This work presents information obtained from high-speed video and electrical monitoring of electrical breakdown (discharge) events during plasma electrolytic oxidation (PEO) of aluminium alloy substrates. Discharges were found to occur in extended sequences termed "cascades" at particular locations. This was a feature common to all the substrates and processing frequencies investigated. As the coating thickness increases, the characteristics remained broadly similar, although discharges become more energetic and longer-lived. Short PEO treatments were applied to existing PEO coatings in order to investigate the microstructural effects of discharge cascades. It was found that cascades persist at particular locations due to the residual deep pore channel left by previous discharges in the cascade. Observations were made of the way the coating was restructured around a cascade location. Samples were illuminated with very high intensity flashes during PEO processing, revealing that relatively large (1 mm diameter) bubbles form where a discharge emerges from the surface of a coating. Analysis of the overall energy consumption, as well as the energetic processes occurring within an individual discharge, indicate that the bubble growth occurs due to rapid volatilisation of water originating from the electrolyte. It is postulated that the growth of this bubble causes the electrical resistance to rise and is responsible for the termination of the discharge current. Investigations of high frequency (2,500 Hz) processing lead to the discovery of discharges occurring during the cathodic half-cycle, after a certain coating thickness had been achieved. Cathodic discharges were more energetic than anodic discharges, and created large craters in the coatings. Gas evolution was found to exceed the electrochemical Faraday yield, and was similar at low and high frequency initially. Once cathodic discharges began, the gas evolution rate increased and the coating mass gain levelled off.

Ultra-fine grained materials with sub-micrometer grain size exhibit superior mechanical properties when compared with conventional fine-grained material as well as coarse-grained materials. Severe plastic deformation (SPD) techniques have been shown to be an effective way to modify the microstructure in order to improve the mechanical properties of the material. Crystalline materials require dislocations to accommodate plastic strain gradients and maintain lattice continuity. The lattice curvature exists due to the net dislocation that left behind in material during deformation. The characterization of such defects is important to understand deformation accumulation and the resulting mechanical properties of such materials. However, traditional techniques are limited. For example, the spatial resolution of EBSD is insufficient to study materials processed via SPD, while high dislocation densities make interpretations difficult using conventional diffraction contrast techniques in the TEM. A new technique, precession electron diffraction (PED) has gained recognition in the TEM community to solve the local crystallography, including both phase and orientation, of nanocrystalline structures under quasi-kinematical conditions. With the assistant of precession electron diffraction coupled ASTARÔ, the structure evolution of equal channel angular pressing processed commercial pure titanium is studied; this technique is also extended to two-phase titanium alloy (Ti-5553) to investigate the existence of anisotropic deformation behavior of the constituent alpha and beta phases.

L'ajout de superplastifiants (SP) dans les ciments est utilisé pour améliorer la mise en œuvre du matériau. Les SP que nous étudions sont des polyélectrolytes anioniques, et plus précisément des polyméthacrylates greffés PEO. Il a été observé qu'une partie de ces SP est immobilisée dans une des premières phases résultant de l'hydratation du ciment : la phase OH-AFm, issue de l'hydratation de l'aluminate tricalcique (C3A). Ces phases appartiennent aux hydroxydes doubles lamellaires dont les feuillets sont chargés positivement et l'espace interfoliaire contient des espèces anioniques. Nous nous intéressons, à l'interaction entre les phases OH-AFm et ces SP, dont la longueur des greffons et le taux de greffage varient. Nous avons prouvé l'intercalation des SP par DRX et RMN dans la phase AFm. La conformation des SP entre les feuillets peut être décrite à partir de l'adaptation d'un modèle de conformation en solution sous forme de chaînes de blobs, élaboré par de Gennes. Des mesures de rayon de giration des polymères en solution saturée en calcium, par diffusion de neutrons aux petits angles, ont permis de valider le modèle des blobs en solution. Nous avons suivi la vitesse de sorption des SP, réalisé des isothermes et étudié la stabilité de la phase SP-AFm vis-à-vis des sulfates, présents en quantité dans les ciments. Indépendamment de leurs caractéristiques, les SP sont fixés à la même vitesse par la phase AFm. Au maximum des isothermes, un SP compense d'autant mieux les charges du feuillet que sa densité de charge est élevée. La phase SP-AFm est plus stable que la phase OH-AFm, mais la présence de sulfates entraîne une libération retardée sur plusieurs heures du SP en solution. L'hydratation du C3A en présence de polymère mène à une structure similaire à celle des phases modèles que nous avons étudiées et les interactions SP-AFm peuvent donc être considérées comme identiques.

