Aplicação da destilação simulada por cromatografia gasosa e da termogravimetria para a avaliação da influência da redução do teor de enxofre sobre as propriedades físico-químicas do óleo diesel

One of the main problems related to the use of diesel as fuel is the presence of sulfur (S) which causes environmental pollution and corrosion of engines. In order to minimize the consequences of the release of this pollutant, Brazilian law established maximum sulfur content that diesel fuel may have. To meet these requirements, diesel with a maximum sulfur concentration equal to 10 mg/kg (S10) has been widely marketed in the country. However, the reduction of sulfur can lead to changes in the physicochemical properties of the fuel, which are essential for the performance of road vehicles. This work aims to identify the main changes in the physicochemical properties of diesel fuel and how they are related to reduction of sulfur content. Samples of diesel types S10, S500 and S1800 were tested according with the methods of the American Society for Testing and Materials (ASTM). The fuels were also characterized by thermogravimetric analysis (TG) and subjected to physical distillation (ASTM D86) and simulated distillation gas chromatography (ASTM D2887). The results showed that the reduction of sulfur turned the fuel lighter and fluid, allowing a greater applicability to low temperature environments and safer for transportation and storage. Through the simulated distillation data was observed that decreasing sulfur content resulted in higher initial boiling point temperatures and the decreasing of the boiling temperature of the medium and heavy fractions. Thermogravimetric analysis showed a loss event mass attributed to volatilization or distillation of light and medium hydrocarbons. Based on these data, the kinetic behavior of the samples was investigated and it was observed that the activation energies (Ea) did not show significant changes throughout conversion. Considering the average of these energies, the S1800 had the highest Ea during the conversion and the S10 the lowest values

Desenvolvimento de novos biolubrificantes hidráulicos derivados dos óleos de maracujá e de moringa in natura e epoxidados

With the increasing environmental awareness, maximizing biodegradability and minimizing ecotoxicity is the main driving force for new technological developments. Thus, can be developed new biodegradable lubricants for use in environmentally sensitive areas. The aim of this study was to obtain new bio-lubricants from passion fruit (Passiflora edulis Sims f. flavicarpa Degener) and moringa (Moringa oleifera Lamarck) epoxidized oils and develop a new additive package using experimental design for their use as a hydraulic fluid. In the first stage of this work was performed the optimization of the epoxidation process of the oils using fractional experimental design 24-1 , varying the temperature, reaction time, ratio of formic acid and hydrogen peroxide. In the second step was investigated the selectivity, thermodynamics and kinetics of the reaction for obtaining the two epoxides at 30, 50 and 70 °C. The result of the experimental design confirmed that the epoxidation of passion fruit oil requires 2 hours of reaction, 50 °C and a ratio H2O2/C=C/HCOOH (1:1:1). For moringa oil were required 2 hours reaction, 50 °C and a ratio of H2O2/C=C/HCOOH (1:1:1.5). The results of the final conversions were equal to 83.09% (± 0.3) for passion fruit oil epoxide and 91.02 (±0,4) for moringa oil epoxide. Following was made the 23 factorial design to evaluate which are the best concentrations of corrosion inhibitor and anti-wear (IC), antioxidant (BHA) and extreme pressure (EP) additives. The bio-lubricants obtained in this step were characterized according to DIN 51524 (Part 2 HLP) and DIN 51517 (Part 3 CLP) standards. The epoxidation process of the oils was able to improve the oxidative stability and reduce the total acid number, when compared to the in natura oils. Moreover, the epoxidized oils best solubilized additives, resulting in increased performance as a lubricant. In terms of physicochemical performance, the best lubricant fluid was the epoxidized moringa oil with additives (EMO-ADI), followed by the epoxidized passion fruit oil with additives (EPF-ADI) and, finally, the passion fruit in natura oil without additives (PFO). Lastly, was made the investigation of the tribological behavior under conditions of boundary lubrication for these lubricants. The tribological performance of the developed lubricants was analyzed on a HFRR equipment (High Frequency Reciprocating Rig) and the coefficient of friction, which occurs during the contact and the formation of the lubricating film, was measured. The wear was evaluated through optical microscopy and scanning electron microscopy (SEM). The results showed that the addition of extreme pressure (EP) and anti-wear and corrosion inhibitor (CI) additives significantly improve the tribological properties of the fluids. In all assays, was formed a lubricating film that is responsible for reducing the coefficient of metal-to-metal wear. It was observed that the addition of EP and IC additives in the in natura vegetable oils of passion fruit and moringa did not favor a significant reduction in wear. The bio-lubricants developed from passion fruit and moringa oils modified via epoxidation presented satisfactory tribological properties and shown to be potential lubricants for replacement of commercial mineral-based fluids.

