Made available in DSpace on 2014-12-17T15:42:01Z (GMT). No. of bitstreams: 1 FranciscoFN_DISSERT.pdf: 2089554 bytes, checksum: 7f494e90c450d766696575e9a76682d2 (MD5) Previous issue date: 2012-02-29 / Universidade Federal do Rio Grande do Norte / This work is combined with the potential of the technique of near infrared spectroscopy - NIR and chemometrics order to determine the content of diclofenac tablets, without destruction of the sample, to which was used as the reference method, ultraviolet spectroscopy, which is one of the official methods. In the construction of multivariate calibration models has been studied several types of pre-processing of NIR spectral data, such as scatter correction, first derivative. The regression method used in the construction of calibration models is the PLS (partial least squares) using NIR spectroscopic data of a set of 90 tablets were divided into two sets (calibration and prediction). 54 were used in the calibration samples and the prediction was used 36, since the calibration method used was crossvalidation method (full cross-validation) that eliminates the need for a validation set. The evaluation of the models was done by observing the values of correlation coefficient R 2 and RMSEC mean square error (calibration error) and RMSEP (forecast error). As the forecast values estimated for the remaining 36 samples, which the results were consistent with the values obtained by UV spectroscopy / Neste trabalho s?o combinadas as potencialidades da t?cnica de espectroscopia no infravermelho pr?ximo NIR e da quimiometria visando ? determina??o do teor de diclofenaco em comprimidos, sem destrui??o da amostra, para o qual utilizou-se como refer?ncia o m?todo de espectroscopia no ultravioleta, que ? um dos m?todos oficiais. Na constru??o dos modelos de calibra??o multivariada estudou-se v?rios tipos de pr?processamento dos dados espectrais NIR, como corre??o do espalhamento da luz, primeira derivada. O m?todo de regress?o usado na constru??o dos modelos de calibra??o foi o PLS (m?nimos quadrados parciais) utilizando dados espectrosc?picos do NIR de um conjunto de 90 comprimidos divididos em dois conjuntos (calibra??o e previs?o). Na calibra??o foram usadas 54 amostras e na previs?o foram usadas 36, uma vez que o m?todo de calibra??o utilizada foi o m?todo de valida??o cruzada (full cross validation) que dispensa a necessidade de um conjunto de valida??o. A avalia??o dos modelos foi feita observando os valores de coeficiente de correla??o R2 e os erros quadrados m?dios RMSEC (erro de calibra??o) e RMSEP (erro de previs?o). Sendo os valores de previs?o estimados para as demais 36 amostras, o qual os resultados se mostraram coerentes com os valores obtidos por espectroscopia no ultravioleta

Made available in DSpace on 2014-12-17T15:42:02Z (GMT). No. of bitstreams: 1 AnaMariaSM.pdf: 217960 bytes, checksum: 2de591943a3cac6bc496d8cf75adf593 (MD5) Previous issue date: 2008-01-25 / Modified polyacrylamides with ≅ 0.2 mol % of N,N-dihexylacrylamide and hydrolysis degree from 0 to 25 % were synthesized by micellar copolymerization. The hydrophobic monomer was obtained by the reaction between acryloyl chloride and N,Ndihexylamine and characterized by infrared (IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. The polymer molecular structures were determined through 1H and 13C NMR spectroscopy and the polymers were studied in dilute and semi-dilute regimes by viscometry, rheometry, static light scattering and photon correlation spectroscopy, at the temperature range from 25 to 55 ?C. The data obtained by viscometry showed that the intrinsic viscosity from the hydrolyzed polymers is larger than the precursor polymers at the same ionic strength. The comparison between the charged polymers showed that the polymer with higher hydrolysis degree has a more compact structure in formation water (AFS). The increase of temperature led to an enhanced reduced viscosity to the polymers in Milli-Q water (AMQ), although, in brine, only the unhydrolyzed polymer had an increase in the reduced viscosity with the temperature, and the hydrolyzed derivatives had a decrease in the reduced viscosity. The static light scattering (SLS) analyses in salt solutions evidenced a decrease of weight-average molecular weight (⎯Mw) with the increase of the hydrolysis degree, due to the reduction of the thermodynamic interactions between polymer and solvent, which was evidenced by the decrease of the second virial coefficient (A2). The polymers showed more than one relaxation mode in solution, when analyzed by photon correlation spectroscopy, and these modes were attributed to isolated coils and aggregates of several sizes. The aggregation behavior depended strongly on the ionic strength, and also on the temperature, although in a lower extension. The polymers showed large aggregates in all studied conditions, however, their solutions did not displayed a good increase in water viscosity to be used in enhanced oil recovery (EOR) processes / Poliacrilamidas modificadas com ≅ 0,2 mol % de N,N-dihexilacrilamida e grau de hidr?lise de 0 a 25 % foram sintetizadas por copolimeriza??o micelar. O mon?mero hidrof?bico foi obtido pela rea??o entre cloreto de acrilo?la e N,N-dihexilamina e foi caracterizado por espectroscopia no infravermelho (IV) e resson?ncia magn?tica nuclear de pr?ton (1H RMN). As estruturas moleculares dos pol?meros foram determinadas atrav?s de espectroscopia de RMN 1H e 13C e os pol?meros foram estudados em regime dilu?do e semidilu?do por viscosimetria, reometria, espalhamento de luz est?tico e espectroscopia de correla??o