PSMMY Sept2012 1

INTRODUCTION TO
MATERIALS SCIENCE
2
Learning Outcomes
Todaywhat do I want you to learn?
Name and describe the two atomic mechanisms
of diffusion.
Discuss on the factors that affect diffusion
process.
Distinguish between steady-state and non-steady
state diffusion.
Write Ficks first and second law in equation
form, and define all parameters.
PSMMY Sept2012
3
Learning Outcomes
Note the kinds of diffusion for which Ficks first and
second law are applied.
Apply Ficks first and second law to steady-state
diffusion problems.
Calculate the diffusion coefficient for some material
at a specified temperature, given the appropriate
diffusion constants.
Todaywhat do I want you to learn?
PSMMY Sept2012
PSMMY May 2012 4
TODAY

5
Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially
Adapted from
Figs. 5.1 and
5.2, Callister &
Rethwisch 8e.
Diffusion
After some time
DIFFUSION
6
DIFFUSION
movement of atoms/ions/electrons/holes
within the material caused by concentration
gradient and temperature.
2 conditions must be met
there must be an empty adjacent site
the atom must have sufficient energy to
break bonds with its neighbouring atoms
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7

Types of Diffusion

1. inter-diffusion or impurity diffusion
- atoms of one metal diffuse into another metal
2. self-diffusion
- same type of atoms exchanging positions
1.
2.
PSMMY Sept2012
Name and describe the two atomic mechanisms of diffusion.
8

Mechanisms of Diffusion
1. Vacancy diffusion
- interchange of an atom from a normal lattice
position to an adjacent vacant lattice site or vacancy
Name and describe the two atomic mechanisms of diffusion.
9

Mechanisms of Diffusion
2. Interstitial diffusion
- atoms migrate from an interstitial position to a
neighbouring one that is empty
- occurs more rapidly compared to vacancy
diffusion. Why??
10
Applications of Diffusion
Processes in Real Life
Carburisation of Surface Hardening of Steels
C in the form of graphite powder or in
gaseous phase will be diffused into the steel
to form a hard case (high wear resistance),
yet has a ductile, tough inner core for
fracture resistance
Diffusion of drugs in blood system
Lost of CO
2
from carbonated drinks over long
period of time.
Contact lenses - moisture diffusion
Kidney function

PSMMY Sept2012
PSMMY May 2012 11
Carburisation
of Steels
carbon rich gas
atmosphere
12
Adapted from
chapter-opening
photograph,
Chapter 5,
Callister &
Rethwisch 8e.
(Courtesy of
Surface Division,
Midland-Ross.)
Case Hardening:
-- Diffuse carbon atoms
into the host iron atoms
at the surface.
-- Example of interstitial
diffusion is a case
hardened gear.
Result: The presence of C
atoms makes iron (steel)
harder.
Processing Using Diffusion
PSMMY Sept2012
Distinguish between steady-state and non-steady state diffusion.
13
Steady-State Diffusion
Across A Thin Plate

direction of
diffusion of
gaseous species
T
h
i
n

Area, A
thin metal plate
flux, J
Concentration gradient
does not change with time
x
1
x
2
14
How do we quantify the amount or rate of
diffusion?
( )( )
s m
kg
or
s cm
mol
time area surface
diffusing mass) (or moles
Flux
2 2
= J
Diffusion
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dx
dC
D J =
Ficks first law of
diffusion
C
1

C
2

x
C
1

C
2

x
1
x
2

D diffusion coefficient
Rate of diffusion independent of time
Flux proportional to concentration gradient =
dx
dC
1 2
1 2
linear if
x x
C C
x
C
dx
dC

=
A
A
~
Steady-State Diffusion
PSMMY Sept2012
Write Ficks first and second law in equation form, and define all parameters.
16

Steady-State Diffusion
Ficks First Law
Ficks First Law states that:
x
c
D
dx
dc
D J
A
A
~ =
Flux, J defined as number
of atoms passing through
a plane of unit area per
unit time (atoms/(m
2
.s))
diffusivity or
diffusion coefficient (cm
2
/s)
concentration gradient
(atoms/(cm
3
.cm))
17
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
cm
2
/s
surface concentrations:

