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Introduction
 Phase diagrams , are also known by the names equilibrium/constitutional
diagrams , are a very important tool used in the study of alloys.
 A phase diagram consists of two parameters – temperature , taken on the
ordinate and the alloy composition taken on the abscissa.
 Role of the phase diagram :-
 Shows the phases in equilibrium for a given allow composition, at a glance.
 Shows the relationship between the composition , temperature, and alloy
structure in series.
 Permits to study and control processes such as Phase separation ,Solidification of
metals and alloys , Purification of materials ,The growth and doping single crystals,
and the structural changes produced by heat treatment ,casting ,etc. .

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 Solid Solutions
• A solid solution is defined as a solid
mixture containing a minor
component uniformly distributed
within the crystal lattice of the
major component. ( as shown in
the two possible cases )
• The key feature of a solid solution is
that the metals retain their
homogeneity and hence their
solubility after their transformation
to a solid crystalline state.
• An example of a solid solution
would be Copper 64% and Zinc 36%
• The solid solutions comprise of
atoms of almost the same atomic
radius , and they tend to form a
single phase and the elements are
soluble in both their solid and liquid
states .

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 Classification of Solid solutions :

Substitutional Interstitial

Disordered Ordered

• Substitutional Solid Solutions have a direct substitution of one type of atom for another
so that solute atoms (Cu) enter the crystal to take positions normally occupied by solvent
atoms (eg . Ni atoms).
• Disordered Substitutional Solid Solutions are those type of solid solutions in which the
solute atoms are randomly distributed in the solvent lattice structure , hence disordered.
• Ordered Substitutional Solid Solutions are those in the disordered solution is cooled
slowly , causing atomic re-arrangement because of the diffusion due to cooling causing
uniform distribution of solute and solvent atoms.
• Interstitial Solid Solutions are those in which the solute atoms occupy the interstitial
positions in the solvent crystal lattice , without any replacement of solvent atoms , on
account of a very small solute atomic size relative to that of the solvent. (around a factor
of 70 )

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esrmnotes.in | Class notes made easy.
 Intermediate phases
• In many binary alloy systems, when the chemical affinity of metals is great, their
mutual solubility becomes limited or reduced and a so called “intermediate
phase” is formed.
• The intermediate phase may have either narrow or wide ranges of homogeneity
and may or may not include a composition having a simple chemical formula.
• For example the phase CuAl exists in a homogeneity ,that does not include the
composition CuAl.
• Intermediate phases may range between ideal solid solutions and the ideal
chemical compound.
• The intermediate phases are the phases that form in the intermediate regions of
the equilibrium diagram.
• They are usually classified into two types : Intermetallic compounds of
• a)fixed composition or b)variable composition.

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 Comparison between the types
Intermetallic compounds of Intermetallic compounds of
fixed composition variable composition

• They obey the usual valency • They do not obey the

laws ,like ordinary chemical valence laws and are also
compounds. Eg. NaCl. known as electron
compounds.
• An example could be Mg2Sn
has 29.08% of Mn. • Examples could be Ratio 3/2
–beta , like Cu3Al,Ratio
21/13-gamma like Cu9Al4 or
ratio 7/4-Epsilon like Cu3Al

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 Phase rules
• The following are the rules which are to be
followed while interpreting the phase diagrams :
• Prediction of Phases
• From a phase diagram , specific information can
be obtained only if a temperature and a
composition is specified.
• This can be done by using both temperature and
composition parameters to identify the point on
the phase diagram.
• Once done , depending on its location ,identify
the phase present at that particular point .

• Phase composition
• To find the phase composition at a particular
temperature like 500 degrees Celsius , draw a
horizontal line OP , that hits the liquidus and a
vertical line that hits the solidus curve from P .
This would automatically indicate the phase
composition for the required temperature.