de f?tons, na faixa de temperatura de 25 a 55 ?C. Os dados obtidos por viscosimetria mostraram que as viscosidades intr?nsecas dos pol?meros hidrolisados s?o maiores que a do pol?mero precursor na mesma for?a i?nica e a compara??o entre os pol?meros carregados mostrou que o pol?mero com maior grau de hidr?lise tem uma estrutura mais compacta em ?gua de forma??o sint?tica (AFS). A eleva??o da temperatura induziu um aumento na viscosidade reduzida dos pol?meros em ?gua Milli-Q (AMQ). Em solu??o salina, apenas o pol?mero neutro apresentou aumento na viscosidade reduzida com a temperatura, enquanto os derivados hidrolisados apresentaram uma diminui??o na viscosidade reduzida. A partir do espalhamento de luz est?tico (SLS), em meio salino, foi evidenciada uma diminui??o da massa molar ponderal m?dia (⎯Mw) com o aumento do grau de hidr?lise, que foi atribu?da ? redu??o das intera??es termodin?micas entre pol?mero e solvente, o que p?de ser deduzido pela diminui??o do segundo coeficiente do virial (A2). Os pol?meros apresentaram mais de um modo de relaxa??o em solu??o, quando analisados por espectroscopia de correla??o de f?tons, e esses modos foram atribu?dos a cadeias isoladas e a agregados de diversos tamanhos. O comportamento de agrega??o dependeu fortemente da for?a i?nica, e tamb?m da temperatura, embora de uma forma menos pronunciada. Os pol?meros apresentaram grandes agregados em todas as condi??es estudadas, contudo, suas solu??es n?o mostraram um bom aumento na viscosidade da ?gua para serem usados em processos de recupera??o melhorada de petr?leo (EOR)

Made available in DSpace on 2014-12-17T15:42:03Z (GMT). No. of bitstreams: 1 EwertonRFT_DISSERT.pdf: 4228292 bytes, checksum: 8fb23445cdaa1e3bfe9b7d317ec439df (MD5) Previous issue date: 2012-10-19 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This work aims to study the influence of two additives, the monomer, acrylamide and its polymer, polyacrylamide, solubilized in microemulsion systems and applied on enhanced oil recovery. By the microemulsion system obtained, it was chosen points into the phase diagram, presenting these compositions: 25%, 30%, 35% C/T; 2% Fo (fixed for all points) e 73%, 68% e 63% Fa, respectively. However, the monomer and the polymer were solubilized in these microemulsion points with 0.1%; 0.5%; 1% e 2% of concentration, ordering to check the concentration influence at the physicochemical properties (surface tension and rheology) of the microemulsion. Through the salinity study, was possible to observe that the concentrations of 1% and 2% of polymer made the solution became blurred, accordingly, the study of surface tension and rheology only was made for the concentrations of 0.1% e 0.5% of monomer and polymer, respectively. By the surface tension study it was observed that how the concentration of active matter (C/T) was increasing the surface tension was amending for each system, with or without additives. In the rheology study, as it increases the concentration of active matter increases both the viscosity of the microemulsion system (SME) with no additive, as the SME with polymer (AD2). After the entire study, it was chosen the lower point of active matter (25% C/T; 2% Fo e 73% Fa), plus additives in concentrations of 0.1% and 0.5% to be used on enhanced oil recovery. Assays were made on sandstone from Botucatu Formation, where after the tests, it was concluded that among the studied points, the point who showed the best efficiency of advanced shift was the microemulsion system + 0.5% AD2, with a recovery of 28% of oil in place and a total of 96,49%, while the other solution with 0.5% of polymer presented the worst result, with 14.1% of oil in place and 67,39% of efficiency of total displacement / Este trabalho tem como objetivo estudar a influ?ncia de dois aditivos, a acrilamida e seu pol?mero, poliacrilamida, solubilizados em sistemas microemulsionados e aplicados na recupera??o avan?ada de petr?leo. Atrav?s da obten??o do sistema microemulsionado, foram escolhidos pontos do diagrama de fases apresentando as seguintes composi??es: 25%, 30%, 35% C/T; 2% Fo (fixa para todos os pontos) e 73%, 68% e 63% Fa, respectivamente. O mon?mero e o pol?mero foram solubilizados nestes pontos de microemuls?o nas concentra??es de 0,1%; 0,5%; 1% e 2%, visando verificar a influ?ncia da concentra??o nas propriedades f?sico-qu?micas (tens?o superficial e reologia) da microemuls?o. Atrav?s do estudo de salinidade, foi poss?vel observar que as concentra??es 1% e 2% de pol?mero turvaram a microemuls?o, portanto, o estudo de tens?o e reologia foi realizado para as concentra??es 0,1% e 0,5% de mon?mero e pol?mero, respectivamente. Atrav?s do estudo de tens?o superficial observou-se que ? medida que aumenta a concentra??o de mat?ria ativa (C/T) altera a tens?o superficial para ambos sistemas com e sem aditivos. No estudo de reologia, ? medida que aumenta a concentra??o de mat?ria ativa, aumenta tanto a viscosidade do sistema microemulsionado (SME) sem aditivo, quanto o SME com pol?mero (AD2). Ap?s esse estudo, foi selecionado o ponto de menor concentra??o de mat?ria ativa (25% C/T; 2% Fo e 73% Fa) acrescido dos aditivos nas concentra??es 0,1% e 0,5% para serem utilizados na recupera??o avan?ada de petr?leo. Os ensaios foram realizados em arenitos da forma??o Botucatu, onde, ap?s terem sido realizados os testes, concluiu-se que dentre os pontos estudados, o que apresentou a melhor efici?ncia de deslocamento avan?ada foi o sistema microemulsionado + 0,5% de poliacrilamida (AD2), com uma recupera??o de 28% de ?leo in place e total de 96,49%, que ao ser comparada a solu??o de 0,5% do mesmo pol?mero apresentou recupera??o avan?ada de 14,1% de ?leo in place e 67,39% de efici?ncia de deslocamento total. A realiza??o deste trabalho mostrou que a utiliza??o de pol?meros em sistemas microemulsionado aparece como uma alternativa vi?vel na recupera??o avan?ada de petr?leo

