Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 197-202). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1997. / Typescript. Vita. Includes bibliographical references (leaves 197-202). Also available on the Internet.

In this work, we study the nonlinear propagation of light in liquid crystals (LCs) and the optical gain provided by LCs when they are polymer- or dye-doped.We will focus on nematic LCs, which are characterized by a mean orientation (also called director) of the elongated molecules and by a subsequent birefringence. After a general introduction on LCs, we focus on the nonlinear propagation of light in nematic LCs, and in particular the soliton-like propagation (nematicon). Indeed, if the light injected in the cell is intense enough, it can create a waveguide that counteracts the diffraction of the light. The light then propagates with an almost constant (or periodic) transverse profile.Our contribution to the subject starts with the numerical modeling of the thermal noise that characterizes the nematic LCs and the study of spatial instabilities of the soliton propagation caused by that noise. In Ch.3 we show that, by explicitly implementing the spatial correlation of the director in the LC thermal noise, it is possible to reproduce some of the features that characterize the LC response, such as the speckle generation or the fluctuating trajectory of the spatial optical soliton in LCs. Indeed, when the nematicon diameter is of the same order ofmagnitude as or smaller than the refractive index perturbations caused by the thermal noise, the nematicon starts to fluctuate in space. These fluctuations are not present when the noise is not correlated, indicating that the long-range interactions in LCs are crucial to explain the fluctuations. The model also allows us to introduce the propagation losses experienced by the nematicon without the use of an ad-hoc term. The simulations are in agreement with the experimental results. This method could also help the modeling of complex nonlinear phenomena in LCs that rely on noise, such as modulation instabilities or filamentation.Then, the optical gain is included in the LCs by dissolving photoluminescent polymers or dyes in it. In particular, we show that a particular polymer, the polyfuorene, when dissolved in nematic LCs, creates an intricate supramolecular pattern composed by homogeneous LC-rich regions surrounded by polymer-rich boundaries. The study of these structures through an ultra-fast spectroscopic technique (the pump-probe technique) and confocal microscopy reveals that the boundaries are composed by ordered and isolated chains of polymers. This particular morphology allows the observation of the optical gain from an oxidized unit of the polymeric chain (keto defects). This signal is usually covered by the absorption caused by the chain aggregation in solid state samples, while in LCs it is clearly visible. The optical gain from the keto defects appears also to be polarized orthogonal to the LC director, which is also the orientation of most of the boundaries. When a dye, one of the pyrromethenes, is dissolved in the LCs, the sample appears to be homogeneous. The optical gain from the dye ispolarized along the LC director and it shows an important spectral blue-shift (10 nm) passing from a polarization parallel to orthogonal to the LC director. The amplified spontaneous emission (ASE) shows the same shift when changing the direction of the sample excitation.When the ASE and the nematicon are generated in the same sample, it is possible to study the interaction between the two. In particular, the waveguide induced by the soliton can be used to guide another signal at another wavelength. We show that the nematicon can collect the ASE generated in the same device and guide it to the same fiber used to inject the nematicon in the LC cell. The extraction of the ASE from the device increases almost one order of magnitude when the soliton is present. However, due to the nematicon spatial fluctuations in LCs, an optimal nematicon power has to be found. Indeed, by increasing the soliton power, the light guiding is improved since the refractive index contrast of the nematicon-induced waveguide is increased. However, very high soliton powers have to be avoided, since the power-dependent soliton fluctuations prevent an optimal collection of the light. The nematicon is also found to increase the spectral purity and the polarization degree of the guided signal.Another LC system is studied, the chiral nematic LCs. In this system, the molecules are disposed following an helicoidal distribution. Due to their optical anisotropy and the periodic distribution, the system presents an optical band-gap. If the LC is also dye-doped, the combination of optical band-gap and gain generates laser emission. We are interested in a fast (sub-ms) reorientation of the helix, with