Phase Transformation
by
Dr. K. C. Sahoo
Introduction
• A phase transformation is a change in the pattern of atoms
in a material.
• It can occur within a phase, such as from one temperature
phase to another (like α to β to γ to delta in Fe), or between
phases, such as from solid to liquid.
• Phase transformations are influenced by factors such as
the chemical composition, temperature and pressure,
and magnetic field of the material.
• Phase transformations affect the properties of the material,
such as its hardness, strength, ductility and electrical
conductivity.
Classification of Transformations
Phase Diagrams
• The study of phase relationships plays an important role in the
understanding of the properties of materials.
• Phase diagrams are maps that give the relationships between
phases in equilibrium in a system as a function of temperature,
pressure and composition.
• Importance of the study of phase diagrams is the first step towards
gaining an insight into the control of microstructure.
• Phases as determined from the microstructure of a material may or
may not correspond to the equilibrium phases indicated by the
phase diagram. In fact, the thermal treatment given to a material
often results in phases other than those in the diagram.
The Phase Rule
• The phase rule enunciated by Gibbs has a simple form:
F=C–P+2
F is the degrees of freedom, C is the number of
components and P is the number of phases in equilibrium in
a system.
Phase
• A phase is a physically distinct, chemically homogeneous and mechanically
separable region of a system. Ex: gaseous, the liquid and the solid states,
form separate phases.
• The gaseous state is always a single phase, as the atoms (or molecules) in
the gas are mixed at the atomic (or molecular) level. A liquid solution is also a
single phase. For example, if salt is dissolved in water, the water molecules,
the sodium ions and the chlorine ions are mixed at the atomic level in the
solution.
• A liquid mixture (e.g. oil and water), on the other hand, forms two separate
phases as there is no mixing at the molecular level.
• In the solid state, different chemical compositions and different crystal
structures are possible so that a solid may consist of several phases.
• For the same composition, different crystal structures represent different
phases. A solid solution has the atoms mixed at the atomic level within the
unit cell and is therefore a single phase.
Components
• The components of a system may be elements, ions or compounds. They
refer to the independent chemical species that comprise the system.
• In the ice–water–steam system, the component is H2O. In the Cu–Ni system,
the elements Cu and Ni are the components, whereas in the Al2O3–Cr2O3
system, the two oxides can be taken to be components. In the Fe–C system,
iron and graphite can be the components, but it may be often convenient to
choose iron and iron carbide (Fe3C) as the components.
• The variables of a system include the two external parameters, temperature
and pressure. Within the system, there are variables that specify the
compositions of the phases present.
• Compositions are expressed as weight (or atom %) so that the number of
variables required to specify completely the composition of a phase is (C –
1), where C is the number of components in the system.
Degrees of freedom
• If there are P phases in a system, the total number of composition
variables is P(C – 1). Including the two external variables (pressure
and temperature), the total number of variables is P(C – 1) + 2.
• The number of independent variables among these gives the
degrees of freedom F. Clearly, this number cannot be more than
the total number of variables.
• F = C – P + 2 ≤ P (C – 1) + 2
• As the number of phases increases, the degrees of freedom
decrease.
• The degree of freedom cannot be less than zero so that we have
an upper limit to the number of phases that can exist in equilibrium
in a given system.
Example 7.1 What are the degrees of freedom of a system of two components when the
number of phases is one, two, three, and so on?
Classification
• Phase diagrams are classified on the basis of the number of
components in the system.
• Single-component systems have unary diagrams, two-
component systems have binary diagrams, three-component
systems give rise to ternary diagrams, and so on.
Single-component Systems
• In single-component systems, there is no composition
variable and the only other variables are temperature and
pressure.
• The phase diagram for iron is shown in Fig.7.1
• Pressure is plotted on the x-axis and temperature on the y-
axis.
• The pressure axis starts from 0.1 MPa but can be extended
to lower pressures
Contd...
• Consider first the single-phase regions on the diagram such as
gas, liquid and several crystal forms of iron. From the phase rule
for C = 1 and P = 1, we have F = 2.
• Therefore, in a single-phase region, both temperature and
pressure can be varied independently within the limits
prescribed by the boundaries of the region.
• When two phases are in equilibrium, F = 1, that is, either
temperature or pressure can be varied independently, but not both.
Two-phase equilibrium exists along the phase boundaries of Fig.
7.1.
• Three-phase equilibrium exists at points on the phase diagram,
where three phase boundaries meet. Two such points are shown in
Fig. 7.1. Such points are called triple points.
• Here, F = 0; neither pressure nor temperature can be varied
arbitrarily. Three phases will co-exist at only one particular
combination of pressure and temperature.
• If we alter pressure or temperature from the fixed triple-point value,
one or two of the phases will disappear.
• On heating to 910°C, changes over to the FCC () form* . On
heating to 1410°C, the iron changes over to the BCC () form.
• As the pressure is increased, the → transition temperature is
lowered, whereas → the transition temperature is increased
