O objetivo desta pesquisa foi verificar a influência de diferentes tamanhos de partículas de carga na tenacidade à fratura (KIc), nos parâmetros do crescimento subcrítico de trinca (n e f0) e de Weibull (m e 0), na longevidade estimada pelo diagrama tensão-probabilidade-tempo (SPT) e no limite de fadiga cíclica (LFC) de compósitos resinosos experimentais. Quatro compósitos foram preparados contendo 78% em massa (59% em volume) de conteúdo inorgânico, constituído por 67% de pó de vidro com diferentes tamanhos de partículas (d50 = 0,5; 0,9; 1,2 e 1,9 µm) e 11% de sílica pirogênica. Dados de KIc obtidos pelo método single-edge notched beam (25x5x2,8 mm; n=15) foram submetidos a ANOVA/teste de Tukey (p < 0,05). n e f0 foram determinados através do ensaio de fadiga dinâmica (10-2 a 102 MPa/s) utilizando um dispositivo de flexão biaxial (12x1,2 mm; n=10). Para determinar m e 0, mais 20 espécimes de cada compósito foram testados na taxa de 100 MPa/s. Os diagramas SPT foram obtidos a partir dos dados da fadiga dinâmica e análise de Weibull. No ensaio de fadiga cíclica, um dispositivo de flexão biaxial (12x1,2 mm) foi utilizado para se obter a resistência à flexão inicial (RFI; n=14) e o LFC (n=20). LFC foi obtido pelo método escada após 105 ciclos. Para todos os testes, os espécimes foram armazenados em água destilada a 37oC por 24h. Foi realizada a fractografia dos espécimes fraturados nas taxas 10-2 e 10-1 MPa/s da fadiga dinâmica e nos ensaios para determinação da RFI e LFC. Houve relação direta entre d50 e KIc (C0,5: 1,2±0,1b; C0,9: 1,3±0,1ab; C1,2: 1,3±0,1ab; C1,9: 1,4±0,2a, em MPa.m0,5). C0,5 (31,2±6,2a) e C1,9 (34,7±7,4a) apresentaram valores de n superiores a C0,9 (20,3±3,0b) e C1,2 (17,3±1,8b). C1,2 (166,42±0,01a) apresentou o maior valor de f0 (em MPa), seguido pelo C1,9 (159,82±0,02b), C0,9 (159,59±0,02c) e C0,5 (158,40±0,02d). Não houve diferença estatística entre os valores de m (6,6 a 10,6) e 0 (170,6 a 176,4 MPa) dos compósitos. As reduções na tensão de fratura para uma probabilidade de falha de 5% após 10 anos estimadas pelo diagramas SPT foram de aproximadamente 22% para C0,5 e C1,9 e 36% para C0,9 e C1,2. Não houve diferença estatística entre as médias de RFI (155,4 a 170,7 MPa). C0,5 (93,0±18,6a) apresentou o maior LFC (em MPa), seguido pelo C1,2 (91,8±11,1ab), C1,9 (87,2±3,0b) e C0,9 (82,5±8,0c). Defeitos sub-superficiais e superficiais foram as principais origens de fratura. A trinca se propagou pela matriz polimérica ao redor das partículas (deflexão de trinca) e todas as superfícies apresentaram características de fratura frágil. Como conclusão, compósitos com partículas maiores apresentaram maior KIC, enquanto que partículas menores contribuíram para um maior LFC. Compósitos com distribuição granulométrica mais ampla, independentemente do d50, apresentaram maior resistência ao SCG. Nos demais parâmetros e propriedades avaliados (m, 0 e RFI) não houve influência do tamanho das partículas. / The aim of this study was to verify the influence of different filler sizes in the fracture toughness (KIc), subcritical crack growth (n e f0) and Weibull (m e 0) parameters, longevity estimated by the strength-probability-time (SPT) diagram and cyclic fatigue limit (CFL) of experimental resin composites. Four composites were prepared, each one containing 78 w% (59 vol%) of inorganic content, in which 67 w% were glass powder with different filler sizes (d50 = 0.5; 0.9; 1.2 e 1.9 µm) and 11 w% were pyrogenic silica. KIc data was obtained by the single-edge notched beam test and submitted to ANOVA/Tukey tests (p < 0.05). n and f0 were determined by the dynamic fatigue test (10-2 a 102 MPa/s) using a biaxial flexural device (12x1.2 mm; n=10). 