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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Avaliação da liberação de monômero residual, absorção de água e porosidade superficial em resinas acrílicas para prótese ocular / Evaluation of residual monomer, water sorption and porosity by acrylic resins used to eye prostheses

Oliveira, Rodrigo Elias de 07 March 2008 (has links)
A necessidade do aprimoramento das técnicas de confecção de próteses oculares que permitam satisfazer, com rapidez e excelência, a demanda de atendimento de pacientes portadores de perdas do bulbo ocular, levou ao desenvolvimento deste estudo comparativo no qual se avalia a porosidade superficial, absorção de água e liberação de monômero residual de resinas acrílicas. Foram estabelecidos quatro grupos de estudo, sendo cada grupo composto por 15 corpos de prova: Grupo 1 - resina acrílica termo polimerizável convencional / ciclo térmico convencional; Grupo 2 - resina acrílica termo polimerizável em microondas / ciclo microondas; Grupo 3 - resina acrílica termo polimerizável convencional / ciclo microondas; Grupo 4 - resina acrílica auto polimerizável com cadeia cruzada / auto polimerização. A avaliação da quantidade de monômero residual liberado foi realizada por meio de espectrofotometria, durante o período de 11 dias. A determinação da absorção de água baseou-se na diferença do peso apresentado pelos corpos de prova nas condições experimentais seco e após submersão em água deionizada por um período de 7 dias. A determinação da porosidade superficial foi calculada sob a forma de porcentagem por área de superfície analisada, empregando-se lupa estereoscópica para captação da imagem a ser processada pelo software ImageLab 2000®. Submetendo-se os dados à análise estatística ANOVA/TUKEY (p<=0,05) observou-se que a liberação de monômero residual foi significantemente maior no primeiro dia para o Grupo 1, semelhante durante todo o período para o Grupo 2, menor a partir do dia 8 para o Grupo 3 e decrescente até o dia 8 para o Grupo 4. A liberação de monômero residual foi semelhante para os Grupos 1 e 3, menor para o Grupo 2 e maior para o Grupo 4. A absorção de água foi semelhante para os quatro grupos de estudo. A maior porosidade ocorreu no Grupo 2, sendo os Grupos 1 e 3 semelhantes entre si. Concluiu-se que os ciclos térmicos de polimerização em água e em microondas não interferiram na liberação de monômero residual da resina acrílica termo polimerizável convencional. A liberação de monômero residual variou em função do tipo de resina acrílica. O tipo de resina acrílica e o ciclo de polimerização a que foram submetidas não interferiram na absorção de água. Os ciclos térmicos de polimerização em água e em microondas não interferiram na porosidade apresentada pela resina acrílica termo polimerizável convencional. A porosidade superficial variou em função do tipo de resina acrílica avaliada. / This comparative evaluation of porosity, water sorption and residual monomer presented by acrylic resins was conducted, looking for excellence and rapidity in the confection of eye prostheses. Four groups, comprising of 15 specimens each, were established and submitted to polymerization cycles: Group 1 - conventional heat polymerizing acrylic resin / conventional heat-polymerization cycle; Group 2 - microwave acrylic resin / microwave cycle; Group 3 - conventional heat polymerizing acrylic resin / microwave cycle; Group 4 - cross-linked auto-polymerizing acrylic resin / auto-polymerizing process. Residual monomer liberation was determined by spectrophotometry during 11 days period. Water sorption was calculated by weighting dried specimens and weighting after 7 days of submersion in deionized water. Superficial porosity was determined by percentage of area, in images processed by the software ImageLab 2000®. Subjecting data to ANOVA/TUKEY test (p<=0,05) it was observed that residual monomer liberation was higher in the first day for Group 1, similar during all the period for Group 2, lower after day 8 for Group 3 and decreasing until day 8 for Group 4. Residual monomer liberation was similar to Groups 1 and 3, lower for Group 2 and higher for Group 4. Water sorption was similar to all groups. Group 2 displayed more superficial porosity, and Group 1 and 3 were similar regarding this test. In conclusion, conventional polymerization and microwave processes did not interfere in residual monomer liberation of conventional acrylic resin. The residual monomer liberation varied according the type of acrylic resin. Microwave cycle provided similar or smaller residual monomer liberation. The type of acrylic resin and the polymerization cycle utilized did not modify water sorption. The conventional heat polymerizing cycle and microwave cycle did not interfere in superficial porosity of conventional heat polymerizing acrylic resin. The superficial porosity varied according to the acrylic resin.
12

