Cálculos AB initio de propriedades estruturais, eletrônicas e ópticas de colmpostos CaXo3 (X=Si, Ge, Sn)

In this work we present a study of structural, electronic and optical properties, at ambient conditions, of CaSiO3, CaGeO3 and CaSnO3 crystals, all of them a member of Ca-perovskite class. To each one, we have performed density functional theory ab initio calculations within LDA and GGA approximations of the structural parameters, geometry optimization, unit cell volume, density, angles and interatomic length, band structure, carriers effective masses, total and partial density of states, dielectric function, refractive index, optical absorption, reflectivity, optical conductivity and loss function. A result comparative procedure was done between LDA and GGA calculations, a exception to CaSiO3 where only LDA calculation was performed, due high computational cost that its low symmetry crystalline structure imposed. The Ca-perovskite bibliography have shown the absence of electronic structure calculations about this materials, justifying the present work

Sistemas Nanoestruturados: Heteroestruturas Quasi-Periódicas de Nitretos e Cálculos Ab initio em Polimorfos CaCO3

The physical properties and the excitations spectrum in oxides and semiconductors materials are presented in this work, whose the first part presents a study on the confinement of optical phonons in artificial systems based on III-V nitrides, grown in periodic and quasiperiodic forms. The second part of this work describes the Ab initio calculations which were carried out to obtain the optoeletronic properties of Calcium Oxide (CaO) and Calcium Carbonate (CaCO3) crystals. For periodic and quasi-periodic superlattices, we present some dynamical properties related to confined optical phonons (bulk and surface), obtained through simple theories, such as the dielectric continuous model, and using techniques such as the transfer-matrix method. The localization character of confined optical phonon modes, the magnitude of the bands in the spectrum and the power laws of these structures are presented as functions of the generation number of sequence. The ab initio calculations have been carried out using the CASTEP software (Cambridge Total Sequential Energy Package), and they were based on ultrasoft-like pseudopotentials and Density Functional Theory (DFT). Two di®erent geometry optimizations have been e®ectuated for CaO crystals and CaCO3 polymorphs, according to LDA (local density approximation) and GGA (generalized gradient approximation) approaches, determining several properties, e. g. lattice parameters, bond length, electrons density, energy band structures, electrons density of states, e®ective masses and optical properties, such as dielectric constant, absorption, re°ectivity, conductivity and refractive index. Those results were employed to investigate the confinement of excitons in spherical Si@CaCO3 and CaCO3@SiO2 quantum dots and in calcium carbonate nanoparticles, and were also employed in investigations of the photoluminescence spectra of CaCO3 crystal

Polaritons em materiais magnéticos nanoestruturados

In this work we present a theoretical study about the properties of magnetic polaritons in superlattices arranged in a periodic and quasiperiodic fashíons. In the periodic superlattice, in order to describe the behavior of the bulk and surface modes an effective medium approach, was used that simplify enormously the algebra involved. The quasi-periodic superlattice was described by a suitable theoretical model based on a transfer-matrix treatment, to derive the polariton's dispersion relation, using Maxwell's equations (including effect of retardation). Here, we find a fractal spectra characterized by a power law for the distribution of the energy bandwidths. The localization and scaling behavior of the quasiperiodic structure were studied for a geometry where the wave vector and the external applied magnetic field are in the same plane (Voigt geometry). Numerical results are presented for the ferromagnet Fe and for the metamagnets FeBr2 and FeCl2

Pecolação em uma rede multifractal

In this work we present the principal fractals, their caracteristics, properties abd their classification, comparing them to Euclidean Geometry Elements. We show the importance of the Fractal Geometry in the analysis of several elements of our society. We emphasize the importance of an appropriate definition of dimension to these objects, because the definition we presently know doesn t see a satisfactory one. As an instrument to obtain these dimentions we present the Method to count boxes, of Hausdorff- Besicovich and the Scale Method. We also study the Percolation Process in the square lattice, comparing it to percolation in the multifractal subject Qmf, where we observe som differences between these two process. We analize the histogram grafic of the percolating lattices versus the site occupation probability p, and other numerical simulations. And finaly, we show that we can estimate the fractal dimension of the percolation cluster and that the percolatin in a multifractal suport is in the same universality class as standard percolation. We observe that the area of the blocks of Qmf is variable, pc is a function of p which is related to the anisotropy of Qmf

Conjuntos numéricos

In this work, we present a text on the Sets Numerical using the human social needs as a tool for construction new numbers. This material is intended to present a text that reconciles the correct teaching of mathmatics and clarity needed for a good learning

