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At least 1,153 records · Page 64

Beyond Local Solvation Structure: Nanometric Aggregates in Battery Electrolytes and their Effect on Electrolyte Properties

Electrolytes are an essential component of all electrochemical storage and conversion devices, such as batteries. In the history of battery development, the complex nature of electrolytes has often been a bottleneck. Fundamental knowledge of electrolyte systems encompasses elucidation of structure-property relationships of the solution species. Recently, nanometric aggregates have been observed in several classes of electrolytes, including super-concentrated, redox-flow, multivalent, polymer, and ionic liquid-based electrolytes. Compared with the well-studied local solvation structures such as contact ion pairs and solvent-separated ions, these aggregates impose unique effects on the ion distribution and transport both within bulk electrolytes and at electrode/electrolyte interfaces. This Perspective highlights the discovery of the aggregates in various battery electrolytes and their impact on electrolyte properties. We also present an outlook for future studies of this emerging field of nanometric aggregates and the need for the development of new experimental and computational tools to study their properties.

Yu, Zhou↗

External Tank Program - Legacy of Success

The largest single element of Space Shuttle is the External Tank (ET), which serves as the structural backbone of the vehicle during ascent and provides liquid propellants to the Orbiter s three Main Engines. The ET absorbs most of the seven million pounds of thrust exerted by the Solid Rocket Boosters and Main Engines. The design evolved through several block changes, reducing weight each time. Because the tank flies to orbital velocity with the Space Shuttle Orbiter, minimization of weight is mandatory, to maximize payload performance. The initial configuration, the standard weight tank, weighed 76,000 pounds and was an aluminum 2219 structure. The light weight tank weighed 66,000 pounds and flew 86 missions. The super light weight tank weighed 58,500 pounds and was primarily an aluminum-lithium structure. The final configuration and low weight enabled system level performance sufficient for assembly of the International Space Station in a high inclination orbit, vital for international cooperation. Another significant challenge was the minimization of ice formation on the cryogenic tanks. This was essential due to the system configuration and the choice of ceramic thermal protection system materials on the Orbiter. Ice would have been a major debris hazard. Spray on foam insulation materials served multiple functions including thermal insulation, conditioning of cryogenic propellants, and thermal protection for the tank structure during ascent and entry. The tank is large, and unique manufacturing facilities, tooling, and handling, and transportation operations were developed. Weld processes and tooling evolved with the design as it matured through several block changes. Non Destructive Evaluation methods were used to assure integrity of welds and thermal protection system materials. The aluminum-lithium alloy was used near the end of the program and weld processes and weld repair techniques had to be refined. Development and implementation of friction stir welding was a substantial technology development incorporated during the Program. Automated thermal protection system application processes were developed for the majority of the tank surface. Material obsolescence was an issue throughout the multi-decade program. Process controls were implemented to assure cleanliness in the production environment, to control contaminants, and to preclude corrosion. Each tank was accepted via rigorous inspections, including non-destructive evaluation techniques, proof testing, and all systems testing. In the post STS-107 era, the project focused on ascent debris risk reduction. This was accomplished via stringent process controls, post flight assessment using substantially improved imagery, and selective redesigns. These efforts were supported with a number of test programs to simulate combined environments. The debris risk was reduced by two orders of magnitude. During this time a major natural disaster was overcome when hurricane Katrina damaged the manufacturing facility. Numerous lessons from these efforts, the manufacturing and material processing issues, the key design features, and evolution of the design will be discussed.

Pilet, Jeffery C.↗

Developing NDE Techniques for Large Cryogenic Tanks

The Shuttle Program requires very large cryogenic ground storage tanks in which to store liquid oxygen and hydrogen. The existing Pads A and B Launch Complex-39 tanks, which will be passed onto future launch programs, are 45 years old and have received minimal refurbishment and only external inspections over the years. The majority of the structure is inaccessible without a full system drain of cryogenic liquid and granular insulation in the annular region. It was previously thought that there was a limit to the number of temperature cycles that the tanks could handle due to possible insulation compaction before undergoing a costly and time consuming complete overhaul; therefore the tanks were not drained and performance issues with these tanks, specifically the Pad B liquid hydrogen tank, were accepted. There is a needind an opportunity, as the Shuttle program ends and work to upgrade the launch pads progresses, to develop innovative non-destructive evaluation (NDE) techniques to analyze the current tanks. Techniques are desired that can aid in determining the extent of refurbishment required to keep the tanks in service for another 20+ years. A nondestructive technique would also be a significant aid in acceptance testing of new and refurbished tanks, saving significant time and money, if corrective actions can be taken before cryogen is introduced to the systems.

