Ion mobility spectrometry (IMS) separates ions on the basis of ion-neutral collision cross-sections (CCS, [omega]), which are determined by the geometry or conformation of the ions. The size-based IM separation can be extended to distinguish conformers that have different shapes in cases where shape differences influence the accessible surface area of the molecule. In recent years, IM has rapidly evolved as a structural characterization technique, which has applied on various structural biology problems. In this work, IMS is combined with molecular dynamics simulation (MDS), specially the integrated tempering sampling molecular dynamics simulation (ITS-MDS) to explore the gas-phase conformation space of two molecular systems (i) protonated tryptophan zipper 1 (trpzip1) ions and its six derivatives (ii) alkali metal ion (Na, K and Cs) adducts of gramicidin A (GA). The structural distributions obtained from ITS-MDS are compared well with results obtained from matrix-assisted laser desorption ionization-ion mobility-mass spectrometry (MALDI-IM-MS) for trpzip 1 series and electrospray ionization-ion mobility-mass spectrometry (ESI-IM-MS) for alkali metal ion adducts of GA. Furthermore, the solvent dependence on conformational preferences of the GA dimer is investigated using a combination of mass spectrometry techniques, viz. ESI-IM-MS and hydrogen/deuterium exchange (HDX)-MS, and MDS. The IM experiments reveal three distinct gramicidin A species, detected as the sodium ion adduct ions, [2GA + 2Na]²⁺, and the equilibrium abundances of the dimer ions varies with solvent polarity. The solution phase conformations are assigned as the parallel and anti-parallel [beta]-helix dimer, and the anti-parallel dimer is the preferred conformation in non-polar organic solvent. The calculated CCS profiles by ITS-MDS agree very well with the experimentally measured CCS profiles, which underscore the utility of the method for determining candidate structures as well as the relative abundances of the candidate structures. The benefit of combining ion mobility measurements with solution-phase H/D exchange is allowing identifications and detail analysis of the solution-phase subgroup conformations, which cannot be uncovered by one method alone.

Gravitational waves are predicted by general relativity theory. Their existence could be confirmed by astronomical observations, but until today they have not yet been measured directly. A measurement would not only confirm general relativity, but also allow for interesting astronomical observations. Great effort is currently being expended to facilitate gravitational radiation measurement, most notably through earth-bound interferometers (such as LIGO and Virgo), and the planned space-based LISA interferometer. Earth-bound interferometers have recently taken up operation, so that a detection might be made at any time, while the space-borne LISA interferometer is scheduled to be launched within the next decade.Among the most promising signals for a detection are the waves emitted by the inspiral of a binary system of stars or black holes. The observable gravitational-wave signature of such an event is determined by properties of the inspiralling system, which may in turn be inferred from theobserved data. A Bayesian inference framework for the estimation of parameters of binary inspiral events as measured by ground- and space-based interferometers is described here. Furthermore, appropriate computational methods are developed that are necessary for its application in practice. Starting with a simplified model considering only 5 parameters and data from a single earth-bound interferometer, the model is subsequently refined by extending it to 9 parameters, measurements from several interferometers, and more accurate signal waveform approximations. A realistic joint prior density for the 9 parameters is set up. For the LISA application the model is generalised so that the noise spectrum is treated as unknown as well and can be inferred along with the signal parameters. Inference through the posterior distribution is facilitated by the implementation of Markov chain Monte Carlo (MCMC) methods. The posterior distribution exhibits many local modes, and there is only a small "attraction region" around the global mode(s), making it hard, if not impossible, for basic MCMC algorithms to find the relevant region in parameter space. This problem is solved by introducing a parallel tempering algorithm. Closer investigation of its internal functionality yields some insight into a proper setup of this algorithm, which in turn also enables the efficient implementation for the LISA problem with its vastly enlarged parameter space. Parallel programming was used to implement this computationally expensive MCMC algorithm, so that the code can be run efficiently on a computer cluster. In this thesis, a Bayesian approach to gravitational wave astronomy is shown to be feasible and promising.

