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All sourcesNASA NTRSDOE OSTI
NASA NTRS2010

Tissuelike 3D Assemblies of Human Broncho-Epithelial Cells

Three-dimensional (3D) tissuelike assemblies (TLAs) of human broncho-epithelial (HBE) cells have been developed for use in in vitro research on infection of humans by respiratory viruses. The 2D monolayer HBE cell cultures heretofore used in such research lack the complex cell structures and interactions characteristic of in vivo tissues and, consequently, do not adequately emulate the infection dynamics of in-vivo microbial adhesion and invasion. In contrast, the 3D HBE TLAs are characterized by more-realistic reproductions of the geometrical and functional complexity, differentiation of cells, cell-to-cell interactions, and cell-to-matrix interactions characteristic of human respiratory epithelia. Hence, the 3D HBE TLAs are expected to make it possible to perform at least some of the research in vitro under more-realistic conditions, without need to infect human subjects. The TLAs are grown on collagen-coated cyclodextran microbeads under controlled conditions in a nutrient liquid in the simulated microgravitational environment of a bioreactor of the rotating- wall-vessel type. Primary human mesenchymal bronchial-tracheal cells are used as a foundation matrix, while adult human bronchial epithelial immortalized cells are used as the overlying component. The beads become coated with cells, and cells on adjacent beads coalesce into 3D masses. The resulting TLAs have been found to share significant characteristics with in vivo human respiratory epithelia including polarization, tight junctions, desmosomes, and microvilli. The differentiation of the cells in these TLAs into tissues functionally similar to in vivo tissues is confirmed by the presence of compounds, including villin, keratins, and specific lung epithelium marker compounds, and by the production of tissue mucin. In a series of initial infection tests, TLA cultures were inoculated with human respiratory syncytial viruses and parainfluenza type 3 viruses. Infection was confirmed by photomicrographs that showed signs of damage by viruses and virus titers (see figure) that indicated large increases in the populations of viruses during the days following inoculation.

Goodwin, Thomas J.↗
DOE OSTI2022

Li2[SeC2Se] · 2 NH3: A Crystalline Ammoniate with a-Se-C=C-Se- Dianion

Reaction of Li2C2 with elemental selenium in a molar ratio of 1:2 in liquid ammonia led to the formation of the ammoniate Li2[SeC2Se] ? 2 NH3. Its crystal structure was solved and refined from high-resolution synchrotron powder diffraction data (P21/c, Z = 4). It contains the ?Se-C?C-Se? anion, unprecedented in a crystalline material, whose existence was corroborated by IR/Raman spectra and electronic-structure theory, showing an almost perfect agreement with calculated spectra. Elaborated magnetic-bottle and velocity-map imaging photoelectron spectroscopic investigations show that the ?Se-C?C-Se? radical anion can be transferred to the gas phase, where it was analyzed by NIPE (Negative Ion Photoelectron) and VMI (Velocity-Map Imaging) spectra, which correlate nicely with simulated spectra based on 2?u ? 3Sg – and 2?u ?1Sg + transitions including spin-orbit couplings

Hetzert, Marc↗
DOE OSTI2018

Role of Surface Friction on Shallow Nonprecipitating Convection

The role of surface friction on shallow nonprecipitating convection is investigated using a series of large-eddy simulations with varying surface friction velocity and with a cloud identification algorithm. As surface friction intensifies, convective rolls dominate over convective cells and secondary overturning circulation becomes stronger in the subcloud layer, thus transporting more moisture upward and more heat downward between the subcloud and cloud layers. Identifying individual clouds, using the identification algorithm based on a three-dimensional topological analysis, reveals that intensified surface friction increases the number of clouds and the degree of tilting in the downstream direction. Highly intensified surface friction increases wind shear across the cloud base and induces cloud tilting, which leads to a vertically parabolic profile of liquid water mixing ratio instead of the classical two-layer structure (conditionally unstable and trade inversion layers). Furthermore, cloud tilting induces more cloud cover and more cloud mass flux much above the cloud base (e.g., 0.8 < z < 1.2 km), but less cloud cover and less cloud mass flux in the upper cloud layer (e.g., z > 1.2 km) because of increased lateral entrainment rate. Similarly, profiles of directly measured entrainment and detrainment rates show that detrainment in the lower cloud layer becomes smaller with stronger surface friction.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Ultrafast visualization of phase transitions in nonequilibrium warm dense matter