Parker, Don↗

Angle between DNA linker and nucleosome core particle regulates array compaction revealed by individual-particle cryo-electron tomography

Abstract The conformational dynamics of nucleosome arrays generate a diverse spectrum of microscopic states, posing challenges to their structural determination. Leveraging cryogenic electron tomography (cryo-ET), we determine the three-dimensional (3D) structures of individual mononucleosomes and arrays comprising di-, tri-, and tetranucleosomes. By slowing the rate of condensation through a reduction in ionic strength, we probe the intra-array structural transitions that precede inter-array interactions and liquid droplet formation. Under these conditions, the arrays exhibite irregular zig-zag conformations with loose packing. Increasing the ionic strength promoted intra-array compaction, yet we do not observe the previously reported regular 30-nanometer fibers. Interestingly, the presence of H1 do not induce array compaction; instead, one-third of the arrays display nucleosomes invaded by foreign DNA, suggesting an alternative role for H1 in chromatin network construction. We also find that the crucial parameter determining the structure adopted by chromatin arrays is the angle between the entry and exit of the DNA and the corresponding tangents to the nucleosomal disc. Our results provide insights into the initial stages of intra-array compaction, a critical precursor to condensation in the regulation of chromatin organization.

59 BASIC BIOLOGICAL SCIENCES↗

Computational Advances in Ionic Liquid Applications for Green Chemistry: A Critical Review of Lignin Processing and Machine Learning Approaches

The valorization and dissolution of lignin using ionic liquids (ILs) is critical for developing sustainable biorefineries and a circular bioeconomy. This review aims to critically assess the current state of computational and machine learning methods for understanding and optimizing IL-based lignin dissolution and valorization processes reported since 2022. The paper examines various computational approaches, from quantum chemistry to machine learning, highlighting their strengths, limitations, and recent advances in predicting and optimizing lignin-IL interactions. Key themes include the challenges in accurately modeling lignin’s complex structure, the development of efficient screening methodologies for ionic liquids to enhance lignin dissolution and valorization processes, and the integration of machine learning with quantum calculations. These computational advances will drive progress in IL-based lignin valorization by providing deeper molecular-level insights and facilitating the rapid screening of novel IL-lignin systems.

09 BIOMASS FUELS↗

A Study of Bubble and Slug Gas-Liquid Flow in a Microgravity Environment

The influence of gravity on the two-phase flow dynamics is obvious.As the gravity level is reduced,there is a new balance between inertial and interfacial forces, altering the behavior of the flow. In bubbly flow,the absence of drift velocity leads to spherical-shaped bubbles with a rectilinear trajectory.Slug flow is a succession of long bubbles and liquid slug carrying a few bubbles. There is no flow reversal in the thin liquid film as the long bubble and liquid slug pass over the film. Although the flow structure seems to be simpler than in normal gravity conditions,the models developed for the prediction of flow behavior in normal gravity and extended to reduced gravity flow are unable to predict the flow behavior correctly.An additional benefit of conducting studies in microgravity flows is that these studies aide the development of understanding for normal gravity flow behavior by removing the effects of buoyancy on the shape of the interface and density driven shear flows between the gas and the liquid phases. The proposal calls to study specifically the following: 1) The dynamics of isolated bubbles in microgravity liquid flows will be analyzed: Both the dynamics of spherical isolated bubbles and their dispersion by turbulence, their interaction with the pipe wall,the behavior of the bubbles in accelerated or decelerated flows,and the dynamics of isolated cylindrical bubbles, their deformation in accelerated/decelerated flows (in converging or diverging channels), and bubble/bubble interaction. Experiments will consist of the use of Particle Image Velocimetry (PIV) and Laser Doppler Velocimeters (LDV) to study single spherical bubble and single and two cylindrical bubble behavior with respect to their influence on the turbulence of the surrounding liquid and on the wall 2) The dynamics of bubbly and slug flow in microgravity will be analyzed especially for the role of the coalescence in the transition from bubbly to slug flow (effect of fluid properties and surfactant), to identify clusters that promote coalescence and transition the void fraction distribution in bubbly and slug flow,to measure the wall friction in bubbly flow. These experiments will consist of multiple bubbles type flows and will utilize hot wire and film anemometers to measure liquid velocity and wall shear stress respectively and double fiber optic probes to measure bubble size and velocity as a function of tube radius and axial location.

