DIFFUSION IN SOLIDS

FICKS LAWS

KIRKENDALL EFFECT
ATOMIC MECHANISMS

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

 To comprehend many materials related phenomenon one must understand

Diffusion.
The focus of the current chapter is solid state diffusion in crystalline materials.

Roles of Diffusion
Oxidation

Creep

Metals

Some mechanisms

Sintering

Aging
Precipitates

Doping

Carburizing

Semiconductors

Steels
Many more

Material Joining
Diffusion bonding

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]

1 dn
J
A dt

Flow direction

Ficks I law
Assume that only B is moving into A
Assume steady state conditions J f(x,t) (No accumulation of matter)

Flux ( J ) atoms / area / time concentration gradient (Truly speaking it is the

chemical potential gradient!)

dc
dx

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

dJ
dc

x

dx
dt
Ficks first law

Continuity equation

Diffusivity (D) f(Concentration of the components, T)

dn
dc
DA
dt
dx

Flow direction

dc
J D
dx
Diffusion coefficient/ Diffusivity
No. of atoms
crossing area A
per unit time

dn
dc
DA
dt
dx

Cross-sectional area
Concentration gradient

ve implies matter transport is down the concentration gradient

Flow direction

A
As a first approximation assume D f(t)

Steady and non-steady state diffusion

Steady state
J f(x,t)

Under steady state conditions

dc
J

0
dt x
x t

If D is NOT constant

c
constant
x

D = f(c)

Diffusion

Substituting for flux from Ficks first law

J
c
D 0
x
x

D f(c)

If D is constant

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

D f(c)
D = f(c)

2c
Slope of c-x plot is constant under steady state
D 2 0 conditions
x

If D increases with concentration then slope (of c-x plot)

decreases with c
If D decreases with c then slope increases with c

Ficks II law
x

Jx

Accumulati on J x J xx
Jx+x

Accumulati on J x J x
x
x

J
c

x
x J x J x
x
t

J
c
x x
x
t

c c
D
t x x

Atoms 1 Atoms
m3 s .m m 2 s J

c
c
D
x
x
t
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

c

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

Also
For upto x~0.6 Erf(x) ~ x
x 2, Erf(x) 1

Exp( u2)

Erf

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

Area

Example where the erf solution can be used

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

f(x)|t
Non-steady
state

Flux
f(t)|x

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

Cavg
t
A

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

B
x
AB = C1
A+B = C2

x
c( x, t ) A B erf

2 Dt

A = (C1 + C2)/2
B = (C2 C1)/2
x
C C2 C2 C1
c( x, t ) 1

erf

2 2
2 Dt

Temperature dependence of diffusivity

Diffusivity depends exponentially on temperature.
This dependence has important consequences with regard to material behaviour
at elevated temperatures. Processes like precipitate coarsening, oxidation, creep
etc. occur at very high rates at elevated temperatures.

D D0 e

Q

kT

Arrhenius type

ATOMIC MODELS OF DIFFUSION

The diffusion of two important types of species needs to be distinguished:
(i) species sitting in a lattice site
(ii) species in a interstitial void

1. Interstitial Mechanism

Usually the solubility of interstitial atoms (e.g. carbon in steel) is small. This implies that
most of the interstitial sites are vacant. Hence, if an interstitial species wants to jump, most
likely the neighbouring site will be vacant and jump of the atomic species can take place.
Light interstitial atoms like hydrogen can diffuse very fast. For a correct description of
diffusion of hydrogen anharmonic and quantum (under barrier) effects may be very
important (especially at low temperatures).

2. Vacancy Mechanism

For an atom in a lattice site (and often we are interested in substitutional atoms) jump to a
neighbouring lattice site can take place if it is vacant. Hence, vacancy concentration plays an
important role in the diffusion of species at lattice sites via the vacancy mechanism.
Vacancy clusters and defect complexes can alter this simple picture of diffusion involving
vacancies

Interstitial Diffusion

Hm
1

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

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

D 2 e

H m

kT

H f H m

kT

Where, is the jump distance

' e

H f H m

kT

Interstitial Diffusion

D e
2

H m

kT

of the form

D D0 e

H m
kT

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

Substitutional Diffusion

D e
2

H f H m

kT

of the form

D D0 e

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

H f H m

kT

Diffusion Paths with Lesser Resistance

Experimentally determined activation energies for diffusion

Qsurface < Qgrain boundary < Qpipe < 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

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 hardening 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).

