Nos últimos anos tem se dado uma evolução muito grande na área industrial de MEMS, e esta se caracteriza por desenvolvimento dos processos de microeletrônica para diminuição de custos e a própria integração de diferentes sistemas que passam a ser muito confiáveis em diferentes aplicações. Motivado pelas tendências de elevar os conhecimentos de processos para obtenção de MEMS, foi proposto um trabalho de corrosão anisotrópica de silício utilizando solução de hidróxido de potássio (KOH) junto com a adição de sais metálicos. O objetivo é comprovar o efeito de compensação cinética da reação e a influência destes metais no caráter anisotrópico e nas taxas de corrosão. Foi analisado o efeito de zinco, alumínio e cobre, e puderam ser observadas alterações nas taxas de corrosão e, conseqüentemente, nas geometrias resultantes no corpo de silício. Com a caracterização dessas mudanças comprovou-se suposições anteriores de que o efeito de compensação cinética encontrado na síntese direta de dimetilclorosilana (DMDCS) e silício, também ocorreria para a corrosão de silício em KOH, pois esses processos obedecem a lei de Arrhenius e tem um comportamento anisotrópico em silício. Os resultados obtidos, graças a um grande detalhamento de todos as etapas de processo e caracterização voltada à tecnologia do silício, comprovaram as suposições teóricas e mostraram como pode ser modificada a taxa de corrosão na anisotropia com a adição de metais em solução. / In the past few years it has been a huge evolution in industrial area of MEMS, and this one is characterized by the development of the processes of microelectronic to reduce cost and to integrate different systems that become very trustful in different applications. It is being done a work in silicon anisotropic etching in Potassium hydroxide (KOH) added with metallic impurities aiming the study of the kinetic compensation effect and the influence of these metals in the anisotropy and in etch rates. It was analyzed the effects of Zinc, Aluminum and Cupper and it could be observed changes in etch rates, and, consequently, in the resulting geometries. After characterization of theses changes it was proved that previous suppositions that the kinetic compensation effects found in direct synthesis of dimethyldichorosilane (DMDCS) and silicon would also occur for silicon anisotropic etching in KOH, due to both reactions follows Arrhenius law and are anisotropic reactions. The obtained results proved the theory suppositions that the etch rate and anisotropy can be modified when adding metals to the solution.

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Distributed Point Source Method (DPSM) was developed by Placko and Kundu 1, as a technique for modeling electromagnetic and elastic wave propagation problems. DPSM has been used for modeling ultrasonic, electrostatic and electromagnetic fields scattered by defects and anomalies in a structure. The modeling of such scattered field helps to extract valuable information about the location and type of defects. Therefore, DPSM can be used as an effective tool for Non-Destructive Testing (NDT). Anisotropy adds to the complexity of the problem, both mathematically and computationally. Computation of the Green's function which is used as the fundamental solution in DPSM is considerably more challenging for anisotropic media, and it cannot be reduced to a closed-form solution as is done for isotropic materials. The purpose of this study is to investigate and implement DPSM for an anisotropic medium. While the mathematical formulation and the numerical algorithm will be considered for general anisotropic media, more emphasis will be placed on transversely isotropic materials in the numerical example presented in this paper. The unidirectional fiber-reinforced composites which are widely used in today's industry are good examples of transversely isotropic materials. Development of an effective and accurate NDT method based on these modeling results can be of paramount importance for in-service monitoring of damage in composite structures.

