Diffusion in Solids

Reading: Chapter 6

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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 What is diffusion?
Phenomenon of material/matter transport by atomic motion.

Often think of diffusion in a medium where atoms are

relatively free to move around such as liquids and gases…

So, why do we care about diffusion in solids?

e.g. Materials processing

Many materials are heat treated to achieve necessary
properties: prefer to develop methods that will allow
relatively high diffusion rates to achieve an
efficient/cost-effectively process (e.g. alloying, case
hardening etc…)

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 PROCESSING USING DIFFUSION (1)
• Case Hardening:
--Diffuse carbon atoms Fig. 5.0,
Callister 6e.
into the host iron atoms (Fig. 5.0 is
courtesy of
at the surface. Surface
Division,
--Example of interstitial Midland-
Ross.)
diffusion is a case
hardened gear.

• Result: The "Case" is

--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.
From Callister 6e resource CD.

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 PROCESSING USING DIFFUSION (2)
• Doping Silicon with P for n-type semiconductors:
• Process:
1. Deposit P rich
layers on surface.

silicon
Fig. 18.0,
2. Heat it. Callister 6e.

3. Result: Doped
semiconductor
regions.

silicon From Callister 6e resource CD.

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 DIFFUSION: THE PHENOMENON
• Interdiffusion: Atoms of one material diffusing into another and vice
versa.
e.g. In an alloy, atoms tend to migrate from regions of large
concentration.
Initially After some time

Adapted from
Figs. 5.1 and
5.2, Callister
6e.

100%

0
Concentration Profiles
From Callister 6e resource CD.

Consider as a concentration gradient (atoms move from high conc. to

low conc.).
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 DIFFUSION: THE PHENOMENON
• Self-diffusion: Atoms within one material
exchanging positions. (i.e. In an elemental solid, atoms
also migrate).

Label some atoms After some time

C
A
D
B
From Callister 6e resource CD.

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 Diffusion mechanisms
How do atoms move in a crystalline solid?
For diffusion to occur:
1. Adjacent site needs to be empty (vacancy or
interstitial).
2. Sufficient energy must be available to break
bonds and overcome lattice distortion.

There are many possible mechanisms but let’s consider

the simple cases:
1. Vacancy diffusion.
2. Interstitial diffusion.

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 Vacancy diffusion
- An atom adjacent to a vacant lattice site moves into it.
First, bonds with the neighboring
atoms need to be broken

Lattice
distortion.
From Callister 6e resource CD.

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 Interstitial Diffusion
- migration from one interstitial site to another (mostly for
small atoms that can be interstitial impurities: e.g. H, C, N,
and O).

Callister fig. 5.3

Typically more rapid than vacancy diffusion. From Callister 6e resource CD.

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 MODELING DIFFUSION: FLUX
Consider atoms (or mass, M) going through a plane

2 atoms passed from left to

right (+ direction)
t=0
1 atom passed from right
t = t’
to left (- direction)

1atom M
Net result: or
area × t ' At '
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 MODELING DIFFUSION: FLUX
• Flux:

• Directional Quantity

From Callister 6e resource CD.

• Flux can be measured for:

--vacancies
--host (A) atoms
--impurity (B) atoms In general: diffusion flux may or may not be
the same over time 11
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 MODELING DIFFUSION
What causes net flow of atoms?
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted

of Cu [kg/m3] of Ni [kg/m3]
from Fig.
5.2(c),
Callister 6e.

Position, x
• Fick's First Law:

From Callister 6e resource CD.

• The steeper the concentration profile, the greater the

flux! 12
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 Steady-state diffusion
• Steady State: the concentration profile doesn't
change with time.

dC
• Apply Fick's First Law: J x = −D
dx
 dC   dC
• If Jx)left = Jx)right , then   = 
 dx  left  dx  right

• Result: the slope, dC/dx, must be constant

(i.e., slope doesn't vary with position)! From Callister 6e resource CD.

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 EX: STEADY-STATE DIFFUSION
• Steel plate at
700C with
geometry
shown:
Adapted
from Fig.
5.4,
Callister 6e.

• Q: How much
carbon transfers
from the rich to
the deficient side?
From Callister 6e resource CD.

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 Note that we’d have to remove carbon from the right
side and add to the left side to keep a constant flux.

Possible in the previous example of processing

using gas source that can be added and removed
but in many cases this may not be possible….

Non steady-state diffusion

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 NON STEADY STATE DIFFUSION
• Concentration profile,
C(x), changes
w/ time.

• To conserve matter: • Fick's First Law:

• Governing Eqn.:

14
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 Non steady-state diffusion
From Fick’s 1st Law: dc
J = −D
dx
Jl Jr
Take the first derivative w.r.t. x:
dJ d  dc 
= − D 
dx dx  dx 
dx c = conc.
inside box
Conservation of mass: dc J r − J l dJ
− =− =
dt dx dx
i.e. fluxes to left and to right have to correspond to concentration change.
Sub into the first derivative:
dc d  dc 
= D  Fick’s 2nd law
dt dx  dx 
Partial differential equation. We’ll need boundary conditions to solve…
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 EX: NON STEADY-STATE DIFFUSION
• Copper diffuses into a bar of aluminum (semi infinite
solid).

C(x,t)
Cs At to, C = Co inside the Al bar
At t > 0, C(x=0) = Cs and C(x=∞) = Co

t2 t3
Adapted from
Fig. 5.5,
t1 Callister 6e.
t
Co o
position, x
• General solution:

"error function" From Callister 6e resource CD.

Values calibrated in Table 5.1, Callister 6e.
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 If it is desired to achieve a specific concentration C1

i.e. C ( x, t ) − Co C1 − Co
= = constant
C s − Co C s − Co

which leads to:

Specified with C1
x
= constant
2 Dt

Known for given system

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MetE 201 20
 PROCESSING QUESTION
• Copper diffuses into a bar of aluminum.
• 10 hours at 600C gives desired C(x).
• How many hours would it take to get the same C(x)
if we processed at 500C?
Key point 1: C(x,t500C) = C(x,t600C).
Key point 2: Both cases have the same Co and Cs.
• Result: Dt should be held constant.

2 Dt

Note: values
• Answer: of D are
provided here.

Adapted from Callister 6e resource CD.

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 Temperature dependence

D has exp. dependence on T

Recall: Vacancy does also!

Dinterstitial >> Dsubstitutional

C in α-Fe Cu in Cu
C in γ-Fe Al in Al
Fe in α-Fe
Fe in γ-Fe
Zn in Cu

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 Diffusion in ionic solids
Need to consider coulomb interactions between ions…

- + - + - + - + - + -

+ - + - + - + - + - +

- + - + - + - + - + -

+ - + - + - - + - +

- + - + - + - + - + -

+ - + - + - + - + - +

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 Diffusion in ionic solids
Which do you expect to diffuse faster, cations
or anions?

Smaller cations will usually diffuse faster. But

analogous to charge neutrality required for
defect formation, each ion will need counter
charge to move with it (e.g. vacancy, impurity
or free electrons or holes).

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 STRUCTURE & DIFFUSION
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• lower melting T materials • higher melting T materials

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

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 Concepts to remember
• Diffusion mechanisms and phenomena.
– Vacancy diffusion.
– Interstitial diffusion.
• Importance/usefulness of understanding
diffusion (especially in processing).
• Steady-state diffusion.
• Non steady-state diffusion.
• Temperature dependence.
• Structural dependence (e.g. size of the diffusing
atoms, bonding type, crystal structure etc.).

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