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At least 325 records · Page 18

Vapor deposition and condensate flow on combustion turbine blades - Theoretical model to predict/understand some corrosion rate consequences of molten alkali sulfate deposition in the field or laboratory

An analysis is undertaken of aerodynamically- and centrifugally-driven liquid condensate layers on nonisothermal combustion turbines' stator vanes and rotor blades. Attention is given to the quantitative consequences of one possible mechanism for the initiation of 'hot corrosion' in the underlying blade material through a 'fluxing' of the protective oxide coating by the molten salt of the Newtonian condensate film. Illustrative calculations are presented for the condensate streamline pattern and the distributions of the steady-state condensate layer thickness, together with the corresponding oxide dissolution rate, for a test turbine blade.

Rosner, Daniel E.↗

Optimizing protic ionic liquid electrolyte for pre-intercalated Ti 3 C 2 T x MXene supercapacitor electrodes

Electrical double-layer capacitors (EDLCs) are of increasing importance in energy storage from renewable sources. The properties of the electrode and electrolyte materials influence the energy and power densities of EDLCs. We examined the specific capacitance and ion dynamics of a protic ionic liquid confined in pre-intercalated Ti 3 C 2 T x MXene. Our electrochemical measurements demonstrated that the creation of a protic ionic liquid, 1-butyl-3-H-imidazolium bis(trifluoromethanesulfonyl)imide (BuIMH-NTf2), using a mixture of ionic liquid, 1-butyl imidazole (BuIM), and salt, bis(trifluoromethanesulfonyl)imide (HNTf2), in a ratio of 0.8:0.2 led to the optimal capacitance. Remarkably, quasi-elastic neutron scattering measurements revealed increased particle mobility at this composition, attributed to the more efficient accumulation of BuIMH + on the electrode surface. This deposit of additional ions results in fewer BuIM molecules away from the surface, enhancing their mobility due to reduced crowding. This composition-dependent electrochemical behavior will guide the formulation of more efficient protic ionic liquid systems, enabling faster ion transport in energy storage devices.

36 MATERIALS SCIENCE↗

Fluorinated Glyme Solvents to Extend Lithium-Sulfur Battery Life (Final Technical Report, Unlimited)

This project investigated a number of partially fluorinated glymes (PFGs) as electrolyte cosolvents to improve the performance of lithium-sulfur (Li-S) batteries. A major issue in Li-S cells is the electrochemical reaction of sulfur in the cathode to form lithium polysulfides (LPS) that dissolve in the electrolyte. Those LPS are electrochemically and chemically reactive at the lithium anode, resulting in lithium sulfide deposition on the anode and also electrochemical reaction at both the anode and cathode, leading to a “polysulfide shuttle” and reduced coulombic efficiency (CE) and self-discharge of the cell. PFGs reduce the solubility of LPS while maintaining good solubility of lithium salts such as LiTFSI. By adjusting the amount of PFG as cosolvent in the electrolyte, we showed that the solubility of LPS in the electrolyte can be tuned. (It is not desirable to completely eliminate LPS in the electrolyte, as they facilitate electrochemical reaction of the electrically insulating S 8 and Li 2 S within the cathode by shuttling charge between them and the conductive carbon.) Another issue in Li-S cells is degradation of the Li anode over many cycles of stripping (discharge) and plating (charge). We showed that PFGs have a beneficial effect on the physical morphology of the Li anode, SEI formation, and the CE of a Li-Li cell. Among the many PFGs tested, we found the best performance from PFGs designated PFG2 and PFG5, and these two PFGs were thoroughly studied. A systematic coin-cell study of electrolyte solvents of 90:10, 80:20, or 70:30 DME:PFG (DME = 1,2-dimethoxyethane) revealed some systematic trends: a higher percentage of PFG solvent led to substantially longer cycle life, but at the same time reduced specific capacity (mAh/g(S)) and cell capacity at higher rates. These studies used LiFSI as the electrolyte salt, as it was found to extend cycle life compared to LiTFSI. Finally, the addition of a small amount of 1,3-dioxolane (DOL) to the electrolyte was found to be beneficial. The overall optimal electrolyte solution was found to be 0.6 M LiFSI + 0.5 M LiNO 3 in 75:5:20 DME/DOL/PFG (either PFG2 or PFG5).

