A Novel Low-Cost Thermal Energy Storage for Building Equipment Peak Load Shifting
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32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
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Atomically dispersed platinum-group metal-free catalysts and method for synthesis of the same
Atomically dispersed platinum-group metal-free catalyst and method for synthesizing the same. According to one embodiment, the catalyst is made by a method in which, in a first step, a metal oxide/zeolitic imidazolate frameworks (ZIF) composite is formed by combining (i) nanoparticles of an oxide of at least one of iron, cobalt, nickel, manganese, and copper, (ii) a hydrated zinc salt, and (iii) an imidazole. Then, in a second step, the metal oxide/ZIF composite is thermally activated, i.e., carbonized, to form an M-N—C catalyst. Thereafter, the M-N—C catalyst may be mixed with a quantity of ammonium chloride, and then the M-N—C/NH 4 Cl mixture may be pyrolyzed. The foregoing NH 4 Cl treatment may improve the intrinsic activity of the catalyst. Then, a thin layer of nitrogen-doped carbon may be added to NH 4 Cl-treated M-N—C catalyst by chemical vapor deposition (CVD). Such CVD treatment may improve the stability of the catalyst.
Wu, Gang↗
Hydrated multivalent cations are new class of molten salt mixtures
Electrical conductance and activation energy measurements on mixtures of calcium and potassium nitrate show the hydrated form to be a new class of molten salt. The theoretical glass transition temperature of the hydrate varied in a manner opposite to that of the anhydrous system.
Angell, C. A.↗
Crustal structure and igneous processes in a chondritic Io
Liquid sulfur can form when metal-free C1 or C2 chondrites are heated. It may be obtained either by direct melting of native sulfur in disequilibrated C1 or C2 chondrites or by incongruent melting of pyrite and other sulfides in thermodynamically equilibrated rocks of the same composition. Hence, Lewis considered C2 chondrites to be the best meteoritic analog for Io's bulk composition. Metal-bearing C3 and ordinary chondrites are too chemically reduced to yield liquid sulfur and are not thought to represent plausible analogs of Io's bulk composition. An important aspect of Lewis' work is that CaSO4 and MgSO4 are predicted to be important in Io. Real C1 and C2 chondrites contain averages of, respectively, 11 percent and 3 percent by mass of salts (plus water of hydration). The most abundant chondritic salts are magnesium and calcium sulfates, but other important components include sulfates of sodium, potassium, and nickel and carbonates of magnesium, calcium, and iron. It is widely accepted that chondritic salts are formed by low-temperature aqueous alteration. Even if Io originally did not contain salts, it is likely that aqueous alteration would have yielded several percent sulfates and carbonates. In any event, Io probably contains sulfates and carbonates. This report presents the results of a model of differentiation of a simplified C2 chondrite-like composition that includes 1.92 percent MgSO4, 0.56 percent CaSO4, 0.53 percent CaCO3, and 0.094 percent elemental sulfur. The temperature of the model is gradually increased; ensuing fractional melting results in these components extruding or intruding at gravitationally stable levels in Io's crust. Relevant phase equilibria were reviewed. A deficiency of high-pressure phase equilibria renders the present model qualitative.
Kargel, J. S.↗
Evolution of Metastable Phases During Mg Metal Corrosion: An In Situ Cryogenic X-ray Photoelectron Spectroscopy Study
Magnesium and its alloys are potential structural materials candidates for a wide variety of applications due to their high strength-to-weight ratio. However, ductility and poor corrosion resistance under ambient environmental conditions are the bottleneck for industrial deployment. Designing passivation layers and/or corrosion resistant alloys requires fundamental understanding of the corrosion process. The traditional ex-situ spectroscopic measurements of polycrystalline metal surface with ubiquitous surface impurities and grain boundaries only provided an indistinct view of the corrosion process. To clearly distinguish the mechanism and sequence of corrosion process, we employed in-situ cryo-based x-ray photoelectron spectroscopy (XPS) measurements on Mg single crystal surface exposed to aqueous salt solution. Clean Mg (0001) surfaces were exposed to pure D2O and NaCl aqueous solution (5 wt% NaCl+95 wt% D2O). The interfacial reactions were studied using multimodal analysis including XPS, x-ray diffraction (XRD) and scanning electron microscopy (SEM). In contrast to previous studies, our experiments demonstrated the formation of magnesium chloride hydroxide hydrate during aqueous salt corrosion processes. Evidence of metastable ClO* radicals were also found during the initial aqueous salt solution exposure.
