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

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At least 181 records · Page 10

BioID/LID System Cartridge Testing Report

LLNL produced two lots of lyophilized LAMP assay containing cartridges, LNL022818 and LNL071818, for testing on Gen3 BioID systems. Thirty-nine cartridges were tested for lot LNL022818. All thirty-nine cartridges performed as expected regarding correct positive control (IPC) and negative control (NTC) reactions. Five different templates were tested on these 39 cartridges. The BioID system detected 79.1% true positives and 9.3% false positives along with 98.9% true negatives and 2.9% false negatives for cartridge lot LNL022818. Thirty cartridges were tested for lot LNL071818. It was noted early that due to a manufacturing issue with the cartridges related to incomplete sonic welding of the cartridge, a large fraction of lot LNL071818 cartridges leaked. Insufficient funds were available to replace this lot of cartridges. Twenty three of 30 cartridges performed as expected regarding correct positive control (IPC) and negative control (NTC) reactions. Four different templates were tested on these 30 cartridges. The BioID system detected 77% true positives and 23% false positives along with 96.9% true negatives and 3.1% false negatives for cartridge lot LNL071818. For all tested cartridges using DNA template, DNA was added at a final concentration of 25 pg/ul. All reactions contained positive control DNA at 2.5 pg/ul.

42 ENGINEERING↗

The Implications of Reduced Ground Reaction Forces During Space Flight for Bone Strains

The specific mechanisms regulating bone mass are not known, but most investigators agree that bone maintenance is largely dependent upon mechanical demand and the resultant local bone strains. During space flight, bone loss such as that reported by LeBlanc et al. may result from failure to effectively load the skeleton and generate sufficient localized bone strains. In microgravity, a gravity replacement system can be used to tether an exercising subject to a treadmill. It follows that the ability to prevent bone loss is critically dependent upon the external ground reaction forces (GRFs) and skeletal loads imparted by the tethering system. To our knowledge, the loads during orbital flight have been measured only once (on STS 81). Based on these data and data from ground based experiments, it appears likely that interventions designed to prevent bone loss in micro-gravity generate GRFs substantially less than body weight. It is unknown to what degree reductions in external GRFs will affect internal bone strain and thus the bone maintenance response. To better predict the efficacy of treadmill exercise in micro-gravity we used a unique cadaver model to measure localized bone strains under conditions representative of those that might be produced by a gravity replacement system in space.

Peterman, Marc M.↗

Calcic micas in the Allende meteorite - Evidence for hydration reactions in the early solar nebula

Two calcic micas, clintonite and margarite, have been identified in alteration products in a calcium- and aluminum-rich inclusion (CAI) in the Allende meteorite. Clintonite replaces grossular in alteration veins, and margarite occurs as lamellae in anorthite. Their occurrence suggests that, in addition to undergoing high-temperature alteration by a volatile and iron-rich vapor that produced the grossular and anorthite, some CAIs underwent alteration at moderate temperatures (400 K or less). Petrographic evidence suggests that the calcic micas formed before accretion but after the formation of the layered rim sequences that surround the CAI. These calcic micas provide strong evidence that, contrary to theoretical calculations, some hydration reactions occurred in the early solar nebula.

Keller, Lindsay P.↗

On the cause of the flat-spot phenomenon observed in silicon solar cells at low temperatures and low intensities

A model that explains the flat-spot power loss phenomenon is presented. Evidence suggests that the effect is due to localized metallurgical interactions between the silicon substrate and the contact metallization. These reactions are shown to result in localized regions in which the P-N junction is destroyed and replaced with a metal semiconductor-like interface. The effects of thermal treatment, crystallographic orientation, junction depth, and metallization are shown along with a method of preventing the effect through the suppression of vacancy formation at the free surface of the contact metallization. Data indicating the effectiveness of a TiN diffusion barrier in preventing the effect are also given.

