The thesis focuses on synthesis and characterization of nanocatalysts for applications in wastewater treatment and hydrogen production through electrochemical water splitting. Different photocatalysts and electrocatalysts are synthesized using wet chemistry techniques as well as Pulsed Laser Deposition (PLD). The synthesized catalysts pave demonstrate excellent catalytic activity thereby paving way for their use on an industrial scale.

Although it is known that gold (Au) is diamagnetic in bulk form, it has been reported that Au displays magnetic properties when reduced to the nano-scale. Researchers found magnetism in Au nanoparticles (NPs) in a size range from 2 to 10 nanometers. Moreover, the Au nanoparticles are usually coated by thiol-containing organic caps, which are believed to be responsible for the magnetism. However, others suggest that organic capping is not necessary to observe magnetism in Au NPs, and magnetism may be an intrinsic property for nano-structured gold. For this investigation, we used pulsed laser deposition to prepare nano-structured gold of different sizes and concentrations to investigate the magnetic properties. Our experiment results confirmed that for the samples in which Au is in the metallic state as nanoparticles with ~5 nm diameter, as well as inthe alloy form, bonded with indium, the samples show ferromagnetism when embedded in an Al2O3 matrix without any thiol-containing organic capping. Our results suggest that ferromagnetism is an intrinsic property of Au nano-structures, which means that it is not necessary to incorporate Au-S bonds with organic coatings in order to observe this phenomenon. We believe due to the significant broken symmetry at the surface of the nanoparticles, holes are generated in d bands of the surface Au atoms. These holes are most possibly responsible for ferromagnetism in Au nanoparticles. The realization of magnetism in Au coupled with the lack of clear understanding of its origin makes the investigation of magnetism of diamagnetic metals ripe for further inquiry. / Ph. D.

Neutron diffusion parameter measurements have been made at 21°C in 20, 50, and 80 percent concentrations of heavy and light water, including pure H20 and D2 0 as moderators. Pulsed neutron techniques were used with a 250-kv Cockcroft-Walton accelerator as the pulsed source. The range of bucklings used was from 0.05 cm⁻² to 0.70 cm⁻². The values for the diffusion coefficient, Dₒ; the diffusion cooling coefficient, C; and the transport mean free path, A_tr, were determined from the expansion of the decay constant to second order using iteration procedure. The values of Dₒ, C, and A_tr are tabulated below for the various concentrations, including pure H₂O and D₂O. <table style="width:100%"> <tr> <th>Percent D₂0</th> <th>Dₒ x 10⁻⁴ (cm²sec⁻¹)</th> <th>C x 10⁻⁵ (cm⁴sec⁻¹)</th> <th>λ_tr (cm)</th> </tr> <tr> <td>0</td> <td>3.634±0.048</td> <td>0.161±0.008</td> <td>0.443</td> </tr> <tr> <td>20</td> <td>3.779±0.017</td> <td>0.170±0.032</td> <td>0.515</td> </tr> <tr> <td>50</td> <td>6.964±0.044</td> <td>0.74±0.12</td> <td>0.915</td> </tr> <tr> <td>80</td> <td>11.75±0.68</td> <td>2.19±0.42</td> <td>1.602</td> </tr> <tr> <td>100</td> <td>19.66±1.37</td> <td>3.56±1.08</td> <td>2.670</td> </tr> </table> / Doctor of Philosophy

In plasma assisted thin film growth, control over the energy and direction of the incoming species is desired. If the growth species are ionized this can be achieved by the use of a substrate bias or a magnetic field. Ions may be accelerated by an applied potential, whereas neutral particles may not. Thin films grown by ionized physical vapor deposition (I-PVD) have lately shown promising results regarding film structure and adhesion. High power impulse magnetron sputtering (HIPIMS) is a relatively newly developed technique, which relies on the creation of a dense plasma in front of the sputtering target to produce a large fraction of ions of the sputtered material. In HIPIMS, high power pulses with a length of ~100 μs are applied to a conventional planar magnetron. The highly energetic nature of the discharge, which involves power densities of several kW/cm2, creates a dense plasma in front of the target, which allows for a large fraction of the sputtered material to be ionized. The work presented in this thesis involves plasma analysis using electrostatic probes, optical emission spectroscopy (OES), magnetic probes, energy resolved mass spectrometry, and other fundamental observation techniques. These techniques used together are powerful plasma analysis tools, and used together give a good overview of the plasma properties is achieved. from the erosion zone of the magnetron. The peak plasma density during the active cycle of the discharge exceeds 1019 electrons/m3. The expanding plasma is reflected by the chamber wall back into the center part of the chamber, resulting in a second density peak several hundreds of μs after the pulse is turned off. Optical emission spectroscopy (OES) measurements of the plasma indicate that the degree of ionization of sputtered Ti is very high, over 90 % in the peak of the pulse. Even at relatively low applied target power (~200 W/cm2 peak power) the recorded spectrum is totally dominated by radiation from ions. The recorded HIPIMS spectra were compared to a spectrum taken from a DC magnetron discharge, showing a completely different appearance. Magnetic field measurements performed with a coil type probe show significant deformation in the magnetic field of the magnetrons during the pulse. Spatially resolved measurements show evidence of a dense azimuthally E×B drifting current. Circulating currents mainly flow within 2 away cm from the target surface in an early part of the pulse, to later diffuse axially into the chamber and decrease in intensity. We record peak current densities of the E×B drift to be of the order of 105 A/m2. A mass spectrometry (MS) study of the plasma reveals that the HIPIMS discharge contains a larger fraction of highly energetic ions as compared to the continuous DC discharge. Especially ions of the target material are more energetic. Time resolved studies show broad distributions of ion energies in the early stage of the discharge, which quickly narrows down after pulse switch-off. Ti ions with energies up to 100 eV are detected. The time average plasma contains mainly low energy Ar ions, but during the active phase of the discharge, the plasma is highly metallic. Shortly after pulse switch-on, the peak value of the Ti1+/Ar1+ ratio is over 2. The HIPIMS discharge also contains a significant amount of doubly charged ions.

