Tin(II)-EDTA complex: kinetic of thermal decomposition by non-isothermal procedures

Tin on the oxide form, alone or doped with others metals, has been extensively used as gas sensor, thus, this work reports on the preparation and kinetic parameters regarding the thermal decomposition of Sn(II)-ethylenediaminetetraacetate as precursor to SnO2. Thus, the acquaintance with the kinetic model regarding the thermal decomposition of the tin complex may leave the door open to foresee, whether it is possible to get thin film of SnO2 using Sn(II)-EDTA as precursor besides the influence of dopants added.The Sn(II)-EDTA soluble complex was prepared in aqueous medium by adding of tin(II) chloride acid solution to equimolar amount of ammonium salt from EDTA under N-2 atmosphere and temperature of 50degreesC arising the pH similar to 4. The compound was crystallized in ethanol at low-temperature and filtered to eliminate the chloride ions, obtaining the heptacoordinated chelate with the composition H2SnH2O(CH2N(CH2COO)(2))(2).0.5H(2)O.Results from TG, DTG and DSC curves under inert and oxidizing atmospheres indicate the presence of water coordinated to the metal and that the ethylenediamine fraction is thermally more stable than carboxylate groups. The final residue from thermal decomposition was the SnO2 characterized by X-ray as a tetragonal rutile phase.Applying the isoconversional Wall-Flynn-Ozawa method on the DSC curves, average activation energy: E-a = 183.7 +/- 12.7 and 218.9 +/- 2.1 kJ mol(-1), and pre-exponential factor: log A = 18.85 +/- 0.27 and 19.10 +/- 0.27 min(-1), at 95% confidence level, could be obtained, regarding the loss of coordinated water and thermal decomposition of the carboxylate groups, respectively. The E-a and logA also could be obtained applying isoconventional Wall-Flynn method on the TG curves.From E-a and log A values, Dollimore and Malek procedures could be applied suggesting R3 (contracting volume) and SB (two-parameter model) as the kinetic model to the loss of coordinated water (177-244degreesC) and thermal decomposition of the carboxylate groups (283-315degreesC), respectively. Simulated and experimental normalized DTG and DSC curves besides analysis of residuals check these kinetic models. (C) 2003 Elsevier B.V. All rights reserved.

Bayesian outlier analysis in binary regression

We propose alternative approaches to analyze residuals in binary regression models based on random effect components. Our preferred model does not depend upon any tuning parameter, being completely automatic. Although the focus is mainly on accommodation of outliers, the proposed methodology is also able to detect them. Our approach consists of evaluating the posterior distribution of random effects included in the linear predictor. The evaluation of the posterior distributions of interest involves cumbersome integration, which is easily dealt with through stochastic simulation methods. We also discuss different specifications of prior distributions for the random effects. The potential of these strategies is compared in a real data set. The main finding is that the inclusion of extra variability accommodates the outliers, improving the adjustment of the model substantially, besides correctly indicating the possible outliers.

Mapeamento do contorno estrutural do embasamento da bacia sedimentar de Curitiba - PR

