As a natural biocomposite, Strombus gigas, commonly known as the giant pink queen conch shell, exhibits outstanding mechanical properties, especially a high fracture toughness. It is known that the basic building block of conch shell contains a high density of growth twins with average thickness of several nanometres, but their effects on the mechanical properties of the shell remain mysterious. Here we reveal a toughening mechanism governed by nanoscale twins in the conch shell. A combination of in situ fracture experiments inside a transmission electron microscope, large-scale atomistic simulations and finite element modelling show that the twin boundaries can effectively block crack propagation by inducing phase transformation and delocalization of deformation around the crack tip. This mechanism leads to an increase in fracture energy of the basic building block by one order of magnitude, and contributes significantly to that of the overall structure via structural hierarchy.
Copper (Cu) nanoparticles (NPs) have received extensive interest owing to their advantageous properties compared with their bulk counterparts. Although the natural oxidation of Cu NPs can be alleviated by passivating the surfaces with additional moieties, obtaining non-oxidized bare Cu NPs in air remains challenging. Here we report that bare Cu NPs with surface excess electrons retain their non-oxidized state over several months in ambient air. Cu NPs grown on an electride support with excellent electron transfer ability are encapsulated by the surface-accumulated excess electrons, exhibiting an ultralow work function of ~3.2 eV. Atomic-scale structural and chemical analyses confirm the absence of Cu oxide moiety at the outermost surface of air-exposed bare Cu NPs. Theoretical energetics clarify that the surface-accumulated excess electrons suppress the oxygen adsorption and consequently prohibit the infiltration of oxygen into the Cu lattice, provoking the endothermic reaction for oxidation process. Our results will further stimulate the practical use of metal NPs in versatile applications.
Dislocations in single-phase concentrated random alloys, including high-entropy alloys (HEAs), repeatedly encounter pinning during glide, resulting in jerky dislocation motion. While solute-dislocation interaction is well understood in conventional alloys, the origin of individual pinning points in concentrated random alloys is a matter of debate. In this work, we investigate the origin of dislocation pinning in the CoCrFeMnNi HEA. In-situ transmission electron microscopy studies reveal wavy dislocation lines and a jagged glide motion under external loading, even though no segregation or clustering is found around Shockley partial dislocations. Atomistic simulations reproduce the jerky dislocation motion and link the repeated pinning to local fluctuations in the Peierls friction. We demonstrate that the density of high local Peierls friction is proportional to the critical stress required for dislocation glide and the dislocation mobility.
17 December 2021 in Energy & Environmental Science
The interface-type resistive switching devices exhibiting bipolar and multi-level resistive switching have been considered as the key component for neuromorphic device applications. To directly observe the microscopic details of underlying electrochemical redox reactions occuring at a metal/oxide interface, we implemented in situ resistive switching of TiN/Pr0.7Ca0.3MnO3 (PCMO)/Pt junction devices in a transmission electron microscope (TEM). The in situ TEM observations directly show that an intermediate reaction layer (TiOxNy), growing and shrinking in the thickness range of a few nanometers at the TiN/PCMO interface in response to the applied voltage, mainly determines the device resistance by limiting the transport of charge carriers via the Poole–Frenkel conduction mechanism. A detailed analysis of in situ TEM observations demonstrates that electrochemical redox reactions at the TiN/PCMO interface are facilitated by the electric field driven drift of oxygen as well as Ti ions with a much stronger influence of the oxygen ions. As such, the reaction kinetics are governed by the electric field acting across the TiOxNy reaction layer. This layer defines the critical field for the onset of switching, which is measured to be of the order of 106 V cm−1, a typical value at which the ionic drift velocity starts increasing exponentially with the field according to the nonlinear ionic drift model. The present results indicate that understanding the nature of the electric field driven drift of ions in a nanoscale solid electrolyte is a key to the precise control of the resistive switching of metal/insulator/metal junction devices via voltage stimulations.