Characterization of Substituted Polynorbornenes for Advanced Lithography

Hoskins, Trevor P. J., II 23 September 2005 (has links)
A fundamental characterization of hexafluoroalcohol substituted polynorbornene (HFAPNB) was completed to improve the final photoresist formulation using these materials. In this work, it was found that the dissolution behavior of these materials was controlled by the ability of polymer chains to form hydrogen bonds. This ability to form interchain hydrogen bonds was affected by stereochemical changes in the polynorbornene backbone as molecular weights increase. These observed changes in backbone polynorbornene stereochemistry were accurately modeled using the "helix-kink" theory, first described by Ahmed and Ludovice. It was found that several material properties altered the interchain hydrogen bonding within these materials, such as the polydispersity, polymerization catalyst, and the polymer film thickness. However, none of these material properties altered the unusual dissolution behavior observed in these materials. To improve the potential formulation of these materials, the interactions between HFAPNB and resist additives were studied. For all tested photoacid generators, it was found that some interchain hydrogen bonding occurred between resist additive molecules and HFA side groups, which retarded the dissolution rate in the formulated material. In particular, one can create a simple resist using unprotected HFAPNB polymer with an iodonium photoacid generator. Finally, a series of norbornene oligomers were evaluated as potential dissolution inhibitors for HFAPNB. It was found that the dissolution rate of HFAPNB can be completely inhibited with dissolution inhibitors at a loading of 15%.
13

Investigation of transient phenomena of proton exchange membrane fuel cells

Songprakorp, Roongrojana 05 September 2008 (has links)
The research presented in this thesis is a contribution to the modeling and understanding of the dynamic behavior of proton exchange membrane fuel cells (PEMFCs). A time-dependent, two-phase non-isothermal model of the membrane electrode assembly was developed and implemented using the finite element method. In addition to solving a phenomenological transport equation for water in the membrane, the model takes into consideration the non-equilibrium water sorption to better capture some of the dynamic characteristics of water transport in the MEA. Mass transfer using Fickian diffusion is implemented in the model. Two different models describing the electrochemical reactions in the catalyst layer including a macro-homogeneous model and an agglomerate model, are also implemented. Conservation of energy is included in the solution procedure in order to assess the impact of thermal effects on the dynamics of the transport in the MEA. For the purpose of model and concept validation, the model was first solved in a steady two-dimensional mode for a through- plane computational domain using a commercial software package, COMSOL Multiphysics version 3.2b. The impact of using a single- and two-phase modeling approaches was evaluated, and the predicted current-voltage performance characteristic are found in good agreement with the experimental data available in the literature. In addition, the developed model was benchmarked against a finite element-based in-house code for further validation and to evaluate numerical accuracy and computational performance. Transient simulations of operation under dynamic voltage sweeps are presented, and parametric studies are conducted to investigate the impact of various model, operation and transport properties on the predicted dynamic cell performance. In particular, the rate of load change, the difference in water content between the anode and cathode, and the water sorptions rate are shown to have significant impact on cell performance in unsteady operation, especially at higher current densities. Parametric studies also address the sensitivity of the model results to physical properties, highlighting the importance of accurately determining certain physical properties of the fuel cell components. Finally, the application of the model to air-breathing fuel cells provides further insight into the dynamic performance characteristic of such type of fuel cells.
14

Compósitos de matriz poliéster com fibras de macambira (Bromélia laciniosa): modelagem, simulação e experimentação. / Polyester matrix composite with macambira fiber (Bromélialaciniosa): modeling, simulation and experimentation.

