JIMMA UNIVERSITY

JIMMA INSTITUTE OF TECHNOLOGY

Faculty of Materials Science and Engineering

Introduction to Materials Science and Engineering

Unit 1 : Atoms, Bonding, Basic Chemistry 3

1.1. Historical Perspective and Materials Science 3
1.2. Materials Science 3
1.3. Classification of Materials 4
1.4. Atomic Structure and Atomic Bonding in Solids 6
1.4.1. Atomic Model 6
1.5. Periodic Table 9
1.6. Atomic bonding in solids 11
1.6.1. Ionic Bonding 11
1.6.2. Covalent Bonding 11
1.6.3. Metallic Bonding 12
1.6.4. Weak Intra-Molecular Bonding 12
1.6.5. Water (Its Volume Expansion Upon Freezing) 13
Unit 2 : Introduction to Crystal Structures 15
2.1. Crystal structures 15
2.2. Polymorphism and Allotrophy 17
2.2.1. Miller indices 18
Unit 3 : Introduction to Metals, Ceramics and Polymers 20
3.1. Applications and Processing of Metal Alloys 20
3.2. Phase Diagrams 24
3.2.1. Solubility Limit 25
3.2.2. Phases 26
3.2.3. Microstructure 27
3.2.4. Phase Equilibria 27
3.2.5. Unitary diagrams: 29
3.2.6. Binary Phase diagram: 29
3.3. Applications and Processing of Ceramics 30
3.4. Applications and Processing of Polymers 35
Unit 4 : Degradation and Failure 40
4.1. Concepts Of Stress And Strain 40
4.2. Elastic deformation 42
4.3. Plastic Deformation 43
4.3.1. Dislocations 44
4.4. Failure 45
4.4.1. Simple fracture 45
4.4.2. Fatigue 46
4.4.3. Creep 47
Unit 5 : Properties of Materials 49
5.1. Thermal Properties 49
5.2. Magnetic Properties 53
5.3. Electrical and Electronic Properties 54

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Nanotechnology (MScE6107) Dr.S.Sathiesh Kumar
 5.4. Optical properties 57
Unit 6 : Nanotechnology 61
6.1. Introduction 61
6.2. What makes nanotechnology special? 63
6.3. Classification and Properties 68
6.3.1. CLASSIFICATION OF NANOMATERIALS 68
6.3.2. Quantum Confinement 69
6.4. Size Dependent Properties: 72
6.4.1. Morphological/Structural Properties 72
6.4.2. Thermal Properties 73
6.4.3. Electromagnetic Properties 73
6.4.4. Optical Properties 73
6.4.5. Mechanical Properties 74

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 UNIT 1 : ATOMS, BONDING, BASIC CHEMISTRY

1.1. HISTORICAL PERSPECTIVE AND MATERIALS SCIENCE

Materials are so important in the development of human civilization that the historians
have identified early periods of civilization by the name of most significantly used material,
e.g.: Stone Age, Bronze Age. This is just an observation made to showcase the importance of
materials and their impact on human civilization. It is obvious that materials have affected
and controlling a broad range of human activities through thousands of decades.
From the historical point of view, it can be said that human civilization started with
Stone Age where people used only natural materials, like stone, clay, skin, and wood for the
purposes like to make weapons, instruments, shelter, etc. Thus the sites of deposits for better
quality stones became early colonies of human civilization. However, the increasing need for
better quality tools brought forth exploration that led to Bronze Age, followed by Iron Age.
When people found copper and how to make it harder by alloying, the Bronze Age started
about 3000 BC. The use of iron and steel, a stronger material that gave advantage in wars
started at about 1200 BC. Iron was abundant and thus availability is not limited to the
affluent. This commonness of the material affected every person in many aspects, gaining the
name democratic material. The next big step in human civilization was the discovery of a
cheap process to make steel around 1850 AD, which enabled the railroads and the building
of the modern infrastructure of the industrial world. One of the most significant features of
the democratic material is that number of users just exploded. Thus there has been a need
for human and material resources for centuries, which still going strong. It’s being said and
agreed that we are presently in Space Age marked by many technological developments
towards development materials resulting in stronger and light materials like composites,
electronic materials like semiconductors, materials for space voyages like high temperature
ceramics, bio materials, etc
In summary, materials constitute the foundation of technology. The history of human
civilization evolved from the Stone Age to the Bronze Age, the Iron Age, the Steel Age, and to
the Space Age (contemporaneous with the Electronic Age). Each age is marked by the advent
of certain materials. The Iron Age brought tools and utensils. The Steel Age brought railroads,
instruments, and the Industrial Revolution. The Space Age brought the materials for stronger
and light structures (e.g., composite materials). The Electronic Age brought semiconductors,
and thus many varieties of electronic gadgets.

1.2. MATERIALS SCIENCE

As engineering materials constitute foundation of technology, it’s not only necessary
but a must to understand how materials behave like they do and why they differ in
properties. This is only possible with the atomistic understanding allowed by quantum
mechanics that first explained atoms and then solids starting in the 1930s. The combination
of physics, chemistry, and the focus on the relationship between the properties of a material

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and its microstructure is the domain of Materials Science. The development of this science
allowed designing materials and provided a knowledge base for the engineering applications
(Materials Engineering). Important components of the subject Materials Science are structure,
properties, processing, and performance.

Why Study Materials Science and Engineering? and Classification of Materials? All
engineers need to know about materials. Even the most "immaterial", like software or
system engineering depend on the development of new materials, which in turn alter the
economics, like software-hardware trade-offs. Increasing applications of system engineering
are in materials manufacturing (industrial engineering) and complex environmental
systems.
Innovation in engineering often means the clever use of a new material for a specific
application. For example: plastic containers in place of age-old metallic containers. It is well
learnt lesion that engineering disasters are frequently caused by the misuse of materials. So
it is vital that the professional engineer should know how to select materials which best fit
the demands of the design - economic and aesthetic demands, as well as demands of strength
and durability. Beforehand the designer must understand the properties of materials, and
their limitations. Thus it is very important that every engineer must study and understand
the concepts of Materials Science and Engineering. This enables the engineer.
 To select a material for a given use based on considerations of cost and performance.
 To understand the limits of materials and the change of their properties with use.
 To be able to create a new material that will have some desirable properties.
 To be able to use the material for different application.

1.3. CLASSIFICATION OF MATERIALS

Like many other things, materials are classified in groups, so that our brain can handle
the complexity. One can classify them based on many criteria, for example crystal structure
(arrangement of atoms and bonds between them), or properties, or use. The main classes of
present engineering materials.

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Metals: These materials are characterized by high thermal and electrical conductivity;
strong yet deformable under applied mechanical loads; opaque to light (shiny if polished).
These characteristics are due to valence electrons that are detached from atoms, and spread
in an electron sea that glues the ions together, i.e. atoms are bound together by metallic
bonds and weaker van der Waalls forces. Pure metals are not good enough for many
applications, especially structural applications. Thus metals are used in alloy form i.e. a metal
mixed with another metal to improve the desired qualities. E.g.: aluminum, steel, brass, gold.
Ceramics: These are inorganic compounds, and usually made either of oxides, carbides,
nitrides, or silicates of metals. Ceramics are typically partly crystalline and partly
amorphous. Atoms (ions often) in ceramic materials behave mostly like either positive or
negative ions, and are bound by very strong Coulomb forces between them. These materials
are characterized by very high strength under compression, low ductility; usually insulators
to heat and electricity. Examples: glass, porcelain, many minerals.
Polymers: Polymers in the form of thermo-plastics (nylon, polyethylene, polyvinyl chloride,
rubber, etc.) consist of molecules that have covalent bonding within each molecule and van
der Waals forces between them. Polymers in the form of thermo-sets (e.g., epoxy, phenolics,
etc.) consist of a network of covalent bonds. They are based on H, C and other non-metallic
elements. Polymers are amorphous, except for a minority of thermoplastics. Due to the kind
of bonding, polymers are typically electrical and thermal insulators. However, conducting
polymers can be obtained by doping, and conducting polymer-matrix composites can be
obtained by the use of conducting fillers. They decompose at moderate temperatures (100 –
400 C), and are lightweight. Other properties vary greatly.
Composite materials: Composite materials are multiphase materials obtained by artificial
combination of different materials to attain properties that the individual components
cannot attain. An example is a lightweight brake disc obtained by embedding SiC particles in
Al-alloy matrix. Another example is reinforced cement concrete, a structural composite
obtained by combining cement (the matrix, i.e., the binder, obtained by a reaction known as
hydration, between cement and water), sand (fine aggregate), gravel (coarse aggregate), and,
thick steel fibers. However, there are some natural composites available in nature, for
example – wood. In general, composites are classified according to their matrix materials.
The main classes of composites are metal-matrix, polymer-matrix, and ceramic-matrix.
Semiconductors: Semiconductors are covalent in nature. Their atomic structure is
characterized by the highest occupied energy band (the valence band, where the valence
electrons reside energetically) full such that the energy gap between the top of the valence
band and the bottom of the empty energy band (the conduction band) is small enough for
some fraction of the valence electrons to be excited from the valence band to the conduction
band by thermal, optical, or other forms of energy. Their electrical properties depend
extremely strongly on minute proportions of contaminants. They are usually doped in order
to enhance electrical conductivity. They are used in the form of single crystals without

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dislocations because grain boundaries and dislocations would degrade electrical behavior.
They are opaque to visible light but transparent to the infrared. Examples: silicon (Si),
germanium (Ge), and gallium arsenide (GaAs, a compound semiconductor).
Biomaterials: These are any type material that can be used for replacement of damaged or
diseased human body parts. Primary requirement of these materials is that they must be
biocompatible with body tissues, and must not produce toxic substances. Other important
material factors are: ability to support forces; low friction, wear, density, and cost;
reproducibility. Typical applications involve heart valves, hip joints, dental implants,
intraocular lenses. Examples: Stainless steel, Co-28Cr-6Mo, Ti-6Al-4V, ultra high molecular
weight poly-ethelene, high purity dense Al-oxide, etc.
Need for Advanced Materials: Though there has been tremendous progress over the
decades in the field of materials science and engineering, innovation of new technologies,
and need for better performances of existing technologies demands much more from the
materials field. Moreover it is evident that new materials/technologies are needed to be
environmental friendly. Some typical needs, thus, of modern materials needs are listed in the
following:
 Engine efficiency increases at high temperatures: requires high temperature
structural materials
 Use of nuclear energy requires solving problem with residues, or advances 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.

1.4. ATOMIC STRUCTURE AND ATOMIC BONDING IN SOLIDS

1.4.1. ATOMIC MODEL

Thomson atomic model
A schematic presentation of the plum pudding model of the atom; in Thomson's
mathematical model the "corpuscles" (or modern electrons) were arranged non-randomly,
in rotating rings. The current model of the sub-atomic structure involves a dense nucleus
surrounded by a probabilistic "cloud" of electrons.

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 The plum pudding model was a model of the atom that incorporated the recently
discovered electron, and was proposed by J. J. Thomson in 1904. Thomson had discovered
the electron in 1897. The plum pudding model was abandoned after discovery of the atomic
nucleus. The plum pudding model of the atom is also known as the "Blueberry Muffin" model.
In this model, the atom is composed of electrons (which Thomson still called
"corpuscles", though G. J. Stoney had proposed that atoms of electricity be called electrons in
1894) surrounded by a soup of positive charge to balance the electrons' negative charges,
like negatively charged "raisins" surrounded by positively charged "pudding". The electrons
(as we know them today) were thought to be positioned throughout the atom, but with many
structures possible for positioning multiple electrons, particularly rotating rings of electrons
(see below). Instead of a soup, the atom was also sometimes said to have had a "cloud" of
positive charge.
With this model, Thomson abandoned his earlier "nebular atom" hypothesis in which
the atom was composed of immaterial vortices. Now, at least part of the atom was to be
composed of Thomson's particulate negative "corpuscles", although the rest of positively
charged part of the atom remained some what nebulous and ill defined.

Rutherford model
Rutherford overturned Thomson's model in 1911 with his well-known gold foil
experiment in which he demonstrated that the atom has a tiny, heavy nucleus. Rutherford
designed an experiment to use the alpha particles emitted by a radioactive element as probes
to the unseen world of atomic structure. Rutherford presented his own physical model for
subatomic structure, as an interpretation for the unexpected experimental results. In it, the
atom is made up of a central charge (this is the modern atomic nucleus, though Rutherford
did not use the term "nucleus" in his paper) surrounded by a cloud of (presumably) orbiting
electrons. In this May 1911 paper, Rutherford only commits himself to a small central region
of very high positive or negative charge in the atom.

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Bohr model
In the early 20th century, experiments by Ernest Rutherford established that atoms
consisted of a diffuse cloud of negatively charged electrons surrounding a small, dense,
positively charged nucleus. Given this experimental data, Rutherford naturally considered a
planetary-model atom, the Rutherford model of 1911 – electrons orbiting a solar nucleus –
however, said planetary- model atom has a technical difficulty. The laws of classical
mechanics (i.e. the Larmor formula), predict that the electron will release electromagnetic
radiation while orbiting a nucleus. Because the electron would lose energy, it would rapidly
spiral inwards, collapsing into the nucleus on a timescale of around 16 picoseconds. This
atom model is disastrous, because it predicts that all atoms are unstable.
Also, as the electron spirals inward, the emission would rapidly increase in frequency
as the orbit got smaller and faster. This would produce a continuous smear, in frequency, of
electromagnetic radiation. However, late 19th century experiments with electric discharges
have shown that atoms will only emit light (that is, electromagnetic radiation) at certain
discrete frequencies.
To overcome this difficulty, Niels Bohr proposed, in 1913, what is now called the Bohr
model of the atom. He suggested that electrons could only have certain classical motions:
1. Electrons in atoms orbit the nucleus.
2. The electrons can only orbit stably, without radiating, in certain orbits (called by Bohr
the "stationary orbits") at a certain discrete set of distances from the nucleus. These
orbits are associated with definite energies and are also called energy shells or energy
levels. In theseorbits, the electron's acceleration does not result in radiation and energy
loss as required by classical electromagnetics.
3. Electrons can only gain and lose energy by jumping from one allowed orbit to another,
absorbing or emitting electromagnetic radiation with a frequency ν determined by the
energy difference of the levels according to the Planck relation.

Modern concept of atomic model (De- Broglie’s atomic model)

In 1925 a new kind of mechanics was proposed, quantum mechanics, in which Bohr's
model of electrons traveling in quantized orbits was extended into a more accurate model of
electron motion. The new theory was proposed by Werner Heisenberg. Another form of the
same theory, wave mechanics, was discovered by the Austrian physicist Erwin Schrödinger
independently, and by different reasoning. Schrödinger employed de Broglie's matter waves,
but sought wave solutions of a three-dimensional wave equation describing electrons that
were constrained to move about the nucleus of a hydrogen-like atom, by being trapped by
the potential of the positive nuclear charge.

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 The shapes of atomic orbitals can be understood qualitatively by considering the
analogous case of standing waves on a circular drum. To see the analogy, the mean
vibrational displacement of each bit of drum membrane from the equilibrium point over
many cycles (a measure of average drum membrane velocity and momentum at that point)
must be considered relative to that point's distance from the center of the drum head. If this
displacement is taken as being analogous to the probability of finding an electron at a given
distance from the nucleus, then it will be seen that the many modes of the vibrating disk form
patterns that trace the various shapes of atomic orbitals. The basic reason for this
correspondence lies in the fact that the distribution of kinetic energy and momentum in a
matter-wave is predictive of where the particle associated with the wave will be. That is, the
probability of finding an electron at a given place is also a function of the electron's average
momentum at that point, since high electron momentum at a given position tends to
"localize" the electron in that position, via the properties of electron wave-packets.

1.5. PERIODIC TABLE

Periodic element classification is the process of categorising the elements into various
classes. This strategy involves grouping like things together and separating those that are
unrelated by comparing the characteristics of several elements. Periodic table is an
arrangement of the known elements based on atomic number and chemical and physical
properties. It aids in our comprehension of how various compounds combine to form various
elements. In the modern periodic table, each box contains four data, as shown in Figure 1.
Besides the element name and symbol, the atomic mass is at the bottom, and the atomic
number is at the top. The elements are arranged in order of increasing atomic number in
horizontal rows called periods.

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According to their increasing atomic numbers, elements are organized. The contemporary
periodic table divides the elements into 7 periods and 18 groups. Vertical columns are
known as groups, and horizontal rows are known as periods. Depending on how many
atomic shells each element has, it is classified into periods. The first period, which only has
two elements—hydrogen and helium—is the shortest. The sixth period in the periodic table
is regarded as the longest period. It contains substances ranging from Radon to Cesium.
Actinides and Lanthanides are included at the bottom of the periodic table.
In the periodic table, elements in columns have similar properties, and elements so related
(like sulfur, selenium, and tellurium) are members of the same group or family and are
congeners of one another. The periodic table displays the pattern of properties of the
elements. The lightest are at the top of the chart; the atomic masses increase toward the
bottom of the chart. The elements to the upper right, above a diagonal line from aluminum
(13) to polonium (84), are nonmetals, about half of which exist as gases under normal
laboratory conditions. All the elements in the middle and left of the table are metals, except
gaseous hydrogen (1). Most of the metals are shiny, deformable solids, but mercury has such
a low melting point that it is a liquid at room temperature. All the metals have high
conductivities for heat and electricity. Many simple chemical compounds are formed from a
metal reacting with a nonmetal.

