Orientador: Isabel Cristina Sales Fontes Jardim / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T10:34:05Z (GMT). No. of bitstreams: 1 Ferreira_ClaudiodeCastro_M.pdf: 1652977 bytes, checksum: b266745fcbc738cc97c41fdc4d79a00b (MD5) Previous issue date: 2014 / Resumo: / Resumo: Neste trabalho, prepararam-se fases estacionárias (FE) fluoradas capeadas para utilização em Cromatografia Líquida de Alta Eficiência em Fase Reversa (CLAE-FR). A preparação da FE consistiu na sorção do polímero poli(metil-3,3,3-trifluorproprilsiloxano) (PMTFS) sobre sílica, tipo B, com tamanho de partícula de 5 ?m, seguido de imobilização térmica a 226 oC, por 12 horas e extração com diclorometano, a fim de eliminar o polímero não aderido ao suporte. A FE imobilizada, Si(PMTFS), foi submetida à reação de capeamento com trimetilclorossilano e hexametildissilaxano, para a redução dos grupos silanóis que não foram recobertos pelo polímero. Testes físico-químicos e cromatográficos comprovaram a eficiência da imobilização do polímero e do capeamento. O desempenho cromatográfico da FE fluorada capeada, Si(PMTFS)ec, foi superior ao da não capeada e os testes de Tanaka e colaboradores demonstraram que o capeamento diminuiu a atividade silanofílica da FE e aumentou a sua hidrofobicidade. A FE Si(PMTFS)ec apresentou o mecanismo "U-shape", pois se observou o aumento da retenção de compostos básicos e polares em altas porcentagens do modificador orgânico na fase móvel. As FE de Si(PMTFS)ec apresentaram estabilidade química superior às FE não capeadas, porém, elas mostraram-se mais instáveis que as FE C8, C18 preparadas no grupo. Embora a estabilidade química à fase móvel em meio básica seja uma desvantagem, a mesma possui o mecanismo "U-shape" que pode ser utilizado para aumentar a retenção dos compostos básicos, sem o uso de condições drásticas de pH, além de ser uma FE mais apropriada quando se emprega o espectrômetro de massas, pois a alta concentração de solvente orgânico na fase móvel melhora a ionização dos analitos, aumentando as suas detectabilidades. A FE Si(PMTFS)ec constitui em uma alternativa bem sucedida para emprego em CLAE-FR, devido a sua capacidade em separar vários tipos de compostos / Abstract: / Abstract: In this work, end-capped fluorinated stationary phases (SP) for use in High-Performance Liquid Chromatography on Reversed Phase (RP-HPLC) were prepared. The preparation of the SP consisted in the sorption of the polymer poly(methyl-3,3,3-trifluorproprilsiloxane) (PMTFS) onto type B silica, with particle size of 5 µm, followed by thermal immobilization at 226 °C for 12 h and extraction with dichloromethane to eliminate the polymer that had not interacted with the support. The immobilized SP, Si (PMTFS), was subjected to an end-capping reaction to reduce the silanol groups that were not covered by the polymer. Physical-chemical and chromatographic tests were conducted to evaluate the efficiency of the immobilization of the polymer and of the end-capping reaction. The chromatographic performance of the end-capped fluorinated SP, Si (PMTFS)ec, was greater than that of the non-end-capped phase. The Tanaka tests showed a decrease in silanophilic activity and an increase in hydrophobicity. The Si (PMTFS)ec SP showed a U-shaped mechanism, because of the observed increase in retention of basic compounds at high percentages of the organic component in the mobile phase. The Si (PMTFS)ec SP showed superior chemical stability to non-end-capped SP, however, less stability than C8 and C-18 SP also prepared by the group. Although chemical stability in alkaline mobile phase is a disadvantage, it has a "U-shape" mechanism that can be used to increase the retention of basic compounds without the use of drastic conditions of pH, and is more appropriate for use with a mass spectrometer. Due to the high concentrations of organic solvent in the mobile phase the ionization of the analytes is better, increasing the detectability. The Si (PMTFS)ec SP can be used in RP-HPLC due to its ability to separate various types of compounds / Mestrado / Quimica Analitica / Mestre em Química

Tato práce se zabývá využitím distribucí neboli zobecněných funkcí k řešení nestacionárních okrajových problémů v mechanice kontinua. Nejprve je zavedena teorie distribucí a jejich definice jako spojitých lineárních funkcionálů na prostoru testovacích funkcí. Druhá část teoretické kapitoly představuje Laplaceovu integrální transformaci. Následující kapitola se věnuje řešení průhybu nosníků pod vlivem nespojitého časově proměnlivého zatížení. Jejím výsledkem je vytvoření obecného modelu řešení průhybových čar nosníků vužitím distribucí. Poslední kapitola se zabývá řešením nestacionárního proudění v trubicích spojených hydraulickými prvky.

