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MM 231

Phase Equilibria and



MM 231
Phase Equilibria & Microstructures


Learning Outcomes
Development of new alloys for specific applications.
Fabrication of these alloys into useful configurations.
Design and control of heat treatment procedures for specific
alloys that will produce the required mechanical, physical, and
chemical properties.
Solving problems that arise with specific alloys in their
performance in commercial applications, thus improving product
Basic knowledge on thermodynamics and kinetic factors
controlling solid state phase transformations in metals and alloys.
Diffusional and diffusionless solid state phase transformations.









Text and Reference Books

Porter, D. A and Easterling, K.E, Phase Transformations in

Metals and Alloys, Chapman & Hall, 2001.
Physical Metallurgy Principles: Reza Abbaschian,Robert
E.Reed Hill, Fourth Edition
Honeycombe, R. W. K., and Bhadeshia, H. K. D. H., Steels,
Microstructures and Properties, Edward Arnold, 2005
Cahn and Haasen, Physical Metallurgy 2001 .
William F. Hosford, University of Michigan, Ann Arbor, USA,
Physical Metallurgy, Second Edition, 2010
Martin, Doherty and Canter, Stability of Microstructures in
Metallic Systems Cambridge University Press, 1997

Grading Policy:
Assignment (min 4)




(min 6)

Presentations /Class Projects


Mid term Exam

30 %

Final Exam


Teaching Methodology : 45 Lectures [03 lectures/week]

Attendance: 100%, (min 80% to sit in the final exam)


Solid Solutions and Hume Rothery Rules

Solid Solutions
Solute + Solvent = Solution
Mixing of atleast two metals

Solid Solutions
Solid Solution:
A solid solution is formed when two metals are
completely soluble in liquid state and also
completely soluble in solid state.
when homogeneous mixtures of two or more kinds
of atoms (of metals) occur in the solid state, they
are known as solid solutions.

Solid Solutions
Question is .
How Solid Solution Forms
Solid Solution occurs in two distinct Types:

Substitutional Solid Solution

Interstitial Solid Solution

Solid Solutions
Substitutional Solid Solution:
If the atoms of the solvent or parent metal are replaced in the crystal lattice
by atoms of the solute metal then the solid solution is known as
substitutional solid solution.
For example, copper atoms may substitute for nickel atoms without
disturbing the FCC. Similarly Ag-Au FCC binary systems and the Mo-W BCC
binary system.


Solid Solutions
In the substitutional solid solutions, the substitution can be either disordered
or ordered.
In disordered substitutional solid solution, the solute atoms have substituted
disorderly for the solvent atoms on their lattice site. In ordered substitutional
solid solution, the solute atoms have substituted in an orderly manner for the
solvent atoms on their lattice site.


Solid Solutions
Ordering in Substitutional Solid solutions
As stated before substitutional solid solutions can be either ordered or random.
This depends on a thermodynamic parameter called enthalpy of mixing,Hmix
Gmix = Hmix - T Smix
Gmix is the Gibbs free energy change and Smix entropy of mixing.
For an ideal solution Hmix = 0.
If Hmix> 0, formation of like bonds (A-A or B-B) is preferred in a solid solution
between metals A and B. This is known as clustering.
If Hmix< 0, unlike bonds (A-B) are preferred. This leads to ordering which may
exist over short range or long range

Solid Solutions
Interstitial Solid Solution:
In interstitial solid solutions, the solute atom does not displace a solvent
atom, but rather it enters one of the holes or interstices between the solvent
The atoms crowd into the interstitial sites, causing the bonds of the solvent
atoms to compress and thus deform.
Elements commonly used to form interstitial solid solutions include H, Li, Na,
N, C, and O. Normally, atoms which have atomic radii less than one angstrom
are likely to form interstitial solid solutions. Examples are atoms of carbon
(0.77 A), nitrogen (0.71 A), hydrogen (0.46 A), Oxygen (0.60 A) etc.
Carbon in iron (steel) is one example of interstitial solid solution.


Hume Rothery Rules

Several factors determine the limits of solubility. These factors are
defined by Hume Rothery Rules


Atomic Size Factor

2. Crystal Structure
3. Valancy
4. Electronegativity

Hume Rothery Rules

Atomic Size Factor (the 15%) Rule:

Extensive substitutional solid solution occurs only if the relative

difference between the atomic diameters (radii) of the two
species is less than 15%. If the difference > 15%, the solubility is
Comparing the atomic radii of solids that form solid solutions,
the empirical rule given by Hume-Rothery is given as:

Hume Rothery Rules

Crystal structure Rule :

For appreciable solid solubility, the two elements should have the same type
of crystal structure i.e., both elements should have either F.C.C. or B.C.C. or
H.C.P. structure.