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1.6. ATOMIC BONDING IN SOLIDS
In order to understand the why materials behave like they do and why they differ in
properties, it is necessary that one should look at atomic level. The study primarily
concentrates on two issues: what made the atoms to cluster together, and how atoms are
arranged. As mentioned in earlier chapter, atoms are bound to each other by number of
bonds. These inter-atomic bonds are primarily of two kinds: Primary bonds and Secondary
bonds. Ionic, Covalent and Metallic bonds are relatively very strong, and grouped as primary
bonds, whereas van der Waals and hydrogen bonds are relatively weak, and termed as
secondary bonds. Metals and Ceramics are entirely held together by primary bonds - the
ionic and covalent bonds in ceramics, and the metallic and covalent bonds in metals.
Although much weaker than primary bonds, secondary bonds are still very important. They
provide the links between polymer molecules in polyethylene (and other polymers) which
make them solids. Without them, water would boil at -80˚C, and life as we know it on earth
would not exist.

1.6.1. IONIC BONDING

This bond exists between two atoms when one of the atoms is negative (has an extra
electron) and another is positive (has lost an electron). Then there is a strong, direct
Coulomb attraction. Ionic bonds are non-directional in nature. An example is NaCl. In the
molecule, there are more electrons around Cl, forming Cl- and fewer electrons around Na,
forming Na+. Ionic bonds are the strongest bonds. In real solids, ionic bonding is usually
exists along with covalent bonding.

1.6.2. COVALENT BONDING

In covalent bonding, electrons are shared between the atoms, to saturate the valency. The
simplest example is the H2 molecule, where the electrons spend more time in between the
nuclei of two atoms than outside, thus producing bonding. Covalent bonds are stereo-specific
i.e. each bond is between a specific pair of atoms, which share a pair of electrons (of opposite
magnetic pins). Typically, covalent bonds are very strong, and directional in nature. The

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hardness of diamond is a result of the fact that each carbon atom is covalently bonded with
four neighboring atoms, and each neighbor is bonded with an equal number of atoms to form
a rigid three- dimensional structure.

1.6.3. METALLIC BONDING

Metals are characterized by high thermal and electrical conductivities. Thus, neither covalent
nor ionic bondings are realized because both types of bonding localize the valence electrons
and preclude conduction. However, strong bonding does occur in metals. The valence
electrons of metals also are delocalized. Thus metallic bonding can be viewed as metal
containing a periodic structure of positive ions surrounded by a sea of delocalized electrons.
The attraction between the two provides the bond, which is non-directional.

1.6.4. WEAK INTRA-MOLECULAR BONDING

Fluctuating Induced Dipole Bonds: Since the electrons may be on one side of the atom or
the other, a dipole is formed: the + nucleus at the center, and the electron outside. Since the
electron moves, the dipole fluctuates. This fluctuation in atom A produces a fluctuating

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electric field that is felt by the electrons of an adjacent atom, B. Atom B then polarizes so that
its outer electrons are on the side of the atom closest to the + side (or opposite to the – side)
of the dipole in A.
Polar Molecule-Induced Dipole Bonds: Another type of secondary bond exists with
asymmetric molecules, also called polar molecules because of positively and negatively
charged regions. A permanent dipole moment arises from net positive and negative charges
that are respectively associated with the hydrogen and chlorine ends of the HCl molecule,
leading to bonding. The magnitude of this bond will be greater than for fluctuating induced
dipoles. These two kinds of bonds are also called van der Waals bonds. Third type of
secondary bond is the hydrogen bond. It is categorized separately because it produces the
strongest forces of attraction in this category.
Permanent Dipole Bonds / Hydrogen bonding: It occurs between molecules as covalently
bonded hydrogen atoms – for example C-H, O-H, F-H – share single electron with other atom
essentially resulting in positively charged proton that is not shielded any electrons. This
highly positively charged end of the molecule is capable of strong attractive force with the
negative end of an adjacent molecule. The properties of water are influenced significantly by
the hydrogen bonds/bridges. The bridges are of sufficient strength, and as a consequence
water has the highest melting point of any molecule of its size. Likewise, its heat of
vaporization is very high.

1.6.5. WATER (ITS VOLUME EXPANSION UPON FREEZING)

Most liquids have a quite simple behavior when they are cooled (at a fixed pressure): they
shrink. The liquid contracts as it is cooled; because the molecules are moving slower they are
less able to overcome the attractive intermolecular forces drawing them closer to each other.
Then the freezing temperature is reached, and the substance solidifies, which causes it to
contract some more because crystalline solids are usually tightly packed.
Water is one of the few exceptions to this behavior. When liquid water is cooled, it contracts
like one would expect until a temperature of approximately 4 degrees Celsius is reached.
After that, it expands slightly until it reaches the freezing point, and then when it freezes it
expands by approximately 9%. This unusual behavior has its origin in the structure of the
water molecule. There is a strong tendency to form a network of hydrogen bonds, where

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each hydrogen atom is in a line between two oxygen atoms. This hydrogen bonding tendency
gets stronger as the temperature gets lower (because there is less thermal energy to shake
the hydrogen bonds out of position). The ice structure is completely hydrogen bonded, and
these bonds force the crystalline structure to be very "open". In the following two pictures,
the first shows a typical structure of liquid water, while the second is an ice structure; note
the extra open space in the ice.

Water Ice

It is this open solid structure that causes ice to be less dense than liquid water. That is why
ice floats on water, for which we should all be thankful because if water behaved "normally"
many bodies of water would freeze solid in the winter, killing all the life within them. Water's
"density maximum" is a product of the same phenomenon. Close to the freezing point, the
water molecules start to arrange locally into ice-like structures. This creates some
"openness" in the liquid water, which tends to decrease its density. This is opposed by the
normal tendency for cooling to increase the density; it is at approximately 4 degrees Celsius
that these opposing tendencies are balanced, producing the density maximum.

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 UNIT 2 : INTRODUCTION TO CRYSTAL STRUCTURES

2.1. CRYSTAL STRUCTURES

All metals, a major fraction of ceramics, and certain polymers acquire crystalline form when
solidify, i.e. in solid state atoms self-organize to form crystals. Crystals possess a long-range
order of atomic arrangement through repeated periodicity at regular intervals in three
dimensions of space. When the solid is not crystalline, it is called amorphous. Examples of
crystalline solids are metals, diamond and other precious stones, ice, graphite. Examples of
amorphous solids are glass, amorphous carbon (a-C), amorphous Si, most plastics.
There is very large number of different crystal structures all having long-range atomic order;
these vary from relatively simple structures for metals to exceedingly complex structures for
ceramics and some polymers. To discuss crystalline structures it is useful to consider atoms
as being hard spheres, with well-defined radii. In this scheme, the shortest distance between
two like atoms is one diameter. In this context, use of terms lattice and unit cell will be handy.
Lattice is used to represent a three-dimensional periodic array of points coinciding with
atom positions. Unit cell is smallest repeatable entity that can be used to completely
represent a crystal structure. Thus it can be considered that a unit cell is the building block
of the crystal structure and defines the crystal structure by virtue of its geometry and the
atom positions within.

Crystalline and Non-crystalline materials

Single Crystals: Crystals can be single crystals where the whole solid is one crystal. Then it
has a regular geometric structure with flat faces.
Polycrystalline Materials: A solid can be composed of many crystalline grains, not aligned
with each other. It is called polycrystalline. The grains can be more or less aligned with
respect to each other. Where they meet is called a grain boundary.
Non-Crystalline Solids: In amorphous solids, there is no long-range order. But amorphous
does not mean random, since the distance between atoms cannot be smaller than the size of

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the hard spheres. Also, in many cases there is some form of short-range order. For instance,
the tetragonal order of crystalline SiO2 (quartz) is still apparent in amorphous SiO2 (silica
glass).
There are 14 major crystal structure that majority of the elements that tend to form.
Major crystal structure types

Apart from these 14 Bravais Crystal Lattices, metallic elements can form crystal structures
of certain types. Most metals and alloys crystallize in one of three very common structures:
body-centered cubic (bcc), hexagonal close packed (hcp), or cubic close packed (ccp, also
called face centered cubic, fcc). Atoms in metallic crystals have a tendency to pack in dense
arrangments that fill space efficiently. Thus simple simple cubic structures are inefficient and
rare among metallic crystal structures. Body- or face-centered structures fill space more
efficiently and more common.

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Density Calculation of Crystals
The density of the unit cell is given as the ratio of mass and volume of the unit cell.
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
Density of the unit cell =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

The mass of the unit cell is equal to the product of the number of total atoms in the unit cell
and the mass of every atom in the unit cell.
Mass of unit cell = number of total atoms in unit cell x mass of every atom

Mass of an atom can be calculated with the help of Avogadro number and molar mass,
𝑀𝑜𝑙𝑎𝑟 𝑀𝑎𝑠𝑠
Mass of an atom =
𝐴𝑣𝑎𝑔𝑎𝑑𝑟𝑜 𝑁𝑢𝑚𝑏𝑒𝑟

2.2. POLYMORPHISM AND ALLOTROPHY

Polymorphism is the ability of a solid material to exist in more than one form or crystal
structure. We can find this characteristic in any crystalline material such as polymers,
mineral, metal, etc. There are several forms of polymorphism as follows:

 Packing polymorphism – depending on the differences in the crystal packing

 Conformational polymorphism – the presence of different conformers of the same
molecule
 Pseudopolymorphism – the presence of different crystal types as a result of hydration or
solvation.

Allotropy is the existence of two or more different physical forms of a chemical element.
These forms exist in the same physical state, mostly in the solid state. Therefore, these are
different structural modifications of the same chemical element. Allotropes contain atoms of
the same chemical element that binds with each other in different ways.

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Moreover, these different forms may have different physical properties because they have
different structures and chemical behavior may vary as well. One allotrope may convert into
another when we change some factors such as pressure, light, temperature, etc. Therefore
these physical factors affect the stability of these compounds. Some common examples for
allotropes are as follows:
 Carbon – diamond, graphite, graphene, fullerenes, etc.
 Phosphorous – white phosphorous, red phosphorous, diphosphorous, etc.
 Oxygen – dioxygen, ozone, tetraoxygen, etc.
 Boron – amorphous boron, alpha rhombohedral boron, etc.
 Arsenic – yellow arsenic, grey arsenic, etc.

2.2.1. MILLER INDICES

It is understood that properties of materials depend on their crystal structure, and
many of these properties are directional in nature. For example: elastic modulus of BCC iron
is greater parallel to the body diagonal than it is to the cube edge. Thus it is necessary to
characterize the crystal to identify specific directions and planes. Specific methods are
employed to define crystal directions and crystal planes.
Methodology to define crystallographic directions in cubic crystal:
 a vector of convenient length is placed parallel to the required direction.
 the length of the vector projection on each of three axes are measured in unit cell
dimensions.
 these three numbers are made to smallest integer values, known as indices, by
multiplying or dividing by a common factor.
 the three indices are enclosed in square brackets, [uvw]. A family of directions is
represented by <uvw>.

Methodology to define crystallographic planes in cubic crystal:

Determine the intercepts of the plane along the crystallographic axes, in terms of unit cell
dimensions. If plane is passing through origin, there is a need to construct a plane parallel to
original plane.
 Take the reciprocals of these intercept numbers.
 Clear fractions.
 Reduce to set of smallest integers.
 The three indices are enclosed in parenthesis, (hkl). A family of planes is represented
by {hkl}.

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For example, if the x-, y-, and z- intercepts of a plane are 2, 1, and 3. The Miller indices are
calculated as:
 Take reciprocals: 1/2, 1/1, 1/3.
 Clear fractions (multiply by 6): 3, 6, 2.
 Reduce to lowest terms (already there). => Miller indices of the plane are (362).
Figure 2.2 depicts Miller indices for number of directions and planes in a cubic crystal.

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 UNIT 3 : INTRODUCTION TO METALS, CERAMICS AND POLYMERS

Materials are classified into three basic groups based on their mechanical and physical
nature as – metals, ceramics and polymers.

3.1. APPLICATIONS AND PROCESSING OF METAL ALLOYS

Metals in actual commercial use are almost exclusively alloys, and not pure metals, since it
is possible for the design engineer to realize an infinite variety of physical properties in the
product by varying the metallic composition of the alloy. 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.
This is why pure metals are used only for specific applications. The alloy is usually more
corrosion resistant and less affected by atmospheric conditions. The conductivity of an alloy
varies with the degree of order of the alloy and the hardness varies with the particular heat
treatment.
In the solid state an alloy may be present in one or more of the following forms:
 As a solid solution
 As an intermediate phase or intermediate chemical compound
 As a finely divided mechanical mixture of solid solution
 As a finely divided mechanical mixture of the metals
 As a finely divided mechanical mixture of chemical compounds of metals, the individual
metals and solid solutions.
Alloys are classified as binary alloys, composed of two components; as ternary alloys,
composed of three components; or as multicomponent alloys. Most commercial alloys are
multicomponent. The composition of an alloy is described by giving the percentage (either
by weight or by atoms) of each element in it. Metal alloys by virtue of composition, are often
grouped into two classes: (i) ferrous and non-ferrous. Ferrous alloys are those in which iron
is the principal constituent, include steels and cast irons. The nonferrous alloys are all alloys
that are not iron based.
Ferrous Alloys
Ferrous alloys (steels and cast irons) are those in which iron is the prime constituent. Most
steels contain less than 1.0 wt% C, and, in addition, other alloying elements, which render
them susceptible to heat treatment (and an enhancement of mechanical properties)
and/or more corrosion resistant. Ferrous alloys are used extensively as engineering
materials because:
 Iron-bearing compounds are abundant.
 Economical extraction, refining, and fabrication techniques are available.
 They may be tailored to have a wide variety of mechanical and physical properties.

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Limitations of ferrous alloys include the following:
 Relatively high densities
 Comparatively low electrical conductivities
 Susceptibility to corrosion in common environments
The most common types of steels are plain low-carbon, high-strength low-alloy,
medium-carbon, tool, and stainless.
 Plain carbon steels contain (in addition to carbon) a little manganese and only
residual concentrations of other impurities.
 Stainless steels are classified according to the main microstructural constituent. The
three classes are ferritic, austenitic, and martensitic.
Long/Tubular Products include bars and rods, rails, wires, angles, pipes, and shapes
and sections. These products are commonly used in the automotive and construction
sectors.
Flat Products include plates, sheets, coils and strips. These materials are mainly used
in automotive parts, appliances, packaging, shipbuilding, and construction.
Other Products include valves, fittings, and flanges and are mainly used as piping
materials.
 Cast irons contain higher carbon contents than steels—normally between 3.0 and
4.5 wt% C—as well as other alloying elements, notably silicon. For these materials,
most of the carbon exists in graphite form rather than combined with iron as
cementite. Gray, ductile (or nodular), malleable, and compacted graphite irons are the
four most widely used cast irons; the latter three are reasonably ductile. Cast iron is
used in a wide variety of structural and decorative applications, because it is relatively
inexpensive, durable and easily cast into a variety of shapes. Applications: Hinges,
Latches, Columns, Balusters, Stairs, Structural Connectors in Buildings and Monuments,
Decorative Features, Fences, Tools and Utensils, Ordnance, Stoves and Firebacks, Piping.

