Rectified and Salt Concentration Dependent Wetting of Hydrophobic Nanopores
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Thermal shock resistance of multilayer silicon carbide receiver tubes for 800°C molten salt concentrating solar power application
CSP power tower receiver systems during rapid transient weather periods can be vulnerable to thermal shock conditions from rain that which can facilitate the onset of leaks and failures that can have catastrophic consequences. Silicon carbide (SiC) materials have attractive receiver application characteristics for being light weight, having high-strength and excellent thermal shock resistance performance which make them a particularly good fit for receiver absorber materials in CSP. In this investigation, the performance characteristics of Ceramic Tubular Products (CTP) SiC ceramic matrix composite (CMC), multilayered tubes were explored with respect to thermal shock performance for solar receiver applications in next generation CSP plants. Here, thermal shock testing was performed at the Sandia National Laboratories (SNL) Solar Furnace facility using a dynamic stage and thermal shock tube test setup. The tubes tested under incident solar heat flux of 100 W/cm2 were heated with inner tube temperatures reaching approximately 800 °C, with outer temperatures exceeding or just reaching 1000 El for the multilayer and monolithic SiC tubes respectively. The tubes were then quenched with simulated rain. The tubes were then cooled and subjected to hoop stress analysis using an Instron device to assess their subsequent mechanical strength. Furthermore, the on-sun study experimental results indicate an average of 24.2% and 97% higher hoop strength for the CMC tubes than those composed of monolithic SiC and aluminum oxide (A1203) respectively.
14 SOLAR ENERGY↗
Freeze-thaw behavior of a moderately halophilic bacterium as a function of salt concentration
Halophilic bacteria growth in freeze-thaw environment, investigating cooling and warming rates and solute concentrations
Deal, P. H.↗
High-temperature (750 – 800°C) Silicon Carbide Receiver Assembly for High Efficiency Gen3 Molten Salt Concentrating Solar Power
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14 SOLAR ENERGY↗
Method for Real-Time Salt Aerosol Concentration and Size Measurements for Molten Salt Reactor Safety Assessments
Licensing a new nuclear reactor involves evaluating credible accident scenarios by developing models that simulate accident progression to predict possible outcomes and their impact on safety. The formation of radionuclide-bearing aerosols in the respirable size range can significantly affect dose consequence and threaten human health and is therefore a focus of nuclear reactor safety assessments. Recent reviews of the literature identified a lack of existing experimental data describing the mechanisms of formation and properties (size, concentration, and composition) of radionuclide-bearing aerosols that may be produced from molten salt reactor (MSR) facilities during postulated accident scenarios. Experiments on aerosol formation from molten salt systems are a high priority need that will support MSR licensing by indicating the radiological consequences of aerosol formation and providing the data required for model development and validation. The evolving conditions that occur during a MSR accident, such as a spill of molten fuel salt, may affect aerosol formation mechanisms and aerosol properties over time. There is a need to conduct experiments that simulate credible MSR accidents in a laboratory to generate aerosols with realistic characteristics and behaviors and a need to measure these aerosols in real time under accident-relevant conditions. This report describes the development of a method that can be used to quantify the size and concentration of salt aerosol particles that form from molten salt systems in real time. This method will be employed in future integral effects tests that are conducted at an engineering scale to simulate realistic MSR accidents and in future separate effects tests that will provide mechanistic insight into aerosol formation and properties to support process model development.
22 GENERAL STUDIES OF NUCLEAR REACTORS↗
Effects of NaCl on metabolic heat evolution rates by barley roots
The effect of salinity stress on metabolic heat output of barley (Hordeum vulgare L.) root tips was measured by isothermal microcalorimetry. Several varieties differing in tolerance to salinity were compared and differences quantified. Two levels of inhibition by increasing salt were found. Following the transition from the initial rate of the first level, inhibition remained at about 50% with further increases in salt concentration up to 150 millimolar. The concentration of salt required to inhibit to this level was cultivar dependent. At highter concentrations (>150 millimolar) of salt, metabolism was further decreased. This decrease was not cultivar dependent. The decreased rate of metabolic heat output at the first transition could be correlated with decreases in uptake of NO3-, NH4+, and Pi that occurred as the salt concentration was increased. The high degree of dependence of the inhibition of metabolic heat output on NaCl concentration points to a highly cooperative reaction responsible for the general inhibition of metabolism and nutrient uptake. The time required to attain the first level of salt inhibition is less than 20 minutes. Inhibition of root tips was not reversible by washing with salt free solutions. In addition to revealing these features of salt inhibition, isothermal microcalorimetry is a promising method for convenient and rapid determination of varietal differences in response to increasing salinity.
