Influence of composition on the structure, electric and magnetic properties of Pd-Mn-P and Pd-Co-P amorphous alloys

The influence of composition on the structure and on the electric and magnetic properties of amorphous Pd-Mn-P and Pd-Co-P prepared by rapid quenching techniques were investigated in terms of (1) the 3d band filling of the first transition metal group, (2) the phosphorus concentration effect which acts as an electron donor and (3) the transition metal concentration.

The structure is essentially characterized by a set of polyhedra subunits essentially inverse to the packing of hard spheres in real space. Examination of computer generated distribution functions using Monte Carlo random statistical distribution of these polyhedra entities demonstrated tile reproducibility of the experimentally calculated atomic distribution function. As a result, several possible "structural parameters" are proposed such as: the number of nearest neighbors, the metal-to-metal distance, the degree of short-range order and the affinity between metal-metal and metal-metalloid. It is shown that the degree of disorder increases from Ni to Mn. Similar behavior is observed with increase in the phosphorus concentration.

The magnetic properties of Pd-Co-P alloys show that they are ferromagnetic with a Curie temperature between 272 and 399°K as the cobalt concentration increases from 15 to 50 at.%. Below 20 at.% Co the short-range exchange interactions which produce the ferromagnetism are unable to establish a long-range magnetic order and a peak in the magnetization shows up at the lowest temperature range . The electric resistivity measurements were performed from liquid helium temperatures up to the vicinity of the melting point (900°K). The thermomagnetic analysis was carried out under an applied field of 6.0 kOe. The electrical resistivity of Pd-Co-P shows the coexistence of a Kondo-like minimum with ferromagnetism. The minimum becomes less important as the transition metal concentration increases and the coefficients of ℓn T and T^2 become smaller and strongly temperature dependent. The negative magnetoresistivity is a strong indication of the existence of localized moment.

The temperature coefficient of resistivity which is positive for Pd- Fe-P, Pd-Ni-P, and Pd-Co-P becomes negative for Pd-Mn-P. It is possible to account for the negative temperature dependence by the localized spin fluctuation model and the high density of states at the Fermi energy which becomes maximum between Mn and Cr. The magnetization curves for Pd-Mn-P are typical of those resulting from the interplay of different exchange forces. The established relationship between susceptibility and resistivity confirms the localized spin fluctuation model. The magnetoresistivity of Pd-Mn-P could be interpreted in tenns of a short-range magnetic ordering that could arise from the Rudennan-Kittel type interactions.

Radiation from a short electric dipole antenna in a hot uniaxial plasma

The effects of electron temperature on the radiation fields and the resistance of a short dipole antenna embedded in a uniaxial plasma have been studied. It is found that for ω < ω_p the antenna excites two waves, a slow wave and a fast wave. These waves propagate only within a cone whose axis is parallel to the biasing magnetostatic field B_o and whose semicone angle is slightly less than sin ^(-1) (ω/ω_p). In the case of ω > ω_p the antenna excites two separate modes of radiation. One of the modes is the electromagnetic mode, while the other mode is of hot plasma origin. A characteristic interference structure is noted in the angular distribution of the field. The far fields are evaluated by asymptotic methods, while the near fields are calculated numerically. The effects of antenna length ℓ, electron thermal speed, collisional and Landau damping on the near field patterns have been studied.

The input and the radiation resistances are calculated and are shown to remain finite for nonzero electron thermal velocities. The effect of Landau damping and the antenna length on the input and radiation resistances has been considered.

The radiation condition for solving Maxwell's equations is discussed and the phase and group velocities for propagation given. It is found that for ω < ω_p in the radial direction (cylindrical coordinates) the power flow is in the opposite direction to that of the phase propagation. For ω > ω_p the hot plasma mode has similar characteristics.

