Estratégia de controle robusto para interconexão de sistemas PV trifásicos à rede elétrica

Atualmente há uma grande preocupação em relação a substituição das fontes não renováveis pelas fontes renováveis na geração de energia elétrica. Isto ocorre devido a limitação do modelo tradicional e da crescente demanda. Com o desenvolvimento dos conversores de potência e a eficácia dos esquemas de controle, as fontes renováveis têm sido interligadas na rede elétrica, em um modelo de geração distribuída. Neste sentido, este trabalho apresenta uma estratégia de controle não convencional, com a utilização de um controlador robusto, para a interconexão de sistemas fotovoltaicos com à rede elétrica trifásica. A compensação da qualidade de energia no ponto de acoplamento comum (PAC) é realizada pela estratégia proposta. As técnicas tradicionais utilizam detecção de harmônicos, já neste trabalho o controle das correntes é feita de uma forma indireta sem a necessidade desta detecção. Na estratégia indireta é de grande importância que o controle da tensão do barramento CC seja efetuado de uma forma que não haja grandes flutuações, e que a banda passante do controlador em regime permanente seja baixa para que as correntes da rede não tenham um alto THD. Por este motivo é utilizado um controlador em modo dual DSM-PI, que durante o transitório se comporta como um controlador em modo deslizante SM-PI, e em regime se comporta como um PI convencional. A corrente é alinhada ao ângulo de fase do vetor tensão da rede elétrica, obtido a partir do uso de um PLL. Esta aproximação permite regular o fluxo de potência ativa, juntamente com a compensação dos harmônicos e também promover a correção do fator de potência no ponto de acoplamento comum. Para o controle das correntes é usado um controlador dupla sequencia, que utiliza o princípio do modelo interno. Resultados de simulação são apresentados para demonstrar a eficácia do sistema de controle proposto

Arquiteturas eficientes para sensoriamento espectral e classificação automática de modulações usando características cicloestacionárias

The increasing demand for high performance wireless communication systems has shown the inefficiency of the current model of fixed allocation of the radio spectrum. In this context, cognitive radio appears as a more efficient alternative, by providing opportunistic spectrum access, with the maximum bandwidth possible. To ensure these requirements, it is necessary that the transmitter identify opportunities for transmission and the receiver recognizes the parameters defined for the communication signal. The techniques that use cyclostationary analysis can be applied to problems in either spectrum sensing and modulation classification, even in low signal-to-noise ratio (SNR) environments. However, despite the robustness, one of the main disadvantages of cyclostationarity is the high computational cost for calculating its functions. This work proposes efficient architectures for obtaining cyclostationary features to be employed in either spectrum sensing and automatic modulation classification (AMC). In the context of spectrum sensing, a parallelized algorithm for extracting cyclostationary features of communication signals is presented. The performance of this features extractor parallelization is evaluated by speedup and parallel eficiency metrics. The architecture for spectrum sensing is analyzed for several configuration of false alarm probability, SNR levels and observation time for BPSK and QPSK modulations. In the context of AMC, the reduced alpha-profile is proposed as as a cyclostationary signature calculated for a reduced cyclic frequencies set. This signature is validated by a modulation classification architecture based on pattern matching. The architecture for AMC is investigated for correct classification rates of AM, BPSK, QPSK, MSK and FSK modulations, considering several scenarios of observation length and SNR levels. The numerical results of performance obtained in this work show the eficiency of the proposed architectures

Utilização da lógica difusa no controle inteligente de sistemas eletro-hidráulicos

Electro-hydraulic servo-systems are widely employed in industrial applications such as robotic manipulators, active suspensions, precision machine tools and aerospace systems. They provide many advantages over electric motors, including high force to weight ratio, fast response time and compact size. However, precise control of electro-hydraulic systems, due to their inherent nonlinear characteristics, cannot be easily obtained with conventional linear controllers. Most flow control valves can also exhibit some hard nonlinearities such as deadzone due to valve spool overlap on the passage´s orifice of the fluid. This work describes the development of a nonlinear controller based on the feedback linearization method and including a fuzzy compensation scheme for an electro-hydraulic actuated system with unknown dead-band. Numerical results are presented in order to demonstrate the control system performance

