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The similarity in atomic/molecular structure between liquids and glasses has stimulated a long-standing hypothesis that the nature of glasses may be more fluid-like, rather than the apparent solid. In principle, the nature of glasses can be characterized by the dynamic response of their rheology in a wide rate range, but this has not been realized experimentally, to the best of our knowledge. Here we report the dynamic response of shear stress to the shear strain rate of metallic glasses over a timescale of nine orders of magnitude, equivalent to hundreds of years, by broadband stress relaxation experiments. The dynamic response of the metallic glasses, together with other 'glasses', follows a universal scaling law within the framework of fluid dynamics. The universal scaling law provides comprehensive validation of the conjecture on the jamming (dynamic) phase diagram by which the dynamic behaviours of a wide variety of 'glasses' can be unified under one rubric parameterized by the thermodynamic variables of temperature, volume and stress in the trajectory space.
Assuntos
Reologia , Estresse Mecânico , Temperatura , TermodinâmicaRESUMO
Understanding the formation and evolution of bicontinuous nanoporous structure during dealloying has been one of the most challenging subjects of dealloying research. However, previous in situ investigations either suffer from insufficient spatial resolution (e.g., X-ray tomography) or lack morphology visualization and mass information (e.g., scanning tunneling microscopy). In this work, we report the kinetics of the whole course of dealloying by utilizing liquid-cell aberration-corrected scanning transmission electron microscopy. With Z-contrast imaging analysis, the in situ sub-nanoscale characterization reveals two new phenomena, an initial period of dealloying indicative of an initial length scale for bulk dealloying and a large volume shrinkage in a nanoscale alloy precursor. We explain the particle-size-dependent volume shrinkage with the formation of a dense shell and quantify the dependence with a simple geometric model. These insights into the mechanisms of dealloying will enable deliberate designs of nanoporous structures.
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The structural characterization of sublayer surfaces of MIL-101 is reported by low-dose spherical aberration-corrected high-resolution transmission electron microscopy (HRTEM). The state-of-the-art microscopy directly images atomic/molecular configurations in thin crystals from charge density projections, and uncovers the structures of sublayer surfaces and their evolution to stable surfaces regulated by inorganic Cr3 (µ3 -O) trimers. This study provides compelling evidence of metal-organic frameworks (MOFs) crystal growth via the assembly of sublayer surfaces and has important implications in understanding the crystal growth and surface-related properties of MOFs.
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The recent observation of the reverse Hall-Petch relation in nanocrystalline ceramics offers a possible pathway to achieve enhanced ductility for traditional brittle ceramics via the nanosize effect, just as nanocrystalline metals and alloys. However, the underlying deformation mechanisms of nanocrystalline ceramics have not been well established. Here we combine reactive molecular dynamics (RMD) simulations and experimental transmission electron microscopy to determine the atomic level deformation mechanisms of nanocrystalline boron carbide (B_{4}C). We performed large-scale (up to â¼3 700 000 atoms) ReaxFF RMD simulations on finite shear deformation of three models of grain boundaries with grain sizes from 4.84 (135 050 atoms) to 14.64 nm (3 702 861 atoms). We found a reverse Hall-Petch relationship in nanocrystalline B_{4}C in which the deformation mechanism is dominated by the grain boundary (GB) sliding. This GB sliding leads to the amorphous band formation at predistorted icosahedral GB regions with initiation of cavitation within the amorphous bands. Our simulation results are validated by the experimental observations of an intergranular amorphous GB phase due to GBs sliding under indentation experiments. These theoretical and experimental results provide an atomistic explanation for the influence of GBs on the deformation behavior of nanocrystalline ceramics, explaining the reverse Hall-Petch relation.
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Although nanoscale spatial heterogeneity of metallic glasses has been demonstrated by extensive experimental and theoretical investigations, the nature of spatial heterogeneity remains poorly known owing to the absence of a structural depiction of the inhomogeneity from experimental insight. Here we report the experimental characterization of the spatial heterogeneity of a metallic glass by utilizing state-of-the-art angstrom-beam electron diffraction and scanning transmission electron microscopy. The subnanoscale electron diffraction reveals that the nanoscale spatial heterogeneity and corresponding density fluctuation have a close correlation with the local structure variation from icosahedronlike to tetragonal crystal-like order. The structural insights of spatial heterogeneity have important implications in understanding the properties and dynamics of metallic glasses.
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Understanding the growth and coarsening mechanisms of metal-organic framework (MOF) nanoparticles is crucially important for the design and fabrication of MOF materials with diverse functionalities and controllable stability. Oriented attachment (OA) growth is a common manner of MOF nanocrystal coarsening and agglomeration, but the underlying molecular mechanisms have not been well understood to date. Here we report the molecular-scale characterization of the OA interfaces of zeolitic imidazolate framework (ZIF) crystals by state-of-the-art low-dose aberration-corrected transmission electron microscopy. A series of OA interfaces with different molecular structures are captured, implying that multiple kinetic steps are involved in the OA growth of ZIF crystals from non-directional physical attractions between primary nanocrystals, lattice-aligned attachment of the ligand-capped nanocrystals, to coherent interfaces with perfect lattice alignment or stacking faults. It was found that the surface-capping organic ligands not only play an essential role in crystal lattice alignment by near-field directional interactions, but also dominate the interfacial reaction kinetics by interfacial diffusion-controlled elimination of excess surface-capping ligands. These observations provide molecular-scale insights into the OA growth mechanisms of ZIF crystals, which is important for engineering MOF crystal growth pathways by designing surface-capping ligands.
