860 resultados para Heat Treatment - Effects
Resumo:
We study semiparametric two-step estimators which have the same structure as parametric doubly robust estimators in their second step. The key difference is that we do not impose any parametric restriction on the nuisance functions that are estimated in a first stage, but retain a fully nonparametric model instead. We call these estimators semiparametric doubly robust estimators (SDREs), and show that they possess superior theoretical and practical properties compared to generic semiparametric two-step estimators. In particular, our estimators have substantially smaller first-order bias, allow for a wider range of nonparametric first-stage estimates, rate-optimal choices of smoothing parameters and data-driven estimates thereof, and their stochastic behavior can be well-approximated by classical first-order asymptotics. SDREs exist for a wide range of parameters of interest, particularly in semiparametric missing data and causal inference models. We illustrate our method with a simulation exercise.
Resumo:
Esta tese é composta por três ensaios sobre o mercado de crédito e as instituições que regem bancarrota corporativa. No capítulo um, trazemos evidências que questionam a ideia de que maiores níveis de proteção ao credor sempre promovem desenvolvimento do mercado de crédito. Desde a publicação dos artigos seminais de La Porta et al (1997,1998), a métrica de proteção ao credor que os autores propuseram -- o índice de proteção ao credor -- tem sido amplamente utilizada na literatura de Law and Finance como variável explicativa em modelos de regressão linear em forma reduzida para determinar a correlação entre proteção ao credor e desenvolvimento do mercado de crédito. Neste artigo, exploramos alguns problemas com essa abordagem. Do ponto de vista teórico, essa abordagem geralmente supõe uma relação monotônica entre proteção ao credor e expansão do crédito. Nós apresentamos um modelo teórico para um mercado de crédito com seleção adversa em que um nível intermediário de proteção ao credor é capaz de implementar equilíbrios first best. Este resultado está de acordo com diversos outros artigos teóricos, tanto em equilíbrio geral quanto em equilíbrio parcial. Do ponto de vista empírico, tiramos proveito das reformas realizadas por alguns países durante as décadas de 1990 e 2000 para implementar uma estratégia inspirada na literatura de treatment effects e estimar o efeito sobre o valor de mercado e sobre a dívida de: i) permitir automatic stay a firmas em recuperação; e ii) conceder aos credores o direito de afastar os administradores. Os resultados que obtivemos apontam para um impacto positivo de automatic stay sobre todas as variáveis que dependem do valor de mercado da firma. Não encontramos efeito sobre dívida, e não encontramos efeitos significativos do direito de afastar administradores sobre valor de mercado ou dívida. O capítulo dois avalia as consequências empíricas de uma reforma na lei de falências sobre um mercado de crédito pouco desenvolvido. No início de 2005, o Congresso Nacional brasileiro aprovou uma nova lei de falências, a lei 11.101/05. Usando dados de firmas brasileiras e não-brasileiras, nós estimamos, usando dois modelos diferentes, o efeito da reforma falimentar sobre variáveis contratuais e não-contratuais de dívida. Ambos os modelos produzem resultados similares. Encontramos um aumento no volume total de dívida e na dívida de longo prazo, e uma redução no custo de dívida. Não encontramos efeitos significativos sobre a estrutura de propriedade da dívida. No capítulo três, desenvolvemos um modelo estimável de equilíbrio em search direcionado aplicado ao mercado de crédito, modelo este que pode ser usado para realizar avaliações ex ante de mudanças institucionais que afetem o crédito (como reformas em leis de falência). A literatura em economia há muito reconhece uma relação causal entre instituições (como leis e regulações) e desenvolvimento dos mercados financeiros. Essa conclusão qualitativa é amplamente reconhecida, mas há pouca evidência de sua importância quantitativa. Com o nosso modelo, é possível estimar como contratos de dívida mudam em resposta a mudanças nos parâmetros que descrevem as instituições da economia. Também é possível estimar o impacto sobre investimentos realizados pelas firmas, bem como caracterizar a distribuição do tamanho, idade e produtividade das firmas antes e depois da mudança institucional. Como ilustração, realizamos um exercício empírico em que usamos dados de firmas brasileiras para simular o impacto de variações na taxa de recuperação de créditos sobre os valores médios e totais de dívida e capital das firmas. Encontramos dívida crescente e capital quase sempre também crescente na taxa de recuperação.
