Esta dissertação poderia ser dividida em duas partes, sem que houvesse prejuízo para o seu entedimento: uma tratando do topázio natural (Al IND.2 SiO IND.4[F, OH] IND.2) e outra, a respeito dos vidros silicatos tipo soda-lime (SiO IND.2+CaO+Na IND.2 O). Em ambas se procura contribuir para o estudo de defeitos com algumas técnicas experimentais, mais enfaticamente as correntes de despolarização termicamente estimuladas (CDTE). Com relação ao topázio, há diversos estudos tratando de sua termoluminescência (TL) e de possíveis aplicações no que tange ao seu emprego como dosímetro termoluminescente. Procuramos complementar esses resultados com medidas de CDTE, técnica que ainda não havia sido utilizada para este material. Localizamos no topázio três bandas de CDTE, porém os resultados não são conclusivos no que se refere às origens dessas bandas. Em parte porque temos consciência de que os resultados variam bastante quando se estudam amostras naturais, com composições que variam dentro de um mesmo pedaço de cristal. No que diz respeito aos vidros soda-lime, o estudo foi mais abrangente. Há várias trabalhos no sentido de se conhecer melhor os efeitos causados pela irradiação de vidros silicatos. Acredita-se que o sódio desempenhe um papel fundamental nas principais mudanças processadas nesse material após irradiação gama. Assim, este estudo procurou comparar os resultados de TL e CDTE, além de absorção óptica, de vidros soda-lime com diferentes concentrações de Na POT.+ e K POT.+. Ao que tudo indica os processos responsáveis pela TL e CDTE dependem da relação entre as concentrações desses íons. Verificaram-se também variações com a taxa de dose, e os efeitos de tratamentos térmicos para situações onde um ou outro íon prevalece. / This work could be split in two different parts without impairment understanding. One of them, on natural topaz (Al2SiOdF,OH] 2) and the other on soda-lime silicate (SLS) glasses (Si02 + CaO + Na20) . In both of them we intend to contribute with more information on their defect composition, using some experimental techniques, especially the so called thermally stimulated depolarization currents (TSDC) . There are many surveys on topaz thermoluminescence (TL) and the possibility of its use as a TL dosimeter. So, one of the purposes of this study was to make a contribution with a technique not used so far with such material. We have detected three TSDC peaks. The results are not conclusive about the origin of those peaks, in part because we are dealing with a natural material whose composition can vary even within the same piece of crystal. As the SLS glasses, the study was more comprehensive. There are plenty of papers on irradiation effects in silicate glasses and attempts to understand the mechanisms responsible for them. It is believed that sodium plays a fundamental role in the main modifications caused by gamma irradiation of these glasses. In addition, this study attempts to compare the TL and TSDC results in SLS glasses with different concentrations of Na+ and K+. From our observations, the processes responsible for both TL and TSCD peaks depend on the relative concentrations of those ions. Furthermore, variations on the signals were also noticed; depending on the irradiation rate and on the thermal treatments performed, in samples where one or another ion prevails.

