33345

Dept. of Mechanical Engineering, St.
Josephs College of Engineering
ME 2253 ENGINEERING MATERIALS & METALLURGY

UNIT I CONSTITUTION OF ALLOYS AND PHASE DIAGRAMS
Constitution of alloys Solid solutions, substitutional and interstitial phase diagrams,
Isomorphous, eutectic, peritectic, eutectoid and peritectroid reactions, Iron Iron carbide
equilibrium diagram. Classification of steel and cast Iron microstructure, properties and
application.
Materials
Materials are very important in development of human civilization. In respect, their
names are associated in history, e.g. stone age, Bronze age, Iron age, etc.
Properties of materials
i.
All solid engineering materials are characterized for their properties.
ii.
Engineering use of a material is reflection of its properties under conditions of
use.
iii.
All important properties can be grouped into six categories: Mechanical,
Electrical, Thermal, Magnetic, Optical, and Deteriorative.
iv.
Each material possess a structure, relevant properties, which dependent on
processing and determines the performance.
v.
Since there are thousands of materials available it is almost impossible to select a
material for a specific task unless otherwise its properties are known.
vi.
There are several criteria on which the final decision is based on.
vii.
There are less chances of material possessing optimal or idle combination of
properties.
viii.
A need to trade off between number of factors!
Material Science
It can be defined as science dealing the relationships that exist between the structures and
properties of materials, which are useful in practice of engineers profession.
Classification of Materials
Three basic groups of solid engineering materials based on atomic bonds and structures:
Metals
Ceramics
Polymers
Classification can also be done based on either properties (mechanical, electrical,
optical), areas of applications (structures, machines, devices). Further we can subdivide
these groups. According to the present engineering needs:
Composites,
Semiconductors,
Biomaterials
Modern Material needs
Dept. of Mechanical Engineering, St. Josephs College of Engineering
Engine efficiency increases at high temperatures; requires high temperature

structural materials.
Use of nuclear energy requires solving problems with residue, or advance in
nuclear waste processing.
Hypersonic flight requires materials that are light, strong and resist high
temperatures.
Optical communications require optical fibers that absorb light negligibly.
Civil construction materials for unbreakable windows.
Structures: materials that are strong like metals and resist corrosion like plastics.
ALLOY
Alloy is a substance that has metallic properties and is composed of two or more
chemical elements, of which at least one is a metal. In which the major proportion of the
metal is called as base metal and the minor proportion of the metal or element is alloying
element.
Alloys can be according to classified by
1. Based on the no of components
2. Based on the no of equilibrium or phases
3. Based on the structures
Alloys may be homogeneous (uniform) or mixtures. If the alloy is homogeneous it will
consist of a single phase and if it is a mixture it will be a combination of several phases.
Phase
A phase can be defined as a homogeneous portion of a system that has uniform physical
and chemical characteristics i.e. it is a physically distinct from other phases, chemically
homogeneous and mechanically separable portion of a system.
Pure Metal
In nature 100% pure metal is impossible to get, hence only 99.99% of pure metal
can exist with 0.01% of impurities.
In the equilibrium conditions, all the metals exhibit a definite melting or freezing
point
This condition implies extremely slow heating and cooling (i.e for any change is
to occur sufficient time must be allowed)
The cooling cure for the pure metal will be a horizontal line at the melting or
freezing point
Based on the no of components
1. Binary alloy system The system if made up of two elements
2. Ternary alloys system - The system is made up of three elements
Based on the structures

Alloy
Homogeneous
Mixture
Intermediate
alloy phase
Any combination of
solid phases
Solid Solution
Substitutiona
l
Interstitial
Intermetallic Interstitial
Electron
Solid Solution
A solid solution is formed when two metals are completely soluble in liquid state and
also completely soluble in solid state. In other words, when homogeneous mixtures of
two or more kinds of atoms (of metals) occur in the solid state, they are known as solid
solutions. The more abundant atomic form is referred as solvent and the less abundant
atomic form is referred as solute. For example sterling silver (92.5 percent silver and the
remainder copper) is a solid solution of silver and copper. In this case silver atoms are
solvent atoms whereas copper atoms are solute atoms. Another example is brass. Brass is
a solid solution of copper (64 percent) and zinc (36 percent). In this case copper atoms
are solvent atoms whereas zinc atoms are solute atoms.
Types of Solid Solutions
Solid solutions are of two types. They are
(a) Substitutional solid solutions.
(b) Interstitial solid solutions.
Substitutional Solid Solutions
If the atoms of the solvent or parent metal are replaced in the crystal lattice by atoms of
the solute metal then the solid solution is known as substitutional solid solution.
The substitutional solid solution is further subdivided into
1. Disordered substitutional solid solution
2. Ordered substitutional solid solution
In disordered substitutional solid , where the solute atoms are randomly substituted for
the solvent atoms. Its shown in the given figure below.
In ordered substitutional solid , where the solute atoms are orderly substituted for the
solvent atoms. Its shown in the given figure below.
Example, copper atoms may substitute for nickel atoms without disturbing the F.C.C.
structure of nickel (Fig. a). In the substitutional solid solutions, the substitution can be
either disordered or ordered. Fig. b shows disordered substitutional solid solution. Here
the solute atoms have substituted disorderly for the solvent atoms on their lattice site. Fig.
c shows an ordered substitutional solid solution. Here the solute atoms have substituted in
an orderly manner for the solvent atoms on their lattice site.
Interstitial Solid Solutions
In interstitial solid solutions, the solute atom does not displace a solvent atom, but rather
it enters one of the holes or interstices between the solvent atoms. Interstitial solid
solutions normally have a limited solunility. Example is iron-carbon system which is
shown in fig.
In this system the carbon (solute atom) atom
occupies an interstitial position between iron
(solvent atom) atoms. Normally, atoms which have
atomic radii less than one angstrom are likely to
form interstitial solid solutions. Examples are atoms
of carbon (0.77 A), nitrogen (0.71 A), hydrogen
(0.46 A), Oxygen (0.60 A) etc.
Intermetallic Compounds
Intermetallic compounds are generally formed when one metal (for example magnesium)
has chemical properties which are strongly metallic and the other metal (for example
antimony, tin or bismuth) has chemical properties which are only weakly metallic.
Examples of intermetallic compounds are Mg2Sn, Mg2Pb, Mg3Sb2 and Mg3 Bi2. These
intermetallic compounds have higher melting point than either of the parent metal. This
higher melting point indicates the high strength of the chemical bond in intermetallic
compounds.
Hume Rothery rules Controls the range of Solubility in alloy system

(a) Crystal structure factor: For complete solid solubility, the two elements should have
the same type of crystal structure i.e., both elements should have either F.C.C. or B.C.C.
or H.C.P. structure.
(b) Relative size factor: As the size (atomic radii) difference between two elements
increases, the solid solubility becomes more restricted. For extensive solid solubility the
difference in atomic radii of two elements should be less than about 15 percent. If the
relative size factor is more than 15 percent, solid solubility is limited. For example, both
silver and lead have F.C.C. structure and the relative size factor is about 20 percent.
Therefore the solubility of lead in solid silver is about 1.5 percent and the solubility of
silver in solid lead is about 0.1 percent. Copper and nickel are completely soluble in each
other in all proportions. They have the same type of crystal structure (F.C.C.) and differ
in atomic radii by about 2 percent.
(c) Chemical affinity factor: Solid solubility is favoured when the two metals have lesser
chemical affinity. If the chemical affinity of the two metals is greater then greater is the
tendency towards compound formation. Generally, if the two metals are separated in the
periodic table widely then they possess greater chemical affinity and are very likely to
form some type of compound instead of solid solution.
(d) Relative valence factor: If the solute metal has a different valence from that of the
solvent metal, the number of valence electrons per atom called the electron ratio. It is
found that a metal of lower valence tends to dissolve more of a metal of higher valence
than vice versa. For example in aluminium-nickel alloy system, nickel (lower valance)
dissolves 5 percent aluminium but aluminium (higher valence) dissolves only 0.04
percent nickel.
Phase Diagrams
Many of the engineering materials possess mixtures of phases, e.g. steel, paints, and
composites. The mixture of two or more phases may permit interaction between different
phases, and results in properties usually are different from the properties of individual
phases. Different components can be combined into a single material by means of
solutions or mixtures. A solution (liquid or solid) is phase with more than one
component; a mixture is a material with more than one phase. Solute does not change the
structural pattern of the solvent, and the composition of any solution can be varied. In
mixtures, there are different phases, each with its own atomic arrangement. It is possible
to have a mixture of two different solutions!
A pure substance, under equilibrium conditions, may exist as either of a phase namely
vapor, liquid or solid, depending upon the conditions of temperature and pressure. A
phase can be defined as a homogeneous portion of a system that has uniform physical
and chemical characteristics i.e. it is a physically distinct from other phases, chemically
homogeneous and mechanically separable portion of a system. In other words, a phase is
a structurally homogeneous portion of matter. When two phases are present in a system,
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it is not necessary that there be a difference in both physical and chemical properties; a
disparity in one or the other set of properties is sufficient.
There is only one vapor phase no matter how many constituents make it up. For pure
substance there is only one liquid phase, however there may be more than one solid phase
because of differences in crystal structure. A liquid solution is also a single phase, even
as a liquid mixture (e.g. oil and water) forms two phases as there is no mixing at the
molecular level. In the solid state, different chemical compositions and/or crystal
structures are possible so a solid may consist of several phases. For the same
composition, different crystal structures represent different phases. A solid solution has
atoms mixed at atomic level thus it represents a single phase. A single-phase system is
termed as homogeneous, and systems composed of two or more phases are termed as
mixtures or heterogeneous. Most of the alloy systems and composites are heterogeneous.
It is important to understand the existence of phases under various practical conditions
which may dictate the microstructure of an alloy, thus the mechanical properties and
usefulness of it. Phase diagrams provide a convenient way of representing which state of
aggregation (phase or phases) is stable for a particular set of conditions. In addition,
phase diagrams provide valuable information about melting, casting, crystallization, and
other phenomena.
Useful terminology:Component is either pure metal and/or compounds of which an alloy is composed. The
components of a system may be elements, ions or compounds. They refer to the
independent chemical species that comprise the system.
System it can either refer to a specific body of material under consideration or it may
relate to the series of possible alloys consisting of the same components but without
regard to alloy composition.
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.
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.
Variables of a system these include two external variables namely temperature and
pressure along with internal variable such as composition (C) and number of phases (P).
Number of independent variables among these gives the degrees of freedom (F) or
variance.
Gibbs Phase Rule
In a system under a set of conditions, the relationship between number of phases (P) exist
can be related to the number of components (C) and degrees of freedom (F) by Gibbs
phase rule.
P+F=C+2
Where, P no of phases (solid, liquid, Gaseous etc)
C No of components in the alloy
F Degrees of freedom refers to the number of independent variables (e.g.:
pressure, temperature) that can be varied individually to effect changes in a
system.
Thermodynamically derived Gibbs phase rule:
In practical conditions for metallurgical and materials systems, pressure can be treated as
a constant (1 atm.). Thus Condensed Gibbs phase rule is written as:
P+F=C+1
Polymorphism and Allotropy
Polymorphism is a physical phenomenon where a material may have more than one
crystal structure. A material that shows polymorphism exists in more than one type of
space lattice in the solid state. If the change in structure is reversible, then the
polymorphic change is known as allotropy. The prevailing crystal structure depends on
both the temperature and the external pressure.
One familiar example is found in carbon: graphite is the stable polymorph at ambient
conditions, whereas diamond is formed at extremely high pressures.
The best known example for allotropy is iron. When iron crystallizes at 2800 oF(1536oC)
it is B.C.C. (d -iron), at 2554 oF(1391oC) the structure changes to F.C.C. (g -iron or
austenite), and at 1666oF(914oC)it again becomes B.C.C. (a -iron or ferrite).
(bcc) (fcc) (bcc) Liquid
Unlimited Solid Solubility: Solute and solvent are mutually soluble at all concentrations,
e.g., Cu-Ni system Meets the requirements of the Hume-Rothery Rules,result is a single
phase alloy
Limited or Partial Solid Solubility: There is a limit to how much of the solute can dissolve
in the solvent before saturation is reached, e.g., Pb-Sn and most other systems. Does not
meet the requirements of the Hume-Rothery Rules. Results in a multi-phase alloy
Equilibrium Phase Diagrams
A diagram that depicts existence of different phases of a system under equilibrium is
termed as phase diagram. It is also known as equilibrium or constitutional diagram.
Equilibrium phase diagrams represent the relationships between temperature and the
compositions and the quantities of phases at equilibrium. In general practice it is
sufficient to consider only solid and liquid phases, thus pressure is assumed to be
constant (1 atm.) in most applications. These diagrams do not indicate the dynamics
when one phase transforms into another. However, it depicts information related to
microstructure and phase structure of a particular system in a convenient and concise
manner. Important information, useful for the scientists and engineers who are involved
with materials development, selection, and application in product design, obtainable from
a phase diagram can be summarized as follows:
- To show phases are present at different compositions and temperatures under
slow cooling (equilibrium) conditions.
- To indicate equilibrium solid solubility of one element/compound in another.
- To indicate temperature at which an alloy starts to solidify and the range of
solidification.
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- To indicate the temperature at which different phases start to melt.

