The alkali elements at ambient conditions are well described by the nearly-free electron (NFE) model, yet show a remarkable departure from this “simple” behaviour with increasing pressure. Low-symmetry complex structures are observed in all, and anomalous melting has been observed in lithium (Li), sodium (Na), rubidium (Rb), and caesium (Cs). In this Thesis, static and dynamic compression techniques have been used to investigate the high-pressure high-temperature behaviour of the alkali elements potassium (K) and Na. Utilising diamond anvil pressure cells and external resistive heating, both in-air and in-vacuum, the melting curve of K has been determined to 24 GPa and 750 K, and is found to be remarkably similar to that of Na, but strikingly different to that reported previously. Furthermore, there is some evidence to suggest that a change in the compressibility of liquid-K occurs at lower pressures than the solid-solid phase transitions, perhaps indicating structural transitions occurring in the liquid phase, similar to those in the underlying solid. This could suggest a mechanism to explain the anomalous melting behaviour observed. Previous ab initio computational studies indicate that the unusual melting curve of Na arises due to structural and electronic transitions occurring in the liquid, mirroring those found in the underlying solid at higher pressures. The discovery that the melting curve of K is very similar to that of Na suggests that the same physical phenomena predicted for Na could be responsible for the high-pressure melting behaviour observed in K. The tI19 phase of K, observed above 20 GPa at 300 K, is a composite incommensurate host-guest structure consisting of 1D chains of guest atoms surrounded by a tetragonal host framework. Along the unique c-axis, the host and guest are incommensurate with each other. During the melting studies described above, it was observed that with increasing temperature, the weaker-bonded guest chains become more disordered while the host structure remains unchanged. To investigate and characterise this order-disorder transition, in situ synchrotron X-ray diffraction studies were conducted on single-crystal and quasi-single crystal samples of tI19-K. An order-disorder phase line has been mapped out to 50 GPa and 650 K. Perhaps the most striking departure from NFE behaviour in the alkali elements is observed in Na at pressures above 200 GPa where it transforms to a transparent electrical insulator. This phase is a so-called elemental “electride”, which may be thought of as being pseudo-ionically bonded. Electrides are predicted to exist in many elements, but at pressures far beyond the current capabilities of static pressure techniques. Utilising laser-driven quasi-isentropic compression techniques, dynamic compression experiments were performed on Na to see if it is possible to observe this electride phase under the timescales of dynamic compression experiment (ns). Optical velocimetry and reflectivity of the sample were measured directly to determine pressure and monitor the on-set of the transparent phase, respectively.

Alkali silica reaction (ASR) and delayed ettringite formation (DEF) are two causes of concrete deterioration. Both mechanisms cause expansion of concrete and thus extensive cracking. Most previous research on ASR and DEF focused on understanding the material science of the mechanisms. This dissertation adds to the smaller body of knowledge about ASR/DEF’s effect on the structural behavior of reinforced concrete columns. It compares the structural performance of ASR/DEF affected concrete columns to mechanically cracked columns, evaluates the relative performance of four different concrete repair methods for strengthening damaged columns, and describes how to model pre-existing cracks in the finite element program ATENA. Previous research on scaled columns used mechanically cracked concrete as an approximation of ASR/DEF cracking damage. These earlier column tests, by Kapitan, were compared to two columns affected by ASR/DEF. Due to a deficiency in original design of the actual columns modeled, all of these scaled column specimens failed in bearing during testing under biaxial bending. The ASR/DEF affected columns exhibited nearly identical performance (including bearing capacity) as Kapitan’s control specimen. Thus, with over one percent expansion due to ASR/DEF, there was no reduction in bearing capacity for these columns. Based on the bearing failure observed in these scaled column specimens, concrete repairs were designed to increase confinement of the column capital to address the bearing capacity deficiency. A series of bearing specimens was constructed, externally reinforced using four different strengthening schemes, and load tested. From this bearing specimen series, both an external post-tensioned repair and a concrete jacketing repair performed well beyond their designed capacities and are recommended for bearing zone confinement repair of similar ASR/DEF affected concrete columns. Further, this dissertation presents how Kapitan’s scaled column results were modeled using ATENA (a reinforced concrete finite element program). A technique for modeling the mechanical cracking was developed for ATENA. Once calibrated, a parametric study used the model to find that a 0.17-inch wide through-section crack in the scaled columnd (5/8 inches in the field) was the threshold that reduced capacity of the scaled column to the factored design load. / text

