Table of Contents

Unit No. Title of Unit Page No.

I Overview of Metallurgy 01-26

II Micro & Macroscopic Study of Metals 27-44

III Iron-Carbon Alloy System & Cast Iron 45-74

IV Heat- Treatment Of Steels 75-96

V Engineering Alloy Steels & Designation 97-112

VI Non Ferrous Metals 113-130

 Unit I Overview of Metallurgy

Unit – I
Overview of Metallurgy

Syllabus:
Methods of metal extraction (Principle only of pyro , hydro & electro metallurgy), cast v/s wrought products,
Related terms and their definitions : System, Phase, Variable, Component, Alloy, Solid solution, Hume
Ruther's rule of solid solubility, Allotropy and polymorphism, Concept of solidification of pure metals &
alloys, Nucleation : homogeneous and heterogeneous, Dendritic growth, super cooling, equiaxed and
columnar grains, grain & grain boundary effect.
Cooling curves, Plotting of Equilibrium diagrams, Lever rule, Coring, Eutectic system, Partial eutectic and
isomorphous system.

Section No. Topic Name Page No.

1.1 Introduction 2
1.2 Methods of Metal Extraction 2
1.3 Cast V/S Wrought Products 3
1.4 Equilibrium Diagram 5
1.5 Related Terms and Their Definition’s 5
1.6 Gibb’s Phase Rule 9
1.7 Concept of Solidification of Pure Metals and Alloys 10
1.8 Nucleation 13
1.9 Supercooling 15
1.10 Equiaxed and Columnar Grains 16
1.11 Grain and Grain Boundary Effect 16
1.12 Cooling Curves 17
1.13 Plotting of Equilibrium or Phase Diagram 20
1.14 Lever Rule 21
1.15 Coring 22
1.16 Eutectic System 22
1.17 Partial Eutectic System 25
1.18 Isomorphous System 26

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 Unit I Overview of Metallurgy

1.1 Introduction
 Metallurgy is a field of material science and engineering
that studies the physical and chemical behaviour of
metallic elements, their intermetallic compounds and their
mixtures, which are called alloys.
 Metallurgy is also the knowledge of metals, the way in
which science is applied to production of metals and the
engineering of metal components for usage in products for
consumers and manufactures.
 The production of metals involves the processing of ores to
extract the metal they contain and the mixture of metals,
sometimes with other elements, to produce alloys.
 In nature all metals will not be available in pure metallic
forms rather they are present in the combined form
minerals. They can be sulphides or oxides, etc.
 In minerals, it is not that they have only metal but with
metal there are some unwanted elements.
 Metallurgy is distinguished from the craft of metalworking,
although metalworking relies on metallurgy.

1.2 Methods of Metal Extraction

 The procedure of taking out pure metal from its ore is
called as Metal Extraction or it is also called as Extractive
Metallurgy. Fig. No. 1.2 Pyrometallurgy of Iron

Fig. No. 1.1 Classification of Extractive Metallurgy Fig. No. 1.3 Different Steps of Pyrometallurgy

1.2.1 Pyrometallurgy i. Calcination:

 Pyrometallurgy is a branch of extractive metallurgy.  In this step, elements like carbon (C) and water are
 It consists of the thermal treatment of minerals and eliminated. This is endothermic reaction.
metallurgical ores and concentrates to bring about physical ii. Roasting:
and chemical transformations in the materials to enable  It is a process in which the ore is brought into
recovery of valuable metals. convertible form. Example: Sulphides ore converted
 Reduction of metal from its oxide is more than sulphides. into oxides.
 Sulphides are roasted (heated) to oxidising temperature to  In this process, oxygen is supplied for chemical
convert inoxide form. conversion.
 The ores are basically fine. If such thing is there, the ore is 1
brought together by agglomeration (collecting in a mass). 𝑍𝑛𝑆 + 𝑂2 → 𝑍𝑛𝑂 + 𝑆𝑂2
2
 At elevated temperature, the ore compounds ore unstable,  It depends on physical condition of ore, time and
due to which we can extract the metal. oxygen (O2).
 Generally, the temperature of reaction in Pyrometallurgy is iii. Smelting:
not less than 500°C and not more than 2000°C.  In this process, the oxides ore converted to metal by
 Pyrometallurgy has following three different steps: reaction with Carbon (C) and Sulphur (S) in blast or
electrical furnace.
 Slag is removed with the help of flux.

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 The charge is solid and the output is liquid metal. In Advantages:

this case, external source is used to supply heat.  Suitable for low grade ore.
 Valuable by products can be recovered.
Advantages  Less environmental pollution.
 As it is a high temperature process, the process of reaction  Less costly compared to Pyrometallurgy.
is fast. Therefore more metal is produced.  The produced metal can be in different forms like nodules,
 The cost of reducing agent and raw materials is less. powder etc.
 Liquid metal and slag separates out and helps in metal  Even in leaching, low temperatures are involved.
extraction process.  Waste liquor can be recycled.
 This method can be used for extraction of reactive metals
like Zr. Disadvantages:
 Processing requires large volume.
Applications  Handling of chemicals needs proper care.
 Metals like Fe, Zn, Pb, Cu, Al, Mg, As, etc. are extracted  Large space is required.
from this method.  Problem of corrosion and erosion in the handling
equipment’s.
1.2.2 Hydrometallurgy:  Disposal of effluments is problematic.

1.2.3 Electrometallurgy:
 It is a branch of metallurgy that deals with the application
of electric current either for electrolytic deposition or as a
source of heat. In other words it is a processes that take
place in some form of electrolytic cell.
 Electrometallurgy is the field concerned with the processes
of metal electrode position.
 There are following four categories of these processes:

Fig. No. 1.4 Process of Hydrometallurgy

Fig. No. 1.5 Categories of Electrometallurgy
 Hydrometallurgy is concerned with processes involving
aqueous solutions to extract metals from ores. i. Electrowinning:
 In earlier days, hydrometallurgy was used for low grade 
It represents the extraction of metal from ores.
ore. ii. Electrorefining:
 Removal of impurities by different physical methods,  It represents the purification of metals. In this category
grinding are the basic processes in preparation of ore in metal powder production is also included.
hydrometallurgy. iii. Electroplating:
 The first step in the hydro metallurgical process is leaching,  It represents the deposition of a layer of one metal on
which involves dissolution of the valuable metals into the another metal.
aqueous solution or a suitable solvent. iv. Electroforming:
 After the solution is separated from the ore solids, the  It includes the manufacturing of thin metal parts
extract is often subjected to various processes of through electroplating.
purification and concentration before the valuable metal is  Example: To produce aluminium from aluminium oxide.
recovered either in its metallic state or as a chemical
compound. 1.3 Cast V/S Wrought Product
 The rate of process will vary with temperature and pressure
1.3.1 Cast Iron
of liquor.
 Cast irons are basically the alloys of iron and carbon in
 This may include precipitation, distillation, adsorption and
which the carbon varies between 2.0 to 6.67 % i.e. more
solvent extraction.
than the solubility limit of carbon in austenite and less than
 Example: A major target of hydrometallurgy is Copper. the carbon content of cementite.

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 Commercial cast irons are complex in composition and castings), etc. Hence, it is widely used in the following
contain carbon in the range of 2.3 to 3.75 % with other applications:
elements such as silicon, phosphorus, sulphur and i. Building construction:
manganese in substantial amount. Underground service lines and electrical conduit.
 Because of their poor ductility and malleability, they ii. Rail road and marine:
cannot be forged, rolled, drawn or pressed into the desired Diesel exhaust and air brake piping, tanker heating coils,
shape; but are formed by melting and casting with or etc.
without machining to the required final shape and size, and iii. Industrial:
hence the same “Cast Irons”. Condenser tubes, unfired heat exchangers, acid and alkali
process lines, etc.
Applications iv. Public works:
 Automobile engine blocks & heads, manifolds for internal Bridge railings, drainage lines, sludge tanks and lines.
combustion engines, gas burners, machine tool bases,
cylinder liners, intake manifolds, soil pipes, counter 1.3.3 Cast and Wrought Products
weights, enclosures and housings.  When we say wrought material it basically means work
 Steering knuckles, gears, automotive and truck suspension which is having many constituents like slag in it and can be
components, brake components, valves, pumps, linkages, further processed for other manufacturing processes.
hydraulic components, wind turbine housing.  When we say cast structure or casting, it is one of the
 Parts for chemical processing plants, petroleum refining, manufacturing process in which required work
food handling, marine service, control of corrosive fluids, piece/material is converted into useful form, shape and
pressure valves. size.
 Casting is always a solid form of material converted into
1.3.2 Wrought Iron the useful form from liquid material. Casting has dendritic
 Wrought iron is a mechanical mixture of a very pure iron structure as cast conditioned products which has specific
and a silicate slag. mechanical properties that can be changed by giving proper
 It is a ferrous material, aggregated from a solidifying mass heat treatment.
of pasty particles of highly refined metallic iron with which  Wrought products can be further processed for all
a minutely and uniformly distributed quantity of slag is manufacturing processes like rolling extrusion, etc.
incorporated without subsequent fusion.  The grain orientation in preferred direction shows flow line
 Generally, wrought iron consists 0.02 % carbon, 0.05 % type pattern.
Phosphorus, 0.02 % Silicon, 0.008 % Sulphur, 0.05 to 1.50
% slag and remaining amount of iron. 1.3.4 Comparison between Cast Products and Wrought
 Wrought iron is never cast, because it’s shaping is Products
accomplished by hammering, pressing, forging, etc.
 Wrought iron is popular for its high ductility and for the Table No. 1.1 Comparison of Cast and Wrought Product
ease with which it can be forged and welded. Sr. Cast Products Wrought Products
 The ultimate strength of wrought iron can be increased No.
considerably by cold working. 1 Cast products are Wrought products are
 It has high resistance towards shock, fatigue and corrosion. obtained from liquid obtained when external
 The mechanical properties of wrought iron are similar to metal by conversion in load is subjected on metal.
pure iron. solid.
 Also, wrought iron has a property of rapid recovering from 2 Casting is final Further manufacturing
overstrain due to sudden recovery and shock without manufacturing process. processes are applied.
permanent failure. 3 Casting gives same It shows directional
 The structure of wrought iron shows the physical properties in all properties.
association of base metal and the slag. The slag or iron directions.
silicate may look like ribbon or platelets or stringer in the 4 It may lead to porosity Porosity is almost zero as
microstructure. problem. it gets eliminated in
mechanical working.
Applications 5 Can be manufactured in Large and complex shapes
Wrought iron is available in various forms such as plates, any shape and size. are not easy to
sheets, bars, structures, rivets, chains, welding fittings, nipples manufacture.
and a wide range of tubular products (pipes, tubes, and 6 Brittle metals can also Brittle material will break
be casted. in processes like rolling.

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1.4 Equilibrium Diagram  It may be composed of solids, liquids, gases or their

 One of the important objectives of engineering metallurgy combinations and may have metals and non-metals
is to determine the properties of material. separately or in any combination.
 The properties of material is a function of the  A system is capable of changing its composition,
microstructure which is further dependent on the overall temperature, pressure, density etc. if such a requirement
composition and variables such as temperature, pressure arises.
and composition.  Systems are classified according to the number of
 Hence, to determine the phases present in the material components that constitute the system. A component is a
system, an equilibrium or phase diagram is plotted. unit of the composition variable of the system.
 Equilibrium diagram or phase diagram is a graphical  If there are two components, it is a binary system, three, a
representation of various phases present in the material ternary, four a quaternary system etc.
system at various temperature and composition points.  Even though compounds are formed in the system, the
 All phase diagrams have temperature as the ordinate (Y- number of components remains the same. However the
axis) and percentage composition by weight as the abscissa components may be selected so that one is a compound.
(X-axis).  Example: The iron-iron carbide system.

1.4.1 Uses of Equilibrium Diagram or Phase Diagram 1.5.2 Phase

 It shows the various phases present at different  A phase is defined as homogeneous, physically distinct
composition and temperature. portions of the system.
 It indicates the solid solubility of one element in the other.  Each portion is homogeneous throughout, and regardless
 It shows the temperature range over which solidification or of where a sample is taken in that portion, the composition
liquification of material system occurs. will be the same. These homogeneous, physically distinct
 In indicates the temperature at which different phases start portions of the system are called phase. Or
to melt.  It is a physically and chemically homogeneous
composition of a substance (system), separated from other
portions by a surface and an interface. But, each portion
have different composition and properties.
 Example: A liquid may exist in equilibrium with a solid
solution or two solid solutions of different compositions
may exist together.
 Many phases exist in some alloys, gray cast iron, for
example, is made up of the following phases in order to
decreasing amounts.
1. A solid solution phase of iron containing some carbon,
silicon and phosphorus.
2. A soft metalloid, graphite (carbon).
3. A hard, brittle compound, Fe3C (cementite).
4. A compound of the impurity sulphur, usually in the form
of MnS.
5. A compound of the impurity, phosphorus, present as Fe 3P
Fig. No. 1.6 Equilibrium or Phase Diagram and found with iron as a mixture called steadite.
6. A very small amount of non-metallic compounds.
1.5 Related Terms and Their Definition’s  The phases in an alloy are not necessarily uniformly
The following are the related terms in equilibrium diagram and distributed throughout the structure. There are certain ways
their definitions as follows: in which these phases may be associated to form the
structure.
1.5.1 System  The association of phases in a recognizably distinct fashion
 A system is a set of interacting or inter dependant may be referred to as a structural constituent of the alloy.
components parts forming a complex / intricate whole is  A eutectic, for example, is an intimate mechanical mixture
called system. Or the substances that are isolated and of two or more phases having a definite melting point and
unaffected by their surrounding are known as system. a definite composition.
 The term system has a wider application, in that it refers to  An alloy may be composed of the eutectic as one structural
any portion of objective space within specified boundaries constituent and one phase not intimately associated with
subject to specified variables. the other phase as a second structural constituent.

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1.5.3 Variable  The element present in the alloy in the largest proportion is
 A variable is defined as related to materials are referred as base metal or parent metal or solvent and the
temperature, pressure and composition. Or a particular other elements are referred as alloying elements or solute.
phase exists under various conditions of temperature,  Solid solution is a type of alloy in which the atoms of
pressure and concentration. These parameters are known as alloying elements are distributed in the base metal and both
the variables of the phase. have similar crystal structure.
 The important state variable over which the materials  The composition of alloying elements may vary but the
engineer has control in establishing microstructure are structure should be similar to the base metal.
temperature, pressure and composition.  Solid solutions can be classified as follows:
 Within the system, there are variable that specify the
compositions of the phases present.

1.5.4 Component
 The component of the system may be elements, ions or
compounds. They refer to the independent chemical
species that comprise the system is called as component.
Or
 These are the substances, either chemical elements or
chemical compounds whose presence is necessary and
sufficient to make a system.
 A pure metal is a one-component system whereas an alloy
of two metals is a two component (binary) system etc.
 In the ice water-steam system, the component is H2O. In
the Cu-Ni system, the elements Cu and Ni are the
components, whereas in the Al2O3-Cr2O3 system, the two Fig. No. 1.7 Classification of Solid Solution
oxides can be taken to be compounds.
 In the iron-iron carbide system, iron and graphite can be  Substitutional Solid Solution
components, but it may be often convenient to choose iron  If the solute atoms take place of some of the solvent atoms
and carbide (Fe3C) as the component. at lattice sites, it is called a Substitutional solid solution. Or
 When the atoms of solute substitute for the atoms of the
1.5.5 Alloy solvent in its lattice, the solution is known as Substitutional
 Alloy is defined as combination of two or more metal to solid solution.
form alloy.
 It is a mixture of two or more elements having metallic
properties. In the mixture, metal is in the large proportion
and the others can be metals or non-metals.
 Metals in their pure form are seldom used in engineering
applications. Most of the metallic materials used in
engineering are combinations of metals known as alloys.
 An alloy is any combination of elements that results in
substance possessing metallic properties. Elements may
combine in different ways to form alloys.
 The components of alloy are usually completely soluble in
the liquid state, i.e. they dissolve in each other in a manner Fig. No. 1.8 Substitutional Solid Solution
similar to that of water and alcohol.
 The element in the largest amount is called as base metal  The solute may incorporate into the solvent crystal lattice
(parent metal) or solvent and the other elements are called substitutionally by replacing a solvent particle in the
as alloying elements or solute. lattice.
 In the solid state, however, the elements may form solid  In Substitutional solid solution, the atoms of alloying
solutions, compounds or mechanical mixtures. elements occupy the atomic sites of the base metal.
 Solute atoms sizes are roughly similar to solvent atoms.
1.5.6 Solid Solution  Due to similar size solute atoms occupy vacant site in
 The atoms of one element become a part of the space lattice solvent atoms.
of the other element, thus forming a solid solution.  They are further classified as:

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a) Regular or ordered substitutional solid solution.  Examples: Fe – C.

b) Random or disordered substitutional solid solution.
1.5.7 Hume-Rothery’s Rules for Solid Solubility
a) Regular or ordered substitutional solid solution  Solid solution is an alloy of two or more elements wherein
 In this type, the substitution of atoms of alloying elements the atomic crystal structure of the alloying element (solute)
is in a definite order in the base metal matrix. is same as that of the base metal matrix (solvent).
 The solubility limit of the solute in the solvent (of the
Copper
alloying element in the base metal matrix) is governed by
(Solute) certain factors.
 These governing factors are known as Hume – Rothery’s
rules for solid solubility.
 These governing factors are as follows:
Silver
(Solvent) 1. Atomic Size
 Alloying elements having similar atomic size as that of the
base metal matrix have better solid solubility.
Fig. No. 1.9 Regular or ordered substitutional solid  The greater the difference in size between the atoms of the
solution two metals involved, the smaller will be the range over
 Examples: Silver (Ag)-Copper (Cu) solid solution below which they are soluble.
400°C.  If atom diameter differ by more than 15% of that of the
solvent metal then solid solubility is generally extremely
b) Random or disordered substitutional solid solution small. But if diameter differ by less than 7% then, other
 In this type, the substitution of atoms of alloying elements things being equal, they will be likely to form solid solution
is in any random order in the base metal matrix. in all proportions.
 Any difference in atomic size will of course produce some
Copper strain in the resultant crystal structure.
(Solvent)
2. Electrochemical Properties/ Chemical Affinity
 The ions of all metals are electropositive but some are more
Zinc electropositive than others.
(Solute)  Generally, the greater difference in electro positivity, the
greater will be the chemical affinity of one ion for another
so that they will tend to form a compound rather than a
solid solution.
Fig. No. 1.10 Random or disordered substitutional solid  If on the other hand their electropositive are similar, then
solution other things being equal, they will very probably from a
 Examples: α – Brass. solid solution.

 Interstitial Solid Solution 3. Relative Valency

 In interstitial solid solution, the atoms of alloying elements  A metal of lower valency is more likely to dissolve one of
occupy the interstitial sites of the base metal. higher valency than vice versa always assuming that other
 This type of solution is formed when the atomic size of the conditions are favourable.
alloying element is much smaller as compared to that of the  This holds true particularly for alloys of the monovalent
base metal. metals copper, silver and gold with many metals of higher
Iron valency.
(Solvent)
4. Crystal Structure
 Crystal structure will have greater solubility. Since atoms
Carbon tend to assume relatively fixed positions.
(Solute)  This gives rise to the formation of crystals in the solid state.
The atoms oscillate about fixed locations and are in
dynamic equilibrium rather than statically fixed.
 From the above, it can be concluded that two metals are
Fig. No. 1.11 Interstitial Solid Solution most likely to form substitutional solid solutions over a

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wide range of compositions. If their atomic sizes are about

equal and if their electrochemical properties are similar. 0.024
= × 100
 These conditions are fulfilled when two metals are very 0.132
close together in the periodic classification of the elements.
Usually side by side in the same period (nickel and copper) = 18.18
or one above the other in the same group (silver and gold). The atomic size difference exceeds 15%, so Hume
 Also if singly they crystallize in the same pattern this will Rothery Rule cannot satisfy for complete solid solubility.
assist simple disordered substitution.
 Pairs of metals which fulfil these conditions and dissolve 1.5.8 Allotropy
in each other in all proportions in the solid state.  It is defined as the ability of a single substance to exist in
more than one physical form. These allotropes are
The atomic radii of aluminium and silicon are generally stable over different temperature ranges.
N  Thus iron (α – iron) is body centered cubic at ambient
0.142 nm and 0.112 nm respectively. Is they satisfy
1.1 temperatures but on heating it loses its ferromagnetism at
Hume Rothery Rule for complete solid solubility?
Solution: 780°C (Curie temperature) though retaining its BCC
Given Data structure.
Atomic radius of aluminium (rAl) = 0.142 nm  This phase is judged to be a different allotrope, β – iron.
Atomic radius of silicon (rSi) = 0.112 nm Further heating to 910°C leads to recrystallization to a face
centered cubic structure (ɣ - iron) which at 1400°C reverts
0.142 − 0.112 to a body-centered cubic form (δ – iron to distinguish it
% 𝐴𝑡𝑜𝑚𝑖𝑐 𝑠𝑖𝑧𝑒 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒 = × 100 from the BCC form existing below 910°C).
0.142
 These allotropic changes are reversible
0.03 780°C 910°C 1400°C
= × 100
0.142 𝛼 − 𝑖𝑟𝑜𝑛 ← 𝛽 − 𝑖𝑟𝑜𝑛 ← 𝛾 − 𝑖𝑟𝑜𝑛 ← 𝛿 − 𝑖𝑟𝑜𝑛
(𝐵𝐶𝐶) → (𝐵𝐶𝐶) → (𝐹𝐶𝐶) → (𝐵𝐶𝐶)
= 21.12  It was pointed out that several metals may exist in more
The atomic size difference exceeds 15%, so Hume than one type of crystal structure depending upon
Rothery Rule cannot satisfy for complete solid solubility. temperature.
 Iron, tin, manganese and cobalt are examples of metals
The atomic radii of Iron and carbon are 0.162 nm which exhibit this property, known as allotropy.
N
and 0.120 nm respectively. Is they satisfy Hume
1.2
Rothery Rule for complete solid solubility?
Solution:
Given Data
Atomic radius of iron (rFe) = 0.162 nm
Atomic radius of carbon (rC) = 0.120 nm
0.162 − 0.120
% 𝐴𝑡𝑜𝑚𝑖𝑐 𝑠𝑖𝑧𝑒 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒 = × 100
0.162
0.042
= × 100
0.162

= 25.92
The atomic size difference exceeds 15%, so Hume
Rothery Rule cannot satisfy for complete solid solubility.

The atomic radii of Copper and Zinc are 0.132

N
nm and 0.108 nm respectively. Is they satisfy
1.3
Hume Rothery Rule for complete solid solubility?
Solution: Fig. No. 1.12 Equilibrium diagram showing metal an
Given Data undergoing two allotropic changes
Atomic radius of Copper (rCu) = 0.132 nm  On an equilibrium diagram, this allotropic change is
Atomic radius of Zinc (rZn) = 0.108 nm indicated by a point or points on the vertical line which
0.132 − 0.108 represents the pure metal. This is shown in Fig. No. 1.12
% 𝐴𝑡𝑜𝑚𝑖𝑐 𝑠𝑖𝑧𝑒 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒 = × 100
0.132

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 In this diagram, the gamma solid-solution field is ‘looped’. Table No. 1.2 Allotropic Transformations in Metals
The pure metal A and alloys rich in A undergo two Sr. Metal Temperature Crystal Structure
transformations. No. range, °C
 Many of the equilibrium diagrams involving iron such as Upto 910 BCC, α – phase
Fe – Si, Fe – Mo and Fe – Cr show this looped solid 910 – 1400 FCC, ɣ - phase
1 Iron
solution field. 1400– 1539 BCC, δ – phase
 Since the type of iron that exists in this temperature range (m.p)
is gamma iron, the field is usually called the gamma loop. Cubic, α – phase
Upto 12
2 Tin Tetragonal, β
12 – 232 (m.p)
1.5.9 Polymorphism phase
 Many substances exist in more than one stable crystalline Upto 421 HCP, α – phase
form. The various forms have the same composition but 3 Cobalt 421 – 1492 FCC, β – phase
different crystal structures. Change in crystal structure is (m.p.)
observed due to either change in pressure or temperature or Upto 20 HCP, β – phase
4 Chromium
both. Such a change of structure is called polymorphism. 20 – 1740 (m.p.) BCC, α – phase
 Polymorphism is observed in pure elements as well as in Upto 880 HCP, α – phase
chemical compounds, both inorganic and organic. 5 Titanium 880 – 1710 BCC, β – phase
 The polymorphism of metals is frequently called as (m.p.)
allotropy and the transformation is reversible with change Orthorhombic, α
in temperature at a given pressure. Upto 668 – phase
 The materials of same composition and of different crystal
structures are called polymorphs, analogues’ to isomers Tetragonal, β –
which are molecules of identical composition with 6 Uranium 668-774 phase
different structures.
 These polymorphs have different densities and mechanical 774 – 1130 BCC, ɣ - phase
properties. A substance which exhibits polymorphism is (m.p.)
described as di – or trimorphic depending on the number of
polymorphic forms in which it exists. Upto 678 Cubic, α – phase
 Polymorphic transformation are classified into two types (58 atoms* per
on the basis of reversibility of transformation as below: unit cell)
678 – 1100 Cubic, β – phase
a) Enantiotropy (20 atoms per unit
7 Manganese
 Enantiotropy forms are mutually transformable reversibly cell)
at some temperature. 1100 – 1138 Tetragonal, ɣ -
 This temperature is called transition temperature or phase
transformation temperature or inversion point. 1138–1245 Tetragonal, δ -
 At this temperature, the two crystalline forms co-exist (m.p.) phase
under equilibrium condition at a given pressure. Any
deviation from this temperature results in the 1.6 Gibb’s Phase Rule
transformation of one form into the other. The Gibb’s phase rule states that under equilibrium conditions,
 Examples: Fe, Zr, Ti, etc. the following relation must be satisfied.
𝑃 +𝐹 =𝐶 +2 ……. (1.1)
b) Monotropy Where,
 Monotropic forms are irreversible in the solid state and P = Number of phases existing in a system under consideration.
cannot be transformed one into the other. Monotropic F = Degree of freedom i.e. the number of variables such as
transition occurs at a temperature above the melting point temperature, pressure or concentration (i.e. composition) that
of the material. can be changed independently without changing the number of
 These forms are obtained either from the liquid state or the phases existing in the system.
vapour state of the material by rapid state by change of C = Number of components (i.e. elements) in the system, and 2
temperature and hence are irreversible. represents any two variables out of the above three i.e.
temperature, pressure and concentration.
 Examples: Phosphorus, Alumina etc.
Most of the studies are done at constant pressure i.e. one
atmospheric pressure and hence pressure is no more a variable.
For such cases, Gibb’s phase rule becomes:

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𝑃 +𝐹 =𝐶 +1 ……. (1.2)  Some level of undercooling is done to promote the growth

In the above rule, 1 represents any one variable out of the of nuclei. Thus, with undercooling i.e. lowering of
remaining two i.e. temperature and concentration. temperature, the vibration of atoms decreases and the
chances of survival of nuclei increases.
1.7 Concept of Solidification of Pure Metals and
Alloys
1.7.1 Solidification of Pure Metal
 Solidification is the most important processing technique
in the manufacturing of materials.
 Most metals are melted and then cast into semi-finished or
finished shape.
 Solidification involves two steps. In the first step, nuclei of
a solid phase (crystallite) form from the liquid. In the
second step these solid crystallites begins to grow as an
atoms until complete liquid solidifies.

Fig. No. 1.14 Variation of rate of nucleation (N) and rate of

growth (G) with temperature

 Growth of nuclei occur by diffusion process which is a

function of temperature. Therefore, the rate of nucleation
(R.N.) and grain growth (G.G.) are functions of
temperature.
 It means, some degree of undercooling is necessary to start
solidification i.e. nucleation and its growth.

1.7.2 Solidifications of Metal

 Molten metal possesses high energy and it will lost when
A-B: Undercooling metal cools to form crystals.
B-C: Evolution of latent heat after undercooling  As the heat loss is more rapid near mould walls than its
Fig. No. 1.13 Time-Temperature curve for the centre, the formation of nuclei (crystallites) starts here.
solidification of a pure metal  The molten metal finds difficulty in starting nucleation
process if there is no nuclei in the form of impurities are
 Hence solidification is the process of forming grains present to start the crystallisation.
(nucleation) and its growth in the melt. The metal exists in
liquid form above the melting point.
 When the metal is cooled below its melting point, nuclei
begin to form in different parts of the melt at the same time.
 The rate of formation of nuclei depends upon the degree of
undercooling or super cooling and on the presence of
impurities which mainly facilitate nucleation. See the fig.
1.13.
 At any temperature below the melting point, a nucleus has
to be of a certain minimum size so that it will grow. This
size is called as critical size of nucleus.
 The critical size is maximum near the melting point, but
there are less chances of forming such a large nucleus.
 If the size of nuclei is smaller than it gets dissolved by the
vigorous bombardment of neighbouring atoms and cannot
grow. These are known as embryos. Fig. No. 1.15 Crystal-melt interface

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 In such cases, undercooling is done to accelerate nucleation  This type of structures are commonly observed in cast
and thus nuclei or crystals are formed. components.
 Nuclei formed tend to grow as an atoms with the release of
energy at crystal-melt interface, refer fig. no. 1.15
 The crystal growth occurs in the dendritic manner.

[Link] Shape of Crystals

 The growth of the crystal varies in different
crystallographic directions.
 In case of cast metals, the resulting preferred direction of
growth is responsible for crystal orientation.
 Slow cooling rate gives growth of crystals uniformly in all
the directions of growth. Also, it gives equiaxed crystals
(the crystals with equal dimensions in all the directions).
 Similarly, rapid cooling rate gives crystals like tree which
are called as dendrites.
 The exact shape of the crystals depend on the conditions
that exist during solidification. Fig. No. 1.16 The mechanism of growth of a dendritic
 For example, if a metal is cast in a large metallic mould, crystal
then it indicates fine grained structure at the surface,
equiaxed structure in the centre and columnar grains
normal to the cooling surface in between the two.

[Link] Dendritic Growth

 A dendrite is a crystal with a tree-like branching structure.
In the current context, we are interested in metallic
dendrites formed when a metal or an alloy of multiple
metals, in liquid form freezes is called dendritic growth.
 When a metal has a cubic lattice, the nucleus has a number
of equivalent crystallographic directions along which
crystal grows.
 A large amount of latent heat is generated in the direction
of crystal growth that increases the temperature of the
adjacent liquid.
 This temperature exceeds the freezing temperature of a
metal hence further growth of the crystal in this direction
will be stopped.
 The liquid region will have a lower temperature in a
perpendicular direction, because there is no crystallisation
and no heat generation.
 Due to this, the crystal will grow in new direction i.e. from Fig. No. 1.17 Dendritic structure of cobalt-samarium-
point 1 to point 3, until heat is dissipated from the initial copper
region of crystal growth. Refer fig. no. 1.16
 If the temperature of this region drops to sufficient value 1.7.3 Solidification of Pure Metals and Alloy
i.e. below the freezing point, the crystal will assume its  After pouring into the mould, the molten metal cools and
original direction of growth up to point 2. At point 2, again solidifies, solidification involves the transformation of the
the temperature will rise and further growth of the crystal molten metal back into the solid state.
will stop.  The solidification process is different as per the metal to be
 After that, again growth of crystal occurs in a direction cast (pure element or alloy).
perpendicular to original direction of growth i.e. from point
2 to point 4. Pure Metal
 This sequence of growth of crystals leads finally to the  A pure metal solidifies at a constant temperature equal to
structure characteristics of dendrites. its freezing point i.e. the same as its melting point. For pure

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metals, the melting points are known from the standard  The solidification process occurs over time as shown in fig.
tables. no. 1.19. It is plotted against temperature and time and it is
 The grain structure of pure metal cast structure solidified called as cooling curve.
in a square mould as shown in fig. no. 1.18  The actual freezing time is called as local solidification
time in casting. During this time the latent heat of fusion of
metal is released into the surrounding mould.
 The total solidification time is the time between the
pouring and complete solidification.
 When the casting is completely solidified, cooling
continues at a rate indicated by the downward slope of the
cooling curve.
 Due to chilling action of the mould wall, a thin skin of solid
metal is initially formed at the interface. This thickness of
skin increases to form a shell around the molten metal as
the solidification progresses towards the centre of the
cavity.

Alloys
 Most of the alloys freeze over a temperature range rather
than at a single temperature.
 The exact range depends on the alloy system and the
particular composition.
 Fig. No. 1.20 shows solidification (cooling curve) of
copper-nickel alloy system.
 The start of freezing is similar to that of pure metal. A thin
skin is formed at the mould wall due to large temperature
a) Solidification of pure metal b) Solidification of pure alloy gradient at the surface. After this, the freezing progresses
Fig. No. 1.18 Grain structure of pure metal similar to pure metal.
 During the solidification of metal alloy where both liquid
 At mould walls metal cools rapidly due to exposure to and solid phases exist known as mushy zone. It is an
ambient temperature. This result in shell of fine equiaxed important factor during solidification.
grain in the chill zone.  This zone present in freezing temperature range. The
 The grain growth through the mould away from wall is columner dendritic structure of grain growth is seen in this
columner. This is known as columner zone. zone.

Fig. No. 1.19 Solidification process (Cooling curves) pure Fig. No. 1.20 Solidification process (Cooling curves) Cu-Ni
metals alloy

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[Link] Casting Structure  Cast ingot structure (macrostructure) and microstructure

 During the casting process, molten metal is poured into are important and affect the mechanical properties of a
moulds and allowed to solidify. component.
 This results in a finished shape called as casting or a simple  The grain structure resulting from the solidification of
shape called as an ingot. molten metal decides the strength, hardness, toughness,
 An ingot needs the various processing methods to form a and etc. properties of a component.
finished product. Hence this macrostructure is also referred  Fig. No. 1.21 shows the effect growth rate (R) and
as ingot structure. temperature gradient (G) on the structure of casting.
 Ingot structure consists of three regions during
solidification. They are as follows 1.8 Nucleation
i) Chill zone  Nucleation is defined as to be the process that determine
ii) Columnar zone how long an observer has to wait before the new phase.
iii) Equiaxed zone  Nucleation is the beginning of a phase transformation. It is
marked by the appearance in the molten metal of tiny
i) Chill Zone regions called nuclei of the new phase which grow to solid
 Chill zone contains narrow band of randomly oriented crystals until the transformation is complete.
grains.  The solidification of metals occurs by nucleation and
 The metal at the mould wall cools to the freezing growth. The same is true of melting (maybe) but the
temperature at first due to higher heat dissipation. barriers are much less.
 The mould wall provides the surfaces at which  Thus, it is possible to achieve significant supercoiling of
heterogeneous nucleation takes place. pure metal liquids. Undercooling or supercooling is
achieved by suppressing heterogeneous nucleation.
ii) Columnar Zone  Prenucleants are assumed to exist in the liquid metal. In
 Columnar zone contains elongated grains oriented in many processes, homogeneous nucleation is assumed to
specific crystallographic directions. occurs
 The grain growth in this region takes place in the direction  The following are the two types of nucleation:
opposite to heat flow.
 Heat is removed from casting by the mould material and
grain grows perpendicular the mould wall.
 This columnar zone has anisotropic properties and
formation of this zone is a growth controlled process.

iii) Equiaxed Zone

 This zone forms in the center of the casting or ingot.
 It contains randomly oriented grains that are relatively
round or equiaxed.
 The formation of equiaxed zone is a nucleation controlled
process and has isotropic properties. Fig. No. 1.22 Types of Nucleation

1.8.1 Homogeneous or Self Nucleation

Fig. No. 1.23 Crystal Nucleus

 Homogeneous nucleation is a type of the nucleation
process where formation of nuclei starts in the interior of a
uniform substance such as pure liquid metals.
 Homogeneous nucleation occurs when where there are no
special objects inside a phase which can cause nucleation.
 It is the slower process and occurs with much more
Fig. No. 1.21 G √𝑹 ratio and pattern of solidification difficulty.

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 For instance, when a pure liquid metal is slowly cooled  For r > rc, particles tend to grow and such particles are
below its equilibrium freezing temperature to a sufficient called as nuclei.
degree, numerous homogeneous nuclei are created by slow  For the particular supercooling temperature, critical radius
moving atoms bonding together in a crystalline form. of particle must be known.
 By providing superheating or supercooling homogeneous
nucleation occurs spontaneously.
 Consider the free energy changes when some atoms in the
liquid collapse and agglomerate to form a solid of radius r.
 Nucleation of supercooled grains depends on the following
two factors:
i) The free energy available from solidification process
depends on the volume of particle formed. Due to change
in phase (molten to solid) a free energy decreases and it
makes the new phase more stable. For a spherical particle,
if the temperature is suddenly dropped below the freezing
point, the free energy change per unit volume is
4
(− 𝜋𝑟 3 × ∆𝑓𝑣 ) where, r is radius of the particle.
3
(Negative sign indicates that free energy decreases).
ii) Another factor is the energy required to form a solid-liquid
interface. Solid-liquid phases possess a surface in between
them. This surface has a positive free energy ‘ɣ’ per unit
area. The creation of a new surface is associated with free Fig. No. 1.24 Free energy changes in homogeneous
energy increase 4𝜋𝑟 2 × 𝛾. nucleation
Hence total free energy change is,
4 1.8.2 Heterogeneous Nucleation
∆𝑓 = − 𝜋𝑟 3 × ∆𝑓𝑣 + 4𝜋𝑟 2 × 𝛾 ….. (1.3)
3  Heterogeneous nucleation consisting of dissimilar
elements or ingredients; not having uniform quality.
For critical particle radius (rc) and critical free energy,  Heterogeneous nucleation is a type of nucleation which
differentiate the above equation (1.3) with respect to ‘r’ and starts at the surfaces, imperfections and severely damaged
equate to zero. regions.
∆𝑓 4
= 0 = − 𝜋∆𝑓𝑣 × 3𝑟𝑐2 + 4𝜋𝛾 × 2𝑟𝑐  As the presence of impurities in molten metal lowers the
∆𝑟 3 liquid-solid interface energy, the amount of supercooling
(undercooling) required to start nucleation will be less.
4 𝜋∆𝑓𝑣 × 𝑟𝑐2 = 4𝜋𝛾 × 2𝑟𝑐
 Hence, nucleation process takes place easily.
2𝛾  Heterogeneous nucleation requires the ability of liquid
𝑟𝑐 = …. (1.4) metal to wet the foreign particle.
𝑓𝑣
Substituting this value in equation (1.3),

4 2𝛾 3 2𝛾
∆𝑓 = − 𝜋( ) × ∆𝑓𝑣 + 4𝜋( )2 × 𝛾
3 𝑓𝑣 ∆𝑓𝑣

32 𝜋𝛾 3 𝜋𝛾 3
∆𝑓 = − + 16
3 (∆𝑓𝑣 )2 (∆𝑓𝑣 )2

16 𝜋𝛾3
∆𝑓 = ….. (1.5)
3 (∆𝑓𝑣 )2

Significance of Critical Radius

 As the particle radius increases, the free energy also
increases till the particle grows up to the critical radius (rc).
 Thereafter increase in the radius will tend to decrease the
free energy till it becomes negative.
 For r < rc, particle tends to redissolve and thus lower the Fig. No. 1.25 Heterogeneous nucleation of solid from liquid
free energy. Such particles are called as ‘embryos’.

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 The foreign particle hence act as a nucleus forming a low 1.9 Supercooling
contact angle and must possess some structural affinity  Supercooling also known as undercooling is the process of
with the solid metal. Refer fig. no. 1.25. lowering the temperature of a liquid or a gas below its
 The foreign matter or impurity is wetted by both solid and freezing point without it becoming a solid is called as
liquid. Hence the force of equilibrium where three surfaces supercooling.
meet together is given by,  A liquid below its standard freezing point will crystalline
𝛾. 𝑓𝑚 . 𝑠 = 𝛾𝑓𝑚 . 𝐿 − 𝛾𝑠. 𝐿. 𝑐𝑜𝑠𝜃 ….. (1.6) in the presence of a seed crystal or nucleus around which a
Where, crystal structure can form creating a solid.
fm = Foreign matter  However, lacking any such nuclei, the liquid phase can be
s = Solid surface maintained all the way down to the temperature at which
L = Liquid surface crystal homogeneous nucleation occurs.
 The total surface energy of heterogeneous nucleation is  Homogeneous nucleation can occur above the glass
equal to solid-Liquid (s-L) surface energy minus net energy transition temperature, but if homogeneous nucleation has
decrease. not occurred above that temperature, an amorphous (non-
 When the foreign matter – solid (fm – s) surface forms, it crystalline) solid will form.
decreases the net energy associated with its area.  If the liquid is just at the freezing point, only a few
∆𝑓𝑐 (𝐻𝑜𝑚𝑜𝑔𝑒𝑛𝑒𝑜𝑢𝑠) > ∆𝑓𝑐 (𝐻𝑒𝑡𝑒𝑟𝑜𝑔𝑒𝑛𝑒𝑜𝑢𝑠) molecules stick, because they have comparatively high
 Heterogeneous nucleation starts at higher temperature than energy.
homogeneous nucleation.  As the liquid is cooled, more molecules can form into
 As the foreign matter acts as a nucleus, no supercooling is nuclei. When the nucleus is big enough (because of
needed to actuate the nucleation. undercooling) the supercooled liquid suddenly changes to
 After formation of initial nucleus, more solid may be a solid.
deposited on the first nucleus and more nuclei may form.  Metals often experience undercooling of 50°C to 500°C.
Homogeneous nucleation usually only occurs in the
1.8.3 Difference between Homogeneous and Heterogeneous laboratory.
Nucleation  Impurities provide a seed for nucleation solidification can
start on a wall. Adding impurities on purpose is called
Table No. 1.3 Difference between Homogeneous and inoculation nucleation begins.
Heterogeneous Nucleation  The process opposite to supercooling, the melting of a solid
Sr. Homogeneous Heterogeneous above the freezing point, is much more difficult, and a solid
No. Nucleation Nucleation will almost always melt at the same temperature for a given
1. Homogeneous Homogeneous pressure. For this reason, it is the melting point which is
nucleation starts in the nucleation starts in the usually identified, using melting point apparatus; even
interior of a uniform interior of a uniform when the subject of a paper is freezing point determination,
substance substance. the actual methodology is the principle of observing the
2. It is a slower process. It is a faster process. disappearance rather than the formation of ice.
3. It occurs with much It occurs easily.  It it, however, possible at a given pressure to superheat a
more difficulty. liquid above its boiling point without it becoming gaseous.
4. In homogeneous In heterogeneous  Supercooling is often confused with freezing point
nucleation, nuclei are nucleation, impurity depression. Supercooling is the cooling of a liquid below
formed from atoms of atom or container its freezing point without it becoming solid.
the solidifying metal. surface acts as a  Freezing point depression is when a solution can be cooled
nucleating agent. below the freezing point of the corresponding pure liquid
5. Homogeneous Heterogeneous due to the presence of the solute.
nucleation occurs at nucleation starts at much  For example, the freezing point depression that occurs
lower temperature than higher temperature. when sodium chloride is added to pure water.
required for
heterogeneous 1.9.1 Application of Supercooling
nucleation.  One commercial application of supercooling is in
6. It requires supercooling It requires little or no refrigeration.
to form first nuclei and supercooling at all.  For example; there are freezers that cool drinks to a
start the nucleation. supercooled level so that when they are opened, they form
a slush.

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 Another example is a product that can super cool the 1.11 Grain and Grain Boundary Effect
beverage in a conventional freezer.  A schematic representation of a grain boundary, as it might
 The Coca-Cola Company also briefly marketed special appear in a metal that crystallizes in the cubic system, is
vending machines containing sprite in the UK, and coke in shown in Fig. No. 1.27
Singapore, which stored the bottles in a supercooled state
so that their content would turn to slush upon opening.

