BINARY PHASE

DIAGRAMS
Relation with
Free Energy-Composition
curves

A SIMPLE PHASE
DIAGRAM

A and B are completely miscible in

both liquid and solid states,
Both are ideal
solutions

SYSTEMS WITH A MISCIBILITY GAP

Free energy curve for a system in
which:
The liquid phase is
ideal
But for solid phase
Hmix > 0
(i.e. A and B atoms dislike
each other)

Therefore, at low
temperatures (T3), the
free energy curve for
the solid assumes a
negative curvature in
the middle.
The solid solution is thus
most stable as a
mixture of two
phases and with
compositions e and f.

SYSTEMS WITH A MISCIBILITY GAP

At higher
temperatures,
when T Smix
becomes larger:
e and f will
approach each other
and eventually
disappear (Fig 1.30d).

The ( + )
region
is
known
as
MISCIBILITY
GAP.

SYSTEMS WITH A MISCIBILITY GAP

The effect of +ve
Hmix in the solid is
also apparent at
higher temperatures
where;
It gives rise to a
minimum melting
point mixture

(simply because the A

and B atoms dislike
each
other
and,
therefore, its easy to
break
them
apart
when
they
are
in
mixture form )

Simple Eutectic System

s

If the H mix is much larger than

zero, the miscibility gap can
extend into the liquid phase.

Simple eutectic
phase diagram
results.

Simple Eutectic System

A similar phase diagram can result when A & B
have different crystal structures

Ordered Alloys
This effect (ordering) arises when, Hmix
<0
In these systems melting
will be more difficult in the
alloys and a maximum
melting point mixture may
appear.
This type of alloy has a
tendency to order at low
temperatures.

If
the
attraction
between
unlike
atoms
is
very
strong, the ordered
phase may extend
as far as the liquid.

PHASE DIAGRAMS WITH INTERMEDIATE

PHASES
When stable
intermediate phases
can form,

Extra free energy curves

appear in the phase diagram

PHASE DIAGRAMS WITH INTERMEDIATE

PHASES
When stable
intermediate phases
can form,

Extra free energy curves

appear in the phase diagram

Peritectic
transformati
on

PHASE DIAGRAMS WITH INTERMEDIATE

PHASES
An interesting result of the common tangent construction
is that:
The stable composition
range of the phase in the
phase diagram need not
include the composition
with the minimum free
energy, but is determined
by the relative free
energies of the adjacent
phases, Figure 1.35.

e.g.
Phase in the Cu-Al
system is usually denoted
as CuAl2
although the
composition XCu = 1/3, XAl
= 2/3 is not covered by
the field on the phase
diagram.

Stable
Compositions

Stoichiometric
composition
(AxBy) with min.
G

PHASE DIAGRAMS WITH INTERMEDIATE

PHASES

Formation of stable intermediate compounds will restrict

primary solid solubility.

The likelihood of the formation of such compounds in an

alloy system is related to the chemical affinity of the
participating elements and will be increased if one element
is more electronegative and the other more electropositive.

The width of the

shaded area
represent the extent
of primary solid
solubility
it becomes more
restricted the greater
the stability of the
intermediate phase.

SPINODAL DECOMPOSITION

Phase separation with no

barrier to nucleation

For compositions at Xo
below a critical
temperature, the alloy
will be unstable because
small fluctuations in
composition that produce
A-rich and B-rich regions
will cause the total free
energy to decrease.

Therefore, uphill
diffusion takes place.