<p>This thesis concerns the development and validation of methods for characterization of multi-component preparative LC systems. Measurements of competitive adsorption isotherms are performed to gain detailed information about the interactions inside the chromatography column. This information increases our understanding of the separation process and makes it possible to perform computer simulations and numerical optimizations to find optimal operating conditions.</p><p>The methods under focus are called “the tracer-pulse method”, “the inverse method”, and “the inverse method on plateaus”. They are extensions of existing methods, with new experimental and numerical procedures to enable rapid and accurate multi-component adsorption isotherm determination. In the validation it was shown that they can produce results agreeing with traditional methods and that the acquired adsorption isotherm parameters can be used in simulations to accurately predict the outcome of preparative LC separations.</p><p>The methods were used to characterize several complex LC systems and two phenomena were discovered and theoretically treated: 1) The presence of invisible deformed peaks in single-component systems. 2) Peak deformations encountered with modern chiral stationary phases, caused by strongly adsorbed eluent additives. The latter type of deformation was highly tuneable and it was possible to adjust the enantiomer peak shapes so that the peaks tailed in opposite directions with the sharp sides in between, yielding baseline resolution at remarkably high sample loads.</p><p>In a final applied study both the LC-based perturbation peak method and a biosensor method based on surface plasmon resonance (SPR) were used for the first time for detailed characterization of chiral drug-protein interactions. The fundamental properties of the two very different methods were compared and it was found that the LC method is more suitable for multi-component analysis and that the SPR method is more suitable for stronger interactions.</p>

Short summary of main work since 1999

This thesis concerns the development and validation of methods for characterization of multi-component preparative LC systems. Measurements of competitive adsorption isotherms are performed to gain detailed information about the interactions inside the chromatography column. This information increases our understanding of the separation process and makes it possible to perform computer simulations and numerical optimizations to find optimal operating conditions. The methods under focus are called “the tracer-pulse method”, “the inverse method”, and “the inverse method on plateaus”. They are extensions of existing methods, with new experimental and numerical procedures to enable rapid and accurate multi-component adsorption isotherm determination. In the validation it was shown that they can produce results agreeing with traditional methods and that the acquired adsorption isotherm parameters can be used in simulations to accurately predict the outcome of preparative LC separations. The methods were used to characterize several complex LC systems and two phenomena were discovered and theoretically treated: 1) The presence of invisible deformed peaks in single-component systems. 2) Peak deformations encountered with modern chiral stationary phases, caused by strongly adsorbed eluent additives. The latter type of deformation was highly tuneable and it was possible to adjust the enantiomer peak shapes so that the peaks tailed in opposite directions with the sharp sides in between, yielding baseline resolution at remarkably high sample loads. In a final applied study both the LC-based perturbation peak method and a biosensor method based on surface plasmon resonance (SPR) were used for the first time for detailed characterization of chiral drug-protein interactions. The fundamental properties of the two very different methods were compared and it was found that the LC method is more suitable for multi-component analysis and that the SPR method is more suitable for stronger interactions.

The feasibility of using superelastic shape memory alloys in the retrofit of multiple frame bridges is investigated. First, three shape memory alloy constitutive models with various levels of complexity are compared in order to determine the significance of including subloops and cyclic loading effects on the structural response. The results show that the structural response is more sensitive to the shape memory alloys strength degradation and residual deformation than the sublooping behavior. Next, two parametric studies are conducted to explore the sensitivity of hinge opening to the mechanical behavior of the superelastic shape memory alloys. The first study is focused on the hysteretic properties of the alloy that could vary depending on the chemical composition or the manufacturing process of the alloy, while the second study targets the changes in the mechanical behavior of shape memory alloys resulting from the variability in the ambient temperature. The results show that the hysteretic behavior of shape memory alloys has only a slight effect on the bridge hinge opening as long as the recentering property is maintained. A detailed study on the effect of temperature shows that a reduction in the ambient temperature tends to negatively affect the hinge opening while an increase in temperature results in a slight improvement. Next, a parametric study is conducted to examine the effectiveness of shape memory alloy retrofit devices in limiting hinge openings in bridges with various properties. In addition, a comparison is made with other devices such as conventional steel restrainers, metallic dampers, and viscoelastic solid dampers. The results illustrate that superelastic shape memory alloys are superior in their effectiveness compared to other devices in the case of bridges with moderate period ratios and high level of ductility, especially when subjected to strong earthquakes.