1.10 Equiaxed and Columnar Grains

Fig. No. 1.27 Grain boundary on lattice scale

(a) (b) (c)  In this figure, one of the axes of each grain is parallel to the
Fig. No. 1.26 Types of crystal structure in ingots other while one of the other axes is rotated.
 At the interface between these two crystals, the atomic
 The overall size and to some degree, the shape of crystals distances are not correct, so that atoms are therefore not in
in a metal ingot varies with the rate of cooling. Rapid stable positions.
cooling gives rise to considerable undercooling and the  These atoms are in a higher energy state. They will tend to
presence of a mould surface helps to nucleate the liquid. adjust their positions to a condition of minimum energy.
 As a result a dense shower of nuclei will form  The lower density of atoms at the boundary provides a
instantaneously and so a layer of very small or chill crystals place for impurity atoms to reside, it is common to observe
will result as shown in fig. no. 1.26 (b) impurity atoms at the grain boundaries.
a) Columnar crystals-excessive segregation of impurities at  If, during the growth process, the development of external
the core. features, such as regular faces, is prevented by interference
b) Zones containing chill, columnar and equi-axed grains. from the growth of other nuclei, each unit is called a grain
c) Large equi-axed grains-less segregation because the rather than a crystal.
cooling rate was low.  The term crystal is usually applied to a group of space
 As the mould warms up progressively and the rate of lattices of the same orientation which shows symmetry by
cooling is reduced, a stage is reached when crystal growth the development of regular faces.
inwards is balanced by heat flow outwards.  Each grain is essentially a single crystal. The size of the
 Fresh nuclei are not formed and so the existing crystals grain depends upon the temperature from which the metal
grow in columnar shape. With large ingots the rate of is cast, the cooling rate, and the nature of the metal.
cooling at the centre may be so low that few nuclei form  Slow removal of heat at the solidification temperature will
since there is little undercooling? produce a few large grains, whereas the rapid removal of
 Consequently the resultant crystals tend to be large and heat will produce many small grains.
equi-axed that is, of equal axes.  Two parameters control the size of grains formed in the
 Columnar grains are long, thin, coarse grains created when solidification of metal; the rate of nucleation and the rate
a metal solidifies rather slowly in the presence of a steep of growth.
temperature gradient.  The first is the number of nuclei that form per unit of time
 Relatively few nuclei are available when columnar grains and is dependent upon temperature.
are produced. Equi-axed and columnar grains are shown in  The second is the velocity of growth expressed in length
the Fig. No. 1.26. The columnar grains have grown per unit of time and is also dependent upon temperature.
perpendicular to the mould faces since large thermal  The rate of nucleation and the rate of growth as a function
gradients were present in those directions. of temperature vary from metal to metal.

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 In one example, this relationship may be shown in Fig. No. metals, the later conditions prevail rapid cooling leads to a
1.28. finer grain structure.

1.12 Cooling Curves

 One method of determining the temperatures at which
phase changes occur in a system consists of following the
temperature as a function of time, as different alloys in the
system are very slowly cooled,
 The data obtained in this manner form a cooling curve for
each of the alloys. This method is particularly useful in
studying the changes that occur during the solidification of
alloys and, in some instances, may be used to advantage in
determining transformation subsequent to solidification.
 However, in the latter case, the method may not be
sufficiently sensitive, hence, other procedures may be
employed.
Fig. No. 1.28 Rate of growth and rate of nucleation versus  If the equilibrium diagram of the antimony-bismuth system
temperature is to be determined, a series of alloys containing different
amounts of antimony and bismuth will be made.
 By the slow cooling of such a metal, crystallization will
take place at a temperature near, but below, the equilibrium  Each sample is heated until molten and uniform in
melting point (at the melting point, equilibrium prevails, composition, and then it is allowed to cool very slowly. A
and the metal crystallizes and melts, since both solid and thermocouple may be employed to determine the
liquid can coexist). temperature as cooling proceeds.
 In the metal illustrated, the grains will be small, since the  Consider the first sample of pure antimony cooling slowly
rate of growth is not large compared with the rate of from the molten state. The cooling curve for this alloy is
nucleation. shown in fig. 1.30 (a)
 If this metal is cooled more rapidly so that crystallization  A hold occurs in the cooling curve beginning at X and
occurs at a temperature at which the rate of nucleation is ending at Y. Examination of the metal in the crucible will
very large compared with the rate of growth, the grain size indicate that solidification begins at the time corresponding
may be very small. to point X and is completed at the time corresponding to
point Y i.e. solidification occurs at the constant
 Much faster cooling in this event will produce a coarser
temperature Tsb 630°C.
grain size, since a point is reached where the rate of
nucleation has decreased and the rate of growth has  The temperature remains constant during the process of
increased. solidification because of the liberation of heat of fusion.
 The relation of the rate of nucleation and the rate of growth
in another instance is illustrated in Fig. No. 1.29.

Fig. No. 1.30 Cooling curves for antimony-bismuth system

 Consider an alloy of antimony and bismuth containing 25%
bismuth and 75% antimony. This homogeneous molten
alloy is allowed to cool very slowly, and observations of
temperature and time are made.
Fig. No. 1.29 Rate of growth and rate of nucleation versus  The cooling curve for this alloy is shown in fig. 1.30 (b)
temperature cooling continues in a uniform manner until the
 In this instance, slow cooling will lead to a coarse grain, temperature reaches the value of 590°C at which a break in
whereas more rapid cooling will yield finer grains. In most the curve is encountered.

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 At this temperature, the rate of cooling decreases.

Examination will show that solidification begins at the
break, or point X, and continues until the temperature
corresponding to point Y, 426°C, is reached.
 At point Y, the cooling rate changes again. This point Y is
designated as a recovery.
 Solidification occurs in this case over a range of
temperature. The structure of the solid material at
temperature below 426°C consists of homogeneous grains,
i.e. all grains are exactly of the same composition.
 It is a one-phase alloy namely, a solid solution of antimony
and bismuth.
 Consider an alloy containing 50% bismuth. These
constituents are melted in a crucible and allowed to cool
slowly.
 The cooling curve of this alloy is shown in fig. 1.30 (c).
The break X (526°C), and the recovery, Y (338°C), occur
at lower temperatures than, for the previous alloy.
 Examination of the structure of the solidified alloy will
reveal that it consists of only one phase, namely, a solid Fig. No. 1.31 Equilibrium diagram of antimony and
solution of bismuth and antimony. bismuth
 An alloy containing 75% bismuth and 25% antimony will  At a temperature of Ti in the equilibrium diagram of the
produce cooling curve as shown in fig. 1.30 (d). antimony-bismuth (Fig. No. 1.31). The composition of the
 This curve has characteristics similar to those found in the liquid and the composition of the solid solution are
preceding two cases break, X (426°C), and the recovery, Y determined by the intersection of this temperature
(293°C), occur at lower temperatures than in the preceding horizontal with the liquids and solidus curves, respectively.
cases.  Any alloy that exists within the area enclosed by the
 The structure of the solid alloy will consists of liquidus and solidus curves will have one degree of
homogeneous grains of solid solution. freedom and will be considered as Univariant.
 The cooling curve of pure bismuth is shown in fig. 1.30 (e).
In this case, a hold occurs in the cooling curve at a 1.12.1 Types of Cooling Curves
temperature of 271°C solidification begins at point X and  Cooling curve is the graphical plot of phases of element on
is completed at point Y. temperature v/s time.
 One may conclude from this discussion that pure metals  The resulting phases during solidification is different for
solidify at constant temperature and their cooling curves various alloy compositions.
exhibit only a hold, whereas the cooling curves of solid  The following are the types of cooling curves:
solutions exhibit a break and a recovery. a) Pure metals
 The results obtained from the cooling curves may now be b) Binary solid solution alloys
plotted in a diagram of temperature as a function of c) Binary eutectic alloys
composition called the equilibrium or phase diagram, fig. d) Off-eutectic binary alloys
No. 1.31.
 The temperature at which solidification begins, as a) Pure metals
indicated by all points designated X in the cooling curves,
will form the liquids curve.
 The temperature at which solidifications is completed,
namely, all points Y of the cooling curves, form the solidus
curve of the equilibrium or phase diagram.
 The liquidus curve is in reality, a plot of the composition
of liquid that will be in equilibrium with solid at any given
temperature similarly, the solidus curve indicates the
composition of solid that will be in equilibrium with liquid
at any given temperature. This is in accord with the phase
rule as stated.
Fig. No. 1.32 Cooling curve of a pure metal

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 Unit I Overview of Metallurgy

 The figure no. 1.32 shows that cooling curve of pure Region AB:
metals. P+F=C+1
 At point B freezing starts and ends at C and between B and 1+F=2+1
C, the metal is in the liquid plus solid state. Above the F=2
temperature observed by point B, the metal is in the liquid The meaning of F = 2 is that both the temperature and
state and below at point C, it is in the solid state. concentration will be different independently without
 According to phase rule applied at different regions. changing the liquid phase existing in the system.
Region AB: Region BC:
P+F=C+1 P+F=C+1
1+F=1+1 2+F=2+1
F=1 F=1
The meaning of F = 1 is that the temperature will be The meaning of F = 1 is that of any one variable out of
different without changing the liquid phase existing in the temperature and composition will be changed
system. independently without altering the liquid and solid phases
Region BC: existing in the system. It is clear that solid solution, alloys
P+F=C+1 solidify over the range of temperature. Melting begins at
2+F=1+1 one temperature and ends at another temperature.
F=0 Region CD:
The meaning of F = 0 is that the temperature will not be P+F=C+1
different without changing the liquid and solid phases 1+F=2+1
existing in the system. If the temperature increased, the F=2
metal goes in the liquid state and if decreased, it goes in the The meaning of F = 2 is that both the temperature and
solid state. Hence, pure metals solidify at constant concentration will be different independently without
temperature. changing the liquid phase existing in the system.
Region CD:
P+F=C+1 c) Binary Eutectic Alloys
1+F=1+1  The fig. no. 1.34 shows that the cooling curve of a binary
F=1 eutectic alloy point A to B, the alloy is in the liquid state.
The meaning of F = 1 is that the temperature will be At point B, freezing begins and simultaneously two solids
changed without changing the solid phase existing in the i.e. S1 and S2 start separating out from the liquid.
system.  This will be continuous at the point C. The alloy gets
completely solidified at point C and gives a mixture of S 1
b) Binary Solid Solution Alloys and S2. At point C to D, there is no change in the solidified
 The fig. no. 1.33 shows that cooling curve of solid solution alloy.
alloys.  According to the phase rule is applied to different regions.
 Point A to B, the alloy is in the liquid state, at point B,
freezing begins and it completes at point C, and between B
and C, the alloy is in the liquid plus solid state. Point C to
D, there is no change in the solid state of the alloy.
 According to phase rule for different regions applied.

Fig. No. 1.34 Cooling curve of binary eutectic alloy

Region AB:
P+F=C+1
1+F=2+1
F=2
The meaning of F = 2 is that both the temperature and
concentration will be different independently without
Fig. No. 1.33 Cooling curve of solid solution alloy changing the liquid phase existing in the system.

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 Unit I Overview of Metallurgy

Region BC: Region AB:

P+F=C+1 P+F=C+1
3+F=2+1 1+F=2+1
F=0 F=2
The meaning of F = 0 is that neither temperature nor Region BC:
concentration will be different without changing the phases P+F=C+1
existing in the system. So the eutectic alloys solidify at 2+F=2+1
constant temperature same to that of pure metals. F=1
Region CD:
P+F=C+1 Region CD:
2+F=2+1 P+F=C+1
F=1 3+F=2+1
Binary eutectic is a homogeneous mixture of two solids F=0
which forms at constant temperature during cooling and Region DE:
melts at constant temperature during heating. Binary P+F=C+1
eutectic transformation reaction can be as follows: 2+F=2+1
F=1
Constant The begins of solidification temperature is liquids
L S 1 + S2 temperature because above this, the metal or alloy is in the
Temperature liquid state; whereas; the end of solidification temperature
is called solidus temperature because of below this, the
Where S1 is one solid and S2 is another solid. The metal or alloy is in the solid state.
temperature at which this transformation reaction obtain is
called eutectic temperature. 1.13 Plotting of Equilibrium or Phase Diagram
 Equilibrium diagrams can be plotted by using several
d) Off- Eutectic Binary Alloys methods such as thermal analysis (cooling curves), electron
 Eutectic reaction occurs for a definite composition and at microscopy, X-ray diffraction, electrical resistivity and
definite temperature. magnetic measurements.
 If the composition of alloy differs from the eutectic  The most commonly used method is thermal analysis.
composition, it is referred as off-eutectic alloy.  Let us consider a binary solid solution alloy of Cu-Ni such
 Off-eutectic alloys with composition less than eutectic that they have 100 % solubility in liquid and solid states.
composition are called hypo-eutectic alloys and those with  The steps used to obtain equilibrium diagram are:
composition more than eutectic composition are called 1. Prepare large number of samples of Cu-Ni alloy by
hyper-eutectic alloys. varying the composition of Ni, in the Cu base (say 11
 During cooling of off-eutectic alloy, either of the two solids samples).
separate out earlier depending on whether the alloy is hypo S 1 2 3 4 5 6 7 8 9 10 11
or hyper eutectic alloy. %Cu 100 90 80 70 60 50 40 30 20 10 0
 Figure no. 1.35 shows typical cooling curve for an off- %Ni 0 10 20 30 40 50 60 70 80 90 100
eutectic binary alloy. 2. Plot the cooling curves of the above 11 samples of Cu-
 According to the phase rule applied to the different regions. Ni alloy as shown in figure no. 1.36.

Fig. No. 1.35 Cooling curve of off- eutectic binary alloy Fig. No. 1.36 Cooling curve of solid solution alloy

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 Unit I Overview of Metallurgy

3. Note down the liquidus temperature of these sample as  Line G-C-H marks transformation from liquid phase to
L1, L2, L3, …….. , L9, L10 and L11. intermediate solid + liquid phase on cooling.
4. Similarly note down the solidus temperature of these  Similarly, G-D-H marks transformation from intermediate
sample as solid + liquid phase to solid phase on further cooling.
S1, S2, S3, …….. , S9, S10 and S11.  Now, we need to calculate exact amount of phases i.e. %
5. Now, plot a graph of temperature vs composition i.e. content of solid and % of liquid at point F.
plot liquidus and solidus temperature vs composition  According to lever rule,
of the sample. Refer Fig. No. 1.37. % 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑
𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑍% 𝐵 𝑎𝑙𝑙𝑜𝑦 𝑐𝑜𝑛𝑠𝑖𝑑𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑎𝑛𝑑
= 𝑡ℎ𝑒 𝑠𝑜𝑙𝑖𝑑𝑢𝑠 𝑙𝑖𝑛𝑒
𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑠𝑜𝑙𝑖𝑑𝑢𝑠 𝑎𝑛𝑑 𝑙𝑖𝑞𝑢𝑖𝑑𝑢𝑠 𝑙𝑖𝑛𝑒

𝑙(𝐹𝐷)
% 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 = × 100
𝑙(𝐶𝐷)
Similarly,
% 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑
𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑍% 𝐵 𝑎𝑙𝑙𝑜𝑦 𝑐𝑜𝑛𝑠𝑖𝑑𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑎𝑛𝑑
= 𝑡ℎ𝑒 𝑠𝑜𝑙𝑖𝑑𝑢𝑠 𝑙𝑖𝑛𝑒
𝐷𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑠𝑜𝑙𝑖𝑑𝑢𝑠 𝑎𝑛𝑑 𝑙𝑖𝑞𝑢𝑖𝑑𝑢𝑠 𝑙𝑖𝑛𝑒

𝑙(𝐶𝐹)
% 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑 = × 100
𝑙(𝐶𝐷)
Now,
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑 𝑙(𝐶𝐹)/𝑙(𝐶𝐷) 𝑙(𝐶𝐹)
Fig. No. 1.37 Equilibrium diagram = =
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑙(𝐹𝐷)/𝑙(𝐶𝐷) 𝑙(𝐹𝐷)
6. Draw a smooth curve passing through the liquidus Therefore,
temperatures L1 to L11. Similarly draw a smooth curve
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑 × 𝑙(𝐹𝐷) = 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 × 𝑙(𝐶𝐹)
passing through the solidus temperatures S1 to S11.
 It means, the line CD acts as a lever arm and the point F
7. The resulting loop is called equilibrium or phase
acts as a fulcrum point as shown in fig. no. 1.39. Hence it
diagram.
is called as lever rule or lever arm principle.
1.14 Lever Rule
 It is the method used to find out the exact amount of a
particular phase existing in a binary system for a given
alloy at any temperature under consideration.
 Let us consider an alloy of metal ‘A’ and ‘B’. Let ‘Z’ be
the composition of alloy under consideration and ‘T’ be the
temperature at which phase content is to be found out.
Refer fig. 1.38 for such a binary system.

Fig. No. 1.39 lever rule or lever arm principle

 From fig. no. 1.39, we can write,
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑 × 𝐼𝑡𝑠 𝑙𝑒𝑣𝑒𝑟 𝑎𝑟𝑚
= 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 × 𝐼𝑡𝑠 𝑙𝑒𝑣𝑒𝑟 𝑎𝑟𝑚
 At any temperature, the amounts of solid and liquid phases
can be found in a similar manner.
Tie Line
 An isothermal (constant temperature) line through the
alloys position on the phase diagram when it is a two phase
field intersecting the two adjacent solubility curves is
called as a Tie line.

Fig. No. 1.38 Binary system of metal ‘A’ and metal ‘B’

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 Unit I Overview of Metallurgy

 The ends of the Tie lines shows the compositions of the b. Coring increases susceptibility to corrosion.
two phases that exist in equilibrium with each other at these c. Coring gives non-uniform mechanical and physical
temperature. properties.
 The above drawbacks of coring can be eliminated by using
1.15 Coring slow cooling rates while solidification of an alloy or by
 At room temperature variation in composition is observed homogenisation heat treatment to the cored castings.
from point to point or centre to surface of a grain or  Coring is commonly observed in cast components of some
dendrite in a solidified alloy. This micro segregation is of the alloys like brasses, bronzes and stainless steel.
known as coring.
 For understanding this phenomenon refer fig. no. 1.40 of 1.16 Eutectic System
isomorphous system.  Eutectic system represents all alloys wherein the two
metals have complete solubility in liquid state and
complete insolubility in solid state.
 These systems form a V-shaped equilibrium diagram.
 Examples: Pb-As, Bi-Cd, Au-Si, etc.
 Eutectic reaction is also called as invariant reaction.
 Invariant reactions are those reactions which occur under
equilibrium conditions at a specific temperature and alloy
composition that cannot be varied.
 Figure No. 1.41 shows a typical equilibrium diagram of a
eutectic system.

Fig. No. 1.40 Cored dendrite

 We know that, the first solid that separates from the liquid
at point 2 has composition given by the point 2’.
 Due to decrement in temperature, the average composition
of the existing solid changes along the solidus line D-4-C
and that of liquid along the liquidus line D-2-C and the last
liquid solidifies at point 4.
 The composition of last liquid that solidifies at point 4 is
given by the point 4’’ hence the last solid formed has a
composition corresponding to point 4’’. Fig. No. 1.41 Typical equilibrium diagram of a eutectic
 It indicates that the first solid i.e. centre of grain (dendrite) system
will be rich in B (high melting point substance) and the last  Figure No. 1.41 shows a system of metals A and B.
solid i.e. surface of grain will be rich in A (low melting  Points C and G represents melting point of metals A and B
point substance). respectively.
 But, the average composition of the grain or dendrite will  By adding metal B into A or A into B, the melting point of
be the same as original. the system reduces along curves CE and GE respectively.
 Due to the inability of the alloy for continuous adjustments  Point E represents the lowest melting temperature above
in compositions of the phases, concentration differences which the system of A and B will melt.
are seen in the structure at the room temperature. Such type  Point E is also called as eutectic point.
of structures are known as cored structures.  Line CEG represents the liquidus line and line CDEFG
 It is seen under the optical microscope by colour represents the solidus line.
differences developed through an etching effect by the  Eutectic reaction is given by:
compositional gradients existing in the dendrite.
 Due to the following adverse effects, coring is not Constant
desirable: L S 1 + S2
a. Coring increases brittleness. Temperature

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 Unit I Overview of Metallurgy

 Slow cooling transformation for eutectic system can be At Point 3

classified as follows: From point 2 to 3, there is no change in the microstructure.
A) Eutectic transformation
B) Hypoeutectic transformation (Composition less than B) Hypoeutectic Transformation
eutectic)  Consider slow cooling along line (II) as shown in fig. no.
C) Hypereutectic transformation (Composition more than 1.44
eutectic)

A) Eutectic Transformation
 Consider slow cooling along line (I) as shown in fig. no.
1.42

Fig. No. 1.44 Hypoeutectic transformation

 Consider points 1, 2, 3 and 4 along the line II.
At Point 1
The system is in complete liquid state. Refer fig. no. 1.45 (a)
Fig. No. 1.42 Eutectic transformation
 Consider points 1, 2, and 3 along the line I.
At Point 1
The system is in complete liquid state. Refer fig. no. 1.43 (a)

Fig. No. 1.45 (a)

At just below point 2
Solidification of metal A starts just below point 2. Metal A
starts separating from the liquid mix of A + B. Microstructure
Fig. No. 1.43 (a) just below point 2 is given by refer fig. no. 1.45 (b).
At Point 2
Eutectic transformation occurs at point 2.
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
𝐿𝑖𝑞𝑢𝑖𝑑 → 𝐴+𝐵
The microstructure appears lamellar with alternate lines of A
and B. Refer fig. no. 1.43 (b)

Fig. No. 1.45 (b)

At just below point 3
Below point 3, eutectic transformation of remaining liquid takes
place. The already separated proeutectic A remains unchanged.
Fig. No. 1.43 (b)

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Microstructure just below point 3 is given by refer fig. no. 1.45 At Point 1
(c). The system is in complete liquid state. Refer fig. no. 1.47 (a)

Fig. No. 1.47 (a)

At Point 2
Solidification of metal A starts just below point 2. Metal B starts
separating from the liquid mix of A + B. Microstructure just
Fig. No. 1.45 (c)
below point 2 is given by refer fig. no. 1.47 (b).
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
𝐿𝑖𝑞𝑢𝑖𝑑 → 𝐴+𝐵
𝑙(3𝐸)
% 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑟𝑜𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 𝐴 =
𝑙(𝐷𝐸)
𝑙(𝐷3)
% 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 =
𝑙(𝐷𝐸)
At Point 4
From point 3 to 4, there is no change in the state of the system.
𝑇𝑜𝑡𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝐴 𝑎𝑡 𝑝𝑜𝑖𝑛𝑡 4
= [𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑟𝑜𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 𝐴]
Fig. No. 1.47 (b)
+ [𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 𝐴]
At Point 3
𝑙(3𝐸) 𝑙(𝐸𝐹) 𝑙(𝐷3) Below point 3, eutectic transformation of remaining liquid takes
=[ ]+[ × ]
𝑙(𝐷𝐸) 𝑙(𝐷𝐹) 𝑙(𝐷𝐸) place. The already separated proeutectic B remains unchanged.
Microstructure just below point 3 is given by refer fig. no. 1.47
C) Hypereutectic Transformation (c).
 Consider slow cooling along line (III) as shown in fig. no.
1.46.

Fig. No. 1.47 (c)

𝑙(𝐸3)
% 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑟𝑜𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 𝐵 =
𝑙(𝐸𝐹)
𝑙(3𝐹)
% 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 =
𝑙(𝐸𝐹)
At Point 4
From point 3 to 4, there is no change in the state of the system.
𝑇𝑜𝑡𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝐵
= [𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑟𝑜𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 𝐵]
+ [𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 𝐵]
Fig. No. 1.46 Hypereutectic transformation 𝑙(𝐸3) 𝑙(𝐷𝐸) 𝑙(3𝐹)
=[ ]+[ × ]
 Consider points 1, 2, 3 and 4 along the line III. 𝑙(𝐸𝐹) 𝑙(𝐷𝐹) 𝑙(𝐸𝐹)

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1.17 Partial Eutectic System

 Partial eutectic system represents all alloys wherein the two
metals have complete solubility in liquid state and partial
solubility in the solid state.
 These systems also form a V-shaped diagram with
adjoining solid solutions on the left and right side.
 Examples: Ag-Cu, Pb-Sn, Sn-Bi, Pb-Sb, Cd-Zn, Al-Si, etc.
 Figure No. 1.48 shows a typical equilibrium diagram of a
partial eutectic system.
 Point C and G represent the melting point of metal A and
B respectively.
 α is the solid solution of B in A and β is the solid solution
of A in B.

Fig. No. 1.49 Ag-Cu partial eutectic equilibrium diagram

Fig. No. 1.50 (a)

At just below point 2
Solidification of metal A starts just below point 2. α starts
separating from the liquid as proeutectic phase. Microstructure
just below point 2 is given by refer fig. no. 1.50 (b).

Fig. No. 1.48 Partial Eutectic System

 Line CEG represents the liquidus line and line CDEFG
represents the solidus line.
 Points D and F indicate the maximum solubility of α and β
at eutectic temperature.
 Point H and K indicate the solubility of α and β at room Fig. No. 1.50 (b)
temperature. At just below point 3
 Let us discuss cooling of partial eutectic alloy considering Below point 3, eutectic transformation of remaining liquid takes
example of Ag-Cu alloy with 15% Cu (hypoeutectic). place. The already separated proeutectic α remains unchanged.
Microstructure just below point 3 is given by refer fig. no. 1.50
Cooling of Ag-Cu alloy with 15% Cu (Hypoeutectic) (c).
 Refer figure no. 1.49 for Ag-Cu partial eutectic alloy.
 Consider transformation along line II with 15% Cu.
 Consider points 1, 2, 3 and 4 along line II.

At Point 1
The system is in complete liquid state. Refer fig. no. 1.50 (a)

Fig. No. 1.50 (c)

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 Unit I Overview of Metallurgy

𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑙(3𝑁)

𝐿𝑖𝑞𝑢𝑖𝑑 → 𝛼+𝛽 % 𝐿𝑖𝑞𝑢𝑖𝑑 =
𝑙(𝑀𝑁)
𝑙(3𝐸) (28.1 − 20)
% 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑟𝑜𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 𝛼 = =
𝑙(𝐷𝐸) (28.1 − 8.8) At just below point 4
= 42.00% The complete system solidifies below point 4. The last liquid
freezes too solid.
𝑙(𝐷3) (20 − 8.8)
% 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑒𝑢𝑡𝑒𝑐𝑡𝑖𝑐 = =
𝑙(𝐷𝐸) (28.1 − 8.8) From point 4 to 5
= 58.00% The system remains in solid state without any change of phase.
At Point 4
From point 3 to 4, there is no change in the state of the system.
The solubility of α goes on decreasing. Hence, β separates out
from α along grain boundaries. University Question

1.18 Isomorphous System November 2019 Examination

 Isomorphous system represents all alloys wherein the two
metals have complete solubility in solid and liquid states. 1. Explain the factors that govern Hume Rothery’s rules
 These systems form a loop type equilibrium diagram. of solid solubility. (Refer Section. 1.5.7)
 Examples: Cu-Ni, Au-Ag, Au-Cu, Au-Ni, Bi-Sb, etc. 2. What is the allotropic transformation? Give any three
 Figure No. 1.51 shows a typical equilibrium diagram of an examples which show allotropic transformation.
isomorphous system. (Refer Section. 1.5.8)
3. What is coring? Which alloys show cored structures
and under what condition. (Refer Section. 1.15)

May 2019 Examination

1. Explain with the help of neat well labelled sketch the
term ‘Dendrite’. (Refer Section. [Link])
2. Differentiate between solid solution and intermetallic
compound. (Refer Section. 1.5.6)

November 2017 Examination

1. Define the following terms:
a) Phase (Refer Section. 1.5.2)
b) Alloy (Refer Section. 1.5.5)
c) Grain (Refer Section. 1.11)
d) Nucleation (Refer Section. 1.8)
Fig. No. 1.51 Isomorphous System
2. Write Hume Rothery’s rule of solid solubility. (Refer
 In above figure, point C represents melting point of metal
Section. 1.5.7)
A and point D represents melting point of metal B.

From point 1 to 2
May 2017 Examination
The alloy is in liquid state and no change occurs. 1. Explain the terms:
a) Allotropy (Refer Section. 1.5.2)
At just below point 2 b) Solid Solution (Refer Section. 1.5.2)
Solidification starts and solid phase starts separating out. c) Solidus Line (Refer Section. 1.13)
2. State and explain Gibbs phase rule. (Refer Section.
From point 2 to 3 1.6)
As temperature decreases, the amount of solid separating out
goes on increasing. At point 3,
𝑙(𝑀3)
% 𝑆𝑜𝑙𝑖𝑑 =
𝑙(𝑀𝑁)

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 Unit II Micro and Macroscopic Study of Metals

Unit – II
Micro and Macroscopic Study of Metals

Syllabus:
Classification of metal observations: their definition, difference & importance.
Microscopy: Various sampling techniques, specimen preparation, specimen mounting (hot & cold mounting)
electrolytic polishing, etching procedure and reagents, electrolytic etching.
Microscopic techniques: optical microscopy, electron microscopy, transmission electron microscopy (TEM),
scanning electron microscopy (SEM), scanning probe microscopy (SPM), AFM etc. (principal & application
only)
Study of Metallurgical microscope .Measurement of grain size by different methods & effect of grain size on
various mechanical properties.
Macroscopy: Sulphur printing, flow line observations, spark test.

Section No. Topic Name Page No.

2.1 Introduction 28
2.2 Classification of Engineering Materials 28
2.3 Metallography 32
2.4 Classification of Metal Observations 32
2.5 Specimen Preparation 33
2.6 Determination of Microstructure 36
2.7 Microscopic Techniques 36
2.8 Optical Metallurgical Microscope 36
2.9 Electron Microscopy 37
2.10 Transmission Electron Microscopy (TEM) 38
2.11 Scanning Electron Microscopy (SEM) 38
2.12 Scanning Probe Microscope (SPM) 39
2.13 Grain Size 40
2.14 Grain Size Determination 40
2.15 Macroscopy 41
2.16 Sulphur Printing 42
2.17 Flow Lines Observations 42
2.18 Spark Test 43

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 Unit II Micro and Macroscopic Study of Metals

2.1 Introduction  Cast iron are formed by melting a metal and casting with
 A material is that, out of which anything is made. It relates or without machining to the desired final shape and size,
itself to matter. hence called cast iron.
 The knowledge of materials and their properties is of great
significance for a design engineer. Characteristics of Cast Iron
 The machine elements should be made from such a  While manufacturing of cast iron, raw materials like pig
materials which has properties suitable for the operating iron, scrap limestone, coke etc. are used. All these elements
conditions. are relatively cheap, hence the cast iron is the cheapest
 Property of a material is a factor that influences amongst all alloys.
qualitatively or quantitatively the response of a given  The melting point of cast iron is low i.e. 1140 to 1240°C.
material under the action of forces, temperature, pressure  Due to high fluidity of melt, cast iron has excellent
etc. castability.
 Property indicates that, whether a material is suitable or  By altering the chemical composition, cast iron can
unsuitable for a particular use in industry. provide a wide range of metallic properties.
 The material property is independent of the dimension or
shape of the material. Advantages of Cast Iron
 It is low cost material.
2.2 Classification of Engineering Materials  It can provide good damping capacity and high
The engineering materials are mainly classified as follows. compressive strength.
 Cast iron has high resistance to wear and abrasion.
 It has high hardness.
 Corrosion resistance of cast iron is fairly good.
 It has excellent machinability.

Limitations of Cast Iron

 It is brittle in nature.
 Its mechanical properties like toughness, stiffness,
resilience etc. are poor.
 Due to brittleness, it is poor against fatigue and impact
loading.

Applications of Cast Iron

Fig. No. 2.1 Classification of Engineering Materials  Machine beds, columns, hammers, road-rollers.
 Pipe fittings, valves, farm equipment's, automotive parts.
2.2.1 Ferrous Metals  Camshafts, crank shafts, gears, ordnance parts.
 The ferrous metals are those which have the iron as their  Motor covers, pump bodies, furnace parts.
main element or constituent.  Engine frames, piston and cylinder, cylinder blocks and
 Ferrous materials are the most important metals in the bearing blocks etc.
metallurgical and mechanical industries because of their
extensive use. Types of Cast Iron
 The commonly used ferrous metals are as follows: Cast Iron are classified as follows:
1. Cast iron 1. White cast iron
2. Alloy cast iron 2. Gray cast iron
3. Steel (Plain carbon steel) 3. Malleable cast iron
4. Nodular cast iron
4. Alloy steel

Cast Iron Alloy Cast Iron

 Cast iron are the alloy of iron and carbon.  Generally, cast iron has low impact resistance, corrosion
 Generally, commercial cast iron are complex in resistance and temperature resistance. Hence, to increase
composition and their carbon content is in the range of 2.3 these properties certain alloying elements are added in
to 3.7 % with other elements like sulphur, manganese, suitable amount.
phosphorus and silicon.  Usually, nickel, chromium, copper, silicon, vanadium,
molybdenum etc. are used for this purpose.

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Properties of alloy cast iron Properties of Alloy Steel

 It has high strength.  They are ductile in nature.
 It has high oxidation resistance.  They have high corrosion resistance.
 It has high wear resistance and corrosion resistance.  They have high strength.
 They are soft and having high toughness.
Applications of alloy cast iron
 Gear, automobile parts like pistons, piston rings, camshaft, Advantages of Alloy Steel
crank shaft, cylinders.  They have high tensile and fatigue strength.
 Brake drum, pulleys, grinding machinery parts, etc.  They have high wear resistance, corrosion resistance and
creep resistance.
Plain Carbon Steel  They have high toughness and resilience.
 Steel is an alloy of iron and carbon with carbon content up
to 1.6 % approximately. Limitations of Alloy Steel
 Carbon content increases the strength and hardness of  Alloy steel cannot be cast into complicated shapes.
steel.  Their vibration damping properties is poor.
 Plain carbon steel or carbon steel is defined as a steel  They are costlier than steel and cast iron.
which has its properties mainly due to its carbon content
and does not contain more than 0.5% of silicon and 1.5% Applications of Alloy Steel
of manganese.  Aircraft engine parts, heat exchangers, wrist watches,
sanitary fittings.
Properties of Plain Carbon Steel  Combustion chamber, furnace parts, gas burners, screws.
 They are ductile in nature.  Valves, pumps, surgical instruments, razor blades, turbine
 They have high fatigue and impact strength. blades, missiles, structural components, etc.
 Their mechanical properties like toughness, stiffness,
resilience, etc. are high. 2.2.2 Non-Ferrous Metals
 Non-ferrous metals are those which contain a metal other
Advantages of Plain Carbon Steel than iron as their main element or constituent.
 They have high tensile strength.  Non-ferrous metals find wide applications in various
 They have high resilience and toughness. industrial sectors because of following advantages:
 They can sustain fatigue and impact load. 1. Low density, hence light in weight.
2. High electrical conductivity.
Limitations of Plain Carbon Steel 3. Easy to fabricate.
 The vibration damping property of steel is poor. 4. High corrosion resistance.
 They cannot be cast into complicated shapes.  The commonly used non-ferrous alloys are as follows:
 They have low wear resistance. 1. Copper and its alloys
 Its cost is more than cast iron. a) Brasses b) Bronzes
2. Aluminium and its alloys
Applications of Plain Carbon Steel
 Stampings, fan blades, rivets, nuts, bolts, wires, structural Copper and its Alloys
steel, grill, shafts.  Copper is one of the most widely used non-ferrous metal.
 Gears, valves, crank shaft, camshaft, axles, screws,  Various alloying elements are added to copper to improve
springs. and add some properties.
 Cutting tools, milling cutters, blades, drill bits, musical  Major alloying elements are zinc, silicon, aluminium, lead,
instruments, agricultural applications, etc. manganese, nickel, phosphorous, tin, magnesium, etc.

Alloy Steel Properties of Copper

 To obtain the specific properties various alloying elements  It has high ductility and malleability.
are added in steel.  It has high electrical and thermal conductivity.
 The specific properties define the applications of steel.  It is non-magnetic in nature.
 The various alloying elements are as follows:  It can be easily alloyed with other metals.
Carbon, Sulphur, Phosphorus, Silicon, Manganese, Nickel,  Its corrosion resistance is also high.
Chromium, Titanium, Tungsten, Molybdenum, Vanadium,
Cobalt etc. Applications of Copper

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 Electrical parts  Valve bodies, ordnance parts, gun barrels, pipe fittings etc.
 Heat exchangers
 Household utensils etc. Aluminium and Its Alloys
 Aluminium is another widely used non-ferrous metal.
Types of Copper Alloys  Aluminium can be easily alloyed with elements like
Copper alloys are basically divided into two major groups: silicon, copper, nickel, zinc, manganese, titanium,
1. Brasses (Alloy of copper and zinc). magnesium etc.
2. Bronzes (Alloy of copper and tin).
Advantages of Aluminium Alloys
Brasses  It has high thermal and electrical conductivity.
 Brasses are alloys of copper and zinc with small amount of  It has high corrosion resistance.
other alloying elements.  It has high toughness.
 According to the percentage of copper and zinc, there are  They are malleable and ductile.
various types of brasses. For example α-brasses.  It can be easily cast and rolled.
 The properties of brasses can be changed by adding small
amount of other alloying elements. Applications of Aluminium Alloys
 Aluminium alloys are widely used in the aircraft industry.
Advantages of Brasses  Motor housings, pump castings, pistons, cylinder heads.
 It has high corrosion resistance.  In food industry, food preparation equipment's,
 It has high ductility and malleability. refrigeration, storage containers, bakery equipment's etc.
 Due to addition of zinc, it has high strength.
 It has high machinability. 2.2.3 Non-Metals
 Now-a-days use of non-metals is increasing in the
Limitations of Brasses industries because of following properties:
 It has low thermal and electrical conductivity. 1. They are having low density.
 Its cost is also high. 2. They are light in weight.
3. Use of non-metals provides flexibility in the design.
Applications of Brasses 4. They have high resistance to heat and electricity.
 Coins, needles, jewellery, condenser tubes. 5. They have low cost.
 Cartridge cases, headlight reflectors, springs.  The commonly used non-metals are as follows:
 Shafts, nuts, bolts, welding rods, machine parts etc. 1. Plastics
2. Ceramics
Bronzes 3. Composites
 Bronzes are alloys of copper and major alloying elements
other than zinc or nickel. Plastics
 But, generally bronzes are alloy of copper and tin.  A large group of engineering materials which have
 Sometimes, it also alloyed with aluminium, beryllium, increasing importance in industrial applications are
silicon etc. composed of natural synthetic organic polymers (Plastics).
 Now-a-days in some of the applications, metal and wood
Advantages of Bronzes parts are replaced by plastics, which have satisfactory
 It has high corrosion resistance. properties and may be produced at lower cost.
 It is comparatively hard than brass.  Plastics are moulded into any required shape by the
 It can be rolled into sheets, rods or wires. applications of pressure and heat, for example toys, chairs,
 It has high tensile strength. refrigerator equipment's and radiator fans etc.
 It has high ductility and malleability.  The plastics can be cast, rolled, laminated and machined
easily.
Limitations of Bronzes  The word ‘mer’ means a unit, monomer stands for a single
 The cost of bronzes is higher than the brasses. unit and polymer means many units joined together by a
chemical reactions.
 The strength of bronzes is lower than the ferrous metals.
Characteristics of polymers/plastics
Applications of Bronzes
 Low density and weight.
 Springs, gears, bearings, electrical appliances.
 High corrosion resistance.
 Bolts, rivets, pressure vessels, bells, marine containers.
 Low thermal, mechanical and electrical properties.

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 Low coefficient of friction.  These type of plastics are used in telephone receivers,
 Excellent surface finish can be obtained. electric plugs, radio and T.V. cabinets, camera parts,
 It can be produced in different colours. automobile parts, switch panels etc.
 It can be produced with close dimensional tolerances.  Some of the commonly used thermosets are: Phenolic,
 It has good mouldability. Epoxies, Aminos (Urea formaldehyde and melamine
 It is more economical than the metals. formaldehyde), unsaturated polyesters etc.

Limitations of polymers/plastics Ceramics

 It has low strength and rigidity.  Ceramics is a compound formed by combination of
 It has poor tensile strength. inorganic and non-metallic materials.
 It has poor temperature resistance.  Ceramics are hard and brittle materials used for high
 It has short life. temperature applications.
 It has poor dimensional stability.  They are mainly oxides, carbides, sulphides and nitrides
of metals.
Types of polymers/plastics
Plastic or polymers are classified into two major categories: Properties of Ceramics
1. Thermoplastic or Thermoplasts (Soften when heated  Ceramics have high hardness and stiffness.
and harden when cooled).  It consists of high strength at high temperatures.
2. Thermosetting or Thermosets (Soften when heated  They have high resistance to abrasion and wear.
and permanently harden when cooled).  Chemical stability of ceramics is good.

Thermoplastics (Thermoplasts) Advantages of Ceramics

 Thermoplastic polymers soften when heated and harden  Ceramics can have excellent compressive strength.
when cooled.  They have low thermal conductivity.
 These types of polymers are soft and ductile.  They have low coefficient of thermal expansion.
 They have low melting temperatures and can be repeatedly  Also, they possess good electrical insulation properties.
moulded and remoulded to the desired shapes.
 These polymers are usually fabricated by the simultaneous Limitations of Ceramics
applications of heat and pressure.  Due to their hardness machinability of ceramics is very
low.
Applications  They are brittle in nature.
 These types of plastics are used in electrical insulations,
toys, machine guards, musical instruments, fuel container Applications of Ceramics
coatings, hoses, photographic films, bottles, gaskets,  Spark-plug insulators, vacuum tubes, metal cutting tool
packing’s, refrigerator parts, floor tiles, plastic lenses etc. tips, grinding wheels, nuclear equipment’s.
 Some of the commonly used thermoplastics are:  Rotor blades in turbines, die materials, engine
Polyamide, Poly-Tetra-Fluaro-Ethylene (PTFE), Poly- components, artificial hip joints, refractory tubes and
Vinyl-Chloride (PVC), Poly-Propylene (PP), Poly- containers.
Ethylene (PE) etc.  Nozzles, bearings, pump parts, electronic parts,
components of paper industry etc.
Thermosetting (Thermosets) polymers
 Thermosetting polymers become soft during first heating Composites
and become permanently hard when cooled. Hence, these  Composite material is defined as a material formed by the
type of polymers cannot be remoulded or reshaped by combination of two or more chemically dissimilar
subsequent heating’s. materials with different boundaries between them.
 These type of plastics are generally more stronger, harder,  Composite material exhibit properties that are vastly
brittle and resistant to heat and solvents than the different from those of the individual constituents and
thermoplast. better suited for a particular applications.
 It they are heated to high temperature, decompositions and  Many composite materials are composed of just two
degradation of the polymer takes place. phases; one is called as matrix (soft phase) which is
continuous and surrounds the other phase i.e. called as
Applications dispersed phase (hard phase).

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Types of Composite Materials  It is the general study of metals and their behaviour with
The composite materials are classified as follows: particular reference to their microstructure and
1. Fiber reinforced composites macrostructure.
2. Particle reinforced composites  Microstructure or microscopic examination involves the
3. Structural composites study of prepared metal surfaces by using a microscope.
 When a higher magnification is used, it gives large number
Fiber Reinforced Composites of structural details of the metals or alloys under
 The hard phase consists of fibres of high strength material. examination.
These fibres are dispersed in the soft and ductile matrix.  Macrostructure or macroscopic examination involves the
 The combined material has better stiffness, strength and study of metals either by the unaided eyes or by using a low
toughness. power magnifying glass.
 The function of fibres is to withstand the load, while  When all features are found by metallographic
matrix ensures uniform distribution of applied load. examination, it is then possible to predict the behaviour of
the metal for a particular service condition with reasonable
Applications accuracy.
 These type of composites are used in piston, connecting  Microstructure and macrostructure of a metal or an alloy
rods, aerospace applications, aircraft wing applications, are closely interrelated with each other and a knowledge of
propeller for ships, cutting tool inserts for machining hard both is necessary for full understanding of any metal.
metals, springs containers, pressure vessels, gaskets etc.
2.4 Classification of Metal Observations
Particle Reinforced Composites  Metallography is a study of the structural characteristics or
 In this type of composites, the strengthening is produced constitution of a metal or alloy, in relation to its physical
by particles of hard material. and mechanical properties:
 The function of particles is to impart strength and stiffness  There are two examination methods in metallography:
to the composite mix. 1. Microscopy
 Matrix ensures uniform distribution of applied load on the 2. Macroscopy
composite. It also provides protective covering to the
particles. 2.4.1 Microscopy
 In microscopy, the examination is done with the prepared
Applications metal specimens, employing magnifications with the
 These type of composites are used in cutting tool materials, optical metallurgical microscope, from 100X to high as
crucibles, jet nozzles, aircraft blades, coatings, bearing 2000X of magnification.
bushing, dies, cylinder liners, brake discs etc.  Microstructural examination can provide quantitative
information about the following parameters:
Structural Composites 1. The grain size of specimen
 Structural composites are made up of two or more 2. The amount of interfacial area per unit volume.
homogeneous materials. 3. The dimensions of constituent phases.
 The properties of these composites depend on the 4. The amount and distribution of phases.
constituent materials and their geometrical design.
 Structural composites can be of laminate type or sandwich 2.4.2 Macroscopy
panel type.  In case of macroscopic examination the nature of in
 In case of laminated composites, two or more layers or homogeneities and flow lines in a metal by unaided dye or
sheets arranged in a stacking order. These sheets are with the help of low power magnifying glass.
cemented by using a bonding agent.  The general distribution and variation in size of non-
 The load on the composites is shared by all the layers. It is metallic inclusions, the uniformity of structure, the location
used as a skin material for aircraft. and extent of segregation, flow lines etc. can be examine
 In case of sandwich panel composites, two strong outer by macroscopy and these cannot be examined by
sheets are separated by a layer of less-dense material. microscopy.
 It is used in roofs, floors and walls of buildings, aircraft 1. Crystalline heterogeneity i.e. manner of solidification
wings etc. and the crystalline growth of the metal or alloy.
2. Chemical heterogeneity i.e. impurities in a metal or
2.3 Metallography alloy.
 Metallography consists of microscopic study of the
structural characteristics of a metal or an alloy.

