Differential thermal analysis heat-flux

The Nomenclature Committee of the International Confederation for Thermal Analysis (ICTA) has defined DSC as a technique in which the difference in energy inputs into a substance and a reference material is measured as a function of temperature whilst the substance and reference material are subjected to a controlled temperature program. Two modes, power compensation DSC and heat flux DSC, can be distinguished depending on the method of measurement used1 . The relationship of these techniques to classical differential thermal analysis (DTA) is discussed by MacKenzie2). 

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.)...

Historically, DSC is a development of differential thermal analysis (DTA) and both techniques measure the heat flux in a sample as a function of temperature. In DTA, the heat flux is measured as a temperature difference between a sample and a reference material... 

Murphy CB. Differential thermal analysis. Anal Chem. May. 1960 32 168R-71R. Murphy CB. Differential thermal analysis. Anal Chem. Apr. 1962 34 298R-301R. Standard Test Method for Steady-State Heat Flux Measurements and Thermal Transmission Properties by Means of the Guarded Hot-Plate Apparatus, ASTM C177, Am Soc. For Testing and Materials. Jan. 11, 2004. 

One of these techniques that brought into science the name DSC, called today power compensation DSC, was created by Gray and O Neil at the Perkin-Elmer Corporation in 1963. The other technique grew out of differential thermal analysis (DTA), and is called heat flux DSC. Differential thermal analysis itself originates from the works of Le Chatelier (1887), Roberts-Austen (1899), and Kurnakov (1904) (see Wunderlich, 1990). It needs to be emphasized that both of these techniques give similar results, but of course, they both have their advantages and disadvantages. 

Temperature difference >> > Differential Thermal Analysis (DTA). Heat flux variation >>> Differential Scanning Calorimeter (DSC). Heat variation >>> Calorimetry. 

In practice, the enthalpy of gasification is rarely calculated because detailed and reliable thermodynamic data for the polymer and its decomposition products are generally unavailable. Direct laboratory measurement of Lg using differential thermal analysis and differential scanning calorimetry has been reported, but Lg is usually measured in a constant heat flux gasification device or fire calorimeter (see under Steady Burning). In these experiments a plot of mass loss rate per unit surface area (mass flux) versus external heat flux has slope 1/Lg where... 

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.)...

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. 

Thermal analysis is not really one subject, because the information gained and the purposes for which it can be used are quite varied. The main truly thermal technique is differential scanning calorimetry (DSC). The heat input and temperature rise for the material under test are compared with those for a standard material, both subjected to a controlled temperature programme. In power compensation DSC the difference in heat input to maintain both test pieces at the same temperature is recorded. In heat flux DSC the difference in heat input is derived from the difference in temperature between the sample and the reference material. Heat losses to the surroundings are allowed but assumed to depend on temperature only. 

However, as with the penetration theory analysis, the difference in magnitude of the mass and thermal diffusivities with cx 100 D, means that the heat transfer film is an order of magnitude thicker than the mass transfer film. This is depicted schematically in Fig. 8, The fall in temperature from T over the distance x is (if a = 100 D) about 0% of the overall interface excess temperature above the datum temperature T.. Furthermore, in considering the location of heat release oue to reaction in the mass transfer film, this is bound to be greatest closest to the interface, and this is especially the case when the reaction becomes fast. Therefore, two simplifications can be introduced as a result of this (i) the release of heat of reaction can be treated as am interfacial heat flux and (ii) the reaction can be assumed to take place at the interfacial temperature T. The differential equation for diffusion and reaction can therefore be written... 

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