Dans la première partie de cette thèse, nous tirons parti du concept de nano-antenne optique afind'apporter une solution innovante au problème d'interprétation de la microscopie champ procheoptique (SNOM). En effet, il est connu que certaines nano-antennes développent des réponsesoptiques dipolaires. Dans cette thèse nous démontrons comment l’utilisation d’une nano-ouverturepapillon (nano-antenne dipolaire), à l’extrémité d’une pointe SNOM, permet de détecter et collecteruniquement une seule composante du champ proche électrique. Ce résultat est démontré d’unpoint de vue théorique par l’utilisation de simulation FDTD (Finite Difference Time Domain) et d’unpoint de vue expérimental par la caractérisation, par cette pointe innovante, d´échantillonsdiélectriques (réseaux, cristaux photoniques) et métalliques (milieux désordonnés plasmoniques).Dans une deuxième partie, nous démontrons comment la sonde développée dans la premièrepartie, peut être utilisée comme détecteur du signal émis par un nano-émetteurs (NE) unique. Il estétudié dans cette partie l’effet de couplage entre ces deux objets. Dans un premier temps, après ladescription complète des grandeurs caractéristiques d’un NE, nous démontrons théoriquementl’effet de la pointe sur la réduction du temps de vie de l’état excité et l’augmentation de lafluorescence d’un NE, en régime saturé et non saturé. Puis dans un deuxième temps nousdémontrons expérimentalement comment cette sonde réduit le temps de vie de l’état excité deboites quantiques placées à son extrémité, en comparaison de pointes SNOM plus conventionnellestelle que la pointe diélectrique et la pointe à ouverture circulaire. / In the first part of this manuscript, we use in our advantage the concept of optical nano-antennas, toget new solutions on the interpretation problems of scanning near-field optical microscope (SNOM)images. Indeed, it is known that some of the developed nano-antennas can express dipolarbehaviours. In this manuscript, we show how a bowtie nano-aperture (dipolar nano-antenna)embedded at the apex of a SNOM probe, can be used to detect and collect only one component ofthe electric near-field. This result is demonstrated as well theoretically, by the use of FDTD (FiniteDifference Time Domain) codes, as experimentally, by the characterisation with this tip, of dielectricsamples (diffraction grating and photonic crystals) and metallic ones (random plasmonic medium).In a second part, we show how the tip previously described, can be used as a detector of the signalfrom single emitter (SE). We study in this part the coupling and interactions between those twoobjects. After a full description of a two level system characteristics, we show theoretically the effectof our probe on the reduction of the excited state life time and the enhancement of thefluorescence of the SE, in both regime, saturated and non-saturated. Then we describeexperimentally how our special tip reduces the excited state life time of quantum dots placed at theapex of it, respect to more conventional SNOM probes as the dielectric and the circular apertureones.

Cette thèse considère de nouvelles architectures prometteuses des métamatériaux plasmoniques pour biosensing, comprenant: (I) des réseaux périodiques 2D de nanoparticules d'Au, qui peuvent supporter des résonances des réseaux de surface couplées de manière diffractive; (II) Reseaux 3D à base de cristaux plasmoniques du type d'assemblage de bois. Une étude systématique des conditions d'excitation plasmonique, des propriétés et de la sensibilité à l'environnement local dans ces géométries métamatérielles est présentée. On montre que de tels réseaux peuvent combiner une très haute sensibilité spectrale (400 nm / RIU et 2600 nm / RIU, ensemble respectivement) et une sensibilité de phase exceptionnellement élevée (> 105 deg./RIU) et peuvent être utilisés pour améliorer l'état actuel de la technologie de biosensing the-art. Enfin, on propose une méthode de sondage du champ électrique excité par des nanostructures plasmoniques (nanoparticules uniques, dimères). On suppose que cette méthode aidera à concevoir des structures pour SERS (La spectroscopie du type Raman à surface renforcée), qui peut être utilisée comme une chaîne d'information supplémentaire à un biocapteur de transduction optique. / This thesis consideres novel promissing architechtures of plasmonic metamaterial for biosensing, including: (I) 2D periodic arrays of Au nanoparticles, which can support diffractively coupled surface lattice resonances; (II) 3D periodic arrays based on woodpile-assembly plasmonic crystals, which can support novel delocalized plasmonic modes over 3D structure. A systematic study of conditions of plasmon excitation, properties and sensitivity to local environment is presented. It is shown that such arrays can combine very high spectral sensitivity (400nm/RIU and 2600 nm/RIU, respectively) and exceptionally high phase sensitivity (> 105 deg./RIU) and can be used for the improvement of current state-of-the-art biosensing technology. Finally, a method for probing electric field excited by plasmonic nanostructures (single nanoparticles, dimers) is proposed. It is implied that this method will help to design structures for SERS, which will later be used as an additional informational channel for biosensing.

