SUBJECT FORENSIC SCIENCE

Paper No. and Title PAPER No. 4: Instrumental Methods and Analysis

Module No. and Title MODULE No. 27: Thermal Analysis

Module Tag FSC_P4_M27

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No. 27: Thermal Analysis
 TABLE OF CONTENTS
1. Learning Outcomes

2. Introduction

3. Components of a thermal analysis system

4. Thermo Gravimetric Analysis (TGA)

5. Differential Thermal Analysis (DTA)

6. Differential Scanning Colorimetery (DSC)

7. Other Techniques

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No. 27: Thermal Analysis
 8. Summary

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No. 27: Thermal Analysis
 1. Learning Outcomes
After studying this module, you shall be able to know about-

 The significance and principle of thermal analytical techniques

 The instrumentation and data analysis of various thermal techniques
 The application of thermal analysis in various fields of science
 The research aptitude by using the concepts of thermal analysis.

2. Introduction
Thermal analysis or TA is a group of analysis which studies the properties of materials when
they change with temperature. The term thermal analysis is associated to the techniques which
involves the measurement of physical parameters as listed while the temperature is changed or
maintained in a controlled and measured manner. The rate of degradation of the material if
measured accurately can help in predicting the properties of the material. Thus in general, it
provides information on the thermally induced processes like decomposition, thermal transitions
etc. These days TA is extensively employed in both industrial and scientific domains. These
techniques can be used to characterize a variety of materials both quantitatively and qualitatively
over a considerable temperature range. The ability of these techniques to characterize,
quantitatively and qualitatively, a huge variety of materials over a considerable temperature
range has been pivotal in their acceptance as analytical techniques. Depending on the physical
property under consideration TA can be distinguished as follow:

Property TA method Abbreviation

Mass Thermogravimetry TGA
(Isobaric mass change determination)
Evolved Gas Detection EGD
Evolved Gas Analysis EGA
Emanation Thermal Analysis ETA
Difference Differential thermal analysis DTA
temperature (Heating or cooling curve determination)

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 Enthalpy Differential scanning calorimetry DSC

Dimensions Thermodiliatometry

Mechanical characteristics Thermochemical measurements

Dynamic thermomechanical measurement
Acoustic characteristic Thermosonimetry
Thermoacoustimetry
Optical characteristic Thermoptometry

Electrical characteristic Thermoelectrometry

Magnetic characteristics Thermomagnetometry

Thermal analysis (TA) is crucial tool which guides us about changes in material properties as
function of temperature. Several different TA methods exist but the focus is on TGA –DTA.
Herein we can combine the two techniques TGA and DTA for a comprehensive study of a
material thermal behavior. While TGA only measures changes caused by mass loss, DTA also
register changes in material where no mass loss occur, e.g. crystal structure changes, melting,
glass transition, etc. Further these techniques can be hybrid with other powerful tools like FTIR
giving well known hyphenated techniques as TGA-FTIR. Another example of such hybrid is
TG-MS (Mass spectrometry). Carefulness required with performance of the experimental
procedure to obtain correct weight loss curves and thermograms (e.g. sample preparation, choice
of crucible, choice of thermal program). The results obtained through such methods are quite
accurate and shows high repeatability factor.

3. Components of a thermal analysis system

The key components of a thermal analysis system can be distinguished as:

i. Sample holder
ii. Furnace
iii. Temperature programmer
iv. Recording system

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 The sample holder assembly comprises of a thermocouple each for the sample and reference,
which is surrounded by a block to make sure an even distribution of heat. The sample is
contained in a small crucible made of materials such as Pyrex, silica, nickel or platinum. The
crucible material depends on the temperature and nature of the tests involved. The direct contact
with the sample and the thermocouples should be avoided to prevent contamination and
degradation. The main requirements of the furnace are that it should supply stable and
sufficiently hot zone. It should also be able to respond promptly to commands from the
temperature programmer. A temperature programmer is crucial in order to obtain constant
heating rates. The recording systems are expected to have low inertia to reproduce variations in
the experimental set up. A schematic representation of TA unit is given in Fig. 1.

Fig.1: Schematic representation of a TA unit

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 4. Thermo Gravimetric Analysis (TGA)

4.1 Principle

In this technique mass of a substance is measured as a function of temperature while it is

subjected to a controlled temperature programme. The resultant is the TG curve or thermo-
gravimetric; time (t) or temperature (T) is plotted on the x-axis or abscissa which increases from
left to right whereas mass is plotted on y-axis or the ordinate which decreases downwards.

