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Crystallisation spectrometerFrancis, Philip Sydney, phil.francis@rmit.edu.au January 2002 (has links)
An improved crystallisation spectrometer has been designed, built and tested. It is to be used by others to gain new knowledge about the solidification of matter by study of the crystallisation of hard sphere colloid samples that are an established model for the behaviour of some aspects of atoms. In this crystallisation spectrometer, expanded and collimated green laser light is Bragg scattered from the colloidal crystals as they form, and the diffracted light is focused by a liquid filled hollow glass hemispherical lens onto low cost CCD array detectors that are rotated about the optical axis to average the intensities around the whole Debye-Scherrer cone of scattered light. The temperature of the sample is controlled to +/-0.1a, and because of the ability to change the refractive index of the sample particles with temperature, this is utilised to control the amount of scattering from the sample Also, this spectrometer uniquely exploits the refractive index match of the colloidal particles, the solvent, the bath liquid, and the glass used for both the sample bottle and the hollow glass hemisphere. A unique facility has been incorporated to permit tumbling of the sample prior to the measurement commencing to shear-melt any pre-existing crystals. This ensures that the sample is completely fluid and is at the correct temperature at the start of the measurement. The instrument is assembled on an optical table and is computer controlled. Results presented show that this new spectrometer with its use of the whole Debye-Scherrer cone of Bragg scattered light and other enhancements gives insight into the crystallisation process more than one order of magnitude of time earlier than previous light scattering experiments, providing new knowledge about the crystallisation process. Read more
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Structuration d’électrode contrôlée pour des applications (bio)électrochimiques / Controlled electrode structuring for (bio)electrochemical applicationsLenz, Jennifer 30 September 2011 (has links)
Ce mémoire a été préparé dans le cadre du projet européen ERUDESP. Il décrit en détail les études qui ont été réalisées dans ce travail. Un bioréacteur sous forme d’une cellule bioélectrochimique à flux a été développé dans le but de servir pour la bioélectrosynthèse enantiopure. Le mémoire est consacré au design de cellules, screenings de différents médiateurs, au test de différentes réactions électroorganiques et électroenzymatiques à la fois dans une cellule électrochimique classique et dans une cellule électrochimique à flux. Un thème central de ce mémoire représente la synthèse d’électrodes macroporeuses tri-dimensionnelles. Grâce à cela, la surface active de l’électrode est augmentée de manière significative. Pour la préparation de ces électrodes une approche de template a été suivie. Des particules de polystyrène monodisperses ont été synthétisées de différentes manières et sont utilisées pour la synthèse des cristaux colloïdaux qui constituent les templates. Comme procédure de préparation contrôlée de ces templates, la technique de Langmuir-Blodgett et la méthode d’évaporation contrôlée, suivi par l’électrodéposition des métaux et des oxydes métalliques sont appliquées. Les diamètres des pores des matériaux macroporeux résultants sont parfaitement contrôlables par le diamètre des particules utilisées. La méthode de Langmuir-Blodgett a été étendue et appliquée pour la première fois à l’utilisation de particules de polystyrène. Le dépôt est réalisé dans les interstices des cristaux colloïdaux préparés préalablement, suivi par la dissolution des particules. De plus, des électrodes poreuses avec une grande surface de 6 x 6 cm2 ont été préparées. Les matériaux obtenus montrent une très bonne interconnéctivité avec une porosité ouverte et une surface active fortement augmentée ce qui se traduit électrochimiquement en une augmentation significative de la puissance du signal. Les matériaux poreux représentent un bénéfice non-seulement pour la (bio)électrosynthèse mais aussi dans le cadre de la (bio)électroanalyse. Dans ce mémoire, d’électrodes poreuses d’oxyde de ruthénium pour l’oxydation direct de NADH avec une surtension significativement améliorée ont été élaborée. La méthode de l’agrandissement de la surface est également appliquée et une meilleure densité de courant a été obtenue. Basé sur le projet ERUDESP, les méthodes apprises pour créer des électrodes poreuses à base de cristaux colloïdales ont dans la suite aussi été appliquées à d’autres domaines d’investigation. L’évolution méthodique de la technique de Langmuir-Blodgett a été utilisée pour le développement d’un système d’électrode renouvelable. Dans ce système, la surface peut être renouvelée sur commande par application d’un potentiel fixe (effet click).Les électrodes de l’oxyde de ruthénium ont non seulement été étudié dans le cadre du projet ERUDESP, mais la miniaturisation de ce matériau poreux et stable sous forme de microélectrodes a permis d’étudier