C3H6 oxidation over a Pt/Al2O3 catalyst with or without NOx present was investigated. In particular, its reaction mechanism was studied using diffuse reflectance infrared spectroscopy (DRIFTS), a reactor system designed for monolith-supported catalysts and a micro-reactor system designed for powder catalysts referred to as CATLAB. These experiments reveal that C3H6 oxidation is inhibited by the presence of NO, NO oxidation is inhibited by the presence of CeH6, and that adsorbed NOx can react with gas phase C3H6. DRIFTS and CATLAB results confirm the reaction between C3H6 and nitrates, which are formed during NOx adsorption, with linear nitrites observed as reaction products. Therefore, a reaction route is proposed for C3H6 oxidation in the presence of NOx, namely, nitrates acting as oxidants. Using NO2 instead of NO, or using a high NOx/C3H6 ratio, which is beneficial for nitrate formation, favors this reaction pathway. Data also showed that Pt is required for this reaction, which suggests the nitrates in proximity to the Pt particles are affected/relevant. Reaction kinetics studies of C3H6 oxidation over Pt/Al2O3 and Pt/SiO2 catalysts were performed in CATLAB using a temperature-programmed oxidation method with different oxidants: O2, NO2 and nitrates. The reaction kinetics of these possible reactions were compared in order to determine which reaction is more important. NOx adsorption does not occur on the SiO2 surface so the reaction between C3H6 and NO2 could be isolated and the effect of nitrates could be observed as well when compared to the results from Pt/Al2O3. The Pt dispersions were determined using H2 chemisorption and were 1.3 and 1.6% for Pt/Al2O3 and Pt/SiO2, respectively. C3H6 oxidation starts at a lower temperature with O2 than with NO2 but the activation energy was lower with NO2. This gives indication that hydrocarbons must be activated first for NO2 to be favored in hydrocarbon oxidation. When the experiment was done with C3H6 and nitrates, the reaction did not occur until NOx started to desorb from the catalyst at higher temperatures, when nitrates become unstable and decompose. Therefore, O2 was added to the system and the reaction began at even lower temperature than with just C3H6 and O2. This proved that hydrocarbons need to be activated in order for surface nitrates to affect C3H6 oxidation and this reaction also resulted in a lower activation energy than with just C3H6 and O2. Nitrate consumption was also observed as less NOx desorbed from the catalyst at the later stage of the temperature ramp compared to the amount desorbed when the catalyst was not exposed to C3H6.

γ-Al2O3 supported Co-W based catalysts with varying Co (1 - 3 wt %) and W (7 - 13 wt %) loadings were prepared using impregnation and sonochemical methods. All prepared catalysts were characterized with elemental analysis, BET analysis, X-ray diffraction (XRD), NH3 temperature programmed desorption (TPD), temperature programmed reduction (TPR) and thermogravimetry analysis (TGA). <p>The performances of all the synthesized catalysts were tested at a pressure of 8.9 MPa, LHSV of 2 h-1 and temperatures of 340, 350 and 360 °C in a laboratory trickle bed microreactor for hydrodesulphurization (HDS) and hydrodenitrogenation (HDN) of light gas oil (LGO) derived from Athabasca bitumen. The performance tests with impregnated catalysts indicated a maximum in activity for HDS and HDN reactions (sulfur and nitrogen conversions at 93.0 and 57.1 % at 360 °C) for Co(3 wt %)-W(10 wt %)/γ-Al2O3 whereas the performance tests with sonochemically prepared catalysts showed a maximum in activity (sulfur and nitrogen conversions at 87.9 and 42.5 % at 360 °C) for Co(3 wt %)-W(11.5 wt %)/ γ-Al2O3. These two catalysts were selected for detail performance, optimization and kinetic studies. The effects of reaction temperature (340 - 380 °C), pressure (7.6 - 10.3 MPa), liquid hourly space velocity (1.5 - 2.0 h-1) and hydrogen gas/gas oil ratio (400 - 800 mL/mL) were examined on HDS and HDN of LGO with these catalysts. The reaction kinetics for HDS was best fitted with a Power Law model whereas same for HDN was found to be best represented by a Langmuir-Hinshelwood model with a reasonable accuracy (0.90 <R2 <0.95). The activation energy for HDS of LGO were 14 and 12 kJ/mol for selected impregnated and sonochemically prepared catalysts whereas the same for HDN were 9 and 14 kJ/mol for these catalysts, respectively. Calculation showed that the fitted HDS rate expressions were apparent and HDN rate expressions were intrinsic under existing reaction conditions. It also showed that the pore diffusion resistances for both HDS and HDN increased with an increase in reaction temperature from 340 to 380 °C.

