Orientador: José Antonio Malmonge / Banca: Haroldo Naoyuki Nagashima / Banca: Eliton Souto de Medeiros / Banca: Maria Alice Martins / Banca: Aldo Eloizo Job / Resumo: Nanowhiskers de celulose (CNF) foram obtidas de microfibras de algodão comercial (MFC) por meio de hidrólise ácida e recobertas com polianilina (PANI) via polimerização "in situ", visando a obtenção de amostras condutoras (CNF-PANI). Nanocompósitos de Borracha Natural (BN) com nanowhiskers (nanofibras) recobertos e não recoberto com PANI também foram obtidos em diferentes proporções em massa, pelo método casting/evaporação, nas proporções em massa 97/03, 95/05, 93/07 e 90/10. Os nanocompósitos foram caracterizados utilizando as técnicas de espectroscopia UV-Vis-NIR, FTIR, DSC, TG/DTG, difratometria de raios-X, MEV-FEG, ensaios de mecânicos em tração e medidas elétricas dc e ac. Pelas as análises elétricas as amostras de CNF-PANI, alcançaram condutividade da ordem de 10-1 S/cm independente do ácido dopante utilizado (DBSA ou HCl). As CNF-PANI também apresentaram estabilidade térmica maior do que as CNF não recobertas, pois a PANI atua como uma barreira protegendo as CNF. Nas análises de TG/DTG foi observado que a estabilidade térmica dos nanocompósitos de BN/CNF e BN/CNF-PANI apresentaram comportamento semelhantes ao da BN. A temperatura de transição vítrea dos nanocompósitos foi similar ao da BN (-63 °C) não sofrendo mudança com a introdução de CNF e de CNF-PANI. A introdução de CNF e CNF-PANI impactaram positivamente nas propriedades mecânicas da BN devido ao fenômeno de percolação mecânica dos nanowhiskers que formam uma rede contínua na matriz de nanopartículas unidas por meio de ligações de hidrogênio. Os nanocompósitos reforçados com CNF (BN/CNF) exibiram maior módulo de Young e resistência mecânica na ruptura, do que os nanocompósitos BN/CNF-PANI. Já as análises elétricas demonstraram que a condutividade elétrica dos nanocompósitos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Cellulose nanowhiskers (CNF) were isolated from cotton microfibrils (MCF) by acid hydrolysis and coated with polyaniline (PANI) by in situ polymerization of aniline onto CNF to produce conductive nanocomposite (CNF-PANI). Nanocomposites of natural rubber (NR) reinforced with CNF and CNF-PANI also were obtained by casting/evaporation method. The samples were characterized by ac and dc electrical conductivity, UV-Vis-NIR and Fourier-transform infrared (FTIR) spectroscopies, X-ray diffraction, DSC, TGA/DTG, SEM and strain-stress technique. Electrical conductivity about 10-1 S/cm was achieved for the CNF-PANI nanocomposites independent of dopant acids (DBSA or HCl). The nanowhiskers coated with PANI shown to be more thermally stable than the uncoated CNF, because the PANI acts as a barrier protecting the CNF. The NR/CNF and NR/CNF-PANI nanocomposites and neat NR sample showed the same thermal profiles. The glass transition temperature of the NR was not affected by nanowhiskers content. The mechanical properties of natural rubber improved with nanofibrils incorporation. Young's modulus and tensile strength were higher for NR/CNF than the NR/CNF-PANI nanocomposites, probably because the CNF is more hydrophobic than CNF-PANI. The electrical conductivity of natural rubber increased five and seven orders of magnitude for NR with 10 wt% of CNF-PANI(HCl) and CNF-PANI(DBSA) content, respectively. A partial PANI dedoping might be responsible for the low electrical conductivity of the nanocomposites compared to CNF-PANI (HCL and DBSA). A statistical model of a resistor network was developed to simulate the structure and reproduced the ac conductivity of the NR/CNF-PANI nanocomposite by the application of a transfer-matrix technique. According to the simulation results, the conduction process between two sites of... (Complete abstract click electronic access below) / Doutor