20 specimens of each composite were tested at 100 MPa/s to determine Weibull parameters. SPT diagrams were constructed using the dynamic fatigue and Weibull data. For the cyclic fatigue test, a biaxial flexural device (12x1.2 mm) was used to obtain the initial flexural strength (IFS; n=14) and CFL (n=20). CFL was determined by staircase method after 105 cycles. For all tests, the specimens were stored in distilled water at 37oC for 24h. It was done the fractography of the fractured specimens that was subjected to the 10-2 e 10-1 MPa/s rates of the dynamic fatigue and to the IFS and CFL tests. There was a direct relation between d50 e KIc (C0.5: 1.2±0.1b; C0.9: 1.3±0.1ab; C1.2: 1.3±0.1ab; C1.9: 1.4±0,2a, in MPa.m0,5). C0.5 (31.2±6.2a) and C1.9 (34.7±7.4a) presented higher n values than C0.9 (20.3±3.0b) and C1.2 (17.3±1.8b). C1.2 (166.42±0.01a) showed the highest f0 value (in MPa), followed by C1.9 (159.82±0.02b), C0.9 (159.59±0.02c) and C0.5 (158.40±0.02d). There were no statistical differences among the m (6.6 to 10.6) and 0 (170.6 to 176.4 MPa) values of the composites. The reductions in fracture stress at 5% failure probability for a lifetime of 10 years estimated by the SPT diagrams were approximately 22% for C0.5 and C1.9 and 36% for C0.9 and C1.2. There were no statistical differences among the IFS means (155.4 to 170.7 MPa). C0.5 (93.0±18.6a) showed the highest CFL (in MPa), followed by C1.2 (91.8±11.1ab), C1.9 (87.2±3.0b) and C0.9 (82.5±8.0c). Near-surface and surface flaws were the main fracture origins. The crack propagated by the polymeric matrix around the fillers (crack deflection) and all the fracture surfaces showed brittle fracture features. As conclusion, composites with large fillers presented the highest KIC, while the small fillers contributed to increase the CFL. Composites with broader granulometric size distribution, regardless of d50, showed higher resistance to SCG. There was no influence of the composites filler sizes in the others parameters and properties evaluated (m, 0 and IFS).

Este trabalho apresenta uma nova abordagem experimental para determinar a reatividade de sistemas subcríticos. O método a ser apresentado utiliza o modelo da cinética subcrítica desenvolvido por Gandini e Salvatores e baseia-se apenas em grandezas medidas, tais como a taxa de contagem no detector, e nos parâmetros que surgem do ajuste dos mínimos quadrados APSD (Auto Power Spectral Density) e CPSD (Cross Power Spectral Density), não sendo necessário lidar com as quantidades de maior complexidade como a eficiência de detector. A única hipótese feita neste método foi que a fração efetiva de nêutrons atrasados e o tempo de geração de nêutrons prontos fossem independentes do nível de subcriticalidade do sistema. O método proposto foi aplicado nas medidas de reatividade de várias configurações subcríticas do reator IPEN/MB-01. Foram realizadas medidas da APSD e CPSD em diversos graus de subcriticalidade (até em torno de -7000 pcm). Nos dados das densidades espectrais foram feitos ajustes por meio do método de mínimos quadrados para obter a constante de decaimento pronto (&alpha;) e outras grandezas. Com a finalide de melhorar as estatísticas de contagem de nêutrons, fonte externa de nêutrons de Am-Be foi instalada próximo ao núcleo, além da fonte de partida. O método experimental proposto mostra claramente que, a teoria da cinética pontual clássica não descreve a reatividade medida. Em vez disso, a reatividade inferida a partir do modelo da cinética pontual clássica é próxima, em seus valores absolutos, ao índice de subcriticalidade (&zeta;) para um determinado arranjo das fontes do experimeno. A concordância dos resultados obtidos por MCNP5 e GPT-TORT, ambos utilizando os dados nucleares da biblioteca ENDF/B-VII.0, com os resultados experimentais correspondentes são de boa qualidade. / This work presents a new experimental approach to determine the reactivity levels of subcritical systems. The method employs the subcritical kinetic model developed by Gandini and Salvatores and it is based only on measured quantities such as counting rates of the detectors employed in the experiments and the parameters arising from the least squares fitting of the APSD (Auto Power Spectral Density) and CPSD (Cross Power Spectral Density). Detector efficiencies, quantity required in other procedures such as Neutron Source Multiplication (NSM) method, are not needed in the proposed method. The only hypothesis made in the method was the independence of the effective