CHY1005 INDUSTRIAL CHEMISTRY FOR ENGINEERS

MODULE 3 PHYSICAL AND MECHANICAL METALLURGY

INTRODUCTION
Materials Science and Engineering is:
 the study of the properties of solid materials and how those properties are determined by
a material’s composition and structure.
 an interdisciplinary study that combines metallurgy, physics, chemistry, and engineering
to solve real-world problems with real-world materials in an acceptable societal and
economical manner.
 the study of Performance, Properties, Structure, Composition, Synthesis and Processing
of materials and also interactions of these aspects of such materials.
The principal goals of a materials science and engineering are to (1) make existing materials
better and (2) invent or discover new phenomena, materials, devices, and applications.
The heart of materials science is the ability to change the properties and/or behavior of
a material to make most materials useful.
Materials science and engineering (MSE) is an interdisciplinary field of science and
engineering that studies and manipulates the composition and structure of materials across
length scales to control materials properties through synthesis and processing.
Materials science involves investigating the relationships between the structures and
properties of materials.
Materials engineering is based on structure–property correlations, designing or
engineering the structure of a material to produce a predetermined set of properties.
One of the most important functions of materials scientists and engineers is to establish the
relationships between a material or a device’s properties and performance and the
microstructure of that material, its composition, and the way the material or the device was
synthesized and processed.
The goal of Materials Science and Engineering is to design materials with a certain set
of properties, which gives a certain desired performance. Using suitable processing
techniques the material can be synthesized and processed. The processing also determines
the microstructure of the material.
Materials can be classified based on Band Structure (Metals, Semi-metals, Semiconductors,
Insulators) or Atomic Structure (Crystals, Quasicrystals, Amorphous phases).
Composition means the chemical make-up of a material.
Structure means a description of the arrangement of atoms.
Materials scientists and engineers deal with the development of materials and also with the
synthesis and processing of materials and manufacturing processes related to the
production of components.
Synthesis refers to how materials are made from naturally occurring or man-made chemicals.
Processing means how materials are shaped into useful components to cause changes in
the properties of different materials.
Structure of a material usually relates to the arrangement of its internal components.
Structure levels are subatomic, atomic, microscopic, and macroscopic.
A property is a material trait in terms of the kind and magnitude of response to a specific
imposed stimulus.
Important properties of solid materials are: mechanical, electrical, thermal, magnetic,
optical and deteriorative.
The structure of a material will depend on how it is processed.
A material’s performance will be a function of its properties.
The interrelationship between processing, structure, properties, and performance is:

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The culmination of ‘New Technologies’, ‘New Materials’ and
‘New Processes’ is the gate way for ‘New products’ of the
present and future modern societies.

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CLASSIFICATION OF MATERIALS
There are different ways of classifying materials. One way is to describe five groups.
1. metals and alloys;
2. ceramics, glasses, and glass-ceramics;
3. polymers (plastics);
4. semiconductors; and
5. composite materials.

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Functional Classification of Materials

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SELECTION OF MATERIALS
Different materials possess different properties to meet the various requirement for
engineering purposes. A good grasp of the fundamental principles which control the
properties of various materials help to make the optimum selection of material.
For selecting a material or designing a component, it is essential to understand the
requirements of the process thoroughly, operating limitations like hazardous or non-
hazardous conditions, continuous or non-continuous operation, availability of raw materials
as well as spares, availability of alternate materials, life span of the instrument/equipment,
reuse/recycle nature, technology level, environmental impact, sustainability, cost etc.
The selection of a specific material for a particular engineering use as per
specifications is based on (i) operating parameters, (ii) manufacturing processes, (iii)
functional requirements and (iv) cost considerations.

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PROPERTIES OF MATERIALS

(a) Mechanical Properties The important mechanical properties affecting the selection
of a material are:
(i) Tensile Strength: This enables the material to resist the application of a tensile force.
To withstand the tensile force, the internal structure of the material provides the
internal resistance.
(ii) Hardness: It is the degree of resistance to indentation or scratching, abrasion and
wear. Alloying techniques and heat treatment help to achieve the same.
(iii) Ductility: This is the property of a metal by virtue of which it can be drawn into wires
or elongated before rupture takes place. It depends upon the grain size of the metal
crystals.
(iv) Impact Strength: It is the energy required per unit cross-sectional area to fracture a
specimen, i.e., it is a measure of the response of a material to shock loading.
(v) Wear Resistance: The ability of a material to resist friction wear under particular
conditions, i.e. to maintain its physical dimensions when in sliding or rolling contact
with a second member.
(vi) Corrosion Resistance: Those metals and alloys which can withstand the corrosive
action of a medium, i.e. corrosion processes proceed in them at a relatively low rate
are termed corrosion-resistant.
(vii) Density: This is an important factor of a material where weight and thus the mass is
critical, i.e. aircraft components.

