"Water-in-salt" electrolytes open up exciting new avenues for expanding the electrochemical window of aqueous electrolytes. We investigated the solvation structure and dynamics of highly concentrated lithium bis(trifluoromethane)sulfonimide aqueous electrolyte using experimentally corroborated molecular dynamics simulations. The simulations revealed that the heterogeneous structure of the electrolyte comprises percolating networks of ion and water domains/aggregates. Interestingly, the ionic regions are composed of more TFSI- ions than Li+ ions. The Li+-ion transport mechanism was further explored. Li+ ions can hop along the coordinated TFSI- ions in the ionic aggregates. The calculated correlated transference number of the 20 m electrolyte is ∼0.32, which is reasonably high for the high concentration due to a weak negative correlation between the motion of cations and anions within the heterogeneous microscopic domains. These molecular dynamics results connect the heterogeneous structure of the electrolyte to the correlated dynamics of the Li+ ion and provide a new understanding of the Li+-ion transport mechanism in this novel electrolyte.

The scattering of neutrons can be used to provide information on the structure and dynamics of biological systems on multiple length and time scales. Pursuant to a National Science Foundation-funded workshop in February 2018, recent developments in this field are reviewed here, as well as future prospects that can be expected given recent advances in sources, instrumentation and computational power and methods. Crystallography, solution scattering, dynamics, membranes, labeling and imaging are examined. For the extraction of maximum information, the incorporation of judicious specific deuterium labeling, the integration of several types of experiment, and interpretation using high-performance computer simulation models are often found to be particularly powerful.

This is the Final report on DE-FG02-90ER45429 for the time period from September 1, 1990 to May 31, 2017. The Principal Investigator is Sow-Hsin Chen, Department of Nuclear Science and Engineering, Massachusetts Institute of Technology (MIT), Cambridge, MA 02139 (email: sowhsin@mit.edu). The Administrative Point of Contact at MIT is Sarah Svenson, Senior Contract Administrator, Office of Sponsored Programs, Tel: 617-253-2495, ssvenson@mit.edu. The DOE Program is the Office of Basic Energy Sciences (BES); Program manager is Dr. P. Thiyagarajan, Neutron Scattering SC-22.2/, Germantown Bldg., Germantown, MD 20874 . During these 27 years, the scientific activities has had a number developing emphases, as reflected from the change of Project Title in 1990 as “Construction of a Small Angle Neutron Scattering Spectrometer for Investigation of Microemulsions and Micellar Solutions in Bulk, in Porous Materials...” to “Neutron and X-Ray Scattering Studies of New Green Cement, and Nanoconfined Water” in the last renewal period, 2015-2017, with many title changes in between. Progress Report for each sub-project period was reported to DOE with detailed activity and budgetary reports. It is fair to summary that the chief activity has been in the use neutron, x-ray and laser spectroscopy to investigate materials properties of complex fluids and soft condensed matter. It started with conducting neutron and X-ray scattering experiments to study the structure and dynamics of glass-forming liquids in general first, then more specifically in the case of supercooled water in confined geometry, and culminating in the final study of new green cement. Experiments were conducted at various DOE supported national neutron facilities including ORNL, ANL, BNL and Los Alamos, as well as at NIST/NCNR. Whenever possible, experiments were also performed at numerous world-class facilities, such as those at Saclay and the Institut Laue Langevin (ILL) in Grenoble, France, and at National Synchrotron Radiation Research Center (NSRRC) in recent years in Taiwan, etc. Leveraging on the large number of international collaborate activities, a substantial percentage of activities were supported with collaborators’ own funding sources. These have help to carry out DOE’s mission and produce impressive research products far beyond what was possible with only DOE funding supports. The chief product during this period, 1990-2017, includes (1) Three hundred and eight scientific articles published in peer-reviewed and high-impacted scientific journals during 1990-2017, and a dozen monographs including four books for scientists and graduate students, (2) Twenty-four scientific conferences organized and 209 papers presented at many national and international conferences, (3) educate and train 9 post-doctoral fellows and 28 students including 22 Ph.D. students, 3 M.S. students, and 3 in other categories by providing a research experience in neutron and X-Ray scattering techniques, most of them were supported wholly or in part in the scientific topic of this award during the funding period and (4) numerous high-visibility awards and honors. This final report summarizes and details these research activities and products. At the close of this funding period, the fund from DOE has been totally spent.

ABSTRACTIn the past fifty years, experimental works based on TEM or grazing incidence X ray diffraction have clearly shown that alloys and ceramics exhibit a nano pattering under irradiation [1,2,3]. Many works were devoted to study the nano patterning induced by ion beam mixing in solids [17,18,19]. Understanding the nano patterning will provide scientific bases to tailor materials with well-defined microstructures at the nanometric scale. The slowing down of impinging particles in solids leads to a complex distribution of subcascades. Each subcascade will give rise to an athermal diffusion of atoms in the medium. In this work, we focused on this point. Based on the well-known Cahn Hilliard Cook (CHC) equation, we analytically calculate the structure factor describing the nano patterning within the mean field approximation. It has shown that this analytical structure factor mimics the structure factor extracted from direct numerical simulations of the time dependent CHC equation. It appears that this structure factor exhibits a universal feature under irradiation.