As the microwave wireless communication systems growing rapidly, microstrip planar ceramic filters attract many attentions because of the advantages of small size, low cost, easy fabrication, higher performance and easy integration. In this thesis, several kinds of bandpass filters are designed for different operating purposes. First, two kinds of dual-mode bandpass filters are designed for 2.4 GHz wideband with the T-shaped I/O arranging in a straight way for easy integration. Second, the hook-coupling and insert-coupling structures are adopted for series connecting of the stepped-impedance resonator structures, and 2.4/5.2 GHz dual-band filtering properties could be achieved. Third, two open-loop rectangular ring resonators and U-shaped I/O are designed for 2.4/5.2 GHz dual-band bandpass filters with deep transmission zeros. The quarter wavelength stubs and groove structures are used for enhancing deep transmission zeros between two passband and ripples of the second passband, respectively. Fourth, the parallel positioned resonators with phase difference method are used to design the dual-band (1.23/2.4 GHz) and quad-band (1.23/2.4/3.5/5.2 GHz) bandpass filter with asymmetrical bandwidths and transmission zeros. In the thesis, high quality Al2O3 ceramic substrates are used to fabricate different kinds of bandpass filters for pattern minimization and low losses. The electromagnetic simulators, HFSS and IE3D, were used to adjust and optimize the associated parameters. The printing method was used to fabricate the proposed bandpass filters, which did not need using the FeCl3 to etch the Cu plate from the surface of Duroid or the FR4 substrates. The proposed filters are measured by Agilent-N5230A with the SMA connectors welding. Finally, the simulated and measured results of proposed bandpass filters are in good agreement.

Epitaxial m-plane (11 ¡Â00) ZnO thin films grown on m-sapphire substrates by atomic layer deposition have been studied. Atomic imaging and electron diffraction conducted in a transmission electron microscope (TEM) and crystallography by X-ray diffractometry all show consistent epitaxial relations with ZnO m-plane // sapphire m-plane, while ZnO [112 ¡Â0] // Al2O3 [0001], and ZnO [0001] // Al2O3 [112 ¡Â0]. The widths (full width at half maximum, or FWHM) of the rocking curves depend on the crystallographic axis of rotation. Dislocations near the interface between the ZnO epi-layers and sapphire substrates can be found from the cross-sectional TEM images when the direction of the incident electron beam, namely, the zone axis, is parallel to ZnO [112 ¡Â0], the a-axis of ZnO. There are stacking faults found in ZnO films away from their interfaces with the substrates. Polarization-dependent photoluminescence by differently polarized incident laser beam have also been investigated. Careful analysis of the spectra via multi-peak fittings revealed optical transitions at 3.32eV for T = 15K, which, however, shifted to 3.28eV at T = 300K. This shift in energy is accounted for by the quadratic temperature dependence of the Fermi level as determined by the positions of the lines of emission corresponding to the band edge transition. The 300K spectrum showed a more distinct peak at 2.48eV when the polarization of the emitted light was along the a-axis of ZnO, as compared to that along the c-axis of ZnO. The origin of this difference remains unaccounted for at the time of writing this thesis. The rest of the peaks have been interpreted in terms of optical transitions involving band gap impurity states, possible exciton formations, and their interactions with phonons.