Orientador: José Antonio Malmonge / Banca: Walter Katsumi Sakamoto / Banca: Neri Alves / Resumo: Compósitos de borracha natural vulcanizada (BV) e Titanato Zirconato de Chumbo (PZT) em diferentes composições foram obtidos a partir do látex pré-vulcanizado e da cerâmica PZT na forma de pó. As composições estudadas foram 90/10, 80/20, 70/30 e 60/40 v/v. Um aumento no coeficiente piezoelétrico (d33) foi verificado com o aumento do volume de cerâmica no compósito, atingindo um valor de aproximadamente 6 pC/N para compósitos de composição 60/40 polarizados a 8MV/m na temperatura de 90°C. Verificou-se um decaimento da atividade piezoelétrica em função do tempo após a polarização para os compósitos com até 30% em volume de cerâmica. Este decaimento foi atribuído principalmente à relaxação da matriz. A adição de nanofibras de celulose para a composição 70/30 nas proporções 5,10 e 15% em massa (em relação à massa da borracha), inibiu o processo de relaxação, como também promoveu uma melhor transferência de tensões mecânicas aplicadas no material aos grãos cerâmicos, ocasionando em um aumento de até 400% nos valores obtidos para o coeficiente piezoelétrico. A incorporação de 5% em massa de nanofibras recobertas com polianilina aumentou três ordens de grandeza a condutividade elétrica dos compósitos 70/30 e 60/40. Por outro lado, uma redução nos valores do coeficiente piezoelétrico foi observada, o que foi atribuído a um efeito de blindagem elétrica dos grãos cerâmicos / Abstract: Vulcanized natural rubber(VNR) and Lead Zirconate Titanate (PZT) composites with different composition were obtained by mixing PZT ceramic powder with prevulcanized latex. The investigated composition of VNR/PZT were 90/10, 80/20, 70/30 and 60/40 v/v. The piezoelectric coefficient d33 increased with increasing of PZT volume fraction in the composite reaching approximately 6 pC/N for composites composition 60/40 %v/v, polarized with 8MV/m at 900C. It was verified that piezoelectric activity decay as a function of time for composite up to 30% of ceramic, that was attributed mainly to matrix relaxation. The incorporation of cellulose nanofibers in the compositions 70/30 and 60/40 %v/v inhibited the matrix relaxation besides of promoting better transference of the applied mechanical stress on the ceramic grains, increasing the piezoelectric coefficient d33 about 400%. The electrical conductivity of composites 70/30 and 60/40 increased three order of magnitude by adding 5% in mass (related to rubber mass), of cellulose nanofiber coated with polyaniline in the composite. On the another hand, the piezoelectricity activity d33 decreased and this behavior was attributed to electrical field shielding of ceramic grain promoted by coated fibers / Mestre

Orientador: Aldo Eloizo Job / Co-orientador: Deuber Lincon da Silva Agostini / Banca: Claudia Merlini / Banca: Neri Alves / O Programa de Pós Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi / Resumo: A técnica de eletrofiação tem sido utilizada na obtenção de fibras com diversos materiais poliméricos. Neste trabalho, foram desenvolvidos, de maneira inédita, materiais eletrofiados a partir de borracha natural e polianilina. Por esta técnica, foram obtidas mantas eletrofiadas com fibras de diâmetro menor que 1 um. Para o desenvolvimento destas mantas eletrofiadas tornou-se necessário primeiramente realizar um amplo estudo sobre os parâmetros de processo, o qual constou em variar o fluxo de vazão da solução polimérica de 0.1, 0,25, 0,5 mL/h, a tensão aplicada ao processo de 10, 12,5....., 15 kV e a rotação do coletor rotativo onde as fibras foram depositadas em 30, 40, 50 rpm. Após o estudo dos parâmetros de eletrofiação, foi selecionada uma série com os melhores parâmetros, que proporcionou a obtenção de mantas de borracha natural denominada BN. Estas mantas foram posteriormente recobertas com polianilina pelo método de polimerização in situ, obtendo mantas de BN/PAni dopada e BN/PAni desdopada. Para fins de comparação foram também produzidas membranas densas pelo método casting, que foram caracterizadas quanto suas propriedades elétricas, onde mostrou bons resultados, se