CRUZ, Valério Carlos de Almeida. 25 September 2018 (has links)
Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-09-25T12:44:58Z No. of bitstreams: 1 VALÉRIO CARLOS DE ALMEIDA CRUZ - TESE (PPGEP) 2013.pdf: 2545282 bytes, checksum: 3f37053bbbe74448ce66d692fa5819c1 (MD5) / Made available in DSpace on 2018-09-25T12:44:58Z (GMT). No. of bitstreams: 1 VALÉRIO CARLOS DE ALMEIDA CRUZ - TESE (PPGEP) 2013.pdf: 2545282 bytes, checksum: 3f37053bbbe74448ce66d692fa5819c1 (MD5) Previous issue date: 2013-02-28 / Capes / O presente trabalho tem como objetivo o estudo teórico/experimental da sorção de água em compósitos poliméricos reforçados com fibras de macambira (Bromélia Laciniosa). Foi utilizado como matriz polimérica uma resina de poliéster insaturado e fibras de Macambira originárias do cariri paraibano. Os compósitos foram confeccionados com 70% de poliéster e 30% de fibras cortadas em tamanhos de aproximadamente 3 cm. Os ensaios de sorção de água foram realizados com amostras de 3 mm e 6 mm de espessura nas temperaturas de 25, 50 e 70°C. Uma modelagem matemática tridimensional transiente foi usada para predizer a transferência de massa durante a sorção de água destes compósitos. A cinética de sorção de água nos compósitos mostrou ser influenciada pela sua relação área/volume. Verificou-se que em tempos curtos, aproximadamente 50 horas, e temperatura de processo mais elevadas, os corpos com maior relação área/volume apresentam uma maior velocidade de sorção. Em tempos longos, os compósitos com maior relação área/volume e maior temperatura de processo apresentam maiores teores de água sorvida. O teor de umidade de equilíbrio dos compósitos com 30% de fibras de Macambira apresentaram valores de 16,8%, a 25°C, 17,00% a 50°C e 19,10% a 70ºC, para as espessuras de 3 mm, e de 12,5% a 25°C, 15,8% a 50°C e 14,8% a 70ºC, para a espessura de 6 mm. Resultados teóricos do teor de umidade médio dos compósitos foram comparados com dados experimentais e um bom ajuste foi obtido. Desta comparação, os coeficientes de difusão de massa foram obtidos para cada condição experimental. / This reseach aims to study theoretically and experimentally water absorption in polymer composites reinforced with macambira fiber (BromeliaLaciniosa). As polymer matrix was used unsaturated polyester resin and macambira fiber from cariri region of the Paraiba state. The composite samples were manufactured with 70% polyester resin and 30% macambira fiber (3cm length). Experiments were carried out in samples with 3 and 6 mm thickness at the temperatures 25, 50 and 70ºC. A transient 3D mathematical model was used to predict mass transfer during water sorption of the composites. It was verified that the water sorption kinetic is affected by area /volume relationships. For short time, approximately 50 h, the sample with lower area/volume relationships and higherprocess temperature presents a larger water absorption velocity, and for long times, these samples presents higher equilibrium water content. Equilibrium moisture content of the samples were 16.8% at 25ºC, 17.00%. at 50ºC and 19.10% at 70ºC, for 3 mm thickness, and 12.5% at 25ºC, 15.8% at 50ºC and 14.8% at 70 ºC, for 6 mm thickness. Predicted results of the moisture content of the composites were compared with experimental data, and a good agreement was verified. From this comparison diffusion coefficients were obtained for different experimental conditions.
15

Avaliação da liberação de monômero residual, absorção de água e porosidade superficial em resinas acrílicas para prótese ocular / Evaluation of residual monomer, water sorption and porosity by acrylic resins used to eye prostheses

