Made available in DSpace on 2014-12-17T14:06:57Z (GMT). No. of bitstreams: 1 SheylaKJM_DISSERT.pdf: 2022444 bytes, checksum: 199284d45ddc8db628d0e2f45da9a7e8 (MD5) Previous issue date: 2011-01-17 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The present work is to study the characteristics and technological properties of soil-cement bricks made from binary and ternary mixtures of Portland cement, sand, water, with or without addition of gravel from the drilling of oil wells, which could be used by industry, aiming to improve its performance and reduce cost by using the residue and, consequently, increasing its useful life. The soil-cement bricks are one of the alternatives to masonry construction. These elements, after a short curing period, provide compressive strength similar to that of solid bricks and ceramic blocks, and the higher the resistance the higher the amount of cement used. We used the soil from the city of S?o Jos? do Mipibu / RN, the banks of the River Baldun, cement CPIIZ-32 and residue of drill cuttings from oil wells drilling onshore wells in the town of Mossley, RN, provided Petrobras. To determine the optimum mix, we studied the inclusion of different residues (100%, 80%, 70%, 60% and 50%) where 15 bodies were made of the test piece. The assessment was made of bricks made from simple compression tests, mass loss by immersion and water absorption. The experimental results proved the efficiency and high utilization of the waste from the drilling of oil wells, making the brick-cement-soil residue with a higher strength and lower water absorption. The best result in terms of mechanical strength and water absorption for the ternary mixture was 10% soil, 14% cement and 80% residue. In terms of binary mixtures, we obtained the best result for the mix-cement residue, which was 14% cement incorporated in the residue / O presente trabalho consiste no estudo das caracter?sticas e propriedades tecnol?gicas de tijolos solo-cimento formulados a partir de misturas bin?rias e tern?rias de cimento Portland, areia, ?gua, com e sem adi??o de cascalho proveniente da perfura??o de po?os de petr?leo, que poder?o ser utilizados pela ind?stria, com o objetivo de melhorar seu desempenho e diminuir seu custo utilizando o res?duo e, conseq?entemente, aumentando sua vida ?til. Os tijolos de solo-cimento constituem uma das alternativas para a constru??o em alvenaria. Esses elementos, ap?s pequeno per?odo de cura, garantem resist?ncia ? compress?o simples similar ? dos tijolos maci?os e blocos cer?micos, sendo a resist?ncia tanto mais elevada quanto maior for ? quantidade de cimento empregada. Foi utilizado o solo proveniente do Munic?pio de S?o Jos? do Mipib?/RN, as margens do Rio Baldun, cimento CPIIZ-32 e res?duo de cascalho de perfura??o de po?os de petr?leo proveniente da perfura??o de po?os Onshore, no munic?pio de Mossor?/RN, fornecido pela Petrobras. Para a determina??o da mistura ?tima, estudou-se a inclus?o de teores de res?duos diferenciados (100%; 80%; 70%; 60% e 50%) onde foram confeccionados 15 corpos-de-prova. A avalia??o dos tijolos confeccionados foi feita a partir de ensaios de compress?o simples, perda de massa por imers?o e absor??o de ?gua. Os resultados experimentais comprovaram a efici?ncia e o elevado potencial de utiliza??o do res?duo proveniente da perfura??o de po?os de petr?leo, tornando o tijolo de solo-cimento-res?duo com uma maior resist?ncia mec?nica e menor absor??o de ?gua. O melhor resultado, em termos de resist?ncia mec?nica e absor??o d ?gua, para a mistura tern?ria, foi de 10% de solo, 14% de cimento e 80% de res?duo. Em termos de misturas bin?rias, obteve-se o melhor resultado para a combina??o cimento-res?duo, que foi de 14% de cimento incorporado no res?duo

Made available in DSpace on 2014-12-17T14:06:58Z (GMT). No. of bitstreams: 1 JaqueligiaBS_Capa_ate_referencias.pdf: 4148676 bytes, checksum: c08764d974461ebcf86494a06a296078 (MD5) Previous issue date: 2008-10-08 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In building, during the implementation process of major or even minor works, there is a considerable waste of plaster in the steps of coating, making it is a negative factor because of the loss of these processes constructive remains incorporated into buildings, as component, whose final dimensions are higher than those projected. Another negative factor is the disposal of waste gypsum in inappropriate places, thus contributing to the degradation of environmental quality, due to the leaching of this waste and may trigger the formation of sulfuric acid. Therefore, based on this picture, processing and reuse of waste coating, combined with the ceramics industry, which is a strong potential in the reuse of certain types of waste, promote mutual benefits. Thus the overall objective of this work is to conduct a search with scientific and technological aspects, to determine the effect of the incorporation of the residue of plaster for coating, from the building, the