Pulsed laser deposition (PLD) was used to deposit hydroxyapatite (HA) thin films on various substrates, including silicon (100) and titanium (Ti-6Al-4V) alloy. Thin films of amorphous HA were deposited at room temperature and then annealed over a range of temperatures. The microstructure and composition of the films were determined using scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), and X-ray diffraction (XRD). The HA films were found to achieve total crystallinity at 350㮠The mechanical properties of the films were studied by means of nanoindentation and scratch adhesion testing. Crystalline and adherent HA thin films prepared using PLD and post deposition annealing have many potential medical and dental applications.

The purpose of this study was to investigate the thermochemical properties of a transient supersonic flame. Creation of the transient flame was controlled by pulsing air in 200 millisecond intervals into a combustor filled with flowing methane. The combustor was designed following well-known principles of jet engine combustors. A flame holder and spark plug combination was used to encourage turbulent mixing and ignition of reactant gases, and to anchor the transient flame. Combustion created a high temperature and pressure environment which propelled a flame through a choked de Laval nozzle. The nozzle accelerated the products of combustion to a Mach number of 1.6, creating an underexpanded transient flame which burned for approximately 25 milliseconds. Qualitative information of the flame was gathered by two optical systems. An intensified charge-coupled device (ICCD) was constructed from constitutive components to amplify and capture the chemiluminescence generated by the transient flame, as well as the spatial structure of the flame at specific phases. To gather temporal data of a single transient event as it unfolded, a z-type schlieren optical system was constructed for use with a high speed camera. The system resolves the data in 1 millisecond increments, sufficient for capturing the transient phenomenon. The transient system was modeled computationally in Cantera using the GRI-3.0 reaction mechanism. Experimental conditions were simulated within the zero- dimensional computation by explicit control of the reacting gas mass flow rates within the system. Results from the computational model were used to describe the ignition process. The major limitation of the zero-dimensional reactor model is homogeneity and lack of spatial mixing. In this work a Lagrangian tracking model was used to describe the flame behavior and properties as it travels within the zero-dimensional reactor towards the nozzle. Following this, the flow expansion through the de Laval nozzle was calculated using one-dimensional isentropic relations. The computed reactor model data was then contrasted to experimental results from the ICCD and high speed schlieren images to fully describe the events in the transient supersonic flame.

ZnO thin films and nanostructures were grown by eclipse pulsed laser deposition (EPLD) for the first time. On bare sapphire held at 600 °C, a complex nanostructured surface was formed when ablating a metallic Zn target in an oxygen ambient. Nanorods grown by a vapor-solid mechanism clumped together in well separated, micron-sized regions. Nanoscale pyramids with 6 fold symmetry formed between the nanorod clumps by vapor-liquid-solid growth. Strong photoluminescence (PL) was observed from the EPLD grown samples, an order of magnitude stronger than PLD grown nanorods formed under similar growth conditions. Low temperature PL was dominated by the I₇ exciton, which still has an unknown origin. Excitation intensity dependence of I₇ was drastically different than the rest of the nearby excitonic features, behavior which has not been previously reported for bound excitons in ZnO. I₇ also showed large, seemingly random variations in intensity across the surface of each sample compared to the other nearby recombinations, suggesting a structural connection. Introduction of a buffer layer had a profound effect on the morphology and PL from EPLD grown ZnO from a metallic Zn target. Pt has a high melting temperature, which helped suppress the vapor-liquid-solid nanostructure growth resulting in thin-film formation. For standard PLD, the ZnO film showed large grains separated by cracks on the surface. Due to the reduced growth rate in the EPLD geometry, the ZnO layer had a high density of nanoscale pores, reminiscent of the porous Pt buffer layer. Strong PL emission, which was dominated by I₇, was observed from the ZnO/Pt/Al₂O₃ which showed unusual blue/violet emission when the EPLD geometry was used for growth. Thin ZnO buffer layers deposited at reduced temperature also had a profound effect on EPLD grown ZnO, resulting in a random array of nanorods with alignment which was dependent on the growth temperature of the buffer layer. Buffer layers offer another dimension in the control over epitaxial structures and show large potential for EPLD growth of ZnO. Pb was the dominant impurity in the Zn targets used for EPLD growth, hinting at a Pb-related origin for the I7 peak. To explore this idea, hydrothermally grown bulk ZnO was ion-implanted with Pb and then annealed in oxygen at 600 °C to repair damage to the crystal. PL emission intensity was substantially reduced in the Pb-implanted ZnO but the line widths were preserved. No evidence of an I₇ feature was seen for Pb concentrations of up to 0.10%, three orders of magnitude higher than the expected level in the EPLD grown ZnO. However, this does not rule out a Pb-related complex as the origin of I₇ since Pb has complicated interactions with the impurities and native defects in ZnO. Instead of I₇, other sharp excitonic features were observed near the band edge. A bound exciton with a localization energy of 12.4 ± 0.2 meV was observed in the Pb-implanted samples and was attributed to neutral interstitial Pb donors. Pb-implantation produced a clear PL signature which is unique enough to unambiguously detect its presence in ZnO. EPLD also proved successful at depositing oxides of the noble metals. Ir, Pt, Pd, and Ru targets were ablated in oxygen and argon ambients and films were collected on room temperature substrates. Growth in argon resulted in pure metal while oxidized layers were obtained in oxygen. This was clearly evident by the semiconductor-like transmission spectra observed for the oxidized samples. The high fluence used for these growths promoted the oxidation of these resilient metals while the shadow mask blocked most of the molten particulates generated by the high fluence. EPLD is an excellent way to produce oxides from metallic targets, a technique which should be explored in more detail for many material systems.