Resumo:
When estimating policy parameters, also known as treatment effects, the assignment to treatment mechanism almost always causes endogeneity and thus bias many of these policy parameters estimates. Additionally, heterogeneity in program impacts is more likely to be the norm than the exception for most social programs. In situations where these issues are present, the Marginal Treatment Effect (MTE) parameter estimation makes use of an instrument to avoid assignment bias and simultaneously to account for heterogeneous effects throughout individuals. Although this parameter is point identified in the literature, the assumptions required for identification may be strong. Given that, we use weaker assumptions in order to partially identify the MTE, i.e. to stablish a methodology for MTE bounds estimation, implementing it computationally and showing results from Monte Carlo simulations. The partial identification we perfom requires the MTE to be a monotone function over the propensity score, which is a reasonable assumption on several economics' examples, and the simulation results shows it is possible to get informative even in restricted cases where point identification is lost. Additionally, in situations where estimated bounds are not informative and the traditional point identification is lost, we suggest a more generic method to point estimate MTE using the Moore-Penrose Pseudo-Invese Matrix, achieving better results than traditional methods.
Resumo:
Esta tese é composta por três artigos e uma nota, sendo um em cada capítulo. Todos os capítulos enquadram-se na área de Microeconomia Aplicada e Economia do Trabalho. O primeiro artigo estende o modelo tradicional de decomposição das flutuações na taxa de desemprego de Shimer (2012), separando o emprego formal do informal. Com essa modificação, os principais resultados da metodologia se alteram e conclui-se que os principais fatores para a queda do desemprego na última década foram (i) a queda na taxa de participação, principalmente pela menor entrada na força de trabalho; (ii) o aumento da formalização, atingido tanto pelo aumento da probabilidade de encontrar um trabalho formal quanto pela probabilidade de deixar a condição de empregado formal. O segundo capítulo apresenta estimativas para o retorno à educação no Brasil, utilizando uma nova metodologia que não necessita de variáveis de exclusão. A vantagem do método em relação a abordagens que utilizam variáveis instrumentais é a de permitir avaliar o retorno médio para todos os trabalhadores (e não somente os afetados pelos instrumentos) e em qualquer instante do tempo. Face aos resultados, concluímos as estimativas via MQO subestimam o retorno médio. Discute-se possíveis explicações para esse fenômeno. O terceiro artigo trata da terceirização da mão de obra no Brasil. Mais especificamente, mede-se o diferencial de salários entre os trabalhadores terceirizados e os contratados diretamente. Os resultados de uma comparação não condicional indicam que os terceirizados têm salário médio 17% menor no período 2007 a 2012. Porém, com estimativas que levam em conta o efeito fixo de cada trabalhador, esse diferencial cai para 3,0%. Além disso, o diferencial é bastante heterogêneo entre os tipos de serviços: aqueles que utilizam trabalhadores de baixa qualificação apresentam salário menores, enquanto nas ocupações de maior qualificação os terceirizados têm salários iguais ou maiores do que os diretamente contratados. Mais ainda, as evidencias apontam para a diminuição do diferencial ao longo do tempo no período analisado. Finalmente, a nota que encerra a tese documenta dois aspectos relevantes e pouco conhecidos da Pesquisa Mensal de Emprego do IBGE que podem levar a resultados imprecisos nas pesquisas que utilizam esse painel se não forem tratados adequadamente.
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This paper estimates the effect of lighting on violent crime reduction. We explore an electrification program (LUZ PARA TODOS or Light for All - LPT) adopted by the federal government to expand electrification to rural areas in all Brazilian municipalities in the 2000s as an exogenous source of variation in electrification expansion. Our instrumental variable results show a reduction in homicide rates (approximately five homicides per 100,000 inhabitants) on rural roads/urban streets when a municipality moved from no access to full coverage of electricity between 2000 and 2010. These findings are even more significant in the northern and northeastern regions of Brazil, where rates of electrification are lower than those of the rest of the country and, thus, where the program is concentrated. In the north (northeast), the number of violent deaths on the streets per 100,000 inhabitants decreased by 48.12 (13.43). This moved a municipality at the 99th percentile (75th) to the median (zero) of the crime distribution of municipalities. Finally, we do not find effects on violent deaths in households and at other locations. Because we use an IV strategy by exploring the LPT program eligibility criteria, we can interpret the results as the estimated impact of the program on those experiencing an increase in electricity coverage due to their program eligibility. Thus, the results represent local average treatment effects of lighting on homicides.
