UNIT III PHASE RULE AND COMPOSITES

Phase rule: Introduction, definition of terms with examples. One component system-
water system; Reduced phase rule; Construction of a simple eutectic phase diagram -
Thermal analysis; Two component system: lead-silver system – Pattinson process.

1. Phase rule – Definition of terms with examples

 Define ‘component’ and ‘Degree of freedom’. (2) (January 2018)
 Define ‘component’. (8) (Nov./Dec. 2019)
 State phase rule and explain the terms involved in it. (8) (April/May 2019)
(8) (January 2022)

Phase Rule:

If the equilibrium between any number of phases is not influenced by gravity,

or electrical, or magnetic forces but are influenced only by pressure, temperature and
concentration, then the number of degree of freedom(F) of the system is related to
number of components and number of phases (P) by the following phase rule equation.

F=C-P+2

Explanation of terms

(i) Phase (P)

Phase is defined as, “any homogeneous physically distinct and mechanically separable
portion of a system which is separated from other parts of the system by definite
boundaries”.

(a) Gaseous phase –Completely miscible –single phase

(b) Liquid phase-Miscible-single phase –eg. Alcohol and water

Immiscible-two phases-eg. Benzene and water

(c)Solid phase-Every solid constitutes a separate phase.

(ii) Component

Component is defined as, “the smallest number of independently variable constituents,

by means of which the composition of each phase can be expressed in the form of a
chemical equation”.

Eg. (a) Consider a water system consisting of three phases.

Ice (g)⇌ Water(l) ⇌Vapour(g)

The chemical composition of all the three phases is H2O, but are in different physical
form. Hence the number of component is one.

(b)PCl5(s) → PCl3(l) + Cl2(g)

This system has three phases, but the number of component is only two.

(iii) Degree of freedom (F)

Degree of freedom is defined as, “the minimum number of independent variable factors
such as temperature, pressure and concentration, which must be fixed in order to define
the system completely”.

A system having 1,2,3 or 0 degrees of freedom is called univariant, bivariant, trivariant

and non variant respectively.

Eg. (a) Ice(g)⇌ Water(l) ⇌Vapour(g)

The above equilibrium has 3 phases and 1 component. The degree of freedom (F) is
given by F=C-P+2, F=1-3+2 = 0

These three phases will be in equilibrium only at a particular temperature and pressure.
Hence, this system does not have any degree of freedom (F), it is nonvariant.

(b) Water(l) ⇌Vapour(g)

The above equilibrium has 2 phases and 1 component. The degree of freedom (F) is
given by F=C-P+2, F=1-2+2 = 1

Any one of the degree of freedom such as T or P has to be fixed to define the system.
Hence it is univariant.

(c) For a gaseous mixture of N2 and H2, we must state both the pressure and
temperature. Hence, the system is bivariant.

2. One component system-water system

 What is triple point? (2) (April/May 2019)

 Explain the phase diagram of water in detail. (10) (January 2019)
 Describe the phase diagram of water system. (10) (Nov./Dec. 2019)
The phase diagram of water system is the study of behavior of three different phases of
water with temperature and pressure. It is a one-component system. The phase diagram
of the water system contains:

Curves OA, OB, OC

The triple point ‘O'

Areas AOC, AOB, BOC

Curve OA: Vaporization curve. It represents the equilibrium between water and
vapour. At any point on the curve the following equilibrium will exist.

Water ⇌ Water vapour

This equilibrium will extend up to the critical temperature (374 0 C). Beyond the critical
temperature the equilibrium will disappear and only water vapour will exist.

Curve OB: sublimation curve of ice.

Ice ⇌ Vapour

It represents the equilibrium between ice and water vapour. At any point on the curve,
the above equilibrium will exist. The equilibrium (line OB) will extend up to the
absolute zero (-2730C), where no vapour can be present and only ice will exist.

Curve OC: Melting point curve of ice

Ice ⇌ Water
It represents the equilibrium between ice and water. At any point on the curve, the
above equilibrium will exist. The curve OC is slightly inclined towards pressure axis.
This shows that melting point of ice decreases with increase of pressure.

Along the curves OA, OB, and OC, since C = 1, and P = 2, applying the phase rule;

F=C–P+2=1–2+2=1 F = 1 (univarient)

The curves are univariant because, for a given value of pressure, the temperature is
automatically fixed on a curve, and vice versa.