O objetivo deste estudo in vitro foi avaliar e comparar a microestrutura e a composição mineral do esmalte e da dentina de dentes decíduos e permanentes. Terceiros molares hígidos e segundos molares decíduos foram selecionados e distribuídos aleatoriamente em grupos, de acordo com o método de análise dos substratos utilizado: Microscopia Eletrônica de Varredura (MEV), Espectroscopia de Energia Dispersiva de Raio X (EDX), Difração de Raio X (DRX) e Microscopia Óptica (MO). Foi realizada comparação qualitativa e quantitativa da estrutura dental. As medidas de densidade numérica e diâmetro dos prismas de esmalte/túbulos dentinários e, de espessura do esmalte, dentina e dentina peritubular foram realizadas por meio de fotomicrografias obtidas pela MEV. Os resultados obtidos por meio da SEM foram analisados estatisticamente pelo teste não-paramétrico de Kruskal-Wallis. A quantidade relativa de íons cálcio (Ca) e fósforo (P) foram determinadas por meio de EDX e as fases químicas presentes em ambos os substratos, por análise de DRX. O valor das medidas de espessura observado para o esmalte e dentina dos dentes decíduos foi de 1.14 mm e 3.02 mm, respectivamente. Para os dentes permanentes, obtiveram-se valores de 2.58 mm para o esmalte e 5.95 mm para a dentina. Com relação ao diâmetro da cabeça dos prismas de esmalte, os resultados foram estatisticamente semelhantes para os dentes decíduos e permanentes, demonstrando uma ligeira diminuição do diâmetro da superfície externa para a região próxima a junção amelodentinária (JAD). A densidade numérica dos prismas foi maior nos dentes decíduos, principalmente próximo à JAD, sendo estatisticamente diferente dos valores observados nos dentes permanentes, independente da região analisada. Na análise do diâmetro e densidade numérica dos túbulos dentinários verificou-se semelhança estatística entre os dentes decíduos e permanentes, havendo aumento gradativo do número de túbulos a partir da JAD em direção a região próxima a polpa. A espessura da dentina peritubular, na região próxima a JAD e central foi, respectivamente, 0.91 e 0.59 mm nos dentes decíduos 1.16 e 0.98 mm nos dentes permanentes. A porcentagem de Ca e P foi maior nos dentes permanentes. Observou-se ainda, que a quantidade de colágeno nos dentes decíduos foi aparentemente menor quando analisados por meio da MO. De acordo com os resultados obtidos neste estudo, pode-se concluir que, de maneira geral, os dentes decíduos apresentam menor porcentagem de Ca e P, menor espessura de esmalte e dentina, maior densidade numérica de prismas e dentina peritubular mais delgada quando comparada aos dentes permanentes. / This study evaluated in vitro the microstructure and mineral composition of dental enamel and dentin comparing the permanent teeth with the deciduous teeth. Sound third molars and second primary molars were selected and randomly assigned to the following groups, according to the analysis methods of the substrates performed: Scanning Electron Microscopy (SEM), X-Ray diffraction (XRD), Energy dispersive X-ray spectrometer (EDS) and Optical Microscopy (OP). A qualitative and quantitative comparison of the dental structure was done. The measurements of the number and diameter of prisms/tubules, thickness of enamel, dentin and peritubular dentin were done in SEM photomicrographs. The microscopic findings were analyzed statistically by a non-parametric test (Kruskal- Wallis). The relative amounts of calcium (Ca) and phosphorus (P) were determined by EDS investigation. Phase present in both types of teeth were observed by the XRD analysis. The mean thickness measurements observed in the deciduous teeth enamel and dentin was, respectively, 1.14 mm and 3.02 mm and in the permanent teeth, 2.58 mm and 5.95 mm. The mean rod head diameter in deciduous teeth was statistically similar to that of permanent teeth enamel, and a slightly decrease from the outer enamel surface to the region next to the enameldentine junction was assessed. The numerical density of enamel rods was higher in the deciduous teeth, mainly near EDJ, that showed statistically significant difference. The mean tubules number and diameter in deciduous teeth were statistically similar to that of permanent teeth, and this numerical density increased from the EDJ to the region near the pulp. The mean thickness measurements of peritubular dentin observed in the regions near EDJ and central were, respectively, 0.91 and 0.59 mm for the primary teeth / 1.16 and 0.98 mm for the permanent teeth. The percentage of Ca and P was higher in the permanent teeth. The collagen level was apparently lower in deciduous teeth when analyzed by OP. The primary teeth structure showed a lower level of Ca and P and a thinner enamel and dentin thickness. The deciduous enamel presented higher numerical density of rods. The peritubular dentin was thicker in the permanent teeth.

