CERAMIC MATERIALS

Prepared by Ushasta & Bisan

 Introduction
Ceramic materials are inorganic, nonmetallic
materials that consist of metallic and nonmetallic
elements bonded together primarily by ionic
and/or covalent bonds. As the ceramic materials
consist of two or more than two elements, the
chemical composition changes with respect to
mother material.

Example:
 metal oxide composites (70% Al2O3 & 30% TiC)
 Silicon aluminum oxynitride (Sialons)
 Cubic Boron Nitride (CBN)
Prepared by Ushasta & Bisan
 CLASSIFICATIONS
Ceramic materials

Traditional ceramic materials Engineering ceramic materials

Al2O3 support base for

integrated circuit in a thermal
Clay, Si, Feldspar conduction module
SiC automotive gas turbine
engine
(glass, bricks, tiles,
electrical porcelain ) Si3N4

Prepared by Ushasta & Bisan

 Properties
 Brittle, low ductility and toughness
 High hot hardness
 Good thermal stability and chemical stability
 High wear resistance
 coefficient of thermal expansion is low
 High melting point
 Good insulation due to absence of conductive electron
 Superior heat dissipation during chip removal process

Prepared by Ushasta & Bisan

Bonding in simple ceramic compounds
In ceramic material we can have two types of bonding.
One is Ionic another one is covalent bonding. Now by
using Pauling’s Equation we can find the % of ionic
character existing in the bonding.

Pauling equation:
2
% ionic character= (1-e(-0.25)(XA-XB) )(100%)

Prepared by Ushasta & Bisan

example:
For Zirconium Oxide (ZrO)
difference in electro negativity is 2.3 = XA- XB in Pauling equation
2
% ionic character= (1-e(-0.25)(XA-XB) )(100%)

So, we get % of ionic character = 73%

% of covalent character = 27%

Prepared by Ushasta & Bisan

 Ionic arrangements found in Ionicaly bonded
solids
Our target is to make a low energy state stable dense closed
packed structure.
 The energies of the atoms are lowered by formation of ions and their
bonding into ionic solid. Ionic solids tend to have their ions packed
together as densely as possible to lower the overall energy of the
solids as possible. Now, the ionic solids consist of anion and cation.
So for maintaining charge neutrality, anions must contact with
central cation. Otherwise the ionic solid become unstable.

 To get densely closed packed structure, the coordination number

must be increased. So, the relative size of ions come into picture.
The radius ratio i.e. rcation/ranion when the ions just touch each other
and contact the central cation, is called critical (min) radius ratio.

Prepared by Ushasta & Bisan

Stable and unstable cation-anion configuration.
RED circles represent anion
BLUE circles represent cation

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Cesium Chloride (CsCl)
Radius ratio = 0.94
crystal structure
Coordination number = 8
z

(½, ½, ½)

x Prepared by Ushasta & Bisan

Sodium Chloride (NaCl) Radius ratio = 0.56
crystal structure z Coordination number = 6

x
Prepared by Ushasta & Bisan
Interstitial sites in FCC & HCP crystal Lattices

In crystal structure lattice, there are empty spaces or voids. Voids

are the interstitial sites where, other than the parent atoms can be
fitted. Now, there are two types of sites-

 Octahedral
 Tetrahedral

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
Octahedral:
In octahedral site there six equidistant atoms ions surrounded the central
void and the centers of the equidistant atom or ions from an eight sided
octahedron. In FCC structures, there are 1/4th of octahedral void per
edge. Total equivalent octahedral void (12X1/4+1=) 4. So, there are four
atoms per FCC unit cell & one octahedral interstitial site/ atom. Now, there
are same no of interstitial sites in case of HCP as it is also a close packed
structure.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
Tetrahedral:

In tetrahedral site there are four nearest atom or ions equidistant from the
centre of the tetrahedral site and a regular tetrahedron is formed when,
centers of the equidistant atom or ions are joined. In FCC, there eight
tetrahedral sites per unit cell or two tetrahedral interstitial sites per atom
of the parent FCC unit cell.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 ZINC BLENDE CRYSTAL STRUCTURE

In ZnS crystal structure, the atom or ions other than the parent one occupy
the half of tetrahedral interstitial sites. In this ZnS unit cell, sulfur atoms
occupy the FCC unit cell atom positions or lattice points and the Zn atoms
occupy half the tetrahedral interstitial positions of the FCC unit cell. Now,
Zn-S bond has 87% covalent character.
Radius of Zn2+ =0.060 nm and S2- =0.174 nm.
So, CN =4.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 CaF2 Crystal Structure