Desenvolvimento e avaliação tribológica de emulsão O/A a partir de óleo vegetal epoxidado para aplicação em fluídos de corte

The cutting fluids are lubricants used in machining processes, because they present many benefits for different processes. They have many functions, such as lubrication, cooling, improvement in surface finishing, besides they decreases the tool wear and protect it against corrosion. Therefore due to new environment laws and demand to green products, new cutting fluids must be development. These shall be biodegradable, non-toxic, safety for environment and operator healthy. Thus, vegetable oils are a good option to solve this problem, replacing the mineral oils. In this context, this work aimed to develop an emulsion cutting fluid from epoxidized vegetable oil, promoting better lubrication and cooling in machining processes, besides being environment friendly. The methodology was divided in five steps: first one was the biolubricant synthesis by epoxidation reaction. Following this, the biolubricant was characterized in terms of density, acidity, iodo index, oxirane index, viscosity, thermal stability and chemical composition. The third step was to develop an emulsion O/A with different oil concentration (10, 20 and 25%) and surfactant concentration (1, 2.5 and 5%). Also, emulsion stability was studied. The emulsion tribological performance were carried out in HFRR (High Frequency Reciprocating Rig), it consists in ball-disc contact. Results showed that the vegetable based lubricant may be synthesized by epoxidationreaction, the spectra showed that there was 100% conversion of the epoxy rings unsaturations. In regard the tribological assessment is observed that the percentage of oil present in the emulsion directly influenced the film formation and coefficient of friction for higher concentrations the film formation process is slow and unstable, and the coefficient of friction. The high concentrations of surfactants have not improved the emulsions tribological performance. The best performance in friction reduction was observed to emulsion with 10% of oil and 5% of surfactant, its average wear scar was 202 μm.

Análise experimental de danos em pistões de motor à gasolina operando com adição de gás hidróxi

The addition of hydrogen gas as an alternative fuel source has been widely used, as well reported in scientific literature. Today, several experiments are underway for the use of hydrogen generators (electrolysers) demand for motor vehicles. In all these products their ads manufacturers claim that this provides a reduction of fuel consumption, reduces the emission levels of toxic gas by the discharge and improves engine life. This research analyzes the physical structure of engine components using electrolysis on demand. To this end, a stationary system was fitted with a power generator of electricity, drum roller and adapted two electrolyzers: a dry cell and wet cell other. In steps observation were consumption analyzes in four work load ranges and observing the piston engine, which has been cut and analyzed by Optical Microscopy (OM), Scanning Electron Microscopy and Dispersive Energy (SEM-EDS), X – Ray Diffraction (XRD) and Confocal Microscopy, the stationary system in each step. The results showed a considerable reduction in fuel consumption and a high corrosion in the original factory piston constituted of aluminum-silicon alloy. As corrosion barrier was made a plasma nitriding in the piston head, which proved resistant to attack by hydrogen, although it has presented evidence also, of having been attacked. It is concluded that the automotive electrolysers can be a good choice in terms of consumption and reducing toxic gas emissions, but the material of the combustion chambers of vehicles must be prepared for this purpose.

Utilização do titâneo na confecção de estruturas metálicas em prótese parcial removível

Due to properties such as excellent biocompatibility, high resistance to corrosion and low specific weight, titanium has been considered a material of great interest for Dentistry. It has been widely used in implants and orthognathic surgeries. Recently, titanium has been seen as a feasible alternative for the fabrication of removable partial denture frameworks, either in pure titanium (99.75%) or in titanium alloy forms (Ti-6Al-4V; Ti-6A1-7Nb). Based on a review of the literature, this work studied the use of titanium for the fabrication of removable partial denture frameworks, focusing on its advantages and disadvantages as well as its characteristics. It was concluded that the use of titanium is a convenient option for partially edentulous arches rehabilitation with quite satisfactory and promising clinical results. However, the need for highly-equipped laboratories increases the cost, preventing its large scale use.