Die Dissertation beinhaltet Untersuchungen mittels optischer Rasternahfeldmikroskopie (SNOM)an epitaktisch gewachsenen Halbleiter-Nanostrukturen des Materialsystems GaAs/(Al,Ga)As, sowie Untersuchungen mittels Rasterkraftmikroskopie (AFM/MFM) an ferromagnetischen MnAs-Schichten auf GaAs. Der erste Teil der Arbeit widmet sich dem Aufbau und der Wirkungsweise eines neuen SNOM fürden Einsatz bei tiefen Temperaturen. Das Auflösungsvermögen des Mikroskopswird einmal in Hinblick auf die topographische Empfindlichkeit des Scanners in Richtung der Oberflächennormale, andererseits optisch-lateral charakterisiert. Es wird gezeigt, welche Möglichkeiten der Einsatz geätzter, unbedampfter Nahfeldsonden bietet. Im zweiten Teil werden nahfeld-optische Untersuchungen an GaAs-Quantenfilmen und GaAs-Quantendrähten vorgestellt. Die Grenzflächeneigenschaften der Quantenfilmstrukturen wurden per Wachstumsunterbrechung dahingehend beeinflusst, dass inselartige Gebiete konstanter Quantenfilmdicke entstehen, deren lateraler Durchmesser einige hundert Nanometer beträgt. Durch Photolumineszenzspektroskopie im SNOM kann die räumliche Verteilung der Inseln detektiert werden. Die optischen Nahfeldbilder geben einen interessanten Einblick in die Grenzflächenmorphologie des Quantenfilms und ermöglichen so Rückschlüsse auf die Wachstumsprozesse. Quantendrähte aus GaAs wurden in die intrinsische Zone einer p-i-n-Struktur eingebaut. Durch räumlich aufgelöste sowie energie-selektive Anregung von Photoströmen mittels SNOMkann das Verhalten von zusätzlich in der Struktur erzeugten Ladungsträgern auf den Gesamtstromfluss untersucht werden. Die Ergebnisse liefern ein verbessertes Verständnis über denProzess der selektiven Elektrolumineszenz, durch den diese Strukturen gekennzeichnet sind. Im letzten Teil werden strukturelle Untersuchungen an MnAs-Schichten vorgestellt, die auf GaAs(001) gewachsen wurden. Epitaktisch gewachsene MnAs-Schichten auf GaAs(001) zeigen eine Phasenkoexistenzvon ferromagnetischem und paramagnetischem MnAs unterhalb der Curie-Temperatur. Auf Grund dieser Besonderheit kommt es zur Ausbildung von periodischen elastischen Domänen in der Schicht. Die Entwicklung solcher Domänen wird mittels temperaturabhängiger Rasterkraftmikroskopiedirekt beobachtet. / In this thesis, investigations on both epitactically grown GaAs/(Al,Ga)As semiconductor nanostructures using near-field scanning optical microscopy (SNOM) as well as ferromagnetic MnAs films on GaAs using scanning force microscopy are presented.Setup, operation modes, and properties of a new SNOM designed for low-temperature experiments are discussed. In terms of resolution, both topographical sensitivity of the scanner and optical limitsare distinguished. Surprisingly, the use of uncoated optical fibre tips enables sufficient optical resolution, while the transmission increases dramtically compared to conventional SNOM probes. Using the SNOM setup, near-field optical experiments on GaAs quantum wells and GaAs quantum wiresare made. The interface properties of the quantum well structures had been influenced during growth by interrupting the growth process. Thus, island-like areas with constant well thickness are prepared, whose lateraldiameter is in the order of a few hundred nanometers.Near-field optical photoluminescence spectroscopy can detect the spatial distribution of the islands.The near-field optical images provide interesting insight into the interface morphology and henceabout the growth process itself. GaAs sidewall quantum wires had been grown such that they are built in the center of the intrinsic layer of a p-i-n LED structure.Applying the SNOM, spatially refined photocurrents are induced in the structure. The initial localisation of photogeneratedcharge carriers can also be chosen by varying the excitation energy.This enables a detailed study of how additionally generated carriers contribute to the photocurrent signal,the outcome of which provides deeper understanding in the process of a selective electroluminescenceof the structure. In the last part, structural investigations on MnAs film are discussed, which had been grown on GaAS(001) substrates.These films exhibit a phase coexistense of ferromagnetic and paramagnetic MnAs below the Curie temperature. As a result, periodic elastic domains of the coexisting phases are formed. The development of such domains is studied using temperature-dependent (magnetic) scanning force microscopy.The structural effects are discussed in connection with a theoretical model.