the aim of studying the effect of this reorientation on the laser emission. The first step is the alignment of the LC helix (without the dye) with its axis parallel to the glass plates that constitute the cell, which is difficult to obtain with a high optical quality. For this reason, an innovative method is developed to align LCs through directional solvent evaporation. The solvent-induced method allows us to obtain particularly homogeneous textures, with a contrast ratio between the bright and the dark states that is a factor of 4 greater than that obtained with traditional methods. The LC samples based on solvent-induced alignment are then stabilized via two-photon photo-polymerization. This technique allows us to polymerize small regions of the device while the rest of the sample can be washed out in a solvent bath. When an achiral material is used to refill the device, it assumes a chiral alignment in the polymerized regions and an achiral nematic distribution in the rest. The first characterization of the laser emission is then presented in the last Chapter, with the aim of achieving sub-ms electrical tuning in future works.In this work a wide range of aspects have been investigated, leading to the realization of novel techniques for the fabrication of liquid crystal devices, the demonstration of novel phenomena for light amplification in liquid crystals and the experimental verification of new numerical modeling tools for light propagation in liquid crystals. The three key aspects of the work are nonlinear propagation, optical amplification and electrical response of different LC-based mixtures. Although the first few chapters deal with some of the aspects separately, in the last chapter these aspects are combined, revealing interesting new phenomena and pointing out a number of new aspects that could be part of future work. The results in this work have potential applications in fast tunable lasers, optical communication systems and lab-on-chip components. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

A major area of research recently has been the study of nonlinear waves in liquid crystals. The availability of commercial liquid crystals and the formation of solitons at mWpower levels has meant that experimental research and the need to understand how the solitons are formed and interact has been boosted. The first part of the thesis looks at how two laser beams in a nematic liquid crystal interact. Specifically research has centred on the problem of directing a signal beam to a target area by varying the input angle of the control beam. Different approximate models are developed to describe this phenomena, with the results from these models compared to a full numerical analysis. The first model developed is called the particle model and is based on the unmodified modulation equations. The results from this model were acceptable when compared with the results obtained from a full numerical analysis. This comparison is indicative that the underlying assumptions of the model did not capture an essential part of interaction between the two laser beams. The second model used to describe the interaction between the two laser beams was based on the law of conservation of momentum in the laser beams. Here the potential between the laser beams was modified to take into account the profile of the beams. The results from this model were in excellent agreement with results from the full numerical analysis, showing the key role potential between the beams plays in the trajectories of the beams. The interaction between dark solitons was also studied. The model used in this case was based on the modulation equations with a suitable trial function for dark solitons. The results from this model were in excellent agreement with the results from the full numerical analysis. The behaviour of the dark solitons shown by the approximate model and the full numerical analysis showing similar key features. This thesis sets out the equations describing the interaction of laser beams in liquid crystals. These are the equations used to carry out a full numerical analysis. This analysis is valuable in its own right and is the standard to compare the results obtained from other models but to achieve a deeper understanding of how laser beams interact in liquid crystals approximate models are developed so that the important parameters in each model can be identified. The Lagrangian describing the interaction of laser beams in liquid crystals is used in all the approximate models. The approximate models can then be developed through the use of suitable trial functions that adequately describe how the laser beams interact. The derivation of the equations and how these equations are solved is described for each model. The results from each model are compared to a full numerical analysis with a discussion of how the results compare.

