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Chapter Chapter
55
CHAPTER 5
Diffusion Diffusion
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Chapter Chapter
55
Topic Contents Topic Contents
Introduction Introduction
Diffusion Mechanisms Diffusion Mechanisms
Vacancy Vacancy Diffusion Diffusion
Interstitial diffusion Interstitial diffusion
Steady Steady--State Diffusion State Diffusion
2
Diffusion and Temperature Diffusion and Temperature
Non Non--steady State Diffusion steady State Diffusion
2
Chapter Chapter
55
At the end of the lecture, students will be able:
1. Name and describe the two atomic mechanisms of diffusion.
2. Distinguish between steady-state and nonsteady-state diffusion.
TOPIC OUTCOMES
g y y
3. (a) write Ficks first and second laws in equation form,
and define all parameter
(b) Note the kind of diffusion for which each of these
equations is normally applied.
4. Write the solution to Ficks second law for diffusion into a semi-
infinite solid when the concentration of diffusing species at the
f h ld t t D fi ll t i thi ti
3
surface held constant. Define all parameters in this equation
5. Calculate the diffusion coefficient for some materials at a
specified temperature, given the appropriate diffusion constant
Chapter Chapter
55
INTRODUCTION
How does diffusion occur?
ISSUES TO ADDRESS... ISSUES TO ADDRESS...
How does diffusion occur?
Why is it an important part of
processing?
How can the rate of diffusion be
predicted for some simple cases?
How does diffusion depend on
4
How does diffusion depend on
structure and temperature?
3
Chapter Chapter
55
Diffusion
Diffusion - Mass transport by
atomic motion, migrate over a atomic motion, migrate over a
period of time
Mechanisms
Gases & Liquids random
(Brownian) motion
5
Solids vacancy diffusion or
interstitial diffusion (similar
with defects/imperfection)
Atomic Movement
Gas > Liquid > Solid
Chapter Chapter
55
Interdiffusion: In an alloy, atoms tend to migrate
from regions of high conc. to regions of low conc.
Initially
Diffusion (solid)
After some time elevated T < T
m
6
4
Chapter Chapter
55
Self-diffusion: In an elemental solid, atoms
also migrate.
In solid, atomic movements are restricted due to a bonding equilibrium.
Diffusion
However, thermal vibrations occurring in solids do allow some atoms to move
Label some atoms
After some time
A
C
C
D
7
A
B
D
A
B
D
Chapter Chapter
55
Diffusion Mechanisms
Several different models for this atomic motion
have been proposed, of these possibilities,
two dominate mechanisms for metallic
diffusion (similar concept with imperfection)
i. Vacancy Diffusion
ii. Interstitial Diffusion
8
ii. Interstitial Diffusion
5
Chapter Chapter
55
I. Substitutional/Vacancies Diffusion Mechanisms
applies to substitutional
impurities
atoms exchange with
vacancies
Atom moves from one site to
another if:
(1) there is enough activation
energy from thermal vibration
9
energy from thermal vibration
(2) if there are vacancies or
crystal defects
increasing elapsed time
Chapter Chapter
55
Applies to interstitial
ii. Interstitial Diffusion Mechanisms
pp
impurities.
More rapid than
vacancy diffusion.
Size of diffusing atoms
must be relatively small
10
7
6
Chapter Chapter
55
The diffusion rate in solid metal crystals is affected by 5 factors:
Type of diffusion mechanism (interstitial & substitutional) depending to
size of atom,ions)
Temperature of diffusion; normally when temp increase, diffusion rate
also increase
Concentration (quantity) of the diffusion species (concentration gradient);
effect the solute atom
11
Type of crystal structure (Lower atom packing order ex. BCC (0.68),
FCC (0.74). Interatomic spaces between ion wider
Type of crystal imperfections present (Ex: grain boundaries less atomic
packing, excess vacancies will increase diffusion rate)
Chapter Chapter
55
Activation Energy (Q)
Def: Energy required to produce the diffusive motion of
one mole of atoms.
Or atoms must overcome some energy barrier to move
This energy barrier called activation energy s e e gy ba e ca ed act at o e e gy
12
7
Chapter Chapter
55
Diffusion
Diffusion is a time-dependent
process p
In a macroscopic sense the
quantity of an element that is
transported within another is a
function of time.
But how fast diffusion occurs?
13
But how fast diffusion occurs?
Chapter Chapter
55
Diffusion
How do we quantify the amount
or rate of diffusion? J= Flux
Measured empirically
Make thin film (membrane) of known surface area
Impose concentration gradient (exp; diff pressure)
Measure how fast atoms or molecules diffuse
( )( ) s m
kg
or
s cm
mol
time area surface
diffusing mass) (or moles
Flux
2 2
= J
14
through the membrane
Different Concentration Profile
(the movement of atoms)
8
Chapter Chapter
55
Diffusion Flux (J)
Def: the mass (or,
equivalently, the
number of atoms) M
diffusing through and
perpendicular to area
cross-sectional area of
lid it f ti
x-direction
Unit area A
through
15
solid per unit of time. which
atoms
move.
Chapter Chapter
55
Flux:
Mathematical Diffusion
J =
M
At
1dM kg atoms
dt
dM
A
l
At
M
J = =
M =
16