Avaliação de dois clones de Escherichia coli recombinante quanto ao crescimento e expressão de antígenos de Leishmania chagasi (kmp11 e P36)

Visceral leishmaniosis caused by Leishmania chagasi, also known as calazar, presented, in the period from 1990 to 2005, tax of incidence in Brazil varying between 1 and 3 cases for 100 000 inhabitants. The Northeast region that up to the year of 2000 contributed with almost 90% of the registered cases is reducing his participation in the current decade, reaching 56% in 2005. Conventional leishmaniasis treatment is costly and it shows high toxicity, demanding more research for alternative treatments, with special interest in development of vaccines and diagnosis kits which include production of recombinant antigens by host cells. Escherichia coli has been the microorganism most studied and used as a host for recombinant protein production. Therefore, the aim of this work was to study the influence of induction on cellular growth and to verify the type of Leishmania chagasi antigens expression (intra or extracellular) during two recombinant E. coli clones (kmp11 and P36) cultivation in rotary incubator (shaker) using three different media (2xTY, TB, FASS+EL). For that, tests were carried out using conditions established in the literature for E. coli (37°C and 200 rpm) and media supplemented with antibiotics to guarantee that only competent cells grows. First, tests were carried out without induction in order to verify the two microorganisms kinetic behavior (growth and substrate consumption) in different media. Next, the induction was carried out through the addition of IPTG (1mM as final concentration), at the first hour of cultivation. It was observed that protein expression were intracellular for all clones and media tested, however the highest level of expression was clearly observed by the electrophoresis band density (intensity) for 2xTY medium and kmp11 protein. Although it contains the lowest substrate concentration, consequently, a reduced cellular concentration when compared to other media, it appeared that this medium and clone combination is the most indicated for recombinant protein production. Therefore, the objective of this work was achieved, since the interested proteins were produced. Consequently, this result motivates new studies for production optimization using different cultivation strategies

Práticas de letramento digital de professores em formação: demandas, saberes e impactos

Over the last decades, the digital inclusion public policies have significantly invested in the purchase of hardwares and softwares in order to offer technology to the Brazilian public teaching institutions, specifically computers and broadband Internet. However, the teachers education to handle these artefacts is put away, even though there is some demand from the information society. With that, this dissertation chooses as an object of study the digital literacy practices performed by 38 (thirty-eight) teachers in initial and continuous education by means of the extension course Literacies and technologies: portuguese language teaching and cyberculture demands. In this direction, we aim at investigating the digital literacy practices of developing teachers in three specific moments: before, while and after this extension action with the intent to (i) delineate the digital literacy practices performed by the collaborators before the formative action; (ii) to narrate the literacy events made possible by the extension course; (iii) to investigate the contributions of the education course to the collaborators teaching practice. We sought theoretical contributions in the literacy studies (BAYNHAM, 1995; KLEIMAN, 1995; HAMILTON; BARTON; IVANIC, 2000), specifically when it comes to digital literacy (COPE, KALANTZIS, 2000; BUZATO, 2001, 2007, 2009; SNYDER, 2002, 2008; LANKSHEAR & KNOBEL, 2002, 2008) and teacher education (PERRENOUD, 2000; SILVA, 2001). Methodologically, this virtual ethnography study (KOZINETS, 1997; HINE, 2000) is inserted into the field of Applied Linguistics and adopts a quali-quantitative research approach (NUNAN, 1992; DÖRNYEI, 2006). The data analysis permitted to evidentiate that (i) before the course, the digital literacy practices focused on the personal and academic dimensions of their realities at the expense of the professional dimension; (ii) during the extension action, the teachers collaboratively took part in the hybrid study sessions, which had a pedagogical focus on the use of ICTs, accomplishing the use of digital literacy practices - unknown before that; (iii) after the course, the attitude of the collaborator teachers concerning the use of ICTs on their regular professional basis had changed, once those teachers started to effectively make use of them, promoting social visibility to what was produced in the school. We also observed that teachers in initial education acted as more experienced peers in collaborative learning process, offering support scaffolding (VYGOTSKY, 1978; BRUNER, 1985) to teachers in continuous education. This occurred because of the undergraduates actualize digital literacy practices were more sophisticated, besides the fact being integrate generation Y (PRENSKY, 2001)

