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CERAMICS MATERIALS

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Outline
3

Thermal

Properties
Heat capacity
Thermal expansion
Thermal conductivity
Thermal tempering

Optical

Properties
Absorption and
transmission
Scattering and
opacity

Thermal Properties of Ceramics

Introduction
5

Physical

properties that determine much of the


usefulness of ceramic materials are those directly
related to temperature changes.
In this instance, related to temperature changes is
the thermal properties of a material

As

a consequence of their brittleness and their low


thermal conductivities, ceramics are prone to
thermal shock, i.e. they will crack when subjected to
large thermal gradient.
Thermal stresses will also develop because of
thermal contraction mismatches in multiphase
materials or anisotropy in a single phase.

Heat capacity
7

One

of the properties related to thermal properties is


heat capacity, which is a measure of the energy
required to raise the temperature of a material or the
increase in energy content per degree of temperature
rise.
Heat capacity is normally measured at constant
pressure, cp, but theoretical calculations are frequently
reported in terms of the heat capacity at constant
volume, cv.

Thermodynamically,
8

the related equations are:

=
; =
=

2 0
=

where Q is the heat exchange, U the internal energy, H


the enthalpy, the volume thermal expansion
coefficient, the compressibility, and V0 the molar
volume.

The
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energy required for raising the temperature of


a material from its minimum energy state at the
absolute zero goes into:
Vibrational energy by which atom vibrate around
their lattice positions with an amplitude and
frequency that depend on temperature,
Rotational energy for molecules in gases, liquids,
and crystals having rotational degrees of
freedom,

Raising

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the energy level of electrons in the


structure,
Changing the atomic position (such as forming
Schottky or Frenkel defects, disordering
phenomena, magnetic orientation, or altering the
structure of glasses at the transformation range).
All these changes correspond to an increase in
internal energy and are accompanied by an
increase in configurational energy.

From
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the classical kinetic theory, the heat requires


that each atom has an average kinetic energy of
kT and an average potential energy of kT for
each degree of freedom, where k is Boltzmanns
constant.
Thus, the total energy for an atom with 3 degrees
of freedom is 3kT, whereas the energy content
per gram atom will be 3NkT where N is
Avogadros number.

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In

this case, it can be shown that:

=
= 3 = 24.94 /. mol

= 5.96 cal/g. atomC

The
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main result of heat capacity for ceramics


system is that the heat capacity increase from a
low value at low temperature to a value near
5.96 cal/g-atomoC at temperatures in the
neighborhood of 1000oC for most oxides and
carbides.
Further increases in temperature do not strongly
affect this value, and it is not much dependent on
the crystal structure.

The
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heat energy required to raise the temperature of


an insulating firebrick is much lower than that required
to raise the temperature of a dense fire brick
valuable and useful properties of insulating materials
for the manufacture of furnace which must be
periodically heated and cooled.
For furnaces that must be rapidly heated or cooled, use
radiation shielding such as molybdenum sheet or low
density fiber or powder insulation which has a low solid
content and thus a low heat capacity per unit volume.

Thermal expansion
15

Thermal

expansion is the fractional change in


volume or linear dimension per degree of
temperature change.
At any particular temperature, we can define
a coefficient of linear expansion and a
coefficient of volume expansion.

16

The

formulas are:

=
; =

V
=
;=
T
VT
For limited temperature ranges an average
value is sufficient

17

The

specific volume of any given crystal


increases with temperature, and the crystal
tends to become more symmetrical.
The general increase in volume with
temperature is mainly determined by the
increased amplitude of atomic vibration about
a mean position.

The
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repulsion between atoms changes more


rapidly with atomic separation than does the
attraction terms; thus the minimum energy trough is
non-symmetrical.
The change in volume due to lattice vibration is
closely related to the increase in energy content;
thus, changes in the thermal expansion coefficient,
= dV/dT, with temperature are parallel to the
changes in heat capacity.

For
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cubic crystal, the expansion coefficient along


different crystalline axes are equal, and the
changes in dimensions with temperature are
symmetrical; and thus the linear expansion
coefficient is the same in any direction.
For non-isometric crystal, the thermal expansion
varies along different crystallographic axes; and
may be negative in one direction resulting in very
low volume expansion

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This

can be used for thermal shock applications


such as aluminum titanate, cordierite, and
various lithium aluminum silicate.
Thermal stresses can also be induced by
differential thermal expansion in multiple
materials or anisotropy in the thermal
expansion coefficient of single phase solid.

Resistance to thermal shock


21

The

capacity of a material to withstand failure due


to the rapid cooling of a brittle body is termed
thermal shock resistance.
For a ceramic body that is rapidly cooled, the
resistance to thermal shock depends not only on the
magnitude of the temperature change, but also on
the mechanical and thermal properties of the
material.

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The

thermal shock resistance is best for ceramics


that have high fracture strengths f and high
thermal conductivities, as well as low moduli of
elasticity and low coefficients of thermal expansion.
The resistance of many materials to this type of
failure may be approximated by a thermal shock
resistance parameter TSR

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TSR

formula is:

where E is the modulus of elasticity and is


coefficient of thermal expansion, f is fracture
strength, and k is thermal conductivity.

Thermal conductivity
24

Thermal

conductivity is the amount of heat conducted


through the body per unit temperature gradient.
The basic equation for thermal conductivity is:

where dQ is the amount of the heat flowing normal to


the area A in time d

The
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heat flow is proportional to the temperature


gradient, -dT/dx, and the proportionality factor being
a material constant, the thermal conductivity k.
Ceramics have low thermal conductivity compared with
metals.
Heat is transported by the conduction band electrons in
metals as well as atomic vibrations, whereas in ceramics
heat is transported only by atomic vibrations.

Thermal conduction process


26

The

conduction process for heat energy transfer


under the influence of a temperature gradient
depends on
The energy concentration present per unit volume,
Its velocity movement, and
Its rate of dissipation with the surroundings.

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In

gases, individual atoms or molecules exchange


kinetic energy by collision;
the heat energy present is simply equal to the heat
capacity per unit volume,
the velocity of molecular motion can be calculated
from kinetic theory, and
the rate of energy dissipation depends on the rate
of collision between atoms or molecules.

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If

a temperature gradient in which the concentration


of molecules is N and their average velocity is v, the
average rate at which molecules pass a unit area in
the x direction is equal to
1

If
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energy equilibrium is obtained by collisions


between molecules and the average distance
between collisions, the mean free path is l,
molecules moving parallel to the x axis have an
energy of

where Eo is the mean energy at x = 0, E/x is the


energy gradient in the x direction.

Combining the previous equations:

=
=

Since

=
=

The conductivity is given by


1
=
3
where c is the heat capacity per unit volume.

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Thermal Conductivity, k
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Thermal Protection System


32

FRSI, felt reusable surface insulation; AFRSI, advanced flexible


reusable surface insulation; LRSI, low-temperature reusable
surface insulation; HRSI, high-temperature reusable surface
insulation; RCC, reinforced carboncarbon composite.

33

This photograph shows a


white-hot cube of a silica fiber
insulation material, which, only
seconds after having been
removed from a hot furnace,
can be held by its edges with
the bare hands.

Initially,
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the heat transfer from the surface is relatively


rapid; however, the thermal conductivity of this
material is so small that heat conduction from the
interior [maximum temperature approximately
1250C (2300F)] is extremely slow.
This material was developed especially for the tiles
that cover the Space Shuttle Orbiters and protect and
insulate them during their fiery reentry into the
atmosphere.

Thermal tempering
35

Because

of transparency and chemical inertness of


inorganic glasses, their use in everyday life are
ubiquitous.
However, for many applications, especially where
safety is concerned, as manufactured, glass is
deemed to be too weak and brittle.

36

Fortunately,

glass can be significantly strengthening


by a process called thermal tempering, which
introduces a state of compressive residual stress on
the surface.
The thermal process involves heating the glass body
to a temperature above its glass transition
temperature, followed by a two-step quenching
process.

