DIFFUSION IN SOLIDS

FICKS LAWS
KIRKENDALL EFFECT
ATOMIC MECHANISMS
Diffusion in Solids
P.G. Shewmon
McGraw-Hill, New York (1963)
Ar H
2

Movable piston
with an orifice
H
2
diffusion direction
Ar diffusion direction
Piston motion
Piston moves in the
direction of the slower
moving species
A B
Inert Marker thin rod of a high melting material which is basically
insoluble in A & B
Kirkendall effect
Materials A and B welded together with Inert marker and given a diffusion
anneal
Usually the lower melting component diffuses faster (say B)
Marker motion
Diffusion
Mass flow process by which species change their position relative to
their neighbours
Driven by thermal energy and a gradient
Thermal energy thermal vibrations Atomic jumps
Concentration / chemical potential
Electric Gradient
Magnetic
Stress
Assume that only B is moving into A
Assume steady state conditions J = f(x,t) (No accumulation of matter)
Flux (J) (restricted definition) Flow / area / time [Atoms / m
2
/ s]
Ficks I law
dx
dc
DA
dt
dn
=
No. of atoms
crossing area A
per unit time
Cross-sectional area
Concentration gradient
Matter transport is down the concentration gradient
Diffusion coefficient/ diffusivity
A
Flow direction
As a first approximation assume D = f(t)
dx
dc
DA
dt
dn
=
gradient ion concentrat time area atoms J / /
dx
dc
J
dx
dc
D J =
dx
dc
D
dt
dn
A
J = =
1
Ficks first law
Diffusivity (D) f(A, B, T)
D = f(c)
D = f(c)
C
1

C
2

Steady state diffusion
x
C
o
n
c
e
n
t
r
a
t
i
o
n

Diffusion
Steady state
J = f(x,t)
Non-steady state
J = f(x,t)
D = f(c)
D = f(c)
D = f(c)
D = f(c)
Ficks II law
J
x
J
x+Ax

Ax
x x x
J J on Accumulati
A +
=
)
`

A
c
c
+ = x
x
J
J J on Accumulati
x x
)
`

A
c
c
+ = A
|
.
|

\
|
c
c
x
x
J
J J x
t
c
x x
| | J
s m
Atoms
m
s m
Atoms

=
(

|
.
|

\
|
2 3
.
1
x
x
J
x
t
c
A
c
c
= A
|
.
|

\
|
c
c
|
.
|

\
|
c
c

c
c
=
|
.
|

\
|
c
c
x
c
D
x t
c
Ficks first law
|
.
|

\
|
c
c
c
c
=
|
.
|

\
|
c
c
x
c
D
x t
c D = f(x)
2
2
x
c
D
t
c
c
c
=
|
.
|

\
|
c
c
2
2
x
c
D
t
c
c
c
=
|
.
|

\
|
c
c
RHS is the curvature of the c vs x curve
x
c

x
c

+ve curvature c as t ve curvature c as t
LHS is the change is concentration with time
2
2
x
c
D
t
c
c
c
=
|
.
|

\
|
c
c
|
.
|

\
|
=
Dt
x
erf B A t x c
2
) , (
Solution to 2
o
de with 2 constants
determined from Boundary Conditions and Initial Condition
( ) ( )
}
=

t

0
2
exp
2
du u Erf
Erf () = 1
Erf (-) = -1
Erf (0) = 0
Erf (-x) = -Erf (x)
u
E
x
p
(

u
2
)

0
Area
A B
Applications based on Ficks II law
x
C
o
n
c
e
n
t
r
a
t
i
o
n

C
avg

t
t
1
> 0 | c(x,t
1
)
t
2
> t
1
| c(x,t
1
)
t = 0 | c(x,0)
A & B welded together and heated to high temperature (kept constant T
0
)
Flux
f(x)|
t

f(t)|
x

Non-steady
state
If D = f(c)
c(+x,t) = c(-x,t)
i.e. asymmetry about y-axis
C(+x, 0) = C
1

C(x, 0) = C
2

C
1

C
2

A = (C
1
+ C
2
)/2
B = (C
2
C
1
)/2

Determination of Diffusivity
|
.
|

\
|

=
kT
Q
e D D
0
Temperature dependence of diffusivity
Arrhenius type
Applications based on Ficks II law
Carburization of steel
Surface is often the most important part of the component, which is
prone to degradation
Surface hardenting of steel components like gears is done by carburizing
or nitriding
Pack carburizing solid carbon powder used as C source
Gas carburizing Methane gas CH
4
(g) 2H
2
(g) + C (diffuses into steel)
x 0
C
1

C
S

C(+x, 0) = C
1

C(0, t) = C
S

A = C
S

B = C
S
C
1
Approximate formula for depth of penetration
Dt x =
ATOMIC MODELS OF DIFFUSION
1. Interstitial Mechanism
2. Vacancy Mechanism
3. Interstitialcy Mechanism
4. Direct Interchange and Ring
Interstitial Diffusion
1 2
1 2
AH
m

At T > 0 K vibration of the atoms provides the energy to overcome the energy
barrier AH
m
(enthalpy of motion)
v frequency of vibrations, v number of successful jumps / time
|
.
|

\
|
A

=
kT
H
m
e ' v v
1
2
Vacant site
o
o
o
c = atoms / volume
c = 1 / o
3

concentration gradient dc/dx = (1 / o
3
)/o = 1 / o
4

Flux = No of atoms / area / time = v / area = v / o
2


2 4
2
'
'
) / (
o v o
o
v
= =

=
dx dc
J
D
|
.
|

\
|
A
=
kT
H
m
e D
2
o v
2
0
o v = D
|
.
|

\
|

=
kT
Q
e D D
0
On comparison
with
Substitutional Diffusion
Probability for a jump o
(probability that the site is vacant) . (probability that the atom has
sufficient energy)
AH
m
enthalpy of motion of atom
v frequency of successful jumps
|
.
|

\
|
A
|
|
.
|

\
|
A
=
kT
H
kT
H
m
f
e e ' v v
|
|
.
|

\
|
A A
=
kT
H H
m f
e ' v v
|
|
.
|

\
|
A A
=
kT
H H
m f
e D
2
o v
As derived for interstitial diffusion
2 4
2
'
'
) / (
o v o
o
v
= =

=
dx dc
J
D
Element AH
f
AH
m
AH
f
+ AH
m
Q
Au 97 80 177 174
Ag 95 79 174 184
Calculated and experimental activation energies for vacancy Diffusion
Interstitial Diffusion
|
.
|

\
|
A
=
kT
H
m
e D
2
o v
Substitutional Diffusion
|
|
.
|

\
|
A A
=
kT
H H
m f
e D
2
o v
D (C in FCC Fe at 1000C) = 3 10
11
m
2
/s
D (Ni in FCC Fe at 1000C) = 2 10
16
m
2
/s
DIFFUSION PATHS WITH LESSER RESISTANCE
Q
surface
< Q
grain boundary
< Q
lattice

Experimentally determined activation energies for diffusion
Core of dislocation lines offer paths of lower resistance
PIPE DIFFUSION
Lower activation energy automatically implies higher diffusivity
Diffusivity for a given path along with the available cross-section for
the path will determine the diffusion rate for that path
Comparison of Diffusivity for self-diffusion of Ag
single crystal vs polycrystal
1/T
L
o
g

(
D
)

Schematic
Polycrystal
Single
crystal
Increasing Temperature
Q
grain boundary
= 110 kJ /mole
Q
Lattice
= 192 kJ /mole