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

"The pulsed plasma thruster (PPT) is an onboard electromagnetic propulsion device currently being considered for use in various small satellite missions. The work presented in this thesis is directed toward improving PPT performance using a control engineering approach along with externally applied magnetic fields. An improved one dimensional electromechanical model for PPT operation is developed. This slug model represents the PPT as an LRC circuit with a dynamics equation for the ablated plasma. The improved model includes detailed derivation for the induced magnetic field and a model for the plasma resistance. A modified electromechanical model for the case of externally applied magnetic fields is also derived for the parallel plate geometry. A software package with a graphical user interface (GUI) is developed for the simulation of various PPT types, geometric configurations, and parameters The simulations show excellent agreement with data from the Lincoln Experimental Satellite (LES)-6, the LES-8/9 PPT and the Univ. of Tokyo PPT. The control objective employed in this thesis involves the maximization of the specific impulse and thrust efficiency of the PPT, which are each directly related with the exhaust velocity of the thruster. This objective is achieved through the use of an externally applied magnetic field as a system actuator. To simulate an open-loop constant-input controller the modified electromechanical PPT model is applied to the various PPT configurations. In this controller the external magnetic field was applied as constant throughout or portions of the PPT channel. For the Univ. of Tokyo PPT a magnetic field applied over the entire 6-cm long channel increases the specific impulse and thrust efficiency by 10% over the case that the filed is applied in the first 1.75 cm of the PPT channel. The magnitude of these increases compare well with the results of the UOT applied B-field experiments. For the LES-6 and LES-9 PPTs, the simulations predicts significant performance enhancements with approximately linear increases for the specific impulse, thrust efficiency and impulse bit. "

"As new, smaller satellites are built, the need for improved on-board propulsion systems has grown. The pulsed plasma thruster has received attention due to its low power requirements, its simple propellant management, and the success of initial flight tests. Successful integration of PPTs on spacecraft requires the comprehensive evaluation of possible plume-spacecraft interactions. The PPT plume consists of neutrals and ions from the decomposition of the Teflon propellant, material from electrode erosion, as well as electromagnetic fields and optical emissions. To investigate the PPT plume, an on-going program is underway at WPI that combines experimental and computational investigations. Experimental investigation of the PPT plume is challenging due to the unsteady, pulsed as well as the partially ionized character of the plume. In this thesis, a triple Langmuir probe apparatus was designed and used to obtain electron temperature and density measurements in the plume of a PPT. This experimental investigation provides further characterization of the plume, much needed validation data for computational models, and is useful in thruster optimization studies. The pulsed plasma thruster used in this study is a rectangular geometry laboratory model built at NASA Lewis Research Center for component lifetime tests and plume studies. It is almost identical in size and performance to the LES 8/9 thruster, ablating 26.6 ug of Teflon, producing an impulse bit of 256 uN-s and a specific impulse of 986 s at 20 J. All experiments were carried out at NASA LeRC Electric Propulsion Laboratory. The experimental setup included triple Langmuir probes mounted on a moveable probe stand, to collect data over a wide range of locations and operating conditions. Triple probes have the ability to instantaneously measure electron temperature and density, and have the benefit of being relatively simple to use, compared to other methods used to measure these same properties. The implementation of this measuring technique is discussed in detail, to aid future work that utilizes these devices. Electron temperature and density was measured from up to 45 degrees from the centerline on planes parallel and perpendicular to the thruster electrodes, for thruster energy levels of 5, 20 and 40 J. Radial distances extend from 6 to 20 cm downstream from the Teflon surface. These locations cover the core of the PPT plume, over a range of energy levels that corresponds to proposed mission operating conditions. Data analysis shows the spatial and temporal variation of the plume. Maximum electron density near the exit of the thruster is 1.6 x 1020, 1.6 x 1021, and 1.8 x 1021 m-3 for the 5, 20 and 40 J discharges, respectively. At 20 cm downstream from the Teflon surface, densities are 1 x 1019, 1.5 x 1020 and 4.2 x 1020 for the 5, 20 and 40 J discharges, respectively. The average electron temperature at maximum density was found to vary between 3.75 and 4.0 eV for the above density measurements at the thruster exit, and 20 cm from the Teflon surface the temperatures are 0.5, 2.5, and 3 eV for the 5, 20 and 40 J discharges. Plume properties show a great degree of angular variation in the perpendicular plane and very little in the parallel plane, most likely due to the rectangular geometry of the PPT electrodes. Simultaneous electron temperature and density traces for a single thruster discharge show that the hottest electrons populate the leading edge of the plume. Analysis between pulses shows a 50% variation in density and a 25% variation in electron temperature. Error analysis estimates that maximum uncertainty in the temperature measurements to be approximately +/- 0.75 eV due to noise smoothing, and the maximum uncertainty in electron density to be +/- 60%, due to assumptions related to the triple probe theory. In addition, analysis of previously observed slow and fast ion components in the PPT plume was performed. The analysis shows that there is approximately a 3 us difference in creation time between the fast and slow ions, and that this correlates almost exactly with the half period of the oscillations in the thruster discharge current."

