Síntese, caracterização e estudo das propriedades magnéticas de ortoferritas de lantânio dopadas com manganês

Orthoferrites AFeO3 (A = rare earth) are an important class of perovskite oxides that exhibit weak ferromagnetism. These materials find numerous applications as chemical sensors, cathodes for fuel cells and catalysis, which make them interesting from the standpoint of science and technology. Their structural, electrical and magnetic properties are dependent on many factors such as the preparation method, heat treatment conditions, chemical composition and replacement of cations in sites A and/or B. In this paper, LaFe1-xMnxO3 (0 ≤ x ≤ 1) orthoferrites-type was prepared by Pechini method and Microwave-assisted combustion reaction in order to evaluate the influence of synthesis route on the formation of oxide, as well as the effect of parcial replacement of iron by manganese and heat treatment on the magnetic properties. The precursor powders were calcined at 700°C, 900°C, 1100°C and 1300°C for 4 hours and they were characterized by the techniques: Thermogravimetric analysis (TGA), X ray diffraction (XRD), Refinement by Rietveld method, Scanning electron microscopy (SEM), Reduction temperature programmed (RTP) and Magnetic hysteresis measurements performed at room temperature. According to the XRD patterns, the formation of perovskite phase with orthorhombic structure was observed for the systems where 0 ≤ x ≤ 0.5 and rhombohedral for x = 1. The results also showed a decrease of lattice parameters with the parcial replacement of iron by manganese and consequently a reduction in cell volume. The hysteresis curves exhibited weak ferromagnetism for the systems prepared by both synthesis methods. However, a dependence of magnetization as a function of dopant content was observed for samples produced by Pechini method. As for the systems prepared by combustion reaction, it was found that the secondary phases exert a strong influence on the magnetic behavior

Effect of pH and temperature on the immunogenicity of glycinin (Glycine max L)

Sensitive immunologic techniques for the detection of alterations that occur in protein antigens were used to evaluate the immunogenicity of soybean glycinin after isolation, heat denaturation and pH alteration. The objective was to determine the effect of these agents on the immunogenic ability of this protein fraction. Immunologic assays performed on heat-denatured glycinin up to 80 degrees C in the presence of antinative glycinin serum demonstrated that glycinin retains its immunogenic properties. Above 90 degrees C this biological property begins to disappear, with protein insolubilization and epitope modification due to the conformational changes imposed by temperature. A reduction in immunogenicity also occurred when glycinin was taken to pH 2.0 (below its pi) and pH 11.00 (above its pi) and exposed to high temperatures in the presence of native antiglycinin serum. From these data one can conclude that, at extreme pH values, intramolecular reactions may occur which, in combination with the structural disorganization caused by high temperatures, may contribute to the reduction of immunogenicity.

SOVLENT REACTIVITY AND INTERFACE EVOLUTION AT MODEL ELECTRODES FOR ENERGY APPLICATIONS

The Li-ion rechargeable battery (LIB) is widely used as an energy storage device, but has significant limitations in battery cycle life and safety. During initial charging, decomposition of the ethylene carbonate (EC)-based electrolytes of the LIB leads to the formation of a passivating layer on the anode known as the solid electrolyte interphase (SEI). The formation of an SEI has great impact on the cycle life and safety of LIB, yet mechanistic aspects of SEI formation are not fully understood. In this dissertation, two surface science model systems have been created under ultra-high vacuum (UHV) to probe the very initial stage of SEI formation at the model carbon anode surfaces of LIB. The first model system, Model System I, is an lithium-carbonate electrolyte/graphite C(0001) system. I have developed a temperature programmed desorption/temperature programmed reaction spectroscopy (TPD/TPRS) instrument as part of my dissertation to study Model System I in quantitative detail. The binding strengths and film growth mechanisms of key electrolyte molecules on model carbon anode surfaces with varying extents of lithiation were measured by TPD. TPRS was further used to track the gases evolved from different reduction products in the early-stage SEI formation. The branching ratio of multiple reaction pathways was quantified for the first time and determined to be 70.% organolithium products vs. 30% inorganic lithium product. The obtained branching ratio provides important information on the distribution of lithium salts that form at the very onset of SEI formation. One of the key reduction products formed from EC in early-stage SEI formation is lithium ethylene dicarbonate (LEDC). Despite intensive studies, the LEDC structure in either the bulk or thin-film (SEI) form is unknown. To enable structural study, pure LEDC was synthesized and subject to synchrotron X-ray diffraction measurements (bulk material) and STM measurements (deposited films). To enable studies of LEDC thin films, Model System II, a lithium ethylene dicarbonate (LEDC)-dimethylformamide (DMF)/Ag(111) system was created by a solution microaerosol deposition technique. Produced films were then imaged by ultra-high vacuum scanning tunneling microscopy (UHV-STM). As a control, the dimethylformamide (DMF)-Ag(111) system was first prepared and its complex 2D phase behavior was mapped out as a function of coverage. The evolution of three distinct monolayer phases of DMF was observed with increasing surface pressure — a 2D gas phase, an ordered DMF phase, and an ordered Ag(DMF)2 complex phase. The addition of LEDC to this mixture, seeded the nucleation of the ordered DMF islands at lower surface pressures (DMF coverages), and was interpreted through nucleation theory. A structural model of the nucleation seed was proposed, and the implication of ionic SEI products, such as LEDC, in early-stage SEI formation was discussed.

