TOPIC 2: 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?

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 Diffusion
Diffusion - Mass transport by atomic motion in
materials (solids, liquids or gases)

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

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 Why diffusion is important?
• Heat treatment (phase transformation from
solid to solid)

• Solidification (liquid to solid)

• Surface hardening of steel

(carburising, nitriding, etc…)

• Coatings

• sintering of ceramics
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 Diffusion in solid materials
Temperature
should be
high enough
to overcome
energy
barriers to
atomic
motion

Heat : causes atoms to vibrate

Vibration amplitude : increases with
temperature
Melting occurs when vibrations are
sufficient to rupture bonds 4
Two types of diffusion in crystalline solids:

(1) impurity diffusion or

interdiffusion
Occurs in a solid material with
more than one type of element
(such as an alloy)
(2) Self-diffusion
Occurs in chemically pure
materials (only one type of
atoms)
 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
7e.

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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 Simulation

• Simulation of
interdiffusion
across an interface:

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

(Courtesy P.M. Anderson)

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 Diffusion mechanism
• Atoms are constantly in motion and
vibrating
• Change of atomic position requires:
•Vacant site
•Energy to break
atomic bonds

Two types of diffusion

mechanism:
•Vacancy diffusion or substitutional
diffusion
•Interstitial diffusion
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 Diffusion Mechanisms
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.

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

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

More rapid than vacancy diffusion because the interstitial

atoms are smaller, thus more mobile. Also, there are more 11
empty interstitial positions than vacancies.
 INTERSTITIAL SIMULATION

• 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 (Courtesy P.M. Anderson)

unit cell edges.

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 Processing Using Diffusion
• Case Hardening:
Adapted from
--Diffuse carbon atoms chapter-opening
into the host iron atoms photograph,
Chapter 5,
at the surface. Callister 7e.
(Courtesy of
--Example of interstitial Surface Division,
Midland-Ross.)
diffusion is a case
hardened gear.

• Result: The presence of C

atoms makes iron (steel) harder.

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 Steady-State Diffusion
Rate of diffusion independent of time (no change in
concentration of solute atoms with 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

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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: C1 = 0.44 g/cm3
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 x 2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

-8 (0.02 g/cm3  0.44 g/cm3 )

2 g
J   (110 x 10 cm /s)  1.16 x 10-5
(0.04 cm) cm2s

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 Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

Arrhenius equation:
 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]

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 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 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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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 Q  1
lnD2  lnD0    and lnD1  lnD0  d  
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 = 573K

T2 = 273 + 350 = 623K

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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 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 Fick’s Second Law is used
Fick’s Second Law C  2
C
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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