Over the last decade, a number of reinforced concrete bent caps within Houston, Texas have exhibited premature concrete damage (cracking, spalling and a loss of material strength) due to alkali-silica reaction (ASR) and/or delayed ettringite formation (DEF). The alarming nature of the severe surface cracking prompted the Houston District of the Texas Department of Transportation to initiate an investigation into the structural implications of the premature concrete damage. Specifically, an interagency contract with the University of Texas at Austin charged engineers at Ferguson Structural Engineering Laboratory to: 1. Establish the time-dependent relationship between ASR/DEF deterioration and the shear capacity of affected bridge bent caps. 2. Develop practical recommendations for structural evaluation of in-service bridge bent caps affected by ASR and/or DEF. To accomplish these objectives, six large-scale bent cap specimens were fabricated within the laboratory. Four of the specimens (containing reactive concrete exposed to high curing temperatures) represented the most severe circumstances of deterioration found in the field. The remaining two specimens (non-reactive) provided a basis for the comparison of long-term structural performance. All of the specimens were subjected to a conditioning regimen meant to foster the development of realistic ASR/DEF-related damage. Resulting expansions were characterized over the course of the study through a carefully-planned monitoring program. Following a prolonged exposure period, three of the six bent cap specimens (representing undamaged, mild, and moderate levels of deterioration) were tested in shear. Observations made over the course of each test captured the service and ultimate load effects of ASR/DEF-induced deterioration. Six shear-critical spans were tested prior to this publication: three deep beam and three sectional shear tests. The remaining six shear spans (contained within the remaining three specimens) were retained to establish the effects of severe deterioration through future shear testing. Subsequent analysis of the expansion monitoring and shear testing data provided much needed insight into the performance and evaluation of ASR/DEF damaged bent structures. The results ultimately formed a strong technical basis for the preliminary assessment of a damaged bent structure within Houston, Texas. / text

No description available.

In many arid and semiarid regions worldwide, high levels of soil salinity is a key driver of land degradation, as well as a key impediment to re-establishing plant cover. Combating land degradation and erosion associated with soil salinity requires experimental determination of plant species that can grow in soils with high levels of salinity and can be used to re-establish plant cover. Herein, we evaluated the responses of untested candidate cultivars of two halophytic grass species to high soil salinity: alkali sacaton (Sporobolus airoides Torr.) and seashore paspalum (Paspalum vaginatum Swartz). We evaluated the growth responses of both species in a greenhouse under control (no-salt) and various levels of NaCl salinity (EC 8, 16, 24, 32, 40, and 48dSm(-1)) using Hoagland solution in a hydroponics system in a randomized complete block design trial. At all salinity levels, sacaton grass had a greater shoot height, shorter root length, lower shoot fresh and dry weights, and poorer color and general quality compared to seashore paspalum. The shoot fresh and dry weights of both grasses were greatest at the low to medium levels of salinity, with the greatest response observed at EC 16dSm(-1). At the highest level, salinity significantly reduced shoot fresh and dry weights of both grasses. Because growth of both halophytic species exhibited high tolerance to salinity stress and were stimulated under low to medium levels of salinity, both species could be considered suitable candidates for re-establishing plant cover in drylands to combat desertification and land degradation associated with high levels of soil salinity.

