Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Pirólise de borras oleosas de petroleo utilizando nanomateriais

The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

Caracterização de superfícies de titânio modificado por oxidação à plasma

Recent years have seen a significant growth in surface modifications in titanium implants, resulting in shorter healing times in regions with low bone density. Among the different techniques, subtraction by chemical agents to increase oxidation has been applied for surface treatment of dental implants. However, this technique is generally unable to remove undesirable oxides, formed spontaneously during machining of titanium parts, raising costs due to additional decontamination stages. In order to solve this problem, the present study used plasma as an energy source to both remove these oxides and oxidize the titanium surface. In this respect, Ti disks were treated by hollow cathode discharge, using a variable DC power supply and vacuum system. Samples were previously submitted to a cleaning process using an atmosphere of Ar, H2 and a mixture of both, for 20 and 60 min. The most efficient cleaning condition was used for oxidation in a mixture of argon (60%) and oxygen (40%) until reaching a pressure of 2.2 mbar for 60 min at 500°C. Surfaces were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), adhesion and cell proliferation. SEM showed less cell spreading and a larger number of projections orfilopodia in the treated samples compared to the control sample. AFM revealed surface defects in the treated samples, with varied geometry between peaks and valleys. Biological assays showed no significant difference in cell adhesion between treated surfaces and the control. With respect to cell proliferation, the treated surface exhibited improved performance when compared to the control sample. We concluded that the process was efficient in removing primary oxides as well as in oxidizing titanium surfaces

Desenvolvimento de microemulsões contendo fotoprotetores inorgânicos nanoparticulador

The inorganic actives, represented mainly by microfine zinc oxide and titanium dioxide, have shown great potential to protect against large UV spectrum. The aim of this study is the development, characterization and analysis of stability in the short term of microemulsions containing inorganic fotoprotection agents. The microemulsions identified by the phases diagram containing the metallic oxides were produced by two different methods and subjected to the centrifugation test and thermal stress cycles, and subsequently characterized by macroscopic evaluation, test dilution, electrical conductivity, pH, particle size, and zeta potential. This study highlights the influence of the metal oxides addition in the structure and distribution of micelles in the microemulsions

Desenvolvimento de antenas de microfita e antenas DRA Broadband

The search for ever smaller device and without loss of performance has been increasingly investigated by researchers involving applied electromagnetics. Antennas using ceramics materials with a high dielectric constant, whether acting as a substract element of patch radiating or as the radiant element are in evidence in current research, that due to the numerous advantages offered, such as: low profile, ability to reduce the its dimensions when compared to other devices, high efficiency of ratiation, suitability the microwave range and/or millimeter wave, low temperature coefficient and low cost. The reason for this high efficiency is that the dielectric losses of ceramics are very low when compared to commercially materials sold used in printed circuit boards, such as fiberglass and phenolite. These characteristics make ceramic devices suitable for operation in the microwave band. Combining the design of patch antennas and/or dielectric resonator antenna (DRA) to certain materials and the method of synthesis of these powders in the manufacture of devices, it s possible choose a material with a dielectric constant appropriate for the design of an antenna with the desired size. The main aim of this work is the design of patch antennas and DRA antennas on synthesis of ceramic powders (synthesis by combustion and polymeric precursors - Pe- chini method) nanostructured with applications in the microwave band. The conventional method of mix oxides was also used to obtain nanometric powders for the preparation of tablets and dielectric resonators. The devices manufactured and studied on high dielectric constant materials make them good candidates to have their small size compared to other devices operating at the same frequency band. The structures analyzed are excited by three different techniques: i) microstrip line, ii) aperture coupling and iii) inductive coupling. The efficiency of these techniques have been investigated experimentally and compared with simulations by Ansoft HFSS, used in the accurate analysis of the electromagnetic behavior of antennas over the finite element method (FEM). In this thesis a literature study on the theory of microstrip antennas and DRA antenna is performed. The same study is performed about the materials and methods of synthesis of ceramic powders, which are used in the manufacture of tablets and dielectric cylinders that make up the devices investigated. The dielectric media which were used to support the analysis of the DRA and/or patch antennas are analyzed using accurate simulations using the finite difference time domain (FDTD) based on the relative electrical permittivity (er) and loss tangent of these means (tand). This work also presents a study on artificial neural networks, showing the network architecture used and their characteristics, as well as the training algorithms that were used in training and modeling some parameters associated with the devices investigated