delayed neutron fraction and the prompt neutron generation time to the subcriticality level of the system. The proposed method was applied to measure the reactivity of several subcritical configurations of the IPEN/MB-01 reactor. Measurements of APSD and CPSD were performed in several degrees of subcriticality (up to around -7000 pcm). The spectral densities data were least squares fitted to get the prompt decay mode (&alpha;) and other quantities. Beside the startup source of the facility, an external neutron source of Am-Be was installed near the core in order to improve neutron counting statistics. The final experimental results are of good quality. The proposed experimental method shows clearly that the classical point kinetic theory cannot describe the measured reactivity. Instead, the reactivity inferred from this model follows closely the subcriticality index (&zeta;) for the source arrangements in the experiment. The agreement of the MCNP5 and GPT-TORT results, both with ENDF/B-VII.0 as the basic nuclear data library, when compared to the corresponding experimental ones was also good.

Em testes físicos de reatores que são realizados na criticalização, após uma troca de combustível, por exemplo, como ocorre nos reatores PWR, é muito importante monitorar continuamente a reatividade durante o processo de criticalização. Medir a reatividade utilizando o método da Cinética Inversa é um processo bastante utilizado durante a operação de um reator nuclear, e é possível determinar a reatividade em tempo real baseado nas equações de cinética pontual. Essa técnica é aplicada com sucesso a altas potências, ou em núcleos que trabalham sem a existência de uma fonte externa, já que nesse caso o Termo Fonte na equação de cinética pontual pode ser desprezado. Para operações a baixas potências, a contribuição da fonte de nêutrons precisa ser levada em consideração, e isso implica em conhecer um valor proporcional à intensidade da fonte e, portanto esse valor precisa ser determinado. O Método dos Mínimos Quadrados em Cinética Inversa (Least Square Inverse Kinetics Method LSIKM) foi testado com modelo teórico e aplicado em experimentos no Reator Nuclear IPEN/MB-01 para a determinação do Termo Fonte com a utilização de um reatímetro que ignora o Termo Fonte em primeira instância. Após a determinação da Fonte S de forma consistente, seu valor foi inserido ao algoritmo de Cinética Inversa, e utilizando dados de detectores durante a criticalização, o reatímetro com Termo Fonte foi usado para medir a reatividade no domínio subcrítico, nos passos de criticalização, após experimento. / In Physical tests which are made during the approach process, after a fuel change, as an example, like those that occur in PWR reactors, monitoring the level of subcritical condition continuously is very important. Measuring reactivity by inverse kinetics method is a process widely used during a nuclear reactor operation, and it is possible to determine reactivity on line, based on the point kinetics equations. This method is applied successfully when the reactor works without an external neutron source, or while the reactor is in the critical domain, because in these cases, the source term in point kinetics equations might be neglected. However, when the power is too low, the source contribution is not negligible and must be taken into account, and this need imply a knowledge of a value proportional to the source intensity, and so this value must be determined. The LSIKM (Least Square Inverse Kinetics Method) has been tested in a theoretical model and applied experimentally in the IPEN/MB Nuclear Reactor facility for the determination of the source term, by using a reactivity meter neglecting the source term in first instance. After the determination of the value proportional to the source contribution, this value has been inserted into the algorithm of inverse kinetics, and using neutron detector data during the approach to critical process, the reactivity meter with source term was used to determinate the reactivity in the subcritical domain, after the experiment performing.

