Engineering Materials

Chapter: 6
DIFFUSION

Engineering Materials
Learning Objectives
After studying this chapter you should be able to do the
following:
Name and describe the two atomic mechanisms of
diffusion. Indicate which type of diffusion occurs more
rapidly, and then explain why this is so.
Distinguish between steady-state and non-steady state
diffusion.
(a) Write Ficks first and second laws in equation form,
and define all parameters. (b) Note the kind of diffusion
for which each of these equations is normally applied.
Define all parameters of Ficks second law for diffusion.
Calculate the diffusion coefficient for some material at a
specified temperature, given the appropriate diffusion
constants.
Give a brief definition of diffusion.

Engineering Materials
Explain the terms interdiffusion and self-diffusion.
Given the mass of material diffusing through a cross-sectional
area over a specified time period, compute the diffusion flux.
Define the terms concentration profile and concentration
gradient.
For steady-state diffusion through a metal sheet, determine the
diffusion flux given values for the diffusion coefficient, the
sheet thickness, and the concentrations of diffusing species at
both surfaces.
Cite the driving force for steady-state diffusion.
Cite two factors that influence diffusion rate (i.e., the
magnitude of the diffusion coefficient).
Given the pre-exponential, Do, the activation energy, the
absolute temperature, and the gas constant, be able to compute
the value of the diffusion coefficient.

Engineering Materials

Diffusion

Diffusion
What is diffusion?
Diffusion is material
transport by atomic
motion.
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.

Why study diffusion?

Answer: to improve

properties of materials.

Industrial Applications of Diffusion

Processes: Case Hardening

Desirable properties of sliding parts (e.g. gears and shafts): soft core for high
fracture toughness; and hard surface for better wear resistance.
Solution:
Enriching carbon content at the surface by
diffusion carburizing

Industrial Applications of
Diffusion Processes: Gas Purification

Another application of diffusion is in the purification of hydrogen gas.

As shown below, a thin sheet of palladium metal separates the two gases.
On one side is a gas composed of hydrogen plus (for example) nitrogen,
oxygen, or water vapour. From this, the hydrogen selectively diffuses
through the sheet to the other side, which has been kept at a constant,
lower hydrogen pressure

Industrial Applications of
Diffusion Processes: Doping of Silicon Wafers

Electrical conductivity of silicon is changed by impurity atoms.

Silicon wafers are placed in a tube furnace exposed to impurity gas.

Industrial Applications of Diffusion

Processes: Hot dip galvanizing

The steel is immersed in molten zinc (temp 4500C)

The clean steel surface reacts with the molten zinc to form a zinc-iron alloy
which is very strongly bonded to the surface
The hot dip galvanized coating forms in 3-5 minutes, depending on the steel
thickness

Galvanized coating

Steel

Examples of diffusion
A balloon filled with helium will deflate a little bit every
day, because helium atoms diffuse out of the balloon
through its wall
When spaghetti is cooked, water molecules diffuse into
the spaghetti strings, making them thicker and more
flexible.
Heat diffuses through the walls of a mug filled with hot
coffee
A sugar cube in a glass of water that is not stirred will
dissolve slowly and the sugar molecules will

Why diffusion occur?

diffusion occurs in response to a concentration
gradient
Copper atoms have
migrated or diffused
into nickel, and nickel
has
diffused
into
copper

Types of Diffusion
1. Inter-diffusion: In an alloy, atoms tend to
migrate from regions of high conc. to regions of
low conc.
After some time
Initially

Types of Diffusion
2. Self-diffusion: In an elemental solid, atoms
also migrate.
Label some atoms
C
A

D
B

After some time

C
D

Diffusion Mechanisms
1. Vacancy Diffusion:
Two conditions to occur:
i.
there must be an empty adjacent site available
ii.
the atom must have sufficient energy to break bonds
with its neighbor atoms and then cause some lattice
distortion during the displacement.
Both self-diffusion and inter-diffusion occur by this
mechanism

increasing elapsed time

Diffusion Mechanisms
Vacancy---Self Diffusion

Vacancy

Vacancy
Atom

Diffusion Mechanisms
2. Interstitial diffusion
A small interstitial atom moves
interstitial site to another.
No vacancy is needed or created.

