MM 501 Ashraf Ali

NED University
1
Diffusion in Solid State
MM-501: Phase Transformations in Solids
Prof. Dr. Ashraf Ali
MM 501 Ashraf Ali
NED University
2
Course Outline
Diffusion - how do atoms move through solids?

! Diffusion mechanisms
" Vacancy diffusion
" Interstitial diffusion
" Impurities
! The mathematics of diffusion
" Steady-state diffusion (Ficks first law)
" Nonsteady-State Diffusion (Ficks second law)
! Factors that influence diffusion
" Diffusing species " Host solid
" Temperature " Microstructure


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Diffusion is easy in liquids and gases where atoms are relatively
free to move around:
e.g. making chocolate milk. Really need to stir the milk to get that
viscous chocolate syrup evenly mixed!

Diffusion is difficult in solids due to bonding and requires, most
of the time, external energy to mobilize the atoms.

In solids, atoms are not fixed at its position but constantly
moves (oscillates). The degree of movement depends on
temperature (extrinsically) and structure (intrinsically) of the
system

Inhomogeneous materials can become homogeneous by diffusion.
For an active diffusion to occur, the temperature should be high
enough to overcome energy barriers to atomic motion.
What is diffusion?
Material transport by atomic motion is called Diffusion.
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Diffusion
Diffusion refers to the process by which
atoms/molecules intermingle as a result of their
kinetic energy of random motion.

Consider two containers of gas A and B
separated by a partition. The molecules of both
gases are in constant motion and make
numerous collisions with the partition. If the
partition is removed as in the lower illustration,
the gases will mix because of the random
velocities of their molecules. In time a uniform
mixture of A and B molecules will be produced
in the container.

The tendency toward diffusion is very strong
even at room temperature because of the high
molecular velocities associated with the thermal
energy of the particles.

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e.g., Materials processing


1. Chemical reactions/treatments require mass transfer (i.e.
diffusion).
e.g. alloying, strengthening of materials via case
hardening etc

2. Many materials are heat treated to achieve necessary
properties: prefer to develop methods that will allow relatively
high diffusion rates to achieve an efficient/cost-effectively
process, Homogenisation for example.
Why do we care about diffusion in solids?
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1. Hard Facing (Carburizing of Steels)
Tough Tools and Parts.
Wear Facing of Gears, Wheels and Rails

2. Chemical Tempering of Glass and Ceramics
Toughened Ceramics (Corel Ware)
Shard resistant safety glass

3. Thin Film Electronics (CMOS and Bipolar
Transistors)
Doping of Semiconductors
Applications of Diffusion in Solids-1
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4. Diffusion Bonding -- (Adhesives and Cements -
ceramic, metallic and polymer)
a. Portland Cement as Bonding for Construction
b. Solvent Cements for PVC Polymeric Piping
c. Thermocouple Junctions

5. Corrosion Protection
Galvanizing, Electroplating, Anodizing,
Inhibiting

6. Gas (Chemical) Separation Processes -
Diffusion membranes
Applications of Diffusion in Solids-2
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PROCESSING USING DIFFUSION (1)
Case Hardening:
--Diffuse carbon atoms
into the host iron atoms
at the surface.
--Example of interstitial
diffusion is a case
hardened gear.
Result: The "Case" is
--hard to deform: C atoms
"lock" planes from shearing.
--hard to crack: C atoms put
the surface in compression.
Fig. 5.0,
Callister 6e.
(Fig. 5.0 is
courtesy of
Surface
Division,
Midland-
Ross.)
From Callister 6e resource CD.
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Diffusion Bonding
Diffusion bonding is a method of creating a
joint between similar or dissimilar metals,
alloys, and nonmetals.

Two materials are pressed together
(typically in a vacuum) at a specific
bonding pressure with a bonding
temperature for a specific holding time.
PROCESSING USING DIFFUSION (2)
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Solid state joining process

Apply heat & pressure across
interface to be joined

Local plastic deformation +
diffusion = joint!

