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京都大学 / 新制・課程博士 / 博士(工学) / 甲第23496号 / 工博第4908号 / 新制||工||1767(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 清水 芳久, 教授 越後 信哉, 准教授 松田 知成 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Advanced oxidation of organic pollutants with TiO2 photocatalysts is limited due to the wide bandgap of TiO2, 3.2 eV, which requires ultraviolet (UV) radiation. When nanosized TiO2 is modified by carbon doping, charge recombination is inhibited and the bandgap is narrowed, allowing for efficient photodegradation under visible light. Here, we propose a flame spray pyrolysis (FSP) technique to create TiO2. The facile process of FSP has been successful in preparing highly crystalline TiO2 nanoparticles. Using the same procedure to deposit TiO2 onto biochar, the photocatalyst was doped by the carbonaceous material. The morphology, crystalline and electronic structure of the FSP TiO2 and TiO2-decorated biochar (TiO2-BC) were characterized by SEM, XRD, TGA, DLS, and diffuse reflectance UV-vis spectroscopy. Photocatalytic performance of TiO2 and TiO2-BC was investigated for model organic contaminants in an aqueous solution under UV and visible light, which will be compared to that of Degussa P25 TiO2 as a control.

<p> Photocatalytic TiO2 coated paper was prepared as antibacterial paper to investigate bactericidal activity of TiO2 in the presence of UV light. When TiO2 exposed to UV light, it produced hydroxyl radicals which were strong oxidative groups and could damage the cell wall causing death of bacteria. The goal of this work was to develop a promising method for microbiological examination of antibacterial paper and to test the disinfection properties of photocatalytic TiO2 coated paper after UV illumination.</p> <p> Three different methods were modified to test antibacterial effect of TiO2 coated paper. The disk diffusion method, the washing method, and the membrane filter method. It was found that disk diffusion technique would not work because of insolubility of TiO2 in water but it could be used for any other antibacterial paper that consisted water soluble agent. The results from membrane filter method agreed with those of washing method showing the reduction of E.coli colonies for TiO2 coated paper after exposure to UV, comparing to blank paper.</p> <p> With use of washing method, it was shown that by changing some functions such as: increasing TiO2 content on the paper, increasing UV irradiation time or UV intensity, survival ratio of the bacteria decreased.</p> / Thesis / Master of Applied Science (MASc)

[ES] La estrategia de la Unión Europea es promover la salud en una población con una elevada esperanza de vida y junto a la necesidad de reducir el gasto sanitario, obligan al desarrollo de aleaciones de titanio y tratamientos superficiales que incrementen el ciclo de vida de los implantes y reduzcan los tiempos de hospitalización. En esta tesis doctoral se propone el desarrollo del proceso de anodizado electroquímico para la obtención de un recubrimiento nanotubular en las aleaciones de titanio beta. Su objetivo principal es la caracterización del recubrimiento superficial con topografía nanotubular en las aleaciones titanio ß para aplicaciones biomédicas. Los resultados obtenidos muestran que la reducción del tamaño de partícula de los polvos refractarios y el incremento de la temperatura máxima de sinterizado, reduce la porosidad residual e incrementa las propiedades mecánicas de la aleación pulvimetalúrgica de Ti35Nb10Ta. El proceso de anodizado electroquímico, empleando el electrolito compuesto por 1M H3PO4 y 0,8% en peso de NaF, ha permitido obtener una topografía nanotubular en la aleación de Ti35Nb10Ta. La aplicación de un tratamiento térmico, posterior al anodizado, reduce el contenido de flúor presente en el óxido con topografía nanotubular y estabiliza la estructura cristalina del óxido de titanio en las aleaciones ß pulvimetalúrgicas. El proceso de anodizado electroquímico, para la obtención de un recubrimiento nanotubular en las aleaciones de Ti35Nb10Ta, incrementa la rugosidad superficial. La topografía nanotubular incrementa el ángulo de contacto y la energía superficial de las aleaciones de titanio. La irradiación con luz ultravioleta modifica a hidrofílico el comportamiento hidrofóbico de las superficies nanotubulares de titanio. La resistencia a la corrosión del acabado superficial de nanotubos, sin tratamiento térmico, es menor que el resto de los acabados superficiales estudiados por su incremento del área superficial relativa. El tratamiento térmico realizado a las superficies nanotubulares estabiliza las fases cristalinas (anatasa y rutilo) del óxido de titanio e incrementa la resistencia a la corrosión de las aleaciones de titanio. Por último, para poder introducir la pulvimetalurgia y el acabado superficial nanotubular en el campo de los biomateriales se necesita seguir