Nonferrous Alloys
All other alloys fall within the nonferrous category, which is further subdivided
according to base metal or some distinctive characteristic that is shared by a group of alloys.
Nonferrous alloys may be further sub-classified as either wrought or cast. Alloys that are
amenable to forming by deformation are classified as wrought. Cast alloys are relatively
brittle, and therefore fabrication by casting is most expedient.
Seven classifications of nonferrous alloys are common - copper, aluminum, magnesium,
titanium, the refractory metals, the superalloys, and the noble metals, as well as
miscellaneous (nickel, lead, tin, zinc, and zirconium). The light alloys, based on aluminium,
magnesium and titanium.
 Aluminium Alloys: About 20% of the world production of aluminium is used for cast
products. Aluminium alloys have a relatively low melting temperature, but exhibit a high
shrinkage during solidification. Shrinkage of between 3.5 and 8.5% may occur, and

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 allowance has to be made for this in mould design in order to achieve dimensional
accuracy. his group includes cast aluminium alloys, aluminium-silicon alloys, aluminium-
copper alloys, aluminium magnesium alloys, aluminium-zinc-magnesium alloys, wrought
aluminium alloys. There are two important aluminium-alloy families under the heading
non-heat-treatable alloys: aluminium-manganese alloys (3XXX series) and aluminium-
magnesium alloys (5 XXX series). There are three important aluminium families under
the head heat-treatable alloys: aluminium copper alloys (2 XXX series), aluminium-
magnesium silicon alloys (6 XXX series) and aluminum-zinc-magniesium alloys (7 XXX
series).
Applications: Food/chemical handling, equipment, heat exchangers, light reflectors
Excellent thermal conductivity – Copper cookware most highly regarded – fast and
uniform heating. Electrical and construction industries are the largest users of Cu.
Electrical wires, roofing, nails, rivets, Automotive radiator, lamp fixture, clutch disk,
diaphragm, fuse clips, springs, battery clamps, light fixtures, Bearings, bushings, valve
seats and guards, Electrical, valves, pumps, Condenser, heat exchanger, piping, valves.
 Magnesium Alloys: This includes cast magnesium alloys, wrought magnesium alloys.
 Titanium Alloys: There are three types of Ti alloy microstructure, namely those with α,
β and mixed α/β structures.
 Copper Alloys: Copper and its alloys are widely used because of their high electrical and
thermal conductivity, corrosion resistance, and ease of fabrication. Copper alloys mainly
includes: Copper alloy of low solute content, copper alloys of high solute content, copper-
nickel alloys, copper-tin alloys or bronzes, copper-rich aluminium alloys known as
aluminium bronzes, etc.
Applications: Excellent thermal conductivity – Copper cookware most highly regarded
– fast and uniform heating. Electrical and construction industries are the largest users of
Cu. Electrical wires, roofing, nails, rivets, Automotive radiator, lamp fixture, clutch disk,
diaphragm, fuse clips, springs, battery clamps, light fixtures, Bearings, bushings, valve
seats and guards, Electrical, valves, pumps, Condenser, heat exchanger, piping, valves.
 Lead Alloys: The most significant applications of lead alloys are lead-acid storage
batteries, and it is also widely used for building construction materials such as sheet
because of its relative inertness to atmospheric attack. Lead is also finding increased
applications as a material for controlling sound and mechanical vibration, due to its high
damping capacity. Because of its low melting point (327.5°C), pure lead undergoes creep
at room temperature, so it usually strengthened by small additions of solute. Thus 1.5 to
3% antimony or traces of calcium are often present in the plates of car batteries, and
different manufactures may use different solutes. The important families of more
concentrated alloys are the lead-tin solders and lead-based bearing alloys, which may
contain antimony, tin and arsenic, for use in internal combustion engines.
 Zinc Alloys: The main uses of Zn are as an alloying element (e.g. in copper) and as a
protective coating for steel (galvanising, etc.). However, Zn-based alloys are also used for
the production of gravity castings, and pressure die-castings of high dimensional
tolerance. The casting alloys are based on the Zn – Al system, and are close to eutectic
composition of 5% Al. The hyperutectic alloys solidify with Zn-rich dendrites, whereas

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 the hyperutectic contain Al-rich dendrites. The commercial alloys contain strengthening
additions of copper and magnesium, but the greatest care has to be taken to prevent
excessive pick-up of harmful impurity elements such as Pb, Cd, Sn, and Fe. The alloys
themselves are prepared from high-purity components, otherwise intergranular
embrittlement of the castings develops over a period of time
 Nickel Alloys: Commercially pure nickel offers excellent corrosion resistance to
reducing environments (in contrast to those metals and alloys which owe their resistance
to the presence of a tenacious oxide film), and are found in the chemical processing
industry, as well as in food processing applications. As an electroplated coating, nickel is
widely used in the electronics industry.
 Ni-Cu Alloys: These alloys possess excellent corrosion resistance, notable in sea water.
The monel (~30% Cu) series of alloys is used for turbine blading, valve parts and for
marine propeller shafts, because of their high fatigue strength in sea water.
 Ni-Cr Alloys: These alloys form the basic alloys for jet engine development – the Nimonic
alloys, or Nibased superalloys. The limitation of the conventionally cast supperalloys was
their lack of creep ductility due to cavitation at the grain boundaries lying perpendicular
to the maximum tensile stress, so directionally solidified and eventually single crystal
alloys were developed.
Alloys are widely used in industry because their physical and chemical properties can be
easily varied to suit the exact individual requirement. One can achieve this by preparing
alloys of different metals. Metallic objects are invariably manufactured from alloys instead
of pure metals. The alloying elements are added to improve one or more of the following
properties: (a) tensile strength, hardness and toughness (b) corrosive and oxidation
resistance, (c) machinability, (d) elasticity (e) hardenability (f) creep strength and (g) fatigue
resistance, etc.
Forming Operations
Forming operations are those in which a metal piece is shaped by plastic deformation. When
deformation is carried out above the recrystallization temperature, it is termed hot working;
otherwise, it is cold working. Forging, rolling, extrusion, and drawing are four of the
more common forming techniques.
Casting: Depending on the properties and shape of the finished piece, casting may be the
most desirable and economical fabrication process. The most common casting techniques
are sand, die, investment, lost foam, and continuous.
Powder metallurgy involves compacting powder metal particles into a desired shape,
which is then densified by heat treatment. P/M is used primarily for metals that have low
ductilities and/or high melting temperatures.
Welding is used to join together two or more workpieces; a fusion bond forms by melting
portions of the workpieces and, in some instances, a filler material.
Annealing Processes is the exposure of a material to an elevated temperature for
an extended time period followed by cooling to room temperature at a relatively slow

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rate is termed annealing. During process annealing, a cold-worked piece is rendered softer
yet more ductile as a consequence of recrystallization. Internal residual stresses that have
been introduced are eliminated during a stress relief anneal. For ferrous alloys,
normalizing is used to refine and improve the grain structure.
Heat Treatment of Steels: For high-strength steels, the best combination of mechanical
characteristics may be realized if a predominantly martensitic microstructure is developed
over the entire cross section; this is converted to tempered martensite during a tempering
heat treatment. Hardenability is a parameter used to ascertain the influence of composition
on the susceptibility to the formation of a predominantly martensitic structure for some
specific heat treatment. Martensite content is determined using hardness measurements.
Precipitation Hardening: Some alloys are amenable to precipitation hardening—that is, to
strengthening by the formation of very small particles of a second, or precipitate, phase.
Control of particle size, and subsequently strength, is accomplished by two heat
treatments: In the first, or solution heat treatment, all solute atoms are dissolved to form a
single-phase solid solution; quenching to a relatively low temperature preserves this state.
During the second or precipitation treatment (at constant temperature), precipitate particles
form and grow; strength, hardness, and ductility are dependent on heat treating
time (and particle size). Strength and hardness increase with time to a maximum and then
decrease during overaging. This process is accelerated with rising temperature. The
strengthening phenomenon is explained in terms of an increased resistance to dislocation
motion by lattice strains, which are established in the vicinity of these
microscopically small precipitate particles.

3.2. PHASE DIAGRAMS

The characteristic of any series of alloys can be easily studied by using alloy phase diagrams.
A phase diagram is a graphical description of the kinds and amounts of the phases that can
be expected in an alloy as a function of its composition, temperature, and pressure, when it
has reached thermodynamic equilibrium. The phases may be liquid, vapour or solid with
various ordered and disordered crystal structures. A phase diagram does not provide
information about how rapidly equilibrium can be reached. When a phase diagram is
determined experimentally, it is necessary not only to find out what phases are present but
also to assure that the alloy is in the stable equilibrium state. Equilibrium is reached when
the Gibbs free energy of the system has reached its lowest possible value. The
thermodynamic principle of minimum Gibbs free energy imposes restrictions on the possible
forms a phase diagram can take, and even a complicated diagram with many phases is
composed of only a few geometrical features.
The following terms are frequently used in the study of solid phases and phase diagrams:
(i) System: A system may be composed of solids, liquids, gases or their combinations and
may have metals and non-metals separately or in any combination. It is explained as the
whole complex of phases of one or several components at different pressures and
compositions. A system is so isolated from its surroundings that it is unaffected by solids,

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liquids, gases or their combinations and is subjected to the change in the overall composition,
temperature, pressure or total volume, only to the extent permitted by the investigator.
(ii) Components: These are the substances, either chemical elements or chemical
compounds, whose presence is essential and sufficient to make a system. A pure metal is
called a one-component system, an alloy of two metals is called a binary or two component
system, etc.
(iii) Phase: It is a homogeneous portion of a system that has uniform physical and chemical
characteristics. The number of phases in a system is the number of different substances that
exist in it in a homogeneous system.
(iv) Phase diagram: A graphical representation of the relationships between environmental
constraints (e.g. temperature and sometimes pressure), composition, and regions of phase
stability, ordinarily under conditions of equilibrium. Most phase diagrams are prepared by
using slow cooling conditions whereby phases are in equilibrium.
One can get following important informations from the phase diagrams
(a) Phases at different composition and temperature
(b) Equilibrium solubility of one element or compound in another element.
(c) Melting points of different phases in an alloy.
(d) Temperature of solidification or range of solidification of an alloy.
(v) Phase Equilibrium: The state of a system where the phase characteristics remain constant
over indefinite time periods. At equilibrium the free energy is a minimum. In an equilibrium
diagram, liquid is one phase and solid solution is another phase.
(vi) Phase Transformation: A change in the number and/or character of the phases that
constitute the microstructure of an alloy.

3.2.1. SOLUBILITY LIMIT

For many alloy systems and at some specific temperature, there is a maximum concentration
of solute atoms that may dissolve in the solvent to form a solid solution; this is called a
solubility limit. The addition of solute in excess of this solubility limit results in the formation
of another solid solution or compound that has a distinctly different composition. To
illustrate this concept, consider the sugar–water (C12H22O11–H2O) system. Initially, as sugar
is added to water, a sugar–water solution or syrup forms. As more sugar is introduced, the
solution becomes more concentrated, until the solubility limit is reached or the solution
becomes saturated with sugar. At this time, the solution is not capable of dissolving any more
sugar, and further additions simply settle to the bottom of the container. Thus, the system
now consists of two separate substances: a sugar–water syrup liquid solution and solid
crystals of undissolved sugar. This solubility limit of sugar in water depends on the
temperature of the water and may be represented in graphical form on a plot of temperature
along the ordinate and composition (in weight percent sugar) along the abscissa, as shown

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in below figure. Along the composition axis, increasing sugar concentration is from left to
right, and percentage of water is read from right to left. Because only two components are
involved (sugar and water), the sum of the concentrations at any composition will equal 100
wt%. The solubility limit is represented as the nearly vertical line in the figure. For
compositions and temperatures to the left of the solubility line, only the syrup liquid solution
exists; to the right of the line, syrup and solid sugar coexist. The solubility limit at some
temperature is the composition that corresponds to the intersection of the given
temperature coordinate and the solubility limit line. For example, at 20°C, the maximum
solubility of sugar in water is 65 wt%. As below figure indicates, the solubility limit increases
slightly with rising temperature.

3.2.2. PHASES
Also critical to the understanding of phase diagrams is the concept of a phase. A phase may
be defined as a homogeneous portion of a system that has uniform physical and chemical
characteristics. Every pure material is considered to be a phase; so also is every solid, liquid,
and gaseous solution. For example, the sugar–water syrup solution just discussed is one
phase, and solid sugar is another. Each has different physical properties (one is a liquid, the
other is a solid); furthermore, each is different chemically (i.e., has a different chemical
composition); one is virtually pure sugar, the other is a solution of H2O and C12H22O11. If more
than one phase is present in a given system, each will have its own distinct properties, and a
boundary separating the phases will exist, across which there will be a discontinuous and
abrupt change in physical and/or chemical characteristics. When two phases are present in
a system, 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. When water and ice
are present in a container, two separate phases exist; they are physically dissimilar (one is a
solid, the other is a liquid) but identical in chemical makeup. Also, when a substance can exist
in two or more polymorphic forms (e.g., having both FCC and BCC structures), each of these
structures is a separate phase because their respective physical characteristics differ.
Sometimes, a single-phase system is termed homogeneous. Systems composed of two or
more phases are termed mixtures or heterogeneous systems. Most metallic alloys and, for
that matter, ceramic, polymeric, and composite systems are heterogeneous. Typically, the
phases interact in such a way that the property combination of the multiphase system is
different from, and more desirable than, either of the individual phases.

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3.2.3. MICROSTRUCTURE
The physical properties and, in particular, the mechanical behavior of a material often
depend on the microstructure. Microstructure is subject to direct microscopic observation
using optical or electron microscopes. In metal alloys, microstructure is characterized by the
number of phases present, their proportions, and the manner in which they are distributed
or arranged. The microstructure of an alloy depends on such variables as the alloying
elements present, their concentrations, and the heat treatment of the alloy (i.e., the
temperature, the heating time at temperature, and the rate of cooling to room temperature).
After appropriate polishing and etching, the different phases may be distinguished by their
appearance. For example, for a two-phase alloy, one phase may appear light and the other
phase dark. When only a single phase or solid solution is present, the texture is uniform,
except for grain boundaries that may be revealed.

3.2.4. PHASE EQUILIBRIA

Equilibrium is another essential concept; it is best described in terms of a thermodynamic
quantity called the free energy. In brief, free energy is a function of the internal energy of a
system and also the randomness or disorder of the atoms or molecules (or entropy). A
system is at equilibrium if its free energy is at a minimum under some specified combination
of temperature, pressure, and composition. In a macroscopic sense, this means that the
characteristics of the system do not change with time, but persist indefinitely—that is, the
system is stable. A change in temperature, pressure, and/or composition for a system in
equilibrium results in an increase in the free energy and in a possible spontaneous change
to another state by which the free energy is lowered.
The term phase equilibrium, often used in the context of this discussion, refers to equilibrium
as it applies to systems in which more than one phase may exist. Phase equilibrium is
reflected by a constancy with time in the phase characteristics of a system. Perhaps an
example best illustrates this concept. Suppose that a sugar–water syrup is contained in a
closed vessel and the solution is in contact with solid sugar at 20°C. If the system is at
equilibrium, the composition of the syrup is 65 wt% C12H22O11–35 wt% H2O, and the
amounts and compositions of the syrup and solid sugar will remain constant with time. If the
temperature of the system is suddenly raised-say, to 100°C-this equilibrium or balance is
temporarily upset and the solubility limit is increased to 80 wt% C12H22O11. Thus, some of
the solid sugar will go into solution in the syrup. This will continue until the new equilibrium
syrup concentration is established at the higher temperature.
This sugar–syrup example illustrates the principle of phase equilibrium using a liquid–solid
system. In many metallurgical and materials systems of interest, phase equilibrium involves
just solid phases. In this regard the state of the system is reflected in the characteristics of
the microstructure, which necessarily include not only the phases present and their
compositions, but, in addition, the relative phase amounts and their spatial arrangement or
distribution

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Equilibrium Phase Diagrams
Give the relationship of composition of a solution as a function of temperatures and the
quantities of phases in equilibrium. These diagrams do not indicate the dynamics when one
phase transforms into another. Sometimes diagrams are given with pressure as one of the
variables. In the phase diagrams we will discuss, pressure is assumed to be constant at one
atmosphere.
Binary Isomorphous Systems
This very simple case is one complete liquid and solid solubility, an isomorphous system.
The example is the Cu-Ni alloy of below figure. The complete solubility occurs because both
Cu and Ni have the same crystal structure (FCC), near the same radii, electronegativity and
valence. The liquidus line separates the liquid phase from solid or solid + liquid phases. That
is, the solution is liquid above the liquidus line. The solidus line is that below which the
solution is completely solid (does not contain a liquid phase.)

Development of microstructure in isomorphous alloys

a) Equilibrium cooling
Solidification in the solid + liquid phase occurs gradually upon cooling from the liquidus line.
The composition of the solid and the liquid change gradually during cooling (as can be
determined by the tie-line method.) Nuclei of the solid phase form and they grow to consume
all the liquid at the solidus line.
b) Non-equilibrium cooling
Solidification in the solid + liquid phase also occurs gradually. The composition of the liquid
phase evolves by diffusion, following the equilibrium values that can be derived from the tie-
line method. However, diffusion in the solid state is very slow. Hence, the new layers that
solidify on top of the grains have the equilibrium composition at that temperature but once
they are solid their composition does not change. This lead to the formation of layered
(cored) grains.
Phase diagrams are of following three types:
 (i) Unitary or single-component phase diagram
 (ii) Binary or two-component phase diagram
 (iii) Ternary or three-component phase diagram

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3.2.5. UNITARY DIAGRAMS:
 Phase diagrams plot pressure (typically in atmospheres) versus temperature (typically
in degrees Celsius or Kelvin). Following figure shows a unitary phase diagram of water.
 The lines represent the combinations of pressures and temperatures at which two phases
can exist in equilibrium. In other words, these lines define phase change points.
 The red line divides the solid and gas phases, represents sublimation (solid to gas) and
deposition (gas to solid). The green line divides the solid and liquid phases and
represents melting (solid to liquid) and freezing (liquid to solid). The blue divides the
liquid and gas phases, represents vaporization (liquid to gas) and condensation (gas to
liquid).
 There are also two important points on the diagram, the triple point and the critical point.
The triple point represents the combination of pressure and temperature that facilitates
all phases of matter at equilibrium. The critical point terminates the liquid/gas phase line
and relates to the critical pressure, the pressure above which a supercritical fluid forms.