from

More rapid than vacancy diffusion

one

Interstitial diffusion

Vacancy & Interstitial diffusion

Simulation
of
the
vacancy
mechanism

Since diffusing atoms and

vacancies
exchange
positions, the diffusion of
atoms in one direction
corresponding to motion of
vacancies in the opposite
direction
Both self-diffusion and
interdiffusion occur by this
mechanism

Simulation of the
direct interstitial
mechanism

Atoms that migrate from an interstitial position

to a neighboring one that is empty.
Hydrogen, carbon, nitrogen, and oxygen which
have atoms that are small enough to fit into the
interstitial positions.
In most metal alloy, interstitial diffusion occurs
much more rapidly than diffusion by vacancy
mode.
Interstitial atoms are smaller and thus more
mobile.

Activation Energy for Diffusion

Activation
energy:
Energy
required for an atom to
change position. Q. (J/mole,
cal/mole, eV/atom)
A diffusion atom must squeeze
past the surrounding atoms to
reach its new site. In order to
do this we must supply energy
to force the atom to its new
position.
The energy barrier that must
be
overcome
by
thermal
activation
Notes:
Q
is
lower
for
interstitial diffusion than for
vacancy diffusion.

Steady-state diffusion:
Steady state diffusion: Diffusion flux does not
change with time
Concentration of diffusion species on both
surface of the plate are held constant
Diffusion flux (J): Mass (or, equivalently, the
number of atoms) M diffusing through and
perpendicular to a unit cross-sectional area
of solid per unit of time
J = M/At
A; area across which diffusion occurring
and t: elapsed diffusion time.
J= (1/A) (dM/dt)
J: kg/m2 -s or atoms/m2 s

Steady-state diffusion:
Flux;
The flux during
diffusion is defined
as the number of
atoms passing
through a plane of
unit area per unit
time
Flux can be measured
for:
--vacancies
--host atoms
--impurity atoms

Steady-state diffusion:
When concentration C is
plotted vs. position (or
distance, the resulting curve
is termed the concentration
profile:
The slope at particular point
on this curve is
the
concentration gradient
Concentration gradient:

=C /x (kg/m3)

Steady-state diffusion:
The flux is proportional to the
concentration gradient through
the expression
J = -D (C)/ (x)
D:
diffusion
coefficient
(m2)/sec
Negative sign: the expression
indicate
the
direction
of
diffusion
is
shown
the
concentration
gradient,
from
high
to
a
low
concentration
Ficks first law

Steady-state diffusion:
EXAMPLE
At a particular temperature, the diffusion coefficient for Pb in naturally occurring
28
2
ZrSiO4 is

D 8.310

cm s

Find the value of the concentration gradient where the flux of lead, J, is equal to

g
J 5.0 10 2
cm s
30

ANSWER

dC
J D
dx
dC
J

dx
D
dC
5 1030 g s

cm2 s

cm2

dx
8.3 1028
dC
3 g
6.02 10 4
cm
dx

Steady-state diffusion:
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 700C
(1300F). If a condition of steady state is achieved, calculate the diffusion flux
of carbon through the plate if the concentrations of carbon at positions of 5
and 10 mm beneath the carburizing surface are 1.2 and 0.8 kg/m3, respectively.
Assume a diffusion coefficient of 310-11m2/s at this temperature.

Steady-state diffusion:
A sheet of steel 1.5mm thick has nitrogen atmosphere on both sides at
1200C and is permitted to achieve a steady-state diffusion condition. The
diffusion coefficient for nitrogen in steel at this temperature is 610-11m2/s,
and the diffusion flux is found to be 1.210-7kg/m2-s. Also, it is known that
the concentration of nitrogen in the steel at the high-pressure surface is 4
kg/m3. How far into the sheet from this high-pressure side will the
concentration be 2.0 kg/m3? Assume a linear concentration profile.