- Amount of each phase in a two-phase mixture can be obtained.
A phase diagram is actually a collection of solubility limit curves. The phase fields in
equilibrium diagrams depend on the particular systems being depicted. Set of solubility
curves that represents locus of temperatures above which all compositions are liquid are
called liquidus, while solidus represents set of solubility curves that denotes the locus of
temperatures below which all compositions are solid.
Every phase diagram for two or more components must show a liquidus and a solidus,
and an intervening freezing range, except for pure system, as melting of a phase occurs
over a range of temperature. Whether the components are metals or nonmetals, there are
certain locations on the phase diagram where the liquidus and solidus meet.
For a pure component, a contact point lies at the edge of the diagram. The liquidus and
solidus also meet at the other invariant positions on the diagram. Each invariant point
represents an invariant reaction that can occur only under a particular set of conditions
between particular phases, so is the name for it.
Phase diagrams are classified based on the number of components in the system.
Single component systems have unary diagrams,
Two-component systems have binary diagrams,
Three-component systems are represented by ternary diagrams, and so on.
When more than two components are present, phase diagrams become extremely
complicated and difficult to represent.
Experimental Methods:
The data for the construction of equilibrium diagrams are determined experimentally by a
variety of methods, the most common methods are:
Metallographic Methods
X-ray Diffraction Technique
Thermal Analysis
Metallographic Methods:
This method is applied by heating samples of an alloy to different temperatures, waiting
for equilibrium to be established, and then quickly cooling to retain their hightemperature structure. The samples then examined microscopically. This method is
difficult to apply to metals at high temperatures because the rapidly cooled samples do
not always retain their high-temperature structure, and considerable skill is then required
to interpret the observed microstructure correctly.
X-ray Diffraction Technique:

This method is applied by measuring the lattice dimensions and indicating the appearance
of a new phase either by the change in lattice dimension or by the appearance of a new
crystal structure. This method is very precise and very useful in determining the changes
in solid solubility with temperature.
Thermal Analysis:
This is by far the most widely used experimental method. It relies on the information
obtained from the cooling diagrams. In this method, alloys mixed at different
compositions are melted and then the temperature of the mixture is measured at a certain
time interval while cooling back to room temperature.
A cooling diagram for each mixture is constructed and the initial and final phase change
temperatures are determined. Then these temperatures are used for the construction of the
phase diagrams.
Cooling Curve of a Pure Metal:
Under equilibrium conditions, all metals exhibit a definite melting or freezing point. If a
cooling curve is plotted for a pure metal. It will show a horizontal line at the melting or
freezing temperature.
Figure 2. Cooling curve for the solidification of a pure metal.

Cooling Curve of a Solid Solution:
A solid solution is a solution in the solid state and consists of two kinds of atoms
combined in one type of space lattice. A solution is composed of two parts: a solute and a
solvent. The solute is the minor part of the solution or the material which is dissolved,
while the solvent constitutes the major portion of the solution. When solidification of the
solution starts, the temperature may be higher or lower than the freezing point of the pure
solvent. Most solid solutions solidify over a range in temperature. Figure 3 shows the
cooling curve for the solidification of a solid solution.
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Figure 3. Cooling curve for a solid solution.
Figure 4. Series of cooling curves for different alloys in a completely soluble system. The
dotted lines indicate the form of the phase diagram.
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Figure 5. Phase Diagram of alloy A+B

Unary diagrams: In these systems there is no composition change (C=1), thus only
variables are temperature and pressure. Thus in region of single phase two variables
(temperature and pressure) can be varied independently. If two phases coexist then,
according to Phase rule, either temperature or pressure can be varied independently, but
not both. At triple points, three phases can coexist at a particular set of temperature and
pressure. At these points, neither temperature nor the pressure can be changed without
disrupting the equilibrium i.e. one of the phases may disappear. Figure-1 depicts phase
diagram for water.
Figure-1: Unary phase diagram for water.

Binary diagrams: These diagrams constitutes two components, e.g.: two metals (Cu and
Ni), or a metal and a compound (Fe and Fe C), or two compounds (Al O and Si O ), etc.
3
In most engineering applications, as mentioned before, condensed phase rule is

applicable. It is assumed that the same is applicable for all binary diagrams, thus the
presentation of binary diagrams becomes less complicated. Thus binary diagrams are
usually drawn showing variations in temperature and composition only. It is also to be
noted that all binary systems consist only one liquid phase i.e. a component is completely
soluble in the other component when both are in liquid state.
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Hence, binary systems are classified according to their solid solubility.

1. Components completely soluble in the liquid state and completely soluble in the
solid state Type I
2. Components completely soluble in the liquid state and insoluble in the solid state
Type II
3. Components completely soluble in the liquid state and partly soluble in the solid
state Type III
4. Components completely soluble in the liquid state and formation of congruentmelting intermediate phase Type IV
5. The Peritectic reaction Type V
6. Components partly soluble in liquid state Monotectic reaction Type VI
7. Components insoluble in the liquid state and insoluble in the solid state Type VII
8. Transformation in solid state
a. Allotropic change
b. Order Disorder
c. The Eutectoid reaction
d. The Peritectoid reaction
Binary Phase diagrams
Components completely soluble in the liquid state and completely soluble in the solid
state Type I
If both the two components are completely soluble in each other in both solid and liquid
state, then the system is called isomorphous system. Hence it can be called as Binary
Isomorphous phase diagram or system
E.g.: Cu-Ni, Ag-Au, Ge-Si, Al O -Cr O .
2
Extent solid solubility for a system of two metallic components can be predicted based on
Hume-Ruthery conditions, summarized in the following:
- Crystal structure of each element of solid solution must be the same.
- Size of atoms of each two elements must not differ by more than 15%.
- Elements should not form compounds with each other i.e. there should be no
appreciable difference in the electro-negativities of the two elements.
- Elements should have the same valence.
All the Hume-Rothery rules are not always applicable for all pairs of elements which
show complete solid solubility.
In systems other than isomorphous systems i.e. in case of limited solid solubility, there
exist solid state miscibility gaps; number of invariant reactions can take place;
intermediate phases may exist over a range of composition (intermediate solid solutions)
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or only at relatively fixed composition (compound). These intermediate phases may

undergo polymorphic transformations, and some may melt at a fixed temperature
(congruent transformations, in which one phase changes to another of the same
composition at definite temperature). A solid solution based on a pure component and
extending to certain finite compositions into a binary phase diagram is called a terminal
solid solution, and the line representing the solubility limit of a terminal solid solution
w.r.t a two-phase solid region is called a solvus line (figure-4).
Binary Isomorphous System
If both the two components are completely soluble in each other in both solid and liquid
state, then the system is called isomorphous system. Hence it can be called as Binary
Isomorphous phase diagram or system
E.g.: Cu-Ni, Ag-Au, Ge-Si, Al O -Cr O .
2
A typical phase diagram for an isomorphous system made of two metallic elements A and
B is shown in figure(a). Any phase diagram can be considered as a map. A set of
coordinates a temperature and a composition is associated with each point in the
diagram. If the alloy composition and temperature specified, then the phase diagram
allows determination of the phase or phases that will present under equilibrium
conditions. There are only two phases in the phase diagram, the liquid and the solid
phases. These single-phases regions are separated by a two-phase region where both
liquid and solid co-exist. The area in the figure above the line marked liquidus (AbB)
corresponds to the region of stability of the liquid phase i.e beginning of the
solidification, and the area below the solidus line (AdB) represents the stable region for
the solid phase i.e end of the solidification.
Figure(b)
Figure (a)
Between two extremes of the horizontal axis of the diagram, cooling curves for different
alloys are shown in below as a function of time and temperature. Cooling curves shown
in figure(b) represent A, U, X, V and B correspondingly in figure-(a). Change in slope
of the cooling curve is caused by heat of fusion. In fact these changes in slope are nothing
but points on either solidus or liquidus of a phase diagram. An experimental procedure
14
where repeated cooling/heating of an alloy at different compositions, and corresponding

changes in slope of cooling curves will be used to construct the phase diagram.
For the interpretation of the phase diagram, lets consider the vertical line ae drawn
corresponding to composition of 50%A +50%B and assume that the system is undergoing
equilibrium cooling. The point a on the line ae signifies that for that particular
temperature and composition, only liquid phase is stable. This is true up to the point b
which lies on the liquidus line, representing the starting of solidification. Completion of
solidification of the alloy is represented by the point, d. Point e corresponds to singlephase solid region up to the room temperature. Point c lies in the two-phase region made
of both liquid and solid phases. Corresponding micro-structural changes are also shown
in figure-2. As shown in figure (a) above liquidus only a liquid phase exists, and below
the solidus single solid phase exists as completely solidified grains. Between these two
lines, system consist both solid crystals spread in liquid phase. It is customary to use L to
represent liquid phase(s) and Greek alphabets (, , ) for representing solid phases.
Another important aspect of interpreting phase diagrams along with phases present is
finding the relative amount of phases present and their individual composition.
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 in figure-(a), from which each of each phase is read. U
represents composition of liquid phase and V represents composition of solid
phase as intersection U meets liquidus line and V meets solidus line.
Procedure to find equilibrium relative amounts of phases (lever rule):
- A tie-line is constructed across the two phase region at the temperature of the
alloy to intersect the region boundaries.
- The relative amount of a phase is computed by taking the length of tie line from
overall composition to the phase boundary for the other phase, and dividing by the
total tie-line length. From figure-(a), relative amounts of liquid and solid phases is
given respectively by
Liquid percent= (cV/UV) X 100
Solid percent% = (cU/UV) X 100
U 28 percent
V 74 percent
c 50 percent
Hence cV = 74 50 = 24 and cU = 50 28 =22, UV = 74-28 = 46
Liquid percent = 24 / 46 = 52.18 percent
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Solid percent = 22 / 46 = 47.82 percent

Example is Cu Ni alloy system Binary Isomorphous system
Example of isomorphous system:

Cu-Ni (the complete solubility
occurs because both Cu and Ni
have the same crystal structure,
FCC,
similar
radii,
electronegativity and valence).
The melting point of Cu is 1085C
and for Ni is 1453C. This consist
of three phases liquid, solid ()
and mixture of liquid and solid
(). Liquidus line represents the
beginning of solidification and
Solidus line represents the end of
the solidification. Here both Cu
and Ni are completely soluble in
both liquid and solid state.
Components completely soluble in the liquid state and Insoluble in the solid state
Type II
Eutectic phase diagram describes behavior of the alloys, two components of which are
completely soluble in liquid state and entirely insoluble in solid state.
This diagram has two liquidus curves,
starting from the freezing points of the two
metals and intersecting in a minimum point
Consider solidification of an alloy with
concentration C.
When the alloy
temperature is higher than TL , single liquid
phase exists (point M on the diagram).
When the temperature reaches the value TL
(point M1 on the liquidus curve)
solidification starts. The primary crystals,
forming in this case are the crystals of the
metal A.
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Further cooling of the alloy causes enrichment of the liquid phase with the metal B
according to the liquidus curve and when the alloy temperature reaches a certain
intermediate value T (position MT ), liquid phase of composition Cy and solid phase,
consisting of A crystals, are in equilibrium.
At the temperature equal to TE (eutectic temperature) formation of the primary crystals
stops and the remainding liquid phase , having composition CE (eutectic composition),
transforms to an intimate mixture of small A and B solid crystals. This is the
eutectic phase transformation.
Relative amounts of the primary crystals and the eutectic mixture may be calculated by
the lever rule :
WP / WE = (CE-C) / C
Where: WP weight of the primary crystals;
WE weight of the eutectic mixture;
Components completely soluble in the liquid state and partly soluble in the solid
state Type III
Eutectic system: Many binary systems have components which have limited solid
solubility, e.g.: Cu-Ag, Pb-Sn. The regions of limited solid solubility at each end of a
phase diagram are called terminal solid solutions as they appear at ends of the diagram.
Many of the binary systems with limited
solubility are of eutectic type, which consists of
specific alloy composition known as eutectic
composition that solidifies at a lower
temperature than all other compositions. This
low temperature which corresponds to the
lowest temperature at which the liquid can exist
when cooled under equilibrium conditions is
known
as
eutectic
temperature.
The
corresponding point on the phase diagram is called eutectic point. When the liquid of
eutectic composition is cooled, at or below eutectic temperature this liquid transforms
simultaneously into two solid phases (two terminal solid solutions, represented by and
). This transformation is known as eutectic reaction and is written symbolically as:
Liquid (L) solid solution-1 () + solid solution-2 ()
This eutectic reaction is called invariant reaction as it occurs under equilibrium
conditions at a specific temperature and specific composition which can not be varied.
Thus, this reaction is represented by a thermal horizontal arrest in the cooling curve of an
alloy of eutectic composition. A typical eutectic type phase diagram is shown in figure-4
along with a cooling curve.
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As shown in figure-4, there exist three single phase regions, namely liquid (L), and
phases. There also exist three two phase regions: L+, L+ and +. These three two
phase regions are separated by horizontal line corresponding to the eutectic temperature.
Below the eutectic temperature, the material is fully solid for all compositions.
Compositions that are on left-hand-side of the eutectic composition are known as hypoeutectic compositions while compositions on right-hand-side of the eutectic composition
are called hyper-eutectic compositions. The phase that forms during cooling but before
reaching eutectic temperature is called pro-eutectic phase.
Example
for completely
soluble in the liquid state and
partly soluble in the solid
state is Pb Sn alloy. In this
the melting point of the Pb is
327C and Sn is 232C. In this
there are 6 phases, liquid,
solid-, solid and mixture
of liquid and solid-, liquid
and solid- , solid- and
solid. Where the Eutectic
reaction takes place at
Eutectic
isotherm
temperature is 183C where
the eutectic reaction takes
place at the 61.9% of Sn.
Eutectic reaction is
Liquid Solid- + Solid-
Type IV
Congruent Melting intermediate phase
When one phase changes into
another
phase
isothermally(at
constant temperature) and without
any
change
in
chemical
composition, it is said to be
congruent phase change or
congruent transformation. All pure
metals solidify congruently. The
given phase diagram shows the
congruent melting intermediate
phase. The vertical line shows the
18
intermediate alloy phase, since it is a compound, it is indicated as AB 2, where 2 is the no

of atoms combined in the compound. E.g is Mg2Sn.This consist of more than one eutectic
reaction also.
Type V Peritectic Reaction
An isothermal, reversible reaction between two phases, a liquid and a solid, that results,
on cooling of a binary, ternary, ... , n system in one, two, ... (n 1) new solid phases.
Liquid + Solid- Solid-
In the given figure, the peritectic reaction takes place at
the point of P.
Invariant reactions: The eutectic reaction, in which a liquid transforms into two solid
phases, is just one of the possible three-phase invariant reactions that can occur in binary
systems those are not isomorphous. Schematically it can be shown as in figure-9. It
represents that a liquid phase, L, transforms into two different solids phases ( and )
upon cooling during the eutectic reaction.
In the solid state analog of a eutectic reaction, called a eutectoid reaction, one solid phase
having eutectoid composition transforms into two different solid phases.
19
Another set of invariant reactions that occur often in binary systems are - peritectic
reaction where a solid phase reacts with a liquid phase to produce a new solid phase, and
in peritectoid reaction, two solid phases react to form a new solid phase. Peritectic
reaction is commonly present as part of more-complicated binary diagrams, particularly if
the melting points of the two components are quite different. Peritectic and peritectoid
reactions do not give rise to micro-constituents as the eutectic and eutectoid reactions do.
Another invariant reaction that involves liquid phase is monotectic reaction in which a
liquid phase transforms into a solid phase and a liquid phase of different composition.
Over a certain range of compositions the two liquids are immiscible like oil and water
and so constitute individual phases, thus monotectic reaction can said to be associated
with miscibility gaps in the liquid state. Example system for monotectic reaction: Cu-Pb
at 954 C and 36%Pb. Analog to monotectic reaction in solid state is monotectoid
reaction in which a solid phase transforms to produce two solid phases of different
compositions. Another notable invariant reaction that is associated with liquid
immiscibility is syntectic reaction in which two liquid phases react to form a solid phase.
All the invariant reactions are summarized in the table-1 showing both symbolic reaction
and schematic part of phase diagram.
Table-1: Summary of invariant reactions in binary systems.
Intermediate phases: An intermediate phase may occur over a composition range