formulation of bodies for red ceramic. The residue of plaster coating was collected and characterized. They were also selected raw materials of two ceramic poles of the state of Rio Grande do Norte and formulations have been made with the intention of obtaining those with the best physical and mechanical properties, the residue was added the percentage of 5%, 10%, 15%, 20%, 25% and 30%, in the best formulation of ceramic industry 1 and, according the properties analyses, 5%, 10% and 15% as the best results of ceramic industry 2. The samples were sintered at temperatures of 850 ?C, 950 ?C and 1050 ?C, the heating rate of 5 ?C / min with isotherm of two hours. They were submitted to testing technology, such as lineal shrinkage, water absorption, apparent porosity, apparent density and bending resistence. The residue incorporation best results in the formulations of mass in red ceramic, were observed between the temperatures of 850 ?C and 950 ?C, in those formulations that have illite clays and medium plastic in their composition, in the range of 0% to 15% residue incorporated / Na constru??o civil, durante o processo de execu??o de grandes ou at? mesmo pequenas obras, h? um desperd?cio consider?vel de gesso nas etapas de revestimento, tornando-se este um fator negativo, pois parte das perdas destes processos construtivos permanece incorporada nas constru??es, na forma de componentes, cujas dimens?es finais s?o superiores ?quelas projetadas. Outro fator negativo ? a disposi??o dos res?duos de gesso em locais inadequados, contribuindo assim para a degrada??o da qualidade ambiental, devido ao processo de lixivia??o deste res?duo, podendo desencadear na forma??o de ?cido sulf?rico. Baseado neste panorama, a transforma??o e o reaproveitamento dos res?duos de revestimento, aliada ? ind?stria da cer?mica, que ? um forte potencial no reaproveitamento de alguns tipos de res?duos, promoveria benef?cios m?tuos. O objetivo geral deste trabalho foi de realizar uma pesquisa com aspectos cient?ficos e tecnol?gicos, para verificar o efeito da incorpora??o do res?duo de gesso para revestimento, proveniente da constru??o civil, na formula??o de massas para cer?mica vermelha. As mat?rias-primas foram coletadas de dois p?los cer?micos do Estado do Rio Grande do Norte e formuladas com o intuito de obter aquelas com as melhores propriedades f?sicas e mec?nica, tendo sido incorporados os percentuais 5%, 10%, 15%, 20%, 25% e 30% de res?duo, na melhor formula??o da ind?stria cer?mica 1 e, de acordo com a an?lise dos seus resultados, de 5%, 10% e 15% na melhor formula??o da ind?stria cer?mica 2. As amostras foram sinterizadas ?s temperaturas de 850 ?C, 950 ?C e 1050 ?C, ? taxa de aquecimento de 5 ?C/min com isoterma de duas horas e submetidas a ensaios tecnol?gicos, como retra??o linear de queima, absor??o de ?gua, porosidade aparente, massa espec?fica aparente e resist?ncia mec?nica ? flex?o. Os melhores resultados de incorpora??o do res?duo nas formula??es de massa de cer?mica vermelha foram observados na faixa de temperatura de 850 ?C a 950 ?C, naquelas que possuem argilas il?ticas e medianamente pl?sticas em sua composi??o, na faixa de 0% a 15% de res?duo incorporado

Made available in DSpace on 2014-12-17T14:06:58Z (GMT). No. of bitstreams: 1 LuizCFS.pdf: 3453741 bytes, checksum: a917d4da21cccce053bc103345ba7ee6 (MD5) Previous issue date: 2008-07-10 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This research is about the use of the coconut?s endocarp (nucifera linn) and the waste of derivatives of wood and furniture as raw material to technological use. In that sense, the lignocellulosic waste is used for manufacture of homogeneous wood sheet agglomerate (LHWS) and lignocellulosic load which take part of a polymeric composite with fiber glass E (GFRP-WC). In the manufacturing of the homogeneous wood sheet agglomerate (LHWS), it was used mamona?s resin as waste s agglutinating element. The plates were taken up in a hydraulic press engine, heated, with temperature control, where they were manufactured for different percentage of waste wood and coconuts nuc?fera linn. Physical tests were conducted to determine the absorption of water, density, damp grade (in two hours and twenty-four hours), swelling thickness (in two hours and twenty-four hours), and mechanical tests to evaluate the parallel tensile strength (internal stick) and bending and the static (steady) flexural. The physical test?s results indicate that the LHWS can be classified as bonded wood plate of high-density and with highly water resistant. In the mechanical tests it was possible to establish that LHWS presents different characteristics when submitted to uniaxial tensile and to the static (steady) flexural, since brittle and elasticity module had a variation according to the amount of dry endocarp used to manufacture each trace of LHWS. The GFRP-WC was industrially manufactured by a hand-lay-up process where the fiber glass E was used as reinforcement the