Chapter 5

Diffusion in Solids

SEM II 2015-2016

Diffusivity

Diffusivity depends upon

Type of diffusion : Whether the diffusion is interstitial or
substitutional.
Temperature: As the temperature increases diffusivity
increases.
Type of crystal structure: BCC crystal has lower APF than FCC
and hence has higher diffusivity.
Type of crystal imperfection: More open structures (grain
boundaries) increases diffusion.
The concentration of diffusing species: Higher concentrations of

diffusing solute atoms will affect diffusivity.

SEM II 2015-2016

Diffusion
Self-diffusion: In an elemental solid, atoms also
migrate.
C
C

D
A

Label some atoms

After some time

SEM II 2015-2016

Diffusion Mechanisms
Atom diffusion can occur by the
motion of vacancies (vacancy
diffusion) or impurities (impurity

diffusion).

SEM II 2015-2016

Substitutional Diffusion
Example: If atom A
has sufficient activation
energy, it moves into the

vacancy

self diffusion.

Activation
Activation
Energy to + Energy to
=
form a
move a
Vacancy
vacancy
As the melting point increases, activation energy also increases

Activation
Energy of
Self diffusion

SEM II 2015-2016

Interstitial Diffusion
More rapid than vacancy diffusion

Atoms move from one

interstitial site to another.
The atoms that move must
be much smaller than the
matrix atom.
Example:
Carbon interstitially
diffuses into BCC or
FCC iron.

Matrix atoms

Interstitial atoms

Self diffusion (motion of atoms

within a pure host) also occurs.
Predominantly vacancy in nature
(difficult for atoms to fit into
interstitial sites because of size.
SEM II 2015-2016

Flux of Diffusion
The flux of diffusing atoms, J, is used to quantify how fast
diffusion occurs. The flux is defined as either in number of
atoms diffusing through unit area and per unit time (e.g.,
atoms/m2-second) or in terms of the mass flux - mass of
atoms diffusing through unit area per unit time, (e.g.,

kg/m2-second).

SEM II 2015-2016

Flux of Diffusion

moles (or mass)diffusing mol

kg
J Flux

or
2
surface areatime
cm s m2s

M=
mass
diffused

M
l dM
J

At A dt

J slope
time

SEM II 2015-2016

Diffusion Temperature
Dependence
Diffusion coefficient is the measure of mobility of diffusing
species.

D0 temperature-independent preexponential (m2/s)

Qd the activation energy for diffusion (J/mol or eV/atom)
R the gas constant (8.31 J/mol-K or 8.6210-5 eV/atom-K)
T absolute temperature (K)
SEM II 2015-2016

Steady State Diffusion

There is no change in concentration of solute atoms at different planes in a system, over a period of time.
No chemical reaction occurs. Only net flow of atoms.

Concentration
Of diffusing
C1
atoms

Solute atom flow

C2
Distance x

Unit
Area

Diffusing
atoms

SEM II 2015-2016

Net flow of atoms

Per unit area per
Unit time = J
10

Ficks Law

The flux or flow of atoms is given by

J D

dc

J = Flux or net flow of atoms.

D = Diffusion coefficient.

dc

= Concentration Gradient.
dx
i.e. for steady state diffusion condition, the net flow of atoms by atomic

dx

diffusion is equal to diffusion D times the diffusion gradient dc/dx .

Example: Diffusivity of FCC iron at 500oC is 5 x 10-15 m2/S and at 1000oC is 3

x 10-11 m2/S

SEM II 2015-2016

11

Steady State Diffusion

The concentration gradient is often called the driving

force in diffusion (but it is not a force in the

mechanistic sense).
The minus sign in the equation means that diffusion
is down the concentration gradient.

SEM II 2015-2016

12

Steady State Diffusion

Rate of diffusion independent of time
Flux proportional to concentration gradient =

dC
dx

C1C1

C2
x1

C2

x2
x

dC C C2 C1
if linear

dx x
x2 x1
SEM II 2015-2016

Ficks first law of

diffusion

dC
J D
dx
D diffusion coefficient
13

Example
The purification of hydrogen gas by diffusion through a palladium
sheet. Compute the number of kilograms of hydrogen that pass per
hour through a 6-mm-thick sheet of palladium having an area of
0.25 m2 at 600C. Assume a diffusion coefficient of 1.7 X 10-8 m2/s,

that the concentrations at the high- and low-pressure sides of the

plate are 2.0 and 0.4 kg of hydrogen per cubic meter of palladium,
and that steady-state conditions have been attained.