Die vorliegende Arbeit beschreibt neue Entwicklungen im Verständnis und in der Umsetzung der optischen Nahfeldmikroskopie (scattering - type scanning near-field optical microscopy, s-SNOM) für die lineare und nichtlineare optische Bildgebung mit ultrahoher Auslösung und Empfindlichkeit. Die fundamentalen Mechanismen, die der Feldverstärkung am Ende von ultrascharfen metallischen Spitzen zugrunde liegen, werden systematisch behandelt. Die plasmonischen Eigenschaften der Spitze wurden erstmalig beobachtet, und ihre Bedeutung für die optische Kopplung zwischen Spitze und Probe sowie für die sich ergebende Einengung des Nahfeldes wird diskutiert. Ein aperturloses Nahfeldmikroskop für die spitzenverstärkte Ramanspektroskopie (tip-enhanced Raman spectroscopy, TERS) wurde entwickelt. Die Grundlagen der TERS und die wesentliche Rolle des plasmonischen Verhaltens der Spitze sowie die klare Unterscheidung von Nahfeld-Ramansignatur und Fernfeld-Abbildungsartefakten werden beschrieben. Nahfeld Raman Verstärkungsfaktoren von bis zu 10 wurden erreicht, was einer Feldverstärkung von bis zu 130 entspricht und Raman-Messungen bis auf Einzel-Molekül-Niveau ermöglichte. Die optische Frequenzverdopplung (second harmonic generation, SHG) an einzelnen Spitzen wurde untersucht. Aufgrund ihrer teilweise asymmetrischen Nanostruktur erlauben die Spitzen eine klare Unterscheidung von lokalen Oberflächen und nichtlokalen Volumenbeiträgen zur nichtlinearen Polarisation sowie die Analyse ihrer Polarisations- und Emissions-Auswahlregeln. Die spitzenverstärkte Frequenzverdopplungs-Spektroskopie und die räumlich hoch aufgelöste Abbildung auf Basis des dielektrischen Kontrasts werden demonstriert. Mit Hilfe einer phasen-sensitiven, Selbst-homodyn-Frequenzverdopplungs-s-SNOM-Abbildungsmethode kann die Oberflächen-Struktur der intrinsischen 180-Domänen im hexagonal multiferroischen YMnO aufgelöst werden. / This thesis describes the implementation of scattering-type near-field optical microscopy (s-SNOM) for linear and nonlinear optical imaging. The technique allows for optical spectroscopy with ultrahigh spatial resolution. New results on the microscopic understanding of the imaging mechanism and the employment of s-SNOM for structure determination at solid surfaces are presented. The method relies on the use of metallic probe tips with apex radii of only few nanometers. The local-field enhancement and its dependence on material properties are investigated. The plasmonic character of Au tips is identified and its importance for the optical tip-sample coupling and subsequent near-field confinement are discussed. The experimental results offer valuable criteria in terms of tip-material and structural parameters for the choice of suitable tips required in s-SNOM. An near-field optical microscope is developed for tip-enhanced Raman spectroscopy (TERS) studies. The principles of TERS and the role of the tip plasmonic behavior together with clear distinction of near-field Raman signature from far-field imaging artifacts are described. TERS results of monolayer and submonolayer molecular coverage on smooth Au surfaces are presented. Second harmonic generation (SHG) from individual tips is investigated. As a partially asymmetric nanostructure, the tip allows for the clear distinction of local surface and nonlocal bulk contributions to the nonlinear polarization and the analysis of their polarization and emission selection rules. Tip-enhanced SH microscopy and dielectric contrast imaging with high spatial resolution are demonstrated. SHG couples directly to the ferroelectric ordering in materials and in combination with scanning probe microscopy can give access to the morphology of mesoscopic ferroelectric domains. Using a phase sensitive self-homodyne SHG s-SNOM imaging method, the surface topology of 180 intrinsic domains in hexagonal multiferroic YMnO is resolved.

