In this study, ethyl methacrylate was polymerized by free radical polymerization at 600C, 700C, 800C at open atmosphere / atom transfer radical polymerization, (ATRP), at 800C in vacuum and in gamma irradiation in vacuum. The polymer obtained was white, hard material. The kinetic curves for free radical polymerization and ATRP by gamma radiation were S-type. However, the curve for polymerization by gamma irradiation raises more smoothly. For ATRP by thermal initiation gives a lineer change of conversion with time. It was observed that the molecular weight can be controlled and low molecular weight polymer could be obtained by ATRP method. The characterization of polymers were made by FTIR, DSC, 1H and 13C NMR techniques.

Orientador: Rogério Lopes Vieites / Banca: João Domingos Rodrigues / Banca: Luciana Costa Lima / Resumo: Este trabalho teve como objetivo prolongar a vida útil de pêssegos cv. Tropic Beauty, provenientes de Holambra II - SP, com o emprego da irradiação gama e o uso de adsorvedores de etileno em frutos refrigerados. Foram realizados dois experimentos: Experimento 1 - frutos irradiados (0,0; 0,4; 0,6; 0,8; 1,0KGy) submetidos à atmosfera modificada passiva (sem adsorção de etileno); e Experimento 2 - frutos irradiados (0,0; 0,4; 0,6; 0,8; 1,0KGy) submetidos à atmosfera modificada ativa (com adsorção de etileno por saches de permanganato de potássio, 12g). Os frutos foram selecionados, embalados e prérefrigerados a 4°C por 12 horas para então serem irradiados na EMBRARAD, localizada em Cotia - SP. Logo após seguiram para o Laboratório de Frutas e Hortaliças, pertencente ao Departamento de Gestão e Tecnologia Agroindustrial, da Faculdade de Ciências Agronômicas - UNESP - Câmpus de Botucatu, SP. Nos dois experimentos, os frutos após os tratamentos, foram armazenados em B.O.D. a 0°C e com 90±5% de UR por 25 dias. As avaliações foram realizadas a cada cinco dias, durante 25 dias de armazenamento. As alterações na qualidade pós-colheita foram detectadas por meio das análises de perda de massa fresca, firmeza, pH, acidez titulável, sólidos solúveis, relação SS/AT "Ratio", ácido ascórbico, açúcares redutores, açúcares redutores totais e respiração. O delineamento estatístico empregado foi inteiramente casualizado com três repetições por tratamento para cada um dos cinco tempos de avaliação, utilizando-se o Teste de Tukey a 5% de probabilidade. Nas condições em que os experimentos foram realizados, os resultados permitem concluir que, a irradiação gama e o uso de adsorvedores de etileno influenciaram as características avaliadas. Analisando os resultados conclui-se que o uso da atmosfera ...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study aimed to prolong the shelf-life of cv. Tropic Beauty peaches, from Holambra II-SP, employing gamma irradiation and the use or not of adsorbent ethylene in refrigerated fruits. Two experiments were conducted: 1- fruit irradiated (0.0, 0.4, 0.6, 0.8, 1.0KGy) submitted to a passive modified atmosphere (no adsorption of ethylene), and 2- fruit irradiated ( 0.0, 0.4, 0.6, 0.8, 1.0KGy) submitted to an active modified atmosphere (with the adsorption of ethylene by potassium permanganate sachets, 12g). The fruits were selected, packaged and pre-chilled at 4°C for 12 hours to be irradiated at EMBRARAD, located in Cotia - SP. They were directed to the Laboratory of Fruit and Vegetables from the Department of Management and Agribusiness Technology of the Agronomical Sciences Faculty - UNESP - Botucatu, Brazil. In both experiments, the fruits after the treatments were stored in B.O.D at 0 ° C with 90 ± 5% RH for 25 days. Evaluations were conducted every five days, during 25 days of storage. Changes in the post-harvest quality were detected by means of the analysis of fresh mass loss, texture (firmness), pH, total titrable acidity, soluble solids, 'Ratio' (SS/TTA), ascorbic acid, reducing ...(Complete abstract click electronic access below) / Mestre