Em testes físicos de reatores que são realizados na criticalização, após uma troca de combustível, por exemplo, como ocorre nos reatores PWR, é muito importante monitorar continuamente a reatividade durante o processo de criticalização. Medir a reatividade utilizando o método da Cinética Inversa é um processo bastante utilizado durante a operação de um reator nuclear, e é possível determinar a reatividade em tempo real baseado nas equações de cinética pontual. Essa técnica é aplicada com sucesso a altas potências, ou em núcleos que trabalham sem a existência de uma fonte externa, já que nesse caso o Termo Fonte na equação de cinética pontual pode ser desprezado. Para operações a baixas potências, a contribuição da fonte de nêutrons precisa ser levada em consideração, e isso implica em conhecer um valor proporcional à intensidade da fonte e, portanto esse valor precisa ser determinado. O Método dos Mínimos Quadrados em Cinética Inversa (Least Square Inverse Kinetics Method LSIKM) foi testado com modelo teórico e aplicado em experimentos no Reator Nuclear IPEN/MB-01 para a determinação do Termo Fonte com a utilização de um reatímetro que ignora o Termo Fonte em primeira instância. Após a determinação da Fonte S de forma consistente, seu valor foi inserido ao algoritmo de Cinética Inversa, e utilizando dados de detectores durante a criticalização, o reatímetro com Termo Fonte foi usado para medir a reatividade no domínio subcrítico, nos passos de criticalização, após experimento. / In Physical tests which are made during the approach process, after a fuel change, as an example, like those that occur in PWR reactors, monitoring the level of subcritical condition continuously is very important. Measuring reactivity by inverse kinetics method is a process widely used during a nuclear reactor operation, and it is possible to determine reactivity on line, based on the point kinetics equations. This method is applied successfully when the reactor works without an external neutron source, or while the reactor is in the critical domain, because in these cases, the source term in point kinetics equations might be neglected. However, when the power is too low, the source contribution is not negligible and must be taken into account, and this need imply a knowledge of a value proportional to the source intensity, and so this value must be determined. The LSIKM (Least Square Inverse Kinetics Method) has been tested in a theoretical model and applied experimentally in the IPEN/MB Nuclear Reactor facility for the determination of the source term, by using a reactivity meter neglecting the source term in first instance. After the determination of the value proportional to the source contribution, this value has been inserted into the algorithm of inverse kinetics, and using neutron detector data during the approach to critical process, the reactivity meter with source term was used to determinate the reactivity in the subcritical domain, after the experiment performing.