C
2
= 0.02 g/cm
3
C
1
= 0.44 g/cm
3
Apply Ficks first and second law to steady-state diffusion problems.
18
s cm
g
10 x 16 . 1
cm) 04 . 0 (
) g/cm 44 . 0 g/cm 02 . 0 (
/s) cm 10 x 110 (
2
5 -
3 3
2 8 -
=

= J
Example (cont).
1 2
1 2
-
x x
C C
D
dx
dC
D J

~ =
D
t
b
6
2

=
glove
C
1

C
2

skin
paint
remover
x
1
x
2

Solution assuming linear conc. gradient
D = 110 x 10
-8
cm
2
/s
C
2
= 0.02 g/cm
3
C
1
= 0.44 g/cm
3
x
2
x
1
= 0.04 cm

Data:
PSMMY Sept2012
19
Diffusion coefficient increases with increasing T.
D
=
D
o
exp
|
\

|
.
|

Q
d

R T
= pre-exponential [m
2
/s]
= diffusion coefficient [m
2
/s]
= activation energy [J/mol or eV/atom]
= gas constant [8.314 J/mol-K]
= absolute temperature [K]
D
D
o
Q
d
R
T
Calculate the diffusion coefficient for some material at a specified temperature, given the appropriate
diffusion constants.
Diffusion and Temperature
20
Activation Energy of Diffusion



Q
v
Q
i
Q
v
>Q
i
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Adapted from Fig. 5.7, Callister & Rethwisch 8e. (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.)
D has exponential dependence on T
D
interstitial
>> D
substitutional
C in o-Fe
C in -Fe
Al in Al
Fe in o-Fe
Fe in -Fe
1000 K/T
D (m
2
/s)
0.5 1.0 1.5
10
-20

10
-14

10
-8

T(C)
1
5
0
0

1
0
0
0

6
0
0

3
0
0

Diffusion and Temperature
D
=
D
o
exp
|
\

|
.
|

Q
d

R T
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22
Example: At 300C the diffusion coefficient and
activation energy for Cu in Si are

D(300C) = 7.8 x 10
-11
m
2
/s
Q
d
= 41.5 kJ/mol

What is the diffusion coefficient at 350C?
|
|
.
|

\
|
=
|
|
.
|

\
|
=
1
0 1
2
0 2
1
ln ln and
1
ln ln
T R
Q
D D
T R
Q
D D
d d
|
|
.
|

\
|
= =
1 2 1
2
1 2
1 1
ln ln ln
T T R
Q
D
D
D D
d
transform
data
D
Temp = T
ln D
1/T
D
=
D
o
exp
|
\

|
.
|

Q
d

R T
PSMMY Sept2012
23
Example (cont.)
(

|
.
|

\
|

=

K 573
1
K 623
1
K - J/mol 314 . 8
J/mol 500 , 41
exp /s) m 10 x 8 . 7 (
2 11
2
D
(

|
|
.
|

\
|
=
1 2
1 2
1 1
exp
T T R
Q
D D
d
T
1
= 273 + 300 = 573 K
T
2
= 273 + 350 = 623 K
D
2
= 15.7 x 10
-11
m
2
/s
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The concentration of diffusing species is a
function of both time and position C = C(x,t)
In this case Ficks Second Law is used:


2
2
x
C
D
t
C
c
c
=
c
c
Ficks Second Law
Write Ficks first and second law in equation form, and define all parameters.
Non-Steady State Diffusion
PSMMY May 2012 25
Non-Steady State
DiffusionProfile:
Ficks Second Law
26
Adapted from
Fig. 5.5,
Callister &
Rethwisch 8e.
B.C. at t = 0, C = C
o
for 0 s x s
at t > 0, C = C
S
for x = 0 (constant surface conc.)
C = C
o
for x =
Copper diffuses into a bar of aluminum.
pre-existing conc., C
o
of copper atoms
Surface conc.,
C of Cu atoms
s
C
s
Non-Steady State Diffusion
Boundary
conditions
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27
The Solution to Ficks Second Law:
C(x,t) = Conc. at point x at
time t
erf (z) = Gaussian error function



erf(z) values are given in Table 5.1
C
S

C
o

C(x,t)
( )
|
.
|

\
|
=

Dt
x
C C
C t , x C
o s
o
2
erf 1
dy e
y
z
2
0
2

}
t
=
Adapted from Fig. 5.5,
Callister & Rethwisch 8e.
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z erf(z)
0 0
0.2 0.2227
0.5 0.5205
0.90 0.7970
0.95 0.8209