Orientador: Keizo Yukimitu / Resumo: Vidros a base de óxidos de metais pesados (TeO2, WO3, Bi2O3) apresentam alto índice de refração, altos valores de não-linearidade óptica e alta constante dielétrica. Essas propriedades físicas possibilitam diversas aplicações, como, por exemplo, para comutação ultrarrápida em dispositivos ópticos e, exibem, quando dopados com terras raras, importantes propriedades de luminescência [1]. Vidros dos sistemas ternários xTeO2 – yB2O3 – zWO3 e xTeO2 – yB2O3 – kBi2O3 foram preparados pelo método “melt-quenching” com x de 70 a 45%mol, y de 40 a 10%mol, z de 30 a 15%mol e k com variação de 20 a 10%mol. Introduzimos o óxido de Boro para dar maior viscosidade ao material e aumentar a estabilidade térmica. Foram obtidas amostras homogêneas e transparentes para as seguintes composições: 70TeO2–10B2O3–20WO3, 70TeO2–20B2O3–10Bi2O3 e 55TeO2 –30B2O3–15Bi2O3. Dados de espectroscopia de IR revelaram que a rede dos vidros consiste basicamente das seguintes unidades estruturais: [TeO4], [WO4], [WO6], [BO4], [BO3] e Te-O-W para o sistema TeO2 – B2O3 – WO3 e de [TeO4], [BiO3], [BiO6], [BO4], [BO3] para o sistema TeO2 – B2O3 – Bi2O3. Medidas de absorção óptica das amostras foram realizadas antes e após a exposição a irradiação gama em doses de 10Gy, 1kGy, 10kGy e 50kGy e forneceram valores das bordas de absorção no intervalo de 378 a 449 nm. Obtiveram-se índices de refração da ordem de n > 2 em 633 nm através do equipamento Interferômetro de Michelson e método do ângulo de Brewster. As energias do g... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Glasses based on heavy metal oxides (TeO2, WO3, Bi2O3) have high refractive index, high values of optical nonlinearity and high dielectric constant. These physical properties enable a variety of applications, such as for ultrafast switching in optical devices and, when doped with rare earths, exhibit important luminescence [1]. Glasses in the ternary systems xTeO2–yB2O3–zWO3 and xTeO2–yB2O3–kBi2O3 were prepared from melt quenching method with x from 70 to 45 mol%, y from 40 to 10 mol%, z from 30 to 15 mol% and k with variation from 20 to 10 mol%. We introduce the Boron oxide to give a higher viscosity to the material, ie, higher thermal stability. Homogeneous and transparent samples were obtained for the following compositions: 70TeO2–10B2O3–20WO3, 70TeO2–20B2O3–10Bi2O3 and 55TeO2 –30B2O3–15Bi2O3. FTIR spectroscopy data revealed that the glass basically consists of the following structural units: [TeO4], [WO4], [WO6], [BO4], [BO3] and Te-O-W to the system TeO2–B2O3–WO3 and [TeO4], [BiO3], [BiO6], [BO4], [BO3] to the system TeO2–B2O3–Bi2O3. Optical absorption measurements of the samples were performed before and after exposure to gamma irradiation at doses of 10Gy, 1kGy, 10kGy and 50kGy and provided absorption edge values in the range of 378 to 449 nm. Were obtained refractive index of the order of n> 2 at 633 nm through the equipment Michelson´s Interferometer and Brewster's angle method. The optical gap energies obtained from these glasses are of the order of ≈ 2 to 3 eV. / Doutor

Made available in DSpace on 2014-06-11T19:26:41Z (GMT). No. of bitstreams: 0 Previous issue date: 2005-06-20Bitstream added on 2014-06-13T20:15:27Z : No. of bitstreams: 1 moreira_gc_me_botfca.pdf: 522936 bytes, checksum: 59249a8e43961d1234678ad95d42c9af (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho teve por objetivo verificar os efeitos do ácido ascórbico e da radiação gama na conservação pós-colheita de maçã Royal Gala minimamente processada, submetida à refrigeração, visando estender a sua vida útil, retardando seu amadurecimento e reduzindo a incidência de patógenos, sem prejuízo das suas características físicas, químicas e organolépticas. Foram realizados 4 experimentos: Experimento 1 - os frutos processados em cubos de 2 x 2 cm; Experimento 2 - os frutos processados em rodelas de 1 cm; Experimento 3 - os frutos cortados em 4 partes. Para os experimentos 1, 2 e 3, após o processamento nos diferentes cortes, os frutos foram acondicionadas em bandejas de isopor envolvidas em filme plástico e submetidas a diferentes concentrações de ácido ascórbico (0%, 1%, 2%, 3% e 4%); Experimento 4 - os frutos processados em cubos de 2 x 2 cm, imersos em solução de 3% de ácido ascórbico, acondicionados em bandejas de isopor envolvidas em filme plástico e irradiadas com diferentes doses de radiação gama (T1 - Testemunha (0,0kGy), T2 - 0,1kGy, T3 - 0,2kGy, T4 - 0,3kGy, T5 - 0,4kGy, T6 - 0,5kGy). As frutas foram irradiadas na EMBRARAD, localizada em Cotia - SP. Foram utilizadas nessa pesquisa maçãs Royal Gala, provenientes da Empresa Agroban (Vacaria - RS). Os frutos foram transportados ao Laboratório de Frutas e Hortaliças, pertencente ao Departamento de Gestão e Tecnologia Agroindustrial, da Faculdade de Ciências Agronômicas - UNESP - Câmpus de Botucatu, SP. Para cada experimento, os frutos após receberem cada tratamento, foram armazenados em câmara fria a 5l1ºC e 85 - 