Electrophoretic displays (EDPs) are an attractive low power technology for small to large area displays. Such display technology has seen a surge of research interest with the launch of successful e-readers in the market place, owing to their lower power consumption and paper-like quality. This work aims to look at the influence of shape on the electrophoretic mobility of particles for such devices. Crosslinked poly(methyl methacrylate) (PMMA) precursor particles with a narrow size distribution were produced by non aqueous dispersion polymerisation utilising a pump-feed method. To produce shape anisotropic particles an adapted version of the dynamic swelling method for polar media was chosen. Suitable monomers were screened by the use of Hansen solubility theory to find monomers which interact with PMMA but not the solvent. It was found that 2- hydroxyethyl methacrylate (HEMA) and N-hydroxyethyl acrylamide (HEAm) were two such suitable monomers, methyl methacrylate (MMA) was also used as a control series.It was found that cluster-like particle morphologies could be produced by the MMA system by the inclusion of small quantities of crosslinking monomer. This was due to precipitation of higher molecular weight polymer segments to the seed particle surface. The cluster-like morphology could be enhanced by use of a polar crosslinking monomer and by sequential reactions. For the polar system, it was found that the reactions with pure monomer were unclean, due to the solubility mismatch of the monomer and the solvent system. This was overcome by a copolymerisation with MMA. The system showed different particle morphologies could be produced by varying the polar monomer content. In one case a sample of pure dumbbell-like particles could be produced. These dumbbell-like particles are thought to be chemical as well as shape anisotropic owing to monomer composition. EPD evaluation for the particles was undertaken and showed that all particles can become highly charged in low dielectric constant media, but that the shape anisotropic particles are prone to adsorption to the cell walls and electrodes.The work outlined in this thesis shows the first reporting of shape anisotropic polymeric particles produced in low dielectric constant solvents system.

Refcoal is a carbon precursor obtained by alkali-mediated extraction of coal with aprotic solvents such as DMF. Refcoal can be converted into a graphitic material through appropriate heat treatment. Graphitisable materials require the development of an intermediate liquid crystalline mesophase. Thus formation of a mesophase during the carbonisation of Refcoal is essential for obtaining highly graphitisable anisotropic cokes suitable for nuclear graphite applications. Anisotropic carbons are even more important in other commercial and industrial application because of their distinctive properties. The formation of anisotropic carbon depends on the nature of the parent precursor, temperature and carbonisation conditions, especially the molecular mobility during the mesophase stage. High-temperature extraction of coal produces Refcoal that yield cokes with a low level of anisotropy. Good control of the mesophase stage during carbonisation may lead to the development of anisotropic cokes. Hydrogen donor additives increase the molecular mobility in the liquid phase by stabilising the free radicals formed by thermal decomposition of coal. Hydrogen donor additives also increase the temperature range over which fluidity occurs, thereby allowing the formation of large sized mosaic structures. Mittal pitches (CTP) and tetralin were examined for their effectiveness as hydrogen donor additives. Refcoal blends containing 10 to 50% by mass additive were prepared by mixing and carbonisation conducted at temperatures ranging form 400 to 1000 °C. Samples were analysed using thermogravimetric analysis (TGA), diffuse reflectance infrared Fourier transform (DRIFT), optical microscope techniques, scanning electron microscopy (SEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that addition of at least 10% tetralin improves the optical texture of Refcoal cokes and also increases the carbon yield. In both tetralin and pitch addition, 20% additive gave coarse circular anisotropic cokes after carbonisation at 650°C. However the carbon yield was reduced for the Refcoal coke treated with Mittal pitch. In fact the yield roughly decreases with an increase in pitch content. Although the cokes from pitch treated Refcoals showed a low ratio of d/g (where d indicates the degree of disordering and g the degree of ordering), Raman and XRD results indicate little further improvement in crystallinity but SEM showed development of a smooth morphology with increasing pitch content. Previous literature results suggest that this indicates that the material must have passed through a mesophase stage. Surprisingly, the addition of tetralin yielded cokes with high ratio of d/g, but improved the carbon yield and optical anisotropy. Increasing tetralin content in the carbonising system increased the size of anisotropic textures but the SEM micrographs show rough morphology with compounds that appear to inhibit mesophase spheres coalescence. / Dissertation (MSc)--University of Pretoria, 2009. / Chemistry / unrestricted

