Calcium phosphate cements (CPCs) are used as bone void fillers and as complements to hardware in fracture fixation. The aim of this thesis was to investigate the possibilities and limitations of the CPCs’ mechanical properties, and find out if these ceramic bone cements can carry application-specific loads, alone or as part of a construct. Recently developed experimental brushite and apatite cements were found to have a significantly higher strength in compression, tension and flexion compared to the commercially available CPCs chronOS™ Inject and Norian® SRS®. By using a high-resolution measurement technique the elastic moduli of the CPCs were determined and found to be at least twice as high compared to earlier measurements, and closer to cortical bone than trabecular bone. Using the same method, Poisson's ratio for pure CPCs was determined for the first time. A non-destructive porosity measurement method for wet brushite cements was developed, and subsequently used to study the porosity increase during in vitro degradation. The compressive strength of the experimental brushite cement was still higher than that of trabecular bone after 25 weeks of degradation, showing that the cement can carry high loads over a time span sufficiently long for a fracture to heal. This thesis also presents the first ever fatigue results for acidic CPCs, and confirms the importance of testing the materials under cyclic loading as the cements may fail at stress levels much lower than the material’s quasi-static compressive strength. A decrease in fatigue life was found for brushite cements containing higher amounts of monetite. Increasing porosity and testing in a physiological buffer solution (PBS), rather than air, also decreased the fatigue life. However, the experimental brushite cement had a high probability of surviving loads found in the spine when tested in PBS, which has previously never been accomplished for acidic CPCs. In conclusion, available brushite cements may be able to carry the load alone in scenarios where the cortical shell is intact, the loading is mainly compressive, and the expected maximum stress is below 10 MPa. Under such circumstances this CPC may be the preferred choice over less biocompatible and non-degradable materials.

Uma grande diversidade de macrofibras poliméricas para reforço de concreto se encontram disponibilizadas hoje em dia. Por natureza estas fibras apresentam grande diversidade de características e propriedades. Estas variações afetam sua atuação como reforço no concreto. No entanto, não há normas brasileiras sobre o assunto e as metodologias de caracterização de normas estrangeiras apresentam divergências. Algumas normas definem que a caracterização do comportamento mecânico deva ser feita nos fios originais e outras que se devam utilizar métodos definidos para caracterização de materiais metálicos. A norma EN14889-2:2006 apresenta maior abrangência, mas deixa dúvidas quanto à adequação dos critérios de caracterização geométrica das fibras e não define um método de ensaio específico para sua caracterização mecânica. Assim, há a necessidade de estabelecimento de uma metodologia que permita a realização de um programa de controle de qualidade da fibra nas condições de emprego. Esta metodologia também proporcionaria uma forma de caracterização do material para estudos experimentais, o que permitiria maior fundamentação científica desses trabalhos que, frequentemente, fundamentam-se apenas em dados dos fabricantes. Assim, foi desenvolvido um estudo experimental focando a caracterização de duas macrofibras poliméricas disponíveis no mercado brasileiro. Focou-se o estudo na determinação dos parâmetros geométricos e na caracterização mecânica através da determinação da resistência à tração e avaliação do módulo de elasticidade. Na caracterização geométrica foi adotada como referência a norma europeia EN14889-2:2006. As medições do comprimento se efetuaram por dois métodos: o método do paquímetro e o método de análise de imagens digitais, empregando um software para processamento das imagens. Para a medição do diâmetro, além das metodologias mencionadas, foi usado o método da densidade. Conclui-se que o método do paquímetro, com o cuidado de esticar previamente as macrofibras, e o método das imagens digitais podem ser igualmente utilizados para medir o comprimento. Já parar determinar o diâmetro, recomenda-se o método da densidade. Quanto à caracterização mecânica, foi desenvolvida uma metodologia própria a partir de informações obtidas de outros ensaios. Assim, efetuaram-se ensaios de tração direta nas macrofibras coladas em molduras de tecido têxtil. Complementarmente, foi avaliado também o efeito do contato abrasivo das macrofibras com os agregados durante a mistura em betoneira no comportamento mecânico do material. Também se avaliou o efeito do método de determinação da área da seção transversal nos resultados medidos no ensaio de tração da fibra. Conclui-se que o método proposto para o ensaio de tração direta da fibra é viável, especialmente para a determinação da resistência à tração. O valor do módulo de elasticidade, por sua vez, acaba sendo subestimado. A determinação da área da seção da fibra através do método da densidade forneceu também os melhores resultados. Além disso, comprovou-se que o atrito das fibras com o agregado durante a mistura compromete o comportamento mecânico, reduzindo tanto a resistência quanto o módulo de elasticidade. Assim, pode-se afirmar que a metodologia proposta para o controle geométrico e mecânico das macrofibras poliméricas é adequada para a caracterização do material. / A wide variety of synthetic macrofibers for concrete reinforcement are available nowadays. By nature, these fibers exhibit great diversity of properties and characteristics. These variations affect its performance as reinforcement in concrete. However, there are no Brazilian standards on the subject and characterization methodologies available in foreign standards present