Shutthanandan, Vaithiyalingam↗
Impact of Ion–Ion Correlated Motion on Salt Transport in Solvated Ion Exchange Membranes
The influence of dynamical ion-ion correlations and ion pairing on salt transport in ion exchange membranes remain poorly understood. In this study, we use the framework of Onsager transport coefficients within atomistic molecular dynamics sim- ulations to study the impact of ion-ion correlated motion on salt transport in hydrated polystyrene sulfonate membranes and compare with the results from aqueous salt so- lutions. At sufficiently high salt concentrations, cation-anion dynamical correlations exert a significant influence on both salt diffusivities and conductivities. Anion-anion distinct correlations, arising from the imbalance between the concentration of free (mo- bile) cations and anions, and the retarding effect of the fixed charge groups on cations, proves to be an additional important feature for polymer membranes. Furthermore, our results demonstrate that dynamical correlations should become an important consideration in experimental measurements of salt diffusivities and conductivities for non-dilute salt solutions in polymer membranes.
36 MATERIALS SCIENCE↗
Local stress within a granular molecular solvent matrix, a mechanism for individual ion hydration
The activity of water is important in many natural systems and directed processes. To better understand water activity, the hydration of individual ions is approximated for a recently developed speciation-based solution model. Here a matrix of values for hydration of complete salts (anion and cation) was used as source data to calculate individual ion hydration values. Some electrolytes were excluded from calculations of individual ion hydration due to the prevalence of ion pairing and resulting liberation of water upon ion pairing. Evaluation of the periodic trends emerging from individual ion hydration values suggests that ionic volume, relative to the volume of molecular water, dictates both modeled hydration requirements (related to vapor-liquid-equilibrium-derived activity) as well as properties historically described by hydrodynamic radius (ion diffusion and solution viscosity). When water is conceptualized as a granular three-dimensional matrix, solutes may function as substitutional defects (dilation or constriction) inducing local compressive or tensile stress. These results have implications on the mechanism of the Hofmeister series and series reversals.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Experimental study on a novel three-phase absorption thermal battery with high energy density applied to buildings
Buildings contribute to 75% of total electricity consumption and 80% of peak electricity demand in the United States. A significant portion of building electricity consumption goes to space conditioning. Therefore, using thermal energy storage (TES) to decouple the building electricity consumption and the fluctuating space-conditioning load has significant potential to shift peak electricity demand and improve the stability of the grid. To provide effective TES within the spatial constraints in buildings, a three-phase absorption thermal battery (TATB) system with very high energy storage density was designed and studied. The TATB stores low-temperature heat in hydrate crystals of salts and supports space conditioning through absorption systems. In this study, a benchtop TATB using lithium chloride (LiCl) hydrate crystals as the storage material was tested under practical operating conditions for its energy storage density and discharge rate. We report the TATB successfully generated LiCl hydrate crystals during charging mode and then dissolved the crystals during discharging mode. A material-based energy storage density of 300 kWh/m 3 (specific energy of 903 kJ/kg) was achieved with a discharge rate of up to 1.3 kW thermal energy. The test results verified the high performance of the TATB and encouraged further development of this technology.
25 ENERGY STORAGE↗
Renal clearance studies of effect of left atrial distension in the dog.