une application comme capteur pH chimiquement et mécaniquement stable avec un meilleur ratio signal sur bruit. Dans ce cas le bruit thermique est diminué grâce à la porosité de l’électrode. Grâce à la technicité acquise par rapport à la synthèse des microélectrodes poreuses, des microélectrodes implantables pour les prothèses de main ont été aussi modifiées avec une couche macroporeuse pour augmenter la surface active et diminuer l’impédance de transition.Nous avons également exploré des couches multicatalyseurs macroporeuses de platine et nickel pour effectuer la génération d’hydrogène in-situ et l’hydrogénation simultanée dans un seul système catalytique.Comme dernière possibilité pour une structuration de surface contrôlée, des îlots de platine d’une étendue nanométrique furent examinées et biofonctionnalisées, ce qui résulte également en une augmentation significatif de la densité de courant. / The present work has been prepared within the framework of the European project ERUDESP and describes the research that has been carried out during this work. A bioreactor as a bioelectrochemical flow-cell was designed and realized with the goal to serve for enantiopure bioelectrosynthesis. The work deals with the cell design and screening of different mediators in a batch-cell and multi-cells, the development of different electroorganic and electroenzymatic reactions in an electrochemical batch- and flow-cell. With respect to the flow-cell, the upscaling of electrochemical reactions was carried out in the present work not only for electroorganic but also for electroenzymatic reactions with regard to the final application. A main focus of the present work represents the synthesis of three-dimensional macroporous electrodes in order to increase significantly the active surface. These macroporous structures were obtained by using the template approach. For the preparation of the templates monodisperse polystyrene particles were synthesized in different ways, and then used for the preparation of colloidal crystals serving as templates. As controlled assembly procedures, the Langmuir-Blodgett technique and the controlled evaporation method with subsequent electrodeposition of metals and metal oxides were chosen. With the present process the pore diameter could be exactly controlled by the diameter of the used particles. The approach of the Langmuir-Blodgett technique has been extended and optimized. For the first time, the Langmuir-Blodgett technique could be used with polystyrene particles. The deposition took place in the interspaces of the prepared colloidal crystals and is followed by the dissolving of the particles. Furthermore, the size of the porous electrodes could be upscaled (6 x 6 cm2). The obtained materials showed a very good interconnectivity with an open porosity and a highly increased active surface, which led to an increased electrochemical signal. The prepared porous materials represent a great benefit not only for (bio)electrosynthesis but also in the field of (bio)electroanalysis. In the framework of this work, the use of porous ruthenium oxide electrodes for direct oxidation of NADH with a significantly improved overvoltage was studied. Also in this context the increase of the surface led to an improved current density. Based on the ERUDESP project, the studied techniques for preparing porous electrodes with colloidal crystals were used for further scientific studies. The new variant of the Langmuir-Blodgett technique has also been used for the elaboration of a renewable electrode system where the surface can be simply renewed by applying a positive potential to the porous multilayers (click effect). The porous ruthenium oxide electrodes have not only been studied with respect to the ERUDESP project, but it was also possible to miniaturize this stable porous material as microelectrodes and use them as chemically and mechanically stable pH sensor with an improved signal to noise ratio. In this case the thermal noise decreased due to the porosity of the electrode. Due to the acquired expertise in the field of the preparation of porous microelectrodes, implantable microelectrodes for hand prosthesis were modified with a porous layer on the surface for increasing the active surface and decreasing their impedance.In addition, macroporous multicatalyst layers of platinum and nickel were synthesized for the simultaneous in-situ generation of hydrogen and hydrogenation reaction in the same catalyst system.As a final example for controlled surface structuring, nanoscale platinum islands were in detail examined and biofunctionalized. This led also to a significant increase of the current density. Read more
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Synthesis and characterization of Prussian red derived microparticles for the heterogeneous photo-fenton oxidation of azo-type textile dyes as pollutantsLai, Joshua 29 October 2020 (has links)
