Diffusion

A process of mass transport

Involves the movement of one atomic species

into another

Occurs by random atomic jumps from one

position to another

Material transport by atomic motion

Dependent on (directly proportional to)

- Temperature
- Concentration gradient

Leads to improved homogeneity in materials

- Inhomogeneous materials can become
homogeneous by diffusion

Takes place in gaseous, liquid and solid states

for all classes of materials

Diffusion

Smaller atoms diffuse more readily than

bigger ones

Diffusion is faster in open lattices or in

open directions

Diffusivity greater through less restrictive

structural regions grain boundaries,
dislocation cores, external surfaces etc.

Before diffusion

After diffusion

 Diffusion faster in
- Open crystal structures

Materials with secondary bonding

Smaller diffusing atoms

Lower density materials

Diffusion slower in
- Close-packed structures
- Materials with covalent bonding
- Larger diffusing atoms
- Higher density materials

Examples/applications

Adding dye
Mixing

Homogenization

Time

IN LIQUIDS: ink in water, etc.

Diffusion in gases
- Swamp gas in air, exhaust fumes into smog

Diffusion: Examples/Applications

Alloy making

The interdiffusion of materials on an atomic scale

Process path showing how an atom must

overcome an activation energy, q, to move from
one stable position to a similar adjacent position
- This Activation Energy barrier that determines the
Rate Limiting Step in any process

Diffusion Mechanisms

Atoms move from the regions higher

concentration to the less concentrated regions
Two main mechanisms of diffusion of atoms
in a crystalline lattice
-

Vacancy or substitutional mechanism

Interstitial mechanism

Diffusion in materials occurs by both mechanisms

vacancy migration and randomly moving
interstitials

Vacancy Mechanism

Vacancy diffusion
-

To jump from one lattice site to the other,

atoms need energy to

--

Break bonds with neighbors

--

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 to the

vacancy flow direction

Vacancy Diffusion
Atomic migration (Diffusion) occurs by a mechanism
of vacancy migration. Note that the overall direction of
material flow (the atom) is opposite to the direction of
vacancy flow

Note: Diffusion is faster

at higher temperature
since more vacancies
will exist in the lattice!
Exchange of position
between a vacancy and
the neighbouring atom

Interdiffusion of Materials A and B

Although any given A or B atom

in a mixture/solution is equally
likely to walk in any random
direction, the concentration
gradients of the two materials
can result in a net flow of A
atoms into the B material, and
vice versa

Interstitial Diffusion

Interstitial diffusion generally faster than

vacancy diffusion because

- Bonding of interstitials to the surrounding

atoms is normally weaker
- There are many more interstitial sites than
vacancy sites to jump to

Requires small impurity atoms (e.g. C, H, O)

to fit into interstices in host.

Interstitial Diffusion

Diffusion by an interstitialcy mechanism

illustrates the random-walk nature of atomic
migration

- Faster as temperature increases

Position of an
interstitial atom

Position of interstitial
after diffusion

Examples/applications

Diffusion in solids
- Alloy preparation
- Heat treatment (phase transformation,
homogenization)
- Surface treatment
- Material synthesis

Carburization

Surface coating

Schematic illustration of how a coating of impurity B can

penetrate more deeply into grain boundaries and even further
along a free surface of polycrystalline A, consistent with the
relative values of diffusion coefficients
(Dvolume < Dgrain boundary < Dsurface)

The mode of distribution

of the diffusing element
is determined mainly by
the diffusion temperature
and time, and concentration
decreases monotonically
from the surface

- Maximum concentration of
a particular diffusing
impurity always at the
surface

Diffusion Flux
The flux of diffusing atoms
Used to quantify how fast diffusion occurs
Defined as
- The number of atoms diffusing through per
unit area per unit time (Atoms/m2-second)
- The mass flux (mass of atoms) diffusing
through unit area per unit time, (kg/m2-sec).
J = M/A.t = 1/A (M/t)
where J: the diffusion flux, M: the mass of atoms
diffusing through the area A during time t

Modes of Diffusion

Steady state of diffusion

Non- steady state of diffusion

Steady-State Diffusion

Flux does not change with time

Concentration is expressed in terms of mass of
diffusing species per unit volume of solid
(kg/m3 or atoms/m3)
Concentration gradient is defined as mass per
unit volume per unit distance (kg/m3-m) i.e.
kg/m2
Flux is proportional to the concentration
gradient i.e. J C/x
(Final Initial) is -ve
- Stated by Ficks first law
J = - D. C/x
- Negative sign indicates direction of gradient
-- higher (initial) to lower (final) concentration
- It is the driving force
- Proportionality const D is termed diffusion
coefficient or diffusivity having unit m2/s

