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Course Update
Ceramic Materials
Why Ceramics have Low Coefficient of Thermal Coefficient
In many ceramic materials relatively strong interatomic bonding forces are found. This is
reflected in comparatively low values typically range between about 0.5 x 10-6/0C and 15 x
10-6/C. For non crystalline ceramics and also those having cubic crystal structures is
isotropic. Otherwise, it is anisotropic; and, in reality, some ceramic materials, upon heating,
contract in some crystallographic directions while expanding in others. for inorganic glass
depends upon the composition. for fused silica (high purity SiO2 glass) has a small value
0.4 x 10-6/C. One can explain this by a low atomic packing density such that interatomic
expansion produces relatively small macroscopic dimensional changes.
Ceramic materials that are subjected to temperature changes must have coefficients of
thermal expansion that are relatively low, and also isotropic. Otherwise, these brittle
materials may experience fracture as a consequence of non-uniform dimensional changes in
what is called thermal shock.

CERAMIC SINTERING
Sintering is part of the firing process used in the manufacture of pottery and other ceramic
objects. Some ceramic raw materials have a lower affinity for water and a lower plasticity
index than clay, requiring organic additives in the stages before sintering. The general
procedure of creating ceramic objects via sintering of powders includes:
Mixing water, binder, deflocculant, and unfired ceramic powder to form a slurry
Spray-drying the slurry
Putting the spray dried powder into a mold and pressing it to form a green body (an
unsintered ceramic item)
Heating the green body at low temperature to burn off the binder
Sintering at a high temperature to fuse the ceramic particles together

Thermal Conductivity of Ceramics

The thermal conductivity of most ceramic materials normally diminishes with increasing
temperature, at least at relatively low temperatures (see figure). Figure indicates that the
thermal conductivity begins to increase at higher temperatures, which is due to radiant heat
transfers; significant quantities of infrared radiant heat may be transported through a
transparent ceramic materials. The efficiency of this process increases with temperature.
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It is interesting to note that porosity in ceramic materials may have a dramatic influence on
thermal conductivity; increasing the pore volume will, under most circumstances, result in a
reduction of thermal conductivity. Interestingly, many ceramics that are used for thermal
insulations are porous. Heat transfer across pores is ordinarily slow and inefficient. Internal
pores normally contain still air, which has an extremely low thermal conductivity

Crystal Structure, Defects in Solids and Diffusion in

Solids
Example (AMIE Summer 2011, 5 marks)

Find the equilibrium concentration of vacancies in aluminium at 0 K and 300 K. Enthalpy of

formation of vacancies in aluminium Hf = 68 kJmol-1; R = 8.314 Jmol-1K-1.

Solution

eV
For aluminium 0.70
vacancy

n H f
We have exp
N RT

n 68x 103
(i) At 0 K exp exp[] 0
N 8.314x 0

n 68x 103
(ii) At 300 K exp exp[27.26]
N 8.314x 300
n
1.45 x 1012
N

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Electronic Properties of Materials
MAGNETIC PERMEABILITY
Some materials become magnetized when placed in a magnetic field; the ability of a material
to become magnetized is called magnetic permeability. An example of this is rubbing a piece
of iron with a magnet: the iron will become magnetized and have its own magnetic field,
meaning it has some degree of magnetic permeability.
Many substances, even water, have a degree of magnetic permeability. When a material is
placed in a magnetic field, it interacts with the field in one manner or another. The
permeability of a substance describes the way the material responds and the effects of the
field on the material. A substance with magnetic permeability will either magnetize itself in
the direction of the field or in opposition to it. Thus, depending on the permeability, the
substance will either be attracted to or repelled by the field.
Scientists represent magnetic permeability with the Greek letter, mu (). The International
System of Units (SI) measures permeability in henrys per meter (H/m) or in Newton per
ampere squared (N/A2).

