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Introduction to Material Science &


Course Contents
1.1 Introduction.
1.2 Engineering Requirements
from Materials.
1.3 Classification of Engineering
1.4 Factors that Govern Material
Selection for Engineering
1.5 Structure of Metals.
1.6 Structure Property Corelation.
1.7 Micro- And Macro-

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1. Introduction to Material Science & Metallurgy

1.1 Introduction
Material Science deals with the physical and chemical internal structure of materials and
correlates the structure with properties. Material Engineering applies knowledge of material
Science to manipulate the properties.
Chemical elements cover a wide range of metals, metalloids and non-metals. Metals have
definite crystal structure, relatively high thermal and electrical conductivity and good
reflectivity. They can be plastically deformed to desired shape (e.g. Fe-iron, Cu- Copper, Al-
Aluminium etc.). Metalloids exhibit some properties like metal and other like non-metals
They show some conductivity but almost no ability to be deformed plastically, (e.g. B, Si, C)
Non-metals include elements like F, CI, Br, S and inert gases.

Metallurgy is the science and technology of metals. Right from extraction of metal form ore,
refining of metals, study and formation of alloys and relationship of structure and properties
of metals.
Metallurgy is classified into
(i) Extractive metallurgy
(ii) Physical metallurgy
(iii) Mechanical metallurgy

Extractive metallurgy: Extractive Metallurgy deals with extraction of metals from their ores
(oxides, sulphides, chlorides, etc) and refining them.
Physical metallurgy: This area of metallurgy is the study of structure property relationship
of metals, optimization of properties by manipulating the structure, alloying of metals, heat
treatments of metals etc. Study of microstructures of metals by different microscopes are
also covered under this stream of Metallurgy.
Mechanical metallurgy: Mechanical working of metals, testing of metals for various
mechanical properties, design of components, fracture/failure study and selection of
materials is covered under this stream of Metallurgy. It is also customary to classify
metallurgy into ferrous metallurgy and Non-ferrous Metallurgy. Ferrous Metallurgy is
Metallurgy of iron, steels and cast irons. Non-ferrous metallurgy deals with metals and
alloys other than Iron and Iron alloys. Copper, Aluminium, Magnesium, Zinc, Tin, Lead and
their alloys are studied in non-ferrous metallurgy.
1.2 Engineering Requirements from Materials
(a) Formability / Fabrication requirement: Ability of material to deform to desired size and
shape plastically and ability to get joined.
(b) Service Requirement / Properties: Enough strength, Abrasion resistance, Anti-wear
property, Resistance to corrosion etc.
(c) Economic Requirement: It should be cost effective i.e. economically viable.
1. Introduction to Material Science & Metallurgy

1.3 Classification of Engineering Materials

Engineering Materials

Metals Polymers Ceramics Composites


Ferrous Non - Ferrous

Metal Metal

Elastomers Plastics

Around 75 % of engineering materials fall under this category.
(1) Ferrous metals
(2) Non ferrous metals
(1) Ferrous metals
Iron and Iron based alloys are called ferrous metals and alloys.
They are pig iron, wrought iron, plain carbon steels, alloy steels, cast irons and alloy cast
(2) Non ferrous metals
Any other metal than iron and their alloys fail under this group, e.g. Cu, Ai, Ni etc and
their alloys, brasses, bronzes etc.

Polymers and their Classification

Nowadays polymers have become substitute to steels and other metals for various
engineering applications.
They have good mouldability, corrosion resistance, surface finish, low density and low
co-efficient of friction.
Natural polymers include-rubber, cotton, leather, wool, silk, wood, starch, cellulose etc.

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1. Introduction to Material Science & Metallurgy

Synthetic polymers include-polyvinyl chloride (PVC), polystyrene, polyethyl

methacrylate etc..
Synthetic polymers are formed by three mechanisms.
Polymers are classified on the basis of their response to the elevated temperature into,
(a) Thermoplastic polymers (b) Thermosetting polymers
(a) Thermoplastic polymers
They soften upon heating and harden upon cooling which is a reversible process.
They are mostly linear and have simple branching.
Thermoplastic polymers are soft and ductile.
They can be remolded several times, e.g. polyvinyl chloride, polystyrene.
(b) Thermosetting polymers
They soften during first heating cycle and become permanently hard upon cooling. They
cannot be softened again by reheating.
They are harder, stronger and more brittle as compared to thermoplastic polymers.
They are formed by extensive crosslinking e.g. epoxies, phenolic resins, bakelite etc.

Rubber also called as elastomer is hydrocarbon polymeric material. It tolerates large and
reversible elastic deformations.
Rubbers are non-crystalline, non-conducting and show good corrosion resistance and
resistance to chemical environment. The most important characteristic of it is its high
energy storing capacity.
Natural rubber
Natural rubber is processed from rubber latex obtained form tropical trees.
It is tough, elastic in nature and has good resistance to tear.
It softens upon heating and hardens at 5C.
Ceramics and Refractories
Oxides, nitrides, carbides, silicates, borides of various metals make ceramics. Rock and
clay are natural ceramics. Sometimes ceramics may contain compounds of non-metallic
elements such as SiC, BaTiOa.
Ceramics are inorganic, nonmetallic solids.
Important characteristics of ceramics are :
(a) Abrasion resistance.
(b) Corrosion resistance
(c) Resistance to high temperatures.
(d) Creep resisting property
(e) Hardness and brittleness
(f) Insulating property.
Examples of ceramic materials are sand, brick, cement, concrete, silicon carbide,
tungsten carbide, boron nitride.
1. Introduction to Material Science & Metallurgy

Refractories are the ceramic compounds used for high temperature applications. They
have high melting point, high fusion temperature, high dimensional stability at elevated
Refractoriness of the material is the ability to withstand high temperatures without
appreciable deformation or softening.
Applications of refractory materials include furnace walls, furnace hearth linings, bricks
supporting heating coils, linings of nuclear reactors etc.

Composites and their Classification

Materials formed by combination of two or more materials is known as composite
One can manipulate the properties by this combination of materials.
Cement and other constituents make concrete which has more useful properties than
cement as far as construction quality is concerned.
Modern engineering applications demand the material to be suitable for a broad
spectrum of properties. This is many-a-times not possible from single material.
Composite material is the solution for this problem. They are Combination of two or
more individual material. Thecombination may be mechanical in nature and done by
means of dispersing of small particles, laminating or coatings of additive materials to the
parent or base material or by reinforcing the matrix with different fibres.
In composites continuous phase is termed as matrix and discontinuous phase added is
termed as reinforcement.
Property spectrum of such combined materials is wide and vivid in nature. Properties of
even opposite natures can also be manipulated by control over the quantity, shape and
fashion of additions.

1.4 Factors that Govern Material Selection for Engineering

During selection of materials, following factors must be taken into] consideration:
1. Properties of material
Properties can be defined as response of material to the external stimulation. Properties
can be classified into six categories based upon the type of external stimulations
provided to act upon the material.
Mechanical properties:Like strength, hardness, toughness.
Electrical properties: Like resistance, conductance.
Magnetic properties: Like permeability, magneticsaturation.
Thermal properties: Like refractoriness.
Optical properties: Like reflectivity, refractive index
Chemical properties: Like oxidation, corrosion resistance.

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1. Introduction to Material Science & Metallurgy

2. Service requirements
Material selected should not only be suitable for withstanding types and magnitude of
various forces but also must withstand the service environments.
e.g. material for furnace doors must withstand high temperatures.
3. Reliability
Reliability is degree of probability that the component and its material retain their
stability in order to serve the function for which it is designed.
e.g. cheap screw drivers are not reliable as they do not show of reliability in properties
as well as in dimensions.
4. Cost and availability
Abundance i.e. easy availability of materials plays important role in selection of materials for
engineering applications cost is also a major constraint in selection of materials.
5. Safety
Chosen material must perform the function efficiently in the service conditions. Materials
showing catastrophic i.e. brittle failures are almost always avoided as they are serious threat
to the safety.
6. Service environments
Material selection is largely influenced by the environment surrounding the material e.g.-
Sea water machinery asks for special quality materials.
7. Biodegradability and recyclability
Bio-degradable and recyclable materials are preferred nowadays as they do not affect
ecological balance adversely.
E-waste, non-biodegradable wastes are serious problems in modern society.
1.5 Structure of Metals
Structure of metal is the arrangement of its internal constituents. Structure can be
described on following four levels (ordered in increasing magnitude).
1. Subatomic structure: Based upon subatomic constituents such as electrons, protons.
2. Atomic structure: Arrangement of atoms and their clustersFCC, BCC etc.
3. Microscopic structure: Arrangement of phases observable under microscope.
4. Macrostructure: When structure can be viewed with unaided eyes.

1.6 Structure Property Co-relation

Reaction offered by the material to various stimulations comesform different levels of
structures, e.g. electrical properties like conductivity are governed by subatomic
structure which is at electronic arrangement level.
Mechanical properties, which is major focus of our interest, are governed by atomic,
microscopic and macroscopic levels of structure.
If atomic density in particular plane and particular direction is more as compared to the
other planes and directions, it is seen that these planes and directions are prone to
plastic deformation.
1. Introduction to Material Science & Metallurgy

If more number of such dense planes and directions are available in the lattice, the
material becomes easily plastically deformable and hence shows higher ductility.

1.7 Micro- And Macro-Examination

Micro-examination Macro-examination
1. Micro-examination or 1. Macro-examination involves the
micrographyinvolves the study of the study of the structure of metals and
structures of metals and their their alloys by the naked eye or by
alloysunder a micro-scope at low power magnification up to X15.
magnifications form X20 to X2000. The observed structure is called the
The observed structure is called the macrostructure
2. Micro-examination involves much 2. Macro-examination gives a broad
smaller areas and brings out picture of the interior of a metal by
information which can never be studying relatively large sectioned
revealed by low magnification. areas.
3. The aim of micro-examination is 3. The aim of macro-examination is
To determine the size and shape of To reveal the size, form and
the crystallites which constitute an arrangement of crystallites.
alloy. To reveal fibers in deformed metals.
To reveal structures characteristic of To reveal shrinkage porosity and gas
certain types of mechanical working cavities
operations. To reveal cracks appearing during
To discover microdefects certain fabrication processes.
To determine the chemical content To show chemical non homogeneity
of alloys in the distribution of certain
To indicate quality of heattreatment, constituents appearing in alloys upon
mechanical properties. their solidification from the liquid
4. Micro-examination requires proper 4. Surface preparation for
surface preparation of the specimen macroexamination follows similar
before studying it under the lines to those for microexamination
microscope. but need not be taken to such a high
degrees of surface finish and so the
final stages of polishing can be
5. Micro-examination requires that the 5. Macro-examination is also carried
polished specimen surface should be out on an etched surface. Various
etched with asuitable reagent. Etching Reagents For Steel
Nitric acid 25 CC
Water 75 CC

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1. Introduction to Material Science & Metallurgy


Specimen preparation or polishing is necessary to study its microstructure, because the
metallurgical microscope discussed earlier makes use of the principle of reflection of light
(from the specimen) to obtain the final image of the metal structure.Satisfactory
metallographic results can be obtained only, when the specimen has been carefully
prepared. Even the most costly microscope will not reveal the metal structure if the
specimen has been poorly prepared.
The procedures for preparing the specimen both macro and micro-examination is the same,
except that in the latter the final surface finish is more important than in the former.

1. Selection of specimen. When investigating the properties of a metal or alloy, it is

essential that the specimen should be selected from that area (of the alloy plate or casting)
which can be taken as representative of the whole mass.

2. Cutting of the specimen. After selecting a particular area in the file mass, the specimen
may be removed with the help of a saw, a. panning tool, an abrasive wheel, etc.

3. Mounting the Specimen.If the specimen is too small to be held in hand for further
processing, it should be mounted in thermoplastic resin or some other low melting point

4. Obtaining Flat Specimen Surface. It is first necessary to obtain a reasonably flat surface
on the specimen. This is achieved by using a fairly coarse file or machining or grinding, by
using a motor driven emery belt.

5. Intermediate and Fine Grinding. Intermediate and fine grinding is carried out using
emery papers of progressively finer grade.

The emery papers should be of very good quality in respect of uniformity of particle
size.Four grades of abrasives used are: 220 grit, 320 grit, 400 grit and 600 grit (from coarse
to fine); the 320 grit has particle sizes (of the silicon carbide) as about 33 microns and 600
grit that of 17 microns (1 micron = 10-4 cm).

The specimen is first ground on 220 grit paper, so that scratches are produced roughly at
right angle to those initially existing on the specimen and produced through preliminary
grinding or coarse filing operation.Having removed the primary grinding marks, the
specimen is wash free of No. 220 grit.Grinding is then continued on the No. 320 paper, again
turning the specimen through 900 and polishing until the previous scratches marks are
removed.The process is repeated with the No. 400 and No. 600 papers.Grinding with the
No. 200, No. 320, etc., papers could be done in the following ways:

a) The specimen may be hand-rubbed against the abrasive paper which is laid over a
flat surface such as a piece of glass plate.
1. Introduction to Material Science & Metallurgy

b) The abrasive paper may be mounted on the surface of a flat, horizontally rotating
wheel and the specimen held, in the hand, against it.
In either case, the surface of the abrasive paper (with a water proof base) shall be lubricated
with water so as to provide a flushing action to carry away the particles cut from the

6. Rough Polishing.A very small quantity of diamond powder (particle size about 6 microns)
carried in a paste that is oil-soluble is placed on the nylon cloth-covered surface of a rotating
polishing wheel. The lubricant used during the polishing operation is specially prepared
oil.The specimen is pressed against the cloth of the rotating wheel with considerable
pressure and is moved around the wheel in the direction opposite to rotation of the wheel
to ensure a more uniform polishing action.

7. Fine Polishing.The polishing compound used is alumina (Al2O3) power (with a particles of
0.05 microns) placed on a cloth covered rotating wheel. Distilled water is used as a
lubricant.Fine polishing removes fine scratches and very thin distorted layer remaining from
the rough polishing stage.

8. Etching.Even after fine polishing, the granular structure in a specimen usually cannot be
seen under the microscope; because grain boundaries in a metal have a thickness of the
order of a few atom diameters at best, and resolving power of a microscope is much too low
to reveal their presence. In order to make the grain boundaries visible, after fine polishing
the, metal specimens are usually etched.Etching imparts unlike appearances to the metal
constituents and thus makes metal structure apparent under the microscope.

Before Etching, the polished specimen is thoroughly washed in running water.Then, the
etching is done either by

Immersing the polished surface (of the specimen) in the etching Reagent or by
Rubbing the polished surface gently with a cotton swab wetted with the Etching
After etching, the specimen is again washed thoroughly and dried.


Macroetching is the procedure in which a specimen is etched and evaluated macro
structurally at low magnifications. It is a frequently used technique for evaluating steel
products such as billets, bars, blooms, and forgings. There are several procedures for rating
a steel specimen by a graded series of photographs showing the incidence of certain
conditions and is applicable to carbon and low alloy steels. A number of different etching
reagents may be used depending upon the type of examination to be made. Steels react
differently to etching reagents because of variations in chemical composition, method of

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1. Introduction to Material Science & Metallurgy

Etching Reagents for Microscopic Examination

No Type of Etchant Composition Uses

1. Nital (i) Cone, Nitric acid 2 CC For etching steels, gray cast
98 CC iron &black heart malleable
(ii) Absolute methyl alcohol

2. Acid ammonium (i) Hydrochloric acid 10 CC For etching stainless steels.

persulphate 10 gms
(ii) Ammonium persulphate
80 CC
(iii) Water
3. Ammonia (i) Ammonium hydroxide 50 CC The best general etchant for
hydrogen (0.880) copper, brasses and bronzes.
peroxide 20-50 CC
(ii) Hydrogen peroxide (3%
50 CC
(iii) Water
4. Dilute hydro- (i) Hydrofluoric acid 0.5 CC A good general etch-ant for Al
fluoric acid 99.5 CC and its alloys
(ii) Water

5. Kellers reagent (i) Hydrofluoric acid 1 CC For (immersion) etching of

1.5 CC Duralumin type alloys
(ii) HCI
2.5 CC
(iii) HNO3 95 CC

(iv) Water
6. Mixed nitric and (i) Nitric acid 50 CC A good general etch-ant for Al
acetic acids 50 CC and its alloys
(ii) Glacial acetic acid


The three basic methods for grain size estimation recommended by the ASTM are:

1 Comparison method
2 Intercept method
3 Planimetrlc (or Jeffries) method
1. Introduction to Material Science & Metallurgy

Comparison MethodThe specimen is prepared and etched according to the metallographic

procedure. The image of the microstructure projected at a magnification of 100x, or a
photomicrograph of the structure at the same magnification, is compared with a series
ofgraded standard grain-size charts (ASTM E112-63). By trial and error a match is secured,
and the grain size of the metal is then designated by a number corresponding to the index
number of the matching chart. Metals showing a mixed grain size are rated in a similar
manner, and it is customary in such cases to report the grain size in terms of two numbers
denoting the approximate percentage of each size present. The comparison method is most
convenient and sufficiently accurate for specimens consisting of equiaxed grains. The ASTM
grain-size number n maybe obtained as follows:

where N is the number of grains observed per square inch at 100x magnification

Intercept MethodThe grain size is estimated by counting on a ground-glass screen, or

photomicrograph, or on the specimen itself, the number of grains intersected by one or
more straight lines. Grains touched by the end of the line count only as half grains. Counts
are made on atleast three fields to assure a reasonable average. The length of the line in
millimeters divided by the average number of grains intersected by it gives the average
intercept length or grain "diameter." The interceptmethod is recommended particularly for
grains that are not equiaxed.

Planimetric (or Jeffries) Method A circle or a rectangle of known area (usually 5,000 sq mm)
is inscribed on a photomicrograph or on the groundglass of the metallograph. A
magnification should be selected which will give at least 50 grains in the field to be counted.
The sum of all the grains included completely within the known area plus one-half the
number of grains intersected by the circumference of the area gives the total number or
equivalent whole grains within the area. Knowing the magnification of the specimen, the
number of grains per square millimeter is determined by multiplying the equivalent number
of whole grains by the corresponding magnification. Thus, if the equivalent number of
whole grains is found to be 75 at a magnification of 100x, the number of grains per square
millimeter is equal to 75 x 2.0, of 150.
In case of dispute, the planimetric method is preferred over the comparisonmethod for
equiaxed grains. it Is important to realize that in using any method to determine grain size,
the estimation is not a precise measurement. A metal structure is a mixture of three-
dimensional crystals of varying sizes and shapes. Even if all the crystals were identical in size
and shape, the cross sections of the grains on the polished surface would show varying
areas depending upon where the plane cuts each individual crystal. Therefore, no two fields
of observation can be exactly the same.


Sulphur present in steel is in the form of FeS, which has low melting point. Presence of
FeS makes steel 'hot short' segregation of FeS is detremental to the properties of steel.

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1. Introduction to Material Science & Metallurgy

The distribution of sulphides, in the cross section prepared can be found out by sulphur
print however estimation of sulphur content is not possible by sulphur print. Sulphur
print provides permanent record of sulphide distribution.
Procedure of sulphur print
Surface under consideration is polished by 0 and 00 emery papers and then washed
under tap water.
Photographic bromide paper is soaked in 2Vo aqueous solution of sulphuric acid for the
duration of 5 to 10 minutes.
Emulsion side of photographic paper soaked with sulphuric acid is brought in close
contact with the polished steel surface to be studied.
The contact time may be 3 to 4 minutes. Roller is used to make close contact between
paper and surface.
Sulphur printing involves following reactions.

(i) FeS H2SO4 FeSO4 H2S

From Steel (On Photographic paper)

From Steel (On Photographic paper)

(ii) H2S 2AgBr Ag2S 2HBr

Emulsion on
Photographic paper Creates dark brown spots
on Photographic paper

Fig. 1.1 Sulphur print

Photographic paper is then removed form the polished surface and washed thoroughly
under tap water.
1. Introduction to Material Science & Metallurgy

Photographic paper is then fixed by dipping it in sodium thiosuphate for 15 minutes to

create the permanent record
The entire process of surphur print is carried out in daylight.
Spark test can be considered as macroexamination as the inspection is carried out by
unaided eyes.
This test is useful in sorting the steels according to their chernical composition by
observing the spark struck by the steel when brought in contact with rotating abrasive
wheel such as grinder. Estimation of contents of constituent elements is not possible by
spark test.
When steel is brought in contact with rotating abrasive wheel, due to friction between
the both steer particres become loose. These hot particles (due to generated heat) move
away in from the wheel in a trajectory called 'carrier lines' .
Hot steel particles following carrier lines contain carbon. Carbon in particles reacts with
oxygen in air to form COz. This reaction develops the internal pressure within the
particles and make them explode. Explosion is expressed as burst or spurt.

The sorting of steel from another is possible because

(a) Carrier lines for different steels vary in number, length, breadth and colour.
(b) Bursts for different steels have difference in number shape and intensity.


Chemical Analysis of steels for Estimation of carbon
Carbon is principal alloying element of steels and largely influences the properties of
steels. carbon in steels is in combined form.
Following are widely used methods of carbon estimation of steels chemical analysis.
(a) carbon by combustion : suitable for carbon content determination in all types of
(b) EggertzMethod : suitable for carbon content determination in plain carbon and
low alloY steels.

(a) Carbon by combustion

principle : oxidation of carbon is effected by combustion at high temperature in a
regulated oxygen stream that converts carbon into carbon dioxide. carbon dioxide is
made free of sulphur gases and moisture' carbon dioxide, then, is absorbed in solid
absorbant. Difference between the final weight of absorbant (after coz is absorbed) and
initial weight of solid absorbant (befor coz is absorbed) is rneasureofcarbon content
ofsteel. Reagents used:
(i) Soda asbestos-Absorbant (L2to30 mesh grade)

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1. Introduction to Material Science & Metallurgy

(ii) Anhydrone - i.e. Magnesium perchlorate

(iii) Chromic - Sulphuric acid solution

Fig. 1.2 Apparatus for carbon by combustion

Maintain the furnace temperature of furnace at 1080C for mai carbon steel samples
and around 1150C for high / alloy steels.
Regulate flow of oxygen B2E ml/min and note manometer level Keeping Nesbitt bulb in
Detach Nesbitt bulb and weigh it.
By attaching the bulb again continue for 10 minutes and again take weight. continue
weighing at every 10 minute interval until constant weight is obtained.
Measare 2.729 gms of clean steel trimmings or drillings and transfer to previously
ignited combustion boat.
Place pure assay grade lead foil on the top of the sample (lead accelerates the
combustion of carbon). To make lead foil carbon free it is washed ln ether and then
Allow the oxygen stream to pass through safety valve ,E,, weighed Nesbitt bulb at'M',
place the boat containing steel into the hot zone of combustion tube and readmit the
oxygen supply to the combustion tube.
combustion starts after one minute and is indicated by reduced oxygen flow through
sulphuric acid tubes. Continue conobustion for 5 more minutes, detach Nesbitt bulb and
weigh it.
The increase in weight of Nesbitt bulb is measure of coz absorbed.
If factor weight i.e. 2.72g gms of steel is taken, the weight of coz is multiplied by 10 to
get percentage of carbon.

(b) Eggertz method for carbon estimation in steel

1. Introduction to Material Science & Metallurgy

Principle : When steels is treated with dilute Nitric acid, combined carbon frorn steel
forms nitrated compound, brown in colour. Intensity of brown colour of this compound
is proportional to the carbon content of the steel. Intensity of brown colour formed by
steel sample is then compared with that of standard specimen and conclusion is arrived
3 to 5 ml of dilute HNO3 with sp. gravity 1.2 is slowly added to 0'1 gm of steel samples.
slow addition is recommended at earlier stages of HNO3 additions in order to avoid
violent reaction.
Heat in a water bath and occasionally shake if bubbling is observed.
Stop heating when steel is completely dissolved.
Remove from water bath and allow the solution to cool.
Take 0.1 gm of standard steel of similar carbon content and treat similarly to obtain the
solution. (It generhlly takes 20 to 30 min)
compare the colours of both solution by taking them in Eggertz tubes after necessary
dilution with water.
Quantities recommended for different steels.
0.2 gm for low carbon steels
0.1 gm for medium carbon steels
0.05 gm for high carbon steels

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Course Contents
2.1 Introduction
2.2 Unit Cell And Its
Lattice Parameters
2.3 Bravais Lattices
2.4 Coordination Number
2.5 Crystal structure of
2.6 Atomic Packing Factor
2.7 Crystallographic Planes
And Directions
2.8 Polymorphism And
2.9 Diffusion In Solids
2.10 Crystallization
2.9 Mechanism
2.11 Nucleation
2.12 Growth of crystal
2.12 Imperfection In

Page 2.1
2. Crystal Geometry Material Science &Metallurgy

Crystallography is the study of the crystal formation of solids, including:
X-ray determination of lattice structures,Crystal habit, (i.e. the form of a crystal),The
shape and defects of crystals.When applied to metals, this science is called
Crystallography is that branch of science in which the internal structure of crystals,
their properties, external or internal symmetries of crystals are studied.
Crystalline materials consist of atoms or molecules arranged in a regular and orderly
manner in a three dimensional pattern.
The various terms associated with crystallography are:

(1) Crystal (2) Structure

(3) Space lattice (4) Unit cell
(5) Crystallographic planes (6) Lattice parameter
(7) Miller indices (8) Atomic packing factor
(9) Coordinate number, etc.

(1) A Crystal is a solid whose constituent atoms or molecules are arranged in a systematic
geometric pattern.
(2) The structure implies the arrangement and disposition of the atoms within a crystal.
(3) The atoms arrange themselves in distinct pattern in space called a space lattice.
(4) The unit cell is the smallest group of atoms possessing the symmetry of the crystal.
(5) The layers of atoms or the planes along which atoms are arranged are known as atomic
or crystallographic planes.
(6) Characteristic intercepts and interfacial angles of a crystal constitute the lattice
parameters of a cell.
(7) Miller Indices is a system of notation for designating crystallographic planes and
directions of crystals.
(8) Atomic packing factor is the ratio of the volume of the atoms per unit cell to the total
volume occupied by the unit cell.
(9) Coordinate number is the number of nearest atoms directly surrounding a given atom
in a crystal i.e., nearest neighbours to an atom in crystal.
Material Science &Metallurgy 2. Crystal Geometry


Fig. 2.1 Unit cell and lattice parameter

Lattice is the regular geometrical arrangement of points in crystalspace.
The atoms arrange themselves in distinct pattern; in space, called a space lattice.
Space lattice is the three dimensional network of imaginary lines connecting the atoms.
A Space lattice can be considered as an infinite array of points in space, so arranged that
it divides space into equal volumes with no space excluded.
An important characteristic of a space lattice is that every point has identical
Space lattice or crystal lattice is the arrangement of atoms in a crystal.
As already explained above, a space lattice can be considered as an infinite array of
points in space, so arranged that it divides space into equal volumes with no space
excluded.Every point, which is called a lattice point, has identical surroundings with
every other point.
The smallest volume that contains the full pattern of repetition is called a unit cell.
Identical unit cells must completely fill the space when they are packed face to face,
thus generating a space lattice . If a unit cell is so chosen that it contains lattice points
only at its corners, it is called a primitive unit cell or simple unit cell.
A primitive unit cell contains only one lattice point because each point at eight corners is
shared equally with eight adjacent unit cells. The edge length of the unit cell, called a
lattice constant or a lattice parameter, is a lattice translation in a given direction. Simple
monoclinic, Triclinic, simple cubic are known as primitive cells. Unit cells for most crystal
structures are parallelepipeds or prisons having three sets of parallel faces.
Fig. shows the unit cell geometry, which is, the shape of the appropriate unit cell
parallelepiped without regard to the atomic positions in the cell.
Within this framework, an x, y, z coordinate system is established with its origin at one
of the unit cell corners; each of the x, y, and z axis coincide with one of the three
parallelepiped edges that extend from this corner, as illustrated in Fig.
2. Crystal Geometry Material Science &Metallurgy

Fig2.2 A unit cell with x, y and z coordinate axis, showing axial lengths (a, b, and c) and
interaxial angles (, and ).

The unit cell geometry is completely defined in terms of six parameters: the three edge
lengths a, b and c and the three interaxial angles , and . These are indicated in Fig.
35.8 and are sometimes termed the Lattice Parameters of a crystal structure.
On this basis, there are found crystals having seven different possible combinations of a,
b, and c and , and , each of which represents a distinct crystal system.


Bravais lattices are the fourteen basic crystal lattices.
Bravais showed that there axe only fourteen possible different networks of lattice points
Therefore, there are only 14 standardspace lattices (Fig. 35.9) that are needed to
describe all possible arrangements of points in space consistent with translational
periodicity. Every crystal structure is based on one of the possible space lattices.
There are only 14 independent ways of arranging points in three dimensions in a crystal.
Bravais lattices named after their originator Mr. Bravais, are the 14 distinguishable
three dimensional space lattices that can be generated by repeated translation of three
non-coplaner vectors a, b, and c of a unit cell in three dimensional space.
Seven sets of axis, are needed to construct the fourteen Bravais lattice. Accordingly, all
crystalline solids can be classified into 7 crystal systems .
The fourteen Bravais lattices continue in three dimensions. Each indicated point has
identical surroundings.
The fourteen Bravais lattices are explained below:
(1) Simple Monoclinic lattice
It has lattice points at the eight corners of the unit cell. It has vectors a b c and
interaxial angles = = 90 (the crystal system).
Material Science &Metallurgy 2. Crystal Geometry

(2) End Centered Monoclinic Lattice

It has lattice points at the eight corners and at two face centres, opposite to each
other. It has vectors a b c , and interaxial angles a = = 90

(3) Triclinic lattice

It has lattice points at the eight corners of the unit cell. It has vectors a b c and
interaxial angles 90.

