Incorporation of monoacetylferrocene to the sulfonated polystyrene ionomers imparted some changes in the properties of sulfonated polystyrene. Sulfonation was carried out by acetic anhydride and concentrated sulphuric acid. The sulfonation reaction and the degree of sulfonation were determined by analytical titration and adiabatic bomb calorimeter . For this purpose, sulfonated polystyrene (SPS) samples with varying percentages of sulfonation were prepared between 0.85% and 6.51%. Monoacetyl ferrocene was used in equivalent amount of sulfonation through addition procedure. FTIR Spectroscopy was one of the major techniques used to support the successful addition of AcFe to the SPS samples. Altering the sulfonation degree did not change the characteristic peak positions, but increased the peak intensities with increasing the degrees of sulfonation. Mechanical properties of resultant polymers were investigated. As a result, elastic modulus of polymers decreased by the amount of monoacetylferrocene. Thermal characteristic were found by Differential Scanning Calorimeter (DSC). Thermal analysis revealed that sulfonated polystyrene samples after addition of monoacetylferrocene displayed lower values of Tg. Microscopic analysis were made by Scanning Electron Microscopy (SEM) and single phase for each sample was observed. Besides, energy dispersed micro analysis showed an increase in the intensity of the iron (II) peaks that is related to the amount of monoacetylferrocene added to the SPS samples. Flame retardancy for each polymer was also examined and found that addition of monoacetylferrocene to sulfonated polystyrene does not change the Limiting Oxygen Index value (LOI)(17). However, LOI value for polystyrene is 18.

De nombreux gestes médicaux utilisent des aiguilles. Il est proposé une solution de principe pour contrôler la trajectoire d’une aiguille lors son insertion. Ce contrôle de trajectoire permet d’éviter des obstacles et atteindre une cible avec plus de précision. La solution de principe proposée repose sur l’utilisation des alliages à mémoires de forme de type Nickel-Titane (NiTi) et des traitements thermiques localisés. Une méthode expérimentale originale pour caractériser les alliages NiTi est développée. Cette méthode repose sur l’utilisation d’un dispositif expérimental permettant de faire des mesures et analyses mécaniques dynamiques (DMA) lors d’un essai de traction ou au cours d’un balayage en température sous contrainte. Ces mesures DMA ont permis de détecter les nombreux phénomènes présents dans ces alliages : élasticité, transformation de phase, réorientation,localisation, plasticité. Les résultats des mesures effectuées sur un fil commercial de NiTi sont présentés et analysés. L’analyse de l’évolution du module de conservation a permis de mettre en évidence les différentes séquences de transformation et de définir les domaines d’existence des phases en fonction de la contrainte et de la température. Des valeurs de modules d’élasticité de l’austénite, de la martensite et de la phase R sont proposées. Enfin,des modèles d’évolution du module de conservation lors d’un essai de traction et d’un balayage en température sous contrainte sont proposés. Une dernière partie concerne l’étude des effets des traitements thermiques sur un fil NiTi étiré à froid. Une gamme de traitements thermiques a été réalisée sur un fil NiTi. Les propriétés thermomécaniques ont été investiguées à la fois par des essais de traction isothermes et des mesures DMA en balayage en température sous contrainte. / Many medical procedures use needles. A solution is proposed to control and modifyneedle trajectory during its insertion. This steerable needle must be able to avoid anobstacle and reach the target with more accuracy. The solution uses Nickel Titanium(NiTi) shape memory alloy. A new experimental method is proposed to characterize NiTiwires. This method is based on experimental device wich allows to perform DynamicMechanical Analysis (DMA) during a tensile test or during a temperature sweep understress. DMA measurements can detect many phenomena : elasticity, phase transformation,reorientation, plasticity. Results for a commercial NiTi wire are presented and analyzed.Storage modulus evolution analysis shows multistage phase transformations for which thestress-temperature diagram has been established. Values of elastic modulus are determinedfor austenite, martensite and R phase. Estimation models are proposed to determinestorage modulus evolution during tensile test with DMA and temperature sweep understress with DMA. The last part of this work studies the effect of heat treatment on acold worked Niti wire. A range of heat treatments was performed. Thermomechanicaltreatment effects were investigated both with tensile tests and temperature sweeps understress with DMA.

Dans cette thèse, les propriétés rhéologiques du sang sont étudiées suivant deux approches differentes. Les propriétés de l'écoulement du plasma sont analysées selon trois modes différents : sous cisaillement, en extension et en constriction. Jusqu'à présent, le plasma était considéré comme un fluide newtonien, et le comportement complexe du sang était simplement attribué à la présence des globules rouges. Les expériences menées ont montré un comportement visco-élastique du plasma, que doit désomais être pris en compte dans les études futures. La deuxième axe traite des globules rouges. Leur assemblage en agrégats rectilignes est à l'origine du comportement rhéofluidifiant, mais les causes de la formation des agrégats restent encore vagues. L'énergie d'interaction entre deux cellules et la distribution des tailles des clusters dans des canaux microfluidiques ont été mesurées en présence de dextran et de fibrinogène. Comme les agrégats sont normalement cassés à des taux de cisaillement élevés, on a cru qu'ils ne jouaient pas de rôle dans l'écoulement du sang. Mais le fait que le nombre de clusters augmente à des concentrations physiologiques de fibrinogène, même pour des taux de cisaillement correspondant à ceux du système microvasculaire, il est clair que l'agrégation ne peut pas être négligée dans la description de l'écoulement du sang en le réseau capillaire. / In this work, the rheological properties of human blood are investigated by two different approaches. The flow properties of plasma, the liquid component of blood, is analyzed under three different conditions: shear flow, elongational flow and contraction flow. Up to now, the plasma was considered as a Newtonian fluid, while the non-Newtonian properties of blood were only attributed to the red blood cells. The performed experiments reveal a viscoelastic behavior of the plasma which has to be considered in future studies. In addition to the plasma, also diluted polymer solutions are analyzed in order to find a good model solution for plasma. The second part concerns the red blood cells. Their adhesion to linear aggregates is held responsible for the well-known shear thinning behavior of blood but the reason for the cluster formation is still not clear. The interaction energy between two red blood cells and the distribution of different sized clusters flowing through narrow channels are measured under the influence of the two macromolecules dextran and fibrinogen. As the aggregates are actually broken at high shear rates, the current understanding is that they would not play a role for the properties of blood flow. However, an increased amount of clusters at physiological fibrinogen concentrations can be shown, even at shear rates which are common in the microvascular system, which clarifies that the aggregation cannot be neglected in the description of blood flow through the capillary network.