J =
1
A
dM
dt

kg
m
2
s






or
atoms
m
2
s






mass
diffused
time
J slope
9
Chapter Chapter
55
State of Diffusion
i. Steady State Diffusion
ii N St d St t Diff i ii. Non - Steady State Diffusion
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Chapter Chapter
55
i. Steady-State Diffusion
Fl ti l t t ti di t
dC
Steady State: the concentration profile doesn't
change with time (not vary with position!). (Ex; H
2
diffuse through Pd non reacting gases)
dC
Ficks first law of diffusion
C
1
C
2
C
1
C
2
Rate of diffusion independent of time
Flux proportional to concentration gradient =
dx
dC
Part A Part B
Thin Metal
18
dx
dC
D J =
2
x
C
2
x
1
x
2
D diffusion coefficient
1 2
1 2
linear if
x x
C C
x
C
dx
dC

=
A
A
~
-ve =diffusion from high to lower concentration
-ve diffusion gradient
10
Chapter Chapter
55
J
x(left)
= J
x(right)
Steady State:
J
x(right)
J
x(left)
i. Steady-State Diffusion
Apply Fick's First Law:
(No change in system with time)
J
x(left)
= J
x(right)
Concentration, C, in the box doesnt change w/time.
x

J
x
= D
dC
dx
D =
diffusivity
(Diffusion
coefficient)
19
12
Result: the slope, dC/dx (concentration gradient) must be constant
(i.e., slope doesn't vary with position)!

dC
dx
|
\

|
.
|
left
=
dC
dx
|
\

|
.
|
right
If J
x
)
left
= J
x
)
right
, then
Chapter Chapter
55
Driving force
Sometimes the term of driving force is used in the
contact of what compels (make) a reaction to
occur.
For diffusion reaction, several forces are possible
But when diffusion is according to Ficks first law,
the concentration gradient is the driving force.
Ficks first law of diffusion
20
dx
dC
D J =
Fick s first law of diffusion
11
Chapter Chapter
55
A plate of iron is exposed to a carburizing
(carbon-rich) atm on one side and a
decarburizing (carbon-deficient) atm on the
Problem1:
other side at 700C. if a condition of steady
state is achieved, calculated the diffusion flux
of carbon through the plate if the
concentration of carbon at positions of 5 and
10 mm (5 x 10
-3
and 10
-2
m) beneath the
carburizing surface are 1 2 and 0 8 kg/m
3
21
carburizing surface are 1.2 and 0.8 kg/m
3
,
respectively. Assume a diffusion coefficient of
3 x 10
-11
m
2
/s at this temperature.
Chapter Chapter
55 How to solve?
22
12
Chapter Chapter
55
Steel plate at
700C with
geometry
h
C
1