(b) Thermal Properties The characteristics of a material, which are functions of the
temperature, are termed its thermal properties.
Specific heat, latent heat, thermal conductivity, thermal expansion, thermal stresses,
thermal fatigue, etc. are few important thermal properties of materials.
These properties play a vital role in selection of material for engineering applications, e.g.
when materials are considered for high temperature service. Now, we briefly discuss few of
these properties:
(i) Specific Heat (c): It is the heat capacity of a unit mass of a homogeneous substance.
For a homogeneous body, c = C/M, where C is the heat capacity and M is the mass of
the body. One can also define it as the quantity of heat required to raise the
temperature of a unit mass of the substance through 1°C. Its units are cal/g°C.
(ii) Thermal Conductivity (K): This represents the amount of heat conducted per unit time
through a unit area perpendicular to the direction of heat conduction when the
temperature gradient across the heat.

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(iii) Thermal Expansion: All solids expand on heating and contract on cooling. Thermal
expansion may take place either as linear, circumferential or cubical. A solid which
expands equally in three mutually orthogonal directions is termed as thermally
isotropic. The increase in any linear dimension of a solid, e.g. length, width, height on
heating is termed as linear expansion.
(iv) The coefficient of linear expansion is the increase in length per unit length per degree
rise in temperature. The increase in volume of a solid on heating is called cubical
expansion. The thermal expansion of solids has its origin in the lattice vibration and
lattice vibrations increases with the rise in temperature.
(v) Thermal Resistance (RT): It is the resistance offered by the conductor when heat flow
due to temperature difference between two points of a conductor.
(vi) Thermal Diffusivity (h): is defined as (thermal conductivity/ [heat capacity x density]).
For a material with low thermal diffusivity more heat must be added to or removed
from the material for effecting a temperature change.
(vii) Thermal Fatigue: This is the mechanical effect of repeated thermal stresses caused by
repeated heating and cooling.

(c) Electrical Properties

Conductivity, resistivity and dielectric strength are few important electrical properties of a
material.
A material which offers little resistance to the passage of an electric current is said to be a
good conductor of electricity.
On the basis of electrical resistivity materials are divided as:
(i) Conductors
(ii) Semiconductors and
(iii) Insulators.
In general metals are good conductors. Insulators have very high resistivity. Ceramic
insulators are most common examples and are used on automobile spark plugs, Bakelite
handles for electric iron, plastic coverings on cables in domestic wiring.
When a large number of metals and alloys are sufficiently cooled below transition
temperature, Tc, enter the state of superconductivity in which the dc resistivity goes to zero.

(d) Magnetic Properties

Materials in which a state of magnetism can be induced are termed magnetic materials.
There are five classes into which magnetic materials may be grouped:
(i) diamagnetic
(ii) paramagnetic
(iii) ferromagnetic
(iv) antiferromagnetic and
(v) ferrimagnetic.
Iron, Cobalt, Nickel and some of their alloys and compounds possess spontaneous
magnetization. Magnetic oxides like ferrites and garnets could be used at high frequencies.
Because of their excellent magnetic properties along with their high electrical resistivity
these materials today find use in a variety of applications like magnetic recording tapes,
inductors and transformers, memory elements, microwave devices, bubble domain devices,
recording hard cores, etc.
Hysteresis, permeability and coercive forces are some of the magnetic properties of
magnetic substances. These properties are to be considered for the manufacture of
transformers and other electronic components.

(e) Chemical Properties

These properties include atomic weight, molecular weight, atomic number, valency,
chemical composition, acidity, alkalinity, etc. These properties govern the selection of
materials particularly in Chemical plants.

(f) Optical Properties

The optical properties of materials, e.g. refractive index, reflectivity and absorption
coefficient etc. affect the light reflection and transmission.

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X-RAY CRYSTALLOGRAPHY
Historically, much of our understanding regarding the atomic and molecular arrangements
in solids has resulted from x-ray diffraction investigations. X-rays are still very important in
developing new materials. The x-ray diffraction phenomenon is used to deduce atomic
interplanar distances and crystal structures.
X-rays are a form of electromagnetic radiation that have high energies and short
wavelengths—wavelengths on the order of the atomic spacings for solids. When a beam of
x-rays impinges on a solid material, a portion of this beam will be scattered in all directions
by the electrons associated with each atom or ion that lies within the beam’s path. Let us now
examine the necessary conditions for diffraction of x-rays by a periodic arrangement of atoms.