L’utilisation de technologies d’extraction est cruciale dans l’industrie cosmétique. Cette étape de procédé consomme beaucoup d’énergie et de grandes quantités de matières premières. De plus, les solvants utilisés ne sont pas tous anodins, et certains sont issus de produits pétroliers. Afin de mieux préserver l’environnement et la santé humaine, il faut trouver des alternatives aux solvants et aux méthodes d’extractions conventionnelles. Pour cela, nous avons utilisé l’eau comme solvant et des technologies innovantes pour créer de nouvelles méthodes. Les travaux présentés dans cette thèse font tout d’abord un état de l’art des méthodes d’extractions utilisant l’eau comme solvant. L’ensemble de ces méthodes très anciennes, comme récentes, ont toutes leurs spécificités en termes de matrices et de molécules extraites. Puis nous nous sommes intéressés à une méthode ancienne qu’est l’hydrodistillation. L’extraction et la séparation simultanée des composés hydrosolubles et volatiles des feuilles de boldo (Peumus boldus, Mol.) est ensuite effectuée à l’aide des micro-ondes. L’optimisation des paramètres ont ensuite aboutis sur un scale-up à l’échelle pilote. L’intensification et la mise en continu de l’extraction des feuilles de boldo assisté par ultrasons sont ensuite explorés. Puis, nous étudions une méthode en cours de maturation avec l’assistance des tensioactifs pour l’extraction de composés hydrophiles et hydrophobes du romarin (Rosmarinus officinalis L.) dans l’eau. Enfin, nous avons exploré une méthode d’extraction encore en R&D. Elle utilise uniquement l’eau pour obtenir des composés hydrophobes de l’écorce d’orange douce ( Citrus sinensis L.) à l’aide d’un appareil micro-ondes pour atteindre un état subcritique. / The use of innovative extraction technologies is of outmost importance in the cosmetic industry. This process step is consuming large amounts of energy and materials. Furthermore, some solvents used are not benign. Some of them are from oil products. In order to better preserve the environment and human health, we must find alternatives to solvents and conventional extraction methods. To pursue this goal, we will use water as solvent and innovative technologies to create new extraction methods of natural products. The work presented in this thesis first establishes a review of extraction methods. All those methods, old as well as new ones, are specific in terms of target matrix or extracted molecules. Then, we focused on a mature extraction method: hydrodistillation. The simultaneous extraction and separation of water soluble compounds as well as volatile compounds from boldo leaves (Peumus boldus, Mol.), is undertaken with the help of microwaves. The parameters optimization leads to a pilot scale-up. The intensification and continuous mode transition of the ultrasound assisted extraction of boldo leaves is then studied. Afterwards, we studied the maturing method of surfactant addition to water. This is in order to extract hydrophilic and hydrophobic compounds of rosemary (Rosmarinus officinalis L.). Finally, we explored an extraction method still in R&D. This method use only water in order to extract hydrophobic compounds of sweet orange peels ( Citrus sinensis L.) with a microwave device.

Ce travail concerne l'extraction de substances naturelles d'origine végétale en utilisant des procédés « verts » tels que l'extraction au CO2 supercritique (CO2-SC, de 90 à 1000 bar) et l'extraction à l'eau sub-critique (SWE). Ces procédés sont une alternative à l'hydrodistillation (HD) et l'extraction par solvant (SE) traditionnellement utilisés dans l'industrie des produits naturels. La majorité du travail a été réalisée sur l'espèce Tetraclinis articulata où les performances des procédés, CO2-SC , HD, SWE et SE, ont été optimisées puis comparées en termes de rendement, composition chimique, durée…, et en particulier activité antioxydante des extraits (évaluée par les tests ABTS+ and DPPH). La plus forte activité antioxydente a été mise en évidence pour les extraits CO2-SC, ceci étant très probablement dû à une moindre dégradation thermique, comme l'a indiqué la comparaison des compositions chimiques. La CO2-SC basse pression (90 bar) a permis d'obtenir un extrait de bonne qualité et, pour ce cas, une modélisation a été proposée pour comprendre et identifier le mécanisme limitant qui s'est avéré être l'équilibre solide-fluide. La modélisation de l'hydrodistillation a également été proposée, basée sur le modèle de Sovová . Ensuite, l'approche a été étendue à d'autres plantes : Eucalyptus cinerea, Eucalyptus Camaldulensis, Cypres sempervirens et callitris. / This work has dealt with extraction of natural substances from plants using « green » processes such as supercritical CO2 extraction (CO2-SC from 90 to 1000 bar) and extraction with subcritical water (SWE). These processes are an alternative to hydrodistillation (HD) and solvent extraction (SE) traditionally used in the natural products industry. Main part of the work was done on the species Tetraclinis articulata, and performance of the different processes, CO2-SC, HD,SWE and SE, were optimized and compared in terms of yield, chemical composition, duration ... and especially antioxidant activity of extracts (assessed by the ABTS+ and DPPH tests). CO2-SC extracts exhibited the strongest antioxidant activity and comparison of chemical compositions of the different extracts indicated that this is very probably due to lower thermal degradation of active molecules. For low pressure CO2-SC (90 bar), a model was proposed to understand and identify the limiting mechanism that proved to be solid-fluid equilibrium. For hydrodistillation, modelling, based on the Sovová 's model was also proposed. Then, the approach was extended to other plants: Eucalyptus cinerea and Eucalyptus camaldulensis, Cypres sempervirens and Callitris.

