A new approach to the modeling of SHS reactions: Combustion synthesis of transition metal aluminides

A recently developed numerical simulation of self-propagating high-temperature synthesis (SHS) using an approach based on microscopic reaction mechanisms and utilizing appropriate physical parameters is applied to the SHS of a fairly large group of transition metal aluminides. The model was utilized to analyze temperature profiles and wave instability and the results were interpreted in terms of chemical and thermal effects. The effect of the particle size of the transition metal, the porosity of the reactant mixtures, and the dilution was iinvestigated. The results are in good agreement with available experimental data

Ignition and reaction mechanism of Co-Al and Nb-Al intermetallic compounds prepared by combustion synthesis

The ignition and propagation mechanism of the self-propagating high-temperature synthesis of several cobalt and niobium aluminides was investigated. Two propagation mechanisms were identified depending on the stoichiometry of the starting mixture. Al-rich compositions propagate through a dissolution-precipitation mechanism while Al-poor mixtures require solid state diffusion. The ignition temperatures were measured by means of microthermocouples in quasi-adiabatic conditions through experiments carried out in thermal explosion mode. Ignition temperatures were found to be characteristic of each system and to depend strongly on reactants particle size. Ignition energies for all compositions were evaluated through a mathematical model

Nanoscale effects on the ionic conductivity of highly doped bulk nanometric cerium oxide

Nanometric ceria powders doped with 30 mol % samaria are consolidated by a high-pressure spark plasma sintering (HP-SPS) method to form > 99 % dense samples with a crystallite size as small as 16.5 nm. A conductivity dependence on grain size was noted: when the grain size was less than 20 nm, only one semicircle in the AC impedance spectra was observed and was attributed to bulk conductivity. In contrast to previous observations on pure ceria, the disappearance of the grain-boundary blocking effect is not associated with mixed conductivity. With annealing and concomitant grain growth, the samples show the presence of a grain-boundary effect

Dependence of the Ce(III)/Ce(IV) ratio on intracellular localization in ceria nanoparticles internalized by human cells

CeO2 nanoparticles (CNPs) have been investigated as promising antioxidant agents with significant activity in the therapy of diseases involving free radicals or oxidative stress. However, the exact mechanism responsible for CNP activity has not been completely elucidated. In particular, in situ evidence of modification of the oxidative state of CNPs in human cells and their evolution during cell internalization and subsequent intracellular distribution has never been presented. In this study we investigated modification of the Ce(iii)/Ce(iv) ratio following internalization in human cells by X-ray absorption near edge spectroscopy (XANES). From this analysis on cell pellets, we observed that CNPs incubated for 24 h showed a significant increase in Ce(iii). By coupling on individual cells synchrotron micro-X-ray fluorescence (μXRF) with micro-XANES (μXANES) we demonstrated that the Ce(iii)/Ce(iv) ratio is also dependent on CNP intracellular localization. The regions with the highest CNP concentrations, suggested to be endolysosomes by transmission electron microscopy, were characterized by Ce atoms in the Ce(iv) oxidation state, while a higher Ce(iii) content was observed in regions surrounding these areas. These observations suggest that the interaction of CNPs with cells involves a complex mechanism in which different cellular areas play different roles

Current effects on neck growth in the sintering of copper spheres to copper plates by the pulsed electric current method

The effect of a pulsed dc on the sintering of copper spheres to copper plates was investigated. It was shown that the current had a marked effect on neck growth between the spheres and the plates. The enhancement of sintering under the effect of the current was attributed to electromigration. Microstructural observations on fracture surfaces of necks formed under high currents showed considerable void formation. It was also observed that the current resulted in increased evaporation and the formation of bunched evaporation steps. Formation of these steps and their location relative to the neck were consistent with current density distributions. The results of this investigation provide direct evidence for the role of the current in the sintering in the pulse electric current sintering method. (c) 2007 American Institute of Physics

Directional electromigration-enhanced interdiffususion in the Cu–Ni system

The effect of a dc on the interdiffusivity D in the Cu-Ni system was investigated over the temperature range of 650-850 degrees C and at current densities in the range of 0-1000 A cm(-2). Interdiffusivities were calculated using the Sauer-Freise-den Broeder method and the values calculated in the absence of a current were in agreement with previously published results. The influence of the current on D depended on its direction relative to the two interfaces in the trilayered Cu-Ni-Cu samples. When the electronic flow was from Ni to Cu (cocurrent interface), the interdiffusivity showed a marked increase relative to copper content but was unchanged when the electronic flow was from Cu to Ni (countercurrent interface). The increase of D in the cocurrent interface depended on concentration and temperature. At lower temperatures, the increase becomes significant at higher copper concentrations but for the same value of current density, the increase is apparent at lower concentrations. The effective activation energy of interdiffusivity depended on concentration and decreased with the application of a current. The decrease was largest for higher copper concentrations. The results are interpreted in terms of a proposed vacancy-atom interaction for copper with the implication that the electron wind effect on Cu is counteracted by the effect of vacancies. (c) 2007 American Institute of Physics

The absence of plasma in “spark plasma sintering”

Spark plasma sintering (SPS) is a remarkable method for synthesizing and consolidating a large variety of both novel and traditional materials. The process typically uses moderate uni-axial pressures (<100 MPa) in conjunction with a pulsing on-off DC current during operation. There are a number of mechanisms proposed to account for the enhanced sintering abilities of the SPS process. Of these mechanisms, the one most commonly put forth and the one that draws the most controversy involves the presence of momentary plasma generated between particles. This study employees three separate experimental methods in an attempt to determine the presence or absence of plasma during SPS. The methods employed include: in-situ atomic emission spectroscopy, direct visual observation and ultra-fast in-situ voltage measurements. It was found using these experimental techniques that no plasma is present during the SPS process. This result was confirmed using several different powders across a wide spectrum of SPS conditions