MATERIAL SCIENCE AND ENGINEERING

Course No. : CHE F243

Instructor-in-charge : Nandini Bhandaru
Instructors : Karthik Chethan V., Nandini Bhandaru

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Scope and Objective of the Course:

 Introduce the fundamentals of materials science to Chemical Engineering undergraduate

students.
 Basic understanding of the structure (crystalline and amorphous) and properties (thermal,
mechanical and electrical) of different types of materials such as metals, ceramics and
polymers.
 How the type of bonding, crystal structure, formation of structure (defects, diffusion, phase
diagrams and phase transformation) and dynamics influence the properties of these
materials.

Learning Outcomes:

 Familiarity with materials and bonding, structure-property correlation, materials

characterization and materials processing that is commonly encountered in chemical,
ceramic, metallurgical, mining, pharmaceutical, food and biotechnology industries.

 Students should attempt to hypothesize and propose to solve materials based issues in a
confident and feasible manner by combining conceptual, numerical and design based
solutions learnt during the course of the semester. The issues can be research, product
development, process, quality control and application related.

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 The students should have learnt the skill of coupling micro and macro aspects of
materials, to combine materials structure-characterization-property and to apply
interdisciplinary skills of science and engineering in problem-solving.

 Finally, the students should be comfortable and skillful in handling real-world projects
that they would encounter in their future endeavors of practice school, placements and
higher education.

Text Book:
T1. MATERIALS SCIENCE AND ENGINEERING-AN INTRODUCTION by
WILLIAM D. CALLISTER, JR. Seventh Edition, John Wiley (2007)

Reference Books:
R1. MATERIAL SCIENCE AND ENGINEERING by V. RAGHAVAN, Fifth Edition,
Prentice-Hall of India private Limited (2004)

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Course Plan:
Lect. No. Learning Objectives Topics to be covered Ref. Chap./ Sec.Book)
1 Introduction Classification of Materials Ch. 2 (TB)
2 Bonding in materials Bonding forces & Energies, Primary and Secondary bonds Ch. 2 (TB)
3-5 Crystallography Unit cell, Crystallographic directions and planes, Crystalline Ch. 3 (TB)
and Noncrystalline materials
6-8 Metallic structures FCC, BCC, Linear and planar densities, close-packed crystal Ch. 4 (TB)
structures
9 Ceramic structures Crystal structures of ceramics Ch. 4 (TB)
10-11 Polymer structures Molecular weight, Molecular configurations of polymers, Ch. 4 and 13 (TB)
and Polymer crystallinity
12-13 X-ray diffraction Determination of crystal structure, Bragg’s Law, Diffraction Ch. 4 (TB)
technique
14-16 Defects and Dislocations Vacancies and interstitials, dislocations and grain boundaries Ch. 5 (TB)

17-19 Diffusion Diffusion mechanisms Ch. 6 (TB)

20-23 Phase diagrams Phases, Microstructure, Phase equilibrium, Iron-Carbon Ch. 7 (TB)
system, Development of microstructure in Fe-C alloys
24-26 Phase Transformations Avrami rate equations, Isothermal transformation, Ch. 8 (TB)
Continuous cooling transformation diagrams
27-29 Mechanical Properties of materials and Stress-Strain, Elastic and plastic deformations, Mechanical Ch. 9 (TB)
characterization properties and behavior of Fe-C alloys.
30-31 Deformation mechanisms Fractography, Slip systems, plastic deformation, Ch. 10 (TB)
strengthening mechanisms, Viscoelastic deformation,
fracture behavior in metals, ceramics and polymers
32-34 Thermal properties of materials and Glass Transition, Crystallization and Melting Phenomenon, Ch. 19 (TB)
characterization calorimetry, thermal conductivity
35-37 Electrical Properties of Materials and Electrical characteristics of Metals, Ceramics and Polymers, Ch. 17 (TB)
characterization dielectric spectroscopy, piezoelectrics
38-39 Magnetic Properties of materials and Diamagnetism, Paramagnetism, Ferromagnetism, Hysterisis, Ch. 18 (TB)
characterization Superconductivity
40-42 Composite materials Fibre phase, Matrix phase, PMC (polymer matrix composite, Ch. 15 (TB)
interfaces and characterization

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Evaluation Scheme:

Component Duration Weightage Date & Time Remarks

Quiz (min 4) TBA 20 % Open book
Assignments & TBA 20% Open book
Presentations
(min 3)
Mid-Term Exam 90 min 20 % Closed book
Comprehensive 3 hours 40 % Open book
Exam.