90% de umidade relativa. As avaliações foram realizadas a cada dois dias, durante 10 dias de armazenamento. As alterações na qualidade pós-colheita foram detectadas por meio das análises de perda de massa fresca... / The present work had as objective to verify the effects of the ascorbic acid and the gamma radiation in the postharvest conservation of the minimally processed apple 'Royal Gala' minimally processed, submitted to the refrigeration aiming to extend its useful life, delaying its ripening and reducing the microorganisms incidence, without damage of its physical, chemistries and sensorial characteristics. Four experiments were accomplished: Experiment 1 - the fruits processed in cubes of 2 x 2 cm; Experiment 2 - the fruits processed in slices of 1 cm; Experiment 3 - the fruits cut in 4 parts. For the experiments 1, 2 and 3, after the processing in the different cuts, the fruits were conditioned in isopor trays involved in plastic film and submitted to different concentrations of ascorbic acid (0%, 1%, 2%, 3% and 4%); Experiment 4 - the fruits processed in cubes of 2 x 2 cm, immersed in solution of 3% of ascorbic acid, conditioned in isopor trays involved in plastic film and irradiated with different gamma radiation doses (T1 - control (0,0kGy), T2 - 0,1kGy, T3 - 0,2kGy, T4 - 0,3kGy, T5 - 0,4kGy, T6 - 0,5kGy). The fruits were irradiated in EMBRARAD, located in Cotia - SP. Apples ' Royal Gala' were used in this research, coming from the Company Agroban (Vacaria - RS). The fruits were transported to the Laboratory of Fruits and Vegetables, belonging to the 'Departamento de Gestão e Tecnologia Agroindustrial', of 'Faculdade de Ciências Agronômicas - UNESP - Campus of Botucatu, SP'. Each fruit after receiving treatment, was stored for each experiment in a cold camera to 5l1ºC and 85 - 90% of relative humidity. The evaluations were accomplished every other day, for 10 days of storage. The alterations in the quality postharvest were detected through the analyses of loss of fresh mass... (Complete abstract, click electronic access below)

La technologie supercondensateur a fait l'objet d'un grand intérêt ces dernières années. Cependant, tandis qu'une grande attention a été donnée aux électrodes, aux électrolytes et aux électrolytes de polymère gélifiée, peu d'études ont été centrées sur l'amélioration des séparateurs macroporeux. Dans le cadre du projet SEPBATT/DURAMAT, les séparateurs macroporeux à base de poly(fluorure de vinylidène) (PVdF) ont été préparés par inversion de phase, pour les supercondensateurs. Nos membranes présentent également une bonne stabilité thermique, en revanche leurs propriétés mécaniques sont significativement plus faibles que celles des membranes commerciales. De plus le séparateur PVdF de porosité 80% rempli par l'électrolyte à base d'AN atteint, à 25°C, 18mS/cm, tandis que dans les mêmes conditions mais avec le séparateur commercial en cellulose, la conductivité n'atteint que 10 mS/cm. Ce travail a été complété par l'étude de techniques de renforcement (addition de composites, réticulation par l'irradiation) appliquées aux membranes précédemment préparées, pour augmenter leur tenue mécanique. Ces membranes ont montré un renforcement des propriétés mécaniques sans nuire aux propriétés de conduction ionique (15 mS/cm). / Abstract In recent years a strong interest has been devoted to supercapacitor technology. However, while great attention has been paid to electrodes, electrolytes and gel polymer electrolytes, only few reports have been dedicated to macroporous separators. Hereby, in the frame of project SEPBATT/DURAMAT, macroporous poly(vinylidene fluoride) (PVdF) based separators were prepared by phase inversion technique for applications of supercapacitors. Their mechanical properties are relatively lower than those of commercial membranes nevertheless such membranes exhibit good thermal stability. Whereas commercial cellulose based separators filled with tetraethyl ammonium tetrafluoroborate + CH3CN electrolyte show 10 mS/cm (at 25°C), our PVdF macroporous separators exhibit significantly higher conductivity (18 mS/cm) under the same conditions. This study was completed with application of reinforcement techniques (addition of composites, crosslinking by irradiation) on to previously prepared membranes in order to increase their mechanical strength. Reinforced membranes showed good high mechanical strength whereas the ionic conductivity is almost maintained (15mS/cm).

