Materials Science

As engineering materials constitute foundation of

technology, it’s not only necessary but a must to
understand how materials behave like they do and why
they differ in properties. This is only possible with the
atomistic understanding allowed by quantum mechanics
that first explained atoms and then solids starting in the
1930s. The combination of physics, chemistry, and the
focus on the relationship between the properties of a
material and its microstructure is the domain of
Materials Science. The development of this science
allowed designing materials and provided a knowledge base for the engineering applications (Materials
Engineering).
Why Study Materials Science and Engineering? and Classification of Materials? All engineers need to know about
materials. Even the most "immaterial", like software or system engineering depend on the development of new
materials, which in turn alter the economics, like software-hardware trade-offs. Increasing applications of system
engineering are in materials manufacturing (industrial engineering) and complex environmental systems.
Thus it is very important that every engineer must study and understand the concepts of Materials Science and
Engineering. This enables the engineer.
 To select a material for a given use based on considerations of cost and performance.
 To understand the limits of materials and the change of their properties with use.
 To be able to create a new material that will have some desirable properties.
 To be able to use the material for different application.
Classification of Materials
Like many other things, materials are classified in groups, so that our brain can handle the complexity. One can
classify them based on many criteria, for example crystal structure (arrangement of atoms and bonds between
them), or properties, or use.
Metals, Ceramics, Polymers, Composites, Semiconductors, and Biomaterials constitute
Metals: These materials are characterized by high thermal and electrical conductivity; strong yet deformable under
applied mechanical loads; opaque to light (shiny if polished). These characteristics are due to valence electrons
that are detached from atoms, and spread in an electron sea that glues the ions together, i.e. atoms are bound
together by metallic bonds and weaker van der Waalls forces. Pure metals are not good enough for many
applications, especially structural applications. Thus metals are used in alloy form i.e. a metal mixed with another
metal to improve the desired qualities. E.g.: aluminum, steel, brass, gold.
Ceramics: These are inorganic compounds, and usually made either of oxides, carbides, nitrides, or silicates of
metals. Ceramics are typically partly crystalline and partly amorphous. Atoms (ions often) in ceramic materials
behave mostly like either positive or negative ions, and are bound by very strong Coulomb forces between them.
These materials are characterized by very high strength under compression, low ductility; usually insulators to heat
and electricity. Examples: glass, porcelain, many minerals.
Polymers: Polymers in the form of thermo-plastics (nylon, polyethylene, polyvinyl chloride, rubber, etc.) consist of
molecules that have covalent bonding within each molecule and van der Waals forces between them. Polymers in
the form of thermo-sets (e.g., epoxy, phenolics, etc.) consist of a network of covalent bonds. They are based on H, C
and other non-metallic elements. Polymers are amorphous, except for a minority of thermoplastics. Due to the kind
of bonding, polymers are typically electrical and thermal insulators. However, conducting polymers can be
obtained by doping, and conducting polymer-matrix composites can be obtained by the use of conducting fillers.
They decompose at moderate temperatures (100 – 400 C), and are lightweight. Other properties vary greatly.
Composite materials: Composite materials are multiphase materials obtained by artificial combination of different
materials to attain properties that the individual components cannot attain. An example is a lightweight brake disc
obtained by embedding SiC particles in Al-alloy matrix. Another example is reinforced cement concrete, a structural
composite obtained by combining cement (the matrix, i.e., the binder, obtained by a reaction known as hydration,
between cement and water), sand (fine aggregate), gravel (coarse aggregate), and, thick steel fibers. However,
there are some natural composites available in nature, for example – wood. In general, composites are classified
according to their matrix materials. The main classes of composites are metal-matrix, polymer-matrix, and ceramic-
matrix.
Semiconductors: Semiconductors are covalent in nature. Their atomic structure is characterized by the highest
occupied energy band (the valence band, where the valence electrons reside energetically) full such that the energy
gap between the top of the valence band and the bottom of the empty energy band (the conduction band) is small
enough for some fraction of the valence electrons to be excited from the valence band to the conduction band by
thermal, optical, or other forms of energy. Their electrical properties depend extremely strongly on minute
proportions of contaminants. They are usually doped in order to enhance electrical conductivity. They are used in
the form of single crystals without dislocations because grain boundaries and dislocations would degrade electrical
behavior. They are opaque to visible light but transparent to the infrared. Examples: silicon (Si), germanium (Ge),
and gallium arsenide (GaAs, a compound semiconductor).
Biomaterials: These are any type material that can be used for replacement of damaged or diseased human body
parts. Primary requirement of these materials is that they must be biocompatible with body tissues, and must not
produce toxic substances. Other important material factors are: ability to support forces; low friction, wear,
density, and cost; reproducibility. Typical applications involve heart valves, hip joints, dental implants, intraocular
lenses. Examples: Stainless steel, Co-28Cr-6Mo, Ti-6Al-4V, ultra high molecular weight poly-ethelene, high purity
dense Al-oxide, etc.