divergences. Some standards define that the characterization of the mechanical behavior should be made in the original filaments and others that the test should be performed according methods for metallic materials characterization. The standard EN14889-2:2006 provides greater coverage about the subject, but leaves doubts about the suitability of the geometric characterization criteria of the fibers and does not set a specific testing method for its mechanical characterization. Thus, there is a need to establish a methodology that allows to carry out a quality control program of the fiber in the onsite conditions. This approach would also provide a way of materials characterization for experimental studies, which would allow better scientific basis of these works, which often rely exclusively on data taken from manufacturers. Thus, an experimental study focusing on the characterization of two polymer macrofibers available in Brazil was developed. The study aims at the determination of the geometrical and mechanical characteristics, such as the tensile strength and the elastic modulus. The geometric characterization was based on the prescriptions of the European standard EN14889- 2:2006. Measurements of length were made by two methods: the caliper method and digital image analysis method, employing software for image processing. For the measurement of the diameter, besides the aforementioned methodologies, the density method was also used. It is concluded that the caliper method, taking care to stretch the macrofibers previously, and the method of digital images can also be used to measure the length. To determine the diameter, it is recommended the density method. As for the mechanical characterization, a methodology was developed taking in consideration the previous information related to other tests. Thus, the direct tensile test was carried out in macrofibers glued in textile fabric frames. In addition, it was also evaluated the effect of the abrasive contact of macrofibers with the aggregates during mixing on the mechanical behavior of the material. Also, the effect of the method of determining the cross-sectional area in the results measured in fiber tensile test was evaluated. It is concluded that the proposed method for direct tensile test of the fiber is feasible, especially for tensile strength assessment. The value of the modulus of elasticity, in turn, has been underestimated. The determination of the fiber section area through the density method also gave the best results. Furthermore, it was found that the friction of the fibers with aggregate during mixing compromises the mechanical behavior reducing both strength and elastic modulus. Thus, it can be said that the proposed methodology for the geometric and mechanical control of polymer macrofibers is suitable for the material characterization.

Restauração provisória é uma importante fase da reabilitação bucal com prótese parcial fixa, deve fornecer proteção pulpar e periodontal, apresentar integridade marginal e estética, ter durabilidade suficiente para resistir às forças mastigatórias. Pacientes com bruxismo ou aqueles cujo tratamento requer períodos longos de uso das restaurações provisórias necessitam de material com melhores propriedades mecânicas. Vários métodos têm sido empregados para reforçar próteses fixas provisórias, como fios metálicos, reforço metálico e incorporação de diferentes tipos de fibras, como carbono, polietileno e vidro, nas resinas para restaurações provisórias. O objetivo desse estudo foi avaliar alteração de cor e propriedades mecânicas de resistência flexural, módulo de elasticidade e carga de ruptura em resinas acrílicas com incorporação de fibras de vidro silanizadas. Para avaliação de cor foram confeccionados quarenta corpos-de-prova circulares (15 x 3mm) de cada marca comercial de resina acrílica quimicamente ativada, usada para confecção de restaurações provisórias, Dencor (Clássico Ltda., São Paulo-SP, Brasil), Duralay (Reliance, Worth-IL, EUA) e Trim Plus II (Bosworth Company, Skokie-IL, EUA), sendo vinte corpos-de-prova controles, e vinte experimentais, com adição de 10% em peso de fibras de vidro moídas (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 dos componentes de cor (L*, a*, b*) em espectrocolorímetro portátil (BYK-Gardner GmbH, Gerestried, Alemanha), com três mensurações em cada corpo-de-prova. Para os ensaios de resistência flexural, módulo de elasticidade e carga de ruptura foram confeccionados 40 corpos-de-prova retangulares (10mm de comprimento, 65mm de largura e 3mm de espessura) de cada marca de resina, sendo vinte do grupo controle e vinte do experimental (com fibras). Os corpos-de-prova foram testados em uma máquina de ensaios universal (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), usando três, com velocidade de 5mm/min. Os dados foram analisados estatisticamente, usando testes paramétricos e não paramétricos, de acordo com a distribuição da amostra. Todos os componentes de cor (L*, a* e b*) foram alterados após a incorporação de fibras de vidro, com exceção do componente b* da resina Duralay. Para o ensaio de resistência flexural, a análise de variância evidenciou significância estatística (p<0,01) apenas para o fator resinas (Duralay: 85,748 N/mm2 (± 8,04) ,Trim Plus: 86,860 N/mm2 (± 7,73) e Dencor: 97,400 N/mm2 (± 8,18)).Na avaliação do módulo de elasticidade, a análise de variância mostrou significância estatística (p<0,01) para o fator tratamentos, sem fibra: 2572,138 MPa (± 290,92) e com fibras: 3446,691 MPa (± 411,13), e para a interação, evidenciando que a incorporação de fibras aumentou o módulo de elasticidade das três resinas avaliadas.Na carga de ruptura, a análise de Variância evidenciou significância estatística (p<0,01) para os fatores tratamentos, sem fibras: 482,607 N (± 53,18322) e com fibras: 557,53 N (± 59,49652), resinas Duralay: 494,06 N (± 86,63), Trim Plus: 525,177 N (± 42,85) e Dencor: 540,971 N (± 58,40). Conclui-se que a incorporação