Studies of Inorganic Layer and Framework Structures Using Time-, Temperature- and Pressure-Resolved Powder Diffraction Techniques

This thesis is concerned with in-situ time-, temperature- and pressure-resolved synchrotron X-ray powder diffraction investigations of a variety of inorganic compounds with twodimensional layer structures and three-dimensional framework structures. In particular, phase stability, reaction kinetics, thermal expansion and compressibility at non-ambient conditions has been studied for 1) Phosphates with composition MIV(HPO4)2·nH2O (MIV = Ti, Zr); 2) Pyrophosphates and pyrovanadates with composition MIVX2O7 (MIV = Ti, Zr and X = P, V); 3) Molybdates with composition ZrMo2O8. The results are compiled in seven published papers and two manuscripts. Reaction kinetics for the hydrothermal synthesis of α-Ti(HPO4)2·H2O and intercalation of alkane diamines in α-Zr(HPO4)2·H2O was studied using time-resolved experiments. In the high-temperature transformation of γ-Ti(PO4)(H2PO4)·2H2O to TiP2O7 three intermediate phases, γ'-Ti(PO4)(H2PO4)·(2-x)H2O, β-Ti(PO4)(H2PO4) and Ti(PO4)(H2P2O7)0.5 were found to crystallise at 323, 373 and 748 K, respectively. A new tetragonal three-dimensional phosphate phase called τ-Zr(HPO4)2 was prepared, and subsequently its structure was determined and refined using the Rietveld method. In the high-temperature transformation from τ-Zr(HPO4)2 to cubic α-ZrP2O7 two new orthorhombic intermediate phases were found. The first intermediate phase, ρ-Zr(HPO4)2, forms at 598 K, and the second phase, β-ZrP2O7, at 688 K. Their respective structures were solved using direct methods and refined using the Rietveld method. In-situ high-pressure studies of τ-Zr(HPO4)2 revealed two new phases, tetragonal ν-Zr(HPO4)2 and orthorhombic ω-Zr(HPO4)2 that crystallise at 1.1 and 8.2 GPa. The structure of ν-Zr(HPO4)2 was solved and refined using the Rietveld method. The high-pressure properties of the pyrophosphates ZrP2O7 and TiP2O7, and the pyrovanadate ZrV2O7 were studied up to 40 GPa. Both pyrophosphates display smooth compression up to the highest pressures, while ZrV2O7 has a phase transformation at 1.38 GPa from cubic to pseudo-tetragonal β-ZrV2O7 and becomes X-ray amorphous at pressures above 4 GPa. In-situ high-pressure studies of trigonal α-ZrMo2O8 revealed the existence of two new phases, monoclinic δ-ZrMo2O8 and triclinic ε-ZrMo2O8 that crystallises at 1.1 and 2.5 GPa, respectively. The structure of δ-ZrMo2O8 was solved by direct methods and refined using the Rietveld method.

Mountain centered icefields in northern Scandinavia

Mountain centered glaciers have played a major role throughout the last three million years in the Scandinavian mountains. The climatic extremes, like the present warm interglacial or cold glacial maxima, are very short-lived compared to the periods of intermediate climate conditions, characterized by the persistence of mountain based glaciers and ice fields of regional size. These have persisted in the Scandinavian mountains for about 65% of the Quaternary. Mountain based glaciers thus had a profound impact on large-scale geomorphology, which is manifested in large-scale glacial landforms such as fjords, glacial lakes and U-shaped valleys in and close to the mountain range. Through a mapping of glacial landforms in the northern Scandinavian mountain range, in particular a striking set of lateral moraines, this thesis offers new insights into Weichselian stages predating the last glacial maximum. The aerial photograph mapping and field evidence yield evidence that these lateral moraines were overridden by glacier ice subsequent to their formation. The lateral moraines were dated using terrestrial cosmogenic nuclide techniques. Although the terrestrial cosmogenic nuclide signature of the moraines is inconclusive, an early Weichselian age is tentatively suggested through correlations with other landforms and stratigraphical archives in the region. The abundance and coherent spatial pattern of the lateral moraines also allow a spatial reconstruction of this ice field. The ice field was controlled by topography and had nunataks protruding also where it was thickest close to the elevation axis of the Scandinavian mountain range. Outlet glaciers discharged into the Norwegian fjords and major valleys in Sweden. The process by which mountain based glaciers grow into an ice sheet is a matter of debate. In this thesis, a feedback mechanism between debris on the ice surface and ice sheet growth is presented. In essence, the growth of glaciers and ice sheets may be accelerated by an abundance of debris in their ablation areas. This may occur when the debris cover on the glacier surface inhibits ablation, effectively increasing the glaciers mass balance. It is thus possible that a dirty ablation area may cause the glacier to advance further than a clean glacier under similar conditions. An ice free period of significant length allows soil production through weathering, frost shattering, and slope processes. As glaciers advance through this assemblage of sediments, significant amounts of debris end up on the surface due to both mass wastage and subglacial entrainment. Evidence that this chain of events may occur, is given by large expanses of hummocky moraine (local name Veiki moraine) in the northern Swedish lowlands. Because the Veiki moraine has been correlated with the first Weichselian advance following the Eemian, it implies a heavily debris charged ice sheet emanating from the mountain range and terminating in a stagnant fashion in the lowlands.