Synchrotron structural characterization of electrochemically synthesized hexacyanoferrates containing K(+): A revisited analysis of electrochemical redox

The presumably soluble KFe(+3)[Fe(2+)(CN)(6)] structure of electrochemically synthesized hexacyanoferrate materials (Prussian Blue) containing K(+) ions was determined for the first time in this study. Prior to drawing conclusions from a structural analysis, the main goal was to make a precise analysis of the inferred soluble structure, that is, KFe(+3) [Fe(2+)(CN)(6)], which is frequently referred to in the literature as the final stable electrochemically synthesized structure. Indeed, a successful X-ray powder diffraction experiment using X-ray synchrotron radiation was made of a powder placed in a 0.5 mm diameter borosilicate glass capillary, which was obtained by removing sixty 90 nm thin films from the substrates on which they were prepared. However, the conclusions were highly unexpected, because the structure showed that the [Fe(CN)61 group was absent from similar to 25% of the structure, invalidating the previously presumed soluble KFe(+3)[Fe(2+)(CN)(6)] structure. This information led to the conclusion that the real structure of Prussian Blue electrochemically synthesized after the stabilization process is Fe(4)[Fe(CN)(6)](3)center dot mH(2)O containing a certain fraction of inserted K(+) ions. In fact, based on an electrogravimetric analysis (Gimenez-Romero et al., J. Phys. Chem. B 2006, 110, 2715 and 19352) complemented by the Fourier maps. it is possible to affirm that the K(+) was part of the water crystalline substructure. Therefore, the interplay mechanism was reexamined considering more precisely the role played by the water crystalline substructure and the K+ alkali metal ion. As a final conclusion, it is proposed that the most precise way to represent the structure of electrochemically synthesized and stabilized hexacyanoferrate materials is Fe(4)(3+) Fe(2+)(CN)(6)](3)center dot[K(h)(+)center dot OH(h)(-)center dot mH(2)O]. The importance of this result is that the widespread use of the terms soluble and insoluble in the electrochemical literature could be reconsidered. Indeed, only one type of structure is insoluble, and that is Fe(4)[Fe(CN)(6)](3)center dot mH(2)O hence, the use of the terms soluble and insoluble is inappropriate from a structural point of view. The result of the presence of the [Fe(CN)61 vacancy a, roup is that the water Substructure cannot be ignored in the ionic interplay mechanism which controls the intercalation and redox process, as was previously confirmed by electrogravimetric analyses (Gimenez-Romero et al., J. Phys. Chem. B 2006, 110, 2715 Garcia-Jareno et al., Electrochim. Acta 1998, 44, 395: Kulesza, Inorg. Chem. 1990, 29, 2395).

Using thermal and spectroscopic data to investigate the thermal behavior of epinephrine

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

Redox Behavior of molybdenum and tungsten in phosphate glasses

In this work, vitreous samples were prepared in the binary system (100 - x)NaPO3-xMO(3) with M = Mo and W and x varying from 10 to 60. The transmittance properties in the UV, visible, and near-infrared were monitored as a function of MO3 concentration. In both cases, an increase in the amount of transition metal results in an intense and broad absorption band in the visible and near-infrared attributed to metal reduction under synthesis conditions. It was shown that this large absorption can be partially or totally removed using specific oxidizing agents or by improving synthesis parameters such as melting temperature or cooling rate of the melt. In addition, structural investigations by Raman and X-ray absorption spectroscopy suggest that reduction only occurs when the metal cation is in octahedral geometry and that the transmittance improvement is not related with any structural changes. These results were explained in terms of thermodynamic equilibrium of redox species in the melt and allowed to obtain for the first time transparent and chemically stable glasses containing high concentrations of MO3 with transition metals in octahedral geometry inside the glass network.