Made available in DSpace on 2014-12-17T15:42:04Z (GMT). No. of bitstreams: 1 LucianeLT_DISSERT.pdf: 3099685 bytes, checksum: cf9ca201e507efce1126bfa70e5a1f3b (MD5) Previous issue date: 2012-03-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This study conducted chemical analyzes of the fruits of Licania tomentosa Benth belonging to the Chrysobalanaceae family, order and superorder Rosiflorae Rosales. Samples were collected in February 2011 in the city of Natal - RN. The fruits were separated into peel, pulp and seed, and the samples were analyzed on moisture and ash by thermogravimetric methods, reducing and total sugars, lipids by Soxhlet extraction, minerals by ICP / OES and other analyzes by physical measurements of the fruit. The fruits for the analysis of determination of flavonoids and phenolic compounds were dried at 40 ? C and ground. For the analyzes to determine the content of phenolics and flavonols was used spectroscopy in the visible region, and also performed the characterization of ethanol extracts by high performance liquid chromatography and test for antioxidant activity hydroethanolic extracts. The results obtained are about 83.9% of the fruits have a length between 4.0 to 6.0 cm with respect to the diameter of the fruit about 97.4% of the fruits have a diameter between 2.0 - 4, 0 cm, mean weight of 36.14 g (7.86), the bark showed 60.5 (1.5)% relative humidity, the flesh 72.3 (0.9) and 44.4 seeds (0.4 )%, the bark showed 0.22 (0.00)% ash, the pulp 1.41 (0.01)% and the seed 1.18 (0.01)%, the bark showed 3.73 (0, 09) mg lipids / 100 g sample of the pulp 0.40 (0.04) and the seed 0.05 (0.00). With respect to reducing sugars and total gave the results, 16.23 (0.23) g/100g and 20.70 (0.24) g/100g. The fruit is presented with a good source of nutrients especially carbohydrates and lipids. The analysis for determining the antioxidant activity tests were performed reducing power and antioxidant capacity, the antioxidant capacity of hydroethanolic extracts of peel and pulp showed similar results, with higher concentrations however hydroethanolic bark extract. Regarding the content of phenolics and flavonoids hidroetan?lico bark extract showed higher concentration values. The characterization of the extracts by high performance liquid chromatography identified the following compounds by retention time indicated by the race of the standards: galic acid, kaempferol and kaempferol derivatives. Considering the results of the fruit Licania tomentosa Benth may be an alternative food by analysis of their nutritional content and has substances with antioxidant action / O presente trabalho realizou das an?lises bromatol?gicas com os frutos da Licania tomentosa Benth que pertence ? fam?lia Chrysobalanaceae, ordem Rosales e superordem Rosiflorae. As amostras foram coletadas no m?s de fevereiro de 2011 no munic?pio de Natal RN. Os frutos foram fracionados em casca, polpa e semente, e com as amostras foram realizadas as determina??es de umidade e cinzas por m?todos termogravim?tricos, a??cares redutores e totais, lip?deos por extra??o com Soxhlet, minerais por ICP/OES e demais an?lises por medi??es f?sicas dos frutos. Os frutos destinados as an?lises de determina??o do teor de flavon?ides e fen?licos totais foram secos a 40?C e triturados. Para as an?lises de determina??o do teor de fen?licos e flavon?is totais se utilizou a espectroscopia na regi?o do vis?vel, sendo tamb?m realizada a caracteriza??o dos extratos etan?licos por cromatografia l?quida de alta efici?ncia e teste de atividade antioxidante para os extratos hidroetan?licos. Como resultados obteve-se cerca de 83,9% dos frutos apresentaram comprimento entre 4,0 6,0 cm, com rela??o ? determina??o do di?metro dos frutos cerca de 97,4 % dos frutos apresentaram di?metro entre 2,0 4,0 cm, peso m?dio de 36,14 (7,86) g, a casca apresentou 60,5 (1,5)% de umidade, a polpa 72,3 (0,9) e a semente 44,4 (0,4)%, a casca apresentou 0,22 (0,00) % de cinzas, a polpa 1,41(0,01)% e a semente 1,18(0,01)%, a casca apresentou 3,73 (0,09)mg de lip?deos/ 100 g de amostra, a polpa 0,40(0,04) e a semente 0,05(0,00). Com rela??o aos teores de a??cares redutores e totais obteve-se os respectivos resultados, 16,23 (0,23) g/100g e 20,70(0,24) g/100g. O fruto se apresenta com uma boa fonte de nutrientes principalmente carboidratos e lip?deos. As an?lises de determina??o da atividade antioxidante realizadas foram os testes de poder redutor e capacidade antioxidante, a capacidade antioxidante dos extratos hidroetan?licos da casca e da polpa apresentaram resultados semelhantes, sendo entretanto superior as concentra??es do extrato hidroetan?lico da casca. Com rela??o ao teor de fen?licos e flavon?ides totais o extrato hidroetan?lico da casca apresentou valores de concentra??o superiores. Na caracteriza??o dos extratos por cromatografia l?quida de alta efici?ncia foram identificados os seguintes compostos por meio do tempo de reten??o indicado pela corrida dos padr?es: ?cido g?lico, campferol e derivados. Diante dos resultados o fruto da Licania tomentosa Benth pode ser uma alternativa de alimento mediante a an?lise de seu conte?do nutricional e por possuir subst?ncias com a??o antioxidante

