Interfaces between national and EU law: time limits in cross-border civil proceedings and their impact on the free circulation of judgments

The thesis aims at exploring possible legal solutions to remove the obstacles to the free circulation of judgments in the civil justice area that arise from the remarkably diverging national rules on procedural time limits. As shown by the case-law of the CJEU, time limits have recently come under closer scrutiny. The interplay between national and EU law illustrates that time limits raise significant deficiencies connected with the right to a fair trial under Art. 6 ECHR and Art. 47 CFR – e.g. the effective recovery of claims, effective judicial protection, effective cross-border enforcement of judgments – which negatively impact EU cross-border civil litigation. In order to overcome some of the weaknesses of the current legal framework governing the cross-border enforcement of judgments and strengthen the parties’ fundamental procedural rights the PhD thesis intends to determine whether and, to what extent time limits can be harmonised at EU level. EU action on time limits would indeed favour the speed, efficiency and proportionality of cross-border proceedings without sacrificing the fairness of the judicial process and the equality of the parties

Capillary bridging and long-range attractive forces in a mean-field approach

When a mixture is confined, one of the phases can condense out. This condensate, which is otherwise metastable in the bulk, is stabilized by the presence of surfaces. In a sphere-plane geometry, routinely used in atomic force microscope and surface force apparatus, it, can form a bridge connecting the surfaces. The pressure drop in the bridge gives rise to additional long-range attractive forces between them. By minimizing the free energy of a binary mixture we obtain the force-distance curves as well as the structural phase diagram of the configuration with the bridge. Numerical results predict a discontinuous transition between the states with and without the bridge and linear force-distance curves with hysteresis. We also show that similar phenomenon can be observed in a number of different systems, e.g., liquid crystals and polymer mixtures. (C). 2004 American Institute of Physics.

Neural-network approach to modeling liquid crystals in complex confinement

Finding the structure of a confined liquid crystal is a difficult task since both the density and order parameter profiles are nonuniform. Starting from a microscopic model and density-functional theory, one has to either (i) solve a nonlinear, integral Euler-Lagrange equation, or (ii) perform a direct multidimensional free energy minimization. The traditional implementations of both approaches are computationally expensive and plagued with convergence problems. Here, as an alternative, we introduce an unsupervised variant of the multilayer perceptron (MLP) artificial neural network for minimizing the free energy of a fluid of hard nonspherical particles confined between planar substrates of variable penetrability. We then test our algorithm by comparing its results for the structure (density-orientation profiles) and equilibrium free energy with those obtained by standard iterative solution of the Euler-Lagrange equations and with Monte Carlo simulation results. Very good agreement is found and the MLP method proves competitively fast, flexible, and refinable. Furthermore, it can be readily generalized to the richer experimental patterned-substrate geometries that are now experimentally realizable but very problematic to conventional theoretical treatments.

Neural-network approach to modeling liquid crystals in complex confinement

Finding the structure of a confined liquid crystal is a difficult task since both the density and order parameter profiles are nonuniform. Starting from a microscopic model and density-functional theory, one has to either (i) solve a nonlinear, integral Euler-Lagrange equation, or (ii) perform a direct multidimensional free energy minimization. The traditional implementations of both approaches are computationally expensive and plagued with convergence problems. Here, as an alternative, we introduce an unsupervised variant of the multilayer perceptron (MLP) artificial neural network for minimizing the free energy of a fluid of hard nonspherical particles confined between planar substrates of variable penetrability. We then test our algorithm by comparing its results for the structure (density-orientation profiles) and equilibrium free energy with those obtained by standard iterative solution of the Euler-Lagrange equations and with Monte Carlo simulation results. Very good agreement is found and the MLP method proves competitively fast, flexible, and refinable. Furthermore, it can be readily generalized to the richer experimental patterned-substrate geometries that are now experimentally realizable but very problematic to conventional theoretical treatments.

Modelos contínuos do solvente: fundamentos

Continuum solvation models are nowadays widely used in the modeling of solvent effects and the range of applications goes from the calculation of partition coefficients to chemical reactions in solution. The present work presents a detailed explanation of the physical foundations of continuum models. We discuss the polarization of a dielectric and its representation through the volume and surface polarization charges. The Poisson equation for a dielectric was obtained and we have also derived and discuss the apparent surface charge method and its application for free energy of solvation calculations.

