Materials Science and Engineering

Introduction and basic principles

Everything around us is made up of materials, and they are basic substances that
have mass and occupy space. The air we breathe, the water we drink and the food we eat and
so on. They can be natural or human-made. Natural materials are materials that come from
animals, plants and rocks and manufactured materials are those obtained from natural
materials through chemical processes. A wide range of materials in nature form an essential
part of the ecosystem in multiple ways. The materials that are used not only in the field of
engineering, but on a day to day basis because of their properties are called engineering
materials. Material engineers develop and test new materials for different specific
applications. A wide range of new products like computer chips, recreational equipment (golf
clubs, bicycles), and building materials for houses, bridges, cars, and aircraft will be created.
Advanced materials refer to all new materials and modifications to existing materials to
obtain superior performance in one or more functional features that are critical for the
application under consideration. The functional materials perform specific functions within a
system. Some recent advances include shape memory alloys and nanomaterials.
Supermaterials of the future include aerogel, carbon nanotube, transparent alumina, e-textiles,
metamaterials, nano-diamond and amorphous metal. Graphene is the thinnest material ever
invented-only one atom thick yet stronger than steel. Every material has a set of physical and
chemical properties that define it. The physical properties include melting point, boiling
point, color, hardness, density and so forth. The chemical properties include reactivity with
water, oxygen, acids, bases, and others. Traditionally, materials were developed keeping in
mind a particular set of properties and were mainly used for making components and
structures. With the advancement of materials science, they are expected to perform the role
of an ‘intelligent’ structure. An excellent example of this would be applications of shape
memory alloys, and they can be used to make deployable antennas. These materials enable
people to explore the design and use of new products to improve the quality of life. Modern
materials are employed in the primary production or manufacturing of a good, and there are
about 3,00,000 different known materials. These include specialty and bulk chemicals,
beverages and food products, metal products and alloys, wood and paper products, rubber and
plastic products, textile and consumer goods, and those used in mining and metallurgy, and
printing and publishing industries.

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 The kind of questions that a student in materials science would like answers to include
the following; What is the densest crystal packing that can be achieved? How do
intermolecular attractions arise? Why is glass transparent and brittle while copper opaque and
ductile? Why is a diamond an efficient thermal conductor, but electrical insulator? Why is it
easier to bend the Al rod as compared to the steel rod? Why is a wire of copper conducting,
while a piece of dry wood non-conducting? How can we change properties like hardness,
flexibility, biocompatibility in a material? Why does the electrical conductivity of Ag
decrease on heating, while that of Si increases? Why does naphthalene (para-
dichlorobenzene) solid evaporate? How can we explain the fact that good thermal conductors
are also good electrical conductors? How can one understand the observations that when we
release the load on a rubber band/spring, it comes back to its original shape while a bent
aluminum rod would not come back? Why is it essential for some objects being transparent?
Why is glass transparent to visible light, but opaque to UV light? Why can aluminum oxide
exist as a transparent, translucent or opaque a material? What are the reasons for the viscosity
of honey, mercury and paraffin oil? Why are composites used instead of metals, ceramics, or
polymers? What is the mechanism behind functional smart materials? What does material
science offer to society? Who can deny the role of materials in human existence? The
answers to such questions could lead the learner to take the subject to higher levels of
understanding, an understanding of the complex structure-property relationships, molecular
mechanisms of material transformations, the development of an active system, to arrive at
practical science-based solutions, and finally better materials management solutions.

Materials technology includes a range of materials used for manufacturing products,

machines, and structures. For example, plastics are used in solid form as synthetic fibers for
textiles, a film for packaging and in composites like fiberglass. Metals like iron or aluminum
continue to be essential for building machines and structures. Concrete is the prime material
for building civil structures such as bridges. Some building materials like steel, concrete, and
bricks are structural while others, such as ceramics and glass are mainly decorative.
Appropriate technology serves local needs using local resources such as stone and wood.
Rubber is used for the soles of shoes and motor tires because of its resilience and elasticity. It
is also used in rubber gloves and rainwear due to its flexibility and waterproof property.
Plaster of Paris (POP) has the distinct feature of setting into a hard mass on wetting with
water. It is used to make castings for statues, toys and decorative materials, for setting broken
or fractured bones in the right position and as a fireproofing material. Thin-film materials are

