Orientador: Julio Carlos Teixeira / Dissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Energia, 2013

Electroanalytical techniques are used to investigate mass transport through density gradient films; lanthanide triflate reduction and oxidation in a Nafion/acetonitrile matrix; and magnetic field effects on hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and lanthanide electrochemistry. Graded density films are more dense at the electrode surface and become less dense out into solution due to a brush polymer structure. Fick's second law expands to account for a diffusion coefficient that varies with distance x normal to the electrode surface. Confocal microscopy, cyclic voltammetry, and computer simulations are used to investigate density graded Ficoll® films. Mass transport approaches steady state (scan rate independence) at slow scan rates where the diffusion length samples the entire film. The use of Ficoll to template an ion exchange polymer is explored by casting Nafion® Ficoll composites. Lanthanide electrochemistry is enabled in acetonitrile at a Nafion modified platinum electrode in the presence of triflate ligands. Formal potentials are shifted into the voltage window of acetonitrile accessible due to triflate complexation. The Nafion further solubilizes the compounds. The mechanism (ECEC) is studied with cyclic voltammetry and x-ray photoelectron spectroscopy. Magnetic field effects on electrochemical systems have been of interest to researchers for the past 65 years. Mass transport effects, such as magnetohydrodynamics and magnetic field gradient effects have been reported, but the Leddy group focuses on electron transfer effects. Electrode surfaces are modified with composite films of magnetic microparticles suspended in ion exchange polymer Nafion. Effects are verified to be electron transfer related and due to the magnetization of chemically inert microparticles. The magnets catalyze the rates of important electron transfer reactions such as hydrogen evolution and oxygen reduction. Magnetic field effects on HER at various noncatalytic metal electrodes are explored with linear scan voltammetry. There is a correlation between the magnetic susceptibility of the electrode metals and the HER exchange currents (reaction rates). Exchange currents are 103× larger for a paramagnetic metal electrode than a diamagnetic one with the same work function. The overpotential at diamagnetic electrodes is decreased by modification with a Nafion + magnetic microparticle composite film. A decrease in overpotential of ∼70 % for all electrodes except platinum is observed. The overpotential decrease correlates with the magnetic susceptibility of the particles. Magnets can enhance differences between lanthanide cyclic voltammograms by shifting current densities at a given potential and enhancing current based on the number of 4f electrons and magnetic moment of each lanthanide ion. Magnetic field effects on ORR in acetonitrile are investigated with cyclic voltammetry. In aprotic solvents, ORR proceeds by a one electron transfer reaction to paramagnetic O2.–. Enhanced reversibility and electron transfer kinetics are observed as well as a decrease in overpotential of ∼100 mV. Magnetic field effects on ORR in a lanthanide triflate solution are also examined. Electron transfer kinetics and reversibility are further enhanced in the presence of lanthanide triflate.

acase@tulane.edu

Electromagnetic microactuators with permanent magnets have many potential applications such as micro-energy scavengers, microswitches, micromirrors and microfluidics. However, many electromagnetic microactuator designs utilize either external permanent magnet or external coil, which do not allow tight integration to other MEMS components and further miniaturization. Furthermore, all of the available permanent magnet microfabrication technologies have some drawbacks and improvements are required. Thus the integrated monolithic electromagnetic microactuator is investigated in this project. The three main components of the electromagnetic actuator have been investigated separately. A novel microfabrication technology called ???Template printing???for the fabrication of polymer bonded permanent magnet has been investigated and developed. It is based on ???Screen printing??? which has its drawbacks on alignment accuracy and poor line definition. This is eliminated in ???Template printing??? by photolithography of the photoresist template. The shape and location of the permanent magnet is defined by the template. A new approach based on the filling of dry magnetic powder and vacuum impregnation has been developed to form the polymer bonded permanent magnet. This allows the use of short pot-life matrix material and the elimination of homogenous mixing. A monolithic electromagnetic microactuator has been fabricated successfully. It consists of a 2-layer planar copper microcoil, surface micromachined polyimide beam and Strontium ferrite/EPOFIX permanent magnet (diameter of 460 ??m and 30 ??m thickness). Large deflection in excess of 100 ??m at 35 mA driving current and magnetic force of 0.39 ??N/mA have been achieved. It compares favourably with other much larger electromagnetic actuators that have been reported. ???Template printing??? has the potential of being a low temperature batch process for the microfabrication of thick polymer bonded permanent magnets with high magnetic properties and low residual stress. The fabrication consistency and the quality of template printed magnet can be improved in future studies.