Gravitational waves are predicted by general relativity theory. Their existence could be confirmed by astronomical observations, but until today they have not yet been measured directly. A measurement would not only confirm general relativity, but also allow for interesting astronomical observations. Great effort is currently being expended to facilitate gravitational radiation measurement, most notably through earth-bound interferometers (such as LIGO and Virgo), and the planned space-based LISA interferometer. Earth-bound interferometers have recently taken up operation, so that a detection might be made at any time, while the space-borne LISA interferometer is scheduled to be launched within the next decade.Among the most promising signals for a detection are the waves emitted by the inspiral of a binary system of stars or black holes. The observable gravitational-wave signature of such an event is determined by properties of the inspiralling system, which may in turn be inferred from theobserved data. A Bayesian inference framework for the estimation of parameters of binary inspiral events as measured by ground- and space-based interferometers is described here. Furthermore, appropriate computational methods are developed that are necessary for its application in practice. Starting with a simplified model considering only 5 parameters and data from a single earth-bound interferometer, the model is subsequently refined by extending it to 9 parameters, measurements from several interferometers, and more accurate signal waveform approximations. A realistic joint prior density for the 9 parameters is set up. For the LISA application the model is generalised so that the noise spectrum is treated as unknown as well and can be inferred along with the signal parameters. Inference through the posterior distribution is facilitated by the implementation of Markov chain Monte Carlo (MCMC) methods. The posterior distribution exhibits many local modes, and there is only a small "attraction region" around the global mode(s), making it hard, if not impossible, for basic MCMC algorithms to find the relevant region in parameter space. This problem is solved by introducing a parallel tempering algorithm. Closer investigation of its internal functionality yields some insight into a proper setup of this algorithm, which in turn also enables the efficient implementation for the LISA problem with its vastly enlarged parameter space. Parallel programming was used to implement this computationally expensive MCMC algorithm, so that the code can be run efficiently on a computer cluster. In this thesis, a Bayesian approach to gravitational wave astronomy is shown to be feasible and promising.

Gravitational waves are predicted by general relativity theory. Their existence could be confirmed by astronomical observations, but until today they have not yet been measured directly. A measurement would not only confirm general relativity, but also allow for interesting astronomical observations. Great effort is currently being expended to facilitate gravitational radiation measurement, most notably through earth-bound interferometers (such as LIGO and Virgo), and the planned space-based LISA interferometer. Earth-bound interferometers have recently taken up operation, so that a detection might be made at any time, while the space-borne LISA interferometer is scheduled to be launched within the next decade.Among the most promising signals for a detection are the waves emitted by the inspiral of a binary system of stars or black holes. The observable gravitational-wave signature of such an event is determined by properties of the inspiralling system, which may in turn be inferred from theobserved data. A Bayesian inference framework for the estimation of parameters of binary inspiral events as measured by ground- and space-based interferometers is described here. Furthermore, appropriate computational methods are developed that are necessary for its application in practice. Starting with a simplified model considering only 5 parameters and data from a single earth-bound interferometer, the model is subsequently refined by extending it to 9 parameters, measurements from several interferometers, and more accurate signal waveform approximations. A realistic joint prior density for the 9 parameters is set up. For the LISA application the model is generalised so that the noise spectrum is treated as unknown as well and can be inferred along with the signal parameters. Inference through the posterior distribution is facilitated by the implementation of Markov chain Monte Carlo (MCMC) methods. The posterior distribution exhibits many local modes, and there is only a small "attraction region" around the global mode(s), making it hard, if not impossible, for basic MCMC algorithms to find the relevant region in parameter space. This problem is solved by introducing a parallel tempering algorithm. Closer investigation of its internal functionality yields some insight into a proper setup of this algorithm, which in turn also enables the efficient implementation for the LISA problem with its vastly enlarged parameter space. Parallel programming was used to implement this computationally expensive MCMC algorithm, so that the code can be run efficiently on a computer cluster. In this thesis, a Bayesian approach to gravitational wave astronomy is shown to be feasible and promising.