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used extensively in sensor applications. Thin film solar cells like amorphous silicon,
cadmium telluride, copper indium gallium selenide and dye-sensitized solar cells are other
examples of important novel materials. The nano-scale effects on sterical and biological
properties include increased selectivity for specific drug transportation and controlled release,
increased permeability through membranes, and improved biocompatibility. The role of
materials science research, technology and innovations extend to almost all fields of human
activity, and this particular domain has a transformational effect on the development in many
areas which include healthcare, food processing, housing, energy, metals and minerals, and
aerospace. The future of materials engineering is to obtain optimal performance by
combining material design innovation with advances in technology involving several smart
features.

Some materials are hard; others are soft. Some are strong; others are weak. Different
materials have various properties because they contain different elements (atomic structure)
and various combinations of ingredients, contain different types of chemical bonds (bonding
between atoms and molecules, have different sizes of units (crystalline structures). The solid-
state structure (microstructure + macrostructure) may include different types of assemblies,
e.g., molecular packing arrangement may be different, or the geometry of linkage in an
extended 3D structure may vary. Physical properties include mechanical and thermal
properties (hardness, tensile strength, influence of coating, velocity of sound, thermal data
and thermodynamic properties, thermal conductivity), electrical and magnetic properties
(electron paramagnetic resonance, nuclear magnetic resonance, electrical conductivity,
switching effect, thermoelectric power, magnetic susceptibility, magnetoresistance, optical
and spectroscopic properties (index of refraction, dielectric constant, infrared spectra, Raman
spectra, absorption in UV and visible range (EMR), photoconductivity, color dichroism,
photoluminescence, The chemical properties include reactions of atoms, adsorption of gases,
reactions with hydrogen/halogens, and reactions with main group/transition metals. The
following factors put together determines the properties of the material; composition, phases
present and their distribution, defect structure (in the phases and between the phases) and
residual stress. The properties of materials also depend on the properties of individual
components, the relative amount of particles, their size, shape, distribution, orientation and
the degree of bonding. The goal of materials science and engineering is to design materials
with a predetermined set of properties using suitable processing techniques, which gives them
a particular microstructure and desired performance. The role of engineers has become very

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important for meeting the complex and specific challenges of making materials with desired
functional characteristics and solve technical issues with a specialized skill set and
knowledge. The specific objective of this chapter is to provide students the vast subject in a
structured and useful manner to equip them with a basic familiarity with materials science
and engineering. It is a learning journey through the fundamental principles underlying the
materials science and engineering and provides the essential vocabulary of these engineering
sciences through inspirations, experiences, practices, and evolutions.

Classification of Materials

All materials used for engineering application can be put into six broad categories;
pure substances (Cu, Ni, Fe), alloys (brass, NiAl), polymers (polyethene, polyvinyl chloride,
polypropylene) ceramics (alumina, glass, zirconia), composites (wood, golf club shaft,
bricks), and miscellaneous materials (lime, gypsum, tiles). The common types of engineering
materials can be classified into different categories based on various parameters. Based on
phase (state of matter) a given material can be divided into gases, liquids or solids. The solid
state is a rigid state, the particles of liquids can move with greater freedom and gas particles
have total freedom of motion. What distinguishes the crystalline state from the liquid and
gaseous states is the nearly perfect positional order of the particles in crystals. Based on the
structure of particles (arrangement of atoms/molecules/ions) materials can be classified into
crystalline (quartz), quasicrystalline (Al-Pd-Mn alloy) or amorphous (glass). Liquid crystals
and solid electrolytes have the properties in between liquids and crystals. Supercritical fluids
have properties in between liquids and gases. Homogeneous materials include pure
substances and solutions that have fixed, specific features. Heterogeneous materials can be
separated into their components by purely mechanical means such as filtration, decantation,
extraction, centrifuging and so on. Based on the size of the particles in question we can find
nanocrystals, nano-quasicrystals, and bulk materials. Materials can be divided into
paramagnetic, diamagnetic, ferromagnetic, ferrimagnetic, and antiferromagnetic materials
based on the magnetic states of matter. Based on electrical conduction, we can categorize the
materials into conductors (Cu, Al, Ag), semiconductors (Ge, Si, GaAs) and insulators (Al 2O3,
-(CH2-CH2-)n). Based on ductility, we can have two categories- ductile (metals, alloys) and

brittle (ceramics, glasses). Materials can be acoustic conductors (bronze) or acoustic

insulators (cotton fiber) based on the capacity to transmit sounds. Materials can be classified
based on the behavior when light strikes as transparent (clear glass windows, clear plastic