Material Structure
Material structure can be classified as: macrostructure, microstructure, substructure, crystal
structure, electronic structure and nuclear structure.
(a) Macrostructure
 Macrostructure of a material is examined by low-power magnification or naked eye.
 It deals with the shape, size and atomic arrangement in a crystalline material.
 In case of some crystals, e.g., quartz, external form of the crystal may reflect the
internal symmetry of atoms.
 Macrostructure may be observed directly on a fracture surface or on a forging specimen.
 The individual crystals of a crystalline material can be visible, e.g. in a brass doorknob by
the constant polishing and etching action of a human hand and sweat.
 Macrostructure can reveal flaws, segregations, cracks etc. by using proper techniques
and one can save much expenses by rejecting defective materials at an early stage.
(b) Micro Structure
 This generally refers to the structure of the material observed under optical microscope.
 Optical microscopes can magnify a structure about 1500 to 3000 times linear, without
loss of resolution of details of the material structure.
 Cracks, porosity, non-metallic inclusions within materials can be revealed by examining
them under powerful optical microscope.
(c) Sub Structure
 When crystal imperfections such as dislocation in a structure are to be examined, a
special microscope having higher magnification and resolution than the optical
microscope is used.
 Electron microscope with magnifications 105 are used for this purpose.
 Field ion microscope can produce images of individual atoms as well as defects in atomic
arrangements.
(d) Crystal Structure
 This reveals the atomic arrangement within a crystal.
 X-ray diffraction techniques and electron diffraction method are commonly used for
studying crystal structure.
 It is usually sufficient to study the arrangement of atoms within a unit cell.
 The crystal is formed by a very large number of unit cells forming regularly repeating
patterns in space.
(e) Electronic Structure
 This refers to the electrons in the outermost shells of individual atoms in the solid.
 Spectroscopic techniques are commonly used for determining the electronic structure.
(f) Nuclear Structure
 This is studied by nuclear spectroscopic techniques, e.g., nuclear magnetic resonance
(NMR) and Mössbauer spectroscopy.

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BRAGG'S LAW
X-rays are a form of electromagnetic radiation that have high energies and short
wavelengths — wavelengths on the order of the atomic spacings for solids. When a beam of
x-rays impinges on a solid material, a portion of this beam will be scattered in all directions
by the electrons associated with each atom or ion that lies within the beam’s path.
Consider the two parallel planes of atoms A–A and B–B in Figure, which have the
same h, k and l Miller indices and are separated by the interplanar spacing dhkl. Now assume
that a parallel, monochromatic and coherent (in-phase) beam of x-rays of wavelength is
incident on these two planes at an angle of . Two rays in this beam, labeled 1 and 2, are
scattered by atoms P and Q. Constructive interference of the scattered rays 1 and 2 occurs
also at an angle to the planes, if the path length difference between 1P1 and 2–Q–2 is
equal to a whole number, n, of wavelengths. The condition (Bragg’s law) for diffraction is

The Bragg’s law relates the x-ray wave length and diffraction angle to interplanar
spacing.
The magnitude of the distance between two adjacent and parallel planes of atoms
(i.e., the interplanar spacing dhkl) is a function of the Miller indices (h, k, and l) as well as
the lattice parameter(s). For example, for crystal structures that have cubic symmetry,

in which a is the lattice parameter (unit cell edge length). Relationships similar to the above
equation, but more complex, exist for the other six crystal systems.

X-RAY DIFFRACTION
One common diffraction technique employs a powdered or polycrystalline specimen
consisting of many fine and randomly oriented particles that are exposed to monochromatic
x-radiation. Each powder particle (or grain) is a crystal, and having a large number of them
with random orientations ensures that some particles are properly oriented such that every
possible set of crystallographic planes will be available for diffraction. The diffractometer is
an apparatus used to determine the angles at which diffraction occurs for powdered
specimens.

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 One of the primary uses of x-ray diffractometry is for the determination of crystal
structure. The unit cell size and geometry may be resolved from the angular positions of the
diffraction peaks, whereas arrangement of atoms within the unit cell is associated with the
relative intensities of these peaks. The intensity of the diffraction lines in the diffraction
pattern allows identification of the crystal structure. Absences of peaks in certain positions
indicate the presence of various planes within the structure as do the relative intensities of
the peaks. This procedure is called crystal structure analysis.
X-rays, as well as electron and neutron beams, are also used in other types of
material investigations. For example, crystallographic orientations of single crystals are
possible using x-ray diffraction (or Laue) photographs.
Other uses of x-rays include qualitative and quantitative chemical identifications and
the determination of residual stresses and crystal size.

DIFFRACTION TECHNIQUES FOR CRYSTAL STRUCTURE ANALYSIS

A crystal structure of a crystalline material can be analyzed using x-ray diffraction
(XRD) or electron diffraction. When a beam of x-rays having a single wavelength on the
same order of magnitude as the atomic spacing in the material strikes that material, x-rays
are scattered in all directions. Most of the radiation scattered from one atom cancels out
radiation scattered from other atoms; however, x-rays that strike certain crystallographic
planes at specific angles are reinforced rather than annihilated. This phenomenon is called
diffraction. The x-rays are diffracted, or the beam is reinforced, when conditions satisfy
Bragg’s law.
When the material is prepared in the form of a fine powder, there are always at least
some powder particles (crystals or aggregates of crystals) with planes oriented at the
proper θ angle to satisfy Bragg’s law. Therefore, a diffracted beam, making an angle of 2θ
with the incident beam, is produced. In a diffractometer, a moving x-ray detector records
the 2θ angles at which the beam is diffracted, giving a characteristic diffraction pattern. If
we know the wavelength of the x-rays, we can determine the interplanar spacings and,
eventually, the identity of the planes that cause the diffraction.

