MECH2272 Diffusion
Diffusion
The Figures used in these slides are taken from:
Materials Science and Engineering: An Introduction
by
William D. Callister, Jr.
David G. Rethwisch
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
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 structure
and temperature?
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 2
MECH2272 Diffusion
Diffusion
Diffusion - Mass transport by atomic motion
Example: salt in water
• Why is diffusion an important part of processing?
Example: Heat treatment and doping
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 3
MECH2272 Diffusion
Diffusion in solids
When two metals that are coupled together are heated for an extend period at
elevated temperature (below melting point), diffusion of atoms across the
interface will occur as shown in the figure below
In an alloy, atoms tend to migrate from regions of high conc. to regions of low
conc.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Interdiffusion: The process whereby the atoms of one metal diffuse
into another is called interdiffusion or impurity diffusion.
Copper-Nickel diffusion couple
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
• Self-diffusion: In an elemental solid, atoms also migrate.
Label some atoms After some time
C
C
A D
A
D
B
B
Question: how can atoms change positions in a crystal?
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 6
MECH2272 Diffusion
Diffusion Mechanisms
For atoms to change position by diffusion the following conditions
must be met:
a. there must be an empty adjacent site
b. the atom must have sufficient energy to break bonds with
neighboring atoms
Recall: atomic vibrations
The common mechanisms for explaining diffusion of atoms are
a. vacancy diffusion – atoms moving from one regular lattice
position to another.
b. interstitial diffusion - atoms moving from one interstitial
position to another
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.
increasing elapsed time
-Q v
N N exp
v
RT
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 8
MECH2272 Diffusion
Interstitial diffusion
Migration of atoms from an interstitial position to a neighboring
interstitial position that is empty.
Found in inter-diffusion of impurities such as hydrogen, carbon,
nitrogen and oxygen, which are so small that they can occupy
interstitial positions
Adapted from Fig. 5.3(b),
Callister & Rethwisch 8e.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Question: which one is faster, vacancy or
interstitial diffusion?
Interstitial atoms are smaller and more mobile
There are more empty interstitial position than
vacancies.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Processing Using Diffusion
• Case Hardening:
-- Diffuse carbon atoms Adapted from
chapter-opening
into the host iron atoms photograph,
Chapter 5, Callister
at the surface. & Rethwisch 8e.
(Courtesy of
Surface Division,
Midland-Ross.)
• Result: The presence of C
atoms makes iron (steel) harder.
For Carbon in Iron:
Question 1: What is the impurity type?
A: Substitutional
B: Interstitial
Question 2: What is the diffusion mechanism?
A: Vacancy diffusion
B: Interstitial diffusion
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 11
MECH2272 Diffusion
Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process:
1. Deposit P rich
layers on surface.
For Phosphorus in Silicon:
silicon Question 1: What is the impurity type?
A: Substitutional
2. Heat it. B: Interstitial
Question 2: What is the diffusion mechanism?
3. Result: Doped
A: Vacancy diffusion
semiconductor B: Interstitial diffusion
regions.
silicon
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 12
MECH2272 Diffusion
Quantification of Diffusion
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Diffusion flux
• How do we quantify the amount or rate of diffusion?
moles (or mass) diffusing mol kg
J Flux or
surface area time cm
2
s m s
2
Diffusion is time dependent, i.e. the amount of atoms that diffuse across a
cross-section is a function of time.
The rate of atoms transfer across a cross-sectional area is termed
diffusion flux
Diffusion Flux (J) can be defined as the mass or number of atoms
diffusing (M) through a perpendicular cross-sectional unit area of solid
per unit time.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Mathematically,
M
J
At
A = cross section area across which diffusion occurs
t = diffusion time
In differential form
1 dM
J
A dt
Units of J = kg/m2-s or atoms/m2-s
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Steady-State Diffusion
If the diffusion flux does not change with time, diffusion is said to steady-state
diffusion.
A typical example of steady-state diffusion is the diffusion of gas atoms through a plate
of metal in which the pressures or concentrations on both surfaces of the plate are held
constant.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
A plot of concentration against distance
gives the concentration profile
The slope of concentration profile is the
concentration gradient
Concentration gradient = dC/dx
Concentration is expressed in mass of
diffusing species per unit volume of solid
(kg/m3 or g/cm3)
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Steady-State Diffusion
1 dM
J
A dt
• Diffusion flux does not change with time
• Concentration profile is linear
• Concentration gradient is constant
C CB -CA
Concentrat ion gradient
x xB -x A
Any correlation between J and
concentration gradient?
Hint: electric current and voltage
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Fick’s Laws of Diffusion
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Fick’s First Law
For one dimensional steady-state diffusion in direction (x) the
diffusion flux (J) is proportional to the concentration gradient:
dC
J - D
dx
The negative sign shows that the direction of the flux is down the
concentration gradient.
D is constant of proportionality called diffusion coefficient
or diffusivity.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Example 1:
A plate of iron is exposed to a carburizing (carbon-rich)
atmosphere on one side and a decarburizing (carbon-
deficient) atmosphere on the other side at 700 C. If a
condition of steady-state is achieved, calculate the
diffusion flux of carbon through the plate if concentrations
of carbon at position of 5 and 10 mm beneath the
carburizing surface are 1.2 and 0.8 kg/m3, respectively.
