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Phase formation studies in the quaternary section Ca_2-<I>y</I>Sr<I>_y</I>Fe_2-<I>x</I>B'<I>_x</I>O<I>_γ</I> : B' = Nb, Ta, 0 ≤ <I>y</I> ≤ 2.0 and 0 ≤ <I>x</I> ≤ 2.0 were carried out. Results are summarised below for B' = Nb; for B' = Ta they were broadly similar. Four solid solution phases were found: i) a cubic solid solution, with a variable compositional extent <I>x</I>, which increased with substitution of Ca by Sr, from 0.45 ≤ <I>x</I> ≤ 0.65 for <I>y</I> = 0, to 0 ≤ <I>x</I> ≤ 1.2 for <I>y</I> = 2.0. ii) A limited orthorhombic solid solution along the Ca₂Fe₂O₅-Ca₂B'₂O₇ join with 0.8 ≤ <I>x</I> ≤ 1.0. iii) A complete range of orthorhombic, brownmillerite solid solution for <I>x</I> = 0 and iv) an orthorhomic, perovskite-related solid solution, isostructural with Ca₂Nb₂O₇, for <I>x</I> = 2.0. A combination of differential thermal analysis, thermogravimetry, Mössbauer spectroscopy, high temperature powder X-ray diffraction, Rietveld refinement, a.c. impedance spectroscopy and magnetic susceptometry has been used to characterise these new phases. Solid solution (i) has variable oxygen content with an oxygen-deficient perovskite structure. As synthesised, for <I>x</I> = 0.6 it contains a mixture of Fe⁴⁺ and Fe³⁺ in the ratio 13/87. The oxygen content could be modified by heat treatment under various atmospheres over the range 5.5. ≤ <I>γ</I> ≤ 5.92 which corresponded to the ratios: 93/7 to Fe³⁺/Fe²⁺ and 42/58 of Fe⁴⁺/Fe³⁺. At higher oxygen contents, <I>γ</I> > 5.7, transformation to an orthorhombic structure was observed. The electrical resistivity was dominated by grain boundary effects. Conduction is electronic and is attributed to hopping between iron in mixed oxidation states. The resistivity increased dramatically on reduction and became <I>n</I>-type, presumably due to a small fraction of Fe²⁺ present.

The NASA Mars Science Laboratory (MSL) rover, Curiosity, began exploring Gale crater, Mars in August, 2012 with the primary goal of assessing the past and present habitability of the martian surface. To meet this goal, Curiosity is equipped with an advanced suite of scientific instruments capable of investigating the geology, geochemistry, and atmospheric conditions on Mars. Among these instruments is the CheMin (Chemistry and Mineralogy) X-ray diffractometer whose function is to identify mineral phases present in sediments and rocks by means of X-ray diffraction (XRD). Characterizing the mineralogical make-up of a rock unit is an important step in determining its geologic history. Primary igneous minerals, such as feldspar, olivine, and pyroxene, give information about parental magmas - their composition, temperature, depth and so on. Secondary alteration minerals, like jarosite or akaganeite, point to distinct weathering or diagenetic processes. As such, understanding the mineral occurrence and abundance in Gale crater provides the MSL team with a robust foundation from which to make geologic interpretations. This dissertation details the methods used to determine the chemical composition of selected mineral phases based solely on XRD patterns from CheMin. Curiosity is equipped with instruments capable of measuring bulk composition of a sample [e.g., APXS (Alpha Particle X-ray Spectrometer)] but has no instrument capable of measuring the composition of a single phase in a multi-phase sample. Therefore, we developed crystal chemical algorithms and calibrations based on refined unit-cell parameters in order to predict mineral phase compositions. We have calculated algorithms for plagioclase, alkali feldspar, Mg-Fe-Ca clinopyroxene, Mg-Fe orthopyroxene, Mg-Fe olivine, Fe-oxide spinel, and alunite-jarosite group minerals. Furthermore, we use the estimated compositions of crystalline material in conjunction with bulk sample chemistry from APXS to estimate of the composition of the X-ray amorphous material present in each of the samples analyzed by CheMin in Gale crater.