Steady-state diffusion:
Example
You want to select a polymer for making plastic bottles that can
be used for storing carbonated beverages. What factors would
you consider in choosing a polymer for this application?
SOLUTION
First, since the bottles are to be used for storing carbonated
beverages, a plastic material with a small diffusivity for
carbon dioxide gas should be chosen.
The bottles should have enough strength so that they can
survive a fall of about six feet. This is often tested using a
drop test.
The surface of the polymer should also be amenable to
printing of labels or other product information.
The effect of processing on the resultant microstructure of
polymers must also be considered

Non-steady-state diffusion
Ficks Second Law
1. The concentration gradient at a specific point along the
diffusion path changes with time, t.
2. This transient condition is represented by a second-order
differential equation also known as Fick's second law.

dC d
dC
[ D. ]
dt dx
dx
3.

It is assumed that D is independent of C, leading to a

2
simplified version of equation

dC
d C
D. 2
dt
dx

Non-steady-state diffusion Ficks Second Law

The solution to this differential

equation with the given BC's is
where:
Erf - a Gaussian error function.
Cs - a constant concentration of the
diffusing atoms at the surface of the
material.
Co - the initial uniform concentration
of the diffusing atoms in the material.
Cx - the concentration of the diffusing
atom at location x below the surface
after time t.
BCs

1. For t =0, C = C0 at 0 x
2. For t > 0, C = Cs at x = 0, C = C0
at x =

Cs C x
x
erf (
)
C s Co
2 Dt

Non-steady-state diffusion Ficks Second Law

z

erf(z)

erf(z)

erf(z)

0.0000

0.55

0.5633

1.3

0.9340

0.025

0.0282

0.60

0.6038

1.4

0.9523

0.05

0.0564

0.65

0.6420

1.5

0.9661

0.10

0.1125

0.70

0.6778

1.6

0.9763

0.15

0.1680

0.75

0.7111

1.7

0.9838

0.20

0.2227

0.80

0.7421

1.8

0.9891

0.25

0.2763

0.85

0.7707

1.9

0.9928

0.30

0.3286

0.90

0.7969

2.0

0.9953

0.35

0.3794

0.95

0.8209

2.2

0.9981

0.40

0.4284

1.00

0.8427

2.4

0.9993

0.45

0.4755

1.1

0.8802

2.6

0.9998

0.50

0.5205

1.2

0.9103

2.8

0.9999

Non-steady-state diffusion Ficks Second Law

Example
Start with steel with a concentration of C of 0.25 wt%. To harden
heat at 950 C. If the surface concentration of C is brought to 1.20
wt%, how long will it take to get a concentration of 0.8 wt % at a
position of 0.5 mm below the surface? The diffusion Coefficient for C
in Fe at this temp. is 1.6 x 10-11 m2/sec
x
C (x, t ) - C o = 1 erf
2 Dt
Cs - Co
Know: Cs = 1.2 %, C0 = 0.25 % and C(x,t) = 0.8
C (x, t ) - C

Cs - Co

0.8 0.25
1.2 0.25

0.5789

Non-steady-state diffusion Ficks Second Law

Example cont.
0. 579 =

x
1 erf

2 Dt

x
erf
= 0.421
2 Dt

From Table extrapolate to get

5 x 10-4 m
x

= 0.392 =
2[ (1.6 x 10-11 m2/s)1/2] ( t)1/2

2 Dt

t = 7.1 h

Example: Design of a Carburizing

Treatment
The surface of a 0.1% C steel gears is to be hardened
by carburizing. In gas carburizing, the steel gears are
placed in an atmosphere that provides 1.2% C at the
surface of the steel at a high temperature Carbon
then diffuses from the surface into the steel. For
optimum properties, the steel must contain 0.45% C
at a depth of 0.2 cm below the surface. Design a
carburizing heat treatment that will produce these
optimum properties. Assume that the temperature is
high enough (at least 900oC) so that the iron has the
FCC structure.

