DTA/TGA-Based Methods

Alexander S. Mukasyan

Thermal analysis (TA) refers to a group of techniques that studies the properties of mate-
rials as they change with temperature [1]. Thermal analysis allows one to obtain a variety
of properties in many compounds and reactive systems, including enthalpy, thermal
capacity, mass changes, and the coefficient of heat expansion. Solid-state chemistry uses
TA for studying reactions in the solid state, thermal degradation reactions, phase transi-
tions, and phase diagrams. TA involves several methods that are distinguished by the
measured property. The methods are thermogravimetric analysis (TGA), differential
thermal analysis (DTA), differential scanning calorimetry (DSC), pressurized TGA, ther-
malmechanical analysis, dilatometry, and evolved gas analysis (EGA). Often different
properties can be measured at the same time: TGA/DTA, TGA/EGA.
The TGA measures changes in weight in relation to changes in temperature. The
measured weight loss curve may give information on changes in sample composition,
its thermal stability, and kinetic parameters for chemical reactions. In DTA, the material
under study and an inert reference are made to undergo identical thermal cycles, while
recording any temperature difference between the sample and reference. The pheno-
mena that may cause changes in heat include physical adsorption and desorption, a
change in crystal structure, crystallization, melting, vaporization, sublimation, chemi-
sorption, gas-solid reactions, and solid-state reactions. DSC shares much in common
with DTA, except that DSC measures the difference in heat, which is needed to flow
to the sample as compared to the reference to maintain both at the same temperature.
TGA/DTA/DSC methods are widely used to investigate the combustion synthesis
reactions. Several issues can be addressed: (i) to study the characteristic temperatures
(e.g., melting point, dissociation, decomposition) of the initial precursors; (ii) to find
the onset temperatures for the reaction; (iii) to measure the heat released during the
SC process; and (iv) to investigate the kinetics of the chemical reaction. TGA/DTA data
on initial precursors can be found in almost all publications with material related to the
solution combustion synthesis. For example, based on TGA/DTA data analysis, it was dem-
onstrated that, in many such systems, onset reaction temperature is related to the decom-
position temperatures of the fuel or oxidizer [2,3]. Another example of using TGA/DSC
methods to analyze reactions in gas-solid system is shown in Fig. 1 [4]. Analysis of such
data allows the authors to explain why the degree of nitridation, as well as the reaction

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94 Concise Encyclopedia of Self-Propagating High-Temperature Synthesis

140 4

1
2
130

2 0

Heat flow (W/g)

120 3
–2
Mass (%)

1409 °C
1043 °C
1260 °C
1356 °C 4 –4
110
110.2%
–6
100
1380 °C
–8
1215 °C
1211 °C
90 –10

800 900 1000 1100 1200 1300 1400 1500 1600

Temperature (°C)
Fig. 1 TG (1, 4) and DSC (2, 3) curves of complex thermal analysis of ferro-silicon powder (1, 2) and
powder of ferro-silicon with 30% ilmenite added (4, 3) in nitrogen.

rate, is lower for a ferro-silicon/ilmenite powder mixture (curve 2,4) than for ferro-
silicon (curve 1,3).
A special task is obtaining kinetic data based on DTA/DSC data analysis, where an iso-
conversional approach is typically used [5]. The principal idea of the isoconversional method
is based on two main assumptions: (i) rate of the processes is defined as a product of two
independent functions, one of temperature the other of degree of conversion; (ii) The effec-
tive activation energy is obtained based on a set of kinetic trials from the dependences
temperature vs heating rate, β, for incremental methods with linear heating rate. For exam-
ple, for the Kissinger-Akahira-Sunose (KAS) method [6] the following relation can be
obtained:
β k0 R E a, η
ln 2 ¼ ln
T ðηÞ Ea, η gðηÞ RT ðηÞ

Thus, for a constant degree of conversion, η, a plot of ln(β/T2(η)) vs 1/T(η) obtained from
thermal curves recorded at several heating rates is a straight line, and its slope allows for
evaluation of the apparent activation energy of the reaction, whereas the intercept allows
the value of the preexponential factor to be obtained. This method has been widely used to
obtain the effective activation energies for a variety of CS reactions [3,7–9].
 DTA/TGA-Based Methods 95

REFERENCES
[1] Gabbott, editor. Thermal analysis: principle and applications. Oxford: Blackwell Publishing; 2008.
[2] Deshpande K, Mukasyan AS, Varma A. Chem Mater 2004;16(24):4896–904.
[3] Kumar A, Wolf EE, Mukasyan AS. AIChE J 2011;57(8):2207–14.
[4] Chukhlomina LN, Vitushkina OG, Vereshchagin VI. Glas Ceram 2011;67:9–10.
[5] Šimon P. J Therm Anal Calorim 2004;76:123–32.
[6] Kissinger HE. Anal Chem 1957;29:1702.
[7] González-Cortes SL, Imbert FE. Appl Catal A Gen 2013;452:117–31.
[8] White J, Reeves RV, Son SF, Mukasyan AS. J Phys Chem A 2009;113:13541–7.
[9] Horvitz D, Klinger L, Gotman I. Scr Mater 2004;50:631–4.