25 ENERGY STORAGE↗

Oxychlorine Detections on Mars: Implications for Cl Cycling

The Sample Analysis at Mars (SAM) instrument has detected evolved O2 and HCl indicating the presence of perchlorate and/or chlorate (oxychlorine) in all 11 sediments analyzed to date. The hyperarid martian climate is believed to have allowed accumulation of oxychlorine and assumed chloride contents similar to those in hyperarid terrestrial settings. The linear correlation of oxychlorine and chloride of Gale Crater sediments is low (r (sup 2) equals 0.64). Correlations present in hyperarid Antarctica and the Atacama Desert are attributed to unaltered atmospheric source coupled with minimal redox cycling by biological activity. Terrestrial semi-arid to arid settings have low correlations similar to Gale Crater and are attributed to additional inputs of Cl minus from sea salt, dust, and/or proximal playa settings, and possible reduction of oxychlorine phases during wetter periods. While microbiological processes could contribute to low oxychlorine/chloride correlations on Mars, several abiotic mechanisms are more likely, such as changing oxychlorine production rates with time and/or post-depositional geochemical redox processes that altered the Gale Crater oxychlorine and chloride contents.

Sutter, B.↗

Densification of Cathode/Electrolyte Interphase to Enhance Reversibility of LiCoO 2 at 4.65 V

For LiCoO 2 (LCO) operated beyond 4.55 V (vs Li/Li + ), it usually suffers from severe surface degradation. Constructing a robust cathode/electrolyte interphase (CEI) is effective to alleviate the above issues, however, the correlated mechanisms still remain vague. Herein, a progressively reinforced CEI is realized via constructing Zr-O deposits (ZrO 2 and Li 2 ZrO 3 ) on LCO surface (i.e., Z-LCO). Upon cycle, these Zr-O deposits can promote the decomposition of LiPF6, and progressively convert to the highly dispersed Zr-O-F species. In particular, the chemical reaction between LiF and Zr-O-F species further leads to the densification of CEI, which greatly reinforces its toughness and conductivity. Further, combining the robust CEI and thin surface rock-salt layer of Z-LCO, several benefits are achieved, including stabilizing the surface lattice oxygen, facilitating the interface Li + transport kinetics, and enhancing the reversibility of O3/H1-3 phase transition, etc. As a result, the Z-LCO||Li cells exhibit a high capacity retention of 84.2% after 1000 cycles in 3–4.65 V, 80.9% after 1500 cycles in 3–4.6 V, and a high rate capacity of 160 mAh g -1 at 16 C (1 C = 200 mA g -1 ). This work provides a new insight for developing advanced LCO cathodes.

25 ENERGY STORAGE↗

Aqueous Alteration on Mars

The occurrence of extensive valley networks and layered deposits of phyllosilicates and sulfates during the late Noachian/Hesperian periods (approx. 3-4 Gyrs) indicates a past martian climate that was capable of maintaining liquid water at the surface. The planet’s climate drastically changed after these early “episodes” of water to a drier and colder environment during the Amazonian period (past 3.0 Gyrs). The objective of this paper is to describe aqueous alteration/weathering scenarios on Mars based on observations returned by rover and lander missions. The chemistry of most outcrops, rocks, and “soils” that have interacted with water has not been extensively changed from average Mars crustal basaltic composition. Little chemical variation suggests closed hydrologic systems were prominent on early Mars and/or the water/rock ratios were low. Open hydrologic systems occur at local scales, e.g., high Si and Ti rocks and “soil” deposits around a volcanic feature in Gusev crater. Geochemical and mineralogical indicators for aqueous alteration include jarosite and other Fe-sulfates at several locations suggesting acid-sulfate alteration conditions. High Si and Ti rocks, sediments, and “soil” deposits are consistent with basaltic residues extenively leached by extremely acidic fluids. Variations in the Fe/Mn ratio of fracture veins infilled with sulfate-rich materials suggest changes in redox and/or pH conditions of the migrating fluids. The increase of nanophase iron oxides and salts with depth in several “soil” pits escavated by the Spirit rover’s wheel in Gusev crater suggests the translocation/mobolization of these phases by liquid water. This “pedogenic” process is the result of limited water movement through the surface sediments during the Amazonian period; however, it is likely that paleosols exist on Mars that formed during the early “wetter” history of the planet. Soil scientists have the opportunity to continue to (and should) be involved in the exploration of the Red planet.