This thesis investigates the effects of varying the crystallographic orientations of epitaxial ZnO thin films to produce functional ZnO P-N diodes. First, with the atomic layer deposition (ALD), a p-type m-oriented ZnO epitaxial layer is deposited onto an also m-oriented Al2O3 substrate. Then an n-type ZnO layer, mostly textured along the c-axis, is grown atop to form a P-N diode by RF sputtering method. The Hall Effect of the m-ZnO thin film is measured separately at various temperatures and magnetic fields in Quantum Design¡¦s Physical Property Measurement System (PPMS) to determine the nature of the charge carriers. The m-oriented ZnO films are found to be p-type semiconductors, with carrier concentration approximately ~ 1021 1/cm3, which falls in the category of highly-doped degenerate semiconductor. In order to further prove that these films are indeed p-type, naturally n-type c-textured ZnO films are put on the m-films at room temperature by magnetron sputtering to see if the current-voltage (I-V) curves do follow the P-N junction characteristics. In optimizing the c-ZnO film quality and reducing the effects of the junction defects, the gas-mixture ratio between argon and oxygen was varied to compare for the changes in the performance of the resulted materials and devices. X-ray diffraction was used to characterize the crystallographic orientations and the general qualities of the samples by 2£c-£s scan, rocking scan, £p-scan and pole figure measurement. Understanding of the P-N diode is acquired through the analysis of the leakage current and the quantum tunneling phenomena as manifested in the I-V characteristics.

Microwave dielectric resonators (DRs) are being widely used in microwave telecommunication devices owing to their excellent characteristics of suitable dielectric constant, good temperature stability, and low dielectric loss. In this study, the crystalline phase and the microwave dielectric properties of the (1-x)Al2O3 - xTiO2 (x=0.08, 0.12, 0.16) compositions with 2wt%, 4wt%, 6wt%, and 8wt% MgO-CaO-Al2O3-SiO2 (MCAS) glass addition have been investigated. By combining the material Al2O3 with negative temperature coefficient of the resonant frequency (£nf = -55 ppm/¢J) and the material TiO2 with positive £nf value (£nf = +450 ppm/¢J), it is desired to produce the ceramics with £nf ~0 ppm/¢J. The MCAS is used as liquid-phase sintering aid to lower down the sintering temperature. In the MCAS-doped (1-x)Al2O3 - xTiO2 system, the Al2TiO5 phase starts to appear at about 1250¢J, and then the crystalline intensity of Al2TiO5 phase increases with the increase of sintering temperatures and MCAS glass content, until the temperatures that TiO2 is consumed. As the sintering temperature increases, the maximum dielectric constants and Q¡Ñf values can be obtained at 1250¢J, and the £nf values shift from positive to negative. The optimum £nf value of ¡V0.6 ppm/¢J exists in the 88mol%Al2O3 - 12mol%TiO2 composition with 2wt% MCAS addition and sintering temperature of 1300¢J. The MCAS content, TiO2 content, and sintering temperature will result in the variation of microwave dielectric properties. In this study, MCAS-doped (1-x)Al2O3 - xTiO2 system exhibits the microwave dielectric properties of¡G £`r=7~9.5, Q¡Ñf=6500~11000, and £nf = -60 to +40ppm/¢J. By adjusting the MCAS content, TiO2 content, and sintering temperatures, ceramics with good microwave properties can be obtained in the MCAS-doped (1-x)Al2O3 - xTiO2 system.

