CHAPTER FOUR

PHASE DIAGRAMS
Chapter Contents
4.1.Introduction
4.2. Fundamental concept of phase and phase diagram
4.3. Phase rule -Gibb’s phase rule and Lever rule
4.4. types of equilibrium diagrams and its applications
4.4.1 Binary isomorphous systems (complete solid solubility-
Cu-Ni)
4.4.2 Binary eutectic systems (limited solid solubility –Pb-Sn,
Al-Cu, Fe-C system)
4.5 Cooling curves, isotropy and polymorphism
4.1 INTRODUCTION PHASE AND PHASE DIAGRAM
Some metals are important as pure
elements (e.g., gold, silver, copper);
most engineering applications require
the improved properties obtained by
alloying.
Alloying is changing chemical
composition of metal by adding other
elements with purpose to improve its
properties.
Through alloying, it is possible to enhance
strength, hardness, and other properties
compared with pure metals.
These properties depending on the
temperature, pressure and overall
composition.
These change can be expressed by
phase diagram
4.2 What Are Phase Diagrams?
Phase diagram is a graphical representation
of all the equilibrium phases as a function of
temperature, pressure, and composition. Or
Phase diagrams are graphical representation
of what phases are present in an alloy at
different conditions of temperature T,
pressure P, or chemical composition C.
Equilibrium
 A system is at equilibrium if at constant temperature,
pressure and composition the system is stable, not
changing with time..
 The diagram describes the suitable conditions for two or
more phases to exist in equilibrium.
 For example, the water phase diagram describes a point
(triple point) where water can coexist in three different
phases at the same time.
 This happens at just above the freezing temperature
(0.01°C) and 0.006 atm.
• For one component systems, the equilibrium state
of the system is defined by two independent
parameters (P andT), (T and C), or (P and C).
 Most phase diagrams are constructed by using equilibrium conditions
and are used by engineers and scientists to understand and predict many
aspects of the behavior of materials.
 Some of the important information obtainable from phase diagrams
is:
 To show what phases are present at different compositions and
temperatures under slow cooling (equilibrium) condition?
 To indicate solid solubility of one element (or compound) in other.
 To indicate the temperature at which an alloy cooled under equilibrium
conditions starts to solidify and the temperature range over which
solidification occurs.
 To indicate the temperature at which different phases start to melt.
 There are four major uses of alloy phase diagrams:
 Development of new alloys based on application
requirements.
 Production of these alloys.
 Development and control of appropriate heat treatment
procedures to improve the chemical, physical, and
mechanical properties of these new alloys.
 Troubleshooting problems that arise in application of
these new alloys, ultimately improving product
predictability.
 WHY IMPORTANT?
• Some properties that might be difficult
to predict using a “common sense”
without the knowledge of the phase
diagrams
• phase diagram are important to know
about, how properties of alloy changes
with composition and temperature.
 When it comes to alloy development, phase
diagrams have helped prevent overdesign for
applications.
 This keeps cost and process time down.
 They also help develop alternative alloys or same
alloys with alternative alloying elements.
 It can help to reduce the need for using scarce,
hazardous, or expensive alloying elements.
 Performance-wise, Appropriate elements can then be
chosen for alloying to prevent machinery breakdown.
 if not chosen properly, may lead to breakdown at
higher temperatures.
 The service life also improves as phase diagrams
show us how to solve problems such as intergranular
corrosion, hot corrosion, and hydrogen damage.
• Melting temperature of a mixture AB
(solution) of two components A and B
could be either lower or higher than the
melting point of each component (!).
• This could be a failure mechanism in
electronic or mechanical components.
Example 1: Tmelt (Sn) = 232 0C, Tmelt (Pb) = 327 0C
……
• but Tmelt(Sn0.62 Pb0.38) = 183 0C, so this is a
common soldering alloy
Example 2 Tmelt (Au) = 1064 0C, Tmelt (Si) = 2550 0C
……
• but Tmelt(Au0.97Si0.03) = 363 0C, so thin layer of
gold is used to attach Si chip to a ceramic substrate
(shock protection)
• Mechanical properties (hardness and
tensile strength) of an alloy could be
largely higher than that of the individual
components
• Example 3: hardness (Ag Cu) about twice
the harness of Ag or Cu)
4.3 Phase Rule
• The phase rule is a generalization given by
Willard Gibbs (1874), which seeks to explain the
equilibria existing in heterogeneous system.
• It may be stated as: “provided the equilibrium
between any number of phases is not influenced
by gravity, or electrical, or magnetic forces or by
surface action and only by
 Temperature,
 Pressure and F +P= C + N
 Concentration,
F +P= C + N ….phase equilibrium