Thermal Properties
THERMAL STRESSES
These are the stresses induced in a material body as a result of changes in temperature. These
stresses can lead to fracture or undesirable plastic deformation.
To understand the origins and nature of thermal stresses, let us consider a homogeneous and
isotropic solid rod that is heated or cooled uniformly; i.e., no temperature gradients are
imposed. For free expansion or contraction, the rod will be stress free. If however, axial
motion of the rod is restrained by rigid end supports, thermal stresses will be introduced. The
magnitude of the stress resulting from a temperature change from T to Tf is expressed as
E (T T f ) E T
where is the linear coefficient of thermal expansion and E is the modulus of elasticity.
Upon heating (Tf > T), the stress ( < 0) is compressive, as the rod expansion has been
constrained. However, if the rod specimen is cooled (Tf < T), a tensile stress ( > 0) will be
imposed. Moreover, the stress in equation is the same as the stress that would be required to
elastically compress (or elongate) the rod back to its original length after length after it has
been allowed to expand (or contract) freely with the T Tf temperature change.
We may note that thermal stresses may be established as a result of temperature gradients
across a body, which are frequently caused by rapid heating or cooling, in that the outside
changes temperature more rapidly than the interior; differential dimensional changes serve to
restrain the free expansion or contraction of adjacent volume elements within the specimen.
For example, upon heating, the exterior of a specimen is rather hotter and, therefore, will

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have expanded more than the interior regions. Obviously, compressive surface stresses are
induced and are balanced by tensile interior stresses. However, the interior-exterior stress
conditions are reversed for rapid cooling such that the surface is put into a state of tension.

TEMPERATURE MEASURING DEVICES (SENSORS)

There are several methods of measuring temperature that can be categorized as follows:
Expansion of a material to give visual indication, pressure, or dimensional change
Electrical resistance change
Semiconductor characteristic change
Voltage generated by dissimilar metals
Radiated energy
Thermometer is often used as a general term given to devices for measuring temperature.
Examples of temperature measuring devices are described below.

Bimetallic strip
Bimetallic strip is a type of temperature measuring device that is relatively inaccurate, slow
to respond, not normally used in analog applications to give remote indication, and has
hysteresis. The bimetallic strip is extensively used in ON/OFF applications not requiring high
accuracy, as it is rugged and cost effective.
These devices operate on the principle that metals are pliable and different metals have
different coefficients of expansion. If two strips of dissimilar metals such as brass and invar
(copper-nickel alloy) are joined together along their length, they will flex to form an arc as
the temperature changes; this is shown in Fig. (a). Bimetallic strips are usually configured as
a spiral or helix for compactness and can then be used with a pointer to make a cheap
compact rugged thermometer as shown in Fig. (b). Their operating range is from 180 to
430C and can be used in applications from oven thermometers to home and industrial
control thermostats.

(a) (b)

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Thermistors
Thermistors are a class of metal oxide (semiconductor material) which typically have a high
negative temperature coefficient of resistance, but can also be positive. Thermistors have high
sensitivity which can be up to 10 percent change per degree Celsius, making them the most
sensitive temperature elements available, but with very nonlinear characteristics. The typical
response times is 0.5 to 5 s with an operating range from 50 to typically 300C. Devices are
available with the temperature range extended to 500C. Thermistors are low cost and
manufactured in a wide range of shapes, sizes, and values. When in use care has to be taken
to minimize the effects of internal heating.

Thermocouples
Thermocouples are formed when two dissimilar metals are joined together to form a junction.
An electrical circuit is completed by joining the other ends of the dissimilar metals together
to form a second junction. A current will flow in the circuit if the two junctions are at
different temperatures.

The current flowing is the result of the difference in electromotive force developed at the two
junctions due to their temperature difference. In practice, the voltage difference between the
two junctions is measured; the difference in the voltage is proportional to the temperature
difference between the two junctions. Note that the thermocouple can only be used to
measure temperature differences.

