In recent years, magnesium and magnesium alloys have received much attention as a new biomaterial in orthopaedic applications due to their biodegradability, biocompatibility, and their mechanical properties that are similar to natural bone tissue. The most common problem associated with magnesium as a biomaterial is low corrosion resistance in physiological solutions. This decreases the mechanical integrity of the implants in the early stages of healing and has a negative impact on the overall biocompatibility. The main goal of this study was to create a multi-layered coating consisting of a silica sol-gel under-layer to protect the substrate from corrosion in body fluids and a mesoporous silica top-layer to enhance the bioactivity of the coated implant material. The results indicate that the deposited multi-layered coating enhances both the bioactivity and the corrosion resistance of the material.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18277号 / 工博第3869号 / 新制||工||1593(附属図書館) / 31135 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 松原 英一郎, 教授 杉村 博之, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Magnetic nanoparticles have been used in many areas owing to their variable characteristic behaviors. Among these iron oxide nanoparticles are one of the mostly preferred type of nanoparticles. In this study Fe3O4, namely magnetite, which is one type of magnetic iron oxide nanoparticles was used. Magnetite nanoparticles with a narrow size distribution were prepared in aqueous solution using the controlled coprecipitation method. They were characterized by electron microscopic methods (SEM and TEM), crystal structure analysis (XRD), particle size analyzer, vibrating sample magnetometer (VSM) and Raman spectrometry. The nanoparticles were coated with a thin (ca 20 nm) silica shell utilizing the hydrolysis and the polycondensation of tetraethoxysilane (TEOS) under alkaline conditions in ethanol. The presence of silica coating was investigated by energy dispersive X-ray spectrometer (EDX) measurement. After surface modification with an amino silane coupling agent, (3-Aminopropyl)triethoxysilane, histidine was covalently linked to the amine group using glutaraldehyde as cross-linker. Carbonyl complexes of rhenium [Re(CO)3(H2O)3]+ was prepared through reductive carboxylation utilyzing gaseous carbon monoxide as a source of carbonyl and amine borane (BH3NH3) as the reducing agent. The complex formation was followed by HPLC- ICP-MS system and 95% conversion of perrhanete into the complex was achieved. The magnetic nanoparticles were then labeled with the Re complex with a yield of 86.8% through the replacement of labile H2O groups with imidazolyl groups. Thus prepared particles were showed good stability in vitro. Herein rhenium was selected as a surrogate of radioactive 99mTc. However radioactive isotopes of rhenium (186-Re and 188 Re) is also used for radioactive therapy.

Magnetic nanoparticles find broad applications in biomedical field such as drug delivery, hyperthermia and magnetic resonance imaging (MRI). For these applications magnetic nanoparticles need to be coated with suitable materials which are soluble, biocompatible and nontoxic. Among these materials, silica is the most often used coating material. This thesis is focused on preparation of silica coated iron oxide magnetic nanoparticles. Magnetic iron oxide nanoparticles are synthesized by thermal decomposition method. In the presence of iron acetylacetonate Fe(acac)3, a high boiling point organic solvent and a reducing agent, particle sizes ranging from about 5 nm to 7 nm were obtained. Nanoparticles were characterized by transmission electron microscopy (TEM). The obtained nanoparticles were coated with ultra thin silica shell via reverse microemulsion method. The influence of the amount of Igepal CO-520, NH4OH and TEOS was studied systematically and their amounts were optimized to yield monodisperse and well defined particles. The size of the silica coated magnetic nanoparticles and their agglomerates were determined by TEM images and particle size analyzer (zeta sizer). X-Ray photoelectron spectroscopy (XPS) was used to confirm the presence of silica whenever the coating could not be seen by TEM measurements. Magnetic nanoparticles having 4-6 nm thickness of silica shell were obtained. The results showed that the amount of surfactant Igepal CO-520 played an important role in the reaction system.