Investigation of the water diuresis of left atrial distension in 16 dogs on the basis of clearance studies employing hydration, chronic and acute salt loading, deoxycorticosterone (DOCA) in excess, and distal tubular nephron blockade with diuretics. The diuresis was found in hydrated and salt-loaded dogs and was independent of DOCA and presumed renin depletion. It was not found in five dogs after distal tubular blockade. No significant reproducible saluresis was ever documented. The water diuresis was always stopped by exogenous vasopressin (seven dogs). Antidiuretic hormone inhibition with distal tubular nephron water permeability changes appears to be the sole mechanism of the diuresis of left atrial distension in the dog.
Kinney, M. J.↗
Growth and Survival of Perchlorate-Reducing Bacteria in Media Containing Elevated Perchlorate Concentrations and UV-C Conditions
Introduction: The identification of perchlorate (ClO4(-)) on Mars has led to the possibility that complete redox couples are available for microbial metabolism in contemporary surface environments. Perchlorate-reducing bacteria (PRB) utilize ClO4(-) and chlorate (ClO3(-)) as terminal electron acceptors due to the high reduction potential. Additionally, ClO4(-) salts have been suggested as a possible source of brines on Mars and spectral evidence indicates that the hydration of ClO4(-) salts in the regolith of Martian is linked to the surface recurring slope lineae (RSL). For these reasons PRB may serve as analog organisms for possible life on Mars. However, there is very little information on the viability of PRB in aqueous environments that contain high levels of perchlorate Microorganisms on or near the surface of Mars, such as in the RSL, would potentially be exposed to high-salinity and high ultraviolet radiation environments. Under these extreme conditions, microorganisms must possess mechanisms for maintaining continued high genome fidelity. To assess possible microbial viability in contemporary Mars analog environments we are investigating the tolerance of two PRB strains in aqueous conditions under high UV-C conditions and high ClO4(-) concentrations.
Bywaters, K. F.↗
Methane Hydrate Formation and Evolution During Sedimentation
We explored methane hydrate formation with sedimentation with a newly developed one-dimensional, multiphase flow, multicomponent transport numerical model. Our model couples methane hydrate formation from in situ microbial methane generation within the hydrate stability zone (HSZ), methane recycling, and microbial methane generation below the base of the hydrate stability zone (BHSZ). Both recycled methane and deeply generated methane are transported into the HSZ by buoyancy-driven free gas flow. Free gas flows through the HSZ by both the processes of capillary-dependent pore fillings and by salt exclusion during hydrate formation, with the former being the dominant mechanism. We quantitively illustrated the formation of enriched hydrate in muddy sediments above, and interconnected free gas below, the BHSZ, which are common features along the world's continental margin. In addition, we showed two ways to form concentrated methane hydrate above the BHSZ. The first mechanism is local free gas flow during methane recycling. This happens at sites with sufficient methane generation above the BHSZ. The second mechanism is deep microbial methane generation which is transported into the HSZ by free gas flow. This mechanism plays a more important role at sites with high sedimentation rates. This study provides new insights into methane hydrate formation and distribution below the seafloor. It is important for understanding the carbon cycle and carbon storage below the seafloor and for resource evaluation and exploitation.
