Photocatalyst TiO(2)-Co: the effect of doping depth profile on methylene blue degradation

In this work, we study the effect of doping depth profile on the photocatalytic and surface properties of TiO(2) films. Two thin film layers of TiO(2) (200 nm) and Co (5 nm), respectively, were deposited by physical evaporation on glass substrate. These films were annealed for 1 s at 100 and 400 A degrees C and the Co layer was removed by chemical etching. Atomic force microscopy (AFM) phase images showed changes in the surface in function of thermal treatment. The grazing-incidence X-ray fluorescence (GIXRF) measurements indicated that the thermal treatment caused migration of Co atoms to below the surface, the depths found were between 19 and 29 nm. The contact angle showed distinct values in function of the doped profile or Co surface concentration. The UV-vis spectra presented a red shift with the increasing of thermal treatment. Photocatalytical assays were performed by methylene blue discoloration and the higher activity was found for TiO(2)-Co treated at 400 A degrees C, the ESI-MS showed the fragments formed during the methylene blue decomposition.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Testes de ajustamento de modelos em processos com longa dependência

Estudamos neste trabalho, o nível de significância empírico dos testes portmanteau baseados nas estatísticas propostas por Ljung e Box (1978), Monti (1994) e Pe˜na e Rodríguez (2002) nos processos ARFIMA(p; d; q). Consideramos o processo ARFIMA(p; d; q) nas situações adequadas para representar séries temporais com características de longa dependência. Para estimar o parâmetro de diferenciação d utilizamos os métodos de estimação propostos por Geweke e Porter-Hudak (1983), Reisen (1994), Robinson (1994) e Fox e Taqqu (1983).

O impacto das políticas de direcionamento de crédito e de depósitos compulsórios no mercado bancário

Esta dissertação tem por objetivo demonstrar que a adoção, pelo Governo Brasileiro, de políticas de direcionamento de crédito para setores considerados prioritários e de depósitos compulsórios sobre o volume de depósitos, ambos com taxas de remuneração subsidiadas em relação às taxas de juros interbancários, gera impactos para uma ampla parcela da sociedade, tanto através das taxas de juros dos empréstimos concedidos a setores não prioritários quanto através das taxas pagas pelos bancos comerciais no mercado de depósitos. Esses efeitos ajudam a explicar por que os spreads bancários no Brasil são maiores do que os da maioria dos países. No primeiro capitulo são discutidos os principais argumentos a favor e contra a adoção dessas políticas. No segundo capítulo é efetuada a modelagem teórica do comportamento dos bancos, através de uma adaptação do modelo Monti-Klein, para se chegar aos impactos da adoção dessas políticas no comportamento dos bancos comerciais. A seguir, são realizadas regressões para encontrar evidências empíricas que comprovem os resultados obtidos na modelagem teórica. Por fim, foram consolidados os resultados obtidos, indicando alternativas de política para a redução dos impactos nocivos na sociedade e indica-se linhas de pesquisa a serem desenvolvidas para aprofundar o entendimento desses impactos.

Emprego da sulfatação na recuperação de metais de lodos galvânicos

Este trabalho relata um estudo de sulfatação, em escala laboratorial, com objetivo de propor um tratamento para a recuperação seletiva de determinados metais presentes em lodos galvânicos (LG). Os metais de interesse são cobre, zinco e níquel e o agente promotor da sulfatação é a pirita, obtida de rejeitos de carvão mineral. A particularidade deste tratamento é o emprego simultâneo de dois resíduos perigosos como matériasprimas. Estes resíduos são gerados em grande quantidade em sítios de extração de carvão (rejeito piritoso) e empresas galvânicas (lodo galvânico). Os resíduos foram caracterizados por fluorescência de raios X (XRF), distribuição granulométrica e percentual de umidade. A caracterização química apresentou lodos com alta concentração de cobre, maior do que 14% (base seca). Na etapa de sulfatação, o lodo galvânico foi misturado com o rejeito piritoso e os parâmetros avaliados foram: razão lodo galvânico/rejeito piritoso, temperatura de sulfatação e tempo de patamar. Depois da sulfatação, o produto da reação foi lixiviado com água, em temperatura ambiente, por 15 min. Nesta etapa hidrometalúrgica, os parâmetros variáveis foram tempo de lixiviação e concentração de sólidos na polpa.As condições que melhor refletem o compromisso de recuperar os metais de interesse e a viabilidade econômica do processo foram alcançados com a razão 1:0,4 lodo galvânico/rejeito piritoso, 90 min de patamar e 550ºC de temperatura de sulfatação, para a etapa pirometalúrgica e 15 min de lixiviação e 14g.L-1 de sólidos em polpa como condições hidrometalúrgicas. Estas condições propiciaram a recuperação de 60% de zinco, 49% de níquel e 50% de cobre.