Planar Topological Defects in Unconventional Superconductors

In this work, we consider the properties of planar topological defects in unconventional superconductors. Specifically, we calculate microscopically the interaction energy of domain walls separating degenerate ground states in a chiral p-wave fermionic superfluid. The interaction is mediated by the quasiparticles experiencing Andreev scattering at the domain walls. As a by-product, we derive a useful general expression for the free energy of an arbitrary nonuniform texture of the order parameter in terms of the quasiparticle scattering matrix. The thesis is structured as follows. We begin with a historical review of the theories of superconductivity (Sec. 1.1), which led the way to the celebrated Bardeen-Cooper- Schrieffer (BCS) theory (Sec. 1.3). Then we proceed to the treatment of superconductors with so-called "unconventional pairing" in Sec. 1.4, and in Sec. 1.5 we introduce the specific case of chiral p-wave superconductivity. After introducing in Sec. 2 the domain wall (DW) model that will be considered throughout the work, we derive the Bogoliubov-de Gennes (BdG) equations in Sec. 3.1, which determine the quasiparticle excitation spectrum for a nonuniform superconductor. In this work, we use the semiclassical (Andreev) approximation, and solve the Andreev equations (which are a particular case of the BdG equations) in Sec. 4 to determine the quasiparticle spectrum for both the single- and two-DW textures. The Andreev equations are derived in Sec. 3.2, and the formal properties of the Andreev scattering coefficients are discussed in the following subsection. In Sec. 5, we use the transfer matrix method to relate the interaction energy of the DWs to the scattering matrix of the Bogoliubov quasiparticles. This facilitates the derivation of an analytical expression for the interaction energy between the two DWs in Sec. 5.3. Finally, to illustrate the general applicability our method, we apply it in Sec. 6 to the interaction between phase solitons in a two-band s-wave superconductor.

Síntese e caracterização de tensoativos e estudo de equilíbrio de fase dos sistemas CnH2n+2/H2O/CnH2n+1COONa/But-OH

The growing utilization of surfactants in several different areas of industry has led to an increase on the studies involving solutions containing this type of molecules. Due to its amphiphilic nature, its molecule presents one polar part and one nonpolar end, which easily interacts with other molecules, being able to modify the media properties. When the concentration in which its monomers are saturated, the airliquid system interface is reached, causing a decrease in interfacial tension. The surfactants from pure fatty acids containing C8, C12 and C16 carbonic chains were synthesized in an alcoholic media using sodium hydroxide. They were characterized via thermal analysis (DTA and DTG) and via infrared spectroscopy, with the intention of observing their purity. Physical and chemical properties such as superficial tension, critical micelle concentration (c.m.c), surfactant excess on surface and Gibbs free energy of micellization were determined in order to understand the behaviour of these molecules with an aqueous media. Pseudo-ternary phase diagrams were obtained aiming to limit the Windsor equilibria conditions so it could be possible to understand how the surfactants carbonic chain size contributes to the microemulsion region. Solutions with known concentrations were prepared to study how the surfactants can influence the dynamic light scattering spectroscopy (DLS) and how the diffusion coefficient is influenced when the media concentration is altered. The results showed the variation on the chain size of the studied surfactant lipophilic part allows the conception of surfactants with similar interfacial properties, but dependent on the size of the lipophilic part of the surfactant. This variation causes the surfactant to have less tendency of microemulsionate oil in water. Another observed result is that the n-alcanes molecule size promoted a decrease on the microemulsion region on the obtained phase diagrams

Caracterização e aplicação de sistemas micelares e microemulsionados como inibidores de corrosão

Corrosion is an important phenomenon that frequently occurs in the oil industry, causing surface ablation, such as it happens on the internal surfaces of oil pipes. This work aims to obtain new systems to reduce this specific problem. The surfactants SDS, CTAB, and UNITOL L90 (in micellar and microemulsionated systems) were used as corrosion inhibitors. The systems were obtained using a C/S ratio of 2, butanol as cosorfactant, kerosene as oil phase and, as water phase, NaCl solutions of 0.5M with pH = 2, 4, and 7. Microemulsion regions were found both for direct and inverse micelles. SDS had the higher microemulsion region and the area was not dependent of pH. The study of micellization of these surfactans in the liquid-gas interface was carried out via the determination of CMC from surface tension measurements. Regarding microemulsionated systems, in the case of CTAB, CMC increased when pH was increased, being constant for SDS and UNITOL L90. Concerning micellar systems, increase in pH caused decrease and increase in CMC for SDC and CTAB, respectively. In the case of UNITOL L90, CMC was practically constant, but increased for pH = 4. The microemulsionated systems presented higher CMC values, except for UNITOL L90 L90. The negative values of free energy of micellization indicated that the process of adsorption was spontaneous. The results also indicated that, comparing microemulsionated to systems, adsorption was less spontaneous in the case of SDS and CTAB, while it did not change for UNITOL L90. SAXS experiments indicated that micelle geometry was spherical, existing also as halter and flat micelles, resuting in a better inght on the adsorption at the liquid-solid interface. Efficiency of corrosion inhibition as determined by electrochemical measurements, from corrosion currents calculated from Tafel extrapolation indicuting heat showed surfactants to be efficient even at low concentrations. Equilibrium isotherm data were fitted to the Freundlich model, indicating that surfactant adsorption occurs in the form of multilayers

