117 resultados para Binding free energy


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In the present work we study an anisotropic layered superconducting film of finite thickness. The film surfaces are considered parallel to the be face of the crystal. The vortex lines are oriented perpendicular to the film surfaces and parallel to the superconducting planes. We calculate the local field and the London free energy for this geometry. Our calculation is a generalization of previous works where the sample is taken as a semi-infinite superconductor. As an application of this theory we investigate the flux spreading at the super conducting surface.

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Phase separation suppression due to external biaxial strain is observed in InxGa1-xN alloy layers by Raman scattering spectroscopy. The effect is taking place in thin epitaxial layers pseudomorphically grown by molecular-beam epitaxy on unstrained GaN(001) buffers. Ab initio calculations carried out for the alloy free energy predict and Raman measurements confirm that biaxial strain suppress the formation of phase-separated In-rich quantum dots in the InxGa1-xN layers. Since quantum dots are effective radiative recombination centers in InGaN, we conclude that strain quenches an important channel of light emission in optoelectronic devices based on pseudobinary group-III nitride semiconductors. (C) 2002 American Institute of Physics.

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The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L-1 H2SO4 solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA](n), polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases ill solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L-1 H2SO4 in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper. (C) 2007 Elsevier Ltd. All rights reserved.

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The influence of the axial organic ligand R on the electrochemical oxidation of the compounds [RCoIII(salen)DMF)], where salen is bis(salicylaldehyde)ethylenediimine, and R CH3, C2H5, n-C3H7, n-C4H9, s-C4H9, i-C4H9, CH2Cl, CF3CH2, c-C6H11CH2, c-C6H11, C6H5, C6H5CH2, p-CH3C6H4CH2, and p-NO2C6H4CH2, was studied by means of cyclic voltametry in dimethylformamide (DMF), 0.2 M in tetraethylammonium perchlorate (TEAP), at 25 and -20°C, with a platinum disc working electrode. The above-mentioned compounds can be classified according to their electrochemical behavior. (a) The complexes with R CH3, C2H5, n-C3H7, n-C4H9, c-C6H11CH2, and C6H5 undergo a reversible one-electron oxidation in the 10-50 V s-1 potential scan range. At slower scan rates, the oxidized product decomposes chemically. At -20°C, this chemical step is slow, and a reversible one-electron electrochemical oxidation is observed. (b) The compounds with R CH2Cl, C6H5CH2, p-CH3C6H4CH2 and p-NO2C6H4CH2 undergo a quasi-reversible one-electron oxidation at room temperaure. At -20°C, the electrochemical process becomes more complex. A following chemical reactions is coupled to the quasi-reversible one-electron transfer. Two reduction peaks are observed. (c) The compounds with R i-C4H9, s-C4H9, and c-C6H11 undergo a reversible one-electron oxidation at -20°C. At room temperature, the irreversible chemical reaction following the electron transfer step is too fast to allow the isolation of the electrochemical step. (d) At -20°C, the derivatives with R C2H5, c-C6H11 CH2 and c-C6H11 are adsorbed at the electrode surface. Evidence indicates that the reagent in these reactions is the pentacoordinated species [RCoIII(salen)]. A linear free-energy relationship between E1/2 (for reversible processes) and the Taft polar parameters o* was obtained with a slope of ρ* = 0.25 ± 0.03. As expected, the benzyl derivatives which present mesomeric effects do not fit this polar correlation. The rated of the electrochemical oxidation is also affected by the nature of the ligand R. For the ligands which are strong electron-withdrawing groups and for the benzyl derivatives, the rate of the electrochemical oxidation of the metal ion decreases at room temperature. At lower temperatures, it is suggested that the oxidation to the CoIV-R species is followed by a chemical reaction in which this complex is partly transformed into a CoIII(R*) species, which is reduced at a much more cathodic potential than the Co(IV) species. © 1979.

