Made available in DSpace on 2014-06-11T19:23:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2005-08-26Bitstream added on 2014-06-13T19:29:33Z : No. of bitstreams: 1 simoes_rd_me_bauru.pdf: 3082806 bytes, checksum: b44fcfd386ae934a75a9814336462470 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O principal objetivo deste trabalho de mestrado foi a obtenção e caracterização estrutural de um material com propriedades físico-químicas compatíveis com aquelas requeridas por um biomaterial. Filmes contendo diferentes volumes de látex de borracha natural em uma massa fixa de poli(fluoreto de vinilideno) (PVDF), na forma de pó foram fabricados por compressão/aquecimento de uma mistura de ambos os materiais sem o uso de qualquer solvente. Este é um fator importante considerando o uso destes filmes no futuro próximo como biomateriais em diferentes aplicações (indução do crescimento do tecido ósseo, por exemplo), uma vez que os solventes convencionais usados para dissolver o PVDF têm se mostrado tóxicos ao organismo humano. Os filmes foram submetidos a um tratamento via descarga corona de forma que amostras com e sem tal tratamento foram caracterizadas através das técnicas de espectroscopia vibracional via espalhamento Raman e absorção no infravermelho (FTIR), análise térmica via termogravimetria (TG), calorimetria exploratória diferencial (DSC) e análise dinâmico-mecânica (DMA) e microscopias ótica e eletrônica (MEV). As medidas termomecânicas mostraram que os filmes obtidos possuem características mecânicas similares àquelas encontradas no osso humano e boa estabilidade térmica considerando-se a aplicação desejada. As medidas via espectroscopia vibracional indicaram que o PVDF e o látex não interagem quimicamente, compondo uma blenda polimérica. Além disto, os resultados obtidos via micro-Raman mostraram que o aumento da quantidade de látex na blenda permite uma melhor dispersão deste látex na matriz de PVDF quando da produção dos filmes... / The main goal of this work was to obtain and characterize structurally a material with physical-chemical properties compatible with those required for a biomaterial. Films containing different volumes of latex of natural rubber in a fixed mass of poly (vinylidene fluoride) (PVDF) powder were fabricated by compressing/annealing a mixture of both materials without using any solvent. This is an important issue having in mind to use these films in the future as biomaterials in different applications (growing of the bone tissue, for instance) once the solvents used to dissolve the PVDF are toxic to human being. The films were submitted to a corona discharge treatment in a way that samples with and without such treatment were characterized using micro-Raman scattering and Fourier transform infrared absorption (FTIR) spectroscopies, thermo-mechanical techniques using thermogravimetry (TG), differential scanning calorimetry (DSC) and dynamical-mechanical analysis (DMA) and optical and scanning electron microscopies (SEM). The thermo-mechanical measurements revealed that the films present mechanical properties close to that found for the human bone and high thermal stability considering the desired applications. The vibrational spectroscopies showed that the latex and PVDF do not interact chemically leading to the formation of a polymeric blend. Besides, the results recorded using the micro-Raman technique revealed that the higher the amount of latex in the blend, the better the miscibility between both materials. In terms of morphology, the blend surface is formed by two domains: one is rougher and contains the latex well dispersed into the PVDF matrix while the other is smoother and contains both materials as well but in a less homogeneous dispersion. However, as the volume of latex is increased from 0.3 to 1.0 mL, the smoother domains become rarer to be found... (Complete abstract, click electronic address below)