Propriedades ópticas de nanocristais de SiGe: efeitos de dopagem e desordem

We have used ab initio calculations to investigate the electronic structure of SiGe based nanocrystals (NC s). This work is divided in three parts. In the first one, we focus the excitonic properties of Si(core)/Ge(shell) and Ge(core)/Si(shell) nanocrystals. We also estimate the changes induced by the effect of strain the electronic structure. We show that Ge/Si (Si/Ge) NC s exhibits type II confinement in the conduction (valence) band. The estimated potential barriers for electrons and holes are 0.16 eV (0.34 eV) and 0.64 eV (0.62 eV) for Si/Ge (Ge/Si) NC s. In contradiction to the expected long recombination lifetimes in type II systems, we found that the recombination lifetime of Ge/Si NC s (τR = 13.39μs) is more than one order of magnitude faster than in Si/Ge NC s (τR = 191.84μs). In the second part, we investigate alloyed Si1−xGex NC s in which Ge atoms are randomly positioned. We show that the optical gaps and electron-hole binding energies decrease linearly with x, while the exciton exchange energy increases with x due to the increase of the spatial extent of the electron and hole wave functions. This also increases the electron-hole wave functions overlap, leading to recombination lifetimes that are very sensitive to the Ge content. Finally, we investigate the radiative transitions in Pand B-doped Si nanocrystals. Our NC sizes range between 1.4 and 1.8 nm of diameters. Using a three-levels model, we show that the radiative lifetimes and oscillator strengths of the transitions between the conduction and the impurity bands, as well as the transitions between the impurity and the valence bands are strongly affected by the impurity position. On the other hand, the direct conduction-to-valence band decay is practically unchanged due to the presence of the impurity

Ondas de spin em quasi-cristais magnônicos

In this paper we investigate the spectra of band structures and transmittance in magnonic quasicrystals that exhibit the so-called deterministic disorders, specifically, magnetic multilayer systems, which are built obeying to the generalized Fibonacci (only golden mean (GM), silver mean (SM), bronze mean (BM), copper mean (CM) and nickel mean (NM) cases) and k-component Fibonacci substitutional sequences. The theoretical model is based on the Heisenberg Hamiltonian in the exchange regime, together with the powerful transfer matrix method, and taking into account the RPA approximation. The magnetic materials considered are simple cubic ferromagnets. Our main interest in this study is to investigate the effects of quasiperiodicity on the physical properties of the systems mentioned by analyzing the behavior of spin wave propagation through the dispersion and transmission spectra of these structures. Among of these results we detach: (i) the fragmentation of the bulk bands, which in the limit of high generations, become a Cantor set, and the presence of the mig-gap frequency in the spin waves transmission, for generalized Fibonacci sequence, and (ii) the strong dependence of the magnonic band gap with respect to the parameters k, which determines the amount of different magnetic materials are present in quasicrystal, and n, which is the generation number of the sequence k-component Fibonacci. In this last case, we have verified that the system presents a magnonic band gap, whose width and frequency region can be controlled by varying k and n. In the exchange regime, the spin waves propagate with frequency of the order of a few tens of terahertz (THz). Therefore, from a experimental and technological point of view, the magnonic quasicrystals can be used as carriers or processors of informations, and the magnon (the quantum spin wave) is responsible for this transport and processing

