Engineering Materials and

Metallurgy
Unit 1 - Alloys and Phase Diagrams
Unit 2 - Heat Treatment
Unit 3 - Ferrous and Non-ferrous Metals
Unit 4 - Non-metallic Materials
Unit 5 - Mechanical Properties and Deformation
Mechanisms
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Unit 1

Alloys and Phase Diagrams

Constitution of alloys - Solid solutions, substitutional and
interstitial - phase diagrams, Isomorphous, eutectic, eutectoid,
peritectic, and peritectoid reactions, Iron - carbon equilibrium
diagram. Classification of steel and cast Iron microstructure,
properties and application.

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Constitution of Alloys
Subject Code: ME6403
Title: Engineering Materials and Metallurgy

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General Objective
To study and understand the concepts of alloy
structure.

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Pre-requisite Knowledge
Engineering materials
Classification of engineering materials
Types of Crystal structure

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Specific Objectives

Classify the solid solution.

Explain the general rules of Hume Rothery.
Differentiate substitutional and interstitial solutions.

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Alloy
An 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.
Alloys may be classified according to their structure, and
complete alloy systems may be classified according to the
type of their equilibrium or phase diagram.
Alloys may be homogeneous (uniform) or mixtures. If the
alloy is homogenous it will consist of a single phase, and if it
is a mixture it will be a combination of more than one phases.

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Solid Solutions
In the solid state there are three possible phases:
1. Pure metal
2. Intermediate alloy phase or compound
3. Solid solution
A solid solution may be defined as a solid that consists of two or
more elements atomically dispersed in a single-phase Structure
A solid solution is composed of two parts.
Solute: A solute is the minor part of the solution or the
material which is dissolved
Solvent: Solvent constitutes the major portion of the solution.
Both the solute and the solvent can be solid, liquid or gas.

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Possibilities of Solid Solutions

There are three possible solid solutions based on the amount of
their elements. They are:
1.Unsaturated solid solution:
If the solvent is dissolving small amount of solute, it is
called unsaturated solid solution.
2. Saturated solid solution:
If the solvent is dissolving limiting amount of solute, it is
called saturated solid solution.
3. Supersaturated solid solution:
If the solvent is dissolving more of solute than it should, it
is called supersaturated solid solution.
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Hume Rothery's Rules

To form an extensive solid solution, the solute and solvent
elements should obey the general rules of Hume Rothery, that
control the range of solubility in alloy systems.
1. Relative-Size factor:
The size factor is favorable for solid-solution formation
when the difference in atomic radii is less than about 15
percent.
If the relative size factor is greater than 15 percent, solidsolution formation is very limited.
Note: silver and lead (difference in atomic radii is 20 %),
solubility only 5%.
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Cont.,
2. Crystal-structure factor:
Complete solid solubility of two elements is never attained
unless the elements have the same type of crystal lattice
structure.
3. Relative-Valence factor:
If the solute metal has a different valence from that of the
solvent metal, the electron ratio will be changed.
The number of valence electrons per atom is called election
ratio.
Crystal structures are more sensitive to a decrease in the
electron ratio than to an increases.
In other words, a metal of lower valence tends to dissolve more
of a metal of higher valence than vice versa.
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Cont.,
4. Electronegativity :
It is the ability of the atom to attract an electron.
The atoms must have approximately the same
electronegativity. If electronegativity differ significantly,
then the compounds will form.
By considering the above four factors, some estimate of the solid
solubility of one metal in another can be determined.
It is important to note that an unfavorable relative-size factor
alone is sufficient to limit solubility to a low value.
If the relative-size factor is favorable, then the other three factors
should be considered in deciding on the probable degree of solid
solubility.
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Types of Solid Solutions

1. Substitutional solid solutions
a) Random
b) Ordered
2. Interstitial solid solutions
1. Substitutional Solid Solutions:
In substitutional solid solution, the atoms of the solvent
substitute for atoms of the solute in the lattice structure of
the solvent.
This type of solid solution is quite common among various
metal systems
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Cont.,
Illustration:
A Ni-Cu system, shown in
Figure, is an example for a
substitutional solid solution.
These two elements are
completely soluble in one
another at all proportions.
This system also satisfies all
the Hume Rothery's rules.

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Random Substitutional Solid Solution

In random substitutional solid solution,
there is no order in the substitution of
the two elements; the solute and
solvent
atoms
are
randomly
distributed.
In the formation of a substitutional
solid solution, the solute atoms do not
occupy any specific position but

are distributed at random in lattice structure of the

solvent. This alloy is said to be in a random or disordered
condition.
Figure illustrates a random substitutional solid solution of
copper-zinc system (i.e., brass). Here the crystal pattern is
not altered.
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Ordered Substitutional solid Solution

If the solute and solvent atoms take up
some preferred position, then the solution
is called ordered substitutional solid
solution or super lattice.
Figure shows an ordered substitutional
solid solution.

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Interstitial Solid Solution

These are formed when atoms of small atomic
radii fit into the spaces or interstices of the
lattices structure of the larger solvent atoms.
Since the spaces of the lattice structure are
restricted in size, only atoms with atomic
radii less than 1 angstrom are likely to form
interstitial solid solution.
Interstitial solid solution can form only when
one atom is much larger than another.

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Cont.,
These are hydrogen (0.46), boron (0.97),
carbon (0.77), nitrogen (0.71) and
oxygen (0.60).
Figure illustrates an interstitial solid
solution that is formed by carbon in FCC
iron just above 912C.
In this case, the atomic radius of carbon
is 0.77 A (angstrom) and that of iron is
1.29 A (angstrom), and so there is an
atomic radius difference of 42%.
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Mind Map

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Objective Type Questions

1. A single phase system are termed as ___________.
a) Homogenous system
b) Heterogeneous system
c) Compound
2. One angstrom is equal to ___________.
a) 10-3 m
b) 10-10 m
c) 10-13 m
3. The Spaces in the lattice structure are called as ___________.
a) Interstices
b) Compound
c) Distortion

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Stimulating Questions
(Lower Order Technique)
Define alloy.
What are the two types of solid solution?
Differentiate random and ordered solid solution.
List out the various factors of hume rothery rules.

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Stimulating Questions
(Higher Order Technique)
What is solid solution? Explain the Hume Rothery rules
governing substitutional solid solution.
How are solid solutions classified? Give two examples for
each.

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References
Sidney H Avner, Introduction to Physical
Metallurgy Tata McGraw-Hill Publishing Co.2007

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