comportando como material ôhmico alcançando a condutividade na ordem de 10-6 S/m para BN/PAni dopada, enquadrado assim entre os materiais semicondutores. Além das propriedades elétricas foram também investigadas as propriedades térmicas, espectroscópicas dos materiais estudados. Os resultados deste trabalho mostraram que é possível eletrofiar a borracha natural formando fibras de diâmetro que alcançaram valores mínimos de até 0,92 um / Abstract: The electrospinning technique has been used to obtain fibers with various polymer materials. In this work were developed in an unprecedented fibers electrospun from natural rubber and polyaniline. For this technique, fibers mats were obtained with fiber diameter of less than 1 micrometers. For the development of these electrospun mats became necessary to first perform an extensive study on the process parameters, which consisted in varying the flow of polymer solution at 0.1, 0.25, 0.5 ml/h, the voltage applied to the process 10, 12.5, 15 kV and rotation of the collector where the fibers were deposited on 30, 40, 50 rpm. After studying the electrospinning parameters, it selected a series with the best parameters, which provided obtaining natural rubber mats called NR. These mats were covered with polyaniline by in situ polymerization method, getting NR/PAni doped and NR/PAni undoped mats. For purposes of comparison were also produced membranes by casting method, which were characterized as its electrical properties, which showed good results, behaving as ohmic materials reaching the conductivity on the order of 10-6 S/m for NR/PAni doped, entering among the semiconductor materials. In addition to the electrical properties were also investigated the thermal, spectroscopic and morphological materials properties. These results showed that it is possible produced natural rubber fibers electrospun forming diameter fibers that have reached minimum values of up to 0.92 micrometers / Mestre

Made available in DSpace on 2014-06-11T19:30:19Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-01-27Bitstream added on 2014-06-13T18:40:19Z : No. of bitstreams: 1 cabrera_fc_me_bauru.pdf: 4656699 bytes, checksum: a5fecfc7e09b6d60f2c221aa0d2cd019 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho, desenvolvido junto ao Grupo de Pesquisa em Novos Materiais e Aplicações, do Departamento de Física, Química e Biologia, da Faculdade de Ciência e Tecnologia FCT/UNESP Campus de Presidente Prudente, propomos realizar a investigação da fabricação de membranas de borracha a partir do látex extraído de árvores do gênero Hevea brasiliensis (clone RRIM 600 - Rubber Research Institute of Malaysia). As membranas são preparadas através da técnica de casting e utilizadas como substratos ativos (agente redutor e estabilizador) nas sínteses de nanopartículas (NPs) metálicas, pelo método de redução in situ, por meio de solução aquosa de cloreto de ouro (AuCl3), de modo que as nanopartículas sejam incorporadas tanto na superfície quanto no volume das membranas. Como objetivo principal propõe-se obter informações relevantes sobre os compostos ligados às membranas de borracha natural aos quais se atribuí a responsabilidade pela redução e estabilização das nanopartículas. Os resultados demonstram que a síntese de nanopartículas pode ser desenvolvida, com tamanhos médios por volta de 48 nm, incorporando-as como agregados na superfície das membranas de borracha natural. A redução das nanopartículas de ouro foi atribuída principalmente a componentes protéicos presentes na Fase Soro do látex. Os compósitos obtidos apresentam boa estabilidade térmica e foram utilizados, como aplicação, na construção de substratos flexíveis para a análise química por meio de espectroscopia micro-Raman analisando o efeito Surface Enhanced Raman Spectroscopy (SERS) e Surface Enhanced Ressonance Raman Spectroscopy (SERRS) e Surface Enhanced Ressonance Raman Spectroscopy (SERRS) / In this work, developed together the Research Group of New Materials and Applications, Department