Chamber Consultation Hour: Tuesday, Thursday 3 PM to 5 PM

Email: nandini@hyderabad.bits-pilani.ac.in,

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INTRODUCTION
Materials – Investigating materials and relationships that exist between the
structure and properties of materials (chemistry and physics).

• Historical Perspective
Stone Age (2.5 million BC), Bronze Age, Iron Age, Materials Age
• Stone, wood, clay, animal skin- Most natural materials without processing
• METALS- Bronze, Iron;
• Processing-Heat treatment, alloying, blending

• Current and Future Materials

Electronic materials, superconductors, etc.
Biodegradable materials, Nanomaterials, “Smart” materials

 What materials are present in your cell phones?

 What are the current problems in the world and can material
engineers help solve them?
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(Based primarily on chemical makeup and atomic structure)

METALS AND ALLOYS POLYMERS CERAMICS AND GLASSES

• Good conductors of electricity • Very large molecules • Thermally and electrically
and heat • Low density, low weight insulating
• Relatively high density • Maybe extremely flexible, • Resistant to high
• Lustrous appearance ductile temperatures and harsh
• Susceptible to corrosion • Low electrical conductivity environments
• Strong, but deformable and non magnetic • Hard, but brittle
• Magnetic properties • PE, Nylon, PS, PC • Al2O3, SiO2, Cement,
• Fe, Al, Mg, Ti, Ni, Zn, Cu Glass

COMPOSITES
• Consist of more than one material type
• Designed to display a combination of
properties of each component
SEMICONDUCTORS
TYPES OF MATERIALS • Electrical properties between
conductors and insulators
• Electrical properties can be
precisely controlled

NANO ENGINEERED
BIOMATERAILS MATERAILS SMART MATERAILS
• Implanted in human body
• Compatible with body tissues Memory spring: Alloy of
Brass, Nitinol
Metamaterials
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PROPERTIES

Density Elastic Modulus

Tensile Strength Electrical Conductivity

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Figures from Chapter 1, T1
EXAMPLE
Polycrystalline Polycrystalline
& porous Three thin disk specimens of aluminum oxide
that have been placed over a printed page in
order to demonstrate their differences in light-
transmittance characteristics. These differences
in optical properties are a consequence of
differences in structure of these materials, which
have resulted from the way the materials were
Single processed.
Crystal
Al2O3 Figure 1.2, T1

Glass-Amorphous material Single Crystal

Polycrystalline material
Amorphous material

Why is Glass Transparent?

Particle size, crystal structure, band

gap and void space
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Example: Glass vs Quartz vs Silicon Particle size, crystal structure, band
Comparison of optical properties gap and void space

• A photon will be absorbed by a transparent material if it has enough energy

to promote an electron from the valence band to the conduction band. The
difference in these energy levels is known as the band gap.

• The band gap of quartz depends on the crystal structure, but is around 6 eV,
which corresponds to photons well into the ultraviolet, with a maximum
wavelength of 180 nm.

• The band gap of glass depends on the glass composition, but is generally
around 3-4 eV, and so the maximum wavelength of absorption is around
275–350 nm.

• Silicon, incidentally, has a band gap of 1.1 eV, which corresponds to a

wavelength of 1100 nm. So silicon is opaque in the visible range, but
transparent to infrared light of longer than 1100 nm wavelength. Because of
this, silicon is often used to make infrared lenses.
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Materials Science and Engineering

Scale and Structure:

 Sub atomic structure
< 0.2 nm

 Arrangement of atoms
0.2-10 nm The materials paradigm.
Wikipedia, © PD

TEM image: AFM image:

 Nano scale structure Au Nano Thin Polymer
1-100 nm particles blends

OM image: AFM image:

 Micro scale structure Pepide fibers Commercial CD ROM
1-1000 mm

 Macroscale structure: Bulk

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Structural Colour Diffraction Anti-reflection
Materials Engineering
• Engineering – on the basis of structure-property correlations
• Pick Application: Determine required Properties
• Properties: Identify candidate Material(s)
• Material: structure, composition. Identify required Processing
• Processing: changes structure and overall shape ex: casting,
sintering, vapor deposition, doping, forming, joining, annealing.

Properties
Mechanical: strength, fracture resistance etc.
Electrical and magnetic: response to magnetic fields.
Thermal: Transmission of heat, heat capacity.
Optical: absorption, transmission and scattering of light.
Chemical stability: corrosion resistance etc.
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Equilibrium and Kinetics

 Stability and Metastability

 Basic Thermodynamics: Gibbs free energy,
Configurational entropy
 Kinetics of a Thermally Activated Process
Maxwell-Boltzmann distribution

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Atomic Structure and Bonding
Subatomic particles: Protons and Neutrons (nucleus) + Electrons

Charges:
Both electrons and protons are electrically charged, the charge magnitude being
1.602 X 10-19 Coulombs
Masses:
Extremely small; protons and neutrons have the same mass, 1.67 X 10-27 kg, which is
significantly larger than that of an electron, 9.11 X 10-31 kg.