The present work is devoted to the study of the nonlinear optical properties of smectic samples containing gold nanoparticles with a rod shape. By using the time-resolved Z-scan technique, we determine the nonlinear refractive and absorptive coefficients at the vicinity of the smectic-A-nematic phase transition. Our results reveal that such coefficients are sensitive to the sample temperature. In particular, we show that the nonlinear refractive index presents a singular behavior close to the transition temperature. Further, we show that a nonlinear optical response may take place at temperatures where the smectic order is well established. We provide a detailed discussion of the effects associated with the introduction gold nanoparticles on the mechanisms behind the optical nonlinearity in liquid-crystal samples. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O presente trabalho é dedicado ao estudo das propriedades ópticas não-lineares de amostras esméticas contendo nanopartículas de ouro com um formato de bastão. Usando a técnica de varredura Z resolvida no tempo, nós determinamos os coeficientes de refração e de absorção não-lineares, nas vizinhanças da transição de fase nemática-esmética-A. Os nossos resultados revelam que esses coeficientes são sensíveis a temperatura da amostra. Em particular, nós mostramos que o índice de refração não-linear apresenta um comportamento singular próximo á temperatura de transição. Além disso,nós mostramos que uma resposta óptica não-linear pode ocorrer em temperaturas onde a ordem esmética está bem estabelecida. Será realizada uma discussão detalhada dos efeitos associados com as nanopartículas de ouro. E uma introdução sobre os mecanismos por trás da não-linearidade óptica em amostras de cristais líquidos esméticos.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo geral deste projeto é propor um modelo bidimensional que descreva o novo estado supercondutor, que apresenta simetria de cristal líquido, chamado de supercondutor nemático. O estudo começa com uma introdução sobre a teoria de Landau-Ginzburg das transições de fase, onde são discutidos conceitos como parâmetro de ordem e as ordens das transições de fase, que são essenciais para o desenvolvimento deste projeto. Em seguida, é feita uma discussão sobre as principais características dos supercondutores como a resistência zero, o efeito Meissner-Ochsenfeld, os tipos de supercondutores, o surgimento de vórtices e uma análise sobre a teoria de Landau-Ginzburg para transição de fase metal-supercondutor. Após isto, é feita uma abordagem sobre os principais tipos de cristais líquidos, com destaque ao cristal líquido nemático, onde é desenvolvida a teoria de Landau-Ginzburg para transição de fase isotrópica-nemática e um estudo sobre o surgimento de disclinações no cristal líquido nemático em duas dimensões. Por fim, é apresentado o modelo proposto para descrever o estado supercondutor nemático, com a construção da teoria de Landau-Ginzburg, o estudo do acoplamento entre as fases e os defeitos topológicos presentes nesse estado. / The objective of this project is to propose a two-dimensional model that describes the new superconducting state, which has liquid crystal symmetry, called nematic superconductor. The study begins with an introduction to the Ginzburg-Landau theory of phase transitions, which are discussed concepts such as order parameter and the orders of phase transitions, which are essential for the development of this project. Then, there is a discussion of the main characteristics of superconductors such as zero resistance, the Meissner effect-Ochsenfeld, the types of superconductors, the appearance of vortex and an analysis of the Landau-Ginzburg theory to metal superconductor phase transition. After this, an approach is made on the main types of liquid crystals, especially the nematic liquid crystal, which is developed Ginzburg-Landau theory for nematicisotropic phase transition and a study about the disclinations in the two dimensional nematic liquid crystal. Finally, the proposed model is presented to describe the nematic superconductor state, with the construction of the Ginzburg-Landau theory, the study of coupling between the phases and the topological defects resent in this state.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo geral deste projeto é propor um modelo bidimensional que descreva o novo estado supercondutor, que apresenta simetria de cristal líquido, chamado de supercondutor nemático. O estudo começa com uma introdução sobre a teoria de Landau-Ginzburg das transições de fase, onde são discutidos conceitos como parâmetro de ordem e as ordens das transições de fase, que são essenciais para o desenvolvimento deste projeto. Em seguida, é feita uma discussão sobre as principais características dos supercondutores como a resistência zero, o efeito Meissner-Ochsenfeld, os tipos de supercondutores, o surgimento de vórtices e uma análise sobre a teoria de Landau-Ginzburg para transição de fase metal-supercondutor. Após isto, é feita uma abordagem sobre os principais tipos de cristais líquidos, com destaque ao cristal líquido nemático, onde é desenvolvida a teoria de Landau-Ginzburg para transição de fase isotrópica-nemática e um estudo sobre o surgimento de disclinações no cristal líquido nemático em duas dimensões. Por fim, é apresentado o modelo proposto para descrever o estado supercondutor nemático, com a construção da teoria de Landau-Ginzburg, o estudo do acoplamento entre as fases e os defeitos topológicos presentes nesse estado. / The objective of this project is to propose a two-dimensional model that describes the new superconducting state, which has liquid crystal symmetry, called nematic superconductor. The study begins with an introduction to the Ginzburg-Landau theory of phase transitions, which are discussed concepts such as order parameter and the orders of phase transitions, which are essential for the development of this project. Then, there is a discussion of the main characteristics of superconductors such as zero resistance, the Meissner effect-Ochsenfeld, the types of superconductors, the appearance of vortex and an analysis of the Landau-Ginzburg theory to metal superconductor phase transition. After this, an approach is made on the main types of liquid crystals, especially the nematic liquid crystal, which is developed Ginzburg-Landau theory for nematicisotropic phase transition and a study about the disclinations in the two dimensional nematic liquid crystal. Finally, the proposed model is presented to describe the nematic superconductor state, with the construction of the Ginzburg-Landau theory, the study of coupling between the phases and the topological defects resent in this state.