de fibras provocou alterações nos componentes de cor e aumentou ambos, módulo de elasticidade e carga de ruptura, contudo não alterou a resistência flexural. / Provisional restoration is an important rehabilitation phase in fixed prosthodontic therapy, it should provide pulpal and periodontal protection, showing marginal integrity and esthetics, should also have enough durability in order to resist to the forces of mastication. Patients with bruxism or those, whose treatment require long-term use of provisional restorations, need material with better mechanical properties. Several methods have been applied to reinforce fixed partial dentures, as well as metal wires, metal reinforcement and the application of different types of fibers, such as carbon, polyethylene and glass in the resins for temporary restorations. The aim of this study was to evaluate the color change as well as the mechanical properties of flexural strength, elastic modulus and load rupture in acrylic resin with silanized glass fibers. In order to evaluate the color, it was fabricated forty circular specimens (15 x 3mm) of each commercial brand of the resins chemically activated, used to make provisional restorations, Dencor (Clássico Ltda., São Paulo-SP, Brasil), Duralay (Reliance, Worth-IL, EUA) e Trim Plus II (Bosworth Company, Skokie-IL, EUA). Twenty specimens were control and the other twenty were experimental with an addition of 10% in glass fiber weights (Reforplás S/A, São Paulo, SP, Brasil). After the superficial finishing of the specimens with silicon carbide paper and rag wheel, it was done an evaluation of the color parameters (L*, a*, b*) with a portable spectrocolorimeter (BYK-Gardner GmbH, Gerestried, Alemanha), in three measures in each specimens. For the flexural strength, elastic modulus and load rupture, forty rectangular specimens were fabricated (10mm in length, 65mm wide and 3mm of thickness) of each resin brand and twenty were experimental with fibers. The specimens were tested on an universal machine (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), using a 3- point bending testing device at a crosshead speed of 5 mm/mim. The data was statistically analyzed using parametric and non-parametric tests, according to the sample distribution. All the color parameter (L*, a* e b*) were altered after putting glass fibers, except the parameter b* from resin Duralay. For flexural resistance, the variance analyzes showed significance statistic (p<0,01) just for the resins ( Duralay: 85,748 N/mm2 (± 8,04) ,Trim Plus: 86,860 N/mm2 (± 7,73) and Dencor: 97,400 N/mm2 (± 8,18)). In the elastic modulus evaluation, the variance analyses showed significance statistic (p<0,01) for the treatment factors, without fibers (2572,138 MPa (± 290,92)) and with fibers (3446,691 (± 411,13)). Regarding the interaction, it showed that the incorporation of the fibers increased the elastic modulus in the three resins analyzed. Regarding the load rupture, the variance analyzed showed significance statistic of (p<0,01) for the treatment factors with fibers: 482,607 N (± 53,18322) and without fibers: 557,53 N (± 59,49652), resins (Duralay: 494,06 N (± 86,63), Trim Plus:525,177 N(± 42,85) e Dencor: 540,971 N (± 58,40)). The results of this study indicated that the incorporation of the fibers caused alterations in the color components and increased both elastic modulus and load rupture; therefore, it didnt increase the flexural resistance.

Restauração provisória é uma importante fase da reabilitação bucal com prótese parcial fixa, deve fornecer proteção pulpar e periodontal, apresentar integridade marginal e estética, ter durabilidade suficiente para resistir às forças mastigatórias. Pacientes com bruxismo ou aqueles cujo tratamento requer períodos longos de uso das restaurações provisórias necessitam de material com melhores propriedades mecânicas. Vários métodos têm sido empregados para reforçar próteses fixas provisórias, como fios metálicos, reforço metálico e incorporação de diferentes tipos de fibras, como carbono, polietileno e vidro, nas resinas para restaurações provisórias. O objetivo desse estudo foi avaliar alteração de cor e propriedades mecânicas de resistência flexural, módulo de elasticidade e carga de ruptura em resinas acrílicas com incorporação de fibras de vidro silanizadas. Para avaliação de cor foram confeccionados quarenta corpos-de-prova circulares (15 x 3mm) de cada marca comercial de resina acrílica quimicamente ativada, usada para confecção de restaurações provisórias, Dencor (Clássico Ltda., São Paulo-SP, Brasil), Duralay (Reliance, Worth-IL, EUA) e Trim Plus II (Bosworth Company, Skokie-IL, EUA), sendo vinte corpos-de-prova controles, e vinte experimentais, com adição de 10% em peso de fibras de vidro moídas (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 dos componentes de cor (L*, a*, b*) em espectrocolorímetro portátil (BYK-Gardner GmbH, Gerestried, Alemanha), com três mensurações em cada corpo-de-prova. Para os ensaios de resistência flexural, módulo de elasticidade e carga de ruptura foram confeccionados 40 corpos-de-prova retangulares (10mm de comprimento, 65mm de largura e 3mm de espessura) de cada marca de resina, sendo vinte do grupo controle e vinte do experimental (com fibras). Os corpos-de-prova foram testados em uma máquina de ensaios universal (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), usando três, com velocidade de 5mm/min. Os dados foram analisados estatisticamente, usando testes paramétricos e não paramétricos, de acordo com a distribuição da amostra. Todos os componentes de cor (L*, a* e b*) foram alterados após a incorporação de fibras de vidro, com exceção do componente b* da resina Duralay. Para o ensaio de resistência flexural, a análise de variância evidenciou significância estatística (p<0,01) apenas para o fator resinas (Duralay: 85,748 N/mm2 (± 8,04) ,Trim Plus: 86,860 N/mm2 (± 7,73) e Dencor: 97,400 N/mm2 (± 8,18)).Na avaliação do módulo de elasticidade, a