Weizer, V. G.↗

Real-time SEM studies in controlled reactive atmospheres

A unique scanning electron accessory has been developed that allows the observation of specimens under partial pressures of any gas. The sample is placed in a metal support boat inside a special sample holder. The sample in the boat is imaged on a CRT and is simultaneously recorded on a videotape, allowing the reaction between the sample and the gas to be observed in real time. Sample changes can be seen continuously as the sample is being heated or cooled. This process allows the observation of material transformations such as phase changes as they happen. Temperatures as high as 1000 C have been used and are continuously monitored using a thermocouple with a digital display on the CRT and videotape. X-ray analyses can also be run before and after any reactions. In the study described here, thick-film screen-printing inks using molybdenum/tin compositions as a replacement for silver were developed to be used on terrestrial photovoltaic cells. Pieces were placed on the sample stage and heated in both O2 and H2 atmospheres. The results were used to determine the most effective frits to be used in the thick-film inks.

Gallagher, B. D.↗

Towards ternary binders involving limestone additions — A review

The review summarises literature to examine the transition from portland limestone cement system to composite ternary binder systems involving limestone. Interest in limestone addition as an ideal component in multicomponent binder systems has surged as evident from the large volume of literature published in the recent past. A ternary blended system, with co-substitution of limestone, has the potential to complement the reaction of the supplementary cementitious materials (SCMs). The direct addition of limestone powder helps to attain higher substitution levels of portland cement clinker, improve early age properties, and supplement SCM's reactivity. However, the dilution of hydrates could hamper the long-term benefits. In this review, the interaction of fine limestone is classified and elaborated under two broad umbrellas: physical and chemical interactions. The physical interactions can manifest in three ways, namely, filler action, shearing action and improved packing, which alters reaction rate and extent at early ages. The chemical interactions also modify the reaction kinetics and phase assemblage due to nucleation of C-S-H on calcite surfaces, preservation of the ettringite phase and formation of carboaluminates. Two different forms of carboaluminate hydrates — hemicarboaluminate and mono-carboaluminate can be present in the hydrate matrix depending on the balance between carbonate ions and aluminates in the pore solution. Several factors such as replacement level, particle size, choice of SCM, its reactivity and reactive aluminates content, sulphate levels, curing temperature, and duration of curing can control the carboaluminate formation, reaction degree of SCMs and chemical interaction from limestone additions. A combination of physical and chemical effects makes fine limestone a potential material for co-substitution with aluminosilicate based SCMs, mainly fly ash, slag, and calcined clay. In this review, the factors affecting limestone-SCM composites are summarised based on a detailed literature survey. The effects of SCM-limestone cement composites on hydration kinetics, reaction chemistry, the reactivity of SCMs, the stability of hydrated phases, and contribution to the physical structure development and macroscopic properties by evaluating hydration and mechanical properties are discussed. The importance of AFm (Al{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}-mono) phases in various deterioration mechanisms in concrete and their influence on performance characteristics in different exposure environment is critically appraised.

36 MATERIALS SCIENCE↗

Mechanistic Insights into Dinitrogen Reduction to Ammonia in Light-Controlled Nanocrystal:Nitrogenase Complexes