Esta dissertação poderia ser dividida em duas partes, sem que houvesse prejuízo para o seu entedimento: uma tratando do topázio natural (Al IND.2 SiO IND.4[F, OH] IND.2) e outra, a respeito dos vidros silicatos tipo soda-lime (SiO IND.2+CaO+Na IND.2 O). Em ambas se procura contribuir para o estudo de defeitos com algumas técnicas experimentais, mais enfaticamente as correntes de despolarização termicamente estimuladas (CDTE). Com relação ao topázio, há diversos estudos tratando de sua termoluminescência (TL) e de possíveis aplicações no que tange ao seu emprego como dosímetro termoluminescente. Procuramos complementar esses resultados com medidas de CDTE, técnica que ainda não havia sido utilizada para este material. Localizamos no topázio três bandas de CDTE, porém os resultados não são conclusivos no que se refere às origens dessas bandas. Em parte porque temos consciência de que os resultados variam bastante quando se estudam amostras naturais, com composições que variam dentro de um mesmo pedaço de cristal. No que diz respeito aos vidros soda-lime, o estudo foi mais abrangente. Há várias trabalhos no sentido de se conhecer melhor os efeitos causados pela irradiação de vidros silicatos. Acredita-se que o sódio desempenhe um papel fundamental nas principais mudanças processadas nesse material após irradiação gama. Assim, este estudo procurou comparar os resultados de TL e CDTE, além de absorção óptica, de vidros soda-lime com diferentes concentrações de Na POT.+ e K POT.+. Ao que tudo indica os processos responsáveis pela TL e CDTE dependem da relação entre as concentrações desses íons. Verificaram-se também variações com a taxa de dose, e os efeitos de tratamentos térmicos para situações onde um ou outro íon prevalece. / This work could be split in two different parts without impairment understanding. One of them, on natural topaz (Al2SiOdF,OH] 2) and the other on soda-lime silicate (SLS) glasses (Si02 + CaO + Na20) . In both of them we intend to contribute with more information on their defect composition, using some experimental techniques, especially the so called thermally stimulated depolarization currents (TSDC) . There are many surveys on topaz thermoluminescence (TL) and the possibility of its use as a TL dosimeter. So, one of the purposes of this study was to make a contribution with a technique not used so far with such material. We have detected three TSDC peaks. The results are not conclusive about the origin of those peaks, in part because we are dealing with a natural material whose composition can vary even within the same piece of crystal. As the SLS glasses, the study was more comprehensive. There are plenty of papers on irradiation effects in silicate glasses and attempts to understand the mechanisms responsible for them. It is believed that sodium plays a fundamental role in the main modifications caused by gamma irradiation of these glasses. In addition, this study attempts to compare the TL and TSDC results in SLS glasses with different concentrations of Na+ and K+. From our observations, the processes responsible for both TL and TSCD peaks depend on the relative concentrations of those ions. Furthermore, variations on the signals were also noticed; depending on the irradiation rate and on the thermal treatments performed, in samples where one or another ion prevails.

This dissertation explores the different ways to create thin film-based biosensors that are capable of rapid and label-free detection of cortisol, a non-specific biomarker closely linked to stress, within the physiological range of 10pM to 10 uM. Increased cortisol levels have been linked to stress-related diseases, such as chronic fatigue syndrome, irritable bowel syndrome, and post-traumatic stress disorder. It also plays a role in the suppression of the immune system as well. Therefore, accurate measurement of cortisol in saliva, serum, plasma, urine, sweat, and hair, is clinically significance to predict physical and mental diseases. In this dissertation, thin film-based electrochemical immunosensors were fabricated using a self-assembled monolayer (SAM) functionalized by cortisol specific antibodies to detect cortisol at 10 pM level sensitivities in the presence of a redox probe. The fabricated electrochemical cortisol immunosensors were able to detect cortisol in human saliva samples and the outcomes were validated using the standard Enzyme Linked Immuno Sorbent Assay (ELISA) technique. With the aim of improving signal amplification and label-free cortisol detection, copper nanoparticles were incorporated on screen-printed carbon electrodes (SPCE) for the fabrication of electrochemical cortisol immunosensor. This SPCE-based sensor showed a sensitivity of 4.21µA/M and the limit of detection 6.6nM. Both the SAM and SPCE-based immunosensors were not thermally stable due to the instability of antibodies at room temperature. To address this issue, an antibody-free immunosensor was fabricated. Molecular Imprinted Polymer (MIP) was used to template the target cortisol molecule. The MIP-based sensing platform was prepared using polypyrrole, a thermally stable conducting polymer. The conductivity of the polymer ensured good electrical performance. The polypyrrole-based MIP was synthesized by means of electrochemical polymerization and was used to detect cortisol within the physiological range at room temperature. MIP-based sensors exhibited the detection limit of 1 pM, and were cost-effective, easy to fabricate, temperature stable, and reusable. The sensing performance of the resulting sensors was comparable to those of commercially available technologies, such as ELISA. Aiming to perform cortisol sensing at point-of-care (POC), an Extended Gate Field Effect Transistor (EGFET) was integrated with a developed MIP cortisol sensor. The as developed MIP-EGFET sensor was used to detect the cortisol concentration in the range of 1 pM to 100 nM. A few of the major advantages of the developed sensor are its ability to provide a direct readout and simpler electronic systems, which are necessary for miniaturized Point of Care devices.