Ionic Liquids (ILs) has been attracting attention, both from academia and industry, given the numerous applications of these systems. ILs are salts, usually composed by an organic ion, and a counterion which could be organic or inorganic, and, interestingly they are found at liquid state at room temperature. Our interest in studying ILs comes from its low toxicity. Some recent studies have shown that the toxicity of the ILs ishigher than believed, in particular for biologically relevant systems. The main goal of this research is to study the influence of the ionic liquid 1-tetradecyl-3-methylimidazolium chloride ([C14MIM][Cl]) with membrane systems. To do so, we made use of different lipids: POPC, Sphingomyelin, Cholesterol, POPG, DPPC, DPPG and DMPC. For each of these systems, the influence of ILs concentration were elucidated by means of a systematic study through different experimental techniques: Small Angle X-ray scattering (SAXS), dynamic light scattering (DLS), fluorescence anisotropy, optical microscopy and z-potential. Since [C14MIM][Cl] has a positive charge on the imidazolium group, the superficial charge of all vesicles increased. For zwitterionic vesicles no significant change in size and melting temperature were noticed. The imidazolium-based ionic liquid diminished the gel-fluid transition temperature for negatively charged lipids. For DPPC:DPPG (1:1), for instance, the transition temperature decreased from 42.50±0.13oC to 25.27±0.33oC and for DPPG from 46.12±0.22 oC to 36.6±0.38 oC. For DPPG, the vesicle hydrodynamic diameter increased from 84±0.1nm to 176±0.1nm, whereas for DPPC:DPPG it increased from 95±0.1nm to 196±0.1nm. The electronic density profile, obtained by SAXS, supported the penetration of the [C14MIM][Cl] into the negative bilayer structure. 15 mol% of [C14MIM][Cl] increased the polar head thickness of DPPC vesicles from 11.1±0.6 Å to 18.0±0.7 Å, without alter significantly the inner region of the membrane.Qualitative results obtained with optical microscopy showed that the IL incorporation destabilize the membrane asymmetry (between the leaflets) leading to the formation of pores (evidenced by optical contrast lost) and the presence of buds. We believe that this work could improve the understanding of the effects of ILs in the presence of biological relevant systems / Os líquidos iônicos (LI) tem atraído grande atenção, tanto da academia quanto da indústria, devido às suas numerosas aplicações. LI são sais, normalmente compostos por um íon orgânico, e um contra-íon que pode ser orgânico ou inorgânico, mas que tem como característica ser encontrado no estado líquido à temperaturas próximas a ambiente. Nosso interesse em estudar LIs vem de sua baixa toxicidade, atribuída a sua baixa volatilidade. Entretanto, alguns estudos recentes mostraram que a toxicidade dos LI é maior do que se acreditava, em particular com sistemas de relevância biológica.O objetivo principal desta dissertação é estudar a influência do líquido iônico 1-tetradecil-3-metilimidazólio cloreto ([C14MIM][Cl]) com sistemas de membrana. Para isso, utilizamos diferentes lipídios, como o POPC, esfingomielina, colesterol, POPG, DPPC,DPPG e o DMPC. Para cada um destes sistemas, a influência da concentração de LI foi elucidada por meio de um estudo sistemático através de diferentes técnicas experimentais, tais como: espalhamento de raio-X a baixos ângulos (SAXS), espalhamento dinâmico de luz (DLS), anisotropia de fluorescência, microscopia óptica e potencial-z. Uma vez que o componente iônico de [C14MIM][Cl] tem uma carga positiva no grupo imidazólio, a carga superficial de todas as vesículas estudadas aqui aumentou. Entretanto, para asvesículas compostas pelos lipídeos zwitteriónicos, não tenha sido observada qualquer alteração significativa no tamanho e na temperatura de transição de fase gel-fluido. O [C14MIM][Cl] altera a organização interna entre as moléculas de lipídio com carga negativa. Consequentemente, à medida que a quantidade de LI aumenta, a temperatura de transição de fase diminui e o tamanho médio das vesículas aumenta. Para o sistema DPPC:DPPG (1:1) a temperatura de transição de fase caiu de 42.50 ± 0.13 oC para 25.27 ± 0.33 oC e para as vesículas de DPPG de 46.12±0.22 oC para 36.6±0.38 oC. Quanto ao diâmetro hidrodinâmico médio, no caso do DPPG este valor aumentou de 84±0.1 nm para 176±0.1 nm, enquanto que para a mistura DPPC:DPPG (1:1) ele passou de 95±0.1nm para 196±0.1nm. Indicando assim que o LI incorpora na bicamada lipídica negativamente carregada. O perfil de densidade eletrônica, obtido por SAXS, confirma a penetração do [C14MIM][Cl] na bicamada lipídica. Diferentemente, para a membrana lipídica zwitteriónica o LI tende a se situar perto da região da cabeça polar sem afetar significativamente a região do interior da bicamada lipídica. Por outro lado, a presença de15 mol% de [C14MIM][Cl] aumenta a espessura da região polar das bicamadas das vesículas de DPPC de ~ 11.1±0.6 Å para ~ 18.0±0.7 Å. Os resultados qualitativos da microscopia óptica mostraram que a incorporação da LI desestabiliza a assimetria da membrana entre as camadas interna e externa, além de sugerir o aparecimento de poros (evidenciado pela perda do contraste ótico das vesículas) e estruturas chamadas de buds. Esperamos que este trabalho melhore a compreensão dos efeitos do LI na presença de organismos biológicos.

