[pt] Este trabalho procura estudar materiais compostos constituídos por uma matriz de resina poliéster reforçada por fibras de vidro, com propriedades de ortotropia, transparência e birrefringência, através do desenvolvimento de métodos apropriados para a sua obtenção e sua caracterização mecânica e ótica. O material foi obtido a partir de um tipo de fibra de vidro disponível no mercado nacional: fio Roving 374, da Ocfibras, que serviu de reforço à resina poliéster Crystic 199PA rígida, comercializada pela Leo Glass, que constituiu a matriz. O material desenvolvido teve ambos comportamentos mecânico e ótico estudados através de diversos modelos sujeitos a estados uniaxiais e biaxiais de tensões. A discussão dos resultados obtidos e do método de análise experimental empregado, conhecido como foto elasticidade ortotrópica, levou à conclusão que este método pode ser aplicado com uma precisão razoável (mais ou menos 20 por cento), a despeito das dificuldades relativas à interpretação da resposta ótica do material, que depende da transparência do mesmo e da existência de baixas tensões residuais elásticas. / [en] The present work aims to study composite materials, more precisely, certain type of reinforced fiberglass polyester resin with orthotropic, birefringent and transparency properties, through the development of appropriate methods for its mechanical and optical characterization. A kind fiberglass available on the Brazilian market was used: roving 374, (by Ocfibras) which was combines with crystic 199 P.A rigid resin matrix (by Leo Glass). Both mechanical and optical behaviors were studied through several models subjected to uniaxial and biaxial states of stress. The discussion of the results and of the experimental methods used leaded to the conclusion that this method reached good resolution – of a maximum of 20 per cent – in spite of difficulties reached in interpreting the optical response this is a function of both material’s transparency and residual elastic stresses.

Ces travaux de doctorat ont été menés dans le cadre d'un contrat CIFRE entre l'entreprise Van Robaeys Frères, l'UBS et l'IFREMER. Les travaux visent à mieux comprendre certains paramètres influençant les propriétés de fibres de lin et celles de matériaux composites. Nous avons tout d'abord mis en évidence l'influence du degré de rouissage du lin sur les propriétés mécaniques des fibres de lin et celles de matériaux composites injectés lin/polypropylène. Ensuite, à l'aide d'une étude comparative, nous avons montré qu'il est possible de réaliser des matériaux composites unidirectionnels aux propriétés mécaniques très proches à partir de filasse ou d'étoupes de lin. Puis, l'influence de l'architecture de trois renforts non tissés de lin sur les propriétés mécaniques de composites à matrice thermoplastique a été soulignée. L'anisotropie des propriétés mécaniques de ces matériaux a été mise en évidence. Enfin, la connaissance des propriétés mécaniques de fibres de lin produites par l'entreprise Van Robaeys Frères a été approfondie. On note une relation directe entre les propriétés mécaniques des fibres et celles de composites à renfort unidirectionnel. La relation est plus complexe dans le cas de composites injectés à fibres courtes. / This research study has been carried out during a CIFRE joint project between the Van Robaeys Frères Company, UBS and IFREMER. The work aims to improve understanding of the properties of both flax fibres and composite materials reinforced with flax.First, the influence of the degree of retting of flax fibers on the tensile properties of single fibers and short fiber/polypropylene composites has been shown.Then, the properties of scutched flax and flax tow were compared. We have shown that it is possible to reach similar tensile properties for unidirectional composite materials manufactured from the two products.Moreover, the influence of three different flax nonwoven reinforcements on the mechanical properties of thermoplastic matrix composites was studied. These materials were found to show anisotropy of tensile properties.Finally, the mechanical properties of the flax fibres processed by the Van Robaeys Frères Company were examined. A straightforward relationship was found between the tensile properties of the fibres and the tensile properties of unidirectional composite materials. The relationship is more complex for short fibre injected composites.

