<p> A brief review of the theoretical and experimental aspects of liquid droplet nucleation from vapours and of crystal nucleation from aqueous solution is presented. In order to study the nucleation and crystal growth of several analytically important metal chelates, methods were developed to measure the size distribution of crystals growing in a supersaturated solution. These methods involved rapid mixing techniques followed by measurement of the size distribution of the precipitated particles using a Coulter counter and multichannel analyser. The size distributions were dumped from the analyser onto magnetic tape and recovered using computer methods. The mixing and counting techniques were calibrated and tested using barium sulphate and spheres of known size distribution. </p> <p> From the size distributions obtained for the metal chelates, conclusions were made regarding the nucleation step, and the parameters important in the classical Volmer-Weber-Becker-Doring theory of nucleation were calculated. The validity of the values were evaluated and comparisons made with values obtained by other workers. </p> <p> The laws controlling the crystal growth of the metal chelates and their importance in elucidating the type of nucleation process were also investigated. </p> / Thesis / Doctor of Philosophy (PhD)

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In this study, the composite of aluminum metal-organic framework MIL-68(Al) and reduced graphene oxide (MA/RG) was synthesized via a one-step solvothermal method, and their performances for pnitrophenol (PNP) adsorption from aqueous solution were systematically investigated. The introduction of reduced graphene oxide (RG) into MIL-68(Al) (MA) significantly changes the morphologies of the MA and increases the surface area. The MA/RG-15% prepared at RG-to-MA mass ratio of 15% shows a PNP uptake rate 64% and 123% higher than MIL-68(Al) and reduced graphene oxide (RG), respectively. The hydrogen bond and pi-pi dispersion were considered to be the major driving force for the spontaneous and endothermic adsorption process for PNP removal. The adsorption kinetics, which was controlled by film-diffusion and intra-particle diffusion, was greatly influenced by solution pH, ionic strength, temperature and initial PNP concentration. The adsorption kinetics and isotherms can be well delineated using pseudo-second-order and Langmuir equations, respectively. The presence of phenol or isomeric nitrophenols in the solution had minimal influence on PNP adsorption by reusable MA/RG composite.

Metal oxide thin films serve as critical components in many modern technologies, including microelectronic devices. Industrial state-of-the-art production utilizes vapor-phase techniques to make high-quality (dense, smooth, uniform) thin film materials. However, vapor-phase techniques require large energy inputs and expensive equipment and precursors. Solution-phase routes to metal oxides have attracted great interest as cost-effective alternatives to vapor-phase methods and also offer the potential of large-area coverage, facile control of metal composition, and low-temperature processing. Solution deposition has previously been dominated by sol-gel routes, which utilize organic ligands, additives, and/or solvents. However, sol-gel films are often porous and contain residual carbon impurities, which can negatively impact device properties. All-inorganic aqueous routes produce dense, ultrasmooth films without carbon impurities, but the mechanisms involved in converting aqueous precursors to metal oxides are virtually unexplored. Understanding these mechanisms and the parameters that influence them is critical for widespread use of aqueous approaches to prepare microelectronic components. Additionally, understanding (and controlling) density and composition inhomogeneities is important for optimizing electronic properties. An overview of deposition approaches and the challenges facing aqueous routes are presented in Chapter I. A summary of thin film characterization techniques central to this work is given in Chapter II. This dissertation contributes to the field of solution-phase deposition by focusing on three areas. First, an all-inorganic aqueous route to high-κ metal oxide dielectrics is developed for two ternary systems. Chapters III and IV detail the film formation chemistry and film properties of lanthanum zirconium oxide (LZO) and zirconium aluminum oxide (ZAO), respectively. The functionality of these dielectrics as device components is also demonstrated. Second, the impact of steam annealing on the evolution of aqueous-derived films is reported. Chapter V demonstrates that steam annealing lowers processing temperatures by effectively reducing residual counterion content, improving film stability with respect to water absorption, and enhancing dielectric properties of LZO films. Third, density and composition inhomogeneities in aqueous-derived films are investigated. Chapters VI and VII examine density inhomogeneities in single- and multi-metal component thin films, respectively, and show that these density inhomogeneities are related to inhomogeneous metal component distributions. This dissertation includes previously published coauthored material.