The performance of a combined vapor-compression cycle/ORC is evaluated using waste-heat from a diesel generator. A flat plate microchannel heat exchanger is employed to provide energy exchange between the diesel exhaust stream and an oil loop, which provides energy to a boiler. This study finds an increased diesel duty corresponds with an increased cooling capacity, for a maximum of 5 kW of cooling (with 13.5 kWe diesel load). System COP is reduced with a higher input power due to limitations in the cooling cycle. A number of solutions are identified to increase the COP and cooling capacity. A new microchannel heat exchanger to recovery heat is designed to increase performance compared to the previous version. / Graduation date: 2012

This thesis presents a new theoretical formalism which incorporates dynamical effects in atomistic electronic structure and related calculations. This research, fundamental by nature, brings about a deeper understanding of the dynamical processes in a range of materials. This establishes technologically important correlation with experimentally measured macroscopic properties and materials characterization. This method—the first of its kind—is a natural and long overdue extension of customary adiabatically separated time-independent electronic structure methods. It accounts explicitly for atomic motion due to thermal and zero-point vibration. The approach developed requires no direct treatment of time dependence in the quantum mechanical calculations, making the method widely applicable utilizing currently available electronic structure and ab-initio molecular dynamics software. The formalism is extensively applied and demonstrated for the linear optical response of bulk gallium arsenide and electronic structure of the C(111) 2 x 1 surface. Both cases are complimented by comparison of key observables to experimental data which may be used to judge the quality of the results. The results are found to be in good agreement with experimental data, with most exceptions being readily explainable and well understood.

På dagens fönsterglasmarknad har produkter med samma funktioner och utseende fått olika namn. Detta är förvirrande och gör det svårt för en person som ska beställa fönsterglas att jämföra olika tillverkares produkter med varandra. Rapporten är tänkt som en översikt på de olika fönsterglasen som finns på marknaden idag och även på sådant som kan bli aktuellt i framtiden. Den berör också sådant som kan vara av värde att veta vid användning av fönsterglas. Målgruppen är alla som kan tänkas ha intresse i ämnet - alltifrån hobbybyggaren till fackmän i byggbranschen. Informationen är sammanställd från böcker, broschyrer, internet och experter på området fönsterglas.

Trapping centres in as-grown TlInS2 layered single crystals have been studied by using a thermally stimulated current (TSC) technique. TSC measurements have been performed in the temperature range of 10-300 K with various heating rates. Experimental evidence has been found for the presence of five trapping centres with activation energies 12, 14, 400, 570 and 650 meV. Their capture cross-sections and concentrations were also determined. It is concluded that in these centres retrapping is negligible as confirmed by the good agreement between the experimental results and the theoretical predictions of the model that assumes slow retrapping. An exponential distribution of traps was revealed from the analysis of the TSC data obtained at different light excitation temperatures. The transmission and reflection spectra of TlInS2 crystals were measured over the spectral region of 400-1100 nm to determine the absorption coefficient and refractive index. The analysis of the room temperature absorption data revealed the coexistence of the indirect and direct transitions. The absorption edge was observed to shift toward the lower energy values as temperature increases from 10 to 300 K. The oscillator and the dispersion energies, and the zero-frequency refractive index were also reported. Furthermore, the chemical composition of TlInS2 crystals was determined from energy dispersive spectroscopic analysis. The parameters of monoclinic unit cell were found by studying the x-ray powder diffraction.

