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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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44 records · Page 3

Soluble minerals in chemical evolution. I - Adsorption of 5-prime-AMP on CaSO4 - A model system

The adsorption of 5-prime-AMP onto solid CaSO4-2H2O was studied in a saturated suspension as a function of pH and electrolyte concentration. The adsorption is pH-dependent and is directly correlated with the charge on the 5-prime-AMP molecule which is determined by the state of protonation of the N-1 nitrogen of the purine ring and the phosphate oxygens. It is proposed that the binding that occurs between the nucleotide and the salt is electrostatic in nature. The adsorption decreases with increasing ionic strength of the solution which means that in a fluctuating environment of wetting and drying cycles, a biomolecule similar to 5-prime-AMP could be expected to desorb during the drying phase. The results indicate that CaSO4-2H2O can serve as a concentrating surface for biomolecules. The significance of this is discussed with regard to the possible role of soluble minerals and their surfaces in a geochemical model consistent with the evolution of the earth and the origin of life.

Orenberg, J. B.↗

Colloidal Stability of PFSA-Ionomer Dispersions Part II: Determination of Suspension pH Using Single-Ion Potential Energies

Perfluorosulfonic acid (PFSA) ionomers serve a vital role in the performance and stability of fuel-cell catalyst layers. These properties, in turn, depend on the colloidal processing of precursor inks. Here, to understand the colloidal structure of fuel-cell catalyst layers, we explore the aggregation of PFSA ionomers dissolved in water/alcohol solutions and relate the predicted aggregation to experimental measurements of solution pH. Not all side chains contribute to measured pH because of burying inside particle aggregates. To account for the measured degree of dissociation, a new description is developed for how PFSA aggregates interact with each other. The developed single-counterion electrostatic repulsive pair potential from Part I is incorporated into the Smoluchowski collision-based kinetics of interacting aggregates with buried side chains. We demonstrate that the surrounding solvent mixture affects the degree of aggregation as well as the pH of the system primarily through the solution dielectric permittivity, which drives the strength of the interparticle repulsive energies. Successful pH prediction of Nafion ionomer dispersions in water/n-propanol solutions validates the numerical calculations. Nafion-dispersion pH measurements serve as a surrogate for Nafion particle-size distributions. The model and framework can be leveraged to explore different ink formulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermodynamics of electrolyte solutions near charged surfaces: Constant surface charge vs constant surface potential

Electric double layers are ubiquitous in science and engineering and are of current interest, owing to their applications in the stabilization of colloidal suspensions and as supercapacitors. While the structure and properties of electric double layers in electrolyte solutions near a charged surface are well characterized, there are subtleties in calculating thermodynamic properties from the free energy of a system with charged surfaces. These subtleties arise from the difference in the free energy between systems with constant surface charge and constant surface potential. In this work, we present a systematic, pedagogical framework to properly account for the different specifications on charged bodies in electrolyte solutions. Our approach is fully variational—that is, all free energies, boundary conditions, relevant electrostatic equations, and thermodynamic quantities are systematically derived using variational principles of thermodynamics. We illustrate our approach by considering a simple electrolyte solution between two charged surfaces using the Poisson–Boltzmann theory. Our results highlight the importance of using the proper thermodynamic potential and provide a general framework for calculating thermodynamic properties of electrolyte solutions near charged surfaces. Specifically, we present the calculation of the pressure and the surface tension between two charged surfaces for different boundary conditions, including mixed boundary conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dual-mass vibratory rate gyroscope with suppressed translational acceleration response and quadrature-error correction capability

A microfabricated vibratory rate gyroscope to measure rotation includes two proof-masses mounted in a suspension system anchored to a substrate. The suspension has two principal modes of compliance, one of which is driven into oscillation. The driven oscillation combined with rotation of the substrate about an axis perpendicular to the substrate results in Coriolis acceleration along the other mode of compliance, the sense-mode. The sense-mode is designed to respond to Coriolis accelerationwhile suppressing the response to translational acceleration. This is accomplished using one or more rigid levers connecting the two proof-masses. The lever allows the proof-masses to move in opposite directions in response to Coriolis acceleration. The invention includes a means for canceling errors, termed quadrature error, due to imperfections in implementation of the sensor. Quadrature-error cancellation utilizes electrostatic forces to cancel out undesired sense-axis motion in phase with drive-mode position.

Clark, William A.↗

Molecular-level design of alternative media for energy-saving pilot-scale fibrillation of nanocellulose