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3. Mechanical heterogeneity i.e. due to cold working or  After selecting a particular area, the specimen may be
heterogeneity occurs in metals or alloy due cold removed from the metallic piece by sawing or cutting using
rolling or forging etc. abrasive wheel which is carried out on abrasive wheel
cutting machine as shown in fig. no. 2.2.
2.5 Specimen Preparation
 Specimen preparation is necessary to study it’s
microstructure as metallurgical microscope makes use of
the principle of reflection of light to obtain image of the
metal structure.
 A satisfactory image of the microstructure can be obtained
only when the specimen has been carefully prepared.
 Even the most expensive microscope will not reveal the
metal structure, if the specimen has been poorly prepared.
 The procedure to be followed in the preparation of a
specimen is simple but the technique gets develop only
after practice.
 The final objective is to produce a flat, scratch free and a
mirror like finish surface.
 The procedure for preparing the specimen for both Fig. No. 2.2 Abrasive cut-off wheel
microscopy and macroscopy examination is the same  The specimen shall be kept cool during the cutting
except that in the case of microscopy the final surface operation. While cutting, care must be taken to minimize,
finish is more important. altering the microstructure of the metal.
 The steps required to prepare a metallographic specimen
are as under: 2.5.3 Rough Grinding
1. Selection of specimen  After cutting, a soft specimen may be made flat by slowly
2. Cutting of specimen moving it up and back across the surface of a smooth file,
3. Rough grinding and hard specimens may be rough ground on a belt grinder.
4. Mounting of specimen
5. Fine grinding
6. Polishing
7. Etching

2.5.1 Selection of Specimen

 Specimen should be selected from, that area of a metal,
which can be taken as representative of the metal that is
being studied.
 In case of study of failures, specimen should be taken as
close as possible to the fracture or to the initiation of the
failure.
 Generally in many cases, specimens are required to be
taken from a sound area for a comparison of structure and
properties. Fig. No. 2.3 Belt Grinder
 After deciding the location of the specimen, the type of  Rough grinding is continued until all scratches due to the
section to be examined must be decided. The location of hacksaw or cut-off wheel are no longer visible and the
surface examined should always be given in reporting surface is flat.
results.  Due to rough grinding surface damages, created by cutting
 Size of specimen be proper for handling during all sample discs, are reduced by grinding. The belt grinding paper is
preparation techniques. made up of silicon carbide abrasive.
 If the specimen sample is too small, then it should be
mounted on the mounting press along with thermosetting 2.5.4 Specimen Mounting
resign or cold mounting process.  It is carried out for convenience in handling it during the
subsequent steps of metallographic preparation and
2.5.2 Cutting of Specimen examination. For this the specimen is mounted.

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 Compression mounting involves mouldings around the is preferred for specimens that are sensitive to head or
specimen by a material like Bakelite, acrylic resins, by pressure, as in case of hot mounting used.
application of heat and pressure. This is known as hot
mounting process. 2.5.5 Fine Grinding
 Epoxy or polyester resins are used for cold moulding, and  After rough grinding the specimen is finely ground using
this is known as cold mounting process. fine abrasive paper (grit sizes from 180 mesh to 600 mesh).
 This abrasive grit size is as per ANSI standards (American
National Standards Institute) system units.
 Fine grinding is generally carried out on many papers, of
grades from 01 to 04 i.e. 01 is coarse grained and its
fineness goes on increasing towards 04.

Fig. No. 2.5 Emerry Papers

 This fine grinding is carried out on a series of stages with
increasing the fineness of the paper i.e. from 01 to 04.
Fig. No. 2.4 Mounting Press  Each grinding operation on a paper, will remove the marks,
 Also due to mounting of metallurgical specimen, serves for produced in the previous operation.
protection of the specimen edges and improvement of its  After each grinding stage the specimen should be
irregular shape, which become more convenient during thoroughly washed in order to prevent carry over the
grinding and polishing. coarser grit to the next grinding paper.
 The grinding direction during each stage should be change
Hot and Cold Mounting by 90° relative to the direction of the previous stage.
 Specimen mounting is necessary because very thin,  This makes easier indication of completion of the grinding
irregular shape specimens are difficult to handle during stage (removal of the scratches from the previous stage).
sample preparation techniques, due to which those
specimen are mounted by two methods. 2.5.6 Polishing
1. Hot mounting  The fine scratches caused by final grinding operation are
2. Cold mounting removed by polishing. Polishing is carried out on single
disc or double disc polisher.
Hot Mounting
 In this process a small hydraulically operated press is used
and which is consists of a small furnace/ heater to heat the
resin material.
 A temperature up to 200°C and a pressure upto 50 kN are
applied during the embedding of the specimen.
 A thermoplastic resin material is used. A small metallic
mould is used to embedding the specimen, in the resin
material.

Cold Mounting Fig. No. 2.6 Double disc polishing machine

 As this process is carried out room temperature it is known  The time consumed and the success of polishing depends
as cold mounting. A resign material in the powder form is largely upon the care that was taken during fine grinding.
mixed with a hardener to provide the mounting compound.
 The final approximately flat scratch free surface is obtained
 This slurry or a mixture is then poured around the by use of a wet rotating wheel covered with special cloth,
specimen, surrounding to metallic mould. Cold mounting charged with abrasive particles.

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 Unit II Micro and Macroscopic Study of Metals

 During polishing, the specimen is rotated in a direction,  Electrolytic polishing does not disturb any metal on the
counter to the rotation of the polishing wheel. specimen surface and therefore ideally suitable for the
 In addition the specimen is continuously moved back and metallographic preparation of soft metals, most single
forth between the centre and edge of the wheel, thereby phase alloys, alloys that work harden readily.
ensuring even distribution of the abrasive and uniform  The disadvantages of electrolytic polishing includes,
wear of the polishing cloth. chemical attack in multiphase alloys due difference in
 A wide range of abrasives is available. Generally alpha electrical potential between phases.
grade of aluminium oxide is used for rough polishing on
one polishing wheel while gamma grade of aluminium 2.5.7 Etching
oxide is used for fine polishing on other polishing wheel.  Etching is defined as, a intentionally made chemical attack
 After polishing i.e. after obtaining a mirror finish image on on the prepared metallic specimen surface, to reveal
the specimen surface, the specimen is washed in warm microstructure or micro constituents.
running water, rinsed with methanol or any other alcohol  The purpose of etching is to make visible structural
that does not leave a residue, and dried in a stream of warm characteristics of the metal or alloy. This is achieved by a
air. use of an appropriate etching reagent which carry out
chemical action on a polished surface.
Electrolytic Polishing  Etching is done by immersing the polished surface in the
 During metallographic sample preparation techniques, reagent or by rubbing the polished surface gently with
even most care is taken during mechanical polishing, some cotton swab, wetted with the etching reagent.
disturbed metal however will remain after preparation of a  After etching the specimen is again washed thoroughly and
metallographic specimen. dried. Now the specimen can be studied under a
microscope.
 The selection of the appropriate etching reagent is
determined by the metal or alloy and the specific structure
desired for viewing.
 The common etching reagents used for various metals and
alloys are as under.
Table No. 2.1 Various etching reagents with their
applications
Etching Composition Use
Reagent
White 4 nitric acid “1
Carbon steels
Nitric Acid to 5 ml ethyl or methyl
and cast iron
alcohol”
Picric acid “4 g ethyl or
Picric Acid Carbon steels
methyl alcohol”
Ferric chloride 5 g Structure of
Ferric
Fig. No. 2.7 Electrolytic Polishing Hydrochloric acid 50 austenitic nickel
chloride
 If the specimen is to be examined in the as polished ml water 100 ml stainless steels
condition, however, or if no surface disturbance can be Ammonium Ammonium hydroxide
accepted or tolerated, either electrolytic polishing or hydroxide & 5 parts water 5 parts Copper and its
chemical polishing is preferred. hydrogen hydrogen peroxide 2 to alloys
 As shown in fig. no. 2.7, an electrolytic reaction cell peroxide 5 parts
containing a liquid electrolyte with two electrodes, an Copper, brass,
Ammonium per
anode and cathode. Ammonium bronze,
sulphate 10 g water 90
 The sample to be polished/etched forms an anode. The per sulphate
ml
aluminium silver,
electrodes are connected to an external power supply and nickel
voltage applied to cause reaction within the cell. Chromic oxide 200 g
Palmerton Zinc and its
 In electrolytic polishing the specimen is the anode in an reagent
sodium sulphate 15 g
alloys
electrolytic cell. Direct current from an external cell is water 1000 ml
applied to the electrolytic cell under specific conditions, Ammonium Molybdic acid 100 g Lead and its
and anodic dissolution results in a levelling and brightening molybdate ammonium hydroxide alloys
of the specimen surface. Hydrofluoric Hydrofluoric acid 0.5 Aluminium and
Acid ml its alloy

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2.6 Determination of Microstructure therefore the complete surface will look brighter under
 As shown in the ray diagram of metallurgical microscope microscope.
(Refer Fig. No. 2.8).  With fig. no. 2.9 (b) shows and microstructure after etching
which reveals grain boundaries, because the light rays
following on grain boundary are get scattered and due to
which they cannot pass through objective lenses.
 Because of which grain boundary will look dark under
microscope while the grain will look bright.
 With reference to fig. no. 2.9 (c) which shows the
microstructure of a multi-phase metal or alloy. It reveals
grain shading and grain boundaries as a result of etching.
 In this example the amount of reflected light captured by
the objective lens of the microscope will vary from one
grain to another.
 This will lead to some grain appearing to be light in colour
and others appearing dark, even though all the grains may
be identical in composition and type.

Fig. No. 2.8 Determination of Microstructure 2.7 Microscopic Techniques

 The prepared specimen is placed perpendicular to the  The microscopic techniques are base classified as follows:
optical axis of the microscope and is illuminated through
the objective lens by light from the source.
 The light rays is then reflected from the surface of the
specimen, which are then magnified in passing through the
objective lens and will continue upward through the plane
glass reflector and gets magnified again by the eye piece.
 The direction of light reflected from specimen depends on
specimen surface condition as shown in fig. no. 2.8.
 The light is reflected from the surface of the specimen in to
objective lens from features approximately normal to the
optical axis and away from objective lens from features
inclined to the optical axis as shown in fig. no. 2.9. Fig. No. 2.10 Classification of Microscopic Techniques

2.8 Optical Metallurgical Microscope

Fig. No. 2.9 Observation of metallography specimen

 The final image of specimen which is formed by the
eyepiece, is therefore bright for all features normal to the
optical axis (grain) and dark for inclined features (grain
boundary).
 In this way the various grain size determination, and the
various microstructural features, inclusions, precipitated
particles etc. can be revealed.
 As shown in fig. no. 2.9 (a) represent metallic specimen
surface duly polished and in unattached condition.
 All the light rays following on the specimen surface, are all
reflected back and passing through objective lenses, Fig. No. 2.11 Optical Metallurgical Microscope

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 Microscope is a device used for obtaining more resolution  All these have a great effect on mechanical properties of
and magnification. Finer details can be easily and clearly material List of Modern Microscopes.
examined by using this microscope. 1 Watson Royal Microscope.
2 Van Lanes Hock Microscope.
3 Glass led Microscope.
4 Baker series Microscope
5 Leitr Microscope
 Opaque metals cannot be viewed by the transmitted light,
hence they are viewed by the reflected light.
Working
 A horizontal beam of light from a suitable light source (like
electric bulb) falls on a silvered portion of a semi-silvered
glass plate which is kept at an angle of 45° with vertical
axis in the movable tube.
 The light get reflected vertically downwards travel through
the objective and fall on the surface of specimen.
 The light rays that are reflected by flat and polished
Fig. No. 2.12 Reflected Light Microscope Anatomy specimen surface travel through the objective and come to
 It consists of a stand which is attached to a movable tube the eyepiece.
which contains the optical parts and device for illuminating  The image can be observed through the eyepiece, or these
the specimen. Refer fig. no. 2.12. rays can be focused on the screen or a photographic plate
 Constructional Details:- The table type can be kept to record the image and view it.
microscopes are consist of  In some of the microscope, instead of semi-silvered glass
 Stage: - A flat movable table supporting specimen. This plate prism reflectors are used.
can be moved up or down by knobs.
 Tubes: - The vertically movable tube containing eyepiece, 2.9 Electron Microscopy
objective and plane reflector. The tube length varies from  Electron microscopes are quite different from optical
160 mm to 250 mm. microscopes.
 Rough & fine focus Adjustments - The limbs of  In these microscopes, a high velocity electron beam is
microscope carry the coarse & fine adjustments to facilitate used instead of ordinary light.
the  The resolving power of electron microscope is very high
 Objective - The body tube carries revolving nose piece as the wavelength of electron beam is small i.e. 0.05 to 0.07
carrying the three objectives. This enables quick change of A°.
the objective which helps for a quick resolving the  The magnification obtained is very high in the range of 1
structure of metal, the magnification of lenses is enlarged to 5 lakhs.
on focal length of the lens used.
 The important properties of an objective are-
1 Magnifying Power
2 Resolving Power.
 It is the property by which an objective shows distinctly
represented two small adjacent bonds in the structure of the
object. This is usually expressed as number of lines per mm
that can be separated which depends on the numerical
operator, the wavelength of the light used. Resolution is
particularly important during the microscopy of the micro
constituents of metals consisting of fine lamination with
core resolution which appears as one uniform area, where
as an objective with higher numerical appearance reveals
deeper nature of the structure.
 Eyepiece - It is named, as it is near to the eye. It is made
up of various Powers such as X5, XI0, X 15 etc.
 Uses - The metallurgical microscope is useful in quality
control department in Industries to observe & study 1) Fig. No. 2.13 Electron Microscope
Differential phases 2) Porosity or defects.

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 The vertical resolution of electron microscope is about 2  The objective lens collects the electrons from the specimen
microns which is much higher than that of optical to form first image with a magnification of say X 40.
microscopes.  Further, additional magnification lenses including final
 All the electron microscopes are built on the principle of projection lens create the final image on the viewing
transmission and hence it is required to have a very thin screen.
sample to study the details clearly with TEM.  This method is useful in identifying defects, their
 The electron beam reflects at an angle of incidence of about crystallographic planes and other parameters.
1° and hence examination of bulky specimens is possible
by using this reflected electron beam. Advantages
 The basic arrangement of electron microscope is shown in  It has a good magnification of about 5000000 X.
fig. no. 2.13.  It is possible to investigate the fault into a greater depth of
field.
2.10Transmission Electron Microscopy (TEM)  TEM has better resolution of 0.2 nm than SEM which has
a resolution of only 2 nm.

Disadvantages
 The images obtained are in black and white form.
 The specimen required in TEM should be very thin.
 It is expensive and time consuming process.

Applications
 Direct observation of dislocations.
 Observation of stacking faults.
 Formation of sub grains without recrystallization in
warm/hot deformation.
 Precipitate behaviour in high temperature alloys.
 The fine phases causing temper brittleness in alloy steels,
etc.

2.11Scanning Electron Microscopy (SEM)

Fig. No. 2.14 Transmission Electron Microscopy

 In the transmission electron microscopes (TEM), which
were developed in the early stages, the samples used are
made very thin, so that the beam penetrates through the
sample and the transmitted beam is used for forming the
image.
 The samples may be replicas of the material surface or
original material in the form of thin films made by
electrochemical or electrolytic polishing methods.
 The electron source (electron gun) can be electrically
heated tungsten filament (or a higher quality source for
probe or high resolution work). Fig. No. 2.15 Scanning Electron Microscopy
 The electron beam is accelerated by the applied voltage and
collimated by condenser lens, so that a parallel beam of  For scanning electron microscopy, bulk specimens can be
about 25 µm or smaller is incident on the thin specimen. suitable as used in optical microscopy, but they have poor
resolution and high image distortion.

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 In a scanning electron microscope electron microscope, an 2.12.1 Atomic Force Microscopy (AFM)
electron beam is focused to a spot of about 20-100 nm
diameter and made to scan the sample surface in a raster.
 The sample will be a thick sample of conducting material.
 The electron gun may operate at 30-60 kV.
 This microscope provides a probe-forming system, with
each lens condensing and demagnifying the electron source
to a focused spot on the sample surface.
 Commonly the probe is 10-40 nm in size. Smaller probes,
around 3 nm or smaller are achieved using higher intensity
probes of coherent, field emission gun (FEG) electron
sources.

Advantages
 SEM is easy to use. Fig. No. 2.16 Atomic Force Microscope
 The sample/specimen required can be any thickness.  In atomic force microscope (AFM), the interaction force
 The sample can be viewed as a 3D image on viewing between the probe and surface structural features is
screen. measured to reveal the surface topography in a direct
fashion.
Disadvantages  The probe is at the tip of a cantilever placed parallel to the
 The resolution is not good as that of TEM. surface.
 The specimen used must be conductive.  In common instruments, the movements of the cantilever
 The specimen can be viewed as a 3D image on viewing are seen in the form of deflection of a laser beam from a
screen. mirror at the back of the cantilever. The measured signal is
then used to control the system.
Applications  The microscope can operate in a constant force or constant
 SEM’s have a variety of applications in a number of height mode.
scientific and industry related fields, especially where  In general, scanning force microscopes measure forces in
characterizations of solid materials is beneficial. the range of 10-9 to 10-6 N and the mechanical properties of
 A scanning electron microscope is used to detect and the cantilever such as the spring constant, the resonant
analyse surface fractures, provide information in frequency and stiffness of the beam are important.
microstructures, examine surface contaminations and  The cantilever must have a very small mass, so micro-
identify the crystalline structure. fabrication techniques are used.
 SEM have industrial and technological applications such
as semiconductor inspection, production line of extremely Advantages
small products and assembly of microchips for computers.  AFM provides three dimensional surface profile.
 Samples viewed by AFM do not require and special
2.12Scanning Probe Microscope (SPM) treatments that would irreversibly change or damage the
 Scanning probe microscopy (SPM) is a branch of sample.
microscopy that forms images of surfaces using a physical  AFM technique can be used both in air and liquid.
probe that scans the specimen.
 An image of the surface is obtained by mechanically Disadvantages
moving the probe in a raster scan of the specimen, line by  The AFM can only image a maximum height of the order
line, and recording the probe-surface interaction as a 10-20 micrometres and maximum scanning area of about
function of position. 150 x 150 micrometres.
 SPM techniques have been applied over a wide range of  The scanning speed of AFM is slow. It cannot scan images
materials. as fast as a SEM.
 Types of scanning probe microscopy are:
1. AFM (Atomic Force Microscopy) Applications
2. EFM (Electrostatic Force Microscopy)  Atomic force microscopy is a powerful and widely used
3. MFM (Magnetic Force Microscopy) imaging technique that can visualize single molecules both
4. STM (Scanning Tunnelling Microscopy), etc. in air and liquid (solution).

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 If we use AFM tip as an end-effector, an atomic force 2.13 Grain Size

microscope can be modified into a nano robot that can  It is important to study the grain size of polycrystalline
manipulate objects in nanoscale. metals.
 Atomic force microscope is now actively used in material  The grain size is specified in terms of average grain
sciences and biological fields. volume, diameter or area.
 The grain size has an influence on the mechanical
Comparison between TEM and SEM properties of the metal viz. ductility, strength, toughness
Table No. 2.2 Comparison of TEM and SEM etc.
S. N TEM SEM  Usually, fine grained structures have better mechanical
TEM has higher SEM has lower properties as compared to coarse grained structures.
1 resolution of about 1 nm resolution of about 2  Hence, many time, special treatments such as heat
or less. nm only. treatment are carried out to refine the grain structure.
Specimen preparation is Specimen preparation  The effect of grain size on some of the mechanical
2
time consuming. is simple and fast. properties is mentioned below:
The specimen required The specimen required Table No. 2.4 Effect of grain size on mechanical properties
3 should be thin. can be of any Coarse Fine
thickness. S.
Property Grained Grained
Transmission electron Scanning electron N.
Structure Structure
4 microscopes are microscope is cheaper 1 Yield Strength Less More
expensive. comparatively. 2 Tensile Strength Less More
The images obtained are The sample can be 3 Toughness Less More
5
in black and white form. viewed as a 3D image. 4 Resilience Less More
TEM shows multiple SEM shows only the 5 Hardness Less More
characteristics of object morphology of
6 6 Fatigue Resistance Less More
such as crystallization, specimens.
7 Creep Resistance More Less
morphology, stress, etc.
8 Corrosion Resistance More Less
They are harmful to SEM are safe to use.
7 9 Ductility Less More
human health.
10 Hardenability More Less
Comparison between Electron Microscope and Optical
Microscope 2.14 Grain Size Determination
Table No. 2.3 Comparison of Electron Microscope and  Determination of grain size essentially depends on the
Optical Microscope properties of polycrystalline materials.
S. N. Electron Microscope Optical Microscope  There are many techniques in which grain size is specified
In electron microscope, In optical microscopy, in terms of average grain volume, diameter or area.
1 high velocity electron ordinary light is used.  Following are the techniques commonly used for the grain
beam I used. size determination.
The resolving power is The resolving power is 1. Comparison Method
2 2. Heyn’s Intercept Method
very high. low comparatively.
The depth of focus is of The depth of focus is of 3. Jefferies Planimetric Method
3
the order 2 µm. the order 0.06 µm.
Magnetic or Optical lens are used in 2.14.1 Comparison Method
electrostatic lens are optical microscope.  Comparison method is mainly used for equiaxed grains and
4 this method is device by ‘ASTM’.
used in electron
microscope.  ASTM has prepared number of standard comparison
The visual image is The image is observed charts, all having different average grain sizes.
obtained on a viewing through a eyepiece.  Each average grain size is characterized by ASTM grain
5 size number.
screen / fluorescent
screen. N = 2n-1
The wavelength of The wavelength of Where, N= Number of grains per square inch at 100X
6 electron microscope is optical microscope is magnification
about 1 nm. about 400-700 nm. n= ASTM grain size number.

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 Following Table No. 2.5 shows the ASTM grain size 2.14.3 Jefferies Plainmetric Method
number along with corresponding average number of  It is similar to the Heyn's intercept method, with the
grains. difference that it is based on area intercept rather the line
Table No. 2.5 ASTM Grain Size Numbers intercept.
Average number  A photomicrograph of the grain structure of the sample is
ASTM Actual average
of grains per obtained with a suitable magnification.
grain diameter of
S. square inch of  The magnification should be such that at least 50 grains
size equivalent spherical
N. 100X should be seen in the above photomicrograph.
number grain in microns (1
(n)
magnification
micron= 10-3 mm)  A circle or a rectangle of known area is drawn on the
(N) photomicrograph.
1 1 1 287  The actual area covered by the circle or rectangle should be
2 2 2 203 at least 5000 mm2.
 The total number of grains covered by the circle or
3 3 4 144 rectangle is counted.
4 4 8 101 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑟𝑎𝑖𝑛𝑠 𝑝𝑒𝑟 𝑠𝑞𝑢𝑎𝑟𝑒 𝑚𝑖𝑙𝑖𝑚𝑒𝑡𝑒𝑟
5 5 16 71.8 = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑟𝑎𝑖𝑛𝑠 𝑐𝑜𝑣𝑒𝑟𝑒𝑑 × 𝐽𝑒𝑓𝑓𝑒𝑟𝑖𝑒𝑠 𝑀𝑢𝑙𝑡𝑖𝑝𝑙𝑖𝑒𝑟 (𝑓)
 Jefferies Multiplier (f) is a function of the magnification
6 6 32 50.7 used as given in the following table no. 2.6.
7 7 64 35.9 Table No. 2.6 Jefferies Multipliers
8 8 128 25.4 Magnification used f
9 9 256 18 1 0.002
10 10 512 12.7 10 0.02
 Larger grain size number represents the smaller grains in 25 0.125
size. 50 0.5
 The specimen in this method must be properly prepared to
disclose the grain structure. 75 1.125
 This specimen is then photographed at 100 x 100 2
magnification. This is known as micrograph. 150 4.5
 The grain structure micrograph is then compared with the
200 8
sizes given in the above charts at 100 x magnification.
 The matching number after matching the structure with 250 12.5
standard charts is found out. 300 18
500 50
2.14.2 Heyn’s Intercept Method
 Intercept method is mainly used for non-equiaxed grains or 750 112.5
elongated grains. 1000 200
 In this method, straight lines of same length are drawn on 1500 450
the photomicrograph of the specimen that shows the grain
structure. 2000 800
 The magnification employed should be such that area
covered is atleast 0.5 mm2 on the actual sample. 2.15 Macroscopy
 Hence, grains intersected by each line are counted.  In case of macroscopic examination the nature of in
 The average grain size at 100 x magnification can be found homogeneities and flow lines in a metal by unaided dye or
out by, with the help of low power magnifying glass.
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑔𝑟𝑎𝑖𝑛 𝑠𝑖𝑧𝑒 𝑎𝑡 100𝑋  The general distribution and variation in size of non-
𝑇𝑜𝑡𝑎𝑙 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑙𝑖𝑛𝑒 𝑎𝑡 100𝑋 metallic inclusions, the uniformity of structure, the location
=
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑔𝑟𝑎𝑖𝑛𝑠 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑙𝑖𝑛𝑒 and extent of segregation, flow lines etc. can be examine
 The result of the above equation is divided by the linear by macroscopy and these cannot be examined by
magnification photo micrograph i.e. by 100 to get the microscopy.
actual grain diameter.  Crystalline heterogeneity i.e. manner of solidification and
the crystalline growth of the metal or alloy.
 Chemical heterogeneity i.e. impurities in a metal or alloy.

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 Mechanical heterogeneity i.e. due to cold working or  Now, the dark brown spots on the print indicates presence
heterogeneity occurs in metals or alloy due cold rolling or of sulphur segregation whereas a random dispersion of the
forging etc. spots denote a more uniform and less harmful distribution
 The results obtained by metallurgical microscopy are not of sulphur.
representative of entire component because of the  The chemical reactions that occurs during the sulphur
heterogeneous nature of these materials. printing are as follows:
 Macroscopic examination is the process of examining the FeS (or MnS) + H2SO4 FeSO4 (or
metals with or without proper etchant and by unaided eyes
or by a magnifying glass. MnSO4) + H2S
 Macroscopy is mainly used for investigation of defects and
structures. 2 AgBr + H2S Ag2S + 2HBr
 As compared to microscopy, a large surface observation is
possible in macroscopy. Also preparation of specimen is
easy in macroscopy.  The entire sulphur printing process can be conducted in day
1. Uniformity of structure light. The good results are obtained only on first and second
2. Distribution of non-metallic inclusions print from the prepared surface of a metal.
3. Extent of segregation  Sulphur printing is used to find the sulphur distribution in
4. Presence of defects an ingot, a forging or a hot rolled product.
5. Examination of fractures
6. Flow lines in extruded, forged and drawn parts. 2.17 Flow Lines Observations
 For correct evaluation of the surface details, high level of  Flow lines indicate the direction in which the steel was
skill and experience is required. mechanically worked.
 For some of the macroscopic examinations like  We know that, forged components have better properties
examination of fractured surfaces, etching of the surfaces than the cast, rolled and machined components.
is not required.  Also the properties of forged components are governed by
the metal flow pattern.
2.16 Sulphur Printing  Hence, it is necessary to know whether the component is
 Sulphur printing is used to detect sulphur in ferrous metals manufactured by forging, casting, rolling or machining.
and alloys.  It is achieved by macro-etching the polished surface of
 It is also produces a permanent record of sulphur component in a 50% aqueous solution of hydrochloric acid
distribution in steel. (HCl) at 60 to 70°C for 5 to 10 minutes.
 To reduce the harmful effect of sulphur, manganese is  Sometimes, 10 to 12% solution of ammonium per sulphate
added. (NH4)2S2O8 can also be used for etching at room
 Sulphur printing is used to determine distribution of temperature.
sulphur impurity in the steel sample. Sulphur impurity has  If the macro-etched surface shows a directional flow
the effect of including brittleness in the steel or the pattern consisting of streaks and striations, it means the
distribution of such impurities in the steel is very component is forged.
important.  The flow lines are observed because the elongated
 The surface of the specimen is initially polished on 0 or 00 inclusions and other elongated heterogeneous areas are
number emery paper and then washed under running water. attacked by the etching reagent.
 A matt finish photographic bromide paper is soaked in 2%  Highly stressed areas are also etched effectively.
aqueous solution of sulphuric acid for 3 to 4 minutes.  It is important to note that, observation of flow lines on the
 The paper is taken out from the solution and excess drops macro-etched surface is an indication of mechanical
of solution are removed. working and not an indication of defect.
 The emulsion side of the paper is then kept in contact with
polished surface of the specimen for 2 to 3 minutes with
moderate pressure.
 The photographic paper is then removed from the surface
of specimen, washed in running water and then it is
immersed in photographic fixer solution for about 15
minutes.
 Finally, the paper is taken out from the solution, washed
in running water for about 60 minutes and dried.
Fig. No. 2.17 Flow Lines Observation

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 Fig. no. 2.17 shows the flow lines in a forged component.

Cast component do not show flow lines. Broken and
discontinuous flow lines are observed for a rolled and
machined component.

2.18 Spark Test

 Spark test is a simple test used for identification of Metals
and their alloys before a detailed chemical analysis.
 This test is performed by holding a piece of metal or alloy
against a revolving grinding wheel.
 The grinding wheel tears off the small particles from the
metal. These heated, glowing particles of metal produce a
visible beam of sparks.
 The characteristics of spark produced are observed to
identify the metal or alloy.
 Various grades of steel gives typical pattern of sparks that
serves as a mean or identification. The colour, shape,
average length of spark helps in determining the material
being tested.

Fig. No. 2.19 Types of Sparks

Fig. No. 2.18 Spark Test

 The fig. no. 2.18, 2.19 and 2.20 shows the various types of
sparks given off by metals. Fig. No. 2.20 Result of Sparks Test

ENGINEERING METALLURGY (202049) 43

 Unit II Micro and Macroscopic Study of Metals

2.18.1 Difference between Microscopic and Macroscopic 2. Explain how Microscopic and Macroscopic
Examination examination are useful in investigation failure analysis
Table No. 2.7 Difference between Microscopic and in metals. (Refer Section. 2.4)
Macroscopic Examination 3. What is spark test? Where is it applicable? (Refer
S. Microscopic Macroscopic Section. 2.18)
N. Examination Examination
This is carried out at
This is carried at lower November 2017 Examination
magnification or with
1 higher magnification 1. Differentiate between microscopy and macroscopy.
naked eyes (less than
(more than 50X).
50X). (Refer Section. 2.18.1)
This requires higher This does not require 2. Explain any two methods of grain size measurement.
2 degree of mirror finish mirror finish specimen (Refer Section. 2.14)
specimen surface. surface. 3. Differentiate between transmission electron
Very high skill is required Not very high skill is microscope and scanning electron microscope. (Refer
3 Table No. 2.2)
for investigation. needed for investigation.
Different types of phases No such phases are
4
can be observed. observed. May 2017 Examination
Very much time
Comparatively fast 1. Is etching of a metallographic sample necessary to
5 consuming (slow
process. measure the grain size of a plain carbon steel sample?
process)
6 Highly expensive Not so expensive Explain why? (Refer Section. 2.5.7)
7 Very high initial cost Very low initial cost 2. What is metallography? What useful information can
Best e.g. observation of be obtained from it? (Refer Section. 2.3)
different phases Best e.g. sulphur printing 3. What is spark test? What is its use? (Refer Section.
8 2.18)
inclusions, flow line observation.
microstructure of a metal.

University Question

November 2019 Examination

1. With the help of a neat sketch explain the difference in
the flow lines observed in forged components and cast
components. (Refer Section. 2.17)
2. State True or False and Justify:
Etching is essential for the study of inclusions. (Refer
Section. 2.5.7)
3. State the working principle and applications of
scanning electron microscopy. (Refer Section. 2.11)

May 2019 Examination

1. What is spark test? What is its use? (Refer Section.
2.18)
2. List the steps in process used to prepare a
metallographic sample for observation under optical
microscope. (Refer Section. 2.6)

November 2018 Examination

1. Is etching essential every time? Explain with suitable
example. (Refer Section. 2.5.7)

ENGINEERING METALLURGY (202049) 44

 Unit III Iron-Carbon Alloy System and Cast Iron

Unit – III
Iron-Carbon Alloy System and Cast Iron

Syllabus:
Iron-iron carbide equilibrium diagram, critical temperatures, solidification and microstructure of slowly cooled
steels, structure & property relationship, classification and application of steels.
Cast Irons: Classification, Manufacturing, Composition , Properties & applications of white C.I., Grey cast iron,
malleable C.I., S.G. cast iron, chilled and alloy cast iron, effect of various parameters on structure and properties
of cast irons. Specific applications such as machine tools, automobiles, pumps, valves etc.
Introduction to non-equilibrium cooling of steels, widmanstaten structure

Part A: - Iron-Carbon Alloy System

Section No. Topic Name Page No.
3.1 Introduction 46
3.2 Pure Iron, Allotropy 46
3.3 Iron-Iron Carbide Equilibrium Diagram 46
3.4 Reactions in Iron-Iron Carbide Equilibrium Diagram 48
3.5 Critical Temperature 50
3.6 Solidification and Microstructures of Slowly Cooled Steels 50
3.7 Non-Equilibrium Cooling of Steels 54
3.8 Widmanstaten Structure 54
3.9 Structure and Property Relationship 55
3.10 Classification and Applications of Steels 55

ENGINEERING METALLURGY (202049) 45

 Unit III Iron-Carbon Alloy System and Cast Iron

3.1 Introduction Stage 1: Temperature 1539°C & Above

 Steel is the most widely used engineering material.  The melting point of Iron is 1539°C.
 Steels are alloys of iron and carbon in which carbon varies  It exists in liquid state above 1539°C.
in between 0.008 to 2%. Stage 2: Cooling from temperature 1539°C to 1400°C
 Steels are most important to the society because of their  Iron starts solidifying below 1539°C.
wide range of properties and versatile applications.  It solidifies in the B.C.C. (delta) form.
 Steels containing only carbon as the alloying element are Stage 3: Cooling from temperature 1400°C to 910°C
referred to as plain carbon steel.  On further cooling at 1400°C, a phase change occurs and
 The equilibrium diagram of plain carbon steels the atoms re-arrange themselves to form F.C.C (gamma)
representing the effects of temperature and composition on structure.
the phases present is known as Iron-Iron carbide  The iron is non-magnetic in this temperature range.
diagram. Stage 4: Cooling from temperature 910°C to 768°C
 The properties of steels depend upon the percentage of  At 910°C, another phase change occurs from F.C.C
carbon and the amount of these phases. (gamma) to B.C.C (alpha).
 The iron is still non-magnetic in this temperature range.
Stage 5: Cooling from temperature 768°C to room
3.2 Pure Iron, Allotropy temperature
 Pure Iron is also referred to as Ingot Iron or Pig Iron.  At 768°C, the non-magnetic B.C.C (alpha) iron becomes
 It is obtained from the blast furnace by reduction of iron magnetic B.C.C (alpha).
ore.  There is no change in the lattice structure.
 Pure Iron also contains small traces of Mn, P, S and Si.  The temperature at which the magnetic property of metal
 It is an Allotropic metal. (It is defined as the ability of a changes is referred to as ‘Curie Temperature’ i.e. 768°C for
single substance to exist in more than one physical form). iron.
 Allotropy is the existence of metal in more than one type  The structural or phase changes during solidification result
of lattice structure (e.g. B.C.C / F.C.C.) at various levels of in volume change of Iron in the temperature range.
temperature.  All the transformation changes give off heat during
 At room temperature, iron is B.C.C. in lattice structure, cooling and absorb heat during heating process.
whereas on heating at 910°C it changes to F.C.C.
 Allotropy of Iron is also termed as Polymorphism of Iron. 3.3 Iron-Iron Carbide Equilibrium Diagram

Fig. No. 3.1 Cooling Curve of Pure Iron indicating phase

transformations Fig. No. 3.2 Iron-Iron Carbide Equilibrium Diagram

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 Unit III Iron-Carbon Alloy System and Cast Iron

 When carbon is added as alloying element, the specific B) Austenite

temperatures at which phase transformation occurs get  It is the interstitial solid solution of carbon in gamma (γ)
altered. iron which is a FCC structure.
 As carbon is the main alloying element in steel, it is  The solubility of carbon in γ-iron is 2.0 % at 1147°C.
important to study the phase diagram of iron and carbon in  It is soft, ductile, malleable & non-magnetic phase.
steel.  It is stable up to 727°C on cooling.
 The Iron-Iron Carbide equilibrium diagram represents the  Below 727°C, austenite decomposes into ferrite and
phase changes that occur during cooling and heating of cementite.
steel.  Hence, most steels are not worked in the soft austenite
 It also establishes a co-relation in between the properties of phase, followed by specific cooling rate to get desired
steel and phases of the microstructure. composition of ferrite and cementite at room temperature.
 The iron and carbon alloys (steel) starts with 0.008%  Region C-E-J-P-R-C represents Austenite Phase.
carbon and extends up to 6.67% carbon as maximum.
 The Iron-Iron Carbide equilibrium diagram begins with
Iron and ends with Iron Carbide.
 The equilibrium diagram is plotted with Carbon % (by
weight) on X-axis versus Temperature (°C) on Y-axis.
 Refer Fig. No. 3.2 for Iron-Iron Carbide Equilibrium
Diagram.
 The diagram shows the following phases or micro-
constituents of Iron and Carbon alloy:

A) Ferrite Fig. No. 3.4 Austenite Microstructure

 It is almost a pure iron phase.
 The name ferrite comes from Latin word ferrum meaning C) Pearlite
Iron.  It is mixture of ferrite & cementite formed by cooling of
 It exists in two forms: austenite.
α-Ferrite:  The ferrite and cementite exist in the form of alternate
 It is the interstitial solid solution of carbon in alpha iron lamellae.
which is a BCC structure.  It exists at room temperature.
 It exists at room temperature.  It shows better strength & hardness.
 The solubility of carbon in α-iron is 0.008% at room
temperature which increases to 0.025% at 727°C.
 It is soft & ductile phase.
 It can be extensively cold worked without cracking.
 It is strongly magnetic up to 768°C, above which on
heating it becomes non-magnetic.
 Region O-D’-D-C-O represents α-ferrite phase.
δ-Ferrite:
 It is the interstitial solid solution of carbon in delta iron Fig. No. 3.5 Pearlite Microstructure
which is a BCC structure.  Refer fig. no. 3.5 for typical micro-structure of pearlite.
 It exists only at high temperature.  The black lines indicate thin plates of cementite over the
 The solubility of carbon in δ-iron is 0.1% at 1492°C. white background of ferrite.
 It is soft & ductile phase.  The properties of pearlite depend upon its interlamellar
 Region R-M-K-R represents δ-ferrite phase. spacing.
 Smaller the spacing, higher are the mechanical properties.

D) Cementite
 It is an inter-metallic compound of iron & carbon.
 It has fixed carbon of 6.67%.
 Its crystal structure is complex orthorhombic.
 It is hardest structure in the equilibrium diagram & is
Fig. No. 3.3 Ferrite Microstructure brittle in nature.

ENGINEERING METALLURGY (202049) 47

 Unit III Iron-Carbon Alloy System and Cast Iron

 Refer Fig. No. 3.7 below showing enlarged Peritectic

region in the upper left hand corner of Iron-Iron Carbide
Diagram.
 Peritectic reaction occurs at point P.
Here, Solid1 = δ-ferrite
Liquid = molten steel
Solid2 = γ-austenite
 The Peritectic reaction is given by,
1492°𝐶
𝛿 + 𝐿 → 𝛾
(0.1%C) (0.55%C) (0.18%C)

Fig. No. 3.6 Cementite Microstructure Consider transformation along line I in Fig. No. 3.7
 It is also termed as iron carbide. Amount of δ-ferrite & liquid steel in the final solid γ-austenite
 It is stable for a wide range of temperature up to around at 1492°C can be obtained by lever rule.
1500°C. 𝑁𝑃
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝛿 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒 = 𝑥 100
𝑁𝑀
E) Ledeburite 0.55 − 0.18
 It is the eutectic mixture of austenite and cementite. = 𝑥100
0.55 − 0.1
 It contains 4.3% of carbon and falls under the group of
Cast Irons. = 82.2 %

3.4 Reactions in Iron-Iron Carbide Equilibrium Consider transformation along line II in Fig. No. 3.7
Diagram Transformation occurring at 0.1%C < carbon < 0.18%C is
termed as hypo-Peritectic steel.
 During cooling of iron and carbon alloy from molten state, 1492℃
a number of reaction/ transformation take place, i.e. 𝛿+𝐿→ 𝛿+ 𝛾
reactions occurring during liquid to solid and solid to solid.
 Following are the three major reactions observed during Consider transformation along line III in Fig. No. 3.7
the solidification of steel. Transformation occurring at 0.18%C < carbon < 0.55%C is
1. Peritectic Reaction termed as hyper-Peritectic steel.
2. Eutectoid Reaction 1492℃
3. Eutectic Reaction 𝛿+𝐿→ 𝛾+𝐿

3.4.1 Peritectic Reaction 3.4.2 Eutectoid Reaction

Fig. No. 3.7 Peritectic Region of Fe-Fe3C Diagram

 It is a high temperature reaction.
 In general, Peritectic reaction is given by,
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
𝑆𝑜𝑙𝑖𝑑1 + 𝐿𝑖𝑞𝑢𝑖𝑑 → 𝑆𝑜𝑙𝑖𝑑2 Fig. No. 3.8 Eutectoid Region of Fe-Fe3C Diagram

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 Unit III Iron-Carbon Alloy System and Cast Iron

 It is a low temperature reaction.  The eutectic mixture of γ-austenite and cementite (Fe3C)
 In general, eutectoid reaction is given by, is called Ledeburite.
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
𝑆𝑜𝑙𝑖𝑑1 → 𝑆𝑜𝑙𝑖𝑑2 + 𝑆𝑜𝑙𝑖𝑑3
 Eutectoid Reaction occurs at point E.
Here, Solid1 = γ-austenite
Solid2 = α- ferrite
Solid3 = Cementite Fe3C
 The eutectoid reaction is given by,
727℃
𝛾 → 𝛼 + 𝐹𝑒3 C
(0.8%C) (0.025%C) (6.67%C)

 The eutectoid mixture of α-ferrite and cementite (Fe3C) is

called Pearlite.
 Pearlite consists of alternate lamellae of cementite in α-
ferrite structure.