Gravitational waves are predicted by general relativity theory. Their existence could be confirmed by astronomical observations, but until today they have not yet been measured directly. A measurement would not only confirm general relativity, but also allow for interesting astronomical observations. Great effort is currently being expended to facilitate gravitational radiation measurement, most notably through earth-bound interferometers (such as LIGO and Virgo), and the planned space-based LISA interferometer. Earth-bound interferometers have recently taken up operation, so that a detection might be made at any time, while the space-borne LISA interferometer is scheduled to be launched within the next decade.Among the most promising signals for a detection are the waves emitted by the inspiral of a binary system of stars or black holes. The observable gravitational-wave signature of such an event is determined by properties of the inspiralling system, which may in turn be inferred from theobserved data. A Bayesian inference framework for the estimation of parameters of binary inspiral events as measured by ground- and space-based interferometers is described here. Furthermore, appropriate computational methods are developed that are necessary for its application in practice. Starting with a simplified model considering only 5 parameters and data from a single earth-bound interferometer, the model is subsequently refined by extending it to 9 parameters, measurements from several interferometers, and more accurate signal waveform approximations. A realistic joint prior density for the 9 parameters is set up. For the LISA application the model is generalised so that the noise spectrum is treated as unknown as well and can be inferred along with the signal parameters. Inference through the posterior distribution is facilitated by the implementation of Markov chain Monte Carlo (MCMC) methods. The posterior distribution exhibits many local modes, and there is only a small "attraction region" around the global mode(s), making it hard, if not impossible, for basic MCMC algorithms to find the relevant region in parameter space. This problem is solved by introducing a parallel tempering algorithm. Closer investigation of its internal functionality yields some insight into a proper setup of this algorithm, which in turn also enables the efficient implementation for the LISA problem with its vastly enlarged parameter space. Parallel programming was used to implement this computationally expensive MCMC algorithm, so that the code can be run efficiently on a computer cluster. In this thesis, a Bayesian approach to gravitational wave astronomy is shown to be feasible and promising.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-20T13:53:22Z No. of bitstreams: 1 WELLINGTON CORDEIRO OLIVEIRA - DISSERTAÇÃO (PPGEM) 2018.pdf: 8813868 bytes, checksum: a538ae4b12c154e17d31068945d4febb (MD5) / Made available in DSpace on 2018-08-20T13:53:22Z (GMT). No. of bitstreams: 1 WELLINGTON CORDEIRO OLIVEIRA - DISSERTAÇÃO (PPGEM) 2018.pdf: 8813868 bytes, checksum: a538ae4b12c154e17d31068945d4febb (MD5) Previous issue date: 2018-04-06 / Os aços ferramenta têm uma importante participação no mercado mundial no que se refere a engenharia. São usados na indústria metal-mecânica como ferramentas de corte, moldes, punções, entre outras aplicações. Devido a sua grande importância, é imprescindível discutir a relação entre a microestrutura e as propriedades mecânicas, devido ser uma prática comum na indústria especificar os tratamentos térmicos com base principalmente na dureza final do material, sem considerar que para um mesmo valor de dureza um aço ferramenta pode apresentar diferentes propriedades mecânicas, isto dependendo do ciclo de tratamento térmico aplicado. Logo, a seleção do tratamento térmico é um aspecto tecnológico relevante no desempenho destes aços. Tendo em vista a vasta possibilidade de propriedades mecânicas obtidas (tenacidade a fratura) com diferentes tratamentos térmicos, esse trabalho teve como objetivo especificar um aço ferramenta nacional e um conjunto de parâmetros de tratamento térmico que possibilite a utilização deste material como forma de substituição de um outro aço importado utilizado na confecção de lâminas de corte usadas no processamento de placas de chumbo. O aço selecionado para o desenvolvimento deste trabalho foi o aço AISI D6, a seleção desse aço foi feita tomando-se como base as características obtidas através de análises realizadas em campo e de microdureza e microestrutura das lâminas de corte já existentes no processo