<p>På dagens fönsterglasmarknad har produkter med samma funktioner och utseende fått olika namn. Detta är förvirrande och gör det svårt för en person som ska beställa fönsterglas att jämföra olika tillverkares produkter med varandra. Rapporten är tänkt som en översikt på de olika fönsterglasen som finns på marknaden idag och även på sådant som kan bli aktuellt i framtiden. Den berör också sådant som kan vara av värde att veta vid användning av fönsterglas. Målgruppen är alla som kan tänkas ha intresse i ämnet - alltifrån hobbybyggaren till fackmän i byggbranschen. Informationen är sammanställd från böcker, broschyrer, internet och experter på området fönsterglas.</p>

During the last decades the specific manipulation of matter on the (sub-) nanometer scale, also known as nanoscience, became possible by technologies such as the scanning tunneling microscope. Nanocatalysts, i.e. catalytic active structures of up to a few nanometers in size, belong to this rather new class of materials. Unlike ordinary ’macroscopic’ catalytic materials, the performance of nanocatalysts does not simply scale, for instance, with the surface to volume ratio of the active material. In this Thesis model nanocatalysts are investigated by means of ab-initio density functional theory calculations. In paper I, we explain the experimentally observed catalytic characteristics of small gold clusters, Au1-4, on a regular magnesium oxide terrace towards the oxidation of carbon monoxide by thoroughly studying the adsorption of CO and O2 on these clusters. In the subsequent paper II, we study the feasibility of a catalytic water-mediated CO oxidation reaction on Au1-4/MgO and find that this reaction mechanism is not assessable for Au2,4/MgO and unlikely for Au1,3/MgO. Papers III and IV concentrate on the reactivity of clusters in the gas phase. Particularly, we focus on the relative stability of Au13 isomers and its potential for O2 dissociation (paper III). We find the lowest energy isomers, which contain a triangular prism at their center surrounded by a ring of the remaining seven atoms, to be generally stable upon O2 adsorption. The dissociation of O2 at certain sites of Au13 is found to be exothermic. In paper IV we performed scans of the Born-Oppenheimer potential energy surfaces of neutral and charged Cu3, Ag3, and Au3 to explore the thermally excited vibrations of these trimers. While the Born-Oppenheimer surface of Cu3 exhibits one fairly deep energy minimum, it is comparatively flat with two shallow minima in the case of Ag3. Hence for Ag3 there exist many thermally accessible geometries in a wide range of angles and bond lengths. For Au3, two distinct energy minima appear, being well-separated by a barrier of 180 meV. Already at room temperature, we find bond lengths changes of up to 5% for the studied trimers. Choosing Au3 as a case study for the changed reactivity of thermally excited modes, we find CO to bind up to 150 meV stronger to the excited cluster. Gold deposited on graphene and graphite was observed to form larger aggregates. In paper V, we study the electronic structures, high mobility, and substrate-mediated clustering processes of Au1-4 on graphene. Already in the 1970s is was speculated that dispersion forces, i.e. van der Waals forces, significantly contribute to the adsorption energies of gold atoms on graphite. We accounted for van der Waals interactions in our density functional theory calculations (paper VI) and investigated the influence of these dispersion forces on the binding of copper, silver, and gold adatoms on graphene. While copper and gold show a mixed adsorption mechanism, i.e. chemical binding plus attraction due to the van der Waals forces, silver is purely physisorbed on graphene. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 719

