Sample thermogravimetry

The non-stoichiometry <5 of Cu2- O has been extensively studied by various methods such as chemical analysis of a quenched sample, thermogravimetry, electrical resistivity measurement, and coulometric titration, but the results obtained are not consistent. 

C with a heating rate of lO C/min under a N2 atmosphere. The measurements were eonducted using 6-10 mg samples. Thermogravimetrie curves were reeorded. 

A second approach to gravimetry is to thermally or chemically decompose a solid sample. The volatile products of the decomposition reaction may be trapped and weighed to provide quantitative information. Alternatively, the residue remaining when decomposition is complete may be weighed. In thermogravimetry, which is one form of volatilization gravimetry, the sample s mass is continuously monitored while the applied temperature is slowly increased. 

Thermogravimetry The products of a thermal decomposition can be deduced by monitoring the sample s mass as a function of applied temperature. (Figure 8.9). The loss of a volatile gas on thermal decomposition is indicated by a step in the thermogram. As shown in Example 8.4, the change in mass at each step in a thermogram can be used to identify both the volatilized species and the solid residue. 

The procedures of measuring changes in some physical or mechanical property as a sample is heated, or alternatively as it is held at constant temperature, constitute the family of thermoanalytical methods of characterisation. A partial list of these procedures is differential thermal analysis, differential scanning calorimetry, dilatometry, thermogravimetry. A detailed overview of these and several related techniques is by Gallagher (1992). 

Thermal analysis helps in measuring the various physical properties of the polymers. In this technique, a polymer sample is subjected to a controlled temperature program in a specific atmosphere and properties are measured as a function of temperature. The controlled temperature program may involve either isothermal or linear rise or fall of temperature. The most common thermoanalytical techniques are (1) differential scanning analysis (DSC), (2) thermomechanical analysis (TMA), and (3) thermogravimetry (TG). 

Thermogravimetry may be used to determine the composition of binary mixtures. If each component possesses a characteristic unique pyrolysis curve, then a resultant curve for the mixture will afford a basis for the determination of its composition. In such an automatic gravimetric determination the initial weight of the sample need not be known. A simple example is given by the automatic determination of a mixture of calcium and strontium as their carbonates. 

The techniques referred to above (Sects. 1—3) may be operated for a sample heated in a constant temperature environment or under conditions of programmed temperature change. Very similar equipment can often be used differences normally reside in the temperature control of the reactant cell. Non-isothermal measurements of mass loss are termed thermogravimetry (TG), absorption or evolution of heat is differential scanning calorimetry (DSC), and measurement of the temperature difference between the sample and an inert reference substance is termed differential thermal analysis (DTA). These techniques can be used singly [33,76,174] or in combination and may include provision for EGA. Applications of non-isothermal measurements have ranged from the rapid qualitative estimation of reaction temperature to the quantitative determination of kinetic parameters [175—177]. The evaluation of kinetic parameters from non-isothermal data is dealt with in detail in Chap. 3.6. 

Thermogravimetry consists of the continual recording of the mass of the sample as it is heated in a furnace, and a schematic diagram of a TG apparatus is given in Fig. 14. The weighing device used in most systems is a microbalance, which permits the accurate determination of milligram changes in the sample mass. The... 

Changes in catalysts during preparation, which often involves thermal calcination, oxidation, and reduction, can also be followed by recording the associated variations in sample weight, as in normal thermogravimetry (TG) or differential thermogravimetiy (DTG) or in sample temperature,... 

The number of experimental factors which influence the results increases considerably when thermogravimetry is combined with other techniques such as DTA, gas chromatography46, mass spectrometry, X-ray etc. A systematic discussion of all these additional factors would lead too far, therefore only a representative example will be discussed here. One of the often-applied multiple techniques is the combination TG-DTA. Besides the actual thermal reactions of the sample, the important factors in DTA are the heat capacity and the thermal conductivity of the sample. Optimum heat transfer is required for such thermoanalytical measurements therefore the shape of the sample and its contact with the crucible is of special importance. 

During investigations on dissociation equilibria by means of thermogravimetry, it was observed that the detailed mechanism of certain carbonate decompositions3 is still not completely clarified. The reason for this is that differences in the decomposition mechanism can be introduced by the nature of the substance, by structural variations and especially by even minor changes of the gas atmosphere around and in the sample. Of course, also the effect of the usual experimental conditions has to be taken into account. 

Each sample was evaluated by thermogravimetry to determine if the thermal stability could be enhanced by removing some residual cobalt chloride. The BTDA-ODA polyimide film thermal stability is reduced about 50 C due to the cobalt chloride dopant. Soa)cing or extraction with water has no positive effect on the thermal stability whereas soxhlett extraction with DMAc severely degrades the polymer stability. For the BDSDA-ODA polyimide films the incorporation of cobalt chloride also reduces the bul)c polymer thermal stability. Soa)cing this film in water for 24 hours, however, increased the bul)c thermal stability slightly from 512 to 532 C. 

The y-form is known to be anhydrous, and contains minimal water. The USP water specification for sorbitol requires that a sample contain less than or equal to 1.0% water in the sample [1]. The thermogravimetry (TG) and Karl Fisher (KF) data for the y-form sorbitol samples analyzed in this study are summarized in Table 4. TG analysis indicated the existence of minimal volatile content in the samples, indicating that the materials were anhydrous. The volatile component was identified as water, based on the KF values obtained for the samples. 

The thermal behavior of the hyperbranched polymer 7, as well as that of the related tetra- and octanuclear dendrimers 1 and 2, was examined by thermal gravimetric analysis (TGA) and derivative thermogravimetry (DTG). The samples were heated at a ramp rate of 10 °Cymin under nitrogen atmosphere in the tenqierature range 25-8(K) °C. The major decompositions occur between 340 and 540 °C for the tetranuclear 1, and between 370 and 520 °C for the octanuclear 2, whereas for polymer 7 a faster rate of weight loss is observed at a higher (480 and 560 C) temperature range. The thermal stability of the network dendrimeric material 7 is... 

Differential thermal analysis (DTA) was performed in air with an OD-102 Derivatograph (MOM, Hungary) using 100 mg samples at a heating rate of 10°C/min. Differential thermogravimetry (DTG) and thermogravimetry... 

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