PHASE AND PHASE

EQUILIBRIUM
Introduction:
 One of the most important objective of engineering
metallurgy is to determine properties of material

 The properties of material is a function of the microstructure

which depend on the overall composition and variable such as
pressure and temperature.
 Hence to determine the phase present in the material system , an
equilibrium or phase diagram is plotted.
 Equilibrium diagram or phase diagram is a graphical
representation of various phase present in material
system at various temperature and composition point.
 All the phase diagrams have temperature as the ordinate as
ordinate(Y-axis) and percentage composition by weight as the
abscissa(X-axis)
 Uses of equilibrium or phase diagram:
The equilibrium diagram is used to obtain following information:
1. It shows the various phase present at different
composition and temperature.
2. It indicate solid solubility of one element in other.
3. It shows the temperature range over which solidification or
liquidification of material system occurs.
4. It indicate the temperature at which different phase start to melt.
Basic Terms:
1. System: The substances that isolated and unaffected by their
surrounding are known as system.
It may be composition of solid, liquid , gases or the combinations
and may have metals and nonmetals separately or in any combination.
A system is capable of changing its composition, temperature,
pressure, density etc.
3. Phase: It is a physically and chemically composition of a
substance(system), separated from the other portion by a surface and
an interface. Each portion have different composition and properties.
In a equilibrium diagram, liquid is one phase and solid solution is
another phase.
3. Variables: A particular phase exists under various condition of
pressure and temperature and composition. These parameters are
known as the variables of the phase.
Basic Terms:
4. Component: These are the substances, element or chemical
compound whose presence is necessary and sufficient to make
a system. A pure metal is one component system whereas and
alloy of metals is a two-component(binary) system etc.
5. Alloy: It is a mixture of two or more elements having metallic
properties. In the mixture, metal is in the large proportion and
the other can be metal and non-metals.
 GIBB’S PHASE RULE
Gibbs phase rule establishes the relationship
between the number of variable (F), the number of
element (C), and the number of phases(P). It is
expressed mathematically as follows:
P+F=C+2
……….(I)
Where, P = Number of phases in system
F = Number of variables that can be
change independently without effecting number of
phases
C = Number of elements
2 = It represent any two variables amongst
 GIBB’S PHASE RULE
In general all equilibrium diagram studied at constant
pressure, hence Gibb’s phase rule is modified to”
P+F=C+1 ……….(II)
 Phase rule helps to determine maximum number of
phase present in an alloy system under equilibrium
conditions at any point in phase diagram.
 The phase rule can also be used to determine the degree of
freedom that can be changed
 Solid solution and Compound
 The element present in the alloy in the largest portion is
referred as base metal or parent metal or solvent and the
other elements are referred as alloying element or solute.
 Solid solution is a type of alloy in which the atoms of
alloying element are distributed in the base metal and both
have similar crystal structure.
 The composition of alloying element may vary but the
structure should be similar to base metal.
 Solid solution and Compound
Solid solution

Substitutional Interstitial
solid solution solid solution

Regular Random
Or Or
Ordered Disordered
 1) Substitutional solid solution
 In substitutional solid solution, atoms of alloying element
occupy the atomic size of base metal.
 They are further classified as:
(a) Regular or ordered substitutional solid solution:
 I n this type, the substitution of atoms of alloying
element is in definite order in the base metal matrix.
 E x a m p l e s : Ni-Al solid solution below 400 C.
Ni (solvent)
Al (solute)
Random or disordered substitutional solid solution:
 In this type, substitution of alloying elements is in any
random order in the base metal matrix.
 Example: Alpha brass

Copper solvent
Zinc solute
(2) Interstitial solid solution:
 In Interstitial solid solution, the atoms of alloying
elements occupy the interstitial sites of base metal.
 T h i s type of solution is formed when atomic size of alloying
element is much smaller compared to that of the base metal.
 Example: Fe-C

Iron (solvent)
Carbon (solute)
 Hume - Rothery’s Rules for Solid Solubility

 Solid solution is an alloy of two or more element wherein the

atomic crystal structure of alloying element (solute) is same
as that of the base metal matrix (solvent).
 The solubility limit of the solute in the solvent ( of the
alloying element in base metal matrix) is governed by certain
factors.
 These governing factors are known as Hume- Rothery’s rules
for solid solubility.
 These governing factor are as follows.
 Hume - Rothery’s Rules for Solid Solubility
1. Atomic size:
 Alloying elements having similar atomic size as that
of the base metal matrix have better solid
solubility.
 For a favorable solid solution formation, the
difference of atomic size of solute and solvent
should be less than 15 %.
2. Chemical affinity:
 Element having lower chemical affinity have greater
solid solubility.
 Element having higher chemical affinity have the
tendency of formation of compound and hence
restrict formation of solid solution.
 In general, the alloy elements located closer in the
periodic table have higher solid solubility.
 Hume - Rothery’s Rules for Solid Solubility

