No description available.

Philosophiae Doctor - PhD / Titanium oxynitride has attracted research interest for the fact that it is a bioactive non-toxic material. It is suitable for surface coating of biomaterials and in other applications such as anti-reflective coatings, while oxygen-rich titanium oxynitride has been applied in thin film resistors and photocatalysis. Two common types of titanium oxynitrides are TiOₓNᵧ. and TiO₂-ₓNᵧ. In this work, titanium mixed metals oxynitrides (Ti-TiO₂, Mg-TiO₂ and Mg-Sn-TiO₂) were synthesized for the first time using ball milling (BM) and annealing processes. Their structural, morphological, surface, optical, and gas sensing properties were studied in detail. Structural analyses showed that upon milling a pure TiO₂ phase, tetragonal to orthorhombic phase transformation occurred. However, when milling TiO₂ mixed with Mg, Sn and Ti no evidence of the transformation was observed. Furthermore, scanning electron microscopy, transmission electron microscopy and atomic force microscopy showed that the milling process promotes particle refinement. The gas sensing analyses also demonstrated that the sensing response of the TiO₂, Mg-TiO₂ and Mg-Sn-TiO₂ materials improved upon milling. Moreover, the Mg-TiO₂ showed improved sensing compared to pure TiO₂ due to incorporation of Mg, which might have resulted in a decrease of charge carrier concentration. The Mg-TiO₂ sensing materials showed fast response-recovery time of ~32 s and ~48 s, respectively, as well as high selectivity to NH₃ gas compared to other gases (H₂, and CH₄). In addition, the improved response observed for the milled samples is due to increased surface area and pore diameter, providing more active sites for the target gas and allowing more gas adsorption with an increase in point defects related to oxygen vacancies (Vo), which are the most favorable adsorption sites for oxygen species and thus can enhance the possibility of interaction with gas molecules. A combination of photoluminescence, x-ray photoelectron spectroscopy, vibrating sample magnetometer and sensing analyses demonstrated that a direct relation exists between the magnetization, sensing and the relative occupancy of the Vo present on the surface of TiO₂ nanoparticles. Therefore, based on these finding we conclude that the milling process promotes particle refinement, resulting in an increased BET surface and partial breaking of Ti–O bonds on the TiO₂ surface layer, which results in the formation of oxygen vacancies in the TiO₂ lattice, therefore anticipating improved sensing response. / National Research Foundation

Made available in DSpace on 2014-12-17T14:06:56Z (GMT). No. of bitstreams: 1 DaniloCB_DISSERT.pdf: 3100682 bytes, checksum: ca6553081fbf48a3fd486b3f20d01cc2 (MD5) Previous issue date: 2011-06-09 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Discs were grade II cp Ti oxynitride by plasma of Ar - N2 - O2 using different proportions of individual gases. These ratios were established from analysis of optical emission spectroscopy (OES) of plasma species. The proportions that resulted in species whose spectra showed an abrupt change of light intensity were chosen for this study. Nanohardness tests revealed that there was a correlation between the intensity of N2 + species with the hardness, because the treatments where they had a higher intensity, obtained a higher value nanohardness, although the crystalline phases have remained unchanged. With respect to topography, it was observed that in general, the surface roughness is related to the intensities of plasma species, because they may have different values depending on the behavior of the species. Images obtained by optical microscopy revealed a surface with grains of different colors to optical reflectance showed a peak of reflection in the red area. Measures the contact angle and surface tension showed hydrophilic properties and hydrophilic with little variation of polar and dispersive components of surface tension / Discos de tit?nio cp grau II foram oxinitretados por plasma de Ar - N2 - O2 usando diferentes propor??es de gases individuais. Essas propor??es foram estabelecidas a partir de an?lises de espectroscopia de emiss?o ?ptica (OES) das esp?cies do plasma. As propor??es que resultaram em espectros cujas esp?cies apresentaram varia??o abrupta de intensidade luminosa foram escolhidas para o presente trabalho. Os ensaios de nanodureza revelaram que houve uma rela??o entre a intensidade da esp?cie N2 + com a dureza, pois para os tratamentos onde estas apresentaram maior intensidade, obteve-se maior valor de nanodureza, embora as fases cristalinas tenham se mantido inalteradas. Com rela??o ?s topografias, observou-se que de um modo geral, a rugosidade superficial est? relacionada com as intensidades das esp?cies do plasma, pois estas podem apresentar valores diferentes dependendo do comportamento das esp?cies. Imagens obtidas por microscopia ?ptica revelaram uma superf?cie com gr?os de diferentes cores e a reflet?ncia ?ptica mostrou um pico m?ximo de reflex?o na regi?o do vermelho. As medidas de ?ngulo de contato e tens?o mostraram superf?cies com propriedades hidrof?licas e pouco hidrof?licas com varia??o das componentes polar e dispersiva da tens?o superficial

