O concreto de elevado desempenho (CED) é aquele que atende aos requisitos de durabilidade e de resistência mecânica da construção, produzido a partir de materiais selecionados, com equipamentos eficientes e procedimentos controlados. Desenvolveu-se, assim, um estudo experimental, tendo como objetivo principal analisar e estabelecer correlações a partir de propriedades mecânicas e de durabilidade com a microestrutura da matriz. Para tanto, considera-se: a) emprego de agregados da região de São Carlos SP, analisando as suas características fundamentais; b) o emprego de cimentos Portland CP II E 32, CP V ARI Plus e CP V ARI RS em conformidade com ABNT, estabelecendo uma sinergia com os outros materiais envolvidos; c) o estabelecimento de dosagens buscando uma maior compacidade; d) a relação entre os constituintes, correlacionando-os com as formas produtivas e características de aplicações; e) o acompanhamento do desenvolvimento da hidratação e da microestrutura das composições estabelecidas e da influência adição da sílica ativa na matriz como um todo. A análise da microestrutura fundamentou-se em ensaios de poro simetria por intrusão de mercúrio, poro simetria por adsorção de gás nitrogênio, microscopia eletrônica de varredura, termogravimetria e difração de raio-X. Os resultados indicam que a sílica ativa tem forte influência na qualidade dos concretos de alto desempenho, principalmente quando em associação com escória de alto fomo, indicando a possibilidade de se produzir concretos duráveis. Da mesma forma, os resultados mecânicos sugerem excelentes perspectivas na produção do CED, com altas resistências à compressão, na faixa de até 110MPa, à tração na flexão da ordem de 10MPa e resistência à abrasão cerca de 40% superior a dos concretos convencionais. / High performance concrete (HPC) is concrete that meets the requisites of hardness and mechanical strength of construction applications, and is produced with selected materiaIs, efficient equipment and controlled procedures. An experimental study was carried out with the main purpose of analyzing and establishing correlations based on mechanical properties and durability of the matrix\'s microstructure. To this end, the following factors were taken into consideration: a) the use of aggregates available in the region of São Carlos, SP, analyzing their fundamental characteristics; b) the use of Portland CP II E 32, CP V AR! Plus and CP V AR! RS cements according to the ABNT code, establishing a synergy with the other materiais involved; c) the establishment of dosages in the search for greater compactness; d) the relation among the constituents, correlating them with the forms of production and characteristics of application; e) follow-up of the development of hydration and of the microstructures of the compositions established, and the influence of the addition of active silica in the matrix as a whole. The microstructural analysis was based on tests of porosity by mercury intrusion, porosity by adsorption of nitrogen gas, scanning electron microscopy, thermogravimetry and X-ray diffraction. The results indicate that active silica exerts a strong influence on the quality of high performance concretes, particularly when associated with slag, indicating the possibility of producing durable concretes. Similarly, the mechanical findings suggest excellent prospects for HPC production, with high compressive strength in the range of up to 110MPa, flexural strength in the order of 10MPa, and abrasive strength approximately 40% superior to that of conventional concretes.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study investigated the effect of thermal treatment technique, used in two treatment conditions: treated wood in an autoclave and after conditioning, subject to the treatment under electric heater (combination), and treated wood by using only electric kiln (oven) on mechanical, hygroscopic and biological properties of Pinus taeda L. and Eucalyptus grandis W. Hill ex Maiden woods, comparing them with the results obtained for the untreated wood. For that three trees with 25 years, were deployed for each species from which it drew the first two logs for making the samples used in the evaluations. In the combination treatment these parts were subjected to thermo treatment by autoclaving at 130°C/ ± 3°C and pressure of 2 kgf/ cm² for 3 hours and after a conditioning period, subjected to electric heat in an oven at 160°C/ ± 1°C for the same period, already parts for just treatment in oven were exposed the last condition. The physical properties consisted in the evaluation of weight loss and specific weight assigned to treatment, equilibrium moisture content, rate of water absorption, effectiveness of water repellency, anti swelling efficiency, tangential, radial, and volumetric swelling and coefficient of anisotropy, the mechanical properties consisted in evaluating the modulus of elasticity and rupture in bending, maximum resistance to compression parallel, Janka hardness, impact resistance, and finally to the biological was employed accelerated decay test in the laboratory using white rot fungi and brown. The effect of heat treatment employed in the two methodologies resulted in different effects than expected with regard to the mechanical and biological. The results indicated that heat treatments used were effective in reducing the hygroscopicity and increased dimensional stability of both species, the best results for the combination method. To provide the mechanical properties of different effects, reaching an increase of resistance to certain properties and for durability of biological parts, treatments favored decay fungi employees, more pronounced effect for the combined method. / A presente pesquisa objetivou investigar o efeito da técnica de retificação térmica, empregada sob duas condições de tratamento: madeira tratada em autoclave e após condicionamento, submetida ao tratamento em estufa (combinação), e madeira tratada pelo uso de estufa elétrica apenas (estufa), nas propriedades mecânicas, higroscópicas e biológicas das madeiras de Pinus taeda L. e Eucalyptus grandis W. Hill ex Maiden, comparando-as com os resultados obtidos para a madeira sem tratamento. Para tanto, foram amostradas três árvores com 25 anos, para cada espécie, de onde se extraíram as duas primeiras toras, para confecção dos corpos de prova utilizados nas avaliações. No tratamento de combinação, as peças foram submetidas a termorretificação em autoclave a 130ºC/±3°C e pressão de 2 kgf/cm², por 3 horas e, após um período de condicionamento, submetidas ao calor em estufa elétrica a 160°C/±1°C, pelo mesmo período; já as peças destinadas apenas ao tratamento em estufa foram submetidas a última condição. As propriedades físicas consistiram na avaliação da perda de peso e massa específica, atribuída ao tratamento, umidade de equilíbrio, taxa de absorção de água, efetividade de repelência à água, eficiência anti inchamento, inchamento tangencial, radial, volumétrico e coeficiente de anisotropia; as propriedades mecânicas consistiram na avaliação do módulo de elasticidade e ruptura em flexão estática, resistência máxima à compressão paralela, dureza de Janka, resistência ao impacto; por fim, para as propriedades biológicas, empregou-se o ensaio de apodrecimento acelerado em laboratório, utilizando fungos de podridão branca e parda. O efeito do tratamento térmico empregado sob as duas metodologias, provocaram resultados diferentes do esperado, no que se refere as propriedades mecânicas e biológicas. Os resultados obtidos indicaram que os tratamentos térmicos empregados, foram eficientes na redução da higroscopicidade e aumento da estabilidade dimensional de ambas as espécies, com os melhores resultados obtidos pelo método de combinação. Para as propriedades mecânicas, os tratamentos térmicos promoveram efeitos diversos, chegando a um incremento da resistência para certas propriedades e, em relação à durabilidade biológica das peças, os tratamentos favoreceram o apodrecimento aos fungos empregados, efeito mais pronunciado para o método combinado.