Pulsed electric field (PEF) processing has been demonstrated to be an effective non-thermal pasteurization method for food-treatment applications. With this method, high voltage, short-duration pulses are applied to a chamber through which liquid food is passed. If the voltage applied and the corresponding electric field develops a potential higher than a critical trans-membrane potential, the pores expand, and the membrane of the living cell is ruptured. Due to the lower amount of energy consumed during a PEF process, the temperature of the liquid is kept much lower than as opposed to conventional pasteurization. The PEF method thus kills bacteria and other microorganisms while preserving the nutrition and taste of the liquid foods. Although the parameter responsible for inactivation is the voltage applied, for any given voltage, the conductivity of the liquid defines a current through the liquid that causes the temperature to rise. Therefore, preventing excessive heating of the liquid requires the application of an efficient waveform. According to the literature, the most efficient waveform is a square wave since the entire energy applied would be used for the inactivation process. Although some power supplies are capable of generating such a waveform, the generation of an efficient waveform that satisfies all the requirements for producing a viable product for PEF applications is still a challenging problem. In this research, a cascadable pulse generator, based on a Marx generator design, was designed and implemented in order to generate a pulsed waveform for the treatment of liquid food. IGBT switches were used to charge capacitors in parallel and to discharge them in series as a means of generating a high voltage at the output. The design was implemented and tested for two stages, generating up to 6 kV and 1.6 kA square pulses with a controllable pulse width from 1 µs to 10 µs. Up to 3 switches were connected in parallel to enhance the current capability of the system. Also investigated are ways to improve the transient time by enhancing the IGBT driver circuit. The effect of design parameters such as pulse width, voltage, and current on the temperature rise in the liquid was also studied. A variety of liquid foods with different conductivities were tested in order to confirm the functionality of the system.