Inorganic colloidal synthesis, without a doubt, lies at the foundation of many contemporary areas of nanoscience and nanotechnology. At the advent of the 21st century, much progress has been made in the size, shape / morphological control and surface engineering of metal oxides resulting in a diverse library of macroscopic crystal architectures with well-defined surface properties. In this thesis, we start by introducing the self-assembly of the iron(oxy-, hydro-)xide while briefly reviewing some fundamental concepts of solid-state chemistry. Specific information on the family of iron oxide and iron(oxy-, hydro-)xide, as relevant to crystalline phase control, has been highlighted to direct our discussion of the synthesis of diverse crystal morphologies. Furthermore, we briefly underline and discuss the kinetic and thermodynamic control of colloidal crystal morphologies through reasonably established knowledge of anisotropic growth rates in the perspective of iron oxides' facets or crystalline planes. Lastly, we review the state-of-the-art wet chemical synthetic approaches, while using different iron(oxy-, hydro-)xide crystals as examples, for the purpose of explaining our synthetic work of choice. The main work of this thesis is entirely focused on the "facile synthesis and fine morphological tuning of branched hematite (??-Fe2O3) crystals for photodegradation of azo-type dyes".. We would discuss the crucial parameters for fine morphological tuning in the context of controlling the anisotropic growth rates of branched ??-Fe2O3 crystals instead of phase transformation. In our work, we have significantly improved the synthesis of dendritic "feather-like" and "starfish-like" for their size reduced variants for use in photocatalysis. Read more
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Controlling Microbial Colonization and Biofilm Formation Using Topographical CuesKargar, Mehdi 13 January 2015 (has links)
This dissertation introduces assembly of spherical particles as a novel topography-based anti-biofouling coating. It also provides new insights on the effects of surface topography, especially local curvature, on cell–surface and cell–cell interactions during the evolution of biofilms.
I investigated the adhesion, colonization, and biofilm formation of the opportunistic human pathogen Pseudomonas aeruginosa on a solid coated in close-packed spheres of polystyrene, using flat polystyrene sheets as a control. The results show that, whereas flat sheets are covered in large clusters after one day, a close-packed layer of 630–1550 nm monodisperse spheres prevents cluster formation. Moreover, the film of spheres reduces the density of P. aeruginosa adhered to the solid by 80%. Our data show that when P. aeruginosa adheres to the spheres, the distribution is not random. For 630 nm and larger particles, P. aeruginosa tends to position its body in the confined spaces between particles. After two days, 3D biofilm structures cover much of the flat polystyrene, whereas 3D biofilms rarely occur on a solid with a colloidal crystal coating of 1550 nm spheres. On 450 nm colloidal crystals, the bacterial growth was intermediate between the flat and 1550 nm spheres. The initial preference for P. aeruginosa to adhere to confined spaces is maintained on the second day, even when the cells form clusters: the cells remain in the confined spaces to form non-touching clusters. When the cells do touch, the contact is usually the pole, not the sides of the bacteria. The observations are rationalized based on the potential gains and costs associated with cell-sphere and cell-cell contacts. I concluded that the anti-biofilm property of the colloidal crystals is correlated with the ability to arrange the individual cells.
I showed that a colloidal crystal coating delays P. aeruginosa cluster formation on a medical-grade stainless-steel needle. This suggests that a colloidal crystal approach to biofilm inhibition might be applicable to other materials and geometries. The results presented in appendix 1 suggest that colloidal crystals can also delay adhesion of Methicillin resistant staphylococcus aureus (MRSA) while it supports selective adhesion of this bacterium to the confined spaces. / Ph. D. Read more
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Thermosensitive Injectable Pluronic Hydrogels for Controlled Drug Release: Characterisation of thermal, rheological and structural properties of injectable pharmaceutical formulationsShriky, Banah January 2018 (has links)
This study seeks to develop smart hydrogel formulations for injectable controlled drug delivery from Pluronics to enhance patients compliance, decrease side effects, reduce dose and frequency.
A biocompatible copolymer, Pluronic F127 was probed as the main ingredient for the injectable systems owing its low gelation concentration and ease of modification the system properties through excipients addition. The matrix properties were studied through a series of thermal, rheological and structural (SAXS/SANS) experiments as a function of concentration and shear rate, covering both static and dynamic environments. It has shown that gelled viscosity (and structure) can be critically controlled by shear rate and the structures recorded do not match those predicted for sheared colloids. Two further Pluronics F68 and F108, were studied showing similar but shifted gelation properties to F127.
