Materials Science and Engineering

Edition
Eighth
Eighth Edition

MATERIALS SCIENCE AND

CHAPTER
ENGINEERING :

5 William D. Callister, Jr.

David G. Rethwisch

Lecture Notes:
Solomon B.
Addis Ababa University
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Diffusion
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Contents

• Learning Objectives • Steady-State Diffusion

• Why Study Diffusion ? • Non-steady-State Diffusion
• Factors That Influence Diffusio
• Introduction n
• Diffusion Mechanisms • Summary
• Vacancy diffusion
• Interstitial diffusion
• Substitutional
Diffusion
• Processing using diffusion
• Modeling Diffusion: Flux

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Learning Objectives
After studying this chapter you should be able to do the
following:
1. Name and describe the two atomic mechanisms of diffusion.
2. Distinguish between steady-state and non-steady-state
diffusion.
3. (a) Write Fick’s 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.
4. Calculate the diffusion coefficient for some material at a
specified temperature, given the appropriate diffusion
constants.

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INTRODUCTION
• Many reactions and processes that are important in the
treatment of materials rely on the transfer of mass
either within a specific solid (ordinarily on a
microscopic level) or from a liquid, a gas, or another
solid phase. This is necessarily accomplished by
diffusion, the phenomenon of material transport by
atomic motion.

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Why Study Diffusion ?

Diffusion plays a crucial role in…

Alloying metals => bronze, silver, gold
Strengthening and heat treatment processes
• Hardening the surfaces of steel
High temperature mechanical behavior
Phase transformations
• Mass transport during FCC to BCC
Environmental degradation

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Diffusion couple
• Diffusion couple, is formed by joining bars of two different metals together so
that there is intimate contact between the two faces
Heat

Diffusion transport by
atomic motion.

• Inhomogeneous material can

become homogeneous by
diffusion. Temperature should be
high enough to overcome energy
barrier.
Inter-diffusion
• Concentration Gradient 
Interdiffusion (or Impurity
Diffusion).
Self-diffusion:
• one-component material, atoms are
of same type

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Carburization for Surface Hardening of Steels

• Let’s say we want a surface, such as the
teeth of a gear, to be hard; however, we
do not want the entire gear to be hard.
• The carburization process can be used to
increase surface hardness.
• In carburization, a source of carbon,
such as a graphite powder or gaseous
phase containing carbon, is diffused into Fig. 5.0, Callister 6e.
steel components such as gears (Fig. 5.0 is courtesy of
Surface Division, Midland-
• Similar to the introduction of carbon, we Ross.)

can also use a process known as

nitriding, in which nitrogen is
introduced into the surface of a metallic
material

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Processing Using Diffusion

• How do interstitial carbon improve
the hardness and strength

Result: The "Case" is

--hard to deform: C atoms
"lock" planes from shearing.

--hard to crack: C atoms put

the surface in compression.

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Processing Using Diffusion

• Doping Silicon with P for n-type semiconductors:
• Process:
0.5mm
1. Deposit P rich
layers on surface.

magnified image of a computer chip

silicon
2. Heat it.
3. Result: Doped
semiconductor light regions: Si atoms
regions.

silicon light regions: Al atoms

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Dopant Diffusion for Semiconductor Devices

• The entire microelectronics industry, as we know it today, would not exist if
we did not have a very good understanding of the diffusion of different atoms
into silicon or other semiconductors.
• The creation of the p-n junction involves diffusing dopant atoms, such as
phosphorous (P), arsenic (As), antimony (Sb), boron (B), aluminum (Al), etc.,
into precisely defined regions of silicon wafers.
• A p-n junction is a region of the semiconductor, one side of which is doped
with n-type dopants (e.g., As in Si) and the other side is doped with p-type
dopants (e.g., B in Si).
• The n-type region contains a relatively large number of free electrons, whereas
the p-type region contains a relatively large number of free holes.

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Creation of Plastic Beverage Bottles

In some applications, we may want to limit the occurrence of
diffusion for certain species. For example, in the creation of certain
plastic bottles, the diffusion of carbon dioxide (CO2) must be
minimized.
This is one of the major reasons why we use polyethylene
terephthalate (PET) to make bottles which ensure that the
carbonated beverages they contain will not lose their fizz for a
reasonable period of time!