3.2.6. BINARY PHASE DIAGRAM:

This kind of phase diagram is a “hybrid” of the diagram with complete solid and liquid
solution and the eutectic diagram (the metals are completely soluble in liquid state and
entirely insoluble in solid state). These phase diagrams shows the relationship between two
components as a function of temperature.
The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram
This is one of the most important alloys for structural applications. The diagram Fe—C is
simplified at low carbon concentrations by assuming it is the Fe—Fe3C diagram.
Concentrations are usually given in weight percent. The possible phases are:
• α-ferrite (BCC) Fe-C solution
• γ-austenite (FCC) Fe-C solution

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• δ-ferrite (BCC) Fe-C solution
• liquid Fe-C solution
• Fe3C (iron carbide) or cementite. An intermetallic compound.

The maximum solubility of C in α- ferrite is 0.022 wt%. δ−ferrite is only stable at high
temperatures. It is not important in practice. Austenite has a maximum C concentration of
2.14 wt %. It is not stable below the eutectic temperature (727 C) unless cooled rapidly
(Chapter 10). Cementite is in reality metastable, decomposing into α-Fe and C when heated
for several years between 650 and 770 C.
 δ-ferrite: – It is solid solution of carbon in δ-iron. Maximum concentration of carbon in δ-
ferrite is 0.09% at 2719 ºF (1493ºC) which is the temperature of the peritectic
transformation. The crystal structure of δ-ferrite is BCC (cubic body centered).
 Austenite: – Austenite is interstitial solid solution of carbon in γ-iron. Austenite has FCC
(cubic face centered) crystal structure, permitting high solubility of carbon i.e. up to
2.06% at 2097 ºF (1147 ºC). Austenite does not exist below 1333 ºF (723ºC) and
maximum carbon concentration at this temperature is 0.83%.
 α-ferrite: – It is solid solution of carbon in α-iron. α-ferrite has BCC crystal structure and
low solubility of carbon – up to 0.025% at 1333 ºF (723ºC). α-ferrite exists at room
temperature.
 Cementite – Cementite is also known as iron carbide, is an intermetallic compound of
iron and carbon, having fixed composition Fe3C. Cementite is a hard and brittle
substance, influencing the properties of steels and cast irons.

3.3. APPLICATIONS AND PROCESSING OF CERAMICS

Ceramics can be defined as heat-resistant, non-metallic, inorganic solids that are (generally)
made up of compounds formed from metallic and non-metallic elements. Although different
types of ceramics can have very different properties, in general ceramics are corrosion-

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resistant and hard, but brittle. Most ceramics are also good insulators and can withstand high
temperatures. These properties have led to their use in virtually every aspect of modern life.
The two main categories of ceramics are traditional and advanced. Traditional ceramics
include objects made of clay and cements that have been hardened by heating at high
temperatures. Traditional ceramics are used in dishes, crockery, flowerpots, and roof and
wall tiles. Advanced ceramics include carbides, such as silicon carbide, SiC; oxides, such as
aluminum oxide, Al2O3; nitrides, such as silicon nitride, Si3N4; and many other materials,
including the mixed oxide ceramics that can act as superconductors. Advanced ceramics
require modern processing techniques, and the development of these techniques has led to
advances in medicine and engineering.
Glass is sometimes considered a type of ceramic. However, glasses and ceramics differ in that
ceramics have a crystalline structure while glasses contain impurities that prevent
crystallization. The structure of glasses is amorphous, like that of liquids. Ceramics tend to
have high, well-defined melting points, while glasses tend to soften over a range of
temperatures before becoming liquids. In addition, most ceramics are opaque to visible light,
and glasses tend to be translucent. Glass ceramics have a structure that consists of many tiny
crystalline regions within a noncrystalline matrix. This structure gives them some properties
of ceramics and some of glasses. In general, glass ceramics expand less when heated than
most glasses, making them useful in windows, for wood stoves, or as radiant glass-ceramic
cooktop surfaces.
Composition
Some ceramics are composed of only two elements. For example, alumina is aluminum oxide,
Al2O3; zirconia is zirconium oxide, ZrO2; Ceramics are good insulators and can withstand
high temperatures. A popular use of ceramics is in artwork. silicon dioxide, SiO2. Other
ceramic materials, including many minerals, have complex and even variable compositions.
For example, the ceramic mineral feldspar, one of the components of granite, has the formula
KAlSi3O8.
The chemical bonds in ceramics can be covalent, ionic, or polar covalent, depending on the
chemical composition of the ceramic. When the components of the ceramic are a metal and
a nonmetal, the bonding is primarily ionic; examples are magnesium oxide (magnesia), MgO,
and barium titanate, BaTiO3. In ceramics composed of a metalloid and a nonmetal, bonding
is primarily covalent; examples are boron nitride, BN, and silicon carbide, SiC. Most ceramics
have a highly crystalline structure, in which a three-dimensional unit, called a unit cell, is
repeated throughout the material. For example, magnesium oxide crystallizes in the rock salt
structure. In this structure, Mg2+ ions alternate with O2− ions along each perpendicular axis.
Manufacture of Traditional Ceramics
Traditional ceramics are made from natural materials such as clay that have been hardened
by heating at high temperatures (driving out water and allowing strong chemical bonds to
form between the flakes of clay). In fact, the word "ceramic" comes from the Greek keramos,
whose original meaning was "burnt earth." When artists make ceramic works of art, they

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first mold clay, often mixed with other raw materials, into the desired shape. Special ovens
called kilns are used to "fire" (heat) the shaped object until it hardens.
Clay consists of a large number of very tiny flat plates, stacked together but separated by thin
layers of water. The water allows the plates to cling together, but also acts as a lubricant,
allowing the plates to slide past one another. As a result, clay is easily molded into shapes.
High temperatures drive out water and allow bonds to form between plates, holding them in
place and promoting the formation of a hard solid. Binders such as bone ash are sometimes
added to the clay to promote strong bond formation, which makes the ceramic resistant to
breakage. The common clay used to make flowerpots and roof tiles is usually red-orange
because of the presence of iron oxides. White ceramics are made from rarer (and thus more
expensive) white clays, primarily kaolin.
The oldest known ceramics made by humans are figurines found in the former
Czechoslovakia that are thought to date from around 27,000 B.C.E. It was determined that
the figurines were made by mixing clay with bone, animal fat, earth, and bone ash (the ash
that results when animal bones are heated to a high temperature), molding the mixture into
a desired shape, and heating it in a domed pit. The manufacture of functional objects such as
pots, dishes, and storage vessels, was developed in ancient Greece and Egypt during the
period 9000 to 6000 B.C.E.
An important advance was the development of white porcelain. Porcelain is a hard, tough
ceramic that is less brittle than the ceramics that preceded it. Its strength allows it to be
fashioned into beautiful vessels with walls so thin they can even be translucent. It is made
from kaolin mixed with china stone, and the mixture is heated to a very high temperature
(1,300°C, or 2,372°F). Porcelain was developed in China around C.E. 600 during the T'ang
dynasty and was perfected during the Ming dynasty, famous for its blue and white porcelain.
The porcelain process was introduced to the Arab world in the ninth century; later Arabs
brought porcelain to Spain, from where the process spread throughout Europe.
Bone china has a composition similar to that of porcelain, but at least 50 percent of the
material is finely powdered bone ash. Like porcelain, bone china is strong and can be formed
into dishes with very thin, translucent walls. Stoneware is a dense, hard, gray or tan ceramic
that is less expensive than bone china and porcelain, but it is not as strong. As a result,
stoneware dishes are usually thicker and heavier than bone china or porcelain dishes.
Manufacture of Advanced Ceramics
The preparation of an advanced ceramic material usually begins with a finely divided
powder that is mixed with an organic binder to help the powder consolidate, so that it can
be molded into the desired shape. Before it is fired, the ceramic body is called "green." The
green body is first heated at a low temperature in order to decompose or oxidize the binder.
It is then heated to a high temperature until it is "sintered," or hardened, into a dense,
strong ceramic. At this time, individual particles of the original powder fuse together as
chemical bonds form between them. During sintering the ceramic may shrink by as much as

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10 to 40 percent. Because shrinkage is not uniform, additional machining of the ceramicmay
be required in order to obtain a precise shape.
Sol-gel technology allows better mixing of the ceramic components at the molecular level,
and hence yields more homogeneous ceramics, because the ions are mixed while in solution.
In the sol-gel process, a solution of an organometallic compound is hydrolyzed to produce a
"sol," a colloidal suspension of a solid in a liquid. Typically the solution is a metal alkoxide
such as tetramethoxysilane in an alcohol solvent. The sol forms when the individual formula
units polymerize (link together to form chains and networks). The sol can then be spread
into a thin film, precipitated into tiny uniform spheres called microspheres, or further
processed to form a gel inside a mold that will yield a final ceramic object in the desired
shape. The many crosslinks between the formula units result in a ceramic that is less brittle
than typical ceramics.
Although the sol-gel process is very expensive, it has many advantages, including low
temperature requirements; the ceramist's ability to control porosity and to form films,
spheres, and other structures that are difficult to form in molds; and the attainment of
specialized ceramic compositions and high product purity. Porous ceramics are made by the
sol-gel process. These ceramics have sponge like structures, with many porelike lacunae, or
openings, that can make up from 25 to 70 percent of the volume. The pore size can be large,
or as small as 50 nanometers (2 × 10−6 inches) in diameter. Because of the large number of
pores, porous ceramics have enormous surface areas (up to 500 square meters, or 5,382
square feet, per gram of ceramic), and so can make excellent catalysts. For example,
zirconium oxide is a ceramic oxygen sensor that monitors the air-to- fuel ratio in the exhaust
systems of automobiles.
Aerogels are solid foams prepared by removing the liquid from the gel during a sol-gel
process at high temperatures and low pressures. Because aerogels are good insulators, have
very low densities, and do not melt at high temperatures, they are attractive for use in
spacecraft.
Properties and Uses
For centuries ceramics were used by those who had little knowledge of their structure.
Today, understanding of the structure and properties of ceramics is making it possible to
design and engineer new kinds of ceramics.
Most ceramics are hard, chemically inert, refractory (can withstand very high heat without
deformation), and poor conductors of heat and electricity. Ceramics also have low densities.
These properties make ceramics attractive for many applications. Ceramics are used as
refractories in furnaces and as durable building materials (in the form of bricks, tiles, cinder
blocks, and other hard, strong solids). They are also used as common electrical and thermal
insulators in the manufacture of spark plugs, telephone poles, electronic devices, and the
nose cones of spacecraft. However, ceramics also tend to be brittle. A major difficulty with
the use of ceramics is their tendency to acquire tiny cracks that slowly become larger until
the material falls apart. To prevent ceramic materials from cracking, they are often appliedas

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coatings on inexpensive materials that are resistant to cracks. For example, engineparts are
sometimes coated with ceramics to reduce heat transfer.
Composite materials that contain ceramic fibers embedded in polymer matrices possess
many of the properties of ceramics; these materials have low densities and are resistant to
corrosion, yet are tough and flexible rather than brittle. They are used in tennis rackets,
bicycles, and automobiles. Ceramic composites may also be made from two distinct ceramic
materials that exist as two separate ceramic phases in the composite material. Cracks
generated in one phase will not be transferred to the other. As a result, the resistance of the
composite material to cracking is considerable. Composite ceramics made from diborides
and/or carbides of zirconium and hafnium mixed with silicon carbide are used to create the
nose cones of spacecraft. Break-resistant cookware (with outstanding thermal shock
resistance) is also made from ceramic composites.
Structure and Properties
The properties of ceramic materials, like all materials, are dictated by the types of atoms
present, the types of bonding between the atoms, and the way the atoms are packed together.
This is known as the atomic scale structure. Most ceramics are made up of two or more
elements. This is called a compound. For example, alumina (Al2O3), is a compound made up
of aluminum atoms and oxygen atoms.
The atoms in ceramic materials are held together by a chemical bond. The two most common
chemical bonds for ceramic materials are covalent and ionic. For metals, the chemical bond
is called the metallic bond. The bonding of atoms together is much stronger in covalent and
ionic bonding than in metallic. That is why, generally speaking, metals are ductile and
ceramics are brittle.
Another structure that plays an important factor in the final property of a material is called
microstructure. The microstructure of a material is the structure that can be seen using a
microscope, but seldom with the naked eye. For ceramics, the microstructure can be entirely
glassy (glasses only); entirely crystalline; or a combination of crystalline and glassy. In the
last case, the glassy phase usually surrounds small crystals, bonding them together.
The atomic structure primarily effects the chemical, physical, thermal, electrical, magnetic,
and optical properties. The microstructure also can effect these properties but has its major
effect on mechanical properties and on the rate of chemical reaction. Due to ceramic
materials wide range of properties, they are used for a multitude of applications. In general,
most ceramics are:
 Hard,
 wear-resistant,
 brittle,
 refractory,
 thermal insulators,
 electrical insulators,
 nonmagnetic,

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 oxidation resistant,
 prone to thermal shock, and chemically stable.
Of course there are many exceptions to these generalizations. For example, borosilicate
glasses (glasses that contain silica and boron as major ingredients) and certain glass
ceramics (glasses that contain a crystalline phase) and NZP ceramics are very resistant to
thermal shock and are used in applications such as ovenware, stove tops and kiln furniture
respectively. Also, some ceramics are excellent electrical conductors and an entire
commercial market is based on the fact that certain ceramics (ferrites) are magnetic.

3.4. APPLICATIONS AND PROCESSING OF POLYMERS

Plastics belong to the family of organic materials. Organic materials are those materials are
derived directly from carbon. They consist of carbon chemically combined with hydrogen,
oxygen and other non-metallic substances, and their structures, in most cases, are fairly
complex. The large and diverse organic group includes the natural materials: wood, coal,
petroleum, natural rubber, animal fibers and food, which have biological origins. Synthesis
include the large group of solvents, adhesives, synthetic fibers, rubbers, plastics, explosives,
lubricants, dyes, soaps and cutting oils etc. which have no biological origins. Of them plastics
and synthetic tubers termed as “Polymers”.
The term “polymer” is derived from the two Greek words: poly, meaning “many”, and meros
meaning “parts” or “units”. Thus polymers are composed of a large number of repeating units
(small molecules) called monomers. The monomers are joined together end- to-end in a
polymerization reaction.
The most common polymers are those made from compounds of carbon, but polymers can
also make from inorganic chemicals such as silicates and silicones. The naturally occurring
polymers include: protein, cellulose, resins, starch, shellac and lignin. They are commonly
found in leather, fur, wool, cotton, silk, rubber, wood and many others. There are also
synthetic polymers such as polyethylene, polystyrene, nylon, Terylene, Dacron etc… termed
under plastics, fibers and elastomers. Their properties are superior to those of the naturally
occurring counterparts. Our concern here is therefore with synthetic polymers, also called
plastics or resins.
Polymerization: The process of linking together of monometers, that is, of obtaining
macromolecules is called “polymerization”. It can be achieved by one of the two processing
techniques i.e., Addition Polymerization and condensation Polymerization.
Polymers can be divided into three broad divisions: plastics, fibers and elastomers. Plastic
derive their name from the fact that in a certain phase of their manufacture, they are present
in a plastic stage that is acquire plasticity, which makes it possible to impart any desired
shape to the product. Plastics fall into a category of known chemically as high polymers.

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Engineering Plastics
The “Plastics” is a term applied to compositions consisting of a mixture of high molecular
compounds and fillers, plasticizers, stains, and pigments, lubricating and other substances,
some of the plastics can contain nothing but resin.
The word plastics is from the Greek word Plastikos, means which are moulded and shaped.
Plastics can be easily machined, formed and joined into required shapes. Hence, plastics find
place in engineering materials and domestic applications. Plastics are available in rods,
sheets, films and tubes.
Types of Plastics
Plastics are classified on the broad basis of whether heat causes them to set (thermosetting)
causes them to soften and melt (thermoplastic). Plastics are classified as:
(a) Thermosetting Plastics: These are formed to shape with heat, with or without
pressure, resulting in a product that is permanently hard. The heat first softens the material,
but as additional heat or special chemicals are added, the plastic is hardened by chemical
change known as “polymerization” and cannot be resoftened. Thermosetting plastics are
phenol-formaldehyde. Urea formaldehyde, epoxy resins etc. Products made by
thermosetting plastics are T.V cabinets, telephone receivers, camera bodies and automobile
parts.
(b) Thermoplastics: Thermoplastics under go no chemical change in moulding. They
remain soft at elevated temperatures until they are hardened by cooling. These plastics can
be reused or recycled by melting and remoulding. Most commonly used thermoplastics are
polystyrene, polytene, P.V.V. (polyvinyl chloride) Nylon, Teflon etc… Products made by
thermoplastics are photographic films, insulating tapes, hose pipes etc.
Properties of Plastics
Their great variety of physico chemical and mechanical properties and the ease with which
they can be made into various articles have found plastics their wide application in the
engineering and the other industries.
 Their comparatively low density, substantial mechanical strength higher strength – to –
weight ratio and high anti friction properties have enabled plastics to be efficiently used
as substitute for metals.
 With certain special properties, plastics can sometimes replace ferrous metals.
 From the productions point of view, their main advantage is their relatively low melting
points and their ability to flow into a mould.
 Simple processing to obtain machine parts. Generally there is only one production
operation required to convert the chemically manufactured plastic in to a finished article.
 Good damping capacity and good surface finish of the product.

