A contribution towards the performance and structural understanding of copper and nickel salts as ammonia stores

The ongoing depletion of fossil fuels and the severe consequences of the greenhouse effect make the development of alternative energy systems crucially important. While hydrogen is, in principle, a promising alternative, releasing nothing but energy and pure water. Hydrogen storage is complicated and no completely viable technique has been proposed so far. This work is concerned with the study of one potential alternative to pure hydrogen: ammonia, and more specifically its storage in solids. Ammonia, NH3, can be regarded as a chemical hydrogen carrier with the advantages of strongly reduced flammability and explosiveness as compared to hydrogen. Furthermore, ammine metal salts presented here as promising ammonia stores easily store up to 50 wt.-% ammonia, giving them a volumetric energy density comparable to natural gas. The model system NiX2–NH3 ( X = Cl, Br, I) is studied thoroughly with respect to ammine salt formation, thermal decomposition, air stability and structural effects. The system CuX2–NH3 ( X = Cl, Br) has an adverse thermal decomposition behaviour, making it impractical for use as an ammonia store. This system is, however, most interesting from a structural point of view and some work concerning the study of the structural behaviour of this system is presented. Finally, close chemical relatives to the metal ammine halides, the metal ammine nitrates are studied. They exhibit interesting anion arrangements, which is an impressive showcase for the combination of diffraction and spectroscopic information. The characterisation techniques in this thesis range from powder diffraction over single crystal diffraction, spectroscopy, computational modelling, thermal analyses to gravimetric uptake experiments. Further highlights are the structure solutions and refinements from powder data of (NH4)2[NiCl4(H2O)(NH3)] and Ni(NH3)2(NO3)2, the combination of crystallographic and chemical information for the elucidation of the (NH4)2[NiCl4(H2O)(NH3)] formation reaction and the growth of single crystals under ammonia flow, a technique allowing the first documented successful growth and single crystal diffraction measurement for [Cu(NH3)6]Cl2.

The symbolic, socio-economic and exchange value of Imperial German and National Socialist medals and badges, 1701 to the present

This thesis examines the manufacture, use, exchange (including gift exchange), collecting and commodification of German medals and badges from the early 18th century until the present-day, with particular attention being given to the symbols that were deployed by the National Socialist German Workers’ Party (NSDAP) between 1919 and 1945. It does so by focusing in particular on the construction of value through insignia, and how such badges and their symbolic and monetary value changed over time. In order to achieve this, the thesis adopts a chronological structure, which encompasses the creation of Prussia in 1701, the Napoleonic wars and the increased democratisation of military awards such as the Iron Cross during the Great War. The collapse of the Kaiserreich in 1918 was the major factor that led to the creation of the NSDAP under the eventual strangle-hold of Hitler, a fundamentally racist and anti-Semitic movement that continued the German tradition of awarding and wearing badges. The traditional symbols of Imperial Germany, such as the eagle, were then infused with the swastika, an emblem that was meant to signify anti-Semitism, thus creating a hybrid identity. This combination was then replicated en-masse, and eventually eclipsed all the symbols that had possessed symbolic significance in Germany’s past. After Hitler was appointed Chancellor in 1933, millions of medals and badges were produced in an effort to create a racially based “People’s Community”, but the steel and iron that were required for munitions eventually led to substitute materials being utilised and developed in order to manufacture millions of politically oriented badges. The Second World War unleashed Nazi terror across Europe, and the conscripts and volunteers who took part in this fight for living-space were rewarded with medals that were modelled on those that had been instituted during Imperial times. The colonial conquest and occupation of the East by the Wehrmacht, the Order Police and the Waffen-SS surpassed the brutality of former wars that finally culminated in the Holocaust, and some of these horrific crimes and the perpetrators of them were perversely rewarded with medals and badges. Despite Nazism being thoroughly discredited, many of the Allied soldiers who occupied Germany took part in the age-old practice of obtaining trophies of war, which reconfigured the meaning of Nazi badges as souvenirs, and began the process of their increased commodification on an emerging secondary collectors’ market. In order to analyse the dynamics of this market, a “basket” of badges is examined that enables a discussion of the role that aesthetics, scarcity and authenticity have in determining the price of the artefacts. In summary, this thesis demonstrates how the symbolic, socio-economic and exchange value of German military and political medals and badges has changed substantially over time, provides a stimulus for scholars to conduct research in this under-developed area, and encourages collectors to investigate the artefacts that they collect in a more historically contextualised manner.