Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Bulk Stabilization”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 181 records · Page 10

Thermodynamic constraints on the textural evolution of eucrite, EET 90020

Basaltic eucrites, which are possibly parts of the Vestan crust, formed as either lava flows or intrusions, and can offer insights into early crust formation. However most eucrites have experienced thermal metamorphism, which exacerbates the challenges of understanding these samples. A variety of petrogenetic models such as, partial melting of a primitive source, fractional crystallization of magmas emplaced in a primitive crust, and/or partial melting of a eucritic source coupled with melt mixing and assimilation have been proposed in order to explain observed petrologic and chemical characteristics of eucrites. EET 90020 is an unbrecciated eucrite that has experienced significant thermal metamorphism, with temperatures of metamorphic equilibration calculated to be ~840-1040°C. Its petrologic history remains contentious, in part due to differences in trace element analyses [10,17, this work], which has led to multiple metamorphic interpretations [8,10-11]. Here, we combined petrologic observations, chemical analyses, and thermodynamic modeling, to interpret micro-domain textures identified in EET 90020 and better constrain its petrologic history. Ultimately, the development of such textures is a direct result of the geologic processes operating on a young Vesta or similar asteroid. Sample description: We identified three textural domains in EET 90020 (Figure 1); (I) A coarse grain domain with granoblastic plagioclase and pyroxene, (II) a medium grain domain with curved grain boundaries between plagioclase and pyroxene, and (III) a fine grain domain dominated by tridymite that fills in interstitial space between spherical plagioclase. Major element chemistry in phases is consistent across domains. Pyroxene have distinctive high Ca lamellae (Wo40.92En28.1Fs31.0) forming from the low-Ca pigeonite host (Wo3.5En33.7Fs62.8). There are small amounts of fayalitic olivine along pyroxene/oxide grain boundaries, where pyroxenes have reacted with ilmenite/chromite clasts. Plagioclase is anorthitic (Avg ~An88), with little variation (An86-92.5). Trace element bulk rock analyses were collected via ICP-MS and individual mineral analyses with LA-ICP-MS (Figure 2). The bulk sample has an observable enrichment in light rare earth elements, with a notable depletion in Eu. Plagioclase is enriched in LREEs, depleted in HREEs, and has a positive Eu anomaly while pyroxene is enriched in HREEs with a negative Eu anomaly. Variations in trace element analyses is likely influenced by the presence of phosphates because are highly enriched in REEs and have a dramatic effect on the bulk domain compositions. Thermodynamic modeling: The software package, Perple_X, was used to calculate mineral phase equilibria over a range of conditions using a Gibbs free energy minimization approach [12]. Models used all major/minor elements except P2O5. Thermodynamic properties from [13] were used to constrain endmember phase stabilities. Activity models were used to describe mixing in phases with solid solution. Isochemical P-T phase diagrams were constructed for the bulk thin section, and the coarse, medium and fine grain domain compositions. Domain compositions were determined using microprobe analyses of phases identified in each domain and observed modal mineral abundancies. Thermodynamically stable pyroxene compositions were extracted from model results and compared to pyroxene compositions collected via EMPA, allowing us to calculate temperatures for metamorphic equilibrium. Results: Results that use the coarse domain composition (Fig. 3a) demonstrate overlap at T ~ 1020°C indicating high T equilibration. There was no overlap for the medium and fine grain domains, or the bulk composition (e.g., Fig. 3b) indicating that these are not equilibrium assemblages. These results were replicated using data from [8,20]. Discussion: The disequilibrium results from the bulk rock, fine grain and medium grain models imply that EET 90020 was modified during and/or after peak metamorphism (open system behavior). However, this is in contrast to the coarse domain where it appears as if equilibrium was maintained. We suggest that this conflict is explained by highly localized equilibrium occurring at millimeter length-scales, which has been observed in terrestrial metamorphism where aqueous fluid infiltrate [14] or melt loss occurs [15]. It is unlikely that aqueous alteration was significant in modifying the bulk composition of EET 90020, because it lacks hydrated minerals. However, the presence of melt is supported by the presence of an abundance of curved grain boundaries and spherical grains in the medium and fine grain domains This contrasts the coarse domain, where grain boundaries are angular. Given the evidence for disequilibrium in the medium and fine grain domains, it would be inappropriate to draw additional conclusions about textural evolution using thermodynamic models of those domains. However, modeling results of the coarse grain domain, where equilibrium was maintained, can provide useful insights into the geologic evolution of EET 90020. We approximate maximum metamorphic temperatures, using the Ca component in pyroxene, at ~1020°C (Fig. 4), which is consistent with previous two-pyroxene thermometry [11]. At this temperature, up to 10 vol % melt can be produced in the coarse grain domain, which is at the boundary of minimum melt needed in order to segregate and form a melt network [16]. Tridymite and plagioclase would be the first minerals to melt out during heating starting ~990°C. This is consistent with the observed melt textures formed by tridymite and plagioclase in the fine grain domain. We suggest that a partial melting model best explains the textural development of EET 90020. Upon heating, melt generated was either trapped, resulting in no net change in the localized rock composition, or migrated, resulting in disequilibrium between pyroxene and the surrounding matrix. A positive Eu anomaly in plagioclase indicates that all of the plagioclase was melted previously. This is consistent with previous studies that have suggested that EET 90020 represents a residual eucrite that experienced partial melting and subsequent melt loss [8]. We speculate that partial melting could have occurred when EET 90020 was heated in the asteroid’s lower crust or adjacent to an intrusion [7]. Future work will study other, texturally heterogeneous samples to see if EET 90020 presents a unique circumstance or whether crustal partial melting was ubiquitous on the eucrite asteroid.