Effects of additives were studied by introducing different Mw PEGs and a model hydrophobic drug ‘ibuprofen’ to a F127 20% formulation. PEGs addition effects on the system properties and gelation transition were largely dependent on the Mw used in the blend, which became more prominent with increasing chain length.
Ibuprofen’s addition has resulted in reduced gelation temperature and smaller hard spheres without having a great effect on the system rheological properties compared to neat gels.
Blends containing both additives PEG and ibuprofen exhibited a synergistic effect, where comparisons show that Ibuprofen had the largest effect on the blends lowering gelation boundaries and slightly increasing the size of the hard spheres indicating the necessity of full characterisation of the formulation with any API. Read more
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Cinétiques de concentration de suspensions colloïdales par évaporation microfluidique : de la solution diluée aux cristaux colloïdauxMerlin, Aurore 26 November 2010 (has links)
Cette thèse est consacrée à l’étude de processus de concentration de solutions colloïdales par voie microfluidique, pour former des matériaux denses et structurés. A partir d’un outil basé sur la perméation de l’eau à travers le PDMS : le microévaporateur, nous proposons de contrôler le séchage de solution pour maîtriser la concentration de solutés afin de former des états denses organisés au choix, alternant cristaux et états amorphes de colloïdes. En adaptant les outils de microévaporation à différentes techniques d’observations, la nucléation et la croissance d’états denses ont été finement étudiées et correlées à un modèle simple de la microévaporation. Ces études expérimentales ont montré le contrôle précis qu’apporte le microévaporateur sur les cinétiques de concentration d’espèces chimiques pour la formation d’états denses de particules.Des études complémentaires ont aussi mis en évidence l’existence d’une dynamique de construction de cristaux colloïdaux avec des réorganisations au niveau du front ainsi qu’un effet de compaction présents lors de la croissance de l’état dense. / This work is devoted to studying processes of colloidal solutions concentration by microfluidic way to shape dense and organized states. Using a tool based on the water permeation through the PDMS: the microevaporator, we propose to control drying of solution for controlling solute concentration to form dense states as one chooses, alternating crystals and amorphous states of colloids.By adapting microevaporation tool at different observation techniques, nucleation and growth are particularly studied and correlated to a simple microevaporation model. This experimental work demonstrates the good control on kinetics of chemical species concentration offered by microevaporation, in order to shape dense states of particles.Further studies also reveal existence of a dynamic construction of colloidal crystal with some reorganization in the front growth and a compaction effect of the dense state during the growth. Read more
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Fabricação de sistemas nanoestruturados de SiO2 pela técnica Roll-to-Roll e aplicações em fotônica / Production of nanostructured SiO2 systems by Roll-to-Roll technique and photonic applicationsCagnani, Giovana Rosso 17 August 2018 (has links)
Pesquisas de desenvolvimento na área de fotônica impressa vão desde sistemas óticos de reflexão e espalhamento de luz, até moduladores e dispositivos fotônicos na escala nanométrica. Para isso, os dispositivos fabricados utilizam das propriedades de estruturas capazes de controlar a emissão e propagação luminosa a níveis elevados de confinamento e guiamento. Estas estruturas são conhecidas como cristais fotônicos. No entanto, os cristais fotônicos encontram dificuldades de aplicação, pois são produzidos por métodos intermitentes e em pequena escala. Neste sentido, este estudo contribuiu para o desenvolvimento de um método de fabricação de cristais coloidais em larga escala. O processo consistiu em depositar nanoesferas de sílica com diferentes diâmetros e em diferentes substratos através da ferramenta wire-bar via processamento Roll-to-Roll. Para o desenvolvimento do trabalho as nanoesferas de sílica foram sintetizadas seguindo o método Stöber e caracterizadas quanto a distribuição dos diâmetros. As imagens das nanoesferas obtidas por Microscopia Eletrônica de Varredura (MEV) foram analisadas pelo software ImageJ®, constatando-se a monodispersividade das esferas. Posteriormente, para a deposição das partículas sobre os substratos, os parâmetros de deposição foram ajustados a fim de produzir um filme monocamada de cristais coloidais em um arranjo hexagonal compacto. Desenvolvemos também uma equação que prediz a concentração ótima das suspensões coloidais, em função dos parâmetros de processamento e o ordenamento de rede, para produzir o filme monocamada. Assim, foram alcançadas estruturas organizadas que exibiram o efeito iridescente mediante a variação do ângulo da luz incidente. Diante das propriedades óticas e periodicidade da rede