Made available in DSpace on 2014-12-17T15:42:08Z (GMT). No. of bitstreams: 1 GenicksonBC_DISSERT.pdf: 3221273 bytes, checksum: 93f5a94a8d409de3a6c9189089010e14 (MD5) Previous issue date: 2012-02-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This work involved the synthesis, characterization and proposing the molecular structure of coordination compounds involving ligands pyrazine-2-carboxamide (PZA) and 4- hydrazide acidic pyridine carboxylic (INH) and metals of the first transition series (M = Co2+, Ni2+ and Cu2+). For the characterization of the compounds used were analytical techniques such as infrared absorption spectroscopy average (FT-IR) molar conductivity measurements, CHN elemental analysis, EDTA Complexometric, measurement of melting point, X-ray diffraction by powder method, Thermogravimetry (TG) and Differential Thermal Analysis (DTA) and Simultaneous Differential Scanning Calorimetry (DSC). The absorption spectra in the infrared region suggested that the ligand coordination to the metal center occurs through the carbonyl oxygen atom and nitrogen alpha pyrazine ring to those complexes formed with PZA. For INH complexes with metal-ligand coordination is through the carbonyl oxygen and nitrogen of the terminal hydrazide grouping. The conductivity measurements of the complexes in aqueous solution they suggest to all behavior of the type 1:2 electrolytes, and conduct of non-electrolytes in acetonitrile. The results obtained by CHN elemental analysis and EDTA Complexometric allowed to infer the stoichiometry of the compounds synthesized. For all of the complexes obtained was possible to record the melting points, neither of which melted near the melting temperature of the free ligands. The X-ray diffraction showed that the complexes of pyrazinamide exhibited diffraction lines, suggesting that these compounds are crystalline, while compounds of isoniazid, with the exception of cobalt, exhibited diffraction lines, indicating that they are crystalline. The results from the TG-DTA and DSC allowed information regarding the dehydration and thermal decomposition of these complexes / Este trabalho consistiu na s?ntese, caracteriza??o e proposi??o da estrutura molecular de compostos de coordena??o envolvendo os ligantes pirazina-2-carboxamida (PZA) e 4- hidrazida ?cida piridincarbox?lica (INH) e os metais da primeira s?rie de transi??o (M = Co2+, Ni2+ e Cu2+). Para a caracteriza??o dos compostos foram utilizadas t?cnicas de an?lise como: Espectroscopia de absor??o no Infravermelho m?dio (FT-IR), medidas de condutividade molar, An?lise Elementar de CHN, complexometria com EDTA, medidas do ponto de fus?o, Difra??o de raios-X pelo m?todo do p?, Termogravimetria (TG) e An?lise T?rmica Diferencial (DTA) simult?nea e Calorimetria Explorat?ria Diferencial (DSC). Os espectros de absor??o na regi?o do infravermelho sugerem que a coordena??o do ligante ao centro met?lico ocorreu atrav?s do ?tomo de oxig?nio carbon?lico e do nitrog?nio alfa do anel piraz?nico para os complexos formados com a PZA. Para os complexos com a INH a coordena??o ligante-metal se d? pelo oxig?nio da carbonila e nitrog?nio terminal do grupamento hidrazida. As medidas de condutividade dos complexos em solu??o aquosa sugerem para todos eles comportamento de eletr?litos do tipo 1:2; e comportamento de n?o eletr?litos em acetonitrila. Os resultados obtidos pela an?lise elementar de CHN e complexometria com EDTA permitiram inferir a estequiometria dos compostos sintetizados. Para todos os complexos obtidos foi poss?vel registrar os pontos de fus?o, sendo que nenhum deles fundiu pr?ximo da temperatura de fus?o dos ligantes livres. Os difratogramas de raios-X mostraram que os complexos da pirazinamida apresentaram linhas de difra??o, sugerindo que estes compostos s?o cristalinos, enquanto os compostos da isoniazida, com exce??o ao de cobalto, apresentaram linhas de difra??o, indicando que os mesmos s?o cristalinos. Os resultados a partir das curvas TG-DTA e DSC permitiram informa??es a respeito da desidrata??o e decomposi??o t?rmica destes complexos

Made available in DSpace on 2014-12-17T15:42:08Z (GMT). No. of bitstreams: 1 AlcidesOWN_TESE.pdf: 3644832 bytes, checksum: b30265cac81e679890142573e54a4e61 (MD5) Previous issue date: 2010-03-06 / Corrosion usually occurs in pipelines, so that it is necessary to develop new surface treatments to control it. Surfactants have played an outstanding role in this field due to its capacity of adsorbing on metal surfaces, resulting in interfaces with structures that protect the metal at low surfactant concentrations. The appearance of new surfactants is a contribution to the area, as they increase the possibility of corrosion control at specific conditions that a particular oil field presents. The aim of this work is to synthesize the surfactants sodium 12 hydroxyocadecenoate (SAR), sodium 9,10-epoxy-12 hydroxyocadecanoate (SEAR), and sodium 9,10:12,13-diepoxy-octadecanoate (SEAL) and apply them as corrosion inhibitors, studying their action in environments with different salinities and at different temperatures. The conditions used in this work were chosen in order to reproduce oil field reality. The study of the micellization of these surfactants in the liquid-gas interface was carried out using surface tensiometry. It was observed that cmc increased as salt concentration was increased, and temperature and pH were decreased, while cmc decreased with the addition of two epoxy groups in the molecule. Using the values of cmc and the Gibbs equation, the values of Gibbs free energy of adsorption, area per adsorbed molecule, and surface excess were calculated. The surface excess increases as salt concentration and temperature