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 The high heat and electric insulation of plastics permits them to be applied in the radio
and electrical engineering industries as dielectrics and as substitutes for porcelain,
ebonite, shellac, mica, natural rubber etc…
 Their good chemical stability when subjected to the action of solvents and certain
oxidizing agents, water resistance, gas and steam proof properties enable plastics to be
used as valuable engineering materials in the automobile and tractor, ship building and
other industries.

Comparison between Thermosetting plastics and Thermoplastics:

Thermosetting plastics
 Once hardened and set, they do not soften with the application of heat.
 These are stronger and harder.
 Objects made by these plastics can be used at comparatively high temperatures.
 These are supplied in monomeric or partially polymerized form in which these are either
liquids or semi solids.
 T.V. Cabinets, Automobile parts are made by these plastics.
Thermoplastics
 They can be repeatedly softened by heat and hardened by cooling.
 They are comparatively softer and less strong.
 Objects made by thermoplastics cannot be used at higher temperatures as these lend to
soften under heat.
 These are usually supplied as granular material.
 Insulating tapes, photographic films are made by these plastics.
Advantages of Plastics:
 Light in weight compared to metals.
 Excellent surface finish.
 Close dimensional tolerances.
 Moisture and corrosion resistance.
 Easy to shape and mould.
Disadvantages of Plastics:
 Low strength.
 Low heat resistance.
 Deteriorate in sunlight.
Applications of Plastics:
Plastics find applications in manufacturing of:
 Photo films in film industry.
 Insulating tapes
 Electrical parts like plugs, switches etc…
 Radio, T.V. cabinets
 Furniture like chairs, tubs

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 Telephone receivers
 Camera bodies
 Gears and Bearings
 Toys, bottles, bucket etc…
 Hose pipes
 Automobile parts
Polymers of Commercial Importance
There are various polymers of commercial importance, which are used in so many different
dominions of sciences, industry and technology. Some are listed below:
Nylon
Nylon is a synthetic polymer prepared in labs and produced by industries for its commercial
importance. It is commonly used in the textile and fabric industry. Nylon comes under the
family of linear polyamides. Nylon 6 and nylon 6,6 are 2 commonly used types of nylon. In fact,
Nylon 6,6 (widely used as fibres) is made from adipic acid and hexamethylene diamine.They have
a compact molecular structure exhibiting excellent abrasion resistance. The monomers are
joined by hydrogen bonding. Nylon’s characteristics which make it such a valuable material can
be attributed to its strength, lustre, elasticity and resistance to damage by oil and chemicals.
Nylon Fibre is used in clothing/apparels in shirts, underwear, raincoats lingeries etc. Industrial
uses of Nylon are the production of Conveyer and seat belts, nets and ropes, parachutes and tents.

Polytetrafluoroethylene
It is commonly known as PTFE is a synthetic fluoropolymer of tetrafluoroethylene. It is of high
molecular weight and made up of mainly carbon and fluorine.The best-known brand name of
PTFE-based formulas is Teflon which is extensively used in cook-wares such as non- stick pans.

Bakelite
Bakelite is one of the oldest polymers that was synthesized by man. It is a thermosetting polymer
and has high strength and retains its shape after moulding. It is one of the first polymer/plastic
created in a laboratory. The polymer is formed by condensation of formaldehyde with phenol.
Its chemical formula is (C6H6O·CH2O)n. Bakelite has a high resistance to heat and chemicals and
also has a low electrical conductivity due to which it is most commonly used for making electrical
switches Bakelite is also used to make the handles of a variety of utensils. It is one of the most
important and extensively used polymers for making components and parts of various items.
Other uses of this polymer are seen in pipe stems.
Polyvinyl Chloride (PVC)
When talking about polymers of commercial importance we must discuss PVC. It is one of the
most widely used polymers in the world. PVC is used extensively across a broad range of
applications (used in building, transport, packaging, electrical etc. products), and this can be
attributed to its highly versatile nature. PVC is a highly durable and long-lasting material. It is
thermoplastic in nature.It is formed after polymerization of vinyl chloride monomer. It is a very
durable and long-lasting material which can be used in a variety of applications, either rigid or
flexible, white black or a range of colours in between. Some common commercial products which
use the polymer PV Care window frames, drainage pipe, medical devices, cable and wire

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insulation. Credit cards and vinyl records are also made using PVC. Recently PVC has also found
a place in the textile industry.

Elastomers
Elastomers (rubbers) are special polymers that are very elastic. They are lightly cross-linked
and amorphous with a glass transition temperature well below room temperature. They can
be envisaged as one very large molecule of macroscopic size. The intermolecular forces
between the polymer chains are rather weak. The crosslinks completely suppress
irreversible flow but the chains are very flexible at temperatures above the glass transition,
and a small force leads to a large deformation. Thus, elastomers have a low Young's modulus
and very high elongation at break when compared with other polymers. The term elastomer
is often used interchangeably with the term rubber, although the latter is preferred when
referring to vulcanized rubbers.
Manufacturing elastomeric parts is achieved in one of three ways: injection molding, transfer
molding, or compression molding. The choice of the molding process depends on various
factors, including the shape and size of the parts, the required tolerance, as well as the
quantity, type of elastomer, and raw material cost. As with almost any material, selecting the
right elastomeric product for the application requires consideration of many factors,
including mechanical and physical service requirements, exposure to chemicals, operating
temperature, service life, manufacturability of the parts, and raw material and
manufacturing cost.

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 UNIT 4 : DEGRADATION AND FAILURE

Many materials are subjected to forces or loads when in service; examples include the
aluminum alloy from which an airplane wing is constructed and the steel in an automobile
axle. In such situations, it is necessary to know the characteristics of the material and to
design the member from which it is made such that any resulting deformation will not be
excessive and fracture will not occur. The mechanical behavior of a material reflects its
response or deformation in relation to an applied load or force. Key mechanical design
properties are stiffness, strength, hardness, ductility, and toughness.

4.1. CONCEPTS OF STRESS AND STRAIN

If a load is static or changes relatively slowly with time and is applied uniformly over a cross
section or surface of a member, the mechanical behavior may be ascertained by a simple
stress–strain test; these are most commonly conducted for metals at room temperature.
There are three principal ways in which a load may be applied: namely, tension,
compression, and shear (Figures a, b, c). In engineering practice many loads are torsional
rather than pure shear; this type of loading is illustrated in below figure d.

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Tension Test
One of the most common mechanical stress–strain tests is performed in tension. As will be
seen, the tension test can be used to ascertain several mechanical properties of materials
that are important in design. A specimen is deformed, usually to fracture, with a gradually
increasing tensile load that is applied uniaxially along the long axis of a specimen. Normally,
the cross section is circular, but rectangular specimens are also used. Engineering stress 𝜎 is
defined by the relationship
𝐹
𝜎=
𝐴0
in which F is the instantaneous load applied perpendicular to the specimen cross section, in
units of newtons (N) or pounds force (lbf), and A0 is the original cross-sectional area before
any load is applied (m2 or in.2). The units of engineering stress (referred to subsequently as
just stress) are megapascals, MPa (SI) (where 1 MPa = 106 N/m 2), and pounds force per
square inch, psi. Engineering strain 𝜀 is defined according to

𝑙𝑖 − 𝑙0 𝛥𝑙
𝜀= =
𝑙0 𝑙0
in which l0 is the original length before any load is applied and li is the instantaneous length.
Sometimes the quantity li − l0 is denoted as Δl and is the deformation elongation or change
in length at some instant, as referenced to the original length. Engineering strain
(subsequently called just strain) is unitless, but meters per meter or inches per inch is often
used; the value of strain is obviously independent of the unit system. Sometimes strain is
also expressed as a percentage, in which the strain value is multiplied by 100.
Compression Tests
Compression stress–strain tests may be conducted if in-service forces are of this type. A
compression test is conducted in a manner similar to the tensile test, except that the force is
compressive and the specimen contracts along the direction of the stress. Equations given in
above section are utilized to compute compressive stress and strain, respectively. By
convention, a compressive force is taken to be negative, which yields a negative stress.
Furthermore, because l0 is greater than li, compressive strains are necessarily also negative.
Tensile tests are more common because they are easier to perform; also, for most materials
used in structural applications, very little additional information is obtained from
compressive tests. Compressive tests are used when a material’s behavior under large and
permanent (i.e., plastic) strains is desired, as in manufacturing applications, or when the
material is brittle in tension.
Shear and Torsional Tests
The shear stress 𝜏 is computed according to
𝐹
𝜏=
𝐴0

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where F is the load or force imposed parallel to the upper and lower faces, each of which has
an area of A0. The shear strain 𝛾 is defined as the tangent of the strain angle 𝜃, as indicated
in the figure.

The units for shear stress and strain are the same as for their tensile counterparts. Torsion
is a variation of pure shear in which a structural member is twisted; torsional forces produce
a rotational motion about the longitudinal axis of one end of the member relative to the other
end. Examples of torsion are found for machine axles and drive shafts as well as for twist
drills. Torsional tests are normally performed on cylindrical solid shafts or tubes. A shear
stress 𝜏 is a function of the applied torque T, whereas shear strain 𝛾 is related to the angle of
twist, 𝜙.

4.2. ELASTIC DEFORMATION

The degree to which a structure deforms or strains depends on the magnitude of an imposed
stress. For most metals that are stressed in tension and at relatively low levels, stress and
strain are proportional to each other through the relationship

𝜎 = E𝜀
This is known as Hooke’s law, and the constant of proportionality E (GPa or psi) is the
modulus of elasticity, or Young’s modulus. For most typical metals, the magnitude of this
modulus ranges between 45 GPa (6.5 × 106 psi), for magnesium, and 407 GPa (59 × 106 psi),
for tungsten. Modulus of elasticity values for several metals at room temperature are
presented in below table.

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Deformation in which stress and strain are proportional is called elastic deformation; a plot
of stress (ordinate) versus strain (abscissa) results in a linear relationship, as shown in
below figure. The slope of this linear segment corresponds to the modulus of elasticity E.
This modulus may be thought of as stiffness, or a material’s resistance to elastic deformation.
The greater the modulus, the stiffer the material, or the smaller the elastic strain that results
from the application of a given stress. The modulus is an important design parameter for
computing elastic deflections.
Elastic deformation is nonpermanent, which means that when the applied load is released,
the piece returns to its original shape. As shown in the stress–strain plot, application of the
load corresponds to moving from the origin up and along the straight line. Upon release of
the load, the line is traversed in the opposite direction, back to the origin.

4.3. PLASTIC DEFORMATION

For most metallic materials, elastic deformation persists only to strains of about 0.005. As
the material is deformed beyond this point, the stress is no longer proportional to strain),
and permanent, nonrecoverable, or plastic deformation occurs. Below figure 6.10a plots
schematically the tensile stress–strain behavior into the plastic region for a typical metal.
The transition from elastic to plastic is a gradual one for most metals; some curvature results
at the onset of plastic deformation, which increases more rapidly with rising stress.
From an atomic perspective, plastic deformation corresponds to the breakingof bonds with
original atom neighbors and then the re-forming of bonds with new neighbors as large
numbers of atoms or molecules move relative to one another; upon removal of the stress,
they do not return to their original positions. The mechanism of this deformation is different
for crystalline and amorphous materials. For crystalline solids, deformation is accomplished
by means of a process called slip, which involves the motion of dislocations. Plastic
deformation in noncrystalline solids (as well as liquids) occurs by a viscous flow mechanism.

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4.3.1. DISLOCATIONS
Edge and screw are the two fundamental dislocation types. In an edge dislocation, localized
lattice distortion exists along the end of an extra half-plane of atoms, which also defines the
dislocation line. A screw dislocation may be thought of as resulting from shear distortion; its
dislocation line passes through the center of a spiral, atomic plane ramp. Many dislocations
in crystalline materials have both edge and screw components; these are mixed dislocations.
Plastic deformation corresponds to the motion of large numbers of dislocations.
An edge dislocation moves in response to a shear stress applied in a direction
perpendicular to its line; the mechanics of dislocation motion are represented in below
figure. The process by which plastic deformation is produced by dislocation motion is
termed slip; the crystallographic plane along which the dislocation line traverses is the slip
plane. Macroscopic plastic deformation simply corresponds to permanent deformation that
results from the movement of dislocations, or slip, in response to an applied shear stress.

The motion of a screw dislocation in response to the applied shear stress is shown in below
figure; the direction of movement is perpendicular to the stress direction. For an edge,
motion is parallel to the shear stress. However, the net plastic deformation for the motion of
both dislocation types is the same. The direction of motion of the mixed dislocation line is
neither perpendicular nor parallel to the applied stress, but lies somewhere in between.
All metals and alloys contain some dislocations that were introduced during solidification,
during plastic deformation, and as a consequence of thermal stresses that result from rapid
cooling. The number of dislocations, or dislocation density in a material, is expressed as the
total dislocation length per unit volume or, equivalently, the number of dislocations that

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intersect a unit area of a random section. The units of dislocation density are millimeters of
dislocation per cubic millimeter or just per square millimeter. Dislocation densities as low
as 103 mm−2 are typically found in carefully solidified metal crystals. For heavily deformed
metals, the density may run as high as 10 9 to 1010 mm−2. Heat-treating a deformed metal
specimen can diminish the density to on the order of 105 to 106 mm−2. By way of contrast, a
typical dislocation density for ceramic materials is between 102 and 104 mm−2; for silicon
single crystals used in integrated circuits, the value normally lies between 0.1 and 1 mm−2.

4.4. FAILURE
The failure of engineering materials is almost always an undesirable event for several
reasons; these include putting human lives in jeopardy, causing economic losses, and
interfering with the availability of products and services. Even though the causes of failure
and the behavior of materials may be known, prevention of failures is difficult to guarantee.
The usual causes are improper materials selection and processing and inadequate design of
the component or its misuse. Also, damage can occur to structural parts during service, and
regular inspection and repair or replacement are critical to safe design. It is the
responsibility of the engineer to anticipate and plan for possible failure and, in the event that
failure does occur, to assess its cause and then take appropriate preventive measures against
future incidents.

4.4.1. SIMPLE FRACTURE

Simple fracture is the separation of a body into two or more pieces in response to an imposed
stress that is static (i.e., constant or slowly changing with time) and at temperatures that are
low relative to the melting temperature of the material. Fracture can also occur from fatigue
(when cyclic stresses are imposed) and creep (time-dependent deformation, normally at
elevated temperatures); Although applied stresses may be tensile, compressive, shear, or
torsional (or combinations of these), the present discussion will be confined to fractures that
result from uniaxial tensile loads. For metals, two fracture modes are possible: ductile and
brittle. Classification is based on the ability of a material to experience plastic deformation.
Ductile metals typically exhibit substantial plastic deformation with high energy absorption
before fracture. However, there is normally little or no plastic deformation with low energy
absorption accompanying a brittle fracture.
Ductile and brittle are relative terms; whether a particular fracture is one mode or the other
depends on the situation. Any fracture process involves two steps—crack formation and

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propagation—in response to an imposed stress. The mode of fracture is highly dependent
on the mechanism of crack propagation. Ductile fracture is characterized by extensive plastic
deformation in the vicinity of an advancing crack. The process proceeds relatively slowly as
the crack length is extended. Such a crack is often said to be stable—that is, it resists any
further extension unless there is an increase in the applied stress. In addition, there typicall
is evidence of appreciable gross deformation at the fracture surfaces (e.g., twisting and
tearing). However, for brittle fracture, cracks may spread extremely rapidly, with very little
accompanying plastic deformation. Such cracks may be said to be unstable,and crack
propagation, once started, continues spontaneously without an increase in magnitude of the
applied stress. Ductile fracture is almost always preferred to brittle fracture for two reasons:
First, brittle fracture occurs suddenly and catastrophically without any warning; this is a
consequence of the spontaneous and rapid crack propagation. By contrast, in ductile
fracture, the presence of plastic deformation gives warning that failure is imminent, allowing
preventive measures to be taken. Second, more strain energy is required to induce ductile
fracture inasmuch as these materials are generally tougher. Under the action of an applied
tensile stress, many metal alloys are ductile, whereas ceramics are typically brittle, and
polymers may exhibit a range of behaviors.

