Análise por meio de espectroscopia de emissão óptica das espécies ativas em nitretação iônica e gaiola catódica

Plasma process like ionic nitriding and cathodic cage plasma nitriding are utilized in order to become hard surface of steels. The ionic nitriding is already accepted in the industry while cathodic cage plasma nitriding process is in industrial implementation stage. Those process depend of plasma parameters like electronic and ionic temperature (Te, Ti), species density (ne, ni) and of distribution function of these species. In the present work, the plasma used to those two processes has been observed through Optical Emission Spectroscopy OES technique in order to identify presents species in the treatment ambient and relatively quantify them. So plasma of typical mixtures like N2 H2 has been monitored through in order to study evolution of those species during the process. Moreover, it has been realized a systematic study about leaks, also thought OES, that accomplish the evolution of contaminant species arising because there is flux of atmosphere to inside nitriding chamber and in what conditions the species are sufficiently reduced. Finally, to describe the physic mechanism that acts on both coating techniques ionic nitriding and cathodic cage plasma nitriding

Síntese e caracterização do líquido iônico tetrafluoroborato de 1-metil-3-(2,6-(S)-dimetiloct-2-eno)-imidazol como eletrólito para produção de hidrogênio via eletrólise da água

Ionic liquids (ILs) are organic compounds liquid at room temperature, good electrical conductors, with the potential to form as a means for electrolyte on electrolysis of water, in which the electrodes would not be subjected to such extreme conditions demanding chemistry [1]. This paper describes the synthesis, characterization and study of the feasibility of ionic liquid ionic liquid 1-methyl-3(2,6-(S)-dimethyloct-2-ene)-imidazole tetrafluoroborate (MDI-BF4) as electrolyte to produce hydrogen through electrolysis of water. The MDI-BF4 synthesized was characterized by thermal methods of analysis (Thermogravimetric Analysis - TG and Differential Scanning Calorimetry - DSC), mid-infrared spectroscopy with Fourier transform by method of attenuated total reflectance (FTIR-ATR), nuclear magnetic resonance spectroscopy of hydrogen (NMR 1H) and cyclic voltammetry (CV). Where thermal methods were used to calculate the yield of the synthesis of MDI-BF4 which was 88.84%, characterized infrared spectroscopy functional groups of the compound and the binding B-F 1053 cm-1; the NMR 1H analyzed and compared with literature data defines the structure of MDI-BF4 and the current density achieved by MDI-BF4 in the voltammogram shows that the LI can conduct electrical current indicating that the MDI-BF4 is a good electrolyte, and that their behavior does not change with the increasing concentration of water

Fiscalização difusa da constitucionalidade e o incidente de argüição de inconstitucionalidade

The present work consists of studying to diffuse control of constitutionality in Brazil, with emphasis in a procedural alternative to the evolution of that model: the incident to challenge of unconstitutionality. Starting from the discussion about the new role of constitutional jurisdiction in peripheral countries and in the globalized society, without forgetting to face inevitable doubts about its legitimacy before other powers of the State, the Brazilian control of constitutionality is revealed, under a diffuse, non-dichotomical view, through a number of inconsistencies and misunderstandings, that compromise social peace, the credibility of democratic institutions and the supremacy of juridical security. In order to achieve the goal, the study in course discussed the main difficulties of the Brazilian mixed model of constitutionality control, as well as, directing its view to the incident of challenge of unconstitutionality, which the most adequate forms to assure its appropriateness, legitimacy, processing and decisory effects are. Is was essential, in this point of view, to establish the difference between the incident of challenge of unconstitutionality conceived in article of the Brazilian Federal Constitution and the incident of challenge of unconstitutionality such as it is known in the European models. The insertion of the incident of challenge of unconstitutionality based on European models in the Brazilian control system, without jeopardizing the North-American essence the Brazilian constitutional history presents since 1981, is the hypothesis that is presented as an improvement of constitutional protection

Sensores de reflectância e fluorescência na avaliação de teores de nitrogênio, produção de biomassa e produtividade do algodoeiro

