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Consider a non-Galois cubic extension K/Q ramified at a single prime p > 3. We show that if K is a subfield of an S_4-extension L/Q ramified only at p, we can determine the Artin conductor of the projective representation associated to L/Q, which is based on whether or not K/Q is totally real. We also show that the number of S_4-extensions of this type with K as a subfield is of the form 2^n - 1 for some n >= 0. If K/Q is totally real, n > 1. This proves two conjectures of Siman Wong.

We propose a new formula for the mineral nickelskutterudite, based on our observation that either (or both) Co or Fe3+ are essential structure constituents. The crystal structure of nickelskutterudite, (Ni,Co,Fe) As-3, cubic, Im (3) over bar, Z = 8: a = 8.2653(6) angstrom, V = 564.65(7) angstrom, has been refined to R-1 = 1.4% for 225 unique reflections I > 2 sigma(1) collected on a Bruker X8 four-circle diffractometer equipped with fine-focus, sealed tube MoKa radiation and an APEX-II CCD detector. This is the first report of the crystal structure of nickelskutterudite. Nickelskutterudite, a member of the skutterudite group of isostructural minerals, adopts a distorted perovskite structure with notably tilted octahedra and an unoccupied to partially occupied icosahedral metal site. In the structure of nickelskutterudite, there is one metal (B) site occupied by Ni, Co, or Fe in octahedral coordination with six As atoms. Procrystal electron density analysis shows each As anion is bonded to two cations and two As anions, resulting in a four-membered ring of bonded As with edges 2.547 and 2.475 angstrom. The extreme tilting of BAs6 octahedra is likely a consequence of the As-As bonding. The nickelskutterudite structure differs from the ideal perovskite structure (A(4)B(4)X(12)) in that As4 anion rings occupy three of the four icosahedral cages centered on the A sites. There are reported synthetic phases isomorphous with skutterudite with the other A site completely occupied by a cation (AB(4)X(12)). Electron microprobe analyses of nickelskutterudite gave an empirical chemical formula of (Ni0.62Co0.28Fe0.12)(Sigma 1.02)(AS(2.95)S(0.05))(Sigma 3.00) normalized to three anions. Pure NiAs3 nickelskutterudite, natural or synthesized, has not been reported. In nature, nickelskutterudite is always observed with significant Co and Fe, reportedly because all non-bonded valence electrons must be spin-paired. This suggests that nickelskutterudite must contain Co3+ and Fe2+, consistent with previous models since Ni4+ cannot spin-pair its seven non-bonded electrons, Co3+ and Fe2+, which can spin-pair all non-bonded electrons, are required to stabilize the structure. No anion deficiencies were found in the course of this study so, including the structurally necessary Co and Fe, the chemical formula of nickelskutterudite (currently given as NiAs3-x, by the IMA) should be considered (Ni,Co,Fe)As-3.

In this study, we focus on the substituent effect of the diketone ligands on the structural variation of £]- diketonato metal complexes containing N,N-dimethyl formamide (DMF). Three £]-diketones (hfac, bztf, bzbz) were used, and six-, five-, four- coordinated complexes were found accordingly. It is surprising to find that all six metal-oxygen bonds in the M(hfac)2(DMF)2 complexes are of equal length, seemly in violation of Jahn-Teller theorem. Possible reasons for this observation were discussed in this thesis.

The proportion of authigenic to detrital clay minerals in terrestrial sediments is variable. It has previously been hypothesized that pure Mg-silicates in regions such as Amboseli Basin in Kenya occur due to the absence of Al-rich detritus. We tested this by replicating two Mg-silicate synthesis experiments while adding Al-rich smectite. The first study produced an X-ray amorphous Mg-silicate gel, with little response to addition of Al-rich smectite. The second experiment shifted the 060 peak associated with clay octahedral sheets, suggesting we synthesized trioctahedral domains in a smectite structure. Peak height increased linearly with more heating, indicating crystallinity changes. These results confirm that Al-rich detritus can influence the mineralogy of authigenic clays in saline, alkaline settings. By examining how clay neoformation is affected by silica saturation, we can better understand how the clays found in Neogene lacustrine environments are formed and the climate and of that time.