Intense ultrafast laser excitation brings materials into highly nonequilibrium states with complex solid–liquid phase transitions. These ultrafast processes yield warm dense matter (WDM) conditions characterized by comparable thermal and Fermi energies, and strong ion–ion coupling. Here, we review recent studies employing mega-electron-volt ultrafast electron diffraction to resolve the structural dynamics of nonequilibrium WDM created by femtosecond laser heating of solids. Furthermore, for the study of warm dense gold, the results showed homogeneous melting that occurs within tens of picoseconds at absorbed energy densities of 0.4–1.4 MJ/kg. These results constrained the electron–ion coupling rate and revealed the melting sensitivity to nucleation seeds. For the study of radiation-damaged tungsten, the results showed a melting transition below the melting temperature. Molecular dynamics simulations suggested that this melting behavior is driven by vacancy defect clusters from radiation damage. These studies provided atomic-level insights into the melting behavior of materials under extreme conditions.

36 MATERIALS SCIENCE↗
NASA NTRS1998

Tropical Oceanic Precipitation Processes over Warm Pool: 2D and 3D Cloud Resolving Model Simulations

Rainfall is a key link in the hydrologic cycle as well as the primary heat source for the atmosphere, The vertical distribution of convective latent-heat release modulates the large-scale circulations of the tropics, Furthermore, changes in the moisture distribution at middle and upper levels of the troposphere can affect cloud distributions and cloud liquid water and ice contents. How the incoming solar and outgoing longwave radiation respond to these changes in clouds is a major factor in assessing climate change. Present large-scale weather and climate models simulate cloud processes only crudely, reducing confidence in their predictions on both global and regional scales. One of the most promising methods to test physical parameterizations used in General Circulation Models (GCMS) and climate models is to use field observations together with Cloud Resolving Models (CRMs). The CRMs use more sophisticated and physically realistic parameterizations of cloud microphysical processes, and allow for their complex interactions with solar and infrared radiative transfer processes. The CRMs can reasonably well resolve the evolution, structure, and life cycles of individual clouds and cloud systems, The major objective of this paper is to investigate the latent heating, moisture and momenti,im budgets associated with several convective systems developed during the TOGA COARE IFA - westerly wind burst event (late December, 1992). The tool for this study is the Goddard Cumulus Ensemble (CCE) model which includes a 3-class ice-phase microphysical scheme, The model domain contains 256 x 256 grid points (using 2 km resolution) in the horizontal and 38 grid points (to a depth of 22 km depth) in the vertical, The 2D domain has 1024 grid points. The simulations are performed over a 7 day time period. We will examine (1) the precipitation processes (i.e., condensation/evaporation) and their interaction with warm pool; (2) the heating and moisture budgets in the convective and stratiform regions; (3) the cloud (upward-downward) mass fluxes in convective and stratiform regions; (4) characteristics of clouds (such as cloud size, updraft intensity and cloud lifetime) and the comparison of clouds with Radar observations. Differences and similarities in organization of convection between simulated 2D and 3D cloud systems. Preliminary results indicated that there is major differences between 2D and 3D simulated stratiform rainfall amount and convective updraft and downdraft mass fluxes.

Tao, W.- K.↗
DOE OSTI2017

Pressure Dependence of the Boson Peak of Glassy Glycerol

The pressure dependence of the Boson peak (BP) of glycerol, including its behavior across the liquid-glass transition, has been studied under pressure using Raman scattering. A significant increase of the BP frequency was observed with pressure up to 11 GPa at room temperature. The pressure dependence of BP frequency ν BP is proportional to (1+P/P 0 ) 1/3 , where P and P 0 are the pressure and a constant, respectively, the spectra are consistent with a soft potential model. The characteristic length of medium range order is close in size to a cyclic trimer of glycerol molecules, which is predicted as the medium range order of a BP vibration using molecular dynamics simulations. The pressure dependence of a characteristic length of medium range order is nearly constant. The pressure induced structural changes in glycerol can be understood in terms of the shrinkage of voids with cyclic trimers remaining up to at least 11 GPa. Lastly, the pressure dependence of intermolecular O-H stretching mode indicates that the intermolecular hydrogen bond distance gradually decreases below the glass transition pressure of ~5 GPa, while it becomes nearly constant in the glassy state indicating the disappearance of the free volume in the dense glass.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Iron Carbides in Fischer–Tropsch Synthesis: Theoretical and Experimental Understanding in Epsilon-Iron Carbide Phase Assignment