ZnO thin films and nanostructures were grown by eclipse pulsed laser deposition (EPLD) for the first time. On bare sapphire held at 600 °C, a complex nanostructured surface was formed when ablating a metallic Zn target in an oxygen ambient. Nanorods grown by a vapor-solid mechanism clumped together in well separated, micron-sized regions. Nanoscale pyramids with 6 fold symmetry formed between the nanorod clumps by vapor-liquid-solid growth. Strong photoluminescence (PL) was observed from the EPLD grown samples, an order of magnitude stronger than PLD grown nanorods formed under similar growth conditions. Low temperature PL was dominated by the I₇ exciton, which still has an unknown origin. Excitation intensity dependence of I₇ was drastically different than the rest of the nearby excitonic features, behavior which has not been previously reported for bound excitons in ZnO. I₇ also showed large, seemingly random variations in intensity across the surface of each sample compared to the other nearby recombinations, suggesting a structural connection. Introduction of a buffer layer had a profound effect on the morphology and PL from EPLD grown ZnO from a metallic Zn target. Pt has a high melting temperature, which helped suppress the vapor-liquid-solid nanostructure growth resulting in thin-film formation. For standard PLD, the ZnO film showed large grains separated by cracks on the surface. Due to the reduced growth rate in the EPLD geometry, the ZnO layer had a high density of nanoscale pores, reminiscent of the porous Pt buffer layer. Strong PL emission, which was dominated by I₇, was observed from the ZnO/Pt/Al₂O₃ which showed unusual blue/violet emission when the EPLD geometry was used for growth. Thin ZnO buffer layers deposited at reduced temperature also had a profound effect on EPLD grown ZnO, resulting in a random array of nanorods with alignment which was dependent on the growth temperature of the buffer layer. Buffer layers offer another dimension in the control over epitaxial structures and show large potential for EPLD growth of ZnO. Pb was the dominant impurity in the Zn targets used for EPLD growth, hinting at a Pb-related origin for the I7 peak. To explore this idea, hydrothermally grown bulk ZnO was ion-implanted with Pb and then annealed in oxygen at 600 °C to repair damage to the crystal. PL emission intensity was substantially reduced in the Pb-implanted ZnO but the line widths were preserved. No evidence of an I₇ feature was seen for Pb concentrations of up to 0.10%, three orders of magnitude higher than the expected level in the EPLD grown ZnO. However, this does not rule out a Pb-related complex as the origin of I₇ since Pb has complicated interactions with the impurities and native defects in ZnO. Instead of I₇, other sharp excitonic features were observed near the band edge. A bound exciton with a localization energy of 12.4 ± 0.2 meV was observed in the Pb-implanted samples and was attributed to neutral interstitial Pb donors. Pb-implantation produced a clear PL signature which is unique enough to unambiguously detect its presence in ZnO. EPLD also proved successful at depositing oxides of the noble metals. Ir, Pt, Pd, and Ru targets were ablated in oxygen and argon ambients and films were collected on room temperature substrates. Growth in argon resulted in pure metal while oxidized layers were obtained in oxygen. This was clearly evident by the semiconductor-like transmission spectra observed for the oxidized samples. The high fluence used for these growths promoted the oxidation of these resilient metals while the shadow mask blocked most of the molten particulates generated by the high fluence. EPLD is an excellent way to produce oxides from metallic targets, a technique which should be explored in more detail for many material systems.