Rotação diferencial em estrelas do tipo solar

Stellar differential rotation is an important key to understand hydromagnetic stellar dynamos, instabilities, and transport processes in stellar interiors as well as for a better treatment of tides in close binary and star-planet systems. The space-borne high-precision photometry with MOST, CoRoT, and Kepler has provided large and homogeneous datasets. This allows, for the first time, the study of differential rotation statistically robust samples covering almost all stages of stellar evolution. In this sense, we introduce a method to measure a lower limit to the amplitude of surface differential rotation from high-precision evenly sampled photometric time series such as those obtained by space-borne telescopes. It is designed for application to main-sequence late-type stars whose optical flux modulation is dominated by starspots. An autocorrelation of the time series is used to select stars that allow an accurate determination of spot rotation periods. A simple two-spot model is applied together with a Bayesian Information Criterion to preliminarily select intervals of the time series showing evidence of differential rotation with starspots of almost constant area. Finally, the significance of the differential rotation detection and a measurement of its amplitude and uncertainty are obtained by an a posteriori Bayesian analysis based on a Monte Carlo Markov Chain (hereafter MCMC) approach. We apply our method to the Sun and eight other stars for which previous spot modelling has been performed to compare our results with previous ones. The selected stars are of spectral type F, G and K. Among the main results of this work, We find that autocorrelation is a simple method for selecting stars with a coherent rotational signal that is a prerequisite to a successful measurement of differential rotation through spot modelling. For a proper MCMC analysis, it is necessary to take into account the strong correlations among different parameters that exists in spot modelling. For the planethosting star Kepler-30, we derive a lower limit to the relative amplitude of the differential rotation. We confirm that the Sun as a star in the optical passband is not suitable for a measurement of the differential rotation owing to the rapid evolution of its photospheric active regions. In general, our method performs well in comparison with more sophisticated procedures used until now in the study of stellar differential rotation

Estudos ecogenômicos e bioprospectivos de Shewanella ssp

Bacteria trom Shewanella and Geobacter ganera are the most studied iron-reducing microorganisms particularly due to their electron transport systems and contribution to some industrial and environmental problems, including steel corrosion, bioenergy and bioremediation of petroleum-impacted sites. The present study was focused in two ways: the first is an in silico comparative ecogenomic study of Shewanella spp. with sequenced genomes, and the second is an experimental metagenomic work to detect iron-reducing Shewanella through PCR-DGGE of a metabolic gene. The in silico study resulted in positive correIation between copy number of 16S rDNA and genome size in Shewanella spp., with clusters of rrn near lhe origin of replication. This way, the genus is inferred as opportunist. There are no compact genomes and their sequences length varied, ranging from 4306142 nt in S. amazonensis SB2B to 5935403 nt in S. woodyi ATCC 51908, without correIation to temperature range characteristic of each specie. Intragenomic 16S rDNA sequences possess little divergence, but reasonable to resuIt in different phyIogenetic trees, depending on the sequence that is chosen to compare. For moIecuIar detection of iron-reducing Shewanella, it is proposed the mtrB gene as new biomarker. because it codes to a fundamental protein at Fe (III)-reduction. The specific primers were designed and evaluated in silico and resulted in a fragment of 360 pb. In the second study, these primers were tested in a genomic sample from S. oneidensis MR-1, amplifying the expected region. After this successfuI resuIt, the primer set was used as a tool to assess the iron-reducing communities of ShewaneIla genus under an environmental stress, i.e. crude oil contamination in mangrove sediment in Rio Grande do Norte State (Brazil). The primers presented high specificity and the reactions performed resulted in one single band of ampIification in the metagenomic samples. The fingerprinting obtained at DGGE reveaIed temporal variation of Shewanella spp. in analyzed samples. The resuIts presented show the detection of a biotechnological important group of microorganisms, the iron-reducing Shewanella spp. using a metabolic gane as target. It is concluded there are eight or more 16S rDNA sequences in Shewanella genus, with little divergence among them that affects the phylogeny; the pair of primers designed to ampIify mtrB sequences is a viable alternative to detect iron-reducing ShewanelIa in metagenomic approaches; such bacteria are present in the mangrove sediment anaIyzed, with temporal variations in the samples. This is the first experimental study that screened the iron-reducing Shewanella genus in a metagenomic experiment of mangrove sediments subjected to oil contamination through a key metabolic gene

Jardim do Seridó: A construção dos espaços públicos na Veneza Seridoense nas primeiras décadas do século XX