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 Lever arm Principle
• Besides indicating the number of phases and phase composition , the phase
diagram also tells the proportion of co-existing phases at a given temperature.
• To determine the relative amount of the two phases , erect an ordinate at a point
say (85% Sb) on the scale which gives the total composition of the alloy.
• The intersection of this vertical blue line and a given isothermal line OP (at a given
temperature) is the fulcrum of the simple lever system and OM and MP are the two
lever arms as shown in the previous figure.
• This is commonly referred to as the lever rule because the amount of a given phase
multiplied by its lever arm is equal to the amount of the other phase multiplied by
its (or the other) lever arm.
• The isothermal line is also referred to as the Tie line since it joins the composition
of the two phases in equilibrium at a specific temperature.
• When expressed mathematically it gives us the foll :
• 1.The amount of solid phase
• i.e. (MP/OP)*100
• 2.The amount of liquid phase
• i.e. (OM/OP)*100

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 Gibbs Phase rule
• The phase rule, also known as the Gibbs Phase Rule, establishes the relationship
between the number of degrees of freedom (F),the number of components(C) and
the number of phases(P).
• It is mathematically expressed as follows :

P+F=C+2
• P->Number of phases (Solid or liquid and so on) ;
• F->Number of degrees of freedom (pressure ,temperature ,concentration and so
on) without altering the equilibrium
• C->Number of Components n the system (For example Pb-Sn)
• In metallurgical systems the pressure is regarded as remaining fixed at one atm
and hence the pressure variation is neglected.
• Phase rule applies to dynamic and reversible processes, where a system is in
heterogeneous equilibrium and where the external variable are only temperature ,
pressure and concentration.
• It is used while dealing with multicomponent systems to determine whether the
microstructures are in equilibrium or not.

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 Energy in the intermediate phase
• The formation of a new intermediate phase in
a system is associated to the change in free
energy of the system.
• The free energy has two components :-
1)Chemical energy 2)Non chemical free
energies.
• Let us assume that “x” be the width of the
new intermediate phase formed in the
system.
• If “G” is the amount of decrease in free
energy/unit volume , then the total free
energy decrease would be G*x , considering
unit cross sectional area of the couple.
• Non chemical free energy is brought into play
for the creation of the new intermediate
phase , and a mechanical work is done while
doing so due to volume change.
• Hence the total free energy change is the sum
of the interfacial energies and the mechanical
work done .

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 Phase diagram
• A great deal of information concerning to phase
changes in many alloy systems has been
accumulated and the best method of recording
the data is in the form of phase diagram.
• A phase diagram shows the limits of
composition and temperature within which
the various constituents or phases of the
alloys are stable.
• The structural changes and compositional
changes of the constituents in equilibrium at a
fixed temperature can be ascertained using the
phase diagrams.
• If two metals of a binary solution ( such as Cu-
Ni) are mixed in different proportions, melted
and cooled , and a cooling curve is constructed
for each composition,.
• When the temperatures at which solidification
starts and completes for various compositions
with respect to time would lead to the phase
diagram.

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 Classification of Phase diagram
• The classification is as follows :-
• Unary (or one component) phase diagram which is plotted as pressure on the
vertical axis and temperature on the horizontal axis .
• Binary (or two components) phase diagram which is plotted with temperature
taken on the vertical axis and the various concentrations taken on the horizontal
axis commonly.
• Ternary (or three components) phase diagram which is plotted three
dimensionally between three components and the equilibrium associated with
each other and the vertical axis usually taken comprises of the temperature as the
common parameter (discussed more in the successive slides).

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 Phase changes in alloys
• Phase changes can be analyzed for the alloys in two ways :-
• 1)For two metals completely soluble in liquid state and insoluble in the solid state
• 2) For two metals completely soluble in liquid state and partially soluble in the
solid state

For two metals completely soluble in liquid state and insoluble in the solid state
Consider the Bismuth Cadmium system as shown :

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Four phase fields are seen on Fig. 5 above:
• a fully molten region,
• two regions in which liquid and solid coexist,
• a completely solid region.