Coronary artery disease (CAD) affects every fifth person in the world. The gold-standard treatment for CAD is stent implantation, however, the existing therapy is not sufficient due to many reasons. For instance, in-stent restenosis, biocompatibility, controlled degradation rate, protein adsorption, and adequate endothelialization are still the main concerns. In the last two decades, the field of stent technology has been grown rapidly and many new stent types and in vitro testing methods for stent characterization have been developed to minimize the aforementioned issues. In this vicinity, there are still many unaddressed issues: i) the quantitative analysis of corrosion is conducted with simpler samples made of stent material instead of stents, in most cases due to the absence of a mathematical model to calculate the entire stent surface area (ESSA); ii) in vitro stent testing in environments that are very far from actual physiological environments; iii) Evaluation of the influence of in-vitro test conditions on coated metallic stents; iv) absence of flow-induced shear stress (FISS) corrosion model, to mention a few. This thesis presents the novel ESSA model, the fluid dynamic experimental setup with the integration of various sensors and pH control, the influence of in vitro degradation behavior of the titanium oxynitride (TiOxNy) coated stainless steel stents and anodized AZ31 samples, and the FISS corrosion model. The results show some important contributions in this field, however, there is still a huge potential for the development of promising stent characterization solutions. / Die koronare Herzkrankheit (KHK) betrifft jeden fünften Menschen auf der Welt. Der Goldstandard bei der Behandlung von KHK ist die Stent-Implantation, doch die bestehende Therapie ist aus vielen Gründen nicht ausreichend. So sind beispielsweise die Restenose im Stent, die Biokompatibilität, die kontrollierte Abbaugeschwindigkeit, die Proteinadsorption und die angemessene Endothelialisierung nach wie vor die Hauptprobleme. In den letzten zwei Jahrzehnten hat sich die Stenttechnologie rasant weiterentwickelt, und es wurden viele neue Stenttypen und In-vitro-Testmethoden zur Stentcharakterisierung entwickelt, um die oben genannten Probleme zu minimieren. In dieser Umgebung gibt es noch viele ungelöste Probleme: i) die quantitative Analyse der Korrosion wird mit einfacheren Proben aus Stentmaterial anstelle von Stents durchgeführt, in den meisten Fällen aufgrund des Fehlens eines mathematischen Modells zur Berechnung der gesamten Stentoberfläche (ESSA); ii) In-vitro-Stent-Tests in Umgebungen, die sehr weit von der tatsächlichen physiologischen Umgebung entfernt sind; iii) Bewertung des Einflusses von In-vitro-Testbedingungen auf beschichtete metallische Stents; iv) Fehlen eines FISS-Korrosionsmodells (flow-induced shear stress), um nur einige zu nennen. In dieser Arbeit werden das neuartige ESSA-Modell, der strömungsdynamische Versuchsaufbau mit der Integration verschiedener Sensoren und pH-Kontrolle, der Einfluss des In-vitro-Degradationsverhaltens der mit Titanoxynitrid (TiOxNy) beschichteten Edelstahlstents und anodisierten AZ31-Proben sowie das FISS-Korrosionsmodell vorgestellt. Die Ergebnisse zeigen einige wichtige Beiträge in diesem Bereich, jedoch gibt es noch ein großes Potenzial für die Entwicklung von vielversprechenden Lösungen zur Charakterisierung von Stents.