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Diffusion

Important Concepts
 Applications of Diffusion
 Activation Energy for Diffusion
 Mechanisms for Diffusion
 Rate of Diffusion (Fick’s First Law)
 Factors Affecting Diffusion
 Composition Profile (Fick’s Second Law)
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Diffusion
• How does diffusion occur?
• Why is diffusion 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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• Interdiffusion (impurity diffusion): In an alloy,
atoms tend to migrate from regions of high
concentration to regions of low concentration.
Initially
Interdiffusion
After some time
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• Self-diffusion: In an elemental solid,
atoms also migrate.
specific atom movement
Self-Diffusion
A
B
C
D
After some time
A
B
C
D
Diffusion Mechanisms
• Atoms in solid materials are in constant motion, rapidly
changing positions.
• For an atom to move, 2 conditions must be met:
1. There must be an empty adjacent site, and
2. The atom must have sufficient (vibrational) energy to
break bonds with its neighboring atoms and then
cause lattice distortion during the displacement.
At a specific temperature, only a small fraction of the
atoms is capable of motion by diffusion. This fraction
increases with rising temperature.
• There are 2 dominant models for metallic diffusion:
1. Vacancy Diffusion
2. Interstitial Diffusion
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Vacancy Diffusion
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurity atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.
increasing elapsed time
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Interstitial Diffusion
• Interstitial diffusion – smaller atoms (H,
C, O, N) can diffuse between atoms.
More rapid than vacancy diffusion due to more
mobile small atoms and more empty interstitial sites.
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Diffusion
• How do we quantify the rate of diffusion?

( )( )
s m
kg
or
s cm
mol
time area surface
diffusing mass) (or moles
Flux
2 2
= ÷ ÷ J
J · slope
dt
dM
A At
M
J
1
= =
M =
mass
diffused
time
• Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane

Rate of diffusion is independent of time; the diffusion flux does
not change with time.
The concentration profile shows the concentration (C) vs the position within
the solid (x); the slope at a particular point is the concentration gradient.
Steady-state diffusion across a thin plate
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Steady-State Diffusion
dx
dC
D J ÷ =
Fick’s first law of diffusion
C
1

C
2

x
C
1

C
2

x
1
x
2

D ÷ diffusion coefficient
Flux proportional to concentration gradient =
dx
dC
1 2
1 2
linear if
x x
C C
x
C
dx
dC
÷
÷
=
A
A
~
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Diffusion and Temperature
• Diffusion coefficient increases with increasing T.
D
=
D
o
exp
|
\

|
.
|
÷
Q
d

R T
= pre-exponential [m
2
/s]
= diffusion coefficient [m
2
/s]
= activation energy [J/mol or eV/atom]
= gas constant [8.314 J/mol-K]
= absolute temperature [K]
D
D
o
Q
d
R
T
Activation energy - energy required to produce the movement
of 1 mole of atoms by diffusion.
• The diffusing species, host material and temperature
influence the diffusion coefficient.
• For example, there is a significant difference in magnitude
between self-diffusion and carbon interdiffusion in α iron
at 500 °C.
Factors that influence diffusion
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Example 2: At 300ºC the diffusion coefficient and
activation energy for Cu in Si are:

D(300ºC) = 7.8 x 10
-11
m
2
/s
Q
d
= 41,500 J/mol

What is the diffusion coefficient at 350ºC?
|
|
.
|

\
|
÷ =
|
|
.
|

\
|
÷ =
350
0 350
300
0 300
1
ln ln and
1
ln ln
T R
Q
D D
T R
Q
D D
d d
|
.
|

\
|
÷ ÷ = = ÷
300 350 300
350
300
350
1 1
ln ln ln
T T R
Q
D
D
D D
d
transform
data
D
Temp = T
ln D
1/T
D = D
o
exp
|
\

|
.
|
÷
Q
d

R T
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Example 2 (cont.)
(
¸
(

¸

|
.
|

\
|
÷
÷
=
÷
K 573
1
K 623
1
K - J/mol 314 . 8
J/mol 500 , 41
exp /s) m 10 x 8 . 7 (
2 11
2
D
(
¸
(

¸

|
|
.
|

\
|
÷ ÷ =
1 2
1 2
1 1
exp
T T R
Q
D D
d
T
1
= 273 + 300 = 573 K
T
2
= 273 + 350 = 623 K
D
2
= 15.7 x 10
-11
m
2
/s
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Nonsteady State Diffusion
• The concentration of diffusing species is a
function of both time and position C = C(x,t).
More likely scenario than steady state.
• In this case, Fick’s Second Law is used.

2
2
x
C
D
t
C
c
c
=
c
c
Fick’s Second Law
• 10 hours at 600˚C gives C(x).
• How many hours would it take to get the same C(x) if processed at 500˚C?
• Answer:
Processing – Ex 6.3
|
.
|

\
|
÷ =
÷
÷
Dt
x
C C
C t x C
o s
o
2
erf 1
) , (
• Copper diffuses into a bar of aluminum.
pre-existing concentration C
o
of copper atoms
Surface concentration
C of Cu atoms
bar
s
115.5 hrs
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Non-steady State Diffusion
• Example 3: An FCC iron-carbon alloy initially
containing 0.20 wt% C is carburized at an
elevated temperature and in an atmosphere that
gives a surface carbon concentration constant at
1.0 wt%. If after 49.5 h the concentration of
carbon is 0.35 wt% at a position 4.0 mm below
the surface, determine the temperature at which
the treatment was carried out.

• Solution: use Eqn. 6.5
|
.
|

\
|
÷ =
÷
÷
Dt
x
C C
C t x C
o s
o
2
erf 1
) , (
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Example 3 Solution (1):

– t = 49.5 h x = 4 x 10
-3
m
– C
x
= 0.35 wt% C
s
= 1.0 wt%
– C
o
= 0.20 wt%

|
.
|

\
|
÷ =
÷
÷
Dt
x
C C
C ) t , x ( C
o s
o
2
erf 1
) ( erf 1
2
erf 1
20 . 0 0 . 1
20 . 0 35 . 0 ) , (
z
Dt
x
C C
C t x C
o s
o
÷ = |
.
|

\
|
÷ =
÷
÷
=
÷
÷
erf(z) = 0.8125
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Example 3 Solution (2):
We must now determine from Table 6.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows
z erf(z)
0.90 0.7970
z 0.8125
0.95 0.8209
7970 . 0 8209 . 0
7970 . 0 8125 . 0
90 . 0 95 . 0
90 . 0
÷
÷
=
÷
÷ z
z = 0.93
Now solve for D
Dt
x
z
2
=
t z
x
D
2
2
4
=
/s m 10 x 6 . 2
s 3600
h 1
h) 5 . 49 ( ) 93 . 0 ( ) 4 (
m) 10 x 4 (
4
2 11
2
2 3
2
2
÷
÷
= =
|
|
.
|

\
|
=
t z
x
D
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• To solve for the temperature at
which D has the calculated
value, we use a rearranged
form of Equation (6.9a);

) ln ln (
o
d
D D R
Q
T
÷
=
from Table 6.2, for diffusion of C in FCC Fe

D
o
= 2.3 x 10
-5
m
2
/s Q
d
= 148,000 J/mol
/s) m 10 x 3 . 2 ln /s m 10 x 6 . 2 K)(ln - J/mol 314 . 8 (
J/mol 000 , 148
2 5 2 11 ÷ ÷
÷
= T

Example 4 Solution (3):
T = 1300 K = 1027°C
D = D
o
exp
|
\

|
.
|
÷
Q
d

R T
Applications of Diffusion
• Furnace for heat treating steel using carburization.
• Carburizing is the addition of carbon to the surface of low-
carbon steels at temperatures ranging from 1560°F to
1740°F.
• Hardening is achieved when a high carbon martensitic case
with good wear and fatigue resistance is superimposed on a
tough, low-carbon steel core.
http://www.americanmetaltreatinginc.com/carburizing.htm
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• Case hardening or surface
hardening is the process of
hardening the surface of a metal,
often a low carbon steel, by diffusing
elements into the material's surface,
forming a thin layer of a harder alloy.
• Carbon atoms diffuse into the iron
lattice atoms at the surface.
• This is an example of interstitial
diffusion.
• The C atoms make iron (steel)
harder.
Case Hardening
“Carbide band saw blade can cut
through case hardened materials.”
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Thermal barrier coatings (TBC) with a ceramic topcoat are widely used for
protecting highly loaded gas turbine components against overheating.
For example, on internally cooled turbine blades the ceramic topcoat maintains a
high temperature difference between the outer surface and the underlying metallic
substrate.
Doping by Diffusion
• Integrated circuits (ICs), found in
numerous electronic devices
have been fabricated using
doping techniques.
• The base material for these ICs
is silicon that has been “doped”
with other materials.
• More precisely, controlled
concentrations of impurities have
been diffused into specific
regions of the device to change
the properties (improve electrical
conductivity).
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• Doping silicon with phosphorus for n-type semiconductors:
• Process:
3. Result: Doped
semiconductor
regions.
silicon
Processing Using Diffusion
magnified image of a computer chip
0.5 mm
light regions: Si atoms
light regions: Al atoms
2. Heat.
1. Deposit P rich
layers on surface.
silicon