Aplicação de sabões de ácidos graxos epoxidados como inibidores de corrosão em oleoduto

Corrosion usually occurs in pipelines, so that it is necessary to develop new surface treatments to control it. Surfactants have played an outstanding role in this field due to its capacity of adsorbing on metal surfaces, resulting in interfaces with structures that protect the metal at low surfactant concentrations. The appearance of new surfactants is a contribution to the area, as they increase the possibility of corrosion control at specific conditions that a particular oil field presents. The aim of this work is to synthesize the surfactants sodium 12 hydroxyocadecenoate (SAR), sodium 9,10-epoxy-12 hydroxyocadecanoate (SEAR), and sodium 9,10:12,13-diepoxy-octadecanoate (SEAL) and apply them as corrosion inhibitors, studying their action in environments with different salinities and at different temperatures. The conditions used in this work were chosen in order to reproduce oil field reality. The study of the micellization of these surfactants in the liquid-gas interface was carried out using surface tensiometry. It was observed that cmc increased as salt concentration was increased, and temperature and pH were decreased, while cmc decreased with the addition of two epoxy groups in the molecule. Using the values of cmc and the Gibbs equation, the values of Gibbs free energy of adsorption, area per adsorbed molecule, and surface excess were calculated. The surface excess increases as salt concentration and temperature decreases, increasing as pH is increased. The area per adsorbed molecule and the free energy of adsorption decrease with salt concentration, temperature, and pH increase. SAXS results showed that the addition of epoxy group in surfactant structure results in a decrease in the repulsion between the micelles, favoring the formation of more oblong micellar structures, ensuring a better efficiency of metal coverage. The increase in salt and surfactant concentrations provides an increase in micellar diameter. It was shown that the increase in temperature does not influence micellar structure, indicating thermal stability that is advantageous for use as corrosion inhibitor. The results of inhibition efficiency for the surfactants SEAR and SEAL were considered the best ones. Above cmc, adsorption occurred by the migration of micelles from the bulk of the solution to the metal surface, while at concentrations below cmc film formation must be due to the adsorption of semi-micellar and monomeric structures, certainly due to the presence of the epoxy group, which allows side interactions of the molecule with the metal surface. The metal resistance to corrosion presented values of 90% of efficiency. The application of Langmuir and Frumkin isotherms showed that the later gives a better description of adsorption because the model takes into account side interactions from the adsorbing molecules. Wettability results showed that micelle formation on the solid surface occurs at concentrations in the magnitude of 10-3 M, which isthe value found in the cmc study. This value also justifies the maximum efficiencies obtained for the measurements of corrosion resistance at this concentration. The values of contact angle as a function of time suggest that adsorption increases with time, due to the formation of micellar structures on metal surface

Índice de aromaticidade baseado na deslocalização, degenerescência e densidade (D3BIA) para acenos e moléculas homoaromáticas

The aromaticity index is an important tool for the investigation of aromatic molecules. This work consists on new applications of the aromaticity index developed by teacher Caio Lima Firme, so-called D3BIA (density, delocalization, degeneracy-based index of aromaticity). It was investigated its correlation with other well-known aromaticity indexes, such as HOMA (harmonic oscillator model of aromaticity), NICS (nucleus independent chemical shielding), PDI (para-delocalization index), magnetic susceptibility (), and energetic factor in the study of aromaticity of acenes and homoaromatic species based on bisnoradamantanyl cage. The density functional theory (DFT) was used for optimization calculations and for obtaining energetic factors associated with aromaticity and indexes HOMA and NICS. From quantum theory of atoms in molecules (QTAIM) it was obtained the indexes D3BIA, PDI and . For acenes, when the over-mentioned indexes were applied it was observed no correlation except for D3BIA and HOMA (R2=0.752). For bisnoradamantenyl dication and its derivatives, it was obtained a good correlation between D3BIA and NICS. Moreover, it was evaluated solely one of the factors used on D3BIA calculation, the delocalization index uniformity (DIU), so as to investigate its possible influence on stability of chemical species. Then, the DIU was compared with the formation Gibbs free energy of some pairs of carbocations, isomers or not, which each pair had small difference in point group symmetry and no difference among other well-known stability factors. The obtained results indicate that DIU is a new stability factor related to carbocations, that is, the more uniform the electron density delocalization, the more stable the is carbocation. The results of this work validate D3BIA and show its importance on the concept of aromaticity, indicating that it can be understood from degeneracy of atoms belonging the aromatic site, the electronic density in the aromatic site and the degree of uniformity of electron delocalization

