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A large amount of research has been done in which the magnetocrystalline anisotropy energy for fcc Ni and bcc Fe was calculated based on the electronic structure of these elements. Unfortunately; the results of these studies don't agree with each other and also differ from the experimental observation. In a previous thesis the effects of numerical errors in the Brillouin zone integrations were investigated. The results of that work explain why different calculations give different results, but do not explain the difference with experiment. The conclusion was that the underlying bandstructure, which was calculated using standard approximations, was not correct. The bandstructure of these elements will be different when improved prescriptions for the exchange-correlation energy are used. There is, however, no clear indication along which lines this approximation should be improved. Here we have taken a different approach to change the bandstructure. We suspected that some important interactions between different atomic orbitals are either ignored or miscounted. In this work, we examined the sensitivity of the energy on the interaction between those orbitals and studied in detail the consequences of changes in some interaction parameters which gave rise to a large energy change. The main result of this work is a better understanding of the relation between changes in the electronic structure in k-space and the resultant change in the magnetocrystalline anisotropy energy. In addition, this work takes another step in trying to find a better understanding how the magnetocrystalline anisotropy energy relates to interactions between neighboring atoms. / Graduation date: 2000

Graduation date: 1995

Controlling the orientation and spatial distribution of discontinuous fibers in composite materials enables product properties to be tailored to anticipated use. Electric fields are already (albeit rarely) used to affect alignment in lignocellulosic (LC) fiber composites. The use of magnetic fields has not, however, been suggested or explored; this is apparently because LC fibers are essentially non-magnetic. The approach may offer, however, some considerable advantages, as long as ferromagnetism may be imparted to the fibers. In the present research several fiber modification processes were considered and two, electroless nickel plating and spray application of a coating containing nickel in suspension, were investigated in more depth. The latter was chosen to render highly engineered, elongated wood particles responsive to magnetic fields. Individual treated particles were suspended in viscous, newtonian silicone fluids and their rotation under the influence of a controlled magnetic field was video recorded. The magnetic torque on the particle was, under the above conditions, directly proportional to the fluid viscosity, to the particle's angular velocity and to a characteristic shape constant. The maximum of the specific magnetic torque (magnetic torque divided by the shape constant) was found to reflect the influence of field strength and particle Ni-treatment on rotation. Results were scaled to an arbitrarily chosen viscosity for comparison. The dependencies of the magnetic torque found in the present research compare with those theoretically predicted for ellipsoidal and cylindrical bodies. For field strengths ranging from 0.07T to 0.15T (below magnetic saturation) the magnetic torque increased almost linearly with increasing field strength. Magnetic torque was also found to increase nearly linearly with increasing bulk Ni-concentration (5g/kg - 50g/kg). Rotational motion was sometimes impeded at low field strengths and this was attributed to a permanent magnetic moment obtained by the particle. A coercive field strength of 7600A/m supported this hypothesis. Judiciously switched field polarity increased magnetic torque at small alignment angles. The present research indicates that orienting LC fibers with magnetic fields is possible and promising. To study dynamics of fiber motion in low viscosity fluids, such as air, a different experimental method is necessary; however, dependencies of the magnetic torque found in the present study still hold true. / Graduation date: 1993