Advanced Materials, Future Materials, and Modern Materials needs
Advanced Materials
These are materials used in High-Tech devices those operate based on relatively intricate and sophisticated
principles (e.g. computers, air/space-crafts, electronic gadgets, etc.). These materials are either traditional
materials with enhanced properties or newly developed materials with high performance capabilities. Hence these
are relatively expensive. Typical applications: integrated circuits, lasers, LCDs, fiber optics, thermal protection for
space shuttle, etc. Examples: Metallic foams, intermetallic compounds, multi-component alloys, magnetic alloys,
special ceramics and high temperature materials, etc.
Future Materials
Group of new and state-of-the-art materials now being developed, and expected to have significant influence on
present-day technologies, especially in the fields of medicine, manufacturing and defense. Smart/Intelligent
material system consists some type of sensor (detects an input) and an actuator (performs responsive and
adaptive function). Actuators may be called upon to change shape, position, natural frequency, mechanical
characteristics in response to changes in temperature, electric/magnetic fields, moisture, pH, etc.
Four types of materials used as actuators: Shape memory alloys, Piezo-electric ceramics, Magnetostrictive
materials, Electro-/Magneto-rheological fluids. Materials / Devices used as sensors: Optical fibers, Piezo-electric
materials, Micro-electro-mechanical systems (MEMS), etc.
Typical applications: By incorporating sensors, actuators and chip processors into system, researchers are able to
stimulate biological human-like behavior; Fibers for bridges, buildings, and wood utility poles; They also help in fast
moving and accurate robot parts, high speed helicopter rotor blades; Actuators that control chatter in precision
machine tools; Small microelectronic circuits in machines ranging from computers to photolithography prints; Health
monitoring detecting the success or failure of a product.
Modern Materials needs
Though there has been tremendous progress over the decades in the field of materials science and engineering,
innovation of new technologies, and need for better performances of existing technologies demands much more
from the materials field. Moreover it is evident that new materials/technologies are needed to be environmental
friendly. Some typical needs, thus, of modern materials needs are listed in the following:
 Engine efficiency increases at high temperatures: requires high temperature structural materials
 Use of nuclear energy requires solving problem with residues, or advances in nuclear waste processing.
 Hypersonic flight requires materials that are light, strong and resist high temperatures.
 Optical communications require optical fibers that absorb light negligibly.
 Civil construction – materials for unbreakable windows.
 Structures: materials that are strong like metals and resist corrosion like plastics.
Atomic Structure and Atomic Bonding in Solids
Atomic Model
Thomson atomic model
A schematic presentation of the plum pudding model of the
atom; in Thomson's mathematical model the "corpuscles" (or
modern electrons) were arranged non-randomly, in rotating rings
The current model of the sub-atomic structure involves a dense
nucleus surrounded by a probabilistic "cloud" of electrons.
The plum pudding model was a model of the atom that incorporated the recently discovered electron, and was
proposed by J. J. Thomson in 1904. Thomson had discovered the electron in 1897. The plum pudding model was
abandoned after discovery of the atomic nucleus. The plum pudding model of the atom is also known as the
"Blueberry Muffin" model. The 1904 Thomson model was disproved by the 1909 gold foil experiment of Hans
Geiger and Ernest Marsden. This was interpreted by Ernest Rutherford in 1911 to imply a very small nucleus of the
atom containing a very high positive charge (in the case of gold, enough to balance about 100 electrons), thus
leading to the Rutherford model of the atom.
Rutherford model
Rutherford overturned Thomson's model in 1911 with his well-known gold foil experiment in which he
demonstrated that the atom has a tiny, heavy nucleus. Rutherford designed an experiment to use the alpha
particles emitted by a radioactive element as probes to the unseen world of atomic structure. Rutherford presented
his own physical model for subatomic structure, as an interpretation for the unexpected experimental results. In it,
the atom is made up of a central charge (this is the modern atomic nucleus, though Rutherford did not use the
term "nucleus" in his paper) surrounded by a cloud of (presumably) orbiting electrons. In this May 1911 paper,
Rutherford only commits himself to a small central region of very high positive or negative charge in the atom.
Bohr model
In the early 20th century, experiments by Ernest Rutherford established that atoms consisted of a diffuse cloud of
negatively charged electrons surrounding a small, dense, positively charged nucleus. Given this experimental data,
Rutherford naturally considered a planetary-model atom, the Rutherford model of 1911 – electrons orbiting a solar
nucleus – however, said planetary- model atom has a technical difficulty. The laws of classical mechanics (i.e. the
Larmor formula), predict that the electron will release electromagnetic radiation while orbiting a nucleus. Because
the electron would lose energy, it would rapidly spiral inwards, collapsing into the nucleus on a timescale of around
16 picoseconds. This atom model is disastrous, because it predicts that all atoms are unstable.