Dendrites Inhibition in Rechargeable Lithium Metal Batteries

The specific high energy and power capacities of rechargeable lithium metal (Li⁰) batteries are ideally suited to portable devices and are valuable as storage units for intermittent renewable energy sources. Lithium, the lightest and most electropositive metal, would be the optimal anode material for rechargeable batteries if it were not for the fact that such devices fail unexpectedly by short-circuiting via the dendrites that grow across electrodes upon recharging. This phenomenon poses a major safety issue because it triggers a series of adverse events that start with overheating, potentially followed by the thermal decomposition and ultimately the ignition of the organic solvents used in such devices.

In this thesis, we developed experimental platform for monitoring and quantifying the dendrite populations grown in a Li battery prototype upon charging under various conditions. We explored the effects of pulse charging in the kHz range and temperature on dendrite growth, and also on loss capacity into detached “dead” lithium particles.

Simultaneously, we developed a computational framework for understanding the dynamics of dendrite propagation. The coarse-grained Monte Carlo model assisted us in the interpretation of pulsing experiments, whereas MD calculations provided insights into the mechanism of dendrites thermal relaxation. We also developed a computational framework for measuring the dead lithium crystals from the experimental images.

Sistemas fotovoltaicos integrados ao perfil de uso da edificação

Nos últimos anos, o consumo de energia vem crescendo mundialmente nos grandes centros urbanos, e esforços na área de eficiência energética estão sendo implantados, a fim de reduzir o consumo no horário da ponta e interrupções da rede. O aproveitamento das fontes renováveis, como o fotovoltaico em uma edificação se torna um atrativo a mais para a matriz energética num momento em que o país prima pela universalização dos serviços de energia e a classificação de edifícios comerciais, de serviço e públicos, além dos residenciais quanto à eficiência energética através do Procel Edifica (RTQ-C e RTQ-R). Os sistemas fotovoltaicos podem configurar perfis de uso nas edificações de modo a gerar energia para consumo próprio ou ligado à rede e ainda ter influência na arquitetura do prédio com revestimento: os perfis podem está em telhados, fachadas ou janelas, amenizando em alguns casos a carga térmica no prédio com sombreamento arquitetônico. Hoje, com o avanço da tecnologia no setor de armazenagem é possível, o atendimento com segurança e eficiência a uma edificação ou direcionar esta armazenagem a uma demanda específica como o atendimento à demanda de ciclo profundo, tais como, iluminação externa e recarga de veículos elétricos. Partindo da premissa de sistemas interruptos de energia, UPS, uso de fonte secundária como FV, baterias e Flywheel é apresentado uma forma de melhor gerenciar a energia armazenada, podendo estender a vida útil da bateria e conseqüentemente de todo o sistema fotovoltaico na edificação. Esta forma de armazenar energia proporciona um serviço de uso contínuo sem percepção das interrupções da rede com garantia de 20 anos, tal qual o módulo fotovoltaico, com esta proposta as perdas de energia elétrica na edificação serão atenuadas, pois a eletricidade será utilizada de forma eficiente e inteligente. O ponto de partida do estudo de caso no prédio do IBAM são os sistemas fotovoltaicos com geração distribuída (mini-redes) conectados à rede que são instalados para fornecer energia ao consumidor, complementando a quantidade de energia demandada, caso haja algum aumento do consumo de energia na edificação, ou ainda utilizar o sistema fotovoltaico na hora da ponta e interrupções do sistema da rede no período fora da ponta. A estocagem inercial por meio do Flywheel tem um papel fundamental nesta mini-rede (Flywheel, bateria VRLA, UPS, inversor e STS), pois a sua utilização pode ser apontada como uma inovação tecnológica quanto à regulação de tensão no sistema de energia elétrica, além de preparar a edificação para o smart-grid. Esta configuração de acumulação de energia permitiu a analise do deslocamento desta energia armazenada para o consumo no horário de ponta, mudando o conceito de sistemas fotovoltaicos autônomos no meio urbano e rural no país. Este conceito de armazenagem se confirma então como um aporte na eficiência de energia na edificação, podendo carrear economia de energia substancial, além de proporcionar uma confiabilidade no serviço de energia, com um baixo retorno do investimento e com uma garantia de funcionamento com pequena ou nenhuma manutenção durante o período de vida de 20 anos.