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food wrap), translucent (frosted glass, wax paper) and opaque materials (aluminum foil,
wood). Based on the bonding, solids can be classified into ionic (table salt, calcium chloride)
molecular (ice, solid carbon dioxide) covalent network (diamond, quartz), and metallic solids
(iron, silver). There are other categories of materials such as raw materials, in-process
materials, finished products, bulk materials, value-added products, and packaging materials.
Further classification of chemicals includes bulk chemicals (sulfuric acid), fine chemicals
(ibuprofen) and specialty chemicals (adhesives).

Metals can be further classified into ferrous (steel, stainless steel, cast iron) and non-
ferrous (aluminum, copper, tungsten) metals. Plastics can be further subdivided into
thermoplastics (polyethene, polyvinyl chloride, teflon), thermosets (bakelite, melamine,
vulcanized rubber) and elastomers (natural rubber, silicones, styrene-butadiene rubber) based
on the response to heat. They can be classified into linear, branched, cross-linked (based on
molecular structure), natural, semisynthetic, synthetic (based on origin), addition and
condensation (based on the method of formation), plastics, elastomers, fibers and resins
(based on applications). Ceramic materials can be categorized into glasses, clay products,
refractories (acid, neutral, basic) abrasive materials, cement and advanced ceramics by an
application. Composites are classified according to the matrix material into ceramic, metal,
and polymer matrix materials, and based on reinforcement geometry into particulate-
reinforced, fiber-reinforced and structural composites. Liquid crystalline materials can be
subcategorized into calamitic, discotic, polycatenar, and bent-core types based on the shapes,
and thermotropic and lyotropic liquid crystals based on the response to temperature or
concentration. The classification of smart materials includes piezoelectric, electrostrictive,
magnetostrictive, thermoelectric, shape memory alloys, photochromic and thermochromic
materials. The classification of biomaterials based on the materials used include polymeric,
metallic, ceramic and composite categories. Nanomaterials could be of natural or synthetic
based on origin and zero, one, two and three-dimensional based on dimension. Electronic
materials are classified into conductors, superconductors, semiconductors, and dielectrics.
Based on their behavior in an applied field, superconductors are classified into two types;
Type-I – soft and Type-II -hard. There are nine classes of hazardous materials; explosives,
flammable gases, combustible liquids, flammable solids, oxidizers, toxic, radioactive,
corrosive and miscellaneous materials.

The research and development of various kinds of materials have been exponential,
and in the future, these types of materials will be used more extensively to meet the needs of

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the society. Material design is of vital importance in the development of different functional
engineering systems, and it depends on multiple factors, including certain microscopic
structural features, texture, sizes, shapes, and density. Understanding how structural patterns
are controlled and how that affects the properties gives engineers greater insight into the
preparation of materials with predetermined properties. The materials have conveniently been
grouped into various classes, and a combination of these materials will give a variety of other
new materials. Apart from the standard categories of materials, future materials include smart
materials, nanomaterials and advanced materials for specialized applications. There is a need
for well-planned effort to synthesize and explore materials with unique property and use. This
overview of the topic should make us think about the identity, composition, structure of
materials in question and study the structure-property relationships, mechanism of change
and its control, and finally the question about benefits, costs, and risks involved. We also
have to take into consideration the ecological properties related to the impact they have on
the environment and the function of biological systems can be exploited to find meaningful
solutions to engineering problems. The qualities of successful material design include
material quality, desired characteristics, ease of use, precision, attractiveness, cost of
manufacture, development cost, development time, and enhanced development capacity. A
multi-step investigation by researchers, exploration of eco-friendly approaches, preparation
of semi-synthetic materials, and preference to use of local materials would go a long way in
promoting sustainable and responsible discovery of novel materials and the development of
new technological methods. We can achieve success in offering world-class materials
through our expertise and experience by doing exceptional and result-oriented, hard work
involving systematic and target-based planning with predictable outcomes. The quality of
materials and their performance in processes and systems is probably the surest guide to the
quality of research in materials science and engineering. These multiple perspectives might
help the right-thinking people ask the right questions on the topic and to create future ideas,
innovations and stable, sustainable, smart and high-quality materials that power the world
through the scientific transformation and paves the way for severe developmental changes.

