UNIT-1

Introduction
In everyday life we encounter a remarkable range of engineering materials around us. Transportation, housing,
clothing, communication, recreation, and food production— virtually every segment of our everyday lives is
influenced to one degree or another by materials. In historical perspective, the development and advancement of
societies have been intimately tied to the society’s ability to produce and manipulate materials. Early
civilizations have been designated by the level of their materials development: Stone Age, Bronze Age, Iron
Age, and Age of advanced materials.

Material science is the investigation of the relationship among processing, structure, properties, and
performance of materials. A better understanding of structure-composition properties relations has led to a
remarkable progress in properties of materials. Example is the dramatic progress in the strength to density ratio
of materials, which resulted in a wide variety of new products, from dental materials to tennis racquets.

Many an applied scientist or engineer, whether mechanical, civil, chemical, or electrical, is at one time or
another exposed to a design problem involving materials, such as a transmission gear, the superstructure for a
building, an oil refinery component, or an integrated circuit chip. Materials scientists and engineers not only
deal with the development of materials, but also with the synthesis and processing of materials and
manufacturing processes related to the production of components. The term ‘structure’ means a description of
the arrangement of atoms, as seen at different levels of detail. The term ‘composition’ means the chemical
make-up of a material. The term ‘synthesis’ refers to how materials are made from naturally occurring or man-
made chemicals. The term ‘processing’ means how materials are shaped into useful components.

In materials engineering, the focus is on how to translate or transform materials into a useful device or structure.
One of the most fascinating aspects of materials science involves the investigation into the structure of a
material. The structure of materials has a profound influence on many properties of materials, even if the overall
composition does not change! For example, if you take a pure copper wire and bend it repeatedly, the wire not
only becomes harder but also becomes increasingly brittle! Eventually, the pure copper wire becomes so hard
and brittle that it will break rather easily. The electrical resistivity of wire will also increase as we bend it
repeatedly. In this simple example, note that we did not change the material’s composition (i.e., its chemical
make-up). The changes in the material’s properties are often due to a change in its internal structure. If you
examine the wire after bending using an optical microscope, it will look the same as before (other than the
bends, of course). However, its structure has been changed at a very small or microscopic scale. The structure at
this microscopic scale is known as microstructure. If we can understand what has changed at a micrometer
level, we can begin to discover ways to control the material’s properties.
Subatomic structure involves electrons within the individual atoms and interactions with their nuclei. On an
atomic level, structure encompasses the organization of atoms or molecules relative to one another. The next
larger structural realm, which contains large groups of atoms that are normally agglomerated together, is termed
microscopic, meaning that which is subject to direct observation using some type of microscope. Finally,
structural elements that can be viewed with the naked eye are termed macroscopic.
A property is a material trait in terms of the kind and magnitude of response to a specific imposed stimulus.
Generally, definitions of properties are made independent of material shape and size. Virtually all important
properties of solid materials may be grouped into six different categories: mechanical, electrical, thermal,
magnetic, optical, and deteriorative. For each, there is a characteristic type of stimulus capable of provoking
different responses. Mechanical properties relate deformation to an applied load or force; examples include
elastic modulus (stiffness), strength, and toughness. For electrical properties, such as electrical conductivity and
dielectric constant, the stimulus is an electric field. The thermal behavior of solids can be represented in terms
of heat capacity and thermal conductivity. Magnetic properties demonstrate the response of a material to the
application of a magnetic field. For optical properties, the stimulus is electromagnetic or light radiation; index
of refraction and reflectivity are representative optical properties. Finally, deteriorative characteristics relate to
the chemical reactivity of materials. The chapters that follow discuss properties that fall within each of these six
classifications.
In addition to structure and properties, two other important components are involved in the science and
engineering of materials—namely, processing and performance. With regard to the relationships of these four
components, the structure of a material depends on how it is processed. A material’s performance is a function
of its properties. Thus, the interrelationship among processing, structure, properties, and performance is as
depicted in the schematic illustration shown in Figure 1.1.
 Classification of Materials
There are different ways of classifying materials. One way is to describe five groups:
1. Metals and Alloys;
2. Ceramics, Glasses, and Glass-Ceramics;
3. Polymers (Plastics);
4. Semiconductors; and
5. Composite materials.

Materials in each of these groups possess different structures and properties.

Metals and Alloys
Metals include aluminum, magnesium, zinc, cast iron, titanium, copper, nickel etc. In general, metals have good
electrical and thermal conductivity. Metal Alloys are composed of one or more metallic elements (e.g., iron,
aluminum, copper, titanium, gold, nickel), and often also nonmetallic elements (e.g., carbon, nitrogen, oxygen)
in relatively small amounts. Atoms in metals and their alloys are arranged in a very orderly manner and are
relatively dense in comparison to the ceramics and polymers. These materials are relatively stiff and strong, yet
are ductile and are resistant to fracture, which accounts for their widespread use in structural or load bearing
applications. Metallic materials have large numbers of non localized electrons—that is, these electrons are not
bound to particular atoms. Many properties of metals are directly attributable to these electrons. For example,
metals are extremely good conductors of electricity and heat, and are not transparent to visible light; a polished
metal surface has a lustrous appearance. In addition, some of the metals (i.e., Fe, Co, and Ni) have desirable
magnetic properties. Although pure metals are occasionally used, combinations of metals called alloys provide
improvement in a particular desirable property or permit better combinations of properties.

Ceramics
Ceramics are compounds between metallic and nonmetallic elements; they are most frequently oxides, nitrides,
and carbides. For example, common ceramic materials include aluminum oxide (or alumina, Al2O3), silicon
dioxide (or silica, SiO2), silicon carbide (SiC), silicon nitride (Si3N4), and, in addition, what some refer to as the
traditional ceramics—those composed of clay minerals (e.g., porcelain), as well as cement and glass. With
regard to mechanical behavior, ceramic materials are relatively stiff and strong. In addition, they are typically
very hard but extremely brittle and are highly susceptible to fracture. However, newer ceramics are being
engineered to have improved resistance to fracture; these materials are used for cookware, cutlery, and even
automobile engine parts. Furthermore, ceramic materials are typically insulative to the passage of heat and
electricity and are more resistant to high temperatures and harsh environments than are metals and polymers.
With regard to optical characteristics, ceramics may be transparent, translucent, or opaque, and some of the
oxide ceramics (e.g., Fe3O4) exhibit magnetic behavior.
Ceramics can be defined as inorganic crystalline materials. Ceramics are probably the most ‘natural’ materials.
Beach sand and rocks are examples of naturally occurring ceramics. Advanced ceramics are materials made by
refining naturally occurring ceramics and other special processes. Advanced ceramics are used in substrates that
house computer chips, sensors and actuators, capacitors, spark plugs, inductors, and electrical insulation. Some
ceramics are used as thermal-barrier coatings to protect metallic substrates in turbine engines. Ceramics are also
used in such consumer products as paints, plastics, tires, and for industrial applications such as the tiles for the
space shuttle, a catalyst support, and oxygen sensors used in cars. Traditional ceramics are used to make bricks,
tableware, sanitary ware, refractories (heat-resistant material), and abrasives. In general, due to the presence of
porosity (small holes), ceramics tend to be brittle. Ceramics must also be heated to very high temperatures
before they can melt. Ceramics are strong and hard, but also very brittle. Normally ceramics are prepared from
fine powders and converted into different shapes. New processing techniques make ceramics sufficiently
resistant to fracture that they can be used in load-bearing applications, such as impellers in turbine engines.
Glass is an amorphous material, often, but not always, derived from molten silica. The term ‘amorphous’ refers
to materials that do not have a regular, periodic arrangement of atoms. The fiber optics industry is founded on
optical fibers made by using high-purity silica glass. Glasses are also used in houses, cars, computer and
television screens, and hundreds of other applications. Glasses can be thermally treated (tempered) to make
them stronger. Forming glasses and nucleating (creating) small crystals within them by a special thermal
process creates materials that are known as glass ceramics. ZerodurTM is an example of a glass-ceramic
material that is used to make the mirror substrates for large telescopes (e.g., the Chandra and Hubble
telescopes). Glasses and glass-ceramics are usually processed by melting and casting.

Polymers
Polymers include the familiar plastic and rubber materials. Many of them are organic compounds that are
chemically based on carbon, hydrogen, and other nonmetallic elements (i.e., O, N, and Si). Furthermore, they
have very large molecular structures, often chainlike in nature, that often have a backbone of carbon atoms.
Some common and familiar polymers are polyethylene (PE), nylon, poly(vinyl chloride) (PVC), polycarbonate
(PC), polystyrene (PS), and silicone rubber. These materials typically have low densities, whereas their
mechanical characteristics are generally dissimilar to those of the metallic and ceramic materials—they are not
as stiff or strong as these other material types. However, on the basis of their low densities, many times their
stiffnesses and strengths on a per-mass basis are comparable to those of the metals and ceramics. In addition,
many of the polymers are extremely ductile and pliable (i.e., plastic), which means they are easily formed into
complex shapes. In general, they are relatively inert chemically and unreactive in a large number of
environments. One major drawback to the polymers is their tendency to soften and/or decompose at modest
temperatures, which, in some instances, limits their use. Furthermore, they have low electrical conductivities
and are nonmagnetic.
Polymers are typically organic materials produced using a process known as polymerization. Polymeric
materials include rubber (elastomers) and many types of adhesives. Many polymers have very good electrical
resistivity. They can also provide good thermal insulation. Although they have lower strength, polymers have a
very good strength-to-weight ratio. They are typically not suitable for use at high temperatures. Many polymers
have very good resistance to corrosive chemicals. Polymers have thousands of applications ranging from
bulletproof vests, compact disks (CDs), ropes, and liquid crystal displays (LCDs) to clothes and coffee cups.
Thermoplastic polymers, in which the long molecular chains are not rigidly connected, have good ductility and
formability; thermosetting polymers are stronger but more brittle because the molecular chains are tightly
linked. Polymers are used in many applications, including electronic devices. Thermoplastics are made by
shaping their molten form. Thermosets are typically cast into molds. The term plastics is used to describe
polymeric materials containing additives that enhance their properties.

Semiconductors
Semiconductors have electrical properties that are intermediate between those of electrical conductors (i.e.,
metals and metal alloys) and insulators (i.e., ceramics and polymers). Furthermore, the electrical characteristics
of these materials are extremely sensitive to the presence of minute concentrations of impurity atoms, for which
the concentrations may be controlled over very small spatial regions. Semiconductors have enabled the
information age. Silicon, germanium, and gallium arsenide-based semiconductors are part of a broader class of
materials known as electronic materials. In semiconductors, the level of conductivity is controlled to enable
their use in electronic devices such as transistors, diodes, etc., that are used to build integrated circuits. In many
applications, we need large single crystals of semiconductors. These are grown from molten materials. Often,
thin films of semiconducting materials are also made using specialized processes.
Composites
A composite is composed of two (or more) individual materials that come from the different categories—
metals, ceramics, and polymers. The design goal of a composite is to achieve a combination of properties that is
not displayed by any single material and also to incorporate the best characteristics of each of the component
materials. Furthermore, some naturally occurring materials are composites—for example, wood and bone.
However, most of those we consider in our discussions are synthetic (or human-made) composites. One of the
most common and familiar composites is fiberglass, in which small glass fibers are embedded within a
polymeric material (normally an epoxy or polyester). The glass fibers are relatively strong and stiff (but also
brittle) with low density, whereas the polymer is more flexible. Another technologically important material is
the carbon fiber–reinforced polymer (CFRP) composite—carbon fibers that are embedded within a polymer.
These materials are stiffer and stronger than glass fiber–reinforced materials but more expensive. CFRP
composites are used in some aircraft and aerospace applications, as well as in high-tech sporting equipment
(e.g., bicycles, golf clubs, tennis rackets, skis/ snowboards) and recently in automobile bumpers. The new
Boeing 787 fuselage is primarily made from such CFRP composites. With composites we can produce
lightweight, strong, ductile, high temperature-resistant materials or we can produce hard, yet shock resistant,
cutting tools that would otherwise shatter.
Functional Classification of Materials
Materials can also be classified based on whether the most important function they perform is mechanical
(structural), biological, electrical, magnetic, or optical.

Aerospace
Light materials such as wood and an aluminum alloy were used in the Wright brothers’ historic flight.
Aluminum alloys, plastics, silica for space shuttle tiles, carbon-carbon composites, and many other materials
belong to this category.

Biomedical
Our bones and teeth are made, in part, from a naturally formed ceramic known as hydroxyapatite. A number of
artificial organs, bone replacement parts, cardiovascular stents, orthodontic braces, and other components are
made using different plastics, titanium alloys, and nonmagnetic stainless steels. Ultrasonic imaging systems
make use of ceramics known as PZT (lead zirconium titanate). Magnets used for magnetic resonance imaging
make use of metallic niobium tin-based superconductors.

Biomaterials are employed in components implanted into the human body to replace diseased or damaged body
parts. These materials must not produce toxic substances and must be compatible with body tissues (i.e., must
not cause adverse biological reactions). All of the preceding materials—metals, ceramics, polymers,
composites, and semiconductors— may be used as biomaterials.
Electronic Materials
As mentioned before, semiconductors, such as those made from silicon, are used to make integrated circuits for
computer chips. Barium Titanate (BaTiO3), Tantalum Oxide (Ta2O5), and many other dielectric materials are
used to make ceramic capacitors and other devices. Superconductors are used in making powerful magnets.
Copper, aluminum, and other metals are used as conductors in power transmission and in microelectronics.

Energy Technology and Environmental Technology

The nuclear industry uses materials such as uranium dioxide and plutonium as fuel. Numerous other materials,
such as glasses and stainless steels, are used in handling nuclear materials and managing radioactive waste. New
technologies related to batteries and fuel cells make use of many ceramic materials such as zirconia (ZrO 2) and
polymers. The battery technology has gained significant importance owing to the need for many electronic
devices that require longer lasting and portable power. Fuel cells are also being used in some cars. The oil and
petroleum industry widely uses zeolites, alumina, and other materials as catalyst substrates. They use Pt, Pt/Rh
and many other metals as catalysts. Many membrane technologies for purification of liquids and gases make use
of ceramics and plastics. Solar power is generated using materials such as crystalline Si and amorphous silicon
(a:Si:H).

Magnetic Materials
Computer hard disks and audio and video cassettes make use of many ceramic, metallic, and polymeric
materials. High-purity iron particles are used for making videotapes. Computer hard disks are made using alloys
based on cobalt-platinum-tantalumchromium (Co-Pt-Ta-Cr) alloys. Many magnetic ferrites are used to make
inductors and components for wireless communications. Steels based on iron and silicon are used to make
transformer cores.

Photonic or Optical Materials

Silica is used widely for making optical fibers. Almost ten million kilometers of optical fiber have been
installed around the world. Optical materials are used for making semiconductor detectors and lasers used in
fiber optic communications systems and other applications. Similarly, alumina (Al 2O3) and yttrium aluminum
garnets (YAG) are used for making lasers. Amorphous silicon is used to make solar cells and photovoltaic
modules. Polymers are used to make liquid crystal displays (LCDs).

Structural Materials
These materials are designed for carrying some type of stress. Steels, concrete, and composites are used to make
buildings and bridges. Steels, glasses, plastics, and composites are also used widely to make automotives. Often
in these applications, combinations of strength, stiffness, and toughness are needed under different conditions of
temperature and loading.

ADVANCED MATERIALS
Materials utilized in high-technology applications are sometimes termed advanced materials. By high
technology, it is meant a device or product that operates or functions using relatively intricate and sophisticated
principles, including electronic equipment (camcorders, CD/DVD players), computers, fiber-optic systems,
spacecraft, aircraft, and military rocketry. These advanced materials are typically traditional materials whose
properties have been enhanced and also newly developed, high-performance materials. Furthermore, they may
be of all material types (e.g., metals, ceramics, polymers etc.) and are normally expensive. Advanced materials
include semiconductors, biomaterials, and what we may term materials of the future (i.e., smart materials and
nano engineered materials).
Smart Materials
Smart (or intelligent) materials are a group of new and state-of-the-art materials now being developed that will
have a significant influence on many of our technologies. A smart material can sense and respond to an external
stimulus such as a change in temperature, the application of a stress, or a change in humidity or chemical
environment. Components of a smart material (or system) include some type of sensor (which detects an input
signal) and an actuator (which performs a responsive and adaptive function). Actuators may be called upon to
change shape, position, natural frequency, or mechanical characteristics in response to changes in temperature,
electric fields, and/or magnetic fields.

Four types of materials are commonly used for actuators: shape-memory alloys, piezoelectric ceramics,
magnetostrictive materials, and electrorheological/magnetorheological fluids. An example of a passively smart
material is lead zirconium titanate (PZT) and shape-memory alloys. Shape-memory alloys are metals that, after
having been deformed, revert to their original shape when temperature is changed. Piezoelectric ceramics
expand and contract in response to an applied electric field (or voltage); conversely, they also generate an
electric field when their dimensions are altered. This effect is used to make such devices as spark generators for
gas grills and sensors that can detect underwater objects such as fish and submarines. The behavior of
magnetostrictive materials is analogous to that of the piezoelectrics, except that they are responsive to magnetic
fields. Also, electrorheological and magnetorheological fluids are liquids that experience dramatic changes in
viscosity upon the application of electric and magnetic fields, respectively. These are magnetic paints that
respond to magnetic fields and are being used in suspension systems of automobiles. Materials/devices
employed as sensors include optical fibers, piezoelectric materials (including some polymers), and
microelectromechanical systems (MEMS). For example, one type of smart system is used in helicopters to
reduce aerodynamic cockpit noise created by the rotating rotor blades. Piezoelectric sensors inserted into the
blades monitor blade stresses and deformations; feedback signals from these sensors are fed into a computer-
controlled adaptive device that generates noise-canceling antinoise. Other examples of smart materials and
systems are photochromic glasses and automatic dimming mirrors based on electro chromic materials.

Nanomaterials
Nano materials have fascinating properties and tremendous technological promise, which may be any one of the
four basic types—metals, ceramics, polymers, or composites. However, unlike these other materials, they are
not distinguished on the basis of their chemistry but rather their size; the nano prefix denotes that the
dimensions of these structural entities are on the order of a nanometer (10 -9 m)—as a rule, less than 100
nanometers (nm; equivalent to the diameter of approximately 500 atoms).
Prior to the advent of nano materials, the general procedure scientists used to understand the chemistry and
physics of materials was to begin by studying large and complex structures and then investigate the fundamental
building blocks of these structures that are smaller and simpler. This approach is sometimes termed top-down
science. However, with the development of scanning probe microscopes, which permit observation of
individual atoms and molecules, it has become possible to design and build new structures from their atomic-
level constituents, one atom or molecule at a time (i.e., “materials by design”). This ability to arrange atoms
carefully provides opportunities to develop mechanical, electrical, magnetic, and other properties that are not
otherwise possible. This is called the bottom-up approach, and the study of the properties of these materials is
termed nanotechnology.
Some of the physical and chemical characteristics exhibited by matter may experience dramatic changes as
particle size approaches atomic dimensions. For example, materials that are opaque in the macroscopic domain
may become transparent on the nano scale; some solids become liquids, chemically stable materials become
combustible, and electrical insulators become conductors. Furthermore, properties may depend on size in this
nano scale domain. Some of these effects are quantum mechanical in origin, whereas others are related to
surface phenomena—the proportion of atoms located on surface sites of a particle increases dramatically as its
size decreases.
Because of these unique and unusual properties, nano materials are finding niches in electronic, biomedical,
sporting, energy production, and other industrial applications. For example:
• Catalytic converters for automobiles
• Nano carbons—Fullerenes, carbon nanotubes, and graphene
• Particles of carbon black as reinforcement for automobile tires
• Nano composites
• Magnetic nano size grains that are used for hard disk drives
• Magnetic particles that store data on magnetic tapes
Whenever a new material is developed, its potential for harmful and toxicological interactions with humans and
animals must be considered. Small nanoparticles have exceedingly large surface area–to–volume ratios, which
can lead to high chemical reactivities. Although the safety of nano materials is relatively unexplored, there are
concerns that they may be absorbed into the body through the skin, lungs, and digestive tract at relatively high
rates, and that some, if present in sufficient concentrations, will pose health risks—such as damage to DNA or
promotion of lung cancer.

Classification of Materials Based on Structure

The term ‘structure’ refers to the internal details oa a material like the arrangement of a material’s atoms. These
arrangements can be viewed at different scales, ranging from a few angstrom units to a millimeter. The
magnification and resolution of the physical aid used are a measure of the level of observation. Some materials
may be crystalline (where the material’s atoms are arranged in a periodic fashion) or they may be amorphous
(where the material’s atoms do not have a long-range order). Some crystalline materials may be in the form of
one crystal and are known as single crystals. Others consist of many crystals or grains and are known as
polycrystalline. The characteristics of crystals or grains (size, shape, etc.) and that of the regions between them,
known as the grain boundaries, also affect the properties of materials.

Depending on the level, the structure of materials can be classified as:

 Macrostructure
 Microstructure
 Substructure
 Crystal structure
 Electronic structure
 Nuclear structure.

Macrostructure
Macrostructure of a material is examined by low-power magnification or naked eye. It deals with the shape, size
and atomic arrangement in a crystalline material. In case of some crystals, e.g., quartz, external form of the
crystal may reflect the internal symmetry of atoms. Macrostructure may be observed directly on a fracture
surface or on a forging specimen. The individual crystals of a crystalline material can be visible, e.g. in a brass
doorknob by the constant polishing and etching action of a human hand and sweat. Macrostructure can reveal
flaws, segregations, cracks etc. by using proper techniques and one can save much expenses by rejecting
defective materials at an early stage.
Microstructure
Microstructure refers to the structure as observed under the optical microscope. Optical microscopes can
magnify a structure up to about 1500 - 3000 times linear, without loss of resolution of details of the structure.
The limit of resolution of the human eye is about 0.1 mm (10 –4 m), that is, the eye can distinguish two lines as
separate lines, only when their distance of separation is more than 0.1 mm. The optical microscope can resolve
details down to a limit of about 0.1 µm (10–7 m). Cracks, porosity, non-metallic inclusions within materials can
be revealed by examining them under powerful optical microscope.
Substructure
Substructure refers to the structure obtained by using a microscope with a much higher magnification and
resolution than the optical microscope. In an electron microscope, a magnification of 10,00,000 times linear is
possible. A wealth of additional information on very fine particles or on crystal imperfections such as
dislocations. Various microscopes used for studying substructure of a material are: transmission electron
microscope, scanning electron microscope, electron probe microanalyzer, field ion microscope etc.
Crystal Structure
Crystal structure gives the details of the atomic arrangement within a crystal. It is usually sufficient to describe
the arrangement of a few atoms within what is called a unit cell. The crystal consists of a very large number of
unit cells forming regularly repeating patterns in space. The main techniques employed for determining the
crystal structure is the X-ray diffraction or electron diffraction.
Electronic Structure
Electronic structure refers to the electrons in the outermost orbitals of individual atoms that constitute the solid.
Spectroscopic techniques are very useful in determining the electronic structure.
Nuclear Structure
Nuclear structure is studied by nuclear spectroscopic techniques such as nuclear magnetic resonance (NMR)
and Mossbauer studies.

Structure–Property Relationships in Materials

In recent years, the number and variety of engineering materials and applications have increased tremendously.
Therefore, it is impossible to describe an adequate number of engineering materials and their properties in one
course. Moreover, our knowledge of the internal structure of materials and how this structure correlates with the
properties has rapidly advanced in recent decades. So, it is more interesting and appropriate to study some of the
key factors that determine the structure–property relationships, rather than give full description of large number
of materials.
The levels of structure which are of the greatest interest in materials science and engineering are the
microstructure, the substructure and the crystal structure. The chemical, mechanical, electrical and magnetic
properties are among the most important engineering properties. The gross composition of a material is
important in determining its structure. Yet, for a given gross composition, radical changes in the structure and
properties can be brought about by subtle changes in the concentration and distribution of minute quantities of
impurities. The same may also be possible by a thermal or a mechanical treatment that involves no change in
the overall composition of the material. Materials Science and Engineering deals more with this kind of changes
rather than with the effect of gross composition on the properties

Environmental and Other Effects on Materials

The structure-property relationships in materials fabricated into components are often influenced by the
surroundings to which the material is subjected during use. This can include exposure to high or low
temperatures, cyclical stresses, sudden impact, corrosion or oxidation. These effects must be accounted for in
design to ensure that components do not fail unexpectedly.

Temperature
Changes in temperature dramatically alter the properties of materials. Metals and alloys that have been
strengthened by certain heat treatments or forming techniques will lose their strength when heated. A tragic
reminder of this is the collapse of the steel beams used in the World Trade Center towers on September 11,
2001.

High temperatures change the structure of ceramics and cause polymers to melt or char. Very low temperatures,
at the other extreme, may cause a metal or polymer to fail in a brittle manner, even though the applied loads are
low. This low temperature embrittlement was a factor that caused the Titanic to fracture and sink. Similarly, the
1986 Challenger accident, in part, was due to embrittlement of rubber O-rings. The reasons why some polymers
and metallic materials become brittle are different.

The design of materials with improved resistance to temperature extremes is essential in many technologies
related to aerospace. As faster speeds are attained, more heating of the vehicle skin occurs because of friction
with the air. At the same time, engines operate more efficiently at higher temperatures. So, in order to achieve
higher speed and better fuel economy, new materials have gradually increased allowable skin and engine
temperatures. But materials engineers are continually faced with new challenges. The X-33 and Venturestar are
examples of advanced reusable vehicles intended to carry passengers into space using a single stage of rocket
engines.

Corrosion
Most of the time, failure of materials occurs as a result of corrosion and some form of tensile overload. Most
metals and polymers react with oxygen or other gases, particularly at elevated temperatures. Metals and
ceramics may disintegrate and polymers and non-oxide ceramics may oxidize. Materials are also attacked by
corrosive liquids, leading to premature failure. The engineer faces the challenge of selecting materials or
coatings that prevent these reactions and permit operation in extreme environments. For example, in space
applications, one has to consider the effects of the presence of radiation, the presence of atomic oxygen, and the
impact from debris.

Fatigue
In many applications, components must be designed such that the load on the material may not be enough to
cause permanent deformation. However, when a material is loaded and unloaded the thousands of times, small
cracks may begin to develop and it fails as these cracks grow. This is known as fatigue failure. In designing
load-bearing components, the possibility of fatigue must be accounted for.
Strain Rate
Silly Putty, a silicone- (not silicon-) based plastic, can be stretched significantly if it is pulled slowly (small rate
of strain). If it ispulled fast (higher rate of strain) it snaps. A similar behavior can occur with many metallic
materials. Thus, in many applications, the level and rate of strain have to be considered. In many cases, the
effects of temperature, fatigue, stress, and corrosion may be interrelated, and other outside effects could affect
the material’s performance.

Atomic Bonding
There are four important mechanisms by which atoms are bonded in engineered materials.

These are:
1. Metallic bond;
2. Covalent bond;
3. Ionic bond; and
4. Van der Waals bond.

In the first three of these mechanisms, bonding is achieved when the atoms fill their outer s and p levels. These
bonds are relatively strong and are known as primary bonds (relatively strong bonds between adjacent atoms
resulting from the transfer or sharing of outer orbital electrons). The Van der Waals bonds are secondary bonds
and originate from a different mechanism and are relatively weaker.

The Metallic Bond

The metallic elements have more electropositive atoms that donate their valence electrons to form a ‘‘sea’’ of
electrons surrounding the atoms. Aluminum, for example, gives up its three valence electrons, leaving behind a
core consisting of the nucleus and inner electrons. Since three negatively charged electrons are missing from
this core, it has a positive charge of three. The valence electrons move freely within the electron sea and
become associated with several atom cores. The positively charged ion cores are held together by mutual
attraction to the electron, thus producing a strong metallic bond. Because their valence electrons are not fixed in
any one position, most pure metals are good electrical conductors of electricity at relatively low temperatures (T
< 300 K). Under the influence of an applied voltage, the valence electrons move, causing a current to flow if the
circuit is complete. Materials with metallic bonding exhibit relatively high Young’s modulus since the bonds
are strong. Metals also show good ductility since the metallic bonds are non-directional. There are other
important reasons related to microstructure that can explain why metals actually exhibit lower strengths and
higher ductility than what we may anticipate from their bonding. Ductility refers to the ability of materials to be
stretched or bent without breaking. In general, the melting points of metals are relatively high. From an optical
properties viewpoint, metals make good reflectors of visible radiation. Owing to their electropositive character,
many metals such as iron tend to undergo corrosion or oxidation. Many pure metals are good conductors of heat
and are effectively used in many heat transfer applications.
The Covalent Bond
Materials with covalent bonding are characterized by bonds that are formed by sharing of valence electrons
among two or more atoms. For example, a silicon atom, which has a valence of four, obtains eight electrons in
its outer energy shell by sharing its electrons with four surrounding silicon atoms. Each instance of sharing
represents one covalent bond; thus, each silicon atom is bonded to four neighboring atoms by four covalent
bonds. In order for the covalent bonds to be formed, the silicon atoms must be arranged so the bonds have a
fixed directional relationship with one another. A directional relationship is formed when the bonds between
atoms in a covalently bonded material form specific angles, depending on the material. In the case of silicon,
this arrangement produces a tetrahedron, with angles of 109.5 0 between the covalent bonds. Covalent bonds are
very strong. As a result, covalently bonded materials are very strong and hard. For example, diamond (C),
silicon carbide (SiC), silicon nitride (Si3N4), and boron nitride (BN) all exhibit covalency. These materials also
exhibit very high melting points, which means they could be useful for high-temperature applications. On the
other hand, the temperature resistance of these materials presents challenges in their processing. The materials
bonded in this manner typically have limited ductility because the bonds tend to be directional. The electrical
conductivity of many covalently bonded materials (i.e., silicon, diamond, and many ceramics) is not high since
the valence electrons are locked in bonds between atoms and are not readily available for conduction. With
some of these materials, such as Si, we can get useful and controlled levels of electrical conductivity by
deliberately introducing small levels of other elements known as dopants. Conductive polymers are also a good
example of covalently bonded materials that can be turned into semiconducting materials. The development of
conducting polymers that are lightweight has captured the attention of many scientists and engineers for
developing flexible electronic components.
The Ionic Bond
When more than one type of atoms are present in a material, one atom may donate its valence electrons to a
different atom, filling the outer energy shell of the second atom. Both atoms now have filled (or emptied) outer
energy levels, but both have acquired an electrical charge and behave as ions. The atom that contributes the
electrons is left with a net positive charge and is called a cation, while the atom that accepts the electrons
acquires a net negative charge and is called an anion. The oppositely charged ions are then attracted to one
another and produce the ionic bond. For example, the attraction between sodium and chloride ions produces
sodium chloride (NaCl), or table salt.

Van der Waals Bonding

The origin of van der Waals forces between atoms and molecules is quantum mechanical in nature. If two
electrical charges +q and -q are separated by a distance d, the arrangement is called a dipole and the dipole
moment is defined as q*d. Atoms are electrically neutral. Also, the centers of the positive charge (nucleus) and
negative charge (electron cloud) coincide. Therefore, a neutral atom has no dipole moment. When a neutral
atom is exposed to an internal or external electric field the atom gets polarized (i.e., the centers of positive and
negative charges separate). This creates or induces a dipole moment. In some molecules, the dipole moment
does not have to be induced—it exists by virtue of the direction of bonds and the nature of atoms. These
molecules are known as polar molecules. An example of such a molecule that has a permanently built-in dipole
moment is water.

There are three types of Van der Waals interactions, namely London forces, Keesom forces, and Debye forces.
If the interactions are between two dipoles that are induced in atoms or molecules, it is referred as London
forces (e.g., carbon tetrachloride). When an induced dipole (that is, a dipole that is induced in what is otherwise
a non-polar atom or molecule) interacts with a molecule that has a permanent dipole moment, this interaction is
referred as a Debye interaction. An example of Debye interaction would be forces between water molecules and
those of carbon tetrachloride. If the interactions are between molecules that are permanently polarized (e.g.,
water molecules attracting other water molecules or other polar molecules), they are referred as Keesom
interactions. The attraction between the positively charged regions of one water molecule and the negatively
charged regions of a second water molecule provides an attractive bond between the two water molecules. The
bonding between molecules that have a permanent dipole moment, known as the Keesom force, is often referred
to as the hydrogen bond, where hydrogen atoms represent one of the polarized regions. Thus, hydrogen bonding
is essentially a Keesom force and is a type of van der Waals force. The Van der Waals bonds are secondary
bonds, with smaller bond energies. However, the atoms within the molecule or group of atoms are joined by
strong covalent or ionic bonds. Thus, heating water to the boiling point breaks the Van der Waals bonds and
changes water to steam, but much higher temperatures are required to break the covalent bonds joining oxygen
and hydrogen atoms. Although termed ‘secondary’,’ based on the bond energies, Van der Waals forces play a
very important role in many areas of engineering. Van der Waals forces between atoms and molecules play a
vital role in determining the surface tension and boiling points of liquids. Van der Waals bonds can change
dramatically the properties of certain materials. For example, graphite and diamond have very different
mechanical properties. In many plastic materials, molecules contain polar parts or side groups (e.g., cotton or
cellulose, PVC, Teflon). Van der Waals forces provide an extra binding force between the chains of these
polymers. This makes PVC relatively more brittle; materials known as plasticizers are added to enhance PVC
ductility.