análise de variância mostrou significância estatística (p<0,01) para o fator tratamentos, sem fibra: 2572,138 MPa (± 290,92) e com fibras: 3446,691 MPa (± 411,13), e para a interação, evidenciando que a incorporação de fibras aumentou o módulo de elasticidade das três resinas avaliadas.Na carga de ruptura, a análise de Variância evidenciou significância estatística (p<0,01) para os fatores tratamentos, sem fibras: 482,607 N (± 53,18322) e com fibras: 557,53 N (± 59,49652), resinas Duralay: 494,06 N (± 86,63), Trim Plus: 525,177 N (± 42,85) e Dencor: 540,971 N (± 58,40). Conclui-se que a incorporação de fibras provocou alterações nos componentes de cor e aumentou ambos, módulo de elasticidade e carga de ruptura, contudo não alterou a resistência flexural. / Provisional restoration is an important rehabilitation phase in fixed prosthodontic therapy, it should provide pulpal and periodontal protection, showing marginal integrity and esthetics, should also have enough durability in order to resist to the forces of mastication. Patients with bruxism or those, whose treatment require long-term use of provisional restorations, need material with better mechanical properties. Several methods have been applied to reinforce fixed partial dentures, as well as metal wires, metal reinforcement and the application of different types of fibers, such as carbon, polyethylene and glass in the resins for temporary restorations. The aim of this study was to evaluate the color change as well as the mechanical properties of flexural strength, elastic modulus and load rupture in acrylic resin with silanized glass fibers. In order to evaluate the color, it was fabricated forty circular specimens (15 x 3mm) of each commercial brand of the resins chemically activated, used to make provisional restorations, Dencor (Clássico Ltda., São Paulo-SP, Brasil), Duralay (Reliance, Worth-IL, EUA) e Trim Plus II (Bosworth Company, Skokie-IL, EUA). Twenty specimens were control and the other twenty were experimental with an addition of 10% in glass fiber weights (Reforplás S/A, São Paulo, SP, Brasil). After the superficial finishing of the specimens with silicon carbide paper and rag wheel, it was done an evaluation of the color parameters (L*, a*, b*) with a portable spectrocolorimeter (BYK-Gardner GmbH, Gerestried, Alemanha), in three measures in each specimens. For the flexural strength, elastic modulus and load rupture, forty rectangular specimens were fabricated (10mm in length, 65mm wide and 3mm of thickness) of each resin brand and twenty were experimental with fibers. The specimens were tested on an universal machine (Emic DL 2000®, Emic, São José dos Pinhais, PR, Brasil), using a 3- point bending testing device at a crosshead speed of 5 mm/mim. The data was statistically analyzed using parametric and non-parametric tests, according to the sample distribution. All the color parameter (L*, a* e b*) were altered after putting glass fibers, except the parameter b* from resin Duralay. For flexural resistance, the variance analyzes showed significance statistic (p<0,01) just for the resins ( Duralay: 85,748 N/mm2 (± 8,04) ,Trim Plus: 86,860 N/mm2 (± 7,73) and Dencor: 97,400 N/mm2 (± 8,18)). In the elastic modulus evaluation, the variance analyses showed significance statistic (p<0,01) for the treatment factors, without fibers (2572,138 MPa (± 290,92)) and with fibers (3446,691 (± 411,13)). Regarding the interaction, it showed that the incorporation of the fibers increased the elastic modulus in the three resins analyzed. Regarding the load rupture, the variance analyzed showed significance statistic of (p<0,01) for the treatment factors with fibers: 482,607 N (± 53,18322) and without fibers: 557,53 N (± 59,49652), resins (Duralay: 494,06 N (± 86,63), Trim Plus:525,177 N(± 42,85) e Dencor: 540,971 N (± 58,40)). The results of this study indicated that the incorporation of the fibers caused alterations in the color components and increased both elastic modulus and load rupture; therefore, it didnt increase the flexural resistance.

Dans la présente étude, la conductivité thermique et le module d'élasticité de revêtementsd’YPSZ élaborés par projection plasma ont été prédits par modélisations numériques 2D et3D de type différences finies et éléments finis.L'influence de la résolution d'image, de la taille et de la valeur du seuil sur les propriétésprédites du revêtement a été étudiée. En outre, les effets de la méthode numérique et du typede condition aux limites ont été étudiés. En particulier, la quantification de l'effet Knudsen(effet de raréfaction) sur le transfert de chaleur à travers une structure poreuse a été réaliséepar modélisation numérique en combinaison avec l'analyse d'image. Les conductivitéseffectives obtenues par modélisation 3D s'avèrent plus élevées que celles obtenues en 2D, etaussi en meilleur accord avec les résultats mesurés. Une corrélation 2D/3D a été trouvéepour la modélisation de la conductivité thermique : cette corrélation permet de prédire lesvaleurs 3D à partir des valeurs calculées en 2D. / In the present study, the thermal conductivity and elastic modulus of thermal spray YPSZcoatings were predicted by 2D and 3D finite differences and finite elements numericalmodeling based on cross-sectional images.The influence of the image resolution, size and threshold on the predicted properties of thecoating was studied. Moreover, the effects of the numerical method and of the boundarycondition were investigated. In particular, the quantification of the Knudsen effect(rarefaction effect) on the heat transfer through a porous structure was realized by numericalmodeling in combination with image analysis. The predicted thermal conductivities obtainedby 3D modeling were found to be higher than those obtained by 2D modeling, and in betteragreement with the measured results. A 2D/3D correlation was sucessfully found for themodeling of thermal conductivity: this correlation allows predicting 3D computed valuesfrom 2D ones.