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CRYSTAL DEFECTS
According to the law of nature nothing is perfect and so crystals need not be perfect.
They always found to have some defects in the arrangement of their constituent particles.
These defects affect the physical and chemical properties of the solid and play an important
role in various processes. For example, a process called doping leads to a crystal
imperfection and it increases the electrical conductivity of a semiconductor material such as
silicon. The ability of ferromagnetic material such as iron, nickel etc., to be magnetized and
demagnetized depends on the presence of imperfections.
Natural crystals always contain defects, often in abundance, due to the uncontrolled
conditions under which they formed. The importance of defects depends upon the material,
type of defect, and properties, which are being considered. Some properties, such as
density and elastic constants, are proportional to the concentration of defects, and so a
small defect concentration will have a very small effect on these. Other properties, e.g. the
colour of an insulating crystal or the conductivity of a semiconductor crystal, may be much
more sensitive to the presence of small number of defects.
There are some properties of materials such as stiffness, density and electrical
conductivity which are termed structure - insensitive, are not affected by the presence of
defects in crystals while there are many properties of greatest technical importance such as
mechanical strength, ductility, crystal growth, magnetic hysteresis, dielectric strength,
condition in semiconductors, which are termed structure sensitive are greatly affected by
the relatively minor changes in crystal structure caused by defects or imperfections. Defects
in materials have a significant influence on their electrical, optical, and magnetic properties.
Crystalline defects can be classified on the basis of their geometry as: (i) Point
imperfections, (ii) Line imperfections, (iii) Surface and grain boundary imperfections and
(iv) Bulk / Volume imperfections.
The dimensions of a point defect are close to those of an interatomic space. With
linear defects, their length is several orders of magnitude greater than the width. Surface
defects have a small depth, while their width and length may be several orders larger.
Volume defects (pores and cracks) may have substantial dimensions in all measurements.
Point Defects
Point defects distort the crystal lattice and have a certain influence on the physical
properties. In commercially pure metals, point defects, increase the electric resistance and
have almost no effect on the mechanical properties. Only at high concentrations of defects
in irradiated metals, the ductility and other properties are reduced noticeably.
Point defect types are:
(i) vacancies
A vacancy is produced when an atom or an ion is missing from its normal site in the
crystal structure. Arise either from imperfect packing during original crystallisation or
from thermal vibrations of the atoms at higher temperatures.
(ii) Interstitial Imperfections
An extra atom or ion is inserted in the interstitial space or void between the regularly
positioned atoms or ions within the crystal structure.
(iii) Frenkel Defect
When an ion jumps from normal lattice point to an interstitial site. It is a combination
of vacancy and interstitial defects. More common in ionic crystals.
(iv) Schottky Defect
a pair of positive and negative ions is missing from a crystal structure. This defect
maintains ionic charge neutrality.
(v) Substitutional Defect
A foreign atom or ion replaces the parent atom of the lattice and thus occupies the
position of parent atom or ion.
(vi) Phonon
When the temperature is raised, thermal vibrations takes place. This results in the
defect of a symmetry and deviation in shape of atoms or ions. This defect has much
effect on the magnetic and electric properties.

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Line Defects
Dislocations are line imperfections in an otherwise perfect crystal. They formed
during solidification of the material or when the material is deformed permanently.
Dislocations influence electronic and optical properties of materials.
Three types of dislocations are: the screw dislocation, the edge dislocation, and the mixed
dislocation.
(i) Screw dislocation can be illustrated by cutting partway through a perfect crystal and
then skewing the crystal by one atom spacing.
(ii) Edge dislocation can be illustrated by slicing partway through a perfect crystal,
spreading the crystal apart, and partly filling the cut with an extra half plane of atoms.
The bottom edge of this inserted plane represents the edge dislocation.
(iii) Mixed dislocations have both edge and screw components, with a transition region
between them.

Screw dislocation Edge dislocation

Mixed dislocations

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Surface Defects
Surface defects are the boundaries, or planes, that separate a material into regions.
For example, each region may have the same crystal structure but different orientations.
Material Surface: The exterior dimensions of the material represent surfaces at which the
crystal abruptly ends. Each atom at the surface no longer has the proper coordination
number, and atomic bonding is disrupted. The exterior surface may also be very
rough, may contain tiny notches, and may be much more reactive than the bulk of the
material. In petroleum refining and many other areas of technology, we make use of
high surface area catalysts for enhancing the kinetics of chemical reactions.
Grain Boundaries: The microstructure of many engineered ceramic and metallic materials
consists of many grains. A grain is a portion of the material within which the
arrangement of the atoms is nearly identical; however, the orientation of the atom
arrangement, or crystal structure, is different for each adjoining grain. A grain
boundary, the surface that separates the individual grains, is a narrow zone in which
the atoms are not properly spaced.
Small Angle & High Angle Grain Boundaries are arrays of dislocations that produce
misorientations between the adjoining crystals. Because the energy of the surface is
less than that of a regular grain boundary, the small angle grain boundaries are not as
effective in blocking slip. Small angle boundaries formed by edge dislocations are called
tilt boundaries, and those caused by screw dislocations are called twist boundaries.
Phase Boundaries exist in multiphase materials, wherein a different phase exists on each
side of the boundary. Each of the constituent phases has its own distinctive physical
and/or chemical characteristics. Phase boundaries play an important role in
determining the mechanical characteristics of some multiphase metal alloys.
A twin boundary is a special type of grain boundary across which there is a specific mirror
lattice symmetry. Atoms on one side of the boundary are located in mirror-image
positions of the atoms on the other side. It is a plane across which there is a special mirror
image misorientation of the crystal structure. Twinning occurs on a definite crystallographic
plane and in a specific direction, both of which depend on the crystal structure.
Twins can be produced when a shear force, acting along the twin boundary, causes
the atoms to shift out of position. Twinning occurs during deformation or heat
treatment of certain metals. Twins result from atomic displacements that are produced
from applied mechanical shear forces (mechanical twins), and also during annealing
heat treatments following deformation (annealing twins). The twin boundaries
interfere with the slip process and increase the strength of the metal.
Stacking faults occur in FCC metals, an error in the stacking sequence of close-packed
planes. Stacking faults interfere with the slip process.
Magnetic domain wall is the boundary that separates regions having different directions
of magnetization.