Mixed Bonding
In most materials, bonding between atoms is a mixture of two or more types. For example, Iron, is bonded by a
combination of metallic and covalent bonding that prevents atoms from packing as efficiently as we might
expect. Compounds formed from two or more metals (intermetallic compounds) may be bonded by a mixture of
metallic and ionic bonds, particularly when there is a large difference in electronegativity between the elements.
Because lithium has an electronegativity of 1.0 and aluminum has an electronegativity of 1.5, we would expect
AlLi to have a combination of metallic and ionic bonding. On the other hand, because both aluminum and
vanadium have electronegativities of 1.5, we would expect Al 3V to be bonded primarily by metallic bonds.
Many ceramic and semiconducting compounds, which are combinations of metallic and nonmetallic elements,
have a mixture of covalent and ionic bonding. As the electronegativity difference between the atoms increases,
the bonding becomes more ionic.
 CRYSTAL STRUCTURES
Lattice, Basis, and Unit Cells

A lattice is a collection of points called lattice points that are arranged in a periodic pattern so that the
surroundings of each point in the lattice are identical. A lattice may be one, two, or three dimensional. The
concept of ‘lattice’ to describe arrangements of atoms or ions. A group of one or more atoms, located in a
particular way with respect to each other and associated with each lattice point, is known as the ‘motif’ or
‘basis’. A crystal structure is obtained by adding the lattice and basis (i.e., crystal structure ¼ lattice þ basis).

The unit cell is the subdivision of a lattice that still retains the overall characteristics of the entire lattice. By
stacking identical unit cells, the entire lattice can be constructed. There are seven unique arrangements, known
as crystal systems, which can be used to fill up a three-dimensional space. These are cubic, tetragonal,
orthorhombic, rhombohedral (also known as trigonal), hexagonal, monoclinic, and triclinic. Although there are
seven crystal systems, there are a total of 14 distinct arrangements of lattice points, known as the Bravais
lattices. Lattice points are located at the corners of the unit cells and, in some cases, at either faces or the center
of the unit cell. The cubic crystal system has simple cubic (SC), face-centered cubic (FCC), and body-centered
cubic (BCC) Bravais lattices. Similarly, the tetragonal crystal system, has simple tetragonal and body centered
tetragonal Bravais lattices. Any other arrangement of atoms can be expressed using these 14 Bravais lattices.
The concept of a lattice is mathematical and does not mention atoms, ions or molecules. A crystal structure can
only be described when a Bravais lattice is taken and begin to define the basis (i.e., one or more atoms
associated with each lattice point). For example, if we take the face-centered cubic lattice and assume that at
each lattice point has one atom, then a face-centered cubic crystal structure is obtained.
METALLIC CRYSTAL STRUCTURES
The atomic bonding in this group of materials is metallic, and thus non directional in nature. Consequently,
there are no restrictions as to the number and position of nearest-neighbor atoms; this leads to relatively large
numbers of nearest neighbors and dense atomic packing’s for most metallic crystal structures. Also, for metals,
using the hard sphere model for the crystal structure, each sphere represents an ion core. The below Table
presents the atomic radii for a number of metals. Three relatively simple crystal structures are found for most of
the common metals: face-centered cubic, body-centered cubic, and hexagonal close-packed.

Body centered cubic structure

Another common metallic crystal structure also has a cubic unit cell with atoms located at all eight corners and
a single atom at the cube center. This is called a body-centered cubic (BCC) crystal structure. A collection of
spheres depicting this crystal structure is shown in Figure (c), whereas Figures (a) and (b) are diagrams of BCC
unit cells with the atoms represented by hard sphere and reduced-sphere models, respectively. Center and corner
atoms touch one another along cube diagonals, and unit cell length a and atomic radius R are related as:

Chromium, iron, tungsten, as well as several other metals listed in earlier Table exhibit a BCC structure. Two
atoms are associated with each BCC unit cell: the equivalent of one atom from the eight corners, each of which
is shared among eight unit cells, and the single center atom, which is wholly contained within its cell. In
addition, corner and center atom positions are equivalent. The coordination number for the BCC crystal
structure is 8; each center atom has as nearest neighbors its eight corner atoms. Since the coordination number
is less for BCC than FCC, so also is the atomic packing factor for BCC lower—0.68 versus 0.74.
Face centered cubic structure
The crystal structure found for many metals has a unit cell of cubic geometry, with atoms located at each of the
corners and the centers of all the cube faces. It is aptly called the face-centered cubic (FCC) crystal structure.
Some of the familiar metals having this crystal structure are copper, aluminum, silver, and gold (see above
Table). Figure (a) shows a hard sphere model for the FCC unit cell, whereas in Figure (b) the atom centers are
represented by small circles to provide a better perspective of atom positions. The aggregate of atoms in Figure
(c) represents a section of crystal consisting of many FCC unit cells.

These spheres or ion cores touch one another across a face diagonal; the cube edge length a and the atomic
radius R are related as
a = 2R√2
For the FCC crystal structure, each corner atom is shared among eight unit cells, whereas a face-centered atom
belongs to only two. Therefore, one eighth of each of the eight corner atoms and one half of each of the six face
atoms, or a total of four whole atoms, may be assigned to a given unit cell. This is depicted in Figure (a), where
only sphere portions are represented within the confines of the cube. The cell comprises the volume of the cube,
which is generated from the centers of the corner atoms as shown in the figure.
Corner and face positions are really equivalent; that is, translation of the cube corner from an original corner
atom to the center of a face atom will not alter the cell structure. Two other important characteristics of a crystal
structure are the coordination number and the atomic packing factor (APF). For metals, each atom has the same
number of nearest-neighbor or touching atoms, which is the coordination number.

For face-centered cubics, the coordination number is 12. This may be confirmed by examination of Figure (a)
the front face atom has four corner nearest-neighbor atoms surrounding it, four face atoms that are in contact
from behind, and four other equivalent face atoms residing in the next unit cell to the front, which is not shown.
The APF is the fraction of solid sphere volume in a unit cell, assuming the atomic hard sphere model, or

For the FCC structure, the atomic packing factor is 0.74, which is the maximum packing possible for spheres all
having the same diameter. Computation of this APF is also included as an example problem. Metals typically
have relatively large atomic packing factors to maximize the shielding provided by the free electron cloud.

Hexagonal closely packed structures

Not all metals have unit cells with cubic symmetry; the final common metallic crystal structure to be discussed
has a unit cell that is hexagonal. Figure (a) shows a reduced-sphere unit cell for this structure, which is termed
hexagonal close-packed (HCP).

An assemblage of several HCP unit cells is presented in Figure (b) The top and bottom faces of the unit cell
consist of six atoms that form regular hexagons and surround a single atom in the center. Another plane that
provides three additional atoms to the unit cell is situated between the top and bottom planes. The atoms in this
mid plane have as nearest neighbors atoms in both of the adjacent two planes. The equivalent of six atoms is
contained in each unit cell; one-sixth of each of the 12 top and bottom face corner atoms, one-half of each of the
2 center face atoms, and all the 3 mid plane interior atoms. If a and c represent, respectively the short and long
unit cell dimensions of Figure (a) the c/a ratio should be 1.633 however, for some HCP metals this ratio
deviates from the ideal value.
The coordination number and the atomic packing factor for the HCP crystal structure are the same as for FCC:
12 and 0.74, respectively. The HCP metals include cadmium, magnesium, titanium, and zinc.
POLYMERS
The word “mer” means a ‘‘unit.’’. The term “mer” refers to a unit group of atoms or molecules that defines a
characteristic arrangement for a polymer. Polymers are materials consisting of giant or macromolecules, chain-
like molecules having average molecular weights from 10,000 to more than 1,000,000 g/mol. They are built by
joining many mers or units through chemical bonding. Molecular weight is defined as the sum of atomic masses
in each molecule.

Most polymers, solids or liquids, are carbon-based; however, they can be inorganic (e.g., silicones based on a
Si-O network). Plastics are materials that are composed principally of polymers containing additives such as
glass fibers, fillers, pigments, and the like that further enhance their properties. Plastics include thermoplastics
(commodity and engineering), thermoset materials, and elastomers (natural or synthetic).

Polymers are lightweight, corrosion-resistant materials with low strength and stiffness, and they are not suitable
for use at high temperatures. These polymers are, however, relatively inexpensive and are readily formed into a
variety of shapes, ranging from plastic bags to mechanical gears to bathtubs. Engineering polymers are designed
to give improved strength or better performance at elevated temperatures. These materials are produced in
relatively small quantities and often are expensive. Some of the engineering polymers can perform at
temperatures as high as 350ºC; others—usually in a fiber form—have strengths that are greater than that of
steel.

Most polymers are electrical insulators, special polymers (such as the acetals) and polymer-based composites
possess useful electrical conductivity. Teflon has a low coefficient of friction and is the coating for nonstick
cookware. Polymers also resist corrosion and chemical attack.
Classification of Polymers
Polymers are classified in several ways: by how the molecules are synthesized, by their molecular structure, or
by their chemical family. One way to classify polymers is to state if the polymer is a linear polymer or a
branched polymer (as shown in Figure).

Figure Schematic showing linear and branched polymers.

(a) Linear unbranched polymer . (b) Linear branched polymer:
(c) Thermoset polymer without branching(d) Thermoset polymer
A linear polymer consists of spaghetti-like molecular chains. In a branched polymer, there are primary polymer
chains and secondary offshoots of smaller chains that stem from these main chains. Note that even though we
say ‘linear’, the chains are actually not in the form of straight lines. A better method to describe polymers is in
terms of their mechanical and thermal behavior. The below Table given is a comparison of the three major
polymer categories:

Thermoplastics are composed of long chains produced by joining together monomers they typically behave in
a ductile manner. The chains may or may not have branches. Individual chains are intertwined. There are
relatively weak vander Waals bonds between atoms of different chains. This is somewhat similar to a few trees
that are tangled up together. The trees may or may not have branches, each tree is on its own and not connected
to another. The chains in thermoplastics can be untangled by application of a tensile stress. Thermoplastics can
be amorphous or crystalline. Upon heating, thermoplastics soften and melt. They are processed into shapes by
heating to elevated temperatures. Thermoplastics are easily recycled.

Thermosetting polymers are composed of long chains (linear or branched) of molecules that are strongly cross-
linked to one another to form three-dimensional network structures. Network or thermosetting polymers are like
a bunch of strings that are knotted to one another in several places and not just tangled up. Each string may have
other side strings attached to it. Thermosets are generally stronger, but more brittle, than thermoplastics.
Thermosets do not melt upon heating but begin to decompose. They cannot easily be reprocessed after the
cross-linking reaction has occurred and hence recycling is difficult.

Elastomers These are known as rubbers. They have an elastic deformation >200%. These may be
thermoplastics or lightly cross-linked thermosets. The polymer chains consist of coil-like molecules that can
reversibly stretch by applying a force.

Thermoplastic elastomers are a special group of polymers. They have the processing ease of thermoplastics
and the elastic behavior of elastomers.

Structure of Long Chain Polymers

Linear Polymers
Linear polymers are those in which the “mer” units are joined together end to end in single chains. These long
chains are flexible and may be thought of as a mass of spaghetti, as represented schematically in Figure (a),
where each circle represents a “mer” unit. For linear polymers, there may be extensive Vander Waals and
hydrogen bonding between the chains. Some of the common polymers that form with linear structures are
polyethylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, nylon, and the fluorocarbons.

Branched Polymers
Polymers may be synthesized in which side-branch chains are connected to the main ones, as indicated
schematically in Figure (b); these are fittingly called branched polymers. The branches, considered to be part
of the main-chain molecule, result from side reactions that occur during the synthesis of the polymer. The chain
packing efficiency is reduced with the formation of side branches, which results in a lowering of the polymer
density. Those polymers that form linear structures may also be branched.

Crosslinked Polymers
In crosslinked polymers, adjacent linear chains are joined one to another at various positions by covalent
bonds, as represented in Figure (c) The process of cross linking is achieved either during synthesis or by a
nonreversible chemical reaction that is usually carried out at an elevated temperature. Often, this cross linking is
accomplished by additive atoms or molecules that are covalently bonded to the chains. Many of the rubber
elastic materials are cross linked; in rubbers, this is called vulcanization.

Network Polymers
Trifunctional mer units, having three active covalent bonds, form three-dimensional networks Figure (d) and are
termed network polymers. Actually, a polymer that is highly cross linked may be classified as a network
polymer. These materials have distinctive mechanical and thermal properties; the epoxies and phenol-
formaldehyde belong to this group. It should be pointed out that polymers are not usually of only one distinctive
structural type. For example, a predominantly linear polymer might have some limited branching and cross
linking.
 UNIT- 2

Types and applications of materials:

INTRODUCTION
Metallic materials are broadly of two kinds – ferrous and non-ferrous materials. This
classification is primarily based on tonnage of materials used all around the world. Ferrous
materials are those in which iron (Fe) is the principle constituent. All other materials are
categorized as non-ferrous materials. Another classification is made based on their formability. If
materials are hard to form, components with these materials are fabricated by casting, thus they
are called cast alloys. If material can be deformed, they are known as wrought alloys. Materials
are usually strengthened by two methods – cold work and heat treatment. Strengthening by heat
treatment involves either precipitation hardening or martensitic transformation, both of which
constitute specific heat treating procedure. When a material cannot be strengthened by heat
treatment, it is referred as non-heat-treatable alloys.
Ferrous materials/metals may be defined as those metals whose main constituent is iron such as
pig iron, wrought iron, cast iron, steel and their alloys. Ferrous means iron. Most common
engineering materials are ferrous materials which are alloys of iron. The principal raw materials
for ferrous metals are pig iron. Ferrous materials are usually stronger and harder and are used in
daily life products. Ferrous material possesses a special property that their characteristics can be
altered by heat treatment processes or by addition of small quantity of alloying elements. Ferrous
metals possess different physical properties according to their carbon content. Iron is the name
given to pure ferrite Fe, as well as to fused mixtures of this ferrite with large amount of carbon
(may be 1.8%), these mixtures are known as pig iron and cast iron. Primarily pig iron is
produced from the iron ore in the blast furnace from which cast iron, wrought iron and steel can
be produced.
FERROUS METAL & ALLOYS:
Ferrous materials are produced in larger quantities than any other metallic material. Three factors
account for it: (a) availability of abundant raw materials combined with economical extraction,
(b) ease of forming and (c) their versatile mechanical and physical properties. One main
drawback of ferrous alloys is their environmental degradation i.e. poor corrosion resistance.
Other disadvantages include: relatively high density and comparatively low electrical and
thermal conductivities. In ferrous materials the main alloying element is carbon (C). Depending
on the amount of carbon present, these alloys will have different properties, especially when the
carbon content is either less/higher than 2.14%. This amount of carbon is specific as below this
amount of carbon, material undergoes eutectoid transformation, while above that limit ferrous
materials undergo eutectic transformation. Thus the ferrous alloys with less than 2.14% C are
termed as steels and the ferrous alloys with higher than 2.14% C are termed as cast irons.
CARBON STEELS:
Plain carbon steel is that steel in which alloying element is carbon. Practically besides iron and
carbon four other alloying elements are always present but their content is very small that they
do not affect physical properties. These are sulphur, phosphorus, silicon and manganese.
Although the effect of sulphur and phosphorus on properties of steel is detrimental, but their
percentage is very small. Sulphur exists in steel as iron sulphide which produces red shortness or
manganese sulphide which does affect its properties. Likewise for production of cold chisels,
punches and dies. Springs, broaches and reamers can be produced for steel containing carbon. As
the percentage of carbon further increases, it can be used for production of milling cutters, anvils,
taps, drills, files, razors, metal cutting tools for lathes, shapers, planner and drawing dies.
Steels:
Steels are alloys of iron and carbon plus other alloying elements. In steels, carbon present in
atomic form, and occupies interstitial sites of Fe microstructure. Alloying additions are necessary
for many reasons including: improving properties, improving corrosion resistance, etc. Arguably
steels are well known and most used materials than any other materials.
Mechanical properties of steels are very sensitive to carbon content. Hence, it is practical to
classify steels based on their carbon content. Thus steels are basically three kinds: low-carbon
steels (% wt of C < 0.3), medium carbon steels (0.3 <% wt of C < 0.6) and high-carbon steels (%
wt of C > 0.6). The other parameter available for classification of steels is amount of alloying
additions, and based on this steels are two kinds: (plain) carbon steels and alloy-steels.
Low carbon steels: These are arguably produced in the greatest quantities than other alloys.
Carbon present in these alloys is limited, and is not enough to strengthen these materials by heat
treatment; hence these alloys are strengthened by cold work. Their microstructure consists of
ferrite and pearlite, and these alloys are thus relatively soft, ductile combined with high
toughness. Hence these materials are easily machinable and weldable. Typical applications of
these alloys include: structural shapes, tin cans, automobile body components, buildings, etc.
A special group of ferrous alloys with noticeable amount of alloying additions are known as
HSLA (high-strength low-alloy) steels. Common alloying elements are: Cu, V, Ni, W, Cr, Mo,
etc. These alloys can be strengthened by heat treatment, and yet the same time they are ductile,
formable. Typical applications of these HSLA steels include: support columns, bridges, pressure
vessels.
Medium carbon steels: These are stronger than low carbon steels. However these are of less
ductile than low carbon steels. These alloys can be heat treated to improve their strength. Usual
heat treatment cycle consists of austenitizing, quenching, and tempering at suitable conditions to
acquire required hardness. They are often used in tempered condition. As hardenability of these
alloys is low, only thin sections can be heat treated using very high quench rates. Ni, Cr and Mo
alloying additions improve their hardenability. Typical applications include: railway tracks &
wheels, gears, other machine parts which may require good combination of strength and
toughness.
High carbon steels: These are strongest and hardest of carbon steels, and of course their ductility
is very limited. These are heat treatable, and mostly used in hardened and tempered conditions.
They possess very high wear resistance, and capable of holding sharp edges. Thus these are used
for tool application such as knives, razors, hacksaw blades, etc. With addition of alloying
element like Cr, V, Mo, W which forms hard carbides by reacting with carbon present, wear
resistance of high carbon steels can be improved considerably.
CAST IRONS:
It is primarily an alloy of iron and carbon. The carbon content in cast iron varies from 1.5 to 4
per cent. Small amounts of silicon, manganese, sulphur and phosphorus are also present in it.
Carbon in cast iron is present either in free state like graphite or in combined state as cementite.
Cast iron contains so much carbon or its equivalent that it is not malleable. One characteristic
(except white cast iron) is that much of carbon content is present in free form as graphite.
Largely the properties of cast iron are determined by this fact. Melting point of cast iron is much
lower than that of steel. Most of the castings produced in a cast iron foundry are of grey cast
iron. These are cheap and widely used. Hard and brittle constituent presented in these alloys,
cementite is a meta-stable phase, and can readily decompose to form α-ferrite and graphite. In
this way disadvantages of brittle phase can easily be overcome. Tendency of cast irons to form
graphite is usually controlled by their composition and cooling rate. Based on the form of carbon
present, cast irons are categorized as gray, white, nodular and malleable cast irons.
The characteristics of cast iron which make it a valuable material for engineering applications
are:
(1) Very good casting characteristics.
(2) Low cost.
(3) High compressive strength.
(4) Good wear resistance.
(5) Excellent machinability.
The main limitation of this metal is brittleness and low tensile strength and thus cannot be used
in those components subjected to shocks.
Gray cast iron: These alloys consists carbon in form graphite flakes, which are surrounded by
either ferrite or pearlite. Because of presence of graphite, fractured surface of these alloys look
grayish, and so is the name for them. Alloying addition of Si (1-3wt.%) is responsible for
decomposition of cementite, and also high fluidity. Thus castings of intricate shapes can be
easily made. Due to graphite flakes, gray cast irons are weak and brittle. However they possess
good damping properties, and thus typical applications include: base structures, bed for heavy
machines, etc. they also show high resistance to wear.
The varieties of cast iron in common uses are:
(1) Grey cast iron
(2) White cast iron
(3) Malleable cast iron
(4) Nodular cast iron
(5) Chilled cast iron
(6) Alloy cast iron
1. Grey Cast Iron
It is the iron which is most commonly used in foundry work. If this iron is machined or broken,
its fractured section shows the greyish colour, hence the name “grey” cast iron. The grey colour
is due to the fact that carbon is present in the form of free graphite. A very good characteristic of
grey cast iron is that the free graphite in its structure acts as a lubricant. This is suitable for those
components/products where sliding action is desired. The other properties are good
machinability, high compressive strength, low tensile strength and no ductility. In view of its low
cost, it is preferred in all fields where ductility and high strength are not required. The grey cast
iron castings are widely utilized in machine tool bodies, automobile cylinder blocks and
flywheels, etc.
2. White Cast Iron
It is so called due to the whitish colour shown by its fracture. White cast iron contains carbon
exclusively in the form of iron carbide Fe3C (cementite). From engineering point of view, white
cast iron has limited applications. This is because of poor machinability and possessing, in
general, relatively poor mechanical properties. It is used for inferior castings and places where
hard coating is required as in outer surface of car wheels. Only crushing rolls such as rollers in
rolling mills are made of white cast iron. But it is used as raw material for production of
malleable cast iron. They are very brittle and extremely difficult to machine. Usually white cast
iron is heat treated to produce malleable iron. When Si content is low (< 1%) in combination
with faster cooling rates.
3. Malleable Cast Iron
Malleable cast iron is produced from white cast iron. The white cast iron is brittle and hard. It is,
therefore, unsuitable for articles which are thin, light and subjected to shock and vibrations or for
small castings used in various machine components. Heat treatments involve heating the material
up to 800-900 ْC, and keep it for long hours, before cooling it to room temperature. The
malleable cast iron is produced from white cast iron by suitable heat treatment, i.e., annealing.
This process separates the combined carbon of the white cast iron into noddles of free graphite.
The malleable cast iron is ductile and may be bent without rupture or breaking the section. Its
tensile strength is usually higher than that of grey cast iron and has excellent machining qualities.
Malleable cast iron components are mainly utilized in place of forged steel or parts where
intricate shape of these parts creates forging problem. Typical applications include: railroad,
connecting rods, marine, pipe fittings and other heavy-duty services.
4. Nodular (or ductile) Cast Iron
It is also known as “spheroidal graphite iron” or ductile iron or High strength “Cast iron”. This
nodular cast iron is obtained by adding magnesium to the molten cast iron. The magnesium
converts the graphite of cast iron from flake to spheroidal or nodular form. In this manner, the
mechanical properties are considerably improved. The strength increases, yield point improves
and brittleness is reduced. Such castings can even replace steel components. Outstanding
characteristics of nodular cast iron are high fluidity which allows the castings of intricate shape.
This cast iron is widely used in castings where density as well as pressure tightness is a highly
desirable quality. The applications include hydraulic cylinders, valves, pipes and pipe fittings,
cylinder head for compressors, diesel engines, etc.
5. Chilled Cast Iron
Quick cooling is generally known as chilling and the iron so produced is “chilled iron”. The
outer surface of all castings always gets chilled to a limited depth about (1 to 2 mm) during
pouring and solidification of molten metal after coming in contact with cool sand of mould.
Sometimes the casting is chilled intentionally and some becomes chilled accidentally to a small
depth. Chills are employed on any faces of castings which are required to be hard to withstand
wear and friction. Chilled castings are used in producing stamping dies and crushing rolls
railway, wheels cam followers, and so on.
6. Alloy Cast Iron
Alloying elements are added to cast iron to overcome inherent deficiencies in ordinary cast iron
to provide requisite characteristics for special purposes. The alloy cast iron is extremely tough,
wear resistant and non-magnetic steel about 12 to 14 per cent manganese should be added.
WROUGHT IRON:
The meaning of “wrought” is that metal which possesses sufficient ductility in order to permit
hot and/or cold deformation. Wrought iron is the purest iron with a small amount of slag forged
out into fibres. The typical composition indicates 99 percent of iron and traces of carbon,
phosphorus, manganese, silicon, sulphur and slag. During the production process, first all
elements in iron (may be C, S, Mn, Si and P) are eliminated leaving almost pure iron molten
slag. In order to remove the excess slag, the final mix is then squeezed in a press and reduced to
billets by rolling milling. The resulting material would consist of pure iron separated by thin
layers of slag material. The slag characteristic of wrought iron is beneficial in
blacksmithy/forging operations and provides the material its peculiar fibrous structure. Further,
the non-corrosive slag constituent makes wrought iron resistant to progressive corrosion and also
helps in reducing effect of fatigue caused by shocks and vibrations.
Wrought iron is tough, malleable and ductile and possesses ultimate tensile strength of 350
N/mm2. Its melting point is 1530°C. It can neither be hardened nor tempered like steel. The
billets of wrought iron can be reheated to form bars, plates, boiler tubing, forgings, crane hook,
railway coupling, bolts and nuts, chains, barbed wire, coal handling equipment and cooling
towers, etc.
Nickel: It may be termed as one of the most important alloying elements. It improves tensile
strength, ductility, toughness and corrosion resistance.
Chromium: Its addition to steel improves toughness, hardness and corrosion resistance.
Boron: It increases hardenability and is therefore very useful when alloyed with low carbon
steels.
Cobalt: It is added to high speed steels to improve hardness, toughness, tensile strength, thermal
resistance and magnetic properties. It acts as a grain purifier.
Tungsten: Tungsten improves hardness, toughness, wear resistance, shock resistance, magnetic
reluctance and ability to retain hardness at elevated temperatures. It provides hardness and
abrasion resistance properties to steel.
Molybdenum: It improves wear resistance, hardness, thermal resistance, ability to retain
mechanical properties at elevated temperatures and helps to inhibit temper brittleness.
Vanadium: It increases tensile strength, elastic limit, ductility, shock resistance and also acts as
a degasser when added to molten steel. It provides improvement to hardenability of steel. It is a
very good deoxidizer and promotes grain growth. It is the strongest carbide former. Titanium is
used to fix carbon in stainless steel and thus prevents the precipitation of chromium-carbide.
Niobium: It improves ductility, decreases hardenability and substantially improves the impact
strength. It also promotes fine grain growth.
STAINLESS STEELS:
The only material known to engineers which possesses a combination of various properties
such as: wide range of strength and hardness, high ductility and formability, high corrosion
resistance, good creep resistance, good thermal conductivity, good machinability, high hot &
cold workability and excellent surface finish is stainless steel. Alloy steels have been developed
for a specific purpose. We shall study them as follows:
They are known as stainless since they do not corrode or rust easily in most of environment and
media. Stainless steels can be further divided into the following three categories:
(1) Ferritic stainless steel: It is that steel when properly heat treated and finished, resists
oxidation and corrosive attacks from corrosive media. Ferritic stainless steels contain 12–18%
chromium, 0.15 to 0.2% carbon besides iron and usual amounts of manganese and silicon. The
steels are stainless and relatively cheap. They are magnetic in nature. Structure of these steels
consists of ferrite phase which cannot be hardened by heat treatment. These steels are actually
iron-chromium alloys and cannot be hardened by heat treatment. Such type of steel is utilized in
manufacture of dairy equipment food processing plants, etc.
(2) Martensitic stainless steel: These steels contain 12–18% chromium and 0.1 to 1.8% carbon.
These steels can be hardened by heat treatment but their corrosion resistance is decreased. Steels
with 12 to 14% chromium and 0.3% carbon are widely used for table cutlery, tools and
equipment. Steel with little less carbon percentage and higher percentage of chromium are used
as springs, ball bearings and instruments under high temperature and corrective conditions.
(3) Austentic stainless steels: These are the most costliest among all stainless steels. In these
steels besides chromium, nickel is also added. Nickel is a very strong austenitic stabilizer and
therefore the microstructure of these steels is austentic at room temperature. These steels contain
12 to 21% chromium and 8 to 15% nickel and carbon less than 0.2%. The most familiar alloy of
this group is known as 18:8 stainless steel i.e. 18% chromium and 8% nickel plus other. Other
elements like carbon, manganese and silicon in very small quantities.
TOOL STEELS:
Tool steels are specially alloyed steels designed for high strength, impact toughness and wear
resistance at room and elevated temperatures. They are normally used in forming and machining
of metals. So the requirements in a tool steel are that it should be capable of becoming very hard
and further that it should be able to retain its hardness at high temperatures normally developed
during cutting of materials. This property is known as “red hardness”. Further, tool steel should
not be brittle for smooth working.
1. High Speed Steel (H.S.S.)
It is the name given to the most common tool steel. As the name implies, it can cut steel at high
cutting speeds. These steels are high in alloy content, have excellent hardenability, maintain their
hardness at elevated temperatures around 650°C, are quite resistant to wear and contain relatively
large amounts of tungsten or molybdenum, together with chromium, cobalt or vanadium. They
are used to produce cutting tools to be operated for various machining operations such as turning,
drilling, milling, etc. A typical composition of H.S.S. is tungsten 18%, chromium 4% and
vanadium 1%, carbon 0.75 to 0.9% and rest iron.
2. Molybdenum High Speed Steel
This steel contains 6% tungsten, 6% molybdenum, 4% chromium and 2% vanadium and has
excellent toughness and cutting ability. The molybdenum high speed steel is better and cheaper
than other types of steel. It is particularly utilized in drilling and tapping operations.
NON FERROUS METAL & ALLOYS:
Non-ferrous materials have specific advantages over ferrous materials. They can be fabricated
with ease, high relatively low density, and high electrical and thermal conductivities. However
different materials have distinct characteristics, and are used for specific purposes. This section
introduces some typical non-ferrous metals and their alloys of commercial importance.
Copper:
Copper is one of the earliest metals discovered by man. The boilers on early steamboats were
made from copper.
The copper tubing used in water plumbing in Pyramids was found in serviceable condition after
more than 5,000 years. The Cu is a ductile metal. Pure Cu is soft and malleable, difficult to
machine. It is very high electrical conductivity – second only to silver. Copper is refined to high
purity for many electrical works.
Applications:
 Excellent thermal conductivity – Copper cookware most highly regarded – fast and
uniform heating.
 Electrical and construction industries are the largest users of Cu.
Copper Alloys:
 Brasses and Bronzes are most commonly used alloys of Cu. Brass is an alloy with Zn.
Bronzes contain tin, aluminum, silicon or beryllium.
 Other copper alloy families include copper-nickels and nickel silvers. More than 400
copper base alloys are recognized.
Applications:
Electrical wires, roofing, nails, rivets. automotive radiator, core, lamp fixture, clutch disk,
diaphragm, fuse clips, springs, Furniture, radiator, fittings, battery clamps, light fixtures,
bearings, bushings, valve seats and guards, Electrical, valves, pumps, condenser, heat exchanger,
piping valves, Tin bronze Sn, bushing, piston rings, gears.
Aluminum:
Aluminum is a light metal & easily machinable; has wide variety of surface finishes; good
electrical and thermal conductivities; highly reflective to heat and light.
 Versatile metal - can be cast, rolled, stamped, drawn, spun, roll-formed, hammered,
extruded and forged into many shapes.
 Aluminum can be riveted, welded, brazed, or resin bonded.
 Corrosion resistant - no protective coating needed, however it is often anodized to
improve surface finish, appearance.
 Al and its alloys - high strength-to-weight ratio (high specific strength) owing to low
density.
 Such materials are widely used in aerospace and automotive applications where weight
savings are needed for better fuel efficiency and performance.
 Al-Li alloys are lightest among all Al alloys and find wide applications in the aerospace
industry.
Application: Food/chemical handling, equipment, heat exchangers, light reflectors, Utensils,
pressure vessels and piping Strain- hardn, Bellows, clutch disk, diaphragm, fuse clips, springs,
Heat treated, Aircraft structure, rivets, truck, wheels, screw, Trucks, canoes, railroad cars,
furniture, pipelines Peak-aged, Aircraft structures and other highly loaded applications, Aircraft
pump parts, automotive transmission, cases, cylinder blocks
Zinc:
Zinc (symbol Zn), in commerce also spelter, is a metallic chemical element. It has atomic
number 30. It is the first element of group 12 of the periodic table. In some respects zinc is
chemically similar to magnesium: its ion is of similar size and its only common oxidation state is
+2. Zinc is the 24th most abundant element in the Earth's crust and has five stable isotopes. The
most common zinc ore is sphalerite (zinc blende), a zinc sulfide mineral. The largest mineable
amounts are found in Australia, Asia, and the United States. Zinc production includes froth
flotation of the ore, roasting, and final extraction using electricity (electro winning). Brass, which
is an alloy of copper and zinc, has been used since at least the 10th century BC in Judea and by
the 7th century BC in Ancient Greece. Zinc metal was not produced on a large scale until the
12th century in India and was unknown to Europe until the end of the 16 th century. The mines of
Rajasthan have given definite evidence of zinc production going back to 6th century BC. To
date, the oldest evidence of pure zinc comes from Zawar, in Rajasthan, as early as the 9th
century AD when a distillation process was employed to make pure zinc. Alchemists burned zinc
in air to form what they called "philosopher's wool" or "white snow".
Applications:
Major applications of zinc include
o Galvanizing (55%)
o Alloys (21%)
o Brass and bronze (16%)
o Miscellaneous (8%)
The metal is most commonly used as an anti-corrosion agent. Galvanization, which is the coating
of iron or steel to protect the metals against corrosion, is the most familiar form of using zinc in
this way. In 2009 in the United States, 55% or 893 thousand tonnes of the zinc metal were used
for galvanization. Zinc is more reactive than iron or steel and thus will attract almost all local
oxidation until it completely corrodes away. A protective surface layer of oxide and carbonate
forms as the zinc corrodes. This protection lasts even after the zinc layer is scratched but
degrades through time as the zinc corrodes away. The zinc is applied electrochemically or as
molten zinc by hot-dip galvanizing or spraying. Galvanization is used on chain-link fencing,
guard rails, suspension bridges, light posts, metal roofs, heat exchangers, and car bodies. The
relative reactivity of zinc and its ability to attract oxidation to itself makes it an efficient
sacrificial anode in catholic protection (CP). For example, cathodic protection of a buried
pipeline can be achieved by connecting anodes made from zinc to the pipe. Zinc acts as the
anode (negative terminus) by slowly corroding away as it passes electric current to the steel
pipeline. Zinc is also used to catholically protect metals that are exposed to sea water from
corrosion. Other similar uses include a plug of zinc attached to a propeller or the metal protective
guard for the keel of the ship. With a standard electrode potential (SEP) of −0.76 volts, zinc is
used as an anode material for batteries. (More reactive lithium (SEP −3.04 V) is used for anodes
in lithium batteries).
Powdered zinc is used in this way in alkaline batteries and sheets of zinc metal form the cases for
and act as anodes in zinc–carbon batteries. Zinc is used as the anode or fuel of the zincair
battery/fuel cell. The zinc-cerium redox flow battery also relies on a zinc-based negative halfcell.
Alloys:
A widely used alloy which contains zinc is brass, in which copper is alloyed with anywhere from
3% to 45% zinc, depending upon the type of brass. Brass is generally more ductile and stronger
than copper and has superior corrosion résistance. These properties make it useful in
communication equipment, hardware, musical instruments, and water valves.
Other widely used alloys that contain zinc include nickel silver, typewriter metal, soft and
aluminum solder, and commercial bronze. Zinc is also used in contemporary pipe organs as a
substitute for the traditional lead/tin alloy in pipes. Alloys of 85–88% zinc, 4–10% copper, and
2–8% aluminum find limited use in certain types of machine bearings. Zinc is the primary metal
used in making American one cent coins since [Link] zinc core is coated with a thin layer of
copper to give the impression of a copper coin. In 1994, 33,200 tonnes (36,600 short tons) of
zinc were used to produce 13.6 billion pennies in the United States. Alloys of primarily zinc with
small amounts of copper, aluminum, and magnesium are useful in die casting as well as spin
casting, especially in the automotive, electrical, and hardware industries. These alloys are
marketed under the name Zamak. An example of this is zinc aluminum. The low melting point
together with the low viscosity of the alloy makes the production of small and intricate shapes
possible. The low working temperature leads to rapid cooling of the cast products and therefore
fast assembly is possible. Another alloy, marketed under the brand name Prestal, contains 78%
zinc and 22% aluminum and is reported to be nearly as strong as steel but as malleable as plastic.
This super plasticity of the alloy allows it to be molded using die casts made of ceramics
and cement.
Similar alloys with the addition of a small amount of lead can be cold-rolled into sheets. An alloy
of 96% zinc and 4% aluminum is used to make stamping dies for low production run
applications for which ferrous metal dies would be too expensive in building facades, roofs or
other applications in which zinc is used as sheet metal and for methods such as deep drawing,
roll forming or bending, zinc alloys with titanium and copper are used unalloyed zinc is too
brittle for these kinds of manufacturing processes.
As a dense, inexpensive, easily worked material, zinc is used as a lead replacement. In the wake
of lead concerns, zinc appears in weights for various applications ranging from fishing to tire
balances and flywheels.
Cadmium zinc telluride (CZT) is a semi conductive alloy that can be divided into an array of
small sensing devices. These devices are similar to an integrated circuit and can detect the energy
of incoming gamma ray photons. When placed behind an absorbing mask, the CZT sensor array
can also be used to determine the direction of the rays.
Aluminium alloys: These are characterized by low density, high thermal & electrical
conductivities, and good corrosion resistant characteristics. As Al has FCC crystal structure,
these alloys are ductile even at low temperatures and can be formed easily. However, the great
limitation of these alloys is their low melting point (660 ْC), which restricts their use at elevated
temperatures. Strength of these alloys can be increased by both cold and heat treatment – based
on these alloys are designated in to two groups, cast and wrought. Chief alloying elements
include: Cu, Si, Mn, Mg, Zn. Recently, alloys of Al and other low-density metals like Li, Mg, Ti
gained much attention as there is much concern about vehicle weight reduction. Al-Li alloys
enjoy much more attention especially as they are very useful in aircraft and aerospace industries.
Common applications of Al alloys include: beverage cans, automotive parts, bus bodies, aircraft
structures, etc. Some of the Al alloys are capable of strengthening by precipitation, while others
have to be strengthened by cold work or solid solution methods.
Copper alloys: As history goes by, bronze has been used for thousands of years. It is actually an
alloy of Cu and Sn. Unalloyed Cu is soft, ductile thus hard to machine, and has virtually
unlimited capacity for cold work. One special feature of most of these alloys is their corrosion
resistant in diverse atmospheres. Most of these alloys are strengthened by either cold work or
solid solution method. Common most Cu alloys: Brass, alloys of Cu and Zn where Zn is
substitutional addition (e.g.: yellow brass, catridge brass, muntz metal, gilding metal); Bronze,
alloys of Cu and other alloying additions like Sn, Al, Si and Ni. Bronzes are stronger and more
corrosion resistant than brasses. Mention has to be made about Beryllium coppers who possess
combination of relatively high strength, excellent electrical and corrosion properties, wear
resistance, can be cast, hot worked and cold worked. Applications of Cu alloys include: costume
jewelry, coins, musical instruments, electronics, springs, bushes, surgical and dental instruments,
radiators, etc.
Magnesium alloys: The most sticking property of Mg is its low density among all structural
metals. Mg has HCP structure, thus Mg alloys are difficult to form at room temperatures. Hence
Mg alloys are usually fabricated by casting or hot working. As in case of Al, alloys are cast or
wrought type, and some of them are heat treatable. Major alloying additions are: Al, Zn, Mn and
rare earths. Common applications of Mg alloys include: hand-held devices like saws, tools,
automotive parts like steering wheels, seat frames, electronics like casing for laptops, camcoders,
cell phones etc.
Titanium alloys: Ti and its alloys are of relatively low density, high strength and have very high
melting point. At the same time they are easy to machine and forge. However the major
limitation is Ti’s chemical reactivity at high temperatures, which necessitated special techniques
to extract. Thus these alloys are expensive. They also possess excellent corrosion resistance in
diverse atmospheres, and wear properties. Common applications include: space vehicles,
airplane structures, surgical implants, and petroleum & chemical industries.
Refractory metals: These are metals of very high melting points. For example: Nb, Mo, W and
Ta. They also possess high strength and high elastic modulus. Common applications include:
space vehicles, x-ray tubes, welding electrodes, and where there is a need for corrosion
resistance.
Noble metals: These are eight all together: Ag, Au, Pt, Pa, Rh, Ru, Ir and Os. All these possess
some common properties such as: expensive, soft and ductile, oxidation resistant.
Ag, Au and Pt are used extensively in jewelry, alloys are Ag and Au are employed as dental
restoration materials; Pt is used in chemical reactions as a catalyst and in thermo couples.
Introduction to Ceramics:
Ceramics form an important part of materials group. Ceramics are compounds between metallic
and nonmetallic elements for which the inter-atomic bonds are either ionic or predominantly
ionic. The term ceramics comes from the Greek word keramikos which means ‘burnt stuff’.
Characteristic properties of ceramics are, in fact, optimized through thermal treatments. They
exhibit physical properties those are different from that of metallic materials. Thus metallic
materials, ceramics, and even polymers tend to complement each other in service.
Ceramic materials are inorganic, nonmetallic compounds, usually oxides like SiO 2, Al2O3
and non-oxides such as carbides, nitrides, and borides. Both ionic and covalent bonds, and
combination of them, can be found in ceramic materials. The dominant characteristics of
ceramics are summarized by the following:
i. They are stable and resistant to chemical attack.
ii. They are brittle, hard, and wear resistant.
iii. They have high temperature strength.
iv. They are good electrical insulators at room temperature.
v. Their thermal conductivities lie between those of polymers and of metals.
Ceramic materials may occur in the form of single crystal and in the form of polycrystalline
material (polycrystals). These polycrystals are oriented with respect to each other in more or less
completely random way. They are also called “grains”. When the grains have a different
composition, the ceramic material is of multiphase. The grains in the monolithic material are of
single phase.
Figure 1 shows a typical cross-section of ceramic
material. It composed of an assembly of irregularly
shaped grains and pores. The solid-solid interfaces are
called "grain boundaries" and the solid-gas interfaces
are called "free surfaces". Grain boundaries and free
surfaces constitute the microstructure of the ceramic
material.
To obtain polycrystalline ceramic material, a
compressed fine-grained powder is subjected to a high
temperature around 65-75% of its melting point. The
process is called "sintering"; in which the powder
Figure 1: Cross section of ceramic material.
compact shrinks during heating, and its bulk density The dark fields represent the pores.
increases to form the ceramic body. The densification
of the powder compact is accompanied by coarsening
of primary grains "grain growth" and elimination or
decrease in volume of intergranular voids "pore
shrinkage". The evolution and rate of these
microstructure changes are referred as "microstructure
development" of the sintered ceramic body.
The mechanical and physical properties of ceramics are depending on their microstructure.
The mechanical properties are correlated to the grain size (the diameter of the sphere of the same
grain volume) while the thermal, magnetic and electrical properties are influenced by the
existence of the interfaces (grain boundaries and free surfaces). The correlation between the
properties of ceramics and their microstructure reflects the importance of sintering studies.
Normally, these studies attempts to attain high density and controlled grain size of the product.
The arrangement of atoms in solids, in general, and ceramics, in particular, will exhibit long-
range order, only short-range order, or a combination of both. Solids that exhibit long-range
order are referred to as crystalline solids, while those in which that periodicity is lacking are
known as amorphous, glassy, or noncrystalline solids.
Types and applications of ceramics:
Ceramics greatly differ in their basic composition. The properties of ceramic materials also vary
greatly due to differences in bonding, and thus found a wide range of engineering applications.
Classification of ceramics based on their specific applications and composition are two most
important ways among many.
Based on their composition, ceramics are classified as:
Oxides,
Carbides,
Nitrides,
Sulfides,
Fluorides, etc.
The other important classification of ceramics is based on their application, such as:
Glasses,
Clay products,
Refractories,
Abrasives,
Cements,
Advanced ceramics.
In general, ceramic materials used for engineering applications can be divided into two groups:
traditional ceramics, and the engineering ceramics. Typically, traditional ceramics are made from
three basic components: clay, silica (flint) and feldspar. For example bricks, tiles and porcelain
articles. However, engineering ceramics consist of highly pure compounds of aluminium oxide
(Al O ), silicon carbide (SiC) and silicon nitride (Si N ).
2 3 3 4
Glasses: The glass is an amorphous solid completely lacking in long range, periodic atomic
structure, and exhibiting a region of glass transformation (transition) behavior. Any material,
inorganic, organic, or metallic, formed by any technique, which exhibits glass transformation
(transition) behavior, is a glass.
 Glasses are a familiar group of ceramics – containers, windows, mirrors, lenses, etc. They
are non-crystalline silicates containing other oxides, usually CaO, Na O, K O and Al O which
2 2 2 3

