Elaboração de pós de ferrita de cobalto, CoFe2O4, nanoestruturados e hierarquizados: influência da morfologia sobre a detecção e oxidação catalítica de gases poluentes

This thesis is part of research on new materials for catalysis and gas sensors more active, sensitive, selective. The aim of this thesis was to develop and characterize cobalt ferrite in different morphologies, in order to study their influence on the electrical response and the catalytic activity, and to hierarchize these grains for greater diffusivity of gas in the material. The powders were produced via hydrothermal and solvothermal, and were characterized by thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy (electron diffraction, highresolution simulations), and energy dispersive spectroscopy. The catalytic and electrical properties were tested in the presence of CO and NO2 gases, the latter in different concentrations (1-100 ppm) and at different temperatures (room temperature to 350 ° C). Nanooctahedra with an average size of 20 nm were obtained by hydrothermal route. It has been determined that the shape of the grains is mainly linked to the nature of the precipitating agent and the presence of OH ions in the reaction medium. By solvothermal method CoFe2O4 spherical powders were prepared with grain size of 8 and 20 nm. CoFe2O4 powders exhibit a strong response to small amounts of NO2 (10 ppm to 200 ° C). The nanooctahedra have greater sensitivity than the spherical grains of the same size, and have smaller response time and shorter recovery times. These results were confirmed by modeling the kinetics of response and recovery of the sensor. Initial tests of catalytic activity in the oxidation of CO between temperatures of 100 °C and 350 °C show that the size effect is predominant in relation the effect of the form with respect to the conversion of the reaction. The morphology of the grains influence the rate of reaction. A higher reaction rate is obtained in the presence of nanooctahedra. In order to improve the detection and catalytic properties of the material, we have developed a methodology for hierarchizing grains which involves the use of carbonbased templates.

Formulações e algoritmos para o problema das p-medianas heterogêneo livre de penalidade

This work presents a new model for the Heterogeneous p-median Problem (HPM), proposed to recover the hidden category structures present in the data provided by a sorting task procedure, a popular approach to understand heterogeneous individual’s perception of products and brands. This new model is named as the Penalty-free Heterogeneous p-median Problem (PFHPM), a single-objective version of the original problem, the HPM. The main parameter in the HPM is also eliminated, the penalty factor. It is responsible for the weighting of the objective function terms. The adjusting of this parameter controls the way that the model recovers the hidden category structures present in data, and depends on a broad knowledge of the problem. Additionally, two complementary formulations for the PFHPM are shown, both mixed integer linear programming problems. From these additional formulations lower-bounds were obtained for the PFHPM. These values were used to validate a specialized Variable Neighborhood Search (VNS) algorithm, proposed to solve the PFHPM. This algorithm provided good quality solutions for the PFHPM, solving artificial generated instances from a Monte Carlo Simulation and real data instances, even with limited computational resources. Statistical analyses presented in this work suggest that the new algorithm and model, the PFHPM, can recover more accurately the original category structures related to heterogeneous individual’s perceptions than the original model and algorithm, the HPM. Finally, an illustrative application of the PFHPM is presented, as well as some insights about some new possibilities for it, extending the new model to fuzzy environments

Incorporação do resíduo de cascalho de perfuração de poços de petróleo em formulações cerâmicas

During its operations, the oil industry generates a lot of waste, including gravel from drilling. Control of environmental impacts caused by this waste represents a major challenge. Such impacts can be minimized when it is given an appropriate management by being properly treated and properly disposed or recycled. The properties of these materials can be greatly influenced when a waste is added to its composition. This work aims to study the incorporation of gravel waste oil-well drilling in the standard body for production of red ceramic from a ceramic industry in São Gonçalo do Amarante / RN. The success of the incorporation can minimize costs in the production of ceramic pieces and reduce the environmental impacts caused by waste. The raw materials used were collected, characterized, and formulated with the percentages of 0%, 20% and 40% by weight of substitution of residue were synthesized at temperatures of 900, 1.010 and 1.120 °C using 30 minute firing intervals, 1 hour and 30min and 2 hours and 30 minutes, based on a factorial design 2³. Samples were then subjected to the tests of Water Absorption, Linear Retraction Firing, Flexural Rupture Strength, Apparent Porosity and Apparent Specific mass and Scanning Electron Microscopy (SEM) of break section. The results showed that the use of the residue for the manufacture of the ceramic products is possible (tiles, bricks and massive hollow bricks) replacing the clay to 40%, meeting the requirements of the standard and the literature for the technological properties of the final product.