lignocellul?sic?s waste as load. The matrix was made with ortofitalic unsaturated polyester resin. Physical and mechanical tests were performed in presence of saturated humidity and dry. The results indicated good performance of the GFRP-WC, as traction as in flexion in three points. The presence of water influenced the modules obtained in the flexural and tensile but there were no significant alteration in the properties analyzed. As for the fracture, the analysis showed that the effects are more harmful in the presence of damp, under the action of loading tested, but despite this, the fracture was well defined starting in the external parts and spreading to the internal regions when one when it reaches the hybrid load / Na presente pesquisam-se a utiliza??o do endocarpo do cocos nuc?fera linn e o res?duo de derivados de madeira e de m?veis como mat?ria-prima para uso tecnol?gico. Nesse sentido, usam-se esses res?duos lignocelul?sico na fabrica??o de chapa de madeira aglomerada homog?nea (CHMC) e, como carga, em comp?sito polim?rico refor?ado com fibra de vidro E (PHFV-MC). Na fabrica??o da chapa de madeira aglomerada homog?nea (CHMC) usou-se a resina ? base de mamona como elemento aglutinante dos res?duos. As chapas foram conformadas em uma prensa hidr?ulica aquecida com controle de temperatura, onde as mesmas foram fabricadas para diferentes percentuais dos res?duos de madeira e do cocos nuc?fera linn. Foram realizados ensaios f?sicos para a determina??o de absor??o de ?gua, densidade, do teor de umidade (em duas horas e vinte e quatro horas), inchamento de espessura (em duas horas e vinte e quatro horas), e ensaios mec?nicos para a determina??o da resist?ncia ? tra??o paralela (ades?o interna) e o ensaio de flex?o est?tica. Os resultados obtidos nos ensaios f?sicos indicam que a CHMC pode ser classificada como chapa de madeira aglomerada de alta densidade e que suporta bem a presen?a de ?gua. Nos ensaios mec?nicos foi poss?vel constatar que a CHMC apresenta caracter?sticas distintas quando submetida ? for?a de tra??o uniaxial e ? flex?o est?tica, uma vez que os m?dulos de ruptura e de elasticidade variaram em fun??o da quantidade do endocarpo seco usado para fabricar cada tra?o da CHMC. A PHFV-MC foi fabricada industrialmente por meio do processo hand-lay-up onde a fibra de vidro-E foi usada como refor?o e os res?duos lignocelul?sicos, como carga. A matriz foi ? base de resina poli?ster ortofit?lica insaturada. Foram realizados ensaios f?sicos e mec?nicos em presen?a de umidade saturada e a seco. Os resultados indicaram um bom desempenho da PHFV-MC, tanto na tra??o quanto na flex?o em tr?s pontos. A presen?a de ?gua influenciou os m?dulos obtidos na flex?o e na tra??o, mas n?o alterou significativamente as propriedades analisadas. Quanto ? fratura, a an?lise mostrou que os efeitos s?o mais danosos em presen?a da umidade, sob a a??o dos carregamentos analisados, mas, apesar disto, a fratura se mostrou bastante caracterizada, iniciando nas regi?es externas e se propagando para as regi?es internas quando atinge a carga h?brida

Apesar de o direito ser feito para trazer estabilidade à sociedade e garantia a seus membros, hoje em dia no Brasil esse propósito não se verifica adequadamente como deveria. Este trabalho se concentra na segurança jurídica, uma expressão no direito romanogermânico que contém a idéia de como o direito deve dar ao povo um sentido de certeza e também embasa a coisa julgada e o controle de constitucionalidade. Na verdade, o sentido de estabilidade no direito brasileiro está em crise. Este estudo procura saber o motivo e tenta achar uma resposta na doutrina e nas decisões do Supremo Tribunal Federal para entender como isso afeta a coisa julgada e o controle de constitucionalidade. A conclusão leva à idéia de que o modelo de controle difuso de constitucionalidade sem a vinculação obrigatória dos precedentes, combinado com um enfoque no controle concentrado e abstrato de constitucionalidade é a causa de vários problemas, afetando não apenas o conceito de coisa julgada mas também trazendo danos à segurança jurídica. / Altough law is made to bring stability to the society, and assurance for its members, nowadays in Brazil its purpose is not occurring properly and as it should do. This work focuses on legal security, a term in civil law that contains the idea of how law must give people a sense of certainty, and also supports the res judicata and judicial review. Actually, the sense of stability in Brazilian law is in crisis. This study wonders why and tries to find an answer in jurisprudence and in the Supremo Tribunal Federal (Brazilian supreme court) decisions to understand how it affects the institutes of res judicata and judicial review. The conclusion leads to the idea that a judicial review model without stare decisis combined with the classic civil law constitutional court is the cause of several problems, affecting not only the concept of res judicata but also damaging the legal security.