La réaction alcali-silice est une réaction endogène du béton qui peut contribuer à diminuer la durée de vie d'ouvrages coûteux. La modélisation est nécessaire pour pouvoir évaluer la durée de vie restante des ouvrages atteints. L'alcali-réaction provoque un gonflement du béton dû à une fissuration microscopique sous pression de produits de réaction qui sont des gels gonflant par absorption d'eau. Si le béton est chargé, la fissuration microscopique se développe en fonction du chargement local du béton, ce qui induit une anisotropie de comportement et de déformation du béton. L'objectif de notre travail est de simuler, à partir d'hypothèses simples sur les mécanismes réactionnels en jeu, pour une classe de granulats à réactivité rapide, le déroulement de la fissuration du béton au niveau microscopique, de façon à estimer les déformations et les propriétés mécaniques du béton attaqué. Nous utilisons pour cela une description micromécanique du béton qui nous permet de calculer les propriétés mécaniques et les déformations en fonction de l'état de fissuration, et un critère énergétique de fissuration de façon à faire évoluer l'état de fissuration. Le fonctionnement du modèle est testé sur de nombreux cas qui font apparaître que l'utilisation d'un critère de rupture énergétique en micromécanique est bien adaptée à l'alcali-réaction. L'identification des paramètres du modèle sur des essais en laboratoire donne de bons résultats pour des chargements en dessous de 10 MPa, mais conduit à des estimations très élevées des énergies mécaniques. Le modèle a en effet une tendance à surestimer l'anisotropie du gonflement qui est compensée par l'augmentation de l'énergie surfacique de fissuration / The alkali-silica reaction is an endogenous chemical reaction affecting concrete. Therefore, it is important to model the effects of the reaction so as to estimate the life span of the attacked structures. The reaction leads to a microscopic cracking, due to the pressure of the reaction products which swell by absorption of water, inducing swelling of the concrete. If the concrete is mechanically loaded, the orientation of the microscopic cracking is affected by the local stress state, which induces anisotropy of the mechanical properties and deformations of the concrete. Our work aims at simulating, starting from simple assumptions about the reaction mechanisms, and for a class of fast-reacting aggregates, the development of cracking at the microscopic scale, so as to estimate the deformations and mechanical properties of the attacked concrete. In this purpose, we use a micromechanical description of the concrete, thanks to which we can compute the mechanical properties and deformations from the state of cracking of the concrete. In addition to that, we use an energy fracture criterion to determine the evolution of cracking as the attack progresses. We tested our model on numerous cases. These tests show that this description is well adapted to studying alkali-silica reaction. The identification of the parameters using laboratory experiments yielded good results as far as compression stresses are below 10 MPa. However, the fracture energies identified are greater than accepted values for concretes. We think that our model overestimates the anisotropy of the reaction, which is balanced by higher fracture energies in the identification