Basic Concepts: Atomic number, Atomic mass, isotopes, Atomic weight,

Atomic Mass Unit,

Periodic table of the elements

indicating atomic number and
atomic weights

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Electronic Structure
 Electrons have wavelike and particulate properties.
Bohr atomic model:
 The energies of electrons are quantized.
 Describe electrons in atoms, in terms of both position
(electron orbitals) and energy (quantized energy levels). Bohr atomic model:

Wave Mechanical Model:

 Electrons are in orbitals defined by a probability.
An electron is no longer treated as a particle moving in a
discrete orbital; rather, position is considered to be the
probability of an electron’s being at various locations
around the nucleus. (Electron cloud)

 Every electron in an atom is characterized by four

parameters called quantum numbers
Electron distribution
in an atom
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Quantum Numbers
Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subshells (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

 Principal quantum number, n:

 Associated with the Bohr model. (Size and Energy)
 Related to the size of an electron’s orbital (or its average distance from the nucleus).

 Second (or azimuthal) quantum number, l:

describes shape of electronic subshell.

 Third (or magnetic) quantum number, ml :

• Number of energy states for each subshell
(describes orientation).

 Spin quantum number describes the spin states (clockwise or anti-clockwise).

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Electron Energy States
Electrons... • have discrete energy states
• tend to occupy lowest available energy state.

4f
4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
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Electron Configurations
Pauli exclusion principle
No two electrons can have the same four electronic quantum numbers.

 Valence electrons – those in unfilled shells

 Filled shells more stable
 Valence electrons are most available for bonding and tend to
control the chemical properties

• Ionization potential and Electronegativity 18

Atomic Bonding in Solids Bond Energy

Attractive force FA depends on the

particular type of bonding that exists
between the two atoms.

Repulsive forces FR arise from

interactions between the negatively
charged electron clouds.

Potential energy, E = ‫𝐫𝐝 𝑭 ׬‬

At the equilibrium separation

distance, the attractive and repulsive
forces just balance.

At this point the potential energy is a

minimum. The slope is zero (F=0).

Equilibrium E0 is the bond energy and r0 is the

length of a bond.
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Bond Energy
• The bond energy E0 corresponds to the energy at this minimum point and
it represents the energy required to separate these two atoms to an
infinite separation. (Units: eV per bond, kJ/mol)

• The force between atoms is repulsive at very small separation distances.

This repulsion is partially electrostatic and partially due to the exclusion
principle.

• Due to the exclusion principle, some electrons in overlapping shells are

forced into higher energy states. The energy of the system increases as if
a repulsive force existed between the atoms.

• The force between the atoms is attractive at larger distances (e.g. due to
shifted more uniform charge distribution, induced dipole-dipole
interaction)

• The magnitude of the attractive part, dominating at large distances,

depends on the particular type of bonding (depth and shape of the curve,
bond lengths and unit cells). 20
Bond Energy Material Properties

• Materials having large bonding energies

typically also have high melting
temperatures

• The mechanical stiffness (or modulus of

elasticity) of a material is dependent on
the shape of its force–versus–
interatomic separation curve. The slope
for a relatively stiff material at r0 position
on the curve will be quite steep

• How much a material expands upon heating or

contracts upon cooling (i.e., its linear coefficient of
thermal expansion) is related to the shape of its E–
versus–r curve. A deep and narrow “trough,”
normally correlates with a low coefficient of thermal
expansion and relatively small dimensional
alterations for changes in temperature. 21
• Properties From Bonding: Tm

• Bond length, r • Melting Temperature, Tm

Energy
r

• Bond energy, Eo ro
r
Energy

unstretched length
ro
r
Eo = Tm is larger if Eo is larger.
“bond energy”
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 The potential energy for interaction between two
atoms can be expressed as

𝐴 𝐵
𝐸 𝑟 =− 𝑛+ 𝑚
𝑟 𝑟

• Where r is the intermolecular separation distance

• m and n are integers (usually)
• A is associated with the attractive force
• B is associated with the repulsive force

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Q) The net potential energy between two adjacent ions,
EN, may be represented by,

EN = EA (attractive potential) + ER (repulsive

potential)

EN = - A/r + B/rn

Calculate the bonding energy EO in terms of parameters

A, B and n.

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 Types of Bonding
• The electronic structure of atoms defines the character of
their interaction among each other.

