Síntese e caracterização de óxidos de zinco e de magnésio suportados em A1SBA-15 para produção de biodiesel

To overcome the challenge of meeting growing energy demand in a sustainable way, biodiesel has shown very promising as alternative energy can replace fossil fuels, even partially. Industrially, the biodiesel is produced by homogeneous transesterification reaction of vegetable oils in the presence of basic species used as catalysts. However, this process is the need for purification of the esters obtained and the removal of glycerin formed after the reaction. This context, the alternative catalysts have that can improve the process of biodiesel production, aiming to reduce costs and facilitate its production. In this study, the AlSBA-15 support with Si / Al ratio = 50 was synthesized, as like as the heterogeneous catalysts of zinc oxide and magnesium supported on mesoporous AlSBA-15 silica, in the concentrations of 5, 10, 15 and 30 %, relative to the support. The textural properties and structural characterization of catalysts and supports were determined by techniques: X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) coupled to the chemical analyzer, adsorption / desorption of N2, thermal analysis (TG / DTG), absorption spectroscopy in the infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). Characterization results indicated that the support AlSBA-15 retained the hexagonal ordered after the incorporation of zinc oxide and magnesium oxide in the holder. For heterogeneous catalysts, ZnO-AlSBA-15, that was observed the presence of zinc oxide nanoparticles dispersed in the surface and interior channels of the mesoporous and microporous support. The catalytic activity was evaluated by the transesterification reaction of sunflower oil via methylic route, and some reaction parameters were optimized with the most active catalyst in biodiesel production by sunflower oil. For the series of heterogeneous catalysts, the sample with 30 % ZnO supported on AlSBA-15 showed a better conversion of triglyceride to methyl esters, about 95.41 % of reaction conditions: temperature 175 °C, with molar ratio of 42:1, stirring at 200 rpm and under a pressure of 14 bar for 6 h. The catalyst MgO-AlSBA-15 showed no catalytic activity in the studied reactions

Estudo cinético da degradação térmica e catalítica de petróleo pesado usando Al-MCM-41

The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API º equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ° C and heating ratios (β) ranging from 5, 10 and 20 °C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41

Degradação térmica e catalítica do resíduo atmosférico de petróleo (RAT), utilizando materiais nanoestruturados do tipo SBA-15

In this work were synthesized and characterized the materials mesoporous SBA-15 and Al- SBA-15, Si / Al = 25, 50 and 75, discovered by researchers at the University of California- Santa Barbara, USA, with pore diameters ranging from 2 to 30 nm and wall thickness from 3.1 to 6.4 nm, making these promising materials in the field of catalysis, particularly for petroleum refining (catalytic cracking), as their mesopores facilitate access of the molecules constituting the oil to active sites, thereby increasing the production of hydrocarbons in the range of light and medium. To verify that the materials used as catalysts were successfully synthesized, they were characterized using techniques of X-ray diffraction (XRD), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). Aiming to check the catalytic activity thereof, a sample of atmospheric residue oil (ATR) from the pole Guamaré-RN was performed the process by means of thermogravimetry and thermal degradation of catalytic residue. Upon the curves, it was observed a reduction in the onset temperature of the decomposition process of catalytic ATR. For the kinetic model proposed by Flynn-Wall yielded some parameters to determine the apparent activation energy of decomposition, being shown the efficiency of mesoporous materials, since there was a decrease in the activation energy for the reactions using catalysts. The ATR was also subjected to pyrolysis process using a pyrolyzer with gas chromatography coupled to a mass spectrometer. Through the chromatograms obtained, there was an increase in the yield of the compounds in the range of gasoline and diesel from the catalytic pyrolysis, with emphasis on Al-SBA-15 (Si / Al = 25), which showed a percentage higher than the other catalysts. These results are due to the fact that the synthesized materials exhibit specific properties for application in the process of pyrolysis of complex molecules and high molecular weight as constituents of the ATR

Síntese e caracterização de zeólita beta hierarquizada e materiais híbridos micro-mesoporosos aplicados no craqueamento de PEAD