• N – (1 or 2) Number of non compositional

variables (Temperature & Pressure),
• (F) -Number of degrees of freedom of the
system(T,P,C)
• (C) - number of components and
• (P) -phases
A) Phase (P)
 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.
 A single-phase system is called homogeneous,
 systems with two or more phases are mixtures or
heterogeneous systems.
• For Example: At freezing point, water
consists of three phase :

• Ice (s)    Water (l)  Water vapour (g)

• Example 2  heterogeneous mixture like :

           CaCO3 (s)     CaO(s) + CO2 (g)

• Consists of three phases   (i.e., two solids and one

gasous).
B. Component(C) –
The elements or compounds which are
present in the mixture . chemically
recognizable species
example
in calcium carbonate,(Ca , C,O)
in carbon steel(Fe and C ),
 in salted water(H2O and NaCl )
sugar solution in water(C11H22 011-H20)
• A component can exist in many phases
• E.g.: In the water system,      
Ice (s)  Water (l) 
vapour (g)
• The chemical composition of all the
three phases is H2O. Hence, it is one
component system.
 AB

Fig 4.1 New structure, concentration (mixing level) at

what temperature? for how long?
C) Degree of freedom or variance (F)
• By the term “degree of freedom is
meant by” the minimum number of
independently variable factors, such
as temperature, pressure and
composition of the phases
• For example-  In case of water system,
Ice(s        Water(l)        Vapour(g), 
• If condition (e.g. Temperature or pressure)
is altered, three phases will not remain in
equilibrium and one of the phases
disappears.
• The three phases can be in equilibrium
only at particular temperature and
pressure
• F +P= C + N, Where N=1T+1P=2
• F +P= C + 2
 Derivation of phase rule
 Consider a heterogeneous system having P phases
and C components.
 Now according to definition the degree of freedom
(F) of the system is minimum of independent
variables which must be fixed arbitrarily to define
the system completely.
 But the number of these variables is equal to the
total number of independent variable minus the
number of relations between them at equilibrium,
since each relation reduces the number of
independent variables by one.
 Now let us calculate the total number of independent
variables:
a) Temperature: At equilibrium, temperature of every
phase is same, so there is only one temperature variable
for the entire system.
b)Pressure: At equilibrium, each phase has the same
pressure, so there is only one pressure variable for the
entire system.
c) Concentration: Concentration of each component is
generally expressed in terms of mole fractions.
As a rule, the number of composition variables required for each phase
is (C-1), since the composition of all components may be expressed by
stating the mole fraction of all except one of the components.
 For example, it there are two components A and B in one phase and if
we know the concentration. (or mole fraction) of one (say A), the
concentration of other (i.e,B) can be automatically found, because the
sum is always unity(one). Thus, if mole fraction of A is 0.4, that of B is
known to be 1-0.4 or 0.6.
Similarly, if we have three components and if the composition of two is
known that of the third can be found out. Thus, if we have C
components, we must know the concentration of C-1 component. So for
P phases the total composition variables are p (C – 1).
 Hence .Total number of variables(TNV)
   = 1(for temperature) + 1(for pressure) + P (C – 1) (for
composition)
      TNV= P (C – 1) + 2 ……………………………..eq 1
  Now let us calculate the number of relations at
equilibrium. Consequently, there are two equilibrium
relationships for each component if there are 3 phases.
Hence, for P phases, the number of such relationships for
each component are ( P -1),so, for C components, such
relationships will be C ( P – 1), ………eq 2
• Degree of freedom, F = Total number of independent variables less
No. of relationships between these variables
• F= [ P( C-1)+2] – [C(P-1)]
• F= C – P + 2
• ~F+P=C+2, this is Gibbs Phase Rule
 In practical conditions for metallurgical and materials systems, pressure
can be treated as a constant (1atm.).Thus pressure has no considerable
effect on phase equilibrium and hence, Gibbs phase rule is written as:
F=C–P+1
 Binary systems -just 2 components (C = 2)
 Independent variables: T and Co (is almost always used, Pressure = 1
atm)
 F+P=C+2
 F+P=4 ⇒F=4-P
4.4 Types of equilibrium diagrams and its
applications
• A diagram that represents existence of different
phases of a system under equilibrium is termed as
phase diagram.
• Phase diagrams are classified according to the
number of component present in a particular
system.
a) It is the system for one-component phase
diagram- Unary phase diagram
b) If a system consists of two components phase
diagram-Binary phase diagram
• Table 4.1 Terminology for the number
of elements in an alloy phase diagram
Number of Example Name of system
components or diagram

