Chapter 5: Diffusion

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
diffusion, the phenomenon of material transport
by atomic motion.
Diffusion Mechanism
For atoms to move, two conditions must be met.

1)There must be an empty adjacent site

2) The atoms must have enough energy to break

the bonds with its neighbor atoms-vibrational
energy through temperature increase. In other
words for an active diffusion to occur, the
temperature should be high enough to
overcome energy barriers to atomic motion.
Demonstration of Diffusion
The mechanism of diffusion can be demonstrated by
considering a diffusion couple. A diffusion couple is formed
by joining bars of two different materials, in this case, copper
(Cu) and nickel (Ni) is considered.
1. The couple is heated to high temperatures for a period of
time (below melting point) and cooled at room temperature.
2. Chemical analysis will show pure copper and pure nickel on
the left and right respectively, separated by a copper-nickel
alloy.
3. This shows that copper atoms have diffused into the nickel
and the nickel atoms have diffused into the copper.
4. This process whereby atoms of one metal diffuse into
another is termed interdiffusion or impurity diffusion.
5. Diffusion also occurs in pure metals. In one-component
material when all atoms that exchange positions are of the
same type then the diffusion is termed as self diffusion.
Vacancy Diffusion
1) This mechanism involves the interchange of
an atom from a normal lattice position to an
adjacent vacant site.
2) Atoms move in one direction corresponding
to the vacancy moving in the opposite direction.
3) This process is not possible without vacancies
and the more vacancies the higher the chances
of vacancy diffusion.
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. This energy comes from the
thermal energy of atomic vibrations (Eav ~ kBT)
The direction of flow of atoms is opposite the vacancy
flow direction.
Interstitial Diffusion
1) Small impurity atoms diffuse through the
interstices of the parent metal.
2) This method of diffusion is generally faster
than by vacancy diffusion because the
impurities are smaller and are more mobile.
The bonding of interstitials species to the
surrounding atoms is normally weaker and
there are many more interstitial sites than
vacancy sites to jump to.
Requires small impurity atoms (e.g. C, H, O)
to fit into interstices in host.
Steady-State Diffusion: Fick’s first law
Fick’s first law of diffusion state that for steady state diffusion
condition, the net flow of atoms by atomic diffusion is equal to
the diffusivity (D) times
the diffusion gradient dC/dx.

D is the diffusivity (diffusion coefficient)

J is the diffusion flux
dC/dx is the concentration gradient
The negative sign indicated the direction of the diffusion in m2/s from
higher to lower concentration
Example
Non Steady State Diffusion
1) In a non-steady state diffusion condition, the concentration
of atoms at any point in the material changes with time.
2) Most diffusion situations are non steady state.
3) The diffusion flux and the concentration gradient at some
particular point in a solid vary with time.

Non-steady-State Diffusion: Fick’s second law

Example
Example
Nitrogen from a gaseous phase is to be diffused into pure
iron at 700C. If the surface concentration is maintained at 0.1
wt% N, what will be the concentration 1 mm from the
surface after 10 h? The diffusion coefficient for nitrogen in
iron at 700C is 2.5 x 1011 m2/s.

This problem asks us to compute the nitrogen concentration (Cx) at the 1

mm position after a 10 h diffusion time, when diffusion is non-steady
state.
Example
Diffusion – Thermally Activated Process
The average thermal energy of an atom (kBT = 0.026 eV for room
temperature) is usually much smaller that the activation energy Em (~ 1
eV/atom) and a large fluctuation in energy (when the energy is “pooled
together” in a small volume) is needed for a jump.
The probability of such fluctuation or frequency of jumps, Rj, depends
exponentially on temperature and can be described by equation that is
attributed to Swedish chemist Arrhenius:
Diffusion – Temperature Dependence
Example
Example
Example
Factors that influence diffusion
Diffusion in material processing
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.
Practice Problems