Bulk / Volume Defects

Bulk / volume defects include pores, cracks, foreign inclusions, and other phases.
They are normally introduced during processing and fabrication steps.

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IMPORTANCE OF CRYSTAL DEFECTS
Dislocations are most significant in metals and alloys since they provide a mechanism
for plastic deformation. Plastic deformation refers to irreversible deformation or change in
shape that occurs when the force or stress that caused it is removed. The applied stress
causes dislocation motion, and the cumulative effect of slip of numerous dislocations is
plastic deformation. The slip process is particularly important in understanding the
mechanical behavior of metals.
First, slip explains why the strength of metals is much lower than the value predicted
from the metallic bond. If slip occurs, only a tiny fraction of all of the metallic bonds across
the interface need to be broken at any one time, and the force required to deform the metal
is small.
Second, slip provides ductility in metals. If no dislocations were present, an iron bar
would be brittle and could not be shaped by metalworking processes, such as forging, into
useful shapes.
Third, we control the mechanical properties of a metal or alloy by interfering with the
movement of dislocations. An obstacle introduced into the crystal prevents a dislocation
from slipping unless we apply higher forces. Thus, the presence of dislocations helps
strengthen metallic materials.
Enormous numbers of dislocations are found in materials.
The dislocation density, or total length of dislocations per unit volume, is usually
used to represent the amount of dislocations present. Dislocation densities of 106 cm/cm3
are typical of the softest metals, while densities up to 1012 cm/cm3 can be achieved by
deforming the material. Dislocations also influence electronic and optical properties of
materials. For example, the resistance of pure copper increases with increasing dislocation
density. We mentioned previously that the resistivity of pure copper also depends strongly
on small levels of impurities. Similarly, we prefer to use silicon crystals that are essentially
dislocation free since this allows the charge carriers such as electrons to move more freely
through the solid. Normally, the presence of dislocations has a deleterious effect on the
performance of photo detectors, light emitting diodes, lasers, and solar cells. These devices
are often made from compound semiconductors such as gallium arsenide-aluminum
arsenide (GaAs-AlAs), and dislocations in these materials can originate from concentration
inequalities in the melt from which crystals are grown or stresses induced because of
thermal gradients that the crystals are exposed to during cooling from the growth
temperature.
Extended and point defects play a major role in influencing mechanical, electrical,
optical, and magnetic properties of engineered materials. In this section, we recapitulate the
importance of defects on properties of materials.

ALLOY FORMATION
A homogeneous mixture of two or more metals or a metal and a non-metal when
fused together at a certain temperature forms a new metal after solidification, termed as an
alloy. Alloys are normally harder than their components, less ductile and may have a much
lower conductivity, whereas the highly purified single crystal of a metal is very soft and
malleable, with high electrical conductivity.
Pure metals are used only for specific applications. The alloy is usually more corrosion
resistant and less affected by atmospheric conditions.
In the solid state an alloy may be present in one or more of the following forms:
(i) As a solid solution
(ii) As an intermediate phase or intermediate chemical compound
(iv) As a finely divided mechanical mixture of solid solution
(v) As a finely divided mechanical mixture of the metals
(vi) As a finely divided mechanical mixture of chemical compounds of metals, the
individual metals and solid solutions.

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 When an alloy is in a liquid state the atoms of the constituent are distributed randomly
through the liquid. When solidification takes place, there appears number of possibilities. A
number of different types of solutions may form, as follows:
(a) Simple Eutectic Type In this case the two components of an alloy system (binary) are
soluble in liquid state but separate out in the solid state, each maintaining its own separate
identity. In the solid state, the two components are said to be insoluble in each other. The
solution is called eutectic type.
(b) Solid Solution Type When the two components of a binary alloy remain completely
mixed in each other both in liquid and solid state, the two components are said to be
soluble in each other and a different type of solution may be formed. It is called a solid
solution.
(c) Combination Type On solidifying, the two components of a binary alloy may show
limited solubility in each other. This type of solution combines characteristics of both
components.
(d) Inter-metallic Compounds It is observed that the elements may combine to form
inter-metallic compounds on solidification, when their affinity is great. These types of
compounds may find place in between the solid solution and chemical compound.

