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Lithium-based molten salts have attracted significant attention due to their applications in energy storage, advanced fission reactors, and fusion devices. Lithium fluorides and particularly 66.6%LiF-33.3%BeF2 (Flibe) are of considerable interest in nuclear systems, as they show an excellent combination of favorable heat transfer, neutron moderation, and transmutation characteristics. For nuclear salts, the range of possible local structures, compositions, and thermodynamic conditions presents significant challenges in atomistic modeling. In this work, we demonstrate that atom-centered neural network interatomic potentials (NNIPs) provide a fast method for performing molecular dynamics of molten salts that is as accurate as ab initio molecular dynamics. For LiF, these potentials are able to accurately reproduce ab initio interactions of dimers, crystalline solids under deformation, crystalline LiF near the melting point, and liquid LiF at high temperatures. For Flibe, NNIPs accurately predict the structures and dynamics at normal operating conditions, high-temperature-pressure conditions, and in the crystalline solid phase. Furthermore, we show that NNIP-based molecular dynamics of molten salts are scalable to reach long time scales (e.g., nanosecond) and large system sizes (e.g., 105 atoms) while maintaining ab initio density functional theory accuracy and providing more than 3 orders of magnitude of computational speedup for calculating structure and transport properties.

Interest in molten salts has increased significantly over the last decade due to their potential application in various clean-energy technologies including hydrogen generation, solar heat storage, advanced fission nuclear power plants, and compact fusion energy systems. In nuclear fission and fusion power plants, high heat capacity molten salts allow operation at high temperature and atmospheric pressure, which could dramatically increase efficiency, reduce capital cost, and enable passive safety features. In many of these systems, the hydrogen isotope is of particular importance due to its ability to corrode structural materials as 3H+ in fluoride salts, and its potential to cause significant radioactive release as diffusive 3H0, which are cited as key barriers to technological deployment. Yet, the chemistry and transport behavior of the hydrogen species remain poorly understood due to the difficulties in handling toxic salts and radioactive materials. Here, using ab initio molecular dynamics, we present a coupled examination of hydrogen speciation in the most common prototypical salts 66.6% LiF–33.3% BeF2 (Flibe) and 46.5% LiF–11.5% NaF–42% KF (Flinak). Using extensively validated calculations on the local structure and dynamics, we find significant difference between 3H0 and 3H+ transport behaviors that are usually overlooked. We find that 3H0, which always exists as H2, diffuses 3–5 times faster than 3H+, which can be ascribed to hydrogen bonding and complexation in solution. This work explains contradicting experimental results and provides useful species transport data for designing hydrogen capture and corrosion control systems for molten salts.

The practical application of room-temperature Na-S batteries is hindered by the low sulfur utilization, inadequate rate capability and poor cycling performance. To circumvent these issues, here, we propose an electrocatalyst composite material comprising of N-doped nanocarbon and Fe3N. The multilayered porous network of the carbon accommodates large amounts of sulfur, decreases the detrimental effect of volume expansion, and stabilizes the electrodes structure during cycling. Experimental and theoretical results testify the Fe3N affinity to sodium polysulfides via Na-N and Fe-S bonds, leading to strong adsorption and fast dissociation of sodium polysulfides. With a sulfur content of 85 wt.%, the positive electrode tested at room-temperature in non-aqueous Na metal coin cell configuration delivers a reversible capacity of about 1165 mA h g−1 at 167.5 mA g−1, satisfactory rate capability and stable capacity of about 696 mA h g−1 for 2800 cycles at 8375 mA g−1., Room-temperature sodium-sulfur batteries are promising electrochemical energy storage systems. Here, the authors proposed a Fe3N/carbon composite to regulate the polysulfides chemistry and improve the performances of sodium-sulfur cells.