decreases, increasing as pH is increased. The area per adsorbed molecule and the free energy of adsorption decrease with salt concentration, temperature, and pH increase. SAXS results showed that the addition of epoxy group in surfactant structure results in a decrease in the repulsion between the micelles, favoring the formation of more oblong micellar structures, ensuring a better efficiency of metal coverage. The increase in salt and surfactant concentrations provides an increase in micellar diameter. It was shown that the increase in temperature does not influence micellar structure, indicating thermal stability that is advantageous for use as corrosion inhibitor. The results of inhibition efficiency for the surfactants SEAR and SEAL were considered the best ones. Above cmc, adsorption occurred by the migration of micelles from the bulk of the solution to the metal surface, while at concentrations below cmc film formation must be due to the adsorption of semi-micellar and monomeric structures, certainly due to the presence of the epoxy group, which allows side interactions of the molecule with the metal surface. The metal resistance to corrosion presented values of 90% of efficiency. The application of Langmuir and Frumkin isotherms showed that the later gives a better description of adsorption because the model takes into account side interactions from the adsorbing molecules. Wettability results showed that micelle formation on the solid surface occurs at concentrations in the magnitude of 10-3 M, which isthe value found in the cmc study. This value also justifies the maximum efficiencies obtained for the measurements of corrosion resistance at this concentration. The values of contact angle as a function of time suggest that adsorption increases with time, due to the formation of micellar structures on metal surface / O fen?meno da corros?o est? presente em oleodutos e por isso existe a necessidade de desenvolver novos materiais que controle tal fen?meno. Os tensoativos t?m se destacado para tal fim devido ao seu poder de adsorver-se em interfaces e formar estruturas que protejam o metal em baixas concentra??es. O surgimento de novos tensoativos ? uma contribui??o para o setor, pois aumentam as possibilidades de controlar a corros?o nas condi??es espec?ficas de cada campo. Este trabalho objetiva, principalmente, sintetizar e aplicar os tensoativos 12 hidroxioctadecenoato de s?dio (SAR), 9,10-ep?xi-12 idroxioctadecanoato de s?dio (SEAR) e 9,10:12,13-diep?xi-octadecanoato de s?dio (SEAL) como inibidores de corros?o, estudando-os em ambientes que apresentam, simultaneamente, salinidade, acidez e temperatura variadas. As condi??es estudadas s?o para reproduzir o m?ximo poss?vel ? realidade do campo. O estudo da miceliza??o destes tensoativos na interface l?quido-g?s foi realizado a partir de medidas de tens?o superficial. Observou-se que a eleva??o da concentra??o salina, abaixamento da temperatura e diminui??o do pH proporcionam aumento nos valores da cmc, com tamb?m os valores da cmc aumentam quando se adiciona um e dois grupos ep?xi na mol?cula, respectivamente. A partir da cmc, usando equa??o de Gibbs, foram encontrados valores para a energia livre de Gibbs de adsor??o, ?rea por mol?cula adsorvida e excesso superficial. O aumento dos valores de excesso superficial ? provocado pela diminui??o da concentra??o salina e temperatura, e aumenta com a eleva??o do pH. A ?rea por mol?cula adsorvida e a energia livre de adsor??o diminuem com aumento da salinidade e temperatura, e com o aumento do pH. Os resultados de SAXS mostraram que a adi??o do grupo ep?xi e o seu aumento na estrutura do tensoativo proporcionam diminui??o na intera??o de repuls?o entre as micelas, assim como favorecem a forma??o de estruturas micelares mais alongadas, garantindo maior efici?ncia na cobertura do metal. O aumento da concentra??o salina e da concentra??o do tensoativo proporciona aumento do di?metro da micela. O aumento da temperatura mostrou que n?o influencia a estrutura micelar, o que indica estabilidade t?rmica, sendo vantajoso para sua atua??o como inibidor de corros?o. Os resultados de efici?ncia para os tensoativos SEAR e SEAL foram os melhores. A cima da cmc a adsor??o se deve a migra??o da micela do seio da solu??o para a superf?cie do metal, enquanto em concentra??es abaixo da cmc a forma??o do filme se deve a adsor??o de estruturas semimicelares e monom?ricas, nas quais s?o caracter?sticas dos tensoativos que apresentam o grupo ep?xi, pois possibilita intera??o lateral da mol?cula com a superf?cie met?lica. A resist?ncia do metal ? corros?o apresentou valores de 90% de efici?ncia. A aplica??o das isotermas de Langmuir e Frumkin mostrou que esta ?ltima melhor valida o fen?meno da adsor??o, devido haver em sua express?o matem?tica o par?metro de intera??o lateral. Os resultados de molhabilidade mostraram que a forma??o da micela na superf?cie do s?lido se d? em concentra??es na ordem de 10-3 M, valor encontrado no estudo da cmc. Este valor justifica, tamb?m, os valores m?ximos de efici?ncia obtidos para as medidas de resist?ncia a corros?o a partir desta concentra??o. Os valores de ?ngulo de contato em fun??o do tempo sugerem que a adsor??o aumenta com o tempo, devido a forma??o de estruturas micelares na superf?cie do metal