Submitted by Ronildo Prado (ronisp@ufscar.br) on 2017-08-23T13:47:40Z No. of bitstreams: 1 DissRB.pdf: 6420019 bytes, checksum: 9a9303246e3fd99e5635cc0d40d684d5 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-08-23T13:47:48Z (GMT) No. of bitstreams: 1 DissRB.pdf: 6420019 bytes, checksum: 9a9303246e3fd99e5635cc0d40d684d5 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-08-23T13:47:53Z (GMT) No. of bitstreams: 1 DissRB.pdf: 6420019 bytes, checksum: 9a9303246e3fd99e5635cc0d40d684d5 (MD5) / Made available in DSpace on 2017-08-23T13:48:00Z (GMT). No. of bitstreams: 1 DissRB.pdf: 6420019 bytes, checksum: 9a9303246e3fd99e5635cc0d40d684d5 (MD5) Previous issue date: 2017-03-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The present study investigated the utilization efficiency of an intermeshing co-rotating twin-screw extruder (ICTSE) in the devulcanization of natural rubber compounds (NR), evaluating the physical, chemical and mechanical characteristics of these materials in each project step. Three accelerated compounds with different sulfur concentrations were submitted to torque rheometry and vulcanized according these results aiming the achievement of elastomers with different crosslinks densities. The influences on the characteristics of the devulcanized material caused by the variation of the extruder barrel temperature, screw rotation, thermoplastics addition and material stiffness were evaluated. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), soluble fraction extraction and crosslink density were performed, evaluating the devulcanized compound. Horikx's theory was also used as an indicator of selective crosslink cleavage, defining the compounds to be revulcanized for comparison with the virgin pure material. The revulcanization was carried out with the mixture of the devulcanized compound with the pure, in the proportions of 30/70 w/w, respectively, and in the devulcanized compound singularly, with addition of complementary vulcanization system in both cases. The mechanical, dynamic-mechanical and crosslink density properties of the revulcanized compounds were characterized and evaluated in relation to the properties of the pure compounds. The increase in the concentration of uncrosslinked BN chains and the concentration of sulfur compounds in the extruded samples was observed by thermal tests and spectrocopy, together with the verification of a high level of devulcanization percentage, according to Flory-Rehner, evidencing the regeneration of the natural rubber existent. Also, satisfactory mechanical properties were found in the revulcanized compounds, especially when using auxiliary thermoplastics, revealing the great potential of ERDCI processing for the reuse of discarded BN compounds. / O presente estudo avaliou a eficiência de utilização de uma extrusora com rosca dupla co-rotacional e interpenetrante (ERDCI) na desvulcanização de compostos de borracha natural (BN), avaliando as características físicas, químicas e mecânicas destes materiais em cada fase do projeto. Três compostos acelerados com diferentes concentrações de enxofre foram submetidos a reometria de torque, e vulcanizados de acordo com a curva reométrica, para obtenção de elastômeros com diferentes densidades de ligações cruzadas. Foram avaliadas as influências nas características do material desvulcanizado, causadas pela variação da temperatura do barril da extrusora, velocidade de rotação das roscas, adição de termoplásticos e módulo elástico do material. Análises de termogravimetria (TGA), calorimetria exploratória diferencial (DSC), espectroscopia no infravermelho (FTIR), fração solúvel (FS) e densidade de ligações cruzadas foram realizadas, avaliandose o composto desvulcanizado. A teoria de Horikx também foi utilizada como indicativa da seletividade de ruptura de ligações cruzadas, definindo os compostos a serem revulcanizados para comparação com o material virgem. A revulcanização foi realizada com a mistura de 30 %(m/m) do composto desvulcanizado e 70 %(m/m) do puro, e também com 100 % do composto desvulcanizado, e adição de sistema de vulcanização complementar. Caracterizou-se os compostos revulcanizados quanto às suas propriedades mecânicas, dinâmico-mecânicas e densidade de ligações cruzadas. Através dos ensaios TGA, DSC, FTIR e a verificação de alto nível de percentual de desvulcanização pela teoria de Flory- Rehner, foi observado o aumento da concentração de cadeias de BN não reticuladas e da concentração de compostos de enxofre nas amostras extrudadas, evidenciando a regeneração da BN presente nos compostos. Também foram encontradas propriedades mecânicas satisfatórias nos compostos revulcanizados, principalmente quando utilizados termoplásticos auxiliares, revelando o grande potencial do processamento por ERDCI para a reutilização de compostos de BN descartados.