SOLID SOLUTION TYPES

A solid solution forms when, as the solute atoms are added to the host material, the
crystal structure is maintained, and no new structures are formed. In other words, when
elements completely dissolve in each other in liquid and or solid state the resulting phase is
called solid solution.
Solid solution may be defined as solution in the solid state which consists of two (or
more) kinds of atoms combined in one type of crystal structure (space lattice).
Solid solutions form readily when solvent and solute atoms have similar sizes and
electron structures, so that it is compositionally or chemically homogeneous and the
component atoms of the elements cannot be distinguished physically or separated
mechanically. There is a homogeneous distribution of the constituents in the solid state so
as to form a single phase or solid solution.
Basically, solid solutions are of two types:
(i) Substitutional Solid Solution
(a) Random substitutional solid solutions
(b) Ordered substitutional solid solutions.
(ii) Interstitial Solid Solution.

Random Ordered Interstitial solid solutions

Substitutional Solid Solution: The solute or impurity atoms replace or substitute for the
host atoms (as shown in Figure). Several features of the solute and solvent atoms
determine the degree to which the solute dissolves in the solvent, are: (1) Atomic size
factor, (2) Crystal structure, (3) Electronegativity and (4) Valences.
Interstitial Solid Solution: In crystal lattice of many metals, small sized atoms of H, N, C
and B can occupy the empty spaces (interstices) to form interstitial solid solutions.
In some alloys both interstitial and substitutional solid solutions are formed to some
good extent. For example, in Cr-Ni Steel the carbon occupies interstitially whereas Cr and Ni
occupy substitutionally in the iron lattice.

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 Lattice distortions appearing on the formation of interstitial solid solutions are stronger
than those in the substitutional solid solutions.
Increase in solute concentration in a solid solution increases the electric resistance,
coercive force, hardness and strength, but decreases the ductility and toughness.
Solid solutions are crystals whose properties are close to those of the solvent, since
they retain the same crystal lattice and type of bond.
Solid solutions of metals have high plasticity and they are readily deformable in the
hot state and many of them, in the cold state.
Solid solutions are the bases of most commercial structural and special alloys.

Summary: Solid solutions in metallic or ceramic materials exist when elements or compounds
with similar crystal structures form a single phase that is chemically homogeneous.
 Solid-solution strengthening is accomplished in metallic materials by the formation of
solid solutions. The point defects created restrict dislocation motion and cause
strengthening.
 The degree of solid-solution strengthening increases when (1) the amount of the
alloying element increases and (2) the atomic size difference between the host
material and the alloying element increases.
 The amount of alloying element (or compound) added to produce solid solution
strengthening is limited by the solubility of the alloying element or compound in the
host material.
 Solid-solution strengthening increases strength and hardness; decreases ductility and
electrical conductivity of metallic materials. It also provides good high-temperature
properties to the alloy.
 In solid-solution formation, solidification begins at the liquidus temperature and is
completed at the solidus temperature.

SOLIDIFICATION OF CASTINGS
Solidification is the transformation of materials from the liquid to the solid crystalline
state on cooling. During solidification, the disordered structure of the liquid transforms to
the orderly arrangement characteristic of the crystal.
Under industrial casting conditions, the kinetics of solidification is often controlled by
heat flow. When a melt is poured into a container or mould, which is at a much lower
temperature than the melt, large supercooling occurs in regions where the melt comes into
direct contact with the cold container walls. This large supercooling results in a rapid rate of
nucleation and a layer of fine crystals is formed adjacent to the wall. The latent heat
released in the formation of this layer increases the temperature and reduces the nucleation
rate in the liquid next to it.
Heat flows out of the mould through the walls. As a result, the crystals adjacent to the
layer of fine crystals at the mould wall grow inwards towards the centre (in a direction
opposite to that of the heat flow) producing long columnar crystals. These crystals
ultimately meet near the centre of the mould and a cross-section after solidification shows
crystals radially branching out from the centre. Quite often, crystals grow preferentially
along certain crystallographic directions, along which the thermal conductivity (and hence
the heat extraction) is a maximum. This fact is exploited in certain applications to produce a
polycrystalline material with crystals aligned in a particular crystal direction. In magnetic
applications, for example, the alignment of crystals enhances the magnetic properties.
In manufacturing components by casting, molten metals are often poured into mould
and permitted to solidify. The mould produces a finished shape, known as a casting. In
other cases, the mould produces a simple shape, called an ingot. An ingot usually requires
extensive plastic deformation before a finished product is created. A macrostructure,
sometimes referred to as the ingot structure, consists of as many as three parts.