Made available in DSpace on 2014-12-17T15:42:13Z (GMT). No. of bitstreams: 1 FrancielAB_DISSERT.pdf: 3637529 bytes, checksum: 50d6de8b3a00a0b045a5b17d540f59d2 (MD5) Previous issue date: 2014-01-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Catalytic processes are widely present in everyday life. This results in large number of studies seeking materials that may combine the low cost catalytic efficiency. Based on this assumption, the clays have long been used as catalysts, with its huge availability, diversity and possibility of improving their properties from structural changes, primarily responsible for this great use. Among the natural clays, vermiculite due to their characteristic properties (high cation exchange capacity and expansion), is suitable for various applications including as catalysts and catalyst supports. In this work, the acid leaching of clay vermiculite was performed, coming from Santa Luzia-PB, with nitric acid (2, 3 and 4 mol / L) and subsequent calcination of the materials obtained. The materials were named as Vx/400, where x is the acid concentration employed and 400 used in calcination temperature. The effectiveness of changes made was determined by XRD techniques, FT-IR, EDS, TG/DTG, nitrogen physisorption and DTP of n-butylamine. Acid leaching has improved some properties of the clay - specific area and acidity - but the control of the acid concentration used is of vital importance, since the highest concentration caused the partial destruction of vermiculite entailing a decline in their properties. For analysis of the catalytic activity of the modified clay was made a comparative study with the SBA -15 mesoporous materials, synthesized via hydrothermal method, using the pyrolysis of low density polyethylene (LDPE). The results showed that the acid plays a fundamental role in the conversion of the polymer into smaller molecules, the material V3/400 was more selective for the source monomer (ethylene) due to their increased acidity, which promotes more breaks bonds in the polymeric chain, while materials and V0/400 V2/400, lower acidity, showed higher selectivity to light hydrocarbons, the range of fuel (41.96 and 41.23%, respectively), due to less breakage and secondary condensation reactions chains; already V4/400 SBA-15/550 and resulted in lower percentages of light hydrocarbons and the partial destruction of the structure and low acidity, respectively, responsible for the inefficiency of materials / Os processos catal?ticos est?o largamente presentes no cotidiano. Isso resulta no grande n?mero de pesquisas buscando materiais que possam aliar baixo custo ? efici?ncia catal?tica. Partindo desse pressuposto, as argilas t?m sido muito utilizadas como catalisadores, sendo sua grande disponibilidade, diversidade e possibilidade de melhoria de suas propriedades, a partir de modifica??es estruturais, os principais respons?veis por esse grande uso. Entre as argilas naturais, a vermiculita devido ?s suas propriedades caracter?sticas (alta capacidade de troca cati?nica e de expans?o), ? apta para diversas aplica??es, entre elas, como suportes catal?ticos e catalisadores. Neste trabalho, foi realizada a lixivia??o ?cida da argila vermiculita, oriunda de Santa Luzia-PB, com ?cido n?trico (2, 3 e 4 mol/L) e posterior calcina??o dos materiais obtidos. Os materiais foram nomeados como Vx/400, onde x corresponde ? concentra??o ?cida empregada e 400 ? temperatura usada na calcina??o. A efici?ncia das modifica??es realizadas foi determinada pelas t?cnicas de DRX, FT-IR, EDS, TG/DTG, fisissor??o de nitrog?nio e DTP de n-butilamina. A lixivia??o ?cida melhorou algumas propriedades da argila ?rea espec?fica e acidez , por?m o controle da concentra??o ?cida empregada ? de vital import?ncia, visto que a maior concentra??o provocou a destrui??o parcial da vermiculita, acarretando em um decr?scimo das suas propriedades. Para an?lise da atividade catal?tica das argilas modificadas fez-se um estudo comparativo com o material mesoporoso SBA-15, sintetizado via m?todo hidrot?rmico, empregando-os na pir?lise de polietileno de baixa densidade (PEBD). Os resultados mostraram que a acidez exerce papel fundamental na convers?o do pol?mero em mol?culas menores; o material V3/400 foi o mais seletivo para o mon?mero de origem (eteno), devido ? sua maior acidez, que promove mais cis?es nas liga??es da cadeia polim?rica; enquanto os materiais V0/400 e V2/400, de menor acidez, apresentaram maior seletividade para hidrocarbonetos leves, da faixa dos combust?veis (41,96 e 41,23%, respectivamente), em virtude de menos cis?es e rea??es secund?rias de condensa??o nas cadeias; j? V4/400 e SBA-15/550 resultaram nos menores percentuais de hidrocarbonetos leves, sendo a destrui??o parcial da estrutura e baixa acidez, respectivamente, respons?veis pela inefici?ncia dos materiais

Made available in DSpace on 2014-12-17T15:42:14Z (GMT). No. of bitstreams: 1 RosemiroMB_DISSERT.pdf: 2340991 bytes, checksum: c71ab28274a335ce511c0a85fd6c1157 (MD5) Previous issue date: 2014-01-07 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The knowledge of the rheological behavior of microemulsionated systems (SME) is of fundamental importance due to the diversity of industrial applications of these systems. This dissertation presents the rheological behavior of the microemulsionated system formed by RNX 95/alcohol isopropyl/p-toulen sodium sulfonate/kerosene/distilled water with the addition of polyacrylamide polymer. It was chosen three polymers of the polyacrylamide type, which differ in molar weight and charge density. It was studied the addition of these polymers in relatively small concentration 0,1% in mass and maximum concentration of 2,0%. It was made analysis of flow to determine the appearing viscosities of the SME and rheological parameters applying Bingham, Ostwald de Waale and Herschell-Buckley models. The behavior into saline environment of