Utilização do titâneo na confecção de estruturas metálicas em prótese parcial removível

Due to properties such as excellent biocompatibility, high resistance to corrosion and low specific weight, titanium has been considered a material of great interest for Dentistry. It has been widely used in implants and orthognathic surgeries. Recently, titanium has been seen as a feasible alternative for the fabrication of removable partial denture frameworks, either in pure titanium (99.75%) or in titanium alloy forms (Ti-6Al-4V; Ti-6A1-7Nb). Based on a review of the literature, this work studied the use of titanium for the fabrication of removable partial denture frameworks, focusing on its advantages and disadvantages as well as its characteristics. It was concluded that the use of titanium is a convenient option for partially edentulous arches rehabilitation with quite satisfactory and promising clinical results. However, the need for highly-equipped laboratories increases the cost, preventing its large scale use.

Estudo da sinterização do aço inox 316L reforçado com 3% Carbeto de Tântalo - TaC

The present work shows a contribution to the studies of development and solid sinterization of a metallic matrix composite MMC that has as starter materials 316L stainless steel atomized with water, and two different Tantalum Carbide TaC powders, with averages crystallite sizes of 13.78 nm and 40.66 nm. Aiming the metallic matrix s density and hardness increase was added different nanometric sizes of TaC by dispersion. The 316L stainless steel is an alloy largely used because it s high resistance to corrosion property. Although, its application is limited by the low wear resistance, consequence of its low hardness. Besides this, it shows low sinterability and it cannot be hardened by thermal treatments traditional methods because of the austenitic structure, face centered cubic, stabilized mainly in nickel presence. Steel samples added with TaC 3% wt (each sample with different type of carbide), following a mechanical milling route using conventional mill for 24 hours. Each one of the resulted samples, as well as the pure steel sample, were compacted at 700 MPa, room temperature, without any addictive, uniaxial tension, using a 5 mm diameter cylindrical mold, and quantity calculated to obtain compacted final average height of 5 mm. Subsequently, were sintered in vacuum atmosphere, temperature of 1290ºC, heating rate of 20ºC/min, using different soaking times of 30 and 60 min and cooled at room temperature. The sintered samples were submitted to density and micro-hardness analysis. The TaC reforced samples showed higher density values and an expressive hardness increase. The complementary analysis in optical microscope, scanning electronic microscope and X ray diffractometer, showed that the TaC, processed form, contributed with the hardness increase, by densification, itself hardness and grains growth control at the metallic matrix, segregating itself to the grain boarders

Avaliação de heterociclo do tipo mesoiônico solubilizado em sistema microemulsionado para aplicação em dutos

The efficiency of inhibition to corrosion of steel AISI 1018 of surfactant coconut oil saponified (SCO) and heterocyclic type mesoionics (1,3,4-triazólio-2-tiolato) in systems microemulsionados (SCO-ME and SCO-ME-MI) Of type O/A (rich in water emulsion) region with the work of Winsor IV. The systems microemulsionados (SCO-ME and SCO-ME-MI) were evaluated with a corrosion inhibitor for use in saline 10,000 ppm of chloride enriched with carbon dioxide (CO2). The assessment of corrosion inhibitors were evaluated by the techniques of linear polarization resistance (LPR) and loss of weight (MW) in a cell instrumented given the gravity and electrochemical devices. The systems were shooting speed of less than 60 minutes and efficiency of inhibition [SCO-ME (91.25%) and SCO-ME-MI (98.54%)]

Obtenção de nanopartículas de hexaferrita de bário pelo método pechini

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

Sinterização de aço inoxidável reforçado com partículas nanométricas dispersas de carbeto de nióbio - NbC