Triple point “O”

Ice ⇌ Water ⇌ Water vapour

The curves OA, OB, and OC, meet at the triple point “O”where all the three phases, liquid
water, ice, and vapour, are in equilibrium. This occurs at 0.0098ºC and 4.58mm Hg
pressure. Since C =1 and P = 3,

F=C–P+2=1–3+2=0

F = 0 (invariant)

The triple point is invariant because, variation of any one of the variables, temperature
or pressure, causes the disappearance of one of the three phases.

Areas AOC, BOC & AOB:

Areas AOC, BOC & AOB, represent the phases, water, vapour, and ice, respectively. In all
the three areas, since C = 1, and P = 1,

F=1–1+2=2 F = 2 (Bivariant)

In order to define the system at any point in the areas, it is essential to specify both
pressure and temperature.

Metastable equilibrium, OB’:

The curve, OB’, is called vapour pressure curve of the super cooled water or metastable
equilibrium where the following equilibrium will exist.

Super cooled water ⇌ vapour

Sometimes water can be cooled below 0o C without the formation of ice is called super
cooled water. Super cooled water is unstable; it can be converted in to solid by slight
disturbance. It has higher vapour pressure than ice at a particular temperature.
 3. Reduced phase rule- Two component system: lead-silver system- Pattinson
process
 State reduced phase rule.(2) (January 2022)
 Write the mathematical expression of reduced phase rule. (2) (January
2019)
 What is Pattinson process? (2) (January 2019)
 Draw and explain the lead silver phase diagram. (10) (January 2019)
 Draw and explain the phase diagram of Pb-Ag eutectic system. (16)
(January 2018)
 Draw and label the phase diagram of lead-silver system. Explain. (8)
(April/May 2019) (8) (January 2022)

Reduced phase rule or Condensed system

The maximum number of degree of freedom in a two component system will be

three, when the system exists as a single phase.

F=C-P+2;F=2-1+2;F=3

To represent graphically three co-ordinates, namely P,T and C are required. This
requires three dimensional diagram, which cannot be conveniently represented on
paper. Therefore, any two of the three variables must be chosen for graphical
representation.

A solid-liquid equilibrium of an alloy has practically no gaseous phase. Thus the system
in which only the solid and liquid phases are considered and the gas phase is
ignored is called a condensed system. Since the pressure is kept constant, the phase
rule becomes

F’=C-P+1

This equation is called reduced phase rule or condensed phase rule.

Two component system: lead-silver system

The system is considered as reduced system.

F’ = C – P + 1,.
a. Curves:

Curve AO: Freezing point curve of Ag.

It shows the effect on freezing point of Ag on addition of lead in small quantities.

A is the melting point of pure Ag (9610C).The curve OA indicates that the melting point
of Ag falls gradually as the addition of Pb increases, till the lowest point O (3030C) is
reached. At point O, the solution gets saturated with respect to lead. Along the curve AO,
solid Ag and liquid melt are in equilibrium

Ag(s) ⇌ Ag-Pb melt (l),

(P = 2, C = 2), and hence, according to reduced phase rule equation: F’ = 2 – 2 + 1 = 1

(univariant). Thus, either composition or temperature is needed to define the system
along the curve AO.

Curve BO: freezing point curve of Pb.

BO represents the effect on freezing point of Pb on gradual addition of small amounts of

Ag to it. Point B is the melting point of pure lead (327 0C). Along BO, the melting point
gradually falls on the addition of Ag, till lowest point O is reached. At O, the solution gets
saturated with respect to Ag. Along the curve BO, Solid Pb and liquid melt are in
equilibrium.

Pb(s) ⇌ Ag-Pb melt (l)

As seen above, along BO, F’ = 1(univariant).

b. Eutectic Point O:

The curve AO and BO meet at O, which is called the eutectic point. Here three
phases, solid Ag, solid Pb, and liquid melt, are in equilibrium. Applying the reduced
phase rule, (P – 3; C = 2), F‟ = C – P + 1 = 2 – 3 + 1 = 0 (non-variant)

Both variables temperature (3030C) and composition (97.4% Pb, 2.6% Ag: eutectic
composition) are fixed. If the temperature is raised above the eutectic temperature, the
solid phases Ag and Pb disappear. Lowest melting point for the Pb-Ag system is the
eutectic temperature.

Areas

Area above AOB:

This region represents the single phase system, the solution of molten Ag and Pb

(P = 1; C = 2). Applying the reduced phase rule; F‟ = C – P + 1 = 2 – 1 + 1 = 2 (Bivariant)

To define a system in this area, both temperature and composition are to be specified.

Area below AO (Solid Ag+ Liquid melt), Area below BO (Solid Pb+ Liquid melt) and area
below point O (Eutectic compound + Solid Ag or Solid Pb) have two phases and two
components. Here F’=2-2+1=1, hence the system is univariant.

