京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19183号 / 工博第4060号 / 新制||工||1626(附属図書館) / 32175 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 吉田 潤一, 教授 杉野目 道紀, 教授 松原 誠二郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19895号 / 工博第4211号 / 新制||工||1651(附属図書館) / 32972 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 吉田 潤一, 教授 松田 建児, 教授 松原 誠二郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 新制・論文博士 / 博士(工学) / 乙第13542号 / 論工博第4205号 / 新制||工||1984(附属図書館) / (主査)教授 杉野目 道紀, 教授 大江 浩一, 教授 松原 誠二郎 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

<p dir="ltr">Nuclear mobile microreactors will serve as a unique, transportable power source, especially for remote communities. Because mobile microreactors are meant to remain operable after initial startup, keeping the microreactor cool during transport is a safety concern that must be taken into consideration. Due to the compact nature of shipping containers, there is no significant room for the installation of active cooling mechanisms. The thermal limitations imposed by current regulatory guidelines lead to a reactor shipment external maximum temperature of 85◦C. Transporting heat from the microreactor's exterior walls to its surrounding air within the shipping container under natural convection will serve as the greatest source of resistance to the decay heat removal. In the event of mechanical failure or local regulations restricting forced cooling systems within the shipping container, natural convection will be the primary method for transferring heat. Before mobile microreactors can reach commercial status, research must be conducted on ensuring continued passive safety. </p><p><br></p><p dir="ltr">During the unavailability of helium circulation, the internal reactor core is designed to cool by block-to-block conduction and radiation, and the reactor vessel surface is cooled by the ambient air. This scenario is anticipated during the transport of the micro-high temperature gas-cooled reactor (HTGR) in a shipping container. The conduction and radiation between the prismatic micro-HTGR blocks in the core can be influenced by variances in the thermal contacts. This work investigated the conduction within a simulated horizontal micro-HTGR core. An experimental setup was used to validate a numerical model for conduction radiation cooldown with postulated thermal contact conductances (TCC). The experimental setup consisted of a hexagonal assembly with scaled prismatic blocks placed within a high-temperature vacuum environment. The gaps between the blocks were well controlled and monitored. The experimental setup was designed in such a way that the temperature variation in the axial direction was minimal, such that the experiment could be observed as a 2D (r,θ) heat transfer problem. The experimental scenario was computationally modelled with a finite element analysis (FEA) program. Once validated, the computational model was used to investigate the impact of gap conductance on overall decay heat removal. Using a conservative estimate for gap conductance value (100 W/m2 − K) between the prismatic blocks, there is a negligible increase in temperature observed during decay heat generation with constant natural convection coefficients. </p><p><br></p><p dir="ltr">However, the internal temperature profile may change drastically depending on the exterior conditions of the microreactor. A second model for the worst case scenario of exterior cooling being limited to natural convection flows was validated against existing benchmark experimental data on natural convection in closed cavities. The investigations have been performed for several configurations, including different reactor sizes, power levels, and scenarios with or without shielding around the reactor pressure vessel (RPV). This conservative safety analysis restricts the power level of the reactor to be equal to 1 MWe. A more realistic analysis with intermittent shutdown of shipping container air circulation demonstrates that a 4 MWe reactor will reach 85◦C Code of Federal Regulations (CFR) limitations after one hour while a 5 MWe reactor reaches the limit after 34 minutes. </p><p><br></p><p dir="ltr">Finally, both models were combined into a conjugate heat transfer model to examine whether thermal contact conductance (TCC) values would affect the external temperature profile as well as the maximum temperature reached by the core to ensure material limitations would be maintained. Studies have been conducted on a micro-HTGR design that originates from the fuel block design of the MHTGR-350 with changes to the overall power level, TCC values, and outer shipping container wall temperatures. Changes to TCC values do not significantly change microreactor exterior temperatures. In addition, the internal temperatures under all examined conditions remained under 875◦C. </p>

