Made available in DSpace on 2017-07-10T14:57:32Z (GMT). No. of bitstreams: 1 HELOUISE_ RIGHI.pdf: 781690 bytes, checksum: e73794e76d42164775e107e6f2160613 (MD5) Previous issue date: 2016-03-02 / With the ample craving for teeth whitening, it is fundamental the production of increasingly clearer materials and also a good color stability, before the possible degradation which are exposed. The camphorquinone (CQ) is the photo initiator most widely applied on the dental composite, but it has the yellow coloration and suffers darkening when exposed to ultraviolet light (UV), endangering the maintenance of the esthetics harmony. The goal of this study was to evaluate in vitro the effect of the photo initiator Phenylpropanodione, singly or in association with the CQ, about the color stability of the resinous photoactive cement and its bond adhesive resistence, by microshear. The null hypotheses are: i) the photo initiator PPD does not interfere with the color changing of the resin cement, after the photoaging motivated by prolonged exposure to UV light; and ii) the photo initiator PPD does not interfere with the resistance of the adhesive bond of resin cement to the ceramic. Four resinous cements where used, which one of them was commercial (RelyX Venner, 3M/ESPE) and three experimental, differing each other's photo initiator's concentration. For the color analysis, ceramic discs were cemented above the bovine dentine, simulating the indirect restorations (n=8), being exposed to 120 h of UV, and tested about the color alterations which were measured applying the CIELab scale, by spectrophotometer of reflectance. The obtained datas were verified about the normal distribution, for then being submited to ANOVA and to the complementary test Tukey, all with 5% significance. The results of color analysis do not statistically significant difference to E of 4 cements studied neither to L , a and b . For the Union of Resistance of all cements studied showed statistically significant differences among themselves, with the highest for commercial cement RelyX Venner® (29.07 MPa), followed by cement with CQ (21.74 MPa) , and cement CQ + PPD (19.09 MPa); and the lowest result was obtained with the cement using only the PPD as photoinitiator (13.99 MPa) . Therefore to the parameters studied in this work, the PDD was not advantageous as photoinitiator resin cements, because made low bond strength value ceramics and not demonstrated superiority as for color stability . / Com o amplo anseio pelo branqueamento dental, é fundamental a produção de materiais cada vez mais claros e que também possuam boa estabilidade de cor, ante às possiveis degradações a que ficam expostos. A Canforoquinona (CQ) é o fotoiniciador mais amplamente empregado nos compósitos odontológicos, porém tem coloração amarelada e sofre escurecimento ao ser exposta à luz ultra violeta (UV), comprometendo a manutenção da harmonia estética. O objetivo deste estudo foi avaliar in vitro o efeito do fotoiniciador Phenilpropanodiona (PPD), isoladamente ou em associação com a CQ, sobre a estabilidade de cor de cimentos resinosos fotoativados, e sua resistência de união adesiva à cerâmica, por teste de microcisalhamento. As hipóteses nulas testadas são: i) o fotoiniciador PPD não interfere na alteração de cor de cimentos resinosos, após o foto envelhecimento provocado por exposição prolongada a luz UV; e ii) o fotoiniciador PPD não interfere na resistência da união adesiva de cimentos resinosos à cerâmica. Foram utilizados 4 cimentos resinosos, sendo um comercial (RelyX Venner®) e 3 experimentais, diferindo entre si quanto ao tipo e concentração dos fotoiniciadores. Para a análise de cor, foram cimentados discos cerâmicos sobre dentina bovina, simulando restaurações indiretas (n=8), sendo expostos a 120 h de UV, e testados quanto às alterações de cor, que foram mensuradas empregando a escala CIELab, por meio de espectrofotômetro de reflectância. Os dados obtidos foram verificados quanto a distribuição normal, para então serem submetidos a ANOVA e ao teste complementar Tukey, todos com significância de 5%. Os resultados do teste de cor não apresentam diferença estatisticamente significante para o E dos 4 cimentos estudados, nem tampouco para L, a e b. Para a resistência de união, todos os cimentos estudados apresentaram diferenças estatisticamente significantes entre si, com o maior resultado para o cimento comercial RelyX Venner® (29,07 Mpa), seguido pelo cimento com CQ (21,74 Mpa), e então pelo cimento de CQ+PPD (19,09 Mpa); e o menor resultado foi obtido com o cimento utilizando apenas o PPD como fotoiniciador (13,99 Mpa). Portanto, para os parâmetros estudados neste trabalho, o PDD não se mostrou vantajoso como fotoiniciador de cimentos resinosos, já que apresentou baixo valor de resistência de união à cerâmica e não demonstrou superioridade quanto à estabilidade de cor.