One H2O Unary

Cu-Ni
Two Pb-Sn
Al-Cu Binary
Fe-C
Three Cu-Fe-S2 Ternary
a) Unary phase diagram-One component system
 The simplest phase diagrams are pressure–temperature
diagrams of a single simple substance, such as water. The
axes correspond to the pressure and temperature.
 The phase diagram shows, in pressure–temperature space,
the lines of equilibrium or phase boundaries between the
three phases of solid, liquid, and gas.At low pressure
(0.006 atm) and temperature (0.01 0C) all the three phases
coexist at a point called triple point.
 If a system consists of just one component (e.g.water),
equilibrium of phases exist is represent by unary phase
diagram.
 For H2O, a typical diagram shows the temperature and
pressure at which ice (solid), water (liquid) and steam (gas)
exist
 Higher P, Higher T
Higher P, Lower T

Lower P, Higher T
Freezing is the phase change as a substance changes from a liquid to a solid.
Melting is the phase change as a substance changes from a solid to a liquid.
Condensation is the phase change as a substance changes from a gas to a liquid.
Vaporization is the phase change as a substance changes from a liquid to a gas.
Sublimation is the phase change as a substance changes from a solid to a gas
without passing through the intermediate state of a liquid.
Deposition is the phase change as a substance changes from a gas to a solid
without passing through the intermediate state of a liquid.
TRIPLE POINT- The temperature and pressure at which the solid, liquid, and
gas phases exist simultaneously.
CRITICAL POINT - The temperature above which a substance will always be a
gas regardless of the pressure.
4.4.1 Binary Phase diagrams (Binary isomorphous systems)
 A mixture of two metals is called a binary alloy and
constitutes a two-component system, since each metallic
element in an alloy is considered a separate component.
 In some binary metallic systems, the two elements are
completely soluble in each other in both the liquid and solid
states.
 In these systems only a single type of crystal structure exists
for all compositions of the components, and therefore they are
called Isomorphous systems.
 In order for the two elements to have complete solid solubility in
each other, they usually satisfy one or more of the following
conditions formulated by Hume-Rothery and known as the Hume-
Rothery solid solubility rules:-
a)The crystal structure of each element of the solid solution must
be the same.
b)The size of the atoms of each element of the two elements must
not differ by more than 15 percent.
c)The element should be from compounds with each other. That
is, there should be no appreciable difference in electro
negativities of the two elements.
d)The elements should have the same valance.
Equilibrium phase diagrams represent the
relationships between temperature, compositions
and the quantities of phases at equilibrium.
A binary phase is a two component(C=2) system.
Binary phase diagrams are most commonly used in
alloy designing.
Melting temperature of a mixture AB (solution) of
two components A and B could be either lower or
higher than the melting point of each component (!).
This could be a failure mechanism in electronic or
mechanical components.
• Consider the binary equilibrium phase
diagram of elements A and B that are
completely soluble in each other
• Binary diagrams are drawn for atmospheric
pressures, thus P is no longer a variable
and the Phase Rule becomes:
• P+F=C+T
~P + F = C + 1
• Independent variables: T and Co (is almost
always used, Pressure = 1 atm).
• At X
Point X lies within the liquid field,
– P = 1 - Liquid
– C = 2 - two components A and B
– F = 2 - two degrees of freedom,
• At Y
Point Y lies on the boundary curve between the fields of Liquid and
A + Liq.
– P = 2 - Solid A and Liquid
– C = 2 - two components A and B,
– F = 1 - one degree of freedom
• At X
Point X lies within the solid field
– P = 1 - solid
– C = 2 - two components A and B
– F = 2 - two degrees of freedom,
 Isomorphous system - complete solid solubility of the two
components (both in the liquid and solid phases).

Three phase region can be identified on the phase diagram:

 Liquid (L) , solid + liquid (α +L), solid (α )
 Liquidus line separates liquid from liquid + solid
 Solidus line separates solid from liquid + solid
 In one-component system melting occurs at a well-
defined melting temperature.
 In multi-component systems melting occurs over the
range of temperatures, between the solidus and liquidus
lines.
 Solid and liquid phases are at equilibrium with each other
in this temperature range.
Microstructure
 The properties of an alloy depend not only on proportions
of the phases but also on how they are arranged
structurally at the microscopic level.
 Thus, the microstructure is specified by the number of
phases, their proportions, and their arrangement in space.
The long gray regions
are flakes of graphite.
The matrix is a fine
mixture of BCC Fe and
Fe3C compound
Phase diagrams will
help us to understand
and predict
microstructures like
the one shown in this
Fig Al and alloy microstructure
simple examples
a) Sugar in Water- phase diagram-This phase diagram is a two-
component system,
Q. What are the phases in this system?
A. liquid (sugar -in-water solution) and a solid (pure crystalline sugar)
Solvent - host or major component in solution,
Solute -minor component.
 depends on species, temperature and pressure
Solubility Limit of a component in a phase is the maximum amount of
the component that can be dissolved in it
 e.g. alcohol has unlimited solubility in water,
 sugar has a limited solubility, oil is insoluble).
Sugar in Water- phase diagram-