Rodrigo Elias de Oliveira 07 March 2008 (has links)
A necessidade do aprimoramento das técnicas de confecção de próteses oculares que permitam satisfazer, com rapidez e excelência, a demanda de atendimento de pacientes portadores de perdas do bulbo ocular, levou ao desenvolvimento deste estudo comparativo no qual se avalia a porosidade superficial, absorção de água e liberação de monômero residual de resinas acrílicas. Foram estabelecidos quatro grupos de estudo, sendo cada grupo composto por 15 corpos de prova: Grupo 1 - resina acrílica termo polimerizável convencional / ciclo térmico convencional; Grupo 2 - resina acrílica termo polimerizável em microondas / ciclo microondas; Grupo 3 - resina acrílica termo polimerizável convencional / ciclo microondas; Grupo 4 - resina acrílica auto polimerizável com cadeia cruzada / auto polimerização. A avaliação da quantidade de monômero residual liberado foi realizada por meio de espectrofotometria, durante o período de 11 dias. A determinação da absorção de água baseou-se na diferença do peso apresentado pelos corpos de prova nas condições experimentais seco e após submersão em água deionizada por um período de 7 dias. A determinação da porosidade superficial foi calculada sob a forma de porcentagem por área de superfície analisada, empregando-se lupa estereoscópica para captação da imagem a ser processada pelo software ImageLab 2000®. Submetendo-se os dados à análise estatística ANOVA/TUKEY (p<=0,05) observou-se que a liberação de monômero residual foi significantemente maior no primeiro dia para o Grupo 1, semelhante durante todo o período para o Grupo 2, menor a partir do dia 8 para o Grupo 3 e decrescente até o dia 8 para o Grupo 4. A liberação de monômero residual foi semelhante para os Grupos 1 e 3, menor para o Grupo 2 e maior para o Grupo 4. A absorção de água foi semelhante para os quatro grupos de estudo. A maior porosidade ocorreu no Grupo 2, sendo os Grupos 1 e 3 semelhantes entre si. Concluiu-se que os ciclos térmicos de polimerização em água e em microondas não interferiram na liberação de monômero residual da resina acrílica termo polimerizável convencional. A liberação de monômero residual variou em função do tipo de resina acrílica. O tipo de resina acrílica e o ciclo de polimerização a que foram submetidas não interferiram na absorção de água. Os ciclos térmicos de polimerização em água e em microondas não interferiram na porosidade apresentada pela resina acrílica termo polimerizável convencional. A porosidade superficial variou em função do tipo de resina acrílica avaliada. / This comparative evaluation of porosity, water sorption and residual monomer presented by acrylic resins was conducted, looking for excellence and rapidity in the confection of eye prostheses. Four groups, comprising of 15 specimens each, were established and submitted to polymerization cycles: Group 1 - conventional heat polymerizing acrylic resin / conventional heat-polymerization cycle; Group 2 - microwave acrylic resin / microwave cycle; Group 3 - conventional heat polymerizing acrylic resin / microwave cycle; Group 4 - cross-linked auto-polymerizing acrylic resin / auto-polymerizing process. Residual monomer liberation was determined by spectrophotometry during 11 days period. Water sorption was calculated by weighting dried specimens and weighting after 7 days of submersion in deionized water. Superficial porosity was determined by percentage of area, in images processed by the software ImageLab 2000®. Subjecting data to ANOVA/TUKEY test (p<=0,05) it was observed that residual monomer liberation was higher in the first day for Group 1, similar during all the period for Group 2, lower after day 8 for Group 3 and decreasing until day 8 for Group 4. Residual monomer liberation was similar to Groups 1 and 3, lower for Group 2 and higher for Group 4. Water sorption was similar to all groups. Group 2 displayed more superficial porosity, and Group 1 and 3 were similar regarding this test. In conclusion, conventional polymerization and microwave processes did not interfere in residual monomer liberation of conventional acrylic resin. The residual monomer liberation varied according the type of acrylic resin. Microwave cycle provided similar or smaller residual monomer liberation. The type of acrylic resin and the polymerization cycle utilized did not modify water sorption. The conventional heat polymerizing cycle and microwave cycle did not interfere in superficial porosity of conventional heat polymerizing acrylic resin. The superficial porosity varied according to the acrylic resin.
16

A Theoretical Study of Carriers in Polymeric Facilitated Transport Membranes for Post-combustion Carbon Capture

Deng, Xuepeng January 2021 (has links)
No description available.
17

Evaluation of water sorption and solubility behavior of nine different polymeric luting materials

