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This dissertation is to obtain an overall understanding of the crack path selection in adhesively bonded joints. Using Dow Chemical epoxy resin DER 331® with various levels of rubber concentration as an adhesive, and aluminum 6061-T6 alloy with different surface pretreatments as the adherends, both symmetric and asymmetric double cantilever beam (DCB) specimens are prepared and tested under mixed mode fracture conditions in this study. Post-failure analyses conducted on the failure surfaces indicate that the failure tends to be more interfacial as the mode II component in the fracture increases whereas more advanced surface preparation techniques can prevent failure at the interface. Through mechanically stretching the DCB specimens uniaxially until the adherends are plastically deformed, various levels of T-stress are achieved in the specimens. Test results of the specimens with various T-stresses demonstrate that the directional stability of cracks in adhesive bonds depends on the T-stress level. Cracks tend to be directionally stable when the T-stress is compressive whereas directionally unstable when the T-stress is tensile. However, the direction of crack propagation is mostly stabilized when more than 3% mode II fracture component is present in the loading regardless of the T-stress levels in the specimens. Since the fracture sequences in adhesive bonds are closely related to the energy balance in the system, an energy balance model is developed to predict the directional stability of cracks and the results are consistent with the experimental observations. Using the finite element method, the T-stress is shown to be closely related to the specimen geometry, indicating a specimen geometry dependence of the directional stability of cracks. This prediction is verified through testing DCB specimens with various adherend and adhesives thicknesses. By testing the specimens under both quasi-static and low-speed impact conditions, and using a high-speed camera to monitor the fracture sequence, the influences of the debond rate on the locus of failure and the directional stability of cracks are investigated. Post-failure analyses suggest that the failure tends to be more interfacial when the debond rate is low and tends to be more cohesive when the debond rate is high. However, this rate dependence of the locus of failure is greatly reduced when more advanced surface preparation techniques are used in preparing the specimens. The post-failure analyses also reveal that cracks tend to be more directionally unstable as the debond rate increases. Finally, employing interface mechanics and extending the criteria for the direction of crack propagation to adhesively bonded joints, the crack trajectories for directionally unstable cracks are predicted and the results are consistent with the overall features of the crack paths observed experimentally. / Ph. D.

For many scientific applications, inverse problems have played a key role in solving important problems by enabling researchers to estimate desired parameters of a system from observed measurements. For example, large-scale inverse problems arise in many global problems and medical imaging problems such as greenhouse gas tracking and computational tomography reconstruction. This dissertation describes advancements in computational tools for solving large-scale inverse problems and for uncertainty quantification. Oftentimes, inverse problems are ill-posed and large-scale. Iterative projection methods have dramatically reduced the computational costs of solving large-scale inverse problems, and regularization methods have been critical in obtaining stable estimations by applying prior information of unknowns via Bayesian inference. However, by combining iterative projection methods and variational regularization methods, hybrid projection approaches, in particular generalized hybrid methods, create a powerful framework that can maximize the benefits of each method. In this dissertation, we describe various advancements and extensions of hybrid projection methods that we developed to address three recent open problems. First, we develop hybrid projection methods that incorporate mixed Gaussian priors, where we seek more sophisticated estimations where the unknowns can be treated as random variables from a mixture of distributions. Second, we describe hybrid projection methods for mean estimation in a hierarchical Bayesian approach. By including more than one prior covariance matrix (e.g., mixed Gaussian priors) or estimating unknowns and hyper-parameters simultaneously (e.g., hierarchical Gaussian priors), we show that better estimations can be obtained. Third, we develop computational tools for a respirometry system that incorporate various regularization methods for both linear and nonlinear respirometry inversions. For the nonlinear systems, blind deconvolution methods are developed and prior knowledge of nonlinear parameters are used to reduce the dimension of the nonlinear systems. Simulated and real-data experiments of the respirometry problems are provided. This dissertation provides advanced tools for computational inversion and uncertainty quantification. / Doctor of Philosophy / For many scientific applications, inverse problems have played a key role in solving important problems by enabling researchers to estimate desired parameters of a system from observed measurements. For example, large-scale inverse problems arise in many global problems such as greenhouse gas tracking where the problem of estimating the amount of added or removed greenhouse gas at the atmosphere gets more difficult. The number of observations has been increased with improvements in measurement technologies (e.g., satellite). Therefore, the inverse problems become large-scale and they are computationally hard to solve. Another example of an inverse problem arises in tomography, where the goal is to examine materials deep underground (e.g., to look for gas or oil) or reconstruct an image of the interior of the human body from exterior measurements (e.g., to look for tumors). For tomography applications, there are typically fewer measurements than unknowns, which results in non-unique solutions. In this dissertation, we treat unknowns as random variables with prior probability distributions in order to compensate for a deficiency in measurements. We consider various additional assumptions on the prior distribution and develop efficient and robust numerical methods for solving inverse problems and for performing uncertainty quantification. We apply our developed methods to many numerical applications such as greenhouse gas tracking, seismic tomography, spherical tomography problems, and the estimation of CO2 of living organisms.