Análise da Conformidade e Caracterização da Matéria- Prima Empregada na Fabricação de Blocos Cerâmicos na Região Metropolitana de Salvador

The potential market of the metropolitan area of Salvador accounts for the estimated consumption of roughly 800 million horizontally perforated extruded clay bricks a year. The growing demand of consumers along with the competitiveness of the structural ceramic sector has driven forward a number of recent efforts and investments towards improving the quality of structural ceramics. In this scenario, the present study focused on sampling and evaluating the conformity of 8-hole horizontally perforated extruded clay bricks manufactured by different plants (A, B and C) in the metropolitan area of Salvador. In addition, representative clay and sandy-clay materials were collected from each plant and characterized by conventional physical, chemical and mineralogical techniques. Finally, experimental compositions designated as A, B and C, according to the source, were prepared by mixing different contents of the raw materials collected in the plants, fired at different temperatures and characterized. The results revealed a series of non conformities regarding ABNT guidelines. The characterization of raw materials revealed the presence of kaolinite and ilite in concentrations ranging from 64 to 90 wt.% along with free quartz (10 - 25%). The sandy-clay samples consisted basically of kaolinite. All raw materials depicted low contents of organics, amorphous constituents, alkaline oxides and feldspar. An analysis of the firing behavior of all different ceramic compositions revealed that the linear contraction of composition A was rather significant considering the temperature range evaluated, and it justifies the significant dimensional non conformity that was shown by bricks made with the ceramic A

Estudo da oxidação superficial de ligas odontológicas de Ni-Cr em plasma pulsado para uso em restaurações metalocerâmicas

Metal ceramic restorations matches aesthetic and strength, and in your making occurs an interface oxide layer, wetting resulting and atomic and ionic interactions resulting between metal, oxide and porcelain. However, frequent clinical fails occurs in this restoration type, because lost homogeneous deposition oxide layer and lost interface bond. Thus, in this study, thought depositate homogeneous oxide films above Ni-Cr samples surfaces polite previously, at plasma oxide environment. Six samples was oxided at 300 and 400ºC at one hour, and two samples was oxided in a comum chamber at 900ºC, and then were characterized: optical microscopic, electronic microscopic, micro hardness, and X ray difratometry. Colors stripes were observed at six samples plasma oxided and a grey surface those comum oxided, thus like: hardness increase, and several oxides from basic metals (Ni-Cr)

Mecanismos de desgaste, história térmica e ciclo de vida de componentes de um motor de combustão interna de aeromodelo

We developed an assay methodology that considered the temperature variation and the scanning electron microscopy as a method to quantify and characterize respectively the consumption evolution in three 46 LA machines, with internal combustion and two-stroke engines, 7.64 cm3 cylinder capacity, 23.0 millimeters diameter and 18.4 millimeters course, RPM service from 2.000 to 16.000 rpm, 1.2 HP power, and 272 grams weight. The investigated engines components were: (1) head of the engine (Al-Si alloy), (2) piston (Al-Si alloy) and (3) piston pin (AISI 52100 steel). The assays were carried out on a desktop; engines 1 and 2 were assayed with no load, whereas in two assays of engine 3 we added a fan with wind speed that varied from 8.10 m/s to 11.92 m/s, in order to identify and compare the engine dynamic behavior as related to the engines assayed with no load. The temperatures of the engine s surface and surroundings were measured by two type K thermopairs connected to the assay device and registered in a microcomputer with data recording and parameters control and monitoring software, throughout the assays. The consumed surface of the components was analyzed by scanning electron microscopy (SEM) and microanalysis-EDS. The study was complemented with shape deformation and mass measurement assays. The temperature variation was associated with the oxides morphology and the consumption mechanisms were discussed based on the relation between the thermal mechanical effects and the responses of the materials characterization

Síntese de pigmentos cerâmicos inorgânicos nanométricos pela rota dos precursores poliméricos

