Acrylonitrile were copolymerized with 2-ethylhexyl acrylate and hexyl acrylate via one step emulsion polymerization using ammonium persulfate (initiator), 1-dodecanthiol (chain transfer agent) and DOWFAX 8390 (surfactant) in the presence of water at about 68 0C. Poly (acrylonitrile-2ethylhexyl acrylate) and poly (acrylonitrile-hexyl acrylate) copolymers with three different comonomer composition (8, 12 and 16 molar percent) were prepared. FTIR and 1H-NMR were used in order to clarify the chemical structure of copolymers. The comonomer amount incorporated into copolymers was determined by using 1H-NMR spectra. The thermal behavior of copolymers was determined by DSC and TGA. Molecular weights of copolymers were determined by intrinsic viscosity (IV) measurements. IV measurements revealed that both poly (acrylonitrile-2ethylhexyl acrylate) and poly (acrylonitrile-hexyl acrylate) have sufficient molecular weight to form nanoporous filtration membranes. Nanoporous filtration membranes were prepared and tested for chromium (IV) removal. It was observed that chromium (VI) rejections of nanoporous filtration membrane were highly dependent on the concentration and the pH of the solutions. Almost complete removal (99, 9 percent Cr (VI)) rejection was achieved at pHs 2, 5 and 7 for solution containing 50 ppm, chromium (VI) with permeate flux within a range from 177 to 150 L/m2h at 689.5 kPa. Also, chemical structure, swelling ratios, sheet resistivity and fracture morphologies of the nanoporous filtration membrane were studied. It should be noted that the nanoporous filtration membranes were fouling resistant.

Les processus de lavage, et plus particulièrement l'utilisation de solutions chlorées, peuvent engendrer une dégradation prématurée des membranes de filtration d'eau. Alors que le marché des technologies membranaires en PVDF est en pleine expansion, peu de travaux portent sur l'étude de leur dégradation sur le long terme. Dans ce contexte, la thèse a porté sur l'étude du vieillissement de membranes de filtration commercialisées en PVDF. Les échantillons sont immergés dans une solution d'hypochlorite de sodium et l'effet du pH sur leur dégradation est approfondi. Les propriétés mécaniques, d'hydrophilie, les performances hydrauliques ainsi que la porosité sont étudiées. L'évolution des propriétés est mise en relation avec la structure chimique étudiée à différentes échelles : moléculaire, macromoléculaire et supramoléculaire. Cette approche n'a à ce jour jamais été utilisée dans le cas des membranes fibres creuses en PVDF. Les analyses en chromatographie d'exclusion stérique révèlent les modifications les plus importantes. La dégradation du PVDF des membranes se traduit par un phénomène prédominant de coupures de la chaîne principale du PVDF accompagné, dans une moindre mesure, d'un phénomène de réticulation. Les principales modifications sont constatées à des pHs inférieurs à 10 révélant la possible action conjointe des radicaux OH•, ClO• et Cl•. Le vieillissement d'une membrane PVDF additivée montre à la fois une dégradation du PVDF et une élimination des additifs. Alors que la membrane sans additif conserve une stabilité de ses propriétés, l'élimination des additifs entraine une évolution de la porosité et une propension au colmatage plus importante. Cependant, les membranes PVDF conservent des propriétés d'utilisation acceptables au regard des conditions extrêmes de vieillissement étudiées. / The cleaning processes, especially the use of chlorine solutions, may cause the untimely degradation of the water filtration membranes. While the market for PVDF membrane-based treatment technologies is rapidly expending, only few works deal with the study of their ageing on a long-term basis. In this context, this project focuses on the study of the ageing of two PVDF filtration membranes. Samples are immersed in a sodium hypochlorite solution and the effect of the chlorine solution pH is investigated. The properties of the membranes are characterized throughout the study by tensile tests, hydrophilicity, hydraulic performances and porosity analysis. The evolution of properties is related to the chemical structure of the membranes at a molecular, a macromolecular and a supramolecular scale. Until now, this approach has never been used in the case of PVDF membranes under chlorine conditions. The size exclusion chromatography analyses revealed the most important modifications. The degradation occurs mainly by chain scissions of the PVDF and crosslinking phenomenon in lesser extent. The main modifications occurred at pH less than 10 proving the joint action of OH•, ClO• and Cl• radicals. The ageing of the PVDF membrane containing additives showed at the same time the PVDF degradation and the elimination of the additives. Whereas the properties of the additive-free PVDF membrane were preserved, the elimination of additives led to a modification of the porosity and an increased fouling. However, even if the PVDF degradation is proved, the using properties of the PVDF membranes remain acceptable taking into consideration extreme conditions of ageing studied.

Submitted by Nadir Basilio (nadirsb@uninove.br) on 2017-08-04T21:21:18Z No. of bitstreams: 1 Sergio Yoshiyuki Nakamura.pdf: 4979450 bytes, checksum: 9478fa7c8bfae19cb13670a88d649473 (MD5) / Made available in DSpace on 2017-08-04T21:21:18Z (GMT). No. of bitstreams: 1 Sergio Yoshiyuki Nakamura.pdf: 4979450 bytes, checksum: 9478fa7c8bfae19cb13670a88d649473 (MD5) Previous issue date: 2017-02-22 / The current global water crisis makes awareness of the problem of its finiteness present in discussion, whether governmental, private, research, ecology or sustainability. The search for better forms of consumption and alternatives of treatment and production of reuse water is increasing importance and intensifying studies in those areas. The objective of this work was to analyze membrane filtration techniques for the treatment of sewage effluents generated by ETE, verifying the technical and economic feasibility of improving the quality of reuse water production in Brazil, specifically in the State of São Paulo, verifying the technical and economic viability. This state was selected because, in the years 2014 and 2015, it experienced an atypical drought that presented low rainfall indices that had not been counted for decades, resulting in a possible rationing of water for the population. An exploratory research was carried out about filter membranes and their applications and an on - site interview with the technical lider of a large sanitation company that produces reuse water from sanitary effluents with a quality 50% higher than required by the standards of potability using this technology. The results of this work indicated positive estimates for the investment in the use of filter membranes for the production of reuse water. Its cost in the plant was estimated at 0.10 R$ / m3 and the average sale price of 1,70 R$ / m3, allowing financial savings for the final consumer, in this case 90.26% / m3, and for the investor, according to those estimates, an attractive return on investment, with a payback of 7.31 years, for a 41-year contract. / A atual crise mundial de água faz com que a conscientização sobre o problema de sua finidade esteja presente em discussões, sejam elas governamentais, da iniciativa privada, de pesquisas, ecologia ou sustentabilidade. A busca por melhores formas de consumo e alternativas de tratamento e produção de água de reuso vem ganhando importância e intensificando os estudos nestas áreas. Este trabalho teve por objetivo analisar as técnicas de filtragem por membranas para tratamento dos efluentes de esgoto sanitário gerados por Estação de Tratamento de Esgoto (ETE), verificando a viabilidade técnica e econômica na melhoria da qualidade da produção de água de reuso no Brasil, especificamente no Estado de São Paulo. Este Estado foi selecionado porque, nos anos de 2014 e 2015, passou por uma estiagem atípica que apresentou reduzidos índices pluviométricos não contabilizados há décadas, resultando em um possível racionamento de água para a população. Foi realizada uma pesquisa exploratória sobre membranas filtrantes e suas aplicações e uma entrevista in loco com o responsável técnico de uma grande empresa de saneamento, que produz água de reuso á partir de efluentes sanitários com uma qualidade 50% superior ao exigido pelos padrões de potabilidade, utilizando esta tecnologia. Os resultados deste trabalho indicaram estimativas favoráveis para o investimento na utilização de membranas filtrantes para a produção de água de reuso. O seu custo na planta foi estimado em 0,10 R$ / m3 e o preço médio de venda de 1,70 R$ / m3, permitindo economia financeira para o consumidor final, neste caso de 90,26 % / m3, e para o investidor, por estas estimativas, um retorno de investimento atrativo, com payback em 7,31 anos, para um contrato de 41 anos.