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Oxidation of Aluminum
You may have heard or know that aluminum does not
“rust.”
In reality, aluminum oxidizes (rusts) more easily than
iron; however, the aluminum oxide (Al2O3) forms a very
protective but thin coating on the aluminum’s surface
preventing any further diffusion of oxygen and hindering
further oxidation of the underlying aluminum.
The oxide coating does not have a color and is thin and,
hence, invisible. This is why we think aluminum does not
rust.

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Optical Fibers and Microelectronic Components

Optical fibers made from silica (SiO2) are coated
with polymeric materials to prevent diffusion of
water molecules. This, in turn, improves the optical
and mechanical properties of the fibers.

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Example 1 Diffusion of Ar /He and Cu/Ni

Consider a box containing an impermeable partition that divides
the box into equal volumes. On one side, we have pure argon (Ar)
gas; on the other side, we have pure helium (He) gas. Explain what
will happen when the partition is opened? What will happen if we
replace the Ar side with a Cu single crystal and the He side with a
Ni single crystal?

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Stability of Atoms and Ions

In Chapter 4, we showed that imperfections are present and also can be
deliberately introduced into a material; however, these imperfections and,
indeed, even atoms or ions in their normal positions in the crystal structures
are not stable or at rest.
Instead, the atoms or ions possess thermal energy, and they will move.
For instance,
• An atom may move from a normal crystal structure location to
occupy a nearby vacancy.
• An atom may also move from one interstitial site to another.
• Atoms or ions may jump across a grain boundary, causing the grain
boundary to move.
The ability of atoms and ions to diffuse increases as the temperature, or
thermal energy possessed by the atoms and ions, increases. Arrhenius
equation:

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The Arrhenius plot of ln(rate) versus 1/T

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Example2 Activation Energy for Interstitial Atoms

Suppose that interstitial atoms are found to
move from one site to another at the rates of
5x108 jumps/s at 500°C and 8 x1010 jumps/s at
800°C. Calculate the activation energy Q for
the process.

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Diffusion mechanisms
• From an atomic perspective, diffusion is just the stepwise
migration of atoms from lattice site to lattice site.
• For an atom to make such a move, two conditions must
be met:
1. there must be an empty adjacent site, and
2. the atom must have sufficient energy to break bonds
with its neighbor atoms and then cause some lattice
distortion during the displacement.
There are three mechanisms of diffusion
 Vacancy diffusion
 Interstitial diffusion
 Impurities

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Vacancy diffusion
One mechanism involves the interchange of an atom from a
normal lattice position to an adjacent vacant lattice site or
vacancy
Atom migration Vacancy migration

Before
After
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.
Therefore, there is an energy barrier.
Energy comes from thermal energy of atomic vibrations (Eav ~ kT)
Atom flow is opposite to vacancy flow direction.
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Interstitial diffusion
The second type of diffusion involves atoms that migrate from an
interstitial position to a neighboring one that is empty.
Interstitial atom Interstitial atom
before diffusion after diffusion

Generally faster than vacancy diffusion because bonding of

interstitials to surrounding atoms is normally weaker and there are
more interstitial sites than vacancy sites to jump to. Smaller energy
barrier
Only small impurity atoms (e.g. C, H, O) fit into interstitial sites.
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Substitutional Diffusion:
• applies to substitutional impurities
• atoms exchange with vacancies
• rate depends on:
--number of vacancies
--activation energy to exchange.

increasing elapsed time

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• Diffusion of copper atoms

into nickel. Eventually, the
copper atoms are randomly
distributed throughout the
nickel.
• The number of vacancies,
which increases as the
temperature increases,
influences the extent of both
self-diffusion and diffusion
of substitutional atoms.