La nécessité de construire de manière durable, rationnelle et écologique incite à l’innovation et la recherche d’alternatives, telles que la géopolymérisation et l’activation alcaline, qui suscitent un intérêt croissant. Dans ce sens, ces technologies permettent de valorise rdes matières premières à plus faible impact environnemental pour le développement d’une nouvelle famille de matériaux. Cependant, ces mécanismes réactionnels sont complexes et il est encore nécessaire de lever plusieurs verrous avant leur implémentation : la confusion entre les deux processus, l’absence d’approches de formulation rationnelles, la méconnaissance de certaines vulnérabilités, etc. La thèse s’intègre dans cette dynamique et a pour objectif une meilleure connaissance des géopolymères et des matériaux alcali-activés. Le cadre de travail est le développement de coulis d’injection. Un programme expérimental basé sur une sélection de compositions est établi afin de caractériser leurs principales propriétés. Les différences entre les deux processus de structuration sont relevées à travers une étude physico-chimique (DRX, RMN) et liées aux évolutions macroscopiques au jeune âge. Un travail d’optimisation de formulation est mené afin de répondre à des critères d’application et définir les paramètres influençant le comportement rhéologique et mécanique des coulis. Une méthodologie basée sur l’analyse micromécanique et l’homogénéisation multi-échelles a permis d’évaluer le module élastique des matériaux et peut servir de plateforme pour une analyse globale du comportement mécanique. Enfin, une étude de la durabilité est entamée en évaluant la sensibilité au séchage et à la lixiviation en milieu acide. / The need for more durable, rational and ecological constructions encourages innovation and the search for alternatives, such as geopolymerization and alkali-activation, with a growing interest. These technologies allow the use of resources with a lower environmental impact in developing a new class of materials. However, both reaction mechanisms are complex and some issues need further investigation before a proper implementation: the confusion between these processes, the absence of a rational design approach, the lack of knowledge concerning some mechanisms of degradation, etc. The present thesis joins this dynamic and aims at a better understanding of geopolymers and alkali activated materials to design soil injection grouts. An experimental program has been established based on selected mix designs to study their main properties. The differences between both structuration processes were determined through a physicochemical study (XRD, NMR). They were correlated to the macroscopic phenomena observed at early age. An optimization of the mixtures was carried to satisfy the application criteria and define the parameters controlling the rheological and mechanical behavior of the grouts. Using a micromechanical characterization and multiscale homogenization, a methodology has been designed to determine the elastic modulus of the materials.This can be used as a first tool to analyze the global mechanical behavior. Finally, the sensitivity to drying and exposure to acid environments was assessed.

Orientador: Aparecido Augusto de Carvalho / Resumo: O desenvolvimento de sistemas capazes de monitorar e controlar informações estão sendo cada vez mais utilizados, permitindo maior refinamento e confiança nos resultados. Na área instrumental de laboratório, existem situações que exigem maior controle sobre o ensaio. Com o atual avanço na área de microprocessadores, microcontroladores, sensores inteligentes, entre outros, têm impulsionado a utilização dos mesmos na melhoria e confiabilidade de processos mecânicos, químicos, físicos, biológicos, de inteligência artificial, de melhoria de qualidade de vida de pessoas com deficiência. Os processos podem ser melhorados utilizando equipamentos que possuem sistemas embarcados capazes de processar informações e fazer o controle a partir de sistemas operacionais que antes só eram possíveis nos computadores. Na área das grandes estruturas de concreto não é diferente, deve-se monitorar algumas variáveis que resultam em uma manifestação patológica conhecida como reação álcali-agregado, que é um fenômeno de expansão que afeta a durabilidade e a resistência mecânica do concreto, este fenômeno está ligado à algumas variáveis, a umidade relativa interna é umas delas. Existem várias pesquisas no sentido de inibir as reações álcali-agregados, e é sabido que um importante passo antes do acontecimento da reação álcali-agregado em obras hidráulicas, como as usinas hidroelétricas é o monitoramento da umidade e da temperatura no interior do concreto e, acompanhamento das fissuras inerentes do proce... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The development of systems able to monitor and control information is increasingly being used, allowing greater refinement and confidence in results. In the instrumental area of the laboratory, there are situations that require greater control over the test. With the current progress in the area of microprocessors, microcontrollers, intelligent sensors, among others, have encouraged the use of these in the improvement and reliability of mechanical, chemical, physical, biological, artificial intelligence, improving the quality of life of people with deficiency. Processes can be improved by using equipment that has embedded systems that can process information and control from operating systems that were previously only possible on computers. In the area of large concrete structures is not different, it is necessary to monitor some variables that result in a pathological manifestation known as alkali-aggregate reaction, which is an expansion phenomenon that affects the durability and the mechanical resistance of the concrete, this phenomenon is connected to some variables, the relative humidity is one of them. There are several researches to inhibit alkali-aggregate reactions and is known that an important step before the occurrence of the alkali-aggregate reaction in hydraulic works such as hydroelectric plants is the monitoring of humidity and temperature inside the concrete and, the inherent fissures of the expansion process. The present work implemented a low cost, temperat... (Complete abstract click electronic access below) / Doutor

