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CHAPTER 6:

DIFFUSION IN SOLIDS
Chapter 5-
ISSUES TO ADDRESS... ISSUES TO ADDRESS... ISSUES TO ADDRESS... ISSUES TO ADDRESS...
How does diffusion occur?
Why is it an important part of processing?
CHAPTER 5:
DIFFUSION IN SOLIDS
Chapter 5-
Why is it an important part of processing?
How can the rate of diffusion be predicted for
some simple cases?
1
How does diffusion depend on structure
and temperature?
DIFFUSION DEFINED :
The phenomenon of material transport by
movement of atoms.
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.
Chapter 5-
Measure the diffusion distance, x, over some time.
Compare the results with theory.
t
o
t
1
t
2
t
3
x
o
x
1
x
2
x
3 mm
s
e
c
Interdiffusion: 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.
DIFFUSION: THE PHENOMENA (1)
Chapter 5-
100%
Concentration Profiles
0
Cu
Ni
3
100%
Concentration Profiles
0
Callister 6e.
DIFFUSION MECHANISMS
Takes place in presence of vacancies and
interstitial voids of suitable size.
The diffusing atoms have enough energy to
break the bonds with neighboring atoms
There are vacant sites where the diffusing atoms
Chapter 5-
There are vacant sites where the diffusing atoms
can move.
Diffusion rate increases at elevated temperature.
mechanisms: self, vacancy, interstitial etc.
Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms After some time
C
C
DIFFUSION: THE PHENOMENA (2)
Chapter 5- 4
A
B
D
A
B
D
Activation energy for self diffusion = act. Energy of
vacancy formation + activation energy of movement
of vacancy
Substitutional Diffusion:
applies to substitutional impurities
atoms exchange with vacancies
rate depends on:
--number of vacancies
--activation energy to exchange.
DIFFUSION MECHANISMS
Chapter 5- 5
increasing elapsed time
Simulation of
interdiffusion
across an interface:
Rate of substitutional
diffusion depends on:
DIFFUSION SIMULATION
Chapter 5-
diffusion depends on:
--vacancy concentration
--frequency of jumping.
(Courtesy P.M. Anderson)
Applies to interstitial
impurities.
More rapid than
vacancy diffusion.
-- shows the jumping of a
smaller atom (gray) from
INTERSTITIAL DIFFUSION
Chapter 5- 7
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.
FACTORS INFLUENCING DIFFUSION
Temperature
size of solute atoms
Chapter 5-
melting point of solvent
packing efficiency of solvent
number of vacancies
Flux:

J =
1
A
dM
dt

kg
m
2
s



(

(
or
atoms
m
2
s



(

(
Directional Quantity
J
y
y
x-direction
MODELING DIFFUSION: FLUX
Chapter 5- 10
Flux can be measured for:
--vacancies
--host (A) atoms
--impurity (B) atoms
J
x
J
y
J
z
x
y
z
Unit area A
through
which
atoms
move.
Concentration Profile, C(x): [kg/m
3
]
Concentration
of Cu [kg/m
3
]
Concentration
of Ni [kg/m
3
]
Position, x
Cu flux Ni flux
CONCENTRATION PROFILES & FLUX
Chapter 5- 11
Fick's First Law:
Position, x
The steeper the concentration profile,
the greater the flux!

J
x
=
D
dC
dx
Diffusion coefficient [m
2
/s]
concentration
gradient [kg/m
4
]
flux in x-dir.
[kg/m
2
-s]
Steady State: the concentration profile doesn't
change with time.
J
x(left)
= J
x(right)
Steady State:
Concentration, C, in the box doesnt change w/time.
J
x(right)
J
x(left)
x
STEADY STATE DIFFUSION
Chapter 5- 12
Apply Fick's First Law:
Result: the slope, dC/dx, must be constant
(i.e., slope doesn't vary with position)!
Concentration, C, in the box doesnt change w/time.