investigando en subprocesos que mejoren la homogeneidad química/microestructural, sus propiedades mecánicas y la resistencia a la corrosión, así como cuantificación del grado mejora de la biocompatibilidad de estos nuevos acabados superficiales. / [CA] L'estratègia de la Unió Europea és promoure la salut en una població amb una elevada esperança de vida, al costat de la necessitat de reduir la despesa sanitària, obliguen al desenvolupament d'aliatges de titani i tractaments superficials que incrementen el cicle de vida dels implants i reduïsquen els temps d'hospitalització. En aquesta tesi doctoral es proposa el desenvolupament del procés de anoditzat electroquímic per a l'obtenció d'un recobriment nanotubular en els aliatges de titani beta. El seu objectiu principal és la caracterització del recobriment superficial amb topografia nanotubular en els aliatges ß titani per a aplicacions biomèdiques. Els resultats obtinguts mostren que la reducció de la grandaria de partícula de les pols refractaris i l'increment de la temperatura màxima de sinterització, redueixen la porositat residual i incrementen les propietats mecàniques de l'aliatge pulvimetal·lúrgic de Ti35Nb10Ta. El procés de anoditzat electroquímic, emprant l'electròlit compost per 1 M H3PO4 i 0,8% en pes de NaF, ha permès obtenir una topografia nanotubular en l'aliatge de Ti35Nb10Ta. L'aplicació d'un tractament tèrmic, posterior a l'anoditzat, redueix el contingut de fluor present en l'òxid amb topografia nanotubular i estabilitza l'estructura cristal·lina de l'òxid de titani en els aliatges ß pulvimetal·lurgics. El procés de anoditzat electroquímic, per a l'obtenció d'un recobriment nanotubular en els aliatges de Ti35Nb10Ta, incrementa la rugositat superficial. La topografia nanotubular incrementa l'angle de contacte i l'energia superficial dels aliatges de titani. La irradiació amb llum ultraviolada modifica a hidrofílic el comportament hidrofòbic de les superfícies nanotubulares de titani. La resistència a la corrosió de l'acabat superficial de nanotubs, sense tractament tèrmic, és menor que la resta dels acabats superficials estudiats pel seu increment de l'àrea superficial relativa. El tractament tèrmic realitzat a les superficies nanotubulares estabilitza les fases cristal·lines (anatasa i rútil) de l'òxid de titani i incrementa la resistència a la corrosió dels aliatges de titani. Finalment, per poder introduir la pulverimetal·lúrgia i l'acabat superficial nanotubular en el camp dels biomaterials es necessita continuar investigant en subprocessos que milloren l'homogeneïtat química/microestructural, les seves propietats mecàniques i la resistència a la corrosió, així com la quantificar del grau millora de la biocompatibilitat d'aquests nous acabats superficials. / [EN] The European Union's strategy is to promote health in a population with an elevated lifemexpectancy, together with the necessity of reducing healthcare costs, forces the development of titanium alloys and surface treatments that increase the implants life cycle and reduce hospitalization times. In this Doctoral Thesis, the development of the electrochemical anodizing process is proposed to obtain a nanotubular coating in beta titanium alloys. The main objective is the characterization of the surface treatment, which presents a nanotubular topography, in ß titanium alloys for biomedical applications. The results show that the particle size reduction on refractory powders and higher maximum sintering temperature reduce the residual porosity and increase the mechanical properties of Ti35Nb10Ta powder metallurgical alloy. The electrochemical anodizing process, using the electrolyte composed of 1M H3PO4 and 0.8% w.t NaF, is capable of obtaining a nanotubular topography in the Ti35Nb10Ta alloy. Heat treatment cycle, after the anodizing process, reduces the fluorine content present in the nanotubular oxide layer and stabilizes the titanium oxide crystalline structure on the powder metallurgy ß titanium alloys. The electrochemical anodization process, to obtain a nanotubular layer in Ti35Nb10Ta alloys, increases the surface roughness. Nanotubular topography increases the contact angle and surface free energy of titanium alloys. The ultraviolet light irradiation modifies the nanotubular titanium surfaces behavior from hydrophobic to hydrophilic. The corrosion resistance for nanotubular surfaces, without heat treatment, is lower than the rest of the surface treatments studied due to its increase in relative surface area. The heat treatment carried out on the nanotubular surfaces stabilizes the titanium oxide crystalline phases (anatase and rutile) and increases titanium alloys corrosion resistance. Finally, in order to introduce the powder metallurgy and the nanotubular surface treatment in biomedical applications, it is necessary to continue researching in subprocesses that will improve the chemical/microstructural homogeneity, the mechanical properties, and corrosion resistance, as well as quantify the degree of biocompatibility improvement on this new surface treatments. / Lario Femenía, J. (2019). Efecto del anodizado electroquímico en la obtención de nanotubos en la superficie de aleaciones beta de titanio [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/129867

