Made available in DSpace on 2014-12-17T15:42:00Z (GMT). No. of bitstreams: 1 GustavoRO_DISSERT.pdf: 3063056 bytes, checksum: e0fe7867cfaf62acb3ba439a1526cef3 (MD5) Previous issue date: 2012-07-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Many pollutants dumped in waterways, such as dyes and pesticides, have become so ubiquitous that they represent a serious threat to human health. The electrochemical oxidation is presented as an alternative clean, efficient and economic degradation of wastewater containing organic compounds and a number of advantages of this technique is to just not make use of chemical reagents, since only electrical energy is consumed during the removal of pollutants organic. However, despite being a promising alternative, still needs some tweaking in order to obtain better efficiency in the elimination of persistent pollutants. Thus, this study sought a relationship between a recently discovered phenomenon that reflects the participation of dissolved oxygen in solution in the electrochemical oxidation process, as an anomaly, present a kinetic model that shows instantaneous current efficiency (ICE) above 100% limited by theory, manifested for some experiments with phenolic compounds with H2SO4 or HClO4 as supporting electrolyte with electrodes under anodic oxidation on boron doped diamond (BDD). Therefore it was necessary to reproduce the data ICE exposes the fault model, and thus the 2-naphthol was used as phenolic compound to be oxidised at concentrations of 9, 12 and 15 mmol L-1, and H2SO4 and HClO4 to 1 mol L-1 as a supporting electrolyte under a current density of 30 mA cm-2 in an electrochemical reactor for continuous flow disk configuration, and equipped with anodes DDB at room temperature (25 oC). Experiments were performed using N2 like as purge gas for eliminate oxygen dissolved in solution so that its influence in the system was studied. After exposure of the anomaly of the ICE model and investigation of its relationship with dissolved O2, the data could be treated, making it possible for confirmation. But not only that, the data obtained from eletran?lise and spectroscopic analysis suggest the involvement of other strongly oxidizing species (O3 (ozone) and O radicals and O2 -), since the dissolved O2 can be consumed during the formation of new strong oxidizing species, not considered until now, something that needs to be investigated by more accurate methods that we may know a little more of this system. Currently the performance of the electrocatalytic process is established by a complex interaction between different parameters that can be optimized, so it is necessary to the implementation of theoretical models, which are the conceptual lens with which researchers see / Muitos poluentes jogados em cursos d'?gua, como corantes e pesticidas, tornaram-se t?o onipresentes que representam uma s?ria amea?a a sa?de humana. A oxida??o eletroqu?mica se apresenta como uma alternativa limpa, eficiente e econ?mica ? degrada??o de efluentes contendo compostos org?nicos e uma das v?rias vantagens desta t?cnica ? justamente n?o fazer uso de reagentes qu?micos, uma vez que apenas a energia el?trica ? consumida durante a elimina??o dos poluentes org?nicos. Por?m, apesar de ser uma alternativa promissora, ainda necessita de alguns ajustes a fim de se obter melhor efici?ncia na elimina??o de poluentes persistentes. Assim este trabalho procurou alguma rela??o entre um fen?meno descoberto recentemente que evidencia a participa??o do oxig?nio dissolvido em solu??o no processo de oxida??o eletroqu?mica, com uma anomalia, presente no modelo cin?tico que apresenta corrente efetiva instant?nea (CEI) acima dos 100% delimitados pela teoria, que se manifesta para alguns experimentos realizados com compostos fen?licos tendo H2SO4 ou HClO4 como eletr?lito suporte sob oxida??o an?dica com eletrodos de diamante dopado em boro (DDB). Para tanto foi preciso reproduzir os dados de CEI que exp?e a anomalia do modelo, sendo assim, o 2-naftol serviu como composto fen?lico modelo, a ser oxidado nas concentra??es de 9, 12 e 15 mmol L-1, tendo H2SO4 ou HClO4 ? 1 mol L-1 como eletr?lito de suporte, sob uma densidade de corrente de 30 mA cm-2 em um reator eletroqu?mico de fluxo cont?nuo em configura??o de disco e equipado com ?nodos de DDB, ? temperatura ambiente (25 oC). Experimentos semelhantes foram realizados utilizando N2 como g?s de purga para eliminar o oxig?nio dissolvido em solu??o para que sua influ?ncia no sistema fosse estudada. Ap?s a exposi??o da anomalia do modelo da CEI e da investiga??o de sua rela??o com O2 dissolvido, os dados puderam ser tratados, o que tornou poss?vel sua confirma??o. Mas n?o ? s? isso, os dados obtidos da eletroan?lise e de an?lises espectrofotom?tricas sugerem a participa??o de outras esp?cies fortemente oxidantes, (O3 (oz?nio) e radicais O e O2 -), uma vez que o O2 dissolvido pode ser consumido durante a forma??o das novas esp?cies fortemente oxidantes, n?o consideradas at? agora, algo que precisa ser investigado por m?todos mais precisos para que possamos conhecer um pouco mais deste sistema. Atualmente o desempenho do processo eletrocatal?tico ? estabelecido por uma intera??o complexa entre diferentes par?metros que podem ser otimizados, por isso faz-se necess?rio a implementa??o de modelos te?ricos, que s?o as lentes conceituais com que os pesquisadores enxergam