J
x
= D
dC
dx

dC
dx
|
\

|

|
left
=
dC
dx
|
\

|

|
right
If J
x
)
left
= J
x
)
right
, then
Steel plate at
700C with
geometry
shown:
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
Carbon
deficient
gas
Steady State =
straight line!
EX: STEADY STATE DIFFUSION
Chapter 5- 13
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
1
0
m
m
gas
x
1
x
2
0
5
m
m
D=3x10
-11
m
2
/s
Diffusion Flux computation Diffusion Flux computation Diffusion Flux computation Diffusion Flux computation
A plate of iron is exposed to carburizing (carbon-rich)
atmosphere on one side and a decarburizing
atmosphere on the other side at 700
0
C. If a condition
of steady state is achieved, calculate the diffusion flux
of carbon through the plate if the concentrations of
carbon at positions 5 and 10 mm beneath carburizing
Chapter 5-
carbon at positions 5 and 10 mm beneath carburizing
surface are 1.2 and 0.8 kg/m
3
, respectively.
J = -D(c
A
-c
B
/x
A
-x
B
)
= -(3 x 10
-11
m
2
/s){(1.2-0.8)kg/m
3
/ (5 x 10
-3
-10
-2
)m}
= 2.4 x 10
-9
kg/m
2
s
NON-STEADY STATE DIFFUSION
The flux is not same at different cross-sections
perpendicular to the diffusion
The flux through a given cross-section varies with
time
There is a net accumulation or depletion of
Chapter 5-
There is a net accumulation or depletion of
diffusing species.
Cs area=unity
x
x
J
x
J
x+x
=(C/t)x
C/t = -J
x
/x
C/t = -/x(-D(C/x)
If D does not depend on concentration
C/t = D(
2
C/x
2
)
Ficks second Law
NON STEADY STATE DIFFUSION
Chapter 5-
The solution to 1D equation is
C(x,t) = A B erf(x/2Dt)
A,B are constants determined from initial and
final boundary conditions of the problem.
Steady State: the concentration profile doesn't
change with time.
J
x(left)
= J
x(right)
Steady State:
Concentration, C, in the box doesnt change w/time.
J
x(right)
J
x(left)
x
STEADY STATE DIFFUSION
Chapter 5- 12
Apply Fick's First Law:
Result: the slope, dC/dx, must be constant
(i.e., slope doesn't vary with position)!
Concentration, C, in the box doesnt change w/time.

J
x
= D
dC
dx

dC
dx
|
\

|

|
left
=
dC
dx
|
\

|

|
right
If J
x
)
left
= J
x
)
right
, then
Steel plate at
700C with
geometry
shown:
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
Carbon
deficient
gas
Steady State =
straight line!
EX: STEADY STATE DIFFUSION
Chapter 5- 13
Q: How much
carbon transfers
from the rich to
the deficient side
per unit area per unit time
(Diffusion Flux, J)?
J
=
D
C
2

C
1
x
2

x
1
=
2.4

10

9
kg
m
2
s
1
0
m
m
gas
x
1
x
2
0
5
m
m
D=3x10
-11
m
2
/s
NON-STEADY STATE DIFFUSION
The flux is not same at different cross-sections
perpendicular to the diffusion
The flux through a given cross-section varies with
time
There is a net accumulation or depletion of
Chapter 5-
There is a net accumulation or depletion of
diffusing species.
Cs area=unity
x
x
J
x +x
J
x
= (C/t)x
C/t = -J
x
/x
C/t = -/x(-D(C/x)
If D does not depend on concentration
C/t = D(
2
C/x
2
)
Ficks second Law
NON STEADY STATE DIFFUSION
Chapter 5-
The solution to 1D equation is
C(x,t) = A B erf(x/2Dt)
A,B are constants determined from initial and
final boundary conditions of the problem.
General solution:
"error function"
C(x, t)