A partir da publicação, em 1994, de um relatório que afirmava que a presença de óleos aromáticos pesados, com altos teores de compostos policíclicos, em formulações de borrachas estaria relacionada ao desenvolvimento de doenças como o câncer, associado ao fato da crescente conscientização ambiental na fabricação de produtos elastoméricos, foi iniciado um estudo sobre a substituição do óleo aromático de origem do petróleo por óleos vegetais de menor risco. Nessa Dissertação de Mestrado foi proposta a substituição do óleo aromático derivado do petróleo por óleos vegetais como o de tungue, palma e linhaça, em composições de borracha natural (NR) contendo diferentes teores do copolímero de butadieno-estireno (0, 10 e 50 phr) e diferentes tipos de carga (negro de fumo N330 e negro de fumo N375). As composições obtidas foram avaliadas quanto a propriedades reométricas, mecânicas e fractográficas. Foi observado que não houve variação significativa na viscosidade Mooney, na resistência à tração, no alongamento na ruptura e na dureza Shore das composições de NR SBR1502 quando o óleo aromático foi substituído pelos óleos vegetais, quando diferentes negros de fumo foram utilizados como carga reforçante e quando foram utilizados teores crescentes de SBR1502. Por outro lado, a resistência ao rasgamento das composições de NR SBR1502 apresentaram melhores resultados quando o negro de fumo N375 foi utilizado. A adição de teores crescentes de SR 1502 levou à diminuição dos valores de rasgo. A natureza do óleo utilizado influenciou esse resultado e melhores valores foram obtidos com o óleo de tungue. Os resultados obtidos foram corroborados pela morfologia do material, avaliadas por microscopia eletrônica de varredura / A study has been started based on a 1994 report which announced that the presence of heavy aromatic oils, with high amount of polycyclic compounds, in rubber formulations has a influence with the appearance of diseases, like cancer, and associated with the growth about environmental concerns in the rubber enterprises, the focus of this study is to evaluate the possibility of changing the aromatic oils for vegetable ones, with lower risks. In this Master Dissertation it has been evaluated the changes on the characteristics when the aromatic oil is changed by palm, tung and linseed oils in natural rubber (RB) compounds, when the quantity of SBR is changed and different kinds of carbon black are used. The mixes have been evaluated measuring rheometric, mechanical and fractographic. It has been observed that the changes made did not affect significantly the Mooney viscosity, tensile strength, elongation at break and hardness Shore among the samples studied. The changes are: different kind of carbon black (N375 and N330), progressive growth of the amount of SBR1502 (0, 10, 50 phr) used with natural rubber and the kind of oil (aromatic, palm, tung and linseed). On the other hand, the tear resistance has done better values when used the carbon black N375 with the NR SBR composition. The progressive addition of SBR1502 has a tendency of finding lower values form tear resistance. The origin of the oil has influenced the properties ant the tung oil has shown a better compromise. The results have been confirmed by the electronic microscopy

O processo de moldagem de pós por injeção (MPI) é uma tecnologia relativamente recente e permite a fabricação de peças e componentes de diversos materiais, com a possibilidade de fabricar peças em larga escala. O processo MPI é composto por quatro etapas: mistura do pó com o material orgânico (ligante), moldagem por injeção, extração do ligante e sinterização. O ligante é um veículo temporário composto por polímeros e/ou ceras e sua função é possibilitar o escoamento da carga injetável para o molde durante a moldagem por injeção e após a moldagem este deve ser totalmente removido da peça. A maioria dos polímeros utilizados no ligante é oriunda do petróleo, que é uma fonte não renovável que gera sérios impactos ambientais. Neste estudo foi proposto a utilização de ligante à base de borracha natural, que além de ser proveniente de fonte renovável, confere elasticidade à peça moldada, que possibilita a fácil desmoldagem de peças com geometria complexa e pequenas espessuras. Também se analisou a substituição da parafina, que estudada em trabalhos anteriores em ligante para injeção de alumina com a borracha natural, pela cera de carnaúba na moldagem por injeção de pó de ferro metálico. Foram avaliados três ligantes