SEM II 2015-2016

14

Example (cont.)
This problem calls for the mass of hydrogen, per hour, that diffuses
through a Pd sheet. It first becomes necessary to employ both
Equations 5.1a and 5.3. Combining these expressions and solving
for the mass yields

SEM II 2015-2016

15

Example: Chemical Protective

Clothing (CPC)
Methylene chloride is a common ingredient of paint removers.
Besides being an irritant, it also may be absorbed through skin. When
using this paint remover, protective gloves should be worn.
If butyl rubber gloves (0.04 cm thick) are used, what is the diffusive
flux of methylene chloride through the glove?
Data:
diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
surface concentrations:
C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
SEM II 2015-2016

16

Example (cont).
Solution assuming linear conc. gradient
glove
C1

J -D

paint
remover

tb

2
6D

skin

C2
x1 x2

Data:

dC
C C1
D 2
dx
x2 x1

D = 110 x 10-8 cm2/s

C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 x1 = 0.04 cm

3
3
(
0
.
02
g/cm

0
.
44
g/cm
)
g
J (110 x 10-8 cm2 /s)
1.16 x 10-5
(0.04 cm)
cm2s

Diffusion Temperature
Dependence
The above equation can be rewritten as

The activation energy Qd and preexponential D0, therefore, can

be estimated by plotting ln D versus 1/T or log D versus 1/T. Such
plots are Arrhenius plots.

SEM II 2015-2016

18

Diffusion Temperature
Dependence

Graph of log D vs. 1/T has slop of Qd/2.3R, intercept of ln Do

SEM II 2015-2016

19

Diffusion Coefficient
Determine activation energy, Qd:

Graph of ln D vs. 1/kT has

gradient of -Qd, intercept ln Do

SEM II 2015-2016

20

Diffusion and Temperature

Diffusion coefficient increases with increasing T.
Qd

D Do exp
RT
D = diffusion coefficient [m2/s]
Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R

= gas constant [8.314 J/mol-K]

= absolute temperature [K]

SEM II 2015-2016

21

Diffusivity Data for Some

Metals
Solute

Solvent

D0
(M2/S)

Q
KJ/mol

Carbon

FCC Iron

2 x 10-5

142

Carbon

BCC Iron

22 x 10-5

122

Copper

Aluminum

1.5 x 10-5

126

Copper

Copper

2 x 10-5

197

Carbon

HCP
Titanium

51 x 10-5

182

SEM II 2015-2016

22

Diffusion Properties for Several

Materials

SEM II 2015-2016

23

Effect of Temperature on
Diffusion

If diffusivity at two temperatures are determined, two equations

can be solved for Q and D0
Example:The diffusivity of silver atoms in silver is 1 x 10-17 at 5000C and 7 x
10-13 at 10000C.
Therefore,

D1000
D500

Q 1 1

exp

exp( Q / RT1 )
R T2 T1

7 1013
1 1017

exp( Q / RT2 )

1
Q 1

exp

R
1273
773

Solving for activation energy Q

Q 183KJ / mol
SEM II 2015-2016

24

Example:
At 300C the diffusion coefficient and activation energy for Cu in Si are
D(300C) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350C?

transform data

Temp = T

ln D

1/T

1
Q
and lnD1 lnD0 d
R
T2
Qd 1 1
D2

lnD2 lnD1 ln

D1
R T2 T1

Qd
lnD2 lnD0
R

1

T1

Example (cont.)
Qd
D2 D1 exp
R

1 1

T2 T1

T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K

D2 (7.8 x 10

11

41,500 J/mol 1
1
m /s) exp

8.314 J/mol - K 623 K 573 K

2

D2 = 15.7 x 10-11 m2/s

SEM II 2015-2016

26

Non-Steady State
In most real situations the concentration profile and the concentration
Diffusion
gradient are changing with time. The changes of the concentration

profile is given in this case by a differential equation, Ficks second law.

Ficks second law:- Rate of compositional change is equal to diffusivity
times the rate of change of concentration gradient.

Plane 1

Plane 2

Change of concentration of solute

Atoms with change in time in
different planes

SEM II 2015-2016

27

Non-steady State Diffusion

The concentration of diffucing species is a function of
both time and position C = C(x,t)
In this case Ficks Second Law is used

C
C
D 2
t
x
2

Ficks Second Law

SEM II 2015-2016

28

Non-steady State Diffusion

Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms

bar
pre-existing conc., Co of copper atoms

Cs

Boundary Conditions
at t = 0, C = Co for 0 x
at t > 0, C = CS for x = 0 (const. surf. conc.)

C = Co SEM
forII 2015-2016
x=

29

Ficks Second Law Solution

The solution to this differential equation with the given boundary condition
is:

x
erf
2 D
Cs C0
t

Cs C x

Cs = Surface concentration of element in gas diffusing

into the surface.
C0 = Initial uniform concentration of element in solid.
Cx = Concentration of element at distance x from
surface at time t1.
x = distance from surface
D = diffusivity of solute
t = time.