La thèse a porté principalement sur la mise en œuvre de procédés d'oxydation avancée permettant l'élimination de trois anti-inflammatoires non stéroïdiens, le kétoprofène, le naproxène et le piroxicam dans l'eau. Ces trois composés sont parmi les médicaments les plus utilisés, dont la présence dans les eaux naturelles présente potentiellement un risque toxicologique. En raison de la faible efficacité d'élimination des produits pharmaceutiques par les stations traditionnels de traitement des eaux usées, les scientifiques se sont mis à la recherche de technologies de traitements efficaces et respectueuses de l'environnement. Les procédés d'oxydation avancée, comme l'ozonation-biofiltration, l'électro-Fenton et l'oxydation anodique peuvent permettre d'atteindre la destruction presque complète des polluants étudiés et de ce fait ils ont suscité un intérêt grandissant au cours des deux dernières décennies. Tout d'abord, ce travail s'intéresse à l'élimination de certains produits pharmaceutiques dans des solutions synthétiques préparées dans l'eau de robinet à l'aide des procédés électro-Fenton et oxydation anodique dans une cellule électrochimique équipée d'une anode de platine ou de diamant dopé au bore et d'une cathode de feutre de carbone. Cette étude a été menée à l'échelle du laboratoire. Les vitesses d'élimination des molécules pharmaceutiques ainsi que le degré de minéralisation des solutions étudiées ont été déterminées sous différentes conditions opératoires. Pendant ce temps, les sous-produits de l'oxidation générés au cours de la minéralisation ont également été identifiés, ce qui nous a permis de proposer les voies d'oxydation possible pour chaque composé pharmaceutique en présence du radical hydroxyl •OH. Enfin, l'évolution de la toxicité au cours des traitements a été suivie en utilisant la méthode Microtox, basée sur l'inhibition de la fluorescence des bactéries Vibrio fischeri. Dans la deuxième partie de ce travail de thèse, les trois anti-inflammatoires non stéroïdiens ont été ajoutés dans une eau déminéralisée ou dans une eau de surface. Ces eaux ont été traitées à l'aide de différentes doses d'ozone; puis le traitement à l'ozone à été combiné à un traitement biologique par biofiltration. Un biofilm biologique déposé à la surface d'un filtre de charbon actif a été utilisé pour déterminer la biodégradabilité des sous-produits d'oxydation formés dans les eaux de surface ozonée. L'identification des intermédiaires formés lors des processus de traitement et des contrôles de toxicité bactérienne ont été menées pour évaluer la voie de dégradation des produits pharmaceutiques et des effets biologiques potentiels, respectivement / The thesis mainly focused on the implementation of advanced oxidation processes for the elimination of three non-steroidal anti-inflammatory drugs-ketoprofen, naproxen and piroxicam in waters. The three compounds are among the most used medicines, whose presence in waters poses a potential ecotoxicological risk. Due to the low pharmaceuticals removal efficiency of traditional wastwater treatement plants, worldwide concerns and calls are raised for efficient and eco-friendly technologies. Advanced oxidation processes, such as ozonation-biofiltration, electro-Fenton and anodic oxidation processes, which attracted a growing interest over the last two decades, could achieve almost complete destruction of the pollutants studied. Firstly, removal of selected pharmaceuticals from tap water was investigated by electrochemical advanced oxidation processes “electro-Fenton” and “anodic oxidation” with Pt or boron-doped diamond anode and carbon felt cathode at lab-scale. Removal rates and minieralization current efficencies under different operatioanl conditions were analysed. Meanwhile, intermediates produced during the mineralization were also identified, which helps to propose plausible oxidation pathway of each compound in presence of •OH. Finally, the evolution of the global toxicity of treated solutions was monitored using Microtox method, based on the fluorescence inhibition of Vibrio fischeri bacteria. In the second part, the three nonsteroidal anti-inflammatory molecules added in organics-free or surface water were treated under varying ozone treatment regimes with the quite well established technology ozone/biofiltration. A bench-scale biological film was employed to determine the biodegradability of chemical intermediates formed in ozonized surface water. Identification of intermediates formed during the processes and bacterial toxicity monitoring were conducted to assess the pharmaceuticals degradation pathway and potential biological effects, respectively

