Microstructural characteristics and electrochemical behavior of Co3O4 sintered electrodes

Co3O4 can be used as electrocatalyst for oxygen evolution reaction. The macro and microstructure of the oxide, obtained by compacting and sintering lithium-doped Co3O4 powder in atmosphere of dry air and in conditions of controlled temperature and time was analyzed by metallographic techniques. The porous material was characterized by XRD, SEM and EDS combined techniques. For working temperatures up to 1200°C, the pellet was consituted of particles with varying sizes over a wide range of particle size and, at higher temperatures CoO is formed and polymorphic transformation was observed. The materials were also characterized electrochemically in alkaline media by open circuit potential and potentiodynamic I/E measurements. The results were compared to those previously prepared by others by thermal deposition.

The Bauru Group: A continental Cretaceous unit in Brazil - Concepts based on micropaleontological, oxygen isotope and stratigraphical data

The integration of outcrop and subsurface information, including micropaleontological data, facies and sequence stratigraphic studies, and oxygen isotope analysis, allow us to present a new stratigraphic model for the Cretaceous continental deposits of the Bauru Group, Brazil. Thirty-eight fossil taxa were recovered from these deposits, including 29 species of ostracodes and 9 species of charophytes. Seven of these ostracode species and three subspecies are new and formally described here. The associations of Chara barbosai - Ilyocypris cf. riograndensis, found in the Adamantina Formation, and Amblyochara sp. - Neuquenocypris minor mineira nov. subsp., found in the Marília Formation. Ponte Alta Member, represent two distinct groups that are respectively Turonian-Santonian and Maastrichtian (probably Late Maastrichtian) in age. Therefore, a hiatus, encompassing more than 11 Ma, separates those two formations. From bottom to top, four depositional cycles were recognized in the Bauru Group in western São Paulo: cycles 1 and 2 belong to Caiuá Formation (fluvio-lacustrine and lacustrine deposits in the Presidente Prudente region), cycle 3 to the Santo Anastácio and lower Adamantina Formation (respectively fluvial and lacustrine deposits), and cycle 4 to the upper Adamantina Formation (fluvio-lacustrine facies). An erosional unconformity separates the Caiuá and Santo Anastácio Formations (between cycles 2 and 3). The Marília Formation is a distinct unit from the underlying succession; it does not occur in western São Paulo, but is found in restricted areas of São Paulo, Minas Gerais, Mato Grosso do Sul and Goiás States. During the deposition of the Bauru Group (Aptian? to Maastrichtian) the climate was hot and arid-semiarid. Shallow lakes underwent fluctuations in expansion (wet phases) and contraction (dry phases), as well as variations in salinity. During the deposition of the Adamantina Formation (Turonian-Santonian) there were long, dry periods that caused segmentation of large lakes (due to topographic irregularities in the basaltic substrate) and sometimes exposures of the lake floors; when flooded these lake floors were colonized by extensive meadows of single species of charophytes. Small ephemeral ponds, that were hydrochemically unstable and colonized by multiple species of charophytes, were the depositional sites for the marls and mudstones of Ponte Alta Member (Maastrichtian, Late Maastrichtian?). Our micropaleontological age control, combined with the Late Cretaceous ages of volcanic ashes found in the southeastern Brazil coastal basins, and the stratigraphic position of analcimites from the Jaboticabal-SP region, suggest a Late Coniacian-Santonian age for important magmatic events occurred in the interior of Brazil (north-central São Paulo State, Triângulo Mineiro, and southwestern Goiás State).

Solid-state NMR, ionic conductivity, and thermal studies of lithium-doped siloxane-poly(propylene glycol) organic-inorganic nanocomposites

Hybrid organic-inorganic ionic conductors, also called ormolytes (organically modified electrolytes), were obtained by dissolution of LiClO 4 in siloxane-poly(propylene glycol) matrixes. The dynamic features of these nanocomposites were studied and correlated to their electrical properties. Solid-state nuclear magnetic resonance (NMR) spectroscopy was used to probe the effects of the temperature and nanocomposite composition on the dynamic behaviors of both the ionic species ( 7Li) and the polymer chains ( 13C). NMR, dc ionic conductivity, and DSC results demonstrate that the Li + mobility is strongly assisted by the segmental motion of the polymer chain above its glass transition temperature. The ac ionic conductivity in such composites is explained by use of the random free energy barrier (RFEB) model, which is agreement with their disordered and heterogenous structures. These solid ormolytes are transparent and flexible, and they exhibit good ionic conductivity at room temperature (up to 10 -4 S/cm). Consequently, they are very promising candidates for use in several applications such as batteries, sensors, and electrochromic and photoelectro-chemical devices.