58 GEOSCIENCES↗
Evaluation of the lgnitability Hazards in Remediated Nitrate Salt Waste
The hazards associated with the characteristic of ignitability in remediated nitrate salt (RNS) waste containing nitric acid (HNO 3 ) and metal nitrate salts, currently stored at the Waste Control Specialists (WCS) facility near Andrews, Texas have been evaluated. For these waste drums there are two ignitability hazards that may apply, each separately distinguished from the other and uniquely correlated to one of two competing reaction mechanisms. One ignitability hazard, designated the autocatalytic thermal runway, is uniquely correlated to an acid/base reaction of hydrolysis of a hydrated metal nitrate salt. The other applicable ignitability hazard, designated the oxidizer property, is uniquely correlated to a redox disproportionation reaction involving an anhydrous metal nitrate salt. Which reaction mechanism pathway is accessible to a given metal nitrate, and therefore which ignitability hazard may apply, depends on the acidity of the metal ion and its corresponding capacity to maintain coordination with water.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Mineralogical Evidence for Environmental Change in the Clay-Sulfate Transition at Gale Crater, Mars
A primary reason for selecting Gale crater as the Mars Science Laboratory (MSL) Curiosity rover landing site was a clear mineralogical transition from Fe/Mg smectite in older strata to hydrated Mg sulfate salts in younger strata observed in orbital visible/shortwave-infrared reflectance data. This transition has been observed in other early-Hesperian terrains on Mars and has been hypothesized to signal a planet-wide change in climate from relatively warm and wet to cold and dry. Curiosity studied the sedimentology and geochemical and mineralogical composition of rocks in this “clay-sulfate transition” region from sols 3052 to 3572 (i.e., March 2021 to August 2022), with arrival at the sulfate unit on sol 3574. Here, we report on the mineralogical measurements made by the CheMin X-ray diffractometer of the six drill targets in the clay-sulfate transition and the first drill target in the sulfate unit. We use compositional data and sedimentological observations to interpret depositional and diagenetic environments and present hypotheses to explain the transition from clay minerals to hydrated Mg sulfates.
E. B. Rampe↗
Structural and chemical complexity of minerals: An update
The complexities of chemical composition and crystal structure are fundamental characteristics of minerals that have high relevance to the understanding of their stability, occurrence and evolution. This review summarises recent developments in the field of mineral complexity and outlines possible directions for its future elaboration. The database of structural and chemical complexity parameters of minerals is updated by H-correction of structures with unknown H positions and the inclusion of new data. The revised average complexity values (arithmetic means) for all minerals are 3.54(2) bits/atom and 345(10) bits/cell (based upon 4443 structure reports). The distributions of atomic information amounts, chemIG and strIG, versus the number of mineral species fit the normal modes, whereas the distributions of total complexities, chemIG,total and strIG,total, along with numbers of atoms per formula and per unit cell are log normal. The three most complex mineral species known today are ewingite, morrisonite and ilmajokite, all either discovered or structurally characterised within the last five years. The most important complexity-generating mechanisms in minerals are: (1) the presence of isolated large clusters; (2) the presence of large clusters linked together to form three-dimensional frameworks; (3) formation of complex three-dimensional modular frameworks; (4) formation of complex modular layers; (5) high hydration state in salts with complex heteropolyhedral units; and (6) formation of ordered superstructures of relatively simple structure types. The relations between symmetry and complexity are considered. The analysis of temporal dynamics of mineralogical discoveries since 1875 with the step of 25 years show the increasing chemical and structural complexities of human knowledge of the mineral kingdom in the history of mineralogy. In the Earth’s history, both diversity and complexity of minerals experience dramatic increases associated with the formation of Earth’s continental crust, initiation of plate tectonics and the Great Oxidation event.
