Defects in the ordered phases

As discussed there could be mainly two types of point defects in pure metals.

Concentration of defects mainly depends on the temperature and the activation

energies.

However, in an ordered phase or intermetallic compound, concentration of

defects depends not only on the temperature but also because of deviation from
the stoichiometric composition.

There are mainly two types of defects present because of which deviation from
the stoichiometry is possible.

One of the very common defect is antisite. In an ordered phase, in general, one
particular element sits on a particular sublattice. However, when it occupies
another sublattice, which is actually for another element is called antisite.

Another type of defect, which is not very common, is called triple defect. It has
three defects. 2 vacancies on one sublattice and another antisite on another
sublattice.

Both the types of defects are found in β phase in different systems.

 Stoichiometric composition of the β-phase

β phase has 50:50 stoichiometric composition (shown by red dash line) and
may deviate from both the sides (A or B rich sides). It shows the
composition deviation, for example, at temperature T.
This phase can have two sublattices, α and β. If α sublattice is occupied by
the element A then β sublattice will be occupied by the element B in a
binary A-B system.
(note: although similar symbol is used, β phase is a compound and β
sublattice shows the position of the atom B)
(a) Crystal structure of a
stoichiometric compound,
ignoring the thermal defects.
(b) In some systems, deviation from
the stoichiometry is possible
because of presence of triple
defects at one side of the
stoichiometry and antisite defects
at other side of the stoichiometry
(for example, in NiAl, CoAl, NiGa,
CoGa phases in the Al or Ga rich
side deviation occurs because of
the presence of triple defects and
in the Ni or Co rich sides deviation
occurs because of the presence
of antisites.
(c) In most of the systems, deviation
from the stoichiometry is possible
because of the presence of
antisite defects at both sides of
the stoichiometry, for example,
AgZn, AuZn.

Antisite defects not necessarily present because of deviation from stoichiometry
only.

For example, in Ni3Al even at stoichiometric 75:25 composition, the concentration
of antisite defects is reasonably high. Concentration of these defects for different
elements vary from the stoichiometric composition depending on the deviation from
the stoichiometry.

Further, vacancy concentration may not be the same on different sublattices.

For example, the concentration of Ni vacancies is much higher than the
concentration of Al vacancies.

Al Ni
Al Ni Ni
Al Ni Ni
Al
Al
Ni
Al VN
VN i

i VAl
VN
i VAl

VAl

1200 K 1400 K 1600 K

Numakura et al. Phil. Mag. 77 (1998) 887
 Calculation of the molar volume

The knowledge of molar volume is prerequisite in most of the diffusion

parameter calculations.

In most of the cases, the calculation is very straightforward.

However, in few cases, concentration of vacancies (if the concentration is

reasonably high) should be considered during calculation as explained.

Molar volume can be calculated from the knowledge of lattice parameter

of a unit cell and number of atoms present in the cell. For example, in a
cubic crystal

Vcell
Vm = N Avo na = total number of atoms in a cell
na
a3 a = lattice parameter
= 6.023 × 10 23
2

Note that the total number of atoms is important to calculate the molar volume, which
may have only one type of element A or two types of elements A and B in an alloy.

Molar volume of alloys in a binary A-B system may not follow the straight line
connecting molar volume of pure elements VA and VB. For example, in the figure below,
it deviates negatively from the straight line.

The knowledge of partial molar volumes of the species in an alloy with particular
composition is also important.
* *

At composition,X B , the molar volume of the alloy is Vm . Then the partial molar
* *
volumes of A, VA and B, VB can be found by taking a slope at the molar volume of that
composition and by extending it to XB = 0 and 1, respectively.

A *
Vm = X A VA* + X B VB*

a
 Cell volume for different crystal structure

Cubic (a = b = c; α = β = γ = 90Ο) : a3
Tetragonal (a = b ≠ c; α = β = γ = 90Ο) : a 2c
Hexagonal (a = b ≠ c; α = β = γ = 90Ο, γ = 120Ο) :
(Note: the volume is one third of the hexagon)
( )
3 2 a 2c

Orthorhombic (a ≠ b ≠ c; α = β = γ = 90Ο): abc

Monoclinic (a ≠ b ≠ c; α = γ = 90Ο ≠ β): abc sin β

Rhombohedral (a = b = c; α = β = γ = equal but ≠ 90Ο): a 3 1 − 3 Cos 2α + 2 Cos 3α

Triclinic (a ≠ b ≠ c; α ≠ β ≠ γ ≠ 90Ο):

a 3 1 − cos 2 α − cos 2 β − cos 2 γ + 2 cos α cos β cos γ

 Calculation of molar volume using
pearson symbol and lattice parameter

In general it is convenient to get the Pearson symbol and lattice

parameter data, especially if the crystal structure is complicated.

Designation in Pearson symbol

a = triclinic (asymmetric), m = monoclinic, o = orthorhombic, t = tetragonal,

h = hexagonal and rhombohedral (trigonal), c = cubic

P = primitive, I = body center, F = face center, C = end center

For example: Nb3Sn phase is designated as cP8: cubic, primitive with 8

atoms in a cell with lattice parameter data a = 0.5169 nm

So the molar volume of the Nb3Sn phase is

Vcell
Vm = N Avo
na
(0.5169)3 x10 -27 3
= × 6.023 ×10 23 = 10.4 x10 −6 m /mole
8

It should be noted that, we actually calculate the molar volume of one mole of
atoms (not the lattice sites).

Not necessarily all the lattice sites are occupied because of the presence of
vacancies.

In general concentration of thermal vacancies is very low and can be ignored.

However, in some cases, the concentration of structural vacancies (because of
which few ordered phases can deviate from the stoichiometric composition) could be
reasonably high as shown in the figure below.

For example, at 55 at.%Al, 10 percent vacancies are present.

In this case, we need to consider it for the calculation of molar volume.

Reference: Chang and Neumann, Prog. Solid State Chem. 14 (1982) 221
 Vcell

Molar volume can be calculated from Vm = No
na

Vm is the molar volume, Vcell is the volume of the cell, na is the number of atoms in
the unit cell and No is the Avogadro number.

It should be noted that in the Ni rich side of the 50:50 stoichiometric
compositions, there are no structural vacancies present and number of lattice sites,
ns is equal to the number of atoms, na.

In the Al rich side, on the other hand, n a = n s − nV

where nV is the number of constitutional vacancies

7.8

Note that the rate of change in molar volume

Vm (x10-6 m3/mol)

7.6
in the Al rich side is higher than the Ni rich
side because of the presence of
7.4
constitutional vacancies.

7.2

7.0
0.40 0.45 0.50 0.55
XAl = NAl/(NAl+NNi)