Thermal Analysis DTA & DSC

Dr. Prafulla Kumar Sahu M.Pharm., Ph.D.

Raghu College of Pharmacy, Visakhapatnam.

Thermal analysis
Thermal analysis includes a group of techniques in which specific physical properties of a material are measured as a function of temperature. The techniques include the measurement of temperatures at which changes may occur, the measurement of the energy absorbed (endothermic transition) or evolved (exothermic transition) during a phase transition or a chemical reaction, and the assessment of physical changes resulting from changes in temperature.

Introduction
Examples of properties:
Heat-related phase changes and degradations, crystallizations, heat capacities, heats of reaction, glass transitions, curing rates for adhesives, and weight changes.

The properties are observed either by monitoring temperature or heat flow in and out of the sample or by monitoring the sample weight during the process.

Classification
Differential thermal analysis (DTA) is a technique in which the temperature difference between the sample tested and a reference material is measured while both are subjected to the controlled temperature program. Differential scanning calorimetry (DSC) is a technique in which the heat flow difference between the sample and reference material is monitored while both are subjected to the controlled temperature program. Thermogravimetric analysis (TGA) is a technique in which the weight of a sample is monitored during the controlled temperature program. Thermomechanical analysis (TMA) Dynamic mechanical analysis Enthalpimetric analysis Thermometry

Trends
Various environments (vacuum, inert, or controlled gas composition) and heating rates from 0.1 to 500C/min are available for temperatures ranging from 190 to 1400C. The analysis of gas(es) released by the specimen as a function of temperature is possible when thermal analysis equipment is coupled with Fourier-transform infrared detection or with a mass spectrometer.

Applications
Environmental measurements: vapor pressure,
thermal stability, flammability, softening temperatures, and boiling points.

Compositional analysis: phase diagrams, free

versus bound water, solvent retention, additive analysis, mineral characterization, and polymer system analysis.

Important area of product reliability: heat-capacity

data, liquid-crystal transitions, solid fat index, purity, polymer cures, polymer quality control, glass transitions, Curie point, and fiber properties.

Applications
Information on stability: modulus changes, creep studies, expansion coefficients, and antioxidant evaluation. Dynamic properties of materials: visco-elastic measurements, impact resistance, cure characteristics, elastic modulus, loss modulus, and shear modulus. Chemical reactions: heats of transition, reaction kinetics, catalyst evaluation, metal gas reactions, and crystallization phenomena.

DTA & DSC

Principles
Both of these methods relate to the monitoring of the heat absorbed or evolved during the heating of a sample and a reference in equivalent environments. Differential thermal analysis (DTA) monitors temperature difference, while differential scanning calorimetry (DSC) measures the power supplied.

 If an inert sample, such as alumina, is heated at a constant rate of 10C min1, the temperature-against-time curve is practically a straight line. A sample that reacts or melts within the temperature range studied will give small changes on its temperature-time curve. By heating both a reactive sample and an inert reference together at the same rate, these small differences may be detected and amplified as a function of temperature. Example: If 10 mg of metallic indium are heated as sample and a similar amount of alumina as reference, both heat at nearly the same rate until around 156C the indium starts to melt. This absorbs energy and the temperature of the indium rises less fast. This goes on until all the indium has melted when the temperatures of the liquid indium and alumina again rise at the same rate.

 Two alternative strategies can now be adopted.

Differential thermal analysis or DTA strategy Power-compensated DSC strategy

DTA strategy
If the temperatures of sample S and reference R are measured and the temperature difference recorded: DTA strategy T = TS TR A downward peak (i.e. a minimum) is recorded. Under carefully controlled instrumental conditions, this may be related to the enthalpy change for the thermal event:

Where, A is the area of the temperature-time peak from initial (i) to final ( f ) point. This leads to quantitative or heat-flux differential scanning calorimetry (heat-flux DSC). The negative sign is required since the enthalpy change on melting is positive, but T for melting is negative.