Advanced composite materials have enabled the conventional aircraft structures to reduce weight, improve fuel efficiency and offer superior mechanical properties. In the past, materials such as aluminum, steel or titanium have been used to manufacture aircraft structures for support of heavy loads. Within the last decade or so, demand for advanced composite materials have been emerging that offer significant advantages over the traditional metallic materials. Of particular interest in the recent years, there has been an upsurge in scientific significance in the usage of adhesively bonded composite joints (ABCJ’s). ABCJ’s negate the introduction of stress risers that are associated with riveting or other classical techniques. In today’s aircraft transportation market, there is a push to increase structural efficiency by promoting adhesive bonding to primary joining of aircraft structures. This research is focused on the issues associated with the durability and related failures in bonded composite joints that continue to be a critical hindrance to the universal acceptance of ABCJ’s. Of particular interest are the short term strength, contamination and long term durability of ABCJ’s. One of the factors that influence bond performance is contamination and in this study the influence of contamination on composite-adhesive bond quality was investigated through the development of a repeatable and scalable surface contamination procedure. Results showed an increase in the contaminant coverage area decreases the overall bond strength significantly. A direct correlation between the contaminant coverage area and the fracture toughness of the bonded joint was established. Another factor that influences bond performance during an aircraft’s service life is its long term strength upon exposure to harsh environmental conditions or when subjected to severe mechanical loading. A test procedure was successfully developed in order to evaluate durability of ABCJ’s comprising severe environmental conditioning, fatiguing in ambient air and a combination of both. The bonds produced were durable enough to sustain the tests cases mentioned above when conditioned for 8 weeks and did not experience any loss in strength. Specimens that were aged for 80 weeks showed a degradation of 10% in their fracture toughness when compared to their baseline datasets. The effect of various exposure times needs to be further evaluated to establish the relationship of durability that is associated with the fracture toughness of ABCJ’s.

La terre est le premier matériau de construction par les hommes, disponible et peu consommateur d’énergie. Aujourd’hui encore, environ 30 % des habitants de la planète vit dans des habitats en terre, et pour les pays en développement, ce pourcentage s’élève à 50 % de la population rurale. De plus, les matériaux à base de terre permettent un meilleur équilibre et contrôle du climat thermique et acoustique intérieur par rapport aux matériaux usuels de construction. Cependant, la majorité des constructions en terre ne répondent pas aux exigences actuelles en termes de contraintes mécaniques, thermiques ou architecturales. Afin de répondre à ces exigences, un travail tant au niveau scientifique qu’au niveau des praticiens est à accomplir dans ce domaine.L’objectif de cette étude est de déterminer l’influence des propriétés des matériaux utilisés sur le comportement mécanique et hygrothermique de composites terre-fibres végétales. Pour cela, différents types de sols et de fibre végétales (paille de lin, paille de blé) ont été utilisés. Ensuite, les performances mécaniques (compression, flexion) et hygrothermiques (sorption/désorption, perméabilité à la vapeur d’eau, conductivité thermique) ont été déterminées pour différents composites terre-fibres végétales. Les résultats montrent que l’utilisation de paille de lin permet d’obtenir des performances mécaniques supérieures à celles obtenues pour la paille de blé. Cependant, il est à noter que l’introduction de fibres aux sols diminue les performances mécaniques due à la diminution de la densité du matériau. Aucune influence claire de la longueur des fibres sur les performances mécanique n’a été constatée. L’étude du comportement hygrothermique a permis de montrer que le comportement à la sorption/désorption du matériau terre-fibres végétales peut être approximer à partir des résultats obtenus pour les matériaux de base. De plus, il a été démontré que l’évolution de la conductivité thermique du matériau terre-fibres végétales au cours du séchage est reliée au comportement au retrait. / Soil is the first construction material used by man, widely available and low energy consuming. Indeed, about 30% of the current world population lives in earthen structures and, in developing countries, this rate rise to 50%, mostly rural. Moreover, earth-based materials allow an improved balance and control of thermal and acoustic indoor climate compared to industrial construction materials. However, most of earthen structures do not reach current requirements in terms of mechanical, thermal or architectural. To respond to these requirements, a work at scientific and craftsman levels is necessary.The objective of this study is to determine the influence of materials’ properties on the mechanical and hygrothermal behaviour of earth-fiber composites. In order to do this, different types of soil and plant fiber (flax straw, wheat straw) were used. Then, mechanical (compression, bending) and hygrothermal performances (sorption / desorption, water vapor permeability, thermal conductivity) were determined for different soil-fiber composites. Results show that the use of flax straw provides better mechanical performances than use of wheat straw. However, it should be noted that fibers addition to soil decreases mechanical performance due to the decrease of material density. No clear influence of fiber length on mechanical performance was found. The study of hygrothermal behaviour has shown that the sorption / desorption behaviour of earth-fiber material can be approximated from the results obtained from basic materials. In addition, it has been shown that the thermal conductivity evolution of earth-fiber material during drying is related to the shrinkage behaviour.

