No description available.

No description available.

No description available.

No description available.

No description available.

The influence of silane treated amorphous fumed silica fillers on properties of the cured epoxy was examined in the first part of the study. Silica particles were treated with 3- aminopropyldiethoxymethylsilane (APDS) and 3-aminopropyltriethoxysilane (APTS) coupling agents. The filler and coupling agents decreased the mobility of the polymer chains in the vicinity of the filler leading to an increase in the activation energy for the glass transition and an increase in cooperativity. Fumed silica did not significantly affect moisture diffusion properties. Next, a linear dilatometer was used to investigate the effects of cure conditions, mold types, and the presence of filler in the model epoxy. These studies revealed that there was substantial shrinkage in the cured epoxy on heating it through its glass transition region. The shrinkage was determined to be the result of stress in the epoxy generated during cure and could be minimized by curing at lower temperatures, followed by a postcuring heat treatment. Additional free volume in the sample increased the magnitude of the shrinkage by allowing increased stress release through increased network mobility. Decreasing the polymer mobility by adding fillers decreased the observed shrinkage. The influence of the model epoxy crosslink density was examined by varying the content of 1,4-butanediol in the model system. Addition of 1,4-butanediol led to a decrease in the modulus and glass transition temperature, which resulted in a reduction in residual stress and subsequent shrinkage. Moisture uptake increased with the addition of 1,4-butanediol due to an increase in the free volume of the epoxy. However, even with greater moisture uptake, the addition of 1,4-butanediol to the epoxy increased its adhesion to quartz by promoting lower residual stress and increased energy dissipation. These results indicate that bulk diffusion of water is not the controlling factor in adhesive degradation in this system. / Ph. D.

A evolução sofrida pelas resinas compostas, aliada à sua característica de restaurar a aparência natural dos dentes em relação à cor e opacidade, torna esses materiais uma das principais escolhas entre os materiais restauradores usados na odontologia. A estabilidade de cor e a opacidade assumem um papel crucial no sucesso do tratamento restaurador estético, pois a alteração destas características pode indicar a substituição das restaurações estéticas. Essas propriedades estão relacionadas ao grau de conversão desses materiais no momento da polimerização. O objetivo deste trabalho foi avaliar a influência do envelhecimento artificial acelerado sobre a estabilidade de cor, opacidade e densidade das ligações cruzadas de compósitos armazenados por 30 e 90 dias em ambientes diferentes (temperatura ambiente/geladeira). Foram utilizados 5 compósitos odontológicos em duas tonalidades: claras e escuras. As embalagens dos compósitos foram mantidas em temperatura ambiente (+/- 25ºC) e em geladeira (+/- 8ºC), sendo armazenados nestes ambientes por 30 e 90 dias, para posterior confecção dos corpos-de-prova (12 mm de diâmetro / 2 mm de espessura). Sobre essas amostras, foram realizadas as leituras da alteração de cor ( E), opacidade (OP), e densidade das ligações cruzadas, previamente e posteriormente a realização do procedimento de envelhecimento artificial acelerado. Após análise estatística (2-way ANOVA - Tukey - nível de significância em p<0.05), observou-se que compósitos QuiXfil Universal, Tetric EvoCeram C3 e SR Adoro A2, apresentaram valores para alteração de cor clinicamente inaceitável ( E 3,3). Quanto à opacidade, as resinas diretas, de tonalidades claras apresentaram menor opacidade que as tonalidades escuras enquanto que a resina indireta apresentou maior opacidade para a tonalidade clara que a escura. Quanto à densidade de ligações cruzadas, o envelhecimento artificial acelerado produziu um aumento na densidade de ligações cruzadas das resinas diretas. Concluiu-se que não houve um comportamento homogêneo dos materiais, em relação às propriedades estudadas, em função do tempo e ambiente de armazenagem sugerindo que a ação do envelhecimento é primordial e mais relevante para a alteração dos materiais ao longo do tempo. / The evolution of composite resins, allied to their characteristic of restoring the natural appearance of teeth regarding color and opacity, makes them one of the main materials of choice among the restorative materials used in dentistry. Color and opacity stability assume a crucial role in a successful aesthetic restoration treatment, since changes in these characteristics may indicate the replacement of aesthetic restorations. These properties are associated with these materials\' degree of conversion at the moment of polymerization. The purpose of this study was to evaluate the influence of artificial accelerated aging on color stability, opacity, and density of cross-links in composites stored for 30 and 90 days in different environments (room temperature/refrigerator). Five dental composites were used, with two shades: light and dark. Composite packages were kept in room temperature (+/- 25ºC) and in a refrigerator (+/- 8ºC), for 30 and 90 days, for posterior specimen fabrication (12 mm in diameter / 2 mm thick). Specimens were subjected to readings for color change ( E), opacity (OP), and cross-link density, before and after artificial accelerated aging. Statistical analysis (2-way ANOVA - Tukey - level of significance at p<0.05), revealed that QuiXfil Universal, Tetric EvoCeram C3, and SR Adoro A2 composites presented clinically unacceptable color changes ( E 3.3). Regarding opacity, light shade direct resins presented less opacity compared to dark shades, whereas light shade indirect resins presented more opacity than dark ones. As to cross-link density, artificial accelerated aging increased crosslink density in direct resins. It is concluded that the materials did not behave homogenously, in terms of the studied properties, under the effects of storage time and environment. This suggests that the effects of aging are imperative and more relevant to material changes over time.