Made available in DSpace on 2016-06-02T20:15:30Z (GMT). No. of bitstreams: 1 5592.pdf: 31266949 bytes, checksum: 2b640b435377cc433450c874294869e3 (MD5) Previous issue date: 2013-11-14 / Financiadora de Estudos e Projetos / In recent decades the study of β-Titanium alloys are attracting the interest to the biomaterials science community in general, since have improved properties as compared with current commercial biomedical alloys which present problems of both mechanical and chemical compatibility. In this sense, the determination and optimization of the mechanical properties, in particular of the elastic modulus, through of control the phases present that are of great importance. In this study was determined the dynamic elastic modulus (E), their relative variation ( ΔE/E) and internal friction (Q-1) as function of temperature by mechanical spectroscopy technique, being that the information provided by these parameters, associated with complementary characterization techniques and theoretical parameters of the literature provided relevant information on the phases stability in some alloys of the Ti-Nb-Zr and Ti- Nb-systems. Thus, complex anelastic relaxation processes were observed which through cyclic heat treatment and aging was possible to dissociate into their component of phase transformations, which highlighted in the temperature range between 300 K and 700 K the sequence β → β + ω → β + ω + α → β + α, and once these transformations are developed, in a joint manner are also present relaxation processes that include interactions of elements containing alloys with interstitial atoms. At low temperature (130 K-300 K), a process of relaxation was observed, which may be related to processes such as β → ω (athermic) transformation and/or H-O interactions. However by the behavior of the elastic modulus this process may be linked in part to the reverse martensitic transformation β→α" being possible to identify Ms and Af temperatures. In addition was characterized a low modulus of elasticity, yielding values between 67 and 54 GPa, which are related to the greater stability of the β phase, being these suitable values regarding the mechanical compatibility as compared with commercial alloys used as biomaterials. / Nas últimas décadas, o estudo de ligas de titânio do tipo β tem despertado o interesse da comunidade científica na área de biomateriais por apresentarem propriedades superiores se comparadas com as atuais ligas biomédicas comerciais, uma vez que, estas últimas apresentam problemas de compatibilidade tanto mecânica como química. Neste sentido, a determinação e otimização das propriedades mecânicas, principalmente através do controle das fases presentes são de grande importância, em especial objetivando obter o módulo de elasticidade próximo ao do osso humano (10-30 GPa). Assim, neste trabalho foram determinados, o módulo de elasticidade dinâmico (E), sua variação relativa (ΔE/E) e o atrito interno (Q-1) em função da temperatura, por meio da técnica de espectroscopia mecânica. A informação proporcionada por estas grandezas, associada a técnicas de caraterização complementares e a parâmetros teóricos da literatura, forneceram informações relevantes sobre a estabilidade das fases em algumas ligas de Ti-β dos sistemas Ti-Nb-Zr e Ti-Nb-Fe. Desta forma, processos de relaxação anelástica complexos foram observados, sendo que, através de tratamentos cíclicos e de envelhecimento foi possível dissociá-los em suas componentes de transformações de fase. Nestes espectros foi evidenciada, na faixa de temperatura entre 300 K e 700 K, a sequência de transformações β→β+ω→β+ω+α→β+α e, uma vez que, estas transformações se desenvolvem, de maneira conjunta, estão presentes processos de relaxação que incluem interações dos elementos que contém as ligas com átomos intersticiais. Em baixa temperatura (130 K a 300 K) foi observado um processo de relaxação, que pode estar relacionado a transformações β→ω (atérmica) e/ou interações H-O, no entanto, devido ao comportamento do módulo de elasticidade este processo pode estar associado em parte à transformação martensitíca reversa β→α , sendo possível identificar as temperaturas Ms e Af. Por outro lado, foi caracterizado um baixo módulo de elasticidade, obtendo-se valores entre 67 e 54 GPa, que estão relacionados com a maior estabilidade da fase β. Estes valores são adequados quanto a compatibilidade mecânica se comparados com as ligas comerciais empregadas como biomateriais.