The continuous microreactor-assisted solution deposition (MASD) process was used for the deposition of CdS thin films on fluorine-doped tin oxide (FTO) glass. The MASD system, including a T-junction micromixer and a microchannel heat exchanger is capable of isolating the homogeneous particle precipitation from the heterogeneous surface reaction. The results show a dense nanocrystallite CdS thin films with a preferred orientation at (111) plane. Focused-ion-beam was used for TEM specimen preparation to characterize the interfacial microstructure of CdS and FTO layers. The band gap of the microreactor-assisted deposited CdS film was determined at 2.44 eV. X-ray Photon Spectroscopy show the bindings of energies of Cd 3d₃/₂, Cd 3d₅/₂, S 2p₃/₂ and S 2p₁/₂ at 411.7 eV, 404.8 eV, 162.1 eV, and 163.4 eV, respectively. The film growth kinetics was studied by measuring the film thickness deposited from 1 minute to 15 minutes in physical (FIB-TEM) and optical (reflectance spectroscopy) approaches. A growth model that accounts for the residence time in the microchannel using empirical factor (η) obtained from previous reported experimental data. Applying this factor in the proposed modified growth model gives a surface reaction rate of 1.61*10⁶ cm⁴ mole⁻¹s⁻¹, which is considerable higher than the surface reaction rates obtained from the batch CBD process. With the feature of separating homogeneous and heterogeneous surface reaction, the MASD process provides the capability to tailor the surface film growth rate and avoid the saturation growth regime in the batch process. An in situ spectroscopy technique was used to measure the UV-Vis absorption spectra of CdS nanoparticles formed within the continuous flow microreactor. The spectra were analyzed by fitting the sum of three Gaussian functions and one exponential function in order to calculate the nanoparticle size. This deconvolution analysis shows the formation of CdS nanoparticles range from 1.13 nm to 1.26 nm using a residence time from 0.26 s to 3.96 s. Barrier controlled coalescence mechanism seems to be a reasonable model to explain the experimental UV-Vis data obtained from the continuous flow microreactor, with a rate constant k' value of 2.872 s⁻¹. Using CFD, low skewness value of the RTD curve at high flow rate (short τ) suggests good radial mixing at high flow rate is responsible for the formation of smaller CdS nanoparticles with a narrower size distribution. The combination of CdS nanoparticle solution with MASD process resulted in the hindrance of CdS thin film deposition. It is hypothesized that the pre-existing sulfide (S²⁻) ions and CdS nanoparticles changes the chemical species equilibrium of thiourea hydrolysis reaction. Consequently, the lack of thiourea slows down the heterogeneous surface reaction. To test the scalability of the MASD process, a flow cell and reel-to-reel (R2R)-MASD system were setup and demonstrated for the deposition of CdS films on the FTO glass (6" x 6") substrate. The film deposition kinetics was found to be sensitive to the flow conditions within the heat exchanger and the substrate flow cell. The growth kinetics of the CdS films deposited by R2R-MASD process was investigated by with a deposition time of 2.5 min, 6.3 min, and 9 min. In comparison with the continuous MASD process, the growth rate in R2R-MASD is higher, however more difficult to obtain a linear relationship with the deposition time. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Jan. 13, 2012 - Jan. 13, 2013

Equipamentos de plasma são muito utilizados para polimerização de filmes finos, orgânicos e inorgânicos. Filmes finos têm uma vasta gama de aplicações no desenvolvimento de dispositivos MEMS (MicroElectroMechanical Systems), tais como sensores, detectores, pré-concentradores, etc. Portanto, neste trabalho é apresentado um equipamento de polimerização por plasma com características distintas, o que permite seu uso para obtenção de novos filmes finos e/ou compósitos em uma única etapa de fabricação. Os filmes obtidos são formados por partes orgânicas distintas, ou mesmo por regiões adsorventes ou repelentes. Alguns filmes possuem partículas orgânicas em mistura com o filme fino, o que facilita o controle da rugosidade e da área superficial, permitindo seu uso em sistemas de retenção. O projeto do reator permite deposições por plasma introduzindo, simultaneamente e sem interrupção do processo, reagentes incompatíveis em plasma ou mesmo a formação seqüencial de camadas, sem a necessidade de abertura do reator entre as etapas do processo (etapa única). O projeto da câmara de plasma foi simulado usando FEMLAB 3.2® e caracterizado utilizando traçadores. Simularam-se fluxo de gás e partículas além de campo elétrico e magnético. As simulações e resultados experimentais mostraram boa coerência. O fluxo permaneceu sem grande vorticidade em toda a faixa de trabalho e o campo magnético foi adequado para o confinamento do plasma. Foram depositados filmes úteis para desenvolvimento de sensores e adsorventes, resistentes a corrosão ou compósitos. Foram polimerizados