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DIFFERENTIAL SCANNING CALORIMETRY

Introduction:
DSC is a technique which is part of a group of techniques called Thermal Analysis (TA). Thermal Analysis is based upon the detection of changes in the heat content (enthalpy) or the specific heat of a sample with temperature. As thermal energy is supplied to the sample its enthalpy increases and its temperature rises by an amount determined, for a given energy input, by the specific heat of the sample. The specific heat of a material changes slowly with temperature in a particular physical state, but alters discontinuously at a change of state. As well as increasing the sample temperature, the supply of thermal energy may induce physical or chemical processes in the sample, e.g. melting or decomposition, accompanied by a change in enthalpy, the latent heat of fusion, heat of reaction etc. Such enthalpy changes may be detected by thermal analysis and related to the processes occurring in the sample.

Principle;
DSC, differs fundamentally from DTA in that the sample and reference are both maintained at the temperature predetermined by the programme even during a thermal event in the sample. The amount of energy which has to be supplied to or withdrawn from the sample to maintain zero temperature differential between the sample and the reference is the experimental parameter displayed as the ordinate of the thermal analysis curve . The sample and reference are placed in identical environments, metal pans on individual bases each of which contain a platinum resistance thermometer (or thermocouple) and a heater. The temperatures of the two thermometers are compared, and the electrical power supplied to each heater adjusted so that the temperatures of both the sample and the reference remain equal to the programmed temperature, i.e. any temperature difference which would result from a thermal event in the sample is 'nulled'. The ordinate signal, the rate of energy absorption by the sample (e.g. millicalories/sec.), is proportional to the specific heat of the sample since the specific heat at any temperature determines the amount of thermal energy necessary to change the sample temperature by a given amount. Any transition accompanied by a change in specific heat produces a discontinuity in the power signal, and exothermic or endothermic enthalpy changes give peaks whose areas are proportional to the total enthalpy change.

In other words, in DSC, the measuring principle is to compare the rate of heat flow to the sample and to an inert material which are heated or cooled at the same rate. Changes in the sample that are associated with absorption or evolution of heat cause a change in the differential heat flow which is then recorded as a peak. The area under the peak is directly proportional to the enthalpic change and its direction indicates whether the thermal event is endothermic or exothermic. DSC Curves:The result of a DSC experiment is a curve of heat flux versus temperature or versus time. There are two different conventions: exothermic reactions in the sample shown with a positive or negative peak, depending on the kind of technology used in the experiment. This curve can be used to calculate enthalpies of transitions. This is done by integrating the peak corresponding to a given transition. It can be shown that the enthalpy of transition can be expressed using the following equation: where is the enthalpy of transition, is the calorimetric constant, and is the area under the curve. The calorimetric constant will vary from instrument to instrument, and can be determined by analyzing a well-characterized sample with known enthalpies of transition. Applications:Differential scanning calorimetry can be used to measure a number of characteristic properties of a sample. Using this technique it is possible to observe fusion and crystallization events as well as glass transition temperatures Tg. DSC can also be used to study oxidation, as well as other chemical reactions. Glass transitions may occur as the temperature of an amorphous solid is increased. These transitions appear as a step in the baseline of the recorded DSC signal. This is due to the sample undergoing a change in heat capacity; no formal phase change occurs.

As the temperature increases, an amorphous solid will become less viscous. At some point the molecules may obtain enough freedom of motion to spontaneously arrange themselves into a crystalline form. This is known as the crystallization temperature (Tc). This transition from amorphous solid to crystalline solid is an exothermic process, and results in a peak in the DSC signal. As the temperature increases the sample eventually reaches its melting temperature (Tm). The melting process results in an endothermic peak in the DSC curve. The ability to determine transition temperatures and enthalpies makes DSC a valuable tool in producing phase diagrams for various chemical systems. The technique is widely used across a range of applications, both as a routine quality test and as a research tool. The equipment is easy to calibrate, using low melting indium at 156.5985 C for example, and is a rapid and reliable method of thermal analysis. ***

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