Nanoporous organic polymers, including hypercrosslinked polymers (HCPs), covalent organic frameworks (COFs), polymers of intrinsic microporosity (PIMs), and conjugated microporous polymers (CMPs) etc., are considered good candidates for potential gas storage and gas separation applications. Porosities and surface areas of a series of semirigid alternating copolymers, which contained tert-butyl carboxylate-functionalized stilbene or tert-butyl carboxylate-functionalized styrene, and maleic anhydride or tert-butyl carboxylate-functionalized phenyl maleimide, were investigated using nitrogen sorption/desorption isotherms at 77 K and molecular simulations. These alternating copolymers were found to have Brunauer-Emmett-Teller (BET) surface areas in the range of 20-40 m2/g. Surface areas of these alternating copolymers increased as the steric crowding of the polymer backbone increased, which was the result of introducing extra phenyl rings and/or N-phenyl substituent maleimide units. Surface areas were found to increase as the persistence length increased. A series of HCPs containing functionalized stilbene and N-substituted phenyl maleimide were synthesized via free radical suspension polymerization. The incorporation of these functionalized, chain stiffening, Tg enhancing comonomers raised the Tgs of precursor polymers before they were crosslinked. Surface areas of these HCPs, obtained from nitrogen adsorption/desorption isotherms at 77 K, were up to 1058 m2/g. However, the surface areas of these HCPs were systematically lower than the controls. The high rigidity of the polymer backbone, which was the result of incorporating Tg enhancing comonomer, likely affected the chain mobility of the precursor polymer, decreased the efficiency of post-crosslinking reactions, and thus resulted in lower surface areas. Amine-functionalized styrene/stilbene polymers were prepared via free radical polymerization or post-modification. Amine-containing silica-based sorbents were prepared using the impregnation method. Sorption of CO2 by these materials was tested using TGA and compared with control samples. Both high amine content and certain levels of surface area were found to be important for a sorbent to achieve high CO2 uptake. Highest CO2 uptake (12 wt%) under our testing condition in these materials was achieved by an amine-containing silica sorbent. / Ph. D.

Information and communication systems enter an increasing number of areas of daily lives. Our reliance and dependence on the functioning of such systems is rapidly growing together with the costs and the impact of system failures. At the same time the complexity of hardware and software systems extends to new limits as modern hardware architectures become more and more parallel, dynamic and heterogenous. These trends demand for a closer integration of formal methods and system engineering to show the correctness of complex systems within the design phase of large projects. The goal of this thesis is to introduce a formal holistic approach for modeling, analysis and synthesis of parallel systems that potentially addresses complex system behavior at any layer of the hardware/software stack. Due to the complexity of modern hardware and software systems, we aim to have a hierarchical modeling framework that allows to specify the behavior of a parallel system at various levels of abstraction and that facilitates designing complex systems in an iterative refinement procedure, in which more detailed behavior is added successively to the system description. In this context, the major challenge is to provide modeling formalisms that are expressive enough to address all of the above issues and are at the same time amenable to the application of formal methods for proving that the system behavior conforms to its specification. In particular, we are interested in specification formalisms that allow to apply formal verification techniques such that the underlying model checking problems are still decidable within reasonable time and space bounds. The presented work relies on an exogenous modeling approach that allows a clear separation of coordination and computation and provides an operational semantic model where formal methods such as model checking are well suited and applicable. The channel-based exogenous coordination language Reo is used as modeling formalism as it supports hierarchical modeling in an iterative top-down refinement procedure. It facilitates reusability, exchangeability, and heterogeneity of components and forms the basis to apply formal verification methods. At the same time Reo has a clear formal semantics based on automata, which serve as foundation to apply formal methods such as model checking. In this thesis new modeling languages are presented that allow specifying complex systems in terms of Reo and automata models which yield the basis for a holistic approach on modeling, verification and synthesis of parallel systems. The second main contribution of this thesis are tailored branching-time and alternating time temporal logics as well as corresponding model checking algorithms. The thesis includes results on the theoretical complexity of the underlying model checking problems as well as practical results. For the latter the presented approach has been implemented in the symbolic verification tool set Vereofy. The implementation within Vereofy and evaluation of the branching-time and alternating-time model checker is the third main contribution of this thesis.