Neste trabalho, construímos um arranjo óptico para realizar medidas de espalhamento de luz dinâmico (Dynamic Light Scattering - DLS). Após o processo de montagem, o experimento foi calibrado por meio de soluções padrão de nanoesferas de poliestireno dispersas em água deionizada. Após a calibração, investigamos sistemas mais complexos como cristais líquidos nemáticos uniaxias, bem como misturas ferronemáticas. A primeira etapa dos estudos teve como objetivo investigar o comportamento das difusividades dos modos hidrodinmicos splay e twist, em função da concentração iônica das misturas. As amostras preparadas se diferenciavam apenas pela quantidades de sal em suas composições. Observamos um aumento em Dsplay e diminuição de Dtwist com o aumento na concentração de sal. Esses efeitos são multifatoriais e podem estar relacionados à blindagem eletrostática intermicelar, favorecendo a aproximaao entre micelas vizinhas. O efeito de backflow também é um fenômeno relevante que minimiza os efeitos dissipativos e está associado as distorções de splay. Por fim, foram realizadas medidas de DLS em misturas ferronemáticas liotrópicas uniaxiais, com o objetivo de investigar o comportamento das difusividades dos modos hidrodinâmicos em função da concentração de nanopartículas magnéticas (ferrofluido FF). O alinhamento do diretor é bastante favorecido com a presença das nanopartículas, como previsto na literatura [32]. Além disso, em baixas concentrações (< 10^13 grãos/mL) as nanopartículas não interferem nos espectros de autocorrelação, sendo possível observar as flutuações orientacionais do diretor nemático. Dessa forma, a incorporação de grãos magnéticos auxiliou nas medidas de DLS, principalmente no que diz respeito à seleção dos modos hidrodinâmicos. Os resultados mostraram que, em fase NC , as difusividades Dsplay e Dbend diminuíram com o aumento da concentração de FF. Por outro lado, a difusividade Dtwist praticamente não foi afetada com a incorporação de FF. No entanto, na fase ND, foi possível observar quedas nos valores de Dsplay e Dtwist , comparando com a mistura sem FF (Nd3). / In the present dissertation we made a Dynamic Light Scattering (DLS) experimental setup as well as their clalibration. We use standard aqueous solution with polystyrene nanospheres, with 20 nm and 200 nm of mean diameter, for system calibation. After this process we investigated more complex systems as uniaxial lyotropic liquid crystals mixtures and ferronematic samples. Firstly, we investigate the behaviour of hydrodynamic modes as a function of ionic concentration. The experiments showed that D splay increases and D twist decreases when ionic concentration increases. There are many factors around this behaviour, one of them is the electrostatic shielding forming between nearby micelles that may favours the approximation between tham. The backflow effect also is a relevante phenomenon that minimize the viscous dissipation process of splay distortion. This effect tends to increase with ionic concentration. We also investigated the hydrodynamic behaviour of uniaxial lyotropic mixtures doped with magnetic nanoparticles (ferrofluid - FF). They were characterized by DLS measure-ments to investigated the role of dopping concetration on splay, twist, and bend distortions. According to our results the nanoparticles favours the director alignment by magnetic field as we can found in the literature [32]. Thus, the DLS measurements had been favored by addition of magnetics grains, particularly with regard to the selection role of hydrodynamic modes. Moreover, we have seen that the director relaxation process is not abruptly affected with incorporation of nanoparticles, at low quantities (< 10^13 grain/mL). In NC phase, Dsplay and Dbend tends to decreases when the FF concetrations increases. However the behavior of Dtwist is not completly clear. In ND phase, the addition of nanoparticles further decreases Dsplay and Dtwist , comparing with the free nanoparticles sample (Nd3).