NASA Discipline Life Support Systems↗
Influence of External NaCl Salt on Membrane Rigidity of Neutral DOPC Vesicles
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effects of Salt on Phase Behavior and Rheological Properties of Alginate–Chitosan Polyelectrolyte Complexes
Oppositely charged polyelectrolytes often form polyelectrolyte complexes (PECs) due to the association through electrostatic interactions. Obtaining PECs using natural, biocompatible polyelectrolytes is of interest in the food, pharmaceutical, and biomedical industries. In this work, PECs were prepared from two biopolymers, positively charged chitosan and negatively charged alginate. We investigate the changes in the structure and properties of PECs by adding sodium chloride (salt doping) to the system. The shear modulus of PECs can be tuned from ~10 to 10 4 Pa by changing the salt concentration. The addition of salt led to a decrease in the water content of the complex phase with increasing shear modulus. However, at a very high salt concentration, the shear modulus of the complex phase decreased but did not lead to the liquid coacervate formation, typical of synthetic polyelectrolytes. This difference in phase behavior has likely been attributed to the hydrophobicity of chitosan and long semiflexible alginate and chitosan chains that restrict the conformational changes. Large amplitude oscillatory shear experiments captured nonlinear responses of PECs. The compositions of the PECs, determined as a function of salt concentration, signify the preferential partitioning of salt into the complex phase. Small-angle X-ray scattering of the salt-doped PECs indicates that the Kuhn length and radius of the alginate–chitosan associated structure qualitatively agree with the captured phase behavior and rheological data. This study provides insights into the structure–property as a function of salt concentration of natural polymer-based PECs necessary for developing functional materials from natural polyelectrolytes.
59 BASIC BIOLOGICAL SCIENCES↗
Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes
Hybrid organic-inorganic block copolymer electrolytes are of interest to enable batteries containing lithium metal anodes. The conductive block is a standard polymer electrolyte of poly(ethylene oxide) and the mechanically rigid block is an inorganic poly(acryloisobutyl polyhedral oligomeric silsesquioxane) polymer. Here, in this paper, we compare a poly(acryloisobutyl polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS) triblock copolymer and a poly(ethylene oxide)-b- poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide salt. We have experimentally measured the limiting current density in lithium symmetric cells containing hybrid organic-inorganic electrolytes at 90 °C. The cells were polarized at a large range of applied current density. The diblock copolymer electrolyte exhibited a clear plateau in cell potential at all current densities below the limiting current density. At low applied current density, the triblock copolymer electrolyte also exhibited a clear plateau in cell potential. At currents approaching the limiting current density, the triblock copolymer electrolyte exhibited an underdamped potential profile. The cell potential did not reach a plateau at current densities above the limiting current in both systems. The diblock and triblock copolymer electrolytes were fully characterized using electrochemical methods to determine the ionic conductivity, cation current fraction, salt diffusion coefficient, and open circuit voltage as a function of salt concentration. Cell potential and salt concentration as functions of position in the cell at various current densities were calculated using Newman's concentrated solution theory. The theoretical limiting current density was calculated to be the current density at which salt is depleted at the cathode. We see quantitative agreement between experimental measurements and theoretical predictions for the limiting current density in the diblock copolymer electrolyte which has an ordered structure at all salt concentrations, while the experimental limiting current density is lower than the theoretical prediction for the triblock copolymer electrolyte, which exhibits a disordered morphology at high salt concentrations.