Also, as the electron spirals inward, the emission would rapidly increase in frequency as the orbit got smaller and
faster. This would produce a continuous smear, in frequency, of electromagnetic radiation. However, late 19th
century experiments with electric discharges have shown that atoms will only emit light (that is, electromagnetic
radiation) at certain discrete frequencies.
To overcome this difficulty, Niels Bohr proposed, in 1913, what is now called the Bohr model of the atom. He
suggested that electrons could only have certain classical motions:
1. Electrons in atoms orbit the nucleus.
2. The electrons can only orbit stably, without radiating, in certain orbits (called by Bohr the "stationary orbits") at a
certain discrete set of distances from the nucleus. These orbits are associated with definite energies and are also
called energy shells or energy levels. In theseorbits, the electron's acceleration does not result in radiation and
energy loss as required by classical electromagnetics.
3. Electrons can only gain and lose energy by jumping from one allowed orbit to another, absorbing or emitting
electromagnetic radiation with a frequency ν determined by the energy difference of the levels according to the
Planck relation
where h is Planck's constant. The frequency of the radiation emitted at an orbit of period T is as it would be in
classical mechanics; it is the reciprocal of the classical orbit period:
Modern concept of atomic model (De- Broglie’s atomic model)
In 1925 a new kind of mechanics was proposed, quantum mechanics, in which Bohr's model of electrons traveling in
quantized orbits was extended into a more accurate model of electron motion. The new theory was proposed by
Werner Heisenberg. Another form of the same theory, wave mechanics, was discovered by the Austrian physicist
Erwin Schrödinger independently, and by different reasoning. Schrödinger employed de Broglie's matter waves, but
sought wave solutions of a three-dimensional wave equation describing electrons that were constrained to move
about the nucleus of a hydrogen-like atom, by being trapped by the potential of the positive nuclear charge.
The shapes of atomic orbitals can be understood qualitatively by considering the analogous case of standing
waves on a circular drum. To see the analogy, the mean vibrational displacement of each bit of drum membrane
from the equilibrium point over many cycles (a measure of average drum membrane velocity and momentum at
that point) must be considered relative to that point's distance from the center of the drum head. If this
displacement is taken as being analogous to the probability of finding an electron at a given distance from the
nucleus, then it will be seen that the many modes of the vibrating disk form patterns that trace the various shapes of
atomic orbitals. The basic reason for this correspondence lies in the fact that the distribution of kinetic energy and
momentum in a matter-wave is predictive of where the particle associated with the wave will be. That is, the
probability of finding an electron at a given place is also a function of the electron's average momentum at that
point, since high electron momentum at a given position tends to "localize" the electron in that position, via the
properties of electron wave-packets (see the Heisenberg uncertainty principle for details of the mechanism).
Atomic bonding in solids
In order to understand the why materials behave like they do and why they differ in properties, it is necessary that
one should look at atomic level. The study primarily concentrates on two issues: what made the atoms to cluster
together, and how atoms are arranged. As mentioned in earlier chapter, atoms are bound to each other by number
of bonds. These inter-atomic bonds are primarily of two kinds: Primary bonds and Secondary bonds. Ionic,
Covalent and Metallic bonds are relatively very strong, and grouped as primary bonds, whereas van der Waals and
hydrogen bonds are relatively weak, and termed as secondary bonds. Metals and Ceramics are entirely held
together by primary bonds - the ionic and covalent bonds in ceramics, and the metallic and covalent bonds in
metals. Although much weaker than primary bonds, secondary bonds are still very important. They provide the
links between polymer molecules in polyethylene (and other polymers) which make them solids. Without them,
water would boil at -80˚C, and life as we know it on earth would not exist.
Ionic Bonding:
This bond exists between two atoms when one of the atoms is negative (has an extra electron) and another is
positive (has lost an electron). Then there is a strong, direct Coulomb attraction. Basically ionic bonds are non-
directional in nature. An example is NaCl. In the molecule, there are more electrons around Cl, forming Cl- and
fewer electrons around Na, forming Na+. Ionic bonds are the strongest bonds. In real solids, ionic bonding is usually
exists along with covalent bonding.
Covalent Bonding:
In covalent bonding, electrons are shared between the atoms, to
saturate the valency. The simplest example is the H2 molecule,
where the electrons spend more time in between the nuclei of
two atoms than outside, thus producing bonding. Covalent
bonds are stereo-specific i.e. each bond is between a specific
pair of atoms, which share a pair of electrons (of opposite
magnetic pins). Typically, covalent bonds are very strong, and
directional in nature. The hardness of diamond is a result of the
fact that each carbon atom is covalently bonded with four
neighboring atoms, and each neighbor is bonded with an equal
number of atoms to form a rigid three- dimensional structure.