The sedimentary Curitiba basin is located in the Central-Southern part of the first Parananense plateau, and comprises Curitiba (PR), and part of the neighbour Municipalities (fig.1). It is supposed to be of Plio-Pleistocene age. It has a shallow sedimentary fulfillment, represented by the Guabirotuba formation (BIGARELLA and SALAMUNI, 1962) which is dristributed over a large area of about 3.000km2. The internal geometry, not entirely known yet, is actually object of detailed research, that shows its geological evolution to Cenozoic tectonic movements. For the purpose of this study the definition of the structural contour of the basement and their depo-centers is fundamental. This paper presents the results of the integration of surface and subsurface data, processed by statistical methods, which allowed a more precise definition of the morphostructural framework of the basement. For the analysis of the geological spacial data, specific softwares were used for statistical processing for trend surfaces analysis. The data used in this study are of following types: a) drilling logs for ground water; b) description of surface points of geological maps (CRPM, 1977); c) description of points of geotechnical drillings and down geological survey. The data of 223 drilling logs for ground water were selected out of 770 wells. The description files of 700 outcrops, as well as planialtimetric field data, were used for the localization of the basement outcrop. Thus, a matrix with five columns was set up: utm E-W (x) and utm N-S (y); surface altitude (z); altimetric cote of the contact between sedimentary rocks and the basement (k); isopachs (l). For the study of the basement limits, the analysis of surface trends of 2(nd) and 3(rd) degree polinomial for the altimetric data (figs. 2 and 3) were used. For the residuals the method of the inverse of the square of the distance (fig.4) was used. The adjustments and the explanations of the surfaces were made with the aid of multiple linear regressions. The analysis of 3rd degree polinomial trend surface (fig.3) confirmed that the basement tends to be more exposed towards NNW-SSE explaining better the data trend through an ellipse, which striking NE-SW and dipping SW axis coincides with the trough of the basin observed in the trending surface of the basement. The performed analysis and the respective images offer a good degree of certainty of the geometric model of the Curitiba Basin and of the morphostructure of its basement. The surface trend allows to sketch with a greater degree of confidence the structural contour of the topgraphic surface (figs. 5 and 6) and of the basement (figs. 7 and 8), as well as the delimitation of intermediate structural heights, which were responsible for isolated and assymmetric depocenters. These details are shown in the map of figures 9 and 10. Thus, the Curitiba Basin is made up by a structural trough stretching NE-SW, with maximum preserved depths of about 80m, which are separated by heights and depocenters striking NW-SE (fig. 11). These structural features seems to have been controlled by tectonic reactivation during the Tertiary (HASUI, 1990) and which younger dissection was conditioned by neotectonic processes (SALAMUNI and EBERT, 1994).

Optimization procedures in the design of continuous induction hardening and tempering installations for magnetic steel bars

An inverse problem concerning the industrial process of steel bars hardening and tempering is considered. The associated optimization problem is formulated in terms of membership functions and, for the sake of comparison, also in terms of quadratic residuals; both geometric and electromagnetic design variables have been considered. The numerical solution is achieved by coupling a finite difference procedure for the calculation of the electromagnetic and thermal fields to a deterministic strategy of minimization based on modified Flctcher and Reeves method. © 1998 IEEE.

Assessing relationships between genetic evaluations using robust regression with an application to holsteins in Uruguay

Globalization of dairy cattle breeding has created a need for international sire proofs. Some early methods for converting proofs from one population to another are based on simple linear regression. An alternative robust regression method based on the t-distribution is presented, and maximum likelihood and Bayesian techniques for analysis are described, including the situation in which some proofs are missing. Procedures were used to investigate the relationship between Holstein sire proofs obtained by two Uruguayan genetic evaluation programs. The results suggest that conversion equations developed from data including only sires having proofs in both populations can lead to distorted results, relative to estimates obtained using techniques for incomplete data. There was evidence of non-normality of regression residuals, which constitutes an additional source of bias. A robust estimator may not solve all problems, but can provide simple conversion equations that are less sensitive to outlying proofs and to departures from assumptions.

Robust linear mixed models with normal/independent distributions and Bayesian MCMC implementation

Linear mixed effects models have been widely used in analysis of data where responses are clustered around some random effects, so it is not reasonable to assume independence between observations in the same cluster. In most biological applications, it is assumed that the distributions of the random effects and of the residuals are Gaussian. This makes inferences vulnerable to the presence of outliers. Here, linear mixed effects models with normal/independent residual distributions for robust inferences are described. Specific distributions examined include univariate and multivariate versions of the Student-t, the slash and the contaminated normal. A Bayesian framework is adopted and Markov chain Monte Carlo is used to carry out the posterior analysis. The procedures are illustrated using birth weight data on rats in a texicological experiment. Results from the Gaussian and robust models are contrasted, and it is shown how the implementation can be used for outlier detection. The thick-tailed distributions provide an appealing robust alternative to the Gaussian process in linear mixed models, and they are easily implemented using data augmentation and MCMC techniques.