Phase Diagrams and Transformations

GIBBS' PHASE RULE
Additional matter
As follows from the phase rule, the number of phases existing simultaneously in a binary
system cannot be more than three. These three phases can only exist at a definite phase
composition and a definite temperature. If the number of phases in a binary system turns out
to be more than three, this means that either the alloy is not in the equilibrium state or the
number of phases and constituents has been determined incorrectly.
In a ternary system no more than four phases may be in equilibrium. When only one phase is
present in a system, the degrees of freedom are equal to the total variables, with the increase
in number of phases, the degrees of freedom decrease. The degree of freedom cannot be less
than zero. Obviously, we have an upper limit to the number of phases that can exist in
equilibrium in a given system.
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At solidification temperature, a pure metal is a one-component system consisting of two
phases of identical composition
F=1+22=0
Clearly, the number of phases and number of degrees of freedom equals zero, i.e. F = 0. This
is known as non-variant equilibrium. When the number of phases is less than the maximum
possible number by one, the number of degrees of freedom will also increase by one (F = 1).
Such type of system is called as monovariant.
An alloy of two metals is a two-phase and two-component system at solidification, F = 1.
When F = 2, the system is said to be a divariant. Obviously, a system may be in equilibrium
at different temperatures and concentrations. One can represent all transformations occurring
in alloys and depending on temperature and concentration (C = 2) by equilibrium diagrams.
The equilibrium diagrams are plotted with concentration as the
abscissa and temperature as ordinate.

TRANSFORMATION OF AUSTENITE UPON CONTINUOUS COOLING

Let us consider a number of specimens of eutectoid steel heated to a temperature t, above the
critical points as shown in figure. At this temperature, the steel is present in the form of stable
austenite. Let the specimen of steel is cooled continuously below the lower critical point, i.e.,
723C at various cooling rates. Let the inclined curves V1, V2, V3, . . . on temperature-time
graph represent these cooling processes.
The slowest cooling rate is represented by the curve V1. Slightly higher cooling rate is
represented by the curve V2. Still more rapid cooling rates are represented by the V3, V4 and
V5. We may note that these curves are straight lines.
Now, we superimpose these cooling curves (V1, V2, V3 . . . ) on the time-temperature
transformation diagrams as shown in figure. From figure, we note that the curve V1 crosses
transformation curves 1 and 2 at points a1 and b1 respectively. Obviously, on slow cooling,
the austenite completely transforms into a ferrite cementite mixture. Since the transformation
takes place at the highest temperature therefore the ferrite cementite mixture is pearlite. The
curve V2 also intersects both the transformation curves at points a2 and b2 respectively.
Austenite, at this cooling rate completely transforms into ferrite-cementite mixture.
The transformation occurs at lower temperature (as compared to V1), the resulting ferrite-
cementite is sorbite. Similarly, the curve V3 also intersects both the curves at points a3 and b3
respectively. The resulting ferrite-cementite mixture is troostite. We note that the curve V4
does not cross both the transformation curves. It intersects only the curve 1 at point a4, and
does not reach the stage of completion. Obviously, a part of austenitic grains transform into
ferrite-cementite mixture, while the other does not transform due to insufficient time. It is
observed that the remaining part of austenite which has not been transformed, undergoes
transformation into martensite on reaching the temperature Ms.

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It is shown by the intersection of the curve V4 and temperature Ms at the point M4. Obviously,
the structure of steel, cooled at the rate of V4, consists partly of troostite and partly of
martensite. This type of structure is common to all steels, which are cooled at a rate faster
than those represented by V3 and slower than by V5. This cooling rate for carbon steels is
achieved by quenching in oil.
We may note that at any cooling rate, higher than V5, e.g. curve V6, of austenite does not
transform into ferrite-cementite mixture. However, the austenite is transformed into
martensite. Point M5 and M6 in given figure represent this transformation. This cooling rate
for carbon steel corresponds to the quenching in water.
We may note that the austenite is never transformed into martensite. This untransformed
austenite is known as retained austenite. The minimum cooling rate, at which all the austenite
is rapidly cooled to temperature Ms and is transformed into martensite is called as critical
cooling rate. It is represented by straight line V5, i.e. the tangent line drawn to the curve 1.
We may see that curves V2 and V3 and others between them have more slope also intersect the
line Ms. Obviously, the martensite is formed at the end of transformation. However, it has
reported that martensite is never formed at such cooling rates. Perhaps, this may be due to the
fact that the curves V2 and V3 and others intersect both the transformation curves. Thus the
complete transformation of the austenite takes place at points b2 and b3 respectively. No
austenite is left in the steel beyond these points. This means that nothing is to be transformed
into martensite. This is why that point M3 in figure has no physical sense.

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