Single-phase metals can be strengthened via cold work, grain refinement, or solid solution hardening. But the yield strength elevation normally comes at the expense of ductility, i.e., a conspicuous decrease of the uniform elongation in uniaxial tension. This strength-ductility trade-off is often a result of inadequate strain hardening rate that can no longer keep up with the elevated flow stress to prevent plastic instability. Here we alleviate this dilemma by designing oxygen interstitial solution hardening in body-centered-cubic niobium: the strain hardening rate is exceptionally high, such that most of the uniform tensile ductility of Nb can be retained despite of quadrupled yield strength. The oxygen solutes impose random force field on moving dislocation line, promoting the formation of cross-kinks that dynamically accumulate vacancy-oxygen complexes. These obstacles enhance the trapping/multiplication of screw dislocations as well as cross-slip, all promoting strain hardening and strain de-localization. This approach utilizes only a low concentration of interstitial solutes to achieve effective strengthening and strain hardening simultaneously, and is an inexpensive and scalable route amenable to the processing of bulk samples.

Body-centred-cubic metallic materials, such as niobium (Nb) and other refractory metals, are prone to embrittlement due to low levels of oxygen solutes. The mechanisms responsible for the oxygen-induced rampant hardening and damage are unclear. Here we illustrate that screw dislocations moving through a random repulsive force field imposed by impurity oxygen interstitials readily form cross-kinks and emit excess vacancies in Nb. The vacancies bind strongly with oxygen and screw dislocation in a three-body fashion, rendering dislocation motion difficult and hence pronounced dislocation storage and hardening. While self-interstitials anneal out fast during plastic flow, the vacancy-oxygen complexes are stable against passing dislocations. The debris in fact amplify the random force field, facilitating the generation of even more defects in a self-reinforcing loop. This leads to unusually high strain hardening rates and fast breeding of nano-cavities that underlie damage and failure.

The resurgence of the Molten-Salt Nuclear Reactors (MSR) creates interesting problems in molten-salt chemistry. As MSRs operate, the composition and physical properties of salts change because of fission and corrosion. Since Cr is the principal corrosion product and NaCl is a common constituent, we studied the atomic structure of molten NaCl-CrCl3. We found networks of CrCl3− 6 octahedra and an intermediate-range order with nonmonotonic temperature behavior in a remarkable agreement between measurements and ab initio simulations. Even though the corrosion results in minute quantities of dissolved Cr, the speciation of Cr could lead to changes in molten-salt properties in nuclear and solar salts. In particular, we found a much lower than expected melting temperature and a broad metastable liquid-solid coexistence phase. The availability of Cr isotopes with very different neutron-scattering properties makes Cr an ideal model multi-valent ion for experimental validation of new atomistic models such as neural network interatomic potentials.

The relationship between the shear modulus and the flexibility volume has been examined using molecular dynamics simulations in fifteen cubic metallic elements over a range of temperatures. We have observed a universal correlation, and identified the applicability range in which this correlation is quantitatively consistent with the prediction based on the Debye model. Deviation is observed for high modulus metals, and its origin is discussed in terms of the Debye assumptions regarding the vibrational mean squared displacement and the phonon density of states.

‘Smaller is stronger’ has been a well-established tenet for the mechanical strength of small-volume single crystals. However, emerging evidence suggests that this trend does not always hold in the deep sub-micrometre regime (

The finite-temperature mechanical strength of nanoscale pristine metals at laboratory strain rates may be controlled by surface dislocation nucleation, which was hypothesized to be only weakly dependent on the sample size. Previous studies on surface dislocation nucleation investigated factors such as surface steps, oxidation layers and surface diffusion, while the role of surface stresses and sample size remains unclear. Here we perform systematic atomistic calculations on the activation free energy barriers of surface dislocation nucleation in sub-50 nm nanowires. The results demonstrate that surface stresses significantly influence the activation processes of surface dislocation nucleation. This renders the strength strongly dependent on sample size; whether it is “smaller is stronger” or “smaller is weaker” depends on the combined effects of surface stress and applied axial stress, which can be universally explained in terms of the local maximum resolved shear stress. A linear relation between the activation entropy and activation enthalpy (Meyer-Neldel compensation rule) was found to work well across a range of stresses and sample sizes.