Developing systems that can efficiently capture photon energy and convert this energy into fuels and chemicals requires understanding how to assemble molecular components with diverse functions into complete systems possessing selectivity and efficiency in directing charge carriers to catalytic reactions. There are many challenges to achieving this goal. One promising approach is the development of hybrid systems that combine semiconductor nanocrystals (NCs) for light capture and enzymes as efficient catalysts. Such biohybrid systems capitalize on the tunable electronic and optical properties of NCs while leveraging the unmatched specificity and efficiency of enzymes in catalyzing chemical reactions, thereby offering opportunities to surpass the limitations of each component alone. Here, we focus on recent progress in developing a biohybrid system that combines CdS NCs for photon capture with the enzyme nitrogenase to accomplish light-driven dinitrogen (N 2 ) reduction to ammonia (NH 3 ). Integrating light-harvesting materials with biological catalysts requires a deep understanding of NC properties, protein stability, and electron transfer (ET), making it an inherently multidisciplinary problem. The reduction of N 2 to NH 3 is a challenging reaction, with a high demand in both agriculture and industrial chemical production. This reaction is intrinsically energy intensive, due to the need to activate the N≡N triple bond. The current standard industrial approach to N 2 reduction, the Haber−Bosch reaction, obtains the necessary energy input from fossil fuels, whereas biological systems capable of N 2 reduction utilize the hydrolysis of ATP as their energy source. Replacing these costly, energy-intensive inputs with renewable light energy represents a critical step toward sustainable NH 3 production. Recent progress has demonstrated that semiconductor CdS NCs can be coupled to the catalytic component of nitrogenase, the MoFe protein, to form a biohybrid CdS NC:MoFe protein complex, enabling light-driven N 2 reduction rather than energy input from fossil fuels or ATP. This illustrates how inorganic NCs can functionally replace the natural Fe protein partner, yielding a biohybrid catalyst that enables controlled electron delivery and provides not only light-driven NH 3 production but also new approaches for probing enzyme catalytic function. The CdS NC:MoFe protein biohybrid system enables light-initiated electron delivery at ambient temperature, as well as temperatures below freezing, allowing for stabilization and spectroscopic characterization of key reaction intermediates. These findings highlight how photochemical biohybrids can serve as both functional catalysts and mechanistic probes. Beyond studies of the nitrogenase mechanism, studies of the CdS NC:MoFe system reveal how variables such as NC size, electrostatic binding interactions, and sacrificial electron donors (SEDs) govern complex stability, charge transfer efficiency, and catalytic performance. In addition, studies of nitrogenase and the high activation barrier for N 2 reduction are enabling investigations of new and interesting questions regarding the properties and limitations of NC biocatalysis. In this Account, we describe the key features of CdS NC:MoFe protein biohybrids and the parameters for optimal light-driven N 2 reduction, and how controlling ET with light illuminates the path to new insights into the nitrogenase mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Olefin methylation over iron zeolites and the methanol to hydrocarbons reaction

The effect of olefin addition to a stream of dimethyl ether on the methanol homologation reaction is investigated using iron-substituted zeolites Fe-beta and Fe-ZSM-5. The reaction was investigated using plug-flow microreactors in the temperature range of 240–400 °C, at a total pressure of 0.239 MPa and a WHSV of 6.12 (g DME/ gcat -hr). For Fe-beta (Si/Fe= 9.2) catalysts, isobutene co-feeding almost doubles dimethyl ether (DME) consumption rate and shifts selectivity towards larger olefins with carbon numbers from 5 to 7. Addition of isobutene above 6.3%, however, resulted in a reduction of DME consumption rates, an effect assigned to the replacement of surface methoxy groups for adsorbed olefins in the zeolite pores. Below a temperature of 340 °C hydride-transfer rates are negligible; reaction rates are stable for over 5.5 h and the products consist almost exclusively of olefins and a small amount of methane. Above 360 °C the onset of catalytic hydride transfer processes is observed leading to fast catalyst deactivation rates and an increase in the concentration of aromatic species. Iron ZSM-5 (Si/Fe = 21.4) catalysts under similar reaction conditions consumes methanol faster than Fe-beta at approximately three times the TOF (on a per iron basis). The Fe-ZSM-5 catalyst was selective to a distribution of products (C5 to C8) as compared to Fe-beta which was selective to primarily C5 and C7. Co-feeding larger olefins (2-methyl-2-butene, 2,3-dimethyl-2-butene, 2,3,3-trimethyl-1-butene, and 2,4,4-trimethyl-2-pentene) at a 3.9% olefin concentration over Fe-beta changed selectivity towards cracking products (C4 compounds such as isobutene). As the size of the olefin increases, a reduction of DME consumption rate is also observed. Here these results show that co-feeding olefins with DME over Fe-zeolites is a promising route to increase methylation rates at relatively low temperatures producing larger branched olefins and that the product distribution is highly dependent on the zeolite pore size and structure of the olefin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Solution-Processable High-Modulus Crystalline Artificial Solid Electrolyte Interphase for Practical Lithium Metal Batteries