Resumo:
Titanium is a biomaterial widely employed in biomedical applications (implants, prostheses, valves, stents). Several heat treatments are usually used in order to obtain physical properties required to different applications. This work studied the influence of the heat treatment on microstructure of commercial pure titanium, and their consequences in growth and proliferation of MC3T3-E1 cells. Discs of titanium were treated in different temperatures, and characterized by optical microscopy, image analysis, wettabillity, roughness, hardness and X-ray diffraction. After the heat treatment, significant modifications in these properties were observed. Pattern images of titanium, before and after the cell culture, were compared by overlapping to analyze the influence of microstructure in microstructure and preferences guidance cells. However, in general, titanium discs that showed a higher residual strength also presented an increase of cells numbers on surface
Resumo:
In this study barium hexaferrite was (general formulae BaFe12O19) was synthesized by the Pechini method under different conditions of heat treatment. Precursors like barium carbonate and iron nitrate were used. These magnetic ceramic, with magnetoplumbite type structure, are widely used as permanent magnet because of its excellent magnetic properties, such as: high Curie temperature, good magnetic anisotropy, high coercivity and corrosion resistance. The samples were characterized by thermal analysis (DTA and TG), X- ray Diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM) end Vibrating sample Magnetometer (VSM). The results confirm the expected phase, which was reinforced according to our analysis. A single phase powder at relatively high temperatures with particle sizes around 100 nm was obtained. The characteristic magnetic behavior one of the phases has been noted (probably superparamagnetic material), while another phase was identified as a ferrimagnetic material. The ferrimagnetic phase showed vortex configuration with two central and slightly inclined plateaus. In general, increase of heat treatment temperature and time, directly influenced the technological properties of the samples
Resumo:
Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process
Resumo:
It seeks to find an alternative to the current tantalum electrolytic capacitors in the market due to its high cost. Niobium is a potential substitute, since both belong to the same group of the periodic table and because of this have many similar physical and chemical properties. Niobium has several technologically important applications, and Brazil has the largest reserves, around 96%. There are including niobium in reserves of tantalite and columbite in Rio Grande do Norte. These electrolytic capacitors have high capacitance specifies, ie they can store high energy in small volumes compared to other types of capacitors. This is the main attraction of this type of capacitor because is growing demand in the production of capacitors with capacitance specifies increasingly high, this because of the miniaturization of various devices such as GPS devices, televisions, computers, phones and many others. The production route of the capacitor was made by powder metallurgy. The initial niobium powder supplied by EEL-USP was first characterized by XRD, SEM, XRF and laser particle size, to then be sieved into three particle size, 200, 400 e 635mesh. The powders were then compacted and sintered at 1350, 1450 and 1550°C using two sintering time 30 and 60min. Sintering is one of the most important parts of the process as it affects properties as porosity and surface cleaning of the samples, which greatly affected the quality of the capacitor. The sintered samples then underwent a process of anodic oxidation, which created a thin film of niobium pentóxido over the whole porous surface of the sample, this film is the dielectric capacitor. The oxidation process variables influence the performance of the film and therefore the capacitor. The samples were characterized by electrical measurements of capacitance, loss factor, ESR, relative density, porosity and surface area. After the characterizations was made an annealing in air ate 260ºC for 60min. After this treatment were made again the electrical measurements. The particle size of powders and sintering affected the porosity and in turn the specific area of the samples. The larger de area of the capacitor, greater is the capacitance. The powder showed the highest capacitance was with the smallest particle size. Higher temperatures and times of sintering caused samples with smaller surface area, but on the other hand the cleaning surface impurities was higher for this cases. So a balance must be made between the gain that is achieved with the cleaning of impurities and the loss with the decreased in specific area. The best results were obtained for the temperature of 1450ºC/60min. The influence of annealing on the loss factor and ESR did not follow a well-defined pattern, because their values increased in some cases and decreased in others. The most interesting results due to heat treatment were with respect to capacitance, which showed an increase for all samples after treatment
Preparação de óxidos mistos de níquel e zinco nanoparticulados a partir de combustíveis alternativos
Resumo:
The field of "Materials Chemistry" has been developing in recent years and there has been a great increase of interest in the synthesis and chemical and physical properties of new inorganic solids. New routes of synthesis and synthesis modified has been developed with the aim not only to optimize the processes in laboratory scale, but also on an industrial scale, and make them acceptable by current environmental legislation. The phenomenology of current solid state chemistry properties coupled with the high temperature superconductivity, ferromagnetism, porosity molecular and colors are evidence affected by the synthesis method, which in turn can influence the technological application of these materials. From this understanding, mixed oxides of nickel and zinc nanoparticulate were synthesized by microwave-assisted combustion route using three specific types of organic fuels employing the weight ratios 1:1/2 and 1:1 of cation metallic/fuel, in order to investigate the influence of such proportions to obtain the solids. The new fuels were chosen to replace, for example, urea or glycine that are the fuels most commonly preferred in this kind of synthesis. The powders without heat treatment were studied by Thermogravimetric analysis (TGA), X-Ray Diffraction (XRD) and then calcined at 900°C. After heat treatment, the samples were characterized by analysis of X Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The modified synthesis route porposed was effective for obtaining powders. Both the alternative fuels chosen as the different weight ratios employed, influenced in the morphology and obtaining oxides
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The synthesis of zeolites from natural sources of silicon and aluminum are promising alternative routes to obtain porous or zeolite MCM family. Such materials are typically used in catalytic processes and / or adsorption is to obtain new products or for separation and purification processes thereof. Environmental legislation is becoming stricter and requires the use of materials more efficient, aiming to achieve pollution prevention, by gas or liquid contaminants in the environment. In order to obtain a material with environmentally friendly features, this study aimed at the synthesis of zeolite A, from an amorphous sediment, diatomite, which is found in abundance in the northeast region of Brazil, may be substituted for conventional products the production of zeolite, involving higher costs. The methodology for obtaining the "Zeolite A" using as a source of silica and alumina diatomite is simple, since this is a source of silicon, not requiring therefore a structural driver, but also by heat treatment, only drying conventional to remove water. The "zeolite A" was obtained from diatomite, but as an intermediate step we obtained the sodalite. The characterization was made by the following techniques: EDX, XRD, FT-IR, SEM and determining a specific area by the BET method and the BJH method for checking the diameter of pores. By characterization of the obtained material was first demonstrated the achievement of sodalite and after modification of the same, there was obtained zeolite A
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The present work deals with the synthesis of materials with perovskite structure with the intention of using them as cathodes in fuel cells SOFC type. The perovskite type materials were obtained by chemical synthesis method, using gelatin as the substituent of citric acid and ethylene glycol, and polymerizing acting as chelating agent. The materials were characterized by X-ray diffraction, thermal analysis, spectroscopy Fourier transform infrared, scanning electron microscopy with EDS, surface area determination by the BET method and Term Reduction Program, TPR. The compounds were also characterized by electrical conductivity for the purpose of observing the possible application of this material as a cathode for fuel cells, solid oxide SOFC. The method using gelatin and polymerizing chelating agent for the preparation of materials with the perovskite structure allows the synthesis of crystalline materials and homogeneous. The results demonstrate that the route adopted to obtain materials were effective. The distorted perovskite structure have obtained the type orthorhombic and rhombohedral; important for fuel cell cathodes. The presentation material properties required of a candidate cathode materials for fuel cells. XRD analysis contacted by the distortion of the structures of the synthesized materials. The analyzes show that the electrical conductivity obtained materials have the potential to act as a cell to the cathode of solid oxide fuel, allowing to infer an order of values for the electrical conductivities of perovskites where LaFeO3 < LaNiO3 < LaNi0,5Fe0,5O3. It can be concluded that the activity of these perovskites is due to the presence of structural defects generated that depend on the method of synthesis and the subsequent heat treatment