dos cristais coloidais, propusemos aplicações como adesivos reflexivos, camada anti-reflexo para células solares e superfícies melhoradas para amplificação do sinal SERS. As estruturas utilizadas em SERS apresentaram limite de detecção para a molécula de Rodamina 123 da ordem de 10-6 M. De maneira geral, este trabalho contribuiu para o desenvolvimento de um método de deposição de cristais coloidais em larga escala através do processamento Roll-to-Roll, que se mostrou bastante versátil, uma vez que permite a aplicação das estruturas fabricadas em diferentes áreas tecnológicas e fácil controle dos parâmetros de processamento. / Development research in printed photonics goes from optical systems of reflection and scattering of light, to modulators and photonic devices at the nanometer scale. For this, the devices manufactured use the properties of structures capable of controlling the emission and light propagation at high levels of confinement and guidance. These structures are known as photonic crystals. However, the photonic crystals find application difficulties because they are produced by intermittent and small scale methods. In this sense, this study contributed to the development of a large-scale method of manufacturing colloidal crystals. The process consisted in depositing silica nanospheres with different diameters and in different substrates through the wire-bar tool in Roll-to-Roll processing. For the development of this work the silica nanospheres were synthesized following the Stöber method and characterized by distribution of diameters. The images of nanospheres obtained by Scanning Electron Microscopy (SEM) were analyzed by ImageJ® software, confirming the monodispersivity of the spheres. Subsequently, for the deposition of the particles on the substrates, the deposition parameters were adjusted to produce a monolayer film of colloidal crystals in a compact hexagonal arrangement. We have also developed an equation that predicts the optimal concentration of the colloidal suspensions, as a function of the processing parameters and the network ordering, to produce the monolayer film. Thus, organized structures were achieved which exhibited the iridescent effect by varying the angle of incident light. Considering the optical properties and periodicity of the colloidal crystals arrangement, we have proposed applications such as reflective adhesives, anti-reflective layer for solar cells and improved surfaces for amplification of SERS signal. The structures used in SERS showed limit of detection for Rhodamine 123 molecule in the order of 10-6 M. In general, this work contributed to the development of a large-scale method of deposition of colloidal crystals through Roll-to-Roll processing, which proved quite versatile, since it allows the application of of fabricated structures in different technological áreas and easy control of processing parametres. In general, the Roll-to-Roll method of colloidal crystals deposition proved to be quite versatile, since it allows the application of fabricated structures in different technological areas, easy control of processing parametres and large-scale production. Read more
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Simulações por dinâmica molecular aplicadas ao estudo de defeitos em cristais coloidais bidimensionais / Simulações por dinâmica molecular aplicadas ao estudo de defeitos em cristais coloidais bidimensionaisSilva, Línder Cândido da 29 August 2008 (has links)
Suspensões coloidais de microesferas de poliestireno carregadas proporcionam um sistema experimental excelente para estudar muitos problemas em física da matéria condensada. Sob condições apropriadas as partículas nessas suspensões podem se auto-organizar em um cristal com ordem de longo alcance, o chamado cristal coloidal. Neste trabalho apresentamos resultados de simulações por Dinâmica Molecular relacionados a defeitos pontuais, vacâncias e interstícios, em um cristal coloidal 2D. Calculamos a energia de formação e a interação destes defeitos pontuais, mostrando que um interstício é mais provável de ser criado do que uma vacância e que a interação entre os defeitos (vacância-vacância e interstício-interstício) é atrativa. Em conjunto esses resultados apontaram que os defeitos pontuais podem afetar o mecanismo de fusão do cristal coloidal 2D. Com relação à dinâmica dos defeitos, o foco foi sobre as vacâncias. Calculamos as entalpias de migração deste defeito de uma forma original, baseada na troca de topologias. Concluímos que a vacância não difunde de acordo com um único mecanismo, mas sim um misto de dois comportamentos, são eles: relação de Arrhenius corrigida e relação de potência com a temperatura. Calculamos também as entalpias e entropias relativas de formação das topologias da vacância, o que possibilitou identificar as topologias mais estáveis. Acreditamos que esses resultados serão importantes para trabalhos experimentais envolvendo interfaces e superfícies sólidas. / Colloidal suspensions of charged polystyrene microspheres provide an excellent experimental system to study many problems in condensed matter physics. Under