Valency Rule :
A metal will dissolve a metal of higher valency to a greater extent than one
of lower valency. The solute and solvent atoms should typically have the
same valence in order to achieve maximum solubility.
For example in aluminium-nickel alloy system, nickel (lower valance)
dissolves 5 percent aluminium but aluminium (higher valence) dissolves
only 0.04 percent nickel.

Hume Rothery Rules

The Electronegativity Rule :

Electronegativity difference close to 0 gives maximum solubility. The more
electropositive one element and the more electronegative the other, the
greater is the likelihood that they will form an intermetallic compound
instead of a substitutional solid solution. The solute and the solvent should
lie relatively close in the electrochemical series.

Hume Rothery Rules

Interstitial solid solution
Hume-Rothery rules can be applied for interstitial solid solutions:
Interstitial solid solutions are formed if:
1. a solute is smaller than pores in the lattice of a solvent;
2. a solute has approximately the same Electronegativity as a solvent.
There are very few elements that create ions, small enough to fit in interstitial
positions, therefore, appreciable solubility is rare for interstitial solid solutions.
Ions that often may be a solute in solid solutions are: H, Li, Na, B.


Gibbs Phase Rule and one

components Phase Diagram

Useful Terminology

Solubility Limit
Phase Equilibrium
Variables of system

Useful Terminology
Phase a portion of a system that has uniform physical and

chemical characteristics. Two distinct phases in a system have

distinct physical and/or chemical characteristics (e.g. water and ice,
water and oil) and are separated from each other by definite phase
boundaries. A phase may contain one or more components.

Useful Terminology
A single-phase system is called homogeneous systems
Homogeneous system:
The one whose chemical composition and physical properties are the same in all parts
of the system, or change continuously from one point to another.
A homogeneous system can be exemplified by
imagining a column of atmospheric air, which is a
mixture of a number of gases, mainly nitrogen and
oxygen. In a system of this kind, acted upon by the
force of gravity, both the composition of the system
and its physical properties will continuously change
from one point to another.

Useful Terminology
Heterogeneous system:
One consisting of two or more homogeneous bodies. The homogeneous
bodies of a heterogeneous system are referred to as phases. Each phase is
separated from other phases by interfaces, or boundaries, and in passing
over such a boundary the chemical composition of the substance or its
physical properties abruptly change.
An example of a heterogeneous system is water with
ice floating in it. This system has two homogeneous
bodies, water and ice. The chemical composition
of the two phases is the same, but their physical
properties differ drastically.

Useful Terminology
Solubility limit:
For almost all alloy systems, at a specific temperature, a
maximum of solute atoms can dissolve in solvent phase to form
a solid solution. The limit is known as solubility limit. In general,
solubility limit changes with temperature.
The same concepts apply to solid phases: Cu and Ni are
mutually soluble in any amount (unlimited solid solubility), while
C has a limited solubility in Fe.
If solute available is more than the
solubility limit that may lead to
formation of different phase, either

Mole Fractions

where XA is called the mole fraction of component A in some phase.

If the same component is used in more than one phase, Then we can define the
mole fraction of component A in phase i as X iA
For a simple binary system, XA + XB = 1

Useful Terminology
is either pure metal and/or compounds of which an alloy is
composed. The components of a system may be elements, ions or
compounds. They refer to the independent chemical species that
comprise the system.
System :
It can either refer to a specific body of material under consideration
or it may relate to the series of possible alloys consisting of the same
components but without regard to alloy composition.
Degree of freedom (or variance) F :

It is the number of variables (T, p, and composition) that can be

changed independently without changing the phases of the system

Equilibrium in terms of free energy

Free energy is a function of
internal energy and randomness
/disorder (entropy) of a atoms or
molecules of a system.

Consider a map of the potential energy (vertical axis) of a system in
four different states:

State (a) is an equilibrium position, which is

stable to small perturbations. It does not,
however represent the lowest energy state
of the system and we refer to it as a metastable equilibrium.
State (b) is an equilibrium position, but is not stable to any small
perturbations. This is an unstable equilibrium position.
State (c) is not an equilibrium position. There is a driving force to the
State (d) is the position of stable equilibrium: it occupies the lowest
energy state, and is stable to perturbations.

Phase Diagrams
Equilibrium Diagrams
Represents phase relationships as a function of temperature, pressure and
composition (equilibrium phases and microstructure)
A phase diagram is a type of graph used to show the equilibrium conditions
between the thermodynamically-distinct phases; or to show what phases are
present in the material system at various T, p, and compositions
But many useful diagrams are constructed for constant pressure of 1
atmosphere, so only composition and temperature are variables
Phase diagrams provides us with information needed for the control of phase
and microstructure in the materials we make

Gibbs Phase Rule

Variables of a system:
These include two external variables namely temperature and pressure
along with internal variable such as composition (C) and number of
phases (P). Number of independent variables among these gives the
degrees of freedom (F) or variance. All these are related for a chosen
system as follows:

which is known as Gibbs Phase rule.

