MATERIAL SCIENCE &

METALLURGY
2131904

Chapter 6
Phase and Phase equilibrium

Prepared by
Prof. Naman M. Dave
Assistant Professor,
Mechanical Engg. Dept.
Gandhinagar Institute of Technology.
 Please do not blindly follow
the presentation files only, refer
it just as reference material.
More concentration should
on class room work and text
book-reference books.
 Contents
• Basic Terms
• Introduction - Components – Phase
• Phases – Solution
• Solid solutions
• Intermediate Alloy Phases
• Non-homogenous Phases / Mechanical Mixtures
• Hume Rothery Rule’s for Solid Solution
• Solidification
• Equilibrium Phase Diagram - Unary
• Cooling Curves
• Binary phase diagram
• Lever Arm Principle
• Gibbs’s Phase Rule
• Reactions in binary phase diagrams
Prof. Naman M. Dave
 Basic terms
1. System
• Thermodynamically, a system is an isolated body of matter
which is under study.
• A substance or a group of substances so isolated from its
surroundings that it is totally unaffected by the surroundings but
changes in its overall composition, temperature, pressure or total
volume can be allowed as per the desire of the person who
investigates it.
• A system may contain solids, liquids, gases or their combination.
• It may have metals ,non-metals separately or in combined form.

2. Phase
• A phase is a substance or a portion of matter which is
homogenous, physically distinct and mechanically separable..
• Physically distinct and mechanically separable means that the
phase will have a definite boundary surface.
• Different phases are given different names or symbols
like α (alpha),ß (Beta), γ (Gamma), etc.

Prof. Naman M. Dave

 Basic terms

Introduction - Components - Phase

• Components are pure metals and/or compounds of which
an alloy is composed. For example, in a copper–zinc
brass, the components are Cu and Zn.
• It refers to a independent chemical species. The
components of a system may be elements, ions or
compounds.
• A component can exist in many phases.
– Water exists as ice, liquid water, and water vapor.
– Carbon exists as graphite and diamond.

Prof. Naman M. Dave

 Basic terms
Components and Phases
• Components:
The elements or compounds that are mixed initially (Al and Cu).
• Phases:
A phase is a homogenous, physically distinct and mechanically
separable portion of the material with a given chemical composition
and structure (a and b).
Aluminum-
Copper
Alloy

Prof. Naman M. Dave

3. Equilibrium :
Basic terms
• Equilibrium in a system is the state of minimum free energy under any specified
combination of overall composition, temperature, pressure and overall volume.
• Once equilibrium is achieved, even a minor change in these parameters of
composition, temperature, pressure, volume within the system means an increase in
free energy.
4. Degrees of Freedom:
• It is also known as variance of system.
• It is defined as number of external or internal factors of the system (temperature,
pressure and concentration) that can be independently changed without altering
equilibrium i.e. without causing disappearance of a phase or formation of a new
phase in the system.
5. Structural Constituent
• Phase distribution in a system is not necessarily uniform throughout the structure.
• These phases are associated in different ways to form the structure. This association
of phases in a recognizably distinct fashion is referred to as “structural constituent”
of the alloy.
Prof. Naman M. Dave
 Basic terms
6.Single and Multiphase Solids
• A single crystal of a material may consist of one phase only while
polycrystalline material may be single or multi-phase depending upon
the nature of individual crystals or grains present.
• Examples : All pure metals are single phase solids
• Alloys like Iron and Steel, Rocks, ceramics, wood, fibre-glass,
polymers, etc. are examples of multi-phase solids.
• Properties of multi-phase solids is dependent upon…
1.Physical and chemical natures of phases present
2.Amount of each phase (%)
3.Distribution of each phase in relation to other phases
4.Size of domain occupied by each phase

Prof. Naman M. Dave

7. Alloys
Basic terms
• Pure metals because of their poor physical and mechanical properties are seldom
used in engineering applications. Most of useful metallic materials are combinations
of metals which are called alloys.
• An alloy can be defined as a substance possessing metallic properties, having
metallic bond and composed of two or more than two elements out of which atleast
one of them is metal.
• Metal present in larger proportion is called base metal while other metallic or non-
metallic element is known as alloying element.
• Elements may combine in different ways to form alloys.
• These elements of alloys usually show complete solubility in liquid state. However,
on cooling them to solid state, they may form mechanical mixtures or
homogenous phases.