The goal of this research was to utilize the morphological control inherently imparted by the electrospinning process to improve the active layer performance in energy conversion devices as well as to better understand the relationship between morphology and performance in energy storage devices. Discrete control of the active layer morphology can promote exciton dissociation in organic photovoltaic cells (OPVs), whereas developing efficient ion diffusion pathways and beneficial polymer-ion interaction in polymer-gel electrolytes is demonstrated to result in enhanced battery performance. We demonstrate the ability to develop unique morphologies in Poly(3-hexafluoro propylene) (P3HT) films with energy storage applications using various electrospinning techniques. Electrospinning in a solvent-saturated atmosphere allows for the design of ribbon architectures with polymer domains on the order of 5-10 um. These ribbon structures form what appear to be bi-continuous films, which could then be filled with an acceptor / fullerene type material to create a bulk heterojucton for OPV devices. Dropping chloroform onto the electrospinning needle during the spinning process results in P3HT fibers with porous surfaces. These fibers have diameters of ~ 2 um. Using a coaxial needle to electrospin a P3HT solution in the core, and a CHCl3 sheath solution created hybrid ribbon-fiber structures. These structures have even smaller domain sizes than the ribbons created using a solvent saturated atmosphere. Cospinning P3HT with sacrificial polymers results in P3HT fiber morphologies upon removal of the sacrificial template polymer. Additionally, introducing P3HT into an established fiber matrix results in fibrous P3HT architectures after the template fibers are removed. Developing hybrid polymer-gel electrolytes using crosslinked PEO electrospun fibers results in membranes with high affinity for liquid electrolyte components. These electrospun PEO fiber mats exhibit excellent ionic conductivities at room temperature (12 mS/cm) exceeding an electrospun PVDF control. Furthermore, the PEO fiber mats can absorb nearly three times as much liquid electrolyte as the PVDF control. PEO has been show to interact with lithium salts to aid in dissociation and diffusion during battery cycling. Although the ionic conductivity data suggest PEO to be a superior electrolyte, pulsed-field-gradient NMR shows that lithium diffusion is faster in PVDF samples. From coin cell discharge experiments, PEO is believed to interact strongly with Li+ ions, inhibiting them from diffusing rapidly during fast charge/discharge rates. However, PEO/PETA fiber electrolytes show nearly 100% theoretical capacity discharge at C/100 and a capacity retention of ~ 35% at a C/5 discharge rate in contrast to a glass fiber separator which shows only a capacity that is approximately 85% of the theoretical value. The unique mechanical properties of PEO/PETA electrospun mats could lead to interesting artificial skin and wound healing applications. Upon crosslinking at elevated temperatures (~40 degrees C), the fiber mats exhibit improved tensile strength and much higher ultimate stress at break. The porous nature of the materials lend to easy oxygen diffusion for wound healing, and the hydrophilicity promotes continued adhesion to existing tissue making these mats possible adhesive-less bandages. / Ph. D.

Ce travail de thèse a pour but l’étude de l’influence du nanoconfinement sur le comportement du radical phénoxyle. Une nouvelle méthodologie de génération des radicaux phénoxyle à l’état solide a été mise au point. Elle fait intervenir la fragmentation de motifs diazène et ne nécessite ni solvant ni co-réactif. Une étude de spin-trapping a permis de valider cette approche. Ainsi a été synthétisée une grande variété de matériaux hybrides organique-inorganiques, de type silice mésoporeuse (SBA 15, MCM-41) et de type polysilsesquioxane lamellaire ou poreux, fonctionnalisés par différents précurseurs de radicaux phénoxyle. Les propriétés spectroscopiques du radical phénoxyle confiné dans ces matériaux ont été étudiées par RPE en onde continue ou pulsée. Ces matériaux permettent d’augmenter de manière remarquable la durée de vie des radicaux phénoxyle. Dans ces conditions, ces derniers peuvent être qualifiés de persistants et dans certains cas de stables. L’influence du confinement a également pu être mis en évidence sur les propriétés de relaxation du radical. Enfin, une application de ces matériaux en tant que photo-initiateurs de polymérisation radicalaire a été développée. / Abstract : The aim of this study is to explore the influence of nanoconfinement on the phenoxyl radical behavior. A new methodology allowing the traceless solid state generation of phenoxyl radical was developed. It relies on the fragmentation of a diazene moieties and no solvent nor co-reagent are needed. A spin-trapping study was used to validate this approach. A wide variety of organic-inorganic hybrid materials, like mesoporous silica (SBA-15, MCM-41) and lamellar or porous polysilsesquioxane, functionalized with various phenoxyl radical precursors was synthesized. The spectroscopic properties of the phenoxyl radical contained in these materials were studied by EPR. These materials enable an amazing increase of the phenoxyl radical lifetime, they transform transient phenoxyl radical into persistent and even stable ones. The influence of the confinement has also been observed on the radical relaxation properties. Finally, an application of these materials as polymerization photo-initiator was successfully developed.