As active phases in low-temperature Fischer–Tropsch synthesis for liquid fuel production, epsilon iron carbides are critically important industrial materials. However, the precise atomic structure of epsilon iron carbides remains unclear, leading to a half-century of debate on the phase assignment of the ε-Fe 2 C and ε’-Fe 2.2 C. Here, we resolve this decades-long question by a combining theoretical and experimental investigation to assign the phases unambiguously. First, we have investigated the equilibrium structures and thermal stabilities of ε-Fe x C, (x = 1, 2, 2.2, 3, 4, 6, 8) by first-principles calculations. We have also acquired X-ray diffraction patterns and Mössbauer spectra for these epsilon iron carbides, and compared them with the simulated results. These analyses indicate that the unit cell of ε-Fe 2 C contains only one type of chemical environment for Fe atoms, while ε’-Fe 2.2 C has six sets of chemically distinct Fe atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Positioning colloids at the surfaces of cholesteric liquid crystal droplets

We report on the internal configurations of aqueous dispersions of droplets of cholesteric liquid crystals (LCs; 5–50 μm-in-diameter; comprised of 4-cyano-4'-pentylbiphenyl and 4-(1-methylheptyloxycarbonyl)phenyl-4-hexyloxybenzoate) and their influence on the positioning of surface-adsorbed colloids (0.2 or 1 μm-in-diameter polystyrene (PS)). When N = 2D/P was less than 4, where D is the droplet diameter and P is the cholesteric pitch, the droplets adopted a twisted bipolar structure (TBS) and colloids were observed to assume positions at either the poles or equator of the droplets. A statistical analysis of the distribution of locations of the colloids revealed a potential well of depth 2.7 k B T near the equator, a conclusion that was supported by computer simulations performed via the minimization of the Landau–de Gennes free energy (well depth of 7 k B T from simulation). In contrast, for N > 4, a majority of the droplets exhibited a radial spherical structure (RSS) characterized by a pair of closely spaced surface defects (angle of separation with respect to the center of the droplet θ < 5°) connected by a disclination winding to/from the droplet center, which led to the positioning of pairs of colloids with well-defined spacing at these surface defects. The separation of the pairs of surface-adsorbed colloids was colloid size-dependent, ranging from 1.11 ± 0.04 μm for 1 μm-in-diameter colloids to 1.7 ± 0.2 μm for 200 nm-in-diameter colloids. We also observed long-lived metastable configurations in which the two surface point defects were separated by much larger distances (corresponding to populations with angles of θ = 20 ± 10° and 85 ± 10° with respect to the center), and observed these pairs of defects to also position pairs of colloids. A third configuration, the diametrical spherical structure (DSS) was also observed. Consistent with the predictions of computer simulations, we found experimentally that the DSS is indeed composed of disconnected defect rings positioned along the diameter of the droplet. Finally, these results reveal that the rich palette of defects exhibited by confined cholesteric LC systems (equilibrium and metastable) provide the basis of a versatile class of templates that enable the surface positioning of colloids in ways that are not possible with achiral LC droplets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Advances and Achievements in In Situ Analysis of Corrosion and Structure–Property Relationship in Mg Alloys