25 ENERGY STORAGE↗
Interactions in Undersaturated and Supersaturated Lysozyme Solutions: Static and Dynamic Light Scattering Results
We have performed multiangle static and dynamic light scattering studies of lysozyme solutions at pH=4.7. The Rayleigh ratio R(sub g) and the collective diffusion coefficient D(sub c) were determined as function of both protein concentration c(sub p) and salt concentration c(sub s) with two different salts. At low salt concentrations, the scattering ratio K(sub c)(sub p)/R(sub theta) and diffusivity increased with protein concentration above the values for a monomeric, ideal solution. With increasing salt concentration this trend was eventually reversed. The hydrodynamic interactions of lysozyme in solution, extracted from the combination of static and dynamic scattering data, decreased significantly with increasing salt concentration. These observations reflect changes in protein interactions, in response to increased salt screening, from net repulsion to net attraction. Both salts had the same qualitative effect, but the quantitative behavior did not scale with the ionic strength of the solution. This indicates the presence of salt specific effects. At low protein concentrations, the slopes of K(sub c)(sub p)/R(sub theta) and D(sub c) vs c(sub p) were obtained. The dependence of the slopes on ionic strength was modeled using a DLVO potential for colloidal interactions of two spheres, with the net protein charge Z(sub e) and Hamaker constant A(sub H) as fitting parameters. The model reproduces the observed variations with ionic strength quite well. Independent fits to the static and dynamic data, however, led to different values of the fitting parameters. These and other shortcomings suggest that colloidal interaction models alone are insufficient to explain protein interactions in solutions.
Muschol, Martin↗
Hot corrosion of four superalloys - HA-188, S-57, IN-617, and TD-NiCrAl
Cyclic oxidation and hot corrosion tests of two cobalt-base and two nickel-base alloys are reported. The alloys were exposed to maximum temperatures of 900 and 1000 C in a Mach 0.3 burner rig whose flame was doped with various concentrations of sea salt and sodium sulfate for hot corrosion tests. The test data were subjected to a regression analysis for the development of model equations relating corrosion to temperature and for the effects of salt concentration and composition on corrosion. The corrosion resistance varied with temperature, sea salt concentration, and salt composition, concluding that the S-57 cobalt-base alloy was the most hot corrosion-resistant alloy, and the TD-NiCrAl nickel-base alloy was the least resistant. However, under straight oxidation conditions, the TD-NiCrAl was most resistant, while S-57 was the least resistant alloy.
Santoro, G. J.↗
How do super concentrated electrolytes push the Li-ion batteries and supercapacitors beyond their thermodynamic and electrochemical limits?
Increasing the energy density of energy storage devices is currently the key target of many battery and supercapacitor research activities. For both types of devices, the electrochemical stability window (ESW) determines the effective energy density of the device. ESWs are defined by the effective oxidation and reduction potentials of the electrolyte, which are controlled by many various factors, including the HOMO/LUMO (highest/lowest unoccupied molecular orbital) energies of the electrolyte molecules, the nature of the electrode/electrolyte interphases, and other physicochemical properties. The concentration of the electrolyte would affect the HOMO/ LUMO levels thus also change the ESW. A higher concentration of salt induces specific arrangements among the anion, cation, and solvent molecules of an electrolyte, altering the bulk behavior of the electrolyte, resulting in drastic change in the electrode interfaces. These uniquely modified physicochemical properties extend the ESW in several different ways, including the enhancement in the kinetic stability of the electrodes, as well as the thermodynamic and Nernst shifts of the oxidation/reduction potentials of the electrolyte. For organic electrolytes, it is the reduced amount of free solvent molecules that plays the key role in such changes; whereas for aqueous electrolytes, it is the scarcity of free water molecules and the reduced water activity that control the key properties of the electrolyte. Here, we focus on elucidating the fundamental structural changes occurring within an electrolyte system with increasing salt concentrations. The underlying mechanisms which not only facilitates the extension of the ESW, but also enables higher rate capabilities and mitigates aluminum dissolution for batteries with organic electrolytes, are meticulously explained. Further, we thoroughly discuss the importance of high-voltage stability in aqueous battery systems by exploiting the changed properties observed with higher concentrations of salts. To finish, high-voltage supercapacitors enabled by superconcentrated electrolytes are also explored.
