Numerical study of density functional theory with mean spherical approximation for ionic condensation in highly charged confined electrolytes

We investigate numerically a Density Functional Theory (DFT) for strongly confined ionic solutions in the Canonical Ensemble by comparing predictions of ionic concentration profiles and pressure for the double-layer configuration to those obtained with Monte Carlo (MC) simulations and the simpler Poisson--Boltzmann (PB) approach. The DFT consists of a bulk (ion-ion) and an ion-solid part. The bulk part includes nonideal terms accounting for long-range electrostatic and short-range steric correlations between ions and is evaluated with the Mean Spherical Approximation and the Local Density Approximation. The ion-solid part treats the ion-solid interactions at the mean-field level through the solution of a Poisson problem. The main findings are that ionic concentration profiles are generally better described by PB than by DFT, although DFT captures the non-monotone co-ion profile missed by PB. Instead, DFT yields more accurate pressure predictions than PB, showing in particular that nonideal effects are important to describe highly confined ionic solutions. Finally, we present a numerical methodology capable of handling nonconvex minimization problems so as to explore DFT predictions when the reduced temperature falls below the critical temperature

The role of phase compatibility in martensite

Shape memory alloys inherit their macroscopic properties from their mesoscale microstructure originated from the martensitic phase transformation. In a cubic to orthorhombic transition, a single variant of marten- site can have a compatible (exact) interface with the austenite for some special lattice parameters in contrast to conventional austenite/twinned martensite interface with a transition layer. Experimentally, the phase compat- ibility results in a dramatic drop in thermal hysteresis and gives rise to very stable functional properties over cycling. Here, we investigate the microstructures observed in Ti50Ni50-xPdx alloys that undergo a cubic to orthorhombic martensitic transformation using a three dimensional phase field approach. We will show that the simulation results are in very good agreement with transmission electron microscopy observations. However, the understanding of the drop in thermal hysteresis requires the coupling of phase transformation with plastic activity. We will discuss this point within the framework of thermoelasticity, which is a generic feature of the martensitic transformation.Comment: Accepted for publication in in Journal of Applied Physic

Direct Observation of Ferrielectricity at Ferroelastic Domain Boundaries in CaTiO3 by Electron Microscopy

High-resolution aberration-corrected transmission electron microscopy aided by statistical parameter estimation theory is used to quantify localized displacements at a (110) twin boundary in orthorhombic CaTiO3. The displacements are 3–6 pm for the Ti atoms and confined to a thin layer. This is the first direct observation of the generation of ferroelectricity by interfaces inside this material which opens the door for domain boundary engineering.\ud \ud Graphical Abstract: http://onlinelibrary.wiley.com/store/10.1002/adma.201103717/asset/image_m/mcontent.jpg?v=1&s=833d8771f847e356acb7c65dffc61a359098e66

Assessment of the U3O7 Crystal Structure by X-ray and Electron Diffraction

Polycrystalline U3O7 powder was synthesized by oxidation of UO2 powder under controlled conditions using in situ thermal analysis, and by heat treatment in a tubular furnace. The O/U ratio of the U3O7 phase was measured as 2.34 ± 0.01. The crystal structure was assessed from X-ray diffraction (XRD) and selected-area electron diffraction (SAED) data. Similar to U4O9−ε (more precisely U64O143), U3O7 exhibits a long-range ordered structure, which is closely related to the fluorite-type arrangement of UO2. Cations remain arranged identical to that in the fluorite structure, and excess anions form distorted cuboctahedral oxygen clusters, which periodically replace the fluorite anion arrangement. The structure can be described in an expanded unit cell containing 15 fluorite-like subcells (U15O35), and spanned by basis vectors A = ap – 2bp, B = −2ap + bp, and C = 3cp (lattice parameters of the subcell are ap = bp = 538.00 ± 0.02 pm and cp = 554.90 ± 0.02 pm; cp/ap = 1.031). The arrangement of cuboctahedra in U3O7 results in a layered structure, which is different from the well-known U4O9−ε crystal structure.status: publishe

Dissolution corrosion of 316L austenitic stainless steels in contact with static liquid lead-bismuth eutectic (LBE) at 500 °C

This work addresses the dissolution corrosion behaviour of 316L austenitic stainless steels. For this purpose, solution-annealed and cold-deformed 316L steels were simultaneously exposed to oxygen-poor (<10-8 mass%) static liquid lead-bismuth eutectic (LBE) for 253e3282 h at 500 _C. Corrosion was consistently more severe for the cold-drawn steels than the solution-annealed steel, indicating the importance of the steel thermomechanical state. The thickness of the dissolution-affected zone was non-uniform, and sites of locally-enhanced dissolution were occasionally observed. The progress of LBE dissolution attack was promoted by the interplay of certain steel microstructural features (grain boundaries, deformation twin laths, precipitates) with the dissolution corrosion process. The identified dissolution mechanisms were selective leaching leading to steel ferritization, and non-selective leaching; the latter was mainly observed in the solution-annealed steel. The maximum corrosion rate decreased with exposure time and was found to be inversely proportional to the depth of dissolution attack.status: publishe

Dedicated TEM on domain boundaries from phase transformations and crystal growth

Investigating domain boundaries and their effects on the behaviour of materials automatically implies the need for detailed knowledge on the structural aspects of the atomic configurations at these interfaces. Not only in view of nearest neighbour interactions but also at a larger scale, often surpassing the unit cell, the boundaries can contain structural elements that do not exist in the bulk. In the present contribution, a number of special boundaries resulting from phase transformations or crystal growth and those recently investigated by advanced transmission electron microscopy techniques in different systems will be reviewed. These include macrotwins between microtwinned martensite plates in Ni–Al, austenite-single variant martensite habit planes in low hysteresis Ni–Ti–Pd, nanotwins in non-textured nanostructured Pd and ferroelastic domain boundaries in CaTiO3. In all discussed cases these boundaries play an essential role in the properties of the respective materials

Dedicated TEM on domain boundaries from phase transformations and crystal growth

Investigating domain boundaries and their effects on the behaviour of materials automatically implies the need for detailed knowledge on the structural aspects of the atomic configurations at these interfaces. Not only in view of nearest neighbour interactions but also at a larger scale, often surpassing the unit cell, the boundaries can contain structural elements that do not exist in the bulk. In the present contribution, a number of special boundaries resulting from phase transformations or crystal growth and those recently investigated by advanced transmission electron microscopy techniques in different systems will be reviewed. These include macrotwins between microtwinned martensite plates in Ni–Al, austenite-single variant martensite habit planes in low hysteresis Ni–Ti–Pd, nanotwins in non-textured nanostructured Pd and ferroelastic domain boundaries in CaTiO3. In all discussed cases these boundaries play an essential role in the properties of the respective materials