N = number of non-compositional variables
N = 1 or 2 for T (temperature) and P (pressure)
N = 1 If P=const or T=const
P is usually constant so N is usually 1)


Gibbs Phase Rule Significance for Phase Diagrams

For Two Dimensional Phase Diagrams:
Stability fields:
Area (T-P,T-X,P-X space) where a phase or phase assemblage (more than one
phase ) is stable.
Equilibrium boundary lines:
These define the limits of stability fields. These represents values of parameter
where phases in adjacent fields coexist.
Triple point:
Points where equilibrium boundary lines meet. All phases in the adjacent stability
fields must coexist.

Silica Phase Diagram and Phase Rule

One Component Phase Diagram

Number of
nt Components

of Phases

Degree of

2 (T,P)

2 (T,P)

1 (T or P)

1 (T or P)

Application of Gibbs Phase Rule

One Component Phase Diagram

Introduction to Binary Phase Diagram

Phase diagrams, also called equilibrium diagrams or constitution diagrams,
are a very important tool in the study of alloys. They define the regions of
stability of the phases that can occur in an alloy system under the condition of
constant pressure (atmospheric).

Isomorphous systems contain metals which are completely soluble in each

other and have a single type of crystal structure.

Cooling Curve
The melting temperature of any pure material (a one-component
system) at constant pressure is a single unique temperature.
The liquid and solid phases exist together in equilibrium only at this
temperature. When cooled, the temperature of the molten material
will steadily decrease until the melting point is reached.
At this point the material will start to
crystallise, leading to the evolution of
latent heat at the solid liquid
interface, maintaining a constant
temperature across the material.
steady cooling resumes. The arrest in
cooling during solidification allows the
melting point of the material to be
identified on a time-temperature

Cooling Curve
Simplified Cooling Curve of Pure Copper

Construction of Binary Phase Diagram

Most systems consisting of two or more
components exhibit a temperature range
over which the solid and liquid phases are in
equilibrium. Instead of a single melting








temperature and the solidus temperature

is the temperature
are needed
to describe
the change above which the system is
and the solidus is the temperature below which the
from liquid
to solid.
system is completely solid. Between these two points the liquid and solid
phases are in equilibrium. When the liquidus temperature is reached,
solidification begins and there is a reduction in cooling rate caused by
latent heat evolution and a consequent reduction in the gradient of the

Construction of Binary Phase Diagram

By taking a series of cooling curves for the










temperatures for each composition can be






liquidus to be mapped to determine the

curves for the same system recorded for different compositions
and then displaced along the time axis. The red regions indicate where
the material is liquid, the blue regions indicate where the material is
solid and the green regions indicate where the solid and liquid phases
are in equilibrium.

Construction of Binary Phase Diagram

By removing the time axis from the curves
and replacing it with composition, the
cooling curves indicate the temperatures
of the solidus and liquidus for a given

This allows the solidus and liquidus to be

plotted to produce the phase diagram

Construction of Isomorphous phase Diagram

Phase Diagram

Phase Diagram of Cu Ni System

Phase Diagram of Cu Ni System

Binary Phase Diagram

There are three main types of binary phase diagrams :

Complete solid and liquid solution diagram
Eutectic diagram (includingEutectic diagram with partial solubility
of the components in solid state andEutectic diagram with
intermetallic compound)
Peritectic diagram

Binary Phase Diagram(Eutectic System)

In most alloy systems,componentsare onlypartially misciblein the solid

state. In other words, solid solution only exist over a limited range of
compositions and temperatures.
Example: Cu and Ag are both FCC, but their lattice parameters and
atomic radii are very different, so they have limited solubility in the solid
This kind of system is called Eutectic System

Eutectic means EASILY MELTED

Construction of Phase Diagram (Eutectic Alloy)

Cooling Curves (Temp Vs. Time ) with addition of

2nd element

Cooling Curves (Temp Vs. composition)

Construction of Phase Diagram (Eutectic Alloy)

Construction of Phase Diagram (Eutectic Alloy)

Eutectic Alloy
In Eutectic System, the two elements are completely soluble in all
proportions in the liquid state. On cooling two possibilities may arise
i-The two elements are completely insoluble in solid state
ii-The two elements are partly soluble in the solid state

Liquid (L)


A+B (Possibility (i)

Where A and B are metals, and

Liquid (L)


+ (Possibility (ii)


Where is A rich solid solution and is B rich solid solution

Eutectic Alloy
These reactions takes place at fixed temperature, called eutectic
temperature, and the composition of participating phases is also fixed.
Gibbs phase rule can be applied to this equilibrium system.
All three phases coexist at a single temperature. This temperature is the
melting point of the eutectic alloy
The characteristic feature of eutectic alloy is,
It melts at fixed temperature just like a pure metal.
It have a good casting characteristics such as fluidity and minimum

Eutectic Alloy

Fig:Partial Phase diagram for the Pb-Sn system, showing the limiting behavior at high and low

The lower part replicates the sugar water behavior ; the solubility of Pb in Sn (and
Sn in Pb) increases with temperature.
Note: Solubilities of these elements in one another is low, especially Pb in Sn on
right of the diagram.
The upper part of the diagram shows the partition behavior from the melting points
of both pure elements.