The solid electrolyte interphase (SEI) has been identified as a key challenge for Li metal anodes. The brittle and inhomogeneous native SEI generated by parasitic reactions between Li and liquid electrolytes can devastate battery performance; therefore, artificial SEIs (ASEIs) have been proposed as an effective strategy to replace native SEIs. Herein, as a collaboration between academia and industrial R&D teams, a multifunctional (crystalline, high modulus, and robust, Li + ion conductive, electrolyte-blocking, and solution processable) ASEI material, LiAl-FBD (where “FBD” refers to 2,2,3,3-tetra-fluoro-1,4-butanediol), for improving Li metal battery performance is designed and synthesized. The LiAl-FBD crystal structure consists of Al 3+ ions bridged by FBD 2– ligands to form anion clusters while Li + ions are loosely bound at the periphery, enabling an Li + ion conductivity of 9.4 × 10 –6 S cm –1 . Further, the fluorinated, short ligands endow LiAl-FBD with electrolyte phobicity and high modulus. The ASEI is found to prevent side reactions and extend the cycle life of Li metal electrodes. Specifically, pairing LiAl-FBD coated 50 μm thick Li with industrial 3.5 mAh cm –2 NMC811 cathode and 2.8 μL mAh –1 lean elec-trolyte, the Li metal full cells show superior cycle life compared to bare ones, achieving 250 cycles at 1 mA cm –2 .

25 ENERGY STORAGE↗

Significant Roles of Surface Hydrides in Enhancing the Performance of Cu/BaTiO 2.8 H 0.2 Catalyst for CO 2 Hydrogenation to Methanol

Abstract Tuning the anionic site of catalyst supports can impact reaction pathways by creating active sites on the support or influencing metal‐support interactions when using supported metal nanoparticles. This study focuses on CO 2 hydrogenation over supported Cu nanoparticles, revealing a 3‐fold increase in methanol yield when replacing oxygen anions with hydrides in the perovskite support (Cu/BaTiO 2.8 H 0.2 yields ~146 mg/h/gCu vs. Cu/BaTiO 3 yields ~50 mg/h/gCu). The contrast suggests that significant roles are played by the support hydrides in the reaction. Temperature programmed reaction and isotopic labelling studies indicate that BaTiO 2.8 H 0.2 surface hydride species follow a Mars van Krevelen mechanism in CO 2 hydrogenation, promoting methanol production. High‐pressure steady‐state isotopic transient kinetic analysis (SSITKA) studies suggest that Cu/BaTiO 2.8 H 0.2 possesses both a higher density and more active and selective sites for methanol production compared to Cu/BaTiO 3 . An operando high‐pressure diffuse reflectance infrared spectroscopy (DRIFTS)‐SSITKA study shows that formate species are the major surface intermediates over both catalysts, and the subsequent hydrogenation steps of formate are likely rate‐limiting. However, the catalytic reactivity of Cu/BaTiO 2.8 H 0.2 towards the formate species is much higher than Cu/BaTiO 3 , likely due to the altered electronic structure of interface Cu sites by the hydrides in the support as validated by density functional theory (DFT) calculations.

He, Yang↗

Relating land surface, water table, and weathering fronts with a conceptual valve model for headwater catchments

Knowing little about how porosity and permeability are distributed at depth, we commonly develop models of groundwater by treating the subsurface as a homogeneous black box even though porosity and permeability vary with depth. One reason for this depth variation is that infiltrating meteoric water reacts with minerals to affect porosity in localized zones called reaction fronts. We are beginning to learn to map and model these fronts beneath headwater catchments and show how they are distributed. The subsurface landscapes defined by these fronts lie subparallel to the earth-air interface but with lower relief. They can be situated above, below, or at the water table. These subsurface landscapes of reaction are important because porosity developed from weathering can control subsurface water storage. In addition, porosity often changes at the weathering fronts, and when this affects permeability significantly, the front can act like a valve that re-orients water flowing through the subsurface. We explore controls on the positions of reaction fronts under headwater landscapes by accounting for the timescales of erosion, chemical equilibration, and solute transport. One strong control on the landscape of subsurface reaction is the land surface geometry, which is in turn a function of the erosion rate. In addition, the reaction fronts, like the water table, are strongly affected by the lithology and water infiltration rate. We hypothesize that relationships among the land surface, reaction fronts, and the water table are controlled by feedbacks that can push landscapes toward an “ideal hill”. In this steady state, reaction-front valves partition water volumes into shallow and deep flowpaths. Furthermore, these flows dissolve low- and high-solubility minerals, respectively, allowing their reaction fronts to advance at the erosion rate. This conceptualization could inform better models of subsurface porosity and permeability, replacing the black box.

