MSE 631a IIT Kanpur

Electroceramic Materials &

Applications (MSE 631a)
2023-24, Semester II
Instructor: Dr. Shobit Omar

Venue: T112
Lecture 1
MSE 631a Course Information IIT Kanpur
Instructor In-Charge: Dr. Shobit Omar
Office: ACMS 203(E), IIT Kanpur
Phone: 7427
Email: somar@

TA 1: Mr. Kammampati Sai Kumar TA 2: Mr. Shivam Aggarwal

Email: saikumark23@iitk.ac.in Email: shivzagg20@iitk.ac.in
Phone: 8688384998 Phone: 8126688091

Lectures: M & W - 17:15 – 18:30

Venue: T112
Credits: 9 credits

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Marks Distribution IIT Kanpur
• Quiz (3): 30%
• Mid-Semester: 30%
• End-Semester: 40%
• Attendance: 5% Bonus Marks

Grading Policy
• For passing the course:
• Minimum 30% in overall course
• Examination Policy:
• Academic dishonesty of any kind would not be tolerated and would be dealt
with severely (for the one who copies as well as for the one who promotes).
Any kind of copying or cheating would draw an F-grade immediately.
• Make-up for mid-sem and end-sem exams would be allowed only on health
grounds. (no make-up for participating in cultural/ technical programs).

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Objectives of the Course IIT Kanpur
• The course intend to give an understanding of the physics and
chemistry behind the electrical characteristics of ceramic
materials.
• To discuss the fundamental electrical phenomena existing in the
wide array of ceramics:
➢ Electronic Conducting Ceramics
➢ Ionic Conducting Ceramics
Brief description
➢ Dielectric Ceramics about their
➢ Ferroelectric applications
➢ Piezoelectric
➢ Thermoelectric
➢ Magnetic Ferrites

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Lecture Schedule IIT Kanpur
Sl.No. TOPICS Number of
Lectures
Structures of common Introduction, FCC packed structures (MgO, CeO2 etc), HCP packed structures 2
electroceramic oxides (LiNbO3 etc), Other structures such as Perovskite (BaTiO3 etc) and Rutile
structures
Introduction to Defects Defects in Elemental Solids and Ionic Compounds, Defect Classes, Point
and Defects, Kröger-Vink Notation, Point Defect Formation & Equilibrium, Law 7
Thermodynamics of Mass-Action and electrical neutrality, Thermodynamics of Intrinsic Defects
and Defect Reactions.
Defect Complexes and Complexes Containing an Impurity Center and an Ionic Defect, Intrinsic Ionic
Associates Defect Associates and Effect of Impurities on the Concentration of Defect
Complexes and Associate.
Defect Equilibria and Defect Equilibria in Pure and Stoichiometric Compounds with Schottky
Brouwer Diagrams Defects, Frenkel Defect Pairs and Intrinsic Ionization of Electrons, Defect
Equilibria in Non-stoichiometric Oxides (Cases of oxygen and metal
deficiency, oxygen and metal excess), Brouwer Diagrams for selected
materials such as YSZ, Undoped and Doped CeO2, TiO2 and BaTiO3.
Ionic and Electronic Basic Concepts of Diffusion, Tracer Diffusion, Self Diffusion, Chemical
Transport Diffusion, Ambipolar Diffusion, Ionic Conduction in Crystalline Solid,
Intrinsic and Extrinsic Ionic Conduction, Transference Number, Nernst-
Einstein Relationship, and Conductivity-Diffusion Relationship, Polaron
4
theory, metal-ceramic interfaces and electronic transport into and through a
dielectric material, Conduction mechanism in terms of Mott insulators,
Mid-Sem semiconductors, Measurement techniques, Examples of ionic transport, in
Exam important applications