Alsheikh, Rasha N. January 2009 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / The cementation procedure is the key to long-term success of fixed restorations. The prognosis of prosthetic restoration is largely impacted by the maintenance of the luting cement and the adhesive bond. When exposed to water or saliva, most restorative materials undergo hydrolytic degradation. The purpose of this study is to evaluate the water solubility and water sorption characteristics of newly introduced acidic polymeric luting agents over a 180-day water-storage period. Nine different luting agents were tested. Fifty-two disc specimens of each material were fabricated using a mold with an internal dimension of 15[plus-minus]0.1 mm in diameter and 1.0 [plus-minus]0.1 mm deep. A constant weight, W0 [subscript zero], was reached after desiccating the specimens. Then, 13 specimens were assigned randomly to one of the four testing periods in the water for seven, 30, 90 and 180 days. After each period, the specimens were removed from the water and weighed to get W1 [subscript one]. A second period of desiccating the samples provided a constant weight W2 [subscript two]. The water sorption and solubility were determined by the following equations: WSP [subscript SP](%) = (W1 [subscript one] W2 [subscript two] ) X 100/ W0 [subscript zero] ,WSL [subscript SL](%) = (W0 [subscript zero] W2 [subscript two) X 100/ W0 [subscript zero]. The resin-modified glass-ionomers showed the highest water sorption/solubility results. The resin luting agents had the lowest sorption/solubility results. The self-adhesives showed a wide range of solubility/sorption; in general, they showed lower results compared with the resin-modified glass-ionomers. All the materials reached some sort of equilibrium after 90-days. Based on the results of our study, we conclude that self-adhesive luting materials were not all alike. Rely X Unicem was the most comparable to the resin luting materials. The resin luting materials had the lowest solubility and sorption. Resin-modified glass-ionomers showed the highest sorption/solubility results.
18

Comportement physicochimique des polymères pariétaux à l’échelle supramoléculaire dans des assemblages bioinspirés de la paroi végétale : application à la fibre native / Physicochemical behaviour at supramolecular scale of plant cell wall polymers in bioinspired assemblies : Application to native fibers.

Muraille, Loïc 14 October 2014 (has links)
En raison des enjeux écologiques actuels, l'utilisation de ressources lignocellulosiques dans l'élaboration de matériaux composites suscite actuellement un intérêt grandissant. Au-delà des applications traditionnelles (papier, panneaux composites, textiles…), les ressources lignocellulosiques constituent une alternative durable aux ressources fossiles pour la production de biocarburant ou d'agrocomposites à base de fibres végétales. Ainsi, si l'on souhaite optimiser les performances de ces nouveaux composites, il est nécessaire de mieux connaitre les propriétés de la fibre et par conséquent réaliser une étude multi-échelle des propriétés physicochimiques et mécaniques des fibres, des polymères constitutifs et de leurs interactions. Dans ce cadre, le premier objectif de la thèse a été de mesurer à l'échelle nanométrique le gradient de propriétés mécaniques et physicochimiques de coupes de fibres végétales par l'intermédiaire de deux techniques utilisant le microscope à force atomique (AFM) visant à cartographier les propriétés nanomécaniques et les caractéristiques spectrales en IR. Puis, pour mieux comprendre le rôle des polymères et de leurs interactions sur les propriétés de la fibre, des systèmes bioinspirés, composés des trois principales classes de polymères pariétaux et de complexité croissante ont été élaborés en veillant à introduire des interactions covalentes et non covalentes entre les polymères, et plus particulièrement entre la lignine et les polysaccharides (cellulose, hémicelluloses). / Due to environmental context, the exploitation of lignocellulosic ressources in the elaboration of composite materials has currently a growing interest. Beside traditional uses (paper, textiles…), lignocellulosic ressources constitute a sustainable alternative to fossils ressources for the production of biofuels and fiber-based agrocomposites. However, optimization of the performance of fiber composites requires a multi-scale study of the physicochemical and mechanical properties of the fibers and of their constitutive polymers and their interactions. To this end, the first goal of the thesis is to measure at nanometric scale, the gradient of the mechanical and physicochemical properties of plant fibers using two AFM-based techniques aiming at the mapping of nanomechanical and IR spectral properties. Then, in order to better understand the role of the polymers and of their interactions on the fibers' properties, bioinspired systems have been designed with three main lignocellulosic polymers while achieving in covalent and non-covalent interactions between the polymers (especially between polysaccharides and lignin).
19

Compósitos de matriz poliéster com fibras de caroá Neoglaziovia variegata: caracterização mecânica e sorção de água.