à base de borracha natural e as ceras: (i) parafina, (ii) cera de carnaúba e (iii) parafina + cera de carnaúba e estudou-se o efeito da composição do ligante em cada etapa do processo MPI. Investigou-se as propriedades químicas e térmicas dos ligantes, o teor de pó admissível nas cargas injetáveis, as rotas de remoção do ligante por via térmica e solvente e as propriedades finais como retração linear, porosidade, microestrutura e resistência à flexão. As composições de ligante a base de borracha natural e cera de carnaúba proporcionaram melhores propriedades ao processo MPI. Nestas composições foi possível a moldagem por injeção de cargas injetáveis com maior teor de pó, apresentaram maior estabilidade reológica, em que a viscosidade apresentou baixa variação em relação à temperatura e maior estabilidade com o aumento do teor de pó. Além disso, foram as únicas amostras que não apresentaram defeitos durante a extração por solvente e apresentaram propriedades finais satisfatórias para o processo MPI de ferro. / The Powder Injection Molding process (PIM) is a relatively new technology and allows the manufacturing of parts and components of various materials, with the possibility of fabricating parts in microscale. The PIM process is composed of four steps: mix the powder with the organic material (binder), injection molding, extraction of the binder and sintering. The binder is a temporary vehicle composed of polymers and/or waxes and its function is to allow the flow of the feedstock into the mold during injection molding, and after molding this should be completely removed from the sample. Most of the polymers used in the binder are derived from petroleum, which is a non-renewable source that generates serious environmental impacts. In this study, it was proposed the use of binder based on polymer and wax from renewable sources that reduce the environmental impact. It was analyzed the substitution of paraffin, which was studied in previous studies with natural rubber, by the carnauba wax in the injection molding of the iron carbonyl. Were evaluated three binders based on polymer and wax: (i) paraffin, (ii) carnauba wax and (iii) paraffin wax carnauba wax and we studied the binder composition effect in each step of PIM process. The chemical and thermal binder properties, the critical powder volume concentration, the solvent and thermal debinding and the sintered properties were analyzed. As results, we found that the natural rubber and carnauba wax binder have better PIM process properties. In this binder was possible an injection molding with higher powder content, showing higher rheological stability, which the viscosity was more stable under temperature and powder content variation. Furthermore, the samples with this binder shown no defects after solvent debinding and suitable sintered properties for the iron PIM process.

La préparation du caoutchouc naturel hydrogéné (HNR) par réaction avec l'hydrazine et le peroxyde d'hydrogène et le latex de caoutchouc naturel a été intéressée. L’influence de conditions de réaction, types et volume de solvants, volume du  réactionnel, la quantité d’hydrazine et de peroxyde d’hydrogène sur le degré d’hydrogénation du caoutchouc naturel a été étudiée. Le structure et  détermination du degré d’hydrogénation des caoutchoucs naturel hydrogénés a été analysée par  résonance magnétique nucléaire (RMN), transformée de fourier infrarouge (FTIR) et spectroscopie Raman. Un degré d'hydrogénation de 18 % a été obtenu à 1.0 - 2.0 du la molaire de d’hydrazine et de peroxyde d’hydrogène, température optimale de 50°C et le temps de réaction de 24h. Afin d'améliorer le degré d'hydrogénation, des solvants tels que le toluène et le hexane et l'effet de le volume du réactionnel ont été étudiée, ce qui a permis d'obtenir des degrés d’hydrogénation  élevés (proches de 65% avec le toluène). D’autre part, des mesures de tailles de particules de latex ont montré que l’hydrogénation du caoutchouc naturel n’avait pas d’effet sur latex de caoutchouc naturel. Un résultat également intéressant concerne le détermination du taux de gel. Ce gel augmente avec le degré d’hydrogénation, prouvant que des réactions de réticulation ont eu lieu. Néanmoins aucun effet de degré d’hydrogénation sur le température de transition vitreuse n’est détecté. La dureté et viscosités Mooney augmentent, en lien avec l’augmentation du taux de gel. Par ailleurs, la résistance thermique du caoutchouc naturel hydrogéné est considérablement améliorée