(intermediate solid solution) or at a relatively fixed composition (compound) inside the
phase diagram and are separated from other two phases in a binary diagram by two phase
regions. Many phase diagrams contain intermediate phases whose occurrence cannot be
readily predicted from the nature of the pure components. Intermediate solid solutions
often have higher electrical resistivities and hardnesses than either of the two
components. Intermediate compounds form relatively at a fixed composition when there
exists a stoichiometric relationship between the components, for example: Mg2Ni and
MgNi2 in Mg-Ni system. These are called inter-metallic compounds, and differ from
other chemical compounds in that the bonding is primarily metallic rather than ionic or
covalent, as would be found with compounds in certain metal-nonmetal or ceramic
systems. Some metal-nonmetal compounds, Fe3C, are metallic in nature, whereas in
others, MgO and Mg2Si, bonding is mainly covalent. When using the lever rules, inter-
20
metallic compounds are treated like any other phase, except they appear not as a wide
region but as a vertical line.
Number of phase transformations may takes place for each system. Phase transformations
in which there are no compositional alternations are said to be congruent
transformations, and during incongruent transformations at least one of the phases will
experience a change in composition. Examples for (1) congruent transformations:
allotropic transformations, and melting of pure materials (2) incongruent transformations:
all invariant reactions, and also melting of alloy that belongs to an isomorphous system.
Intermediate phases are sometimes classified on the basis of whether they melt
congruently or incongruently. MgNi2, for example, melts congruently whereas Mg2Ni
melts incongruently since it undergoes peritectic decomposition.
21
22
The iron carbon system, phase transformations

A study of iron-carbon system is useful and important in many respects. This is because
(1) steels constitute greatest amount of metallic materials used by man (2) solid state
transformations that occur in steels are varied and interesting. These are similar to those
occur in many other systems and helps explain the properties.
Iron-carbon phase diagram shown in figure given below is not a complete diagram. Part
of the diagram after 6.67 wt% C is ignored as it has little commercial significance. The
6.67%C represents the composition where an inter-metallic compound, cementite (Fe3C),
with solubility limits forms. In addition, phase diagram is not true equilibrium diagram
because cementite is not an equilibrium phase. However, in ordinary steels
decomposition of cementite into graphite never observed because nucleation of cementite
is much easier than that of graphite. Thus cementite can be treated as an equilibrium
phase for practical purposes.
The Fe-Fe3C is characterized by five individual phases and four invariant reactions. Five
phases that exist in the diagram are: ferrite (BCC) Fe-C solid solution, -austenite
(FCC) Fe-C solid solution, -ferrite (BCC) Fe-C solid solution, Fe3C (iron carbide) or
cementite - an inter-metallic compound and liquid Fe-C solution. Four invariant reactions
that cause transformations in the system are namely eutectoid, eutectic, monotectic and
peritectic.
As depicted by left axes, pure iron upon heating exhibits two allotropic changes. One
involves ferrite of BCC crystal structure transforming to FCC austenite, -iron, at
910C. At 1400 C, austenite changes to BCC phase known as -ferrite, which finally
melts at 1536 C.
Carbon present in solid iron as interstitial impurity, and forms solid solution with ferrites
/ austenite as depicted by three single fields represented by , and .
Carbon dissolves least in ferrite in which maximum amount of carbon soluble is 0.02%
at 723 C. This limited solubility is attributed to shape and size of interstitial position in
BCC ferrite. However, carbon present greatly influences the mechanical properties of
ferrite. ferrite can be used as magnetic material below 768 C.
Solubility of carbon in -iron reaches its maximum, 2.11%, at a temperature of 1147 C.
Higher solubility of carbon in austenite is attributed to FCC structure and corresponding
interstitial sites. Phase transformations involving austenite plays very significant role in
heat treatment of different steels. Austenite itself is non-magnetic.
Carbon solubility in -ferrite is maximum (0.1%) at 1495 C. As this ferrite exists only
at elevated temperatures, it is of no commercial importance
23
24
25
Cementite, Fe3C an inter-metallic compound forms when amount of carbon present

exceeds its solubility limit at respective temperatures. Out of these four solid phases,
cementite is hardest and brittle that is used in different forms to increase the strength of
steels. ferrite, on the other hand, is softest and act as matrix of a composite material.
By combining these two phases in a solution, a materials properties can be varied over a
large range.
For technological convenience, based on %C dissolved in it, a Fe-C solution is classified
as: commercial pure irons with less than 0.008%C; steels having %C between 0.0082.11; while cast irons have carbon in the range of 2.11%-6.67%. Thus commercial pure
iron is composed of exclusively ferrite at room temperature. Most of the steels and cast
irons contain both ferrite and cementite. However, commercial cast irons are not
simple alloys of iron and carbon as they contain large quantities of other elements such as
silicon, thus better consider them as ternary alloys. The presence of Si promotes the
formation of graphite instead of cementite. Thus cast irons may contain carbon in form of
both graphite and cementite, while steels will have carbon only in combined from as
cementite.
As shown in figure-above and mentioned earlier, Fe-C system constitutes four invariant
reactions:
- peritectic reaction at 1495 C and 0.16%C, -ferrite + L -iron (austenite)
- monotectic reaction 1495 C and 0.51%C, L L + -iron (austenite)
- eutectic reaction at 1147 C and 4.3 %C, L -iron + Fe3C (cementite) [ledeburite]
- eutectoid reaction at 723 C and 0.8%C, -iron ferrite + Fe3C (cementite)
[pearlite]
Product phase of eutectic reaction is called ledeburite, while product from eutectoid
reaction is called pearlite. During cooling to room temperature, ledeburite transforms into
pearlite and cementite. At room temperature, thus after equilibrium cooling, Fe-C
diagram consists of either ferrite, pearlite and/or cementite. Pearlite is actually not a
single phase, but a micro-constituent having alternate thin layers of ferrite (~88%) and
Fe3C, cementite (~12%). Steels with less than 0.8%C (mild steels up to 0.3%C, medium
carbon steels with C between 0.3%-0.8% i.e. hypo-eutectoid Fe-C alloys) i.e. consists
pro-eutectoid ferrite in addition to pearlite, while steels with carbon higher than 0.8%
(high-carbon steels i.e. hyper-eutectoid Fe-C alloys) consists of pearlite and pro-eutectoid
cementite. Phase transformations involving austenite i.e. processes those involve
eutectoid reaction are of great importance in heat treatment of steels.
In practice, steels are almost always cooled from the austenitic region to room
temperature. During the cooling upon crossing the boundary of the single phase -iron,
first pro-eutectoid phase (either ferrite or cementite) forms up to eutectoid temperature.
With further cooling below the eutectoid temperature, remaining austenite decomposes to
eutectoid product called pearlite, mixture of thin layers of ferrite and cementite.
Though pearlite is not a phase, nevertheless, a constituent because it has a definite
appearance under the microscope and can be clearly identified in a structure composed of
several constituents.
26
The decomposition of austenite to form pearlite occurs by nucleation and growth.

Nucleation, usually, occurs heterogeneously and rarely homogeneously at grain
boundaries. When it is not homogeneous, nucleation of pearlite occurs both at grain
boundaries and in the grains of austenite. When austenite forms pearlite at a constant
temperature, the spacing between adjacent lamellae of cementite is very nearly constant.
For a given colony of pearlite, all cementite plates have a common orientation in space,
and it is also true for the ferrite plates. Growth of pearlite colonies occurs not only by the
nucleation of additional lamellae but also through an advance at the ends of the lamellae.
Pearlite growth also involves the nucleation of new colonies at the interfaces between
established colonies and the parent austenite. The thickness ratio of the ferrite and
cementite layers in pearlite is approximately 8 to 1. However, the absolute layer thickness
depends on the temperature at which the isothermal transformation is allowed to occur.
The temperature at which austenite is transformed has a strong effect on the interlamellar spacing of pearlite. The lower the reaction temperature, the smaller will be interlamellar spacing. For example, pearlite spacing is in order of 10-3 mm when it formed at
700 C, while spacing is in order of 10-4 mm when formed at 600 C. The spacing of
the pearlite lamellae has a practical significance because the hardness of the resulting
structure depends upon it; the smaller the spacing, the harder the metal. The growth rate
of pearlite is also a strong function of temperature. At temperatures just below the
eutectoid, the growth rate increases rapidly with decreasing temperature, reaching a
maximum at 600 C, and then decreases again at lower temperatures.
Additions of alloying elements to Fe-C system bring changes (alternations to positions of
phase boundaries and shapes of fields) depends on that particular element and its
concentration. Almost all alloying elements causes the eutectoid concentration to
decrease, and most of the alloying elements (e.g.: Ti, Mo, Si, W, Cr) causes the eutectoid
temperature to increase while some other (e.g.: Ni, Mn) reduces the eutectoid
temperature. Thus alloying additions alters the relative amount of pearlite and proeutectoid phase that form.
Fe-C alloys with more than 2.11% C are called cast irons. Phase transformations in cast
irons involve formation of pro-eutectic phase on crossing the liquidus. During the further
cooling, liquid of eutectic composition decomposes in to mixture of austenite and
cementite, known as ledeburite. On further cooling through eutectoid temperature,
austenite decomposes to pearlite. The room temperature microstructure of cast irons thus
consists of pearlite and cementite. Because of presence of cementite, which is hard, brittle
and white in color, product is called white cast iron. However, depending on cooling rate
and other alloying elements, carbon in cast iron may be present as graphite or cementite.
Gray cast iron contains graphite in form of flakes. These flakes are sharp and act as stress
risers. Brittleness arising because of flake shape can be avoided by producing graphite in
spherical nodules, as in malleable cast iron and SG (spheroidal graphite) cast iron.
Malleable cast iron is produced by heat treating white cast iron (Si < 1%) for prolonged
periods at about 900 C and then cooling it very slowly. The cementite decomposes and
27
temper carbon appears approximately as spherical particles. SG iron is produced by

adding inoculants to molten iron. In these Si content must be about 2.5%, and no
subsequent heat treatment is required.
Review on FeFe3C system
Phases in FeFe3C Phase Diagram
-Ferrite - solid solution of C in BCC Fe
Stable form of iron at room temperature.
The maximum solubility of C is 0.022 wt%
Transforms to FCC g-austenite at 912 C
Austenite - solid solution of C in FCC Fe
The maximum solubility of C is 2.14 wt %.
Transforms to BCC d-ferrite at 1395 C
Is not stable below the eutectic temperature (727 C) unless cooled rapidly
-Ferrite solid solution of C in BCC Fe
The same structure as a-ferrite
Stable only at high T, above 1394 C
Melts at 1538 C
Fe3C (iron carbide or cementite)
This intermetallic compound is metastable, it remains as a compound
indefinitely at room T, but decomposes (very slowly, within several years) into aFe and C (graphite) at 650 - 700 C
Fe-C liquid solution
C is an interstitial impurity in Fe. It forms a solid solution with a, g, d phases of iron
Maximum solubility in BCC a-ferrite is limited (max. 0.022 wt% at 727 C) - BCC has
relatively small interstitial positions Maximum solubility in FCC austenite is 2.14 wt% at
1147 C - FCC has larger interstitial positions Mechanical properties: Cementite is very
hard and brittle - can strengthen steels. Mechanical properties also depend on the
microstructure, that is, how ferrite and cementite are mixed. Magnetic properties: a ferrite is magnetic below 768 C, austenite is non-magnetic
Classification. Three types of ferrous alloys:
Iron: less than 0.008 wt % C in a-ferrite at room T
Steels: 0.008 - 2.14 wt % C (usually < 1 wt % )
-ferrite + Fe3C at room T (Chapter 12)
Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)
28
Classification Of Metal Alloys
Classification of Steels
29
Classification of Steels
30
Low Alloys: Low Carbon

