Crystal Structure of LiRh-type IrZn Determined by Powder X-ray and Selected Area Electron Diffraction

The LiRh-type crystal structure of the equiatomic intermetallic compound IrZn turns out to be a competitor to the otherwise energetically favored CsCl-type structures of congeneric transition metal zinc phases, thus enlightening the structural impact of element-specific factors beyond the Hume-Rothery concept.     

Crystal structure, physical properties and HRTEM investigation of the new oxonitridosilicate EuSi2O2N2

The new layered oxonitridosilicate EuSi₂O₂N₂ has been synthesized in a radio‐frequency furnace at temperatures of about 1400 °C starting from europium(III ) oxide (Eu₂O₃) and silicon diimide (Si(NH)₂). The structure of the yellow material has been determined by single‐crystal X‐ray diffraction analysis (space group P1 (no. 1), a=709.5(1), b=724.6(1), c=725.6(1) pm, α=88.69(2), β=84.77(2), γ=75.84(2)°,V=360.19(9)×10⁶ pm³, Z=4, R1=0.0631, 4551 independent reflections, 175 parameters). Its anionic Si₂O₂N₂^2? layers consist of corner‐sharing SiON₃ tetrahedra with threefold connecting nitrogen and terminal oxygen atoms. High‐resolution transmission electron micrographs indicate both ordered and disordered crystallites as well as twinning. Magnetic susceptibility measurements of EuSi₂O₂N₂ exhibit Curie–Weiss behavior above 20 K with an effective magnetic moment of 7.80(5) μ_B Eu^?1, indicating divalent europium. Antiferromagnetic ordering is detected at 4.5(2) K. EuSi₂O₂N₂ shows a field‐induced transition with a critical field of 0.50(5) T. The four crystallographically different europium sites cannot be distinguished by ¹⁵¹Eu Mössbauer spectroscopy. The room‐temperature spectrum is fitted by one signal at an isomer shift of δ=?12.3(1) mm s^?1 subject to quadrupole splitting of ΔE_Q=?2.3(1) mm s^?1 and an asymmetry parameter of 0.46(3). Luminescence measurements show a narrow emission band with regard to the four crystallographic europium sites with an emission maximum at λ=575 nm.     

Structure and dynamics of the fast lithium ion conductor "Li7La3Zr2O12"

The solid lithium-ion electrolyte "Li(7)La(3)Zr(2)O(12)" (LLZO) with a garnet-type structure has been prepared in the cubic and tetragonal modification following conventional ceramic syntheses routes. Without aluminium doping tetragonal LLZO was obtained, which shows a two orders of magnitude lower room temperature conductivity than the cubic modification. Small concentrations of Al in the order of 1 wt% were sufficient to stabilize the cubic phase, which is known as a fast lithium-ion conductor. The structure and ion dynamics of Al-doped cubic LLZO were studied by impedance spectroscopy, dc conductivity measurements, (6)Li and (7)Li NMR, XRD, neutron powder diffraction, and TEM precession electron diffraction. From the results we conclude that aluminium is incorporated in the garnet lattice on the tetrahedral 24d Li site, thus stabilizing the cubic LLZO modification. Simulations based on diffraction data show that even at the low temperature of 4 K the Li ions are blurred over various crystallographic sites. This strong Li ion disorder in cubic Al-stabilized LLZO contributes to the high conductivity observed. The Li jump rates and the activation energy probed by NMR are in very good agreement with the transport parameters obtained from electrical conductivity measurements. The activation energy E(a) characterizing long-range ion transport in the Al-stabilized cubic LLZO amounts to 0.34 eV. Total electric conductivities determined by ac impedance and a four point dc technique also agree very well and range from 1 × 10(-4) Scm(-1) to 4 × 10(-4) Scm(-1) depending on the Al content of the samples. The room temperature conductivity of Al-free tetragonal LLZO is about two orders of magnitude lower (2 × 10(-6) Scm(-1), E(a) = 0.49 eV activation energy). The electronic partial conductivity of cubic LLZO was measured using the Hebb-Wagner polarization technique. The electronic transference number t(e-) is of the order of 10(-7). Thus, cubic LLZO is an almost exclusive lithium ion conductor at ambient temperature.     

Combined MR-relaxation and MR-cryoporometry in the study of bone microstructure.