Effect of Bonding on Properties

The two important contributing factors to the properties of materials are the atomic
structure and the nature of bonding. The properties of solids depend both on the arrangements
of particles and on the attractive forces between them. A chemical bond is defined as a force
that acts between two or more atoms to hold them together in a stable arrangement. Bonding

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in materials could involve strong interactions such as ionic, covalent and metallic bonds and
weak interactions like van der Waals forces and hydrogen bond. Solids can be classified
according to the nature of the bonding between their atomic or molecular components into
ionic solids, covalent network solids, molecular solids and metallic solids. Typical examples
of these classes have distinctive electron distributions and binding energies, and
thermodynamic, electronic, and mechanical properties. We have to note that this is not a rigid
classification scheme and bonding in solids can be of mixed or intermediate kinds.
Ionic bond: A net electrostatic attraction between the positive (cation) and negative (anion)
ions formed by transfer of electrons from metal to a non-metal atom constitutes an ionic bond
(electrovalent bond). There are no rigid, directional bonds in an ionic material and the strong
ionic bonding continues throughout the solid crystal resulting in giant structure. Some
examples of ionic compounds include MgCl2, CaO, ZnS, Al2O3. The characteristic properties
of ionic compounds are the following; They are solids at room temperature. The crystals of
ionic solids are hard and brittle. They possess high melting and boiling points. They do not
conduct electricity in the solid state but are good conductors of electricity in the molten state
or aqueous solution. They are soluble in polar solvents, but insoluble in nonpolar solvents.
They do not exhibit isomerism. More common structures are the Rock salt structure which
has a face-centered cubic (f.c.c.) unit cell and the Cesium chloride structure, which has a
body-centered cubic (b.c.c.) unit cell. Less common structures include the Zincblende
structure, Wurtzite, Fluorite, and Rutile structures. An ionic solid consist of cation and anions
arranged in such a way that each ion is surrounded by as many nearest neighbors of opposite
charge as possible and there is local neutralization of charge. There could be partial ionic
character in predominantly ionic bonds in compounds with large anions, small cations, high
charge on one of either ion, and non-noble gas electron configuration of the cation.

Covalent bond: Covalent bonds are formed by an overlap of atomic orbitals and mutual
sharing of electrons. A covalent bond is typically formed by two non-metals having similar
electronegativities and each bonded atom may contribute one electron to the shared electron
pair or one atom may contribute both electrons. Covalently bonded compounds usually form
molecular structures. Molecular solids are collections of distinct molecules held together by
intermolecular forces such as dispersion forces, dipole-dipole forces, and hydrogen bonds.
Typical examples of covalent molecular crystals include the noble gases, oxygen, nitrogen,
the halogens, CO2, H2O, C12H22O11, I2, and the vast majority of organic compounds.
Depending on the number of shared electrons covalent bonds can be single (F 2), double (O2)