Die vorliegende Abhandlung befasst sich mit der Thematik der gezielten Festigkeitssteigerung silikatkeramischer Werkstoffe. Dabei liegt das Interesse auf der Korrelation der Bruchspannung verschiedener Versuchswerkstoffe, mit den sich in Abhängigkeit der Rohstoffzusammensetzung bildenden Gefügemerkmalen. Die Grundlage der Versuche ist die Modifikation eines chemisch-technischen Feinsteinzeuges, bestehend aus bildsamen Rohstoffen, den Tonen und zweier unbildsamen Komponenten, den Schamotten. Durch die Substitution der unbildsamen Schamotten mit Feldspatrohstoffen und Aluminiumoxid gelingt die Veränderung der Gefüge bei gleichzeitiger Steigerung der Festigkeit gegenüber dem Referenzwerkstoff. Dabei korrelieren die Substitute eng miteinander. Die Feldspatrohstoffe liefern die erforderliche Menge Alkaliionen zur Intensivierung der Flüssigphasensinterung. In dieser Konsequenz entsteht ein vermehrter Anteil röntgenamorpher Phase. Zudem wird die Mullitkristallisation begünstigt. Das kristalline Al2O3 führt zu einem Verbund mit der amorphen Matrix, der deutlich geringeren Spannungen unterliegt, als es der Fall für den durch die Rohstoffe eingebrachten und ungelösten Restquarz ist. Dieser zeichnet sich vorrangig durch ein vollständiges oder teilweises Ablösen von der Matrix und damit einer kritischen Gefügeschädigung aus. Die damit einhergehende Beeinträchtigung der Werkstoffe wird durch den Vergleich mit einem Werkstoff höheren Quarzanteils bekräftigt. Eingehende röntgenografische Analysen der heterogenen Werkstoffe ermöglichen es, Tendenzen hinsichtlich der Diskrepanz des thermischen Dehnungsverhaltens zwischen Glas- und Mineralphasen aufzuzeigen und somit einen Bezug zu inneren Spannungen herzustellen. Neben derartigen Spannungen im Gefüge zeigt sich die Relevanz des sich während der Werkstoffkonsolidierung bildenden Sekundärmullits. Mikro- und nanoskalige Mullitnadeln, eingebettet in der amorphen Matrix, münden in deren Bewehrung, wodurch ein Beitrag zur Festigkeitssteigerung des Werkstoffes geleistet wird. Die Ergebnisse liefern die grundsätzliche Erkenntnis, dass die unterschiedlichen Wirkmechanismen zur Steigerung der Festigkeit in silkatkeramischen Werkstoffen in kausalem Zusammenhang stehen und nicht ausschließlich individuell betrachtet werden sollten.:1 Einleitung und Problemstellung 1 2 Grundlagen und Stand der Technik 4 2.1 Merkmale des Feinsteinzeugs und Porzellans . . . . . . . . . . . . . . . 4 2.2 Relevante Rohstoffe und deren Eigenschaften . . . . . . . . . . . . . . . 5 2.2.1 Tone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.2.2 Schamotte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.3 Aluminiumoxid . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.4 Feldspat und Feldspatvertreter . . . . . . . . . . . . . . . . . . . 9 2.3 Mechanische Eigenschaften keramischer Werkstoffe . . . . . . . . . . . 11 2.4 Bruchmechanisches Verhalten keramischer Werkstoffe . . . . . . . . . . 12 2.5 Festigkeitstheorien in Abhängigkeit bestimmter Gefügemerkmale . . . . 14 2.5.1 Mullit und die Mullithypothese . . . . . . . . . . . . . . . . . . 14 2.5.2 Gefügespannungstheorie . . . . . . . . . . . . . . . . . . . . . . 16 2.5.3 Dispersionsverstärkung der Matrix . . . . . . . . . . . . . . . . 19 2.5.4 Glasphase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.5.5 Einfluss der Porosität . . . . . . . . . . . . . . . . . . . . . . . . 21 2.5.6 Statistische Auswertung der Bruchspannungsswerte - DieWeibull- Statistik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.6 Grundlagen zur Bestimmung des Mineralphasengehaltes . . . . . . . . . 23 3 Experimentelle Methodik 25 3.1 Grundlagen und Vorgehensweise zur Entwicklung der Masseversätze . . 25 3.1.1 Auswahl der Rohstoffe . . . . . . . . . . . . . . . . . . . . . . . 25 3.1.2 Grundlagen der Versatzberechnung . . . . . . . . . . . . . . . . 26 3.1.3 Erläuterung der Versuchsbezeichnungen . . . . . . . . . . . . . . 28 3.1.4 Zusammenstellung der Versuchsversätze . . . . . . . . . . . . . 29 3.1.5 Aufbereitung der experimentellen Versätze . . . . . . . . . . . . 30 3.2 Charakterisierung der Werkstoffeigenschaften . . . . . . . . . . . . . . . 31 3.2.1 Vorgehensweise zur Bestimmung und statistischen Auswertung der Festigkeitswerte . . . . . . . . . . . . . . . . . . . . . . . . . 31 3.2.2 Bestimmung des Wärmeausdehnungskoeffizienten der Glasmatrix 33 3.2.3 Bestimmung der Deformation während des Sinterprozesses . . . 35 3.2.4 Analyse des Erweichungsverhalten mit dem Erhitzungsmikroskop 36 3.2.5 Wasseraufnahme, Rohdichte und offene Porosität . . . . . . . . 36 3.2.6 Reindichtebestimmung . . . . . . . . . . . . . . . . . . . . . . . 37 3.3 Röntgenographische Untersuchungen . . . . . . . . . . . . . . . . . . . 37 3.3.1 Röntgenbeugungsanalytik . . . . . . . . . . . . . . . . . . . . . 37 3.3.2 Rasterelektronenmikroskopie . . . . . . . . . . . . . . . . . . . . 40 3.3.3 Röntgenfluoreszenzanalyse . . . . . . . . . . . . . . . . . . . . . 