motion,TJ TJ
by virtue of the magnitudes TJ
of their vibrational
energies.

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 Diffusion Mechanism
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Several different models for this atomic motion have been proposed; of
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these possibilities, two dominate for metallic diffusion.

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• Vacancy Diffusion
TJ • Interstitial diffusion
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 Diffusion Mechanisms
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Vacancy Diffusion:
TJ • atoms exchange
TJ with vacanciesTJ TJ TJ
• applies to substitutional impurities atoms
• rate depends on:
TJ TJ
-- number of vacancies TJ TJ
Since diffusing atoms and vacancies exchange positions,
TJ
-- activation energy to
TJ TJ
exchange. the
TJdiffusion of atoms in one direction corresponds
TJ to the
motion of vacancies in the opposite direction.

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increasing elapsed time 10

 Diffusion Mechanisms
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• Interstitial diffusion – smaller atoms can diffuse between

TJ
atoms. TJ TJ TJ TJ

TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ TJ TJ TJ

TJ TJ from Fig. 5.3(b), Callister & Rethwisch

Adapted TJ 8e. TJ

More rapid than vacancy diffusion

This mechanism is found for interdiffusion of impurities such
interstitial diffusion occurs much more rapidly than diffusion
as hydrogen, carbon, nitrogen, and oxygen, which have
by the vacancy mode, reason ?? 11
atoms that are small enough to fit into the interstitial positions.
Processing Using Diffusion
• Case Hardening:
Adapted from
-- Diffuse carbon atoms into the host iron chapter-opening
atoms at the surface. photograph,
Chapter 5,
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.

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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 &
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Rethwisch 8e.
 Diffusion
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• How do we quantify the amount or rate of diffusion?

TJ TJ
moles (or mass)TJdiffusing mol TJ
kg TJ
J  Flux   or
surface area time  2
cm s m2s
TJ TJ TJ TJ
• Measured empirically
TJ – Make thin film (membrane)
TJ TJ of known surface area
TJ TJ
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
TJ TJ
membrane TJ TJ TJ

TJ TJ M = TJ TJ
M l dM mass J  slope
J  diffused
At A dt
time
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 It postulates that the flux goes from regions of high
concentration to regions of low concentration, with a
Steady-State Diffusion magnitude that is proportional to the concentration gradient

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Rate of diffusion independent of time
dC
TJ Flux proportional
TJ to concentration
TJ gradient = TJ TJ
dx
TJ
C1 C1
TJ Fick’sTJfirst law of diffusionTJ
TJ TJ TJ TJ TJ
dC
C2 C2 J  D
TJ TJ TJ dxTJ TJ

x1 x2
TJ x TJ TJ TJ
D  diffusion coefficient
dC C C2  C1
if linear  
dx x x2  x1
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 Example: Chemical Protective Clothing (CPC)
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• Methylene chloride is a common ingredient of paint removers. Besides

TJ
being an irritant, it TJ
also may be absorbed TJ
through skin. WhenTJ
using this TJ

paint remover, protective gloves should be worn.

TJ TJ
• If butyl rubber gloves (0.04 cm thick) are used,TJwhat is the diffusiveTJflux of
TJ methylene chloride
TJ through the glove?
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• Data:
TJ • diffusion coefficient
TJ in butyl rubber: TJ TJ TJ
D = 110 x10-8 cm2/s
• surface
TJ concentrations: TJ TJ
C = 0.44 g/cm3 TJ
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 ) -5 g

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

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 Diffusion and Temperature
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• Diffusion coefficient increases with increasingTJT. TJ

TJ TJ TJ TJ TJ
 Qd 
D  Do exp 
TJ TJ  RT  TJ TJ

TJ TJ TJ
D = diffusion coefficient [m2/s] TJ TJ

Do = pre-exponential [m2/s]
TJ QdTJ= activation energy [J/mol
TJ or eV/atom] TJ TJ

R = gas constant [8.314 J/mol-K]

TJ TJ temperature [K]
T = absolute TJ TJ

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 Diffusion and Temperature
TJ D has
TJ exponential dependence
TJ on T TJ TJ

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TJ TJ TJ
Dinterstitial TJ
>> Dsubstitutional
C in a-Fe Al in Al
C in g-Fe Fe in a-Fe
Fe in g-Fe 19
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 
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 Example (cont.)
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 Qd  1 1 
D2  D1 exp    
TJ TJ R
  T2 T1  TJ TJ TJ

TJ T1 = 273 + 300TJ= 573 K TJ TJ

TJ TTJ
2 = 273 + 350 = 623K
TJ TJ TJ

TJ TJ 11 2   41TJ
,500 J/mol  1 TJ 1  TJ
D2  (7.8 x 10 m /s) exp    
 8.314 J/mol - K  623 K 573 K 
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D2 = 15.7 x 10-11 m2/s