Eucrites↗

Engineering of a Coupled Nanocomposite as a High-Performance Protonic Ceramic Fuel Cell Cathode

The lack of high-performance cathode catalysts is a salient issue that bedeviled the commercialization of protonic ceramic fuel cells (PCFCs). Here, in this work, we report a remarkable electrocatalytic activity and stability enhancement of cathode electrodes by engineering a coupled nanocomposite. The as-prepared Pr 0.3 (Ba 0.5 Sr 0.5 ) 0.7 Co 0.8 Fe 0.2 O 3−δ nanocomposite possesses a bulk cubic phase on which homogeneous and intimate orthorhombic PrCo 0.5 Fe 0.5 O 3−δ nanoparticles are uniformly decorated. X-ray diffraction and Raman spectroscopy reveal the excellent thermal stability of the nanocomposite. It achieves a high peak power density of 1.02 W cm –2 based on protonic electrolytes at 600 °C. No noticeable structural degradation is observed over ∼210 h at 550 °C according to scanning electron microscopy analysis. This work demonstrates an effective strategy to boost the performance of perovskite oxides for PCFCs via nanocomposite engineering. It may apply to other catalyst designs and discoveries, such as for batteries, electrolyzers, and membrane reactors.

08 - HYDROGEN↗

While legume-based rotation influences the chemical composition of mineral-associated organic matter, tillage has little effect on its persistence

Legume-based rotations are key to enhancing soil carbon (C) storage in stable forms such as mineral-associated organic matter (MAOM), improving soil health, and helping maintain long-term C stock. This study investigates how plant inputs and tillage practices influence the distribution, composition, and persistence of MAOM in wheat cropping systems when legumes are incorporated into the rotation. Soil samples were collected from Walla Walla silty loam of northeast Oregon, including conventional tillage (CT) and no-till (NT) treatments in a long-term dryland winter wheat (Triticum aestivum L.) and spring pea (Pisum sativum L.) rotation experiment, with an adjacent grass pasture (GP) plot serving as the baseline. Bulk soil, particulate organic matter (POM), and MAOM fractions were scanned using mid-infrared (Mid-IR) spectroscopy and analyzed for total C and nitrogen (N) as well as radiocarbon age, aggregate stability, and mineralizable C. In WP systems, NT promoted greater C accumulation and stabilization in MAOM than CT, reaching levels similar to those under native GP conditions. Furthermore, our findings indicate that decades of continuous legume-based rotation were insufficient to restore total bulk C content to levels observed in the undisturbed reference site (GP) in the 0–30 cm layer, with increases limited to the surface layer. The Mid-IR data provided insights into how cultivation may alter the chemical composition of MAOM. An increase in amide bands was observed in GP, while legume-based rotation systems favored an abundance of aliphatic (C-H) components in the MAOM fraction. In cultivated soils, C in MAOM exhibited longer residence times under arable conditions than in grassland, while POM remained an actively cycled pool across all treatments. Despite variations in the chemical composition of MAOM across treatments, mineralizable C emissions from MAOM fractions remained statistically unchanged during the 96-hour incubation period. Our findings suggest that soil physical protection, enhanced by reduced tillage, is the primary factor influencing MAOM cycling.