40 4 Darstellung und Diskussion der Ergebnisse 42 4.1 Betrachtung der mechanischen Festigkeit . . . . . . . . . . . . . . . . . 42 4.2 Reproduzierbarkeit der Ergebnisse der Bruchspannungsmessungen . . . 48 4.3 Festigkeitsentwicklung in Abhängigkeit der Porosität . . . . . . . . . . 49 4.4 Ergebnisse der mineralogischen Zusammensetzung . . . . . . . . . . . . 55 4.4.1 Qualitative Darstellung der Mineralogie . . . . . . . . . . . . . . 55 4.4.2 Quantitative Darstellung der Mineralogie . . . . . . . . . . . . . 58 4.4.3 Verifizierung der Ergebnisse aus der Mineralphasenquantifizierung nach der modifizierten RIR-Methode . . . . . . . . . . . . 66 4.5 Elektronenmikroskopische Aufnahmen . . . . . . . . . . . . . . . . . . 67 4.5.1 Vergleichende Betrachtung der Gefüge in Abhängigkeit der unterschiedlichen Rohstoffe . . . . . . . . . . . . . . . . . . . . . . 68 4.5.2 Vergleich der Werkstoffgefüge mit Al2O3 und Feldspatrohstoff . 79 4.5.3 Betrachtung der Mullitkristallisation . . . . . . . . . . . . . . . 80 4.6 Wärmdehnungsverhalten der Glasphase . . . . . . . . . . . . . . . . . . 82 4.7 Deformationsverhalten während des Sinterprozesses . . . . . . . . . . . 87 5 Zusammenfassung und Ausblick 90 Literatur- und Quellenverzeichnis 95 Appendix 108 / The theme of the present work is the strength of silicate ceramic materials. In this regard it is of interest to correlate the fracture stress of various experimentally investigated materials with microstructural characteristics dependent on different raw material compositions. The basis of these investigations is the modification of a porcelain stoneware consisting of different types of clay and non plastic chamottes. Substitution of the chamottes with different types of feldspar and alumina leads to significant changes of the microstructure and to an associated increase in mechanical strength relative to the reference material. The feldspar raw materials provide the required concentration of alkali ions to enhance the liquid-phase sintering. As a result, the amount of the amorphous phase inreases and the crystallisation of mullite is promoted. The crystalline alumina becomes embedded in the glassy matrix and thereby leads to significantly lower stresses than would be the case for undissolved residual quartz introduced by the raw materials. Quartz is characterised by a complete or partial detachment from the matrix and thus a critical material failure. This is confirmed by comparison with a material consisting of a high quartz concentration. X-ray analysis of the heterogenous materials reveals trends regarding thermal expansion mismatch between the amorphous and crystalline phases. Thus a relationship to internal stresses is established. In addition, the relevance of the secondary mullite formed during the consolidation process is shown. Micro- and nanoscaled mullite needles, embedded in the amorphous matrix, contribute to the strength of the materials by reinforcing the matrix. The results provide the fundamental insight that the different mechanisms of increasing the strength in silicate ceramic materials are causally related and should not be considered in isolation.:1 Einleitung und Problemstellung 1 2 Grundlagen und Stand der Technik 4 2.1 Merkmale des Feinsteinzeugs und Porzellans . . . . . . . . . . . . . . . 4 2.2 Relevante Rohstoffe und deren Eigenschaften . . . . . . . . . . . . . . . 5 2.2.1 Tone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.2.2 Schamotte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.3 Aluminiumoxid . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.2.4 Feldspat und Feldspatvertreter . . . . . . . . . . . . . . . . . . . 9 2.3 Mechanische Eigenschaften keramischer Werkstoffe . . . . . . . . . . . 11 2.4 Bruchmechanisches Verhalten keramischer Werkstoffe . . . . . . . . . . 12 2.5 Festigkeitstheorien in Abhängigkeit bestimmter Gefügemerkmale . . . . 14 2.5.1 Mullit und die Mullithypothese . . . . . . . . . . . . . . . . . . 14 2.5.2 Gefügespannungstheorie . . . . . . . . . . . . . . . . . . . . . . 16 2.5.3 Dispersionsverstärkung der Matrix . . . . . . . . . . . . . . . . 19 2.5.4 Glasphase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2.5.5 Einfluss der Porosität . . . . . . . . . . . . . . . . . . . . . . . . 21 2.5.6 Statistische Auswertung der Bruchspannungsswerte - DieWeibull- Statistik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.6 Grundlagen zur Bestimmung des Mineralphasengehaltes . . . . . . . . . 23 3 Experimentelle Methodik 25 3.1 Grundlagen und Vorgehensweise zur Entwicklung der Masseversätze . . 25 3.1.1 Auswahl der Rohstoffe . . . . . . . . . . . . . . . . . . . . . . . 25 3.1.2 Grundlagen der Versatzberechnung . . . . . . . . . . . . . . . . 26 3.1.3 Erläuterung der Versuchsbezeichnungen . . . . . . . . . . . . . . 28 3.1.4 Zusammenstellung der Versuchsversätze . . . . . . . . . . . . . 