C
o
C
s

C
o
=
1

erf
x
2 Dt
|
\

|

|
NON STEADY STATE DIFFUSION
Boundary conditions
the two media are considered to be semi-infinite
Chapter 5- 15
the two media are considered to be semi-infinite
concentrations on either side of the interface
change abruptly and are uniform
x=0 at the interface
t=0 when diffusion begins
Tabulation of Error function Table 5.1
NON STEADY STATE DIFFUSION
C
o
C
s
position, x
C(x,t)
t
o
t
1
t
2
t
3
Chapter 5-
At t=0(t
o
) C(x,0) = C
o
for 0<x< (0.25 wt %)
At t>0 C(x,t) = C
x
for 0<x< (0.80 wt %)
C(0,t) = C
s
for x=0 (1.20 wt %)
C(-x,t) = C
s
for x=- (1.20 wt %)
(D
c in steel
= 1.6 x 10
-11
m
2
/s, x = 0.5 mm ) t = ?
position, x
Case Hardening:
--Diffuse carbon atoms
into the host iron atoms
at the surface.
--Example of interstitial
diffusion is a case
hardened gear.
PROCESSING USING DIFFUSION (1)
Chapter 5-
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.
8
Carburization of steel
Carburizing atmosphere
Steel
C
s
C
1
0
x
C(x,0)=c
1
x> 0
C(0,t)=c
s
C(x,0)=c
2
x< 0
Chapter 5-
Decarburizing atmosphere
C
2
Steel
C
s
0
x
C(x,0)=c
2
x< 0
C(0,t)=c
s
PROCESSING USING DIFFUSION (3)
Corrosion resistance of duralumin
Alloy of Al with 4% Cu
Much higher strength
than Al
Chapter 5-
Corrosion resistance
poor compared to Al
Duralumin sheets covered with thin Al sheets on both
sides ALCLAD
Experimental determination of D
Can be determined using a diffusion couple
Bar 2
Bar 1
t = 0
t
2
>t
1
t
1
>0
c
2
c
C
o
n
c
e
n
c(x,0)= c
1
x>0
Chapter 5-
0
Distance x
c
1
n
t
r
a
t
i
o
n
c(x,0)= c
1
x>0
c
2
x<0
c(x,t) = A B erf x/2Dt
A=(c
1
+c
2
)/2
B=(c
2
c
1
)/2
ATOMIC MODEL OF DIFFUSION
H
m
P.
E
Atom jumps to a vacant site
Needs enough energy
Breaking of bond in initial site
Formation of bond at final site
Chapter 5-
1 2 H
m
enthalpy of motion
Probability of atom to have sufficient vibrational
energy to overcome the P.E. barrier
exp(- H
m
/RT)
DIFFUSION AND TEMPERATURE
Diffusivity D=D
o
exp(-H
m
/RT) (for interstitial
diffusion)
D also depends on the probability of finding a
vacant site (for vacancy/substitutional diffusion)
n/N=exp(-H
f
/RT)
Chapter 5-
f
So D=D
o
exp(-(H
m
+H
f
)/RT)
Activation energy Q
d
= (H
m
+H
f
)
Is the energy required to diffuse from one site to the
next
Diffusivity increases with T.
Experimental Data:
T(C)
1
5
0
0
1
0
0
0
0
0
0
0
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)
Chapter 5-
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!
19
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 IN COMPOUNDS
Diffusion process is helped by presence of point
defects.
Diffusion coefficients are different for cations and
anions
Diffusion also aided by other imperfections
Chapter 5-
Diffusion also aided by other imperfections
Q
lattice
> Q
grain boundary
> Q
surface
D
lattice
< D
grain b
< D
surface
C.S. area of mass transport usually smaller in
special diffusion paths.
At higher temp diffusion through bulk prevails.
Diffusion FASTER for...
open crystal structures
lower melting T materials
Diffusion SLOWER for...
close-packed structures
higher melting T materials
SUMMARY:
STRUCTURE & DIFFUSION
Chapter 5- 20
materials w/secondary
bonding
smaller diffusing atoms
cations
lower density materials
materials w/covalent
bonding
larger diffusing atoms
anions
higher density materials