The isotope exchange depth profiling (IEDP) technique using SIMS and LEIS

The determination of the mass transport kinetics of oxide materials for use in electrochemical systems such as fuel cells, sensors and oxygen separators is a significant challenge. Several techniques have been proposed to derive these data experimentally with only the oxygen isotope exchange depth profile technique coupled with secondary ion mass spectrometry (SIMS) providing a direct measure of these kinetic parameters. Whilst this allows kinetic information to be obtained, there is a lack of knowledge of the surface chemistry of these complex processes. The advent of low-energy ion scattering (LEIS) now offers the opportunity of correlating exchange kinetics with chemical processes at materials atomic surfaces, giving unprecedented levels of information on electrochemical systems with isotopic discrimination. Here, the challenges of these techniques, including sample preparation, are discussed and the advantages of the combined approach of SIMS and LEIS illustrated with reference to key literature data.     

Derivation of Smoluchowski equations with corrections for Fokker-Planck and BGK collision models

The time evolution of the phase space distribution function for a classical particle in contact with a heat bath and in an external force field can be described by a kinetic equation. From this starting point, for either Fokker-Planck or BGK (Bhatnagar-Gross-Krook) collision models, we derive, with a projection operator technique, Smoluchowski equations for the configuration space density with corrections in reciprocal powers of the friction constant. For the Fokker-Planck model our results in Laplace space agree with Brinkman, and in the time domain, with Wilemski and Titulaer. For the BGK model, we find that the leading term is the familiar Smoluchowski equation, but the first correction term differs from the Fokker-Planck case primarily by the inclusion of a fourth order space derivative or super Burnett term. Finally, from the corrected Smoluchowski equations for both collision models, in the spirit of Kramers, we calculate the escape rate over a barrier to fifth order in the reciprocal friction constant, for a particle initially in a potential well.     

Formation of H and D atoms in pyrolysis of 1,3-butadiene and 1,3 butadiene-1,1,4,4,-d4 behind shock waves

Highly dilute mixtures of 1,3-butadiene and 1,3-butadiene-1,1,4,4-d₄ were pyrolyzed behind reflected and incident shock waves, respectively. Concentrations of H and D atoms were measured by resonance absorption spectroscopy. In the early stages of the reaction, nearly equal amounts of H and D were formed from CD₂CHCHCD₂, indicating that loss of H from C₂ followed by loss of D from C₁ is a more important reaction than breaking of the central C? C bond. Overall, rate constants for atom-forming reactions are much slower than rate constants for disappearance of butadiene in earlier experiments, suggesting that most of the butadiene disappears by processes that do not involve H or D atoms or by radicals that produce them rapidly.     

A new technique to examine individual pollutant particle and fibre deposition and transit behaviour in live mouse trachea

During respiration, particles suspended in the air are inhaled and unless cleared by airway defences they can remain and affect lung health. Their size precludes the use of standard imaging modalities so we have developed synchrotron phase-contrast X-ray imaging (PCXI) methods to non-invasively monitor the behaviour of individual particles in live mouse airways. In this study we used these techniques to examine post-deposition particle behaviour in the trachea. PCXI was used to monitor the deposition and subsequent behaviour of particles of quarry dust and lead ore; fibres of asbestos and fibreglass; and hollow glass micro-spheres. Visibility was examined in vitro and ex vivo to avoid the complicating effects of surrounding tissue and respiratory or cardiac motion. Particle behaviour was then examined after deposition onto the tracheal airway surfaces of live mice. Each particle and fibre looked and behaved differently on the airway surface. Particles lodged on the airway shortly after deposition, and the rate at which this occurred was dependent on the particle type and size. After the live-imaging experiments, excised airway samples were examined using light and electron microscopy. Evidence of particle capture into the airway surface fluids and the epithelial cell layer was found. PCXI is a valuable tool for examining post-deposition particulate behaviour in the tracheal airway. These first indications that the interaction between airways and individual particles may depend on the particle type and size should provide a novel approach to studying the early effects of respired particles on airway health.     