Made available in DSpace on 2014-10-09T12:54:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:58Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:54:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:58Z (GMT). No. of bitstreams: 0 / Os óleos lubrificantes automotivos durante o seu uso sofrem degradação parcial de compostos orgânicos e incorporam elementos inorgânicos indesejáveis. Estas substâncias tornam o óleo lubrificante usado classificado como perigoso e altamente tóxico. Assim, no que diz respeito à conservação ambiental, o consenso mundial é que a melhor solução para os óleos lubrificantes usados objetive no tratamento para a sua reutilização. Dentro deste contexto e visando o uso de uma tecnologia alternativa, neste trabalho foi proposto um estudo sobre a eficiência e a viabilidade técnica do processo de oxidação avançada (POA) por radiação gama para o tratamento de óleo lubrificante automotivo usado. Amostras de óleo lubrificante usado foram diluídas em concentrações variadas com peróxido de hidrogênio e água Milli-Q. Estas amostras foram submetida a um irradiador de Cobalto-60, tipo Gammacell, com as doses absorvidas de 100, 200 e 500 kGy. Os resultados das análises inorgânicas por fluorescência de raios X (WDXRF) mostraram que o tratamento proposto permite a remoção de elementos inorgânicos, principalmente enxofre, cálcio, ferro e níquel em níveis aceitáveis pela legislação ambiental para reuso destes óleos. Os resultados por cromatografia gasosa (CG/MS) mostraram que este tratamento, também, promove a degradação dos compostos orgânicos, formando principalmente, os compostos tridecano, 2-metil-naftaleno, trietilamina e uréia-tetrametil, os quais são de grande aplicação industrial. A análise multivariada, análise de Cluster (CA), confirmou que a aplicação POA é um tratamento promissor e viável para o reuso de óleo lubrificante usado. INORGANIC / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Les systèmes plastiques à usage unique sont destinés aux industries biopharmaceutiques et biotechnologiques. Ils sont composés de polymères et sont appréciés pour leurs propriétés barrières au gaz et à la vapeur d’eau assurant une préservation des solutions contenues dans ces systèmes. Ces dispositifs présentent de nombreux avantages pour les industriels : ils permettent d’éviter un nettoyage des cuves en inox et ainsi de limiter des risques de contamination croisée. En vue de leur utilisation, ces dispositifs sont stérilisés par irradiation γ. Le but de cette étude est de mettre en évidence l'impact de la stérilisation γ sur certains polymères et sur certains antioxydants utilisés dans la fabrication des polymères. Plusieurs échantillons sont analysés avant et après la stérilisation en utilisant différentes doses de rayonnement γ et au cours du temps (vieillissements naturels). Les modifications de structure des polymères γ-irradiés (EVA, PE et EVOH) ont été caractérisées par diverses méthodes analytiques : IRTF, spectroscopie Raman, RPE, chromatographie… Les résultats sont traités en utilisant des méthodes chimiométriques, comme l’ACP (Analyse en Composantes Principales), l’AComDim (ANOVA Common Dimensions) et SIMPLISMA (Simple-to-use interactive self-modeling mixture analysis). L’ACP a permis de mettre en évidence l’impact de la dose d’irradiation sur le polymère. L’AComDim a conduit à identifier les facteurs responsables de l’évolution des structures (la dose γ, les temps et l’interaction dose γ × temps), alors que les différents lots n’induisent pas de déviation. Enfin, la méthode de résolution de courbe SIMPLISMA a été appliquée pour l’étude du cœur du matériau. / The single use plastic systems are designed for biopharmaceutical and biotechnology industries. They are principally made of polymers and they are very appreciated for their barrier properties to gas and water vapor ensuring preservation of the solutions contained in these single-use systems. These devices have many advantages for industrial: they avoid cleaning stainless steel tanks and thus limit the risk of cross-contamination. In view of their future use, these devices are sterilized by γ-irradiation. The purpose of this study is to highlight the impact of γ sterilization on some polymers and on some antioxidants used in the manufacture of polymers. The samples are analyzed before and after sterilization using different γ-doses and over time (natural ageing). The structural modifications of γ-irradiated polymers (EVA, EVOH and PE) were characterized by various analytical methods: FTIR, Raman spectroscopy, ESR, chromatography… Some results are analyzed using chemometric methods such as PCA (Principal Component Analysis), AComDim (ANOVA Common Dimensions), and SIMPLISMA (Simple-to-use interactive self-modeling mixture analysis). The PCA allowed to highlight the impact of the irradiation dose on the polymer. The AComDim method led to the identification of the factors contributing to the evolution of structures (γ-dose, ageing and γ × ageing interaction), whereas the several lots do not involve variation. Finally, the curve resolution method, SIMPLISMA, was applied to the study of the core of the material.