Pattinson process

Desilverisation of Argentiferrous lead is called Pattinson’s process

The argentiferrous lead contains small amount of silver (0.1% of Ag). It is melted at a
temperature above the melting point of pure lead (3270C). Let the point p represent
molten lead on the diagram. It is then allowed to cool, the temperature of the melt falls
along the dashed line pq. When the point q on the curve BO is reached, solid pure lead
begins to separate. On further cooling, more of pure lead separates along the curve qO
until the eutectic point O is reached. Lead is continuously removed by means of ladles
and the percentage of silver in the melt goes on increasing up to 2.6%. This process is
called de-silverisation of lead or Pattinson’s process.

4. Construction of a simple eutectic phase diagram - Thermal analysis

 With two cooling curves for pure substance and mixture, discuss briefly
about thermal analysis. (16) (January 2018)

It involves the study of cooling curve of various compositions of two solids during
solidification. In this method a mixture of two components A & B of known composition
is heated to get a homogeneous liquid melt. The melt is then cooled at a slow rate with
constant stirring. The cooling temperature is recorded at regular intervals till it
completely solidifies. The same method is repeated for different compositions of alloy
mixture ranging from 0 to 100%. The plots are known as cooling curves for a particular
composition.

Example 1: Consider a pure solid substance in the fused state. Allow it to cool slowly.
The temperature is noted at different time intervals. Then a graph is plotted between
temperature and time.

Cooling curve of a pure metal

a : Represents the pure metal is in molten state.

ab : Along ‘ab’, the temperature of the melt decreases gradually wit h time.
b : The point ‘b’ indicates the temperature at which the molten metal starts freezing at
its surface.

bc: Along ‘bc’ the liquid melt and solid metal are in equilibrium. Further the
temperature remains constant until the liquid melt is completely solidified because the
liquid melt and solid metal have same composition.

c : Indicates the end of freezing.

cd: Along ‘cd’, the temperature of the solid metal again decreases wit h time.

Example 2: Consider a mixture of two solids A & B

Cooling curve of a mixture of two solids A & B

a : Represents a mixture of solid A and solid B in molten state.

ab : Along ‘ab’, the temperature of the mixture A & B decreases gradually with t ime.

b : The point ‘b’ indicates the temperature at which the freezing of base metal ( either
A or B depends upon their freezing point) starts from the liquid mixture.

bc : Along ‘bc’ the liquid melt and solid metal A (or solid metal B) are in equilibrium.
Further, the line ‘bc’ indicates the composition of molten mixture progressively changes
due to continuous separation of solid A (or B) with time.

c : The point at which the liquid mixture (containing both A&B) starts freezing into
solid A and solid B (eutectic mixture)

cd : Along „cd‟, the liquid mixture and solid A & B are in equilibrium.

d : Indicates the end of freezing of eutectic mixture.

de : Along ‘de’, the temperature of the solid again decreases with time.
Construction of Simple Eutectic diagram

It is possible to construct a complete phase diagram for the two component system on
the basis of large number of cooling curves of various compositions. Each curve
corresponds to a definite composition of A and B. The first break or discontinuity in the
graph (a, b, c, d, e, f, g, h, i) denotes phase transformation (freezing point of either A or
B). The eutectic phase diagram is obtained by plotting various compositions of two
substances (in X-axis) against the first break point (in Y-axis), which is nothing but
characteristic temperature.

COOLING CURVES OF VARIOUS COMPOSITIONS OF TWO SOLIDS

(1) Pure A (6) 30% A + 70 % B

(2) 80% A + 20 % B (7) 20% A + 80 % B

(3) 70% A + 30 % B (8) 10% A + 90 % B

(4) 60% A + 40 % B (9) Pure B

(5) 40% A + 60 % B

Uses of Cooling Curves

 Melting point and Eutectic point can be noted from cooling curve.
 The behavior of the compound can be clearly understood from the cooling
curve.
 Percentage purity of the compounds can be noted from the cooling curve.
 The composition corresponding to its freezing point yields the composition of
the alloy.
 The procedure of thermal analysis can be used to derive the phase diagram of
any two component system.
 Composites
Composites: Introduction: Definition & Need for composites; Constitution: Matrix
materials (Polymer matrix, metal matrix and ceramic matrix) and Reinforcement (fiber,
particulates, flakes and whiskers). Properties and applications of: Metal matrix
composites (MMC), Ceramic matrix composites and Polymer matrix composites. Hybrid
composites - definition and examples.

