Thermal Characterization of Materials.

Introduction:
Thermal characterization is a study in which physical and chemical property of a material is
measured by controlled temperature program. The changes in the properties of the material
during heating/cooling could result from purely physical phenomena such as melting,
vaporization or polymorphic transformations or chemical processes such as thermal
decompositions of materials, oxidation of metals and alloys, reduction of solid metal oxides, etc.

Different techniques are used for thermal characterization of materials. Some of important
techniques are:
1. Differential Scanning Calorimeter (DSC)
2. Thermos Gravimetric Analysis (TGA)
3. Differential Thermal Analysis (DTA)

1-Differential Scanning Calorimeter (DSC)

Principle
A thermo analytical technique in which difference in amount of heat, required to increase the
temperature of sample and reference, are measured as a function of temperature.
The result of DSC experiment is a curve of heat flux vs temperature (or time).

Working
The sample is placed in a suitable pan and sits upon a constantan disc on a platform in the DSC
analysis cell with a thermocouple underneath. A thermocouple under the constantan disc
measures the sample temperature. An empty reference pan sits on a symmetric platform with its
own underlying thermocouple. Heat flow is measured by comparing the difference in
temperature across the sample and the reference chromel wafers.
Information obtained from DSC (for Polymers)

 Glass transition temperature (Tg) of polymers , the temperature below which polymer is
hard, brittle & above it is soft, rubber like)
 Crystallization (ordered structure)
 Thermal reactions in polymers
 Type of polymer (it tells the type of polymer i.e. thermoplastic or thermosetting but it
doesn’t tell which polymer is whether it is PVC, PU etc.)

DSC Curve Interpretation

Two types of curves/signals can be obtained:

1. Step change
2. Peak

Step Change
A step change curve is shown in figure below with Tg.
Glass Transition Temperature (Tg) is the point at which a material alters state – going from a
glass-like rigid solid to a more flexible, rubbery material.

Two things can happen with the curve either change of location of Tg or change in size of Tg.
From the Size of curv the amount of change of amorphous materials can be indicated
Larger the step size means larger will be the amorphous materials vice versa.

A material with Lower Tg mean having easy transformation comapred with the one having
higher Tg value
A step change curve gives information about:

1. Shift of Tg
On the basis of Tg we can differentiate between two materials.
Larger the Tg mean more difficult is the material to transform. Tg2> Tg1
Figure below shows shift of Tg.

2 Shape change
Curves indicate Shape change at constant Tg

Larger the step means more will be amorphous material. Solid

curve is having more amorphous material than the dotted one.
Peaks
Two types of peaks can be be obtain in
DSC curves.

 Exothermic peak (heat evolved

by the sample)
 Endothermic Peak (heat absorb
by the sample)

Exothermic peaks
Exothermic peaks gives two types of information
i. Crystallization
During crystalization disordered stucture becomes ordred and heat is released.
ii. Thermal reaction (not involve melting)
Q- How can one differentiate between crystalization and a thermal reaction ?

Ans. An exothermic peak followed by an endothermic peak in a DSC curve is an indication of

crytallization. Because endothermic peak is an indication of melting of crytals. Absence of
endothermic peaks after exothermic peak is an indication of a thermal reaction. A DSC curve
below confirms crystallization process.
Endothermic Peaks
Phase change is indicated by endothermic peaks e.g. solid to liquid, crystaline to amorphous,
liquid to vapour.

 Area under the curve gives amount of heat released or absorbed.

Multiple Peaks
A DSC curve below shows multiple peaks (which means different morphologies)

Curve shows two phases, one at low temperature and the other at high temperature.

DSC Curve indicate either morphologies of one polmer at different temperatures or two
different kind of polmers.e.g A polymer blend

Confirmation of presence of different mophologies or different polmers. If the second run(dotted

line) re-trace the same curve it means two materials with different morphologies

Another multiple peaks curve shows below

On second run if second dotted peak increased in its area then it means that all crystallizes in
one stable condition.
It indicates one material with two different morphologies.

 The technique is very useful for polymer and pharmaceutical industries.

2-Thermogravimetric analysis (TGA)

Principle
TGA is a therml analysis process in which changes in physical and chemical properties of
materials are studied as a fuction of temperature or time.

Simply it measures changes in mass of sample as a fuction of temperature or time in a controlled

invironment.

Working
The thermogravimetric analysis
instrument usually consists of a
high-precision balance and sample
pan. The pan holds the sample
material and is located in a furnace
that is heated or cooled during the
experiment.
A thermocouple is used to
accurately control and measure the
temperature within the oven. The
mass of the sample is constantly
monitored during the analysis. An inert or reactive gas may be used to purge and control the
environment.

The analysis is performed by gradually raising the temperature and plotting the substances
weight against temperature. A computer is utilized to control the instrument and to process the
output curves (temperature vs. weight). As shown below.
Prperties Determine by TGA involves:
Thermogravimetric analysis (TGA) is a reliable method to determine endotherms, exotherms,
measure oxidation processes, thermal stability, decomposition points of explosives,
characteristics of polymers, solvent residues, the level of organic and inorganic components of a
mixture, degradation temperatures of a material, and the absorbed moisture content of materials.

Materials Characterized by TGA involves

Petroleum, chemicals, biological samples, polymers, composites, plastics, adhesives, coatings,
organic materials, and pharmaceuticals.

Differential Thermal Analysis (DTA)

Principle
The basic principle is that the temperature difference between the test sample and the innert
reference under controlled and identical condition of heating or cooling is recorded continously
as a fuction of temperature or time.

Working
The test sample and the innert reference materials are placed in two containers in the furnace.
Thermocouples are connected to each of the container material to measure the heat changes.
Now as the heat is supplied under regulated condition, the innert reference will not go under any
change but the test sample undergo various physical and chemical transformations, its
temperature changes significantly (due to change in enthalpy) with respect to the reference and
the temperature difference is recorded.

Prperties Determine by DTA involves:

Decomposition or volatilization,melting, crytallization, changes in solid crystal phases,
homogenious reaction in solid state. The main use of DTA is to detect thermal processes and
characterized them as exothermic or endothermic.

 The technique is very useful for metals, composites and ceramics.