Optimization of nonvolatile holographic recording by application of an external electric field

The dependences of the recording properties of LiNbO3:Fe:Mn crystals on an external electric field (applied in the recording or fixing phase of the nonvolatile holographic recording process) are numerically investigated and the optimal conditions for applying an external electric field in this two-step process of nonvolatile holographic recording are discussed in detail. Significant improvement of the photorefractive performance has been found and experimental verifications using a small external electric field are described. Moreover, direct measures relating to the dominant photovoltaic mechanism in the doubly doped LiNbO3 crystals and the unconventional grating-enhanced fixing are revealed by applying an external electric field in the recording and the fixing phases, respectively.

Improvement in refractive-index change in LiNbO3 : Ce : Cu by applying an external electric field

By jointly solving two-centre material equations with a nonzero external electric field and coupled-wave equations, we have numerically studied the dependence of the non-volatile holographic recording in LiNbO3:Ce:Cu crystals on the external electric field. The dominative photovoltaic effect of the non-volatile holographic recording in doubly doped LiNbO3 crystals is directly verified. And an external electric field that is applied in the positive direction along the c-axis (or a large one in the negative direction of the c-axis) in the recording phase and another one that is applied in the negative direction of the c-axis in the fixing phase are both proved to benefit strong photorefractive performances. Experimental verifications are given with a small electric field applied externally.

Part I. Electric birefringence studies of deoxyribonucleic acids. Part II. Selective dissociation of nucleohistone complexes

Part I

The electric birefringence of dilute DNA solutions has been studied in considerable detail and on a large number of samples, but no new and reliable information was discovered concerning the tertiary structure of DNA. The large number of variables which effect the birefringence results is discussed and suggestions are made for further work on the subject.

The DNA molecules have been aligned in a rapidly alternating (10 to 20 kc/sec) square wave field confirming that the orientation mechanism is that of counterion polarization. A simple empirical relation between the steady state birefringence, Δn_st, and the square of the electric field, E, has been found: Δn_st = E²/(a E² + b), where a = 1/Δn_s and b = (E²/Δn_st)_E→o. Δn_s is the birefringence extrapolated to infinite field strength.

The molecules show a distribution of relaxation times from 10^-4 to 0.2 sec, which is consistent with expectations for flexible coil molecules. The birefringence and the relaxation times decrease with increasing salt concentrations. They also depend on the field strength and pulse duration in a rather non-reproducible manner, which may be due in part to changes in the composition of the solution or in the molecular structure of the DNA (other than denaturation). Further progress depends on the development of some control over these effects.

Part II

The specificity of the dissociation of reconstituted and native deoxyribonucleohistones (DNH) by monovalent salt solutions has been investigated. A novel zone ultracentrifugation method is used in which the DNH is sedimented as a zone through a preformed salt gradient, superimposed on a stabilizing D₂O (sucrose) density gradient. The results, obtained by scanning the quartz sedimentation tubes in a spectrophotometer, were verified by the conventional, preparative sedimentation technique. Procedures are discussed for the detection of microgram quantities of histones, since low concentrations must be used to prevent excessive aggregation of the DNH.

The data show that major histone fractions are selectively dissociated from DNH by increasing salt concentrations: Lysine rich histone (H I) dissociates gradually between 0.1 and 0.3 F, slightly lysine rich histone (H II) dissociates as a narrow band between 0.35 and 0.5 F, and arginine rich histone (H III, H IV) dissociates gradually above 0.5 F NaClO₄.

The activity of the partially dissociated, native DNH in sustaining RNA synthesis, their mobility and their unusual heat denaturation and renaturation behavior are described. The two-step melting behavior of the material indicates that the histones are non-randomly distributed along the DNA, but the implications are that the uncovered regions are not of gene-size length.