this system was studied for a solution of KCl 2,0%, replacing the distilled water. It was determined the behavior of microemulsions in relation with the temperature through curves of flow in temperatures of 25 to 60?C in variations of 5?C. After the analysis of the results the microemulsion without the addition of polymer presented a slight increase in its viscosity, but it does not mischaracterize it as a Newtonian fluid. However the additive systems when analyzed with low concentration of polymer adjusted well to the applied models, with a very close behavior of microemulsion. The higher concentration of the polymer gave the systems a behavior of plastic fluid. The results of the temperature variation point to an increase of viscosity in the systems that can be related to structural changes in the micelles formed in the own microemulsion without the addition of polymer / O conhecimento do comportamento reol?gico de sistemas microemulsionados (SME) ? de fundamental import?ncia, devido ? diversidade de aplica??es industriais desses sistemas. Esse trabalho apresenta o comportamento reol?gico do sistema microemulsionado formado por RNX 95/?lcool isoprop?lico/p-tolueno sulfonato de s?dio/Querosene/?gua destilada com a adi??o do pol?mero poliacrilamida. Foram escolhidos tr?s pol?meros do tipo poliacrilamida, que diferem quanto a massa molar e sua densidade de carga. Estudou-se a adi??o desses pol?meros em concentra??o relativamente baixa 0,1% em massa e concentra??o m?xima de 2,0%. Foram realizadas an?lises de escoamento para a determina??o das viscosidades aparente dos SME e par?metros reol?gicos aplicando os modelos de Bingham, Ostwald de Waale e Herschell-Buckley. O comportamento em meio salino desse sistema foi estudado para uma solu??o de KCl 2,0%, em substitui??o ? ?gua destilada. Foi determinado o comportamento das microemuls?es em rela??o ? temperatura atrav?s de curvas de escoamento a temperaturas de 25 a 60?C com varia??es de 5?C. Ap?s an?lise dos resultados a microemuls?o sem adi??o de pol?mero apresentou um ligeiro aumento em sua viscosidade, mas o que n?o a descaracteriza como um fluido newtoniano. Os sistemas aditivados quando analisados com concentra??o baixa de pol?mero ajustaram-se bem aos modelos aplicados, com comportamento muito pr?ximo da microemuls?o. J? a concentra??o mais elevada de pol?mero deu aos sistemas comportamento de fluido pl?stico. Os resultados da varia??o de temperatura apontam para um aumento na viscosidade dos sistemas que pode estar relacionado a mudan?as estruturais nas micelas formadas na pr?pria microemuls?o sem adi??o de pol?mero

Made available in DSpace on 2014-12-17T15:42:15Z (GMT). No. of bitstreams: 1 LoildeDB_TESE.pdf: 2292456 bytes, checksum: 7268473c8f078f403990f633d690589e (MD5) Previous issue date: 2012-10-07 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The contamination by metal ions has been occurring for decades through the introduction of liquid effluent not treated, mainly from industrial activities, rivers and lakes, affecting water quality. For that the effluent can be disposed in water bodies, environmental standards require that they be adequately addressed, so that the concentration of metals does not exceed the limits of standard conditions of release in the receptor. Several methods for wastewater treatment have been reported in the literature, but many of them are high cost and low efficiency. The adsorption process has been used as effective for removal of metal ions. This paper presents studies to evaluate the potential of perlite as an adsorbent for removing metals in model solution. Perlite, in its natural form (NP) and expanded (EP), was characterized by X-ray fluorescence, X-ray diffraction, surface area analysis using nitrogen adsorption (BET method), scanning electron microscopy and Fourier transform infrared spectroscopy. The physical characteristic and chemical composition of the material presented were appropriate for the study of adsorption. Adsorption experiments by the method of finite bath for model solutions of metal ions Cr3+, Cu2+, Mn2+ and Ni2+ were carried out in order to study the effect of pH, mass of the adsorbent and the contact time on removal of ions in solution. The results showed that perlite has good adsorption capacity. The NP has higher adsorption capacity (mg g-1) than the EP. According to the values of the constant of Langmuir qm (mg g-1), the maximum capacity of the monolayer was obtained and in terms of proportion of mass, we found the following order experimental adsorption: Cr3+ (2.194 mg g- 1) > Ni2+ (0.585 mg g-1) > Mn2+ (0.515 mg g-1) > Cu2+ (0.513 mg g-1) and Cr3+ (1.934 mg g-1)> Ni2+ (0.514 mg g-1) > Cu2+ (0.421 mg g-1) > Mn2+ (0.364 mg g-1) on the NP and EP, respectively. The experimental data were best fitted the Langmuir model compared to Freundlich for Cu2+, Mn2+ and Ni2+. However, for the Cr3+, both models fit the experimental data / A contamina??o por ?ons met?licos vem ocorrendo h? d?cadas atrav?s do lan?amento de efluentes l?quidos n?o tratados, principalmente de atividades industriais, nos rios e lagos, comprometendo a qualidade da ?gua. Para que os efluentes possam ser descartados em corpos d'?gua, as normas ambientais exigem que os mesmos sejam adequadamente tratados, de modo que a concentra??o dos metais n?o ultrapasse os limites de condi??es padr?es de lan?amento no corpo receptor. V?rios m?todos para tratamento de efluentes t?m sido apresentados na literatura, por?m muitos deles s?o de alto custo e baixa efici?ncia. O processo de adsor??o vem sendo utilizado como eficaz para remo??o de ?ons met?licos. Neste