(4) Hexagonal lattice

It has points at the twelve corners of the hexagonal prism and at the centres of the
two hexagonal faces of the unit cell. It has vectors a b = c and interaxial angles =
= 90 and = 120.

(5) Rhombohedral lattice

It has lattice points at the eight corners of the unit cell. It has vectors a = b = c and
interaxial angles = = 90.

(6) Simple Orthorhombic lattice

It has lattice points at the eight corners of the unit. cell. It has vectors a b cand
interaxial angles = = 90.

(7) Body Centered Orthorhombic lattice

It has lattice points at the eight corners and at the body centre. It has vectors a b
c and interaxial angels = = = 90.

(8) End-Centered Orthorhombic lattice

It has lattice points at the eight corners and at two face centres opposite to each
other. It has vectors a b c and interaxial angles = = = 90.

(9) Face Centered Orthorhombic lattice

It has lattice points at the eight corners and at the six face centres of the unit cell. It
has vectorsa b c and interaxial angles = = = 90.

(10) Simple Cubic lattice

It has lattice points at the eight corners of the unit cell. It has vectors .a = b = c and
interaxialangels = = = 90.
2. Crystal Geometry Material Science &Metallurgy

(11) Body Centered Cubic lattice

It has lattice points at the eight corners and at the body centre. It has vectors a = b =
c and interaxial angles = = = 90.

(12) Face Centered Cubic lattice

It has lattice points at the eight corners and at the face centres of the unit cell. It has
vectors a = b = c and interaxial angles = = = 90.

(13) Simple Tetragonal lattice

It has lattice points at the eight corners of the unit cell. It has vectorsa = b c and
interaxial angles = = = 90.

(14) Body Centered Tetragonal lattice

It has lattice points at the eight corners and at the body centre. It hasvectors a = b
cand interaxial angles = = = 90.

Fig. 2.3 Bravais lattice

Every atom in a crystal is surrounded by other atoms. By the term coordination
number, we mean the number of nearest atoms which are directly surrounding a given
Material Science &Metallurgy 2. Crystal Geometry

The coordination number may also be defined as the nearest neighbours to an atom in
a crystal.
Fig shows that the coordination number of carbon atom is four, because it has four
hydrogen atoms around it.
When the coordination number is larger, the structure is more closely packed.
Coordination numbers for a simple cubic, BCC and FCC lattice have been discussed

Fig. 2.4 Coordination number

(1) Simple Cubic Structure

There is one atom at each of the (eight) corners of the cube. Any corner atom has four
nearest neighbour atoms in the same plane and two nearest neighbours (one exactly
above and other exactly below) in a vertical plane.
Hence coordination number for simple cubic structure is 4 + 2 = 6.

(2) Body Centered Cubic (B.C.C.) Structure

In B.C.C. structure, there is one atom at each corner of the cube and one atom at the
centre of cube. For any corner atom of the unit cell, the nearest atoms are the atoms
which are at the centres of unit cells.
As such corner atom is surrounded by eight unit cells having eight body centred atoms,
hence coordination number is 8.
Similarly by considering the centred atom of each unit cell, we can say that the
coordination number is 8 because every centred atom is surrounded by eight
equidistant neighbours.
Hence, coordination number for B.C.C. structure is 8.
(3) Face-centred Cubic (F.C.C.) Structure
In F.C.C. structure, there is one atom at each corner of the cube and one atom at the
centre of each face of the cube .
For any corner atom of the unit cell, the nearest are the face centred atoms.
2. Crystal Geometry Material Science &Metallurgy

For any corner atom, there will be 4 face centred atoms of the surrounding unit cells in
its own plane, 4 face centred atoms below this plane and 4 face centred atoms above
this plane.
Hence the coordination number for this case is 4 + 4 + 4 = 12

2.5 Crystal structure of metals

1. Body centered cubic(B.C.C.) If the atoms are represented as spheres, the center atom
touches each corner atom but they do not touch each other. Since each corner atom is
shared by eight adjoining cubes and the atom in the center cannot be shared by any
other cubes.

Fig. 2.5 Unit cell of B.C.C. structure

The unit cell of B.C.C. structure contains.

8 Atoms at the corner * () = 1 Atom

1 center atom = 1 Atom
Total = 2 Atom

2. Face centered cubic (F.C.C.)

In addition to an atom at each corner of the cube, there is one in the center of each face but
none in the center of the cube. Each face atom touches its nearest corner atom. Since each
corner atom is shared by eight adjoining cubes and each face is shared by only one adjacent
Material Science &Metallurgy 2. Crystal Geometry

Fig. 2.6 Unit cell of F.C.C. structure

The unit cell of F.C.C. contains:

8 Atoms at the corner* = 1 Atom

6 Face-centered Atom* = 3 Atom
Total = 4 Atom
This indicates that F.C.C. structure is more densely packed than the B.C.C. structure.

Example: Aluminum, Nickel, Copper, Gold, Silver Lead, Platinum & Gamma () iron.

3. Close packed Hexagonal (C.P.H.)

C.P.H. shows two based planes in the form of regular hexagons with atoms at each corner of
the hexagon and one atom at the center.
In addition there are three atoms in the term of a triangle midway between the two based
plane. If the based plane is divided in to six equilateral triangles, the additional 3 atoms are
nested in the center of alternate equilateral triangle.

Fig. 2.7 Unit cell of C.P.H. structure

2. Crystal Geometry Material Science &Metallurgy

Unit cell of B.C.C. & F.C.C. can be specified by lattice parameter a. The hexagonal unit cell
requires width of hexagon a and the distancebetweentwo based plane c. These
determine axial ratio cross section ( ) The axial ratio varies from 1.58 far beryllium to 1.88

Atomic packing Factor is 0.74.

Example: Zinc, Cadmium, Beryllium, magnesium.

No. of atoms in H.C.P.


Atomic Radius:
Assume that atoms are spherical in space and are in contact in a crystal.Atomic radius can
be design as half the distance betweenthe centers of two neighboring atoms.

1. Atomic radius of simple cubic structure:

a is the lattice parameter
Then, a =2r

2. Atomic Radius of F.C.C. structure:

Here a = Lattice parameter
r = Atomic radius
Then, AC2 = AB2 + BC2
(4r)2= a2 + a2
16r2 = 2a2

Material Science &Metallurgy 2. Crystal Geometry

3. Atomic radius of B.C.C. structure:

Let a = Lattice parameter
r = Atomic Radius

Let,HereAG = r+ 2r + r = 4r
Let EG2= a2+ a2 = 2a2
AG2= AE2+ EG2
(4r)2= a2+2a2= 3a2
16r2= 3a2

Atomic packing factor(APF):

1. APF for simple cubic structure:

Put or a=2r

( )

2. APF for F.C.C. structure:


3. APF for B.C.C. structure:

2. Crystal Geometry Material Science &Metallurgy


The layers of atoms or the planes along which atoms are arranged are known as atomic
or crystallographic planes.
As one becomes more and more involved in the study of crystals, the need for symbols
to describe the orientation in space, of important crystallographic planes and directions
become evident.
The Miller system of designating indices for crystallographic planes and directions is
universally accepted for the purpose.
Miller indices is a system of notation that denotes the orientation of the faces of a
crystal and the planes and directions of atoms within that crystal.
Miller Indices for Planes
One corner of the unit cell is assumed to be the origin (O) of thespace co-ordinates,
thenFind the intercepts on the three axis in multiples or fractions of the unit distances
on each axis (if a plane is parallel to,an axis it intersects it at infinity).
For example, consider plane ABC. It intersects .Y-axis at 1 unit, Y-axis at 3 units and Z-axis
at 2 units from origin O.
With this fill in the first (i) line of Table (ii) Take the reciprocal of these numbers; see (ii)
line of Table

(ii) Take the reciprocal of these numbers; see (ii) line of Table (iii) Change these
reciprocals to the smallest integers having the same ratio, i.e., by multiplying each
reciprocal (or fraction) by the same number such as the common denominator. Refer
line (III) of Table (iv) Enclose the values in parenthesis (hkl)Figs. (b), (c), (d) and (e) show
a number of crystallographic planes and their miller indices in a cubic lattice.

Page 2.12
Material Science &Metallurgy (2131904) 2. Crystal Geometry

If a plane cuts any axis on the negative side of the origin, the index will be negative and
is indicated by placing a minus sign above the index, as (hkl). For example, the miller
indices of plane ODEF which goes through the origin (O) cannot be determined without
changing the location of the origin. Change the origin from point O to point P .
The plane ODEF intersects X-axis and Z-axis at infinity but intersects Y-axis at - 1. The
plane hastherefore miller indices at (010).

Fig. 2.8(a) Miller Indices

2. Crystal Geometry Material Science &Metallurgy (2131904)

Fig. 2.8(b) Miller Indices

Miller Indices for Directions
The crystallographic direction can be defined as a line joining any two points of the
lattice. For example, in Fig. 35.23 (a) OQ OD and OE are all crystallographic directions.
Direction indices are simply the vector components of the directions resolved along
each of the axes.
Consider direction OE The point E lies in the plane OEFG. OE is 1 unit along X-axis, it
neither intercepts Y-axis nor Z-axis. Thus the coordinates of point E and the miller indices
of direction OE is [100] ( x = 1, y = 0, z = 0).
Similarly line OC, passes through the origin and the point C having .coordinatesx = l9y - 0,z
= 1; and thus the miller indices are [101]. Based on the same reasoning, indices of OD is
A general rule for finding the Miller indices of a crystallographic direction is :
Material Science &Metallurgy (2131904) 2. Crystal Geometry

Draw a vector from origin parallel to the direction whose indices are desired. For example,
if indices of AE is desired, draw a line OH parallel to AE through origin O. Draw CE in the
downward direction (dotted), let it cut OH at I and then draw IJ parallel to X-axis to cut Z-
Now OI is the line that passes through origin and is parallel to EA whose indices is to be
determined. The point I has coordinates x =1, y =0,z = -1 and thus the indices of line EA is
[101] (Parallel lines have same indices).

Fig. 2.8(c) Miller Indices


The ability of the material to have more than one structure is called
It is the behavior of material to show different crystal structure at certain
temperature or within a temperature range.
The atomic arrangement may change according to change in temperature such a
change in crystal structure is called as polymorphic change.
If the change in crystal structure is reversible then polymorphic change is known
as allotropy.
For example iron(-Fe) is BCC at room temperature but it becomes FCC (-Fe) when
heated to above 910C .
On further heating to above 1400 C it reverts to BCC (-Fe).
These changes are reversed on cooling hence iron changes its structure by
allotropoic change.
Diffusion refers to the transport of atoms through a crystalline or glassy solid.
Many processes occurringin metals and alloys, especially at elevated
temperatures, are associated with self-diffusion or diffusion.
2. Crystal Geometry Material Science &Metallurgy (2131904)

Diffusion processes play a crucial role in many solid-state phenomena and in the
kinetics of microstructural changes during metallurgical processing and
applications; typical examples include phase transformations, nucleation,
recrystallization, oxidation, creep, sintering, ionic conductivity, and intermixing in
thin filmdevices.
Direct technological uses of diffusion include solid electrolytes for advanced
battery and fuel cell applications, semiconductor chip and microcircuit fabrication
and surface hardening of steels through carburization. The knowledge of
diffusion phenomenon is essential for the introduction of a very small
concentration of an impurity in a solid state device.
(i) Self Diffusion: It is the transition of a thermally excited atom from a site of
crystal lattice to an adjacent site or interstice.
(ii) Inter Diffusion: This is observed in binary metal alloys such as the Cu-Ni
(iii) Volume Diffusion: This type of diffusion is caused due to atomic movement in
bulk in materials.
(iv) Grain Boundary Diffusion: This type of diffusion is caused due to atomic
movement along the grain boundaries alone.
(v) Surface Diffusion: This type of diffusion is caused due to atomic movement
along the surface of a phase.

Diffusion is the transfer of unlike atoms which is accompanied with a change of
concentration of the components in certain zones of an alloy. Various
mechanisms have been proposed to explain the processes of diffusion. Almost all
of these mechanisms are based on the vibrational energy of atoms in a solid.
Direct interchange, cyclic, interstitial, vacancy etc. are the common diffusion
mechanisms. Actually, however, the most probable mechanism of diffusion is
that in which the magnitude of energy barrier (activation energy)to be overcome
by moving atoms is the lowest.
Activation energy depends on the forces of interatomic bonds and crystal lattice
defects which facilitate diffusion transfer (the activation energy at grain
boundaries is only one half of that in the bulk of a grain). For metal atoms, the
vacancy mechanism of diffusion is themost probable and for elements with a
small atomic radius (H, N and C), the interstitial mechanism. Now,we will study
these mechanisms.
(i) Vacancy Mechanism: This mechanism is a very dominant process for diffusion
in FCC, BCC and HCP metals and solid solution alloy. The activation energy for this
Material Science &Metallurgy (2131904) 2. Crystal Geometry

process comprises the energy required to create a vacancy and that required to
move it. In a pure solid, the diffusion by this mechanism is shown
Diffusion by the vacancy mechanism can occur by atoms moving into adjacent
sites that arevacant. In a pure solid, during diffusion by this mechanism, the
atoms surrounding the vacant site shift their equilibrium positions to adjust for
the change in binding that accompanies the removal of a metal ion and its
valency electron.
We can assume that the vacancies move through the lattice and produce random
shifts of atoms from one lattice position to another as a result of atom jumping.
Concentration changes takes place due to diffusion over a period of time. We
must note that vacancies are continually being created and destroyed at the
surface, grain boundaries and suitable interior positions, e.g. dislocations.
Obviously, the rate of diffusion increases rapidly with increasing temperature.

Fig. 2.9 Diffusion

If a solid is composed of a single element, i.e. pure metal, the movement of

thermally excited atom from a site of the crystal lattice to an adjacent site or
interstice is called self diffusion because the moving atom and the solid are the
same chemical-element.
The self-diffusion in metals in which atoms of the metal itself migrate in a
random fashion throughout the lattice occurs mainly through this mechanism.
We know that copper and nickel are mutually soluble in all proportions in solid
state and form substitutional solid solutions, e.g., plating of nickel on copper
excited atom from a site of the crystal lattice to an adjacent site or interstice is
called self diffusion because the moving atom and the solid are the same chemical-
element. The self-diffusion in metals in which atoms of the metal itself migrate in a
random fashion throughout the lattice occurs mainly through this mechanism.
2.8 Crystallization
Crystallization is the (natural or artificial) process of formation of
solid crystals precipitating from a solution, melt or more rarely deposited directly
from a gas. Crystallization is also a chemical solidliquid separation technique, in
2. Crystal Geometry Material Science &Metallurgy (2131904)

which mass transfer of a solute from the liquid solution to a pure solid crystalline
phase occurs. In chemical engineering crystallization occurs in a crystallizer.
Crystallization is therefore an aspect of precipitation, obtained through a variation of
the solubilityconditions of the solute in the solvent, as compared to precipitation due
to chemical reaction.
2.9 Mechanism Of Crystallization
The crystallization process consists of two major events, nucleation and crystal
growth. Nucleation is the step where the solute molecules dispersed in
the solvent start to gather into clusters, on the nanometer scale (elevating solute
concentration in a small region), that become stable under the current operating
These stable clusters constitute the nuclei. However, when the clusters are not
stable, they dissolve. Therefore, the clusters need to reach a critical size i n order
to become stable nuclei. Such critical size is dictated by the operating conditions
(temperature, supersaturation, etc.). It is at the stage of nucleation that the
atoms arrange in a defined and periodic manner that defines the crystal
structure note that "crystal structure" is a special term that refers to the
relative arrangement of the atoms, not the macroscopic properties of the crystal
(size and shape), although those are a result of the internal crystal structure.
The crystal growth is the subsequent growth of the nuclei that succeed in
achieving the critical cluster size. Nucleation and growth continue to occur
simultaneously while the supersaturation exists.
Supersaturation is the driving force of the crystallization, hence the rate of
nucleation and growth is driven by the existing supersaturation in the solution.
Depending upon the conditions, either nucleation or growth may be predominant
over the other, and as a result, crystals with different sizes and shapes are obtained
(control of crystal size and shape constitutes one of the main challenges in
industrial manufacturing, such as for pharmaceuticals).
Once the supersaturation is exhausted, the solidliquid system reaches
equilibrium and the crystallization is complete, unless the operating conditions
are modified from equilibrium so as to supersaturate the solution again.
Many compounds have the ability to crystallize with different crystal structures, a
phenomenon called polymorphism. Each polymorph is in fact a different
thermodynamic solid state and crystal polymorphs of the same compound exhibit
different physical properties, such as dissolution rate, shape (angles between
facets and facet growth rates), melting point, etc. For this reason, polymorphism
is of major importance in industrial manufacture of crystalline products.
Material Science &Metallurgy (2131904) 2. Crystal Geometry

2.11 Nucleation
It is the first step in the formation of either a new thermodynamic phase or a new
structure via self-assembly orself-organisation. Nucleation is typically defined to
be the process that determines how long we have to wait before the new phase
or self-organised structure, appears.
Nucleation is often found to be very sensitive to impurities in the system.
Because of this, it is often important to distinguish between heterogenous
nucleation and homogeneous nucleation. Heterogeneous nucleation occurs
at nucleation sites on surfaces in the system.Homogenous nucleation occurs
away from a surface.
Nucleation the initial process that occurs in the formation of a crystal from a
solution, a liquid, or a vapour, in which a small number of ions, atoms, or
molecules become arranged in a pattern characteristic of a crystalline solid,
forming a site upon which additional particles are deposited as the crystal grows.

Nucleation processes are classed as heterogeneous or homogeneous. In the

former, the surface of some different substance, such as a dust particle or the
wall of the container, acts as the centre upon which the first atoms, ions, or
molecules of the crystal become properly oriented; in the latter, a few particles
come into correct position in the course of their random movement through the
bulk of the medium. Heterogeneous nucleation is more common, but the
homogeneous mechanism becomes more likely as the degree of supersaturation
or supercooling increases. Substances differ widely in the likelihood that they will
crystallize under conditions in which the crystalline state is the inherently stable
one;glycerol is a well-known example of a compound prone to supercooling.


Once the first small crystal, the nucleus, forms it acts as a convergence point (if
unstable due to supersaturation) formolecules of solute touching or adjacent to
the crystal so that it increases its own dimension in successive layers. The pattern
of growth resembles the rings of an onion, as shown in the picture, where each
colour indicates the same mass of solute; this mass creates increasingly thin
layers due to the increasing surface area of the growing crystal. The
supersaturated solute mass the original nucleus may capture in a time unit is
called the growth rate and is a constant specific to the process. Growth rate is
influenced by several physical factors, such as surface tension of
solution, pressure, temperature, relative crystal velocity in the solution, Reynolds
number, and so forth.
2. Crystal Geometry Material Science &Metallurgy (2131904)

The main values to control are therefore:

Supersaturation value, as an index of the quantity of solute available for the
growth of the crystal;
Total crystal surface in unit fluid mass, as an index of the capability of the solute
to fix onto the crystal;
Retention time, as an index of the probability of a molecule of solute to come
into contact with an existing crystal;
Flow pattern, again as an index of the probability of a molecule of solute to come
into contact with an existing crystal (higher in laminar flow, lower in turbulent
flow, but the reverse applies to the probability of contact).

The first value is a consequence of the physical characteristics of the solution, while the
others define a difference between a well- and poorly designed crystallizer.


For a crystalline solid we have tacitly assumed that perfect order exists
throughoutthe material on an atomic scale. However, such an idealized solid
does not exist;all contain large numbers of various defects or imperfections.
As a matter of fact,many of the properties of materials are profoundly sensitive
to deviations fromcrystalline perfection; the influence is not always adverse, and
often specific characteristicsare deliberately fashioned by the introduction of
controlled amounts ornumbers of particular defectsBy crystalline defect is
meant a lattice irregularity having one or more ofits dimensions on the order of
an atomic diameter. Classification of crystallineimperfections is frequently made
according to geometry or dimensionality of thedefect.


The simplest of the point defects is a vacancy, or vacant lattice site, one
normallyoccupied from which an atom is missing All crystalline solids
containvacancies and, in fact, it is not possible to create such a material that is
free ofthese defects.
The necessity of the existence of vacancies is explained using principlesof
thermodynamics; in essence, the presence of vacancies increases the
entropy(i.e., the randomness) of the crystal.
Plastic deformation

Course Contents
3.1 Introduction
3.2 Edge and Screw
3.3 Deformation by slip
3.4 Deformation by
3.5 Recovery
3.6 Recrystallization
3.7 Grain growth
Material Science &Metallurgy 3. Plastic deformation

This type of deformation is irreversible. However, an object in the plastic deformation
range will first have undergone elastic deformation, which is reversible, so the object
will return part way to its original shape.
Plastic deformation is a process in which enough stress is placed on metal or plastic to
cause the object to change its size or shape in a way that is not reversible. In other
words, the changes are permanent; even when the stress is removed, the material will
not go back to its original shape.
Sometimes referred to simply as plasticity, this type of deformation can take be
conducted under controlled circumstances as well as unintentionallyBoth the
deformation of plastic and the deformation of metals involve changes to the makeup of
the material itself. For example, metals that undergo this process of plastic deformation
experience a condition known as dislocation. As stress of some type is exerted on the
metal, the material reaches a point known as the yield strength. When this point is
achieved, the pattern of the molecules that make up the metal begin to shift. The end
result is that the molecules realign in a pattern that is shaped by the exterior stress
placed on the object.
In an edge dislocation, localized lattice distortion exists along the end of an extra half-
plane of atoms.
A screw dislocation results from shear distortion.
Many dislocations in crystalline materials have both edge and screws components;
these are mixed dislocations.

Fig.3.1 Edge and Screw Dislocations

The process by which plastic deformation is produced by dislocation motion is called
slip (movement of dislocations).
The extra 1/2-plane moves along the slip plane.
Dislocation movement is similar to the way a caterpillar moves. The caterpillar hump is
representative of the extra -plane of atoms.
3. Plastic deformation Material Science &Metallurgy

When metals are plastically deformed, some fraction (roughly 5%) of energy is retained
internally; the remainder is dissipated as heat. Mainly, this energy is stored as strain
energy associated with dislocations. Lattice distortions exist around the dislocation line.

Slip Systems
Dislocations move more easily on specific planes and in specific
directions.Ordinarily,there is a preferred plane (slip plane), and specific directions
(slip direction)along which dislocations move.The combination of slip plane and slip
direction is called the slip system.

Slip System FCC example

Fig.3.2 Slip System

Deformation in a single crystal

For a single crystal in tension, slip will occur along a number of equivalent & most
favorably oriented planes and directions at various positions along the specimen.
Each step results from the movement of a large number of dislocations along the
same slip plane

Fig.3.3 Deformation in a single crystal

Material Science &Metallurgy 3. Plastic deformation


In addition to slip, plastic deformation can occur by twinning. A shear force can produce
atomic displacements so that on one side of the plane (the twin boundary), atoms are
located in mirror image positions to atoms on the other side.

Fig.3.4 Deformation by Twinning

Strain hardening or work hardening

The phenomenon where ductile metals become stronger and harder when they are
deformed plastically is called strain hardening or work hardening. Intensity of strain
hardening can be gagedfrom the slope of the flow curve, defined by the parameter
strain hardening exponent, n. It is measure of the ability of a metal to strain harden .
For a given amount of plastic strain, higher the value of n, greater is the strain
hardening. Increasing temperature lowers the rate of strain hardening, and thus the
treatment is given, usually, at temperatures well below the melting point of the
material. Thus the treatment is also known as cold working.
The consequence of strain hardening a material is improved strength and hardness but
materials ductility will be reduced.
Strain hardening is used commercially to enhance the mechanical properties of metals
during fabrication procedures. In addition to mechanical properties, physical properties
of a material also changes during cold working. There is usually a small decrease in
density, an appreciable decrease in electrical conductivity, small increase in thermal
coefficient of expansion and increased chemical reactivity (decrease in corrosion
resistance).Procedure to find equilibrium concentrations of phases:
A tie-line or isotherm (UV) is drawn across two-phase region to intersect the
boundaries of the region.
Perpendiculars are dropped from these intersections to the composition axis,
represented by U and V, from which each of each phase is read. Urepresents
3. Plastic deformation Material Science &Metallurgy

composition of liquid phase and V represents composition of solid phase as intersection

U meets liquidus line and V meets solidus line.

3.5 Recovery
This usually occurs at low temperatures and involves motion and annihilation ofpoint
defects as well as annihilation and rearrangement of dislocations resulting in the
formationof subgrains and subgrain boundaries (e.g., tilt and/or twist low-angle
A distinctivefeature of the recovery process is that it does not involve any change in the
grain structure of thecold-worked metal, the only changes taking place are the
dislocation arrangements within theexisting grains. Small changes in hardness that are
sometimes observed during recovery canbe attributed to the decrease in the
dislocation and point defect density and to the growth ofthe subgrains.

3.6 Recrystallization
If increased thermal activation is available (i.e., if the temperature israised) nucleation
and growth of strain-free grains in the deformed matrix will take place. Asthese grains
grow, the dislocations in the matrix are annihilated at the boundaries of the
newlyformedgrains. Strength and hardness decrease considerably and ductility
Thelowest temperature at which stress-free grains appear in the structure of a
previously plasticallydeformed metal is termed the recrystallization temperature. This
depends upon the grain size,the severity of plastic deformation, and the presence of
solute atoms or second phase particles.
The recrystallization temperature is usually 1/3-1/2 the absolute melting point of the

3.7 Grain growth

If a recrystallized material is further annealed at the same temperature or at ahigher
temperature grain growth usually occurs. Boundaries between annealed grains
migrateand larger grains grow by an increase in the average grain size (or a decrease in
the ASTM grainsize number, n).
Grain growth depends on the fact that the grain boundary energy of thematerial is
reduced due to the decrease in grain boundary area for a given volume of material.
The effect of recovery, recrystallization and grain growth on grain size, internal stress
andstrength (or hardness) of a plastically deformed material .
Material Science &Metallurgy 3. Plastic deformation

Solidification Defects

Course Contents
4.1 Introduction
4.2 solidification defects
4.3 Methods to control
grain structure
4. solidification defects Material Science &Metallurgy (2131904)

Solidification of Metals:
Solidification involves the transformation of the molten metal back into the solid state.The
solidification process differs depending on weather the metal is pure element or an alloy.
A pure metal solidifies at a constant temperature equal to its freezing point, which is the
same as its melting point. The process occurs over and over time as shown.

Fig. 4.1 Solidification of metals

Characteristic grain structure in a casting of a pure metal, showing randomly oriented grains
of small size near the mold wall and large, columnar grains oriented toward the center of
the casting as shown in the figure.

Fig. 4.2 Grain structure in a casting of pure metal

Most alloys freeze over a temperature range rather than at a single temperature. The exact
range depends on the alloy system and the particular composition solidification of analloy
can be explained with reference to figure which shows the phase diagram for a particular
alloy system and the cooling curve for a given composition.
Material Science &Metallurgy (2131904) 4. solidification defects


Gas Porosity
We shall start by considering gas porosity. This can again be sub -divided into a furtherthree

Firstly, gas held in solution in the molten metal can be precipitated as the metalsolidifies,
simply as a result of the reduced solubility on freezing. Secondly, if the mould is filled under
very poor conditions, air can be entrained in themetal stream and then trapped as the
metal solidifies. Finally, the sand binders used to make the moulds and cores often break
down whenin contact with the molten metal and the gaseous decomposition products can
forcetheir way into the solidifying metal, leading to defects which are normally known
as'blows'.These different types of gas porosity defect vary in their size, distribution,
distancebelow the casting surface and morphology. It follows therefore that the cause of
suchdefects in a real casting can be deduced from a careful examination.

Air Entrapment
Moving on to the entrapment of air, we shall take as an example a sump casting that
hasbeen deliberately made badly using a conical pouring basin, a parallel downsprueand
Nowell base. In addition, we have a non-tapered runner bar
andinsufficientgates.generates surface turbulence in the metal stream as it fills the mould,
leading to achaotic, scrambled mess of metal and air. The air cannot escape easily
because it is heldin place by the oxide film. Furthermore, as the air bubbles move through
the moltenmetal, they leave behind a collapsed sac of oxide, forming a bubble trail which
isanother form of defect in the casting.

Page 4.3
4. solidification defects Material Science &Metallurgy (2131904)

4.3 Methods to control the grain structure

To produce the castings with iseotropic properties and improved strength by grain size
strengthening, the solidification of casting should be controlled in a way to produce a large
number of small equiaxed grains.
Also, to improve strength of casting and refine microshrinkage & gas porosity, the dendrites
should be as small as possible. This too requires the control of solidification.

