DIFFERENTIAL THERMAL

ANALYSIS (DTA)

Submitted By: Sarbani Parida

Roll: 25604
Regd. no: 0601105037
Department of Metallurgical & Materials Engg.

1
 INTRODUCTION
Differential thermal analysis (DTA) is a powerful method
that can be used to study the thermal behaviour of materials
and the reactions they undergo.

Differential
thermal analysis (DTA) began soon after the
development of the thermocouple. It has progressed
through the systematic development to produce better
equipment.

Differential-thermal analysis (DTA) is widely used for

investigating the thermodynamics of chemical reactions and
phase transitions.
 HISTORY
The development of differential thermal analysis has
progressed through several stages.
 As early as 1887 le Chatelier described the use of
thermocouple as a difference thermocouple and
published DTA curves of kaolinite. From that time until
Orcel (1935) began the systematic differential thermal
analyses of clays.
 Another stage began with the design of good furnaces,
simple holders, and photographic recording equipment by
Norton (1939) and Hendricks (1939).
 Refinements of this design by Grim and Rowland (1942)
were followed by further developments by Berkelhamer
and Spiel (1944).
 THERMAL ANALYSIS
 Thermal analysis comprises a group of techniques in which a
physical property of a substance is measured as a function of
temperature, while the substance is subjected to a controlled
temperature programme.

 Thermal analysis (TA) offers the ability to evaluate and

compare materials. The information that TA provides
includes:
 Curing kinetics
 Thermal stability (in different environments)
 Oxidative stability
 Purity
 Degree of cure
 Thermal expansion rates (negative and positive)
 DIFFERENTIAL THERMAL ANALYSIS
 In DTA, the material under study and an inert reference are
made to undergo identical thermal cycles, while recording
any temperature difference between sample and reference.
 This differential temperature is then plotted against time, or
against temperature (DTA curve or thermogram).
 Changes in the sample can be either exothermic or
endothermic and are detected relative to the inert
reference.
 A DTA curve provides data on the transformations that have
occurred, such as glass transitions, crystallization, melting
and sublimation.
 The area under a DTA peak is the enthalpy change and is
not affected by the heat capacity of the sample.
Figure-1:Schematic differential thermogram different
types of changes encounter with polymeric material
 Differentialthermal analysis is carried out by heating the
sample together with a reference standard under identical
thermal conditions in the same oven.
 As soon as the sample changes state, crystal form or melts;
the latent heat of phase transition will be absorbed and the
temperature of the sample will lag behind that of the
reference material. In this way any change in state will be
shown and the temperature at which it occurs will be
recorded.
 The reference standard must not suffer any change in state
over the temperature range employed to examine the
sample.
 Alumina and silicon carbide are satisfactory reference
standards for solids whereas silicone oils have been used as
standards for liquids.
 The sample and the reference standard are placed in containers
situated in two cavities contained in a high thermal capacity block.
 Thermocouples are situated in the sample and the reference
materials and are connected so that only a temperature difference
between the two will be recorded.
 An alternative method is also used to avoid the thermal lag
resulting from the time required for the heat transfer to the
materials and then to the thermocouples.

Figure-2. The Basic Figure-3. An Alternative

Differential Thermal Analysis Differential Thermal Analysis
Apparatus Apparatus
 Features of DTA
 Temperature range : -150°C up to +2400°C
 Low heat capacity measuring head
 Different furnaces available : -150°C up to +2400°C
 Vacuum up to 105 Mbar
 Static and dynamic gas atmospheres
 The shape of a DTA peak depends on sample weight
and the heating rate used
 APPARATUS USED
 There are fundamentally four essential parts:
(1) Specimen holder,
(2) Furnace,
(3) Rate of heating controller, and
(4) Differential thermocouple recorder.

Figure-3.Schematic
Illustration of a DTA cell
 INTERPRETATION OF DATA
 Peaks corresponds to the evolution or absorption of heat.
 The onset of the DTA peak gives the start temperature.
 The apparatus is calibrated with materials of precisely
known melting points.
 The peak area (A) is related to enthalpy changes in the test
sample and is enclosed between the peak and the
interpolated baseline.

where,
m is the sample mass,
q is the enthalpy change per unit mass,
g is the shape factor
K is the thermal conductivity of sample
 APPLICATION OF DTA
 Used as a finger print for identification purposes of phase
diagrams.
 Widely used in the pharmaceutical and food industries.
 Used in cement industry, mineralogical research and in
environmental studies.
 Used to date bone remains or to study archaeological
materials.
 Used for investigation of plant material.
 Used to determine the curing temperature range of a
fluoroelastomer compound.
 Helps in determining the melting, boiling, and decomposition
points of organic compounds.
 Also, applied to the study and characterization of polymeric
material.
 EXAMPLE
Figure-5.
Differential
thermogram of
CaC2O4.H2O in
the presence
of O2

 The two minima indicate that the sample becomes cooler

than the reference material as a consequence of the heat
absorbed by two endothermic processes.
 The single maxima indicates that the reaction to give calcium
carbonate and carbon dioxide is exothermic.
ADVANTAGES:
• In this method, any type of reactions occurring in any type
of material, such as organic, inorganic, polymer, etc. can be
detected.
• The apparatus used is simple and easy to handle.

LIMITATIONS:
• System errors of less than one Kelvin is difficult to achieve.
• Reference material should be carefully chosen so that its
temperature doesn't changes during the process.
• At elevated temperature, there is no guarantee of accuracy
of thermocouple.
 CONCLUSION
 DTA has progressed through the systematic development
of equipment and cataloguing the typical DTA curves for a
variety of materials.

 DTA is widely used in chemical and material sciences;

pharmaceutical and food industries; for investigation of
plant material; in determining the melting, boiling, and
decomposition points of organic compounds; and for
characterization of polymeric material.
 REFERENCE
 Chiu, J . Ed_ Polymer Characterization by Thermal Methods
of Analysis. Marcel Dekker, New York (1974).
 Griffin, W.R . Thermal Analysis (Eds) Kambe, H . and Gare,
P.D. John Wiley, New York (1974).
 Barrall, E M. and L. B. Rogers (1962) Differential thermal
analysis of organic compounds. Anal Chem., 34, 1106-llll.
 Mackenzie, R. C. (1970) Differential Thermal Analysis, Vol. I
Academic Press, London, p. 616, I 109, 11 10.
 Zuberi,Z. H. and O. C. Kopp (1976) Differential reaction
analysis (DRA)-a technique for obtaining differential thermal
analysis data from inert substances Am Mineral.. 61.281-286.
 J. A. Pask and M. F. Warner, Differential thermal analysis
methods and techniques, Bui. Am. Ceram. Soc. 33, 168-175
(1954).
 H. T. Smyth, Temperature distribution during mineral inversion
and its significance in differential thermal analysis, J. Am.
Ceram. Soc. 34, 221-224 (1951).