A catalyst of great interest to the scientific community tries to unite the structure of ordered pore diameter from mesoporous materials with the properties of stability and acid activity to microporous zeolites. Thus a large number of materials was developed in the past decades, which although being reported as zeolites intrinsically they fail to comply with some relevant characteristics to zeolites, and recently were named zeolitic materials of high accessibility. Among the various synthesis strategies employed, the present research approaches the synthesis methods of crystallization of silanized protozeolitic units and the method of protozeolitic units molded around surfactant micelles, in order for get materials defined as hierarchical zeolites and micro-mesoporous hybrid materials, respectively. As goal BEA/MCM-41 hybrid catalysts with bimodal pore structure formed by nuclei of zeolite Beta and cationic surfactant cetyltrimethylammonium were developed. As also was successfully synthesized the hierarchical Beta zeolite having a secondary porosity, in addition to the typical and uniform zeolite micropores. Both catalysts were applied in reactions of catalytic cracking of high density polyethylene (HDPE), to evaluate its properties in catalytic activity, aiming at the recycling of waste plastics to obtain high value-added raw materials and fuels. The BEA/MCM-41 hybrid materials with 0 days of pre-crystallization did not show enough properties for use in catalytic cracking reactions, but they showed superior catalytic properties compared to those ordered mesoporous materials of Al-MCM-41 type. The structure of Beta zeolite with hierarchical porosity leads the accessibility of HDPE bulky molecules to active centers, due to high external area. And provides higher conversion to hydrocarbons in the gasoline range, especially olefins which have great interest in the petrochemical industry

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Reciclagem química de Polietileno utilizando Sílica Mesoporosa tipo SBA-15 avalizada por Termogravimetriae Espectrometria de Massas

The chemical recycling of polyolefins has been the focus of increasing attention owing potential application as a fuel and as source chemicals. The use of plastic waste contributes to the solution of pollution problems.The use of catalysts can enhance the thermal degradation of synthetic polymers, which may be avaliated by Themogravimetry (TG) and mass spectrometry (MS) combined techniques. This work aims to propose alternatives to the chemistry recycling of low-density polyethylene (LDPE) on mesoporous silica type SBA-15 and AlSBA-15.The mesoporous materials type SBA-15 and AlSBA-15 were synthesized through the hydrothermal method starting from TEOS, pseudobohemite, cloridric acid HCl and water. As structure template was used Pluronic P123. The syntheses were accomplished during the period of three days. The best calcination conditions for removal of the organic template (P123) were optimized by thermal analysis (TG/DTG) and through analyses of Xray diffraction (XRD), infrared spectroscopy (FT-IR), nitrogen adsorption and scanning electron microscopy (SEM) was verified that as much the hydrothermal synthesis method as the calcination by TG were promising for the production of mesoporous materials with high degree of hexagonal ordination. The general analysis of the method of Analog Scan was performed at 10oC/min to 500 oC to avoid deterioration of capillary with very high temperatures. Thus, with the results, we observed signs mass/charge more evident and, using the MID method, was obtained curve of evolution of these signals. The addition of catalysis produced a decrease in temperature of polymer degradation proportional to the acidity of the catalyst. The results showed that the mesoporous materials contributed to the formation of compounds of lower molecular weight and higher value in the process of catalytic degradation of LDPE, representing an alternative to chemical recycling of solid waste

Estudo de materiais mesoporosos funcionalizados com diferentes aminas para captura do dióxido de carbono através do processo de adsorção

Intensive use of machinery and engines burning fuel dumps into the atmosphere huge amounts of carbon dioxide (CO2), causing the intensification of the greenhouse effect. Climate changes that are occurring in the world are directly related to emissions of greenhouse gases, mainly CO2, gases, mainly due to the excessive use of fossil fuels. The search for new technologies to minimize the environmental impacts of this phenomenon has been investigated. Sequestration of CO2 is one of the alternatives that can help minimize greenhouse gas emissions. The CO2 can be captured by the post-combustion technology, by adsorption using adsorbents selective for this purpose. With this objective, were synthesized by hydrothermal method at 100 °C, the type mesoporous materials MCM - 41 and SBA-15. After the synthesis, the materials were submitted to a calcination step and subsequently functionalized with different amines (APTES, MEA, DEA and PEI) through reflux method. The samples functionalized with amines were tested for adsorption of CO2 in order to evaluate their adsorption capacities as well, were subjected to various analyzes of characterization in order to assess the efficiency of the method used for functionalization with amines. The physic-chemical techniques were used: X- ray diffraction (XRD), nitrogen adsorption and desorption (BET/BJH), scanning electron microscopy (SEM), transmission electron microscopy (TEM), CNH Analysis, Thermogravimetry (TG/DTG) and photoelectron spectroscopy X-ray (XPS). The CO2 adsorption experiments were carried out under the following conditions: 100 mg of adsorbent, at 25 °C under a flow of 100 ml/min of CO2, atmospheric pressure and the adsorption variation in time 10-210 min. The X-ray diffraction with the transmission electron micrographs for the samples synthesized and functionalized, MCM-41 and SBA-15 showed characteristic peaks of hexagonal mesoporous structure formation, showing the structure thereof was obtained. The method used was efficient reflux according to XPS and elemental analysis, which showed the presence of amines in the starting materials. The functionalized SBA -15 samples were those that had potential as best adsorbent for CO2 capture when compared with samples of MCM-41, obtaining the maximum adsorption capacity for SBA-15-P sample