Following explains some of the methods to control the grain structure during solidification:
1. Inoculation: By using appropriate inoculating or grain refining agents, a wide spread
nucleation can be produced during solidification that result in fine grain structure.

2. Rapid solidification: By encouraging rapid solidification, a very small spacing of

secondary dendrite arms many be achieved. The rate of solidification for any given can be
influenced by the size of the casting, the mould material and the casting process.

Thick casting solidifies slowly than thin casting.

Mold materials having a high density, thermal conductivity & heat capacity
produce more rapid solidification.
Metal mold casting process gives the highest strength casting due to rapid
3. Directional solidification: In many application, a small equiaxed grain structure in
casting is not desirable. Casting used for blades and vanes in turbine are such applications.
Phase and Phase equilibrium

Course Contents

5.1 Introduction
5.2 Useful terminology
5.3 Cooling curves
5.4 Phase diagram
5.5 Interpretation of Phase diagram
5.6 Gibbs phase rule
5.7 Classification of equilibrium
5.8 Two metals completely soluble
in the liquid and solid state
5.9 Eutectic system
5.10 Two metals completely soluble
in the liquid state, but only
partly soluble in the solid state
5.11 Peritectic reaction
5.12 Eutectoid transformation
5.13 Peritectoid transformation
5.14 Types of solid solution
5.15 Hume - Rothary law
5. Phase and Phase equilibrium Material Science and Metallurgy

Phase diagrams, also known as Equilibrium Diagrams are a very important tool in the
study of alloys.
A phase diagram has temperature as its ordinate (Y-axis) & alloy composition as
abscissa (X-axis).
Ideally the phase diagram will show the phase relationship under equilibrium
conditions, in which there is no change with the time.
Equilibrium conditions may be approached by extremely slow heating and cooling so
that if a phase change is to occur, sufficient time is allowed.


System: A system is a substance (or group of substances) so isolated from its
surroundings that it is unaffected by these and is subjected to changes in overall
composition, temperature, pressure or total volume only to the extent allowed by
the investigator.
Alloy System: It is defined as a combination of two or more elements, forming alloys
which are considered within a specified range of temperature, pressure and
Component: It is a unit of the composition variable of the system.
A system having one component is called a Unary system and the system having two,
three and four components are known as Binary, Ternary and Quaternary systems,
Phase: A phase can be defined as any part or portion of a chemical system which
processes distinctive physical characteristics, is limited by definite bonding surfaces,
and may conceivably be mechanically separated from its surroundings.
Structural constituent: The association of phases in a recognizably distinct fashion
may be referred as a structural constituent of the alloy.
Solid solution: It consists of atoms of at least two different types where solute atoms
occupy either substitutional or interstitial positions in the solvent lattice and the
crystal structure of the solvent is maintained.
Solubility limit: For almost all alloy systems, at a specific temperature, a maximum of
solute atoms can dissolve in solvent phase to form a solid solution. The limit is
known as solubility limit. In general, solubility limit changes with temperature. If
solute available is more than the solubility limit that may lead to formation of
different phase, either a solid solution or compound.

Page 1.2
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium

Phase equilibrium: It refers to the set of conditions where more than one phase may
exist. It can be reflected by constancy with time in the phase characteristics of a
system. In most metallurgical and materials systems, phase equilibrium involves just
solid phases. However the state of equilibrium is never completely achieved because
of very slow rate of approach of equilibrium in solid systems. This leads to non-
equilibrium or meta-stable state, which may persist indefinitely and of course, has
more practical significance than equilibrium phases. An equilibrium state of solid
system can be reflected in terms of characteristics of the microstructure, phases
present and their compositions, relative phase amounts and their spatial
arrangement or distribution.



A method to determine the temperature at which phase changes (liquidsolid)

occur in an alloy 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 forms a cooling curve for each of the alloys.
This method is useful in,
o Studying the changes that occur during the solidification of alloys and also
in determining transformations subsequent to solidification.

Fig. 5.1 Cooling curves for (a) Pure Metal or compound (b) Binary solid solution (c) Binary eutectic

5. Phase and Phase equilibrium Material Science and Metallurgy

There are mainly 3 types of cooling curves.

a)Cooling curve of pure metal or compound:
Liquid metal cools from P to Q. First crystals begin to form at point Q.
From Q to R, the melt liberates latent heat of fusion in such amounts that the
temperature from Q to R remains constant, until the whole mass has entirely
solidified (at point R). Between Q and R the mass is partly liquid and partly solid.
On further cooling from R to S, the solid metal cools and tends to reach room
The slopes of PQ and RS lines depend on the specific heats of liquid and solid metals

b) Cooling curve of a binary solid solution:

Curve portion PQ is similar no matter it is for a pure metal or for a binary system
consisting of two metals forming a solid solution.
However, in a binary system, during freezing (i.e.QR) period, the temperature does
not remain constant, but it drops along line QR till the whole mass is solid at point R.
The dropping trend of QR indicates that the alloy does not solidify at constant
temperature , but it possesses a freezing range which is due to the changes in the
composition of the solid and liquid phases which naturally result in variable freezing
(or melting) points.
The solid cools along RS to attain the room temperature.

c) Cooling curve of a binary eutectic system:

In this system, the two components are completely soluble in the liquid state but
entirely insoluble in solid state.
Liquid cools along PQ until the temperature Q is reached.
At Q, one component that is in excess will crystalize and the temperature will drop
along QR.
At point R the liquid composition has been reached at which the two components
crystalize simultaneously from the solution.
The temperature remains constant until the whole mass is solid.
Cooling from S to T is as usual.
Fig 5.2 shows a series of cooling curves for different alloys in a completely soluble
system (such as Cu-Ni system).
The figure shows how a phase equilibrium diagram (shown dotted) can be
constructed from the cooling curves of different alloys in the system.

Page 1.4
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium

Fig.5.2 Series of cooling curves giving rise to a phase diagram


A huge amount of information concerning the phase changes in many alloys systems
has been accumulated and the best way to record this data is in the form of Phase
diagram, which is also termed as Equilibrium diagram or Constitutional diagram.
An equilibrium diagram shows the limits of composition and temperature within
which the various constituents or phases of an alloy are stable.
Changes of structure and the composition of the constituents in equilibrium at a
fixed temperature can be determined from a phase diagram.
If two metals of a binary solid solution (such as Cu-Ni) system are mixed in various
proportions, melted and then cooled, and a cooling curve is constructed for each
composition (Fig 5.2), the resulting diagram obtained by joining Q1,Q2,Q3. And
R1,R2,R3, will be the phase diagram.
Q1,Q2,Q3 are the temperatures at which solidification completes.
This phase diagram shows two different and distinct phases; one is liquid metal
solution and the other is solid solution.
Within this two phases or within liquidus and solidus , the two phases i.e., liquid and
solid exist together, which can be mechanically separated by decantation of the
liquid phase.
Liquidus is that line above which the alloy is in liquid state and from where the
solidification starts.
Solidus is that line below which the alloy is in solid state and where solidification
5. Phase and Phase equilibrium Material Science and Metallurgy

If in a phase diagram adequate time is provided to attain equilibrium conditions, if

equilibrium conditions are not achieved then the non equilibrium solidification
results in porous, dendritic material.


The following three useful conclusions are the rules necessary for interpreting phase
The phases that are present.
The chemical composition of each phase.
The Lever Rule (the amount of each phase)

Rule-1: Prediction of Phases

From a phase diagram, specific information can be obtained only if a temperature
and a composition are specified.
For example, the state of the alloy of composition 30% Bistmuth can be determined
only with reference to a certain temperature. Thus when this alloy is at 1200F, point
1 is located (Fig 5.3) and when it is at 900F and 600F, points 2 and 3 are located
The next step is to determine the phase or phases present at points number 1, 2, and
Point-1: With 30% Bi 70%Sb alloy at 1200F, only liquid phase is
Point-2: With the same alloy but at 900F, two phases are present, i.e. Liquid
solution and Solid solution.

Fig.5.3 Interpretation of phase diagram (Sb Bi)

Page 1.6
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium

Point-3: With the same alloy, but at 600F, only one phase, i.e. The solid solution is
Similar analysis can be made for any other alloy composition and temperature in
phase diagram.

Rule 2: Phase Composition

To find out the composition of phases which are stable at a given temperature (say
900F, Fig 5.4), draw a horizontal (isothermal) line, OP at the given temperature.
The projections upon the X axis of the intersections (i.e. O & P) of the isothermal line
with the solidus and liquidus respectively , give the compositions of the solid and
liquid, which co-exist in equilibrium at that temperature.
For Example,
Liquid phase (point P) has the composition roughly 62% Bismuth.
Solid phase (point O) has the composition roughly 14% Bismuth.

Rule 3: Lever Arm Principle

Besides indicating the number of phases and phase composition, the phase diagram
also tells the proportion of co-existing phases at any given temperature.
To determine the relative amount of two phases, erect an ordinate at a point (say
30% Bi) on the composition scale which gives the total or overall composition of the
The intersection of this composition vertical (AL) and a given isothermal line OP (i.e.
point M) is the fulcrum of a simple lever system and OM and MP are lever arms,(fig
This is called as the lever rule because the amount of a given phase multiplied by its
lever arm is equal to the amount of the other phase multiplied by its (i.e. other) lever
The lever rule or principle may be expressed mathematically as:
The amount of solid phase,
(62 30)
= 100 = 100 = 66.67%
(62 14)

The amount of liquid phase,

(30 14)
= 100 = 100 = 33. 33%
(62 14)
5. Phase and Phase equilibrium Material Science and Metallurgy


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

P + F = C +2

Where P = Number of Phases (e.g. solid, liquid etc.)

F = Number of degree of freedom or the number of physical variables

(pressure, temperature, concentration) that can be independently changed
without altering the equilibrium, i.e., without causing disappearance of a
phase or the formation of new phase in the system.

C = Number of components in the system; for example, Pb and Sn are the

components of PbSn equilibrium diagram (fig 5.7).

In metallurgical systems where pressure is regarded as remaining fixed at one

atmosphere, the pressure variable is often omitted and equation is simplified in to,



Since the degree of freedom cannot be less than zero,

So, C + 1 P 0, or P C + 1
This means the number of Phases (P) in a system cannot exceed the number of
components plus one.
Therefore in a Binary system having value C=2, not more than 2+1=3 phases may be
in equilibrium.
Considering the figure 5.4, it is required to determine the number of degrees of
freedom using the phase rule.
1. Point X, in the region above the liquidus

Number of components C=2, since it is a binary system of Bi and Sb,

Number of phases P=1(liquid)

Applying the rule, F = C + 2 P

= 2+2-1

= 3 degrees of freedom

Page 1.8
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium

2. Point Y, between the liquidus and solidus

Number of components C=2

Number of phases P=2(liquid and solid)

Applying the rule, F = C + 2 P


=2 degrees of freedom


An equilibrium diagram has been defined as a plot of the composition of phases as a
function of temperature in any alloy system under equilibrium conditions.
Equilibrium diagram may be classified according to the relation of the components in
the liquid and solid states as follows:
1. Components completely soluble in the liquid state,
a) and also completely soluble in the liquid state,
b) but partly soluble in the solid state (EUTECTIC REACTION)
c) but insoluble in the solid state(EUTECTIC REACTION)
d) The PERITECTIC Reaction
2. Components partially soluble in the liquid state,
a) but completely soluble in the solid state,
b) and partly soluble in the solid state.
3. Components completely insoluble in liquid state and completely insoluble in the
solid state.



A system that illustrates an equilibrium diagram in which there is complete solubility

in the liquid and solid states is that of Antimony Bismuth system shown in figure
5.4 .
Since the two metals are completely soluble in the solid state, the only type of solid
solution formed will be substitutional solid solution.
Actually the solidification of a liquid alloy of this type consists of two processes :

(i) (a) Formation of crystals in the melt (at say point S),

(b) Growth of crystals (just as at point M).

5. Phase and Phase equilibrium Material Science and Metallurgy

(ii) Homogenization of the composition in various parts of each crystal:

(a) By diffusion between core and encasement.

(b) By diffusion between core and melt.


In an eutectic reaction, when a liquid solution of fixed composition, solidifies at a
constant temperature, forms a mixture of two or solid phase without an
intermediate pasty stage. This process reserves on heating.
Liquid solid1 + solid2
In eutectic system, there is always a specific alloy, known as eutectic composition (fig
5.4), that freezes at a lower temperature than all other compositions.

Fig.5.4 Cooling curves for two metals insoluble in solid state

Under conditions approaching equilibrium (slow cooling), it (specific alloy) freezes at

a single temperature like a pure metal.
In other respects, the solidification reaction of this composition is quite different
from that of a pure metal since it freezes to form a mixture of two different solid
At the eutectic temperature, two solids form simultaneously from a single liquid
The eutectic temperature and composition determine a point on the phase diagram
called as eutectic point.

Page 1.10
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium

Binary alloy eutectic system can be classified as:

(a) One in which, two metals are completely soluble in the liquid state but are
insoluble in each other in solid state.
(b) The other in which, two metals are completely soluble in the liquid state but are
partly soluble in each other in the solid state.
(a) Two metals completely soluble in the liquid state but completely insoluble
in the solid state.
Technically, no two metals are completely insoluble in each other. However, in some
cases the solubility is so restricted that for practical purposes they may be
considered insoluble, e.g. Tin Zinc or Bismuth Cadmium.
Fig 5.5 shows cooling curves for a series of two metals that are insoluble in the solid
state such as Bismuth and Cadmium. The figure also shows, how by joining a1b1,
a2b2,.points, the equilibrium diagram for such a system can be obtained.
To explain this type of system it is necessary to consider the cooling and
solidification of three compositions 1, 2 and 3.(fig 5.5)

Alloy-3: 80% Cd and 20% Bismuth.

As the temperature falls to T1, crystal nuclei of pure Cd begin to form. Since pure Cd
is deposited, it follows that the liquid becomes richer in Bi; the composition of liquid
moves to left 3' and as indicated by the diagram, no further Cd deposits until
temperature falls to T2.

Fig.5.5 The Bismuth Cadmium Equilibrium Diagram

At T2 more Cd is deposited and dendrites begin to develop from the already formed
nuclei (Fig. 5.5 (D)).
5. Phase and Phase equilibrium Material Science and Metallurgy

The growth of the Cd dendrites, on the one hand, and the consequent enrichment of
the remaining liquid in Bi, on the other, continues until the temperature has fallen to
140C, the eutectic temperature in this case.
The remaining liquid then contains 40% Cd and 60% Bi, the eutectic composition.

Alloy-1: 20% Cd and 80% Bi

Contrary to alloy 3, in this case crystal of pure Bi form first, enriching the melt with
The composition of the melt (or liquid) moves to right until ultimately the point E is
reached and the remaining liquid solidifies as eutectic (40% Cd and 60% Bi).

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

No solidification occurs until the melt reaches the eutectic temperature (140C)
At the eutectic temperature, the two pure metals crystallize together to give a
characteristically fine aggregate [Fig. 5.5 (C)] known as eutectic.
Eutectic consists of alternate layers of Cd and Bi which form at the eutectic
temperature (140C in this case).



Since most metals show some solubility for each other in the solid state, this type is
the most common and, therefore, the most common alloy system.
Metals such as Pb-Sn and Pb-Sb are partly soluble in each other in the solid state. -
Fig. 5.6 shows the Tin-Lead equilibrium diagram with microstructure obtained under
non-equilibrium condition of solidification.
The figure shows that:
(i) Tin will dissolve up to maximum of 2.6% Pb at the eutectic temperature, forming
the solid solution .
(ii) lead will dissolve up to a maximum of 19.5% tin at the eutectic temperature,
giving the solid solution .
(iii) Slope of BA and CD indicate that the solubility of Pb in Sn () and that of Sn in Pb
() decrease as the temperature falls.
Consider an alloy of composition Z (70%Pb 30%Sn). As the melt temperature falls
to T1, dendrites of composition Y will deposit.
The alloy solidifies as a solid solution until at 183C , the last layer of solid to form is
of composition C (80.5% Pb 19.5% Sn).

Page 1.12
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium

Fig. 5.6 The Tin Lead equilibrium diagram.

The remaining liquid which has the eutectic composition (38% Pb 62% Sn) then
solidifies by depositing, in the form of a eutectic, i.e. alternate layers of and , of
compositions B and C respectively.
If cooled slowly to room temperature the compositions of the solid solutions and
will follow the line BA and CD i.e. will become progressively poorer in lead and in


It is the reaction that occurs during the solidification of some alloys where the liquid
phase reacts with a solid phase to give a solid phase of different structure.
The reaction reverses on melting.

Like solid solution formation and eutectic reaction, peritectic reaction is also a
mechanism of solidification shown by various metal systems, but it is comparatively
less common.
A peritectic reaction is, actually, just the opposite of the eutectic reaction.
Refer to Fig. 5.7 showing the peritectic reaction.
5. Phase and Phase equilibrium Material Science and Metallurgy

Fig. 5.7 Peritetric Reaction

Assuming very slow rates of cooling, the peritectic reaction will occur only in those
Pt-Ag alloys that contain between 12 and 69% silver (Ag).
Consider a liquid (melt) of composition Z, i.e., containing 25% Ag. Solidification
commences at T1 and dendrites of , initially of composition W, begin forming.
Selective crystallization of continues down to Tp, the peritectic temperature; when
the alloy reaches this temperature, it is composed of solid -dendrites of
composition B and liquid of composition D in the proportion : liquid = RD:RB.
At peritectic temperature (1185C, in this case) the dendrites begin to react with
the remaining liquid and form solid solution , which contains 45% silver
(composition C). Since ZZ1 (point R ) lies between B and C this means that there is an
excess of the liquid solution , so that the liquid is used up first. Hence the final
structure will consist of containing 12% silver (composition B) and , containing
45% silver (composition C). These phases will be in the ratio
( )
( )

Consider another alloy Y.

The first stage in the solidification of alloy Y is the same as in alloy Z: solidification
begins at T2 and when the peritectic is reached, the alloy consists, similarly, of
dendrites of , of composition B and liquid of composition D, but in the proportions,
: liquid = Y1D: Y1B.
At peritectic temperature, all the reacts with some of the liquid to form of
composition C, the proportion of to remaining liquid is Y1D : Y1C.

Page 1.14
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium

After the peritectic reaction has occurred, the temperature falls and the remaining
liquid tends to solidify as which changes in composition along CY2. At Y2
solidification will be complete and the structure will consist of crystals of uniform
(of the same composition as that of the original liquid).
In actual practice, fast cooling tends to produce heterogeneous grains and may cause
some to be retained in the centre of the () grains.


Unlike Eutectic or Peritectic transformations which are liquid- solid transformations,
Eutectoid involves a solid-solid transformation.
Eutectoid reaction is an isothermal reversible reaction in which a solid phase (usually
a solid solution) is converted into two or more intimately mixed solids on cooling, the
number of solids formed being the same as the number of components in the

Eutectoid point : The point in the equilibrium diagram indicating the composition of
the eutectoid and its temperature of transformation.
Eutectoid structure : The structure, frequently lamellar, produced by the
simultaneous precipitation of the components of the eutectoid from the solid
Eutectoid reaction is found in many systems such as Cu-Al, Cu-Zn, Al-Mn, Cu-Be, etc.
Fig. 5.8 shows an eutectoid-diagram.

Fig. 5.8 Eutectoid diagram

5. Phase and Phase equilibrium Material Science and Metallurgy

Consider the alloy-1. As it is slowly cooled, solid solution is formed when the
liquidus line is crossed at Y1. More and more is formed until the solidus line is
crossed at Y2. It remains a uniform solid solution until the solvus line is crossed at Y3.
The pure metal A must now start to undergo an allotropic change, forming the
solid solution.
The composition of is gradually moving down and along the line ME ; solution
becomes richer in metal B.
When alloy reaches the eutectoid temperature Te, the reaches eutectoid point E.
The microstructure at room temperature consists of primary or proeutectoid
which was formed between Y3 and Y4 surrounded by the eutectoid mixture of + .


The peritectoid reaction is the transformation of two solids into a third solid.
It is an isothermal reversible reaction in which a solid phase reacts with a second
solid phase to produce yet a third solid phase on cooling.

Fig. 5.9 shows a Peritectoid Diagram, which can be explained on lines similar to those
for eutectoid diagram (Refer section 5.12).
L is the liquid phase.
, and are solid phases.
A and B are two metals.
Ep is the peritectoid point.
Tp is the peritectoid temperature.

Fig. 5.9 A Peritectoid diagram

Page 1.16
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium


Solid solutions occur in either of two distinct types, namely

Substitutional solid solution

1) Disordered
2) Ordered
Interstitial solid solution.
Substitutional solid solution: In substitutional solid solution, there is a direct
substitution of one type of atom for another so that solute atoms (Cu) enter the
crystal to take positions normally occupied by solvent atoms (e.g., nickel atoms); In
other words, in substitutional solid solution, the atoms of the solute substitute for
atoms of the solvent in the lattice structure of the solvent.Substitutional solid
solution forms when the solute and solvent atoms possess equal or approximately
equal (within 7.5%) diameters; for example, atomic diameter of copper is 2.551
and that of nickel is 2.487 , and the two (i.e., Cu and Ni) form substitutional solid
solution. The great majority of the solid solutions are of substitutional type.

Fig. 5.10 Substitutional Solid Solution

Disordered substitutional solid solution: In the formation of a substitutional

solid solution the solute atoms do not occupy any specific position but are
distributed at random in the lattice structure of the solvent. This alloy is said to be in
a disordered condition. In the disordered condition, the concentration of solute
atoms can vary considerably throughout the lattice structure.
When a disordered substitutional solid solution crystallizes from the melt, there is a
natural tendency for the core of the dendrite to contain rather more atoms of the
metal with higher melting point, whilst the outer fringes of the crystal will contain
correspondingly more atoms of the metal of the lower melting point.
5. Phase and Phase equilibrium Material Science and Metallurgy

Fig. 5.11 Disordered substitutional solid solution

Ordered substitutional solid solution: The alloy in the disordered condition, if

it is cooled slowly, under goes a rearrangement of the atoms because of the
diffusion that takes place during cooling. Diffusion tends to produce uniform
distribution of solute and solvent atoms. The solute atoms move into definite orderly
positions in the lattice.

Fig. 5.12 Ordered substitutional solid solution

This structure is now known as ordered substitutional solid solution or super lattice.
Prolonged annealing tends to produce still more uniform and ordered solid solution.
Cu- Zn, Au-Cu, Cu2MnAI are some examples of ordered structures.
Interstitial solid solution: Interstitial solid solution forms when solute atoms are
very small as compared to the solvent atoms, they are unable to substitute solvent
atoms (because of the large difference in diameters of solvent and solute atoms) and
can only fit into the interstices or spaces in the crystal lattice of solvent atoms .
Those atoms which have atomic radii less than 1 angstrom (1 ) are likely to form
interstitial, solid solutions. Such atoms are carbon (0.77 ), nitrogen (0.71 ),
hydrogen (0.46 ), oxygen (0.6 ), etc. Actually, atomic size is not the only factor that
determines whether or not an interstitial solid solution will form.

Page 1.18
Material Science and Metallurgy(161901) 5. Phase and Phase equilibrium

Fig. 5.13 Interstitial Solid solution

Small interstitial solute atoms dissolve much more readily in transition metals (such
as Fe, Ni, Mn, Mo, Cr, W, etc.) than in other metals. Carbon forms an interstitial solid
solution with F.C.C. iron during the solidification of steel but it can also be absorbed
by solid iron provided the latter is heated to a temperature at which the structure is
F.C.C. This is the basis of carburizing steels. Nitrogen also dissolves interstitially in
solid steel, during the nitriding process.


Several factors are now known, largely through the work of Hume-Rothery that
controls the range of solubility in alto systems. The different rules or factors are:
1. Crystal Structure Factor: The crystal lattice structure of the two (metal)
elements should same (i.e., both should be of b.c.c., f.c.c, or h.c.p. structure) for
complete solubility, otherwise the two solutions would not merge into each other.
Also, for complete solid solubility the size factor must usually be to than 8%.
2. Relative Size Factor: If two metals are to exhibit extensive solid solubility in
each other it is essential that their atomic diameters shall be fairly similar, since
atoms is essential that their atomic diameters shall be fairly similar, since atoms
differering greatly in size cannot be accommodated readily in the same structure (as
a substitutional solid solution) without producing excessive strain and corresponding
instability. This is what is referred to when the term size-factor is employed and
extensive solid solubility is encountered only when the two different atoms differ in
size by less than 15%, called a favourable size factor (e.g., Cu-Ni).
If the relative size factor is between 8% and 15%, the alloy system usually shows a
minimum and if this factor is greater than 15%, substitutional solid solution
formation is very limited.
5. Phase and Phase equilibrium Material Science and Metallurgy

3. Chemical-affinity Factor: The greater the chemical affinity of two metals, the
more restricted is their solid solubility. When their chemical affinity is great, two
metals tend to form an intermediate phase rather than a solid solution. Generally,
the farther apart the elements are in the periodic table, the greater is their chemical
4. Relative Valence (Valency) Factor: Consider two atoms, one with large
valence electrons and the other with small number of valence electrons. It has been
found that the metal of high valence can dissolve only a small amount of a lower
valence metal, while the lower valence metal may have good solubility for the higher
valence metal.
For example, in the Al-Ni alloy system, both metals have f.c.c. structure. The relative
size factor is approximately 14%.However; Ni is lower in valence than Al and thus
solid nickel dissolves 5% aluminium, but the higher valence Al dissolves only 0.04%

Page 1.20
The Iron Iron Carbide Equilibrium Diagram

Course Contents
6.1 Allotropy of Iron.
6.2 The Iron Iron Carbide
6.3 Definition of Structure.
6.4 Carbon Solubility in Iron.
6.5 Slow Cooling of Steel.
6. The Iron Iron Carbide Equilibrium Diagram Material Science & Metallurgy (2131904)

6.1 Allotropy of Iron:

The metal iron is a primary constituent of some of the most important engineering
In an almost pure form, known as ingot iron it is used for drainage culverts, roofing
and ducts, and as a base for porcelain enamel in refrigerator cabinets, stoves, washing
machines, etc.
Chemical analysis Mechanical properties
Carbon : 0.012% Tensile strength : 40000 PSI
Manganese : 0.017% Elongation in 2 inch : 40%
Phosphorous : 0.005% Hardness : 30 HRB
Sulpher : 0.025%
Silicon : Trace
Iron is an allotropy metal which means that can exist in more than one type of lattice
structure depending upon temperature.

Fig. 6.1 Cooling curve for pure iron.

When iron first solidifies at 2800F, it is in the B.C.C. (delta) form. Upon further cooling
at 2554F a phase change occurs and the atoms rearrange themselves into the
(gamma) form, which is F.C.C. and non-magnetic. When the temperature reaches
1666F, another phase changes occurs from F.C.C. non-magnetic iron to B.C.C. non-
magnetic (alpha) iron. Finally, at 1414F, iron becomes magnetic without a change in
lattice structure.
Material Science & Metallurgy (2131904) 6. The Iron Iron Carbide Equilibrium Diagram

Originally, non-magnetic iron was called iron until subsequent x ray studies
showed no change in lattice structure at 1414 F. Since this magnetic transformation
does not affect the heat treatment of iron carbon alloys.
All the allotropic changes give off heat (exothermic) when iron is cooled and absorb heat
(endothermic) when iron is heated (Refer Figure 6.1).

6.2 The Iron Iron Carbide Diagram:

The temperature at which the allotropic changes take place in iron is influenced by
alloying elements, the most important of which is carbon. The portion of the iron
carbon alloy system which is of interest is shown in Fig.6.2.
This is the part between pure iron and interstitial compound, iron carbide, Fe 3C,
containing 6.67% carbon by weight. Therefore, we will call this portion the iron- iron
carbide equilibrium diagram.

Fig. 6.2 The delta region for iron iron carbon diagram.
The diagram shows three horizontal lines which indicate isothermal reactions. The
solid solution is called austenite. The portion of the diagram in the upper left corner of is
expanded in Figure 6.2. This is known as delta region, because of the solid solution.
Horizontal line at 2720F is being peritectic reaction. The equation of the peritectic
reaction may be written as

The maximum solubility of carbon in B.C.C. iron is 0.10% (point M) while in F.C.C. iron
the solubility is much greater. The presence of carbon influences the iron to iron
allotropic change.
As carbon is added to iron, the temperature of the allotropic change increases from
2554F to 2720F at 0.10% carbon.
6. The Iron Iron Carbide Equilibrium Diagram Material Science & Metallurgy (2131904)

Consider the significance of the line NMPB. On cooling, the portion NM represents the
beginning of the crystal structure changes from B.C.C. iron to F.C.C. iron for alloys
containing less than 0.10% carbon.
The portion MP represents the beginning of this crystal structure change by means of a
peritectic reaction for alloys between 0.10% and 0.18% carbon.
For the alloys containing less than 0.18% carbon on cooling, the end of crystal structure
change is given by line NP.
On line PB, for alloy between 0.18 and 0.50% carbon, the allotropic change begins and
ends at constant temperature.
Any alloy containing more than 0.50% carbon will cut the diagram to the right of point
B and will solidify austenite only.
Since No commercial heat treatment is done in the delta region.