Combination of the Calphad method and theoretical calculations provides new possibilities for the study of materials science. This work is a part of the efforts within the CCT project (Centre of Computational Thermodynamics) to combine these methods to facilitate modeling and to extend the thermodynamic databases with critically assessed volume data. In this work, the theoretical calculations refer to first-principles and Debye-Grüneisen calculations. The first-principles (i.e. ab initio) electronic structure calculations, based on the Density- Functional Theory (DFT), are capable of predicting various physical properties at 0 K, such as formation energy, volume and bulk modulus. The ab initio simulation software, VASP, was used to calculate the binding curves (i.e. equation of state at 0 K) of metallic elements, cubic carbides and nitrides. From the binding curves, the equilibrium volumes at 0 K were calculated for several metastable structures as well as stable structures. The vibrational contribution to the free energy was calculated using the Debye-Grüneisen model combined with first-principles calculations. Two different approximations for the Grüneisen parameter, γ, were used in the Debye-Grüneisen model, i.e. Slater’s and Dugdale-MacDonald’s expressions. The thermal electronic contribution was evaluated from the calculated electronic density of states. The calculated thermal expansivities for metallic elements, cubic carbides and nitrides were compared with Calphad assessments. It was found that the experimental data are within the limits of the calculations using the two approximations for γ. By fitting experimental heat capacity and thermal expansivity around Debye temperatures, we obtained optimal Poisson’s ratio values and used them to evaluate Young’s and Shear moduli. In order to reach a reasonable agreement with the experiments, it is necessary to use the logarithmic averaged mass of the constitutional atoms. The agreements between the calculations and experiments are generally better for bulk modulus and Young’s modulus than that for shear modulus. A new model describing thermodynamic properties at high pressures was implemented in Thermo-Calc. The model is based on an empirical relation between volume and isothermal bulk modulus. Pure Fe and solid MgO were assessed using this model. Solution phases will be considered in a future work to check the model for compositional dependence.

In this work, scanning multiprobes microscopes were used to study the physical properties of biological, vitreous and ceramics samples. In particular, we have used three different scanning probe microscopy techniques to the study the samples. At first, an atomic force microscope was used to evaluate the mechanical properties of macrophages due to cell adhesion to an extracellular matrix and to study the changes in DNA molecules conformation treated with thymol and adsorbed onto a mica surface modified by poly-L-lysine. The results of these studies show that the cytoskeleton-mediated cell-matrix interactions directly affect biomechanical events in cells by modifying physical properties of the cytoskeleton and that the modification of mica surface using poly-L-Lysine provides a strong and firm bond with DNA. This strong fixation of DNA, allows the study of DNA conformational change on mica when interacting with tymol. The atomic force microscope was also used in studies of laser induced thermal expansion in commercial phosphate glasses. The ability of this technique to detect nanoscale surface deformations and the good agreement between theoretical and experimental results show the potential of this technique to study the amplitude and the dynamic of thermal effects in solid materials. In another study, conductive atomic force microscopy was used to analyze electrical properties of barium titanate semiconductor ceramic and their correlation with specific topographic features of the sample. Finally, using the scanning near-field optical microscopy, we studied interactions between cells and gold nanoparticles, without the need of fluorescent labeling on the nanoparticles, with high spatial resolution. During the presentation of these studies the challenges and necessary instrumentation for their realization was discussed. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, microscópios de varredura multi-sondas foram utilizados para o estudo de propriedades físicas de amostras biológicas, vítreas e cerâmicas. Em especial, usamos três diferentes técnicas de microscopia de varredura por sonda no estudo destas amostras. Primeiramente, um microscópio de força atômica foi usado para avaliar os efeitos na mecânica da membrana de macrófagos, verificando a interferência da adesão celular por uma matriz extracelular. Em seguida, estudamos as mudanças de conformação de moléculas de DNA tratadas com Timol e adsorvidas sobre uma superfície de uma mica modificada por poli-L-lisina. Os resultados destes estudos implicam que as interações célula-MEC mediada pelo citoesqueleto afetam diretamente os eventos biomecânicos das membranas, modificando as propriedades físicas do citoesqueleto celular, e que a modificação da superfície da mica utilizando poli-L-Lisina proporciona uma ligação forte e firme com o DNA. Esta forte fixação do DNA, permitiu o estudo da mudança conformacional do DNA na mica quando interagindo com o timol. O microscópio de força atômica também foi usado para realizar de estudos da expansão térmica em vidros fosfatos comerciais, induzida por um laser. A capacidade desta técnica de detectar deformações superficiais em nano-escala e a boa concordância dos resultados teóricos e experimentais mostra o potencial desta técnica para o estudo da amplitude e dinâmica de efeitos térmicos em materiais sólidos. Num outro estudo, a microscopia força atômica condutora foi usada para a análise de propriedades elétricas de cerâmicas de titanato de bário semicondutor e suas correlações com características topográficas específicas da amostra. Por fim, estudamos interações entre células e nanopartículas de ouro, com o uso da microscopia de varredura em campo próximo, sem a necessidade de marcação fluorescente nas nanopartículas e com alta resolução espacial. Durante a apresentação de cada um destes estudos foi discutido os desafios e parte da instrumentação necessárias para a realização dos mesmos.