Effect of IR laser radiation on the structure and optical properties of PC-PBT/Pd polymer nanocomposite films

ABSTRACT

Bayfol (PC-PBT blend ?lm) is a class of polymeric solid-state nuclear track detector which has a lot of applications in several radiation detection ?elds. It is a bisphenol-A polycarbonate PC blended with polybutylene terephthalate PBT. Bayfol/Palladium (PC-PBT/Pd) nanocomposite films have been deposited using the molding technique. It is worth mentioning that this report is almost the first one dealing with the topic of the changes of physical properties of Bayfol/Pd nanocomposite due to laser exposure. Samples from PC-PBT/Pd (5?wt%) nanocomposite were exposed to IR-pulsed laser of 5-W power, capable of producing 2000 pulses per second with pulse duration of 200?ns at 904?nm. The laser fluences were in the range 2–25?J/cm². The resultant modi?cations in the exposed nanocomposite samples have been studied as a function of fluence using different characterization techniques such as X-ray diffraction (XRD), UV spectroscopy and color difference studies. The results indicate the proper dispersion of Pd nanoparticles in the PC-PBT matrix that causes a strong intermolecular interaction between Pd and PC-PBT, resulted in an increase in refractive index and the amorphous phase. Also, it is found that the laser exposure reduces the optical energy gap that could be attributed to the increase in structural disorder of the exposed PC-PBT/Pd nanocomposites due to crosslinking. Further, the color intensity ΔE, which is the color difference between the exposed samples and the non-exposed one, was increased with increasing the laser fluence, convoyed by a significant increase in the green and yellow color components.     

Distribution of hydraulic conductivity in single scale anisotropy

The cluster statistics of percolation theory are used to find the distributions of hydraulic conductivity, K, of anisotropic (truncated) random fractal media. Rescaling of variables to transform anisotropic to isotropic media also produces deformations of, for example experimental volumes, and the resulting non-equidimensional shapes may generate interesting size effects on K. Previously, the most likely value of K was obtained by comparing the correlation length from percolation theory with system dimensions, a procedure analogous to those developed for hopping conduction in disordered systems to calculate the longitudinal conductivity of thin films. The result probably explains the frequent tendencies of measurements of K in anisotropic fracture networks and agricultural soils to increase with the scale of measurement, similarly to how the longitudinal conductivity of a thick film would be larger than the corresponding conductivity of a thin film (three- rather than two-dimensional conduction). However, the same procedure applied to the conductivity in the perpendicular direction (analogous to the transverse electrical conductivity of a thin film) shows a diminishing function of spatial scale. Collectively, these ‘scale effects’ disappear if the shape of the experimental volume is selected to maintain the relationships of conduction in the various directions as the scale of the experiment is increased analogously to equidimensional volumes in isotropic media. The increase in K is, thus, merely due to an increase in the dimensionality of conduction from one to three with increasing system size. The paper, thus, provides a solid argument against a common assumption in the porous media communities that the connectivity of highly conducting regions of a medium should increase with increasing scale of measurement.     

Longitudinal dispersion of solutes in porous media solely by advection

The purpose of this work is to predict the transport of non-sorbing solutes through water flow in the subsurface. We derive what we consider to be the first reliable calculations of the entire distribution of arrival times, W(t), for non-sorbing solutes in advective flow in strongly disordered porous media. Solutes treated can be contaminant plumes from any source or radioactive tracers, both experimentally and naturally generated. Our approach is microscopic and based on effects of disorder. It generates longitudinal dispersion (in the direction of flow) in the absence of diffusion. Effects on dispersion from a single capillary tube velocity distribution, known to produce long-tailed arrival time distributions, are also neglected. On the other hand, our calculations are based on effects generated from real porous media, such as wide pore-size distributions and complex connectivity. In particular, the calculation of the distribution of arrival times is based on a distribution of conserved fluxes and the known tortuosity of the associated geometrical paths. The results are found to be predictive when compared with simulations of two-dimensional flow on percolation structures, and appear to have relevance for experiments as well.