Consider transformation along line IV in Fig. No. 3.8

Amount of α-ferrite & cementite in the final solid pearlite can
be obtained by lever rule.
𝐸𝐹
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝛼 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒 = 𝑥 100
𝐷𝐹
6.67 − 0.8 Fig. No. 3.9 Eutectic Region of Fe-Fe3C Diagram
= 𝑥100  Hence, austenite on cooling gets transformed to pearlite.
6.67 − 0.025
 The microstructure at room temperature, thus consists of
= 88.1 % pearlite and cementite.
𝐷𝐸
𝐴𝑚𝑜𝑢𝑛𝑡 𝑐𝑒𝑚𝑒𝑛𝑡𝑖𝑡𝑒 = 𝑥 100 Consider transformation along line VII in Fig. No. 3.9
𝐷𝐹
0.8 − 0.025 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑒𝑎𝑟𝑙𝑖𝑡𝑒 & 𝑐𝑒𝑚𝑒𝑛𝑡𝑖𝑡𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑓𝑖𝑛𝑎𝑙 𝑠𝑜𝑙𝑖𝑑 𝑠𝑡𝑒𝑒𝑙 𝑐𝑎𝑛 𝑏𝑒
= 𝑥100
6.67 − 0.025 𝑜𝑏𝑎𝑡𝑖𝑛𝑒𝑑 𝑏𝑦 𝑎𝑝𝑝𝑙𝑦𝑙𝑖𝑛𝑔 𝑙𝑒𝑣𝑒𝑟 𝑟𝑢𝑙𝑒
𝑈𝑉
= 11.9 % 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑝𝑒𝑎𝑟𝑙𝑖𝑡𝑒 = 𝑥 100
𝐽𝑉
Consider transformation along line V in Fig. No. 3.8 6.67 − 4.3
Transformation occurring at 0.025%C < carbon% < 6.67%C is = 𝑥100
6.67 − 2.0
termed as hypo-eutectoid steel.
= 40.4 %
Consider transformation along line VI in Fig. No. 3.8 𝐽𝑈
Transformation occurring at 0.8%C < carbon% < 6.67%C is 𝐴𝑚𝑜𝑢𝑛𝑡 𝑐𝑒𝑚𝑒𝑛𝑡𝑖𝑡𝑒 = 𝑥 100
𝐽𝑉
termed as hyper-eutectoid steel.
4.3 − 2.0
3.4.3 Eutectic Reaction = 𝑥100
6.67 − 2.0
 It is a low temperature reaction.
 In general, eutectoid reaction is given by, = 59.6 %
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
𝐿𝑖𝑞𝑢𝑖𝑑 → 𝑆𝑜𝑙𝑖𝑑1 + 𝑆𝑜𝑙𝑖𝑑2 Consider transformation along line VIII in Fig. No. 3.9
 Eutectic Reaction occurs at point U Transformation occurring at 2.0%C < carbon % < 4.3%C
Here, Liquid = Molten steel is termed as hypo-eutectic steel.
Solid1 = δ- austenite
Solid2 = Cementite Fe3C Consider transformation along line IX in Fig. No. 3.9
Transformation occurring at 4.3%C < carbon % < 6.67%C
1147℃ is termed as hyper-eutectic steel.
𝐿 → 𝛾 + 𝐹𝑒3 C
(4.3%C) (2%C) (6.67%C)

ENGINEERING METALLURGY (202049) 49

 Unit III Iron-Carbon Alloy System and Cast Iron

3.5 Critical Temperatures

 Critical temperatures are those at which the phase changes
occur during heating and cooling in an equilibrium
diagram.
 These critical temperatures and temperature at which
magnetic property changes are denoted by symbols in the
equilibrium diagram.

A0 (Curie temperature for cementite) 210°C.

 It is the temperature above which on heating, the cementite
loses its magnetism i.e. it becomes paramagnetic.
 It is indicated by dotted line AB in Fig. No. 3.2.

A1 (Lower Critical temperature) 727°C.

 It denotes the temperature above which on heating,
pearlite gets transformed into soft austenite.
 It is also called at eutectoid temperature.
 It is indicated by line DEF in Fig. No. 3.2. Fig. No. 3.10 Eutectoid Transformation for 0.2% C in Fe-
Fe3C Diagram
A2 (Curie temperature for ferrite) 768°C. At point 1:
 It is the temperature above which on heating, the ferrite  The microstructure contains 100% γ-austenite. (Solid
loses its magnetism i.e. it becomes paramagnetic. solution).
 It is indicated by dotted line GHEF in Fig. No. 3.2.  Refer Fig. No. 3.11 (a) for the microstructure at point 1.

A3 (Critical temperature for hypo-eutectoid steels) 727°C to

910°C.
 It is the temperature above which on heating, free ferrite
gets dissolved to form 100% austenite.
 It represents the boundary between (γ+α) and γ phase.
 The temperature ranges from 727°C at 0.8% C to 910°C at
2.0% C.
 It is indicated by line CHE in Fig. No. 3.2.
Fig. No. 3.11 (a)
Acm (Critical temperature for hyper-eutectoid steels) 727°C At point 2:
to 1147°C.  Point 2 marks the transformation from liquid γ-austenitic
 It is the temperature above which on heating, free to a combination of proeutectoid α-ferrite and solid
cementite gets dissolved to form 100% austenite. solution γ-austenite.
 It represents the boundary between (γ+Fe3C) and γ phase.
 The temperature ranges from 727°C at 0.8% C to 1147°C At point 3:
at 2.0% C.  Cooling from Point 2 to 3, causes separation of
 It is indicated by line EJ in Fig. No. 3.2. proeutectoid α-ferrite from the γ-austenite phase.
 At a point just above point 3, the structure is as shown in
A4 (Upper Critical temperature) 1400°C to 1492°C. the Fig. No. 3.11 (b).
 It is the temperature above which on heating, austenite
gets transformed into δ-ferrite.
 It is indicated by line RP in Fig. No. 3.2.

3.6 Solidification and Microstructures of Slowly

Cooled Steels
3.6.1 Hypo-Eutectoid Steel
Consider Slow Cooling of 0.2% C Steel
 Consider slow cooling along the dotted line I for 0.2% C
from austenitic region to room temperature. Fig. No. 3.11 (b)

ENGINEERING METALLURGY (202049) 50

 Unit III Iron-Carbon Alloy System and Cast Iron

 It consists of solid solution γ-austenite which transforms, 0.2 − 0.008

= 𝑥100
at constant temperature of 727°C, to a lamellar 0.8 − 0.008
microstructure called pearlite.
 The amount of proeutectoid α-ferrite is = 24.24%
𝑙(3𝐸)
= 𝑥100 Consider Slow Cooling of 0.4% C Steel
𝑙(𝐷𝐸)  Consider slow cooling along the dotted line I for 0.4% C
from austenitic region to room temperature.
0.8 − 0.2
= 𝑥100
0.8 − 0.025

= 77.42%
 The amount of proeutectoid pearlite is
𝑙(𝐷3)
= 𝑥100
𝑙(𝐷𝐸)

0.2 − 0.025
= 𝑥100
0.8 − 0.025

= 22.58%

At point 4:
 From point 3 to 4, the microstructure contains solid pearlite
and proeutectoid α-ferrite.
 α-ferrite appears as white space and cementite appears as
thin black lines.
 Refer Fig. No. 3.11 (c).

Fig. No. 3.12 Eutectoid Transformation for 0.4% C in Fe-

Fe3C Diagram
At point 1:
 The microstructure contains 100% γ-austenite. (Solid
solution).
 Refer Fig. No. 3.13 (a) for the microstructure at point 1.

Fig. No. 3.11 (c)

 Pearlite (Combination of α and Fe3C) appears as inter

lamellar structure.
 Proeutectoid α-ferrite is observed as dendrites.
 The microstructure can be easily observed under a
microscope by etching. Fig. No. 3.13 (a)
 At room temperature,
Amount of proeutecto𝑖𝑑 𝛼 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒 At point 2:
0.8 − 0.2  Point 2 marks the transformation from solid solution γ-
= 𝑥100 austenitic to a combination of proeutectoid α-ferrite and
0.8 − 0.008
solid solution γ-austenite.
= 75.76%  At a point just above point 2 the microstructure is 100%
solid solution γ-austenite.
Amount of pearlite  The composition of proeutectoid α-ferrite varies along line
CE.

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 Unit III Iron-Carbon Alloy System and Cast Iron

At point 3:  Pearlite (Combination of α and Fe3C) appears as inter

 Cooling from Point 2 to 3, causes separation of lamellar structure.
proeutectoid α-ferrite from the γ-austenite phase.  Proeutectoid α-ferrite is observed as dendrites.
 At a point just above point 3, the structure is as shown in  The microstructure can be easily observed under a
the Fig. No. 3.13 (b). microscope by etching.
 At room temperature,
Amount of proeutecto𝑖𝑑 𝛼 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒
0.8 − 0.4
= 𝑥100
0.8 − 0.008

= 50.51%
Amount of pearlite
0.4 − 0.008
= 𝑥100
0.8 − 0.008
Fig. No. 3.13 (b) = 49.49%
 It consists of solid solution γ-austenite which transforms,
at constant temperature of 727°C, to a lamellar 3.6.2 Eutectoid Steel
microstructure called pearlite. Consider Slow Cooling of 0.8% C Steel
 The amount of proeutectoid α-ferrite is
𝑙(3𝐸)
= 𝑥100
𝑙(𝐷𝐸)
0.8 − 0.4
= 𝑥100
0.8 − 0.025
= 51.61%

 The amount of proeutectoid pearlite is

𝑙(𝐷3)
= 𝑙(𝐷𝐸) 𝑥100

0.4 − 0.025
= 𝑥100
0.8 − 0.025

= 48.39%
At point 4:
 From point 3 to 4, the microstructure contains solid pearlite
and proeutectoid α-ferrite. Fig. No. 3.14 Eutectoid Transformation for 0.8% C in Fe-
 α-ferrite appears as white space and cementite appears as Fe3C Diagram
thin black lines.  Consider slow cooling along line III for 0.8% C from
 Refer Fig. No. 3.13 (c). austenite region to room temperature.
At point 1:
 The microstructure contains 100% γ-austenite. (Solid
solution).
 Refer Fig. No. 3.15 (a) for the microstructure at point 1.

Fig. No. 3.13 (c)

Fig. No. 3.15 (a)

ENGINEERING METALLURGY (202049) 52

 Unit III Iron-Carbon Alloy System and Cast Iron

At point 2:
 At point 2, the eutectoid transformation takes place at
constant temperature of 727°C.
727℃
𝛾 → 𝛼 + 𝐹𝑒3 𝐶
Amount of 𝛼 − 𝑓𝑒𝑟𝑟𝑖𝑡𝑒
𝑙(𝐸𝐹)
= 𝑥100
𝑙(𝐷𝐹)

6.67 − 0.8
= 𝑥100
6.67 − 0.025

= 88.337%
Amount of 𝐹𝑒3 𝐶
𝑙(𝐷𝐸)
= 𝑥100
𝑙(𝐷𝐹)

0.8 − 0.025 Fig. No. 3.16 Eutectoid Transformation for 1.2% C in Fe-
= 𝑥100 Fe3C Diagram
6.67 − 0.025

= 11.663%
At point 3:
 The microstructure below point 2 is as shown in Fig. No.
3.15 (b).

Fig. No. 3.17 (a)

 At a point just above point 2, the structure is 100% solid
solution γ-austenite.
 The composition of γ-austenite varies along line EJV.
Fig. No. 3.15 (b)
 The eutectoid mixture obtained consists of α-ferrite and
At point 3:
cementite.
 Cooling from point 2 to 3 causes separation of proeutectoid
 α-ferrite appears as white and cementite appears as thin
Fe3C from γ-austenite solid solution phase.
black lines.
 At a point just above point 3, the structure is as shown in
Fig. No. 3.17 (b).
3.6.3 Hyper-Eutectoid Steel
Consider Slow Cooling of 1.2% C Steel
 Consider slow cooling along the dotted line IV for 1.2% C
from austenite region to room temperature.
 Refer Fig. No. 3.16.

At point 1:
 The microstructure contains 100% γ-austenite.
 Refer Fig. No. 3.17 (a) for microstructure at point 1.

At point 2:
 Point 2 marks the transformation from solid solution γ- Fig. No. 3.17 (b)
austenite to a combination of proeutectoid Fe3C and liquid  It consists of solid solution γ-austenite and solid
γ-austenite. proeutectoid Fe3C.

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 Unit III Iron-Carbon Alloy System and Cast Iron

At point 4:  The transformation from austenite to pearlite is referred to

 Cooling from point 3 to 4, the microstructure contains solid as eutectoid transformation at eutectoid temperature of
pearlite and proeutectoid cementite. 727°C under slow cooling conditions.
 Refer Fig. No. 3.17 (c).  But due to fast cooling, there is a shaft in the eutectoid
temperature.
 Refer Fig. No. 3.18 for effects of non-equilibrium cooling
on eutectoid transformation.

Fig. No. 3.17 (c)

 α-Ferrite appears as white spaces and cementite as thin
black lines.
 Pearlite (Combination of α and Fe3C) appears as
interlamellar structure.
 Proeutectoid Fe3C appears as dendritic structure.
 At point 3, the existing γ-austenite transforms at constant
temperature of 727°C to a lamellar structure of ferrite and
cementite called pearlite.
Amount of 𝑃𝑟𝑜𝑒𝑢𝑡𝑒𝑐𝑡𝑜𝑖𝑑 𝐹𝑒3 𝐶
𝑙(𝐸3) Fig. No. 3.18 Effects of non-equilibrium cooling on
= 𝑥100 eutectoid transformation
𝑙(𝐸𝐹)
 For fast cooling, the eutectoid transformation temperature
1.2 − 0.8 moves along the line XY as in Fig. No. 3.18.
= 𝑥100  The eutectoid carbon for equilibrium cooling is 0.8%C.
6.67 − 0.8
 For non-equilibrium cooling, the eutectoid carbon shifts
= 6.81% towards lower values for hypo-eutectoid steels.
Amount of 𝑃𝑒𝑎𝑟𝑙𝑖𝑡𝑒  Similarly, for hyper-eutectoid steels the eutectoid carbon
𝑙(3𝐹) shifts towards higher values.
= 𝑥100  Thus for a given steel composition, the amount of
𝑙(𝐸𝐹)
proeutectoid phase decreases and pearlite phase increases.
6.67 − 1.2  Also, due to fast cooling rates, the nucleation rate
= 𝑥100 increases.
6.67 − 0.8
 This results in decrease in the interlamellar spacing of
= 93.19% pearlite.
 Due to change in transformation phases and interlamellar
3.7 Non-Equilibrium Cooling of Steels spacing, the mechanical properties are affected to a greater
 Slow cooling from austenite region results in formation of extent.
pearlite which is a combination of cementite and ferrite.
 Non-equilibrium cooling i.e. fast cooling results in a 3.8 Widmanstaten Structures
different microstructure transformation.  During cooling of steel from austenite region, proeutectoid
 This also results in significant change in properties of phase separates along with grain boundary.
steels.  The phase sometimes separates not only along the grain
 The concept of heat treatment is based on these effects. It boundaries but also in the grain interiors.
uses controlled departures from equilibrium conditions to  It separates out in a specific orientation. These types of
obtain required structure and properties. structure are called as Widmanstaten structure.
 Widmanstaten structure is higher if the steel has a
composition deviating from the eutectoid point.

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 Fig. No. 3.21 shows the effect of carbon content on

different properties of plain carbon steel.

Fig. No. 3.19 Widmanstaten Structure

Fig. No. 3.21 Properties Vs Weight Percentage Carbon

 Tensile strength and yield strength increases to about 0.8%
carbon. The percentage of elongation and reduction in
Widmanstaten cross sectional area drops perfectly with increase in carbon
Structure percentage.
 The impact strength can be decreased perfectly up to 0.8%
carbon.
 The properties of steel depends upon the proportion of the
Fig. No. 3.20 Microstructure of Widmanstaten Structure
phases.
 Tensile strength of ferrite is 40,000 psi & cementite is
 These structures are occur in steels having carbon content
40,000 to 60,000 psi.
up to 0.8% and above 0.9%.
 Pearlite is having high tensile strength 1, 00,000 psi.
 In hypereutectoid steels, with widmanstaten structure is
 The hardness can be between ferrite & cementite.
desirable because of the hard & brittle cementite phase
does not appear in the form of continuous network along  Normally, for two phase material having phases such as A
with grain boundary. & B, the average property.
 In hypoeutectoid steels widmanstaten structure reduces  Avg. property = (Amount of A x Property of A) +
low toughness & ductility values. This is because breaking (Amount of B x Property of B).
the continuity of ferrite.
3.10 Classification and Application of Steels
3.9 Structure and Property Relationship  The steels are classified by different methods, according to
 When carbon percentage in the steel, there is some phases definite criteria. The different criterions as follows:
obtained. a) Carbon content
b) Alloying elements and carbon
 The phases are pearlite, ferrite and cementite. The pearlite
c) Amount of deoxidation
is soft and having good strength. Ferrite is very soft and
d) Method of manufacture
ductile and cementite is very hard phase.
e) Classification based on application
 Therefore, the properties of steel depends upon the
proportion of the phases.
3.10.1 On basis of carbon content
 As the carbon contents goes on increasing, the hardness
 The plain carbon steels are classified into three groups.
goes on increasing. The carbon contents increases up to
These are as follows:
2%.

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 Unit III Iron-Carbon Alloy System and Cast Iron

a) Low Carbon Steels (0.008 to 0.30% C) 3. It is used for nails.

b) Medium Carbon Steels (0.30 to 0.60% C) 4. It is used in screws.
c) High Carbon Steels (0.60 to 2% C) 5. They are used in welding rods.
6. It is used in ship plates.
Low Carbon Steels (0.008 to 0.30% C) 7. They are used in boiler plates and tubes.
 The different steels produced in the greatest quantities fall 8. They are used for fan blades.
within the low carbon classification. 9. It is used in gears.
 These generally contain 0.008 to 0.30 % carbon and are 10. They are used in cam shafts.
unresponsive to heat treatments intended to form 11. It is used in crank shafts.
martensite; strengthening is accomplished by cold work. 12. They are used for connecting rods.
 The microstructure shown in Fig. No. 3.22 shows that there 13. It is used in railway axles.
are two phases such as pearlite (25%) at the grain 14. They are used in cross-heads.
boundaries of grain and remaining is ferrite (75%) which 15. They are used in panels.
is in white colour.
Medium Carbon Steels (0.30 to 0.60% C)
 These alloys may be heated by quenching and then
tempered to improve their mechanical properties.
 The plain medium carbon steels have low hardenability's
and can be successfully heat treated only in very thin
sections and with very rapid quenching rates. They usually
do not work.
 The microstructure shown in Fig. No. 3.23 shows two
phases such as pearlite (60%), which is in dark colour and
remaining is ferrite, which is in white colour.
(a) Ferrite (40 %)

Pearlite (60 %)

(a)

(b)
Fig. No. 3.22 Microstructure of Low Carbon Steel (0.2%C)

Properties of Low Carbon Steels

1. They are relatively soft.
2. They are ductile.
3. They are malleable.
4. Yield strength is 26 kg/mm2.
5. Ultimate tensile strength is 42 to 56 kg/mm2.
6. Elongation is 23%.

Applications of Low Carbon Steels

(b)
1. Automobile body components.
Fig. No. 3.23 Microstructure of Medium Carbon Steel
2. They are used for rivets.
(0.4%C)

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Properties of Medium Carbon Steels Properties of High Carbon Steels

1. They are medium hard. 1. They are hardest and strongest.
2. They are not so ductile. 2. They are least ductile.
3. It is not so malleable. 3. High wear resistance.
4. They are medium high. 4. They are brittle.

Applications of Medium Carbon Steels Applications of High Carbon Steels

1. They are used for railway wheels. 1. They are used for blacksmith tools.
2. It is used for gears. 2. It is used for wood working tools.
3. They are used for crank shafts. 3. They are used for forging dies.
4. It is used for bolts, axles, lock washers, springs, wires, 4. They are used for balls and races for ball bearings.
rods, turbine rotors, cylinder liners, crank pins etc. 5. They are used for punches, hammers, springs, clutch
discs, car bumpers, vice jaws, shear blades, music
High Carbon Steels (0.60 to 2% C) wires, cutters etc.
 The high carbon steels are hardened by heat treatment.
 The hardness produced after hardening is high. 3.10.2 On basis of Alloying Elements and Carbon
 The depth of hardening is also high.  Alloying elements such as Cr, Mo, V, Mn, Ni etc. are added
 The hardenability is more as compared to medium carbon to steels in certain amounts to increase mechanical
steels. properties.
 The microstructure is shown in Fig. No. 3.24  Steels are classified on the basis of alloying elements and
microstructure consists of the 100% fine resolved pearlite. carbon as below
1. Low alloy steels (<10%)
2. High alloy steels (>10%)

Total content of alloying

Carbon content
elements
Low carbon (0.3%)
Medium carbon (0.3 to 0.6%) Low alloy (<10%)
High carbon (>0.6%) High alloy (>10%)

3.10.3 On basis of Amount of Deoxidation

 During steel-manufacturing processes, combination of
(a) carbon and oxygen takes place to form a gas.
 If the oxygen is not removed before or during casting the
gaseous products continue to evolve during solidification.
 The type of steel produced is determined by the control of
the mount of gas evolved during solidification.
 If no gas is evolved, the steel is called “Killed” because it
lies quietly in moulds. Increasing degree of gas evolution
results in semi-killed, capped or rimmed steels.
 Some carbon steels and high strength low-alloy steels can
be supplied in all four types. Alloy steel and stainless and
heat resisting steels are normally manufactured as killed
steel.

Killed Steel
 It is produced by involving the use of several deoxidizing
elements which act with varying intensities.
 The common of these are silicon and aluminium.
 Killed steel, because of greater uniformity in chemical
(b) composition and soundness is used for forging,
Fig. No. 3.24 Microstructure of High Carbon Steel carburizing, heat treatment and other applications.
(0.8%C)

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 They are strongly deoxidised and are characterized by high  During solidification of semi-killed steel, gas is evolved in
composition and property uniformity. the body of the ingot, tending to compensate in part of
entirely for the shrinkage accompanying solidification.
 Since pipe cavities are minimized, semi-killed steels are
usually cast in big-end-down molds without hot-tops.
 This type of steel is suitable for drawing operation.

Rimmed Steel
 In rimmed steel, the aim is to produce a clean surface low
in carbon content, rimmed steel is also known as drawing
quality steel.
 The typical structure results for a marked gas evolution
during solidification of outer rim.
 They exhibit greatest difference in chemical composition
across and from top to bottom of the ingot.

Fig. No. 3.25 Killed Steel

 All forging steels and in general, all steels containing more
than 0.25% carbon are killed.
 These types of steels are free from blow holes and
segregation.
 Symbol K stands for killed steel.

Semi Killed Steel

 It has characteristics intermediate those of killed or rimmed
steels.
 Structural steels containing 0.15 to 0.25% carbon are Fig. No. 3.27 Rimmed Steel
generally semi-killed.  They have an outer rim that is lower in carbon, phosphorus
 In semi-killed steel, the aim is to produce metal free from and sulphur than the average composition of the whole
surface blowhole and pipe. ingot and an inner portion or core that is higher the average
in those elements.
 In rimming, the steel is partially deoxidized. Carbon
content is less than 0.25% and manganese content is less
than 0.6%.
 They do not retain any significant percentage of highly
oxidizable elements such as Aluminium, Silicon or
Titanium.
 A wide variety of steels for deep drawing is made by the
rimming process, especially where ease of forming and
surface finish are major consideration.
 These steel are, therefore ideal for rolling, large number of
applications and is adapted to cold-bending, cold-forming
and cold header applications.

3.10.4 On basis of Method of Manufacture

 This classification criterion focuses only on the
manufacturing method for producing steels.
Fig. No. 3.26 Semi Killed Steel  It does not focus on the composition and mechanical
 The surface should have a sound kin of considerable properties of steels.
thickness.  Steel can be classified as follows:
 They are used for general structural applications. 1. Basic oxygen process

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2. Electric furnace Classification of Steel on the basis of carbon content

3. Acid open hearth Table No. 3.1 Uses according to carbon content
4. Basic open hearth Types of Carbon
Uses
5. Acid Bessemer Steel Content
0.05 to Chain, rivets, fan blades, wires,
3.10.5 On basis of Classification based on Applications 0.15 nails.
 According to the applications, the steels are classified as Low
0.15 to Screws, structural steels-RCC Bar,
follows: Carbon
0.20 Machine Parts
1. Tool Steels Steel
0.20 to Gears, shaft, levers, forging.
2. Machinery Steels 0.30
3. Boiler Steels 0.30 to Connecting rod, Bolts, Nuts shaft,
4. Free Cutting Steels 0.40 axles.
5. Deep Drawing Steels Medium
0.40 to Crank shaft, axles, gears, and shaft.
6. Structural Steels Carbon
0.50
7. Corrosion Resistant Steels Steel
0.50 to Rails, Laminated Springs, Wire
8. Electrical Steels 0.60 ropes.
0.60 to Screw drivers, saws, drop hammer
Tool Steels: 0.70 dies.
They are used for cutting of metals and having carbon contain 0.70 to Band saws, hammers, large dies for
more than 0.6%. They are in the group of high carbon steels. 0.80 cold presses.
0.80 to Cold Chisels, Shear Blades,
Machinery Steels: 0.90 Punches.
They are used for the manufacture of machinery parts, 0.90 to Spring, High Tension Wires, Dies,
automotive parts and carbon content is between 0.3 to 0.55%. High
1.0 Sitar wire.
They are in the group of medium carbon steels. Carbon
1.0 to Drills, Tabs, Milling Cutters.
Steel
1.1
Boiler Steels:
1.1 to Dies, Drills, Lathe tools, Wood
They are used for the construction of boilers. These steels are
1.2 Working tools.
of low carbon steels having carbon content less than 0.25% and
1.2 to Files, Broaches, Lathe and Wood
they can be cold formed without cracking due to their better
1.3 working tools.
forming properties.
1.3 to Saws, Boring tools and finishing
1.4 tools
Free Cutting Steels:
These steels can be easily machined and are used for the
manufacture of screws, bolts and nuts etc. Elements such as Pb,
Te, Se, S and P increase machinability and hence, these steels
contain the above elements.

Deep Drawing Steels:

They are suitable for deep drawing purpose due to their high
formability and used for refrigerators, stoves, automobile
bodies etc. The carbon content is below 0.10%.

Structural Steels:
These steels are used in the construction of bridges, buildings,
cars, ships etc. The carbon content between 0.15 to 0.30%.

Corrosion Resistant Steels:

They are having high corrosion and oxidation resistance and
used for high temperature conditions e.g. high chromium steels.

Electrical Steels:
These steels have good electrical characteristics and they are
used for the manufacture of electrical machineries. The Si and
carbon content is below 0.05%.

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 Unit III Iron-Carbon Alloy System and Cast Iron

Unit – III
Iron-Carbon Alloy System and Cast Iron

Syllabus:
Iron-iron carbide equilibrium diagram, critical temperatures, solidification and microstructure of slowly cooled
steels, structure & property relationship, classification and application of steels.
Cast Irons: Classification, Manufacturing, Composition , Properties & applications of white C.I., Grey cast iron,
malleable C.I., S.G. cast iron, chilled and alloy cast iron, effect of various parameters on structure and properties
of cast irons. Specific applications such as machine tools, automobiles, pumps, valves etc.
Introduction to non-equilibrium cooling of steels, widmanstaten structure

Part B: - Cast Iron

Section No. Topic Name Page No.
3.11 Introduction 61
3.12 Characteristics of Cast Iron 61
3.13 Classification of Cast Iron 61
3.14 IS Specification of Cast Iron 62
3.15 Factors Affecting Microstructure of Cast Iron 62
3.16 White Cast Iron 63
3.17 Malleable Cast Iron 65
3.18 Gray Cast Iron 67
3.19 Nodular or Spheroidal Graphite Cast Iron 69
3.20 Mottled Cast Iron 70
3.21 Chilled Cast Iron 71
3.22 Alloy Cast Iron 72
3.23 Specific Applications of Cast Iron 72

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3.11 Introduction It has limited It has excellent

 Cast iron, an alloy of iron contains 2 to 6.67% carbon, castability. castability
along with varying amounts of silicon and manganese and
Cast irons have
traces of impurities such as sulphur and phosphorus. Alloy steels have high
good corrosion
 High carbon tends to make the cast iron brittle, most corrosion resistance.
resistance
commercially manufactured types are in the range of 2.5
to 3.7% carbon. Because of their malleability, they cannot It has high
be forged, rolled, drawn or worked at room temperature. It has good hardness
compressive
 Lower melting temperature (1150°C to 1250°C) as and strength
strength
compared to steels.
 Due to low ductility and malleability of cast iron, they Cast iron are used
cannot be forged, rolled, drawn or pressed into the required in pipe fittings,
Steels are used in
shape. valves, farm
crankshaft, gears,
 But, cast iron are formed by melting a metal and casting equipment’s,
axles, cutting tools,
with or without machining to the desired final shape and crankshafts, gears,
Applications dies, heat exchangers,
size, hence called as cast iron. axles, low
aircraft parts, surgical
temperature dies,
instruments, gas
3.11.1 Advantages of Cast Iron over Steel various automobile
burners etc.
1. Cast iron is cheaper than steel. casting
2. Cast iron has low melting point than steel. components etc.
3. Cast iron having good casting ability than steel.
4. Cast iron have good damping capacity than steel.
5. Cast iron is not stronger than steel. 3.13 Classification of Cast Iron
Cast iron are classified according to the following criteria:
3.12 Characteristics of Cast Iron
3.13.1 According to furnace used for their
 While manufacturing of cast iron, raw materials like pig
manufacturing:
iron, cast iron scrap, steel scrap, Ferro-silica, iron ore,
 Cupola cast iron
limestone, coke etc. are used.
 Air furnace cast iron
 These all the elements from which cast iron are
 Duplex cast iron (it is melted in one type of furnace and
manufactures are relatively cheap hence, cast iron is the
superheated in another furnace)
cheapest amongst the all commercial alloys.
 Electric furnace cast iron
 Cast iron are having low melting point (1150°C to
1250°C) than steels hence, easy to melt.
3.13.2 According to composition and purity:
 Corrosion resistance of cast iron is fairly good.
 Low carbon and low silicon cast iron
 By altering chemical composition and heat treatment, cast
 High carbon and low sulphur cast iron
iron can provide a wide range of metallic properties.
 Cast iron with nickel alloy
 Cast iron can provide good damping capacity and high
compressive strength.
3.13.3 According to microstructure and appearance of
 Cast iron is also having high hardness, high resistance to
fracture:
wear and abrasion.
White Cast Iron
 On cast iron various machining operations can be done.
 In this type of cast iron, all the carbon is in the combined
 In general, cast iron is brittle and its mechanical properties form i.e. cementite.
like toughness, stiffness are poor than steels.
3.12.1 Comparison between Steels and Cast Iron Malleable Cast Iron
 It contains free carbon (graphite) in the form of irregular
Parameter Steels Cast Iron spheroids which is called as temper carbon graphite
Carbon in the nodules i.e. rosettes.
Composition Less than 2 % carbon range of 2% to  Generally, it is produced from white cast iron by a heat
6.67% treatment which is termed as malleablization.
High melting Low melting
temperature 1340 to temperature 1150 Gray Cast Iron
Properties  It contains free carbon (graphite) in the form of flakes.
1450°C to 1250°C

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Nodular Cast Iron For Spheroidal Graphite Cast Iron

 It contains free carbon (graphite) in the form of nodules/  Minimum tensile strength in kgf/mm2 is given along with
spheroids. the minimum % elongation.
 It is produced from high grade of gray cast iron by adding  For example: SG 70/2 is spheroidal graphite cast iron with
a small amount of magnesium but prior to pouring. 70 kgf/mm2 minimum tensile strength and 2% minimum
elongation.
Mottled Cast Iron
 It contains microstructures of both white cast iron and gray For Other Castings
cast iron.  Minimum tensile strength is given for all the sectional
thickness.
Chilled Cast Iron  For example: PM 60 is pearlitic malleable cast iron with
 It shows white cast iron on the surface and gray cast iron at minimum tensile strength of 60 kgf/mm2.
the centre.
3.14.3 Chemical Composition
Alloy Cast Iron  Chemical composition criteria for designation of cast iron
 As per the requirement, some alloying elements are added indicate the all-important alloying element in cast iron.
to the cast iron which is called as alloy cast iron.  The following are the various examples for chemical
 Generally, following types of alloy cast iron are mostly composition system:
used: Designation Meaning
1. Ni-hard cast iron FG -Gray Cast Iron
2. Ni-resist cast iron FG 35 Si15 35- % C 10= 3.5% C
3. Meehanite Si15 - % Si 10 = 1.5% Si
ASG- Austenitic Spheroidal Graphite
3.14 IS Specification of Cast Iron ASG Ni20 Cr2 Cast Iron.
 Indian Standard (IS) designation system for cast iron Ni20- 20% Nickel Cr2- 2% Chromium
specify the cast iron with various symbols that indicate the
various characteristics of cast iron. 3.15 Factors Affecting Microstructure of Cast
 Also, properties and composition of various types of cast Iron
iron is mentioned in this system.
Carbon Content
 The following are the important designation criteria for
 Carbon is a graphitizer and with increasing its content,
cast iron:
there are chances of formation of graphite by the
1. Type of Casting
decomposition of cementite which leads to the formation
2. Mechanical Properties
of gray cast iron.
3. Chemical Composition
 Also, if carbon content is higher and cooling rate is slow
then the matrix becomes a ferrite.
3.14.1 Type of Casting
The type of casting is indicated by the following letters:  With increase in carbon content hardness of cast iron
decreases.
Symbol Specification
FG Gray Cast Iron Silicon Content
BM Black Heart Malleable Cast Iron  Actually, silicon is a strong graphitizer, which promotes
WM White Heart Malleable Cast Iron graphitization (decomposition of cementite into iron and
PM Pearlite Malleable Cast Iron graphite), so to control graphitization its amount is
SG Spheroidal Graphite Cast Iron controlled.
AFG Austnitic Flake Spheroidal Graphite Cast Iron  Generally amount of silicon in commercial cast iron varies
ASG Austnitic Spheroidal Graphite Cast Iron from 0.5% to 3.0%.
 When amount of silicon is lower, it solidifies as a white
3.14.2 Mechanical Properties cast iron and when higher, it solidifies as a gray cast iron.
For Grey Cast Iron  A perfect balance of silicon and carbon gives optimum
 Minimum tensile strength in kgf/mm2 is given for 30 mm strength to the cast iron.
sectional thickness.
 For example: FG 40 is cast iron with minimum tensile Phosphorus Content
strength 40 kgf/mm2 for 30 mm thickness.  Like silicon, phosphorous also a strong graphitizer and its
amount varies from 0.1 to 0.3%.

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 Generally, phosphorous combines with iron and forms  The cementite which precipitates from the melt forms as
iron phosphide which, separates eutectic mixture with relatively large particles, usually in a eutectic mixture,
cementite and austenite. where other phase is austenite (which on fast cooling
 The formed ternary eutectic of iron phosphide, austenite transform to martensite).
and cementite is termed as steadite.  White cast iron is too brittle for use in many structural
 A small amount of phosphorous produces large amount of components, but with good hardness and abrasion
steadite, which is brittle in nature. resistance and relatively low cost.
 Steadlite reduces toughness and increases brittleness of
cast iron.
 Also, phosphorous increases fluidity of cast iron, hence
very thin and complex sections can be produced.
Austenite
Sulphur Content
 Sulphur reacts with iron and forms iron sulphide which is
hard, brittle and hence increases brittleness of cast iron.
 So, to reduce the detrimental effect of sulphur, manganese
is added.
 Also sulphur having greater affinity towards manganese as
compared to iron and it forms manganese sulphide instead
of iron sulphide. Cementite
 This formed MnS is of round shape and well distributed
and if it is in large amount then only it affects the properties
of cast iron.
 Generally, the amount of sulphur in cast iron is between
0.06 to 0.12%.

Manganese Content
 In any commercial cast iron, the amount of manganese is
between 0.5 to 1.0%.
 It is an important element in the cast iron, because it
reduces the brittleness which formed because of iron
sulphide.

Cooling Rate
 On the microstructure of cast iron, cooling rate has a
considerable effect.
 Fast cooling rate increases the graphitization and forms Fig. No. 3.28 Microstructure of White Cast
white structure.  As there is no graphitization, the solidification of a white
 Whereas, slow cooling rate promotes graphitization and cast iron and microstructural changes are indicated by Fe-
results in gray structure. Fe3C equilibrium diagram.
 If, the cooling rate is intermediate, then there is formation  The carbon content is 6.67% due to that cementite phase is
of white cast iron at the surface and gray cast iron in the obtained so the limited application in industries.
centre.
 Also, cooling rate largely affects mechanical and 3.16.1 Manufacturing of White Cast Iron
structural properties of cast iron, hence it is an important  White cast iron is used in the manufacture of a wide range
parameter. of castings where in these characteristic are required.
 The martensitic and lower bainitic structure in white cast
3.16 White Cast Iron iron is achieved in the known processes by employing a
 In white cast iron, all the carbon is present in the combined relatively high content of hardenability increasing alloys.
form i.e. cementite and there is no free carbon (graphite).  The increase in hardenability obtained by adding certain
 Due to absence of graphite a fractured surface appears alloying elements to the iron results from delaying the
white, hence called as white cast iron. transformation times of the higher temperature
transformation.

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 Unit III Iron-Carbon Alloy System and Cast Iron

 Many of the hardenability increasing alloys, such as nickel,  They are used for shot blasting nozzles.
chromium, molybdenum, copper and vanadium are  It is used for crushers.
expensive alloys and the cost of these alloy is a substantial
factor in the cost of productivity martensitic and lower 3.16.5 Limitations of White Cast Iron
bainitic white cast iron. Because of extreme brittleness and black of machinability,
 Molten iron of white cast iron composition is proud in to a white cast irons find limited engineering applications.
sand mould or into a permanent mould such as cast iron or
graphite mould. The graphitization is suppressed by,
 After pouring, the casting is allowed to solidify in the 1. Hypoeutectic cast iron (2 to 4.3% C)
mould and, at some time after the casting has solidified, it 2. Eutectic cast iron (4.3% C)
is removed from mould. 3. Hypereutectic cast iron (% C is more than 4.3%)
 It has been generally believed that rapid cooling of the 3.16.6 Hypoeutectic White Cast Iron
casting from a high shake out temperature to below the Ms
Temperature sets up stresses in the casting which are very
undesirable in material of this extremely brittle nature and
may cause cracking.

3.16.2 Composition of White Cast Iron

Carbon: 2.2 to 2.70%
Silicon: 0.90 to 1.40%
Manganese: 0.40 to 1%
Phosphorus: 0.10 to 0.20%
Sulphur: 0.05 to 0.10%

3.16.3 Properties of White Cast Iron

 White cast iron of a certain composition is the first step in
the production of malleable cast iron castings.
 White cast iron can be made on the surface of a gray iron
casting provided the material is of specific composition.
 White cast iron castings can be made in sand moulds.
 Because of its poor fluidity it does not fill the mould freely.
 It can be obtained by rapid cooling of metal. Fig. No. 3.29 Fe-Fe3C Equilibrium diagram for 3.5%
 Tensile strength is good. carbon alloy
 Highly resistant to wear.
 The carbon is in the combined form.  Consider, white cast iron at 3.5% carbon on iron-iron
 It is hard, brittle and cannot be machined. carbide diagram and cooling from molten condition is
 The BHN is in the range of 350 to 500 BHN. explained as follows: (Refer Fig. No. 3.29).
 Compression strength is 140 to 175 kg/mm2.
From Point 1 to 2
 Modulus of elasticity 24 to 28 million Psi.
 The alloy exists in the liquid condition and there is no
change in the condition from point 1 to 2.
3.16.4 Applications of White Cast Iron
 They are used for making malleable castings.
From Point 2 to 3
 They are used for dies and extrusion nozzles.
 When cooling starts below point 2, separating of austenite
 They are used for grinding balls. starts from the liquid and further cooling will increase the
 It is used for mill liners. amount of austenite. It continues up to point 3.
 It is used for pump liners.  The proeutectic austenite is in the dendritic form hence, it
 They are used for road roller surface. separates from the liquid state. As per lever rule amount of
 It is used for wearing plates e.g. in rim of freight car wheel austenite at just above point 3 will be:
or railway brake blocks.  Amount of austenite
 Used for inferior castings and does not rust so much as grey 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑎𝑢𝑠𝑡𝑒𝑛𝑖𝑡𝑒
variety. 4.3 − 3.5
 It is used for liners for cement mixers. = × 100
4.3 − 2.0
 They are used for brake shoes.

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 Unit III Iron-Carbon Alloy System and Cast Iron

= 62 % of cementite and pearlite which is called as transformed

 The remaining 38% of the alloy is in liquid state with 4.3% Ledeburite.
carbon.
3.16.8 Hypereutectic White Cast Iron
At Point 3  Microstructural changes of hypereutectic white cast iron
 Liquid of eutectic composition solidifies at constant temp. are similar to the hypoeutectic white cast iron except
I.e. 1147°C and forms a eutectic mixture of austenite and instead of cementite, austenite will separate from the
cementite, which is known as Ledeburite. liquid.
1147℃  While freezing, primary cementite separates from the
Liquid → γ + Fe3C liquid in the dendritic form up to the eutectic temperature.
(4.3%C) (2%C) (6.67%C) At that temperature the remaining liquid solidifies as
eutectic mixture of cementite and austenite.
From Point 3 to 4  The remaining changes in hypereutectic white cast iron are
 There is no change in the existing structure. Only the similar to hypoeutectic cast iron.
amount of Fe3C increases which is called as proeutectoid
cementite.

At Point 4
 All the austenite (primary and eutectic) transforms
isothermally to a eutectoid mixture of ferrite and cementite
which is known as pearlite.
727℃
γ → α + Fe3C Fig. No. 3.31 Microstructure of hypereutectic white cast
(0.8%C) (0.025%C) (6.67%C) iron
 Fig. No. 3.31 shows the microstructure of hypereutectic
From Point 4 to 5 white cast iron. At room temperature the microstructure
 There is almost no change in microstructure but amount of contains dendrities of primary cementite in the matrix of
Fe3C increases slightly. transformed Ledeburite.
 At room temperature pearlite is in a matrix of transformed 3.17 Malleable Cast Iron
is in a matrix of transformed Ledeburite (Fe3C + Pearlite).  In this type of cast iron, most or all of the carbon is
 It is due to solubility of carbon in ferrite from 0.025% to uncombined in the form of irregular round particles known
0.008%. as temper carbon. This is obtained by heat treatment of
white cast iron.
3.16.7 Eutectic White Cast Iron
 It solidifies at eutectic temperature of 1147°C by a eutectic 3.17.1 Manufacturing of Malleable Cast Iron
transformation process and gives a Ledeburite with no  Malleable (soft) cast iron is produced from white cast iron
proeutectic phase. casting by using malleablizing heat treatment.
 Cooling from eutectic temperature (1147°C) to eutectoid  In malleablizing heat treatment white casting is slowly
temperature (727°C) increases only the amount of Fe3C heated at 900°C and held at this temperature for a long time
without any change in structure. It is due to decrease in followed by cooling to room temperature.
solubility of carbon in austenite.  Fig. No. 3.32 shows malleablizing heat treatment cycle.
 Further cooling from 727°C to room temperature slightly
increases the amount of cementite Fe3C.

Fig. No. 3.30 Microstructure of eutectic white cast iron

 Fig. No. 3.30 shows the microstructure of eutectic white
cast iron. At room temperature the microstructure consists Fig. No. 3.32 Malleablizing heat treatment cycle

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 Unit III Iron-Carbon Alloy System and Cast Iron

 Because of heating at 900°C (point 1), cast iron structure  Through the above critical range the eutectoid reaction
consists of austenite and cementite. would take place. During the slow cooling the carbon
 Cementite being a metastable phase decomposes to dissolved in the austenite is converted to graphite on the
austenite and graphite with long holding time, which gives existing temper carbon particles and remaining austenite
rise to rough, ragged, irregular nodules or spheroids. These transformation into ferrite.
spheroids are called as rosettes of temper carbon graphite.  Once graphitization is complete no further structural
 Hence, at point 2 the rosettes are in a matrix of austenite. changes takes place during cooling to room temperature
 With moderate rate of cooling up to room temperature, and the structure consist of temper carbon nodules in a
austenite is transformed into pearlite at eutectoid ferrite matrix. This is called as ferrite malleable cast iron.
temperature hence at point 3 the microstructure shows
rosettes of temper carbon graphite in pearlite form. Properties of ferrite malleable cast iron
 Graphite nodules also serve to lubricate cutting tools,
which accounts for the very high machinability of
malleable cast iron.
 The ferrite malleable cat iron shows higher strength and
ductility than gray cast iron.
 Graphite nodules lubricate the cutting tools leading to good
machinability of malleable cast iron.

Ferrite Application of ferrite malleable cast iron

 They are used for pipe fittings.
 Expansion joints.
 Railing casting on bridges
Rosettes of temper  Bearing blocks
carbon  Valves
 Farm equipment
Fig. No. 3.33 Microstructure of malleable cast iron  Chains
 If the rate of cooling is slow, the cementite from pearlite  Reducing gear housings
may decompose giving ferrite and graphite. Hence, at point  Rear-axle housings
3’ it shows rosettes of temper carbon graphite in the matrix  Hubs
of ferrite.  Hooks
 Fig. No. 3.33 shows microstructure of malleable cast iron.  Leads
 Nuts
3.17.2 Composition of Malleable Cast Iron  Flanges
Carbon: 2.16 to 2.90%  Couplings
Silicon: 0.90 to 1.90%
Manganese: 0.15 to 1.25% Pearlitic malleable cast iron
Sulphur: 0.02 to 0.20%  To obtain pearlitic matrix, 1% manganese is added to cat
Phosphorus: 0.020 to 0.15% iron, or second stage graphitisation is replaced by a quench,
usually air, which cools the casting through the eutectoid
3.17.2 Types of Malleable Cast Iron range fast enough to retain combined carbon throughout
1. Ferrite malleable cast iron the matrix.
2. Pearlitic malleable cast iron  The amount of pearlite formed depends upon the
3. Whiteheart malleable cast iron temperature at which the quench starts and rate of cooling.
4. Blackheart and pearlitic malleable cast iron If the air quench produces a fast enough cooling rate
through the eutectoid, the matrix will be completely
Ferrite malleable cast iron pearlitic.
 The structure consists of nodules of temper carbon  A fully ferritic malleable cast iron may be converted into
embedded in ferrite matrix (Due to slow cooling in pearlitic malleable cast iron by reheating above the lower
eutectoid temperature range). critical temperature, followed by rapid cooling.
 As these nodules break the continuity to lesser damaging  At higher temperature carbon will be dissolved from the
extent of tough ferrite. The castings are cooled slowly at graphite nodules and subsequent cooling retain the
the rate of 5° to 15° F/hr. combined carbon.