29 3.1.5 Aufbereitung der experimentellen Versätze . . . . . . . . . . . . 30 3.2 Charakterisierung der Werkstoffeigenschaften . . . . . . . . . . . . . . . 31 3.2.1 Vorgehensweise zur Bestimmung und statistischen Auswertung der Festigkeitswerte . . . . . . . . . . . . . . . . . . . . . . . . . 31 3.2.2 Bestimmung des Wärmeausdehnungskoeffizienten der Glasmatrix 33 3.2.3 Bestimmung der Deformation während des Sinterprozesses . . . 35 3.2.4 Analyse des Erweichungsverhalten mit dem Erhitzungsmikroskop 36 3.2.5 Wasseraufnahme, Rohdichte und offene Porosität . . . . . . . . 36 3.2.6 Reindichtebestimmung . . . . . . . . . . . . . . . . . . . . . . . 37 3.3 Röntgenographische Untersuchungen . . . . . . . . . . . . . . . . . . . 37 3.3.1 Röntgenbeugungsanalytik . . . . . . . . . . . . . . . . . . . . . 37 3.3.2 Rasterelektronenmikroskopie . . . . . . . . . . . . . . . . . . . . 40 3.3.3 Röntgenfluoreszenzanalyse . . . . . . . . . . . . . . . . . . . . . 40 4 Darstellung und Diskussion der Ergebnisse 42 4.1 Betrachtung der mechanischen Festigkeit . . . . . . . . . . . . . . . . . 42 4.2 Reproduzierbarkeit der Ergebnisse der Bruchspannungsmessungen . . . 48 4.3 Festigkeitsentwicklung in Abhängigkeit der Porosität . . . . . . . . . . 49 4.4 Ergebnisse der mineralogischen Zusammensetzung . . . . . . . . . . . . 55 4.4.1 Qualitative Darstellung der Mineralogie . . . . . . . . . . . . . . 55 4.4.2 Quantitative Darstellung der Mineralogie . . . . . . . . . . . . . 58 4.4.3 Verifizierung der Ergebnisse aus der Mineralphasenquantifizierung nach der modifizierten RIR-Methode . . . . . . . . . . . . 66 4.5 Elektronenmikroskopische Aufnahmen . . . . . . . . . . . . . . . . . . 67 4.5.1 Vergleichende Betrachtung der Gefüge in Abhängigkeit der unterschiedlichen Rohstoffe . . . . . . . . . . . . . . . . . . . . . . 68 4.5.2 Vergleich der Werkstoffgefüge mit Al2O3 und Feldspatrohstoff . 79 4.5.3 Betrachtung der Mullitkristallisation . . . . . . . . . . . . . . . 80 4.6 Wärmdehnungsverhalten der Glasphase . . . . . . . . . . . . . . . . . . 82 4.7 Deformationsverhalten während des Sinterprozesses . . . . . . . . . . . 87 5 Zusammenfassung und Ausblick 90 Literatur- und Quellenverzeichnis 95 Appendix 108

El desarrollo tecnológico del sector construcción ha permitido incursionar en nuevas técnicas de procesos constructivos, implementación de nuevos productos, y el desarrollo de nuevas tendencias en la industria de la construcción. Actualmente, una de las prioridades de esta industria es el desarrollo social, pero con visión y conceptos de preservación del medio ambiente. En ese sentido, la presente investigación busca mejorar la resistencia mecánica de los muros portantes de las viviendas informales de Lima Este, mediante la implementación de un nuevo producto con mejor desempeño mecánico, sobre todo con uso de materiales reciclados y amigable con el ambiente. Desde muchos años, Lima ha pasado por varias crisis de migraciones, los cuáles han dejado al descubierto la falta de planificación urbanística para brindar espacios seguros y sobre todo ha dado paso al sector informal de la construcción. Sumado a ello la falta de asesoramiento profesional se obtiene un panorama poco favorable al bienestar y seguridad de las familias frente a desastres naturales. La fibra de coco, la ceniza de cáscara de arroz y el uso de concretos reciclados como agregados, prometen un mejor desempeño de los muros portantes en el sentido de soportar mejor las cargas muertas y vivas de una vivienda; asimismo, un mejor desarrollo ante esfuerzos de corte. La metodología de esta investigación se basa en la evaluación y diseño de mezclas, para identificar los porcentajes de reemplazos óptimos y sus respectivos parámetros de diseño, de manera que se cumplan con el marco normativo. / The technological development of the construction sector has allowed us to venture into new techniques of construction processes, implementation of new products, and the development of new trends in the construction industry. Currently, one of the priorities of this industry is social development, but with a vision and concepts of environmental preservation. In this sense, the present research seeks to improve the mechanical resistance of the bearing walls of informal homes in East Lima, by implementing a new product with better mechanical performance, especially with the use of recycled materials and friendly with the environment. For many years, Lima has gone through several migration crises, which have increased the lack of urban planning to provide safe spaces and, above all, it has given way to the informal construction sector. In addition to the lack of professional advice, an unfavorable picture is obtained of the well-being and safety of families in the face of natural disasters. Coconut fiber, rice husk ash and the use of recycled concrete as aggregates, promise better performance of load-bearing walls in the sense of better supporting the dead and live loads of a home; likewise, a better development before tensile stresses. The methodology of this research is based on the evaluation and design of mixtures, to identify the percentages of optimal replacements and their respective design parameters, so that they comply with the regulatory framework. / Tesis

