New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.

Estudos de Durabilidade Frente ao Ataque Ácido de Compósitos Portland-Polímero para Cimentação de Poços de Petróleo

Portland-polymers composites are promising candidates to be used as cementing material in Northeastern oil wells of Brazil containing heavy oils submitted to steam injection. In this way, it is necessary to evaluate its degradation in the commonly acidizind agents. In addition, to identify how aggressive are the different hostile environments it is an important contribution on the decision of the acidic systems to be used in. It was investigated the performance of the Portland-polymer composites using powdered polyurethane, aqueous polyurethane, rubber tire residues and a biopolymer, those were reinforced with polished carbon steel SAE 1045 to make the electrochemical measurements. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) and HAc 10 % + HF 1,5 % were used as degrading environment and electrolytes. The more aggressive acid solution to the plain Portland hardened cement paste was the regular mud acid, that showed loss of weight around 23.0 %, followed by the soft mud acid, the showed 11.0 %, 15.0 % HCl with 7,0 % and, at last the 10.0 % HAc plus HF 1.5 % with just 1.0 %. The powdered polyurethane-composite and the aqueous polyurethane one showed larger durability, with reduction around 87.0 % on the loss of weight in regular mud acid. The acid attack is superficial and it occurs as an action layer, where the degraded layer is responsible for the decrease on the kinetic of the degrading process. This behavior can be seen mainly on the Portland- aqueous polyurethane composite, because the degraded layer is impregnated with chemically modified polymer. The fact of the acid attack does not have influence on the compressive strength or fratography of the samples, in a general way, confirms that theory. The mechanism of the efficiency of the Portland-polymers composites subjected to acid attack is due to decreased porosity and permeability related with the plain Portland paste, minor quantity of Ca+2, element preferentially leached to the acidic solution, wave effect and to substitute part of the degrading bulk for the polymeric one. The electrolyte HAc 10 % + HF 1,5 % was the least aggressive one to the external corrosion of the casing, showing open circuit potentials around +250 mV compared to -130 mV to the simulated pore solution to the first 24 hours immersion. This behavior has been performed for two months at least. Similar corrosion rates were showed between both of the electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and big polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirm its efficiency. In this way, Portlandpolymers composites are possible solutions to be succeed applied to oilwell cementing concomitant submitted to steam injection and acidizing operation and the HAc 10,0 % + HF 1,5 % is the less aggressive solution to the external corrosion of the casing

Are cutout handles used when available in real occupational settings? Description of grips and upper extremities movements during industrial box handling

In order to achieve better postures and decrease musculoskeletal risks adequate design of hand/box couplings for manual materials handling (MMH) are still needed. No studies evaluating upper limb movement thorough direct measurements during box handling in workplace were identified in the literature. In this study we describe the types of grip and movements adopted by ten workers when handling redesigned boxes with cutout handles between different heights on industrial pallets. The new handles were used by 90% of the workers through different types of grip. Electrogoniometric measurements showed relatively safe forearm and wrist movements, although elbow inadequate range of movement was recorded. Despite the good acceptance of the cutout by workers, the new design requires extra internal space in the boxes reducing applications for this alternative of box.

Uso de técnicas de otimização baseadas em derivadas como suporte do planejamento operacional de redes de distribuição de energia elétrica