por plasma: hexametildisilazana (HMDS) com produção de filme hidrofóbico e adsorvente; metil-nonafluoro(iso)butil-éter (HFE 7100®), obtendo-se filmes com características adsorventes, mas oleofóbicos e medianamente hidrofílicos e 2,3-dihidrodecafluoropentano (Vertrel®) com formação de filmes com boa resistência à corrosão além de facilidade de adsorção. Partículas de amido foram recobertas com filme a base de HMDS e de HFE 7100 e mostraram boas propriedades para retenção de moléculas orgânicas de tamanho médio. Neste equipamento, filmes à base de HMDS mostraram-se úteis para retenção de compostos orgânicos, em fase líquida ou gasosa. Espectroscopia de infravermelho, da produção simultânea de filme a base de HMDS e de Vertrel, mostrou espécies de flúor e silício e eventualmente CO, porém CHn é a espécie em menor intensidade. Microscopia óptica dos filmes revela boa aderência em metais e acrílico e, para os fluorados, resistência a solventes orgânicos e à exposição a solução aquosa ácida ou básica. Intermixing e dupla camada só são obtidas em condições muito estreitas, entretanto, existe a possibilidade de formação de ilhas. Microbalança de quartzo mostrou que 2-propanol permeia no filme formado por intermixing de HFE7100 e HMDS, porém não existe nenhuma sensibilidade a n-hexano. Um microreator fabricado, com microcanais de 73 cm de comprimento, pôde reter aproximadamente 9.10-4 g/cm2 de 2-propanol em fase gasosa, usando-se o filme obtido por intermixing. Portanto, o filme é um bom candidato a preconcentração de compostos orgânicos voláteis em ambiente corrosivo. Uma microestrutura produzida com as partículas de amido recobertas foi proposta para avaliar em fluxo contínuo a contaminação de soluções aquosas. Foi possível determinar a contaminação na proporção de 1:200 em vol. de 2-propanol, com saturação em 25% em vol. / Plasma equipment is quite useful for polymerization of organic/inorganic thin films. Thin films have a vast range of applications as sensor, detectors, preconcentrators and so on. In this work plasma polymerization equipment is presented with innovative characteristics that it should allow the obtaining of new fine films and composites. These films can be formed not only with different organic parts but also with areas adsorbents and repellents. Some films will present particles, ceramic or metallic, in mixture with the organic thin film, which will facilitate the control of the roughness and of the superficial area, allowing its use in retention systems. The design of the reactor allows plasma depositions introducing more than one reactant simultaneously and without process interruption, or even sequential formation of layers, without the need of chamber opening among process steps, i. e., in a single step. It was simulated and characterized parts of the equipment, such as: gas flow and particles admission; electric and magnetic fields profiles. Therefore, a new plasma chamber with atypical geometry was simulated and projected and manufactured to obtain multiple layers and/or composites. The simulation and experimental results showed good coherence. The gas flow stayed without great vorticity in the all range of the work and the magnetic field was adequate for plasma confinement. As the main objective of this work is the production and characterization of news materials, thin films were deposited with purpose of being adsorbent; corrosion resistant; and composite, all useful for development of sensor. It was plasma polymerized: hexamethyldisilazane (HMDS), a well known organic silicon compound, methyl nonafluoro (iso) butyl ether: should have good resistance to the corrosion besides easiness of adsorption; and 2,3-dihydrodecafluoropentane: adsorbent, hydrophobic and oleophobic. Particles (starch 5mm), were recovered with HMDS and HFE 7100 and showed good properties for retention of medium size organic molecules, such as dye. The results were useful for retention of organic compounds, in liquid or gaseous phase. Not only, HMDS is possible in any configuration of electrodes and the obtained films are hydrophobic but also, fluorinated compounds polymerized, however, intermixing and couple layer is only obtained in very narrow conditions, but the possibility of formation of islands exists. The chemical characterization was determined for infrared spectroscopy, it showed species composed by fluorocompounds, and eventually CO, however CHn is the smallest species. The hydrophobic character, organophylic and oleophobic were obtained through contact angle measurements. Optical Microscopy not only reveals good adherence in metals and acrylic but also resistance to organic solvents, acid and exhibition of basic aqueous solution. A manufactured micro-reactor, with micro channels of 73 cm of length, can keep approximately 9.10-4 g/cm2 of 2-propanol in gaseous phase. Therefore, the film is a good candidate in organic preconcentration of volatile organic compounds even on corrosive environment.