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Activation Energy for Diffusion

• A diffusing atom must squeeze past the surrounding atoms to
reach its new site. In order for this to happen, energy must be
supplied to allow the atom to move to its new position, as shown
schematically for vacancy and interstitial diffusion
• The atom is originally in a low-energy, relatively stable location.
In order to move to a new location, the atom must overcome an
energy barrier. The energy barrier is the activation energy Q
• Normally, less energy is required to squeeze an interstitial atom
past the surrounding atoms; consequently, activation energies are
lower for interstitial diffusion than for vacancy diffusion
• A low-activation energy indicates easy diffusion

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Activation Energy for Diffusion

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STEADY-STATE DIFFUSION
• Diffusion is a time-dependent process—that is, in a macroscopic sense,
the quantity of an element that is transported within another is a function
of time.
• Often it is necessary to know how fast diffusion occurs, or the rate of
mass transfer (diffusion flux (J))
Diffusion flux:
• defined as the mass (or, equivalently, the number of atoms) M diffusing
through and perpendicular to a unit cross-sectional area of solid per unit
of time

where A denotes the area across which diffusion is occurring and t is the
elapsed diffusion time. In differential form, this expression becomes

• If the diffusion flux does not change with time, a steady-state condition
exists.

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Concentration Gradient
• When concentration C is plotted versus position (or distance) within the
solid x, the resulting curve is termed the concentration profile
• The concentration gradient shows how the composition of the material varies
with distance

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Rate of Diffusion [Fick’s First Law]

• Adolf Eugen Fick (1829–1901) was the first scientist to provide a
quantitative description of the diffusion process. Interestingly, Fick
was also the first to experiment with contact lenses in animals and
the first to implant a contact lens in human eyes in 1887–1888!
• The rate at which atoms, ions, particles or other species diffuse in a
material can be measured by the flux J. Here we are mainly
concerned with diffusion of ions or atoms.

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Steady State Diffusion

the concentration profile doesn't
• Steady State:
change with time.
Steady State:
J x(left) J x(right) J x(left) =J x(right)
x
Concentration, C, in the box doesn’t change w/time.
dC
• Apply Fick's First Law: J x  D
dx
dC  dC
• If Jx)left = Jx)right , then    
dx left dx right
• Result: the slope, dC/dx, must be constant
(i.e., slope doesn't vary with position)!

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Example3 Semiconductor Doping

One step in manufacturing transistors, which

function as electronic switches in integrated
circuits, involves diffusing impurity atoms into a
semiconductor material such as silicon (Si).
Suppose a silicon wafer 0.1 cm thick, which
originally contains one phosphorus atom for every
10 million Si atoms, is treated so that there are 400
phosphorous (P) atoms for every 10 million Si
atoms at the surface. Calculate the concentration
gradient (a) in atomic percent cm and (b) in . The
lattice parameter of silicon is 5.4307Å.

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Factors Affecting Diffusion

Temperature and the Diffusion Coefficient
• The kinetics of diffusion are strongly dependent on
temperature. The diffusion coefficient D is related to
temperature by an Arrhenius-type equation,

• The temperature dependence of D is shown in below for some metals

and ceramics.
• Covalently bonded materials, such as carbon and silicon have unusually
high activation energies, consistent with the high strength of their atomic
bonds.
• The activation energies are high and the rates of diffusion are lower for
ionic materials than those for metals
• When the temperature of a material increases, the diffusion coefficient D
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Factors Affecting Diffusion

Types of Diffusion

• In volume diffusion, the atoms move through the crystal from one
regular or interstitial site to another. Because of the surrounding
atoms, the activation energy is large and the rate of diffusion is
relatively slow.
• Atoms can also diffuse along boundaries, interfaces, and surfaces in
the material. Atoms diffuse easily by grain boundary diffusion,
because the atom packing is disordered and less dense in the grain
boundaries. Because atoms can more easily
• squeeze their way through the grain boundary, the activation energy
is low. Surface diffusion is easier still because there is even less
constraint on the diffusing atoms at the surface.

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Factors Affecting Diffusion

Time
• Diffusion requires time. The units for flux are (ATOMS/CM2.S) . If
a large number of atoms must diffuse to produce a uniform
structure, long times may be required, even at high temperatures.
Times for heat treatments may be reduced by using higher
temperatures or by making the diffusion distances (related to ∆x)
as small as possible.

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Example, Tungsten Thorium Diffusion Couple

Consider a diffusion couple between pure tungsten and a tungsten
alloy containing 1 at% thorium. After several minutes of exposure at
2000°C, a transition zone of 0.01 cm thickness is established. What
is the flux of thorium atoms at this time if diffusion is due to (a)
volume diffusion, (b) grain boundary diffusion, and (c) surface
diffusion? (See Table 5-2.)

