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.

In this thesis, we aim to investigate the thermoresponsive behaviour, especially negative thermal expansion (NTE), in metal dicarboxylate metal organic frameworks (MOFs) using X-ray diffraction techniques. Four materials with the UiO-66 topology [Zr6O4(OH)4(bdc)12], [Zr6O6(bdc)12], [Zr6O6(bpdc)12] and [Zr6O6(2,6-ndc)12] (bdc = 1,4-benzenedicarboxylate, bpdc = 4,4’-biphenyldicarboxylate and 2,6-ndc = 2,6-napthalenedicarboxylate) were investigated, all of which contain a zero-dimensional inorganic cluster. All four members show NTE behaviour over the observed temperature ranges as a result of the twisting motion of the carboxylate groups of the organic linkers. This twisting motion introduces a concerted rocking motion within the inorganic cluster which causes an apparent decrease in the size of the cluster and hence overall volume contraction. Alteration of the structure of the organic linker has an effect on the magnitude of the expansivity coefficient which is believed to be related to the existence of specific vibrational modes of that particular organic linker. Four members of the MIL-53 family [Al(OH)(bdc)], [AlF(bdc)], [Cr(OH)(bdc)] and [VO(bdc)] were studied. All four materials show elements of NTE behaviour related to a “wine rack” thermo-mechanical mechanism which is determined by the connectivity of the framework. The thermoresponsive behaviour in these materials is dominated by the changes in the plane of the pore opening. These changes result from a combination of three distinct types of motion of the bdc linker including the rotation of the bdc linker about the chain of the inorganic octahedra, the “knee cap” bending mode of the carboxylate groups about the O-O vector and possibly the transverse vibrations within the bdc linker. The latter motion was not evident in this work due to the limitations of the structure refinements. The former two motions appear to be correlated and depend on the rigidity of the metal-centred octahedra which is determined by the constituent metal cation and anion types. The rigidity of the octahedra is also found to play an important role in determining whether the material undergoes a “breathing” phase transition at low temperature. [Sc2(bdc)3] shows NTE behaviour over the observed temperature range which is partially driven by a “wine rack” thermo-mechanical mechanism, but with an opposite framework compression direction when compared to the MIL-53 types MOFs. This is due to the presence of an additional bdc connecting linker in the plane of the pore opening. This extra connection inverses the compression direction and also impedes the structural changes in the plane of the pore opening. The contraction of the chain of inorganic octahedra is the main contributor to the overall unit cell contraction and is caused by the twisting motion of the carboxylate groups of the bdc linker while the magnitude of this contraction is determined by the flexibility of the chain of inorganic octahedra.

No description available.

There has been significant interest in BiFeO₃ over the past decade. This interest has focused on the magnetic and electrical properties, which in the long term may prove useful in device applications. This thesis focuses on the synthesis, electrical characterisation, and structural origin of the electrical properties of rare earth doped bismuth ferrite. Two systems have been studied: BiFeO₃ doped with lanthanum and neodymium (Bi₁₋ₓREₓFeO₃ RE= La, Nd). Specific examples have been highlighted focusing on a detailed structural analysis of a lanthanum doped bismuth ferrite, Bi₀.₅La₀.₅FeO₃, and a neodymium analogue, Bi₀.₇Nd₀.₃FeO₃. Both adopt an orthorhombic GdFeO₃-type structure (space group: Pnma) with G-type antiferromagnetism. Structural variations were investigated by Rietveld refinement of temperature dependent powder neutron diffraction using a combination of both conventional “bond angle/bond length” and symmetry-mode analysis. The latter was particularly useful as it allowed the effects of A-site displacements and octahedral tilts/distortions to be considered separately. This in-depth structural analysis was complemented with ac-immittance spectroscopy using the multi-formulism approach of combined impedance and modulus data to correlate structural changes with the bulk electrical properties. This approach was essential due to the complex nature of the electrical response with contributions from different electroactive regions. The structural variations occur due to a changing balance between magnetic properties and other bonding contributions in the respective systems. This results in changes in the magnitude of the octahedral tilts, and A-site displacements giving rise to phenomena such as negative thermal expansion and invariant lattice parameters i.e., the invar effect. More specifically, analysis of Bi₀.₅La₀.₅FeO₃ highlights a structural link between changes in the relative dielectric permittivity and changes in the FeO₆ octahedral tilt magnitudes, accompanied by a structural distortion of the octahedra with corresponding A-site displacement along the c-axis; this behaviour is unusual due to an increasing in-phase tilt mode with increasing temperature. The anomalous orthorhombic distortion is driven by magnetostriction at the onset of antiferromagnetic ordering resulting in an Invar effect along the magnetic c-axis and anisotropic displacement of the A-site Bi³⁺ and La³⁺ along the a-axis. This contrasts with the neodymium analogue Bi₀.₇Nd₀.₃FeO₃ in which a combination of increasing A-site displacements in the ac-plane and decrease in both in-phase and anti-phase tilts combine with superexchange giving rise to negative thermal expansion at low temperature. The A-site displacements correlate with the orthorhombic strain. By carefully changing the synthesis conditions, a significant change in bulk conductivity was observed for a number for Bi₁₋ₓLaₓFeO₃ compositions. A series of Bi₀.₆La0.₄FeO₃ samples are discussed, where changes in the second step of the synthesis result in significantly different bulk conductivities. This behaviour is also observed in other compositions e.g. Bi₀.₇₅La₀.₂₅FeO₃. Changes in the electrical behaviour as a function of temperature are discussed in terms of phase composition and concentration gradients of defects. Activation energies associated with the conduction process(es) in Bi₁₋ₓLaₓFeO₃ samples, regardless of composition, fall within one of two broad regimes, circa. 0.5 eV or 1.0 eV, associated with polaron hopping or migration of charge via oxygen vacancies, respectively. The use of symmetry-mode analysis, in combination with conventional crystallographic analysis and electrical analysis using multi-formulism approach, presents a new paradigm for investigation of structure-property relationships in rare earth doped BiFeO₃.