Synthesis and Structural Studies of Er3+ Containing Lead Cadmium Fluoroborate Glasses and Glass-Ceramics

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

Optical and structural properties of GaAs/GaInP quantum wells grown by Chemical Beam Epitaxy

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

Photoluminescent behavior of SrBi2Nb2O9 powders explained by means of beta-Bi2O3 phase

Photoluminescence (PL) behavior of SrBi2Nb2O9 (SBN) powders was explained by means of beta-Bi2O3 phase on the SBN lattice. Oxygen vacancies and recombination of electrons holes in the valence band lead to the formation of [NbO5 center dot V-O(x)], [NbO5 center dot V-O(center dot)] and [NbO5 center dot V-O(center dot center dot)] complex clusters which are the main reason for the PL at room temperature. X-ray diffraction and Fourier transform Raman spectroscopy were used as tools to investigate the structural changes in SBN lattice allowing to correlate [NbO5 center dot V-O(center dot)]/[NbO6](') ratio with the evolution of the visible PL emission in the SBN powders. (c) 2007 American Institute of Physics.

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO3-BaF2 WO3 tertiary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L-I and L-III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (≥ 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

Behavior of plant tissue in osmotic solutions

The effect of the concentration of sucrose solutions on the cellular structure of potato tissue in equilibrium at 27 degreesC was Studied. Two different methods of investigation were used to determine the volume of the different phases composing the cellular tissue of the potato when in equilibrium with the solutions. one based on data of the concentration itself and the overall volume of 2 mm slices after 48 h at equilibrium, and the other on microscopic images of cells in thin slices of fresh tissue stained with neutral red after an hour in equilibrium to show protoplasts, vacuoles and plasmolysis spaces. The results of these methods were compared with those obtained by a predictive thermodynamic approach considering the semipermeability of cell membranes. Phase volume data obtained from microscopic analysis were more similar to what was predicted by the theoretical model than those obtained by means of composition measurement. where the long equilibrium time apparently led to the loss of semi permeability of the cell membranes, since total volumes calculated without consideration of the cell membranes were similar to those measured. This suggests that the length of time of osmotic dehydration brings about a change in cell structure and the consequent involvement of a different mechanism in mass transfer. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Small-angle X-ray scattering study of the smart thermo-optical behavior of zirconyl aqueous colloids

The smart thermo-optical systems studied here are based on the unusual thermoreversible sol-gel transition of zirconyl chloride aqueous solution modified by sulfuric acid in the molar ratio Zr/SO4:3/1. The transparency to the visible light changes during heating due to light scattering. This feature is related to the aggregates growth that occurs during gelation. These reversible changes can be controlled by the amount of chloride ions in solution. The thermoreversible sol-gel transition temperature increases from 323 to 343 K by decreasing the molar ratio Cl/Zr from 7.0 to 1.3. In this work the effect of the concentration of chloride ions on the structural characteristics of the system has been analyzed by in situ SAXS measurements during the sol-gel transition carried out at 323 and 333 K. The experimental SAXS curves of sols exhibit three regions at small, medium and high scattering vectors characteristics of Guinier, fractal and Porod regimes, respectively. The radius of primary particles, obtained from the crossover between the fractal and Porod regimes, remains almost invariable with the chloride concentration, and the value (4 Angstrom) is consistent with the size of the molecular precursor. During the sol-gel transition the aggregates grow with a fractal structure and the fractal dimensionality decreases from 2.4 to 1.8. This last value is characteristic of a cluster-cluster aggregation controlled by a diffusion process. Furthermore, the time exponent of aggregate growth presents values of 0.33 and 1, typical of diffusional and hydrodynamic motions. A crossover between these two regimes is observed.