The doctoral thesis focuses on a Vold-Kalman filter (VKF). Theoretical part describes properties of VKF and other order tracking methods, namely computed order tracking (COT) and Gabor order tracking (GOT). It also characterizes requirements for rotational speed measurements as one of the key elements for correct functionality of VKF. Practical part depicts own filter implementation and its properties. Main stress is put on computational efficiency, that is in result better than in available codes. Thesis also points out possible issues with numerical instabilities within calculation caused by limited dynamic range of double data type. This is solved by restricting the inputs to prevent the instabilities. Restriction is applied also to cases where the result is numerically correct but unusable. Following part extends the comparison with methods STFT, COT and GOT, where benefits of VKF for nonstationary conditions are shown. The last section shows given information used on simulated signals. This is then applied to show mentioned techniques on experimental data, for instance from turbo engine or electric motor, where the ability of VKF in checking the accordance between speed profile and vibration data is illustrated.

Tato práce se zabývá a analyzuje možnosti, kterými je možno zjistit geografickou polohu ze snímků nebo videa pouze za použití vizuální informace z obrazu.    Výsledkem práce jsou dvě rozdílné metody geo-lokalizace. První z nich pracuje na principu hledání časů východu a západu Slunce. Hlavní výhodou této metody je její univerzálnost. Funguje s jakoukoliv kamerou umístěnou v externích prostorech a nevyžaduje přítomnost žádných specifických objektů ve scéně. Pro správný výsledek je třeba alespoň celodenní záznam z kamery. Výsledky jsou uspokojivé za každého počasí. Druhá metoda pracuje na základě analýzy stínů ve scéně. Správnou pozici je možno určit, s poměrně velkou přesností, pouze na základě dvou snímků pořízených v různém čase. Tato metoda vyžaduje přítomnost dvou objektů v obraze, které vrhají stín. Přesnosti výsledků navržených metod jsou vyhodnoceny a porovnány. Z výsledků vyplývá, že obě metody lze úspěšně použít pro odhad geografické polohy. Dále byla v rámci práce pořízena rozsáhlá datová sada obrazových sekvencí z volně přístupných webových kamer.

Ces dernières années, de nouveaux matériaux bidimensionnels aux propriétés surprenantes ont été découverts, le plus connu étant le graphène. Dans ces matériaux, les électrons du niveau de Fermi ont une masse apparente nulle, et peuvent être décrits par l’équation de Dirac sans masse. Un tel phénomène apparaît dans des situations très générales, pour les matériaux bidimensionnels ayant une structure périodique en « nid d’abeille ». De plus, la prise en compte d’interactions mène à des équations de Dirac non linéaires. Ces équations apparaissent également dans l’étude des paquets d’ondes lumineuses dans certaines fibres optiques. Le but de cette thèse est d’étudier l’existence et la stabilité de solutions stationnaires de ces équations avec termes non linéaires sous-critiques et critiques, et de montrer qu’ils sont la limite de solutions stationnaires de l’équation de Schrödinger non linéaire à potentiel périodique dans certains régimes de paramètres. Du point de vue mathématique, on devra résoudre les équations d’Euler-Lagrange de fonctionnelles d'énergie fortement indéfinies faisant intervenir l’opérateur de Dirac. Il s’agira en particulier d’étudier le cas des non-linéarités avec exposant critique, encore mal comprises pour ce type de fonctionnelle, et qui apparaissent naturellement en optique non linéaire. Les résultats de cette thèse pourraient avoir un impact important en physique, en particulier en physique du solide et optique non linéaire. / Recently, new two-dimensional materials possessing unique properties have been discovered, the most famous being the graphene. In this materials, electrons at the Fermi level behave as massless particles and can be described by the massless Dirac equation. This phenomenon is quite general, and it is a common features of "honeycomb" periodic structures. Moreover, taking into account interaction leads to non-linear Dirac equations, which also appear in the description of light propagation in particular waveguides. The aim of the thesis is to study existence and stability of stationary solutions for those equations with both sub-critical and critical nonlinearities, and to show that they are limit of stationary solutions to the Schroedinger equation with honeycomb potential, for a suitable choice of parameters. This amounts to solving the Euler-Lagrange equation for strongly indefinite energy functionals, involving the Dirac operator. We will deal with critical nonlinearities, which are still poorly understood, and appear naturally in non-linear optics. This results may have an impact on the understanding some solid state or nonlinear optics systems.

The paper considers systems of linear first-order ODEs with a randomly perturbed system matrix and stationary additive noise. For the description of the long-term behavior of such systems it is necessary to study their stationary solutions. We deal with conditions for the existence of stationary solutions as well as with their representations and the computation of their moment functions. Assuming small perturbations of the system matrix we apply perturbation techniques to find series representations of the stationary solutions and give asymptotic expansions for their first- and second-order moment functions. We illustrate the findings with a numerical example of a scalar ODE, for which the moment functions of the stationary solution still can be computed explicitly. This allows the assessment of the goodness of the approximations found from the derived asymptotic expansions.