Carbon stabilization↗

Nonlinear Response of Layer Growth Dynamics in the Mixed Kinetics-Bulk-Transport Regime

In situ high-resolution interferometry on horizontal facets of the protein lysozyme reveal that the local growth rate R, vicinal slope p, and tangential (step) velocity v fluctuate by up to 80% of their average values. The time scale of these fluctuations, which occur under steady bulk transport conditions through the formation and decay of step bunches (macrosteps), is of the order of 10 min. The fluctuation amplitude of R increases with growth rate (supersaturation) and crystal size, while the amplitude of the v and p fluctuations changes relatively little. Based on a stability analysis for equidistant step trains in the mixed transport-interface-kinetics regime, we argue that the fluctuations originate from the coupling of bulk transport with nonlinear interface kinetics. Furthermore, step bunches moving across the interface in the direction of or opposite to the buoyancy-driven convective flow increase or decrease in height, respectively. This is in agreement with analytical treatments of the interaction of moving steps with solution flow. Major excursions in growth rate are associated with the formation of lattice defects (striations). We show that, in general, the system-dependent kinetic Peclet number, Pe(sub k) , i.e., the relative weight of bulk transport and interface kinetics in the control of the growth process, governs the step bunching dynamics. Since Pe(sub k) can be modified by either forced solution flow or suppression of buoyancy-driven convection under reduced gravity, this model provides a rationale for the choice of specific transport conditions to minimize the formation of compositional inhomogeneities under steady bulk nutrient crystallization conditions.

Vekilov, Peter G.↗

Stable Metal–Organic Electrocatalysts for Anion-Exchange Membrane Water Electrolyzers by Defect Engineering

Developing efficient and durable catalysts for the alkaline oxygen evolution reaction (OER) is vital to achieving practical anion-exchange membrane water electrolyzers (AEMWE) for green hydrogen production. In this work, we break the activity-stability trade-off of electrocatalysis by defect engineering of Ni-based metal-organic electrocatalysts (Ni-benzene dicarboxylate; Ni-BDC) through coordinating ferrocenecarboxylates (Fc) to the metal sites. Experimental results collectively reveal that the defect MOF (Ni-BDC:Fc_5:1) exhibits a high OER turnover frequency of 0.75 O 2 s -1 at 300 mV overpotential. Operando Raman spectroscopy and isotope-labelling electrochemical mass spectrometry measurements indicate the structure of Ni-BDC:Fc_5:1 is also more stable in service than that of pure Ni-BDC. The high activity and stability could be attributed to the moderate defects (i.e., unsaturated Ni sites) in the structure that not only increase the intrinsic activity and stability of the local active environment by inhibiting lattice oxygen exchange, but also electrochemically activates the bulk of the catalysts by creating a porous network that facilitates internal H 2 O/OH - conduction with enhanced electronic conduction. Accordingly, an AEMWE employing Ni-BDC:Fc_5:1 as the OER catalyst delivers an industrial-level current density of 1 A cm -2 at 1.73 V cell and can be steadily operated for more than 120 hours.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Manufacturing in space.

Space, in contrast to earth, offers total gravity control and unequaled vacuum, temperature, pressure, and radiation characteristics. In zero-g molecular forces such as cohesion and adhesion become controlling factors even in the largest bulk processes. The absence of relative mass accelerations eliminates the need for support of solid matter. Stability in liquid-solid, liquid-liquid, or liquid-gas mixtures, and the absence of thermal convection is obtained because there is no relative motion in fluids due to differences in density. Applications of these characteristics include liquid-matrix preparation of composites, fine-grain castings, supersaturated alloys, combinations which exhibit liquid-phase immiscibility, the containerless free suspension of materials, surface-tension casting, surface-tension drawing, adhesion casting, and controlled density casting.