Made available in DSpace on 2016-06-02T20:16:53Z (GMT). No. of bitstreams: 1 5978.pdf: 11727715 bytes, checksum: 7ecd56710aed6f64b6e687a355a259bf (MD5) Previous issue date: 2014-07-24 / Financiadora de Estudos e Projetos / The growing demand for increasingly resistant and biocompatible with the human body implantable materials, has led to an increase in demand for new metallic biomaterials. Some materials, such as titanium and its alloys, especially the Ti-6Al-4V, are widely used in the manufacture of orthopedic implants due to their excellent biocompatibility, high corrosion resistance and low density. However, the characteristics of these materials are not considered optimal, mainly because they have a high value of the elastic modulus when compared to the human bone. Include, that in the last decade studies have revealed diseases associated with elements such as Al and V, present in the alloy Ti-6Al-4V. Thus, it have looked for alternatives to the alloys used as biomaterials, still having one common element titanium, but having no toxic elements such as 𝛽 type titanium alloys, formed by non-toxic elements such as Nb, Ta, Zr, Mo and Sn has shown that lower values of modulus, greater fatigue resistance and corrosion resistance, exhibiting excellent biocompatibility. Accordingly, the alloys formed by Ti-Ta become promising candidates as biomaterials, since it has been observed that the content of Ta affects the value of the elastic modulus. For some compositions of this alloy, lower modulus values of this alloys that are currently used in biomedical applications were observed. However, the alloys formed by Ti-Ta still have properties that have been little studied. Thereby, the objectives of this master s project consist in getting the alloy Ti-40Ta and its characterization by means of the technique of mechanical spectroscopy, as of its elements that compose the alloy. The technique of mechanical spectroscopy to be non-destructive, it is widely used for providing the anelastic spectrum (oscillation frequency and internal friction as a function of temperature) is considered sensitive to phase transitions and dynamic processes, which are essential for understanding the structural changes occurring in these materials. This study was determined the dynamic elastic modulus for the pure Ti and Ta elements, and the Ti-40Ta through flexural vibrations. The elastic modulus found for the alloy at room temperature was (71 ± 5) GPa, which is in accordance with results available in the literature. The value of modulus of the alloy is lower when compared to the commercial biomedical alloys and is closer to that of human bone, which makes the alloy Ti-40Ta a potential candidate to be used in biomedical applications. / A crescente demanda por materiais implantáveis cada vez mais resistentes e biocompatíveis com o organismo humano, tem levado a um aumento na procura por novos biomateriais metálicos. Alguns materiais, como o titânio e suas ligas, com destaque para a liga Ti-6Al-4V, são largamente utilizados na fabricação de implantes ortopédicos devido as suas excelentes características como biocompatibilidade, alta resistência à corrosão e baixa densidade. Entretanto, as características desses materiais ainda não são consideradas ideais, principalmente porque apresentam um alto valor do módulo de elasticidade quando comparado com o osso humano. Cabe mencionar, que na última década estudos revelaram doenças associadas a elementos como o Al e V, presentes na liga Ti-6Al-4V. Desta forma, busca-se alternativas às ligas empregadas como biomateriais, ainda contendo como elemento principal o titânio, mas que não possuam elementos tóxicos. Estudos recentes mostram que as ligas de titânio tipo 𝛽, formadas por elementos não tóxicos como Nb, Ta, Zr, Mo e Sn, tem apresentado valores mais baixos módulo de elasticidade, maior resistência à fadiga e maior resistência à corrosão, além de exibir uma excelente biocompatibilidade. Neste sentido, as ligas formadas por Ti-Ta tornaram-se candidatas promissoras como biomateriais, uma vez que, foi observado que o teor de Ta afeta o valor do módulo de elasticidade. Para algumas composições, desta liga, foram observados valores de módulo inferiores as ligas de Ti que atualmente são empregadas em aplicações biomédicas. No entanto, as ligas formadas por Ti-Ta ainda possuem propriedades pouco estudadas. Deste modo, os objetivos deste projeto de mestrado consistem na obtenção da liga Ti-40Ta e na sua caracterização por meio da técnica de espectroscopia mecânica, bem como a de cada elemento que compõem a liga. A técnica de espectroscopia mecânica, por ser não destrutiva, é amplamente usada por fornecer o espectro anelástico (frequência de oscilação e atrito interno em função da temperatura), sendo considerada sensível a transições de fase e a processos dinâmicos, que são essenciais para compreender as alterações estruturais que ocorrem nestes materiais. Neste estudo, determinou-se o módulo de elasticidade dinâmico para os elementos puros, Ti e Ta, e para a liga Ti-40Ta por meio das vibrações flexurais. O módulo de elasticidade encontrado para a liga, em temperatura ambiente, foi de (71 ± 5) GPa, estando em concordância com os resultados disponíveis na literatura. O valor de módulo da liga é menor quando comparado ao das ligas biomédicas comerciais e está mais próximo a do osso humano, o que a torna a liga Ti-40Ta uma potencial candidata a ser empregada em aplicações biomédicas.