Estruturas líquidas cristalinas estão presentes em materiais compostos por moléculas com anisotropia de forma e são caracterizadas por uma ordem orientacional de longo alcance. Na mesofase nemática as moléculas alongadas tendem a se alinhar paralelas entre si, a direção média de orientação define é caracterizada por um vetor unitário, chamado de diretor n. Os cristais líquidos liotrópicos são obtidos usualmente a partir da dispersão de moléculas anfílicas em água. Essas moléculas anfílicas, por terem uma parte polar e uma parte apolar, tendem a formar agregados anisotrópicos, com a parte polar da molécula na superfície. Esse tipo de estrutura esta presente em todos os seres vivos e o exemplo mais clássico é a membrana da célula. A existência de uma superfície de contorno ou uma fronteira modifica as propriedades de um material na vizinhança dessa fronteira. Isso é particularmente verdadeiro para os cristais líquidos, que são muitos sensíveis as condições de contorno, mesmos quando estas não são tão intensas. De fato essa propriedade e bastante útil para a fabricação de dispositivos eletro-ó pticos. Um dos efeitos de superfície mais evidente é a mudança no ordenamento das moléculas devido a quebra de simetria na superfície. Nas fases nemáticas esse efeito microscópico resulta na formação de uma camada superficial com uma ordem posicional que se estende ao longo de uma certa distância no volume. 0 outro efeito resulta da origem a mudanças significativas no estado orientacional das moléculas no volume devido a presença de forças superficiais. Esse efeito é conhecido como ancoramento. Na ausência de campos extemos ou condições de contorno qualquer orientação é igualmente provável. Neste trabalho serão apresentados os resultados de investigação das propriedades de cristais líquidos liotrópicos na interface com um substrata. Estudamos o comportamento dinâmico da camada superficial quando o campo magnético é aplicado e induz uma re­ orientação do diretor. Nesse estudo são utilizadas amostras de cristal líquidos liotrópicos. / Liquid crystalline structures are found in materials made from molecules which are anisotropic in shape; such material are characterized mainly by a long range orientational order. In the nematic phase, the rodlike molecules tend to align parallel to each other. The average orientation defines a unit vector, called director n. Lyotropic liquid crystals are usually obtained by the dispersion of amphiphilic molecules in water. Due the fact that these molecules present a polar head and a non-polar tail, they tend to form aggregates with the polar part at the aggregate surface. This type of struc­ ture is present in all living being; the most classical example is the cell membrane. The existence of a boundary surface affects the properties of a material close to this boundary. This particularly true for liquid crystals, which are very sensitive to boundary conditions, even when weak. Indeed, this property is quite useful in the fabrication of electro-optic devices. One of the most obvious surface effect is the change in the molecules organization due to a breaking of the symmetry at the boundary surface. In the nematic phases, this microscopic effect results in the formation of a surface la yer with a positional order that extends through the bulk up to a certain distance from the surface. The other effect of the surface results in a change in the orientational state of the molecules in the volume due to the sur face forces. This macroscopic effect is known as anchoring. In the absence of any external field or boundary conditions, all molecular orientation is equally probable. In this work, we will present some results of the investigation of the properties of lyotropic liquid crystals at the interface with a solid substrate. We have studied the dy­ namic of the surface layer when a applied magnetic field induces a reorientation of the nematic director. In this study different systems were used: lyotropic liquid crystals in the nematic phase, ferronematics (nematic phase doped with ferrofluid) and filled nematics (nematic phase doped with silica nano-spheres). By means of transmittance measurements.