One phase present

Two phase present

 The addition of solute in excess of this solubility limit results in the
formation of another solid solution or compound that has a distinctly
different composition.
 To illustrate this concept, consider the sugar—water (C11H22 011-H20)
system.
 Initially as sugar is added to water, a sugar—water solution or syrup
forms.
 As more sugar is introduced the solution becomes more concentrated, until
the solubility limit is reached or the solution becomes saturated with sugar.
 At this time the solution is not capable of dissolving any more sugar and
further additions simply settle to the bottom of the container.
 Thus the system now consists of two separate substances: a sugar-water
syrup liquid solution and solid crystals of undissolved sugar.
b) Cu-Ni Phase Diagram (simple binary diagram)

Remember Sugar in Water- phase diagram- and

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.
A binary diagram plots the phase changes as a
function of temperature for a system with
varying composition of two components
Cu-Ni Phase Diagram

Both have the same crystal structure (FCC) and

have similar electro negativities and atomic radii
suggesting high mutual solubility.
 Cu-
Ni

Phase B
Phase A

Nickel atom
Copper atom
Binary isomorphous systems
Periodic Table

Binary eutectic systems

What happens when Cu and Ni are mixed?

4.4 a Phase Diagram for Cu-Ni system

For a pure component, complete melting occurs
before T increases (sharp phase transition fig 4.4 a).
But for multi component systems, there is usually a
coexistence of L and S
1

2
3
 Three phase region can be identified on the
phase diagram:
Liquid (L), solid + liquid (S +L), solid (S)
a) Liquidus line separates liquid from liquid + solid
b) Solidus line separates solid from liquid + solid
 It can be noted that the two metals are soluble in
each other in the entire range of compositions in
both liquid and solid state. This kind of system is
known as ‘Isomorphous’ system
 When the properties of a material are the same
in all directions, the material is said to be
isotropic.
Finding the composition in a two phase region:
1. Locate composition and temperature in diagram
2. In two phase region draw the tie line or isotherm
3. Note intersection with phase boundaries. Read
compositions at the intersections.
The liquid and solid phases have these compositions.
What is The Tie Line?
• The composition of phases in the two-phase region is not
same.
• To find the composition of the individual phases in the
two phase region, a horizontal line (XY), called tie line, is
drawn and its intercepts on the liquidus and solidus lines,
Cl (composition for liquid) and Cs(composition of solid),
are taken as the composition of the liquid and solid
respectively.
• The relative fractions of the phases at a given
temperature for an alloy composition C is obtained by
the lever rule.
-Using the same horizontal line as before that indicates overall
composition at a given temperature, measure the distances between
the aggregate composition and the intersection points with the
liquidus and solidus, identifying the distances as CL and CS,
respectively;
From above diagram Finding the amounts of phases in a
two phase region or calculate Mass (volume) fractions by
lever rule
Derivation of the lever rule
1) All material must be in one phase or the other:
Wα + WL = 1
2) Mass of a component that is present in both phases equal to
the mass of the component in one phase + mass of the
component in the second phase:
WαCα + WLCL = Co
3) Solution of these equations gives us the lever rule.
• Examples. A 53% Ni Cu-Ni alloy is cooled from
liquid state to 1300C. The tie line at 1300 C
intersects solidus at 58% Ni and liquidus at 45%
Ni.
• calculate the % of Liquid and solid at 1300 C.

• Apply the lever rule to get the liquid fraction

draw a tie line at 1300oC
Solution
Development of microstructure in isomorphous
alloys
Equilibrium (very slow) cooling
 Solidification in the solid + liquid phase occurs
gradually upon cooling from the liquidus line.
 The composition of the solid and the liquid
change gradually during cooling (as can be
determined by the tie-line method.)
 Nuclei of the solid phase form and they grow to
consume all the liquid at the solidus line.
Equilibrium (very slow) cooling in a Cu-Ni Binary
 Lesson 2
4.4.2 Binary eutectic systems (limited solid
solubility –Pb-Sn, Al-Cu, Fe-C system)

4.5 Cooling curves, isotropy and polymorphism

Chapter 5