lorsque le degré d’hydrogénation augmente. Le partie suivante est consacrée à la vulcanisation du caoutchouc. Deux types de réticulation ont été utilisés : au soufre et au peroxyde. Les élastomères HNR réticulés montrent une meilleure résistance à l’ozone et l’UV que le NR réticulé. De plus, cette résistance à l’ozone et l’UV est plus élevée pour le réticulation au soufre, comparée à le réticulation au peroxyde. Une bonne corrélation entre les images de microscopie optique et les résultats des analyses Raman est obtenue. La préparation et l’étude de mélanges HNR/PP obtenus par vulcanisation dynamique en utilisant du peroxyde et du soufre comme agents de réticulation. Un degré d’hydrogénation de 65% a été choisi, et différentes ratio HNR/PP ont été étudiés, et comparés avec des mélanges NR/PP. La morphologie des mélanges a été caractérisée par spectroscopie Raman, ce qui a permis d’obtenir des images cartographie Raman indiquant de façon précise le localisation et la distribution des phases de caoutchouc et de PP.  Une bonne corrélation entre le cartographie Raman et les images de microscopie électronique à balayage (SEM) est obtenue. Ainsi il apparaît que les particules de caoutchouc sont dispersées dans une phase continue de PP, ceci à la fois pour le HNR et le NR. L’étude des propriétés mécaniques a montré que celles-ci étaient gouvernées principalement par le phase continue de PP. / The non-catalytic hydrogenation of natural rubber latex (NRL) was carried out by using diimide generated in situ from the reaction between hydrazine (N2H4) and hydrogen peroxide (H2O2). The effects of mole ratios of [C=C]:[N2H4]:[H2O2], reaction conditions, solvent types, solvent volumes and reaction scale-up on the hydrogenation levels were investigated. Nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and Raman spectroscopic techniques were employed to investigate the chemical structure of the hydrogenated natural rubber (HNRs) and to quantify the hydrogenationlevels. It was found that variations in moles of N2H4 and H2O2 in the range of 1.0-2.0 moles resulted in degrees of hydrogenation in the range of 10-18%. Little improvement in hydrogenation levels of HNRs was obtained when NRL particles were swollen in solvents by which toluene yielded better results than hexane. The increase in toluenevolume resulted in the increase in hydrogenation levels up to 42 %. TEM micrographs revealed that swelling mainly occurred at the surface of NRL particles, implying that hydrogenation reaction confined largely at the surface of NRL particles. After removal of toluene, particle size and particle size distribution of partially hydrogenated NRL remained unchanged. To further improve degrees of hydrogenation, the reaction volume was extended and 65% hydrogenation levels were obtained. Therefore, 14%HNR, 33%HNR, and 65%HNR were successfully prepared under suitable reaction conditions. However, crosslinking and cis-trans isomerization were side-reactions occurring during hydrogenation. Gel and trans contents increased with increasing hydrogenation levels, leading to the increase in hardness of HNRs. Mooney viscosities of HNRs increased with increasing degrees of hydrogenation due to the increased gel contents. Mooney torquerelaxation of NR and HNRs were similar. Thermogravimetric analysis revealed that vi HNRs had greater thermal stability than NR and thermal stability increased with increasing degrees of hydrogenation. HNR vulcanizates were much better resistant to ozone and UV than cured NR. Sulfur-vulcanized rubbers had greater ozone resistance than peroxide-cure rubbers due to less amounts of carbon-carbon double bonds present in rubbers. In addition, modulus at low strain and tensile strength of sulfur-cured rubbers were higher than those of peroxide-cured rubbers, but lower elongation due to higher crosslink densities. Also, modulus at low strain and tensile strength increased with increasing hydrogenation levels of HNRs, in contrast to strain at break. Thermoplastic vulcanizates (TPVs) from blends of HNR and Polypropylene (PP) were prepared via dynamic vulcanization using peroxide and sulfur as curing agents. The effects of blend ratios on mechanical properties of TPVs were investigated. Tensile strength increased with increasing PP portions, but breaking strain decreased. Morphology of TPVs was characterized with Raman mapping and scanning electron microscope (SEM). The phase sizes of crosslinked rubber obtained from both techniques were correlated well.