Assume a diffusion coefficient of 3 x 10-11 m2/s at this
temperature.
dC
J - D
dx
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Data: D = 3 x 10-11 m2/s
CA = 0.44 g/cm3
Iron plate
C1 CB = 0.02 g/cm3
2
t
Carbon-
6D
b xB – xA = 0.04 cm
Carbon-
rich deficient
C2 C C
J D
B A
xA xB x B
x A
( 0 . 8 1 . 2 ) kg / m
3
11
( 3 10
2
m / s) 2 3
(10 5 10 )m
9
2 . 4 10
2
kg / m s
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
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]
T = absolute temperature [K]
Question: how activation energy can be determined if diffusivity at
a particular temperature can be determined?
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 23
MECH2272 Diffusion
Diffusion and Temperature
D has exponential dependence on T
1500
1000
600
300
T(C)
10-8
D (m2/s) Dinterstitial >> Dsubstitutional
C in a-Fe (BCC) Al in Al
10-14 C in g-Fe (FCC) Fe in a-Fe
Fe in g-Fe
Question: why C in a-Fe > C in g-Fe ?
10-20
0.5 1.0 1.5 1000 K/T
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.)
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 24
MECH2272 Diffusion
In-class discussion: Determine the activation energy for diffusion if the
diffusivities are D1 at T1 and D2 at T2.
Qd
D Do exp
RT
D transform ln D
data
Temp = T 1/T
Qd 1 Qd 1
ln D 2 ln D 0 and ln D 1 ln D 0
R T2 R T1
D2 Qd 1 1
ln D 2 ln D 1 ln
D1 R T2 T1
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 25
MECH2272 Diffusion
Example: At 300ºC the diffusion coefficient and activation energy for Cu in
Si are
Qd
D Do exp
D(300ºC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol RT
What is the diffusion coefficient at 350ºC?
D transform ln D
data
Temp = T 1/T
Qd 1 Qd 1
ln D 2 ln D 0 and ln D 1 ln D 0
R T2 R T1
D2 Qd 1 1
ln D 2 ln D 1 ln
D1 R T2 T1
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 26
MECH2272 Diffusion
Example (cont.)
Q 1 1
D2 D 1 exp
d
R T
2 T 1
T1 = 273 + 300 = 573 K
T2 = 273 + 350 = 623 K
11 2 41 ,500 J/mol 1 1
D 2 ( 7 . 8 x 10 m /s) exp
8 . 314 J/mol - K 623 K 573 K
D2 = 15.7 x 10-11 m2/s
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 27
MECH2272 Diffusion
Non-steady State Diffusion
In non steady-state diffusion, the diffusion flux changes with time.
This results in non-linear concentration profile with varying
concentration gradient
Cs
Adapted from
Fig. 5.5, Callister
& Rethwisch 8e.
It is the common type encountered in practice
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 28
MECH2272 Diffusion
Under nonsteady-state condition,
C(x, t) C(x, t)
D
t x x
This expression is known as Fick’s Second Law
If D is independent of composition, the equation simplifies to
C
2
C
D
t x
2
There are lots of analytical solutions to this
differential equation depending on the type of
boundary conditions.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Example of Analytical Solution of Ficks Second Law Equation:
Consider a semi-infinite solid in which surface concentration is held constant at
Cs and assuming that:
a. The diffusing atoms in the solid before diffusion are uniformly distributed with
concentration Co.
b. The value of x at the surface is zero and increases with distance into the solid.
c. Time is taken to be zero at the instant before the start of diffusion process
• Copper diffuses into a bar of aluminum.
Surface conc.,
C s of Cu atoms bar
pre-existing conc., Co of copper atoms
For t = 0, C = Co at 0 x
For t > 0, C = Cs (the constant surface concentration) at x = 0
C = Co at x =
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Solution:
C x ,t C o x
1 erf
Cs Co 2 Dt
C(x,t) = Conc. at point x at CS
time t
erf (z) = error function
2 z
y
2 C(x,t)
0
e dy
Co
erf(z) values are given in Table
5.1
Adapted from Fig. 5.5,
Callister & Rethwisch 8e.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed. 31
MECH2272 Diffusion
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Error function: erf(X)
http://en.wikipedia.org/wiki/Error_function
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Example 2
Consider a steel alloy that initially has a uniform carbon
concentration of 0.25 wt % and is to be heated 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 temperature is 1.6 x 10-11 m2/s:
assume that the steel piece is semi-infinite.
C x, t
- C o x
1 - erf
C s
C o 2 Dt
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
C - C x
1 - erf
x o
C s
C o 2 Dt
C C 0 . 80 0 . 25 5 10
4
m
1 erf
x 0
C C 1 . 20 0 . 25 2 (1 . 6 10
11
m
2
/ s )( t )
s 0
1
62.5 s 2
0.4210 erf
t
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
1
62.5 s 2
0.4210 erf
t
Linear interpolation
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
1
62.5 s 2
0.392
t
t 25,400 s 7.1 hrs
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
MECH2272 Diffusion
Other Diffusion Paths
Migration of atoms can occur along: dislocations, grain boundaries
and external surfaces.
These diffusion paths are called short-circuit diffusion paths
because of accelerated rate of diffusion associated with them.
As a result of their small cross-sectional areas, compared to the
bulk lattice, the contributions of these paths to total diffusion can
be small, even though the rates of diffusion along them are rapid.
Ref: Materials Science and Engineering: An Introduction by William D. Callister, Jr. and David G. Rethwisch, 8th Ed.