54 ENVIRONMENTAL SCIENCES↗

Phosphine Ligand Binding and Catalytic Activity of Group 10–14 Heterobimetallic Complexes

We report heterobimetallic complexes have attracted much interest due to their broad range of structures and reactivities as well as unique catalytic abilities. Additionally, these complexes can be utilized as single-source precursors for the synthesis of binary intermetallic compounds. An example is the family of bis(pyridine-2-thiolato)dichloro-germanium and tin complexes of group 10 metals (Pd and Pt). The reactivity of these heterobimetallic complexes is highly tunable through substitution of the group 14 element and the neutral ligand bound to the transition metal. Here, we study the binding energies of three different phosphorous-based ligands, PR 3 (R = Bu, Ph, and OPh) by density functional theory and restricted Hartree–Fock methods. The PR 3 ligand-binding energies follow the trend of PBu 3 > PPh 3 > P(OPh) 3 , in agreement with their sigma-bonding ability. These results are confirmed by ligand exchange experiments monitored with 31 P NMR spectroscopy, in which a weaker binding PR 3 ligand is replaced with a stronger one. Furthermore, we demonstrate that the heterobimetallic complexes are active catalysts in the Negishi coupling reaction, where stronger binding PR 3 ligands inhibit access to an active site at the metal center. Similar strategies could be applied to other complexes to better understand their ligand-binding energetics and predict their reactivity as both precursors and catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A model of smoldering combustion applied to flexible polyurethane foams

Smoldering combustion, particularly in upholstery and bedding materials, has been proven a serious life hazard. The simplest representation of this hazard situation is one-dimensional downward propagation of a smolder wave against a buoyant upflow (cocurrent smolder); the configuration treated here is identical in all respects to this except for the presence of a forced flow replacing the buoyant one. The complex degradation chemistry of the polyurethanes is here reduced to the two major overall reactions of char formation and char oxidation. The model solutions, which are in reasonable agreement with experimental results, show the smolder process to be oxygen-limited, which leads to some very simple trends. More subtle behavior aspects determine actual propagation velocity, fraction of fuel consumed, and apparent equivalence ratio (all of which are variable). The self-insulating character of the smolder wave makes it viable in a wide-ranging set of conditions if the igniting stimulus is sufficiently long. These results have significant implications regarding the problem of smolder prevention or hindrance.

Ohlemiller, T. J.↗

On the alteration of Allende chondrules and the formation of matrix

Recent SEM observations of the Allende chondrules and matrix are reported. Intergrowths of both Fe-rich olivine (with a composition near Fa50), and clinoenstatite (with a composition of about Fs2). All of the clinoenstatite was involved in associations along the outer margins, grain boundaries, and internal crack surfaces of the chondrule. Most of the chondrules also contain abundant opaque inclusions which must have been strongly altered and partially replaced before chondrule formation. It is suggested that the Fe-rich olivine formed from the clinoenstatite by a reaction of the type Fe + 1/202 + MgSiO3 to (Fe,Mg)2SiO4. It is argued that a variation of the small, internally-heated planetesimal provides the most plausible environment for the chemical reaction.

