Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell

The electrocatalysis of CO tolerance of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C at a PEM fuel cell anode has been investigated using single cell polarization and online electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), in situ X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO(2) start at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particulary for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H(2)/CO, the formation of CO(2) is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. (C) 2008 Elsevier Ltd. All rights reserved.

Application of multivariable control using artificial neural networks in a debutanizer distillation column

LOPES, Jose Soares Batista et al. Application of multivariable control using artificial neural networks in a debutanizer distillation column.In: INTERNATIONAL CONGRESS OF MECHANICAL ENGINEERING - COBEM, 19, 5-9 nov. 2007, Brasilia. Anais... Brasilia, 2007

Ambiente de simulação híbrido integrando hysys e rede industrial Foundation Fieldbus aplicado ao controle de uma coluna de destilação

The main purpose of this work is to develop an environment that allows HYSYS R chemical process simulator communication with sensors and actuators from a Foundation Fieldbus industrial network. The environment is considered a hybrid resource since it has a real portion (industrial network) and a simulated one (process) with all measurement and control signals also real. It is possible to reproduce different industrial process dynamics without being required any physical network modification, enabling simulation of some situations that exist in a real industrial environment. This feature testifies the environment flexibility. In this work, a distillation column is simulated through HYSYS R with all its variables measured and controlled by Foundation Fieldbus devices

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

Construção de um sistema de caracterização das propriedades de transporte de filmes finos pelo efeito Hall

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Determination of the properties of an experimental glass polyalkenoate cement prepared from niobium silicate powder containing fluoride

Objectives. The purpose of this paper is to modify the conventional calcium fluoro-aluminosilicate glass, which is used in the formation of glass ionomer cements (CIGs) by the niobium addition and to study the properties of GICs obtained.Materials and methods. Sol-gel process was used to prepare the powder at lower temperature than fusion method. Glass-ceramic powder obtained in this way was used to prepare the GICs. The properties such as working and setting times, microhardness and diametral tensile strength were evaluated for the experimental GICs and a commercial luting cement.Results. The ideal powder:liquid (P:L) ratio determined to prepare the experimental GICs was equal to 1:1. The cements prepared using this ratio showed working and setting times similar to the commercial GICs. in mechanical tests it was observed that microhardness and diametral tensile strength of the experimental GICs decreased significantly with the reduction of P:L ratio. on the other hand, the results obtained in microhardness tests indicated that the presence of niobium was a positive factor.Significance. The chemical process allows the development of glass-ceramic powder at 600 degrees C which is the goal of the present paper. It was concluded that GICs containing niobium might be used in dental applications and these results encourage further researches on other compositions. (c) 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Comparison of crystallinity between natural hydroxyapatite and synthetic cp-Ti /HA coatings

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Recobrimento de apatitas in vitro sobre titânio: influência do tratamento térmico

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Characterization of amorphous niobium silicates powders synthesized by polymeric precursor method

In this paper 4.5SiO(2)-3Al(2)O(3-x)Nb(2)O(5)-2CaO powders have been synthesized using a chemical process the Polymeric Precursor Method. The process of glass formation has been investigated by XRD and DTA, the results confirm that the prepared powders are glasses. Experimental data show that amount of Nb2O5 had a considerable effect on the T-g values. The structures of glasses prepared. have been determined by Si-29 and Al-27 MAS NMR and the results indicated that the network is formed by SiO4 and AlO4 tetrahedral linked and probably Si-O-Nb bonds are present in the vitreous network. (C) 2005 Elsevier B.V. All rights reserved.

A novel approach for the development of photoluminescent material

We report on several amorphous compounds based on different metal oxianions with intense photoluminescence at room temperature. These compounds were synthesised by a soft chemical process and deposited on Si (100) by a spin-coating technique. To select these different metal oxianions, a classic concept based on a metal oxide network former is used. We describe a minimum set of requirements to obtain an amorphous metal oxide with photoluminescence emission at room temperature.

Electrical conduction mechanism and phase transition studies using dielectric properties and Raman spectroscopy in ferroelectric Pb0.76Ca0.24TiO3 thin films

We have studied the phase transition behavior of Pb0.76Ca0.24TiO3 thin films using Raman scattering and dielectric measurement techniques. We also have studied the leakage current conduction mechanism as a function of temperature for these thin films on platinized silicon substrates. A Pb0.76Ca0.24TiO3 thin film was prepared using a soft chemical process, called the polymeric precursor method. The results showed that the dependence of the dielectric constant upon the frequency does not reveal any relaxor behavior. However, a diffuse character-type phase transition was observed upon transformation from a cubic paraelectric phase to a tetragonal ferroelectric phase. The temperature dependency of Raman scattering spectra was investigated through the ferroelectric phase transition. The soft mode showed a marked dependence on temperature and its disappearance at about 598 K. on the other hand, Raman modes persist above the tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive above the phase transition temperature. The origin of these modes must be interpreted in terms of a local breakdown of cubic symmetry by some kind of disorder. The lack of a well-defined transition temperature suggested a diffuse-type phase transition. This result corroborate the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in the thin film. The leakage current density of the PCT24 thin film was studied at elevated temperatures, and the data were well fitted by the Schottky emission model. The Schottky barrier height of the PCT24 thin film was estimated to be 1.49 eV. (C) 2003 American Institute of Physics.

Effect of boron powder purity on superconducting properties of MgB2

The effect of the properties of starting boron powders on the superconducting properties of MgB2 has been studied. The 92% and 96% pure powders produce lower surface reactivity and larger particle size than the 99% boron powder, as can be seen from Brunauer - Emmett - Teller (BET) and scanning electron microscopy (SEM) results, indicating that the low purity powders cannot be used to archive the same superconducting properties as those of samples made from pure 99% boron powder. However, the purity of 92% and 96% boron powders can be improved by using a simple chemical process, leading to enhanced magnetic critical current densities J(c). From x-ray diffraction (XRD) measurement, oxide impurity has been observed, which might be originated from the B2O3 phase in the boron powders. In order to get high performance MgB2, it is obviously important to control the phase composition and microstructure of amorphous boron starting powders and solid reaction conditions.

An investigation of metal oxides which are photoluminiscent at room temperature

Amorphous thin films, based on different network formers, were processed by a soft chemical process called the polymeric precursor method. The resultant amorphous metal oxides, displayed intense photoluminescence (PL) at room temperature. Heat treatment increases the PL intensity of these materials. Theoretical ab initio calculations are correlated with the observed experimental trends. (C) 2004 Elsevier B.V. All rights reserved.

Structural and ferroelectric properties of Pb1-xSrxTiO3 thin films

Strontium-modified lead titanate (PST) thin films with composition Pb1-xSrxTiO3 (0.10 < x &LE; 0.60) were grown on Pt/Ti/SiO2/Si substrates using a soft chemical process. The crystallization of the PST thin films was achieved by heat treatment at 600&DEG;C. The structural and microstructural modifications in the films were studied using X-ray diffraction (XRD) and atomic force microscopy, respectively. The XRD study shows that the lattice parameters of polycrystalline PST thin films calculated from X-ray data indicate a decrease in lattice tetragonality with the increase in strontium content in these films. This indicates a gradual change from tetragonal to cubic structure. By atomic force microscopy analysis, the average grain size of the thin films was systematically reduced with the increase in Sr content. The dielectric property of the thin films was found to be strongly dependent on the Sr concentration. With 60 at.% Sr content, a ferroelectric to paraelectric phase transition was observed at room temperature.

Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.