[pt] A síntese de pós nanométricos do Al2Mo3O12 para otimização de seu coeficiente de expansão térmica na forma maciça tem como objetivo principal aproximar o comportamento térmico intrínseco e extrínseco do material. A expansão térmica intrinseca de escala atomica é medida por difração de raios-X a partir do aumento dos parametros de rede, por outro lado, a tecnica de dilatometria mede ambos os efeitos tanto intrinsecos quanto extrinsecos provenientes da microestrutura. Materiais anisotropicos apresentam coeficientes de expansão termica diferentes ao longo dos eixos cristalograficos, e com isso são encontradas maiores diferenças entre as propriedades intrinseca e maciça da expansão termica. Dessa forma a aplicação desses materias anisotropicos na forma maciça é comprometida devido a formação de microtrincas. O Al2Mo3O12 foi obtido na forma nanometrica pela síntese por coprecipitação e na forma micrométrica pela síntese de sol-gel assistido com álcool polivinilico e por reação em estado solido. Dessa forma o resultado de CET maciço obtidos pelos três métodos foram comparados entre si e também comparados aos existentes na literatura para comportamento intrínseco e maciço. Os resultados mostraram que o Al2Mo3O12 na forma nanometrica possui resultado de CET maciço muito próximo ao intrínseco, diferente do obtido para o micrométrico e também do já reportado na literatura,o que confirma que a partir de um tamanho de cristal critico não seria mais possível obter um mesmo CET intrínseco e maciço para um mesmo material. / [en] Optimization of the bulk thermal expansion coefficient of the Al2Mo3O12 using nanometric powder in order to approximate the intrinc and the extrinsic thermal properties.When a solid body is exposed to temperature variation, a change of dimensions will occur due to emergence of different effects originating at atomic (intrinsic) or microstructural (extrinsic) scales. The intrinsic thermal expansion is measured by X-ray diffraction from lattice parameters increase, on the other hand, the technique of dilatometric measures both the intrinsic as both extrinsic effects may then be defined as their CTE solid (bulk). Cubic materials exhibit isotropic behavior during thermal expansion, and thus may be insignificant variations between intrinsic and CTE s massive. Anisotropic materials have different coefficients of thermal expansion along the crystallographic axes, and presents major differences between the intrinsic properties and thermal expansion of the bulk, being mostly a bulk CTE smaller than the intrinsic one. The application of these anisotropic materials is difficult because bulk CTE massive changes expected due to formation of microcracks. The Al2Mo3O12 was obtained by three routes :coprecipitation (nanometric way) , sol-gel assisted with polyvinyl alcohol (PVA) and by solid state reaction (micrometric ways). Thus the result of bulk CET obtained by the three methods were compared and also compared with those found in the literature for intrinsic behavior and bulk. The nanometric Al2Mo3O12 showed a bulk linear CTE close to the intrinsic value, whereas micrometric one showed a negative bulk CTE ,which confirms that from a critical cristal size it is no possible to obtain bulk CTE close to the intrinsic one.