A evolução sofrida pelas resinas compostas, aliada à sua característica de restaurar a aparência natural dos dentes em relação à cor e opacidade, torna esses materiais uma das principais escolhas entre os materiais restauradores usados na odontologia. A estabilidade de cor e a opacidade assumem um papel crucial no sucesso do tratamento restaurador estético, pois a alteração destas características pode indicar a substituição das restaurações estéticas. Essas propriedades estão relacionadas ao grau de conversão desses materiais no momento da polimerização. O objetivo deste trabalho foi avaliar a influência do envelhecimento artificial acelerado sobre a estabilidade de cor, opacidade e densidade das ligações cruzadas de compósitos armazenados por 30 e 90 dias em ambientes diferentes (temperatura ambiente/geladeira). Foram utilizados 5 compósitos odontológicos em duas tonalidades: claras e escuras. As embalagens dos compósitos foram mantidas em temperatura ambiente (+/- 25ºC) e em geladeira (+/- 8ºC), sendo armazenados nestes ambientes por 30 e 90 dias, para posterior confecção dos corpos-de-prova (12 mm de diâmetro / 2 mm de espessura). Sobre essas amostras, foram realizadas as leituras da alteração de cor ( E), opacidade (OP), e densidade das ligações cruzadas, previamente e posteriormente a realização do procedimento de envelhecimento artificial acelerado. Após análise estatística (2-way ANOVA - Tukey - nível de significância em p<0.05), observou-se que compósitos QuiXfil Universal, Tetric EvoCeram C3 e SR Adoro A2, apresentaram valores para alteração de cor clinicamente inaceitável ( E 3,3). Quanto à opacidade, as resinas diretas, de tonalidades claras apresentaram menor opacidade que as tonalidades escuras enquanto que a resina indireta apresentou maior opacidade para a tonalidade clara que a escura. Quanto à densidade de ligações cruzadas, o envelhecimento artificial acelerado produziu um aumento na densidade de ligações cruzadas das resinas diretas. Concluiu-se que não houve um comportamento homogêneo dos materiais, em relação às propriedades estudadas, em função do tempo e ambiente de armazenagem sugerindo que a ação do envelhecimento é primordial e mais relevante para a alteração dos materiais ao longo do tempo. / The evolution of composite resins, allied to their characteristic of restoring the natural appearance of teeth regarding color and opacity, makes them one of the main materials of choice among the restorative materials used in dentistry. Color and opacity stability assume a crucial role in a successful aesthetic restoration treatment, since changes in these characteristics may indicate the replacement of aesthetic restorations. These properties are associated with these materials\' degree of conversion at the moment of polymerization. The purpose of this study was to evaluate the influence of artificial accelerated aging on color stability, opacity, and density of cross-links in composites stored for 30 and 90 days in different environments (room temperature/refrigerator). Five dental composites were used, with two shades: light and dark. Composite packages were kept in room temperature (+/- 25ºC) and in a refrigerator (+/- 8ºC), for 30 and 90 days, for posterior specimen fabrication (12 mm in diameter / 2 mm thick). Specimens were subjected to readings for color change ( E), opacity (OP), and cross-link density, before and after artificial accelerated aging. Statistical analysis (2-way ANOVA - Tukey - level of significance at p<0.05), revealed that QuiXfil Universal, Tetric EvoCeram C3, and SR Adoro A2 composites presented clinically unacceptable color changes ( E 3.3). Regarding opacity, light shade direct resins presented less opacity compared to dark shades, whereas light shade indirect resins presented more opacity than dark ones. As to cross-link density, artificial accelerated aging increased crosslink density in direct resins. It is concluded that the materials did not behave homogenously, in terms of the studied properties, under the effects of storage time and environment. This suggests that the effects of aging are imperative and more relevant to material changes over time.