appropriate conditions the particles in these suspensions organize themselves in a long-range-ordered crystal, the so-called colloidal crystal. In this thesis we report Molecular Dynamics simulations on point defects, vacancies and interstitials, in a 2D colloidal crystal. We have calculated the formation energy and interaction of these point defects, as well as the energy barriers between the various topological configurations that the defects may adopt while in thermal equilibrium. It is shown that the interstitials are more likely to be formed than the vacancies, and the interaction between defects (vacancy-vacancy and interstitial-interstitial) is attractive. Taken together, these results indicate that point defects may affect the melting process of a 2D colloidal crystal. With regard to the dynamics of the defects, emphasis was placed on the vacancies. The enthalpy for migration of a vacancy was calculated on the basis of exchanges between topologies. We concluded that the vacancy does not diffuse according to a single mechanism, but rather through a mixture of two processes: one is a modified Arrhenius mechanism and the other is represented by a power-law dependence on the temperature. We also calculated the relative enthalpies and entropies associated with the formation of the different topologies of vacancies, which allowed identification of the most stable topologies. We believe these results may have important bearing on experimental works involving interfaces and solid surfaces. Read more
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Simulações por dinâmica molecular aplicadas ao estudo de defeitos em cristais coloidais bidimensionais / Simulações por dinâmica molecular aplicadas ao estudo de defeitos em cristais coloidais bidimensionaisLínder Cândido da Silva 29 August 2008 (has links)
Suspensões coloidais de microesferas de poliestireno carregadas proporcionam um sistema experimental excelente para estudar muitos problemas em física da matéria condensada. Sob condições apropriadas as partículas nessas suspensões podem se auto-organizar em um cristal com ordem de longo alcance, o chamado cristal coloidal. Neste trabalho apresentamos resultados de simulações por Dinâmica Molecular relacionados a defeitos pontuais, vacâncias e interstícios, em um cristal coloidal 2D. Calculamos a energia de formação e a interação destes defeitos pontuais, mostrando que um interstício é mais provável de ser criado do que uma vacância e que a interação entre os defeitos (vacância-vacância e interstício-interstício) é atrativa. Em conjunto esses resultados apontaram que os defeitos pontuais podem afetar o mecanismo de fusão do cristal coloidal 2D. Com relação à dinâmica dos defeitos, o foco foi sobre as vacâncias. Calculamos as entalpias de migração deste defeito de uma forma original, baseada na troca de topologias. Concluímos que a vacância não difunde de acordo com um único mecanismo, mas sim um misto de dois comportamentos, são eles: relação de Arrhenius corrigida e relação de potência com a temperatura. Calculamos também as entalpias e entropias relativas de formação das topologias da vacância, o que possibilitou identificar as topologias mais estáveis. Acreditamos que esses resultados serão importantes para trabalhos experimentais envolvendo interfaces e superfícies sólidas. / Colloidal suspensions of charged polystyrene microspheres provide an excellent experimental system to study many problems in condensed matter physics. Under appropriate conditions the particles in these suspensions organize themselves in a long-range-ordered crystal, the so-called colloidal crystal. In this thesis we report Molecular Dynamics simulations on point defects, vacancies and interstitials, in a 2D colloidal crystal. We have calculated the formation energy and interaction of these point defects, as well as the energy barriers between the various topological configurations that the defects may adopt while in thermal equilibrium. It is shown that the interstitials are more likely to be formed than the vacancies, and the interaction between defects (vacancy-vacancy and interstitial-interstitial) is attractive. Taken together, these results indicate that point defects may affect the melting process of a 2D colloidal crystal. With regard to the dynamics of the defects, emphasis was placed on the vacancies. The enthalpy for migration of a vacancy was calculated on the basis of exchanges between topologies. We concluded that the vacancy does not diffuse according to a single mechanism, but rather through a mixture of two processes: one is a modified Arrhenius mechanism and the other is represented by a power-law dependence on the temperature. We also calculated the relative enthalpies and entropies associated with the formation of the different topologies of vacancies, which allowed identification of the most stable topologies. We believe these results may have important bearing on experimental works involving interfaces and solid surfaces. Read more