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Ceramic filters are cellular structures that can be produced by various techniques, among which we highlight the replication method, or method of polymeric sponge. This method consists of impregnating polymeric foam with ceramic slurry, followed by heat treatment, where will occur decomposition of organic material and the sinter of the ceramic material, resulting in a ceramic whose structure is a replica of the impregnated sponge. Ceramic filters have specific properties that make this type of material very versatile, used in various technological applications such as filters for molten metals and burners, make these materials attractive candidates for high temperature applications. In this work we studied the systems Al2O3-LZSA ceramic filters processed in the laboratory, and commercial Al2O3-SiC ceramics filters, both obtained by the replica method, this work proposes the thermal and mechanical characterization. The sponge used in the processing of filters made in the laboratory was characterized by thermogravimetric analysis. The ceramic filters were characterized by compressive strength, flexural strength at high temperatures, thermal shock, permeability and physical characterization (density and porosity) and microstructural (MEV and X-rays). From the results obtained, the analysis was made of the mechanical behavior of these materials, comparing the model proposed by Gibson and Ashby model and modified the effective area and the tension adjusted, where the modified model adapted itself better to the experimental results, representing better the mechanical behavior of ceramic filters obtained by the replica method
Resumo:
Thin commercial aluminum electrolytic and passed through reactions was obtained with anodic alumina membranes nanopores. These materials have applications in areas recognized electronic, biomedical, chemical and biological weapons, especially in obtaining nanostructures using these membranes as a substrate or template for processing nanowires, nanodots and nanofibers for applications noble. Previous studies showed that the membranes that have undergone heat treatment temperature to 1300° C underwent changes in morphology, crystal structure and optical properties. This aim, this thesis, a study of the heat treatment of porous anodic alumina membranes, in order to obtain and to characterize the behavior changes structures during the crystallization process of the membranes, at temperatures ranging between 300 and 1700° C. It was therefore necessary to mount a system formed by a tubular furnace resistive alumina tube and controlled environment, applying flux with special blend of Ag-87% and 13% N2, in which argon had the role of carrying out the oxygen nitrogen system and induce the closing of the pores during the densification of the membrane. The duration of heat treatment ranged from 60 to 15 minutes, at temperatures from 300 to 1700° C respectively. With the heat treatment occurred: a drastic reduction of porosity, grain growth and increased translucency of the membrane. For the characterization of the membranes were analyzed properties: Physical - thermogravimetric, X-ray diffraction, BET surface area; morphological - SEM, EDS through compositional and, optical absorbance, and transmittance in the UV-VIS, and FTIR. The results using the SEM showed that crystallization has occurred, densification and significant changes in membrane structure, as well as obtaining microtube, the BET analysis showed a decrease in specific surface area of the membranes has to 44.381 m2.g-1 to less than 1.8 m2.g-1 and in the analysis of transmittance and absorbance was found a value of 16.5% in the range of 800 nm, characteristic of the near infrared and FTIR have confirmed the molecular groups of the material. Thus, one can say that the membranes were mixed characteristics and properties which qualify for use in gas filtration system, as well as applications in the range of optical wavelength of the infra-red, and as a substrate of nanomaterials. This requires the continuation and deepening of additional study
Resumo:
Studies indicate that a variation in the degree of crystallinity of the components of a polymer blend influences the mechanical properties. This variation can be obtained by subjecting the blend to heat treatments that lead to changes in the spherulitic structure. The aim of this work is to analyze the influence of different heat treatments on the variation of the degree of crystallinity and to establish a relationship between this variation and the mechanical behavior of poly(methyl methacrylate)/poly(ethylene terephthalate) recycled (PMMA / PETrec) with and without the use of compatibilizer agent poly(methyl methacrylate-al-glycidyl methacrylate-al-ethyl acrylate) (MMAGMA- EA). All compositions were subjected to two heat treatments. T1 heat treatment the samples were treated at 130 ° C for 30 minutes and cooled in air. In T2, the samples were treated at 230 ° C for 5 minutes and cooled to approximately -10 ° C. The variation of the degree of crystallinity was determined by the proportional relationship between crystallinity and density, with the density measured by pycnometry. The mechanical behavior was verified by tensile tests with and without the presence of notches and pre-cracks, and by method of fracture toughness in plane strain (KIC). We used the scanning electron microscopy (SEM) to analyze the fracture surface of the samples. The compositions subjected to heat treatment T1, in general, showed an increase in the degree of crystallinity in tensile strength and a tendency to decrease in toughness, while compositions undergoing treatment T2 showed that the opposite behavior. Therefore, this work showed that heat treatment can give a polymer blend further diversity of its properties, this being caused by changes in the crystal structure