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 Normally, after air cooling, the pearlitic malleable cast iron  The microstructure of blackheart malleable cast iron has a
is obtained. matrix essentially of ferrite.
 Castings are heated to higher temperature at 550 to 650°C.  The microstructure of pearlitic malleable cast iron has a
Malleable iron is rarely used due to the formation of brittle matrix, according to the grade specified of pearlite or other
and low strength white cast iron under the weld bead. transformation produces of austenite.
 The presence of larger amount of silicon in white cast iron  Graphite is present in the form of temper carbon nodules.
castings helps to graphitize it during malleable heat The microstructure shall not contain flake graphite.
treatment. But a thick casting having higher silicon may
result in gray cast iron, in the centre while causing it. As 3.18 Gray Cast Iron
the casting should be of white iron up to the centre before  Graphite flakes is surrounded by a matrix of either pearlite
malleable heat treatment is given, silicon content has to be or α-ferrite. Exhibits gray fracture surface due to fracture
kept low in the composition, which makes graphitization occurring along with graphite plates. The carbon is in free
during malleable treatment a long and difficult process. form in the gray cast iron.
 The fracture appearance is gray colour due to this it is
Properties of pearlitic malleable cast iron called as gray cast iron. The strength of gray iron depends
 The malleable cast iron have reasonable ductility. on the strength of steel matrix and the size and character pf
 High strength graphite flakes in it. A typical feature of gray iron is that
 Toughness and even bendable graphite is in the form of flakes in microstructure.
 Low cost  Gray cast iron is the most versatile of all foundry metals.
 Easy of machining The high carbon content is responsible for ease of melting
and casting in the foundry and for ease of machining in
Applications of pearlitic malleable cast iron subsequent manufacturing. The low degree or absence of
 High strength and hardness shrinkage and high fluidity provide maximum freedom of
 They are used for cam shafts design for the engineer.
 Crank shafts  All of the carbon in gray iron, other than that combined
 Axles with iron to form pearlite in the matrix, is present as
 Differential housing in automobile jaws of universal joint graphite in the form of flakes of varying size and shape.
shafts  It is the presence of these flakes also imparts most of the
 Links and rollers of conveyer chains desirable properties to gray iron.
 Bushings  The properties of gray iron are affected by the amount of
 Couplings brake shoes graphite present as well as the shape, size and distribution
 Malleable irons are used chiefly for thin walled castings of the graphite flakes.
because there restriction in section thickness.  Grey cast iron is easily cast but it cannot forged. It is much
stranger in compression then in tension, therefore it is
Limitations of pearlitic malleable cast iron commonly found in columns, but not in structural beams.
 Pearlitic malleable cast iron has limitations of section
thickness.
Graphite Flakes
 Lower damping capacity
 Impact resistance

Whiteheart malleable cast iron

 The microstructure of whiteheart malleable cast iron
depends upon section size. Small sections contain pearlite Pearlite
and temper carbon in ferritic substrate. In the large sections
there exist three different zones.
 Surface zone which contains pure ferrite.
 Intermediate zone which has pearlite, ferrite and temper
carbon.
 Core zone containing pearlite, temper carbon and ferrite
inclusions. The microstructure shall not contain flake
graphite. Ferrite
Blackheart and pearlitic malleable cast iron

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 Unit III Iron-Carbon Alloy System and Cast Iron

 Strength of the iron depends almost entirely on the matrix

in which the graphite is embedded.

3.18.2 Composition of Gray Cast Iron

Carbon: 2.4 to 3.8%
Silicon: 1.2 to 3.5%
Manganese: 0.5 to 1.0%
Sulphur: 0.06 to 0.12%

3.18.3 Formation of Graphite Flakes

 Commercial gray cast iron is either hypoeutectic or eutectic
Fig. No. 3.34 Microstructure of gray cast iron in nature. We neglect the presence of dendrites and primary
 It is highly susceptible to corrosion when exposed to austenite in hypoeutectic iron due to which the constraints
moisture and it has several typical problems which usually are imposed on radial growth of the eutectic cell.
can be identified by visual inspections.  Fig. No. 3.36 shows the stages in the formation of graphite
flakes form the eutectic liquid present. Once graphite has
nucleated, solidification takes place at nuclei fig. no.3.36
3.18.1 Manufacturing of Gray Cast Iron (a), from each of which is formed a roughly spherical lump
 In manufacturing of gray cast irons, the tendency of called the eutectic cell.
cementite to separate into graphite and austenite or ferrite
is favoured by controlling alloy composition and cooling
rate.
 These alloys solidify by first forming primary austenite.
The graphitization process is added by high carbon content,
high temperature and the proper amount of graphitizing
elements mostly silicon.

Fig. No. 3.36 (a), (b) and (c) stages in the formation of
graphite flakes (d) growth of graphite flakes
 It grows approximately in radial manner, where there is
simultaneous growth of austenite and graphite. Later on,
when in continuous contact with the liquid, the flakes bend,
twist and branch as depicted in fig. no. 3.36 (d).
 There is continuous branched skeleton of graphite in each
eutectic cell like a cabbage. When the rate of cooling is
increased, there is more undercooling, then the skeleton is
branched more frequently with the rapid radial growth of
the cell and thus, finer graphite flakes are observed.
 The diameter of the eutectic cell decreases as the number
of cells per unit volume increase, and this results in higher
tensile strength, though the soundness of the casting is
affected adversely.
Fig. No. 3.35 Iron graphite equilibrium diagram  The number of nuclei can be increased by inoculants as
 With proper control of above factors, alloy will follow the well as by sulphur. Super heating or holding time of molten
stable iron graphite equilibrium diagram forming austenite metal reduces the number of nuclei.
and graphite at the eutectic temperature of 1154°C at any
rate any cementite which is formed will graphite rapidly. Properties of gray cast iron
 During continuous cooling there is additional precipitation  Low cast of production
of carbon because of the decrease in solubility of carbon in  Low melting point
austenite. This carbon is precipitate as graphite.  Good castability
 Good machinability

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 Unit III Iron-Carbon Alloy System and Cast Iron

 Good wear resistance  Nodular cast iron is produced from gray cast iron by
 Good damping capacity adding small quantity of certain elements which are called
 High compressive strength as nodulizing elements.
 High thermal conductivity  The elements used for this purpose are magnesium,
 Good resistance to atmosphere corrosion calcium, cerium, barium, lithium etc.
 Notch-insensitive  All the nodulizing elements have low density and are
highly chemically reactive.
Applications of gray cast iron  If these elements are added in the pure form, they float at
 They are used in flywheels. the top of bath and burn at the surface.
 Guards and frames around hazardous machinery.  During addition of nodulizing elements to the molten bath,
 It is used in gear housings. large amount of gases are produced which gets dissolved
 Useful in pump housings. in the melt.
 They are used steam turbine housings.  These gases give rise to large number of blow holes in the
 Used in motor frames. solidified casting.
 They are used in sewer covers.  Hence, careful design of the mould is necessary to avoid
shrinkage cavities in the solidified casting.
 Used for enclosures for electrical equipment’s.
 They have used for manhole covers.
 Useful for rolling mill and general machinery parts like
lathe bed.
 Useful for gas or water pipes for underground purpose. Ferrite
 They are used in ingot moulds.
 It is used in sanitary works.
 Used in household appliance.
 They are used for brake drums and clutch plates.
 Used in pressure pipe fittings.

Limitations of gray cast iron Pearlite

 Apart from the low ductility and toughness, gray cast irons
are section sensitive i.e. depending on the section thickness
of the casting the microstructure and thus the properties
vary.
 Thick sections have low strength and care has to be taken, Graphite Nodules
when designing the castings.

3.18.4 Advantages of Gray Cast Iron Over White Cast Iron

 Gray cast iron, carbon is free form but in white cast iron
carbon is combined form.
 In gray cast iron graphite flakes obtained but in white cast
iron dendrites are obtained.
 Gray cast iron very good damping capacity as compared to
white cast iron.
 Gray cast iron has good machinability than white cast iron.
 They gray cast iron contain more silicon than white cast
iron. Fig. No. 3.37 Microstructure of Nodular Cast Iron

3.19.1 Manufacturing of Nodular or Spheroidal Graphite

3.19 Nodular or Spheroidal Graphite Cast Iron Cast Iron
 It consists of graphite in the form of nodules or spheroids.
 The following are the steps of manufacturing of spheroidal
 Nodular cast iron is also called as, Spheroidal Graphite graphite cast iron.
Cast Iron or Ductile Cast Iron. 1. Desulphurisation
 Nodular cast iron produces less interruption in steel like 2. Nodulising
matrix as compared to gray cast iron. 3. Inoculation
 This increases tensile strength, ductility and toughness.

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 Unit III Iron-Carbon Alloy System and Cast Iron

Desulphurisation Properties of Nodular/Spheroidal Graphite Cast Iron

 Sulphur helps to form graphite as flakes. Thus, the raw  Good machinability
material for producing iron should have low sulphur (less  Good damping capacity
than 0.1%) or remove sulphur from iron during melting or  High wear resistance
by mixing iron with a desulphurising agent such as calcium  Reasonable castability
carbide or soda ash.  Ductile iron has a high fluidity
 In nodular cast iron graphite appears as rounded particles
Nodulising or nodules or spheroids.
 Magnesium is added to remove sulphur and oxygen still  Soft annealed grades of nodular cast iron can be turned at
present in the liquid alloy and provides 0.04% magnesium very high feeds and speeds.
which causes growth of graphite to be spheroid.  The properties of nodular cast iron depend upon metal
 Magnesium treatment desulphurises the iron to below composition and cooling rate.
0.02% sulphur before alloying with it. Magnesium and  Tensile strength range is 39 to 80 kg/mm2.
such elements have strong affinity for sulphur and thus
 Percentage elongation range is 8 to 20%.
sulphur from the molten alloy’s an initial step or, producing
 Hardness is 100 to 300 BHN.
spheroidal graphite iron.
 These additions are expensive to increase the cost of
Application of Nodular/Spheroidal Graphite Cast Iron
spheroidal graphite iron produced. Thus, sulphur molten
 They are used cylinder blocks and heads.
alloy, before nodulising, should be kept low.
 They are used in piston.
 Magnesium is added when melt is near 1500°C but
 It is used in bearing blocks.
magnesium vaporizes at 1150°C magnesium, being lighter
floats on the top of the bath, and being reactive burn off at  It is used in pipes.
the surface.  They are used in furnace doors.
 In such cases magnesium is added as Ni-Mg, Ni-Si-Mg  They are used in sheet metal dies.
alloy or magnesium coke to reduce violence of reaction and  It is used in punch dies.
to have saving in magnesium. Magnesium metal can be  They are used in gears.
added as metal itself. The method of addition include ladle  They are used in crank shafts.
transfer covered ladle techniques porous plug.  They are used in metal working rolls.
 They are used in values and fittings.
Inoculation  It is used in internal combustion engines.
 As magnesium is carbide former, ferrosilicon is added  They are used in paper industries and machinery.
immediately as inoculant. Remelting cause’s reversion to  It is used in construction machinery.
flake graphite due to the loss of magnesium stirring of  They are used in farm implements and tractors.
molten alloy after addition of nodulising element evolves a
lot of gas, which gets dissolved in liquid alloy and forms 3.20 Mottled Cast Iron
blow holes in solid casting.
 Mottled cast iron shows free cementite and graphite flakes
 The contraction during solidification of nodular cast iron in their microstructure.
castings is much greater than of grey iron castings, which
needs careful design of moulds to avoid shrinkage cavities
in solidified castings.
 In spite of these drawbacks, nodular cast iron is replacing
gray iron and steels in applications. Nodules of graphite
weakens the steel matrix to a lesser extent than gray iron
flakes. The nodules do not act very much as stress-raisers. White C.I
3.19.2 Composition of Nodular or Spheroidal Graphite Cast
Iron
Carbon: 3.7%
Silicon: 2.5%
Manganese: 0.3%
Sulphur: 0.02%
Phosphorus: 0.02% Graphite Flakes/
Magnesium: 0.04% Gray C.I
Fig. No. 3.38 Microstructure of Mottled Cast Iron

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 Unit III Iron-Carbon Alloy System and Cast Iron

 For a given composition, fast rate of cooling gives white  Chilling to certain depth (12 to 30 mm) is because of the
cast iron whereas, slow rate of cooling gives gray cast iron. cooling (chilling) obtained due to high thermal
 For intermediate cooling rates, mottled cast iron is conductivity of metal mould. The composition of molten
observed. alloy is so chosen that normal cooling results in grey cast
 Mottled structure has some bad properties and hence it iron in the whole section, but fast cooling of the whole
should be avoided. surface, or a depth of the surface yields white cast iron.
 For this purpose carbon and silicon content is increased so  The fast cooling is obtained by employing metal or
that melt solidifies as gray instead of mottled under the graphite plates called chills in the sand mould.
existing cooling conditions.  To calculate chill depth in chilled casting chill test is
 Fig. No. 3.38 shows a microstructure of a mottled cast iron. used.
 Chill depth is evaluated by solidifying the cast iron melt
3.20.1 Manufacturing of Mottled Cast Iron in a suitable shaped mould (wedge or step bar) which
 In mottled cast iron, fast cooling rate is used to obtain white gives different cooling rate while solidification.
cast iron and slow cooling rate is used to grey cast iron.  A test sample of melt from cupola is poured into a sand
But, we use moderate cooling rate to cool iron carbon and mould of wedge or step bar shape.
thus, mottled cast iron is formed.  The test sample is fractured and the chill depth i.e. the
region which appears white is evaluated.
3.20.2 Composition of Mottled Cast Iron
Carbon: 3.32%
Manganese: 0.72%
Silicon: 1.40%
Phosphorus: 0.08%
Sulphur: 0.01%
Chromium: 0.28%

Properties of Mottled Cast Iron

 Surface hardness is high.
 Good wear resistance.

Applications of Mottled Cast Iron

 They are used for mill rolls.
 They are used for brake shoes.
 They are used for flour milling shafts.
 They are used for roller.

3.21 Chilled Cast Iron

 Chilled cast iron shows white structure at surface and gray
in the centre.
Fig. No. 3.40 Step bar test piece for Chill depth
 Hence, good properties of white cast iron i.e. hardness and
wear resistance and gray cast iron i.e. machinability,  Chilled cast iron having 3 to 3.3% carbon.
damping capacity can be coupled together.  The depth of chill decreases and the hardness of chilled
zone increases with increasing carbon content.
 The depth of chill is decreases with increasing silicon
content. Phosphorus decreases the depth of chill with
carbon and silicon constant, an increase of 0.1%
phosphorous will decrease the depth of chill. About 0.1
inch nickel reduces the chill depth and refines the carbide
structure.
 Chromium is used in small amount to control chill depth.
Manganese decreases the depth of chill unit. The formation
of manganese sulphide after that increases chill depth and
hardness.
 Molybdenum improves the resistance of the chilled face to
Fig. No. 3.39 Microstructure of Chilled Cast Iron spalling, pitting, chipping and heat checking.

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 Unit III Iron-Carbon Alloy System and Cast Iron

3.21.1 Manufacturing of Chilled Cast Iron  Because of more carbon and alloying elements in
 The process begins with the highest quality chilled cast austenite; martensite finish temperature is below the room
iron castings. temperature.
 The hard alloy surface (48-52 Rc) is poured first followed  Hence, austenite to martensite transformation does not
by the gray cast iron core, which assures long life of the completed at room temperature.
rolling surface.  As nickel is a graphitizer, if only Nickel is added for the
 The roll castings are then stress relieved and allowed to above purpose there is chance of graphitization.
cool, rough turned and rough bored in large lathes.  Generally, amount of Nickel is between 3 to 5% and
 The casting is then hardness tested in several locations on chromium is between 1 to 3%.
the rolling surface and ultrasonically inspected to insure  Ni-hard cast iron shows hardness in the range of 550 to 700
that there are no voids or cracks in the castings. BHN.
 The casting is then precision bored for shafts as specified  Ni-hard cast iron has poor impact strength and fatigue
by Ross Roll manufacturing and then precision ground. resistance.
 After final inspections, a serial number is stamped with a  To improve these properties continuous carbide is replaced
unique number on the end of each roll casting that by discontinuous carbides by increasing Nickel and
identifies the roll throughout its useful life. Chromium content.
3.21.2 Composition of Chilled Cast Iron 3.22.2 Ni-Resist
Carbon: 2.8 to 3.6%  By adding large amount of Nickel, corrosion resistance of
Silicon: 0.5 to 0.8% gray or nodular cast iron is increased.
Manganese: 0.4 to 0.6%
 As Ni is an austenite stabilizer, the matrix becomes
austenitic.
Properties of Chilled Cast Iron
 Hence, such cast iron is called as austenitic cast iron.
 High wear resistance.
 Generally, amount of Nickel is 14 to 36% and Cr is 1 to
 Good abrasion resistance.
5%.
 Good damping capacity.
 The microstructures contains flakes or nodules of graphite
 Low notch sensitivity. uniformly distributed in the austenite matrix.
Applications of Chilled Cast Iron  Ni-Resist cast iron has better corrosion resistance, good
 Chilled cast iron used as rail-freight car wheel. erosion resistance and wear resistance.
 Cane crushing roll.  Up to 800°C they have good scaling and growth resistance
 Road rollers. after stabilizing treatment.
 Grinding balls.
 Liners. 3.22.3 Silal and Nicrosilal
 To increase oxidation resistance and prevent growth of cast
 Stamp shoes and dies.
iron at high temperatures, silicon is added to low carbon
 Sprockets.
cast iron.
 Generally, the amount of silicon is between 5 to 7%.
3.22 Alloy Cast Iron  The microstructure of this cast iron contains Ferrite and
 Generally, cast iron has low impact resistance, corrosion fine graphite which is called as Silal.
resistance and temperature resistance.  The main drawback of silal is that it is brittle in nature.
 To increase these properties certain alloying elements are  For this purpose Ni and Cr are added which changes
added in suitable amount. ferritic matrix to austenitic matrix, such a cast is called as
 Mostly, Ni, Cr, Mo, V, Cu, Si are used for this purpose. Nicrosilal.
 Some of the popular cast iron from this group are as  C- 2 to 2.3%, Si- 5 to 6%, Ni- 18 to 22%, Cr- 2 to 4%
follows:
1. Ni-Hard
2. Ni-Resist
3.23 Specific Applications of Cast Iron
3.23.1 Specific Applications such as Machine Tools
3. Silal & Nicrosilal
 Machine tool is a machine for shaping or machining metal
3.22.1 Ni-Hard or other rigid materials, usually by cutting, boring,
grinding, shearing or other forms of deformation.
 By the addition of Ni and Cr, hardness and wear resistance
of white cast iron is increased.  Machine tools employ some sort of tool that does the
cutting or shaping. All machine tools have some means of
 Due to increased hardenability, austenite transforms to
martensite during solidification of alloy.

ENGINEERING METALLURGY (202049) 72

 Unit III Iron-Carbon Alloy System and Cast Iron

constraining the work piece and provide a guided stainless steel as well as in cast iron. If customization is
movement of the parts of the machine. required to meet specific needs, the pumps can be equipped
 Thus the relative movement between the work piece and with special seal solutions.
the cutting tool which is called ass tool path is controlled
or constrained by the machine to at least some extent, rather 3.23.4 Specific Applications such as Valves
than being entirely off hand or freehand.  Bronze valves are commonly used for plumbing, heating
 Today machine tools are typically powered other than by and air conditioning non-specific applications or used in
human, used to make manufactured parts in various ways water supply systems.
that include cutting or certain other kinds of deformation.  Bronze valves are generally when the line size in under 3”
With their inherent precision, machine tools enable the and low cost and availability are important.
economical production of interchangeable parts.  Bronze valves are made by pouring a copper alloy into sand
molds. Valves are also made up of iron. The valve body
3.23.2 Specific Applications such as Automobiles material may or may not be made of the same material for
 Drum brakes, levers, and rods or cables operated the shoes the valve trim.
mechanically. Oil pressure in a small wheel cylinder and  Valves are also made of ductile iron. Another name of
pistons operated the brakes, though some vehicles ductile iron is nodular iron. Ductile iron is most often used
continued with purely mechanical systems for decades. in marine industry and for underground pipe line.
 Some design have two wheel cylinders. The shoes in drum  Ductile iron valves can be used in applications that
brakes wear thinner and brakes required regular adjustment experience vibration and shock. Ductile iron absorbs shock
until the introduction of self-adjusting drum brakes. Disc and also has good corrosion resistance.
brakes gradually replaced drum brakes on the front wheels  While there are no size limitations for iron valves, these
of cars. Now practically all cars use disc brakes on the front valves have temperature limits. Cast iron has a temperature
wheels and many use disc brakes on all wheels. limit of approximately 232°C and ductile iron has a limit
 However, drum brakes are still often used for hand brakes, of 343°C.
as it has proven very difficult to design a disc brake suitable  Valves are also made of steel and stainless steel. Steel
for holding a parked car. Moreover, it is very easy to fit a valves can be separated into two categories based on how
drum hand brake inside a disc brake so that one unit serves the valve is made.
as both service brake and hand brake.  Forged steel and or cast steel. Forged steel is formed heated
 Early brake shoes contained asbestos. When working on slugs, which are forged into the valve shape by huge
brake systems of older cars, care must be taken not to forging hammers and presses. Cast steel is melted in a
inhale any dust present in the brake assembly. furnace and then poured into moulds in a foundry.
 To regulate asbestos production, and brake manufactures
had to switch to non-asbestos linings. Owners initially University Question
complained of poor braking with the replacements.
 A majority of daily driven older vehicles have been fitted
with asbestos free linings. Many other countries also limit November 2019 Examination
the use of asbestos in brakes. 1. Draw Fe-C equilibrium diagram and label the
temperature composition and phrase. (Refer Section.
3.23.3 Specific Applications such as Pumps 3.3)
 Depending on the specific application the pumps can be 2. Why do hypoeutectoid steels with Widmanstaten
customized to perfectly match every requirement. structures have low toughness and ductility values?
 Pumps can be supplied in different lengths and with the (Refer Section. 3.8)
exact pressure and flow required for different material. 3. Differentiate between malleable cast iron and gray cast
Equally suitable for vertical and horizontal installation, the iron with the help of the following criteria:
pumps even offer complete freedom in terms of design. 1. Method of formation of graphite
 Furthermore, the pumps can be optionally supplied with 2. Damping capacity
integrated frequency converters or an advanced E-solution 3. Machinability
to increase system efficiency and optimize processes, 4. Applications
including lowering heat input into the cooling lubricant. (Refer Section. 3.17 and 3.18)
 Specifically for grinding and boring processes, impressive May 2019 Examination
range of high-pressure pumps includes models that
efficiently handle up to 120 bar which is required. 1. Draw neat diagram of microstructures and indicate
 For example, deep hole boring. The entire pump range phases present and their amounts in the following
targeted at machine tool applications is available in plain carbon steels under equilibrium conditions:

ENGINEERING METALLURGY (202049) 73

 Unit III Iron-Carbon Alloy System and Cast Iron

1. 0.4% carbon steel

2. 1.2% carbon steel
(Refer Section. 3.6)
2. Sketch and label microstructure of the following steels
1. Hypoeutectoid Steel
2. Eutectoid steel
(Refer Section. 3.6.1 and 3.6.2)
3. State two advantages of alloy steels over plain carbon steel
and two advantages of plain carbon steel over alloy steel.
(Refer Section. 3.10)

November 2018 Examination

1. Draw Iron Carbon diagram showing all details, like
temperature, composition, Phases, critical lines and
reactions. (Refer Section. 3.3)
2. Classify cast iron and explain why they are called as
cast irons only? (Refer Section. 3.13 and 3.11)
3. Compare steel and cast iron on the basis of
composition, properties and application. (Refer
Section. 3.12.1)

November 2017 Examination

1. What are the different types of cast iron? Explain
gray cast iron microstructure. State and justify the
use of gray cast iron in two applications. (Refer
Section. 3.13 and 3.18)
2. Draw neat diagram of microstructure of
microstructure and indicate phases present and
their amounts into the following plain carbon
steels under equilibrium conditions:
0.2% carbon steel
0.8% carbon steel
(Refer Section. 3.6)
3. Explain with the help of figure, widmanstaten
structure. (Refer Section. 3.8)
4. Explain classification of steels on the basis of
composition. (Refer Section. 3.10)

May 2017 Examination

1. What is meant by critical temperature line in an
equilibrium diagram? What changes take place, during
cooling, at A1 temperature in an Iron-Iron carbide
phase diagram? (Refer Section. 3.5)
2. Write properties and applications of grey cast iron.
(Refer Section. 3.18)
3. What are the advantages of Nodular cast iron over grey
cast iron? Draw a typical microstructure of Nodular
cast iron. (Refer Section. 3.19)
4. Explain classification of steel. (Refer Section. 3.10)

ENGINEERING METALLURGY (202049) 74

 Unit IV- Heat Treatment of Steels

Unit – IV
Heat Treatment of Steels

Syllabus:
Transformation products of Austenite, Time Temperature Transformation diagrams, critical cooling rate,
continuous cooling transformation diagrams. Heat treatment of steels: Annealing, Normalising, Hardening &
Tempering, quenching media, other treatments such as Martempering, Austempering, Patenting, Ausforming.
Retention of austenite, effects of retained austenite. Elimination of retained austenite (Subzero treatment).
Secondary hardening, temper embrittlement, quench cracks, Hardenability & hardenability testing, Defects due to
heat treatment and remedial measures.
Classification of surface hardening treatments, Carburising, heat treatment after Carburizing, Nitriding, Carbo-
nitriding, Flame hardening, and Induction hardening.

Section No. Topic Name Page No.

4.1 Introduction 76
4.2 Transformation Products of Austenite 76
4.3 Time-Temperature-Transformation (T-T-T) Diagram 79
4.4 Critical Cooling Rate 80
4.5 Continuous Cooling Transformation Diagram 80
4.6 Heat Treatment of Steels 81
4.7 Austempering 84
4.8 Martempering 84
4.9 Ausforming 85
4.10 Patenting 85
4.11 Retention of Austenite 86
4.12 Effects of Retained Austenite 86
4.13 Elimination of Retained Austenite 86
4.14 Secondary Hardening 86
4.15 Temper Embrittlement 87
4.16 Quench Cracks 87
4.17 Hardenability 87
4.18 Defects due to Heat Treatment and Remedial Measures 89
4.19 Surface Hardening Treatments 89
4.20 Carburizing 89
4.21 Heat Treatment after Carburizing 91
4.22 Nitriding 92
4.23 Carbo-Nitriding 92
4.24 Flame Hardening 93
4.25 Induction Hardening 94

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 Unit IV- Heat Treatment of Steels

4.1 Introduction 2) Bainite

 In previous unit 3, we have learned the wide range of 3) Martensite
applications where alloys of iron and carbon are used.
 This wide range of applications is possible because of the 4.2.1 Transformation of Austenite to Pearlite
ease with which the properties of steels can be modified
and suited to the requirement.
 These properties can be easily altered without melting the
alloys with the help of various heat treatments.
 Heat treatment is the defined as a series of processes
involving heating and cooling operation (in a specified
sequence) as applied to a material, so as to modify its
internal microstructure.
 The extent of change in required within the internal
microstructure can be easily controlled through variation in
cycle time of the heat treatment.
 The internal microstructure is influential in determining
the physical, mechanical and chemical properties of a Fig. No. 4.1 Austenite to Pearlite Transformation
material.  As seen in fig. no. 4.1 (i), the first plate of Fe3C nucleates
out along the austenite grain boundary.
4.1.1 Objectives of Heat Treatment  As the Fe3C plate grows in the edgewise direction, carbon
 Increase hardness, wear and abrasion resistance and cutting from the austenite matrix diffuses towards its flat surfaces.
ability of steel.  This reduces the carbon near the adjacent region of the
 Re-soften the steel after it has been hardened by other heat growing cementite (Fe3C) plate.
treatment or cold working.  When the carbon content reduces below a critical value, the
 Adjust its mechanical, physical or chemical properties. ferrite plates, develops by nucleation process on either side
 Obtain desired microstructure. of the cementite phase. Refer Fig. No. 4.1 (ii).
 Reduce or eliminate internal residual stresses as internal  The ferrite phase continues to grow along the edgewise
stresses lead to premature or brittle failure of the direction and hereby rejecting the excess carbon.
components.  This rejected carbon combines locally and leads to
 Induce controlled residual stress. nucleation of new parallel cementite (Fe3C) plate on both
 Decrease or increase grain size. sides. Refer Fig. No. 4.1 (iii).
 Produce special microstructure to increase machinability  This repetition of nucleation of cementite plate and ferrite
and corrosion resistance. phase continues to grow.
 Stabilize the steel so that it does not show changes in  This results in formation of lamellar structure i.e. creation
dimensions with time. This property is highly essential for of colony of alternate parallel plates of cementite (Fe3C)
application in precision gauges and measuring instruments. and ferrite. Refer Fig. No. 4.1 (iv).
 Eliminate gases, particularly hydrogen, which embrittles  These alternate layers of cementite and ferrite together are
the steel. called as pearlite.
 Change the composition of the surface by diffusion of C,
N, Si etc. so as to increase wear resistance, fatigue life and
corrosion resistance.

4.2 Transformation Products of Austenite

 In Iron-Iron Carbide equilibrium diagram Austenite is a
metastable phase which is existing above 727°C.
 It has been observed through Iron-Iron Carbide
equilibrium diagram that Austenite does not exist at room
temperature.
 It gets transformed into different phases based on the
cooling rate.
 Following are the transformation observed during its
cooling:
1) Pearlite Fig. No. 4.2 100% Resolved Pearlite

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 Unit IV- Heat Treatment of Steels

 The first colony during its growth also nucleates other

colonies until a nodule containing many pearlite colonies
gets formed. Refer Fig. No. 4.1 (v).
 It is observed that lower is the transformation temperatures,
the rate of nucleation is higher, which gives finer pearlite.
 Finer is the pearlite better is the hardness and strength.
 Vice-versa, higher transformation temperatures gives
coarse pearlite, which has less hardness and strength.
 The main characteristics of Pearlite transformation are:
1. It’s diffusion transformation.
2. It’s time and temperature dependent.
 Refer Fig. No. 4.2, for actual appearance of austenite to
pearlite microstructure under optical microscope.
(a) Upper Bainite (40-50 Rc Hardness)
4.2.2 Transformation of Austenite to Bainite

(b) Lower Bainite (50-60 Rc Hardness)

Fig. No. 4.3 Austenite to Bainite Transformation Fig. No. 4.4 Microstructure of Bainite
 If the transformation of Austenite is allow to take place  Similarly, the bainitic transformation occurring at lower
below 550°C it results in non-lamellar structure called as temperature is called as lower Bainite.
Bainite.  The lower Bainite has acicular i.e. needle like appearance.
 If the austenite is rapidly cooled below 550°C and held  For a given steel, the hardness goes on increasing in the
isothermally, the morphology formed is not lamellar but transformation of austenite-pearlite-upper Bainite-lower
needle like. Bainite.
 Bainite is an extremely fine mixture of ferrite and  For eutectoid steel, the hardness of upper Bainite is in the
cementite. range of 40-50 Rc and that of lower Bainite is in the range
 Unlike nucleation of cementite resulting in formation of of 50-60 Rc.
pearlite, bainitic transformation starts by nucleation of
ferrite. Refer Fig. No. 4.3 (i). 4.2.3 Transformation of Austenite to Martensite
 The carbon in the vicinity of ferrite combines to form  If the austenite is cooled at a very fast rate, i.e. a thermally,
cementite. Refer Fig. No. 4.3 (ii). the morphology formed is knows as martensite.
 As bainitic transformation takes place at low temperatures,  This microstructure appears like a rod/needle type is
the rate of nucleation is very high with reduced growth rate. referred as Martensite.
 Thus, a microstructure consisting of very fine distribution  In case of martensitic transformation being a fast cooling
of cementite in ferrite is formed. rate carbon item will get and entrapped within the unit cell
 The bainitic transformation occurring at higher leads to the formation of martensitic structure.
temperature is called as upper Bainite.  This super saturated solution of carbon in α-iron B.C.T.
 The upper Bainite has a feathery appearance and its (Body Centered Tetragonal) structure is called as
microstructure looks like tiny plates of cementite oriented Martensite.
parallel to long ferrite needles.

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 Unit IV- Heat Treatment of Steels

 Low carbon martensite steel appears like rod / strip and is

referred to as Lath Martensite.
 High carbon martensite steel appears like needles and is
referred to as Plate Martensite.

Fig. No. 4.5 B. C. T. Crystal Structure

 In a B. C. C. structure, the lattice parameters are equal i.e.
a = b = c.
 In a B. C. T. structure, two of the lattice parameters are
equal, while the third is expanded because of trapped
carbon. Hence a = b ≠ c. Refer Fig. No. 4.5.
 The transformation from austenite to martensite is
Fig. No. 4.7 Appearance of Martensite under the
diffusionless and independent of time.
Microscope
 In involves no change in composition of steel.
 Refer Fig. No. 4.7 for appearance of plate martensite.
 The transformation occurs by a shear mechanism and
proceeds at the speed of sound.
4.2.4 Summary of Transformation Products of Austenite
 The c/a ratio increases in this transformation. Table No. 4.1 Transformation products of Austenite
 There is positive volumetric change in this transformation.
Parameter Pearlite Bainite Martensite
It is a metastable phase.
It occurs by
 Refer Fig. No. 4.6 for transformation of austenite to It starts by
It starts by a shear
martensite. nucleation
Initiation nucleation mechanism
of
of ferrite & proceeds
cementite
rapidly
It occurs
It grows as It grows as instantly as
Growth of
platelets in platelets in diffusion
Transformati
edge-wise edge-wise less
on
pattern pattern transformati
on
It is
lamellar
It has a
containing It has strip
Microstructu feathery &
Fig. No. 4.6 Martensite Transformation alternate (rod) like
re needle-like
layers of appearance
 During cooling from austenite region, austenite starts appearance
ferrite &
transforming into martensite at a temperature referred to as
cementite
Ms (Martensite Starts).
The
 As temperature further decreases, the austenite content
microstructu
decreases and amount of martensite formed progressively Nucleation Nucleation
re starts as
increases. Growth continues continues
strip-like &
 The temperature at which 99 % austenite is transformed to pattern to form in the form
forms
martensite is referred to as Mf (Martensite Finishes). colonies of needles
needle-like
 The transformation does not go to completion and that structure
some amount of austenite will exists at temperatures below
Transformati It is the It is the
Mf which is called as retained austenite.
on range of range of It occurs
 The appearance of martensite under the microscope temperature 727°C to 550°C to below 200°C
depends on the carbon content of steel. for 0.8 %C 550°C 300°C

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 Unit IV- Heat Treatment of Steels

4.3 Time-Temperature-Transformation (T-T-T)

Diagram
 Steels above A3 & Acm temperature exist in austenitic
region.
 Depending on the cooling rate i.e. instantaneous
temperature, different transformation reaction take place.
 Thus, depending on the cooling rate austenite may
transform to pearlite, Bainite or Martensite.
 The relationship of temperature Vs time and
transformation is thus established for specific composition
of steel and is represented as T.T.T. curve.
 It helps to determine a specific microstructure in materials
after having deferent cooling rates.
 T-T-T diagram is also referred as Isothermal
Fig. No. 4.8 T-T-T Curve
Transformation (I.T.) diagram, S-Curve, C-Curve or
 Typical T-T-T curve for Eutectoid, Hypo-eutectoid and
Bain’s Curve.
Hyper-eutectoid steel is shown in Fig. No. 4.9 (a), (b) and
(c) respectively.
4.3.1 Plotting of T-T-T Curve
 Obtain a large number of relatively small specimens of a
particular steel composition.
 Place the specimens in a molten salt bath at a proper
austenitizing temperature. (The austenitizing temperature
must be kept constant throughout the experiment). Care
should be taken to avoid any de-carburizing or oxidation of
steel.
 Soak the specimens for sufficient long time to ensure
formation of homogeneous austenite. The time for soaking
should be kept constant throughout the experiment.
 Transfer the specimens to another salt bath kept at some
constant temperature in between AC1 and Ms Temperature
values.
 Allow the specimens to take transformation and then
remove it and quench in cold water or brine.
 The first specimen may be allowed to react isothermally for
2 secs, next specimen for about 4 secs, third specimen for
8 secs, and so on up to say 15 hours. (a) T-T-T diagram for Eutectoid Steel
 Isothermal transformation causes transformation from
austenite to pearlite. More the time given to react
isothermally more is the amount of pearlite formed.
 Depending on the time given to react isothermally, the
austenite may get transformed into pearlite, Bainite and
martensite.
 For specimens that had less isothermal soaking time, the
microstructure would consists more of martensite and less
of the pearlite and vice a versa.
 After the cooling the specimen will be observed under
microscope and a transformation curve of percentage of
pearlite verses time is plotted for a given austenising
temperature. The same process is repeated at a different
austenising temperatures and from that the transformation
points are taken on temperature v/s time axis.
 All these points together will plot a T-T-T curve as shown
in Fig. No. 4.8.

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 Unit IV- Heat Treatment of Steels

Fig. No. 4.10 Critical Cooling Rate

Importance of Critical Cooling Rate

1. It is important for heat treatment of steels.
Fig. No. 4.9 T-T-T Diagram of Eutectoid Steel 2. For hardening, the cooling rate must be higher (Faster) than
the critical rate.
Terms used in the T-T-T Diagram 3. Critical cooling rate determines the microstructure formed
A : Austenite on cooling.
Ps : Start of formation of pearlite 4. Final properties of steel depend on the critical cooling rate.
Pf : Finish of pearlite formation
Bs : Start of formation of Bainite Factors Affecting Critical Cooling Rate
Bf : Finish of Bainite formation Percentage of Carbon Content
M : Martensite Composition of carbon in steel affects the T.T.T curve. For
Ms : Start of formation of martensite both, hypo and hyper eutectoid steel, the T.T.T. curve shifts
Mf : Finish of martensite formation towards left and hence the critical cooling rate increases i.e.
faster cooling is required to obtain martensite.
Transformation in T-T-T Diagram
Pearlite Percentage of Alloying Elements
It is formed in between the A1 temperature and nose Similar to the effect of carbon on T.T.T. curve, alloying
temperature. elements also cause the T.T.T. curve to shift towards left except
element like cobalt.
Bainite
It is formed in between the nose temperature and Ms Hardening Temperature
Temperature with isothermal cooling. Higher the hardening temperature, faster in the cooling rate
required to obtain martensite.
Martensite
It is formed in between the Ms and Mf temperature. 4.5 Continuous Cooling Transformation (C.C.T)
Diagram
4.4 Critical Cooling Rate  During plotting of T-T-T curve, the transformation from
 Critical Cooling Rate is the cooling rate which just avoids austenite (to pearlite and Bainite) were considered
entering the pearlite and Bainite region i.e. it by-passes the isothermal in nature.
nose of the T.T.T. curve. Refer Fig. No. 4.10.  But in actual heat treatment process cycle, the cooling is
 It can also be defined at the slowest cooling rate which will not isothermal rather it is continuous cooling.
result in all austenite getting transformed into martensite.  The cooling rates (similar to T-T-T curve) obtained under
 Critical cooling rate can also be defined as the rate of continuous cooling conditions result in a graph called
cooling necessary to just suppress the diffusion continuous cooling transformation diagram.
transformation and avoid the nose of T-T-T curve and enter
into diffusionless transformation to martensite.

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 Unit IV- Heat Treatment of Steels

 When steel is cooled continuously from a high temperature Cooling Rate-II:

to low temperature, the T-T-T curve shifts towards the  It also results in diffusionless transformation from
bottom right corner. austenite to martensite.
 Refer Fig. No. 4.8 for superimposition of T-T-T curve and  It just touches the nose of T-T-T curve.
C-C-T curve.  It is called as the critical cooling rate.
 The C-C-T curve is indicated by shaded region and is
shifted towards the bottom right side as compared to the T- Cooling Rate-III:
T-T curve.  It results in transformation from austenite to pearlite.
 The pearlite formed is fine.

Cooling Rate-IV:
 It also results in transformation from austenite to pearlite.
 The pearlite formed is coarse in this case.

4.5.1 Difference between T-T-T Curve and C-C-T Curve

Table No. 4.2 T-T-T Curve V/s C-C-T Curve
T.T.T. Curve C.C.T Curve
The relationship of temp. Vs The relationship of temp. Vs
time & transformation time & transformation
obtained under isothermal obtained under continuous
cooling is referred to as cooling is referred to as
T.T.T. diagram. C.C.T. diagram.
It is a curve obtained under The practical heat treatment
ideal equilibrium cooling cycle involves continuous
conditions. cooling of steel.
Since the cooling is Since cooling is continuous,
isothermal, the curve the curve obtained shifts
Fig. No. 4.11 Superimposition of T-T-T curve and C-C-T obtained is ideal. towards the bottom right
curve corner.
Determination of C-C-T Curve The transformation is smooth The transformation takes
 The method of plotting the C-C-T curve is similar to that and fast. longer time due to shifting
of T-T-T curve, except that the cooling is continuous in this of the curve towards right
case. side.
 Heat the specimens in the austenitic region.
 Allow soaking of the specimens for sufficient time in the 4.6 Heat Treatment of Steels
austenite region.
 As the name implies, it is a series of treatments in which
 Remove the specimen one by one and directly quench in heat is used to alter the properties of a metal or alloy.
cold water or brine.
 Heat treatment can be further defined as a series of time
 Direct quenching results in continuous cooling of steel. temperature treatments.
 The time allowed for transformation start and finish of  Heat treatments are used for a variety of purpose, the most
different phases can be controlled by varying the cooling important being to control the mechanical properties,
rates. especially hardness, ductility, strength, toughness and
 The time and temperature noted are plotted and a smooth internal stresses.
curve is drawn through the points.  In the manufacturing processes of many machine parts and
 The graph so obtained is called as continuous cooling tools, heat treatment plays an important role.
transformation diagram.  It is possible to impart high mechanical properties to
metals by heat treatment.
Transformation reactions and cooling rates  Heat treatment is also a combination of heating and
Refer Fig. No. 4.11 which shows four different cooling rates
cooling operations, timed and applied to a metal or alloy in
marked as I, II, III and IV. the solid state to obtain desirable condition.
Cooling Rate- I:
 Heat treatment may be carried out for the following
 It results in diffusionless transformation from austenite to
purposes.
martensite.
1. To improve ductility.
 It avoids the nose of T-T-T curve.

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2. To relieve internal stresses.  This process eliminates internal stresses or residual

3. To harden and strengthen metals. stresses, induced by welding, casting or cold working.
4. To refine grain size.  In this process, the cold worked steel is heated to a
5. To improve machinability. temperature between 500 to 550°C, held at this temperature
6. To improve electrical and magnetic properties. for about 1 to 2 hours and cooled to room temperature.
7. To increase resistance to wear, heat and corrosion.  Due to this treatment internal stresses are relieved without
8. To produce a hard surface on a ductile interior.
change in microstructure. If these stresses are not relieved,
they might be later on, cause war-page or even failure of
4.6.1 Classification of Heat Treatment Processes
the metallic component.
 Stress relict annealing is best suitable for both ferrous as
well as non-ferrous metals and alloys.

