Orientador: Peter Hammer / Banca: Cecilio Sadao Fugivara / Banca: Hudson Wallace Pereira de Carvalho / Resumo: Este projeto visa a investigar a relação entre a estrutura e as propriedades dos materiais epoxi-silica preparados pelo método sol-gel. Os híbridos foram preparados pela reação de cura entre o poly(Bisphenol A-co-epichlorohydrin) (DGBEA), e o dietil triamina (DETA) assim como pelo processo Sol-Gel de hidrolise e condensação entre GPTMS (3-Glycidoxypropyl)methyldiethoxysilane) e TEOS. Ressonância magnética nuclear (RMN), espectroscopia de fotoelétrons de raios X (XPS), espalhamento de raios X a baixo ângulo (SAXS), espectroscopia de Infravermelho e RAMAN, microscopia de força atômica (AFM) assim como termogravimétria foram utilizadas com o proposito de investigar a morfologia e as propriedades estruturais do material. Finalmente as propriedades anticorrosivas dos filmes foram testadas em uma solução salina por meio de espectroscopia de impedância eletroquímica (EIS). Durante a fase inicial do projeto diferentes amostras com diferentes concentrações de TEOS foram preparadas. A estabilidade térmica como as propriedades anticorrosivas foram testadas. Os resultados mostraram que para maiores concentrações de TEOS, as propriedades anticorrosivas e térmicas dos híbridos melhoram significativamente. Vários resultados interessantes foram obtidos, para híbridos com razoes molares de TEOS : GPTMS : DGBEA = 1 : 1: 1, tendo módulos de impedância de até 1010 Ω cm-2. Durante a segunda fase do projeto, duas series de amostras com concentrações diferentes de GPTMS a TEOS foram prepar... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work aims to investigate the relationship between the structure and the properties of the sol-gel prepared epoxy-silica materials. The organic-inorganic hybrids were prepared from the curing reaction of poly(Bisphenol A-co-epichlorohydrin) (DGBEA), with Diethyltriamine (DETA) and (3-Glycidoxypropyl)methyltriethoxysilane) (GPTMS) combined with the sol-gel hydrolysis and condensation reactions between Tetraethoxysilane (TEOS) and GPTMS. Nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), Infrared and Raman spectroscopy (IR), Atomic force microscopy, as well as thermogravimetry (TG) have been used with the purpose to investigate the morphological and structural properties of the material. Finally the anticorrosive properties of the hybrid coated carbon steel were evaluated in saline solution using electrochemical impedance spectroscopy (EIS). During the initial phase of the project different samples with increasing concentrations of TEOS have been prepared and their thermal stability as well as their anticorrosive properties were tested. It was found, that for increasing TEOS concentration, the hybrid's anticorrosive and thermal properties can be improved. Several interesting results were obtained for hybrid coatings at a TEOS : GPTMS : DGBEA = 1 : 1 : 1 ratio, having an impedance modulus of up to 1010 Ω cm-2. During the second phase of the work, a series of epoxy-silica hybrids were synthetized varying the concentrations of GPTMS and TEOS. Their str... (Complete abstract click electronic access below) / Mestre

Malgré leur grande activité antioxydante, l'utilisation de phénols naturels en tant qu'additifs antioxydants phénoliques pour les polyoléfines est limitée en raison de leur faible stabilité thermique et de leur caractère hydrophile. Nous présentons ici une synthèse chimio-enzymatique durable d’antioxydants lipophiles renouvelables spécifiquement conçus pour surmonter ces restrictions en utilisant de l’acide férulique naturel (présent dans la lignocellulose) et des huiles végétales (c.-à-d. acides lauriques, palmitiques, stéariques et glycérol). L'activité antiradicalaire (DPPH) ainsi que l'activité anti-oxydante (OIT) de ces nouveaux additifs entièrement biosourcés ont été rapportées à des antioxydants à base de carbone fossile disponibles dans le commerce tels que l'Irganox 1010® et l'Irganox 1076®. En outre, les tests d'activité œstrogénique n'ont révélé aucune perturbation du système endocrinien pour ces bisphénols nouvellement créés. La glycidylation de tous les composés a donné des précurseurs époxy biosourcés inoffensifs. Les analyses DSC, ATG et DMA démontrent que les propriétés thermomécaniques des résines époxy-amine obtenues peuvent être adaptées avec précision par le choix la longueur de la chaîne d’acides gras. / Despite their great antioxidant activities, the use of natural phenols as antioxidant additives for polyolefins is limited owing to their weak thermal stability and hydrophilic character. Herein, we report a sustainable chemo-enzymatic synthesis of renewable lipophilic phenolic antioxidants specifically designed to overcome these restrictions using naturally occurring ferulic acid (found in lignocellulose) and vegetal oils (i.e., lauric, palmitic, stearic acids, and glycerol) as starting materials. Antiradical activity (DPPH) as well as antioxidant activity (OIT) of these new fully biobased additives were reported to commercially available fossil-based antioxidants such as Irganox 1010® and Irganox 1076®. In addition, estrogenic activity tests revealed no endocrine disruption for newly created bisphenols. Glycidylation of all compounds afforded innocuous bio-based epoxy precursors. DSC, TGA and DMA analysis demonstrated that the thermo-mechanical properties of the obtained epoxy-amine resins can be finely tailored by judiciously selecting the fatty acid chain length.