Princípio da Indução Matemática no Ensino Médio

We developed this dissertation aiming its in the process of teaching and learning of the Principle of Mathematical Induction and we set our efforts so that the students of the first year of the high school can assimilate the content having the knowledge seen in the basic education as foreknowledge. With this, we seek to awake in the student the interest on proofs, showing how much it s needed in examples that involve contents that he is already seen

Estudo da digestão de sedimento de curtume visando a extração do cromo por microemulsão

Leather tanneries generate effluents with high content of heavy metals, especially chromium, which is used in the mineral tanning process. Microemulsions have been studied in the extraction of heavy metals from aqueous solutions. Considering the problems related with the sediment resulting from the tanning process, due to its high content in chromium, in this work this sediment was characterized and microemulsion systems were applied for chromium removal. The extraction process consists in the removal of heavy metal ions present in an aqueous feeding solution (acid digestion solution) by a microemulsion system. First three different solid sludge digestion methods were evaluated, being chosen the method with higher digestion capacity. For this digestion method, seeking its optimization, was evaluated the influence of granule size, temperature and digestion time. Experimental results showed that the method proposed by USEPA (Method A) was the most efficient one, being obtained 95.77% of sample digestion. Regarding to the evaluated parameters, the best results were achieved at 95°C, 14 Mesh granule size, and 60 minutes digestion time. For chromium removal, three microemulsion extraction methods were evaluated: Method 1, in a Winsor II region, using as aqueous phase the acid digestion solution; Method 2, in a Winsor IV region, being obtained by the addition of the acid digestion solution to a microemulsion phase, whose aqueous phase is distilled water, until the formation of Winsor II system; and Method 3, in a Winsor III region, consisting in the formation of a Winsor III region using as aqueous phase the acid digestion solution, diluted in NaOH 0.01N. Seeking to optimize the extraction process only Method 1 (Systems I, II, and VIII) and Method 2 (System IX) were evaluated, being chosen points inside the interest regions (studied domains) to study the influence of contact time and pH in the extraction percentiles. The studied systems present the following compositions: System I: Surfactant Saponified coconut oil, Cosurfactant 1-Butanol, Oil phase Kerosene, Aqueous phase 2% NaCl solution; System II: Aqueous phase Acid digestion solution with pH adjusted using KOH (pH 3.5); System VIII: Aqueous phase - Acid digestion solution (pH 0.06); and System IX Aqueous phase Distilled water (pH 10.24), the other phases of Systems II, VIII and IX are similar to System I. Method 2 showed to be the more efficient one regarding chromium extraction percentile (up to 96.59% - pH 3.5). Considering that with Method 2 the microemulsion region only appears in the Winsor II region, it was studied Method 3 (System X) for the evaluation and characterization of a triphasic system, seeking to compare with a biphases system. System X is composed by: Surfactant Saponified coconut oil, Cosurfactant 1-Butanol, Oil phase Kerosene, Aqueous phase Acid digestion solution diluted with water and with its pH adjusted using 0.01N NaOH solution. The biphasic and triphasic microemulsion systems were analyzed regarding its viscosity, extraction efficiency and drop effective diameter. The experimental results showed that for viscosity studies the obtained values were low for all studied systems, the diameter of the drop is smaller in the Winsor II region, with 15.5 nm, reaching 46.0 nm in Winsor III region, being this difference attributed to variations in system compositions and micelle geometry. In chromium extraction, these points showed similar results, being achieved 99.76% for Winsor II system and 99.62% for Winsor III system. Winsor III system showed to be more efficient due to the obtaining of a icroemulsion with smaller volume, with the possibility to recover the oil phase in excess, and the use of a smaller proportion of surfactant and cosurfactant (C/S)

Estudo do desempenho de catalisadores tipo Ni/CexM1-xO2 (M = Zr ou Mn) na reação de oxidação parcial do metano