This thesis deals with the development of new methods for efficient synthesis and analysis in asymmetric catalysis. It focuses on the preparation of chiral cyanohydrins by enantioselective addition of cyanide to prochiral aldehydes. The initial part of the thesis describes the development of a dual Lewis acid– Lewis base activation system for efficient synthesis of chiral O-acylated and Ocarbonylated cyanohydrins. This system was used for the preparation of a variety of cyanohydrins in high isolated yields and with up to 96% ee. Activation of the cyanide by nucleophilic attack of the Lewis base at the carbonyl carbon atom was supported experimentally. Secondly, convenient procedures for the synthesis of polymer-bound chiral YbCl3-pybox and Ti-salen complexes are described. The polymeric complexes were employed in cyanation of benzaldehyde. A T-shaped microreactor was used for screening of reaction conditions for the enantioselective cyanation of benzaldehyde using trimethylsilyl cyanide and acetyl cyanide as cyanide sources. A microreactor charged with the polymeric Tisalen complex was used for enantioselective cyanation of benzaldehyde. Finally, an enzymatic method for high throughput analysis of ee and conversion of products from chiral Lewis acid–Lewis base-catalysed additions of α- ketonitriles to prochiral aldehydes was developed. The method could be used for the analysis of a variety of O-acylated cyanohydrins. Microreactor technology was successfully combined with high throughput analysis for efficient catalyst optimisation. / QC 20100809

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2017-04-25T14:08:17Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO José Vinícius O. Carneiro-Final (BC).pdf: 3473579 bytes, checksum: 53d2c12ba53b539b7c125ce7329018ff (MD5) / Made available in DSpace on 2017-04-25T14:08:17Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO José Vinícius O. Carneiro-Final (BC).pdf: 3473579 bytes, checksum: 53d2c12ba53b539b7c125ce7329018ff (MD5) Previous issue date: 2016-09-01 / Diante da necessidade de tratar os contaminantes emergentes (CEs) presentes em águas residuais, o presente trabalho surge como uma rota alternativa de processo terciário a ser implantada nas estações de tratamento de efluentes (ETEs) convencionais. A fotodegradação do diclofenaco de sódio (DCF) mediante processos oxidativos avançados (POA), ocorreu via fotocatálise heterogênea utilizando nanotubos de TiO2 (NTs de TiO2) como fotocatalisadores. Empregou-se um reator em batelada com fotocatalisadores em placa (NTs de TiO2 e NTs de TiO2-Au ) e um reator tubular carregado com um microrreator (fotocatalisador) dotado de NTs de TiO2 sensibilizado ou não com nanopartículas de ouro (NPs Au). A síntese dos NTs de TiO2 ocorreu pelo processo de anodização utilizando como substrato folhas de titânio metálico (Ti). As matrizes nanotubulares foram cristalizadas por tratamento térmico (400°C por 3h). A sensibilização com NPs de Au foi realizada in situ por redução através da radiação UV. A fotodegradação foi realizada a partir da irradiação do simulador solar NEWPORT modelo 67005 com uma lâmpada de Xenônio-Mercúrio (com potência calibrada para 1 SOL), na ausência ou presença de filtro (UV ou visível). A fase cristalina anatase dos NTs de TiO2 foi identificada pela difração de raios X (DRX). Foi estimada pelo refinamento de Rietveld uma cristalinidade de 77% para a superfície fotocatalítica, com a anatase (NTs de TiO2 cristalizados) representando 92,4% desta fase cristalina. A energia de band gap dos fotocatalisadores de 3,23 eV foi determinada pela espectroscopia de reflectância difusa. Através da microscopia eletrônica de varredura (MEVEDD) foi possível visualizar para a folha