Avaliação do nível de multicaminho no posicionamento relativo GPS e sua atenuação através da análise de multiresolução

The multipath effect affects the differential and relative positioning, even that one involving short baselines. So it is necessary to detect this effect, check the caused error level, and mainly, its removal. This paper aims at analysing and comparing some useful components in the detection of this effect. These components are the Signal to Noise Ratio (SNR), the values of MP1 and MP2 obtained from the TEQC software that indicates the multipath level in the carriers L1 and L2, the multipath repeatability in consecutive days and the elevation angle and the azimuth of the satellites. For this purpose, an experiment is carried out, comparing such components in the presence and the absence of reflector objects that cause the multipath. Not only there is clear multipath repeatability in the residuals, but it also appears in the measures SNR, MP1 and MP2, reaching up 99% of correlation. For reduction, at least, of the high frequency multipath effect, the Multi-Resolution Analysis using wavelets is applied in the double differences (DD) measures. Some statistical tests were accomplished, which indicate results improvement, and mainly, larger reliability in the solution of the ambiguities, reaching up 49% of improvement concerning the Ratio test without applying the proposed method.

Aplicação da Geoestatística Não-paramétrica para a compartimentação geomecânica de uma extensão típica do túnel do metrô - Linha 4, da cidade de São Paulo

In view of the limited number of drill holes, interpolation of the data becomes a relatively complex task. In this study, we sought to make estimates associated with lithological types, since a quantification based on lithology can be extracted from the empty spaces in the sampling. For example, QBarton is always below the median of the biotitic litotype, information which can be used in the elaboration of geostatistical models in situations where samples are lacking. To overcome bias in the data, required by geostatistical conceptualization, we worked with the residuals obtained from the adjustment of a surface and the observed values, for the variographic analysis. The final results made possible a more optimized evaluation of the final costs required for the construction project.

Spectral analysis and low-frequency multipath mitigation for kinematic applications

Low-frequency multipath is still one of the major challenges for high precision GPS relative positioning. In kinematic applications, mainly, due to geometry changes, the low-frequency multipath is difficult to be removed or modeled. Spectral analysis has a powerful technique to analyze this kind of non-stationary signals: the wavelet transform. However, some processes and specific ways of processing are necessary to work together in order to detect and efficiently mitigate low-frequency multipath. In this paper, these processes are discussed. Some experiments were carried out in a kinematic mode with a controlled and known vehicle movement. The data were collected in the presence of a reflector surface placed close to the vehicle to cause, mainly, low-frequency multipath. From theanalyses realized, the results in terms of double difference residuals and statistical tests showed that the proposed methodology is very efficient to detect and mitigate low-frequency multipath effects. © 2008 IEEE.

An effective wavelet method to detect and mitigate low-frequency multipath effects

To ensure high accuracy results from GPS relative positioning, the multipath effects have to be mitigated. Although the careful selection of antenna site and the use of especial antennas and receivers can minimize multipath, it cannot always be eliminated and frequently the residual multipath disturbance remains as the major error in GPS results. The high-frequency multipath from large delays can be attenuated by double difference (DD) denoising methods. But the low-frequency multipath from short delays is very difficult to be reduced or modeled. In this paper, it is proposed a method based on wavelet regression (WR), which can effectively detect and reduce the low-frequency multipath. The wavelet technique is firstly applied to decompose the DD residuals into the low-frequency bias and high-frequency noise components. The extracted bias components by WR are then directly applied to the DD observations to correct them from the trend. The remaining terms, largely characterized by the high-frequency measurement noise, are expected to give the best linear unbiased solutions from a least-squares (LS) adjustment. An experiment was carried out using objects placed close to the receiver antenna to cause, mainly, low-frequency multipath. The data were collected for two days to verify the multipath repeatability. The ground truth coordinates were computed with data collected in the absence of the reflector objects. The coordinates and ambiguity solution were compared with and without the multipath mitigation using WR. After mitigating the multipath, ambiguity resolution became more reliable and the coordinates were more accurate.