[pt] O aproveitamento sustentável do ouriço da castanha do brasil em materiais compósitos constitui a questão principal desta dissertação. A castanha do brasil é um fruto típico de grande representatividade cultural e econômica para a região amazônica e durante a sua extração há o descarte em abundância do invólucro lenhoso denominado ouriço. Este trabalho adotou metodologia experimental e está dividido em duas etapas. A primeira é a fase informativa constituída pela investigação dos conceitos de fundamentação sobre sustentabilidade, design e ciência dos materiais. A segunda descreve todo o processo de desenvolvimento do eco-compósito a partir do reaproveitamento do ouriço com resina vegetal. É apresentado desde a preparação dos experimentos á realização dos ensaios, como o de abrasão, cujo resultado indicou viabilidade técnica para aplicação do material em piso, já que o mesmo apresentou boa resistência à desgastes por atrito. As investigações realizadas contribuem para o aperfeiçoamento e adequação de tecnologia artesanal de fabricação, visando possibilitar a transferência desse conhecimento para comunidades ribeirinhas futuramente e contribuir para valorização desse produto da sociobiodiversidade. / [en] The sustainable use hedgehog chestnut Brazil in composite materials is the main issue of this thesis. The Brazil nut is a typical fruit of great economic and cultural representation to the Amazon region and during extraction for disposal in plenty of hard shell called hedgehog. This study adopted experimental methodology and is divided into two stages. The first phase is constituted by informative investigation of the concepts of reasoning on sustainability, design and materials science. The second describes the process of developing the eco-composite from resin-reused hedgehog plant. It appears from the preparation of experiments will perform the tests , such as abrasion , which results indicated the technical feasibility for application of the material in the ground, since it showed good resistance to chafing. The investigations contribute to the improvement and adaptation of technology artisanal manufacturing, aiming to make possible the transfer of this knowledge to future riverine communities and contribute to the enhancement of the product sociobiodiversity.

[pt] Os materiais termoplásticos compósitos, tais como o polipropileno reforçado com fibras de vidro curtas, são usados cada vez mais em diversos setores industriais. O reforço da fibra de vidro é uma forma utilizada para melhorar as propriedades mecânicas dos termoplásticos, devido ao elevado módulo das fibras e à melhor adesão entre as fibras e a matriz polimérica. No entanto, há poucas informações referentes às propriedades desses fluidos na literatura. No presente trabalho, um estudo das propriedades cisalhantes e elongacionais do polipropileno reforçado com fibras de vidros curtas é apresentado. As viscosidades cisalhantes e elongacionais foram obtidas em um reômetro capilar através da medição da queda de pressão na entrada convergente de um capilar axissimétrico. Utilizaram-se duas geometrias diferentes na entrada do capilar, para a obtenção dos dados experimentais: as geometrias semi-hiperbólica convergente e cônica convergente. Neste último, a viscosidade elongacional foi obtida a partir da queda de pressão na entrada, utilizando as análises de Cogswell e Binding. Simulações numéricas foram realizadas com o objetivo de investigar o comportamento do polipropileno em um processo de extrusão. As equações de conservação de massa e quantidade de movimento foram resolvidas utilizando o método dos elementos finitos a partir do programa comercial Polyflow (Ansys). Para modelar o comportamento da mecânico viscoelástico do polipropileno foram utilizados os modelos de Maxwell, Oldroyd-B e Phan-Thien Tanner (PTT), no entanto a comparação entre os resultados numéricos e os experimentais obtidos no reômetro capilar não apresentaram concordância satisfatória. / [en] Composite thermoplastic materials, like glass fiber reforced polypropropylene, are used increasingly in several industries. In particular, glass fiber reinforcement is used to improve the mechanical properties of thermoplastics, due to the high fiber modulous and to the better adesion between the fibers and the polymeric matrix. However, few data of material properties of these fluids are avaiable in the literature. In this work, a study of shear and elongational properties of a commercial short glass fiber reinforced polypropylene is presented. The shear and elongational viscosities were obtained using the pressure drop measured at a capillary rheometer, with axisymmetric converging dies. Two different die geometries were used: semihyperbolically convergent dies and conical convergent dies. In the last case, the elongational viscosity was obtained using the Cogswell and Binding analysis. Numerical simulations were also performed, to investigate the flow field through the extrusion die process, and to evaluate the pressure drop and elongational viscosity. The conservation equations of mass and momentum were solved via the finite element method, using the commercial program POLYFLOW (Ansys). The Maxwell, Oldroyd B and Phan Thien-Tanner (PTT) constitutive equations were used to model the viscoelastic mechanical behavior of Polypropylene, but the comparison between numerical results and experimental data obtained from the capillary rheometer did not show good agreement.

