Week-01
New Topics:
Diffusion
Reference Materials:
1)Chapter-2, 'Phase Transformations in Metals and Alloys'', by D.A. Porter and K.E.
Easterling; Chapman & Hall
2) Lecture Note
What is Diffusion?
● In materials science, diffusion is the process by which
atoms, molecules, or ions move from regions of higher
concentration to regions of lower concentration within a
material.
● This movement occurs due to the random thermal motion of
particles, leading to their redistribution and mixing over
time.
● Diffusion is a fundamental mechanism that influences
various material properties, such as composition, phase
transformations, growth, and chemical reactions.
● It plays a crucial role in shaping the behavior and
performance of materials in diverse applications, from
metallurgy to electronics and beyond.
● The reason why diffusion occurs is always so as to produce
a decrease in Gibbs free energy.
● As a simple illustration of this consider Fig. 2.1.
● Two blocks of the same A-B solid solution, but with
different compositions, are welded together and held at a
temperature high enough for long-range diffusion to occur.
● If the molar free energy diagram of the alloy is as shown in
Fig. 2.1b, the molar free energy of each part of the alloy will
be given by G1 and G2 , and initially the total free energy of
the welded block will be G3.
● However, if diffusion occurs as indicated in Fig. 2.1a so as
to eliminate the concentration differences, the free energy
will decrease towards G4 , the free energy of a
homogeneous alloy.
● Thus, in this case, a decrease in free energy is produced by A
and B atoms diffusing away from the regions of high
concentration to that of low concentration, i.e. down the
concentration gradients.
● In alloy systems that contain a miscibility gap the free energy
curves can have a negative curvature at low temperatures.
● If the free energy curve and composition for the A-B alloy
shown in Fig. 2.1a were as drawn in Fig. 2.1d the A and B
atoms would diffuse towards the regions of high
concentration, i.e. up the concentration gradients, as shown
in Fig. 2.1c.
● As can be seen in Fig. 2.1e and f the A and B atoms are
diffusing from regions where the chemical potential is high
to regions where it is low, i.e. down the chemical potential
gradient in both cases.
● In practice the first case mentioned above is far more
common than the second case, and it is usually assumed that
diffusion occurs down concentration gradients.
● However, it can be seen that this is only true under special
circumstances and for this reason it is strictly speaking better
to express the driving force for diffusion in terms of a
chemical potential gradient.
● Diffusion ceases when the chemical potentials of all atoms
are everywhere the same and the system is in equilibrium.
● Since case 1 above is mainly encountered in practice and
because concentration differences are much easier to
measure than chemical potential differences, it is
nevertheless more convenient to relate diffusion to
concentration gradients.
● The remainder of this chapter will thus be mainly concerned
with this approach to diffusion.
Atomic Mechanism of Diffusion
● Two common mechanisms enable atomic diffusion in
solids, determined by lattice site type.
● Substitutional atoms diffuse via vacancies; smaller
interstitial atoms migrate by moving between larger
atoms (interstitially).
● Substitutional atoms in a crystal vibrate around a site,
surrounded by similar neighboring atoms.
● Each atom's average vibrational energy (3kT)
increases proportionally with absolute temperature.
● Vibrational energy rises by increasing oscillation
amplitude due to constant mean frequency of
vibration.
● Movement of substitutional atoms is restricted by
neighbors; they can jump to a vacant site during
violent oscillation.
● Illustration in Fig. 2.2 shows atoms' movement to
vacant site requiring shaded atoms to separate,
enabling migration.
● Jump probability depends on acquiring sufficient
vibrational energy for atoms to jump into vacant sites.
● Atom migration rate depends on encountering
vacancies, influenced by vacancy concentration.
● Both jump probability and vacancy concentration are
extremely temperature-sensitive.
● Solute atoms smaller than solvent occupy interstitial
sites; FCC's interstitial sites are on cube edges (Fig.
2.3a).
● These sites form octahedrons with six surrounding
atoms; in BCC, interstitials occupy edge/face-
centering sites (Fig. 2.3b).
● Concentration of interstitial atoms is low, leaving most
sites vacant.
● Each interstitial atom, surrounded by vacant sites, can
frequently jump due to thermal energy overcoming
strain energy barriers (Fig. 2.4).