de Ti lisa, estruturas cilíndricas dos NTs de TiO2 que cresceram perpendicular ao substrato, apresentando um diâmetro médio de 78,87 nm e comprimentos na ordem de 2 µm, no caso da folha de Ti ondulada os NTs de TiO2 cresceram em direções variadas apresentando um diâmetro médio de 81,09 nm e comprimentos na ordem de 3 µm. A presença das NPs Au foi identificada pela espectroscopia de energia dispersiva (EDD). A determinação e quantificação de produto e reagente da fotocatálise heterogênea na degradação do DCF foram realizadas pela combinação de métodos analíticos (Cromatografia líquida de alta eficiência, Ressonância Magnética e Infravermelho por transformada de Fourier), obtendo uma conversão de 100% do DCF para testes no reator em batelada e de 37,0% no reator com recirculação para o melhor sistema fotocatalítico. Foi estimado através da análise de carbono orgânico total (COT) uma mineralização de 18,5% do DCF inicial para o sistema fotocatalítico mais eficiente utilizando o reator com recirculação. A ecotoxicidade do DCF e seus produtos de fotodegradação foi avaliada utilizando microcrustáceos (Artêmias Salinas) como bioindicador. / Faced with the need to address emerging contaminants (ECs) in waste water, this work is an alternative route of tertiary process to be implemented in conventional wastewater treatment plants (WTPs). Sodium diclofenac photodegradation (DCF) by advanced oxidation processes (AOP), occurred via heterogeneous photocatalysis using TiO2 nanotubes (TiO2 NTs) as photocatalysts. He employed a batch reactor with photocatalysts plate (TiO2 NTs and TiO2 - Au NTs) and a tubular reactor charged with a microreactor (photocatalyst) having TiO2 NTs sensitized or not with gold nanoparticles (NPs Au). The synthesis of TiO2 NTs occurred by anodization process using as substrate sheets of metallic titanium (Ti). The nanotubulares matrices were crystallized by heat treatment (400 ° C for 3h). The sensitization Au NPs was performed in situ by reduction by UV radiation. The photodegradation was carried from the irradiation NEWPORT solar simulator 67005 model with a xenon-mercury lamp (calibrated power for 1 SUN) in the absence or presence of filter (UV or visible). The anatase crystalline phase of TiO2 NTs was identified by X-ray diffraction (XRD). It was estimated by Rietveld refinement a crystallinity of 77% at the photocatalytic surface with anatase (TiO2 crystallized NTs) representing 92.4% of this crystalline phase. The energy band gap of 3.23 eV photocatalysts was determined by diffuse reflectance spectroscopy. By scanning electron microscopy (SEM-EDS) it was possible to view the Ti smooth sheet, cylindrical structures of TiO2 NTs that grew perpendicular to the substrate, with an average diameter of 78.87 nm and lengths in 2 µm order, in the case of the corrugated Ti sheet the TiO2 NTs grew in different directions with a mean diameter of 81.09 nm and lengths on the order of 3 µm. The presence of NPs Au was identified by energy dispersive spectroscopy (EDS). The determination and quantification of product and reactant of heterogeneous photocatalytic on the degradation of DCF were performed by a combination of analytical methods (high-performance liquid chromatography, Magnetic Resonance and Infrared Fourier transform ), whereby a conversion of 100 % DCF for testing in batch reactor and 37.0 % in the reactor for recirculating the best photocatalytic system. It was estimated by analyzing total organic carbon (TOC) a mineralization of 18.5 % of the initial DCF for more efficient photocatalyst system using the reactor with recirculation. The ecotoxicity of DCF and its photodegradation products was evaluated using microcrustaceans (Artemias Salinas) as bioindicator.

