Marc Widenmeyer

Crystal structure determination of Hägg carbide, χ-Fe5C2 by first-principles calculations and Rietveld refinement

Abstract X-ray powder-diffraction data recorded using different wave lengths as well as neutron powder diffraction data on Hägg carbide, χ-Fe5C2, were evaluated by Rietveld or Pawley refinements, respectively. Likewise, employing different starting models, first-principles calculations using density functional theory (DFT) involving structure optimisation with respect to energy were performed for χ-Fe5C2. The results from diffraction and DFT imply a crystal structure having a monoclinic C2/c symmetry with a quite regular (monocapped) trigonal-prismatic coordination of C by Fe atoms. The anisotropy of the microstrain broadening observed in the powder-diffraction patterns agrees with the anisotropy of the reciprocal Young’s module obtained from elastic constants calculated by DFT. The anisotropic microstrain broadening can to some degree, be modelled allowing for a triclinic distortion of the metric of χ-Fe5C2 (deviation of the lattice angle γ from 90°) involving reflection spitting, which mimics the hkl-dependently broadened reflections. This distortion corresponds to the most compliant shear direction of the monoclinic χ-Fe5C2. The anisotropic microstrain broadening results from microstress induced e.g. by anisotropic thermal expansion inducing misfit between the grains, in association with the intrinsic anisotropic elastic compliance of χ-Fe5C2. This anisotropic microstrain broadening was likely the origin of previous proposals of triclinic P-1 space-group symmetry for the crystal structure of χ-Fe5C2, which is rejected in the present work.

Ultrahigh Damping Capacities in Lightweight Structural Materials

The demand to outperform current technologies pushes scientists to develop novel strategies, which enable the fabrication of materials with exceptional properties. Along this line, lightweight structural materials are of great interest due to their versatile applicability as sensors, catalysts, battery electrodes, and acoustic or mechanical dampers. Here, we report a strategy to design ultralight (ρ = 3 mg/cm3) and hierarchically structured ceramic scaffolds of macroscopic size. Such scaffolds exhibit mechanical reversibility comparable to that of microscopic metamaterials, leading to a macroscopically remarkable dynamic mechanical performance. Upon mechanical loading, these scaffolds show a deformation mechanism similar to polyurethane foams, and this resilience yields ultrahigh damping capacities, tan δ, of up to 0.47.

A self-forming nanocomposite concept for ZnO-based thermoelectrics

Zinc oxide (ZnO) has a very broad and versatile range of applications provided by its high abundance and optical and electrical properties, which can be further tuned by donor substitution. Al-doped ZnO is probably the most thoroughly investigated material with regard to thermoelectric properties. Fairly reasonable electrical properties of donor-doped zinc oxide are usually combined with high thermal conductivity limiting potential applications. Here we report a new self-forming nanocomposite concept for ZnO-based thermoelectrics, where a controllable interplay between the exsolution of the nanophases and modification of the host matrix suppresses the thermal transport while imparting enhanced electrical performance. The thermoelectric performance of the best-obtained composite, described by the dimensionless figure-of-merit ZT, at 920–1200 K is almost twice that of the pure matrix composition and reaches up to 0.11. The proposed approach invokes controlled interactions between composite components as a novel tool for decoupling the electrical and thermal transport parameters and shows clear prospects for an implementation in other thermoelectric oxide systems. The results indicate that the proposed concept may also constitute a promising pathway to achieve stable electrical performance at high temperatures, which currently represents one of the major challenges towards achieving ZnO-based thermoelectrics.