EME 1166 MATERIALS SCIENCE

CHAPTER 5
DIFFUSION
Introduction
Many reactions and processes that are important
in the treatment of materials rely on the transfer
of mass either within a specific solid or from a
liquid, a gas or another solid phase. This is
necessarily accomplished by diffusion, the
phenomenon of material transport by atomic
motion.
This chapter discusses:
1. Diffusion
2. Diffusion mechanisms
3. Steady-state diffusion
4. Nonsteady-state diffusion
5. Factors that influence diffusion

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1. Diffusion
 Diffusion is a phenomenon of
material/mass transport by atomic
motion.
 It is a process by which a matter is
transported through another matter.
 There are 2 types of diffusion:
i. Interdiffusion
ii. Self-diffusion
1. Diffusion
 Examples:
 Movement of smoke particles in air :Very fast.
 Movement of dye in water : Relatively slow.
 Solid state reactions : Very restricted
movement due to bonding.
 Interdiffusion
 In an alloy, atoms tend to migrate from
regions of high concentration to regions
of low concentration.
 The process whereby atoms of one metal
diffuse into another is termed
interdifussion or impurity diffusion.

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Interdiffusion
Diffusion of Cu atoms
Cu Ni Cu Cu-Ni alloy Ni
Diffusion of Ni atoms

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Self-diffusion
 Atomic migration in pure metals.
 All atoms exchanging positions are of
the same type.

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 2. Diffusion Mechanisms
 The migration of atoms from lattice site to
lattice site is only possible if the following 2
conditions are met:
1) There must be an empty adjacent site,
2) The atom must have sufficient energy
to break bonds with its neighbor atoms
and then cause some lattice distortation
during the displacement.
 Diffusion rate is higher at high temperatures.

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 2. Diffusion Mechanisms
 There are 2 dominate diffusion
mechanisms:
1) Vacancy diffusion
2) Interstitial diffusion

 For a given host metal, interstitial atomic

species generally diffuse more rapidly.

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 Vacancy Diffusion
 It involves the interchange of an atom from a
normal lattice position to an adjacent vacant
lattice site (vacancy).

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 Vacancy Diffusion
• The rate of diffusion depends on:
- Number of vacancies
- Activation energy to exchange.

 Both self-diffusion & interdiffusion occur by this

mechanism.

Increasing elapsed time 11

 Substitutional Diffusion
 Example: If atom ‘A’
has sufficient activation
energy, it moves into the
vacancy self diffusion.

Activation Activation Activation

Energy of = Energy to + Energy to
Self diffusion form a move a
Vacancy vacancy

 As the melting point increases, activation energy

also increases
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Interstitial diffusion
 A diffusion mechanism whereby atomic
motion is from interstitial site to interstitial
site.
 It is found for interdiffusion of impurities
which have atoms that are small enough to fit
into the interstitial positions.
 Example: Hydrogen (H), carbon (C), nitrogen
(N2) and oxygen (O2) .
 Host/substitutional impurity atoms
rarely diffuse via this mechanism.
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Interstitial diffusion
Interstitial diffusion
 It is more rapid than vacancy
diffusion in most metal alloys
because:
i. The interstitial atoms are smaller
and more mobile.
ii. There are more empty interstitial
positions than vacancies.
Applications of Diffusion in Processing
 CaseHardening:
- An Example of interstitial diffusion is a
case hardened gear.
- Carbon atoms diffuse into the host iron
atoms at the surface.
- Result: The presence of C atoms makes iron
(steel) harder.

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Industrial Applications of Diffusion –
Case Hardening
 Sliding and rotating parts needs to have hard
surfaces.
 These parts are usually machined with low carbon
steel as they are easy to machine.
 Their surface is then hardened by carburizing.
 Steel parts are placed at elevated temperature
(927°C) in an atmosphere of hydrocarbon gas
(CH4).
 Carbon diffuses into iron surface and fills
interstitial space to make it harder.

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Carburizing
C%

Carbon Gradient in
Carburized Metals
Low carbon diffusing
steel part carbon atom

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 Diffusion is a time-dependent process; that is, in
macroscopic sense, the quantity of an element
that is transported within another is a function of
time.
 It is necessary to know how fast diffusion occurs,
or the rate of mass transfer.
 This rate is expressed as a diffusion flux (J).

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

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Can be measured empirically
 Make thin film (membrane) of known
surface area
 Impose concentration gradient
 Measure how fast atoms or molecules
diffuse through the membrane
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Steady-State Diffusion
 There is no change in concentration of
solute atoms at different planes in a system,
over a period of time.
 No chemical reaction occurs. Only net flow
of atoms.
 The rate of diffusion is independent of
time.
 It is governed by the Fick’s First Law of
diffusion which states that the diffusion flux
is proportional to the concentration gradient.
 Example: Purification of hydrogen gas
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

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Fick’s First law

Figure: (a) Steady-state diffusion across a thin plate. (b) A

linear concentration profile for the diffusion situation in (a).

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 Non-Steady State Diffusion


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 Fick’s Second Law – Solution
 Consider the diffusion of some solute atoms
in a solid bar.

 Surface concentration, Cs of solute

atoms

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

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1. Before diffusion, any of the diffusing solute atoms
in the solid are uniformly distributed with
concentration of C0.
2. At the surface x = 0 & increases with distance
into the solid.
3.Before the diffusion process begins, time t = 0.

These boundary conditions are simply stated as:

 For t = 0, C = C0 at 0 ≤ x ≤ ∞
 For t > 0:
- C = CS(constant surface concentration) at x = 0
- C = Co at x = ∞
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Figure: Concentration profiles for nonsteady-state diffusion
taken at three different times, t1, t2, and t3.

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

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

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 Suppose that it is desired to achieve some
specific concentration of solute, C1, in an
alloy, the eq. becomes;

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Example 4

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Factors That Influence Diffusion
1.Type of diffusion: Whether the diffusion is
interstitial or substitutional.
2.Temperature: As the temperature increases
diffusivity increases.
3.Type of crystal structure: BCC crystal has lower
APF than FCC and hence has higher diffusivity.
4.Type of crystal imperfection: More open
structures (grain boundaries) increases diffusion.
5.The concentration of diffusing species: Higher
concentrations of diffusing solute atoms will affect
diffusivity
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

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 The activation energy Qd is the energy required to produce
the diffusive motion of one mole of atoms.

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 Since D has exponential dependence on 1/T, if
log D is plotted versus 1/T, a straight line is
obtained.

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The End

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