Coherent twin boundaries (CTBs) are internal interfaces that can play a key role in markedly enhancing the strength of metallic materials while preserving their ductility. They are known to accommodate plastic deformation primarily through their migration, while experimental evidence documenting large-scale sliding of CTBs to facilitate deformation has thus far not been reported. We show here that CTB sliding is possible whenever the loading orientation enables the Schmid factors of leading and trailing partial dislocations to be comparable to each other. This theoretical prediction is confirmed by real-time transmission electron microscope experimental observations during uniaxial deformation of copper pillars with different orientations and is further validated at the atomic scale by recourse to molecular dynamics simulations. Our findings provide mechanistic insights into the evolution of plasticity in heavily twinned face-centered cubic metals, with the potential for optimizing mechanical properties with nanoscale CTBs in material design., Coherent twin boundaries (CTBs) in face-centered cubic metals are usually considered unable to slide at room temperature. Here, the authors use in situ transmission electron microscopy and molecular dynamics to show CTB sliding in copper nanopillars when leading and trailing partial dislocations have similar Schmid factors.

High-entropy and medium-entropy alloys are presumed to have a configurational entropy as high as that of an ideally mixed solid solution (SS) of multiple elements in near-equal proportions. However, enthalpic interactions inevitably render such chemically disordered SSs rare and metastable, except at very high temperatures. Here we highlight the wide variety of local chemical ordering (LCO) that sets these concentrated SSs apart from traditional solvent-solute ones. Using atomistic simulations, we reveal that the LCO of the multi-principal-element NiCoCr SS changes with alloy processing conditions, producing a wide range of generalized planar fault energies. We show that the LCO heightens the ruggedness of the energy landscape and raises activation barriers governing dislocation activities. This influences the selection of dislocation pathways in slip, faulting, and twinning, and increases the lattice friction to dislocation motion via a nanoscale segment detrapping mechanism. In contrast, severe plastic deformation reduces the LCO towards random SS., Multi-principal-element alloys have been assumed to have the configurational entropy of an ideal solution. Here, the authors use atomistic simulations to show that instead NiCoCr exhibits local chemical order, raising the activation barriers of dislocation activities to elevate mechanical strength.

Summary Molten salts are a promising class of ionic liquids for clean energy applications, such as nuclear and solar energy. However, efficient and accurate evaluation of salt properties from a fundamental, microscopic perspective remains a challenge. Here, we apply artificial neural networks to atomistic modeling of molten NaCl to accurately reproduce the properties from ab initio quantum mechanical calculations based on density functional theory (DFT). The obtained neural network interatomic potential (NNIP) effectively captures the effects of both long-range and short-range interactions, which are crucial for modeling ionic liquids. Extensive validations suggest that the NNIP is capable of predicting the structural, thermophysical, and transport properties of molten NaCl as well as properties of crystalline NaCl, demonstrating near-DFT accuracy and 103× higher efficiency in atomistic simulations. This application of NNIP suggests a paradigm shift from empirical/semiempirical/ab initio approaches to an efficient and accurate machine learning scheme in molten salt modeling.

Gas generation degrades material properties in nuclear applications. The construction of self-assembled bubble channels was proposed to help release gas to the surface. In this study, thermal desorption spectroscopy, in-situ TEM heating and molecular dynamics simulations were carried out to assess the outgassing feasibility in helium-irradiated Cu/Nb multilayers with low structural damage. We found that the formation of outgassing networks has a hybrid diffusive-displacive nature, with diffusive bubble coalescence and crack-induced displacive fracture. The latter could destroy the integrity of the multilayer structure. This suggests that the outgassing strategy making use of self-assembled cavity networks should be carefully designed to avoid large-scale structural failure.

Under very high stresses, dislocations can be accelerated to approach the speed of shear wave over a distance as short as 101 nm. Our atomistic simulations demonstrate that dislocations with such high speeds often react in counter-intuitive manners that are beyond textbook descriptions of conventional dislocation behavior. A high-speed dislocation can “rebound” when hitting a free surface rather than simply annihilate. When two high-speed dislocations collide, they can “penetrate” through each other. An individual dislocation can even spontaneously generate multiple dislocations via self-dissociation. These anomalous mechanisms lead to rapid proliferation of dislocations that are strongly correlated both spatially and temporally, and as such may play a role in high-stress and high-strain-rate plastic deformation; a potentially related case is nanoscale pristine single crystals, which often yield via a large strain burst at ultrahigh stresses.