McQuillen, J.↗

Maximizing ion dynamics and electrochemical performance of ionic liquid-acetonitrile electrolyte in Ti 3 C 2 T x MXene

Modification of the structure and morphology of MXene electrodes and the formulation of the electrolytes used in their supercapacitor configurations are significant factors affecting the performance of electrochemical devices. In this study, we investigated the electrochemical performance and ion dynamics of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [EmimTFSI], ionic liquid in the presence of acetonitrile (ACN) at different concentrations in Ti 3 C 2 T x MXene supercapacitor. We found an optimum concentration of ACN, at which more cations from the ionic liquid attach to the MXene electrode surface, providing higher electrochemical performance. This higher capacitance is also associated with increased microscopic dynamics of the cation away from the pore wall. These findings give a guideline to optimize the performance of MXene-based supercapacitors using organic solvents-ionic liquid-based electrolyte systems.

36 MATERIALS SCIENCE↗

Symmetric U(1) and Z 2 spin liquids on the pyrochlore lattice

The geometrically frustrated three-dimensional pyrochlore lattice has been long predicted to host a quantum spin liquid, an intrinsic long-range entangled state with fractionalized excitations. To date, most proposals for pyrochlore materials have focused on quantum spin ice, a U(1) quantum spin liquid whose only low energy excitations are emergent photons of Maxwell type. Here, we explore the possibility of finding pyrochlore quantum spin liquids whose low energy theories go beyond this standard one. We give a complete classification of symmetric U ( 1 ) and Z 2 spin liquids on the pyrochlore lattice within the projective symmetry group framework for fermionic spinons. We find 18 U ( 1 ) spin liquids and 28 Z 2 spin liquids that preserve pyrochlore space-group symmetry while, upon further imposing time-reversal symmetry, the numbers of classes become 16 and 48, respectively. For each class, the most general symmetry-allowed spinon mean-field Hamiltonian is given. Interestingly, we find that several U(1) spin liquid classes possess an unusual gapless multi-nodal-line structure (“nodal star”) in the spinon bands, which is protected by the projective actions of the threefold rotation and screw symmetries of the pyrochlore space group. Through a simple model, we study the effect of gauge fluctuations on such a nodal star spin liquid and propose that the leading terms in the low temperature specific heat have the scaling form C / T ~ T + T / ln T , in contrast to the form C / T ~ T 2 of the standard U(1) pyrochlore spin liquid with gapped spinons.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

More About Nonobstructive Particle Damping

Report presents additional information about engineering concept described in "Nonobtrusive Damping For Parts Vibrating In Flows", (MFS-29572). Implies "nonobstructive particle damping" (NOPD) applicable not only to vanes immersed in flows but also to other vibrating structures. Furthermore, damping fillings include not only powders and balls but also slurries or even liquids. NOPD treatment offers additional advantages: lasts much longer than more conventional treatments; slight decrease in weight of structure; is largely independent of temperature, pressure, centrifugal force, or other environmental parameters; and relatively easy to implement because damping holes drilled routinely during fabrication.

Panossian, Hagop V.↗

Structural Effects of Postulated Hydrogen Explosions in Process Piping and Vessels - 20274

At Savannah River Site (SRS), preparations to startup new liquid waste operations and recent advances in understanding thermolytic hydrogen generation have led to several recent studies on the structural effects of postulated hydrogen explosions. This paper reports on seven representative piping and vessel cases that are evaluated for deflagrations, detonations, and deflagration-to-detonation transition (DDT) assuming the initial mixture is stoichiometric hydrogen and air. The evaluations are based on the approach used by the Department of Defense for analyzing structures subjected to accidental explosions and include inelasticity, dynamic structural amplification, and material strain-rate effects. Evaluation criteria consider the potential for repeated explosions causing fatigue but also consider that some degree of permanent plastic deformation is acceptable as long as rupture is prevented. Specific conclusions depend on the assumed pre-ignition pressure. If the pre-ignition pressure is atmospheric and if the components are designed to a code from the American Society of Mechanical Engineers, the components evaluated are expected to plastically deform but not rupture under the explosion scenarios considered. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Slowly and Rapidly Propagating "Liquid Flames" in Gravitational Fields