Ce travail concerne l'étude du comportement rhéologique de nanocomposites modèles à base de Laponite dans du polyoxyde d'éthylène ou des mélanges polyoxyde d'éthylène avec du polyméthacrylate de méthyle. L'influence des paramètres moléculaires, masse molaire de la matrice et mode de protection des particules sur les propriétés rhéologiques a été étudiée. La meilleure dispersion est obtenue à partir d'une solution, la dilution d'un mélange maître conduisant à des matériaux hétérogènes. Les mélanges POE/PMMA sont compatibles à l'état fondu dans toute la gamme de concentrations mais hétérogènes à température ambiante au-dessus de 30% en poids de particules. En diluant un mélange Laponite/PEO dans le PMMA, nous avons montré que ces domaines se concentrent en particules en dessous de 30% de PEO et qu'une cocontinuité de phases PEO contenant les particules et PMMA essentiellement pur est formée au-dessus de 30% de PEO. La présence des particules diminue fortement la cristallinité.

The research discussed in this dissertation was conducted to understand drop formation of inkjet printing with inks containing polymer. Solutions containing a water soluble polymer, poly ethylene oxide (PEO), with different molecular weights and polydispersities were used as inks. A flash photographic technique was used to visualize the whole process of DOD drop formation of dilute polymer solutions. The effects of driving signal, frequency and liquid properties on drop speed, drop size, breakup time and the formation of satellites were studied in detail. The addition of PEO increases the shear viscosity at all molecular weights, but the change is small for dilute solutions. However, the addition of a small amount of PEO can have a significant effect on the DOD drop formation process, increasing breakup time, decreasing primary drop speed and decreasing the number of satellites in some cases. The effects depend on both molecular weight and concentration. At lower molecular weights (14k and 35k g/mol), the effect of PEO was small when the drop formation process for the dilute solution was compared with that of a Newtonian liquid having similar shear viscosity, and the effect of PEO was small even at concentrations large enough that the solution does not fall in the dilute regime. As molecular weight is increased, the effects of PEO on DOD drop formation increase significantly, and the effects of concentration become important. These effects are explained by the fluid elasticity which increases with increasing in molecular weight and concentration. When the liquid jets out of the nozzle, the polymer chains are stretched, and thus depart from their ideal coiled state. As a result, an elastic stress develops in the liquid column and resists capillarity-driven pinch off from the nozzle and is responsible for the decrease in drop speed and longer breakup time. DOD drop formation data were shown to correlate closely with effective relaxation time, proposed by Tirtaatmadja based on Rouse-Zimm theory. When driving voltage amplitude is 44.2 V, two important parameters (breakup time and primary drop speed) in DOD drop formation for solutions containing monodispersed PEO and aqueous solutions containing mixtures of monodispersed PEO were closely predicted by correlation equations involving effective relaxation time . A mixture rule was developed to calculate the relaxation time for mixtures of monodispersed PEO. However, for polydispersed PEO, effective relaxation time was based on viscous molecular weight since the molecular weight distributions of the polydispersed PEO were unknown. When breakup time was plotted versus effective relaxation time for 1000k g/mol PEO, the data did not lie on the same line as that for the 100k and 300k g/mol PEO. This is believed to be due to the molecular weight distributions of the polydispersed PEO. When more than one species are present, viscous average molecular weight does not adequately account for the long chain species making up the polymer sample. DOD drop formation dynamics is highly affected by the actuating waveform, including the driving voltage, waveform shape, and frequency. The effects of parameters (jetting frequency, voltage amplitude and the shape of waveform) characterizing the signal were investigated. The open time and first drop problem were also studied. Research in this dissertation gives a better understanding of DOD drop formation process of polymer solutions, which may lead to improvement of inkjet printing quality for a variety of industry inks and polymer micro scale deposition and patterning in large areas.

