Ceramics and Glasses Lecture Dr.Nabaa S.

Radhi

The First Lecture

1- Introduction to Ceramics
In metals, the bonding is predominantly metallic, where delocalized
electrons provide the "glue" that holds the positive ion cores together.
This delocalization of the bonding electrons is responsible for properties
most associated with metals: ductility, thermal and electrical
conductivity, reflectivity, and other distinctive properties.
Polymers consist of very long, C-based chains to which other organic
atoms (for example; C, H, N, Cl, F) and molecules are attached. The
bonding within the chains is strong, directional, and covalent, while the
bonding between chains is relatively weak. Thus, the properties of
polymers as a class are dictated by the weaker bonds, and consequently
they possess lower melting points, higher thermal expansion coefficients,
and lower stiffnesses than most metals or ceramics.
Ceramic materials are inorganic, nonmetallic compounds, usually
oxides like SiO2, Al2O3 and non-oxides such as carbides, nitrides, and
borides. Both ionic and covalent bonds, or 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 Figure 1: Cross section of ceramic material.
ceramic material. The dark fields represent the pores.
Ceramics and Glasses Lecture Dr.Nabaa S. Radhi

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
compact shrinks during heating, and its bulk density 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.
Semiconductors are subgroup of ceramics; they are covalently bonded
solids that, in addition to well-known Si and Ge, include GaAs, CdTe,
and InP …etc. Other semiconductors outside the electronic materials are
SiC, TiO2, ZnO, and others.
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.
2- Elementary Crystallography
A long-range order requires that atoms be arrayed in a three
dimensional pattern that repeats. The simplest way to describe a pattern is
to describe a unit cell within that pattern. A unit cell is defined as the
smallest region in space that, when repeated, completely describes the
three-dimensional pattern of the atoms of a crystal. Geometrically, it can
be shown that there are only seven unit cell shapes, or crystal systems,
that can be stacked together to fill three-dimensional space. The seven
systems, shown in Figure 3, are cubic, tetragonal, orthorhombic,
rhombohedral, hexagonal, monoclinic, and triclinic. The various systems
are distinguished from one another by the lengths of the unit cell edges
and the angles between the edges, known as the lattice parameters or
lattice constants (a, b, c, a, α,  and γ in Figure 2).
 Ceramics and Glasses Lecture Dr.Nabaa S. Radhi

Figure 4: The Unit Cel

Figure 2: The Unit Cel

The unit cell has a number of

permutations, primitive, base
centered, body centered, and face
centered. However, symmetry
considerations limit the total Figure 3: Seven Crystal Systems and 14 Bravais Lattices

number of possible permutations to

14 Bravais lattices. See Figure 3.
3- 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.
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
Ceramics and Glasses Lecture Dr.Nabaa S. Radhi

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.
Ceramics and Glasses Lecture Dr.Nabaa S. Radhi

Some of the common applications are listed in next table:

Property Applications (examples)
1. Thermal
Insulation High-temperature furnace linings for insulation
(oxide fibers such as SiO2, A12O3, and ZrO2)
Refractoriness High-temperature furnace linings for insulation and
containment of molten metals and slags
Thermal conductivity Heat sinks for electronic packages (A1N)
2. Electrical and dielectric
Conductivity Heating elements for furnaces (SiC, ZrO2, MoSi2)
Ferroelectricity Capacitors (Ba-titanate-based materials)
Low-voltage insulators Ceramic insulation (porcelain, steatite, forsterite)
Insulators in electronic Substrates for electronic packaging and electrical
applications insulators in general (Al2O3, A1N)
Insulators in hostile environments Spark plugs (Al2O3)
Ion-conducting Sensor and fuel cells (ZrO2, A12O3, etc)
Semiconducting Thermistors and heating elements (oxides of Fe, Co,
Mn)
Nonlinear I-V characteristics Current surge protectors (Bi-doped ZnO, SiC)
Gas-sensitive conduct Gas sensors (SnO2, ZnO)
3. Magnetic and
superconductive
Hard magnets Ferrite magnets [(Ba, Sr)O6Fe2O3]
Soft magnets Transformer cores [(Zn, M)Fe2O3, with M = Mn, Co,
Mg]; magnetic tapes (rare-earth garnets)
Superconductivity Wires and SQUID magnetometers (YBa2Cu3O7)
4. Optical
Transparency Windows (soda-lime glasses), cables for optical
communication (ultra-pure silica)
Translucency and chemical Heat- and corrosion-resistant materials, usually for
inertness Na lamps (Al2O3MgO)
Nonlinearity Switching devices for optical computing (LiNbO3)
IR transparency Infrared laser windows (CaF2, SrF2, NaCl)
5. Chemical
Catalysis Filters (zeolites); purification of exhaust gases
Anticorrosion Heat exchangers (SiC), chemical equipment in
corrosive environments
Biocompatibility Artificial joint prostheses (Al2O3)
6. Biomedical and Biomaterials
7. Mechanical
Hardness Cutting tools (SiC whisker-reinforced A12O3, Si3N4)
High-temperature strength and Stators and turbine blades, ceramic engines (Si3N4)
retention (withstanding)
Wear resistance Bearings (Si3N4)
8. Nuclear applications
Fission Nuclear fuel (UO2, UC), fuel cladding (C, SiC),
neutron moderators (C, BeO)
Fusion Tritium breeder materials (zirconates and silicates of
Li, Li2O); fusion reactor lining (C, SiC, Si3N4)