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Chill Zone: The chill zone is a narrow band of randomly oriented grains at the surface of
the casting. The metal at the mold wall is the first to cool to the freezing temperature.
The mold wall also provides many surface sites at which heterogeneous nucleation takes place.
Columnar Zone: The columnar zone contains elongated grains oriented in a particular
crystallographic direction. As heat is removed from the casting by the mold material,
the grains in the chill zone grow in the direction opposite the heat flow, or from the
coldest toward the hottest areas of the casting. This tendency usually means that the
grains grow perpendicular to the mold wall.
Equiaxed Zone: Although the solid may continue to grow in a columnar manner until all of
the liquid has solidified, an equiaxed zone frequently forms in the center of the casting
or ingot. The equiaxed zone contains new, randomly oriented grains, often caused by
a low pouring temperature, alloying elements, or grain refining or inoculating agents.
Small grains or dendrites in the chill zone may also be torn off by strong convection
currents that are set up as the casting begins to freeze. These also provide the
heterogeneous nucleation sites for what ultimately become equiaxed grains. These
grains grow as relatively round, or equiaxed, grains with a random orientation, and
they stop the growth of the columnar grains.
The formation of the equiaxed zone is a nucleation controlled process and causes that
portion of the casting to display isotropic behavior.

Development of the ingot structure of a casting during solidification: (a) Nucleation begins,
(b) the chill zone forms, (c) preferred growth produces the columnar zone, and (d) additional
nucleation creates the equiaxed zone.
STRUCTURAL EXAMINATION USING MICROSCOPY
Optical, electron, and scanning probe microscopes are commonly used in
microscopy. These instruments aid in investigations of the microstructural features of all
material types. Microscopic examination is an extremely useful tool in the study and
characterization of materials.
1. Optical microscopy: Conventional light microscopy, Fluorescence microscopy,
confocal/multiphoton microscopy and Stimulated emission depletion microscopy.
2. Scanning probe microscopy: Scanning tunnelling microscopy (STM), Atomic force
microscopy (AFM), Near-field scanning optical microscopy and others.
3. Electron microscopy: Scanning electron microscopy (SEM), Transmission electron
microscopy (TEM), Scanning transmission electron microscopy (STEM), Focus ion
beam microscopy (FIB)
Several important applications of microstructural examinations are as follows:
to ensure that the associations between the properties and structure (and defects) are
properly understood,
to predict the properties of materials once these relationships have been established,
to design alloys with new property combinations, to determine whether a material has
been correctly heat-treated, and to ascertain the mode of mechanical fracture.
to analyse the material structural aspects in
(i) Crystal morphology and symmetry - Crystal fragments, classify isotropic and
anisotropic substances, check possible symmetry;

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 (ii) Phase identification, purity and homogeneity - standard optical data (refractive
indices and optical axes) for comparison, phase analysis (impurities with separated
crystalline / amorphous phase), single vs. twinned crystal;
(iii) Crystal defects – grain boundaries and dislocations and;
(iv) Refractive index determination.
Optical Microscopy
With optical microscopy, the light microscope is used to study the microstructure;
optical and illumination systems are its basic elements. For materials that are opaque to
visible light (all metals and many ceramics and polymers), only the surface is subject to
observation, and the light microscope must be used in a reflecting mode. Contrasts in the
image produced result from differences in reflectivity of the various regions of the
microstructure. Investigations of this type are often termed metallographic, because metals
were first examined using this technique.
Normally, careful and meticulous surface preparations are necessary to reveal the
important details of the microstructure. The specimen surface must first be ground and
polished to a smooth and mirror-like finish. The microstructure is revealed by a surface
treatment using an appropriate chemical reagent in a procedure termed etching. The
chemical reactivity of the grains of some single-phase materials depends on crystallographic
orientation. Consequently, in a polycrystalline specimen, etching characteristics vary from
grain to grain. The lustre or texture of each grain depends on its reflectance properties.
Also, small grooves form along grain boundaries as a consequence of etching. Because
atoms along grain boundary regions are more chemically active, they dissolve at a greater
rate than those within the grains. These grooves become discernible when viewed under a
microscope because they reflect light at an angle different from that of the grains themselves.
When the microstructure of a two-phase alloy is to be examined, an etchant is often
chosen that produces a different texture for each phase so that the different phases may be
distinguished from each other.
Electron Microscopy
The upper limit to the magnification possible with an optical microscope is
approximately 2000 times. Consequently, some structural elements are too fine or small to
permit observation using optical microscopy. Under such circumstances the electron
microscope, which is capable of much higher magnifications, may be employed.
An image of the structure under investigation is formed using beams of electrons
instead of light radiation. High magnifications and resolving powers of these microscopes
are consequences of the short wavelengths of electron beams. The electron beam is focused
and the image formed with magnetic lenses; otherwise the geometry of the microscope
components is essentially the same as with optical systems. Both transmission and
reflection beam modes of operation are possible for electron microscopes.