Avec l'intégration de circuits intégrés de plus en plus denses, le besoin d'outils de caractérisation adaptés à ces échelles se fait ressentir. Identifier et analyser les problèmes de fiabilité survenant dans ces structures à des dimensions inférieures à 100 nm demande la mise au point d'instruments innovants. Ce travail de thèse a consisté dans un premier temps à développer un appareil à champs proches sensible aux propriétés mécaniques de surface, et dans un second temps à analyser les résultats expérimentaux en s'appuyant sur des approches analytiques et/ou numériques. Désigné sous le nom de microscope à force atomique à résonance de contact (CR-AFM), cet appareil est sensible à la rigidité effective de films minces sur substrat, ce qui lui permet de cartographier la rigidité mécanique de films minces. Nous avons mené un important travail de développement instrumental afin d'obtenir des résultats expérimentaux répétables et fiables, condition indispensable à une analyse quantitative. Puis nous avons utilisé le CR-AFM sur divers échantillons : empilements modèles (films de silice sur silicium, avec épaisseurs variables de silice), films de silice avec porosité variable, structures damascènes d'interconnexion cuivre,… Des images traduisant les variations d'élasticité de surface ont ainsi pu être construites. Pour quantifier ces variations, nous avons analysé nos résultats à l'aide de différents modèles (approches analytiques et numériques). Des simulations par éléments finis ont été réalisées pour étayer ces résultats. / The reduction of feature size in integrated circuits has raised an increasing need for characterization tools displaying small-scale resolution. Reliability issues taking place in these structures with dimensions below 100 nm require the development of innovative instruments. This thesis has first focused on the development of near field apparatus displaying sensitivity to surface mechanical properties. Afterwards analytical and numerical modelings have been developed to analyze the obtained experimental data. Known as contact resonance atomic force microscope (CR-AFM), this apparatus is sensitive to the effective stiffness of thin film on substrate, allowing the mapping of the mechanical stiffness. A significant work on the apparatus setting-up and procedure has been done to obtain repeatable and reliable experimental data, which is a prerequisite for quantitative analysis. Then CR-AFM experiments have been done on various samples: model stacks (silica thin films on silicon with varying silica thickness), silica films with tuned porosity, Damascene copper interconnect structures,… The mapping of elastic stiffness of such samples has been built-up. In order to quantify these contrasts, our experimental results have been analyzed through different models (analytical and numerical). Finite element simulations were also performed to support these results.

Placas oclusais são dispositivos intraorais utilizados no manejo de pacientes que apresentam desordens do sono, migrânia do tipo tensional e outros. No entanto são os cirurgiões dentistas que predominantemente utilizam as placas oclusais como tratamento do equilíbrio das arcadas dentárias nas disfunções temporomandibulares, prevenção de desgaste dental em pacientes com hábitos parafuncionais e na prevenção de traumas em atletas. Vários métodos têm sido empregados para reforçar resinas acrílicas, como reforço metálico e atualmente a incorporação de diferentes tipos de fibras tais como: carbono, polietileno e vidro. Contudo a adição de fibras de vidro com partículas menores em algumas propriedades mecânicas ainda permanecem desconhecidas. Objetivo: O objetivo desse estudo foi avaliar algumas propriedades mecânicas como a rugosidade de superfície, microdureza, módulo de elasticidade e resistência flexural em resinas acrílicas após a incorporação de fibras de vidro particuladas pré silanizadas. Material e método: Para avaliação das propriedades foram confeccionados vinte e quatro corpos de prova (65 x 10 x 3 mm) de cada marca comercial de resina acrílica, utilizadas para confecção de placas oclusais, Vipi Flash (autopolimerizável), Vipi Wave (termopolimerizável por calor de microondas), Vipi Crill, Lucitone e QC-20 (termopolimerizáveis por calor de banho de água), sendo doze corpos-de-prova controles, e doze experimentais, com adição de 10% em peso de fibras de vidro particuladas (Reforplás S/A, São Paulo, SP, Brasil). Após a realização do acabamento superficial dos corpos de prova com lixas de carborundum e feltros era realizada a avaliação da rugosidade superficial em rugosímetro (Mitutoyo®) com três leituras ao longo dos corpos-de-prova, a microdureza Vickers era analisada em um microdurômetro (Micro Hardness Tester, Shimadzu, Japan) com cinco mensurações em cada corpo-de-prova, e para avaliar os ensaios de resistência flexural e módulo de elasticidade os corpos-de-prova foram avaliados por meio uma máquina de ensaios universal (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), com velocidade de 5mm/min. Os dados foram analisados estatisticamente, usando testes paramétricos e não paramétricos, de acordo com a distribuição da amostra. Resultados: As médias e desvios padrões do teste de rugosidade superficial em Ra foram Vipi Flash sem fibra (0,10 ± 0,03); Vipi Flash com fibra (0,12 ± 0,01); Vipi Wave sem fibra (0,16 ± 0,02); Vipi Wave com fibra (0,13 ± 0,02); Vipi Cril sem fibra (0,12 ± 0,03); Vipi Crill com fibra (0,15 ± 0,03); Lucitone sem fibra (0,10 ± 0,02); Lucitone com fibra (0,09 ± 0,04); QC-20 sem fibra (0,11 ± 0,02) e QC-20 com fibra (0,18 ± 0,03). As médias e desvios-padrão ao teste de microdureza Knoop com relação às marcas comerciais foram: Vipi Flash sem fibra (15,35 ± 0,3); Vipi Flash com fibra (15,51 ± 0,4); Vipi Wave sem fibra (16,60 ± 0,8); Vipi Wave com fibra (17,25 ± 0,9); Vipi Cril sem fibra (17,78 ± 2,27); Vipi Crill com fibra (18,02 ± 1,0); Lucitone sem fibra (15,72 ± 0,3); Lucitone com fibra (16,69 ± 0,6); QC-20 sem fibra (15,91 ± 0,4) e QC-20 com fibra (15,63 ± 0,2). As médias e desvios-padrão ao teste de módulo de elasticidade foram: Vipi Flash sem fibra (2952,76 ± 292,12); Vipi Flash com fibra (3373,49 ± 403,76); Vipi Wave sem fibra (2511,69 ± 