Thesis (Ph.D.) -- Mississippi State University. Dave C. Swalm School of Chemical Engineering.. / Title from title screen. Includes bibliographical references.

Not available / text

M. Tech. Polymer Technology. / The gas permeability of composite epoxy resins formulated with graphene platelets and glass flakes was investigated. The purpose of researching the gas permeability of the composite resins was to develop a possible coating system that could prevent or limit the release of radioactive gases like tritium from irradiated graphite waste which may accumulate in underground repositories. Helium was used as a substitute gas to simulate the diffusive properties of tritium gas.

M. Tech. Polymer Technoliogy. / Studies the basic curing, rheological and thermomechanical behaviours of hybrids composed of a VE resin and acrylated epoxidised soyabean oil (AESO). The hybrid systems were cured by free radical initiated radical copolymerisation with styrene. The prospective outcomes were: To find suitable initiators/accelerators for the VE/AESO hybrids which work within the entire composition range? To contribute to the selection of VE resins for AESO modification To establish the optimal quantity of AESO required obtaining the best cure characteristics, the most acceptable reduction in Tg, and stiffness as compared with the parent VE resin.

El present treball té com objectiu l'obtenció de materials entrecreuats conservant una mesofase cristall líquid fixada, comunment denominats LCTs. La majoria de LCTs s'obtenen per entrecreuament de reïnes epoxi cristall líquid amb amines aromàtiques primàries. L'entrecreuament dins de la mesofase porta a materials amb un menor coeficient d'expansió tèrmica i en alguns casos amb un augment considerable del mòdul d'emmagatzematge. L'orientació dels LCTs per entrecreuament dins d'un camp magnètic porta a materials anisòtrops amb una millora de les propietats mecàniques en la direcció del camp aplicat. En aquest cas, s'han sintetitzat sis sèries de monòmers diepoxídics mesomorfs amb estructura de dímer i que contenen un grup imina dins la unitat mesogènica. S'ha estudiat la influència de la diferent llargària de l'espaciador central i la incorporació de grups èter i èster als extrems del mesògen en el comportament mesomorf. L'estudi de les característiques de cristall líquid s'han caracteritzat mitjançant calorimetria diferncial d'escombrat, microscopia òptica de llum polaritzada i difracció de raigs X. A més d'aquestes tècniques, s'han caracteritzat les propietats mecàniques dels LCTs obtinguts mitjançant anàlisi termodinamomecànica. Dues de les sèries han mostrat mesofases esmèctiques i la resta únicament una mesofase nemàtica. Els resultats obtinguts confirmen la importància de la polaritat del mesogen i de la posició del grup ester entre l'espaciador central i els mesògens per a la formació de mesofases esmèctiques.S'han obtingut LCTs a partir de l'entrecreuament d'aquest monòmers amb cantitats estequiomètriques de 2,4-diaminotoluè, 4,4'-aminoacetofenona azina, i 2,4-toluendiisocianat sol i catalitzat per 4-N,N-dimetilaminopiridina. També s'han obtingut LCTs per entrecreuament amb 4-N,Ndimetilaminopiridina i diazabiciclo[2,2,2]octà en quantitats catalítiques. Els LCTs obtinguts s'han caracterizat per fixar majoritàriament ordenacions nemàtiques i en alguns casos ordenacions esmèctiques C. En els LCTs obtinguts s'ha posat de manifest la importància de la polaritat del mesogen per l'obtenció de LCTs i de la posició del grup ester entre l'espaciador central i els mesògens per a la formació de LCTs amb ordenacions esmèctiques.S'han estudiat les propietats mecàniques dels LCTs entrecreuats amb 2,4-diaminotoluè, 4-N,N-dimetilaminopiridina i diazabiciclo[2,2,2]octà. S'han comparat tres tipus diferents de materials, materials isòtrops, orientats en microdominis i materials macroscòpicament orientats. S'han obtingut graus d'orientació petits, tot i que els materials orientats van mostrar anisotropia en el coeficient d'expansió tèrmica.Obtention of LCTs from liquid crystal epoxy resins with dimeric structure. / The search for new materials with unusual mechanical and thermal properties led to research into liquid crystalline thermosets (LCT's). LC epoxies are the monomers that have been most frequently studied to obtain LCT's. If the crosslinking is carried out in the mesophase, the LCTs obtained have unusual mechanical and thermal properties, low shrinkage upon cure, low thermal expansion coefficients, low dielectric constants and enhanced reaction rates because the ordered structures mean that the reacting groups are close to one another. Several publications describe the physical properties of oriented and unoriented LCT's. Macroscopically oriented LCTs obtained by curing in the mesomorphic state inside a magnetic field led to thermal expansion coefficient and storage modulus having anisotropic characteristics. Thus, the thermal expansion coefficient of macroscopically oriented materials must be lower than that of unoriented materials and the storage modulus must be expected to increase considerably in the direction of the orientation. I have synthesized six series of liquid-crystalline epoxy resins with aromatic azomethine groups and dimeric architecture, and varied the length of the alkyl spacer. The liquid crystal behaviour of these dimeric glycidylic compounds was studied by diferential scanning calorimetry (DSC), hot stage polarized optical microscopy (POM) and X-Ray Diffraction (WAXS). Two series of them show smectic mesophases and the other show nematic mesophase. From the results we have confirmed the importance of the polarization of the mesogenic groups and the presence of an ester group in the inner position in the formation of smectic mesophases.I obtained LCT's from these monomers by isothermal curing with equimolecular amounts of 2,4-diaminotoluene, 4,4'-aminoacetophenone azine, and 2-4-toluendiisocyanate alone and catalized with 4-N,N-dimethylaminopyridine. Another LCT's have obtained by isothermal curing with catalytic amounts of 4-N,N-dimethylaminopyridine or diazabicicle[2,2,2]octane. By curing these monomers with primary and tertiary amines we make clear the polarization of the mesogenic groups and the presence of an ester group in the inner position are also determinant to obtain LCTs with a different degree of order. Most monomers produced nematic-like networks, but in one case smectic C mesophase was also locked.Finally, the mechanical characterization of the LCTs obtained by curing with 2,4-diaminotoluene, 4-N,N-dimethylaminopyridine and diazabicicle[2,2,2]octane was studied by thermodinamicmechanical analysis. The orientation experiments were made by conducting the curing in the same conditions in a NMR probe with a magnetic field of 7.1 T. I compare isotropic materials, LCTs and LCTs obtained inside a magnetic field. Low orientation degrees have led. Macroscopically oriented