RESUMO A tensão de contração desenvolvida durante a polimerização de um compósito aderido às paredes do preparo cavitário pode comprometer a integridade da interface dente/restauração. O objetivo deste trabalho foi verificar a relação entre a tensão de contração e o grau de conversão em compósitos híbridos (Z250 e Tetric Ceram) e microparticulados (A110 e Heliomolar). Para o teste de tensão de contração foram utilizados bastões de vidro de silicato de boro (Pyrex), com 5 mm de diâmetro e 5 cm de altura. Os bastões foram presos às garras de uma máquina de ensaios (modelo 5565, Instron, Canton, MA, EUA) e o compósito foi aplicado às superfícies planas do vidro, as quais passararam por jateamento com óxido de alumínio (250 mm), seguido de silanização e aplicação de adesivo. A distância entre as superfícies dos vidros foi ajustada em 2 mm (Fator C=1,25). O grau de conversão (GC) foi determinado através de espectroscopia fotoacústica no infravermelho (PAS-IR) utilizando-se as razões entre as bandas correspondentes às duplas ligações carbônicas alifáticas (1640 cm -1 ) e aromáticas (1610 cm -1 ). Para cada compósito, tanto no teste de tensão como na análise do grau de conversão, foram constituídos cinco grupos variando-se o tempo de irradiação, a fim de se obter diferentes níveis de densidade de energia (4,8; 13,5; 27,0; 54,0 e 108,0 J/cm 2 ). Foram registrados os valores de tensão máxima e de grau de conversão observados no período de 10 minutos, contados a partir do início da fotoativação. A análise de dados foi feita através de ANOVA de fator duplo e teste de Tukey (a=0,05). Para os valores de tensão de contração, a interação compósito x densidade de energia foi significante. Os valores de tensão de contração para o compósito A110 variaram entre 1,2 e 7,0 MPa, para o Heliomolar entre 0,6 e 6,6 MPa, para o compósito Tetric Ceram entre 1,3 e 8,1 MPa e para o Z250 entre 2,0 e 6,6 MPa. Em geral, valores de tensão maiores foram observados nos níveis de densidade de energia mais elevados. Para o compósito A110 4,8<13,5<27,0<54,0=108,0 J/cm 2 . Para o compósito Heliomolar todos os níveis foram diferentes exceto entre 27,0 e 54,0 J/cm 2 . O compósito Tetric Ceram apresentou 4,8<13,5<27,0<54,0=108,0 J/cm 2 enquanto o compósito Z250 obteve 4,8=13,5<27,0=54,0<108,0 J/cm 2 . O GC foi influenciado pelo compósito (A110: 24% = Heliomolar: 28% = Z250: 32% < Tetric: 39%) e pela densidade de energia. As densidades de energia de 27,0 (33%); 54,0 (35%) e 108,0 (36%) J/cm 2 forneceram graus de conversão estatisticamente semelhantes, o mesmo ocorrendo entre 4,8 (23%) e 13,5 (26%) J/cm 2 e entre 13,5 e 27,0 J/cm 2 . Os resultados mostraram ainda que existe uma relação não-linear entre a tensão de contração e o grau de conversão de compósitos restauradores. Pode-se concluir que densidades de energia elevadas não necessariamente contribuem para um aumento significante no GC, mas podem acentuar o desenvolvimento de tensões de contração. / ABSTRACT The contraction stress developed during polymerization of composites bonded to cavity walls cavity is often associated with marginal gaps and interfacial failure. The aim of this study was to verify the relationship between contraction stress and degree of conversion (DC) in four composites (Z250, A110 – 3M ESPE; Tetric Ceram, Heliomolar – Vivadent). For the contraction stress test, composite (2 mm thick) was bonded between sandblasted and silane-treated glass stubs (Pirex: 5 mm diameter), mounted in a testing machine (model 5565, Instron, Canton, MA, EUA) equipped with a tensilometer to monitor the distance between the rods (C-factor=1.25). DC was determined by Infrared Photoacustic spectrometry (PAS-IR). The ratio between the aliphatic (1640 cm -1 ) and the aromatic (1610 cm -1 ) carbon double-bonds was used for calculating the DC. In both tests, each composite was light-cured for different times in order to provide different energy densities (4.8, 13.5, 27.0, 54.0, 108.0 J/cm 2 ). Maximum contraction stress and DC were measured 10 minutes after the beginning of polymerization. Results were