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Non-conservative dislocation climb plays a unique role in the plastic deformation and creep of crystalline materials. Nevertheless, the underlying atomic-scale mechanisms of dislocation climb have not been explored by direct experimental observations. Here, we report atomic-scale observations of grain boundary (GB) dislocation climb in nanostructured Au during in situ straining at room temperature. The climb of a edge dislocation is found to occur by stress-induced reconstruction of two neighboring atomic columns at the edge of an extra half atomic plane in the dislocation core. This is different from the conventional belief of dislocation climb by destruction or construction of a single atomic column at the dislocation core. The atomic route of the dislocation climb we proposed is demonstrated to be energetically favorable by Monte Carlo simulations. Our in situ observations also reveal GB evolution through dislocation climb at room temperature, which suggests a means of controlling microstructures and properties of nanostructured metals.
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The failure of superhard materials is often associated with stress-induced amorphization. However, the underlying mechanisms of the structural evolution remain largely unknown. Here, we report the experimental measurements of the onset of shear amorphization in single-crystal boron carbide by nanoindentation and transmission electron microscopy. We verified that rate-dependent loading discontinuity, i.e., pop-in, in nanoindentation load-displacement curves results from the formation of nanosized amorphous bands via shear amorphization. Stochastic analysis of the pop-in events reveals an exceptionally small activation volume, slow nucleation rate, and lower activation energy of the shear amorphization, suggesting that the high-pressure structural transition is activated and initiated by dislocation nucleation. This dislocation-mediated amorphization has important implications in understanding the failure mechanisms of superhard materials at stresses far below their theoretical strengths.
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Highly active, cost-effective and durable electrocatalysts for the oxygen reduction reaction (ORR) are critically important for renewable energy conversion and storage. Here we report a 3D bicontinuous nitrogen doped nanoporous graphene electrocatalyst co-anchoring with atomically dispersed nickel and copper atoms ((Ni,Cu)-NG) as a highly active single-atom ORR catalyst, fabricated by the combination of chemical vapor deposition and high temperature gas transportation. The resultant (Ni,Cu)-NG exhibits an exceptional ORR activity in alkaline electrolytes, comparable to the Pt-based benchmarks, from the synergistic effect of the CuNx and NiNx complexes. Endowed with high catalytic activity and outstanding durability under harsh electrochemical environments, rechargeable zinc-air batteries using (Ni,Cu)-NG as the cathodes show excellent energy efficiency (voltage gap of 0.74 V), large power density (150.6 mW cm-2 at 250 mA cm-2) and high cycling stability (>500 discharge-charge cycles at 10 mA cm-2). This study may pave an efficient avenue for designing highly durable single-atom ORR catalysts for metal-air batteries.
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Transition metal (TM) doping has been demonstrated to be an efficacious way to boost the catalytic activity of molybdenum disulfide (MoS2) for energy storage and conversion, especially for the hydrogen evolution reaction (HER). Real-space visualization of the atomic structure of Ni doped MoS2 is crucial to understand the role of heteroatoms in enhancing electrocatalysis. By utilizing aberration corrected scanning transmission electron microscopy (STEM), we found that Ni dopants occupy Mo sites in MoS2 synthesized by a one-pot hydrothermal method. Such selective occupation of the single-atom Ni dopants leads to significant lattice distortion and electronic structure modification of the catalytically inert basal planes of MoS2, which are responsible for the enhanced HER catalysis of MoS2 in both acidic and alkaline solutions.
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The coarsening of crystalline nanoparticles, driven by reduction of surface energy, is the main factor behind the degeneration of their physical and chemical properties. The kinetic phenomenon has been well described by various models, such as Ostwald ripening and coalescence. However, the coarsening mechanisms of metallic glass nanoparticles (MGNs) remains largely unknown. Here we report atomic-scale observations on the coarsening kinetics of MGNs at high temperatures by in situ heating high-resolution transmission electron microscopy. The coarsening of the amorphous nanoparticles takes place by fast coalescence which is dominated by facet-free surface diffusion at a lower onset temperature. Atomic-scale observations and kinetic Monte Carlo simulations suggest that the high surface mobility and the structural isotropy of MGNs, originating from the disordered structure and unique supercooled liquid state, promote the fast coalescence of the amorphous nanoparticles at relatively lower temperatures.
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We report experimental observation of room-temperature superplasticity and the distinct nanosize effect on the deformation mechanisms of Au nanowires. The Au nanowires were subjected to in situ tensile straining in a transmission electron microscope by using a home-made strain actuator, and a super large plastic strain with â¼150% uniform elongation and â¼260% total strain were observed before fracture. The plastic deformation started through full dislocation slip and was followed by the activities of stacking fault ribbons (or dissociated full dislocations) that were generated from surface sources and disappeared at the other end surfaces. With the reduction of the diameter of Au nanowires, the deformation changed to the twinning mode through partial dislocation emissions from sample surfaces. The mechanisms behind the observed phenomena are discussed in detail. These results shed light on the size-controlled plasticity of nano-metals.
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The mechanical properties of crystalline materials can be quantitatively described by crystal defects of solute atoms, dislocations, twins, and grain boundaries with the models of solid solution strengthening, Taylor strain hardening and Hall-Petch grain boundary strengthening. However, for metallic glasses, a well-defined structure feature which dominates the mechanical properties of the disordered materials is still missing. Here, we report that nanoscale spatial heterogeneity is the inherent structural feature of metallic glasses. It has an intrinsic correlation with the strength and deformation behavior. The strength and Young's modulus of metallic glasses can be defined by the function of the square root reciprocal of the characteristic length of the spatial heterogeneity. Moreover, the stretching exponent of time-dependent strain relaxation can be quantitatively described by the characteristic length. Our study provides compelling evidence that the spatial heterogeneity is a feasible structural indicator for portraying mechanical properties of metallic glasses.