Carbon Nanotubes are thought to have tremendous potential as reinforcements for the next generation of composite materials. In the past decade, the enhancing effects of the nanotubes on the mechanical, electrical as well as multi-functional properties of polymer composites have been reported. However, the same nanotubes/polymer composites investigated by different research groups, in many cases, do not show a good agreement with one another. The root cause of this variability is believed to lie in the processing methodology employed to prepare the composites. Before one can propose an ideal and systematic processing condition, it is imperative to have a fundamental understanding of the effect of these nanotubes on the processing of the nanotube-based composites. In this study, the effect of 0.2wt.% functionalized single walled carbon nanotubes on the various thermo mechanical and thermo chemical properties of aerospace grade epoxy was investigated. Namely, the thermal degradation, rheological behavior, cure kinetics as well as the thermal expansion behavior of the epoxy were addressed. In addition, the effect of the application small quantity of nanotube/epoxy composite film on the interlaminar shear strength (ILSS) of a conventional laminated carbon fibre/epoxy prepregs was also investigated. The characterization results show that the presence of the nanotubes has a very significant effect on some of the inherent physical and chemical properties of the epoxy. The presence of these nanotubes leads to a delay in the degradation temperature of the epoxy. The viscosity sees a seven-fold increase at room temperature and the resin also gels at a lower temperature in the presence of the nanotubes. At the same time, the total heat of reaction is also lowered on addition of the nanotubes. The mechanical test, however, shows that the addition of the nanotube/epoxy film does not affect the ILSS of the laminated carbon fibre/epoxy composite. This ILSS value is also found to be dependant on the controlled alignment of the nanotubes and the method of application of the film at the interfaces of the laminates. Finally, it was observed that the nanotubes, when used in such low contents, also had no effect on the thermo mechanical properties of the epoxy. / Les nanotubes de carbone sont considérés comme ayant un potentielénorme pour assurer le rôle de renforts dans la prochaine génération de matériauxcomposites. Dans les décennies précédentes, les effets des nanotubes surl'amélioration des propriétés mécaniques, électriques et multi-fonctionnelles despolymères ont été révélés. Par contre, dans la plupart des cas, les études réaliséespar différents groupes de recherche et portant sur les mêmes composites faits depolymère renforcé de nanotubes ne présentent pas toutes des résultatscomparables. La cause majeure de cette variabilité est la méthodologie utiliséelors du procédé de fabrication de ces composites. Avant que quiconque ne suggèreune méthodologie idéale et systématique, il est impératif de comprendre les basesfondamentales de l'effet des nanotubes sur le procédé de fabrication. Dans cetterecherche, les effets des nanotubes de carbone à paroi simple sur les propriétésthermo mécaniques et thermo chimiques d'une résine époxy de gradeaéronautique ont été investigués. Les caractéristiques étudiées comprennent ladégradation thermique, le comportement rhéologique, la cinétique depolymérisation, ainsi que l'expansion thermique. L'effet de l'application d'unfilm de nanotube/époxy sur la résistance interlaminaire au cisaillement aégalement été étudié avec un préimprégné conventionel de fibre de carbone etd'époxy. Les résultats de caractérisation montrent que les nanotubes ont un effetsignificatif sur certaines propriétés physiques et chimiques inhérentes à l'époxy.La présence des nanotubes crée un délai dans la température de dégradation del'époxy. La viscosité de la résine est 7 fois plus élevée à la température de la pièceet sa température de gélification est inférieure. De plus, la chaleur totale deréaction est diminuée. Par contre, les tests mécaniques montrent que l'applicationd'un film de nanotube/époxy ne cause pas de changement dans la résistanceinterlaminaire au cisaillement d'un préimprégné de fibre de carbone et d'époxy.Par ailleurs, cette valeur de résistance est dépendante de l'alignement desnanotubes et de la méthode d'application du film sur les interfaces du laminé.Finalement, il a été observé que les nanotubes n'ont aucun effet sur les propriétésthermo mécaniques.

Thesis (M.S.)--Oregon State University, 2008. / Printout. Includes bibliographical references. Also available on the World Wide Web.