Every year, TMS Magnesium Committee carefully selects a special topic in magnesium (Mg) related research and development not only having the hottest subject from both academic and industrial perspectives but also demonstrating major achievements within this subject. Following last year’s topic on Mg microallying [1], this year’s focus is on in-situ methods and associated techniques in their broad definition spanning from laboratory- to large- scale facilities to process monitoring. The applications of in-situ techniques have a wide spectrum from the analysis of melts and liquid-solid transitions to solid-state phenomena during thermo-mechanical processing and heat treatments to surface interactions with various environments. Therefore, such works are of significant interest to scientists working in the area of Mg alloy development as well as to a much broader audience from both academia and industry. This interest is primarily caused by challenges in the analysis of structure-property relationship in Mg alloys, and even cursory glance of literature reveals sharp increase of publications relevant to this topic recently. For instance, very high reactivity of Mg as well as its well-known propensity to substantially alter structure upon unloading in mechanical testing makes it difficult to understand and thus to simulate correlation between microstructures observed in post-mortem analysis and physical processes during testing or fabrication. However, recent advances in in-situ analysis based on large-scale research facilities such as neutron scattering and synchrotron radiation sources as well as microscopy-based, acoustic emission, and other more traditional techniques allowed significant achievements. Apart from apparent development of relevant experimental techniques, a significant part of this success should also be attributed to increasing accessibility of the facilities and simplification of their use from a user perspective. The selection of articles in this special topic is quite far from comprehensive review covering all aspects of in-situ methods available for metallic materials development. However, this was not the purpose in any case. Instead, this selection is intended to present several studies on Mg alloys and Mg-based composites with the use of in-situ techniques. In addition, it overviews two techniques, ‘Acoustic Emission’ (AE) and ‘Ambient-Pressure X-ray Photoelectron Spectroscopy’ (AP-XPS), that are rather novel to the Mg community. These studies are supposed to give readers representative examples of such techniques potential and to help in navigating the spectrum of modern state-of-the-art analytical methods facilitating the development of Mg alloys. These articles are organized in the order corresponding to typical Mg alloy lifecycle from material preparation and solidification to thermo-mechanical processing and product fabrication to degradation.

36 MATERIALS SCIENCE↗
NASA NTRS1996

Development of a Pressure Box to Evaluate Reusable-Launch-Vehicle Cryogenic-Tank Panels

A cryogenic pressure-box test machine has been designed and is being developed to test full-scale reusable-launch-vehicle cryogenic-tank panels. This machine is equipped with an internal pressurization system, a cryogenic cooling system, and a heating system to simulate the mechanical and thermal loading conditions that are representative of a reusable-launch-vehicle mission profile. The cryogenic cooling system uses liquid helium and liquid nitrogen to simulate liquid hydrogen and liquid oxygen tank internal temperatures. A quartz lamp heating system is used for heating the external surface of the test panels to simulate cryogenic-tank external surface temperatures during re-entry of the launch vehicle. The pressurization system uses gaseous helium and is designed to be controlled independently of the cooling system. The tensile loads in the axial direction of the test panel are simulated by means of hydraulic actuators and a load control system. The hoop loads in the test panel are reacted by load-calibrated turnbuckles attached to the skin and frame elements of the test panel. The load distribution in the skin and frames can be adjusted to correspond to the tank structure by using these turnbuckles. The seal between the test panel and the cryogenic pressure box is made from a reinforced Teflon material which can withstand pressures greater than 52 psig at cryogenic temperatures. Analytical results and tests on prototype test components indicate that most of the cryogenic-tank loading conditions that occur in flight can be simulated in the cryogenic pressure-box test machine.

Ambur, Damodar R.↗
NASA NTRS1996

Development of a Pressure Box to Evaluate Reusable-Launch-Vehicle Cryogenic-Tank Panels

A cryogenic pressure-box test machine has been designed and is being developed to test full-scale reusable launch vehicle cryogenic-tank panels. This machine is equipped with an internal pressurization system, a cryogenic cooling system, and a heating system to simulate the mechanical and thermal loading conditions that are representative of a reusable launch vehicle mission profile. The cryogenic cooling system uses liquid helium and liquid nitrogen to simulate liquid hydrogen and liquid oxygen tank internal temperatures. A quartz lamp heating system is used for heating the external surface of the test panels to simulate cryogenic-tank external surface temperatures during re-entry of the launch vehicle. The pressurization system uses gaseous helium and is designed to be controlled independently of the cooling system. The tensile loads in the axial direction of the test panel are simulated by means of hydraulic actuators and a load control system. The hoop loads in the test panel are reacted by load-calibrated turnbuckles attached to the skin and frame elements of the test panel. The load distribution in the skin and frames can be adjusted to correspond to the tank structure by using these turnbuckles. The seal between the test panel and the cryogenic pressure box is made from a reinforced Teflon material which can withstand pressures greater than 52 psig at cryogenic temperatures. Analytical results and tests on prototype test components indicate that most of the cryogenic-tank loading conditions that occur in flight can be simulated in the cryogenic pressure-box test machine.

