京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20001号 / 工博第4245号 / 新制||工||1657(附属図書館) / 33097 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 作花 哲夫, 教授 安部 武志, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Industrial production of hydrogen from the syngas, generated from steam reformation of natural gas or coal gasification, sets conditions for hydrogen separation membranes in terms of operating conditions. An alternative source for hydrogen is a syngas generated by gasification of municipal solid wastes which are likely to set more stringent conditions for the separation membranes. There is therefore, a growing demand for separation membranes with improved permeability and particularly of low cost. Among various alternatives, metallic membranes are particularly attractive due to their high selectivity and permeability for hydrogen, exemplified by palladium (Pd). However, due to high cost of Pd there is still a demand to develop alternative metallic membranes that are of low cost and have improved durability. Efforts have therefore concentrated on either alloying Pd so as to reduce its cost or on alternative membrane compositions of particularly b.c.c. structure. The current study deals with hydrogen separation membranes and aims to develop infrastructure for rapid identification of membrane compositions with improved permeability. The study is made up of three parts / i) development of sputter deposition system that would allow deposition of multiple compositions in a single experiment, ii) development of substrate material that would support the thin film membranes and would allow permeability measurement and iii) development of a set-up to measure the permeability of the thin film membranes. In the present thesis, a sputter deposition system incorporating three targets was successfully constructed. The system as tested with palladium-niobium-titanium (Pd-Nb-Ti) ternary system after necessary adjustment would yield thin films of homogenous thickness (&le / 7%) over a sample area of &asymp / 150 mm diameter. A total of 21 substrates each in 19 mm diameter arranged in triangular form in the substrate holder could successfully be deposited where composition distributions covered a greater portion of Pd-Nb-Ti ternary phase diagram. The structure of the deposited thin films can successfully be controlled by substrate temperature as well as by the pressure of plasma gas (argon). With the help of these parameters, structural diversity can also be produced beside the compositional variation. As for substrates, two materials were investigated. These were titanium dioxide (TiO2) modified porous stainless steel (PSS) and anodic porous alumina (AAO). TiO2 modified PSS due to its associated surface roughness leads to the deposition of films with defected structure which as a result is not gas tight. AAO produced via anodization of aluminum foil had a regular (40-60 nm) pore structure that provides a suitable surface for thin film depositions which could be defect free. However, AAO is very delicate and fragile which makes it difficult to adapt it as a support material for permeability measurement/hydrogen separation purposes. Finally, a set-up was developed for measurement of hydrogen permeability which is capable of measurement over a wide pressure and temperature conditions, i.e. hydrogen pressures up to 10 bar and temperature as high as 450 &deg / C. It is recommended that so as to identify compositions with improved permeability, Nb or a similar metal which has extremely high permeability could be used as a support material. This would tolerate the evaluation of the films which are not totally defect free.

Vertically aligned Multiwalled Carbon Nanotubes (MWCNTs) were grown in the pores of Anodized Aluminum Oxide (AAO) templates and investigated for resistive sensor applications. High Sensitivity of 23% to low concentration (100 ppm) of ammonia was observed. An equivalent circuit model was developed to understand the current flow path in the resistive sensor. This helped us in achieving high sensitivities through amorphous carbon (a-C) layer thickness tailoring by employing post-growth processing techniques like plasma etching. A simulation model in MATLAB was developed to calculate the device resistance and the change in the sensitivity as a function of device parameters. The steady state response and transient response of the model to the number of ammonia molecules and its adsorption rate were studied. Effects of oxygen plasma, argon plasma and water plasma etch on thinning of the a-C layer were studied. In order to enhance the sensitivity, the top and bottom a-C layers were replaced by a more conductive metal layer. This also helped in understanding the current flow in the device and in the estimation of the resistivity of the a-C layer.