Ficks First Law of Diffusion

Thin metal plate

Gas
pressure
PB

PA: constant
Gas
pressure
PA

Direction of
diffusion

Surfae area of
diffusion: A

C/x = (CB-CA)/(XB-XA)
J = -D (dC/dX)

Diffusing species Concentration

PA >PB

Quantifying Diffusion: Ficks First Law is a

statement of Material Flux across a Barrier

moles (or mass) diffusing

mol
kg
J Flux

or
2
surface area time
cm s m2s

Fe
plate

Factors Controlling Diffusivity

Type of bonding

Diffusion mechanism
- Substitutional vs interstitial

Temperature
- Higher diffusivity with increasing temperature
Type of crystal structure of the host lattice

- Interstitial diffusion easier in BCC than in FCC

Type of crystal imperfections

- Diffusion takes place faster along grain
boundaries than elsewhere in a crystal
- Diffusion is faster along dislocation lines
than through bulk crystal
- Excess vacancies will enhance diffusion

Concentration gradient of the diffusing species

The migration of grain boundary under the

influence of preferential solute diffusion along
it is termed as diffusion induced grain boundary
migration (DIGM).

Diffusion and Temperature

Diffusion coefficient seen in Ficks Laws increases
with increasing T and, along with vacancy
formation, is a Classic Arrhenius Model:

D = Do e(-Q/RT)
D = diffusion coefficient [m2/s]
Do = pre-exponential [m2/s]
Qd = activation energy for diffusion [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

Diffusion Coefficient, cm2/s

Reciprocal Temperature, oC

Reciprocal Temperature, 1000/K

Diffusion coefficient
Diffusing
species

Host
Metal

Do(m2/s)

Activation energy, Q
kJ/mole
eV/atom

Calculated D values
Temp,oC

D (m2/s)

Arrhenius plot of the diffusivity of carbon in -iron

over a range of temperatures

Arrhenius plot of diffusivity data for a number of metallic

systems

Similar Data also exists for Ionic (and Organic) Compounds:

And in a Tabular Form:

Non Steady State Diffusion

Diffusion flux and the concentration gradient at
some particular point in a solid vary with time,
with a net accumulation or depletion of the
diffusing species

Concentration of diffusing species

Ficks second law applies (when D is

independent of composition)

t1<t2<t3
t3
t1

t2

Distance

Practical Implications of Diffusion

Solutions to the diffusion equations are possible

when physically meaningful boundary conditions
are specified

Particularly important solution semi-infinite

solid in which surface concentrations are
constant, diffusing species is usually a gas and
the partial pressure is maintained at a constant
value

This solution applies to gas diffusion into a

solid as in case hardening (carburization of
steels), impurity doping of semiconductors,
surafce coating etc.

Ficks 2nd Law of Diffusion

The rate of change of the number of atoms in the

slice of volume dV
= (The rate of entry of atoms in the slice) (the
rate of atoms leaving the slice)

Ficks 2nd Law of Diffusion

The rate of change of composition (concentration

of element) at any 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 (Cx/x), with respect to
the distance (x)

Ficks Second Law is a statement of

Concentration Variation over time across a
Barrier
cx cx

D
t x x
in the usual case where D is
independent of Concentration

cx
2 cx
D 2
t
u

Solution to Ficks second law for the case of a semi-infinite solid,

constant surface concentration of the diffusing species cs , initial bulk
concentration c0 , and a constant diffusion coefficient, D

 The impurity concentration C(x,t) as a function

of depth below the surface, x, and
diffusion time, t, is determined from Ficks 2nd
law of diffusion

Non-steady State Diffusion

Copper diffuses into a bar of aluminum.
Surface conc.,
bar
C s of Cu atoms
pre-existing conc., Co of copper atoms
Cs

The concentration decreases at

increasing x (from surface) while it
increases at a given x as time increases!

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

Boundary Conditions
For t = 0, C = Co at 0 < x
For t > 0, C = CS at x = 0

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
erf = error function = erf[(x/2(Dt)] is the
Gaussian error function this is like a continuous
probability density function from 0 to x/2(Dt)

The equation demonstrates the relationship

between concentration, position, and time

Cx being a function of the dimensionless

parameter x/2(Dt) may be determined at
any time and position if parameters Co, Cs
and D are known

Mathematical Solution:
C x ,t Co
x
1 erf

Cs Co
2 Dt

CS

C(x,t)

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

erf (z) = error function

z
0

y 2

dy

Co

Copper diffuses into aluminum

Effective penetration distance

In general, for most diffusion problems
xeff=
where : a geometry-dependent parameter
= 1 for a flat plate
= 2 for cylinders

One practically important solution is for a semi-infinite solid (as

illustrated in the previous graph) in which the surface
concentration is held constant. Frequently source of the
diffusing species is a gas phase, which is maintained at a constant
pressure value.
A bar of length l is considered to be semi-infinite when:

l 10 Dt
The following assumptions are implied for a good solution:
1.

