<p>Diffusion of liquids into and through polymers is an important factor that negatively may influence the durability or lifetime of a polymer structure used in industrial applications. In this work two types of polymers, a liquid crystalline polymer (LCP, Vectra A950) and various thermoset resins as used in fibre reinforced plastics (FRP) process equipment were studied with regard to barrier properties, chemical resistance and long-term performance. LCP are known for their outstanding chemical resistance and barrier properties. FRP used in process equipment may be a cost-efficient solution in chemically aggressive environments where standard carbon or stainless steel cannot be used due to its limited corrosion resistance. Transport properties of typical industrial environments were determined for the LCP and the influence of annealing and orientation was investigated to study whether the barrier properties can be improved. The possibility to use LCP as cost-effective lining for FRP was explored. Special focus was put on the diffusion of water and its effect on long-term transport properties and stability of thermoset resins as the performance of FRP is strongly related to the diffusion of water. </p><p>The results showed that Vectra A950 was suitable for organic solvent and non-oxidising acid environments. Its transport properties were gravimetrically determined and found to be 10 to 102 times lower than that of a high barrier fluoropolymer of type FEP. The degree of molecular packing increased with annealing time both below and above the melting point. Below the melting point this was – at least – partly due to crystal formation whereas above the melting point other mechanisms were involved. The effects of annealing and orientation on the transport properties in LCP were, however, very small or not significant and probably significantly longer annealing times are required. LCP has potential to be used as lining material for FRP as the use of an LCP-lining substantially reduced the permeability of and the solute sorption in a bisphenol A epoxy-based vinyl ester resin. The bonding strength was improved significantly by a combined abrasive and oxygen plasma treatment.</p><p>The long-term sorption of water in thermoset resins including bisphenol A epoxy-based vinyl ester, novolac-based vinyl ester, urethane modified vinyl ester and bisphenol A polyester resins was found to increase with exposure time whereas the diffusion coefficient was not significantly affected. It was shown that the presence of water induced relaxation processes that were considered to be the primarily reason for the increase in sorption coefficient in comparison to degradation processes, such as hydrolysis, causing osmotic processes. A general relationship for the estimation of the sorption coefficient at 80ºC in dependence of the water activity and the sorption coefficient at unit activity independent of the resin type was established.</p>

A simple method for increasing the stable temperature range of the liquid crystalline blue phase is demonstrated, by mixing a non-mesogenic polymer of low molecular weight into the blue phase material. In a mixture of cholesteryl benzoate and cholesteryl nonanoate the addition of polystyrene increased the stable blue phase range from 0.5K to 12K. This was measured strictly on heating from the chiral nematic phase through the blue phase in order to minimise non-equilibrium effects, and is one of the largest ranges so measured. The stability range can be closely tuned by changing the polymer concentration and molecular weight. The maximum range found by adding a particular compound seems only to depend on its saturation point in the liquid crystal, and the dependence of the range on concentration is non-linear. These features were explained by a numerical model of a blue phase unit cell incorporating the mean field Flory-Huggins and Maier-Saupe theories where the polymer could fill the high energy defect regions. Two of the oligomers which are shown to stabilise the blue phase are fluorescent, at 450nm and 500nm respectively, and it is proposed that tests on these mixtures could reveal photonic effects caused by the concentration of the fluorophores in the blue phase defect regions. The twist-grain boundary (TGB) phase is present in mixtures of cholesteryl oleyl carbonate and cholesteryl nonanoate over a range of up to 0.3K. The addition of polystyrene has no effect on the stability of the TGB phase. Conventional, in situ UV-initiated polymer stabilisation does not appear to stabilise the TGB phase, but is capable of stabilising over at least 30K the micron-size filaments which appear in the TGB phase when it is heated from the smectic phase in a cell with homeotropic alignment. Some notes are made on the causes and structure of this filament texture, and it is observed that the filaments tend to grow with a characteristic curvature. It is shown theoretically that the correct material could stabilise the TGB phase similarly to the polymers in the blue phase, by extending the previous model to include the Kobayashi-McMillan theory of smectic ordering. A second theoretical model of chirality around the transition to the smectic phase is then presented which takes account of fluctuations, based on an analogy with the state of a smectic-forming material infiltrated into an aerogel. A phase resembling the TGB phase emerges from this model. The model gives two first order transitions in accordance with experiments on the TGB phase, and reflects other experimental pitch and calorimetry measurements too. The electrochemical polymerisation of an acrylate monomer in the nematic and smectic-C* phases is investigated. 30-100V is applied across a cell containing the liquid crystal-monomer mixture, with no additional initiating compound. In both phases, the texture during polymerisation is frozen in by the polymer formed. In a nematic phase in a cell with initially planar alignment, the director in the field off state can be observed to tilt toward the homeotropic over a number of hours. In the ferroelectric case, as well as the textural freezing there is a somewhat reversible agglomeration of polymer strands into micron-scale structures. Scanning electron microscopy reveals a range of structures on both electrode surfaces, including in the nematic case corrugations with a periodicity of 500-750nm. There is no evidence of a polymer network spanning the thickness of the cell - rather the liquid crystal seems to be realigned by a polymer film at the electrode surfaces.