trabalho s?o apresentados estudos para avaliar a potencialidade da perlita como adsorvente na remo??o de metais em solu??o modelo. A perlita, na sua forma natural (PN) e expandida (PE), foi caracterizada por fluoresc?ncia de raios X, difra??o de raios X, an?lise da ?rea superficial usando adsor??o f?sica de nitrog?nio (m?todo BET), microscopia eletr?nica de varredura (MEV) e espectroscopia de infravermelho com transformada de Fourier (FTIR). As caracter?sticas f?sicas e a composi??o qu?mica apresentadas pelo material foram adequadas para o estudo de adsor??o. Ensaios de adsor??o pelo m?todo de banho finito para solu??es modelo dos ?ons met?licos Cr3+, Cu2+, Mn2+ e Ni2+ foram realizados, com intuito de estudar o efeito do pH, da massa do adsorvente e do tempo de contato na remo??o de ?ons em solu??o. Os resultados demonstraram que a perlita apresenta boa capacidade de adsor??o. A PN apresenta maior capacidade de adsor??o (mg g-1) do que a PE. De acordo com os valores da constante de Langmuir, qm (mg g-1), a capacidade m?xima da monocamada foi obtida e em termos de propor??o de massa, encontrou-se a seguinte ordem experimental de adsor??o: Cr3+ (2,384 mg g-1) > Ni2+ (0,585 mg g-1) > Mn2+ (0,515 mg g-1) > Cu2+ (0,513 mg g-1) sobre a PN e Cr3+ (1,932 mg g-1) > Ni2+ (0,514 mg g-1) > Cu2+ (0,421 mg g-1) > Mn2+ (0,364 mg g-1) sobre a PE. Os dados experimentais se ajustaram melhor ao modelo de Langmuir em rela??o ao de Freundlich para os ?ons Cu2+, Mn2+ e Ni2+. No entanto, para os ?ons Cr3+, ambos, os modelos se ajustaram adequadamente aos dados experimentais

Made available in DSpace on 2014-12-17T15:42:15Z (GMT). No. of bitstreams: 1 FrancineB_DISSERT.pdf: 3873354 bytes, checksum: 665d87a2180d2517b91bf821d327dc87 (MD5) Previous issue date: 2014-05-22 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Two pillaring methods were tested to synthesize pillared clays containing mixed Al/Co pillars. Using the first method, based on the traditional procedure, were obtained materials containing different Co concentrations: 10, 25, 50, 75 and 100 % of Co in the pillaring solution. Just the experiments with low concentrations (10 and 25 % of Co) has formed pillared clays, whereas the sample with 25 % of cobalt showed best results compared with the one obtained just using Al as pillaring agent (basal spacing higher than 18 ? and surface area bigger than 300 m?/g). The 27Al NMR results pointed out the formation of mixed Al/Co pillars due to decreased between the intensities of AlVI/AlIV signals, indicating that the AlIV content decreased while Co content increased, suggesting the isomorphic substitution of Al atoms for Co in the Keggin ion structure (pillaring agent). For the samples containing 75 and 100 % of cobalt, it was verified the formation of others materials, which could be identified as hydrotalcite like compounds. The second pillarization method was named mixed layers, because the objective was to intercalate clay layers with hydrotalcite layers. Thus, after calcination, the hydrotalcite layers would dehydroxylate, resulting just in the metals oxides, intercalated between the clay sheets, thus generating, a pillared clay. For this purpose, were tested 4 synthesis procedures: physical mixture, mixture in water, ionic exchange under reflux and in situ synthesis. Of these, the method which showed the best results was the in situ synthesis, in which basal spacings of 14 ? (after calcination) were obtained, indicating that the samples are intercalated with metal oxides (Mg and Al). This procedure was reproduced with a Co-Al LDH (layered double hydroxide) and similar results were obtained, testifying the method reproducibility / Dois m?todos de pilariza??o de argilas foram testados a fim de se obter argilas pilarizadas com pilares mistos Al/Co. Utilizando o primeiro m?todo, baseado no procedimento tradicional, foram obtidos materiais contendo diferentes teores de Co: 10, 25, 50, 75 e 100 % de Co na solu??o pilarizante. Apenas os m?todos contendo baixos teores (10 e 25 % de Co) resultaram na forma??o de argilas pilarizadas, sendo que, a amostra contendo 25 % de cobalto apresentou resultados superiores aos obtidos apenas com Al (espa?amento basal acima de 18 ? e ?rea espec?fica BET maior que 300 m?/g). Os resultados de RMN de 27Al indicaram a forma??o de pilares mistos Al/Co devido ? diminui??o entre as intensidades dos sinais AlVI/AlIV, indicando que o teor de AlVI diminuiu conforme ocorreu o aumento do teor de Co, sugerindo a substitui??o isom?rfica de ?tomos de Al por Co na estrutura do ?on de Keggin (agente pilarizante). Para as amostras contendo 75 e 100 % de cobalto, verificou-se a forma??o de outros materiais, os quais foram identificados como sendo compostos do tipo hidrotalcita. O segundo m?todo de pilariza??o foi chamado de lamelas mistas, pois o objetivo era intercalar lamelas de argila com lamelas de hidrotalcita, assim ap?s a calcina??o, ocorreria a desidroxila??o da camada de HDL (hidr?xido duplo lamelar), resultando apenas nos ?xidos de metais, intercalados entre as lamelas da argila, gerando uma argila pilarizada. Para tal, foram testados 4 procedimentos de s?ntese: mistura f?sica, mistura em ?gua, troca i?nica em refluxo e s?ntese in situ. Desses, o m?todo que apresentou os resultados mais promissores foi o de s?ntese in situ, no qual espa?amentos da ordem de 14 ? (ap?s calcinar) foram obtidos, indicando que as amostras est?o intercaladas com ?xidos de metais (Mg e Al). Esse procedimento foi reproduzido com uma HDL contendo Co-Al, e resultados semelhantes foram obtidos, comprovando a reprodutibilidade do m?todo