Considering the constant evolution of technology in growth and the need for production techniques in the ceramics area to move forward together, we sought in this study, the research and development of polymeric precursor method to obtain inorganic ceramic pigments. Method that provides quality to obtain the precursor powders of oxides and pigments at the same time, offers time and cost advantages, such as reproducibility, purity and low temperature heat treatment, control of stoichiometry. This work used chromium nitrate and iron nitrate as precursors. The synthesis is based on the dissolution of citric acid as a complexing agent, addition of metal oxides, such as ion chromophores; polymerization with ethylene glycol and doping with titanium oxide. Passing through precalcination, breakdown, thermal treatments at different temperatures of calcination (700 to 1100 oC), resulting in pigments: green for chromium oxide deposited on TiO2 (CrTiO3) and orange for iron oxide deposited on TiO2 ( FeTiO3). Noticing an increase of opacity with increasing temperature. Were performed thermal analysis (TG and ATD) in order to evaluate its thermodecomposition. The powders were also characterized by techniques such as XRD, revealing the formation of crystalline phases such as iron titanate (FeTiO3) and chrome titanate (CrTiO3), SEM, demonstrating formation of rounded particles for both oxides and Spectroscopy in the UV-Visible Region, verifying the potential variation and chromaticity os pigments. Thus, the synthesized oxides were within the requirements to be applied as pigments and shown to be possible to propose its use in ceramic materials

Redução carbotérmica de TiO2 por descarga em cátodo oco

In this study we used the plasma as a source of energy in the process of carbothermic reduction of rutile ore (TiO2). The rutile and graphite powders were milled for 15 h and placed in a hollow cathode discharge produced by in order to obtain titanium carbonitride directly from the reaction, was verified the influence of processing parameters of plasma temperature and time in the synthesis of TiCN. The reaction was carried out at 600, 700 and 800˚C for 3 to 4 hours in an atmosphere of nitrogen and argon. During all reactions was monitored by plasma technique of optical emission spectroscopy (EEO) to check the active species present in the process of carbothermal reduction of TiO2. The powder obtained after the reactions were characterized by the techniques of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The technique of EEO were detected in all reactions the spectra CO and NO, and these gas-phase resulting from the reduction of TiO2. The results of X-ray diffraction confirmed the reduction, where for all conditions studied there was evidence of early reduction of TiO2 through the emergence of intermediate oxides. In the samples reduced at 600 and 700˚C, there was only the phase Ti6O11, those reduced to 800˚C appeared Ti5O9 phases, and Ti6O11 Ti7O13, confirming that the carbothermal reduction in plasma, a reduction of the ore rutile (TiO2) in a series of intermediate titanium oxide (TinO2n-1) where n varies between 5 and 10

Estudo do aproveitamento do rejeito da mineração de esmeraldas na produção de refratários conformados isolantes

Emerald mining is an important area of the economy in Brazil, country which is in second place among the exporting nations of this gem. Due to the process of extraction, a great amount of reject is generated. Since there is no appropriate destination, the reject is abandoned around the mining industries, contributing to environment degradation. Nowadays, some of the most relevant things to an industry in general are: energy conservation, cost reduction, quality and productivity enhancement. The production of isolating, transformed refractory materials achieves the sustainability dimension when protection of the environment is incorporated to such process. This work investigates the use of emerald mining rejects in the ceramic body of refractory materials, aiming at obtaining a product whose characteristics are compatible with commercial products and, at the same time, allow the use of such rejects to solve the environmental issue caused by its disposal in nature. X-ray fluorescence analysis show that the emerald reject obtained after the flotation to extract molybdenum and mica has 70% of silica and alumina (SiO2+Al2O3) and 21% of a basic oxides and alkaline metals and earthy alkaline mixture (Na2O, K2O, CaO e MgO). Because of the significant amount of silica and alumina present in the reject, four refractory ceramic bodies were prepared. Samples with a rectangular shape and dimensions 100x50x10 mm were pressed in a steel mold at 27,5 MPa and sintered at 1200ºC for 40 min. under environment atmosphere in a resistive oven. The sintered samples were characterized in relation to the chemical composition (FRX), mineralogical composition (DRX), microstructure (MEV) and physical and mechanical properties. The results indicate that the mixture with 45% of reject, 45% of alumina and 10% of kaolin presents a refractory quality of 1420ºC, dimensional linear variation below 2.00%, apparent specific mass of 1,56 g/cm3 and porosity of 46,68%, which demonstrates the potential use of the reject as raw material for the industry of isolating transformed refractory materials

Estudo tribológico de biolubrificantes com adição de nanopartículas de óxidos (zinco e cobre)

