MSE 280: Introduction to Engineering Materials

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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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
(Fig. 5.0
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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

PROCESSING USING DIFFUSION (2)

• Doping Silicon with P for n-type semiconductors:
• Process: 0.5mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip

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

3. Result: Doped light regions: Si atoms

semiconductor
regions.

light regions: Al atoms

silicon From Callister 6e resource CD.
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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.

Cu Ni
100% 100%

0 0
Concentration Profiles Concentration Profiles
From Callister 6e resource CD.

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

low conc.). 5
© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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
C
A D
A
D
B
B
From Callister 6e resource CD.

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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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 manyy p possible mechanisms but let’s consider

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

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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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 MODELING DIFFUSION: FLUX
• Flux:
1 dM ⎡ kg ⎤ ⎡ atoms ⎤
J= ⇒⎢ ⎥ or ⎢ ⎥
A dt ⎣m 2 s ⎦ ⎣ m2 s ⎦
• Directional Quantity
y J x-direction
y
From Callister 6e resource CD.

Jx
Jz x Unit area A
z through
• Flux can be measured for: which
--vacancies atoms
--host (A) atoms move.
--impurity (B) atoms In general: diffusion flux may or may not be
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the same over time
© 2007, 2008 Moonsub Shim, University of Illinois MSE280

MODELING DIFFUSION
What causes net flow of atoms?
• Concentration Profile, C(x): [kg/m3]
Cu flux Ni flux

Concentration Concentration Adapted from

Fig. 5.2(c),
of Cu [kg/m 3 ] of Ni [kg/m 3 ] Callister 6e.

Position, x
• Fick's First Law:
Diffusion coefficient [m 2 /s]
flux in x-dir.
[kg/m 2 -s] dC
Jx = −D concentration
dx gradient [kg/m 4 ]
From Callister 6e resource CD.

• The steeper the concentration profile, the greater the flux! 12

© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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 Steady-state diffusion
• Steady State: the concentration profile doesn't
change with time.
Steady State:
J x(left) J x(right) J x(left) = J x(right)
x
Concentration, C, in the box doesn’t change w/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. 13
© 2007, 2008 Moonsub Shim, University of Illinois MSE280

EX: STEADY-STATE DIFFUSION

• Steel plate at 3
g /m
700C with =1
.2 k
m
3
geometry C1 . 8kg/
=0
shown: Carbon C2 Steady State =
rich straight line! Adapted from
Fig. 5.4,
gas Carbon Callister 6e.
deficient
gas
D=3x10 -11 m 2 /s
0 x1 x2
10
5m

• Q: How much
m
m

carbon transfers
from the rich to C2 − C 1 kg
J = −D = 2 .4 × 10 −9
the deficient side? x2 − x 1 m 2s
From Callister 6e resource CD.
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

Non steady-state diffusion

From Fick’s 1st Law: dc
J = −D
dx Jr
Jl
T k the
Take th first
fi t derivative
d i ti w.r.t.
t x:
dJ d ⎛ dc ⎞
= − ⎜D ⎟
dx dx ⎝ dx ⎠
dx c = conc.
Conservation of mass: dc J r − J l dJ
inside box
− =− =
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… 16
© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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 EX: NON STEADY-STATE DIFFUSION
• Copper diffuses into a bar of aluminum (semi infinite solid).
Surface conc.,
C s of Cu atoms bar
pre-existing
i ti conc., C o off copper atoms
t
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.

Co t o
position, x
• General solution: C(x, t ) − C o = ⎛ x ⎞
1 − erf ⎜ ⎟
Cs − Co ⎝ 2 Dt ⎠
"error function" From Callister 6e resource CD.
Values calibrated in Table 5.1, Callister 6e. 17
© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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.
C (x, t ) − Co ⎛ x ⎞
= 1 − erf ⎜ ⎟ (Dt) 500ºC =(Dt) 600ºC
C −C ⎝ 2 2Dt
Dt ⎠
s o
5.3 x10 -13 m 2 /s 10hrs
(Dt )600 Note: values
• Answer: t 500 = = 110 hr of D are
D500 provided here.
4.8x10 -14 m 2 /s
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Adapted from Callister 6e resource CD.
© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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 Temperature dependence
pre-exponential [m 2 /s] (see Table 5.2, Callister 6e )
activation energy
⎛ Q ⎞ [J/mol],[eV/mol]
diffusivity D = Do exp ⎜− d ⎟ ((see Table 5.2,, Callister 6e )
⎝ RT ⎠
gas constant [8.31J/mol-K]

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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

Diffusion: design example

• During a steel carburization process at 1000oC, there is
a drop
p in carbon concentration from 0.5 at% to 0.4 at%
between 1 mm and 2 mm from the surface (γ-Fe at
1000oC).
– Estimate the flux of carbon atoms at the surface.
Do = 2.3 x 10-5 m2/s for C diffusion in γ-Fe.
Qd = 148 kJ/mol
ργ-Fe = 7.63 g/cm3
AFe = 55.85 g/mol

– If we start with Co = 0.2 wt% and Cs = 1.0 wt% how long does it
take to reach 0.6 wt% at 0.75 mm from the surface for different
processing temperatures?

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 Diffusion: design example cont’d
1011

10
9 T (oC) t (s) t (h)

107
300 8.5 x 1011 2.4x108 27782 yrs!
time (hours)

105
900 106,400 29.6
950 57,200 15.9
1000
1000 32,300 9.0
10
1050 19,000 5.3
0.1
200 400 600 800 1000 1200
T (K)

Need to consider factors such as cost of maintaining furnace at different

T for corresponding times.

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Design example 2
Metal Concentrations (in mol/m3)
plate ⎛ 27.8kJ / mol ⎞
C H 2 = 2.5 ×103 pH 2 exp⎜ − ⎟
⎝ RT ⎠

H2 ⎛ 37.6kJ / mol ⎞
C N 2 = 2.75 ×103 p N 2 exp⎜ − ⎟
(0.1013MPa)
H2 ⎝ RT ⎠
(0.051MPa) Diffusion coefficients (in m2/s)
⎛ 13.4kJ / mol ⎞
DH 2 = 1.4 ×10 −7 exp⎜ − ⎟
N2 N2 ⎝ RT ⎠
((0.1013MPa)) (
(0.01013MPa)
)
⎛ 76.15kJ / moll ⎞
DN 2 = 3.0 ×10 −7 exp⎜ − ⎟
⎝ RT ⎠
Δx
Given the above info, determine whether or not it will
be possible to use this metal plate for gas separation.
If so, at what temperature? 24
© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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

- + - + - + - + - + -

+ - + - + - + - + - +

- + - + - + - + - + -

+ - + - + - - + - +

- + - + - + - + - + -

+ - + - + - + - + - +

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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

Concepts to remember
• Diffusion mechanisms and phenomena.
– Vacancy diffusion.
diffusion
– Interstitial diffusion.
• Importance/usefulness of understanding
diffusion (especially in processing).
• Steady-state diffusion.
• Non steady-state
y diffusion.
• Temperature dependence.
• Structural dependence (e.g. size of the diffusing
atoms, bonding type, crystal structure etc.).
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280

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