NÓBREGA, Múcio Marcos Silva. 26 September 2018 (has links)
Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-09-26T13:42:32Z No. of bitstreams: 1 MÚCIO MARCOS SILVA NÓBREGA - TESE (PPGEP) 2007.pdf: 5674260 bytes, checksum: b79349f8d5a305a7090f3fa7ae22559e (MD5) / Made available in DSpace on 2018-09-26T13:42:32Z (GMT). No. of bitstreams: 1 MÚCIO MARCOS SILVA NÓBREGA - TESE (PPGEP) 2007.pdf: 5674260 bytes, checksum: b79349f8d5a305a7090f3fa7ae22559e (MD5) Previous issue date: 2007-11-21 / CNPq / O presente trabalho tem como objetivo o desenvolvimento de compósitos poliméricos reforçados com fibras de Caroá Neoglaziovia variegata para avaliação de seu desempenho mecânico, bem como suas características de sorção de água. Foi utilizado como matriz polimérica uma resina de poliéster insaturado e fibras de Caroá originárias do cariri paraibano. Os compósitos foram confeccionados com diferentes teores de fibras, cortadas em tamanhos de aproximadamente 3 cm, e moldados por compressão em molde metálico para avaliação das propriedades mecânicas. A composição de amostras de melhor desempenho mecânico foi escolhida para os ensaios de sorção de água, com amostras de 20x20mm² com 3cm e 6cm de espessura na temperatura de 25°C, 50°C e 70°C. Uma modelagem matemática tridimensional transiente foi usada para predizer a transferência de massa durante a sorção de água destes compósitos. Os resultados indicam que as propriedades mecânicas em tração dos compósitos estudados aumentam com o teor de fibras acima de 24% em massa até um volume crítico, em torno de 30%.Resistência ao impacto aumentou para todas as composições em virtude da eficiência de transferência de tensão para as fibras. Os resultados obtidos para o módulo de elasticidade dos compósitos evidenciam que estes são superiores ao da matriz, para todos os teores abaixo de 45% de fibras, o que é associado às características das fibras. A cinética de sorção de água nos compósitos mostrou ser influenciada pela relação área/volume. Pôde-se observar que em tempos curtos, aproximadamente 100 horas, os corpos com menor relação apresentam uma maior velocidade de sorção. Em tempos longos os compósitos com maior relação área/volume apresentam maiores teores de água sorvida. O teor de umidade de equilíbrio dos compósitos com 30% de fibras de caroá apresentaram valores de 14,48% à 25ºC e 16,52% à 70ºC, para as espessuras de 3 e 6 mm, respectivamente. A modelagem matemática utilizada para a obtenção da solução numérica de sorção de água nos compósitos reforçados por fibras de caroá foi adequada e satisfatória e a técnica de volumes finitos mostrou-se eficiente para discretizar a equação de difusão no sistema de coordenadas cartesianas para um sólido paralelepípedo, possibilitando a análise de fenômenos difusivos transientes nestes sólidos. / This research has the objective of developing polymeric composites enhanced with Caroá fibers Neoglaziovia variegata, in order to evaluate its mechanical performance and water sorption. It was used as polymeric matrix an unsaturated polyester resin and Caroá fibers originated from Paraiba state. The composites were made with different fiber contents, cut approximately with 3cm length and molded by compression in a metallic mould in order to evaluate its mechanical properties. The better mechanical composition of the sample was chosen to water sorption test in sample with dimension 20x20mm² and 3cm and 6cm thickness in the temperature of 25°C, 50°C and 70°C. A tri-dimensional transient mathematical modeling was used to predict mass transfer during the water sorption by these composites. Results indicates enhancement of mechanical properties of composites with 24% of mass made of the fibers until a critical volume of 30%. For the impact resistance this increases occurred for all compositions because of the transference of tension for the fibers. The results for elasticity modulus of composite shows that are higher than to the matrix for all fiber contents lower than 45%, which is related with the fiber properties. The water sorption kinetic was related with the area/volume relationship. We can observe that in short period of time, 100 hours, that composites with lower area/volume relationship absorbs water faster. On the order hand, the ones with higher area/volume relationship show more sorption in longer periods of time. The equilibrium moisture content for 30% fiber composite show results of 14.48% in 25°C and 16.52% in 70°C, for 3mm and 6mm thickness respectively. Mathematical models used to obtain numerical solution of water sortion in composites enhanced with Caroá fibers were satisfactory and the finite volume techniques was adequated to discretize the diffusion equation in Cartesian coordinate system for a parallelepiped solids, permitting the analyze of transient diffusive phenomena in this solids.
20