Wuenscher, H. F.↗

Estimation of the average exchanges in momentum and latent heat between the atmosphere and the oceans with Seasat observations

Ocean-surface momentum flux and latent heat flux are determined from Seasat-A data from 1978 and compared with ship observations. Momentum flux was measured using the Seasat-A scatterometer system (SASS) heat flux, with the scanning multichannel MW radiometer (SMMR). Ship measurements were quality selected and averaged to increase their reliability. The fluxes were computed using a bulk parameterization technique. It is found that although SASS effectively measures momentum flux, variations in atmospheric stability and sea-surface temperature cause deviations which are not accounted for by the present data-processing algorithm. The SMMR-latent-heat-flux algorithm, while needing refinement, is shown to given estimations to within 35 W/sq m in its present form, which removes systematic error and uses an empirically determined transfer coefficient.

Liu, W. T.↗

Analysis of ProSEDS Test of Bare-Tether Collection

NASA's tether experiment ProSEDS will be placed in orbit on board a Delta-II rocket to test bare-tether electron collection, deorbiting of the rocket second stage, and the system dynamic stability. ProSEDS performance will vary because ambient conditions change along the orbit and tether-circuit bulk elements at the cathodic end follow the step-by-step sequence for the current cycles of operating modes (open-circuit, shunt and resistor modes for primary cycles; shunt and battery modes for secondary cycles). In this work we discuss expected ProSEDS values of the ratio L,/L*, which jointly with cathodic bulk elements determines bias and current tether profiles; L, is tether length, and L* (changing with tether temperature and ionospheric plasma density and magnetic field) is a characteristic length gauging ohmic versus baretether collection impedances. We discuss how to test bare-tether electron collection during primary cycles, using probe measurements of plasma density, measurements of cathodic current in resistor and shunt modes, and an estimate of tether temperature based on ProSEDS orbital position at the particular cycle concerned. We discuss how a temperature misestimate might occasionally affect the test of bare-tether collection, and how introducing the battery mode in some primary cycles, for an additional current measurement, could obviate the need of a temperature estimate. We also show how to test bare-tether collection by estimating orbit-decay rate from measurements of cathodic current for the shunt and battery modes of secondary cycles.

Sanmartin, J. R.↗

Thermodynamic and Diffusion Model Estimates on Metamorphic Temperatures and Timescales for Basaltic Eucrite GRA 98098

