TOPIC 2: Diffusion in Solids

Why diffusion is important?

Heat treatment (phase transformation from
solid to solid)

ISSUES TO ADDRESS...
How does diffusion occur?

Solidification (liquid to solid)

Why is it an important part of processing?

Surface hardening of steel

(carburising, nitriding, etc)

How can the rate of diffusion be predicted for

some simple cases?

Coatings

How does diffusion depend on structure

and temperature?

sintering of ceramics
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Diffusion

Diffusion in solid materials

Diffusion - Mass transport by atomic motion in

{G
GG
GG
GG
G
GG
G

materials (solids, liquids or gases)

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

oGaGGGG
}GGaGGG

tGGGGGG
GGG

Diffusion

Two types of diffusion in crystalline solids:

Self-diffusion: In an elemental solid, atoms

also migrate.

OXP GGG

vGGGGGG
GGGGGG
OGGGP
OYPGzT
vGGGG
GOGGGG
P

Label some atoms

C
A
D
B

After some time

A
B

Diffusion

Diffusion Simulation

Interdiffusion: In an alloy, atoms tend to migrate

from regions of high conc. to regions of low conc.
Initially

Simulation of
interdiffusion
across an interface:

After some time

Adapted from
Figs. 5.1 and
5.2, Callister
7e.

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

(Courtesy P.M. Anderson)

Diffusion Mechanisms

Diffusion mechanism

Interstitial diffusion smaller atoms can

diffuse between atoms.

Atoms are constantly in motion and

vibrating
Change of atomic position requires:
}G

lGGG

{GGGG
a
}GGGG

pG

Adapted from Fig. 5.3 (b), Callister 7e.

Diffusion Mechanisms

More rapid than vacancy diffusion because the interstitial

atoms are smaller, thus more mobile. Also, there are more
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empty interstitial positions than vacancies.

INTERSTITIAL SIMULATION

Vacancy Diffusion:

atoms exchange with vacancies

applies to substitutional impurities atoms
Both self diffusion and interdiffusion occur by this mechanism
rate depends on:
--number of vacancies
--activation energy to exchange.

Applies to interstitial
impurities.
More rapid than
vacancy diffusion.
Simulation:
--shows the jumping of a
smaller atom (gray) from
one interstitial site to
another in a BCC
structure. The
interstitial sites
considered here are
at midpoints along the
unit cell edges.
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(Courtesy P.M. Anderson)

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Example: Chemical Protective

Clothing (CPC)

Processing Using Diffusion

Case Hardening:
Adapted from
chapter-opening
photograph,
Chapter 5,
Callister 7e.
(Courtesy of
Surface Division,
Midland-Ross.)

--Diffuse carbon atoms

into the host iron atoms
at the surface.
--Example of interstitial
diffusion is a case
hardened gear.

Result: The presence of C

atoms makes iron (steel) harder.

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

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15

Steady-State Diffusion

Example (cont).

Rate of diffusion independent of time (no change in

concentration of solute atoms with time)
dC
Flux proportional to concentration gradient = dx
C1 C1

glove
C1

Ficks first law of diffusion

C2
x1

if linear

Solution assuming linear conc. gradient

C2

J  D

paint
remover

tb 

"2
6D

skin
C2

dC
dx

J -D

x1 x 2

dC
C  C1
 D 2
dx
x2  x1

Data:

D = 110 x 10-8 cm2/s

C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 x1 = 0.04 cm

x2

dC C C2  C1


dx x
x2  x1

D  diffusion coefficient

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J   (110 x 10-8 cm2 /s)

(0.02 g/cm3  0.44 g/cm3 )

g
 1.16 x 10-5
(0.04 cm)
cm2s

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Example: At 300C the diffusion coefficient and

activation energy for Cu in Si are

Diffusion and Temperature

D(300C) = 7.8 x 10-11 m2/s

Qd = 41.5 kJ/mol

Diffusion coefficient increases with increasing T.

Arrhenius equation:

What is the diffusion coefficient at 350C?

 Qd 

D  Do exp

 RT 

transform
data

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]

Temp = T

Qd = activation energy [J/mol or eV/atom]

T = absolute temperature [K]

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 Q
D2  D1 exp  d
 R

D has exponential dependence on T

300

600

1000

Qd
R

 1

T1 

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Example (cont.)

Diffusion and Temperature

1500

1/T

1
Q

and lnD1  lnD0  d

R
T2 
Q  1 1
D
 lnD2  lnD1  ln 2   d


D1
R T2 T1 

lnD2  lnD0 

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

10-8

ln D

T(C)

 1 1 

 
T2 T1 

T1 = 273 + 300 = 573K

D (m2/s)

Dinterstitial >> Dsubstitutional

C in -Fe
C in -Fe

10-14

10-20
0.5

1.0

1.5

Al in Al
Fe in -Fe
Fe in -Fe

T2 = 273 + 350 = 623K

  41,500 J/mol  1
1 

D2  (7.8 x 1011 m2 /s) exp 


 8.314 J/mol - K 623 K 573 K 

1000 K/T

D2 = 15.7 x 10-11 m2/s

Adapted from Fig. 5.7, Callister 7e. (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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Non-steady State Diffusion

The concentration of diffusing species is a function of
both time and position C = C(x,t).
In most cases non-steady state diffusion is occurs,
where the concentration of solute atoms at any point
in the materials changes with time.
e.g. If carbon is being diffused in the surface of a steel
camshaft to harden its surface, the concentration of
carbon under the surface at any point will change
with time as the diffusion process progresses.
In this case Ficks Second Law is used
C
 2C
Ficks Second Law
D 2
t
x
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Summary
Diffusion FASTER for...

Diffusion SLOWER for...

open crystal structures

close-packed structures

smaller diffusing atoms

larger diffusing atoms

lower density materials

higher density materials

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