Ming, Douglas W.↗

Carbonate Platform Development and Stromatolite Morphogenesis: Constraints on Environmental and Biological Evolution

Work this past year has focused on the globally significant events of faunal turnover, tectonic reorganization, and biogeochemical change that closely coincided with the Precambrian-Cambrian boundary in the Sultanate oilman. Higher temporal and chronostratigraphic resolution are required in order to answer this question. Stratigraphic sections must contain fossils, volcanic rocks, and abundant carbonates with little or no diagenetic overprint. The Ara Group of the South Oman Salt Basin presents such a succession - with carbonate rocks tightly enclosed in a protective envelope of impermeable halite, these rocks have likely never exchanged with younger fluids. Our work has had two thrusts. The first pertains to the geochemistry of the Athel Formation, a deep water deposit formed at the Precambrian-Cambrian boundary which contains unique records of ocean anoxia for that time interval. This unit is important because it will enable tighter focus on the links which existed between global biogeochemical events and episodes of faunal extinction and radiation. The second direction involves a comparison of terminal Proterozoic thrombolites between Oman (subsurface) and Namibia (outcrop). These thrombolites are important not only as significant deposits of ancient microbial communities, but because they formed the key substrate for growth of the oldest calcified metazoans - Cloudina and Namacalathus.

Grotzinger, John P.↗

A Simple Halogen-Free Magnesium Electrolyte for Reversible Magnesium Deposition through Cosolvent Assistance

Rechargeable Mg batteries are one of the most investigated polyvalent-metal storage batteries owing to the increased safety associated with the nondendritic nature of Mg electrodeposition, high volumetric capacity, and low cost. To realize the commercial applications of Mg batteries, there are still a number of challenges remaining unsolved, in particular, the lack of halogen free Mg electrolytes, as the use of the halogens remains a major limiting factor to achieving high voltage cathodes. The research presented here introduces an innovative approach to prepare a halogen-free Mg-based electrolyte in a simple, nonsynthetic method that can plate and strip Mg reversibly. Results suggest that by introducing a secondary amine cosolvent the magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2 ) salt can be easily dissolved into a wide array of polar but aprotic ether solvents. A systematic structural investigation of a representative Mg(TFSI) 2 electrolyte in the cosolvent systems with the secondary amine was performed using pair distribution function (PDF) analysis, single crystal diffraction analysis, and NMR. The experimental atomic scale understanding reveals an ion pair structure of Mg 2+ coordinated with six oxygen donors from the bis(trifluoromethanesulfonyl)imide (TFSI) anions and the THF solvent located in the first solvation shell. The as-formed neutral ion pair structure acts as the active component for reversible Mg deposition. We believe this new route of preparing Mg electrolytes can extend the current understanding of Mg electrolyte functionality for rechargeable Mg batteries and offers more guidance for the future electrolyte design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A High Energy–Density, Cobalt–Free, Low–Nickel LiNi 0.7 Mn 0.25 Al 0.05 O 2 Cathode with a High–Voltage Electrolyte for Lithium–Metal Batteries

Cobalt-free cathode materials have garnered increased attention for applications in next-generation batteries for electric vehicles, as cobalt is considered to have at a high supply chain risk. Here, the use of a localized saturated electrolyte (LSE) to enable stable cycling of a cobalt-free, low-nickel layered-oxide cathode LiNi 0.7 Mn 0.25 Al 0.05 O 2 (NMA-70) to higher voltages (4.6 V) in a lithium-metal battery is demonstrated. Compared to the baseline LP57 electrolyte, the LSE extends the cycle life from ≈100 cycles to ≈400 cycles before reaching 80% capacity retention. Visual indicators of cell degradation, such as product deposition, are observed on electrodes cycled in LP57. It is shown that cycling NMA-70 in LSE reduces the overall active material loss and overpotential growth during extended cycling. This is attributed to the formation of a beneficial fluorinated interphase layer, a lower degree of rock-salt phase formation, and a reduction in the gas evolution from the cathode surface. The decrease in gas evolution from the cathode cycled in LSE reflects a lower degree of electrolyte reactivity and an overall improvement in the safety characteristics of the cell. Furthermore, this study highlights the importance of a stable electrolyte to enable the high-voltage cycling of alternative, lower nickel, and cobalt-free cathodes.

