The following thesis applies an experimental design framework to investigate properties of electron transfer kinetics and homogeneous catalytic reactions. The approach is model-based and the classical Butler-Volmer description is chosen to describe the fundamental electrochemical reaction at a conductive interface. The methodology focuses on two significant design variables: the applied potential at the electrode and mass transport mode induced by physical arrangement. An important problem in electrochemistry is the recovery of model parameters from output current measurements. In this work, the identifiability function is proposed as a measure of correspondence between the parameters and output variable. Under diffusion-limit conditions, plain Monte Carlo optimization shows that the function is globally non-identifiable, or equivalently the correspondence is generally non-unique. However by selecting linear voltammetry as the applied potential, the primary parameters in the Butler-Volmer description are theoretically recovered from a single set of data. The result is accomplished via applications of Sobol ranking to reduce the parameter set and a sensitivity equation to inverse these parameters. The use of hydrodynamic tools for investigating electron transfer reactions is next considered. The work initially focuses on the rotating disk and its generalization - the rocking disk mechanism. A numerical framework is developed to analyze the latter, most notably the derivation of a Levich-like expression for the limiting current. The results are then used to compute corresponding identifiability functions for each of the above configurations. Potential effectiveness of each device in recovering kinetic parameters are straightforwardly evaluated by comparing the functional values. Furthermore, another hydrodynamic device - the rotating drum, which is highly suitable for viscous and resistive solvents, is theoretically analyzed. Combined with previous results, this rotating drum configuration shows promising potential as an alternative tool to traditional electrode arrangement. The final chapter illustrates the combination of modulated input signal and appro- priate mass transport regimes to express electro-catalytic effects. An AC voltammetry technique plays an important role in this approach and is discussed step-by-step from simple redox reaction to the complete EC′ catalytic mechanism. A general algorithm based on forward and inverse Fourier transform functions for extracting harmonic currents from the total current is presented. The catalytic effect is evaluated and compared for three cases: macro, micro electrodes under diffusion control condition and in micro fluidic environments. Experimental data are also included to support the simulated design results.

A definition of fractional Fourier transform as the generalization of ordinary Fourier transform is given at the beginning. Then due to optical reasons the fractional transform of a so-called chirp functions is considered in both theory and practical simulations. Because of a quadratic phase factor which is common in the definition of the transform and some optical concepts, a comparison between these concepts such as Fresnel diffraction, spherical wave, thin lens and free space propagation and the transform has been done. Finally an optical setup for performing the fractional transform is introduced.

Visual inspection is the current method for determining if a wire rope needs to be removed from service. It can be time consuming and inaccurate. The point of this research is to prove that vibration testing could be used on rope to find damage. For this research, capacitive accelerometers were used. A program ran a Fast Fourier Transform (FFT) as the main analysis. From the data produced, it was determined that a damaged rope's vibration signature was different from the vibration signature of the undamaged rope. There were four different types of vibrations used: an impulse while measuring the axial response, a harmonic excitation while measuring the axial response and both transverses directions. The impulse did not provide consistent results to adequately find damage with an acceptable degree of confidence. The harmonic excitations did provide results that showed a different signature. This was the case for all three directions measured. As a result, it was determined that vibrations can be used to find damage in a wire rope.

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Orientador: Lucio Tunes dos Santos / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Matematica, Estatistica e Computação Cientifica / Made available in DSpace on 2018-08-06T01:09:38Z (GMT). No. of bitstreams: 1 Camargo_AnaCarolina_M.pdf: 3666219 bytes, checksum: 1c8c0d68b9fefa425dbd20b478818406 (MD5) Previous issue date: 2006 / Resumo: É comum ser preciso reconstruir funções cujas amostras não estão numa grade igualmente espaçada. Isto é devido ao fato que alguns dos algoritmos mais usados requerem amostras em uma grade Cartesiana regular (uniforme). Portanto, é necessário fazer uma reamostragem uniforme, i.e., interpolar as amostras não uniformes em um conjunto de pontos igualmente espaçados. Neste trabalho, primeiro mostramos que o problema de reamostragem pode ser formulado como um problema de resolver um sistema de equações lineares. Uma solução para este sistema pode ser encontrada utilizando a matriz pseudoinversa, um processo que é impraticável para um número grande de variáveis. A partir de características do problema, é possível desenvolver um algoritmo melhor, o qual usa apenas um número limitado de amostras para calcular cada amostra uniforme, transformando o problema original numa seqüência de sistemas lineares com menos variáveis. O resultado final pode ser visto como ótimo e computacionalmente eficiente. Aplicações são apresentadas para demonstrar a eficiência deste método / Abstract: Its common to be needed to reconstruct functions which samples falls on a nonequally spaced grid. This is due to the fact that some of the most used algorithms require samples in a regular (uniform) Cartesian grid. Therefore, it is necessary to make an uniform resampling, i.e., to interpolate the nonuniform samples in a set of equally spaced points. In this work, it is first shown that the resampling problem can be formulated as a problem of solving a system of linear equations. A solution for this system can be found using the pseudoinverse matrix, a process that is impractical for a large number of variables. From particular characteristics of the problem, it is possible to develop a better algorithm, which only uses a limited number of samples to calculate each uniform sample, transforming the original problem into a sequence of linear systems with less variables. The final result can be viewed as both optimal and computationally efficient. Applications are presented to demonstrate the efficiency of the method / Mestrado / Mestre em Matemática Aplicada