Before diffusion, any of the diffusing solute atoms in the solid are
uniformly distributed with concentration of C0.

2.

The value of x (position in the solid) is taken as zero at the surface

and increases with distance into the solid.

3.

The time is taken to be zero the instant before the diffusion process
begins.

Similar F.S.L. Diffusion Studies have been documented for

other than Semi-Infinite Solids:

The parameter cm is the average concentration of diffusing species

within the sample. Again, the surface concentration, cs , and diffusion
coefficient, D, are assumed to be constant.

Example
The carburization of a steel gear at a temperature of 1000oC in gaseous CO/CO2 mixture,
took 10 hours. How long will take to carburize the steel gear to attain similar
concentration conditions at 1200oC? For C in iron, D = 0.2 exp{ -34000 / 2T} cm2/s

Processing Using Diffusion

Case Hardening
- Diffuse carbon atoms
into the host iron atoms at
the surface
- Example of interstitial
diffusion to produce a surface
(case) hardened gear The
- Carbon atoms (interstitially)
diffuse from a carbon rich
atmosphere into the steel
through the surface
- The presence of C atoms makes the iron
(steel) surface harder

Example: (Ficks2nd Law)

Determine the time it takes to obtain a carbon
concentration of 0.24%at depth 0.01cm beneath the
surface of an iron bar at 1000oC. The initial concentration
of carbon in the iron bar is 0.20% and the surface
concentration is maintained at 0.40%.
The Fe has FCC structure and the diffusion coefficient is

Known: T=1000oC, depth x = 0.01cm, CX= 0.24%,

CO = 0.2%,CS = 0.4%, R = 8.314 J/K
Find: time t =?

(B) The diffusion coefficients for copper in aluminum at 500

and 600oC are 4.8x10-14 and 5.3x10-13 m2s-1, respectively.
Determine the approximate time at 500oC that will
produce the same diffusion results (in terms of
concentration of Cu at some specific point in Al) as a 10
hour heat treatment at 600oC.
Solution:
Ficks second law, as it is desired to achieve some specific
concentration conditions.

(C) For the problem (B) compute the activation energy for the
diffusion of Cu in Al.

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 (Cs ) 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 the following equation

C( x, t ) Co
x
1 erf

Cs Co
2 Dt

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 )
C s Co
1.0 0.20
2 Dt
0.1875 1 erf ( z )
erf ( z ) 0.8125
erf(z) = 0.8125

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 By LINEAR Interpolation:

z 0.90
0.8125 0.7970

0.95 0.90 0.8209 0.7970

z 0.93
And now solve for D:

x
z
2 Dt

x2
4z 2t

3
2
x2
(
4
x
10
m)
1h

2.6 x 10 11 m2 /s
4z 2t ( 4)(0.93 )2 ( 49 .5 h) 3600 s

The solution requires the use of the erf function which was
developed to model conduction along a semi-infinite rod

Now, Returning to the Solution to our Carburizing problem:

To solve for the temperature at which D has

above value, we use a rearranged the D
(Arrhenius) Equation:

Qd
T
R(lnDo lnD )

142,000 J/mol
T
(8.314 J/mol- K)(ln 2.0x105 ln 2.6x1011 )
142,000 J/mol
142,000 J/mol
T

(8.314 J/mol- K)(13.553) 112.681 J/mol- K

T 1260.2 K 987 C

Following Up:
In industry one may wish to speed up this
process
This can be accomplished by increasing:
Temperature of the process
Surface concentration of the diffusing species

If we choose to increase the temperature,

determine how long it will take to reach the
same concentration at the same depth as in the
previous study?

Diffusion time calculation:

Given target X (depth of case) and concentration are equal:
Here we known that D*t is a constant for the diffusion process (where D is a
function of temperature)

D1260 was 2.6x10-11m2/s at 987C while the process took 49.5 hours
How long will it take if the temperature is increased to 1250 C?