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

Solved
Example

A 0.2% carbon steel needs to be surface carburized such that the concentration
of carbon at 0.2mm depth is 1%. The carburizing medium imposes a surface
concentration of carbon of 1.4% and the process is carried out at 900C
(where, Fe is in FCC form).

Data: D0 (C in -Fe) 0.7 104 m2 / s

Q 157 kJ / mole

Given: T = 900 C, C0 = C(x, 0) = C(, t) = 0.2 % C,

Cf = C(0.2 mm, t1) = 1% C (at x = 0.2 mm), Cs = C(0, t) = 1.4% C
The solution to the Fick second law: C ( x, t ) A B erf

2 Dt

(1)

The constants A & B are determined from boundary and initial conditions:
C (0, t ) A CS 0.014 , C (, t ) A B C0 0.002 or C ( x,0) A B C0 0.002
B

x
CS C0 0.012 , C ( x, t ) 0.014 0.012 erf

2 Dt

2 10-4
4
C (2 10 m , t1 ) 0.01 0.014 0.012 erf

2 Dt
1

1
erf
3

2 10-4

2 Dt
1

(2)

x
C ( x, t ) CS (CS -C0 ) erf

2 Dt
C ( x, t ) CS

C0 CS

x
= erf

2 Dt

The following points are to be noted:

The mechanism of C diffusion is interstitial diffusion
Q
The diffusivity D has to be evaluated at 900C using: D D0 exp

RT

2
157 103
Q
4
12 m
D D0 exp
(0.7 10 ) exp 8.314 1173 7.14 10
s
RT

1.4

From equation (2)

1.2

%C

1.0

erf 1 (0.3333) 0.309

0.8
0.6

0.2

t = 7000s

0.2

0.4

0.6

0.8

2 10-4

7.14 10
12

t = 1000s
t =0

2 10-4

2 Dt
1

t1

104
1
t1
14580 s
12
0.33
7.14 10

t = t1 = 14580s

0.4

1
erf
3

1.0

x (in mm from surface)

1.2

1.4

Approximate formula for depth of penetration

x Dt

C ( x, t ) CS
x c( x, t ) C0

= erf
C C 1 erf
C

C
2 Dt
S
0

0
S

2 Dt

Let the distance at which

[(C(x,t)C0)/(CSC0)] = be called x1/2
(which is an effective penetration depth)
1
1 erf
2

x1 2

2 Dt

1 1
erf
2 2

x1 2 1
erf

2
Dt

x1 2 1

2 Dt 2

x penetration Dt
The depth at which C(x) is nearly C0 is (i.e. the distance beyond which is un-penetrated):
x
0 1 erf
2 Dt

2 Dt

Erf(u) ~ 1 when u ~ 2
x 4 Dt

End

Another solution to the Ficks II law

A thin film of material (fixed quantity of mass M) is deposited on the surface of another
material (e.g. dopant on the surface of a semi-conductor). The system is heated to allow
diffusion of the film material into the substrate.
For these boundary conditions we get a exponential solution.

Boundary and Initial conditions

C(+x, 0) = 0

cdx M

x2
M
c ( x, t )
exp

4
Dt
Dt

Diffusion in ionic materials

Ionic materials are not close packed
Ionic crystals may contain connected void pathways for rapid diffusion
These pathways could include ions in a sublattice (which could get disordered)
and hence the transport is very selective
alumina compounds show cationic conduction
Fluorite like oxides are anionic conductors
Due to high diffusivity of ions in these materials they are called superionic
conductors. They are characterized by:
High value of D along with small temperature dependence of D
Small values of D0
Order disorder transition in conducting sublattice has been cited as one of the
mechanisms for this behaviour

Calculated and experimental activation energies for vacancy Diffusion

Element

Hf

Hm

Hf + Hm

Au

97

80

177

174

Ag

95

79

174

184

 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

Q

kT

3. Interstitialcy Mechanism
Exchange of interstitial atom with a regular host atom (ejected from its regular
site and occupies an interstitial site)
Requires comparatively low activation energies and can provide a pathway for
fast diffusion
Interstitial halogen centres in alkali halides and silver interstitials in silver halides

Steady state diffusion

D f(c)

Concentration

C1

D = f(c)
x

C2

4. Direct Interchange and Ring