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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Liquid Phase Exfoliation of Chemically Prelithiated Bilayered Vanadium Oxide in Aqueous Media for Li-Ion Batteries

Bilayered vanadium oxides are attractive for energy storage due to their high initial specific capacities, which could be stabilized by integrating the bilayers with conductive nanoflakes often produced in a form of aqueous dispersions. Therefore, exfoliation of the bilayered vanadium oxides in water with high yield is desirable. Here, this work introduces the first aqueous exfoliation of chemically prelithiated bilayered vanadium oxide (i.e., δ-Li x V 2 O 5 ·nH 2 O or LVO) followed by vacuum filtration to produce a free-standing film, exhibiting a lamellar stacking of the bilayered vanadium oxide nanoflakes as evidenced by scanning electron microscopy. Due to the hydrated nature of bilayered vanadium oxides, the relationship between interlayer water content and the vacuum drying temperature (105 °C vs 200 °C) was studied using X-ray diffraction, thermogravimetric analysis, and Raman spectroscopy. It was found that vacuum drying the LVO nanoflakes at 200 °C enabled more efficient removal of crystallographic water than drying at 105 °C, and did not induce a phase transformation. Scanning transmission electron microscopy confirmed the layered structure of the samples, which was more well-ordered in the 200 °C case and had no clear boundaries between flakes at the atomic scale. Furthermore, electrochemical testing in nonaqueous Li-ion cells revealed that vacuum drying at 200 °C led to improvements in ion storage capacity and electrochemical stability. Improvements in electrochemical charge storage properties of the electrodes obtained via LVO exfoliation and free-standing film assembly in water dried at 200 °C reveal that conventional battery electrode drying protocols need to be revised as new electrochemically active materials are synthesized, such as hydrated layered oxides with expanded interlayer regions. The remaining capacity fading can be attributed to the structural LVO degradation, dissolution of vanadium oxide in electrolyte, and parasitic effects of the remaining interlayer water molecules. Our results establish an environmentally friendly and safe approach to obtain two-dimensional (2D) bilayered vanadium oxide nanoflakes and create a pathway to constructing novel 2D heterostructures for improved performance in energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

In Silico Discovery of Multistep Chemistry Initiated by a Conical Intersection: The Challenging Case of Donor–Acceptor Stenhouse Adducts

Detailed mechanistic understanding of multistep chemical reactions triggered by internal conversion via a conical intersection is a challenging task that emphasizes limitations in theoretical and experimental techniques. We present a discovery-based, hypothesis-free computational approach based on first-principles molecular dynamics to discover and refine the switching mechanism of donor–acceptor Stenhouse adducts (DASAs). We simulate the photochemical experiment in silico, following the “hot” ground state dynamics for 10 ps after photoexcitation. Using state-of-the-art graphical processing units-enabled electronic structure calculations we performed in total ~2 ns of nonadiabatic ab initio molecular dynamics discovering (a) critical intermediates that are involved in the open-to-closed transformation, (b) several competing pathways which lower the overall switching yield, and (c) key elements for future design strategies. Finally, our dynamics describe the natural evolution of both the nuclear and electronic degrees of freedom that govern the interconversion between DASA ground-state intermediates, exposing significant elements for future design strategies of molecular switches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Computational Study of Field Initiated Surface Reactions for Synthesis of Diamond and Silicon

This project involves using quantum chemistry to simulate surface chemical reactions in the presence of an electric field for nanofabrication of diamond and silicon. A field delivered by a scanning tunneling microscope (STM) to a nanometer scale region of a surface affects chemical reaction potential energy surfaces (PES) to direct atomic scale surface modification to fabricate sub-nanometer structures. Our original hypothesis is that the applied voltage polarizes the charge distribution of the valence electrons and that these distorted molecular orbitals can be manipulated with the STM so as to change the relative stabilities of the electronic configurations over the reaction coordinates and thus the topology of the PES and reaction kinetics. Our objective is to investigate the effect of applied bias on surface reactions and the extent to which STM delivered fields can be used to direct surface chemical reactions on an atomic scale on diamond and silicon. To analyze the fundamentals of field induced chemistry and to investigate the application of this technique for the fabrication of nanostructures, we have employed methods capable of accurately describing molecular electronic structure. The methods we employ are density functional theory (DFT) quantum chemical (QC) methods. To determine the effect of applied bias on surface reactions we have calculated the QC PESs in various applied external fields for various reaction steps for depositing or etching diamond and silicon. We have chosen reactions which are thought to play a role in etching and the chemical vapor deposition growth of Si and diamond. The PESs of the elementary reaction steps involved are then calculated under the applied fields, which we vary in magnitude and configuration. We pay special attention to the change in the reaction barriers, and transition state locations, and search for low energy reaction channels which were inaccessible without the applied bias.

Musgrave, Charles Bruce↗
NASA NTRS2013

Mineralogical, Chemical, and Isotopic Heterogeneity in Zagami: Evidence for a Complex Petrogenesis

Textural variations in the shergottite Zagami were initially interpreted as evidence that it formed in a heterogeneous lava flow. Variations in initial Sr-87/Sr-86 ratios between a Coarse Grained (CG) and a Fine Grained (FG) lithology and evidence for more extensive fractionation of the Rb/Sr ratio in a Dark Mottled Lithology (DML) are consistent with such an interpretation. More recently, Niihara et al. and Misawa et al. have reported the mineralogy and Sr-isotopic systematics of an Olivine Rich Lithology (ORL) found in association with the coarse-grained DML lithology in the Kanagawa Zagami specimen [6,7]. Here we call this lithology DML(Ka) to maintain a distinction with DML(USNM) as studied. An Ar-Ar study by Park et al. of a late stage K-rich melt enriched in K2O to approx 7% and intruded into ORL yielded an Ar-Ar age of 202+/0 7 Ma. The present work extends the study of Kanagawa Zagami to Nd-isotopes.