The usual programs for load flow calculation were in general developped aiming the simulation of electric energy transmission, subtransmission and distribution systems. However, the mathematical methods and algorithms used by the formulations were based, in majority, just on the characteristics of the transmittion systems, which were the main concern focus of engineers and researchers. Though, the physical characteristics of these systems are quite different from the distribution ones. In the transmission systems, the voltage levels are high and the lines are generally very long. These aspects contribute the capacitive and inductive effects that appear in the system to have a considerable influence in the values of the interest quantities, reason why they should be taken into consideration. Still in the transmission systems, the loads have a macro nature, as for example, cities, neiborhoods, or big industries. These loads are, generally, practically balanced, what reduces the necessity of utilization of three-phase methodology for the load flow calculation. Distribution systems, on the other hand, present different characteristics: the voltage levels are small in comparison to the transmission ones. This almost annul the capacitive effects of the lines. The loads are, in this case, transformers, in whose secondaries are connected small consumers, in a sort of times, mono-phase ones, so that the probability of finding an unbalanced circuit is high. This way, the utilization of three-phase methodologies assumes an important dimension. Besides, equipments like voltage regulators, that use simultaneously the concepts of phase and line voltage in their functioning, need a three-phase methodology, in order to allow the simulation of their real behavior. For the exposed reasons, initially was developped, in the scope of this work, a method for three-phase load flow calculation in order to simulate the steady-state behaviour of distribution systems. Aiming to achieve this goal, the Power Summation Algorithm was used, as a base for developing the three phase method. This algorithm was already widely tested and approved by researchers and engineers in the simulation of radial electric energy distribution systems, mainly for single-phase representation. By our formulation, lines are modeled in three-phase circuits, considering the magnetic coupling between the phases; but the earth effect is considered through the Carson reduction. It s important to point out that, in spite of the loads being normally connected to the transformer s secondaries, was considered the hypothesis of existence of star or delta loads connected to the primary circuit. To perform the simulation of voltage regulators, a new model was utilized, allowing the simulation of various types of configurations, according to their real functioning. Finally, was considered the possibility of representation of switches with current measuring in various points of the feeder. The loads are adjusted during the iteractive process, in order to match the current in each switch, converging to the measured value specified by the input data. In a second stage of the work, sensibility parameters were derived taking as base the described load flow, with the objective of suporting further optimization processes. This parameters are found by calculating of the partial derivatives of a variable in respect to another, in general, voltages, losses and reactive powers. After describing the calculation of the sensibility parameters, the Gradient Method was presented, using these parameters to optimize an objective function, that will be defined for each type of study. The first one refers to the reduction of technical losses in a medium voltage feeder, through the installation of capacitor banks; the second one refers to the problem of correction of voltage profile, through the instalation of capacitor banks or voltage regulators. In case of the losses reduction will be considered, as objective function, the sum of the losses in all the parts of the system. To the correction of the voltage profile, the objective function will be the sum of the square voltage deviations in each node, in respect to the rated voltage. In the end of the work, results of application of the described methods in some feeders are presented, aiming to give insight about their performance and acuity

Uso de técnicas de otimização baseadas em derivadas como suporte do planejamento operacional de redes de distribuição de energia elétrica

The usual programs for load flow calculation were in general developped aiming the simulation of electric energy transmission, subtransmission and distribution systems. However, the mathematical methods and algorithms used by the formulations were based, in majority, just on the characteristics of the transmittion systems, which were the main concern focus of engineers and researchers. Though, the physical characteristics of these systems are quite different from the distribution ones. In the transmission systems, the voltage levels are high and the lines are generally very long. These aspects contribute the capacitive and inductive effects that appear in the system to have a considerable influence in the values of the interest quantities, reason why they should be taken into consideration. Still in the transmission systems, the loads have a macro nature, as for example, cities, neiborhoods, or big industries. These loads are, generally, practically balanced, what reduces the necessity of utilization of three-phase methodology for the load flow calculation. Distribution systems, on the other hand, present different characteristics: the voltage levels are small in comparison to the transmission ones. This almost annul the capacitive effects of the lines. The loads are, in this case, transformers, in whose secondaries are connected small consumers, in a sort of times, mono-phase ones, so that the probability of finding an unbalanced circuit is high. This way, the utilization of three-phase methodologies assumes an important dimension. Besides, equipments like voltage regulators, that use simultaneously the concepts of phase and line voltage in their functioning, need a three-phase methodology, in order to allow the simulation of their real behavior. For the exposed reasons, initially was developped, in the scope of this work, a method for three-phase load flow calculation in order to simulate the steady-state behaviour of distribution systems. Aiming to achieve this goal, the Power Summation Algorithm was used, as a base for developping the three phase method. This algorithm was already widely tested and approved by researchers and engineers in the simulation of radial electric energy distribution systems, mainly for single-phase representation. By our formulation, lines are modeled in three-phase circuits, considering the magnetic coupling between the phases; but the earth effect is considered through the Carson reduction. Its important to point out that, in spite of the loads being normally connected to the transformers secondaries, was considered the hypothesis of existence of star or delta loads connected to the primary circuit. To perform the simulation of voltage regulators, a new model was utilized, allowing the simulation of various types of configurations, according to their real functioning. Finally, was considered the possibility of representation of switches with current measuring in various points of the feeder. The loads are adjusted during the iteractive process, in order to match the current in each switch, converging to the measured value specified by the input data. In a second stage of the work, sensibility parameters were derived taking as base the described load flow, with the objective of suporting further optimization processes. This parameters are found by calculating of the partial derivatives of a variable in respect to another, in general, voltages, losses and reactive powers. After describing the calculation of the sensibility parameters, the Gradient Method was presented, using these parameters to optimize an objective function, that will be defined for each type of study. The first one refers to the reduction of technical losses in a medium voltage feeder, through the installation of capacitor banks; the second one refers to the problem of correction of voltage profile, through the instalation of capacitor banks or voltage regulators. In case of the losses reduction will be considered, as objective function, the sum of the losses in all the parts of the system. To the correction of the voltage profile, the objective function will be the sum of the square voltage deviations in each node, in respect to the rated voltage. In the end of the work, results of application of the described methods in some feeders are presented, aiming to give insight about their performance and acuity

