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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 1,729 records · Page 96
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Effect of ball milling conditions on microstructure and lithium storage properties of LiNi0.5Mn1.5O4 as cathode for lithium-ion batteries

Highlights: • Precursors of LNM respectively synthesized by dry and wet ball-milling. • Under wet ball-milling raw materials form slurry and mix well in microscale. • LNM-w12 sample presents proper stoichiometric composition and the highest D{sub Li}{sup +}. • At 0.1 C rate LNM-w12 delivers 133 mAh g{sup −1} at 100 cycle close to theoretical value. • LNM-w12 delivers 97 mAh g{sup −1} at 10 C rate and remains 78% after 1000 cycles. - Abstract: In this work, the precursors of LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} (LNM) are respectively synthesized by dry and wet ball-milling. Under wet ball-milling, the problem of sticky residue in dry ball-milling is effectively resolved, the three raw materials form homogeneous slurry and mix well in micrometers level. LNM-w12 sample synthesized by using precursor added 12 mL milling medium gains the atomic composition closed to the theoretical value, ordered crystal structure and the highest lithium diffusion coefficient. At 0.1 C rate, LNM-w12 delivers the capacity of 136 mAh g{sup −1} at the first cycle, and 133 mAh g{sup −1} at the 100th cycle. Moreover, LNM-w12 delivers the initial capacity of 97 mAh g{sup −1} at 10 C rate, and remains 78% after 1000 cycles. The great rate capability of LNM-w12 can be attributed to the well-formed crystal structure, ordered and stable surface structure, which is conducive to the diffusion of lithium ions and prevents the dissolution of the material at high voltage.

25 ENERGY STORAGE↗
DOE OSTI2018

TiO2 nanotubes grown on Ti substrates with different microstructure

Highlights: • TiO{sub 2} nanotube layers were grown on four different Ti substrates by anodization. • Ti substrates with completely different microstructures were used. • The grain size of the substrates ranged from nanocrystalline to single-crystalline. • Differences between the nanotubes grown on these substrates were evaluated. • Similar nanotube dimensions were received on all Ti substrates. - Abstract: Four Ti substrates with various microstructures were investigated for the anodic growth of TiO{sub 2} nanotube layers: nanocrystalline and single-crystalline ingots as well as microcrystalline thick Ti sheets and microcrystalline thin Ti foils. All substrates were anodized in a conventional ethylene glycol based electrolyte under identical conditions. The resulting TiO{sub 2} nanotube layers were compared in dimensions and the consumption of Ti required for their growth. Unexpectedly, the results showed that on all substrates nanotube layers with a similar thickness and nanotube diameter, as well as a similar degree of ordering and after annealing the same crystallographic orientation of anatase were received, regardless the microstructures. However, the nanotube layers grown on a Ti sheet revealed a slightly higher thickness compared to the other substrates which were assigned to slower field-assisted dissolution rates due to different impurities found in this substrate compared to other ones.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Stabilizing Ni-rich layered cathode for high-voltage operation through hierarchically heterogeneous doping with concentration gradient

High-nickel LiNi x Mn y Co 1-x-y O 2 (NMC) cathodes have demonstrated superior energy density, yet their stability is compromised under high voltage conditions. To address this, here we propose a strategy of heterogeneous doping with a concentration gradient, specifically through Sr–Zr co-modification. We synthesized Ni-rich NMC particles featuring several micron-sized secondary particles composed of micron-sized primary grains. This design aims to harness the structural robustness of single-crystalline grains and the favorable diffusion kinetics of polycrystalline secondary particles. Systematic characterization using a combination of electrochemical measurements and synchrotron analytics reveals an intriguing pattern of hierarchically heterogeneous Sr–Zr co-doping. It demonstrates a depth-dependent concentration gradient at the secondary particle level and competing dopant segregation over the buried grain boundaries. This unique characteristic creates opportunities for enhancing battery performance, particularly by optimizing precursors and implementing advanced modulation techniques. We also investigate the dissolution and precipitation of the cathode's transition metal cations upon high-voltage cycling. These insights suggest that a tailored compositional variation can be a viable approach to effectively design the next-generation high-Ni NMC cathode materials for high-voltage lithium batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Recycling of a post-industrial printed multilayer plastic film containing polyurethane inks by solvent-targeted recovery and precipitation