Made available in DSpace on 2014-12-17T14:08:54Z (GMT). No. of bitstreams: 1 AliDGK_DISSERT.pdf: 1533034 bytes, checksum: 5570fc0acd3b2b8bab1dc04b3e8c619f (MD5) Previous issue date: 2014-01-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Modeling transport of particulate suspensions in porous media is essential for understanding various processes of industrial and scientific interest. During these processes, particles are retained due to mechanisms like size exclusion (straining), adsorption, sedimentation and diffusion. In this thesis, a mathematical model is proposed and analytical solutions are obtained. The obtained analytic solutions for the proposed model, which takes pore and particle size distributions into account, were applied to predict the particle retention, pore blocking and permeability reduction during dead-end microfiltration in membranes. Various scenarios, considering different particle and pore size distributions were studied. The obtained results showed that pore blocking and permeability reduction are highly influenced by the initial pore and particle size distributions. This feature was observed even when different initial pore and particle size distributions with the same average pore size and injected particle size were considered. Finally, a mathematical model for predicting equivalent permeability in porous media during particle retention (and pore blocking) is proposed and the obtained solutions were applied to study permeability decline in different scenarios / A modelagem do transporte de suspens?es em meios porosos ? essencial para o entendimento de diversos processos de interesse industrial e cient?fico. Durante esses processos as part?culas podem ser retidas devido a diferentes mecanismos, dos quais citamos: exclus?o pelo tamanho, adsor??o, sedimenta??o e difus?o. Neste trabalho, um modelo matem?tico para o mecanismo de exclus?o pelo tamanho foi proposto e solu??es anal?ticas foram encontradas. As solu??es anal?ticas para o modelo proposto, que incorpora as distribui??es de tamanho de poros e de part?culas, foram utilizadas para prever a reten??o de part?culas, o bloqueio de poros e a redu??o de permeabilidade durante a microfiltra??o direta (dead-end microfiltration) em membranas. Foram analisados diversos cen?rios, considerando diferentes distribui??es de tamanho de poros e de part?culas. Os resultados obtidos mostraram que o processo de bloqueio de poros e redu??o de permeabilidade ? fortemente influenciado pelas distribui??es iniciais de tamanho de poros e de part?culas. Esta caracter?stica foi observada mesmo quando diferentes distribui??es iniciais de tamanho de poros e de part?culas com um mesmo tamanho m?dio de part?culas e de poros foi considerado. Finalmente, um modelo matem?tico para a previs?o da permeabilidade equivalente em meios porosos durante a reten??o de part?culas (e bloqueio de poros) foi proposto e as solu??es obtidas foram aplicadas para o estudo do decl?nio da permeabilidade em diferentes cen?rios / 2020-01-01

La caractérisation des propriétés électriques et diélectriques des membranes d’UF et de NF constitue une étape essentielle pour la compréhension de leurs performances de filtration. Une nouvelle approche a été développée pour déterminer les propriétés diélectriques d’une membrane de NF par spectroscopie d’impédance. Celle-ci repose sur l’isolement de la couche active du support membranaire et sur l’utilisation de mercure comme matériau conducteur, ce qui nous a permis de prouver que la constante diélectrique de la solution à l’intérieur des nanopores est inférieure à celle de la solution externe. Deux configurations de cellule (fibres immergées dans la solution d’étude ou fibres noyées dans un gel isolant) ont été étudiées pour la réalisation de mesures électrocinétiques tangentielles sur fibres creuses et la solution autour des fibres s’est avérée influencer à la fois le courant d’écoulement et la conductance électrique de la cellule. De plus, la contribution importante du corps poreux des fibres au courant d’écoulement ne permet pas de convertir cette grandeur en potentiel zêta luminal. Les propriétés intéressantes de ces membranes ont finalement été mises à profit pour décontaminer des solutions contenant des ions métalliques. Les performances de dépollution, en termes de rétention des polluants et d’impact écotoxicologique, ont été étudiées sur des solutions synthétiques et un rejet issu de l’industrie du traitement de surface. Bien que les performances de rétention aient été remarquables, la toxicité de l’effluent réel n’a pu être totalement annihilée. Une étude approfondie de la rétention des polluants non métalliques s’avère donc nécessaire. / The characterization of electrical and dielectric properties of UF and NF membranes is an essential step to understand their filtration performance. A new approach has been developed to determine the dielectric properties of a NF membrane by impedance spectroscopy. This is based on the isolation of the membrane active layer and the use of mercury as conductive material, which allowed us to prove that the dielectric constant of the solution inside nanopores is lower than that of the external solution. Two cell configurations (fibers immersed in the solution or fibers embedded in an insulating gel) were investigated for the implementation of tangential electrokinetic measurements with hollow fibers and the solution around the fibers was found to influence both streaming current and cell electrical conductance. Moreover, the important contribution of the fiber porous body to the streaming current does not allow the conversion of the latter to luminal zeta potential. The advantageous properties of these membranes were finally used to decontaminate solutions containing metal ions. Decontamination performances in terms of both pollutant retention and ecotoxicological impact were studied on synthetic solutions and a discharge water from surface treatment industry. Although retention performances were remarkable, the toxicity of the real effluent could not be totally annihilated. A thorough study of the retention of non-metallic contaminants is thus required.