Useful for joining difficult to
weld metals, dissimilar materials,
metals and ceramics

B-18
Application of Diffusion Bonding
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Doping of Silicon with P for n-type semiconductors:
Process:
1. Deposit P rich
layers on surface.
2. Heat it.
3. Result: Doped
semiconductor
regions.
silicon
silicon
Fig. 18.0,
Callister 6e.
From Callister 6e resource CD.
PROCESSING USING DIFFUSION (3)
Thin Film Electronics (CMOS and Bipolar Transistors)

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DIFFUSION: THE PHENOMENON
Self-diffusion: Atoms within one material exchanging
positions. (i.e. In an elemental solid, atoms also migrate).
Label some atoms After some time
A
B
C
D
From Callister 6e resource CD.
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NED University
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DIFFUSION: THE PHENOMENON
Interdiffusion: Atoms of one material diffusing into another and vice
versa. For example, in an alloy, atoms tend to migrate from regions of large
concentration (Impurity Diffusion).
Initially After some time
100%
Concentration Profiles
0
Adapted from
Figs. 5.1 and
5.2, Callister 6e.
From Callister 6e resource CD.
Consider a concentration gradient then atoms move from high conc. to low conc..
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Diffusion Mechanisms
How do atoms move in a crystalline solid?
For diffusion to occur:
1. Adjacent site needs to be empty (vacancy or
interstitial).
2. Sufficient energy must be available to break
bonds and overcome lattice distortion.
There are many possible mechanisms but lets consider
the simple cases:
1. Vacancy diffusion.
2. Interstitial diffusion.
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Vacancy Mechanism

Atoms can move from one site to another if
there is sufficient energy present for the
atoms to overcome a local activation energy
barrier and if there are vacancies present
for the atoms to move into.

The activation energy for diffusion is the
sum of the energy required to form a
vacancy and the energy to move the
vacancy.


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Vacancy diffusion
- An atom adjacent to a vacant lattice site moves into it.
Essentially looks like
an interstitial atom:
lattice distortion
First, bonds with the neighboring
atoms need to be broken
From Callister 6e resource CD.
To jump from lattice site to lattice site,
atoms need energy to break bonds
with neighbors, and to cause the
necessary lattice distortions during
jump. This energy comes from the
thermal energy of atomic
vibrations (Eav ~ kT)

Materials flow (the atom) is opposite
the vacancy flow direction.
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Interstitial atoms like hydrogen, helium,
carbon, nitrogen, etc) must squeeze through
openings between interstitial sites to diffuse
around in a crystal.

The activation energy for diffusion is the
energy required for these atoms to squeeze
through the small openings between the
host lattice atoms.

Interstitial Mechanism
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Interstitial Diffusion
Migration from one interstitial site to another (mostly for small atoms that can
be interstitial impurities: (e.g. H, C, N, and O) to fit into interstices in host.
Carbon atom in Ferrite
Interstitial diffusion is generally faster
than vacancy diffusion because bonding of
interstitials to the surrounding atoms is normally
weaker and there are many more interstitial sites
than vacancy sites to jump to.
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Interstitial Diffusion-Animation
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Diffusivity -- depends on:

1. Diffusion mechanism. Substitutional vs interstitial.
2. Temperature.
3. Type of crystal structure of the host lattice.
Interstitial diffusion easier in BCC than in FCC.
4. Type of crystal imperfections.
(a) Diffusion takes place faster along grain
boundaries than elsewhere in a crystal.
(b) Diffusion is faster along dislocation lines
than through bulk crystal.
(c) Excess vacancies will enhance diffusion.
5. Concentration of diffusing species.

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MODELING DIFFUSION: FLUX (J)
Consider atoms, M, going through a plane of area, A, in time, t:
t = 0
t = t
2 atoms passed from left to right (+ direction)
1 atom passed from right to left (- direction)
Net result:
'
1
t area
atom

or
' At
M
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MODELING DIFFUSION: FLUX
Flux (J): No. of Atoms diffusiong through Unit area and per Unit Time OR Materials
diffusion through unit area per unit time.
Directional Quantity
Flux can be measured for:
--vacancies
--host (A) atoms
--impurity (B) atoms
In general: diffusion flux may or may not be the same over time
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MODELING DIFFUSION
What causes net flow of atoms?
Concentration Profile, C(x): [kg/m
3
]
Concentration
of Cu [kg/m
3
]
Concentration
of Ni [kg/m
3
]
Position, x
Cu flux Ni flux
The steeper the concentration profile, the greater the flux!
Adapted from
Fig. 5.2(c),
Callister 6e.
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Steady-State Diffusion: Ficks First Law
Ficks first law: the diffusion flux along direction x is
proportional to the concentration gradient.
where D is the diffusion coefficient
The concentration gradient is often called the driving force in diffusion.