=

1
.
2
k
g
/
m
3
C
2

=
0
.
8
k
g
/
m
3
Carbon Steady State =
Solution 1:
shown:
Q: How much
Carbon
rich
gas
1
0
m
Carbon
deficient
gas
x
1
x
2 0
5
m
m
D=3x10
-11
m
2
/s
Steady State
straight line!
23
Q: How much
carbon transfers
from the rich to
the deficient side?
J
=
D
C
2

C
1
x
2

x
1
=
2.4

10
9
kg
m
2
s
m
m
m
m
Chapter Chapter
55
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
Problem2: Chemical Protective Clothing (CPC)
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 10
8 2
/
24
D = 110 x10
-8
cm
2
/s
surface concentrations:
C
2
= 0.02 g/cm
3
C
1
= 0.44 g/cm
3
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Chapter Chapter
55
Solution 2:
1 2
C C
D
dC
D J

glove
C
1
assuming linear conc. gradient
1 2
1 2
-
x x
D
dx
D J

~ =
D
t
b
6
2

=
1
C
2
skin
paint
remover
x
1
x
2
D = 110x10
-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:
25
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
Chapter Chapter
55
Factor That Influence Diffusion:
i. Diffusing Species
ii. Temperature Environments
26
14
Chapter Chapter
55
i. Diffusing Species
It depend on diffusion coefficient (D) of
specific materials.
Example: Ionics species Li
+
, Na
+
, K
+
Diffusion Rate: Li
+
>Na
+
>K
+
why?
27
Atom seize: Li
+
<Na
+
<K
+
Effect?
ionic conduction: Li
+
>Na
+
>K
+
Chapter Chapter
55
i. Diffusing Species (cont).
Relative saiz for atoms and ions
Radius in nanometer unit
28
15
Chapter Chapter
55
ii. Diffusion and Temperature
Diffusion coefficient increases with increasing T
(major influence).
D
=
D
o
exp
|
\

|
.
|

Q
d
RT
= temp-independent in range for which equation is valid [m
2
/s]
= diffusion coefficient/diffusivity [m
2
/s]
= activation energy [J/mol or eV/atom]
D
D
o
Q
d
29
gy [ ]
= gas constant [8.314 J/mol-K]
= absolute temperature [K]
d
R
T
Chapter Chapter
55
D has exponential dependence on T
T(C) 5
0
0
0
0
0
6
0
0
3
0
0
ii. Diffusion and Temperature (cont).
D
interstitial
>> D
substitutional
C in o-Fe
C in -Fe
Al in Al
Fe in o-Fe
Fe in -Fe
D (m
2
/s)
10
-14
10
-8
( )
1 1 6 3
30
1000K/T
0.5 1.0 1.5
10
-20
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Chapter Chapter
55
The temperature dependence of the
diffusion coefficients is:
ii. Diffusion-Temperature Equations
D = D
o
exp (-Q
d
/RT)
In natural log:
ln D = ln Do (Q
d
/R)(1/T)
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In term of log base 10,
log D = log Do (Q
d
/2.3R)(1/T)
Chapter Chapter
55
At 300C the diffusion coefficient and activation energy for Cu in Si
are
D(300C) = 7.8 x 10
-11
m
2
/s
Q = 41 5 kJ/mol
Problem3:
Q
d
= 41.5 kJ/mol
What is the diffusion coefficient (D) at 350C?
transform
data
D ln D
32
|
|
.
|

\
|
=
|
|
.
|

\
|
=
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
Temp = T
1/T
17
Chapter Chapter
55

|
|
.
|

\
|
=
1 2
1 2
1 1
exp
T T R
Q
D D
d
Solution 3:

|
.
|

\
|

=

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
T
1
= 273 + 300 = 573K
T
2
= 273 + 350 = 623K
33