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Fabricação de sistemas nanoestruturados de SiO2 pela técnica Roll-to-Roll e aplicações em fotônica / Production of nanostructured SiO2 systems by Roll-to-Roll technique and photonic applicationsGiovana Rosso Cagnani 17 August 2018 (has links)
Pesquisas de desenvolvimento na área de fotônica impressa vão desde sistemas óticos de reflexão e espalhamento de luz, até moduladores e dispositivos fotônicos na escala nanométrica. Para isso, os dispositivos fabricados utilizam das propriedades de estruturas capazes de controlar a emissão e propagação luminosa a níveis elevados de confinamento e guiamento. Estas estruturas são conhecidas como cristais fotônicos. No entanto, os cristais fotônicos encontram dificuldades de aplicação, pois são produzidos por métodos intermitentes e em pequena escala. Neste sentido, este estudo contribuiu para o desenvolvimento de um método de fabricação de cristais coloidais em larga escala. O processo consistiu em depositar nanoesferas de sílica com diferentes diâmetros e em diferentes substratos através da ferramenta wire-bar via processamento Roll-to-Roll. Para o desenvolvimento do trabalho as nanoesferas de sílica foram sintetizadas seguindo o método Stöber e caracterizadas quanto a distribuição dos diâmetros. As imagens das nanoesferas obtidas por Microscopia Eletrônica de Varredura (MEV) foram analisadas pelo software ImageJ®, constatando-se a monodispersividade das esferas. Posteriormente, para a deposição das partículas sobre os substratos, os parâmetros de deposição foram ajustados a fim de produzir um filme monocamada de cristais coloidais em um arranjo hexagonal compacto. Desenvolvemos também uma equação que prediz a concentração ótima das suspensões coloidais, em função dos parâmetros de processamento e o ordenamento de rede, para produzir o filme monocamada. Assim, foram alcançadas estruturas organizadas que exibiram o efeito iridescente mediante a variação do ângulo da luz incidente. Diante das propriedades óticas e periodicidade da rede dos cristais coloidais, propusemos aplicações como adesivos reflexivos, camada anti-reflexo para células solares e superfícies melhoradas para amplificação do sinal SERS. As estruturas utilizadas em SERS apresentaram limite de detecção para a molécula de Rodamina 123 da ordem de 10-6 M. De maneira geral, este trabalho contribuiu para o desenvolvimento de um método de deposição de cristais coloidais em larga escala através do processamento Roll-to-Roll, que se mostrou bastante versátil, uma vez que permite a aplicação das estruturas fabricadas em diferentes áreas tecnológicas e fácil controle dos parâmetros de processamento. / Development research in printed photonics goes from optical systems of reflection and scattering of light, to modulators and photonic devices at the nanometer scale. For this, the devices manufactured use the properties of structures capable of controlling the emission and light propagation at high levels of confinement and guidance. These structures are known as photonic crystals. However, the photonic crystals find application difficulties because they are produced by intermittent and small scale methods. In this sense, this study contributed to the development of a large-scale method of manufacturing colloidal crystals. The process consisted in depositing silica nanospheres with different diameters and in different substrates through the wire-bar tool in Roll-to-Roll processing. For the development of this work the silica nanospheres were synthesized following the Stöber method and characterized by distribution of diameters. The images of nanospheres obtained by Scanning Electron Microscopy (SEM) were analyzed by ImageJ® software, confirming the monodispersivity of the spheres. Subsequently, for the deposition of the particles on the substrates, the deposition parameters were adjusted to produce a monolayer film of colloidal crystals in a compact hexagonal arrangement. We have also developed an equation that predicts the optimal concentration of the colloidal suspensions, as a function of the processing parameters and the network ordering, to produce the monolayer film. Thus, organized structures were achieved which exhibited the iridescent effect by varying the angle of incident light. Considering the optical properties and periodicity of the colloidal crystals arrangement, we have proposed applications such as reflective adhesives, anti-reflective layer for solar cells and improved surfaces for amplification of SERS signal. The structures used in SERS showed limit of detection for Rhodamine 123 molecule in the order of 10-6 M. In general, this work contributed to the development of a large-scale method of deposition of colloidal crystals through Roll-to-Roll processing, which proved quite versatile, since it allows the application of of fabricated structures in different technological áreas and easy control of processing parametres. In general, the Roll-to-Roll method of colloidal crystals deposition proved to be quite versatile, since it allows the application of fabricated structures in different technological areas, easy control of processing parametres and large-scale production. Read more
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