The recently reported Solvent-Targeted Recovery And Precipitation (STRAP) strategy is used to deconstruct multilayer plastic packaging films into their constituent resins by selective polymer dissolution. To broaden the applicability of STRAP, we demonstrate the process with a flexible post-industrial printed multilayer plastic film used for food packaging. The material was a reverse printed film composed of polyethylene (PE), ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), and polyurethane (PU)-based inks. Removal of all colors was observed with biomass-derived gamma-valerolactone (GVL) and the recovered polymers possessed comparable properties to the corresponding virgin resins. A technoeconomic analysis indicates that this STRAP process could be economically feasible at a processing capacity of 6,000 tons per year. Furthermore, the production of plastic films with materials recovered by this STRAP process can have a lower climate change impact than the production of films from virgin polymers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Grouping nanomaterials to predict their potential to induce pulmonary inflammation

The rapidly expanding manufacturing, production and use of nanomaterials have raised concerns for both worker and consumer safety. Various studies have been published in which induction of pulmonary inflammation after inhalation exposure to nanomaterials has been described. Nanomaterials can vary in aspects such as size, shape, charge, crystallinity, chemical composition, and dissolution rate. Currently, efforts are made to increase the knowledge on the characteristics of nanomaterials that can be used to categorise them into hazard groups according to these characteristics. Grouping helps to gather information on nanomaterials in an efficient way with the aim to aid risk assessment. Here, we discuss different ways of grouping nanomaterials for their risk assessment after inhalation. Since the relation between single intrinsic particle characteristics and the severity of pulmonary inflammation is unknown, grouping of nanomaterials by their intrinsic characteristics alone is not sufficient to predict their risk after inhalation. The biokinetics of nanomaterials should be taken into account as that affects the dose present at a target site over time. The parameters determining the kinetic behaviour are not the same as the hazard-determining parameters. Furthermore, characteristics of nanomaterials change in the life-cycle, resulting in human exposure to different forms and doses of these nanomaterials. As information on the biokinetics and in situ characteristics of nanomaterials is essential but often lacking, efforts should be made to include these in testing strategies. Grouping nanomaterials will probably be of the most value to risk assessors when information on intrinsic characteristics, life-cycle, biokinetics and effects are all combined. - Highlights: • Grouping of nanomaterials helps to gather information in an efficient way with the aim to aid risk assessment. • Different ways of grouping nanomaterials for their risk assessment after inhalation are discussed. • Grouping of nanomaterials by their intrinsic characteristics alone is not sufficient to predict their risk after inhalation. • To link physicochemical characteristics of nanomaterials to an effect, information on their biokinetic behaviour is needed. • To be of most value, grouping should combine information on intrinsic characteristics, life-cycle, biokinetics and effects.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2014

Nuclear envelope breakdown induced by herpes simplex virus type 1 involves the activity of viral fusion proteins

Herpesvirus infection reorganizes components of the nuclear lamina usually without loss of integrity of the nuclear membranes. We report that wild-type HSV infection can cause dissolution of the nuclear envelope in transformed mouse embryonic fibroblasts that do not express torsinA. Nuclear envelope breakdown is accompanied by an eight-fold inhibition of virus replication. Breakdown of the membrane is much more limited during infection with viruses that lack the gB and gH genes, suggesting that breakdown involves factors that promote fusion at the nuclear membrane. Nuclear envelope breakdown is also inhibited during infection with virus that does not express UL34, but is enhanced when the US3 gene is deleted, suggesting that envelope breakdown may be enhanced by nuclear lamina disruption. Nuclear envelope breakdown cannot compensate for deletion of the UL34 gene suggesting that mixing of nuclear and cytoplasmic contents is insufficient to bypass loss of the normal nuclear egress pathway. - Highlights: • We show that wild-type HSV can induce breakdown of the nuclear envelope in a specific cell system. • The viral fusion proteins gB and gH are required for induction of nuclear envelope breakdown. • Nuclear envelope breakdown cannot compensate for deletion of the HSV UL34 gene.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2013

Nickel recovery from electronic waste II Electrodeposition of Ni and Ni–Fe alloys from diluted sulfate solutions