The preparation and thermophysical properties of some In(I), Ga(I) and Ag(I) substituted NZP type materials were explored. Many compositions with the NZP framework show low and negative thermal expansion. Previously reported material, GaZr2(PO4(3, transforms from one NZP related phase into another NZP type phase due to oxidation under air above 300oC. In addition, it exhibits hysteresis under inert atmosphere; the cell parameters are different on heating and cooling cycles for a given temperature. The synthesis, and characterization of a new material, InZr2(PO4)3, is outlined. It crystallizes in space group R -3 c. In addition, as GaZr2(PO4)3, it oxidizes above 300oC under air and exhibits hysteresis under inert atmosphere. Furthermore, the synthesis of AgTixZr2-x(PO4)3 solid solution compositions, their ion exchange characteristics with Ga(I) and their thermophysical properties are described. Thermal expansion anisotropy (the difference between a and c ) of the solid solutions decreases as the bigger ion, Zr4+, is substituted by the smaller one, Ti4+. Thermal expansion characteristics of GaZr2(PO4)3, InZr2(PO4)3 and AgZr2(PO4)3 are compared with MZr2(PO4)3 ( M = Li, Na, K, Rb, Cs). Ionic radii for Ga(I) and In(I) in a six coordinate oxygen environment were proposed.

Zirconium tungstate (ZrW2O8) is a ceramic that shows large isotropic negative thermal expansion over a wide range of temperature. This unique property makes it an interesting candidate for applications where thermal expansion mismatch between components constitutes a problem. ZrW2O8 is typically produced by solid-state reaction between zirconium oxide and tungsten oxide at 1200oC. In some studies, ZrW2O8 precursors have been produced from relatively expensive zirconium and tungsten sources. While the origin of negative thermal expansion has been the main focus in the majority of publications, production of particles with controlled size, distribution and morphology has not been studied extensively. Electrospinning is a simple technique for producing micron/nano sized fibers from polymer solutions. The method can also be used for producing ceramic or polymer/ceramic composite fibers by electrospinning of a mixture of ceramic precursors or ceramic nanoparticles with suitable polymers. Ceramic precursors could be synthesized either by sol-gel or chemical precipitation routes before mixing them with polymer solutions and a final burnout step would be needed, in case the fiber is desired to be composed of the ceramic phase. Electrospinning technique has not been employed to the production of ZrW2O8 ceramic fibers. In this study a novel precursor for ZrW2O8 from relatively cheaper and abundant starting chemicals, namely zirconium acetate and tungstic acid were used. Experimental details of development of the precursor are presented with a discussion on the effects of solution parameters on the phase purity of the fired product. Besides the solution parameters investigated (i.e. solubility of tungstic acid, adjustment of the stoichiometry, final pH of the solution, ageing time), evolution of the heat treatment protocol was used in the production of phase pure ZrW2O8. Second, the suitability of the developed precursor for producing ZrW2O8 in fiber form was investigated. Preliminary studies involved the adjustment of the viscosity of precursor solution for electrospinning with poly (vinyl alcohol) (PVA). Optimum PVA concentration leading to bead-free nanofiber mats and a method to increase the fiber production rate were reported. The characterization of the products was achieved by SEM and XRD.

This work focuses on the chemical substitution of cations and anions in the frameworks of materials that have been known to exhibit negative thermal expansion (NTE). Zr2(PO4)2(SO4) is a member of the A(2)M(3)O(12) family which has been known to exhibit NTE. We have shown that Zr2(PO4)2(SO4) exhibits anisotropic positive thermal expansion. We have also shown that this material has been characterized in the wrong space group. Hf2(PO4)2(SO4) behaves similarly to Zr2(PO4)2(SO4) and follows this trend. Under pressure, Hf2(PO4)2(SO4) appears to undergo a phase transition. We have still yet to determine what space group the materials transitions to. While many members of the AX(2)O(7) family of frameworks have been fully characterized, the thermal expansion of PbP2O7 has yet to be reported. We were unable to obtain a reproducible procedure for synthesis of PbP2O7 from its precursor. Finally, variable temperature and variable pressure studies were performed on ZrMo2O8 in an attempt to learn more about the local structure. We found that space groups P213 and Pa-3 gave poor fits of the local structure at low r. Behavior of the nearest neighbor Zr-Mo distance was very similar to the bulk CTE. On compression, pressure induced amorphization is observed in ZrMo2O8. All interatomic correlations above 4 angstroms are washed out. Zr-O-Mo linkages remain well defined and do not massively deform as the pressure is increased. Finally, we we observed that Zr-O-Mo linkages change geometry reversibly as the pressure is increased.