Yes / The tribological performance of a nanocrystalline coating is heavily influenced by its composition, morphology, and microstructural characteristics. This research work describes the effect of heat treatment temperature on the microstructural, morphological, and mechanical behavior of nanocrystalline Ni/TiO2 coatings produced by electrophoresis. The surface morphology and coating cross section were characterized by scanning electron microscopy (SEM). The composition of coatings and the percentage of TiO2 nanoparticles incorporated in the Ni matrix were studied and estimated by using an energy-dispersive spectroscopic (EDS) analysis, while x-ray diffractometry (XRD) was used to investigate the effect of heat treatment temperature on phase structure. The results showed agglomeration of TiO2 nanoparticles on the surface of the coating. The high hardness and wear resistance recorded for the as-deposited coating was attributed to the uniform distribution of TiO2 nanoparticle clusters throughout the cross section of the coating. Heat treatment of the Ni/TiO2 coatings to temperatures above 200 °C led to significant grain growth that changed the surface morphology of the coating and reduced the strengthening effects of the nanoparticles, thus causing a reduction in the hardness and wear resistance of the coatings.

Mesoporous semiconductors such as TiO2 nanoparticles, as well as transparent conducting oxides (TCOs) such as indium tin oxide films are typically employed for setting up the photo-electrode module in variety of photoelectrochemical cells including Dye-Sensitized Solar Cells (DSSCs). In order to exhibit a high performance efficiency, the photo-electrodes in such applications are required to be able to harvest the light and transport the generated electrons effectively. Accordingly mesoporous layers with high values of surface area and well-established pore structure along with highly transparent and conductive TCOs are deposited on suitable substrates through the physical or chemical vapor deposition methods. The processing facilities and materials required to fabricate such high-quality devices with high values of efficiency are complicated and expensive, whereas devices of lower quality do not fulfill the demands. This issue is of particular importance regarding the energy production and developing the solar cell technologies, as it is considered by the concept of “cost per watt”. Thus, a great deal of effort is being carried out globally to enhance the efficiency of affordably-produced solar cells such as low-cost DSSCs. Utilizing the wet chemical techniques such as sol-gel method which provide a considerably more affordable route to synthesize nanoparticles and deposit thin films without the need of applying high temperature or vacuum condition is a widely-used approach to decrease the processing expenses. However, to achieve an acceptable cost-per-watt ratio requires enhancing the obtained efficiency value as well, and therefore, modifying the processing procedures to improve the required features of the products are highly encouraged. This thesis focuses on two individual activities: synthesis of TiO2 nanoparticles, and also thin film deposition of a promising TCO called aluminum-doped zinc oxide (AZO); both obtained through the sol-gel route that is modified to contribute to nanostructures with suitable features for application in photoelectrochemical devices such as DSSC. In the first part, mesoporous anatase nanoparticles were synthesized through the surfactant-mediated sol–gel route. Through changing the refluxing time and water-to-surfactant molar ratio, as-prepared nanocrystals of high density and large and narrowly-distributed pore sizes were obtained, displaying surface area values up to 240 m2·g-1, much higher than the reported values for commercial TiO2-based catalysts. In the second part, sol–gel dip–coating of ZnO thin films doped with 2 at.% of aluminium ions was carried out. By altering the hydrolysis reaction and changing the thermal treatment procedure, thin films of highly c-axis preferred orientation were obtained with optical transmittance of around 80% and resistivity values down to 6 – 15 mΩ·cm, corresponding to sheet resistance of around Rsh ~ 500 Ω/sq. The obtained conductivity values, even though one order magnitude lower than those reported for the AZO thin film prepared via expensive techniques, are in the suitable range to improve the cost per watt ratio in applications such as inkjet printing of low-cost printed electronics and more affordable DSSC devices.