Aplicações de Dispositivos de Microondas utilizando Substrato EBG/PBG para Comunicações Móveis

The modern society depends on an efficient communications system able to of transmitting and receiving information with a higher speed and reliability every time. The need for ever more efficient devices raises optimization techniques of microstrip devices, such as techniques to increase bandwidth: thicker substrates and substrate structures with EBG (Electromagnetic Band Gap) and PBG (Photonic Band Gap). This work has how aims the study of the application of PBG materials on substrates of planar structures in microstrip, more precisely in directional quadrature couplers and in rat-race and impedance of transformers. A study of the planar structures in microstrip and substrates EBG is presented. The PBG substrates can be used to optimize the radiation through the air, thus reducing the occurrence of surface waves and the resulting diffraction edge responsible for degradation of radiation pattern. Through specific programs in FORTRAN Power Station obtained the frequencies and couplings for each structure. Are used the program PACMO - Computer Aided Design in Microwave. Results are obtained of the frequency and coupling devices, ranging the frequency band used (cellular communication and Wimax systems) and the permittivity of the substrate, comparing the results of conventional material and PBG materials in the s and p polarizations.

Fases e criticalidade no modelo ashkin - teller de três cores

The usual Ashkin-Teller (AT) model is obtained as a superposition of two Ising models coupled through a four-spin interaction term. In two dimension the AT model displays a line of fixed points along which the exponents vary continuously. On this line the model becomes soluble via a mapping onto the Baxter model. Such richness of multicritical behavior led Grest and Widom to introduce the N-color Ashkin-Teller model (N-AT). Those authors made an extensive analysis of the model thus introduced both in the isotropic as well as in the anisotropic cases by several analytical and computational methods. In the present work we define a more general version of the 3-color Ashkin-Teller model by introducing a 6-spin interaction term. We investigate the corresponding symmetry structure presented by our model in conjunction with an analysis of possible phase diagrams obtained by real space renormalization group techniques. The phase diagram are obtained at finite temperature in the region where the ferromagnetic behavior is predominant. Through the use of the transmissivities concepts we obtain the recursion relations in some periodical as well as aperiodic hierarchical lattices. In a first analysis we initially consider the two-color Ashkin-Teller model in order to obtain some results with could be used as a guide to our main purpose. In the anisotropic case the model was previously studied on the Wheatstone bridge by Claudionor Bezerra in his Master Degree dissertation. By using more appropriated computational resources we obtained isomorphic critical surfaces described in Bezerra's work but not properly identified. Besides, we also analyzed the isotropic version in an aperiodic hierarchical lattice, and we showed how the geometric fluctuations are affected by such aperiodicity and its consequences in the corresponding critical behavior. Those analysis were carried out by the use of appropriated definitions of transmissivities. Finally, we considered the modified 3-AT model with a 6-spin couplings. With the inclusion of such term the model becomes more attractive from the symmetry point of view. For some hierarchical lattices we derived general recursion relations in the anisotropic version of the model (3-AAT), from which case we can obtain the corresponding equations for the isotropic version (3-IAT). The 3-IAT was studied extensively in the whole region where the ferromagnetic couplings are dominant. The fixed points and the respective critical exponents were determined. By analyzing the attraction basins of such fixed points we were able to find the three-parameter phase diagram (temperature £ 4-spin coupling £ 6-spin coupling). We could identify fixed points corresponding to the universality class of Ising and 4- and 8-state Potts model. We also obtained a fixed point which seems to be a sort of reminiscence of a 6-state Potts fixed point as well as a possible indication of the existence of a Baxter line. Some unstable fixed points which do not belong to any aforementioned q-state Potts universality class was also found

