Phase Diagrams and Solidification 

Aims
On completion of this TLP you should:

 understand the thermodynamic principles behind free-energy curves

 understand how free-energy curves relate to equilibrium phase diagrams
 be able to construct a binary phase diagram from cooling curves
 be able to use phase diagrams to predict the composition and volume fraction
of phases

A typical simple binary phase diagram is as follows:

Where L stands for liquid, and A and B are the two components
and α and β are two solid phases rich in A and B respectively. The blue lines
represent the liquidus and solidus lines, which are relatively simple to measure. The
red lines involve a solid-to-solid transition, and so require much more sensitive
equipment

Free energy curves

For any phase the free energy, G, is dependent on the temperature, pressure and
composition.

Pure Substances
For pure substances the composition does not vary and there is little dependence on
pressure. Therefore the free energy varies greatest with temperature.

The phase with the lowest free energy at a given temperature will be the most stable.
The curves for the free energies of the liquid and solid phases of a substance have
been plotted below. It shows that below the melting temperature the solid phase is
most stable, and above this temperature the liquid phase is stable. At the melting
temperature, where the two curves cross, the solid and liquid phases are in
equilibrium.

Phase diagrams 1
Free energy curves can be used to determine the most stable state for a system, i.e.
the phase or phase mixture with the lowest free energy for a given temperature and
composition. Below is a schematic free-energy curve for the solid phase of an alloy.
The solid shown could either exist as a mixture or as a homogeneous solution of A
and B. The figures below show that an alloy of composition C can exist in different
configurations with differing free energies. In the first figure (below) the free energy
of unmixed A and B is shown as the diagonal black line. The free energy of this
mixture at composition C is shown as a red point.

The system can reduce its free energy by existing as a mixture of two phases
Though the system has reduced its free energy from that of the mixture, the most
stable configuration for the system is a solid solution. This allows the free energy of
the system to sit on the free energy curve.

For most systems there will be more than one phase and associated free-energy
curve to consider. At a given temperature the most stable phase for a system can
vary with composition. While the system could consist entirely of the phase which is
most stable at a given composition and temperature, if the free energy curves for the
two phases cross, the most stable configuration may be a mixture of two phases with
compositions differing from that of the overall system. The total free energy of the
system in any given two-phase configuration can be found by linking the two phases
in question with a straight line on a free-energy plot.
Taking a line that is a common tangent to the two free-energy curves produces the
lowest possible free energy for the system as a whole. Where the line meets the free
energy curves defines the composition of each phase.

For positions where it is not possible to draw a common tangent between the two
free-energy curves the system will sit entirely in the phase with the lowest free
energy. The borders between the single- and two-phase regions mark the positions
of the solidus and liquidus on the phase diagram.

When the temperature is altered the compositions of the solid and liquid in
equilibrium change and build up the shape of the solidus and liquidus curves on a
phase diagram.

Below, a binary system can be seen along with the free-energy curves for the liquid
and solid phases at a range of temperatures shown on the phase diagram.
Phase diagrams 2
The free-energy curves and phase diagrams discussed in Phase Diagrams 1 were all
for systems where the solid exists as a solution at all compositions and temperatures.
In most real systems this is not the case. This is due to a positive ΔHmix caused by
unfavourable interactions between unlike neighbour atoms. As the temperature is
reduced the ΔHmix term becomes more significant and the curve turns upward at
intermediate compositions, resulting in a curve with two minima and one maximum
as described earlier. A common tangent can then be drawn between the two minima
showing that the system can reduce its free energy through existing as a mixture of
two distinct phases.

The free energy of a system of composition Co can be minimised by existing as a

mixture of two solid phases of composition C1 and C2:

This effect can result in a system which, though single-phase upon solidification, will
separate into two solid phases on cooling (e.g. Cr-W).

Another possible result is that the free-energy curve for the liquid will intersect the
up turned section of the free-energy curve for the solid before the temperature is
high enough to induce the formation of a solid solution. As the temperature is
increased, the free-energy curve for the liquid moves downward relative to the solid
curve and reaches a position where it is possible to link two parts of the solid free
energy curve and one part of the liquid free energy curve with a common tangent. At
this temperature three phases are in equilibrium.

Here the system is at the eutectic temperature and three phases can be joined by a
common tangent:

This is known as the eutectic temperature. At this temperature there will be a

composition which solidifies at a single temperature through the co-operative
growth of the two solid phases. This is the eutectic composition. It is this
composition which will exhibit the lowest melting point for the system.

At temperatures above that of the eutectic there will be two common tangents
producing two two-phase regions at the same temperature. The two different solid
phases are commonly labeled as α and β

Eutectic systems therefore have a liquidus which contains a V to the eutectic point
where it meets the eutectic invariant-reaction line.
Here is an example of a eutectic phase diagram. α and β are both solid phases.

The two-phase solid region on the phase diagram will consist of a mixture of eutectic
and either α or β phase depending on the whether the alloy composition is
hypoeutectic or hypereutectic. The constitution of an alloy under equilibrium
conditions can be found from its phase diagram. This will be discussed in a later
section.

The lever rule

If an alloy consists of more than one phase, the amount of each phase present can
be found by applying the lever rule to the phase diagram.

The lever rule can be explained by considering a simple balance. The composition of
the alloy is represented by the fulcrum, and the compositions of the two phases by
the ends of a bar. The proportions of the phases present are determined by the
weights needed to balance the system.

So,

fraction of phase 1 = (C2 - C) / (C2 - C1)

and,

fraction of phase 2 = (C - C1) / (C2 - C1).

Lever rule applied to a binary system

Point 1
At point 1 the alloy is completely liquid, with a composition C. Let

C = 65 weight% B.

Point 2
At point 2 the alloy has cooled as far as the liquidus, and solid phase β starts to form.
Phase β first forms with a composition of 96 weight% B. The green dashed line below
is an example of a tie-line. A tie-line is a horizontal (i.e., constant-temperature) line
through the chosen point, which intersects the phase boundary lines on either side.

Point 3
A tie-line is drawn through the point, and the lever rule is applied to identify the
proportions of phases present.
Intersection of the lines gives compositions C1 and C2 as shown.

Let

C1 = 58 weight% B

and

C2 = 92 weight% B

So,

fraction of solid β = (65 - 58) / (92 - 58) = 20 weight%

and

fraction of liquid = (92 - 65) / (92 - 58) = 80 weight%

Point 4

Let

C3 = 48 weight% B

and

C4 = 87 weight% B

So

fraction of solid β = (65 - 48) / (87 - 48) = 44 weight%.

As the alloy is cooled, more solid β phase forms.

At point 4, the remainder of the liquid becomes a eutectic phase of α+β and

fraction of eutectic = 56 weight%

Point 5
Let

C5 = 9 weight% B

and

C6 = 91 weight% B

So

fraction of solid β = (65 - 9) / (91 - 9) = 68 weight%

and

fraction of solid α = (91 - 65) / (91 - 9) = 32 weight%.