Figure: (a) Highly ductile fracture in which the specimen necks down to a point. (b) Moderately ductile
fracture after some necking. (c) Brittle fracture without any plastic deformation.

4.4.2. FATIGUE
Fatigue is a form of failure that occurs in structures subjected to dynamic and fluctuating
stresses (e.g., bridges, aircraft, machine components). Under these circumstances, it is
possible for failure to occur at a stress level considerably lower than the tensile or yield
strength for a static load. The term fatigue is used because this type of failure normally occurs
after a lengthy period of repeated stress or strain cycling. Fatigue is important in as much as
it is the single largest cause of failure in metals, estimated to be involved inapproximately
90% of all metallic failures; polymers and ceramics (except for glasses) are also susceptible
to this type of failure. Furthermore, fatigue is catastrophic and insidious, occurring very

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suddenly and without warning. Fatigue failure is brittle-like in nature even in normally
ductile metals in that there is very little, if any, gross plastic deformation associated with
failure. The process occurs by the initiation and propagation of cracks, and typically the
fracture surface is perpendicular to the direction of an applied tensile stress.
The process of fatigue failure is characterized by three distinct steps: (1) crack initiation, in
which a small crack forms at some point of high stress concentration; (2) crack propagation,
during which this crack advances incrementally with each stress cycle; and (3) final failure,
which occurs very rapidly once the advancing crack has reached a critical size. Cracks
associated with fatigue failure almost always initiate (or nucleate) on the surface of a
component at some point of stress concentration. Crack nucleation sites include surface
scratches, sharp fillets, keyways, threads, dents, and the like. In addition, cyclic loading can
produce microscopic surface discontinuities resulting from dislocation slip steps that may
also act as stress raisers and therefore as crack initiation sites. The region of a fracture
surface that formed during the crack propagation step may be characterized by two types of
markings termed beachmarks and striations. Both features indicate the position of the crack
tip at some point in time and appear as concentric ridges that expand away from the crack
initiation site(s), frequently in a circular or semicircular pattern. Beachmarks (sometimes
also called clamshell marks) are of macroscopic dimensions, and may be observed with the
unaided eye. These markings are found for components that experienced interruptions
during the crack propagation stage—for example, a machine that operated only during
normal workshift hours. Each beachmark band represents a period of time over which crack
growth occurred.

4.4.3. CREEP
Materials are often placed in service at elevated temperatures and exposed to static
mechanical stresses (e.g., turbine rotors in jet engines and steam generators that experience
centrifugal stresses; high-pressure steam lines). Deformation under such circumstances is
termed creep. Defined as the time-dependent and permanent deformation of materials when
subjected to a constant load or stress, creep is normally an undesirable phenomenon and is
often the limiting factor in the lifetime of a part. It is observed in all materials types; for
metals, it becomes important only for temperatures greater than about 0.4Tm, where Tm is
the absolute melting temperature. Amorphous polymers, which include plastics and rubbers,
are especially sensitive to creep deformation.
A typical creep test consists of subjecting a specimen to a constant load or stress while
maintaining the temperature constant; deformation or strain is measured and plotted as a
function of elapsed time. Most tests are the constant-load type, which yield information of an
engineering nature; constant-stress tests are employed to provide a better understanding of
the mechanisms of creep.
Below figure is a schematic representation of the typical constant-load creep behaviour of
metals. Upon application of the load, there is an instantaneous deformation, as indicated in
the figure, that is totally elastic. The resulting creep curve consists of three regions, each of
which has its own distinctive strain–time feature.

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Primary or transient creep occurs first, typified by a continuously decreasing creep rate—
that is, the slope of the curve decreases with time. This suggests that the material is
experiencing an increase in creep resistance or strain hardening, deformation becomes more
difficult as the material is strained. For secondary creep, sometimes termed steady-state
creep, the rate is constant—that is, the plot becomes linear. This is often the stage of creep
that is of the longest duration. The constancy of creep rate is explained on the basis of a
balance between the competing processes of strain hardening and recovery, recovery being
the process by which a material becomes softer and retains its ability to experience
deformation. Finally, for tertiary creep, there is an acceleration of the rate and ultimate
failure. This failure is frequently termed rupture and results from microstructural and/or
metallurgical changes—for example, grain boundary separation, and the formation of
internal cracks, cavities, and voids. Also, for tensile loads, a neck may form at some point
within the deformation region. These all lead to a decrease in the effective cross-sectional
area and an increase in strain rate.

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 UNIT 5 : PROPERTIES OF MATERIALS

In determining the fabrication and possible practical applications, the mechanical properties
of materials, their strength, rigidity and ductility are of vital importance. The important
mechanical properties of materials are: elasticity, plasticity, strength, ductility, hardness,
brittleness, toughness, stiffness, resilience, malleability, fatigue, creep, etc. Materials exhibit
a wide range of mechanical properties ranging, e.g., from the ductility of pure copper to the
hardness of diamond and most surprising elastic behaviour of rubber. There are several
materials behave quite differently when stressed in different ways, e.g. steel and wood are
stronger in tension whereas cast iron, cement and bricks are much stronger in compression.
Obviously, stresses can produce a shape change and may also cause a material to break or
fracture. For materials which have to withstand high temperatures, the melting point is also
of importance. The combination of high yield strength and good fracture toughness or
ductility makes steel an excellent structural material. Modern high strength low alloy (HSLA)
steels have a very fine grain size around 10 micro-meters which provides both high strength
and good crack growth resistance or fracture toughness.

5.1. THERMAL PROPERTIES

The kinetic model of matter can be used to explain the structure of solids, liquids and
gases. This model is based on the following suggestions:
 Matter is formed of particles
 The particles can move
 The particles experience intermolecular forces
Most substances experience 3 distinct phases, which are determined by the energy of
the substance. These phases are solid, liquid and gas, and can be explained using the
kinetic model as below:
 Solid - Particles are fixed but can vibrate since the intermolecular forces are large.
Particles are very close together.
 Liquid - Particles have more energy, are much more free to move and are further
apart than in a solid. Intermolecular forces are smaller than in a solid but still relatively
large.
 Gas - Particles are much further apart and can move even more freely since th
intermolecular forces are very weak. Particles have more energy than in a liquid

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The internal energy of a body is equal to the sum of all of the kinetic energies and potential
energies of all its particles. The kinetic and potential energies of a body are randomly
distributed. When the state of a substance is changed, its internal energy also changes. This
is because the potential energy of the system changes, whilst the kinetic energy of the system
is kept constant. This can be demonstrated by measuring the temperature of water as it boils
and melts:
 Boiling: The temperature increases up until 100°C, after which the energy gained through
heating the water is no longer used to increase the temperature (and therefore kinetic
energy), but instead is used to break bonds between water molecules so it can change
state to water vapour, and so the potential energy is increased.
 Melting: The temperature of ice increases up until 0°C, after which the energy gained
through heating the water is no longer used to increase the temperature, but instead is
used to break bonds between water molecules so it can change state to liquid water, and
so the potential energy is increased.
Below is a graph showing how the internal energy of a substance varies with temperature:

The specific heat capacity of a substance is the amount of energy required to increase the
temperature of 1 kg of a substance by 1 °C/1 K, without changing its state. You can measure
the amount of energy required to change the temperature of a substance using the following
formula:
Q = mcΔθ
Where Q is energy required, m is the mass, c is the specific heat capacity, θΔ and is the change
in temperature. The specific latent heat of a substance is the amount of energy required to
change the state of 1 kg of material, without changing its temperature. There are two types
of specific latent heat: the specific latent heat of fusion (when solid changes to liquid) and
specific latent heat of vaporisation (when liquid changes to gas).
The amount of energy required to change the state of a substance can be measured using the
following formula:
Q = ml
Where Q is energy required and l is the specific latent heat.

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The specific latent heat of vaporisation is usually larger than the specific latent heat of fusion
of the same substance as more intermolecular bonds must be broken (so more work must
be done) to change a substance from a liquid to a gas, than when changing from a solid to a
liquid.
As mentioned above, the kinetic energies of particles in a liquid will be random and once a
particle in a liquid gains enough energy, it will leave the liquid and evaporate, leaving behind
particles with lower kinetic energies. Therefore the kinetic energy of particles decreases and
as kinetic energy is proportional to temperature, the temperature of the liquid will decrease.
The specific heat capacity (c) of a material can be calculated by:
 Measuring the mass of the material that will be heated (m) using a top-pan balance
 Measuring the energy input into the material (Q) by calculating the power input by the
heater (using values of voltage and current) and multiplying this by the time it is turned
on
 Calculating the temperature change (Δθ) by finding the difference between the initial and
final temperatures
And then using the following formula:
𝑄
C=
𝑚Δθ

The calculated specific heat capacity will be larger than the actual value due to energy losses
to the environment through resistance in the wires in the circuit, and heat being radiated
away from the material. Energy losses to the environment can be decreased by insulating the
material.
Thermal Expansion:
Thermal expansion arises from the addition of heat energy in the atoms and their subsequent
movement away from their equilibrium positions as the temperature rises in solid. This
expansion or contraction resulting from increase or decrease in temperature is three
dimensional but in practice linear thermal expansion is used for simplicity instead of volume
expansion. The increase in length per unit length per degree rise in temperature is called
coefficient of linear expansion. Thermal expansion does not necessarily vary uniformly with
temperature but it is sufficiently linear over narrow ranges of temperature.
If the bonds between the atoms are strong and highly directional as in ionic and covalent
solids, the thermal expansion will be relatively small. If on the other hand the atoms are more
loosely bound as in metals, a greater degree of expansion is there. In molecular solid, where
bonding least resists the movement of the molecules, the thermal expansion will be the
greatest. The thermal expansion of solid is related to other thermal properties such as
specific heat and melting point as all these properties have their origin in lattice vibrations
which increase with the temperature. The atoms or molecules as earlier explained oscillate
(vibrate) with a certain amplitude about their equilibrium positions.

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The amplitude of this vibration increases as the temperature rises resulting in moving
further away of atoms and molecules from their equilibrium position causing an increase in
volume (or linear expansion) of solid. In this way magnitude of the coefficient of thermal
expansion of solids will depend on their interatomic and intermolecular forms and also on
their structural arrangement. It has been observed that between absolute zero temperature
and the melting point, total volume range of elements is approximately constant. This can be
interpreted that materials with lower softening (melting) points will have higher expansion
coefficients. This also means that thermal expansion will approach zero at the absolute zero
temperature. Organic polymers such as plastics and rubber have many times higher
expansion coefficients than metals because of their relatively lower softening point. This may
be reduced by addition of filler materials (such as glass fibre, asbestos, alumina etc.)
possessing lower thermal expansion coefficients. Alloying of metals have a minor effect on
this property.
Melting Point:
Melting point or softening point is a significant temperature level as it represents transition
point between solid and liquid phases having different structural arrangement of the atoms
within the material. As heat is added to a solid, its thermal energy increases until the atoms
or molecules on the surface begin to break away from their equilibrium positions. There is a
link between interatomic spacing at which the bonding force is maximum and the amplitude
of thermal vibration at which this breaking away occurs as if the atoms can be separated at
this point, no further increase in force is needed to separate them further. After melting
commences, any further heat is all used up in activating more particles of solids which in
turn collide with neighbouring particles transmitting their energy to them.
The structure is therefore transformed from a solid having definite equilibrium positions to
a liquid having only short range order. During melting no further rise in temperature occurs
and solid and liquid phases exist at the same temperature. Melting temperature depends
upon the amount of thermal energy required. This in turn depends on the nature of
interatomic and intermolecular bonds. Therefore higher melting point is exhibited by those
materials possessing stronger bonds. Covalent, ionic, metallic and molecular types of solids
have decreasing order of bonding strength and thus the melting points. Crystalline solids
have a sharp melting point at which there is sudden transformation from solids to liquid
states. Amorphous solids such as glasses, plastics and rubbers and also clays do not have
definite melting points but soften gradually over a certain temperature range.
Heat Resistance:
Melting point determines the heat resistance of a material as any material for high
temperature application should have its melting point above the service temperature.
Ceramic materials are known to have high melting points and good chemical stability but
they are difficult to fabricate and cannot take thermal or mechanical shock.
Thermal Shock:
Thermal shock is the effect of a sudden change of temperature on a material whereas thermal
shock resistance can be defined as the ability of material to withstand thermal stresses due
to sudden and severe changes in the temperature at the surface of a solid body.

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If a solid structure is prevented so that it cannot expand or contract freely on heating or
cooling, excessive thermal stresses may result culminating in thermal shock and causing
failure of the body. Thermal shock resulting from cooling which results in tensile stresses at
the surface is much more dangerous than that from heating.
Thermal Diffusivity:
Thermal diffusivity (h) is defined as

cp ρ represent heat requirement per unit volume. A material having high heat requirement
per unit volume possesses a low thermal diffusivity because more heat must be added to or
removed from the material for affecting a temperature change. Thermal diffusivity is
therefore associated with the diffusion of thermal energy and may be taken to represent an
energy flux arising from the motion of phonons through a relatively stationary atomic array.
As phonons are in the nature of waveform, the atoms vibrate in unison but are not physically
transported.
Thermal Stresses:
When expansion or contraction of a body due to temperature change is wholly or partially
prevented, thermal stress will be developed in body. Thermal stress may arise from external
bodies connected to one under stress as for example, welded structure, railway line shrink
fit components. Or, it may be due to non-uniform expansion of the body itself, for example
bimetallic strips used in thermostatic controls. The value of thermal stress, expansion or
contraction can be calculated by applying simple stress calculation theory.
Thermo-Elastic Effect:
When a solid is subjected to a load, work is done on it and it changes in volume. If this work
is done at constant temperature, an adiabatic temperature rise (without transfer of heat to
or from the surroundings) occurs. This will appear in the form of rise of temperature of solid
when it is in stretched condition. Similarly when the solid is rapidly relaxed, -it will feel. cool.
This warming or cooling phenomenon is called thermoelastic effect.

5.2. MAGNETIC PROPERTIES

Magnetism has a very ancient history: it is one of the topics in which considerable
advances have been made, both in theoretical understanding and in experimental work, over
the last few decades. It is perhaps that aspect of solid state physics which has been familiar
to man as early as 800 BC. Infact, almost every thing known about the magnetic properties
has been derived from experimental work and from a few stimulated guesses.
Some of the important features of magnetic materials are listed below:
(i) Some materials are magnetic even without the application of any magnetic field and
become more magnetic when a weak magnetic field is applied to such materials.

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(ii) Several other materials lose their initially strong magnetism when heated above certain
critical temperature and become comparatively weakly magnetized.
(iii) Some materials show a magnetic response in a direction opposite to that of any
externally applied field.
The source of magnetism in solids is mainly due to the motion of the electrons and in
the permanent magnetic moments of the atoms and electrons. The application of a magnetic
field induces a change in the atomic orbital states causing the diamagnetic phenomena,
which is quite weak. On the other hand paramagnetism is the result of the presence of
permanent atomic or electronic magnetic moments. In this case the magnetic moments line
up with the magnetic field to decrease the total energy. In diamagnetism, there is slight
repulsion of a material by the magnetic field, where as in paramagnetism, there is a slight
attraction of a material by the magnetic field. However ferromagnetism occurs when
quantum mechanical exchange interaction align adjacent magnetic moments in the same
direction in the absence of a magnetic field below a critical temperature, called the curie
temperature. Above the curie temperature, the ferromagnetic materials become
paramagnetic. If the exchange interaction aligns the moments in opposite directions,
cancellation takes place and the material is known as an antiferromagnetic material. The
total moment over a finite volume is zero. The antiferromagnetism vanishes above a critical
temperature, called the Neel temperature. In ferromagnetism, the number of atoms with
opposite spins are unequal and hence there is a net magnetic moment. Below figure shows
the magnetic ordering ofthe different kinds of the said magnetic materials. The interesting
information is that ferro and ferromagnetic materials consist of domains of completely
magnetized regions, separated by boundaries.

Various types of magnetic ordering. Each arrow indicates a magnetic moment and its orientation
(a) Ferromagnetic (b) Anti Ferromagnetic (c) Ferrimagnetic

5.3. ELECTRICAL AND ELECTRONIC PROPERTIES

Materials are classified based on their electrical properties as conductors, semiconductors,
insulators and superconductors. n electric current results from the motion of electrically
charged particles in response to forces that act on them from an externally applied electric
field. Positively charged particles are accelerated in the field direction, negatively charged
particles in the direction opposite. Within most solid materials a current arises from the flow
of electrons, which is termed electronic conduction. In addition, for ionic materials a net
motion of charged ions is possible that produces a current; such is termed ionic conduction.
Energy Band Structures in Solids: In all conductors, semiconductors, and many insulating
materials, only electronic conduction exists, and the magnitude of the electrical conductivity

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is strongly dependent on the number of electrons available to participate in the conduction
process. For each individual atom there exist discrete energy levels that may be occupied by
electrons, arranged into shells and subshells.