complexity↗
Synthesis and characterization of super occluded LiCl-KCl in zeolite-4A as a chloride salt waste form intermediate
Here, this paper reports the hygroscopic properties of eutectic LiCl-KCl after absorption into zeolite-4A, up to salt loadings of 75 wt%. Samples of the salt occluded zeolite were hydrated in a humidity chamber at constant temperature and relative humidity for up to 100 h. At up to 45 wt% salt loading, the un-occluded phase of salt consisted primarily of NaCl, which forms when the Na + ions present in the zeolite framework exchange with Li + and K + ions from the eutectic LiCl-KCl. This results in minimal water absorption and corrosion of contacted stainless steel. At greater than 45 wt% salt loading, water absorption and corrosion progressively worsened. The mixture has a significant amount of excess LiCl-KCl, making it highly hygroscopic. This study reveals an option for the intermediate treatment of waste salt from spent nuclear fuel electrorefiners that could facilitate it to be stored in a non-inert atmosphere for extended periods of time before final conversion into a permanent waste form.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Physical properties of cryovolcanic brines: Applications to the evolution of Ganymede
Carbonaceous chondrites contain abundant veins of water soluble salts, including carbonates and hydrated sulfates of Mg, Ca, Na, Ni, and Fe. These constitute over 1/4 of the mass of the meteorite Orgueil. Magnesium sulfate is the most abundant salt, constituting nearly half the mass of all salt components combined (anhydrous), and 73 pct. of the highly water soluble salts. The assumption that icy satellites and asteroids contain rock compositionally similar to carbonaceous chondrites suggests that salts may be important in the cryoigneous evolution of icy satellites and asteroids. Ordinary chondrites, an alternative rock component of icy satellites, lack abundant salts, although their anhydrous silicate assemblages are unstable with respect to water and would react to produce salts upon initial melting of ice. Some basic physiochemical properties are reviewed of likely cryovolcanic brines and how the existence of soluble salts in Ganymede might affect its structure and evolution is considered. Observations indicate late stage (post heavy bombardment and post tectonic) volcanism on Ganymede. The highly fluid character of Ganymedian volcanism is consistent with extrusions of either water or salt water brines.
Kargel, Jeffrey S.↗
UT-GOM2-2 Drilling Fluid (Technical Note)
It is proposed that a salt-saturated, water-based mud might improve borehole stability for UT-GOM2-2 relative to a fresh-water-based mud. However, the primary objective for UT-GOM2-2 is to safely and successfully acquire uncompromised hydrate-bearing sediment cores. This can only be done if conditions stay within the hydrate stability zone, and well away from the hydrate stability boundary. The addition of salt to the drilling mud, shifts the hydrate stability boundary closer to estimated conditions. This shift, by some estimates of pressure and temperature, where conditions now fall outside of the hydrate stability zone, may result in borehole enlargement and the release of free gas into the borehole. This shift by all estimates, even when coring conditions stay inside the hydrate stability zone, shrinks the window between the estimated conditions and the hydrate stability boundary. This shift is likely to compromise the hydrate-bearing cores while they are being recovered from the bottom-hole to the rig floor. In this report we present two examples: 1) Assuming temperature and pressure from in-situ estimates: Hydrate within the target reservoirs (Orange and Blue) at Walker Ridge Block 313 (WR 313) will be outside the hydrate stability zone in the presence of a drilling mud with 9.5 wt.% salinity (the salinity of the proposed 10.5 ppg salt-based mud) at in situ pressure and temperature. Thus, the hydrate will be unstable. A 10.5 ppg salt-based mud may result in dissociation of the hydrate into its components: water and gas. 10.5 ppg salt-based mud may enlarge the borehole, release free gas into the borehole, and compromise the cores. 2) Assuming temperatures equal to the measured LWD borehole temperatures at this location: Hydrate within the target reservoirs will be stable with a salinity of 9.5 wt.% (the salinity of the proposed 10.5 ppg salt-based mud), but possibly unstable (just at the methane hydrate stability boundary) for a salinity of 17.2 wt.% (the salinity of the proposed 13.5 ppg salt-based kill mud). if the borehole has the same temperature as recorded during previous LWD drilling at this location. A 13.5 ppg salt-based kill mud may destabilize the borehole. More importantly, a 10.5 ppg salt-based mud does not provide a large enough window between the estimated conditions and the hydrate stability boundary. Core temperatures and pressures fluctuate from the bottom-hole conditions as the core is brought up from the bottom-hole to the rig floor. These fluctuations are likely to cause the hydrate in the cores to touch or cross the stability boundary. Therefore, cores captured using a 10.5 ppg salt-based mud are likely to be compromised during core recovery to the rig floor.
03 NATURAL GAS↗