We consider the combustion, in a gravitational field, of a heterogeneous powder mixture compressed into a solid sample, in which the high temperature ahead of the reaction zone destroys the solid, due, e.g. to melting of some of components of the mixture. Thus, a suspension is formed, consisting of a liquid bath containing solid or liquid particles. Processes such as heat and mass transfer as well as chemical reactions in the suspension determine the structure of the combustion wave and its propagation velocity. Under the influence of gravitational forces there is the possibility of relative motion of the liquid and solid. Previous theoretical analyses considered the rate of beat transfer between the solid and liquid phases to be sufficiently large that their two distinct temperatures rapidly equilibrated to a single temperature. In addition to this case, we also consider the case when the rate of heat transfer is not so large and the model involves the separate temperatures of the solid and liquid phases. We find that multiplicity of traveling wave structures is possible. In particular, in addition to a low velocity structure, which is essentially the same as that obtained from the one temperature description, we find a high velocity structure, which does not exist in the one temperature description, but rather depends on the fact that the solid and fluid temperatures differ from each other. Both structures can exist for the same parameter values in a given range. We describe the dependence of the combustion characteristics of the two structures on gravitational forces and other factors. In particular, we compare the characteristics in gravity and microgravity environments.

Shkadinsky, K. G.↗

Rolling Beam Umbilical System

The decision to make the Centaur Vehicle a Space Transportation System (STS) payload meant that new ground support equipment provisions at Launch Pads Pads 39A and 39B were required. These new equipment provisions were needed to service the Centaur vehicle while it was installed in the Orbiter's payload bay prior to launch. This paper describes the design of a new rolling beam umbilical syste (RBUS) being added to the pad fixed service structure (FSS) in order to provide the primary functions of liquid hydrogen (LH2) fill, drain, and vent. The carrier plate itself is a Government-furnished equipment item and of necessity became a T-O disconnect. This permits quick offloading in the event of an abort prior to lift-off. In addition to the rolling beam structure, mechanisms, and fluid lines, it was necessary to design and build a carrier plate simulator to support early development testing of the mast at the Launch Equipment Test Facility at Kennedy Space Center. The RBUS is designed to be compatible with the rotating service structure (RSS) to the extent that the umbilical may be deployed with the RSS mated with the vehicle. It is also designed to clear the RSS as the RSS rotates back out of the way. Accessibility to the Orbiter aft compartment via the 50-1 door had to be maintained.

Tatem, B. C., Jr.↗

Interfacial and Hydrodynamic Behavior of Thin Spherical Bubbles of Smectic Liquid Crystal in Microgravity

The Observation and Analysis of Smectic Islands in Space (OASIS) project comprises a series of experiments that probe the interfacial and hydrodynamic behavior of thin spherical bubbles of smectic liquid crystal in microgravity. Smectic films are the thinnest known structures formed of condensed phases, making them ideal for studies of two-dimensional (2D) coarsening dynamics and thermocapillary phenomena. The OASIS flight hardware was launched on SpaceX-6 in April 2015 and experiments were carried out on the International Space Station using four different smectic A and C liquid crystal materials in separate sample chambers. We will describe the behavior of collective island dynamics on the bubbles, including temperature-gradient-induced thermomigration, 2D Rayleigh-Plateau Instability, Oswald ripening dynamics, the single and multiple island diffusion on the curved surface and coalescence-driven coarsening dynamics of island emulsions in microgravity. On Earth, such island emulsions would rapidly sediment to the bottom of the bubble and coalesce, but in microgravity, coarsening of the emulsion can be observed free of gravitational effects.

liquid crystal↗

Crowded electrolytes containing redoxmers in different states of charge: Solution structure, properties, and fundamental limits on energy density

Nonaqueous redox flow batteries use liquid electrolytes containing redox-active organic molecules (redoxmers) as their energy storage medium. To maximize energy density, the redoxmer concentration needs to be maximized while maintaining low viscosity and high ionic conductivity. During charge, a redoxmer molecule pairs with an ion in the electrolyte while another ion migrates across the membrane to maintain electric neutrality. In a crowded electrolyte, this reconstitution changes physical and chemical properties of the solution. To explore these behaviors, a phenothiazine redoxmer fully miscible with acetonitrile was used, and electrochemical charge was mimicked by chemical oxidation. The solutions were examined using small-angle X-ray scattering, nuclear magnetic resonance, and conductometry and modeled using classical molecular dynamics. Overall, our study indicates that physical and structural properties of redoxmer solutions in both states of charge make it exceedingly difficult to increase the redoxmer concentrations over 2 M at any temperature without compromising dynamic properties of such solutions. The cause for this limitation is proximity to a gel-like regime in which fluidity, diffusivity, and ionic conductivity exponentially decrease with increasing concentration. This tendency is compounded by non-Arrhenius behavior of the electrolyte: a small increase in the concentration outruns gains in fluidity and conductivity at a higher temperature. Thus the properties of crowded electrolytes generally make it impossible to operate when gel-like behavior sets in. Pushing the redoxmer concentration to 2.5-3 M might be possible for small redoxmer molecules, but it would require the use of ionic liquid electrolytes at 340-360 K. (C) 2021 Elsevier B.V. All rights reserved.

