DIFFUSION IN SOLIDS

FICKS LAWS
KIRKENDALL EFFECT
ATOMIC MECHANISMS

Diffusion in Solids
P.G. Shewmon
McGraw-Hill, New York (1963)

H2 diffusion direction

Ar

H2

Movable piston
with an orifice

Piston motion

Ar diffusion direction

Piston moves in the

direction of the slower
moving species

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)
A

Marker motion

Inert Marker thin rod of a high melting material which is basically

insoluble in A & B

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

Gradient

Electric
Magnetic
Stress

 Flux (J) (restricted definition) Flow / area / time

[Atoms / m2 / s]

Assume that only B is moving into A

Assume steady state conditions J f(x,t) (No accumulation of matter)

Ficks I law
No. of atoms
crossing area A
per unit time

dn
dc
DA
dt
dx

Diffusion coefficient/ diffusivity

Cross-sectional area
Concentration gradient

Matter transport is down the concentration gradient

Flow direction
A
As a first approximation assume D f(t)

J atoms / area / time concentration gradient

dc
J
dx
dc
J D
dx
1 dn
dc
J
D
A dt
dx
dn
dc
DA
dt
dx

Ficks first law

 Diffusivity (D) f(A, B, T)

Steady state diffusion

D f(c)

Concentration

C1

D = f(c)
x

C2

D f(c)
Steady state
J f(x,t)
D = f(c)

Diffusion
Non-steady state
J = f(x,t)

D f(c)
D = f(c)

Ficks II law
x

Accumulation J x J x x
J
Accumulation J x J x
x
x

Jx

Jx+x

J
c

x J x J x
x
t

Atoms 1 Atoms
m 3 s .m m 2 s J

J
c

x x
x
t

c
c

D
x
x
t

c
c

D
t x x

D f(x)

Ficks first law

2c
c

D 2
x
t

 2c
c

D 2
x
t

RHS is the curvature of the c vs x curve

LHS is the change is concentration with time

+ve curvature c as t

ve curvature c as t

D 2
x
t

x
c( x, t ) A B erf

2 Dt
Solution to 2o de with 2 constants
determined from Boundary Conditions and Initial Condition

2
exp

u
du

Exp( u2)

Erf

Erf () = 1
Erf (-) = -1
Erf (0) = 0
Erf (-x) = -Erf (x)

Area

Determination of Diffusivity

Applications based on Ficks II law

A & B welded together and heated to high temperature (kept constant T0)
t2 > t1 | c(x,t1)

t1 > 0 | c(x,t1)

t = 0 | c(x,0)

Concentration

C2

C1

f(x)|t
Flux
f(t)|x

Cavg

If D = f(c)
c(+x,t) c(-x,t)
i.e. asymmetry about y-axis

t
A

B
x

C(+x, 0) = C1
C(x, 0) = C2

Non-steady
state

A = (C1 + C2)/2
B = (C2 C1)/2

Temperature dependence of diffusivity

D D0 e

kT

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 CH4 (g) 2H2 (g) + C (diffuses into steel)
CS

x
C(+x, 0) = C1
C(0, t) = CS

C1

A = CS
B = CS C1

Approximate formula for depth of penetration

x Dt

ATOMIC MODELS OF DIFFUSION

1. Interstitial Mechanism

2. Vacancy Mechanism

3. Interstitialcy Mechanism

4. Direct Interchange and Ring

Interstitial Diffusion
Hm

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

' e

H m

kT

 c = atoms / volume
c=1/3
concentration gradient dc/dx = (1 / 3)/ = 1 / 4
Flux = No of atoms / area / time = / area = / 2

J
' 4
D
2 ' 2
(dc / dx)
D 2 e

Vacant site

On comparison
with

H m

kT

D D0 e

D0 2

kT

Substitutional Diffusion
Probability for a jump
(probability that the site is vacant) . (probability that the atom has
sufficient energy)
Hm enthalpy of motion of atom
frequency of successful jumps

' e

H f

kT

H m

kT

As derived for interstitial diffusion

D 2 e

H f H m

kT

' e
D

H f H m

kT

J
'
2 4 ' 2
( dc / dx)

Calculated and experimental activation energies for vacancy Diffusion

Element

Hf

Hm

Hf + Hm

Au

97

80

177

174

Ag

95

79

174

184

Interstitial Diffusion

D 2 e

H m

kT

D (C in FCC Fe at 1000C) = 3 1011 m2/s

Substitutional Diffusion

D 2 e

H f H m

kT

D (Ni in FCC Fe at 1000C) = 2 1016 m2/s

DIFFUSION PATHS WITH LESSER RESISTANCE

Experimentally determined activation energies for diffusion

Qsurface < Qgrain boundary < Qlattice

Lower activation energy automatically implies higher diffusivity
Core of dislocation lines offer paths of lower resistance
PIPE DIFFUSION
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

Log (D)

Schematic

Polycrystal

Single
crystal
1/T
Increasing Temperature

Qgrain boundary

= 110 kJ /mole

QLattice

= 192 kJ /mole