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.

Interfaces e lacunas na assistência prestada ao adolescente soropositivo

O objetivo desta dissertação foi estudar as várias interfaces e possíveis insuficiências no atendimento prestado aos adolescentes que vivem com HIV / AIDS. Assim, a área de pesquisa concentrou-se em algumas unidades de saúde da área do Rio de Janeiro - Programa municipal 2.2. O primeiro capítulo descreve um esboço histórico da formação do Estado moderno e as bases para a política social sustentável do Estado capitalista contemporâneo culminando com a análise da construção de um modelo de proteção social no Brasil, depois dos anos trinta. Desta forma, o Estado é visto como uma área atravessada por paradoxal interesses conflitantes e as políticas sociais, administradas no interior do estado, sendo fruto de processos históricos, econômicos e políticos. No segundo capítulo, os problemas da política de saúde no Brasil são discutidos, enfocando as orientações das políticas sobre a AIDS e a adolescência. Em primeiro lugar, os aspectos históricos sobre as políticas de AIDS são analisados e, em seguida, há uma investigação do conceito de adolescência e os princípios norteadores do Estatuto da Criança e do Adolescente e do Programa Saúde do Adolescente. No terceiro capítulo o material coletado na pesquisa por profissionais de saúde é analisado e relacionado com o estudo documental com a crítica das políticas destinadas. A conclusão mostra que, apesar de todo o progresso clínico e / ou farmacológico para o tratamento de pessoas vivendo com AIDS e na formulação de políticas públicas para garantir os direitos, os adolescentes precisam de espaços de boas-vindas nas relações sociais, onde nem a família, a religião, a escola e seus pares estão preparados para essa proximidade. Outra questão importante é a incapacidade dos profissionais de saúde para lidar com os vários aspectos da doença. Contas de contenção e abuso são comuns, revelando que as unidades de saúde nem sempre desenvolvem o seu potencial para cuidar.

Chemical and Electrochemical Behavior of Graphene-Covered Silicon Photoanodes

This dissertation describes efforts over the last five years to develop protective layers for semiconductor photoelectrodes based on monolayer or few-layer graphene sheets. Graphene is an attractive candidate for a protective layer because of its known chemical inertness, transparency, ease of deposition, and limited number of electronic states. Monolayer graphene was found to effectively inhibit loss of photocurrent over 1000 seconds at n-Si/aqueous electrolyte interfaces that exhibit total loss over photocurrent over 100 seconds. Further, the presence of graphene was found to effect only partial Fermi level pinning at the Si/graphene interface with respect to a range of nonaqueous electrolytes. Fluorination of graphene was found to extend the stability imparted on n-Si by the monolayer sheet in aqueous Fe(CN)₆^3-/4- electrolyte to over 100,000 seconds. It was demonstrated that the stability of the photocurrent of n-Si/fluorinated graphene/aqueous electrolyte interfaces relative to n-Si/aqueous electrolyte interfaces is likely attributable to the inhibition of oxidation of the silicon surface.

This dissertation also relates efforts to describe and define terminology relevant to the field of photoelectrochemistry and solar fuels production. Terminology describing varying interfaces employed in electrochemical solar fuels devices are defined, and the research challenges associated with each are discussed. Methods for determining the efficiency of varying photoelectrochemical and solar-fuel-producing cells from the current-voltage behavior of the individual components of such a device without requiring the device be constructed are described, and a range of commonly employed performance metrics are explored.

Theoretical model for a periodically driven semiconductor laser subject to optical feedback from a microcantilever

We propose a theoretical model for analyzing the dynamics of a periodically driven semiconductor laser subject to optical feedback from a microcantilever. We numerically investigate the temporal evolution of the light intensity of the semiconductor laser, and we show the interspikes of the light intensity. These interspikes of light intensity are also demonstrated in our experiment. The validity of the theoretical model is verified. The observed phenomenon has a potential application for resonant sensing. (C) 2008 Optical Society of America.

Instabilities in a grating feedback external cavity semiconductor laser

Output power fluctuations in a grating external cavity diode laser with Littman configuration are described, showing peculiar chaotic behaviors of self-pulsation at the L-I curve kink points. Different spectral characteristics with multiple peaks are observed at upper and lower state of the self-pulsation. It is found also that P-N junction voltage jumps in a same pace with the pulsation. The observed phenomena reflect competition between different longitudinal modes, and transient variation of transverse modes in addition. These experimental results may contain information about the mechanisms of the chaotic instability in strong filtered feedback semiconductor lasers. (C) 2008 Optical Society of America

A mathematical and experimental investigation of microcycle spectral estimates of semiconductor flicker noise

The experimental portion of this thesis tries to estimate the density of the power spectrum of very low frequency semiconductor noise, from 10^-6.3 cps to 1. cps with a greater accuracy than that achieved in previous similar attempts: it is concluded that the spectrum is 1/f^α with α approximately 1.3 over most of the frequency range, but appearing to have a value of about 1 in the lowest decade. The noise sources are, among others, the first stage circuits of a grounded input silicon epitaxial operational amplifier. This thesis also investigates a peculiar form of stationarity which seems to distinguish flicker noise from other semiconductor noise.

In order to decrease by an order of magnitude the pernicious effects of temperature drifts, semiconductor "aging", and possible mechanical failures associated with prolonged periods of data taking, 10 independent noise sources were time-multiplexed and their spectral estimates were subsequently averaged. If the sources have similar spectra, it is demonstrated that this reduces the necessary data-taking time by a factor of 10 for a given accuracy.

In view of the measured high temperature sensitivity of the noise sources, it was necessary to combine the passive attenuation of a special-material container with active control. The noise sources were placed in a copper-epoxy container of high heat capacity and medium heat conductivity, and that container was immersed in a temperature controlled circulating ethylene-glycol bath.

Other spectra of interest, estimated from data taken concurrently with the semiconductor noise data were the spectra of the bath's controlled temperature, the semiconductor surface temperature, and the power supply voltage amplitude fluctuations. A brief description of the equipment constructed to obtain the aforementioned data is included.

The analytical portion of this work is concerned with the following questions: what is the best final spectral density estimate given 10 statistically independent ones of varying quality and magnitude? How can the Blackman and Tukey algorithm which is used for spectral estimation in this work be improved upon? How can non-equidistant sampling reduce data processing cost? Should one try to remove common trands shared by supposedly statistically independent noise sources and, if so, what are the mathematical difficulties involved? What is a physically plausible mathematical model that can account for flicker noise and what are the mathematical implications on its statistical properties? Finally, the variance of the spectral estimate obtained through the Blackman/Tukey algorithm is analyzed in greater detail; the variance is shown to diverge for α ≥ 1 in an assumed power spectrum of k/|f|^α, unless the assumed spectrum is "truncated".

Subwavelength imaging with two symmetrical interfaces by dielectric-tube photonic crystals

As distinct from coated photonic crystals, in this paper we propose a novel one that is made of dielectric tubes arranged in a close-packet square lattice. Without metallic cores, this structure is low-loss and convenient to fabricate. A left-handed frequency region is found in the second band by dispersion characteristic analysis. Without inactive modes for the transverse electric mode, negative refraction and subwavelength imaging are demonstrated by the finite-difference time-domain simulations with two symmetrical interfaces, i.e. Gamma X and Gamma M.

O design de interfaces epiteliais dinâmicas: como as novas tecnologias afetam o projeto de tatuagens

A tatuagem é uma antiga forma de inscrição corporal que apesar de sua idade não sofreu alterações em termos de materiais e técnicas. O desenvolvimento de tecnologias para a concepção de novas modalidades de intervenção orgânica terá ramificações em diversas áreas, permitindo o uso de novas interfaces epiteliais interativas (tatuagens dinâmicas responsivas), e criando novas vias de interação e comunicação incorporada. Em contraste à prática tradicional de imagens estáticas, as tatuagens dinâmicas (TDs) permitem a geração de imagens dinâmicas e interativas na pele. Nosso objetivo aqui é apresentar este novo campo de pesquisa e refletir sobre o papel do designer no projeto de tatuagens dinâmicas e as implicações destas tatuagens que transformam a pele em uma nova fonte de inscrições interativas e reversíveis.