Diffusion of liquids into and through polymers is an important factor that negatively may influence the durability or lifetime of a polymer structure used in industrial applications. In this work two types of polymers, a liquid crystalline polymer (LCP, Vectra A950) and various thermoset resins as used in fibre reinforced plastics (FRP) process equipment were studied with regard to barrier properties, chemical resistance and long-term performance. LCP are known for their outstanding chemical resistance and barrier properties. FRP used in process equipment may be a cost-efficient solution in chemically aggressive environments where standard carbon or stainless steel cannot be used due to its limited corrosion resistance. Transport properties of typical industrial environments were determined for the LCP and the influence of annealing and orientation was investigated to study whether the barrier properties can be improved. The possibility to use LCP as cost-effective lining for FRP was explored. Special focus was put on the diffusion of water and its effect on long-term transport properties and stability of thermoset resins as the performance of FRP is strongly related to the diffusion of water. The results showed that Vectra A950 was suitable for organic solvent and non-oxidising acid environments. Its transport properties were gravimetrically determined and found to be 10 to 102 times lower than that of a high barrier fluoropolymer of type FEP. The degree of molecular packing increased with annealing time both below and above the melting point. Below the melting point this was – at least – partly due to crystal formation whereas above the melting point other mechanisms were involved. The effects of annealing and orientation on the transport properties in LCP were, however, very small or not significant and probably significantly longer annealing times are required. LCP has potential to be used as lining material for FRP as the use of an LCP-lining substantially reduced the permeability of and the solute sorption in a bisphenol A epoxy-based vinyl ester resin. The bonding strength was improved significantly by a combined abrasive and oxygen plasma treatment. The long-term sorption of water in thermoset resins including bisphenol A epoxy-based vinyl ester, novolac-based vinyl ester, urethane modified vinyl ester and bisphenol A polyester resins was found to increase with exposure time whereas the diffusion coefficient was not significantly affected. It was shown that the presence of water induced relaxation processes that were considered to be the primarily reason for the increase in sorption coefficient in comparison to degradation processes, such as hydrolysis, causing osmotic processes. A general relationship for the estimation of the sorption coefficient at 80ºC in dependence of the water activity and the sorption coefficient at unit activity independent of the resin type was established.

Chromonic liquid crystals are a relatively new class of lyotropic liquid crystals. In an effort to understand this lyotropic phase better, studies on the phase behavior, defects formed in these systems and characterization of the order were performed. We studied three chromonic liquid crystal materials in nematic and biphasic regions: Sunset Yellow FCF (SSY, a food dye), a cationic perylene diimide derivative (PDI, a conducting dye) and cromolyn sodium (DSCG, a drug). For SSY chromonics in the nematic region, order parameters ( and ) were obtained by polarized Raman measurements. Using the order parameters the flow behavior was predicted and was found to be non-flow aligning. A comprehensive viscoelastic property set of SSY chromonics was obtained by studying the statics and dynamics of defects during the formation of planar aligned monodomain. Applications of PDI thin films as vapor sensors were explored; anisotropic electronic properties of oriented PDI films show good conductivity along the columns presumably arising from the overlap between the ? systems. In the biphasic region, growth and fluctuation of SSY tactoids and interesting patterns of biphasic DSCG under capillary geometry were observed; elastic properties and surface tension were estimated based on the shape of DSCG tactoids. Polymer dispersed lyotropic chromonic liquid crystals with different drop shapes and director configurations were also fabricated using various water-soluble polymers.