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-16T18:20:30Z No. of bitstreams: 1 ANGELA LUCÍNIA URTIGA VASCONCELOS - TESE PPGEQ 2015..pdf: 3505212 bytes, checksum: 24fcdf4a2acef884f73f1502723a100d (MD5) / Made available in DSpace on 2018-03-16T18:20:30Z (GMT). No. of bitstreams: 1 ANGELA LUCÍNIA URTIGA VASCONCELOS - TESE PPGEQ 2015..pdf: 3505212 bytes, checksum: 24fcdf4a2acef884f73f1502723a100d (MD5) Previous issue date: 2015-08 / Capes / As operações de processos químicos periodicamente são interrompidas para realização de procedimentos de manutenção preventiva e/ou corretiva nos equipamentos que fazem parte do processo. Após a parada e as etapas do comissionamento dos equipamentos, dá-se início a operação de partida. A operação de partida dos processos químicos, em especial das colunas de destilação, é uma das etapas mais complexas observadas na prática industrial. O procedimento de partida de uma coluna de destilação pode levar desde algumas horas até dias para atingir o estado estacionário. Quanto maior o tempo necessário para que a operação da coluna alcance o regime estacionário, maior será a quantidade de produtos fora de especificação e maior será o consumo de energia, o que eleva os custos da operação. Embora a operação de partida seja uma etapa de extrema importância nas plantas químicas, ainda é pouco o número de pesquisas realizadas com relação a esse tema. Além disso, não foi encontrado na literatura consultada nenhum trabalho sobre a operação de partida dos sistemas de colunas de destilação termicamente acopladas. O sistema estudado consiste de duas colunas de destilação interconectadas por duas correntes, uma corrente no estado vapor e outra no estado líquido, onde uma das colunas é do tipo extrativa, utilizada para a separação da mistura azeotrópica etanol-água, e a outra é uma coluna de recuperação do solvente etilenoglicol. O presente trabalho teve por objetivo o desenvolvimento de procedimento de partida para o sistema de destilação extrativa termicamente acoplado estudado. Foi avaliado o comportamento dinâmico do sistema durante a operação de partida, bem como o efeito da variação do perfil da vazão do vapor de aquecimento no refervedor sobre o tempo total da partida, do efeito da composição da corrente de alimentação da coluna de recuperação sobre o tempo total da partida e do efeito do instante de alimentação do solvente na coluna extrativa sobre o tempo total da partida. A partir dos resultados e das análises realizadas, foi observado que a coluna de recuperação é quem demanda mais tempo para que a operação de partida do sistema seja concluída, logo quanto menor a quantidade de etanol que é alimentada na coluna de recuperação, menor o tempo total da partida do sistema. Foi observado também, que o solvente deve ser alimentado desde o início da operação de partida, pois quanto mais tardia a alimentação do solvente na coluna extrativa, maior é o tempo total da partida. / Preventive and/or corrective maintenance procedures in equipment’s process operations provoke periodically shut down in the plants. After the maintenance and commissioning step conclusions, initiate the equipment’s startup operation. The start-up operation of chemical processes, in particular distillation columns, is one of the most complex operations in industrial practice. The start-up procedure of a distillation column occurs in few hours or can to wait days to reach steady state. The longer the time required for the operation of the column reaches the steady state, the greater the amount of off-spec product and greater energy consumption. Therefore, the starting operation has a significant impact on operating costs. Although the startup operation is a step of great importance in chemical plants, still is little the number of researches performed with respect to this subject. Moreover, the literature focuses on startup conventional distillation columns. To fill this gap, this work focused startup distillation column thermally coupled. The system studied consists of two distillation columns. One of the columns is extractive distillation type used for separating the azeotropic mixture ethanol-water. The other is a solvent recovery column. The two column is interconnected by two streams. A stream is in vapor phase, and the another stream is in liquid phase. The dynamic behavior of the system was evaluated during the startup operation in a reference configuration. Then was studied the effect of varying the heating steam flow profile in the reboiler, the effect of the feed stream composition of the recovery column and the effect of the start solvent feed extraction column in the total startup time. From the results obtained, it was observed that the recovery column is responsible for most of the time required for completion of the starting. The smaller the amount of ethanol fed to the recovery column, the lower the total time of system startup. It was also observed that the solvent should be fed since the beginning of the start-up operation, because the later the feed of the solvent in the extractive column, the greater the total start-up time.