analyzed by two-way ANOVA and Tukey’s test (a=0.05). For contraction stress, the interaction between composite and energy density was significant. Contraction stress values for A110 were between 1,2 and 7,0 MPa, Heliomolar between 0,6 and 6,6 MPa, Tetric Ceram between 1,3 and 8,1 Mpa and Z250 between 2,0 and 6,6 MPa. In general, contraction stress increases with higher energy density levels. For A110, 4.8<13.5<27.0<54.0=108.0 J/cm 2 . Heliomolar showed significant differences between all energy densities, except 27.0 and 54.0 J/cm 2 . Tetric was 4.8<13.5<27.0<54.0=108.0 J/cm 2 and Z250 showed 4.8=13.5<27.0=54.0<108.0 J/cm 2 . DC was influenced by composite (A110: 24%;Heliomolar: 28%, Z250: 32%; Tetric: 39%) and by energy density. The 27.0 (33%), 54.0 (35%) and 108.0 (36%) J/cm 2 energy densities showed similar DC, the same occurring with 4.8 (23%) and 13.5 (26%) J/cm 2 and between 13.5 and 27.0 J/cm 2 .The results showed a non-linear relationship between contraction stress and degree of conversion. It can be concluded that higher energy densities will not necessary contribute to increase DC, but may result in increased contraction stress development.

ii ABSTRACT Percolation phenomena involving the electrical conductivity, dielectric constant, Hall coefficient, magnetoconductivity, relative magnetoresistivity, 1/ f noise and thermoelectric power are investigated in graphite (G) and hexagonal boron-nitride (BN) powder mixtures. Two kinds of systems are used in the experiments: highly compressed discs and parallelepipeds, cut from these discs, as well as 50%G-50%BN and 55%G-45%BN powder mixtures undergoing compression. The measured DC conductivities follow the power-laws 0"( <p, 0) ex: (<p-<Pc)t (<p > <Pc) and O"(<p, 0) ex: (<Pc-<Pti (<p < <Pc), and the low frequency (lOOHz & 1000Hz) dielectric constant varies as c( <p, W ~ 0) ex: (<Pc - <P )-S( <P < <Pc), where <Pc is the percolation threshold, t and s are the conductivity exponents, and s is the dielectric exponent. Near the percolation threshold and at high frequencies, the AC conductivity varies with frequency as 0"( <p, w) ex: WX and the AC dielectric constant varies as c( <p, w) ex: w-Y, where the exponents x and y satisfy the scaling relation x + y = 1. The crossover frequency We scales with DC conductivity as Wc ex: O"q( <p, 0) (<p > <Pc), while on the insulating side, Wc ~ 1, resulting in q ~O for the three G-BN systems. The loss tangent tan t5( <p, w) (<p < <Pc) is found to have a global minimum, in contrary to the results of computer simulations. The Hall constant could not be measured using existing instrumentation. The measured magnetoconductivity and relative magnetoresistivity follow the power-laws - 6. 0" ex: (<p - <Pc)3.08 and 6.R/ R ex: (<p - <Pc)O.28 respectively. These two exponents, iii 3.08 and 0.28, are not in agreement with theory. The 1/ f noise was measured for the conducting discs and parallelepipeds. The normalized 1/ f noise power varies as Sv I V2 ex RW with the exponents w = 1.47 and 1.72 for the disc and parallelepiped samples respectively. Furthermore, the normalized noise power near the percolation threshold is, for the first time, observed to vary inversely with the square-root of sample volume. Based on the Milgrom-Shtrikman-Bergman-Levy (MSBL) formula, thermoelectric power of a binary composite is shown to be a linear function of the WiedemanFranz ratio. A scaling scheme for the Wiedeman-Franz ratio for percolation systems is proposed, which yields power-law behavior for the thermoelectric power. The proposed power-laws for the thermoelectric power can be written as (Sm - Md ex (<p - <Pc)h 1 for <P > <Pc and as (Sm - /~1d ex (<Pc - <p)-h2 for <p < <Pc, where Sm is the thermoelectric power for the composites, Afl is a constant for a given percolation system, and hI and h2 are the two critical exponents. The experimental thermoelectric power data for the G-BN conducting parallelepipeds was fitted to the above powerlaw for <p > <Pc. A least squares fit yielded the exponent hI = -1.13 and parameter MI =9.511l V I I< respectively.