This thesis will talk about the difference between c-plane and m-plane GaN. We use C-V measurement and try to find the difference from C-V result. We use atomic layer deposit (ALD) to deposit Al2O3 no n-Si (111), p-Si (111), c-GaN, m-GaN, c-InN and m-InN for making MOS structure. And use 100 kHz to measure high frequency C-V and charge-voltage method to measure quasi-static capacitance and leakage current. The process and how the instrument work will present in article. In Si (111) case, the flat-band voltage is far away from ideal value. This tells us charge in oxide. Result of quasi-static method shows interface state density is between 1011 cm-2¡DeV-1 to 1012 cm-2¡DeV-1. From Ref. 13, SiO2-Si system with 1011 cm-2 interface trap charge density for Si (111). We compare C-V carrier concentration with Hall carrier concentration and find some difference. We put C-V result of experiment and simulated with COX and Hall carrier concentration we measured. In GaN case, here is deep depletion in C-V result. And quasi-static result also shows deep depletion of GaN. This phenomenon means generate time of hole of n-type GaN is very long. And we use light to excite electron and hole and measure C-V for average surface density of state. The density of stay of Al2O3/m-GaN and Al2O3/c-GaN system is similar. Only appearance difference between Al2O3/m-GaN and Al2O3/c-GaN is position of flat-ban voltage. flat-ban voltage of c-GaN is more negative than m-GaN. For InN, we see ¡§the middle is lower than edge¡¨ curve. Recently, few group present complete C-V curve of InN. We can not sure whether we can use typical way to analyze this data.

Recently, wet sand blasting on coated cutting tool inserts has drawn interest to the tooling industry due to its positive effects on cutting performance and tool life. This performance boost has partly been attributed to the buildup of compressive residual stresses in the coating during the blasting process. However, the mechanism of forming residual stresses in ceramic coatings during sand blasting is not fully understood. This work utilize x-ray diffraction as the main tool to study the formation and relaxation of residual stresses after wet sand blasting and annealing on 001, 012 and 110 textured α-Al2O3 coatings. To minimize the influence of stress gradients in the samples, all stress measurements were set up with a fixed analysis depth of 2 µm. Sand blasting was made with an alumina based slurry at 2, 3.2 and 4 bar pressure and the anneal was done at temperatures from 400 to 1000 °C for 2 hours or more. The coating hardness was evaluated by nanoindentation. Finally, the activation energy for the relaxation of residual stresses was estimated using the Zener-Wert-Avrami function. The results reveal the highest compressive residual stress with up to -5.3 GPa for the 012 texture while the stresses for the 001 and 110 textures peaked at -3.1 and -2.0 GPa, respectively. Further, a hardness gradient was present after blasting of the 001 and 012 textured samples indicating a higher stress at the surface of the coating. The 110 textured sample is the most brittle resulting in flaking of the coating during sand blasting. The different deformation mechanisms are related to difference in active slip planes between coatings with different textures. Both the stress and hardness decreased after heat treatment and the activation energy for stress relaxation was found to be as 1.1 ± 0.3 eV, 1.9 ± 0.2 eV and 1.2 ± 0.1 eV for the 001, 012 and 110 textures, respectively.