Highlights: • Ni can be recovered from EG wastes as pure Ni or as Ni–Fe alloys. • The control of the experimental conditions gives a certain alloy composition. • Unusual deposits morphology shows different nucleation mechanisms for Ni vs Fe. • The nucleation mechanism was progressive for Ni and instantaneous for Fe and Ni–Fe. - Abstract: This study focuses on the electrodeposition of Ni and Ni–Fe alloys from synthetic solutions similar to those obtained by the dissolution of electron gun (an electrical component of cathode ray tubes) waste. The influence of various parameters (pH, electrolyte composition, Ni{sup 2+}/Fe{sup 2+} ratio, current density) on the electrodeposition process was investigated. Scanning electron microscopy (SEM) and X-ray fluorescence analysis (XRFA) were used to provide information about the obtained deposits’ thickness, morphology, and elemental composition. By controlling the experimental parameters, the composition of the Ni–Fe alloys can be tailored towards specific applications. Complementarily, the differences in the nucleation mechanisms for Ni, Fe and Ni–Fe deposition from sulfate solutions have been evaluated and discussed using cyclic voltammetry and potential step chronoamperometry. The obtained results suggest a progressive nucleation mechanism for Ni, while for Fe and Ni–Fe, the obtained data points are best fitted to an instantaneous nucleation model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Sample preparation and biomass determination of SRF model mixture using cryogenic milling and the adapted balance method

Highlights: • An alternative sample comminution procedure for SRF is tested. • Proof of principle is shown on a SRF model mixture. • The biogenic content of the SRF is analyzed with the adapted balance method. • The novel method combines combustion analysis and a data reconciliation algorithm. • Factors for the variance of the analysis results are statistically quantified. - Abstract: The biogenic fraction of a simple solid recovered fuel (SRF) mixture (80 wt% printer paper/20 wt% high density polyethylene) is analyzed with the in-house developed adapted balance method (aBM). This fairly new approach is a combination of combustion elemental analysis (CHNS) and a data reconciliation algorithm based on successive linearisation for evaluation of the analysis results. This method shows a great potential as an alternative way to determine the biomass content in SRF. However, the employed analytical technique (CHNS elemental analysis) restricts the probed sample mass to low amounts in the range of a few hundred milligrams. This requires sample comminution to small grain sizes (<200 μm) to generate representative SRF specimen. This is not easily accomplished for certain material mixtures (e.g. SRF with rubber content) by conventional means of sample size reduction. This paper presents a proof of principle investigation of the sample preparation and analysis of an SRF model mixture with the use of cryogenic impact milling (final sample comminution) and the adapted balance method (determination of biomass content). The so derived sample preparation methodology (cutting mills and cryogenic impact milling) shows a better performance in accuracy and precision for the determination of the biomass content than one solely based on cutting mills. The results for the determination of the biogenic fraction are within 1–5% of the data obtained by the reference methods, selective dissolution method (SDM) and {sup 14}C-method ({sup 14}C-M)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

A solvent-targeted recovery and precipitation scheme for the recycling of up to ten polymers from post-industrial mixed plastic waste

Solvent-Targeted Recovery and Precipitation (STRAP TM ) separates polymers within a plastic waste stream by selective dissolution. In this work, the STRAP framework, which combines computational modeling and experiments, was applied to develop a series of steps to separate up to 10 polymers from post-industrial mixed plastic waste (MPW) and the main components recovered were LDPE, HDPE, and PET. The STRAP steps were initially demonstrated with a physical polymer mixture containing LDPE, HDPE, PS, PVC, EVOH, PET, PP, PA6, PA66, and PA66/6, in which recoveries of 89% or higher were achieved for each polymer. Furthermore, this paper demonstrates a solvent selection approach that can be applied to separate unknown plastics materials into purer components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reactive Transport Modeling of Shale–Fluid Interactions after Imbibition of Fracturing Fluids

Injection of hydraulic fracturing fluid (HFF) into shale formations for unconventional oil/gas production results in chemical reactions in the shale matrix. Our recent experimental study determined the depths to which different types of reactions between the shale matrix and the HFF extended. In the present study, we built continuum-scale reactive transport models to understand the coupling of chemical reactions and the transport of aqueous species in these shale–HFF systems. Calibration of the model with our previous experimental results reveals that it takes hours to months for the shale matrix to completely neutralize the imbibed acids, depending primarily upon the carbonate content of the shale. Both the HFF pH and pore pH affect the location of barite precipitation, resulting in unique barite precipitation profiles extending millimeters into calcite-rich Eagle Ford shale but only tens of micrometers into low-carbonate Marcellus shale. In addition, dissolved oxygen and extracted bitumen are key to reproducing the experimental observation of Fe(III) (oxyhydr)oxide formation in the shale matrix as a result of pyrite dissolution in the shales. A comparison between the modeling results of porosity in the present study to experimentally measured permeabilities in our previous study suggests that chemical reactions occurring at a greater depth than the observable reaction zone might have impacted permeability. Our model serves as a benchmark for efficiently modeling water–rock interactions in similar systems where bulk rock samples react with a solution in batch reactors. Important reactive transport processes were ascertained via modeling, which allows for quantitative prediction of shale–HFF interactions in shale matrices given the shale and HFF compositions.