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or triple bond (N2) types. The common spatial arrangements of atoms in covalent molecular
solids include linear, angular, trigonal plane, trigonal pyramid, tetrahedron, square plane and
octahedral structures. A covalent network solid has atoms at the crystal lattice sites that are
linked together by covalent bonds into a three-dimensional array, e.g. C (diamond), SiO 2
(quartz). These solids are hard and high melting. Silica is the most abundant covalent solid in
nature and carborundum (SiC) is the most common synthetic solids. The characteristic
properties of covalent molecular compounds are the following; they are gases, liquids or
solids at room temperature. Covalent solids are soft and easily deformed. They have low
melting and boiling points. They are soluble in organic solvents. They are rigid and
directional and can cause stereoisomerism. They do not conduct electricity in any state.
Metallic bond: The bonding which holds the metal atoms firmly together by force of
attraction between metal ions and the mobile electrons is called metallic bond. Typical
examples of metals include Na, Fe, Cu, Mg and Al. A metallic solid has metal atoms that
occupy the crystal lattice sites in hexagonal close-packed (h.c.p.), cubic-close-packed (c.c.p.)
or body-centered cubic (b.c.c.) structures. If many metal atoms are brought together, the outer
electrons of each can merge together and overlap. These valence electrons are shared by
nuclei of all the atoms that make up the solid (giant structure). These electrons have become
delocalized and hence more stable. A block of metal can be thought of as an array of positive
ions immersed in a sea of delocalized electrons. The great cohesive forces resulting from the
delocalization is responsible for the great strength noted in metals. The type of bonding found
in metals involves the manifold of closely spaced sublevels that can be regarded as a band.
Using the band theory of metals, we can explain the properties of metals. The characteristic
properties of metals include the following; they have bright metallic lustre. Metals are
malleable and ductile. They have high electrical and thermal conductivity. The melting points
vary according to the efficiency of metallic bonding and highest melting elemental metal,
tungsten melts at 3410 oC. Those elements with intermediate electronegativity, exist as solids
on the border between metallic and covalent, called metalloids. Silicon and germanium are
semiconductors, with electrical conductivities significantly lower than those of metals, but far
higher than those of true insulators like a diamond.
Intermolecular forces: To explain the properties of different materials, it is necessary to
consider several types of intermolecular forces. These bonds are weaker than the
intramolecular covalent bonds (for example, it takes only 1.2 kJ to overcome a mole of Ar-Ar
interatomic attractions but it takes 239 kJ to break a mole of Cl-Cl covalent bonds).
Intermolecular forces are much less directional than covalent bonds and they operate at

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longer range than covalent bonds. It is useful to distinguish types of forces based on their
strength, directionality, and range. It exists in the inert gases, and between molecules in
covalent molecular solids that arise from atomic or molecular dipoles. All inert gas materials
are gaseous at high temperatures as the high kinetic energy of the molecules disrupts all
possible attractions. At lower temperatures, where materials are in the liquid state, molecules
are close together and details of the intermolecular potential energy determine the properties
of materials. The physical properties of molecular solids and liquids are because of
intermolecular forces. The boiling and melting points of different substances reflect the
strengths of the intermolecular forces. The stronger the intermolecular attractive forces, the
higher is the boiling point of the liquid and the melting points of solids increase as the
strengths of the intermolecular forces increase. The types of intermolecular forces include
hydrogen-bonding forces, London dispersion forces, dipole-dipole interactions, and ion-
dipole forces. The first three types are also known as van der Waals forces and all are
electrostatic in nature.
Hydrogen bond: The electrostatic attraction between an H-atom covalently bonded to a
highly electronegative atom X such as nitrogen, oxygen or fluorine and a lone pair of
electrons on X in another molecule is called hydrogen bonding. The compounds like H 2O,
NH3, and HF have abnormally high boiling points because of hydrogen bonding. Water has a
high melting point, a high specific heat and a high heat of vaporization because of the
abnormally strong intermolecular forces between water molecules. The hydrogen-bond
attraction can occur between molecules (intermolecular) or within different parts of a single
molecule (intramolecular). The examples of intermolecular hydrogen bonding include (HF)n,
(H2O)n, (NH3)n and (CH3COOH)2. The examples of intramolecular hydrogen bonding include
o-nitrophenol, 2-nitrobenzoic acid and o-fluorophenol. Though the H-bonds are weak forces,
they are strong enough to influence physical properties such as boiling points, solubility,
viscosity, and crystal structure. The energy associated with hydrogen bonding lies in between
15 to 40 kJ/mole, and they are much weaker than ordinary chemical bonds. These bonds help
stabilize the structure of proteins and DNA in biological systems. Ice floats on the top of the
water when a lake freezes in winter because of its lower density compared to liquid water,
thereby insulating the water below and protecting most of the aquatic life. Hydrogen bonds
tend to be the strongest type of intermolecular force.
Ion-dipole forces: This type of force exists between an ion and the partial charge on the end
of a polar molecule, e.g. KBr/NaCl in water. The negative ions are attracted to the positive