Process Annealing
 This is also known as intermediate annealing, this is mainly
used in sheet metal and wire drawing industries.
 In these industries a heavy cold working operation is done,
Fig. No. 4.12 Classification of Heat Treatment Processes
for which initial 50% cold working is done, then process
4.6.2 Annealing annealing is carried out to soften the steel by
 This operations consist of heating the metal to a certain recrystallization and then further cold working is carried
predetermined temperature holding at that temperature for out.
a sufficient time to allow the necessary changes to occur  In this process, the initially cold worked steel is heated
and then cooling slowly, by switching off the furnace. above its recrystallization temperature (about 600°C) i.e.
 Then the charge inside the furnace, gets cool to room below 727°C in iron iron carbon equilibrium diagram and
temperature along with the furnace itself. held at this temperature for sufficient length of time and
 It is a very slow cooling rate. then cooled to room temperature.
 Annealing heat treatment is mainly carried out to obtain the  Due to this treatment, recrystallization occurs and the steel
following properties: gets softened so that further cold working can be carried
1. To relieve internal stresses induced by previous cold out.
working operations.
2. To improve machinability. Spheroids Annealing
3. To soften the steel.  Generally hyper eutectoid steel (high carbon steels)
4. To refine and homogenize the microstructure. contains pearlite and cementite network at room
5. To induce stable structure. temperature, due to which these possesses poor
6. To produce desired microstructure. machinability because the cutting tool cannot penetrate
7. To improve mechanical, physical, electrical and magnetic through the hard and brittle cementite plates.
properties.  But in this spheroids annealing or spherodising process
 Annealing heat treatment process can be classified as produces spheroidal or globular form of cementite from its
follows: plates of cementite, so that the machinability will be
1) Stress relief annealing improved.
2) Process annealing  This process consist of heating the steel to a 650 to 700°C
3) Spheroids annealing and held for a socking time, then cooled to room
4) Full annealing temperature.

Stress Relief Annealing Full Annealing

 When the metal is cold worked, it gets work hardened or  The main purpose of full annealing is to refine grains, to
strain hardened. Also the microstructure becomes distorted induce softness, to improve electrical and magnetic
due to increase in dislocation density. properties and in certain cases to improve machinability.
 As the metal is cold worked, its hardness and strength  In this process, steels are heated above 800°C by 30-50°C,
increases, while ductility decreases. after giving a proper socking time, then cooled slowly in
 To restore toughness in the metal by removing the internal the furnace itself, by sweltering off the furnace at high
stresses induced by cold working operations, a stress relief temperature to room temperature.
annealing is carried out.

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 Due to very slow cooling causes the austenite to  Due to this rapid cooling austenite changes
decompose at low degree, so at to form a pearlite + ferrite instantaneously into a micro constituent called martensite.
structure in hypo eutectoid steel and pearlite + cementite This martensite is very hard and strong but equally brittle
structure in hyper-eutectoid steels. crystalline phase.
 The hardness after quenching depends upon the chemical
composition and the cooling rate during quenching.
 When the steel is quenched to room temperature, the
outside surface cools faster than the interior, setting up
counteraction stresses in the steel.
 Then when austenite transform to martensite, there is a
volume expansion that causes large residual tensile stresses
on the surface. This combined effect of these contraction
and expansion stresses can cause distortion and even some
times cracking.
 The quenching rate or cooling rate in oil is much milder
than water or brine water, which minimises residual
quenching stresses.
 The main purpose of hardening is:
1. To increase the hardness of the steel and tool steels are
hardened to improve their cutting ability.
2. To improve wear resistance of steel.
Fig. No. 4.13 Temperature range for heat treatment of 3. To improve magnetic properties.
steels
4.6.5 Tempering
4.6.3 Normalising  Steels after hardening are not suitable for engineering
 Steels are normalized by heating 50 to 60°C in to the applications because, the martensite phase which is
austenite phase, which is higher than the annealing produced is very hard and brittle, and higher internal
treatment, followed by cooling at a medium rate or stresses are produced.
normalizing means air cooling.  Therefore to restore some toughness in the steel and to
 Many steels are normalized to establish a uniform adjust the hardness according to applications tempering
microstructure and grain size. heat treatment is carried out.
 Due to faster cooling rate in normalizing results in a much  Also some times after hardening process, some amount of
finer microstructure, which is harder and stronger than austenite remains in the microstructure at room
produced by full annealing. temperature, this is known as retained austenite.
 Generally steels are normalized to refine grain size, make  This retained austenite in the microstructure is not
its structure more uniform, make more responsive to desirable because that reduced the overall hardness of the
hardening and to improve machinability. steel.
 When steels are heated to high temperature; the carbon can  So subsequent transformation of this retained austenite
readily diffuse, resulting in a reasonably uniform into other stable phase a tempering heat treatment is very
composition all over the component matrix. much necessary.
 The main purpose of normalizing is:  A tempering treatment is carried out for the following
1. To produce harder and stronger steel compared to full purpose:
annealing. 1. To relieve internal stresses.
2. To improve machinability. 2. To reduce hardness.
3. To modify and refine the grain. 3. To improve ductility and toughness.
4. To homogenize the microstructure. 4. To reduce retained austenite.
5. To improve machinability.
4.6.4 Hardening  Tempering treatment is further divided into three stages:
 In this process steels are heated above the upper critical 1. Low temperature tempering
temperature for hypoeutectoid steels, held at this 2. Medium temperature tempering
temperature for sufficient length of time and then quenched 3. High temperature tempering
in water, oil, brine water etc. to room temperature.

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Low Temperature Tempering rapidly in a salt bath furnace which is maintain at a

 This treatment is carried out from 100 to 200°C. Where the temperature between below nose of T-T-T curve and above
hardened steel components are heated to pre-determined Ms line.
temperature, soaked and then cooled to room temperature.  The component is left in the bath until the transformation
 This reduces internal stresses. to Bainite is complete. The steel is caused to go directly
 Hardened martensite, decomposes in to low carbon from austenite to Bainite.
martensite.  Austempering produces Bainite in the steel, which usually
 The brittleness of hardened steel decreases. No do not require final tempering. It improves the metals
appreciable change is observed in hardness. ductility and toughness, produces higher impact and
fatigue strength.
Medium Temperature Tempering  Also increases wear resistance, as well as reducing
 This treatment is carried out from 200 to 500°C. Soaked cracking and minimizing distortion.
and then cooled to room temperature.
 The hardness of the steel decreases with improvement in Advantages
toughness and ductility. 1. Less distortion and cracking than Martempering.
2. No need for final tempering.
High Temperature Tempering 3. Improvement of toughness.
 This treatment is carried out from 500 to 700°C. Soaked 4. Improved ductility.
and then cooled to room temperature.
 This produces spheroidal cementite in ferrite matrix. Disadvantages
Hardness is reduced to low level and due to which 1. Hardness produced is not so high, as compared with
machinability increases. hardening process.
 From these above tempering treatments can be clearly 2. The holding time is so long and due to which the
seen that as the tempering temperature increases, the process is expensive.
hardness of the steel decreases accordingly, but the
toughness is increases. 4.8 Martempering

4.7 Austempering

Fig. No. 4.15 Martempering Process

 Martempering is also known as marquenching which
Fig. No. 4.14 Austempering Process permits the transformation of austenite to martensite,
 As shown in Fig. No. 4.14, the quenching is interrupted at throughout the cross-section of component, without any
temperature above the Ms Line and allows the metal at the cracking or distortion. The Martempering is carried out as
centre of the part to reach the same temperature as that of shown in Fig. No. 4.15.
the surface.  Martempering can be used for hardening steel gears, gear
 By maintaining that temperature, both the centre and the train guide bars, valves, hand tools, drive shafts and
surface are allowed to transform to ‘Bainite’ and are then bearing assemblies.
cooled to room temperature, i.e. the end product is 100%  Both Martempering and Austempering are designed to
Bainite. overcome the technical limitations of conventional
 It is accomplished by first heating the metallic component quenching and tempering. Particularly with regard to the
to the proper austenitizing temperature followed by cooling

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development of micro cracks, distortion and dimensional at this stage the component is then mechanically worked
changes. by rolling or forging to produce large deformations, of the
 As shown in the Fig. No. 4.15 from austenitic temperature, order of 80-90% reduction of area.
the steel is quenched in a salt bath maintain at a temperature  The steel is then quenched to form martensite. The
just above Ms line i.e. cooling severity using interrupted resultant micro-structure consists of fine martensite. The
quenching in a bath of molten salt, allow sufficient time for size and dispersion of fine martensite can be governed by
the surface and core to cool at same rate, resulting in more prior austenite grain size and the magnitude of plastic
uniform transformation and a strong microstructure. deformation. Refer Fig. No. 4.16.
 A care must be taken that the holding in a salt bath, should  Ausforming process produces superior ductility, toughness
not cross the transformation start line of T-T-T diagram, and impact strength. For Ausforming steel should contain
otherwise 100% martensitic structure will not obtain. alloying elements such as Cr, Mo, V etc. to form carbides
 After removing from bath, the steel is cooled fast to room in solution. After Ausforming steel may be tempered for a
temperature. The cooling is continued through the stress relieving purpose.
martensite region, followed by the usual tempering.  For e.g. highly stressed structural parts for aircraft and
 Martempered components are usually tempered to convert automotive leaf springs are particularly, manufactured by
them into a more ductile material. This process prevents Ausforming process.
cracking and substantially reduces distortion.
 Martempering typically carried out at temperature up to 4.10 Patenting
260°C and Austempering up to 400°C.
 In Martempering the soaking times is shorter, i.e. between
20 to 30 minutes, whereas austempered parks are soaked
for 3 to 4 hours or more, to achieve the bainitic
transformation.

4.9 Ausforming

Fig. No. 4.17 Patenting Process

 The process is very much similar to Austempering, except
in the range of temperature used for the isothermal
transformation. The process is as shown in the Fig. No.
4.17.
 It consists of quenching an austenitised steel in molten salt
bath furnace maintain a constant temperature slightly
above or below the nose of T-T-T diagram.
 Holding at this temperature, until the transformation is
complete and then cooling to room temperature at any
Fig. No. 4.16 Ausforming Process desired rate. The 100% transformation from austenite to
 Ausforming may be defined as deforming metastable steel pearlite is obtained, and commonly called as patenting.
while in austenite phase. Since addition of alloying  This pearlitic microstructure is very much suitable for wire
elements will delay the beginning of phase transformation, drawing, which allows further drawing without difficulties.
it is possible to combine heat treating and strain hardening  In this way transformation conditions must be such that
advantageously. martensite or Bainite are completely avoided, also the
 This principle is utilized in Ausforming. An alloy steel metallic structure of the patented steel wire must not be too
containing about 0.45% carbon is heated to form austenite soft, and to which 100% pearlitic structure is most
is then quenched in a molten salt bath (maintain at 500°C), beneficial for wire drawing.

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4.11 Retention of Austenite 4.13.1 Sub-zero Treatment

 The transformation of austenite to martensite is a  It involves cooling the hardened steel to a temperature well
diffusionless transformation. below the room temperature.
 It is temperature dependent transformation.  Commonly used cooling medium for such treatment ranges
 When steel is cooled from austenitization temperature at a from Ice + Salt bath (- 23°C), liquid air (- 183°C) to liquid
rapid rate such that is bypasses the critical cooling rate, the helium (- 269°C).
microstructure formed is martensite.  If the quenched steel is held at room temperature for some
 When the temperature is just below Ms, the formation of time before subjected to sub-zero treatment then less
martensite starts which is accompanied by volume austenite gets transformed to martensite.
expansion and hereby developing compressive stresses in  Hence, sub-zero treatment should be done immediately
austenite. after quenching.
 These compressive stresses restrict further transformation  This treatment is used for high carbon hardened
from austenite to martensite and equilibrium is reached. components such as tools steels etc.
 When the steel is further cooled, both the transformed
martensite and austenite contracts. 4.13.2 Tempering
 The contraction of martensite is more than that of austenite  It is the process of heating the hardened steel to some
thus releasing the compressive stresses on austenite and temperature below the A1 temperature and then cooling to
some more austenite gets transformed into martensite. room temperature.
 This process continues as formation of alternate  This process eliminates retained austenite from steel.
equilibrium and martensite structure.  This treatment can be used for small and large amount of
 It continues until Mf temperature is reached, whereby retained austenite.
almost 99% austenite gets transformed into martensite,
while small (< 1%) amount of austenite in highly 4.14 Secondary Hardening
compressed form still remains as un-transformed or
retained austenite.
 Thus, for all practical purposes it is assumed that 99%
austenite gets transformed to martensite.
 The amount of retained austenite depends on the cross-
section of steel component and quenching medium used.

4.12 Effects of Retained Austenite

4.12.1 Benefits of retained austenite
 Retained austenite is a soft phase and reduces the tendency
of cracking during hardening. It is desirable to have about
100% retained austenite.
 In case, the amount of retained austenite is about 30-40%,
the steel can be cold worked to certain degree without
cracking.

4.12.2 Disadvantages of retained austenite

 Retained austenite reduces hardness of the steel.
 It also increases brittleness of steel.
 Over a period of time, austenite gets transformed to Bainite Fig. No. 4.18 Secondary Hardening-Resulting in Increased
which has different properties. Hardness
 Retained austenite is not-at-all desirable in certain  It is been observed that when alloy steels are tempered,
applications such as tool and die block. their hardness increases.
 This is because of formation of complex carbides when the
steel is heated to tempering temperature.
4.13 Elimination of Retained Austenite
 Such a hardening that takes place during tempering is
 For high carbon steels, the Mf temperature is below the
referred to as secondary hardening.
room temperature.
 These alloy steels retain their hardness even at high
 Thus, 100% austenite is not transformed into martensite.
temperatures up to 600°C.
 Following methods are employed to obtain complete
 Fig. No. 4.18 shows such a secondary hardening cycle.
martensitic diffusionless transformation:

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4.15 Temper Embrittlement (Brittleness) 1. Quenching from higher austenitizing temperatures

produces coarse grained martensite which is prone to
cracking.
2. Improper selection of quenching medium can also lead
to cracking. Selecting a quenching medium which
gives higher cooling rate than the one required may
lead to cracking.
3. Improper shifting and immersing of austenitised steel
in quenching medium with respect to the shape of
component leads to non-uniform volume changes
causing cracks.
4. If long time gap is provided between hardening and
tempering treatment it may lead to cracking in
components.
5. Complex geometric shapes of components such as
presence of key ways, holes, and sharp changes may
lead to cracking.
Fig. No. 4.19 Temper Embrittlement
6. The presence of inclusions may also enhance
 It is a brittleness resulting from holding certain steels
possibility of cracking.
within a particular temperature below the transformation
7. The banded microstructures have alternate bands of
range or by slow cooling through this range.
ferrite and pearlite. Such a microstructure does not get
 The brittleness appears at or below the room temperature. converted to a homogeneous austenite and is likely to
 It means, after quenching and tempering some alloy steels develop cracks during quenching.
lose their impact resistance and becomes brittle; if, after
tempering, they are slowly cooled or held for longer time
in the temperature range of 600 to 300°C.
4.17 Hardenability
 Hardenability is the ability of material to be hardened at a
 Such a steel may suffer from temper brittleness when
given depth by thermal treatment.
tempered in the range of 250 to 400°C. They generally
show normal ductility in the standard tension test.  Hardness is the ability of material to resists penetration.
 If steel is tempered above 400°C, it is essential to cool the  Therefore hardenability of a metal or alloy is the depth up
steel quickly in oil through the range in which temper to which a metal is hardened after putting through a heat
brittleness is produced. treatment cycle. The unit of hardenability is the same as of
length (i.e. in mm).
 High amount of Mn, P and Cr promotes susceptibility of
temper embrittleness whereas an addition of 0.5% Mo will  It is an indication how deep into the metal certain hardness
reduce the effect. (Rc 50) can be achieved.
 Steel tempered about 400°C appears blue in colour and  The hardenability of a metal or alloy is a function of:
hence the brittleness observed is called as blue brittleness. 1. The carbon content in the steel
2. The alloy content in the steel
 Temper brittleness is associated with fracture along the
3. The grain size of the austenite
grain boundaries and it is due to segregation of traces of
4. Quenching medium
phosphorous to these boundaries.
 There are two commonly used methods to determine the
hardenability of steel:
4.16 Quench Cracks 1. Jominy End Quench Test
 Quenching process involves rapid cooling of steel from 2. Grossman’s Method
austenitizing temperatures.
 During rapid cooling, the circumferential surface of 4.17.1 Jominy End Quench Test
component cools rapidly while the centre or core area of  The test is conducted with standard sample as shown in Fig.
component cools slowly. No. 4.20, prepared from the steel of which hardenability is
 This results in different phase transformation at surface and to be found out.
centre.  The test setup is as shown in Fig. No. 4.20 and 4.21, along
 Thus rapid cooling produces non-uniform volume changes with the dimensions of standard samples.
which cause heavy distortions and cracking of components.  This standard sample is then heated to proper austenitizing
 The major reasons for formation of such quench cracks can temperature and after a proper socking time, the specimen
be ascertained as below: is removed from the furnace and placed on the support.

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 Then a water jet is started the flow of water is so adjusted

that the cooling effect will be obtain only on the bottom
most surface of the specimen and gradually it cools up to
collar end. The water jet should show umbrella shape.

Fig. No. 4.20 Jominy End Quench Test Setup

Fig. No. 4.22 Hardenability Curve

Fig. No. 4.23 Hardenability Curve

Fig. No. 4.21 Standard Specimen for Jominy End Quench  As the cooling rate will be highest at the end being
Test quenched, and will decrease as distance from the quench
 After the bar has been cool to temperature, for measuring end increases.
the hardness, one band is grind from collar end up to  The hardenability is found by measuring the hardness
quench end and polished, for proper hardness along the bar as shown in Fig. No. 4.22.
measurement.  A higher hardness is obtained at the quench end where the
 The hardness is measured on Rockwell hardness tester with highest cooling rate was obtained and gradually the
Rc scale. At a distance of 1/16 interval in each hardness hardness decreases towards the collar end. A hardenability
point as shown in Fig. No. 4.22 curve is obtained as shown in Fig. No. 4.23.

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 As shown in the curve above, the measure of hardenability  In critical components of I.C. engines such as gears, crank
is a point where we get 50 Rc as a hardness and the depth shafts, valves etc. defects seen in quench parts are often due
of hardening can be found out by drawing the to high thermal and phase transformation stresses.
perpendicular to the x axis as shown.  The typical defects include excessive distortion, surface
decarburization, quench cracks, large grain growth and
4.17.2 Factors Affecting Hardenability residual stresses. Surface decarburization before quenching
Alloying Elements: may lead to high surface residual tension and post heat
The alloying elements in steel have a big influence on treatment cracking.
hardenability, alloying elements in steel increases  Sometimes quenching process are required to be modified
hardenability. to solve the problem in many cases.
 Both distortions in gears during quenching due to high
Austenitic Grain Size: residual stresses, a press quenching is recommended,
Hardenability is also affected by the austenitic grain size. A fine because to reduce the machining coat after heat treatment,
grain size reduces hardenability, because of larger number minimum distortion is preferred.
density of heterogeneous nucleation sites.  Surface decarburization affects the surface hardness
achieved by quenching process. In many cases this
Severity of Quench: decarburized layer can be ground off, so that high hardness
Certainly fast cooling with water or brine water will give lower region can be exposed.
hardenability as compared with oil quenching increases
hardenability as the cooling rate is slightly slower. 4.19 Surface Hardening Treatment
 Many applications such as gears, crankshafts, camshafts
Carbon content in steel:
require hard and wear resistant surface and a tough core to
Generally increase in percentage of carbon, increases
withstand the impact load.
hardenability, but up to some extent. Otherwise at very high
carbon, hardenability decreases.  Such a requirement is difficult to achieve by using a
homogeneous composition of steel because high carbon
steel have high hardness and lower toughness while low
4.18 Defect due to Heat Treatment and Remedial carbon steel have high toughness and lower hardness.
Measures  Thus, surface hardening is required to improve the
 Following are the few defects, which are arise during heat hardness of internally tough materials.
treatment:
1. Overheating Table No. 4.3 Summary of Surface Hardening Methods
2. Burning Surface Hardening
3. Decarburization Principle
Methods
4. Quenching Cracks Increasing carbon content on the
5. Deformation and volume change after hardening Carburizing surface and subsequent heat
6. Warping treatment.
7. Insufficient hardness after quenching Including nitrogen on the surface to
8. Soft spots Nitriding produce hard nitride surface.
9. Corrosion
 Heat treatment errors, often results in regions of decrease Including carbon and atomic
Carbo-Nitriding nitrogen on the surface to produce
in hardness i.e. soft spots, decarburisation, over tempering
etc. hard carbo-nitride surface.
 If these defects remain undetected, which may leads to Hardening without any change in
failure of a component, operating under load, as a result it Flame Hardening composition of surface.
is necessary to detect grinding and heat treatment defects, Hardening without any change in
as they occur so that steps may be taken to correct the Induction Hardening composition of surface.
process immediately and prevent the faulty parts to put in
service.
 As grinding and heat treating processes are important steps 4.20 Carburizing
in the industrial production of most finished metallic  Carburizing is the method of increasing carbon on the
components, therefore controlled hardness, improved surface of steel followed by subsequent heat treatment.
toughness and reliable dimensional control are important  Usually carburising is carried out in the temperature range
factors to see. of 900 to 950°C, and carbon in the surface layer is
increased up to 0.7 to 0.9%.

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 Since the solubility of carbon is more in austenite state than  This CO2 reacts with carbon in the charcoal to form carbon
in ferrite state, therefore fully austenite phase is required monoxide.
for carburising. CO2 + C ⟶ 2CO
 This can be achieved by heating the steel above the critical 2CO + Fe ⟶ Fe (C) + CO2
temperature.  Where this atomic carbon with iron (Fe) gets diffused into
 When the steel is kept in content with carbonaceous the surface layer of a component.
material, which is higher in carbon content, and due to  Case depth required will be depending upon the holding
technical reaction, the atomic carbon gets diffuse into steel time at high temperature i.e. to get deeper case depth the
surface layer. components should be carburized for longer time and to get
 The carbonaceous material or atmosphere which may be a shallow depth, those should be carburized for shorter time.
solid, a liquid or a gas, depending on it there are three Generally for a carburizing time of 6 to 8 hours, the case
general methods of carbonizing. depth obtained will be in the range of 1 mm to 2 mm.
1. Solid Carburizing (Pack or Box Carburizing)
2. Gas Carburizing Applications
3. Liquid Carburizing  This treatment is used to increase hardness of small
components required in batches.
4.20.1 Solid Carburizing (Pack or Box)  At 925 - 950°C the case depth varies from 1.0 to 2.5 mm
for total carburizing time of 6 to 15 hrs.

4.20.2 Gas Carburizing

Fig. No. 4.24 Pack Hardening

 This is also known as solid carburizing. In this process the
components of low carbon steel are packed with a
carbonaceous solid mixture of 80% charcoal powder and
20% barium chloride (BaCO3).
 Here BaCO3 acts as a accelerator to fasten the process of Fig. No. 4.25 Gas Carburizing
carburizing. As shown in the Fig. No. 4.24. In a heat  In this type of carburizing, components are heated in the
resistant box, the components are so placed that no presence of some carbonaceous gas such as methane (CH4),
component touches one another or even the side of the box. ethane (C2H6), propane, butane etc. and diluted with a
 The carbonaceous mixture is place around and then the box carrier gas such as flue gas.
is sealed. This box is then placed in a furnace to heat up to  These carbonaceous gases decompose and diffuse carbon
900 to 950°C for 6 to 8 hours. After a proper socking time, in the steel.
the box is cooled to room temperature along with  It should be ensured that gas composition and its
components inside the furnace itself. circulation over the components is uniform and properly
 During the carburizing processes the following reaction controlled.
take place at high temperature and the surface layer get  Refer Fig. No. 4.25 for set-up of gas carburising.
enriched with carbon.  Gas carburizing produces extremely uniform cases within
 The energizer BaCO3 decompose in to shorter times.
BaCO3 ⟶ BaO + CO2  It does not require heating of any box and solid carburiser
as in case of pack carburising.

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 The temperature at which carbon diffusion takes place is  Case depths between 0.1 to 0.5 mm can be obtained in a
also lower (900 to 925°C) than that for solid carburizing. period of ½ to 1 hour at the usual carburising temperatures.

Applications 4.21 Heat Treatment after Carburizing

 This treatment is used to obtain thin cases of high  Only after carburising, the carbon in the surface layer
uniformity. increases, it do not increase the surface hardness of low
 Case depth up to 0.2 to 0.5 mm can be obtained in 1 to 2 carbon steel.
hrs at temperature of 900°C.  Therefore carburising must be followed by hardening
 It is used for large volume production and accurate control treatment and then by tempering to attain required hardness
of case depth and surface carbon content. and toughness at surface and core respectively.

4.20.3 Liquid Carburizing

Fig. No. 4.27 Quench Cycle on Carburized Components

Direct Quench (Refer Cycle 1)

 In involves rapid quenching of carburized components in
water or oil and tempered to reduce brittleness of case.
 Faster cooling produces martensite at the surface of steel
Fig. No. 4.26 Liquid Carburizing and retains fine ferrite at the centre.
 In this method, carburizing is carried out by immersing the  It is the simplest and fastest after-treatment on carburized
steel components in a liquid carbonaceous fused salt bath components and produces minimum distortion.
medium at temperature in the austenitic region.
 The salt bath consists of sodium cyanide (approximate Double Quench (Refer Cycle 2)
10%), sodium carbonate and sodium chloride.  Slow cooling from carburizing temperature to room temp
 Also added to the salt bath are alkaline earth salts of and thus avoiding distortion & cracking of the surface.
barium, calcium or strontium to encourage the cyan amide  Reheating to upper critical temperature of the core and
shift. again quenching hereby producing fine ferrite at the core.
 Refer Fig. No. 4.26 for the set-up of liquid carburizing.  Reheating to a temperature just above the lower critical
 Following reaction occurs in presence of oxygen: temperature of the case & quenching to improve the case
2NaCN + O2 ⟶ 2NaCNO properties.
3NaCNO ⟶ NaCN + Na2CO3 + C + 2N
4NaCNO ⟶ 2NaCN + Na2CO3 + CO + 2N Case-Refining Quench (Refer Cycle 3)
2NaCN + 2O2 ⟶ Na2CO3 + CO + 2N  This involves direct quenching from the carburizing
2CO ⟶ C + CO2 temperature to room temperature followed by reheating to
 Atomic nitrogen thus produced diffuses and results in just above the critical temperature of the case & again
carburizing and Nitriding. quenching.
 If alkaline earth salts are present, then excess of O2 to salt  This after-treatment produces refine grain size with
bath can be reduced and formation of cyan ate (NaCNO) reduced amount of retained austenite.
can be reduced.
BaCO3 + 2NaCN ⟶ Ba (CN)2 + Na2CO3 Core-Refining Quench (Refer Cycle 4)
Ba(CN)2 ⟶ BaCN2 + C  This treatment involves slow cooling from the carburizing
t temperature to room temperature followed by reheating to
Applications just above the upper critical temperature of the core and
 It is used for rapid production of relatively thin carburised again quenching to room temp.
cases of small components.  This after treatment gives superior core properties with
compromise in properties obtained at the case.

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4.22 Nitriding  It gives excellent wear resistant.

 Nitride component possesses better fatigue properties.
 Nitriding gives good corrosion resistance.
 Post nitriding heat treatment is not required.

Disadvantages
 Long time consuming cycle.
 Only alloy steels should be nitride.
 Costly process.
 Machining is not possible after nitriding.
 Nitride case is usually brittle.

4.23 Carbo-Nitriding
Fig. No. 4.28 Nitriding
 This is also one of the surface modification technique,
which is used to increase the surface hardness and wear
resistance.
 In this process nitrogen is diffused in the surface layer of
steel component.
 Nitriding is carried out at 500°C with ammonia
atmosphere.
 As the process temperature is very low, so that nitriding
can be achieved with the components in terrific state. As Fig. No. 4.29 Carbo-Nitriding Process
compared with carburising, where the components must be  It is the combination of carburizing and nitriding surface
in austenitic state. hardening treatment.
 In nitriding finished components are heat treated initially  Carburizing improves service life of component and
by conventional hardening and tempering heat treatment, nitriding provides high surface hardness.
so that required core properties can be obtained.  Refer Fig. No. 4.29 for the illustration of Carbo-nitriding
 In nitriding process temperature of 500°C for about 40 to process.
100 hrs in ammonia atmosphere.  The source of carbon and atomic nitrogen can be fused salt
 This atomic nitrogen thus formed diffuses in to iron and bath or any gaseous medium containing methane, ethane
forms hard nitrides by combining with iron and certain etc. with 5 to 10% ammonia.
alloying elements present in steel.  The surface of the components is heated to a temperature
 Therefore steels used for nitriding treatment should contain above the lower critical temperature in the range of 750 to
alloying elements like aluminium, chromium and 850°C.
molybdenum etc. as those alloying element possess more  Atomic nitrogen diffuses in the ferrite phase and carbon
affinity towards nitrogen. diffuses in the austenite.
 In nitriding treatment a very high surface hardness is  The amount on nitriding and carburizing can be controlled
obtain, and also since the process temperature is very low by varying the temperatures.
as compared with other surface hardening treatments, no  This is followed by oil quenching to produce martensite.
quenching is required and due to which no distortion and  The case depth obtained is less hence the carbo-nitrided
cracking takes place. components are directly used without any further
 The surface layer which is generally known as white layer, machining or treatment.
possess a very good resistance to corrosion, wear and  Depending on the medium used, the process can be liquid
fatigue resistance. or gas carbo-nitriding.
 Since liquid Carbo-nitriding uses a cyanide salt bath, it is
Advantages also termed as cyaniding.
 No quenching is required, due to which no distortion and  The treatment is best suitable for alloy steels.
cracking takes place.
 For finished components, nitriding treatment can be Advantages
applicable.  By proper temperature control, properties of both
 Complex shaped components can be easily nitride. carburizing and nitriding can be obtained.

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 The carbo-nitride components have high surface hardness  Continuous flame hardening and quenching across the
and high toughness. length of surface.
 It produces excellent wear resistance.
 The hardness of nitride case is unaffected by heating to 4.24.3 Spinning Flame Hardening
temperatures below the original nitriding temperature.
 Fatigue resistance is also an important advantages of
nitriding.

Disadvantages
 Precise control over temperatures is required.
 It is expensive.

4.24 Flame Hardening

 Flame hardening is the process of heating the surface layer
of the steel to a temperature above its upper critical
temperature by means of a burning flame followed by
water quenching to transform surface austenite to hard
Fig. No. 4.32 Spinning Flame Hardening
martensite.
 It consists of stationary flame and rotating or spinning
 The flame generally used is oxyacetylene.
work piece to be case hardened.
4.24.1 Spot Flame Hardening
4.24.4 Combination Flame Hardening

Fig. No. 4.30 Spot Flame Hardening

 Spot or localized area being heated and quenched.

4.24.2 Progressive Flame Hardening

Fig. No. 4.33 Combination Flame Hardening

 It consists of rotating work piece and transverse moving
flame torch.

Advantages
 Process is simple.
 Variety of steels can be hardened.
 Can be applied to any shape.
 Selective hardening can be done.
 It is cheaper if only a few parts are to surface hardened.

Disadvantages
 Difficult to control temperature, overheating may take
place; resulting in formation of coarse martensite.
 An expensive method for mass production.
 Case depth cannot be adjusted exactly.
Fig. No. 4.31 Progressive Flame Hardening  Some oxidation or de-carburization always occurs.

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 Explosive gases are required continuously.  Good properties are obtained for low grade steels.
 No oxidation/de-carburization.
Applications  Case depth can be controlled.
 Medium carbon steel used for auto drive shafts, gears etc.  High hardness is obtained.
 High carbon steel used for hard tools, drills and rock bits.  High fatigue strength.
 Alloy steels used for automobile valves and bearings etc.  It can be used in production line.
 Large sized components such as lathe beds etc.
Disadvantages
4.25 Induction Hardening  Not suitable for irregular shaped components.
 Not economical for small scale production.

4.25.1 Comparison
Table No. 4.4 Induction Hardening V/s Flame Hardening
Flame Hardening Induction Hardening
Flame hardening treatment Induction hardening
works on the principle of treatment works on the
heating the surface of steel principle of heating the
using oxyacetylene flame, surface of steel using high
followed by surface frequency electrical current,
quenching. followed by surface
quenching.
Fig. No. 4.34 Induction Hardening An expensive method for Economical for mass
 Induction hardening treatment works on the principle of mass production. production.
heating the surface of steel using high frequency electrical Some oxidation or de- No oxidation or de-
current, followed by surface quenching. carburization always occurs. carburization occurs.
 The component is heated by means of an inductor coil Case depth cannot be Case depth can be
which consists of large number of turns of water-cooled adjusted automatically. controlled.
hollow copper tubes. Can be applied to any shape. Not suitable for irregular
 Fig. No. 4.34 shows the arrangement of workpiece held in shaped components.
between the inductor coils.
 Alternating magnetic field is generated by the high Table No. 4.5 Carbo Nitriding V/s Flame Hardening
frequency A.C. current flowing through the copper tubes. Carbo Nitriding Induction Hardening
 This electro-magnetic current produces eddy currents of It is the process of inducting It is the process of hardening
high frequency in the surface layer hereby heating it to the carbon and atomic nitrogen without any change in
upper critical temperature. on the surface to produce composition of surface.
 This phenomenon is known as skin effect. hard carbo-nitrided surface.
 Depth of hardening is inversely proportional to the square The source of carbon and It uses the oxyacetylene
root of the frequency of induced current. atomic nitrogen can be fused flame to heat the surface
 The usual depth of hardening obtained are 0.5 to 6 mm salt bath or any gaseous layer of the steel above its
through a frequency of 1000 to 100000 Hz. medium containing upper critical temperature
 The heated components are then quenched in water. methane, ethane etc. with 5 followed by water
 Due to fast heating and quenching, the martensite produced to 10% ammonia. quenching.
is fine grained. Case depth obtain is very It produces case depth up to
 Induction hardening is usually followed by tempering. less. 0.8 to 6 mm.
 Steel with carbon content between 0.3 to 0.6% can be Temperature control is Difficult to control the
satisfactorily hardened by induction hardening treatment. possible during process. temperature and overheating
 Steels with carbon content less than 0.3%, contain limited of component may takes
carbon thereby reducing martensitic transformation in place.
steel. This process does not require The process required
any explosive gases. explosive gases
Advantages continuously.
 Selective localized hardening. It is an expensive method. This method is cheaper if
 Economical for mass production. only a few parts are to
 Operating cost is less. surface hardened.

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Table No. 4.6 Carburizing V/s Nitriding Table No. 4.8 Annealing V/s Normalizing
Carburizing Nitriding Annealing Normalizing
Carburizing is the method of Nitriding is the process of Steel after annealing become Steel after normalizing
increasing carbon on the forcing diffusion of atomic very soft due to which lower possess better strength and
surface of steel followed by nitrogen in the steel to form strength and hardness. hardness than annealing
subsequent heat treatment. respective nitrides and process.
increase surface hardness. Steels are cooled in furnace Steels are cooled in air from
Carburizing is performed at Nitriding is performed at itself from high temperature high temperature to room
higher temperature than the relatively lower to room temperature. temperature.
nitriding. Quenching is temperatures and no Very slow cooling rate. Moderate cooling rate, not
required after carburizing. quenching is required. very slow as annealing
Some complex parts cannot Complex parts can be case process.
be case hardened hardened satisfactorily by Grain size obtain is very Grain size obtain is smaller
satisfactorily by carburizing. nitriding without difficulty. large. than as obtain in annealing.
Carburized component Nitrided components retain Very large time consuming Not so large time consuming
begins to lose its hardness at high hardness up to 600°C. process. process.
relatively lower There is intermediate There is no such
temperatures. annealing process. intermediate normalizing.
Wear resistance and fatigue Wear resistance, fatigue There are total different 4 to There is no such different
resistance of a carburized resistance of a nitrided 5 types of annealing process. types of normalising
component is lower than component is higher than process.
Nitrided component. carburized component. Tool room products are Tool room products are
Carburized cases have Nitriding produces case with always annealed after never normalized after
hardness of up to 835 VPN. hardness in the range 1000- machining. machining.
1200 VPN.
Requires less time- 1 to 2 Requires more time- 24 to 72
hours for liquid and gas hours. University Question
carburizing and 6 to 15 hours
for solid carburizing.
Case depth can be more than Case depth is usually less November 2019 Examination
0.5 mm up to 2.5 mm. than 0.5 mm.
1. Differentiate between Annealed and Normalised components
Table No. 4.7 Hardness V/s Hardenability with the help of the following criteria:
Hardness Hardenability i) Tensile Strength
Hardness is the ability of Hardenability is the ability ii) Microstructure
material to resists of material to be hardened at iii) Grain size distribution
penetration. a given depth by thermal iv) Internal stresses
treatment. (Refer Section 4.6.2 & 4.6.3, Table No. 4.8)
Hardness can be determined Hardenability can be 2. Define the critical cooling rate of steel and show the same
by the Brinell’s hardness determined by Jominy End on T-T-T diagram. State the main factors responsible for the
test, Rockwell hardness test Quench Test and critical cooling rate. (Refer Section 4.4)
Grossman’s method. 3.”Hardening of steel is always followed by tempering”, is it
Hardness can be measured in Hardenability presumes that true or false? Justify. (Refer Section 4.6.4 & 4.6.5)
the material in any the material will be heat
condition. treated to achieve a targeted May 2019 Examination
hardness up to given depth.
It indicates that how hard is It indicate the depth up to 1. As the tempering temperature of a hardened component is
the material to resist the which material is hardened. increased, the hardness of the component decreases, Explain
scratching, abrasion or why the hardness of the component decreases with
cutting. temperature? (Refer Section 4.6.5)
2. What is Martempering? What are the advantages of
Martempering over conventional hardening? (Refer Section
4.8)

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November 2018 Examination

1. State whether the following statements are True or False and
justify your choice correctly:
a) Pack carburising is most suitable for large scale of
production. (Refer Section 4.20.1)
2. Define Hardenability and explain the test with suitable figure.
(Refer Section 4.17)
3. Differentiate between the following:
a) Austempering and Martempering (Refer Section 4.7 and
4.8)
b) Annealing and Hardening (Refer Section 4.6.2 and 4.6.4)
4. Write a short note on Quench Cracks in Hardening Process.
(Refer Section 4.16)
5. What is the importance of T-T-T diagrams in Heat Treatment
Processes? (Refer Section 4.3)
6. What is Sub Zero Treatment and why is it necessary? (Refer
Section 4.13.1)

November 2017 Examination

1. Give brief explanation of austenite to pearlite
transformation? (Refer Section 4.2.1)
2. Differentiate between Martempering and Austempering.
(Refer Section 4.7 and 4.8)

May 2017 Examination

1. What is Retained austenite? List effect of retained austenite?
Explain sub-zero treatment of elimination of retain austenite?
(Refer Section 4.11, 4.12 and 4.13.1)
2. Why carburising is carried out at a temperature range above
900°C. (Refer Section 4.20)

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 Unit V- Engineering Alloy Steels and Designation

Unit – V
Engineering Alloy Steels and Designation

Syllabus:
Classification of alloy steels & Effect of alloying elements, examples of alloy steels, stainless steels, sensitization
& weld decay of stainless steel, tool steels, heat treatment of high speed steel, special purpose steels with
applications, super alloys. Heat affected zone. Designation (for plane & alloy steels): IS, AISI, SAE, and DIN etc.

Section No. Topic Name Page No.

5.1 Introduction 98
5.2 Effect of Alloying Elements 98
5.3 Properties and Uses of Alloying Elements 99
5.4 Prominent Alloy Steels 99
5.5 Classification of Alloy Steels 100
5.6 Stainless Steels 101
5.7 Weld Decay of Stainless Steel 104
5.8 Sensitization 104
5.9 Tool Steels 105
5.10 18-4-1 High Speed Tool Steel 107
5.11 Special Purpose Steels 107
5.12 Super Alloys 108
5.13 Heat Affected Zone 108
5.14 Designation (For Plane and Alloy Steels) 109
5.15 Indian Standard Designation System (IS) 109
5.16 AISI/SAE Designation System 109
5.17 British Standard Designation System 110
5.18 DIN 110

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5.1 Introduction
 Alloy steels is a steel in which various elements other than
carbon like nickel, manganese, tungsten, aluminium,
copper, molybdenum etc. are added to obtain the desired
properties.
 Generally, these elements are added to increase
mechanical, electrical, thermal, magnetic or resistant
properties.
 The main cause of adding alloying elements in steel are as
follows:
1. To increase the hardness and wear resistance.
2. To increase corrosion resistance.
3. To increase resistance to abrasion and wear.
4. To increase ductility and machinability.
5. To improve mechanical, electrical and thermal properties.
6. To impart a fine grain size to steel.
7. To increase casehardening properties.

5.1.1 Advantages and Limitations of Alloy Steels

Advantages Fig. No. 5.1 Relationship between alloying elements and
 Greater strength at elevated temperatures. hardness of steels
 High hardenability.
 Improved ductility and cracking. 5.2.3 Formation of Inclusions (Oxides)
 Higher elastic ratio and endurance strength.  Usually de-oxidants are added to remove dissolved free
oxygen from the steel.
 Better machinability at high hardness.
 These de-oxidations combine with oxygen to form oxide
 Less internal stresses.
inclusions.
Limitations  E.g. Al, Si, Cr, Mn etc.
 Higher cost than plain carbon steels.
5.2.4 Formation of Intermediate Compounds
 Care should be taken during handling.
 Some alloying elements form intermediate compounds
 Tendency to have retained austenite.
with iron.
 Certain grades show temper brittleness.
 These compounds improve wear resistance and other
mechanical properties.
5.2 Effect of Alloying Elements  E.g. Cr, V, W, Ni, Si etc.
 Alloying elements such as Ni, Mn, Cr, Mo, V etc. are added
to steels to enhance mechanical, thermal, magnetic and 5.2.5 Shifting / Lowering of Critical Cooling Rate
resistant properties.  Different alloying elements have different critical
 Following are the effects of alloying elements: temperatures.
 Ferrite stabilizers raise the eutectoid temperature (A1)
5.2.1 Solid Solution Strengthening/Hardening while austenite stabilizers lower the eutectoid temperature
 Alloying elements are soluble in ferrite. They form solid (A1).
solutions with ferrite.  E.g. Mo, Ti-ferrite stabilizers, Mn, Ni-austenite
 Solid solutions are harder and stronger than pure metals, stabilizers.
thereby increasing the strength and hardness of the steel.
 Refer Fig. No. 5.1 indicating relationship between the 5.2.6 Changes in Volume during Transformation
alloying elements and hardness.  The changes in microstructure result in change in the
 Examples: Mn, Mo, V, Cr, Ni, P, Si etc. volume of unit cell.
 Alloys are added to reduce the volume impact.
5.2.2 Formation of Carbides  E.g. Cr, Ni, Si, Mn, Mo, V, Cr, Ni, P, Si etc.
 Some alloying elements combine with carbon to form its
carbides. 5.2.7 Other Effects
 The alloy carbides so formed increase the hardness and  Besides those mentioned above, alloying elements are
wear resistance. added to improve corrosion resistance, creep strength etc.
 E.g. Cr, Ti, W, Mn, V etc.

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5.3 Properties and Uses of Alloying Elements  It reduce de-carburization.

Following are the common alloying elements used and its
function in the alloy steel: Molybdenum (Mo)
 It increases hardenability.
Carbon (C)  It makes grain finer.
 It increases hardness and strength.  It forms carbides and increases wear resistance.
 It increases machinability.  It reduce de-carburization.

Sulphur (S) Vanadium (V)

 It forms manganese sulphide (MnS) which is hard and  It promotes fine grain structure.
brittle.  It increases hardenability.
 MnS promotes chip formation and hence increase  Its properties are similar to those of W and Mn.
machinability.
Cobalt (Co)
Phosphorous (P)  It reduces hardenability.
 It dissolves in ferrite.  It improves strength.
 It increases tensile strength and hardness.  It promotes fine grained structure.
 It is a solid solution strengthened.  It improves heat resistance.
 It forms Iron Phosphide (Fe3P) which is hard and brittle.
 It also increases machinability. Aluminium (Al)
 It is used as a de-oxidiser.
Silicon (Si)  It promotes fine grained structure.
 It is a ferrite solid solution strengthened.
 It improves oxidation resistance. Boron (Br)
 It reduces hysteresis losses.  It increases hardenability.
 It increases toughness.  It improves wear and tear resistance.

Manganese (Mn) 5.4 Prominent Alloy Steels

 It combines with sulphur present in steel to form MnS and The following are the popular alloy steels:
improves machinability.
 It dissolves in ferrite and improves strength and toughness. 5.4.1 Silicon Steel
 It lowers ductility if present in higher percentage. Composition
C- 0.1%
Nickel (Ni) Si- 1.0%
 It is a ferrite solid solution strengthened. Mn- 0.6%
 It dissolves in ferrite. Properties
 It increases tensile strength and hardness.  High strength & fatigue resistance
 It increases corrosion and oxidation resistance.  Improved electrical properties
 It is austenite stabilizer and lowers critical temperatures.  Stronger steel
 It reduces co-efficient of thermal expansion. Applications
Bridges, Structures
Chromium (Cr)
 It forms chromium carbides which increases hardenability. 5.4.2 Nickel Steel
 It increases wear resistance. Composition
 It increases corrosion and oxidation resistance. C- 0.35%
Ni- 3.5%
Titanium (Ti) Properties
 It is strong carbide former.  Increased Strength
 It prevents localized precipitation of chromium carbides. Applications
 Low temperature applications
Tungsten (W)  Storage of liquefied gases
 It increases hardenability.  Heavy forgings, turbine blades etc.
 It forms carbides and increases wear resistance.