O efeito de dois óleos vegetais, óleo de linhaça e óleo de amendoim, em composições de borracha natural (NR) foi avaliado. Um sistema de vulcanização convencional foi escolhido e, após a mistura, os parâmetros reométricos (Sℓ, Sh, ts1 e t90) foram analisados. A cinética de vulcanização foi estudada através de dois modelos cinéticos um modelo simplificado e o modelo proposto por Coran. Os resultados experimentais permitem concluir que os óleos vegetais sozinhos ou combinados são capazes de atuar como ativadores e, juntamente com os demais ingredientes da composição, de vulcanizar a borracha. No entanto, uma densidade de ligações cruzadas satisfatória só é atingida quando o ácido esteárico está presente. O modelo cinético de Coran permitiu também estudar os diferentes estágios da vulcanização e verificar que a etapa crítica do processo é a formação do precursor de ligações cruzadas (A → B). Provavelmente, a presença significativa de ácidos graxos insaturados na composição dos óleos vegetais (principalmente, os ácidos oléico e linolênico) permita reações laterais não esperadas, o que diminui o rendimento final em ligações cruzadas dos vulcanizados. / The effect of two vegetable oils, linseed oil and peanut oil, in natural rubber (NR) compositions was available. A conventional system was chosen and, after mixture, rheometer parameters (Sℓ, Sh, ts1 e t90) were analyzed. Vulcanization kinetics was studied by two kinetic models a simplified model and a model proposed by Coran. Experimental results allow concluding that vegetable oils alone or combined are able to act as activators and, together with others ingredients of composition, vulcanizing the rubber. However, crosslinking density adequate is only reached when stearic acid is present. Kinetic model of Coran also allowed to study the different steps of vulcanization and to identify that a critical step is the formation of crosslink precursor (A → B). Probably, significant presence of insaturated fatty acids in the chemical composition of the vegetables oils (mainly, oleic and linolenic acids) allow side reactions unexpected, which decrease the final yield of crosslink in the vulcanizates.

A partir da publicação, em 1994, de um relatório que afirmava que a presença de óleos aromáticos pesados, com altos teores de compostos policíclicos, em formulações de borrachas estaria relacionada ao desenvolvimento de doenças como o câncer, associado ao fato da crescente conscientização ambiental na fabricação de produtos elastoméricos, foi iniciado um estudo sobre a substituição do óleo aromático de origem do petróleo por óleos vegetais de menor risco. Nessa Dissertação de Mestrado foi proposta a substituição do óleo aromático derivado do petróleo por óleos vegetais como o de tungue, palma e linhaça, em composições de borracha natural (NR) contendo diferentes teores do copolímero de butadieno-estireno (0, 10 e 50 phr) e diferentes tipos de carga (negro de fumo N330 e negro de fumo N375). As composições obtidas foram avaliadas quanto a propriedades reométricas, mecânicas e fractográficas. Foi observado que não houve variação significativa na viscosidade Mooney, na resistência à tração, no alongamento na ruptura e na dureza Shore das composições de NR SBR1502 quando o óleo aromático foi substituído pelos óleos vegetais, quando diferentes negros de fumo foram utilizados como carga reforçante e quando foram utilizados teores crescentes de SBR1502. Por outro lado, a resistência ao rasgamento das composições de NR SBR1502 apresentaram melhores resultados quando o negro de fumo N375 foi utilizado. A adição de teores crescentes de SR 1502 levou à diminuição dos valores de rasgo. A natureza do óleo utilizado influenciou esse resultado e melhores valores foram obtidos com o óleo de tungue. Os resultados obtidos foram corroborados pela morfologia do material, avaliadas por microscopia eletrônica de varredura / A study has been started based on a 1994 report which announced that the presence of heavy aromatic oils, with high amount of polycyclic compounds, in rubber formulations has a influence with the appearance of diseases, like cancer, and associated with the growth about environmental concerns in the rubber enterprises, the focus of this study is to evaluate the possibility of changing the aromatic oils for vegetable ones, with lower risks. In this Master Dissertation it has been evaluated the changes on the characteristics when the aromatic oil is changed by palm, tung and linseed oils in natural rubber (RB) compounds, when the quantity of SBR is changed and different kinds of carbon black are used. The mixes have been evaluated measuring rheometric, mechanical and fractographic. It has been observed that the changes made did not affect significantly the Mooney viscosity, tensile strength, elongation at break and hardness Shore among the samples studied. The changes are: different kind of carbon black (N375 and N330), progressive growth of the amount of SBR1502 (0, 10, 50 phr) used with natural rubber and the kind of oil (aromatic, palm, tung and linseed). On the other hand, the tear resistance has done better values when used the carbon black N375 with the NR SBR composition. The progressive addition of SBR1502 has a tendency of finding lower values form tear resistance. The origin of the oil has influenced the properties ant the tung oil has shown a better compromise. The results have been confirmed by the electronic microscopy

