Thermal Analysis

Thermal analysis (TA) is a group of analytical techniques that measure properties

or property changes of materials as a function of temperature.

Temperature can change the following properties of materials:

-dimension, mass, phase, and mechanical behavior.

TA methods are relatively simple because changing the temperature of a sample is

less complicated than probing a sample using high-energy X-ray, electron or ion
beams in techniques of spectroscopy. Many TA methods have been developed for
a variety of examination purposes.
Common Characteristics

Thermal Events
TA relies on material reactions to thermal energy flow in or out of solids. Such
reactions are referred to as thermal events.

At absolute zero, a solid does not have any thermal energy, and it means that its atoms
are static: there is no vibration or rotation of atomic bonds. With increasing
temperature, thermal energy gains in the solid will increase vibrations and rotations of
atomic bonds. When the amplitudes of vibrations reach a certain level, the following
changes in the solid may occur if the solid is in an inert atmosphere:
-solid-phase transformation,
-glass transition,
-melting,
-sublimation, and
-thermal decomposition.
 Solid-phase transformation may occur for solids that have different equilibrium crystalline
phases in different temperature ranges. Example: Pure Fe

 Glass transition occurs in noncrystalline solids. With increasing temperature, a rigid

noncrystalline solid in a glass phase may change to a rubber-like solid. The glass transition is
referred to as a second-order phase transition. The glass transition is an important property of
polymeric materials.

 Melting is simply the phase transformation from solid to liquid, and sublimation is the phase
transformation from solid to gas.

 Thermal decomposition is referred to as a change in a solid containing more than one type of
atom or molecule. For example, solid CaCO3 will decompose to form solid CaO and gaseous

CO2 over a certain temperature range.

Enthalpy Change
Enthalpy is the thermodynamic parameter that is useful for describing the thermal events of a
material under constant pressure, for example, 1 atm. The meaning of enthalpy and enthalpy
change is express by the first law of thermodynamics.

If the work is mechanical work of volume change in the system under constant pressure, then
the first law should be written as follows

QP represents the heat required for internal energy change under constant pressure.
Enthalpy is defined as H.

Thus, under constant pressure, the enthalpy change will be written

or

we can conclude

Thus, the heat flowing in or out of a system under constant pressure is equal to its
enthalpy change.
Instrumentation

All TA techniques have certain features in common in their instrumentation: -a

furnace in which a sample is heated (or cooled) with a controllable environment
and
-a transducer by which the property changes in materials are monitored.

The sample is analyzed under a designed temperature profile (a constant heating rate,
a modulated heating rate (for example, a sinusoidal heating curve), or even an
isothermal profile.

The measurements are displayed as TA curves (peaks, discontinuities, and slope

changes) which are related to thermal events.
Figure 10.1 General instrumentation for thermal analysis.
Experimental Parameters
TA results can be significantly affected by experimental parameters such as
-sample dimension and mass,
-heating (or cooling) rates, atmosphere surrounding the sample, and
-thermal and mechanical history of the sample.

Reproducible results of a chemical species may not be obtained when the instrumental and
experimental parameters are not identical. The main reason for this is that TA is highly sensitive
to heat-transfer conditions and to accuracy of temperature measurements. The following
considerations can help ensure reliable TA data.
1. Sample dimension and mass should be small (sample mass less than 10 mg are
preferred).
2. Samples to be analyzed should have the same thermal and mechanical history.
3. A slow heating rate is often favorable in order to approach thermal equilibrium
during TA.
4. The atmosphere surrounding the sample serves to transfer heat and supply
or remove gaseous reactants or products. In most TA methods, we need an
inert atmosphere to prevent the sample from oxidation reactions.
 Answer the following questions within 05 minutes

1. List the properties that can be changed by temperature. 2

2. What is thermal events? 2

3. What type of considerations are required to obtain reliable
thermal analysis data.
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