influence the glass properties and its color. Typical property of glasses that is important in
engineering applications is its response to heating. There is no definite temperature at which the
liquid transforms to a solid as with crystalline materials. A specific temperature, known as glass
transition temperature or fictive temperature is defined based on viscosity above which material
is named as super cooled liquid or liquid, and below it is termed as glass. Super-cooling a
viscous liquid into the glass state is called vitrification.
Common types of glass
The following is a list of the more common types of silicate glasses, and their ingredients,
properties, and applications:
1. Fused quartz, also called fused silica glass, vitreous silica glass, is silica (SiO2) in vitreous or
glass form (i.e., its molecules are disordered and random, without crystalline structure). It has
very low thermal expansion, is very hard, and resists high temperatures (1000–1500°C). It is
also the most resistant against weathering (caused in other glasses by alkali ions leaching out
of the glass, while staining it). Fused quartz is used for high temperature applications such as
furnace tubes, lighting tubes, melting crucibles, etc.
2. Soda-lime-silica glass, window glass: silica (SiO2) 72% + sodium oxide (Na2O) 14.2% + lime
(CaO) 10.0% + magnesia (MgO) 2.5% + alumina (Al2O3) 0.6%. It is transparent, easily
formed, and most suitable for window glass (flat glass). It has a high thermal expansion and
poor resistance to heat (500–600°C). It is used for windows, some low temperature
incandescent light bulbs, and tableware. Container glass is a soda-lime glass that is a slight
variation on flat glass, which uses more alumina and calcium, and less sodium and magnesium
which are more water-soluble. This makes it less susceptible to water erosion.
3. Sodium borosilicate glass, Pyrex: silica (SiO2) 81% + boric oxide (B2O3) 12% + soda (Na2O)
4.5% + alumina (Al2O3) 2.0%. Stands heat expansion much better than window glass. Used
for chemical glassware, cooking glass, car headlamps, etc.
4. Borosilicate glasses (e.g. Pyrex) have as main constituents: silica and boron oxide. They have
fairly low coefficients of thermal expansion (7740 Pyrex CTE is 3.25×10 –6/°C as compared to
about 9×10−6/°C for a typical soda-lime glass, making them more dimensionally stable. The
lower CTE also makes them less subject to stress caused by thermal expansion, thus less
vulnerable to cracking from thermal shock. They are commonly used for reagent bottles,
optical components, and household cookware.
5. Lead-oxide glass, crystal glass: silica 59% + lead oxide (PbO) 25% + potassium oxide (K2O)
12% + soda (Na2O) 2.0% + zinc oxide (ZnO) 1.5% + alumina 0.4%. Because of its high
density (resulting in a high electron density) it has a high refractive index, making the look of
glassware more brilliant (called "crystal", though of course it is a glass and not a crystal). It
 also has a high elasticity, making glassware 'ring'. It is also more workable in the factory, but
cannot stand heating very well.
6. Aluminosilicate glass: silica 57% + alumina 16% + lime 10% + magnesia 7.0% + barium
oxide (BaO) 6.0% + boric oxide (B2O3) 4.0%. Extensively used for fiberglass, used for
making glass-reinforced plastics (boats, fishing rods, etc.) and for halogen bulb glass.
7. Oxide glass: alumina 90% + germanium oxide (GeO2) 10%. Extremely clear glass, used for
fiber-optic waveguides in communication networks. Light loses only 5% of its intensity
through 1 km of glass fiber. However, most optical fiber is based on silica, as are all the
glasses above.
Clay products: clay is the one of most widely used ceramic raw material. It is found in great
abundance and popular because of ease with which products are made. Clay products are mainly
two kinds – structural products (bricks, tiles, sewer pipes) and white-wares (porcelain,
chinaware, pottery, etc.).
Refractories: these are described by their capacity to withstand high temperatures without
melting or decomposing; and their inertness in severe environments. Thermal insulation is also
an important functionality of refractories.
Abrasive ceramics: these are used to grind, wear, or cut away other material. Thus the prime
requisite for this group of materials is hardness or wear resistance in addition to high toughness.
As they may also exposed to high temperatures, they need to exhibit some refractoriness.
Diamond, silicon carbide, tungsten carbide, silica sand, aluminium oxide / corundum are some
typical examples of abrasive ceramic materials.
Cements: cement, plaster of paris and lime come under this group of ceramics. The characteristic
property of these materials is that when they are mixed with water, they form slurry which sets
subsequently and hardens finally. Thus it is possible to form virtually any shape. They are also
used as bonding phase, for example between construction bricks.
Advanced ceramics: these are newly developed and manufactured in limited range for specific
applications. Usually their electrical, magnetic and optical properties and combination of
properties are exploited. Typical applications: heat engines, ceramic armors, electronic
packaging, etc.
Some typical ceramics and respective applications are as follows:
Aluminium oxide / Alumina (Al2O3): it is one of most commonly used ceramic material. It is
used in many applications such as to contain molten metal, where material is operated at very
high temperatures under heavy loads, as insulators in spark plugs, and in some unique
applications such as dental and medical use. Chromium doped alumina is used for making lasers.
Aluminium nitride (AlN): because of its typical properties such as good electrical insulation but
high thermal conductivity, it is used in many electronic applications such as in electrical circuits
operating at a high frequency. It is also suitable for integrated circuits. Other electronic ceramics
include – barium titanate (BaTiO ) and Cordierite (2MgO-2Al O -5SiO ).
3 2 3 2
Diamond (C): it is the hardest material known to available in nature. It has many applications
such as industrial abrasives, cutting tools, abrasion resistant coatings, etc. it is, of course, also
used in jewelry.
Lead zirconium titanate (PZT): it is the most widely used piezoelectric material, and is used as
gas igniters, ultrasound imaging, in underwater detectors.
Silica (SiO2): is an essential ingredient in many engineering ceramics, thus is the most widely
used ceramic material. Silica-based materials are used in thermal insulation, abrasives, laboratory
glassware, etc. it also found application in communications media as integral part of optical
fibers. Fine particles of silica are used in tires, paints, etc.
Silicon carbide (SiC): it is known as one of best ceramic material for very high temperature
applications. It is used as coatings on other material for protection from extreme temperatures. It
is also used as abrasive material. It is used as reinforcement in many metallic and ceramic based
composites. It is a semiconductor and often used in high temperature electronics. Silicon nitride
(Si N ) has properties similar to those of SiC but is somewhat lower, and found applications in
3 4
such as automotive and gas turbine engines.
Titanium oxide (TiO2): it is mostly found as pigment in paints. It also forms part of certain glass
ceramics. It is used to making other ceramics like BaTiO .
3
Titanium boride (TiB2): it exhibits great toughness properties and hence found applications in
armor production. It is also a good conductor of both electricity and heat.
Uranium oxide (UO2): it is mainly used as nuclear reactor fuel. It has exceptional dimensional
stability because its crystal structure can accommodate the products of fission process.
Yttrium aluminium garnet (YAG, Y3Al5O12): it has main application in lasers (Nd-YAG lasers).
Zirconia (ZrO2): it is also used in producing many other ceramic materials. It is also used in
making oxygen gas sensors, as additive in many electronic ceramics. Its single crystals are part
of jewelry.
Traditional Versus Advanced Ceramics
Traditional ceramics, pottery, sculpture, sanitary ware, tiles, etc., are characterized by mostly
silicate-based porous microstructures that are quite coarse, non-uniform, and multiphase. They
are typically formed by mixing clays and feldspars, followed by forming either by slip casting or
on a potter's wheel, firing in a flame kiln to sinter them, and finally glazing.
In a much later stage of development, other ceramics that were not clay or silicate-based
depended on much more sophisticated raw materials, such as binary oxides, carbides,
perovskites, and other completely synthetic materials for which there are no natural equivalents.
The microstructures of these modern or technical ceramics were at least an order of magnitude
finer, more homogeneous, and much less porous than the traditional.
General Characteristics of Ceramics
Ceramic materials are generally:
1. Hard 6. Electrically insulative
2. Wear-resistant 7. Thermally insulative
3. Brittle 8. Refractory
4. Nonmagnetic 9. Vulnerable (susceptible) to thermal shock
5. Intrinsically transparent 10. Oxidation-resistant, Chemically stable
 However, there will be exceptions; some ceramics are electrically and thermally quite
conductive, while others are even superconducting. An entire industry is based on the fact that
some ceramics are magnetic.
Why ceramics exhibit these properties?
The answer of this question is one of the goals of the study of the structure and
microstructure of ceramics.
Applications
Ceramic materials have a wide range of applications. Some modern applications are:
1. Ceramic engines for transportation and turbines for energy production due to the
refractoriness of ceramics and their ability to sustain high loads at high temperatures,
together with their low densities
2. Optical communications such as fiber optics due to optical properties of a glass
3. Electrooptic applications like displays and transparent displays (semiconductive optical
ceramics)
4. Laser materials (the active materials)
5. Substrates in electronic circuits; due to insulative properties, low-loss factors, and
excellent thermal and environmental stability
6. Ceramic capacitors due to exceedingly large dielectric constants of the perovskite family
7. Magnetic ceramics based on the spinel ferrites
8. Piezoelectric ceramics for sensors and actuators
9. The nonlinear I-V characteristics for circuit protection
10. Ionically conducting ceramics for use as solid electrolytes in high-temperature fuel cells
and as chemical sensors
11. Electrodes in photoelectrochemical devices or cells PEC, which are solar cells that
produce electrical energy or hydrogen in a process similar to the electrolysis of water
12. A new revolution in silicate ceramics (Stone Age materials) is taking place to make them
materials for the future. Alkali-activated cements and mortars (also called geopolymers)
are an example.
In principle, the advantages of an all-ceramic engine are several and include lower weight, a
higher operating temperature that translates to higher efficiencies, and less pollution. It is also
predicted that such engines would not require cooling and maybe not even any lubrication, which
once more would simplify the design of the engine, reducing the number of moving parts, and
lowering the overall weight of the vehicle.
Ceramic Microstructures
Crystalline solids exist as either single crystals or polycrystalline solids. A single crystal is a
solid in which the periodic and repeated arrangement of atoms is perfect and extends throughout
the entire specimen without interruption. A polycrystalline solid is comprised of a collection of
many single crystals, termed grains, separated from one another by areas of disorder known as
grain boundaries.
Typically, in ceramics the grains are in the range of 1 to 50 μm and are visible only under a
microscope. The shape and size of the grains, together with the presence of porosity, second
phases, etc., and their distribution describe what is termed the microstructure. Many of the
properties of ceramics are microstructure-dependent.
Fibres and Plastics:

Fibres and Fabrics:

The clothes are made of fabrics. Fabrics are made from fibres obtained from natural or artificial
sources.
Types of Fibres:
1. Natural fibres: These are obtained from natural sources, called natural resources. Examples:
cotton, silk, wool, etc.
Fabrics are made by weaving fibres (or threads) obtained from natural or artificial sources. They
can be of two types:
2. Synthetic fibres: These are man-made are called man-made or synthetic fibres. Examples:
rayon, nylon, acrylic, etc.
(i) Synthetic fibres are made of small units of chemicals joined together in the form of large
chain. The formed chain is called polymer.
(ii) Polymer is a Greek word in which ‘poly’ means many and ‘mer’ means units. So, a polymer
is made of many repeating units.
(iii) Polymers occur in nature also. Example: Cotton is a polymer called cellulose. Cellulose is
made up of a large number of glucose units.
Fabrics are made by weaving fibres (or threads) obtained from natural or artificial sources. They
can be of two types:
Types of Synthetic Fibres:
1. Rayon:
(i) Fibre is obtained by chemical treatment of wood pulp. This fibre is called rayon or artificial
silk.
(ii) Rayon fibre can be made in different colours by dyed. Rayon is very cheap compared to silk.
(iii) Rayon is mixed with cotton to make bed sheets or mixed with wool to make carpets.

Use of Rayon Fibres

2. Nylon:
(i) Nylon is man-made fibre. It was first fully synthesized fibre. The production of nylon was
started without using any natural raw material (from plant or animal) almost simultaneously in
New York and London, thus it got its name (NY for New York and Lon for London) as nylon. It
is synthesized from coal, water and air. Cloths from nylon are very strong elastic and light
lustrous and easy to wash.
(ii) Firstly nylon was used in making bristle of toothbrush commercially. After that, it was used
for making fabrics.
(iii) Nylon is used for making clothes, ropes, socks, curtains, sleeping bags, parachutes, etc. The
nylon fibre is stronger than a steel wire.
3. Polyester:
(i) Polyester (Poly + ester) is made up of the repeating units of a chemical called an ester.
(ii) Polyester is a man made or synthetic fibre. Fabric made from this fibre does not get wrinkled
easily, remains crisp and easy to wash. Example: shirts, pants, jacket, bed sheets, curtains, sarees,
mouse-pad, etc.
(iii) Polyester is used to make ropes, fabrics for conveyor belt, cushioning and insulating material
in pillow, etc.
(iv) Terrycot is made by mixing of two types of fibres terylene and cotton. Polycot, polywool,
etc. are other fabrics are made by the mixing of polyester with other natural fibres.
(v) PET is a very familiar form of polyester. It is used for making bottles, utensils, films, wires
and many other useful products.

Polyester is made up of two words - 'poly' which means many, and 'ester' which is a chemical.
Esters are chemicals which give fruits their smell.
Name some types of Polyester fibres.
Some popular polyester fibres are:
 Terylene (often known by brand name Dacron) which can be drawn into a very fine fibre and
can be woven like any other yarn.
 Polyethylene terephthalate (P.E.T.) is used for making wires, films, bottles, utensils and other
products.
What are blended fibres? Give some examples.
Blended fibres are formed by mixing natural and synthetic fibres. Polyester is often used in
blended fibres. For Example,
 Polywool is made by mixing polyester and wool.
 Polycot is made my mixing polyester and cotton.
 Terrycot is made by mixing Terylene and cotton.
Uses of Polyester
Since polyester is strong, wrinkle-resistant and water-resistant, it has several uses. It can be used
to:
 Make a variety of textiles (including sarees, curtains, dress materials etc.) and can be blended
with natural fibres (like cotton and wool)
 Make films, magnetic recording tapes, etc (as Mylar)
 Make sails of sailboats
 Make water hoses for firefighting purposes
4. Acrylic:
(i) Acrylic is man-made or synthetic fibre. Acrylic resembles wool. It is also called as artificial
wool or synthetic wool. Acrylic is cheaper than natural wool and can be made in various colours
by dyeing.
(ii) Clothes are made from acrylic are relatively cheaper than cloths are made by wool.
(iii) Acrylic is used in making sweaters, blanket, and other many clothes.
Acrylic is a strong, lightweight and warm synthetic fibre that resembles wool. It is available in a
number of colours and is more durable and affordable than natural wool.
Acrylic fibre, fabric, plastic or paint are all made from acrylic acid. The word 'acrylic' means
'containing acryl (or acrolein)' Acrolein is the sharp and bitter liquid in onions and has its roots
in two Latin words - 'acer' which means 'sharp', and 'olere' which means 'to smell'.
Why storage of acrylic clothes is easier than woollen clothes?
Woollen clothes need naphthalene balls to protect them from attack by insects. Acrylic is
synthetic wool and is hence, resistant to the action of moths and insects.
Uses of Acrylic Fibre
Acrylic can mimic wool as well as cotton at times and is hypoallergenic in nature. It means that
people who have sensitive skin can wear it easily. Some acrylic fibres are very resilient – more
than other natural or synthetic fibres. It can be used to:
 Make woollen clothes like hats, scarves, gloves, sweaters, blankets, and other home-
furnishing fabrics.
 Make fake fur used for making toys and fur accessories.
 Make garments for babies (as the fabric is machine-washable).
Characteristics of Synthetic Fibres:
(i) Synthetic fibres are cheaper, stronger and durable than natural fibre.
(ii) It is easy to maintain, easy to wash, dry up in less time and readily available.
(iii) Synthetic fibres possess unique characteristics which make them popular dress materials.
Characteristics of Synthetic Fibres
What are synthetic fibres made up of?
All the synthetic fibres are manufactured by processing raw materials of petroleum origin in a
number of ways. The raw materials of petroleum origin are called Petrochemicals.
Why should we not wear synthetic clothes in the kitchen?
Synthetic fibres melt on heating. If the clothes catch fire, the fabric made up of synthetic fibres
will melt and stick to one's body. Hence, it is recommended that one should not wear synthetic
clothes while working in the kitchen or laboratory.
Plastics:
Plastic is a polymer (like the synthetic fibre) which can be moulded into different shapes. The
word ‘plastic’ originates from the Greek word ‘plastikos’ which means ‘that can be moulded
or shaped’. Plastic polymers can have different types of arrangement of monomers:

Plastic is easily mouldable in all types of possible shapes. Plastic can be recycled, coloured,
reused, rolled into sheets or made into wires.
(i) Plastic is used in making toys, suitcase, bags, cabinets, brush, chairs, tables, and many other
countless items.
(ii) Polythene (Poly + ethene) is one of the most famous examples of plastic, which is used in
manufacturing of carry bags.

Types of Plastic:
Plastic can be divided into two main types – Thermoplastics and Thermosetting.
 Plastics as Materials of Choice
Advantages of Plastic
Not-reactive(does not rust like iron when
Lower Good Easy Poor conductor of
Lightweight exposed to water and air, and doesnot
price strength handling heat and electricity
corrode easily)
Give Reasons Why:
Buckets are made of plastic these days.
Plastic buckets are strong, lightweight, and do not rust.
Bakelite plastic is used to make electrical switches.
Bakelite is a poor conductor of heat and electricity. Hence, they would not give anyone an
electric shock when someone touches the switch.
Melamine is used to make crockery.
Melamine is unbreakable, fire resistant, and tolerates heat better than plastics. Hence, it can be
used to make crockery that can hold hot liquids or dishes served in it.
Plastics are used in cars, aircraft and spacecraft.
Plastics are strong, durable, lightweight, and corrosion-resistant.
Chemicals are stored in plastic bottles.
Plastic bottles are lightweight, unbreakable, corrosion-resistant, and are resistant to the action of
chemicals. Hence, they are suitable for storing chemicals.
Which plastic is used to make:
Non-stick coating on Cookware: Teflon
Insulation covering on Wires: PVC
Polythene Bags: Polythene
Flame-resistant Uniforms: Melamine
Special uses of Plastic

Besides being used in packaging for food and non-food items and several daily-used items (such
as furniture, electrical switches, slippers etc.), plastic also has special uses such as:
 Used in the healthcare industry for packaging of tablets, syringes, doctor's gloves, a number of
medical instruments, and threads for stitching wounds.
 Used to make cookware used in microwave ovens
 Used as a non-stick coating on cookware (made of a special plastic called Teflon is used on
which oil and water do not stick)
 Used to make the fire-resistant uniform for firefighters (made of Melamine)
1. Thermoplastic:
(i) Such plastics which get easily bent or deform on heating are known as thermoplastic.
Examples of thermoplastics are PVC and Polythene. (ii) It is used in making toys, bottles,
combs, containers, etc.
2. Thermosetting plastic:
(i) Such plastics which when mould once, cannot be softened or deformed by heating. These are
called thermosetting plastics. Examples of thermosetting plastics are Bakelite and melamine.
(ii) These plastics are used in making hard board, electric switch, handles of electrical
appliances, handles of kitchen utensils, floor tiles, etc.
(iii) Melamine is versatile material and poor conductor of heat. It resists fire, thus it is used in
making floor tiles, kitchen materials, fabrics which resist fire.
(iv) Bakelite is poor conductor of electricity and heat, thus it is used for making electrical
switches, handles of various utensils and other electrical appliances.

