El presente trabajo de Tesis Doctoral se centró en la preparación y en el estudio de las propiedades fotoelectroquímicas de electrodos nanoestructurados de dióxido de titanio compuestos por partículas de diferente morfología: nanopartículas, nanohilos, nanotubos, nanocolumnas y nanofibras. Por un lado se estudió la influencia de la fase cristalina (anatasa y rutilo) y por otro, la influencia del tamaño de las partículas y su morfología sobre las propiedades fotoelectroquímicas de electrodos nanoestructurados de dióxido de titanio. Para estudiar la influencia de la fase cristalina se prepararon electrodos de anatasa y rutilo con la misma morfología (nanohilos) y tamaño de partícula (~ 2nm). Estos electrodos se emplearon para estudiar la estructura electrónica de ambas fases cristalinas. También se realizó un estudio de la distribución de los estados electrónicos empleando electrodos con diferente morfología de nanopartículas (nanotubos, nanocolumnas, nanopartículas). Los estudios se llevaron a cabo empleando voltametría cíclica, cronoamperometría, cronopotenciometría y métodos espectroscópicos (espectroscopía ultravioleta-visible, espectroscopía de voltaje superficial y espectroscopía de resonancia paramagnética electrónica). Las propiedades fotoelectroquímicas para las diferentes nanoestructuras se estudiaron tanto en medio ácido como en medio alcalino empleando diferentes compuestos orgánicos modelo (ácido fórmico, metanol e hidracina). Se estudió la influencia del tratamiento térmico de los nanohilos sobre su cristalinidad y sus propiedades fotoelectoquímicas. También se prepararon estructuras organizadas jerárquicamente basadas en nanotubos de anatasa decorados con nanohilos tanto de anatasa como de rutilo. El efecto del sustrato se estudió comparando electrodos de nanotubos de dióxido de titanio preparados sobre titanio y sobre vidrio conductor. En el presente trabajo también se estudió la actividad de dióxido de titanio modificado con nanopartículas de oro en el rango visible del espectro empleando métodos espectroscópicos.

The medical field has been a part of the smart textile area for quite some time. With time come technological advancement and the two fields converge on more and more areas. One such area is that of using textile electrodes, textrodes, for measuring bioelectrical activity, such as heart rate for ECG analysis. There are many components that make for a successful textile electrode and though many studies have been made in the subject there are several aspects that still are difficult. By using textile electrodes the problem with skin irritation from electrolyte gels, commonly used for conventional electrodes, is avoided, however dry textrodes create disturbances in the output signal (heart rate) while subjected to movement and internal dimensional changes. The addition of moisture to a textrode has shown to decrease these intermittent disturbances but the knowledge about fundamental textile structural influence in the matter has not been fully investigated. This study investigates a flat, a 2-thread fleece and an open structure, and their relation to moisture both as textile structures and as textrodes. This way the possibilities of utilising moisture to increase performance in a textrode purpose can be examined and to what extent the textile structure plays a part in that exploitation. The material composition of textile structures also affects their properties The introduction of assistive materials, polyester and viscose, into the Shieldex (conductive yarn) structures is done to test core moisture management properties such as surface tension, absorption and moisture content, and correlate them to electrical properties necessary for textrode function. In the end the gap between textile structure and end product in form of a textrode is closed as the impedance and microclimate of the textrodes are studied. This is mainly to tie together the fundamental textile structures with a complex textile construction. In conclusion the complexity is also confirmed as structural, materialistic and external influences has an impact on the results. The influence of moisture on lowered resistance and impedance in the structures is confirmed but the impact of textile structure can also be seen. The 2-thread fleece and open structures often has a more positive impact on results and therefore has the possibility of enhancing performance of a textrode for bioelectrical signal monitoring. With these results a more effective way of producing long-lasting, patient-friendly, textrodes can be derived and in the future lead to better care in the medical areas.