Cette thèse, menée dans le cadre d'une Convention Industrielle de Formation par la Recherche (CIFRE) avec l'entreprise MENARD, est consacrée à l'étude de la durabilité d'un procédé particulier de renforcement de sol appelé Colonnes à Module Contrôlé (CMC). Cette application consiste en la mise en place d'un réseau d'inclusions verticales semi-rigides dans un sol afin d'améliorer les caractéristiques globales du terrain avant construction. Ces travaux font suite aux travaux de thèse de François Duplan (2011-2014) sur le développement de nouveaux composites cimentaires destinés à cette application. Dans ce but, il avait optimisé des compositions de mortiers incorporant des granulats spéciaux tels que des billes d'argile expansée ou des granulats en caoutchouc issus du broyage de pneus usagés. Les effets de l'introduction de ces granulats dans les composites ont été analysés aussi bien à l'état frais qu'à l'état durci et complètent les précédentes analyses de F. Duplan, notamment en termes d'indicateur de durabilité (perméabilité aux gaz, diffusion aux ions chlorures) et de comportement mécanique à long terme (retrait et fluage). A l'issue d'une analyse environnementale de l'application, trois mécanismes potentiels de dégradation ont été sélectionnés pour des investigations sur la durabilité des CMC : l'attaque acide, l'attaque sulfatique externe et la dégradation par cristallisation de sels. La réalisation d'essais accélérés en laboratoire a permis de mettre en évidence la pertinence du ciment CEM III/C, utilisé actuellement par MENARD, dans la majorité des cas. La faible teneur en C3A de ce liant permet en effet de limiter la production d'éléments expansifs dans le cas d'une attaque sulfatique externe et sa proportion limitée en hydrates du clinker (en particulier en portlandite) ainsi que le faible rapport C/S des C-S-H assurent une meilleure tenue aux attaques acides. La dégradation par remontée capillaire et cristallisation de sels dépendant avant tout des caractéristiques du réseau poreux et des conditions d'évaporation et beaucoup moins du type de ciment, l'utilisation du ciment CEM III/C présente moins d'intérêt. L'incorporation de granulats en caoutchouc ou de billes d'argile expansée dans les composites ne modifie qu'à la marge leur tenue aux mécanismes de dégradations testés. La majorité des phénomènes de dégradation de l'application étant liée à la pénétration d'agents agressifs au cœur des composites cimentaires, la prédiction des propriétés diffusives du matériau est essentielle dans l'estimation des risques encourus par l'application. Un nouveau modèle prédictif est proposé et comporte deux échelles d'homogénéisation : la première au niveau de la pâte de ciment et la deuxième au niveau du mortier. Les résultats obtenus par ce modèle sont fidèles aux résultats expérimentaux avec des erreurs relatives inférieures à 15%. L'estimation du coefficient de diffusion est globalement plus précise pour les composites incorporant des billes d'argile expansée que pour ceux incorporant des granulats en caoutchouc, une conséquence de la forme sphérique de ces billes mieux en accord avec les hypothèses du modèle mis en œuvre. / This CIFRE PhD-thesis carried out within the framework of Convention Industrielle de Formation par la REcherche (CIFRE) with the company MENARD, focuses on the durability of a specific soil-reinforcement system called Controlled Modulus Columns (CMC) which consists in a network of semi-rigid vertical inclusions cast into the ground in order to enhance its global characteristics before building. This study comes after the PhD work conducted by François Duplan (2011-2014) on the design of new cementitious composites intended for the CMC application and incorporating innovative aggregates like expanded clay grains or rubber aggregates obtained by grinding end-of-life tyres. The effects of addition of such aggregates into the composites have been studied both at fresh and hardened states and complete Duplan previous findings in particular with regards durability indicators (gas permeability, chloride diffusion) and mechanical long-term behaviour (creep and shrinkage). Three potential degradation mechanisms have been selected for the CMC system after an environmental analysis: acid attack, external sulphate attack and salt crystallisation. Laboratory accelerated tests highlighted that CEM III/C cement, actually used by MENARD, is suitable in most of the cases. The low C3A content of this binder reduces the production of expansive products in the case of external sulphate attack and its limited clinker hydrates proportions (in particular in portlandite), along with the low C/S ratio of the C-S-H enhance the resistance to acid attack. Salt crystallisation through capillary rise primarily depends on the porous network characteristics and less on the cement ones, meaning that CEM III/C cement is less relevant in that specific case. Based on the tested degradation mechanisms, incorporating rubber aggregates or expended clay ones into the cementitious composites does not significantly affect their durability. Most of the application degradation phenomenon being linked to the ingress of aggressive agents into the composites; the prediction of their diffusive properties is crucial to assess the risks involved for the application. A new predictive model is proposed with a dual homogenisation process: the first one at the cement paste level and the second one on the mortar level. Predicted results are in agreement with ones from experimental tests with a relative error less than 15%. Diffusion coefficient estimates are globally better for composites that contain expended clay aggregates than those incorporating rubber aggregates due to spherical shape of the first in accordance with the model hypotheses.