The use of high-voltage pulsed electric fields in biotechnology and medicine has lead to new methods of cancer treatment, gene therapy, drug delivery, and non-thermal inactivation of microorganisms. Regardless of the application, the objective is to open pores in the cell membrane and hence either facilitate the delivery of foreign materials inside the cell or to kill the cell completely. Pulsed power supplies are needed for electroporation, which is the process of applying pulsed electric fields to biological cells to induce a temporary permeability in the cell membrane. The applications of pulsed electric fields are dependent on the output pulse shape and pulse parameters, both of which can be affected by the circuit parameters of the pulsed power supply and the conductivity of the media being treated. <br /><br /> In this research, two Metal Oxide Field Effect Transistor (MOSFET)-based pulsed power supplies that are used for electroporation experiments were designed and built. The first used up to three MOSFETs in parallel to deliver high voltage pulses to highly conductive loads. To produce pulses with higher voltages, a second pulsed power supply using two MOSFETs connected in series was designed and built. The parallel and series MOSFET-based pulsed power supplies are capable of producing controllable square pulses with widths of a few hundred nanoseconds to dc and amplitudes up to 1500 V and 3000 V, respectively. The load in this study is a 1-mm electroporation cuvette filled with a buffer solution that is varied in conductivity from 0. 7 mS/m to 1000 mS/m. The results indicate that by controlling the circuit parameters such as the number of parallel MOSFETs, gate resistance, energy storage capacitance, and the parameters of the MOSFET driver gating pulses, the output pulse parameters can be made almost independent of the load conductivity. <br /><br /> Using the pulsed power supplies designed in this work, an investigation into electroporation-mediated delivery of a plasmid DNA molecule into the pathogenic bacterium <em>E. coli</em> O157:H7, was conducted. It was concluded that increasing the electric field strength and pulse amplitude resulted in an increase in the number of transformants. However, increasing the number of pulses had the effect of reducing the number of transformants. In all of the experiments the number of cells that were inactivated by the exposure to the pulsed electric field was measured.

The use of high-voltage pulsed electric fields in biotechnology and medicine has lead to new methods of cancer treatment, gene therapy, drug delivery, and non-thermal inactivation of microorganisms. Regardless of the application, the objective is to open pores in the cell membrane and hence either facilitate the delivery of foreign materials inside the cell or to kill the cell completely. Pulsed power supplies are needed for electroporation, which is the process of applying pulsed electric fields to biological cells to induce a temporary permeability in the cell membrane. The applications of pulsed electric fields are dependent on the output pulse shape and pulse parameters, both of which can be affected by the circuit parameters of the pulsed power supply and the conductivity of the media being treated. <br /><br /> In this research, two Metal Oxide Field Effect Transistor (MOSFET)-based pulsed power supplies that are used for electroporation experiments were designed and built. The first used up to three MOSFETs in parallel to deliver high voltage pulses to highly conductive loads. To produce pulses with higher voltages, a second pulsed power supply using two MOSFETs connected in series was designed and built. The parallel and series MOSFET-based pulsed power supplies are capable of producing controllable square pulses with widths of a few hundred nanoseconds to dc and amplitudes up to 1500 V and 3000 V, respectively. The load in this study is a 1-mm electroporation cuvette filled with a buffer solution that is varied in conductivity from 0. 7 mS/m to 1000 mS/m. The results indicate that by controlling the circuit parameters such as the number of parallel MOSFETs, gate resistance, energy storage capacitance, and the parameters of the MOSFET driver gating pulses, the output pulse parameters can be made almost independent of the load conductivity. <br /><br /> Using the pulsed power supplies designed in this work, an investigation into electroporation-mediated delivery of a plasmid DNA molecule into the pathogenic bacterium <em>E. coli</em> O157:H7, was conducted. It was concluded that increasing the electric field strength and pulse amplitude resulted in an increase in the number of transformants. However, increasing the number of pulses had the effect of reducing the number of transformants. In all of the experiments the number of cells that were inactivated by the exposure to the pulsed electric field was measured.

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.