In the last two decades much has been published on the behaviour of certain elements in the magmatic , hydrothermal, sedimentary and weathering environments , but the information is scattered throughout the literature . This situation prompted the present study on the elements Ni, Co, Cu, Pb , Zn , Au, Ag , Mo , Sn, W and U. The behaviour of the elements Ni, Cu, Pb , ZN, Au, Sn , W and U has been studied experimentally in some depth. Ag has been moderately studied, but there is very little information about Co and Mo. Studies on the complexes formed by the elements within the hydrothermal and aqueous environment are often inconclusive and controversial , but conclusions are drawn as to the more likely complexes formed . A genetic classification of ore deposits is used as a framework for the discussion . The source of the elements is regarded as being the mantle, and therefore discussion on other possible sources is beyond the scope of this dissertation. The crystal chemistry and geochemistry of the elements are presented and the essay concludes with a discussion on the elements within their depositional environments

This dissertation is focused on the design of the Open Data Repository's Data Publisher (ODR), a web-based central repository for scientific data, primarily focused on mineralogical properties, but also applicable to other data types, including for instance, morphological, textural and contextual images, chemical, biochemical, isotopic, and sequencing information. Using simple web-based tools, the goal of ODR is to lower the cost and training barrier so that any researcher can easily publish their data, ensure that it is archived for posterity, and comply with the mandates for data sharing. There are only a few databases in the mineralogical community, including RRUFF (http://rruff.info) for professionals, and mindat.org (http://www.mindat.org) for amateurs. These databases contain certain specific mineral information, but none, however, provide the ability to include, in the same platform, any of the many datatypes that characterize the properties of minerals. The ODR framework provides the flexibility required to include unforeseen data without the need for additional software programming. Once ODR is completed, the RRUFF database will be migrated into ODR and populated with additional data using other analytical techniques, such as Mössbauer data from Dr. Richard Morris and NVIR data from Dr. Ralf Milliken. The current ODR pilot studies are also described here, including 1) a database of the XRD analysis performed by the CheMin instrument on the Mars Science Laboratory rover Curiosity, 2) the NASA-AMES Astrobiology Habitable Environments Database (AHED), which aims to provide a central, high quality, long-term data repository for relevant astrobiology information, 3) the University of Arizona Mineral Museum (UAMM), with over 21,000 records of minerals and fossils from the museum collection, and 4) the Mineral Evolution Database (MED), that uses the ages of mineral species and their localities to correlate the diversification of mineral species through time with Earth's physical, chemical and biological processes. A good database design requires understanding the fundamentals of its content, so part of this thesis is also focused on developing my skills in mineral analysis and characterization, through the study of the crystal-chemistry of diverse minerals using X-ray diffraction, Raman spectroscopy and microprobe analysis, as principal techniques.

The design and synthesis of novel functional materials with fine-tunable physical and chemical properties has been an aspiration of materials scientists since at least Feynman's famous speech "There's Plenty of Room at the Bottom" which has fittingly been credited with ushering in the nanotechnology era. Crystal engineering, as the solid-state manifestation of supramolecular chemistry, is well positioned to make substantial contributions to this worthwhile endeavor. Within the realm of crystal engineering resides the subdiscipline of metal-organic materials (MOMs) which pertains most simplistically to the coordination bond and includes such objects as coordination polymers, metal-organic frameworks (MOFs), and discrete architectures, each of which share the common aspect that they are designed to be modular in nature. While metal-organic materials have been studied for quite some time, only recently have they enjoyed an explosion in significance and popularity, with much of this increased attention being attributed to two realizations; that this inherent modularity ultimately results in an almost overwhealming degree of diversity and subsequently, that this diversity can give rise to effective control of the properties of functional materials. At long last the goal of attaining fine-tunablity may be within our grasp. In addition to high levels of diversity, MOMs are also characterized by a broad range of complexity, both in their overall structures and in the nature of their constituents. From the simplest molecular polygons to extended 3-periodic frameworks of unprecedented topologies, MOMs have the capacity to adopt an array of structural complexities. Moreover, there has been a recent trend of increasing complexity of the very building blocks that construct the framework. It is the aim of the research presented in this dissertation to survey these two principle aspects of MOMs, diversity and complexity, by focusing upon the use of polycarboxylates and first row transition metals to synthesize several series of closely related materials imbued with varied levels of complexity. Through the use of single crystal X-ray diffraction and the charcterization of the materials' properties, the structure-function relationship has been probed. Finally, novel design strategies incorporating supermolecular building blocks for the creation of a new generation of MOMs has been addressed.