25 ENERGY STORAGE↗
Novel interaction interfaces mediate the interaction between the NEIL1 DNA glycosylase and mitochondrial transcription factor A
The maintenance of human mitochondrial DNA (mtDNA) is critical for proper cellular function as damage to mtDNA, if left unrepaired, can lead to a diverse array of pathologies. Of the pathways identified to participate in DNA repair within the mitochondria, base excision repair (BER) is the most extensively studied. Protein-protein interactions drive the step-by-step coordination required for the successful completion of this pathway and are important for crosstalk with other mitochondrial factors involved in genome maintenance. Human NEIL1 is one of seven DNA glycosylases that initiates BER in both the nuclear and mitochondrial compartments. In the current work, we scrutinized the interaction between NEIL1 and mitochondrial transcription factor A (TFAM), a protein that is essential for various aspects of mtDNA metabolism. We note, for the first time, that both the N- and C- terminal domains of NEIL1 interact with TFAM revealing a unique NEIL1 protein-binding interface. The interaction between the two proteins, as observed biochemically, appears to be transient and is most apparent at concentrations of low salt. The presence of DNA (or RNA) also positively influences the interaction between the two proteins, and molar mass estimates indicate that duplex DNA is required for complex formation at higher salt concentrations. Hydrogen deuterium exchange mass spectrometry data reveal that both proteins exchange less deuterium upon DNA binding, indicative of an interaction, and the addition of NEIL1 to the TFAM-DNA complex alters the interaction landscape. The transcriptional activity of TFAM appears to be independent of NEIL1 expression under normal cellular conditions, however, in the presence of DNA damage, we observe a significant reduction in the mRNA expression of TFAM-transcribed mitochondrial genes in the absence of NEIL1. Overall, our data indicate that the interaction between NEIL1 and TFAM can be modulated by local environment such as salt concentrations, protein availability, the presence of nucleic acids, as well as the presence of DNA damage.
59 BASIC BIOLOGICAL SCIENCES↗
Electrodeposited nickel coatings for exceptional corrosion mitigation in industrial grade molten chloride salts for concentrating solar power
Molten chloride salt eutectics are attractive candidates for use as thermal energy storage media and heat transfer fluids in generation-three concentrating solar thermal power (Gen3 CSP) plants. However, corrosion of alloys in molten chloride salts, especially at high temperatures, is an extremely challenging problem that studies focus on lower temperatures, shorter durations, or analytical grade, and high-purity, salts. To date, there has been no study on corrosion or corrosion mitigation in an industrial-grade salt at a high temperature such as 750 °C. To alleviate this knowledge gap, the study presents new multiscale fractal-textured Ni coatings on various alloy surfaces for effective corrosion mitigation at 750 °C in molten chloride salts. Using the electrodeposition method, durable double-layer textured coatings were formed on stainless steel alloys (SS316, SS310, and SS347) and In800H. The corrosion performance of the coatings is investigated in both analytical-grade purity and, for the first time, practically relevant industrial-grade chloride salts. Ni-coated ferrous alloys showed an exceptionally reduced corrosion rate in the range of 350–480 μm/y in analytical-grade salts, and between 450 and 490 μm/y in purified industrial-grade salts at 750 °C. Ni coatings on ferrous alloys reduced corrosion rates by as much as 70% compared to uncoated surfaces and were comparable to the expensive Ha230 alloy with a high Ni content. As a result, by the use of innovative fractal corrosion mitigation coatings, for the first time, low-cost structural alloys are rendered viable for use with industrial-grade chloride salts, which is profoundly beneficial in practical systems.