Influência da técnica de fabricação e dos materiais sobre o ajuste da interface pilar/implante em infraestruturas implantossuportadas

The aim of this study was to compare the misfit vertical, horizontal and passivity of zirconia and cobalt-chromium frameworks fabricated for CAD / CAM technology and conventional method of casting. Sixteen frameworks in one-piece, were obtained from a metallic matrix containing three Brånemark compatible implants with regular platform (Titamax Cortical Ti, Neodent). Eight frameworks were fabricated by CAD / CAM system (NeoShape, Neodent): four in zirconia (ZirCAD) and four cobalt-chromium (CoCrcad). Eight other frameworks were obtained by conventional casting method: four cobalt-chromium with UCLA abutment premachined Co-Cr (CoCrUCci) and four cobalt-chromium with UCLA abutment castable (CoCrUCc). The fit vertical, horizontal and passivity by one-screw test were measured using scanning electron microscopy with magnification of 250x. Initially evaluated the passivity by one-screw test and subsequently to assess the vertical and horizontal misfit, tightened all the screws with a torque of 20 Ncm. Mean, standard deviation, minimum and maximum values were calculated for each group. Measurements of horizontal misfit were transformed into cumulative frequency for categorization of the variable and the group later comparison groups. To evaluate the existence of quantitative differences between the groups tested for vertical misfit and passivity, we used the Kruskal-Wallis test. The Mann-Whitney test was used to compare group to group statistical differences (p <0.05). Were observed the respective mean and standard deviation for vertical misfit and passivity in micrometers: ZirCAD (5.9 ± 3.6, 107.2 ± 36), CoCrcad (1.2 ± 2.2, 107.5 ± 26 ), CoCrUCci (11.8 ± 9.8, 124.7 ± 74), CoCrUCc (12.9 ± 11.0, 108.8 ± 85). There were statistical differences in measures of vertical misfit (p = 0.000). The Mann-Whitney test revealed statistical differences (p <0.05) between all groups except between CoCrUCci and CoCrUCc (p = 0.619). No statistical difference was observed for the passivity. In relation to the horizontal misfit groups ZirCAD and CoCrcad did not show best values in relation to CoCrUCci and CoCrUCc. Based on the results it can be concluded that frameworks fabricated by CAD / CAM technology had better values of vertical fit than those manufactured by the casting method, nevertheless, the passivity was not influenced by manufacturing technique and material used. The horizontal fit obtained by frameworks manufactured by CAD / CAM was not superior to those manufactured by casting. A lower variability in vertical adjustment and passivity was observed when frameworks were fabricated by CAD / CAM technology

Passividade na interface prótese/pilar intermediário de infraestrutura implantossuportadas confeccionadas pela tecnologia CAD/CAM e método convencional

The objective of this research was to evaluate the passivity and strain induced in infrastructures screwed on abutments, made by CAD/CAM technology, and to compare these samples with parts manufactured by conventional casting. Using CAD/CAM technology, 4 samples were made from zirconia (Zircad) and 4 samples were manufactured from cobaltchrome (CoCrcad). The control groups were 4 specimens of cobalt-chrome, made by onepiece casting (CoCrci), for a total of 12 infrastructures. To evaluate the passivity, the infraestructures were installed on the abutments. One end was tightened and the vertical gap between the infrastructure and the prosthetic abutment was measured with scanning electron microscopy (250×). The mean strain in these infrastructures was analyzed via the photoelasticity test. A significant difference (p = 0.000) in passivity was observed between the control (CoCrci) and sample groups (CoCrcad and CoCrci). CoCrcad exhibited the best value of passivity (48.76 ± 13.45 μm) and CoCrci the worst (187.55 ± 103.63 μm), Zircad presented an intermediate value (103.81 ± 43.15 μm). When compared to the other groups, CoCrci showed the highest mean strain around the implants (17.19 ± 7.22 kPa). It was concluded that the zirconia infrastructure made by CAD / CAM showed a higher vertical marginal misfit than those made in cobalt-chromium alloy with the same methodology, however, the tension generated in the implants was similar. The CAD/CAM technology is more accurate for passivity and mean strain of infrastructure screwed on abutments than conventional manufacturing techniques

Evaluation of Deformation, Mass Loss, and Roughness of Different Metal Burs After Osteotomy for Osseointegrated Implants