In the last decade, there has been a sustained resurgence of the Molten-Salt Nuclear Reactor (MSR) concept. As the MSRs operate, chemical compositions and physical properties of salts change because of the creation of fission products, and the effects of corrosion and radiolysis. Therefore, computer simulations of the microscopic structure of multi-component molten salts are necessary to predict changing thermophysical properties. However, first-principles simulations inevitably involve simplifying approximations and therefore require careful experimental validation. Here we present detailed experimental and simulation studies of the structure of molten NaCl-CrCl3 and NaCl-CrCl2 near-eutectic mixtures. These compositions have been chosen to elucidate the behavior of Cr ions in the melts since Cr is the most important corrosion product. Although the corrosion will result in relatively small quantities of Cr in the melt, we used much larger Cr concentration to measure the structure around Cr ions with high resolution. The results of X-ray and neutron diffraction with isotopic substitution, X-ray absorption spectroscopy, and ab initio molecular-dynamic simulations are in agreement. In NaCl-CrCl3 we found CrCl6 3+ octahedra and their networks, as well as intermediate-range order, which manifests itself in the prepeak at ~ 1 Å-1 with non-monotonic temperature behavior. Figure 1 shows one of the main results of this work, namely the comparison of measured and calculated total and partial PDFs of the molten NaCl-CrCl3 near-eutectic mixture. The consistency between the measured and calculated PDFs is remarkable. Neutron diffraction with isotopic substitution allows for a high-fidelity determination of the distances between Cr ions and other species in the melt. By utilizing a combination of neutron diffraction with isotopic substitution of 53Cr, X-ray diffraction, and ab-initio molecular dynamic simulations, we discovered the formation of chains of CrCl6 3- corner-, edge-, and face-sharing octahedra, with Cr-Cl distances of 2.4 Å, and Cl-Cl distance of 3.3 Å. We also found evidence for intermediate-range order that is likely related to inter-chain correlations. In this regard, these ternary salt shows a structure that is reminiscent of that of KCl-MgCl2, LiF-BeF2, and NaCl-UCln. Neutron and X-ray diffraction augment each other to determine partial PDFs Neutrons are particularly useful for studies involving, for example, Cr and Ni, where isotopes with a large difference in neutron cross-section are available. But when isotopic substitution is not achievable, the combination of X-rays and neutrons can extract the information about partial PDFs not otherwise available. The combination of neutrons and X-rays is also useful to overcome experimental constraints, such as compatibility between the salts and crucibles, potential radiation damage to crucibles, and sometimes large background from the sample environment. For example, quartz crucibles are suitable for both neutrons and X-rays and can be used with chloride salts but not with fluoride salts. The latter can be contained in vanadium crucibles for neutrons experiments. Our measurements demonstrate the relative strengths and weaknesses of both techniques for understanding the structure of multi-component salts. In conclusion, the understanding of the structure around Cr ions will be used to calculate properties of molten salt components (e.g., diffusivity) in the presence of Cr impurities. These properties will affect macroscopic thermo-physical properties such as thermal conductivity and viscosity of melts containing that, in turn, are necessary for designing safe and efficient MSRs. The extension of these methods to study melts containing up to 10 components will be discussed. We acknowledge useful discussions with Richard Mayes, Stephen Raiman, Jake Mcmurray (ORNL), and Raluca Scarlat (UC Berkeley). This material is based upon work supported by the Department of Energy under Award Number DE-NE0008751. This research used resources at the Spallation Neutron Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated by the Oak Ridge National Laboratory, and the beamline 28-ID-1 (PDF) of the National Synchrotron Light Source II, a DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Figure 1

When microscopic and macroscopic specimens of metals are subjected to cyclic loading, the creation, interaction, and accumulation of defects lead to damage, cracking, and failure. Here we demonstrate that when aluminum single crystals of submicrometer dimensions are subjected to low-amplitude cyclic deformation at room temperature, the density of preexisting dislocation lines and loops can be dramatically reduced with virtually no change of the overall sample geometry and essentially no permanent plastic strain. This "cyclic healing" of the metal crystal leads to significant strengthening through dramatic reductions in dislocation density, in distinct contrast to conventional cyclic strain hardening mechanisms arising from increases in dislocation density and interactions among defects in microcrystalline and macrocrystalline metals and alloys. Our real-time, in situ transmission electron microscopy observations of tensile tests reveal that pinned dislocation lines undergo shakedown during cyclic straining, with the extent of dislocation unpinning dependent on the amplitude, sequence, and number of strain cycles. Those unpinned mobile dislocations moving close enough to the free surface of the thin specimens as a result of such repeated straining are then further attracted to the surface by image forces that facilitate their egress from the crystal. These results point to a versatile pathway for controlled mechanical annealing and defect engineering in submicrometer-sized metal crystals, thereby obviating the need for thermal annealing or significant plastic deformation that could cause change in shape and/or dimensions of the specimen.