Metal powder sintering appears to be promising option to achieve new physical and mechanical properties combining raw material with new processing improvements. It interest over many years and continue to gain wide industrial application. Stainless steel is a widely accepted material because high corrosion resistance. However stainless steels have poor sinterability and poor wear resistance due to their low hardness. Metal matrix composite (MMC) combining soft metallic matrix reinforced with carbides or oxides has attracted considerable attention for researchers to improve density and hardness in the bulk material. This thesis focuses on processing 316L stainless steel by addition of 3% wt niobium carbide to control grain growth and improve densification and hardness. The starting powder were water atomized stainless steel manufactured for Höganäs (D 50 = 95.0 μm) and NbC produced in the UFRN and supplied by Aesar Alpha Johnson Matthey Company with medium crystallite size 16.39 nm and 80.35 nm respectively. Samples with addition up to 3% of each NbC were mixed and mechanically milled by 3 routes. The route1 (R1) milled in planetary by 2 hours. The routes 2 (R2) and 3 (R3) milled in a conventional mill by 24 and 48 hours. Each milled samples and pure sample were cold compacted uniaxially in a cylindrical steel die (Ø 5 .0 mm) at 700 MPa, carried out in a vacuum furnace, heated at 1290°C, heating rate 20°C stand by 30 and 60 minutes. The samples containing NbC present higher densities and hardness than those without reinforcement. The results show that nanosized NbC particles precipitate on grain boundary. Thus, promote densification eliminating pores, control grain growth and increase the hardness values

Desenvolvimento de tubulação em compósito polimérico revestida externamente com poliuretano de alta densidade

Pipelines for the transport of crude oil from the production wells to the collecting stations are named production lines . These pipes are subjected to chemical and electrochemical corrosion according to the environment and the type of petroleum transported. Some of these lines, depending upon the composition of the fluid produced, may leak within less than one year of operation due to internal corrosion. This work aims at the development of composite pipes with an external protecting layer of high density polyurethane for use in production lines of onshore oil wells, meeting operational requirements. The pipes were manufactured using glass fibers, epoxy resin, polyester resin, quartz sand and high density polyurethane. The pipes were produced by filament winding with the deposition of high density polyurethane on the external surface and threaded ends (API 15 HR/PM-VII). Three types of pipes were manufactured: glass/epoxy, glass/epoxy with an external polyurethane layer and glass/epoxy with an intermediate layer of glass fiber, polyester, sand and with an external polyurethane layer. The three samples were characterized by Scanning Electronic Microscopy (SEM) and for the determination of constituent content. In addition, the following tests were conducted: hydrostatic test, instant rupture, shorttime failure pressure, Gardner impact, transverse stiffness and axial tension. Field tests were conducted in Mossoró RN (BRAZIL), where 1,677 meters of piping were used. The tests results of the three types of pipes were compared in two events: after two months from manufacturing of the samples and after nine months of field application. The results indicate that the glass/epoxy pipes with an intermediate layer of fiber glass composite, polyester e sand and with an external layer of high density polyurethane showed superior properties as compared to the other two and met the requirements of pressure class, axial tensile strength, transverse stiffness, impact and environmental conditions, for onshore applications as production lines

Estudos de Durabilidade Frente ao Ataque Ácido de Compósitos Portland-Polímero para Cimentação de Poços de Petróleo

Portland-polymers composites are promising candidates to be used as cementing material in Northeastern oil wells of Brazil containing heavy oils submitted to steam injection. In this way, it is necessary to evaluate its degradation in the commonly acidizind agents. In addition, to identify how aggressive are the different hostile environments it is an important contribution on the decision of the acidic systems to be used in. It was investigated the performance of the Portland-polymer composites using powdered polyurethane, aqueous polyurethane, rubber tire residues and a biopolymer, those were reinforced with polished carbon steel SAE 1045 to make the electrochemical measurements. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) and HAc 10 % + HF 1,5 % were used as degrading environment and electrolytes. The more aggressive acid solution to the plain Portland hardened cement paste was the regular mud acid, that showed loss of weight around 23.0 %, followed by the soft mud acid, the showed 11.0 %, 15.0 % HCl with 7,0 % and, at last the 10.0 % HAc plus HF 1.5 % with just 1.0 %. The powdered polyurethane-composite and the aqueous polyurethane one showed larger durability, with reduction around 87.0 % on the loss of weight in regular mud acid. The acid attack is superficial and it occurs as an action layer, where the degraded layer is responsible for the decrease on the kinetic of the degrading process. This behavior can be seen mainly on the Portland- aqueous polyurethane composite, because the degraded layer is impregnated with chemically modified polymer. The fact of the acid attack does not have influence on the compressive strength or fratography of the samples, in a general way, confirms that theory. The mechanism of the efficiency of the Portland-polymers composites subjected to acid attack is due to decreased porosity and permeability related with the plain Portland paste, minor quantity of Ca+2, element preferentially leached to the acidic solution, wave effect and to substitute part of the degrading bulk for the polymeric one. The electrolyte HAc 10 % + HF 1,5 % was the least aggressive one to the external corrosion of the casing, showing open circuit potentials around +250 mV compared to -130 mV to the simulated pore solution to the first 24 hours immersion. This behavior has been performed for two months at least. Similar corrosion rates were showed between both of the electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and big polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirm its efficiency. In this way, Portlandpolymers composites are possible solutions to be succeed applied to oilwell cementing concomitant submitted to steam injection and acidizing operation and the HAc 10,0 % + HF 1,5 % is the less aggressive solution to the external corrosion of the casing

