Power-compensated DSC instruments

The power compensation DSC instrument was first described by Watson et al.3) and by O Neill4) and it was developed into a commercial instrument by the Perkin-Elmer Corporation. It utilises separate sample and reference holders of low thermal mass, with individual heaters and platinum thermometers, as shown schematically in Fig. 1. In addidion to controlling the average temperature the instrument employs a... 

DTA as well as power compensation DSC instruments, and is called temperature modulated DSC, or TMDSC. The following trade marks are used by different TA instrument manufacturers for their temperature modulated differential scanning calorimeters Modulated DSC (MDSC ) of TA Instruments Inc., Oscillating DSC (ODSC ) of Seiko Instruments Inc., Alternating DSC (ADSC ) of Mettler-Toledo Inc. and Dynamic DSC (DDSC ) of Perkin-Elmer Corp. 

In T.MDSC, a perturbation in the form of an oscillating sine wave of known frequency is applied to the linear temperature control program. This variation can be applied in principle to heat-flux DSC and to power compensation DSC instruments. The thermal response is analyzed using Fourier transformation, with the component in-phase with the temperature oscillation thought to be caused by reversible or equilibrium changes in the sample, and the out-of-phase component associated with non-reversible changes. 

Mg. 2. A schematic representation of a power compensation DSC instrument and its operation (7). 

C and 80 C is of special interest melting enthalpies are between 100 and 200 J/g. In the context of quality control, such calorimetric curves can be used as fingerprints for the considered fats. As examples. Figs. 2 and 3 present the thermal polymorphism of two glycerides, distearin and tristearin, as displayed by a power compensation DSC instrument. 

Most commonly used DSC instruments fall into two categories (Laye, 2002) power compensation (PC) instruments, for which the term DSC was coined when this type became available in 1963 (Wendlandt, 1974), and heat flux (HF) instruments (Figure 22.2). The latter are essentially quantitative DTA instruments classical DTA is a qualitative, or at best semi-quantita-tive, technique (Wright, 1984). 

Two principal DSC designs are commercially available—power compensated DSC and heat flux DSC. The two instruments provide the same information but are fundamentally different. Power-compensated DSCs heat the sample and reference material in separate furnaces while their temperatures are kept equal to one another (Fig. IB). The difference in power required to compensate for equal temperature readings in both sample and reference pans are recorded as a function of sample temperature. Heat flux DSCs measure the difference in heat flow into the sample and reference, as the temperature is changed. The differential heat flow to the sample and reference is monitored by chromel/ constantan area thermocouples (Fig. IC). ... 

Fig. 1 Schematic diagrams of the (A) differential thermal analysis (DTA) (B) power-compensated DSC and (C) heat-flux DSC cells. (From Ref adapted from DuPont Instruments Systems Brochure.)...

Manufacturers use two methods of measurements. In the first method called heat flux DSC, the instrument measures this temperature difference (DTA). Through calibration, this temperature difference is transformed into a heat flow, dq/dt. Therefore, there is a thermal factor that may vary with temperature. In the second method, called power compensation DSC, two individual heaters are used in order to monitor the individual heating rates of the two individual ovens. A system controls the temperature difference between sample and reference. If any temperature difference is detected, the individual heatings are corrected in such a way that the temperature is kept the same in both pans. That is, when an endothermic or exothermic process occurs, the instrument delivers the compensation energy in order to maintain equal temperature in both pans. 

Figure 10.4 Differential scanning calorimetry (DSC) instrumentation design (a) heat flux DSC and (b) power compensation DSC. A, furnace B, separate heaters and C, sample and reference holders. (Reproduced with permission from E.L. Charsley and S.B. Warrington, Thermal Analysis Techniques and Applications, Royal Society of Chemistry, Cambridge, UK. 1992 Royal Society of Chemistry.)...

This is one of the most frequently used methods to study solid-state properties. The flux t5q)e DSC involves heating the sample and reference samples at a constant rate using thermocouples, to determine how much heat is flowing into each sample and thus finding the differences between the two. Examples of such DSC instrumentation are those provided by Mettler and duPont. The power compensation DSC (e.g., Perkin-Elmer), an exothermic or endothermic event, occurs when a sample is heated, and the power added or subtracted to one or both of the furnaces... 

The term differential scanning calorimetry has become a source of confusion in thermal analysis. This confusion is understandable because at the present time there are several entirely different types of instruments that use the same name. These instruments are based on different designs, which are illustrated schematically in Figure 5.36 (157). In DTA. the temperature difference between the sample and reference materials is detected, Ts — Tx [a, 6, and c). In power-compensated DSC (/), the sample and reference materials are maintained isothermally by use of individual heaters. The parameter recorded is the difference in power inputs to the heaters, d /SQ /dt or dH/dt. If the sample is surrounded by a thermopile such as in the Tian-Calvet calorimeter, heat flux can be measured directly (e). The thermopiles surrounding the sample and reference material are connected in opposition (Calvet calorimeter). A simpler system, also the heat-flux type, is to measure the heat flux between the sample and reference materials (d). Hence, dqjdi is measured by having all the hot junctions in contact with the sample and all the cold junctions in contact with the reference material. Thus, there are at least three possible DSC systems, (d), (c), and (/), and three derived from DTA (a), [b), and (c), the last one also being found in DSC. Mackenzie (157) has stated that the Boersma system of DTA (c) should perhaps also be called a DSC system. 