La problématique initiale part du constat que les échecs d’implants sont souvent causés par une inadéquation entre les propriétés élastiques de l’os et celles de l’implant. Aujourd’hui, ce problème de biocompatibilité mécanique suscite un intérêt croissant et a conduit au développement d’alliages de titane β-métastables qui possèdent un module d’élasticité faible, moitié moindre que celui de l’alliage Ti-6Al-4V classiquement utilisé dans les applications d’implantologie. De plus, les structures architecturées ou treillis font, elles aussi, l’objet d’intenses recherches dans le but de réduire le module d’élasticité et de maximiser la résistance. Leur mise en forme, avec une maîtrise précise de l’architecture, est possible grâce à la fabrication additive et les nombreuses possibilités qu’elle offre : liberté de design, gain matière, pièces complexes, customisation de masse... Ce travail de thèse porte sur la mise en œuvre de l’alliage de titane à bas module d’élasticité Ti-26Nb(%at.) par la technologie de fusion laser sur lit de poudres. Une stratégie d’élaboration in situ de ces alliages à partir de poudres élémentaires de Ti et de Nb est explorée, à la fois pour permettre d’éventuels ajustements de composition, et pour pallier au manque de disponibilité des alliages de titane sous forme de poudres. La démarche est réalisée avec deux morphologies de poudre, irrégulière et sphérique. Les effets des nombreux paramètres de ce procédé (puissance du laser, vitesse et stratégie de balayage...) sur l’homogénéité et la porosité des pièces élaborées sont quantifiés. Un alliage homogène peut être obtenu sous réserve de l’utilisation d’une densité d’énergie adaptée et d’une granulométrie de poudre tenant compte des températures de fusion respectives des éléments. La caractérisation de la microstructure met en évidence une texture marquée, dépendante de la stratégie de balayage. Les pièces élaborées présentent un bas module d’élasticité associé à une résistance mécanique élevée, avec une déformation élastique favorable par rapport à un alliage de référence coulé. Par ailleurs, un algorithme d’optimisation est développé et permet de contrôler les propriétés mécaniques d’une structure architecturée à partir de ses paramètres géométriques (rayon, longueur et orientation des poutres). La combinaison de cet alliage de titane à bas module d’élasticité et d’une structure architecturée développée à partir ce cet algorithme a été appliqué à une prothèse totale de hanche, qui a fait l’objet de simulations par éléments finis. L’évaluation du phénomène de stress-shielding montre que, comparativement à un modèle massif plus rigide, ce type de prothèse permet de réduire de façon significative la déviation des contraintes. En se rapprochant du modèle dit physiologique, cette prothèse peut être qualifiée de « biomimétique » sur le plan du comportement mécanique / The initial problematic arises from the fact that implant failure is often caused by a mismatch between the elastic properties of the bone and those of the implant. Nowadays, an increasing interest is given to this mechanical biocompatibility and led to the development of β-metastable titanium alloys that possess low Young’s modulus, about half that of the conventionally used Ti-6Al-4V alloy. Moreover, lattice structures are currently being the subject of many investigations with the aim of achieving low Young’s modulus and high strength. Their fabrication, with accurate control over the architecture, is made possible thanks to additive manufacturing processes and the several possibilities they offer: design freedom, reduced material usage rate, complex shapes, mass customisation... The present work focuses on the implementation of low modulus titanium alloy Ti-26Nb(at.%) by the means of selective laser melting. An in situ elaboration strategy, based on a mixture of elemental powders, is explored in order to allow potential composition adjustments and to overcome the unavailability of titanium alloy powders. The approach is carried out using two distinct powder morphologies, spherical and irregular. The effects of the numerous parameters of the process (laser power, speed, scanning strategy...) on homogeneity and porosity of the manufactured parts is quantified. A homogeneous alloy can be obtained subject to the use of suitable energy density levels and powder size distributions that take into account the respective fusion temperatures of both elements. Microstructure characterisation highlights a pronounced texture resulting from the scanning strategy. The elaborated samples display a low Young’s modulus associated with a high strength, and hence a favourable strength to elastic modulus ratio compared to the reference cast alloy. Furthermore, an optimization algorithm is developed and allows controlling the mechanical properties of a lattice structure with its geometrical parameters (radius, length and orientation of struts). The combined use of this low Young’s modulus titanium alloy with a lattice structure developed through this algorithm was applied to the design of a total hip prosthesis that was subjected to finite element simulations. Stress-shielding evaluation shows that, compared to a solid design, this kind of prosthesis permits to reduce stress-shielding significantly. By getting closer to a physiological model, this prosthesis can be qualified as “biomimetic” in terms of mechanical behaviour