One of the main applications of methane is in the production of syngas, a mixture of hydrogen and carbon monoxide. Procedures used in this process are steam reforming, CO2 reforming, partial oxidation and autothermal reforming. The present study evaluated and compared the behavior of nickel catalysts supported on mixed oxides of cerium and manganese in the partial oxidation of methane with that of nickel catalysts supported on mixed oxides of cerium and zirconium. Mixed oxides of cerium and zirconium or cerium and manganese were synthesized using two different preparation methods, the polymeric precursor based on Pechini method and combustion reaction using a microwave. This was followed by impregnation with nickel content of 15 %. Samples were calcined at 300, 800 and 900 °C and characterized by specific surface area (SSA), X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed reduction (TPR) and the reaction of partial oxidation of methane. The specific areas of samples decrease with the rise in calcination temperature and after nickel impregnation. Metal-cerium solid solution was formed and the presence of other manganese species outside the solid solution structure was confirmed in the compound with the highest amounts of manganese oxides showed. With regard to scanning electron microscopy, supports based on cerium and zirconium prepared by Pechini method exhibited agglomerated particles without uniform geometry or visible pores on the surface. However, compounds containing manganese presented empty spaces in its structure. Through synthesis by combustion reaction, morphology acquired independently of the proposed composition demonstrated greater porosity in relation to Pechini synthesis. Although catalysts were prepared using different synthesis methods, the insertion of nickel showed very similar reduction profiles (TPR). In relation to nickel catalysts supported on mixed oxide of cerium and zirconium, there is an initial reduction of NiO species that present certain interaction with the support. This is followed by the reduction of Ce4+ in Ce3+ surface, with subsequent bulk reduction. For catalysts containing manganese, a reduction of nickel oxide species occurs, followed by two stages of reduction for species Mn2O3 in Mn3O4 and Mn3O4 in MnO, with subsequent reduction of bulk. With respect to partial oxidation reactions, the nickel catalyst supported on mixed oxide of cerium and zirconium, prepared using the Pechini method, exhibited CH4 conversion of approximately 80 %, with conversion of 81 % when prepared by combustion. This behavior continued for 10 hours of reaction. Manganese content was also found to directly influence catalytic activity of materials; the greater the manganese oxide content, the faster deactivation and destabilization occurred in the catalyst. In both synthesis methods, the nickel catalyst supported on mixed oxide of cerium and zirconium maintained an H2/CO ratio very close to 2 during the 10 hours of partial oxidation reaction. Samples containing manganese displayed smaller H2/CO ratios and lower performance in partial oxidation.

Sistema microemulsionado: caracterização e aplicação na indústria de petróleo

Alkyl polyethoxylates are surfactants widely used in vastly different fields, from oil exploitation to pharmaceutical applications. One of the most interesting characteristics of these surfactants is their ability to form micellar systems with specific geometry, the so-called wormlike micelle. In this work, microemulsions with three distinct compositions (C/T = 40 %, 30 % and 25 %) was used with contain UNITOL / butanol / water / xylene, cosurfactant / surfactante (C/S) ratio equal to 0,5. The microemulsion was characterized by dynamic light scattering (DLS), capillary viscometry, torque rheometry and surface tensiometry experiments carried out with systems based on xylene, water, butanol (cosurfactant) and nonaethyleneglycolmonododecyl ether (surfactant), with fixed surfactant:cosurfactant:oil composition (with and without oil phase) and varying the overall concentration of the microemulsion. The results showed that a transition from wormlike micelles to nanodrops was characterized by maximum relative viscosity (depending on how relative viscosity was defined), which was connected to maximum effective diameter, determined by DLS. Surface tension suggested that adsorption at the air water interface had a Langmuir character and that the limiting value of the surfactant surface excess was independent of the presence of cosurfactant and xylene. The results of the solubilization of oil sludge and oil recovery with the microemulsion: C/S = 40%, 30% and 25% proved to be quite effective in solubilization of oil sludge, with the percentage of solubilization (%solubilization) as high as 92.37% and enhanced oil recovery rates up to 90.22% for the point with the highest concentration of active material (surfactant), that is, 40%.

Síntese e caracterização de compostos de coordenação homolépticos e heterolépticos com o ligante ácido kójico

The present work has as main objective to contribute to the coordination chemistry of the ligand kojic acid, with the synthesis and characterization of the homoleptic compounds [Al(kj)3], [Fe(kj)3], [Fe(kj)2], [Cu(kj)2] e [Ru(kj)3], and the new heteroleptic complexes, trans- K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2]. The obtained compounds were characterized by vibrational spectroscopy in the infrared region (IV) and Electronic spectroscopy in the ultraviolet and visible region (Uv-Vis). The infrared results indicated the coordination of the bidentate ligand kojic acid, due to reductions in the values of the stretching frequencies of the carbonyl and double bonds, compared to the free ligand for all complexes obtained. The presence of new vibrational modes indicated the change of symmetry of the molecules in the new compounds synthesized. Additionally, the presence of vibrational modes assigned to metal-oxygen also contributed to confirm the ligand coordinating to the metal ions. Through this technique, was also possible to perform correlations of the numbers of vibrational modes, in the region 1400-900 cm-1 and the compounds geometry. The heteroleptic compounds exhibited υC≡N in 2065 and 2053 cm-1, respectively, for the trans-K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2], indicating coordination of the cyano ligand to metal ions FeII e RuII. Comparing the obtained values with literature data was possible to identify the complex isomerism as trans. In relation to the results of electronic spectroscopy, studies of pH variation of kojic acid provided information on the distribution of electron density in the molecule, showing characteristic spectral profile of kojic ion and its protonated form (Hkj, kojic acid), with two bands at 215 and 269 nm, or deprotonated (kj-), with bands at 226 and 315 nm. The electronic spectra obtained for all complexes in aqueous medium, in the ultraviolet region, exhibited variations of the energies assigned to kojic acid intraligand transitions while in the visible region, only transitions assigned to charge transfer of iron and ruthenium complex have been identified