Fig. 6.3 The iron iron carbide equilibrium diagram labeled with the common names for the
In Figure 6.3 shows a eutectic reaction at 2065F at horizontal line CED, at point E where
4.3% carbon. Since the horizontal line CED represents the eutectic reaction, whenever
an alloy crosses this line the reaction must be take place.
Material Science & Metallurgy (2131904) 6. The Iron Iron Carbide Equilibrium Diagram

Any liquid that is present when this line is reached must now solidify in to the very fine
intimate mixture of the two phases that are at either end of the horizontal line, namely
austenite and iron carbide (called cementite). This eutectic mixture has given the name
ledeburite and equation may be written as

austenite cementite
Liquid heating
eutectic mixture ledeburite

The eutectic mixture is not usually seen in the microstructure, since austenite is not
stable at room temperature and must undergo another reaction during cooling.
There is a small solid solution area to the left of line GH. We know that 1666F
represents the changes in crystal structure of pure iron from F.C.C. iron to B.C.C.
iron. That area is a solid solution of small amount of carbon dissolved in B.C.C. iron and
is called Ferrite.
The diagram shows a third horizontal line HJK, which represents a eutectoid reaction.
The eutectoid point J is at 0.80% carbon and 1333F. Any austenite present must now
transform in to the very fine eutectoid mixture of Ferrite + Cementite called Pearlite.
The equation may be written as

ferrite cementite
Liquid heating
eutectoid mixture pearlite

On the basis of carbon content, iron carbide diagram divides in two parts.

Alloys contain < 2% carbon Steels.

Alloys contain > 2% carbon Cast irons.

Steel < 0.8% carbon Hypo eutectoid steels.

Steel in between 0.8% to 2% carbon Hyper eutectoid steel.

Cast iron < 4.3% carbon Hypo eutectoid Cast irons.

Cast iron > 4.3% carbon hyper eutectoid Cast irons.

6.3 Definition of Structure:

1. Cementite: (Iron Carbide)
Chemical formula Fe3C contain 6.67% carbon by weight.
It is typical hard and brittle interstitial compound of low tensile strength and high
compressive strength.
Its crystal structure is orthorhombic.
2. Austenite:
Austenite is the name given to solid solution.
It is an interstitial solid solution of carbon dissolved in (F.C.C.) iron.
6. The Iron Iron Carbide Equilibrium Diagram Material Science & Metallurgy (2131904)

Maximum solubility is 2% at 2065F (point C).

Fig. 6.4 Austenite

Tensile strength 150000 PSI.
Elongation 10% in 2 inch.
Hardness Rockwell C40 approx.
High toughness.
It is normally not stable at room temperature.
3. Ledeburite:
It is eutectic mixture of austenite and cementite.
It contains 4.3% carbon and is formed at 2065F.
4. Ferrite:
It is the name given to solid solution.
It is an interstitial solid solution of a small amount of carbon dissolved in (B.C.C.) iron.
The maximum solubility is 0.025% carbon at 1333F at point H and it dissolves only
0.008% carbon at room temperature.
It is the soft structure that appears on the diagram.

Fig. 6.5 Ferrite

Tensile strength 40000 PSI.
Elongation 40% in 2 inch.
Material Science & Metallurgy (2131904) 6. The Iron Iron Carbide Equilibrium Diagram

Hardness Less than Rockwell C 0 or Less than Rockwell B 90.

5. Pearlite:
It is the eutectoid mixture containing 0.80 % carbon and is formed at 1333F on very
slow cooling.
It is very fine plate like OR lamellar mixture of ferrite and cementite. The fine finger print
mixture called Pearlite shown in Figure 6.6(c). The white ferritic background or matrix
which makes up most of the eutectoid mixture contains thin plates of cementite. The
same structure magnified, 17000 times with electron microscope shown in Figure 6.6(d).

Fig. 6.6 (c) Pearlite with 2500X (d) Pearlite with 17000X

Tensile strength 120000 PSI
Elongation 20% in 2 inch
Hardness Rockwell C20
Rockwell B 95-100
BHN 250-300

6.4 Carbon Solubility in Iron:

Austenite, being F.C.C. with four atoms per unit cell, represents a much denser packing of
atoms than ferrite, which is B.C.C. with two atoms per unit cell. This is shown by the
expansion that takes place when austenite changes to ferrite on slow cooling. If the iron
atoms are assumed to be spheres, it is possible, from the lattice dimensions and assuming
the distance of closet approach to be equal to the atom diameter, to calculate the amount
of empty space in both crystal structures.
6. The Iron Iron Carbide Equilibrium Diagram Material Science & Metallurgy (2131904)

The calculation shows that the percentage of unfilled space in the F.C.C. lattice is 25%, and
in the B.C.C. lattice 32%. In both austenite and ferrite, the carbon atoms are dissolved
interstitially, that is, in the unfilled spaces of the

Fig. 6.7 Interstices of the B.C.C. (left) and F.C.C. (right).

lattice structure. In view of the above calculations, it may seem strange that the solubility of
carbon in austenite is so much greater than it is in ferrite. This seemingly unusual behavior
may be explained by a study of Fig. 6.7. The largest hole in B.C.C. ferrite is halfway between
the center of the face and the space between the two corner atoms. Two of the four
possible positions for a carbon atom on the front face of a body centered cube are shown in
Fig. 6.7. The largest interstitial sphere that would just fit has a radius of 0.36 (10 -8) cm. The
largest hole in F.C.C. austenite is midway along the edge between two corner atoms. One
possible position for a carbon atom on the front face of face centered cube is shown in Fig.
6.7. The largest interstitial sphere that would just fit has a radius of 0.52 (10 -8) cm.
Therefore, austenite will have a greater solubility for carbon than ferrite. Since the carbon
atom has a radius of about 0.70 (10-8) cm, the iron atoms in austenite are spread apart by
the solution of carbon so that, at the maximum solubility of 2%, only about 10% of the holes
are filled. The distortion of the ferrite lattice by the carbon atom is much greater than in the
case of austenite; therefore, the carbon solubility is much more restricted.

6.5 Slow Cooling of Steel:

Alloy 1 (Figure 6.8) is a hypo eutectoid steel containing 0.20% carbon.
In the austenite range, these alloys consist of uniform interstitial solid solution. Each
grain contains 0.20% carbon dissolved in the space of the F.C.C. iron lattice structure
(Figure 6.8(a)).
Upon slow cooling nothing happen until the line GJ is crossed at point X 1. This line is
known as the upper critical temperature line on the hypo eutectoid side and is labeled
The allotropic change from F.C.C. to B.C.C. iron takes place at 1666F for pure iron and
decrease in temperature with increasing carbon content as shown by the A 3 line.
Therefore at X1, ferrite must begin to form at the austenite grain boundaries (Figure
Material Science & Metallurgy (2131904) 6. The Iron Iron Carbide Equilibrium Diagram

6.8(b)). As the cooling progress and the amount of ferrite increases, the remaining
austenite becomes richer in carbon.

Fig. 6.8 Schematic representation of the changes in microstructure during the slow cooling of 0.2%
carbon steel.
a) Austenite
b) Formation of ferrite grains at austenite grain boundaries.
c) Growth of ferrite grains composition of austenite is now 0.8% carbon
d) Austenite transforms to pearlite at 1333F

Its carbon content is gradually moving down and to the right along the A3 line.
Finally, the line HJ is reached at point X2. This line is known as lower critical temperature
line on the hypo eutectoid side and is labeled A1. The line A1 is the eutectoid
temperature line and is the lowest temperature at which F.C.C. iron can exist under
equilibrium condition
Just above A1, line the microstructure consists of 25% austenite and 75% ferrite (Figure

ferrite cementite
Austenite heating
6. The Iron Iron Carbide Equilibrium Diagram Material Science & Metallurgy (2131904)

Note that it is only austenite which is changing at the A1 line. Therefore when the
reaction is complete the microstructure will show approximately 25% Pearlite and 75%
ferrite (Figure 6.8(d)).

Fig. 6.9 Schematic picture of the formation and growth of pearlite.

Let us consider the eutectoid reaction in a little more detail. Austenite is to change to
ferrite. Austenite is an interstitial solid solution with each remaining grain dissolving 0.8
% C in F.C.C. Fe. Ferrite, however, is B.C.C. Fe and dissolves very little carbon, so the
change in crystal structure cannot occur until the carbon atoms come out of solution.
Therefore, the first step is the precipitation of the carbon atoms to form plates of
cementite (iron carbide). In the area immediately adjacent to the cementite plate the
iron is depleted of carbon, and the atoms may now rearrange themselves to form B.C.C.
ferrite. Thin layers of ferrite are formed on each side of the cementite plate. The process
continues by the formation of alternate layers of cementite and ferrite to give the fine
fingerprint mixture known as pearlite. The reaction usually starts at the austenite grain
boundary, with the pearlite growing along the boundary and into the grain, see Fig.6.9.

Since ferrite and pearlite are stable structures, the microstructure remains substantially
the same down to room temperature and consists of approximately 75 % proeutectoid
ferrite (formed between the A3 and A1 lines) and 25% pearlite (formed from austenite at
the A1 line). Figure 6.10 (a) shows the microstructure of a 0.2 % C steel slow cooled. As
predicted, it consists of 75 % proeutectoid ferrite (light areas) and 25% pearlite (dark
areas). The dark areas in this micro certainly do not look like a mixture, which pearlite is
supposed to be. Higher magnification (Fig.6.10 (b)), however, reveals the fine fingerprint
mixture of pearlite.

The changes just described would be the same for any hypoeutectoid steel. The only
difference would be in the relative amount of ferrite and pearlite. The closer the carbon
content to the eutectoid composition (0.8 % C), the more pearlite will be present in the
microstructure. The microstructure of a 0.4 % C steel slow cooled (Fig.6.10(c)) shows
approximately 50 % pearlite, while the eutectoid composition (0.8 % C) shows 100 %
pearlite (Fig.6.10 (d)).
Material Science & Metallurgy (2131904) 6. The Iron Iron Carbide Equilibrium Diagram

Fig. 6.10 Photomicrographs of (a) 0.20 percent carbon steel, slow cooled,100X;
(b) Same as (a), but at 500X;
(c) 0.40 percent carbon steel, slow cooled, 100X;
(d) eutectoid (0.80 percent carbon)steel, slow
All samples etched with 2 percent nital. Dark areas are pearlite; light are ferrite.

Alloy 2 (Fig.6.11) is a hypereutectoid steel containing 1% carbon. In the austenite range,

this alloy consists of a uniform F.C.C. solid solution with each grain containing 1 %
carbon dissolved interstitially (Fig.6.11(a)). Upon slow cooling nothing happens until the
line CJ is crossed at point x3. This line is known as the upper- critical-temperature line on
the hypereutectoid side and is labeled Acm. The Acm line shows the maximum amount of
carbon that can be dissolved in austenite as a function of temperature. Above the A cm
line, austenite is an unsaturated solid solution. At the Acm line, point x3, the austenite is
saturated in carbon. As the temperature is decreased, the carbon content of austenite,
that is, the maximum amount of carbon that can be dissolved in austenite, moves down
along the Acm line toward point J. Therefore, as the temperature decreases from x3 to x4,
the excess carbon above the amount required to saturate austenite is precipitated as
6. The Iron Iron Carbide Equilibrium Diagram Material Science & Metallurgy (2131904)

cementite primarily along the grain boundaries (Fig.6.11(b),(c)). Finally the eutectoid
temperature line is reached at x4. This line is called the lower critical temperature line
on the hypereutectoid side and is labeled A3,1. Just above the A3,1 line the microstructure
consists largely of austenite, with the excess proeutectoid cementite as a network
surrounding the austenite grains (Fig.6.11(c)). Applying Rule II with cementite on the
right side of the line, the amount of cementite would be
1.0 0.8
% cementite 100 3.4 %
6.67 0.8

and the amount of austenite would be

6.67 1.0
% austenite 100 96.6 %
6.67 0.8

Fig. 6.11 Schematic representation of the changes in microstructure during the slow cooling of a 1.0
percent carbon steel. (a) Austenite; (b) formation of excess cementite at austenite grain boundaries;
(c) growth of excess cementite to form a network austenite composition is now 0.8 percent carbon;
(d)Austenite transforms to pearlite at 1333 F.
Material Science & Metallurgy (2131904) 6. The Iron Iron Carbide Equilibrium Diagram

Fig. 6.12 Photomicrographs of (a) 1 percent carbon steel, slow cooled, 500X;
(b) 1.2 percent carbon steel, slow cooled, 300X.
Pearlite areas surrounded by a white proeutectoid cementite network. Note the increase
in thickness of the cementite network with the increase in carbon content.

The A3,1, line for hypereutectoid steels represents the beginning and the end of the
allotropic change from F.C.C. austenite to B.C.C. ferrite. By the same process described
earlier, the remaining austenite (containing 0.8 % carbon) transforms to the eutectoid
mixture, pearlite (Fig.6.8 (d)). At room temperature the microstructure consists of 96.6
% pearlite (formed from austenite at the A3,1 line) and a network of 3.4 % proeutectoid
cementite (formed between the Acm and A3,1, lines). Look closely at Fig. 6.12(a),
particularly where the pearlite areas meet, to see the thin, white proeutectoid
cementite network. The story just described would be the same for any hypereutectoid
steel, slow cooled. As the carbon content of the alloy increases, the thickness of the
proeutectoid cementite network generally increases. Figure 6.12 (b) shows the
microstructure of a 1.2 % carbon steel. Both photomicrographs show very clearly the
lamellar (platelike) structure of pearlite.
6. The Iron Iron Carbide Equilibrium Diagram Material Science & Metallurgy (2131904)

Note the difference in significance of the upper critical temperature lines, the A3 and
Acm. The former line involves an allotropic change, whereas the latter involves only a
change in carbon solubility.
The mechanical properties of an alloy depend upon the properties of the phases and the
way in which these phases are arranged to make up the structure. Ferrite is relatively
soft with low tensile strength, while cementite is hard with very low tensile strength.
The combination of these two phases in the form of the eutectoid (pearlite) produces an
alloy of much greater tensile strength than that of either phase. Since the amount of
pearlite increases with an increase in carbon content for hypoeutectoid steels, the
strength and Brinell hardness will also increase up to the eutectoid composition of 0.80
% carbon. The ductility, as expressed by percent elongation and reduction in area, and
impact strength decrease with increasing carbon content. Beyond the eutectoid
composition, the strength levels off and may even show a decrease due to the brittle
cementite network. The Brinell hardness, however, continues to increase due to the
greater proportion of hard cementite.
Heat Treatment of Steels

Course Contents
7.1 Heat Treatment & its
7.2 Types of Heat Treatment
7.3 Factors affecting hardening
7.4 Surface Heat Treatment or
Case Hardening
7.5 Austempering or
Isothermal Quenching
7.6 Martempering or Marquenc
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

7.1 Heat Treatment:

Heat treatment is defined as the combination of operations involving heating of metals
or alloys in solid state and cooling it at a suitable rate to obtain the desired properties.
Purpose of heat treatment:
1. Relieving the internal stresses.
2. Refinement of grain size.
3. Improvement of ductility.
4. Increasing hardness or tensile strength.
5. Achieving changes in the chemical composition of metal.
6. Improvement in machinability.
Parameter affects the heat treatment process
1. Temperature
2. Holding time
3. Rate of heating and cooling
All basic heat treating processes for steel involve the transformation or decomposition
of austenite.
Highly stressed materials produced by cold work should be heated more slowly than
stress free materials to avoid distortion.
7.2 Types of Heat Treatment:
1. Full Annealing:
This process consists of heating the steel to the proper temperature and then cooling
slowly through the transformation range. Preferably in the furnace or in any good heat
insulating materials.
1. To refine the grain size
2. Induce softness
3. Improve electrical and magnetic properties
4. Improve machinability
Structure changes:
Aim: We have 0.20% carbon steel (Hypoeutectoid steel) and desired to refine the grain size
by annealing (See Figure 7.1a).

When this steel is heated, no change will occur until A1(lower critical temperature line) is
crossed, when A1 is crossed at that temperature pearlite area will transform to small
grains of austenite by means of eutectoid reactions, but the original large ferrite grains
will remain unchanged (Figure 7.1b). Cooling from this temperature will not refine the
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

Continued heating between A1 and A3 lines will allow the large ferrite grains to
transform to small grains of austenite so that above A3 (upper critical temperature line)
line the entire microstructure will show only small grains of austenite. (Figure 7.1c)

Fig. 7.1 schematic representation of the changes in microstructure during annealing of

0.20% carbon steel
a) Original structure. Coarse grained ferrite and pearlite
b) Just above the A1 line; pearlite has transformed to small grains of austenite, ferrite
c) Above the A3 line ;only fine grained austenite
d) After cooling at room temperature; fine grained ferrite and small pearlite areas.

Subsequent furnace cooling will result in small grains of pro eutectoid ferrite and small
area of coarse lamellar pearlite. (Figure 7.1d) So, proper annealing temperature for hypo
eutectoid steel is approximately 50F above A3 line.
Refinement of the grain size of hyper eutectoid steel will occur about 50F above the
lower critical temperature line (A3, 1). Heating above this temperature will coarsen the
austenite grains which, on cooling will transform to large pearlite areas.
The microstructure of annealed hyper eutectoid steel will consist of coarse lamellar
pearlite areas surrounded by a network of pro eutectoid cementite (Fig.7.2). Because
this excess cementite network is brittle and tends to be a plane of weakness, annealing
should never be a final heat treatment for hyper eutectoid steels. The presence of a
thick, hard grain boundary will also result in poor machinability.
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

Approximate tensile strength of annealed hypo eutectoid steel may be determined by

the proportion of ferrite and pearlite present.
40000percent ferrite 120000percent pearlite
Approximate Tensile Strength =

Example: Annealed 0.2% carbon steel

Approx 25% pearlite

75% ferrite

400000.75 1200000.25
Approximate Tensile Strength =

= 60000 PSI

This same idea cannot be applied to hyper eutectoid steel, since their strength is
determined by the cementite network which forms the continuous phase. The presence
of the brittle network results in a drop in tensile strength above 0.8% carbon (Refer
Table 7.1).

Fig. 7.2 Photomicrographs of (a) 1 percent carbon steel, slow-cooled, 500X;

(b) 1.2 percent carbon steel, slow-cooled, 300X. Pearlite areas surrounded by
a white pro-eutectoid cementite network. Note the increase in thickness of
the cementite network with the increase in carbon content.
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

Table 7.1 Mechanical properties of normalized and annealed steels

2. Spheroidising Annealing:
To improve the machinability and ductility of high carbon steel and air hardening alloy
steel. This process will produce a spheroidal or globular form of carbide in a ferrite

(b) The Spheroidisation of cementite

(c) Microstructure of spheroidised

steel 800X
Fig. 7.3
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

Method to produce spheroidised structure:

1. The first method consists of heating steel to a temperature just below the lower critical
temperature at that temperature for a prolonged period and followed by slow cooling.
2. The second method involves heating and cooling the steel alternately just above and
below the lower critical temperature.
3. The third method consists of heating the steel to a temperature above the lower critical
temperature followed by slow cooling to a temperature below the lower critical
temperature and holding that temperature for a long period.
Structure change:
In this process, no phase change takes place. The lamellar and free cementite in to tiny
spheroids due to surface tension effect. The final structure consists of spheroids of
carbide in a matrix of ferrite.
The degree of spheroidisation depends on the heat treatment temperature and holding
time. More ever fine pearlite coalesces more easily than the coarse pearlite.
1. The micro structure of high carbon steel contains a network of cementite, since the
cementite plates are hard and brittle, the cutting tool cannot cut through this plate and
it is subjected to a continuous shock load. Hence, this type of steel shows poor
machinability. By the Spheroidising process, cementite plates are broken in to tiny
spheroids. This improves the machinability of high carbon steel.
2. During cold forming, lamellar shapes of cementite act as stress raisers and initiate crack
formation. But spheroidal are less conductive stress concentration because of their
rounded shape and prevent the initiation of cracks.

3. Stress Relief Annealing:

Residual stresses are induced during different operations like solidification of casting,
forming, machining, welding, grinding and phase transformation. Steels with residual
stresses fail by stress corrosion cracking under a corrosive environment.
These stresses also enhance the warpage and dimensional in stability in steels.
To eliminate or reduce residual stresses, steel is subjected to stress relief annealing.
Steel is heated uniformly below the lower critical temperature line (1000F to 1250F)
and held at this temperature for a sufficient period of time, followed by uniform cooling.
The magnitude of stress relieved depends on the temperature and holding time.
Structural change:
Since this process is carried out below the lower critical temperature to relieve only
residual stress, no further micro structural changes occur during this process.
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

4. Process Annealing/ Recrystallisation Annealing:

This heat treatment is used in sheet and wire industry .Cold working of steels increase
the hardness and strength but decrease the ductility. Moreover, the grains are deformed
and residual stresses are deformed. So it is necessary to soften the metal to increase the
ductility at the expense of hardness, for further cold working (example wire drawing).
The annealing process employed for this is referred to as Recrystallisation annealing.
The process consists of heating the steel above Recrystallisation temperature or below
lower critical temperature (1000F to 1250F), holding at this temperature for a
particular period of time then followed by cooling.
It depends on the following parameters.
1. Chemical composition
2. Amount of deformation
3. Holding time and initial grain size

Fig. 7.4 Microstructure of (a) Cold worked steel (b) Recrystallised steel
Structural changes:
The final structure after this treatment consists of strain free equipped grains at the
expense of deformation grains. Properly changes produced by cold working are removed
and steel returns very nearly to its original properties.
Therefore, hardness and strength decreases whereas the ductility increases.
Manufacturing in steel wires, sheets or strips.

5. Normalizing:
The purpose of Normalizing is to perform harder and stronger steel than full annealing.
So that for some applications normalizing may be final heat treatment.
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

Normalizing may also be used to improve machinability modified and refine cast
dendritic structure, refine the grain and homogenize the microstructure in order to
improve the response in hardening operations.
Steel is heated to about approximately 100F above upper critical temperature (A 3 or
Acm), hold at that temperature for a sufficient period of time and then cooled in still air.
The increase in cooling rate due to air cooling as compared with furnace cooling affects
the transformation of austenite and resultant microstructure in several ways.
Structural change:
In this process, the homogeneity of austenite increase since the temperature involved is
more than that for annealing. It results in better dispersion of ferrite and cementite in
the final structure. The grain size is finer in the normalized structure then in annealed
one. This results in a slightly higher strength and hardness but lower ductility than full

Fig. 7.5(a) Structural changes during normalizing Fig. 7.5(b) Normalized 0.50% carbon steel,
heated to 1800F and air cooled
Figure 7.5 (b) shows the microstructure of normalized 0.5% carbon steel.
In annealed condition 62% pearlite + 38% proeutectoid ferrite. Due to air cooling this
sample has 10% proeutectoid ferrite which is the white network surrounding the dark
pearlite areas.
For hypereutectoid steel, normalizing will reduce the continuity of proeutectoid
cementite network, and in some cases it may be suppressed entirely.
Since it was the presence of cementite network which reduce strength of annealed
hyper eutectoid steels, normalized steel should show an increase in strength. (Table 7.1)
particularly for steels containing more than 0.8%carbon.
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

Rolled and forged steels possessing coarse grains are subjected to normalizing for grain

Difference between Annealing and Normalizing:

Normalizing Annealing
1. Air cooling 1. Furnace cooling
2. Due to normalizing there is different 2. The furnace imposes identical cooling at
cooling at different locations, hence all the locations so identical properties.
different thickness regions will have
different properties.
3. Micro structure contains less ferrite 3. Microstructure contains less ferrite.
than annealing. Example: 0.5% carbon steel
Example: 0.5% carbon steel 38% ferrite and 62% pearlite
10% ferrite and 90% pearlite
4. Ferrite cementite lamella in pearlite is 4. Ferrite cementite lamellae in pearlite is
fine. coarse.
5. Comparatively higher strength and 5. Comparatively lower strength and
hardness. hardness.
6. Less expensive 6. Here energy is needed and it is time
consuming so treatment is expensive.
7. It improves the machinability of low 7. It improves the machinability of
carbon steel. medium carbon steel.

6. Hardening:
The main purpose of hardening is to develop a high hardness level in components
extended for heavy duty service.
Hardening treatment consist of heating the steel to hardening temperature, holding at
that temperature for a particular time followed by rapid cooling such as quenching in
water, oil, salt bath.
a. Hypo eutectoid steel are heated about 30-50C above the upper critical
temperature line (A3).
b. Hyper eutectoid steel are heated about 30-50C above the lower critical
temperature line (A1).
c. Rapid cooling means the cooling rate is just in excess of the critical cooling rate.
Structure change:
In hypo eutectoid steel, ferrite and pearlite transform to austenite at hardening
temperature. This austenite transforms to martensite on rapid cooling.
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

In hypereutectoid steel, the find structure is blend of cementite and martensite. Since
cementite is harder than the martensite, the wear resistance is better than that
achieved by martensite alone.
Tensile strength and yield strength are improved by hardening structural steel
components like gears, shafts, bearings.
The wear resistance and cutting ability of steel are increased.

7. Tempering:
Hardening treatment develops maximum hardness, excellent wear resistance and high
strength in the steel.
At the same time, it affects property such as ductility and toughness. Hence in hardened
condition steels are generally brittle.
The degree of brittleness increased with increasing carbon content and severity in the
cooling rate.
More ever, high residual stresses are developed due to formation of martensite.
Therefore hardening is always followed by another treatment known as tempering.
The purpose of tempering is to relieve the residual stresses and improve ductility and
toughness of the steel. The grain in ductility and toughness is usually attained at the loss
of hardness and wear resistance.
The process consist of heating the steel below lower critical temperature (typically 150
630 C) followed by cooling in air or at any other desired cooling rate.
Structural changes:
As martensite is a super saturated solid solution, if energy is supplied by tempering, it
decomposes to a two phase microstructure consisting of B.C.C. ferrite and small
particles of carbide.
1. Low temperature tempering about 200C high carbon and low alloy steel
2. Medium temperature tempering about 200 - 400C coil and laminated spring
3. High temperature tempering about 400 - 650C medium carbon steel, shafts,
7.3 Factors affecting hardening process:
1. Hardening temperature:
Hypoeutectoid steel 30-50C above the upper critical temperature line (A3).
Hyper eutectoid steel 30-50C above the lower critical temperature line (A1).
2. Holding time:
Recommended holding time is 1 hour for each 25mm thickness or diameter.
3. Quenching medium:
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

Different industrial quenching media available are water, brine, air, oil, molten
salt bath and synthetic quenchants.
Quenching medium characteristics such as temperature, specific heat, and
thermal conductivity, latent heat of vaporization, viscosity and agitation affect
the cooling+
4. Cooling rate:
The critical cooling rate (CCR) largely depends upon the alloying element. Alloy
steel have less CCR and hence some of alloy steels are hardened by air cooling.
High carbon steels have slightly more CCR and have to be hardened by oil
Medium carbon steels have still higher CCR hence water or brine quenching is
5. Shape and size of steel parts:
Larger parts or parts with variable thickness are heated at a very slow rate
because at a faster cooling rate, thermal gradient is set up between inner and
outer surface or between thick and thin surface.
These parts are held at the hardening temperature for a sufficient period time to
attain a uniform temperature.
The quenching medium contacts the surface of the parts only. So that the ratio of
surface to mass is an important factor in determining the actual cooling rate.
6. Surface condition:
The surface condition of the steel components also affects the hardening
The presence of scale, oil, grease and other foreign particle are not desirable. Oil
and grease burn during the heating and leave behind a residue which is a bad
conduction of heat. These residue, scale or foreign particle result in variable
cooling rates at different points on the surface.
7.4 Surface Heat Treatment or Case Hardening:
Numerous industrial applications require a hard wear resistance surface called the case
and relatively soft, tough inside called core.
Case hardening methods:
1. Carburizing
2. Nitriding
3. Cyaniding or carbo nitriding
4. Flame hardening
5. Induction hardening
The first three method change the chemical composition
Carburizing addition of carbon
Nitriding addition of nitrogen
Cyaniding addition of both
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

Last two methods do not change the chemical composition of the steel. In flame and
induction hardening the steel must be capable of being hardened, therefore the carbon
contain must be about 0.3% or carbon or higher.

1. Carburizing:
Carburizing is a process by which the carbon content of steel is increased.
A low carbon steel, usually about 0.2% carbon or lower is placed in an atmosphere that
contains substantial amount of carbon monoxide.
This process is used for machine parts including cams, pistons, gears, pump shafts etc.
The process consist if heating the steel to a temperature 1700F (900-930C) in contact
with a carburizing medium, holding at that temperature for a sufficient period of time
and cooling it to the room temperature.
As the steel is now in austenite region and the solubility of carbon is more in this region,
the carbon from the medium is diffuses in to austenite (1.2% of carbon at surface).