Ohm’s Law
One of the most important electrical characteristics of a solid material is the ease with which
it transmits an electric current. Ohm’s law relates the current I—or time rate of charge
passage—to the applied voltage V as follows:
V= IR
where R is the resistance of the material through which the current is passing. The electrical
resistivity 𝜌 is independent of specimen geometry but related to R through the expression
𝑅𝐴
𝜌=
𝑙
where l is the distance between the two points at which the voltage is measured and A is the
cross-sectional area perpendicular to the direction of the current
Electrical conductivity 𝜎 is used to specify the electrical character of a material. It is simply
the reciprocal of the resistivity, or
1
𝜎=
ρ

and is indicative of the ease with which a material is capable of conducting an electric
current. The units for 𝜎 are reciprocal ohm-meters [(Ω·m)−1]. An electric current results from
the motion of electrically charged particles in response to forces that act on them from an
externally applied electric field. Positively charged particles are accelerated in the field
direction, negatively charged particles in the direction opposite. Within most solid materials
a current arises from the flow of electrons, which is termed electronic conduction. In
addition, for ionic materials, a net motion of charged ions is possible that produces a current;
this is termed ionic conduction.
At room temperature (say 300 K), the materials classified as semiconductors have
resistivity some where between that of a good conductor such as a metal and that of a typical
insulator. Fundamental difference between the three materials can be easily explained based
on energy band theory.
The resistivity of semiconductors greatly depends on the following factors,
remembering

i. As the temperature increases (in metals) scattering by phonons increases and hence
the mobility decreases. Hence in copper the resistivity increases as the temperature
increases assuming n (concentration or density of free electrons) remains fairly
constant over normal range of operating temperatures. Thus metals have a positive
temperature coefficient.

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 ii. (ii) But the temperature coefficient of resistance is negative in semiconductors. Here
as the temperature increases the number of charge carriers increases exponentially
which masks the decreasing effect of mobility. Hence in semiconductors resistivity
decreases as temperature increases. i.e. they have a negative temperature
coefficient.
iii. (iii) Resistivity in semiconductors decreases in brighter surroundings.
iv. (iv) Current in semiconductors does not obey Ohm’s law and increases rapidly than
voltage. i.e. semiconductors are non-linear resistors.
v. (v) Even a small trace of suitable chemical impurity added into pure semiconductors
may change the electrical properties many fold; even a change of mechanism of
conduction is possible.
The elemental semiconductors are germanium (Ge), silicon (Si), selenium (Se), grey
(crystalline) tin, tellurium (Te), boron, etc. A large number of compounds are also
semiconductors, like cuprous oxide (Cu2O), indium antimonide, bismuth telluride, etc.
Semiconductor materials and fabricated devices are used in many vital areas mainly because
of their small size and low operating voltage. They are used as rectifiers and transistors.
Semiconductors, whose resistance is temperature dependent are employed as thermistors;
if it is voltage dependent, the semiconductors may be used as a varistor, and if light
dependent, as a photoelectric device. Semiconductors are used in heating appliances, photo
cells, refrigerators, measuring instruments, automatic and remote control systems, etc.
Devices made out of p-n junction helped to replace the bulky valves operated at high
voltages. New devices coming up every year using semiconductors make significant
contributions right from animation work in computer engineering to reduction of weight in
space ships.

The band gap is 0 for metals (over lapping of conduction band and valence band) and
it is 6 eV for the insulator carbon in the diamond structure. Pure germanium and pure silicon
where electrons and holes are produced by phonons (thermal activation) or by photons of
suitable frequency are called intrinsic semiconductors. In the other type the charge carriers
are produced by the addition of suitable chemical impurities. Such semiconductors are called

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extrinsic semiconductors or impurity semiconductors. The impurities injected are called
dopants.
The valence band and the conduction band in a semiconductor are separated by a small
energy gap of the order of 1 eV. At 0 K the valence band is completely filled and the
conduction band is empty provided the semiconductor is pure and free from defects or
imperfections. Even if an electric field is established at this low temperature (0 K), the
electrons in the valence band cannot acquire additional energy as there are no unoccupied
energy states in the valence band to which the electrons can be raised. Thus there will be no
electric current and the solid will be an insulator. At high temperatures (can be even lower
than 300 K), a reasonable number of electrons in the valence band may acquire sufficient
energy and get excited into the conduction band (as the energy gap is small). They may also
acquire additional energy in an applied electric field. This gives rise to an electric current
and such solids are intrinsic semiconductors. If an electron in the completely filled valence
band of a semiconductor is removed from that band, a vacancy is left behind in that band
which is called a ‘hole’. Removal of electrons from the valence band is possible either by
thermal excitation (intrinsic one) or by adding dopants (impurity semiconductor). When a
vacancy is created in the valence band, a lower energy electron in the band may be excited
to the higher energy vacant level by an applied electric field. The hole then moves down to
the lower energy level. Since the hole moves in a direction opposite to that of the electron,
we can treat the hole as a positively charged particle. The energy of the hole increases when
it moves from a higher electronic level to a lower electronic level. Thus we conclude that the
hole gains energy in an applied electric field and to cause a current.

5.4. OPTICAL PROPERTIES

Optical property deals with the response of a material against exposure to electromagnetic
radiations, especially to visible light. When light falls on a material, several processes such
as reflection, refraction, absorption, scattering etc.
Refraction: When light photons are transmitted through a material, they causes polarization
of the electrons in the material and by interacting with the polarized materials, photons lose
some of their energy. As a result of this, the speed of light is reduced and the beam of light
changes direction.
Reflection: When a beam of photons strikes a material, some of the light is scattered at the
interface between that we media even if both are transparent. Reflectivity, R, is a measure of
fraction of incident light which is reflected at the interface.
Absorption: When a light beam is striked on a material surface, portion of the incident beam
that is not reflected by the material is either absorbed or transmitted through the material.
The fraction of beam that is absorbed is related to the thickness of the materials and the
manner in which the photons interact with the material’s structure.

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Rayleigh scattering: Here photon interacts with the electron orbiting around an atom and
is deflected without any change in photon energy. This is more vital for high atomic number
atoms and low photon energies. Ex. Blue colour in the sunlight gets scattered more than
other colors in the visible spectrum and thus making sky look blue.
Transmission: The fraction of beam that is not reflected or absorbed is transmitted through
the material. Thus the fraction of light that is transmitted through a transparent material
depends on the losses incurred by absorption and reflection. Thus,
R + A + T = 1,
where R = reflectivity, A = absorptivity, and T = transitivity.
Thermal Emission: When a material is heated electrons are excited to higher energy levels
generally in the outer energy levels where the electrons are less strongly bound to the
nucleus. These excited electrons, upon returning back to the ground state, release photons
in process termed as thermal emission. By measuring the intensity of a narrow band of the
emitted wavelengths with a pyrometer, material’s temperature can be estimated.
Electro-Optic Effect: The behaviour of a material in which its optical isotropic nature
changes to anisotropic nature on application of an electric field. This effect is seen in LiNbO3,
LiTiO3 etc.
Photoelectric Effect: Phenomenon in which the ejection of electrons from a metal surface
takes place, when the metal surface is illuminated by light or any other radiation of suitable
frequency (or wavelength). Several devices such as phototube, solar cell, fire alarm etc. work
on this effect (principle).
Photo Emissivity: Phenomenon of emission of electrons from a metal cathode, when
exposed to light or any other radiations.
Optical Properties of Non-Metals:
 These materials may be transparent, translucent, or opaque. Therefore, they exhibit
different optical properties such as reflection, refraction, absorption and transmission.
The phenomenon of refraction is more dominant in them.
 The non-metals which are transparent are generally coloured due to light absorption and
remission in the visible region by them. Absorption of light occurs due to: Electronic
polarization.
 Excitation of electrons from filled valence band to empty state within conduction band,
and Wide band gaps in dielectric materials.
 The non-metallic transparent materials transmit light due to net energy formed by
absorption and reflection processes.
Optical Properties of Metals:
 In metals, the valence band is partially filled and so there are large number of quasi
continuous vacant energy levels available within the valence band. When light is incident
on metals the valence electrons absorb all frequencies of visible light and get excited to

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 vacant states inside the valence band (intra-band transitions). This result in the opacity
of metals.
 The total absorption of light by the metal surface is within a very thin outer layer of less
than 0.1 jam. The excited electrons return back to lower energy states thereby causing
emission of radiation from the surface of the metal in the form of visible light of the same
wavelength. This emitted light which appears as the reflected light is the cause of the
lustrous appearance of metals.
 In copper, inter-band transitions occur for energies greater than 2.2 eV i.e. the photons
of energy greater than 2.2 eV are strongly absorbed. This energy corresponds to
wavelength below 5625 Å. This means that the radiation in the blue-violet range is
absorbed. This is reason for the reddish-orange colour of copper.
 In silver and aluminium, there is no absorption in the full range of visible radiation. So,
the re-emission occurs over the entire wavelength range of the visible spectrum due to
which the white colour of these metals exist.
 Gold appears yellow because there is absorption in green portion and reflection in yellow
and red region.
Optical Properties of Semiconductors:
 Intrinsic semiconductors at low temperatures have a completely filled valence band and
an empty conduction band. So no intra-band transitions can occur in semiconductors.
 Radiation of low frequencies, i.e. infrared radiation are not absorbed and that’s why
semiconductors are transparent to infra-red radiation.
 The energy gaps in semiconductors are in the range of 0.5 – 3eV. So inter-band absorption
occurs for radiation in this range which corresponds to near infra-red and visible range,
this is responsible for the opacity of semiconductors.
Luminescence:
Luminescence is the property by which a material emits the light. In semiconducting
materials, the light is emitted under certain conditions which are as below: (i) When
electron-hole pairs (EHP) are generated, or (ii) When the carriers fall to their equilibrium
state after being excited to higher impurity levels. There are various types of luminescence,
Photo-Luminescence: It is the phenomenon of emission of light from a semiconductor on
account of recombination of excited electron-hole pair (EHP). Here one photon is emitted
from each photon absorbed. Recombination in semiconductors takes place at varying rates;
fast and slow. Accordingly, the photo-luminescence may be of following two types:
a) Fluorescence: It is a fast process property of material in which the emission of photon
stops in about 10–8s after the excitation is removed.
Example:
(i) Glass surface coated with tungstates or silicates such as in fluorescent lamps.
(ii) Television screen coated with sulphides, oxides, tungstates etc.
b) Phosphorescence: Slow process property of material in which the emission of photon
continues for a longer duration, lasting for seconds and minutes after removal of
excitation. Materials falling in this category are termed as phosphors, example:

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 (i) ZnS coated with Cu an impurity
(ii) CdS coated with Ag as impurity
(iii) KCI coated with Tl as impurity
(iv) Nal coated with Tl as impurity
Example: ‘Fluorescent lamp’. It is a glass tube filled with a gas, which is generally the
mixture of mercury vapours and argon. The inside of the tube has a fluorescent
coating. When an electric discharge is induced between electrodes of the tube, the
atoms of the gas are excited and emit photons.
Electro-Luminescence: This effect can be created by introducing the electric current into a
semiconductor. The electrical current can be used in different ways to generate the photon
emission from semiconductors. One such way is ‘injection’. The name of the process is
injection electro-luminescence which is use in making light-emitting diodes (LEDs). In them
the minority carriers are injected by electric current, into the regions of a crystal where they
can recombine with majority carriers. It results in emission of recombination radiation. The
effect of electro-luminescence can be found in devices incorporating the phosphor powder
(such as of ZnS) in a plastic binder. This phosphor gives-off the light when an alternating
current (a.c.) filed is applied on it. Such device is known as ‘electro-luminescence cell’, which
is used as lighting panel.
Optical Properties of Insulators:
 Insulators have completely filled valence band and so like as in semiconductors, no intra-
band transitions can occur.
 The energy gap in insulators are greater than 5 eV and so no inter-band transition can
occur in the visible range of radiation.
 Absorption occurs only for the ultraviolent radiation. Insulators are transparent from
infra-red up to the ultra-violet radiation.
Examples:
a) Perfect diamond crystal
b) Fused quartz
c) Window glass
Non-Transparent Insulator:
a) Enamels,
b) Porcelains,
c) Opal glass etc.

 Above materials are opaque because the incident radiation gets scattered in all direction
by the small particles present in these materials.
 Due to this, there cannot be perfect transmission. Part of the radiation is diffusely
transmitted and part is diffusely reflected. This makes the materials appear opaque.
 If the particle size is of the order of the wavelength of visible radiation, there will be
maximum scattering.
 For some applications, such particles are deliberately introduced in dielectrics to make
them opaque.

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 UNIT 6 : NANOTECHNOLOGY

6.1. INTRODUCTION
Nanotechnology is defined as the study, design, construction and utilization of functional
structures between 1 nanometer and 100 nanometers in size, and involves developing
materials or devices within that size. Nanotechnology is an umbrella term that encompasses
all fields of science that operate on the nanoscale. Nanotechnology is an extremely diverse
and multidisciplinary field, ranging from novel extensions of conventional device physics, to
completely new approaches based upon molecular self-assembly, to developing new
materials with dimensions on the nanoscale, even to speculation on whether we can directly
control matter on the atomic scale. Nanotechnology has the potential to create many new
materials and devices with wide-ranging applications, such as in medicine, electronics, and
energy production. One nanometer (nm) is one billionth, or 10-9 of a meter. For comparison
purposes, the width of an average hair is 100,000 nanometers. Human blood cells are 2,000
to 5,000 nm long, a strand of DNA has a diameter of 2.5 nm, and a line of ten hydrogen atoms
is 1 nm.

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 Before going the various concepts of nanotechnology, I will introduce you to the various
commercial nanotechnology based products. One example is the Samsung air conditioner,
containing silver nanoparticles. The silver nanoparticles are proven to have antimicrobial
effect and purifies the air. Nano paints have self-cleaning properties, they can degrade the
dust particles by themselves. Ujala Techno Bright washing powder contains nano enzymes,
which can be able to wash the clothes more effectively.

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 Everyone talks about nanotechnology, people who manufacture air conditioners, paints,
washing powder, people who wants destroy world and those who want to save the world.
Why everyone is so much interested in nanotechnology?
Why there is so much hype about nanotechnology?

6.2. WHAT MAKES NANOTECHNOLOGY SPECIAL?

There are two factors that attract the interest of everybody towards nanotechnology.
Factor 1: Increase in Surface Area
Surface area is defined as the outside part or uppermost layer of something. Every
material shows reactivity/properties mainly on their surface. So, what happens when the
surface area is increased? It can be given with a simple example of cooking a potato.
How do we cook a potato? We first wash it, then cut it and boil it.

Why do we want to cut the potates? Why can it be boiled as a whole?

Because if we boil it as a whole it will take long time to boil or the center part remains
uncooked. So, when we cut the potato, the potato cooks faster. This is because, when we cut
the potato, the surface area of the potato that contacts the boiling water is increased. All the
inner areas are also exposed. If we can improve the speed of the cooking process just by
cutting the potatoes into macro pieces, imagine how fast we can cook if we can cut the potato
into nano size. The potatoes can be cooked in fraction of seconds.
This is the effect of increase in the surface area. Similarly, the effectiveness and efficiency
of any process can be improved by converting the materials into nano size.
Factor 2: Change in Properties
The second factor is change in properties. When we convert the materials into nano size
they are exhibiting different properties. For example, we all know the color of gold, but when
we make the gold into gold nanoparticles, they exhibit different colors red, purple, blue, etc.

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Similarly, carbon is very poor conductor at macro size, but the Carbon Nano Tube (CNT) is
an excellent conductor. Copper is the best known conductor, which is used in all wirings. But,
CNT conducts electricity 10 times faster than copper.
Just by converting the materials from macro size to nano size, normal materials are
behaving with extraordinary properties.

(a)

(b)

Figure: Comparison of a) Macro gold with b) Gold nanoparticles of different size

But why do materials do like that, why a material which is yellow in color, changes its
color to red or blue when they change to nano size. We are not changing anything, we are not
converting or mixing anything with gold, we are just reducing its size.