Ο σκοπός της παρούσης διδακτορικής διατριβής ήταν η θεωρητική και πειραματική μελέτη της επίδρασης της αναπτυσσόμενης βλάβης που προέρχεται από διαφορετικές αιτίες στην μηχανική συμπεριφορά συνθέτων υλικών. Οι πηγές βλάβης που μελετήθηκαν ήταν: 1.Υγροθερμική Κόπωση 2. Θερμική Κόπωση 3. Ύπαρξη κεντρικής κυκλικής οπής διαφορετικών διαμέτρων ή εγκοπής διαφορετικών μηκών 4. Διαφορετικοί ρυθμοί παραμόρφωσης 5. Ερπυσμός και επανάταξη, και 6. Συνδυασμός των παραπάνω, όπως: ερπυσμός μετά από υγροθερμική ή θερμική κόπωση, ερπυσμό σε διαφορετικές θερμοκρασίες και χρονικές διάρκειες. Τα σύνθετα υλικά που μελετήθηκαν ήταν κοκκώδη, ινώδη και τύπου σάντουιτς σύνθετα υλικά. Για την καλύτερη μελέτη της μηχανικής και βισκοελαστικής συμπεριφοράς των συνθέτων υλικών, εφαρμόστηκε ένας σημαντικός αριθμός θεωρητικών μοντέλων, όπως είναι: 1. Το μοντέλο των τεσσάρων παραμέτρων. 2. Το μοντέλο των τριών παραμέτρων. 3. Το μοντέλο εναπομένουσων ιδιοτήτων, RPM. 4. Το θεωρητικό μοντέλο ανάλυσης των διεπιφανειακών ιδιοτήτων σε σάντουιτς υλικά. 5. Το μοντέλο πρόβλεψης βισκοελαστικής συμπεριφοράς στη μη γραμμική περιοχή. Τα συμπεράσματα που προέκυψαν από την παραπάνω μελέτη ήταν ιδιαίτερα ενδιαφέροντα. / The aim of the present investigation is to study not only experimentally but also theoretically the effect of damage due to different damage sources, which analytically are: a) hygrothermal fatigue, b) thermal fatigue, c) the existence of central hole (with different diameters) or notch (with different lengths), d) creep and relaxation, e) different stain rates and f) combination of the previous such as creep after hygrothermal or thermal fatigue and creep on different temperatures and time, on the mechanical and viscoelastic behavior of composites materials (reinforced with fibers and grains ), sandwich structures and different types of resin. For the better observation of the mechanical and viscoelastic behavior of composites materials, it was applied several theoretical models, which are: a) The four parameter model, b) the three parameter model, c) the RPM model (Residual Property Model) for the prediction of the residual mechanical properties of materials after damage from different sources, d) the theoretical model for the analysis of interfacial properties of sandwich structures and e) the viscoelastic model for the determination of the non elastic properties of composites material in function of the applied stress. From the present investigation useful conclusions were conducted for the determination of the mechanical behavior of composites materials (reinforced with fibres and grains or sandwich structures). In addition, the experimental results of this study were in great deal with those results of the application of the already mentioned theoretical models.

