Obtenção e caracterização físico-química de blendas poliméricas, baseadas em POE e PMMA, dopadas com dióxido de titânio

The study of polymer blends has been an alternative method in the search field of new materials for obtaining materials with improved properties. In this work blends of poly(methyl methacrylate) (PMMA) and poly(ethylene oxide) (PEO) doped with titanium dioxide (TiO2) were studied. The PEO is a polymer semicrystalline structure varying between, 70 and 84% crystallinity, while the PMMA exhibits behavior amorphous in their structure. The use of TiO2 is related to corrosion-resistant of titanium as well as good heat transfer and other characteristics. The study of these polymer blends doped TiO2 gives the properties junction organic (polymer) and inorganic (oxide) which leads to modification of the properties of the resultant material. The blends were doped TiO2 (POE/PMMA/TiO2) in different proportions of the PMMA with the PEO and TiO2 fixed. The ratios were: 90/10/0,1; 85/15/0, 1; 80/20/0,1, 75/25/0,1 and 70/30/0,1. The resulting material was obtained in powder form and being characterized by Fourier Transformed Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and Electrochemical Impedance Spectroscopy (EIS). The infrared spectra (IR) for the blends in different ratios showed a band at 1744 cm-1, characteristic of the C=O stretching, which increases in intensity with increasing PMMA composition, while in the spectrum of pure PEO this band is absent. This may suggest that the interaction is occurring between the polymers. In the micrographs of the blends also observed change in their surfaces with variation of the composition of PMMA, contributing to the change of the electrical properties of the material. The EIS data showed that the material exhibited conductivity of the order of 10-6 S.cm-1. The blend in the ratio B2(85/15/0, 1) showed better conductivity, σ = 1.56 x 10-6 S.cm-1. It was observed that the diffusion coefficient for the blends, B5(70/30/0, 1) was the largest, 1.07 x 10-6 m2.s-1. The XRD data showing that, with the variation in the composition of the PMMA blend crystallinity of the material is decreased reaching a minimum B3(80/20/0,1), and then increases again. Thermal analysis suggests that blends made from the material obtained can be applied at room temperature

Craqueamento térmico e termocatalítico do óleo de girassol (Hellianthus annus L.) sobre materiais micro e mesoporosos

Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it

Confecção e caracterização físico-química de filmes compósitos autossustentáveis NaAlg-TiO2-WO3

A new self-sustainable film was prepared through the sol-gel modified method, previously employed in our research group; sodium alginate was used as the polymer matrix, along with plasticizer glycerol, doped with titanium dioxide (TiO2) and tungsten trioxide (WO3). By varying WO3 concentration (0,8, 1,6, 2,4 and 3,2 μmol) and keeping TiO2 concentration constant (059 mmol), it was possible to study the contribution of these oxides on the obtained films morphological and electrical properties. Self-sustainable films have analyzed by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XDR), Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS) and Electrochemical Impedance Spectroscopy (EIS). By the IR specters, it was possible identify the TiO2, and posteriorly WO3, addition has provided dislocation of alginate characteristics bands to smaller vibrations frequencies indicating an electrostatic interaction between the oxides and the polymer matrix. Diffractograms show predominance of the amorphous phase in the films. SEM, along with EDX, analysis revealed self-sustainable films showed surface with no cracks and relative dispersion of the oxides throughout the polymer matrix. From Impedance analysis, it was observe increasing WO3 concentration to 2,4 μmol provided a reduction of films resistive properties and consequent improvement of conductive properties

Avaliação da poatencialidade da perlita natural e expandida na adsorção de metais