Ce travail de thèse a pour objectif d’élaborer de nouveaux matériaux composites (élastomères, adhésifs) en utilisant les nanocelluloses (NCC et NFC) comme renforts mécaniques biosourcés. Une méthode de fonctionnalisation des nanocelluloses en conditions aqueuses a d’abord été développée, dans le but ultime d’améliorer leur compatibilité avec les matrices polymères. La réaction, basée sur la transestérification des esters de vinyle, a été optimisée à partir de l’acétate de vinyle utilisé comme réactif modèle. Le greffage en conditions basiques s’est avéré efficace, mais a également conduit à la formation de poly(acétate de vinyle) (PVAc) comme produit secondaire. Pour pallier à ce problème, un deuxième protocole en conditions neutres a également été développé, mais des rendements moins bons ont été obtenus dans ce cas. Les nanocelluloses non modifiées et acétylées ont ensuite été dispersés dans une matrice caoutchouc naturel (NR) afin d’étudier l’impact de cette charge sur les performances thermomécaniques du matériau cru ou vulcanisé. Une amélioration des propriétés mécaniques a pu être observée en présence de NCC ou NFC, mais l’acétylation des nanoparticules n’a pas conduit à de meilleures performances. Enfin, une valorisation du PVAc produit lors de l’acétylation des nanocelluloses en conditions aqueuses basiques a été proposée. La dispersion des NCC acétylés dans le PVAc polymérisé in-situ a en effet permis de produire des composites aux propriétés améliorées. L’utilisation ultérieure de ces composites comme charge (mélange-maître) dans des matrices NR ou EVA a été discutée. / The objective of this research work consists in the elaboration of novel composite materials (elastomers, adhesives) using nanocelluloses (CNC and NFC) as biobased reinforcing fillers. A method allowing the functionalization of nanocelluloses in aqueous conditions was first developed, with the aim of ultimately improving their compatibility with polymer matrices. The reaction, based on the transesterification of vinyl esters, was optimized with vinyl acetate selected as model reactant. The grafting performed in basic aqueous conditions was efficient, but also led to the formation of poly(vinyl acetate) as a by-product. To limit this problem, a second protocol in neutral aqueous conditions was also developed, but lower yields were obtained in that case. The unmodified and acetylated nanocelluloses were then dispersed in a natural rubber matrix (NR), to study the impact of this filler on the thermomechanical performances of the crude and vulcanized material. An improvement of the mechanical properties was observed in the presence of NCC or NFC, but the acetylation of the nanoparticles did not enhance further the performances. Finally, a valorization of the PVAc produced during the acetylation of the nanocelluloses in basic aqueous conditions was proposed. The dispersion of the acetylated NCC in the PVAc polymerized in-situ indeed led to the production of composites with improved properties. The subsequent utilization of these composites as filler (master batch) in NR or EVA matrices was discussed.

Dans les conditions réelles d’utilisation, de multiples facteurs sont à l’origine de l’évolution des propriétés mécaniques des caoutchoucs (température, oxygène, conditions de chargement mécaniques…). Les pièces en élastomère pour l’antivibratoire automobile sont généralement massives (plusieurs millimètres d’épaisseur), le vieillissement conduit alors à des évolutions de propriétés hétérogènes. Ceci peut être induit par plusieurs mécanismes de dégradation liés, par exemple, à la présence ou non d’oxygène. Pour comprendre et identifier les mécanismes de dégradation prépondérants, une campagne de vieillissement accéléré a été menée pour une large gamme de températures représentative des conditions de service rencontrées sur véhicule (de 40°C à 120°C). De nombreux échantillons de géométries différentes (films minces, éprouvettes de caractérisation et éprouvettes de structure) ont été utilisés afin, d’une part, de faciliter l’interprétation, et d’autre part, de viser la transposition des résultats à l’échelle des pièces industrielles. L’étude présentée ici vise à identifier les mécanismes physico-chimiques et/ou évolutions microstructurales à l’origine du processus de dégradation, et de quantifier les conséquences de ceux-ci sur le comportement mécanique et les propriétés en fatigue. Ces résultats permettront de fournir les éléments nécessaires à la modélisation et la prise en compte fine des effets du vieillissement dans le processus de conception de pièces antivibratoires automobiles. / Under service conditions, many factors are responsible for the evolution of the mechanical properties of rubber parts (temperature, oxygen, mechanical loadings, etc.). Automotive anti-vibration parts using rubber-like materials are usually massive and ageing can therefore lead to heterogeneous properties. To understand the degradation process and especially the effect of oxygen, aerobic and anaerobic ageing conditions have been studied for a wide range of temperatures (from 40°C to 120°C). Numerous samples have been used with different geometries (from thin films to massive structural samples) to ease the interpretation but also to remain as close as possible from the final applications. The mechanical consequences of the ageing have been investigated for both static and fatigue properties throughout a wide experimental database (about 1000 specimens tested in fatigue, for example). The study aims at identifying the physicochemical mechanisms and/or microstructural evolution that cause the processes of degradation and to quantify the consequences on the mechanical behavior and the fatigue properties. These results will provide the necessary elements needed for the integration of thermo-oxidative effects in the fatigue design loop of automotive anti-vibration parts.