Citotoxicidade da associação de agrotóxicos da rizicultura em hepatócitos de Zebrafish

No plantio do arroz parte de um corpo d’água (rio, lago, lagoa) é desviado para a irrigação da plantação, e, posteriormente, a água utilizada nas lavouras é devolvida ao rio/lago/lagoa de origem. Assim, seja por lixiviação ou por qualquer outro fator, a água entra em contato com os agrotóxicos que, anteriormente, foram utilizados na plantação, podendo causar danos à qualidade do recurso hídrico e à fauna lacustre, devido à exposição a estes poluentes. O presente trabalho teve por objetivo verificar a citotoxicidade de agrotóxicos (herbicida e inseticida), utilizados na rizicultura no estado do Rio Grande do Sul, em células hepáticas da linhagem ZF-L. A partir da análise de funcionalidade de três alvos celulares diferentes, integridade da membrana celular, estabilidade lisossomal e atividade mitocondrial frente à exposição ao Roundup Transorb® , ao Furadan 350 SC® e à associação destes produtos. Foi analisada ainda, a capacidade de defesa das células, expostas aos poluentes escolhidos, no que diz respeito à atividade de proteínas extrusoras de xenobióticos, assim como à expressão de tais proteínas. A partir dos resultados obtidos foi verificado efeito citotóxico de ambos os agrotóxicos, bem como a mistura destes para todos os alvos verificados, apresentando ainda efeito inibitório à atividade de extrusão de xenobióticos pelas glicoproteínas P (P-gps). Apenas quando expostas ao inseticida e à mistura as células apresentaram um aumento na expressão de glicoproteínas (P-gp). Verificou-se a existência de correlação negativa entre a citotoxicidade apresentada, principalmente na atividade mitocondrial e na integridade lisossomo e a atividade das P-gps. Em conclusão, percebeu-se que as concentrações abaixo do permitido pela legislação brasileira, para os princípios ativos dos agrotóxicos testados, mostraram-se tóxicas para todos os alvos de citotoxicidade testados neste estudo, com exceção da mitocôndria, sugerindo que esta toxicidade apresentada pode ser devido aos surfactantes presentes nas formulações comerciais.

Estudo numérico do impacto das emissões veiculares e fixas da cidade de Manaus nas concentrações de poluentes atmosféricos da região amazônica