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Innovative Al Alloys for High Performance Automotive Pistons: Enhancement of Specific Strength at High Temperature and Resistance to Knock Damage

The increasingly strict regulations on greenhouse gas emissions make the fuel economy a pressing factor for automotive manufacturers. Lightweighting and engine downsizing are two strategies pursued to achieve the target. In this context, materials play a key role since these limit the engine efficiency and components weight, due to their acceptable thermo-mechanical loads. Piston is one of the most stressed engine components and it is traditionally made of Al alloys, whose weakness is to maintain adequate mechanical properties at high temperature due to overaging and softening. The enhancement in strength-to-weight ratio at high temperature of Al alloys had been investigated through two approaches: increase of strength at high temperature or reduction of the alloy density. Several conventional and high performance Al-Si and Al-Cu alloys have been characterized from a microstructural and mechanical point of view, investigating the effects of chemical composition, addition of transition elements and heat treatment optimization, in the specific temperature range for pistons operations. Among the Al-Cu alloys, the research outlines the potentialities of two innovative Al-Cu-Li(-Ag) alloys, typically adopted for structural aerospace components. Moreover, due to the increased probability of abnormal combustions in high performance spark-ignition engines, the second part of the dissertation deals with the study of knocking damages on Al pistons. Thanks to the cooperation with Ferrari S.p.A. and Fluid Machinery Research Group - Unibo, several bench tests have been carried out under controlled knocking conditions. Knocking damage mechanisms were investigated through failure analyses techniques, starting from visual analysis up to detailed SEM investigations. These activities allowed to relate piston knocking damage to engine parameters, with the final aim to develop an on-board knocking controller able to increase engine efficiency, without compromising engine functionality. Finally, attempts have been made to quantify the knock-induced damages, to provide a numerical relation with engine working conditions.

Pressure of massless hot scalar theory in the boundary effective theory framework

We use the boundary effective theory approach to thermal field theory in order to calculate the pressure of a system of massless scalar fields with quartic interaction. The method naturally separates the infrared physics, and is essentially nonperturbative. To lowest order, the main ingredient is the solution of the free Euler-Lagrange equation with nontrivial (time) boundary conditions. We derive a resummed pressure, which is in good agreement with recent calculations found in the literature, following a very direct and compact procedure.

Effects of acidic treatments on the pore and surface properties of Ni catalyst supported on activated carbon

Activated carbon as catalyst support was treated with HCl, HNO3, and HF and the effects of acid treatments on the properties of the activated carbon support were studied by N-2 adsorption, mass titration, temperature-programmed desorption (TPD), and X-ray photoelectron spectrometry (XPS). Ni catalysts supported on untreated and treated activated carbons were prepared, characterized and tested for the reforming reaction of methane with carbon dioxide. It is found that acid treatment significantly changed the surface chemical properties and pore structure of the activated carbon. The surface area and pore volume of the carbon supports are generally enhanced upon acid treatment due to the removal of impurities present in the carbon. The adsorption capacity of Ni2+ on the carbon supports is also increased, and the increase can be closely correlated with the surface acidity. The impregnation of nickel salts decreases the surface area and pore volume of carbon supports both in micropores and mesopores. Acid treatment results in a more homogeneous distribution of the nickel salt in carbon. When the impregnated carbons are heated in inert atmosphere, there exists a redox reaction between nickel oxide and the carbon. Catalytic activity tests for methane reforming with carbon dioxide show that the activity of nickel catalysts based on the acid-treated carbon supports is closely related with the surface characteristics of catalysts. (C) 1998 Elsevier Science Ltd. All rights reserved.

Comprehensive study of surface chemistry of MCM-41 using Si-29 CP/MAS NMR, FTIR, pyridine-TPD, and TGA

A comprehensive study was conducted on mesoporous MCM-41. Spectroscopic examinations demonstrated that three types of silanol groups, i.e., single, (SiO)(3)Si-OH, hydrogen-bonded, (SiO)(3)Si-OH-OH-Si(SiO)(3), and geminal, (SiO)(2)Si(OH)(2), can be observed. The number of silanol groups/nm(2), alpha(OH), as determined by NMR, varies between 2.5 and 3.0 depending on the template-removal methods. All these silanol groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol(-1), respectively. However, only free silanol groups (involving single and geminal silanols) are highly accessible to the silylating agent, chlorotrimethylsilane. Silylation can modify both the physical and chemical properties of MCM-41.