58 GEOSCIENCES↗
DOE OSTI2022

Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides

Transformation of metastable Fe(III) oxyhydroxides is a prominent process in natural environments and can be significantly accelerated by the coexisting aqueous Fe(II) (Fe(II) aq ). Recent evidence points to the solution mass transfer of labile Fe(III) (Fe(III) labile ) as the primary intermediate species of general importance. However, a mechanistic aspect that remains unclear is the dependence of phase outcomes on the identity of the metastable Fe(III) oxyhydroxide precursor. Here, we compared the coupled evolution of Fe(II) species, solid phases, and Fe(III) labile throughout the Fe(II)-catalyzed transformation of lepidocrocite (Lp) versus ferrihydrite (Fh) at equal Fe(III) mass loadings with 0.2–1.0 mM Fe(II) aq at pH = 7.0. Similar to Fh, the conversion of Lp to product phases occurs by a dissolution–reprecipitation mechanism mediated by Fe(III) labile that seeds the nucleation of products. Though for Fh we observed a transformation to goethite (Gt), accompanied by the transient emergence and decline of Lp, for initial Lp we observed magnetite (Mt) as the main product. Further, a linear correlation between the formation rate of Mt and the effective supersaturation in terms of Fe(III) labile concentration shows that Fe(II)-induced transformation of Lp into Mt is governed by the classical nucleation theory. When Lp is replaced by equimolar Gt, Mt formation is suppressed by opening a lower barrier pathway to Gt by heterogeneous nucleation and growth on the added Gt seeds. The collective findings add to the mechanistic understanding of factors governing phase selections that impact iron bioavailability, system redox potential, and the fate and transport of coupled elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Copper Nanoparticle Induced Cytotoxicity to Nitrifying Bacteria in Wastewater Treatment: A Mechanistic Copper Speciation Study by X-ray Absorption Spectroscopy

With the inclusion of engineered nanomaterials in industrial processes and consumer products, wastewater treatment plants (WWTPs) could serve as a major sink for these emerging contaminants. Previous research has demonstrated that nanomaterials are potentially toxic to microbial communities utilized in biological wastewater treatment (BWT). Copper-based nanoparticles (CuNPs) are of particular interest based on their increasing use in wood treatment, paints, household products, coatings, and byproducts of semiconductor manufacturing. A critical step in BWT is nutrient removal through nitrification. This study examined the potential toxicity of uncoated and polyvinylpyrrolidone (PVP)-coated CuO, and Cu 2 O nanoparticles, as well as Cu ions to microbial communities responsible for nitrification in BWT. Inhibition was inferred from changes to the specific oxygen uptake rate (sOUR) in the absence and presence of Cu ions and CuNPs. X-ray absorption fine structure spectroscopy, with linear combination fitting (LCF), was utilized to track changes to Cu speciation throughout exposure. Results indicate that the dissolution of Cu ions from CuNPs drive microbial inhibition. Here, the presence of a PVP coating on CuNPs has little effect on inhibition. LCF analysis of the biomass combined with metal partitioning analysis supports the current hypothesis that Cu-induced cytotoxicity is primarily caused by reactive oxygen species formed from ionic Cu in solution via catalytic reaction intermediated by reduced Cu(I) species.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Dissolved Organic Matter Affects Arsenic Mobility and Iron(III) (hydr)oxide Formation: Implications for Managed Aquifer Recharge

During managed aquifer recharge (MAR), injected water significantly alters water chemistry in an aquifer, affecting arsenic mobility. To elucidate the effects of dissolved organic matter (DOM) on arsenic mobilization during MAR, this bench-scale study examined arsenic mobilization from arsenopyrite (FeAsS, an arsenic-containing sulfide) in the presence of Suwannee River natural organic matter, humic acid, and fulvic acid (SRNOM, SRHA, and SRFA), alginate (Alg), polyaspartate (PA), and glutamate (Glu). Suwannee River DOM (SRDOM) decreased arsenic mobility in the short term (<6 h) via inhibiting arsenopyrite oxidative dissolution, but increased arsenic mobility over a longer experimental time (~7 days) via inhibiting secondary iron(III) (hydr)oxide precipitation and decreasing arsenic adsorption onto iron(III) (hydr)oxide. In situ grazing incidence small-angle X-ray scattering measurements indicated that SRDOM decreased iron(III) (hydr)oxide nucleus sizes and growth rates. A combined analysis of SRDOM and other proteinaceous or labile DOM (Alg, PA, and Glu) revealed that DOM with higher molecular weights would cause more increased arsenic mobility. Finally, these new observations advance our understanding of the impacts of DOM in injected water on arsenic mobility and secondary precipitate formation during MAR, and in other systems where interactions between DOM, arsenic, and iron(III) (hydr)oxides take place.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Crystallization and Phase Transformations of Aluminum (Oxy)hydroxide Polymorphs in Caustic Aqueous Solution