This thesis explores the thermal expansion and high pressure behavior of some materials with the ReO₃ structure type. This structure is simple and has, in principle, all of the features necessary for negative thermal expansion (NTE) arising from the transverse thermal motion of the bridging anions and the coupled rotation of rigid units; however, ReO₃ itself only exhibits mild NTE across a narrow temperature range at low temperatures. ReO₃ is metallic because of a delocalized d-electron, and this may contribute to the lack of NTE in this material. The materials examined in this thesis are all based on d⁰ metal ions so that the observed thermal expansion behavior should arise from vibrational, rather than electronic, effects. In Chapter 2, the thermal expansion of scandium fluoride, ScF₃, is examined using a combination of in situ synchrotron X-ray and neutron variable temperature diffraction. ScF₃ retains the cubic ReO₃ structure across the entire temperature range examined (10-1600 K) and exhibits pronounced negative thermal expansion at low temperatures. The magnitude of NTE in this material is comparable to that of cubic ZrW₂O₈, which is perhaps the most widely studied NTE material, at room temperature and below. This is the first report of NTE in an ReO₃ type structure across a wide temperature range. Chapter 3 presents a comparison between titanium oxyfluoride, TiOF₂, and a vacancy containing titanium hydroxyoxyfluoride, Tiₓ(O/OH/F)₃. TiOF₂ was originally reported to adopt the cubic ReO₃ structure type under ambient conditions, therefore the initial goal for this study was to examine the thermal expansion of this material and determine if it displayed interesting behavior such as NTE. During the course of the study, it was discovered that the original synthetic method resulted in Tiₓ(O/OH/F)₃, which does adopt the cubic ReO₃ structure type. The chemical composition of the hydroxyoxyfluoride is highly dependent upon synthesis conditions and subsequent heat treatments. This material readily pyrohydrolyizes at low temperatures (~350 K). It was also observed that TiOF₂ does not adopt the cubic ReO₃ structure; at room temperature it adopts a rhombohedrally distorted variant of the ReO₃ structure. Positive thermal expansion was observed for TiOF₂ from 120 K through decomposition into TiO₂. At ~400 K, TiOF₂ undergoes a structural phase transition from rhombohedral to cubic symmetry. High pressure diffraction studies revealed a cubic to rhombohedral phase transition for Tiₓ(O/OH/F)₃ between 0.5-1 GPa. No phase transitions were observed for TiOF₂ on compression. In Chapter 4, an in situ variable pressure{temperature diffraction experiment examining the effects of pressure on the coefficients of thermal expansion (CTE) for ScF₃ and TaO₂F is presented. In the manufacture and use of composites, which is a possible application for low and NTE materials, stresses may be experienced. Pressure was observed to have a negligible effect on cubic ScF₃'s CTE; however, for TaO₂F the application of modest pressures, such as those that might be experienced in the manufacture or use of composites, has a major effect on its CTE. This effect is associated with a pressure-induced phase transition from cubic to rhombohedral symmetry upon compression. TaO₂F was prepared from the direct reaction of Ta₂O₅ with TaF₅ and from the digestion of Ta₂O₅ in hot hydro uoric acid. The effects of pressure on the two samples of TaO₂F were qualitatively similar. The slightly different properties for the samples are likely due to differences in their thermal history leading to differing arrangements of oxide and uoride in these disordered materials. In Chapter 5, the local structures of TiOF₂ and TaO₂F are examined using pair distribution functions (PDFs) obtained from X-ray total scattering experiments. In these materials, the anions (O/F) are disordered over the available anion positions. While traditional X-ray diffraction provides detailed information about the average structures of these materials, it is not suffcient to fully understand their thermal expansion. Fits of simple structural models to the low r portions of PDFs for these materials indicate the presence of geometrically distinct M{X{M (M = Ti, Ta; X = O, F) linkages, and a simple analysis of the TaO₂F variable temperature PDFs indicates that these distinct links respond differently to temperature.

The A2Mo3O12 family, where A3+ is a large trivalent cation, can show interesting thermal properties such as negative thermal expansion, also known as thermomiotic behavior, where the overall volume of the material contracts with increasing temperature. A selection of compounds in this family, namely HfMgMo3O12, In2Mo3O12, Y2Mo3O12, Al2Mo3O12, In(HfMg)0.5Mo3O12, and In1.5(HfMg)0.25Mo3O12, have been synthesized using solid-state and mechanical activation techniques as well as a simplified sol-gel approach (Al2Mo3O12). Coefficients of thermal expansion were found to range from large-negative to low-positive in the orthorhombic phase, including near-zero in In(HfMg)0.5Mo3O12 and In1.5(HfMg)0.25Mo3O12. This set of materials provided insight into the role of low-frequency phonon modes in open-framework materials. Low-temperature heat capacity and thermal conductivity measurements confirmed that low-frequency modes were active in thermomiotic materials, and also present to some extent in all members of the open-framework A2Mo3O12 family examined. A clear correlation exists between the magnitude and sign of the coefficient of thermal expansion in the orthorhombic phase and the contribution of low-energy modes to the low-temperature heat capacity, with negative thermal expansion materials having a larger contribution. The low-frequency phonon modes result in low thermal conductivity and reduced phonon mean free paths when compared to conventional ceramics and indicate that these low values are characteristic of open-framework materials in NTE families even if the materials in the families are not thermomiotic themselves.