Contribution of oxygen related defects to the electronic transport in SnO2 sol-gel films

SnO2 deposited by sol-gel is a polycrystalline film with small grain size. Oxygen present at a less grain boundary traps electrons and then the depletion layer around the potential barrier of the grain boundary becomes wider, comparable to the grain size. We have modeled the conductivity taking into account the trapped charge at the depletion layer of the grain boundary and other scattering mechanisms such as ionized impurity and polar optical. Experimental data of photoconductivity of SnO2 sol-gel films are simulated considering the dominant scattering at grain boundary and crystallite bulk. The fraction of trapped charge at the grain boundary depends on temperature and wavelength of irradiating light, being as high as 50% for illumination in the range 500-600 nm for SnO2-2%Nb as grown sample annealed in air to 550°C. This fraction can be quite reduced depending on exposure to light and annealing under different oxygen partial pressure conditions.

Oxygen uptake kinetics and time to exhaustion in cycling and running: A comparison between trained and untrained subjects

The objective of the present study was to compare pulmonary gas exchange kinetics (VO 2 kinetics) and time to exhaustion (Tlim) between trained and untrained individuals during severe exercise performed on a cycle ergometer and treadmill. Eleven untrained males in running (UR) and cycling (UC), nine endurance cyclists (EC), and seven endurance runners (ER) were submitted to the following tests on separate days: (i) incremental test for determination of maximal oxygen uptake (VO 2max) and the intensity associated with the achievement of VO 2max (IVO 2max) on a mechanical braked cycle ergometer (EC and UC) and on a treadmill (ER and UR); (ii) all-out exercise bout performed at IVO 2max to determine the time to exhaustion at IVO 2max (Tlim) and the time constant of oxygen uptake kinetics (τ). The τ was significantly faster in trained group, both in cycling (EC = 28.2 ± 4.7 s; UC = 63.8 ± 25.0 s) and in running (ER = 28.5 ± 8.5 s; UR = 59.3 ± 12.0 s). Tlim of untrained was significantly lower in cycling (EC = 384.4 ± 66.6 s vs. UC; 311.1 ± 105.7 s) and higher in running (ER = 309.2 ± 176.6 s vs. UR = 439.8 ± 104.2 s). We conclude that the VO 2 kinetic response at the onset of severe exercise, carried out at the same relative intensity is sensitive to endurance training, irrespective of the exercise type. The endurance training seems to differently influence Tlim during exercise at IVO 2max in running and cycling. © 2003 Taylor & Francis Ltd.

Quantitative structural analysis of the transition from LT-Li xCoO2 to HT-LixCoO2 using the rietveld method: Correlation between structure and electrochemical performance

A quantitative phase analysis was made of LixCoO2 powders obtained by two distinct chemical methodologies at different temperatures (from 400 to 700°C). A phase analysis was made using Rietveld refinements based on X-ray diffraction data, considering the Li xCoO2 powders as a multiphase system that simultaneously contained two main phases with distinct, layered and spinel-type structures. The results showed the coexistence of both structures in LixCoO 2 obtained at low temperature (400 and 500°C), although only the layered structure was detected at higher temperatures (600 and 700°C), regardless of the chemical powder process employed. The electrochemical performance, evaluated mainly by the cycling reversibility of Li xCoO2 in the form of cathode insertion electrodes, revealed that there is a close correlation between structural features and the electrochemical response, with one of the redox processes (3.3 v/3.9 v) associated only with the presence of the spinel-type structure. © 2003 Elsevier B.V. All rights reserved.

Anelastic spectroscopy in TiO2

Titanium dioxide (rutile) has a lot of interesting and useful features and hence is widely utilized for application. It has been used as white pigment, photocatalyst, biocompatible material and semiconductor material used in solar battery. In semiconducting TiO2 oxygen vacancies are said to play an important role in the electrical conduction. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature can distinguish among the different atomic jumps, which occur in the various phases or at different local ordering. In this paper, it is reported anelastic relaxation measurements in TiO2 samples using a torsion pendulum operating in frequencies around 40Hz, in the temperature range between -173°C to 330°C with heating rate of 1°C/min. The results shown a reduction in the elasticity modulus with the increase in the corn starch content used for this consolidation.