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 It can be explained with a simple example, imagine a class room full of students with a
teacher standing in front, the behavior of the students will be very ordered and polite. Now,
if the teacher goes out, the order is lost. Imagine a group of students (friends) sitting in the
class, do they be same as they were in the class full of students? Definitely not. Still, if I reduce
the number of big group to a small group of close friends, do you still behave in the similar
manner? NO.
Why the same person (who’s having one character) behaves differently in different
situations. Why cannot the person be same in all the four situations?
When a person moves from the first place to the fourth, the factors influencing the
persons behavior is reducing i.e. the number of people are reduced. So when the number of
people around a person is reduced, the person start to behave in different manner. When he
is the fourth place (when he is with a small group of close friends), the influence is very
minimum, so there only he show his original inner nature.
Similarly, when we take one gram of gold (or any other material), there will be one
million atoms, so each atom is under the influence of 1 million atoms. An atom does not have
the freedom to react individually, it should react collectively with other one million atoms.
Imagine yourself in a big auditorium with thousands of people gathered for a comedy show,
If someone tell as joke in the stage, and everyone laugh at the joke. But here don’t like the
joke at all, what will you do, will you simple sit without lauging, not possible. You will also
laugh with everybody, even if you don’t like it. This is what will happen, when an atom is
surrounded by one million atoms.
But when we reduce it to nano size, there will be only thousand atoms, it’s like you are
with small group of friends. The atoms are free to exhibit their own nature (i.e. the true
nature). This can also be explained with the concept of QUANTUM CONFINEMENT, which
will covered in the later part of this notes.
Now, we all understand, why nanotechnology is so special?
1. Increase in surface area: drastically improving the efficiency of any process
2. Change in properties at nano size: provide new technologies and open up new
possibilities for exploration

First of all why we need these new properties, because we have lot of unsolved problems
in the world. These problems cannot be solved by existing material properties. For example,
if we transmit 1000 Mega Watts of electricity from an electricity production which is 500
Miles away to the city, we will lose nearly 200 Megawatts due to transmission losses. As we
are using aluminum cables, the resistance in the cables tend to lose electric power while
transmission. What is we can reduce this resistance? By blending the CNT with aluminium,
then we can save the power due to transmission loss. We are producing more power and
wasting the nature’s energy resource, but we are gaining more electric power just by
preventing the loss. Aluminium wire could not do this, but nanomaterials can do it, similarly,

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there are variety of unsolved problems, which could not be solved with existing material
properties, but nanomaterials can provide new avenues for solving the global problems.

History
Nanotechnology is new, but research on nanometer scale is not new at all. The study of
biological systems and the engineering of many materials such as colloidal dispersions,
metallic quantum dots, and catalysts have been in the nanometer regime for centuries.
Metallic gold, when divided into fine particles ranging from sizes of 10–500 nm particles, can
be suspended in water. In the Indian medical system called Ayurveda, gold is used in several
preparations. One popular preparation is called ‘Saraswatharishtam’, prescribed for
memory enhancement. Gold is also added in certain medicinal preparations for babies, in
order to enhance their mental capability. All these preparations use finely ground gold.
Indians also used Gold / Silver nanoparticles, in the name of ‘Bhasma’ dating back form
5000 BCE (Swarna Bhasma means Gold nanoparticles and Rajata Bhasma means silver
nanoparticles). These bhasmas are proven to be very effective against lot of alignments
including arthritis. The Chinese are known to use gold nanoparticles as an inorganic dye to
introduce red color into their ceramic porcelains more than thousand years ago. Romans,
Lycurgus Cup is another example, whereby gold nanoparticles present in the glass cause this
ancient object to change colour when subjected to different angles of light.
Use of colloidal gold has a long history, though a comprehensive study on the preparation
and properties of colloidal gold was first published in the middle of the 19 th century. Colloidal
dispersion of gold prepared by Faraday in 1857, was stable for almost a century before being
destroyed during World War II. A number of diseases were diagnosed by the interaction of

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colloidal gold with spinal fluids obtained from the patient. In 1890, the German bacteriologist
Robert Koch found that compounds made with gold inhibited the growth of bacteria. He won
the Nobel prize for medicine in 1905.

Figure: Lycurgus Cup

Nanotechnology was first introduced to the modern scientists in 1959, in a talk by the
Nobel Prize-winning physicist, entitled "There's Plenty of Room at the Bottom". Richard
Feynman proposed using a set of conventional-sized robot arms to construct a replica of
themselves, but one-tenth the original size, then using that new set of arms to manufacture
an even smaller set, and so on, until the molecular scale is reached. If we had many millions
or billions of such molecular-scale arms (This was presented in the movie Transcendence),
we could program them to work together to create macro-scale products built from
individual molecules — a "bottom-up manufacturing" technique, as opposed to the usual
technique of cutting away material until you have a completed component or product —
"top-down manufacturing". But only in 1986, K. Eric Drexler wrote "Engines of Creation" and
introduced the term nanotechnology.
Scientific research really expanded over the last decade. Inventors and corporations
aren't far behind -- today, more than 13,000 patents registered with the U.S. Patent Office
have the word "nano" in them.

Richard Feynman K. Eric Drexler

What has changed recently is an explosion in our ability to image, engineer and
manipulate systems in the nanometer scale. What is really new about nanotechnology is the
combination of our ability to see and manipulate matter on the nanoscale and our
understanding of atomic scale interactions. With the development of highly powered

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microscopes (the scanning electron microscope and the transmission electron microscope,
later the atomic force microscope and the scanning tunneling microscope) and an ever-
growing knowledge of the physical interactions of molecules and atoms, the concept of
nanotechnology has become a material reality. Although study on materials in the
nanometer scale can be traced back for centuries, the current fever of nanotechnology is at
least partly driven by the continuous shrinking of the electronic devices in the
semiconductor industry and supported by the availability of characterization and
manipulation techniques at the nanometer level.
Nano in Nature: Nature makes nano objects of varying kind. Magnetite (Fe3O4) particles of
nanometer size are made by the bacteria, Magnetosperillum magnetotacticum. These
bacteria make particles of specific morphology. For a bacterium, the magnetism caused by
the particles helps in finding a direction favourable for its growth. There are several bacteria
like the familiar Lactobacillus which can take up metal ions added into buttermilk, and
reduce them inside the cell and make nanoparticles.

6.3. CLASSIFICATION AND PROPERTIES

6.3.1. CLASSIFICATION OF NANOMATERIALS

The nanomaterials are primarily classified based on the number of dimensions of a
material, which are outside the nanoscale (<100 nm) range. Accordingly,
 Zero-dimensional nanomaterials (0D): all the dimensions are measured within the
nanoscale (no dimensions are larger than 100 nm). Most commonly, 0D nanomaterials
are quantum dots.
 One-dimensional nanomaterials (1D): one dimension is outside the nanoscale. This
class includes nanotubes, nanorods and nanowires.
 Two-dimensional nanomaterials (2D): two dimensions are outside the nanoscale.
This class exhibits plate-like shapes and includes graphene, nanofilms, nano layers and
nano coatings.
 Three-dimensional nanomaterials (3D): are materials that are not confined to the
nanoscale in any dimension. This class can contain nano powders and dispersions of
nanoparticles.

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 Figure: Classification of Nanomaterials based on dimensional confinement

6.3.2. QUANTUM CONFINEMENT

Quantum confinement is change of electronic and optical properties when the material
sampled is of sufficiently small size - typically 10 nanometers or less. The bandgap increases
as the size of the nanostructure decreases. Specifically, the phenomenon results from
electrons and holes being squeezed into a dimension that approaches a critical quantum
measurement, called the exciton Bohr raduis. The quantum confinement effect is observed
when the size of the particle is too small to be comparable to the wavelength of the electron.
To understand this effect we break the words like quantum and confinement, the word
confinement means to confine the motion of randomly moving electron to restrict its motion
in specific energy levels (discreteness) and quantum reflects the atomic realm of particles.
So as the size of a particle decrease till we reach a nano scale, the decrease in confining
dimension makes the energy levels discrete and this increases or widens up the band gap
and ultimately the band gap energy also increases.

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 On the other hand, the nanoparticles can also be classified into the organic, inorganic and
carbon based.

Organic Nanoparticles: Dendrimers, micelles, liposomes and ferritin, etc. are commonly
knows the organic nanoparticles or polymers. These nanoparticles are biodegradable, non-
toxic, and some particles such as micelles and liposomes has a hollow core, also known as
nanocapsules and are sensitive to thermal and electromagnetic radiation such as heat and
light. These unique characteristics makes them an ideal choice for drug delivery. The drug
carrying capacity, its stability and delivery systems, either entrapped drug or adsorbed drug
system determines their field of applications and their efficiency apart from their normal
characteristics such as the size, composition, surface morphology, etc. The organic
nanoparticles are most widely used in the biomedical field for example drug delivery system
as they are efficient and also can be injected on specific parts of the body that is also known
as targeted drug delivery.

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 Figure: Organic nanoparticles: a) Dendrimers, b) Liposomes and c) Micelles.

Inorganic Nanoparticles: Inorganic nanoparticles are particles that are not made up of
carbon. Metal and metal oxide based nanoparticles are generally categorized as inorganic
nanoparticles
Metal based Nanoparticles that are synthesized from metals to nano metric sizes either by
destructive or constructive methods are metal based nanoparticles. Almost all the metals can
be synthesized into their nanoparticles. The commonly used metals for nanoparticle
synthesis are aluminium (Al), cadmium (Cd), cobalt (Co), copper (Cu), gold (Au), iron (Fe),
lead (Pb), silver (Ag) and zinc (Zn). The nanoparticles have distinctive properties such sizes
as low as 10 to 100nm, surface characteristics like high surface area to volume ratio, pore
size, surface charge and surface charge density, crystalline and amorphous structures,
shapes like spherical and cylindrical and colour, reactivity and sensitivity to environmental
factors such as air, moisture, heat and sunlight etc.
Metal oxides based nanoparticles are synthesized to modify the properties of their
respective metal based nanoparticles, for example nanoparticles of iron (Fe) instantly
oxidises to iron oxide (Fe2O3) in the presence of oxygen at room temperature that increases
its reactivity compared to iron nanoparticles. Metal oxide nanoparticles are synthesized
mainly due to their increased reactivity and efficiency. The commonly synthesized are
Aluminium oxide (Al2O3), Cerium oxide (CeO2), Iron oxide (Fe2O3), Magnetite (Fe3O4), Silicon
dioxide (SiO2), Titanium oxide (TiO2), Zinc oxide (ZnO). These nanoparticles have possess an
exceptional properties when compared to their metal counterparts.

Carbon based: The nanoparticles made completely of carbon are knows as carbon based.
They can be classified into fullerenes, graphene, carbon nano tubes (CNT), carbon nanofibers
and carbon black and sometimes activated carbon in nano size and are presented in Figure.

Figure: Carbon based nanoparticles: a) fullerenes, b) graphene, c) carbon nanotubes,

d)carbon nano fibers and e)carbon black

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Fullerenes (C60) is a carbon molecule that is spherical in shape and made up of carbon
atoms held together by sp2 hybridization. About 28 to 1500 carbon atoms forms the
spherical structure with diameters up to 8.2 nm for a single layer and 4 to 36 nm for multi-
layered fullerenes.
Graphene is an allotrope of carbon. Graphene is a hexagonal network of honeycomb lattice
made up of carbon atoms in a two dimensional planar surface. Generally the thickness of the
graphene sheet is around 1 nm.
Carbon Nano Tubes (CNT a graphene nanofoil with a honeycomb lattice of carbon atoms is
wound into hollow cylinders to form nanotubes of diameters as low as 0.7 nm for a single
layered and 100 nm for multi-layered CNT and length varying from a few micro metres to
several milli metres. The ends can either be hollow or closed by a half fullerene molecule.
Carbon Nanofiber, the same graphene nano foils are used to produce carbon nano fiber as
CNT but wound into a cone or cup shape instead of a regular cylindrical tubes.
Carbon black is an amorphous material made up of carbon, generally spherical in shape
with diameters from 20 to 70 nm. The interaction between the particles are so high that they
bound in aggregates and around 500 nm agglomerates are formed.

6.4. SIZE DEPENDENT PROPERTIES:

As mentioned above, with the decreasing particle size, the solid particles generally tend
to show different properties from the bulk material and even the physical properties like
melting point and dielectric constant themselves which have been considered as specific
properties may change, when the particles become in several nanometer size. These changes
in the fundamental properties with the particle size is called “size effect” in a narrower sense.
On the contrary, in a broader sense, it could also include the change in the various
characteristics and behaviors of particles and powders with the particle size. The
nanoparticles have various unique features in the morphological/structural properties,
thermal properties, electromagnetic properties, optical properties, mechanical properties as
described briefly in the following:

6.4.1. MORPHOLOGICAL/STRUCTURAL PROPERTIES

The ultrafine size of the nanoparticles itself is one of useful functions. For example, the
finer particles are apt to be absorbed more easily through the biological membrane. It is
known as the enhanced permeation and retention (EPR) effect, that the particles having a
particle size from about 50 to 100nm, which would not be transferred to the normal cells
through the vascular wall could be delivered selectively to a certain affected cells because of
the enlarged cell gap of this part. As mentioned above, the large specific surface area of the
nanoparticles is an important property to the reactivity, solubility, sintering performance
etc. related with the mass and heat transfer between the particles and their surroundings
from the morphological viewpoint apart from the control of the surface and inner structures
of the nanoparticles. Furthermore, the crystal structure of the particles may change with the
particle size in the nanosized range in some cases.

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6.4.2. THERMAL PROPERTIES
As the atoms and molecules located at the particle surface become influential in the
nanometer order, the melting point of the material decreases from that of the bulk material
because they tend to be able to move easier at the lower temperature. For example, the
melting point of gold is 1336 K as a bulk but starts to decrease remarkably below the particle
size of about 20 nm and drastically below 10 nm and then becomes more than 500 degrees
lower than that of the gold bulk around 2 nm. The reduction of the melting point of ultrafine
particles is regarded as one of the unique features of the nanoparticles related with
aggregation and grain growth of the nanoparticles or improvement of sintering performance
of ceramic materials.

6.4.3. ELECTROMAGNETIC PROPERTIES

The nanoparticles are used as the raw material for a number of electronic devices. The
electric properties and particle size of these nanoparticles play a great role for the
improvement of the product performance there is a strong demand for the materials with a
high dielectric constant to develop small and thin electronic devices. As described in the
previous sections, when electrons are confined to a small space then their electronic
properties are drastically altered. A clear example would be CNT and Graphene, which
acquires very good electronic properties, when compared to their native amorphous carbon.
As for the magnetic property, ferromagnetic fine particles have a single magnetic domain
structure as they become very small as in the order less than about 1 μm and show super-
paramagnetic property, when they get further finer. In this case, although the individual
particles are ferromagnetic with the single magnetic domain structure, the particles
collectively behave as a paramagnetic. It is magnetized as a whole in the same direction of
the external magnetic field but the magnetization disappears by the thermal fluctuation,
when the external magnetic field is taken away. The time for disappearing of magnetization
depends upon the particle size, namely the magnetization of the material responds promptly
with the external magnetic field as a paramagnetic when the particles are small enough but
it decreases gradually as the particle size becomes larger. As a result of such change in the
electromagnetic properties of nanoparticles, it is known for instance that the gold which is a
stable substance as a bulk shows unique catalytic characteristics as nanoparticles

6.4.4. OPTICAL PROPERTIES

As the size of particles becomes in the several nanometers range, they absorb the light
with a specific wavelength as the plasmon absorption caused by the plasma oscillation of the
electrons and the transmitted light with different color depending upon the kind of metal
and particle size is obtained. In case of gold nanoparticles, it is reported that the maximum
light absorption wavelength is 525 nm for the particles of 15nm but it is enlarged by about
50 nm for 45 nm particles. In this way, these gold and silver nanoparticles show the color
phenomena with splendid tinting strength, color saturation and transparency compared
with the conventional pigments for the paint in the submicron size and the tinting strength
per unit volume of silver nanoparticles becomes about 100 times higher than that of organic
pigments. Furthermore, since the nanoparticles are smaller than the wavelength of visible

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light and the light scattering by the particles becomes negligible, higher transparency can be
obtained with the nanoparticles than the conventional pigment. On the other hand,
concerning the light emitting performance, the indirect transition type substances like
silicon and germanium, which do not emit the light as bulk material, give high light emitting
efficiency as the direct transition type substances as a result of quantum effect, when the
particle size is reduced down to several nanometers.

6.4.5. MECHANICAL PROPERTIES

It is known that the hardness of the crystalline materials generally increases with the
decreasing crystalline size, and that the mechanical strength of the materials considerably
increases by micronizing the structure of the metal and ceramic material or composing them
in the nano range. Furthermore, with the ceramic material having crystalline size less than
several hundred nanometers, the unique super-plastic phenomenon is seen that it is
extended several to several thousand times from the original size at the elevated
temperature over 50 % of the melting point, which may provide the possibility of forming
and processing of ceramics like metallic materials.
The nanoparticles usually exhibit collective functions. Therefore, the dispersing state and
the surrounding conditions in addition to the physical properties of the particles themselves
are important. In many cases, the nanoparticles exist as aggregates of the primary particles
by the adhesion and bonding during the production process because of their high
adhesiveness. The existing state of the nanoparticles is greatly influenced by the surrounding
conditions if they are in gas, liquid, solid or in a vacuum and what sort of interaction they
have with the surrounding materials. The nanoparticles are rarely used by themselves but
dispersed in other materials or combined with them. The dispersing process of the
nanoparticles is a key for the nanoparticle technology as well as their preparation methods,
since the performance of the final products are affected by their dispersing conditions. In
this way, it is expected with great possibility to develop various new materials and
applications by the nanoparticle technology producing and processing the nanoparticles,
which have different properties from the bulk material by the size effects as mentioned
above.

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