Orientador: Carlos José Leopoldo Constantino / Banca: Neri Alves / Banca: Osvaldo Novais de Oliveira Júnior / 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 da Unesp / Resumo: O principal objetivo deste trabalho de mestrado foi a obtenção e caracterização estrutural de um material com propriedades físico-químicas compatíveis com aquelas requeridas por um biomaterial. Filmes contendo diferentes volumes de látex de borracha natural em uma massa fixa de poli(fluoreto de vinilideno) (PVDF), na forma de pó foram fabricados por compressão/aquecimento de uma mistura de ambos os materiais sem o uso de qualquer solvente. Este é um fator importante considerando o uso destes filmes no futuro próximo como biomateriais em diferentes aplicações (indução do crescimento do tecido ósseo, por exemplo), uma vez que os solventes convencionais usados para dissolver o PVDF têm se mostrado tóxicos ao organismo humano. Os filmes foram submetidos a um tratamento via descarga corona de forma que amostras com e sem tal tratamento foram caracterizadas através das técnicas de espectroscopia vibracional via espalhamento Raman e absorção no infravermelho (FTIR), análise térmica via termogravimetria (TG), calorimetria exploratória diferencial (DSC) e análise dinâmico-mecânica (DMA) e microscopias ótica e eletrônica (MEV). As medidas termomecânicas mostraram que os filmes obtidos possuem características mecânicas similares àquelas encontradas no osso humano e boa estabilidade térmica considerando-se a aplicação desejada. As medidas via espectroscopia vibracional indicaram que o PVDF e o látex não interagem quimicamente, compondo uma blenda polimérica. Além disto, os resultados obtidos via micro-Raman mostraram que o aumento da quantidade de látex na blenda permite uma melhor dispersão deste látex na matriz de PVDF quando da produção dos filmes... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The main goal of this work was to obtain and characterize structurally a material with physical-chemical properties compatible with those required for a biomaterial. Films containing different volumes of latex of natural rubber in a fixed mass of poly (vinylidene fluoride) (PVDF) powder were fabricated by compressing/annealing a mixture of both materials without using any solvent. This is an important issue having in mind to use these films in the future as biomaterials in different applications (growing of the bone tissue, for instance) once the solvents used to dissolve the PVDF are toxic to human being. The films were submitted to a corona discharge treatment in a way that samples with and without such treatment were characterized using micro-Raman scattering and Fourier transform infrared absorption (FTIR) spectroscopies, thermo-mechanical techniques using thermogravimetry (TG), differential scanning calorimetry (DSC) and dynamical-mechanical analysis (DMA) and optical and scanning electron microscopies (SEM). The thermo-mechanical measurements revealed that the films present mechanical properties close to that found for the human bone and high thermal stability considering the desired applications. The vibrational spectroscopies showed that the latex and PVDF do not interact chemically leading to the formation of a polymeric blend. Besides, the results recorded using the micro-Raman technique revealed that the higher the amount of latex in the blend, the better the miscibility between both materials. In terms of morphology, the blend surface is formed by two domains: one is rougher and contains the latex well dispersed into the PVDF matrix while the other is smoother and contains both materials as well but in a less homogeneous dispersion. However, as the volume of latex is increased from 0.3 to 1.0 mL, the smoother domains become rarer to be found... (Complete abstract, click electronic address below) / Mestre