A investigação estrutural de materiais desordenados tem grande interesse devido ao rápido progresso de suas aplicações tecnológicas. A ressonância magnética, particularmente a ressonância paramagnética eletrônica (RPE) de onda contínua (CW) e pulsada, tem demonstrado ser um método altamente sensível para a análise das propriedades físicas e químicas de materiais vítreos e amorfos. Neste trabalho, aplicamos essas técnicas, em particular as técnicas de RPE pulsada, electron spin echo envelope modulation (ESEEM) com seqüências de dois e três pulsos e a de echo detected field sweep (EDFS) no estudo de três materiais distintos. No primeiro trabalho é apresentado um estudo das mudanças estruturais fotoinduzidas em filmes do sistema vítreo [Sb(PO3)3]nSb203 dopados com Cu2+.Esse material possui a propriedade de fotocontração quando exposto à luz ultravioleta. As medidas de RPE CW e de EDFS mostram que ocorre uma distorção na estrutura local quando o filme é irradiado por UV. Os espectros de ESEEM mostram a presença e uma linha de 31P que diminui drasticamente quando o filme é irradiado. O segundo trabalho descreve o estudo do xerogel pentóxido de vanádio, V2O3:nH2O com n = 1.8. Os espectros de RPE CW do V4+ na temperatura ambiente exibem uma estrutura hiperfina isotrópica tipicamente observada em líquidos. Em baixas temperaturas (65K) o espectro é anisotrópico e corresponde ao observado para amostras sólidas em pó. As simulações dos espectros CW estão em acordo com os resultados experimentais. Estudos de ESEEM em baixas temperaturas, efetuados para diversos valores do campo externo mostram que as modulações correspondentes aos núcleos 1 H existem somente para as componentes perpendiculares do espectro de ii EDFS. Os resultados obtidos são consistentes com o modelo estrutural no qual quatro radicais OH estão situados em posições equivalentes no plano equatorial da estrutura do V4+. Uma molécula de água pode estar localizada no sitio oposto da ligação axial V=0. No terceiro trabalho são estudados vidros foto-termo-refrativos (phototherino - refractive ou PTR). Vidros PTR do sistema O-Si-Na-Zn-Al-K-F-Br dopados com Ce, Ag, Sn, Sb exibem cristalização em nano-escala, induzidas após irradiação com luz ultravioleta e subseqüentes tratamentos térmicos. Neste trabalho, conjuntos de amostras irradiadas e/ou tratadas termicamente são analisados por RPE CW, EDFS e ESEEM. RPE CW não forneceu informações confiáveis sobre a estrutura do vidro. Mudanças significativas foram observadas nos espectros de EDFS, indicando mudanças estruturais na vizinhança dos centros paramagnéticos. Medidas sistemáticas de ESEEM em várias posições de campo magnético mostram claramente a modulação característica de 23Na, indicando que núcleos de Na são parte da estrutura ligante ao redor do centro observado. Para a amostra irradiada e tratada por 1 hora a 450°C e 2 horas a 520°C, o espectro de ESEEM obtido nas proximidades de g = 2 mostra a presença adicional de uma linha que pode ser atribuída a íons de 19F. Comparando-se com resultados de RMN, pode-se concluir que domínios de NaF são formados nas proximidades desse centro paramagnético. O quarto trabalho está relacionado com a simulação numérica de espectros de RPE CW e consiste em um estudo teórico a respeito da determinação dos autocampos de um Hamiltoniano de spin. O algoritmo proposto pode ser resolvido pelo \"Filter Diagonalization Method\", ou FDM, sugerindo uma nova metodologia capaz de resolver o problema de uma maneira mais direta do que a empregada pelos métodos usuais / The structural investigation of disordered materiais has been of great interest due to fast progress in technological applications. Magnetic resonance, particularly the pulsed and continuous wave electron paramagnetic resonance (EPR), has demonstrated to be a high sensibility method to analyze chemical and physical properties of disordered and vitreous materiais. In this work, we applied these techniques, particularly the electron spin echo envelope modulation (ESEEM) with two and three pulses and echo detected field sweep (EDFS) to investigate three different materiais. In the first investigation, we show a study of photo-induced structural changes in the [Sb(PO3)3]nSb203 vitreous system films doped with Cu2+ ions. This material has photo-contraction properties when exposed to UV light. EPR CW and EDFS measurements show that the local structure is distorted when the fim is UV irradiated. The ESEEM spectra show the presence of a 31P line that vanishes for irradiated films. The second work describes the study of vanadium pentoxide xerogel V205: nH2O with n = 1.8. The CW EPR spectra of V4+ at room temperature exhibts the isotropic hyperfine structure typical of liquid phases. At low temperatures (65 K) the spectrum is anysotropic, as expected for solid powder samples. Numerical simulations of the EPR spectra in the two temperature limits are in good agreement with the experimental data. An ESEEM study carried out at low temperatures and for different static field values show that the nuclear modulations associated to 1H nuclei are observable only for the perpendicular components of the EDFS spectrum. Results are consistent with the structural model in which the four OH radicals are placed in iv equivalent positions of the V4+ structure equatorial plane. A water molecule can be placed in the opposite site of the axial V=O bond. In the third work, CW and pulsed EPR spectroscopy techniques were applied to study the effects of the thermal treatments and UV irradiation on photo-thermorefractive (PTR) glasses. PTR glasses of the system 0-Si-Na-Zn-Al-K-F-Br doped with Ce, Ag, Sn, Sb exhibit NaF crystallization at nano-scale, induced after U.V. irradiation and subsequent thermal treatments. Sets of irradiated and/or thermal treated samples were analyzed at the X-band by CW and pulsed techniques, such as EDFS and ESEEM. The forth work is related to the numerical simulation of CW EPR spectra and reports a new technical approach to the resonance field problem associated with a given spin hamiltonian. The proposed alghoritm can be solved by the \"filter diagonalization method\" (PIM), suggesting a new methodology, which is capable to solve the problem in a more straightforward way when compared to existing methods

No description available.

No description available.