The main aim of this study was to evaluate the impact of the urban pollution plume from the city of Manaus by emissions from mobile and stationary sources in the atmospheric pollutants concentrations of the Amazon region, by using The Weather Research and Forecasting with Chemistry (WRF-Chem) model. The air pollutants analyzed were CO, NOx, SO2, O3, PM2.5, PM10 and VOCs. The model simulations have been configured with a grid spacing of 3 km, with 190 x and 136 y grid points in horizontal spacing, centered in the city of Manaus during the period of 17 and 18 of March 2014. The anthropogenic emissions inventories have gathered from mobile sources that were estimated the emissions of light and heavy-duty vehicles classes. In addition, the stationary sources have considered the thermal power plants by the type of energy sources used in the region as well as the emissions from the refinery located in Manaus. Various scenarios have been defined with numerical experiments that considered only emissions by biogenic, mobile and stationary sources, and replacement fuel from thermal power plant, along with a future scenario consisting with twice as much anthropogenic emissions. A qualitative assessment of simulation with base scenario has also been carried out, which represents the conditions of the region in its current state, where several statistical methods were used in order to compare the results of air pollutants and meteorological fields with observed ground-based data located in various points in the study grid. The qualitative analysis showed that the model represents satisfactorily the variables analyzed from the point of view of the adopted parameters. Regarding the simulations, defined from the base scenarios, the numerical experiments indicate relevant results such as: it was found that the stationary sources scenario, where the thermal power plants are predominant, resulted in the highest concentrations, for all air pollutants evaluated, except for carbon monoxide when compared to the vehicle emissions scenario; The replacement of the energy matrix of current thermal power plants for natural gas have showed significant reductions in pollutants analyzed, for instance, 63% reductions of NOx in the contribution of average concentration in the study grid; A significant increase in the concentrations of chemical species was observed in a futuristic scenario, reaching up to a 81% increase in peak concentrations of SO2 in the study area. The spatial distributions of the scenarios have showed that the air pollution plume from Manaus is predominantly west and southwest, where it can reach hundreds of kilometers to areas dominated by original soil covering.

Redução do Impacto Ambiental de Poluentes Orgânicos Persistentes

Nos dias de hoje a contaminação dos solos e águas subterrâneas com pesticidas através da agricultura tornou-se um problema. Problema este, considerado ainda maior nas áreas onde o abastecimento de água potável é quase totalmente à base de água subterrânea, causando deste modo risco para a saúde humana devido à exposição directa de possíveis resíduos de pesticidas na água potável. É certo que a persistência dos pesticidas no solo é importante para obter um bom controlo sob as ervas daninhas durante a sua época de crescimento, contudo o uso desses pesticidas contamina não só o solo como as águas superficiais. As questões acerca do uso de pesticidas na actualidade continuarão a persistir, uma vez que existem muitos factores e características inerentes a este processo que necessitam de ser abordadas e mais importante que isso estudadas, como por exemplo a sua degradação e toxicidade. Neste trabalho efectuou-se o encapsulamento de pesticidas em moléculas de β – ciclodextrina (β-CD). O que se pretende com este encapsulamento, é aumentar a hidrofilicidade do pesticida de forma a garantir que este persista o tempo suficiente permitindo um bom controlo das ervas daninhas, tendo sempre em conta as preocupações inerentes ao uso dos pesticidas, como por exemplo a dificuldade de biodegradação. O estudo centrou-se em torno de dois dos pesticidas mais utilizados em Portugal: MCPA e Bentazona. Estes herbicidas foram encapsulados individualmente na β-CD formando assim complexos, mais solúveis e eventualmente mais estáveis quimicamente garantindo uma redução dos efeitos dos pesticidas no meio ambiente. Este estudo foi dividido essencialmente em duas partes: a síntese e caracterização dos complexos pesticida-β-CD e posteriormente a avaliação da estabilidade química em solução aquosa e da solubilidade dos complexos formados. A utilização de diversas técnicas analíticas nomeadamente DSC, FTIR, Espectrofotometria de UV, HPLC e Electroquímica permitiram concluir que o pesticida MCPA encapsula pela acção da β-CD aquando do complexo formado em solução etanólica e numa proporção estequiométrica MCPA:β-CD de 1:2 respectivamente. Obteve-se para as várias soluções estudadas, todas elas com concentrações diferentes de β-CD, uma constante de estabilidade de 102,4. No caso da Bentazona, os resultados preliminares obtidos indiciam claramente a formação de um complexo com a β-CD para o complexo formado em solução etanólica.