Introduction: HED meteorites are thought to rep-resent igneous rocks from Vesta’s basaltic crust and preserve evidence of early crustal metamorphism. Determining the temperatures and timescales of thermal metamorphism is important for reconstructing crustal evolution in the early solar system. Here, we study basaltic eucrite Graves Nunataks (GRA) 98098, which has been identified as a highly metamorphosed eucrite [1]. We present new estimates on metamorphic temperatures determined via thermodynamic modeling as well as the initial results from diffusion models constraining timescales of thermal metamorphism. Sample Description: GRA 98098 is an unbrecciated eucrite with a granoblastic plagioclase and pyroxene mineralogy. Millimeter to cm-long lathes of tridymite cross-cut and poikilitically enclose plagioclase and pyroxene [1,this work]. Pyroxene grains have exsolved into Ca-rich (~Wo38En29Fs33) and Ca-poor (~Wo4.5En36Fs59.5) lamellae. Both unzoned and zoned plagioclase grains are observed. Unzoned plagioclase grains are found solely with tridymite laths. These grains have ~An92 compositions. The cores of the zoned plagioclase grains have the same composition and thin, relatively sodic rims (~An67), (Fig. 1). The bulk sample is unusually enriched in highly in-compatible elements and has one of the most fractionated REE patterns reported [1]. Maximum metamorphic temperatures of 985±78°C have been estimated using two-pyroxene thermometry [2]. Methods: Thermodynamic modeling. Thermodynamic models were constructed using the software Perple_X, which employs a Gibbs free energy minimization in order to determine the most stable phase assemblage for a given bulk rock composition [3]. Bulk composition was calculated using mineral com-positions acquired via EMPA (this study) and the observed abundancies present in the thin section. Two bulk compositions were estimated; 1) includes all phases present in the thin section, (assumes that all phases are present during metamorphism), 2) excludes tridymite from the bulk calculation (assumes that tridymite was not present during metamorphism). In order to determine whether metamorphic equilibria was achieved and estimate temperatures of metamorphism, we compared measured pyroxene compositions with thermodynamically predicted compositions [4, Fig. 2]. Diffusion Modeling. Several time-temperature de-pendent diffusion profiles were calculated in order to determine the best match for XAn chemical profiles observed at the edges of the zoned plagioclase (Fig. 3). We assumed that the start condition was a stepwise gradient at the plagioclase/pyroxene interface. We also assumed an average diffusion coefficient (D) and a constant temperature using the equation in [5]. D was determined for two temperatures (T = 1060ºC; near eucrite solidus [6] and T = 985ºC; metamorphism reported in [4]) and then XAn was calculated as a function of distance from plagioclase core to rim using an error function solution to Fick’s second law. Results: Thermodynamic model results are summarized in Fig. 2. For a bulk composition that includes all phases in the thin section, pyroxene endmember compositions plot in the following temperature ranges: Fs ~660-860ºC, En~1000ºC & 1150ºC, and Wo~760-900ºC (Fig. 2a). For a bulk composition that excludes tridymite from the peak metamorphic assemblage (i.e., the bulk composition minus the contribution from tridymite), a temperature range could not be determined for the Fs component of pyroxene. For Wo, T~760-900ºC and En, T~1000ºC & 1150ºC (Fig. 2b). Fig. 3 summarizes the diffusion model results. For T = 1060°C & 985°C, the most appropriate time interval was estimated based on which diffusion curve most matched (solid lines, Fig. 3) the EMPA data. For T = 1060°C, the best looking match was t = 500 ka. For T = 985°C, the best match was t = 7 Ma. Discussion and future work: Temperature estimates from thermodynamic models are not conclusive because the temperature ranges determined for pyroxene endmember stability do not overlap (colored fields in Fig. 2), thus implying that there is disequilibrium between pyroxene crystals and the bulk composition considered [4]. Thus, additional exploration is needed to define a metamorphically equilibrated do-main that accurately records peak temperature. The utility of defining metamorphically equilibrated do-mains to improve the accuracy and level of detail elucidated regarding the petrogenetic history of metamorphose samples has been demonstrated previously [4,7]. We suggest that in the case of Fig. 2a, the thin section composition is not representative of the length scales over which metamorphic equilibrium was achieve and in the case of Fig. 2b, the assumption that tridymite was not present during metamorphism was incorrect. However, results from thermodynamic models can provide insight into the relative timing of mineral and compositional textures. For example from texture alone, it is unclear whether tridymite was igneous in origin and represents the last bits of melt in a crystallizing magma chamber, or if it formed during (and possibly initiated) open system thermal metamorphism. The latter could be consistent with a partial melt hypothesis [8,9] while the former implies that simple fractional crystallization can yield the textures present in GRA 98098. The lack of coincidence be-tween pyroxene endmember compositions in Fig. 2b suggest that the bulk composition minus tridymite was not the assemblage in equilibrium with the pyroxene, suggesting that tridymite was present during metamorphism and formed during igneous crystallization. We conclude that the development of the Na-rich plagioclase rims likely occurred during or immediately after peak thermal metamorphism, because eucrites of similar metamorphic grade and texture have unzoned plagioclase (~An92) [2,4,8], and Na zoning is only observed in the plagioclase not included in the tridymite. This suggests that the zoning formed after tridymite formation, and therefore after igneous crystallization. Thus, the timescales calculated via diffusion modeling possibly represent the time interval over which thermal metamorphism occurred. Cooling rates approximated for the Vestan crust predict that the crust cooled below 300°C around 35-40 Ma after formation[10]. This is consistent with our modeling results that predict formation of the Na rich plagioclase rims occurring at higher temperatures over a period of 0.5 to 7 Ma years. Future work. Additional thermodynamic modeling work will focus on selecting an equilibrated bulk rock domain in which to elucidate metamorphic conditions. Diffusion models currently provide a minimum time-scale, since diffusion slows down as the system cools. Future work with will focus on integrating cooling into the diffusion models and constraining the depth at which thermal metamorphism occurs because it could be used to determine whether the range of time-scales calculated for thermal metamorphism are consistent with the geologic environment.

J S Gorce↗

Phenoxy Resins Containing Pendent Ethynyl Groups

Ethynyl-containing phenoxy resins have excellent shelf life in solution or in bulk. Cured ethynyl-containing phenoxy resins offer lower moisture absorption, higher use temperatures, and better thermal stability over stateof-the-art cross-linked phenoxy resins. Depending upon cross-link density, cured ethynyl-modified phenoxy resins are solvent resistant but still thermoformable and relatively tough. Modified resins show potential for use as adhesives, composite matrices, solvent-resistant coatings, membranes, insulators, and films.