D1250C D0e

QD

142000

RT

2.0 10 e

8.311523

D1250C 2.0 10 1.341 10 2.68 10

D1250C t1250C D1027 C t1027 C t1250 C
t1250C

2.6 1011 49.5hr

4.8 hr
10
2.68 10

10

m2

D987 C t987 C
D1250C

Considering a First Law or Steady-State Diffusion

Case
Here, The Rate of diffusion is independent of time
dC
Flux is proportional to concentration gradient =
dx

Note, steady state diffusion concentration gradient ( dC/dx) is linear

C1 C1

C2
x1

C2

dC
J D
dx
D is the diffusion coefficient

x2

dC C C2 C1
if Behavior is linear

dx x
x2 x1

F.F.L. Example: Chemical Protective Clothing

(CPC)
Methylene chloride is a common ingredient in 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 of MeChl in butyl rubber: D = 110 x10-8 cm2/s
surface concentrations:

C1 = 0.44 g/cm3 (outside surface)

C2 = 0.02 g/cm3(inside surface)

Example (cont).
J -D

glove
C1
paint
remover

tb

2
6D

skin

Data:

C2
x1 x2

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 = X = 0.04 cm

-8

J (110 x 10

(0.02 g/cm3 0.44 g/cm3 )

g
cm /s)
1.16 x 10-5
(0.04 cm)
cm2s
2

What happens to a Worker?

If a person is in contact with the irritant and more than about 0.5 gm of the

irritant is deposited on their skin they need to take a wash break

If 25 cm2 of glove is in the paint thinner can, How Long will it take before

they must take a wash break?

Flux 1.16 105 g

cm -s

if the exposed area of the gloves are 25 cm

how long will it take to get 0.5g of M-C onto the hands?
Flux

25cm 2 1.16 10 5 g

Exposure time= 0.5g

cm -s

2.9 104 g

2.9 10 g

1724s 0.48 hr

Another Example: Chemical Protective

Clothing (CPC)
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 (at all)?
Data: diffusion coefficient of Me-Chl in butyl
rubber
D = 110 x10-8 cm2/s (as earlier)

Example 3 (cont).
Solution assuming linear conc. gradient
glove

2
tb
6D

C1
paint
remover

skin
C2

x1 x2
x2 x1 0.04 cm
tb

D = 110 x 10-8 cm2/s

(0.04 cm)2
-8

(6)(110 x 10

240 s 4 min

cm /s)

Time before breakthrough is circa. 4 min

Self-diffusion coefficients for silver (and other materials in other

metals) depend on the diffusion path. In general, diffusivity is greater
through less-restrictive structural regions. (From J. H. Brophy, R. M.
Rose, and J. Wulff, The Structure and Properties of Materials, Vol. 2:
Thermodynamics of Structure, John Wiley & Sons, Inc., New York,
1964.)

While shown for

self-diffusion
this type of
diffusing behavior
is typical Areas
high in vacancies
are ones where
diffusion occurs at
a faster rate!

Generation of Point Defects

Point defects are caused by:
1. Thermal energy

Example: If, at 400oC, the concentration of vacancies in aluminum is 2.3 x 10-5, what is
the excess concentration of vacancies if the aluminum is quenched from 600oC to room
temperature? What is the number of vacancies in one cubic m of quenched aluminum?
Given, Es= 0.62 eV; k = 86.2 x 10-6eV/K, ; rAl= 0.143 nm

Typical Arrhenius plot of data compared with

Equation 5.2. This behavior controls most
molecular movement driven behavior (like
vacancy formation or diffusion). The slope
equals Q/R, and the intercept (at 1/T = 0) is
ln(C)

rate Ce

Q
RT

where:
C is a constant (rate w/o temperature)
Q is activation energy
T is absolute temperature

Note: this is a Semi-log

plot

The overall thermal expansion (L/L) of aluminum is measurably greater than

the lattice parameter expansion (a/a) at high temperatures because vacancies
are produced by thermal agitation (a). A semilog (Arrhenius-type) plot of
ln(vacancy concentration)

(b) versus 1/T based on the data of part (a). The slope of the plot (Ev/k)
indicates that 0.76 eV of energy is required to create a single vacancy in
the aluminum crystal structure. (From P. G. Shewmon, Diffusion in Solids,
McGraw-Hill Book Company, New York, 1963.)

Thermal Diffusion of Impurities into Silicon

The ability to modify the properties of a
semiconductor through the addition of
controlled amounts of impurity atoms is an
important aspect of silicon device and IC
manufacture
There are two principal methods to introduce
impurities into silicon, thermal diffusion and
ion implantation

Thermal diffusion is a high temperature

process where the dopant atoms are deposited
on to or near the surface of the wafer from the
gas phase

(A) For an ASTM grain size of 6, approximately

how many grains would there be per square
inch at a magnification of 100?
Soln.

This problem asks that we compute the

number of grains per square inch for an ASTM
grain size of 6 at a magnification of 100x. All
we need to do is solve for the parameter N in
the equation below, in as much as n= 6. Thus
N=2 n1= 261= 32 grains/in2