Plastic as a material of choice:

Plastic has light weight, lower price, good strength and easy handling. Being lighter as compared
to metals, plastics are used in cars, aircrafts and spacecrafts, too.
Characteristic properties of plastics:
1. Plastic is non-reactive:
(i) Plastics do not react with water and air that’s whyit does not get rusted like iron. They are not
corroded easily. That is why they are used to store various kinds of material, including many
chemicals.
(ii) Due to this property of plastic, it is suitable for making of container, water tank, water bottle,
plastic pipes, taps, chair, table and other many types of furniture.
2. Plastic is light, strong and durable:
(i) Plastics are light weight, durable, cheap, very strong and can be moulded into different shapes
and sizes.
(ii) Due to this property of plastic, it is very much in need today. It is used for various purposes
like polythene bags or pencil box, water bottle or umbrella, furniture or air craft, the use of
plastic can be seen everywhere.
3. Plastics are poor conductors:
(i) Plastics are poor conductor of heat and electricity.
(ii) Due to this property of plastics, it is suitable to make the insulating covering of electric wires,
handles of electrical appliances, handles of utensils, handles of screw drivers, kitchenware, floor
tiles, etc.
Some Uses of Plastic in Various Fields:
(i) Plastics find extensive use in the health-care industry. Plastics are used for the packaging of
tablets, threads used for stitching wounds, syringes, doctors’ gloves and a number of medical
instruments.
(ii) Special plastic cookware is used in microwave ovens for cooking food without affecting the
plastic vessel.
(iii) Teflon is a special plastic on which oil and water do not stick. It is used for making non-stick
coating on cook wares.
(iv) Fire-proof plastics: Synthetic fibre catches fire easily. The uniforms of firemen have coating
of melamine plastic to make them flame resistant.
Biodegradable and Non-biodegradable:
1. Biodegradable:
A substance which gets decomposed through natural processes, such as action by bacteria, is
called biodegradable. Examples: peels of vegetables, food stuffs, fruit, paper, cotton cloths,
wood, etc.

2. Non-biodegradable:
A substance which is not easily decomposed or takes many years to get decomposed by natural
processes is termed as non-biodegradable. Examples: tin, aluminium, plastics, etc.

Plastics and the Environment:

Plastic is a threat to the environment as it is non-biodegradable. Its disposal is a big problem.

Biodegradable: Plastic is a non-biodegradable material. It takes many years to get decomposed
or either does not get decomposed. Material which gets decomposed through natural processes
(such as bacterial action) is called Biodegradable.
 Non-biodegradable: Material which cannot be easily decomposed by natural processes is
called Non-biodegradable. Due to non-biodegradable property of plastic, it is a very major
problem for environment.
How do plastics cause environmental pollution?
Plastics cause pollution as they:
 are non-biodegradable, and
 release toxic fumes when burnt (and hence, cause air pollution).
Problem:
(i) Now days, plastic is very popular and used it for many purposes. As a result, we generate a
large amount of plastic waste. Since plastic has non-biodegradable property, so plastic waste is
getting accumulated in the environment. It causes environmental pollution.
(ii) Accumulated plastic waste is a major concern as it does not get completely burnt easily. In
the process it releases lots of poisonous fumes into the atmosphere causing air pollution.
Preventive measures:
(i) We should avoid the use of plastics things as far as possible.
(ii) Do not throw plastic bags in the water bodies or on the road.
(iii) The biodegradable and non biodegradable wastes should be collected separately and
disposed off separately.
For dealing with plastic waste, we should follow the three Rs, i.e. Reduce, Reuse and Recycle.
1. Reduce:
We should reduce the use of plastic. Examples: We should use cloth or jute bag for purchasing
any things instead of using plastic bags.
2. Reuse:
We should reuse some plastic things and containers in our homes and offices, For example:
Empty plastic bottles and container should be used for keeping other items in the home and
kitchen.
3. Recycle:
Thermoplastic can be recycled. So, items made of thermoplastic should be sent to the recycling
industry. Examples: Toys, buckets, mugs etc.

Mechanical properties of metals:

Most of the materials used in engineering are metallic in nature. The prime reason simply is the
versatile nature of their properties those spread over a very broad range compared with other
kinds of materials. Many engineering materials are subjected to forces both during
processing/fabrication and in service. When a force is applied on a solid material, it may result in
translation, rotation, or deformation of that material. Aspects of material translation and rotation
are dealt by engineering dynamics. We restrict ourselves here to the subject of material
deformation under forces. Deformation constitutes both change in shape, distortion, and change
in size/volume, dilatation. Solid material are defined such that change in their volume under
applied forces in very small, thus deformation is used as synonymous to distortion. The ability of
material to with stand the applied force without any deformation is expressed in two ways, i.e.
strength and hardness. Strength is defined in many ways as per the design requirements, while
the hardness may be defined as resistance to indentation of scratch.
Material deformation can be permanent or temporary. Permanent deformation is irreversible i.e.
stays even after removal of the applied forces, while the temporary deformation disappears after
removal of the applied forces i.e. the deformation is recoverable. Both kinds of deformation can
be function of time, or independent of time. Temporary deformation is called elastic
deformation, while the permanent deformation is called plastic deformation. Time dependent
recoverable deformation under load is called an elastic deformation, while the characteristic
recovery of temporary deformation after removal of load as a function of time is called elastic
aftereffect. Time dependent i.e. progressive permanent deformation under constant load/stress is
called creep. For visco-elastic materials, both recoverable and permanent deformations occur
together which are time dependent. When a material is subjected to applied forces, first the
material experiences elastic deformation followed by plastic deformation. Extent of elastic- and
plastic- deformations will primarily depend on the kind of material, rate of load application,
ambient temperature, among other factors. Change over from elastic state to plastic state is
characterized by the yield strength (σ0) of the material.
Forces applied act on a surface of the material, and thus the force intensity, force per unit area, is
used in analysis. Analogous to this, deformation is characterized by percentage change in length
per unit length in three distinct directions. Force intensity is also called engineering stress (or
simply stress, s), is given by force divided by area on which the force is acting.
Elastic deformation:
When the stress is removed, the material returns to the dimension it had before the load was
applied. Valid for small strains (except the case of rubbers).Deformation is reversible, non
permanent.
Plastic deformation:
When the stress is removed, the material does not return to its previous dimension but there is a
permanent, irreversible deformation. In tensile tests, if the deformation is elastic, the stress-strain
relationship is called Hooke's law: σ = E ε
That is, E is the slope of the stress-strain curve. E is Young's modulus or modulus of elasticity. In
some cases, the relationship is not linear so that E can be defined alternatively as the local slope:
E = dσ/dε
Shear stresses produce strains according to:
τ=Gγ
where G is the shear modulus. Elastic moduli measure the stiffness of the material. They are
related to the second derivative of the inter atomic potential, or the first derivative of the force
vs. inter nuclear distance. By examining these curves we can tell which material has a higher
modulus. Due to thermal vibrations the elastic modulus decreases with temperature. E is large for
ceramics (stronger ionic bond) and small for polymers (weak covalent bond). Since the inter
atomic distances depend on direction in the crystal, E depends on direction (i.e., it is anisotropic)
for single crystals. For randomly oriented policrystals, E is isotropic.
Volumetric strain or cubical dilatation is defined as the change in volume per unit volume.
The ratio of transverse strain to longitudinal strain is known as Poisson’s ratio.
The proportional relation between the stress and the elastic strain is given by Hooke’s law.
Tensile Properties:
Yield point. If the stress is too large, the strain deviates from being proportional to the stress.
The point at which this happens is the yield point because there the material yields, deforming
permanently (plastically).
Yield stress. Hooke's law is not valid beyond the yield point. The stress at the yield point is
called yield stress, and is an important measure of the mechanical properties of materials. In
practice, the yield stress is chosen as that causing a permanent strain of 0.002. The yield stress
measures the resistance to plastic deformation. The reason for plastic deformation, in normal
materials, is not that the atomic bond is stretched beyond repair, but the motion of dislocations,
which involves breaking and reforming bonds. Plastic deformation is caused by the motion of
dislocations.
Tensile strength: When stress continues in the plastic regime, the stress-strain passes through a
maximum, called the tensile strength, and then falls as the material starts to develop a neck and it
finally breaks at the fracture point. For structural applications, the yield stress is usually a more
important property than the tensile strength, since once it is passed, the structure has deformed
beyond acceptable limits.
Ductility: The ability to deform before braking. It is the opposite of brittleness. Ductility can be
given either as percent maximum elongation åmax or maximum area reduction.
%EL = åmax x 100 %
%AR = (A0 - Af)/A0
These are measured after fracture (repositioning the two pieces back together).
Resilience: Capacity to absorb energy elastically. The energy per unit volume is the area under
the strain-stress curve in the elastic region.
Toughness: Ability to absorb energy up to fracture. The energy per unit volume is the total area
under the strain-stress curve. It is measured by an impact test.
True Stress and Strain
When one applies a constant tensile force the material will break after reaching the tensile
strength. The material starts necking (the transverse area decreases) but the stress cannot increase
beyond tensile strength. The ratio of the force to the initial area, what we normally do, is called
the engineering stress. If the ratio is to the actual area (that changes with stress) one obtains the
true stress.
Let us start with some observations
 An Al rod when bent through a large angle does not come back to its original shape.
 Steel is more difficult to deform as compared to Al.
 A steel piece is easier to deform when heated (as compared to when it is cold).
 ‘Chinese’ Clay when deformed does not regain its original shape.
 ‘Silly putty’ deforms like Chinese clay when slowly deformed. However, when one
bounces a ball of silly putty it bounces like a rubber ball.
Important points to be kept in mind
 There is no volume change during plastic deformation (by slip/twinning).
 Shear stresses lead to plastic deformation in metallic materials  Pure hydrostatic
stresses cannot cause plastic deformation (metals).
 Shear stresses can arise due to: (i) shear loading, (ii) geometry of loading, (iii) orientation
of planes within the material. Crystals unlike glasses can have planes which are weak in
shear or tension (which can lead to failure; these are like the “weakest link in the chain”).
 Fracture strain is strongly influenced by hydrostatic stresses.
 Plastic deformation by slip (motion of dislocations leaving the crystal/grain) involves
shear stresses at the level of the slip plane (i.e. even if we apply tensile forces, certain
planes may feel shear stresses, which can lead to slip).
 Amorphous materials can deform by ‘flow’ (e.g. glass blowing of heated glass), etc. →
these are not the focus of the current chapter.
 Plastic deformation in the broadest sense means permanent deformation in the absence of
external constraints (forces, displacements)
(i.e. after the removal of external loads and constraints which caused the deformation).
 Plastic deformation of crystalline materials takes place by mechanisms which are very
different from that for amorphous materials (glasses). The current chapter will focus on
plastic deformation of crystalline materials. Glasses deform by shear banding etc. below
the glass transition temperature (Tg) and by ‘flow’ above Tg.
 Though plasticity by slip is the most important mechanism of plastic deformation, there
are other mechanisms as well. Many of these mechanisms may act in conjunction/parallel
to give rise to the observed plastic deformation. Twinning is perhaps the second most
important one.
 Orientation across the slip plane is same and orientation across the twin plane is different.
The atomic movements are equal to atomic distances; the atomic movements are lesser
than atomic distances in the twins. The atoms are moving in only one plane (slip plane)
and the atoms moving in all planes in the region of twin. Slip takes place in milli seconds
and twin takes place less than micro seconds. Slip takes place at low strain rates where as
 in twin takes place at high strain rates. No sound is created by the slip and a click sound
(tin cry) by the twin.

Note: Plastic deformation in amorphous materials occur by other mechanisms including flow
(~viscous fluid) and shear banding

Path to understanding plasticity

 The following aspects need to be understood to comprehend plasticity*:
 External process parameters (Temperature, strain rate, etc.)
 Macroscopic and Microscopic aspects of plasticity
 Continuum and Discrete views of plasticity
 Plasticity in single crystals
 Plasticity in polycrystals
 Plasticity in multiphase materials
 Plasticity in nanomaterials

 O  unloaded specimen
 OY  Elastic  Linear Region in the plot (macroscopic linear elastic region)
 Y  macroscopic yield point (there are many measures of yielding as discussed later)
Occurs due to collective motion of many dislocations finally leaving the grain boundary
or crystal surface.
The stress at this point is called yield strength. [i.e. stress  strength]
  YF  Elastic + Plastic regime
 If specimen is unloaded from any point in this region, it will unload parallel to OY and
the elastic strain would be recovered. Actually, more strain will be recovered than
unloading from Y (and hence in some sense in the region YF the sample is ‘more elastic’
than in the elastic region OY).
 In this region the material strain hardens  flow stress increases with strain.
 This region can further be split into YN and NF as below.
 YN  Stable region with uniform deformation along the gauge length
 N  Plastic Instability in tension  Onset of necking
True condition of uniaxiality broken  onset of triaxial state of stress (loading remains
uniaxial but the state of stress in the cylindrical specimen is not).
 NF  most of the deformation is localized at the neck
 Specimen in a triaxial state of stress
 F  Fracture of specimen (many polycrystalline materials like Al show cup and cone
fracture)
Notes:
 In the - plot there is no distinct point N and there is no drop in load (as instantaneous
area has been taken into account in the definition of ) in the elastic + plastic regime
(YF).
 The stress is monotonically increasing in the region YF  true indicator of strain
hardening.
Information which can be obtained from a uniaxial tension test:

 Young’s modulus*→ slope of the OY (elastic part of the curve).

 Yield stress (or proof stress)→ stress corresponding to point Y.
 Ultimate Tensile Stress (UTS) → point N (maximum) in s-e plot.
 Fracture stress→ stress corresponding to point F.
 Ductility→ measured as: (a) strain at fracture (in %), (b) % reduction in area.
 Resilience (area under the curve elastic portion- OY).
 Toughness (area under the curve total)→ has unit of Energy/volume [J/m3].
 Strain hardening exponent (from - plot).
 As we shall see that during the tension test localized plastic deformation occurs after
some strain (called necking). This leads to inhomogeneity in the stress across the length
of the sample and under such circumstances true stress should be used.
 Twinning is a prominent mechanism of plastic deformation in some metallic materials. It
is a shear force that can produce atomic displacements.
 Twinning may be produced by mechanical deformation or as the result of annealing
following plastic deformation. High strain rates, low stacking-fault energy and low
temperatures facilitate deformation twinning. Twinning is polar (unidirectional), while
slip usually is not. Twinning is also known as mechanical twinning .
 The mechanical work of deformation twinning is dissipative, resulting from the defect
motion associated with shearing. The important role of twinning in plastic deformation is
that it causes changes in plane orientation so that further slip can occur.
 The quantity of bulk plastic deformation from twinning is relatively small compared to
slip. However, the real importance of twinning lies with the accompanying
 crystallographic reorientations; twinning may place new slip systems in orientations that
are favorable relative to the stress axis such that the slip process can take place.
 Twinning differs from slip in several respects. First, for slip, the crystallographic
orientation above and below the slip plane is the same both before and after the
deformation; for twinning, there is a reorientation across the twin plane.


Careful experimentation has to be done to capture the full details of the Yield Point Phenomena
region (not done here!)
Notes
 The cross head velocity is in mm/min.
 Steel has a higher yield stress and UTS.
 It is not a good idea to calculate Young’s modulus (or the elongation in the elastic region)
from the stress-strain plots. This is because the machine compliance is in series with the
specimen compliance.
 In materials like steel the Yield Point Phenomenon is observed. This occurs due to
‘locking’ of dislocations by carbon atoms (more about this elsewhere).
 This phenomenon is also observed in other materials (like LiF crystals), wherein there is
a paucity of mobile dislocations.
Result of an actual stress(s)-strain(e) plots
 Thus by point ‘P’ some plastic deformation must have already
 True (it is very confusing!). We have the macroscopic picture and the microscopic
picture.
 In the macroscopic picture, we have three quantities related to the limit of elasticity or
start of yielding in a uniaxial tension test.
1) Proportional limit  the point ‘C’ the linear portion.
2) Elastic limit the point ‘D’ from where if the specimen is unloaded it will return to
‘O’.
3) 0.2% offset  the point ‘P’ obtained by drawing a line parallel to OC starting at point
‘S’ (a strain of 0.2%) to intersect the curve at P. The stress corresponding to ‘P’ is called
the 0.2% offset proof stress and is a practical measure of yield stress.
 Microscopically, the region OD can be divided into three parts:
1) Region OA  ‘truly’ elastic. Region where dislocations do not move.
2) Region AB  Also Elastic. Dislocations move reversibly (i.e. dislocations start to
move, but do not leave the grains, return to original configuration on release of load).
3) Region BD  Microscopically plastic. Macroscopically elastic. Region where
dislocations move and leave the crystal, but this is not manifested in the stress strain
curve.
 Yielding begins when a stress equal to y (yield stress) is applied; however to cause
further plastic deformation to be applied  i.e. the material hardens with plastic
deformation → known as woincreased stress has rk hardening/strain hardening.
 Beyond necking the state of stress becomes triaxial (in a cylindrical specimen
considered). Technically the yield criterion in uniaxial tension cannot be applied beyond
this point.
 We shall keep our focus on plastic deformation by slip.
 y is yield stress in an uniaxial tension test (i.e. plastic deformation will start after
crossing yield stress only under uniaxial tensile loading) and should not be used in other
states of stress (other criteria of yield should be used for a generalized state of stress).
 I.e in uniaxial tension the yield criterion is very simple:
Yielding starts when:   y . Note:  is a field variable and y is a material property.
 Hydrostatic pressure (leading to hydrostatic stress in a material) does not lead to yielding
in a continuous solid (usually!).
 This implies that the stress deviator holds the key to yielding.
 For an isotropic material the yield criterion will not be independent of the choice of the
axes (i.e. a invariant function). Hence, for an isotropic material the yield criteria (we will
note that there are more than one) will be a function of the invariants of the stress
deviator.
 Two commonly yield criteria are:
 Von Mises or Distortion-Energy Criterion
 Maximum shear stress or Tresca Criterion. (We will consider these later).
Plastic deformation by slip:
 Now we try to understand the underlying mechanisms for plastic deformation.
 As we noted in the beginning of the chapter plastic deformation can occur by many
mechanisms  SLIP is the most important of them. At low temperatures (especially in
BCC metals) twinning may also be come important.
 At the fundamental level plastic deformation (in crystalline materials) by slip involves the
motion of dislocations on the slip plane  finally leaving the crystal/grain* (creating a
step of Burgers vector).
 Slip is caused by shear stresses (at the level of the slip plane). Hence, a purely hydrostatic
state of stress cannot cause slip (or twinning for that matter).
 A slip system consists of a slip direction lying on a slip plane.
 Under any given external loading conditions, slip will be initiated on a particular slip
system if the Resolved Shear Stress (RSS)** exceeds a critical value [the Critical
Resolved Shear Stress (CRSS)].
 For slip to occur in polycrystalline materials, 5 independent slip systems are required.
Hence, materials which are ductile in single crystalline form, may not be ductile in
polycrystalline form. CCP crystals (Cu, Al, Au) have excellent ductility.
 At higher temperatures more slip systems may become active and hence polycrystalline
materials which are brittle at low temperature, may become ductile at high temperature.
 In CCP, HCP materials the slip system consists of a close packed direction on a close
packed plane.
 Just the existence of a slip system does not guarantee slip  slip is competing against
other processes like twinning and fracture. If the stress to cause slip is very high (i.e.
CRSS is very high), then fracture may occur before slip (like in brittle ceramics).
 What is ‘ductility’ and what are the factors which affect the ductility?
 Ductility implies the ability of the material to undergo plastic deformation (typically
before fracture). We have to distinguish between macroscopic and microscopic ductility.
Often, there might be no/little visible macroscopic ductility, but considerable amount of
plastic deformation at the microscopic level.
 Broadly, we can think of three factors which affect the ductility of a material, as shown in
the flow diagram below. Needless to point out, the material properties are to considered
at the test conditions and hence these two aspects are intimately linked.
 A material which may be brittle at low T, may become ductile at high temperatures.
 At high strain rates (which results from a high loading rate) a ductile material (i.e. under
low rates of loading) may behave in a brittle manner.
 Sometimes less importance is paid to the geometry or state of stress. The geometry of the
component plays an important role in deciding the loading conditions on the material.
E.g. a spring pulled in tension leads to torsion at the material level.
We have already seen that a ‘neck’ in the specimen (which is like a blunt crack) leads to a
triaxial state of stress, which suppresses plastic deformation. The worst case scenario is
‘hydrostatic’ state of stress, wherein there is no plane which experiences shear stresses. Since
shear stresses are required for plastic deformation, this state of stress is not conducive for plastic
deformation. This implies that the material will seem brittle, albeit the fact that the material is
still “ductile”
Tensile stress-strain curves:
As shown in figure-2, at initial stages load is proportional to elongation to a certain level (elastic
limit), and then increases with elongation to a maximum (uniform plastic deformation), followed
by decrease in load due to necking (non-uniform plastic deformation) before fracture of the
specimen occurs. Magnified view of the initial stage of the curve is shown in figure-3. Along the
segment AB of the curve, engineering stress is proportional to engineering strain as defined by
Hooke’s law, thus point-B is known as proportional limit. Slope of the line AB gives the elastic
modulus of the material. With further increase in stress up to point-C, material can still be elastic
in nature. Hence point-C is known as elastic limit. It is to be noted that there is no point where
exactly material starts deform plastically i.e. there is no sharp point to indicate start of the yield.
Otherwise point-C can also be called yield point. Thus it is common to assume that stress value
at 0.2% offset strain as yield strength (σ0), denoted by point-D. This offset yield strength is also
called proof stress. Proof stress is used in design as it avoids the difficulties in measuring
proportional or elastic limit. For some materials where there is essentially no initial linear
portion, offset strain of 0.5% is frequently used. In figure-3 distance between points-B, C and D
is exaggerated for clarity. For many materials it is difficult to make any difference between
points-B and C, and point-D also coincides with point-B/C. After the yield point, point-D, stress
reaches a maximum at point-E (tensile strength (σf) as figure-4.4) till where plastic deformation
is uniform along the length of the specimen. Stress decreases hereafter because of onset of
necking that result in non-uniform plastic deformation before specimen fractures at point-F,
fracture limit. Yield strength and tensile strength are the parameters that describe the material’s
strength, while percent elongation and reduction in cross-sectional area are used to indicate the
material’s ductility – extent of material deformation under applied load before fracture.
Figure-2: Typical load – elongation / engineering stress – engineering strain / true stress – true
strain curve.
It is well known that material deforms under applied loads, and this deformation can be
characterized by stress-strain relations. The stress-strain relation for a material is usually
obtained experimentally. Many kinds of experiments those differ in way of loading the material
are standardized. These include tension test, compression test (upsetting), plane strain
compression test, torsion test, etc.
The engineering tension test is commonly used to provide basic design information on the
strength characteristics of a material. Standardized test procedure is explained by ASTM
standard E0008-04. In this test a specimen is subjected to a continually increasing uni-axial
tensile force while measuring elongation simultaneously. A typical plot of load-elongation is
given in the figure-2. The curve also assumes the shape of an engineering stress – engineering
strain curve after dividing the load with initial area and the elongation with initial length. The
two curves are frequently used interchangeably as they differ only by constant factors. The shape
and relative size of the engineering stress-strain curve depends on material composition, heat
treatment, prior history of plastic deformation, strain rate, temperature and state of stress
imposed on specimen during the test.
 Figure-3: Magnified view of initial part of stress-strain curve.
Creep:
Creep is the time-varying plastic deformation of a material stressed at high temperatures.
Examples: turbine blades, steam generators. Keys are the time dependence of the strain and the
high temperature.
Though plasticity by slip is the most important mechanism of plastic deformation, there are other
mechanisms as well (plastic deformation here means permanent deformation in the absence of
external constraints):

 In some sense creep and superplasticity are related phenomena: in creep we can think of
damage accumulation leading to failure of sample; while in superplasticity extended
plastic deformation may be achieved (i.e. damage accumulation leading to failure is
delayed).
 Creep is permanent deformation (plastic deformation) of a material under constant load
(or constant stress) as a function of time. (Usually at ‘high temperatures’ → lead creeps at
RT).
 Normally, increased plastic deformation takes place with increasing load (or stress)
 In ‘creep’ plastic strain increases at constant load (or stress)
 Usually appreciable only at T > 0.4 Tm  High temperature phenomenon.
 Mechanisms of creep in crystalline materials is different from that in amorphous
materials. Amorphous materials can creep by ‘flow’.
 At temperatures where creep is appreciable various other material processes may also
active (e.g. recrystallization, precipitate coarsening, oxidation etc.- as considered before).
 Creep experiments are done either at constant load or constant stress and can be classified
based on Phenomenology or underlying Mechanism.
Constant load creep curve:
 In a typical creep test the load and temperature are kept constant and the elongation is
monitored with time. The strain (typically engineering strain) computed from the
elongation is plotted as function of time. The loads employed are typically below the
elastic limit.
 Three stages may be observed in such a plot: (i) decreasing rate with time, (ii)
approximately constant rate, (iii) increasing rate with time. These stages have to be
understood keeping in view underlying mechanisms (& necking in stage-III).
The instantaneous strain seen (0) is the elastic strain, which develops on the application of the
load.

Stage-III
 Absent (/delayed very much) in constant stress tests (shown later).
 Necking of specimen starts in this stage.
 Specimen failure processes set in.
Constant Stress creep curve:
 In stage-III (due to necking) the engineering stress is no longer a correct measure of the
state of stress. To keep the stress constant, the instantaneous area has to be taken into
account.
 If this is done, then the increasing strain rate part is not observed. Note: if load is kept
constant then in stage-III the stress is actually increasing (for the material it is stress
which matters and not load).
Effect of stress on the creep curve (constant load)
 On increasing the load at which the experiment is conducted: (i) the instantaneous strain
(elastic) increases, (ii) for a given time (say t1) the strain is more, (iii) the time to failure
(tf) decreases (i.e. as expected, specimens fail earlier).

Creep Mechanisms of crystalline materials

 Stress and temperature are the two important variables, which not only affect the creep
rate, but also the mechanism operative. Three kinds of mechanisms are operative in
creep:
1 dislocation related,
2 diffusional,
3 grain boundary sliding.
These and their sub-classes are shown in the next page.
 At high temperatures the grain boundary becomes weaker than the grain interior and two
grains can slide past one another due to shear stress. The temperature at which the grain
is as strong as the grain boundary is called the equicohesive temperature.
 A combination of these mechanisms could also be responsible for the creep strain.
 Depending on the stress and temperature other mechanisms of plastic deformation or
microstructural changes may occur concurrently with creep. These include plastic
deformation by slip and dynamic recrystallization.
 Deformation mechanism maps can be drawn with homologous temperature (T/T m) and
normalized shear stress (/G) as the axis (other combination of variables may also be
chosen for these plots: T/Tm vs shear strain rate, normalized shear stress vs shear strain
rate, etc.). Typically these maps overlay descriptors, which are based both on
phenomenology and mechanism.
Creep Resistant Materials:

 The is a growing need for materials to operate at high temperatures (and in some
applications for long times). For example, higher operating temperatures gives better
efficiency for a heat engine. Hence, there is a need to design materials which can
withstand high temperatures.
 It is to be noted that material should also be good in other properties for high temperature
applications (like it should possess good oxidation resistance). Factors like cost, ease of
fabrication, density, etc. play an important role in determining the final choice of a
material.
 Some of the material design strategies, which work at low temperature are not useful at
high temperatures (e.g. work hardening, precipitation hardening with precipitates which
coarsen, grain size reduction, etc.).
 Some strategies which work are: (i) having grain boundaries aligned along the primary
loading axis, (ii) produce single crystal components (like turbine blades), (iii) use
precipitates with low interfacial energy for strengthen (which will not coarsen easily),
(iv) use dispersoids for strengthening.

 Commonly used materials → Fe, Ni (including superalloys), Co base alloys.

 Precipitation hardening involving ‘usual precipitates*’ is not a good method as
precipitates coarsen (smaller particles dissolve and larger particles grow  interparticle
separation ↑ thus lowering the strength)
 Ni-base superalloys have Ni3(Ti,Al) precipitates, which form a low energy interface with
the matrix. This reduces the driving force for coarsening. (Note: other phenomena like
rafting may lead to the deterioration of the properties of such materials).
 Cold work cannot be used for increasing creep resistance, as recrystallization can occur
which will produced strain free crystals.
 Fine grain size is not desirable for creep resistance (this is contrary to what is usually
practiced for increasing the low temperature strength)→ grain boundary sliding can cause
creep elongation/cavitation. Hence, the following two strategies can be used:
► Use single crystals (single crystal Ti turbine blades in gas turbine engine have been
used though they are very costly).
► Aligned/oriented polycrystals → as all the grain boundaries are aligned along the
primary tensile axis, they experience no shear stress and creep is negated.
The Creep Curve:
Creep in metals is defined as time dependent plastic deformation at constant stress (or load) and
temperature. The form of a typical creep curve of strain versus time is in Figure. The slope of
this curve is the creep rate dε/dt. The curve may show the instantaneous elastic and plastic strain
that occurs as the load is applied, followed by the plastic strain which occurs over time. Three
stages to the creep curve may be identified:
Primary creep: in which the creep resistance increases with strain leading to a decreasing creep
strain rate.
Secondary (Steady State) creep: in which there is a balance between work hardening and
recovery processes, leading to a minimum constant creep rate.
Tertiary creep: in which there is an accelerating creep rate due to the accumulating damage,
which leads to creep rupture, and which may only be seen at high temperatures and stresses and
in constant load machines.
The minimum secondary creep rate is of most interest to design engineers, since failure
avoidance is required and in this region some predictability is possible. In the USA two
Standards are commonly used: (i) The stress to produce a creep rate of 0.0001% per hour (1% in
10,000 hours). (ii) The stress to produce a creep rate of 0.00001% per hour (1% in 100,000 hours
or approximately 11.5 years). The first requirement would be typical of that for gas turbine
blades, while the second for steam turbines. Constant load machines simulate real engineering
situations more accurately, but as the specimen extends its cross section area reduces, leading to
a rising stress. Machines designed to reduce the load to compensate for the reduced area and
maintain constant stress may produce an extended steady state region.

FATIGUE:
Salient Features & Overview Points:
 It is observed that materials subjected to dynamic/repetitive/fluctuating load (stress) fail
at a stress much lower than that required to cause fracture in a single application of a
load.
 Damage of material due to varying load (of magnitude usually less than the yield
stress) ultimately leading to failure is termed as fatigue of material (or fatigue failure).
 It is estimated that fatigue accounts for ~90% of all service failures due to mechanical
causes. Corrosion being the other major cause of failures.
 The insidious part of the phenomenon of fatigue failure is that it occurs without any
obvious warning. Usually, fatigue failures occur after considerable time of service.
  The surface which has undergone fatigue fracture appears brittle without gross
deformation at fracture (in the macroscale).
 On a macroscopic scale the fracture surface is usually normal to the direction of the
principal tensile stress.
 Fatigue failure is usually initiated at a site of stress concentration (E.g. a notch in the
specimen or an acicular inclusion).
 The term fatigue is borrowed from human reaction of ‘tiredness’ due to repetitive work!
 Fatigue testing is often conducted in bending or torsion mode (rather than
tension/compression mode). Bending tests are easy to conduct. In pipes fatigue tests may
be done by internal pressurization with a fluid.
 If the stress have a origin in thermal cycling, then the fatigue is called thermal fatigue.
Factors affecting fatigue failure:
 Three factors play an important role in fatigue failure:
(i) value of tensile stress (maximum),
(ii) magnitude of variation in stress,
(iii) number of cycles.
 Geometrical (specimen geometry) and microstructural aspects also play an important role
in determining fatigue life (and failure). Stress concentrators from both these sources
have a deleterious effect. Residual stress can also play a role.
 A corrosive environment can have a deleterious interplay with fatigue.