of Physics, Chemistry and Biology from Faculty of Science and Technology FCT/UNESP in Presidente Prudente, proposes to conduct research the manufacture of rubber membranes from natural latex extracted from trees from Hevea brasiliensis (clone RRIM 600 - Rubber Research Institute of Malaysia). This membranes were prepared by casting technique and used as active substrates (both reducing and stabilizer agent) in the synthesis of metal nanoparticles (NPs) by in situ reduction method, using gold chloride (AuCl3) aqueous solution, so that the nanoparticles are incorporated both on surface and embebbed into the membrances. The main objective is obtaining relevant information on the compounds of the natural rubber membrances which assigns responsability for the reduction and stabilization of nanoparticles. The results obtained demonstrate that the synthesis of nanoparticles achieved, with average sizes around 48 nm, incorporated on the surface of natural rubber membranes. The reduction of gold nanoparticles is attributed mainly to the protein components present in the serum phase of the latex. The composites showing good thermal stability and were used, as application, in the construction of flexible substrate for chemical analysis using micro-Raman spectroscopy evaluated the Surface Raman Spectroscopy (SERS) and Surface Enhanced Ressonance Raman Spectroscopy (SERRS) effects

Improvements to the properties of recycled rubber, by developing a more selective breakdown process, is an important issue and a global challenge. Devulcanization is the most promising way to achieve this. It is a process which aims to totally or partially cleave monosulfidic (C-S-C), disulfidic (C-S-S-C) and polysulfidic (C-Sx-C) crosslinks of vulcanized rubber. In this study, the devulcanization of sulfur-vulcanized natural rubber with a variety of diphenyldisulfides has been studied using 2,3-dimethyl-2-butene and squalene as model compounds, vulcanized by sulfur and 2-bisbenzothiazole-2,2’-disulfide. 2-aminodiphenyldisulfide; 4-amino-diphenyldisulfide; bis(2-benzamido-)diphenyldisulfide and 2,2’-bithiosalicylic acid were used as aromatic disulfides devulcanization agents. Thermal analysis was used to investigate interactions between various combinations of curatives in the vulcanization systems in the absence of model compounds. Thermogravimetric analysis was used to detect mass changes during vulcanization and whether the samples decompose/evaporate so as not to contaminate differential scanning calorimetry instrumentation. Differential scanning calorimetry was used to investigate reactions occurring between curatives. Comparison of reversing and non-reversing signals in modulated experiments are suggestive of reactions between devulcanization agents and sulfur, and accelerators Vulcanization of the model compounds were performed in 10m evacuated sealed glass ampoules placed in an oil bath at 160 °C and agitated for the duration of vulcanization. After 60 min the ampoules were removed and quenched. These were then devulcanized by exposure to a devulcanization agent in a sealed ampoule at 180 for 60 min. Crosslinked 2,3-dimethyl-2-butene species were isolated and analysed by reversed phase high performance liquid chromatography. Particular attention was paid to changes in the number of sulfur atoms in the crosslinks. Results indicate that of the devulcanization agents tested 4-amino-diphenyldisulfide was the most effective. No detrimental effect on devulcanization efficiency was caused by the substitution of a basic amino group with an acidic carboxylic acid group Gel permeation chromatography was performed on devulcanized squalene crosslinks using a tetrahydrofuran eluent. GPC investigations with squalene were less effective than HPLC experiments with 2,3-dimethyl-2-butene at evaluating the relative efficiency of individual devulcanization agents. Results were, however, consistent with 4-amino-diphenyldisulfide again being the most efficient devulcanization agent.