confeccionadas com aço importado. Com o aço selecionado em mãos, aplicou-se dois tratamentos térmicos diferentes de têmpera e revenido (um proposto pelo fabricante e outro proposto pelo trabalho em execução), onde avaliou-se o efeito dos tratamentos térmicos sobre as propriedades mecânicas e microestrutural do material. Através da análise dos resultados da relação entre dureza e tenacidade, constatou-se que para os dois tratamentos térmicos aplicados, não houve variações significativas das propriedades mecânicas do material, e que os dois tratamentos apresentaram resultados satisfatórios. O aço ferramenta nacional especificado apresentou-se como alternativa para substituição do aço importado utilizado atualmente. Testes obtidos em campo com a lâmina fabricada com o aço nacional especificado nesse estudo e que recebeu o tratamento térmico proposto pelo fabricante (FAB), corroboraram com a análise das propriedades, visto que se constatou aumento do tempo de vida de corte em mais de 30%. / The tool steels have an important participation in the world market with regard to engineering. They are used in the metal-mechanic industry as cutting tools, molds, punches, among other applications. Because of its great importance, it is essential to discuss the relationship between the microstructure and the mechanical properties, since it is a common practice in industry to specify thermal treatments based mainly on the final hardness of the material, without considering that for a same hardness value a steel tool may have different mechanical properties, depending on the heat treatment cycle applied. Therefore, the selection of heat treatment is a relevant technological aspect in the performance of these steels. Considering the wide possibility of mechanical properties obtained (fracture toughness) with different thermal treatments, this work had the objective of specifying a national tool steel and a set of thermal treatment parameters that allow the use of this material as a substitute for a another imported steel used in the manufacture of cutting blades used in the processing of lead plates. The steel selected for the development of this work was AISI D6 steel, the selection of this steel was made taking as a base the characteristics obtained through field analysis and microhardness and microstructure of the cutting blades already in the process made with steel imported. With the selected steel in hand, two different tempering and tempering treatments were applied (one proposed by the manufacturer and another proposed by the work in progress), where the effect of the thermal treatments on the mechanical and microstructural properties of the material was evaluated. By analyzing the results of the relationship between hardness and toughness, it was found that for the two thermal treatments applied, there were no significant variations of the mechanical properties of the material, and that both treatments presented satisfactory results. The specified national steel tool was presented as an alternative to replace the currently used imported steel. Field tests with the blade manufactured with the national steel specified in this study and that received the thermal treatment proposed by the manufacturer (FAB), corroborated with the analysis of the properties, as it was observed an increase in the cutting life time in more than 30 %.

Ovako Sweden AB i Hällefors har vid seghärdning av stål problem med sprickor. Studier visar på att tillsatser av polymer i kylvattnet ger ett långsammare och jämnare kylförlopp, vilket minskar risken för sprickor. För att fastställa vilken mängd polymer som är lämplig att tillsätta i kylvattnet vid härdning av deras låglegerade segment av seghärdat stål, så har undersökningar utförs på två stålsorter. Skillnaden i härdresultat mellan de olika testade koncentrationsnivåerna var små, men vid högre polymerkoncentration så fördelades hårdheten något jämnare genom hela tvärsnittet. / Ovako Sweden AB have problems with cracks during the process of hardening of steel. Studies show that the additives of polymer in the cooling water gives a slower and more even cooling process, which reduce the risk of crack onset. To decide the amount of polymer that is suitable to put in the cooling water at the hardening of their low-alloy steel segment of quenched and tempered steel, so studies have been conducted on two types of steel. The difference in hardening results between different tested concentration levels were small, but at higher polymer concentration the hardness was distributed slightly more evenly throughout the cross section.