• The two liquidus lines slope downwards from the

melting points of the pure materials to meet at a
point known as the eutectic point (E).
• Material of the eutectic composition will undergo
the transformation liquid -> solid (Bi+Cd) at the
temperature 144 degrees Celsius.
• Since the formation of the two solids occurs
simultaneously, this will be also reflected in the
microstructure.
• The two solids are strongly mixed in this eutectic
structure, sometimes as particles or ”stars” of one
solid surrounded by the other, or maybe as
laminations as shown in the drawing.
• Note that unlike all other alloys, eutectic
compositions have no extended freezing range but
they freeze at a definite temperature similarly to
pure metals.

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• For two metals completely soluble in liquid state and partially soluble in the solid
state

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• A eutectic system can occur when terminal solid solutions exist on both ends of the
binary equilibrium phase diagram. An example of a binary eutectic system is lead (Pb) -
tin (Sn).
• Although the atomic size difference is less than 10%, Pb has an FCC crystal
structure while Sn is an unusual metal with a non-cubic tetragonal structure. This results
in limited solid state solubility with the maximum solubility of Sn in the FCC Pb equal to
19.2 wt%Sn while only 2.5wt% of Pb is soluble in the tetragonal Sn structure.
• At compositions and temperatures, which exceed these solubility limits, two solid
phases
will exist in equilibrium. The phase is the FCC Pb with some substitutional Sn atoms
and the phase is tetragonal Sn with only a few substitutional Pb atoms.
• These maximum solid-state solubility both occur at 183 deg. Cel. which is referred to
as the eutectic temperature.
• At this temperature, there exists a point on the phase diagram
(a single combination of composition and temperature) where three phases (the two
solids and a liquid) can exist simultaneously in equilibrium.

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 Ternary Phase diagrams
• The properties of a pure metal are improved
by the addition of alloy elements.
• Simple binary alloys process certain improved
properties than the pure metals.
• Further improvement in qualities or
properties of a binary alloy is frequently
gained by adding a third element, eg , the
addition of nickel to Steel (Fe-C) improves
toughness and the addition of lead to brass
(Cu-Zn) improves machinability.
• A ternary equilibrium diagram presents a
three component system , that is it deals
with three metals say A,B and C.
• The complete equilibrium is indicated in a
three dimensional figure.
• The temperature is always plotted vertically.
• We have liquidus and solidus planes in a
ternary system unlike the liquidus and solidus
lines in a binary system .

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 Cooling Curves

• A mathematical curve while plotting the temperature as a function of

time as different alloys in the system are very slowly cooled.
• This method is basically used to determine the temperature at which
phase change ( from solid to liquid ) occurs.
• The study is useful in :-
– Studying the changes that occur during solidification of alloys, and
– In determining transformations subsequent to solidification .

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 Cooling curve of pure metal or compound

• The liquid metal initially cools at a rate

called as the cooling rate until we
reach the beginning of the thermal
arrest.
• During thermal arrest the phase
change occurs and the metal liberates
its latent heat of fusion while keeping
the temperature constant to reach to
the end of the thermal arrest.
• This point is referred to as the freezing
point of the metal.
• On further cooling the metal tends to
reach the room temperature.
• The Slopes before and after thermal
arrest ,by value , depend upon the
specific heats of the liquid and solid
metals , respectively.

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Equilibrium diagrams of Iron and Iron -Carbide diagram

• Iron is molten above 1536 deg.

Celsius. It solidifies in a BCC
Structure (Delta).
• On further cooling at 1400 Celsius
, a phase change occurs and the
atoms rearrange themselves into
the Gamma from which is FCC
and non magnetic.
• On further cooling at 910 Celsius,
another phase change occurs
from FCC non magnetic gamma
iron to BCC non magnetic alpha
iron.
• Finally at 768 Celsius ,the alpha
iron becomes magnetic without a
change in the lattice structure . Cooling curve for Iron

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Equilibrium diagram for Iron Carbide System

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• The iron carbon equilibrium diagram indicates the phase changes that occur during heating
and cooling and the nature and amount of the structural components that exist in any
temperature. It also establishes a relation between the microstructure and properties of steel
and cast irons and provides a basis for the understanding of the principles of heat treatment.
• The iron carbon equilibrium has a peritectic point , eutectic and eutectoid point.
• When Delta iron + liquid when cooled below peritectic point causes it to be converted to
Austenite. (Occurs around 2720 Fahrenheit)
• The liquid cools to an eutectic mixture of austenite and cementite at a temperature of 2066
Fahrenheit and the reaction is called as a eutectic reaction.
• Eutectic point is at 4.3% carbon content and the eutectic mixture is not usually seen in the
microstructure, because austenite is not stable at room temperature and must undergo
another reaction during cooling.
• The eutectoid reaction occurs at 1333 Fahrenheit and is represented by a horizontal line with
the eutectic point at 0.83% carbon content .