O objetivo deste trabalho foi avaliar o potencial de utilização dos sensores de reflectância e fluorescência na avaliação de teores de N‑NO3‑ no pecíolo, na produção de biomassa e na produtividade do algodoeiro. Utilizou-se o delineamento experimental de blocos ao acaso em arranjo fatorial 3x4, com quatro repetições. Os tratamentos consistiram de três variedades de algodão (ST‑4288‑B2RF, ST‑4498‑B2RF e DP-164‑B2RF) e quatro doses de N (0, 45, 90 e 135 kg ha‑1). Aos 120 dias após a semeadura, foram realizadas leituras com sensores ópticos de reflectância e fluorescência. Não houve correlação significativa dos teores de N‑NO3‑ no pecíolo com os índices de reflectância; porém, houve correlação destes com a produção de biomassa (0,39) e a produtividade (0,32 a 0,41). Os índices do sensor de fluorescência correlacionaram-se significativamente com teores de N‑NO3‑ no pecíolo (0,34 a 0,61), produção de biomassa (0,30 a 0,53) e produtividade (0,34). em comparação com os índices de reflectância, os de fluorescência apresentam maior capacidade de avaliar os teores de N‑NO3‑ no pecíolo, capacidade semelhante em detectar variação na biomassa e menor capacidade de detectar variação da produtividade do algodoeiro, quando se aplicam doses crescentes de N.

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

Diagnóstico de descarga de cátodo oco de ar e pós-descarga Ar N2 por espectroscopia de emissão óptica e espectrometria de massa

Many applications require that the plasma discharge is produced apart from the surface to be processed, thus preventing damage caused by bombardment and/or plasma radiation. In the post-discharge regime in various applications thermally sensitive materials can be used. In this work, active species produced by discharge and post-discharge hollow cathode were diagnosed by optical emission spectroscopy and mass spectrometry. The discharge was produced with the gases Ar and Ar - N2 gas flow ranging from 1 to 6 cm3/min and electric current between 150 to 600 mA. It was estimated that the ion density inside the hollow cathode, with 2 mm diameter ranged between 7.71 and 14.1 x 1015 cm-3. It was observed that the gas flow and the electric current changes the emission intensity of Ar and N2 species. The major ionic species detected by quadrupole mass spectrometry were Ar+ and N2+. The ratio of optical emission intensities of N2(1 +)/Ar(811 nm) was related to the partial pressure of N2 after the hollow cathode discharge at low pressure

Controle por modos deslizantes com compensação difusa aplicado a sistemas com descontinuidade

The development of non-linear controllers gained space in the theoretical ambit and of practical applications on the moment that the arising of digital computers enabled the implementation of these methodologies. In comparison with the linear controllers more utilized, the non -linear controllers present the advantage of not requiring the linearity of the system to determine the parameters of control, which permits a more efficient control especially when the system presents a high level of non-linearity. Another additional advantage is the reduction of costs, since to obtain the efficient control through linear controllers it is necessary the utilization of sensors and more refined actuators than when it is utilized a non-linear controller. Among the non-linear theories of control, the method of control by gliding ways is detached for being a method that presents more robustness, before uncertainties. It is already confirmed that the adoption of compensation on the region of residual error permits to improve better the performance of these controllers. So, in this work it is described the development of a non-linear controller that looks for an association of strategy of control by gliding ways, with the fuzzy compensation technique. Through the implementation of some strategies of fuzzy compensation, it was searched the one which provided the biggest efficiency before a system with high level of nonlinearities and uncertainties. The electrohydraulic actuator was utilized as an example of research, and the results appoint to two configurations of compensation that permit a bigger reduction of the residual error

Monitoramento em tempo real de processos fermentativos por espectroscopia no infravermelho próximo (NIRS)

A chemical process optimization and control is strongly correlated with the quantity of information can be obtained from the system. In biotechnological processes, where the transforming agent is a cell, many variables can interfere in the process, leading to changes in the microorganism metabolism and affecting the quantity and quality of final product. Therefore, the continuously monitoring of the variables that interfere in the bioprocess, is crucial to be able to act on certain variables of the system, keeping it under desirable operational conditions and control. In general, during a fermentation process, the analysis of important parameters such as substrate, product and cells concentration, is done off-line, requiring sampling, pretreatment and analytical procedures. Therefore, this steps require a significant run time and the use of high purity chemical reagents to be done. In order to implement a real time monitoring system for a benchtop bioreactor, these study was conducted in two steps: (i) The development of a software that presents a communication interface between bioreactor and computer based on data acquisition and process variables data recording, that are pH, temperature, dissolved oxygen, level, foam level, agitation frequency and the input setpoints of the operational parameters of the bioreactor control unit; (ii) The development of an analytical method using near-infrared spectroscopy (NIRS) in order to enable substrate, products and cells concentration monitoring during a fermentation process for ethanol production using the yeast Saccharomyces cerevisiae. Three fermentation runs were conducted (F1, F2 and F3) that were monitored by NIRS and subsequent sampling for analytical characterization. The data obtained were used for calibration and validation, where pre-treatments combined or not with smoothing filters were applied to spectrum data. The most satisfactory results were obtained when the calibration models were constructed from real samples of culture medium removed from the fermentation assays F1, F2 and F3, showing that the analytical method based on NIRS can be used as a fast and effective method to quantify cells, substrate and products concentration what enables the implementation of insitu real time monitoring of fermentation processes