The contamination by metal ions has been occurring for decades through the introduction of liquid effluent not treated, mainly from industrial activities, rivers and lakes, affecting water quality. For that the effluent can be disposed in water bodies, environmental standards require that they be adequately addressed, so that the concentration of metals does not exceed the limits of standard conditions of release in the receptor. Several methods for wastewater treatment have been reported in the literature, but many of them are high cost and low efficiency. The adsorption process has been used as effective for removal of metal ions. This paper presents studies to evaluate the potential of perlite as an adsorbent for removing metals in model solution. Perlite, in its natural form (NP) and expanded (EP), was characterized by X-ray fluorescence, X-ray diffraction, surface area analysis using nitrogen adsorption (BET method), scanning electron microscopy and Fourier transform infrared spectroscopy. The physical characteristic and chemical composition of the material presented were appropriate for the study of adsorption. Adsorption experiments by the method of finite bath for model solutions of metal ions Cr3+, Cu2+, Mn2+ and Ni2+ were carried out in order to study the effect of pH, mass of the adsorbent and the contact time on removal of ions in solution. The results showed that perlite has good adsorption capacity. The NP has higher adsorption capacity (mg g-1) than the EP. According to the values of the constant of Langmuir qm (mg g-1), the maximum capacity of the monolayer was obtained and in terms of proportion of mass, we found the following order experimental adsorption: Cr3+ (2.194 mg g- 1) > Ni2+ (0.585 mg g-1) > Mn2+ (0.515 mg g-1) > Cu2+ (0.513 mg g-1) and Cr3+ (1.934 mg g-1)> Ni2+ (0.514 mg g-1) > Cu2+ (0.421 mg g-1) > Mn2+ (0.364 mg g-1) on the NP and EP, respectively. The experimental data were best fitted the Langmuir model compared to Freundlich for Cu2+, Mn2+ and Ni2+. However, for the Cr3+, both models fit the experimental data

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

Encapsulação de nanopartículas de magnetita em matriz de poli(metacrilato de metilacoácido metacrílico) por processo de polimerização em miniemulsão

Magnetic particles are systems with potential use in drug delivery systems, ferrofluids, and effluent treatment. In many situations, such as in biomedical applications, it is necessary to cover magnetic particles with an organic material, as polymers. In this work, magnetic particles were obtained through covering magnetite particles with poly(methyl methacrylate‐comethacrylic acid) via miniemulsion polymerization process. The resultant materials were characterized X‐ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), zeta potential (��) measurements and vibrating sample magnetometry (VSM). XRD results showed magnetite as the predominant cristalline phase in all samples and that cristallites had nanometric dimensions. Thermogravimetric analysis revealed an increase in polymer thermal stability as a result of magnetite encapsulation. TGA results showed also that the encapsulation efficiency was directly related to nanoparticles s hidrofobicity degree. VSM measurements showed that magnetic polymeric particles were superparamagnetic, so that they may be potentially used for magnetic (bio)separation

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 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

A inserção das mulheres na luta pela terra: movimento de participação e/ou submissão

The following dissertation studies the insertion of peasant women in the conflict for land since the occupation process, dispossession and construction of the settlement New Horizon II, in the municipal district of Maxaranguape. It analyses their participation in the conflict Valley of the Hope", that resulted in the settlements New Life II and New Horizon II in the municipal district of Maxaranguape. The analysis exposes the reasons which took the peasant women, after the land conquest, to go back into domestic space and/or to assume positions of lesser relevance in the political organizations of the settlement. In the conflict Valley of the Hope, the women had a fundamental role, facing the police violence, being front line of the conflicts against the repression forces, risking their lives and the life of their families. After the conquest of the land, transformed into the New Horizon II Settlement, there are a lot of changes in the participation of the women. We can observe that, despite the protagonism of the families, in special of the women in the Valley of the Hope conflict, these female workers still experiment unequal social, economic, political and cultural conditions in relation to the men, expressing the gender inequalities which are found in the daily life of the settlement: in the community, in the domestic and agricultural task. The conflict for the land in the Valley of the Hope and the conquest of the settlement did not necessarily mean the incorporation of the emancipation of the peasant women. However, the political participation in the development of the conflicts allowed to the women the self discovering and the beginning of an emancipation process as gender. There are signals of continuities and ruptures of the present culture, almost always stimulated by the organization of the agricultural female workers