Equipamentos de plasma são muito utilizados para polimerização de filmes finos, orgânicos e inorgânicos. Filmes finos têm uma vasta gama de aplicações no desenvolvimento de dispositivos MEMS (MicroElectroMechanical Systems), tais como sensores, detectores, pré-concentradores, etc. Portanto, neste trabalho é apresentado um equipamento de polimerização por plasma com características distintas, o que permite seu uso para obtenção de novos filmes finos e/ou compósitos em uma única etapa de fabricação. Os filmes obtidos são formados por partes orgânicas distintas, ou mesmo por regiões adsorventes ou repelentes. Alguns filmes possuem partículas orgânicas em mistura com o filme fino, o que facilita o controle da rugosidade e da área superficial, permitindo seu uso em sistemas de retenção. O projeto do reator permite deposições por plasma introduzindo, simultaneamente e sem interrupção do processo, reagentes incompatíveis em plasma ou mesmo a formação seqüencial de camadas, sem a necessidade de abertura do reator entre as etapas do processo (etapa única). O projeto da câmara de plasma foi simulado usando FEMLAB 3.2® e caracterizado utilizando traçadores. Simularam-se fluxo de gás e partículas além de campo elétrico e magnético. As simulações e resultados experimentais mostraram boa coerência. O fluxo permaneceu sem grande vorticidade em toda a faixa de trabalho e o campo magnético foi adequado para o confinamento do plasma. Foram depositados filmes úteis para desenvolvimento de sensores e adsorventes, resistentes a corrosão ou compósitos. Foram polimerizados por plasma: hexametildisilazana (HMDS) com produção de filme hidrofóbico e adsorvente; metil-nonafluoro(iso)butil-éter (HFE 7100®), obtendo-se filmes com características adsorventes, mas oleofóbicos e medianamente hidrofílicos e 2,3-dihidrodecafluoropentano (Vertrel®) com formação de filmes com boa resistência à corrosão além de facilidade de adsorção. Partículas de amido foram recobertas com filme a base de HMDS e de HFE 7100 e mostraram boas propriedades para retenção de moléculas orgânicas de tamanho médio. Neste equipamento, filmes à base de HMDS mostraram-se úteis para retenção de compostos orgânicos, em fase líquida ou gasosa. Espectroscopia de infravermelho, da produção simultânea de filme a base de HMDS e de Vertrel, mostrou espécies de flúor e silício e eventualmente CO, porém CHn é a espécie em menor intensidade. Microscopia óptica dos filmes revela boa aderência em metais e acrílico e, para os fluorados, resistência a solventes orgânicos e à exposição a solução aquosa ácida ou básica. Intermixing e dupla camada só são obtidas em condições muito estreitas, entretanto, existe a possibilidade de formação de ilhas. Microbalança de quartzo mostrou que 2-propanol permeia no filme formado por intermixing de HFE7100 e HMDS, porém não existe nenhuma sensibilidade a n-hexano. Um microreator fabricado, com microcanais de 73 cm de comprimento, pôde reter aproximadamente 9.10-4 g/cm2 de 2-propanol em fase gasosa, usando-se o filme obtido por intermixing. Portanto, o filme é um bom candidato a preconcentração de compostos orgânicos voláteis em ambiente corrosivo. Uma microestrutura produzida com as partículas de amido recobertas foi proposta para avaliar em fluxo contínuo a contaminação de soluções aquosas. Foi possível determinar a contaminação na proporção de 1:200 em vol. de 2-propanol, com saturação em 25% em vol. / Plasma equipment is quite useful for polymerization of organic/inorganic thin films. Thin films have a vast range of applications as sensor, detectors, preconcentrators and so on. In this work plasma polymerization equipment is presented with innovative characteristics that it should allow the obtaining of new fine films and composites. These films can be formed not only with different organic parts but also with areas adsorbents and repellents. Some films will present particles, ceramic or metallic, in mixture with the organic thin film, which will facilitate the control of the roughness and of the superficial area, allowing its use in retention systems. The design of the reactor allows plasma depositions introducing more than one