Hergenrother, P. M.↗

The stability of a sample in a diamond anvil cell

A theoretical analysis of the stability of a gasketed sample in a diamond anvil cell is reported, demonstrating that the stability of the sample depends principally on the yield strength and the thickness of the gasket, the bulk modulus and the radius of the sample, and the geometry of the culet. The results yield a simple methodology that can be used to obtain stable samples in a diamond anvil cell.

Moss, William C.↗

Simulation studies for surfaces and materials strength

Computer simulation studies were conducted to investigate materials properties. All the calculations were carried out using atomic level simulation techniques which are based on semiempirical or model functions. During this project, functions with varying degrees of complexity were derived and employed in simulations. Investigations include covalently bonded materials as well as systems involving metal atoms. For small clusters calculated results provided information on various energy- and structure-related properties along with vibrational characteristics. Also, energy barriers for configurational transitions were calculated for selected cases. Simulation calculations for surfaces produced new results in areas related to surface energies, reconstructions and relaxations, surface defects, surface stresses as well as adsorption and nucleation processes. Simulations were also performed on bulk materials. Calculated results provided an atomic level understanding on energetics and structures of point defects, crystal stability, elastic properties, and materials strength for various systems. Calculations involving polymeric materials include studies of polar polymer melts and polymer/solid interfaces. Simulations employing specially developed codes provided significant information about energetics and conformational characteristics of different polymeric chains.

Halicioglu, Timur↗

What's on the Surface? Physics and Chemistry of Delta-Doped Surfaces

Outline of presentation: 1. Detector surfaces and the problem of stability 2. Delta-doped detectors 3. Physics of Delta-doped Silicon 4. Chemistry of the Si-SiO2 Interface 5. Physics and Chemistry of Delta-doped Surfaces a. Compensation b. Inversion c. Quantum exclusion. Conclusions: 1. Quantum confinement of electrons and holes dominates the behavior of delta-doped surfaces. 2. Stability of delta-doped detectors: Delta-layer creates an approx 1 eV tunnel barrier between bulk and surface. 3. At high surface charge densities, Tamm-Shockley states form at the surface. 4. Surface passivation by quantum exclusion: Near-surface delta-layer suppresses T-S trapping of minority carriers. 5. The Si-SiO2 interface compensates the surface 6. For delta-layers at intermediate depth, surface inversion layer forms 7. Density of Si-SiO2 interface charge can be extremely high (>10(exp 14)/sq cm)

detectors↗

Effects of 9.5 years warming on SOC concentration and composition in bulk soil and density fractions

Original data of whole-soil warming experiment after 9.5 years at Blodgett Forest Research Station. The Blodgett Forest is a mixed coniferous temperate forest with Mediterranean climate. The annual air temperature is 12.5℃ and the annual precipitation is 1774 mm yr-1- The soil is mesic ultic Alfisol of granitic origin, equivalent to Dystric Cambisol according to The World Reference Base for Soil Resources (WRB) system. The soil is warmed down to 1 m at + 4℃ by vertically installed heating cables. At the time of soil sampling on 1 May 2023, the whole-soil warming experiment had been running for approximately 9.5 years, from January 2014 to May 2023. The dataset includes: - Bulk_EA: C, N content, δ13C, and CN ratio of bulk soil; - Density_fractionation: organic carbon concentration, δ13C, and C/N ratio of free light fraction (fLF), occluded ligh fraction (oLF), and heavy fraction (HF); - PCA_DRIFT_AUC: original data of area under the curve (AUC) values of eight carbon bond types integrated on diffuse reflectance infrared fourier transform spectroscopy for each soil sample and soil fraction, which are consequently used for principal component analysis (PCA); - DRIFTS_stability_index: the calculation of aliphatic C–H (3000–2800 cm-1) to aromatic C=C (1670–1600 cm-1) ratios for each bulk soil sample and soil fraction. All data are provided in CSV format and can be viewed using Microsoft Excel.