Biologically inspired design is used as an approach for sustainable engineering. Taking a biologically inspired approach, one abstracts ideas and principles from nature, an inherently sustainable system, and uses them in engineering applications with the goal of producing environmentally superior designs. One such biological idea with potential environmental benefits for engineering is microscale and nanoscale surface roughness found on the Lotus plant and many other surfaces in nature. These surfaces repel water and aid in contaminant removal; this self-cleaning phenomenon is called the "Lotus Effect," in honor of the plant first observed to exhibit it. The structures responsible for the Lotus Effect inspired research and development of many technologies capable of creating hydrophobic, self-cleaning surfaces, and many potential self-cleaning surface applications exist beyond nature's intended application of cleaning. While statements have been made about the environmental benefits of using a self-cleaning surface, only limited scientific data exist. Artificial self-cleaning surfaces are successfully cleaned using fog or mist. This shows that such surfaces can be cleaned with less energy and water intensive methods than the more conventional methods used to clean regular surfaces, such as spray or solvent cleaning. This research investigates the potential environmental burden reductions associated with using these surfaces on products. A life cycle assessment is performed to determine the environmental burdens associated with manufacturing a self-cleaning surface, for three production methods: a chemical coating, a laser ablated steel template, and an anodized aluminum template. The environmental benefits and burdens are quantified and compared to those of more conventional cleaning methods. The results indicate that self-cleaning surfaces are not necessarily the environmentally superior choice.

Orientadores: Gilberto Medeiros Ribeiro, Jose A. Brum / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-11T11:03:18Z (GMT). No. of bitstreams: 1 FernandezSiles_PabloRoberto_M.pdf: 9728988 bytes, checksum: 0fd358f0e4752f26b8ebfa6e4a5e3c5a (MD5) Previous issue date: 2006 / Resumo: A Oxidação anódica local em substratos tanto semicondutores quanto metálicos através do Microscópio de Força Atômica tem surgido ao longo dos últimos anos como uma das técnicas de litografia mais confiáveis e versáteis para a fabricação de dispositivos e estruturas em escala nanométrica. Embora aspectos fundamentais, como a dinâmica envolvida no processo de oxidação anódica em relação a diferentes parâmetros de controle, é ainda objeto de estudo. Pretende-se neste trabalho realizar uma caracterização de diferentes processos de litografia por AFM, com o objetivo de obter um melhor entendimento da cinética envolvida na oxidação assim como também determinar e quantificar a influência dos principais parâmetros de controle envolvidos no processo. Através de um processo de oxidação dinâmico, onde a ponta do microscópio encontra-se em movimento sobre a superfície da amostra durante o processo de oxidação, são determinadas as taxas de formação das estruturas de óxido em relação a parâmetros como a tensão aplicada na interface ponta-amostra, a umidade e a velocidade de varredura do microscópio. Finalmente, implementa-se a técnica para a fabricação de dispositivos em pequena escala. A construção de dispositivos passa por duas etapas de litografia, uma de ajuste grosso de padrões microscópicos, uma de ajuste fino onde linhas e demais geometrias são gravadas em uma escala de dezenas de nanômetros. O objetivo neste trabalho é de se fazer ambos os passos, sendo que a litografia fina será realizada por litografia por oxidação anódica local através do microscópio de força atômica. Para a definição das estruturas em escala nanométrica é proposta aqui, uma estrutura de duas camadas (PMMA-Ge), utilizada como resist. O sistema a ser estudado centra-se primeiramente nos pontos quânticos auto-formados (QDs). Pretende-se, em se integrando esta litografia e o crescimento de QDs, reunir o melhor de cada um destes processos, a precisão da litografia por oxidação anódica local e as propriedades eletrônicas limpas dos QDs, de maneira a estudar as propriedades eletrônicas de um pequeno número de QDs isolados / Abstract: Local Anodic Oxidation of conducting and non-conducting substrates by means of Atomic Force Microscopy has raised in the last years as a solid and versatile lithographic technique for fabrication of devices and structures in a nanometric scale. Although, fundamental aspects, as the kinetics involved during the oxidation, are still under study. The objective of this work is to develop a characterization process of this AFM lithographic technique aiming not only to obtain a better understanding of the kinetics involved in the oxidation process but also be able to determine and quantify the influence of the main processing parameters that control the anodic oxidation reaction in the probe-sample interface. By means of a dynamic oxidation process, where the AFM probe is scanning the sample's surface during the oxidation process, we determine the volumetric growth rates of the oxide patterns as a function of the applied voltage in the probe-sample interface, the humidity and the scanning rate of the microscope. As an example of the potential of this technique, it is implemented for the fabrication of devices in a sub-micrometric scale.The fabrication of nano-scaled devices is developed by means of two stages of lithography, first a course adjustment of microscopic patterns and then a fine adjustment where lines and other geometries are patterned in a scale of dezens of nanometers. The goal of this work is to develop both processes. Fine lithography will be done by means of local anodic oxidation (LAO oxidation) with an Atomic Force Microscopy (AFM). A two-layer (PMMA-Ge) resist structure is proposed here for de½nition of structures in a nanometric scale. The system to be studied is essentially based on the self-assembled quantum dots (QDs). The idea of the implementation of LAO oxidation and growth of QDs is to obtain the best performance of each of these processes, the high precision of local anodic lithography and the clean electronic properties of the QDs, aiming to study electronic properties of a small number of isolated QDs / Mestrado / Física da Matéria Condensada / Mestre em Física