Power-compensated DSC strategy

The second strategy is to control the amount of heat supplied to sample and reference so that their temperatures stay as nearly the same as possible. Using separate heaters for sample and reference allows measurement of the difference in power P to be measured. With proper control and calibration, this will give the enthalpy change of the peak directly:

 A reference material that does not melt in the temperature range. Its temperature would match the temperature of the surroundings (TE) for the entire temperature program. Consider plotting the difference (T = TS TR) between the temperature of the sample (TS) and the temperature of the reference material (TR) vs. the temperature of the surroundings. Initially, there would be no difference, T = 0, since the sample and surroundings are heated equally. However, when the sample melts, TS lags behind TR temporarily, making T negative. After melting is complete, the sample catches up such that the two temperatures are again equal, T = 0. A plot of T vs. TE then results a negative peak in the DTA curve when the sample melts.

DTA curve of the endothermic process

Endothermic curve
The negative peak shown is a result of an endothermic process (a process that absorbs heat) such as melting. Other endothermic processes, other than melting, would also produce a negative peak. Examples: a chemical reaction or a decomposition. The particular characteristics of this peak (shape, width, sharpness, smoothness, etc.) provide clues concerning the sample composition and properties that are the object of a DTA.

Exothermic curve
DTA curve of the exothermic process

Exothermic processes (processes that evolve heat) may also occur during the experiment. This would produce a surge in the sample temperature, it would produce a positive peak in the T vs. TE plot. Exothermic processes include crystallization as well as some chemical and decomposition reactions.

DTA curve of kaolinite

Schematic diagram of DTA or DSC apparatus ( represents either the temperature or

Instrumentation
The temperature, both for the sample and the reference and also the furnace is measured by thermocouples, or resistance sensors. Higher sensitivity and greater stability are obtained if multiple sensors of inert material are used.

Factors influencing thermal analysis

The sample is generally about 10 mg of powder, fibers or reactants such as monomers for plastic production. These are placed into the crucible, which should be unreactive and stable over the temperature range used. Platinum, silica, aluminum, or alumina crucibles are commonly used. The sample and reference pans (either with alumina powder or sometimes an empty pan) are placed in their holders within the furnace, generally a wire-wound electrical heater controlled by the computer program. The rate of heating is user-determined, often about 10 K min1, but for the best approach to equilibrium, low heating rates are needed, and isothermal experiments may also be carried out. High heating rates save time, and can simulate situations like burning.

 The atmosphere surrounding the samples can be controlled. A slow flow of nitrogen gas will give an almost inert atmosphere and sweep away harmful products. Oxygen may be used to study the oxidative stability of polymers. Carbon dioxide will react with some oxides to form carbonates. The mass of the sample, together with its volume and packing is important since these determine the heat transfer and the diffusion of gases across the sample.

Applications
Unlike other thermal methods, DTA and DSC are not compound-specific, they are still most important test methods for a wide variety of disciplines and materials. Inorganic materials, salts and complexes : physical properties, chemical changes and qualitative thermal behavior. Minerals and fuel (coal and oil) New materials (e.g. liquid crystals) are discovered, DSC is frequently used to test. The greatest use is in the pharmaceutical and polymer industries.

Applications
One special use of DSC for physical changes is the determination of purity. While a pure substance melts sharply, perhaps over a few tenths of a degree near its true melting point, an impure sample may start to melt several degrees below this temperature, and will give a broad peak. Computer analysis of the shape of this peak allows an estimation of purity, but does not provide any information on the nature of the impurities.

Applications
Many studies of inorganic complexes, of polymer degradations and reactions between samples and reactive gases. Oxidation of polyethene is tested by heating samples in oxygen or holding them isothermally at around 200C and then changing the surrounding atmosphere to oxygen and noting the time at which oxidative reaction starts. This is a most useful test for blue polyethene water pipes.