In this unit cell the Ca2+ ions occupy the FCC lattice sites, while the F- ions
are located at the tetrahedral sites. As Ca2+ has valence two & F- has one,
so there are one Ca2+ ion for every two F- ion for maintaining neutrality.
The four remaining are octahedral sites. There are four Ca2+ ions & eight F-
ions per unit cell.

e.g. UO2, BaF2, AuAl2, PbMg2.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Corundum Crystal Structure

In Al2O3 crystal structure the oxygen ions are located the lattice sites of a
hexagonal close packed unit cell. There are same no. of octahedral sites as
in FCC. As, Al3+ has a valence three & O2- has two, so there two Al3+ ions for
every three O2- ions to maintain electrical neutrality. Thus Al ions can
occupy only 2/3 of the octahedral sites of the HCP. Al2O3 lattice which
leads to some distortion of this structure.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Perovskite Crystal Structure

In CaTiO3 structure theCa2+ & O2- ions from an FCC unit cell with the Ca2+
ions at the corners of the unit cell and the O2- ions in the centers of the
faces of unit cell. The highly charged Ti4+ ion is located the octahedral
interstitial site at the centre of the unit cell.

Prepared by Ushasta & Bisan

Unit cell of BaTiO3

Prepared by Ushasta & Bisan

 Carbon and Its Allotropes
Carbon has many allotropes, i.e. it can exist in many crystalline forms. The
carbon atom in the ground state has the electron configuration 1s22s22p2.
The electron arrangement indicates that carbon should form two covalent
bonds with its two half-filled 2p orbital. But, the carbon has a tendency to
produce hybrid orbital by hybridization. In this section the structure and
properties of graphite, diamond, buckyball and buckytube will be
discussed.

Prepared by Ushasta & Bisan

 Graphite

When one of the 2s electrons is

promoted to 2p orbital and fill the
orbital, then three sp2 hybrid orbital
are generated. And, though it has a
sp2 hybridization, it has a trigonal
structure. The hybrid orbital are 120o
apart from each other and they are in
a same plane.

Prepared by Ushasta & Bisan

sp2 hybridization
Prepared by Ushasta & Bisan
 The orbital having the unhybridized p electron is perpendicular to
that plane. Graphite has a layered structure in which the carbon
atoms in the layers are strongly bonded in hexagonal arrays. The
layers are bonded by weak secondary bonds and can slide past
each other easily. The free electron can easily travel from one side
to other of a layer but don’t easily from one layer to other. Thus
graphite is anisotropic. Density of it is 2.26 g/cm3 which is low. It is a
good thermal conductor in the basal plane not in perpendicular
plane

Properties:
Ø Layered structure with strong bonding within the planar
layers and weak, van der Waals bonding between layers
Ø Easy interplanar cleavage, applications as a lubricant
and for writing (pencils)
Ø Good electrical conductor
Ø Chemically stable even at high temperatures
Ø Applications include furnaces, rocket nozzles, welding
electrodes
Prepared by Ushasta & Bisan
 Diamond
In case of diamond, the 2s electron is
promoted with the 2p electrons to from
sp3 hybridized orbital. There, one 2s orbital
combines with three 2p orbitals to form four
sp3, hybridized orbitals. Because of this
diamond has a tetrahedral shape.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 As, here is no free electron, so, diamond is isotropic, has a higher
density of about 3.15 g/cm3. The structure of diamond accounts for
the extremely high hardness of diamond and its high bond strength
and melting temperature. Diamond has a bond energy of 711 KJ/mol
(170 Kcal/mol) and a melting temperature of 3550oc.

But, Natural diamond is extremely expensive. However, synthetic diamonds

have comparable hardness, are cheaper.
Properties:
 Has diamond-cubic structure (like Si, Ge)
 One of the strongest/hardest material
known
 High thermal conductivity (unlike ceramics)
 Transparent in the visible and infrared, with high
index
of refraction, looks nice, costs $$$
 Semiconductor (can be doped to make
electronic
devices)
 Metastable (transforms to carbon when heated)
Prepared by Ushasta & Bisan
 Buckminster Fullerenes (Buckyball)

It is a new polymorph of carbon which is generated by the presence of

clusters of carbon atoms in a molecular range of C30 to C100. This new
polymorph is called fullerenes or buckyball. The buckyball looks very
similar to a soccer ball that is made of 12 pentagons and 20 hexagons. The
diameter of the C60 fullerene is 0.710 nm and classified as a nanocluster.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Nanotubes
When a single graphite atomic layer with the conventional hexagonal
structure is rolling into a tube using two hemifullerenes made up of only
pentagons, then we obtain the structure of nanotubes. The tensiles
strength is 45 GPa and elastic modulas of 1.3x1012 Pa. Nanotubes are
classified in single wall nanotube & multiwall nanotubes. It is used in STM
tips, field emitters in flat panel display, channel sensors.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Silicate Structures
Many ceramic materials contain silicate structures, which consist of silicon
and oxygen atoms bonded together in various arrangement. Some of the
arrangements are following-