L’érosion des berges est un processus clé de la dynamique fluviale. Elle influence considérablement la charge sédimentaire des rivières et contrôle l’évolution latérale des chenaux. Les méthodes de caractérisation des mécanismes et des variables affectant l’érosion des berges sont toutefois imprécises et difficiles à appliquer. Ce projet a pour objectif de caractériser la dynamique actuelle des berges de deux tributaires contrastés du Saint-Laurent : les rivières Saint-François et Batiscan. Le premier objectif vise à quantifier les caractéristiques géotechniques de deux tronçons des rivières à l’étude près de l’embouchure avec le Saint-Laurent en décrivant la stratigraphie à différents sites typiques et en recueillant des échantillons de sédiments afin de mesurer différentes variables géotechniques (granulométrie, limites d’Atterberg, résistance à l’érosion mécanique, résistance à l’érosion fluviale). Le second objectif vise à quantifier les principales caractéristiques hydrodynamiques (précipitations, débits, cisaillements, vitesses) des deux sections de rivière. Le troisième et dernier objectif cherche à mesurer les taux d’érosion à l’échelle saisonnière en utilisant des relevés GPS et des chaînes d’érosion et à identifier les mécanismes d’érosion qui opèrent sur les rivières. Les résultats montrent une érosion importante des berges sur chacun des tributaires, mais les mécanismes qui la cause diffèrent. La Batiscan possède des berges dont le matériel est cohésif et ses berges sont principalement marquées par des ruptures de masse. La Saint-François présente des berges peu cohésives ce qui favorise l’érosion fluviale. Le taux de recul sur la rivière Saint-François est de l’ordre de 1 à 3 m/an dans certaines sections de la rivière. Une nouvelle méthode de mesure du cisaillement critique d’érosion fluviale à l’aide d’un chenal expérimental a été élaborée. Les cisaillements critiques obtenus se situent entre 1,19 et 13,41 Pa. Les résultats montrent que les facteurs jouant sur l’érosion des berges ont une variabilité intrinsèque et systémique difficile à mesurer. Le protocole expérimental développé dans ce projet s’est toutefois avéré utile pour étudier les principales variables qui influencent l’érosion des berges, tout en quantifiant les taux d’érosion et les mécanismes d’érosion de berge de deux tributaires importants du fleuve Saint-Laurent. Ce protocole pourrait être utile dans d’autres contextes. / Bank erosion is a key process in fluvial dynamics. It affects sedimentary load in rivers and controls channel lateral evolution. Until now, the methodology used to characterize bank erosion mechanisms and other controlling factors is still imprecise and difficult to apply in many cases. The aim of this project is to characterize bank dynamics in two contrasted Saint-Lawrence tributaries: the Batiscan and Saint-François rivers. The first objective of this study is to quantify geotechnical properties of a section on each river. To achieve this objective, we have described stratigraphic sections at different sites and collected bank material samples in order to measure geotechnical variables in the laboratory (grain size analysis, Atterberg limits, mechanical strength, erosional strength). The second objective is to quantify the hydrodynamic characteristics (precipitations, discharge, shear stress, velocity) of the two river sections. The third and last objective is to measure bank erosion rates with GPS data and erosion pins at a seasonal scale and to identify bank erosion mechanisms occurring in the studied reaches. The results show a high erosional sensitivity of the banks on each tributary, but the observed mechanisms differ from on river to the other. Bank material on the Batiscan River is cohesive and is more susceptible to mass failure. Bank material on the Saint-François River is less cohesive and is mainly affected by fluvial erosion. Bank erosion rates measured on Saint-François River are between 1 to 3 m/year in some sections of the studied reach. A new method of measuring fluvial erosion critical shear stress has been developed with a flume. The critical shear stresses are estimated to be between 1,19 and 13,41 Pa. The results demonstrate the high variability of the response of banks to erosional processes and the difficulty of measuring the intrinsic and systemic factors acting on bank erosion. The experimental protocol developed in this project for the study of the main variables that determine erosion bank, erosion rates and bank mechanisms in two tributaries of the Saint-Lawrence could be applied successfully to other rivers.