The effect of increment addition of monomer, during the emulsion polymerization of styrene, upon the molecular homogeneity of polystyrene has been investigated. This procedure results in a polymer containing large amounts (greater than 60%) of benzene insoluble material indicating that there is a considerable degree of cross-linking during the process. A small amount of the product (less than 20%) exhibits a fair degree of homogeneity with respect to the molecular weight. Low molecular weight polystyrene can be obtained by the use of mercaptan modifiers. The mercaptan appears to be carried into the reaction loci by the styrene during the early stages of the polymerization. Later, the effectiveness of the modifier is governed by diffusion through the aqueous phase. / Science, Faculty of / Chemistry, Department of / Graduate

Orientador: João Sinezio de Carvalho Campos / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-07T22:02:16Z (GMT). No. of bitstreams: 1 Alves_MarciaReginadaCosta_M.pdf: 616913 bytes, checksum: c2dabea0f9dddf03128007fd60e70195 (MD5) Previous issue date: 2004 / Resumo: Esta pesquisa trata da caracterização e comparação entre as principais borrachas naturais utilizadas em pneumáticos, GEB-1, STR, SMR-20 e RSS-3, utilizando-se um único composto e alterando-se apenas a borracha. A caracterização e comparação foram feitas medindo-se as propriedades mecânicas (dinamométricas), reométricas, queima, viscosidade, densidade e dureza. O composto estudado foi uma mistura típica contendo borracha natural, negro de fumo, óleo plastificante, auxiliares de processamento, antioxidantes, adesivante, acelerante e vulcanizante, todos numa quantidade pré-estabelecida. Antes de iniciar o trabalho de mistura dos compostos do estudo, foi realizada a caracterização das borrachas utilizadas. Desta caracterização, a borracha RSS-3 (Ribbed Smoked Sheet) se difere das demais principalmente pela viscosidade e pelo PRI que são maiores. As borrachas SMR-20, GEB-1 e STR são semelhantes e no composto final isto pôde ser observado. Na análise dinamométrica, o módulo de alongamento à 100% e tensão de ruptura foram mais altos para o composto com a borracha RSS-3, porém com menor dispersão em comparação às demais. A Borracha GEB-1 apresentou um desvio padrão maior entre as várias análises efetuadas. O alongamento à ruptura ficou menor com a borracha RSS-3. A borracha RSS-3 conferiu maior viscosidade ao composto final, já esperado uma vez que sua viscosidade e PRI são maiores que as outras três borrachas estudadas. Concluindo que para obtenção dos mesmos valores de viscosidade, que é um parâmetro importante no processamento do composto, o ciclo de confecção deste composto deveria ser alterado, para isto é aconselhado um novo estudo. Para todas as borrachas a densidade apresentou valores semelhantes, com dispersão também uniforme, concluindo que a mistura dos compostos em todos os casos estavam homogêneas e que o ciclo de confecção utilizado foi suficiente para garantir a boa mistura. A partir dos resultados obtidos conclui-se que nos períodos de entre-safra pode-se utilizar outras borrachas em substituição à indisponível, desde que o ciclo de confecção seja alterado e que uma pequena alteração das características do composto final sejam permitidas / Abstract: The present research concerns the characterization and comparison among the main natural rubber used in tires, GEB-1, STR, SMR-20 and RSS-3, utilizing one compound and altering only the rubber. Both characterization and comparison were made by measuring the mechanical properties (dynamometric, rheometric, burning, viscosity, density and hardness). The studied compound was a typical mixture containing natural rubber, carbon black, plasticizing oil, processing auxiliaries, antioxidants, adhesives, accelerants and vulcanizer, all in a specific pre-established quantity. Prior to initiating the process of the mixture of the compounds, a characterization of the used rubbers was carried out. In the course of this characterization it was observed that the RSS-3 rubber (Ribbed Smoked Sheet) differs from the others, mainly due to its viscosity and by the PRI, which are higher. The MST-20, GEB-1 and STR rubbers are similar, fact which was observed in the final composition. In the dynamometric analysis, the stretch module at 100% and load of rupture were higher for the RSS-3 compound, although with a lower dispersion if compared with the other rubbers. The GEB-1 rubber presented a standard deviation, the highest among the several analyses that were performed. The stretch to the rupture was lower with the RSS-3 rubber. The RSS-3 rubber presented more viscosity to the final composition, which was expected since its viscosity and PRI are higher then the other three studied rubbers. Therefore, in order to obtain the same values of viscosity, which is an important parameter in the compound process, the cycle of confection of this compound must be altered. Such alteration would require a new study. The density presented similar results to all rubbers, also with a uniform dispersion, concluding that the mixture of the compounds in all cases were homogenous and that the cycle utilized was sufficient to guarantee a good mixture. From the obtained results one concludes that during the between-harvest seasons one can use other rubbers as a substitution to the available one, as long as the cycle of confection is modified and that a small alteration of the characteristic of the final composition be allowed. / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