Índice de aromaticidade baseado na deslocalização, degenerescência e densidade (D3BIA) para acenos e moléculas homoaromáticas

The aromaticity index is an important tool for the investigation of aromatic molecules. This work consists on new applications of the aromaticity index developed by teacher Caio Lima Firme, so-called D3BIA (density, delocalization, degeneracy-based index of aromaticity). It was investigated its correlation with other well-known aromaticity indexes, such as HOMA (harmonic oscillator model of aromaticity), NICS (nucleus independent chemical shielding), PDI (para-delocalization index), magnetic susceptibility (), and energetic factor in the study of aromaticity of acenes and homoaromatic species based on bisnoradamantanyl cage. The density functional theory (DFT) was used for optimization calculations and for obtaining energetic factors associated with aromaticity and indexes HOMA and NICS. From quantum theory of atoms in molecules (QTAIM) it was obtained the indexes D3BIA, PDI and . For acenes, when the over-mentioned indexes were applied it was observed no correlation except for D3BIA and HOMA (R2=0.752). For bisnoradamantenyl dication and its derivatives, it was obtained a good correlation between D3BIA and NICS. Moreover, it was evaluated solely one of the factors used on D3BIA calculation, the delocalization index uniformity (DIU), so as to investigate its possible influence on stability of chemical species. Then, the DIU was compared with the formation Gibbs free energy of some pairs of carbocations, isomers or not, which each pair had small difference in point group symmetry and no difference among other well-known stability factors. The obtained results indicate that DIU is a new stability factor related to carbocations, that is, the more uniform the electron density delocalization, the more stable the is carbocation. The results of this work validate D3BIA and show its importance on the concept of aromaticity, indicating that it can be understood from degeneracy of atoms belonging the aromatic site, the electronic density in the aromatic site and the degree of uniformity of electron delocalization

Computabilidade no espaço dos intervalos reais: um modelo BSS intervalar

A matemática intervalar é uma teoria matemática originada na década de 60 com o objetivo de responder questões de exatidão e eficiência que surgem na prática da computação científica e na resolução de problemas numéricos. As abordagens clássicas para teoria da computabilidade tratam com problemas discretos (por exemplo, sobre os números naturais, números inteiros, strings sobre um alfabeto finito, grafos, etc.). No entanto, campos da matemática pura e aplicada tratam com problemas envolvendo números reais e números complexos. Isto acontece, por exemplo, em análise numérica, sistemas dinâmicos, geometria computacional e teoria da otimização. Assim, uma abordagem computacional para problemas contínuos é desejável, ou ainda necessária, para tratar formalmente com computações analógicas e computações científicas em geral. Na literatura existem diferentes abordagens para a computabilidade nos números reais, mas, uma importante diferença entre estas abordagens está na maneira como é representado o número real. Existem basicamente duas linhas de estudo da computabilidade no contínuo. Na primeira delas uma aproximação da saída com precisão arbitrária é computada a partir de uma aproximação razoável da entrada [Bra95]. A outra linha de pesquisa para computabilidade real foi desenvolvida por Blum, Shub e Smale [BSS89]. Nesta aproximação, as chamadas máquinas BSS, um número real é visto como uma entidade acabada e as funções computáveis são geradas a partir de uma classe de funções básicas (numa maneira similar às funções parciais recursivas). Nesta dissertação estudaremos o modelo BSS, usado para se caracterizar uma teoria da computabilidade sobre os números reais e estenderemos este para se modelar a computabilidade no espaço dos intervalos reais. Assim, aqui veremos uma aproximação para computabilidade intervalar epistemologicamente diferente da estudada por Bedregal e Acióly [Bed96, BA97a, BA97b], na qual um intervalo real é visto como o limite de intervalos racionais, e a computabilidade de uma função intervalar real depende da computabilidade de uma função sobre os intervalos racionais

Construção de mosaicos georreferenciados usando imagens aéreas de pequeno formato