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end of a dipole, and positive ions are attracted to the negative end. These are important for
solutions of ionic substances in polar solvents.
Dipole-dipole bonds: The strongest secondary bonding type exists between adjacent polar
molecules. The associated binding energies are significantly higher than for bonds involving
induced dipoles and they are weaker than ion-dipole forces. HCl, H2S, and CH3Cl are some
examples of polar molecules. For molecules of approximately equal mass and size, the
strengths of intermolecular attractions increase with increasing polarity. The positive end of
one dipole attracts the negative end of the other. There is the overall effect of net attraction
between the polar molecules because two molecules that are drawing each other spend more
time near each other than do those that are repelling each other. Generally, such attractions
are about 1 % as strong as a covalent bond. The boiling point increases as the dipole moment
increases. They are sufficiently strong to influence melting points, and molecular orientations
in solids.
Dipole-induced dipole bonds: Permanent dipole moments exist in some molecules by an
asymmetrical arrangement of positively and negatively charged regions. The polar molecules
will induce a dipole in adjacent nonpolar molecules, and a bond will form as a result of
attractive forces between the dipole and induced dipole. The magnitude of this interaction
depends on the magnitude of the dipole moment of the polar molecule and the polarizability
of the non-polar molecule. Eg. Solution of polar solutes in nonpolar solvents.
London forces: A dipole may be created or induced in an atom or molecule that is normally
electrically symmetric; that is, the overall spatial distribution of the electrons is symmetric
with respect to the positively charged nucleus. All atoms are experiencing constant
vibrational motion that can cause instantaneous and short-lived distortions of this electrical
symmetry for some of the atoms or molecules and the creation of small electric dipoles. One
of these dipoles can, in turn, produce a displacement of the electron distribution of an
adjacent molecule or atom, which induces the second one also to become a dipole that is then
weakly attracted or bonded to the first. The momentary attraction between the molecules of a
liquid caused by the instant dipole and induced dipole are called London Forces. These
attractive forces may exist between large numbers of atoms or molecules, which forces are
temporary and fluctuate with time. Liquefaction [e.g.Ar(l)] and, in some cases, the
solidification of the inert gases and other electrically neutral and symmetric molecules such
as H2, I2 (s) and Cl2 are realized because of this types of bonding. Melting and boiling
temperatures are extremely low in materials for which induced dipole bonding predominates;
of all possible intermolecular bonds, these are the weakest. Dispersion forces operate between

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all polar and non-polar molecules. Polar molecules experience dipole-dipole interactions in
addition to dispersion forces. The dispersion forces are approximately equal when the
molecules have comparable molecular weights and shapes. The strength increases with
increasing molecular weight, though molecular shape is also an important factor.
The Road Ahead
It is essential to study the effect of several environmental conditions such as heat,
radiation, carbon dioxide, oxygen, water and various pollutants in finer detail to obtain the
full picture. The study may reveal the number of critical molecules that can be exploited for
both creating new materials and functional purposes. Finally, better technology using the
finest ingredients and expert techniques to create innovative materials with practical utility
and responsible sourcing becomes critical in this age of specialized domain expertise. Long-
term stability and safety standards for new materials matters in some applications. The
microscopic details make all the difference in the material world that turn ideas, dreams and
the future into reality. Innovating in finding new ways of adding value to unique products
makes the complex systems more efficient and make a positive transformation of society.
Advanced material characterization remains a challenge because of several factors, including
structure related (molecular geometry, 2D structure, perovskite structure), bonding pertaining
(bond length, angle, strength, order), and condition/treatment-related (pressure, temperature,
radiation) factors. Regular follow up of processes is essential from three perspectives. First,
to understand if the method is working and what is the progress of material formation.
Second, it helps to modify the method or alter treatment conditions based on the
improvement. Lastly, if there are undesired events, necessary actions can be taken to prevent
those. The sophisticated techniques such as wide angle X-ray diffraction, field emission
scanning electron microscopy (FE-SEM), tensile strength tester, simultaneous TG-DTA/DSC
apparatus, and acoustic material testing with impedance tube are used for characterization of
final stable material. It remains to be seen that a multipronged approach to preparing modern
materials soon could lead to better systems to enable sustainable development and the
material progress of human beings.

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