Chapter 6: Diffusion

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Case Hardened Steel Gear

Diffusion of carbon during

high-temperature treatment

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 DIFFUSION DEMO
• Glass tube filled with water.
• At time t = 0, add some drops of ink to one end
of the tube.
• Measure the diffusion distance, x, over some time.
• Compare the results with theory.

to x (mm)
t1
t2
t3
time (s)
xo x1 x2 x3

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 Diffusion Couple
Initially After some time

Cu Ni
100% 100%

0 0
Concentration Profiles Concentration Profiles
Heated for an extended period at an elevated temperature

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Diffusion Mechanisms

Vacancy Diffusion

Interstitial Diffusion

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 Interstitial Diffusion

• For atoms such as H, C, N, O

• Interstitial diffusion is faster than vacancy diffusion.

¾ Interstitial atoms are smaller and more mobile.
¾ There are more empty interstitial positions
than vacancies.

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Vacancy Diffusion

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Vacancy Diffusion

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Vacancy Diffusion

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Vacancy Diffusion

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 Vacancy Diffusion

Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

increasing elapsed time

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 Vacancy Diffusion

Rate of substitutional diffusion depends on:

--vacancy concentration
--frequency of jumping.
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 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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 Interstitial Diffusion

• 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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 MODELING DIFFUSION: FLUX
• Flux:
1 dM ⎡ kg ⎤ ⎡ atoms⎤
J= ⇒⎢ ⎥ or ⎢ ⎥
A dt 2
⎣m s ⎦ 2
⎣ m s ⎦
• Directional Quantity x-direction
y J
y

Jx Unit area A
Jz x through
z which
• Flux can be measured for: atoms
--vacancies move.
--host (A) atoms
--impurity (B) atoms
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 CONCENTRATION PROFILES & FLUX

• Concentration Profile, C(x): [kg/m3]

Cu flux Ni flux

Concentration Concentration
of Cu [kg/m3] of Ni [kg/m3]

Position, x
• Fick's First Law:
flux in x-dir. Diffusion coefficient [m2/s]
[kg/m2-s] dC
Jx = − D concentration
dx gradient [kg/m4]
• The steeper the concentration profile,
the greater the flux!
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 STEADY STATE DIFFUSION

• Steady State: the concentration profile doesn't

change with time.
Steady State:
Jx(left) Jx(right) Jx(left) = Jx(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)!
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STEADY STATE DIFFUSION

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 EX: STEADY STATE DIFFUSION
• Steel plate at m
3
g/
700C with 1 .2k 3
= /m
C1 kg
geometry = 0. 8
shown: Carbon C2 Steady State =
rich straight line! Adapted
gas Carbon
from Fig.
5.4,
Callister 6e.
deficient
gas
D=3x10-11m2/s
0 x1 x2

10
• Q: How much 5m

m
m

m
carbon transfers
from the rich to C2 − C1 = × −9 kg
J = −D 2.4 10
the deficient side? x2 − x1 m2s

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 NON STEADY STATE DIFFUSION

• Concentration profile,
dx
C(x), changes J(left) J(right)
w/ time.
Concentration,
C, in the box
• To conserve matter: • Fick's First Law:
J(right) − J(left) = dC dC
− J = − D or
dx dt dx
dJ = dC dJ = d2 C (if D does
− −D not vary
dx dt dx dx2 with x)
equate
• Governing Eqn.:
dC d2C
=D
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Solution of Fick’s 2nd Law for Semi-Infinite Solid

dC d2C
=D
dt dx 2
Boundary Conditions
For t=0, C=Co at 0≤ x ≤ ∞
For t>0, C=Cs at x=0
C=Co at x=∞

C(x, t) − Co = − ⎛ x ⎞
1 erf ⎜⎝ ⎟
Cs − Co 2 Dt ⎠

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Solution of Fick’s 2nd Law for Semi-Infinite Solid

C(x, t) − Co = − ⎛ x ⎞
1 erf ⎜⎝ ⎟
Cs − Co 2 Dt ⎠

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 EX: NON STEADY STATE DIFFUSION
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., C o of copper atoms
C(x,t)
Cs

t3 Adapted from
t2 Fig. 5.5,

t t1 Callister 6e.

Co o
position, x
• General solution: C(x, t) − Co = − ⎛ x ⎞
1 erf ⎜⎝ ⎟
Cs − Co 2 Dt ⎠
"error function"
Values calibrated in Table 5.1, Callister 6e.
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 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
Cs − Co 2Dt ⎠

5.3x10-13m2/s 10hrs
(Dt)600 Note: values
• Answer: t 500 = = 110 hr of D are
D500 provided here.
4.8x10-14m2/s
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 DIFFUSION DEMO: ANALYSIS
• The experiment: we recorded combinations of
t and x that kept C constant.
to
t1
t2
t3
xo x1 x2 x3

C(x i , t i ) − Co ⎛ x ⎞
= 1− erf ⎜⎜ i ⎟
⎟ = (constant here)
C s − Co ⎝ 2 Dt i ⎠

• Diffusion depth given by:

x i ∝ Dt i
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 DATA FROM DIFFUSION DEMO
( )
4
BBBBB
3.5 B B BBB
B B
3 B
B
2.5
2 Linear regression fit to data:
1.5 ln[x(mm)] = 0.58 ln[t(min)] + 2.2
1 R2 = 0.999
0.5
0
0 0.5 1 1.5 2 2.5 3
ln[t(min)]

• Experimental result: x ~ t0.58

• Theory predicts x ~ t0.50
• Reasonable agreement!
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 DIFFUSION AND TEMPERATURE
• Diffusivity increases with T.
pre-exponential [m2/s] (see Table 5.2, Callister 6e)
Arrehenius Equation activation energy
⎛ Q ⎞ [J/mol],[eV/mol]
diffusivity D = D exp ⎜− d ⎟ (see Table 5.2, Callister 6e )
o ⎝ RT ⎠
gas constant [8.31J/mol-K]
• Experimental Data:
1500
1000

600

300
T(C)
10-8 D has exp. dependence on T
C
in

D (m2/s) Ci Recall: Vacancy does also!

γ-

nα
Fe

-Fe Dinterstitial >> Dsubstitutional

10-14 C in α-Fe Cu in Cu
Zn

C in γ -Fe Al in Al
Fe

in Cun α-

Al

Fe in α-Fe
Cu in Fe
F

in
in
ei e

Fe in γ -Fe
Al
γ-F

Zn in Cu
10-20
Cu

0.5 1.0 1.5 2.0 1000K/T

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Example

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