Estudo sobre o efeito dos parâmetros de processamento dos pós e sinterização do aço inox 316l reforçado com NbC

This masther dissertation presents a contribution to the study of 316L stainless steel sintering aiming to study their behavior in the milling process and the effect of isotherm temperature on the microstructure and mechanical properties. The 316L stainless steel is a widely used alloy for their high corrosion resistance property. However its application is limited by the low wear resistance consequence of its low hardness. In previous work we analyzed the effect of sintering additives as NbC and TaC. This study aims at deepening the understanding of sintering, analyzing the effect of grinding on particle size and microstructure and the effect of heating rate and soaking time on the sintered microstructure and on their microhardness. Were milled 316L powders with NbC at 1, 5 and 24 hours respectively. Particulates were characterized by SEM and . Cylindrical samples height and diameter of 5.0 mm were compacted at 700 MPa. The sintering conditions were: heating rate 5, 10 and 15◦C/min, temperature 1000, 1100, 1200, 1290 and 1300◦C, and soaking times of 30 and 60min. The cooling rate was maintained at 25◦C/min. All samples were sintered in a vacuum furnace. The sintered microstructure were characterized by optical and electron microscopy as well as density and microhardness. It was observed that the milling process has an influence on sintering, as well as temperature. The major effect was caused by firing temperature, followed by the grinding and heating rate. In this case, the highest rates correspond to higher sintering.

Estudo da sinterabilidade de ligas de níquel obtidas por meio dos portadores de liga sic, si3n4 ou si metálico com grafita

Nickel alloys are frequently used in applications that require resistance at high temperatures associated with resistance to corrosion. Alloys of Ni-Si-C can be obtained by means of powder metallurgy in which powder mixtures are made of metallic nickel powders with additions of various alloying carriers for such were used in this study SiC, Si3N4 or Si metal with graphite. Carbonyl Ni powder with mean particle size of 11 mM were mixed with 3 wt% of SiC powders with an average particle size of 15, 30 and 50 μm and further samples were obtained containing 4 to 5% by mass of SiC with average particle size of 15 μm. Samples were also obtained by varying the carrier alloy, these being Si3N4 powder with graphite, with average particle size of 1.5 and 5 μm, respectively. As a metallic Si graphite with average particle size of 12.5 and 5 μm, respectively. The reference material used was nickel carbonyl sintered without adding carriers. Microstructural characterization of the alloys was made by optical microscopy and scanning electron microscopy with semi-quantitative chemical analysis. We determined the densities of the samples and measurement of microhardness. We studied the dissociation of carriers alloy after sintering at 1200 ° C for 60 minutes. Was evaluated also in the same sintering conditions, the influence of the variation of average particle size of the SiC carrier to the proportion of 3% by mass. Finally, we studied the influence of variation of the temperatures of sintering at 950, 1080 and 1200 ° C without landing and also with heights of 30, 60, 120 and 240 minutes for sintering where the temperature was 950 °C. Dilatometry curves showed that the SiC sintered Ni favors more effectively than other carriers alloy analyzed. SiC with average particle size of 15 μm active sintering the alloy more effectively than other SiC used. However, with the chemical and morphological analyzes for all leagues, it was observed that there was dissociation of SiC and Si3N4, as well as diffusion of Si in Ni matrix and carbon cluster and dispersed in the matrix, which also occurred for the alloys with Si carriers and metallic graphite. So the league that was presented better results containing Si Ni with graphite metallic alloy as carriers, since this had dispersed graphite best in the league, reaching the microstructural model proposed, which is necessary for material characteristic of solid lubricant, so how we got the best results when the density and hardness of the alloy

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