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Magneto-structural correlations have been made for a number of pyridine and pyrazine complexes of iron(II) and copper(Il), involving anions of a range of coordinating abilities, for example, sulfonate, RS0₃⁻ (where R is CF₃, CH₃ or p-CH₃C₆H₄); halide, Cl⁻ Br⁻ or I⁻; pseudohalide, NCO⁻ or NCS⁻; perchlorate and hexafluoroarsenate. Structure was determined by infrared, electronic and Mössbauer spectroscopy and differential scanning calorimetry, and, in some instances, by single-crystal X-ray diffraction. Spectroscopic results were used to investigate the nature of both anion and neutral ligand coordination. In complexes of stoichiometry ML₄ (RS0₃)₂ (where M is Fe or Cu, L is pyridine, pyrazine or 2-methylpyrazine and R is CF₃, CH₃ or p-CH₃C₆H₄), the neutral ligands were found to adopt a unidentate mode of coordination. For several of these complexes, X-ray crystallography revealed a square-planar array of pyridine ligands around the central metal, with anions coordinated in a unidentate mode above and below this plane. A monomeric molecular structure results in which the paramagnetic centres are well isolated from each other giving rise to magnetically-dilute species. In complexes of stoichiometry M(pyz)₂X₂ (where M is Fe or Cu and X⁻ is CF₃S0₃⁻, CH₃S0₃⁻, Cl⁻, Br⁻, I⁻, C10₄⁻ or NCS⁻), pyrazine was found to coordinate through both nitrogen donor atoms and inorganic coordination polymers were produced. X-ray crystallography revealed a two-dimensional lattice in Cu(pyz)₂(CH₃S0₃)₂ with two distinct kinds of bridging pyrazine groups and monodentate sulfonate anions. For the remaining bis(pyrazine) complexes, spectroscopic evidence supports similar structures with unidentate anion coordination and bidentate bridging pyrazine ligands leading to sheet-like polymers. Cu(pyz)₂(CH₃S0₃)₂ and Fe(pyz)₂(NCS)₂ exhibit magnetic susceptibilities which reveal the antiferromagnetic nature of these materials (ˣmax at temperatures of 7.0 and 8.0 K respectively); the data were analysed in terms of a two-dimensional Heisenberg model. For the copper complex, in which the structure shows stronger pyrazine coordination along one dimension, the data were also analysed in terms of a linear chain model. Mössbauer spectroscopy showed Fe(pyz)₂(NCS)₂ to undergo a transition to a magnetically-ordered state at 9.2 K. The magnitude of the exchange coupling through bridging pyrazine in Fe(pyz)₂X₂ complexes (where X⁻ is CF₃S0₃⁻, CH₃S0₃⁻, Cl⁻, Br⁻, I⁻ or C10₄⁻) is considerably less than that present in either Cu(pyz)₂(CH₃SO₃)₂ or Fe(pyz)₂(NCS)₂. Spectroscopic evidence indicates that for Fe(py)₂(CF₃S0₃)₂ and complexes of stoichiometry M(pyz)X₂ (where M is Fe or Cu and X⁻ is CF₃S0₃⁻, p-CH₃C₆H₄S0₃⁻, Cl⁻ or NCO⁻) bridging anionic ligands are present and for the mono(pyrazine) complexes the neutral ligand also coordinates in a bridging mode. Fe(pyz)(CF₃S0₃)₂, Fe(pyz)(NCO)₂ and Cu(pyz)(CF₃SO₃)₂ all exhibit magnetic susceptibility data characteristic of antiferromagnetic materials (ˣmax at temperatures of 4.4, 38 and 7.0 K respectively). The magnetic susceptibilities for these materials were analysed in terms of the two-dimensional Heisenberg model and a linear chain model. Mössbauer spectroscopy shows both Fe(pyz)(CF₃S0₃)₂ and Fe(pyz)(NCO)₂ to undergo a transition to long-range magnetic ordering at temperatures of 3.9 and 27.0 K respectively. Low-temperature (4.2-130 K) magnetic susceptibility measurements for the iron(II) sulfonate compounds, Fe(RS0₃)₂ (where R is F, CF₃, CH₃ or p-CH₃C₆H₄) are reported. For the compounds where R is F, CF₃ or p-CH₃C₆H₄ the magnetic moment data were assessed in terms of crystal-field splitting effects. The magnetic moment data for ɑ and β forms of Fe(CH₃S0₃)₂ are indicative of antiferromagnetic exchange interactions and the characteristics of the susceptibility curve for the β isomer are explained on the basis of a transition from short-range to long range three-dimensional magnetic ordering at 22 K. / Science, Faculty of / Chemistry, Department of / Graduate

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