Diffusion Callister

WHY STUDY DIFFUSION?
Materials often heat treated to improve properties

Atomic diffusion occurs during heat treatment
Depending on situation higher or lower diffusion rates
desired
Heat treating temperatures and times, and heating or cooling
rates can be determined using the mathematics/physics of
diffusion
Example: steel gears are case-hardened by
diffusing C or N to outer surface
Topic 5:
DIFFUSION IN SOLIDS
A
M
I
E

N
B
C
A
F
E

w
w
w
w
.
a
m
i
e
.
n
b
c
a
f
e
.
i
n
/
p
h
p
b
b
ISSUES TO ADDRESS...
Atomic mechanisms of diffusion
Mathematics of diffusion
Influence of temperature and diffusing species on
Diffusion rate
Topic 5:
DIFFUSION IN SOLIDS
DIFFUSION
Phenomenon of material transport by atomic or particle
transport from region of high to low concentration
What forces the particles to go from left to right?
Does each particle know its local concentration?
Every particle is equally likely to go left or right!
At the interfaces in the above picture, there are
more particles going right than left this causes
an average flux of particles to the right!
Largely determined by probability & statistics
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.
t
o
t
1
t
2
t
3
x
o
x
1
x
2
x
3
time (s)
x (mm)
DIFFUSION DEMO
100%
Concentration Profiles
0
Cu
Ni
Interdiffusion: In an alloy or diffusion couple, atoms tend
to migrate from regions of large to lower concentration.
Initially (diffusion couple) After some time
100%
Concentration Profiles
0
Adapted from
Figs. 5.1 and
5.2, Callister
6e.
DIFFUSION: THE PHENOMENA (1)
Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms After some time
A
B
C
D
A
B
C
D
DIFFUSION: THE PHENOMENA (2)
Conditions for diffusion:
there must be an adjacent empty site
atom must have sufficient energy to break bonds with its
neighbors and migrate to adjacent site (activation energy)
DIFFUSION MECHANISMS
Diffusion at the atomic level is a step-wise migration of atoms from
lattice site to lattice site
Higher the temperature, higher is the probability that an atom will have
sufficient energy
hence, diffusion rates increase with temperature
Types of atomic diffusion mechanisms:
substitutional (through vacancies)
interstitial
Substitutional Diffusion:
applies to substitutional impurities
atoms exchange with vacancies
rate depends on:
-- number of vacancies
-- temperature
-- activation energy to exchange.
increasing elapsed time
DIFFUSION MECHANISMS
ACTIVATION ENERGY FOR
DIFFUSION
Also called energy barrier for diffusion
Initial state Final state Intermediate state
Energy Activation energy
Simulation of
interdiffusion
across an interface:
Rate of substitutional
diffusion depends on:
-- vacancy concentration
-- activation energy (which is
related to frequency of jumping).
(Courtesy P.M. Anderson)
DIFFUSION SIMULATION
(Courtesy P.M. Anderson)
Applies to interstitial impurities.
More rapid than vacancy
diffusion (Why?).
Interstitial atoms smaller and
more mobile; more number of
interstitial sites than vacancies
INTERSTITIAL SIMULATION
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.
Case Hardening:
-- Example of interstitial
diffusion is a case
hardened gear.
-- Diffuse carbon atoms
into the host iron atoms
at the surface.
Result: The "Case" is
--hard to deform: C atoms
"lock" planes from shearing.
Fig. 5.0,
Callister 6e.
(Fig. 5.0 is
courtesy of
Surface
Division,
Midland-
Ross.)
PROCESSING USING DIFFUSION (1)
--hard to crack: C atoms put
the surface in compression.
Doping Silicon with P for n-type semiconductors:
1. Deposit P rich
layers on surface.
2. Heat it.
3. Result: Doped
semiconductor
regions.
silicon
silicon
magnified image of a computer chip
0.5mm
light regions: Si atoms
light regions: Al atoms
Fig. 18.0,
Callister 6e.
PROCESSING USING DIFFUSION (2)
Process
Flux: amount of material or atoms moving past a unit area in unit time
Flux, J = M/(A t)

J =
1
A
dM
dt
kg
m
2
s

(

(
or
atoms
m
2
s

(

(
Directional Quantity
Flux can be measured for:
--vacancies
--host (A) atoms
--impurity (B) atoms
J
x
J
y
J
z
x
y
z
x-direction
Unit area A
through
which
atoms
move.
MODELING DIFFUSION: FLUX
Concentration Profile, C(x): [kg/m
3
]
Fick's First Law:
Concentration
of Cu [kg/m
3
]
Concentration
of Ni [kg/m
3
]
Position, x
Cu flux Ni flux
The steeper the concentration profile,
the greater the flux!
Adapted from
Fig. 5.2(c),
Callister 6e.

J
x
=
D
dC
dx
Diffusion coefficient [m
2
/s]
concentration
gradient [kg/m
4
]
flux in x-dir.
[kg/m
2
-s]
CONCENTRATION PROFILES & FLUX
Steady State: Steady rate of diffusion from one end to the other.
Implies that the concentration profile doesn't change with time. Why?
Apply Fick's First Law:
Result: the slope, dC/dx, must be constant
(i.e., slope doesn't vary with position)!
J
x(left)
= J
x(right)
Steady State:
Concentration, C, in the box doesnt change w/time.
J
x(right)
J
x(left)
x

J
x
= D
dC
dx

dC
dx
|
\

|
.
|
left
=
dC
dx
|
\

|
.
|
right
If J
x
)
left
= J
x
)
right
, then
STEADY STATE DIFFUSION
Steel plate at
700C with
geometry
shown:
Q: How much
carbon transfers
from the rich to
the deficient side?
J
=
D
C
2
C
1
x
2
x
1
=
2.4
10
9
kg
m
2
s
Adapted from
Fig. 5.4,
Callister 6e.
C
1

=

1
.
2
k
g
/
m
3
C
2

=

0
.
8
k
g
/
m
3
Carbon
rich
gas
1
0
m
m
Carbon
deficient
gas
x
1
x
2
0
5
m
m
D=3x10
-11
m
2
/s
Steady State =
straight line!
EX: STEADY STATE DIFFUSION
Note: Steady state does not set in instantaneously.
STEADY STATE DIFFUSION:
ANOTHER PERSPECTIVE
Hose connected to tap; tap turned on
At the instant tap is turned on, pressure is high at the tap
end, and 1 atmosphere at the other end
After steady state is reached, pressure linearly drops
from tap to other end, and will not change anymore
Tap end Flow end
Pressure
Increasing time
Steady state
Concentration profile,
C(x), changes
w/ time.
To conserve matter: Fick's First Law:
Governing Eqn.:
Concentration,
C, in the box
J
(right)
J
(left)
dx
dC
dt
=
D
d
2
C
dx
2
dx
=
dC
dt
J
(left)
J
(right)
NON STEADY STATE DIFFUSION
Ficks second law
dJ
dx
=
dC
dt
dJ
dx
=
D
d
2
C
dx
2
(if D does
not vary
with x)
equate
J
=
D
dC
dx
Copper diffuses into a bar of aluminum.
Boundary conditions:
For t = 0, C = C
0
at x > 0
For t > 0, C = C
s
at x = 0
C = C
0
at x =
pre-existing conc., C
o
of copper atoms
Surface conc.,
C
s
of Cu atoms
bar
C
o
C
s
position, x
C(x,t)
t
o
t
1
t
2
t
3
Adapted from
Fig. 5.5,
Callister 6e.
EX: NON STEADY STATE DIFFUSION
dC
dt
=
D
d
2
C
dx
2
General solution:
"error function"
Values calibrated in Table 5.1, Callister 6e.
C(x, t)
C
o
C
s
C
o
=
1
erf
x
2 Dt
|
\

|
.
|
pre-existing conc., C
o
of copper atoms
Surface conc.,
C
s
of Cu atoms
bar
C
o
C
s
position, x
C(x,t)
t
o
t
1
t
2
t
3
Adapted from
Fig. 5.5,
Callister 6e.
EX: NON STEADY STATE DIFFUSION
Suppose we desire to achieve a specific concentration C1
at a certain point in the sample at a certain time
PROCESS DESIGN EXAMPLE
|
.
|
\
|
=
Dt
x
erf
C C
C t x C
s
2
1
) , (
0
0
|
.
|
\
|
= =
Dt
x
erf
C C
C C
s
2
1 constant
0
0 1
becomes
constant
2
=
Dt
x
The experiment: record combinations of
t and x that kept C constant.
t
o
t
1
t
2
t
3
x
o
x
1
x
2
x
3
Diffusion depth given by:
x
i
Dt
i