 Engineering fatigue data is usually plotted as a S-N curve. Here S is the stress and N the
number of cycles to failure (usually fracture). The x-axis is plotted as log(N).
 The stress plotted could be one of the following: a, max, min. Each plot is for a constant
m, R or A.
 It should be noted that the stress values plotted are nominal values and does not take into
account local stress concentrations.
 Most fatigue experiments are performed with m = 0 (e.g. rotating beam tests).
 Typically the stress value chosen for the stress is low (< y) and hence S-N curves deal
with fatigue failure at a large number of cycles (> 105 cycles). These are the high cycle
fatigue tests.
 It is to be noted that the nominal stress < y, but microscopic plasticity occurs, which
leads to the accumulation of damage.
 As obvious, if the magnitude of Stress increases the fatigue life decreases.
 Low cycle fatigue (N < 104 or 105 cycles) tests are conducted in controlled cycles of
elastic + plastic strain (strain control mode, instead of stress control).
 Broadly two kinds of S-N curves can be differentiated for two classes of materials.
(1) those where a stress below a threshold value gives a ‘very long’ life (this stress value
is called the Fatigue Limit / Endurance limit). Steel and Ti come under this category.
 (2) those where a decrease in stress increases the fatigue life of the component, but no
distinct fatigue life is observed. Al, Mg, Cu come under this category.
 From a application point of view having a sharp fatigue limit is useful (as keeping service
stress below this will help with long life (i.e. large number of cycles) for the component).
 S-N curve in the high cycle region can be described by the Basquin equation:
where, a is the stress amplitude, p & C empirical constants.
N ap  C
 The S-N curve is usually determined using 8-12 specimens. Starting with a stress of two-
thirds of the static tensile strength of the material the stress is lowered till specimens do
not fail in about 107 cycles. As expected, there is usually there is considerable scatter in
the data.
 UNIT-3

Thermal properties of metals:

Engineering materials are important in everyday life because of their versatile structural
properties. Other than these properties, they do play an important role because of their
physical properties. Prime physical properties of materials include: electrical properties;
thermal properties; magnetic properties; and optical properties. Selection of materials for use
at elevated temperatures and/or temperature changes require an engineer to know and
understand their thermal properties. This chapter deals with the thermal properties of
materials. Physical property of a solid body related to application of heat energy is defined as
a thermal property.

This chapter shall describe thermal properties like heat capacity, thermal expansion, thermal
conductivity, and thermal stresses. It is important to know and understand the concept of
thermal expansion which is the root cause for thermal stresses. Thermal stresses are stresses
leading to failure of engineering structures at elevated temperatures.

Heat capacity

Many engineering solids when exposed to heat experiences an increase in temperature i.e. it
absorbs heat energy. This property of a material i.e. material’s ability to absorb heat energy is
called its heat capacity, C. It is defined as the energy required to change a material’s
temperature by one degree. Mathematically, it is expressed as:

C= dT/dQ, J/mol-K or Cal/mol-K

Where dQ is the energy required to produce a temperature change equal to dT.

Heat capacity is not an intrinsic property i.e. total heat a material can absorb depends on its
volume / mass. Hence another parameter called specific heat, c, it defined as heat capacity per
unit mass (J/kg-K, Cal/kg-K). With increase of internal energy, geometrical changes may
occur. Accordingly, heat capacity is measured either at constant volume, C , or at constant
v

external pressure, C . The magnitude of C is always greater than C but only marginally.
p p v

Heat energy absorption of a (solid, liquid or gaseous) material exists in mode of thermal
energy vibrations of constituent atoms or molecules, apart from other mechanisms of heat
absorption such as electronic contribution. With increase of energy, atoms vibrate at higher
frequencies. However, the vibrations of adjacent atoms are coupled through atomic bonding,
which may lead to movement of lattices. This may be represented as elastic waves (phonon)
or sound waves. Vibrational contribution of heat capacity of solids varies with temperature
according to the following relation at low temperatures:

Cv= AT3

C is equal to zero at 0 K, but increase rapidly with temperature. It represents increased ability
v

of atomic vibrations or enhanced energy of lattice waves with ascending temperature. Above
a temperature called Debye temperature, θ , dependence of volumetric heat capacity value
d

reaches saturation. This saturation values if approximately equal to 3R (≈ 6 cal/mol-K), R

being the universal gas constant. For many solids, value of θ is below room temperature.
d

Figure 15-1: Heat capacity as a function of temperature.

Thermal expansion

After heat absorption, vibrating atoms behaves as though they have larger atomic radius,
which leads to increase in materials dimensions. The phenomenon is called thermal
expansion. It is quantified in terms of thermal expansion coefficient. Linear coefficient of
thermal expansion (α) defined as the change in the dimensions of the material per unit length,
and is expressed as:

α = lf-l0/l0(Tf-T0)

where T and T are the initial and final temperatures (in K), l and l are the initial and final
0 f 0 f
-1
dimensions of the material and ε is the strain. α has units as (°C) . For most metals α is the
-6 -6 -6
range of 5-25x10 , for ceramics 0.5-15x10 , and for polymers 50-400x10 .
A volume coefficient of thermal expansion, α (=3α) is used to describe the volume change
v

with temperature.

α = Δv / v0ΔT

An instrument known as dilatometer is used to measure the thermal expansion coefficient. It

is also possible to trace thermal expansion using XRD.

At microscopic level, thermal expansion can be attributed to the increase in the average
distance between the atoms. Thus, the coefficient of thermal expansion of a material is related
to the strength of the atomic bonds. The relation between inter-atomic distance and potential
energy is shown in the figure 15.2. As shown in the figure, the potential energy curve has
trough and is characterized by a minimum. This minimum corresponds to the equilibrium
inter-atomic distance ay 0 K. With increase in temperature of the material, vibrational
amplitude increase, and the mean of it represents the average inter-atomic distance. Because
of asymetric nature of the potential energy trough, rather than the increase in atomic vibration
amplitude, the average inter-atomic distance increases with the temperature of a material.

Figure 15.2: Change if inter-atomic distance with temperature.

If a very deep energy trough caused by strong atomic bonding is characteristic of the
material, the atoms separate to a lesser and the material has low linear coefficient of thermal
expansion. This relationship also suggests that materials having a high melting temperature –
also due to strong atomic bonds – have low thermal expansion coefficients. Most ceramics
having strong atomic bonds, thus, have low thermal expansion coefficients compared with
metals and polymers. However, as a consequence of non-uniform dimensional changes,
brittle materials like ceramics may experience fracture, known as thermal shock. The capacity
of material to withstand this failure is known as thermal shock resistance. (TSR).

TSR ≅ σf k /Eα

where σ – fracture strength.

f

Thermal shock behavior is affected by several factors: thermal expansion coefficient – a low
value is desired; thermal conductivity – a high value is desired; elastic modulus – low value is
desired; fracture strength – high value is desired; phase transformations. Thermal shock may
be prevented by altering the external conditions to the degree that cooling or heating rates are
reduced and temperature gradients across the material are minimized. Thermal shock is
usually not a problem in most metals because metals normally have sufficient ductility to
permit deformation rather than fracture. However, it is more of a problem in ceramics and
glass materials. It is often necessary to remove thermal stresses in ceramics to improve their
mechanical strength. This is usually accomplished by an annealing treatment.

Thermal conductivity

The ability of a material to transport heat energy from high temperature region to low
temperature region is defined as thermal conductivity. Similar to diffusion coefficient,
thermal conductivity is a microstructure sensitive property. The heat energy, Q, transported
across a plane of area A in presence of a temperature gradient ΔT/Δl is given by

Q = kA ΔT/Δl

where k is the thermal conductivity of the material. It has units as W/m.K. Metals have k
values in the range 20-400, ceramics 2-50, while polymers have in order of 0.3.

Heat energy in solids in transported by two mechanisms: lattice vibrations (phonons) and free
electrons. However, usually only one or other predominates the proceedings. Valence
electrons gain energy, move toward the colder areas of the material, and transfer their energy
to other atoms. The amount of energy transported depends on number of excited electrons,
their mobility i.e. type of material, lattice imperfections, and temperature. The thermal energy
associated with phonons is transported in the direction of their motion.

In metals, since the valence band is not completely filled, with little thermal excitation
number of electron move and contribute to the transfer of heat energy. Thus thermal
conduction I metals is primarily due to movement of electrons. It is the same for electrical
conduction. Both conductivities are related through the following relation:
 k/σT= L
-9 2 -8 2
where L – Lorentz constant, 5.5x10 [Link]/sec.K or 2.44x10 [Link]/ K . The relation is
termed as Wiedemann-Franz law. Lorentz constant is supposed to be independent of
temperature and the same for all metals if the heat energy is transported entirely by free
electrons. Thus, the relationship is followed to a limited extension in many metals.

With increase in temperature, both number of carrier electrons and contribution of lattice
vibrations increase. Thus thermal conductivity of a metal is expected to increase. However,
because of greater lattice vibrations, electron mobility decreases. The combined effect of
these factors leads to very different behavior for different metals. For example: thermal
conductivity of iron initially decreases then increases slightly; thermal conductivity decreases
with increase in temperature for aluminium; while it increases for platinum.

In ceramics, phonons are primarily responsible for thermal conduction. Since the electronic
contribution is absent, the thermal conductivity of most ceramics is lower than that of metals.
However, main reason for experimentally observed low conductivity of ceramics is the level
of porosity, as phonons are effectively scattered by imperfections. The scattering of phonons
becomes more pronounced with rising temperature. Hence, the thermal conductivity of
ceramic materials normally diminishes with increasing temperature. Advanced ceramic
materials like AlN, SiC are good thermal conductors, they are also electrical insulators.
Therefore these materials are useful as electronic packaging substrates where heat dissipation
is needed.

Thermal conductivity of polymers is even low, compared with ceramic materials. Vibration
and movement/rotation of molecular chains transfer heat energy. In these materials thermal
conductivity depends on degree of crystallinity; a polymer with highly crystalline and ordered
structure will have higher conductivity than amorphous polymer.

Thermal stresses:

Apart from thermal shock, another instance of problem exists with thermal expansion of a
material where there is no scope of dimensional changes. Thus due to temperature changes,
material may experience thermal stresses (σ ).
thermal

σthermal = αEΔT

where E – elastic modulus of the material. Thermal stresses in a constrained body will be of
compressive nature if it is heated, and vice versa.
Another source for thermal stresses is thermal gradient within the body when a solid body is
heated or cooled. It is because temperature distribution will depend on its size and shape.
These thermal stresses may be established as a result of temperature gradients across a body,
which are frequently caused by rapid heating or cooling.

Engineering materials can be tailored using multi-phase constituents so that the overall
material can show a zero thermal expansion coefficient. For example: Zerodur – a glass-
ceramic material that consists of 70-80% crystalline quartz, and the remaining as glassy
phase. Negative thermal expansion coefficient of glassy phase compensates for the positive
thermal expansion coefficient of the crystalline base, leading to a zero thermal expansion.
This material has many applications like parts of telescopes in astronomy. Many ceramic
materials for critical thermal applications are developed based on sodium-zirconium-
phosphate (NZP) that have a near-zero thermal expansion coefficient.
THERMAL FATIGUE:
The change of temperature imposed upon a body of the specimen produces alternate thermal
gradients and hence changing stresses. These changing stresses have the effect of creating
thermal fatigue in the [Link] stresses generated by changing temperature are often
high in magnitude creating plastic [Link] such conditions, the material fails due
to low cycle thermal fatigue. The failure of the material is further hastened because of bad
effects of temperature on mechanical strength.
THERMAL SHOCK:
Thermal shock is generation of sudden and high stresses due to sudden and severe changes in
[Link] shocks created by cooling are much more dangerous than those from
heating as this process creates tensile stresses on the surface. Surface of any material is
weaker than inside surface of the material for various reasons. For ductile metals and
polymers, alleviation of thermally induced stresses may be accomplished by plastic
deformation. However, the non-ductility of most ceramics enhances the possibility of brittle
fracture from these stresses. Brittle materials are weak in [Link] capacity of a material
body to withstand the thermal stresses brought about by sudden and severe temperature
changes is termed its thermal shock resistance (TSR) and usually denoted by P. P will be
function of elastic properties and thermal conductivity of the material and expressed as
P (TSR) = [σfK]/Eα
= [σu/Eα] 𝐾/𝜌𝐶
where σf is high fracture strength, σu → ultimate tensile strength, E →modulus of elasticity,
α→ coefficient of thermal expansion, ρ→ density and C →specific heat.
One may prevent the thermal shock by altering the external conditions to the degree that
cooling or heated rates are reduced and temperature gradients across a body are minimized.
Modification of the thermal and/or mechanical characteristics in Eq. (29) may also enhance
the thermal shock resistance of a material. The introduction of some relatively large pores or
ductile second phase may also help to improve the thermal shock characteristics of a material,
i.e., both serve to impede the propagation of thermally induced cracks.
Usually, there is a necessity to remove thermal stresses in ceramic materials as a means of
improving their mechanical strengths and optical characteristics. This may be achieved by an
annealing heat treatment.
ELECTRICAL PROPERTIES

INTRODUCTION:

Engineering materials are important in everyday life because of their versatile structural
properties. Other than these properties, they do play an important role because of their
physical properties. Prime physical properties of materials include: electrical properties;
thermal properties; magnetic properties; and optical properties. The electrical behaviour of
engineering materials are diverse, and so are their uses in electrical applications. Few
examples of electrical applications: copper and aluminium wires used in power transmission;
amorphous silicon in solar cells; LEDs; gallium-arsenide chips used in modern day
computers, cell phones, digital assistants; etc. The electrons in the outermost shell of atoms
controls the electrical and magnetic behaviour of substances. Recent developments in the
field of electronic structure of substances have accelerated the growth of number of useful
solid state devices.

ELECTRICAL CONDUCTION

Electrical conductivity of a material is defined in terms of ease with which a material

transmits an electrical current. Electrical current (I) is flow of electrons, and driving force for
the flow of electrons is called voltage (V). Ohm’s law relates these parameters as follows:

VαI

V = IR(1)

where R – is the materials resistance to flow of electrons through it.

V, I, and R respectively have units as volts, amperes, and ohms (Ω).

Electrical resistance of a material is influenced by its geometric configuration; hence a new

parameter called electrical resistivity (ρ) is defined such as it is independent of the geometry.

RA/l= ρ(2)

Ρ=VA/Il (3)

where A – cross-sectional area perpendicular to the direction of the current, and l – the
distance between points between which the voltage is applied. Units for ρ are ohm-meters
(Ω-m).

Reciprocal of the electrical resistivity, known as electrical conductivity (σ), is used to express
the electrical behavior of a material, which is indicative of the ease with which a material
allows of flow of electrons.

σ =1/ ρ=l/ RA (4)

Electrical conductivity has the following units: (Ω-m)-1 or mho/meter.

Electrical conductivity is indicative of the ease with which a material is capable of

conducting an electrical current. It is also expressed in Siemens/m.
When an electric field E is applied to a conductor an electric current begins to flow and the
current density by Ohm’s law is
J = σ E (5)
The conductivity may be defined as the movement of electrical charge from one point to
another and
it depends on the number of charge carriers (n), the charge per carrier (e) and the mobility of
carriers (µ),i.e.
σ = neµ (6)
The unit of mobility (µ) is m2 V–1s–1. Mobility is an important term in the study of
semiconductors.
One can obtain the expression (6) from first principle as follows:
Let E be the electric field applied to a conductor, e be the charge on the electron and m the
mass of the electron. The electrons move in a specific direction under the influence of the
electric field. The directional motion of a free electron is called a drift. The average velocity
gained during this drift motion is termed as drift velocity.
As electron is being negatively charged particle, the force acting on it under the electric field
intensity
E is,
F = –eE (7)
The electron drift is in a direction opposite to that of the applied field. During the accelerated
motion, the electron collides with the defects in the lattice. As a result of the consequence
scattering, the electron loses the velocity it gained from the electric field. The effect of the
crystal lattice may be reduced considerably due to a retarding force (may be due to damping).
This force is proportional to the velocity v and mass m of the electron. The retarding force is
represented as –αmv, where α is a constant. We can write the equation of motion of the
electron as
m=dv/dt= –eE = –αmv (8)
or dv = – (eE/m)dt
or v = – (eE/m)t + constant (9)
If the average time between collisions is 2Ʈ then, during this time, the electron is acted upon
by a force F given by Eq. (7). But at t = 0, v = 0 (immediately after each collision) and hence
the integeration constant in (9) is zero. Thus (9) takes the form
v = - (eE/m)Ʈ
Obviously, the mean velocity = –eEƮ /m, where Ʈ is called the relaxation time and is time
interval in which there is unit probability of a collision.
When there is a collision of lattices (resistance), the current density J due to n electrons per
unit volume of charge e and drift velocity v is expressed as
J = nev (10)
= ne( eEƮ/m) (11)
= σ E (12)
σ =J/E=ne2 Ʈ/m=ne (eƮ ) (13)
The velocity in a unit electric field, i.e. v/E is the mobility (µ) of the electron. Hence
µ = v/E=1/(E/v)(EeƮ/m)=eƮ/m
Using Eqs. (10) and (12), one obtains
J = neµE
and σ = neµ(14)
Equation (14) is of immense importance for solid materials. From (14), we note that electrical
conductivity depends on two factors: (i) the number n of charge carriers per unit volume and
(ii) their mobility,µ.
Resistivity or conductivity does not depend on the dimensions of the material. These
properties are microstructure-sensitive instead, like many other intrinsic properties, for
example yield strength. Thus either of it (usually conductivity) allows us to compare different
materials. Solid engineering materials exhibit very wide range of electrical conductivity
(about 27 orders of variation). Hence the materials for electrical applications are classified
according to their electrical conductivity as: conductors, semiconductors and
insulators/dielectrics. Metals are conductors having conductivities in range of 107 (Ω-m)-1,
while semiconductors have conductivities in range from 10-6 to 104 (Ω-m)-1, and materials
with conductivity lower than 10-10(Ω-m)-1 are termed as insulators.

ELECTRONIC AND IONIC CONDUCTION:

We have seen that an electric current results from the motion of electrically charged particles
in response to the forces that act on them from an externally applied field. Positively charged
particles are accelerated in the electric field direction, and negatively charged particles in the
direction opposite to the electric field direction. A current arises within most solid materials
due to flow of electrons and this is termed as electronic conduction. In addition, for ionic
materials a net motion of charged ions is possible that produces a electric current; such is
termed ionic conduction.

BAND STRUCTURE IN SOLIDS:

A solid may be thought of as consisting of a large number, say N, of atoms initially separated
from one another, which are subsequently brought together and bonded to form the ordered
atomic arrangement exhibited by the crystalline material. At relatively large separation
distances, each atom is independent of all the other atoms as will have the atomic energy
levels and electron configuration as if isolated. However,as the atoms in a solid come within
the close proximity of one another, electrons are acted upon, orperturbed, by the electrons
and nuclei of adjacent atoms. This influence is such that each distinct atomic state may split
into a series of closely spaced electron states in the solid, to form what is termed an electron
energy band. The extent of splitting of atomic states depends on interatomic separation (Fig.
14.1) and begins with the outermost electron shells, since they are the first to be perturbed as
the atoms coalesce. Within each band, the energy states are discrete, yet the difference
between adjacent states is exceedingly small. At the equilibrium spacing, band formation may
not occur for the electron subshells nearest the nucleus (Fig. 14.2(b)). Moreover, gaps may
exist between adjacent bands, as also shown in Fig. 14.2(a),normally energy lying within
these band gaps are not available for electron occupancy. The conventional way of
representing electron band structure is shown in Fig. 14.2(a).
The number of states within each band will equal the total of all states contributed by the N
atoms, e.g. a s-band will consists of N-states, and a p-band of 3 N states. With regard to
occupancy, each energy state with accommodate two electrons, which must have oppositely
directed spins. Moreover, bands will contain the electrons that resided in the corresponding
levels of the isolated atoms; for e.g., a 4s energy band in the solid will contain those isolated
atom’s 4s electrons. Of course, there will be empty band and, possibly,bands that are only
partially filled.
The electrical properties of a solid material are a consequence of its electron band structure,
i.e. the arrangement of outermost electrons in bands and the way in which they are filled with
electrons. A distinctive band structure type exists for metals, for semiconductor, and for
insulators.
The band structure in a solid determines whether the solid is an insulator or a conductor or a
[Link] bands are filled upto a certain level by the electrons within each atom.
The highest band in which electrons are still predominantly attached to their atoms are found
is called valence band. This is the band in which the valence (outermost) electrons from each
atom will be located. These are the electrons that are the possible carriers of electricity.
However, in order for an electron to conduct, it must get up to slightly higher energy so that it
is free of the grip of its atom. At 0 K four different types of band structures are possible. In
the first (Fig. 14.3(a)), one outermost band is only partially filled with electrons. The energy
corresponding to the highest filled energy state of 0 K is called the Fermi energy EF, as
indicated in [Link] energy band structure is typified by some metallic conductors in
particular those that have a single s valence electron, e.g. copper, etc. Each copper atom has
one 4s electron. However, for a solid comprised of N atom, the 4s band is capable of
accommodating 2N electrons. Obviously, only half the available electron positions within this
4s band are filled.
For the second band structure, also found in metallic conductors (Fig. 14.3(b)), there is an
overlap of an empty band and a filled band. Magnesium has this type of band structure. Each
isolated Mg has two 3s electrons. However, when a solid is formed, the 3s and 3p bands
overlap. In this instance and at 0K, the Fermi energy, EF is taken as that energy below which,
for N atoms, N states are filled, two electrons per state. Therefore, the band theory tells us
that we have a conductor, when
(i) the valence band is not filled, so electron can move to higher states in the valence band
and be free(energy gaps between valence band and conduction band are very small), or
(ii) when there is no energy gap between the valence band and the conduction band, i.e. there
is overlapping,so electrons can easily make the transitions from the valence to the conduction
bands. The final two band structures (Fig. 14.3(c) and (d)) are similar; one band (the valence
band) that is completely filled with electrons that is separated from an empty conduction
band and an energy band gap lies between them.
When energy band gap is of the order of 1 eV (for Si, Eg = 1.12 eV; and for Ge, Eg= 0.72
eV). These materials with narrow band gap are called [Link] the energy band
gap is relatively wide ~ 5 eV or even more, the materials are called insulators.
The band theory of solids tells us that an insulator is a material in which the valence band
(VB) are filled and the energy band gap Eg between VB and conduction band (CB) is too
large so that valence electrons cannot jump at normal temperatures from VB to CB. An
insulator does not conduct at 0 K or even at room temperature because there are no
conduction electrons in it. However, an insulator may conduct if its temperature is very high
or if a high voltage is applied across it. This is known as breakdown of an insulator.

ELECTRICAL RESISTIVITY:

Most metals are extremely good conductors of electricity. Room temperature conductivities
of few common metals are given in Table. Metals have high conductivities due to the large
number of free electrons that have been excited into empty states above the Fermi energy.
Obviously, n has a large value in the conductivity expression.

Let us now discuss conduction in metals in terms of the resistivity (the reciprocal of
conductivity).The crystalline defects serve as scattering centers for conduction electrons in
metals and increase in their number raises the resistivity, i.e. lowers the conductivity. The
concentration of these imperfections depends on temperature, composition, and the degree of
cold work of a metal specimen. It has been observed experimentally that the total resistivity
of a metal is the sum of the contributions from the thermal vibrations,impurities and plastic
deformation; i.e., the scattering mechanism act independently of one another.
Mathematically,we can write this as follows:
ρtotal = ρt +ρ i +ρd (15)
where ρt, ρi and ρd are the individual thermal, impurity and deformation resistivity
contributions, respectively. Equation (15) is sometimes called as Matthiessen’s rule. Figure
14.6 shows a plot of resistivity versus temperature for copper and several copper-nickel
alloys in annealed and deformed states. Figure also show the influence of each _ variable on
the total resistivity. The additive character of the individual resistivity contributions is
demonstrated at –100°C.

FACTORS AFFECTING RESISTIVITY:

(i)Influence of Temperature: Any rise in temperature of a conductor (which contains small
amounts of impurities) increases thermal agitation of the metallic ions as they vibrate about
their mean position. This reduces the mean free path and restricts the free movement of
electrons, thus reducing the conductivity of the metal, i.e. this increases the resistivity of
metal. For the pure metal and all the copper-nickel alloys shown in Fig. 14.6, the resistivity
rises linearly with temperature above about –200°C. Thus
ρt = ρo + aT (16)
where ρo and a are constants for each particular metal.

(ii) Influence of Impurities: Another factor which reduces the mean free path of electrons is
the impurity or solute atoms. The solute atoms provide the breakage in the regular crystalline
structure, thus presenting an obstacle in the movement of electron waves. A solid solution
alloy will always have lower conductivity than its pure components though both individual
components have higher conductivity than the alloy. For addition of a single impurity that
forms a solid solution, the impurity resistivity ρi is related to the impurity concentration Ci in
terms of the atom fraction (at %/100) as follows:
ρi = ACi (1 – Ci)
where A is a composition-independent constant that is a function of both the impurity and
host metals. The influence of Ni impurity additions at about room temperature resistivity of
Cu is shown in Fig. 14.7, upto50 Wt% Ni; over this composition range Ni is completely
soluble in [Link] may note that Ni atoms in Cu act as scattering centres, and increasing the
concentration of Ni in Cu results in the enhancement of [Link] can use the rule of
mixtures expression for a two-phase alloy consisting of α and β phases to approximate the
resistivity as follows:
ρi = ραVα+ ρβVβ(18)

where the V’s and ρ’s represent volume fractions and individual resistivities for the respective
phases.
(iii) Influence of Plastic Deformation: Plastic deformation also raises the electrical resistivity
as a result of increased number of electron-scattering dislocations. The effect of plastic
deformation on resistivity is also shown in Fig.14.6.

(iv) Effect of Pressure: At room temperature the general behaviour of ρ of metal is to

decrease initially with increasing pressure and it may pass through a minimum. The initial
decrease is due to the effect of pressure in reducing the amplitude of lattice vibrations. The
subsequent increase is probably due to modification of the electron band structure which
leads to increased phonon scattering.
ELECTRICAL CHARACTERISTICS OF ALLOYS USED FOR COMMERCIAL
PURPOSES:
Copper is the most widely used metallic conductor due to its electrical and other properties.
For many electrical applications, oxygen-free-high-conductivity (OFHC) copper having
extremely low oxygen and other impurity contents is produced. Aluminium, having about
one-half conductivity that of copper, is also frequently used as an electrical conductor. Silver
has higher conductivity than either Cu or Al, however, its use is restricted due its very high
cost compared to Cu and Al.
On occassion, it is necessary to improve the mechanical strength of a metal alloy without
impairing significantly its conductivity. Both solid solution alloying and cold working
improve strength at the expense of conductivity, and thus a trade off must be made for these
two properties. Most often strength is enhanced by introducing a second phase that does not
have so adverse an effect on conductivity, e.g. copper-beryllium alloys are precipitation
hardened, but even so, the conductivity is reduced by about a factor of 075 over high purity
Cu.
 UNIT-4
Magnetic materials: Terminology and classification, magnetic moments due to electron
spin, ferromagnetism and related phenomena, soft magnetic materials and hard magnetic
materials.
Dielectric materials: Polarization, temperature and frequency effects, electric breakdown,
ferroelectric materials.
Insulating materials: Types and Properties

MAGNETIC MATERIALS
Magnetism is the phenomenon by which materials exert an attractive or repulsive force or
influence on other materials. Magnetism arises from the magnetic moment or magnetic dipole
of the magnetic materials. When the electron revolves around the positive nucleus, orbital
magnetic moment arises. Similarly when the electron spins, spin magnetic moment arises.
Magnetic materials are those materials that are capable of being magnetised in a magnetic
field i.e., they are capable of creating self-magnetic field in the presence of external magnetic
field. There are nearly eleven types of magnetic materials. Some of them are Dia-magnetic,
Para-magnetic and Ferro-magnetic, Anti-Ferro-magnetic and Ferri-magnetic etc.
Many modern technological devices rely on magnetism and magnetic materials, including
electrical power generators and transformers, electric motors, radio, television, telephones,
computers, and components of sound and video reproduction systems.

TERMINOLOGY
Following are the important terms in magnetism:
Magnetic Induction or Magnetic Flux Density (B): It represents the magnitude of the
internal field strength within a substance that is subjected to an H field. In the presence of
magnetic field in vacuum, the magnetic induction, B (in units of tesla or weber per square
meter (Wb/m2)) is related to the field strength, H (in units of A–m–1) as follows:
B=µH
Where µ is the permeability of the solid material through which the magnetic lines of force
pass. The ratio µ/µ0 is the relative permeability of the medium and designated by µr. It is
unitless.
µr=µ/µ0
Where, µ0 is called the permeability of free space (vacuum), a universal constant, which has a
value of 4π*10-7 (1.257*10-6) H/m
Magnetic Field (H): It is said to occupy a region when the magnetic effect of an electric
current or of a magnet upon a small test magnet which is brought in the vicinity is detectable.
Magnetic field strength (H) is expressed in units of A-m–1 (Ampere/meter).
Magnetization (M) or Intensity of Magnetization (I): It is defined as the magnetic dipole
moment per unit volume of the bar. Magnetization is the process of converting a non-
magnetic bar into a magnetic bar. This term is almost analogous to the polarization in
dielectric materials. Unit: A-m-1
 B = µH = µ0µrH
B = µ0µrH + µ0H - µ0H
B = µ0H + µ0H(µr – 1)
B = µ0H + µ0M
Magnetic Susceptibility (χ): The magnitude of the magnetization, M is proportional to the
applied field as follows:
M=χH
Where χ is called the magnetic susceptibility, which is unitless. The magnetic susceptibility
and the relative permeability are related as follows:
χ = µr –1 = M/H
There is a dielectric analogue for each of the foregoing magnetic field parameters. The B and
H fields are, respectively, analogous to the dielectric displacement D and the electric field E,
whereas the permeability µ is analogous to the permittivity ε. Furthermore, the magnetization
M and polarization P are correlates
D= εE
D= ε0E+P
Magnetic Permeability (µ): The permeability or relative permeability of a material is a
measure of the degree to which the material can be magnetized, or the ease with which a B
field can be induced in the presence of an external H field. Unit: H-m-1 (henry/ meter)
µ=B/H
Magnetic Dipoles: Magnetism is dipolar, i.e. magnetism is characterized by having two
opposite poles: north (N) and south (S). Magnetic dipoles are found to exist in magnetic
materials, which, in some respects are analogous to electric dipoles. The strength of a
magnetic dipole is measured by the product of the pole strength and the distance between the
poles. This is called magnetic moment. Magnetic dipoles are influenced by magnetic fields
and within a magnetic field; the force of the field itself exerts a torque that tends to orient the
dipoles with the magnetic field. Magnetic dipole moment is the measure of the object’s
tendency to align with a magnetic field. It is a vector quantity
τ = mB
Where, τ is the torque acting on the dipole, m is the magnetic moment and B is the external
magnetic field
ORIGIN OF MAGNETIC MOMENTS
The electric current through a conductor develops magnetic field around it or current through
a coil of wire will act as a magnet. There is an intimate relation between electric current and
magnetic field.
The macroscopic magnetic properties of materials are a consequence of magnetic moments
associated with the following:
 The orbital magnetic moment of the electrons arising due to electron’s revolution
around nucleus.
 The spin magnetic moment of electrons corresponding to the spin quantum number
arising due to electron’s spin or rotation about its own axis
 The spin magnetic moment of the nucleus arising due to nucleus’s spin or rotation
about its own axis
Of these three, the spin magnetic moments of the electrons are most important.