MR-Relaxation (MRR) of 1H nuclei and MR-Cryoporometry (MRC) are combined to assess their feasibility and their potential in the study of bone microstructure. In principle, both techniques are able to give information on the structure of the pore space confining the fluids. Cow femur samples were carefully cored and cleaned in order to remove the natural fluids inside. For MRR analysis quasi-continuous distributions of T(1) and T(2) were obtained on samples fully saturated with water. Cyclohexane was used as a saturating fluid for MRC analysis. All T(1) and T(2) quasi-continuous distributions of water confined in bone samples are more than three decades wide, showing sufficient details to differentiate the samples. Pore size distributions obtained by MRC also differentiate the samples showing different characteristics of the pore space structure in the range of the highest sensitivity of the method (typically 3 to 100 nm, mesopore range). In particular, in samples where MRR shows a large fraction of signal with relaxation times below 10(2) ms, MRC indicates a large fraction of pore volume with pore sizes in the mesopore range.     

High performance PtRuIr catalysts supported on carbon nanotubes for the anodic oxidation of methanol

We report the formation of a new PtRuIr catalyst using an organic colloid synthesis method, involving acetone as the solvent, ethylene glycol as the reducing agent, citrate as a complexing agent and stabilizer, and multiwall carbon nanotubes (CNT, diameter 8-10 nm) as the support. This catalyst has a very high real surface area and is highly active toward the oxidation of methanol, relevant to fuel cell applications. The Ir component appears to act as a promoter, and the splitting of the Pt(111) XRD feature into four peaks and the shift to larger d spacing reflect the high dispersion of the metallic components.     

Breakup densities of hot nuclei

Breakup densities of hot 197Au-like residues have been deduced from the systematic trends of Coulomb parameters required to fit intermediate-mass-fragment kinetic-energy spectra. The results indicate emission from nuclei near normal nuclear density below an excitation energy E(*)/A less, similar 2 MeV, followed by a gradual decrease to a near-constant value of rho/rho(0) approximately 0.3 for E(*)/A greater, similar 5 MeV. Temperatures derived from these data with a density-dependent Fermi-gas model yield a nuclear caloric curve that is generally consistent with those derived from isotope ratios.     

A hybrid stress approach for laminated composite plates within the First-order Shear Deformation Theory

This paper presents a hybrid stress approach for the analysis of laminated composite plates. The plate mechanical model is based on the so called First-order Shear Deformation Theory, rationally deduced from the parent three-dimensional theory. Within this framework, a new quadrilateral four-node finite element is developed from a hybrid stress formulation involving, as primary variables, compatible displacements and elementwise equilibrated stress resultants. The element is designed to be simple, stable and locking-free. The displacement interpolation is enhanced by linking the transverse displacement to the nodal rotations and a suitable approximation for stress resultants is selected, ruled by the minimum number of parameters. The transverse stresses through the laminate thickness are reconstructed a posteriori by simply using three-dimensional equilibrium. To improve the results, the stress resultants entering the reconstruction process are first recovered using a superconvergent patch-based procedure called Recovery by Compatibility in Patches, that is properly extended here for laminated plates. This preliminary recovery is very efficient from the computational point of view and generally useful either to accurately evaluate the stress resultants or to estimate the discretization error. Indeed, in the present context, it plays also a key role in effectively predicting the shear stress profiles, since it guarantees the global convergence of the whole reconstruction strategy, that does not need any correction to accommodate equilibrium defects. Actually, this strategy can be adopted together with any plate finite element. Numerical testing demonstrates the excellent performance of both the finite element and the reconstruction strategy.     

Crack propagation in an orthotropic medium with coupled elastodynamic properties

In this paper the Mode-I elastodynamic problem of a crack propagating in an orthotropic medium is studied under the condition that the matrix of elastodynamic coefficients has repeated eigenvalues. It is shown that the crack is constrained in an elastodynamic state which is defined through a compulsory condition coupling its velocity with the elastic parameters of the orthotropic medium. The dynamic stress and displacement components ahead of the crack tip as well as the energy release rate are explicitly obtained.     

Detection of crack location using cracked beam element method for structural analysis

The local flexibility introduced by cracks changes the dynamic behavior of the structure and, by examining this change, crack position and magnitude can be identified. In order to model the structure for FEM analysis, a special finite element for a cracked Timoshenko beam is developed. Shape functions for rotational and translational displacements are used to obtain the consistent mass matrix for the cracked beam element. Effect of the crack on the stiffness matrix and consistent mass matrix is investigated. Proposed is a procedure for identifying cracks in structures using modal test data.