In this thesis, the common law crime of obstructing or defeating the course of justice as currently applied in South African law, is considered critically. The purpose of the study is to determine whether the ambit of the crime should be extended to target all conduct which undermines the proper administration of justice in South Africa. The interests protected by the crime are investigated, and those important constitutional values which underpin the crime, are identified. These values are: (i) constitutional supremacy (ii) the rule of law (iii) the doctrine of separation of powers, and (iv) the independence of the courts. In a post-constitutional era, the question raised is whether the crime as developed in the common law adequately protects these important democratic values. The historical background and development of the offence are discussed. This is followed by a comparative legal study which considers the existence and ambit of the offence in certain foreign jurisdictions. The foreign legal systems considered are England, Australia, Canada and the United States of America. The study reveals that the crime has been codified in most of these jurisdictions. Codification was driven by the need for legal certainty and compliance with constitutional imperatives. The study concludes that similar reform is necessary in South African criminal law. It is recommended that the common law offence of obstructing or defeating the course of justice be repealed and replaced with a comprehensive statutory offence which criminalises all manifestations of conduct which are intended to defeat or obstruct the proper administration of justice. The proposals are based upon the identified constitutional imperatives which underpin the crime. It is argued that the legislature is the proper institution to initiate reform in this regard. Detailed recommendations are made, which include draft legislation. / Law / LL.D.

O advento da Lei n 9.868/99 alterou significativamente o sistema de controle de constitucionalidade brasileiro, importante instrumento de defesa da manutenção do Estado Democrático de Direito, com a quebra do dogma da nulidade dos atos inconstitucionais, e a autorização expressa da modulação dos efeitos das declarações de inconstitucionalidade. A pesquisa realizou análises qualitativa e quantitativa, mediante levantamento de dados correspondentes a 1.232 acórdãos de julgamento de mérito proferidos pelo plenário do Supremo Tribunal Federal, entre os anos de 1988 a 30 de junho de 2013, em sede de controle abstrato de constitucionalidade. O objetivo foi identificar se há influência político partidária na modulação de efeitos da declaração de inconstitucionalidade, identificando os fatores externos e internos que interferiram nos julgados estudados. A pesquisa avaliou as amostras disponibilizadas nas listagens de estatísticas de ações de controle abstrato de constitucionalidade, existente no site do Supremo Tribunal, o que permitiu localizar cada ação julgada em seu mérito, e consultar voto a voto. A pesquisa descobriu que, entre 1988 a 2013, 18 (dezoito) casos tiveram indeferimento expresso do pedido de modulação, e 37 (trinta e sete) acórdãos acolheram a alteração da eficácia pro futuro, ex nunc ou em data prefixada, correspondendo a 4,5% dos processos julgados no mérito. O trabalho classificou os dados quanto ao prazo modulado, os beneficiários e o objeto das modulações. Dos 37 (trinta e sete) casos identificados com modulação, a pesquisa diagnosticou 13 (treze) com fortes indícios de influência político partidária. Os votos mostraram também outros fatores de interferência: influência interna pelos pares na Corte, questões sociais e econômicas (metódica estruturante do direito), e até a busca ainda que eventual pela coerência decisória com outro precedente (teoria da integridade de Dworkin). Em todos os treze julgados, os pedidos de modulação foram formulados por chefe do Poder Executivo Estadual ou Federal. Em 7 (sete) casos houve retificação de votos para aderir à modulação consensualmente debatida. Em todos os casos, havia discussão de fatores econômico- financeiros que envolviam erário. O estudo comparou os valores encontrados com a doutrina constitucional estrangeira e a experiência jurisprudencial da Áustria, dos Estados Unidos e da Alemanha, que influenciaram direta ou indiretamente o sistema constitucional pátrio. Essa análise descreveu as semelhanças e as diferenças na composição e na funcionabilidade da Corte, bem como as espécies, extensão e efeitos das decisões de inconstitucionalidade. Comprovou-se a hipótese problematizada na pesquisa, quanto à ocorrência de influência político-partidária, o que ocorre também nos tribunais estrangeiros, cuja composição é determinada pelo Parlamento ou pelo Chefe do Executivo, mas sem que essa influência tivesse o caráter exclusivo na determinação da modulação de efeitos da sentença de inconstitucionalidade. Conclui-se que, no Brasil, a escolha de 8 (oito) dos 11 (onze) ministros por um mesmo partido foi determinante para que a Corte sofresse influência político-partidária ao longo dos anos. A possibilidade de modulação da inconstitucionalidade interfere diretamente nas políticas públicas implantadas pelos governos estaduais e federal, o que agrava a pressão política sofrida pelos julgadores. Como a modulação utiliza conceitos indeterminados de segurança jurídica e relevante interesse social, ainda que se tenha constatado tantas influências externas ao sistema positivado, o anseio social exige o cumprimento dos limites mínimos previstos no próprio sistema para o preenchimento dessa "textura aberta da norma", para evitar arbitrariedades.