SOLUTION

SOLUTION (Continued)

Example Design of a More Economical

Heat Treatment
We find that 10 h are required to successfully
carburize a batch of 500 steel gears at 900oC, where
the iron has the FCC structure. We find that it costs
$1000 per hour to operate the carburizing furnace at
900oC and $1500 per hour to operate the furnace at
1000oC. Is it economical to increase the carburizing
temperature to 1000oC? What other factors must be
considered?

SOLUTION

Example Silicon Device Fabrication

Devices such as transistors (Figure 5.2) are made by doping
semiconductors with different dopants to generate regions that have
p- or n-type semiconductivity.[1] The diffusion coefficient of
phosphorus (P) in Si is D = 65 10-13 cm2/s at a temperature of
1100oC.[13] Assume the source provides a surface concentration of
1020 atoms/cm3 and the diffusion time is one hour. Assume that the
silicon wafer contains no P to begin with. Calculate the depth at
which the concentration of P will be 1018 atoms/cm3. State any
assumptions you have made while solving this problem.

SOLUTION

Factors that affect

diffusion
1. Concentration gradient:
- Higher dc/dx higher J.
- dc/dx decreases and J also decreases with time.

2. Temperature:
- higher temp, higher diffusion rate. (higher D values)
Diffusion Coefficient:

Do

D Do e

Q
(
)
RT

= a proportionality constant independent of

temperature.
R = gas constant, 1.987 cal/mole.K,
8.31 J/mole.K,
8.62 x 10-5 eV/atom
T = absolute temperature, K
-Diffusion rates are very low when temp is lower than
0.4 Tm.

Factors that affect

diffusion
3. Activation energy and diffusion mechanism:
(diffusion species)
Interstitial diffusion occurs an order of magnitude of
faster than vacancy, or substitutional diffusion.
Diffusion is easier in BCC than in FCC.
Q is lower for diffusion of atoms in materials with a
low Tm.
Q is lower for small substitutional atoms compared to
large atoms.
Q increases almost linearly with the melting
temperature of the metal.

4. Time: Diffusion requires time.

5. Atom size: C atoms have a smaller diameter
than Ni, so it can have a higher diffusivity in
Iron.

Factors that affect

diffusion
6. Bond strength:
Cu diffuses more readily in Al than in Cu
because Cu-Cu bonds are stronger than ALAl bonds.
7. APF: Atoms have higher diffusivity in BCC
than in FCC
8. Atom arrangement:
The diffusion proceeds more rapidly along the
grain boundary because this is a zone of
crystal imperfection.

SUMMARY:
STRUCTURE & DIFFUSION
Diffusion FASTER for...

Diffusion SLOWER for...

open crystal structures

close-packed structures

lower melting T materials

higher melting T materials

materials w/secondary
bonding

materials w/covalent
bonding

smaller diffusing atoms

larger diffusing atoms

cations

anions

lower density materials

higher density materials

Summary

Diffusion is the process by which atoms in a material transport them selves

from one location within the substance to another.
Diffusion can occur between solids, gases, liquids, or any combination of the
three as long as the conditions are right.
Case hardening, carburizing, heat treating, etc. are all examples of how we use
diffusion to enhance the properties of materials, i.e. make the stronger,
less prone to corrode or rust, etc.
Solid-state diffusion in metals
In solid-state diffusion we examine the transport of mass through solids.
Interdiffusion occurs between two dissimilar metals.
Self-diffusion occurs within a pure metal.

Diffusion Mechanisms in Metals: Two models on How it Works?

vacancy diffusion:
interstitial diffusion:

Steady-state diffusion
In general diffusion rate (J) can be defined as the rate of mass (M) transfer per unit
time (t) per unit cross-sectional area (A).
If the rate of diffusion does not change with time, it is governed by
Ficks First Law

Non-steady state diffusion:

Now we assume that the rate of change of the concentration is not constant.
Diffusion now must follow Ficks second Law: