CERAMICS MATERIALS

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 Outline
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 ThermalProperties  Optical Properties

 Heat capacity  Absorption and
 Thermal expansion transmission
 Thermal conductivity  Scattering and

 Thermal tempering
opacity
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Thermal Properties of Ceramics

 Introduction
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 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
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 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
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 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, the related equations are:
𝜕𝑄 𝜕𝐻 𝜕𝑄 𝜕𝑈
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𝑐𝑝 = = ; 𝑐𝑣 = = ;
𝜕𝑇 𝑝
𝜕𝑇 𝑝 𝜕𝑇 𝑣 𝜕𝑇 𝑣
𝛼 2 𝑉0 𝑇
𝑐𝑝 − 𝑐𝑣 =
𝛽
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.
  Theenergy required for raising the temperature of
a material from its minimum energy state at the
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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 the energy level of electrons in the
structure,
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 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 the classical kinetic theory, the heat requires
that each atom has an average kinetic energy of
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½kT and an average potential energy of ½kT for

each degree of freedom, where k is Boltzmann’s
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
Avogadro’s number.
12
 In this case, it can be shown that:

𝜕𝑈
𝑐𝑣 = = 3𝑁𝑘 = 24.94 𝐽/𝐾. mol
𝜕𝑇 𝑣
= 5.96 cal/g. atom°C
  The main result of heat capacity for ceramics
system is that the heat capacity increase from a
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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 heat energy required to raise the temperature of
an insulating firebrick is much lower than that required
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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
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 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.
  The formulas are:
𝑑𝑙 𝑑𝑉
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𝑎= ;𝛼 =
𝑙𝑑𝑇 𝑉𝑑𝑇

Δ𝑙 ΔV
𝑎= ;𝛼=
𝑙ΔT VΔT
 For limited temperature ranges an average
value is sufficient
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 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 repulsion between atoms changes more
rapidly with atomic separation than does the
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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 cubic crystal, the expansion coefficient along
different crystalline axes are equal, and the
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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
20
 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
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 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
  TSR formula is:
𝜎𝑓 𝑘
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𝑇𝑆𝑅 ≅
𝐸𝛼
 where E is the modulus of elasticity and  is
coefficient of thermal expansion, f is fracture
strength, and k is thermal conductivity.
 Thermal conductivity
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 Thermal conductivity is the amount of heat conducted

through the body per unit temperature gradient.
 The basic equation for thermal conductivity is:
𝑑𝑄 𝑑𝑇
= −𝑘𝐴
𝑑𝜃 𝑑𝑥
where dQ is the amount of the heat flowing normal to
the area A in time d
  The heat flow is proportional to the temperature
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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
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 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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 Ifa 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
𝑁𝑣
3
  Ifenergy equilibrium is obtained by collisions
between molecules and the average distance
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between collisions, the mean free path is l,

molecules moving parallel to the x axis have an
energy of
𝐸
𝐸𝑜 + 𝑙
𝑥
where Eo is the mean energy at x = 0, E/x is the
energy gradient in the x direction.
  Combining the previous equations:
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𝑞 𝜕𝑇 1 𝜕𝐸
=𝑘 = 𝑁𝑣𝑙
𝐴 𝜕𝑥 3 𝜕𝑥
 Since
𝜕𝐸 𝜕𝐸 𝜕𝑇 𝜕𝑇
𝑁 =𝑁 =𝑐
𝜕𝑥 𝜕𝑇 𝜕𝑥 𝜕𝑥
 The conductivity is given by
1
𝑘 = 𝑐𝑣𝑙
3
where c is the heat capacity per unit volume.
 Thermal Conductivity, k
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 Thermal Protection System
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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 carbon–carbon 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,the heat transfer from the surface is relatively
rapid; however, the thermal conductivity of this
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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
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 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.
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 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.
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 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 soda-
lime silicate glass can be raised sufficient to permit
its use in large doors and windows or safety lenses.
  Another reason for using this techniques is that the
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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.
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Optical Properties of Ceramics

 Introduction
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 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
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 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 intensity, I, is the energy flux unit area and
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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.
 There are several optical properties of ceramics
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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 β high reflection 
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(up to R = 1)

 β and R determine how light interacts with a material

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Refractive index n
 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 ε0 and μ0
 v can be related to ε and μ

Due to small susceptibilities of

ceramics
  Values between ≈ 1 and ≈ 4
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 air: 1.003
 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
 Reflection and refraction
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n can be expressed with the angles

of incidence and refraction

n can be used to describe

reflectivity R

n and R vary with wavelength

 Absorbance and color
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 Non-reflected light can be transmitted or absorbed

 Absorption process is a function of energy
(wavelength)
 Absorption: fractional change of light intensity
  Absorption coefficient β is a material property and a
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function of the wavelength
4𝜋𝑘
𝛽=
𝜆
 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)
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 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
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 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