Dans cette thèse, l'interaction entre les grains colloïdaux avec une ligne de disclinaison dans un cristal liquide nématique est explorée. Deux types de colloïdes ont été utilisés; sphérique (billes de silice) et allongé (nanotubes de carbone). En plus, différents types d'ancrage sur leur surface sont obtenus; planaire, homéotrope, et Janus (moitié planaire - moitié homéotrope). Ces paramètres ont été modifiés dans le but d'examiner et d'évaluer la force nématique agissant entre les grains colloïdaux et la ligne de disclinaison, qui est le résultat de l'interaction élastique entre les deux. Cette force est de l'ordre du pico-Newton et capable d'attirer et de fixer les colloïdes dispersés dans le cristal liquide nématique sur la ligne de disclinaison. Une fois que les colloïdes sont fixés sur la ligne de disclinaison, ils peuvent être collés ensemble par électropolymérisation de pyrrole. Ce qui donne lieu à un nanofil conducteur en 3 dimensions, qui est auto-assemblé et auto-connecté à des électrodes prédéfinies à l'intérieur du cristal liquide nématique. / Throughout this thesis, the interaction between the colloidal grains with a disclination line in a nematic liquid crystal is explored. Two types of colloids were used; spherical (silica beads) and elongated (carbon nanotubes). In addition different types of anchoring conditions on their surface is obtained; planar, homeotropic, and Janus (half planar – half homeotropic). These parameters were varied in the aim to examine and evaluate the nematic force acting between the colloidal grains and the disclination line, which is a result of the elastic interaction between the two respectively. This force is in the order of pico-newton, and capable of attracting and fixing the dispersed colloids, in the nematic liquid crystal, on the disclination line. Once the colloids are fixed on the disclination line, they can be glued together by means of electropolymerization of pyrrole. This gives rise to a 3 dimensional conductive nanowires, which are auto-assembled, and auto-connected to predesigned electrodes inside the nematic liquid crystal.

Gegenstand der Arbeit ist die Analyse der bei hohen Verformungsgraden in Werkstoffen durch kollektive Bewegung der Versetzungen entstandenen neuen Defektkonfigurationen, die auf der mesoskopischen Skala agieren. Diese so genannte Disklinationen rufen neben starken Gitterdehnungen auch erhebliche lokale Gitterrotationen hervor. Es wurde der Nachweis der Existenz der Disklinationen in plastisch verformten Kristallen geliefert sowie die qualitative und quantitative Analyse der Disklinationskonfigurationen und der Disklinationsstärke durchgeführt. Die Untersuchungen an stark verformten Ein- und Vielkristallen wurden mittels sowohl lokalen Methoden der Transmissions- (TEM, CBED) und Rasterelektronenmikroskopie (REM, EBSD) als auch der integralen Methoden der Röntgenstrukturanalyse (XRD) durchgeführt. Die Ergebnisse haben gezeigt, dass die Entwicklung der Zellblockstruktur mit erheblichem Anstieg der Desorientierungen und Versetzungsdichten in Versetzungswänden verbunden ist und durch die Bildung der Netzwerke von Disklinationen gefördert wird.

Submitted by Vasti Diniz (vastijpa@hotmail.com) on 2017-09-19T14:26:49Z No. of bitstreams: 1 arquivototal.pdf: 24337857 bytes, checksum: 4dcf09dcc5c804cc2b7b0de0feb30331 (MD5) / Made available in DSpace on 2017-09-19T14:26:49Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 24337857 bytes, checksum: 4dcf09dcc5c804cc2b7b0de0feb30331 (MD5) Previous issue date: 2013-03-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The Graphene is a two-dimensional(2-D) semiconductor crystal with null gap, where charge carriers behave as massless particles. In this speci c dynamics in the limit of low energies, the energy dispersion relation is linear, and this material can be described by massless Dirac equation contrasts with the semiconductors, for which the charge carriers are massive. In this framework, there is the problem of the electronic con nement in graphene because of tunneling. For overcome this di culty, is proposed a new model of quantum ring, based on Dirac oscillator and models of rings Tan-Inkson and Bakke- Furtado. From this new coupling, are obtainable the energy spectrum, persistent currents and positive spinors to a graphene sheet with / without topological defect type disclination by massless Dirac equation (2+1). / O grafeno e um cristal bidimensional(2-D) semicondutor com gap nulo, onde os portadores de cargas se comportam como part culas sem massa. Nesta din^amica espec ca, no limite de baixas energias, a rela c~ao de dispers~ao de energia e linear, sendo que este material pode ser descrito pela equa c~ao de Dirac sem massa contrastando com os semicondutores, cujos portadores de cargas t^em massa. Neste quadro, h a o problema do con namento eletr^onico no grafeno devido ao tunelamento. Para contornar esta di culdade, e proposto um novo modelo de anel qu^antico, baseado no oscilador de Dirac e nos modelos de an eis de Tan-Inkson e Bakke-Furtado. A partir desse novo acoplamento, s~ao obtidos o espectro de energia, as correntes persistentes e os espinores positivos para uma folha de grafeno com/sem defeito topol ogico do tipo desclina c~ao, via equa c~ao de Dirac (2+1) sem massa

No description available.