A coherent optical THz (1.5 THz, 200 µm) source was developed based on pulsed, near IR, fiber lasers, and frequency mixing in nonlinear crystals. The generated THz frequency is determined by the difference frequency of two high peak power pulsed fiber lasers at 1550 nm and 1538 nm. When incident to the crystal, the near IR lasers induce a polarization at their beat frequency which generates the THz radiation. The pulsed fiber lasers are single transverse mode, have high pulse energy and peak powers of 0.38 mJ and 128 kW respectively. They are transform limited at a few ns in duration with very good beam quality of M² ≈ 1.2. The pulse seed was created by modulating a constant laser beam with an electro-optic modulator. An arbitrary waveform generator was used to pre-shape these pulses to compensate for pulse distortion caused by pump gain depletion in the subsequent fiber amplifiers. Pre-amplifiers were constructed using commercial erbium doped silica fiber. Special, highly doped, large core, phosphate fiber was developed in-house to further amplify the pulses, while avoiding nonlinear scattering processes such as stimulated Brillouin scattering and stimulated Raman scattering. THz generation was achieved in both ZnGeP₂ and GaP which were chosen based on their low pump and THz absorption, as well as high nonlinear coefficient. Angle tuning was used to phase match all three optical frequencies in ZnGeP₂ thanks to its birefringence. Layers of GaP ~500 µm thick were pressed together alternately rotated 180° around the normal to quasi-phase match the pump and THz frequencies. To increase the efficiency of the THz generation an external optical cavity was used to enhance and recycle the IR pump pulses. The nonlinear crystal was placed inside the cavity and 151 times enhancement of THz power was observed.

Este trabalho tem como finalidade usar a técnica do pulso eletroacústico (PEA) para investigar a formação de carga espacial em materiais poliméricos utilizados na isolação elétrica, tais como, polietileno de alta densidade e o XLPE e a também investigar a resposta ferroelétrica do PZT durante o processo de polarização. O método de pulso eletroacústico é baseado na propagação do sinal acústico gerado pela aplicação de um pulso de tensão elétrico de 5ns de largura. Apresentamos todas as etapas da montagem do sistema PEA, a análise do sistema elétrico e o tratamento matemático dos sinais de forma obter urna melhor resposta do sistema. Iniciamos o trabalho utilizando duas amostras de PET polarizadas previamente no triodo corona. O par de amostras carregado com a mesma polaridade foi unido pelas faces carregadas eletricamente e foi determinada a origem do sinal obtido na interface inferior amostra-eletrodo. Confrontamos os resultados experimentais obtidos no PEA (com a amostra em curto-circuito) com a análise teórica o qual nos forneceu subsídios para determinar o sinal da carga que aparece nas faces da amostra e de onde o sinal era proveniente na interface. Empregamos a mesma idéia aplicada ao PET para determinar a origem do sinal na interface PZT-eletrodo, concluímos que a origem do sinal era proveniente do material de maior impedância acústica. Investigamos com a técnica do pulso eletroacústico, originalmente desenvolvido para polímeros, o chaveamento ferroelétrico de cerâmicas ferroelétricas. Abordamos o comportamento do decaimento da polarização ferroelétrica após a remoção do campo elétrico de saturação, determinamos a curva de histerese e o perfil do campo elétrico dentro da amostra quando se aplica rampa de tensão com taxa muito baixa e admitimos que o processo era quase-estacionário. Nos polímeros utilizados na isolação elétrica investigamos a formação da carga espacial no PE e nos materiais relacionados sob alto campo elétrico e em função do tempo de polarização. / The purpose this work was using to PEA method for investigation of the ferroelectrics response in PZT and space charge formation in polymeric materials (PE, XLPE) used as electrical insulation for high voltage devices. The PEA method is based on propagation acoustic signal generated by the application of a short electric field pulse, typically 5 ns in duration. Show all the steps of the experimental set-up PEA system, analysis of the electrical system and the mathematical treatment of the signals. Start up the work with double layer PET samples previously poled in corona triode with aim of determination of the origin of the signal obtained to in the sample-lower electrode interface and the experimental results obtained to PEA satisfactorily explain the theory. Make up his mind to apply a same idea to PZT, but only one sample it was poling. From that measurements with PET and PZT, is found that the signal come from of material biggest acoustic impedance. With the PEA method, in the first place development for polymers, it was investigated the ferroelectrics ceramics: ferroelectric switching, decaying of ferroelectric polarization after removal saturation electrical field, hysteresis loop measurements and the determination of coercive field. To obtain the electrical field profile through the thickness of the ferroelectrics ceramics it was applied ramp voltage method in process steady-state (low rate). The space charge formation in polymers under high electric field and in time function was investigated.