Fig. 7.6 Pack carburizing

In this method steel components to be carburizing are packed with carburizing medium
in a heat resistance boxes.
The carburizing medium consists of 80% mixture of charcoal coke and 20% barium
carbonate (energizer). The boxes are placed in the furnace and heated to 230C. The
parts are maintained at this temperature until the desired degree of penetration is
1. Barium carbonate decompose on heating
BaCO3 BaO + CO2
2. In the presence of carburizing material, CO2 gives CO
CO2 + C 2CO
3. The main carburizing reaction takes place at the surface of the steel. The carbon
produced is in nascent form and it diffuses in to steel
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

2CO C+ CO2
Fe + (C) Fe(C)
4. The CO2 produced reacts with the carburizing components to form more CO.
CO2 + C 2CO
The depth obtained varies from 1 to 2 mm and carburizing time varied from 6 to 8 hrs.
It does not require the use of prepared atmosphere.
It is efficient and economical for industrial processing of parts in small lots or for large
massive parts.
Not suitable for the production of thin carburized cases.
Close control of surface carbon cannot be achieved.
Liquid carburizing:
Liquid carburizing is also known as salt bath carburizing. The carburizing medium is a
fused salt bath composed of sodium cyanide (Na CN), sodium chloride (NaCl) and barium
chloride (BaCl2). The both are melted in a steel cast pot type furnace heated by oil or
gas. The process is carried out by immersing the steel components n the both
maintained at a temperature of 815 - 900C for a periods varying from 5 min to 1 hrs.
Depending upon the case depth require. The components are then quenched.
The reactions in the salt bath are as follows:

2NaCN + BaCl2 Ba (CN)2 + 2NaCl

Ba (CN)2 BaCN2 + (C)
The carbon atoms dissolve interstially in the steel. A small amount of liberated nitrogen
is also absorbed.

This process gives a thin and clear hardened layer up to a case depth of 0.08 mm. High
temperature salt bath are used for producing a deep case.

Fig. 7.7 Liquid carburizing

7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

Rapid and uniform heat transfer, low distortion, negligible surface oxidation and rapid
absorption of carbon.
Highly uniform case depths are obtained with uniform carbon content.
The cycle time for liquid carburizing is shorter than gas or pack carburizing.
Cyanide salts are extremely poisonous so case is required during its storage and
The salt sticks to the components and must be thoroughly washed after treatment.
Regular checking and adjustment of both compositions is necessary to obtain uniform
case depth.

Gas carburizing:

Fig. 7.8 Gas carburizing

Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

This is most widely used carburizing method for mass production.

The steel is heated in contact with carbon monoxide or hydrocarbon which is readily
decomposed at carburizing temperature. The hydrocarbon may be methane, propane,
natural gas or vaporized fluid hydrocarbon.
Gas carburizing is carried out in an air tight retort furnace capable of maintaining
positive pressure.
The furnace is initially purged (wash out) with a carrier gas consisting of a mixture of CO,
N2 and H2. The furnace operates at the carburizing temperature of 930C.
The components are loaded in basket and lowered in to the furnace, so that a free flow
of gas could pass around them. A fan is suited at the top of the furnace which circulates
and mixes the gas.
When the material reaches the carburizing temperature, methane or propane is added
to maintain specific carbon potential.
During gas carburizing the following reaction takes place:

1. The carbon monoxide in the carrier gas is the active carburizing agent.
2CO CO2 +(C) ------ 1
The carbon thus releases dissolved interstially in to the surface of steel.
2. Methane also release carbon
CH4 2H2 + (C)
3. Carbon dioxide formed in -1 reacts with methane
CO2 + CH4 2H2 + 2CO

The concentration of carbon monoxide is thus maintained, so that carburizing continuous.

Gas carburizing is commonly used to obtain thin carbon between 0.2 0.5 mm.

This method is used for large volume production.
Process provides accurate control of case depth and surface carbon content.
It is cleaner process.
It allows quicker handling by direct quenching.
Less labor cost but highly skilled personnel are required to maintain the necessary

Heat treatment after carburizing:

After carburizing excess cementite (Fe3C) occurs as a network in the case and induce
brittleness. However a case containing 1% or more carbon may be soft at the surface
after quenching due to retention of austenite. Prolonged heating in austenite range
during carburizing introduces a coarse grain to the whole structure.
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

Fig. 7.9 Heat treatment for carburized steel (a) Direct quench
(b) Double heat treatment
The objective of heat treatment after carburizing are:
1. To break the cementite network
2. To achieve higher hardness at the surface
3. To refine the coarse grains of the core and case.
1. Direct quench:
In this method, the components are quenched in a quenching both directly, from the
carburizing temperature and then tempered to reduce the brittleness of the case.
Due to faster cooling from the austenite region, martensite is produced in the surface
and reasonably fine ferrite is produced in the centre. This process is good for only fine
grained steels.
2. Double heat treatment:
If the steel is coarse grained through the cross section then double heat treatment
Steps involved in the process are:
1. Slow cooling from the carburizing temperature to room temperature. This reduces
the residual stresses which in turn reduce the tendency of distortion and cracking.
2. Reheating the steel above upper critical temperature (850 - 900C) and quenching.
Austenite is finer at this temperature and these results in finer ferrite grains at the
core. The additional advantage is that the carbide network also dissolves on heating
and does not appear after quenching.
3. Reheating to a temperature just above the lower critical temperature (750 780C)
and quenching. By this treatment refining and hardening of case are achieved. On
quenching austenite transforms to martensite at the surface of the steel. The core
does not get hardened.
4. Tempering the steel to relive internal stresses and brittleness of the case.
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

2. Carbo nitriding:

Fig. 7.10 Carbo nitriding

Carbonitriding process involves the diffusion of both carbon and nitrogen in to the steel
This process is specifically used for plain carbon steel (0.3 0.4% C) to improve the wear
This process is carried out in a gas atmosphere furnace. The gas mixture consists of
carburizing gas which is a mixture of methane (5%), ammonia (15%) and remaining
natural gas.
The process is performed at a lower temperature in the range if (800 - 870C). The phase
present in steel at this temperature is ferrite and austenite.
The carburizing gas is the source of carbon. Ammonia dissolves to provide nitrogen.
Carbon and nitrogen diffuse simultaneously in to the surface of the steel in the
austenitic ferritic condition.
Nitrogen is more effective in increasing the Hardenability of the case when compared to
After carbo nitriding, quenching is done in oil followed by tempering at 150 - 180C.
The core depth is in the order of 0.05 0.75mm and having hardness approximately 60
65 HRC. The method is applied for bolts, nuts and gears.

It has advantages over carburizing as lower heat treating temperature is required and
less drastic quench is needed. The less drastic quench significantly reduces the
The wear resistance and surface Hardenability are better than carburizing process.
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

3. Cyaniding:

Fig. 7.11 Cyaniding

Cyaniding process involves the diffusion of both carbon and nitrogen in to the surface of
the steel.
This process is used for low carbon steel (0.2%C) and is similar to liquid carburizing
because of the use of cyanide salt bath.
The steel is immersed in a molten salt bath of sodium cyanide heated by immersed
electrodes. The concentration of sodium cyanide varies between 25% and 90%. The
most commonly used concentration is 30%.
The bathe is heated at a temperature between 800 870 C.
The basic reaction in the bath are:
1. Molten cyanide decomposes in the presence of air at the surface of the bath to produce
sodium cyanate.
2NaCN + O2 2NaCNO
2. Sodium cyanate further dissociates to liberate carbon and nitrogen.
4NaCNO Na2CO3 + 2NaCN + CO + 2(N)
2CO CO2 + (C)
Carbon and nitrogen are so formed are absorbed at the surface of the steel. After
cyaniding the process are quenched directly in to oil or water.
The case depth obtained is in the range of 0.025 0.25 mm and surface hardness is up
to 65 HRC. It is used for small parts like nuts, bolts and gears.
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

Process is less time consuming.
Sodium salts are very poisonous, care is required.

This process is not suitable for parts which are subjected to shock, fatigue and impact
because nitrogen addition has an adverse effect on such properties.

4. Nitriding:

Fig. 7.12 Nitriding

In the nitriding process, atomic nitrogen is diffused into the surface of the steel being
This process is more effective for special alloy steel containing aluminum, chromium,
vanadium and molybdenum. These elements form hard and stable nitrides as soon as
they come into contact with nitrogen at the surface of work piece.
Before being nitride, the steel parts are heated to produce the required core property.
The heat treatment is done by heating the steel to 930C, quenching in oil followed by
tempering. All rough and finish machining are carried out before nitriding.
The steel parts are placed in a retort and heated to a temperature of about 550C. At
this temperature ammonia (NH3) gas is allowed to circulate. The ammonia gas
dissociates as follows the equation.
2NH3 2(N) + 3H2
The atomic nitrogen is absorbed by the surface of steel forming nitrides bath with iron
and other elements. The parts are maintained at this temperature for about 40 100
hours according to the core required.
Nitriding does not involve a quench and the parts are slow coated in the retort itself.
Core depth in the range of 0.1 0.5 mm is obtained and hardness up to 1100 VHN.
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

Nitriding is used for air craft engine parts such as cams, cylinder, liners, valve stems,
shaft and piston rings. Nitride steels are more corrosion resistant and have higher
endurance limit than most of the plain carbon carburized steels.
Parts such as gauges, forming dies, bearing parts are surface hardened by nitriding.
During nitriding white layer of Fe4N and Fe2N formed at the outer layer of the surface.
The white layer is brittle and hence has a determintal effect on the fatigue life of
nitirded parts and this is normally removal.
No quenching is required after nitriding, cracking or distortion is unlikely.
A very high surface hardness is obtained. (1100 VHN)
Resistance to corrosion is good.
Fatigue resistance is important advantages.
Hardness is retained up to 500C where as in carburized component hardness begins to
fall at low temperature. (200C)
It is very clean process compared with cyanide bath.
This process is economical only when large number of components is to be treated.
To obtain maximum hardness, special alloy steel has to be used.
The cycle times are long requiring 50 90 hours to produce a maximum case depth of
0.5 0.8 mm.

5. Flame hardening:
Flame hardening and induction hardening do not change the chemical composition of
In this process the surface of the steel is heated by oxy acetylene gas flame to
austenitising temperature followed by a quenching spay. The austenite is transformed to
The steel for flame hardening must have sufficient carbon content (0.3 0.6 %C).

Fig. 7.13 Progressive method of flame hardening, showing the hardness pattern developed.
(From Metals Handbook, Vol.2, American Society for Metals, Metals Park, Ohio, 1964.)
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

Fig. 7.14 Flame hardening (progressive)

Methods of flame hardening:

1. Stationary (Torch and work piece stationary)
2. Progressive (Torch moving, work piece stationary)
3. Spinning (Torch stationary, work piece moving)
4. Progressive spinning (Torch and work piece moving)
In stationary method both torch and work are stationary. This method is used for spot
hardening of small parts such as valve stems, open and wrenches, tip of screw etc.
In the progressive method, the torch moves over a stationary work piece. This is used for
hardening of large parts such as way of lathe bed, teeth of large gears.
In the spinning method, the torch is stationary while the work piece rotates such as
precision gears, pulleys and drums.
In progressive spinning method, in which the torch moved over a rotating work piece. It
is used for surface harden of long circular parts such as shaft and rolls.
In all the procedure, provision must be made for rapid quenching after surface has been
heated to the required temperature.
This may be accomplished by use of water spray, by quenching the entire piece in water
or oil or even air cooling in some steels.
After quenching the parts should be stress relieved by heating in the range of (350 400
F) and air cooled. Such treatment does not appreciable reduce surface hardness.
Hardness zone is much deeper than obtained by carburizing range from (1/8 1/4)
inch in depth. Thinner cases of order of 1/16 can be obtained by increasing the speed
of heating and quenching.

The required area can be hardened.
Large machine surface can be hardened economically.
Ability to treat component offer surface finishing, since there is a little scaling,
decarburization or distortion.
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

The possibility of overheating and thus damaging the parts.
Difficulty is producing hardened zone less than 1/16 in depth.
To obtain optimum results, a technique has to be developed for each design.

6. Induction hardening:

Fig. 7.15 Typical works coils for high frequency units and the heat patterns developed by each.

(From Metals Handbook, Vol.2, American Society for Metals, Metals Park, Ohio, 1964.)

(a) Inductor block with copper coil (b) Electronic circuit

Fig. 7.16 Induction hardening

Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

Due to very fast heating and no holding time, the austenite formed fine and this result in
fine grained martensite.
Induction hardening is normally followed by a low temperature tempering at (160 200
The depth of hardening is controlled by frequency of alternating currents where
(see the Table)
The steels with carbon content 0.4 0.5% are more suitable for this process.

Table 7.2 Effect of frequency on depth of case hardness

Theoretical depth on
Practical depth of case
Frequency, Hz penetration of electrical
hardness, inch
energy, inch
1000 0.059 0.180 to 0.350
3000 0.035 0.150 to 0.200
10000 0.020 0.100 to 0.150
120000 0.006 0.060 to 0.100
500000 0.003 0.040 to 0.080
1000000 0.002 0.010 to 0.030

Crank shaft, cam shaft, axles, gears, rolls, bearing bars, brakes drums, overhead
travelling crane wheels etc.

Fast heating and absence of holding time leads to an increase in production rate.
No decarburization occurs.
Less distortion because the heating is only at the surface.
Easy control over the depth of hardening by control of frequency of supply voltage and
time of holding.

Because of the cost of the equipment, the process is not suitable for small scale
Irregular shaped parts cannot be handled economically.
High maintenance cost.

7.5 Austempering or Isothermal Quenching:

Austempering is a hardening process. The purpose of Austempering is either to reduce
the tendency towards distortion and cracking during conventional quenching or to
improve the ductility and toughness while maintaining the hardness.
7. Heat Treatment of Steels Material Science & Metallurgy (2131904)

Fig. 7.17 Austempering

Steel is heated above austenitising temperature and then quenched in a bathe
maintained at a temperature just above Ms temperature within the bainitic region
(between 400 800F) 200 400 C in general. It is held at that temperature in the salt
bath for a sufficient period of time until the all the austenite is transformed in to bainite.
Since the transformation occurs at a constant temperature, this process is known as
isothermal hardening.
After complete transformation the steel is taken out of the bath and cooled to room
temperature by any desired rate.
Structural changes:
Depending on the transformation temperature the structure could be upper bainite or
lower bainite. But the lower bainite is preferable as it has better mechanical properties
than tempered martensite.
Austempering is applied for heat treating components of intricate sections. Such
components might distort or crack when they are treated by the conventional quench
hardening. This is avoided in Austempering.

7.6 Martempering or Marquenching:

It is also a hardening process. The purpose of martempering is similar to Austempering.
Martempering steels have fewer tendencies to crack, distort and develop residual
stresses during heat treatment.
Material Science & Metallurgy (2131904) 7. Heat Treatment of Steels

Fig. 7.18 Martempering

In this process the steel is heated to austenitising temperature. It is then quenched in a
constant temperature bath (180 250 C) maintained above Ms temperature. It is held
in this bath until the temperature is uniform through the part. Then it is removed the
bath and cooled in air.
This process removes most of the quenching stress.
Structure changes:
During cooling in air, the structure obtained is martensite. The steel is generally
tempered in order to improve the property.
This process is more suitable for high carbon steel and alloy steel.
Alloy Steels

Course Contents
8.1 Plain Carbon Steel
8.2 Alloy Steel
8.3 Popular Alloy Steel
8.4 Tool Steel
8.5 Stainless Steel
Material Science & Metallurgy (2131904) 8. Alloy Steels

8.1 Plain carbon steel:

Plain carbon steel is an alloy of iron and carbon and it is malleable.
Carbon steel are different from cast iron regarding % of carbon
Carbon steel : 0.10 to 1.50 % carbon
Cast iron : 1.80 to 4.20% carbon
Types of steel:
1. Low carbon steel (Mild steel).
2. Medium carbon steel.
3. High carbon steel.
1. Low Carbon Steel:
A) Dead mild steel:
Carbon: 0.05 0.15 %.
Application: steel wire, sheets, rivets, screw, pipe, chain.
Tensile strength 390 N/mm2 and hardness 115 BHN.
B) Mild steel:
Carbon: 0.15 0.20 %.
Application: cam shaft, fan, blades, welded tubing, drag lines.
Tensile strength 420 N/mm2 and hardness 125 BHN.
C) Mild steel:
Carbon: 0.20 - 0.30%.
Application: gears, crankshaft, connecting rod, railway axle, forging components etc.
Tensile strength 555 N/mm2 and hardness 140 BHN.
Carbon : 0.3-0.70 %
Steel with carbon 0.35-0.35% having tensile strength 750 N/mm2
Application: connecting rods, gear shaft, spring clips, axles, small and medium forging
Steel with carbon 0.45- 0.55% having tensile strength 1000 N/mm2
Application: axles, spline shaft, railway coach, crankshaft
Steel with carbon 0.60-0.70% having tensile strength 1230 N/mm2 and hardness 400-450
Application: die blocks, punch plate, drop forging dies, valve springs, set screws, self
tapping screw etc.
Carbon: 0.7 1.5%
Steel with carbon 0.70 - 0.80 % having tensile strength 1400 N/mm2 and hardness 450-
500 BHN.
Application: cold chisels, pneumatic drill, wrenches, jaw of vices, wire for structural
work, shear blades etc.
8. Alloy Steels Material Science & Metallurgy (2131904)

Steel with carbon 0.80 - 0.90 % having tensile strength 660 N/mm2 and hardness 500-
600 BHN.
Application: rock drill, railway rails, machine chisels, punch and dies, leaf spring, music
wire etc.
Steel with carbon 0.90 - 1.0 % (high carbon tool steel) having tensile strength 580
N/mm2 and hardness 500-600 BHN.
Application: punch and dies, springs, shear blades, keys etc.
Steel with carbon 1.0 - 1.1 %
Application: machine tool, tap, mandrels, railway spring etc.
Steel with carbon 1.1 - 1.2 %
Application: tap, thread metal die, twist drill etc.
Steel with carbon 1.2 - 1.3 %
Application: file, reamer, metal cutting tool etc.
Steel with carbon 1.3 - 1.5 %
Application: wire drawing dies, tools for turning chilled iron, metal cutting saws etc.

8.2 Alloy steel:

Plain carbon steels are very satisfactory when strength and other requirements are not
too serve.
They are also used successfully at ordinary temperature and in atmosphere that are not
highly corrosive but their relatively low hardenability limits the strength that can be
obtained except in firmly thin sections.
Most of limitations of plain carbon steels may be overcome by the use of alloying

Steel is considered to be alloy steel when the maximum of the range given for the
content of alloying elements exceeds one or more of the following limits:

Manganese : 1.65% (In plain carbon steel upto 0.90%)

Silicon : 0.60% (In plain carbon steel upto 0.30%)
Copper : 0.60%

OR in which a definite range OR a definite maximum quality of any of the following

elements is specified OR required within the recognized field of constructional alloy steel
Al, B, Cr up to 3.99 % , Co, Mo, Ni, Ti, W, V or other alloying element added to obtain a
desired alloying effect.
Alloying elements alter the properties of steel and put it into slightly different class from
ordinary carbon steel.
Material Science & Metallurgy (2131904) 8. Alloy Steels

Purpose of alloying:
1. Increase hardenability.
2. Improve strength of ordinary temperature.
3. Improve mechanical properties at high or low temperature.
4. Improve toughness at any minimum hardness or strength.
5. Increase wear resistance.
6. Increase corrosion resistance.
7. Improve magnetic properties.

Effect of alloying elements:

1. Carbon:
Carbon content in steel effects in hardness, tensile strength, machinability, and melting
2. Nickel:
Nickel increase toughness and resistance to impact.
Lessens distortion in quenching.
Lowers the critical temperature of steel and widens the range of successful heat
Strengthens steels.
Does not unite with carbon.
3. Chromium:
Joins with carbon to form chromium carbide, thus adds to depth hardenability with
improved resistance to abrasion and wear.
4. Silicon:
Improve oxidation resistance.
Strengthens low alloy steels.
Act as a deoxidizer.
5. Titanium:
Prevents localized depletion of chromium in stainless steels during long heating.
Prevents formation of austenite in high chromium steels.
Reduce martensite hardness and hardenability in medium chromium steels.
6. Molybdenum:
Promotes hardenability of steel.
Make steel fine grained.
Makes steel unusually tough at various hardness levels.
Counteracts tendency towards temper brittleness.
Raise tensile and creep strength at high temperatures.
Enhance corrosion resistance in stain less steel.
Forms abrasion resisting particles.
7. Vanadium:
Vanadium (0.15-0.5%) added to steel.
8. Alloy Steels Material Science & Metallurgy (2131904)

Is a powerful carbide former.

Stabilizers cementite and improves the structure of the chill.
Promotes fine grains in steel.
Increase hardenability.
Imparts strength and toughness to heat treated steel.
Causes marked secondary hardening.
8. Tungsten:
Increase hardness.
Promotes fine grain.
Resists heat.
Promotes strength at elevated temperature.
9. Manganese:
Contributes markedly to strength and hardness.
Counteracts brittleness from sulpher.
Lowers both ductility and weldability if it is present in high percentage with high carbon
content in steel.
10. Copper:
Copper (0.2-0.5%) added to steel.
Increase resistance to atmospheric corrosion.
Acts as strengthening agent.
11. Boron:
Increase hardenability or depth to which steel will harden when quenched.
12. Aluminium:
Acts as a deoxidizer.
Produces fine austenitic grain size.
If present in an amount of 1% it helps promoting nitriding.
13. Cobalt:
Improves mechanical properties such as tensile strength, fatigue strength and hardness.
Refines the graphite and pearlite.
Is a mild stabilizer of carbides.
Improves heat resistance.
Retards the transformation of austenite and thus increases hardenability and freedom
from cracking and distortion.

8.3 Popular Alloy Steel:

1. Nickel steel:
It contains
Carbon: 0.35% Nickel: 3.5%
Addition of nickel to structural steel results in an increase of strength, without a
proportionality great decrease of ductility.
Material Science & Metallurgy (2131904) 8. Alloy Steels

Nickel steels are used for storage cylinder for liquefied gases and other low temperature
Other use of nickel steels are heavy forging, turbine blades, high stressed screw, bolts
and nuts (40 Ni 3 steel).
2. Chromium steel:
Chromium is less expensive alloying element than nickel and forms simple carbide
(Cr7C3, Cr4C) or complex carbides [(FeCr)3C].
These carbides have high hardness and good wear resistance.
It increases tensile strength and corrosion resistance of low alloy steel.

% Of Cr in Steel Use
8 Electrical use
15 Spring ball and roller bearing

3. Nickel- Chromium steel:

Chromium nickel steel combines the effect of nickel (Increasing toughness and
ductility) and chromium (Improving hardenability and wear resistance).
The low carbon nickel chromium alloy steel are carburized. The chromium supplies the
wear resistance to the case, while both alloying element improves toughness.
With 1.5% nickel and 0.6% chromium steel is used for worm gears and piston pins etc.
With 3.5% nickel and 1.5% chromium steel used as heavy duty applications such as air
craft gears, shafts, cams etc.
Medium carbon nickel chromium steels are used in the manufacture of automotive
connecting rods and drive shafts.
4. Molybdenum steel:
Molybdenum is a relatively expensive alloying element.
Molybdenum has a strong effect on hardenability and increase high hardness and
strength of steels.
The plain molybdenum steel with low carbon content are generally carburized and used
for alpine shaft and transmission gears.
With higher carbon they are used for automotive coil and leaf springs.
Chromium molybdenum steels are relatively cheap and posses good deep hardening
characteristics, ductility and weldability. They have been used for pressure vessels,
aircrafts, structural parts, automobile axles and other applications.
Nickel molybdenum steel have the advantage of the high strength and ductility from
nickel combined with deep hardening and improved machinability by molybdenum.
They have good toughness combined with high fatigue strength and wear resistance.
Application: gear, chain, pins, shafts, bearing etc.
8. Alloy Steels Material Science & Metallurgy (2131904)

Nickel chromium molybdenum steels are used for the structural parts of wings
assembly and loading gears.

8.4 Tool steel:

Tool steel is defined as special steel used for cutting or forming purpose.

1. According to quenching media
a. Water hardening steel.
b. Oil hardening steel.
c. Air hardening steel.
2. According to alloy content
a. Carbon tool steel.
b. Low alloy tool steel.
c. Medium alloy tool steel.
3. According to application
a. Hot work steel.
b. Shock resisting steel.
c. High speed steel.
d. Cold work steel.

AISI suggest group and symbol of tool steel:

Group Symbol & Type

Water hardening W
Shock resisting S

O Oil hardening
Cold work A Medium alloy air hardening
D High carbon, High chromium

H : H1 H19 Chromium base

Hot work H20 H39 Tungsten base
H40 H59 Molybdenum base

T Tungsten base
High speed
M Molybdenum base
Mold P Mold steel
L Low alloy
Special purpose
F carbon-tungsten
Material Science & Metallurgy (2131904) 8. Alloy Steels

Application of tool steel:

Cutting tool like drill, tape reamer etc. (multi cutting tool).
Shearing tool use for shear, punch and blanking die.
Drawing and extrusion die.
Thread rolling die.
Single cutting tool in lathe and planning machine.

High speed tool steel:

These steels are the most highly alloyed of the tool steel usually contain large amount of
tungsten or molybdenum along with chromium, vanadium and sometimes cobalt.
Carbon content varies from 0.7 1.0% and sometimes up to 1.5%.
Application of high speed steel is for cutting tools also they are used for making
extrusion dies, burnishing tools and blanking punches and dies.

Excellent red hardness (tool can operate at high temperature).
Good shock resistance.
Good non deforming properties.
Good wear resistance.
Fair machinability.
Fair to poor resistance to decarburization.

1. Molybdenum base (Group M).
2. Tungsten base (Group T).
Tungsten base is known as 18 4 1
18% tungsten, 4% chromium, 1% vanadium.
Molybdenum base is known as 6 6 4 2
6% molybdenum, 6% tungsten, 4% chromium, 2% vanadium.
Molybdenum steel is lower in price, so over 80% of H.S.S. is produced of molybdenum
type steel.
When better than average red hardness is required, steel containing cobalt is
Higher vanadium content is desirable when the material cut is highly abrasive.
In T-15 steel, a combination of cobalt and vanadium provides red hardness and abrasion
Application: cutting tools such as tool bits, drills, reamers, broaches, milling cutters,
hobs, saws, wood working tools etc.

8.5 Stainless steels:

Concept: When 11.5% or more chromium is added to iron, a fine film of chromium oxide
forms spontaneously on the surface exposed to air. The film acts as a barrier to retard
8. Alloy Steels Material Science & Metallurgy (2131904)

further oxidation, rust or corrosion. As these steel cannot be strained easily it is called
stainless steel.
A three numerical numbering system is used to identify stainless steel. The last two
numbers have no particular significance but the first numerical indicates the group as

Series Designation Groups

2XX Chromium, nickel manganese, non hardenable,

austenitic, non magnetic
3XX Chromium nickel, non hardenable, austenitic,
non magnetic
4XX Chromium, hardenable, martensitic, magnetic
4XX Chromium, non hardenable, ferritic, magnetic
5XX Chromium, low chromium, heat resisting

1. Martensitic stainless steel:

These steels are primarily straight chromium steel containing 11.5 18% chromium.
Example: 403, 410, 416, 420, 440, 501 and 502.
410 and 416 are most popular alloys in this group and used for turbine blades and
corrosion resistant casting.
Martensitic stainless steel is identify by their martensitic microstructure in hardened
Heat treatment process for martensitic steel is same as for plain carbon or low alloy
steel where strength and hardness depends upon carbon content.
These steels are magnetic in all conditions and possess the best thermal conductivity of
the stainless steel types.
Application: springs, machine parts, pumps, shafts, ball bearings, air craft fittings, valve
parts, and surgical instruments.
2. Austenitic stainless steel:
These are chromium nickel stainless steel (type 3XX) and chromium nickel
manganese stainless steel (type 2XX).
These types are austenitic and non magnetic in annealed condition and do not harden
by heat treatment.
They can be hot worked and cold worked.
Extremely shock resistance and difficult to machine (303, 303E).
Best high temperature strength and resistance to scaling of the stainless steel.
Corrosion resistance of austenitic steel is usually better than that of martensitic or
ferritic steels.
Material Science & Metallurgy (2131904) 8. Alloy Steels

Application: air craft industries, chemical processing industries, food processing

industries, house hold items, transportation industries.
3. Ferritic stainless steel:
This group of straight chromium stainless steels contains approximately 14 27%
chromium and includes types 405, 430 and 446.
Low in carbon content and higher in chromium than martensitic grades.
Not hardened by heat treatment.
They are magnetic and can be cold work or hot worked but they develop their maximum
softness, ductility and corrosion resistance in the annealed condition.
The only heat treatment applied to truly ferritic steel is annealing. This treatment serves
primarily to relieve welding or cold working stresses.
Application: lining for petroleum industries, heating element for furnaces, interior
decorative work, screws and fitting, oil burner parts.
8. Alloy Steels Material Science & Metallurgy (2131904)

Cast Iron

Course Contents
9.1 Introduction
9.2 Classification Of Materials
9.3 Pig Iron
9.4 Wrought Iron
9.5 Cast Iron and Types
9.5.1 Gray Cast Iron
9.5.2 Malleable Cast Iron
9.5.3 Nodular Cast Iron
9.5.4 White Cast Iron
9.5.5 Chilled Cast Iron
9.5.6 Alloy Cast Iron
Material Science & Metallurgy (2131904) 9. Cast Iron

9.1 Introduction:
Ferrous materials contain iron.
Ferrous materials are the most important metals/ alloys in the metallurgical and
mechanical industries because of their very expensive uses.