Using nanoscale electrical-discharge-induced rapid Joule heating, we developed a method for ultrafast shape change and joining of small-volume materials. Shape change is dominated by surface-tension-driven convection in the transient liquid melt, giving an extremely high strain rate of ~106 s–1. In addition, the heat can be dissipated in small volumes within a few microseconds through thermal conduction, quenching the melt back to the solid state with cooling rates up to 108 K·s-1. We demonstrate that this approach can be utilized for the ultrafast welding of small-volume crystalline Mo (a refractory metal) and amorphous Cu49Zr51 without introducing obvious microstructural changes, distinguishing the process from bulk welding.

Prof. W.-Z. Han, Dr. L. Huang, Q.-J. Li, B.-Y. Liu, Prof. J. Li, Prof. E. Ma, Prof. Z.-W. Shan Center for Advancing Materials Performance from the Nanoscale and Hysitron Applied Research Center in China State Key Laboratory for Mechanical Behavior of Materials Xi’an Jiaotong University Xi’an 710049 , P. R. China E-mail: zwshan@mail.xjtu.edu.cn Prof. S. Ogata, Prof. H. Kimizuka Department of Mechanical Science and Bioengineering Osaka University Osaka 560-8531 , Japan Prof. S. Ogata Center for Elements Strategy Initiative for Structural Materials Kyoto University Kyoto 606-8501 , Japan Prof. Z.-C. Yang Department of Mechanical Engineering and Materials Science and Department of Bioengineering University of Pittsburgh Pittsburgh , PA 15261 , USA Prof. C. Weinberger Sandia National Laboratories Albuquerque , NM 87185 , USA Prof. C. Weinberger Mechanical Engineering and Mechanics Department Drexel University Philadelphia , PA 19104 , USA Prof. X.-X. Zhang Division of Physical Science and Engineering King Abdullah University of Science & Technology Thuwal 23955-6900 , Saudi Arabia E-mail: xixiang.zhang@kaust.edu.sa Prof. J. Li Department of Nuclear Science and Engineering and Department of Materials Science and Engineering Massachusetts Institute of Technology Cambridge , MA 02139 , USA Prof. E. Ma Department of Materials Science and Engineering Johns Hopkins University Baltimore , MD 21218 , USA

For metallic glasses, ``flexibility volume'' has recently been introduced as a property-revealing indicator of the structural state the glass is in. This parameter incorporates the atomic volume and the vibrational mean-square displacement, to combine both static structure and dynamics information. Flexibility volume was shown to quantitatively correlate with the properties of metallic glasses [J. Ding et al., Nat. Commun. 7, 13733 (2016)]. However, it remains to be examined if this parameter is useful for other types of glasses with bonding characteristics, atomic packing structures, as well as properties that are distinctly different from metallic glasses. In this paper, we tackle this issue through systematic molecular-dynamics simulations of amorphous silicon $(a$-Si) models produced with different cooling rates, as $a$-Si is a prototypical covalently bonded network glass whose structure and properties cannot be characterized using structural parameters such as free volume used for metallic and polymeric glasses. Specifically, we demonstrate a quantitative prediction of the shear modulus of $a$-Si from the flexibility for atomic motion. This flexibility volume descriptor, when evaluated on the atomic scale, is shown to also correlate well with local packing, as well as with the propensity for thermal relaxations and shear transformations, providing a metric to map out and explain the structural and mechanical heterogeneity in the amorphous material. This case study of a model of covalently bonded network $a$-Si, together with our earlier demonstration for metallic glasses, points to the universality of flexibility volume as an indicator of the structure state to link with properties, applicable across amorphous materials with different chemical bonding and atomic packing structures.