Ambur, Damodar R.↗
DOE OSTI2022

ExaCA: A performance portable exascale cellular automata application for alloy solidification modeling

Modeling the as-solidified grain structures that form during alloy processing is a critical component in understanding process-property relationships, particularly for additive manufacturing (AM) where grain structure is very sensitive to processing conditions. While cellular automata (CA)-based models have proven able to predict aspects of microstructure for several alloys and AM process conditions, long run times and large resource sets required limit the utility and the problem size to which existing CA models can be applied. As part of the ExaAM project, an initiative within the Exascale Computing Project (ECP) to develop, test, and optimize an exascale-capable coupled and self-consistent model of AM parts, we developed ExaCA (https://github.com/LLNL/ExaCA) for the liquid–solid phase transformation in the wake of AM melt pools. The CA-based code is parallelized using MPI and the Kokkos programming model, the latter enabling simulation on both CPUs and GPUs within a single-source implementation. Here, we detail the steps taken to transform a baseline, MPI-based CA code into one that is performant on CPUs and GPUs. Performance testing of ExaCA on Summit (a pre-exascale machine at Oak Ridge National Laboratory) was used to quantify CPU–GPU speedup comparing with equal numbers of nodes. Testing showed comparable CPU performance to the MPI-only CA code and a 5-20x speedup when running AM-based test problems using GPUs. The improved performance of CA through GPU utilization and the performance portable nature of ExaCA will enable accurate part-scale modeling by harnessing the power of current and future generations of high performance computing resources. Future work will include improving the strong scaling of ExaCA on GPUs by reducing load imbalance associated with the locality of the problem, and continuing performance optimization across exascale hardware.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Third-body stabilization of supercritical CO 2 in CO oxidation: development and application of a ReaxFF force field for the CO/O/CO 2 system

Supercritical CO 2 (scCO 2 ) plays a crucial role as a solvent in separation processes, advanced power cycles, and materials processing. Nonetheless, the atomistic comprehension of how the dense scCO 2 matrix influences the fundamental reaction of carbon monoxide (CO) is still insufficiently explored. Experimental studies and molecular dynamics (MD) simulations frequently fail to detect the highly reactive, transient intermediates, such as atomic oxygen (O), that drive these reactions. Here, to address this issue, we have developed a novel ReaxFF reactive force field for the CO 2 /CO/O system. The force field parameters were calibrated using density functional theory and second-order Møller-Plesset calculations to model CO 2 crystal properties, intermolecular interactions, bond dissociation curves, and reaction energy barriers. The force field reproduces the cohesive energy of the CO 2 crystal, the pressure characteristics of bulk scCO 2 , the equation-of-state behavior over a wide pressure–density range, the pressure dependence of the C–O bond length under compression, and the structural properties of liquid and scCO 2 , as documented by experiments, ab-initio MD, and prominent non-reactive models. The force field was subsequently applied to study the CO + O → CO 2 reaction. In a dilute environment, the reaction is inefficient as the newly formed CO 2 rapidly dissociates due to excess kinetic and potential energy acquired from the exothermic reaction. Conversely, in a dense scCO 2 environment, the surrounding matrix acts as an efficient third body, stabilizing the emerging CO2 product via molecular collisions. Statistical analysis confirms an average excess energy dissipation of 133.9 ± 3.6 kcal/mol over 112.4 ± 17.9 ps. Kinetic energy decomposition reveals that ∼ 92% of the excess kinetic energy is stored in internal (rotational and vibrational) degrees of freedom. This ReaxFF force field establishes a mechanistic foundation for third-body stabilization in dense reactive environments.