Cette étude réalisée dans le cadre du procédé SPS (Suspension Plasma Spraying) a pour but de mieux appréhender les mécanismes de formation des lamelles résultant de l'impact de particules submicroniques par une approche adimensionnelle. Cette approche repose sur la diminution de la vitesse d'impact à l'échelle micrométrique (40 µm) pour se rapprocher des conditions d'impact des particules sub-microniques (300 nm). Un banc dédié permet d'étudier la dynamique d'étalement de gouttes micrométriques. Cette étude comprend - une étude expérimentale de l'étalement de gouttes isolées durant le procédé, - une approche adimensionnelle comparant les comportements à l'étalement de gouttes aux échelles micrométrique et sub-micrométrique, - une étude de la morphologie des lamelles avec la rugosité des substrats. Les résultats acquis permettent de définir une rugosité la mieux adaptée à un étalement maximal des lamelles aux deux échelles de mesure et d'éviter la présence de défauts à l'interface dépôt/substrat. Des essais de tractions sur des dépôts projetés montreront que le profil de rugosité joue un rôle décisif sur l'adhérence des dépôts. / As part of the Suspension Plasma Spraying process (SPS), this study aims at a better understanding of the impact behavior of sub-micrometric droplets. Using a dimensionless approach, the governing mechanisms of splat formation are studied. This approach is based on the velocity decrease of the micrometric droplet (40 µm), in order to be closer to sub-micrometric particle impact conditions. A specific test bench is used to study the dynamic flattening of micrometric droplets. This work includes - an experimental study of the impact of single droplets on a substrate, - a dimensionless approach to compare flattening behaviors of micrometric and sub-micrometric droplets - a study of splat morphology related to the substrate roughness. The results allow to define the substrate roughness for maximum splat flattening for both measuring scales, and to prevent the formation of any defects at the coating / substrate interface.