Apesar de o direito ser feito para trazer estabilidade à sociedade e garantia a seus membros, hoje em dia no Brasil esse propósito não se verifica adequadamente como deveria. Este trabalho se concentra na segurança jurídica, uma expressão no direito romanogermânico que contém a idéia de como o direito deve dar ao povo um sentido de certeza e também embasa a coisa julgada e o controle de constitucionalidade. Na verdade, o sentido de estabilidade no direito brasileiro está em crise. Este estudo procura saber o motivo e tenta achar uma resposta na doutrina e nas decisões do Supremo Tribunal Federal para entender como isso afeta a coisa julgada e o controle de constitucionalidade. A conclusão leva à idéia de que o modelo de controle difuso de constitucionalidade sem a vinculação obrigatória dos precedentes, combinado com um enfoque no controle concentrado e abstrato de constitucionalidade é a causa de vários problemas, afetando não apenas o conceito de coisa julgada mas também trazendo danos à segurança jurídica. / Altough law is made to bring stability to the society, and assurance for its members, nowadays in Brazil its purpose is not occurring properly and as it should do. This work focuses on legal security, a term in civil law that contains the idea of how law must give people a sense of certainty, and also supports the res judicata and judicial review. Actually, the sense of stability in Brazilian law is in crisis. This study wonders why and tries to find an answer in jurisprudence and in the Supremo Tribunal Federal (Brazilian supreme court) decisions to understand how it affects the institutes of res judicata and judicial review. The conclusion leads to the idea that a judicial review model without stare decisis combined with the classic civil law constitutional court is the cause of several problems, affecting not only the concept of res judicata but also damaging the legal security.

The thesis entitled "Pushing the Limits of NMR Sensitivity and Chiral Analysis: Design of New NMR Methods and Bio-molecular Tools" consists of six chapters. The research work reported in this thesis is focused on the development of novel chemical and NMR methodological approaches for enantiomeric analysis and mea- surement of residual dipolar couplings (RDCs), and the development of sensitivity enhanced slice selective NMR experiments for obtaining pure shift 1H spectra and the measurement of scalar couplings. The thesis is divided into two parts. The Part I comprises chapters 2-4, where the enantiomeric analysis is discussed, which includes newly developed chiral reagents, two new weak chiral aligning media and design of novel NMR techniques. Part II comprises chapters 5 and 6, which discusses new sensitivity enhanced slice selective NMR techniques. Chapter 1 gives a general introduction to NMR and the problems investigated in the remaining chapters of the thesis. The chapter starts with a brief discussion on the introduction, advancements and general applications of NMR, discussion is also given on the NMR approaches for enantiomeric analysis both in isotropic and anisotropic phases and the measurement of RDCs, including the benefits and limitations associated with each approach. The chapter sets the tone by discussing limitations of the existed NMR enantiomeric approaches and slice-selective techniques, and builds the bridge for the rest of the chapters by addressing these limitations. The chapter also introduces slice selective experiments, their benefits over other conventional methods and limitations. Additional introductory notes are also given on some related concepts. Part I : NMR Chiral analysis and RDCs measurements Chapter 2 discusses chiral sensing properties of RNA nucleosides and their utility as chiral derivatizing agents for the enantio-discrimination of 1o-amines using one dimensional 1H NMR. A three component protocol has been proposed for the complexation of nucleosides with amines, which is rapid, economical and provides maximum diastereomeric conversion. The chiral differentiating ability of nucleosides are examined for different amines based on the 1H NMR chemical shift differences between the diastereomers (∆δ R, S ). Enantiomeric differentiation has been observed at multiple chemically distinct proton sites. It is observed that adenosine and guanosine exhibit large chiral differentiation (∆δ R, S ) due to the presence of a purine ring. The comparison of the diastereomeric excess (de) measured by NMR with those of the gravimetrically prepared ratios are in excellent agreement with each other confirming the robustness of these RNA nucleosides in discriminating primary amines. Chapter 3 establishes the smooth connectivity with the chapter 2 by discussing the limitations of the enantiomeric discrimination