O objetivo do presente trabalho foi avaliar diferentes tratamentos na remineralização do esmalte desmineralizado em situação de alto desafio cariogênico. Foram utilizados 55 fragmentos de esmalte bovino (4mmX4mmX2mm) planificados e polidos. Os espécimes foram cobertos com resina composta ficando exposta apenas a metade da superfície externa (2mmX4mm) e então, foram imersos em solução tampão de acetato (pH 4,7) por 43 horas para formar a lesão de desmineralização. Os espécimes foram divididos aleatoriamente em 5 grupos (n=11), de acordo com os tratamentos preventivos: 1- Controle (sem tratamento); 2- Verniz fluoretado a 5% Duraphat®; 3- Flúor-gel 1,23%; 4- MI PasteTM; e 5- MI Paste PlusTM. Os tratamentos foram realizados uma vez por semana durante 3 semanas. Nos intervalos das aplicações os espécimes foram submetidos a ciclos de pH (DES/RE) num total de 21 dias. Após a finalização da ciclagem os fragmentos foram seccionados longitudinalmente, sendo que em uma metade foi analisada a microdureza longitudinal, pelo cálculo da variação percentual da dureza e na outra metade foi avaliada a profundidade de desmineralização do esmalte através de microscopia óptica. Para a análise em FTIR, pó do esmalte foi obtido dos espécimes em três diferentes momentos: inicial sem desmineralização da superfície, após a desmineralização por 43 horas e após o tratamento. Para análise da microdureza longitudinal empregou-se a variação da dureza. Os dados foram analisados quanto a sua distribuição, porém como não foram normais realizou-se uma análise não paramétrica comparando grupo contra grupo pelo Mann Whitney test com &alpha;=5%. Para análise da profundidade de desmineralização, como os dados se apresentaram normais e homogêneos, realizou-se a análise de variância a 1 critério e teste Holm- Sidak para comparação das médias com &alpha;=5%. Para análise em FTIR fez-se apenas uma análise descritiva dos dados. Na análise dos dados pode-se observar que houve diferença estatística significante entre o grupo controle (G1) com o grupo flúor-gel (G3) (p<0,05), o qual apresentou menor perda de dureza e menor profundidade de desmineralização. Os grupos 2, 4 e 5 foram similares entre si e com o G1 para as duas propriedades analisadas. Na análise da absorbância nos diferentes comprimentos de onda pode-se observar um padrão similar em todas as amostras; a banda de fosfato inicial foi mais larga e posicionada em número de ondas menores. Após a desmineralização, esta banda ficou mais estreita e deslocada para número de ondas maiores. Esse comportamento se repetiu e foi similar para todos os grupo. Baseado nos resultados obtidos pode-se concluir que nenhum dos tratamentos preventivos realizados foi capaz de inibir o processo de desmineralização ou promover a remineralização em situações de alto risco a cárie, embora o flúor-gel tenha permitido uma evolução mais lenta da desmineralização / The aim of this study was to evaluate different treatments on remineralization of demineralized enamel in a high cariogenic challenge. 55 enamel fragments (4mmX4mmX2mm) flat and polished were used. The specimens were covered with composite exposed only half of the outer surface (2mmX4mm) and then were immersed in acetate buffer solution (pH 4.7) for 43 hours to form the demineralization lesion. The specimens were randomly divided into 5 groups (n = 11) according with the preventive treatments: 1 - Control (no treatment); 2 - 5% fluoride varnish Duraphat ®; 3 - Fluoride-gel 1.23%; 4 - MI PasteTM; and 5 - MI Paste PlusTM. The treatments were carried out once a week for 3 weeks. During intervals and among applications the specimens were subjected to pH cycles (DES / RE) for a total of 21 days. After finished of the cycling, the samples were longitudinally sectioned, and one half in the longitudinal microhardness was analyzed and the other half the depth of enamel demineralization using optical microscopy was evaluated. For data analyzed was calculate the percentage change in the hardness. For FTIR analysis, the enamel powder was obtained from specimens at three different times: without demineralization of the surface, after