Composition: less than ~ 0.25% C
Microstructure: ferrite and pearlite
Properties: relatively soft and weak, but possess high ductility and toughness
Other features: moderately priced, machinable and weldable
Applications: auto-body components, structural shapes, sheets etc.
Plain carbon steels: residual concentration of impurities are unresponsible to heat
treatment
High-strength low alloy (HSLA) steels: up to 10 wt% of alloying elements, such as
Mn, Cr, Cu, V, Ni, Mo can be strengthened by heat-treatment
Examples of HSLA Steels:
Weathering steels, exhibit superior atmospheric corrosion resistance
Control-rolled steels, has a highly deformed austenite structure that transforms
to a very fine equiaxed ferrite structure on cooling
Pearlite-reduced steels, strengthened by very fine-grain ferrite and precipitation
hardening with a little or no pearlite in the microstructure
Microalloyed steels, with very small additions of Ni, V and/or Ti for refinement of
grain size and/or precipitation hardening
Acicular ferrite steel, very low carbon steels with sufficient hardenability to
transform on cooling to a very fine high-strength acicular ferrite structure
Low Alloys: Medium Carbon Steels
Composition: 0.25< C0 <0.6 C wt.%
Processing: Increasing the carbon content to approximately 0.5% with an
accompanying
increase in manganese allows medium carbon steels to be used in the quenched and
tempered condition.
Microstructure: typically tempered martensite
Properties: stronger than low-carbon steels, but in expense of ductility and toughness
Applications: couplings, forgings, gears, crankshafts other high-strength structural
components. Steels in the 0.40 to 0.60% C range are also used for rails, railway wheels
and rail axles.
Low Alloys: High&Ultra High - Carbon Steels
High-carbon steels contain from 0.60 to 1.00 % C with manganese contents ranging
from
0.30 to 0.90%. High-carbon steels are used for spring materials, high-strength wires,
cutting tools and etc.
Ultrahigh-carbon steels are experimental alloys containing 1.25 to 2.0% C. These
steels
are thermo-mechanically processed to produce microstructures that consist of ultra-fine,
equiaxed grains of spherical, discontinuous proeutectoid carbide particles.
31
High-Alloy Steels: Stainless Steels (SS)

The primarely alloying element is Cr (11 wt.%)
Highly resistance to corrosion
Four major classes:
(a) The austenitic SS has -Fe microstructure at room temperature!! This fcc
structure normally stable only above 910 C is stabilized in SS by addition of
Ni extremely corrosion resistant and NOT magnetic;
(b) The ferritic SS has Fe bbc structure. Not so corrosion resistant as
austenitic SS, but less expensive magnetic steel;
(d) The martensitic SS this fine magnetic bct structure is produced by rapid
quenching and possesses high yield strength and low ductility. Applications:
springs.
(e) The precipitation hardening SS producing multiple microstructure form
a single-phase one, leads to the increasing resistance for the dislocation motion
(a) and (b) are hardening and strengthening by cold work
32
High-Alloy Steels: Tools steels

Provide the necessary hardness with simpler heat-treatment and
retain this hardness at high temperature
The primary alloying elements are: Mo, W and Cr
CAST IRON
The cast irons are the ferrous alloys with greater that 2.14 wt % carbon, but typically
contain 3-4.5 wt % of C as well as other alloying elements, such as silicon (~3 wt.%)
which controls kinetics of carbide formation
There are four general types of cast irons:
1. White iron has a characteristics white, crystalline fracture surface. Large amount of
Fe3C are formed during casting, giving hard brittle material
2. Gray iron has a gray fracture surface with finely faced structure. A large Si content (23 wt %) promotes C flakes precipitation rather than carbide
3. Ductile iron: small addition (0.05 wt.%) of Mg to gray iron changes the flake C
microstructure to spheroidal that increases (by factor ~20) steel ductility
4. Malleable iron: traditional form of cast iron with reasonable ductility. First cast to
white iron and then heat-treated to produce nodular graphite precipitates.
White and Malleable cast iron
The low-silicon cast irons (<1.0wt.%), produced under rapid cooling conditions
Microstructure: most of cementite
Properties: extremely hard very but brittle
White iron is an intermediate for the production of malleable iron
In white cast iron light Fe3C regions surrounded by pearlite
In malleable cast iron dark graphite rosettes in -Fe matrix
Gray and Ductile Cast Irons
The gray irons contain 1-31.0 wt.% of Si
Microstructure: flake shape graphite in ferrite matrix
Properties : relatively weak and brittle in tension BUT very effective in damping
vibrational energy an high resistive to wear!!
Ductile (or Nodular) iron : small addition of Mg or/and Ce to the gray iron composition
before casting
Microstructure: Nodular or spherical-like graphite structure in pearlite or ferric matrix
Properties: Significant increase in material ductility
Applications: valves pump bodies, gears and other auto and machine components.
33
Micro Structures of steel

Cementite
Cementite is also known as iron carbide which has a chemical formula, Fe 3C. It contains
6.67 % Carbon by weight. It is a typical hard and brittle interstitial compound of low
tensile strength (approximately 5,000 psi) but high compressive strength. Its crystal
structure is orthorhombic
Austenite
It is also known as ( ) gamma-iron, which is an interstitial solid solution of carbon
dissolved in iron with a face centered cubic crystal (F.C.C) structure. Average properties
of austenite are: High toughness.
Austenite is normally unstable at room temperature. Under certain conditions it is
possible to obtain austenite at room temperature.
Ferrite
It is also known as ( ) alpha -iron, which is an interstitial solid solution of a small
amount of carbon dissolved in iron with a Body Centered Cubic (B.C.C.) crystal
structure. It is the softest structure on the iron-iron carbide diagram. Average properties
are: Low toughness and low hardness
Pearlite:
It is the eutectoid mixture containing 0.83 % Carbon and is formed at 1333 oF on very
slow cooling. It is very fine platelike or lamellar mixture of ferrite and cementite. The
structure of pearlite includes a white matrix (ferritic background) which includes thin
plates of cementite.
Alloying Elements of Steel
Plain carbon steels contain traces of certain elements (Si, Mn, S, P), which unavoidably
entered the steel during the iron and steel making processes. However, these are not
considered alloying elements, unless their content exceeds the amount corresponding to
the production process. Steel is considered alloyed when in addition to the basic
components ( Fe & C), other alloying y p ), y g elements are added intentionally to assure
certain properties, that cannot be assured without alloying.
The most important and most frequently applied alloying elements of steel are manganese
(Mn), nickel (Ni), chromium (Cr), tungsten (W), vanadium (V), molybdenum (Mo),
titanium (Ti), niobium (Nb) and boron (B).
34
The main aim of alloying steels is to:

Improve mechanical properties (e.g. strength, ductility, toughness)
Increase resistance to corrosion (chemical resistance)
Improve certain physical properties (e.g. magnetic, electrical properties)
Improve complex properties of technological workability (e.g. formability,
weldability,
machinability)
The objectives can be achieved in various ways depending on the relationship of the
alloying elements to the base material (Fe) and to the fundamental alloying element of
steels, that is carbon (C ).
35
Effect of Alloying elements
36
37
UNIT II HEAT TREATMENT
11
Definition Full annealing, stress relief, recrystallisation and spheroidizing normalising,

hardening and Tempering of steel. Isothermal transformation diagrams cooling curves
superimposed on I.T. diagram CCR - Hardenability, Jominy end quench test
Austempering, martempering case hardening, carburising, nitriding, cyaniding,
carbonitriding Flame and Induction hardening.
Heat Treatment
A combination of heating and cooling operations timed and applied to a metal or alloy in
the solid state in a way that will produce desired properties.
All basic heat treatment process for steel involve the transformation or decomposition of
austenite. In the heat treatment of steel is to heat the material to some temperature in or
above the critical range in order to form the austenite
I. HEAT TREATMENT PROCESSES
A. The process of heating a metal workpiece to a high temperature to changeit's
properties, normally to make the workpiece harder or softer.
B. Basic heat treatment steps and equipment:
1. Heating to the correct temperature.
a. Equipment normally a heat-treating furnace, a blowtorch, gas welding torch, or a forge.
2. Holding or soaking at this temperature for a certain length of time.
a. Equipment can be the same furnace or forge.
3. Cooling in a way that will produce the desired results.
a. Equipment can be container of water, tempering oil or brine.
C. Heat treatment processes and uses.
1. Hardening
a. The process:
(1). Heating and cooling steel to increase its hardness and tensile strength, to reduce its
ductility.
(2). Requires a steel with a minimum of 0.20% carbon content.
b. Uses:
(1). To produce sharp-edged cutting tools.
(2). To make bearing surfaces wear better/longer.
38
(3). To put "spring" in a spring.

2. Tempering
a. The process
(1). Process of reducing the degree of hardness (removing brittleness) and strength and
increasing toughness.
(2). If a part is too hard, it will chip; if it is not hard enough, it will bend. Tempering
achieves the balance between hardness and strength.
b. Uses:
(1). Knife blades, screw driver tip, cold chisel tip, axes, shears.
3. Annealing
a. The process:
(1). Process of softening metal to relieve internal strain and to make the metal easier to
shape and cut.
b. Uses:
(1). Reusing old springs or files for other projects not requiring hardness.
(2). To relieve built up stresses and prevent cracking of manufactured metals.
II. HOT METAL FORMING PROCESSES
A. Techniques to give objects shape or form without adding or removing any
materials from the part.
B. Metal forming operations.
1. Bending.
a. The process:
(1). Process by which metal is uniformly strained or stretched around a straight axis
and results in a product having a linear or straight shape.
b. Uses:
(1). Decorative grillwork.
2. Forging (blacksmithing).
a. The process:
(1). Forming is achieved by hammering or applying steady pressure to a workpiece,
forcing it to take the shape of a die. May be done with the workpiece either hot or
cold.
39
b. Uses:
(1). Making small tools (chisels and center punches), horseshoes, ornamental ironwork.
I. CLASSIFICATION AND USES OF METALS

A. Ferrous metal types ("ferrous" = containing iron and alloys)
1.Iron.
a. Rare in the pure state; pure iron is not used commercially.
2. Wrought iron.
a. Contains:
(1). Iron, alloyed (combined) with,
(2). Less than 0.03% carbon.
b. True wrought iron is scarce and expensive.
c. True wrought iron forges well, can be easily bent hot or cold and can be welded.
d. "Wrought iron" is currently used to refer to almost any malleable low carbon steel.
3. Carbon steels, or "steel".
a. Contains:
(1). Iron, alloyed (combined) with,
(2). Carbon,
(3). Less than 1.65% manganese,
(4). Less than 0.60% copper, and
(5). Smaller amounts of silicon, sulfur and phosphorous.
b. Types:
(1). Low-carbon ("mild") steels
(a). Between 0.05% and 0.30% carbon.
(b). Tough and ductile. Easily formed, machined and welded.
(c). Most commonly used of the carbon steel types.
(2). Medium-carbon steels
(b). Strong and hard, but less ductile.
(c). Not as easily welded, due to tendency to crack after welding.
(d). Used for gears.
40
(3). High-carbon steels

(b). Very hard and strong, less ductile.
(c). Special electrodes and welding procedures are required, to prevent brittleness
and cracking.
(d). Used for cold chisels and hammers.
(4). Very-high-carbon steels
(b). Super hard and strong.
(c). Seldom welded; special electrodes and procedures used.
(d). Used for tools and springs.
(e). Can be used for items that must be hardened and tempered. (See paragraph IV.
below for definition of these terms).
4. Rolled steels.
a. Bar, rod and structural steels produced by rolling the steel into shape, much like an old
clothes wringer.
Cold rolled steel.
Steel formed when cold.
Results in more accurately sized, better surface finished product.
Hot rolled steel.
Metal formed into shape while the metal is red hot.
Produces a uniform quality, commonly used steel.
Bluish scale on the surface formed when water sprayed on the steel as it
passes between rollers.
5. Galvanized steel.
a. Mild steel coated with zinc to prevent rusting.
b. Care should be taken not to inhale toxic fumes when welding this
material.
II. PROPERTIES OF METALS
A. Tensile Strength.
41
1. Ability to resist being pulled apart in tension. Metal failures are often caused by forces
exceeding the tensile strength of the part.
B. Ductility.
1. Ability to be stretched or pulled through a die to form wire.
2. Copper is a very ductile metal.
C. Hardness.
1. Ability to resist penetration.
2. Hardness can be increased by heat treatment or work hardening.
III. IDENTIFICATION OF METALS
A. Numbering system for carbon and alloy steels.
1. Four digit (sometimes five digits) numbering system to identify carbon and alloy
steels:
a. First digit usually indicates the principle element in the steel as follows:
SERIES TYPES AND
DESIGNATION CLASSES
10XX Non-resulferized carbon steel grades (plain carbon steel)
13xx Manganese 1.75%
20xx Nickel steels
23xx Nickel 3.5%
30xx Nickel-chromium steels*
31xx Nickel 1.25% - chromium 0.65 or 0.80%
40xx Molybdenum 0.25%
41xx Chromium 0.50 0.95% - molybdenum 0.15 or 0.20%
43xx Nickel 1.80% - chromium 0.50 or 0.80% - molybdenum 0.25%*
50xx Chromium 0.28 or 0.40%
51xx Chromium 0.80, 0.90, 0.95, 1.00 or 1.05%
5xxxx Carbon 1.00% - chromium 0.50, 1.00 or 1.45%
60xx Chrome-vanadium steels
61xx Chromium 0.80 or 0.95% - vanadium 0.10 or 0.15% min.
70xx Heat resisting casting alloys
80xx Nickel chrome molybdenum steels*
42
86xx Nickel 0.55% - chromium 0.50 or 0.65% - molybdenum 0.20%