Effects of oxide promoters on metal dispersion and metal-support interactions in Ni catalysts supported on activated carbon

Various oxide-promoted Ni catalysts supported on activated carbon were prepared, and the effect of promoters on the surface structure and properties of Ni catalysts was studied. Physical adsorption (Na adsorption), thermogravimetric analysis (TGA), temperature-programmed desorption (TPD), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts. It is found that nickel is fairly uniformly distributed in the pores of the carbon support. Addition of promoters produces a more homogeneous distribution of nickel ion in carbon. However, distributions of promoters in the pores are varying. Addition of promoters increases the dispersion of nickel in carbon. Promoters also change the interaction between the carbon and Ni, resulting in significantly different behaviors of catalysts under various environments. CaO and MgO promoters improve the reactivity of nickel catalysts with O-2 but retard the interaction between nickel oxide and carbon. La2O3 shows some inhibiting effect on the interactions between nickel oxide and oxygen as well as carbon.

Role of central nitric oxide in behavioral thermoregulation of toads during hypoxia

Nitric oxide (NO) is thought to play a key role in the development of hypoxia-induced anapyrexia in mammals, acting on the preoptic region of the anterior hypothalamus to activate autonomic heat loss responses. Regarding behavioral thermoregulation, no data exists for NO modulation/mediation of thermoregulatory behavior changes during hypoxia. Therefore, we tested the hypothesis that NO is involved in the preferred body temperature (Tb) reduction in the hypoxic toad Chaunus schneideri (formerly Bufo paracnemis), a primarily behavioral thermoregulator. Toads equipped with a temperature probe were placed in a thermal gradient chamber, and preferred Tb was monitored continuously. We analyzed the effect of intracerebroventricular injections of the nonselective NO synthase inhibitor L-NMMA (200, 400 and 800 microg per animal) or mock cerebrospinal fluid (mCSF, vehicle) on the preferred Tb of toads. No significant difference in preferred Tb was observed after L-NMMA treatments. Another group of toads treated with 2 mg kg(-1) (400 microg per animal) of L-NMMA or mCSF was submitted to hypoxia (3% inspired 02) for 8 h. The vehicle group showed a reduction of preferred Tb, a response that was inhibited by L-NMMA. A 3rd group of hypoxic animals was injected with Ringer or L-NMMA (2 mg kg(-1)) into the lymph sac and both treatments induced no change in the anapyretic response to hypoxia. These results indicate that NO acting on the central nervous system has an excitatory role for the development of hypoxia-induced anapyrexia in toads. (C) 2008 Elsevier Inc. All rights reserved.

Preparação de adsorventes mesoporosos para a adsorção de poluentes em águas

Mestrado Engenharia Química. Ramo Tecnologias de Protecção Ambiental

Grafting of adipic anhydride to carbon nanotubes through a Diels-Alder cycloaddition/oxidation cascade reaction

Accepted Manuscript

Sensitivity of the Amazon biome to high resolution climate change projections

ABSTRACT: Despite the reduction in deforestation rate in recent years, the impact of global warming by itself can cause changes in vegetation cover. The objective of this work was to investigate the possible changes on the major Brazilian biome, the Amazon Rainforest, under different climate change scenarios. The dynamic vegetation models may simulate changes in vegetation distribution and the biogeochemical processes due to climate change. Initially, the Inland dynamic vegetation model was forced with initial and boundary conditions provided by CFSR and the Eta regional climate model driven by the historical simulation of HadGEM2-ES. These simulations were validated using the Santarém tower data. In the second part, we assess the impact of a future climate change on the Amazon biome by applying the Inland model forced with regional climate change projections. The projections show that some areas of rainforest in the Amazon region are replaced by deciduous forest type and grassland in RCP4.5 scenario and only by grassland in RCP8.5 scenario at the end of this century. The model indicates a reduction of approximately 9% in the area of tropical forest in RCP4.5 scenario and a further reduction in the RCP8.5 scenario of about 50% in the eastern region of Amazon. Although the increase of CO2 atmospheric concentration may favour the growth of trees, the projections of Eta-HadGEM2-ES show increase of temperature and reduction of rainfall in the Amazon region, which caused the forest degradation in these simulations.

Ab initio study of NOx compounds adsorption on SnO2 surface

An ab initio study of the adsorption processes on NOx compounds on (1 1 0) SnO2 surface is presented with the aim of providing theoretical hints for the development of improved NOx gas sensors. From first principles calculations (DFT¿GGA approximation), the most relevant NO and NO2 adsorption processes are analyzed by means of the estimation of their adsorption energies. The resulting values and the developed model are also corroborated with experimental desorption temperatures for NO and NO2, allowing us to explain the temperature-programmed desorption experiments. The interference of the SO2 poisoning agent on the studied processes is discussed and the adsorption site blocking consequences on sensing response are analyzed.

Preparación y caracterización de la zeolita MCM-22 y de su precursor laminar

The layered precursor of MCM-22 was prepared with different Si/Al ratios: 15, 25, 50, 100 and ¥. Upon heat treatment these precursors form MCM-22 zeolite. Both layered precursor and MCM-22 zeolite were characterized by several techniques: Chemical Analysis by Atomic Absorption Spectroscopy (AAS), X-Ray Diffraction (XRD), Thermo-gravimetric Analysis (TGA), Pore Analysis by N2 and Ar adsorption, Scanning Electron Microscopy (SEM), Infrared Spectroscopy (IR) and Temperature Programmed Desorption of ammonium (TPD).