In this study, zinc oxide (ZnO) nanotip and nanorod were grown on glass substrate by aqueous solution deposition (ASD). Both characteristics of the two nanostructures were investigated. For fabrication of ZnO nanostructure UV photodetector, In-Zn inter-digitated metal electrode was evaporated on the top of the grown ZnO nanostructure to form the contact via. Compared with the common value (375 nm), both the peaks from the PL spectra of ZnO nanotip and nanorod are red-shifted (409 nm) due to the massive defects in nanotip and nanorod. In order to improve the photosensiblity, heterojunction of ZnO nanostructure/TiO2 film was prepared and were made into UV photodetector. Photoresponses of both nanotip and nanorod were improved after N2O annealing at 300oC. With the heterojunction of ZnO 1D nanostructure on TiO2 film, the photoresponses of both ZnO nanotip/TiO2 film can reach to 22.85, and the rise time and decay time are 40 and 82 seconds, respectively. On the other side, the photoresponses of both ZnO nanorod/TiO2 film can reach to 27.44, and the rise time and decay time are 22 and 133 seconds, respectively.

This study presents a new way for new 3D energy harvesting energy with vertically aligned nanorods arrays. ZnO nanoparticles array on Au/Cr/Si substrate are directly patterned by electrospray. First, gel solutions with zinc acetate, monoethanolamine and 2-methoxyethanol as the precursor by sol-gel technology were formulated. Then, the solutions were stirred to become clear and homogeneous liquid. Second, the precursor solutions were prepared by electrospray, where a Taylor cone was formed to produce ZnO nanoparticles. Then the ZnO nanoparticles were annealed as seed layers for nanorods. By varying the property of the ZnO solution, needle with collector distance, applied voltage, annealing temperature and molar ratio were discussed. After annealing, the orientation of the ZnO nanorods depend on the crystalline orientation of ZnO nanoparticles. The ZnO nanorods were obtained at a temperature of 90 ¢XC by aqueous solution method. The experimental parameters of lengths, diameters, and pH level of the reaction medium of the Zno nanorod were observed and controlled. The physical structures of ZnO were characterized by X-ray diffraction (XRD) and Field Emission Scanning Electron Microscopy (FESEM) analyses. The results show that the ZnO nanoparticles become more intensity with increasing in annealing temperature. The SEM analysis reveals that the ZnO nanorods have diameters about 100-400 nm and length about 200-1200 nm. Finally, Pt electrode atop as Schottky contacts were packed to fabricate nanogenerator with ZnO nanorods. Then the nanogenerator was driven by ultrasonic wave vibration. The wave drives the electrode up and down to vibrate the nanorods, and its voltage and current were also characterized. The measurement results show the maximum power is 0.004х10-8 W during the operation frequency of 42 kHz.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-01-21T10:28:15Z No. of bitstreams: 0 / Made available in DSpace on 2015-01-21T10:28:15Z (GMT). No. of bitstreams: 0 / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Low level nuclear waste arising from UK nuclear sites, research establishments, hospitals and industry is currently disposed of at the Drigg Disposal Facility in Cumbria. Waste is packed into steel canisters before being compacted and grouted into larger steel storage containers. The aqueous chemistry of wastes, especially radionuclides, in the presence of grout material is of major interest. The gout used at the Drigg site is a mixture of Ordinary Portland Cement and Pulverised Fly Ash additive, from which ingressing water will leach high levels of calcium, sodium and potassium and produce waters of a high pH. Aerobic environments are expected to dominate over the early period of the vault life, after which the combined effect of canister corrosion and microbial activity will lead to anaerobic conditions. After a much longer period (100,000 years) anaerobic conditions may cease and yield once again an aerobic environment where migration of radionuclides may be sorption-controlled rather than on hydroxide precipitation at high pH. Work has been performed under both aerobic and anaerobic conditions to study uranium solubility in the presence of complexing ligands that may be present in the waters of the nearfield of a low-level waste disposal vault. Eleven ligands have been investigated: carbonate, phosphate, chloride, sulphate, acetate, citrate, EDTA, NTA and organic matter- humic acid, fulvic acid and iso-sacchannic acid. Anaerobic conditions were achieved by two different procedures; the first used ferrous ions in hydroxide solution and the second used dithionite in hydroxide solution. Both methods produce reducing electrode potentials and high pH. Computer software has been used to model experimental results, thereby predicting uranium solubilities and speciation, and to propose new formation constants to fit the experimental results more closely. Studies have also been perforined to measure uranium sorption by grout material at high pH in the presence of the above ligands. This work makes a significant contribution to the understanding of uranium solubility and speciation in waters. at high pH and under conditions relevant to low level nuclear waste disposal.