This thesis focuses on transport properties and durability of liquid crystalline polymers (LCP)and fibre reinforced plastics (FRP) with regard to application in industrial process equipment.In the first part of the study the possibility of using a thermotropic LCP of type Vectra A950as lining material for FRP process equipment was investigated. Its performance wascompared to that of a fluorinated ethylene propylene copolymer (FEP) with respect tochemical and permeation resistance. Transport property and chemical resistance data wereestablished for different types of LCP film (compression molded, uniaxially and biaxiallyoriented film) exposed to selected chemicals chosen to represent typical industrial processenvironments. Annealing of the LCP, which may reduce the disclination density and henceimprove the barrier properties, induced a crystallinity increase, but did not significantlyimprove the barrier and chemical resistance properties. Different surface treatments toincrease the bonding between the LCP and FRP were explored. The conclusion was that LCPhas potential to serve as lining material for FRP in contact with water, organic solvents andnon-oxidizing acid environments, although certain issues, such as jointing techniques, stillhave to be evaluated. The second part of the study focused on transport and long-termproperties of commercial thermoset and FRP materials for industrial process equipment inaqueous environments (50 – 95 °C, water activity 0.78 – 1, exposure time ≤ 1000 days). Thewater transport properties in different thermosets were related to their chemical structureusing the solubility parameter concept. The transport of water in the thermosets with differentchemical structures could be predicted from the water activity, regardless of the actual type ofionic or non-ionic solute in the solution. An empirical relationship, independent of boththermoset chemistry and temperature, was established to describe the water concentration inthe thermoset as a function of water activity and the water concentration in pure water. Inlong-term, the water concentration in the thermosets increased with exposure time. Thisseemed to be primarily related to stress relaxation processes induced by water absorption andcertain leaching effects. The effects of hydrolysis seemed to be small. The glass fibrereinforcement may to various extents affect the water transport properties by capillarydiffusion and additional absorption around fibre bundles. The extent of such processesseemed to depend on temperature, water activity and the type of thermoset and reinforcement.The present work may be a useful contribution to an increased understanding of water effectsand durability of FRP process equipment. However, open questions still remain for a morecomprehensive durability analysis. / QC20100629

Submitted by Vasti Diniz (vastijpa@hotmail.com) on 2017-09-18T13:45:16Z No. of bitstreams: 1 arquivototal.pdf: 1340608 bytes, checksum: 8cceaa9c73ae05a5a903b4b78e3fa6ba (MD5) / Made available in DSpace on 2017-09-18T13:45:16Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1340608 bytes, checksum: 8cceaa9c73ae05a5a903b4b78e3fa6ba (MD5) Previous issue date: 2010-04-15 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / It is presented a review on three subjects: the origin and nature of topological defects, the non-relativistic and relativistic quantum mechanics, and the gravitational and eletrostatic selfforces that emerge from a conical spacetime surrounding a cosmic string. After setting up this theoretical framework, it is studied the behavior of a charged particle in the presence of a cosmic string, parallel to an uniform, constant magnetic field, which may be used as a model to a primordial large-scale magnetic field that permeates the universe. The geometry of a negative disclination is taken into account, this being a typically condensed matter physics topological defect equivalent to a cosmic string, where a wedge of material is inserted into the lattice. We computed exactly, the topological and electrostatic influences on the particles energy spectrum, and the phase shift for the charged scalar particle scattered states. Switching to a flat-spacetime context, spherically symmetric systems were studied, solving exactly, Klein-Gordon and Dirac equations which describe a scalar particle subject to a Coulomb vector potential and scalar central potentials. / Apresentamos uma revisão sobre a origem e a natureza dos defeitos topológicos, que surgem a partir de transições de fase que podem ter ocorrido no início do processo de formação do universo; sobre a mecânica quântica não-relativística e relativística; e sobre as auto-forças gravitacional e eletrostática que emergem da topologia cônica do espaço-tempo gerado pela corda cósmica. Utilizando estas ferramentas, estudamos o movimento de uma partícula carregada na presença de uma corda cósmica, paralela a um campo magnético uniforme, de magnitude constante, que poderia servir de modelo para um campo magnético primordial. Também consideramos a geometria anti-cônica de uma desclinação negativa, defeito topológico análogo à corda cósmica estudado em matéria condensada. Calculamos, exatamente, a influência da topologia e do campo magnético no espectro de energia da partícula e encontramos o ângulo de mudança de fase para seus estados espalhados. No espaço-tempo plano, estudamos sistemas com simetria esférica e investigamos a dinâmica de uma partícula escalar, resolvendo, exatamente, as equações de Klein-Gordon e Dirac, considerando potenciais centrais.