Anomalous electric dipole internal conversion

Electric dipole internal conversion has been experimentally studied for several nuclei in the rare earth region. Anomalies in the conversion process have been interpreted in terms of nuclear structure effects. It was found that all the experimental results could be interpreted in terms of the j ∙ r type of penetration matrix element; the j ∙ ∇ type of penetration matrix element was not important. The ratio λ of the El j ∙ r penetration matrix element to the El gamma-ray matrix element was determined from the experiments to be:

Lu¹⁷⁵,396 keV, λ = - 1000 ± 100;

282 keV, λ = 500 ± 100;

144 keV, λ = 500 ± 250;

Hf¹⁷⁷, 321 keV λ = - 1400 ± 200;

208 keV λ = - 90 ± 40;

72 keV |λ| ≤ 650;

Gd¹⁵⁵, 86 keV λ = - 150 ± 100;

Tm¹⁶⁹, 63 keV λ = - 100 ± 100;

W¹⁸², 152 keV, λ = - 160 ±80;

67 keV, λ = - 100 ± 100.

Predictions for λ are made using the unified nuclear model.

I. Electronic processes in α-sulfur. II. Polaron motion in a D.C. electric field

Part I: The mobilities of photo-generated electrons and holes in orthorhombic sulfur are determined by drift mobility techniques. At room temperature electron mobilities between 0.4 cm²/V-sec and 4.8 cm²/V-sec and hole mobilities of about 5.0 cm²/V-sec are reported. The temperature dependence of the electron mobility is attributed to a level of traps whose effective depth is about 0.12 eV. This value is further supported by both the voltage dependence of the space-charge-limited, D.C. photocurrents and the photocurrent versus photon energy measurements.

As the field is increased from 10 kV/cm to 30 kV/cm a second mechanism for electron transport becomes appreciable and eventually dominates. Evidence that this is due to impurity band conduction at an appreciably lower mobility (4.10^-4 cm²/V-sec) is presented. No low mobility hole current could be detected. When fields exceeding 30 kV/cm for electron transport and 35 kV/cm for hole transport are applied, avalanche phenomena are observed. The results obtained are consistent with recent energy gap studies in sulfur.

The theory of the transport of photo-generated carriers is modified to include the case of appreciable thermos-regeneration from the traps in one transit time.

Part II: An explicit formula for the electric field E necessary to accelerate an electron to a steady-state velocity v in a polarizable crystal at arbitrary temperature is determined via two methods utilizing Feynman Path Integrals. No approximation is made regarding the magnitude of the velocity or the strength of the field. However, the actual electron-lattice Coulombic interaction is approximated by a distribution of harmonic oscillator potentials. One may be able to find the “best possible” distribution of oscillators using a variational principle, but we have not been able to find the expected criterion. However, our result is relatively insensitive to the actual distribution of oscillators used, and our E-v relationship exhibits the physical behavior expected for the polaron. Threshold fields for ejecting the electron for the polaron state are calculated for several substances using numerical results for a simple oscillator distribution.

Stability of Electrode-Electrolyte Interfaces during Charging in Lithium Batteries

In this thesis we study the growth of a Li electrode-electrolyte interface in the presence of an elastic prestress. In particular, we focus our interest on Li-air batteries with a solid electrolyte, LIPON, which is a new type of secondary or rechargeable battery. Theoretical studies and experimental evidence show that during the process of charging the battery the replated lithium adds unevenly to the electrode surface. This phenomenon eventually leads to dendrite formation as the battery is charged and discharged numerous times. In order to suppress or alleviate this deleterious effect of dendrite growth, we put forth a study based on a linear stability analysis. Taking into account all the mechanisms of mass transport and interfacial kinetics, we model the evolution of the interface. We find that, in the absence of stress, the stability of a planar interface depends on interfacial diffusion properties and interfacial energy. Specifically, if Herring-Mullins capillarity-driven interfacial diffusion is accounted for, interfaces are unstable against all perturbations of wavenumber larger than a critical value. We find that the effect of an elastic prestress is always to stabilize planar interfacial growth by increasing the critical wavenumber for instability. A parametric study results in quantifying the extent of the prestress stabilization in a manner that can potentially be used in the design of Li-air batteries. Moreover, employing the theory of finite differences we numerically solve the equation that describes the evolution of the surface profile and present visualization results of the surface evolution by time. Lastly, numerical simulations performed in a commercial finite element software validate the theoretical formulation of the interfacial elastic energy change with respect to the planar interface.

