On The Thermally Induced Cracking Of A Segmented Coating Deposited On The Outer Surface Of A Hollow Cylinder

In this work, the thermally induced cracking behavior of a segmented coating has been investigated. The geometry under consideration is a hollow cylinder with a segmented coating deposited onto its outer surface. The segmentation cracks are modeled as a periodic array of axial edge cracks. The finite element method is utilized to obtain the solution of the multiple crack problem and the Thermal Stress Intensity Factors (TSIFs) are calculated. Based on dimensional analysis, the main parameters affecting TSIFs are identified. It has been found that the TSIF is a monotonically increasing function of segmentation crack spacing. This result confirms that a segmented coating exhibits much higher thermal shock resistance than an intact counterpart, if only the segmentation crack spacing is narrow enough. The dependence of TSIF on some other parameters, such as normalized time, segmentation crack depth, convection severity as well as material constants, has also been discussed. (C) 2008 Elsevier B.V. All rights reserved.

The mechanism of PEO process on Al–Si alloys with the bulk primary silicon

This study focuses on mechanism of ceramic coating on Al-Si alloys with bulk primary Si using plasma electrolytic oxidation (PEO) technology. Al-Si alloys with 27-32% Si in weight were used as substrates. The morphologies, composition and microstructure of PEO coatings were investigated by scanning electron microscopy (SEM) with energy dispersive X-ray system (EDX). Results showed that the PEO process had four different stages. The effect of bulk Si is greatly on the morphology and composition of coatings at first three stages. Anodic oxide films formed on Al and Si phases, respectively. When the voltage exceeded 40 V, glow appeared and concentrated on the localized zone of interface of Al and Si phase. Al-Si-O compounds formed and covered on the dendrite Si phase surface, and the coating on bulk Si, which was silicon oxide, was rougher than that on other phase. If the treatment time was long enough, the coatings with uniform surface morphologies and elements distribution will be obtained but the microstructure of inner layer is looser due to the bulk Si.

On a novel method of impact by a front-end-coated bullet to evaluate the interface adhesion between film and substrate

A preliminary experiment was carried out to validate the feasibility of the method of impact by a front-end-coated bullet to evaluate the interface adhesion between film and substrate. The theoretical description of the initiation, propagation and evolution of the stress pulse during impact was generalized and formulized. The effects of the crucial parameters on the interface stress were further investigated with FEM. The results found the promising prospect of the application of such a method and provided useful guidance for experimental design.

Economics of co-managing water quality and invasive species for California and Baja California coastal boats

Regulatory action to protect California’s coastal water quality from degradation by copper from recreational boats’ antifouling paints interacts with efforts to prevent transport of invasive, hull-fouling species. A copper regulatory program is in place for a major yacht basin in northern San Diego Bay and in process for other major, California boat basins. “Companion” fouling control strategies are used with copper-based antifouling paints, as some invasive species have developed resistance to the copper biocide. Such strategies are critical for boats with less toxic or nontoxic hull coatings. Boat traffic along over 3,000 miles of coastline in California and Baja California increases invasive species transport risks. For example, 80% of boats in Baja California marinas are from the United States, especially California. Policy makers, boating businesses and boat owners need information on costs and supply-side capacity for effective fouling control measures to co-manage water quality and invasive species concerns. (PDF contains 3 pages)

Proton transfers at the air-water interface

Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes.

Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H₃O⁺(g), can protonate most (non-alkane) organic species, whereas H₃O⁺(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the ‘function’ of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided valuable information regarding the structure of aqueous interfaces, but structure alone is inadequate to decipher the function. By similar analogy, theoretical predictions based on classical molecular dynamics have remained limited in their scope.

Recently, we have adapted an analytical electrospray ionization mass spectrometer (ESIMS) for probing reactions at the gas-liquid interface in real time. This technique is direct, surface-specific,and provides unambiguous mass-to-charge ratios of interfacial species. With this innovation, we have been able to investigate the following:

1. How do anions mediate proton transfers at the air-water interface?

2. What is the basis for the negative surface potential at the air-water interface?

3. What is the mechanism for catalysis ‘on-water’?

In addition to our experiments with the ESIMS, we applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the molecular scale. Our results unambiguously demonstrated the role of electrostatic-reorganization of interfacial water during proton transfer events. With our experimental and theoretical results on the ‘superacidity’ of the surface of mildly acidic water, we also explored implications on atmospheric chemistry and green chemistry. Our most recent results explained the basis for the negative charge of the air-water interface and showed that the water-hydrophobe interface could serve as a site for enhanced autodissociation of water compared to the condensed phase.

Fracture of materials undergoing solid-solid phase transformation

A large number of technologically important materials undergo solid-solid phase transformations. Examples range from ferroelectrics (transducers and memory devices), zirconia (Thermal Barrier Coatings) to nickel superalloys and (lithium) iron phosphate (Li-ion batteries). These transformations involve a change in the crystal structure either through diffusion of species or local rearrangement of atoms. This change of crystal structure leads to a macroscopic change of shape or volume or both and results in internal stresses during the transformation. In certain situations this stress field gives rise to cracks (tin, iron phosphate etc.) which continue to propagate as the transformation front traverses the material. In other materials the transformation modifies the stress field around cracks and effects crack growth behavior (zirconia, ferroelectrics). These observations serve as our motivation to study cracks in solids undergoing phase transformations. Understanding these effects will help in improving the mechanical reliability of the devices employing these materials.

In this thesis we present work on two problems concerning the interplay between cracks and phase transformations. First, we consider the directional growth of a set of parallel edge cracks due to a solid-solid transformation. We conclude from our analysis that phase transformations can lead to formation of parallel edge cracks when the transformation strain satisfies certain conditions and the resulting cracks grow all the way till their tips cross over the phase boundary. Moreover the cracks continue to grow as the phase boundary traverses into the interior of the body at a uniform spacing without any instabilities. There exists an optimal value for the spacing between the cracks. We ascertain these conclusion by performing numerical simulations using finite elements.

Second, we model the effect of the semiconducting nature and dopants on cracks in ferroelectric perovskite materials, particularly barium titanate. Traditional approaches to model fracture in these materials have treated them as insulators. In reality, they are wide bandgap semiconductors with oxygen vacancies and trace impurities acting as dopants. We incorporate the space charge arising due the semiconducting effect and dopant ionization in a phase field model for the ferroelectric. We derive the governing equations by invoking the dissipation inequality over a ferroelectric domain containing a crack. This approach also yields the driving force acting on the crack. Our phase field simulations of polarization domain evolution around a crack show the accumulation of electronic charge on the crack surface making it more permeable than was previously believed so, as seen in recent experiments. We also discuss the effect the space charge has on domain formation and the crack driving force.

Three-dimensional self-assembly of brush block copolymers to photonic crystals

The development of Ring Opening Metathesis Polymerization has allowed the world of block copolymers to expand into brush block copolymers. Brush block copolymers consist of a polymer backbone with polymeric side chains, forcing the backbone to hold a stretched conformation and giving it a worm-like shape. These brush block copolymers have a number of advantages over tradition block copolymers, including faster self-assembly behavior, larger domain sizes, and much less entanglement. This makes them an ideal candidate in the development of a bottom-up approach to forming photonic crystals. Photonic crystals are periodic nanostructures that transmit and reflect only certain wavelengths of light, forming a band gap. These are used in a number of coatings and other optical uses. One and two dimensional photonic crystals are commercially available, though are often expensive and difficult to manufacture. Previous work has focused on the creation of one dimensional photonic crystals from brush block copolymers. In this thesis, I will focus on the synthesis and characterization of asymmetric brush block copolymers for self-assembly into two and three dimensional photonic crystals. Three series of brush block copolymers were made and characterized by Gel Permeation Chromatography and Nuclear Magnetic Resonance spectroscopy. They were then made into films through compressive thermal annealing and characterized by UV-Vis Spectroscopy and Scanning Electron Microscopy. Evidence of non-lamellar structures were seen, indicating the first reported creation of two or three dimensional photonic crystals from brush block copolymers.

High fidelity probe and mitigation of mirror thermal fluctuations

Thermal noise arising from mechanical loss in high reflective dielectric coatings is a significant source of noise in precision optical measurements. In particular, Advanced LIGO, a large scale interferometer aiming to observed gravitational wave, is expected to be limited by coating thermal noise in the most sensitive region around 30–300 Hz. Various theoretical calculations for predicting coating Brownian noise have been proposed. However, due to the relatively limited knowledge of the coating material properties, an accurate approximation of the noise cannot be achieved. A testbed that can directly observed coating thermal noise close to Advanced LIGO band will serve as an indispensable tool to verify the calculations, study material properties of the coating, and estimate the detector’s performance.

This dissertation reports a setup that has sensitivity to observe wide band (10Hz to 1kHz) thermal noise from fused silica/tantala coating at room temperature from fixed-spacer Fabry–Perot cavities. Important fundamental noises and technical noises associated with the setup are discussed. The coating loss obtained from the measurement agrees with results reported in the literature. The setup serves as a testbed to study thermal noise in high reflective mirrors from different materials. One example is a heterostructure of Al_xGa_1−xAs (AlGaAs). An optimized design to minimize thermo–optic noise in the coating is proposed and discussed in this work.

Magnetic alignment of high-aspect ratio microwires into vertical arrays

Fundamental studies of magnetic alignment of highly anisotropic mesostructures can enable the clean-room-free fabrication of flexible, array-based solar and electronic devices, in which preferential orientation of nano- or microwire-type objects is desired. In this study, ensembles of 100 micron long Si microwires with ferromagnetic Ni and Co coatings are oriented vertically in the presence of magnetic fields. The degree of vertical alignment and threshold field strength depend on geometric factors, such as microwire length and ferromagnetic coating thickness, as well as interfacial interactions, which are modulated by varying solvent and substrate surface chemistry. Microwire ensembles with vertical alignment over 97% within 10 degrees of normal, as measured by X-ray diffraction, are achieved over square cm scale areas and set into flexible polymer films. A force balance model has been developed as a predictive tool for magnetic alignment, incorporating magnetic torque and empirically derived surface adhesion parameters. As supported by these calculations, microwires are shown to detach from the surface and align vertically in the presence of magnetic fields on the order of 100 gauss. Microwires aligned in this manner are set into a polydimethylsiloxane film where they retain their vertical alignment after the field has been removed and can subsequently be used as a flexible solar absorber layer. Finally, these microwires arrays can be protected for use in electrochemical cells by the conformal deposition of a graphene layer.

裂缝光纤传感的工程应用

光纤传感的灵敏性及工程"存活率"是其工程实用化的两个关键技术参量,对光纤-混凝土结构两种常用裂缝光纤传感光信号对裂缝宽度的灵敏性与存活率进行了实验研究,对光纤涂覆层对灵敏性影响的大小和机理进行了分析,并制作了灵敏性与存活率均较高的光纤试验样本,与裂缝成45°夹角时,相比于等直径的普通二次涂覆粗光纤(10/125/900μm),样本的灵敏性提高近65%,而存活率亦高出约15%。研究结果可为裂缝光纤传感的优化设计和工程应用提供了基本参照。

光纤涂敷层对光纤裂缝传感器分布式监测能力的影响

基于混凝土模型试验，对涂敷层的传感光纤的裂缝复用能力进行了定量分析，得到了传感光纤和工程结构裂缝夹角在30°，45°，60°时的复用能力与裂缝宽度的关系曲线。对由软性材料构成的光纤涂敷层来说，光纤的复用能力随涂敷层厚度的增加而增大，在与裂缝夹角成45°时，二次涂敷粗光纤的复用能力约为细光纤的5倍，表明光纤敷层对光纤裂缝监测的复用能力具有较大影响。对这种影响的机理进行了理论分析和试验研究，发现当混凝土开裂时，光纤沿混凝土界面的滑移是光纤涂敷层影响光纤裂缝复用能力的主要原因，在光纤与裂缝夹角成45°时，这一影

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.

Estudo da influência do teor de segmentos hidrofílicos na síntese de poliuretanos dispersos em água

Considerações ambientais têm aumentado a pesquisa e o desenvolvimento de sistemas poliméricos aquosos para diversos tipos de aplicações, principalmente como revestimentos. Nesta dissertação, foram sintetizadas formulações não-poluentes à base de poliuretanos dispersos em água (PUDs), com 40% de teor de sólidos, na ausência de solventes orgânicos. Os monômeros empregados foram copolímeros em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), com teor de 25% de segmento hidrofílico EG, poli (glicol propilênico) (PPG), ácido dimetilolpropiônico (DMPA), diisocianato de isoforona (IPDI) e hidrazina (HYD), como extensor de cadeia. Foram variadas as razões entre o número de equivalente-grama de grupamentos isocianato e hidroxila (NCO/OH) e a proporção em equivalente-grama de PPG e dos copolímeros em bloco (EG-b-PG). Foi observado que a incorporação de altas quantidades de copolímero dificultou a síntese dos poliuretanos dispersos em água, levando à formação de géis. O tamanho médio de partícula e a viscosidade das dispersões foram determinados. Os filmes vazados a partir dessas dispersões foram avaliados quanto à capacidade de absorção de água, resistência mecânica, termogravimetria (TG), e caracterizados por espectroscopia na região do infravermelho (FTIR). As dispersões poliuretânicas produzidas se mostraram satisfatórias quando aplicadas como revestimento para madeira, metais e vidro

Electrocatalytic reduction of dioxygen at chemically modified electrodes

The kinetics of the reduction of O₂ by Ru(NH₃)₆⁺² as catalyzed by cobalt(II) tetrakis(4-N-methylpyridyl)porphyrin are described both in homogeneous solution and when the reactants are confined to Nafion coatings on graphite electrodes. The catalytic mechanism is determined and the factors that can control the total reduction currents at Nafion-coated electrodes are specified. A kinetic zone diagram for analyzing the behavior of catalyst-mediator-substrate systems at polymer coated electrodes is presented and utilized in identifying the current-limiting processes. Good agreement is demonstrated between calculated and measured reduction currents at rotating disk electrodes. The experimental conditions that will yield the optimum performance of coated electrodes are discussed, and a relationship is derived for the optimal coating thickness.

The relation between the reduction potentials of adsorbed and unadsorbed cobalt(III) tetrakis(4-N-methylpyridyl)porphyrin and those where it catalyzes the electroreduction of dioxygen is described. There is an unusually large change in the formal potential of the Co(III) couple upon the adsorption of the porphyrin on the graphite electrode surface. The mechanism in which the (inevitably) adsorbed porphyrin catalyzes the reduction of O₂ is in accord with a general mechanistic scheme proposed for most monomeric cobalt porphyrins.

Four new dimeric metalloporphyrins (prepared in the laboratory of Professor C. K. Chang) have the two porphyrin rings linked by an anthracene bridge attached to meso positions. The electrocatalytic behavior of the diporphyrins towards the reduction of O₂ at graphite electrodes has been examined for the following combination of metal centers: Co-Cu, Co-Fe, Fe-Fe, Fe-H₂. The Co-Cu diporphyrin catalyzes the reduction of O₂ to H₂O₂ but no further. The other three catalysts all exhibit mixed reduction pathways leading to both H₂O₂ and H₂O. However, the pathways that lead to H₂O do not involve H₂O₂ as an intermediate. A possible mechanistic scheme is offered to account for the observed behavior.

Estudo da incorporação de diferentes tipos de argilas hidrofílicas em dispersões aquosas de poliuretanos para formação de nanocompósitos

Neste trabalho foram sintetizados nanocompósitos à base de poliuretanos em dispersão aquosa (NWPUs) e argilas hidrofílicas do tipo montimorilonita (MMT) de natureza sódica e cálcica. Os monômeros empregados na síntese foram: poli(glicol propilênico) (PPG); copolímero em bloco à base de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), com teor de 7% de EG; ácido dimetilolpropiônico (DMPA) e diisocianato de isoforona (IPDI). Os NWPUs tiveram as argilas, previamente deslaminadas em água e incorporadas à formulação no momento da dispersão do prepolímero. Dispersões aquosas (WPUs), sem a presença de argila, foram sintetizadas como base, nas quais foram variadas a razão NCO/OH e a proporção de copolímero em relação ao PPG. Nas formulações NWPUs, foram variados também o teor de argila em relação à massa de prepolímero e o tipo de argila sódica e cálcica. As dispersões foram avaliadas, quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade. Os filmes vazados a partir das dispersões foram caracterizados por espectrometria na região do infravermelho (FTIR), difração de raios-x (XRD) e microscopia eletrônica de varredura (SEM). A resistência térmica dos filmes foi determinada por termogravimetria (TG) e a resistência mecânica dos filmes foi avaliada por ensaios mecânicos em dinamômetro. O grau de absorção de água dos filmes também foi determinado. A formação de nanocompósitos à base de água foi confirmada pela ausência do pico de XRD, característico das argilas empregadas na maioria dos filmes analisados. As micrografias obtidas por SEM confirmam uma dispersão homogênea das argilas na matriz poliuretânica. Os filmes à base de nanocompósitos (NWPUs) apresentaram propriedades superiores às apresentadas por aqueles obtidos a partir das dispersões sem argilas (WPUs). Os revestimentos formados a partir da aplicação das dispersões aderiram à maioria dos substratos testados (metal, vidro, madeira e papel) formando superfícies homogêneas