Diimide generated from the hydrazine/hydrogen peroxide/catalyst system can be used to hydrogenate unsaturated polymers in latex form. As an economical and environmentally benign alternative to the commercial processes based on hydrogen/transition metal catalysts, this method is of special interest to industry. This thesis provides a detailed description of the diimide hydrogenation process. Reaction kinetics, catalysts and gel formation mechanism have been investigated. <br /> <br /> Four main reactions and a mass transfer process form three parallel processes in this system: diimide is generated at the interface of the latex particles; diimide diffuses into the organic phase to saturate carbon-carbon double bonds; diimide may be consumed at the interface by hydrogen peroxide, and may also be consumed by the disproportionation reaction in the organic phase. The two side reactions contribute to the low hydrogenation efficiency of hydrogen peroxide. Slowing down hydrogen peroxide addition and using stable interfacial catalysts may totally suppress the side reaction in the aqueous phase. The actual catalytic activity of metal ions in the latex depends on the hydrogen peroxide concentration and the addition procedure of reactants. Cupric ion provides better selectivity for hydrogenation than ferric ion and silver ion do. Boric acid as a promoter provides improved selectivity for hydrogenation and faster diimide generation rate. The side reaction in the rubber phase results in low efficiency and gel formation. The rate constants of the four reactions in this system are estimated. <br /> <br />It is shown that the hydrogenation of nitrile rubber latex with an average particle diameter of 72 nm is mainly a reaction-controlled process. Diimide diffusion presents limitation upon hydrogenation at high hydrogenation degree range. Antioxidants can not effectively inhibit gel formation during hydrogenation. Hydrogenation of a core-shell latex with NBR as the shell layer should be able to achieve a higher efficiency, a higher degree of hydrogenation and a lower level of crosslinking.

Diimide generated from the hydrazine/hydrogen peroxide/catalyst system can be used to hydrogenate unsaturated polymers in latex form. As an economical and environmentally benign alternative to the commercial processes based on hydrogen/transition metal catalysts, this method is of special interest to industry. This thesis provides a detailed description of the diimide hydrogenation process. Reaction kinetics, catalysts and gel formation mechanism have been investigated. <br /> <br /> Four main reactions and a mass transfer process form three parallel processes in this system: diimide is generated at the interface of the latex particles; diimide diffuses into the organic phase to saturate carbon-carbon double bonds; diimide may be consumed at the interface by hydrogen peroxide, and may also be consumed by the disproportionation reaction in the organic phase. The two side reactions contribute to the low hydrogenation efficiency of hydrogen peroxide. Slowing down hydrogen peroxide addition and using stable interfacial catalysts may totally suppress the side reaction in the aqueous phase. The actual catalytic activity of metal ions in the latex depends on the hydrogen peroxide concentration and the addition procedure of reactants. Cupric ion provides better selectivity for hydrogenation than ferric ion and silver ion do. Boric acid as a promoter provides improved selectivity for hydrogenation and faster diimide generation rate. The side reaction in the rubber phase results in low efficiency and gel formation. The rate constants of the four reactions in this system are estimated. <br /> <br />It is shown that the hydrogenation of nitrile rubber latex with an average particle diameter of 72 nm is mainly a reaction-controlled process. Diimide diffusion presents limitation upon hydrogenation at high hydrogenation degree range. Antioxidants can not effectively inhibit gel formation during hydrogenation. Hydrogenation of a core-shell latex with NBR as the shell layer should be able to achieve a higher efficiency, a higher degree of hydrogenation and a lower level of crosslinking.

No description available.