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The kinetics of the reactions of Ru(II) complexes with CS2N- 3 ions were studied spectrophotometrically. The formation rate constants data for trans-[Ru(NH3)4L(CS2N3)] are 2.2 × 102, 1.8 × 10 and 1.3 × 102 M-1 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3), respectively [μ = 1.0 M (NaCF3COO), 25°C]. Under the same experimental conditions, the values of k-1 (specific rate for the aquation reaction) are 1.5 × 10-2, 5.0 × 10-2 and 4.5 × 10 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3, respectively. The free-energy change (ΔG≠) for the systems where L = P(OEt)3 and SO2- 3 are in agreement within the experimental error. It was observed that the affinity of the CS2N- 3 ion decreases with the increasing π-acidity of the auxiliary ligand L. The order of affinity of the CS2N- 3 ion for the Ru(II) center studies is SO2- 3 > HSO- 3 > P(OEt)3 >SO2. © 1986.

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We write the London limit of the Lawrence Doniach free energy in terms of the local magnetic field and of the average supercurrent over the interplane distance. Starting from this formulation we study a model where the supercurrent at the buffer layers is obtained from the superconducting sheets by a Taylor expansion. The continuum limit of this model gives corrections to the anisotropic London theory due to the layered structure.

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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.

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The size effects in the magnetization of a long cylindrical wire of circular cross section in the presence of an external magnetic field are investigated. For this study the London theory is used 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 positions. The ground state of the vortex lattice for n = 1 up to 18 vortices for a given radius of the cylinder is obtained. It is found that the finite size of the sample provokes a matching effect in the magnetization, as found in experiments with superconducting samples of finite size but different geometry. © 1999 American Institute of Physics.

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We obtain the vortex configurations, the matching fields, and the magnetization of a superconducting film with a finite cross section. The applied magnetic field is normal to this cross section, and we use the London theory to calculate many of its properties, such as the local magnetic field, the free energy, and the induction for the mixed state. Thus previous similar theoretical works, done for an infinitely long superconducting film, are recovered here, in the special limit of a very long cross section. ©1999 The American Physical Society.

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We analyze the average performance of a general class of learning algorithms for the nondeterministic polynomial time complete problem of rule extraction by a binary perceptron. The examples are generated by a rule implemented by a teacher network of similar architecture. A variational approach is used in trying to identify the potential energy that leads to the largest generalization in the thermodynamic limit. We restrict our search to algorithms that always satisfy the binary constraints. A replica symmetric ansatz leads to a learning algorithm which presents a phase transition in violation of an information theoretical bound. Stability analysis shows that this is due to a failure of the replica symmetric ansatz and the first step of replica symmetry breaking (RSB) is studied. The variational method does not determine a unique potential but it allows construction of a class with a unique minimum within each first order valley. Members of this class improve on the performance of Gibbs algorithm but fail to reach the Bayesian limit in the low generalization phase. They even fail to reach the performance of the best binary, an optimal clipping of the barycenter of version space. We find a trade-off between a good low performance and early onset of perfect generalization. Although the RSB may be locally stable we discuss the possibility that it fails to be the correct saddle point globally. ©2000 The American Physical Society.

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Hybrid organic-inorganic ionic conductors, also called ormolytes (organically modified electrolytes), were obtained by dissolution of LiClO 4 in siloxane-poly(propylene glycol) matrixes. The dynamic features of these nanocomposites were studied and correlated to their electrical properties. Solid-state nuclear magnetic resonance (NMR) spectroscopy was used to probe the effects of the temperature and nanocomposite composition on the dynamic behaviors of both the ionic species ( 7Li) and the polymer chains ( 13C). NMR, dc ionic conductivity, and DSC results demonstrate that the Li + mobility is strongly assisted by the segmental motion of the polymer chain above its glass transition temperature. The ac ionic conductivity in such composites is explained by use of the random free energy barrier (RFEB) model, which is agreement with their disordered and heterogenous structures. These solid ormolytes are transparent and flexible, and they exhibit good ionic conductivity at room temperature (up to 10 -4 S/cm). Consequently, they are very promising candidates for use in several applications such as batteries, sensors, and electrochromic and photoelectro-chemical devices.

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In this paper a hybrid solid oxide fuel cell (SOFC) system is analyzed. This system applies a combined cycle utilizing gas turbine associated to a SOFC for rational decentralized energy production. Initially the relative concepts about the fuel cell are presented, followed by some chemical and technical informations such as the change of Gibbs free energy in isothermal fuel oxidation (or combustion) directly into electricity. This represents a very high fraction of the lower heating value (LHV) of a hydrocarbon fuel. In the next step a methodology for the study of SOFC associated with a gas turbine system is developed, considering the electricity and steam production for a hospital, as regard to the Brazilian conditions. This methodology is applied to energetic analysis. Natural gas is considered as a fuel. In conclusion, it is shown by a Sankey Diagram that the hybrid SOFC system may be an excellent opportunity to strengthen the decentralized energy production in Brazil. It is necessary to consider that the cogeneration in this version also is a sensible alternative from the technical point of view, demanding special methods of design, equipment selection and mainly of the contractual deals associated to electricity and fuel supply.