Effect of thermal treatment under oxygen atmosphere on the superconducting properties of RuSr2GdCu2O8

The discovery of the spatial uniform coexistence of superconductivity and ferromagnetism in rutheno-cuprates, RuSr2GdCu2O8 (Ru-1212), has spurred an extraordinary development in the study of the competition between magnetism and superconductivity. However, several points of their preparation process and characterization that determine their superconductive behavior are still obscure. The improvement of sample preparation conditions involves some thermal treatments in inert atmosphere. The first treatment results in the immediate formation of Sr2GdRuO 6. Using the CuO composition as a precursor, we produced Ru-1212. To turn it metallic and superconductor, besides the previous treatment, a final sinterization is carried out in oxygen flow for several days. Three Ru-1212 samples were produced by varying the last sinterization time (two, four, and six days under oxygen flow). Through measurements of x-ray diffraction, scanning electron microscopy, differential thermal analysis, magnetic susceptibility and mechanical spectroscopy, it was studied the influence of the treatments under oxygen atmosphere on the structural and superconducting properties of the material.

Does cotinine act upon reactive oxygen species and peroxidases?

Nicotine, an oxidizing agent, is certainly one of the most widely used alkaloids in the world. It is, together with its main metabolite, cotinine, responsible for tobacco-dependence. The use of tobacco is closely associated with lung disease, morphological leukocyte modification and generation of oxidant species. The aim of this study was to look for a possible relationship between cotinine, oxidant species generation and oxidative processes. After studying the action of cotinine in some chemical oxidation models and on the enzymatic kinetics of peroxidases (myeloperoxidase and horseradish peroxidase), we concluded that cotinine does not act directly upon H 2O 2, HOCl, taurine chloramines, horseradish peroxidase or myeloperoxidase.

Profile of Maytenus aquifolium action over free radicals and reactive oxygen species

Reactive oxygen species (ROS) and free radical species have been implicated in initiating, accompanying or causing many diseases in living organisms; there is thus, a continual need for antioxidants molecules to inactivate ROS/free radicals. Many studies of plants crude extracts have demonstrated free-radical scavenging and antioxidant action. Maytenus species have long been used, in several countries, as traditional medicines against gastric ulcers, dyspepsia and others gastric problems and for their anti-inflammatory properties. In this study, Maytenus aquifolium (Celastraceae) root bark ethanol extract was assessed for its ability to scavenge free radicals and reactive oxygen species. The results were expressed as percentage inhibition of the active species. The extract was efficient against studied reactive species: DPPH radical (obtained inhibition = 35.5 ± 1.3 %), ABTS.+ (IC50 = 0.0036 ± 0.0003 mg/mL), HOCl (IC50 = 0.002 ± 0.0001 mg/mL), O2 .- (obtained inhibition = 36.0 ± 2.1 %), and NO. (obtained inhibition = 18.3 ± 0.4 %). Uniterms Oxidant species Free radicals Maytenus aquifolium Oxidative damage.

Mechanical damping of the snoek peak in tantalum - Oxygen system

Interstitial solutes in body-centered cubic metals, such as oxygen in tantalum, produce ideally Snoek effects when they are in solutions enough diluted. However, for higher concentration of these solutes, more complex relaxation process can occur, as interaction between interstitial solutes and dislocations. Anelastic relaxation measurements were carried out in polycrystalline tantalum samples, using torsion pendulum inverted, operating between 300 K and 680 K and oscillation frequencies in the hertz bandwidth, for three different experimental sample conditions: as received sample, annealed and annealed followed by a treatment in an oxygen atmosphere. These measurements have revealed the following behavior: the intensity of the internal friction peak associated to matrix-interstitial interaction Ta-O decreased between the first run and the next runs, and this phenomenon did not occur for the others conditions. The variation of relaxation strength of Ta-O peak, with number of runs is due to a decrease of an amount of oxygen in solid solution, which can be associated with the precipitation of new phases in Ta sample and with the trapping of oxygen atoms by dislocations.

Oxygen reduction on PtFe/C electrocatalysts prepared in microemulsions

PtFe/C nanocatalysts of different compositions and nearly constant particle size were prepared by a microemulsion method. Crystallite sizes and degree of alloying were determined by X-ray diffraction. Particle size and distribution were characterized by transmission electron microscopy and average composition was determined by energy dispersive X-ray analysis. Measurements of electrocatalytic activity for oxygen reduction were done using the rotating disk electrode technique in O2 saturated 0.5 mol L-1 sulfuric acid solutions, at room temperature. For all catalysts oxygen reduction begins at ̃ 0.90V. Tafel plots show slopes of c.a. 60 and 120 mV dec in the regions of low and high overpotentials, respectively. The best results for the ORR were obtained for the PtFe/C catalyst of composition Pt:Fe 70:30. This catalyst was also found to exhibit the largest methanol tolerance. © The Electrochemical Society.