Analyse et modélisation cinétique du vieillissement thermique des matrices PEI et PEEK et ses conséquences sur l’absorption d’eau / Kinetic analysis and modelling of thermal aging of PEI and PEEK matrices and its consequences on water absorption

Courvoisier, Emilie 06 March 2017 (has links)
Le PEI et le PEEK sont des thermoplastiques aromatiques haute performance. Il est envisagé de les utiliser comme matrice de structures composites en environnement de moteur d’avion. En conditions de service, ils seront soumis à des cycles hygrothermiques complexes consistant à des vieillissements thermo-oxydant jusqu’à 180 °C en continu et des vieillissements humide à 70 °C dans 85 % HR. Leur durabilité ayant fait l’objet de peu de travaux de recherche, l'objectif de cette thèse était d’étudier les effets isolés et combinés des vieillissements thermique et humide de ces deux matrices. Tout d’abord, des films minces de PEI et de PEEK ont été oxydés à différentes températures (entre 180 et 320 °C) et pressions partielles d’oxygène (entre 0,21 et 50 bars). Ils ont ensuite été caractérisés aux différentes échelles structurales pertinentes : moléculaire, macromoléculaire, morphologique et macroscopique. Cette caractérisation multi-techniques et multi-échelles a permis de déterminer leurs mécanismes de dégradation thermique. Ensuite, le vieillissement humide du PEI et du PEEK a été étudié entre 30 et 70 °C, entre 10 et 100 % HR, avant et après vieillissement thermique. A partir d’une compilation des données de la littérature pour une large variété de polymères contenant un seul type de groupe polaire dans l’unité monomère, des relations structure - propriété de transport de l'eau ont été établies. Elles confirment que l’hydrophilie et la diffusion d’eau résultent essentiellement d’interactions moléculaires entre les molécules d’eau et les groupes polaires de la matrice polymère. Enfin, un modèle cinétique de thermo-oxydation a été établi pour les matrices PEI et PEEK et a été interfacé avec les relations structure – propriété de transport d’eau. Il permet de simuler l’ensemble des données expérimentales accumulées dans ce travail de thèse. / PEI and PEEK are high performance aromatic thermoplastics. They are planned to be used as matrices of composite materials in aircraft engine environment. In service conditions, they will be subjected to complex hygrothermal cycles consisting in a series of thermo-oxidative agings up to 180 °C and humid agings at 70 °C in 85 % RH. As their durability has been little studied in the literature, the aim of this PhD thesis is to study the separated and combined effects of thermal and humid agings of these two matrices. At first, thin PEI and PEEK films have been oxidised at different temperatures (between 180 and 320 °C) and oxygen partial pressures (between 0.21 and 50 bars). There have been then characterized at different structural scales: molecular, macromolecular, morphological and macroscopic. This multi-technique and multi-scale characterization has enabled the determination of their thermal degradation mechanisms. Then, the humid aging of PEI and PEEK has been studied between 30 and 70 °C and between 10 and 100 % RH, before and after thermal aging. From a literature compilation of data for a large variety of polymers containing a single type of polar group in their monomer unit, structure – water transport property relationships have been established. They confirm that hydrophilicity and water diffusion result essentially from the molecular interactions between water molecules and polar groups in polymer matrices. Finally, a thermos-oxidation kinetic model has been established for PEI and PEEK matrices and has been juxtaposed with the structure – water transport property relationships. It enables to simulate all the experimental data obtained in this PhD work.

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