Transmission Electron Microscopy

The image seen with a transmission electron microscope (TEM) is formed by an
electron beam that passes through the specimen. Details of internal micro-structural features
are accessible to observation; contrasts in the image are produced by differences in beam
scattering or diffraction produced between various elements of the microstructure or defect.
Because solid materials are highly absorptive to electron beams, a specimen to be
examined must be prepared in the form of a very thin foil; this ensures transmission

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through the specimen of an appreciable fraction of the incident beam. The transmitted
beam is projected on to a fluorescent screen or a photographic film so that the image may
be viewed. Magnifications approaching 1,000,000X are possible with transmission electron
microscopy, which is frequently used to study dislocations.
Scanning Electron Microscopy
A more recent and extremely useful investigative tool is the scanning electron
microscope (SEM). The surface of a specimen to be examined is scanned with an electron
beam, and the reflected (or back-scattered) beam of electrons is collected, and then
displayed at the same scanning rate on a cathode ray tube (similar to a CRT television
screen). The image on the screen, which may be photographed, represents the surface
features of the specimen.
The surface may or may not be polished and etched, but it must be electrically
conductive; a very thin metallic surface coating must be applied to non-conductive
materials. Magnifications ranging from 10 to in excess of 50,000 times are possible, as are
also very great depths of field. Accessory equipment permits qualitative and
semiquantitative analysis of the elemental composition of much localized surface areas.
Scanning Probe Microscopy
The scanning probe microscope (SPM) generates a topographical map, on an atomic scale,
that is a representation of surface features and characteristics of the specimen being examined.
Some of the features that differentiate the SPM from other microscopic techniques are as follows:
 Examination on the nanometer scale is possible in as much as magnifications as high as 109X
are possible; much better resolutions are attainable than with other microscopic techniques.
 Three-dimensional magnified images are generated that provide topographical
information about features of interest.
 Some SPMs may be operated in a variety of environments (e.g., vacuum, air, liquid);
thus, a particular specimen may be examined in its most suitable environment.
Scanning probe microscopes employ a tiny probe with a very sharp tip that is brought
into very close proximity (i.e., to within on the order of a nanometer) of the specimen
surface. This probe is then raster-scanned across the plane of the surface. During scanning,
the probe experiences deflections perpendicular to this plane, in response to electronic or
other interactions between the probe and specimen surface.
The in-surface-plane and out-of-plane motions of the probe are controlled by
piezoelectric ceramic components that have nanometer resolutions. Furthermore, these
probe movements are monitored electronically and transferred to and stored in a computer,
which then generates the three-dimensional surface image.
These new SPMs, which allow examination of the surface of materials at the atomic
and molecular level, have provided a wealth of information about a host of materials, from
integrated circuit chips to biological molecules.
Indeed, the advent of the SPMs has helped to usher in the era of nanomaterials -
materials whose properties are designed by engineering atomic and molecular structures.
Scanning Tunnelling Microscopy
A scanning tunnelling microscope works by moving an exceptionally sharp
piezoelectric tip (often only one atom thick at its point) across the surface of a conductive
solid, such as a piece of crystalline nickel in an evacuated chamber. When a small voltage is
applied to the tip of the STM, a tunnelling current develops whenever the tip is close to the
surface of a Ni atom. This tunnelling current is proportional to the distance between the tip
of the probe and the atoms on the surface of the crystal. By adjusting the STM so that the
tunnelling current is a constant, the tip will move up and down as it crosses the surface of
the crystal and encounters electron density around the nuclei of the nickel atoms. A
computer is then used to map out the three-dimensional contour of the nickel surface and
to colour it different shades of blue in this case, depending on the distance that the tip has
moved. The STM can also be used to pick up atoms and to move them around on a surface.

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 STM Microscope Principle STM image of (110) face of Ni crystal
Atomic Force Microscopy
Atomic force microscope works by monitoring the interaction force between sample
surface atoms with the cantilever sensor tip to for (1) Image – surface topology in
nanometer resolution of polymers, (2) Force mapping – surface variation of softness,
elasticity and stickiness of composite materials, (3) Dip-pen nanolithography and
(4) Nanofabrication.

Schematic depiction of: Light microscopy (LM), transmission electron microscopy (TEM),
Scanning electron microscopy (SPM) and Scanning probe microscopy (SPM).
Summary: Microscopic Techniques
 The microstructure of a material consists of defects and structural elements that are of
microscopic dimensions. Microscopy is the observation of microstructure using some
type of microscope.
 Both optical and electron microscopes are employed, usually in conjunction with
photographic equipment.
 Transmissive and reflective modes are possible for each microscope type; preference is dictated
by the nature of the specimen as well as the structural element or defect to be examined.
 In order to observe the grain structure of a polycrystalline material using an optical
microscope, the specimen surface must be ground and polished in order to produce a
very smooth and mirror-like finish. Some type of chemical reagent (or etchant) must
then be applied in order to either reveal the grain boundaries or produce a variety of
light reflectance characteristics for the constituent grains.
 The two types of electron microscopes are transmission (TEM) and scanning (SEM).
 For TEM an image is formed from an electron beam that, while passing through the
specimen, is scattered and/or diffracted.
 SEM employs an electron beam that raster-scans the specimen surface; an image is
produced from back-scattered or reflected electrons.
 A scanning probe microscope employs a small and sharp-tipped probe that raster-scans
the specimen surface. Out-of-plane deflections of the probe result from interactions with
surface atoms. A computer generated and three-dimensional image of the surface
results having nanometer resolution.

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