The work presented herein focuses on the synthesis and characterization of new cyanide bridged molecular magnetic materials that form discrete molecules as well as three dimensional networks. This research is inspired by the recognition that the Prussian blue (PB) family exhibits a wide range of interesting magnetic properties such as photomagnetism, spin crossover, and high TC magnets owing to the presence of the cyanide bridge that promotes magnetic communication between adjacent metal spins. An underexplored facet of this research is the systematic development of the topic with anisotropic metal ions research that was undertaken as part of this dissertation. The resulting discoveries are materials that exhibit a wide range of bistable magnetic properties, including photomagnetism, long range magnetic ordering, SMM, and exchange-biased SMM behavior. New Prussian Blue analogs are presented in Chapter II of this thesis that are based on the nearly unexplored hexacyanoosmate(III) ion. A family of CoII PB derivatives of OsIII were found to exhibit photomagnetic and charge transfer induced spin transition (CTIST) behavior and a study of alkali metal cation dependence revealed marked differences in both the photomagnetic and CTIST properties, with the highest ordering temperature being observed for the K+ analog which exhibits a TC of 28.5 K. The phenomenon of linkage isomerism reported for PB analogs and other molecular materials that incorporate the [Cr(CN)6]3- ion wherein the CN ligand reverses its binding mode between the two metal centers was studied in detail as described in Chapter III. Small molecule models that incorporate [Cr(CN)6]3- and CoII ions were investigated by single crystal X-ray crystallography, magnetism, and solution IR studies and the data led to useful mechanistic information about the nature of the cyanide reversal process. The use of the anisotropic hexacyanoosmate(III) anion to form a trinuclear species with MnIII was undertaken in the study described in Chapter IV. The first SMM based on the hexacyanoosmate(III) ion was discovered and found to exhibit a very rare exchange biased SMM phenomena in one of its crystal forms. In Chapter V new building blocks with the pentadentate MPPA ligand are described which are ideally suited for the preparation of a range of model compounds of the dinuclear and trinuclear variety.

In the field of electric machine design, a trend in many applications has been to design machines with increasing torque density. When machines fail to meet torque density requirements or are simply incapable of matching load torque, gears are commonly used. Magnetic gears have been proposed as a means of increasing torque density within electromechanical systems, while avoiding problems associated with traditional mechanical gears. While the idea behind magnetic gears goes back to early patents, their study and use in industry has been very limited to date. This study looks into variations of the gear which could lead to more industrial use. The effect of pole count upon torque ripple is investigated with finite element analysis (FEA). The analysis is extended to new magnetic layouts which borrow from permanent magnet machine design. One of the most critical components of the gear, the stator pole pieces, are also investigated for variations which aid in construction while maintaining the performance of the gear. As a means of supplementing analysis of the gear, winding function theory (WFT) is used to analyze the gear. Winding function theory has enjoyed success with induction, synchronous, and even switched reluctance machines in the past. This study is the first of its kind to apply winding function theory to a device devoid of windings altogether. It is shown that this method is capable of generating the stall torque and steady-state torque ripple waveforms which have been commonly attempted with FEA. While magnetic gears enjoy distinct advantages over mechanical gears such as inherent overload protection, they are not as torsionally stiff as their mechanical counterparts. As such, the use of damper windings for the purpose of stiffening the gear against transient oscillations is also investigated. Several competing designs are investigated for their performance, and a final design is studied which is capable of arresting transient oscillations in less than a second. In addition, a prototype has been fabricated and will be used to verify the analysis undertaken. The prototype is used to verify variations of the stator pole pieces as well as the inner rotor magnetic layout. A dynamometer has been assembled to test the performance of the prototype. A new design is also proposed for future work.

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Thesis (Ph. D.)--University of Texas at Austin, 2003. / Vita. Includes bibliographical references. Available also from UMI Company.