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-07-21T16:17:26Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) ATUALIZADA DISSERTAÇÃO_ARTHUR_UFPE_.pdf: 6640779 bytes, checksum: 54162674f1fcaee2b4fef8836f21cd72 (MD5) / Made available in DSpace on 2016-07-21T16:17:26Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) ATUALIZADA DISSERTAÇÃO_ARTHUR_UFPE_.pdf: 6640779 bytes, checksum: 54162674f1fcaee2b4fef8836f21cd72 (MD5) Previous issue date: 2016-03-30 / CNPQ / O estudo das propriedades de materiais orgânicos tem chamado atenção devido sua versatilidade estrutural e de composição que podem moldar suas propriedades físicas e químicas. Neste trabalho preparamos seis cromóforos rígidos contendo o heterociclo tiazolo[5,4-d]tiazol (Thz) como espaçador aromático, e grupos terminais piridínicos ou carboxílicos. Desta forma trabalhamos com duas linhas de pesquisa: foto-eletroquímica para os derivados piridínicos e síntese e caracterização de cristais líquidos (CLs). Investigamos as propriedades fotoquímicas e processos redox das bipiridinas X,X'-(tiazolo[5,4-d]tiazol-2,5- dil)bis(piridil) (X,X’ = 2,2’; 3,3’ ou 4,4’). Em solução, apresentaram propriedades acidocrômica via foto- e eletrodissociação de solventes clorados. A seguir, preparamos sais de trifluoracetato dos bipiridínio (viologens), que apresentaram propriedades fotocromáticas via transferência de elétron quando expostos à radiação UVB. Utilizamos os derivados carboxílicos como centros rígidos para a preparação de cristais líquidos. Escolhemos o grupo carboxilato como precursor sintético dos conectores orgânicos: éster, amida e 1,3,4-oxadiazol. Planejamos os cristais líquidos contendo tais conectores e cadeias alquílicas dodeciloxi (-OC12H25), obtendo materiais com estrutura geral: centro rígido + conectores + cadeias alcóxi. De acordo com a estrutura dos centros rígidos, preparamos treze mesógenos calamíticos (ácido tiazolo[5,4- d]tiazol-2,5-dicarboxílico), das quais seis apresentaram mesofases calamítica (comportamento esperados) e três apresentaram mesofases discóticas. O fotocromismo apresentado pelos sais de bipiridinas frente à radiação UVB nos permite sugerir aplicações como dosimetria desta radiação, presente na luz solar. As propriedades mesomórficas ainda estão em estudo. No entanto, conseguimos obter CL’s discóticos a temperatura ambiente e uma mesofase discótica nemática, bastante rara. / The study properties of organic materials has drawn attention due to its structural versatility and composition versatility, which can shape their physical and chemical properties. In this work, we prepared six rigid chromophores containing the heterocycle thiazolo[5,4-d] thiazole (Thz) as aromatic spacers, and pyridyl or carboxylic terminal groups. Hence, we have worked with two research lines: photo-electrochemistry for the pyridine derivatives and synthesis and characterization of liquid crystals (LCs). We investigated the photochemical properties and redox processes of the bipyridines X,X'-(thiazolo[5,4-d] thiazole-2,5-diyl)bis(pyridyl) (X,X' = 2,2 '; 3,3' or 4,4 '). In solution, these compounds showed acidochromic properties via photonand electrodissociantion of chlorinated solvents. Next, we prepare bipyridinium trifluoroacetate salts (viologens), which exhibited photochromic properties through electron transfer when exposed to UVB radiation. We used the carboxylic derivatives as rigid centers for the preparation of liquid crystals. We chose the carboxylate group as a synthetic precursor of organic connectors: esther, amide, and 1,3,5-oxadiazole. We plannned the liquid crystal containing these connectors and the alkoxy chains dodecyloxy (-OC12H25), obtaining materials with general structure: rigid center + connectors + alkoxy chains. According to the rigid center structure, we obtained thirteen calamitic (acid thiazolo [5,4-d] thiazole-2,5-dicarboxylic acid), six of which had mesophases calamítica (expected behavior) and three had discóticas mesophases. The photochromic presented by bipyridinium salts when exposed of UVB radiation allows suggest applications such as dosimetry of sunlight radiation. The mesomorphic properties are still under study. However, we obtained room temperatures discóticos LCs, as well as a nematic discótica mesophase which are quite rare.