Metals Dr.

Aseel Hadi

Construction of Phase Diagrams

Phase Equilibria
The term phase equilibrium refers to equilibrium as it applies to
systems in which more than one phase may exist. Phase equilibrium is
reflected by a constancy(‫ )ثبات‬with time in the phase characteristics of a
system.
The best example illustrates this concept. Suppose that a sugar–
water syrup is contained in a closed vessel(Figure 9.1)
Equilibrium is another essential concept that is best described in terms of
a thermodynamic quantity called the free energy. In brief, free energy is a
function of the internal energy of a system, and also the randomness or
disorder of the atoms or molecules (or entropy). A system is at
equilibrium if its free energy is at a minimum under some specified
combination of temperature, pressure, and composition.
In a macroscopic sense, this means that the characteristics of the system
do not change with time but persist(‫ )دام‬indefinitely ( ‫ ;)غير محدود‬that is,
the system is stable. A change in temperature, pressure, and/or
composition for a system in equilibrium will result in an increase in the
free energy and in a possible spontaneous change to another state
whereby the free energy is lowered.
 Metals Dr. Aseel Hadi

Types of Equilibrium Diagrams

1)One-Component Phase Diagrams
A phase diagram, also often termed an equilibrium diagram. Now,
there are three externally controllable parameters that will affect phase
structure—viz. temperature, pressure, and composition— and phase
diagrams are constructed when various combinations of these parameters
are plotted against one another.
The simplest and easiest type of phase diagram to understand is that
for a one-component system, in which composition is held constant (i.e.,
the phase diagram is for a pure substance); this means that pressure and
temperature are the variables. This one-component phase diagram (or
unary phase diagram) [sometimes also called a pressure–temperature
(or P–T) diagram] is represented as a two-dimensional plot of pressure
(vertical axis) versus temperature horizontal axis). Most often, the
pressure axis is scaled logarithmically.
We illustrate this type of phase diagram and demonstrate its
interpretation using as an example the one for , which is shown in Figure
(9.2). At one atmosphere pressure, during heating the solid phase
transforms to the liquid phase (i.e., melting occurs) at the point labeled 2
on Figure 9.2 (i.e., the intersection of the dashed horizontal line with the
solid-liquid phase boundary); this point corresponds to a temperature of
melting. Of course, the reverse transformation (liquid-to-solid, or
solidification) takes place at the same point upon cooling. Similarly, at
the intersection of the dashed line with the liquid-vapor phase boundary
[point 3 (Figure 9.2), at 100°C] the liquid transforms to the vapor phase
(or vaporizes) upon heating.
 Metals Dr. Aseel Hadi

2)Binary Phase Diagrams

Another type of extremely common phase diagram is one in which
temperature and composition are variable parameters, and pressure is held
constant—normally 1 atm. An explanation(‫ )تفسير‬the phase diagrams can
be demonstrated(‫ )شرح‬using binary alloys even though most alloys
contain more than two components. Binary phase diagrams are maps that
represent the relationships between temperature and the compositions and
quantities of phases at equilibrium, which influence the microstructure of
an alloy. Many microstructures develop from phase transformations, the
changes that occur when the temperature is altered (ordinarily upon
cooling).This may involve the transition from one phase to another, or the
appearance or disappearance of a phase.
 Metals Dr. Aseel Hadi

Binary Isomorphous Systems

The easiest type of binary phase diagram to understand and interpret

is the type that is characterized by the copper–nickel system (Figure
9.3a).
Three different phase regions, or fields, appear on the diagram, an alpha
( α) field, a liquid (L) field, and a two-phase field(α+L). The liquid ( L) is
a homogeneous liquid solution composed of both copper and nickel. The
(α) phase is a substitutional solid solution consisting of both Cu and Ni
atoms. Furthermore, with regard to phase boundaries, the line separating
the L and(α+ L) phase fields is termed the liquidus line, as indicated in
Figure 9.3a; the liquid phase is present at all temperatures and
compositions above this line. The solidus line is located between(α) the
(α+ L) and regions, below which only the solid phase exists.
For example, the melting temperatures of pure copper and nickel are
1085°C and1453 °C respectively. Heating pure copper corresponds to
moving vertically up the left-hand temperature axis. Copper remains solid
until its melting temperature is reached.
To compute the equilibrium concentrations of the two phases, the
following procedure is used:
1. A tie line is constructed across the two-phase region at the temperature
of the alloy.
2. The intersections of the tie line and the phase boundaries on either side
are noted.
3. Perpendiculars are dropped from these intersections to the horizontal
composition axis, from which the composition of each of the respective
phases is read. For example, consider again the 35 wt% Ni–65 wt% Cu
alloy at1250 C, located at point B in Figure 9.3b and lying within the (α+
L)region. Thus, the problem is to determine the composition (in wt% Ni
 Metals Dr. Aseel Hadi

and Cu) for both the and liquid phases. The tie line has been constructed
across the(α+ L) phase region, as shown in Figure 9.3b. The
perpendicular from the intersection of the tie line with the liquidus
boundary meets the composition axis at 31.5 wt% Ni–68.5 wt% Cu,
which is the composition of the liquid phase,C1 . Likewise, for the
solidus–tie line intersection, we find a composition for the α ,solid-
solution phase, Cα, of 42.5 wt% Ni–57.5 wt% Cu.
Metals Dr. Aseel Hadi