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Lecture Schedule IIT Kanpur
Sl.No. TOPICS Number of
Lectures
Theory of Linear Basics of dielectrics, Clausius-Mossotti Relationship, Polarization mechanisms
Dielectrics (Electronic, atomic dipole, space charge polarization) and estimation of
polarizabilities:, Frequency Dependence of permittivity and dielectric Loss,
5
Intrinsic and extrinsic contributions to polarization, Relaxation phenomena:
Debye equations, Cole-Cole plots, Impedance spectroscopy, Dielectric
breakdown and degradation
Non-linear dielectrics Polar and nonpolar ceramics: Crystal structure and Noncentrosymetricity,
Tensor representation of properties, Piezoelectrics, Pyroelectrics, Ferroelectrics,
Antiferroelectrics, Relaxors Phenomenological theory (phase transitions) and 4
soft mode theory, domain switching and domain-dynamics., Measurement
methods, Applications
Thermoelectric Oxides See-back and Peltier effect, materials and applications 1
Magnetic Ferrites Ferrites structure and properties and their applications 1
Multiferroics and Principles, Classification, Magnetoelectric Coupling, Materials, Issues and
1
Magnetoelectrics Possible Applications
End-Sem Superconductors Basic theory, Oxide superconductors such as YBCO, Applications 1
Exam Total 26

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Suggested Reading IIT Kanpur

• A.J. Moulson & J. M. Herbert, “Electroceramics: Materials,

Properties, Applications”, Publisher : Wiley
• D. M. Smyth, “The Defect Chemistry of Metal Oxides”, Publisher:
Oxford University Press, ISBN10: 0195110145
• M. W. Barsoum, “Fundamentals of Ceramics”, Publisher:
Institute of Physics
• Introduction to Ceramics by W.D. Kingery, Wiley
• Y.M. Chiang, Dunbar P. Birnie & W.D Kingery, “Physical Ceramics-
Principles for Ceramic Science and Engineering”, Publisher: John
Wiley & Sons

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Ceramic Materials IIT Kanpur
• Ceramics are usually associated with “mixed” bonding – a
combination of ionic, covalent, and sometimes metallic.
• According to Kingery, ceramic is a nonmetallic, inorganic solid.
Thus, all inorganic semiconductors, such as SiC, GaN, Si, etc., are
ceramics.
• Glass is a “supercooled liquid”, but it is a ceramic.
• Difficult to define ceramic based on properties.
➢ They are brittle but we found superplasticity in Si3N4 and SiC
➢ They are mainly electrical insulators, but YBCO ceramic is a
superconductor @ 90 K.
➢ They are mainly poor conductor of heat, but diamond has the
highest thermal conductivity.

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Common Properties of IIT Kanpur
Ceramics
• Brittleness- contain mixed ionic-covalent bonding that
holds the constituent atoms together
• Poor Electrical Conductivity – do not have free delocalized
electrons available for conduction
• Compressive Strength – stronger in compression than in
tension
• Chemical insensitivity – they have a high melting point and
are resistant to many corrosive chemicals
• Poor Thermal Conductivity - do not have free delocalized
electrons available for conduction
• Transparent Nature – show poor electrical conductivity so
the scattering of electrons do not occur.
MSE 631A 8th January 2024 Venue-T112 Lecture 1
MSE 631a Crystalline Materials IIT Kanpur
Crystal = Lattice + Motif
Lattice: An infinite array of points in space such that every point has identical surroundings.
Two Important Properties of Lattices:
• Lattices are infinite
• Lattice have translational symmetry

Translationally periodic arrangement of points in space is called a lattice

Motif or Basis: An entity (typically an atom or a group of atoms) associated with
each lattice point
Lattice ➢ how to repeat
Motif ➢ what to repeat
Lattice Crystal
Translationally periodic Translationally periodic
arrangement of points arrangement of motifs
MSE 631a Lattices & Crystal Systems IIT Kanpur
• Bravais Lattices → 14 different ways to arrange
lattice points
• Crystal Systems → 7 unique shapes that can be used
to fill 3-dimensional space.

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Bravais Lattice in 2D IIT Kanpur

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Crystal Systems in Materials IIT Kanpur

Simple Centered

Shape of a crystal is defined by a, b, c, α, β and γ

Question: Why do we not have base centered tetragonal?