The outstanding mechanical properties, light weight, and biodegradability of cellulose nanofibrils (CNFs) make them promising components of renewable and sustainable next-generation reinforced composite biomaterials and bioplastics. Manufacturing CNFs at a pilot scale requires disc-refining fibrillation of dilute cellulose fibers in aqueous pulp suspensions to shear the fibers apart into their nanodimensional forms, which is, however, an energy-intensive process. Here, in this study, we used atomistic molecular dynamics (MD) simulation to examine media that might facilitate the reduction of interactions between cellulose fibers, thereby reducing energy consumption in fibrillation. The most suitable medium found by the simulations was an aqueous solution with 0.007:0.012 wt.% NaOH:urea, and indeed this was found in pilot-scale experiments to reduce the fibrillation energy by ~21% on average relative to water alone. The NaOH:urea-mediated CNFs have similar crystallinity, morphology, and mechanical strength to those formed in water. The NaOH and urea act synergistically on CNFs to aid fibrillation but at different length scales. NaOH deprotonates hydroxyl groups leading to mesoscale electrostatic repulsion between fibrils, whereas urea forms hydrogen bonds with protonated hydroxyl groups thus disrupting interfibril hydrogen bonds. This suggests a general mechanism in which an aqueous medium that contains a strong base and a small organic molecule acting as a hydrogen-bond acceptor and/or donor may be effectively employed in materials processes where dispersion of deprotonable polymers is required. The study demonstrates how atomic-detail computer simulation can be integrated with pilot-scale experiments in the rational design of materials processes for the circular bioeconomy.

36 MATERIALS SCIENCE↗

pH-dependent reactivity of water at MgO(100) and MgO(111) surfaces

Facet-dependent surface charging of metal oxides in water dominates the ion transport behavior across the interface, in turn impacting many natural and industrial processes such as adsorption, the formation and stabilization of nanoparticle suspensions, corrosion, and heterogeneous catalysis. Here we investigated the pH-dependent surface chemistry of two low-index MgO single crystal surfaces, namely MgO(100) and MgO(111), using vibrational sum frequency generation (vSFG) spectroscopy. This allowed us to evaluate facet-dependent pH effects on the hydration and hydroxylation at the solid/aqueous interface and point-of-zero charge (PZC) values. The MgO system is complicated by its thermodynamic instability with respect to Mg(OH) 2 in water at ambient conditions. Here, for both hydroxylated MgO(100) and MgO(111) surfaces, the PZC is found to be around pH ∼ 12, which compares well with reported values for MgO single crystal and nanoparticle surfaces. However, structure specific differences in the molecular water hydrogen bonding network near the surface are evident at mildly acidic pH. To our knowledge, this is the first account of the PZC values for the MgO(111) single-crystal surface, an electrostatically unstable MgO termination that is prone to reconstruction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Critical Shear Stresses for Erosion from Yield Stresses

The critical shear stress for erosion is important in many fields of engineering and science that involve suspension of particles from settled particle beds. However, determining the critical shear stress for erosion remains intricate, particularly where interparticle forces play a key role. Because these forces vary widely (Pease, et al., 2019), a more convenient means of estimating the critical shear stress for erosion would be advantageous. Here we evaluate the assertion that critical shear stresses for erosion may be derived from yield stresses for nominally cohesive particle beds across the full range of particle Reynolds numbers. The critical shear stress for erosion for non-cohesive particle beds may be estimated from the Shields diagrams or the analytical expressions from conservation of force about a particle at the interface. However, equivalent diagrams for cohesive particle beds have remained elusive. In 1992, pioneering analysis by Dade included the influence of the van der Waals force in particle forces balances to show that the critical shear stresses for erosion may be related to yield stresses subject to the limitations of small particle Reynolds numbers, flat particle beds, uniform particle diameters, and negligible electrostatic forces. Here we relax these restrictions. We find that the critical shear stress for erosion does relate to the yield stresses in a linear fashion for sufficiently large yield stresses. A criterion is developed to determine when the yield stresses may be important. Pease LF, AJ Fuher, JA Bamberger, and MJ Minette. 2024. Shields Diagrams for Cohesive Particle Beds. Manuscript. Dade WB, ARM Nowell and PA Jumars. 1992. “Predicting erosion resistance of muds.” Marine Geology, 105 (1992) 285-297.

shear stress, erosion, yield stress, slurry, settl↗

Applications of Electrified Dust and Dust Devil Electrodynamics to Martian Atmospheric Electricity

Atmospheric transport and suspension of dust frequently brings electrification, which may be substantial. Electric fields of 10 kV m(exp. -1) to 100 kV m(exp. -1) have been observed at the surface beneath suspended dust in the terrestrial atmosphere, and some electrification has been observed to persist in dust at levels to 5 km, as well as in volcanic plumes. The interaction between individual particles which causes the electrification is incompletely understood, and multiple processes are thought to be acting. A variation in particle charge with particle size, and the effect of gravitational separation explains to, some extent, the charge structures observed in terrestrial dust storms. More extensive flow-based modelling demonstrates that bulk electric fields in excess of 10 kV m(exp. -1) can be obtained rapidly (in less than 10 s) from rotating dust systems (dust devils) and that terrestrial breakdown fields can be obtained. Modelled profiles of electrical conductivity in the Martian atmosphere suggest the possibility of dust electrification, and dust devils have been suggested as a mechanism of charge separation able to maintain current flow between one region of the atmosphere and another, through a global circuit. Fundamental new understanding of Martian atmospheric electricity will result from the ExoMars mission, which carries the DREAMS (Dust characterization, Risk Assessment, and Environment Analyser on the Martian Surface) MicroARES (Atmospheric Radiation and Electricity Sensor) Instrumentation to Mars in 2016 for the first in situ electrical measurements.

Lighting Discharge↗