90xx Silicon manganese steels
92xx Manganese 0.85% - silicon 2.00%
93xx Nickel 3.25% - chromium 1.20% - molybdenum 0.12%
*Stainless steels always have a high chromium content, often considerable amounts of
nickel, and sometimes contain molybdenum and other elements. Stainless steels are
identified by a three-digit number beginning with 2, 3, 4, or 5.
b. Second digit (in alloy steels) represents the approximate percentage of alloy
element.
c. Third and fourth digits show the carbon content in points (where a point
equals 100 times the percentage carbon).
d. Examples:
(1). 1095 steel is a carbon steel with 0.95% (95 points) carbon.
(2). 2511 steel is nickel steel with approximately 5% nickel and 0.11% carbon.
Various heat treatment process are
1. Annealing
a. Process annealing
b. Full annealing
c. Stress relief annealing
d. Spheroidize annealing
2. Normalizing
3. Hardening
4. Tempering
a. Austempering
b. Martempering
43
Annealing Processes
Annealing is a heat treatment where the material is taken to a high temperature, kept there
for some time and then cooled. High temperatures allow diffusion processes to occur
fast. The time at the high temperature (soaking time) is long enough to allow the desired
transformation to occur. Cooling is done slowly to avoid the distortion (warping) of the
metal piece, or even cracking, caused by stresses induced by differential contraction due
to thermal inhomogeneities. Benefits of annealing are:
relieve stresses
increase softness, ductility and toughness
produce a specific microstructure
44
Annealing techniques
Process annealing applied to
cold worked materials to negate
effects of cold work. Commonly
sandwiched between two cold
work
operations.
Improves
ductility. This is used to treat
worked metals, such as two
pieces of metal that have been
welded together. This makes it
possible for the metal to undergo
further work without fracturing.
The metal is heated to just below
the A1 temperature line (see blue
arrow); it is held there long
enough for the metal to change
the size and distribution of its
grain structure and then cooled
naturally in air. This process is
cheaper than Full Annealing or
Normalizing because the metal is
not heated to high temperatures
Stress relief purpose of it is to remove stresses. Temperatures are low such that cold
work effects are not affected. Reduces the residual stresses in large castings and welded
parts. These stresses are caused by thermal cycling or work hardening. The metal is
heated to 600 degrees Celsius (see green line), held at that temperature level for over an
hour and then cooled in air.
Full annealing used for products that are to be machined later-on. Cooling is done in
furnace itself. Hardness and strength are restored by additional heat treatments after
machining. Is the process of slowly raising the temperature above the Austenitic.
Temperature line A3 (see the red arrow). Austenitic steel is the most ductile of the steels
and has a very high relative strength. It is held at this temperature until all the material
transforms and then slowly cools in a furnace to about 50 degrees Celsius when it can be
then cooled through convection in the room
Normalizing used to refine the grains and produce a more uniform and desirable size
distribution. It involves heating the component to attain single phase (e.g.: austenite in
steels), then cooling in open air atmosphere.Is the same as the Full Anneal, the metal is
heated above the A3 temperature line (see red arrow). However, the metal is cooled right
away through room convection, rather than through a furnace. This makes normalizing
cheaper since a furnace is not used to cool the metal in a controlled environment. Both of
these processes make the metal more soft, which makes it more machineable, the
45
difference is that the Full annealed metal is uniformly soft while the Normalized metal
varies in its softness.
Tempering: This is used to remove brittleness found in quench hardened parts. It is done
to improve hardness, ductility, toughness and strength. It must be done immediately after
a metal has been quenched and then cooled to 40 degrees Celsius. It is then reheated to
between 150-400 degrees Celsius. This heating is usually done in an oil bath; this ensures
that every part of the metal will undergo the same temperature and tempering.
Quenching operation is usually followed by tempering.
Tempering involves heating martensitic steel at a temperature below the eutectoid
transformation temperature to make it softer and more ductile. Here Martensite
transforms to ferrite embedded with carbide particles.
Martempering is used to minimize distortion and cracking. It is the interrupted cooling
procedure used for steels to minimize the stresses, distortions and cracking of steels that
may develop during rapid quenching. It involves cooling the austenized steel to
temperature just above Ms temperature, holding it there until temperature is uniform,
followed by cooling at a moderate rate to room temperature before austenite-to-bainite
transformation begins. The final structure of martempered steel is tempered Martensite.
Austempering involves austenite-to-bainite transformation. Thus, the final structure of
austempered steel is bainite. Austempering is an isothermal heat treatment that, when
applied to ferrous materials, produces a structure that is stronger and tougher than
comparable structures produced with conventional heat treatments. Conventional heat
treaters heat the parts to "red heat" in a controlled atmosphere and then quench them in a
bath of oil or water that is near room temperature. (Maybe even as high as a few hundred
degrees Fahrenheit). This produces a crystalline structure known as Martensite, a hard,
brittle phase. The parts are then tempered in another furnace at 350F (177c) to 1100F
(593c) to decrease the "brittleness."
Austempering starts the same way. The parts are

heated to red heat in a controlled atmosphere (so
they don't scale) but then are quenched in a bath
of molten salt at 450F (232c) to 750F (399c).
The quench temperature is above the Martensite
starting temperature. Therefore, a different
structure
(not
Martensite)
results.
In
Austempered Ductile Iron and Austempered
Gray Iron the structure is Ausferrite, and in steel,
it is Bainite.
46
Transformation rate effects and TTT diagrams, Microstructure and Property

Changes in Fe-C Alloys
Solid state transformations, which are very important in steels, are known to be
dependent on time at a particular temperature, as shown in figure-14(b). Isothermal
transformation diagram, also known as TTT diagram, measures the rate of transformation
at a constant temperature i.e. it shows time relationships for the phases during isothermal
transformation. Information regarding the time to start the transformation and the time
required to complete the transformation can be obtained from set of TTT diagrams. One
such set of diagram for reaction of austenite to pearlite in steel is shown in figure-17. The
diagram is not complete in the sense that the transformations of austenite that occur at
temperatures below about 550 C are not shown.
As mentioned in previous section, thickness of layers in pearlite depends on the

temperature at which the transformation occurred. If the transformation took place at a
temperature that is just below the eutectoid temperature, relatively thick layers of
ferrite and cementite are produced in what is called coarse pearlite. This is because of
high diffusion rates of carbon atoms. Thus with decreasing transformation temperature,
sluggish movement of carbon results in thinner layers ferrite and cementite i.e. fine
pearlite is produced.
At transformation temperatures below 550 C, austenite results in different product
known as bainite. Bainite also consists of ferrite and cementite phases i.e.
transformation is again diffusion controlled but morphologically it consists of very small
47
particles of cementite within or between fine ferrite plates. Bainite forms needles or
plates, depending on the temperature of the transformation; the microstructural details of
bainite are so fine that their resolution is only possible using electron microscope.
It differs from pearlite in the sense that different mechanism is involved in formation ob
bainite which does not have alternating layers of ferrite and cementite. In addition,
because of equal growth rates in all directions pearlite tends to form spherical colonies,
whereas bainite grows as plates and has a characteristic acicular (needlelike) appearance.
Upper bainite, formed at the upper end of the temperature range (550 C-350 C), is
characterized by relatively coarse, irregular shaped cementite particles in ferrite plates.
If the transformation is taking place at lower temperatures (350 C-250 C), the
ferrite plates assume a more regular needlelike shape, and the transformation product is
called lower bainite. At the same time carbide particles become smaller in size and
appear as cross-striations making an angle of about 55 to the axis of the ferrite plate.
Upper bainite has large rod-like cementite regions, whereas lower bainite has much finer
cementite particles as a result of sluggish diffusion of carbon atoms at lower
temperatures.
Lower bainite is considerably harder than upper bainite. Another characteristic of bainite
is that as it has crystallographic orientation that is similar to that found in simple ferrite
nucleating from austenite, it is believed that bainite is nucleated by the formation of
ferrite. This is in contrast to pearlite which is believed to be nucleated by formation of
cementite.
Basically, bainite is a transformation product that is not as close to equilibrium as
pearlite. The most puzzling feature of the bainite reaction is its dual nature. In a number
of respects, it reveals properties that are typical of a nucleation and growth type of
transformation such as occurs in the formation pearlite and also a mixture of ferrite and
cementite though of quite different morphology (no alternate layers), but at the same time
it differs from the Martensite as bainite formation is athermal and diffusion controlled
though its microstructure is characterized by acicular (needlelike) appearance.
The time-temperature dependence of the bainite transformation can also be presented
using TTT diagram. It occurs at temperatures below those at which pearlite forms i.e. it
does not form until the transformation temperature falls below a definite temperature,
designated as Bs. Above this temperature austenite does not form bainite except under
external stresses. Below Bs, austenite does not transform completely to bainite. The
amount of bainite formed increases as the isothermal reaction temperature is lowered. By
reaching a lower limiting temperature, Bf, it is possible to transform austenite completely
to bainite. The Bs and Bf temperatures are equivalent to the Ms and Mf temperatures for
Martensite.
48
In simple eutectoid steels, pearlite and bainite transformations overlap, thus transition
from the pearlite to bainite is smooth and continuous i.e. knees of individual pearlite and
bainite curves are merged together. However each of the transformations has a
characteristic C-curve, which can be distinguishable in presence of alloying elements.
As shown in complete TTT diagram for eutectoid steel in figure-18, above approximately
550 C-600 C, austenite transforms completely to pearlite. Below this range up to
450C, both pearlite and bainite are formed. Finally, between 450 C and 210 the
reaction product is bainite only. Thus bainite transformation is favored at a high degree of
supercooling, and the pearlite transformation at a low degree of supercooling. In middle
region, pearlitic and bainitic transformations are competitive with each other.
As explained in earlier section, martensitic transformation can dominate the proceedings
if steel is cooled rapid enough so that diffusion of carbon can be arrested. Transformation
of austenite to Martensite is diffusion-less, time independent and the extent of
transformation depends on the transformation temperature. Martensite is a meta-stable
phase and decomposes into ferrite and pearlite but this is extremely slow (and not
noticeable) at room temperature. Alloying additions retard the formation rate of pearlite
and bainite, thus rendering the martensitic transformation more competitive. Start of the
transformation is designated by Ms, while the completion is designated by Mf in a
transformation diagram. Martensite forms in steels possesses a body centered tetragonal
crystal structure with carbon atoms occupying one of the three interstitial sites available.
This is the reason for characteristic structure of steel Martensite instead of general BCC.
Tetragonal distortion caused by carbon atoms increases with increasing carbon content
and so is the hardness of Martensite. Austenite is slightly denser than Martensite, and
therefore, during the phase transformation upon quenching, there is a net volume
increase. If relatively large pieces are rapidly quenched, they may crack as a result of
internal stresses, especially when carbon content is more than about 0.5%.
Mechanically, Martensite is extremely hard, thus its applicability is limited by brittleness
associated with it. Characteristics of steel Martensite render it unusable for structural
applications in the as-quenched form. However, structure and thus the properties can be
altered by tempering, heat treatment observed below eutectoid temperature to permit
diffusion of carbon atoms for a reasonable period of time.
During tempering, carbide particles attain spherical shape and are distributed in ferrite
phase structure called spheroidite. Spheroidite is the softest yet toughest structure that
steel may have. At lower tempering temperature, a structure called tempered Martensite
forms with similar microstructure as that of spheroidite except that cementite particles are
much, much smaller.
The tempering heat treatment is also applicable to pearlitic and bainitic structures. This
mainly results in improved machinability. The mechanism of tempering appears to be
first the precipitation of fine particles of hexagonal -carbide of composition about
Fe2.4C from Martensite, decreasing its tetragonality. At higher temperatures or with
49
increasing tempering times, precipitation of cementite begins and is accompanied by

dissolution of the unstable -carbide. Eventually the Martensite loses its tetragonality and
becomes BCC ferrite, the cementite coalesces into spheres. A schematic of possible
transformations involving austenite decomposition are shown in figure-19.
Tempering of some steels may result in a reduction of toughness what is known as

