Notes Adapted From:

Introduction to Materials Science for Engineers

Author: James F. Shackelford
Foundations of Materials Science and Engineering
Authors: William F. Smith and Javad Hashemi
Materials Science and Engineering an Introduction
Author: Wiliam D. Callister, Jr.
The Science and Design of Engineering Materials
Authors: Schaffer, Saxena, Antolovich, Sanders and Warner
The Science and Engineering of Materials
Author: Donald R. Askeland
Understanding Solids: The Science of Materials
Author: Richard Tiley
Source for Figures:
Introduction to Materials Science for Engineers
Author: James F. Shackelford
Materials Science and Engineering an Introduction
Author: Wiliam D. Callister, Jr.

Diffusion
Materials of all types are heat treated to improve
their properties. The phenomena that occur during a
heat treatment almost always involve atomic diffusion
Example: Carburization of steels, in which the surface
is hardened by the diffusion of carbon atoms from a
carbon-rich environment
Heat-treating temperatures and times and/or cooling
rates are often predictable using the mathematics of
diffusion and appropriate diffusion constants

Diffusion
Diffusion: The phenomenon of material transport by
atomic motion
Atoms in gases, liquids and solids are in constant
motion and migrate over a period of time
In gases, atomic movement is relatively rapid
Atomic movements in liquids are in general slower than
in gases
In solids, atomic movements are restricted due to
bonding to equilibrium positions

Diffusion
Thermal vibrations occurring in solids do allow some
atoms to move
Diffusion of atoms in metals and alloys is important
since most solid-state reactions involve atomic
movements
Diffusion is essentially statistical in nature, resulting
from many random movements of individual atoms
While the path of an individual atom may be zigzag
and unpredictable, when large numbers of atoms make
such movements they produce a systematic flow

Diffusion Couple
Diffusion couple is formed by joining bars of two
different metals together so that there is an intimate
contact between the two faces
Example: Diffusion couple between Copper and Nickel

Diffusion Couple

Figure source: Materials Science and Engineering an Introduction

Author: Wiliam D. Callister, Jr.

Interdiffusion and Self-Diffusion

Interdiffusion or impurity diffusion: The process
whereby atoms of one metal diffuse into another is
termed interdiffusion or impurity diffusion
Interdiffusion may be discerned from a macroscopic
perspective by changes in concentration that occur
over time
Self-Diffusion: Diffusion may also occur for pure
metals, but all atoms exchanging positions are of the
same type

Diffusion Mechanisms
Atomic perspective Diffusion is stepwise migration
from one lattice site to lattice site

For an atom to make such a move, two conditions

must be met

There must be an empty adjacent site

The atom must have sufficient energy to break

bonds with its neighbor atoms and then cause
some lattice distortion during the displacement.
This energy is vibrational in nature

Diffusion Mechanisms
At a specific temperature, some small fraction of the
total number of atoms is capable of diffusive motion by
virtue of the magnitudes of their vibrational energies
This fraction increases with rising temperature
Two models of metallic diffusion

Vacancy Diffusion
Interstitial Diffusion

Vacancy Diffusion
Vacancy diffusion involves the interchange of an atom
from a normal lattice position to a vacant lattice site
or vacancy
Since diffusing atoms and vacancies exchange positions
the diffusion of atoms in one direction corresponds to
the motion of vacancies in the opposite direction
Both self-diffusion and interdiffusion occur by this
mechanism

Vacancy Diffusion

Figure source: Introduction to Materials Science for Engineers

Author: James F. Shackelford

Interstitial Diffusion
Interstitial diffusion involves atoms that migrate from an
interstitial position to a neighboring one that is empty

Figure source: Introduction to Materials Science for Engineers

Author: James F. Shackelford

Interstitial Diffusion
This mechanism is found for interdiffusion of impurities
such as hydrogen, carbon, nitrogen and oxygen which
have atoms that are small enough to fit into the
interstitial positions
Interstitial diffusion occurs much more rapidly than
diffusion by the vacancy mode. This is because
Interstitial atoms are smaller and thus more
mobile
There are more empty interstitial positions than
vacancies. Therefore the probability of interstitial
atomic movement is greater than for vacancy
diffusion

Diffusion Flux
Diffusion is a time-dependent process. That is the
quantity of an element that is transported within
another is a function of time
How fast diffusion occurs or the rate of mass transfer
is frequently expressed as diffusion flux (J)
Diffusion flux J, is defined as the mass M diffusing
through and perpendicular to an unit cross-sectional
area of solid per unit of time
J = M / At ; Units of J = Kg m-2 s-1
In differential form
J = (1/A) (dM/dt)
where M is the mass of atoms diffusing through the
area A during time t

Steady-State Diffusion
Steady state diffusion: Diffusion flux does not
change with time
When concentration C is plotted versus position within
the solid x, the resulting curve is called the
concentration profile
dC
dx

Concentration gradient: (Kg.m-3): The slope

at a particular point on concentration profile.

dC C CA CB

=
dx x XA XB

Steady-State Diffusion Ficks First Law

Ficks first law: The diffusion flux along direction x is
proportional to the concentration gradient

dC
J = D
dx

Figure source: Introduction to Materials Science for Engineers

Author: James F. Shackelford

Steady-State Diffusion Ficks First Law

Ficks first law: the diffusion flux along direction x is
proportional to the concentration gradient

dC
J = D
dx
D is a measure of the mobility of the diffusing species
Units of D: m2/s
Negative sign in the above equation indicates that the
direction of diffusion is down the concentration gradient
from a high to a low concentration

Steady-State Diffusion
In steady-state diffusion, the concentration profile does
not change with time

Figure source: Materials Science and Engineering an Introduction

Author: Wiliam D. Callister, Jr.

In steady-state

J X( Left ) = J X ( Right )
Applying Ficks first law
J X( Left ) = J X ( Right )
dC
dC
D
= D
dx Left
dx Right

Steady-State Diffusion
Cancelling D, we get
dC
dC
=
dx Left dx Right

Which states that slope

dC
dx

must be constant

Non Steady-State Diffusion

Most practical diffusion situations are nonsteady-state
ones
In non steady-state diffusion 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 diffusion species resulting
Under non steady-state conditions, the below equation
is no longer valid

dC
J = D
dx

Non Steady-State Diffusion

Ficks Second Law
Under non steady-state conditions, concentration profile
c(x) changes with time

Figure source: Materials Science and Engineering an Introduction

Author: Wiliam D. Callister, Jr.

Rate of accumulation = - flux gradient

J
c

=
t
x
Now
dC
J = D
dx
c C

= D
t x x

Non Steady-State Diffusion

Ficks Second Law
c C
= D
t x x

Ficks second law: This law states that the rate of

compositional change is equal to diffusivity times the rate
of change of concentration gradient.
If D is independent of composition
2C
c
=D 2
t
x

Solutions to this expression (concentration in terms of both

position and time) are possible when physically meaningful
boundary conditions are specified.

Non Steady-State Diffusion

Ficks Second Law
Solution to Ficks second law for the case of a semiinfinite solid

Figure source: Introduction to Materials Science for Engineers

Author: James F. Shackelford

Steady vs. Non steady state

Diffusion
In steady-state diffusion
Flux in = Flux out

c
=0
t

J
=0
x

In non steady-state diffusion

Flux in is not equal to Flux out
Accumulation or depletion