As the space and the city are objects of desires, interests, seduction, sedition, appropriations, battles, victories, defeats, require to be analyzed historically. This research investigates and discusses the construction of public spaces in Jardim do Seridó City, backwoods of Rio Rio Grande do Norte, in the first decades of twentieth century, when the municipality was chaired by Heráclio Pires Fernandes, who ruled from 1917 to 1930 and was graduated from the University of Pharmacy of Recife, where he contacted the architectural, political and artistic influences circulating in the capital of Pernambuco. In the first decades of the twentieth century, the space of Jardim earns statements and practices, against the discourse of modernity, which sought to justify the title of Veneza Seridoense . At the time, the city had undergone several transformations in its public spaces through the construction of the Butchery, the Market, the Public Roads connecting the city to other urban centers, the building of the Bridge of the Pedra Lavrada Farm, the Elementary School Antônio de Azevedo , the creation of the Music Band Euterpe Jardinense , the Literary and Recreative Guild, the pavilion, the paving, tree planting, lighting, streets naming and listing of the annual painting of households, the arrival of automobiles, mail and telegraph. The construction of these new sceneries and the arrival of equipments generated impacts in the daily life of the population and were received differentiated ways by individuals involved in the process, which shows the tension between old and new, the relationship between history and space

Correlato eletroencefalográfico do estado vibracional

O estado vibracional (EV) é descrito como uma sensação de vibração intensa por todo o corpo, em que o sujeito se mantém num estado de relaxamento psicofisiológico que pode ser gerado de forma espontânea ou autoinduzida. Pessoas que aplicam esta técnica relatam alterações do estado mental e emocional, tais como: relaxamento, disposição, limpidez de pensamento, equilíbrio emocional, melhoria do raciocínio, bemestar, entre outros. Estas são, entretanto observações subjetivas, sendo a mensuração deste fenômeno uma lacuna e um desafio para a ciência. O objetivo desta pesquisa é explorar sistematicamente o estado vibracional no âmbito da neurociência. Desta forma, medidas eletroencefalográficas (EEG) foram utilizadas para observar se a sensação subjetiva de EV é acompanhada por mudanças na atividade elétrica cerebral. Além disso, para avaliar se o EV provoca algum efeito positivo em funções cognitivas como atenção e memória, foi utilizado um teste de reconhecimento de palavras antes e depois da aplicação da técnica de EV. Foram também aplicados questionários de dados gerais socioeconômicos e de saúde, do perfil de estados de humor, de qualidade do sono, além de inventários psicológicos. O foco inicial do trabalho foi a análise estatística dos dados de EEG, ficando as outras análises para uma etapa posterior. Dois grupos de voluntários foram analisados, o primeiro formado por 14 sujeitos que praticam a técnica de EV há pelo menos 10 anos (Grupo Experiente - GEXP), e o segundo formado por 11 sujeitos que nunca haviam realizado a técnica (Grupo Controle - GCONT). O GCONT obteve instruções sobre a técnica de EV antes dos experimentos. Foram realizadas análises estatísticas dos registros eletroencefalográficos, para comparar os grupos, em quatro condições: Basal, Relaxamento, Não-EV (período em que o sujeito está engajado na tarefa, mas ainda não percebe o EV) e EV (período em que o sujeito percebe o EV). Uma vez que os sujeitos do GCONT relataram não ter conseguido atingir a condição de EV propriamente, a comparação entre grupos foi feita apenas nas três condições, Basal, Relaxamento e Não-EV. Para isso, foi usado o teste de Mann-Whitney U com um limiar estatístico de p<0,05. De forma geral, o GEXP apresentou maior potência na banda de frequência alfa 2 (9,5-11,0 Hz) em todas as condições. Durante o período Não-EV, o GEXP também apresentou uma maior potência na banda de frequência alfa 3 (11,5-13,0 Hz) na região temporal esquerda, e gama 1 (30,5-55,0 Hz) e gama 2 (65,0-80,0 Hz) em regiões central, parietal e temporal esquerda, mas menor potência na banda de frequência teta 1 (3,5 - 5,0 Hz), em regiões centro-parietais. Para a análise estatística intragrupo, entre as condições, utilizou-se o teste estatístico Wilcoxon pareado. Observaram-se diferenças significativas (p<0,005), principalmente em regiões centrais, em teta 1 (3,5-5,0 Hz), sendo maior no Relaxamento, quando comparado com as condições Basal e Não-EV, no GCONT, e com o Não-EV e EV, no GEXP. No GEXP, a potência de gama 1 (30,5-55,0 Hz) e gama 2 (65,0-80,0 Hz) foi difusamente maior durante o EV, se comparado às outras três condições. Para o GCONT, apenas a condição Basal apresentou maior potência de gama 1 (30,5-55,0 Hz) e gama 2 (65,0- 80,0 Hz), se comparado com o Relaxamento. O aumento de teta 1 no Relaxamento, principalmente no GCONT, pode estar associado a uma maior sonolência deste grupo durante esta condição. Já o aumento de alfa 2 durante o Não-EV e o EV, pode estar associado com processos de atenção e cognição (DOLPPERMAYR et al., 2002; FELL et al., 2010; KLIMESCH et al., 1999; RAY E COLE, 1985). Por outro lado, o aumento da potência de gama em sujeitos experientes na técnica de EV encontrado aqui e em trabalhos anteriores, em meditadores experientes (FELL et al., 2010; LEHMANN et al., 2001; LUTZ et al., 2004), poderia estar associado a alterações nos processos mentais e cognitivos destes praticantes, tais como atenção, memória operacional, aprendizagem e percepção consciente embora, análises adicionais devam ser realizadas para excluir a possibilidade de interferência de artefatos musculares nos dados de EEG. Estes resultados suscitam a hipótese de que no engajamento da tarefa do EV e durante o EV, os sujeitos do GEXP conseguem manter-se em um estado de alerta, porém com maior nível de relaxamento e concentração. Uma inspeção mais detalhada dos dados, além de outros experimentos com diferentes protocolos, um maior número de sujeitos e pesquisas longitudinais são necessários para que testar esta hipótese