temper embrittlement. This may be avoided by (1) compositional control, and/or (2)
tempering above 575 or below 375, followed by quenching to room temperature. The
effect is greatest in Martensite structures, less severe in bainitic structures and least
severe in pearlite structures. It appears to be associated with the segregation of solute
atoms to the grain boundaries lowering the boundary strength. Impurities responsible for
temper brittleness are: P, Sn, Sb and As. Si reduces the risk of embrittlement by carbide
formation. Mo has a stabilizing effect on carbides and is also used to minimize the risk of
temper brittleness in low alloy steels.
TTT diagrams are less of practical importance since an alloy has to be cooled rapidly and
then kept at a temperature to allow for respective transformation to take place. However,
most industrial heat treatments involve continuous cooling of a specimen to room
temperature. Hence, Continuous Cooling Transformation (CCT) diagrams are generally
more appropriate for engineering applications as components are cooled (air cooled,
furnace cooled, quenched etc.) from a processing temperature as this is more economic
than transferring to a separate furnace for an isothermal treatment. CCT diagrams
measure the extent of transformation as a function of time for a continuously decreasing
temperature.
For continuous cooling, the time required for a reaction to begin and end is delayed, thus
the isothermal curves are shifted to longer times and lower temperatures. Both TTT and
CCT diagrams are, in a sense, phase diagrams with added parameter in form of time.
Each is experimentally determined for an alloy of specified composition. These diagrams
allow prediction of the microstructure after some time period for constant temperature
and continuous cooling heat treatments, respectively. Normally, bainite will not form
during continuous cooling because all the austenite will have transformed to pearlite by
the time the bainite transformation has become possible. Thus, as shown in figure-20,
region representing austenite-pearlite transformation terminates just below the nose.
50
Hardenability of steels
Jomniy End Quench Test
Full annealing and Spheroidizing: to produce softer steel for good machining and forming
Normalization: to produce more uniform fine structure that tougher than coarse-grained
one Quenching: to produce harder alloy by forming martensitic structure
Note: cooling rates before reaching Austenite Martensite transformation are in the
range 1 -50 C/s. Measuring cooling rates at every point (e.g. by thermocouples) and
finding rates correlations with the hardness one may develop quenching rate hardness
diagram
51
Instead, a Jominy Test is used to compare hardenabilities of steel. This is a standard test
adopted by ASTM (American Society for Testing & Materials) and by SAE (Society for
Automotive Engineers). uto ot e g ee s). A steel bar 100mm long and 25mm in diameter
is austenitised, placed into a fixture and sprayed with one end with a jet of water of
specified flow rate and temperature. After the test, Rockwell hardness measurements are
made along the test specimen every 1/16 inch from the quenched end for the first inch.
The distance(s) between hardness tests for the remaining length of the bar is at the
discretion of the tester.
A plot of hardness vs. distance from quenched end is plotted to produce a hardenability
curve. This method of quenching results in different rate of cooling along the length of
the test piece. The quenched end cools the most rapidly and exhibits the maximum
hardness, since 100% martensite is formed. The cooling rate at the opposite end can be
considered to be air cooled, a very slow cooling rate, producing a structure which is less
hard. The distance from the quenched end is the Jominy distance and is related to the
cooling rate. We need to know the hardness at different cooling rates, rather than the
hardness at different distances.Each steel alloy has its own unique hardenability curve.
This standard quench process produces a common cooling rate gradient along the Jominy
bar, for all carbon and low alloy steels. Thermal properties are nearly identical for these
iron carbon alloys
52
Precipitation Hardening
Enhancing the strength and hardness of the alloy by the formation (as a result of specific
heat-treatment) of the fine uniformly dispersed particles of the second phase, which
impede dislocations.
53
Two-stage heat-treatment:
(1) Solution formation: relatively high T to provide single-phase solution formation +
quenching to form a non-equilibrium supersaturated solution;
(2) Precipitation: relatively low T, within two-phase zone, to form second phase particles
Effect of Alloying Elements
Hardenability - Alloy steels have high hardenability.
Effect on the Phase Stability - When alloying elements are added to steel, the
binary Fe-Fe3C stability is affected and the phase diagram is altered.
Shape of the TTT Diagram - Ausforming is a thermomechanical heat treatment in
which austenite is plastically deformed below the A1 temperature, then permitted
to transform to bainite or martensite.
Tempering - Alloying elements reduce the rate of tempering compared with that
of a plain-carbon steel.
Surface Treatments
Selectively Heating the Surface - Rapidly heat the surface of a medium-carbon
steel above the A3 temperature and then quench the steel.
Case depth - The depth below the surface of a steel at which hardening occurs by
surface hardening and carburizing processes.
Carburizing - A group of surface-hardening techniques by which carbon diffuses
into steel.
Cyaniding - Hardening the surface of steel with carbon and nitrogen obtained
from a bath of liquid cyanide solution.
Carbonitriding - Hardening the surface of steel with carbon and nitrogen obtained
from a special gas atmosphere.
Case Hardening or Surface Hardening

Many materials applications require good wear resistance, and resistance to high contact
stresses at the surface, while at the same time providing good toughness at the core of the
material. These requirements need hi h hardness and strength at the surface while keeping
the ore requirements high strength surface, while keeping core or inner section of the
material soft and having low strength. This gradient in properties through the section of
54
the part or component can

be
achieved
through
surface hardening in which
a hard martensitic structure
is produced at the surface,
while non martensitic
structures,
pearlite
or
bainite, are at the inner
section or core of the part.
Surface
hardening
is
usually specified to a
certain depth from the
surface resulting in a shell
or case of hard material. Thus, it is also commonly referred to as case hardening. It may
be achieved with or without change of the surface composition.
Purpose of Case or Surface hardening

Increase wear resistance
Increase surface strenght for load carrying (crush resistance)
Induce suitable residual and compressive stresses
Improve fatigue life
Impact resistance
Carburising
Involves changing the carbon content of the surface, followed by a quenching process to
convert the surface layers to martensite. Carbon content in the surface layers increases
from less than 0.2% to 0.7 to 0.8%. Carburising can be done when the source of carbon is
either in the:
solid state Pack carburising
55
liquid state Liquid carburising or salt bath carburising or cyaniding

gaseous state Gas carburising
A case-hardening process in which carbon is dissolved in the surface layers of a lowcarbon steel part at a temperature sufficient to render the steel austenitic, followed by
quenching and tempering to form a martensitic microstructure;
2CO C(in Fe) +CO2
CO + H2 C(in Fe) + H2O
Methods: gas carburizing, vacuum carburizing, plasma (ion) carburizing, salt-bath
carburizing, and pack carburizing; Majority of carburized parts processed by gas
carburizing,
using
natural
gas,
propane,
or
butane.
Gas Carburising
Carbonsource: gaseous hydrocarbons (methane (CH4), propane (C3H3), butane
(C4H10)),
vaporized
hydro-carbon
liquids;
Pack carburizing:
Carbon monoxide derived from a solid compound decomposes at the metal surface into
nascent carbon and carbon dioxide; nascent carbon is absorbed into the metal, and the
carbon dioxide immediately reacts with carbonaceous material present in the solid
carburizing compound to produce
fresh carbon monoxide;
Carburizing compounds: contain 1020% alkali or alkaline earth metal
carbonates bound to hardwood
charcoal or to coke by oil, tar, or
molasses;
Barium
carbonate
(BaCO3) is the principal energizer
comprising about 50 to 70% of the
total carbonate content (CaCO3&
Na2CO3);
Process control: carbon potential,
temperature (815-955oC), time, steel
composition;
The steel component is heated to above the A3 temperature while in a sealed metal box
which contains the carburising medium, e.g. a carbon rich Liquid carburising or salt
bath carburizing material such as charcoal and an energiser such as barium carbonate.
The oxygen present in the box reacts with the carbon to produce carbon monoxide. This
carbon rich atmosphere in contact with the hot steel results in carbon diffusing into the
surface austenite layers.
Liquid Carburising
56
Parts are held in a molten salt that will introduce carbon and nitrogen, or carbon alone,
into the metal. Diffusion of the carbon from the surface toward the interior produces a
case that can be hardened, usually by fast quenching from the bath;
This involves heating the component in a bath of suitable carbon rich salts. Sodium
cyanide is mainly used. The carbon from the molten salt diffuses into the component.
This method produces relatively thin, hardened layers with high carbon content. This
occurs because carburising takes place very quickly. Problems with this method include
the dangers that the poisonous cyanide may pose, and the removal of salt from the
hardened component after treatment, which can be particularly difficult with threaded
parts and blind holes.
Nitriding:
Nitrogen diffused into surface of special alloy steels (aluminum or chromium)
Nitride compounds precipitate out
Gas nitriding - heat in ammonia
Liquid nitriding - dip in molten cyanide bath
Case thicknesses between 0.001 and 0.020 in. with hardness up to HRC 70.
Involves changing the surface composition of a steel by diffusing nitrogen into it to
produce hard nitride compounds. Prior to the nitriding treatment, the steel is hardened &
tempered to the properties required by the core, provided that the tempering temperature
is higher than the temperature of the nitriding process. Otherwise, the nitriding process
would temper the steel & change the properties of the core. Unlike carburising, nitriding
is carried out at temperatures below the stable austenitic state. The process consists of
heating a component in an atmosphere of ammonia gas & hydrogen (temperatures 500
to 530C).
The time taken for the nitrogen to react with the elements in the surface of the steel is
often as much as 100 hours. The depth to which the nitrides are formed in the steel
depends on the temperature & the time allowed for the reaction. The depth of hardening
is unlikely to exceed about 0.7mm. After the treatment, the component is allowed to cool
slowly in the ammoniahydrogen atmosphere. Since with nitriding, no quenching
treatments are involved, cracking and distortion are less likely than with other surface
hardening treatments.
Nitrogen diffused into the surface of a ferrous product to produce a hard case high
surface hardness, improved wear resistance, increased fatigue resistance, and improved
corrosion resistance;
Performed between 500 and 550oC, quenching is not required minimum distortion and
excellent control;
Purposes: to obtain high surface hardness; to increase wear resistance and antigalling
properties; to improve fatigue life; to improve corrosion resistance (except for stainless
steels); to obtain a surface that is resistant to the softening effect of heat at temperatures
up to the nitriding temperature;
57
Processes: gas nitriding, liquid nitriding, plasma (ion) nitriding;

Structure: diffusion zone (original core microstructure with nitride precipitates and
nitrogen solid solution) with or without a compound zone (Fe 4N and Fe2-3N
intermetallics).
Factors affecting the microhardness profile of a nitrided steel.The hardness of the
compound zone is unaffected by alloy content, while the hardness of the diffusion zone is
determined by nitride-forming elements (Al, Cr, Mo, Ti, V, Mn).
Applications
Aluminum-containing low- alloy steels: Nitralloys;
Medium-carbon, chromium-containing low-alloy steels: 4100, 4300, 5100, 6100, 8600,
8700, and 9800 series;
Low-carbon, chromium-containing low-alloy steels: 3300, 8600, and 9300 series;
Hot-working die steels containing 5% Cr: H11, H12, and H13;
Air-hardenabletool steels: A2, A6, D2, D3, and S7;
High-speed tool steels: M2 and M4;
Nitronic stainless steels: 30, 40, 50, and 60;
Ferritic and martensitic stainless steels: 400 series;
Austenitic stainless steels: 200 and 300 series;
Gas nitriding:
Nitrogen is introduced into the surface of a solid ferrous alloy by holding the metal at a
suitable temperature (495 to 525oC) in contact with a nitrogenous gas, usually ammonia;
Single-stage process: brittle nitrogen-rich compound zone known as the white nitride
layer at the surface of the nitrided case;
Double-stage process (Floe process):reducing the white nitrided layer thickness; the
second stage is added which either by continuing at the first-stage temperature or
increasing the temperature to 550 to 565oC higher-temperature second stage lowers the
case hardness and increases the case depth.
FLAME HARDENING
This involves heating the surface of a steel with an oxyacetylene flame (transforming the
structure of the surface layers to austenite), and then immediately quenching the surface
with cold water (changing the austenite to martensite). The depth of hardening depends
on the heat supplied per unit surface area per unit time. Thus, the faster the burner is
moved over the surface, the less the depth of hardening. The temperatures used in this
method are typically of the order of 850C or more, i.e. above the A temperature
58
INDUCTION HARDENING
This method involves placing the steel component within a coil, through which a high
frequency current is passed. The form of the induction coil depends on the shape of the
component being hardened hardened. The alternating current induces another alternating
current to flow within the surface layers of the steel component, the induced electrical
currents heating the surface layers. The temperatures so produced cause the surface layers
to change to austenite. When the surface has reached the austenitizing temperature, the
surface is sprayed with cold water to transform the austenite to martensite. The depth of
heating produced by this method, and hence the depth of hardening, is related to the
frequency of the alternating current used. The higher the frequency, the less the hardened
depth
59
Process
Metals
Element
hardened
added to
Procedure
General
Typical
Characteristics
applications
surface
Carburizi
Low-
Heat steel at 870 A hard, high- Gears, cams,
ng
carbon
950 C (16001750 carbon
steel
F) in an atmosphere is
(0.2%
of
C), alloy
gases
steels
carburizing)
(0.08
carbon-containing
mm ( < 0.020 to
0.2% C)
solids
0.060 in.). Some
(pack
surface shafts,
produced. bearings,
carbonaceous Hardness 55 to piston pins,

(gas 65 HRC. Case sprockets,
or depth < 0.51.5 clutch plates
carburizing). distortion
Then quench.
of
part during heat

treatment.
Carbonitr Lowiding
C and N
Heat steel at 700 Surface
Bolts, nuts,
carbon
800 C (13001600 hardness 55 to gears
steel
F) in an atmosphere 62 HRC. Case

of carbonaceous gas depth 0.07 to
and ammonia. Then 0.5 mm (0.003
quench in oil.
to
0.020
in.).
Less distortion
than in
carburizing.
Cyanidin
Low-
C and N
carbon
845 C (14001550 hardness up to screws,
steel
F) in a molten bath 65 HRC. Case small gears
(0.2%
of
C), alloy
cyanide (e.g., 30% 0.25 mm (0.001
steels
sodium cyanide) and to
(0.08
other salts.
solutions
0.2% C)
60
Bolts, nuts,
of depth 0.025 to
0.010
in.).
Some distortion.
Nitriding
Steels
Gears,
(1% Al,
600 C (9251100 hardness up to shafts,
1.5% Cr,
F) in an atmosphere 1100 HV. Case sprockets,
0.3%
of ammonia gas or depth 0.1 to 0.6 valves,
Mo),
mixtures of molten mm (0.005 to cutters,
alloy
cyanide
steels
further treatment.
salts.
No 0.030 in.) and boring bars,

0.02 to 0.07 mm fuel-
(Cr, Mo),
(0.001
injection
stainless
to 0.003 in.) for pump parts
steels,
high speed steel.
highspeed
tool
steels
Boronizi
Steels
ng
Part is heated using Extremely hard Tool and die

boron-containing
gas
or
solid
and
wear steels
in resistant
contact with part.
surface.
Case
depth
0.025
0.075
mm
(0.001
0.003 in.).
Flame
Medium-
None
Surface
is
heated Surface
Gear
and
hardenin
carbon
with
steels,
oxyacetylene torch, 60 HRC. Case teeth, axles,
cast irons
then quenched with depth 0.7 to 6 crankshafts,
an hardness 50 to sprocket
water spray or other mm (0.030 to piston rods,

quenching methods.
0.25 in.). Little lathe

distortion.
and centers
Induction Same as None
Metal part is placed Same as above
Same
hardenin
in copper induction
above
above
61
beds
as
coils and is heated

by high frequency
current,
then
quenched.
62
UNIT III
MECHANICAL PROPERTIES AND TESTING
Mechanism of plastic deformation, slip and twinning Types of fracture Testing of

materials under tension, compression and shear loads Hardness tests (Brinell, Vickers
and Rockwell), Impact test - Izod and Charpy, Fatigue and creep tests, fracture toughness
tests.
Mechanism of Plastic Deformation