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 Diffusion as Function of Time and Position
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 Non-steady State Diffusion
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TJ • The concentration
TJ of diffusingTJspecies is a function
TJ of TJ
both time and position C = C(x,t)
TJ • In this case Fick’s
TJ Second Law is used TJ TJ

TJ TJ
Fick’s Second Law
TJ
C  2C TJ TJ
D 2
t x
TJ TJ TJ TJ TJ

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 Non-steady State Diffusion
TJ • Copper
TJ diffuses into a bar
TJof aluminum. TJ TJ
Surface conc.,
Cs of Cu atoms bar
TJ TJ TJ
pre-existing conc., Co of copper atomsTJ TJ

Cs
TJ TJ TJ TJ
Adapted from
TJ TJ TJ TJ Fig. 5.5, TJ
Callister &
Rethwisch 8e.

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TJ
B.C. at t = 0, CTJ= Co for 0  x   TJ TJ

at t > 0, C = CS for x = 0 (constant surface conc.)

C = Co for x =  24
 Solution:
TJ TJ C x , t   Co TJ  x  TJ TJ
 1  erf  
Cs  Co  2 Dt 
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C(x,t) = Conc. at point x at CS
time t
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erf (z) = error function
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2 z C(x,t)

y 2
 e dy
TJ

TJ
0
CTJ
o
TJ TJ
erf(z) values are given in
TJ Table 5.1 TJ TJ TJ
Adapted from Fig. 5.5,
Callister & Rethwisch 8e.

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 Non-steady State Diffusion
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• Sample Problem: An FCC iron-carbon alloy initially containing 0.20 wt% C

TJ
is carburized at anTJ
elevated temperature TJ TJ
and in an atmosphere that gives TJ

a surface carbon concentration constant at 1.0 wt%. If after 49.5 h the

concentration
TJ of carbon isTJ0.35 wt% at a position
TJ 4.0 mm below theTJ

TJ
surface, determine
TJ
the temperature
TJ
at which the treatment
TJ
was carried out.
TJ

• Solution:
TJ use Eqn. TJ
5.5 TJ TJ TJ
C ( x, t )  C o  x 
 1  erf  
Cs  Co  2 Dt 
TJ TJ TJ TJ

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 C ( x , t )  Co  x 
Solution (cont.):  1  erf  
Cs  Co  2 Dt 
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TJ TJ TJ TJ TJ
• t = 49.5 h x =4x 10-3 m
• Cx = 0.35 wt% Cs = 1.0 wt%
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• Co = 0.20 wt%
TJ ( x, t )  Co 0.35  0.20
CTJ TJ  x  TJ TJ
  1  erf    1  erf ( z )
Cs  Co 1.0  0.20  2 Dt 
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 erf(z) = 0.8125
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 Solution (cont.):
TJ We TJ
must now determine from TJTable 5.1 the value of zTJ
for which the TJ
error function is 0.8125. An interpolation is necessary as follows
TJ TJ TJ TJ TJ
z  0.90 0.8125  0.7970
z erf(z) 
0.95  0.90 0.8209  0.7970
0.90 0.7970
TJ TJ TJ TJ
z 0.8125 z  0.93
TJ TJ0.95 0.8209 TJ TJ TJ

TJ Now solve for

TJ D x TJ x2 TJ TJ
z D
2 Dt 4z 2t
TJ TJ TJ TJ
 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
TJ TJ T  TJ
which D has the aboveTJvalue, we R(ln Do  ln D )
TJ

use a rearranged form of

TJ EquationTJ(5.9a); TJ TJ TJ

from Table 5.2, for diffusion of C in FCC Fe

TJ TJ TJ TJ
Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol
TJ TJ TJ TJ TJ

148,000 J/mol
TJ  T  TJ TJ TJ TJ
5 2 11 2
(8.314 J/mol - K)(ln 2.3 x10 m /s  ln 2.6 x10 m /s)
TJ TJ TJ TJ

T = 1300 K = 1027ºC

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 Example: Chemical Protective Clothing (CPC)
TJ TJ TJ TJ TJ

• Methylene chloride is a common ingredient of paint removers. Besides being an irritant, it

TJalso may be absorbedTJ through skin. When using TJ this paint remover, protective
TJ gloves TJ
should be worn.
• If butylTJrubber gloves (0.04 cmTJ thick) are used, what is TJ
the breakthrough time (tbTJ
), i.e., how
long could the gloves be used before methylene chloride reaches the hand?
TJ • Data TJ TJ TJ TJ
• diffusion coefficient in butyl rubber:
TJ D = 110 x10-8 cm2/s
TJ TJ TJ TJ

TJ TJ TJ TJ

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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
  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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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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 VMSE: Student Companion Site
Diffusion Computations & Data Plots

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