Fig. 2 Basic model of TGA

The first thermobalance were build by Kotaro Honda in 1915. With the help of this balance the
first TG curves were obtained for MnSO4·H2O, CaCO3 and CrCO3. The basic principle
underlined here is that as a sample is heated, its mass changes. This change can be utilized to
determine the foremost the composition of a material or its thermal stability, up to 1000 oC. The
sample which is analyzed loses weight as it is heated up which may due to chemical phenomena
like decomposition, reduction, or evaporation. In some cases the sample could also gain weight
due to oxidation or absorption from the atmosphere in which it is analyzed.

A microbalance is used to keep the track of the change of weight of the sample, while
temperature is easily monitored via a thermocouple. Using TGA one can also monitor change in

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 weight as a function of time. Data can be plotted as weight percent or time vs. temperature (oC).
The TGA output curves can be interpreted in a number of ways. If one wants to know the
stoichiometry, of the compound then the molar weight of the component being burned off can be
ascertained based on the weight percent lost and the total molar weight of the material. In the
case of a nonstoichiometric material, the curves can be interpreted by measuring the
decomposition temperature of different components.

4.2 Instrumentation

Fig. 3: Instrumentation of TGA

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 In thermogravimetric analysis the samples are placed in a crucible or shallow dish or basket
which is positioned in a furnace on a quartz beam attached to a recoding balance. The quartz
beam is maintained at null position by the current flowing through the transducer of
electromagnetic balance. The movement of the beam is maintained through the photosensitive
diodes which are position sensitive. Any change in the weight of the sample is detected through
the deflection in beam which is sensed by the photodiodes. The current is proportional to the
change in the weight of the sample. The heating rates are usually 5 to 10°C /min. The amount the
sample ranges from 1 to 300 mg. The computer software allows computation of ∆w/∆t.

5. Differential Thermal Analysis (DTA)

5.1 Principle
A technique in which the temperature difference between a substance and a reference material is
measured as a function of temperature whilst the substance and reference material are subjected
to the same controlled temperature programme. The resultant is the TG curve or thermo-
gravimetric; time (t) or temperature (T) is plotted on the x-axis or abscissa which increases from
left to right whereas mass is plotted on y-axis or the ordinate which decreases downwards. The
term quantitative differential thermal analysis i.e. Quantitative DTA, cover those uses of DTA
where the equipment is designed to produce quantitative results in terms of energy and / or any
other physical parameter. Usually the physical changes like vaporization, sublimation and
absorption are endothermic in nature. The chemical changes like oxidation, polymerization and
catalytic reactions are usually exothermic. Further the orientation of exo and endo varies with the
instrument.

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 Fig. 4: Endothermic and Exothermic orientation

5.2 Instrumentation
In DTA, the furnace contains a block and identically and symmetrical located chambers as
shown in Fig. 5. The sample is placed in one chamber and a reference material such as α – Al2O3
is placed in the other chamber. A Thermocouple is placed in the each chamber in the centre of
the material. The furnace and the sample blocks are then heated by heating element. The
difference in temperature between sample and reference (S & R) thermocouples couples
connected in series is continuously measured. With amplification of high Signal and low noise
the data is collected. Because the thermocouples are placed in direct with the sample, DTA
provides the highest thermometric accuracy of all thermal methods. DTA can be used in
temperature range from ~ 190 - 1600°C.

Although the area DTA peaks are proportional to the heat of the reaction and the mass of the
sample, it is inversely proportional to the sample thermal diffusivity.

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 Fig. 5: DTA instrumentation

6. Differential Scanning Colorimetery (DSC)

6.1 Principle

Differential scanning calorimetry (DSC) is a technique of thermal analysis which looks into the
heat effects associated with phase transitions and chemical reactions as a function of temperature
and is a very informative method in physical characterization of a compound. In Differential
Scanning Calorimetry, the difference in heat flow to the sample and a reference at the same
temperature is recorded as a function of temperature. The reference is an inert material such as
alumina. The temperature of both the sample and reference are increased at a constant
rate. Differential Scanning Calorimeter is at constant pressure, heat flow is equivalent to
enthalpy changes:

(dq/dt) p = dH/dt

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 Here dH/dt is the heat flow measured in mcal/sec. The heat flow difference between the
sample and the reference is:

ΔdH/dt = (dH/dt) sample – (dH/dt) reference

And can be either positive or negative. In an endothermic process, such as most phase
transitions, heat is absorbed and, therefore, heat flow to the sample is higher than that to the
reference. Hence ΔdH/dt is positive.