SEM II 2015-2016

Cs

Time = t2

Time= t1

Cx

Time = t0
C0

Distance x

erf function Gaussian error

function, based on integration of
the bell shaped curve
30

Solution:
C x, t Co
1 erf
Cs Co

C(x,t) = Conc. at point x at

time t
erf (z) = error function

2 z y 2

e dy

2 Dt

CS

C(x,t)

erf(z) values are given in TableCo

5.1

SEM II 2015-2016

31

Tabulation of Error
Function Values

SEM II 2015-2016

32

Non-steady State Diffusion

Sample Problem: An FCC iron-carbon alloy initially containing 0.20
wt% C is carburized at an elevated temperature and in an
atmosphere that gives a surface carbon concentration constant at
1.0 wt%. If after 49.5 h the concentration of carbon is 0.35 wt% at a
position 4.0 mm below the surface, determine the temperature at
which the treatment was carried out.
Solution: use Eqn. 5.5

C( x, t ) Co
x
1 erf

Cs Co
2 Dt
SEM II 2015-2016

33

Solution (cont.):
C( x ,t ) Co
x
1 erf

Cs Co
2 Dt
t = 49.5 h
Cx = 0.35 wt%
Co = 0.20 wt%

x = 4 x 10-3 m
Cs = 1.0 wt%

C( x, t ) Co 0.35 0.20
x

1 erf
1 erf ( z )
Cs Co
1.0 0.20
2 Dt

erf(z) = 0.8125
SEM II 2015-2016

34

Solution (cont.):
We must now determine from Table 5.1 the value of z for which the
error function is 0.8125. An interpolation is necessary as follows
z

erf(z)

0.90
z
0.95

0.7970
0.8125
0.8209

Now solve for D

z 0.90
0.8125 0.7970

0.95 0.90 0.8209 0.7970

z 0.93

x
z
2 Dt

x2
4z 2t

3 2
x2
(
4
x
10
m)
1h

2.6 x 1011 m2 /s
4z 2t ( 4)(0.93)2 ( 49.5 h) 3600 s

SEM II 2015-2016

35

Solution (cont.)
To solve for the temperature at which D has above value, we use a
rearranged form of Equation (5.9a);

Qd
T
R( lnDo lnD )
from Table 5.2, for diffusion of C in FCC Fe
Do = 2.3 x 10-5 m2/s Qd = 148,000 J/mol

148,000 J/mol
(8.314 J/mol - K)(ln 2.3x105 m2 /s ln 2.6x1011 m2 /s)

T = 1300 K = 1027C
SEM II 2015-2016

36

Example: Chemical Protective

Clothing (CPC)
Methylene chloride is a common ingredient of paint removers.
Besides being an irritant, it also may be absorbed through skin.
When using this paint remover, protective gloves should be
worn.
If butyl rubber gloves (0.04 cm thick) are used, what is the
breakthrough time (tb), i.e., how long could the gloves be used
before methylene chloride reaches the hand?
Data (from Table 22.5)
diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
SEM II 2015-2016

37

Example (cont).
Solution assuming linear conc. gradient

glove
C1
paint
remover

2
tb
6D

skin

x2 x1 0.04 cm

C2

D = 110 x 10-8 cm2/s

x1 x2
tb

(0.04 cm)2
-8

(6)(110 x 10

240 s 4 min

cm /s)

Time required for breakthrough ca. 4 min

Industrial Applications of
Diffusion Case Hardening
Sliding and rotating parts needs to have hard surfaces.
These parts are usually machined with low carbon steel as
they are easy to machine.
Their surface is then hardened by carburizing.
Steel parts are placed at elevated temperature (9270C) in an
atmosphere of hydrocarbon gas (CH4).
Carbon diffuses into iron surface and fills interstitial space to
make it harder.

SEM II 2015-2016

39

Carburizing
C%

Low carbon
Steel part

Diffusing carbon
atoms
SEM II 2015-2016

Carbon Gradients
In Carburized metals
40

Impurity Diffusion into Silicon

wafer
Impurities are made to diffuse into silicon wafer to change its electrical
characteristics.
Used in integrated circuits.
Silicon wafer is exposed to vapor of impurity at 11000C in a quartz tube
furnace.
The concentration of
impurity at any point
depends on depth and
time of exposure.

SEM II 2015-2016

41

Summary
Diffusion FASTER for...

Diffusion SLOWER for...

open crystal structures

close-packed structures

materials w/secondary
bonding

materials w/covalent
bonding

smaller diffusing atoms

larger diffusing atoms

lower density materials

higher density materials

SEM II 2015-2016

42