Influence of Environmental Conditioning on the Shear Behavior of Poly(phenylene sulfide)/Glass Fiber Composites

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Synthesis and photoluminescence behavior of Bi4Ti3O12 powders obtained by the complex polymerization method

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis and electrochemical behavior of single-crystal magnetite nanoparticles

Water-dispersed magnetite nanoparticle synthesis from iron(II) chloride in dimethyl sulfoxide (DMSO)-water solution at different DMSO-water ratios in alkaline medium was reported. TEM and XRD results suggest a single-crystal formation with mean particle size in the range 4-27 nm. Magnetic nanoparticles are formed by the oxidative hydrolysis reaction from green rust species that leads to FeOOH formation, followed by autocatalysis of the adsorbed available Fe(II) on the FeOOH surfaces. The available hydroxyl groups seem to be dependent on the DMSO-water ratio due to strong molecular interactions presented by the solvent mixture. Goethite phase on the magnetite surface was observed by XRD data only for sample synthesized in the absence of DMSO. In addition, cyclic voltammetry with carbon paste electroactive electrode (CV-CPEE) results reveal two reduction peaks near 0 and +400 mV associated with the presence of iron(III) in different chemical environments related to the surface composition of magnetite nanoparticles. The peak near +400 mV is related to a passivate thin layer surface such as goethite on the magnetite nanoparticle, assigned to the intensive hydrolysis reaction due to strong interactions between DMSO-water molecules in the initial solvent mixture that result in a hydroxyl group excess in the medium. Pure magnetite phase was only observed in the samples prepared at 30% (30W) and 80% (80W) water in DMSO in agreement with the structured molecular solvent cluster formation. The goethite phase present on the, magnetite nanoparticle surface like a thin passivate layer only was detectable using CV-CPEE, which is a very efficient, cheap, and powerful tool for surface characterization, and it is able to determine the passivate oxyhydroxide or oxide thin layer presence on the nanoparticle surface.

Analysis of aluminum plates under heating in electrical and natural gas furnaces

This paper analyzes the thermal storage characteristics of aluminum plates in furnaces during their heating for lamination under two sources of heat: an electrical resistance bank and a combustion process carried out with natural gas. The set of equations to model the furnace under operation with electrical energy, for air as the fluid, is presented. This supports the theoretical analysis for the system under operation with natural gas combustion products. A numerical procedure, using the software ANSYS, is applied to determine the convection heat transfer coefficients for heating by the air flow. Temperatures measured in a plate inside a real furnace are used as parameters to determine these coefficients. Then convection and radiation heat transfer coefficients are determined for the natural gas combustion products. Results are compared, indicating a possible gain of 5.5 h in relation to a 19.5 h period of conventional electrical heating per plate.

Structural analyzes of the use of residues of tires in reinforced concrete

The search for an adequate destination to the tires without use is a problem for many countries. The use of tire rubber in concrete through the partial substitution of the small aggregate has for objective the withdrawal of this material of the environment besides serving as alternative material in places that present sand scarcity. However, to use this type of concrete in civil construction it's necessary to verify its structural behavior. The behavior of the adherence enters the bar of armor and the concrete surrounding it has decisive importance with relation to the load capacity of the structures of reinforced concrete. In this context, this work presents, argues and evaluates the results of the experimental studies for determination of the adherence tension according to pulling up assays pull-out normalized for CEB RC6 and also related in the ASTM C-234 in concrete with and without rubber residues. Armors of nominal diameter of 10,0; 12,5 and 16 mm had been used and concrete contend 10% of rubber fibres in substitution to the sand in volume.

Comparison of the biological behavior of wollastonite bioceramics prepared from synthetic and natural precursors

Wollastonite bioceramics prepared from synthetic and natural precursors were implanted in rats in bone and subcutaneous tissues. The implant sites were excised after 7, 30 and 120 days, fixed, dehydrated, embedded in paraffin wax for serial cutting and examined under transmitted light microscope. It was found a very similar behavior for both wollastonite bioceramics. They were biocompatible, bioactive and biodegradable when implanted in rat bone. The synthetic ceramic was more reabsorbable than the one from natural powder. When implanted in subcutaneous rat tissue, both materials elicited a mild initial inflammatory reaction that practically disappeared after 120 days. Both materials were encapsulated with a very thin fibrous capsule and slightly reabsorbed at their surfaces. None of the materials induced ectopic osteogenesis. According to the results, the studied materials seem to be able for manufacturing reabsorbable bone implants.