Cooperativas de crédito e formação da taxa de juros nas operações bancárias: teoria e evidências empíricas para o Brasil.

O presente trabalho tem como objetivo estudar se as cooperativas de crédito influenciam as taxas de juros praticadas pelos bancos comerciais e múltiplos com carteira comercial em suas operações de crédito e de depósitos a prazo. A pesquisa baseou-se no modelo de oligopólio de Monti-Klein (para os bancos), no modelo de Smith (para as cooperativas de crédito) e na teoria de Fama e Jensen sobre problemas de agência para criar uma estrutura teórica que permite entender a interação entre bancos e cooperativas de crédito nos mercados de crédito e de depósitos a prazo. A validade desta estrutura teórica foi testada empiricamente e os resultados evidenciaram que as cooperativas de crédito brasileiras influenciam as taxas de juros de crédito praticadas pelos bancos por meio de sua participação de mercado (market share). Uma maior participação de mercado das cooperativas de crédito está associada a maiores taxas de juros cobradas pelos bancos nas operações de crédito. Os resultados empíricos também evidenciaram que a participação de mercado das cooperativas de crédito não impacta as taxas de juros dos bancos para os depósitos a prazo.

Catalisadores de vanádio (V) contendo ligante tris(pirazolil)borato : rotas de imobilização e avaliação em polimerização de etileno