Ficks first law applies to steady state flux in a
uniform concentration gradient.
The minus sign in the equation means that
diffusion is down the concentration gradient.
Concentration gradient: dC/dx (Kg m-4) is the
slope at a particular point on concentration
profile.
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Example
The total membrane surface area in the lungs (alveoli)
may be on the order of 100 square meters and have
a thickness of less than a millionth of a meter, so it is
a very effective gas-exchange interface.
Fick's law is commonly used to model transport processes in:

Foods,
Biopolymers,
Biomedical
Pharmaceuticals,
Porous soils,
Semiconductor doping process, etc.
Where can we use Ficks Law?
CO
2
in air has D~16 mm
2
/s, and, in water, D~ 0.0016 mm
2
/s
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Steady-State Diffusion: the concentration profile doesn't
change with time.
Steady-State Diffusion
Apply Fick's First Law:
Result: the slope, dC/dx, must be constant
(i.e., slope doesn't vary with position)!

J
x
= D
dC
dx

dC
dx
|
\

|
.
|
left
=
dC
dx
|
\

|
.
|
right
If J
x
)
left
= J
x
)
right
, then
From Callister 6e resource CD.
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Steel plate at 700
0
C with geometry shown:
Q: In steady-state, how much carbon transfers
from the rich to the deficient side?
Adapted from Fig.
5.4, Callister 6e.
Example: Steady-state Diffusion
Knowns:
C
1
= 1.2 kg/m
3
at 5mm
(5 x 10
3
m) below surface.

C
2
= 0.8 kg/m
3
at 10mm
(1 x 10
2
m) below surface.

D = 3 x10
-11
m
2
/s at 700 C.
700 C
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Concentration profile,
C(x), changes w/ time.
14
To conserve matter:
Fick's First Law:
Governing Eqn.:
Non-Steady-State Diffusion
In most real situations the concentration profile and the
concentration gradient are changing with time. The
changes of the concentration profile is given in this case
by a differential equation, Ficks second law.
Called Ficks second law
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Fick's Second Law of Diffusion





In words, the rate of change of composition at position x
with time, t, is equal to the rate of change of the product of the
diffusivity, D, times the rate of change of the concentration
gradient, dC
x
/dx, with respect to distance, x.

|
.
|

\
|
x d
C
d
D
x d
d
=
t d
C
d
x x
Non-Steady-State Diffusion
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Copper diffuses into a bar of aluminum.
15
General solution:
"error function"
Values calibrated in Table 5.1, Callister 6e.
C
o
C
s
position, x
C(x,t)
t
o
t
1
t
2
t
3
Adapted from Fig.
5.5, Callister 6e.
Example: Non Steady-State Diffusion
t
3
>t
2
>t
1
Fig. 6.5: Concentration profiles nonsteady-state diffsion taken at three different times
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|
.
|

\
|
T R
Q
-
D
= D
d
o
exp
T R
Q
-
D
= D
d
o
ln ln
Where
D is the Diffusivity or Diffusion Coefficient ( m2 / sec )
Do is the prexponential factor ( m2 / sec )
Qd is the activation energy for diffusion ( joules / mole )
R is the gas constant ( joules / (mole deg) )
T is the absolute temperature ( K )
Temperature Dependence of the
Diffusion Coefficient
OR
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Carburizing or Surface
Modifying System

Species A achieves a surface concentration of C
s

and at time zero the initial uniform concentration of
species A in the solid is C
o
. Then the solution to
Fick's second law for the relationship between the
concentration C
x
at a distance x below the surface at
time t is given as




where C
s
= surface concentration,
C
o
= initial uniform bulk concentration
C
x
= concentration of element at distance x
from surface at time t.
x = distance from surface
D = diffusivity of diffusing species in host
lattice
t = time

|
.
|

\
|
Dt 2
x
erf - 1 =
C
-
C
C
-
C
o s
o x
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Carburizing or Surface Modifying System
Species A achieves a surface concentration of Cs and at time zero the
initial uniform concentration of species A in the solid is Co . Then the
solution to Fick's second law for the relationship between the
concentration Cx at a distance x below the surface at time t is given as:
|
.
|