Atomistic simulations are employed in this thesis to investigate defect nucleation and free volume of grain boundaries and nanocrystalline materials. Nanocrystalline materials are of particular interest due to their improved mechanical properties and alternative strain accommodation processes at the nanoscale. These processes, or deformation mechanisms, within nanocrystalline materials are strongly dictated by the larger volume fraction of grain boundaries and interfaces due to smaller average grain sizes. The behavior of grain boundaries within nanocrystalline materials is still largely unknown. One reason is that experimental investigation at this scale is often difficult, time consuming, expensive, or impossible with current resources. Atomistic simulations have shown the potential to probe fundamental behavior at these length scales and provide vital insight into material mechanisms. Therefore, work conducted in this thesis will utilize atomistic simulations to explore structure-property relationships of face-centered-cubic grain boundaries, and investigate the deformation of nanocrystalline copper as a function of average grain size. Volume-averaged kinematic metrics are formulated from continuum mechanics theory to estimate nonlocal deformation fields and probe the nanoscale features unique to strain accommodation mechanisms in nanocrystalline metals. The kinematic metrics are also leveraged to explore the tensile deformation of nanocrystalline copper at 10K. The distribution of different deformation mechanisms is calculated and we are able to partition the role of competing mechanisms in the overall strain of the nanocrystalline structure as a function of grain size. Grain boundaries are observed to be influential in smaller grained structures, while dislocation glide is more influential as grain size increases. Under compression, however, the resolved compressive normal stress on interfaces hinders grain boundary plasticity, leading to a tension-compression asymmetry in the strength of nanocrystalline copper. The mechanisms responsible for the asymmetry are probed with atomistic simulations and the volume-averaged metrics. Finally, the utility of the metrics in capturing nonlocal nanoscale deformation behavior and their potential to inform higher-scaled models is discussed.

Die vorliegende Arbeit befasst sich mit der kontinuumsmechanischen Formulierung des Aushärteverhaltens polymerer Werkstoffe sowie der Implementierung und Simulation von Aushärtestoffgesetzen im Rahmen der Finite-Elemente-Methode. Auf Basis eines allgemeinen Modellierungsrahmens wird ein konkretisiertes Stoffgesetz für die Nachbildung von Aushärteprozessen eines acrylischen Knochenzements entwickelt. Darüber hinaus werden verschiedene Finite-Elemente-Simulationen zum klinischen Verfahren der Vertebroplastie präsentiert. / This work deals with the continuum mechanical formulation of curing phenomena in polymers as well as the implementation and simulation of curing models within the finite element method. Based on a general modelling framework, a specified material model for the simulation of curing processes in an acrylic bone cement is developed. Moreover, different finite element simulations regarding the clinical procedure of vertebroplasty are presented.

A major instrumented geosynthetic reinforced approach embankment was constructed to 5.5 m elevation above ground, with prefabricated vertical drains, over a soft compressible clay deposit at Leneghan, Newcastle, Australia in May 1995. The field monitoring of settlements for over six years shows that the embankment manifests significant creep. The instrumentation, field performance and the finite element analyses for predicting the long-term performance of this embankment are described in this thesis. The maximum settlement of 1.1 m was observed one year after the completion of construction. However, the embankment continued to settle at a rate of 0.4 mm/day for the next 5 years. The horizontal displacements of 0.09-0.14 m at various locations and the maximum reinforcement strains of 0.67% were recorded. A numerical model was developed to perform a fully coupled large deformation elasto-viscoplastic finite element analysis for this performance prediction based on creep model proposed by Kutter and Sathialingam (1992). The foundation soil was modelled with creep material behaviour using six noded linear strain triangular elements. A well-documented case history ??? Sackville embankment, New Brunswick, Canada was analysed using this model as a benchmark problem and the model was found to predict all the behaviour characteristics reasonably well. The results obtained from finite element analysis using this model are shown to be in reasonable agreement with the observed performance of Leneghans embankment in terms of settlements, horizontal displacements, excess pore pressures and geosynthetic strains. But, the prediction of settlements was less than satisfactory beyond April 1999. Finite element analyses were performed to study the sensitivity of this embankment behaviour on the variation of hydraulic conductivity values and geosynthetic reinforcement properties. This sensitivity study indicated that the kv variation, the kh/kv ratio and the nominal values of geosynthetic properties adopted in the benchmark analysis are reasonable enough for the long-term behaviour prediction.