It has been conjectured that a 1st order liquid-to-liquid (L-L) phase transition (LLPT) between high density liquid (HDL) and low density liquid (LDL) in supercooled water may exist, as a thermodynamic extension to the liquid phase of the 1st order transition established between the two bulk solid phases of amorphous ice, the high density amorphous ice (HDA) and the low density amorphous ice (LDA). In this paper, we first recall our previous attempts to establish the existence of the 1st order L-L phase transition through the use of two neutron scattering techniques: a constant Q elastic diffraction study of isobaric temperature scan of the D2O density, namely, the equation of state (EOS) measurements. A pronounced density hysteresis phenomenon in the temperature scan of the density above P = 1500 bar is observed which gives a plausible evidence of crossing the 1st order L-L phase transition line above this pressure; an incoherent quasi-elastic scattering measurements of temperature-dependence of the a-relaxation time of H2O at a series of pressures, namely, the study of the Fragile-to-Strong dynamic crossover (FSC) phenomenon as a function of pressure which we interpreted as the results of crossing the Widom line in the one-phase region. In this new experiment, we used incoherent inelastic neutron scattering (INS) to measure the density of states (DOS) of H atoms in H2O molecules in confined water as function of temperature and pressure, through which we may be able to follow the emergence of the LDL and HDL phases at supercooled temperature and high pressures. We here report for the first time the differences of librational and translational DOSs between the hypothetical HDL and LDL phases, which are similar to the corresponding differences between the well-established HDA and LDA ices. This is plausible evidence that the HDL and LDL phases are the thermodynamic extensions of the corresponding amorphous solid water HDA and LDA ices.

Nucleate pool boiling heat transfer has been experimentally studied at ambient temperature, on a surface with a novel nanofiber mat coating. The nano-textured surface was made of alumina ceramic substrate covered by an electrospun polymer nanofiber mat with a thickness of about 30 μm and immersed in saturated HCFC-123. The surfaces of the individual polymer nanofibers in the mat were copper-plated. Significant enhancements in nucleate boiling heat transfer as well as reduction of surface temperature have been achieved for the copper nanofiber-coated surface compared to a bare surface.

Abstract The Lower and Middle Ordovician paleocave systems form an important type of reservoirs in the Tarim basin, China. To better understand the impact of fractures on the paleocave reservoir development, with acquired wide azimuth 3D seismic data, both post-stack volumetric geometric attributes and P-wave azimuthal AVO analysis are applied to characterize multiscale fracture distributions. In this study, volumetric seismic attributes including dip, discontinuity and curvature are used to identify sub-seismic faults and associated fracture corridors and to describe subtle folds and flexures within the reservoirs. P-wave azimuthal AVO analysis is applied to detecting high angle fractures. Six azimuth-sectored stacks are used to compute P-wave seismic anisotropy from which fracture density and orientation are estimated. Two major sets of conductive fractures trending northeast and northwest, associated with different tectonic events, are identified using imaging logs from seven wells in the study area. Fractures predicted from geometric attributes and from the P-wave azimuthal AVO analysis are compared. The feasibility of two approaches for characterizing and mapping various types of fractures is investigated. Our results show that geometric attributes can better allow detecting and imaging subseismic faults and fracture corridors. The azimuthal AVO analysis allows detecting zones associated with both large scale fracture corridors and small scale diffuse fractures. However, the poor quality data and local geological structures may prevent from using obtained fracture predictions in a quantitative way. Integrating geometric attributes and azimuthal AVO analysis allows obtaining a comprehensive fracture distribution from fracture networks on the corridor scale to diffuse fracture distributions on the small scale. In this paper, case studies are used to illustrate how these two approaches can be integrated to provide a comprehensive multi-scale fracture distributions calibrated with well data and validated against the conceptual fracture models.

This is a response to Soper's two comments (1) regarding our papers (2, 3) in PNAS that (a) the distribution of water across the pores is not uniform and (b) the majority of water may reside outside the pores. Here, we show that we have given proper consideration to both issues and have reconfirmed the validity of our method and conclusion as elaborated in the following.

This is a response to Soper's two comments (1) regarding our papers (2, 3) in PNAS that (a) the distribution of water across the pores is not uniform and (b) the majority of water may reside outside the pores. Here, we show that we have given proper consideration to both issues and have reconfirmed the validity of our method and conclusion as elaborated in the following. The possibility that layering effects across the pores may introduce errors in associating the (100) interchannel peak height with density is not a new idea (reference 3 in ref. 1), and it has already been addressed (2). The arguments of Sopor (4) mainly rest on the assumption that the average density of water does not depend on temperature.