Uma grande diversidade de macrofibras poliméricas para reforço de concreto se encontram disponibilizadas hoje em dia. Por natureza estas fibras apresentam grande diversidade de características e propriedades. Estas variações afetam sua atuação como reforço no concreto. No entanto, não há normas brasileiras sobre o assunto e as metodologias de caracterização de normas estrangeiras apresentam divergências. Algumas normas definem que a caracterização do comportamento mecânico deva ser feita nos fios originais e outras que se devam utilizar métodos definidos para caracterização de materiais metálicos. A norma EN14889-2:2006 apresenta maior abrangência, mas deixa dúvidas quanto à adequação dos critérios de caracterização geométrica das fibras e não define um método de ensaio específico para sua caracterização mecânica. Assim, há a necessidade de estabelecimento de uma metodologia que permita a realização de um programa de controle de qualidade da fibra nas condições de emprego. Esta metodologia também proporcionaria uma forma de caracterização do material para estudos experimentais, o que permitiria maior fundamentação científica desses trabalhos que, frequentemente, fundamentam-se apenas em dados dos fabricantes. Assim, foi desenvolvido um estudo experimental focando a caracterização de duas macrofibras poliméricas disponíveis no mercado brasileiro. Focou-se o estudo na determinação dos parâmetros geométricos e na caracterização mecânica através da determinação da resistência à tração e avaliação do módulo de elasticidade. Na caracterização geométrica foi adotada como referência a norma europeia EN14889-2:2006. As medições do comprimento se efetuaram por dois métodos: o método do paquímetro e o método de análise de imagens digitais, empregando um software para processamento das imagens. Para a medição do diâmetro, além das metodologias mencionadas, foi usado o método da densidade. Conclui-se que o método do paquímetro, com o cuidado de esticar previamente as macrofibras, e o método das imagens digitais podem ser igualmente utilizados para medir o comprimento. Já parar determinar o diâmetro, recomenda-se o método da densidade. Quanto à caracterização mecânica, foi desenvolvida uma metodologia própria a partir de informações obtidas de outros ensaios. Assim, efetuaram-se ensaios de tração direta nas macrofibras coladas em molduras de tecido têxtil. Complementarmente, foi avaliado também o efeito do contato abrasivo das macrofibras com os agregados durante a mistura em betoneira no comportamento mecânico do material. Também se avaliou o efeito do método de determinação da área da seção transversal nos resultados medidos no ensaio de tração da fibra. Conclui-se que o método proposto para o ensaio de tração direta da fibra é viável, especialmente para a determinação da resistência à tração. O valor do módulo de elasticidade, por sua vez, acaba sendo subestimado. A determinação da área da seção da fibra através do método da densidade forneceu também os melhores resultados. Além disso, comprovou-se que o atrito das fibras com o agregado durante a mistura compromete o comportamento mecânico, reduzindo tanto a resistência quanto o módulo de elasticidade. Assim, pode-se afirmar que a metodologia proposta para o controle geométrico e mecânico das macrofibras poliméricas é adequada para a caracterização do material. / A wide variety of synthetic macrofibers for concrete reinforcement are available nowadays. By nature, these fibers exhibit great diversity of properties and characteristics. These variations affect its performance as reinforcement in concrete. However, there are no Brazilian standards on the subject and characterization methodologies available in foreign standards present divergences. Some standards define that the characterization of the mechanical behavior should be made in the original filaments and others that the test should be performed according methods for metallic materials characterization. The standard EN14889-2:2006 provides greater coverage about the subject, but leaves doubts about the suitability of the geometric characterization criteria of the fibers and does not set a specific testing method for its mechanical characterization. Thus, there is a need to establish a methodology that allows to carry out a quality control program of the fiber in the onsite conditions. This approach would also provide a way of materials characterization for experimental studies, which would allow better scientific basis of these works, which often rely exclusively on data taken from manufacturers. Thus, an experimental study focusing on the characterization of two polymer macrofibers available in Brazil was developed. The study aims at the determination of the geometrical and mechanical characteristics, such as the tensile strength and the elastic modulus. The geometric characterization was based on the prescriptions of the European standard EN14889- 2:2006. Measurements of length were made by two methods: the caliper method and digital image analysis method, employing software for image processing. For the measurement of the diameter, besides the aforementioned methodologies, the density method was also used. It is concluded that the caliper method, taking care to stretch the macrofibers previously, and the method of digital images can also be used to measure the length. To determine the diameter, it is recommended the density method. As for the mechanical characterization, a methodology was developed taking in consideration the previous information related to other tests. Thus, the direct tensile test was carried out in macrofibers glued in textile fabric frames. In addition, it was also evaluated the effect of the abrasive contact of macrofibers with the aggregates during mixing on the mechanical behavior of the material. Also, the effect of the method of determining the cross-sectional area in the results measured in fiber tensile test was evaluated. It is concluded that the proposed method for direct tensile test of the fiber is feasible, especially for tensile strength assessment. The value of the modulus of elasticity, in turn, has been underestimated. The determination of the fiber section area through the density method also gave the best results. Furthermore, it was found that the friction of the fibers with aggregate during mixing compromises the mechanical behavior reducing both strength and elastic modulus. Thus, it can be said that the proposed methodology for the geometric and mechanical control of polymer macrofibers is suitable for the material characterization.