9.2 Classification of Materials:

9.3 Pig Iron:

Pig iron is the raw material for all iron and steel product. Pig iron is of great importance
in the foundry and steel making industry.
Pig iron for foundry is roughly 20X9X4.
Raw material for pig iron is ore. (Iron oxide or carbonate lime stone and coke).
Pig iron produced in blast furnace, is the first product in the process of converting iron
ore into useful metal.
Iron ores are rocks and minerals from which metallic iron can be economically extracted.
The iron ore becomes pig iron which the impurities are burned out in a blast furnace.
Though, still containing some impurities, pig iron has a high metal content.
Pig iron the product of blast furnace has following composition.

Carbon : 3.0-4.0% Phosphorous : 0.3-1.7%

Silicon : 1.0-3.0% Manganese : 0.1-1.0%
Sulpher : Under 1.0% Iron : Remaining
9. Cast Iron Material Science & Metallurgy (2131904)

1. Pig iron partly refined in a cupola produces various grades of cast iron.
2. By pudding process, wrought iron is produced.
3. Steel is produced from pig iron by various steel making process such as Bessemer, open
hearth, oxygen, electric and spray steel making.

Classification of Pig iron:

1. Basic pig iron:
It is used for steel making and is low in silicon (1.5% maximum) to prevent attack of the
refractory lining of refining furnaces.
Basic pig iron must be low in Sulpher (0.04% minimum). Since Sulpher is an active
impurity in steel and is not eliminated in the refining furnaces.
Phosphorous : <1.0%
Manganese : 1.0-2.0%
Carbon : 3.5-4.4%
2. Foundry pig iron:
It is used for the production of casting.
It contains
Carbon : 3.0-4.5% Phosphorous : 0.035-0.9%
Silicon : 0.5-3.5% Manganese : 0.4-1.25%
Sulpher : Upto 0.05% Iron : Remaining
3. Ferroalloys:
Ferroalloys are of pig iron, each rich in one specific element.
They are used as additives in iron and steel industries to control or alter the properties
of iron and steel.
Ferrosilicon(FeSi) : Which is pig iron with 5 to 17 % silicon
Ferromanganese(FeMn): Which is pig iron with 74 to 82 % manganese
Other examples like SiMn, AlMn and CaSi etc.
Material Science & Metallurgy (2131904) 9. Cast Iron

9.4 Wrought Iron:

Wrought iron is a mixture of very pure iron and silicate slag.
Wrought iron was originally produced by hand pudding process later by mechanical
pudding and since 1930 by Bayer or Aston process. There are 3 steps for the
manufacturing of wrought iron.
1. To melt and refine the base metal.
2. To produce and keep molten a proper slag.
3. Disintegrate the base metal and mechanically incorporate with it the desired amount
of slag.

Fig. 9.1 Wrought Iron

Properties of wrought iron:

Quality wrought iron is distinguished by its low carbon and manganese content.
Carbon is generally below 0.08% and manganese content below 0.06%.
Phosphorous is higher than that of steel and ranges from 0.05 to 0.160%.
Sulpher content is kept low and silicon content 0.10 to 0.20% is concentrated almost
entirely in the slag.
The slag content usually varies about 1.0 to 3.0% by weight.
A typical chemical analysis of wrought iron is as under.

Carbon : 0.6% Sulpher : 0.009%

Silicon : 0.101% Slag by weight : 1.97%
Phosphorous : 0.068% Iron : Balanced
Manganese : 0.045%

Wrought iron is a composite metal. Figure shows the fracture of wrought iron.
The mechanical properties of wrought iron are largely those of pure iron. Because of
nature of slag distribution the tensile strength and ductility are greater in longitudinal
9. Cast Iron Material Science & Metallurgy (2131904)

It has ability to resist corrosion. As corrosion continues the slag fibers begin to function
as rest resistors.
Wrought iron is never cast. All shaping is accomplished by hammering, pressing and
It is possible to improve the strength of wrought iron by alloying. The most popular alloy
wrought irons are those containing 1.5 to 3.5% nickel.
Tensile properties of wrought iron.

Property Longitudinal Transverse

Tensile strength in PSI 48000-50000 36000-38000

Yield strength in PSI 27000-30000 27000-30000

% Elongation in 8 inch 18-25 2-5

Reduction in area % 35-45 3-6

Tensile properties of unalloyed and nickel wrought iron.

Property Unalloyed Wrought Iron Nickel Wrought Iron

Tensile strength in PSI 48000 60000

Yield strength in PSI 30000 45000

% Elongation in 8 inch 25 22

Reduction in area % 45 42

Application of wrought iron:

Wrought iron is available in the form of plates, sheets, bars, forging blooms and billets,
rivets and wide range of tubular products like pipe, tubing and casing cold drawn tubing
and welding fittings.
1. Building construction : Service lines and electrical conduits, soil, waste.
2. Public work : Bridge, railing, blast plates, towers etc.
3. Industrial : Condenser tubes, heat exchangers, acid and alkali process
4. Rail road and marine : Diesel exhaust and air brake piping.
5. Others : Coal handling equipments, cooling towers, spray pond piping.
Material Science & Metallurgy (2131904) 9. Cast Iron

9.5 Cast Iron:

Cast iron is basically alloy of iron and carbon. Cast iron contains 2.0-6.67% carbon. Since
higher carbon content tends to make the cast iron very brittle.
Most common commercial manufactured cast iron is in the range if 2.5 to 4.0% carbon.
The ductility of cast iron is very low, and it cannot be rolled, drawn or worked at room
temperature. Cast iron melts readily and can be cast into complicated shapes which are
usually machined into final dimensions.
The common cast iron is brittle and has lower strength property than most steel.
In addition by proper alloying, good foundry control and appropriate heat treatment the
property of cast iron may be varied over a wide range.

Types of Cast Iron:

The best method of classifying cast iron is according to metallographic structure.
There are four variables for types of cast iron.

1. Carbon content.
2. The alloy and impurity content.
3. Cooling rate during and after freezing.
4. Heat treatment after casting.

These variables control the conclusion of carbon and its physical form. The carbon may
be combined as iron carbide in cementite or free carbon in graphite. The shape and
distribution of free carbon particles will influence the physical property of cast iron.

1. Gray cast iron : Most of or all the carbon is uncombined in the form of graphite flanks.
2. White cast iron : All the carbon is in the combined form as cementite.
3. Malleable cat iron: All the carbon is uncombined in the form of irregular round particle
known as temper carbon. This is obtained by heat treatment of white cast iron.
4. Chilled cast iron: In which white cast iron layer at the surface is combined with gray cast
iron interior.
5. Nodular cast iron: In which by special alloy addition the carbon is largely uncombined in
the form of compact spheroids.

This structure offers from malleable iron is that it is obtained directly from solidification
and round carbon particles are more regular in shape.

9.5.1 Gray Cast Iron:

A low cost material that can be used for many purpose. Available to the foundry as virgin
and selected scrap.
9. Cast Iron Material Science & Metallurgy (2131904)

Fig. 9.2 Graphite flakes in gray cast iron

Mechanical properties:
1. High compressive strength.
2. Low tensile strength.
3. High rigidity.
4. High stability after weathering.
Casting properties:
1. High fluidity and ability to male sound casting.
2. Relatively low melting temperature 1130 - 1250 C.
Easily machined to a good finish once the skin has been removed forms a discontinuous
Special properties:
1. Self damping does not vibrate.
2. Self lubricating.
3. Good anti friction properties.
1. Gray cast iron basically an alloy of carbon and silicon with iron.
2. It is readily cast into desired shape in a sand mold.
3. It contains

Carbon : 2.5-3.8% Manganese : 0.4-1.0%

Silicon : 1.1-2.8% Sulpher : 0.1%
Phosphorous : 0.15%
4. It is marked by the presence of graphite flankes in a matrix of ferrite or pearlite.
5. Graphite flankes occupy 10% of metal volume.
6. Length of flankes may vary from 0.05 to 0.1 mm.
7. When fractured a bar of gray cast iron gives gray appearance.
Material Science & Metallurgy (2131904) 9. Cast Iron

8. It contain lowest melting point of ferrous alloys.

9. It possess high fluidity and hence it can be cast into complex shapes and thin sections.
10. It possess better machinability then steel.
11. It has high resistance to wear.
12. It possess high vibration damping capacity.
13. It has low ductility and low impact strength as compare to steel.
14. Gray cast iron has solidification range of 2400 -2000 F
15. It has shrinkage of 1/8 inch/foot.(1mm/100mm)
16. It associated low cost combined with hardness and rigidity.
17. It possess high compressive strength.

Machine tool structure (bed, frame and details).
Gear housing, pump housing, system turbine housing.
Motor frame.
Gas or water pipe for underground purpose.
Manhole cover.
Cylinder blocks and heads for IC engines, piston rings.
Tunnel segments.
Sanitary wares.
Rolling mills and general machinery parts.
Household applications.

9.5.2 Malleable cast iron:

The purpose of malleabilisation is to convert all combine carbon (Fe3C) in white iron into
irregular nodules of temper carbon (graphite) and ferrite. Commercially, this process is
carried in two steps known as I and II steps of annealing.

1. Malleable cast iron is one which can be hammered and rolled to obtain different shapes.
2. Malleable cast iron is obtained from hard and brittle white iron through controlled heat
conversion process.
3. a) A ferritic malleable cast iron has ferrite matrix.
b) A pearlitic malleable cast iron has pearlite matrix.
c) An alloy malleable cast iron contains chromium and nickel and possesses high
strength and corrosion resistance.
4. Malleable cast iron possesses high yield strength.
5. It has high youngs modulus and low co-efficient of thermal expansion.
6. It possesses good wear resistance and vibration damping capacity.
7. It has shrinkage 1.5mm per 100mm.
8. It has low moderate cost.
9. Cast Iron Material Science & Metallurgy (2131904)

Fig. 9.3 a) Malleable iron unetched, irregular nodules of graphite called temper carbon
b) Ferritic malleable iron, temper carbon (black) in ferritic metrix. Etched in 5% natal

9. Chemical composition of malleable cast iron is

Carbon : 2.0-3.0% Manganese : 0.25-0.55%

Silicon : 0.6-1.4% Sulpher : 0.05%
Phosphorous : less than 0.18%

Tensile properties of malleable cast iron:

Tensile strength Yield strength Elongation
Type BHN
1000 PSI 1000 PSI % in 2 inch
Ferritic 50-60 32-39 20-10 110-145
Pearlitic 65-120 45-100 16-20 163-269

Axle and differential housing, cam shaft and crank shaft in automobiles.
Gears, chain link, sprockets, elevator brackets in conveyor equipments.
Pumps, nozzles, cam, rocker arms as machine parts.
Gun mounts, tank parts, pistol parts etc and hammers wrenches etc.

9.5.3 Nodular cast iron:

Nodular cast iron is known as ductile iron or spheroidal cast iron, which is cast iron in
which graphite is present as a spheroids or tiny balls.
Material Science & Metallurgy (2131904) 9. Cast Iron

The compact spheroids interrupt the continuity of matrix much less than graphite flanks
these results in higher strength and toughness compare with similar gray iron.
Nodular cast iron differs from malleable iron in that it is usually obtained as a result of
solidification and does not require heat treatment. The spheroids are more rounded
than the irregular aggregates of temper carbon found in malleable iron.
The total carbon content of nodular iron is the same as in gray cast iron.
Spheroidal graphite particles form during solidification because of the presence of small
amount of alloying element.
The nodule forming addition, usually magnesium or cerium is made to the laddle just
before casting. Since these elements have strong affinity for sulpher the base iron alloy
sulpher content must be below 0.015% for the treatment to be effective and the alloy
are described as desulphurised.
The amount of ferrite in the cast matrix depends on composition and rate of cooling.
Nodular iron with matrix having a maximum 10% pearlite is known as ferritic iron. This
structure gives maximum ductility, toughness and machinability.
A matrix structure which is largely pearlite can be produced as cast or by normalizing.
A martensite matrix may be obtained by quenching in oil or water from 1600-1700 F.
The quenched structure is usually tempered after hardening to the desired strength and
hardness levels.
Austenitic ductile irons are highly alloyed types which retain their austenitic structure
down to at least -75 F. These irons are of interest because of their high corrosion
resistance and good creep properties at elevated temperature.
Chemical composition:
Carbon : 3.2-4.2% Manganese : 0.3-0.8%
Silicon : 1.1-3.5% Sulpher : 0.2%
Phosphorous : 0.08%

(a) (b)
Fig. 9.4 a) Nodular iron unetched, showing spheroids.
b) Ferritic nodular iron showing graphite spheroids n a ferrite matrix, etched in 2% nital.
9. Cast Iron Material Science & Metallurgy (2131904)

Agricultural: Tractor and implement parts.
Automotive and diesel: Crank shaft, piston and cylindrical head.
Electrical fittings: Switch box, motor frame, circuit breaker parts.
Mining: Hoist drums, drive pulley, flywheel and elevator bracket.
Steel mill rolls.
Furnace doors.
Bearings, tools and dies, wrenches.
Miscellaneous dies for shaping steel, aluminium, bronze and titanium.

9.5.4 White cast iron:

The typical microstructure of white cast iron consists of dendrities of transformed
austenite (pearlite) in which interdendritic network of cementite. Higher magnification
of some sample reveals that the dark areas are pearlite.
Cementite is a hard, brittle interstitial compound. Since white cast iron contains a
relatively large amount of cementite as continuous interdendritic network, it makes the
cast iron hard and wear resistance but extremely brittle and difficult to machine.
White cast irons are limited in engineering applications because of brittleness and lack
of machinability

Fig. 9.5 white cast iron

Examples: liners for cement mixers, ball mills, drawing dies, extrusion nozzles.
It is used as a starting material for the manufacturing of malleable cast iron.
Its freshly broken surface shows bright white fracture.
It contains
Material Science & Metallurgy (2131904) 9. Cast Iron

Carbon : 1.8-3.6% Manganese : 0.2-0.8%

Silicon : 0.5-2.0% Sulpher : 0.1%
Phosphorous : 0.18%

Shrinkage is 1mm per 100mm.

Mechanical properties
BHN : 375-600
Tensile strength : 20000-70000 PSI
Compressive strength : 200000-250000 PSI
Modulus of elasticity : 24-28 million PSI

9.5.5 Chilled cast iron:

Chilled cast iron is obtained by casting the molten metal against a metal chiller, resulting
in a surface of white cast iron.

Fig. 9.6 Fracture of chilled iron casting showing the white, mottled and gray portions

This hard abrasion-resistant white cast iron surface of core is baked up by a soft gray
iron core. This core structure is obtained by careful control of overall alloy composition
and adjustment of cooling rate.
Freezing starts first, and the cooling rate is most rapid where the molten metal is in
contact with mould walls. The cooling rate decreases as the centre of casting is
approached. A chilled cast iron may be produced by adjusting the composition of the
iron so that the normal cooling rate at the surface is just enough to produce white iron
while the slower cooling rate below the surface will produce gray iron.
9. Cast Iron Material Science & Metallurgy (2131904)

Chromium 1-4% is used in small amount to control chill depth. It increase hardness and
abrasion resistance.

Railway car wheels.
Crushing rolls.
Stamp shoe and die.
Heavy duty machine parts.

9.5.6 Alloy cast iron:

An alloy cast iron is one in which contain specially added element to produce
measurable modification in the physical or mechanical properties.
Alloying elements may be silicon, manganese, sulpher, phosphorous, chromium, copper,
nickel and vanadium.
Alloying elements are added to cast iron for special properties such as; Resistance to
corrosion, heat and wear resistance, improve mechanical properties etc.
Chromium increases combined carbon by forming complex iron-chromium carbides that
are stable than iron carbides. Small amount of chromium increases strength, hardness,
depth of chill and resistance to wear and heat but decreased machinability.
Copper is graphitizer. Copper content is 0.25-2.5%. Copper tends to break up massive
cementite and strength than the matrix.
Molybdenum improves mechanical properties and ranges from 0.25- 1.25%. It increases
fatigue strength, tensile strength, heat resistance and hardness and hardenability.
Vanadium is a powerful carbide former and ranges from 0.1-0.25%. It increases tensile
strength, transverse strength and hardness.
Nickel is a graphitizer. The purpose of nickel (0.5-0.6%) in engineering gray iron is to
control the structure by retarding austenite transformation, stabilizing pearlite and
maintaining combined carbon at eutectoid quality.
For excellence abrasion resistance about 4% nickel in combination with 1.5% chromium
is added to white cast iron. Hardness 600-750 BHN along with good strength and
Addition of 14-38% nickel to gray cast iron result in high heat resistance, high corrosion
resistance and low expansivity.
Material Science & Metallurgy (2131904) 9. Cast Iron


Course Contents
10.1 Introduction
10.2 Copper and copper
10.3 Brass and Brass alloys
10.4 Bronze and bronz
10.5 Gun metal
10.6 Bearing materials
10.7 Magnesium and its
10.8 Lead and its alloys
10.9 Tin and tin alloys
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)

Ferrous alloys are consumed in exceedingly large quantities because they have such a wide range of
mechanical properties, can be fabricated with relative ease and are economical to produce.
However, they possess some distinct limitations, chiefly
1. A relatively high density; therefore heavier in weight,
2. A comparatively low electrical conductivity, and
3. An inherent susceptibility to corrosion in some common on environments.
Thus, for many applications it is advantageous or even necessary to utilize other alloys e.g., non-
ferrous alloys, having more suitable property combinations. On occasion, a distinction is made (in
non-ferrous alloys) between cast and wrought alloys. Alloys that are so brittle that forming or
shaping by appreciable deformation is not possible ordinarily are cast; these are classified as cast
alloys. On the other hand, those that are amenable to mechanical deformation are termed wrought
In addition, the heat treatability of an alloy system is mentioned frequently. Heat-treatable
designates an alloy whose mechanical strength is improved b y precipitation hardening etc.
Non-ferrous metals/alloys are not iron-based. The more common non-ferrous materials are the
following metallic elements and their alloys:
1. Copper 4. Lead 7. Zinc
2. Aluminium 5. Nickel 8. Cobalt etc.
3. Magnesium 6. Tin


The main grades of raw copper used for cast copper base alloys are:
a) High conductivity copper (electrolytic) having not less than 99.9% Cu. The oxygen content
may be of the order 0.40%, Pb and Fe less than 0.005% each. Ag 0.002% and Bi less than
0.001%. Electrolytic copper is used for electrical purposes.
b) Deoxidized copper having not less than 99.85% Cu, less than 0.05% As, 0.03% Fe, and
0.003% Bi. Other elements may be of the order of 0.05% P, 0.01% Pb, 0.10% Ni, 0.003% and
0.005% Ag and Sb respectively.
c) Arsenical deoxidized copper having; 0.4% At, 0.04% P and remaining copper. It is used for
welded vessels and tanks.
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys

d) Arsenical touch pitch copper containing 0.4% As, 0.065% oxygen, 0.02% Pb, 0.15% Ni,
0.006% Ag, 0.01% Sb and less than 0.005% Bi, less than 0.020% Fe and remaining copper.
e) Oxygen free copper contains 0.005% Pb, 0.001% Ni, 0.001% Ag and less than 0.0005% and
0.001% Fe and Bi respectively. It is melted and cast in non-oxidising atmosphere.
- Excellent resistance to corrosion.
- Non-magnetic properties.
- Easy to work, it is ductile a d malleable.
- Moderate to high hardness and strength.
- High thermal and electrical conductivity.
- It can be easily polished, plated and possesses a pleasing appearance.
- Resistance to fatigue, abrasion and corrosion.
- It can be soldered, brazed or welded.
- Very good machinability.
- Ease of forming alloys with other elements like Zn, Sri, Al, Pb, Si, Ni, etc.
- Copper is used for the Electrical parts, Heat exchangers, Screw machine products, for
making various copper alloys, such as brass and bronze, household utensils, etc.
Copper Alloys
- Copper alloys normally possess excellent corrosion resistance, electrical and thermal
conductivities and formability.
- Some copper alloys combine high strength and corrosion resistance, a combination
desirable for marine applications.
- Some copper alloys because of their wearing properties, high hardness or corrosion
resistance are used as surfacing metals.
- Some copper alloys are selected for decorative applications because of appearance.
- Elements such as aluminium, zinc, tin, beryllium, nickel, silicon, lead etc., form alloys with
- High copper alloys contain 96.0 to 99.3% copper.
- They possess enhanced mechanical properties due to the addition of small amounts of
alloying elements such as chromium, zirconium, beryllium and cadmium.
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)

- A few typical high copper alloys are:

1. Cu, 1% Cd 3. Cu, 0.12-0.30% Zr
2. Cu, 0.8% Cr 4. Cu, 1.5-2.0% Be
- Such alloys are used for electrical and electronic components, as resistance welding
electrodes, wire conductors, diaphragms and pump parts.

10.3 Brass and Brass Alloys

- Brasses contain zinc as the principle alloying element.
- Brasses are subdivided into three groups;
1. Cu-Zn alloys,
2. Cu-Pb-Zn alloys or leaded brasses, and
3. Cu-Zn-Sn alloys or tin brasses.
- Brass has high resistance to corrosion and is easily machinable. It also acts as good bearing
material. Zinc in the brass increases ductility along with strength.
- Brass possesses greater strength than copper, however, it has a lower thermal and electrical
conductivity. Various types of brasses are discussed below:
(1) Gilding Metal
- The gilding metals cover a range from 5% to 15% Zn (balance Cu) and possess shades of
colour from the red of copper to a brassy yellow.
- They are supplied mainly in the form of sheet strip and wire for jewellery and many other
decorative purposes. Like copper, gilding metal is hardened and strengthened by cold work.
Gilding metal is used for making coins, medals, tokens, fuse caps etc.
(2) Cartridge Brass
- Cartridge brass normally contains 70% Cu and 30% Zn. In the fully annealed condition it has
a tensile strength of over 300 N/mm2.
- Greater % elongation and tensile strength make this brass satisfactory for cold deformation
in presses and by spinning or other means, and have led to its almost universal adoption for
cartridge and shell cases, W, well as for countless cupped articles like the caps of electric
lamp bulbs, door furniture etc.
- Cartridge brass work hardens when deformed in the cold, and must be annealed if many
successive operations are to be performed. An annealing temperature of about 600C is
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys

satisfactory in most cases.

(3) Admiralty brass
- Admiralty brass contains Cu 71%, Zn 28%, and Sri 1%.
- The small amount of tin added to brass improves its resistance to certain types of corrosion.
- Admiralty brass, though, it has been to a greater extent superseded by better materials for
the exacting conditions of marine condensers, it is still widely used for the tubes and other
parts of condensers coded by fresh water and for many other purposes. For such
applications, the modern alloy contains about 0.04% Arsenic, which improves resistance to a
penetrative form of corrosion known as dezincification.
(4) Aluminium brass
- Aluminium brass contains 76% Cu, 22% Zn and 2% Al; a little arsenic is added to inhibit
- In contact with sea water, a protective film builds up on the surface of this alloy in the early
stages of corrosion and prevents further attack. Moreover, if the film is damaged, by the
abrasive action of sand particles, for instance, it is self-healing.
(5) Basis brass
- Basis brass contains copper 61.5-64%, the remainder being zinc.
- Basis brass is used for press work where a relatively cheap material is required, and the
main commercial forms are sheet, strip and wire.
(6) Muntz metal
- Muntz metal or yellow metal contains 60% of copper and 40% of zinc and is essentially a hot
working material. It is manufactured in the form of hot rolled plate, and hot rolled rod or
extruded sections in a great variety of shapes and sizes. Yellow metal is frequently used as a
brazing alloy for steel.
- Other applications of muntz metal are as: Ship sheathing, Perforated metal, Valve stems,
Condenser tubes, Architectural work etc.
(7) Leaded 60:40 brass
- Leaded 60:40 brass is the chief material fed to automatic lathes and similar machines,
usually in the form of extruded bar.
- Lead is added to Cu-Zn alloy to promote machinability. The lead content ranges from about
0.5% to as much as 3.5%. Where machinability is the chief consideration, the lead content is
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)

high, but alloys relatively low in lead are preferred for hot forging operations. Lead has no
marked effect on the tensile strength, which is approximately the same as that of straight 60
: 40 brass, though lead tends to impair the weldability, ductility and impact strength.
- Leaded brass is used for: Keys, Lock-parts, Gears, Clock parts, Valve parts, Pipe unions, Items
for automatic water heaters.
(8) Naval brass
- Naval brass contains Cu 60%, Zn 39.25% and Sn 0.75%. The purpose of tin is to improve the
resistance to corrosion.
- Naval brass is used for structural applications and for forgings, especially in cases where
contact with sea water is likely to induce corrosion.
- Naval brass is obtainable as hot-rolled plate particularly for marine condenser plates, and in
the form of extruded rod for the production of machined or hot forged components. Both
sand and die castings are also available.
- Other applications of naval brass are: Propeller shafts, Valve stems, Pump impellers etc.
(9) Admiralty brass
- Admiralty brass contains 71% Cu, 28% Zn, and 1% Sn.
- It is used for decorative and architectural applications, screw machine products, heat
exchanger components, pump impellers etc.


- Bronze is a broad term defining an alloy of copper and elements other than nickel or zinc.
- Bronze is basically an alloy of copper and tin. Bronze possesses superior mechanical properties
and corrosion resistance than brass. Bronze is comparatively hard and it resists surface wear.
- Bronze can be shaped or rolled into wire, rod and sheets. Types of bronzes are:
(1) Phosphor Bronze
- Phosphor Bronze containing approximately 4% each of tin, lead and zinc has excellent free-
cutting characteristics.
- The most important copper-tin alloys are those which have been deoxidized with phosphorus
during the refining process and hence are known as phosphor bronze.
- The amount of residual phosphorus may range from a trace to about 0.35% or even higher in
some special grades.
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys

- The excess phosphorus, which exists in solid solution, materially increases the hardness and
strength of the alloy, but it does so at the expense of ductility.
- In amounts greater than 1.0% phosphorus causes excessive brittleness and impairs surface
appearance but affords a good bearing surface, as is evident by the use of high phosphorus
bronze compositions for gears and other machine parts subject to wear.
- Standard Phosphor bronze for bearing applications contains 90% Cu, 10% Sri (min), and 0.5% P
(min). In sand cast condition it has a tensile strength of 220-280 N/mm2 and % elongation 3 to
- Phosphor bronze for gears contains 88% Cu, 12% Sri, 0.3% (max) Zn, 0.50% (mw.) Pb and 0.15%
(min) P. In sand cast condition, it has a tensile strength of 220-310 N/mm2 and 5-15%
elongation. This alloy is also utilised for general bearings, where its rigidity is of advantage.
- Leaded phosphor bronze contains 87% Cu, 7.5% Sn, 2.0% (max)Zn, 3.5% Pb, 0.3% (min) P and
1.0% (max) Ni. In sand cast condition, it has a tensile strength of 190-250 N/mm2 and %
elongation is 3-12. This material is satisfactory for many bearing applications.
- In general phosphor bronze
Has high strength and toughness Has good load bearing capacity and
Is resistant to corrosion Has low coefficient of friction.
- Phosphor bronze is used for bearing applications, making pump parts, linings, springs,
diaphragms, gears, clutch discs, bellows etc.
(2) Aluminium bronzes
Aluminium bronzes have the following compositions:
Cu Al Fe Sn Mn(%)
89 7 3.5 0.35 -
91 6-8 1.5-3.5 - 1(max)
Aluminium bronzes possess the following properties:
- Good strength - Good heat resistance
- High corrosion resistance - Good cold working properties, etc
Aluminium bronze finds the following uses:
- Bearings - Propellers - Imitation jewellery
- Valve seats - Slide valves - Pump parts etc.
- Gears - Cams
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)

(3) Silicon bronze

Silicon bronzes have compositions:
- Si 1-4% - Mn 0.25-1.25%
- Fe 0.5-1.0% - Cu Balance
- Lead when added as 0.5% improves machinability.
- Silicon bronzes possess high strength and toughness as that of mild steel and corrosion
resistance as that of copper.
- Silicon bronze can be cast, rolled, forged and pressed hot or cold.
- Silicon bronzes find the following uses:
Bearings Screw down nuts Marine hardware
Ways and gibs Turntable bushings Die cast parts etc.
Roll mill sleepers Boiler parts


- Gun metal is an alloy of copper, tin and zinc.
- Zinc cleans the metal and increases its fluidity.
- A small amount of lead may be added to improve castability and machinability.
- Admirality gun metal contains 10% Sri, 2% Zn, 1.5% max. Pb, 1.5% max Ni and balance Cu. It
has tensile strength of 260-340 N/mm2. It is widely used for pumps, valves and
miscellaneous castings and is also used for statuary.
- Nickel gun metal contains 7% Sri, 2.25% Zn, 0.3% Pb, 5.5% Ni and balance copper. When
sand cast and heat treated it has a tensile strength of 430-480 N/nun2.
- Leaded gun metal contains 5% Sri, 5% Zn, 5% Pb, 2.0% max Ni. When sand cast it has a
tensile strength of 200-270 N/mm2. This is among the most widely used grades, particularly
where pressure tightness is required.
- In general gun metal is used for Bearings, Steam pipe fittings, Marine castings, Hydraulic
valves, Gears, etc


Bearings support moving parts, such as shafts and spindles, of a machine or mechanism.
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys

Bearings may be classed as

(1) Rolling contact (i.e., Ball and roller) bearings, (2) Plain bearings.
Copper-based alloys
- The term bronze covers a large number of copper alloys with varying percentages of Sri, Zn
and Pb.
- Typical compositions of bearing bronze are: Cu 80%, Sn 10%, Pb 10%
- Bronze is one of the oldest known bearing materials.
- Bronze (a) is easily worked; (b) has good corrosion resistance; (c) is reasonably hard.
- Tin bronze (10 to 14% tin remainder copper) is used in the machine and engine industry for
bearing bushes made from thin walled drawn tubes.
- Copper-based alloys are employed for making bearings required to heavier pressures such
as in railways.