304,09); Vipi Wave com fibra (3225,01 ± 248,66); Vipi Cril sem fibra (2745,61± 288,86); Vipi Crill com fibra (3671,67 ± 329,91); Lucitone sem fibra (1904,53 ± 149,05); Lucitone com fibra (3056,87 ± 126,11); QC-20 sem fibra (1913,86 ± 147,80) e QC-20 com fibra (2858,32 ± 185,26). As médias e desvios-padrão ao teste de resistência flexural foram Vipi Flash sem fibra (81,62 ± 4,82); Vipi Flash com fibra (83,98 ± 4,98); Vipi Wave sem fibra (83,52 ± 8,79); Vipi Wave com fibra (88,98± 8,47); Vipi Cril sem fibra (64,17± 5,46); Vipi Crill com fibra (93,37 ± 9,97); Lucitone sem fibra (74,71± 9,43); Lucitone com fibra (87,29 ± 4,73); QC-20 sem fibra (75,80 ± 8,82) e QC-20 com fibra (81,67± 12,97). Conclusão: Conclui-se que a incorporação de fibras provocou alterações em praticamente todas as propriedades analisadas, sendo, portanto facilmente utilizável como um reforço adicional às resinas acrílicas. Com relação à dureza superficial as resinas acrílicas termopolimerizável por banho de água e termopolimerizável por calor de microondas apresentaram maiores valores quando comparados com a resina acrílica autopolimerizável. Além disso, a adição de fibras de vidro particuladas aumentou os valores de rugosidade de algumas resinas acrílicas Vipi Crill, Vipi Flash e Vipi Wave e se manteve constante nas resinas Lucitone e QC-20. A adição de fibra de vidro não aumentou significantemente a microdureza Knoop nos grupos em estudo. Com relação à resistência flexural as fibras de vidro particuladas aumentaram significantemente todos os valores, assim como o módulo de elasticidade das resinas acrílicas reforçadas pela adição de fibras de vidro. / Intraoral Occlusal splints are devices used in the management of patients with sleep disorders, migraine type tension and others. But dentists who are predominantly using the plates as a treatment of occlusal balance of the dental arches in temporomandibular disorders, prevention of tooth wear in patients with habits and prevention of injuries in athletes. Several methods have been used to strengthen acrylic resins, such as metal reinforcement and are currently incorporating different types of fibers such as carbon, polyethylene and glass. However the addition of glass fibers with smaller particles on mechanical properties are still unknown. Objective: The objective of this study was to evaluate some mechanical properties such as surface roughness, hardness, elastic modulus and flexural strength in acrylic resins after the incorporation of glass fiber particulate pre silanized. Methods: To evaluate the properties were made twenty-four specimens (65 x 10 x 3 mm) of each brand of acrylic resin, used for fabrication of occlusal splints, Vipi Flash (self-curing), Vipi Wave (by thermo microwave heat), Vipi CRILL, Lucitone and QC-20 (thermo heat water bath), with twelve specimes controls, and twelve experimental, with the addition of 10 wt% glass fiber particulate (Reforplás S / A, São Paulo, Brazil). After completion of the roughness of the specimens with grit carborundum and felt it was evaluated the surface roughness on roughness tester (Mitutoyo ®) with three readings over the specimes, the microhardness was examined with a hardness ( Micro Hardness Tester, Shimadzu, Japan) with five measurements in each specime, and evaluate the tests for flexural strength and modulus of elasticity of the specimes was evaluated using a universal testing machine (Emic DL 2000 ®, Emic, São José dos Pinhais, PR, Brazil), with speed 5mm/min. The data were statistically analyzed using parametric and nonparametric tests, according to the sample distribution. Results: The mean and standard deviation of the test surface roughness were Vipi Flash without fiber (0.10 ± 0.03); Flash Vipi with fiber (0.12 ± 0.01); Vipi Wave without fiber (0, 16 ± 0.02); Vipi Wave with fiber (0.13 ± 0.02); Vipi Cril without fiber (0.12 ± 0.03); Vipi CRILL with fiber (0.15 ± 0.03); Lucitone without fiber (0.10 ± 0.02); Lucitone with fiber (0.09 ± 0.04), QC-20 fiber without (0.11 ± 0.02) and QC-20 with fiber (0.18 ± 0.03). Means and standard deviations for Knoop microhardness test with respect to trademarks were Vipi Flash without fiber (15.35 ± 0.3); Flash Vipi with fiber (15.51 ± 0.4); Vipi Wave without fiber (16.60 ± 0.8); Vipi Wave with fiber (17.25 ± 0.9); Vipi Cril without fiber (17.78 ± 2.27); Vipi CRILL with fiber (18.02 ± 1.0 ); Lucitone without fiber (15.72 ± 0.3); Lucitone with fiber (16.69 ± 0.6), QC-20 without fiber (15.91 ± 0.4) and QC-20 with fiber (15 , 63 ± 0.2). Means and standard deviations to test elastic modulus were Vipi Flash without fiber (2952.76 ± 292.12); Flash Vipi with fiber (3373.49 ± 403.76); Vipi Wave without fiber (2511.69 ± 304.09); Vipi Wave with fiber (3225.01 ± 248.66); Vipi Cril without fiber (2745.61 ± 288.86); Vipi CRILL with fiber (3671.67 ± 329.91); Lucitone without fiber (1904.53 ± 149.05); Lucitone with fiber (3056.87 ± 126.11), QC-20 without fiber (1913.86 ± 147.80) and QC-20 with fiber (2858.32 ± 185 26). Means and standard deviations for flexural strength were Vipi Flash without fiber (81.62 ± 4.82); Flash Vipi with fiber (83.98 ± 4.98); Vipi Wave without fiber (83.52 ± 8 , 79); Vipi Wave with fiber (88.98 ± 8.47); Vipi Cril without fiber (64.17 ± 5.46); Vipi CRILL with fiber (93.37 ± 9.97); Lucitone without fiber ( 74.71 ± 9.43); Lucitone with fiber (87.29 ± 4.73), QC-20 without fiber (75.80 ± 8.82) and QC-20 with fiber (81.67 ± 12.97). Conclusion: the conclusion is that the incorporation of fibers resulted in changes in almost all properties examined, and thus easily used as an additional reinforcement for acrylic resins. With respect to the surface roughness of acrylic resins by thermo water bath and microwave thermo heat showed higher values when compared with acrylic resin. Moreover, the addition of glass fiber particulate increased the roughness values of some acrylic resins Vipi CRILL, Vipi Flash and Vipi Wave and remained constant in the resins Lucitone and QC-20. The addition of glass fiber does not increase significantly the microhardness in the groups. With respect to flexural strength glass fiber particulate significantly increased all values, as well as the modulus of acrylic resin reinforced by the addition of glass fibers.