Uso de índices de reflectância das folhas para avaliar o nível de nitrogênio em grama-bermuda

A reflectância da folha em determinados comprimentos de onda pode ser uma alternativa para estimar a concentração de nitrogênio (N) na planta, devido à relação entre o teor de clorofila e de N no tecido foliar. Este trabalho teve por objetivo avaliar índices da cor verde em grama-bermuda para predizer o nível de N na planta. O experimento foi conduzido em área comercial de produção de grama-bermuda, localizada na cidade de Capela do Alto/SP. O delineamento experimental utilizado foi de blocos ao acaso, com cinco tratamentos (0, 150, 300, 450 e 600kg de N ha-1) e quatro repetições. Foi avaliada a reflectância das folhas pelo uso de medidor de cor de grama, clorofilômetro, e por meio de análise da imagem digital. O matiz (H) e índice de cor verde escuro (ICVE), calculados com base nos índices de reflectância da imagem digital, o ICVE, obtido com medidor de cor de grama, e a intensidade de coloração verde (ICV), obtida com o clorofilômetro, apresentaram forte correlação positiva com a concentração de N e a taxa de cobertura do solo (TCS) da grama-bermuda, podendo ser utilizados como índices auxiliares na recomendação de adubação nitrogenada para a cultura. Os valores obtidos que podem servir como primeiros índices para avaliação do estado nutricional em N na grama-bermuda Celebration são: H de 88 a 109o e ICVE de 0,54 a 0,66 (imagem digital); H de 67 a 76o e ICVE de 0,41 a 0,44 (medidor de cor da grama TCM 500); e ICV de 374 a 471 (clorofilômetro CM 1000).

A influência da poluição difusa e do regime hidrológico peculiar do semiárido na qualidade da água de um reservatório tropical

In semiarid region of northeast Brazil, the majority of reservoirs used for public supply has suffered degradation of water quality affected by diffuse pollution from agricultural and livestock areas of the watershed and by hydrologic regime peculiar to the region, characterized by a rainy season with higher volumes stored in reservoirs and a dry season with a reduction in water level due to high evaporation and increase of eutrophication. The Dourado reservoir, located in Currais Novos city, semiarid region of Rio Grande do Norte state, is one example of a water supply reservoir that can have degradation of water quality and impracticability of their use, due to the high external input of nutrients from non-point sources of watershed during the rainy season and increasing of eutrophication due to decrease the stored volume during the dry period. This study aimed to investigate and quantify diffuse pollution and the hydrologic regime of semiarid region in order to establish standards regarding the water quality of Dourado reservoir. The study period was between the months of May 2011 to March 2012. The diffuse pollution was quantified in terms of watershed from the mass balance of phosphorus in the reservoir, as in relation to areas under different types of land use within the riparian zone of the reservoir from the assessment of soil chemical properties and losses of phosphorus in each area. The influence of hydrological regime on water quality of the reservoir was evaluated from the monthly monitoring of the morphometric, meteorological and limnological features throughout the study period. The results showed that the reservoir has received a high load of phosphorus coming from the drainage basin and presents itself as a system able to retain some of that load tributary, giving an upward trend of the eutrophication process. Diffuse pollution by nutrients from areas under different types of land use within the riparian zone of the reservoir was higher in areas under the influence of livestock, being this area considered a potential diffuse source of nutrients to the reservoir. Regarding the water regime during the rainy season the reservoir was characterized by high concentrations of nutrients and small algal biomass, while in the dry season the reduction of volume and increase of the water retention time of the reservoir, contributing to the excessive growth algal biomass, favoring an increase in eutrophication and deterioration of water quality. In synthesis the water quality of Dourado reservoir is directed by diffuse pollution coming from the drainage basin and the hydrological regime of the peculiar semiarid region, where the rainy season is characterized by high input of allochthonous compounds from the tributaries and erosion of the soil in the reservoir riparian zone, and the dry season characterized by reducing the storage volume due to high evaporation, high residence time of water and consequent degradation of water quality due to the increase of eutrophication process