Metallic Bonding:
Metals are characterized by high thermal and electrical conductivities. Thus,
neither covalent nor ionic bondings are realized because both types of bonding
localize the valence electrons and preclude conduction. However, strong bonding
does occur in metals. The valence electrons of metals also are delocalized. Thus
metallic bonding can be viewed as metal containing a periodic structure of
positive ions surrounded by a sea of delocalized electrons. The attraction between
the two provides the bond, which is non-directional.

Fluctuating Induced Dipole Bonds:

Since the electrons may be on one side of the atom or the other, a dipole is
formed: the + nucleus at the center, and the electron outside. Since the electron moves, the dipole fluctuates. This
fluctuation in atom A produces a fluctuating electric field that is felt by the electrons of an adjacent atom, B. Atom B
then polarizes so that its outer electrons are on the side of the atom closest to the + side (or opposite to the – side)
of the dipole in A.
Polar Molecule-Induced Dipole Bonds:
Another type of secondary bond exists with asymmetric molecules, also called polar molecules because of
positively and negatively charged regions. A permanent dipole moment arises from net positive and negative
charges that are respectively associated with the hydrogen and chlorine ends of the HCl molecule, leading to
bonding. The magnitude of this bond will be greater than for fluctuating induced dipoles.
These two kinds of bonds are also called van der Waals bonds. Third type of secondary bond is the hydrogen bond. It
is categorized separately because it produces the strongest forces of attraction in this category.
Permanent Dipole Bonds / Hydrogen bonding: It occurs between molecules as covalently bonded hydrogen atoms –
for example C-H, O-H, F-H – share single electron with other atom essentially resulting in positively charged proton
that is not shielded any electrons. This highly positively charged end of the molecule is capable of strong attractive
force with the negative end of an adjacent molecule. The properties of water are influenced significantly by the
hydrogen bonds/bridges. The bridges are of sufficient strength, and as a consequence water has the highest melting
point of any molecule of its size. Likewise, its heat of vaporization is very high.
Crystal Structures, Crystalline and Non-Crystalline materials
Crystal structures
All metals, a major fraction of ceramics, and certain polymers acquire crystalline form when solidify, i.e. in solid state
atoms self-organize to form crystals. Crystals possess a long-range order of atomic arrangement through repeated
periodicity at regular intervals in three dimensions of space. When the solid is not crystalline, it is called amorphous.
Examples of crystalline solids are metals, diamond and other precious stones, ice, graphite. Examples of amorphous
solids are glass, amorphous carbon (a-C), amorphous Si, most plastics.
There is very large number of different crystal structures all having long-range atomic order; these vary from
relatively simple structures for metals to exceedingly complex structures for ceramics and some polymers. To
discuss crystalline structures it is useful to consider atoms as being hard spheres, with well-defined radii. In this
scheme, the shortest distance between two like atoms is one diameter. In this context, use of terms lattice and unit
cell will be handy. Lattice is used to represent a three-dimensional periodic array of points coinciding with atom
positions. Unit cell is smallest repeatable entity that can be used to completely represent a crystal structure. Thus it
can be considered that a unit cell is the building block of the crystal structure and defines the crystal structure by
virtue of its geometry and the atom positions within.
Important properties of the unit cells are
 The type of atoms and their radii R.
 Cell dimensions (Lattice spacing a, b and c)
in terms of R and
 Angle between the axis α, β, γ
 a*, b*, c* - lattice distances in reciprocal
lattice , α*, β*, γ* - angle in reciprocal lattice
 n, number of atoms per unit cell. For an atom that is shared with m adjacent unit cells,
we only count a fraction of the atom, 1/m.
 CN, the coordination number, which is the number of closest neighbors to which an
atom is bonded.
 APF, the atomic packing factor, which is the fraction of the volume of the cell actually
occupied by the hard spheres. APF = Sum of atomic volumes/Volume of cell.
Some very common crystal structures and relevant properties are listed in table below.

Crystalline and Non-crystalline materials

Single Crystals: Crystals can be single crystals where the whole solid is one crystal. Then it has a regular geometric
structure with flat faces.
Polycrystalline Materials: A solid can be composed of many crystalline grains, not aligned with each other. It is
called polycrystalline. The grains can be more or less aligned with respect to each other. Where they meet is called a
grain boundary.
Non-Crystalline Solids: In amorphous solids, there is no long-range order. But amorphous does not mean random,
since the distance between atoms cannot be smaller than the size of the hard spheres. Also, in many cases there is
some form of short-range order. For instance, the tetragonal order of crystalline SiO2 (quartz) is still apparent in
amorphous SiO2 (silica glass).