Um dos problemas que contribui para a diminuição do desempenho de células a combustível de membrana trocadora de prótons é o cruzamento de combustível do compartimento anódico para o catódico. Um método de avaliar o contato do combustível anódico com o cátodo consiste da exposição do catalisador oxidado à molécula de interesse, em condições de circuito aberto. Do ponto de vista fundamental, a análise desses transientes de circuito aberto pode fornecer informações importantes acerca do mecanismo reacional associado. São apresentados nessa Dissertação, resultados da interação entre metanol ou etanol e superfícies oxidadas de paládio, em meio alcalino. Entre os parâmetros investigados, maior ênfase foi dada ao efeito da natureza do cátion alcalino presente no eletrólito. Observou-se que a presença de Li+ ou K+ no eletrólito influencia desde a quantidade de óxido formada, até o tempo requerido para a redução desses óxidos pela molécula orgânico dissolvida. A natureza do composto orgânico presente também exerce diferenças consideráveis no transiente de circuito aberto. Finalmente, foram propostos esquemas reacionais para representar a interação de circuito aberto com o metanol e etanol. Em ambos os casos, os mecanismos incluem a produção auto-catalítica de sítios livres de paládio. / One of the problems that contributes to the performance decreasing observed in proton exchange membranes is the fuel crossover from the anodic to the cathodic compartment. A method to evaluate the contact of the anodic fuel with the cathode consists of exposing the oxidized catalyst to the molecule of interest under open circuit conditions. From the fundamental point of view, the analysis of the open circuit transients may provide relevant information on the associated reaction mechanism. In this Dissertation, results of the open circuit interaction between methanol or ethanol with oxidized palladium surfaces, in alkaline media, are presented. Among the distinct investigated parameters, emphasis will be put on the effect of the nature of the alkali cation present in the electrolyte. It was observed that the presence of Li+ or K+ influences several aspects, from the amount of oxide formed to the time needed for the reduction of the oxide by the dissolved organic molecules. The identity of the dissolved organic molecule also exerts marked influence on the open circuit transients. Finally, two reaction schemes for the open circuit interaction with methanol or ethanol were proposed. In both cases, the mechanisms include the auto-catalytic production of free palladium sites.

A montagem de um sistema que permite a detecção de modulação no coeficiente de absorção ótica, devido ao campo elétrico aplicado, foi concluída. A máxima sensibilidade atingida foi de &#916 K / K = 1,5 x 10-6 com resolução em comprimento de onda de 3 nm. O efeito Stark de 2&#170 ordem, na freqüência dupla da do campo elétrico aplicado foi medido para o centro F em KCl e KBr e comparado com provisões teóricas. Os valores obtidos para o KCl coincidem com os de Chiarotti, o que confirma o bom funcionamento do sistema, e diferem dos valores calculados teoricamente. Essa diferença é atribuída à correção do campo local. Os valores obtidos experimentalmente para a variação relativa do coeficiente de absorção foram: para KCl: &#916K / K = 2,93 x 10-5 (78&#176 K) para KBr: &#916K / K = 2,85 x 10-5 (78&#176 K) / The assembly of a system which allows the detection of modulation in the coefficient of optical absorption, due to the applied electrical field, was completed. The maximum sensitivity achieve was &#916 K / K = 1,5 x 10-6, in wave length, of 3 nm. The Stark effect of second order, in the frequency twice as that of the applied electrical field was measured for the center F in KCl and KBr and compared with theoretical previsions. The values obtained for KCl coincide with those of Chiarotti\'s, which confirms the good functioning of the system, and differ from the values calculated theoretically. This difference in ascribed to the correction of the local field. for KCl: &#916K / K = 2,93 x 10-5 (78&#176 K) for KBr: &#916K / K = 2,85 x 10-5 (78&#176 K).