Features :-
1)When steel of 0.4 % carbon (hypoeutectoid steel) is converted entirely into austenite above
• The upper critical temperature line and whencooled below the line the structure of iron
changes from FCC TO BCC causing ferrite crystals to grow in size at the expense of austenite.
At 1344 Fahrenheit , austenite has 0.83 % (max limit it can hold in solid solution) , the
temperature drops further , and carbon precipitates as cementite at 723 degrees Celsius.

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• Cementite and still separating Ferrite form alternate layers until all the remaining austenite is
consumed. The lamellae structure contains 0.83% of carbon and is known as pearlite.
• Other transformations are also possible such as eutectoid steel into pearlite as well as
hypereutectoid steel to cementite.

Ledeburite Structure
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esrmnotes.in | Class notes made easy.
 ME1022 MATERIALS TECHNOLOGY

UNIT III - PHASE DIAGRAMS AND HEAT TREATMENTS

By
Mr. S.SHAKTHIVEL
A.P(Sr.G)
Department of Mechanical Engineering
SRM Univeristy
Kattankulathur

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UNIT III - PHASE DIAGRAMS AND HEAT TREATMENTS (9 hours)
Introduction - Solid solutions - Intermediate phases - Phase rules - Free
energy in intermediate phases - Phase diagrams - Phase changes in alloys –
Determination of phase diagrams - Ternary phase diagrams - Cooling curves
– Equilibrium diagrams of Iron and Iron -Carbide diagram - Definition of
structures – Annealing – Normalizing – Tempering – Hardening

Solid Solution
If we pour the water into the alcohol and stir, only one phase is produced.
The glass contains a solution of water and alcohol that has unique properties
and composition. Water and alcohol are soluble in each other. Furthermore,
they display Unlimited solubility.
Regardless of the ratio of water and alcohol, only one phase is produced
when they are mixed together.

If the liquid copper-nickel alloy solidifies and cools to room temperature,

only one solid phase is produced. After solidification, the copper and nickel
atoms do not separate but, instead, are randomly located within
the FCC crystal structure.
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Within the solid phase, the structure, properties, and composition
are uniform and no interface exists between the copper and nickel atoms.
Therefore, copper and nickel also have unlimited solid solubility. The solid
phase is a solid solution of copper and nickel.
Another example of a system forming a solid solution is that of barium
titanate (BaTiO3) and strontium titanate (SrTiO3), which are compounds
found in the BaO–TiO2–SrO ternary system.

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If we add a small amount of liquid zinc to liquid copper, a single liquid
solution is produced. When that copper-zinc solution cools and solidifies, a
single solid solution having an FCC structure results.
If the liquid solution contains more than about 30% Zn, some of the
excess zinc atoms combine with some of the copper atoms to form a CuZn
compound.
Two solid phases now coexist: a solid solution of copper saturated with about
30% Zn plus a CuZn compound.
The solubility of zinc in copper is limited.
Hence arises two phases and phase diagram

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Pure metallic elements have engineering applications; for example, ultra-
high purity copper (Cu) or aluminum (Al) is used to make microelectronic
circuitry.
In most applications, however, we use alloys.An “alloy” as a material that
exhibits properties of a metallic material and is made from multiple
elements.
A plain carbon steel is an alloy of iron (Fe) and carbon (C).
Corrosion-resistant stainless steels are alloys that usually contain iron (Fe),
carbon (C), chromium (Cr), nickel (Ni), and some other elements.
Similarly, there are alloys based on aluminum (Al), copper (Cu), cobalt
(Co), nickel (Ni), titanium (Ti), zinc (Zn), and zirconium (Zr).
There are two types of alloys: Single-phase alloys and Multiple phase
alloys.