La conception et le dimensionnement des structures stratifiées sont aujourd’hui globalement maîtrisés grâce à la théorie classique des stratifiés. Cependant, les problèmes de délaminage près des bords libres et des jonctions posent encore de nombreuses difficultés. En effet, dans ces zones, la discontinuité des propriétés mécaniques entre les plis d’orientation différente engendre des contraintes tridimensionnelles aux interfaces interlaminaires.L’objectif de ce travail est d’étudier expérimentalement les effets de bords et de mettre en évidence les paramètres susceptibles de les influencer. Pour cela la démarche a consisté à définir un protocole de mesure par corrélation d’images des champs cinématiques, à l’échelle des plis (échelle mésoscopique), sur le bord libre d’éprouvettes stratifiées sollicitées en traction.Trois matériaux de propriétés mécaniques et de microstructures différentes ont été étudiés ainsi que deux géométries d’éprouvettes : planes et avec sauts de plis. Des calculs par éléments finis ont permis de choisir la séquence [(15/-15)2]s pour laquelle les effets de bords sont les plus importants.Cette étude a permis de montrer l’existence de gradients de déplacements et de pics de déformations de cisaillement au voisinage des interfaces interlaminaires dont l’intensité dépend des gradients de propriétés mécaniques, de l’épaisseur de l’interface interlaminaire, et de la présence d’une discontinuité géométrique. D’autre part, les observations montrent l’apparition de fissures aux interfaces fibre / matrice à l’échelle microscopique le long des interfaces interlaminaires qui se traduisent à l’échelle mésoscopique par une évolution non linéaire du cisaillement / The use of composite materials has become more and more widespread in many industrial applications. Thanks to Classical Laminates Theory, design of composite structures is today globally well mastered. However, local effects, such as delamination near free edges or junctions, remain a problem. Indeed, mismatches between elastic properties of adjacent plies induce strong three-dimensional interlaminar stresses in the vicinity of free edges and interlaminar interfaces.The aim of this work is to experimentally study these edge effects and to highlight the parameters which could influence them. The approach has consisted in measuring the mechanical fields by Digital Image Correlation at ply scale (mesoscopic scale) on free edges of laminated samples under tensile loading.Three different materials, with different mechanical properties and microstructures have been studied as well as two sample geometries: plane samples and with ply drops. Finite element calculations allowed choosing the stacking sequence [(15/-15)2]s to be studied for experimental tests in which the edge effects are the most important and measurable.The results highlight the presence of displacements gradients and shear strain concentrations near free edges and interlaminar interfaces which depends on the inter-plies gradient of mechanical properties, width of interlaminar interfaces, and presence of a geometrical discontinuity. Moreover, observations at the microscopic scale show the presence of fissures at fiber / matrix interfaces which induce a non-linear shear behavior at mesoscopic scale

Made available in DSpace on 2014-06-11T19:32:11Z (GMT). No. of bitstreams: 0 Previous issue date: 2005-11-21Bitstream added on 2014-06-13T20:42:55Z : No. of bitstreams: 1 gimenes_r_dr_araiq.pdf: 2947108 bytes, checksum: f3c4ec92aee4a4b292c3bf0d47a82b2e (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho, foi conduzido um estudo sistemático da síntese de compósitos poli(fluoreto de vinilideno-trifluoretileno)/titanato de bário - P(VDF-TrFE)/BT - para uso em Regeneração Tecidual Guiada (GTR). Esta técnica osteopromotiva tem sido amplamente empregada em tratamentos do periodonto. A GTR emprega uma barreira física (membrana) para promover a formação de osso pela migração de células ósseas na região isolada. Desta forma, estas células são capazes de regenerar o defeito ósseo pela exclusão da competição com células não-osteogênicas na reabsorção do coágulo. Desta forma, membranas de compósitos