Estudo de Fractalidade e Evolução Dinâmica de Sistemas Complexos

In this work, the study of some complex systems is done with use of two distinct procedures. In the first part, we have studied the usage of Wavelet transform on analysis and characterization of (multi)fractal time series. We have test the reliability of Wavelet Transform Modulus Maxima method (WTMM) in respect to the multifractal formalism, trough the calculation of the singularity spectrum of time series whose fractality is well known a priori. Next, we have use the Wavelet Transform Modulus Maxima method to study the fractality of lungs crackles sounds, a biological time series. Since the crackles sounds are due to the opening of a pulmonary airway bronchi, bronchioles and alveoli which was initially closed, we can get information on the phenomenon of the airway opening cascade of the whole lung. Once this phenomenon is associated with the pulmonar tree architecture, which displays fractal geometry, the analysis and fractal characterization of this noise may provide us with important parameters for comparison between healthy lungs and those affected by disorders that affect the geometry of the tree lung, such as the obstructive and parenchymal degenerative diseases, which occurs, for example, in pulmonary emphysema. In the second part, we study a site percolation model for square lattices, where the percolating cluster grows governed by a control rule, corresponding to a method of automatic search. In this model of percolation, which have characteristics of self-organized criticality, the method does not use the automated search on Leaths algorithm. It uses the following control rule: pt+1 = pt + k(Rc − Rt), where p is the probability of percolation, k is a kinetic parameter where 0 < k < 1 and R is the fraction of percolating finite square lattices with side L, LxL. This rule provides a time series corresponding to the dynamical evolution of the system, in particular the likelihood of percolation p. We proceed an analysis of scaling of the signal obtained in this way. The model used here enables the study of the automatic search method used for site percolation in square lattices, evaluating the dynamics of their parameters when the system goes to the critical point. It shows that the scaling of , the time elapsed until the system reaches the critical point, and tcor, the time required for the system loses its correlations, are both inversely proportional to k, the kinetic parameter of the control rule. We verify yet that the system has two different time scales after: one in which the system shows noise of type 1 f , indicating to be strongly correlated. Another in which it shows white noise, indicating that the correlation is lost. For large intervals of time the dynamics of the system shows ergodicity

Recuperação de sinais esparsos. Investigação numérica sobre a quantidade de medidas necessárias para recuperar um sinal esparso

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Modelo de risco com dependência entre os valores das indenizações e seus intervalos entre ocorrências

We present a dependent risk model to describe the surplus of an insurance portfolio, based on the article "A ruin model with dependence between claim sizes and claim intervals"(Albrecher and Boxma [1]). An exact expression for the Laplace transform of the survival function of the surplus is derived. The results obtained are illustrated by several numerical examples and the case when we ignore the dependence structure present in the model is investigated. For the phase type claim sizes, we study by the survival probability, considering this is a class of distributions computationally tractable and more general

Estudo geoquímico e geocronológico Rb-Sr e Sm-Nd em zonas de cisalhamento mineralizadas em ouro e suas relações com as rochas encaixantes e geocronológico Sm-Nd em mineralizações de scheelita na faixa Seridó