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A phase can be defined as any portion, including the whole, of a system which
is physically homogeneous within itself and bounded by a surface that
separates it from any other portions.
For example, water has three phases—liquid water, solid ice, and steam.
A phase has the following characteristics:
1. the same structure or atomic arrangement throughout;
2. roughly the same composition and properties throughout; and
3. a definite interface between the phase and any surrounding or adjoining
phases.

Phase rule:Gibbs developed the phase rule in 1875–1876. It describes the

relationship between the number of components and the number of phases for
a given system and the conditions that may be allowed to change (e.g.,
temperature, pressure, etc.).
It has the general form :2 + C = F + P
(when temperature and pressure both can vary)
C is the number of chemically independent components, usually elements or
compounds, in the system

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 F is the number of degrees of freedom, or the number of variables (such as
temperature, pressure, or composition), that are allowed to change
independently without changing the number of phases in equilibrium;
P is the number of phases present (please do not confuse P with “pressure”).
The constant “2” in Equation implies that both the temperature and pressure
are allowed to change.

POINTS TO NOTE:
The term “chemically independent” refers to the number of different
elements or compounds needed to specify a system. For example, water (H2O) is
considered as a one component system, since the concentrations of H and O in H2O
cannot beindependently varied.

Phases do not always have to be solid, liquid, and gaseous forms of a material. An
element, such as iron (Fe), can exist in FCC and BCC crystal structures. These two
solid forms of iron are two different phases of iron that will be stable at different
temperatures and pressure conditions

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 UNARY PHASE DAIGRAM OF PURE MAGNESIUM
A Magnesium Unary (C = 1) phase diagram
has lines divide the liquid, solid, and vapor
phases. Aslo known as Pressure-Temperature or
P-T diagram. Depending on the temperature
and pressure, there may be one, two, or even
three phases present at any one time: solid
magnesium, liquid magnesium, and magnesium
vapor.
Note that at atmospheric pressure (1 atm), the
intersection of the lines in the phase diagram
give the usual melting and boiling temperatures
for magnesium. At very low pressures, a solid
such as magnesium (Mg) can sublime, or go
directly to a vapor form without melting, when
it is heated.
At this point A , magnesium is all liquid. The
number of phases is one (liquid). The phase rule
tells us that there are two degrees of freedom.
2 + C = F + P,
therefore, 2 + 1 = F + 1 (i.e., F = 2)
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At point B, the boundary between the solid and
liquid portions of the diagram.The number of
components, C, is still one, but at point B, the
solid and liquid coexist, or the number of
phases P is two. From the phase rule
2 + C = F + P,
therefore, 2 + 1 = F + 2 (i.e, F = 1)
Fixing one degrees of freedom the other is
Found.
Finally, at point X, solid, liquid,and vapor
coexist.the number of components is still one,
there are three phases. The number of degrees
of freedom is zero.

A point on the phase diagram at which the

solid, liquid, and gaseous phases coexist under
equilibrium conditions is the triple point

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Phase Diagrams -types
A phase diagram shows the phases and their compositions at any combination of
temperature and alloy composition. When only two elements or two compounds are
present in a material, a binary phase diagram.
In the Isomorphous systems, which include the copper-nickel and NiO-MgO systems
only one solid phase forms and the two components in the system display complete
solid solubility.
A ternary phase diagram is a phase diagram for systems consisting of three
components. CaO . SiO2 and SrO . SiO2
In a pseudo-binary diagram, we represent equilibria between three or more
components using two compounds

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Free energy in intermediate phases
Free Energy is a thermodynamic quantity given by the subtraction between the
internal energy of a system and the product of its absolute temperature and
entropy.
In Chemistry terms, it is also known as the difference between the enthalpy
and the multiplication of the absolute temperature and entropy of a system.
Free Energy, is the energy found in a physical system that can be made into
work.
Free energy determines whether a chemical reaction is spontaneous or not
spontaneous
Two theory
i)Helmholtz Free Energy, which is energy that can be turned into work at a
constant temperature and volume.
ii)Gibbs Free-Energy, the measure of total entropy changes along with the
surroundings with constant pressure.
Helmholtz free energy is the thermodynamic potential found in a system of
constant species with constant temperautre and constant volume, given by the
formula: ΔF = ΔE – TΔS