Fig. The magnetic moment associated with (a) an orbiting electron and (b) a spinning
electron.
Each electron revolving around the nucleus in an atom constitutes a circulating electric
charge or current and thus produces a small magnetic field. Moreover, each spinning electron
on its axis also can be conceived as a circulating charge and also produce a small magnetic
field. In each atom, orbital moments of some electron pairs cancel each other; this also holds
true for the spin moments. The spin moment of an electron with spin up cancels that of one
with spin down. The net magnetic moment, then, for an atom is just the sum of the magnetic
moments of each of the constituent electrons, including both orbital and spin contributions,
and taking into account moment cancellation. For an atom having completely filled electron
shells or subshells, when all electrons are considered, there is total cancellation of both orbital
and spin moments. Materials composed of atoms having completely filled electron shells are
not capable of being permanently magnetized. This category includes the inert gases (He, Ne,
Ar, etc.) as well as some ionic materials.
CLASSIFICATION OF MAGNETIC MATERIALS
The types of magnetism include diamagnetism, paramagnetism, and ferromagnetism; in
addition, antiferromagnetism and ferrimagnetism are considered to be subclasses of
ferromagnetism. The behavior depends on the response of electron and atomic magnetic
dipoles to the application of an externally applied magnetic field (i.e. magnetic susceptibility
and net magnetic moment).
Diamagnetic Materials:
Diamagnetic materials lack permanent dipoles. Diamagnetism is a very weak form of
magnetism that is nonpermanent and persists only while an external field is being applied.
When the material is placed in a magnetic field, an extra torque is applied to the electron,
resulting in an antiparallel alignment of the atomic magnetic moment. Thus, the relative
permeability µr is less than unity (however, only very slightly), and the magnetic
susceptibility is negative—that is, the magnitude of the B field within a diamagnetic solid is
less than that in a vacuum. The volume susceptibility χm for diamagnetic solid materials is on
the order of -10-5. However, a superconductor, which is perfectly diamagnetic with
susceptibility value of –1. All the lines of force are repelled by the superconductor, thus
making them useful for the purpose of shielding out magnetic fields. In a diamagnetic
material the value of susceptibility is independent of temperature. When placed between the
poles of a strong electromagnet, diamagnetic materials are attracted toward regions where the
field is weak.
Figure below illustrates schematically the atomic magnetic dipole configurations for different
materials with and without an external field; here, the arrows represent atomic dipole
moments, whereas for the preceding discussion, arrows denoted only electron moments.
Diamagnetism is found in all materials, but because it is so weak, it can be observed only
when other types of magnetism are totally absent. This form of magnetism is of no practical
importance.
The examples for diamagnetic materials are organic solids like naphthalene, benzene, etc.;
metals like bismuth (strongly diamagnetic), zinc, silver, gold and copper; atoms with rare gas
configurations like, A, He, Ne, etc. As diamagnetism is importantly an expelling of magnetic
fields within a material, the strong diamagnetic materials can be levitated. Superconducting
magnets are the foremost elements of most magnetic resonance imaging (MRI) systems and
are among the most important applications of diamagnetism. Bismuth is used in guns,
Paramagnetic Materials:
Paramagnetic materials are those in which individual atoms, ions or molecules have a number
of incomplete cancellations of spins and thus possess permanent magnetic moment. In the
absence of an external magnetic field, the orientations of these atomic magnetic moments are
random, such that a piece of material possesses no net macroscopic magnetization. But in
presence of an external field, these atomic dipoles are free to rotate and align along the field;
this is the phenomenon of paramagnetism. The aligning force on the permanent moments of
the atoms with ordinary magnetic fields is rather small, so that the paramagnetic effect is
weak. Relative permeability is greater than unity and the paramagnetic susceptibility is small
and positive, of the order of 10–5 to 10–2. With increasing temperature, thermal energy tends
to randomize the alignment. As a result susceptibility decreases. The linear temperature
dependence of the magnetic susceptibility in paramagnetic materials is given by Curie’s Law:
M = C (B/T)
Where, M is the magnetization (magnetic moment per unit volume), C is the Curie constant,
B is the magnetic flux density and T is temperature.
The Curie’s Law applies only to paramagnets. The magnetic susceptibility of paramagnetic
materials is also temperature dependent. When B=0, the magnetization is also 0. This means
that when a paramagnet is not in a magnetic field, it has zero net magnetization.
The examples for paramagnetic materials are Liquid oxygen, sodium, magnesium, aluminum,
chromium, platinum, molybdenum, lithium, tantalum and iron salts. Superparamagnets are
the elements that not only show a net paramagnetic response but they also tend to exhibit
strong ferromagnetic or ferrimagnetic ordering mostly at a microscopic level. These materials
also follow Curie law and have very large Curie constants. Ferrofluids is a superparamagnet.
Ferromagnetic Materials:
Certain metallic materials possess a permanent magnetic moment in the absence of an
external field and manifest very large and permanent magnetizations. Permanent magnetic
moments in ferromagnetic materials result from atomic magnetic moments due to uncanceled
electron spins as a consequence of the electron structure. There is also an orbital magnetic
moment contribution that is small in comparison to the spin moment.
Ferromagnetic materials have unpaired electron spins which line up parallel with each other
in a region called a domain. Within the domain, the magnetic field is intense, but in a bulk
sample the material will usually be unmagnetized because the many domains will themselves
be randomly oriented with respect to one another. When a ferromagnetic material is placed in
an external magnetic field, it can cause the magnetic domains to line up with each other and
the material is said to be magnetized. The driving magnetic field will then be increased by a
large factor which is usually expressed as a relative permeability for the material.
Ferromagnets will tend to stay magnetized to some extent after being subjected to an external
magnetic field. This tendency to “remember their magnetic history” is called hysteresis. A
fraction of the saturation magnetization which is retained when the driving field is removed is
called the remanence of the material, and is an important factor in permanent magnets.
Ferromagnets have strong, and positive magnetic susceptibility, in the range 10 2–105.
Consequently, H << M. Ferromagnetism is possible only when atoms are arranged in a lattice
and the atomic magnetic moments interact to align parallel with each other. This effect is
explained in classical theory by the presence of a molecular field within the ferromagnetic
material, which was first postulated by Weiss in 1907. This field is sufficient to magnetize
the material to saturation.
Curie-Weiss Law:
𝐶
𝜒=
𝑇−𝜃
Where, 𝜒 refers to susceptibility, C is Curie constant (Fe: C = 0.2 K/cm3), T is absolute
temperature and 𝜃 is Curie temperature.
In the periodic table of elements only Fe, Co and Ni are ferromagnetic at and above room
temperature. As ferromagnetic materials are heated, then the thermal agitation of the atoms
means that the degree of alignment of the atomic magnetic moments decreases and hence the
saturation magnetization also decreases. When thermal energy exceeds the spin coupling
(exchange) energy, the coupling breaks down and the material behaves as a paramagnet; the
temperature of this transition is the Curie temperature, TC (Fe: TC =770°C, Co: TC =1131°C
and Ni: TC = 358°C). Above TC the susceptibility varies according to the Curie-Weiss law. It
is to be noted that at Curie temperature the intensity of magnetization is low, but not zero.
Just below the Curie temperature, the susceptibility can be 102 to 103, increasing with
decrease in temperature, as the alignment becomes more complete. The Curie temperature is
a function of the magnitude of the exchange energy. Cobalt that has the highest exchange
energy has the highest Curie temperature, 1400 K. Gadolinium with small exchange energy
has a Curie temperature below room temperature.
The examples for ferromagnetic materials are iron, nickel, cobalt and some of the rare earths
(gadolinium, dysprosium). Samarium and neodymium in alloys with cobalt have been used to
fabricate very strong rare-earth magnets.
There are many practical applications of ferromagnetic materials, such as the electromagnet.
Ferromagnetic materials will respond mechanically to an impressed magnetic field, changing
length slightly in the direction of the applied field. This property, called magnetostriction,
leads to the familiar hum of transformers as they respond mechanically to 50 Hz AC voltages.

Antiferrimagnetic Materials
Magnetic moment coupling between adjacent atoms or ions also occurs in materials other
than those that are ferromagnetic. In one such group, this coupling results in an antiparallel
alignment or when the exchange integral is negative; the alignment of the spin moments of
neighboring atoms or ions in exactly opposite directions is termed antiferromagnetism.
When a magnetic field is applied, a small magnetization appears in the direction of the field
which increases further with temperature. Such a behaviour is typical of an antiferromagnetic
material. The magnetization becomes the maximum at a critical temperature TN, called the
Neel temperature, which is analogous to the Curie temperature in the paramagnetic or
ferromagnetic substances (Cr: TN =37ºC). This is the transition temperature below which the
spontaneous magnetic ordering takes place. Above this temperature, the magnetization, the
magnetization decreases continuously which is indicative of the paramagnetic state of the
material.
Magnetic susceptibility is positive and very [Link] most characteristic property of an
antiferromagnetic material is that its susceptibility χ shows a maximum as a function of
temperature, as shown in figure below. The variation of susceptibility with temperature is
governed by
𝐶
𝜒=
𝑇+𝜃
where 𝜃 = TN is called the Neel temperature.
The material’s susceptibility changes around the Neel temperature. As the temperature is
raised from 0 K the interaction which leads to anti-parallel spin alignment becomes less
effective until at TN the spins are free. The susceptibility increases inversely with temperature
above TN and decreases inversely below this temperature.

Many oxides and chlorides of the transition metals are examples including both chromium
and α-manganese, and also manganese–copper alloys. Prominent example is Manganese
oxide (MnO), which is a ceramic material that is ionic in character, having both Mn 2+ and O2-
ions. No net magnetic moment is associated with the O2- ions because there is a total
cancellation of both spin and orbital moments. However, the Mn2+ ions possess a net
magnetic moment that is predominantly of spin origin. These Mn2+ ions are arrayed in the
crystal structure such that the moments of adjacent ions are antiparallel. The opposing
magnetic moments cancel one another, and, as a consequence, the solid as a whole possesses
no net magnetic moment.

Schematic representation of antiparallel alignment of spin magnetic moments for

antiferromagnetic manganese oxide
Hund’s Rule
Hund’s rule is a manifestation of the spin dependent electrostatic energy of the electrons in an
orbital. When the electrons have the same momentum and the same spin, a certain distance
must separate them from one another, in order to be consistent with the Pauli exclusion
principle. This physical separation tends to increase their kinetic energy, but reduces the
electrostatic repulsive energy between them. Whether the electrons will align their spins or
not will depend on the sign of the net change in energy. The stable, energetically favoured
order of filling of electronic orbitals in atoms is given by Hund’s rule.
In the solid state, the outer electronic orbitals of neighbouring atoms overlap and produce
energy bands. Consider the overlapping and the formation of energy bands in the first
transition metals. At the left end of the series, the radius of the 3d orbitals in the atoms is
large enough to result in good overlap between neighbours in the crystalline state. The 3d
band then contains all paired up electrons and there is no net magnetic moment in the crystal.
We can say that the atoms are antiferromagnetically coupled, as the magnetic moments of a
pair of atoms exactly cancel out.
As we go to the right in the transition series, the 3d orbitals shrink due to greater attraction
from the increasing charge on the nucleus and consequently the overlap of the 3d orbitals
decreases. The elements Fe, Co and Ni are in special situation. The unpaired electrons in the
3d orbitals of neighbouring atoms align their spins in a parallel fashion and thereby lower
their spin dependent electrostatic energy. This lowering is partly offset by the rise in the
Fermi level and the consequent increase in the average kinetic energy of the electrons. The
increase in the Fermi level is directly attributable to the greater physical separation between
electrons. The net gain in energy, Eunmagnetized – Emagnetized, called the exchange
interaction energy is a sensitive function of the ratio of the atomic diameter to the 3d orbital
diameter. This ratio for some of the first transition elements is shown as follows:
Element Ti Cr Mn Fe Co Ni
datomic/d3d orbital 1.12 1.18 1.47 1.63 1.82 1.98
It turns out that, only when this ratio lies between 1.5 and 2.0, the exchange energy is positive
and parallel spins are energetically favoured. Among the common metals, only Fe, Co and Ni
have positive exchange energy and are in the spontaneously magnetized state. These metals
or their ions form the basis of the majority of magnetic materials.
No overlap of the d orbitals occurs in the higher transition series, as the d electrons are
strongly attracted to their respective nuclei, which have larger positive charges. The only
other elemental crystals where the exchange energy is appreciable belong to the first rare
earth series such as gadolinium, terbium and dysprosium. Here, the 4f electrons align
themselves in a parallel fashion.
Antiferromagnetic materials may have a net magnetization due to spin quantum, lattice
defects, and in nanoscale particles, frustrated surface spins. In the periodic table the only
element exhibiting antiferromagnetism at room temperature is chromium.
Antiferromagnetic materials have applications in MRAMs, GMR detectors, magnetic sensors,
pixy dust etc.
Ferrimagnetism
Some magnetic materials e.g. in some ceramics, etc., have properties which are intermediate
between those of anti-ferromagnetic and ferromagnetic. The constituent atoms may be
antiferromagnetically coupled but with different magnetic moments. This gives rise to a
relatively strong net magnetization (particularly when compared to antiferromagnets) which
is comparable in order of magnitude to ferromagnets. N´eel has called this phenomenon
ferrimagnetism. It is compared with ferromagnetism and antiferromagnetism. Ferrimagnetism
is only observed in compounds, which have more complex crystal structures than pure
elements.

Ferromagnetism Antiferromagnetism Ferrimagnetism

The principles of ferrimagnetism are illustrated with the cubic ferrites - oxides of various
metal elements. The prototype ferrite is Fe3O4—the mineral magnetite, sometimes called
lodestone. The formula for Fe3O4 may be written as Fe2+O2-–(Fe3+)2(O2-)3, in which the Fe
ions exist in both +2 and +3 valence states in the ratio of 1:2. A net spin magnetic moment
exists for each Fe2+ and Fe3+ ion, which corresponds to 4 and 5 Bohr magnetons, respectively,
for the two ion types (Fig. 14.30). Furthermore, the O 2- ions are magnetically neutral. There
are antiparallel spin-coupling interactions between the Fe ions, similar in character to
antiferromagnetism. However, the net ferrimagnetic moment arises from the incomplete
cancellation of spin moments. Net magnetic moments for six cations are given in Table
below.

Schematic diagram showing the spin magnetic moment configuration for Fe 2+ and Fe3+
ions in Fe3O4
Ferrites of the general formula Me2+Fe3+2O2–4 can be ferrimagnetic. The divalent metal cation
(Me2+) in the formula is usually Fe2+, Ni2+, Zn2+, Mg2+, Co2+, Ba2+, Mn2+ or some
combination of these ions. These compounds crystallize mostly as the inverse spinel
structure. By adjustment of composition, ferrite compounds having a range of magnetic
properties may be produced. For example, nickel ferrite has the formula NiFe 2O4. Other
compounds may also be produced containing mixtures of two divalent metal ions such as
(Mn, Mg)Fe2O4, in which the Mn2+:Mg2+ ratio may be varied; these are called mixed ferrites.
Ceramic materials other than the cubic ferrites are also ferrimagnetic and include the
hexagonal ferrites and garnets. Hexagonal ferrites have a crystal structure similar to the
inverse spinel crystal structure, with hexagonal symmetry rather than cubic. The chemical
formula for these materials may be represented by AB12O19, in which A is a divalent metal
such as barium, lead, or strontium, and B is a trivalent metal such as aluminum, gallium,
chromium, or iron. The two most common examples of the hexagonal ferrites are PbFe 12O19
and BaFe12O19. The most versatile of ferrimagnetic systems are the rare earth iron garnets.
The garnets have a very complicated crystal structure, which may be represented by the
general formula M3Fe5O12; here, M represents a rare earth ion such as samarium, europium,
gadolinium, or yttrium. Yttrium iron garnet (Y3Fe5O12), sometimes denoted YIG, is the most
common material of this type.
Ferromagnetic materials which finds wide applications in electrical engineering have a
disadvantage, that they have low electrical resistivity. This disadvantage of the ferromagnetic
materials limit their application in high frequency alternating current applications, high eddy
current losses and poor magnetic utilization of metals occur in sheets even at low frequencies.
The saturation magnetization for ferrimagnetic materials are not as high as for ferromagnets.
Moreover, ferrites being ceramic materials, are good electrical insulators. Strontium ferrite is
extensively used in applications such as electric motors, because of these properties and low
material costs.
All the five categories of magnetic materials have been discussed and some examples are
given in Table below to illustrate the effect of magnetic susceptibility on the classification of
magnetic materials. The table will show that for a particular type of magnetic material, the
value of magnetic susceptibility lies in a particular region.
BROAD CLASSIFICATION OF MAGNETIC MATERIALS
Magnetic materials are broadly classified into two groups, i.e. (i) soft magnetic materials and
(ii) hard magnetic materials.
The size and shape of the hysteresis curve for ferro- and ferrimagnetic materials are of
considerable importance. The area within a loop represents a magnetic energy Loss per unit
volume of material per magnetization–demagnetization cycle; this energy loss is manifested
as heat that is generated within the magnetic specimen and is capable of raising its
temperature. This is called hysteresis loss. Both ferro- and ferrimagnetic materials are
classified as either soft or hard on the basis of their hysteresis characteristics.
B-H Curve of Hard & Soft Magnetic Materials
The nature of the B-H characteristics curve for ferromagnetic and ferrimagnetic materials is
as given in figure below:

In the Hysteresis curve above, H is the magnetic field strength, B is the magnetic flux
density, βr is the remanence and Hc is the coercive force. The size and shape of the hysteresis
curve is of considerable practical importance. The area within a loop represents a magnetic
energy loss per unit volume of material per magnetization-demagnetization cycle.
Depending on the preferential selectivity of magnetization, we can apply magnetizing force
in a particular direction to have either a soft magnetic material or a hard magnetic material. If
we apply magnetizing force along (1,0,0) then it would be soft magnetic material. If the
magnetizing force is applied along (1,1,1) it would be hard magnetic material.

Soft Magnetic Materials

Soft magnetic materials are those materials that are easily magnetised and demagnetised.
They are characterized by their low loss, low retentivity, low coercivity and high
permeability.
 Hysteresis curve for soft magnetic materials
The saturation field or magnetization is determined by the composition of the material.
Analogous to grain boundaries, the domain walls tend to get pinned down by dislocation
tangles, impurity atoms, voids and nonmagnetic precipitates and inclusions. However,
susceptibility and coercivity (Hc), which also influence the shape of the hysteresis curve, are
sensitive to structural variables rather than to composition. A low value of coercivity
corresponds to the easy movement of domain walls as the magnetic field changes magnitude
and/or direction. Structural defects, e.g. particles of a non magnetic phase or voids in the
magnetic material tend to restrict the motion of domain walls, and thus increase the coercivity
(Hc). Hence, a soft magnetic material must be free from such structural defects.
Initial permeability, is improved by minimizing all sources of magnetic anisotropy. A high
maximum permeability, necessary for motors and power transformers, is increased by the
alignment of the anisotropy, for e.g., through development of crystal texture or magnetically
induced anisotropy. For this reason the relative area within the hysteresis loop must be small;
it is characteristically thin and narrow.
Soft magnetic materials should have low hysteresis losses and low eddy current losses. The
hysteresis loss may be kept low by using a material with a narrow hysteresis loop (one with
low coercive force Hc, the value of H required to reduced B to zero). Easy domain wall
motion is the key factor in keeping the hysteresis losses to a minimum.
In addition to hysteresis energy losses, energy losses may result from electrical currents,
called eddy currents. Increasing the electrical resistivity of the magnetic medium reduces
eddy current losses. This is achieved in ferromagnetic materials by alloying. Soft magnetic
materials have iron, which is the cheapest of the ferromagnetic elements, as the main
constituent. The desired characteristics of soft magnetic materials may be obtained by
alloying iron with silicon for low frequency applications. Oxide magnetic materials, such as
ferrites, are also employed for high frequency applications, since they not only have low
hysteresis losses, but also, being oxides, have high electric resistance compared to magnetic
alloys; this leads to extremely low eddy current losses.
The hysteresis characteristics of soft magnetic materials may be enhanced for some
applications by an appropriate heat treatment in the presence of a magnetic field. This may
produce a square hysteresis loop, which is desirable in some magnetic amplifier and pulse
transformer applications. The ceramic ferrites are commonly used for applications requiring
soft magnetic materials because they are intrinsically insulators. However, their applicability
is limited, as they have relatively small susceptibilities. Moreover soft magnetic materials are
used in generators, motors, dynamos, and switching circuits..
The important applications of soft magnetic materials are in transformer and manufacturing
cores of electric motors, and as memory cores in computers.

Common Soft Magnetic Materials

There are seven major groups of commercially important materials: iron and low carbon
steels, ironsilicon alloys, iron-aluminium-silicon alloys, nickel-iron alloys, iron-cobalt alloys,
ferrites and amorphous alloys. Common soft materials are listed below:
Iron and Silicon Alloys (Silicon Steel)
Soft magnetic materials should be pure as they are economically possible. Iron is the main
constituent of soft magnetic materials. The characteristics of iron can be changed by adding
certain alloying constituents. The addition of silicon in iron (upto 5%) raises the maximum
permeability, reduces the area of hysteresis loop, eliminates ageing, and substantially raises
the electrical resistivity. On the other hand, it reduces magnetization, and introduces
difficulties with mechanical properties. It is a useful alloy for electrical equipment,
particularly magnetic cores of transformers operating at power frequencies. Silicon steels are
also extremely used in large alternators and high frequency rotating machines.
Ferromagnetic single crystals have highly directional properties. For iron and silicon iron, the
cube edge direction is the direction of high permeability. The silicon doping increases the
resistivity of the material for which eddy current loss is reduced.
Iron—Cobalt Alloys
An alloy containing 49% iron, 49% cobalt, 2% vanadium has high saturation density. This is
used for airborne high speed generator and motor and also in servomotors, loud speakers,
telephone diaphragms and magnetic pole tips. The high curie temperature of this alloy makes
it useful for high temperatures. Presence of vanadium makes the alloy malleable.
Nickel—Iron Alloys
A nickel—iron alloy with nickel content of about 25% is practically nonmagnetic with BCC
crystallographic fuse. As nickel content is increased, a wide range of remarkable magnetic
properties may be obtained with appropriate choice of heat treatment. The alloys can be
divided into three groups: 36% Ni, 50% Ni and 77% I, although other compositions are also
used. 36% Ni alloys have high resistivity and are used for high frequency devices. 50% Ni
alloys have high flux density and maximum permeability. Such alloys can be made to give
rectangular hysteresis loop by heavy cold rolling process. 77% Ni alloys have high initial
permeability and low losses.

Hard magnetic materials

Hard magnetic materials are those which retain a considerable amount of their magnetic
energy after the magnetizing force has been removed i.e. the materials, which are difficult to
demagnetize. These materials are also called permanent magnetic materials.
 Hysteresis curve for hard magnetic materials

A hard magnetic material has high remanence, coercivity, and saturation flux density, as well
as low initial permeability, high Curie temperature, to minimize easy demagnetization, and
high hysteresis energy losses. Figure below shows a comparison of the hysteresis
characteristics of hard and soft magnetic materials. The area within the hysteresis loop for
hard magnetic material is greater compared to that of soft magnetic materials.

Magnetization curves for soft and hard magnetic material

The two most important characteristics relative to applications for these materials are the
coercivity and what is termed the energy product, designated as (BH) max. This (BH)max
corresponds to the area of the largest B–H rectangle that can be constructed within the second
quadrant of the hysteresis curve, as shown in figure below; its units are kJ/m 3. The value of
the energy product is representative of the energy required to demagnetize a permanent
magnet—that is, the larger (BH)max, the harder the material in terms of its magnetic
characteristics.
The value of (BH)max is representative of the energy required to demagnetize a permanent
magnet, i.e., the larger (BH)max the harder is the magnetic material in terms of its magnetic
characteristics. Although the overall quality of a permanent magnet depends on (BH)max, but
the design considerations, high Hc, high residual induction BT (the magnetic induction when
H is reduced to zero) and reversibility of permeability µ may also be controlling factors.
The hysteresis behaviour of a material is related to the ease with which the magnetic domain
boundaries move; by impending domain wall motion, the coercivity and susceptibility are
enhanced, such that a large external field is required for demagnetization. Moreover, these
characteristics are interrelated to the microstructure of the material. To understand the
relation between the resistance to demagnetization, i.e., the coercivity Hc, and the
metallurgical microstructure, it is essential to understand the mechanisms of magnetization
reversal. The two major mechanisms are reversal against a shape anisotropy and reversal
through nucleation and growth of reverse magnetic domains against crystal anisotropy.

Conventional Hard magnetic materials

Hard magnetic materials can be studied under two main categories: Conventional and high
energy hard materials. The conventional hard magnetic materials have (BH)max values that
range between about 2 and 80 kJ/m3. Ferromagnetic materials—magnet steels, cunife (Cu-Ni-
Fe) alloys, alnico (Al-Ni Co) alloys as well as hexagonal ferrites (BaO-6Fe 2O3) are
conventional hard magnetic materials.
The hard magnet steels are generally alloyed with tungsten and/or chromium. These two
elements readily combine with carbon in the steel to form tungsten and chromium carbide
precipitate particles, which are especially effective in obstructing domain wall motion under
the proper heat-treating conditions. An appropriate heat treatment for the other metal alloys
forms extremely small single domain and strongly Fe-Co particles within a non magnetic
matrix phase.
High Energy Hard magnetic materials
Recently, some intermetallic compounds having a variety of compositions have been
developed. These permanent magnetic materials have (BH)max in excess of about 80 kJ/m3.
The two that have found commercial exploitation are SmCo5 and Nd2Fe14B
Samarium Cobalt Permanent magnets
SmCo5 is a member of a group of alloys that are combinations of Co or Fe and a light rare-
earth element; a number of these alloys exhibit high-energy, hard magnetic behaviour. One
uses powder metallurgical techniques to fabricate SmCo5 magnets. The piece is then sintered
at an elevated temperatures, and heat treated to improve the magnetic properties of the
material.
Neodymium-Iron-Boron Permanent Magnets
Sm is a rare and relatively expensive material. Moreover, the price of Co is variable and its
sources are unreliable. This is why, the Nd2Fe14B alloys have become the materials of choice
for a large number and wide diversity of applications requiring hard magnetic materials.
The magnetization and demagnetization behaviour of these hard magnetic materials is a
function of domain wall mobility, which, in turn, is controlled by the final microstructure-i.e.,
the size, shape and the orientation of the crystallites and grains, as well as the nature and
distribution of any second-phase particles that are present. There are two different processing
techniques available for the fabrication of Nd2Fe14B magnets: powder metallurgy (sintering)
and rapid solidification (melt spinning).
Hard materials are used in motors, loudspeakers, meters, holding devices and in a host of
different devices in a variety of technological fields. Permanent magnets are far superior to
electromagnets in that their magnetic fields are continuously maintained and without the
necessity of having to expend electrical power. Moreover, no heat is generated during
operation. This is why permanent magnets are preferred in motors. The important
applications of permanent magnets are in meters, in cordless drills and screw drivers; in
automobiles (starters, window winter, wiper, washer and fan motors); transducers, electron
tubes, focusing magnets in television tubes, audio and video recorders, speakers in audio
systems, lightweight earphones, hearing aids, in clocks, and computer peripherals etc.
Other Hard Magnetic Materials
Hardened Steel
These include carbon steel, chromium and tungsten steels and several cobalt steels. They
have relatively low energy products. These materials have high physical strength, good
workability and in some cases low cost. They are used in the form of hot rolled bars, rods or
strips.
Carbon for Non-machinable Alloys
This group is comprised of materials in ‘Alnico’ class, which are produced in magnetic form
by cooling and grinding process. Alnico contains aluminum, nickel and cobalt. Other
elements such as copper and titanium are also found in some types. Some of these alloys are
heat-treated in a magnetic field during the course of their manufacture, a few are cast in such
a way as to produce grain-oriented structure. The latter material costs more than other
alnicos. They are isotropic, so can be magnetized in any direction.
Alnico alloys find application in all cases where a permanent magnet can be used. Their
magnetic properties are very stable with time, temperature and shock.
Pressed or Sintered Metalled Powder Magnets
Pressed-powder magnets made of finely divided iron and iron cobalt powders have inherent
advantage over other types of permanent materials. They require no heat treatment to produce
their permanent magnetic qualities and they have the desirable loss tolerances typical of die-
pressed powders. Sintered powder magnets are also made by sintering metal powders at high
temperature using conventional powder metallurgy techniques. Very small magnets can be
made in this manner more readily than by the use of casting methods.
Oxide Magnets
Magnets made from iron oxides or components of iron oxides and the oxides of other metals
can be made to combine good permanent magnet properties with high chemical stability,
lower than average density, and very high electrical resistivity.
 DIELECTRICS MATERIALS
Dielectrics are the materials having electric dipole moment permanently or temporarily by
applying the electric field. Then are mainly used to store electrical energy and as electrical
[Link] dielectrics are electrical insulators, But all electrical insulators are need not to
be [Link] example the vaccum is a perfect insulator. But it is not a dielectric. The
function of any insulator is to prevent the flow of electricity through it when a difference of
potential is applied across its ends. The study of dielectrics is essentially the study of
[Link] dielectrics, all the electrons are bound to their parent molecules and there are no
free charges. Further at the ordinary temperatures, the electrons cannot be dislodged either by
thermal vibrations or by ordinary applied voltages. Generally the dielectrics are non-metallic
materials of high specific resistance and have negative temperature coefficient of resistance.

Fundamental definitions in dielectrics

(1) Dielectric constant ‘Ԑr’
The dielectric characteristics of a material are determined by the dielectric constant or
relative permittivity ‘Ԑr’ of that material. The dielectric constant determines the share of the
electric stress which is absorbed by the material. It is the ratio between the permittivity of the
medium and the permittivity of free space.
Ԑr= Ԑ /Ԑc
the dielectric constant ‘Ԑr’ has no unit and it is a measure of the electrical polarisation in the
dielectric material.
(i) Electric polarisation
When an electric field is applied to a crystal or a glass containing positive and negative
charges,the positive charges are displaced in the direction of the field, while the negative
charges are displaced in the opposite direction. This displacement produces local dipoles
throughout the [Link] the process of producing dipoles by an electric field is called
polarisation in dielectrics.
(ii) Polarisation vector p
It is found that the strength of the induced electric dipole moment is proportional to the
applied electric field.
i.e., µ=αE
where α is the constant of proportionality, called the polarisability. If µ¯ is the average dipole
moment per molecule and N is the number of molecules per unit volume then the polarisation
of the solid is given by the polarisation vector P and it can be written as,
P = N¯µ
So the polarisation vector P is the dipole moment per unit volume of the dielectric material.
(iv) Electric displacement vector D'
The electric displacement vector (or) electric induction 'D' is a quantity which is a very
convenient function for analysing the electrostatic fields in the dielectrics and is given by
D=ԐE = ԐoE+P
From this one can get

=Ԑ-Ԑo=Ԑo (Ԑr-1)

This quantity D' is similar to the magnetic induction B' in [Link] the electtric
displacement vector ‘D’ has the remarkable property that its sources are only the free electric
charges.
(v) Electric susceptibility ‘Xe’
The polarisation vector ‘P’ is proportional to the total electric field intensity E and is in the
same direction of E. Therefore the polarisation vector can be written as P= Ԑ oXeE Where the
constant Xe is referred as the electric susceptibility and is a characteristic of every dielectric.

Therefore Xe= = Ԑr -1 (or) Ԑr =1+Xe

Ԑ
DIFFERENT TYPES OF ELECTRIC POLARISATION
Polarisation occurs due to several microscopic mechanisms. Particularly in the [Link]
fields,the macroscopic polarisation vector ‘P’ is created by four types of microscopic
polarisation mechanisms:
a. Electronic Polarisation
b. Ionic Polarisation
c. Orientational Polarisation
d. Space charge Polarisation

Different types of polarisation mechanisms a. Electronic Polarisation b. Ionic Polarisation

c. Orientational Polarisation d. Space charge Polarisation

a. Electronic polarisation
Electronic polarisation is defined as an electric strain produced in an atom due to the
application of electric field. It is the result of the displacement of the positively charged
nucleus and the (negative) electrons of an atom in opposite directions on the application of
the electric field. This kind of polarisation is present in all materials. Further it is proportional
to the volume of the atoms in the material and is independent of temperature.
b. Ionic polarisation
The ionic polarisation is due to the displacement of cations and anions in opposite directions
and occurs in an ionic solid. This displacement is also independent of [Link] does not
occur in typical covalent crystals such as diamond. Suppose an electric field is applied in the
+ve x direction(figure (b)). Then the +ve ions move to the right and –ve ions move to the left.
c. Orientational polarisation
The orientational polarisation is due to the presence of polar molecules in the dielectric
medium. Polar molecules have permanent dipole moments even in the absence of field. When
an electric field is applied on the dielectric medium with polar molecules, the electric field
tries to align these dipoles along its direction. Due to that there is a resultant dipole moment
in that material and this process is called orientational polarisation. The difference between
the polar dielectrics and the non-polar dielectrics is given below:

Since the polar molecules have permanent dipoles, they align their dipoles in the field
direction with a decrease in potential energy. This phenomenon is similar to the alignment of
permanent magnetic moments of atoms in a magnetic field giving rise to paramagnetism. Just
as in paramagnetism, the orientational polarization is a function of temperature.
d. Space - charge polarisation
Space-charge polarisation occurs due to the accumulation of charges at the electrodes
interfaces in inultiphase dielectrics. This is possible when one of the phases present has much
higher resistivity than the other. It is found in ferrites and semiconductors. Since the value of
space-charge polarisability is very small when we compare it with polarisabilities, the total
polarisability of a gas 'α' can be written as

This Equation is known as Langevin-Debye Equation.