Escafoldes em alumina foram fabricados e em suas superfícies impregnou-se biovidro e hidroxiapatita; realizou-se análise das propriedades mecânica e de interação célula-escafolde in vitro. Estruturas porosas denominadas escafoldes são utilizadas como suportes para crescimento de tecidos, devem apresentar poros abertos interconectados, com morfologia, distribuição e quantidade de poros que confiram resistência mecânica e induzam o crescimento ósseo. Os escafoldes simulam a matriz extracelular e são a chave para a engenharia de tecidos que está conceituada na cultura prévia de células com proteínas morfogenéticas, oferecendo suporte para o crescimento celular na formação do tecido maduro. Neste trabalho desenvolveu-se técnica de manufatura onde foram conformados escafoldes como corpos-de-prova em alumina, em hidroxiapatita e em alumina infiltrada com biovidro e hidroxiapatita. Os escafoldes foram submetidos a ensaios mecânicos de compressão e sofreram análise de interação com células in vitro. A morfologia e a concentração da porosidade dos escafoldes foram analisadas por microscopia de varredura eletrônica e apresentaram porosidade volumétrica de aproximadamente 70% e diâmetro médio de poros em torno de 190 µm. Observou-se interação das células mais vigorosas e com pronunciada mitose nos escafoldes infiltrados relativamente aos escafoldes de alumina e hidroxiapatita. Os resultados indicaram resistência mecânica para os corpos infiltrados de 43,27 MPa, valor inferior ao observado nos escafolde de alumina 52,27 MPa e muito superior aos de hidroxiapatita 0,28 MPa. Conclui-se que os escafoldes de alumina infiltrados com biovidro e hidroxiapatita apresentaram uma combinação promissora nas características mecânicas e biológicas in vitro com viabilidade econômica. / Alumina scaffolds were manufactured and surface impregnated with bio-glass and hydroxyapatite; the mechanical properties and the in vitro bone-cell and scaffold interaction were analyzed. Porous matrices are usually denominated as scaffolds in tissue engineering and they are used as supports for the tissue growing; they may have open and interconnected pores, with known porous geometry and distribution and with good mechanical strength and be able to induce the tissue cells growing. Scaffolds can work as extra cell matrices, mimic the desired tissue and are considered as the key for the tissue engineering, offering support for the cellular growing in the formation of mature tissue. In this work, manufacture techniques were developed where scaffolds were conformed in alumina, in hydroxyapatite and in alumina infiltrated with bio-glass and hydroxyapatite, as test bodies. The scaffolds were submitted to mechanical compression tests and to the interaction with bone cells in vitro. The morphology and the concentration of the scaffold porosity were analyzed by scanning electronic microscopy (SEM) and they presented porosity concentration near 70,0 vol% and medium diameter of pores around 190,0 µm. The cells interaction strongest and more vigorous bone cell interaction with pronounced mitosis was observed in the alumina scaffolds infiltrated with bio-glass and hydroxyapatite when compared with the alumina scaffolds and hydroxyapatite scaffolds. The results obtained shown lower values of the mechanical strength for the infiltrated scaffolds (43,27 MPa), higher values for non infiltrated alumina scaffold (52,27 MPa) and very low values for the hydroxyapatite scaffolds (0,28 MPa). As observed, final results shown that alumina scaffolds infiltrated with bio-glass and hydroxyapatite presented a promising combination in the mechanical and biological in vitro characteristics with economic viability.

Les céramiques polycristallines pour application dentaire sont aujourd’hui majoritairement des zircones dopées à l’yttrium (Y-TZP). Ce matériau présente des avantages indéniables en terme de résistance à la rupture, de propriétés esthétiques ou encore de ténacité grâce au phénomène de renforcement par transformation de phase. Les problèmes de stabilité de la Y-TZP en présence d’eau peuvent être limités par un travail d’optimisation des poudres, mais la sensibilité intrinsèque du matériau vis-à-vis de l’eau ou des fluides biologiques demeure et représente un risque, spécialement dans le cadre d’applications cliniques. Les matériaux à base de zircone dopée au cérium (Ce-TZP) présentés dans cette étude ont été développés afin de répondre au triple objectif de ténacité, résistance et stabilité. A partir de la Ce-TZP, connue pour sa ténacité et sa stabilité en présence d’eau importantes, un travail d’optimisation de la microstructure a été réalisé afin d’obtenir une résistance à la rupture maximale. Différentes voies ont été explorées afin d’élaborer des microstructures permettant une augmentation de la résistance mécanique de la Ce-TZP, notamment le frittage SPS ou l'élaboration de composites par mélange de poudres commerciales. Parmi les résultats présentés, le plus marquant est sans doute l’élaboration de composites dans le système 10Ce-TZP/MgAl2O4, caractérisés par une combinaison de propriétés mécaniques inédite (Sigma R = 900 MPa, KIc >15MPa.m1/2), et une stabilité à très long terme en présence d’eau . La mise en forme de ce matériau par des procédés industriels de pressage a été rendue possible grâce à une étape de granulation par atomisation ultrasonique. Enfin, un axe de recherche a été dédié à l’élaboration de poudres composites à base de Ce-TZP en une seule étape, par synthèse chimique. Ces travaux plus prospectifs montrent qu’un mélange très intime de deux phases peut-être obtenu par des méthodes de chimie douce dans une poudre composite. Ces poudres permettent l’élaboration de matériaux nanostructurés, dont les propriétés pourraient dépasser celles des composites conventionnels. / Yttria-doped tetragonal zirconia ceramics (often referred as Y-TZP) are today of major interest in biomedical and particularly dental applications, due to their excellent combination of strength and aesthetic features. Nevertheless, the moderate toughness of 3Y-TZP, and its still possible low temperature degradation (LTD) leaves space for new materials development. The purpose of this study is to assess the potential benefit of using ceria-doped zirconia (Ce-TZP) based ceramics as an tough, strong and stable alternative to Y-TZP. Ce-TZP generally possesses high toughness, but moderate strength when compared to 3Y-TZP, which is related to a larger grain size. In order to improve the strength of Ce-TZP, three microstructural optimizations have been carried out. First, Spark Plasma Sintering (SPS) has been used, showing a good potential for the development of nanostructured materials, which can be dense and mainly tetragonal, but aesthetically incompatible with a dental application. Cerium reduction effects on color and phase repartition have been studied. Adding a second step of conventional sintering in air has led to fully dense submicron 12Ce-TZP with acceptable color, but unsufficient strengthening. In a second step, a conventional composite approach has been used, by mixing commercial powders. The most striking result is certainly the uncommon combination of mechanical properties (Sigma R = 900 MPa, KIc > 15MPa.m1/2) obtained in the system 10Ce-TZP/MgAl2O4, together with a long term stability in presence of water. Pilot scale processing of this material has been set up by mean of ultrasonic spray-drying. Finally, a third research axis has been devoted to the synthesis of composite powders based on Ce-TZP, in one step. This work has shown that a very close mix of two phases can be obtained par soft chemistry methods in a composite powder. Nanostructured materials can be obtained from these powders, which properties could exceed those of conventional composites.