(EN) Cellulose tris-(3,5-dimethylphenylcarbamate) chiral stationary phase was used for separation of selected 24 analytes. Enantioseparations were realized using two systems, high performance liquid chromatography and supercritical fluid chromatography. Effect of mobile phase composition was studied. Five different aditives (isopropylamine, diethylamine, triethylamine, trifluoroacetic acid, isopropylamine combined with trifluoroacetic acid) and their influence on enantioseparation were tested. Influence of two different modifiers (methanol, propan-2-ol) combined with all aditives was also tested in supercritical fluid chromatography system. The aim of this work was to find optimized composition of mobile phase which was suitable for separation of the analytes studied and to compare separation potential among all mobile phases and also between used separations systems. The supercritical fluid chromatography was shown to yield better results, i.e. better resolution in shorter analysis time. However examples of analytes better resolved under optimized conditions in high performance liquid chromatography system have also been found. Keywords (EN) Chirality, enantiomers, enantioselective separation, chiral stationary phase, high performance liquid chromatography, supercritical fluid chromatography.

(EN) This dissertation thesis is focused on physicochemical and chromatographic characterization of polyaniline-coated stationary phases. In the first part, surfaces of bare silica and octadecyl silica sorbents were modified by in-situ chemical polymerization of aniline hydrochloride and their subsequent systematic characterization was performed by using the linear solvation energy relationship approach in the HILIC mode of capillary LC. In addition, several common physicochemical techniques were used to characterize properties of these altered materials. The modified sorbents were then packed into capillary columns. The retention interactions taking place between solute and the separation system were evaluated on the basis of retention data of a number of various solutes. The results showed that polyaniline coating had a significant effect on the retention promoting interactions of both polyaniline-coated stationary phases. The assumed mixed-mode retention mechanism was proven for both the stationary phases. The second part dealt with investigation of the separation potential of polyaniline- coated silica stationary phase in different chromatographic modes. The retention factor curves of structurally similar solutes were constructed as a function of organic modifier portion in the mobile phase....

The test facility ROCOM (Rossendorf Coolant Mixing Model) has been built for the investigation of coolant mixing processes in the reactor pressure vessel of pressurised water reactors (PWR). ROCOM is a 1:5 model of the German PWR KONVOI and has been designed for a wide range of different mixing scenarios. ROCOM disposes of four loops with fully controllable coolant pumps. The test facility is operated with demineralised water. For the investigation of mixing, tracer solution (water labelled with salt) is injected into the facility. The transient distribution of the electrical conductivity is is measured at different positions of the flow path by means of wire-mesh sensor technique with high resolution in space and time. The measured conductivity is transformed into a dimensionless mixing scalar. The mixing at quasi-stationary conditions (constant loop mass flow rates) has been investigated in the presented experiments. That concerned nominal operation conditions, the operation with a reduced number of loops and the investigation of cold-water transients with running pumps and conditions of developed natural circulation. In special experimental series, the reproducibility of the results at identicla boundary conditions within the confidence intervalls has been shown. Further, the influence of various factors on the mixing has been investigated. This included the pressure losses at the core bottom plate, the global coolant flow level and the influence of the loop flow rate on the perturbed sector at the core inlet. An analysis of the measurement error of the used measurement technique completes the report.

According to the 20-20-20 targets set by the European Union, 50 percent of the Swedish electricity share is to be provided by renewable energy sources by 2020. The Smart Grid Gotland (SGG) project has emerged as a response to this target. The project aims at demonstrating a proof of concept on how smart grid solutions can be used to integrate large quantities of renewable energy sources in an existing network. The outcomes of the project are intended to pave the way for future renewable energy integration projects in Sweden. The Thesis focuses on one of the technical objectives of the SGG project, i.e. to increase the hosting capacity of wind power on Gotland from 195 MW to 200 MW by using Demand-Response (DR) from households and industries. DR consist of shifting peak-loads to peakproduction hours. The integration of additional wind power causes a risk of exceeding the transmission capacity of the power export cable between Gotland and the Swedish mainland. The approach considered for this Thesis is to use an Ancillary Service (AS) toolbox scheme based on multi-agent systems. The AS toolbox consist of flexibility tools such as DR on long-term, short-term, a battery energy storage system and a wind curtailment scheme. The DR activity includes space heating and domestic hot water consumption from detached houses on Gotland. The simulation results indicate that 1900 household participants are sufficient to balance the additional 5 MW for worst case scenarios. Furthermore, it is shown that the DR participation from industries contributes in some cases to a reduction of 700 household participants. The findings helped conclude that using an AS toolbox solution on Gotland is fully possible from a technical perspective. However, barriers that stand against its realisation are of economical nature and need to be investigated in future studies.