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5.4.3 Molybdenum Steel Properties

Composition  Increased strength and hardness.
C- 0.35%  High strength and antifatigue properties.
Mo- 0.76% Applications
Properties  Crankshafts, Compressor discs, springs, gears etc.
 Increased elastic limit
 Improved hot hardness & strength 5.5 Classification of Alloy Steels
 Unaffected by temper brittleness 5.5.1 Free Cutting Steels
Applications  These steels can be machine or cut with fast speed because
 Aircraft landing gear, leaf springs, pressure vessels etc. of their high machinability and hence known as free cutting
steels.
5.4.4 Manganese Steel  Low carbon steels produce rough surface and responsible
Composition for heating the tool.
C- 0.18 to 0.48%  So Mg, S and P are added to improve machinability.
Mn- 1.6 to 1.9%  Mg combines with S and favors chip formation and also
Si- 0.2 to 0.35% increase hardness and strength.
S- 0.04%
 Phosphorus also combines with iron and favors chip
P- 0.04%
formation.
Properties
 S and P are present in 0.6 and 0.12% while Mg is 5 to 8
 Increased hardness, tensile strength and resistance to
times the amount of sulphur.
abrasion
 In high carbon steels lead is added in 0.35% to increase
 Withstand shocks excellently
machinability.
Applications
 Grinding and crushing machinery, railway tracks, power 5.5.2 High Strength Low Alloy Steels (HSLA)
shovel buckets
 Contain C- 0.07 to 0.13% with 0.5 Al.
 These steels shows good ductility, malleability,
5.4.5 Chrome Nickel Steel
formability toughness and weldability because its strength
Composition
increases up to 50-80 Kg/mm2 and widely used in
C- 0.35%
automotive industry.
Ni-1.25%
Cr-0.6%  Low-alloy steels are usually used to achieve better
hardenability, which turn improves its other mechanical
Properties
properties.
 Increased toughness and ductility
 Alloying elements are added in lower percentages (less
 Improved hardenability and wear resistance
than 5%) to increase strength or hardenability, or in larger
Applications
percentages (over 5%) to achieve special properties, such
 Axles and crankshafts, Aircraft and heavy vehicle
as corrosion resistance.
component, highly stressed shafts, gears etc.
5.5.3 Maraging Steels
5.4.6 Tungsten Steel
 Maraging steels are steels, which are known for possessing
Composition
superior strength and toughness without losing
C- 0.5%
malleability, although they cannot hold a good cutting
W-2 to 15%
edge.
Cr-1.7%
 These steels contain 0.03% C, 18.25% Ni, 3 to 5% Mo, 3
Properties
to 8% Co, 0.2 to 1.6% Ti and small amount Al.
 Hard and tough sustain high temperatures
 These steel shows strength up to 210 Kg/mm2 and used for
Applications
special application such as rocket, engine component and
 High speed cutting tools, permanent magnets
pressure vessel.
 Due to the low carbon content maraging steels have good
5.4.7 Vanadium Steel
machinability and offer good weldability.
Composition
V- 0.15 to 0.25%  Due to the high alloy content maraging steels have a high
C- 0.35% hardenability. The steels can be nitride to increase case
Cr- 3% hardness, and polished to a fine surface finish.

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 It is also used in surgical components and hypodermic 5.5.8 Alloys for Heating Elements
syringes, but is not suitable for scalpel blades because the  Large number of heating device such as furnace, oven
lack of carbon prevents it from holding a good cutting edge. required special materials for conversion of electrical
 They are suitable for engine component, such as energy into heat.
crankshafts and gears, and the firing pins of automatic  These materials should have high resistance to oxidation,
weapons that cycle from hot to cool repeatedly while under sufficient strength and good resistivity.
substantial load.  Nickel-Cr alloy is suitable up to temperature 1150°C.
 Their uniform expansion and easy machinability before  Iron-Cr and Al alloy up to 1300°C, platinum up to 1480°C
aging make maraging steel useful in high-wear and Mo-W alloy can be used up to 1750-2500°C.
components of assembly lines and dies.
5.5.9 Rail Steels
5.5.4 Dual Phase Steels  These steels show a good combination of strength,
 These are low carbon steels with or without addition of ductility, high impact resistance and fatigue resistance.
alloying elements. These are obtained by heat treatment.  Medium carbon steel having carbon in the range of 0.04 to
 The steel is heated just above A1 temperature and rapidly 0.06% with small additions of manganese and chromium
cooled to the room temperature. up to 1% are used for making rails.
 Due to this treatment, the ferrite-pearlite microstructure is
changed to a mixture of martensite dispersed in a ferrite 5.5.10 Spring Steels
matrix. The amount of martensite varies from 15 to 30%.  These are used under various loads as compression, tension
 This microstructure is called as dual phase structure. and torsion.
 This steel shows high tensile strength and widely used for  These steels have high elastic limit, better elongation and
wheels, bumpers, disc, door panel etc. because of better high fatigue resistance.
formability.  A typical spring steels shows 0.06% carbon, 0.85% Mn and
2.0% Silicon.
5.5.5 Creep Resisting Steels  Cr, Ni, Mo and V may be added to replace silicon.
 These steels are used for high temperature applications
such as in thermal or hydropower plants because of their 5.5.11 Stellites
high temperature resistance, oxidation resistance and  They are the alloy tools having high hardness with wear
corrosion resistance. resistance and corrosion resistance.
 Temperature resistance is increased by addition of W, Mo,  These alloys contain Cr, W, C and in a Co matrix, the major
V, Cr and Co. constituent being Cr.
 A typical grade consists of 30% Cr, 19% W, 2% C, 3.5%
5.5.6 High Temperature Alloys (Super Alloys) Ni and remaining is Co.
 The strength of steel increases with increase in carbon  They can be used up to a temperature of 550°C without
contents. much of a decrease in performance.
 Low carbon steels show good ductility, formability,
weldability and low strength. 5.6 Stainless Steels
 However, the strength can be improved by addition of  These steels have high corrosion resistance and hence do
small quantities of alloying elements. These are called as not corrode under normal environmental conditions i.e.
high strength low alloy steels. they are free from stains.
 Used for high temperature applications, they have high  The high corrosion resistance of stainless steels is due to
strength, hardness, wear resistance, creep resistance and the presence of alloying elements, namely Chromium.
oxidation resistance.  When chromium is present is excess of 13%, a thin film of
chromium oxide is formed on the surface that is exposed to
5.5.7 Low Expansion Steels air.
 These are the alloys of nickel and iron containing 36% Ni,  This film restricts any further oxidation, rust or corrosion
02% C, 0.5% Mn and balance iron. of the inner layer of steel.
 This is called invar contains 36% Ni, 12% Cr and W with  Chromium in steel also combines with carbon to form
balance iron. complex chromium carbides.
 These steels have very low coefficient of expansion and it  Hence, it needs to be ensured that the amount of chromium
is widely used for the application such as gauges, tapes and in the steel in solid solution form is above 13%.
micro meters.  Other major alloying elements added are Molybdenum and
Nickel.

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 Nickel improves stability of austenite at room Table No. 5.1 Composition of Austenitic Stainless Steels
temperature, making the steel ductile and improves impact Type C Mn Si Cr Ni Others
strength. AISI % % % % % %
 Molybdenum also supports high corrosion resistance. 201 0.15 5-7 1 16-18 3.5-5.5 0.25 N
 Stainless steels are used for both corrosion and heat 202 0.15 7-10 1 17-19 4-6 0.25 N
resisting applications. A three-numeral numbering system 301 0.15 2 1 16-18 6-8 -
302 0.15 2 1 17-19 8-10 -
is used to identify stainless steels.
302 B 0.15 2 2-3 17-19 8-10 -
 The last two numerals have no particular significance, but
303 F 0.15 2 1 17-19 8-10 0.15 S
the first numeral indicates the group as follows:
304 0.08 2 1 18-20 8-12 0.15 Se
Series
Groups 304 L 0.03 2 1 18-20 8-12 -
Designation
305 0.12 2 1 17-19 10-13 -
Chromium-Nickel-Manganese; non- 308 0.08 2 1 19-21 10-12 -
2XX
Hardenable, austenitic non-magnetic.
309 0.2 2 1 22-24 12-15 -
Chromium-Nickel; non-Hardenable, 309 L 0.08 2 1 22-24 12-15 -
3XX
austenitic, non-magnetic. 310 0.25 2 1.5 24-26 19-22 -
Chromium, Hardenable, Martensitic, 314 0.25 2 1-3 23-26 19-22 -
4XX
Magnetic. 316 0.28 2 1 16-18 10-14 2-3 Mo
4XX Chromium, Hardenable, ferritic, Magnetic. 316 L 0.03 2 1 16-18 10-14 2-3 Mo
317 0.08 2 1 18-20 11-15 3-4 Mo
5XX Chromium, Low chromium, heat resisting. 321 0.08 2 1 17-19 9-12 Ti
 The corrosion-resisting property is due to thin, adherent, 347 0.08 2 1 17-19 9-13 Cb-Ta
stable chromium oxide or nickel oxide film that effectively 348 0.08 2 1 17-19 9-13 Cb-Ta
protects the steels against many corroding media.  These are the chromium-nickel (Type 3XX) and
 This property is not evident in low-chromium structural chromium-nickel manganese stainless steels (Type 2XX).
steels that is previously discussed and is apparent only  These types are austenitic, are essentially non-magnetic in
when the chromium content exceeds about 10%. the annealed condition, and do not harden by heat
 Since, stainless steels contain relatively large amounts of treatment.
chromium, the iron chromium-carbon alloys belong to a  The total content of nickel and chromium is at least 23 %.
They can be hot worked readily and can be cold worked
ternary system.
when proper allowance is made for their rapid work.
5.6.1 Classification of Stainless Steels based on  Hardening cold working develops a wide range of
Microstructure mechanical properties and the steel in this condition may
1. Austenitic Stainless Steel (Group C): become slightly magnetic.
 They possess austenitic microstructure at room  They are extremely shock resistance and difficult to
temperature. machine unless they contain sulphur and selenium (Types
 Nickel, an alloying element aids stability of austenite over 303 and 303 Se). These steels have the best high-
wide range of temperatures. temperature strength and resistance to scaling of the
 This category of steel has the highest corrosion resistance stainless steels.
of all stainless steels.  The corrosion resistance of the austenitic stainless steels is
usually better than that of the martensitic or ferritic steels.
Composition
C- 0.03 to 0.25% Application
Cr- 16 to 26% Aircraft engine part, Heat exchangers, cooking utensils, wrist
Ni- 3.5 to 22% watches, transportation trailers, sanitary fittings.
Si- 1 to 2%
Mn- 2.0 to 10.0% 2. Ferritic Stainless Steel (Group B):
Mo- Small Traces  They possess ferritic microstructure at room temperature.
 As ferrite is a non-hardenable phase, this category of steel
Properties cannot be hardened by heat treatment.
Ductile, Highest Corrosion Resistance, High Strength, Non-  Though, they can be moderately hardened by cold working
magnetic, Expensive. process followed by annealing.

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Composition Application
C- 0.08 to 0.20% Combustion chamber, Lining for petroleum industry, furnace
Cr- 11 to 27% parts, nozzles, gas burners, screws & fittings, vessels in
Si- 1.0% chemical industry.
Mn- 1.0 to 1.5%
3. Martensitic Stainless Steel (Group A):
Properties  They possess martensitic microstructure at room
Non-hardenable, soft, ductile, corrosion resistant, magnetic. temperature.
 They have high carbon content and hence are hardenable
Table No. 5.2 Composition of Ferritic Stainless Steels by heat treatment.
Type C Mn Si Cr Ni Others %  Low carbon grade martensitic stainless steel can also be
AISI % % % % % cold worked.
405 0.08 1 1 13-14 - 0.1-0.3 Al
430 0.12 1 1 14-18 - - Composition
430 F 0.12 1-2 1 14-18 - 0.15 S-0.15 Se C- 0.15 to 1.2%
442 0.2 1 1 18-23 - - Cr- 11.5 to 18%
446 0.2 1.5 1 23-27 - 0.25 N Si- 1.0 %
 This group of straight chromium stainless steel contains Mn- 1.0 %
approximately 14 to 27 % chromium and includes type
405, 430 and 446. Properties
 In stainless steels, low carbon contents but generally higher Hardenable, High strength, toughness, ductile, magnetic.
chromium contents than the martensitic grades are found.
 These steels are not hardened by heat treatment and are Table No. 5.3 Composition of Martensitic Stainless Steels
moderately hardened by cold working. Type C Mn Si Cr Ni Others
 They are magnetic and can be cold-worked or hot worked, AISI % % % % % %
but they develop their maximum softness, ductility and 403 0.15 1 0.5 12-13 - -
corrosion resistance in the annealed condition. 410 0.15 1 1 12-14 - -
 In the annealed condition, the strength of these is 414 0.15 1 1 12-14 1-2 -
approximately 50 % higher than that of carbon steel and 416 0.15 1-2 1 12-14 - 0.15 S
they are superior to the martensitic stainless steels in 416 Se 0.15 1 1 12-14 - 0.15 Se
corrosion resistance and machinability. 420 >0.15 1 1 12-14 - -
 Since the ferritic steel may be cold-formed easily, they are 431 0.2 1 1 15-17 1-2 -
used extensively for deep-drawn parts such as vessels for 440 A 0.65 1 1 16-18 - 0.75 Mo
chemical and food industries and for architectural and 440 B 0.85 1 1 16-18 - 0.75 Mo
automotive trim. 440 C 1.1 1 1 16-18 - 0.75 Mo
 The only heat treatment applied to truly ferritic steels in  These steels are primarily straight chromium steels
annealing. This treatment serves primarily to relieve containing between 11.5 and 18 % chromium.
welding or cold working stresses.  Some examples of this group are types 403, 410, 416, 420,
 An important form of brittleness peculiar to the ferritic 440 A.
grades can develop from prolonged exposure to or slow  Types 410 and 416 are the most popular alloys in this group
cooling within, the temperature range from about 398°C to and are used for turbine blades and corrosion-resistance
510°C. castings.
 Certain heat treatment such as furnace cooling for  The martensitic types of stainless steels are steels are
maximum ductility, must be controlled to avoid magnetic and can be cold-worked without difficulty,
embrittlement. especially with low carbon content can be machined
 Ferritic steels are usually annealed at temperature above satisfactorily and have good toughness, show good
the range for 454°C embrittlement and below temperature corrosion resistance to weather and to some chemicals and
at which austenite when heated treated above the A1 line are easily hot-worked.
to obtain maximum ductility, these steels are then cooled  They attain the best corrosion resistance when hardened
slowly. from the recommended temperature but are not as good as
 They are not tempered, since the amount of martensite the austenitic or ferritic stainless steels.
found is negligible, and because of possible embrittlement  The heat treatment process for martensitic steels is
in the 454°C range. essentially the same as for plain-carbon or low-alloy steels,

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where maximum strength and hardness depend chiefly on  During welding of austenitic steels, the temperature near
carbon contents. the welding is high and hence it cools fast, thus suppressing
 The principal difference is that the high alloy content of the the separation of Cr-carbides.
stainless grades causes the transformation to be so sluggish  But at some distance away from the weld where the
and the hardenability so high that maximum hardness is temperature is in the range of 500-800°C, the Cr-carbide
produced by air cooling. precipitates occurs.
 These steels are normally hardened by heating the above  The Cr-carbides preferentially separate out and the region
the transformation range to temperature near 1009°C, then gets corroded by intergranular corrosion.
cooling in air or coil.  Weld Decay can be avoided by the following techniques:
 Time at temperature is held to a minimum to prevent 1. Use fast cooling rates in regions away from weld.
decarburization or excessive grain growth. 2. Use low carbon steels so that the overall amount of
 Tempering of steels in this group should not be done in the carbides are reduced.
range of 398°C to 593°C due to the change in impact 3. Use fine grained steel since fine grains increase the grain
properties. boundary area reducing the precipitation rate.
 Tempering is usually done above 593°C. The higher 4. Use ferrite forming elements in austenite steel such as Si,
tempering temperatures will cause some precipitation of
Mo, W, V etc.
carbides with a subsequent reduction in corrosion
resistance. However with the carbon on the low side of the
5.8 Sensitization (Carbide Precipitation)
range, the lowering of corrosion resistance is not too
severe.
 Stainless steels as a group are much more difficult to
machine than plain carbon steels. The use of a small
amount of sulphur in type 416 and selenium in type 416
improves the machinability.

Application
Valves, pumps, surgical instruments, razors, blades, turbine
blades.

4. Precipitation Hardenable Stainless Steel:

 They contain high amount of alloying elements which are
used to improve strength and toughness.
 The alloying elements used are Mo, Cb, Ti, Al, Cu or N
along with C, Cr and Ni.
 These alloying elements form complex precipitates of their
compounds.
Fig. No. 5.2 Depletion of Chromium due to Carbide
Composition Precipitation
High content of alloying elements such Mo, Cb, Ti, Al, Cu, N.  The equilibrium structure of 18-8 stainless steel consists of
α, γ and Cr carbides but, during rapid cooling condition
Properties only γ is obtained.
High strength, toughness.  If this austenitic stainless steel is heated between 500 to
800°C for some period, then the carbides (FeCr) 4C will
Application precipitate along the grain boundaries.
Aircraft engines, missiles, structural components.  These carbides are rich in chromium (more than 70% Cr).
This Cr is taken from the adjacent region of the carbides.
5.7 Weld Decay of Stainless Steels  Hence Cr content goes below 13% i.e. below the minimum
 It is a phenomena of intergranular corrosion observed requirement for good corrosion resistance.
during welding.  The area in which Cr is depleted become anodic with
 This phenomenon tales place during welding of austenitic respect to the other high Cr areas and steel gets corroded.
stainless steels.  Precipitation of Cr carbides makes the steel sensitive to
 If an austenitic stainless steel is heated around 500-800°C intergranular corrosion. Hence, the precipitation of
and allowed to cool slowly, the Cr-carbide precipitates out. carbides along the grain boundaries is known as
sensitization.

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 The reduction in corrosion resistance due to Cr carbides Applications

precipitation can be eliminated by heating the steel Blanking and forming dies, blades, gauges, cutting tools.
between 1000 to 1100°C and rapid cooling to room
temperature.  These steels contains small amount of alloying elements.
 Because of heating between 1000 to 1100°C, carbides are  Their hardenability is better than water hardening steels.
dissolved in austenite and due to rapid cooling to room  The distortion during hardening is less and hence they are
temperature their separation is prevented. also called as Oil hardening Non shrinkage steels (OHNS).

5.9 Tool Steels c) Air Hardening Steels (A-Series)

Alloying Elements
 As the name suggests, this type of steel is used as material
Carbon- 0.6 to 1.4 %
for mechanical working tools.
(W + Mn + Cr + Mo + V) > 5%
 These are specially developed for use as working on
metals, cutting, forming and bending operations.
Properties
 In general, all tool steels have following properties:  Better Hardenability – Air quenching.
1. Hardness
 High wear resistance.
2. Toughness
 Less distortion.
3. Wear Resistance
4. Red Hardness  Good depth of hardening.
5. Depth of Hardening
6. Machinability Applications
7. Non-deforming Thread rolling, drawing dies, punches, master gauges, slitting
dies.
 Tools steels are classified based on the quenching method,
applications and mechanical properties.
 They have alloying elements in excess of 5%.
 AISI (American Iron and Steel Institute) has classified and
designated the tools as follows:  They have high wear resistance, hence are used for
precision applications.
5.9.1 Cold Work Tool Steel
a) Water Hardening Steels (W-Series) d) High Carbon High Chromium Steels (D-Series)
Alloying Elements Alloying Elements
Carbon – 0.6 to 1.4%. Carbon > 1.5%
Balance is iron. Cr > 12%
Alloys < 5%
Properties Balance is Iron
 Relatively low hardenability-Water quenching.
Properties
 Low red hardness.
 High hardenability.
 Tendency towards oxidation.
 Less distortion.
Applications  High red hardness.
Small Hammers, chisels, rivets, drills, taps, reamers, forming
tools, knives, razors. Applications
Drawing dies, punches, blanking dies, coining dies, thread
rolling dies, forming dies, cutting tools.
 Because of low carbon content, they are less hard but can
be used for shock loading conditions.
 They contain high amount of alloying elements such as Cr,
 They are hardened by quenching in water.
W, and Mo etc.
 Because of low red hardness, they cannot be used at high
 These alloys form complex carbides which increases the
temperatures.
hardness of steel.
b) Oil Hardening Steels (O-Series)  They maintain hardness up to a temperature of 500°C.
Alloying Elements  Since the amount of chromium in solid solution form
Carbon- 0.6 to 1.4% (remaining after complex carbide formation) is 13%, these
(W + Mn + Cr + Mo + V) < 5% steels are not categorized as stainless steel.

Properties 5.9.2 Hot Work Tool Steel (H-Series)

 Better Hardenability – Oil quenching, less distortion. a) Chromium Type

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Alloying Elements Properties

Carbon- 0.35 to 0.55%  High red hardness.
Cr- 3 to 7%  High wear resistance.
(W + Mo + V) < 5%  Cutting ability.
 Expensive.
Properties
 High ductility, Toughness. Applications
 Resistance to splitting. High speed cutting tools such as drills, reamers, milling cutters,
lathe tools, drawing dies.
Applications
Al and Mg extrusion dies, casting dies, forging dies, mandrels. b) M-Series (Molybdenum)
Alloying Elements
 The amount of alloying elements is less and hence carbide Carbon < 0.12%
formation is low. W < 10%
 They possess high ductility, toughness and hence used for Cr, V
Al and Mg dies.
Properties
b) Tungsten Type  High red hardness.
Alloying Elements  High wear resistance.
Carbon- 0.3 to 0.5%  Cutting ability.
Cr- 2 to 12%  Relatively cheaper.
W- 9 to 18%
Applications
Properties High speed cutting tools such as drills, reamers, milling cutters,
High red hardness, strength, toughness, wear resistance. lathe tools, drawing dies.

Applications  High speed tool steels maintain high hardness up to 550°C.

Hot extrusion dies, forging dies, hot punches.  They are used for cutting of metals at high speeds.
 The alloying elements form respective carbides which
 These steels have excellent red hardness and resistance to increases red hardness, wear resistance and cutting ability.
wear at elevated temperatures.
5.9.4 Special Purpose Tool Steels
c) Molybdenum Type a) S-Series (Shock Resisting)
Alloying Elements Alloying Elements
Carbon- 0.55 to 0.65% Carbon < 0.5%,
(Mo + Cr + V + W)- 14 to 20% (Mn, Cr, W, Mo, V, Si)
Properties Properties
Properties are intermediate to chromium type and tungsten type. Better shock resistance, less hardness.
Applications Applications
Casting dies, forging dies, extrusion dies. Rivets, cold punches, forming dies, chisels, bearings.
 These steels are intermediate in properties of chromium  Because of less carbon, these steels cannot be hardened
type and tungsten type. much.
 They are used where compromise in resistance to high  They have excellent shock and impact resisting
temperature and toughness is required. characteristics.
5.9.3 High Speed Tool Steels b) L-Series (Low Alloy)
a) T-Series (Tungsten) Alloying Elements
Alloying Elements Alloying elements such as Cr, W, V, Mo and Ni
Carbon < 0.12%
W < 20% Properties
Cr, V Less distortion during hardening, high wear resistance.

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Applications
Rollers, bearings, cams, wrenches, gauges.

 They are similar in properties to water hardening tool

steels.
 The major alloying element is Cr.

c) F-Series (Carbon-Tungsten)
Alloying Elements
C > 1%

Properties
High wear and abrasion resistance.

Applications
High speed reamers, taps, broachers, burnishing tools.

 The major alloying element is tungsten.

 They have better wear resistance than L-series tool steels.
Fig. No. 5.3 Hardening and Tempering Cycle of 18-4-1
d) P-Series (Mould Steels) High Speed Tool Steel
Alloying Elements  The steel is initially heated to around 800°C and
C < 0.2% maintained at that temperature for 5-10 minutes.
Cr, Ni  The pre-heated steel is then transferred to a salt bath
furnace maintained at around 1300°C.
Properties  Salt bath heating reduces chances of oxidation and de-
High abrasion resistance and shock absorbing capacity. carburization.
 The steel is soaked at this temperature for couple of
Applications minutes.
Plastic Moulds  At this temperature, almost all the carbides get dissolved in
austenite.
 They are used for making of dies for plastic injection  The microstructure at this stage is: 90% austenite + 10%
moulding. complex alloy carbides.
 They have high hardness at the surface layer to take care of  The steel is then quenched in oil to room temperature
abrasion of plastic powders and soft inner core to take care producing martensitic transformation.
of the shock loading on the dies.  The microstructure at this stage is: 60% martensite + 30%
retained austenite + 10% alloy carbides.
5.10 18-4-1 High Speed Tool Steel  To increase the hardness and strength of the steel, the
 It is the most widely used grade of Tungsten High Speed retained austenite is eliminated by tempering treatment.
Tool Steel (T-series).  Tempering is carried out at 550°C with a soaking period of
 It contains 0.7%C, 18%W, 4% Cr and 1%V. 2 to 2.5 Hrs.
 It retains high hardness up to temperature of about 600°C.  At the end of the tempering treatment, the microstructure
 It has very high wear resistance and cutting ability. consists of: Tempered Martensite + Low alloy Low carbon
martensite + Alloy carbides.
5.10.1 Heat Treatment Cycle of 18-4-1 Steels
 The presence of alloying elements in high proportion in the 5.11 Special Purpose Steel
steel increases the eutectoid temperature and shifts the  Many steels have been developed for special applications.
eutectoid composition from 0.8%C to 0.25%C. There are steels intended for high-temperature and low-
 Thus the austenitizing temperature of 18-4-1 steels is very temperature service, for springs; for pressure vessels, for
high. boilers, for use in concrete, for railroads, and for all sorts
 Fig. No. 5.3 shows the hardening and tempering cycle for of service conditions.
this steel.  In addition to steels for specific types of service there are
 Heating this steel to austenitizing temperature is done in steels with various coatings (For example, tin plate and
two stages to avoid thermal shock and cracking of steel. aluminized).

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 These can be applied to any type of service, and 3. High creep resistance
specifications center on base metal and coating 4. High oxidation resistance
characteristics. The AISI has product specifications on
coated steels, rail steels, and steels for various building 5.13 Heat Affected Zone
applications.  The heat affected zone is the region that experiences a peak
 There is no numbering system on these steels, and product temperature that is well below the solidus temperature
information is best obtained from the AISI steel product while high enough that can change the microstructure of
hand books. the material.
 The AISI has specifications on many coated products, rail  The amount of change in microstructure in HAZ depends
products and steels intended for particular types of service. on the amount of heat input, peak temperature reached,
The ASTM specification number can be used for time at the elevated temperature, and the rate of cooling.
specifying these steels.  As a result of the marked change in the microstructure, the
 There in an AITM index that supplies information on the mechanical properties also change in HAZ and usually, this
availability of specifications on these types of steels. zone remains as the weaked section in a weldment.
Special purpose steels and many steels from the other  The unaffected base metal zone surrounding the HAZ is
categories mentioned are converted by competitive alloy likely to be in a stable of high residual stress, due to the
designation system developed by various government shrinkage in the fusion zone.
regulatory bodies.  However, this zone does not undergo any change in the
 These alloy designation system are usually mandated for microstructure.
government work, but in private industry the  The fusion zone and HAZ of welded joint can exhibit very
predominating alloy-designation systems for steels used in different mechanical properties from that of the unaffected
machines are the AISI and ASTM. base metal as well as between themselves.
 For example, the fusion zone exhibit a typical cast structure
5.11.1 Applications of Special Purpose Steel while the HAZ will exhibit a heat treatment.
 It is used for cams.
 It is used for chucks.
 It is used for collects.
 It is used for tube drawing.
 It is used for wire drawing.
 It is used for cold extrusion.
 It is used for dies.
 It is used for brass cutting tools.

5.12 Super Alloys

 Superalloys are also called as high temperature alloys
because these alloys are mainly used for high temperature
applications.
 They can be iron base alloys, nickel base alloys, cobalt base
alloys or refractory metals and alloys.
 Iron base alloys contain V, W, Mo and Cr as alloying
elements. High speed and super high speed steels come
under this category of steel.
 Nickel base alloys contain Mo, Cr and Co. The alloys
which comes under this category are Inconel's, hastelloys,
nimonics and waspaloy.
 Cobalt base alloys contain Cr, Mo and Ni. The alloys
which comes under this group are stellites. Fig. No. 5.4 Different zones in a steel weld iron carbon
 Refractory metals like W, Mo, Cr, Co and their alloys are equilibrium diagram
used at high temperatures because of their high  Structure involving phase transformation, recrystallization
recrystallization temperature. and grain growth.
 The important characteristics of Superalloys are as follows:  The unaffected base metal, on the other hand, will show the
1. High resistance and strength original rolled structure with a slight grain growth.
2. High wear resistance  Fig. No. 5.4 shows that different zones of a steel weldment
can be indicated on an iron carbide equilibrium diagram.

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5.14 Designation (For Plain and Alloy Steels) 7. 35 C 10 S 14:- Steel with average C- 0.35%, Mn- 1%
 Steels are specified on the basis of certain criteria like the and S- 0.14%.
method of manufacture, chemical composition, heat 8. 80T11:- Tool steel with average carbon of 0.8% and
treatment, mechanical properties, quality etc. 1.1% Mn
 Every country has different way of specification. But 9. 20 Ni55 Cr 50 Mo20:- Steel with average carbon of
majority of specification are based on chemical 0.20%, Ni-0.55%, Chromium 0.50% and Mo-0.20%.
composition because the chemical composition gives 10. 14 C 6:- Steel with average composition of C- 0.14%,
information about heat treatment and resulting mechanical Mn- 0.6%.
properties. 11. 113 C 6:- Steel with average composition of C- 1.13%,
 The knowledge of these specifications helps in selecting Mn- 0.6%.
proper type of steel from those available in the market for 12. 10 C 8 S 10:- Steel with average composition of C-
particular service requirement. 0.1%, S- 0.8%, Mn- 1%.
13. 15 Cr 65:- Steel with average composition of C-
0.15%, Cr- 0.65%.
5.15 Indian Standard Designation System (IS) 14. 20 Mn Cr 1:- Steel with average composition of C-
 Indian standard code for designation of steel was adopted 0.2%, Mn- 1%, Cr- 1%.
by the Indian standard institution (ISI) in 1961. 15. 25 Cr 4 Mo 2:- Steel with average composition of C-
 In 1974, these standards are revised in two parts: 0.25%. Cr- 1%, Mo- 0.2%.
16. XT 98 W 6 Mo 5 Cr 4 V 1:- Alloy tool steel with
Part 1: average composition of C- 0.98%, W- 6%, Mo- 5%,
 It covers the designation of steel based on letter symbols. Cr- 4%, V- 1%.
17. X 10 Cr 18 Ni 9:- Alloy tool steel with average
Part 2: composition of C- 0.10%, Cr- 18%, Ni- 9%.
 It covers the designation of steel based on Numerals, for 18. T 75 W 18 Cr 4 V 1:- Tool steel with average
the purpose of code designation. composition of C- 0.75%, W- 18%, Cr- 4%, V- 1%.
 Steel have been classified on the basis of mechanical 19. T 35 Cr 5 Mo 1 V 30:- Tool steel with average
properties and chemical composition. composition of C- 0.35%, Cr- 5%, Mo- 1%, V- 0.30%.
 Code designation on the basis of mechanical properties
base on tensile strength or yield strength. 5.16 AISI/SAE Designation System
 Symbol Fe is for minimum tensile strength and FeE to  American Iron and Steel Institute (AISI) and Society of
designate minimum yield strength in N/mm2. Automotive Engineers (SAE) have established a system of
 But when tensile strength and yield strength are in kg/mm2 specifying steel based on the chemical composition.
it is denoted as “St” and “St E” respectively.  The system consists of designating the steel with four or
 Designation of steels on the basis chemical composition five numerical digits.
consists of mechanical figures indicating 100 times the  The first digit indicates the type of steel. (Refer Table No.
average % of carbon content.
5.4)
 Letter ‘C’ is used for plain carbon steels and ‘T’ is used for
 The second digit indicates approximate % of predominant
tool steels. Letter C or T is followed by figure indicating
10 times the average percent of manganese content. alloying element.
 Symbols S, Se, Te, Pb or P are used to indicate free cutting  The last two or three digits divided by 100 indicates
steels followed by a figure indicating 100 times the percent average carbon content.
content of the respective element.  The following are some important types of steels in
 Some examples are as: AISI/SAE system:
1. Fe 200:- Steel with minimum tensile strength of 200 1. Carbon steels
N/mm2. 2. Nickel steels
2. Fe E 225:- Steel with minimum yield strength 225 3. Ni-Cr steels
N/mm2. 4. Molybdenum steels
3. Fe 200 K:- Killed steel with minimum tensile strength 5. Chromium steels
of 200 N/mm2. 6. Cr-V steels
4. St 42:- Steel with minimum tensile strength of 42 7. Tungsten steels
kg/mm2. 8. Ni-Cr-Mo steels
5. C20:- Steel with average carbon of 0.2%. 9. Si-Mn steels
6. 25C5:- Steel with average carbon of 0.25% and Mn
of 0.5%.

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Table No. 5.4 Some Important AISI/SAE Steel  Some important steels designated by En series are listed
Designation Groups below.
S. AISI/SAE
Details of the steel
N. Group Table No. 5.6 British Standard System
1 Carbon Steels 1XXX En No. Composition
i) Plain Carbon 10XXX En 1 C- 0.07 to 0.15%
ii) Free Cutting Steel 11XX, 12XX Mn- 0.8 to 1.2%
iii) Manganese Steel 13XX S- 0.2 to 0.30%
2 Nickel Steels 2XXX P- 0.07%
i) 0.50% Ni 20XX Si- 0.1%
ii) 1.5% Ni 21XX En 8 C- 0.35 to 0.45 %
iii) 3.5% Ni 23XX Mn- 0.6 to 1.0%
iv) 5.0% Ni 25XX S and P- 0.06%
3 Nickel-Chromium Steels 3XXX Si- 0.05 to 0.35%
i) Various combination of Ni 31XX to 34XX En 24 C- 0.35 to 0.45%
and Cr Mn- 0.45 to 0.70%
4 Molybdenum Steels 4XXX Ni- 1.3 to 1.8%
i)Cr-Mo 41XX Cr- 0.9 to 1.4%
ii) Cr-Ni-Mo (High) 43XX Mo- 0.2 to 0.35%
iii) Ni-Mo 46XX to 48XX Si- 0.1 to 0.35%
5 Chromium Steels 5XXX En 36 C- 0.15%
6 Chromium-Vanadium Steels 6XXX Mn- 0.3 to 0.6%
7 Tungsten Steels 7XXX Ni- 3 to 3.75%
8 Ni-Cr-Mo Steels (Low) 8XXX Cr- 0.6 to 1.1%
9 Silicon Steels 92XX Si- 0.1 to 0.35%
En 42 C- 0.07 to 0.85%
Some examples of AISI/SAE steel composition. Mn- 0.55 to 0.75%
S and P- 0.05
Table No. 5.5 Examples of AISI/SAE Steels Si- 0.1 to 0.4%
S. En 353 C- 0.10 to 0.20%
AISI No. Composition % Si- 0.35%
N.
1 1040 Plain Carbon Steel with C- 0.4% Mn- 0.5 to 1.0%
2 2440 Nickel Steel with 4%-Ni and C-0.4% Cr- 0.75 to 1.25%
3 1010 Plain Carbon Steel with C-0.1% Mo- 0.08 to 0.15%
4 1035 Plain Carbon Steel with C-0.35% Ni- 1.0 to 1.5%
5 1095 Plain Carbon Steel with C-0.95%
6 1112 Free Machining Steel 0.12% C
7 12 L 14 0.12% C, 0.14% Lead, F.M.S
5.18 DIN
8 1330 0.3% C, Mn Steel Carbon with Mn as  DIN stand for ‘Deutsches Institut fur Normung’ it means
major alloying element C- 0.3%, Mn- German Institute for Standardisation.
3%  DIN standards that starts with DINV (Vornorm Means
9 2317 Nickel Steel with C-0.17%, Ni-3% Preissue) are the result of standardisation work but due to
10 9260 Silicon Steel with C-0.6%, Si- 2% certain reservations on the content or due to divergent
compared to a standard installation procedure of DIN, they
are not yet published standards.
5.17 British Standard Designation System
 The designation of DIN standard shows its origin (#
 This system is used in British to designate steels and is also
denoted a number):
known as En series. 1. DIN # is used for German standards with primarily
 En stands for Emergency Number, since it was developed domestic significance or designed as a first step
during World War II. towards international status. E DIN # is a draft
 It is represented as En XX, i.e. En- followed by numerical. standard and DIN V # is a preliminary standard.
 The En number does not have any co-relation with the 2. DIN EN # is used for the German edition of European
composition of mechanical properties of the steel. Standards.

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3. DIN ISO # is used for the German edition of ISO ii) XT75W18Cr4V1
standards. (Refer Section 5.15)
4. DIN EN ISO # is used if the standard has also been 2. What influence does Molybdenum (Mo) addition have on
adopted as a European Standard. steel? Why is Mo used as an alloying element?
5. DIN EN ISO # is used if the standard has also been (Refer Section 5.3)
adopted as a European Standard. 3. What is stainless steel? Why are these steels stainless?
 Examples of DIN standards are: (Refer Section 5.6)
1. DIN 476: International paper sizes. 4. Mention the names of alloying elements used and the amount
2. DIN 1451: Used by German railways and on traffic in percent of alloy used in the following steels.
signs. i) C40
3. DIN 72552: Electrical terminal numbers in ii) AISI 1040
(Refer Section 5.15 and 5.16)
automobiles.

University Question November 2018 Examination

1. What is HAZ? Explain with suitable figure.
November 2019 Examination (Refer Section 5.13)
2. What is IS, AISI, SAE and DIN? Explain in detail.
1. State the composition of the following steel which is (Refer Section 5.15, 5.16 and 5.18)
specified as per Indian Standard Designation System:
i) T75W18Cr4V1
ii) Fe410K November 2017 Examination
(Refer Section 5.15)
2. Explain classification of Alloying Elements of Steel with
respect to the relation with carbon. Give examples for each 1. What do you understand by weld decay of austenite stainless
category. steel? State the methods of prevention of weld decay.
(Refer Section 5.5) (Refer Section 5.7)
3. Explain the function of Addition of Tungsten as an Alloying 2. Prepare a table comparing alloy steels and plain carbon steels
Element in steel. on the basis of the following:
(Refer Section 5.3) i) Corrosion resistance
4. Some of the High Carbon High Chromium (HCHC) tool steel ii) Hardenability
contains carbon more than 2% still they are classified as steels iii) Cost
and not cast irons. Why? iv)Toughness
Ans: - 1) Part of the carbon combines with allowing elements (Refer Section 5.1)
like Cr, W, Mo and V and the remaining carbon goes in 3. What will be the AISI equivalent of the following?
austenite in the solid solution form. This remaining carbon is i) C40
always less than 2.0% ii) T80
2) Also there is no eutectic formation in these compositions at (Refer Section 5.15 and 5.16)
any of the temperatures cast irons show eutectic formation. 4. Explain with a neat sketch heat treatment cycle of high speed
5. Explain the importance of manganese as an alloying element steel with proper reasoning.
in steel. How does it influence the isothermal transformation (Refer Section 5.10.1)
diagram? Give a typical composition of steel which has
excellent wear resistance and is non-magnetic.
(Refer Section 5.3)
May 2017 Examination
6. What are super alloys? State any three types of super alloys
with a suitable example. 1. Explain classification of alloy steel.
(Refer Section 5.12) (Refer Section 5.5)
2. Explain Heat Affected Zone. Due to which manufacturing
process is it formed?
May 2019 Examination (Refer Section 5.13)
3. What is stainless steel? Explain classification of stainless
1. Mention the names of alloying elements used and percent of steel based on microstructure.
alloy used in the following steels. (Refer Section 5.6 and 5.6.1)
i) T70

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4. Explain the effect of Nickel and Chromium on microstructure

and Mechanical properties of steel.
(Refer Section 5.3)
5. Explain the heat treatment of High Speed Steel.
(Refer Section 5.10)

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 Unit VI- Non Ferrous Metals

Unit – VI
Non Ferrous Metals

Syllabus:
Classification of nonferrous metals. Importance of nonferrous metals in engineering applications & compositions,
study of different mechanical properties: Cu & Cu based alloys, Al and Al based alloys, Ni and Ni based alloys,
Co and Co based alloys, Titanium & its alloys, Tin & Lead base alloys, bearing materials: important properties &
applications.

Section No. Topic Name Page No.

6.1 Introduction 114
6.2 Importance of Non-Ferrous Metals in Engineering 114
6.3 Copper and Its Alloys 114
6.4 Aluminium and Its Alloys 120
6.5 Nickel and Its Alloys 122
6.6 Cobalt and Its Alloys 123
6.7 Titanium and Its Alloys 124
6.8 Tin and Its Alloys 125
6.9 Lead and Its Alloys 125
6.10 Bearing Materials 126
6.11 Soldering Alloys 128
6.12 Brazing Alloys 128

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6.1 Introduction 6.3 Copper and its Alloys (Cu)

 Metallic materials are broadly classified as ferrous and The total consumption of copper and copper alloys in the form
non-ferrous. (Refer Fig. No. 6.1) of different products is as shown in Fig. No. 6.2, and the
different alloying elements which are added in pure copper and
their effect on metal properties is shown in Fig. No. 6.3

Fig. No. 6.1 Classification of metallic materials

 Many non-ferrous materials find wide applications in
various industry sectors.
 In this unit, we will study the composition, characteristics
and properties of important non-ferrous materials.
 The important non-ferrous materials included in this unit
are:
1. Copper and its alloys
2. Aluminium and its alloys
3. Nickel and its alloys
4. Bearing materials Fig. No. 6.2 Different use of copper and copper alloys
5. Titanium and its alloys
6. Soldering and brazing alloys

6.2 Importance of Non-Ferrous Metals in

Engineering
 Non-ferrous metals are those which contain a metal other
than iron as their main element or constituent.
 Non-ferrous metals find wide applications in various
industrial sectors because of following advantages:
1. Low density, hence light in weight.
2. High electrical conductivity.
3. Easy to fabricate.
4. High corrosion resistance.

Ferrous metals Non-ferrous metals

Ferrous metals mostly contains Non-ferrous metals do not
iron as a main constituent. contain iron. Fig. No. 6.3 Alloying element added in copper
Ferrous metals are magnetic. Non-ferrous metals are non-  Copper, which is a pinking red metal possesses the
magnetic following properties:
They give little resistance to They are usually more 1) Good ductility and malleability
corrosion resistant to corrosion than 2) High electrical and thermal conductivity
ferrous metals. 3) Non-magnetic
Ferrous metals includes mild Non-ferrous metals includes 4) Can be easily alloyed with other metals
steel, carbon steels, cast iron, copper, aluminium, nickel, 5) Good corrosion resistance
wrought iron etc. tin, lead, zinc etc.  Copper is available in wires, rods, tubes, thin sheets, strips
Ferrous metals are heavier, Non-ferrous metals are much and foils. The relative density of copper is 8.93 and the
have high strength and higher and malleable than melting point is 1083°C, with FCC structure.
durability. ferrous metals.  Various alloying elements are added to copper to improve/
They are suitable for building They are suitable for or add some properties.
construction, rail-road, electrical wiring, electronic  Major alloying elements are: Zn, Sn, Al, P, Pb, Be, Fe, Si,
bridges, piping etc. components, heat exchangers Ni, Mg and Mn.
etc.  The alloys of copper are classified as brass and bronzes.

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 Brasses are alloys of copper and Zinc with small amount of 3. γ : Hard and brittle
other alloying elements.  Brasses are classified as:
 Bronzes are alloys of copper and any other alloying 1) α-brasses : Containing Zinc <30%
elements but not zinc. 2) α-β brasses : Containing Zinc 30-44%

1) α- Brasses:
 They contain Zn up to 30%.
 α-phase is a soft and ductile phase.
A) Red Brass
 Brasses containing Zn <20% are referred as Red Brasses.