In this work we propose a technique that uses uncontrolled small format aerial images, or SFAI, and stereohotogrammetry techniques to construct georeferenced mosaics. Images are obtained using a simple digital camera coupled with a radio controlled (RC) helicopter. Techniques for removing common distortions are applied and the relative orientation of the models are recovered using projective geometry. Ground truth points are used to get absolute orientation, plus a definition of scale and a coordinate system which relates image measures to the ground. The mosaic is read into a GIS system, providing useful information to different types of users, such as researchers, governmental agencies, employees, fishermen and tourism enterprises. Results are reported, illustrating the applicability of the system. The main contribution is the generation of georeferenced mosaics using SFAIs, which have not yet broadly explored in cartography projects. The proposed architecture presents a viable and much less expensive solution, when compared to systems using controlled pictures

Geração procedural de cenários orientada a objetivos

The game industry has been experiencing a consistent increase in production costs of games lately. Part of this increase refers to the current trend of having bigger, more interactive and replayable environments. This trend translates to an increase in both team size and development time, which makes game development a even more risky investment and may reduce innovation in the area. As a possible solution to this problem, the scientific community is focusing on the generation of procedural content and, more specifically, on procedurally generated levels. Given the great diversity and complexity of games, most works choose to deal with a specific genre, platform games being one of the most studied. This work aims at proposing a procedural level generation method for platform/adventure games, a fairly more complex genre than most classic platformers which so far has not been the subject of study from other works. The level generation process was divided in two steps, planning and viusal generation, respectively responsible for generating a compact representation of the level and determining its view. The planning stage was divided in game design and level design, and uses a goaloriented process to output a set of rooms. The visual generation step receives a set of rooms and fills its interior with the appropriate parts of previously authored geometry

Condicionamento estrutural das zonasa de cisalhamento da região de Forquilha, domínio Ceará Central: uma abordagem integrada de sensoriamento remoto e geologia estrutural

The studied region, named Forquilha and localized in northwestern Central Ceará domain (northern portion of Borborema Province), presents a lithostratigraphic framework constituted by paleoproterozoic metaplutonics, metasedimentary sequences and neoproterozoic granitoids. The metasedimentary rocks of Ceará group occupy most part of the area. This group is subdivided in two distinct units: Canindé and Independência. Canindé unit is represented basically by biotite paragneisses and muscovite paragneisses, with minor metabasic rocks (amphibolite lens). Independência sequence is composed by garnetiferous paragneisses, sillimanite-garnet-quartz-muscovite schists and quartz-muscovite schists, pure or muscovite quartzites and rare marbles. At least three ductile deformation events were recognized in both units of Ceará group, named D1, D2 and D3. The former one is interpreted as related to a low angle tangential tectonics which mass transport is southward. D2 event is marked by the development of close/isoclinal folds with a N-S oriented axis. Refolding patterns generated by F1 and F2 superposition are found in several places. The latest event (D3) corresponds to a transcurrent tectonics, which led to development of mega-folds and several shear zones, under a transpressional regime. The mapped shear zones are Humberto Monte (ZCHM), Poço Cercado (ZCPC) and Forquilha (ZCF). Digital image processing of enhanced Landsat 7-ETM+ satellite images, combined with field data, demonstrate that these penetrative structures are associated with positive and negative geomorphologic patterns, distributed in linear and curvilinear arrangements with tonal banding, corresponding to the ductile fabric and to crests. Diverse color composites were tested and RGB-531 and RGB-752 provided the best results for lineament analysis of the most prominent shear zones. Spatial filtering techniques (3x3 and 5x5 filters) were also used and the application of Prewitt filters generated the best products. The integrated analysis of morphological and textural aspects from filtered images, variation of tonalities related to the distribution of geologic units in color composites and the superposition over a digital elevation model, contributed to a characterization of the structural framework of the study area. Kinematic compatibility of ZCHM, ZCPC, ZCF shear zones, as well as Sobral-Pedro II (ZCSPII) shear zone, situated to the west of the study area, was one of the goal of this work. Two of these shear zones (ZCHM, ZCPC) display sinistral movements, while the others (ZCSPII, ZCF) exhibit dextral kinematics. 40Ar/39Ar ages obtained in this thesis for ZCSPII and ZCPC, associated with other 40Ar/39Ar data of adjacent areas, indicate that all these shear zones are related to Brasiliano orogeny. The trend of the structures, the opposite shear senses and the similar metamorphic conditions are fitted in a model based on the development of conjugate shear zones in an unconfined transpression area. A WNW-ESE bulk shortening direction is infered. The geometry and kinematic of the studied structures suggest that shortening was largely accommodated by lateral extrusion, with only minor amounts of vertical stretch