When loss of material due to sliding of two solids is promoted/prevented, in the presence of chemically reacting liquid or gas, tribochemical wear is said to occur. Tribochemical wear, in which corrosive media promotes material loss, is a serious concern in a variety of applications like machining, bio-implants, gas turbine engines etc. The most pervasive corrosive media encountered in applications are water and air. Air also contains water vapour along with oxygen, both of which adsorb and react with most materials, thus influencing their wear behaviour. The need for higher operating temperatures and compression ratios in gas turbine engines require development of high temperature wear resistant coatings to protect their soft metallic components. Ti based nitride coatings with Ti, Al, Si, Cr, Ta, Nb, V are known for wear resistance because of their high hardness which is second only to diamond and c-BN. High O affinity of these elements, induce the coatings to form passive oxide scale up to reasonably high temperatures and offer superior corrosion and oxidation resistance. However, sliding can remove the passivating layer, exposing the native surface to the environment which can lead to enhanced tribochemical wear. Oxidation resistance under static conditions does not guarantee low tribochemical wear; however, the tribochemical reactions causing the corrosion are of interest. Another concern is that sliding in unison with high temperatures can activate processes like enhanced diffusion, phase transformations in nitride coatings as well as in the substrate. Hence one of our objectives is to perform wear tests at high temperatures to understand the dominant mechanisms that affect wear in nitride coatings. Wear tests in the range of room temperature up to the oxidation limit of these coatings are designed.In this study TiN and high aluminium containing TiAlN coatings are chosen to study understand the wear behaviour as function of temperature up to 800°C [1]–[3]. In order to study wear of coatings, it is necessary to identify the best possible materials and methods. Though under the targeted application the coatings have to perform under fretting tests, pin on disk configuration is used which simplifies the analysis and gives deeper insight into the wear mechanism. Coated ball is used as the pin which is stationary unlike many earlier studies where the coating is applied on the rotating disk. The purpose of keeping the pin stationary is to minimize the counter-face wear and, instead, accelerate wear in these hard coatings. This method also enables easy and accurate measurement of wear depth and volume by using an optical microscope, while the conventional coated disk method requires profilometry and statistically sound measurements. To enable coating performance, substrate should not undergo much loss of strength before 800°C and hence aerospace grade IN718 alloy is chosen as the substrate which softens slowly beyond 650°C. Alumina is used as counter-face, since it has high hardness, excellent mechanical, chemical and thermal stability. In the current study, TiAlN coating is tested for wear in the range of room temperature to 800°C. Figure 1 represents the data obtained from the wear experiments. It is found that the wear is higher with large scatter at room temperature while it remains constant from 200- 750°C. Two important observations are made, firstly that the TiAlN is susceptible to some kind of a corrosive wear at room temperature which depended on the timing of the tests and secondly that the coating shows a surprisingly constant wear behaviour over the temperature range of 200-750°C. The scatter at room temperature is found to be linked with seasonal fluctuation of humidity which is verified by performing tests under controlled humidity conditions. Water vapour and oxygen are potential reacting gases present in air. Oxidation and oxidative wear is known to occur in many materials as temperatures increase which seem to be linked to thermal activation of oxidation. However lower wear at 200°C and above compared to room temperatures suggests something else to be happening .It is evident then that between room temperature and 200°C lies a transition of some kind in the tribochemical reaction which is responsible for the observed wear behaviour of TiAlN. A detailed study to understand this transition is then undertaken for the composition of TiN coatings so that benchmarking and comparison with TiAlN is possible. Also if the wear behaviour of TiN is found similar to TiAlN then it would indicate a general phenomenon which can be extended to Ti based nitrides. Figure 1 Wear rate as a variation of temperature for TiAlN coatings In contrast to low temperature wear behaviour of TiAlN, a constant wear in the range of 200-750°C is surprising because the primary suspect which is oxidation is thermally activated. The oxide scale though expected to be thin at low temperatures, has to increase in thickness with temperature due to increased diffusion and reaction rates. The oxide scale also undergoes a change in morphology and composition which indicate a lower oxidation resistance as temperature increases. A preliminary characterization of the wear scar on the ball shows that the oxide inside the worn region is thinner than the oxide outside at 750°C. The amount of O within the wear scar is similar to levels observed on as deposited surface while the surface outside the wear scar shows oxidation and discolouration. The results suggest that oxidation