25 ENERGY STORAGE↗

Two-step spin-coating of vacancy-ordered double perovskites enables growth of thin films for electronic devices

Vacancy-ordered double perovskites (VODPs), such as Cs 2 TeX 6 (X = Cl, Br, I), are lead-free alternatives to conventional metal-halide perovskites (MHPs). One limitation of VODPs is the lack of processes to form thin films relevant for physical characterization and electronic devices. A two-step spin-coating method was developed for synthesizing high-quality films of Cs 2 TeBr 6 . Independently depositing CsBr and TeBr 4 enables high precursor concentrations and control over crystallization kinetics. By optimizing the spin-coating parameters, conversion of precursors to phase pure films was observed using structural and surface characterization methods. The growth of mixed-halide systems was investigated using alternative salts including CsCl and CsI. The formation of halide alloys was found to depend on the existence of routes to byproducts. Lastly, single carrier diodes of Cs2TeBr6 were designed following valence band characterization with photoelectron spectroscopy. Temperature-dependent space-charge-limited current measurements revealed that transport occurs by hopping and the hole mobility is 3.2 × 10 −5 cm 2 V −1 s −1 near room temperature. As a result, the insights from the 2-step procedure provide a pathway towards making semiconducting devices from VODPs.

Kuklinski, Owen [University of California, Santa B↗

PDADMAC/PSS Oligoelectrolyte Multilayers: Internal Structure and Hydration Properties at Early Growth Stages from Atomistic Simulations

We analyze the internal structure and hydration properties of poly(diallyl dimethyl ammonium chloride)/poly(styrene sulfonate sodium salt) oligoelectrolyte multilayers at early stages of their layer-by-layer growth process. Our study is based on large-scale molecular dynamics simulations with atomistic resolution that we presented recently [Sánchez et al., Soft Matter 2019, 15, 9437], in which we produced the first four deposition cycles of a multilayer obtained by alternate exposure of a flat silica substrate to aqueous electrolyte solutions of such polymers at 0.1M of NaCl. In contrast to any previous work, here we perform a local structural analysis that allows us to determine the dependence of the multilayer properties on the distance to the substrate. We prove that the large accumulation of water and ions next to the substrate observed in previous overall measurements actually decreases the degree of intrinsic charge compensation, but this remains as the main mechanism within the interface region. We show that the range of influence of the substrate reaches approximately 3 nm, whereas the structure of the outer region is rather independent from the position. This detailed characterization is essential for the development of accurate mesoscale models able to reach length and time scales of technological interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructural Underpinnings of Giant Intrinsic Exchange Bias in Epitaxial NiCo 2 O 4 Thin Films

Understanding intrinsic exchange bias in nominally single-component ferromagnetic or ferrimagnetic materials is crucial for simplifying related device architectures. However, the mechanisms behind this phenomenon and its tunability remain elusive, which hinders the efforts to achieve unidirectional magnetization for widespread applications. Inspired by the high tunability of ferrimagnetic inverse spinel NiCo 2 O 4 , the origin of intrinsic exchange bias in NiCo 2 O 4 (111) films deposited on Al 2 O 3 (0001) substrates are investigated. The comprehensive characterizations, including electron diffraction, X-ray reflectometry and spectroscopy, and polarized neutron reflectometry, reveal that intrinsic exchange bias in NiCo 2 O 4 (111)/Al 2 O 3 (0001) arises from a reconstructed antiferromagnetic rock-salt Ni x Co 1-x O layer at the interface between the film and the substrate due to a significant structural mismatch. Remarkably, by engineering the interfacial structure under optimal growth conditions, it can achieve exchange bias larger than coercivity, leading to unidirectional magnetization. Such giant intrinsic exchange bias can be utilized for realistic device applications. This work establishes a new material platform based on NiCo 2 O 4 , an emergent spintronics material, to study tunable interfacial magnetic and spintronic properties.