Made available in DSpace on 2014-06-11T19:23:28Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-03-28Bitstream added on 2014-06-13T20:30:13Z : No. of bitstreams: 1 antonio_ca_me_bauru.pdf: 1720399 bytes, checksum: 396bef6efc3f71eb7d1f9f3cad7c2279 (MD5) / Apesar da excelente relação resitência/peso das ligas de alumínio, a aplicação tecnológica destas ligas é limitada pela baixa resistência ao desgaste. Neste trabalho, amostras de uma liga de alumínio (AA 5052) foram tratadas pelo processo de oxidação por plasma eletrolítico, com tempo de exposição variando de 150 a 900 s. A composição e a estrutura química dos revestimentos assim produzidos foram analisadas por espectroscopia de absorção no infravermelho. Um método baseado na medida de correntes parasitas e a perfilometria foram usados, respectivamente, na determinação da espessura e da rugosidade das camadas depositadas. O revestimento formado porssui espessura de até 9,2um. Análises da morfologia dos revestimentos foram feitas com microscopia eletrônica de varredura enquanto a resistência a desgastte das superfícies foi avaliada com um sistema pino-sobre-disco. Os resultados revelaram a deposição de um revestimento cerâmico, que conferiu expressivo aumento à resistência a desgaste da liga, o qual mostrou que as amostras tratadas suportaram uma carga aplicada de 13,44 vezes em comparação com amostras sem tratamento / Despiste the excellent strengh/weight ratio, technological applications of aluminum aloys are limited by their low wear resistance. In this work, samples of AA 5052 aluminum alloy have been modified by plasma electrolytic oxidation, with exposure time ranging from 150 s to 900 soconds. Compositional characterization has been performed by fourier transform infrared spectroscopy. Eddy current and profilometry have been used, respectively, to evaluate thickness and roughness of the deposited layers. The coating formed has a thickness of up to 9,2 micrometers. Morphological investigations have been performed with scanning electron microscopy while wear resitance has been assessed using a pin-on-disk devide. The results have revealed the deposition of ceramic layers with significant enhancement of wear resistance, which showed that the treated samples resistance, which showed that the treated samples resist an applied load 13.44 times more compared with untreated samples

Submitted by ROSANA FERNANDES ANTONIO null (rosanafernandes@terra.com.br) on 2016-05-31T17:28:39Z No. of bitstreams: 1 TESE-revisão final completa.pdf: 3847881 bytes, checksum: e10b8224324efd0b693acb74474081b5 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-06-01T13:12:10Z (GMT) No. of bitstreams: 1 antonio_rf_dr_bauru.pdf: 3847881 bytes, checksum: e10b8224324efd0b693acb74474081b5 (MD5) / Made available in DSpace on 2016-06-01T13:12:10Z (GMT). No. of bitstreams: 1 antonio_rf_dr_bauru.pdf: 3847881 bytes, checksum: e10b8224324efd0b693acb74474081b5 (MD5) Previous issue date: 2016-04-28 / O tântalo vem se destacando entre os biomateriais metálicos devido a propriedades como baixa reatividade química, ótima duc¬tibilidade, elevada resistência à corrosão e ótima bioatividade. Neste trabalho foi utilizada a técnica de oxidação eletrolítica assistida por plasma (PEO- do ingês, Plasma Electrolytic Oxidation) em substrato de tântalo, utilizando-se como eletrólito uma solução de acetato de cálcio e glicerofosfato dissódio, com a finalidade de se crescer um revestimento de hidroxiapatita sobre a superfície metálica. No processo PEO empregou-se pulsos de tensão contínua com frequência de 100 Hz e foram avaliados os efeitos da variação da diferença de potencial aplicada entre os eletrodos, que foi variada de 350 a 500 V, e do tempo de tratamento, que variou de 60 a 600 s. Para análises da composição química e estrutural dos revestimentos foram utilizadas espectroscopias de reflexão/absorção no infravermelho (IRRAS) e de energia dispersiva de raios X (EDS) e difração de raios X (XRD), enquanto que a morfologia da superfície foi avaliada por microscopia eletrônica de varredura (MEV). Empregando-se a técnica de perfilometria determinou-se a rugosidade das superfícies tratadas. A bioatividade dos revestimentos foi avaliada a partir de ensaios de adesão e crescimento de células osteoblásticas. Os melhores resultados foram obtidos com amostras tratadas em 500V com um tempo mínimo de 300 s. Nestas condições foi possível a formação de um revestimento de hidroxiapatita cristalina, confirmada por XRD. Os espectros obtidos com IRRAS também confirmaram a presença de espécies químicas responsáveis pela formação de hidroxiapatita como fosfatos (PO43-), hidroxilas (OH-) e carbonatos (CO3-2). As amostras tratadas apresentaram bioatividade e viabilidade celular maiores que as observadas com o tântalo como recebido, devido às estruturas cristalinas de hidroxiapatita juntamente com a elevada rugosidade superficial obtida com o tratamento. A energia térmica gerada nas amostras durante o tratamento foi um fator determinante para se explicar a formação da hidroxiapatita. / Tantalum is becoming increasingly important amongst metallic biomaterials due to its special properties such as low reactivity, excellent ductility, high resistance to corrosion as well as high bioactivities. In this work Plasma Electrolytic Oxidation technique PEO, was employed on Tantalum substrate using a calcium acetate and glycerophosphate sodium with the goal of generating a coating of hydroxyapatite on the metallic surface. In this PEO process, DC pulses of 100 Hz were used. The differential of potential between the electrodes in the range of 350 V to 500 V were applied that lasted from 60s to 600s and their *effects were evaluated. For chemical composition and structural analysis of coating, Infrared Reflection Absorption Spectroscopy (IRRAS) were employed together with energy dispersive X-ray spectroscopy (EDS) and diffraction of X-ray (XRD). The morphology of the surface was evaluated with Electronic Scanning Microscopy. With profilometry techniques the roughness of the treated surface was determined. The bioactivity of the coating was assessed by testing the adhesion and development of osteoblastic cells. The best results were obtained with samples undergoing a tension of 500 V lasting for a minimum of 300 s. Under these conditions it was possible to form hydroxyapatite crystal that was confirmed by DRX. The spectra obtained with IRRAS also confirmed the presence of chemical species responsible for the formation of hydroxyapatite such as phosphate groups (PO43-), hydroxyls (OH-) and carbonates (CO32-). The treated samples show greater cellular bioactivity and viability than those observed in raw tantalum due to the crystal structure of hydroxyapatite together with high surface roughness obtained as a result of the treatment. The thermal energy generated in samples during the treatment was a determining factor for explaining the formation of hydroxyapatite.