CNPQ / O presente trabalho tem como objetivo o desenvolvimento de um biosensor, utilizando redes de Bragg em fibras óticas, capaz de mensurar deformações em tecido ósseo. Inicialmente foram realizados testes de esterilização e desinfecção com sensores, após o processo completo, os sensores foram testados quanto a sua sensibilidade. Com isso os métodos de esterilização e desinfecção autoclave, óxido etileno, hipoclorito de sódio, cloramina T e ácido peracético, foram eficazes para eliminação e ou inativação dos microrganismos, sem que haja alterações no comportamento das FBGs. Com isso definem-se métodos aplicáveis para possíveis estudos, onde fibras óticas foram implantadas em animais in vivo para estudos de comportamento metabólico com a presença de materiais inorgânicos. Na continuidade dos trabalhos foram realizados testes de compatibilidade de fibras óticas inseridas no tecido subcutâneo de ratos. Baseado na análise descritiva dos cortes histológicos pode-se concluir que as fibras ópticas sem revestimento e com revestimento foram biocompatíveis quando implantadas em subcutâneo de ratos. Sendo assim, foi possível contemplar o desenvolvimento de um sensor baseado em redes de Bragg em fibras óticas para implantação direta no tecido ósseo. Posteriormente foram realizados testes-piloto para o desenvolvimento da metodologia de construção e implante no desenvolvimento de biosensores. Com todo o trabalho feito até à data, o desenvolvimento e construção de um biosensor que foi implantado in vivo foi possível. O biossensor foi fixado na região mandibular de um bovino quatro meses de idade. Uma semana após a implantação, os animais receberam diferentes tipos de alimentos e foi monitorizada durante a ingestão de alimentos. Com as deformações medidas foi possível a análise dos diferentes padrões mastigatórios e diferentes magnitudes de força e frequência mastigatória que o animal desempenhada durante o processo de mastigação. / This study aims to develop a biosensor using Bragg gratings in optical fibers, capable of measuring deformation in bone tissue for this took a lot of work. Initially sterilization and disinfection with sensors tests were performed after the entire process, the sensors were tested for their sensitivity. In the same study methods of sterilization and disinfection have been tested to assess its efficiency. Thus methods of sterilization and disinfection autoclave, ethylene oxide, sodium hypochlorite, chloramine T and peracetic acid were effective for removing or inactivating microorganisms and, without changes in the behavior of the FBGs. With this set up methods applicable for possible studies, where optical fibers are implanted in in vivo animal studies metabolic behavior in the presence of inorganic materials. Continuing the work was carried out optical fiber compatibility tests inserted in the subcutaneous tissue of rats. Based on the descriptive analysis of histological sections can be concluded that the optical fiber uncoated and coated were biocompatible when implanted in rat subcutaneous tissue. Thus it is possible to contemplate the development of a sensor based on Bragg gratings in optical fibers for direct implantation into the bone tissue. Following on from the work were carried out pilot tests for development of construction methodology and implant in biosensor development. With all the work done to date, the development and construction of a biosensor that was implanted in vivo was possible. The biosensor was fixed in the mandibular region of a bull four months old. A week after implantation, the animal received different types of food and was monitored during the intake of foods. With the deformations measured parse the different masticatory patterns and different magnitudes of force and masticatory frequency that the animal developed during the chewing process completing the objectives of this study.