Purpose: This study used bovine ribs to comparatively assess the deformation, roughness, and mass loss for 3 different types of surface treatments with burs, used in osteotomies, for the installation of osseointegrated implants.Materials and Methods: The study used 25 bovine ribs and 3 types of helical burs (2.0 mm and 3.0 mm) for osteotomies during implant placement (a steel bur [G1], a bur with tungsten carbide film coating in a carbon matrix [G2], and a zirconia bur [G3]), which were subdivided into 5 subgroups: 1, 2, 3, 4, and 5, corresponding to 0, 10, 20, 30, and 40 perforations, respectively. The surface roughness (mean roughness [Ra], partial roughness, and maximum roughness) and mass (in grams) of all the burs were measured, and the burs were analyzed in a scanning electron microscope before and after use. Data were tabulated and statistically analyzed by use of the Kruskal-Wallis test, and when a statistically significant difference was found, the Dunn test was used.Results: There was a loss of mass in all groups (G1, G2, and G3), and this loss was gradual, according to the number of perforations made (1, 2, 3, 4, and 5). However, this difference was not statistically significant (P < .05). Regarding the roughness, G3 presented an increase in Ra, partial roughness, and maximum roughness (P < .05) compared with G2 and an increase in Ra compared with G1. There was no statistically significant difference (P > .05) between G1 and G2. The scanning electron microscopy analysis found areas of deformation in all the 2.0-mm samples, with loss of substrates, and this characteristic was more frequent in G3.Conclusions: The 2.0-mm zirconia burs had a greater loss of substrates and abrasive wear in the cutting area. They also presented an increased roughness when compared with the steel and the tungsten carbide coating film in carbon matrix. There was no statistically significant difference (P < .05) between G1 and G2 in any mechanical test carried out. (C) 2012 American Association of Oral and Maxillofacial Surgeons J Oral Maxillofac Surg 70:e608-e621, 2012

Effect of Metal-Ceramic or All-Ceramic Superstructure Materials on Stress Distribution in a Single Implant-Supported Prosthesis: Three-Dimensional Finite Element Analysis

Purpose: This three-dimensional finite element analysis study evaluated the effect of different material combinations on stress distribution within metal-ceramic and all-ceramic single implant-supported prostheses. Materials and Methods: Three-dimensional finite element models reproducing a segment of the maxilla with a missing left first premolar were created. Five groups were established to represent different superstructure materials: GP, porcelain fused to gold alloy; GR, modified composite resin fused to gold alloy; TP, porcelain fused to titanium; TR, modified composite resin fused to titanium; and ZP, porcelain fused to zirconia. A 100-N vertical force was applied to the contact points of the crowns. All models were fixed in the superior region of bone tissue and in the mesial and distal faces of the maxilla section. Stress maps were generated by processing with finite element software. Results: Stress distribution and stress values of supporting bone were similar for the GP, GR, TP, and ZP models (1,574.3 MPa, 1,574.3 MPa, 1,574.3 MPa, and 1,574.2 MPa, respectively) and different for the TR model (1,838.3 MPa). The ZP model transferred less stress to the retention screw (785 MPa) than the other groups (939 MPa for GP, 961 MPa for GR, 1,010 MPa for TP, and 1,037 MPa for TR). Conclusion: The use of different materials to fabricate a superstructure for a single implant-supported prosthesis did not affect the stress distribution in the supporting bone. The retention screw received less stress when a combination of porcelain and zirconia was used. Int J Oral Maxillofac Implants 2011;26:1202-1209

Evaluation of the Effect of Retightening and Mechanical Cycling on Preload Maintenance of Retention Screws

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of Superstructure Materials and Misfit on Stress Distribution in a Single Implant-Supported Prosthesis: A Finite Element Analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of Vertical Misfit on Screw Joint Stability of Implant-Supported Crowns

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influence of Nb content on the corrosion resistance and saturation magnetic density of FeCuNbSiB alloys

Nanocrystalline FeCuNbSiB alloys obtained from the partial crystallization of amorphous alloys have attracted technological attention due to their excellent magnetic properties, but the relationship between corrosion resistance and magnetic properties is not well established. The influence of Nb as an alloying element and effect of partial crystallization on the corrosion resistance of Fe73.5Si13.5B10Cu1, Fe73.5Si13.5B7Nb3Cu1 and Fe73.5Si13.5B5Nb5Cu1 amorphous alloys were studied and the effect of corrosion on magnetization saturation flux density, B-s, was investigated. The addition of niobium on amorphous alloys increases the corrosion resistance. The raise of Nb content from 3 to 5% increases the corrosion resistance also. A partial crystallization increases the corrosion resistance of the samples with Nb. However, in the samples without Nb, the partial crystallization diminishes the corrosion resistance. The values of B-s depend on the alloy corrosion resistance.) (C) 2002 Elsevier B.V. B.V. All rights reserved.