Prof. Naman M. Dave

 Phases - Solution
• A solution (liquid or solid) is phase with more than one component;
a mixture is a material with more than one phase.
• Solute (minor component of two in a solution) does not change the
structural pattern of the solvent, and the composition of any solution
can be varied.
• In mixtures, there are different phases, each with its own atomic
arrangement. It is possible to have a mixture of two different
solutions!
• For many alloy systems and at some specific temperature, there is a
maximum concentration of solute atoms that may dissolve in the
solvent to form a solid solution; this is called a solubility limit.
• 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.
Prof. Naman M. Dave
Prof. Naman M. Dave
 Phases
Homogenous Phases Non-Homogenous Phases or
Heterogeneous Phases or
Mechanical Mixtures

Solid Solutions Intermediate Alloy Phases • Can be any combination i.e.

combination of pure metal and a
2 metals mixed 2 metals mixed solid solution (homogenous
within solubility beyond solubility phase)
limits limits • combination of pure metal and
an intermediate alloy phase, etc.

Substitutional Interstitial Intermediate Intermediate

Solid Solid Solid Compounds
Solutions Solutions Solutions

• Chemical Compounds
Substitutional Interstitial • Inter-metallic Compounds
Solid Solid • Interstitial Compounds
Solutions Solutions • Electron Compounds
• Lave’s Phases

Ordered Disordered
Substitutional Substitutional
Solid Solid
Solutions Solutions
Prof. Naman M. Dave
 Homogenous phases
• When two elements are completely soluble when coming into solid state
from liquid state and form compounds by chemical reaction, they form
phases known as homogenous phases.
• Each component of such phases loses its own identity, properties and
crystal structure.
1. Solid Solutions
• When two elements completely mix or dissolve in each other in liquid as
well as solid state (during process of solidification), then the resulting
structure or phase is known as a solid solution.
• In a solid solution, there can be more than two components. But in general,
the metal which is in higher proportion is known as base metal or solvent
and the other component (metal or non-metal) is called alloying element
or solute.
• There are two types of Solid Solutions – Substitutional Solid Solution
and Interstitial Solid Solution.

Prof. Naman M. Dave

 Solid solutions
• A solid solution is simply a solution in the solid state that
consists of two kinds of atoms combined in one type of space
lattice.
• There is a homogeneous distribution of two or more constituents
in the solid state.
• A solid solution is the result of, metals dissolving in each other’s
crystal lattice.

Solid Solution

Substitutional Solid Solution Interstitial Solid Solution

Ordered

Disordered
Prof. Naman M. Dave
 Solid solutions

Disordered Substitutional Solid Solution

Substitutional Solid Solution

Ordered Substitutional Solid Solution

Interstitial Solid Solution

Prof. Naman M. Dave
 Types of Solid Solutions
• When a solid solution form, the atoms of alloying element (solute) occupy certain
places in the lattice structure of the base metal (solvent).
• Depending upon the types of places occupied by the solute atoms, solid solutions
formed are of two types
1) Substitutional Solid Solution
• If atoms of alloying element (solute) replace
the atoms of the base metal (solvent) and
occupy their normal lattice sites, the resulting
solid solution is known as Substitutional
solid solution.
• For example, Copper atoms may substitute
Nickel atoms without disturbing their FCC
structure of Nickel.
• Thus they have unlimited solid solubility
whereas in case of Brass, FCC Copper
atoms (base/solvent) are replaced by HCP i.e.
Zinc atoms (alloying element/solute) which
has limited solubility.
Prof. Naman M. Dave
 2) Interstitial Solid Solution
• In Interstitial Solid Solution, the alloying element (solute) atoms do not replace the
base metal (solvent) atoms but enter into the empty spaces or interstices of the
lattice structure of the solvent atoms.
• As the empty spaces of lattice structure are limited in size, the interstitial solid
solution can only from when the solute atom is small enough to fit into these
spaces.
• The radii of atoms of commercial alloys is in the range of 1.2-1.6A0. It means that
the atoms with atomic radius less than 1A0 are likely to form interstitial solid
solution.
• It may be noted that if the alloying element is a transition element, there are
maximum chances of formation of Interstitial Solid Solution. This is not only
because of their small atomic radii but also due to their unusual electronic
structure.