Efeitos de acoplamentos biquadráticos e campos aleatórios em vidros de spins

In this work we have studied the effects of random biquadratic and random fields in spin-glass models using the replica method. The effect of a random biquadratic coupling was studied in two spin-1 spin-glass models: in one case the interactions occur between pairs of spins, whereas in the second one the interactions occur between p spins and the limit p > oo is considered. Both couplings (spin glass and biquadratic) have zero-mean Gaussian probability distributions. In the first model, the replica-symmetric assumption reveals that the system presents two pha¬ses, namely, paramagnetic and spin-glass, separated by a continuous transition line. The stability analysis of the replica-symmetric solution yields, besides the usual instability associated with the spin-glass ordering, a new phase due to the random biquadratic cou¬plings between the spins. For the case p oo, the replica-symmetric assumption yields again only two phases, namely, paramagnetic and quadrupolar. In both these phases the spin-glass parameter is zero. Besides, it is shown that they are stable under the Almeida-Thouless stability analysis. One of them presents negative entropy at low temperatures. We developed one step of replica simmetry breaking and noticed that a new phase, the biquadratic glass phase, emerge. In this way we have obtained the correct phase diagram, with.three first-order transition lines. These lines merges in a common triple point. The effects of random fields were studied in the Sherrington-Kirkpatrick model consi¬dered in the presence of an external random magnetic field following a trimodal distribu¬tion {P{hi) = p+S(hi - h0) +Po${hi) +pS(hi + h0))- It is shown that the border of the ferromagnetic phase may present, for conveniently chosen values of p0 and hQ, first-order phase transitions, as well as tricritical points at finite temperatures. It is verified that the first-order phase transitions are directly related to the dilution in the fields: the extensions of these transitions are reduced for increasing values of po- In fact, the threshold value pg, above which all phase transitions are continuous, is calculated analytically. The stability analysis of the replica-symmetric solution is performed and the regions of validity of such a solution are identified

Efeito Kerr magneto-óptico; Ressonância ferromagnética; Acoplamento bilinear; Acoplamento biquadrático

In this work, we investigated the magnetic properties of a monocrystalline Fe thin film and of Fe(80 Å)/Cr(t)/Fe(80 Å) tri-layers, with the nonmagnetic metallic Cr spacer layer thickness varying between 9 Å < t < 40 Å. The samples were deposited by the DC Sputtering on Magnesium Oxide (MgO) substrates, with (100) crystal orientation. For this investigation, experimental magneto-optical Kerr effect (MOKE) magnetometry and ferromagnetic resonance (FMR) techniques were employeed. In this case, these techniques allowed us to study the static and dynamical magnetization properties of our tri-layers. The experimental results were interpreted based on the phenomenological model that takes into account the relevant energy terms to the magnetic free energy to describe the system behavior. In the case of the monocrystalline Fe film, we performed an analytical discussion on the magnetization curves and developed a numerical simulation based on the Stoner-Wohlfarth model, that enables the numerical adjustment of the experimental magnetization curves and obtainment of the anisotropy field values. On the other hand, for the tri-layers, we analyzed the existence of bilinear and biquadratic couplings between the magnetizations of adjacent ferromagnetic layers from measurements of magnetization curves. With the FMR fields and line width angular dependencies, information on the anisotropy in three layers was obtained and the effects of different magnetic relaxation mechanisms were evidenced. It was also possible to observe the dependence of the epitaxy of the multilayers with growth and sputtering parameters. Additionally it was developed the technique of AC magnetic susceptibility in order to obtain further information during the investigation of magnetic thin films