\
|
Dt 2
x
erf - 1 =
C
-
C
C
-
C
o s
o x
where
Cs = surface concentration,
Co = initial uniform bulk concentration
Cx = concentration of element at
distance x from surface at time t.
x = distance from surface
D = diffusivity of diffusing species in
host lattice
t = time

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Experimental Determination of
Diffusion Coefficient
Tracer method
Radioisotopic tracer atoms are deposited at surface of solid by e.g. electro
deposition
isothermal diffusion is performed for a given time t, often quartz ampoules are
used (T<1600C)
Sample is then divided in small slices either mechanically, chemically or by
sputtering techniques
Mechanically: for diffusion length of > 10 m; D>10-11 cm2/s
Sputtering of surface: for small diffusion length (at low temperatures) 2nm
10m, for the range D = 10-21 10-12 cm2/s
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Experimental Determination of
Diffusion Coefficient
Example:
Diffusion of Fe in Fe
3
Si
From those figures the
diffusion constant can be
determined with an accuracy
of a few percent
Stable isotopes can be used
as well, when high
resolution SIMS is used
This technique is more
difficult

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Diffusion Data
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Non-Steady-State Diffusion: c(x,t)


Fic k 's S e c ond "Law ":
cc
ct
=
c
cx
D
cc
cx
|
\



|
.
|
|
|
~ D
cc
2
cx
2
|
\




|
.
|
|
|
|

C(x,t)C
0
C
s
C
0
=1erf
x
2 Dt
|
\



|
.
|
|
|
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Copper diffuses into a bar of aluminum.
10 hours processed at 600 C gives desired C(x).
How many hours needed to get the same C(x) at 500 C?
16
Result: Dt should be held constant.
Answer:
Note: values of D are
provided.
Key point 1: C(x,t
500C
) = C(x,t
600C
).
Key point 2: Both cases have the same C
o
and C
s
.
Processing Question
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17
The experiment: we recorded combinations of
t and x that kept C constant.
Diffusion depth given by:

C(x
i
, t
i
) C
o
C
s
C
o
= 1 erf
x
i
2 Dt
i
|
\


|
.
|
|
= (constant here)
Diffusion Analysis
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Non steady-state diffusion
From Ficks 1
st
Law:
dx
dc
D J =
Take the first derivative w.r.t. x:
|
.
|

\
|
=
dx
dc
D
dx
d
dx
dJ
Conservation of mass:
i.e. flux to left and to right has to correspond to concentration change.
dx
dJ
dx
J J
dt
dc
l r
=

=
Sub into the first derivative:
|
.
|

\
|
=
dx
dc
D
dx
d
dt
dc
Ficks 2
nd
law
J
r
J
l
dx
c = conc.
inside box
Partial differential equation. Well need boundary conditions to solve
In most practical cases steady-state conditions are
not established, i.e. concentration gradient is not
uniform and varies with both distance and time. Lets
derive the equation that describes non steady-state
diffusion along the direction x.
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If it is desired to achieve a specific concentration C
1

i.e.
=

o s
o
o s
o
C C
C C
C C
C t x C
1
) , (
constant
which leads to:
=
Dt
x
2
constant
Known for given system
Specified with C
1
1
1
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PROCESSING QUESTION
Copper diffuses into a bar of aluminum.
10 hours at 600C gives desired C(x).
How many hours would it take to get the same C(x)
if we processed at 500C?
Result: Dt should be held constant.
Answer:
Note: values
of D are
provided here.
Key point 1: C(x,t
500C
) = C(x,t
600C
).
Key point 2: Both cases have the same C
o
and C
s
.
Adapted from Callister 6e resource CD.
Dt 2
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Diffusivity increases with T.
Experimental Data:
D has exp. dependence on T
Recall: Vacancy does also!
(see Table 6.2 Callister 6e)
D
interstitial
>> D
substitutional
C in o-Fe
C in -Fe
Al in Al
Cu in Cu
Zn in Cu
Fe in o-Fe
Fe in -Fe
Adapted from Fig. 5.7, Callister 6e.
Diffusion and Temperature

ln D= ln D
0

Q
d
R
1
T
|
\

|
.
|
log D= log D
0

Q
d
2.3R
1
T
|
\

|
.
|
Note:
pre-exponential [m
2
/s]
activation energy
gas constant [8.31J/mol-K]
D
=
D
o
Exp