The purpose of this study is to examine the propagation of waves of finite deformation in rubbers through experiments and analysis. First, attention is focused on the propagation of one-dimensional dispersive waves in strips of latex and nitrile rubber. Tensile wave propagation experiments were conducted at high strain-rates by holding one end fixed and displacing the other end at a constant velocity. A high-speed video camera was used to monitor the motion and to determine the evolution of strain and particle velocity in rubber strips. Analysis of the response through the theory of finite wave propagation indicated a need for an appropriate constitutive model for rubber; by quantitative matching between the experimental observations and analytical predictions, an appropriate instantaneous elastic response for the rubbers was obtained. This matching process suggested that a simple power-law constitutive model was capable of representing the high strain-rate response for both rubbers used. Next, the propagation of one-dimensional shock waves in strips of latex and nitrile rubber is examined. Shock waves have been generated under tensile impact in pre-stretched rubber strips; analysis of the response yields the tensile shock adiabat for rubbers. The propagation of shocks is analyzed by developing an analogy with the theory of detonation. Attention is then focused on the propagation of unloading waves of finite deformation in a rubber specimen analytically and experimentally. A rubber strip stretched to many times its initial length is released at one end and the resulting unloading is examined. Dispersive waves as well as shock waves are observed in these experiments. Quantitative discrepancies between the analytical model and experimental observations are again used to motivate a power-law model. Hysteresis in the response is attributed to strain-induced crystallization and melting phase transitions in natural latex rubber, and to nonequilibrium microstructural deformation in nitrile rubber. Finally, a Kolsky experiment is conducted and analyzed under the framework of dispersive loading and unloading waves utilized in the previous experiments. In this experiment, a phase boundary is introduced separating low and high strain phases of the rubber and is demonstrated to persist as a stationary boundary in latex rubber. / text

No description available.

L’étude de la durabilité des élastomères des stators des pompes Moineau a été menée en utilisant à la fois des simulations numériques, des essais thermomécaniques et des analyses physico-chimiques. Les simulations numériques ont eu pour principal objectif de permettre de déterminer la localisation et le niveau des maximums des champs mécaniques dans le stator. Les essais ont permis quant à eux de caractériser le comportement mécanique du matériau élastomère sous sollicitations mécaniques cycliques à différentes températures. Une première étude a permis d’analyser l’évolution de l’effet Payne en fatigue. Une seconde s’est concentrée sur l’analyse de l’effet de l’application d’un chargement thermomécanique sur l’évolution de la microstructure du matériau élastomère. / The study of the sustainability of the rubber, which is the main constitutive material of the Moineau pump stator, was carried out using finite element analyses, thermomechanical experiments and physic-chemical analysis. The numerical simulations were performed to identify the range and location of the maximal stress and strain within the pump stator. The experimental tests allowed to characterize the mechanical behaviour of rubber under cyclic solicitation at several temperatures. The first part of the study focused on the Payne effect during fatigue loading while the second dealt with the effect of a thermomechanical loading on the rubber microstructure evolution.

Chemical modification is an important way to improve the properties of existing polymers, and one of the important examples is the hydrogenation of nitrile butadiene rubber (NBR) in organic solvent by homogeneous catalysis in order to extend its application. This process has been industrialized for many years to provide high performance elastomers (HNBR) for the automotive industry, especially those used to produce components in engine compartments. In the current commercial process, a batch reactor is employed for the hydrogenation step, which is labor intensive and not suitable for large volume of production. Thus, novel hydrogenation devices such as a continuous process are being developed in our research group to overcome these drawbacks. In order to make the process more practical for industrial application, high concentration polymer solutions should be targeted for the continuous hydrogenation. However, many problems are encountered due to the viscosity of the high concentration polymer solution, which increases tremendously as the reaction goes on, resulting in severe mass transfer and heat transfer problems. So, hydrogenation kinetics in high concentration NBR solution, as well as the rheological properties of this viscous solution are very essential and fundamental for the design of novel hydrogenation processes and reactor scale up. In the present work, hydrogenation of NBR in high concentration solution was carried out in a batch reactor. A commercial rhodium catalyst, Wilkinson’s catalyst, was used with triphenylphosphine as the co-catalyst and chlorobenzene as the solvent. The reactor was modified and a PID controller was tuned to fit this strong exothermic reaction. It was observed that when NBR solution is in a high concentration the kinetic behavior was greatly affected by mass transfer processes, especially the gas-liquid mass transfer. Reactor internals were designed and various agitators were investigated to improve the mechanical mixing. Experimental results show that the turbine-anchor combined agitator could provide superior mixing for this viscous reaction system. The kinetic behavior of NBR hydrogenation under low catalyst concentration was also studied. It was observed that the hydrogenation degree of the polymer could not reach 95% if less than 0.1%wt catalyst (based on polymer mass) was used, deviating from the behavior under a normal catalyst concentration. The viscosity of the NBR-MCB solutions was measured in a rotational rheometer that has a cylinder sensor under both room conditions and reaction conditions. Parameters that might affect the viscosity of the solutions were studied, especially the hydrogenation degree of polymer. Rheological properties of NBR-MEK solutions, as well as NBR melts were also studied for relevant information. It is concluded that the hydrogenation kinetics deviates from that reported by Parent et al. [6] when polymer is in high concentration and/or catalyst is in low concentration; and that the reaction solution (HNBR/NBR-MCB solution) deviates from Newtonian behavior when polymer concentration and hydrogenation degree are high.