[ES] La presente Tesis Doctoral tiene dos objetivos claramente diferenciados, siendo el primero de ellos la realización de un estudio de optimización de la síntesis de nanoestructuras de óxido de wolframio (WO3) mediante el uso de un diseño de experimentos, mientras que el segundo de ellos es el uso de estas nanoestructuras en la degradación fotoelectrocatalítica de 4 pesticidas organofosforados de diferentes subfamilias (diazinon, fosmet, clorfenvinfos y fenamifos). El uso del óxido de wolframio como fotocatalizador en el proceso fotoelectrocatalítico (FEC) despierta un gran interés, ya que se trata de un semiconductor con gran fotoestabilidad en electrolitos acuosos ácidos, excelente conductividad eléctrica, tiene la capacidad de absorber la parte azul del espectro visible además de la luz ultravioleta, y el borde superior de la banda de valencia es mayor que el potencial de oxidación de H2O/O2. Todo ello hace que el WO3 sea capaz de fotooxidar eficazmente una amplia gama de compuestos orgánicos. Las nanoestructuras estudiadas en la Tesis Doctoral se sintetizaron mediante anodizado electroquímico, ya que se trata de una técnica sencilla que permite un control de sus parámetros de manera fácil y efectiva, permitiendo obtener las nanoestructuras directamente sobre el propio sustrato metálico. Además, la necesidad de controlar y eliminar los contaminantes emergentes en el medio ambiente se ha vuelto cada vez más crucial durante las últimas décadas. Así, en esta Tesis se han degradado 4 pesticidas tóxicos y persistentes en el medioambiente mediante la técnica de fotoelectrocatálisis (FEC) utilizando las nanoestructuras de WO3. En esta técnica, los fenómenos electrolíticos y fotocatalíticos actúan juntos para mineralizar el contaminante orgánico. Además, la FEC está atrayendo la atención de los investigadores por su capacidad para degradar contaminantes orgánicos y transformarlos en compuestos inocuos con condiciones de trabajo no extremas. Por tanto, en el diseño de experimentos realizado en la Tesis Doctoral se modificaron 3 variables con tres niveles cada una, por tanto se escogió un diseño 33. Las variables que se modificaron fueron el electrolito utilizado durante el anodizado, la temperatura y atmosfera en el proceso de post-anodizado (tratamiento térmico), obteniendo de esta manera nanoestructuras con diferentes propiedades tanto estructurales como fotoelectroquímicas. Los resultados obtenidos mostraron que las nanoestructuras que presentan mejores propiedades morfológicas y fotoelectroquímicas, y con una estructura cristalina más adecuada fueron las obtenidas con el ácido metanosulfónico (CH4O3S) como electrolito y calentadas en el proceso de post-anodizado a 600 ¿C y en atmósfera de aire. Con estas nanoestructuras optimizadas, se realizó el proceso de degradación de los 4 pesticidas seleccionados mediante fotoelectrocatálisis. En este proceso, se partió de una concentración inicial de 20 ppm en todos los pesticidas, haciéndose un seguimiento del pesticida mediante UV-Visible y cromatografía líquida de ultra alto rendimiento acoplada a la espectrometría de masas (UHPLC-MS/Q-TOF). Tras 24 horas de ensayo se consiguió degradar el diazinón hasta 2 ppm (consiguiendo un 90% de degradación), el clorfenvinfos se degradó hasta 1 ppm (consiguiendo un 95% de degradación) y el fosmet y fenamifos se degradaron al 100%. Para cada uno de los pesticidas se ha propuesto una ruta de degradación según los compuestos intermedios identificados mediante el UHPLC-MS/Q-TOF, dando como resultado final moléculas más pequeñas y más inocuas para los seres humanos y para el medioambiente. / [CA] La present tesi doctoral té dos objectius clarament diferenciats, sent el primer la realització d'un estudi d'optimització de la síntesi de nanoestructures d'òxid de wolframi (WO3) mitjançant l'ús d'un disseny d'experiments, mentre que el segon és l'ús d'aquestes nanoestructures en la degradació fotoelectrocatalítica de quatre pesticides organofosforats de diferents subfamílies (diazinon, fosmet, clorfenvinfòs i fenamifòs). L'ús de l'òxid de wolframi com a fotocatalitzador en el procés fotoelectrocatalític (FEC) desperta un gran interès, ja que es tracta d'un semiconductor amb gran fotoestabilitat en electròlits aquosos àcids; amb una excel·lent conductivitat elèctrica; té la capacitat d'absorbir la part blava de l'espectre visible, a més de la llum ultraviolada, i la vora superior de la banda de valència és major que el potencial d'oxidació d'H2O/O2. Tot això fa que el WO3 siga capaç de fotooxidar eficaçment una àmplia gamma de compostos orgànics. Les nanoestructures estudiades en la tesi doctoral es van sintetitzar mitjançant anodització electroquímica, ja