Ce travail de thèse explore l’excitation électrique de micro-OLEDs en régime d’impulsion afin d’évaluer la possibilité d’atteindre le seuil laser dans les diodes laser organiques qui restent encore à démontrer. Ils’agit d’identifier des solutions scientifiques et techniques ouvrant la voie vers des densités d’excitations électriques équivalentes aux seuils laser observés en pompage optique. Dans la littérature, les seuils les plus bas sont équivalents à des densités de courant entre 0.72 et 4kA/cm² si on suppose une efficacité quantique externe de 1%. De telles densités de courant imposent un régime d’excitation électrique impulsionnel pour s’affranchir des risques de destructions par effet thermique et des pertes par annihilation singulet-triplet dès lors que l’on travaille avec des durées d’impulsion de l’ordre de la nanoseconde. Et pour espérer des réponses électriques et optiques efficaces à de telles durées d’impulsions, il est proposé ici de combiner l’électronique hyperfréquence et l’optoélectronique organique. A cet effet, un modèle électrique équivalent de l’OLED permettant d’accéder à son temps de réponse en mode tout-ou-rien est développé. De plus, des électrodes spécifiques sont dimensionnées et structurées sous forme de lignes coplanaires d’impédance caractéristique 50Ω afin de maîtriser l’impédance du circuit d’excitation et d’assurer le transfert du maximum d’énergie de l’impulsion d’excitation vers celui-ci. Après dépôts de l’hétéro-structure organique basée sur le système hôte-dopant Alq3:DCM, les composants ainsi réalisés sont caractérisés électriquement et optiquement avec différentes techniques par analyse vectorielle, en régime continu et en régime d’impulsion. En régime d’impulsion de très courtes durées (2.5~20ns) et à faible taux de répétition (100Hz), des temps de réponse de 330ps etdes densités de courant maximales entre 4 et 6kA/cm² ont été mesurés alors que le maximum de luminance culmine à 4.11x10⁶ cd/m². / This thesis explores the pulsed electrical excitation of micro-OLEDs in order to evaluate the possibility of reaching the laser threshold in organic laser diodes that have not yet be demonstrated. The main goal is the identification of the scientific and technical solutions towards high electrical excitation current densities equivalent to the laser thresholds observed under optical pumping. In the literature, the lowest reported thresholds are equivalent to current densities between 0.72 and 4kA/cm², assuming an external quantum efficiency of 1%. Such current densities imply a pulsed electrical excitation regime to prevent the risks of device breakdown by Joule heating effects and to avoid losses by excitons annihilation processes, as long as the pulses duration are in nanosecond range. To expect efficient electrical and optical responses to such pulse durations, it is suggested to combine microwave electronics and organic optoelectronics. For this purpose, an equivalent electrical model of the organic light emitting device, allowing access to its on-off mode time response, is developed. Additionally, specific electrodes are designed and patterned in the coplanar waveguide configuration with characteristic impedance of 50Ω, inorder to control the impedance of the excitation circuit and to ensure the maximum energy transfer of the excitation pulse to the device. After deposition of organic hetero-structure based on the Alq3:DCM host-guest system, the device is characterized electrically and optically with different techniques by vector network analysis, in continuous mode and in pulse mode. In pulse excitation regime with very short pulses durations (2.5~20ns) and low repetition rate (100Hz), time response of 330ps and maximum current densities between 4 and 6kA/cm² are recorded while the maximum of luminance peaks at 4.11x10⁶ cd/m².