Natural and synthetic common-rock forming minerals were examined using single-crystal X-ray diffraction (SXRD) and electron microprobe (EMP) analyses. The influences of common defect features, such as inclusions in spinel and oxygen positional disorder and twinning in kalsilite, were reported on the respective structures. The case studies show that these defect features could lead to a misinterpretation of X-ray intensity data. The structural interpretations obtained from these XSRD analyses could be significantly different when physical properties of the crystals are considered.In the second part of my dissertation, comparative crystal chemical studies on mantle-derived minerals such as spinel, clinopyroxene, and olivine are reported. These studies were carried out to examine temperature, pressure, and compositional effects on the structures of these phases. In particular, packing arrangements of oxygen atoms were examined in detail to investigate how the packing affects element partitioning among upper-mantle minerals. At ambient conditions, oxygen packing is more distorted in the order of spinel < olivine < clinopyroxene. The packing of oxygen atoms in olivine might have a significant control on element substitutions at high pressure. Because elements whose radius is larger than that of Mg distort the packing of mantle olivine (Fo~89), olivine might limit the amount of those elements, such as Fe2+, entering the structure. In contrast, substitutions of smaller cations in C2/c clinopyroxenes increase packing distortion. For clinopyroxenes enclosed in peridotite and eclogite, higher equilibration pressures are associated with more distorted, less efficiently packed structures. Unlike many minerals reported in Thompson and Downs (2001), spinel becomes more packed with rising temperature when intracrystalline cation exchange reactions are possible. Despite wide chemical variations, spinel samples from one geological environment display a constant packing distortion, which might suggest that spinel is capable of achieving an optimal packing configuration at a given P and T.

The aim of this research project was to synthesise both the normal and inverse cobalt aluminate spinels by various methods and characterise them mainly by Raman spectroscopy with the support of X-ray powder diffraction (XRD), Fourier transform infra-red spectroscopy (FT-IR), energy disperse spectroscopy (EDS), and scanning electron microscopy (SEM). Four different synthesis methods (glycine-gel, citrate-gel, polyol and solid-state) were used to synthesise the cobalt aluminate powders with the general formula CoIICoIIIxAl2-xO4 (where x = 0-2). The gel or powder precursors were annealed at various temperatures ranging from 350ºC - 1000ºC. The properties of the intermediate and final products, influenced by the synthesis method, processing temperature, processing time and particle size, were compared. Raman spectra and XRD patterns indicating the presence of both normal and inverse cobalt aluminate spinel were observed. The inverse spinel was identified both as a transitional phase as well as a final phase, depending on the synthesis method and annealing temperature used. The various synthesis methods were also used to gain further insight into the crystal chemistry of cobalt aluminate. The solid-state method is the more traditional synthesis method. Solution techniques (glycine-gel, citrate-gel and polyol) were used in an attempt to synthesise blue cobalt aluminate at relatively low temperatures and processing times in order to obtain homogeneous, nanosized crystals with broad applicability. The polyol method was found to be most favourable for the synthesis of blue cobalt aluminate with regard to processing temperature and processing time. The various characterisation methods used, show that the intensity of the colour of the powders produced are strongly related to the degree of material crystallinity as well as Al/Co ratio. Inverse (Co2AlO4) and Co3O4 spinels are formed at lower temperatures or when the Co/Al ratio is greater than 0.5. The normal spinel (CoAl2O4) is produced at higher temperatures or when the Co/Al ratio is 0.5. The XRD patterns of CoAl2O4, Co2AlO4 and Co3O4, are very similar because they share the same spinel cubic structure (space group Fd3m) differing only slightly in the lattice size. It has been demonstrated that Raman and XRD can be used to distinguish between inverse and normal spinels while FT-IR and EDS are useful for assessing the purity of the powders produced. As predicted by group theory, five Raman and four IR active vibrations were evident in the results. / Dissertation (MSc)--University of Pretoria, 2009. / Chemistry / unrestricted

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