Permanent plastic deformation is due to shear process atoms change their neighbors.
Inter- atomic forces and crystal structure plays an important role during plastic
deformation.
Cumulative movement of dislocations leads to gross plastic deformation.
Edge dislocation move by slip and climb, while screw dislocation move by slip and
cross-slip.
During the movement, dislocations tend to interact. The interaction is very complex
because of number of dislocations moving over many slip systems in different directions.
While some materials are elastic in nature up point of fracture, many engineering
materials like metals and thermo-plastic polymers can undergo substantial permanent
deformation. This characteristic property of materials makes it feasible to shape them.
However, it imposes some limitations on the engineering usefulness of such materials.
Permanent deformation is due to process of shear where particles change their neighbors.
During this process inter-atomic or inter-molecular forces and structure plays important
roles, although the former are much less significant than they are in elastic behavior.
Permanent deformation is broadly two types plastic deformation and viscous flow.
Plastic deformation involves the relative sliding of atomic planes in organized manner in
crystalline solids, while the viscous flow involves the switching of neighbors with much
more freedom that does not exist in crystalline solids.
It is well known that dislocations can move under applied external stresses. Cumulative
movement of dislocations leads to the gross plastic deformation. At microscopic level,
dislocation motion involves rupture and reformation of inter-atomic bonds. The necessity
of dislocation motion for ease of plastic deformation is well explained by the discrepancy
between theoretical strength and real strength of solids, as explained in chapter-3. It has
been concluded that one-dimensional crystal defects dislocations plays an important
role in plastic deformation of crystalline solids. Their importance in plastic deformation
is relevant to their characteristic nature of motion in specific directions (slip-directions)
on specific planes (slip-planes), where edge dislocation move by slip and climb while
screw dislocation can be moved by slip and cross-slip.
63
The onset of plastic deformation involves start of motion of existing dislocations in real
crystal, while in perfect crystal it can be attributed to generation of dislocations and
subsequently their motion. During the motion, dislocations will tend to interact among
themselves. Dislocation interaction is very complex as number of dislocations moving on
number of slip planes in various directions. When they are in the same plane, they repel
each other if they have the same sign, and annihilate if they have opposite signs (leaving
behind a perfect crystal). In general, when dislocations are close and their strain fields
add to a larger value, they repel, because being close increases the potential energy (it
takes energy to strain a region of the material). When unlike dislocations are on closely
spaced neighboring slip planes, complete annihilation cannot occur. In this situation, they
combine to form a row of vacancies or an interstitial atom.
An important consequence interaction of dislocations that are not on parallel planes is
that they intersect each other or inhibit each others motion. Intersection of two
dislocations results in a sharp break in the dislocation line. These breaks can be of two
kinds:
(a) A jog is break in dislocation line moving it out of slip plane.
(b) A kink is break in dislocation line that remains in slip plane.
Other hindrances to dislocation motion include interstitial and substitutional atoms,
foreign particles, grain boundaries, external grain surface, and change in structure due to
phase change. Important practical consequences of hindrance of dislocation motion are
that dislocations are still movable but at higher stresses (or forces), and in most instances
that leads to generation of more dislocations. Dislocations can spawn from existing
dislocations, and from defects, grain boundaries and surface irregularities. Thus, the
number of dislocations increases dramatically during plastic deformation. As further
motion of dislocations requires increase of stress, material can be said to be strengthened
i.e. materials can be strengthened by controlling the motion of dislocation.
Mechanisms of plastic deformation in metals
Plastic deformation, as explained in earlier section, involves motion of dislocations.
There are two prominent mechanisms of plastic deformation, namely slip and twinning.
Slip is the prominent mechanism of plastic deformation in metals. It involves sliding of
blocks of crystal over one other along definite crystallographic planes, called slip planes.
In physical words it is analogous to a deck of cards when it is pushed from one end. Slip
occurs when shear stress applied exceeds a critical value. During slip each atom usually
moves same integral number of atomic distances along the slip plane producing a step,
but the orientation of the crystal remains the same. Steps observable under microscope as
straight lines are called slip lines.
Slip occurs most readily in specific directions (slip directions) on certain crystallographic
planes. This is due to limitations imposed by the fact that single crystal remains
homogeneous after deformation. Generally slip plane is the plane of greatest atomic
density, and the slip direction is the close packed direction within the slip plane. It turns
64
out that the planes of the highest atomic density are the most widely spaced planes, while
the close packed directions have the smallest translation distance. Feasible combination
of a slip plane together with a slip direction is considered as a slip system. The common
slip systems are given in table
In a single crystal, plastic deformation is accomplished by the process called slip, and
sometimes by twinning. The extent of slip depends on many factors including external
load and the corresponding value of shear stress produced by it, the geometry of crystal
structure, and the orientation of active slip planes with the direction of shearing stresses
generated. Schmid first recognized that single crystals at different orientations but of
same material require different stresses to produce slip. The dependence of various
factors has been summarized using a parameter critical resolved shear stress, R, given
as
Slip in polycrystalline material involves generation, movement and (re-)arrangement of

dislocations. Because of dislocation motion on different planes in various directions, they
may interact as well. This interaction can cause dislocation immobile or mobile at higher
stresses. During deformation, mechanical integrity and coherency are maintained along
the grain boundaries; that is, the grain boundaries are constrained, to some degree, in the
shape it may assume by its neighboring grains. Once the yielding has occurred, continued
plastic deformation is possible only if enough slip systems are simultaneously operative
so as to accommodate grain shape changes while maintaining grain boundary integrity.
According to von Mises criterion, a minimum of five independent slip systems must be
operative for a polycrystalline solid to exhibit ductility and maintain grain boundary
integrity. This arises from the fact that an arbitrary deformation is specified by the six
components of strain tensor, but because of requirement of constant volume, there are
only independent strain components. Crystals which do not possess five independent slip
systems are never ductile in polycrystalline form, although small plastic elongation may
be noticeable because of twinning or a favorable preferred orientation.
65
Twinning
plane (twin boundary) mirror the atoms on the other side.
Displacement magnitude in the twin region is proportional to the atoms

distance from the twin plane
takes place along defined planes and directions depending upon the system.
o
Ex: BCC twinning occurs on the (112)[111] system
The second important mechanism of plastic deformation is twinning. It results when a

portion of crystal takes up an orientation that is related to the orientation of the rest of the
untwined lattice in a definite, symmetrical way. The twinned portion of the crystal is a
mirror image of the parent crystal. The plane of symmetry is called twinning plane. Each
atom in the twinned region moves by a homogeneous shear a distance proportional to its
distance from the twin plane. The lattice strains involved in twinning are small, usually in
order of fraction of inter-atomic distance, thus resulting in very small gross plastic
deformation. The important role of twinning in plastic deformation is that it causes
changes in plane orientation so that further slip can occur. If the surface is polished, the
twin would be still visible after etching because it possesses a different orientation from
the untwined region. This is in contrast with slip, where slip lines can be removed by
polishing the specimen.
Properties of Twinning
It occurs in metals with BCC or HCP crystal structure
occurs at low temperatures and high rates of shear loading (shock

loading)
pccurs in conditions in which there are few present slip systems
(restricting the possibility of slip)
In which small amount of deformation when compared with slip.
66
Twinning also occurs in a definite direction on a specific plane for each crystal structure.
However, it is not known if there exists resolved shear stress for twinning. Twinning
generally occurs when slip is restricted, because the stress necessary for twinning is
usually higher than that for slip. Thus, some HCP metals with limited number of slip
systems may preferably twin. Also, BCC metals twin at low temperatures because slip is
difficult. Of course, twinning and slip may occur sequentially or even concurrently in
some cases. Twinning systems for some metals are given in table-
67
Fractures
Failure of a material component is the loss of ability to function normally orto perform
the intended job
Three general ways failure: Excessive elastic deformation, E.g.:buckling. Controlled by
design and elastic modulus of the material.Excessive plastic deformation, Controlled by
yield strength of the material. E.g.:loss of shape, creep and/ or stress-rupture at elevated
temperatures.Fracture, involves complete disruption of continuity of a component under
static load: brittle or ductile, under fluctuating/cyclic load: fatigue, mode in which most
machine parts fail in service.
Fracture defined as the separation or fragmentation of a solid body into two or more parts
under the action of stress.
Fracture is classified based on several characteristic features:
68
Fracture Modes
Ductile and Brittle are relative terms. Most of the fractures belong to one of the following
modes: (a) rupture, (b) cup-&-cone
and (c) brittle.
Ductile fracture in tension occurs after appreciable plastic deformation. It is usually

preceded by necking. It exhibits three stages -(1) formation of cavities (2) growth of
cavities (3) final failure involving rapid crack propagation at about 45to the tensile axis.
Fractography of ductile fracture reveals numerous spherical dimples separated by thin
walls on the fractured surface.
Stages of void nucleation, void growth, crack initiation and eventual fracture under
ductile fracture mode:
69
Brittle Fracture
Brittle fracture intakes place with little orno preceding plastic deformation. It occurs,
often at unpredictable levels of stress, by rapid crack propagation. Crack propagates
nearly perpendicular to the direction of applied tensile stress, and hence called cleavage
fracture. Most often brittle fracture occurs through grains i.e. transgranular. Three stages
of brittle fracture -(1) plastic deformation that causes dislocation pile-ups at obstacles, (2)
micro-crack nucleation as a result of build-up of shear stresses, (3) eventual crack
propagation under applied stress aided by stored elastic energy.
Brittle farcture - Griffth Theory
Creep Fracture
Deformation that occurs under
constant load/stress and elevated
temperatures which is time-dependent
70
is known as creep. Creep deformation (constant stress) is possible at all temperatures

above absolute zero. However, it is extremely sensitive to temperature. Hence, creep in
usually considered important at elevated temperatures (temperatures greater than 0.4 Tm,
Tm is absolute melting temperature). Creep test data is presented as a plot between time
and strain known as creep curve. The slope of the creep curve is designated as creep rate.
Creep curve is considered to be consists of three portions. After initial rapid elongation,
0, the creep rate decreases continuously with time, and is known as primaryor transient
creep. Primary creep is followed by secondaryor steady-stateor viscous creep, which is
characterized by constant creep rate. This stage of creep is often the longest duration of
the three modes. Finally, a third stage of creep known as, tertiary creepoccurs that is
characterized by increase in creep rate.
First stage creep is associated with strain hardening of the sample. Constant creep rate
during secondary creep is believed to be due to balance between the competing processes
of strain hardening and recovery. Creep rate during the secondary creep is called the
minimum creep rate. Third stage creep occurs in constant load tests at high stresses at
high temperatures. This stage is greatly delayed in constant stress tests. Tertiary creep is
believed to occur because of either reduction in cross-sectional area due to necking or
internal void formation. Third stage is often associated with metallurgical changes such
as coarsening of precipitate particles, recrystallization, or diffusional changesin the
phases that are present. Two most important parameter that influence creep rate are:
stress and temperature. With increase in either stress or temperature (a) instantaneous
elastic strain increases (b) steady state creep rate increases and (c) rupture lifetime
decreases.
Brinell Hardness Test
Dr. J. A. Brinell invented the Brinell test in Sweden in 1900. The oldest of the hardness
test methods in common use today, the Brinell test is frequently used to determine the
hardness of forgings and castings that have a grain structure too course for Rockwell or
Vickers testing. Therefore, Brinell tests are frequently done on large parts. By varying the
test force and ball size, nearly all metals can be tested using a Brinell test. Brinell values
are considered test force independent as long as the ball size/test force relationship is the
same.
Brinell Test Method

All Brinell tests use a carbide ball indenter. The test procedure is as follows:
The indenter is pressed into the sample by an accurately controlled test force.
The force is maintained for a specific dwell time, normally 10 - 15 seconds.
After the dwell time is complete, the indenter is removed leaving a round indent
in the sample.
71
The size of the indent is determined optically by measuring two diagonals of the
round indent using either a portable microscope or one that is integrated with the load
application device.
The Brinell hardness number is a function of the test force divided by the curved
surface area of the indent. The indentation is considered to be spherical with a radius
equal to half the diameter of the ball. The average of the two diagonals is used in the
following formula to calculate the Brinell hardness.
The Brinell number, which normally ranges from HB 50 to HB 750 for metals, will
increase as the sample gets harder. Tables are available to make the calculation simple. A
typical Brinell hardness is specified as follows:
356HBW
Where 356 is the calculated hardness and the W indicates that a carbide ball was used.
Note- Previous standards allowed a steel ball and had an S designation. Steel balls are no
longer allowed.
Applications
Because of the wide test force range the Brinell test can be used on almost any metallic
material. See the application guide. The part size is only limited by the testing
instrument's capacity.
72
UNIT IV FERROUS AND NON FERROUS METALS