Estudos de sorção de um corante aniônico modelo em partículas de quitosana reticulada

Textile activity results in effluents with a variety of dyes. Among the several processes for dye-uptaking from these wastewaters, sorption is one of the most effective methods, chitosan being a very promising alternative for this end. The sorption of Methyl Orange by chitosan crosslinked particles was approached using equilibrium and kinetic analyses at different pH s. Besides the standard pseudo-order analysis normally effectuated (i.e. pseudo-first-order and pseudo-second-order), a novel approach involving a pseudo-nth-order kinetics was used, nbeing determined via non-linear regression, using the Levenberg-Marquardt method. Zeta potential measurements indicated that electrostatic interactions were important for the sorption process. Regarding equilibrium experiments, data were well fitted to a hybrid Langmuir-Freundlich isotherm, and estimated Gibbs free energy of adsorption as a function of mass of dye per area of chitosan showed that the process of adsorption becomes more homogeneous as the pH of the continuous phase decreased. Considering the kinetics of sorption, although a pseudo-nth-order description yielded good fits, a kinetic equation involving diffusion adsorption phenomena was found to be more consistent in terms of a physicochemical description of the sorption process

A stability transition at mildly acidic pH in the alpha-hemolysin (alpha-toxin) from Staphylococcus aureus

The effects of mildly acidic conditions on the free energy of unfolding (Delta G(u)(buff)) of the pore-forming alpha-hemolysin (alpha HL) from Staphylococcus aureus were assessed between pH 5.0 and 7.5 by measuring intrinsic tryptophan fluorescence, circular dichroism and elution time in size exclusion chromatography during urea denaturation, Decreasing the pH from 7.0 to 5.0 reduced the calculated Delta G(u)(buff) from 8.9 to 4.2 kcal moI(-1), which correlates with an increased rate of pore formation previously observed over the same pH range, It is proposed that the lowered surface pH of biological membranes reduces the stability of alpha HL thereby modulating the rate of pore formation. (C) 1999 Federation of European Biochemical Societies.

On the entropy operator for the general SU(1,1) TFD formulation

In this Letter, an entropy operator for the general unitary SU(1, 1) TFD formulation is proposed and used to lead a bosonic system from zero to finite temperature. Namely, considering the closed bosonic string as the target system, the entropy operator is used to construct the thermal vacuum. The behaviour of such a state under the breve conjugation rules is analyzed and it was shown that the breve conjugation does not affect the thermal effects. From this thermal vacuum the thermal energy, the entropy and the free energy of the closed bosonic string are calculated and the appropriated thermal distribution for the system is found after the free energy minimization. (C) 2004 Elsevier B.V. All rights reserved.

Vortex lattice and matching fields for a long superconducting wire

We investigate the flux penetration patterns and matching fields of a long cylindrical wire of circular cross section in the presence of an external magnetic field. For this study we write the London theory for a long cylinder both for the mixed and Meissner states, with boundary conditions appropriate for this geometry. Using the Monte Carlo simulated annealing method, the free energy of the mixed state is minimized with respect to the vortex position and we obtain the ground state of the vortex lattice for N=3 up to 18 vortices. The free energy of the Meissner and mixed states provides expressions for the matching fields. We find that, as in the case of samples of different geometry, the finite-size effect provokes a delay on the vortex penetration and a vortex accumulation in the center of the sample. The vortex patterns obtained are in good agreement with experimental results.

Predição do desempenho de gasificadores de biomassa utilizando equilíbrio químico

A tecnologia de gasificação tem sido objeto de estudo de vários pesquisadores ao redor do planeta, principalmente para aplicações na geração de eletricidade a partir de biomassa. Neste trabalho é apresentado um modelo simplificado para gasificação de biomassa baseado nas considerações de equilíbrio químico. O modelo consiste da aplicação das leis de conservação de massa e energia acompanhadas da aplicação da minimização da energia livre de Gibbs no gás produzido. Apesar da simplicidade do modelo seus resultados são confiáveis ao predizer os parâmetros de trabalho de sistemas de gasificação. A composição da biomassa, temperatura do ar, teor de umidade e perdas de calor são parâmetros que podem ser variados para se fazer a análise dos diferentes pontos de operação do gasificador. Os resultados obtidos foram comparados com resultados experimentais e apresentaram boa concordância com mos mesmos.