Chowdhury, Emdadul Haque [Pennsylvania State Univ.↗
DOE OSTI2021

Bulk Glassy GeTe 2 : A Missing Member of the Tetrahedral GeX 2 Family and a Precursor for the Next Generation of Phase-Change Materials

Vitreous germanium disulfide GeS 2 and diselenide GeSe 2 belong to canonical chalcogenide glasses extensively studied over the past half century. Their high-temperature orthorhombic polymorphs are congruently melting compounds, and the tetrahedral crystal and glass structure is largely preserved in the melt. In contrast, the ditelluride counterpart is absent in the Ge-Te phase diagram, which shows only a single compound, monotelluride GeTe. Phase-change materials based on GeTe have become a technologically important class of solids, and their structure and properties are also widely studied. Surprisingly, very scarce information is available for alloys having GeTe 2 stoichiometry. Using a fast quenching procedure in silica capillaries, high-energy X-ray diffraction, and Raman spectroscopy supported by first-principles simulations, we show that bulk glassy GeTe 2 differs substantially from the lighter GeX 2 members, revealing 46% of trigonal germanium, 31% of three-fold coordinated tellurium, and only 20% of edge-sharing tetrahedra or pyramids. The fraction of homopolar Ge-Ge bonds is low; however, the population of dominant Te-Te dimers and Te n oligomers, n <= 10, appears to be significant. The complex structural and chemical topology of g-GeTe 2 is directly related to the thermodynamic metastability of germanium ditelluride, schematically represented by the following reaction: GeTe 2 $\rightleftarrows$ GeTe + Te. Disproportionation is complete above liquidus in the temperature range of semiconductor-metal transition, and the dense metallic GeTe 2 liquid, mostly consisting of five-fold coordinated Ge species, exhibits high fluidity, strong fragility (m = 99 ± 5), and presumably a fast structural transformation rate combined with low atomic mobility in the vicinity of the glass transition temperature, favorable for reliable long-term data retention in nonvolatile memories. The observed and predicted characteristic features make GeTe 2 a promising precursor for the next generation of phase-change materials, especially coupled with additional metal doping, depolymerizing the tetrahedral interconnected glass network and accelerating (sub)nanosecond crystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Toward a First-Principles Framework for Predicting Collective Properties of Electrolytes

Conspectus Given the universal importance of electrolyte solutions, it is natural to expect that we have a nearly complete understanding of the fundamental properties of these solutions (e.g., the chemical potential) and that we can therefore explain, predict, and control the phenomena occurring in them. In fact, reality falls short of these expectations. But, recent advances in the simulation and modeling of electrolyte solutions indicate that it should soon be possible to make progress toward these goals. In this Account, we will discuss the use of first-principles interaction potentials based in quantum mechanics (QM) to enhance our understanding of electrolyte solutions. Specifically, we will focus on the use of quantum density functional theory (DFT) combined with molecular dynamics simulation (DFT-MD) as the foundation for our approach. The overarching concept is to understand and accurately reproduce the balance between local or short-ranged (SR) structural details and long-range (LR) correlations, allowing the prediction of the thermodynamics of both single ions in solution as well as the collective interactions characterized by activity/osmotic coefficients. In doing so, relevant collective motions and driving forces characterized by chemical potentials can be determined. Here, in this Account, we will make the case that understanding electrolyte solutions requires a faithful QM representation of the SR nature of the ion–ion, ion–water, and water–water interactions. However, the number of molecules that is required for collective behavior makes the direct application of high-level QM methods that contain the best SR physics untenable, making methods that balance accuracy and efficiency a practical goal. Alternatives such as continuum solvent models (CSMs) and empirically based classical molecular dynamics have been extensively employed to resolve this problem but without yet overcoming the fundamental issue of SR accuracy. We will demonstrate that accurately describing the SR interaction is imperative for predicting both intrinsic properties, namely, at infinite dilution, and collective properties of electrolyte solutions. DFT has played an important role in our understanding of condensed phase systems, e.g., bulk liquid water, the air–water interface, ions in bulk, and at the air–water interface. This approach holds huge promise to provide benchmark calculations of electrolyte solution properties that will allow for the development and improvement of more efficient methods, as well as an enhanced understanding of fundamental phenomena. However, the standard protocol using the generalized gradient approximation with van der Waals (vdW) correction requires improvement in order to achieve a high level of quantitative accuracy. Simply simulating with higher level DFT functionals may not be the best route considering the significant computational cost. Alternative methods of incorporating information from higher levels of QM should be explored; e.g., using force matching techniques on small clusters, where high level benchmark calculations are possible, to develop ideal correction terms to the DFT functional is a promising possibility. We argue that DFT with statistical mechanics is becoming an increasingly useful framework enabling the prediction of collective electrolyte properties.