36 MATERIALS SCIENCE↗

Carbonate-sulfate volcanism on Venus?

Venusian canali, outflow channels, and associated volcanic deposits resemble fluvial landforms more than they resmeble volcanic features on Earth and Mars. Some canali have meandering habits and features indicative of channel migration that are very similar to meandering river channels and flood plains on Earth, venusian outflow channels closely resemble water-carved outflow channels on Mars and the Channeled Scabland in Washington, collapsed terrains at the sources of some venusian channels resemble chaotic terrains at the sources of martian outflow channels, venusian lava deltas are similar to bird's-foot deltas such as the Mississippi delta, and venusian valley networks indicate sapping. We have developed an alternative possibility that the lava had a water-like rheology and a melting point slightly greater than Venus' surface temperature, thus accounting for the unusual behavior of the lava. Unlike silicate lavas, some carbonatites (including carbonate-sulfate-rich liquids) have these properties; thus they can flow great distances while retaining a high fluidity, significant mechanical erosiveness, and substantial capacity to transport and deposit sediment. Venusian geochemistry and petrology are consistent with extensive eruptions of carbonatite lavas, which could have crustal and/or mantle origins. Venus' atmosphere (especially CO2, HCl, and HF abundances) and rocks may be in local chemical equilibrium, which suggests that the upper crust contains large amounts of calcite, anhydrite, and other salts. Chemical analyses indicate, according to some models, that Venusian rocks may contain 4-19% calcite and anhydrite. Mixtures of crustal salts could melt at temperatures a few tens to a few hundred Kelvins higher than Venus' surface temperature; hence, melting may be induced by modest endogenetic or impact heating. Salts may have many of the same geologic roles on Venus as water and ice have on Mars. A molten salt (carbonatite) 'aquifer' may exist beneath a few hundred meters to several kilometers of solidified salt-rich 'permafrost.' Many geologic features can be explained by carbonatite magmatism: (1) impact melting of crustal salts can explain crater outflows, (2) small, sustained eruptions from molten salt aquifers can explain sapping valleys, (3) large, sustained eruptions may explain canali and their flood plans, and (4) catastrophic outbursts amy have formed outflow channels and chaotic terrain. Landforms created by carbonate-rich lavas would be thermally stable on Venus' surface, though some minerals may weather to other solid substances.

Kargel, Jeffrey S.↗

Evidence for a Noachian-Aged Ephemeral Lake in Gusev Crater, Mars

Gusev crater was selected as the landing site for the Spirit rover because of the likelihood that it contained an ancient lake. Although outcrops rich in Mg-Fe carbonate dubbed Comanche were discovered in the Noachian-aged Columbia Hills, they were inferred to result from volcanic hydrothermal activity. Spirit encountered other mineral and chemical indicators of aqueous activity, but none was recognized as definitive evidence for a former lake in part because none was associated with obvious lacustrine sedimentary deposits. However, water discharge into Martian crater basins like Gusev may have been episodic, producing only small amounts of sediment and shallow ephemeral lakes. Evaporative precipitation from such water bodies has been suggested as a way of producing the Mg- and Fe-rich carbonates found in ALH84001 and carbonates and salts in some nakhlites a hypothesis we examine for the Comanche carbonate.