reactant simultaneously and without process interruption, or even sequential formation of layers, without the need of chamber opening among process steps, i. e., in a single step. It was simulated and characterized parts of the equipment, such as: gas flow and particles admission; electric and magnetic fields profiles. Therefore, a new plasma chamber with atypical geometry was simulated and projected and manufactured to obtain multiple layers and/or composites. The simulation and experimental results showed good coherence. The gas flow stayed without great vorticity in the all range of the work and the magnetic field was adequate for plasma confinement. As the main objective of this work is the production and characterization of news materials, thin films were deposited with purpose of being adsorbent; corrosion resistant; and composite, all useful for development of sensor. It was plasma polymerized: hexamethyldisilazane (HMDS), a well known organic silicon compound, methyl nonafluoro (iso) butyl ether: should have good resistance to the corrosion besides easiness of adsorption; and 2,3-dihydrodecafluoropentane: adsorbent, hydrophobic and oleophobic. Particles (starch 5mm), were recovered with HMDS and HFE 7100 and showed good properties for retention of medium size organic molecules, such as dye. The results were useful for retention of organic compounds, in liquid or gaseous phase. Not only, HMDS is possible in any configuration of electrodes and the obtained films are hydrophobic but also, fluorinated compounds polymerized, however, intermixing and couple layer is only obtained in very narrow conditions, but the possibility of formation of islands exists. The chemical characterization was determined for infrared spectroscopy, it showed species composed by fluorocompounds, and eventually CO, however CHn is the smallest species. The hydrophobic character, organophylic and oleophobic were obtained through contact angle measurements. Optical Microscopy not only reveals good adherence in metals and acrylic but also resistance to organic solvents, acid and exhibition of basic aqueous solution. A manufactured micro-reactor, with micro channels of 73 cm of length, can keep approximately 9.10-4 g/cm2 of 2-propanol in gaseous phase. Therefore, the film is a good candidate in organic preconcentration of volatile organic compounds even on corrosive environment.

Ce travail porte sur le développement de nouvelles méthodes de mesure permettant la caractérisation de réactions chimiques très exothermiques dans des conditions de sécurité. Pour cela, nous souhaitons combiner l’analyse thermique des réactions et la technologie microfluidique. L’utilisation de la microfluidique rend possible l’utilisation de très faibles volumes réactionnels limitant ainsi tout risque lié à la dangerosité des réactions explosives. Le premier appareil développé est un microcalorimètre qui mesure le flux de chaleur global dégagé lors d’un écoulement co-courant ou gouttes. Plusieurs paramètres peuvent être déterminés : enthalpie de mélange et de réaction, concentration par dosage calorimétrique et cinétique. Le deuxième dispositif consiste à mesurer le champ de température du milliréacteur isopéribolique à l’aide d’une caméra InfraRouge et ainsi de suivre localement l’évolution de la réaction pour déterminer les paramètres thermocinétiques. / This work deals with the development of new measurement methods in order to characterize high exothermic chemical reactions in safe conditions. Thus, we combine thermal analysis with microfluidic technology. The use of microfluidics allows to manipulate a very small amount of product safely. First, we have developed a microcalorimeter to measure the global heat flux produced in co-flow or droplet-flow configurations. Several parameters can be determined: reaction and mixing enthalpy, concentrations by calorimetric titration and kinetics. The second method uses an InfraRed camera to measure the temperature field of the isoperibolic millireactor. Then, the local evolution of the reaction is estimated by thermal processing. From such inverse methods, the thermokinetic parameters can be determined.