Great part of the gold mineralizations are associated with shearing zones through which circulate a great volume of fluids, that interact with the host rocks, originating leaching or precipitation of chemical elements, including gold. The studied mineralizations are inserted in the Seridó Belt. The tungsten mineralization in Brejuí Mine is hosted in calcsilicate rocks from Jucurutu Formation. The São Francisco auriferous mineralization has as host rocks mica-schists from Seridó Formation, while the Ponta da Serra and Fazenda Simpático mineralizations are hosted in orthogneisses of this fold belt basement. The research conducted on these mineralizations had the purpose of integrate the data of chemical elements behavior during the shearing/mineralizing event, and its influence on the isotopic systems Rb-Sr and Sm-Nd. The studies of chemical mobility in the auriferous mineralizations showed that elements that during the shearing displayed in general an immobile behavior were Al, Ti and Zr. Among the elements that were mobilized during the event, K and Rb showed mass gain in ali belts of transformed rocks, while the elements Ca, Na and Sr normally lost mass. Petrographic studies showed that the minerais biotite and plagioclase, in all investigated mineralizations, played an important role in the chemical reactions occurred in the transformed rocks to the generation of muscovite, cordierite and sillimanite, justifying the input of K to the formation of muscovite, and the release of Na and Ca from plagioclase to the fluid phase. In the São Francisco auriferous mineralization, the results of the Rb-Sr isotopic analysis yielded ages of 645 ± 19 Ma and 596 ± 17 Ma, with both samples, from original and transformed rocks. Two ages, 569 ± 20 Ma. and 554 ± 19 Ma., were obtained with samples frem the transformed rocks domain. These ages suggest that there were two metamorphic pulses during the emplacement of the mineralized shearing zone. The Sm-Nd data yielded TDM ages of 1,31 Ga and 1,26 Ga with 3Nd (0,6 Ga) of -0,26 e -0,40 for the original and final transformed rocks, respectively. In case of the orthogneisses of Caicó Complex, e.g. the Ponta da Serra and Fazenda Simpático mineralizations, the Rb-Sr data did not yield ages with geological significance. In the Ponta da Serra mineralization, the Sm-Nd isotopic data yielded T DM ages of 2,56 Ga and 2,63 Ga to the original rocks and of 2,71 Ga to the mineralized sheared rock, and values of 3Nd (2,0 Ga) between -3,70 e -5,42 to the original and sheared rock, respectively. In the Fazenda Simpático, Sm-Nd data yielded TDM between 2,65 and 2,69 Ga with values of 3Nd (2,0 Ga) between -5,25 e -5,52. Considering the Sm-Nd data, the TDM ages may be admitted as the age of the parental magma extraction, producer of the protoliths of the orthogneisses from Ponta da Serra and Fazenda Simpático mineralizations. The chemical mobility studies showed that in the basement hosted mineralizations, Rb achieved mass while Sr lost mass, as Sm as well as Nd were strongly mobilized. The Sm/Nd ratio remained constant, however, confirming the isochemical character of those elements. In the basement mineralizations, Rb-Sr ages are destituted of geological significance, because of the partial opening of the isotopic system during the tectono-metamorphic transformations. In the tungsten mineralization, the diagram Sm-Nd constructed with the whole-rock data of calcsilicatic and the high-temperature paragenesis (garnet, diopside and iron-pargasitic hornblende) indicated an 631 ± 24 Ma age, while with the whole-rock data and low-temperature paragenesis (vesuvianite, epidote and calcite), a 537 ± 107 Ma age was obtained. These ages, associated with the petrographic observations, suggest that there was a time gap among the hydrothernal events responsible by the formation of the high and low temperature paragenesis in the calcsilicatic rocks mineralized in scheelite

Evolução geomorfológica, (des)caracterização e formas de uso das Lagoas da cidade do Natal-RN

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Efeito de valores discrepantes em grupos de contemporâneos na predição dos valores genéticos

Foram simuladas nove populações, cada uma com cinco replicações da variável ganho médio diário (GMD1) com distribuição normal e média 100, variando o tamanho dos grupos e os desvios-padrão. Cada replicação foi dividida de modo a formar grupos que representariam grupos de contemporâneos (GC) e de progênie dentro de GC. Cada GC tinha dez pais. Obtiveram-se três conjuntos: o conjunto 1 com 1.000 grupos de contemporâneos (GC), cada um com 100 observações e dez observações por pai; o conjunto 2, com 2.500 GC, 40 observações e quatro observações por pai; e o conjunto 3, com 5.000 GC, 20 observações e dois filhos por pai. em cada população, gerou-se GMD1, a qual foi transformada em outra variável, da seguinte forma: DIAS1 = 100/GMD1. Calcularam-se para cada pai, dentro de cada GC, as contribuições de cada GC ao valor de cada pai, para GMD1 (Cx) e DIAS1 (Cy). Os efeitos do máximo e da média de DIAS1 no grupo sobre o valor absoluto de Cy foram significativos, mas o R² foi baixo (máximo de 16%). O mínimo de DIAS1 não influenciou o valor de Cy. O máximo e o mínimo de GMD1 sobre Cx foram significativos, mas os R² foram muito baixos (máximo de 2%). A média não influenciou Cx. em grupos de contemporâneos com um animal com valor de GMD muito baixo, o valor de DIAS desse animal será relativamente muito mais alto, o que afetará a média do grupo e os valores de todos os animais do grupo. Esse efeito se refletirá na avaliação de seus pais e será mais uma importante fonte de erros na avaliação genética do rebanho. Assim, a utilização de DIAS em substituição ao GMD como critério de seleção para o melhoramento de bovinos é contra-indicada, pois deverá reduzir a possibilidade de ganho genético para crescimento.