6.2 Instrumentation

Two modes, power-compensation differential scanning calorimetry (power-compensation DSC)

and heat-flux differential scanning calorimetry (heat-flux DSC), can be distinguished depending
on the method of measurement used. In the former case the temperature difference between the
sample and reference is maintained constant as the sample is scanned. The resulting power
difference is proportional to heat flow. In the latter case temperature difference is allowed to
vary, and the signal is converted to heat flow through the equation:

q = DT/R

Where R= the well-defined thermal resistance of the transducer.

A power compensation instrument can generally heat or cool faster, and provide better resolution
for sharp events, but the signal is inherently less stable as it is comprised of the very small
difference between two very large numbers. As a result, the baseline is less flat and stable, and
the short-term noise is higher. A heat flux instrument cannot achieve the rapid scan rates of a
power compensation design, generally less than 200°C/min. However, the baseline is usually
straighter and more repeatable, providing higher sensitivity for subtle events. [Fig. 6]

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 Fig. 6: (a) Power-compensation differential scanning calorimetry (power-compensation
DSC); (b) heat-flux differential scanning calorimetry (heat-flux DSC).

7. Other Techniques

7.1 Evolved Gas Analysis (EGA)

Fig. 7 Block diagram of Evolved Gas Analysis

The analysis of the purge gas exit stream from DTA, DSC and TGA is useful in establishing
mechanism and stoichiometric relationships of thermal decompositions. In Evolved Gas Analysis
(EGA) the absolute identities of the gaseous components are determine, whereas in evolved
detection the presence only an single preselected components of the evolved gas is sensed .

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 This analysis can be coupled with other techniques like Mass Spectrometer (MS) and Fourier
transform infra-red spectroscopy (FTIR).

7.2 Thermo- Mechanical Analysis (TMA)

TMA provides measurement of penetration, expansion, contraction and extension of materials as
a function of temperature. The probe is attached Linear Variable Differential Transformer
(LVDT) which is further attached to the sample through quartz probe that contains thermocouple
for measurement to sample temperature. Any movement in the sample is detected through the
transformer core and results in output.

Fig. 8: Thermomechanical analyzer

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 7.2.1 Advantages
The advantage include the following –
 Determination of moisture or hydrate water content.
 The stability of the samples under heating and cooling can be studied
 Determination of the drying temperature for gravimetric.
 Each TGA graph is fingerprint of the substance so it can be used for the identification of
binary samples, there stoichiometry.
 The purity of the sample can be checked using these techniques.(melting point check)
 Determination of volatile compounds.

7.2.2 Application
The major applications of thermal analysis are in the

 Corrosion studies (oxidation or reaction with reactive gases)

 Gas absorption and desorption processes can be studied
 Calorimetric titrations in identify the compounds
 Phase transition can be elaborated through them.
 Drug analysis can be done pharmaceutical and polymer industries.
 Cement chemistry, mineralogical research and in environmental studies.

8. Summary

 Thermal analysis plays a vital role in analysis of materials with variation in temperature.

 Several techniques like TGA (Thermo Gravimetric Analysis), DTA (Differential Thermal
Analysis), DSC (Differential Scanning Colorimetery), EGA (Evolved Gas Analysis), DTM
(Dynamic Thermomechanical Measurement) etc. had been a crucial techniques in various
fields.

 The major role of thermal analysis lies in the detection of composition of compounds, their
stoichiometry, and the amount of water molecules present.

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  The temperature variation in instrument is usually done from thermopiles attached. The
sample usually rest on the sample holder with the reference holder in few cases.

 Several hyphenated techniques that are coupling with thermal methods had been improving
the data quality. TGA in combination with Mass spectrometery and FTIR (Fourier transform
infra-red spectroscopy) are few examples of such type.

 The data obtained from such methods are quite effective and accurate. Thermal analysis had
been an important tool in various field of science including corrosion studies, gas absorption
and desorption, phase transition, pharmaceuticals, forensic, calorimetric titration etc.

 This wide scale of applicability had made it an important part of characterization.

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