As sínteses, caracterizações e estudos referentes a polimerização do etileno de uma série de complexos {TpMs*}V(NtBu)Cl2 (1), {TpMs*}V(O)Cl2 (2), {TpMePh]V(NtBu)Cl2 (3) e {Tp*}V(O)Cl2 (4) são descritas. A reação destes complexos com MAO geram espécies catalíticas ativas para a polimerização do etileno. Para as reações de polimerização realizadas em tolueno a 30°C, as atividades variaram entre 71 e 1.126 kg de PE/mol[V]·h·atm. A atividade mais alta foi obtida usando o precursor catalítico 1. As curvas de DSC mostraram a formação de polietileno de alta densidade com temperaturas de fusão entre 134 e 141ºC. Visando a obtenção de catalisadores suportados, o complexo 1 foi imobilizado através do método direto sobre os seguintes suportes inorgânicos: SiO2, SiO2 modificada com MAO, SiO2-Al2O3, MCM-41, MgO e MgCl2. O teor de metal imobilizado, determinado por XRF, permaneceu entre 0,22 e 0,50 % g V/g suporte (p/p %).Os maiores teores de metal foram encontrados para os suportes com maiores áreas superficiais (SiO2–Al2O3 e MCM-41). Todos os sistemas mostraram-se ativos na polimerização do etileno na presença de MAO ou TiBA/MAO (1:1) (Al/V = 1000). A atividade catalítica mostrou-se dependente da natureza do suporte, ficando esta entre 8 e 89 kg de PE/mol[V]·h·atm. Os melhores resultados foram obtidos para sílica. Suportes ácidos ou básicos forneceram sistemas catalíticos menos ativos. Os polietilenos apresentaram pesos moleculares médios (Mw) superiores a 2.000.000 g/mol, sugerindo a produção de polímeros com ultra-alto peso molecular. Baseado nos resultados referentes a imobilização de 1, o complexo 2 foi imobilizado sobre SiO2 e SiO2 modificada com MAO. As reações de polimerização deste catalisador suportado foram realizadas em tolueno a 30ºC, utilizando MAO ou TiBA/MAO (1:1) (Al/V = 1000). Os resultados de atividade variaram entre 7 e 236 kg de PE/mol[V]·h·atm, sendo a maior atividade encontrada para o sistema suportado 2/SiO2/MAO(4,0 % Al/SiO2) na presença da mistura de cocatalisadores TiBA/MAO (1:1). Os complexos 1 e 2 foram imobilizados “in situ” utilizando SiO2 e SiO2/MAO (4,0 % em peso de Al/SiO2) como suportes, empregando 0,02 % em peso de V/g suporte. Todos os sistemas estudados foram ativos nas reações de polimerização do etileno. Para o complexo 1, a maior atividade (1.903 kg de PE/mol[V]·h·atm) foi obtida utilizando o sistema 1/SiO2/MAO (4,0 % em peso de Al/SiO2) na presença do MAO. Cabe ressaltar que, para este sistema catalítico, o uso de TMA ao invés de MAO proporciona a formação de um sistema catalítico altamente ativo (1.342 kg de PE/mol[V]·h·atm). A maior atividade (1.882 kg de PE/mol[V]·h·atm) para o complexo 2 foi encontrada quando o mesmo foi suportado “in situ” sobre SiO2, utilizando MAO como cocatalisador. O catalisador de vanádio preparado “in situ” sobre o suporte na presença do MAO apresentou uma atividade catalítica de 22 kg de PE/mol[V]·h·atm) sendo a mesma inferior àquela obtida utilizando o sistema via imobilização do catalisador “in situ”. Várias rotas sintéticas (hidrolíticas e não-hidrolíticas) objetivando a preparação “in situ” do catalisador sobre sílicas-híbridas foram empregadas, entretanto todas as tentativas falharam devido à alta reatividade do grupo NCO com alguns reagentes empregados no processo de preparação das mesmas. Uma série de catalisadores híbridos foram preparados pela combinação e imobilização seqüencial de {TpMs*}V(NtBu)Cl2 (1) e [LFeCl2] (8) (L = 2,6-bis(imino)piridila) sobre SiO2/MAO (4,0% em peso de Al/SiO2) em diferentes proporções (1:1) e (1:3). Todos os sistemas foram ativos na polimerização do etileno na presença de MAO como cocatalisador. A atividade mostrou-se dependente da natureza do complexo e da ordem de imobilização. A maior atividade foi obtida para o sistema V/Fe/SMAO-4 (1:1) (117 kg de PE/mol[M]·h·atm). Baseado nas curvas de DSC, diferentes tipos de PE podem ser obtidos dependendo da natureza do complexo imobilizado e da ordem da adição dos catalisadores no suporte. Para os sistemas híbridos, a presença do Fe determina a formação de PE com dois picos de fusão.

Otimização de uma metodologia para análise mineralógica racional de argilominerais

VARELA, M.L. et al. Otimização de uma metodologia para análise mineralógica racional de argilominerais. Cerâmica, São Paulo, n. 51, p. 387-391, 2005.

Influência do lodo de ETE na massa para fabricação de cerâmica vermelha

The WTP produce many kinds of residue on your treatment stages, but the sludge is the more problematic from the final disposition point view. The actual rate of residue production deriving from technological evolution and the crescent population needs prevents the subtle equilibrium generation between consumption and recycling/reuse, creating problems of pollution resulting from inappropriate management of residues. Thus, is necessary achieve a new equilibrium between the grow from raw materials and energy and the residue generation. This equilibrium should be achieved by technical and economic feasibility of environmental supported models through recycling and reuse. The red ceramic industry stand out in residue absorption question as raw material due their clay mass heterogeneity, constituted by clay minerals and non-clay minerals with wide mineralogical variation, allowing residue inclusion which act like plastic or non-plastic materials, contributing to retain heavy metals contained in residues in the vitreous mass formed during the burning of the ceramic bodies. This work propose the study of the influence of incorporation of 25 wt.% sludge from wastewater treatment plant, according preliminary results, in the mass to produce ceramic bodies. The raw materials was characterized through chemical composition analyses by XRF, mineralogical analyses by XRD, thermal analyses by TG and DTA, Atterberg limits and thermodilatometry. Subsequently was composed the mass with 75 wt.% of clay and 25 wt.% of dried wastewater sludge from UFRN WWTP. Samples with 6,0 x 2,0 x 0,5 cm was produced with unidirectional compacting under pressure of 20MPa and burned in temperatures between 950 and 1,200ºC. After fired, the ceramic bodies have been submitted to physical and mechanical analyses through the measure of firing shrinkage, water absorption, density, apparent porosity and flexural strength; crystallographic analyses through XRD and microstructure analyses by SEM. The technological properties obtained was satisfactory to production of roof tiles with 25 wt.% at 1,200 ºC, but the production of others products at lower temperatures was not feasible