Basic Structural unit of the silicate

structures
Basic structural unit of the silicate has tetrahedron structures. By Pauling’s
equation we can find 50% covalent and 50% ionic character of Si-O bond
in SiO44-. The radius ratio of Si-O bond is 0.29

Prepared by Ushasta & Bisan

 Island, Chain & Ring Structures of silicates

 In SiO44-., each oxygen atom has a free electron, so net charge of a basic
structural unit is negative. Now, if one oxygen atom bonded with a
positive ion then ISLAND structure is produced. E.g. (Mg, Fe)2SiO4
 If two corners of each SiO44- tetrahedron are bonded with the corners of
other tetrahedron, a CHAIN or RING structure will generate. E.g. MgSiO3
has a Chain structure and Be3Al2(SiO3) 6 has ring silicate structure

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Sheet structures of Silicates

Silicates sheet structures form when three corner in the same plane of a
silicate tetrahedron are bonded to the corners of three other silicate
tetrahedrons. It has the unit chemical formula of Si2O52-. The negatively
charged silicate sheet can bond with a positively charged sheet of Al2 (OH)
2+
4 to form a composite sheet of KAOLINITE.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
Prepared by Ushasta & Bisan
 Silicate network
Silica:
When all four corners of the silicate tetrahedron share oxygen atoms, an
SiO2 network called silica is produced. There three basic silica structures-
 Quartz
 Tridymite
 Crytobalite
Above 1710oC silica is liquid.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Feldspars
When some Al3+ ions replace some Si4+ ions to form a network with a net
negative charge, the feldspar silicate structural network is formed. This
negative charge is balanced with large ions of Ceramic.

Prepared by Ushasta & Bisan

Glasses

Prepared by Ushasta & Bisan

 Introduction

A glass is a ceramic material which is made from inorganic material at high

temperature. An inorganic product of fusion that has cooled to a rigid
condition without crystallization, is glass. As glass has a non crystalline
structure, so that the molecules in a glass are not arranged in a defined
manner and having a short range order.

Prepared by Ushasta & Bisan

 General properties

 A noncrystalline/ amorphous structure

 combination of transparency & hardness
 good corrosion resistance
 good insulating property
 provide vaccum tight enclosure
 high chemical resistance

Prepared by Ushasta & Bisan

 Glass transition temperature

There are two types of solids, one is crystalline another one is non
crystalline. A liquid that fors crytalline solids by solidification, will normally
start crystallization at its melting point and specific volume drastically falls.
Now, in figure the path is indicated by blue color. But as glass is a non
crytalline solid it does not follow this path. Because as the temperature is
decreasing there is not a uniform decrement of specific volume i.e.
increment of viscosity and, transforms from a rubbery, soft plastic state to
rigid, brittle glassy state in a narrow temperature range where the slope of
specific volume versus temperature curve is marked decreased. The point
of intersection two slopes, where the transformation occurs is called
GLASS TRANSITION TEMPERATURE (Tg)

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Structure of Glasses
Glasses’s structure has mainly three kinds of oxides-

1.Glass forming oxides:

Silica,Si02 is the main ingredient of most of the inorganic glasses. the main
subunit of silica is SiO44- group which has a tetrahedral structure, where
the central Si4= is bonded with four O22- and each oxygen has a free
electron. So, there eager to make with another SiO2. But as glass is non
crystalline solid the Silica tetrahedral are not arranged in a regular manner.
So, There will be a formation of loose network with no long-range order.
Another glass forming oxide is B2O3.

Prepared by Ushasta & Bisan

Crystalline structure Non crystalline structure

Prepared by Ushasta & Bisan

2. Glass Modifying Oxides

Oxides that break up the glass network are known as network modifiers.
Some alkali oxides Na2O and K2O and Alkaline earth oxides such as CaO,
MgO are glass modifying oxides. The main objective to add this additives
to lower the viscosity so that it can be worked and formed more easily.

Na2O 2Na+ + O2-

This oxygen enters the silica network and joins there by breaking the
network The Na+ does enter the network but remain as metal ion filling
the interstices.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
3. Intermediate oxides

This oxides can not form a network but can join an existing network. Al2O3
is an intermediate oxides. It can enter the network as a AlO44- tetrahedral
replacing SiO44- groups. As aluminium has valance of three instead of +4
so an alkali metal ion is required to maintain charge neutrality and by
adding this type of oxides the glass can withstand higher temperature.