FREQUENCY AND TEMPERATURE EFFECTS ON POLARISATION
On application of an alternating field across the material, the polarisation occurs as a function
of time. Electronic polarisation is extremely rapid and is comi instant of time even when the
frequency of the voltage is very high in the opticalra it occurs at all frequencies (figure
below). But ionic polarisation is slower and the i respond at all when the voltage corresponds
to visible optical frequencies. That is, the field here is changing too rapidly for the ions to
reorient themselves in response to the final each time it is reversed. So the ionic polarisation
does not occur at visible optical frequencies The orientational polarisation is slower than the
ionic polarisation and occurs only at electrical frequencies which are smaller than the infrared
frequencies. Space - charge polarisation is the slowest process and occurs only at power
frequencies (50 - 60 Sec-'). Thus at low frequencies, the value of the total polarisation is very
high and at high frequencies (optical frequencies) the value of the total polarisation is very
small.
Usually orientational polarisability depends strongly on temperature whereas the electronic
and the ionic polarisabilities are practically independent of temperature for normal
temperatures. Normal temperatures will oppose the permanent dipoles to align in the field
direction. But higher temperatures facilitate the movement of ions and molecules so that a
given polarisation process, which is not possible at higher frequencies at normal temperatures
can occur at higher frequencies at elevated temperatures.

Frequency dependence on Polarization

DIELECTRIC BREAKDOWN
When a dielectric loses its insulation resistance and permits large currents to pass through it,
it is said to breakdown. In practical applications, the failure or breakdown of a dielectric
material is of great concern to the Engineer. There are many causes for dielectric breakdown.
Important types of dielectric breakdowns are
a. Intrinsic breakdown
b. Thermal breakdown
c. Electrochemical breakdown
d. Discharge breakdown and
e. Defect breakdown
a. Intrinsic breakdown
In a dielectric, the charge displacement increases with increasing field strength. Beyond a
critical value of the field strength, there is an electric breakdown due to the physical
deterioration of the dielectric material. The dielectric strength is defined as the breakdown
voltage per unit thickness of the material. When the applied electric field is large,some of the
electrons in the valance band cross over the large conduction band across the band gap giving
rise to large conduction [Link] this condition,the strength of local field is of the order
of 1 mega volt/[Link] the liberation or movement of electrons from valance band is called
internal emission of electrons and this breakdown is called intrinsic breakdown or Zener
[Link] electrons moving under the high accelerating electric force collide with the
atoms or [Link] release more electrons and holes by breaking covalent bonds
between [Link] the current density increases. The covalent bonds between atoms and
moleculesare broken continuously and finally dielectric breakdown [Link] type of
breakdown is called Avalanche [Link] in the dielectric material create
additional energy levels in the energy gap and so they help the intrinsic breakdown to occur
at lower applied voltage.
Characteristics
1. This can occur even at low temperatures.
2. This requires relatively large electric fields.
3. Mostly this kind of breakdown occurs in thin samples.
4. This does not depend on the electrodes configuration and shape of the material.

b. Thermal Breakdown
This is due to the attainment of an excessive temperature in the dielectric. The electrical
energy loss has to be dissipated as heat and if the heat dissipated is less than the heat
generated there a progressive increase in the temperature of the dielectric which eventually
results in local [Link] that time enormous current will flow through the material and
immediately dielectric breakdown will occur.
Characteristics
1. This can occur only at high temperatures.
2. The strength of the electric field to create dielectric breakdown depends upon the
materials size and shape.
3. The breakdown time is of the order of few milliseconds.
4. Since the dielectric loss is directly proportional to frequency ,the electric field
strength to create this dielectric breakdown will be smaller for alternating fields amd
higher for D.C fields.

c. Electrochemical breakdown
Chemical and electrochemical breakdown have a close relationship with thermal breakdown.
When temperature rises, mobility of ions increases and hence electrochemical reaction takes
place. When temperature rises, mobility of ions increases and hence electrochemical reaction
takes place. When ionic mobility increases leakage current also increases and this will lead to
dielectric breakdown. The chemical reaction gradually decreases the insulation resistance and
finally creates the dielectric breakdown. Not only by the application of electric field but also
by so many ways the chemical reaction can occur.
i. Some of the insulating materials become oxides of those insulating materials in
the presence of air or ozone. Particularly if we take Rubber, it is converted into
oxide in air and cracks are produced in it in the Ozone atmosphere. Since it is
converted to oxide, the dielectric properties are decreasing gradually.
ii. Some of the organic materials working at high temperatures have lost their
stability towards chemical properties.
iii. Due to moisture and temperature the electrical and mechanical properties of
cellulose esters are decreasing gradually.
iv. When foreign materials are joined with insulating materials, the insulation
properties of them are reduced due to some chemical reactions.
v. Thus due to chemical reactions, the electrical and mechanical properties of
insulating materials are changed and finally these will lead to breakdown.
Characteristics
1. Electrochemical breakdown is determined by the leakage current, density of ions,
temperature and permanent dipoles in the material.
2. To reduce electrochemical reactions, the foreign materials would not be mixer pure
insulating materials.
3. Electrochemical reactions are accelerated by high temperatures. So to avoid
breakdown, insulating materials should not be operated at high temperatures.
4. If there are layers of materials with permanent dipoles on the insulating material,then
there may be large leakage current which leads to breakdown. Therefore the materials
having permanent dipole moment should not be used as high temperature insulating
materials.
d. Discharge breakdown
Gas discharge breakdown occurs when the insulator contains occluded gas bubbles. Since
gases require smaller ionization potential than solids, the gaseous atoms ionize first and the
gaseous ions bombard the solid dielectric causing electrical deterioration.
Characteristics
1. Thus can occur at low voltages where there are large number of occluded gas bubbles in
the insulating material.
2. When discharge takes place at a point, the surrounding places are burnt and hence their
electrical properties are affected. Thus the life of the insulation of an insulating material
depends upon the number of discharges which are taking place inside the material. That
is, it depends upon the frequency of the applied voltage.

e. Defect breakdown
It is due to cracks and pores at the surface of the material. Moisture and other impurities can
collect at these discontinuities leading to breakdown.

Thus to avoid breakdown, an insulating material should have the following properties.
1. Dielectric strength as good as that of mica.
2. Mechanical strength as good as that of steel.
3. Fire proofing quantities as good as that of silica.
4. Chemical inertness as good as that of platinum.
5. Water proofing quality as good as that of paraffin wax.
6. Volume and surface resistivities as good as that of sulphur.
7. Surface finish as good as that of ebonite.
8. Thermal conductivity as good as that of silver.
9. Thermal expansion as low as that of invar.
FERROELECTRIC MATERIALS
Materials which exhibit electric polarisation even in the absence of the applied field are
known as Ferroelectric materials. These have permanent dipole moment in each atom or
molecule. The dielectric constants of these materials are some three orders of magnitude
larger than that in ordinary dielectrics. Ferroelectricity refers to the creation of enormous
value of induced dipole moment in a weak electric field as well as existence of electric
polarisation even in the absence of applied electric field. Ferroelectricity is a result of
dielectric hysteresis. Since these materials exhibit hysteresis effects, similar to those
observed in ferromagnetic materials, they are called ferroelectric materials. Barium titanate
(BaTi03), Potassium dihydrogen phosphate (KH 2PO4), Ammonium dihydrogen phosphate
(NH4H2PO4), Lithium Niobate (LiNbO3) and Rochelle salt (NaKC4H4O64H20) are the typical
examples of ferroelectric materials.

Dielectric hysteresis in Ferroelectric materials

Properties of Ferroelectric materials

1. Ferroelectric materials can be easily polarised even by very weak electric fields.
2. They exhibit dielectric hysteresis. Lagging of polarisation behind the applied electric
field is called dielectric hysteresis. Ferroelectricity is a result of dielectric hysteresis.
3. Ferroelectric materials possess spontaneous polarisation, which is a polarization that
persists when the applied field is zero.
4. They possess permanent electric dipoles and internal electric field which develop
spontaneous polarisation at ferroelectric curie temperature.
5. Ferroelectric materials exhibit ferroelectricity when the temperature T is less tha or
equal to Tc where Tc = ferroelectric curie temperature. When T > Tc they are
converted to paraelectric materials.
 6. They exhibit domain structure as in the case of ferromagnetic materials.
7. Ferroelectric materials exhibit piezoelectricity. Piezoelectricity means the creation of
polarisation by mechanical stress. Piezoelectricity means the creation of electric
polarisation by thermal stress.
Piezoelectric materials are used to make pressure transducers, ultrasonic transducers
and microphones.
(Examples:
i. Quartz, Lithium Niobate and Barium Titanate among the crystalline materials.
ii. lead Zirconium Titanate, Calcium Barium Titanate and Lead Barium Niobate
among the ceramic materials)
Pyroelectric materials are used to make high sensitive infrared detectors. (Examples:
Barium Titanate, Triglycine sulphate, Lithium Niobate. Lithium Tantalare and Polyvinyl
fluoride).
8. Some ferroelectric semiconductors like BaTiO3-SiTiO3, BaTiO3- PbTiO3, and SrTiO3-
PbTiO3, are used to make posistors which are used to measure and control temperature
like thermistors. These have positive temperature coefficient of resistance.
9. Electrets are ferroelectric materials and are electrostatic analog of permanent magnets.
Electrets possess a gross permanent electric dipolement. They are manufactured from
certain types of waxes, plastics and ceramics. When these waxes are subjected to high
electric fields (~ 106V/m) they are polarised in their molten state and retain a permanent
polarisation after solidifying eventhough the extemal polarising field is removed.
Electrets are used in capacitor microphones and gas filters to capture submicron particles
by electrostatic attraction. Further the electret bondages are used over the fractured bones
to speed up the healing process.
 INSULATING MATERIALS

Even though the dielectric materials are essentially insulating materials, the function of an
insulating material is to obstruct the flow of electric current while the function material is to
store electrical energy.
Important applications of insulating materials
i. Electric wiring in houses is made up of conductors made of copper or aluminium
which are insulated with a covering of plastic, rubber or some kind of varnished
cotton.
ii. Overhead conductors in the street for distribution of electricity comprises aluminium
or steel-cored aluminium conductor and air between the conductors acts as isulator.
iii. Electric iron comprises high resistance conducting wire for heat generation and mica
or asbestos insulation is to prevent the flow of electric current in the outer body of the
iron.
iv. Electric fan comprises a single phase motor having copper winding on the stator and
varnished cotton acts as insulator.
Important applications of dielectric materials
The dielectric materials are used in capacitors to store electrical energy. Depending upon the
type of dielectric used, the capacitor may be grouped into the following four categories.
ii. Capacitors which use vacuum, air & gases as dielectrics: Dielectric losses in these
capacitors are very small. The value of these capacitances is not very large. Therefore
these are used in radio frequency circuits and in low frequency measuring circuits
where precision is highly desirable.
iii. Capacitors in which the dielectric is a mineral oil : Dielectric losses are not very
small. The values of these capacitors are very large. So these are so these are used in
high voltage applications.
iv. Capacitors which use a combination of solid and liquid dielectrics: Papers, films
of synthetic materials, glass, mica etc. and mineral oil, castor oil, silicon liquids are
used as dielectrics. This type of capacitors are used for power factor correction in
electric power distribution system where precision is not so important but a high
value of capacitance is required.
v. Capacitors with only a solid dielectric: Glass, mica, titanium oxide, etc, are used in
these capacitors. This type of capacitors are used in laboratories as standard
capacitors. The dielectric constant of mica does not change much with temperature
variation and time. Further it has high value dielectric constant and high insulation
resistance.
Electrical properties of insulating materials
a) Insulation resistance
The main reason of the failure of any electric equipment is the insulation failure. The major
function of the insulation resistance is to prevent the flow of electricity through it and at the
same time it must conduct the heat generated inside the material. For an insulating material,
insulation resistance should be as high as possible. Insulation resistance is of two types:
1. Volume resistance and 2. Surface resistance
Volume resistance is the resistance offered to the current which flows straight through the
volume of insulating [Link] resistance can be expressed as

Rv = ρ v

Where ρv = volume resistivity expressed in ohm - m

𝑙 = the length of current path through the material in metre

a = the area of cross section of the current path in m2
Surface resistance is the resistance offered to the current ‘Ia’ which flows over the surface of
the insulating material. Surface resistivity is numerically equal to the resistance of a square
of unit area on the surface of the insulating material and is expressed in ohm/m 2.
Factors affecting the insulation resistance
i. Temperature: Insulation resistance decreases with the rise of temperature and is very
much affected by temperature variations.
ii. Moisture: Surface resistance of the insulation decreases if it is expressed to moisture.
iii. Voltage : The value of insulation resistance is also affected by the voltage applied
and to a small extent by the direction in which the voltage is applied. Insulation
resistance decreases with the increase in applied voltage.
iv. Age : Insulation resistance decreases with age.

b) Dielectric strength
Dielectric strength or electric strength or breakdown voltage is the minimum voltage
required to produce dielectric breakdown. It is expressed in volts per unit thickness of the
insulating material. For example the breakdown potential of air is 3 Mega volt/m which
means that the maximum potential difference that 1m thickness of air can withstand is 3
mega volts. If the voltage increases beyond this value then air insulation will breakdown.
Dielectric strength decreases with the rise of temperature and humidity.
c) Dielectric constant or Relative permittivity
Dielectric constant determines the share of the electric stress which is absorbed by the
material. Greater the dielectric constant, greater will be the capacitance of the insulating
material.
d) Dielectric loss
When a dielectric is subjected to a.c, voltage the electrical energy is absorbed by the material
and is dissipated in the form of heat. This dissipation of energy is called dielectric loss.
Dielectrics should have low dielectric loss. The rise of the temperature, humidity, high
voltage and high frequency increase the dielectric loss.

Mechanical properties
The insulating materials should possess sufficient mechanical strength which is an important
requirement. Rise of temperature and humidity affect the mechanical strength of insulating
materials. It is not desired to have a dielectric of high porosity. Since high porosity insulating
materials will increase the moisture holding capacity which is not desired because it
adversely affects the electrical properties. In the manufacture of solid insulating it should be
able to be easily moulded and machined into the required shape. For liquid insulating
material, the surface tension should be low because it causes greater wetting of the electrical
components and this gives better cooling, impregnation and greater voltage uniformity.
Mechanical strength depends on the viscosity, solubility and density. Finally an insulating
material should be uniform throughout in order to keep minimum electrical lossses and
uniform electrical electric stresses under high voltage differences.

Thermal properties
A dielectric which is capable of withstanding higher temperatures without the other
properties being affected can be used for higher temperature applications. In any electrical
apparatus the insulation is intended to be operated at some fixed temperature. The operating
temperature affects the life of the insulation. The life of insulation is halved for each 8 to
10°C rise above the recommended operating temperature for a given apparatus. The melting
point of liquid dielectric used with solid dielectric should be sufficiently high. Thermal
expansion should be very small. Thermal expansion is of significant importance where heavy
currents are involved. An insulating material should have high thermal conductivity because
the heat produced due to I2R losses and dielectric losses will be dissipated to the atmosphere
and will not allow rise in temperature. Insulating materials exposed to arcing should be non-
ignitable.

Chemical properties
Chemically a material is a better insulating material if it resists chemical action. The chemical
resistance requirements of insulating materials used in underground cables, which are likely
to operate under severe chemical condition due to water, salts, acids and alkalies will be more
demanding than those of the insulating materials used in motor winding. Paraffin and
polythene are non hygroscopic. But certain insulating materials absorb moisture from the
atmosphere and so all the electrical properties are affected badly. The insulating materials are
also affected by the contact with the conducting and structural materials. If rubber is in
contact with copper, chemical action takes place. To avoid it, a coating of tin 18 a copper
before putting on the rubber insulation.

Visual Properties
These properties are not of any significant importance from the engineering point of view
therefore do not have any effect on the performance of insulating materials. However the
colour should be bright and dark, and there is a smooth finish to have good appearance. These
properties count to some extent towards the customer's selection for the insulating materials.

Different types of dielectric materials

Based on the applications we have two types of dielectric materials
i. Active dielectrics (Ferroelectrics, piezoelectrics and pyroelectrics)
ii. Passive dielectrics (electrical insulating materials).
Active dielectrics or Ferroelectric materials
Active dielectrics are the materials which can be adapted to generate, amplify, modulate
Convert electrical signals. These can store electrical energy.
Passive dielectrics (or) Insulating materials
The function of the insulating material is to obstruct the flow of electric current.

Classification of insulating materials

Insulating materials are classified into three categories
a. Solid insulating materials: Mica, Porcelain, asbestos, backelite, rubber, PVC, polythene,
glass, cotton, silk, wood and ceramics.
b. Liquid insulating materials: Varnish, transformer oil, cable oil, silicon fluids and fluoro
organic fluids.
c. Gaseous insulating materials: Air, hydrogen, nitrogen, halogens and sulphur hexa
fluoride.
Let us see first the important solid insulating materials.
i. Ceramic insulating materials
Ceramics are also be called potter's earth or clay. It is the product which is produced
by the action of fire on an earthly material. Structurally ceramics are crystals bonded
together. These are generally inorganic, non metallic, ionic or covalent compounds. Ceramics
can be produced by mixing finely ground clay and metal oxide with water just sufficient to
make a paste which is shaped according to the requirements. This mould is finally dried and
fired at temperature ranging between 1200°C and 1700°C. Ceramics are hard, strong and
dense. They are completely stable at high temperatures. They are not affected by moisture
and by chemical action except with strong acids and alkalies.
Ceramic materials can be classified as clay products, refractories and glasses.
Porcelain is the important clay product. It is used in line insulators, transformer bushing pins,
switches, plugs, fuse holders and sockets. It is also used to make discs for electric stoves,
kettles, etc., beads to insulate heating conductors and conductors connecting heating
elements.
Materials subjected to high temperatures which do not deteriorate or disintegrate are
commonly known as refractory materials. Alumina is an important refractory material. It is
primarily made of aluminium oxide. Its manufacturing is difficult due to extreme temperature
which is of the order of 1750°C. It has high compressive strength, absorbs less moisture and
is excellent in heat conduction. It is used in high temperature appliances like furnaces.
Silica glass, Pyrex and fibre glass are the important glass insulating materials. Glass is
an inorganic material made by the fusion of different oxides like silicon oxide, zinc oxide and
magnesium oxide. Glass is brittle and hard. It has low dielectric loss and has on strength. It is
highly chemical resistant to most corrosive agents and is a good insulator with good
appearance. It is insoluble in water. Glass is used as dielectric in capacitors. It is used as
insulator in radio and television tubes, electrical lamps and laminated boards. Toughened
glass is employed for insulation in extra high voltage lines having voltages above 100
kilovolt.
ii. Mica
Mica is a mineral compound of silicate of aluminium with silicates of soda potash and
magnesia. It has high dielectric strength and low power loss. It is not affected by moisture. It
is rigid, touch and strong. Mica sheets are used as insulation between commutator segments.
Thick mica tape is used for taping the stator coils of high voltage alternators. It is also used in
electric irons, hot plates and toasters for insulation purposes. Mica flakes are used in motor
slot lining and transformers as insulation; Mica paper is used as insulation for armature and
field coils of rotating machines.
iii. PVC materials
When acetylene and hydrogen chloride are combined in presence of catalyst at temperature of
about 50°C polyvinyl chloride (PVC) resin is produced. Due to having good mechanical and
electrical properties it is widely used in the insulation of wires and cables. PVC films, tapes
and sheets are commonly used for insulation in dry batteries, conductors and cables.
iv. Rubber is used for insulation of thick wires carrying high current. Further increased
sulphur content and extended vulcanization treatment on natural rubber give a hard rubber
product. It possesses good dielectric properties and high tensile strength. It is used in the
construction of storage battery housings and panel boards.
v. Asbestos is naturally occurring mineral material of fibrous structure. It has high dielectric
loss and low dielectric strength. Asbestos finds extensive use in electrical machines because
of its ability to withstand very high temperature (400°C). Further it is also used for making of
cloth tapes and paper boards for insulation purposes. It is used for covering on wire for
electric heating devices, ovens, electric irons, etc. It is used as arcing barrier in switches and
circuit breakers, etc.
Liquid insulating materials can be divided into three groups.
i. Mineral insulating oils: Transformer oil, cable oil, capacitor oil, etc.
ii. Synthetic insulating oils: Askarels, aroclors, sovol and sovtol.
iii. Miscellaneous insulating oils : Vegetable oils, vaseline and silicon liquids.
Generally liquid dielectric materials have moderate dielectric strengths. But insulating
liquids improve the insulating properties of other solid materials (fibrous especially) by
eliminating the other gases. They offer good heat dissipation media and facilitate coolings of
the windings which emit heat due to losses in the windings. They are sometimes required for
extinguishing arcs in certain applications like circuit breakers.
Mineral insulating oils
These oils are obtained from crude petroleum by distillation and have high oxidation
resistance and good thermal stability. These are used in transformers and capacitors.
Transformer oil is the important mineral insulating oil with high dielectric strength, viscosity
and cooling properties. This oil is used for insulation and cooling of transformer. It transfers
heat by convection from the windings and cores to the cooling surfaces. It maintains the
insulation of the windings. Now a days synthetic oil is used as an insulator in transformers in
place of transformer oil (mineral oil) because synthetic oils are very much resistant to
oxidation and to fire hazards. Instead of pure mineral insulating oil, a mixture of mineral
insulating oil and synthetic insulating oil is commonly used to get high oxidation resistance
as well as to reduce the cost of the oil.
Synthetic insulating oils
When we compare this with mineral insulating oil, the properties are degraded. But these oils
are very cheap and non inflammable. Due to longer life and safer in operating conditions
synthetic oil is used as coolant and insulant in H.V. transformers. Particularly Askarels have
thermal stability upto 110°C and are manufactured from chlorinated hydrocarbons.
Miscellaneous insulating oils
Silicon liquids have stability upto 200°C and are costly. The dielectric strength of these
liquids is same as that of mineral oils and power factor is very low. There are used in H.V.
Transformers. Further these are used to increase the surface resistivity of ceramic insulators.
Vaseline has high viscosity and high dielectric constant. It is used for impregnation of papers
used in capacitors.
Gaseous insulating materials
a. Air is the most important material available in nature and is used for insulation
between the two conductors of high voltage transmission lines. It is also used in
air capacitors. The power loss is practically zero. The dielectric constant of air is
increased linearly with the increase of pressure. Air can be used as insulation only
in the low voltage applications.
b. Nitrogen is chemically inert. It prevents oxidation and reduces the rate of
deterioration. For example, in oil filled transformers, the Nitrogen is used to
replace oxidizing atmosphere. This is also used in capacitors and in cables under
pressure.
c. Inert gases are used in electronic tubes and discharge tubes as insulators.
d. Sulphur hexafluoride is formed by burning of sulphur in fluorine atmosphere. It
has high dielectric strength and non-inflammable. It has superior cooling
properties to those of air and nitrogen. It has high chemical stability upto 100 0C
and is used in transformers and electric switches. Further it is also used in Vande
Graff voltage stabilizer and X-ray apparatus for insulation purposes.
 UNIT-5
SPV Materials, mono crystalline and poly crystalline materials, amorphous materials
Nano materials: Classification of nano materials, processing of nano materials and properties of
nano materials mechanical, electrical, magnetic and other properties of materials.
Material selection: Economic consideration, Environmental and societal considerations. Issues
in material science - Recycling issues in material science.

SPV Materials / Solar Photo Voltaic Materials

Materials used in solar photo voltaic devices are SPV materials. Common SPV materials are
silicon (monocrystalline, polycrystalline or amorphous), gallium arsenide, metal chalcogenides
and organometallics. Silicon is used in approximately 90% of solar cell semiconductors sold
today. Sand is the source of silicon. Although it is the second most abundant material, it has to
go through complex purification process to obtain 99.99% pure silicon.
The solar cell is based on semiconducting materials which vary from system to system. Most
commonly, solar cells contain two different types of semiconducting materials: a p-type and an
n-type semiconductor, leading to a p-n-junction.
When the light of appropriate wavelength impinges on the solar cell, energy is absorbed
promoting electrons to the conduction band of the semiconductor and leaving behind a hole in
the valence band.

Monocrystalline materials
Within the past few years, single crystals have become extremely important in many of our
modern technologies, in particular electronic microcircuits, which employ single crystals of
silicon and other semiconductors. For a crystalline solid, when the periodic and repeated
arrangement of atoms is perfect or extends throughout the entirety of the specimen without
interruption, the result is a single crystal. All unit cells interlock in the same way and have the
same orientation. This allows the free movement of electrons within the material. Single crystals
exist in nature, but they may also be produced artificially. They are ordinarily difficult to grow,
because the environment must be carefully controlled. Hence they are costlier compared to
polycrystalline materials.

Polycrystalline Materials
Most crystalline solids are composed of a collection of many small crystals or grains; such
materials are termed polycrystalline. The solidification of a polycrystalline specimen undergoes
various stages. Initially, small crystals or nuclei form at various positions. These have random
crystallographic orientations, as indicated by the square grids. The small grains grow by the
successive addition from the surrounding liquid of atoms to the structure of each. The extremities
of adjacent grains impinge on one another as the solidification process approaches completion.
The crystallographic orientation varies from grain to grain. Also, there exists some atomic
mismatch within the region where two grains meet; this area, called a grain boundary. These
grain boundaries restrict the free movement of electrons and in turn decreasing conductivity.
Hence the efficiency of polycrystalline materials is lesser than monocrystalline materials. To
improve efficiency, crystalline silicon is coated with chemicals such as silicon nitride or titanium
dioxide.
Amorphous Materials
Any material that exhibits only a short-range order of atoms or ions is an amorphous material;
that is, it has no crystal structure. Glasses, which typically form in ceramic and polymer systems,
are good examples of amorphous materials. Amorphous materials often offer a unique and
unusual blend of properties since the atoms or ions are not assembled into their ‘‘regular’’ and
periodic arrangements. Similar to inorganic glasses, many plastics are also amorphous. They do
contain small portions of material that are crystalline.
Amorphous silicon, denoted a:Si-H, is an important example of a material that has the basic
short-range order of crystalline silicon. In amorphous silicon, the silicon tetrahedra are not
connected to each other in the periodic arrangement seen in crystalline silicon. Also, some bonds
are incomplete or ‘dangling’. Thin films of amorphous silicon are used to make transistors for
active matrix displays in computers. It is used to create a thin-film solar cell and is commonly
found in smaller solar panels such as those on calculators or to power private homes. The cells
are manufactured by vapor depositing silicon in a very thin film (approximately 1µm) onto a
metal or glass frame. Amorphous silicon solar panels only achieve an efficiency of around 7%,
due to a degradation of the material when first exposed to sun rays.
SPV Materials:
1) Amorphous silicon (multijunction)
2) Cadmium Telluride (CdTe) thin film
3) Copper-Indium-Gallium-Selenium (CIGS)
4) Gallium Arsenide (GaAs)
5) Multi crystalline or polycrystalline silicon
6) Mono crystalline silicon
7) High performance mono-crystalline silicon
8) Triple-junction (GaInP/GaAs/Ge) cell
 NANO MATERIALS
Introduction
The word ‘nano’ is to a Greek prefix meaning dwarf or something very small and depicts one
billionth (10–9) of a unit. Nano materials have extremely small size, in the order of 1 nm to 100
nm. They can be of any chemical elements: metals, ceramics, polymers or composites. The
modifications in the properties due to reduction in grain size to nanoscale dimensions are very
large, and in most cases the resultant properties are superior to those of conventional materials.

CLASSIFICATION OF NANO MATERIALS

Nanomaterials can be created with various modulation dimensionalities. According to Siegel,
Nanostructured materials are classified as
(a) 0D spheres and clusters,
(b) 1D nanofibers, wires, and rods,
(c) 2D films, plates, and networks,
(d) 3D nanomaterials.

Fig. Classification of Nanomaterials (a) 0D spheres and clusters, (b) 1D nanofibers, wires, and rods, (c)
2D films, plates, and networks, (d) 3D nanomaterials.

Nanomaterials are materials which are characterized by an ultra-fine grain size (< 50 nm) or by a
dimensionality limited to 50 nm. They can exist in single, fused, aggregated or agglomerated
forms with spherical, tubular, and irregular shapes. Common types of nanomaterials include
nanotubes, dendrimers, quantum dots and fullerenes. Nano materials have applications in the
field of nano technology, and displays different physical chemical characteristics from normal
chemicals (i.e., silver nano, carbon nanotube, fullerene, photocatalyst, carbon nano, silica).
(a) Zero-dimensional: These particles have all three dimensions in nanorange.
E.g.: The submicroscopic particles of CuAl2 that precipitate during ageing of a duralumin
alloy and carbide particles that form during the early stages of tempering of martensite in
steels. However, they are nanoparticles embedded in a bulk material
(b) One-dimensional: These particles have two dimensions in nanorange and the third
dimension is much larger.
 E.g.: Nanorods, nanowires and nanotubes. Carbon nanotubes are typical examples. They
are cylindrical tubes of carbon atoms with diameter in the range of 1-2 mm and a much
larger length reaching up to a mm.
(c) Two-dimensional: These particles have one dimension in nanorange and the other two are
much larger.
E.g.: Nanofilms, nanosheets and nanocoatings. 2D crystalline nanosheets have thickness
in the nanoscale. In addition, the internal structure of the sheet can be nanosized grains.
(d) Three-dimensional: These particles have all three dimensions much larger than
nanorange. They are sometimes called bulk nanoparticle. Although all dimensions are
beyond nanorange, they are still classified as nanoparticles because the bulk solid itself
may be composed of nanoparticles.
E.g.: nanosized crystals in a bulk polycrystalline material.

PROCESSING OF NANO MATERIALS

Nano materials deal with very fine structures: a nanometer is a billionth of a meter. This indeed
allows us to think in both the ‘bottom up’ or the ‘top down’ approaches (Fig.) to synthesize
nanomaterials, i.e. either to assemble atoms together or to dis-assemble (break, or dissociate)
bulk solids into finer pieces until they are constituted of only a few atoms. This domain is a pure
example of interdisciplinary work encompassing physics, chemistry, and engineering up to
medicine.

Fig. Schematic illustration of the preparative methods of nanoparticles

1. The top down method: a microcrystalline material is fragmented to yield a nanocrystalline
material. For example, the synthesis of porous silicon by electrochemical etching, high-energy
ball milling, sliding wear and high pressure torsion.
2. The bottom up method: individual atoms and molecules are brought together or self-assembled
to form nanostructured materials in at least one dimension. For example, sol-gel method,
Physical/Chemical Vapor Deposition (PVD/CVD), Inert Gas Condensation (IGC), Laser
Ablation, sputtering, electrodeposition, high temperature evaporation, flame synthesis and
plasma synthesis etc.
Usually, the bottom-up techniques can give very fine nanostructures of individual nanoparticles,
nanoshells, etc., with narrow size distributions, if the process parameters are effectively
controlled. The top-down techniques do not usually lead to individual nanoparticles; however,
they can produce bulk nanostructured materials.