Este trabalho apresenta uma nova abordagem experimental para determinar a reatividade de sistemas subcríticos. O método a ser apresentado utiliza o modelo da cinética subcrítica desenvolvido por Gandini e Salvatores e baseia-se apenas em grandezas medidas, tais como a taxa de contagem no detector, e nos parâmetros que surgem do ajuste dos mínimos quadrados APSD (Auto Power Spectral Density) e CPSD (Cross Power Spectral Density), não sendo necessário lidar com as quantidades de maior complexidade como a eficiência de detector. A única hipótese feita neste método foi que a fração efetiva de nêutrons atrasados e o tempo de geração de nêutrons prontos fossem independentes do nível de subcriticalidade do sistema. O método proposto foi aplicado nas medidas de reatividade de várias configurações subcríticas do reator IPEN/MB-01. Foram realizadas medidas da APSD e CPSD em diversos graus de subcriticalidade (até em torno de -7000 pcm). Nos dados das densidades espectrais foram feitos ajustes por meio do método de mínimos quadrados para obter a constante de decaimento pronto (&alpha;) e outras grandezas. Com a finalide de melhorar as estatísticas de contagem de nêutrons, fonte externa de nêutrons de Am-Be foi instalada próximo ao núcleo, além da fonte de partida. O método experimental proposto mostra claramente que, a teoria da cinética pontual clássica não descreve a reatividade medida. Em vez disso, a reatividade inferida a partir do modelo da cinética pontual clássica é próxima, em seus valores absolutos, ao índice de subcriticalidade (&zeta;) para um determinado arranjo das fontes do experimeno. A concordância dos resultados obtidos por MCNP5 e GPT-TORT, ambos utilizando os dados nucleares da biblioteca ENDF/B-VII.0, com os resultados experimentais correspondentes são de boa qualidade. / This work presents a new experimental approach to determine the reactivity levels of subcritical systems. The method employs the subcritical kinetic model developed by Gandini and Salvatores and it is based only on measured quantities such as counting rates of the detectors employed in the experiments and the parameters arising from the least squares fitting of the APSD (Auto Power Spectral Density) and CPSD (Cross Power Spectral Density). Detector efficiencies, quantity required in other procedures such as Neutron Source Multiplication (NSM) method, are not needed in the proposed method. The only hypothesis made in the method was the independence of the effective delayed neutron fraction and the prompt neutron generation time to the subcriticality level of the system. The proposed method was applied to measure the reactivity of several subcritical configurations of the IPEN/MB-01 reactor. Measurements of APSD and CPSD were performed in several degrees of subcriticality (up to around -7000 pcm). The spectral densities data were least squares fitted to get the prompt decay mode (&alpha;) and other quantities. Beside the startup source of the facility, an external neutron source of Am-Be was installed near the core in order to improve neutron counting statistics. The final experimental results are of good quality. The proposed experimental method shows clearly that the classical point kinetic theory cannot describe the measured reactivity. Instead, the reactivity inferred from this model follows closely the subcriticality index (&zeta;) for the source arrangements in the experiment. The agreement of the MCNP5 and GPT-TORT results, both with ENDF/B-VII.0 as the basic nuclear data library, when compared to the corresponding experimental ones was also good.