Avaliação do comportamento termoanalítico e oxidativo do biodiesel de mamona

In this work biodiesel was gotten through the transesterification reaction using the oil of castor as source of triglycerides and using the methylic route for obtaining of esters. For the characterization of biodiesel and its mixtures with mineral diesel oil, physical chemical parameters and several analytical techniques had been used, as well as: gas chromatography (GC), nuclear magnetic resonance of proton (1H NMR), infrared spectroscopy (IR) and thermal analysis. The chromatography confirmed the complete reaction of esters in biodiesel presenting a 97,08% conversion. The 1H - NMR presented singlet in 3,6 ppm corresponding to the hydrogen of the group ester RCOO CH3. The infrared presented a strong band in 1741 cm-1 referring to stretching C=O of ester and an average band in 1175 cm-1 referring C O deformation. With the data of thermal analysis it was possible to observe the thermal and oxidative stability of the samples changing the atmospheres of synthetic air and nitrogen, where stages of the thermal decomposition had been verified and had been attributed to the volatilization and/or decomposition of the triacylglycerides. The thermal degradation of the samples was carried through 150 and 210°C during 1, 12, 24 and 48 hours and was observed change in the thermogravimetric profile, therefore an increase in the number of stages of the thermal decomposition also occurred indicating characteristic intermediate composites of polymerization, being this confirmed through the rheological study that presented brusque increase of viscosity. The kinetic study showed that the activation energy has the following order: biodiesel > mineral diesel oil > mixtures biodiesel/diesel