Chronic changes in cardiac load can cause the vertebrate heart to remodel. For ectotherms, ambient temperature can directly alter cardiac load. Therefore, long-term ambient temperature change can initiate a dynamic cardiac remodelling response to preserve cardiac function. The aims of my PhD thesis were to study the effects of chronic temperature change on the ectothermic heart and cardiovascular system, using the cold-active rainbow trout and the cold-dormant freshwater turtle. In contrast to the majority of previous studies, my experiments focused on the passive, rather than active, properties of the heart. In results chapters 3, 4, 5 and 6, I studied the effects of thermal remodelling on the rainbow trout heart. Chronic cold caused a global increase in chamber stiffness, both at the whole chamber and micromechanical level, with an associated myocardial fibrosis. In the ventricle and atrium there was an up-regulation of collagen promoting genes. In the ventricle, I found cold-induced hypertrophy of the spongy myocardium with an up-regulation of hypertrophic growth factors, which was associated with an increase in tissue lipid suggesting an increase in fatty acid oxidation (FAO). In the atrium, there was no hypertrophy, but there was an increase in extra-bundular sinus, suggesting chronic dilation. Chronic warming initiated an opposite response, with increased cardiac compliance associated with an up-regulation of collagen degrading genes in the ventricle and atrium. In the outflow tract (OFT) and atrium, this increased activity of matrix metalloproteinase (MMPs) and in the OFT abundance of MMPs was increased. The warmed ventricle showed atrophy of the spongy myocardium with a decrease in lipid and an increase in glycogen suggesting a switch in cellular energetics from FAO to glycolytic pathways. In chapters 7, 8 and 9, I studied the effects of thermal remodelling on the freshwater turtle heart. I found an in vivo decrease in systemic resistance causing an increased right to left cardiac shunt flow, associated with an increased elastin content of the major outflow vessels. Cold acclimation increased cardiac sensitivity to preload as well as whole chamber passive stiffness and micromechanical stiffness of tissue sections, associated ventricular fibrosis and increased collagen coherency. In addition, chronic cold decreased the gelatinase activity of MMPs and increased mRNA expression of a tissue inhibitor of MMPs. Furthermore, chronic cold was associated with a decrease in tissue lipid and phosphates, but an increase in tissue protein, glycogen and lactate. These changes in tissue biochemistry suggest a switch in cellular energetics from FAO to glycolytic pathways, likely due to the decreased oxygen availability associated with winter inactivity. Overall, the chambers of the ectothermic heart show distinct remodelling phenotypes, which likely reflect their in cardiac function. Thermal remodelling of the fish ventricle serves both cardio-protection, from the haemodynamic strain of changes in cardiac preload and afterload, as well as compensation for the direct effects of temperature. In the turtle, changes in compliance and cellular energetics of the ventricle suggest a cardio-protective mechanism preparing the heart for increased haemodynamic stress and hypoxic or anoxic conditions during inactive winter hibernation.

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The Fourier transform is one of the most useful tools in science and engineering and can be expanded to multi-dimensions and curvilinear coordinates. Multidimensional Fourier transforms are widely used in image processing, tomographic reconstructions and in fact any application that requires a multidimensional convolution. By examining a function in the frequency domain, additional information and insights may be obtained. In this thesis, the development of a symbolic computer algebra toolbox to compute two dimensional Fourier transforms in polar coordinates is discussed. Among the many operations implemented in this toolbox are different types of convolutions and procedures that allow for managing the toolbox effectively. The implementation of the two dimensional Fourier transform in polar coordinates within the toolbox is shown to be a combination of two significantly simpler transforms. The toolbox is also tested throughout the thesis to verify its capabilities.

M.Sc. (Chemistry) / The usefulness of vibrational spectroscopy in identifying surface species, determining adsorbate structures and studying surface reactions has been widely demonstrated. Most of the infrared work on surface species is currently performed using the transmission technique with very thin pressed discs of self supported catalysts. This technique has several disadvantages of which the limited transmission of many catalysts and the loss of available surface area during sample preparation, are but a few. Because of these limitations, information obtained from conventional transmission studies has limited application in terms of understanding and/or improving commercial catalysts. An alternative method which does not suffer from these limitations is Diffuse Reflectance Infrared Fourier Transform Spectroscopy or DRIFTS as it is commonly known. This spectroscopic technique has only recently been extended into the infrared region because of the progress in FTIR instrumentation. Because this is a reflectance technique, the sample is most appropriately a powder, so a high surface area catalyst in its normal powder form can be examined directly without altering its state. A spectroscopic facility which is capable of obtaining DRIFT spectra of adsorbed species at high sensitivity and in situ operating conditions has been established. This facility consists of an FTIR instrument fitted with a diffuse reflectance unit, a heatable high pressure cell and the necessary attachments for gas flow, pressure and temperature control. The project work consisted of an investigation into CO-adsorption on supported rhodium catalysts. By using different combinations of the three parameters: reduction temperature, metal loading and support material, several different species of surface bonded CO have been identified. The three rnein species being: geminal dicarbonyl, linear and bridging CO. As each of these species is associated with a specific Rh-site, conclusions concerning the oxidation state and dispersion of the Rh on the surface could be made. The thermal stability of the different CO-species was studied by increasing the catalyst temperature in a linear fashion. It was found that the geminal dicarbonyl species was the most stable in an oxidising atmosphere. The interconversion of chemisorbed . CO-species at higher temperatures has been spectroscopically verified. A mechanism for CO-dissociation on Rh-catalysts was proposed. In additional experiments the sensitivity of DRIFTS for adsorbed hydrocarbons has been demonstrated. It is concluded that this spectroscopic technique has been proven to be of great significance in the study of surface species on heterogeneous catalysts.