Suite Chapter 1 Phase Transformations

Thermodynamic equilibrium: is described quantitatively by the free energy G = H - TS
H is enthalpy, which is a function of the internal energy of a system,

S is entropy, the disorder of atoms or molecules.
A system is at equilibrium if its free energy is at a minimum under a certain specified combination
of temperature, pressure and composition: dG = 0.
Macroscopically: the characteristics of the system do not change over time but persist indefinitely;
in other words, the system is stable.
A change in temperature, pressure and/or composition for a system which is initially in equilibrium
will result in a change in the free energy  a spontaneous transition to another state for which the
free energy is lowered.
Phase diagrams:
Much of the information about controlling the phase structure of a system is given on a phase
diagram, also often called an equilibrium diagram.
There are three external parameters that can control the phase structure: temperature, pressure
and composition. Phase diagrams are constructed when various combinations of these
parameters are plotted against each other.
The simplest and easiest type of phase diagram to understand is the one-component diagram, in
which the composition is kept constant: pressure and temperature are the variables.
This one-component phase diagram (or unary phase diagram) is represented by a two-
dimensional graph P = f (T).
There are three different phases (regions): solid, liquid and vapor. These regions are delimited by
lines which are phase boundaries (marked aO, bO and cO). Each phase exists under equilibrium
conditions of temperature and pressure.
At any point on one of the curves marked aO, bO and cO, the two phases on either side of the
curve are in equilibrium (or coexisting) with each other. That is, the equilibrium between the solid
and vapor phases is along curve aO - similarly for the solid-liquid, curve bO, and the liquid-vapour,
curve cO.
When a boundary is crossed (as temperature and/or pressure is altered), one phase is
transformed into another.
Example: at atmospheric pressure, during heating, the solid phase transforms into the liquid
phase (i.e. melting occurs) at the point labelled 2 corresponding to a temperature of 0 ◦C.
The reverse transformation (liquid-solid, or solidification) takes place at the same point after
cooling.
Gibss phase rule:
It describes the relationship between the number of components and the number of phases for a
given system and the conditions that may be allowed to change (e.g., temperature, pressure, etc.).
It has the general form: 2 + C = F + P (when temperature and pressure both can vary)
where: C: number of constituents; F: number of independent variables (T, P or composition); P:
number of phases in equilibrium.
Example:
Let’s consider the case of pure magnesium (Mg). Figure below shows a unary (C =1) phase
diagram.
Suppose we have a combination of pressure and temperature that put us at point A in the phase
diagram. At this point, all magnesium is liquid.
The number of phases is one (liquid)the phase rule tells us that there are two degrees of
freedom. 2 + C = F + P; therefore; 2 + 1 = F +1  F = 2
F = 2? We can change the pressure, the temperature, or both, and still be in an all-liquid portion of
the diagram. Another way, we must fix both the temperature and the pressure to know precisely
where we are in the liquid portion of the diagram.
Consider point B: the boundary between the solid and liquid portions of the diagram:
- The number of components, C, is still one,
- At point B, the solid and liquid coexist, or the number of phases P = 2.
From the phase rule Equation, 2 + C = F + P F = 1: there is only one degree of freedom.
If we change the temperature, the pressure must also be adjusted if we are to stay on the
boundary where the liquid and solid coexist. On the other hand, if we fix the pressure, the phase
diagram tells us the temperature that we must have if solid and liquid are to coexist.
At point X, solid, liquid, and vapor coexist: C = 1, P = 3  F = 0: we have no degrees of freedom;
all three phases coexist only if both the temperature and the pressure are fixed. A point on the
phase diagram at which the solid, liquid, and gaseous phases coexist under equilibrium conditions
is the triple point.
Binary phase diagrams:
Another extremely common type of phase diagram is one in which temperature and composition
are variable parameters, and pressure is held constant (1 bar).
Binary phase diagrams are maps that represent the relationships between temperature and
equilibrium phase compositions and quantities, which influence the microstructure of an alloy.
Many microstructures develop from phase transformations, the changes that occur when
temperature is altered (usually during cooling). This can involve the transition from one phase to
another, or the appearance or disappearance of a phase.
Binary phase diagrams are useful for predicting phase transformations and the resulting
microstructures (equilibrium or non-equilibrium).
Liquidus and Solidus Temperatures:
We define liquidus temperature as the temperature above which a material is completely liquid.
The solidus temperature for an alloy is the temperature below which the alloy is 100% solid.
The temperature difference between the liquidus and the solidus is the freezing range of the alloy
The simplest binary phase diagram to understand and interpret is the Cu-Ni type: The temperature
is plotted on the ordinate, and the abscissa represents the composition of the alloy (in mass or
atomic percentage). The composition ranges from 0 wt.% Ni (100 wt.% Cu) on the horizontal left to
100 wt.% Ni (0 wt.% Cu) on the right.
Example:
Determine the degrees of freedom in a Cu-40% Ni
alloy at (a) 1300 °C, (b) 1250 °C, and (c) 1200 °C.

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Thermodynamic equilibrium: is described quantitatively by the free energy G = H - TS

H is enthalpy, which is a function of the internal energy of a system,

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