Ondas de spin em nanofilmes nagnéticos acoplados quasiperiodicamente

We studied the spin waves modes that can propagate in magnetic multilayers composed of ferromagnetic metallic films in the nanometer scale. The ferromagnetic films (iron) are separated and coupled through the nonmagnetic spacer films (chromium). The films that make up the multilayer are stacked in a quasiperiodic pattern, following the Fibonacci and double period sequences. We used a phenomenological theory taking into account: the Zeeman energy (between the ferromagnetic films and the external magnetic field), the energy of the magneto-crystalline anisotropy (present in the ferromagnetic films), the energy of the bilinear and biquadratic couplings (between the ferromagnetic films) and the energy of the dipole-dipole interaction (between the ferromagnetic films), to describe the system. The total magnetic energy of the system is numerically minimized and the equilibrium angles of the magnetization of each ferromagnetic film are determined. We solved the equation of motion of the multilayer to find the dispersion relation for the system and, as a consequence, the spin waves modes frequencies. Our theoretical results show that, in the case of trilayers (Fe/Cr/Fe), our model reproduces with excellent agreement experimental results of Brillouin light scattering, known from the literature, by adjusting the physical parameters of the nanofilms. Furthermore, we generalize the model to N ferromagnetic layers which allowed us to determine how complex these systems become when we increase the number of components. It is worth noting that our theoretical calculations generalize all the results known from the literature

Static potential in QED(3) with nonminimal coupling

Here we study the effect of the nonminimal coupling j(mu)epsilon(munualpha)partial derivative(nu)A(alpha) on the static potential in multiflavor QED(3). Both cases of four and two components fermions are studied separately at leading order in the 1/N expansion. Although a nonlocal Chern-Simons term appears, in the four components case the photon is still massless leading to a confining logarithmic potential similar to the classical one. In the two components case, as expected, the parity breaking fermion mass term generates a traditional Chern-Simons term which makes the photon massive and we have a screening potential which vanishes at large intercharge distance. The extra nonminimal couplings have no important influence on the static potential at large intercharge distances. However, interesting effects show up at finite distances. In particular, for strong enough nonminimal coupling we may have a new massive pole in the photon propagator, while in the opposite limit there may be no poles at all in the irreducible case. We also found that, in general, the nonminimal couplings lead to a finite range repulsive force between charges of opposite signs.

Confinement of spinless particles by Coulomb potentials in two-dimensional space-time

The problem of confinement of spinless particles in 1 + 1 dimensions is approached with a linear potential by considering a mixing of Lorentz vector and scalar couplings. Analytical bound-states solutions are obtained when the scalar coupling is of sufficient intensity compared to the vector coupling. (c) 2005 Elsevier B.V. All rights reserved.

Restrictions over two-dimensional gauge models with Thirring-like interaction

Some years ago, it was shown how fermion self-interacting terms of the Thirring-type impact the usual structure of massless two-dimensional gauge theories [1]. In that work only the cases of pure vector and pure chiral gauge couplings have been considered and the corresponding Thirring term was also pure vector and pure chiral respectively, such that the vector ( or chiral) Schwinger model should not lose its chirality structure due to the addition of the quartic interaction term. Here we extend this analysis to a generalized vector and axial coupling both for the gauge interaction and the quartic fermionic interactions. The idea is to perform quantization without losing the original structure of the gauge coupling. In order to do that we make use of an arbitrariness in the definition of the Thirring-like interaction.

Confinement of fermions by mixed vector-scalar linear potentials in two-dimensional space-time

The problem of confinement of fermions in 1 + 1 dimensions is approached with a linear potential in the Dirac equation by considering a mixing of Lorentz vector and scalar couplings. Analytical bound-states solutions are obtained when the scalar coupling is of sufficient intensity compared to the vector coupling. (C) 2002 Elsevier B.V. B.V. All rights reserved.