Desenvolvimento de formulações para produção de grés porcelanato a partir de matérias-primas da região da bacia do Parnaíba

Brazil is a great ceramic raw materials productor because of the its big number of clay deposits, in various areas of the ceramic industry. Although, the majority of the natural reservations are unknown or not studied yet, so there is no scientific technical dates that can guide their usage and industrial application, as well as the racional and optimazed way of usage by the industrial sector. The state of Maranhão has a gigant mineral wealth as esmectite, bentonite, kaolin, clays, feldspates, marine salt, iron and others, but produce only products with small agregated value compared to the porcelanato, one of the most expensives ceramic cover tiles, the reason for that is the low water absorption (lower than 0,5%), beside present amazing tecnicals features, like mechanical resistence. The main objective of the work is to do the characterization of four clays, with the finallity of find an application by the results and develop formulations to produce porcelanato using these raw materials from Timon-MA. For this were made the raw materials characterization using X ray fluorecence; X ray diffraction; Differencial thermal analysis; Dilatometric analysis and Tecnological properties, planing three formulations that were sinterized at six different temperatures: 1150, 1170, 1190, 1210, 1230 and 1250ºC for 7 minutes. After the sinteratization, the samples were submitted to tension resistance analysis. Were attained two formulations with the requested properties to produce porcelanato

Qualidade do ar interior em lares de idosos e a exposição ocupacional aos poluentes atmosféricos

Os lares de idosos são espaços com características específicas, onde a garantia de condições de trabalho saudáveis é fundamental para o bem-estar dos trabalhadores e dos idosos. O objectivo deste trabalho consistiu em avaliar a exposição ocupacional dos trabalhadores dos lares de idosos aos poluentes do ar interior e em verificar qual a prevalência de sintomas/doenças. A amostragem foi não probabilística quanto ao tipo e por conveniência quanto à técnica. A amostra foi constituída por 8 lares de idosos sedeados no concelho de Tondela e 155 trabalhadores. Foram administrados inquéritos aos trabalhadores e avaliada a qualidade do ar, bem como os níveis de temperatura e humidade relativa. Os dados foram tratados através do software estatístico IBM SPSS versão 21.0. A interpretação dos testes estatísticos foi realizada com base no nível de significância de p=0,05, com intervalo de confiança de 95%. Verificámos que as concentrações médias de dióxido de carbono, compostos orgânicos voláteis e partículas com diâmetro <10, registados em alguns lares de idosos ultrapassaram o limiar de protecção sendo essa concentração, em média, mais elevada nos lares localizados em zonas urbanas. Os sintomas/doenças com maior prevalência foram as dores de cabeça, crise de espirros, tonturas e alergias. Os edifícios apresentavam Síndroma do Edifício Doente (SED) e a maioria dos trabalhadores que indicaram possuir sintomas/doenças trabalhavam em lares de idosos localizados em zonas urbanas e residiam em zonas rurais. Torna-se perceptível que as instituições realizem monitorizações contínuas de QAI de modo a não exporem os trabalhadores e os idosos a situações de risco.

Estudo da incorporação de cascalho proveniente da perfuração de poços de petróleo em formulações para tijolos de solo-cimento

The present work is to study the characteristics and technological properties of soil-cement bricks made from binary and ternary mixtures of Portland cement, sand, water, with or without addition of gravel from the drilling of oil wells, which could be used by industry, aiming to improve its performance and reduce cost by using the residue and, consequently, increasing its useful life. The soil-cement bricks are one of the alternatives to masonry construction. These elements, after a short curing period, provide compressive strength similar to that of solid bricks and ceramic blocks, and the higher the resistance the higher the amount of cement used. We used the soil from the city of São José do Mipibu / RN, the banks of the River Baldun, cement CPIIZ-32 and residue of drill cuttings from oil wells drilling onshore wells in the town of Mossley, RN, provided Petrobras. To determine the optimum mix, we studied the inclusion of different residues (100%, 80%, 70%, 60% and 50%) where 15 bodies were made of the test piece. The assessment was made of bricks made from simple compression tests, mass loss by immersion and water absorption. The experimental results proved the efficiency and high utilization of the waste from the drilling of oil wells, making the brick-cement-soil residue with a higher strength and lower water absorption. The best result in terms of mechanical strength and water absorption for the ternary mixture was 10% soil, 14% cement and 80% residue. In terms of binary mixtures, we obtained the best result for the mix-cement residue, which was 14% cement incorporated in the residue