Housley, R. M.↗

Development of Scalable Reactive Transport Framework for PFAS

Research on PFAS chemicals is extensive and covers all aspects, including analytical quantification, determination of properties, toxicology, ex situ treatment, and in situ remediation. PFAS chemicals are very stable and thus persistent/recalcitrant in the environment. Although there are many unknowns about PFAS chemicals, degradation pathways, reaction rates, etc., many different sorption, oxidation, reduction, biological, and innovative treatment approaches are being developed. Sorption with activated carbon is currently the only fully available in situ treatment technology for PFAS-impacted groundwater. Given the wide array of PFAS chemicals and transformation products, remediation may need multi-step treatment trains to fully address the PFAS contamination. The work here provides kinetic reaction modules that represent an initial cut at functionality representing PFAS migration and reaction in groundwater aquifer flow and transport models. One reaction kinetics module provides a method to model kinetically limited adsorption using a mass transfer model. The second reaction module represents biological transformation of 8:2 FTOH and daughter species, illustrating how a complex reaction pathway network can be represented. Both reaction modules allow for spatially variable parameter values so that a variety of remediation approaches (e.g., a PRB or volumetric treatment or variations in geochemical conditions) can be simulated. The intent with these PFAS reaction modules is to provide tools for practitioners to aid in the selection, design, and assessment of potential in situ PFAS remediation strategies. It is anticipated that, as PFAS remediation technologies and scientific understanding advances, these modules would be refined or replaced to match new knowledge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Catalytic Activity of a Vanadium-Doped Mesoporous Octahedral Molecular Sieve-2 (K-OMS-2) toward Hydrogen Evolution Reaction

Hydrogen evolution reaction (HER) is the cathodic reaction in electrochemical water splitting that produces H 2 in a renewable pathway, primarily to be used in fuel cells. K-OMS-2, a manganese octahedral molecular sieve, has the potential to replace Pt as a catalyst for HER due to its redox and electrochemical properties, which can be further improved by doping metal cations into the K-OMS-2 framework. In this work, we synthesized 1, 5, and 10% vanadium- (V) doped mesoporous K-OMS-2 under mild acidic reaction conditions. Here, the mesoporous nature of the samples was confirmed by BET analysis. X-ray photoelectron spectroscopy confirmed that Mn has 2+, 3 +, and 4+ oxidation states, and V is present as V 4+ in V-K-OMS-2 samples. HER performance of 1% V-K-OMS-2 in an acidic medium shows the best activity with -0.32 V overpotential. The overpotential was lowered by 0.56 V upon doping 1% V into the K-OMS-2 framework. The 1% V-K-OMS-2 material has a Tafel slope of 129 mV/decay and an electrochemically active surface area (ECSA) of 127.5 cm 2 ECSA .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalysts by pyrolysis: Direct observation of transformations during re-pyrolysis of transition metal-nitrogen-carbon materials leading to state-of-the-art platinum group metal-free electrocatalyst

Transition metal-nitrogen-carbon (M-N-C) materials have been the focus of scientists’ efforts to address the rising need for earth-abundant materials solutions for energy technology and decarbonization of the economy. They are viewed as one of the most promising candidates to replace platinum group metal (PGM) catalysts in the fuel cell and energy conversion fields, including the application of oxygen reduction reaction, carbon dioxide reduction reaction, and nitrogen reduction reaction. In the effort to improve M-N-C materials properties and achieve atomic dispersity of the transition metal in the carbonaceous matrix, a re-pyrolysis process has been proposed. This secondary heat treatment process of already obtained primary pyrolysis-derived M-N-C materials has been widely reported to substantially improve the electrochemical performance and operational stability of the catalysts. Here, we report a systematic investigation of this process used on samples of templated M-N-C catalysts to obtain state-of-the-art catalysts via in situ heating X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), and X-ray computed tomography (CT) characterization methods. It is found that the re-pyrolysis of M-N-C materials could result in the partial amorphization of the carbonaceous substrate. It causes the rearrangement and transformation of multitudinous N moieties, leading to optimization of their morphological display and association with atomically dispersed transition metal dopants. Ultimately, the re-pyrolysis results in an increase in uniformity of the active Fe-Nx sites distribution without the formation of nano-crystalline phases (metallic or carbide) and with overall preservation of the morphology of the carbonaceous framework achieved during the first formative pyrolysis step of the templated synthesis. Finally, these observations provide confirmation that empirically established re-pyrolysis is recommended to be used on all M-N-C materials despite the different synthesis routes to obtain a practical advanced catalytic material.

36 MATERIALS SCIENCE↗