Duignan, Timothy T.↗
DOE OSTI2020

Review of Emerging Potassium–Sulfur Batteries

Abstract This is the first review on potassium–sulfur (K–S) batteries (KSBs), which are emerging metal battery (MB) systems. Since KSBs are quite new, there are fundamental questions regarding the electrochemistry of S‐based cathode and of K metal anode, as well as the holistic aspects of full‐cell performance. The manuscript begins with a critical discussion regarding the potassium–sulfur electrochemistry and on how it differs from the much better‐known lithium–sulfur. Cathodes are discussed next, focusing on the role of sulfur structure, carbon host chemistry and porosity, and electrolytes in establishing the reversible potassium sulfide K 2 S n phase sequence, the parasitic polysulfide shuttle, pulverization‐driven capacity fade, etc. Following is a discussion of solid‐state electrolytes (SSEs), including of hybrid solid–liquid systems that show much promise. Potassium metal anodes are then critically reviewed, emphasizing electrolyte reactions to form stable versus unstable solid electrolyte interphase (SEI), covering the current understanding of potassium dendrites, and highlighting the deep‐eutectic K–Na alloying approaches for room temperature liquid anodes. The manuscript concludes with K–S batteries, focusing on cell architectures and providing quantitative performance comparisons as master plots. Unanswered scientific/technological questions are identified, emerging research opportunities are discussed, and potential experimental and simulation‐based studies that can unravel these unknowns are proposed.

Ding, Jia↗
DOE OSTI2022

Water Weakening of Calcium Oxide

Chemomechanical processes such as water weakening can control the permeability and deformation of rocks and manmade materials. Here, atomistic modeling and nanomechanical experiments were used to identify molecular origins of chemomechanical effects in calcium oxide (CaO) and its effect on observed elastic, plastic, and brittle deformation. Classical molecular dynamics simulations with the bond order-based reactive force-field ReaxFF were used to assess brittle fracture. In the presence of water, CaO fractured earlier and more often during quasi-static loading, with a calculated reduction in fracture toughness of ~80% associated with changes in the stress distribution around the crack tip. Experimentally, elastic and plastic deformation of CaO surfaces exposed to water was assessed experimentally using in situ liquid nanoindentation. Nanoindentation showed that following exposure to water, the contact hardness decreased by 1–2 orders of magnitude and decreased the modulus by 2–3 orders of magnitude due to surface hydroxylation. Furthermore, the strong chemomechanical effects on the mechanical processes in CaO suggests that minerals with similar structures may exhibit comparable effects, influencing the stability of cements and geomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Critical role of slags in pitting corrosion of additively manufactured stainless steel in simulated seawater

Abstract Pitting corrosion in seawater is one of the most difficult forms of corrosion to identify and control. A workhorse material for marine applications, 316L stainless steel (316L SS) is known to balance resistance to pitting with good mechanical properties. The advent of additive manufacturing (AM), particularly laser powder bed fusion (LPBF), has prompted numerous microstructural and mechanical investigations of LPBF 316L SS; however, the origins of pitting corrosion on as-built surfaces is unknown, despite their utmost importance for certification of LPBF 316L SS prior to fielding. Here, we show that Mn-rich silicate slags are responsible for pitting of the as-built LPBF material in sodium chloride due to their introduction of deleterious defects such as cracks or surface oxide heterogeneities. In addition, we explain how slags are formed in the liquid metal and deposited at the as-built surfaces using high-fidelity melt pool simulations. Our work uncovers how LPBF changes surface oxides due to rapid solidification and high-temperature oxidation, leading to fundamentally different pitting corrosion mechanisms.

36 MATERIALS SCIENCE↗