Ruff, S. W.↗

Manuscript model outputs, model source code, and figure scripts: The role of geomorphology in mediating biomass allocation impacts on salt-marsh resilience and carbon accumulation

This data package provides model source code (C++), model outputs, and figure generation scripts (R) needed to reproduce the following manuscript: Bruns, Nicholas E., Genevieve L. Noyce, and Matthew L. Kirwan. "The Role of Geomorphology in Mediating Biomass Allocation Impacts on Salt-Marsh Resilience and Carbon Accumulation." Estuarine, Coastal and Shelf Science 327 (December 2025): 109549. https://doi.org/10.1016/j.ecss.2025.109549. This manuscript investigates how geomorphology mediates the impact of biomass allocation shifts on salt marsh persistence and carbon (C) sequestration under sea level rise. We use a 1-D soil-column model (Kirwan and Mudd 2012) to perform experiments across a range of static root:shoot ratios (RSR = 1-4) spanning observed values. The model explicitly simulates interactions between tidal inundation, productivity, inorganic sediment deposition, and organic matter accumulation. Experiments determine whether geomorphic feedbacks amplify, dampen, or leave unchanged the ecosystem response to biomass allocation shifts. A first experiment uses constant sea level rise (2.5 mm/yr) to examine equilibrium dynamics and their influence on carbon accumulation rates across different suspended sediment concentrations (SSC). A second set of experiments calculates threshold sea level rise rates for marsh drowning across RSR and SSC combinations. Final experiments apply accelerating sea level rise scenarios (2000-2200) derived from NOAA projections (Sweet et al. 2022) to generate an envelope of expected responses, quantifying the importance of biomass allocation shifts on marsh carbon accumulation and persistence. All experiments are repeated across SSC ranging from 5-50 mg/L to investigate how these interactions vary in micro-tidal marshes with different sediment supplies. Package contents: * README.txt with detailed description of package contents and instructions for reproducing manuscript figures and model outputs * R scripts for generating all manuscript figures * C++ baseline model code from Kirwan and Mudd (2012) * C++ source code for 4 experimental model variants used in the manuscript, extending above baseline code * Model input files (.csv, .txt) including sea level rise scenarios * Model output files (.txt) used in manuscript analyses Temporal coverage: Model simulations span years 1900-2200, with accelerating sea level rise scenarios for 2000-2200. Key variables: Root:shoot ratio, suspended sediment concentration, carbon accumulation rate, vertical accretion rate, marsh elevation, inundation depth, threshold sea level rise rate.

54 ENVIRONMENTAL SCIENCES↗

Quantifying Species Populations in Multivalent Borohydride Electrolytes

Multivalent batteries represent an important beyond Li-ion energy storage concept. The prospect of calcium batteries, in particular, has emerged recently due to novel electrolyte demonstrations, especially that of a ground-breaking combination of the borohydride salt Ca(BH 4 ) 2 dissolved in tetrahydrofuran. Recent analysis of magnesium and calcium versions of this electrolyte led to the identification of divergent speciation pathways for Mg 2+ and Ca 2+ despite identical anions and solvents, owing to differences in cation size and attendant flexibility of coordination. To test these proposed speciation equilibria and develop a more quantitative understanding thereof, we have applied pulsed-field-gradient nuclear magnetic resonance and dielectric relaxation spectroscopy to study these electrolytes. Additionally, concentration-dependent variation in anion diffusivities and solution dipole relaxations, interpreted with the aid of molecular dynamics simulations, confirms these divergent Mg 2+ and Ca 2+ speciation pathways. These results provide a more quantitative description of the electroactive species populations. We find that these species are present in relatively small quantities, even in the highly active Ca(BH 4 ) 2 /tetrahydrofuran electrolyte. This finding helps interpret previous characterizations of metal deposition efficiency and morphology control and thus provides important fundamental insight into the dynamic properties of multivalent electrolytes for next-generation batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Materials SIG quantification and characterization of surface contaminants

When LDEF entered orbit its cleanliness was approximately a MIL-STD-1246B Level 2000C. Its burden of contaminants included particles from every part of its history including a relatively small contribution from the shuttle bay itself. Although this satellite was far from what is normally considered clean in the aerospace industry, contaminating events in orbit and from processing after recovery were easily detected. The molecular contaminants carried into orbit were dwarfed by the heavy deposition of UV polymerized films from outgassing urethane paints and silicone based materials. Impacts by relatively small objects in orbit could create particulate contaminants that easily dominated the particle counts within a centimeter of the impact site. During the recovery activities LDEF was 'sprayed' with a liquid high in organics and water soluble salts. With reentry turbulence, vibration, and gravitational loading particulate contaminants were redistributed about LDEF and the shuttle bay.

Crutcher, E. Russ↗