Lead oxide is another intermediate oxide

Prepared by Ushasta & Bisan

 Composition of Glass
Fused Silica Glass
 most important single component glass (99.5% Silica)
 high spectral transmission
 not subjected to radiation damage
 used in wind tunnel window, space vehicle window etc.
 very expensive

Soda Lime Glass

 Most commonly produced glass

 71 to 73% Silica, 12-14% Na2O, 10-12% Cao
 Na2O, CaO decrease softening point to make easy to form
 1-4% MgO is added to prevent devitrification and 05-1.5% Al2O3 to
increase durability
 Used for flat glass, container etc.

Prepared by Ushasta & Bisan

Borosilicate Glass
 replacement of alkali oxides by boric oxides
 Low expansion glass
 Used in laboratory purpose and piping ovenware etc.

Lead Glass
 low melting points
 Useful for shielding from energy radiation
 Used in radiation windows, television bulbs etc.
 High refractive index
 Used for some optical glasses and for decorative purposes.

Prepared by Ushasta & Bisan

Prepared by Ushasta & Bisan
 Viscous deformation of glasses
Viscosity is a measure of a non-crystalline (glass or liquid) material’s
resistance to deformation. High-viscosity fluids resist flow; low-viscosity
fluids flow easily. How readily a moving layer of fluid molecules drags
adjacent layers of molecules along with it determines its viscosity.
Units are Pa-s, or Poises (P)
1 P = 0.1 Pa-s
Viscosity of water at room temp is ~ 10-3 P
Viscosity of typical glass at room temp >> 1016 P

As glass behaves likes a viscous liquid above its glass transition temperature
the silicate atoms try to slide past each other but the intermolecular
bonding strength will resist that transformation. But when stress is applied
then the sliding tendency overcomes the resistive force and deformation
occurs according to Arrhenius equation

Prepared by Ushasta & Bisan

 ŋ*=ŋ0e+Q/RT
ŋ*= viscosity of glass
ŋ0= preexponential constant
Q= molar activation energy
for viscous flow

Prepared by Ushasta & Bisan

 On the viscosity scale several specific points that are important in the
fabrication and processing of glasses are labeled:

Prepared by Ushasta & Bisan

 Thermal tempering
The strength of a glass piece may be enhanced by intentionally inducing
compressive residual surface stresses. This can be accomplished by a heat
treatment procedure called thermal tempering. With this technique, the
glassware is heated to a temperature above the glass transition region yet
below the softening point. It is then cooled to room temperature in a jet
of air or, in some cases, an oil bath. The residual stresses arise from
differences in cooling rates for surface and interior regions. Initially, the
surface cools more rapidly and, once having dropped to a temperature
below the strain point, becomes rigid. At this time, the interior, having
cooled less rapidly, is at a higher temperature (above the strain point) and,
therefore,is still plastic. With continued cooling, the interior attempts to
contract to a greater degree than the now rigid exterior will allow.Thus,
the inside tends to draw in the outside, or to impose inward radial
stresses. As a consequence, after the glass piece has cooled to room
temperature, it sustains compressive stresses on the surface, with tensile
stresses at interior regions.

Prepared by Ushasta & Bisan

The failure of ceramic materials almost always results from a crack that is
initiated at the surface by an applied tensile stress. To cause fracture of a
tempered glass piece, the magnitude of an externally applied tensile
stress must be great enough to first overcome the residual compressive
surface stress and, in addition, to stress the surface in tension sufficiently
to initiate a crack, which may then propagate. For an untempered glass, a
crack will be introduced at a lower external stress level, and, consequently,
the fracture strength will be smaller.
Tempered glass is used for applications in which high strength is
important; these include large doors and eyeglass lenses.

Prepared by Ushasta & Bisan

 Chemically Strengthened Glass
If a sodium alluminosilicate glass is immerged in a bath of potassium nitrate
at a temperature 500C (below its stress point) for 6 to 7 hours, the smaller
sodium ions near the surface of the glass are replaced by potassium ions.
This leads to a generation of compressive stress which creates a
corresponding tensile stress and strengthening the glass

Prepared by Ushasta & Bisan

 Summary
• Various crystal structure of ceramic
• Description of interstitial sites
• Carbon and it’s allotropes
• Silicate structure and network
• Glass and it’s properties

Prepared by Ushasta & Bisan

Thank You

Prepared by Ushasta & Bisan