• Examples of Interstitial Solid Solutions are – C

in Steel causing hardening, N in Steel causing
hardening, H in Steel during welding causing
embrittlement of weld area.
 Types of Substitutional Solid Solutions
• Depending on the order of replacement of base
metal (solvent) atoms by alloying element
(solute) atoms, there are two types of solid
solutions
1. Disordered or Random Substitutional solid
solution
• This is formed when the alloying element
(solute) atoms do not occupy any specific
orderly positions but replace the atoms in lattice
structure of base metal (solvent) atoms at
random then the phase is known as disordered
or random substitutional solid solution. It is
normally observed at high temperatures.
2. Ordered Substitutional solid solution
• This is formed when the alloying element
(solute) atoms occupy specific orderly positions
in the lattice structure of base metal (solvent)
atoms then the phase is known as ordered
substitutional solid solution. It is normally
observed at room temperatures.
 Intermediate Alloy Phases
• Addition of an alloying element to a given metal to an
excessive amount than solid solubility results in a second
phase appearance with the solid solutions. This second
phase is known as Intermediate Alloy Phase.
• It differs in both crystal structure and properties from
solid solutions.
• Intermediate phases may range between ideal solid
solutions on one hand and ideal chemical compounds on
the other hand.
• Intermediate alloy phases could be either intermediate
solid solutions or intermediate compounds.
Prof. Naman M. Dave
 Types of Intermediate Alloy Phases

1. Intermediate Solid Solutions

• In many alloy systems, crystal structures or phases are found which are different
from those of elementary components (pure metals).
• If these structures occur over a range of compositions, they are, in all respects,
solid solutions and therefore known as intermediate solid solutions.
• They have lattice structure which is different from that of solvent (base metal)
lattice.
2. Intermediate Compounds
• When different type of atoms combine in a definite proportion they form
compounds.
• Compounds can be denoted by chemical formula.
• Most common examples of compounds are water (H2O) and common salt (NaCl).
• Unlike mechanical mixtures, the combining elements in compounds lose their
individual identity and characteristic properties. For example – Sodium is very
active metal and oxidizes rapidly. Therefore , it is usually stored under kerosene.
Chlorine, if inhaled, is a poisonous gas. Now, when Sodium and Chlorine
combine they form Sodium Chloride or table salt which is a harmless compound.
Prof. Naman M. Dave
Types of Intermediate Compounds
• Depending upon the characteristics of combining elements, the compounds
can be of different types. They are as under.
1. Chemical Compounds :
• They are known as valency compounds.
• When two chemically dissimilar elements have greater chemical affinity
for each other , they form chemical compounds.
• For example, mixing of electropositive elements like Na, K, Al, Mg, etc.
with electronegative elements like Sn, Pd, As, Sb, Se, S, etc. result into
chemical compounds like AlSb, Mg3As2,Mg2Sn, MgSe, Cu2Se, CaSe, etc.
• Properties
• Composition of these compounds satisfy the valency laws
• They have generally ionic or covalent bonds
• They are non-metallic in properties
• They are generally hard, brittle and poor conductors with high melting
points.

Prof. Naman M. Dave

Types of Intermediate Compounds
2. Intermetallic Compounds :
• Unlike chemical compounds, intermetallic compounds rarely obey the laws of
chemical valence.
• They have complex lattice structures and are characterized by high hardness,
brittleness and melting point.
• Examples are Cu2Zn3, Cu3Sn4, CuAl2, SnSb, etc.
• These type of compounds have metallic bonding and valence electrons are
free to move in lattice giving good electrical conductivity property to these
substances.
3. Interstitial Compounds :
• These can be considered as a special case of intermetallic compounds.
• They are formed when the solubility limit of interstitial elements in a solid
solution is exceeded.
• The open spaces between the atoms are known as interstices.
• Atoms of elements like H, O, C, B and N have small radii and therefore they
can occupy the interstitial space between atoms of other metals.
• The base metal (solvent) is generally a transition, metal like Sc, Ti, Ta, W, Fe,
etc Prof. Naman M. Dave
Types of Intermediate Compounds
4. Interstitial Compounds :
• Like most intermetallic compounds, interstitial compounds do not obey normal
valency rules.
• Interstitial compounds are extremely hard, metallic in nature and have high
melting and boiling points.
• Their hardness is utilized in dispersion hardened alloys and high speed cutting
tool tips.
• Fe3C is an important interstitial compound of steel which governs many
properties.
• Other examples of this group include TiC, Fe4N, W2C, TiH, etc.
5. Electron Compounds
• These are intermediate phases which again do not obey the normal valency
rules.
• They are formed in metals having similar electrochemical properties and a
favourable size factor but different no. of valence electrons.
• They can be characterized by a definite ratio of valence electrons to the no. of
atoms (3/2, 21/13 or 7/4) with a particular crystal lattice corresponding to each
ratio. Prof. Naman M. Dave
Types of Intermediate Compounds
6. Electron Compounds
• Electronic compounds can be formed by 2 metals from following groups :
• Group-1 : Cu, Ag, Au, Fe, Co, Ni, Pd and Pt
• Group-2: Be, Zn, Cu, Al, Sn and Si
• Electron compounds are found in many alloys of commercial importance
like copper-zinc, copper-tin, copper-aluminium, copper-silicon, etc.
7. Lave’s Phases
• When the difference between the atomic radii of two elements is about 20-
30% then Lave’s phases are formed.
• The stochiometric formula of this compound is AB2.
• The atomic radii of the elements forming these phases are in a ratio of
approximately 1:1.2.
• Examples are – MgCu2, MgZn2, MgNi2, etc.