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F = Helmholtz Free Energy in Joule
E = Energy of the System in Joule
T = Absolute Temperature in Kelvin
S = Entropy in Joule/Kelvin

Gibbs' Free Energy is the sum of its enthalpy (H) and the product of the
temperature and the entropy (S) of the system.
ΔG = ΔH − TΔS
change in free energy= change in enthalpy - (temperature) change in entropy
Spontaneous - is a reaction that is consider to be natural because, it is a
reaction that occurs by itself without any external action towards it.
Non spontaneous - needs constant external energy applied to it in order for
the process to continue and once you stop the external action the process will
cease.
When solving for the equation, if change of G is negative, then it's
spontaneous. If change of G if positive, then it's non spontaneous

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EFFECT OF FREE ENERGY
Free energy is important because it determines whether or not a phase
transformation is thermodynamically possible.
Essentially, the change in free energy, either ∆F or ∆G, must be negative for a
reaction to occur; that is, the reaction must result in an overall reduction of
the free energy of the system.
If the free-energy change is zero, the system is in a state of equilibrium,
and no reaction will occur (there is no driving force, or energy, for change).
Likewise, if the free-energy change is positive, the reaction will not occur.
To summarize:
If ∆F or ∆G >0 or positive, the reaction will not occur.
If ∆F or ∆G=0, the system is in equilibrium, and the reaction will not occur.
If ∆F or ∆G<0 or negative, the reaction will occur.
The more negative the free-energy change (the larger the magnitude of the
negative number), the greater is the driving force for a transformation.
In other words, if the free-energy change is a small negative number, the
driving force is low, and as it becomes more negative

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PHASE EQUILIBRIUM:
Equilibrium is another essential concept that is best described in terms of a
thermodynamic quantity called the free energy.
In brief, free energy is a function of the internal energy of a system, and also
the randomness or disorder of the atoms or molecules (or entropy).
A system is at equilibrium if its free energy is at a minimum under some
specified combination of temperature, pressure, and composition.
In a macroscopic sense, this means that the characteristics of the system do
not change with time but persist indefinitely; that is, the system is stable.
A change in temperature, pressure, and/or composition for a system in
equilibrium will result in an increase in the free energy and in a possible
spontaneous change to another state whereby the free energy is lowered.
The term phase equilibrium, refers to equilibrium as it applies to systems
in which more than one phase may exist.
Phase equilibrium is reflected by a constancy with time in the phase
characteristics of a system.

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Suppose that a sugar–water syrup is
contained in a closed vessel and the solution
is in contact with solid sugar at 20C.
If the system is at equilibrium, the
composition of the syrup is 65 wt%
C12H22O11–35 wt% H2O and the amounts
and compositions of the syrup and solid
sugar will remain constant with time.
If the temperature of the system is suddenly
raised to 100C this equilibrium or balance is
temporarily upset in that the solubility limit
has been increased to 80 wt% C12H22O11 .
Thus, some of the solid sugar will go into
solution in the syrup.
This will continue until the new equilibrium syrup concentration is established at the
higher temperature. This sugar–syrup example illustrates the principle of phase
equilibrium using a liquid–solid system

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In many metallurgical and materials systems of interest, phase equilibrium
involves just solid phases.
In this regard the state of the system is reflected in the characteristics of the
microstructure, which necessarily include not only the phases present and their
compositions but, in addition, the relative phase amounts and their spatial
arrangement or distribution.
It is often the case, especially in solid systems, that a state of equilibrium is
never completely achieved because the rate of approach to equilibrium
is extremely slow; such a system is said to be in a none quilibrium or
metastable state.
A metastable state or microstructure may persist indefinitely, experiencing
only extremely slight and almost imperceptible changes as time progresses.
Often, metastable structures are of more practical significance than
equilibrium ones.
For example, some steel and aluminum alloys rely for their strength on the
development of metastable microstructures during carefully designed heat
treatments

