Topic-5: Phase Diagrams

Important concept
Phase: A phase is defined as a macroscopically homogeneous body of matter.
 In pure materials they seem to be different ways of arranging the atoms or molecules
 When we mix different compounds, we can extend the idea of phases.
Example of phase: Solid, liquid, gaseous,

Please remember: phase transformation is a thermodynamics concept and material will always tend to take
up its lowest energy state

Phase diagram is a graphical representation of the physical states of a substance under different conditions of
temperature and pressure. A typical phase diagram has pressure on the y-axis and temperature on the x-axis. As
we cross the lines or curves on the phase diagram, a phase change occurs.

Component and System: A system, as used in the sense usually employed in thermodynamics, or physical
chemistry, is an isolated body of matter. The components of a system are often the metallic elements that make up
the system. Pure copper or pure nickel are by themselves one-component systems, while alloys formed by mixing
these two elements are two-component systems.

Metallic elements are not the only types of components that can be used to form metallurgical systems; it is
possible to have systems with components that are pure chemical compounds.
Example: Steels are normally considered to be two-component systems consisting of iron (an element) and
iron carbide (Fe3C), a compound.
 Phase Diagram
Phase diagrams show areas of the predominance of phases with varying temperature, composition or pressure

Here we plot the areas of stability of different phases with composition for alloys composed of two types of atoms, A and
B, with temperature. By convention, unless the pressure is stated, standard room pressure is assumed.

The diagram is interpreted as follows:

 At high temperatures a single phase exists for all compositions, the liquid L. This is very typical for molten metals.
 A pure melt of A would then solidify and transform two a solid phase α. This phase α has an increasing capacity to
take B into its structure as the temperature decreases and its stability relative to the liquid increases - the alloy
‘wants’ to be solid.
 Similarly, a pure melt of B would solidify (at a different temperature to A) and form a phase β.
 Therefore for a dilute alloy of B in A a two-phase region can exist, where solid α co-exists with liquid L.
 At some point, it becomes more favorable to form a mixture of α and β instead of either
 L + α or L + β , and the alloy becomes completely solid.
 Therefore there are regions in the diagram where a single phase can exist and regions where a mixture of two phases
exists.
 The number of phase can co-exist in a phase field- follow the Gibbs phase rule (Comes from the thermodynamics)

Gibbs Phase rule: P + F = C +2 P: number of phases (ie. solid, liquid, or gas)

C: number of components
F: Degree of freedom
 Phase Diagram of water(H2O)[Single component System]
Gibbs Phase rule: P + F = C +2

Water:
a) At the triple point: P = 3 (solid, liquid, and gas)
C= 1 (water)
P+F=C+2
F = 0 (no degree of freedom)

b) liquid-solid curve: P = 2
2+F = 1 + 2
F= 1
One variable (T or P) can be changed

c) Liquid: P =1
So F =2
Two variables (T and P) can be varied independently and the system will remains a
single phase
 Phase Diagram of water(H2O)[Single component System]

 In a pure material (single component system), this means that

under any given external conditions (here, Pressure and
Temperature), only one phase is stable.
 There are lines at the boundary of stability of each phase where
the two coexist;
 An ice-water mixture can stably exist at a range of temperatures
for pressures above TP in the Figure. At room pressure this is at
0 ◦C, of course; similarly water and steam coexist at 100 °C at
room pressure (105 Pa).
 In this diagram there also exists a single unique point, the
TriplePoint, where all three phases can coexist.

Pressure-Temperature diagram for pure water

 An alloy composed mostly of A with limited amounts of B where the two elements are soluble in each other, then we
can form a single phase material, called a solid solution

 Only a few pairs of atom form a solid solution over the entire range of compositions from 100% A to 100% B but when
this occurs each grain or crystal is a random mixture, at the atomic scale, of the two elements- Complete Solid solution
Possible in substitutional solid solution only (discussed in topic-3).
 Complete solid solubility is rare, most combinations of elements have some solubility in each other- Partial solubility
Substitutional solid solution and interstitial solid solution both are possible.
 Combinations of elements of complete insoluble in each other is alloy possible ( not very common) – Immiscible system
not solid solution.
 Some times intermetallic is also possible to form (intermediate compounds)

Note: The phase transformation will be discussed in this chapter will be during solidification

Solidification process:
 In a pure metal, or any pure material, the liquid-solid transition occurs at a single
temperature, the melting point, at which latent heat is evolved.
 This latent heat is the energy difference between the high energy, disordered, liquid
state and the lower energy, ordered, solid state - in the liquid the atoms are arranged
randomly whereas in the solid they are arranged on a regular crystal lattice.
 Solidification reaction is exothermic, i.e. it produces heat.
 Phase Diagram of Binary alloys [Two component System]
 A mixture of two metals is called a binary alloy and constitutes a two-component system.
 Each metallic element in an alloy is called a separate component.

 Depending on the solid solubility and the phase transformation there are different type of binary phase diagram
is possible

1. Isomorphous systems : Contain metals which are completely soluble in each other and have a single type of
crystal structure. Example: Cu-Ni System.
2. Eutectic system: In systems of this type, there is always a specific alloy, known as the eutectic composition, that
freezes at a lower temperature than all other compositions. Example: Cu-Ag System
3. Peritectic System: Peritectic transformations are also similar to eutectic reactions. Here, a liquid and solid
phase of fixed proportions react at a fixed temperature to yield a single solid phase. Example: Al-Zr System
4. Monotectic System (No solid solubility): Monotectic represent another form of three-phase transformation in
which a liquid phase transforms into a solid phase and a liquid phase of different composition. Monotectic
transformations are associated with miscibility gaps in the liquid state. Example: Cu-Pb System

Note: Isomorphous systems and Eutectic system will be discussed in detailed

Types of solid solution

Discussed in Imperfection in Solids

 Binary phase diagram: Isomorphous System

A Cooling Curve of A-B alloys showing complete solubility.

 Alloy 1- 20%Ni
 Alloy 2- 40%Ni
 Alloy 1- 60%Ni
Cu-Ni equilibrium phase diagram
Constriction of Phase diagram: Experimental process
Microstructure during solidification

All liquid

Solid crystals start nucleating

Solid crystals grow

Solidification complete
 Lever rule
Determination of phase fraction in microstructure

Note: Practice the determination of phase fraction using lever rule from reference book
 Binary phase diagram: Eutectic system
 Eutectic system between two metals A and B
 Form two solid solutions (limited solubility), one rich in A (α) and another rich in
B (β).

Three phases (L+α+β) coexist at point E. This point is called eutectic point or composition.
Left of E is called hypoeutectic whereas right of E is called hypereutectic.
Binary phase diagram: Eutectic system
Microstructure during solidification
 Binary phase diagram: Eutectic system

A eutectic composition solidifies as a eutectic mixture of α and β phases. The

microstructure at room temperature (RT) may consist of alternate layers or
lamellae of α and β.
Solidification and solid-state precipitation in a two-phase alloy
Solidification sequence in a near-eutectic alloy
 Binary phase diagram: Eutectic system
Pb-Sn Phase diagram

a) A Hypoeutectic alloy (40wt.% Sn), showing

dendrites of primary Pb in a Pb-Sn
eutectic, (b) a eutectic Pb-Sn alloy, (c) a
hypereutectic alloy (80wt.% Sn) with dendrites of
primary Sn in a Pb-Sn eutectic, (d) the Pb-Sn binary
eutectic phase diagram [micrographs from Richard
Dashwood; diagram from ASM handbook]