25 ENERGY STORAGE↗

Validating first-principles molecular dynamics calculations of oxide/water interfaces with x-ray reflectivity data

Metal oxide/water interfaces play a crucial role in many electrochemical and photocatalytic processes, such as photoelectrochemical water splitting, the creation of fuel from sunlight, and electrochemical CO 2 reduction. First-principles electronic structure calculations can reveal unique insights into these processes, such as the role of the alignment of the oxide electronic energy levels with those of liquid water. An essential prerequisite for the success of such calculations is the ability to predict accurate structural models of these interfaces, which in turn requires careful experimental validation. Here we report a general, quantitative validation protocol for first-principles molecular dynamics simulations of oxide/aqueous interfaces. The approach makes direct comparisons of interfacial x-ray reflectivity (XR) signals from experimental measurements and those obtained from ab initio simulations with semilocal and van der Waals functionals. The protocol is demonstrated here for the case of the Al 2 O 3 (001)/water interface, one of the simplest oxide/water interfaces. We discuss the technical requirements needed for validation, including the choice of the density functional, the simulation cell size, and the optimal choice of the thermodynamic ensemble. Our results establish a general paradigm for the validation of structural models and interactions at solid/water interfaces derived from first-principles simulations. Furthermore, while there is qualitative agreement between the simulated structures and the experimental best-fit structure, direct comparisons of simulated and measured XR intensities show quantitative discrepancies that derive from both bulk regions (i.e., alumina and water) as well as the interfacial region, highlighting the need for accurate density functionals to properly describe interfacial interactions. Our results show that XR data are sensitive not only to the atomic structure (i.e., the atom locations) but also to the electron-density distributions in both the substrate and at the interface.

36 MATERIALS SCIENCE↗

Application of the ASME Boiler and Pressure Vessel Code in the Design of SRF Cavities at Fermilab

Jacketed Superconducting Radio Frequency (SRF) cavities structurally comprise of an inner niobium vessel surrounded by a liquid helium containment vessels. The pressure of the helium bath and/or its volume might be such that a jacketed SRF cavity shall be considered a system of pressure vessels. Thus, methods described in the American Society of Mechanical Engineers (ASME) Boiler and Pressure Vessel Code (BPVC) should be used to analyze the structural soundness of jacketed SRF cavities. This paper will report the use of the set of rules developed at Fermilab for the design of SRF cavities, such as jacketed 1.3 GHz cavities for LCLS-II HE and jacketed Single Spoke Resonator type~2 (SSR2) for PIP-II, to ensure a similar level of safety as prescribed by the ASME BPVC.

43 PARTICLE ACCELERATORS↗

Overview of the TJ-II stellarator research programme towards model validation in fusion plasmas

TJ-II stellarator results on modelling and validation of plasma flow asymmetries due to on-surface potential variations, plasma fuelling physics, Alfvén eigenmodes (AEs) control and stability, the interplay between turbulence and neoclassical (NC) mechanisms and liquid metals are reported. Regarding the validation of the neoclassically predicted potential asymmetries, its impact on the radial electric field along the flux surface has been successfully validated against Doppler reflectometry measurements. Research on the physics and modelling of plasma core fuelling with pellets and tracer encapsulated solid pellet injection has shown that, although post-injection particle radial redistributions can be understood qualitatively from NC mechanisms, turbulence and fluctuations are strongly affected during the ablation process. Advanced analysis tools based on transfer entropy have shown that radial electric fields do not only affect the radial turbulence correlation length but are also capable of reducing the propagation of turbulence from the edge into the scrape-off layer. Direct experimental observation of long range correlated structures show that zonal flow structures are ubiquitous in the whole plasma cross-section in the TJ-II stellarator. Alfvénic activity control strategies using ECRH and ECCD as well as the relation between zonal structures and AEs are reported. Finally, the behaviour of liquid metals exposed to hot and cold plasmas in a capillary porous system container was investigated.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