Desenvolvimento de um novo complexo macrocíclico do sistema cobalto cyclam

In this work were synthesized and studied the spectroscopic and electrochemical characteristics of the coordination compounds trans-[Co (cyclam)Cl2]Cl, trans- Na[Co(cyclam)(tios)2], trans-[Co(en)2Cl2]Cl and trans-Na[Co(en)2(tios)2], where tios = thiosulfate and en = ethylenediamine. The compounds were characterized by: Elemental Analysis (CHN), Absorption Spectroscopy in the Infrared (IR), Uv-Visible Absorption Spectroscopy, Luminescence Spectroscopy and Electrochemistry (cyclic voltammetry). Elemental Analysis (CHN) suggests the following structures for the complex: trans- [Co(cyclam)Cl2]Cl.6H2O and trans-Na[Co(cyclam)(tios)2].7H2O. The electrochemical analysis, when compared the cathodic potential (Ec) processes of the complexes trans- [Co(cyclam)Cl2]Cl and trans-[Co(en)2Cl2]Cl, indicated a more negative value (-655 mV) for the second complex, suggesting a greater electron donation to the metal center in this complex which can be attributed to a greater proximity of the nitrogen atoms of ethylenediamine in relation to metal-nitrogen cyclam. Due to the effect of setting macrocyclic ring to the metal center, the metal-nitrogen bound in the cyclam are not as close as the ethylenediamine, this fact became these two ligands different. Similar behavior is also observed for complexes in which the chlorides are replaced by thiosulfate ligand, trans-Na[Co(en)2(tios)2] (-640 mV) and trans-Na[Co(cyclam)(tios)2] (-376 mV). In absorption spectroscopy in the UV-visible, there is the band of charge transfer LMCT (ligand p d* the metal) in the trans-Na[Co(cyclam)(tios)2] (350 nm, p tios  d* Co3+) and in the trans-Na[Co(en)2(tios)2] (333 nm, p tios d* Co3+), that present higher wavelength compared to complex precursor trans- [Co(cyclam)Cl2]Cl (318 nm, pCl  d* Co3+), indicating a facility of electron density transfer for the metal in the complex with the thiosulfate ligand. The infrared analysis showed the coordination of the thiosulfate ligand to the metal by bands in the region (620-635 cm-1), features that prove the monodentate coordination via the sulfur atom. The νN-H bands of the complexes with ethylenediamine are (3283 and 3267 cm-1) and the complex with cyclam bands are (3213 and 3133 cm-1). The luminescence spectrum of the trans-Na[Co(cyclam)(tios)2] present charge transfer band at 397 nm and bands dd at 438, 450, 467, 481 and 492 nm.

Estudo de titanatos nanoestruturados obtidos por tratamento hidrotérmico de óxido de titânio em meio alcalino

TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase

Síntese e Caracterização de Titanatos de Cobalto e Níquel, dopados com Praseodímio, obtidos a partir da decomposição de Nitrilotriacetatos

In recent years, studies about the physicochemical properties of mixed oxides, call attention of the scientific community, properties like as piezoelectricity, photoluminescence, or applications as catalysts, arise in these compounds, when their chemical compositions are modified, in this context some routes are employed in the synthesis of these materials, among which can be cited these methods: ceramic, combustion, co-precipitation, Pechini or polymeric precursor method, hydrothermal, sol-gel; these routes are divided into traditional routes or chemical routes. In this work were synthesized oxides with variable composition, from the thermal decomposition of titanium, cobalt, nickel and praseodymium nitrilotriacetates. The nitrilotriacetates were characterized by IR Spectroscopy (FTIR), Thermogravimetric (TG/ DTG) and Differential Scanning Calorimetry (DSC), while oxides have been characterized by X-ray diffraction (XRD), Spectrofluorimetry and IR Spectroscopy (FTIR). From FTIR data, it was demonstrated that the displacement of the band corresponding to the carboxylate group (νCOOH) at 1712 cm-1, present in nitrilotriacetic acid (H3NTA), for 1680-1545 cm-1, these stretches are characteristics of coordinated nitrilotriacetates, By thermal analysis (TG/DTG /DSC), it was suggested, that in an oxidizing atmosphere (air) oxides are obtained at lower temperatures than in an inert atmosphere N2(g). By results from X-ray Diffraction (XRD), it was determinated that the oxides are crystalline and the predominant phases obtained are summarized titanate phases rutile and ilmenite. By fluorimetry was observed that the intensity of emission bands are directly proportional to the concentration of ions Ni2+, Co2+ and Pr3+, and IR spectroscopy (FTIR) from oxides, demonstrated the disappearance of characteristic bands by nitrilotriacetates, determining the complete decomposition of the nitrilotriacetates in oxides