Under ultrahigh stresses (e.g., under high strain rates or in small-volume metals) deformation twinning (DT) initiates on a very short time scale, indicating strong spatial-temporal correlations in dislocation dynamics. Using atomistic simulations, here we demonstrate that surface rebound of relativistic dislocations directly and efficiently triggers DT under a wide range of laboratory experimental conditions. Because of its stronger temporal correlation, surface rebound sustained relay of partial dislocations is shown to be dominant over the conventional mechanism of thermally activated nucleation of twinning dislocations.

Sublimation is an important endothermic phase transition in which the atoms break away from their neighbors in the crystal lattice and are removed into the gas phase. Such debonding process may be significantly influenced by dislocations, the crystal defect that changes the bonding environment of local atoms. By performing systematic defects characterization and in situ transmission electron microscopy (TEM) tests on a core--shell MgO-Mg system, which enables us to "modulate" the internal dislocation density, we investigated the role of dislocations on materials' sublimation with particular focus on the sublimation kinetics and mechanism. It was observed that the sublimation rate increases significantly with dislocation density. As the density of screw dislocations is high, the intersection of screw dislocation spirals creates a large number of monatomic ledges, resulting in a "liquid-like" motion of solid-gas interface, which significantly deviates from the theoretically predicted sublimation plane. Our calculation based on density functional theory demonstrated that the remarkable change of sublimation rate with dislocation density is due to the dramatic reduction in binding energy of the monatomic ledges. This study provides direct observation to improve our understanding on this fundamental phase transition as well as to shed light on tuning materials' sublimation by "engineering" dislocation density in applications.

Through in situ scanning electron microscope microcompression tests, we demonstrated that the strain-rate sensitivity of body-centered cubic single crystal iron pillars will be reduced by one order when the pillar size was reduced from 1000 to about 200 nm. In addition, size-strengthening exponent exhibited obvious strain-rate dependence. We propose that the observed behavior is a result of the high stresses required to induce curvature bowout of dislocation arms at small sample or grain sizes, which overwhelms the lattice friction stress contribution and diminishes the role played by the mobility difference between edge and screw dislocations., National Science Foundation (U.S.) (Grants DMR-1120901 and DMR- 1240933), National Natural Science Foundation (China) (Grants (51231005, 51321003 and 11132006), National Basic Research Program of China (973 Program) (Grants 2010CB631003 and 2012CB619402), National 111 Project of China (Grant B06025)

Because of crystal symmetry, body centred cubic (BCC) metals have large differences in lattice friction between screw and edge dislocations, and manifest generally different mechanical behaviours from face centred cubic (FCC) metals. Although mechanical annealing (significant drop in stored dislocation density in response to applied stress) has been observed in FCC metals, it has not been observed in BCC metals so far. Here we show that significant mechanical annealing does occur in BCC Mo pillars, when their diameters decrease to hundreds of nanometers. In addition, there exists a critical diameter for focused ion beam milled pillars, below which the strengthening exponent increases dramatically, from ~0.3 to ~1. Thus, a new regime of size effects in BCC metals is discovered that converges to that of FCC metals, revealing deep connection in the dislocation dynamics of the two systems., National Natural Science Foundation (China) (Grant 50925104), National Natural Science Foundation (China) (Grant 50720145101), National Natural Science Foundation (China) (Grant 50831004), National Basic Research Program of China (973 Program) (Grant 2010CB631003), National Basic Research Program of China (973 Program) (Grant 2012CB619402), National Science Foundation (U.S.) (CMMI-0728069), National Science Foundation (U.S.) (DMR-1008104), National Science Foundation (U.S.) (DMR-1120901), United States. Air Force Office of Scientific Research (FA9550-08-1-0325)

In situ transmission electron microscope compression testing of submicron Al pillars shows two sample size regimes with contrasting behavior underlying the large strain bursts. For small pillars, the bursts originate from explosive and highly correlated dislocation generation, characterized by very high collapse stresses and nearly dislocation-free post-collapse microstructure. For larger pillars, the bursts result from the reconstruction of jammed dislocation configurations, featuring relative low stress levels and retention of dislocation network after bursts.