Um dos sistemas de proteção de substratos metálicos mais comumente empregado na indústria é o de tintas. Os fatores favoráveis à utilização das tintas em pó incluem a não utilização de solventes, facilidades de processamento/aplicação e possibilidade de reaproveitamento do material que não aderiu na superfície da peça. As características térmicas, mecânicas e químicas da tinta são influenciadas principalmente pelo tipo de resina utilizada. As tintas em pó híbridas (epóxi/poliéster) visam conciliar a característica de resistência ao intemperismo e ação dos raios UV com as características de resistência química e mecânica. Nas tintas em pó podem ser adicionados nanocargas que tem por finalidade melhorar as propriedades térmicas, mecânicas e químicas dos revestimentos. Outra característica das nanocargas é o baixo custo financeiro, decorrente da utilização de uma menor quantidade de carga, com elevado nível de desempenho. Dentre as nanocargas utilizadas, pode-se citar a mica muscovita e a montmorilonita 30B (MMT 30B) que, quando incorporadas às tintas, mesmo em baixas concentrações, apresentam propriedades de barreira superiores que às cargas convencionais. Este trabalho tem por objetivo desenvolver e caracterizar uma tinta em pó híbrida contendo diferentes teores de mica muscovita e MMT 30B. Os argilominerais foram incorporados numa formulação padrão de tinta em pó híbrida nas proporções de 2, 4 e 6% (m/m), separadamente. Antes da aplicação da tinta, os substratos metálicos foram submetidos a um pré-tratamento de fosfatização com fosfato de zinco. Após isso, a tinta em pó foi aplicada em painéis com dimensões de 70 x 120 x 0,65 mm de aço carbono AISI 1010 através de pulverização eletrostática. Os argilominerais, a tinta em pó e o revestimento foram analisados empregando diferentes técnicas de caracterização, tais como análise granulométrica, análise termogravimétrica (TGA), calorimetria exploratória diferencial (DSC), espectroscopia de infravermelho por transformada de Fourier (FTIR) e microscopia eletrônica de varredura por emissão de campo (MEVFEG). O efeito da incorporação dos argilominerais nas propriedades físicas e de proteção à corrosão das tintas foi avaliado com ensaios de medida de brilho, aderência, flexibilidade, resistência ao impacto, impedância eletroquímica (EIE), exposição à névoa salina (NS) e ensaio de chama. Para todas as tintas contendo argilominerais foi constatado o aumento da dureza superficial e a redução de brilho com o aumento do teor do argilomineral, sendo este efeito mais pronunciado com a adição de 6% (m/m) de MMT 30B. A aderência da tinta ao substrato não foi alterada pela presença dos argilominerais. As tintas contendo mica muscovita apresentaram melhores resultados nos ensaios de resistência ao impacto e de flexibilidade quando comparados as tintas contendo MMT 30B, nas concentrações testadas. A amostra TH/6/MICA apresentou melhor resultado no ensaio de impedância eletroquímica em relação aos outros sistemas estudados. No ensaio de névoa salina todas as amostras apresentaram elevada proteção à corrosão. Não foram observados bolhas ou pontos de corrosão na superfície de nenhuma das amostras. Porém, no ensaio subsequente de migração subcutânea, a amostra TH/2/MMT 30B foi a que apresentou maior desplacamento. No ensaio de chama, as tintas com incorporação de mica muscovita apresentaram melhores resultados que as tintas com MMT 30B. Após a análise de todos os ensaios, conclui-se que a adição de mica muscovita na proporção de 4% resultou em uma tinta com melhores propriedades térmicas, mecânicas e químicas. / Submitted by Ana Guimarães Pereira (agpereir@ucs.br) on 2016-06-20T18:52:21Z No. of bitstreams: 1 