Sustainability presents a pathway for future generations to have a better life. Cradle to cradle methodology is the essence of sustainability. In cradle to cradle approach, we aim to reuti-lize a given waste instead of disposing or landfilling it. Each year, millions of waste tires are dis-posed of in landfills. This poses a major challenge environmentally and economically. Environ-mentally, those tires become prone to fire hazards as well as being a place for rodents and mos-quitos to reside at. Economically, on the other hand, each tire has an average of about 50% valu-able polymers as well as oily components. One of the methods to utilize the valuable raw materi-als in waste tires is to recycle it in the form of ground tire rubber also known as crumb rubber modifier (CRM). Although CRM has been widely used as an asphalt modifier, however, due to the complexity of asphalt as well as the waste nature of CRM, the full understanding of the CRM modification mechanism with asphalt has not been fully understood. Understanding of the modi-fication mechanisms involved in the CRM interaction with asphalt would enable us to produce a crumb rubber modified asphalt (CRMA) with enhanced properties. In the current research work, an attempt is made to better understand the mechanism of interaction between CRM and asphalt and the nature of components from asphalt and CRM that take part in the interaction between them. In addition, we investigate the effectiveness of CRM as a modifier for asphalt on the mac-ro and microscale aspects. Another part of the current research work deals with a second waste material; used motor oil. Used motor oil (UMO) presents yet another challenge to environment. With the ever increas-ing motor vehicles produced with advanced technologies and increased advanced motor oil de-mand. This presents a burden on the environment, with the continuous production of UMO. In the current research work, we investigated the feasibility of utilizing UMO as a modifier for asphalt and CRMA. We also investigated the effect of UMO on the micro and macroscale aspects of asphalt.

Recycling of millions of scrap tires produced everyday is crucial challenge encountered by waste management systems. Recycling tire rubbers in form of ground tire rubber, known as crumb rubber modifier (CRM), in asphalt industry was introduced in early 1960's and is proved as an effective recycling method. Interaction between CRM and asphalt is physical in nature which happens mainly due to exchange of components between CRM and asphalt and enhances the time temperature dependant properties of asphalt. In this work, the interaction between CRM and asphalt was evaluated through monitoring the evolutions of CRM in asphalt in macro and micro-level. The mechanism and extent of CRM dissolution were monitored under several interaction conditions. The composition of materials released from CRM was investigated using thermo-gravimetric analysis (TGA). The molecular status of the released components were studied using gel permeation chromatography (GPC) analysis. The composition analysis indicated that the CRM start releasing its polymeric components into the asphalt matrix at dissolutions higher than 20%. The released polymeric component of CRM alters the microstructure of the asphalt and creates an internal network at certain interaction temperatures according to viscoelastic analysis. At these temperatures, the released polymeric components are at their highest molecular weight based on GPC results. The effect of released components of CRM on the time temperature dependent properties of asphalt and its glass transition kinetic was monitored using dynamic shear rheometer (DSR) and differential scanning calorimetry (DSC), respectively. The DSC results showed that the intensity of glass transition of the asphalt binder which is mainly defined by the aromatic components in asphalt reduced by absorption of these components by CRM. The evolution of CRM was investigated during short-term aging of the modified asphalt binder. In addition, the effect of presence of CRM and release of its component on oxidization of asphalt binder was evaluated using Fourier transform infrared spectroscopy (FTIR). The results revealed that CRM continue absorbing the aromatic components of asphalt during aging which stiffen the asphalt binder. Also, it was observed that release of oily components of the CRM, which contain antioxidant, reduces oxidization rate of asphalt significantly. / National Science Foundatio (Grant No. 0846861)

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