Q
d
R T
diffusivity
[J/mol],[eV/mol]
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Diffusion: Design Example
During a steel carburization process at 1000
o
C, there is a drop in
carbon concentration from 0.5 at% to 0.4 at% between 1 mm and
2 mm from the surface (g-Fe at 1000
o
C).

Estimate the flux of carbon atoms at the surface.
D
o
= 2.3 x 10
-5
m
2
/s for C diffusion in -Fe.
Q
d
= 148 kJ/mol
r
-Fe
= 7.63 g/cm
3
A
Fe
= 55.85 g/mol

If we start with C
o
= 0.2 wt% and C
s
= 1.0 wt% how long does it
take to reach 0.6 wt% at 0.75 mm from the surface for different
processing temperatures?
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T (
o
C) t (s) t (h)
300 8.5 x 10
11
2.4x10
8
900 106,400 29.6
950 57,200 15.9
1000 32,300 9.0
1050 19,000 5.3
Need to consider factors such as cost of maintaining furnace at different T for
corresponding times.
27782 yrs!
Diffusion: Design Example Contd
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- Thin Film Electronics (CMOS and Bipolar
Transistors)
Doping of Semiconductors

- Diffusion Bonding -- (Adhesives and Cements -
ceramic, metallic and polymer)
Portland Cement as Bonding for Construction
Solvents Cements for PVC Polymeric Piping
Solders and Welds for Thermocouple
Junctions

- Corrosion Protection
Galvanizing, Electroplating, Anodizing,
Inhibiting

- Gas (Chemical) Separation Processes -
Diffusion membranes

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| |
K) * J/(atom
10
1.38x = constant s Boltzmann = k
K e, temperatur absolute = T

e
y Probabilit
23 -
kT
E -
E
-
*
'
|
|
.
|

\
|

Diffusion is a RATE PROCESS IN SOLIDS

Probability of Finding an atom with energy E
*

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Fraction of atoms or molecules having energies greater
than E
*
which is itself much greater than the average
energy E.
constant = C
eV/K
10
8.62x = constant s Boltzmann = k
K e, temperatur absolute = T
system in molecules or atoms of number total =
N

E
than greater energy with atoms of number = n where

e
C =
N
n
5 -
total
*
kT
E
-
total
*
'
(

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Arrhenius' equation for the rate of many
chemical reactions
constant rate = C
K) cal/(mol 1.986 or K) * J/(mol 8.314 = constant gas molar = R
K e, temperatur absolute = T
cal/mol or J/mol energy, activation = Q where,

e
C = Reaction of Rate T R
Q
- |
.
|

\
|
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T R 2.303
Q
- C = rate

T R
Q
- C = rate
10 10
log log
ln ln
Rewritten as linear functions of the reciprocal of the
absolute temperature.

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Composition Specification
Definition: Amount of impurity (B) and host (A)
in the system.
Weight %
Two descriptions:
Atom %
Conversion between wt % and at% in an A-B alloy:
C
B
=
C'
B
A
B

C'
A
A
A
+ C'
B
A
B
x 100
Basis for conversion:
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Example problem: conversion
Determine the composition in at% of an
alloy with 80wt% Al and 20wt% Cu
A
Al
= 26.98g/mol
A
Cu
= 63.55g/mol
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Average alloy density
B A
B A
avg
V V
m m
volume total
mass total
+
+
= =
_
_

With
A
A
A
m
V

=
and
B
B
B
m
V

=
B B A A
B A
avg
m m
m m

/ / +
+
=
Usually we know concentrations rather than total mass of each component
or
100
+
=
B A
A
A
m m
m
C 100 = +
A
A
B A
C
m
m m
B B A A
avg
C C

/ /
100
+
=
Also noting that:
B
A
B
A
m
m
C
C
=
Then we have: In terms of at% C
n
B B B A A A
B B A A
avg
A C A C
A C A C

/ /
' '
' '
+
+
=
B A
B
A
A
A
B B A A
A
A
avg
m
m
C
C
m m
C
m

+
=
+
=
100
/ /
100
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Example problem: alloy density
For the alloy with the composition given below,
calculate number of Mo atoms/cm
3
.