1. Ultrasonic studies of binary liquid structure in the critical region. Theory and experiment for the 2,6-lutidine/water system. 2. Hartree-Fock calculations of electric polarizabilities of some simple atoms and molecules, and their practicality. 3. Calculation of vibrational transition probabilities in collinear atom-diatom and diatom-diatom collisions with Lennard-Jones interaction

Part 1. Many interesting visual and mechanical phenomena occur in the critical region of fluids, both for the gas-liquid and liquid-liquid transitions. The precise thermodynamic and transport behavior here has some broad consequences for the molecular theory of liquids. Previous studies in this laboratory on a liquid-liquid critical mixture via ultrasonics supported a basically classical analysis of fluid behavior by M. Fixman (e. g., the free energy is assumed analytic in intensive variables in the thermodynamics)--at least when the fluid is not too close to critical. A breakdown in classical concepts is evidenced close to critical, in some well-defined ways. We have studied herein a liquid-liquid critical system of complementary nature (possessing a lower critical mixing or consolute temperature) to all previous mixtures, to look for new qualitative critical behavior. We did not find such new behavior in the ultrasonic absorption ascribable to the critical fluctuations, but we did find extra absorption due to chemical processes (yet these are related to the mixing behavior generating the lower consolute point). We rederived, corrected, and extended Fixman's analysis to interpret our experimental results in these more complex circumstances. The entire account of theory and experiment is prefaced by an extensive introduction recounting the general status of liquid state theory. The introduction provides a context for our present work, and also points out problems deserving attention. Interest in these problems was stimulated by this work but also by work in Part 3.

Part 2. Among variational theories of electronic structure, the Hartree-Fock theory has proved particularly valuable for a practical understanding of such properties as chemical binding, electric multipole moments, and X-ray scattering intensity. It also provides the most tractable method of calculating first-order properties under external or internal one-electron perturbations, either developed explicitly in orders of perturbation theory or in the fully self-consistent method. The accuracy and consistency of first-order properties are poorer than those of zero-order properties, but this is most often due to the use of explicit approximations in solving the perturbed equations, or to inadequacy of the variational basis in size or composition. We have calculated the electric polarizabilities of H₂, He, Li, Be, LiH, and N₂ by Hartree-Fock theory, using exact perturbation theory or the fully self-consistent method, as dictated by convenience. By careful studies on total basis set composition, we obtained good approximations to limiting Hartree-Fock values of polarizabilities with bases of reasonable size. The values for all species, and for each direction in the molecular cases, are within 8% of experiment, or of best theoretical values in the absence of the former. Our results support the use of unadorned Hartree-Pock theory for static polarizabilities needed in interpreting electron-molecule scattering data, collision-induced light scattering experiments, and other phenomena involving experimentally inaccessible polarizabilities.

Part 3. Numerical integration of the close-coupled scattering equations has been carried out to obtain vibrational transition probabilities for some models of the electronically adiabatic H₂-H₂ collision. All the models use a Lennard-Jones interaction potential between nearest atoms in the collision partners. We have analyzed the results for some insight into the vibrational excitation process in its dependence on the energy of collision, the nature of the vibrational binding potential, and other factors. We conclude also that replacement of earlier, simpler models of the interaction potential by the Lennard-Jones form adds very little realism for all the complication it introduces. A brief introduction precedes the presentation of our work and places it in the context of attempts to understand the collisional activation process in chemical reactions as well as some other chemical dynamics.

Modelization and analysis of the electric arc in low voltage circuit breakers

246 p.

Electric and magnetic losses and gains in determining the sign of refractive index

Within the framework of classic electromagnetic theories, we have studied the sign of refractive index of optical medias with the emphases on the roles of the electric and magnetic losses and gains. Starting from the Maxwell equations for an isotropic and homogeneous media, we have derived the general form of the complex refractive index and its relation with the complex electric permittivity and magnetic permeability, i.e. n = root epsilon mu, in which the intrinsic electric and magnetic losses and gains are included as the imaginary parts of the complex permittivity and permeability, respectively, as epsilon = epsilon(r) + i(epsilon i) and mu = mu(r) + i mu(i). The electric and magnetic losses are present in all passive materials, which correspond, respectively, to the positive imaginary permittivity and permeability epsilon(i) > 0 and mu(i) > 0. The electric and magnetic gains are present in materials where external pumping sources enable the light to be amplified instead of attenuated, which correspond, respectively, to the negative imaginary permittivity and permeability epsilon(i) < 0 and mu(i) < 0. We have analyzed and determined uniquely the sign of the refractive index, for all possible combinations of the four parameters epsilon(r), mu(r), epsilon(i), and mu(i), in light of the relativistic causality. A causal solution requires that the wave impedance be positive Re {Z} > 0. We illustrate the results for all cases in tables of the sign of refractive index. One of the most important messages from the sign tables is that, apart from the well-known case where simultaneously epsilon < 0 and mu < 0, there are other possibilities for the refractive index to be negative n < 0, for example, for epsilon(r) < 0, mu(r) > 0, epsilon(i) > 0, and mu(i) > 0, the refractive index is negative n < 0 provided mu(i)/epsilon(i) > mu(r)/vertical bar epsilon(r)vertical bar. (c) 2006 Elsevier B.V. All rights reserved.

Diseño y montaje de un identificador y conmutador para carga de baterías en serie

[ES]El objetivo de este proyecto es diseñar y construir un circuito identificador y conmutador para carga de baterías en serie autónomo. La funcionalidad de este dispositivo es determinar cual es la batería menos cargada de un banco de baterías de ácido plomo que alimenta un coche al estándar de 48 voltios(conformado por cuatro baterías de 12 voltios). Una vez determinado cual es la batería menos cargada debe re-­‐ direccionar la corriente dada por una placa solar a dicha batería. Todo esto debe hacerlo de forma autónoma, a través de un programa específico, implementado en un microcontrolador. En las diferentes fases del proyecto se ha diseñado el software, se ha diseñado y montado el hardware y se ha verificado su correcto funcionamiento. Además se presentan los costes y la viabilidad de una propuesta de fabricación estandarizada a partir de los planos resultantes del proyecto. Este proyecto surge como respuesta a la actual necesidad de aumentar la limitada autonomía de los coches eléctricos y hacerlos más eficientes. El proyecto se ha llevado a cabo en el laboratorio de electrónica de la ETSI de Bilbao y pretende promover el uso de los coches eléctricos y energías renovables.

Influencia del vehículo eléctrico en la red eléctrica, en función del comportamiento social.

[ES]En la actualidad, el modelo de transporte apenas ha avanzado en el intento de frenar el Cambio Climático o en el cuidado del medio ambiente. Además, el gran negocio que existe detrás del petróleo hace que este tipo de transporte sea poco sostenible. Es por eso que se está desarrollando, a nivel nacional e internacional, una solución a dicho problema que es el uso del vehiculó eléctrico (VE). La introducción masiva del VE permitirá el uso extensivo de fuentes de energía no contaminantes e intermitentes, como son las energías renovables. Sin embargo, los VEs están lejos de ser una tecnología probada. Existen aún muchos problemas en torno a él que deben ser resueltos, entre ellos se encuentra el desarrollo de las baterías, su modelo de negocio y coste o la influencia de la conexión del VE sobre la red eléctrica. Este último problema, estará muy influenciado por el comportamiento social del futuro conductor, lo cual es el eje central del proyecto.