Adição de cascalho de perfuração da bacia potiguar em argilas para uso em materiais cerâmicos: influência da concentração e temperatura de queima.

One of waste produced on large scale during the well drilling is the gravel drilling. There are techniques for the treatment of the same, but there isn t consensus on what are the best in terms of economic and environmental. One alternative for disposal of this waste and objective of this paper is the incorporation and immobilization of gravel clay matrix to assess their technological properties. The Raw Materials used were characterized by the following techniques: Chemical Analysis by X-ray fluorescence (XRF), mineralogical analysis by X-ray Diffraction (XRD), Grain Size Analysis (FA) and Thermal Analysis by Thermogravimetry (TG) and thermodiferential (DTA). After characterizing, samples were formulated in the following percentages: 0, 5, 10, 15, 25, 50, 75, 100% (weight) of gravel drilling, then the pieces were pressed, dried (110 ° C) and sintered at temperatures of 850, 950 and 1050 ° C. After sintering, samples were tested for water absorption, linear shrinkage, flexural strength, porosity, density, XRD and test color. The results concluded that the incorporation of gravel drilling is a viable possibility for solid masonry bricks and ceramic blocks manufacture at concentrations and firing temperature described here. Residue incorporation reduces an environmental problem, the cost of raw materials for manufacture of ceramic products

Estudo e desenvolvimento de um capacitor eletrolítico de nióbio

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

O efeito do tratamento da atapulgita no desenvolvimento de compósito com o polietileno reciclado

The study aimed at the treatment of attapulgite for the development and characterization of composite recycled low density polyethylene - PEBD_rec embedded with natural attapulgite - ATP_NAT, sifted - ATP_PN and attapulgite treated with sulfuric acid - ATP_TR in different compositions (1, 3 and 5%) and compared with the PEBD_rec. The atapulgitas, natural, screened and treated, were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), particle size analysis, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and determining the area specific surface (BET). The composites were characterized by thermogravimetry (TG), differential scanning calorimetry (DSC), Xray diffraction (XRD), torque rheometry, scanning electron microscopy (SEM) and traction. The composite PEBD_rec / ATP (natural, sieved and treated) were produced by mixing in the molten state in a single screw extruder matrix wire with subsequent reprocessing matrix tape. It was found that the screening of attapulgite not reduce the quantity of quartz and the acid treatment completely extracted dolomite aggregate impurities of the channels attapulgite, and increase their surface area. The addition of attapulgite in PEBD_rec acts as a catalyst, reducing the thermal stability of the polymer. The increased concentration of attapulgite, increases resistance and reduces the elongation at break and modulus of elasticity of the composite PEBD_rec / attapulgite

Estudo do efeito da adição da escória de aciaria no processamento e propriedades finais de telhas cerâmicas

This research presents an overview of the addition steelwork dust of ceramic shingles in order to contribute to the utilization use of such residue. The ceramic industry perspective in the Brazilian State of Piauí is quite promising. Unlike other productive sectors, the ceramic industry uses basically natural raw materials. Its final products are, in short, the result of transforming clay compounds. These raw materials are composed primarily of aluminum oxide, silicon, iron, sodium, magnesium, end calcium, among others. It was verified that steelwork dust is composed primarily of these same oxides, so that its incorporation in to structural ceramics is a very reasonable idea. Both clay and steelwork powder were characterized by AG, XRF, XRD, TGA and DTA. In addition, steelwork dust samples containing (0%, 5%, 10%, 15%, 20% and 25%) were extruded and burned at 800°C, 850°C, 900°C and 950°C. Then t echnological tests of linear shrinkage, water uptake, apparent porosity, apparent density and flexural strengthwere carried at. The results showed the possibility of using steelwork powder in ceramic shingles until 15% significant improvement in physical and mechanical properties. This behavior shows the possibility of burning at temperatures lower than 850ºC, thus promoting a product final cost reduction

