FACULTY OF ENGINEERING & THE BUILT ENVIRONMENT

Department of Civil, Mining & Process Engineering

MATERIALS SCIENCE 124

Mrs J.T. Kurasha
CHAPTER 5 - DIFFUSION
 Thinking points
• What drives diffusion?
• What are the applications of diffusion in materials?
 OBJECTIVES
➢We will study the phenomenon of diffusion - how do
atoms move through solids?

• OBJECTIVES

✓Diffusion mechanisms
✓The mathematics of diffusion
➢ Steady-state diffusion (Fick’s first law)
➢ Nonsteady-State Diffusion (Fick’s second law)
✓Factors that influence diffusion
 Definition
• Diffusion refers to the phenomenon of material
transport by atomic or ionic motion, i.e the net flux
of ions or atoms which depends on
➢initial gradient and
➢concentration.
• A number of processes which are important in the
treatment of materials depend on diffusion.
 INTER -DIFFUSION AND SELF
DIFFUSION

➢ Interdiffusion or impurity diffusion occurs in

response to a concentration gradient.
HEAT
➢ Self-diffusion is diffusion in a one-
component material, when all atoms which
exchange positions are of the same type.

BEFORE AFTER
 Mechanisms of Diffusion
• For atomic diffusion to occur, there should be an empty
adjacent site, and the atom should have sufficient energy to
break bonds with its neighbors.

• There are two main mechanisms in diffusion mainly,

➢Vacancy diffusion
➢Interstitial diffusion
 Vacancy diffusion
• An atom from a given lattice interchanges with an adjacent vacant lattice site or
vacancy. The diffusion of atoms in one direction corresponds with the
movement of vacancies in the opposite direction.
• Rate of diffusion depends on;
➢ Number of vacancies
➢ Activation energy to migrate

Impurity diffusion
Self diffusion (pure metal)
 Cont’d
• To jump from lattice site to lattice site, atoms need energy
to break bonds with their neighbours, and to cause the
necessary lattice distortions during jump.

• This energy comes from the thermal energy of atomic

vibrations.
 Interstitial diffusion
• It involves atoms that migrate from an interstitial position to a
neighbouring one that is empty.

• Impurities such as carbon, hydrogen, nitrogen and oxygen which

have atoms that are small enough to fit into interstitial positions
are usually involved, i.e. small impurity atoms (e.g. C, H, O) fit into
interstices in the host easily.

• Interstitial diffusion is generally faster than vacancy diffusion

because bonding of interstitials to the surrounding atoms is
normally weaker and there are many more interstitial sites than
vacancy sites to jump to.
 Cont’d

Self diffusion (pure Impurity diffusion

metal)
 Rate of Diffusion
• Diffusion is time-dependent because the amount of matter
transferred depends on time.

• The rate at which atoms or ions diffuse in a given material can be

measured by the flux, J, which is defined as the number of atoms
or ions passing through a plane of unit area per unit time.

• The flux of diffusing atoms, J, is used to quantify how fast

diffusion occurs.

• The flux is defined as either the:

➢ number of atoms diffusing through unit area per unit time(
Atoms/m2.s) or the
➢ mass of atoms diffusing through unit area per unit time (Kg/m2..s)
 Cont’d
• For example, for the mass flux we can write
Diffusion Flux, as:
𝑴 𝑴𝒂𝒔𝒔 (𝒐𝒓 𝒂𝒕𝒐𝒎𝒔 𝒐𝒓 𝒎𝒐𝒍𝒆𝒔)
J = 𝑨𝒕
= 𝑨𝒓𝒆𝒂 𝒙 𝒕𝒊𝒎𝒆
(Kg/m2..s)

In differential form, it becomes:

𝟏 𝜹𝑴
J(t) = (Kg/m2..s)
𝑨 𝜹𝒕

where M is the mass of atoms diffusing through the area

A, during time t.
 Activation Energy
• Energy is required for an atom to migrate from one position to another.

• An energy barrier, defined as the activation energy, Q or Em must be

overcome.

• Normally the activation energy required for interstitial diffusion to occur

is lower than that required for vacancy diffusion because of the
relatively small size of interstitial atoms.

• A low activation energy signifies easy diffusion.

• In self-diffusion, the activation energy is equal to the energy needed to

create a vacancy and to cause the movement of the atom.
Cont’d
 Concentration gradient
• The concentration gradient shows how the
composition of the diffusing species varies with
distance.

• ΔC is the difference in concentration over a

distance Δx.

ΔC
Concentration gradient =
Δx
 Steady State diffusion
• Steady state condition exists when the diffusion flux does not change
with time.
• Concentrations(pressures) of two species are held constant, PA and PB
 Cont’d
• The concentration gradient dc/dx is the slope of the
concentration profile at a particular point.
 Fick’s first law of diffusion-Steady
state diffusion
• The diffusion flux along a direction x, is proportional to the concentration gradient.

FICK’S FIRST LAW

J – flux
D- diffusivity or diffusion coefficient in Cm2/s or m2/s

dc/dx- concentration gradient

• The negative sign indicates that the direction of diffusion is down the
concentration gradient.

• At the microscale, the thermodynamic driving force for diffusion is the concentration gradient.
The steeper the concentration gradient, the greater will be the diffusion or the mass transfer.
 Example
A plate of iron is exposed to a carburizing
atmosphere on one side and a decarburizing
atmosphere on the other side at 700oC. If a condition
of steady state is achieved, calculate the diffusion
flux of carbon through the plate if the concentrations
of carbon at positions 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.
Solution
Non-Steady State Diffusion- Fick’s
second law of diffusion
• In many real situations, the concentration profile & concentration
gradient, do change with time, causing a net accumulation or depletion.
• Fick’s Second Law describes the non-steady diffusion of atoms using a
differential equation.