16.4wt% Mo (atomic weight = 95.94 g/mol)
83.6wt% W (atomic weight = 183.84 g/mol)

Densities of each element:

Mo
= 10.22 g/cm
3

W
= 19.30 g/cm
3
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A Look at Diffusion Bonding
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Introduction
Diffusion bonding is a method of creating a joint between
similar or dissimilar metals, alloys, and nonmetals.

Two materials are pressed together (typically in a vacuum) at a
specific bonding pressure with a bonding temperature for a
specific holding time.

Bonding temperature
Typically 50%-70% of the melting temperature of the most
fusible metal in the composition
Raising the temperature aids in the interdiffusion of atoms
across the face of the joint.

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How does diffusion bonding
work?
Bonding pressure
Forces close contact between the edges of
the two materials being joined.
Deforms the surface asperities to fill all of the
voids within the weld zone .
Disperses oxide films on the materials,
leaving clean surfaces, which aids the
diffusion and coalescence of the joint.
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How does diffusion bonding
work?
Holding Time
Always minimized
Minimizing the time reduces the physical force on
the machinery.
Reduces cost of diffusion bonding process.
Too long of a holding time might leave voids in the
weld zone or possibly change the chemical
composition of the metal or lead to the formation of
brittle intermetallic phases when dissimilar metals
or alloys are being joined.
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How does diffusion bonding
work?
Sequence for diffusion
bonding a ceramic to a
metal
a) Hard ceramic and soft metal
edges come into contact.
b) Metal surface begins to
yield under high local stresses.
c) Deformation continues
mainly in the metal, leading to
void shrinkage.
d) The bond is formed



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Advantages of diffusion bonding
Properties of parent materials are generally unchanged.

Diffusion bonding can bond similar or dissimilar metals
and nonmetals.

The joints formed by diffusion bonding are generally of
very high quality.

The process naturally lends itself to automation.

Does not produce harmful gases, ultraviolet radiation,
metal spatter or fine dusts.

Does not require expensive solders, special grades of
wires or electrodes, fluxes or shielding gases.
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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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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
|
.
|

\
|
=

Dt
x
C C
C t x C
o s
o
2
erf 1
) , (
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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
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To solve for the
temperature at which D
has 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
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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 (t
b
), 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
cm
2
/s
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Example (cont).
Time required for breakthrough ca. 4 min
glove
C
1

C
2

skin
paint
remover
x
1
x
2

Solution assuming linear conc. gradient
D
t
b
6
2

=
Equation 22.24
cm 0.04
1 2
= = x x
D = 110 x 10
-8
cm
2
/s
min 4 s 240
/s) cm 10 x 110 )( 6 (
cm) 04 . 0 (
2 8 -
2
= = =
b
t
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Summary II
1. Diffusion is just one of many mechanisms for
mass transport.

2. Electrical field can produce mass transport.

3. Magnetic field can produce mass transport.

4. Combination of fields can produce mass
transport such as electrochemical transport.
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Application: Homogenization time
Solidification usually results in chemical
heterogeneities
Represent it with a sinusoid of wavelength,
Composition should homogenize when, x > /2
The approximate time necessary is:
Homogenization time
- increases with 2
- decreases exponentially with T
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Application:
Service Life of a Microelectronic Device
Microelectronic devices
have built-in heterogeneities
Can function only as long as these doped regions survive
To estimate the limit on service life, ts
Let doped island have dimension,
Device is dead when, x ~ /2, hence
Service life
- decreases with miniaturization (2)
- decreases exponentially with T
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Influence of Microstructure on Diffusivity
Interstitial species
Usually no effect from microstructure
Stress may enhance diffusion

Substitutional species
Raising vacancy concentration increases D
Quenching from high T
Solutes
Irradiation
Defects provide short-circuit paths
Grain boundary diffusion
Dislocation core diffusion