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Liquidus and Solidus Temperatures
Liquidus temperature as the temperature
above which a material is completely liquid.
The upper curve in Figure known as the
liquidus, represents the liquidus
temperatures for copper-nickel alloys of
different compositions.
By heating a copper-nickel alloy above the
liquidus temperature to produce a
completely liquid alloy that can then be cast
into a useful shape.
The liquid alloy begins to solidify when the
temperature cools to the liquidus
temperature.
For the Cu-40% Ni alloy in Figure, the
liquidus temperature is 1280°C.

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The solidus temperature is the temperature below
which the alloy is 100% solid.
The lower curve in Figure, known as the solidus,
represents the solidus temperatures
for Cu-Ni alloys of different compositions.
A copper-nickel alloy is not completely solid until
the material cools below the solidus temperature.
If we use a copper-nickel alloy at high
temperatures, we must be sure that the service
temperature is below the solidus so that no melting
occurs.
For the Cu-40% Ni alloy in Figure, the solidus
temperature is 1240°C.
The temperature difference between the liquidus
and the solidus is the freezing range of the alloy.
Within the freezing range, two phases coexist: a
liquid and a solid.
The solid is a solution of copper and nickel atoms
and is designated as the phase. For the Cu-40% Ni
alloy ( phase) in Figure, the freezing range is .
1280 - 1240 = 40°C
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INTERPRETATION OF PHASE DIAGRAMS
For a binary system of known composition and temperature that is at
equilibrium, at least three kinds of information are available:
(1) the phases that are present,
(2)the compositions of these phases, and
(3) the percentages or fractions of the phases..
Phases Present
Locate the temperature–composition point
on the diagram and notes the phase(s) with
which the corresponding phase field is
labeled.
For example, an alloy of composition
60 wt% Ni–40 wt% Cu at 1100C would be
located at point A in Figure because this is
within the region, only the single phase
will be present.
On the other hand, a 35 wt% Ni–65 wt%
Cu alloy at 1250C (point B) will consist of
both and liquid phases at equilibrium.
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Determination of Phase Compositions
The first step in the determination of phase
compositions (in terms of the
concentrations of the components) is to
locate the temperature–composition point
on the phase diagram.
Different methods are used for single- and
two-phase regions.
If only one phase is present, the procedure
is as l: the composition of this phase is
simply the same as the overall composition
of the alloy.
For example, consider the 60 wt% Ni–40
wt% Cu alloy at 1100C (point A, ).
At this composition and temperature, only
the phase is present, having a composition
of 60 wt% Ni– 40 wt% Cu.

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For an alloy having composition and
temperature located in a two-phase region,
the situation is more complicated.
In all two-phase regions (and in two-phase
regions only), one may imagine a series of
horizontal lines, one at every temperature;
each of these is known as a tie line, or
sometimes as an isotherm.
These tie lines extend across the two-phase
region and terminate at the phase boundary
lines on either side. To compute the equilibrium
concentrations of the two phases, the
following procedure is used:
1. A tie line is constructed across the two-phase
region at 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.
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For example, consider again the 35 wt% Ni–65
wt% Cu alloy at 1250C, located at point B in
Figure and lying within the α+L region
Thus, the problem is to determine the
composition (in wt% Ni and Cu) for both the α
and liquid phases.
The tie line has been constructed across the
α+ L phase region, as shown in Figure.
The perpendicular from the intersection of the
tie line with the liquidus boundary meets the
composition axis at 31.5 wt% Ni–68.5 wt% Cu,
which is the composition of the liquid phase,
CL.
Likewise, for the solidus–tie line intersection,
we find a composition for the α solid-solution
phase, of 42.5 wt% Ni–57.5 wt% Cu.