que es tracta d'una tècnica senzilla que permet un control dels seus paràmetres de manera fàcil i efectiva, i permet obtenir les nanoestructures directament sobre el mateix substrat metàl·lic. A més, la necessitat de controlar i eliminar els contaminants emergents en el medi ambient s'ha tornat cada vegada més crucial durant les últimes dècades. Així, en aquesta tesi s'han degradat quatre pesticides tòxics i persistents en el medi ambient mitjançant la tècnica de la fotoelectrocatàlisi (FEC) utilitzant les nanoestructures de WO3. En aquesta tècnica, els fenòmens electrolítics i fotocatalítics actuen junts per a mineralitzar el contaminant orgànic. La FEC està atraient l'atenció del personal investigador per la seua capacitat per a degradar contaminants orgànics i transformar-los en compostos innocus amb condicions de treball no extremes. Per tant, en el disseny d'experiments realitzat en la tesi doctoral es van modificar tres variables amb tres nivells cadascuna, per tant, es va triar un disseny 33. Les variables que es van modificar van ser: l'electròlit utilitzat durant l'anodització, la temperatura i l'atmosfera en el procés de postanodització (tractament tèrmic), i es van obtenir d'aquesta manera nanoestructures amb diferents propietats, tant estructurals com fotoelectroquímiques. Els resultats obtinguts van mostrar que les nanoestructures que presenten millors propietats morfològiques i fotoelectroquímiques, i amb una estructura cristal·lina més adequada, van ser les obtingudes amb l'àcid metanosulfònic (CH4O3S) com a electròlit, i calfades en el procés de postanodització a 600 ¿C i en atmosfera d'aire. Amb aquestes nanoestructures optimitzades, es va realitzar el procés de degradació dels quatre pesticides seleccionats mitjançant fotoelectrocatàlisi. En aquest procés, es va partir d'una concentració inicial de 20 ppm en tots els pesticides, i es va fer un seguiment del pesticida mitjançant UV visible i cromatografia líquida d'ultraalt rendiment acoblada a l'espectrometria de masses (UHPLC-MS/Q-TOF). Després de 24 hores d'assaig, es va aconseguir degradar el diazinon fins a 2 ppm (es va assolir un 90% de degradació), el clorfenvinfòs es va degradar fins a 1 ppm (es va assolir un 95% de degradació) i el fosmet i el fenamifòs es van degradar al 100%. Per a cadascun dels pesticides s'ha proposat una ruta de degradació segons els compostos intermedis identificats mitjançant l'UHPLC-MS/Q-TOF, que dona com a resultat final molècules més xicotetes i més innòcues per als éssers humans i per al medi ambient. / [EN] This Doctoral Thesis has two clearly differentiated objectives. The first objective is to carry out an optimization study of the synthesis of tungsten oxide nanostructures (WO3) using a design of experiments. The second objective is to use of these nanostructures in the photoelectrocatalytic degradation of 4 organophosphate pesticides of different subfamilies (diazinon, phosmet, chlorfenvinphos and fenamiphos). The use of tungsten oxide as a photocatalyst in the photoelectrocatalytic (PEC) process arouses great interest, since it is a semiconductor with great photostability in acidic aqueous electrolytes, excellent electrical conductivity, it has the ability to absorb the blue part of the visible spectrum in addition to ultraviolet light, and the upper edge of the valence band is greater than the oxidation potential of H2O / O2. All this makes WO3 capable of efficiently photo-oxidizing a wide range of organic compounds. The nanostructures studied in the Doctoral Thesis were synthesized using electrochemical anodization, since it is a simple technique that permits the control their parameters easily and effectively, allowing the nanostructures to be obtained directly on the metal substrate itself. Furthermore, the need to control and eliminate emerging pollutants in the environment has become increasingly crucial over the past decades. Thus, in this Thesis, 4 toxic and persistent pesticides in the environment have been degraded by the photoelectrocatalysis (PEC) technique using the WO3 nanostructures. In this technique, the electrolytic and photocatalytic phenomena act together to mineralize the organic contaminant. PEC is attracting the attention of researchers for its ability to degrade organic pollutants and transform them into harmless compounds under non-extreme working conditions. Therefore, in the design of experiments carried out in the Doctoral Thesis, 3 variables were modified with three levels each one, therefore a 33 design was chosen. The variables that were modified were the electrolyte used during the anodization, the temperature and the atmosphere in the post-anodization process (annealing treatment), thus