C3H6 oxidation over a Pt/Al2O3 catalyst with or without NOx present was investigated. In particular, its reaction mechanism was studied using diffuse reflectance infrared spectroscopy (DRIFTS), a reactor system designed for monolith-supported catalysts and a micro-reactor system designed for powder catalysts referred to as CATLAB. These experiments reveal that C3H6 oxidation is inhibited by the presence of NO, NO oxidation is inhibited by the presence of CeH6, and that adsorbed NOx can react with gas phase C3H6. DRIFTS and CATLAB results confirm the reaction between C3H6 and nitrates, which are formed during NOx adsorption, with linear nitrites observed as reaction products. Therefore, a reaction route is proposed for C3H6 oxidation in the presence of NOx, namely, nitrates acting as oxidants. Using NO2 instead of NO, or using a high NOx/C3H6 ratio, which is beneficial for nitrate formation, favors this reaction pathway. Data also showed that Pt is required for this reaction, which suggests the nitrates in proximity to the Pt particles are affected/relevant. Reaction kinetics studies of C3H6 oxidation over Pt/Al2O3 and Pt/SiO2 catalysts were performed in CATLAB using a temperature-programmed oxidation method with different oxidants: O2, NO2 and nitrates. The reaction kinetics of these possible reactions were compared in order to determine which reaction is more important. NOx adsorption does not occur on the SiO2 surface so the reaction between C3H6 and NO2 could be isolated and the effect of nitrates could be observed as well when compared to the results from Pt/Al2O3. The Pt dispersions were determined using H2 chemisorption and were 1.3 and 1.6% for Pt/Al2O3 and Pt/SiO2, respectively. C3H6 oxidation starts at a lower temperature with O2 than with NO2 but the activation energy was lower with NO2. This gives indication that hydrocarbons must be activated first for NO2 to be favored in hydrocarbon oxidation. When the experiment was done with C3H6 and nitrates, the reaction did not occur until NOx started to desorb from the catalyst at higher temperatures, when nitrates become unstable and decompose. Therefore, O2 was added to the system and the reaction began at even lower temperature than with just C3H6 and O2. This proved that hydrocarbons need to be activated in order for surface nitrates to affect C3H6 oxidation and this reaction also resulted in a lower activation energy than with just C3H6 and O2. Nitrate consumption was also observed as less NOx desorbed from the catalyst at the later stage of the temperature ramp compared to the amount desorbed when the catalyst was not exposed to C3H6.

Made available in DSpace on 2016-06-02T19:56:49Z (GMT). No. of bitstreams: 1 4870.pdf: 2993448 bytes, checksum: 8f7dd0a2deb8145ffb95c1d81c5dc45a (MD5) Previous issue date: 2012-04-26 / Universidade Federal de Sao Carlos / In this work the activity of nickel catalysts were appraised regarding the dry reforming of methane. Due to the low surface area, the catalysts were supported on SiO2 and Al2O3, in order to verify the effect of the support on the catalytic activity. For that, catalysts 12%Ni/xOBa/SiO2 and 12%Ni/xOBa/Al2O3 (x=6, 8 and 12%) were prepared, characterized and submitted to catalytic assays in the methane reforming reaction with carbon dioxide, with the objective of evaluating the effect of the addition of barium to the support. The catalysts were prepared by the wet impregnation method and characterized by powder x-ray diffraction, nitrogen physisorption by the B.E.T.method, area, volume and pore radius, temperature programmed reduction with H2 and X-ray fluorescence. The catalytic assays showed that all the catalysts were shown active in the dry reforming of methane and the conversion of the products was dependent on the type of catalyst appraised. According to the obtained results, they stand out the catalysts with 12% barium in mass addition supported on SiO2 as well as Al2O3. / Neste trabalho foram avaliadas as atividades de catalisadores de níquel frente à reforma a seco do metano. Devido à baixa área superficial, esses foram suportados em SiO2 e Al2O3, a fim de verificar o efeito do suporte na atividade catalítica. Para isso, catalisadores 12%Ni/xOBa/SiO2 e 12%Ni/xOBa/Al2O3 (x= 6, 8 e 12%), foram preparados, caracterizados e submetidos a ensaios catalíticos na reação de reforma do metano com dióxido de carbono, com o objetivo de avaliar o efeito da adição do bário ao suporte. Os catalisadores foram preparados pelo método de impregnação úmida e caracterizados por difração de raios X pelo método do pó, fisissorção de nitrogênio pelo método B.E.T., área, volume e raio do poro, redução à temperatura programada com H2 e fluorescência de raios X. Os ensaios catalíticos mostraram que todos os catalisadores mostraram-se ativos nas reações de reforma a seco do metano e a conversão dos produtos foi dependente do tipo do catalisador avaliado. De acordo com os resultados obtidos, destacam-se os catalisadores com 12% teor de adição de bário em massa, tanto o suportado em SiO2 quanto em Al2O3.