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Figure 4: Reaction temperatures observed during dehydration of MgCl2 * 6 H2O and a MgCl2 * 6 H2O : graphite composite (1 : 0.45) at different heating rates, 25 – 200°C. Also, at a heating rate of 0.1°C / min, the occurrence of thermal decomposition can be clearly observed using TGA/DSC at temperatures above 125°C, reaching its peak at 160°C. This is an important finding, as it explains the more or less parallel occurrence of beginning thermal decomposition together with the third dehydration step in most published material [e.g. 19]. When working under vacuum, the temperatures at which the different reactions occur are lowered further [20], leading to observable acid formation at even lower temperatures then 125°C. It is hardly possible to investigate a higher number of samples using a heating rate of 0.1°C, because of the long time needed for a single TGA/DSC run of 30h. Therefore, with these results in mind, we investigated other possible additives using 1°C / min heating rate. Figure 5 shows the obtained results using different additives. Sand and zeolite were used as possible structure supporting agents, whereas copper and graphite could act as ingredients that are able to enhance heat conductivity. However, an influence of higher heat conductivity of the materials cannot be clearly deduced from these measurements, as the addition of sand shows results very similar to those adding an equivalent amount of copper to the sample. The graphite composite contains a higher amount of MgCl2 * 6 H2O, possibly accounting for higher observed reaction temperature at 1°C / min heating rate. In contrast, the zeolite composite shows a different behavior. Whilst the observed peak temperatures are similar to those obtained by using copper and sand as additives, zeolite is altering the peak shape, leading to a more peak tailing in contrast to the fronting observed in other experiments. A comparison of peak heat fluxes during dehydration step II, which shows the highest heat flux of the three observed steps, normalized to MgCl2 * 6 H2O content (Figure 6), shows, that reactivity of pure MgCl2 * 6 H2O is more or less comparable to the zeolite and copper composites.PDF Image | THERMOCHEMICAL STORAGE MATERIALS RESEARCH
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