obtaining nanostructures with different structural and photoelectrochemical properties. The results obtained showed that the nanostructures with the best morphological and photoelectrochemical properties, and with adequate crystalline structure werethose obtained with methanesulfonic acid (CH4O3S) as electrolyte and annealed in the post-anodization process at 600 ¿C and in an air atmosphere. With these optimized nanostructures, the degradation process of the 4 selected pesticides was carried out by photoelectrocatalysis. This process started from an initial concentration of 20 ppm in all pesticides, using UV-Visible and Ultra-High Performance Liquid Chromatography coupled to Mass Spectrophotometry (UHPLCMS / Q-TOF) to monitoring the process. After 24 hours of experiment, the diazinon was degraded to 2 ppm (achieving 90% degradation), chlorfenvinphos was degraded to 1 ppm (achieving 95% degradation) and phosmet and fenamiphos were 100% degraded. For each of the pesticides, a degradation route has been proposed according to the intermediate compounds identified by UHPLC-MS/Q-TOF, resulting in smaller and more innocuous molecules for humans and the environment. / Agradezco a la Generalitat Valenciana y al Fondo Social Europeo por la ayuda predoctoral recibida para la realización de la presente Tesis Doctoral (ACIF 159- 2018) así como para la realización de una estancia predoctoral en la Universidad de Lisboa. También quiero agradecer al Ministerio de Economía, Industria y Competitividad, por la concesión de los proyectos CTQ2016-79203-R (2016) y PID2019-105844RB-I00 (2019) en los cuales he podido participar durante la Tesis Doctoral. / Roselló Márquez, G. (2021). Eliminación de pesticidas organofosforados mediante fotoelectrocatálisis con fotoánodos de WO3 [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/174712 / TESIS

Les infections nosocomiales liées aux dispositifs médicaux, et plus particulièrement ceux de la perfusion, sont un problème majeur dans le milieu hospitalier. Ces infections sont liées à la présence de biofilm. Pour lutter contre le biofilm, les mesures préventives en hygiène ne sont pas suffisantes. Les recherches se dirigent vers la modification des surfaces des matériaux des dispositifs médicaux: ajout de substances biocides, développement de surfaces antiadhésives par voie chimique ou topographique. L’objectif de cette thèse est de créer des polymères nanostructurés pouvant entrer dans la composition de dispositifs médicaux de la perfusion et de tester leur impact sur l’adhésion bactérienne et le développement du biofilm. Dans un premier temps, la technique de nanostructuration choisie repose sur la réplication d’un moule nanostructuré en alumine nanoporeuse qui se caractérise par des nanopores auto-organisés en nid d’abeille. Après avoir mis en place une station d’anodisation permettant la nanostructuration de ce moule, la reproductibilité du procédé de fabrication a été validée (diamètre des pores : 51 ± 6 nm, profondeur: 97 ± 9 nm, espace interpores: 102 ± 6 nm). Ensuite, les travaux de réplication ont été effectués avec le polymère ABS (acrylonitrile-butadiène-styrène). Plusieurs méthodes de réplication ont été testées à partir de dépôt de solutions de polymères ou de fonte du matériau sur le moule d’alumine. La méthode sélectionnée sur des critères de reproductibilité et de facilité de transposition industrielle donne des nanostructures de type nanopicots (diamètres des picots : 56 ± 7 nm, distances interpicots : 101 ± 16 nm, longueurs : 73 ± 33 nm). Les surfaces développées sont ensuite caractérisées (MEB, DSC analyse calorimétrique différentielle, spectrométrie Infra Rouge, angle de contact). La fabrication des nanostructures ne semble pas dégrader le matériau ABS et la modification topographique rend la surface plus hydrophile. Une étude de stabilité montre que les nanostructures résistent à plusieurs modes de stérilisation (oxyde d’éthylène, plasma H2O2 et rayon Beta) et sont conservés dans le temps, ce qui les rend applicables à la surface d’un dispositif médical. La seconde étape du travail consiste à évaluer l’adhésion bactérienne sur les surfaces témoins et nanostructurées. Différents tests de culture de biofilm ont été réalisés avec S. epidermidis en conditions statique ou dynamique. Après un temps de 3 à 48h, les bactéries sont décrochées de la surface puis dénombrées sur gélose. Il n’y a pas de différence significative d’adhésion bactérienne entre les deux types de surface. L’observation en microscopie électronique à balayage et confocale à 24h semble confirmer ce résultat. Des tests réalisés avec d’autres souches bactériennes (S. aureus, K. pneumoniae, P. aeruginosa) en condition