Aluminium is a silvery white metal and it possesses the following characteristics:
- It is a light metal, with a density about a third that of steel or brass.
- Aluminium is a very good conductor of electricity. On a weight-for-weight basis aluminium is
a better conductor than copper.
- Aluminium has a higher resistance to corrosion than many other metals, owing to the
protection conferred by the thin but tenacious film of oxide which forms on its surface.
- Aluminium is a good conductor of heat.
- Aluminium is very ductile.
- Aluminium is non-magnetic.
- Melting point of pure aluminium is about 650C and the fusion range of most of the
aluminium alloys varies between 520 and 650C.
Aluminium Alloys
- Although pure aluminium is not particularly strong, it forms high strength alloys in
conjunction with other metals such as Cu, Cr, Ni, Fe, Zn, Mn, Si and Mg.
- Some of these aluminium alloys are more than 4 times as strong as the same weight of mild
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)

- They are malleable and ductile.

- They exhibit toughness and become stronger at temperatures below the ordinary
atmospheric range.
- They do not work well at temperatures of the order of 300 to 400C.
- Aluminium and its alloys can be Cast, Forged, Welded, Extruded, Rolled, etc.
Uses of Al and Al-alloys
The intensive demand for Al and its alloys arises chiefly from their attractive physical, mechanical
and chemical properties. Aluminium and its alloys are frequently used for
- Transportation industry-structural frame-work, engine parts, trim and decorative features,
hardware, doors, window frames, tanks, furnishing and fittings.
- Trains, trucks, buses, automobile cars and aeroplanes use many component parts made up
of aluminium alloys.
- Overhead conductors and heat exchanger parts.
- In food industry, aluminium alloys find applications as food preparation equipments,
refrigeration, storage containers, bakery equipment, shipping containers, etc.
- In architectural field, aluminium alloys find uses such as window frames, doors hardware,
roofing, coping sills, railings, fasteners, lighting fixture, solar shading, grills, etc.
- Cryogenic applications.
- As heavy duty structures such as dragline booms, travelling cranes, hoists, conveyor
supports, bridges, etc.
- In process industries, parts made up of aluminium and its alloys are used to handle organic
chemicals, petrochemicals and drugs. Tanks, drums, pipes, heat exchangers, gratings,
smoke-stacks, precipitators, centrifuges, valves, fittings, etc. are produced from aluminium
- Types of aluminium alloys are:
1. Al-Mn 4. Al-Mg-Si 7. Al-Cu-Mg-Pb
2. Al-Mg 5. Al-Cu-Mg 8. Al-Mg-Si-Pb
3. Al-Mg-Mn 6. Al-Cu-Si 9. Al-Zn-Mg-Cu
- Aluminium alloys can be classified as follows:
1. Wrought alloys 3. Heat-treatable alloys
2. Cast alloys 4. Non-heat-treatable alloys.
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys


- Magnesium is a silvery white metal and has the lowest density of the common structural
- It has a specific gravity of 1.74 and weighs only about 1 oz/cu in (1.73 gm/cu cm).
- Aluminium weighs 1.5 times more, iron and steel 4 times more, and copper and nickel alloys
5 times more.
- Magnesium has a melting point of 650C.
- Magnesium is not employed in its pure state for use for engineering purposes because it is
not sufficiently strong. Usually it is necessary to use considerable thickness or utilize deep
sections so as to obtain adequate stiffness.
- Magnesium corrodes badly under many conditions and therefore need to be painted or
given some surface finish to avoid corrosion.
- Magnesium being costly, finds applications where light weight is a very important
requirement, such as in aircraft industry.
Magnesium Alloys
Magnesium is alloyed with elements such as Al, Zn, Mn, Zr, etc., to make it useful for engineering
applications. Alloying increases strength and corrosion resistance.
- High strength-to-weight ratio. - Good damping capacity.
- Good fatigue strength. - High thermal conductivity.
- Good dimensional stability. - Relatively high elect. Conductivity.
- For making parts such as airframes, engines, gear boxes, flooring, seating, etc., for
aeroplanes, helicopters, missiles and satellites.
- For parts such as engines, transmission pumps, differentials, floors and body panels of
ground transportation vehicles (trucks, etc.).
- For material handling equipments such as hand trucks, barrel skids, grain shovels, gravity
conveyors, foundry equipment, etc.
- For storage tanks and hoppers, ladders and scaffolds, electric drills, chain saws, power
hammers, etc.
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)

- Moving parts of textile machines and printing equipment.

- Furniture, griddles, ladders and lawn movers.
- Typewriters, dictating machines, calculators, etc.
- Binocular and camera bodies.
- In the production of Uranium, beryllium, zirconium, titanium, etc.
Types of Magnesium Alloys
(1) Cast alloys of magnesium
Sr. No. % Composition (Balance Mg) Characteristics
1. Rare earth metal 3.0, Zn 2.5, Zr Creep resistant upto 250C, Excellent
0.6 castability. Pressure tight and weldable.
2. Al 8, Zn 0.5, Mn 0.3 General purpose alloy, Good founding
properties. Good ductility, strength and shock
3. Al 8, Zn 0.5, Mn 0.3, Be 0.0015 General purpose pressure die casting alloy.
4. Al 7.5-9.5, Zn 0.3-1.5, Mn 0.15 General purpose alloy with good average
min. properties.

(2) Dow metal

- It contains 90% magnesium, 10% Aluminium and a small addition of manganese.
- Dow metal finds applications in auto and aircraft industries.
- Dow metal is extremely light and can be welded and machined.
(3) Wrought Magnesium Alloys
Sr. No. % Composition (Balance Mg) Characteristics
1. Zn 3.0, Zr 0.6 High strength sheet, extrusion and forging
alloy. Weldable under good conditions.
2. Th 0.8, Zn 0.6, Zr 0.6 Creep resistant up to 350C, fully weldable.
3. Al 8.5, Zn 0.5, Mn 0.12 Min High strength alloy for forgings of simple
4. Al 6.0, Zn 1.0, Mn 0.3 General purpose alloy, gas and arc weldable.


Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys

Lead is the oldest of the commonly used metals and the softest of the heavy metals. When it is cast
or cut, it is a lustrous silvery colour to begin with. After standing for a time, however, the surface
turns a dull bluish grey due to oxidation. Lead is poisonous and should not be brought into contact
with food. Lead has a F.C.C. crystal structure.
- It has a low melting point of 327C and density is 11.34 kg/dm3.
- It is very resistant to corrosion, against most acids, but not against HCl-HNO3 mixture.
- Its strength, hardness and elasticity are low, e.g., tensile strength 15 NNmm2, extensibility
up to 60%.
- It has low resistance to deformation but high formability, cold forming is preferred.
- Lead can be easily soldered, welded and cast. It can be spread over other metal surfaces.
- In addition lead has: Heavy weight, High density, Softness, Malleability, Lubricating
properties, High coefficient of expansion, Low electrical conductivity and poisnous.
Uses and applications of lead
- As an alloying element to improve the machinability of bronzes, brasses and free machining
- Tank linings for corrosion protection.
- Manufacture of storage batteries.
- Pipe and drainage fittings.
- Bearing metals.
- Lead compounds in paints.
- Lead sheathing of electric cable.
- Low melting solders.
- Terne plate (lead-tin coated), etc.
- Radiation protection (from x-rays).
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)
Lead Alloys
- Lead alloys containing 8% to 10% Pb are used as bearing (antifriction) metals, in
cable sheaths, accumulation plates, etc.
- Antimony makes the alloy hard.
- Lead compounds include red lead and white lead.
- Lead glass (lead crystal glass) refracts light strongly.
Alloy Composition in % Uses
Lg Pb Sb 12 Sb 10.5-13, Cu 0.3-1.5, Ni 0- In mechanical engineering, easily
(Bearing hard lead) 0.3, As 0-1.5, Rest lead soldered to steel, for lining
Pb (Sb) Sb 0.2-0.3, Rest lead Drain pipes


- The element nickel (along with the elements Fe and Co) constitute the transition
group in the fourth series of the periodic table.
- It has an atomic number of 28, an atomic weight of 58.71, density 8.908 g/cu cm at
20C and melting point of 1453C.
- The normal crystallographic system of nickel is F.C.C. at all temperatures.
- The usual commercial grade of wrought nickel ('A' nickel) nominally contains 99.0%
nickel + up to 0.4% cobalt, which traditionally are combined and reported as 99.4%
- Commercially pure nickel is almost as hard as low-carbon steel.
- Nickel work-hardens rapidly when cold worked.
- With suitable modifications in temperatures, tools, pressures, rates etc., wrought
nickel is amenable to most of the fabrication processes used for mild steel. It can be
forged, rolled, bent, extruded, sheared, punched, spun, deep drawn, machined,
ground, polished and buffed.

Properties of Nickel
- Is a hard lustrous white metal.
- Possesses good corrosion and oxidation resistance.
- Has high tensile strength and can be easily formed hot or cold.
- Can take up high polish.
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys
- Can be fabricated using processes similar for mild steel.
- Is ferromagnetic at ordinary and low temperatures but becomes paramagnetic at
elevated temperatures.
- Melting point ... 1453C
- Density, gm/cu cm, at 20C ... 8.908
- Coefficient of Thermal expansion x 10-6/C (25 toJ00C) 13.3
- Tensile strength 65000 - 115000 psi (From hot (4565 to 8075 kg/cm2) to cold drawn)
- Modules of Elasticity ... 30 x 106 psi (2.11 x 106 kg/cm2)
- Hardness RB 40 to 100 (depends on whether Ni is hot rolled, annealed or cold
Uses of Nickle
- For corrosion protection of iron and steel parts and Zn-base die castings used in the
automotive field.
- In the chemical, soap, caustic and allied industries for the construction of
evaporators, tanks, jacketed kettles, heating coils, tubular condensers and many
other processing types of equipment.
- As an alloying element in both ferrous and non-ferrous alloys. Nickel is a strong
austenite stabilizer and with chromium is used to form the important AISI 300 series
of non-magnetic austenitic stainless steels.
- As a coating for parts subjected to corrosion and wear. Therefore the second
important use of nickel is in electroplating.
- In the incandescent lamp and radio industries.
- In electronic (vacuum electronic tubes) and low-current electrical applications.
- As permanent magnets.
Nickel Alloys:
Various nickel alloys are:
A. Nickel-Iron alloys D. Nickel-Chromium alloys
B. Nickel-Copper alloys E. Nickel-Molybdenum alloys
C. Nickel-Copper-Zinc alloys F. Super alloys
(A) Nickel-Iron alloys
- Nickel and iron form a series of alloys with thermal-expansion and magnetic
characteristics of commercial importance.
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)
- Invar is the Trademark for an iron-nickel alloy containing 40-50% nickel and is
characterized by an extremely low coefficient of thermal expansion. Invar is used for
making precision instruments, measuring tapes, weights etc.
- The addition of 12% chromium, in lieu of some of the iron, produces an alloy
(Elinvar) with an invariable modulus of elasticity over a considerable temperature
range as well as a fairly low coefficient of expansion.
(B) Nickel-Copper alloys
1. The major nickel-based alloy with copper is Monel which nominally contains 66% Ni,
31.5% Cu, 1.35% Fe, 0.90% Mn, plus residuals.
- Monel has a brighter appearance than nickel, is stronger and tougher than mild
steel, has excellent resistance to atmospheric and sea-water Corrosion and generally
is more resistant than nickel to acid, less resistant to alkalies and equally resistant to
- Monel is used in architectural and marine applications where appearance and
corrosion resistance is important and in specialized equipment used by the food
pharmaceutical, paper, oil and chemical industries.
2. Several variations of monel have been produced to obtain an additional
characteristic. These include:
- An age-hardenable grade (K Monel),
- A free machining grade (R Monel),
- A hard-casting grade (H Monet),
- An age-hardenable casting grade (S Monel), etc.
3. Constantan, another alloy of nickel and copper contains 45% Ni and 55% Cu.
- Constantan has highest electrical resistivity, lowest temperature coefficient of
resistance, and highest thermal emf against platinum, of any of the copper-nickel
- Uses in Electrical resistors, Thermocouples, Wheatstone bridges, etc.
(C) Ni-Cu-Zn alloys (Nickel-Silver)
- Nickel-copper-zinc alloys though known as nickel-silver, do not contain silver, and in
actuality they are brasses with sufficient nickel added to give a silvery white colour,
improved corrosion resistance and high strength.
- These alloys are used as low cost substitutes for silver in tableware and jewellery,
usually with silver or gold electroplate on the surface.
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys
- Nickel silvers are also construction materials for many musical, drafting and scientific
instruments and are also used for marine and architectural applications.
(D) Nickel-Chromium alloys
- Nickel-chromium alloys with or without iron, form a series of corrosion and heat-
resistant materials.
- In this group the 80% Ni, 14% Cr, 6% Fe alloy (Inconel) with many modifications
resists progressive oxidation below 1093C and is used in applications such as
furnace chambers, salt pots, aircraft exhaust manifolds, and high-temperature
- It was originally developed for use in the milk industry as a corrosion-resistant alloy
and now is much used in many chemical industries because of its excellent corrosion
- The 80% Ni, 20% Cr alloy (Chromel A, Nichrome V, Tophet A) and the 60% Ni, 16% Cr,
24% Fe alloy (Nichrome, Chromel C, Tophet C) form the bulk of materials used for
heater elements.
- The 90% Ni, 10% Cr (Chromel P) alloy in combination with alumel is much used as a
dependable base-metal thermocouple.
(E) Nickel-Molybdenum alloys
- Nickel-Molybdenum alloys such as Hastelloy A, Hastelloy C and Hastelloy D possess
very good resistance to corrosion.
Type of % Composition
Properties and Uses
Alloy Ni Mo Fe Cr W
Hastelloy A 57 20 20 - - High strength and ductility. Can be forged and
rolled. Resists attack of acids. Used in chemical
industry for equipments such as storage tanks
and for material handling and transportation.
Hastelloy C 54 17 5 15 4 Can he cast and machined. Resistant to HNO3,
free chlorine and acid solutions of salts such as
cupric and ferric. Used in chemical industry for
pumps, valves, spray nozzles etc.

(F)Super alloys
- The super alloys have superlative combinations of properties.
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)
- These materials are classified according to the predominant metal in the alloy, which
may be cobalt, nickel or iron.
- Other alloying elements include the refractory metals (Nb, Mo, W, Ta), chromium
and titanium.
- Super alloys are at least five times as strong as steels routinely used for making
bridges and large buildings. They can withstand enormous strains and exhibit
remarkable resistance to metal fatigue. They possess high impact strength and
superior strength-to-mass ratio. They are probably the toughest materials ever
- Super alloys are used in aircraft turbine components, which must withstand
exposure to severely oxidizing environments and high temperatures for reasonable
time periods.
- Mechanical integrity under these conditions is critical; in this regard, density is an
important consideration because centrifugal stresses are diminished in rotating
members when the density is reduced.


Tin is it non-toxic white, soft and pliable metal adaptable to cold working such as rolling,
extrusion and spinning. Tin melts at a low temperature (231.9C), is highly fluid when
molten and has a high boiling point (2270C), which facilitates its use as a coating for other
metals. It can be electrodeposited readily on all common metals.
- Boiling point ... 2270C
- Specific gravity - -form (gray tin) ... 5.77, -form (white tin) ... 7.29
- Coefficient of linear expansion, 0C ... 19.9 x 106
- Solidification shrinkage, % ... 2.8
- BHN 10 kg/5m, 180 sec - 20C ... 3.9, 220C ... 0.7
- Tensile strength, as cast 200C 0.65 x 103 psi (45.65 kg/cm2)
15C 2.1 x 103 psi (147.4 kg/cm2)
- 40C 2.9 x 103 psi (204 kg/cm2)
- Tin has good resistance to acid corrosion. Therefore, it is used as a coating on steel
containers for food.
- Tin alloys with Cu, Sb, Bi, Cd and Ag and its hardness increases.
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys
- Tin is usually sold as ingots; however, it can be obtained in a number of forms such
as granulated, mossy, fine powder, sheet, foil and wire.

Tin Alloys
(1) Soft Solders 20 to 70% tin and remaining lead.
Symbols Composition in % by weight Uses
and melting point range
L-Pb Sn 35 Sb containing Sn 34.5-35.5, Sb 0.5-2.0, Rest Solder for copper, tin, zinc,
antimony Pb 186C-225C used with soldering iron or
L-Sn 50 Ph (Sb) Tin-lead Sn 49.5-50.5, Sb 0.12-0.5, Tinning, fine soldering,
solder low antimony Rest Pb 183C-215C electrical engineering
L-Sn 60 Pb Ag Sn 59.5-60.5, Ag 3.0-4.0, Rest Electronics, precision
Pb 178C -180C mechanics, production of
electrical appliances
- The eutectic alloy, with 63% tin is used extensively in electrical industry.
- Alloy with 50% tin is general-purpose solder.
- Lower tin solders (15-20% tin) are used as dipping solders for sealing automotive
radiator cores.
- Bi, Cd, Pb and tin alloys are used as fuses for fire-extinguishing equipment, boiler
plugs, etc.
(2) Copper-tin alloys (bronzes)
- Phosphor bronze containing 8-12% tin with small additions of phosphorus is used for
springs, condenser tubes, bearings, bushings and diaphragms.
- The gun metals, tin-bronze casting alloys with 1 to 6% Zn are used for valves and
fittings for water and steam lines.
- Babbitt bearing metals are essentially tin-base alloys.
(3) Aluminium-tin alloys

- The 6% tin-aluminium alloys can be bonded to steel by rolling.

- Low tin-aluminium alloys possess high fatigue strength and thus can carry fluctuating
(4) Pewter,
10. Non - Ferrous Alloys Material Science & Metallurgy (2131904)
- Its tarnish resistant alloy containing 7% antimony and 2% copper, is easy to cast and
to work into complicated shapes by spinning and hammering and is available as
plates, trays, bowls, pitchers, etc.
(5) Alloys of titanium
- Contains 2.5% Sn and 5% Al (or 13% Sn with 2.75% Al) find use in aircraft industry.


- Zinc is a blue to gray metallic element.

1. Relatively low melting point, 419.5C (die-casting).
2. Good resistance to atmospheric corrosion.
3. Solubility in copper (brass).
4. Inherent ductility and malleability.
5. Volume coef. of Ther Exp. 20-400C ... 8.9 x 10-5/C.
6. Thermal conductivity at 18C ... 0.27 cal/sec/cm/C
- Zn is produced commercially as slab, Anode, strip, wire, Powder and rod.

- Stampings - Building materials (as for flashings,
- Die castings roofing, gutters, etc.)
- Anodes for electro-galvanising - Engravers' plates.
- Coating on steel (to protect it) - Wire for metallizing.
- Making different alloys - Lithographers' sheets, etc.
- Fabricated (and rolled) shapes.
- Shells for dry batteries.

Typical chemical composition (%):

(Pb + Cd + Zn
Pb Fe Cd Cu
Rolled zinc 0.05 to 0.012 0.005 0.65 to - Remainder
0.12 max Max Max 1.25
Material Science & Metallurgy (2131904) 10. Non Ferrous Alloys
High grade Slab zinc 0.07 0.02 0.07 - < 0.10 Remainder
Selected grade slab zinc 0.80 0.04 0.75 - < 1.25 Remainder
Zinc Alloys
Zinc alloys can be fabricated by Drawing, Bending, Extrusion, Spinning, Rolling, Soldering.
Zn makes alloys with:
1. Al 3. Cu 5. Mg 7. Fe, and
2. Pb 4. Cd 6. Sn 8. Ni
- Pb stimulates intercrystalline corrosion in Zn alloy die castings.
- Cd exerts an important hardening effect and raises the recrystallization temperature.
Zn containing Cd can absorb considerable amounts of work hardness during cold
rolling or drawing.
- Fe, some iron is desirable but excessive amounts are harmful to properties.
- Cu, Cu-Zn alloys are more ductile and easier to roll. Copper enters into solid solution
in zinc up to approximately 1%.
- Mg, when added in the presence of copper, increases resistance to creep.
Powder Metallurgy

Course Contents
11.1 Introduction
11.2 Applications of
powder metallurgy
11.3 Advantages of powder
11.4 Limitations of powder
11.5 Powder metallurgy
11.6 Production of metal
11.7 Characteristic of metal
11.8 Blending and mixing
of powder
11.9 Compacting
11.10 Presintering and
11.11 Secondary operation
Material Science & Metallurgy (2131904) 11. Powder Metallurgy

11.1 Introduction:
Powder metallurgy is an art and science of producing fine metal powders and
then making objects from individual, mixed or alloyed metal powders with or
without the inclusion of non-metallic constituents. Components are produced in
their final form by pressing metal powders into the desired shape, usually in a
metal mold, and then heating the compacted powder, either concurrently or
subsequently, for a period of time at a temperature below the melting point of
the major constituent.
For making a component by powder metallurgy,
1. The metal in the powder form must be able to respond to solid phase
2. The metal powder must be capable of sufficiently close packing under
pressure to permit welding to take place and, in case of alloying, be
capable of being sufficiently intimately mixed

11.2 Applications of Powder Metallurgy:

Porous products, e.g., bearings and filters.
Refractory parts, e.g., components made out of Tungsten, Tantalum and
Molybdenum are used in electric bulbs, radio valves, oscillator valves, X-ray
tubes in the form of filament, cathode, anode, control grids, etc.
Products of complex shapes that require considerable machining when made by
other processes, e.g., toothed components such as gears.
Automotive components such as electrical contacts, crankshaft drive or
camshaft sprocket, piston rings and rocker shaft brackets, door mechanisms,
connecting rods and brake linings, etc.
Products made from materials that are very difficult to machine, e.g., tungsten
carbide, etc.
Components are: gauges, wire drawing dies, wire guides, deep drawing,
stamping and blanking tools, stone hammers, rock drilling bits, etc.
Products where the combined properties of two metals or of metals and non-
metals are desired: non-porous bearings, electric motor brushes, etc.
Atomic energy applications.
Tungsten parts are employed in plasma jet engines, etc., which are operated at
about 1850C. Silver infiltrated tungsten is used in nozzles for rockets and
missiles. Use as parts in military and defence systems, e.g., in military arms.
Parts made by powder metallurgy have also been used in clocks and timing
devices, typewriters, adding machines, calculators, permanent magnets,
laminated bimetallic strips, etc.
Grinding wheels that incorporate steel and diamond powder may be
manufactured by powder metallurgy
11. Powder Metallurgy Material Science & Metallurgy (2131904)

11.3 Advantages Of Powder Metallurgy:

The dimensional accuracy and surface finish obtainable are such that for many
applications all machining can be eliminated.
Cleaner and quieter operation and longer life of the components.
High production rates.
Control of grain size, relatively much uniform structure and defect (e.g., voids,
blowholes, etc.) free components.
No material is wasted as scrap; the process makes use of 100% raw material unlike
casting, press forming, etc.
Quite complex shapes can be produced
Components shapes obtained possess excellent reproducibility. Porous parts can be
produced that could not be made in any other way. Parts with wide variations in
compositions and materials can be produced. Structure and properties can be
controlled more closely than in other fabricating processes.
Highly qualified or skilled labour is not required.
Impossible parts (e.g., super-hard cutting tool bits) can be produced.\
The use of diamond in industry has been made possible mainly through
Powder metallurgy is free from the limitations imposed by phase diagram. For
example, it is difficult to produce copper-lead bearing alloys containing large
amounts of lead, since the two metals are insoluble as liquids. However, mixed
powders of copper and lead can be successfully shaped by powder metallurgy.

11.4 Limitations Of Powder Metallurgy:

Complicated shapes, such as produced by casting, cannot be made by powder
metallurgy, because metallic powders lack the ability to flow to the extent of molten
Parts made by powder metallurgy, in most cases, do not have as good physical
properties as wrought or cast parts.
Relatively high tool and die cost is associated with the process
The size of products (as compared to casting) is limited because of the large
presses and expensive tools which would be required for compacting.
Powdered metals are considerably more expensive than those in wrought forms.
Extreme care is required in handling pyrophoric powders (e.g.,Mg, Th, Zr) to prevent
fires or explosions and with toxic powders (e.g., U, Be, Th) to minimize health
Material Science & Metallurgy (2131904) 11. Powder Metallurgy

11.5 Powder Metallurgy Process:

The principal steps in powder metallurgy process include:

Obtaining/producing metal powders in a suitable degree of fineness and

Weighing and mixing of the necessary powders (and lubricants) to arrive
at a composition which processes satisfactorily and which produces desired
properties in the fabricated part.
Pressing the powder (mixture) in a suitable mold (of required size and shape)
to cause cohesion to occur between the powder particles.
Presintering the powder compact by heating and holding it at a moderate
temperature. Presintering develops additional green strength.
Finishing and sizing the final product.
Repressing for greater density or closer dimensional control.
Machining, polishing
Rolling, forging or drawing.
Surface treatments to protect against corrosion.

Fig. 11.1 Powder Metallurgy Process

11. Powder Metallurgy Material Science & Metallurgy (2131904)

11.6 Production of Metal Powders:

The particle size of powders falls into a range of 1 to 100(x (micron), with the range of 10 to
20 (micron) being predominant. There are various methods of manufaccturing powders of
this size, but those commonly used are:
1. Atomization
2. Reduction
3. Electrolysis
4. Crushing
5. Milling
6. Condensation of metal vapours


Fig. 11.2 Methods of producing metal powders

(1) In Atomization, the molten metal is directed through an orifice and as it

emerges, a highpressure stream of gas or liquid impinges on it causing it to atomize
into fine particles. Frequently an inert gas is employed in order to improve the purity
of the powder. Atomization is used mostly for low melting point metals because of
the corrosive action of the metal on the orifice (or nozzle) at high temperatures.

(2) In Reduction process, the compounds of metals (usually oxides, e.g., iron
Material Science & Metallurgy (2131904) 11. Powder Metallurgy

oxide)arereduced with CO or H2 at temperatures below the melting point of the

metal (e.g., iron) is an atmosphere-controlled furnace. The reduced product is then
crushed and ground.
Sponge-iron powder is produced this way.
Fe304 + 4C = 3Fe + 4CO
Fe304 + 4CO = 3Fe + 4C02

Copper powder can be produced by the same method i.e., by heating copper oxide
in a stream of hydrogen,
Cu20 + H2 = 2Cu + H2 0

Powders of W, Mo, Ni and CO are also manufactured by reduction process.

Reduction process is a convenient, economical and flexible method and perhaps the
largest volume of metallurgical powders is made by the process of oxide reduction.

(3) Electrolysis is principally used for the production of extremely pure powders of
copper(and Iron). Electrolysis is similar to electroplating. For making copper powder,
copper plates are placed as anodes in a tank of electrolyte, whereas aluminium
plates are placed into the electrolyte to act as cathodes. High amperage produces a
powdery- deposit of anode metal on the cathodes.

After a definite time period, the cathode plates are taken out from the tank, are
rinsed to remove electrolyte and are dried. The (Cu) deposit on the cathode plates, is
then scraped off and pulverized to produce powder of the desired grain size.

(4) Crushing requires equipments such as stamps, hammers, jaw crushers or

gyratorycrushes. Various ferrous and non-ferrous alloys can be heat-treated in order
to obtain a sufficiently brittle material which can be easily crushed into powder

(5) Milling operation is carried out by using equipments such as ball mill, impact mill,
eddymill, disk mill, vortex mill, etc. Milling (or grinding) can be classified as
comminution of brittle, friable, tough and hard materials and pulverization of
malleable and ductile metals.