Στην παρούσα διπλωματική εργασία γίνεται χρήση λεπτών υμενίων TiO2 ως στερεό υπόστρωμα για την ακινητοποίηση πρωτεϊνών με απώτερο σκοπό την ανάπτυξη ενός αμπερομετρικού βιοαισθητήρα με ευαισθησία στο υπεροξείδιο του υδρογόνου (H2O2). Αρχικά περιγράφεται η λειτουργία των βιοαισθητήρων καθώς και οι σημαντικότεροι τύποι βιοαισθητήρων που έχουν κατασκευαστεί μέχρι σήμερα. Σημαντικό ρόλο στην επιτυχή κατασκευή ενός βιοαισθητήρα παίζει η επιλογή του υλικού που θα χρησιμοποιηθεί ως υπόστρωμα / ηλεκτρόδιο (υμένια TiO2) καθώς και ο τρόπος που ακινητοποιείται το βιομόριο πάνω σε αυτό, γι’ αυτό και έχει δοθεί έμφαση στην ανάλυση των παραπάνω πληροφοριών. Επίσης περιγράφεται η δομή και η φυσική λειτουργία της πρωτεΐνης, (κυτόχρωμα c), που χρησιμοποιήθηκε ως το βιομόριο επιλογής για την ανάπτυξη του βιοαισθητήρα. Αναλύθηκαν επίσης οι κρυσταλλικές δομές του διοξειδίου του τιτανίου, οι βασικές φυσικοχημικές τους ιδιότητες και οι λόγοι που επιλέξαμε την ανατάση για τη συγκεκριμένη εργασία. Περιγράφεται η πειραματική διαδικασία εναπόθεσης των υμενίων του TiO2 σε υποστρώματα αγώγιμου υάλου. Στη συνέχεια περιγράφονται οι πειραματικές διατάξεις που χρησιμοποιήθηκαν τόσο για τον χαρακτηρισμό των υμενίων διοξειδίου του τιτανίου (TiO2) όσο και για την αναλυτική μελέτη της ακινητοποίησης του κυτοχρώματος c πάνω σε αυτά. Τέλος περιγράφεται η ηλεκτροχημική κυψελίδα 3 ηλεκτροδίων και η τεχνική της κυκλικής βολταμετρίας που επιλέχθηκαν τόσο για τη μελέτη των ηλεκτροχημικών ιδιοτήτων των υμενίων TiO2 με ή χωρίς ακινητοποιημένη πρωτεΐνη όσο και για την ανάπτυξη ενός αμπερομετρικού βιοαισθητήρα με ευαισθησία στο H2O2. / In the present study, the use of thin nanocrystalline TiO2 films as solid substrates for protein immobilization and for the development of an electrochemical biosensor for hydrogen peroxide (H2O2) are investigated. First of all, a general description of biosensors and their most important types that have been developed to date is given. For the successful development of a biosensor, the choice of material/substrate used as the surface/electrode (thin film of TiO2) for the attachment of the bio-molecule of interest, as well as the manner in which the bio-molecule is immobilized upon it are critical and therefore emphasis is given for the analysis of this information. Furthermore, a description of the structure and basic functions of the bio-molecules (cytochrome c and hemoglobin), used for the immobilization studies and for the development of the biosensor is presented. Additionally, the crystalline structures of titanium dioxide have been analyzed, along with its basic physicochemical properties and the reasons for choosing its anatase structure for the specific project. In the experimental part, the deposition of the colloidal TiO2 paste on conducting glass for the preparation of the thin mesoporous TiO2 films is described in detail. Also described are the experimental techniques used for the characterization of these films as well as a thorough analysis of the binding of cytochrome c upon them and the parameters that influence its adsorption. Finally, description of the 3-elecrode electrochemical cell used in this study of perform of cyclic voltammetry experiments in order to investigate the electrochemical properties of the TiO2 thin films with or without immobilized protein is given. The same setup is also used for the development of an electrochemical biosensor for H2O2.