Prof. Naman M. Dave

 Non-homogenous Phases / Mechanical Mixtures
• When two elements are completely insoluble when coming into solid
state from liquid state and cannot form compounds by chemical reaction,
they form phases known as mechanical mixtures.
• Each component of such phases retains its own identity, properties and
crystal structure.
• Suppose two such metals A and B are mixed and melted together and the
microstructure after solidification is as under.

• Properties of mixture will be between A

and B i.e. depending upon proportion
of each
• Now if you separate A and B from the
mixture by converting it to liquid state
(using heat) and then cool them down
individually, you will find that
properties of both A and B are same as
they were in pure form.
Prof. Naman M. Dave
 Hume Rothery Rule’s for Solid Solution
• Hume Rothery’s rules govern the formation of substitutional solid solution
and aid in the proper selection of such alloying elements :

1. Crystal Structure Factor

2. Relative Size Factor
3. Chemical Affinity Factor
4. Relative Valance Factor

1. Crystal Structure Factor of two metals

(elements) should be same.

Prof. Naman M. Dave

 2. Relative Size Factor
• Atomic diameter shall be fairly similar, since atoms differing directly
greatly in size cannot be accommodated readily in the same structure (as a
substitutional solid solution).
• When the term size factor is employed and extensive solid solubility is
encountered only when the two different atoms differ size by less than
15%,called a favorable size factor.
• If the relative size factor is between 8%-15%, the alloy system usually
shows a minimum and If this factor is greater than 15% substitutional
solid solution formation is very limited.
 3. Chemical affinity Factor
• The greater the chemical affinity of two metals, the more restricted
their solubility is their solid solubility.
• When their chemical affinity of two metals is great, two metals tend
to form an intermediate phase rather than a solid solution.
• Generally, the farther apart the elements are in the periodic table the
greater the chemical affinity.
• If the elements have
similar
electronegativity,
they will make a
solid solution,
• if they have a
different
electronegativity, a
intermetallic
compound Prof. Naman M. Dave
 4. Relative valence Factor
• Consider a two atoms, one with large valance electrons and the other
with small number of valance electron.
• It has been found that high valance can dissolve only a small amount
of a lower valance metal , while the lower valance metal may have
good solubility for higher valance metal.
Solidification …
 Equilibrium Phase Diagram
• A diagram that depicts existence of different phases of a
system under equilibrium is termed as phase diagram.
• It is actually a collection of solubility limit curves. It is
also known as equilibrium or constitutional diagram.
• Equilibrium phase diagrams represent there relationships
between temperature, compositions and the quantities of
phases at equilibrium.
• These diagrams do not indicate the dynamics when one
phase transforms into another.

Prof. Naman M. Dave

 Equilibrium Phase Diagram
• Important information, useful in materials development and
selection, obtainable from a phase diagram.
• It shows phases present at different compositions and
temperatures under slow cooling (equilibrium) conditions.
• It indicates equilibrium solid solubility of one element /
compound in another.
• It suggests temperature at which an alloy starts to solidify
and the range of solidification.
• It signals the temperature at which different phases start to
melt.
• Amount of each phase in a two-phase mixture can be
obtained
Prof. Naman M. Dave
 Unary phase diagram
• If a system consists of just one component(e.g.:water),
equilibrium of phases exists depicted by unary phase diagram.
The component may exist in different forms, thus variables here
are–temperature and pressure.

Prof. Naman M. Dave

Cooling Curves

Prof. Naman M. Dave

Cooling Curves

Prof. Naman M. Dave

Cooling Curves

Prof. Naman M. Dave

Cooling Curves

Prof. Naman M. Dave

 Binary phase diagram
If a system consist soft components, equilibrium of phases exist is
depicted by binary phase diagram. Pressure is constant, thus in
dependently variable parameters are– temperature and composition.
 Two component
systems are classified
based on extent of
mutual solid solubility
• completely soluble in
both liquid and solid
phases (isomorphous
system)
• completely soluble in
liquid phase where as
solubility is limited in
solid state. Prof. Naman M. Dave
Binary phase diagram

Prof. Naman M. Dave

 Lever Arm Principle
• Proportion of co-existing phase at any given temperature.

• Determine the relative

amount of two phases, erect
an ordinate at a point
(30%Bi) on the composition
scale which gives the total
or overall composition of
the alloy.