Sol-gel process
The sol-gel method is the basis for producing a wide variety of materials in the nanosize range
including ceramics, paints, cosmetics and detergents. Composites can also be made by mixing a
monomer with a nanocrystalline ceramic powder, followed by polymerization.
The sol-gel process, involves the evolution of inorganic networks through the formation of a
colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid phase
(gel). Sol is, by definition, a type of colloid in which solid particles are suspended in a
continuous liquid phase. Colloid is a homogeneous mixture in which the dispersed particles with
diameters of 1-100 nm do not settle out. Gel is an interconnected solid network of polymeric
chains in a liquid matrix with pores of submicrometer dimensions. It is a wet chemical method
for self-assembling a nanomaterial. The precursors (starting material) for synthesizing these
colloids consist usually of a metal or metalloid element surrounded by various reactive ligands
(ligand is an ion or molecule, which donates a pair of electrons to the central metal atom or ion to
form a coordination complex). The starting material is processed to form a dispersible oxide and
forms a sol in contact with water or dilute acid. Removal of the liquid (surfactant) from the sol
yields the gel, and the sol/gel transition controls the particle size and shape. Calcination of the
gel produces the oxide (nanomaterial). Sol-gel processing refers to the hydrolysis and
condensation of alkoxide-based precursors such as Si(OMe)4 (tetramethyl orthosilicate, or
TMOS) or Si(OEt)4 (tetraethyl orthosilicate, or TEOS). The reactions involved in the sol-gel
chemistry based on the hydrolysis and condensation of metal alkoxides M(OR)z can be
described as follows:

MOR + H2O → MOH + ROH (hydrolysis)

MOH + ROM → M-O-M + ROH (condensation)
 Schematic representation of sol-gel process of synthesis of nano materials

Sol-gel method of synthesizing nano materials is very popular amongst chemists and is widely
employed to prepare oxide materials. The sol-gel process can be characterized by a series of
distinct steps:
1. Formation of different stable solutions of the alkoxide or solvated metal precursor.
2. Gelation resulting from the formation of an oxide- or alcohol- bridged network (the gel) by a
poly condensation reaction that results in a dramatic increase in the viscosity of the solution. The
characteristic of the network are greatly influenced by the size of particles and degree of cross-
linking prior to gelation. The sol transforms into gel by collision and growth of the particles
which gradually become more and more interconnected and at some point can support stress
elastically, this is defined the gelation point.
3. Aging of the gel (Syneresis), during which the polycondensation reactions continue until the
gel transforms into a solid mass, accompanied by contraction of the gel network and expulsion of
solvent from gel pores. Ostwald ripening (also referred to as coarsening, is the phenomenon by
which smaller particles are consumed by larger particles during the growth process) and phase
transformations may occur concurrently with syneresis. The aging process of gel can exceed 7
days and is critical to the prevention of cracks in gels that have been cast. Structural changes of
gel, such as decrease of porosity and increase of thickness, take place in order to increase the
strength of the gel as it needs to resist during drying.
4. Drying of the gel, when water and other volatile liquids are removed from the gel network.
This process is complicated due to fundamental changes in the structure of the gel. The drying
process has itself been broken into four distinct steps: (i) the constant rate period, (ii) the critical
point, (iii) the falling rate period, (iv) the second falling rate period. If isolated by thermal
evaporation, the resulting monolith is termed a xerogel. If the solvent (such as water) is extracted
under supercritical or near super critical conditions, the product is an aerogel.
5. Dehydration, during which surface- bound M-OH groups are removed, there by stabilizing the
gel against rehydration. This is normally achieved by calcining the monolith at temperatures up
to 8000C.
6. Densification and decomposition of the gels at high temperatures (T>800 0C). The pores of the
gel network are collapsed, and remaining organic species are volatilized.
The interest in this synthesis method arises due to the possibility of synthesizing nonmetallic
inorganic materials like glasses, glass ceramics or ceramic materials at very low temperatures
compared to the high temperature process required by melting glass or firing ceramics.
The major difficulties to overcome in developing a successful bottom-up approach is controlling
the growth of the particles and then stopping the newly formed particles from agglomerating.
Other technical issues are ensuring the reactions are complete so that no unwanted reactant is left
on the product and completely removing any growth aids that may have been used in the process.
Also production rates of nano powders are very low by this process. The main advantage is one
can get mono sized nano particles by any bottom up approach.

Gas Condensation Processing/ Gas Phase Condensation (GPC)

In this technique, a metallic or inorganic material, e.g. a suboxide, is vaporized in refractory
metal crucibles (W, Ta or Mo) using thermal evaporation sources such as Joule heating, electron
beam evaporation devices or sputtering sources in an atmosphere of 1-50 mbar He (or another
inert gas like Ar, Ne, Kr). If metals with high melting points or metals which react with the
crucibles, are to be prepared, sputtering, i.e. for W and Zr, or laser or electron beam evaporation
has to be used.

Fig. Schematic representation of typical set-up for gas condensation synthesis of nanomaterials followed
by consolidation in a mechanical press or collection in an appropriate solvent media.
Clusters form in the vicinity of the source by homogenous nucleation in the gas phase and grow
by coalescence and incorporation of atoms from the gas phase. The cluster or particle size
depends critically on the residence time of the particles in the growth system and can be
influenced by the gas pressure, the kind of inert gas, i.e. He, Ar or Kr, and on the evaporation
rate/vapor pressure of the evaporating material. With increasing gas pressure, vapor pressure and
mass of the inert gas used the average particle size of the nanoparticles increases.
Originally, a rotating cylindrical device cooled with liquid nitrogen was employed for the
particle collection: the nanoparticles in the size range from 2-50 nm are extracted from the gas
flow by thermophoretic forces and deposited loosely on the surface of the collection device as a
powder of low density and no agglomeration. Subsequently, the nanoparticles are removed from
the surface of the cylinder by means of a scraper in the form of a metallic plate.
However, this method can only be used in a system designed for gas flow, i.e. a dynamic vacuum
is generated by means of both continuous pumping and gas inlet via mass flow controller. A
major advantage over convectional gas flow is the improved control of the particle sizes.
Depending on the flow rate of the He-gas, particle sizes are reduced by 80% and standard
deviations by 18%.
Composite materials such as Cu/Bi or W/Ga have been synthesized by simultaneous evaporation
from two separate crucibles onto a rotating collection device. It has been found that excellent
intermixing on the scale of the particle size can be obtained. However, control of the
composition of the elements has been difficult and reproducibility is poor. Nanocrystalline oxide
powders are formed by controlled post oxidation of primary nanoparticles of a pure metal (e.g.
Ti to TiO2) or a suboxide (e.g. ZrO to ZrO2).

Inert-gas Condensation Method

It is a slight modification of gas-condensation method and one of the early techniques developed.
It is a bottom up method with two basic steps:
1. Evaporation of the material: It is done inside a chamber filled with an inert gas like helium of
partial pressure equal to a few hundred pascals. The vaporization of the material can be carried
out by any sort of the source as sputtering, plasma heating, laser vaporization, electric arc
discharge or thermal vaporization.
2. Controlled condensation of the evaporated atoms: The evaporated atoms collide with the
helium atoms, lose their energy and condense as discrete crystals of loose nanosized powder. The
powder particles condense on the surface of a rod cooled by liquid nitrogen, are scrapped off and
sent for compaction
The whole procedure is processed in an atmosphere of inert gas (He, Xe or Ar). The breakdown
of the source to atomic level, which can be done to both solid or gaseous state sources and then
the production of the required size of the nanoparticles are determined by the nature of the inert
gas (He, Xe or Ar) present in the chamber and the pressure of the present gas in the chamber.
Depending on the source of breaking down the source to the metallic nuclei, the method can be
called as Chemical Vapor Deposition or Chemical Vapor Condensation.
 As illustrated in the figure, there are scattered,
evaporation sources in the main UHV chamber
having the metal or inorganic substance in solid or
liquid form, placed inside it. The containing units
have one of the vaporization techniques deployed
in them.
Once the procedure is started, it turns the non-
gaseous state matter into a gaseous state. An inert
gas inlet is made into the chamber to make sure
the flow and the presence of inert gas in the UHV
chamber.
To collect the grown particles of the metallic
nanoparticles in the chamber, a long tube is placed
in the chamber with its outlet source outside of the
chamber. Liquid nitrogen, acting as cooling agent,
is passed through the tube to keep the surface of
the tube on the inner side of the UHV chamber
cool. This allows the collection and rapid
condensation of the particles collected on the outer
surface of the tube containing nitrogen.
When the collection procedure is completed, the
nanoparticles and nanocomposites drop down into the collecting funnel and into the chamber, in
which the nanoparticle and nanocomposites are treated in low- and high-pressure compaction
units respectively to make sure the desired physical properties.

Sputtered Plasma Processing:

In this method the source material (alloy, ceramic or compound) is a sputtering target and this
target is sputtered using rare gases (high energy ions) and the constituents are allowed to
agglomerate to produce nanomaterial. Low deposition time and a low temperature of the
substrate help in preventing the growth of the nano particles into larger ones. Reactive sputtering
or multi target sputtering has been used to make alloys and/or oxides, carbides, nitrides of
materials. This method is specifically suitable for the preparation of ultrapure and non-
agglomerated nanoparticles of metal.
Mechanical grinding/ Mechanical milling/ ball milling
Mechanical attrition is a typical example of ‘top down’ method of synthesis of nanomaterials,
where the material is prepared not by cluster assembly but by the structural decomposition of
coarser-grained structures as the result of severe plastic deformation. This has become a popular
method to make nanocrystalline materials because of its simplicity, the relatively inexpensive
equipment needed, and the applicability to essentially the synthesis of all classes of materials.
The major advantage often quoted is the possibility for easily scaling up to tonnage quantities of
material for various applications. Similarly, the serious problems that are usually cited are;
1. Contamination from milling media and/or atmosphere, and
2. To consolidate the powder product without coarsening the nanocrystalline microstructure.

Fig. Schematic representation of the principle of mechanical milling

Mechanical milling is typically achieved using high energy shaker, planetary ball, or tumbler
mills. In this method, small hard balls made of hardened steel (or steel covered with WC
particles) are placed along with the material to be crushed in a rotating drum. During rotation, the
collision with the balls breaks up the material into fine particles and also causes heavy plastic
deformation. A continuous refinement of the internal structure occurs. The energy transferred to
the powder from refractory or small hardened steel balls depends on the rotational (vibrational)
speed, size and number of the balls, ratio of the ball to powder mass, the time of milling and the
milling atmosphere. The average grain size can be reduced to a few nm after extended milling.
Once again, the challenge is to retain the nanograin sizes during the subsequent process of
compaction, as grains tend to grow owing to recovery processes.
Milling in cryogenic liquids can greatly increase the brittleness of the powders influencing the
fracture process. As with any process that produces fine particles, an adequate step to prevent
oxidation is necessary. Hence this process is very restrictive for the production of non-oxide
materials since then it requires that the milling take place in an inert atmosphere and that the
powder particles be handled in an appropriate vacuum system or glove box. This method of
synthesis is suitable for producing amorphous or nanocrystalline alloy particles, elemental or
compound powders. If the mechanical milling imparts sufficient energy to the constituent
powders a homogeneous alloy can be formed. Based on the energy of the milling process and
thermodynamic properties of the constituents the alloy can be rendered amorphous by this
processing.

Laser Ablation

Laser ablation is used to produce nano particles of metal, metal oxides and metal carbides. It can
be performed directly on to solids (target) in inert gas atmosphere or by placing the target in a
solution.
A base system consists of a target, substrate carrier which is mounted in a vacuum chamber. A
high power pulsed laser is focused onto the target material and, when the laser influence exceeds
the ablation threshold value for the material, chemical bonds are broken and the material is
fractured into energetic fragments, typically a mixture of neutral atoms, molecules, and ions. A
unique property of the ablation process is that most of the absorbed energy is deposited in the
ejected material, so that there is little or no thermal damage to the surrounding target material.
The plume is typically directed towards the substrate where a thin-film is deposited.

Physical vapor deposition (PVD) and chemical vapor deposition (CVD)

Physical vapor deposition (PVD) and chemical vapor deposition (CVD) are considered to be the
most attractive surface coating technologies and have a wide range of applications in various
industries.
 Physical Vapor Deposition Chemical Vapor Deposition
Definition Physical vapor deposition (PVD) is a Chemical vapor deposition (CVD) is
series of vacuum deposition methods a vacuum deposition method. In a
used to produce films and coatings. typical CVD, the wafer (substrate) is
PVD is characterized by a process in exposed to one or more volatile
which the material changes from a precursors that react and/or
condensed phase to a gas phase and decompose on the surface of the
then back to the condensed phase of substrate to produce the desired
the film (physical process). The most deposit. Volatile by-products are
common PVD processes also typically produced which are
are sputtering and evaporation. removed by the gas stream through
the reaction chamber.
Application PVD is used to make articles that Chemical vapor deposition (CVD) is
require films for mechanical, optical, used to produce high quality, high-
chemical or electronic functions. For performance solid materials. This
example, semiconductor devices, thin- process is commonly used in the
film solar panels, glass coatings, and semiconductor industry to produce
etc. thin films.
Temperature Relatively low The process temperature of CVD
method is very high, usually exceeds
the tempering temperature of the
high speed steel. Thus in order to
restore the hardness, the tools must
be subjected to vacuum heat
treatment after coating.
Cleaning High Low
Requirement
Film thickness about 2.5 μm about 7.5 μm
Surface The PVD coating well reflects the The surface of the CVD coating is
surface of the tool and has a good slightly rougher than the surface of
metallic luster without grinding. the substrate.
Crafting Nearly all PVD technologies have CVD occurs in a low-vacuum
Process poor coating performance both on the gaseous environment and has good
back and sides of the tool due to low coating performance. Therefore,
air pressure. The PVD reactor must except for the support points, all the
reduce the loading density to avoid surfaces of the cutters sealed in the
shadow formation, and the loading and reactor, even deep holes and inner
fixing are complicated. walls, can be completely coated.
Cost More expensive Less expensive
Safety PVD is a kind of “green engineering”, The reactive gas and reaction tail gas
which produces little pollution during of CVD may have certain
the process because it is “physical”. corrosiveness, flammability and
toxicity, and there may be powdery
and fragmented substances in the
reaction tail gas.
PROPERTIES OF NANOMATERIALS
Nanomaterials have the structural features in between of those of atoms and the bulk materials.
While most micro structured materials have similar properties to the corresponding bulk
materials, the properties of materials with nanometer dimensions are significantly different from
those of atoms and bulks materials. This is mainly due to the nanometer size of the materials
which render them: (i) large fraction of surface atoms; (ii) high surface energy; (iii) spatial
confinement; (iv) reduced imperfections, which do not exist in the corresponding bulk materials.
Due to their small dimensions, nanomaterials have extremely large surface area to volume ratio,
which makes a large to be the surface or interfacial atoms, resulting in more “surface” dependent
material properties. Especially when the sizes of nanomaterials are comparable to length, the
entire material will be affected by the surface properties of nanomaterials. This in turn may
enhance or modify the properties of the bulk materials. For example, metallic nanoparticles can
be used as very active catalysts.
Chemical sensors from nanoparticles and nanowires enhanced the sensitivity and sensor
selectivity. The energy band structure and charge carrier density in the materials can be modified
quite differently from their bulk and in turn will modify the electronic and optical properties of
the materials. For example, lasers and light emitting diodes (LED) from both of the quantum dots
and quantum wires are very promising in the future optoelections. High density information
storage using quantum dot devices is also a fast developing area.
Reduced imperfections are also an important factor in determination of the properties of the
nanomaterials. By self-purification process the impurities and intrinsic material defects will
move to near the surface upon thermal annealing. This increased materials perfection affects the
properties of nanomaterials. For example, the chemical stability for certain nanomaterials may be
enhanced, the mechanical properties of nanomaterials will be better than the bulk materials. The
superior mechanical properties of carbon nanotubes are well known
Electrical properties
In a 3D nano material, no electron confinement occurs in occurs in any direction. In a 3D
crystalline solid, grain boundaries become effective centers of scattering. Consequently electrical
conductivity decreases. In a 2D nanosheet, electron confinement occurs in thickness direction.
The electrons are however free to move in the other two directions.
In 1D nanomaterials, electron confinement occurs in two directions and electron flow is possible
only along the length of the tube or wire. In carbon nanotubes, the electron and phonon motion
occur without any scattering along the length of the tube. The electrical and thermal
conductivities along the tube length are found to be very much larger than that of copper. In 0D
nanoparticles (called quantum dots), electron confinement occurs in all three directions.
With decreasing diameter of the wire, the number of electron wave modes contributing to the
electrical conductivity becomes increasingly smaller by well-defined quantized steps.
Nanocrystalline materials are used as very good separator plates in batteries, because they can
hold more energy than the bulk materials.
Electrical resistivity of nano particles are increased by 3 times.
Mechanical properties
Mechanical Properties of Nanoparticles compare to bulk materials have:
1. Higher young’s modulus and tensile strength.
2. Lower plastic deformation
3. Increased brittleness, toughness and hardness
4. They are more wear resistant and corrosion resistant
Refinement of grain size increases the strength of materials without loss of ductility. Grain
boundaries are obstacles to the movement of dislocations. Hence finer grain size impedes
dislocation motion and improving strength (3-7 times).
Porosity in nanoparticles decreases the elastic modulus.
Nano particles possesses lower melting point than the bulk materials. Gold nanoparticles melt at
lower temperature 3000C for 2.5 nm, but Gold slab melts at 1064 0C.
Magnetic properties
Bulk gold and Pt are non-magnetic, but at the nano size they are magnetic. Surface atoms are not
only different to bulk atoms, but they can also be modified by interaction with other chemical
species, that is, by capping the nanoparticles. Also the non-ferromagnetic bulk materials can
exhibit ferromagnetic-like behavior when prepared in nano range. In the case of Pt and Pd, the
ferromagnetism arises from the structural changes associated with size effects. However, gold
nanoparticles become ferromagnetic when they are capped with appropriate molecules: the
charge localized at the particle surface gives rise to ferromagnetic-like behavior. Surface and the
core of Au nanoparticles with 2 nm in diameter show ferromagnetic and paramagnetic character,
respectively.
The large spin-orbit coupling of these noble metals can yield to a large anisotropy and therefore
exhibit high ordering temperatures. More surprisingly, permanent magnetism was observed up to
room temperature for thiol-capped Au nanoparticles. For nanoparticles with sizes below 2 nm the
localized carriers are in the 5d band. Bulk Au has an extremely low density of states and
becomes diamagnetic, as is also the case for bare Au nanoparticles. This observation suggested
that modification of the d band structure by chemical bonding can induce ferromagnetic like
character in metallic clusters.
Chemical Properties
One of the important factors for the chemical applications of nanomaterials is the increment of
their surface area which increases the chemical activity of the material. Due to their enhanced
chemical activity, nanostructural materials can be used as catalysts to react with such noxious
and toxic gases as carbon monoxide and nitrogen oxide in automobile catalytic converters and
power generation equipment to prevent environmental pollution arising from burning gasoline
and coal.
Bulk gold is chemically inert and thus considered to be not active or useful as a catalyst.
However, gold nanoparticles can have excellent catalytic properties. Au nanoparticles exhibit
extraordinary high activity for partial oxidation of hydrocarbons, hydrogenation of unsaturated
hydrocarbons and reduction of nitrogen oxides.
Fuel cell technology is another important application of the noble metal nanoparticles relating
the catalysis of the reactions. In the present, the fuel cell catalysts are based on platinum group
metals (PGM). Pt and Pt-Ru alloys are some of the most frequently used catalysts from this
group. In fact, the use of these metals is one major factor for cell costs, which has been one of
the major drawbacks preventing it from growing into a more important technology. One
possibility to produce economical catalysts is the use of bimetallic nanoparticles.
Optical properties
One of the most fascinating and useful aspects of nanomaterials is their optical properties. The
properties like color and transparency are considered as optical properties. These properties are
observed to change at nanoscale level. For example: (1) Bulk gold appear yellow in color while
in nanosize gold appear red in color. (2) Bulk silicon appears grey in color while nanosized
silicon appears red in color. (3) Zinc oxide, which at bulk scale blocks ultraviolet light and
scatters visible light and gives white appearance. While nanoscale zinc oxide is very small in
particle size compared with wavelength of visible light and it does not scatters it. Thus it appears
transparent.
The main reason for change in optical properties at nanoscale level is that nanoparticles are so
small that electrons in them are not as free to move as in case of bulk material. Due to this
restricted movement of electrons, nanoparticles react differently with light as compared to bulk
material.
The optical properties of nanomaterials depend on parameters such as feature size, shape, surface
characteristics, and other variables including doping and interaction with the surrounding
environment or other nanostructures. With the CdSe semiconductor nanoparticles, a simple
change in size alters the optical properties of the nanoparticles.
Applications based on optical properties of nanomaterials include optical detector, laser, sensor,
imaging, phosphor, display, solar cell, photocatalysis, photoelectrochemistry and biomedicine.

APPLICATIONS OF NANOMATERIALS
 Cutting tools and inserts, made of nanocrystalline carbides and other ceramics
 Specialty bicycle frames, baseball bats, and tennis racquets, using carbon nanotubes
 Silver nanoparticles have good antibacterial properties, and are used in surgical
instruments, refrigerators, air-conditioners, water purifiers etc.
 Gold nanoparticles are used in catalytic synthesis of silicon nano wires, sensors carrying
the drugs and in the detection of tumors.
 ZnO nanoparticles are used in electronics, ultraviolet (UV) light emitters, piezoelectric
devices and chemical sensors.
 TiO2 nanoparticles are used as photocatalyst and sunscreen cosmetics (UV blocking
pigment).
 Antimony-Tin-Oxide (ATO), Indium-Tin-Oxide (ITO) nanoparticles are used in car
windows, liquid crystal displays and in solar cell preparations.
 MATERIAL SELECTION

Economic Considerations
It goes without saying that engineering practice involves utilizing scientific principles to design
components and systems that perform reliably and satisfactorily. Another critical driving force in
engineering practice is that of economics; simply stated, the company or institution must realize
a profit from the products that it manufactures and sells. The product must be offered for sale at a
price that is attractive to the consumer, and, in addition, return a suitable profit to the company.
There are three factors over which the materials engineer has control and which affect the cost of
a product; they are (1) component design, (2) the material(s) used, and (3) the manufacturing
technique(s) that are employed. These factors are interrelated in that component design may
affect which material is used, and both component design and the material used will influence
the choice of manufacturing technique(s).
Component Design
Some fraction of the cost of a component is associated with its design. In this context,
component design is the specification of size, shape, and configuration, which will affect in-
service component performance. For example, if mechanical forces are present, then stress
analyses may be required. Detailed drawings of the component must be prepared; computers are
normally employed, using software that has been generated for this specific function. It is often
the case that a single component is part of a complex device or system consisting of a large
number of components (e.g., the television, automobile, VCR, etc.). Thus, design must take into
consideration each component’s contribution to the efficient operation of the complete system.
Component design is a highly iterative process that involves many compromises and trade-offs.
The engineer should keep in mind that an optimal component design may not be possible due to
system constraints.
Materials
In terms of economics, it is desirable to select the material(s) having the appropriate combination
of properties which are the least expensive. Once a family of materials has been selected that
satisfy the design constraints, cost comparisons of the various candidate materials may be made
on the basis of cost per part. Material price is usually quoted per unit mass. The part volume may
be determined from its dimensions and geometry, which is then converted into mass using the
density of the material. In addition, during manufacturing there ordinarily is some unavoidable
material waste, which should also be taken into account in these computations.
Manufacturing Techniques
As stated previously, the choice of manufacturing process will be influenced by both the material
selected and part design. The entire manufacturing process normally consists of primary and
secondary operations. Primary operations are those that convert the raw material into a
recognizable part (e.g., casting, plastic forming, powder compaction, molding, etc.), whereas
secondary ones are those subsequently employed to produce the finished part (e.g., heat
treatments, welding, grinding, drilling, painting, decorating).
The major cost considerations for these processes include capital equipment, tooling, labor,
repairs, machine downtime, and waste. Of course, within this cost analysis, rate of production is
an important consideration. If this particular part is one component of a system, then assembly
costs must also be addressed. And, finally, there will undoubtedly be costs associated with
inspection and packaging of the final product.
There are also other factors not directly related to design, material, or manufacturing that figure
into the product selling price. These factors include labor fringe benefits, supervisory and
management labor, research and development, property and rent, insurance, profit, taxes, and so
on.
Environmental and Societal Considerations
Our modern technologies and the manufacturing of their associated products impact our societies
in a variety of ways—some are positive, others are adverse. Furthermore, these impacts are
economic and environmental in type, and international in scope in as much as:
(1) The resources required for a new technology often come from many different countries,
(2) The economic prosperity resulting from technological development is global in extent, and
(3) The environmental impacts extending beyond the boundaries of a single country.
Materials play a crucial role in this technology-economy-environment scheme. A material that is
utilized in some end product and then discarded passes through several stages or phases; these
stages are represented in figure, which is sometimes termed the ‘total materials cycle’ or just
‘materials cycle,’ and represents the ‘‘cradle-to-grave’’ life circuit of a material.

Beginning on the far left side of figure, raw materials are extracted from their natural earthly
habitats by mining, drilling, harvesting, etc. These raw materials are then purified, refined, and
converted into bulk forms such as metals, cements, petroleum, rubber, fibers, etc. Further
synthesis and processing results in products that are what may be termed ‘engineered materials’;
examples include metal alloys, ceramic powders, glass, plastics, composites, semiconductors,
elastomers.
Next, these engineered materials are further shaped, treated, and assembled into products,
devices, and appliances that are ready for the consumer—this constitutes the ‘product design,
manufacture, assembly’ stage. The consumer purchases these products and uses them (the
‘applications’ stage) until they wear out or become obsolete, and are discarded. At this time the
product constituents may either be recycled/reused (whereby they reenter the materials cycle) or
disposed of as waste, normally being either incinerated or dumped as solid waste in municipal
land-fills—as such, they return to the earth and complete the materials cycle.
It has been estimated that worldwide, on the order of 15 billion tons of raw materials are
extracted from the earth every year; some of these are renewable and some are not. The earth is
virtually a closed system relative to its constituent materials, and its resources are finite. In
addition, as our societies mature and populations increase, the available resources become
scarcer, and greater attention must be paid to more effective utilization of these resources relative
to this materials cycle.
Furthermore, energy must be supplied at each cycle stage; in the United States it has been
estimated that approximately one-half of the energy consumed by manufacturing industries goes
to produce and fabricate materials. Energy is a resource that, to some degree, is limited in supply
and measures must be taken to conserve and more effectively utilize it in the production,
application, and disposal of materials.
And, finally, there are interactions with and impacts on the natural environment at all stages of
the materials cycle. The condition of the earth’s atmosphere, water, and land depends to a large
extent on how carefully we traverse this materials cycle. Some ecological damage and landscape
spoilage undoubtedly result during the extraction of raw materials phase. Pollutants may be
generated that are expelled into the air and water during the synthesis and processing stage; in
addition, any toxic chemicals that are produced need to be disposed of or discarded.
The final product, device, or appliance should be designed such that during its lifetime, any
impact on the environment is minimal; furthermore, at the end of its life that, at best, provision
be made for recycling of its component materials, or at least for their disposal with little
ecological degradation (i.e., it should be biodegradable).
Recycling of used products rather than disposing of them as waste is a desirable approach for
several reasons. First of all, using recycled material obviates the need to extract raw materials
from the earth, and thus conserves natural resources and eliminates any associated ecological
impact from the extraction phase. Second, energy requirements for the refinement and processing
of recycled materials are normally less than for their natural counterparts; for example,
approximately 28 times as much energy is required to refine natural aluminum ores than to
recycle aluminum beverage can scrap. And, finally, there is no need to dispose of recycled
materials. Thus, this materials cycle is really a system that involves interactions and exchanges
among materials, energy, and the environment.
In many countries, environmental problems and issues are being addressed by the establishment
of standards that are mandated by governmental regulatory agencies. Furthermore, from an
industrial perspective, it becomes incumbent for engineers to propose viable solutions to existing
and potential environmental concerns. Correcting any environmental problems associated with
manufacturing will influence product price. That is, manufacturing cost is normally greater for a
‘green’ (or ‘environmentally friendly’) product than for its equivalent that is produced under
conditions wherein environmental issues are minimized. Thus, a company must confront the
dilemma of this potential economic-environmental trade-off and then decide the relative
importance of economics and of environmental impact. One approach that is being implemented
by industry to improve the environmental performance of products is termed life cycle
analysis/assessment. With this approach to product design, consideration is given to the cradle-
to-grave environmental assessment of the product, from material extraction to product
manufacture to product use, and, finally, to recycling and disposal; sometimes this approach is
also labeled as ‘green design.’ One important phase of this approach is to quantify the various
inputs (e.g., materials and energy) and outputs (e.g., wastes) for each phase of the life cycle. In
addition, an assessment is conducted relative to the impact on both global and local
environments in terms of the effects on the ecology, human health, and resource reserves.

Recycling Issues in Materials Science

Important stages in the materials cycle where materials science and engineering plays a
significant role are recycling and disposal. The issues of recyclability and disposability are
important when new materials are being designed and synthesized. Furthermore, during the
materials selection process, the ultimate disposition of the materials employed should be an
important criterion. From an environmental perspective, the ideal material should be either
totally recyclable or completely biodegradable. Recyclable means that a material, after having
completed its life cycle in one component, could be reprocessed, could reenter the materials
cycle, and could be reused in another component—a process that could be repeated an indefinite
number of times. Completely bio degradable means, by interactions with the environment
(natural chemicals, microorganisms, oxygen, heat, sunlight, etc.), the material deteriorates and
returns to virtually the same state in which it existed prior to the initial processing. Engineering
materials exhibit varying degrees of recyclability and biodegradability.
Metals and Alloys
Most metal alloys (e.g., Fe, Cu), to one degree or another experience corrosion and are also
biodegradable. However, some metals (e.g., Hg, Pb) are toxic and, when land-filled, may present
health hazards. Furthermore, alloys of most metals are recyclable; on the other hand it is not
feasible to recycle all alloys of every metal. In addition, the quality of alloys that are recycled
tends to diminish with each cycle. Product designs should allow for the dismantling of
components composed of different alloys. Another of the problems of recycling involves
separation of various alloys types (e.g., aluminum from ferrous alloys) after dismantling and
shredding; in this regard, some rather ingenious separation techniques have been devised (e.g.,
magnetic and gravity). Joining of dissimilar alloys presents contamination problems; for
example, if two similar alloys are to be joined, welding is preferred over bolting or riveting.
Coatings (paints, anodized layers, claddings, etc.) may also act as contaminants, and render the
material nonrecyclable.
Aluminum alloys are very corrosion resistant, and, therefore, nonbiodegradable. Fortunately,
however, they may be recycled; in fact, aluminum is the most important recyclable nonferrous
metal. Since aluminum is not easily corroded, it may be totally reclaimed. A low ratio of energy
is required to refine recycled aluminum relative to its primary production. In addition, there are a
large number of commercially available alloys that have been designed to accommodate impurity
contamination. The primary sources of recycled aluminum are used beverage cans and scrapped
automobiles.
Glass
Glass is the one ceramic material that is consumed by the general public in the greatest quantities
in the form of containers. Glass is a relatively inert material, and, as such, it does not decompose;
thus, it is not biodegradable. A significant proportion of municipal land-fills consist of waste
glass; so also does incinerator residue. In addition, there is not a significant economic driving
force for recycling glass. Its basic raw materials (sand, soda ash, and limestone) are inexpensive
and readily available. Furthermore, salvaged glass (also called ‘cullet’) must be sorted by color
(clear, amber, and green), by type (plate vs. container), and by composition (lime, lead, and
borosilicate [or Pyrex]); these sorting procedures are time-consuming and expensive. Therefore,
scrap glass has a low market value, which diminishes its recyclability. Advantages of utilizing
recycled glass include more rapid and increased production rates and a reduction in pollutant
emissions.
Plastics and Rubber
One of the reasons that synthetic polymers (including rubber) are popular as engineering
materials lies with their chemical and biological inertness. On the down side, this characteristic is
really a liability when it comes to waste disposal. Polymers are not biodegradable, and, as such,
they constitute a significant land-fill component; major sources of waste are from packaging,
junk automobiles, automobile tires, and domestic durables. Biodegradable polymers have been
synthesized, but they are relatively expensive to produce. On the other hand, since some
polymers are combustible and do not yield appreciable toxic or polluting emissions, they may be
disposed of by incineration.
Thermoplastic polymers, specifically polyethylene terephthalate, polyethylene, and
polypropylene, are those most amenable to reclamation and recycling, since they may be
reformed upon heating. Sorting by type and color is necessary. In the United States, type sorting
of packaging materials is facilitated using a number identification code; for example, a ‘1’
denotes high-density polyethylene (HDPE). The recycled plastic is less costly than the original
material, and quality and appearance are generally degraded with each recycle. Typical
applications for recycled plastics include shoe soles, tool handles, and industrial products such as
pallets.
The recycling of thermoset resins is much more difficult since these materials are not easily
remolded or reshaped due to their cross linked or network structures. Some thermosets are
ground up and added to the virgin molding material prior to processing; as such, they are
recycled as filler materials.
Rubber materials present some disposal and recycling challenges. When vulcanized, they are
thermo set materials, which makes chemical recycling difficult. In addition, they may also
contain a variety of fillers. The major source of rubber scrap in the United States is discarded
automobile tires, which are highly non-biodegradable. Scrap tires have been utilized as a fuel for
some industrial applications (e.g., cement plants), but yield dirty emissions. Recycled rubber
tires that have been split and reshaped are used in a variety of applications such as automotive
bumper guards, mud flaps, door mats, and conveyor rollers; and, of course, used tires may also
be recapped. In addition, rubber tires may be ground into small chunks that are then recombined
into the desired shape using some type of adhesive; the resulting material may be used in a
number of non-demanding applications such as place mats and rubber toys. The most viable
recyclable alternatives to the traditional rubber materials are the thermoplastic elastomers. Being
thermoplastic in nature they are not chemically cross linked and, thus, are easily reshaped.
Furthermore, production energy requirements are lower than for the thermo set rubbers since a
vulcanization step is not required in their manufacture.
Composite Materials
Composites are inherently difficult to recycle because they are multiphase in nature. The two or
more phases/materials that constitute the composite are normally intermixed on a very fine scale;
consequently, complete phase/material separation is virtually impossible, and recycling
procedures that require material separation are impractical.