O objetivo desta pesquisa foi verificar a influência de diferentes tamanhos de partículas de carga na tenacidade à fratura (KIc), nos parâmetros do crescimento subcrítico de trinca (n e f0) e de Weibull (m e 0), na longevidade estimada pelo diagrama tensão-probabilidade-tempo (SPT) e no limite de fadiga cíclica (LFC) de compósitos resinosos experimentais. Quatro compósitos foram preparados contendo 78% em massa (59% em volume) de conteúdo inorgânico, constituído por 67% de pó de vidro com diferentes tamanhos de partículas (d50 = 0,5; 0,9; 1,2 e 1,9 µm) e 11% de sílica pirogênica. Dados de KIc obtidos pelo método single-edge notched beam (25x5x2,8 mm; n=15) foram submetidos a ANOVA/teste de Tukey (p < 0,05). n e f0 foram determinados através do ensaio de fadiga dinâmica (10-2 a 102 MPa/s) utilizando um dispositivo de flexão biaxial (12x1,2 mm; n=10). Para determinar m e 0, mais 20 espécimes de cada compósito foram testados na taxa de 100 MPa/s. Os diagramas SPT foram obtidos a partir dos dados da fadiga dinâmica e análise de Weibull. No ensaio de fadiga cíclica, um dispositivo de flexão biaxial (12x1,2 mm) foi utilizado para se obter a resistência à flexão inicial (RFI; n=14) e o LFC (n=20). LFC foi obtido pelo método escada após 105 ciclos. Para todos os testes, os espécimes foram armazenados em água destilada a 37oC por 24h. Foi realizada a fractografia dos espécimes fraturados nas taxas 10-2 e 10-1 MPa/s da fadiga dinâmica e nos ensaios para determinação da RFI e LFC. Houve relação direta entre d50 e KIc (C0,5: 1,2±0,1b; C0,9: 1,3±0,1ab; C1,2: 1,3±0,1ab; C1,9: 1,4±0,2a, em MPa.m0,5). C0,5 (31,2±6,2a) e C1,9 (34,7±7,4a) apresentaram valores de n superiores a C0,9 (20,3±3,0b) e C1,2 (17,3±1,8b). C1,2 (166,42±0,01a) apresentou o maior valor de f0 (em MPa), seguido pelo C1,9 (159,82±0,02b), C0,9 (159,59±0,02c) e C0,5 (158,40±0,02d). Não houve diferença estatística entre os valores de m (6,6 a 10,6) e 0 (170,6 a 176,4 MPa) dos compósitos. As reduções na tensão de fratura para uma probabilidade de falha de 5% após 10 anos estimadas pelo diagramas SPT foram de aproximadamente 22% para C0,5 e C1,9 e 36% para C0,9 e C1,2. Não houve diferença estatística entre as médias de RFI (155,4 a 170,7 MPa). C0,5 (93,0±18,6a) apresentou o maior LFC (em MPa), seguido pelo C1,2 (91,8±11,1ab), C1,9 (87,2±3,0b) e C0,9 (82,5±8,0c). Defeitos sub-superficiais e superficiais foram as principais origens de fratura. A trinca se propagou pela matriz polimérica ao redor das partículas (deflexão de trinca) e todas as superfícies apresentaram características de fratura frágil. Como conclusão, compósitos com partículas maiores apresentaram maior KIC, enquanto que partículas menores contribuíram para um maior LFC. Compósitos com distribuição granulométrica mais ampla, independentemente do d50, apresentaram maior resistência ao SCG. Nos demais parâmetros e propriedades avaliados (m, 0 e RFI) não houve influência do tamanho das partículas. / The aim of this study was to verify the influence of different filler sizes in the fracture toughness (KIc), subcritical crack growth (n e f0) and Weibull (m e 0) parameters, longevity estimated by the strength-probability-time (SPT) diagram and cyclic fatigue limit (CFL) of experimental resin composites. Four composites were prepared, each one containing 78 w% (59 vol%) of inorganic content, in which 67 w% were glass powder with different filler sizes (d50 = 0.5; 0.9; 1.2 e 1.9 µm) and 11 w% were pyrogenic silica. KIc data was obtained by the single-edge notched beam test and submitted to ANOVA/Tukey tests (p < 0.05). n and f0 were determined by the dynamic fatigue test (10-2 a 102 MPa/s) using a biaxial flexural device (12x1.2 mm; n=10). 