37

During

the first quenching stage, initially the surface


layer contracts more rapidly than the interior and
become rigid while the interior is still in a viscous
state.
During the second quenching step, the entire glass
sample is cooled to room temperature.

38

Given

that the interior will have cooled at a slower


rate than its exterior, its final specific volume will be
smaller than that of exterior.
By using this techniques, the mean strength of sodalime silicate glass can be raised sufficient to permit
its use in large doors and windows or safety lenses.

Another
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reason for using this techniques is that the


release of large amount of stored elastic energy upon
fracture tends to shatter the glass into great many
fragments which are less dangerous than larger shards.
Windshield are made of two sheets of tempered glass
in between which a polymer layer embedded.
The function of latter is to hold the fragments of glass
together in case of fracture and to prevent them from
becoming lethal projectiles.

40

Optical Properties of Ceramics

Introduction
41

Since

the beginning of civilization, the allure of


materials was mainly because of aesthetic and priced
because of their transparency, brilliance, and color.
In today advent of technology, the optical properties of
glass and ceramics are even more important, for
example in commercial fiber-optic networks to transfer
gigabits of information per second.

The basic
42

The

basic principles of ceramics optical properties are


based on the interaction between light or
electromagnetic radiation impinging on a solid, which
can be transmitted, absorbed, and scattered.
For a total incident flux of photons Io energy
conservations requires that Io = IT + IR + IA where IT, IR,
and IA represent the transmitted, reflected, and
absorbed intensities, respectively.

The
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intensity, I, is the energy flux unit area and


has the unit of J/m2.s
Dividing both sides of the previous equation with
Io yields
1=T+R+A
where T, R, and A are the fraction of light
transmitted, reflected, and absorbed, respectively.
A material cannot simultaneously be highly
absorptive, reflective and transmissive.

44

There are several optical properties of ceramics


materials:
Refraction: apparent bending of light rays as they pass
from one medium to another. For example, a rod
immersed in a fluid will appear bent.
Reflection; not all light that is incident on a surface is
refracted, a portion of it can be reflected.
Absorbance and transmittance; the transmittance T
through a transparent medium is proportional to the
amount of light that is neither reflected nor absorbed.

Shininess and inability to transmit visible light indicates high


absorption linear absorption coefficient high reflection
(up to R = 1)

and R determine how light interacts with a material

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Refractive index n
46

velocity of light in vacuum: c = 299,792,458 m/s

velocity of light in any other medium: v (v < c)

refractive index n = c/v

c can be related to 0 and 0

v can be related to and

Due to small susceptibilities of


ceramics

Values between 1 and 4

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silicate glasses: 1.5 to 1.9


solid oxide ceramics: 2.7
Dependent on structure-type and packing geometry
glasses and cubic crystals: n is independent of direction
other crystal systems: n larger in closed-packed directions
SiO2: glass = 1.46, tridymite = 1.47, cristobaltite = 1.49,
quartz = 1.55

air: 1.003

Reflection and refraction


48

can be expressed with the angles


of incidence and refraction

can be used to describe


reflectivity R

and R vary with wavelength

Absorbance and color


49

Non-reflected

light can be transmitted or absorbed


Absorption process is a function of energy
(wavelength)
Absorption: fractional change of light intensity

Absorption
50

coefficient is a material property and a


function of the wavelength
4
=

Absorption of photon: excitation of electron from


valence to conduction band. Only if photon energy >
band gap hv Eg
Magnitude of band gap determines if the material
does not absorb (transparent)
absorbs certain wavelength (opaque)

51

Absorption

of certain
wavelength results in color
Generating color in ceramics:
Addition of transition
elements with incomplete d
band filling V, Cr, Mn, Fe, Co,
Ni

References
52

M.W.

Barsoum, Fundamental of Ceramics, Institute


of Physics Publishing, Philadelphia, 2003.
W.D. Kingery, H.K. Bowen, D.R. Uhlmann,
Introduction to Ceramics, 2nd ed., John Wiley &
Sons, New York, 1976.
W.D. Callister, Fundamentals of Materials Science and
Engineering, 5th ed. 2001

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