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Determination of Phase Amounts
The relative amounts (as fraction or as
percentage) of the phases present at
equilibrium may also be computed with
the aid of phase diagrams.
Again, the single and two-phase
situations must be treated separately.
The solution is obvious in the
single-phase region: because only one
phase is present, the alloy is composed
entirely of that phase; that is, the phase
fraction is 1.0 or, alternatively, the
percentage is 100%.
For example of 60 wt% Ni–40 wt% Cu
alloy at 1100C (point A in Figure ), only
the α phase is present; hence, the alloy
is completely or 100% α.

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If the composition and temperature position is located within a two-phase
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), which is applied as follows:
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.
5. If phase percentages are desired, each phase fraction is multiplied by 100.
When the composition axis is scaled in weight percent, the phase fractions
computed using the lever rule are mass fractions—the mass (or weight) of a
specific phase divided by the total alloy mass (or weight). The mass of each
phase is computed from the product of each phase fraction and the total alloy
mass.

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Lever Rule Derivation
Consider the phase diagram for copper and nickel
(Figure) and alloy of composition C0 at 1250C, and
let Ca, CL, Wa, and WL represent the same parameters
as given earlier.
This derivation is accomplished through two
conservation-of-mass expressions.
With the first, because only two phases are
present, the sum of their mass fractions must be
equal to unity; that is, Wa+ WL =1.

For the second, the mass of one of the components

(either Cu or Ni) that is present in both of the phases
must be equal to the mass of that component in
the total alloy, or

Simultaneous solution of these two equations leads

to the lever rule expressions for this particular
situation.

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For an alloy consisting of α and β phases, the volume fraction of the phase,
Vα, is defined as

where Vα and V denote the volumes of the respective phases in the alloy

On occasion conversion from mass fraction to volume fraction (or vice versa)
is desired. Equations that facilitate these conversions are as follows:

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Application of Lever rule
Consider an example in which at 1250C both
and liquid phases are present for a 35 wt%
Ni–65 wt% Cu alloy.
The problem is to compute the fraction of
each of the α and liquid phases. The tie line
has been constructed that was used for the
determination of α and L phase
compositions.
Let the overall alloy composition be located
along the tie line and denoted as C0, and
mass fractions be represented by WL and Wα
for the respective phases. From the
lever rule, WL may be computed according to

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Composition need be specified in terms of only one of the constituents for a binary
alloy; for the preceding computation, weight percent nickel will be used (i.e., C0
35 wt% Ni,, Cα=42.5wt%Ni, and CL =31.5 wt% Ni), and

Similarly, for the phase,

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esrmnotes.in | Class notes made easy.
Cooling Curves of pure metal A cooling curve shows how the temperature
of a material (in this case, a pure metal)
decreases with time.
The liquid is poured into a mold at the
pouring temperature, point A.
The difference between the pouring
temperature and the freezing temperature is
the superheat.
The specific heat is extracted by the mold
until the liquid reaches the freezing
temperature (point B).Further it is
undercooled (point B to C).
The slope of the cooling curve before
solidification begins is the cooling
rate . ∆T/∆t.
As nucleation begins (point C), latent heat
of fusion is given off, and the temperature
rises.
This increase in temperature of the
undercooled liquid as a result of nucleation
is known as recalescence (point C to D).
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Cooling Curves of pure metal Solidification proceeds isothermally at the
melting temperature (point D to E) as the
latent heat given off from continued
solidification is balanced by the heat lost
by cooling. This region between points D
and E, where the temperature is constant,
is known as the thermal arrest.
A thermal arrest, or plateau, is produced
because the evolution of the latent heat of
fusion balances the heat being lost
because of cooling.
At point E, solidification is complete, and
the solid casting cools from point E to
room temperature

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Cooling Curves of pure metal If the liquid is well-inoculated, the extent
of undercooling and recalescence is
usually very small and can be observed in
cooling curves only by very careful
measurements.
When a metal casting freezes, impurities in
the melt and the walls of the mold in which
solidification occurs serve as heterogeneous
nucleation sites.
Sometimes we intentionally introduce
nucleating particles into the liquid.
Such practices are called grain refinement or
inoculation.
Chemicals added to molten metals to promote
nucleation and, hence, a finer grain size, are
known as grain refiners or inoculants.

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esrmnotes.in | Class notes made easy.