20 specimens of each composite were tested at 100 MPa/s to determine Weibull parameters. SPT diagrams were constructed using the dynamic fatigue and Weibull data. For the cyclic fatigue test, a biaxial flexural device (12x1.2 mm) was used to obtain the initial flexural strength (IFS; n=14) and CFL (n=20). CFL was determined by staircase method after 105 cycles. For all tests, the specimens were stored in distilled water at 37oC for 24h. It was done the fractography of the fractured specimens that was subjected to the 10-2 e 10-1 MPa/s rates of the dynamic fatigue and to the IFS and CFL tests. There was a direct relation between d50 e KIc (C0.5: 1.2±0.1b; C0.9: 1.3±0.1ab; C1.2: 1.3±0.1ab; C1.9: 1.4±0,2a, in MPa.m0,5). C0.5 (31.2±6.2a) and C1.9 (34.7±7.4a) presented higher n values than C0.9 (20.3±3.0b) and C1.2 (17.3±1.8b). C1.2 (166.42±0.01a) showed the highest f0 value (in MPa), followed by C1.9 (159.82±0.02b), C0.9 (159.59±0.02c) and C0.5 (158.40±0.02d). There were no statistical differences among the m (6.6 to 10.6) and 0 (170.6 to 176.4 MPa) values of the composites. The reductions in fracture stress at 5% failure probability for a lifetime of 10 years estimated by the SPT diagrams were approximately 22% for C0.5 and C1.9 and 36% for C0.9 and C1.2. There were no statistical differences among the IFS means (155.4 to 170.7 MPa). C0.5 (93.0±18.6a) showed the highest CFL (in MPa), followed by C1.2 (91.8±11.1ab), C1.9 (87.2±3.0b) and C0.9 (82.5±8.0c). Near-surface and surface flaws were the main fracture origins. The crack propagated by the polymeric matrix around the fillers (crack deflection) and all the fracture surfaces showed brittle fracture features. As conclusion, composites with large fillers presented the highest KIC, while the small fillers contributed to increase the CFL. Composites with broader granulometric size distribution, regardless of d50, showed higher resistance to SCG. There was no influence of the composites filler sizes in the others parameters and properties evaluated (m, 0 and IFS).

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Fracture mechanics is an effective approach for characterizing material resistance to interfacial failure and for making interface reliability predictions. Because interfacial bond integrity is a major concern for performance and reliability, the need to evaluate the fracture and delamination resistance of an interface under different environmental conditions is very important. This study investigates the effects of temperature, solution chemistry and environmental preconditioning, in several solutions on the durability of silicon/epoxy and glass/epoxy systems. A series of experiments was conducted using wedge test specimens to investigate the adhesion performance of the systems subjected to a range of environmental conditions. Both silicon and glass systems were relatively insensitive to temperature over a range of 22-60°C, but strongly accelerated by temperatures above 60°C, depending on the environmental chemistry and nature of the adhesive system used. Silicon/commercial epoxy specimens were subjected to preconditioning in deionized (DI) water and more aggressive solution mixtures prior to wedge insertion to study the effect of prior environmental exposure time on the system. The wedge test data from preconditioned specimens were compared with standard wedge test results and the system was insensitive to preconditioning in DI water but was affected significantly by preconditioning in aggressive environments. Plots describing - G (crack velocity versus applied strain energy release rate) characteristics for a particular set of environmental conditions are presented and a comparison is made for different environmental conditions to quantify the subcritical debonding behavior of systems studied. A kinetic model to characterize subcritical debonding of adhesives for microelectronic applications is also proposed based on molecular interactions between epoxy and a silane coupling agent at the interface and linear elastic fracture mechanics, which could help predict long-term deterioration of interfacial adhesion. / Master of Science