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Durham e-Theses
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Thermoreponsive behaviour of AM(_2)O(_8) materials

Allen, Simon (2003) Thermoreponsive behaviour of AM(_2)O(_8) materials. Doctoral thesis, Durham University.

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This thesis investigates the synthesis and structural characterisation of AM(_2)O(_8) phases, many of which show negative thermal expansion (NTE); relevant literature is reviewed in Chapter One. Chapter Two describes the synthesis, structure solution, and mechanistic role of a new family of low-temperature (LT) orthorhombic AM(_2)O(_8) polymorphs (A(^TV) = Zr, Hf; M(^VI) = Mo, W). These materials are key intermediates in the preparation of cubic AM(_2)O(_8) phases from AM(_2)O(_7)(OH)(_2)(H(_2)O)(_2). The structure of LT-AM(_2)O(_8) has been elucidated by combined laboratory X-ray and neutron powder diffraction. Variable temperature X-ray diffraction (VTXRD) studies have shown LT- AM(_2)O(_8) phases exhibit anisotropic NTE. LT-ZrMo(_2)O(_8) has been shown to undergo spontaneous rehydration, allowing preparation of ZrMo(_2)O(_7)(OD)(_2)(D(_2)O)(_2) and assignment of D(_2)O/OD positions within the structure by neutron diffraction. Using this result, a reversible topotactic dehydration pathway from AM(_2)O(_7)(OH)(_2)(H(_2)O)(_2) to LT-AM(_2)O(_8)s is proposed.Chapter Three investigates the order-disorder phase transition with concurrent oxygen mobility in cubic AM(_2)O(_8) materials; studies include comprehensive VT neutron diffraction of cubic ZrMo(_2)O(_8) to reveal a static to dynamic transition at 215 K, and novel quench-anneal/quench-warm variable temperature/time diffraction experiments on ZrMo(_2)O(_8) which lead to an activation energy of 40 kJmol(^-1) for oxygen migration. In Chapter Four (^17)O-labelled cubic ZrW(_2)O(_8) has been prepared to understand the oxygen migration process by VT MAS NMR. In situ hydrothermal studies of cubicZrMo(_2)O(_8) using synchrotron radiation have shown direct hydration to ZrMo(_2)O(_7)(OH)(_2)(H(_2)O)(_2).. In Chapter Five VTXRD of trigonal a-AMo(_2)O(_8) phases reveals a previously unknown second-order phase transition at 487 K (A = Zr) or 463 K (A = Hf) from P31c to P3ml. Rigid-body Rietveld refinements have shown this is due to alignment of apical Mo-O groups with the c axis in the high-temperature, a' phase.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:2003
Copyright:Copyright of this thesis is held by the author
Deposited On:01 Aug 2012 11:35

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