demineralization for 43 hours and after treatment. Data were analyzed for their distribution, but they were not normal there was a non-parametric analysis comparing group versus group by t test (Mann- Whitney test) with &alpha;= 5%. To analyze the depth of demineralization, as the data were normal and homogeneous, we performed analysis of variance criterion 1 and Holm-Sidak test for comparison of means with &alpha;= 5%. For FTIR was realized of descriptive analysis of the data. Data analyzed showed statistically significant difference between the control group (G1) with the fluoride gel group (G3) (p <0.05), which showed less loss of lower hardness and depth of demineralization. Groups 2, 4 and 5 were similar among them and with G1 for two properties analyzed. The analysis of the absorbance at different wavelengths can be observed a similar pattern in all samples; band initial phosphate was wider and placed on the number of smaller waves. After demineralization, this band became narrower and shifted to higher wave number. This behavior was similar for all groups and it is repeated for every group. Based on the results this study it can be concluded that none of the preventive treatment carried out was able to inhibit the demineralization or promote remineralization in high caries risk situations, although fluoride gel has allowed a slow evolution of demineralization

Welding of duplex stainless steel pipeline material for the oil and gas industry is now common practice. To date, research has been conducted primarily on the parent material and heat affected zones in terms of its susceptibility to various forms of corrosion. However, there has been little research conducted on the degree of sensitisation of the various successive weld layers, namely the root, fill and cap layers. The focus of this research study was to: (i) provide an in-depth microstructural analysis of the various weld passes, (ii) study the mechanical properties of the weld regions; (iii) determine degree of sensitisation of the various weld passes; and (iv) investigate the residual stress levels within the various regions/ phases of the welds. Four test conditions were prepared using manual Gas Tungsten Arc Welding with 'V' and 'U' bevel configuration. Structural analysis consisted of (i) optical microscopy, scanning electron microscopy and magnetic force microscopy; (ii) ferrite determination using Magna-Gauge, Fischer Ferrite-scope and Point Count method. Mechanical testing consisted of Vickers hardness measurements, Charpy impact studies and transverse tensile testing. The degree of sensitisation was determined by three test methods: a modified ASTM A262, ASTM A923 and a modified Double Loop Electrochemical Potentiodynamic Reactivation (DL-EPR) test. Residual stress levels were determined using two neutron diffraction techniques: a reactor source and a time of flight spallation source. Microstructure observed by optical microscopy and magnetic force microscopy shows the formation of both fine and coarse structures within the weld metal. There was no evidence of secondary austenite, being present in any of the weld metal conditions examined. In addition, no detrimental intermetallic phases or carbides were present. The DL-EPR test results revealed that the fill layer regions for all four conditions and the base material showed the highest values for Ir/Ia and Qr/Qa. All four test conditions passed the ASTM A262 and A923 qualitative type tests, even under restricted and modified conditions. Residual stress measurements by neutron diffraction conducted at Lucas Heights Hi-Flux Reactor revealed that the ferrite phase stress was tensile in the heat affected zones and weld, and appeared to be balanced by a local compressive austenite phase stresses in the normal and transverse directions. Residual stress measurements by neutron diffraction conducted at Los Alamos Nuclear Science Centre revealed that in the hoop direction, ferrite (211) and austenite (311) exhibit tensile strains in the weld. In the axial and radial direction, the strains for both phases were more compressive. Correlations between the degree of sensitization and microstructural changes / ferrite content were observed. Higher degrees of sensitization (Ir/Ia and Qr/Qa) were associated with reduced ferrite (increased austenite) content. Correlations between the stresses generated, the evolved microstructures and degree of sensitization were evident. Stresses within the cap region were generally shown to be of a tensile nature in the transverse and longitudinal direction. In summary, the study has shown that correlations exist between the weld microstructure, susceptibility to sensitisation and levels / distribution of internal stresses within the weld regions.