Bringing together several materials into a single nanoparticle is an attractive way to design systems that exhibit diverse physical and chemical properties. Cobalt nanoparticles are extensively used in magnetic separation, ferrofluids, and magnetic storage media. The deposition of gold nanoparticles onto cobalt core significantly affects their optical properties due to the introduction of surface Plasmon. Here the synthesis of gold nanoparticles decorated cobalt-silica nanoparticles are reported for the first time. Their optical and magnetic properties and capacity as a surface enhanced Raman scattering (SERS) substrate were investigated. This nano-material is of particular interest as a dual agent allowing both magnetic separation and SERS detection. The synthesis involves three steps: i) synthesis of Co nanoparticles / ii) deposition of a silica shell around the Co core and introduction of amine functional groups on the surface / iii) decoration of the surface with gold nanoparticles. Co nanoparticles were prepared in an inert atmosphere in the presence of capping and reducing agents. Size of the cobalt nanoparticles was varied by changing the concentration of the capping agent. Since cobalt particles are easily oxidized, they were coated with silica shell both to prevent oxidation and allow further functionalization. Silica coating of the particles were performed in water/ethanolic solution of tetraethyl orthosilicate (TEOS). Thickness of silica coating was controlled by varying the concentrations of TEOS. Besides, by adding 3-aminopropyl-triethoxysilane (APTS) to the reaction medium, primarily amine groups were introduced on the silica surface. For further modifications citrate stabilized gold nanoparticles were appended onto the surface of amine modified core-shell cobalt-silica nanoparticles. Gold decorated magnetic core-shell structures were used as SERS substrate with Raman dyes / brilliant cresyl blue (BCB) and rhodamine 6G (R6G). They were also utilized for preconcentration and SERS detection of 4-mercapto benzoic acid (4-MBA). Gold nanoparticles on the silica and thiol group on the 4-MBA were very selective to each other, thus, 4-MBA could be attached on to gold surface and it could be easily separated magnetically from the reaction medium and identified by Raman spectroscopy. Characterization of the cobalt, cobalt-silica and gold modified cobalt-silica nanoparticles was done by Field Emission Scanning Electron Microscopy (FE-SEM), Scanning-Transmission Electron Microscopy (S-TEM), Energy-Dispersive X-ray Spectroscopy (EDX), UV-Vis spectrometry, and Raman microscope system.

The deposition of amorphous silica from aqueous solution on to rutile particles has been studied with the aim of elucidating the nature of the silica-titania interactions occurring and of following the progressive build up of the silica coating. The coating process, which involves the addition of an aqueous sodium silicate solution to an aqueous dispersion of titanium dioxide, has been investigated by performing a series of controlled preparations and using the technique of microelectrophoresis. Prepared silica-coated rutile samples ranging from partial to full silica coatings have been characterized using transmission electron microscopy, microelectrophoresis and nitrogen, argon and water sorption. Nitrogen and argon adsorption isotherms have been analysed using the equation of Brunauer, Emmett and Teller (BET). Differential energies of adsorption of nitrogen and argon have been determined calorimetrically. Water sorption isotherms have been analysed using the BET equation and the Frenkel - Halsey - Hill (FHH) equation. It has been shown that uniform silica coatings can be produced if adsorption of monomeric silica is followed by polymerization of silica at the solid/liquid interface. Surface cations on rutile may be hydroxylated or co-ordinately bound to water molecules and it appears that monomeric silica adsorbs preferentially by replacing ligand water molecules. Rutile particles with silica coatings thicker than approximately 2.5nm exhibit characteristics typical of silica and not of the base rutile. Silica coatings deposited at pH 10 contain narrow channels which are accessible to water molecules but not to nitrogen or argon. Neutralization to pH 7 reduces the volume in the coating accessible to water molecules.

Pressure oxidation of refractory gold ores containing carbonate minerals is conducted under neutral/alkaline conditions in order to promote fast kinetics, reduced reagent consumption and suppressing the formation of elemental sulphur and CO2 (which reduces the effectiveness of the process). In this work, both the addition of sodium carbonate and the presence of silica were investigated during the pressure oxidation of pyrite in the presence of calcium carbonate. It was found that the shift to an alkaline leaching environment favours the formation of soluble sulphate products over anhydrite (an industrial scale), but that the increase in kinetics is likely due to an increase in pH and carbonate/bicarbonate concentrations. The presence of silica in the autoclave induces the formation of an in situ iron oxyhydroxide silicate coating and a significant reduction in pyrite oxidation, which was minimized by addition of sodium carbonate.

Pressure oxidation of refractory gold ores containing carbonate minerals is conducted under neutral/alkaline conditions in order to promote fast kinetics, reduced reagent consumption and suppressing the formation of elemental sulphur and CO2 (which reduces the effectiveness of the process). In this work, both the addition of sodium carbonate and the presence of silica were investigated during the pressure oxidation of pyrite in the presence of calcium carbonate. It was found that the shift to an alkaline leaching environment favours the formation of soluble sulphate products over anhydrite (an industrial scale), but that the increase in kinetics is likely due to an increase in pH and carbonate/bicarbonate concentrations. The presence of silica in the autoclave induces the formation of an in situ iron oxyhydroxide silicate coating and a significant reduction in pyrite oxidation, which was minimized by addition of sodium carbonate.