Gaussion Error Function
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Non-steady State Diffusion:
Example
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
|
.
|

\
|
=

Dt
x
C C
C t x C
o s
o
2
erf 1
) , (
Apply Ficks first and second law to steady-state diffusion problems.
30
Solution (cont.):
t = 49.5 h x = 4 x 10
-3
m
C
x
= 0.35 wt% C
s
= 1.0 wt%
C
o
= 0.20 wt%

|
.
|

\
|
=

Dt
x
C C
C ) t , x ( C
o s
o
2
erf 1
) ( erf 1
2
erf 1
20 . 0 0 . 1
20 . 0 35 . 0 ) , (
z
Dt
x
C C
C t x C
o s
o
= |
.
|

\
|
=

erf(z) = 0.8125
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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 0.7970
z 0.8125
0.95 0.8209
7970 . 0 8209 . 0
7970 . 0 8125 . 0
90 . 0 95 . 0
90 . 0

z
z = 0.93
Now solve for D
Dt
x
z
2
=
t z
x
D
2
2
4
=
/s m 10 x 6 . 2
s 3600
h 1
h) 5 . 49 ( ) 93 . 0 ( ) 4 (
m) 10 x 4 (
4
2 11
2
2 3
2
2

= =
|
|
.
|

\
|
=
t z
x
D
PSMMY Sept2012
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To solve for the temperature at
which D has the above value, we
use a rearranged form of Equation
(5.9a);

) ln ln ( D D R
Q
T
o
d

=
from Table 5.2, for diffusion of C in FCC Fe

D
o
= 2.3 x 10
-5
m
2
/s Q
d
= 148,000 J/mol
/s) m 10 x 6 . 2 ln /s m 10 x 3 . 2 K)(ln - J/mol 314 . 8 (
J/mol 000 , 148
2 11 2 5

= T

Solution (cont.):
T = 1300 K = 1027C
PSMMY Sept2012
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Factors Affecting Diffusion
Concentration gradient
Temperature
Diffusing species
Diffusion paths
Diffusion mechanism
PSMMY Sept2012
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Diffusion FASTER for...

open crystal structures

materials w/secondary
bonding

smaller diffusing atoms

lower density materials
Diffusion SLOWER for...

close-packed structures

materials w/covalent
bonding

larger diffusing atoms

higher density materials
Also
PSMMY Sept2012
35
SUMMARY
occurs because of the presence of point defects (vacancy,
interstitial defects)
is a thermally activated process, defined as the movement of
atoms/ions caused by concentration gradient and temperature.
requires activation energy, Q.
two kinds: self and inter-diffusion
two mechanisms: vacancy and interstitial
The rate of diffusion is governed by the Arrhenius equation.
Ficks First Law says that the the flux of a diffusing species is
proportional to the concentration gradient at a constant
temperature.
Fick's Second Law states that the rate of change of
concentration in a volume element of a membrane, within the
diffusional field, is proportional to the rate of change of
concentration gradient at that point in the field.
36
CONCLUSIONS
You should be able to:

Name and describe the two atomic mechanisms
of diffusion.
Discuss on the factors that affect diffusion process.
Distinguish between steady-state and non-steady
state diffusion.
Write Ficks first & second law in equation form,
and solve related problems.
PSMMY Sept2012
37
QUESTIONS TO PONDER
How do grain boundaries affect
diffusion?
What have you not understood well?
PSMMY Sept2012
38
NEXT


Measurement of
Mechanical Properties

PSMMY Sept2012