A neutron scattering methodology is proposed to simultaneously determine the total hydrogen adsorption, the excess hydrogen adsorption, and hydrogen gas confined in the porous sample. This method is capable of an absolute measurement of the hydrogen content without need for any calibration. It involves the least amount of corrections and is not likely to be affected by the instrumental factors compared to the traditional gravimetric and volumetric methods. We used this method to study the physisorption behavior at room temperature (RT) of a Pt-doped activated carbon sample as a function of hydrogen pressure. This method will become a simple and important tool for solving various problems arising from the traditional measurements of RT hydrogen storage capacities. It can be combined with an in situ small-angle neutron scattering to study the hydrogen spillover effect in the kinetic adsorption process. Storage capacity and spatial distribution of the hydrogen adsorbed due to spillover are concurrently revealed.

This review article describes our neutron scattering experiments made in the past four years for the understanding of the single-particle (hydrogen atom) dynamics of a protein and its hydration water and the strong coupling between them. We found that the key to this strong coupling is the existence of a fragile-to-strong dynamic crossover (FSC) phenomenon occurring at around T L = 225±5 K in the hydration water. On lowering of the temperature toward FSC, the structure of hydration water makes a transition from predominantly the high density form (HDL), a more fluid state, to predominantly the low density form (LDL), a less fluid state, derived from the existence of a liquid–liquid critical point at an elevated pressure. We show experimentally that this sudden switch in the mobility of hydration water on Lysozyme, B-DNA and RNA triggers the dynamic transition, at a temperature T D = 220 K, for these biopolymers. In the glassy state, below T D , the biopolymers lose their vital conformational flexibility resulting in a substantial diminishing of their biological functions. We also performed molecular dynamics (MD) simulations on a realistic model of hydrated lysozyme powder, which confirms the existence of the FSC and the hydration level dependence of the FSC temperature. Furthermore, we show a striking feature in the short time relaxation ( β -relaxation) of protein dynamics, which is the logarithmic decay spanning 3 decades (from ps to ns). The long time α -relaxation shows instead a diffusive behavior, which supports the liquid-like motions of protein constituents. We then discuss our recent high-resolution X-ray inelastic scattering studies of globular proteins, Lysozyme and Bovine Serum Albumin. We were able to measure the dispersion relations of collective, intra-protein phonon-like excitations in these proteins for the first time. We found that the phonon energies show a marked softening and at the same time their population increases substantially in a certain wave vector range when temperature crosses over the T D . Thus the increase of biological activities above T D has positive correlation with activation of slower and large amplitude collective motions of a protein.

Many of the anomalous properties of water are amplified in the deeply supercooled region. Here we present neutron scattering measurements of the density of heavy water confined in a nanoporous silica matrix MCM-41-S (\approx15 {\AA} pore diameter), namely, the equation of state {\rho}(T,P), in a temperature-pressure range, from 300 K to 130 K and from 1 bar to 2900 bar, where bulk water will crystalize. A sudden change of slope in the otherwise continuous density profile (a "kink") is observed below a certain pressure Pc; however, this feature is absent above Pc. Instead, a hysteresis phenomenon in the density profiles between the warming and cooling scans becomes prominent above Pc. Hence, the data can be interpreted as a line of apparent 2nd-order phase transition at low pressures evolving into a line of 1st-order phase transition at high pressures. If so, the existence of a "tricritical point" at Pc \approx 1500 bar, Tc \approx 210 K becomes another possible scenario to explain the exceptionally rich phase behavior of low-temperature confined water.

Many of the anomalous properties of water are amplified in the deeply supercooled region. Here we present neutron scattering measurements of the density of heavy water confined in a nanoporous silica matrix MCM-41-S (\approx 15 {\AA} pore diameter), in a Temperature-Pressure range inaccessible for the bulk (between 300 K and 130 K, and from ambient pressure to 2900 bar), namely, the equation of state {\rho}(T,P). A sudden change of slope in the otherwise continuous density profile (a "kink") is observed below a certain pressure Pc; however, this feature is absent above Pc. Instead, a hysteresis phenomenon in the density profiles between the warming and cooling scans becomes prominent above Pc. Hence, the data can be interpreted as a line of apparent 2nd-order phase transition at low pressures evolving into a line of 1st-order phase transition at high pressures. If so, the existence of a "tricritical point" at Pc \approx 1500 bar, Tc \approx 210 K becomes a possible scenario to explain the exceptionally rich phase behavior of supercooled confined water.

The spatial distribution of hydrogen physically adsorbed in a nanoporous carbon at room temperature (RT) as a function of H-2 gas pressure is investigated for the first time using small-angle neutron scattering (SANS). A hierarchical pore structure consisting of micropores and a fractal mesopore network of the used activated carbon is also studied to correlate the relationship between the spatial distribution of hydrogen and the pore confinement. The cylinder-like cluster of aggregated hydrogen is formed and is confined in the disklike micropore. The evolution of spatial structures of adsorbed hydrogen with hydrogen pressure is elucidated. A direct experimental observation of the spatial distribution and the behavior of hydrogen adsorbed in the porous materials at RT is still scarce to date. The analysis results obtained by SANS provide new information for the future investigations of the RT storage mechanism of hydrogen in the nanoporous materials developed for the purpose of on-board hydrogen storage.