No description available.

Este estudo se propôs a analisar os efeitos das diferentes larguras temporais de pulso do laser de Er:YAG na rugosidade superficial, na perda de volume do material e na altura do degrau formado em uma Y-TZP (Yttrium-stabilized Tetragonal Zirconia Polycrystal) pré-sinterizada. Foram utilizados 5 blocos de Y-TZP pré-sinterizados destinados ao uso CAD/CAM que foram seccionados, obtendo-se 63 espécimes padronizados. Em seguida, esses espécimes foram lixados com uma sequência decrescente de lixas para padronização da superfície. Os grupos experimentais foram compostos a partir de 1 fator de variação - o tratamento de superfície. Os espécimes foram irradiados com o laser de Er:YAG (Fidelis III Fotona, Eslovênia) - 2,94 ?m, 100 mJ, 15,87J/cm2, 10 Hz, 1W, 7 mm, 60% água/40% ar. Assim formaram-se 7 grupos experimentais (n=9): G1 (50 ?s); G2 (100 ?s); G3 (300 ?s); G4 (600 ?s); G5 (1000 ?s); G6 (Abrasão triboquímica com partículas de 30 ?m); G7 (Sem tratamento). Após os tratamentos de superfície, os espécimes foram sinterizados em forno específico, de acordo com as recomendações do fabricante. Foram capturadas imagens em Microscópio Confocal a Laser 3D de cada espécime e avaliadas por meio de um software. A análise dos grupos irradiados revelou um aumento da rugosidade nos grupos G1, G2, G3 e G4 quando comparados aos grupos G6 e G7. O grupo G5 apresentou superfície totalmente plana e desfavorável para retenção. No que se refere à perda de volume e formação de degrau, os grupos G1, G2 e G3 demonstraram grande perda de volume e grande altura de degrau formado, o que pode levar a uma desadaptação da peça protética. No grupo G4 foram observados valores de rugosidade satisfatórios com pouca perda de volume e pequena altura de degrau formado, semelhante ao que foi notado para a abrasão trioboquímica (G6), podendo ser indicada para tratamento de superfície de Y-TZP pré-sinterizada. A irradiação com o laser de Er:YAG promoveu um padrão morfológico com muitas irregularidades, característico de ablação para os grupos G1, G2, G3 e G4 e, para todos os protocolos utilizados, não foi observada a presença de trincas ou carbonização. Sugere-se que a largura temporal de 600 ?s (G4) seja a mais indicada como alternativa para tratamento de superfície, objetivando a criação de micro-retenções superficiais, com pouca perda de volume de material e que, ao mesmo tempo, não provoque danos à estrutura da cerâmica policristalina. / This study evaluated the effects of different Er:YAG laser pulse width protocols on surface roughness, loss of volume of the material and the step height formed of pre-sintered Yttrium-stabilized tetragonal Zirconia Polycrystal (Y-TZP) by three-dimensional profilometric assessment. Blocks of pre-sintered Y-TZP were cut providing 63 standard 5mm thick samples which were divided by surface treatment, as follows (n=9): G1 (50?s); G2 (100?s); G3 (300?s); G4 (600?s); G5 (1000?s); G6 (tribochemical silica coating); G7 (Untreated). Laser settings: The Er:YAG laser (Fidelis III; Fotona, Ljubljana, Slovenia) 100mJ, 15,87J/cm2, 10Hz, 1W, (60%) and air (40%) cooling. After treated or not, samples were sintered according to the manufacturer\'s recommendations. Roughness, volume loss and step and were analyzed by 3D profilometric assessment with confocal laser microscopy. Irradiated groups showed an increased roughness in the groups G1, G2, G3 and G4 when compared to G6 and G7 groups. The G5 group showed a completely flat and unfavorable surface for retention. The groups G1, G2 and G3 shown great loss of volume and the step height formed, which can lead to a gap on the crowns. In G4 were observed satisfactory roughness with little loss of volume and the step height formed similar to G6. Irrespective of laser protocol, any of the specimens showed presence of cracks and carbonization. It is suggested that the pulse width 600?s (G4) is the most suitable pulse width protocol as an alternative surface treatment, promoting micro-retention, with little loss of volume of material, comparable to gold standard treatment.