Actuellement, la qualité de l’imagerie provenant de systèmes optiques spatiaux est limitée par la taille de leurs miroirs et la masse des structures supportant le miroir. Le développement de systèmes athermiques légers (un seul matériau) constitue le principal challenge dans l’amélioration de ces systèmes. De matériaux légers, résistants mécaniquement (E/ρ3 > 10, σf > 100 MPa) et stables thermiquement (< 2,0.e-6/K) doivent être développés. Dans ce cadre, notre travail porte sur l’élaboration de composites céramiques associant un matériau à coefficient de dilatation thermique (CTE) positif résistant mécaniquement (alumine ou zircone cériée) et un matériau à CTE très négatif (tungstate de zirconium ou β-eucryptite). L'étude du tungstate de zirconium a révélé plusieurs problèmes de décomposition et de réactions avec certaines matrices oxydes, menant à l’abandon de cet oxyde dans l’élaboration des composites. Dans le cas de la β-eucryptite, un phénomène de vermiculation a été mis en évidence, conduisant à la formation d’une porosité intragranulaire. L’optimisation des paramètres de frittage a permis de limiter cette porosité. L’étude du comportement thermique de la β-eucryptite confirme que son CTE très négatif provient principalement d’un phénomène de fissuration, généré par l’anisotropie de dilatation de sa maille cristalline. Cette fissuration est dépendante de la taille des grains mais également de la taille des agrégats de grains dans le cas des poudres. Ainsi, bien que le CTE intrinsèque de la β-eucryptite soit très faible (-0,4.e-6/K), son CTE extrinsèque peut atteindre des valeurs jusqu'à -10,9.e-6/K selon les conditions d’élaboration. Dans ce travail, deux stratégies d’élaboration de composites sont étudiées. Le premier cas consiste à diminuer le CTE des matrices oxydes à partir d’une poudre de β-eucryptite non microfissurée (-0,4.e-6/K) tandis que le second cas consiste à obtenir des matériaux à CTE très faible à partir d’une poudre de β-eucryptite microfissurée (-3,0.e-6/K). Lors de l’utilisation de la matrice en zircone cériée, le taux de dopage au cérium est optimisé afin de limiter la transformation de phase de la zircone. Cette transformation, induite par les contraintes de tension exercées par la β-eucryptite, affecte la linéarité du comportement thermique du composite. Dans les deux cas d’étude, les composites denses montrent une modification du CTE intrinsèque de la β-eucryptite passant de -0,4.e-6/K à plus de +3,2.e-6/K en raison des contraintes de compression appliquées par la matrice (alumine ou zircone cériée). La relaxation de ces contraintes nécessite une sous-densification des composites. A partir de ces observations, différents composites à CTE très faible sont élaborés. Toutefois, le sous-frittage des composites associé à la microfissuration de la β-eucryptite diminuent fortement les propriétés mécaniques des matériaux ainsi élaborés. / High resolution satellite imagery from space optical systems is mainly limited by the mirror size and the mass of structures supporting the mirror. Nowadays, the development of light athermal systems is the major challenge to improve these optical systems. So, light materials having good mechanical properties (E/ρ3 > 10, σf > 100 MPa) and thermal stability (< 2.0e-6/K) are required. Within this context, our project consists in processing new ceramic composites by combining positive thermal expansion coefficient (TEC) materials having good mechanical properties (alumina or ceria doped zirconia) and negative TEC materials (zirconium tungstate or β-eucryptite) The processing of zirconium tungstate-based materials showed several decomposition and chemical reactions with some oxide matrix leading to its giving up. In the case of β-eucryptite, vermicular phenomenon occurs during sintering leading to the formation of intragranular porosity. Sintering parameters optimization can limit this porosity. The study of the thermal behavior of pure β-eucryptite materials shows that the very negative TEC results from microcracking, generated by the TEC anisotropy of its crystal lattice. This microcracking depends on the grain size and the aggregate size in the case of powder materials. Despite the fact that the TEC of its lattice (called intrinsic TE C equals to -0.4e-6/K) is very low, its bulk (or extrinsic) TEC can reach values until -10.9e-6/K according to the processing conditions. In this work, two strategies for developing composites were studied. The first one consists in decreasing the matrix TEC using an uncracked β-eucryptite powder (-0.4e-6/K) while the second one consists in elaborating near zero TEC materials from a microcracked β-eucryptite powder (-3.0e-6/K). When ceria-doped zirconia is used, ceria content must be adjusted in order to limit zirconia phase transformation. This transformation is driven by tensile stresses induced by the β-eucryptite and modifies the composite thermal behavior linearity. In both studied cases, dense composites show a modification of the β-eucryptite intrinsic TEC from -0.4e-6/K to more than +3.2e-6/K as a consequence of compressive stresses applied by the oxide matrix. An uncompleted densification of composites is required to relax these stresses. Taking into account these observations, several very low TEC composites were elaborated. However, the uncompleted densification of composites and the β-eucryptite microcracking greatly decrease the mechanical properties of these materials.