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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 Reading

– Chapter 5
- Section 5.1 Introduction
- Section 5.2 Diffusion mechanisms
- Section 5.3 Fick’s first law
- Section 5.5 Factors that influence diffusion

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 Atomic Diffusion in Solids

– Diffusion is a process by which a matter is transported through another

matter.
– Examples:
 Movement of smoke particles in air : Very fast.
 Movement of dye in water : Relatively slow.
 Solid state reactions : Very restricted movement due to
bonding.

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 Kirkendall Effect

Discovered in 1942, the Kirkendall effect describes what happens when

two solids diffuse into each other at different rates.

For a general case, the Kirkendall

experiment considers a diffusion couple A
and B, where the diffusion rates of the
two species are different (|JA| > |JB|).

Since the diffusion fluxes are different,

there will be a net flow of matter past the
inert markers, causing the couple to shift
bodily with respect to the markers.

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 Diffusion
• Interdiffusion: In an alloy, atoms tend to migrate from regions
of high concentration to regions of low concentration

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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 How does diffusion occur?

a) b) c)

The atomic diffusion mechanism showing (a) a direct exchange

mechanism, (b) ring mechanism, and (c) vacancy mechanism.
H. Nakajima “The Discovery and Acceptance of the Kirkendall Effect: The Result of a Short Research Career”, JOM 49 (6) (1997), pp. 15-19
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 Diffusion Mechanisms

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 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 Mechanisms

– Interstitial diffusion – smaller atoms can diffuse between

atoms.

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

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 Question Time

Which mechanism is the fastest:

vacancy or interstitial diffusion? Justify

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 Processing Using Diffusion

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

• Result: The presence of C

atoms makes iron (steel) harder.

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 Diffusion

– How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

J ≡ Flux ≡ = or
(surface area )(time ) cm2s m2s
– 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 1
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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 Question time

Carbon atoms will diffuse faster in α-Fe (BCC) or

γ-Fe (FCC)? Justify

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 Diffusivity

– Diffusivity depends upon

 Type of diffusion : Whether the diffusion is interstitial
or substitutional.
 Temperature: As the temperature increases diffusivity
increases.
 Type of crystal structure: BCC crystal has lower APF
than FCC and hence has higher diffusivity.
 Type of crystal imperfection: More open structures
(grain boundaries) increases diffusion.
 The concentration of diffusing species: Higher
concentrations of diffusing solute atoms will affect
diffusivity.

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 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]

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 Diffusion and Temperature

D has exponential dependence on T

1500

1000
T(°C)

600

300
10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in α-Fe Al in Al
10-14 C in γ-Fe Fe in α-Fe
Fe in γ-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 2
Temperature effect on diffusion coefficient

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?

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 Conclusion on the Chapter: Question Time

Diffusion FASTER for...

a) open crystal structures or close-packed structures?

b) large diffusing atoms or small diffusing atoms?

c) lower density materials or higher density materials?

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