Estudo de coprólito da bacia sedimentar do Araripe por meios de espectroscopia FT-IR e difração de Raios-X

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Aplicação da espectroscopia de absorção de raios X no estudo do comportamento do íon Cu2+ em micelas inversas

This work deals with the application of X-Ray Absorption Spectroscopy on the study of the behavior of Cu2+ ions in inverse micelles. The formation of copper nanoparticles in water-in-oil microemulsions in pseudo-ternary systems of cetyl trimethylammonium Bromide (CTAB) surfactant, butanol co-surfactant, heptane as oil phase and aqueous solutions of CuSO4.5H2O, and NaBH4. The microemulsions were prepared with a fixed percentage (60 %) of oil phase and a variable water to tensoative proportion. It was observed an increase on Cu2+ reduction by the sodium borohydride in microemulsions with 13 % of aqueous phase, independent of the reaction time. For the microemulsions in which the aqueous phase is composed only by the CuSO4 solution, it was observed that the color of the solution depends on the water to surfactant ratio. These changes in color were attributed to a competition for the hidratation water between the polar head of the tensoative and Cu2+ ions with the eventual substitution of oxygen by bromine atoms in the first coordination shell of Cu2+ ions

Determinação do teor de diclofenaco sódico em comprimidos por espectroscopia no infravermelho próximo NIR com calibração multivariada PLS

This work is combined with the potential of the technique of near infrared spectroscopy - NIR and chemometrics order to determine the content of diclofenac tablets, without destruction of the sample, to which was used as the reference method, ultraviolet spectroscopy, which is one of the official methods. In the construction of multivariate calibration models has been studied several types of pre-processing of NIR spectral data, such as scatter correction, first derivative. The regression method used in the construction of calibration models is the PLS (partial least squares) using NIR spectroscopic data of a set of 90 tablets were divided into two sets (calibration and prediction). 54 were used in the calibration samples and the prediction was used 36, since the calibration method used was crossvalidation method (full cross-validation) that eliminates the need for a validation set. The evaluation of the models was done by observing the values of correlation coefficient R 2 and RMSEC mean square error (calibration error) and RMSEP (forecast error). As the forecast values estimated for the remaining 36 samples, which the results were consistent with the values obtained by UV spectroscopy

Espectroscopia no infravermelho próximo e métodos de calibração multivariada aplicados à determinação simultânea de parâmetros bioquímicos em plasma sanguíneo

In this work, the quantitative analysis of glucose, triglycerides and cholesterol (total and HDL) in both rat and human blood plasma was performed without any kind of pretreatment of samples, by using near infrared spectroscopy (NIR) combined with multivariate methods. For this purpose, different techniques and algorithms used to pre-process data, to select variables and to build multivariate regression models were compared between each other, such as partial least squares regression (PLS), non linear regression by artificial neural networks, interval partial least squares regression (iPLS), genetic algorithm (GA), successive projections algorithm (SPA), amongst others. Related to the determinations of rat blood plasma samples, the variables selection algorithms showed satisfactory results both for the correlation coefficients (R²) and for the values of root mean square error of prediction (RMSEP) for the three analytes, especially for triglycerides and cholesterol-HDL. The RMSEP values for glucose, triglycerides and cholesterol-HDL obtained through the best PLS model were 6.08, 16.07 e 2.03 mg dL-1, respectively. In the other case, for the determinations in human blood plasma, the predictions obtained by the PLS models provided unsatisfactory results with non linear tendency and presence of bias. Then, the ANN regression was applied as an alternative to PLS, considering its ability of modeling data from non linear systems. The root mean square error of monitoring (RMSEM) for glucose, triglycerides and total cholesterol, for the best ANN models, were 13.20, 10.31 e 12.35 mg dL-1, respectively. Statistical tests (F and t) suggest that NIR spectroscopy combined with multivariate regression methods (PLS and ANN) are capable to quantify the analytes (glucose, triglycerides and cholesterol) even when they are present in highly complex biological fluids, such as blood plasma