MSE 631A 8th January 2024 Venue-T112 Lecture 1
MSE 631a Grains and Grain Boundaries IIT Kanpur
In ideal case, unit cell repeats itself infinitely in all he directions

Grain Boundary Phase Boundary

Surface

Boundary with grain Boundary with

Boundary with air
having same chemical grain having
composition and structure different chemical
composition

www.doitpoms.ac.uk www.doitpoms.ac.uk
www.doitpoms.ac.uk
MSE 631A 8th January 2024 Venue-T112 Lecture 1
MSE 631a Interstitial Sites IIT Kanpur

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Perfect Crystal IIT Kanpur
Structure of Metal
Face Centered Cubic Crystal Structure

Number of atoms = 4
Co-ordination number = 12
Number of Octahedral Sites = 4
Atomic packing factor = 0.74
Number of Tetrahedral Sites = 8

MSE 631A 8th January 2024 Venue-T112 Lecture 1

 Perfect Crystal
MSE 631a IIT Kanpur
Structure of Metal
Body Centered Cubic Crystal Structure

Number of atoms = 2
Co-ordination number = 8
Number of Octahedral Sites = 3
Atomic packing factor = 0.68

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Effect of Phase Transformation IIT Kanpur
Change in volume of Fe on heating

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Perfect Crystal IIT Kanpur
Structure of Metal
Number of atoms = 6
Co-ordination number = 12
Number of Tetrahedral Sites = 12
Atomic packing factor = 0.74
Number of Octahedral Sites = 6

x x x

Tetrahedral
sites x
x
x x x

Hexagonal Closed Packed Crystal Structure x x

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Homework Assignment IIT Kanpur
Question 1: Identify octahedral and tetrahedral sites
in hexagonal closed-packed crystal structures.

Question 2: What is the size of octahedral hole in

terms of the radius of a hard sphere atom?

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Question IIT Kanpur
Question 1: Identify octahedral and tetrahedral sites in hexagonal
closed packed crystal structure
# Tetrahedral sites = 2 +2 +2 +2 +2 +2 =12

x x x
Tetrahedral
voids x x
x x x
x x

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Question IIT Kanpur
Identify octahedral sites in hexagonal closed packed crystal structure

Number of octahedral sites =

1x3 +1 x3=6

MSE 631A 8th January 2024 Venue-T112 Lecture 1

 Stability of Ionic Crystal
MSE 631a IIT Kanpur
Structures
Why ionic crystal structure is preferred over the same number
of isolated molecules?

Energetic Stability?

A+ B-

The interaction energy of a pair of anion and cation consists of

two terms: electrostatic attractive energy and repulsion energy

Constant
Z M Z X e2 B
E=− + n Born Exponent

4 o r r

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Potential Energy Curve IIT Kanpur

Coloumbic Repulsive
Interaction Interaction

Z M Z X e2 B
E=− + n
4 o r r
MSE 631A 8th January 2024 Venue-T112 Lecture 1
MSE 631a Madelung Constant IIT Kanpur
Madelung constant is defined as the ratio of the electrostatic
interaction energy of an ion pair in a crystal to the electrostatic
interaction energy of an isolated pair at the same separation.

Electrostatic Z M Z X e2 Interaction energy

Interaction energy Ecol = −  of an isolated pair
of an ion pair in a 4 o r MX
crystal
Zi Z j
A = − Rij = rij r
i Z i Z j rij

If A (Madelung constant) > 1 then crystal is energetically stable

MSE 631A 8th January 2024 Venue-T112 Lecture 1

MSE 631a Madelung Constant IIT Kanpur
Linear array of ions in AB type compound
Reference ion

A+ B- A+ B- A+ B- A+ B- A+

Zi Z j
A = −
i Z i Z j rij
A = 2  [1 − 1 / 2 + 1 / 3 − 1 / 4...]
2 3 4
x x x
ln(1 + x) = x − + − + ...
2 3 4
A = 2 ln 2
MSE 631A 8th January 2024 Venue-T112 Lecture 1
MSE 631a Madelung Constant IIT Kanpur
Madelung constant in NaCl structure

Rij = rij r
3r

r
2r

A = −(6 / 2)(−1) / 1 − (12 / 4)(1) / 2 − (8 / 8)(−1) / 3

= 1.456
Doubling the cell edge,

A = 1.75
MSE 631A 8th January 2024 Venue-T112 Lecture 1
 Stability of Ionic Crystal
MSE 631a IIT Kanpur
Structures
Structure Co-ordination Madelung Constant
number

NaCl 6:6 1.747

CsCl 8:8 1.763 When the energy

difference between
Zinc Blende 4:4 1.638
two structures of
the same
Wurtzite 4:4 1.641
compound then
Fluorite 8:4 2.519 polymorphism
occurs
Rutile 6:3 2.408

MSE 631A 8th January 2024 Venue-T112 Lecture 1