14 SOLAR ENERGY↗
Lack of Evidence for Prenucleation Aggregate Formation in Lysozyme Crystal Growth Solutions
There have been numerous claims of large concentrations of prenucleation aggregates in supersaturated as well as undersaturated lysozyme solutions at high salt concentrations. The presence of these aggregates was derived from measurements of the light or neutron scattering intensity, ultracentrifugation and dialysis behavior, as well as over-simplified crystal growth kinetics considerations. In all these interpretations it has been assumed that lysozyme solutions are either ideal or that protein interactions are independent of salt concentration. Contrary to these presumptions, our static and dynamic light scattering experiments provide evidence that lysozyme forms highly non-ideal, strongly interacting solutions. At low salt concentrations, the scattering intensities fall well below the values expected for an ideal, monomeric solution at the same protein concentration, while diffusivities increase with increasing protein concentration. Upon increase in salt concentration, these trends are eventually reversed. This enhancement in scattering intensity and decrease in diffusivity was widely interpreted as sign of aggregate formation. Yet, a quantitative interpretation of the scattering behavior over the whole salt concentration range can only be given in terms of a transition from net repulsion to net attraction between lysozyme monomers. Increased salt screening of the electrostatic repulsion among the protein macro-ions, together with attractive protein interactions, such as van der Waals, hydrophobic and hydration forces, provide an unambiguous mechanism for the observed transition and a more physical interpretation of the various observations.
Muschol, Martin↗
A Unified Description of Salt Effects on the Liquid–Liquid Phase Separation of Proteins
Protein aggregation via liquid-liquid phase separation (LLPS) is ubiquitous in nature and is intimately connected to many human diseases. Although it is widely known that the addition of salt has crucial impacts on the LLPS of proteins, full understanding of the salt effects remains an outstanding challenge. Here, we develop a molecular theory that systematically incorporates the self-consistent field theory for charged macromolecules into the solution thermodynamics. The electrostatic interaction, hydrophobicity, ion solvation, and translational entropy are included in a unified framework. Our theory fully captures the long-standing puzzles of the nonmonotonic salt concentration dependence and the specific ion effect. We find that proteins show salting-out at low salt concentrations due to ionic screening. The solubility follows the inverse Hofmeister series. In the high salt concentration regime, protein continues salting-out for small ions but turns to salting-in for larger ions, accompanied by the reversal of the Hofmeister series. We reveal that the solubility at high salt concentrations is determined by the competition between the solvation energy and translational entropy of the ion. Furthermore, we derive an analytical criterion for determining the boundary between the salting-in and salting-out regimes, which is in good agreement with experimental results for various proteins and salt ions.
36 MATERIALS SCIENCE↗
Physical chemistry and evolution of salt tolerance in halobacteria
The cellular constituents of extremely halophilic bacteria not only tolerate high salt concentration, but in many cases require it for optical functioning. The characteristics affected by salt include enzyme activity, stability, allosteric regulation, conformation and subunit association. The salt effects are of two major kinds: electrostatic shielding of negative charges by cations at low salt concentration, and hydrophobic stabilization by salting-out type salts at high salt concentration. The composition of halobacterial proteins shows an excess of acidic amino acids and a deficiency of nonpolar amino acids, which accounts for these effects. Since the cohesive forces are weaker and the repulsing forces are stronger in these proteins, preventing aggregation in salt, these structures are no longer suited for functioning in the absence of high salt concentrations. Unlike these nonspecific effects, ribosomes in halobacteria show marked preference for potassium over sodium ions. To ensure the proper intracellular ionic composition, powerful ion transport systems have evolved in the halobacteria, resulting in the extrusion of sodium ions and their replacement by potassium. It is likely that such membrane transport system for ionic movements is a necessary requisite for salt tolerance.
Lanyi, J. K.↗
Relative susceptibility of titanium alloys to hot-salt stress-corrosion
Susceptibility of titanium alloys to hot-salt stress-corrosion cracking increased as follows: Ti-2Al-11Sn-5Zr-0.2Si(679), Ti-6Al-2Sn-4Zr-2Mo(6242), Ti-6Al-4V(64), Ti-6Al-4V-3Co(643), Ti-8Al-1Mo-1V(811), and Ti-13V-11Cr-3A1(13-11-3). The Ti-5Al-6Sn-2Zr-1Mo-0.25Si(5621S) alloy was both the least and most susceptible depending on heat treatment. Such rankings can be drastically altered by heat-to-heat and processing variations. Residual compressive stresses and cyclic exposures also reduce susceptibility to stress-corrosion. Simulated turbine-engine compressor environmental variables such as air velocity, pressure, dewpoint, salt concentration, and salt deposition temperature have only minor effects. Detection of substantial concentrations of hydrogen in all corroded alloys confirmed the existence of a hydrogen embrittlement mechanism.
Gray, H. R.↗