Diffusion

Diffusion – movement of atoms within a solid

solution; particularly important since most
solid-state reactions involve atomic movements
that occur in solid solutions
Examples:
1. Homogenization of cast alloys – movement of
component atoms from regions of high
concentration to low concentration
2. Addition of carbon to the surface of low
carbon steel for surface hardening
Diffusion Mechanisms in a Crystalline Lattice

1. Vacancy or substitutional mechanism – recall

that activation energy for self-diffusion consists
of the activation energy to form a vacancy and
the activation energy to move the vacancy;
- Also occurs in alloys; However, due to
differences in atomic size and chemical bonding
of components and their solid solubility,
substitutional diffusion data must be obtained
experimentally
2. Interstitial Diffusion Mechanism – interstitial
(small sized atoms such as hydrogen, oxygen,
nitrogen and carbon) atoms move from one
interstitial site to another neighboring
interstitial site without permanently displacing
any of the atoms in the matrix crystal lattice;
- presence of vacancies not required for the
solute atoms to move
 Kirkendall Effect
• Confirmation of the vacancy mechanism
• Atoms in the FCC, BCC and HCP move in the
crystal lattice as a result of vacancy motion
• In a binary solid solution, each of the two
atomic forms can move with a different
velocity as will be seen in the next slides
At the start of the diffusion experiment;
• The wires are inert markers (refractory metal
that will not dissolve in the alloy system to be
studies;
• Afterwards, diffusion couple heated close to
melting point of the metals comprising the bar
and maintained for a relatively long time (say,
for a number of days since solid diffusion very
much slower compared to gases and liquids)
Penetration curves – flow of A atoms to the left
while B atoms flow to the right
Observe that markers at the diffusion interface moved slightly
in the opposite direction to the faster diffusing component
• Movement of wires during the diffusion
process – can only be explained with A atoms
diffusing faster than the B atoms
• Element with the lower melting point diffuses
faster
• Voids or pores form in the region of the
diffusion zone which suffers a loss of mass
because it loses more atoms than it gains
• Equivalent flow of vacancies in the reverse
direction to the net flow of atoms
• Net flow of vacancies occurs from the nickel
rich side of the bar toward the copper rich side
(dislocation climb – sink and sources of
vacancies)
Steady State Diffusion – no change in the concentration
of solute atoms in planes x1 and x2
Note the negative sign to denote a negative diffusion gradient (net
flow of atoms from a higher concentration to a lower
concentration)
Diffusion flux – rate of mass transfer (kgs or
atoms/meter squared/sec)
 Non-Steady State Diffusion
• Steady-state diffusion - not commonly
encountered with engineering materials
• Non steady state diffusion – concentration of
solute atoms at any point in the material
changes with time
For example, surface hardening
If the diffusivity of gas A in solid B is independent of position,
• Relationship between concentration,
position and time
• Cx being a function of the dimensionless
parameter (error function)
• Cx may be determined at any time and
position if the parameters Co, Cs and D
are known
Magnitude of diffusion coefficient D indicative of
the rate at which atoms diffuse;
 Factors that Influence Diffusion
1. diffusing species and host material influence
the diffusion coefficient – At 500◦C, compare
self diffusion of α Fe and diffusion of C in α
Fe
Type of diffusion mechanism – self
diffusion occurs by a vacancy mechanism
while carbon diffusion in iron is from one
interstitial site to another
• Interstitial diffusion occurs much more rapidly
than vacancy diffusion since interstitial atoms
are smaller and thus more mobile
• There are also more empty interstitial
positions than vacancies
2. Temperature
3. Type of crystal structure of the solvent lattice
- compare diffusivity of carbon in
BCC iron and FCC iron
4. Type of crystal imperfections – “short circuit”
diffusion paths along dislocations, grain
boundaries and external surfaces; much faster
than bulk diffusion
- overall diffusion rate would be higher in a
fine grained metal