Point defects in potassium thiocyanate: Impurity diffusion and conduction in lead-doped crystals

The diffusion rates of ${}^{210}\text{Pb}{}^{\mathrm{2+}}$ and ${}^{35}\text{S}{}^{\mathrm{2?}}$ into single crystals of nominally pure potassium thiocyanate have been measured. The impurity diffusion coefficients are about 1% of the values for the host anion and cation (reported previously), and this supports the view that ionic diffusion in this solid occurs mainly via a vacancy pair process. The electrical conductivity of polycrystalline samples of KSCN doped with Pb²⁺ has been measured as a function of temperature and of lead content. The results show that cation vacancies are mobile in the solid and that the overall conduction behavior of KSCN is dominated by impurity effects.     

Approaching non-destructive surface chemical analysis of CMSX-4 superalloy with double-pulsed laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) was performed on the CMSX-4 Ni-based superalloy using a femtosecond pulsed laser. An orthogonal double-pulse technique was used to minimize surface damage associated with LIBS. With this technique, the depth of ablation craters was reduced from 200 nm for single-pulse LIBS down to less than 60 nm using orthogonal double-pulse LIBS. The technique also allowed the average velocity of the ablated material to be determined, which ranged from 4720 ± 560 m/s at a pump laser fluence of 3.1 J/cm² to 8150 ±1800 m/s at 10.1 J/cm².     

Fluoroarylphosphines as ligands

This short review concentrates on important aspects of fluoroarylphosphines, in particular their synthesis, ligand properties and chemical and catalytic properties of their complexes. Although the electronic, steric and chemical properties of fluoroarylphosphines have been known for 30 years, their use as ligands for homogeneous catalysis and in the synthesis of elaborate multidentate ligands has occurred more recently. The number of recent reports suggests that their importance is growing.     

High-Resolution Deformation Mapping Across Large Fields of View Using Scanning Electron Microscopy and Digital Image Correlation

This paper details the creation of experimental and computational frameworks to capture high-resolution, microscale deformation mechanisms and their relation to microstructure over large (mm-scale) fields of view. Scanning electron microscopy with custom automation and external beam control was used to capture 209 low-distortion micrographs of 360 μm?×?360 μm each, that were individually correlated using digital image correlation to obtain displacement/strain fields with a spatial resolution of 0.44 μm. Displacement and strain fields, as well as secondary electron images, were subsequently stitched to create a 5.7 mm × 3.4 mm field of view containing 100 million (7678?×?13,004) data points. This approach was demonstrated on Mg WE43 under uniaxial compression, where effective strain was shown to be relatively constant with respect to distance from the grain boundary, and a noticeable increase in the effective strain was found with an increase in the basal Schmid factor. The ability to obtain high-resolution deformations over statistically relevant fields of view enables large data analytics to examine interactions between microstructure, microscale strain localizations, and macroscopic properties.     

Measurement of Strain Localization Resulting from Monotonic and Cyclic Loading at 650 <Superscript>∘</Superscript>C in Nickel Base Superalloys

A methodology is presented for the use of the oxide scale that develops in polycrystalline Ni-base superalloys at service temperature, as a speckle pattern for μm-scale resolution strain measurements. Quantitative assessment of the heterogeneous strain field at the grain scale is performed by high-resolution SEM digital image correlation under monotonic and cyclic loading in polycrystalline Ni-base superalloys up to 650 ^°C. In the René 88DT superalloy, strain localization is observed near twin boundaries during low cycle fatigue (LCF) at intermediate temperatures, correlating with activation of {111} 〈110〉 and {111} 〈112〉 slip systems. A strong correlation between the microstructural configuration that promotes strain localization during monotonic loading and crack initiation at 650 ^°C in low cycle fatigue was observed.     

New Adventures in Thermal Analysis

This paper describes recent advances in thermal analysis instrumentation which combine the high resolution imaging capabilities of the atomic force microscope with physical characterisation by thermal analysis. Images of the surface may be obtained according to the specimen's thermal conductivity and thermal expansivity differences in addition to the usual topographic relief. Localised equivalents of modulated temperature differential scanning calorimetry, thermomechanical and dynamic mechanical analysis have been developed with a spatial resolution of a few micrometres. A form of localised thermogravimetry-evolved gas analysis has also been demonstrated. The same instrument configuration can be adapted to allow IR microspectrometry at a resolution better than the optical diffraction limit. This revised version was published online in August 2006 with corrections to the Cover Date.     

A Technical Critique of Some Parts of the Free Energy Principle

We summarize the original formulation of the free energy principle and highlight some technical issues. We discuss how these issues affect related results involving generalised coordinates and, where appropriate, mention consequences for and reveal, up to now unacknowledged, differences from newer formulations of the free energy principle. In particular, we reveal that various definitions of the “Markov blanket” proposed in different works are not equivalent. We show that crucial steps in the free energy argument, which involve rewriting the equations of motion of systems with Markov blankets, are not generally correct without additional (previously unstated) assumptions. We prove by counterexamples that the original free energy lemma, when taken at face value, is wrong. We show further that this free energy lemma, when it does hold, implies the equality of variational density and ergodic conditional density. The interpretation in terms of Bayesian inference hinges on this point, and we hence conclude that it is not sufficiently justified. Additionally, we highlight that the variational densities presented in newer formulations of the free energy principle and lemma are parametrised by different variables than in older works, leading to a substantially different interpretation of the theory. Note that we only highlight some specific problems in the discussed publications. These problems do not rule out conclusively that the general ideas behind the free energy principle are worth pursuing.