Submitted by Automação e Estatística (sst@bczm.ufrn.br) on 2018-04-11T20:54:51Z No. of bitstreams: 1 ArlindoBalbinoDoNascimentoNeto_TESE.pdf: 17361179 bytes, checksum: 6648d2a7b9ce65ae1f54a644cf1af237 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2018-04-16T22:32:13Z (GMT) No. of bitstreams: 1 ArlindoBalbinoDoNascimentoNeto_TESE.pdf: 17361179 bytes, checksum: 6648d2a7b9ce65ae1f54a644cf1af237 (MD5) / Made available in DSpace on 2018-04-16T22:32:13Z (GMT). No. of bitstreams: 1 ArlindoBalbinoDoNascimentoNeto_TESE.pdf: 17361179 bytes, checksum: 6648d2a7b9ce65ae1f54a644cf1af237 (MD5) Previous issue date: 2017-12-13 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Até a presente data muitos estudos têm sido realizados em busca de materiais biocompatíveis para a fabricação de implantes, principalmente na área ortopédica e odontológica. Nesse sentido as ligas de titânio desempenham um papel importante para o uso em implantes devido à sua baixa densidade, não toxicidade, resistência à corrosão e biocompatibilidade. O titânio puro na presença dos fluidos biológicos apresenta uma fina camada passiva de óxido responsável pela biocompatibilidade quando inserido no organismo. No entanto, esta camada de óxido espontânea pode ser perdida, rapidamente, se inserido em ambientes adversos. Consequentemente, a modificação superficial apropriada se faz necessária para as ligas a base de titânio, melhorando as propriedades de superfície e sua bioatividade. Existe um grande espectro de técnicas de modificação de superfície disponíveis, tais como deposição física de vapor, deposição química a vapor, anodização, pulverização de plasma e Oxidação Eletrolítica por Plasma (PEO). Entre essas técnicas, o PEO apresenta-se como uma técnica atrativa para aplicações biomédicas devido as suas características que favorecem a osseointegração. Contudo, não se conhece as características e viabilidade da produção de revestimentos realizados em amostras cilíndricas, quando esses são produzidos em quantidade dentro da mesma solução eletrolítica. Portanto, faz-se necessário um estudo e melhor compreensão dos aspectos fundamentais desta tecnologia sob essa condição. Isso pode avançar a compreensão científica do processo PEO, o que poderia permitir um melhor uso da técnica para aplicações em larga produção. Baseado no que foi exposto, realizou-se revestimentos em banho eletrolítico por 1, 8 e 16 minutos, respectivamente, com tensão de 290 V CC. Realizou-se os tempos citados acima para 1, 2 e 3 amostras submersa simultaneamente na mesma solução eletrolítica. Para caracterizar a espessura do revestimento das amostras foram utilizados as técnicas de Microscopia Ótica (MO) e Eletrônica de varredura (MEV). Para obter a composição química e fase do revestimento, foram utilizados as técnicas de caracterização de Espectroscopia de Energia Dispersiva (EED), Difratometria de Raio-X (DRX). Com o objetivo de identificar a porosidade superficial utilizou-se o rugosímetro, o MEV e o método da figura de Lissajous. Para análise de desgaste no revestimento foi utilizado o método tribológico pino sobre haste. No estudo da molhabilidade utilizou-se o método da gota séssil. Os resultados obtidos foram revestimentos homogêneos, porosos, hidrofílicos e com resistência mecânica ao contato. Através do método da figura de Lissajous pode ser determinado o nível de porosidade presente nos revestimentos PEO. Os resultados obtidos mostraram a capacidade de escalabilidade de produção com características que demonstram ser favoráveis para se ter uma osseointegração homogênea e estável para implantes. / To date, many studies have been carried out in search of biocompatible materials for the manufacture of implants, mainly in the orthopedic and dental