Neste trabalho é apresentado um método para a identificação de falha causada por barras quebradas em rotores de motores de indução trifásicos através da análise de sua deformação dinâmica, utilizando redes de Bragg em fibra óptica (FBG) como elemento sensor. A análise da deformação dinâmica permite a detecção e diagnóstico de uma série de falhas mecânicas como desalinhamento, desbalanceamento, falhas em rolamentos e folga mecânica. Além de falhas mecânicas é possível identificar falhas elétricas como quebras ou trincas em anéis ou barras do rotor. Para as medidas de deformação dinâmica foram utilizados sensores baseados em redes de Bragg em fibra óptica que possuem como características principais a grande capacidade de multiplexação, imunidade à radiação eletromagnética e capacidade de operação a longas distâncias. Ensaios foram feitos em um motor de indução de pequeno porte (3 CV) afim de validar o método e futuramente aplicar em máquinas de médio e grande porte. O motor foi alimentado por três diferentes fontes de alimentação: rede elétrica da concessionária, geradores síncronos e inversor de frequência, para condições de 75% e 100% de sua carga nominal. Nos ensaios foram utilizados um rotor sem defeito de barra e, posteriormente, um rotor com uma barra interrompida. Através dos ensaios foi possível identificar a falha para as duas condições de carga ensaiadas e com as três diferentes fontes de alimentação. A falha de barra quebrada no rotor é identificada em duas regiões do espectro de frequência obtidos com os três conjuntos de ensaios realizados. A primeira região em torno da frequência mecânica de rotação do rotor e a segunda em torno do dobro da frequência elétrica da fonte de alimentação. O sistema se mostrou bastante sensível, com boa relação sinal ruído e com vantagens em relação aos principais métodos e sensores comumente utilizados para a identificação da falha de barras quebradas em motores de indução. / This work presents the rotor broken bar failure identification through strain analysis using fiber Bragg gratings (FBG) as sensor. The dynamic strain analysis allow the diagnostic and detect several mechanical failures like misalignment, unbalances, bearing failures and mechanical clearance, also electrical failures like rotor broken rings and rotor broken bar. Fiber Bragg gratings sensors were used to measure the dynamic deformation, some advantages of FBG are high multiplexing capability, electromagnetic interference immunity and long distance operation capability. Tests were conducted in a small induction motor (3 HP) in order to validate the method and allow it to be applied inthe future in medium and big size machines. The motor was fed through three different sources (directly from the electrical grid, synchronous generators and by one frequency inverter) at 75% and 100% of rated load condition. Tests were conducted with one healthy rotor and then with a rotor with a broken bar. The tests allow identifying the rotor broken bar failure in both load conditions. Rotor broken bar failure could be identified in two spectrum regions for all conducted tests. The first one was the region around the motor mechanical rotational frequency and the second one was the region around twice times power supply frequency. The system have been presented a high sensibility, a god signal to noise relationship (SNR) and some advantages over the main common sensors and methods used to identify and analyze the dynamic eccentricity and rotor broken bar failures in induction motors.

Les garnitures mécaniques sont utilisées dans de multiples applications pour réaliser l'étanchéité autour d'arbres en rotation. Ces composants peuvent fonctionner efficacement pendant plusieurs années en conditions stables, mais leur durée de vie est significativement réduite lorsque les conditions varient. L'objectif de ce travail de recherche est de développer et d’utiliser un banc d'essais et code de calcul pour étudier l'impact de pulsations de pression, d’inversions de pression et du chargement dynamique résultant sur les performances de garnitures mécaniques ayant des faces mésalignées et présentant des défauts de planéité.Le solveur fluide d'un modèle numérique de garnitures mécaniques a été étendu aux conditions transitoires. Un module résolvant la dynamique des forces et des moments a été ajouté afin de prédire le déplacement axial et les déplacements angulaires de la face montée de manière flexible. Afin de caractériser les performances de garnitures, un banc d'essais générant des pulses de pression a été instrumenté et des méthodes de mesure de perte de volume d'huile et d'entrée d'eau mises en place.Des garnitures mécaniques à faces parallèles puis mésalignées, fonctionnant sous pulsations et inversions de pression, ont été testées expérimentalement et simulées. Seules de très faibles augmentations d'eau dans l'huile ont été observées, sans augmentation au cours du temps, et sans fuite d'huile mesurable. Les faibles valeurs d'entrées d'eau sont dues à la faible épaisseur de film et à la courte durée des inversions de pression. Une garniture mécanique expérimentale à fort défaut de planéité a aussi été testée. Contrairement aux autres paramètres, le défaut de planéité semble augmenter significativement la fuite et promouvoir les entrées d'eau et pourrait ainsi être à l'origine de certaines défaillances. / Face seals are mechanical devices used to seal rotating shafts in numerous applications. While they can operate efficiently under steady conditions for years, they tend to fail prematurely when operating in severe, or rapidly varying conditions. The focus of this research work is the development and use of an experimental and a numerical method to investigate the impact of pressure pulses, pressure inversions and induced dynamic loading on the performance of mechanical face seals exhibiting face misalignment and waviness.The fluid solver of a state-of-the art face seal numerical model was extended to transient conditions and a module solving the dynamics for the axial and angular degrees of freedom of the flexibly-mounted stator added. A system-level experimental setup generating pressure pulses was instrumented and methods to characterise face seal performance in terms of oil volume loss and ingression of water outer-fluid selected and implemented.Face seals, with flat and misaligned faces, operating under pressure pulses and pressure inversions were experimentally tested and simulated. They show only slight increase of water in the oil, no increase over time, and no measurable oil leakage. The low water ingression is due to low film thickness combined with the short duration of pressure inversions. An exploratory face seal of high waviness was also experimentally tested. Contrary to the other parameters, the waviness appears to significantly increase the leakage and promote water ingression and could thus be at the origin of some seal failures.