Avaliação da potencialidade dos resíduos de gesso de revestimento incorporados em formulações de massas cerâmicas

In building, during the implementation process of major or even minor works, there is a considerable waste of plaster in the steps of coating, making it is a negative factor because of the loss of these processes constructive remains incorporated into buildings, as component, whose final dimensions are higher than those projected. Another negative factor is the disposal of waste gypsum in inappropriate places, thus contributing to the degradation of environmental quality, due to the leaching of this waste and may trigger the formation of sulfuric acid. Therefore, based on this picture, processing and reuse of waste coating, combined with the ceramics industry, which is a strong potential in the reuse of certain types of waste, promote mutual benefits. Thus the overall objective of this work is to conduct a search with scientific and technological aspects, to determine the effect of the incorporation of the residue of plaster for coating, from the building, the formulation of bodies for red ceramic. The residue of plaster coating was collected and characterized. They were also selected raw materials of two ceramic poles of the state of Rio Grande do Norte and formulations have been made with the intention of obtaining those with the best physical and mechanical properties, the residue was added the percentage of 5%, 10%, 15%, 20%, 25% and 30%, in the best formulation of ceramic industry 1 and, according the properties analyses, 5%, 10% and 15% as the best results of ceramic industry 2. The samples were sintered at temperatures of 850 ºC, 950 °C and 1050 °C, the heating rate of 5 ºC / min with isotherm of two hours. They were submitted to testing technology, such as lineal shrinkage, water absorption, apparent porosity, apparent density and bending resistence. The residue incorporation best results in the formulations of mass in red ceramic, were observed between the temperatures of 850 ºC and 950 ºC, in those formulations that have illite clays and medium plastic in their composition, in the range of 0% to 15% residue incorporated

Análise do risco de lixiviação de poluentes orgânicos de lodos de esgotos em cultivos de milho.

Por hipótese, o uso de lodos de esgotos como fertilizantes agrícolas pode contaminar solos e águas subterrâneas com poluentes orgânicos. O objetivo desse trabalho foi analisar o risco de lixiviação de trinta e oito poluentes orgânicos de lodos de esgotos. Para tanto, foi assumido um cultivo de milho em um solo Latossolo vermelho distrófico, característico de solos de regiões produtoras de milho, no qual foi aplicada uma dose de lodo de esgotos como fertilizante agrícola. A lixiviação dos poluentes foi simulada utilizando-se o modelo CMLS94 e os dados climáticos de mil anos independentes e igualmente prováveis gerados pelo simulador de clima WGEN, a partir de uma seqüência de quatorze anos consecutivos observados e registrados pela Estação Experimental do Instituto Agronômico de Campinas - IAC. A análise de risco indicou que os poluentes benzidina > n-nitrosodi-n-propilamina > fenol > 2,4-dinitrofenol > isoforano > nitrobenzeno > p-cresol > o-cresol > m-cresol > 2- clorofenol, nessa ordem, devem ser monitorados prioritariamente em águas subterrâneas de regiões de solos similares a Latossolo vermelho distrófico nos quais foram aplicados doses de lodo.

Sintomas de fitotoxicidade em soja transgênica induzidos por diferentes formulações de glifosate.

Apesar de não haver relatos de quebra na produtividade, a soja geneticamente modificada (RR) pode apresentar sintomas de injúrias ao glifosate dependendo, dentre outros, de fatores ambientais, formulação e doses. Ensaios preliminares indicaram a possibilidade da ocorrência de injúrias na soja RR devido à presença do adjuvante aminado presente nas formulações comerciais. Neste trabalho verificou-se a ocorrência de injúrias em plântulas de soja RR frente a diferentes formulações de glifosate, variando quanto ao seu sal e à presença do adjuvante aminado na formulação comercial. Os resultados confirmaram ser esse composto o responsável pelas injúrias observadas nas plântulas de soja RR tratadas com as diferentes formulações.