Effect of alloying additions on steel (Mn, Si, Cr, Mo, V Ti & W) - stainless and tool
steels HSLA - maraging steels Gray, White malleable, spheroidal - Graphite - alloy
castirons
Copper and Copper alloys Brass, Bronze and Cupronickel Aluminum and Al-Cu
precipitation strengthening treatment Bearing alloys.
HSLA steel
High strength low alloy (HSLA) steel is a type of alloy steel that provides better
mechanical properties or greater resistance to corrosion than carbon steel. HSLA steels
vary from other steels in that they aren't made meet a specific chemical composition, but
rather to specific mechanical properties. They have a carbon content between 0.050.25%
to retain formability and weldability.
Other alloying elements include up to 2.0% manganese and small quantities of copper,
nickel, niobium, nitrogen, vanadium, chromium, molybdenum, titanium, calcium, rare
earth elements, or zirconium. Copper, titanium, vanadium, and niobium are added for
strengthening purposes. These elements are intended to alter the microstructure of carbon
steels, which is usually a ferrite-pearlite aggregate, to produce a very fine dispersion of
alloy carbides in an almost pure ferrite matrix. This eliminates the toughness-reducing
effect of a pearlitic volume fraction, yet maintains and increases the material's strength by
refining the grain size, which in the case of ferrite increases yield strength by 50% for
every halving of the mean grain diameter.
CAST IRON
The cast irons are the ferrous alloys with greater that 2.14 wt % carbon, but typically
contain 3-4.5 wt % of C as well as other alloying elements, such as silicon (~3 wt.%)
which controls kinetics of carbide formation
There are four general types of cast irons:
1. White iron has a characteristics white, crystalline fracture surface. Large amount of
Fe3C are formed during casting, giving hard brittle material
2. Gray iron has a gray fracture surface with finely faced structure. A large Si content (23 wt %) promotes C flakes precipitation rather than carbide
3. Ductile iron: small addition (0.05 wt.%) of Mg to gray iron changes the flake C
microstructure to spheroidal that increases (by factor ~20) steel ductility
4. Malleable iron: traditional form of cast iron with reasonable ductility. First cast to
white iron and then heat-treated to produce nodular graphite precipitates.
White and Malleable cast iron
The low-silicon cast irons (<1.0wt.%), produced under rapid cooling conditions
73
Microstructure: most of cementite

Properties: extremely hard very but brittle
White iron is an intermediate for the production of malleable iron
In white cast iron light Fe3C regions surrounded by pearlite
In malleable cast iron dark graphite rosettes in -Fe matrix
Gray and Ductile Cast Irons
The gray irons contain 1-31.0 wt.% of Si
Microstructure: flake shape graphite in ferrite matrix
Properties : relatively weak and brittle in tension BUT very effective in damping
vibrational energy an high resistive to wear!!
Ductile (or Nodular) iron : small addition of Mg or/and Ce to the gray iron composition
before casting
Microstructure: Nodular or spherical-like graphite structure in pearlite or ferric matrix
Properties: Significant increase in material ductility
Applications: valves pump bodies, gears and other auto and machine components.
74
Effect of Alloying elements
75
76
Copper and its Alloys

Copper: soft and ductile; unlimited cold-work capacity, high electrical conductivity, high
thermal thermal conductivity, resist to corrosion, cannot be welded, but difficult to
machine. Cold-working and solid solution alloying. It is the oldest one widely used.
Main types of Copper Alloys:
Brasses(Cu-Zn): 36% of zinc (Zn) and Pb, Al, Mn are added with it. It exists in brasses, -brasses. It is soft ductile, cold worked, stronger than copper, lowthermal and
electrical conductivity than copper.Applications: cartridges, auto-radiator. Musical
instruments, coins.
Bronzes(Cu-Sn): tin (Sn), aluminum (Al), Silicon (Si) and nickel (Ni); stronger than
brasses with high degree of corrosion resistance. It can be shaped or rolled into wires,
rods and sheets.
Heat-treated (precipitation hardening) Cu-alloys: beryllium coopers; relatively high
strength, excellent electrical and corrosion properties BUT expensive; applications: jet
aircraft landing gear bearing, surgical and dental instruments.
- Cupronickel (Cu-Ni) It is ductile and malleable and it is good corrosive resistant for sea
water. It can be shaped to any form.
Copper advantage as primary metal and recycled metal, for brazed, long-life radiators and
radiator parts for cars and trucks:
Applications: Manufacturing of power cables, telephone cables, water tanks in food and
chemical industries and in heat exchangers
Aluminum and its Alloys
It is light weight, low specific gravity, high strength to weight ratio. Low density (~2.7
g/cm3), high ductility (even at room temperature), high electrical and thermal
conductivity and resistance to corrosion BUT law melting point (~660C).
Main types of Aluminum Alloys:
- Wrought Alloys
- Cast Alloys
- Others: e.g. Aluminum-Lithium Alloys
Applications: form food/chemical handling to aircraft structural parts
77
Magnesium and its Alloys

Key Properties:
Light weight
Low density (1.74 g/cm3 two thirds that of aluminium)
Good high temperature mechanical properties
Good to excellent corrosion resistance
Very high strength-to density ratios (specific strength)
In contrast with Al alloys that have fcc structure with (12 ) slip systems and thus high
ductility, hcp structure of Mg with only three slip systems leads to its brittleness.
Applications: from tennis rockets to aircraft and missiles
Example: Aerospace
RZ5 (Zn 3.5 - 5,0 SE 0.8 - 1,7 Zr 0.4 - 1,0 Mg remainder), MSR (AG 2.0 - 3,0 SE 1.8 2,5Zr 0.4 - 1,0 Mg remainder) alloys are widely used for aircraft engine and gearbox
casings. Very large magnesium castings can be made, such as intermediate compressor
casings for turbine engines. These include the Rolls Royce Tay casing in MSR, which
weighs 130kg and the BMW Rolls Royce BR710 casing in RZ5. Other aerospace
applications include auxiliary gearboxes (F16, Euro-fighter 2000, Tornado) in MSR or
RZ5, generator housings (A320 Airbus, Tornado and Concorde in MSR) and canopies,
generally in RZ5.
Titanium and its Alloys (1)
Titanium and its alloys have proven to be technically superior and cost-effective
materials of construction for a wide variety of aerospace, industrial, marine and
commercial applications.
The properties and characteristics of titanium which are important to design engineers in
a broad spectrum of industries are:
- Excellent Corrosion Resistance: Titanium is immune to corrosive attack by salt water
or marine atmospheres. It also exhibits exceptional resistance to a broad range of acids,
alkalis, natural waters and industrial chemicals.
78
- Superior Erosion Resistance: Titanium offers superior resistance to erosion, cavitation

or impingement attack. Titanium is at least twenty times more erosion resistant than the
copper-nickel alloys.
- High Heat Transfer Efficiency: Under "in service" conditions, the heat transfer
properties of titanium approximate those of admiralty brass and copper-nickel.
Titanium alloys capable of operating at temperatures from sub zero to 600C are used in
engines for discs, blades, shafts and casings from the front fan to the last stage of the high
pressure compressor, and at the rear end of the engine for lightly loaded fabrications such
as plug and nozzle assemblies.
Alloys with strength up to 1200MPa are used in a wide variety of airframe applications
from small fasteners weighing a few grams to landing gear trucks and large wing beams
weighing up to 1 ton.
Currently titanium makes up to 10% of empty weight of aircraft such as the Boeing 777.
Other Alloys
The Refractory Metals: Nb (m.p.=2468C); Mo (C); W (C); Ta(3410C)
- Also: large elastic modulus, strength, hardness in wide range of temperatures
The Superalloys possess the superlative combination of properties
- Examples:
- Applications: aircraft turbines; nuclear reactors, petrochemical equipments
The Noble Metal Alloys: Ru(44), Rh (45), Pd (46), Ag (47), Os (75), Ir (77), Pt (78),
Au (79)
- expensive are notable in properties: soft, ductile, oxidation resistant
- Applications: jewelry (Ag, Au, Pt), catalyst (Pt, Pd, Ru), thermocouples (Pt, Ru),
dental materials etc.
Miscellaneous Nonferrous Alloys:
Nickel and its alloy: high corrosion resistant (Example: monel 65Ni/28Cu/7wt%Fe
pumps valves in aggressive environment)
Lead, tin and their alloys: soft, low recrystalization temperature, corrosion resistant
(Applications: solders, x-ray shields, protecting coating).
79
UNIT-V
Polymers are materials of complex structure. Polymer consists of many units.
In polymer, molecules of ordinary sizes are combined in long chains.
Types of polymers
Plastics
Fibers
Elastomers
Polymers with fillers, solvents, plasticers and pigments are known as plastic.
Types of plastics:
Thermo plastic
Thermoset plastic
Major Characteristics of plastics are:

Non crystalline structure
Low softening temperature
Resistance to chemical reaction
Visco- elastic behaviour
Non-conductors
Low thermal conductivity
Engineering thermoplastics are:
Polythene
Polyvinylchloride
Polypropene
Polystyrene
Polymethyl Methacrylate
Polyesters
Polycarbonates
Polyamides
ABS
Polymers
The word polymeris originated from Greek word meros, which means a part.
Polymers are primarily organic compounds, however few polymers are made of inorganic
compounds. Characteristics of ceramics are:-low temperature stability-low hardness-low
mechanical strength-high elongation under application of stress-low thermal and
electrical conductivities-high sensitivity of properties to their morphology
Polymer classification
Polymers are classified in many ways. The prime classification based on their industrial
usage is: plastics and elastomers.
Plastic polymers are again classified based on their temperature dependence of their
structure as follows:-thermoplastsand-thermosets
80
Thermo Plastic
Plastics which softens up on heating and hardens up on cooling where the softening and
hardening are totally reversible processes. Hence thermoplastscan be recycled. They
consist of linear molecular chains bonded together by weak secondary bonds or by interwinding. Cross-linking between molecular chains is absent in theromplasts. E.g.:
Acrylics, PVC, Nylons, Perspex glass, etc.
Thermosets
Plastics which are setunder the application of heat and/or pressure. This process is not
reversible, hence thermosetscan not be recycled.
They consist of 3-D network structures based on strong covalent bonds to form rigid
solids. linear molecular chains bonded together by weak secondary bonds or by interwinding.
Characterized by high modulus / rigidity / dimensional stability when compared with
thermoplasts.
E.g.: Epoxies, Amino resins, some polyester resins, etc.
Elastomers
These polymers are known for their high elongations, which are reversible upon release
of applied loads. They consist of coil-like molecular chains, which straightens up on
application of load. Characterized by low modulus / rigidity / strength, but high
toughness.E.g.: natural and synthetic rubber.
Polymer Synthesis
Processing of polymers primarily limits to synthesis followed by forming. Polymers are
synthesized by process known as polymerization. Polymerization is process in which
multi-functional monomers are attached to form linear/3-D macro molecular chains.
When polymerization process involves single kind of monomers i.e. in Additional
polymerization, resultant macro-molecules composition is an exact multiplication of
composition of individual monomer.
Additional polymerization process involves three stages namely initiation, propagation
and termination. Initiation process will be started by an initiator (e.g.benzoylperoxide)
which forms an reactive site where carbon atom of another monomer is attracted, upon
which reaction site transfers to different place leading to molecular chain growth. As
molecular chain grows longer, reaction rate decreases. However the growth process is
terminated either by the combination or disproportionation process.
Polymer Synthesis
81
Degree of Polymerisation
Extant of polymerization is
characterized in terms of degree of
polymerization. It is defined as
number of mer units in molecular chain or ration of average molecular weight of polymer
to molecular weight of repeat unit. Average molecular weight is defined in two ways:
Weight average molecular weight(based on weight fraction) and Number average
molecular weight(based on the number fraction). Number average molecular weight is
always smaller than the weight average molecular weight.
Ceramics
The word ceramicis originated from greekword keromikos, which means burnt stuff.
Ceramics are compounds of metallic and non-metallic elements. Characteristics of
ceramics are:-high temperature stability-high hardness-brittleness-high mechanical
strength-low elongation under application of stress-low thermal and electrical
conductivities. Ceramics are classified in many ways. It is due to divergence in
composition, properties and applications. Based on their composition, ceramics are:Oxides-Carbides-Nitrides-Sulfides-Fluoridesetc.
Classification of Ceramics
Based on their specific applications, ceramics are classified as:-Glasses-Clay productsRefractories-Abrasives-Cements-Advanced ceramics for special applications
Based on their engineering applications, ceramics are classified into two groups as:
traditional and engineering ceramics.
Traditional ceramics most made-up of clay, silica and feldspar
Engineering ceramics these consist of highly purified aluminium oxide (Al2O3), silicon
carbide (SiC) and silicon nitiride(Si3N4)
82
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Dept. of Mechanical Engineering, St.

Josephs College of Engineering

ME 2253 ENGINEERING MATERIALS & METALLURGY

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Engine efficiency increases at high temperatures; requires high temperature

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Based on the structures

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Hume Rothery rules Controls the range of Solubility in alloy system

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

- To indicate the temperature at which different phases start to melt.

Dept. of Mechanical Engineering, St. Josephs College of Engineering

X-ray Diffraction Technique:

Figure 2. Cooling curve for the solidification of a pure metal.

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Figure 3. Cooling curve for a solid solution.

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Figure 5. Phase Diagram of alloy A+B

Figure-1: Unary phase diagram for water.

In most engineering applications, as mentioned before, condensed phase rule is

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Hence, binary systems are classified according to their solid solubility.

Dept. of Mechanical Engineering, St. Josephs College of Engineering

or only at relatively fixed composition (compound). These intermediate phases may

Dept. of Mechanical Engineering, St. Josephs College of Engineering

where repeated cooling/heating of an alloy at different compositions, and corresponding

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Solid percent = 22 / 46 = 47.82 percent

Example of isomorphous system:

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

intermediate alloy phase, since it is a compound, it is indicated as AB 2, where 2 is the no

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Intermediate phases: An intermediate phase may occur over a composition range

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

The iron carbon system, phase transformations

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Cementite, Fe3C an inter-metallic compound forms when amount of carbon present

Dept. of Mechanical Engineering, St. Josephs College of Engineering

The decomposition of austenite to form pearlite occurs by nucleation and growth.

Dept. of Mechanical Engineering, St. Josephs College of Engineering

temper carbon appears approximately as spherical particles. SG iron is produced by

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Classification Of Metal Alloys

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Low Alloys: Low Carbon

Dept. of Mechanical Engineering, St. Josephs College of Engineering

High-Alloy Steels: Stainless Steels (SS)

Dept. of Mechanical Engineering, St. Josephs College of Engineering

High-Alloy Steels: Tools steels

Dept. of Mechanical Engineering, St. Josephs College of Engineering

Micro Structures of steel

Dept. of Mechanical Engineering, St. Josephs College of Engineering