No description available.

Cette étude vise à mieux comprendre les mécanismes physiques à l'origine des propriétés mécaniques et des propriétés ultimes des caoutchoucs renforcés. Des échantillons de caoutchouc naturel dans lequel sont dispersés des agrégats de Silice précipitée ou de Noir de Carbone et vulcanisés au Soufre ont étés mis en oeuvre. Les principaux paramètres étudiés sont la densité de réticulation et l'interface charge-caoutchouc modifiée au moyen de différents traitements de surface de silice. L'impact des charges et du type d'interface sur les propriétés mécaniques dans le domaine des faibles déformations (effet Payne) et des grandes déformations est présenté. Le phénomène de cristallisation sous étirement dans le caoutchouc naturel est étudié par diffraction des rayons X in-situ au cours d'essais de traction quasi-statiques ou d'essais dynamiques couplés à un système d'acquisition stroboscopique. Nous montrons une corrélation des mesures du module, du degré de gonflement à l'équilibre, de l'orientation des chaînes mesurée par diffusion de rayons X et de la densité de réticulation mesurée par RMN dans le caoutchouc naturel non chargé. Dans le caoutchouc naturel renforcé, les corrélations établies à l'aide de ces mêmes mesures permettent de préciser les mécanismes de renforcement aux faibles et aux grandes déformations. Enfin, la résistance à la déchirure est évaluée en géométrie cisaillement pur sur les matériaux non-renforcés et renforcés. Les effets du type d'interface, de la densité de réticulation et de la vitesse d'essai sur la résistance à la déchirure sont présentés. Nous discutons également les profils de déformation locale obtenus par corrélation d'image / This study aims at better understanding the physical mechanisms responsible for the mechanical and ultimate properties in reinforced rubber materials. Sulfur vulcanized samples made of a Natural Rubber matrix in which aggregates of precipitated Silica or Carbon Black are dispersed have been manufactured. The main control parameters are the crosslink density and the filler/rubber interactions through different silica surface treatments. The effect of fillers and interface type on the mechanical properties in the small strain regime (Payne effect) and large strain regime is presented. X-ray diffraction experiments have been performed to study the phenomenon of strain-induced crystallization (SIC) both during quasi-static tensile tests and dynamical tests coupled to a stroboscopic acquisition device. Mechanical measurements have proved to correlate fairly well to the crosslink density measured by NMR, to equilibrium swelling degree and to the average chain segment orientation measured by X-ray scattering in unfilled natural rubber in agreement with the rubber elasticity theory. In reinforced materials, the correlation of those different measurements of local chain stretching give new insights on the reinforcement mechanisms at small and large strain. Tear experiments have been performed on Pure Shear pre-notched unfilled and filled samples. The influence of interface type, crosslink density and test drawing speed on tear resistance are presented. Local strain profiles obtained from digital image correlation and the crystallized fraction profiles from in-situ X-ray diffraction are also discussed