Information and communication systems enter an increasing number of areas of daily lives. Our reliance and dependence on the functioning of such systems is rapidly growing together with the costs and the impact of system failures. At the same time the complexity of hardware and software systems extends to new limits as modern hardware architectures become more and more parallel, dynamic and heterogenous. These trends demand for a closer integration of formal methods and system engineering to show the correctness of complex systems within the design phase of large projects. The goal of this thesis is to introduce a formal holistic approach for modeling, analysis and synthesis of parallel systems that potentially addresses complex system behavior at any layer of the hardware/software stack. Due to the complexity of modern hardware and software systems, we aim to have a hierarchical modeling framework that allows to specify the behavior of a parallel system at various levels of abstraction and that facilitates designing complex systems in an iterative refinement procedure, in which more detailed behavior is added successively to the system description. In this context, the major challenge is to provide modeling formalisms that are expressive enough to address all of the above issues and are at the same time amenable to the application of formal methods for proving that the system behavior conforms to its specification. In particular, we are interested in specification formalisms that allow to apply formal verification techniques such that the underlying model checking problems are still decidable within reasonable time and space bounds. The presented work relies on an exogenous modeling approach that allows a clear separation of coordination and computation and provides an operational semantic model where formal methods such as model checking are well suited and applicable. The channel-based exogenous coordination language Reo is used as modeling formalism as it supports hierarchical modeling in an iterative top-down refinement procedure. It facilitates reusability, exchangeability, and heterogeneity of components and forms the basis to apply formal verification methods. At the same time Reo has a clear formal semantics based on automata, which serve as foundation to apply formal methods such as model checking. In this thesis new modeling languages are presented that allow specifying complex systems in terms of Reo and automata models which yield the basis for a holistic approach on modeling, verification and synthesis of parallel systems. The second main contribution of this thesis are tailored branching-time and alternating time temporal logics as well as corresponding model checking algorithms. The thesis includes results on the theoretical complexity of the underlying model checking problems as well as practical results. For the latter the presented approach has been implemented in the symbolic verification tool set Vereofy. The implementation within Vereofy and evaluation of the branching-time and alternating-time model checker is the third main contribution of this thesis.

The thesis is devoted to the study of in-chain impurities in spin 1/2 antiferromagnetic Heisenberg chains (S=1/2 aHC's)---a model which accompanies the research on magnetism since the early days of quantum theory and which is one of the few integrable spin systems. With respect to impurities it is special insofar as an impurity perturbs the system strongly due to its topology: there is no way around the defect. To what extend the one-dimensional picture stays a good basis for the description of real materials even if the chains are disturbed by in-chain impurities is an interesting question which is addressed in this work. For this purpose, Cu Nuclear Magnetic Resonance (NMR) measurements on the cuprate spin chain compounds SrCuO2 and Sr2CuO3 intentionally doped with nickel (Ni), zinc (Zn) and palladium (Pd) are presented. These materials are well known to be among the best realizations of the S=1/2 aHC model and their large exchange coupling constants allow the investigation of the low-energy dynamics within experimentally easily feasible temperatures. NMR provides the unique ability to study the static and dynamic magnetic properties of the spin chains locally which is important since randomly placed impurities break the translational invariance. Because copper is the magnetically active ion in those materials and the copper nuclear spin is most directly coupled to its electron spin, the NMR measurements have been performed on the copper site. The measurements show in all cases that there are changes in the results of these measurements as compared to the pure compounds which indicate the opening of gaps in the excitation spectra of the spin chains and the emergence of oscillations of the local susceptibility close to the impurities. These experimental observations are compared to theoretical predictions to clarify if and to what extend the already proposed model for these doped systems---the finite spin chain---is suitable to predict the behavior of real materials. Thereby, each impurity shows peculiarities. While Zn and Pd are know to be spin 0 impurities, it is not clear if Ni carries spin 1. To shed some light on this issue is another scope of this work. For Zn impurities, there are indications that they avoid to occupy copper sites, other than in the layered cuprate compounds. Also this matter is considered.

No description available.