C(x
i
, t
i
) C
o
C
s
C
o
= 1 erf
x
i
2 Dt
i
|
\

|
.
|
|
= (constant here)
DIFFUSION DEMO: ANALYSIS
Experimental result: x ~ t
0.58
Theory predicts x ~ t
0.50
Reasonable agreement!

B
B
B
B
B
B
B
B
B
B
B
B
B
B
0
0.5
1
1.5
2
2.5
3
3.5
4
0 0.5 1 1.5 2 2.5 3
( )
ln[t(min)]
Linear regression fit to data:
ln[x(mm)]
=
0.58ln[t(min)]
+
2.2
R
2
=
0.999
DATA FROM DIFFUSION DEMO
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, given D
500
and D
600
?
(Dt)
500C
=(Dt)
600C
s
C(x,t)
C
o
C C
o
=
1
erf
x
2
Dt
|
\

|
.
|
Result: Dt should be held constant.
Answer:
Note: values
of D are
provided here.
Key point 1: C(x,t
500C
) = C(x,t
600C
).
Key point 2: Both cases have the same C
o
and C
s
.
t
500
=
(Dt)
600
D
500
=
110
hr
4.8x10
-
14
m
2
/s
5.3x10
-
13
m
2
/s
10hrs
PROCESSING QUESTION
Diffusivity increases with T.
pre-exponential [m
2
/s] (see Table 5.2, Callister 6e)
activation energy
gas constant [8.31J/mol-K]
D
=
D
o
exp
Q
d
RT
|
\

|
.
|
diffusivity
[J/mol],[eV/mol]
(see Table 5.2, Callister 6e)
DIFFUSION AND TEMPERATURE
Remember vacancy concentration: N
V
= N exp(-QV/kT)
QV is vacancy formation energy (larger this energy,
smaller the number of vacancies)
Qd is the activation energy (larger this energy, smaller
the diffusivity and lower the probability of atomic diffusion)
ACTIVATION ENERGY FOR
DIFFUSION
Also called energy barrier for diffusion
Initial state Final state Intermediate state
Energy Activation energy
Experimental Data:
1000K/T
D (m
2
/s)
C

i
n

-
F
e
C

i
n

-
F
e
A
l

i
n

A
l
C
u

i
n

C
u
Z
n

i
n

C
u
F
e

i
n

-
F
e
F
e

i
n

-
F
e
0.5 1.0 1.5 2.0
10
-20
10
-14
10
-8
T(C)
1
5
0
0
1
0
0
0
6
0
0
3
0
0
D has exp. dependence on T
Recall: Vacancy does also!
pre-exponential [m
2
/s] (see Table 5.2, Callister 6e)
activation energy
gas constant [8.31J/mol-K]
D
=
D
o
exp
Q
d
RT
|
\

|
.
|
diffusivity
[J/mol],[eV/mol]
(see Table 5.2, Callister 6e)
D
interstitial
>> D
substitutional
C in -Fe
C in -Fe
Al in Al
Cu in Cu
Zn in Cu
Fe in -Fe
Fe in -Fe
Adapted from Fig. 5.7, Callister 6e. (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.)
DIFFUSION AND TEMPERATURE
NOTE: log(D) = log(D0) Qd/(RT)
Diffusion FASTER for...
open crystal structures
lower melting T materials
materials w/secondary
bonding
smaller diffusing atoms
lower density materials
Diffusion SLOWER for...
close-packed structures
higher melting T materials
materials w/covalent
bonding
larger diffusing atoms
higher density materials
SUMMARY:
STRUCTURE & DIFFUSION

Diffusion Callister

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WHY STUDY DIFFUSION?

Materials often heat treated to improve properties

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