1. Definition & Need for composites

Definition

A composite material is a material system consisting of two or more distinct

phases whose combination results in properties that differ from those of its
constituents

Need for composites:

Composites are needed for the following reasons,

 Due to their lower weight, consumption of fuel and emission will be reduced,

 Composites never rust and have less fracture toughness than metals,

 To reduce maintenance cost and ensure long-term stability composites

 Acording to the needs, using different fibres and matrix, properties of composites
can be modified.

 In telecommunication industries, need of power transmission along with data

transmission is' increasing, so composites are highly' essential.

Advantages of composites:

 Posses higher specific strength and lower specific gravity.

 Have lower electrical conductivity and thermal expansion.
 Better creep, fatigue strength, corrosion and oxidation resistance.
 Maintain very good strength, even up to high temperatures.

2. Constitution: Matrix materials and Reinforcement

Composites consist of two important constituents,

(i) Matrix materials (or) Matrix phase

(ii) Reinforcements (or) Dispersed phase

(i) Matrix Phase

Matrix phase is the continuous body constituent, which encloses the composite.
Matrix phase may be metals, ceramics (or) polymers (liquid resins), composites using
these matrixes are known as

 Metal Matrix Composites (MMC)

 Ceramic Matrix Composites (CMC)
 Polymer Matrix Composites (PMC)

(ii) Dispersed Phase (or) Reinforcement

Dispersed phase is the structural constituent, which determines the internal

structure of composite. Examples: Fibres, Particulates, Flakes, Whiskers.

Reinforcement

 It is a process of improving the characteristics of the plastic matrix by adding

reinforcing agents.
 The reinforcing agents may be organic (or) inorganic in nature. They may be in
the, form of powder, flakes, fibres.
 These, materials are characterised by high· strength to weight ratio, excellent
resistance to erosion, corrosion, etc., and ease of fabrication.
 For effective structural performance, there should be a strong adhesive bond
between the matrix phase (or) matrix resin and the dispersed phase (or)
reinforcing agents.

(a) Fibres

Fibres are long and thin' filament of any macromolecular substance such as polymer,
metal (or) cerarmic having high length to diameter ratio at least 100: 1.

Characteristics of fibres

 Fibres possesses high tensile strength,

 It possesses high stiffness.

 It lowers overall density of composites.

Classification of Fibres

The fibres used in reinforcements are classified as

(i) Natural fibres: These are derived from naturally available sources. Eg. Cotton, wool,
silk, sisal, jute and coir.
(ii) Semi-synthetic fibres: These are produced by modifying the naturally occurring
materials. Examples: Rayon, cellulosic.

(iii) Synthetic fibres: These are produced exclusively by the laboratory processes.

Examples: Polyester fibre, polypropylene and carbon fibre (poly acrylonitrile) glass
fibres, aramid fibres.

(iv) Aramid fibres: These are aromatic polyamides. Example: Kevlar.

(b) Whiskers

Whiskers are thin strong fibre like material made by growing a crystal,

ExampIes : Graphite, silicon carbide, silicon nitride.

 Perfect whiskers possess much higher strength than in bulk, but

irregularities decreases their strength.
 They possess high elastic modulus and high degree of crystallinity.
 They possess exceptionally high strength.
 As it is costly and difficult to incorporate in matrix they find limited use in
composite.

(c) Flakes:

Flakes are very thin solid like materials,

Example: Mica flakes

 They impart equal strength in all directions in a plane compared to fibres

which reinforce unidirectionally only.

 Flakes can be packed more efficiently than fibres (or) spherical particles.

 Flakes especially mica can be used III electrical and thermal insulating
appliances.

(d) Particulates

 Particulates are small pieces of hard solid materials.

 They may be metallic (or) non-metallic. Generally distribution of particles
in a given matrix is random, so the resulting composites are usually
isotropic.
 Due to the inherent hardness, the particle in a composite causes
constraint on the plastic deformation on the matrix.
 Effect of particulate in particulate composite

 Surface hardness gets increased.

 Wear' and abrasion resistance are increased.
 Performance at elevated temperature is improved.

3. Properties and applications of: Metal matrix composites (MMC), Ceramic

matrix composites and Polymer matrix composites

 Discuss the important types of fiber reinforced composites. (8) (January

2022)
 Discuss the properties and applications of metal matrix composites. (8)
(January 2022)

(a) Ceramic Matrix composites

Properties

 CMC are used at temperatures above 15000c because of their good

corrosion resistance, high stability at elevated temperatures and high
compressive stregth.
 Ceramics provide necessary strength at high temperature with good
oxidation resistance.
 The matrixes used are glass, ceramics, carbides nitrides, oxides and
borides, the reinforcements are A12O3, B, C, SiC and SiO2

Uses

They are used in re-entry thermal shields in space vehicles and tiles, pump seal,
round- rings, brake linings etc.