Chemical modification is an important way to improve the properties of existing polymers, and one of the important examples is the hydrogenation of nitrile butadiene rubber (NBR) in organic solvent by homogeneous catalysis in order to extend its application. This process has been industrialized for many years to provide high performance elastomers (HNBR) for the automotive industry, especially those used to produce components in engine compartments. In the current commercial process, a batch reactor is employed for the hydrogenation step, which is labor intensive and not suitable for large volume of production. Thus, novel hydrogenation devices such as a continuous process are being developed in our research group to overcome these drawbacks. In order to make the process more practical for industrial application, high concentration polymer solutions should be targeted for the continuous hydrogenation. However, many problems are encountered due to the viscosity of the high concentration polymer solution, which increases tremendously as the reaction goes on, resulting in severe mass transfer and heat transfer problems. So, hydrogenation kinetics in high concentration NBR solution, as well as the rheological properties of this viscous solution are very essential and fundamental for the design of novel hydrogenation processes and reactor scale up. In the present work, hydrogenation of NBR in high concentration solution was carried out in a batch reactor. A commercial rhodium catalyst, Wilkinson’s catalyst, was used with triphenylphosphine as the co-catalyst and chlorobenzene as the solvent. The reactor was modified and a PID controller was tuned to fit this strong exothermic reaction. It was observed that when NBR solution is in a high concentration the kinetic behavior was greatly affected by mass transfer processes, especially the gas-liquid mass transfer. Reactor internals were designed and various agitators were investigated to improve the mechanical mixing. Experimental results show that the turbine-anchor combined agitator could provide superior mixing for this viscous reaction system. The kinetic behavior of NBR hydrogenation under low catalyst concentration was also studied. It was observed that the hydrogenation degree of the polymer could not reach 95% if less than 0.1%wt catalyst (based on polymer mass) was used, deviating from the behavior under a normal catalyst concentration. The viscosity of the NBR-MCB solutions was measured in a rotational rheometer that has a cylinder sensor under both room conditions and reaction conditions. Parameters that might affect the viscosity of the solutions were studied, especially the hydrogenation degree of polymer. Rheological properties of NBR-MEK solutions, as well as NBR melts were also studied for relevant information. It is concluded that the hydrogenation kinetics deviates from that reported by Parent et al. [6] when polymer is in high concentration and/or catalyst is in low concentration; and that the reaction solution (HNBR/NBR-MCB solution) deviates from Newtonian behavior when polymer concentration and hydrogenation degree are high.