Abstract not available

In this work, a series of simple, rapid and effective photoelectrochemical methodologies have been developed and successfully applied to the study of kinetic and thermodynamic characteristics of photocatalytic oxidation processes at TiO2 nanoparticulate films. As an application of the systematic studies of photocatalytic processes by photoelectrochemical techniques, a rapid, direct, absolute, environmental-friendly and accurate COD analysis method was successfully developed. In this work, the TiO2 nanoparticles colloid was prepared by the sol-gel method. The TiO2 nanoparticles were immobilized onto ITO conducting glass slides by dip-coating method. Thermal treatment was carried out to obtain nanoporous TiO2 films of different structures. At low calcination temperature (below 600°C), nanoporous TiO2 films of pure anatase phase were prepared. At high calcination temperature (above 600°C), nanoporous TiO2 films of mixed anatase and rutile phases were obtained. At these film electrodes, the work was carried out. By employing steady state photocurrent method and choosing phthalic acid as the model compound, the photocatalytic activity of the TiO2 nanoporous films calcined at various temperatures and for different lengths of time was evaluated. It was found that the films with mixed anatase and rutile phases calcined at high temperature exhibited high photocatalytic activity. Based on semiconductor band theory, a model was proposed, which explained well this finding. By employing linear sweep voltammetry (under illumination) and choosing glucose (an effective photohole scavenger) as a model compound, the characteristics of the photocatalytic processes at nanoparticulate semiconductor electrodes were investigated. Characteristics of the nanoporous semiconductor electrodes markedly different from bulk semiconductor electrodes were observed. That is, within a large range of electrode potentials above the flat band potential the electrodes behaved as a pure resistance instead of exhibiting variable resistance expected for bulk semiconductor electrodes. The magnitude of the resistance was dependent on the properties of the electrodes and the maximum photocatalytic oxidation rate at TiO2 surface determined by the light intensity and substrate concentration. A model was proposed, which explained well the special characteristics of particulate semiconductor electrodes (nanoporous semiconductor electrodes). This is the first clear description of the overall photocatalytic process at nanoparticulate semiconductor electrodes. The investigation set a theoretical foundation for employing photoelectrochemical techniques to study photocatalytic processes. By using the transient technique (illumination step method analogous to potential step method in conventional electrochemistry), the adsorption of a number of strong adsorbates on both low temperature and high temperature calcined TiO2 nanoporous films was investigated. Similar adsorption characteristics for different adsorbates on different films were observed. In all the cases, three different surface bound complexes were identified, which was attributed to the heterogeneity of TiO2 surface. The photocatalytic degradation kinetics of the pre-adsorbed organic compounds of different chemical nature was also studied by processing the photocurrent-time profiles. Two different photocatalytic processes, exhibiting different rate characteristics, were observed. This was, again, attributed to the heterogeneity of the TiO2 surface corresponding to heterogeneous adsorption characteristics. The catalytic first order rate constants of both fast and slow processes were obtained for different organic compounds. It was found that for different adsorbates of different chemical nature the magnitudes of rate constant for the slow kinetic process were very similar, while the magnitudes of rate constant for the fast process were significantly affected by the photohole demand characteristics of different adsorbates. Photohole demand distribution that depends on the size and structure of the adsorbed molecules was believed to be responsible for the difference. By employing steady state photocurrent method, the photocatalytic degradation kinetic characteristics of both strong adsorbates and weak adsorbates of different chemical structures were compared at pure anatase TiO2 nanoporous TiO2 films as well as at anatase/rutile mixed phase TiO2 nanoporous film electrodes. At the former electrodes for all the different organic compounds studied, the photocatalytic reaction rate increased linearly with concentration at low concentrations. Under such conditions, it was demonstrated that the overall photocatalytic process was controlled by diffusion and was independent of the chemical nature of organic compounds. However, the linear concentration range and the maximum photocatalytic reaction rate at high concentrations were significantly dependent on the chemical nature of the substrates. This was explained by the difference in the interaction of different organic compounds with TiO2 surface, the difference in their photohole demand distributions at the TiO2 surface and the difference in their nature of intermediates formed during their photocatalytic mineralization. In contrast, at the latter electrodes for the photocatalytic oxidation of different organic compounds the linear ranges (diffusion control concentration range) and the maximum reaction rates at high concentration were much larger than at the former electrodes and much less dependent on the chemical nature of the organic compounds. The spatial separation of photoelectrons and photoholes (due to the coexistence of rutile phase and anatase phase) and the increase in the lifetime of photoelectrons and photoholes are responsible for the excellent photocatalytic activity of the electrodes. By employing the thin-layer photoelectrochemical technique (analogous to the thin-layer exhaustive electrolytic technique), the photocatalytic oxidation of different organic compounds at the mixed phase TiO2 nanoporous electrodes were investigated in a thin layer photoelectrochemical cell. It was found that the charge derived from exhaustive oxidation agreed well with theoretical charge expected for the mineralisation of a specific organic compound. This finding was true for all the compounds investigated and was also true for mixtures of different organic compounds. The photocatalytic degradation kinetics of different organic compounds of different chemical identities in the thin layer cell was also investigated by the photoelectrochemical method. Two kinetic processes of different decay time constants were identified, which were attributed to the degradation of preadsorbed compounds and the degradation of compounds in solution. For the degradation of compounds in solution, a change in the overall control step from substrate diffusion to heterogeneous surface reaction was observed. For different organic compounds, the variation of the rate constant was determined by the photohole demand rather than by the chemical identities of substrates. The kinetics of the fast kinetic process, on the other hand, was greatly affected by the adsorption properties of the substrates. For the strong adsorbates, the rate was much larger than for weak adsorbates. However, the rate constant of the process was independent of the chemical identities of the substrates and the variation of the constant was also determined by the photohole demand. Based on the principles of exhaustive photoelectrocatalytic degradation of organic matter in a thin layer cell, a novel, rapid, direct, environmental-friendly and absolute COD analysis method was developed. The method was tested on synthetic samples as well as real wastewater samples from a variety of industries. For synthetic samples with given compositions the COD values measured by my method agree very well with theoretical COD value. For real samples and synthetic samples the COD values measured by my method correlated very well with those measured by standard dichromate COD analysis method.

<p>Denna rapport avhandlar en tio veckors period på Otto Bock Scandinavia AB i Norrköping. Där analyserades en manuell testutrusning för funktionstest av myoelektroder, för att mäta muskelspänningar. Myoelektroderna används till att styra gripfunktionen hos handproteser, för patienter som förlorat en del av sin arm. Analysen ska resultera i att ge ett förslag på en automatiserad test av elektroderna. En stor del av rapporten består av studier kring hur testmetoderna fungerar och elektrodernas användning och funktion. Slutligen behandlas även ett förslag på en automatiserad test för elektroderna. </p> / <p>The present report concerns a ten weeks period at Otto Bock Scandinavia AB in Norrköping. An analyse of a manual test equipment for testing myoelectrodes, who is used to measure muscle potential in the arm. The myoelectrodes are used to control a grip function on hand prostheses, which is used by persons who has lost their lower arm. The analyse should result in a proposal of an automation of the manual test equipment for the electrodes. </p><p>A significant part of the report discusses the function of test methods and who the electrodes are used for and their function. Finally, discusses a proposal on an automated test for the electrodes.</p>

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 204-217).

Thesis (Ph. D.)--University of Texas at Austin, 2006. / Vita. Includes bibliographical references.

No description available.

No description available.