Dissertacao Natanael Relosi.pdf: 12806476 bytes, checksum: ebcfd4e992e53e3683c5ce7a0245866c (MD5) / Made available in DSpace on 2016-06-20T18:52:23Z (GMT). No. of bitstreams: 1 Dissertacao Natanael Relosi.pdf: 12806476 bytes, checksum: ebcfd4e992e53e3683c5ce7a0245866c (MD5) Previous issue date: 2016-06-20 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior. / One of metallic substrates protection systems most commonly used in the industry is the paint. Factors favorable to the use of powder coatings include non-use of solvents, processing facilities/application and the possibility of reuse of material that did not adhere to the surface of the pieces. The thermal, mechanical and chemical characteristics of the obtained paint are influenced principally by the type of resin used. Hybrid (epoxy/polyester) powder coatings aimed at reconciling the weathering resistance characteristic and action of UV rays with the chemical resistance and mechanical characteristics. In the powder coatings can be added nanofillers which aims to improve the thermal, mechanical and chemical coatings. Another feature of nanofillers is the low financial cost resulting from the use of a lesser amount of filler, with a high level of performance. Among the nanofiller used, it can be cited muscovite mica and montmorillonite 30B (MMT 30B) that, when incorporated into the coatings, even at low concentrations, have higher barrier properties than conventional fillers. This work aims to develop and characterize a hybrid powder coating containing different amounts of muscovite mica and MMT 30B. Clayminerals have been incorporated in a standard formulation hybrid powder coatings in proportions of 2, 4 and 6% (w/w). Before applying the coating, the metal substrates were subjected to a pretreatment phosphating with zinc phosphate. After this, the powder paint was applied to panels with dimensions 70 x 120 x 0.65 mm carbon steel AISI 1010 through electrostatic spraying. The clayminerals, the powder paint and coating were analyzed using various characterization techniques, such as particle size analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), infrared spectroscopy in Fourier transform (FTIR) and scanning electron microscopy for field emission (SEM-FEG). The effect of the incorporation of clayminerals in the physical properties and corrosion protection of coatings was evaluated with brightness measurement tests, adhesion, flexibility, impact resistance, electrochemical impedance spectroscopy (EIS), exposure to fog saline (NS) and flame test. For all coatings containing clayminerals was found to increase the surface hardness of the coating and reduced gloss with increasing clay content, this being more pronounced effect with the addition of 6% (w/w) of MMT 30B. The adhesion of the coating to the substrate was not altered by the presence of clayminerals. The coatings containing mica muscovite showed better results in impact resistance tests and flexibility when compared to coatings containing MMT 30B. The sample TH/6/MICA showed better results in the electrochemical impedance test in relation to other systems studied. In the salt spray test all samples showed high corrosion protection. There were no blistering or corrosion spots on the surface of any of the samples. However, in the subsequent test of subcutaneous migration, the sample TH/2/MMT 30B showed the greatest peeling. In the flame test, coatings with incorporation of muscovite mica showed better results than coatings with MMT 30B. After analyzing all the tests, it is concluded that the addition of muscovite mica in the proportion of 4% resulted in an paint with improved thermal, mechanical and chemical properties.