Neste trabalho de Dissertação de Tese, composições do copolímero de butadieno-acrilonitrila (NBR) foram vulcanizadas utilizando como agentes de vulcanização, a resina fenólica e o enxofre, com diferentes proporções de resina fenólica e uma única proporção de enxofre. O sistema ativador foi composto por policloropreno e óxido de zinco para as composições com resina fenólica, enquanto que por ácido esteárico e óxido de zinco para a composição com enxofre. Os materiais foram vulcanizados em uma temperatura de 190C. Foi avaliada a influência da variação dos componentes das composições sobre as propriedades reométricas, físico-mecânicas e reológicas dos materiais. Para auxiliar na interpretação dos resultados obtidos para as propriedades reométricas e físico-mecânicas, foi utilizado um planejamento estatístico de análise de variância para verificar a possibilidade da influência das variáveis e suas possíveis combinações nas propriedades avaliadas. Para as composições vulcanizadas com resina fenólica, os resultados mostraram que a composição de borracha nitrílica se tornou mais rígida com a presença da resina. Também foi observada a ocorrência de pós-cura nas composições vulcanizadas com resina fenólica. Os ensaios reológicos revelaram uma homogeneidade nas amostras submetidas aos testes de varredura de deformação, com desvio de linearidade a partir de 10% de deformação. / In this Thesis Dissertation, acrylonitrile-butadiene rubber (NBR) compositions were vulcanized using phenolic resin and sulfur as vulcanization agents with different proportions of phenolic resin and only one proportion of sulfur. The activator system was composed of polycloroprene and zinc oxide to phenolic resin compositions, while stearic acid and zinc oxide to sulfur composition. The materials were vulcanized in a temperature of 190C. The influence of the components content on rheometric, physico-mechanical and rheological properties of the materials was evaluated. In order to assist in the interpretation of the to physico-mechanical and rheometric properties results, a statistical planning of variant analysis was used to observe a possible influence of the variables and also their possible associations into the evaluated properties. The results showed that the nitrile rubber become more stiffness with the presence of phenolic resin. It was also observed the occurrence of post-vulcanization on the compositions vulcanized with phenolic resin. The rheological results showed homogeneity of the samples submitted to a strain sweep test, with a linear plateau until 10% of strain.