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Plasma processing of the surfaces of biomaterials is interesting because it enables modification of the characteristics of a surface without affecting bulk properties. In addition, the results are strongly influenced by the conditions of the treatment. Therefore, by adjusting the plasma parameters it is possible to tailor the surface properties to best fulfill the requirements of a given application. In this work, polyurethane substrates have been subjected to sulfur hexafluoride glow discharge plasmas. The influences of different SF 6 plasma exposure times and pressures on the adhesion of Staphylococcus aureus and Pseudomonas aeruginosa to the polymer have been investigated. The wettability and surface free energy have been evaluated via contact angle measurements. At low pressure (6.7 Pa) the contact angle decreases with increasing exposure time in the 180 s to 540 s interval, but at higher pressure (13.3 Pa) it increases as a function of the same variable. Bacterial adhesion has been quantified from in vitro experiments by determining the growth of colonies on Petri dishes treated with agar nutrient. It has been observed that the surface properties play an important role in microbe adhesion. For instance, the density of adhered P. aeruginosa decreased as the surface contact angle increased. S. aureus preferred to adhere to hydrophobic surfaces. © 2011 by Begell House, Inc.

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Banana is an agricultural product of great economic importance for various developing countries. The relationship between moisture content and water activity provides useful information for the processing and storage of banana waste. The water activity and moisture content of three banana (Mussa spp. Haploid AAB cv. Nanica) waste items were analyzed to determine the desorption isotherms at six different temperatures (20, 30, 40, 50, 60 and 70°C). The desorption isotherms of the peel, pedicel and pulp of overripe bananas were determined in wide ranges of moisture content (0.001-6.360 kg kg-1 d.b.) and water activity (0.02-0.907). The theoretical GAB model was used for modelling the desorption isotherms. An analytical solution of the Clausius-Clapeyron equation was proposed to compute the isosteric heat of sorption, the differential entropy and Gibbs' free energy by way of the GAB model when the effect of temperature on the hygroscopic equilibrium was considered. © 2012 de Gruyter. All rights reserved.

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Objective: This study investigated the effect of experimental photopolymerized coatings, containing zwitterionic or hydrophilic monomers, on the hydrophobicity of a denture base acrylic resin and on Candida albicans adhesion. Methods: Acrylic specimens were prepared with rough and smooth surfaces and were either left untreated (control) or coated with one of the following experimental coatings: 2-hydroxyethyl methacrylate (HE); 3-hydroxypropyl methacrylate (HP); and 2-trimethylammonium ethyl methacrylate chloride (T); and sulfobetaine methacrylate (S). The concentrations of these constituent monomers were 25%, 30% or 35%. Half of the specimens in each group (control and experimentals) were coated with saliva and the other half remained uncoated. The surface free energy of all specimens was measured, regardless of the experimental condition. C. albicans adhesion was evaluated for all specimens, both saliva conditioned and unconditioned. The adhesion test was performed by incubating specimens in C. albicans suspensions (1 × 10 7 cell/mL) at 37 °C for 90 min. The number of adhered yeasts were evaluated by XTT (2,3-bis[2-methoxy-4-nitro-5-sulfophenyl]-5-[{phenylamino} carbonyl]-2H-tetrazolium-hydroxide) method. Results: For rough surfaces, coatings S (30 or 35%) and HP (30%) resulted in lower absorbance values compared to control. These coatings exhibited more hydrophilic surfaces than the control group. Roughness increased the adhesion only in the control group, and saliva did not influence the adhesion. The photoelectron spectroscopy analysis (XPS) confirmed the chemical changes of the experimental specimens, particularly for HP and S coatings. Conclusions: S and HP coatings reduced significantly the adhesion of C. albicans to the acrylic resin and could be considered as a potential preventive treatment for denture stomatitis. © 2012 Elsevier Ltd.