Differential Thermal Analysis (DTA)

• Introduction:
The principle of the DTA technique resumes to heating (or cooling) a test sample (S) and
an inert reference (R) under identical conditions while measuring the temperature
difference DT between S and R.
The differential temperature DT is then plotted against time or against temperature.
Chemical, physical, structural and micro structural changes in the sample S lead to the
absorption (endothermal event) or evolution of heat (exothermal event) relative to R. If
the response of two inert samples submitted to an applied heat-treatment program is not
identical, differential temperatures DT arise as well. Therefore, DTA can also be used to
study thermal properties and phase changes which do not necessarily lead to a change in
enthalpy.
The baseline of the DTA curve exhibits discontinuities at transition temperatures and the
slope of the curve at any point will depend on the micro structural constitution at that
temperature. The area under a DTA peak can be related to the enthalpy change and is not
affected by the heat capacity of the sample.
• DTA Instruments:
The basic components of a differential thermal analysis (DTA) cell are shown in Fig.1.

Schematic illustration of a DTA cell.

The sample environment consists of a ceramic (or metallic) block to ensure an uniform
heat distribution, specimen crucibles and thermocouples (for the sample and reference).
Metallic blocks are less likely to cause baseline drifts compared with porous ceramics,
but the DTA signal is smaller, due to the higher thermal conductivity of metals.

The samples are placed in Pyrex, silica, Ni or Pt crucibles (according to the temperature
program and purpose of the experiment). Thermocouples should not be placed in direct
contact with the sample to avoid contamination and degradation, even though sensitivity
may be compromised. The sample assembly is isolated against electrical interference
with the wiring of the oven with an earthed metallic or Pt-coated ceramic sheath.
For heating experiments up to about 500°C, an uniform transfer of heat away from the
sample may be difficult. Disc-shaped thermocouples must then be used to ensure
optimum thermal contact with the bottom-side of the sample container (Al or Pt foil). The
furnace should provide a stable, large enough hot-area and a fast response to the
temperature-controller commands. Data acquisition and/or the real-time display is
handled by a computer system or an analog device (plotter).

Experimental details: potential sources of error.

Experimental parameters such as specimen environment, chemical composition, size,
surface-to-volume ratio must carefully be selected, since they might modify for example
the thermal decomposition of powder materials even though their solid-state phase
transitions are not affected. The packing state of powder samples is important in these
thermal decomposition reactions and may lead to significant differences in thermal
behavior between otherwise identical samples. Moreover, DTA measurements on powder
materials do not always correctly illustrate the thermal behaviour of bulk specimens, for
which most phase transitions will also exhibit the influence of built-in strain energy.
The heat flow rate may sometimes saturate the response capability of the DTA system. It
is then advisable to dilute the specimen with a thermally-inert material. For the detection
of phase transition temperatures, one must also check that the peak temperature.
Application of DTA:
• It is used to determine the influence of the thermal history on the degree of
vitrification in the system CaO-MgO-SiO2.
• Differential Thermal Analysis is used in the investigation of thermoplastics.