Submitted by Avital Rosa (avitalgabriel@hotmail.com) on 2018-01-23T16:54:36Z No. of bitstreams: 2 Dissertação de Mestrado_PPGCM _Aluno Avital Gabriel de Almeida Rosa.pdf: 5418816 bytes, checksum: f6f7f278fa5c0f54a96a91c4b6a87ad0 (MD5) Carta comprovante da versão final - Avital.png: 3621222 bytes, checksum: 7228740ac2bf0d70ebaad75deb22b89d (MD5) / Approved for entry into archive by Milena Rubi ( ri.bso@ufscar.br) on 2018-01-23T17:13:20Z (GMT) No. of bitstreams: 2 Dissertação de Mestrado_PPGCM _Aluno Avital Gabriel de Almeida Rosa.pdf: 5418816 bytes, checksum: f6f7f278fa5c0f54a96a91c4b6a87ad0 (MD5) Carta comprovante da versão final - Avital.png: 3621222 bytes, checksum: 7228740ac2bf0d70ebaad75deb22b89d (MD5) / Approved for entry into archive by Milena Rubi ( ri.bso@ufscar.br) on 2018-01-23T17:13:31Z (GMT) No. of bitstreams: 2 Dissertação de Mestrado_PPGCM _Aluno Avital Gabriel de Almeida Rosa.pdf: 5418816 bytes, checksum: f6f7f278fa5c0f54a96a91c4b6a87ad0 (MD5) Carta comprovante da versão final - Avital.png: 3621222 bytes, checksum: 7228740ac2bf0d70ebaad75deb22b89d (MD5) / Made available in DSpace on 2018-01-23T17:13:44Z (GMT). No. of bitstreams: 2 Dissertação de Mestrado_PPGCM _Aluno Avital Gabriel de Almeida Rosa.pdf: 5418816 bytes, checksum: f6f7f278fa5c0f54a96a91c4b6a87ad0 (MD5) Carta comprovante da versão final - Avital.png: 3621222 bytes, checksum: 7228740ac2bf0d70ebaad75deb22b89d (MD5) Previous issue date: 2017-11-18 / Não recebi financiamento / The three cylinder motors tend to vibrate more than the conventional four cylinder ones. In this new condition the transmission system and in particular the torsional damper of the clutch disc is subjected to sever wear and friction. The great challenge is to select new materials with low wear rate and adequate friction coefficient to attenuate this new vibration level. In this work three different candidate materials to be used as friction rings inside the torsional damper of clutch discs were tested in terms of wear resistance and friction. Two of the studied materials are currently used in the market (PA66 35 GF and NBR) in four cylinder motors and the third is currently used in clutch facing (NBR matrix composite). The materials were purchased from Schaeffler suppliers. The first step was the microstructural characterization and determination of the thermal stability of the three materials without the influence of friction. For that, the microstructure was analyzed by optical and electronic microscopy of Scanning (SEM), the amount of fibers and inorganic reinforcers was determined by burning tests and,the transition temperatures were determined by differential calorimetry. Two aging temperatures were studied 80 and 150oC. The effect of the ageing time was determined by hardness and infrared spectroscopy measurements. Among the three materials and clutch facing, they show a more stable structure in the temperature range between 80 and 150ºC. The PA66GF35 suffered changes in crystalline content and the NBR thermal degradation. The second step consisted in determining the wear characteristics of the material in bench tests with the objective of measuring the wear rate and friction coefficient of the material under extreme conditions of specific pressure and velocity (DIN50320, 1979). The results of the friction test had the following classification: NBR (0.13)> PA66GF35 (0.11)> clutch facing (0.09). Despite having a lower coefficient of friction, the clutch facing was the only material that achieved the minimum wear resistance required for the friction ring. Therefore the clutch facing is the best material for a 3 cylinder engine that requires a higher wear and thermal resistance on the clutch plate. / O motor de três cilindros tende a ter vibrações maiores que do motor de quatro cilindros. Nesta nova configuração o sistema de transmissão e, em particular, o amortecedor torcional do disco de embreagem fica sujeito a condições de desgaste e atrito mais severas. O grande desafio atual está na busca de componentes com baixo desgaste e um coeficiente de atrito adequado e que elimine os ruídos. Neste trabalho foram caracterizados os materiais utilizados na fabricação de anéis de atrito do amortecedor torcional de discos de embreagem quanto à resistência ao desgaste e atrito. Dois dos três materiais são hoje utilizados no mercado como componente de anel de atrito (PA66GF35 e elastômero NBR) em motores de quatro cilindros e o terceiro é atualmente utilizado em Lonas de embreagem. A primeira etapa consistiu na caracterização microestrutural e determinação da estabilidade térmica dos três materiais sem a influência de atrito. Para isso foram realizadas análises em microscopia óptica e eletrônica de varredura (MEV), teste de queima para porcentagem de fibra e tratamentos de envelhecimento, seguido de análises através de calorimetria diferencial, dureza, espectroscopia no infravermelho. Dentre os três materiais a lona de embreagem mostrou ser a mais estável na faixa de temperaturas entre 80 e 150ºC. O PA66GF35 sofreu alteração de cristalinidade e o NBR endurecimento devido à degradação térmica. A segunda consistiu na determinação das características de desgaste do material em função das variáveis de influência em condições controladas de laboratório. Para isso foi realizado um teste de bancada com o objetivo de medir a taxa de desgaste e coeficiente de atrito do material em condições extremas de pressão específica e velocidade (DIN50320, 1979). Os resultados do ensaio o atrito teve a seguinte classificação: NBR (0,13) >PA66GF35 (0,11)>Lona (0,09). Apesar de ter um coeficiente de atrito menor, a Lona de embreagem foi o único material que atingiu a resistência ao desgaste mínima exigida para o anel de atrito. Portanto a Lona de embreagem é o melhor material para um motor 3 cilindros que exige uma maior resistência ao desgaste e térmica, no disco de embreagem.