FICK’S SECOND
LAW
 Cont’d
• The solution of the equation depends on the given
boundary conditions. One solution
of the equation is:

Gaussian error
function (z)

Cx : Concentration at depth x
Cs: Concentration at the surface
Co: Initial concentration
 Example
A steel alloy is surface hardened through
carburization at 950oC. The alloy has an initial
uniform carbon concentration of 0.25 wt%. 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 this scenario is 1.6 x 10-11
m2/s.
 Solution
This is non-steady state diffusion, and Fick’s second
law of diffusion applies. From the question,
Co = 0.25 wt%
Cs = 1.20 wt%
Cx = 0.80 wt%
x = 0.50 mm = 5 x 10-4m
D = 1.6 x 10-11 m2/s
 Cont’d
𝐶𝑥 −𝐶𝑜 0.80−0.25 (5 𝑥 10−4 )
= = 1 - erf[ ]
𝐶𝑠 − 𝐶𝑜 1.20−0.25 2 1.6 𝑥 10−11 )(𝑡)
62.5𝑠1/2
0.4210 = erf[ ]
𝑡
From the error function tables, determine the value
of z for which the error function is 0.4210.
interpolation is necessary since there is no exact
value of z for 0.4210.
Z Erf(z)
0.35 0.3794
z 0.4210
0.40 0.4284
 Cont’d
𝑧−0.35 0.4210−0.3794
=
0.40−0.35 0.4284−0.3794
z = 0.392
Therefore,
62.5𝑠 1/2
= 0.392
𝑡
Solving for t,
62.5𝑠1/2 2
t = ( ) = 25 400s
0.392
= 7.1 hrs.
 Factors Affecting Diffusion
1.Diffusing species - Different materials have
different diffusion coefficients (Do), which is also the
indication of the diffusion rate.
2. Crystal structure – FCC, BCC, HCP,…..
3. Imperfections - (grain boundary, dislocation,
vacancy, lattice).
4. Temperature - Diffusion is a thermally activated
process.
 Rate of Diffusion- effect of
temperature
• The rate of diffusion is strongly dependent on temperature.
• The diffusion coefficient, D is a measure of the mobility of
the diffusing species. It is related to temperature by an
Arrhenius type equation;
•

Where
Q- activation energy in cal/mol or J/mol for the
diffusing species
𝑄
D = Do exp (- ) R- the gas constant
𝑅𝑇 Do- a constant for a given diffusion system
T- absolute temperature, Kelvin
 Cont’d
• The latter equation can be rewritten as;
𝑄𝑑 1
In D = In Do - ( )
𝑅 𝑇

𝑄𝑑 1
or Log D = log Do - ( )
2.3𝑅 𝑇

• The activation energy, 𝑄𝑑 , and the pre-exponential

constant Do can be estimated by plotting ln D vs 1/T
or log D vs 1/T.
• Such plots are known as Arrhenius plots.
 Example
• At 300°C the diffusion coefficient and activation
energy for
Cu in Si are
• D(300°C) = 7.8 x 10-11m2/s

• Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350°C?
Solution
Cont’d
Cont’d
Diffusion-The role of
microstructure

self-diffusion coefficients for Ag

 Cont’d
• The preceding figure shows the self-diffusion coefficients for Ag
dependent on the diffusion path.
• In volume diffusion, the atoms move from one regular or interstitial site
to another. Because of surrounding atoms, the activation energy is large
and the rate of diffusion is relatively slow.
• Atoms can also diffuse along boundaries, surfaces and interfaces in
materials. Generally, the diffusivity if greater through less restrictive
structural regions –grain boundaries, dislocation cores, external
surfaces. However, in most cases the contributions of these ‘short-
circuit’ paths to the overall diffusion flux, is insignificant due to their
extremely small cross-sectional areas.
• Atoms easily diffuse by grain –boundary diffusion since the atomic
packing is disordered and less dense in the grain boundaries. Surface
diffusion is easier still because there is less constraint on the diffusing
atoms at the surface.
 Importance of Diffusion in
materials processing
➢Heat Treatment of Metals
➢Case hardening of steel (carbon diffusion in steel)
➢Oxidation of metals
➢Thin film electronics (doping of semiconductors)
➢Sintering (fusion of powder particles at solid state).
 Case Hardening
• Hardening the surface of a metal by exposing it to impurities that diffuse into
the surface region and increase surface hardness.
• Common example of case hardening is carburization of steel. Diffusion of carbon
atoms (interstitial mechanism) increases concentration of C atoms and makes
iron (steel) harder.
Doping in semiconductors
 Sintering of ceramics/Cemented
carbides
• Sintering is when high
temperature causes
particles to join, gradually
reducing the volume of
pore space between them.

• In order to reduce the total

energy of material, atoms
diffuse to points of contact,
allowing the particles to be
bonded together.
Metal Oxidation
Heat Treatment
References
1. Callister, W. D. Jr. & Rethwisch, D. G. (2011).
Materials Science and Engineering – An
introduction. 9th Edition. Asia: John Wiley & Sons.
2. Askeland, D. R. & Fulay, P. P. & Wright, W. J.
(2006). The Science and Engineering of Materials.
6th Edition. Canada: Global Engineering.
3. Shackleford, J.F. Introduction to Materials Science
for Engineers (1996), S.I Edition. Prentice-Hall,
New Jersey.