area. In this sense, titanium alloys play an important role for use in implants because of their low density, non-toxicity, corrosion resistance and biocompatibility. Pure titanium in the presence of biological fluids has a thin passive layer of oxide responsible for biocompatibility when inserted into the body. However, this spontaneous oxide layer can be lost, quickly, if inserted in adverse environments. Accordingly, appropriate surface modification is required for titanium based alloys, improving the surface properties and their bioactivity. There is a wide spectrum of surface modification techniques available, such as physical vapor deposition, chemical vapor deposition, anodizing, plasma spraying and Plasma Electrolytic Oxidation (PEO). Among these techniques, PEO is an attractive technique for biomedical applications because of its characteristics that favor osseointegration. However, the characteristics and feasibility of producing coatings made on cylindrical samples are not known when they are produced in quantity within the same electrolytic solution. Therefore, it is necessary to study and better understand the fundamental aspects of this technology under this condition. This may advance the scientific understanding of the PEO process, which could allow a better use of the technique for large-scale applications. Based on the above, electrolytic coatings were made for 1, 8 and 16 minutes, respectively, with a voltage of 290 VDC. The times mentioned above were performed for 1, 2 and 3 samples submerged simultaneously in the same electrolytic solution. To characterize the coating thickness of the samples, the techniques of Optical Microscopy (MO) and Scanning Electron (SEM) were used. To obtain the chemical composition and phase of the coating, the characterization techniques of Dispersive Energy Spectroscopy (EED), X-ray Diffraction (XRD) were used. In order to identify the surface porosity, the rugosimeter, the SEM and the Lissajous figure method were used. For the analysis of wear on the coating, the tribological method was used. In the study of wettability, the sessile drop method was used. The results were homogeneous, porous, hydrophilic and with mechanical resistance to contact. By the Lissajous figure method the level of porosity present in the PEO coatings can be determined. The results showed the capacity of production scalability with characteristics that prove to be favorable to have a homogeneous and stable osseointegration for implants.

In recent years, polymer-inorganic nanoparticle compositions have been a subject of considerable interest in order to achieve desired chemical, physical properties and mechanical properties. In this study a polymer nanocomposites have been prepared by incorporating silica nanoparticles (~20 nm) as fillers into poly(ethylene oxide) matrix. The composites of poly(ethylene oxide) and silica nanoparticles were prepared by solution blending. The product composites were powders. The thermal properties of the composites were investigated using the Differential Scanning Calorimetry. The Nuclear Magnetic Resonance (13C solid state, T1ρ), Atomic Force Microscopy, X-ray diffraction and Fourier Transform Infrared Spectroscopy were used to investigate the effect of the nanoparticles on the polymer matrix. The results suggest that the silica nanoparticles were reasonably well dispersed in the PEO 35K. The dispersion was accompanied by slightly reduced the crystallinity. However, with increasing the SiO2 nanoparticles the aggregation Phenomenon appears. Moreover, with increase in the MW of the PEO to 100K the dispersion of the nanoparticles decreased and aggregation phenomenon is observed even at lower of SiO2 contents.

No description available.