The corrosion behaviour of cast Al-Mg alloy A535 and its composites containing 10 wt.% and 15 wt.% fly ash, and 10 wt.% hybrid reinforcement (5 wt.% fly ash + 5 wt.% SiC) was investigated using weight-loss and electrochemical corrosion tests, optical microscopy, Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). The tests were conducted in fresh water collected from the South Saskatchewan River and 3.5 wt.% NaCl solution at room temperature. The pH of the salt solution varied from 3 to 9. For comparison, two other aluminum alloys, AA2618 and AA5083-H116, were tested in the same electrolytes. The results of the weight-loss corrosion test showed that unreinforced A535 alloy had a lower corrosion rate in fresh water and seawater environments than the composites at all the tested pH values. The corrosion rate of the composites increased with increasing fly ash content. As expected, the corrosion rates of A535 alloy and the composites tested in fresh water were lower than those in salt solution. The results of the potentiodynamic and cyclic polarization electrochemical tests showed that the corrosion potential (Ecorr) and pitting potential (Epit) of the alloy were more positive than those of the composites. The corrosion and pitting potentials of the composites became more negative (active) with increasing fly ash content. The composites showed more positive (noble) repassivation or protection potential (Erp) than the matrix alloy, with the positivity increasing with fly ash content. Analysis of the electrochemical noise data showed that pitting corrosion was the dominant mode of corrosion for the alloy in 3.5 wt.% NaCl solution. Optical microscopy and SEM revealed that Mg2Si phase and Al-Mg intermetallics corroded preferentially to the matrix. The EDS data indicated that the protective oxide film formed on A535 contained Al2O3 and MgO.

En este trabajo se ha desarrollado un microscopio de fuerzas (SFM) provisto de microscopía electrostática (ESFM) y microscopía Kelvin (KPM) especialmente diseñado para integrarse en un microscopio óptico invertido de forma que combine simultáneamente las técnicas de campo cercano con las técnicas ópticas. Tras una introducción (capítulo 1) y la descripción de las técnicas experimentales (capítulo 2), se detallan las características del diseño de un primer prototipo, así como las medidas realizadas con él con el fin de comprobar su correcto funcionamiento (capítulo 3). El capítulo 4 muestra el diseño de un segundo prototipo con las mejoras que incorpora respecto al primero, que lo convierten en un sistema más completo, versátil y fácil de manejar. También figuran las medidas realizadas con él. El capítulo 5 muestra un estudio de fotodegradación en polímeros conductores en función de la radiación incidente, combinando microscopía electrostática y Kelvin con técnicas ópticas. / In this work we have developed an Scanning Force Microscope (SFM) equipped with Electrostatic and Kelvin Probe Microscopy (ESFM, KPM), specially designed for integration into an inverted optical microscope in order to combine near-field techniques with optical techniques. After an introduction (Chapter 1) and the description of the experimental techniques (Chapter 2), are described the features of the design of a first prototype, as well as the measurements made with it in order to verify proper operation (Chapter 3). The Chapter 4 shows the design of a second prototype that incorporates the improvements over the first, making it more comprehensive, versatile and easy to handle. Also are shown the measurements performed with it. The Chapter 5 shows a photodegradation study of conductive polymers as a function of incident radiation combining KPM with optical techniques.