Eutectic Alloy

Fig: Completed solid phase and two phase

To complete the diagram, consider where the falling solidus boundaries
meet the rising solvus boundaries.
The point where they intersect represent the points of maximum
solubility in the single phase solids.

Eutectic Alloy

Fig: The completed phase diagram for the Pb-Sn system, showing the
eutectic point
Thermodynamics dictates that liquid boundaries meet the horizontal line
at a single point, and the liquid field closes in a shallow V. At this
special composition, two solid phases and liquid of that composition can
co-exist. This point on the diagram is very important , and is known as a
eutectic point.

Interpretation of Eutectic Phase Diagram

Limited Solid Solubility

is solid A with small amount of solid B dissolved in it
is solid B with small amount of solid A dissolved in it
Components have different solid solubilities

Interpretation of Eutectic Phase Diagram

Applications of Eutectic Alloys

Eutectic alloys forsoldering, composed oftin(Sn),lead(Pb) and
sometimessilver(Ag) orgold(Au) especially Sn63Pb37alloy formula
for electronics
Casting alloys, such
composition of 4.3%

asaluminium-silicon andcast iron(at the

carbon in iron producing an austenite-

Silicon chipsare bonded to gold-plated substrates through a silicon-gold

eutectic by the application ofultrasonicenergy to the chip.
Brazing, where diffusion can remove alloying elements from the joint, so
that eutectic melting is only possible early in the brazing process.





Eutectic alloys ofsodiumandpotassium(NaK) that are liquid at room

Construction of Phase Diagram (Eutectic Alloy)

Interpretation of Phase Diagrams

A binary phase diagram can be used to determine three important types of

(1) The phases, that are present
(2) The composition of the phases
(3) The percentages or fractions of the phases.

Prediction of Phases
The phases that are present can be determined by locating the
temperature-composition point on the diagram and noting the phase(s)
present in the corresponding phase field.
30wt%Ni-70wt%Cu at 1315 C (2400 F)
Point lies totally within the liquid field, the alloy would
be a liquid.
The same alloy at 1095 C (2000 F), designated point c
within the solid solution, , field, only the single phase
would be present.
At alloy at 1190 C (2170 F)
(point b) would consist of a two-phase mixture of
Solid solution, , and liquid, L.

Prediction of Chemical Compositions of Phases

To compute the equilibrium concentrations/Chemical Composition of the
two phases, the following procedure is used:

1. A tie line is constructed across 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.

Prediction of Chemical Compositions of Phases

Locate the point on the phase diagram. If

composition of the phase is the overall
composition of the alloy.
At Point (A), at corresponding T, only
Liquid is present , so composition will be

At Point (C) only the phase is present, so

the composition is 30wt%Ni-70wt%Cu.

Prediction of Chemical Compositions of Phases

At Point (B) considering the 30wt%Ni-70wt%Cu alloy at 1190 C (2170 F)
with the two-phase, + L, field.
The perpendicular line from the liquidus boundary
to the composition axis is 20wt%Ni-80wt%Cu,
which is the composition, CL, of the liquid phase.

The composition of the solid-solution phase, C,

is read from the perpendicular line from the
solidus line down to the composition axis, in
this case 35wt%Ni-65wt%Cu.

Prediction of Amounts of Phases

The relative amounts (fraction/%) computed with phase diagrams.
The single and two-phase situations
must be treated separately.
In the single phase region: Since only
one phase is present, the alloy is
composed entirely of that phase; i.e. the
phase fraction is 1.0 or 100%.
At 60 wt% Ni40 wt% Cu alloy at
1100oC(point A),
Only is present
completely or 100%

alloy is

Prediction of Amounts of Phases

If the composition and temperature position is located within a twophase region, things are more complex. The tie line must be utilized in
conjunction with a procedure that is often called the lever rule (or the
inverse lever rule)
Steps to determine Phase Amount using Lever Rule
1. The tie line is constructed across the two-phase region at the
temperature of the alloy.
2. The overall alloy composition is located on the tie line.
3. The fraction of one phase is computed by taking the length of tie line
from the overall
alloy composition to the phase boundary for the other phase, and
dividing by the total
tie line length.
4. The fraction of the other phase is determined in the same manner.