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Factors Affecting Diffusion

• Dependence on Bonding and Crystal
Structure
• A number of factors influence the activation energy for diffusion and,
hence, the rate of diffusion.

• Interstitial diffusion, with a low-activation energy, usually occurs much

faster than vacancy, or substitutional diffusion.

• Activation energies are usually lower for atoms diffusing through open
crystal structures than for close-packed crystal structures.

• Because the activation energy depends on the strength of atomic bonding,

it is higher for diffusion of atoms in materials with a high melting
temperature.

• We also find that, due to their smaller size, cations (with a positive charge)
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Composition Profile [Fick’s Second Law]

Most practical diffusion situations are nonsteady-state ones.

• That is, the 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 resulting.

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Fick’s second law,

• Fick’s second law, which describes the dynamic, or non-steady state,
diffusion of atoms, is the differential equation

• If we assume that the diffusion coefficient D is not a function of

location x and the concentration (c) of diffusing species, we can
write a simplified version of Fick’s second law as follows

• The solution to this equation depends on the boundary conditions

for a particular situation. One solution is

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Solving Fick’s Second Law

Assumptions
1. Before diffusion, any of the diffusing solute atoms in the solid
are uniformly distributed with concentration of C0.
2. The value of x at the surface is zero and increases with distance
into the solid.
3. The time is taken to be zero the instant before the diffusion
process begins.
These boundary conditions are simply stated as

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Example. Design of a Carburizing Treatment

1. The surface of a 0.1% C steel gear 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 900°C) so
that the iron has the FCC structure.

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Example. Nonsteady-State Diffusion Time Computation I

• For some applications, it is necessary to harden the surface of a steel
(or iron–carbon alloy) above that of its interior. One way this may be
accomplished is by increasing the surface concentration of carbon in a
process termed carburizing; the steel piece is exposed, at an elevated
temperature, to an atmosphere rich in a hydrocarbon gas, such as
methane (CH4).
• Consider one such alloy that initially has a uniform carbon
concentration of 0.25 wt% and is to be treated at 950 0C. 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 1.6x10 -11
m2/s; assume that the steel piece is semi-infinite.

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Example. Nonsteady-State Diffusion Time Computation II

• The diffusion coefficients for copper in aluminum at 500 and

600C are 4.8x10-14 and 5.3x10-13 m2/s, respectively. Determine
the approximate time at 5000C that will produce the same
diffusion result (in terms of concentration of Cu at some
specific point in Al) as a 10-h heat treatment at 6000C.

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Diffusion And Temperature

• Diffusivity increases with T.
pre-exponential [m2/s] (see Table 5.2,Callister 6e)
activation energy
 Q  [J/mol],[eV/mol]
diffusivity D  Do exp  d  (see Table 5.2,Callister 6e)
 RT 
• Experimental Data: gas constant [8.31J/mol-K]
1500
1000

600

300
T(C)
10-8 C i D has exp. dependence on T
n
D (m2/s)
-F
e Ci Recall: Vacancy does also!
n
-Fe Dinterstitial>> D
substitutional
10-14 C in -Fe Cu in Cu
Zn Fe e

C in -Fe Al in Al
Fe

Al
in Cuin -

Fe in -Fe
Cu in Fe

in
in 

Fe in -Fe
Al
-F

Zn in Cu
10-20
Cu

0.5 1.0 1.5 2.0 1000K/T

Adapted from Fig. 5.7, Callister 6e. (Date for Fig. 5.7 taken
from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
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Factors that Influence Diffusion

 Temperature - diffusion rate increases very rapidly with
increasing temperature

 Diffusion mechanism - interstitial is usually faster than

vacancy

 Diffusing and host species - Do, Qd is different for every solute,

solvent pair

 Microstructure - diffusion faster in polycrystalline vs. single

crystal materials because of the rapid diffusion along grain
boundaries and dislocation cores.

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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 • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• cations • anions

• lower density materials • higher density materials

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Summary
Make sure you understand

Activation energy
Concentration gradient
Diffusion
Diffusion coefficient
Diffusion flux
Driving force
Fick’s first and second laws
Interdiffusion
Interstitial diffusion
Self-diffusion
Steady-state diffusion
Vacancy diffusion
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