Síntese e caracterização de TaC e óxido misto de tântalo e cobre nanoestruturados a partir do precursor oxálico de tântalo através de reações gás-sólido e sólido-sólido a baixa temperatura

The research and development of nanostructured materials have been growing significantly in the last years. These materials have properties that were significantly modified as compared to conventional materials due to the extremely small dimensions of the crystallites. The tantalum carbide (TaC) is an extremely hard material that has high hardness, high melting point, high chemical stability, good resistance to chemical attack and thermal shock and excellent resistance to oxidation and corrosion. The Compounds of Tantalum impregnated with copper also have excellent dielectric and magnetic properties. Therefore, this study aimed to obtain TaC and mixed tantalum oxide and nanostructured copper from the precursor of tris (oxalate) hydrate ammonium oxitantalato, through gas-solid reaction and solid-solid respectively at low temperature (1000 ° C) and short reaction time. The materials obtained were characterized by X-ray diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), Spectroscopy X-Ray Fluorescence (XRF), infrared spectroscopy (IR), thermogravimetric (TG), thermal analysis (DTA) and BET. Through the XRD analyses and the Reitiveld refinement of the TaC with S = 1.1584, we observed the formation of pure tantalum carbide and cubic structure with average crystallite size on the order of 12.5 nanometers. From the synthesis made of mixed oxide of tantalum and copper were formed two distinct phases: CuTa10O26 and Ta2O5, although the latter has been formed in lesser amounts

Desenvolvimento de um sistema misto de pasta à base de geopolímero e cimento portland para correção de perda de circulação

The materials engineering includes processes and products involving several areas of engineering, allowing them to prepare materials that fulfill the needs of various new products. In this case, this work aims to study a system composed of cement paste and geopolymers, which can contribute to solving an engineering problem that directly involves the exploitation of oil wells subject to loss of circulation. To correct it, has been already proposed the use of granular materials, fibers, reducing the drilling fluid or cement paste density and even surface and downhole mixed systems. In this work, we proposed the development of a slurry mixed system, the first was a cement-based slurry and the second a geopolymer-based slurry. The cement-based slurry was formulated with low density and extenders, 12.0 ppg (1.438 g/cm ³), showing great thixotropic characteristics. It was added nano silica at concentrations of 0.5, 1.0 and 1.5 gps (66.88, 133.76 and 200.64 L/m3) and CaCl2 at concentrations of 0.5, 1, 0 and 1.5%. The second system is a geopolymer-based paste formulated from molar ratios of 3.5 (nSiO2/nAl2O3), 0.27 (nK2O/nSiO2), 1.07 (nK2O/nAl2O3) and 13.99 (nH2O/nK2O). Finally, we performed a mixture of these two systems, for their application for correction of circulation lost. To characterize the raw materials, XRD, XRF, FTIR analysis and titration were performed. The both systems were characterized in tests based on API RP10B. Compressive strength tests were conducted after curing for 24 hours, 7 and 28 days at 58 °C on the cement-based system and the geopolymer-based system. From the mixtures have been performed mixability tests and micro structural characterizations (XRD, SEM and TG). The results showed that the nano silica, when combined with CaCl2 modified the rheological properties of the cement slurry and from the concentration of 1.5 gpc (200.64 L / m³) it was possible to obtain stable systems. The system mixture caused a change in the microstructure of the material by favoring the rate of geopolymer formation to hinder the C3S phase hydration, thus, the production of CSH phases and Portlandite were harmed. Through the mixability tests it can be concluded that the system, due to reduced setting time of the mixture, can be applied to plug lost circulation zones when mixed downhole