One of the most important additives in High Speed Steels (HSS) is cobalt, mainly for its effect on the hot properties. Based on statistic data about the increased price of cobalt and its negative effect on human health, an ethical and financial barrier in the steel industry have occurred. In order to solve the problem, it is of great importance to examine the future cobalt price and accessibility, as well as examine the possibility of finding alternative substitutes to cobalt. The purpose of this project was therefore to examine alternatives to cobalt as an alloying element in HSS. A qualitative literature study was performed by analyzing the economy of cobalt, studying the main reasons for cobalts tendency to improve the hot properties of the steel and finding alternative elements to replace, or at least reduce, cobalt in HSS without degrading the hot properties. Cobalt is used both in the chemical and metallurgical business. But the demand of cobalt is largely driven by chemical purposes with the focus on its rechargeable battery applications. The analysis shows that there is nothing pointing at a significant decrease of the price of cobalt. Lithium ion batteries stands for about 50% of current cobalt supply, which is why the price has surged the recent years. The market for electric vehicles and rechargeable batteries has skyrocketed. To decrease the price of cobalt, a substitute for cobalt in rechargeable batteries would need to be found, which is not very likely for the time being. The effect of cobalt in HSS is mainly on the red hardness and tempering resistance. Cobalt increases the bonding strength in the steel matrix and changes the microstructure of the finer secondary carbides. Also the growth rate and coalescence rate of the carbides decreases. This causes the red hardness and the tempering resistance to increase. To replace cobalt, several alternative alloying elements have been researched. Among the most promising are niobium, nitrogen and aluminium, where niobium were found to be of most interest, due to the broad support of relevant articles in the field of powder metallurgical processing. The positive effect of niobium could be regarded as three-fold. The first contribution is the refinement of grain size and homogeneity of the primary carbides, which increases the overall hardness. The second effect is that the addition of niobium shifts the phase equilibria in such a way that the precipitation of primary carbides mainly will be in the form of hard and stable NbC. The majority of the other alloying elements will hence be precipitated as secondary carbides during tempering. The final effect is an increase in secondary hardness, as a consequence of the large amounts of vanadium and smaller amounts of niobium that is being precipitated during tempering to the secondary carbides. This enables a high matrix hardening potential in the optimal state of tempering.

Made available in DSpace on 2014-10-09T12:55:34Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:54Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Os tratamentos de cementação, têmpera, revenimento e jateamento por granalhas são muito utilizados na produção seriada de peças da indústria automobilística, como engrenagens e eixos. Variações destes processos podem influenciar a vida em fadiga por flexão dos componentes descritos. O objetivo deste trabalho foi estudar a influência de variações no tempo de jateamento por granalhas, variações na temperatura de revenimento e de diferentes profundidades de oxidação intergranular, no crescimento de trincas curtas por fadiga na camada cementada do aço DIN 20MnCr5. Para isso foram feitos ensaios de fadiga por flexão em quatro pontos, utilizando corpos de prova de seção retangular e sem entalhe. Para o acompanhamento do crescimento de trincas curtas foi utilizado o método de réplicas de acetato. Foram estudados seis níveis de jateamento, quatro níveis de revenimento e dois níveis de oxidação intergranular. Como resultados principais, foram obtidas curvas de comprimento de trinca por número de ciclos e taxa de crescimento de trinca por tamanho médio da trinca. Amostras jateadas entre trinta minutos e uma hora, revenidas à 160&#176C e com oxidação intergranular por volta de dez mícrons, apresentaram os melhores resultados em relação à vida em fadiga. / Carburizing, quenching, tempering and shot peening treatments are often used in mass production of automotive parts, such as gears and shafts. Changes in these treatments can influence the bending fatigue life of these parts. The purpose of this study was to measure the influence of different shot peening times, different tempering temperature and different internal oxidation depths, on the short fatigue crack growth in case carburized DIN 20MnCr5 steel. Four-point-bend fatigue tests were carried out in rectangular section specimens without notch. The surface short crack growth was monitored by means of acetate replication technique. Six levels of shot peening, four levels of tempering temperatures and two levels of internal oxidation were studied in this work. Crack length versus number of cycles and crack growth rate versus mean crack length were obtained as principal results. Shot peening from 30 minutes to one hour, tempering at 160#176C and a lO~m depth of internal oxidation showed the best results in fatigue life.