Orientador: Aldo Eloizo Job / Resumo: O Brasil tem sido destaque na produção agrícola mundial, exportando uma grande variedade de grãos para o mundo todo. Para que esses patamares de produção sejam alcançados é necessário o emprego de diversos insumos agrícolas, como os herbicidas, dentre os quais o mais comum e utilizado comercialmente é o glifosato. No entanto, o aumento no uso de defensivos agrícolas tem, por consequência, aumentado o índice de contaminação de águas pluviais ou de lençol freático. Dentre os métodos de remoção de poluentes de água, como o de coagulação, eletro-floculação, filtração por membrana e oxidação, destaca-se o processo de adsorção, ecológico e eficaz na remoção de contaminantes orgânicos e inorgânicos de águas e gases. Neste trabalho, realizou-se o tratamento químico do bagaço de cana-de-açúcar com hidróxido de sódio e ácido sulfúrico a fim de utilizá-lo como material adsorvente para remoção de glifosato em meio aquoso. Foram feitos ensaios para determinar o potencial de carga zero, pH, capacidade e intensidade da adsorção assim como a cinética do processo. Os resultados demonstraram que o bagaço submetido ao tratamento alcalino se mostrou mais eficiente que o tratamento ácido, com pH ideal de adsorção igual a 9, e ajuste ao modelo de Langmuir, indicando que a quimiossorção governa o mecanismo de adsorção cuja máxima capacidade de adsorção foi de 13,720 mg g-1 obtida em quarenta minutos. / Abstract: Brazil has been prominent in world agricultural production, exporting a wide variety of grains to the whole world. In order to reach these production levels, it is necessary to employ several agricultural inputs, such as herbicides, among which the most common and commercially used is glyphosate. However, the increased use of pesticides has, consequently, increased the index of contamination of rainwater or groundwater. Among the methods of water pollutant removal such as coagulation, electro-flocculation, membrane filtration and oxidation, highlight the adsorption process, ecological and efficient in the removal of organic and inorganic contaminants from water and gasses. In this work, the chemical treatment of sugarcane bagasse with sodium hydroxide and sulfuric acid was carried out in order to use it as an adsorbent material to remove glyphosate in aqueous solution. Assays were performed to determine zero charge potential, pH, capacity and adsorption intensity as well as process kinetics. The results showed that the bagasse submitted to the alkaline treatment was more efficient than the acid treatment, with an ideal adsorption pH by 9, and adjustment to the Langmuir model, indicating that the chemosorption governs the adsorption mechanism whose maximum adsorption capacity was higher of 13,720 mg g-1 obtained in forty minutes. / Mestre

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22068号 / 工博第4649号 / 新制||工||1725(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 邑瀬 邦明, 教授 宇田 哲也, 教授 杉村 博之 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM