Orientadores: Amauri Garcia, Wislei Riuper Osorio / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-13T18:01:29Z (GMT). No. of bitstreams: 1 Peixoto_LeandroCesardeLorena_M.pdf: 5871010 bytes, checksum: f7403606c814ec8a30965352f0a93e87 (MD5) Previous issue date: 2009 / Resumo: Produtores de baterias chumbo-ácido têm modificado os processos de produção e composição química das ligas utilizadas nas grades das baterias com intuito de diminuir o seu peso final, bem como reduzir os custos de produção e também aumentar o ciclo de vida útil e a resistência à corrosão. As morfologias das estruturas de solidificação, caracterizadas principalmente por arranjos celulares e dendríticos, e suas grandezas representadas por espaçamentos celulares e dendríticos controlam a distribuição de soluto, segundas fases dentro das regiões intercelulares ou interdendríticas, que determinam as propriedades finais. O comportamento mecânico e as características estruturais dos componentes de bateria têm papel importante no desempenho das baterias. O presente trabalho pretende contribuir para o entendimento do desenvolvimento microestrutural de ligas diluídas do sistema Pb-Sn (Pb-1,0%Sn e Pb-2,5%Sn) que possuem elevada importância para a indústria na fabricação de componentes de baterias automotivas e estacionárias. Os experimentos de solidificação realizados em dispositivo no qual o calor é extraído somente pelo sistema de resfriamento a água, localizado na base do conjunto lingote/lingoteira (solidificação ascendente). As variáveis térmicas de solidificação foram determinadas a partir do registro de temperaturas de termopares posicionados dentro da lingoteira em diferentes posições em relação à superfície refrigerada do lingote. Amostras das mencionadas ligas Pb-Sn foram utilizadas para analisar as influências das variáveis térmicas de solidificação e da concentração de soluto nas macro e microestruturas resultantes e na resistência mecânica. Foram determinados os limites de resistência à tração e alongamentos específicos em função do espaçamento celular e a influência da microestrutura no comportamento eletroquímico foi avaliada por intermédios dos ensaios de espectroscopia de impedância eletroquímica, extrapolação de Tafel, curvas de polarização e análise por circuito equivalente em solução eletrolítica de ácido sulfúrico. Observou-se que a resistência a corrosão diminui e o limite de resistência a tração aumenta com a diminuição do espaçamento celular. / Abstract: Lead-acid batteries manufacturers have modified the manufacturing processes and the chemical composition of alloys used in battery grids in order to decrease their weight as well as to reduce the production costs, and to increase the battery life-time cycle and the corrosion-resistance. The morphological microstructures characterized by cellular and dendritic arrays and its correspondents cellular and dendrite arm spacings control the solute distribution, second phases in the intercellular and interdendritic regions affecting the resulting properties. The mechanical behavior and microstructural characteristics of lead-acid battery components have an important role in the battery performance. The present work aims to contribute to the understanding of the microstructural development of dilute Pb-1,0 wt.%Sn and Pb-2.5 wt.%Sn alloys which are widely applied in the manufacturing of automobile and stationary lead-acid batteries. A water-cooled vertical upward unidirectional solidification system was used to obtain the samples. The experimental set-up was designed in such a way that the heat was extracted only through the water-cooled bottom, promoting upward directional solidification. Thermal readings were obtained by thermocouples positioned at different distances from the heat-extracting surface at the casting bottom. Pb-Sn alloy samples were used to analyze the effects of the thermal solidification variables and solute content on the resulting macro and microstructures and on the mechanical properties. The ultimate tensile strength and the elongation were determined as a function of the cellular arm spacing. The effect of the resulting microstructure on the electrochemical corrosion behavior was also analyzed based on electrochemical parameters, determined by Tafel plots, polarization curves and an equivalent circuit analysis after corrosion tests carried out in a sulphuric acid solution. It was observed that the corrosion resistance decreases and the ultimate tensile strength increases with decreasing cellular spacing. / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Commercial decisions are been made with respect to the competitive advantage of manufacturing catalytic converters in South Africa. This thesis identifies those factors relating to the sourcing of stainless steel and the impact it has of securing future business in a competitive environment. The catalytic converter industry requires the support of a stainless steel plant that provides high quality products at a competitive price, while keeping abreast with international developments.

Commonly used amines in power industry, including morpholine, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), and DMA (dimethylallylamine) were evaluated for their effect on AISI 1018 steel at 250oF. Samples were exposed to an autoclave containing amine added aqueous solution at pH of 9.5 for 1, 2, 4, 6, 8, and 12 hours. Morphology studies were carried using scanning electron microscope (SEM), phase analysis was done utilizing Fourier transform infrared spectroscopy (FTIR), and weight loss was performed to assess kinetics of oxidation. Control samples showed the highest metal dissolution rate. DBU showed the best performance in metal protection and SEM indicated the presence of a free-crack layer formed by fine particles in that set. FTIR showed that DBU apparently favored the formation of magnetite. It is believed that fine particles impede intrusion of aggressive ions into the metal surface by forming a barrier layer. FTIR demonstrated that DMA formed more oxyhydroxides, whereas morpholine presented magnetite to hematite transformation as early as 2 hours. SEM revealed that control and DMA produced acicular particles characteristic of oxyhydroxides while morpholine and DBU presented more equiaxed particles.

Hierarchical arrangement of biological composites such as nacre and bone containing high filler (ceramic) content results in high strength and toughness of the natural material. In this study we mimic the design of layered bone microstructure and fabricate an optimal multifunctional bio-nanocomposite having strength, toughness and corrosion resistance. Poly (butylene adipate-co-terephthalate) (PBAT), a biodegradable polymer was used as a substrate material with the reinforcement of LDH (Layered double hydroxide) as a nanofiller in different concentrations to achieve enhancement in mechanical properties as well as processing related thermostability. Corrosion resistance was increased by mimicking a layered structured which incorporated a tortuous diffusion path.

The new nickel/layered silicate nanocomposites were electrodeposited from different pHs to study the influence on the metal ions/layered silicate plating solution and on the properties of the deposited films. Nickel/layered silicate nanocomposites were fabricated from citrate bath atacidic pHs (1.6−3.0), from Watts’ type solution (pH ~4-5), and from citrate bath at basic pH (~9). Additionally, the new nickel/molybdenum/layered silicate nanocomposites were electrodeposited from citrate bath at pH 9.5. The silicate, montmorillonite (MMT), was exfoliated by stirring in aqueous solution over 24 hours. The plating solutions were analyzed for zeta potential, particle size, viscosity, and conductivity to investigate the effects of the composition at various pHs. The preferred crystalline orientation and the crystalline size of nickel, nickel/layered silicate, nickel/molybdenum, and nickel/molybdenum/layered silicate films were examined by X-ray diffraction. The microstructure of the coatings and the surface roughness was investigated by scanning electron microscopy and atomic force microscopy. Nickel/molybdenum/layered silicate nanocomposites containing low content of layered silicate (1.0 g/L) had increase 32 % hardness and 22 % Young’s modulus values over the pure nickel/molybdenum alloy films. The potentiodynamic polarization and electrochemical impedance measurements showed that the nickel/molybdenum/layered silicate nanocomposite layers have higher corrosion resistance in 3.5% NaCl compared to the pure alloy films. The corrosion current density of the nickel/molybdenum/layered silicate nanocomposite composed of 0.5 g/L MMT is 0.63 µA·cm-2 as compare to a nickel/molybdenum alloy which is 2.00 µA·cm-2.

Superhydrophobic coatings (SHC) with excellent self-cleaning and corrosion resistance property is developed on magnetite coated AISI SAE 1020 steel by using a simple immersion method. Roughness measurement, scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), contact angle measurement (CAM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS), and qualitative characterization of self-cleaning behavior, antifouling property and durability of the coatings are assessed. A water contact angle as high as 152o on the coated surface with excellent self-cleaning and resistivity to corrosion and good longevity in atmospheric air is obtained. Self-cleaning test results prove that these surfaces can find applications in large scale production of engineering materials. Potentiodynamic polarization tests and EIS tests confirm that the superhydrophobic low carbon steel surfaces have better resistance to corrosion compared to bare steel and magnetite coated steel in 3.5% NaCl solution. But the longevity of the coated steel surfaces in 3.5% salt solution is limited, which is revealed by the immersion durability test. However, hydrophobic coatings (HC) have better stability in normal tap water, and it can stay unharmed up to 15 days. Finally, hydrophobic coatings on low carbon steel surface retains hydrophobic in open atmosphere for more than two months. Results of this investigation show surface roughness is a critical factor in manufacturing hydrophobic steel surfaces. Higher contact angles are obtained for rougher and more uniform surfaces. A linear mathematical relationship (y =6x+104; R2 = 0.93) is obtained between contact angle (y) and surface roughness (x).

A área de microfabricação de dispositivos de interesse em química analítica tem se expandido muito ao longo dos últimos anos. Uma série de produtos e processos tem sido proposta, tendo como base as tecnologias da área de microeletrônica. Muito destes processos são bastante sofisticados, estando além das necessidades para produção de alguns dispositivos relativamente simples e que são bastante úteis para a química analítica. Este é o caso, por exemplo, dos microcanais para implementação de sistemas eletroforéticos ou micro sistemas em fluxo. Neste contexto, surge a proposta deste trabalho, qual seja desenvolver processos e produtos de interesse nesta área. Esse objetivo foi alcançado pelo desenvolvimento de dois processos: um para produção de microcanais em resina de poliéster através de moldagem e outro de corrosão de vidro utilizando toner de impressora laser como resiste. O primeiro partiu de fotolito para produção de molde em silício através de processo de corrosão por plasma de SF6. Peças de resina de poliéster isoftálica são produzidas por polimerização sobre este molde. Para garantir a desmoldagem não traumática e boa reprodução de detalhes, foi incorporado óleo de silicone durante a preparação da resina. Com este procedimento, foi possível obter canais com 14,0 µm de profundidade e irregularidades superficiais de 1,4 µm para um molde com 15,3 µm de elevação e 0,5 µm de irregularidades superficiais. Com o uso de uma manta flexível de silicone como contraparte, foi possível gerar microcanais cuja altura foi avaliada como sendo da ordem de 5 a 7 µm. Esta avaliação foi conseguida através de medida de condutância após o preenchimento do microcanal com solução de KCl. No segundo processo, toner de impressora laser foi utilizado como resiste para corrosão de vidrO. O layout era diretamente impresso sobre papel aditivado com maltodextrina ou papel utilizado como suporte para etiquetas autocolantes através de uma impressora HP LaserJet 6L com resolução de 600 dpi. Após a transferência térmica da imagem para lâminas de vidro alcalino de 1,0 mm de espessura, a corrosão em ácido fluorídrico permitiu obter canais com 7,1 µm de profundidade e irregularidades de 1,0 µm. Embora este segundo processo apresente desvantagens com relação à resolução tanto no plano da lâmina como na profundidade do canal, quando comparado ao primeiro, deve-se ressaltar a extrema simplicidade, rapidez e baixo custo do processo que deve ser interessante para a produção de protótipos. Já para o primeiro processo, destaca-se a adequação à produção em pequena escala de dispositivos microcanais de baixo custo. / Several processes and products have been proposed to build and use microstructures for chemical purposes. Most of these processes were adapted from microelectronic technologies, which resulted in products with excellent resolution and quality. However, there are some devices that could be generated by simpler and rougher processes. In this work, two processes were developed in order to allow producing simple devices based on microchannels. The first process is a method to produce polyester based devices. A conventional microelectronic process was used to produce a silicon matrix. This matrix was used to produce blocks of isophthalic resin by in situ polymerization. The best results were obtained by adding 1 % (w/w) silicone oil during the polyester resin preparation. This additive improves the mold relief and the smoothness of the device surface. Channels 14.0-µm depth and roughness of 1.4 µm were obtained with a mold with structure height of 15.3 µm and roughness of 0.5 µm. A flexible sheet of silicone allows forming enclosed microchannels with depth of 5-7 µm. This dimension was evaluated by conductance measurement after filling the channel with KCl solution. A process for glass corrosion, using laser printer toner as resist, was proposed. In this method, the layout is printed over a special sheet of paper using a HP LaserJet 6L laser printer. The paper is used to transfer the toner to a soda-lime glass lamina by a thermic process. Hydrofluoric acid solution was used to promote the selective glass corrosion. Channels 7.1-µm depth and roughness of 1.0 µm were obtained. Although this second method does not give the saroe resolution and aspect ratio as the first one, it is suitable to easy and fast prototyping. Gn the other hand, the first method is suitable for low-cost production of devices in small scale.

A corrosão metálica é um problema que afeta a economia mundial, sendo responsável pelo aumento dos custos de geração, transmissão e distribuição de energia elétrica e pode ser influenciada por atividades microbianas, podendo levar a aceleração ou inibição do processo. O presente trabalho teve por objetivo isolar e identificar as bactérias associadas a processos de corrosão em torres de transmissão de energia, bem como avaliar a resistência destas bactérias a diferentes metais pesados buscando selecionar micro-organismos com potencial para biorremediação. A identificação taxonômica dos isolados associados a elementos metálicos foi efetuada por análise filogenética das sequências parciais do gene RNA ribossomal 16S, resultando em 101 bactérias distribuídas em oito gêneros: Lysinibacillus, Serratia, Stenotrophomonas, Pseudomonas, Exiguobacterium, Chryseobacterium, Bacillus e Acinetobacter. Todos os gêneros foram resistentes a mais de um metal, sendo que o metal que menos afetou o crescimento dos isolados foi o cromo e o que mais afetou foi o mercúrio. / Metallic corrosion is a problem that affects the world economy, being responsible for the increased costs of generating, transmission and distribution of electricity and can be influenced by microbial activities, leading to inhibition or acceleration of the process. This study aimed to isolate and identify bacteria associated with corrosion processes in metallic structures of power transmission towers, as well as evaluating the resistance of these bacteria to different heavy metals, in order to select microorganisms with potential for biorremediation. The taxonomic identification of the isolates of bacteria associated with metallic elements was performed by phylogenetic analysis of partial sequences of 16S ribosomal RNA gene, resulting in 101 bacteria distributed in eight genera: Lysinibacillus, Serratia, Stenotrophomonas, Pseudomonas, Exiguobacterium, Chryseobacterium, Bacillus and Acinetobacter. All genera were resistant to more than one metal. Chromium and mercury were the metals that least and most affected the growth of isolates, respectively.

Aluminium smelting is a high temperature electrometallurgical process, which suffers considerable inefficiencies in power utilization and equipment maintenance. Aluminium smelting cell works in the extreme environments that contain extraordinarily aggressive gases, such as HF, CO and SO2. Mild steel used as a structural material in the aluminium industry, can be catastrophically corroded or oxidized in these conditions. This project was mainly concerned with extending the lifetime of metal structures installed immediately above the aluminium smelting cells. An aluminium-rich coating was developed on low carbon steel A06 using pack cementation technique. Yttria (Y2O3) was also used to improve the corrosion resistance of coating. Kinetics of the coating formation were studied. XRD, FESEM and FIB were employed to investigate the phase constitution and the surface morphology. Together with other potentially competitive materials, aluminium-rich coating was evaluated in simulated plant environments. Results from the long time (up to 2500h) isothermal oxidation of materials at high temperature (800??C) in air showed that the oxidation resistance of coated A06 is close to that of stainless steel 304 and even better than SS304 in cyclic oxidation tests. Coated A06 was also found to have the best sulfidation resistance among the materials tested in the gas mixture contains SO2 at 800??C. Related kinetics and mechanisms were also studied. The superior corrosion resistance of the coated A06 is attributed to the slow growing alpha-Al2O3 formed. Low temperature corrosion tests were undertaken in the gas mixtures containing air, H2O, HCl and SO2 at 400??C. Together with SS304 and 253MA, coated A06 showed excellent corrosion resistance in all the conditions. The ranking of the top three materials for corrosion resistance is: 253MA, coated A06 and SS304. It is believed that aluminised A06 is an ideal and economical replacement material in the severe corrosive aluminium smelting cell environment.

Ph.D. / Electrical Engineering / A novel combinatory on-line technique coupling Electrochemistry (EC) with Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) for in-situ quantitative determination of the corrosion mechanism in magnetic thin film structures has been developed in this research. Detailed construction of a system and a comprehensive methodology was described in this dissertation. Uniformly coated multi-layer magnetic thin film samples with multi-elemental alloys containing CoCrPtB and CrMo/Cr on the Ni/P substrate were used in this research for demonstrations. In-situ quantifications conducted in a series of experiments revealed that elemental dissolution was a predominant mechanism during corrosion courses of metallic thin film materials. At the microscopic scale, using results from depletion rate determination as well as cross-sectional analyses of microstructures and magnetic features, elemental passivity was observed to occur, depending on corrosion conditions. Without external influences, surface topographic measurements indicated that passive film could be produced at the macro-scale. The dependence of the dissolution rate of each metallic ion of alloys on electrolyte concentration, potential bias, scanning rate, and corrosion duration suggested that the most critical influential factor in corrosion mechanisms was epitaxial microstructures with strongly-oriented arrangements of grains and grain boundaries. Through the use of cross-sectional microstructural analysis, including high resolution TEM micrography, electron FFT diffraction, and nano-probe with EDS profiling, variations of elemental spatial distributions at grains and grain boundaries due to the corrosion phenomena were discovered, which provided a comprehensive understanding of occurrences of micro-corrosion in thin film structures. Because of the unique magnetic property of magnetic thin films, extensive studies of field strengths from the surface were also performed in this research. Important magnetization variations were noticed when cross-sectional images were obtained. Finally, models of corrosion kinetics in the multiple layers of magnetic thin film structures were proposed.