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Adding Vacancies Increases D
Quench from high T
Rapid cooling freezes in high cv
D decreases as cv evolves to equilibrium

Add solutes that promote vacancies
High-valence solutes in ionic solids
Mg++ increases vacancy content in Na+Cl-
Ionic conductivity increases with cMg
Large solutes in metals
Interstitials in metals

Processes that introduce vacancies directly
Irradiation
Plastic deformation
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Grain Boundary Diffusion
Grain boundaries have high defect densities
Effectively, vacancies are already present
QD ~ Qm

Grain boundaries have low cross-section
Effective width =
Areal fraction of cross-section:
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Jumps of Interstitial Atoms
Atom motion
Must overcome barrier Gm to move from site to site (~ 1eV)
Attempts with vibrational frequency e ~ 1014/sec

Number of jumps per unit time
= (# attempts/time)(probability of jump/attempt)
(of the order of 105/sec at room T)
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Jumps of Substitutional Atoms
For a Substitutional atom to jump
There must be a neighboring vacancy to permit the jump
The atom must overcome its barrier and jump
= [P(vacant site)][P(jump given vacant site)]
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Diffusion Thermally Activated
Process (I)
In order for atom to jump into a
vacancy site, it needs to posses
enough energy (thermal energy) to
break the bonds and squeeze
through its neighbors. The energy
necessary for motion, Em, is called
the activation energy for vacancy
motion.

At activation energy Em has to be
supplied to the atom so that it could
break inter-atomic bonds and to
move into the new position.
Schematic representation of the
diffusion of an atom from its original
position into a vacant lattice site.
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Diffusion Thermally Activated
Process (II)
The average thermal energy of an atom (kBT = 0.026 eV for room
temperature) is usually much smaller that the activation energy
Em (~ 1 eV/atom) and a large fluctuation in energy (when the
energy is pooled together in a small volume) is needed for a
jump.

The probability of such fluctuation or frequency of jumps, Rj,
depends exponentially from temperature and can be described by
equation that is attributed to Swedish chemist
Arrhenius :


where R0 is an attempt frequency proportional to the frequency of
atomic vibrations.
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Diffusion Thermally Activated Process (III)
For the vacancy diffusion mechanism the probability for any atom in a solid to
move is the product of the probability of finding a vacancy in an adjacent
lattice site (see Chapter 4):

and the probability of thermal fluctuation needed to overcome the
energy barrier for vacancy motion
The diffusion coefficient, therefore, can be estimated as
Temperature dependence of the diffusion coefficient, follows the Arrhenius
dependence.
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Diffusion Temperature Dependence (I)
Diffusion coefficient is the measure of
mobility of diffusing species.
D
0
temperature-independent preexponential (m2/s)
Q
d
the activation energy for diffusion (J/mol or eV/atom)
R the gas constant (8.31 J/mol-K or 8.62x10
5
/atom-K
T absolute temperature (K)

The above equation can be rewritten as
The activation energy Q
d
and preexponential D
0
, therefore, can be estimated by
plotting lnD versus 1/T or logD versus 1/T. Such plots are Arrhenius plots.
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Diffusion Temperature Dependence (II)
Graph of log D vs. 1/T has
slop of Q
d
/2.3R, intercept
of ln D
o
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Diffusion Temperature Dependence (III)
Arrhenius plot of diffusivity data for some metallic systems
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Diffusion of different species
Smaller atoms diffuse more readily than big ones, and diffusion is
faster in open lattices or in open directions
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Diffusion: Role of the microstructure (I)
Self-diffusion coefficients
for Ag depend on the
diffusion path.

In general, the diffusivity is
greater through less
restrictive structural regions
grain boundaries,
dislocation cores, external
surfaces.
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Diffusion: Role of the
microstructure (II)
The plots (opposite) are from the computer
simulation by T. Kwok, P. S. Ho, and S. Yip.

Initial atomic positions are shown by the
circles, trajectories of atoms are shown by
lines.

We can see the difference between atomic
mobility in the bulk crystal and in the grain
boundary region.
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Exercise
1. A thick slab of graphite is in contact with a 1mm thick sheet of
steel. Carbon steadily diffuses through the steel at 925C. The carbon
reaching the free surface reacts with CO
2
gas to form CO, which is
then rapidly pumped away.