Currently, vegetable oils have been studied for bio-lubricants base that fits the new environmental standards. Since, in a world full of finite natural resources, mineral oils bring consequences to the environment due to its low biodegradability and toxicity, also it is important to consider that synthetic oils have a high cost The aim of this work is to obtain a biolubricant additived with oxide nanoparticles (ZnO and CuO) for better resistance to friction and wear, which is not toxic to the environment and have better adherence under boundary lubrication. The methodology consisted in the synthesis of bio-lubricants (soybean and sunflower base) by epoxidation reaction. Then, some physical-chemical analysis in bio-lubricants are made to characterize theses lubricants, such as, density, acidity, iodine value, viscosity, viscosity index. Later, the lubricants were additive with nanoparticles. The tribological performance was evaluated by the equipment HFRR (High Frequency Reciprocating Rig) consisting of a wear test ball-plan type. The characterization of wear analysis was performed by SEM / EDS. The results show that bio-lubricants may be synthesized by reaction of epoxidation with good conversion. Tribological point of view, the epoxidized oils are more effective than lubricant additived with the oxide nanoparticles, they had lower coefficients of friction and better rate of film formation in the study. However, because they are environmentally friendly, bio-lubricants gain the relevant importance in tribological field

Formulação de novos combustíveis base diesel: avaliação de desempenho e emissões

The industry, over the years, has been working to improve the efficiency of diesel engines. More recently, it was observed the need to reduce pollutant emissions to conform to the stringent environmental regulations. This has attached a great interest to develop researches in order to replace the petroleum-based fuels by several types of less polluting fuels, such as blends of diesel oil with vegetable oil esters and diesel fuel with vegetable oils and alcohol, emulsions, and also microemulsions. The main objective of this work was the development of microemulsion systems using nonionic surfactants that belong to the Nonylphenols ethoxylated group and Lauric ethoxylated alcohol group, ethanol/diesel blends, and diesel/biodiesel blends for use in diesel engines. First, in order to select the microemulsion systems, ternary phase diagrams of the used blends were obtained. The systems were composed by: nonionic surfactants, water as polar phase, and diesel fuel or diesel/biodiesel blends as apolar phase. The microemulsion systems and blends, which represent the studied fuels, were characterized by density, viscosity, cetane number and flash point. It was also evaluated the effect of temperature in the stability of microemulsion systems, the performance of the engine, and the emissions of carbon monoxide, nitrogen oxides, unburned hydrocarbons, and smoke for all studied blends. Tests of specific fuel consumption as a function of engine power were accomplished in a cycle diesel engine on a dynamometer bench and the emissions were evaluated using a GreenLine 8000 analyzer. The obtained results showed a slight increase in fuel consumption when microemulsion systems and diesel/biodiesel blends were burned, but it was observed a reduction in the emission of nitrogen oxides, unburned hydrocarbons, smoke index and f sulfur oxides

Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões

The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market

Propriedades física de molécilas orgânicas e compostos do tipo perovskita CdSiO3 e CaPbO3

In the first part of this work our concern was to investigate the thermal effects in organic crystals using the theory of the polarons. To analyse such effect, we used the Fröhlich s Hamiltonian, that describes the dynamics of the polarons, using a treatment based on the quantum mechanics, to elucidate the electron-phonon interaction. Many are the forms to analyzing the polaronic phenomenon. However, the measure of the dielectric function can supply important information about the small polarons hopping process. Besides, the dielectric function measures the answer to an applied external electric field, and it is an important tool for the understanding of the many-body effects in the normal state of a polaronic system. We calculate the dielectric function and its dependence on temperature using the Hartree-Fock decoupling method. The dieletric function s dependence on the temperature is depicted by through a 3D graph. We also analyzed the so called Arrhenius resistivity, as a functionof the temperature, which is an important tool to characterize the conductivity of an organic molecule. In the second part we analyzed two perovskita type crystalline oxides, namely the cadmium silicate triclinic (CdSiO3) and the calcium plumbate orthorhombic (CaPbO3), respectively. These materials are normally denominated ABO3 and they have been especially investigated for displaying ferroelectric, piezoelectric, dielectrics, semiconductors and superconductors properties. We found our results through ab initio method within the functional density theory (DFT) in the GGA-PBE and LDA-CAPZ approximations. After the geometry optimization for the two structure using the in two approximations, we found the structure parameters and compared them with the experimental data. We still determined further the angles of connection for the two analyzed cases. Soon after the convergence of the energy, we determined their band structures, fundamental information to characterize the nature of the material, as well as their dielectrics functions, optical absorption, partial density of states and effective masses of electrons and holes