statique montrent également que l’adhésion est également identique sur les deux surfaces. Par conséquent, nous pouvons conclure que nos surfaces ABS développées avec ces nanopicots spécifiques n’ont pas un effet anti-adhésion sur les bactéries testées. Des recherches récentes mettent en évidence que l’espacement entre les nanopciots est un facteur critique sur l’adhésion bactérienne. L’étape suivante de notre travail consiste à tester de nouvelles nanostructures réalisées avec un moule AAO ayant une distance interpore plus grande. / Medical device-related infections are a public health concern and an economic burden. The role of biofilms in medical device-related infections is clearly established. Preventive hygiene measures are not often sufficient to prevent biofilms formation. One promising way of preventing device-related infections is the development of medical devices with surfaces or materials that reduce either microbial viability using biocidal substances or microbial adhesion with topographical modifications.Developing nanostructured polymeric surfaces, which could have applications in medical devices, and testing their impact on bacterial adhesion and biofilm development were the main goals of this thesis. First of all, the polymer was replicated on an aluminum anodized oxide nanostructured mold (AAO), characterized by highly ordered nanopores. An anodization station was made in order to create molds. Then, the reproducibility of the process fabrication was validated (pore diameter: 51 ± 6 nm, deepness 97 ± 9 nm, interpore espace: 102 ± 6 nm). Several replication techniques with ABS were tested including polymers solutions and melted polymers. The selected method was the one with the most reproducible results pillar diameter: 56 ± 7 nm, interpillar distance: 101 ± 16 nm, length: 73 ± 33 nm) and the most representative of industrial injection processes. The created surfaces were then characterized (MEB, DSC, ATR-FTIR, wettability). The fabrication process does not seem to degrade the ABS material and the topographical change increases the hydrophilicity of the surface. A stability study showed that the nanopillars were resistant to several sterilization processes (ethylene oxide, H2O2 plasma, Beta irradiation) and were maintained through time, which is an important element for applications in medical-devices.The second step of our work consisted of assessing bacterial adhesion on control and nanostructured ABS samples. Several biofilm tests were made with S. epidermis in static and dynamic conditions. Between 3 and 48 hours of culture, bacteria were removed from the surfaces and then viable plate counting was performed. No significant differences were observed between the samples. Microscopic observations (MEB, CSLM) seemed to confirm this result. Other bacteria with different morphologies were tested (S. aureus, K. pneumoniae, P. aeruginosa): bacterial adhesion was similar for the two surfaces. Therefore, we can conclude that our developed ABS surfaces with these specific nanopillars do not have an anti-adhesion effect on the tested bacteria. Recent researches showed that spacing between nanopillars is a critical factor on bacterial adhesion. The following step of our work would be to test new nanostructures using AAO molds with bigger interpore distance.

L'objectif premier de ce projet est la mise au point de procédés de fabrication microélectroniques/microtechnologiques compatibles avec l'utilisation d'un support papier. Pour cela, des techniques comme l'évaporation thermique sous vide, la photolithographie, l'électrodéposition et l'anodisation d'aluminium ont été développées et adaptées à ce support. Des bancs de caractérisations structurels, électriques et flexibles ont été aussi mis en œuvre pour étudier la fiabilité des couches déposées sur un tel substrat. En application, un capteur d'humidité à base d'oxyde d'aluminium flexible a été fabriqué et les tests en humidité ont montré d'excellents résultats permettant de valider le travail effectué. / The primary objective of this project is the implementation of microelectronics/microtechnology processes compatible with the use of paper-based substrate. For this purpose, techniques such as thermal vacuum evaporation, photolithography, electroplating and anodizing aluminum have been developed and adapted to this substrate. Structural, electrical and flexible characterizations benches have also been implemented to study the reliability of the layers deposited on such substrate. A moisture sensor based on flexible aluminum oxide was made and humidity tests have shown excellent results which validate the work.

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