Prof. Naman M. Dave

 Lever Arm Principle
• The intersection of this composition vertical (AL) and a given isothermal
line OP (i.e., point M is the fulcrum of a simple lever system and OM and
MP are two lever arms.)
• The relative lengths of the
lever arms multiplied by the
amounts of the phase present
must balance.

• This is called 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 (i.e., other) lever arm.

Prof. Naman M. Dave

 Lever Arm Principle
• It can also be seen that the proportion of solid corresponds to
the length of the segment adjacent to liquidus line, whereas
the fraction of liquid corresponds to the length of segment
adjacent to the solidus line.
• The isotherm (line OMP) can be
considered as a tie line, since it joins
the composition of two phases in
equilibrium at a specific
temperature.

Prof. Naman M. Dave

Relative amount of each phase
• % Liquid = (M2/MN) x 100 = [(50-25)/(65-25)] x 100 = 62.5%
• % Solid = (2N/MN) x 100 = [(65-50)/(65-25)] x 100 = 37.5%
 Gibbs’s Phase Rule
• The Phase Rule, known as 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
expressed mathematically as follows:
P+F=C+2

– where, P is the number of phases (e.g., solid, liquid etc.)

– F is the number of degrees of freedom or the number of
physical ' variables (pressure, temperature and concentration)
that can be independently changed without altering the
equilibrium, i.e., without causing disappearance of a phase or
the formation of a new phase in the system.
– C is the number of components in the system (for example, Pb
and Sn are the components of Pb-Sn equilibrium diagram.
Prof. Naman M. Dave
 Gibbs’s Phase Rule
• “Provided the equilibrium between any no. of phases is not influenced by
gravity or electrical forces or magnetic forces or surface tension, and
influenced only by the temperature, pressure and concentration then the no. of
degrees of freedom (F) of the system is related to no. of components (C) and
phases (P) can be related by the phase rule equation. F = C – P + 2
• In studying the chemical equilibrium, temperature and pressure are
considered as external factors determining the state of the system. Therefore
in the phase rule equation, the digit 2 stands for these two variables –
temperature and pressure.
• In applying the Gibb’s phase rule to the metal systems, the pressure is
considered as remaining fixed at one atmosphere. Thus, the effect of pressure
is neglected, leaving only one variable factor i.e. temperature.
• The phase rule equation then simplifies to F = C – P + 1
• since the degrees of freedom F cannot be less than zero
• C + 1 – P => 0, OR P <= C + 1 which means the number of Phases can not
exceed the number of component plus one.
Prof. Naman M. Dave
Gibbs’s Phase Rule

Prof. Naman M. Dave

 Gibbs’s Phase Rule
 In equilibrium, all factors have definite (non-zero) values. Therefore, all
degrees of freedom cannot be less than zero. Mathematically,
F > 0 => C – P + 1 > 0 => C + 1 > P
 This means that the no. of phases in a system cannot exceed the no. of
components in a system plus one.
 For, a Binary alloy (2 metal alloy) system, no. of components C = 2
 Now, if
• P = 1 => F = 2 – 1 + 1 = 2 This is called Bi-variant System
• P = 2 => F = 2 – 2 + 1 = 1 This is called Mono-variant System
• P = 3 => F = 2 – 3 + 1 = 0 This is called Non-variant System
 Now, if
• F = 2 => Both temperature and pressure can be varied independently
• F = 1 => Only one out of temperature and pressure can be varied
independently
• F = 0 => Neither temperature nor pressure can be varied independently.
 Reactions
CLASIFICATION OF EQUITIBRIUM DIAGRAMS
- An equilibrium diagram has been defined as a plot of the composition of phases is
function of temperature in any alloy system under equilibrium conditions
- Equilibrium diagrams may be classified according to the relation of the component
in the liquid and solid states as follows:
 Components completely soluble in the liquid state,
• and also completely soluble in the solid state,
• but partly soluble in the solid state (EUTECTIC REACTION Type I).
• but insoluble in the solid state (EUTECTIC REACTION Type II)
• The PERITECTIC Reaction
 Transformation in solid state
• Eutectoid reaction
• Peritectoid reaction
 Types of reactions in binary phase diagrams
• Eutectic Reaction
• Peritectic Reaction
• Eutectoid reaction
• Peritectoid reaction
Prof. Naman M. Dave
Eutectic Reaction I-Type

Prof. Naman M. Dave

Eutectic Reaction II-Type
Peritectic Reaction

Prof. Naman M. Dave

Eutectoid reaction
Peritectoid reaction
Types of reactions in binary phase diagrams

Prof. Naman M. Dave