This thesis will present the synthesis, characterization and magnetic measurements of lanthanide complexes with varying nuclearities (Ln, Ln2, Ln3 and Ln4). EuIII, GdIII, TbIII, DyIII, HoIII and YbIII have been selected as the metal centers. Eight polydentate Schiff-base ligands have been synthesized with N- and mostly O-based coordination environments which chelate 7-, 8- or 9-coordinate lanthanide ions. The molecular structures were characterized by single crystal X-ray crystallography and the magnetic properties were measured using a SQUID magnetometer. Each chapter consists of crystal structures and magnetic measurements for complexes with the same nuclearity. There are eight DyIII SMMs in this thesis which are discrete molecules that act as magnets below a certain temperature called their blocking temperature. This phenomenon results from an appreciable spin ground state (S) as well as negative uni-axial anisotropy (D), both present in lanthanide ions owing to their f electron shell, generating an effective energy barrier for the reversal of the magnetization (Ueff). The ab initio calculations are also included for the SMMs with high anisotropic energy barriers to understand the mechanisms of slow magnetic relaxation in these systems.

Soft materials are ubiquitous in every aspect of our daily life. These materials composed of a wide range of subfields including surfactants, foams, emulsions, pastes, slurries, polymers, gels, and colloidal suspensions. In recent years, there has been a great interest focusing on the understanding of the macroscopic properties of various types of soft materials as a function of their microstructures. For example, the structure-property relationship of physically-associating triblock copolymer gels can be controlled by selecting different types of solvents and changing the temperature. In these systems, gelation occurs due to the significant changes in the solubility of one or more of the blocks with temperature compared to the other blocks. Therefore, changing the temperature can lead to the structural transitions and macroscopic properties. The other strategy that can be used to modify the macroscopic performance of polymer gels is through the incorporation of nanoparticles, such as graphene nanoplatelets and nanotubes. The addition of nanoparticles can also affect the mechanical properties of concentrated suspensions in which, understanding the structure/flow properties is vital for processing and manufacturing of a product. Despite significant advances in the field of soft materials, our understanding in linking the structure-property relationships of polymer gels and concentrated suspensions is incomplete. With this perspective, in this dissertation, shear-rheometry and scattering techniques were used to understand the structural changes of the self-assembled triblock copolymer gels over a wide length-scale and broad temperature-range. Graphene nanoplatelets have been incorporated into this system to investigate the self-assembly behavior and mechanical properties as a function of graphene concentration. On the other hand, in concentrated suspensions of functionalized nanoparticles in a low-molecular- weight polymeric media, the effect of nanoparticles on the rheological properties were investigated. The present work provides a better understanding of the nanoparticles’contributions on microstructure and mechanical behavior of soft materials.

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Structural refinements have been completed using data recorded for a Mg-rich cordierite at 24°C, 375°C, 775°C and 24°C (after heating to 775°C) and for an Fe-rich cordierite at 24°C and 375°C. The mean T-0 bond lengths in both cordierites remain unchanged but the mean octahedral bonds (M-0) lengthen upon heating. The unusually low thermal expansion of the Mg-cordierite is the result of its relatively "rigid" tetrahedral framework and the anisotropic expansion of octahedra isolated from each other. This anisotropic expansion leads to a slight rotation of the six-membered rings, a concomitant collapse of the structure parallel to c, and an expansion parallel to a and b. In the Fe-cordierite, the Fe-octahedron is more flattened, resulting in c being smaller and a and b being larger than the cell dimensions in the Mg-cordierite. Upon heating Fe-cordierite, there is no evidence for a rotation of the rings and a, b and c increase as the M-O bonds expand. A re-examination of the water orientation in the cavities of the Mg-cordierite using neutron and X-ray Δp maps confirms the orientation obtained previously by spectroscopic methods for type I water, i.e., H-O-H near (100) with the H-H vector nearly parallel to e. However, no evidence was found in the Δp maps for type II water. A peak ascribed to the alkali atoms that centers the six-membered ring becomes elongated parallel to a upon heating through 375°C, while the peak ascribed to the oxygen associated with H2O is absent in the Mg-cordierite at 775°C and in the Fe-cordierite at 375°C. After heating the Mg-cordierite to 775°C the peak reappeared in the Δp maps computed from data recorded at 24°C, but it no longer showed an elongation parallel to a as it did before heating. / Master of Science