L’utilisation du procédé d’osmose inverse (OI) pour le traitement d’effluents nucléaires aqueux pose la problématique des effets de radiolyse et de vieillissement des membranes sous irradiation ɣ. Les performances des membranes (perméabilité, taux de rétention en strontium et césium) après irradiation ɣ ont été étudiées. L’irradiation par une source externe (60Co) a été réalisée dans différentes conditions représentatives de situations réelles (0,1 à 1 MGy, à 0,5 et 5 kGy.h-1, présence ou absence d’eau et d’oxygène). Une démarche analytique innovante et complémentaire (FTIR-ATR, XPS, production de gaz et d’espèces hydrosolubles) a été mise en œuvre afin d’obtenir des informations pertinentes sur les effets de l’irradiation sur les matériaux constitutifs. La chute des performances, débutant entre 0,2 MGy et 0,5 MGy, en présence d’oxygène et d’eau (débit de dose 0,5 kGy.h-1), est liée à des scissions de chaînes localisées sur la couche active de la membrane. Les dégradations se sont révélées plus faibles en absence d’oxygène et d’eau et à débit de dose à élevé. Les performances des membranes ont ensuite été évaluées sur trois matrices aqueuses différentes représentant respectivement des effluents radioactifs issus de situation post-accidentelle, accidentelle ou procédé. Les essais menés à l’échelle laboratoire et pilote montrent que dans chaque cas, l’utilisation de l’OI est possible en choisissant des membranes et des conditions opératoires adaptées. Pour finir, le temps pour atteindre une valeur seuil de dose intégrée reçue par les membranes a été estimé grâce au logiciel RABBI : une dizaine de jours pour l’effluent accidentel, plusieurs années pour les deux autres cas. / The treatment of nuclear liquid wastes by reverse osmosis (RO) involved issues of the water radiolysis and the membrane ageing due to ɣ irradiation effects. Membrane performances (permeability, strontium and cesium retention) were assessed after ɣ irradiation. Irradiation was carried out with an external 60Co source in different conditions that simulated real used of the process (dose from 0.1 to 1 MGy, dose rate of 0.5 and 5 kGy.h-1, with or without oxygen or water). Several analytical methods were performed to evaluate irradiation effects (ATR-FTIR, XPS, gas production, water soluble species released from the membrane). The methodology developed led to relevant information due to an innovative analytical protocol. Membrane performances started dropping between 0.2 and 0.5 MGy with oxygen and water (dose rate 0.5 kGy.h-1). This shift was linked to chains scissions inside the membrane active layer. The membrane degradation was weaker without oxygen or water or at high dose rate (5 kGy.h-1). Results showed that each analysis comforted each other. Membrane performances were also evaluated with three different types of liquid effluents, representing radioactive effluents from a post-disaster situation (groundwater type), disaster situation (seawater) or process water. Experiments were carried out at lab and pilote scales. Results indicated that the treatment of each effluent was possible by RO with an adequate choice of membrane and operating parameters. Finally, the time to reach an integrated dose threshold for the membrane in real conditions was estimated with the RABBI software : a dozen of days in the case of disaster situation to several years in the two other cases.

To assess the effects of gamma radiation at low doses, spores of Penicillium expansum NRRL 971 and Penicillium patulum NRRL 989 were exposed to doses of 0, 50, 100, 150, and 200 krads. The amount of patulin for each culture was quantitatively determined and growth at each dose was evaluated. The results showed a 31% increase in the amount of patulin synthesis after a dose of 150 krads for Penicillium expansum At 200 krads, both fungi showed low levels of patulin production and inhibited growth. Eight color mutants of P. expansum and eight color mutants of P. patulum were produced by exposing spores of each fungus to doses of 150 and 200 krads of gamma radiation. An evaluation of patulin production and growth for each mutant showed that color mutation could result in mutants with an enhanced ability to grow or produce increased levels of patulin. When grown at a subatmospheric pressure of 320 mm Hg, P. expansum produced 30% more patulin per flask, when compared to control cultures. At 160 mm Hg, P. expansum showed a 75% decrease over the control cultures. P. patulum was greatly affected by the temperature of 15℃ and showed decreases both in growth and patulin production. Effective control of growth and patulin synthesis was found for these fungi at 160 mm Hg.