polímero-cerâmica piezoelétrica podem promover osteogênese por meio de potenciais elétricos produzidos e prover proteção mecânica a região isolada. Membranas deste tipo podem ser consideradas como barreiras alternativas para GTR. Nesta direção, as propriedades estruturais e elétricas dos compósitos P(VDF-TrFE)/BT foram avaliadas, bem como, sua biocompatibilidade in vitro. Os compósitos foram preparados pela mistura de pós de titanato de bário e poli(fluoreto de vinilideno-trifluoretileno) (VDF = 80mol%) em meio de dimetilformamida (DMF0). As membranas de compósitos foram obtidos utilizando os seguintes métodos: espalhamento de solução sobre substrato (SC), deposição em spincoating (SP) e precipitação em água seguido de prensagem a quente (WHP). Compósitos obtidos por precipitação em água apresentaram microestrutura heterogênea e superfícies adequadas. Compósitos com fração volumétrica de 0,55 apresentaram os melhores valores de polarização remanescente e constante dielétrica relativa (33,1mC/cm2 e 78, respectivamente). Compósitos com fração volumétrica de 0,10 e 0,50 apresentaram coeficiente piezoelétrico d33 igual a 15,5 e ~0 pC/N respectivamente. P(VDF-TrFE)/BT demonstraram melhor biocompatibilidade in vitro... / In this work, a systematic study on synthesis of poly(vinylidene fluoride-trifluoroethylene)/barium titanate - P(VDF-TrFE)/BT - composites for used in Guided Tissue Regeneration (GTR) was carried out. This osteopromotive technique has been widely employed on periodontal treatment. GTR utilizes a physical barrier (membrane) to promote bone-forming cell to migrate into secluded space. Hereby, these cells are able to regenerate the osseous defect, by the exclusion of competing non-osteogenic soft tissue cells on reabsorption. The osteogenic process also can be enhanced by application of electrical energy (direct current or pulsed electromagnetic field). Thereby, membranes of polymer-ceramic piezoelectric composites can promote the osteogenesis by means of electrics potentials produced and to provide mechanical protection to the secluded space. This kind of membrane can be considered an alternative barrier to GTR. In this way, the structural and electrical properties of P(VDF-TrFE)/BT composites were evaluated, as well as, their in vitro biocompatibility. The composites were prepared by mixing Barium Titanate powders and P(VDF-TrFE) (VDF=80mol%) on dimethylformamide medium (DMF). Composites membranes were made by following methods: solvent casting (SC), spincoating (SP), and precipitation on water followed by hot pressing (WHP). Composites obtained by WHP showed heterogeneous microstructure and adequate surfaces. The composite of ceramic fraction of 0.55 presented the best values of remanent polarization and relative dielectric constant (33.1mC/cm2 and 78, respectively). The piezoelectric coefficient d33 was 15,5 and ~0 pC/N for composites with volumetric fraction of 0.10 and 0.50 respectively. P(VDF-TrFE)/BT presented better in vitro biocompatibility when compared to commercial e-PTFE GTR barrier. Therefore, P(VDF-TrFE)/BT membrane developed could be an alternative to be used in GTR.

RESUMO A tensão de contração desenvolvida durante a polimerização de um compósito aderido às paredes do preparo cavitário pode comprometer a integridade da interface dente/restauração. O objetivo deste trabalho foi verificar a relação entre a tensão de contração e o grau de conversão em compósitos híbridos (Z250 e Tetric Ceram) e microparticulados (A110 e Heliomolar). Para o teste de tensão de contração foram utilizados bastões de vidro de silicato de boro (Pyrex), com 5 mm de diâmetro e 5 cm de altura. Os bastões foram presos às garras de uma máquina de ensaios (modelo 5565, Instron, Canton, MA, EUA) e o compósito foi aplicado às superfícies planas do vidro, as quais passararam por jateamento com óxido de alumínio (250 mm), seguido de silanização e aplicação de adesivo. A distância entre as superfícies dos vidros foi ajustada em 2 mm (Fator C=1,25). O grau de conversão (GC) foi determinado através de espectroscopia fotoacústica no infravermelho (PAS-IR) utilizando-se as razões entre as bandas correspondentes às duplas ligações carbônicas