Climate change↗

Structural effects of composition tuning in A-site disordered perovskite La0.5Li0.5−xMxTiO3 (M = Na, K) nanorods for fast interfacial transport for solid composite electrolyte design

Polymer-ceramic composite electrolytes (CPE) have emerged as promising replacements for currently used liquid organic electrolytes, which pose as safety hazards, in Li-ion batteries. Limits in conductivity enhancement in CPEs is often attributed to a high resistance for Li-ion transport along the interface due to the incompatibility of the polymer and ceramic phases. A clear understanding of the interfacial structure and how this impacts interfacial Li-ion transport is needed in order to efficiently design a CPE with optimal ionic conductivity. In this study, density functional theory (DFT) calculations, in conjunction with scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS), are used to unveil the bulk and surface structure of La0.5Li0.5−xMxTiO3 (M = Na, K) (LMTO) nanorods, a newly-reported ceramic system with promising applications in CPEs, and the LMTO interactions with the poly(lithium sulfonyl (trifluoromethane sulfonyl)imide methacrylate) (p(MTFSILi)) polymerized ionic liquid. Substitution of lithium for sodium and potassium onto the A-site perovskite lattice is shown to increase the stability of the preferred pseudocubic perovskite phase because of their increased cation size which allows them to reduce the TiO6 octahedral rotations in the bulk and at the surface. STEM and EELS results show that LMTO nanorods with differing compositions have Ti-enriched (110)-oriented surfaces. Increased sodium and potassium compositions in LMTO is also shown using the DFT calculations to weaken the binding of the lithium atom to the MTFSI unit when LiMTFSI is adsorbed to the LMTO surface. This weakening of lithium binding to the polymer at the LMTO interface indicates that the lithium mobility is increased, correlating to an increase in interfacial Li-ion transport. Overall, this work provides insights into how to tune the interfacial interactions between the polymer (p(MTFSI)) and ceramic (LMTO) for optimal CPE design.

Shepard, Lauren B [Pennsylvania State University, ↗

Solvation-guided inhibition of manganese dissolution of lithium- and manganese- rich cathode via cyclic carbonate molecular engineering

Lithium and manganese-rich (LMR) layered oxides represent a leading class of high-energy cathode materials, but their practical realization is fundamentally limited by severe manganese (Mn) dissolution, a process that triggers structural degradation and rapid capacity fade. While mitigation efforts have predominantly focused on interfacial engineering, the intrinsic contribution of bulk electrolyte solvation to this degradation pathway remains largely unexplored, primarily due to the difficulty of deconvolving its effects from concurrent cathode-electrolyte interphase (CEI) formation. Here, we report an experimental design to isolate the role of solvation. We systematically varied the electrolyte solvent solvation power by substituting the strongly coordinating ethylene carbonate (EC) with its weaker coordinating fluorinated derivatives, fluoroethylene carbonate (FEC) and trans-4,5-Difluoro-1,3-dioxolan-2-one (DFEC), while maintaining a consistent interfacial chemistry. Remarkably, the electrolyte formulated with the weakest solvent, DFEC, exhibits superior cycling stability, suppressing Mn dissolution by up to 63% relative to the conventional EC-based system. Post-mortem analysis unequivocally attributes this performance enhancement to the preservation of the LMR cathode's structural integrity, a direct consequence of mitigated Mn dissolution. This work provides conclusive evidence that modulating bulk electrolyte solvation is a potent and direct strategy for stabilizing LMR cathodes, establishing a vital design principle for next-generation battery systems.

25 ENERGY STORAGE↗

Effect of Impurities on the Redox Properties of Goethite

Iron oxide minerals regulate the flux of electrons in the environment and are important hosts for trace and minor, yet critical, elements. Here, we present the first evidence of a direct link between the local coordination environments of Ni and Zn and the redox properties of their host phase goethite (α-FeOOH), the most abundant Fe(III) (oxyhydr)oxide at Earth’s surface. Here, we used aqueous redox measurements to show that the redox potential E H 0 , and hence the mineral’s stability, follows the order: pure goethite ≥ Zn-goethite > Ni-goethite. Parallel X-ray absorption and scattering measurements demonstrate, using quantum-informed analysis, that the local coordination environment of the smaller impurity, Ni, causes more bulk strain energy than Zn, which nearly accounts for the difference in E H 0 between Ni- and Zn-goethite. Our theory-informed, experimental study reveals how two common impurities affect the stability of goethite with implications for the biogeochemical reactivity of Fe(III) (oxyhydr)oxide in mediating elemental and electron fluxes in the environment.

42 ENGINEERING↗