Phase Diagram

Phase
• A chemically and structurally homogeneous
portion of the microstructure.
• A single-phase microstructure can be
polycrystalline.
• Phases are formed from distinct chemical
substances (components).
• Degree of freedom are the number of
independent variables available to the system.
• A pure metal at melting temperature has no degree
of freedom.
Gibbs Phase Rule
Number of Degrees of Freedom (F) can be expressed as,
State variables are limited
𝐹 =𝐶−𝑃+2 to two (Temperature and
Pressure)
Number of Number of
Components Phases

Materials processing mostly involve solids and liquids phases (condensed

system). The effect of pressure for such system is very minimum. (Presure is
fixed at 1atm)
The phase rule can be rewritten for such system as,
𝐹 =𝐶−𝑃+1
Sample problem 1

At 200 °C, a 50:50 Pb-Sn solder alloy exist as two phases, a lead-rich
alloy and a tin-rich liquid. Calculate the degrees of freedom for this
alloy and comment on its practical significance.
Phase Diagram
• A phase diagram is any kind of graphical representation of the state
variables associated wit microstructure through Gibbs phase rule.
• Binary diagrams
• two component systems
• Widely used in materials science & Engineering
• Ternary diagrams
• Three component systems
• Phase diagrams are maps
• Binary diagrams are maps of the equilibrium phases associated with various
combinations of temperature and composition
 Complete solid Solution

• Two components show complete solid

solution in each other in both the solid
and the liquid states.
• L – Liquid phase field
• SS – Solid Solution Phase Field
• L + SS – Mixture of Solid Solution and
Liquid
Complete Solid Solution
Eutectic Diagram with No Solid Solution

Eutectic composition have the lowest

melting temperature
Eutectic Diagram with Limited Solid Solution
 Pb-Sn phase diagram • Common solder alloys are made
using Pb-Sn alloys close to
eutectic composition.
• Solders with less than 5% tin:
• Sealing containers, coating
and joining metals.
• Solders with between 10 and
20% tin:
• Sealing automobile radiators.
• Filling seams and dents in
automobile bodies.
• General purpose solders are 40
to 50% tin.
• These alloys have pasete like
consistency due to liquid and
Eutectic composition ( ~60% tin) is used to solder heat solid phases above 183 °C.
sensitive electronic components.
 Al-Si Phase Diagram
• Al rich 𝛼 phase (Al-Si solid solution) is
an important region to produce
different Al Alloys.
• Eutectic composition has the lowest
melting point.
• 𝛽 region (very narrow – not possible
to see in the diagram) is a solid
solution rich in Si. In semiconductor
Si doping with Al to produce p-type,
this region is significant.
 Eutectoid Diagram
• Eutectic reaction
𝑐𝑜𝑜𝑙𝑖𝑛𝑔
𝐿 𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 𝛼+𝛽

• Eutectoid Reaction
𝑐𝑜𝑜𝑙𝑖𝑛𝑔
𝛾 𝑒𝑢𝑡𝑒𝑐𝑡𝑜𝑖𝑑 𝛼+𝛽
Fe-C phase diagram
Fe-C phase diagram Fe-Fe3C phase diagram
Peritectic Diagrams
• Congruent Melting:
Liquid formed upon melting has the same
composition as the solid from which it was
formed.
• Incongruent Melting:
Liquid formed upon melting has a composition
other than the solid.
ℎ𝑒𝑎𝑡𝑖𝑛𝑔
• Peritectic Reaction: 𝐴𝐵 𝐿+𝐵
 Al2O3-SiO2 binary diagram
Refractory Silica bricks are
nearly pure SiO2 (0.1 to 0.6 mol
% Al2O3.)
Composition is critical as theses
materials should withstand
temperatures above 1600 °C.

Refractoriness dramatically
increase at the composition of
the incongruently melting
compound mullite (3Al2O3.2SiO2
 General Binary Diagrams

Intermediate compound:
A chemical compound formed between components
in the binary system.
This diagram is equal to A-AB system and AB-B system.
It is a common practice
Microstructure analysis is done using that kind of
systems.
The Lever Rule
Consider 100g of 50 wt% composition. Then the mass
balance can be written as,

𝑚𝐿 + 𝑚𝑆𝑆 = 100𝑔 (1)

Independent mass balance for each component can also

be written.

For B: 0.33𝑚𝐿 + 0.80𝑚𝑆𝑆 = 50𝑔 (2)

By solving the equations (1) and (2), amounts of each

phase can be calculated
𝑚𝐿 = 60𝑔 and 𝑚𝑆𝑆 = 40𝑔

Similarly we can obtain a general mass balance

The Lever Rule
For Two phases 𝛼 and 𝛽,
𝑥𝛼 𝑚𝛼 + 𝑥𝛽 𝑚𝛽 = 𝑥 𝑚𝛼 + 𝑚𝛽

𝑥𝛼 and 𝑥𝛽 are the compositions of

the two phases and 𝑥 is the overall
composition.

𝑚𝛼 𝑥𝛽 − 𝑥
=
𝑚𝛼 + 𝑚𝛽 𝑥𝛼 − 𝑥𝛽
And These two equations together are
𝑚𝛽 𝑥 − 𝑥𝛼 called lever rule.
=
𝑚𝛼 + 𝑚𝛽 𝑥𝛽 − 𝑥𝛼