Refractory high-entropy alloys (HEAs) are a class of emerging multi-component alloys, showing superior mechanical properties at elevated temperatures and being technologically interesting. However, they are generally brittle at room temperature, fail by cracking at low compressive strains and suffer from limited formability. Here we report a strategy for the fabrication of refractory HEA thin films and small-sized pillars that consist of strongly textured, columnar and nanometre-sized grains. Such HEA pillars exhibit extraordinarily high yield strengths of ∼10 GPa—among the highest reported strengths in micro-/nano-pillar compression and one order of magnitude higher than that of its bulk form—and their ductility is considerably improved (compressive plastic strains over 30%). Additionally, we demonstrate that such HEA films show substantially enhanced stability for high-temperature, long-duration conditions (at 1,100 °C for 3 days). Small-scale HEAs combining these properties represent a new class of materials in small-dimension devices potentially for high-stress and high-temperature applications.
The electrical conductivity of dense and nanoporous zirconia‐based thin films is compared to results obtained on bulk yttria stabilized zirconia (YSZ) ceramics. Different thin film preparation methods are used in order to vary grain size, grain shape, and porosity of the thin films. In porous films, a rather high conductivity is found at room temperature which decreases with increasing temperature to 120 °C. This conductivity is attributed to proton conduction along physisorbed water (Grotthuss mechanism) at the inner surfaces. It is highly dependent on the humidity of the surrounding atmosphere. At temperatures above 120 °C, the conductivity is thermally activated with activation energies between 0.4 and 1.1 eV. In this temperature regime the conduction is due to oxygen ions as well as protons. Proton conduction is caused by hydroxyl groups at the inner surface of the porous films. The effect vanishes above 400 °C, and pure oxygen ion conductivity with an activation energy of 0.9 to 1.3 eV prevails. The same behavior can also be observed in nanoporous bulk ceramic YSZ. In contrast to the nanoporous YSZ, fully dense nanocrystalline thin films only show oxygen ion conductivity, even down to 70 °C with an expected activation energy of 1.0 ± 0.1 eV. No proton conductivity through grain boundaries could be detected in these nanocrystalline, but dense thin films.
c -axis oriented epitaxial films of the ferroelectric BaTiO3 have been grown on (001) Si by reactive molecular-beam epitaxy. The orientation relationship between the film and substrate is (001) BaTiO3‖(001) Si and [100] BaTiO3‖[110] Si. The uniqueness of this integration is that the entire epitaxial BaTiO3 film on (001) Si is c-axis oriented, unlike any reported so far in the literature. The thermal expansion incompatibility between BaTiO3 and silicon is overcome by introducing a relaxed buffer layer of BaxSr1−xTiO3 between the BaTiO3 film and silicon substrate. The rocking curve widths of the BaTiO3 films are as narrow as 0.4°. X-ray diffraction and second harmonic generation experiments reveal the out-of-plane c-axis orientation of the epitaxial BaTiO3 film. Piezoresponse atomic force microscopy is used to write ferroelectric domains with a spatial resolution of ∼100nm, corroborating the orientation of the ferroelectric film.
Metals with nanometer-scale grains or nanocrystalline metals exhibit high strengths at ambient conditions, yet their strengths substantially decrease with increasing temperature, rendering them unsuitable for usage at high temperatures. Here, we show that a nanocrystalline high-entropy alloy (HEA) retains an extraordinarily high yield strength over 5 GPa up to 600 °C, 1 order of magnitude higher than that of its coarse-grained form and 5 times higher than that of its single-crystalline equivalent. As a result, such nanostructured HEAs reveal strengthening figures of merit-normalized strength by the shear modulus above 1/50 and strength-to-density ratios above 0.4 MJ/kg, which are substantially higher than any previously reported values for nanocrystalline metals in the same homologous temperature range, as well as low strain-rate sensitivity of ∼0.005. Nanocrystalline HEAs with these properties represent a new class of nanomaterials for high-stress and high-temperature applications in aerospace, civilian infrastructure, and energy sectors.
Amorphous cobalt silicate nanobelts@carbon composites turned out to be excellent anode materials for lithium ion batteries.
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