Efeito da adição de feldspato e/ou resíduo de caulin em formulações à base de argila ilítica

The red pottery industry in Piauí state is well developed and stands out at the national context for the technical quality of its products. The floor and wall tile industry, however, is little developed since the state has only one company that produces red clay-based ceramic tiles. This thesis aims at using the predominantly illitic basic mass of the above mentioned industry, with the addition of feldspar and/or kaolin residue in order to obtain products of higher technical quality. Kaolin residue consists basically of kaolinite, muscovite mica and quartz; the feldspar used was potassic. In this experiment, basic mass (MB) was used for experimental control and fifteen formulations codified as follows: F2, F4, F8, F16, F32, FR2, FR4, FR8, FR16, FR32, R2, R4, R8, R16 and R32. All raw materials were dry-milled, classified, formulated and then humidified to 10% water. Thereafter, test samples were produced by unixial pressing process in a rectangular steel matrix (60.0 x 20.0 x 5.0) mm3 at (25 MPa). They were fired at four temperatures: 1080°C, 1120°C, 1160°C, with a heating rate of 10°C/min during up to 10 min in an electric oven, and the last one in an industrial oven with a peak of 1140°C, aim ing to confirm the results found in laboratory and, finally, technological tests were performed: MEA, RL, AA, PA, TRF and PF. The results revealed that the residue under study can be considered a raw material with large potential in the industry of red clay-based ceramic tiles, since the results found both in laboratory and in the industry have shown that the test samples produced from the formulations with up to 4% feldspar and those produced with up to 8% feldspar and residue permitted a reduction in the water absorption rate and an increase in the mechanical resistance while those samples produced with up to 4% residue had an increase in the mechanical resistance when compared to those produced from the basic mass and that the formulation with 2% feldspar and residue presented the best technological properties, lowering the sintering temperature down to 1120°C

Uso de resíduo e de minerais de pegmatito da região do seridó RN e de argilas portuguesas em formulações de grês porcelanato

In the State Rio Grande do Norte, Brazil, the most significant deposits of minerals in the production of granite and pegmatite are Seridó region. Municipalities of Parelhas and Equador are the main responsible for the production of feldspar, quartz, kaolin and granite. The ceramic industries are always in search of competitiveness by investing in new products or improving existing techniques. The stoneware is a type of pottery that stands in the market because it presents technical and aesthetic characteristics superior to other existing products. Characteristics of the raw materials initially obtained with chemical analysis and mineralogical analysis are crucial in getting a product that satisfies the conditions in a manufacturing process and is, in principle, directly related to the firing cycle. This research aimed at developing new formulations for the mass production of ceramic stoneware. The raw materials initially characterized were feldspar, quartz, kaolin and granite. As part of the research was developed at the University of Aveiro, in Portugal, we used two clays used in the production of Portuguese ceramics. The raw material Brazilian and Portuguese and the final product, both in Portugal and Brazil, were analyzed for X-ray fluorescence, X-ray diffraction, granulometric analysis, dilatometric analysis, thermal analysis and analysis of scanning electron microscopy (MEV). The specimens prepared at the University of Aveiro (DECV) were sintered at 10000C and 12000C and the specimens prepared in UFRN were sintered at 10000C, 10500C, 11000C, 11500C, 12000C, 12500C and 13000C, but the best results and demonstrating the presence of the mineral mullite were at temperatures of 12000C, 12500C and 13000C. The results showed that the granite waste used may be considered raw material of excellent quality for use in the ceramic industry and coating floors and more accurately by the industry of stoneware. Physical and mechanical tests conducted on samples of the formulations F01 and F02 developed in UFRN showed a water absorption and mechanical strength suitable for the stoneware