alifáticas (1640 cm -1 ) e aromáticas (1610 cm -1 ). Para cada compósito, tanto no teste de tensão como na análise do grau de conversão, foram constituídos cinco grupos variando-se o tempo de irradiação, a fim de se obter diferentes níveis de densidade de energia (4,8; 13,5; 27,0; 54,0 e 108,0 J/cm 2 ). Foram registrados os valores de tensão máxima e de grau de conversão observados no período de 10 minutos, contados a partir do início da fotoativação. A análise de dados foi feita através de ANOVA de fator duplo e teste de Tukey (a=0,05). Para os valores de tensão de contração, a interação compósito x densidade de energia foi significante. Os valores de tensão de contração para o compósito A110 variaram entre 1,2 e 7,0 MPa, para o Heliomolar entre 0,6 e 6,6 MPa, para o compósito Tetric Ceram entre 1,3 e 8,1 MPa e para o Z250 entre 2,0 e 6,6 MPa. Em geral, valores de tensão maiores foram observados nos níveis de densidade de energia mais elevados. Para o compósito A110 4,8<13,5<27,0<54,0=108,0 J/cm 2 . Para o compósito Heliomolar todos os níveis foram diferentes exceto entre 27,0 e 54,0 J/cm 2 . O compósito Tetric Ceram apresentou 4,8<13,5<27,0<54,0=108,0 J/cm 2 enquanto o compósito Z250 obteve 4,8=13,5<27,0=54,0<108,0 J/cm 2 . O GC foi influenciado pelo compósito (A110: 24% = Heliomolar: 28% = Z250: 32% < Tetric: 39%) e pela densidade de energia. As densidades de energia de 27,0 (33%); 54,0 (35%) e 108,0 (36%) J/cm 2 forneceram graus de conversão estatisticamente semelhantes, o mesmo ocorrendo entre 4,8 (23%) e 13,5 (26%) J/cm 2 e entre 13,5 e 27,0 J/cm 2 . Os resultados mostraram ainda que existe uma relação não-linear entre a tensão de contração e o grau de conversão de compósitos restauradores. Pode-se concluir que densidades de energia elevadas não necessariamente contribuem para um aumento significante no GC, mas podem acentuar o desenvolvimento de tensões de contração. / ABSTRACT The contraction stress developed during polymerization of composites bonded to cavity walls cavity is often associated with marginal gaps and interfacial failure. The aim of this study was to verify the relationship between contraction stress and degree of conversion (DC) in four composites (Z250, A110 – 3M ESPE; Tetric Ceram, Heliomolar – Vivadent). For the contraction stress test, composite (2 mm thick) was bonded between sandblasted and silane-treated glass stubs (Pirex: 5 mm diameter), mounted in a testing machine (model 5565, Instron, Canton, MA, EUA) equipped with a tensilometer to monitor the distance between the rods (C-factor=1.25). DC was determined by Infrared Photoacustic spectrometry (PAS-IR). The ratio between the aliphatic (1640 cm -1 ) and the aromatic (1610 cm -1 ) carbon double-bonds was used for calculating the DC. In both tests, each composite was light-cured for different times in order to provide different energy densities (4.8, 13.5, 27.0, 54.0, 108.0 J/cm 2 ). Maximum contraction stress and DC were measured 10 minutes after the beginning of polymerization. Results were analyzed by two-way ANOVA and Tukey’s test (a=0.05). For contraction stress, the interaction between composite and energy density was significant. Contraction stress values for A110 were between 1,2 and 7,0 MPa, Heliomolar between 0,6 and 6,6 MPa, Tetric Ceram between 1,3 and 8,1 Mpa and Z250 between 2,0 and 6,6 MPa. In general, contraction stress increases with higher energy density levels. For A110, 4.8<13.5<27.0<54.0=108.0 J/cm 2 . Heliomolar showed significant differences between all energy densities, except 27.0 and 54.0 J/cm 2 . Tetric was 4.8<13.5<27.0<54.0=108.0 J/cm 2 and Z250 showed 4.8=13.5<27.0=54.0<108.0 J/cm 2 . DC was influenced by composite (A110: 24%;Heliomolar: 28%, Z250: 32%; Tetric: 39%) and by energy density. The 27.0 (33%), 54.0 (35%) and 108.0 (36%) J/cm 2 energy densities showed similar DC, the same occurring with 4.8 (23%) and 13.5 (26%) J/cm 2 and between 13.5 and 27.0 J/cm 2 .The results showed a non-linear relationship between contraction stress and degree of conversion. It can be concluded that higher energy densities will not necessary contribute to increase DC, but may result in increased contraction stress development.