Environmental evaluation of cogeneration scenarios in sugar industry

The development of new techniques that allow the analysis and optimization of energy systems bearing in mind environmental issues is indispensable in a world with finite natural resources and growing demand of energy. Among the energy systems that deserve special attention, cogeneration in the sugar industry must be pointed out, because it uses efficiently a common fuel for generation of useful heat and power. Within this frame, thermoeconomical optimization - 2nd Law of Thermodynamics analysis by exergy function and economic evaluation of the thermal system - gradually is taking importance as a powerful tool to assist to the decision making process. Also, the explicit consideration of environmental issues offers a better way to explore trade-offs between different aspects to support the decisions that must be made. In this work it is used the technique of Life Cycle Analysis (LCA) which allows to consider environmental matters as an integral part of the problem, in opposite to most of the environmental approaches that only reduce residuals generation , without taking into account impacts associated to other related processes. On the other hand, the consideration of environmental issues in optimization of energy systems is a novel and promissory contribution in the state of the art of energy optimization and LCA. The system under study is a sugar plant of Tucumán (Argentina) given the particular importance that this industry had inside the regional economy of the Argentinean Northwest. Although cogeneration comes being used a while ago in sugar industry, being the main objective the generation of heat and as secondary objective the electric power generation and mechanic power to cover several needs of working machineries, to the date it is no available a versatile tool that allows to analyze economical feasible alternatives bearing in mind environmental issues. At sugar plants, steam is generated in boilers using as fuel bagasse - cellulosic fiber waste obtained crushing the sugar cane- and it is used to give useful heat and shaft work to the plant, but it can also be used to generate electricity with export opportunities to the electrical network. The great number of process alternatives outlines a serious decision making problem in order to take advantage of the resources. Although the problem turns out to be a mixed non-linear problem (MINLP), the main contribution of this work is the development of a hybrid strategy to evaluate cogeneration alternatives that combines optimization approaches with environmental indicators. This powerful tool for its versatility and robustness to analyze cogeneration systems, will be of great help in the decision making process, because of their easy implementation to analyze the kind of problems presented in the sugar industry.

Alignment of the CMS silicon tracker during commissioning with cosmic rays

The CMS silicon tracker, consisting of 1440 silicon pixel and 15 148 silicon strip detector modules, has been aligned using more than three million cosmic ray charged particles, with additional information from optical surveys. The positions of the modules were determined with respect to cosmic ray trajectories to an average precision of 3-4 microns RMS in the barrel and 3-14 microns RMS in the endcap in the most sensitive coordinate. The results have been validated by several studies, including laser beam cross-checks, track fit self-consistency, track residuals in overlapping module regions, and track parameter resolution, and are compared with predictions obtained from simulation. Correlated systematic effects have been investigated. The track parameter resolutions obtained with this alignment are close to the design performance. © 2010 IOP Publishing Ltd and SISSA.

Concentrations of Cu, Fe, Mn, and Zn in tropical soils amended with sewage sludge and composted sewage sludge

Sewage sludge may be used as an agricultural fertilizer, but the practice has been criticized because sludge may contain trace elements and pathogens. The aim of this study was to compare the effectiveness of total and pseudototal extractants of Cu, Fe, Mn, and Zn, and to compare the results with the bioavailable concentrations of these elements to maize and sugarcane in a soil that was amended with sewage sludge for 13 consecutive years and in a separate soil that was amended a single time with sewage sludge and composted sewage sludge. The 13-year amendment experiment involved 3 rates of sludge (5, 10, and 20 t ha-1). The one-time amendment experiment involved treatments reflecting 50, 100, and 200 % of values stipulated by current legislation. The metal concentrations extracted by aqua regia (AR) were more similar to those obtained by Environmental Protection Agency (EPA) 3052 than to those obtained by EPA3051, and the strongest correlation was observed between pseudo(total) concentrations extracted by AR and EPA3052 and bioavailable concentrations obtained by Mehlich III. An effect of sewage sludge amendment on the concentrations of heavy metals was only observed in samples from the 13-year experiment. © 2012 Springer Science+Business Media B.V.

Generating virtual images from oblique frames

Image acquisition systems based on multi-head arrangement of digital camerasare attractive alternatives enabling a larger imaging area when compared to a single framecamera. The calibration of this kind of system can be performed in several steps or byusing simultaneous bundle adjustment with relative orientation stability constraints. Thepaper will address the details of the steps of the proposed approach for system calibration,image rectification, registration and fusion. Experiments with terrestrial and aerial imagesacquired with two Fuji FinePix S3Pro cameras were performed. The experiments focusedon the assessment of the results of self-calibrating bundle adjustment with and withoutrelative orientation constraints and the effects to the registration and fusion when generatingvirtual images. The experiments have shown that the images can be accurately rectified andregistered with the proposed approach, achieving residuals smaller than one pixel. © 2013 by the authors; licensee MDPI, Basel, Switzerland.

Multicontroladores para melhoria da robustez e acomodação de falhas em sistemas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)