. \
K 573 K 623 K J/mol 314 . 8
D
2
= 15.7 x 10
-11
m
2
/s
Chapter Chapter
55
Problem 4:
Find the activation energy (Q
d
) for material by experimental
method
34
18
Chapter Chapter
55
Solution 4:
35
Chapter Chapter
55
Most practical diffusion situations
Diff i fl d th t ti
ii. Non Steady State Diffusion
Diffusion flux and the concentration
gradient at some particular point in a
solid vary with time
Follow Ficks Second Law
36
19
Chapter Chapter
55
Copper diffuses into a bar of aluminum.
pre-existing conc., C
o
of copper atoms
Surface conc.,
C
s
of Cu atoms
bar
C(x t)
Example : Non steady state diffusion
C
o
C
s
position x
C(x,t)
t
o
t
1
t
2
t
3
C
x
t
3
>t
2
>t
1
X
37
15
General formulation: Ficks 2
nd
Law
C(x, t)

C
o
C
s

C
o
=
1

erf
x
2 Dt
|
\

|
.
|
position, x
"error function"
Chapter Chapter
55
Concentration, C
Non steady state diffusion
C
s
C
x
C
0
- -- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
- -- - - - - - - -
- -- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -- - - - - -
- -
C
s
C
0
C
x
C
0
38
Distance from interface, x
20
Chapter Chapter
55
erf - "error function"
39
Chapter Chapter
55
Problem5: NonSteady-State Diffusion
Consider one such alloy that initially has a
uniform carbon concentration of 0.25 wt% and
is to be treated at 950C If the concentration is to be treated at 950 C. If the concentration
of carbon at the surface is suddenly brought to
and maintained at 1.20 wt.%, how long will it
take to achieve a carbon content of 0.80 wt.%
at a position 0.5 mm below the surface? The
diffusion coefficient for carbon in iron at this
40
diffusion coefficient for carbon in iron at this
temperature is 1.6 x 10
-11
m
2
/s; assume that
the steel piece is semi-infinite.
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Chapter Chapter
55
Cs = 1.2 wt.% C
Co = 0.25 wt. % C
Cx = 0.80 wt.% C
X = 0.50 mm = 5 x 10
-4
m
D = 1.6 x 10
-11
m
2
/s
Solution 5:
D 1.6 x 10 m /s
Using formula: Ficks 2
nd
Law
C
x
C
o
= 1 erf (x/2Dt)
C
s
- C
o
erf (x/2Dt) = 0.4210
or
erf (z) = 0.4210
41
From table 5.1, get the z value (use ratio concept)
z erf (z)
0.35 0.3794 z - 0.35 = 0.4210 0.3794
z 0.4210 0.40 - 0.35 0.4284 - 0.3794
0.40 0.4284
z = 0.392
Chapter Chapter
55
z = 0.392 z 0.392
0.392 = (x/2Dt)
Rearranged equation include x and D value from question
t = 25400 s = 7.1 h
42
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Chapter Chapter
55
Diffusion FASTER for...
open crystal structures
Diffusion SLOWER for...
close-packed structures
Summary
open crystal structures
materials w/secondary
bonding
smaller diffusing atoms
lower density materials
close-packed structures
materials w/covalent
bonding
larger diffusing atoms
higher density materials
43
lower density materials higher density materials
Chapter Chapter
55
Applications
Case hardening of steel by gas carburizing
Impurity diffusion into silicon wafers for
integrated circuits
44
23
Chapter Chapter
55
Exercise 1
Consider the gas carburizing of gear steel
t 927C C l l t ti i i t at 927C. Calculate time in minutes
necessary to increase the carbon content
to 0.40% at 0.50 mm below the surface.
Assume that the carbon content at the
surface is 0.90% and that the steel has a
nominal carbon content of 0.20%
Given D
927C
= 1.28 x 10
-11
m
2
/s
45
Chapter Chapter
55
Exercise 2
From exercise 1, calculate the carbon
t t t 0 50 b th th f content at 0.50 mm beneath the surface
of the gear after 5 h carburizing time.
Assume that the carbon content of the
surface of the gear is 0.90% and the steel
has a nominal carbon content of 0.20%
46
24
Chapter Chapter
55
Answers
Exercise 1: 143 minutes
Exercise 2: 0.52%
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