inside worn region at high temperatures might be slower than the expected parabolic oxidation occurring outside the wear region. It is speculated that a double layer oxide is formed with TiO2 towards the surface and Al2O3 towards the nitride which is responsible for the lower wear at high temperature. This is supported by the fact that larger amount of Ti is found in the wear debris as temperature inceases. Superficial surface cracks appear at higher loads at temperatures as low as 600°C but they affect wear only above 800°C due to substrate softening. This shows that the coatings are still limited by the substrate softening temperature and could be used at higher temperatures. Tribo-reaction in metals, nitrides and carbides can be brought about in the presence of O2 or water vapour. Tribochemical wear of SiN, SiC, TiN, TiAlN, alumina and most other ceramics at room temperature are found to depend on humidity[4]–[6]. But only tribo-oxidation due to O2 is found to operate at high temperatures[7], [8]. Notwithstanding, it is known that SiC and SiN are more resistant to attack from O2 above 800°C than from steam. Hence the role played by water vapour is found to be convoluted. Moreover, relative humidity is the frequently mentioned quantity with regard tribochemical wear at room temperatures. It should be noted that relative humidity is not a measure of chemical activity of water vapour. Rather the water vapour pressure which represents the chemical activity of water, is not given much importance in the earlier studies. In this study, the importance of humidity, water vapour pressure and temperature in influencing wear, is studied by performing controlled wear tests on TiN. To explore the effect of temperature and water vapour pressure, TiN is tested varying temperature range of 28 °C to 90°C and water vapour pressure in the range of 3-35 mm-of-Hg. Wear tests are conducted keeping temperature constant with varying water vapour pressure and vice versa. The results show that, wear increased with humidity/vapour pressure at a fixed temperature but wear dropped drastically with increase in temperature at constant vapour pressure up to a critical temperature beyond which wear remained constant. This is one of the major unexpected findings since temperature is expected to increase wear volume. Also the critical temperature is found to shift to higher temperatures as water vapour pressures increased. It was suspected that capillary condensation was playing a role in the wear which was later verified. The whole wear behaviour is shown to be correlated with the amount of capillary condensed water. The large radius of curvature of the asperities on the polished coating surface and the smooth surface formed on the counter-face due to debris compaction form conditions favourable for capillary condensation. Any two hydrophilic surfaces which come in contact can form capillary condensation to occur at the cusps formed around the contact. However a threshold pore size of about 1nm existed below which condensation did not influence wear. Another observation is that the water vapour did not affect wear significantly in the absence of condensation for TiN coatings. As temperatures increased condensation became unfavourable, but the high vapour pressure present showed no signs of wear enhancement. This is surprising and unexpected compared to earlier reports.[9], [10] On contrary tests in liquid water showed expected behaviour for tribochemical reaction i.e wear increased with temperature. The wear in liquid water is highest when compared studies in air at any given temperature. The X-ray electron emission spectroscopy (XPS) analysis is performed to understand the surface reactions. It appears that O2 forms a barrier oxide which protects the nitride from reacting with water vapour. However when condensation occurs or in water, the oxygen and water collude into forming softer hydroxide layer which is easily removed. Though chemically water and water vapour are same, they affect wear in TiN very differently. Summarising the synopsis, exploration into high temperature wear of TiAlN reveals that it can handle oxidative wear upto 750°C showing constant wear over the temperature range of 200-750°C. Reduction in residual stresses and substrate softening may be responsible for higher wear at higher loads since the cracking is observed at 5N is absent at 3N. The substrate is expected to soften above 650°C but this does not necessarily affect wear until the load is increased or the temperature is sufficiently high. However TiAlN and TiN coatings showed susceptibility to tribo-corrosion in water and high humidity at room temperature. At high humidity, condensation of water leads to increase in wear. The dependence of wear on humidity is found to be because of capillary condensation. The negligible dependence of wear on humidity in the absence of condensation is ascribed to formation of oxide layer due to reaction with O2 and coating. The oxide barrier formed due to atmospheric O2 protects the coating from reacting with the water vapour. The oxide barrier on TiN forms faster indicating O2 reaction to be faster than the reaction with water vapour. In the presence of capillary condensation or water, O2 is depleted from contacting surfaces thus hindering the formation of the barrier oxide, increasing wear. As temperature increases the condensation becomes unfavourable and barrier oxide dominates the wear mechanism upto high temperatures which is dominated by oxidative wear.