Determine the carbon concentration, C
2
, adjacent to the free surface,
and the find the carbon flux in the steel, given that the reaction
velocity for C+CO
2
2CO is o=3.010
-6
cm/sec.

At 925C, the solubility of carbon in the steel in contact with
graphite is 1.5wt% and the diffusivity of carbon through steel is
D=1.710
-7
cm
2
/sec. The equilibrium solubility of carbon in steel,
C
eq
, is 0.1wt% for the CO/CO
2
ratio established at the surface of the
steel.

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Exercise
Pe =
ol
D
=1.76
The Pclet number is
Note: The value of the Pclet number suggests mixed kinetic behavior is expected.
C
2
= C
eq
+
C
0
C
eq
1+
o l
D
= 0.1+
1.5 0.1
1+1.76
, [wt%]
C
2
= 0.61wt%.
The carbon concentration in
the steel at the free surface,
C
2
, is

The steady-state flux is
J
ss
= 1.51 10
-6
[wt% C cm/s]
J
ss
= 1.18 10
-7
[g/ cm
2
-s]
Divide by the density of steel, =12.8 cm
3
/100g to obtain the steady-state flux of
carbon



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Exercise
2. Two steel billetsa slab and a solid cylindercontain 5000ppm
residual H
2
gas. These billets are vacuum annealed in a furnace at
725C for 24 hours to reduce the gas content. Vacuum annealing is
capable of maintaining a surface concentration in the steel of
10ppm H
2
at the annealing temperature.

Estimate the average residual concentration of H
2
in each billet
after vacuum annealing, given that the diffusivity of H in steel at
725C is D
H
=2.2510
- 4
cm
2
/sec.
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Exercise
1
5

c
m
2
h
=
1
0

c
m
2h=10 cm
1
5

c
m
10 cm
2h = 10 cm
2
h

=

1
0

c
m

Rectangular and cylindrical slabs of steel
10 cm
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Solution in the Class
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Given:
t=24 hr=86400 s
C
o
= Initial Concentration= 5000 ppm
C
s
= Surface concentration= 10 ppm
D
H
= 2.25x10-4 cm2/s
C
1
= average residual concentration=?
We know that:
(C
1
-C
o
) / (C
s
-C
o
) = Constant(z) and also
X \(Dt) or x = Constant x \(Dt)
or Constant(z) = (Dt) / x
2
Now we can write:
(C
1
-C
o
) / (C
s
-C
o
) = (Dt) / x
2
or C1= (C
o
-C
s
) x (f) + C
s

Therefore,
For slab:
C1= (C
o
-C
s
) x (f
long
x f
short
x f
short
) + C
s
and
For Cylinder:
C1= (C
o
-C
s
) x (f
long
x f
short
) + C
s
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STRUCTURE & DIFFUSION
Diffusion FASTER for...

open crystal structures

lower melting T materials

materials with secondary
bonding

smaller diffusing atoms

lower density materials
Diffusion SLOWER for...

close-packed structures

higher melting T materials

materials with covalent
bonding

larger diffusing atoms

higher density materials
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Factors that Influence Diffusion:
Summary
" Temperature - diffusion rate increases very rapidly with
increasing temperature
" Diffusion mechanism - interstitial is usually faster
than vacancy
" Diffusing and host species - D
o
, Q
d
is different for
every solute, solvent pair
" Microstructure - diffusion faster in polycrystalline vs.
single crystal materials because of the accelerated diffusion
along grain boundaries and dislocation cores.
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Concepts to remember
Diffusion mechanisms and phenomena.
Vacancy diffusion.
Interstitial diffusion.
Importance/usefulness of understanding
diffusion (especially in processing).
Steady-state diffusion.
Non steady-state diffusion.
Temperature dependence.
Structural dependence (e.g. size of the diffusing
atoms, bonding type, crystal structure etc.).
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Summary
" Activation energy
" Concentration gradient
" Diffusion
" Diffusion coefficient
" Diffusion flux
" Vacancy diffusion
Make sure you understand language and concepts:
" Driving force
" Ficks first and second laws
" Interdiffusion
" Interstitial diffusion
" Self-diffusion
" Steady-state diffusion
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Next Class


Nucleation and Growth Kinetics