A ball mill is a horizontal barrel-shaped container holding a quantity of balls which,

being free to tumble about as the container rotates, crush and abrade any powder
particles that are introduced into the container.Generally, a large mass to be
powdered, first of all, goes through heavy crushing machines, then through crushing,
rolls and finally through a ball mill to produce successively finer grades of powder
11. Powder Metallurgy Material Science & Metallurgy (2131904)

(6) Condensation of metal powders. This technique can be applied in tne case 01
meiais,such as Zn, Cd, and Mg, which can be boiled and the vapour are condensed in
a powder form. A rod of metal (say Zn) is fed into a high temperature flame. The
vaporized droplets of metal are allowed to condense on to a cool surface of a
material to which they will not adhere.

11.7 Characteristics of Metal Powders:

Most important characteristic of metal powder are:

1. Purity, 5. Particles shape,

2. Chemical composition, 6. Particle microstructure
3. Particle size, 7. Apparent density, and
4. Size distribution. 8. Flow rate.

Chemical Composition implies the type and percentage of alloying elements and
impuritiesandusually determines the particle hardness and compressibility. The
chemical composition of a powder can be determined by chemical analysis methods.

Particle Size is expressed by the diameter for spherical shaped particles and by the
averagediameter for non-spherical particles as determined by sieving method or
microscopic examination. Metal powders used in powder metallurgy usually vary in
size from 4 to 200 microns. Particle size influences mold strength, density/porosity of
the compact, permeability, flow and mixing characteristics, dimensional stability etc.

Particle-size Distribution is specified in terms of a sieve analysis, i.e., the amount of

powderpassing through 100-, 200-, etc., mess sieves. Particle-size distribution
influences packing of the powder and its behaviour during molding and sintering.

Particle Shape influences the packing and flow characteristics of powders. There are
variousshapes of metal powders, e.g.

Spherical (Condensed zinc)

Rounded (Atomized copper)
Angular (Mechanically atomized antimony). Acicular, dendritic, flakes,
irregular, etc.

Particle Microstructure reveals various phases, impurities, inclusions, fissures and

Material Science & Metallurgy (2131904) 11. Powder Metallurgy

Apparent Density is defined as the weight of a loosely heaped quantity of powder

necessaryto fill a given die cavity completely. Apparent density is influenced by
chemical composition, particle shape, size, size distribution, method of manufacture,
etc. The apparent density of iron powder (electrolytic) having average particle size of
63 microns is 2.56 gm/cc.

Flow Rate is defined as the rate at which a metal powder will now under gravity
from acontainer through an orifice both having the specific shape and finish.
Flow rate measures the ability of a powder to be transferred. Flow rate is an
important characteristic because the die must be filled rapidly with powder to
achieve high rate ofproduction and economy.

Flow rate depends upon particle size, shape, apparent density, etc. Spherical shaped
metal powders possess maximum flow rates whereas dendritic ones the least.

11.8 Blending and Mixing Of Powders:

Before the powders are pressed into shape, they are usually blended for the
following reasons:
To add lubricants (such as stearic acid, graphite, oils, paraffin, glycerin, etc.)
(to powder) to reduce friction during the pressing operations. Powder
particles get coated with lubricants. This reduces die wear and lowers the
pressure required for pressing.
To mix powders of different materials (i.e., alloying action), in order to
obtain properties of heat resistance, friction, heavy weight and hardness.
To obtain uniform distribution of particle sizes.
To add volatilizing agents to give a desired amount of porosity.

Different powders in correct proportions are thoroughly mixed either wet or dry, in a
ball mill. In wet mixing, water or a solvent is used to obtain better mixing. Moreover,
wet mixing.

Reduces dust,
Lessens explosion hazards which are present with some finely divided
powders, and
Prevents surface oxidation.
Proper blending and mixing of the powders are essential uniformity of the finished
product. However, over-mixing should be avoided since it may decrease particle size and
work hardens the particles.
11. Powder Metallurgy Material Science & Metallurgy (2131904)

11.9 Compacting:
After blending and mixing, the next step is that of compacting or pressing the
powders into their semi-finished form preparatory to sintering.

The purpose of compacting is to consolidate the powder into the desired shape and
as closely as possible to final dimensions, taking into account any dimensional
changes that result from sintering. Compacting also imparts
1. The desired level and type of porosity, and
2. Adequate strength for handling.
Powders are compacted by using high pressures. The degree of pressure depends

1. The required density of the final product, and

2. The ease with which the powder particles will weld together. Compacting
pressures may be applied in the following ways:
1. Die Pressing
2. Roll pressing
3. Extrusion

1. Die pressing is done in special presses that include a feed hopper for the powder,
theshaping die to form the product, an upper punch and a lower punch to apply
correct pressures onto the powder being compacted. Weighed- quantity of powder
is placed in the die through the hopper and is compressed under pressure ranging
from 8 to 158 kg/sq. mm.

2. Roll pressingis used for production of continuous strip section, using a system as
shownin Fig. 8.3There are two rolls of appropriate size into which a regulated stream
of powder is guided, so that the rolls are able to apply the necessary compacting
pressure in a continuous sequence.

Fig. 11.3 Roll compacting

Material Science & Metallurgy (2131904) 11. Powder Metallurgy

3. The Extrusion method of compacting does not give such efficient control as that
given bypressing or by rolling. It is difficult to obtain high densities and some
porosity is always left.

g. 11.4 Extrusion Method

11.10 Presintering and Sintering:


Frequently, powder metallurgy is used to make parts from materials that are
very difficult to machine.
When some machining is required on such parts, one goes lot presintering
before the actual sintering operation.
After presintering operation, the compacted part acquires sufficient strength
to behandled and machined without difficulty. Moreover, very little
dimensional change takes place, then in the final sintering, therefore,
machining after final sintering may be eliminated.
11. Powder Metallurgy Material Science & Metallurgy (2131904)

For presintering, the compacted parts are heated for a shot time at a
temperature considerably below the final sintering temperature.
Presintering is necessary when holes are to be drilled in hard to machine
parts. Presintering, in addition, removes lubricants and binders added to the
powders during the blending operation.
Presintering can be eliminated if no machining of the final product is

After being compressed into a briquette of the shape required in the finished
component, the agglomerated metals are sintered. Sintering is done to
achieve all possible final strength and hardness needed in the finished
Sintering consists of heating pressed metal or cermet compacts in batch or
continuous furnaces' to a temperature below the melting point of the major
constituent in an inert or reducing atmosphere (of hydrogen, dissociated
ammonia or cracked hydrocarbon), where time, temperature, heating rate
and cooling rate are automatically controlled.Most metals are sintered at 70
to 80% of the melting temperature. Certain refractory materials may be
sintered at 90% of the melting point.
The sintering time varies from thirty minutes up to several hours. Sintering
temperatures and times vary considerably with different materials, e.g.,
Porous bronze bearings require treatment for only a few minutes at 800C;
iron base compacts and cemented carbides require treatment for up to 2
hours at 1200-1250C, etc.
Sintering is essentially a process of bonding solid bodies (particles) by atomic
Bonding of powder particles during sintering can take place in any of the
three ways:

1. Melting of a minor constituent,

2. Volume diffusion, although surface diffusion, evaporation and condensation
also contribute to bonding.

11.11 Secondary Operations:

In many cases, the metal parts may be used in the as-sintered condition, but in other
cases where desired surface finish, tolerance or metal structure cannot be obtained
by briquettingsize and shape. The briquette is considered fairly fragile, but it can be
handled), certain additional operations must follow. They are
Material Science & Metallurgy (2131904) 11. Powder Metallurgy

1. Sizing 4. Impregnation 7. Heat treatment

2.Coining 5. Infiltration 8. Joining

3.Machining 6.Plating

1. Sizing
Sintering process produces some distortion and alterations in size. After the part has
been sintered, in order to make it dimensionally correct, it is placed in a die and is
repressed. Sizing improves surface finish of the component also. However, a slight
change in density occurs during sizing.

2. Coining.
The sintered part is repressed in the die to reduce the void space and impart the
required density.

3. Machining.
Features such as threads, under cuts, grooves etc., are usually not practical for
powder metallurgy fabrications, and are generally machined on parts after they
have been presintered. Boring, turning, drilling, tapping, etc., can be done on
presintered parts using tungsten carbide cutting tools.

4. Impregnation
Sintered parts may be impregnated with oil, grease, wax or other lubricating
materials, in case self-lubricating properties are desired. Parts are immersed in
lubricants heated to approximately 93C. The porous structure gets completely
(about 90%) impregnated in 10 to 20 minutes. The lubricant is retained in the
part by capillary action.
The sintered part may be impregnated with plastics also. This is done in order to,

1. Improve corrosion resistance,

2. Seal prior to plating.
3. Improve machinability.
4. Introduce pressure tightness.

5. Infiltration
A part is first pressed and sintered from iron powder to about 77% of theoretical
density. Then a replica (or infiltration) blank of copper (or brass) is placed over the
part which is sent through the furnace. The infiltrant melts and soaks through the
porous part, producing a density close to 100%.
11. Powder Metallurgy Material Science & Metallurgy (2131904)

6. Plating
Plating is carried out in order to,

1. Impart a pleasing appearance (Cr plating).

2. Protect from corrosion (Ni plating).
3. Improve wear resistance (Ni or Cr plating).
4. Improve frictional (Tin plating) and hardness characteristics (Cr plating)
5. Improve electrical conductivity (Cu and Ag plating).
6. Before plating, the part is impregnated with plastic resin so that the
electrolyte is not entrapped in the porous structure during plating.
7. Sintered parts, then, may be plated with Cr, Ni, Co, Cd, Zn, brass, etc.

7. Heat treatment
Sintered parts are heat treated in order to
1. Wear resistance. 3. Hardness
2. Grain structure. 4. Strength.
To prevent oxidation of the internal structure, the heat treatment is carried out in
controlled atmosphere. The porosity of sintered parts decreases the heat
conductivity, therefore longer heating and shorter cooling periods are required.
Following heat treatment processes are usually applied to parts made by powder
1. Stress relieving 5. Through hardening
2. Carburizing 6. Induction hardening
3. Carbonitriding
4. Nitriding

8. Joining of sintered parts

Parts may be joined after they have been sintered or the joining may be
incorporated into sintering operation. Various joining, techniques are
1. Soldering (on A1 and Cu based sintered parts).
2. Brazing (carried out in vacuum or controlled atmosphere. High frequency
heating is preferred).
3. Welding (TIG welding, projection welding, friction welding, electron beam
Non Destructive Testing

Course Contents
12.1 Non Destructive Test

12.2 Types of NDT

12.3 Liquid Penetrant Inspection


12.4 Magnetic Particle Inspection

12.5 Radiography of Metals

12.6 Ultrasonic Inspection

12.7 Eddy Current Inspection

12.8 Jominey End Quench Test

12. Non Destructive Testing Material Science & Metallurgy (2131904)

12.1 Non Destructive Test:

A nondestructive test is an examination of an object in any manner which will not impair
the future usefulness of the object.
In most cases NDT test do not provide a direct measurement of mechanical properties,
they are very valuable in locating material defects that could impair the performance of
a machine member when placed in service.
Such test is used to detect faulty materials before it is formed or machined into
components parts, to detect faulty components before assembly, to measure thickness
of metal, and to discover defects that may have developed during processing or use.
Parts may be examined in service permitting their removal before failure occurs.
Non destructive tests are used to make more reliable, safe and economical.
During and just after world war-II the significance of imperfections to the useful life of
product assumed greater importance.
Example: In air craft design, in nuclear technology and in space exploration, high hazards
and costs have made maximum reliability essential.

12.2 Types of NDT:

1. Radiography
2. Fluorescent penetrant inspection (liquid penetrant inspection)
3. Ultrasonic inspection
4. Eddy current inspection

12.3 Liquid Penetrant Inspection (DPT):

The principle of the technique is that a liquid is drawn by capillary attraction in the
defects and after sub sequent development, any surface barking defects may be
rendered visible to the human eye.
In order to achieve good defect visibility the penetrating liquid will either be coloured
with bright and persistent dye or else contain fluorescent component.
In DPT the dye is generally red and developed surface can be viewed in natural or
artificial light but in the latter case the compound must be viewed under ultraviolet
light if indications of defects are to be seen.
DPT is an important to indicate the presence of defects such as cracks, laminations, laps
and zones of surface porosity in wide range of components. It is employed for the
inspection of wrought and cast products in both ferrous and non-ferrous metals and
alloys, ceramics glass and some polymer components.

Five steps in liquid penetrant inspection:

1. Surface preparation
2. Application of penetrant
3. Removal of excess penetrant
4. Development
5. Observation and inspection

Fig. 12.1 Major steps for in fluorescent-penetration inspection

The surface of a component must be free from oil, grease and other contaminants if
successful indication of defect is to be achieved.
After surface preparation, liquid penetrate is applied by brush, spray or immersion so as
to form a film of penetrate over the component surface.
Penetrant will seep in to fairly large flows in a few seconds but it may take up to 30 min
for the liquid to penetrate into very small defects and tight cracks.
After the penetration stagge, it is necessary to remove excess penetrant from the surface
of the component. Some penetrant can be washed off the surface with water, while
other requires the use of specific solvents.
The development stage is necessary to reveal clearly the presence of any defects. The
developer is usually a very fine chalk powder. This may be appliied dry, but more
commonly is applied by spraying the surface with chalk dust suspended in a volatile
carrier fluid. A thin uniform layer of chalk is deposited on the surface of component.
Penetrant liquid present within defects will be slowly down by capillary action in to the
pairs of the chalks. There will be some spread of penetrant within the developer and this
will magnify the apparent width of defect.
When dye penetrant is used, the dye colour must be sharp contrast to the uniform white
of the chalk covered surface.
Dye penetrant inspection is carried out in strong lighting conditions, while fluorescent
penetrant inspection is performed using ultraviolet light.

Advantage of DPT:
1. DPT is simple as no electronic system is involved.
2. It is cheaper than other NDT tests.

Limitations of DPT:
1. It can detect surface breaking defects only.
12. Non Destructive Testing Material Science & Metallurgy (2131904)

2. This method is not suitable for naturally porous material such as unglazed ceramics and
some thermo plastic material as it affects by penetrant fluid.

Applications of DPT:
Aerospace, automotive and general manufacturing industries for the quality control of
production and by users during regular maintenance and safety checks.
Examples: Turbine rotor discs, blades, pistons, cast cylinder head wheel, forged
components. Weld assembly.

12.4 Magnetic particle inspection:

Magnetic particle inspection is a sensitive method of locating surface and some sub
surface defects in ferromaagnetic components.
When discontinuity is open to the surface, the magnetic field leaks out to the surface
and terms north and south poles and that attract magnetic particles.
When a ferromagnetic material is magnetized, magnetic discontinuities that lie a
direction approximately perpendicular to the field direction will result in a formation of
strong leakage field. This leakage field is present at and above the surface of the
magnetized component, and its presence can be detected using finely divided magnetic
particles. The application of dry particles or wet particles in a liquid carrier over the
surface of the component results in a collection of magnetic particles at a discontinuity.
This magnetic bridge indicates the location, size and shape of the discontinuity.
When discontinuities are under the surface some parts of the field may still be deflected
to the surface, but the leakage is less and few particles are attracted, so that indication
obtained is much weaker. If the discontinuity is far below the surface, no leakage of the
field will be obtained and consequently no indication.

Fig. 12.2 Principle of magnetic flux test

Fig. 12.3 Methods of magnetic flux test

Fig. 12.4 Magnetic flaw detection

As shown in figure for longitudinal magnetization the magnetic field may be produced in
a direction parallel to the long axis of work piece by placing the piece in a coil excited by
an electric current so that the long axis of the piece is parallel to the axis of coil. Very
long parts are magnetized in steps by moving the coil along the length.
In case of circular magnetization, a magnetic field transverse to the long axis of the work
piece is readily produced by passing the magnetizing current through the piece along
this axis.
All machine parts that have been magnetized for inspection must be put through a
demagnetizing operation. If these parts placed in service without demagnetizing, they
will attract filing, grinding, chips and other steel particle which cause scaring of bearing
and other engine parts.
12. Non Destructive Testing Material Science & Metallurgy (2131904)

12.5 Radiography of Metals:

Radiography of metals may be carried out by using X-rays or gamma rays short wave
length electromagnetic rays capable of going through large thickness of metals.
Gamma rays may be obtained from naturally radioactive material such as radium or
radioactive isotope such as cobalt-60
Gamma radiation is more penetrating than that of X-rays but the inferior sensitivity
limits its application.
X-rays are produced when matter is bombarding by a rapidly moving stream of
electrons. When electrons are suddenly stopped by a matter a part of their kinetic
energy is converted in to energy of radiation or X-rays.

Fig. 12.5 Schematic representation of the use of X-rays for examination of a welded plate

Fig. 12.6 Types of Radiographs

The essential conditions for the generation of X-rays are:
1. A filament (cathode) to provide source of electron proceeding towards the target.
2. A target (anode) located in the path of electrons.
3. Voltage difference between anode and cathode will regulate the velocity of
electrons striking the target and thus regulate the wavelength of X-rays produced.
4. A means of regulating tube current to control the number of electrons striking the
X- Rays are potentially dangerous and adequate safe guards must be employed to
protect operating person.
Radiography is a shadow picture of a material more or less transparent to radiation. The
X-rays darken the film so those regions by lower density which readily permit
penetration appear dark on the negative as compared with region of higher density
which absorbs more of the radiation. Thus hole or crack appears as a darker area.

Fig. 12.7 A simple radiation thickness gauge

Radiography of metals has been used for inspection of casting and welded products; it
may be used to measure the thickness of materials also. Figure 1.30 shows a simple
radiation thickness gauge. The radiation from the source is influenced by the material
being tested. As the thickness increases, the radiation intensity reading the detector
decreases. If the response of the detector is calibrated for known thickness, the detector
reading can be used to indicate the thickness of the inspected material with a suitable
feedback circuit; the detector may be used to control the thickness between
predetermined limits.

12.6 Ultrasonic Inspection:

1. It is used to detect and locate defects such as shrinkage, cavities, cracks, porosity and
large metallic inclusions wall thickness can be measured in close vessel.
2. Ultrasonic vibrations can be used to locate defects in ferrous and nonferrous metals,
plastics and ceramics.
12. Non Destructive Testing Material Science & Metallurgy (2131904)

3. Ultrasonic inspection for flow detection makes use of acoustic waves with frequency in
the range of 20 KHz and 20 MHz which can be transmitted through solids and get
reflected by subsurface defects.
4. The use of sound waves to determine a defect is a very old / ancient method. If a piece
of metal is struck by a hammer it will radiate certain audible/easy to hear notes, of
which pitch and clamping may be influenced by the presence of internal flows. However
this technique of hammering and listening is useful only for the determination of large
5. Here sound waves above audible range with frequency 1 to 5 million Hz (cycle/sec)
hence it is known as ultrasonic.
6. Ultrasonic is a fast, reliable, non destructive testing method which employs
electronically produced high frequency sound waves that will penetrate metals, liquids
and other metals at a speed of several thousand feet/sec.
7. Ultrasonic waves for NDT are usually produced by piezoelectric materials. These
materials undergo a change in physical dimensions when subjected to electric field.
8. This conversion of electrical energy to mechanical energy is known as piezoelectric
effect. If an alternating electric field is applied to a piezoelectric crystal, the crystal will
expand during the first half of cycle and contact when the electric field is reversed. By
varying the frequency of the alternating electric field, we can vary the frequency of the
mechanical vibration (sound wave) produced in the crystal. Quartz is a widely used
ultrasonic transducer. A transducer is a device for converting one form of energy to
Ultrasonic test methods:
1. Through Transmission Method:
This method uses an ultrasonic transducer on each side of the object being inspected. If an
electrical pulse of the desired frequency is applied to the transmitting crystal, the ultrasonic
waves produced will travel through the specimen to the other side. The receiving transducer
on the opposite side receive the vibrations and converts them in to an electrical signed than
can be amplified and observed on the cathode ray tube of an oscilloscope, a meter or some
other indicator. If the ultrasonic wave travels through the specimen without encountering
any flow, the signal received is relatively large. If there is a flow in the path of the ultrasonic
wave part of the energy will be reflected and the signal received by the receiving transducer
will be reduced.

Fig. 12.8 The through-transmission and pulse echo methods of ultrasonic inspection
2. The Pulse Echo Method:
This method uses one transducer which serves as both transmitter and receiver. It is
same as the transmission method.
As sound wave enters the material being tested, part of it is reflected back to the crystal
where it is converted back to an electrical impulse.
This impulse is amplified and rendered visible as an indication or pip on the screen of the
oscilloscope. When the sound wave reached the other side of the material, it is reflected
back and shows a pip on the screen further to the right of first pip. If there is a flow
between front and back surface of the material, it will shows as a third pip on the screen
between the two indications for the front and back surfaces.

Fig. 12.9 Oscilloscope pattern for the pulse eco method of ultrasonic inspection

Fig. 12.10 Detection of crack with ultrasonic machine

Since the indications on the oscilloscope screen measure the elapsed time between
reflection of the pulse from the front and back surfaces, the distance between
indications is a measure of the thickness of the material. The location of a defect may
therefore be accurately determined from the indications on the screen.
12. Non Destructive Testing Material Science & Metallurgy (2131904)

For larger parts, a film of oil ensured proper contact between the crystal searching unit
and test piece. Smaller parts may be placed in a tank of water, oil or glycerin. The crystal
searching units transmits sound waves through the medium and into material being
Close examination of the oscilloscope screen in the picture shows the presence of three
pips. The left pip indicates the front of the piece. The right pip the back of the piece and
the smaller center pip is an indication of flow.
1. It is used to detect and locate such defect as shrinkage cavities, internal bursts or cracks,
porosity and large non metallic inclusions.
2. Wall thickness can be measured in a close vessel.

12.7 Eddy current inspection:

Current techniques are used to inspect electrically conducting materials for defects,
irregularities in structure, and variations in composition. In eddy current testing, a varying
magnetic field is produced if a source of a source of alternating current is connected to a
coil. When this field is placed near a test specimen capable of conducting an electrical
current, eddy currents will be induced in the specimen. The eddy currents, in turn, will
produce a magnetic field of their own. The detection unit will measure this new magnetic
field and convert the signal into a voltage that can read on a meter or a cathode ray tube.
Properties such as hardness, alloy composition, chemical purity, and heat treat condition
influence the magnetic field and may be measured directly by a single coil.

An important use for eddy current testing is sorting material for heat treat variations or
composition mix-ups. This application requires the use of two coils.(see fig.) A standard
piece is placed in one coil and the test piece in other coil. Acceptance or rejection of the test
piece may be determined by comparing the two patterns on the oscilloscope screen.

Eddy current testing may be used to detect surface and sub-surface defects, plate or tubing
thickness, and coating thickness.

Fig. 12.11 Eddy current test

Fig. 12.12 Eddy Current Inspection

Table 12.1: Major nondestructive testing methods

Inspection When to use Where to use Advantages Limitations


Eddy current Measuring Tubing and bar High speed, False indication
variations in wall stock, parts of noncontact, result from
thickness of thin uniform automatic. many variables;
metals or coatings; geometry, flat only good for
detecting stock, or sheet conductive
longitudinal seems and wire. materials;
or cracks in tubing; limited depth of
determining heat penetration.
treatments and
metal compositions
for sorting.


x-rays Detecting internal Assemblies of

flaws and defects; electronic parts,
finding welding casting, welded
flows, cracks, vessels; field
seams, porosity, testing of welds;
holes, inclusions, corrosion
lack of fusion, surveys;
Provides permanent High initial cost;
measuring component of
records on film; power source
variations in nonmetallic
thickness. materials. Works well on thin required;
sections; high radiation
sensitivity; hazard; trained
12. Non Destructive Testing Material Science & Metallurgy (2131904)

Gamma x-rays Detecting internal Forgings, fluoroscopy technicians

flaws, cracks, castings, tubing, techniques needed.
seams, holes, welded vessels; available;
inclusions, weld field testing adjustable energy
defects; measuring welded pipe; level.
thickness variations. corrosion

Magnetic Detecting surface or Only for Economical, simple Material must

particle shallow subsurface ferromagnetic in principle, easy to be magnetic;
flaws, cracks, materials; parts perform, portable; demagnetizing
porosity, of any size, fast for production after testing is
nonmetallic shape, testing. required;
inclusions, and weld composition, or power source
defect. heat treatment. needed; parts
must be
cleaned before

Penetrant Locating surface All metals, glass, Simple to apply, Limited to

crack, porosity, laps, and ceramics, portable, fast, low surface defects;
cold shuts, and lack castings, forgings, in cost; results easy surface must be
of weld bond, machined parts, to interpret; no clean.
fatigue, and and cutting tools; elaborate setup
grinding cracks. field inspections. required.

Ultrasonic pulse Finding internal All metals and Fast, dependable, Requires
echo defects, cracks, lack hard nonmetallic easy to operate; contact or
of bond, materials, sheets, lends itself to immersion of
laminations, tubing, rods, automation, result part;
porosity, forgings, castings, of test immediately interpretation
determining grain field and known; relatively of readings
structure and production portable, highly requires
thicknesses. testing; in service accurate, sensitive. training.
part testing;
brazed and
adhesive bonded
12.8 Jominey End Quench Test:
The usual method of purchasing steel is on the basis of chemical composition. This
allows a considerable variation in the carbon and alloy of the steel.
Example: AISI 4340 Steel
C = 0.38-.043% Ni = 1.65 2.0%
Mn = 0.60-0.80% Cr = 0.70 0.90%
Si = 0.20 0.35% Mo = 0.20 0.30%

Lets determine percentage variation in each alloying element.

For C
Difference between 0.43 and 0.38=0.05
= 12.5 %
(. . )/

So % variation for difference metal and alloy is given as.

Mn = 28.7% Ni = 19.1% Mo = 40%

Si = 53.8% Cr = 25%
This variation in chemical composition within a particular grade will cause a variation in
the critical cooling rate and in turn a variation in the response of the steel to heat
Therefore buying a steel according to chemical composition is No assurance that full
hardness will be attained under certain quenching conditions. It is therefore necessary o
have a test that will predict he Hardenability of the steel.
In test has been standardized by ASTM, SAE & AISI. In conducing this test 1 round
specimen 4 long is heated uniformly o he proper Ausetnizing temperature. It is then
removed from the furnace on a placed on a fixture where a jet of water impinges on the
bottom face of the specimen. The size of the orifice, from the orifice to the bottom of
the specimen and temperature and circulation of water all are standardized. So that
every specimen quenched in this fixtures receives the same cooling rate. After 10
minutes on the fixture, the specimen is removed and two parallel surfaces are ground
longitudinally to a depth of 0.015 inch. Rockwell C scale hardness reading is taken at
1/16 interval from the quenched end. The results are expressed as a curve of Hardness
Vs Distance from the quenched end.
End quench Hardenability curve readily shows that how Hardenability varies with actual
cooling rates for particular steel.
12. Non Destructive Testing Material Science & Metallurgy (2131904)

When a steel piece of large cross section is heated to a austenite temperature and then
quenched, the cooling rate decreases from the surface to the interior. Martensite is
obtained at the surface due to highest cooling rate. But it is not possible to get a
martensitic structure at the center due to the relatively slow cooling rate. Hence, a
gradient of hardness exists from the surface to the center. Since every grade of steel has
its own transformation characteristics, the depth of penetration of hardness across the
cross section differs. The measure of these properties termed as Hardenability of the
Hardenability is defined as the relative ability of steel to be hardened by quenching and
it determines the depth and distribution of hardness across the cross section.
Hardenability should not be confused with maximum hardness of steel.
Hardenability is very useful and important property of steel. It determines the rate at
which the given steel should be quenched. Maximum hardness is mainly a function of
carbon content. Hardenability of steel depends on
1. Composition of steel
2. Method of manufacture
3. Section of the steel
4. Quenching medium
5. Quenching method
In industry, a simple experiment called Jominey End Quench Test (named after Walter
Jominey, American Metallurgist) is used to determine Hardenability of steel.
The objective of the experiment is to take readings in the Rockwell C scale along the flat
surface of the Jominey specimen and to plot the graph Hardness vs. Distance from
quenched end.
1. Electric furnace
2. Jominey end quench test fixture
3. Jominey specimen (made as per ASTM standard)
4. Rockwell hardness tester
Test Procedure:
1. Preheat the furnace to 1700 F (910C-920 C)
2. Place the Jominey specimen in the furnace and soak for one hour.
3. Turn the water on at Jominey sink. Adjust the free water column about 2.5 inches.
Swivel the baffle plate to block the water column so that there is no contact between
water and the test specimen when the test specimen is initially placed on the fixture.
4. Remove the Jominey specimen from the furnace and place in the fixture as shown in
figure. Swivel the baffle out of position so that water impinges on the bottom of the
specimen without wetting the sides of specimen. Leave water running for about 15

Fig. 12.13 Apparatus used in the test and Standard form of test piece

5. Remove the Jominey specimen from the fixture and grind a flat on the side of the
6. Mark points on the ground surface at an interval of 1.6mm distance from the quench
end as shown in figure.
7. Take reading at an interval of 1.6mm intervals. Near the quenched end, this interval is
reduced to 0.8mm as hardness values vary rapidly.

Fig. 12.14Hardness variation in quenched Jominey bar

8. The results are expressed as a curve of hardness value vs. distance from the quenched
end (Jominey distance). This curve is called the Jominey Hardenability curve.