(b) Polymer matrix composites

The fibre reinforced polymer composites constitute more than 90% (by weight)
of the total composites used in various industries. The advantages of using polymer" in
structural composites is the ease of fabrication of complex structural shapes. It can be
easily manufactured.

Preparation

Fibre-reinforced plastic are produced by suitably bonding a fibre material with a resin
matrix and curing them under pressure and heat The, main reinforcing agents used in
FRP composites are glass, graphite, alumina, carbon, boron etc. The reinforcement
material can be in different forms such as short fibres, continuous filaments (or) woven
fabrics.

The resin matrix commonly used in FRP is polyesters, epoxy, phenolic, silicone, and
polyamide polymer resins. .

Characteristics (or) Properties of' FRP

 It possess superior properties like higher yield strength, fracture strength and
fatigue life. ·
 Since fibre prevents slip and crack propagation, the mechanical properties of
FRP gets increased. .
 It possesses high corrosion resistance and heat resistance property.

The properties of FRP mainly depends on nature of the resin matrix,

Polyester resin – To provide very good strength and mechanical properties.

Epoxy resin – To impart good mechanical properties.

Silicone resins – To impart excellent thermal and electrical properties.

Phenolic resins – To withstand high temperatures

Thermoplastics (polyamide, PET,etc) – Because of its repeatability and repairability.

Types of FRP composites,

Glass FRP, Boron FRP, Carbon FRP, Aramid FRP, Alumina FRP etc.

Advantages of polymer composites (FRP)

 Polymer composite has very high strength to weight ratio than the metal,

 The weight of FRP is 75% lower than the weight of steel, so it improves
performance, reduces- energy need, simplifies handling.

 Using polymer composite devices both capacitance and leakage current can
be reduced.

 FRP offers better corrosion resistance to a wide range of chemicals resulting

in longer service life less maintenance and repair down time.

 FRP possesses excellent durability and fire resisting properties.

 It is ideal for outdoor installation, because it is impervious to the effect of

sunlight heat, cold and other weather conditions.
  Specifying the orientation of reinforcing fibres, an increase the strength and
resistance to deformation of the polymer.

 GRP (glass reinforced polymer) are strongest and most resistive to deforming
forces, when the polymer fibres are parallel to the force being exerted and
are weakest when the, fibres are perpendicular.

(c) Metal Matrix Composites

Properties

 Metal matrix composites exhibit extremely good thermal stability, high

strength, good stiffness and low specific weight.
 MMCs also have other advantages like fracture toughness, ductility and
enhanced elevated temperature performance
 They can withstand at elevated temperatures in corrosive environment than
polymer composites.

Uses

 Polymer based composites cannot be utilized for engine parts due to their
limitations in their applications at high temperatures where as MMCs are
suitable alternatives with Al, Ti, Ni alloys as one of the matrix material and
A12O3, B, C, SiC as one of the reinforcements.
 They are used in engine blades, combustion chambers,etc.
 Al and Mg MMCs are used in automotive industry.

4. Hybrid composites - Definition and examples

 Give two examples of hybrid composites. (2)(January 2022)

Hybrid composites

Hybrid composites are new class of materials composed of a suitable polymer

matrix reinforced' 'with two different fibres (or) fillers.

Functionally hybrid composites are of three types

a) Structurally hybridized composites

b) Materials hybridized in chemical bond

c) Functionally hybridized composites.

Eg.: Carbon –glass hybrid composite, glass aluminium laminates

Properties

 Hybrid composites possess very good properties compared to their single

fibre composites.
 They possess strong, tough and higher impact resistance.
 When hybrid composites are stressed in tension failure does not occur
suddenly,
 They possess balanced strength and stiffness,
 They also have balanced thermal distortion stability, reduced weight, and
improved fatigue resistance.
 They exhibit superior mechanical and tribological properties than other
composites.

Uses

 It is used in light-weight transport (land, water (or) oil) structural

Components.
 It is also used in light weight orthopaedic component and sporting goods.
 It is used to make furniture like chair, table and bath tubs
 It is used in railway coach interiors.
 It is also used in making daily used applications like plates and spoons.
 Automobile industry utilizes hybrid composites in many of the interior
and exterior applications.