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Longitudinal growth of long bone occurs at growth plates by a process called endochondral ossification. Endochondral ossification is affected by both biological and mechanical factors. This thesis focuses on the mechanical modulation of femoral bone growth occurring at the proximal growth plate, using mechanobiological theories reported in the literature. Finite element analysis was used to simulate bone growth. The first study analyzed the effect of subject-specific growth plate geometry over simplified growth plate geometry in numerical prediction of bone growth tendency. Subject-specific femur finite element model was constructed from magnetic resonance images of one able- bodied child. Gait kinematics and kinetics were acquired from motion analysis and analyzed further in musculoskeletal modelling to determine muscle and joint contact forces. These were used to determine loading on the femur in finite element analysis. The growth rate was computed based on a mechanobiological theory proposed by Carter and Wong, and a growth model in the principal stress direction was introduced. Our findings support the use of subject- specific geometry and of the principal stress growth direction in prediction of bone growth. The second study aimed to illustrate how different muscle groups’ activation during gait affects proximal femoral growth tendency in able-bodied children. Subject-specific femur models were used. Gait kinematics and kinetics were acquired for 3 able-bodied children, and muscle and joint contact forces were determined, similar to the first study. The contribution of different muscle groups to hip contact force was also determined. Finite element analysis was performed to compute the specific growth rate and growth direction due to individual muscle groups. The simulated growth model indicated that gait loading tends to reduce neck shaft angle and femoral anteversion during growth. The muscle groups that contributes most and least to growth rate were hip abductors and hip adductors, respectively. All muscle groups’ activation tended to reduce the neck shaft and femoral anteversion angles, except hip extensors and adductors which showed a tendency to increase the femoral anteversion. The third study’s aim was to understand the influence of different physical activities on proximal femoral growth tendency. Hip contact force orientation was varied to represent reported forces from a number of physical activities. The findings of this study showed that all studied physical activities tend to reduce the neck shaft angle and anteversion, which corresponds to the femur’s natural course during normal growth. The aim of the fourth study was to study the hypothesis that loading in the absence of physical activity, i.e. static loading, can have an adverse effect on bone growth. A subject-specific model was used and growth plate was modeled as a poroelastic material in finite element analysis. Prendergast’s indicators for bone growth was used to analyse the bone growth behavior. The results showed that tendency of bone growth rate decreases over a long duration of static loading. The study also showed that static sitting is less detrimental than static standing for predicted cartilage-to-bone differentiation likelihood, due to the lower magnitude of hip contact force. The prediction of growth using finite element analysis on experimental gait data and person- specific femur geometry, based on mechanobiological theories of bone growth, offers a biomechanical foundation for better understanding and prediction of bone growth-related deformity problems in growing children. It can ultimately help in treatment planning or physical activity guidelines in children at risk at developing a femur or hip deformity. / <p>QC 20170616</p>

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.

The San Bernardino Mountains are well known for their rich mining history, especially, gold in the mid-1800s and the current mining of one of the world’s largest deposits of high purity limestone. The purpose of this study was to compile new, current, and historical data of the major economic resources that are present and mining that has gone on in the San Bernardino Mountains. It is estimated that historical mining of the Holcomb Valley recovered $457,660,000 of gold or about 350,000 troy ounces based on samples collected for this study and 2013 gold price. The current major geologic resource is the limestone deposits on the north slope of the San Bernardino Mountains. Presently, there are three operators: Omya, Specialty Minerals, and Mitsubishi Cement. The San Bernardino Mountains are well known for skarn gold deposits. New work indicates that the placer gold from Holcomb Valley is often of very high purity. Placer gold samples were analyzed using the scanning electron microscope and energy dispersive x-ray spectra to determine the purity of the gold. Rim and core analysis of the placer gold was used to determine if the gold was transported from its source and to give an estimate of transportation distance. Results show some of the placer gold of Holcomb Valley has been rounded and flattened by weathering and transportation with increased gold purity in the rims while other gold grains still sustain their octahedral crystalline structure. Rims range in gold purity from 84.26% to 100%, with core gold purity ranging from 79.51% to 99.79%. Gold samples were weighed, photographed, measured, and classified by shape, angularity and texture, to assess the effects of transportation. Gold weights where used to calculate an economic value of gold. Geographic Information System “GIS” was used to visually display geology, historical and current mine locations, locations of samples used in this study, and to help calculate the volume of the Holcomb Valley TsE rock unit, which is where the placer gold is deposited. Sediment sample 15 from TsE had the lowest gold value of .002 ounces per cubic yard. This value is inferred to represent the amount of gold remaining after mining. Based on this assumption and the estimated volume of TsE at 50,027,000 cubic yards, the estimated total weight of gold remaining in the deposit is about 100,000 troy ounces, with a dollar value of about $130,760,000, using gold values for 2013. Sample 17 had the highest gold value, with .014 ounces per cubic yard. This is inferred to represent the concentration of placer gold deposits within parts of Holcomb Valley that have never been mined. This yields a total weight of the deposit of roughly 700,000 troy ounces, with an estimated value of $915,320,000 using gold prices for 2013. The gold values were calculated using November 7, 2013 gold spot price of $1,307.60.