• Filled outer shells result in a stable configuration as in noble

inert gases. Atoms with incomplete outer shells strive to
reach this noble gas configuration by sharing or transferring
electrons among each other for maximal stability.

• Strong primary bonding results from the electron sharing or

transfer.

• Weaker secondary bonds result from a more subtle

attraction between positive and negative charges with no
actual transfer or sharing of electrons.
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PRIMARY INTERATOMIC BONDS
• Primary bonding: electrons are transferred or shared
• Strong (100-1000 KJ/mol or 1-10 eV/bond)
• Ionic: Strong Coulomb interaction among negative
atoms (have an extra electron each) and positive atoms
(lost an electron). Example: Na+Cl-
• Covalent: Electrons are shared between neighboring
atoms, to saturate the valency. Example: Cl2
• Metallic: Atoms are ionized, loosing some electrons
from the valence band. Those electrons form a
electron sea, which binds the charged nuclei in place.

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Ionic Bonding
• Bond between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable stable
Coulombic
Attraction
 Atoms of a metallic element easily give up their valence electrons to the
nonmetallic atoms. In the process, all the atoms acquire stable or inert gas
configurations (i.e., completely filled orbital shells) and, in addition, an electrical
charge—that is, they become ions. 27
• Bond Energy: Ionic Bonding

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Example of NaCl in details:

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Example of NaCl in details:
• A strong electrostatic attraction between positively
charged Na+ ions and negatively charged Cl- atoms
along with Na+ - Na+ and Cl- - Cl- repulsion result in the
NaCl crystal structure which is arranged so that each
sodium ion is surrounded by Cl- ions and each Na+ ion is
surrounded by Cl- ions.

• Electroneutrality is important.

• Any mechanical force that tries to disturb the electrical

balance in an ionic crystal meets strong resistance: ionic
materials are strong and brittle. In some special cases,
however, significant plastic deformation can be
observed, e.g. NaCl single crystals can be bent by hand
in water.
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Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
H
C: has 4 valence e-, CH 4
from carbon atom
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

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Covalent Bonding
• In covalent bonding, electrons are shared between the atoms. In this case
the electrons are not transferred as in the ionic bonding, but they are
localized between the neighboring ions and form directional bond
between them. The ions repel each other, but are attracted to the
electrons that spend most of the time in between the ions.

Formation of covalent bonds:

• Cooperative sharing of valence electrons
• Can be described by orbital overlap
• Covalent bonds are HIGHLY directional (sharing)
• Bonds - in the direction of the greatest orbital overlap (electron density is
highest)
• Covalent bond model: an atom can covalently bond with at most 8-
number of valence electrons

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Schematic

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Metallic Bonding
• Delocalized electrons.
• Non directional.
• Free electrons: good conductors of both electricity and heat.
• Example: Cu, Al, Au, Ag, etc.

• Valence electrons are detached from atoms, and

spread in an 'electron sea' that "glues" the positive
ions together.
• Atoms pack closely. The “bonds” do not “break” when
atoms are rearranged – metals can experience a
significant degree of plastic deformation.
• Transition metals (Fe, Ni, etc.) form mixed bonds that
are comprising of metallic bonds and covalent bonds
involving their 3d-electrons. As a result the transition
metals are more brittle (less ductile) that Au or Cu.
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Metallic Bonding

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Secondary Bonding

• Secondary Bonding: no e- transferred or shared

• Interaction of atomic/molecular dipoles
• Weak (< 100 KJ/mol or < 1 eV/atom)
• Fluctuating Induced Dipole
• Permanent dipole bonds (polar molecules - H2O, HCl...)
• Polar molecule-induced dipole bonds (a polar molecule
induces a dipole in a nearby nonpolar atom/molecule)
• Dipole-dipole
• Dipole-ion

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Lennard-Jones potential Curve (also termed the 6-12 potential)
• For interaction between two instantaneous dipoles

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Secondary Bonding

• Dispersion force (attractive force between two

nonpolar molecules). The dispersion force is a
temporary attractive force that results when the
electrons in two adjacent atoms occupy positions that
make the atoms form temporary dipoles. Dispersion
forces are the attractive forces that cause nonpolar
substances to condense to liquids and to freeze into
solids when the temperature is lowered sufficiently.

• Hydrogen bonding (dipole-dipole)

• Weak Dipole-ion
Dispersion Force Schematic
• Hydrogen Bonding Schematic
• Hydrogen Bonding (different phases of ice/water)

Prof. Yoshinori Furukawa, Hokkaido University

Hydrogen Bonding in Biological Molecules

Protein folding

DNA
Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
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