Magnetic oxides exhibit rich complexity in their fundamental physical properties determined by the intricate interplay between structural, electronic and magnetic degrees of freedom. The common themes that are often present in these systems are the phase coexistence, strong magnetostructural coupling, and possible spin frustration induced by lattice geometry. While a complete understanding of the ground state magnetic properties and cooperative phenomena in this class of compounds is key to manipulating their functionality for applications, it remains among the most challenging problems facing condensed-matter physics today. To address these outstanding issues, it is essential to employ experimental methods that allow for detailed investigations of the temperature and magnetic field response of the different phases. In this PhD dissertation, I will demonstrate the relatively unconventional experimental methods of magnetocaloric effect (MCE) and radio-frequency transverse susceptibility (TS) as powerful probes of multiple magnetic transitions, glassy phenomena, and ground state magnetic properties in a large class of complex magnetic oxides, including La0.7Ca0.3-xSrxMnO3 (x = 0, 0.05, 0.1, 0.2 and 0.25), Pr0.5Sr0.5MnO3, Pr1-xSrxCoO3 (x = 0.3, 0.35, 0.4 and 0.5), La5/8−xPrxCa3/8MnO3 (x = 0.275 and 0.375), and Ca3Co2O6. First, the influences of strain and grain boundaries, via chemical substitution and reduced dimensionality, were studied via MCE in La0.7Ca0.3-xSrxMnO3. Polycrystalline, single crystalline, and thin-film La0.7Ca0.3-xSrxMnO3 samples show a paramagnetic to ferromagnetic transition at a wide variety of temperatures as well as an observed change in the fundamental nature of the transition (i.e. first-order magnetic transition to second order magnetic transition) that is dependent on the chemical concentration and dimensionality. Systematic TS and MCE experiments on Pr0.5Sr0.5MnO3 and Pr0.5Sr0.5CoO3 have uncovered the different nature of low-temperature magnetic phases and demonstrate the importance of coupled structural/magnetocrystalline anisotropy in these half-doped perovskite systems. These findings point to the existence of a distinct class of phenomena in transition-metal oxide materials due to the unique interplay between structure and magnetic anisotropy, and provide evidence for the interplay of spin and orbital order as the origin of intrinsic phase separation in manganites. While Pr0.5Sr0.5MnO3 provides important insights into the influence of first- and second-order transitions on the MCE and refrigerant capacity (RC) in a single material, giving a good guidance on the development of magnetocaloric materials for active magnetic refrigeration, Pr1-xSrxCoO3 provides an excellent system for determining the structural entropy change and its contribution to the MCE in magnetocaloric materials. We have demonstrated that the structural entropy contributes significantly to the total entropy change and the structurally coupled magnetocrystalline anisotropy plays a crucial role in tailoring the magnetocaloric properties for active magnetic refrigeration technology. In the case of La5/8−xPrxCa3/8MnO3, whose bulk form is comprised of micron-sized regions of ferromagnetic (FM), paramagnetic (PM), and charge-ordered (CO) phases, TS and MCE experiments have evidenced the dominance of low-temperature FM and high-temperature CO phases. The "dynamic" strain liquid state is strongly dependent on magnetic field, while the "frozen" strain-glass state is almost magnetic field independent. The sharp changes in the magnetization, electrical resistivity, and magnetic entropy just below the Curie temperature occur via the growth of FM domains already present in the material, even in zero magnetic field. The subtle balance of coexisting phases and kinetic arrest are also probed by MCE and TS experiments, leading to a new and more comprehensive magnetic phase diagram. A geometrically frustrated spin chain compound Ca3Co2O6 provides an interesting case study for understanding the cooperative phenomena of low-dimensional magnetism and topological magnetic frustration in a single material. Our MCE studies have yielded new insights into the nature of switching between multi-states and competing interactions within spin chains and between them, leading to a more comprehensive magnetic phase diagram.

Permanent magnet machines have become an attractive topology for several applications due to their high power density and brushless qualities as compared to conventional wound field machines or squirrel cage machines. The presences of permanent magnets provide distinct advantages, but at the same time unique behaviors that must be accounted for. Recent work has developed permanent magnet machines for high-power and high-speed applications such as may be found in the petro-chemical industry, naval ships, and energy storage systems. / text