I) Cap Copper
Composition
 Zn- 2 to 5%
 Balance is Cu.
Properties
 Zn is used as a de-oxidizer to avoid formation of copper
oxide.
 Copper oxide is a hard, brittle layer.
 Cap copper is highly ductile.
Applications
 Caps of detonators in ammunition factories, coins, tokens.

II) Gliding Copper

Fig. No. 6.4 Alloys of copper Composition
 Zn- 5 to 15%
6.3.1 Brasses  Balance is Cu.
 Brasses are alloys of Copper and Zinc with small amount Properties
of other alloying elements.  Addition of Zn improves strength.
 It has good ductility and pressing ability.
 Improved corrosion resistance.
Applications
 Coins, needles, emblems, jewellery, bullet envelopers,
condenser tubes.

B) Yellow Brass
 Brasses containing Zn >20% are referred as Yellow
Brasses.

I) Cartridge Brass (70:30 Brass)

Composition
 Zn- 30%
 Balance is Cu.
Properties
 It has high resistance to corrosion.
 It has high ductility and malleability.
 It is a dual phase alloy.
Fig. No. 6.5 Copper-Zinc Equilibrium Diagram  The microstructure in the cast form is dendritic.
 The equilibrium diagram of Copper-Zinc system is as  After cold working and subsequent annealing, its
shown in Fig. No. 6.5. microstructure is observed to be equi-axed grains.
 The phases in Copper-Zinc system are: Applications
1. α : Highly ductile  Cartridge cases, radiator fins, headlight reflectors, lamp
2. β : Increases the tensile strength and lower ductility fixtures, rivets, springs, plumbing accessories etc.

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II) Admiralty Brass (71:28:1 Brass) C) Leaded Brass / Free Cutting Brass (60:38:2 Brass)
Composition Composition
 Zn- 28%  Zn- 38%
 Sn-1%  Pb-up to 2%
 Balance is Cu.  Balance is Cu.
Properties Properties
 It has properties similar to cartridge brass.  Addition of lead improves machinability.
 Addition of Sn improves corrosion resistance.  Lead exists in the alloy in the form of globules (insoluble)
 In applications such as marine environments, excessive which aids in breaking of chips during machining.
de-zincification occurs, i.e. zinc corrodes preferentially  Hence it is also referred as free cutting brass.
leaving behind copper in porous form. Applications
 To overcome this, sometimes Al and small amount of Ar  Machine parts and hardware's.
is also added to Admiralty Brass.
Applications D) High Tensile Brass
 Condenser tubes, heat exchanger in steam power plants. Composition
 It is typically a 60:40 brass (Muntz metal) with alloying
2) α-β Brasses: elements added to it.
 They contain Zn in the range of 30 to 40%.  The alloying elements that are added include Al, Fe, Mn,
 β-phase has more strength. Sn and Ni.
 They are generally hot worked for fabrication work. Properties
 These are cheaper than α-brasses as zinc is cheaper than  The alloying elements improve the tensile strength of
copper. brass.
 They have poor corrosion resistance.  It is further classified as Al-brass, Mn-brass, Sn-brass
(Naval brass) etc.
A) Muntz Metal (60:40 Brass)  It has tensile strength in the range of 40 to 55 kg/mm2 and
Composition elongation of 20 to 30%.
 Zn- 40%  It has high corrosion resistance.
 Balance is Cu. Applications
Properties  Marine pump parts, propeller shafts, gear and valve bodies.
 It becomes single phase above 700°C.
 They are hard and strong as compared to α-brasses. E) Brazing Brass (50:50 Brass)
 At high temperature, β has more ductility and malleability. Composition
 Hence, it is usually hot worked, rolled and extruded.  Zn- 50%
 It has tensile strength in the range of 35 to 40 kg/mm2 and  Balance is Cu.
hardness of 100 to 120 VPN. Properties
Applications  Zn has low melting point - 870°C.
 Pump parts such as valves, condenser tubes, shafts, nuts,  At low temperature, Zn-brass melts and can be used for
bolts, utensils, brazing rods etc. joining of two individual brass alloy components.
 It is a brittle phase and can be easily crushed to powder.
B) Naval Brass (60:39:1 Brass) Applications
Composition  Brazing (Joining) of brasses.
 Zn- 39%
 Sn-1% 6.3.2 Season Cracking of Brasses
 Balance is Cu.  Both α and α-β brasses are prone to a defect phenomenon
Properties known as Season Cracking.
 It has properties similar to Muntz Metal.  It is a defect, wherein spontaneous cracks are observed in
 Addition of Sn improves corrosion resistance. the material.
 It is used in marine environment, hence called Naval  During cold working of brasses, internal/residual stresses
Brass. of tensile nature are induced in the component.
Applications  These stresses can be due to pressing, drawing or some
 Marine hardware, propeller, piston rods, welding rods, nuts other cold working operation.
and bolts, water taps etc.  The localized stressed area becomes anodic with respect
to the other area of the component.

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 It leads to intergranular corrosion resulting in subsequent 𝛽 → 𝛼 + 𝛾2

disintegration and failure of the component.  Commercial Al-Bronzes contain Al in the range of 4 to
 Such a defect phenomenon is called as season cracking. 11%.
 Season cracking can be avoided by annealing the  In addition alloying elements such as Fe, Ni, Si, Zn, Mn
component to remove internal stresses. etc. are added for improvement of certain properties.
 Annealing of brasses is performed at a temperature in  Al-bronzes are also referred as imitation gold due to their
between 280° C and 300° C. lustrous finish, golden colour and fine polishing.

6.3.3 Bronzes Properties of Aluminium

 Bronzes are alloys of Copper and any other major alloying  Its specific weight is only 2.7 gm/cm3 compared to 7.8
element but not Zinc (such as Al, Be, Sn etc). gm/cm3 for steel and 8.8 gm/cm3 for copper.
 Bronzes sometimes also contain zinc but in small  Its electrical conductivity is about 60% of that of copper.
properties to take advantages of its properties.  It has high thermal conductivity.
 The major bronzes that are commercially used and  It has high corrosion resistance because of oxidation and
discussed in this chapter are: formation of protective Al2O3 layer.
1) Al-bronze  It has great affinity for oxygen.
2) Sn-bronze  It is non-magnetic.
3) Be-bronze
4) Si-bronze Al-Bronzes are of two types:
1. Single phase Al-bronze (Contains Al in the range of 4 to
1) Al- Bronze (Aluminium-Bronze) 7.5%).
 Aluminium bronzes are alloys wherein, copper is the base 2. Two phase Al-bronze (Contains Al in the range of 7.5 to
metal and aluminium is the major alloying element. 11%).
 The equilibrium diagram of Cu-Al system is shown in Fig.
No. 6.6. I) Single phase Al-Bronze
Composition
 Al content (4 to 7.5%)
Properties
 The tensile strength is 35 kg/mm2 & % elongation is 50%.
 They have good ductility and malleability because of single
phase structure.
 They can be cold worked by processes such as drawing,
pressing, rolling etc.
 They are available in the form of sheet, tubes and plates.
Applications
 Jewellery, condenser tubes, marine applications, cigarettes
cases, heat exchangers, corrosion resistant vessels,
chemical plants etc.

II) Two phase Al-Bronze

Composition
 Al content (7.5 to 11%)
Properties
 The tensile strength is 45 kg/mm2 & % elongation is 20 to
30%.
 At high temperature it consists of α and β structure.
 They can be hot worked at elevated temperature.
Fig. No. 6.6 Copper-Aluminium Equilibrium Diagram  They have high shrinkage %, hence adequate tolerance is
 The solubility of Al in copper increase with decrease in provided on dies.
temperature. Applications
 The solubility of Aluminium in Copper is 7.4 % at 1040°C  Pump casting parts, valve fittings, propellers, cylinder
and 8.4 % at 565°C heads, gears, forming and drawing dies, bearings, spark
 The eutectoid transformation occurs at 11.8% Al and plug bodies, electrical contacts etc.
565°C.

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2) Sn- Bronze (Tin-Bronze)  Other Alloying Elements in Sn-Bronzes

 Tin bronzes are alloys wherein, Copper is the base metal Lead:
and Tin is the major alloying element.  Addition of 2% lead increases machinability.
 The equilibrium diagram of Cu-Sn system as shown in Fig.  Addition of 8 to 30% lead improves the bearing properties.
No. 6.7.  It also increases fluidity.
Nickel:
 Addition of 1% nickel ensures uniform distribution of lead
globules.
 Higher addition of nickel increases tensile strength.
 Some of the important Tin-Bronzes Alloys:

I) Coinage Bronze
Composition
 Cu- 94%
 Sn-5%
 Zn-1%
Properties
 It is soft and ductile.
 Zinc is added for de-oxidation of the melt.
Applications
 Coins.

II) Gun Metal

Fig. No. 6.7 Copper-Tin Equilibrium Diagram
Composition
 The solubility of Tin in copper varies with the temperature
 Cu- 88%
and is higher in the temperature region of 350°C to 798°C.
 Sn-10%
 The following reactions take place at different
 Zn-2%
temperatures in the equilibrium diagram.
Properties
Table No. 6.1 Transformation Reactions in Cu-Sn
Equilibrium Diagram  Zinc is used as a de-oxidizer.
Reaction Temperature Transformation  Zinc also improves fluidity.
 The solid alloy shows dendrites of α and islands of α + δ
Peritectic Reaction 798°C α+L⟶β
eutectoid.
Eutectoid Reaction of β 586°C β⟶α+γ  It has excellent corrosion resistance.
Eutectoid reaction of δ 350°C δ⟶α+ε Applications
 The Cu-Sn equilibrium diagram shows wide separation of  Gun barrels and ordinance parts, marine castings, gears,
liquidus line from solidus line. bearings, valve bodies etc.
 This result in coring.
 Coring is observed in cast alloys containing more than 8% III) Phosphor Bronze
Sn.  Phosphor bronze is an alloy of Cu, Sn and P.
 Tin has good affinity towards oxygen and forms tin oxide.  Phosphorous is an excellent de-oxidizer.
 Tin oxide is hard and brittle and reduces ductility and  Higher amount of Phosphorous improves mechanical
malleability. properties and castability of the alloy.
 Hence, De-oxidizers (P, Zn etc.) are often added during
melting. A) Wrought Phosphor Bronze
Table No. 6.2 Classification and Application of Sn-Bronzes Composition
% content of  Sn- 2.5 to 8%
Tin (Sn)
Applications  P-0.1 to 0.35%
Up to 8% Sheets, wires, coins, electrical switches  Balance is Cu.
Properties
8-12% Pumps, gears, marine components  It is a single phase α solid solution.
12-20% Bearings, Bushings  It can be cold worked to improve strength and contacts etc.
Applications
20-25% Bells  Wire gauges, springs, wire brushes, electrical contacts etc.

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B) Cast Phosphor Bronze 3) Si- Bronze (Silicon-Bronze)

Composition  Silicon bronzes are alloys wherein, Copper is the base
 Sn- 5 to 13% metal and Silicon is the major alloying element.
 P-0.3 to 1%  The maximum solubility of silicon in copper is 5.3% at
 Balance is Cu. 845°C and decreases to less than 4% at room temperature.
Properties  Si-Bronze composition is Cu-94.5 to 99%; Si- 1 to 5.5%.
 It has better fluidity than wrought phosphor bronze.  These bronzes have high corrosion resistance, tensile
 It also leads to formation of Cu3P, which is brittle. strength and toughness.
 It has better antifriction properties.  They can be further cold worked to improve mechanical
Applications properties.
 Gears, bushings, valves etc.  They can also be hot worked and even be used for casting.
 They are cheaper than Sn-bronzes.
IV) Statuary Bronze
 Other alloying elements that are added to Si-bronzes
Composition
include Mn, Zn, Sn, Pb and Fe.
 Cu- 86%
 Sn-10% Applications
 Zn- 2%  High strength bolts, rivets, springs, pressure vessels,
 Pb- 2%. marine containers, propeller shafts, bells etc.
 Its composition is similar to gun metal but contains about
2% lead. 4) Be- Bronze (Beryllium-Bronze)
Properties  Beryllium Bronzes are alloys wherein, Copper is the base
 It has better fluidity. metal and beryllium is the major alloying element.
 Its colour is brownish-black.  The equilibrium diagram of Cu-Be system is shown in Fig.
 It has high corrosion resistance. No. 6.8.
Applications
 Statues.

V) 80-10-10 Bronze
Composition
 Cu- 80%
 Sn-10%
 Pb- 10%.
Properties
 It has good castability.
 Higher amount of Pb improves bearing properties.
Applications
 They are used for heavy pressure bearings and bushings.

VI) 85-5-5-5 Bronze

Composition
 Cu- 85%
 Sn-5%
Fig. No. 6.8 Copper-Beryllium Equilibrium Diagram
 Zn-5%
 The solubility of Be in Cu is 2.1% at 864°C and decreases
 Pb- 5%.
further to 0.25% at room temperature.
Properties
 This drastic change in solubility gives rise to precipitation
 It has good castability and machinability.
hardening.
 They have better mechanical properties.
 The precipitation cycle consists of heating the alloy at
Applications
around 800°C and quenching in water.
 Bearings, low pressure valves, pipe fittings, small gears
 This is followed by further heating from 300 to 320°C for
and ornamental fixtures.
a couple of hours to accelerate ageing treatment.
 Be-bronzes have good corrosion and fatigue resistance.
 They have high resilience and good bearing properties.

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 They have low hysteresis and non-sparking  It is the second most used non-ferrous metal. In pure form
characteristics. i.e. 99.9% pure aluminium does not have sufficient
strength and hardness. It is very soft and ductile.
Applications  The important properties of Aluminium are:
 Springs, diaphragms, flexible bellows, gears, bearings,
1. It is ductile and malleable.
electrical appliances, non-sparking tools etc.
2. Its specific weight is only 2.7 gm/cm3 compared to 7.8
Table No. 6.3 Comparison between Brasses and Bronze gm/cm3 for steel and 8.8 gm/cm3 for copper.
Brass Bronze 3. Its electrical conductivity is about 60% of that of copper.
Brasses are alloys of Copper Bronzes are alloys of Copper 4. It has high thermal conductivity.
and zinc with small amount and any other major alloying 5. It has high corrosion resistance because of oxidation and
of other alloying elements. element but not Zinc (Such formation of protective Al2O3 layer.
as Al, Be, Sn etc.) 6. It has great affinity for oxygen.
Brasses are classified on the Bronzes are classified on the 7. It is non-magnetic.
basis of the phases in basis of alloying element  Aluminium can be easily alloyed with elements such as Si,
Copper-Zinc system such as such as Al-Bronze, Sn- Mg, Cu, Ni, Zn, Mn, Ti etc.
α-Brass and α-β Brass. Bronze, Be-Bronze, Si-  Because of all this properties and considering all these
Bronze. properties, Aluminium is mainly used for electrical
Brass appears more Bronze appears brownish conductors, cooking utensils, food containers, and
greenish, bluish in colour. golden in colour. transportation industry, chemical and automobile industry.
Not expensive than bronze Expensive  Aluminium alloys are designated by LM (i.e. Light Metal)
Brass is less strong, harder Bronze is much stringer, series.
and corrosion resistance than harder and corrosion
bronze. resistant than brass. 6.4.1 Aluminium-Copper Alloys (Al-Cu)
Brass machines and polishes Bronze is difficult to  Aluminium is the base metal and copper is the major
much easily. machine and polish. alloying element.
Brass melts at lower Bronze melts at higher
temperature. temperature. I) LM 11
Composition
 Al-95.5%
6.4 Aluminium and its Alloys (Al)  Cu-4.5%.
 Aluminium is one of the most widely used non-ferrous Properties
metals.  It is precipitation Hardenable alloy.
 Consumption of Al and Al alloys as shown in Fig. No. 6.9.  It produces good strength after precipitation hardening.
 It has good mechanical and shock resisting properties.
 It is susceptible to hot tearing.
Applications
 Castings for aircrafts and high stressed parts.

II) Duralumin
Composition
 Al-94.5%
 Cu-4.5%
 Mg-0.5%
 Mn-0.5%
Properties
 It produces good strength after precipitation hardening.
 It has good mechanical and shock resisting properties.
 It also has good corrosion resistance.
Applications
 Aircraft industry.

Fig. No. 6.9 Different use of Al and Al alloys III) LM 14 (Y-alloy)

Composition

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 Al-92.5%  The eutectic transformation from liquid to solid state takes

 Cu-4% place at a constant temperature of 577°C.
 Mg-1.5% Liquid ⟶ Solid1 + Solid2
 Ni-2%  The eutectic transformation occurs at alloy composition of
Properties 12.2% silicon.
 It has excellent ability to retain strength at elevated
temperature. I) LM 6
 It has low thermal expansion. Composition
 It has high resistance to corrosion.  Al-88%
 It can be easily cast and rolled.  Si-12%.
Applications Properties
 Pistons, Cylinder heads of I.C. Engines.  It has excellent fluidity due to presence of Silicon.
 It has high corrosion resistance.
IV) RR 350 (Hinduminium)  It has less shrinkage during solidification.
Composition Applications
 Al-92%  Intricate castings such as water cooled manifolds and
 Cu-5% jackets, motor housings, pump castings, etc.
 Ni-1.5%
 Small amount of Mn, Ti, Sb, Co and Zr. II) LM 13
Properties Composition
 It has excellent ability to retain strength at elevated  Al-83.4%
temperature.  Si-12%
 It is superior to Y-alloy in regards to creep resistance.  Ni-2.5%
Applications  Cu-0.9%
 Aircraft engines, high temperature.  Mg-1.2%.

6.4.2 Aluminium-Silicon Alloys (Al-Si)

 Aluminium is the base metal and silicon is the major Properties
alloying element.  It is a precipitation Hardenable alloy.
 The phase transformation diagram of aluminium and  It has excellent ability to retain strength at elevated
silicon alloy is shown in Fig. No. 6.10. temperature.
 It has low coefficient of thermal expansion.
 It has good bearing properties.
 It can be easily forged.
Applications
 Forged pistons and other automobile parts.

6.4.3 Aluminium-Magnesium Alloys (Al-Mg)

 Aluminium is the base metal and Magnesium is the major
alloying element.

I) LM 5 (Magnalium)
Composition
 Al-94.5%
 Mg-5.0%
 Mn-0.5%.
Properties
 It has high resistance to corrosion.
 It has good machinability and weldability.
 It can be easily anodized and gives better finish.
Applications
 Marine applications.

Fig. No. 6.10 Aluminium-Silicon Equilibrium Diagram

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II) LM 10 I) Dura Nickel

Composition Composition
 Al-90%  Ni-94%
 Mg-10%.  Al-4.5%
Properties  Small amount of C, Mn, Fe, S, Si, Cu, Ti etc.
 It has poor castability because the molten metal gets easily Properties
oxidized and picks up gas on standing.  It is age Hardenable alloy.
 Hence, small amount of beryllium is added to reduce  It can also be cold-worked to increase strength.
oxidation.  It has good corrosion resistance.
 Sometimes degassing is also done to remove trapped Applications
gases.  Diaphragms, bellows, snap-switch blades, fish hooks,
Applications jewellery and optical frames.
 Aircraft and automobile components, dairy equipment,
architectural work etc. II) Perma Nickel
Composition
6.5 Nickel and its Alloys (Ni)  Ni-98.5%
 World demand for nickel is growing constantly, at an  Small amount of C, Mn, Fe, S, Si, Cu, Ti, Mg etc.
average rate of 5% per annum. Properties
 The consumption of pure nickel is as shown in Fig. No.  It is age Hardenable alloy.
6.11. Which clearly shows that the majority of pure nickel  It also has high corrosion resistance and good mechanical
metal (66%) is consumed for making stainless steel and properties.
alloys.  It has better electrical and thermal conductivity.
 While only 10% and 5% is consumed in chemical industry  It has better magnetic properties than Dura-Nickel.
and tooling. Applications
 There for nickel alloys has great importance in engineering  Similar to Dura-Nickel alloy where higher electrical
application. conductivity and better magnetic properties are required.

III) Hastelloys D
Composition
 Ni-87%
 Si-10%
 Cu-3%.
Properties
 It has good casting properties.
 It has better mechanical strength and toughness.
 Due to its high hardness, it is difficult to machine.
 It has high corrosion resistance even at elevated
temperatures.
Applications
 Evaporators, reaction vessels, pipelines for chemical
industry.

Fig. No. 6.11 The total consumption of Nickel IV) Monel

Composition
 The important properties of Nickel are:  Ni-64%
1. It has FCC structure.  Cu-30%
2. It has good ductility and malleability.  Si-2%
3. It exhibits good resistance to corrosion and oxidation.  Small amount of other elements.
4. It has fairly good electrical conductivity. Properties
5. It has better formability.  It has good casting properties.
6. It is chemically inert hence used for electroplating.  It has high corrosion resistance.
7. It is highly used in production of stainless steel, nickel Applications
alloys, permanent magnets etc.  Marine casting parts, valve seats, pump liners etc.

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V) Invar Applications
Composition  Heaters, furnace parts, carburizing containers,
 Ni-36% thermocouple covering tubes, exhaust manifolds of aero
 Fe-64% engines, mufflers etc.
Properties
 Invar means invariable. IX) Inconel X
 It has the lowest coefficient of thermal expansion. Composition
 It has good resistance to corrosion.  Ni-73.5%
Applications  Cr-15%
 Length standards, measuring tapes and instruments such as  Fe-8%
scales, Vernier's etc.  Ti-2.5%
 Variable condensers, tuning forks, special springs etc.  Al-1%
Properties
VI) Elinvar  It is age Hardenable alloy.
Composition  It can retain mechanical strength and toughness even at
 Ni-36% elevated temperatures of up to 800°C.
 Cr-12% Applications
 Fe-52%  High temperature applications such as gas turbines,
Properties superchargers, jet propulsion parts.
 The modulus of elasticity remains fairly constant for a wide
range of temperature. X) Permalloys
 It has negligible elastic changes with respect to Composition
temperature.  Ni-78%
Applications  Fe-22%.
 Hair springs, balance wheel in watches, other springs used Properties
in precision instruments.  It has high magnetic permeability.
 It has low hysteresis losses, and low electrical resistivity.
VII) Ni-Cr-Fe-Alloys Applications
Composition  Used for apparatus that work on magnetic waves such as
 Ni-60%, Cr-16%, Fe-24% radio, transmitters, communication circuits etc.
 Ni-35%, Cr-20%, Fe-45%
Properties XI) Alnico
 These alloys have high resistance to oxidation and to the Composition
action of carburizing gases.  Ni-14 to 28%
 They have high thermal conductivity and emissivity.  Al-8 to 12%
 They have high melting point because of presence of Fe  Co-5 to 35%
and Cr.  Fe-25 to 73%.
Applications Properties
 Electrical heating elements for toasters, hair driers, hot  It has excellent magnetic properties.
water heaters, rheostats etc. Applications
 Heat treating equipment’s, furnace parts, carburising and  Permanent magnets in motors, generators, speakers,
nitriding containers etc. microphones etc.

VIII) Inconel 6.6 Cobalt and its Alloys (Co)

Composition  Cobalt is a silvery white metal with a faint bluish touch.
 Ni-77%  It is similar to nickel in appearance and mechanical
 Cr-15% properties.
 Fe-8%  Its chemical properties are combination of nickel and iron.
Properties  Cobalt is main used as an alloying element in nickel base
 It has good corrosion and oxidation resistance. alloys as cobalt base alloys. Apart from this cobalt is also
 It maintains good strength at elevated temperatures. an important ingredients in other materials like paint
 It can withstand repeated heating and cooling cycles. pigment, cemented carbide tool steel, magnetic materials
etc.

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 Below 421°C cobalt has HCP structure and above 421°C This alloy is mainly used for jet engine blades.
it has FCC structure.
Applications of Cobalt Alloys
6.6.1 Cobalt Alloys  Cobalt alloys are used as high temperature alloys.
 Stellite alloys has composition of 26-33% Cr, 5-14% W, 1-  They can be used as permanent magnets.
2.5% C and remaining cobalt.  They are used in components of jet aircraft engine like gas
 These alloys have high resistance to corrosion. Also they turbines, super chargers, turbines blades, nozzles etc.
have high reflectivity and high resistance to abrasion.  They are used in nuclear reactors and wear resistance
Hence, they are also known as hard facing alloys. components in nuclear submarines.
 The Co-Cr based alloys for dental and surgical applications  Also used in dies, cutting tools, search light reflectors,
are not attacked by the body fluids and hence do not motor cases etc.
irritation of the tissue. Thus Vitallium alloys used as bone
replacements. Advantages
 The composition of vitallium alloys is 64% Co, 30% Cr  They have high melting point, due to which very suitable
and 5% Mo. for making jet turbine blades.
 Cobalt reduces hardenability of steel. When dissolved in  Good hot corrosion resistance.
ferrite cobalt provides resistant to softening at high  Better weldability and thermal fatigue resistance.
temperatures.  Good wear resistance.
 The high melting point of cobalt (1121°C) provides high
damping characteristics useful for alloys subjected to Disadvantages
vibration like high pressure and high temperature steam  They have low strength.
turbines.  Lower ductility and fracture toughness.
 Cobalt alloys can be cast, forged, rolled, extruded, drawn,
welded, brazed or it can be shaped by powder metallurgy. 6.7 Titanium and its Alloys (Ti)
 Cobalt alloys are commercially available as ingot, wire,  Titanium is a strong, light weight and corrosion resistant
sheet, bar, tube, rod, plate, foil, powder etc. metal.
 Some typical Co-based alloys and their composition:  Titanium ores are initially reduced to titanium in a furnace
and then converted into Ticl4 in chlorine atmosphere. This
I) Stellite 21 compound is reduced with magnesium to produce titanium
Composition sponge.
 Ni- 2%  Titanium has two allotropic forms i.e. HCP alpha phase
 Cr- 28% and BCC beta phase. The transformation occurs at 885°C
 n- 5.5% from alpha to beta phase. To affect the transformation
 C- 0.3% alloying elements are added.
 Balance Co.  The alloying elements that raises this transformation
This alloy has a good wear resistance. temperature and stabilises the alpha phase are known as
alpha stabilisers.
II) Stellite 31  The alloying elements that lowers the transformation
Composition temperature and stabilises the beta phase are known as beta
 Ni- 10% stabilisers.
 Cr- 20%
 W- 15% 6.7.1 Major characteristics and properties of Titanium
 C- 0.1%  They are 40% lighter than the steel and 60% heavier than
 Balance Co. the aluminium.
 Titanium has good corrosion resistance.
III) Mar M 302  Melting point of titanium is higher than the iron.
Composition  It has low thermal conductivity.
 Cr- 21.5%  Its thermal coefficient of expansion is low.
 W- 10%  Its electrical resistivity is also high.
 Ta- 9%
 Zr- 0.05% 6.7.2 Titanium Alloys
 C- 0.85%  According to the phases present the titanium alloys are
 Balance Co classified as follows:

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I) Alpha Alloys (Rich in alpha stabilizers) 6.8.1 Properties of Tin

Composition  Tin is a non-toxic, white, soft and pliable metal.
 Ti- 92%  It has density of 7.30 gm/cm3, melts at 231.9°C and its
 Al- 5% corrosion resistance is high.
 Sn- 2.5%  Tin shows an allotropic transformation at about 13°C
 Small amount of zirconium, vanadium and columbium. when white tin changes to brittle gray tin.
Properties  Tin alloys with copper, antimony, cadmium and silver and
 It has excellent weldability and good strength at high its hardness increases.
temperatures.
 It has good oxidation resistance. 6.8.2 Applications of Tin
 It has good formability.  Large quantity of tin is used for the coating on other metals
Applications like iron, steel, copper, brass etc.
 It is used in aircraft engine compressor blades and ducts,  Steel sheets coated with tin are used in the manufacturing
steam turbine blades etc. of tin cans.
 It is used in cold working processes like rolling, extrusion
II) Beta Alloys (Rich in beta stabilizers) and spinning.
Composition  It is also used as foil for wrapping food products and for
 Ti- 73% the manufacturing of collapsible tubes.
 Al- 3%
 V- 13% 6.8.3 Tin Alloys
 Cr- 11% I) Copper-Tin Alloys (Cu-Sn)
Properties  Copper-tin alloys (Bronzes) or phosphor bronze containing
 These alloys are less strong, easier to work and unstable at 8 to 12% tin with small additions of phosphorus is used for
high temperature. springs, condenser tubes, bearings etc.
 It responds to heat treatment.  The gun metals, tin-bronze casting alloys with 1 to 6 % zinc
 They have low toughness and fatigue strength. are used for valves and fittings for water and steam lines.
 They become brittle at temperature below - 40°C.  Babbit bearing metals are basically tin base alloys.
Applications
 It is used in high strength fasteners, rivets, sheet metal parts II) Aluminium-Tin Alloys (Al-Sn)
and tubing for aerospace.  Al-Sn alloys possesses high fatigue strength and hence it
can carry fluctuating loads.
III) Alpha-Beta Alloys  The 6% Tin-Aluminium alloys can be bonded to steel by
Composition rolling.
 Ti- 90%
 Al- 6% III) Pewter or Britannia Metal
 V- 4%  It is a tarnish resistant alloy containing 7% antimony, 2%
Properties copper and remaining lead.
 It has high formability.  It is used for domestic applications like trays, plates, bowls
etc. It is also used for decorative applications like vases,
 It has low toughness and it is difficult to weld.
candle sticks, book ends etc.
 Due to its high hardness, it is difficult to machine.
 It has good impact and fatigue strength.
Applications 6.9 Lead and its Alloys (Pb)
 It is used in rocket motor cases, blades and discs of aircraft  Lead is the oldest of the commonly used metals and the
turbines and compressors, structural forgings and fasteners, softest of the heavy metals.
orthopaedic implants etc.  In the nature, lead exist in the form of sulphide or oxide.
 When it is cast or cut, it is lustrous silvery colour initially,
6.8 Tin and its Alloys (Sn) but after some time, the surface turns a dull bluish grey
because of oxidation.
 Tin is normally white, soft and malleable metal.
 It is very much similar in properties to lead.
6.9.1 Properties of Lead
 Tin can available as granulated, fine powder, sheet, foil
 Lead has a FCC crystal structure.
and wire.
 It has good ductility and malleability.

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 It is poisonous and should not be brought into contact with  It solidifies quickly without passing through a weak pasty
food items. region.
 It is very soft and it has low melting point (327°C) with  A solder containing between 20% to 40% Sn starts
high density. solidification in the temperature range of 280°C to 240°C
 It has high coefficient of thermal expansion and low and hence remains pasty for long time.
electrical conductivity.  This helps the plumber wiping the joints in lead pipes,
 It can be easily soldered, welded and cast. cable sheaths etc. Hence any solder within this composition
 It has high resistance to corrosion against most acids. range is known as Plumber’s Solder.
 Its X-rays and γ-rays absorbing power is high.  Generally this solder contains 33% Sn and 67% Pb.
 It has low strength.  In a lead-tin alloy if the amount of tin is between 10 to 25%
 It also possesses good lubricating properties. and it is known as Terne Metal. It is commonly used to coat
the steel sheets for roofing and automotive fuel tanks,
6.9.2 Applications of Lead containers etc.
 It is commonly used in the manufacturing of storage
batteries. 6.10 Bearing Materials
 In case of high grade petrol tetraethyl lead is used as an  Bearing materials are anti-friction materials used as
antiknocking ingredient. rotating shaft holders or supporters.
 Used in tank linings for corrosion protection.  These shaft holders or supporters transmit loads to a shaft
 It is used in pipe and drainage fittings. rotating relative to the bearing.
 It is used as compounds in paints and sheathing  Bearings are required in various applications such as
(Protection) of electric cable. machinery, engines, reciprocating parts etc.
 It is used as an alloying element to improve the  Bearing are classified as:
machinability of bronzes, brasses and free machining 1. Sliding contact bearings
steels. 2. Rolling contact bearings
 It is used as a coating on steel wires, used as a joining 3. Thrust bearings
material for cast iron pipes and used in the manufacturing
of alloys like babbits, solders etc. 6.10.1 Requirements of Bearings
 It is also used for shielding against X-rays and γ-rays.  A properly lubricated bearing should ensure a film of oil in
between the moving parts, under all working conditions.
6.9.3 Lead Alloys  However, during starting, stopping and serve running
 The most common alloying elements with lead are conditions, it is difficult to maintain the oil film.
antimony (Sb) and Tin (Sn).  This results in metal-to-metal contact causing wear and
 Antimony is added to lead to increase the recrystallization subsequent seizure of the bearing.
temperature and to increase the hardness and strength.  The following properties are essential for a good bearing:
 Tin is added to lead to reduce the melting point of the 1. The bearing and rotating parts should have the least
material and it also increases the mechanical properties of friction to reduce power loss in transmission.
the lead. 2. The bearing material should be hard and wear
resistance for longer life.
I) Lead-Antimony (Pb-Sb) Alloy 3. It should have adequate mechanical properties and
 The Pb-Sb phase diagram is of eutectic type with eutectic load bearing ability at ambient and elevated
composition of 11.2% Sb and eutectic temperature of temperatures.
251.2°C. 4. It should have enough plasticity and deformability to
 The commercial alloys containing 1 to 12% antimony are sustain large deflection and misalignment of the shaft.
used for storage battery plates, collapsible tubes, building 5. It should possess high fatigue strength.
construction, cable sheathing, drain pipes etc. 6. It should have good resistance to corrosion, galling
and seizing.
II) Lead-Tin (Pb-Sn) Alloy 7. It should possess better thermal conductivity to
 In case of Pb-Sn equilibrium diagram the eutectic point is dissipate the frictional heat generated during working.
at 61.9% Sn and 183°C temperature. 8. It should be able to retain oil on the bearing surface.
 Lead-tin alloys have good flow characteristic hence they 9. It should have good machinability.
are commonly used as solders. 10. It should be cheap and easy to service.
 A solder of Pb-Sn alloy of eutectic composition is known
as Timman’s Solder or Quick Solder (62% Sn).

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6.10.2 Bearings Alloys Applications

I) White Metal Alloys (Babbitt’s)  Bearings in automotive and aerospace applications.
a) Lead-Based Babbitt’s
Composition III) Tin-Bronzes
 Pb- 80% Composition
 Sb- 10% Gun Metal
 Sn- 10%  Cu- 88%
 Small amounts of Cu, Cd and As.  Sn- 10%
Properties  Zn- 2%
 During solidification, Sn-Sb combines early and forms Phosphor Bronze
hard cuboids.  Cu- 75 to 80%
 These hard cuboids float on the surface of the material,  Sn- 10 to 15%
while the internal microstructure consists of soft matrix of  P- 10%
eutectic. Properties
 This makes the bearing hard at the surface and soft from  Zinc and phosphorus added here to the function of
within. deoxidizers.
 They have high strength and toughness.
b) Tin-Based Babbitt’s  They have good resistance to corrosion.
Composition  They have good bearing properties.
 Sn- 90% Applications
 Sb- 5%  Bearings for heavy load applications where lubrication
 Cu- 5% availability is scarce.
 Small amount of Pb and As.
Properties IV) Silver Bearings
 To reduce formation of hard cuboids and it’s floating on Composition
the surface, rapid cooling is usually done.  Steel bearing- plated with Silver, Followed by coating of
 Sometimes, copper is also added to avoid / reduce Lead and then Iridium.
formation of hard cuboids. Properties
 Copper will combine with Sn to form hard needles of Cu-  Lead reduces risk of seizure.
Sn and reduce formation of Sn-Sb.  Iridium protects Lead against any acidic actions of oil.
 This ensures uniform distribution of cuboids within the  They are used for heavy load conditions.
material matrix.  They have high fatigue strength.
 Tin-based Babbitt’s have better corrosion and wear  They have high corrosion resistance and excellent ant
resistance. seizing properties.
 Lead is a soft material and reduces the load carrying Applications
capacity of the bearing.  Bearings for aircraft industry.
Applications
 Bearings of I.C. engines, lathe machine, milling machine, V) Aluminium Alloys
electric motors etc. Composition
 It contains alloying elements such as Sn, Cu, Ni, Fe, Si and
II) Copper-Lead Alloys Mn.
Composition Properties
 Pb- 20 to 40%  These are used for high loads and high speeds.
 Cu- 60 to 80%  They have high strength and toughness.
 Small amount of Sn.  They have high resistance to corrosion.
Properties  They possess high fatigue strength and anti-seizure
 Lead is insoluble in Copper. property.
 It is a soft material and gets uniformly distributed in the Applications
hard matrix of Copper.  Bearings required for high loads and high speeds such as
 Tin added in the bearing prevents acidic attack of oil on connecting rods and I.C. engines.
Lead.
 These bearings are manufactured by castings or powder VI) Porous Self-Lubricating Bearings
metallurgy. Composition

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Copper-Based Bearing the flux should remain in the liquid form at the soldering
 Cu- 90% temperature.
 Sn- 10%  The filler metals used in soldering are known as solders
 Additional amount of graphite. which are the alloys of low melting point metals.
Iron-Based Bearing  Due to the flow characteristics of lead and tin alloys, they
 Fe- 96% are widely used as solders.
 C- 4%  It solidifies quickly without passing through a weak pasty
Properties region. It is used for joining T.V, radio and electrical
 These are manufactured by Powder Metallurgy Process. instrument wires.
 They have porosity as high as 40 to 50%.  A solder which contains 20 to 40% tin starts solidifying in
 They are impregnated with oil. the temperature range of 280 to 240°C. Hence, it remains
 When the shaft is not rotating, the oil gets filled in the pores pasty for a long time.
of the bearing.  This wider solidification range helps the plumber for
 As temperature increases, due to capillary action oil comes wiping the joints in lead pipes hence this solder is called as
out of the pores and forms a thin layer between the rotating plumber’s solder.
shaft and the bearing.  Generally, the plumber solder contains 67% lead and 33%
 They do not require any external lubrication and they avoid tin. A solder which contains 58% lead and 42% tin is
wastage/ replacement of oil. known as electrician’s solder.
Applications  A lead-tin alloy that contains tin between 10 to 25% is
 Food processing industries, paper and textiles industries. known as Terne metal and it is used to coat steel sheets for
automotive components and roofing.
VII) Non-Metallic Bearings  There are two types’ solders i.e. soft solders and hard
Composition solders.
 Teflon, Nylon, Graphite, Molybdenum Disulphide.  Soft solders are used in sheet metal work for joining parts
Properties which are not exposed to high temperature action and not
 They are dry and anti-corrosive material based bearings. subjected to excessive loads and forces. It is used for
 These materials are used to avoid contamination of joining wires and small parts.
surrounding parts.  Hard solders melt at high temperatures and they are
 They are used in areas which are difficult to access / stronger than those used in soft solders. Silver soldering is
service. a hard soldering method and lead or cadmium or tin alloyed
with silver is used as a hard solder.
 They cannot take heavy load.
Applications
 Food processing industries, paper and textiles industries. 6.12 Brazing Alloys
 Brazing is the joining process of metals or alloys by using
6.11 Soldering Alloys another metal or alloy that has a melting point above 500°C
and below the melting point of the metals to be joined.
 Soldering is the joining process of metals or alloys by using
 In brazing process also, the molten filler metal is drawn
another metal or alloy that has a melting point below 500°C
into the joint by a capillary action.
and below the melting point of the metals to be joined.
 Brazed joints are stronger that the soldered joints.
 In this process, the molten filler metal is drawn into the
joint by a capillary action.  Fluxes are used in brazing operation and they have the
same function as they have in soldering and welding.
 In case of soldering process, rosin and rosin plus alcohol
are commonly used as fluxes for joining of electrical wires.  Generally, the fluxes used are combinations of boric acid,
These fluxes contain acid hence they are likely to corrode chlorides, fluorides and tetraborates with other wetting
the joint. agents.
 For this drawback the components are cleaned after  A commonly used flux for ferrous materials is combination
soldering process. Fluxes like ammonium chloride and zinc of borax (75%) and boric acid (25%).
chloride are generally used because of their quick action to  For brazing of stainless steel, aluminium bronze, silicon
produce good joints. bronze etc. alkaline bifluorides are used. Also for brazing
 For soldering of non-electrical wires or parts these fluxes of tungsten to copper a special flux that contains sodium
are commonly used. cyanide is used.
 Fluxes can be available in liquid, paste, powder or in the  These fluxes are corrosive in the presence of moisture at
form of core in the solder metal. But, it is necessary that room temperature hence the joint should be cleaned after
brazing.

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 The brazing process consists of applying a proper flux at This is a high strength aluminium alloy and contains about 4%
the joint, heating the joint to the liquidus temperature of the Copper, 2% Nickel and 1.5% Magnesium.
filler metal and applying the filler material that flows into It has an excellent ability to retain strength at elevated
the gap by capillary action. temperatures with fairly good corrosion resistance.
 The filler material is available in various forms like wires, It can be easily cast and rolled
rod, sheet, powder etc. Application: Pistons and cylinder heads of diesel and high duty
 The filler metals used in brazing are as follows: petrol engines.
4. Which are the elements in a Tin Bronze Alloy? What is the
I) Aluminium-Silicon (Al-Si) need of Deoxidizing Tin Bronze? Which are the common
 It is a general purpose brazing filler metal used where deoxidizers used for the purpose of deoxidizing tin bronze.
controlled flow is required. (Refer Section 6.3.3 (2))
5. State any three desirable properties that need to be possessed
II) Magnesium (Mg) by a good Bearing Material. What is a bimetal bearing? (Refer
 It is used for brazing of magnesium alloys. Section 6.10.1)
6. State any four properties that makes Aluminium alloy
III) Copper and Copper-Zinc (Cu and Cu-Zn) eligible to be used as a material for connecting rods and main
 It is used in all brazing processes on steel, nickel base bearing in automobiles. (Refer Section 6.4)
alloys giving a better colour match.
May 2019 Examination
IV) Gold
 It is used for joining parts in electron tube assemblies
1. Differentiate between ferrous and Non-ferrous metals alloy.
where volatile components are undesirable.
Give examples of each. (Refer Section 6.2)
2. Why is it not advisable to repair by welding a structure made
V) Silver-Brazing Alloys
of non-heat treatable Aluminium alloy? (Refer Section 6.4)
 They are used for joining most ferrous and non-ferrous
3. What is season cracking of brasses? How can it be avoided?
metals except aluminium and magnesium using all
(Refer Section 6.3.2)
methods of heating.
4. Which alloy is used for soldering of electronic components?
Why? (Refer Section 6.11)
University Question
November 2018 Examination
November 2019 Examination
1. State merits and demerits of Non-Ferrous metals over ferrous
1. Which alloying element is used in Free-Cutting Copper and
metals. (Refer Section 6.2)
why is it called so? State the application of free cutting copper.
2. Why are Aluminium and Copper metals known as corrosion
Ans:
resistant? (Refer Section 6.3 and 6.4)
Copper containing about 0.6% Tellurium is called free-cutting
3. What is Stellite 21 and Stellite 31? What are their advantages
copper.
and disadvantages? (Refer Section 6.6.1)
It’s called so as it has an excellent machinability.
Applications: Bolts, studs, welding tips and electrical parts like
contact pins, switch gears, relays and precision electrical November 2017 Examination
equipment’s.
2. What is equivalent Zinc of Brass? Give an example and
1. Give classification of copper alloys. Differentiate between
explain its significance and usefulness.
brass and bronze. (Refer Section 6.3 and Table No. 6.3)
Ans:
2. Write a short note on bearing materials. (Refer Section 6.10)
Most of the elements which are added to brasses to develop high
3. State true or false and Justify:
strength affect the microstructure in the same way as increasing
a) Aluminium alloys are widely used in aeronautic and
the zinc content.
automobile application. (Refer Section 6.4)
Example
b) Tin Bronze show pronounced coring. (Refer Section 6.3.3
1% Si equivalent Zinc 10%, Zinc 6%, 1% Al.
(2))
The concept helps in evaluating the amount of α and β phases.
c) 60/40 brass can be easily cold worked. (Refer Section 6.3.1)
3. State the composition of Y-alloy. State its properties and
4. Name the base metal for the following alloys:
application.
a) Duralumin (Refer Section 6.4.1)
Ans:
b) Gun Metal (Refer Section 6.3.3)

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c) Beryllium Bronze (Refer Section 6.3.3)

d) Monel (Refer Section 6.5)

May 2017 Examination

1. Cartridge brass is easily cold worked but Muntz metal cannot
be cold worked. Explain why it is so. (Refer Section 6.3.1)
2. State any two important properties of copper or copper alloys
and explain how that is used in an application. (Refer Section
6.3)
3. Why is Al-12% Si (LM 6) alloy a very popular casting
material for automotive applications? (Refer Section 6.4.2)
4. Write short note on Nickel and Nickel alloys. (Refer Section
6.5)
5. Explain classification of Aluminium alloys. (Refer Section
6.4)

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