O Brasil é um país de dimensões continentais, onde existe uma considerável distância entre a geração e os principais centros de consumo. Dessa forma, o estudo e desenvolvimento de novas tecnologias de transmissão a longas distâncias é de fundamental importância para o desenvolvimento do país. A solução mais utilizada atualmente é a transmissão em corrente alternada. Entretanto a transmissão em corrente continua também é uma solução viável para longas distâncias. O sistema brasileiro é composto principalmente por linhas 500 kV em corrente alternada (também há 230; 345; 440 e 750 kV), bem como em corrente continua (em ±600 e ±800 kV). O presente estudo apresenta uma solução de transmissão em corrente alternada por linhas de 1000 kV, que se mostrou mais econômico na transmissão de potências superiores a 3.500 MW e distâncias de 1400km. Nos próximos anos, a geração de energia elétrica no Brasil será expandida de forma significativa, ocorrerá um aumento principalmente na geração de energia eólica e solar, localizadas em sua maioria na região Nordeste do país. Esse aumento na geração exigirá a transmissão de grandes blocos de energia elétrica por distâncias significativas, devido à falta de proximidade entre a geração e os principais centros consumidores, que estão localizados no Sudeste. Neste estudo, serão mostradas as etapas de definição de condutor economicamente mais adequado e projeto da geometria da torre. Com base nos dados obtidos, será feita a avaliação do desempenho da linha 1000 kV, durante a operação normal de fluxo de carga, curtos-circuitos e estabilidade. / Brazil, a country of continental proportions, have significant distance between the power generation centers and the main consumer centers. In such way, the study and development of new transmission technologies over long distances is of fundamental importance for the development of the country. Nowadays, the most commonly used solution is alternating current transmission. However, direct current transmission is also a viable solution for long distances. The Brazilian system mainly consists of 500 kV alternating current lines (along with 230, 345, 440 and 750 kV) and direct current lines (± 600 and ± 800 kV). This study provides a solution for transmission in alternating current by lines of 1000 kV, which proved to be more economical in power transmission over 3,500 MW and distances beyond 1400km. In the coming years, the electric power generation in Brazil will expand significantly; a boost will take place mainly in wind and solar power generation, located mostly in the Northeast of the country. This generation expansion will require transmission of large blocks of electric power over considerable distances, due to the lack of proximity between generation sites and main consumer centers located in the Southeast. This study will show the setting stages of the most economically applicable conductor and tower geometry design. Based on the data obtained, the performance of the 1000 kV line will be evaluated during the regular load flow operation, short circuits and stability.

Les performances des cellules photovoltaïques organiques de type hétérojonction en volume sont entre autres influencées par les propriétés opto-électroniques du polymère semiconducteur donneur d’électrons. L’objectif de cette thèse était de développer de nouveaux polymères π-conjugués pour permettre une meilleure exploitation du spectre solaire et donc améliorer la photogénération des charges. Pour cela, plusieurs dérivés de polythiophènes comportant des substituants aromatiques phényles ont été synthétisés par la méthode de GRIM, à noter l’homopolymère poly[(3-(4-hexylphényl) thiophène] (P3HPT) et le copolymère à blocs poly[3-(4-hexylphényl)thiophène]-bloc-poly(3-hexylthiophène) (P3HPT-b-P3HT). Nous avons également étudié une nouvelle famille de polymères à faible bande interdite basés sur l’alternance d’unités thiophène et dithiéno[3,2-b:2′,3′-d]silole riches en électrons et 2,1,3- benzothiadiazole pauvres en électrons. Après synthèse des différents monomères, les copolymères alternés ont été ensuite obtenus par polycondensation par couplage de Stille. Les différents matériaux synthétisés ont été d’abord caractérisés par analyse thermogravimétrique et par calorimétrie différentielle à balayage afin d’étudier leurs propriétés thermiques. Ensuite, des caractérisations structurales (en particulier DRX et neutrons), optiques (UV-visible) et morphologiques (AFM) ont été réalisées. A partir des résultats obtenus, nous avons pu évaluer les relations entre les structures et les propriétés des matériaux. Finalement, des cellules photovoltaïques à base des polymères synthétisés ont été réalisées et leurs performances ont été corrélées aux propriétés des matériaux. / The performances of organic solar cells based on the concept of bulk heterojunction configuration are strongly influenced by the optoelectronic properties of the electron donor polymer. The aim of this thesis was to develop new π-conjugated polymers to allow a better exploitation of the solar spectrum and thus improving the photogeneration of charges. For this,several polythiophene derivatives substituted by phenyl aromatic groups have been synthesized by the GRIM method, note the homopolymer poly[(3-(4-hexylphenyl)thiophene] (P3HPT) and the diblock copolymer poly[3-(4- exylphenyl)thiophene]-block-poly(3- hexylthiophène) (P3HPT-b-P3HT). We also studied a new family of low band gap polymers based on the alternation of electron-rich thiophene and dithieno[3,2-b:2′,3′-d]silole units andelectron-deficient 2,1,3-benzothiadiazole units. After synthesis of the various monomers, alternating copolymers were then obtained by Stille cross-coupling polycondensation. The different synthesized materials were first characterized by thermogravimetric analysis and by differential scanning calorimetry to study their thermal properties. Then, structural(especially XRD and neutron), optical (UV-visible) and morphological (AFM) characterizations were performed. From the obtained results, we were able to evaluate the relation between structures and properties of materials. Finally, photovoltaic cells based on the synthesized polymers were performed and their performances were correlated to material properties.