using NMR in isotropic solutions. This chapter discusses two new water compatible aligning media that were developed based on self-assembling strategy of small bio-molecules. The self-assembled folic acid, and the binary mixture of 50-GMP and guanosine are introduced as two novel weak aligning media. The properties of these low ordered media have been systematically studied for their easy preparation, physical parameter dependent tunability of their degree of alignment, mesosphere sustainability over a broad range of temperature and the concentration of the ingredients, and the phase reproducibility. The applications of both these new media are demonstrated for chiral and pro-chiral discrimination and also for the measurement of RDCs. Both these liquid crystalline media could be tuned to very low degree of alignment (order parameter of the order of 10−4), which provides simple first order spectra of molecules aligned in them, the analysis provide order dependent NMR spectral parameters. The 50-GMP:guanosine orienting medium can be prepared in less than 1 hour, and has been demonstrated to be an ideal medium for the determination of RDCs that are used as restraints in the structure calculations of small molecules. Chapter 4 describes 1H NMR spectral complexity in isotropic and anisotropic phases and its consequences on enantiomeric analysis. In circumventing such problems, new NMR techniques have been developed and the spin dynamics involved in the designed sequences are discussed. The newly developed 2D 1H NMR experimental method termed as RES-TOCSY, and its applicability for resolving R and S enantiomeric or diastereomeric peaks of all the coupled proton spins in isotropic phase is discussed. The utility of the developed method is demonstrated in diverse situations, such as, for suppressing impurities peaks, resolving the severely overlapped peaks and unraveling the peaks masked due to severe line broadening when metal complexes are used as chiral auxiliaries. The advantages and limitations of the method over other methods available in the literature are discussed and the significant advantage of the present method is illustrated by spectral comparison with J-resolved experiment. The appli- cation of the method for the accurate measurement of enantiomeric excess has also been demonstrated. The chapter also introduces another NMR experimental technique developed for resolving enantiomeric peaks and complete unraveling of R and S spectra in anisotropic phase. The developed 2D NMR method is cited in the literature as CH-RES-TOCSY. In addition to spectroscopic visualization of R and S spectra, the method also yields C-H RDCs. The applicability of the new experiment has been demonstrated on a chosen example. The wide utility of the method has also been demonstrated for the assignment of symmetric cis- and trans- isomers. Part II : Sensitivity Enhancement of Slice selective NMR Experiments Chapter 5 describes applications of slice selective NMR experiments over conven tional NMR methods and their limitations as far as the sensitivity of signal detection is concerned, especially in low concentrated samples. The chapter introduces the implementation of Acceleration by Sharing Adjacent Polarization (ASAP) technique in slice selective experiments. It is convincingly demonstrated that ASAP helps in reducing inter scan relaxation delay and consequently permits acquisition of more number of scans in a given time, resulting in the gain in signal enhancement by a factor of two. The pulse sequences have been suitably designed for obtaining the pure shift 1H spectra and in G-SERF experiment for the measurement of 1H-1H couplings, both with significantly enhanced signal intensities. Chapter 6 describes new sensitivity enhanced slice selective NMR methods for mea- surement of scalar couplings. A new experiment has been developed which is named as Quick G-SERF (QG-SERF). It is a 1D NMR slice selective method developed based on real time spin manipulation technique. The method gives multiple scalar couplings of a selected spin with simplified multiplets, which is analogous to the 2D G-SERF but with considerable saving in instrument time by 1-2 orders of magnitude. The rapidness of the experiment arises due to reduced dimensionality. The spin dynamics involved in the pulse sequence and its working principle have been described. The application of the method is illustrated for the measurement of 1H-1H couplings. The sequence has been further improved to obtain the heteronuclear couplings between two abundant spins in an orchestrated manner and has been demonstrated for measurement of 1H-19F couplings. This sequence cited as HF-QG-SERF has been implemented on the molecules containing number of chemically non-equivalent fluorine atoms.

Made available in DSpace on 2014-12-17T14:09:17Z (GMT). No. of bitstreams: 1 MarcilioPR_TESE.pdf: 2753388 bytes, checksum: 58b3cf541e2ed39d0ec5675d37151b31 (MD5) Previous issue date: 2014-02-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Petroleum evaluation is analyze it using different methodologies, following international standards to know their chemical and physicochemical properties, contaminant levels, composition and especially their ability to generate derivatives. Many of these analyzes consuming a lot of time, large amount of samples , supplies and need an organized transportation logistics, schedule and professionals involved. Looking for alternatives that optimize the evaluation and enable the use of new technologies, seven samples of different centrifuged Brazilian oils previously characterized by Petrobras were analyzed by thermogravimetry in 25-900? C range using heating rates of 05, 10 and 20?C per minute. With experimental data obtained, characterizations correlations were performed and provided: generation of true boiling point curves (TBP) simulated; comparing fractions generated with appropriate cut standard in temperature ranges; an approach to obtain Watson characterization factor; and compare micro carbon residue formed. The results showed a good chance of reproducing simulated TBP curve from thermogravimetry taking into account the composition, density and other oil properties. Proposed correlations for experimental characterization factor and carbon residue followed Petrobras characterizations, showing that thermogravimetry can be used as a tool on oil evaluation, because your quick analysis, accuracy, and requires a minimum number of samples and consumables / A avalia??o de petr?leo consiste em analis?-lo por diferentes metodologias, seguindo normas internacionais para conhecer suas propriedades qu?micas, f?sico-qu?micas, teor de contaminantes, composi??o e principalmente sua capacidade em gerar derivados. Muitas dessas an?lises s?o demoradas, consomem uma grande quantidade de amostras, insumos e precisam de uma organizada log?stica de transporte, cronograma de realiza??o e profissionais envolvidos. Para buscar alternativas que otimizem essa avalia??o e permitam a utiliza??o de novas tecnologias, sete amostras de diferentes petr?leos brasileiros centrifugados e caracterizados previamente pela Petrobr?s foram analisadas por termogravim?trica numa faixa de temperatura de 25 a 900?C utilizando raz?es de aquecimento de 05, 10 e 20?C por minuto. Com os dados obtidos experimentalmente, foram realizadas correla??es com as caracteriza??es disponibilizadas que permitiram: a gera??o de curvas de pontos de ebuli??o verdadeiros (Curva PEV) simulada; a compara??o entre as fra??es geradas com as devidas faixas de temperaturas de corte padr?o; uma aproxima??o para obter o fator de caracteriza??o de Watson; e comparar os res?duos de carbono micro. Os resultados mostraram uma boa possibilidade de reproduzir uma curva PEV simulada a partir da termogravimetria levando em considera??o a composi??o, densidade e outras propriedades do petr?leo; as correla??es propostas experimentalmente para o fator de caracteriza??o e res?duo de carbono acompanharam as caracteriza??es informadas pela Petrobr?s, mostrando que a termogravimetria pode ser utilizada como ferramenta na avalia??o de petr?leos, apresentando rapidez na an?lise, precis?o, al?m de necessitar de uma quantidade m?nima de amostras e insumos

Made available in DSpace on 2015-03-03T15:02:47Z (GMT). No. of bitstreams: 1 IzabellyLL_TESE.pdf: 7496453 bytes, checksum: d39fc896ff5d9d4982952835ef786c26 (MD5) Previous issue date: 2013-07-12 / The molecular distillation is show as an alternative for separation and purification of various kinds of materials. The process is a special case of evaporation at high vacuum, in the order from 0.001 to 0.0001 mmHg and therefore occurs at relatively lower temperatures, preserves the material to be purified. In Brazil, molecular distillation is very applied in the separation of petroleum fractions. However, most studies evaluated the temperature of the evaporator, condenser temperature and flow such variables of the molecular distillation oil. Then, to increase the degree of recovery of the fraction of the distillate obtained in the process of the molecular distillation was evaluated the use nonionic surfactants of the class of nonylphenol ethoxylate, molecules able to interact in the liquid-liquid and liquid-vapor interface various systems. In this context, the aim of this work was to verify the influence of commercial surfactant (Ultranex-18 an Ultranex-18-50) in the molecular distillation of a crude oil. The physicochemical characterization of the oil was realized and the petroleum shown an API gravity of 42?, a light oil. Initially, studied the molecular distillation without surfactant using star design experimental (2H ? ) evaluated two variables (evaporator temperature and condenser temperature) and answer variable was the percentage in distillate obtained in the process (D%). The best experimental condition to molecular distillation oil (38% distillate) was obtained at evaporator and condenser temperatures of 120 ?C and 10 ? C, respectively. Subsequently, to determine the range of surfactant concentration to be applied in the process, was determined the critical micellar concentration by the technique of scattering X-ray small angle (SAXS). The surfactants Ultranex-18 an Ultranex-18-50 shown the critical micelle concentration in the range of 10-2 mol/L in the hydrocarbons studied. Then, was applied in the study of distillation a concentration range from 0.01 to 0.15 mol/L of the surfactants (Ultranex- 18 and 50). The use of the nonionic surfactant increased the percentage of hydrocarbons in the range from 5 to 9 carbons in comparison to the process carried out without surfactant, and in some experimental conditions the fraction of light compounds in the distilled was over 700% compared to the conventional process. The study showed that increasing the degree of ethoxylation of Ultranex18 to Ultranex-50, the compounds in the range of C5 to C9 reduced the percentage in the distilled, since the increase of the hydrophilic part of the surfactant reduces its solubility in the oil. Finally, was obtained an increase in the degree of recovery of light hydrocarbons, comparing processes with and without surfactant, obtained an increase of 10% and 4% with Ultranex-18 and Ultranex-50, respectively. Thus, it is concluded that the Ultranex- 18 surfactant showed a higher capacity to distillation compared with Ultranex-50 and the application of surfactant on the molecular distillation from petroleum allowed for a greater recovery of light compounds in distillate / A destila??o molecular apresenta-se como uma alternativa para separa??o e purifica??o de diversos tipos de materias. O processo ? um caso especial de evapora??o a alto v?cuo, na ordem 0,001 a 0,0001 mmHg, e consequentemente, ocorre ? temperaturas relativamente mais baixas, preservando ao m?ximo o material a ser purificado. No Brasil, a destila??o molecular ? muito aplicada na separa??o de fra??es de petr?leo. No entanto, boa parte dos estudos relacionados a destila??o molecular de petr?leo avalia apenas as vari?veis do processo, tais como: a temperatura do evaporador, temperatura do condensador, vaz?o e etc. Dessa forma, com o prop?sito de favorecer a destila??o molecular, visando aumentar o grau de recupera??o da fra??o do destilado obtido no processo, avaliou-se a aplica??o de tensoativos n?o i?nicos da classe do nonilfenol etoxilado, uma vez que tais mol?culas apresentam a capacidade de interagir na interface l?quido-l?quido e l?quido-vapor de diversos sistemas. Portanto, o objetivo deste trabalho foi verificar a influ?ncia de tensoativo comerciais do tipo Ultranex-18 e Ultranex-50 na destila??o molecular de um petr?leo bruto. Nesse estudo, realizou-se a caracteriza??o f?sico-qu?mica do petr?leo a ser destilado, determinando-se que o mesmo apresentava um grau API de 42?, o que confere a amostra a ser destilada uma caracter?stica de fra??o leve. Na etapa do estudo das destila??es moleculares realizadas sem tensoativo, aplicou-se um planejamento estrela (2K ? ) com duas vari?veis (temperatura do evaporador e temperatura do condensador), tendo como resposta a porcentagem de destilado obtida no processo (%D). Verificou-se que a melhor condi??o experimental para a destila??o molecular do petr?leo estudado foi aplicando uma temperatura do evaporador de 120?C e do condensador de 10?C, obtendo-se uma porcentagem de destilado de 38 %. Posteriormente, para determinar uma faixa de concentra??o de tensoativo a ser aplicado no processo determinou-se a concentra??o micelar critica aplicando a t?cnica de espalhamento de raio-X de baixo ?ngulo (SAXS). Atrav?s da t?cnica, constatou-se que para os tensoativos da classe do nonilfenois etoxilados a concentra??o micelar cr?tica encontra-se na faixa de 10-2 mol/L para os hidrocarbonetos estudados. A partir dessa constata??o, aplicou-se no estudo das destila??es com tensoativo (Ultranex-18 e 50) uma faixa de concentra??o entre 0,01 a 0,15 mol/L. Nesta etapa, verificou-se que a presen?a do tensoativo n?o i?nico aumentou a destila??o de hidrocarbonetos na faixa de 5 a 9 carbonos em compara??o ao processo realizado sem tensoativo, e que em alguns casos a fra??o de compostos leves no destilado do processo foi superior a 700 % em rela??o ao processo convencional. O estudo mostrou que o aumento do grau de etoxila??o do Ultranex-18 para o Ultranex-50, reduziu a porcentagem de compostos destilados na faixa de C5 a C9, uma vez que o aumento da parte hidrof?lica do tensoativo reduz sua solubilidade no petr?leo. Finalmente, verificou-se que o aumento no grau de recupera??o de hidrocarbonetos leves, comparando os processos com o tensoativo e sem tensoativo, resultou em um aumento de 10 % para o processo empregando o Ultranex-18 e 4% para o Ultranex-50. Dessa forma, conclui-se que o Ultranex-18 apresentou maior capacidade de destila??o frente ao Ultranex-50 e que a aplica??o de tensoativo na destila??o molecular de petr?leo favoreceu o processo, j? que houve o aumento da concentra??o de compostos leves obtidos