Orientadores: Kleber Roberto Pirota, Fanny Béron / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-31T01:32:45Z (GMT). No. of bitstreams: 1 CostaArzuza_LuisCarlos_D.pdf: 5838350 bytes, checksum: f92268a1c7835ed7d3d7f0a83abe2e63 (MD5) Previous issue date: 2016 / Resumo: Este trabalho visa estudar a inversão da magnetização de redes de nanofios de níquel modulados, incorporados em membranas porosas de alumina. A modulação do nanofio foi obtida a partir da variação do diâmetro, resultando em nanofios com dois segmentos. O diâmetro de cada segmento está ao redor do diâmetro crítico do Ni (40 nm), onde, abaixo e acima do mesmo, a inversão da magnetização acontece por meio de diferentes estruturas da parede de domínio; transversais e vórtex. A caracterização magnética das redes de nanofios foi feita usando simulações micromagnéticas e curvas de histerese magnética e de reversão de primeira ordem (método FORC). As medidas foram realizadas em vários arranjos de nanofios ordenados com diferentes razões de comprimento e diâmetros de segmentos, e estas foram comparadas com o arranjo de nanofios sem variação do diâmetro. Simulações micromagnéticas em nanofios isolados e arranjo de nanofios de primeiros vizinhos, mostram que a estrutura da parede de domínio, a qual depende do diâmetro do segmento, sofre uma transformação ao cruzar a região da modulação do diâmetro, porém a dinâmica da transformação depende das dimensões de cada segmento do nanofio. O comportamento magnético experimental do arranjo é atribuído a um campo de interação não homogêneo entre os nanofios, o qual surge devido a modulação do diâmetro. Este campo dá origem a uma interação mais forte na extremidade com diâmetro maior em relação à extremidade com diâmetro menor, resultando em um comportamento da susceptibilidade bastante complexo. Consideramos como principal resultado deste trabalho à possibilidade de controlar o mecanismo de inversão da magnetização em rede de nanofios modulados através da modulação do diâmetro. Os resultados obtidos foram interpretados através dos diagramas FORC, onde o processo dinâmico da inversão da magnetização é evidenciado por meio de diagramas estáticos (diagramas FORC), similar a uma foto estroboscópica / Abstract: We studied the magnetization reversal in modulated nickel nanowire arrays, embedded in porous alumina membranes. The modulation of the nanowire was obtained from the variation in diameter, resulting in nanowires with two segments. The diameter of each segment is below and above the critical diameter for Ni (40 nm), for which the reversal of magnetization changes from transversal to vortex domain wall structure. Magnetic characterization of nanowire networks was made using micromagnetic simulations, magnetic hysteresis and First-order reversal curves (FORC method). The measurements were performed in nanowire arrays with different ratios of length and diameter. The results were compared with the arrangement of nanowires without diameter variation. Micromagnetic simulations for isolated nanowires and nanowire array with few magnetic entities show that the structure of domain wall, which depends on the segment diameter, changes when it crosses the separation region of the diameter modulation and the dynamics of transformation depends on the dimensions of each nanowire¿s segment. The experimental magnetic behavior of the nanowire array is attributed to an inhomogeneous interaction field among the nanowires due to diameter modulation. This effect gives rise to a stronger interaction in the larger diameter segment resulting in a very complex susceptibility behavior. We consider the possibility to control the reversal magnetization mechanism in nanowire array through diameter modulation as the main result of this work. The results were interpreted using the FORC diagrams where the dynamic process of magnetization reversal is evidenced by static diagrams (FORC diagrams), similar to a stroboscopic picture / Doutorado / Física / Doutor em Ciências / 1060136/2011 / CAPES

The content of this thesis deals with the manufacturing of the prototyped series of low friction ring, proposing of the serial production and economical and technical evaluation. This thesis also solves the surfacing of low friction rings and testing. The thesis is devided into two main parts. First part deals with selection of material, tools and process of manufacturing low friction ring. Second part concerns surfacing and after testing. The thesis ends with economic and technical evaluation.

The diploma thesis deals with force-distance spectroscopy method as a tool for determining pull-off force on graphit/graphene sheets under varied conditions. There is described also a contact angle method which is used to idetify contact angles of water on six investigated samples. Results of both method were discussed with respect to utilization of force-distance spectroscopy in wetting measurements of materials. Finally it was carried out modification of graphen sheet by local anodic oxidation.

This diploma thesis summarizes knowledge from the fields of synthesis, characterization and application of titanium dioxide nanotubes and its combination with silver nanoparticles for biomedical purposes. Basic protocols of working with cell cultures and bacteria are also included. Experimental part of this diploma thesis focuses mainly on the synthesis of tubular structures made of titanium dioxide via anodic oxidation of 500nm titanium layer and their subsequent decoration with silver by electrodeposition. Last section of the experimental part is devoted to testing of antibacterial properties of the new material and examining the effect of different silver concentrations on the adhesion of MG-63 cells. All results are compared to reference samples consisting of titanium dioxide nanotubes without silver.

Táto práca sa zaoberá technikou výroby samousporiadaných nanoštruktúr pre elektrické aplikácie. Prototypy boli pripravené anodickou oxidáciou v dvoch dĺžkach a tromi rôznymi tepelnými úpravami. Štrukturálna charakterizácia bola spravená pomocou techniky SEM, TEM a EDX a vyhodnotenie nielen z štrukturálneho, ale aj z materiálového hľadiska. Jedinečná koreňová štruktúra samousporiadaných nanotyčiniek bola vyhodnotená a porovnaná po troch rôznych tepelných úpravách: po anodizácii, po vákuovom žíhaní, a po žíhaní vo vzduchu. Všetky prototypy obsahujú nanotyčinky s amorfnou štruktúrou, ale našli sa však aj nanokryštály pod koreňovými štruktúrami. Elektrická charakterizácia prototypov ukázala: odporové spínacie správanie (RS), diódové charakteristiky a charakteristiku podobnú pre diódy s kapacitorom. Aktívny povrch pre spínací mechanizmus je v hornej časti nanoštruktúr na rozhraní nanotyčiniek a zlatej elektródy. Výška Schottkyho bariéry na rozhraní Ti / TiO2 bola vypočítaná dvoma spôsobmi a pre všetky tri zariadenia bola nižšia ako 1,11 eV.