A contração de polimerização das resinas compostas é uma característica indesejável que compromete a integridade da interface dente/restauração. O objetivo deste estudo foi avaliar in vitro a influência de diferentes materiais usados em restaurações classe II de resina composta, quanto ao grau de conversão, tensão de contração, resistência a flexão, módulo de elasticidade e formação de fenda marginal. Foram realizados preparos classe II com dimensões de 4x4x2mm em terceiros molares recém-extraídos para a avaliação da formação de fenda marginal. As cavidades foram niveladas com cimento de ionômero de vidro Riva Light Cure (SDI) (CIV), resina de baixa contração SureFilSDR (Dentsply) (SDR), resina flow FiltekZ350Flow (3M/ESPE) (Z350F) e resina composta FiltekP90 (3M/ESPE) (P90). As restaurações (n=3) foram avaliadas com lupa estereoscópica. A resistência a flexão foi avaliada por meio de ensaio de flexão em três pontos. Para este ensaio foram confeccionados dez corpos de prova (n=10) de cada material com dimensões de 10x2x1mm. Para o teste de tensão de contração foram utilizados cilindros de polimetacrilato com 5 mm de diâmetro e 13 ou 28mm de comprimento. Os bastões foram fixados na EMIC com um espaço de 2mm entre eles, onde os materiais foram inseridos. Foram realizadas cinco repetições para cada grupo (n=5) e a tensão proveniente da contração foi medida por até 10 minutos após o início da fotopolimerização. O Grau de Conversão (GC) foi determinado por espectroscopia no infravermelho com transformada de Fourier (FTIR). Os resultados foram tratados estatisticamente por análise de variância (ANOVA) e Teste de Tukey (p<0,05). Fenda marginal: Z350F = CIV > SDR = P90. Tensão de contração: Z350F > SDR > CIV = P90. Resistência a flexão: P90 > SDR = Z350F > CIV. Módulo de Elasticidade: P90 > CIV = SDR = Z350F. GC: Z350F = SDR > P90 > CIV. Conclusões: existe correlação entre a formação de fenda marginal e as propriedades físico químicas dos materiais testados, sendo as resinas de baixa contração que proporcionaram melhor adaptação marginal; existe correlação entre resistência a flexão, módulo de elasticidade, tensão de contração e a composição dos materiais, já que os compósitos com melhores resultados foram os que apresentaram os maiores percentuais de carga, no entanto, maior grau de conversão não representou melhores propriedades mecânicas. / The shrinkage of composite resin polymerization is an undesirable characteristic that compromises the integrity of the tooth / restoration interface. The aim of this study was to evaluate in vitro the influence of different materials used in composite resin class II restorations in terms of contraction stress, flexural strength, degree of conversion and marginal gap formation. Class II preparation were performed with 4x4x2mm dimensions in third molars freshly extracted for the evaliation of marginal gap formation. The cavities were filled with Riva Light Cure (SDI) glass ionomer cement (CIV), SureFil SDR (Dentsply) low shrinkage resin (SDR), Filtek Z350Flow (3M/ESPE) flowable composite (Z350F) and Filtek P90 (3M/ESPE) composite resin (P90). The restorations (n = 3) were evaluated with magnifying stereoscopic. The flexural strength was assessed by means of three point bending test. For this test ten specimens (n = 10) of each material were made, each with 10x2x1mm dimensions. For the shrinkage stress test polymethacrylate cylinders with 5 mm in diameter and 13 or 28mm in length were used. Bats were attached to the EMIC with a 2mm space between them, where the materials were inserted. The test were repeated five times for each group (n = 5) and the contraction stress was measured for up to 10 minutes after initiation of photopolymerization. The Degree of Conversion (DC) was determined by Fourier transform infrared (FTIR). The results were statistically analyzed by the variance analysis (ANOVA) and Tukey test (p <0.05). Marginal gap: Z350F = CIV > SDR = P90. Contraction stress: Z350F > SDR> CIV = P90. Flexural strength: P90 > SDR = Z350F > CIV. Elasticity Modulus: P90 > CIV = SDR = Z350F. DC: Z350F = SDR > P90 > CIV. Conclusion: There is a correlation between formation of marginal gap and physicochemical properties of the materials tested whereas low shrinkage resins provided better marginal adaptation; correlation exists between flexural strength, elastic modulus, shrinkage stress and material composition, since better results were obtained from composites with larger quantity of load; higher conversion degree did not represent better mechanical properties.

Este trabalho apresenta dois tipos de ensaios não destrutivos para a correlação do módulo dinâmico com a resistência à compressão para elementos de concreto. Os métodos de ensaio são a ultrassonografia e o método de excitação por impulso utilizando o equipamento Sonelastic®. Neste trabalho estão descritos seus funcionamentos, aplicações e limitações. A ultrassonografia, através da propagação de ondas sonoras, fornece, indiretamente, o módulo de elasticidade dinâmico. Com o método de excitação por impulso obtêm-se as frequências naturais e os modos de vibração do elemento estudado, o que permite determinar seu módulo dinâmico. Primeiramente, estes ensaios foram utilizados em corpos-de-prova cilíndricos e lajes alveolares produzidas em laboratório para a obtenção das curvas de correlação e, em seguida, estes mesmos ensaios foram realizados na fábrica de concreto pré-moldado. Para elementos de geometria complexa, como é o caso das lajes alveolares, apresenta-se uma metodologia para a obtenção de uma equação analítica para o cálculo do módulo dinâmico no ensaio de excitação por impulso. Estes métodos tiveram o objetivo final de avaliar a resistência à compressão do concreto na pista de protensão da fábrica, e então determinar o melhor momento para a desforma e corte do cabo de protensão. Com ambos os métodos, obteve-se ótimas correlações do módulo dinâmico com a resistência à compressão dos elementos em laboratório. Na fábrica de concreto pré-moldado não foi possível obter uma curva de correlação representativa de toda a laje na pista de protensão, porém foi possível registrar um bom indicativo de que é possível obter boas correlações para futuras pesquisas no assunto / This work presents two types of non-destructive testing for the correlation of the dynamic elastic modulus with the compressive strength. The test methods are the ultrasonography and the impulse excitation using the Sonelastic® equipment. In this work the equipaments operations, applications and limitations are also described. The ultrasound test indirectly supplies the dynamic elastic modulus through the propagation of sound waves. The natural frequencies and the vibration modes of the studied elements are obtained through impulse excitation method allowing to determine its dynamic modulus. To start, these tests were used in cylindrical specimens and hollow core slabs produced in the laboratory to obtain the correlation curves, and then these same methods were performed in the pre-cast concrete plant. As for complex geometric elements, as in the case of hollow core slabs, a methodology is applied in order to obtain an analytic equation to calculate the dynamic modulus in the impulse excitation test. These methods had the final goal the evaluation of the strength of prestressed concrete lying on track of the plant, so as to determine the best moment to demold and cut the prestressed cable. Excellent correlations of the dynamic modulus with compressive strength of the elements made in laboratory were obtained using both methods. It was not possible to obtain in the precast concrete plant a representative correlation curve of the whole slab on the track, nevertheless, it was possible to record a good indication that it is possible to obtain good correlations for future research.