Gibbsite, bayerite, and boehmite are important aluminum (oxy)hydroxide minerals in nature and have been widely deployed in various industrial applications. They are also major components in caustic nuclear wastes stored at various U.S. locations. Knowledge of their crystallization and phase transformation processes contributes to understanding their occurrence and could help optimize waste treatment processes. While it has been reported that partial conversion of bayerite and gibbsite to boehmite occurs in basic solutions at elevated temperatures, systematic studies of factors affecting the phase transformation as well as the underlying reaction mechanisms are non-existent, particularly in highly alkaline solutions. We explored the effects of sodium hydroxide concentrations (0.1~3 M), reaction temperature (60~100 ?) and aluminum concentrations (0.1~1 M) on the crystallization and transformation of these aluminum (oxy)hydroxides. Detailed structural and morphological characterization by X-ray diffraction (XRD), scanning electron microscopy (SEM), and nuclear magnetic resonance (NMR) spectrometry revealed that these processes depend largely on the reaction temperature and the Al/OH- ratio. When 1 = Al/OH- = 2.5, the reactions favor formation of high crystallinity precipitates, whereas at Al/OH- ratio ? 2.5 precipitation ceases unless the Al concentration is higher than 1 M. We identified pseudoboehmite, bayerite and gibbsite as intermediate phases to bayerite, gibbsite and boehmite, respectively, all of which transform via dissolution-reprecipitation. Gibbsite transforms to boehmite in both acidic and weak caustic environments at temperatures above 80 oC. However, a ‘bar-shaped’ gibbsite morphology dominates in highly caustic environments (3 M NaOH). The findings enable a robust basis for selection of various solid phases by tuning the reaction conditions.

aluminum (oxy)hydroxide polymorphs, crystallizatio↗
DOE OSTI2025

Water-In-Glass: A Self-Supporting Inorganic Aqueous Electrolyte

Aqueous rechargeable sodium-ion batteries (ARNIBs) are emerging as cost-effective and safe candidates for large-scale energy storage applications. However, their advancement has been constrained by the narrow electrochemical stability window (ESW) of conventional aqueous electrolytes (1.23 V). Here, in this study, we present a transformative approach using an inexpensive and rapidly dissolvable inorganic glass material, water glass (W-glass), to significantly enhance the ESW and enable the development of solid-state, self-supporting aqueous film (SSA film) electrolytes. These SSA film electrolytes exhibit an extended ESW of up to 3.5 V and a conductivity of ∼10 –4 S/cm at room temperature. Structural analysis using magic-angle spinning nuclear magnetic resonance (NMR) and solution-state NMR reveals that the dissolution of W-glass in water is driven by the interdependent hydrolysis of P–O–P linkages and Na + –H + ion exchange. This work offers a cost-effective and scalable solution for advancing high-performance ARNIB technology, addressing critical barriers to commercial adoption.

Electrochemical stability window↗
DOE OSTI2017

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shape enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3 Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Elaboration of Aggregated Polysulfide Phases: From Molecules to Large Clusters and Solid Phases

With the increasing strategies aimed at repressing shuttle problems in the lithium–sulfur battery, dissolved contents of polysulfides are significantly reduced. Except for solid-state Li 2 S 2 and Li 2 S, aggregated phases of polysulfides remain unexplored, especially in well confined cathode material systems. Here, we report a series of nanosize polysulfide clusters and solid phases from an atomic perspective. The calculated phase diagram and formation energy evolution process demonstrate their stabilities and cohesive tendency. It is interesting to find that Li 2 S 6 can stay in the solid state and contains short S 3 chains, further leading to the unique stability and dense structure. Simulated electronic properties indicate reduced band gaps when polysulfides are aggregated, especially for solid phase Li 2 S 6 with a band gap as low as 0.47 eV. In conclusion, their dissolution behavior and conversion process are also investigated, which provides a more realistic model and gives further suggestions on the future design of the lithium–sulfur battery.

25 ENERGY STORAGE↗