3. Relative valency:
 Metals having lower valency have more solubility for metals
having higher valency.
 Hence, for better solubility, the base metal selected should
be one that has lower valency as compared to that of
alloying elements.
4. Crystal structure:
 As mentioned earlier, solid solution is an alloy of
element having similar crystal structure.
 Difference in crystal structure limits the solid solubility
of elements.
 Cooling Curves
 cooling curve is the graphical plot of phases of
element on temperature v/s time.
 The resulting phase during solidification is
different for various alloy composition.
The most common coolingcurves are:
1. For pure metals
2. For binary solid solution(alloy)
3. For eutectic binary alloy
4. For off-eutectic binary alloy
 1. Cooling Curves for Pure Metals

F=1

F=0 F=1
 Region AB represent liquid state, solidification starts at
B and continue until C, region CD represent solid state.
Application of Gibb’s phase rule in various regions:

(1)Region AB
P+F=C+1
1+F=1+1
• Therefore,

F=1
•Thus F = 1 means that only one variable i.e
temperature can be varied without changing the
(2) Region BC
P+F=C+1
2+F=1+
1
Therefore,

F=0
Thus F = 0 means that no variable amongst temperature and
pressure can be varied with out changing the Liquid + Solid phase of
system. If the temperature is increased the metal goes into liquid
state and if the temperature is lowered it goes into solid state.

(3) Region CD
P+F=C+1
1+F=1+
1
Therefore,
2. Cooling Curves for Binary solid solution (alloy)
 Region AB represent liquid state, solidification starts
at B and continue until C, region CD represent solid
state.
Application of Gibb’s phase rule in various regions:
(1) Region AB
P+F=C+1
1+F=2+
1
Therefore,

F=2
Thus F = 2 means any two variables temperature and
composition can be varied without effecting liquid
(2) Region BC
P+F=C+1
2+F=2+
1
Therefore,

F=1
Thus F = 1 means that only one variable i.e temperature can
be varied without changing Liquid + Solid phase of system.

(3) Region CD
P+F=C+1
1+F=2+
1
Therefore,
 Application of Gibb’s phase rule in various regions:

(1) Region
AB P + F =
C+1 1+F
=2+1
Therefore,

F=2
Thus F = 2 means any two variables temperature and composition can be varied
without effecting liquid phase of the system.
(2) Region BC
In this region, either or start separating out by solidification.
P+F=C+1
2+F=2+1
Therefore, F=1
(3) Region CD
In this region, the other starts separating out by solidification
P+F=C+1
3+F=2+1
Therefore, F = 0
Thus F = 0 means that no variable amongst temperature and
composition can varied without changing the Liquid + Solid
state of the system.
(4)Region DE
P+F=C+1
2+F=2+
1
Therefore, F
=1
Thus F = 1 means that only one variable i.e temperature can
Binary solutions with unlimited solubility (VI)
• Example of isomorphous system: Cu-Ni (the complete solubility occurs
because both Cu and Ni have the same crystal structure, FCC, similar
radii, electronegativity and valence).
• EUTECTIC SYSTEM
– In an eutectic reaction, when a liquid solution of fixed composi-
tion, solidifies at a constant temperature, forms a mixture of two or
more solid phases without an intermediate pasty stage. This
process reverses on heating.

– In eutectic system, there is always a specific alloy, known as

eutectic composition, that freezes at a lower temperature than all
other compositions.
– At the eutectic temperature, two solids form simultaneously from a
single liquid phase.
– The eutectic temperature and composition determine a point on
the phase diagram called the eutectic point.
– Binary alloy eutectic system can be classed as:

1. One in which, two metals are completely soluble in the liquid

state but are insoluble in each other in the solid state.
2. two metals are completely soluble in the liquid state but are
partly soluble in each other in the solid state.
1. Two metals completely soluble in the liquid state but
completely insoluble in the solid state.
– Technically, no two metals are completely insoluble in each
other. However, in some cases the solubility is so restricted that
for practical purposes they may be considered insoluble.
• Alloy-3: 80% Cd and 20% Bismuth.
– As the temperature falls to T1, crystal nuclei of pure Cd begin to
form. Since pure Cd is deposited, it follows that the liquid
becomes richer in Bi; the composition of liquid move s to left 3’
and as indicated by the diagram, no further Cd deposits until
temperature falls to T2.
– At T2 more Cd is deposited and dendrites begin to develop from
the already formed nuclei.
– The growth of the Cd dendrites, on the one hand, and the
consequent enrichment of the remaining liquid in Bi, on the
other, continues until the temperature has fallen to 140°C, the
eutectic temperature in this case.
– The remaining liquid then contains 40% Cd and 60% Bi, the
eutectic composition.
• Alloy-1: 20% Cd and 80% Bi
– Contrary to alloy 3, in this case crystal of pure Bi form first, enriching
the melt with Cd.
– The composition of the melt (or liquid) moves to right until Ultimately
the point E is reached and the remaining liquid solidi-fies as eutectic
(40% Cd and 60% Bi).

• Alloy-2: 40% Cd and 60% Bi (eutectic alloy)

– No solidification occurs until the melt reaches the eutectic
temperature (140°)
– At the eutectic temperature, the two pure metals crystallize together
to give a characteristically line aggregate known as eutectic.
– Eutectic consists of alternate layers of Cd and Bi which form at
the eutectic temperature (140°C in this case).
 EX. The following data is for Pb-Sn alloy system : (Lead-Tin Solder)
Melting point of lead (Pb) - 327ºC
Melting point of Tin (Sn) - 232ºC
Eutectic alloy is formed at 183ºC with 62% Sn –38% Pb
Maximum solid solubility of tin in lead at 183ºC –19%
Maximum solid solubility of lead in tin at 183ºC –3%
Maximum solubility of tin and lead at room
temperature is negligible.
(1)Draw the phase diagram with the help of above data and label all
the points, lines and regions on it.
(2)For 70%Pb – 30%Sn alloy composition, determine the amounts of
proeutectic and eutectic constituents at room temperature.
2. Two metals completely soluble in the liquid state, but only
partly soluble in the solid state
– Since most metals show some solubility for each other in the solid
state, this type is the most common and, therefore, the most
common alloy system.
– Metals such as Pb-Sn and Pb-Sb are partly soluble in each other in
the solid state.
– Fig. shows the Tin-Lead equilibrium diagram with micro-structures
(of course) obtained under non-equilibrium condition of
solidification.
I. Tin will dissolve up to maximum of 2.6% Pb at the temperature,
forming the solid solution α.
II. Lead will dissolve up to a maximum of (100-80.5) i.e. 19 .5% tin at
the eutectic temperature, giving the solid solution β.
III. Slope of BA and CD indicate that the solubility of Pb in Sn (α) and
that of Sn in Pb (β) decrease as temperature falls

–. Consider an alloy of composition Z (70% Pb-30% Sn). As the melt

– The alloy solidifies as a solid solution until at 183°C, the last layer of
solid to form is of composition C (80.5% Pb-19.5% Sn).
– The remaining liquid which has the eutectic composition (38% Pb-62%
Sn) then solidifies by depositing, in the form of a eutectic, i.e.,
alternate layers of α and β, of compositions B and C respectively.
– If cooled slowly to room temperature the compositions of the solid
solutions α and β will follow the line BA and CD, i.e., α will become
progressively poorer in lead and β in tin.
– Take another alloy of composition Z' (95% Pb-5% Sn). When cooled
slowly, solidification starts at R and is complete at P, the resultant
solid being a homogeneous single phase, the β solid solution.
– As the alloy cools, the solvus line is reached at point Q. The β solution
is now saturated in tin. Below this temperature, under conditions of
slow cooling, the excess tin must come out of solution. Since tin is
soluble in lead, the precipitate does not come out as the pure metal
tin, but rather the α solid solution.
• Peritectic reaction:
– It is the reaction that occurs during the solidification of some
alloys where the liquid phase reacts with a solid phase to give a
solid phase of different structure.
– Assuming very slow rates of cooling, the peritectic reaction will
occur only in those Pt-Ag alloys that Contain between 12 and 69%
silver (Ag).
– Consider a liquid (melt) of composition Z, i.e., containing 25% Ag.
Solidification commences at T1 and dendrites of α, initially of
composition W, begin forming.
– Selective crystallization of α continues down to Tp, the peritectic
temperature; when the alloy reaches. this temperature, it is
composed of solid α-dendrites of composition B and liquid of
composition D in the proportion α : liquid = RD : RB.
• Eutectoid Transformation:
– Eutectoid reaction is an isothermal reversible reaction in which a
solid phase (usually solid solution) is converted into two or more
intimately mixed solids on cooling, the number of solids formed
being the same as the number of component in the system.
• Peritectoid Transformation:

– The peritectoid reaction is the transformation of two solid into a

third solid.