En raison de leur petite taille, les nanoparticules (NP) (< 100 nm) peuvent coaguler très rapidement ce qui favorise leur pénétration dans l’organisme sous forme d’agglomérats. L’objectif de cette recherche est d’étudier l’influence de l’état d’agglomération de NP de dioxyde de titane (TiO2) de trois tailles de départ différentes, 5, 10-30 ou 50 nm sur la toxicité pulmonaire chez le rat mâle (F344) exposé à des aérosols de 2, 7 ou 20 mg/m3 pendant 6 heures. Dans une chambre d’inhalation, six groupes de rats (n = 6 par groupe) ont été exposés par inhalation aiguë nez-seulement à des aérosols ayant une taille primaire de 5 nm, mais produits sous forme faiblement (< 100 nm) ou fortement (> 100 nm) agglomérée à 2, 7 et 20 mg/m3. De façon similaire, quatre autres groupes de rats ont été exposés à 20 mg/m3 à des aérosols ayant une taille primaire de 10-30 et 50 nm. Les différents aérosols ont été générés par nébulisation à partir de suspensions ou par dispersion à sec. Pour chaque concentration massique, un groupe de rats témoins (n = 6 par groupe) a été exposé à de l’air comprimé dans les mêmes conditions. Les animaux ont été sacrifiés 16 heures après la fin de l’exposition et les lavages broncho-alvéolaires ont permis de doser des marqueurs d’effets inflammatoires, cytotoxiques et de stress oxydant. Des coupes histologiques de poumons ont également été analysées. L’influence de l’état d’agglomération des NP de TiO2 n’a pu être discriminée à 2 mg/m3. Aux concentrations massiques de 7 et 20 mg/m3, nos résultats montrent qu’une réponse inflammatoire aiguë est induite suite à l'exposition aux aérosols fortement agglomérés. En plus de cette réponse, l’exposition aux aérosols faiblement agglomérés à 20 mg/m3 s’est traduite par une augmentation significative de la 8-isoprostane et de la lactate déshydrogénase. À 20 mg/m3, les effets cytotoxiques étaient plus importants suite à l’exposition aux NP de 5 nm faiblement agglomérées. Ces travaux ont montré dans l'ensemble que différents mécanismes de toxicité pulmonaire peuvent être empruntés par les NP de TiO2 en fonction de la taille de départ et de l’état d’agglomération. / Given their small size, nanoparticles (NP) (< 100 nm) can coagulate quickly, which promotes their entry into the body in the form of agglomerates. The objective of this study is to evaluate the influence of the agglomeration state of three different primary particle sizes (5, 10-30 and 50 nm) of titanium dioxide (TiO2) NP on the pulmonary toxicity of male rats (F344) exposed to aerosols at 2, 7 or 20 mg/m3 for 6 hours. In an inhalation chamber, six groups of rats (n = 6 per group) were acutely exposed by nose-only inhalation to aerosols with a 5-nm primary particle size, produced in the form of small agglomerates (< 100 nm) (SA) or large agglomerates (> 100 nm) (LA) at 2, 7 and 20 mg/m3. Similarly, four other groups of rats were exposed to aerosols at 20 mg/m3 with a primary particle size of 10-30 and 50 nm. The different aerosols were generated by nebulization of suspensions or by dry dispersion. For each mass concentration, one group of control rats (n = 6 per group) was exposed to compressed air under the same conditions. The animals were sacrificed 16 hours after the end of exposure, and analysis of the bronchoalveolar lavage fluids was used to measure markers of inflammatory, cytotoxicity and oxidative stress effects. Lung sections were also analyzed for histopathology. The influence of the agglomeration state of TiO2 NP (5 nm) could not be determined at 2 mg/m3. For mass concentrations of 7 and 20 mg/m3, our results showed that an acute inflammatory response was induced following exposure to LA aerosols. In addition to this response, exposure to SA aerosols resulted in a significant increase in 8-isoprostane and lactate dehydrogenase. At 20 mg/m3, the cytotoxic effects were greater after exposure to the 5-nm NP in the SA aerosol. This study showed that TiO2 NP use different mechanisms to induce their pulmonary toxicity as a function of their primary particle size and their agglomeration state.

Ces derniers temps, des procédés commerciaux basés sur la technologie photocatalytique, sont arrivés sur le marché, afin de satisfaire la demande croissante du traitement de l’air intérieur. L’objectif de ce présent travail est de développer une nouvelle méthodologie pour évaluer l’efficacité de ce nouveau procédé. Pour l’étude de l’application de la photocatalyse au traitement de l’air intérieur, un dispositif expérimental a été mis au point et deux méthodes analytiques ont été développées (ATD-GCMS et GC-PDHID). La performance de la dégradation photocatalytique du 2-propanol et du toluène à faibles concentrations (ppbv) a été étudiée. L’influence des différents paramètres (humidité relative, débit, concentration initiale, etc.) et leurs interactions sur la conversion, la formation des intermédiaires et la minéralisation au CO2 a été établie / Many commercial systems based in the photocatalytic technology have reached the market recently in order to address the growing demand for improve poor indoor air qualities. The present work deals with the development of a new methodology in order to evaluate the efficiency of this process. For the study of photocatalytic oxidation for indoor air applications, an experimental set-up was designed and two analytical tools (ATD-GC-MS and GC-PDHID) were developed. The performance of the photocatalytic treatment of 2-propanol and toluene at indoor air concentrations levels (ppbv) were realised. The influence of several parameters and their interactions effects on the conversion, by-product formation and mineralization to CO2 were established