There are three different types of DSC instruments power-compensated DSC, heat-flux DSC, and modulated DSC, Each produces a plot o power or heat flow versus temperature, called a thernuf ram. ... 

MTDSC represented something of a revolution in thermal analysis with an impact which has been compared to that of the original introduction of power compensation DSC. Numerous publications have appeared devoted to the complexity of the theory and the data manipulation techniques needed before useful information can be obtained. Fortunately all the hard work is done by the instrument software. Rather like conventional DSC, useful information can be obtained without recourse to the detailed theory. 

In power compensated DSC the small size of the individual sample and reference holders makes for rapid response. The temperature sensors are platinum (Pt) resistive elements. The individual furnaces are made of Pt/Rh alloy. It is important that the thermal characteristics of the sample and reference assemblies be matched precisely. The maximum operating temperature is limited to about 750 °C. High temperature DSC measurements (750-1600°C) are made by heat flux instruments using thermocouples of Pt and Pt/Rh alloys. The thermocouples often incorporate a plate to support the crucible. The use of precious metal thermocouples is at the expense of a small signal strength. Both chromel/alumel and chromel/constantan are used in heat flux DSC equipment for measurements at temperatures to about 750 °C. Multiple thermocouple assemblies offer the possibility of an increased sensitivity - recently a 20-junction Au/Au-Pd thermocouple assembly has been developed. Thermocouples of W and W/Re are used in DTA equipment for measurements above 1600°C. The operating temperature is the predominant feature which determines the design and the materials used in the con-... 

An alternative method [2] of determining Mi uses the fact that in power compensation DSC the proportionality constant between the transition peak area and Mi is equivalent to the constant which relates the sample heat capacity and the sample baseline increment. By measuring the specific heat capacity of a standard sapphire sample, an empty sample vessel and the sample of interest, from the difference in the recorded DSC curves of the three experiments Mi for the sample transition can be calculated. The advantage of this method is that sapphire of high purity and stability, whose specific heat capacity is very accurately known, is readily available. Only one standard material (sapphire) is necessary irrespective of the sample transition temperature. The linear extrapolation of the sample baseline to determine Mi has no thermodynamic basis, whereas the method of extrapolation of the specific heat capacity in estimating Mi is thermodynamically reasonable. The major drawbacks of this method are that the instrument baseline must be very flat and the experimental conditions are more stringent than for the previous method. Also, additional computer software and hardware are required to perform the calculation. 

There are two main types of DSC instrumentation, heat-flux DSC and power-compensated DSC. A schematic of a commercial heat-flux DSC is presented in Figure 16.19. In a heat-flux instrument, the same furnace heats both the sample and the reference. In heat-flux DSC, the temperature is changed in a linear manner, while the differential heat flow into the sample and reference is measured. The sample and reference pans sit on the heated thermoelectric disk, made of a Cu/Ni alloy (constantan). The differential heat flow to the sample and reference is monitored by area thermocouples attached to the bottom of the sample and reference positions on the thermoelectric disk. The differential heat flow into the pans is directly proportional to the difference in the thermocouple signals. The sample temperature is measured by the alumel/chromel thermocouple under the sample position. This temperature is an estimated sample temperature because the thermocouple is not inserted into the sample itself. The accuracy of this temperature will depend on the TC of the sample and its container, the heating rate, and other factors. As shown in Figure 16.19, the sample and reference pans both have lids and the reference pan is an empty pan. A schematic of a power-compensated DSC is presented in Figure 16.20. The major difference in power-compensated DSC... 

Compared with a heat-flux DSC, higher scanning rates can be used with a power compensation DSC, with a maximum reliable scanning rate of 60 K min. Maintaining the linearity of the instrument baseline can pose problems at high operating temperatures or in the sub-ambient mode. 

The DTA/DSC-EGD coupled simultaneous technique and relevant equipment have been investigated since 1979 [62, 74, 75]. The Model CDR-1 power compensation DSC analyzer (ambient temperature ca 720 C) was developed by the Tian Ping Instrumental Factory (Shanghai, China). The EGD detector is a thermal conductivity detector (TCD) in the GC analyzer. The CDR-1 DSC analyzer coupled with GC was constructed using a specially designed gas conduit. A schematic diagram of the on-line coupled simultaneous DTA/DSC-EGD apparatus is shown in Figure 2.33. 

Zahra and Zahra (8) reviewed a recent version of this type of DSC instrumentation. Figure 2 provides a schematic representation of the power compensation DSC. 

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