Nyquist, L. E.↗
DOE OSTI2020

Standoff Detection of Chemical Plumes Using Swept-ECQCL Remote Detection Technology: Results from EMRTC Complex Terrain Dual Tracer Experiment

As part of the Complex Terrain Dual Tracer Experiments performed in support of the LYNM program, a swept-wavelength external cavity quantum cascade laser (swept-ECQCL) remote detection system was deployed to measure chemical plume propagation with high temporal resolution. The swept-ECQCL remote detection technology was initially developed at PNNL, and is now under further development at Opticslah, LLC under SBIR funding from DOE (DOE SBIR Phase I Project DE-SC0019855, Remote Detection Technologies, Program Manager Chris Ramos). The swept-ECQCL technology provides a single-frequency infrared laser source which is rapidly scanned over a large wavelength range to measure the infrared absorption of gases, liquids, or solids. Analysis of the measured infrared absorption spectrum is used to detect, identify, and quantify the chemical species which are present. While most previous laser-based techniques used small wavelength tuning ranges to measure only a few isolated spectral lines of a few species, the swept-ECQCL provides the large tuning range needed to measure multiple species simultaneously, and to detect broad absorption features from large molecules or condensed phase materials. In addition, the swept-ECQCL systems have high enough spectral resolution and sensitivity to measure narrow lines of small molecules and determine isotope ratios. The remote detection system for gas plumes is based on the swept-ECQCL technology, and consists of a swept-ECQCL source, infrared detector, control electronics, and beam transmitting and alignment optics. The remote detection system directs the infrared output of the swept-ECQCL to a target retro reflector typically located at ~10-10,000 m distance. The swept-ECQCL wavelength is varied continuously over a large wavelength range (>1000 nm) at rates up to 1000 Hz. The swept ECQCL light reflected from the remote target is collected and focused onto an infrared photodetector. By measuring the detector signal continuously as the swept-ECQCL wavelength is varied, a time-series of absorption spectra are measured for the gases along the beam line of-sight. Based on analysis and fitting of the measured absorption spectra, the time-dependent chemical concentrations of species are determined. Multiple species and mixtures can be detected simultaneously, for all species with absorption features above the sensor noise floor. The sensor output is thus a continuous, high-speed record of identified chemicals along with their concentrations and isotope ratios of interest. The high-speed operation enables low-noise operation in conditions of atmospheric turbulence and allows tracking of fluctuating concentrations in transient chemical plumes as needed for reliable remote detection applications. All components operate with minimal cooling requirements and no cryogens are needed. In addition, the output infrared light is invisible with an intensity below the maximum permissible exposure (MPE) threshold of 100 mW/cm2 for these infrared wavelengths and thus eye safe. The measurement concept for plume detection using the swept-ECQCL remote detection system is as follows. The ECQCL beam is directed toward a remote retro-reflector, which reflects the beam back to the ECQCL system where it is focused onto an infrared photodetector. The line-of-sight from the ECQCL system to the retro-reflector defines the measurement path. The detected infrared signal is recorded continuously and detects the absorption of molecular species along the measurement path. Before a plume release, the system measures absorption from atmospheric constituents, which in this LWIR band consist primarily of lines from H 2 O and CO 2 , with additional weaker absorption from N 2 O, NH 3 , and O 3 possibly contributing. The system then measures any changes in absorption due to the tracer compounds when they enter the measurement path. The shape of absorption features is used to distinguish and identify the different tracer compounds, and the strength of the absorption is used to determine the path-integrated concentration – also called the column density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Magnesian anorthosites from the western highlands of the Moon: Isotope geochemistry and petrogenesis

Breccias from the Apollo 14 landing site have provided a wealth of information on the genesis of the lunar highlands. Various pristine rock-types have been discovered in relative abundance including rare ferroan anorthosites and alkali-suite and magnesian-suite rocks. Mineral-chemical and radiogenic isotopic data are reported here for a newly discovered Mg-suite anorthosite from Apollo 14, sample 14303,347. Meyer et al. reported U-Pb zircon analyses of Mg-suite highlands rocks from the western limb of the Moon. We have compiled these ages and generated a weighted average age of 4211 = 6 Ma; some 200 Ma younger than ferroan anorthosites. Utilizing this age for Mg-anorthosite 14303,347, our data results in an initial epsilon(sub Nd) value of -1.0 and initial Sr-87/Sr-86 of 0.69915. Based on trace-element, isotopic, and mineral-chemical data, the western highlands Mg-suite is interpreted to be crustal precipitates of a picritic magma, which assimilated KREEPy trapped liquid from upper-mantle cumulates during its transport to the crust.

Snyder, Gregory A.↗
DOE OSTI2022

Feasibility of Prelithiation in LiFePO 4

Lithium iron phosphate (LiFePO 4 ) is widely applied as the cathode material for the energy storage Li-ion batteries due to its low cost and high cycling stability. However, the low theoretical specific capacity of LiFePO 4 makes its initial capacity loss more concerning. Therefore, lithium compensation by way of prelithiation and applications of sacrificial Li-rich additives in LiFePO 4 is imminent in elevating the energy density and/or prolonging the lifetime of the LiFePO 4 -based Li-ion batteries (LIBs). Prelithiation in LiFePO 4 is herein carried out by electrochemical and chemical methods and its feasibility is proved on the basis of the electrochemical evaluations such as the initial charge capacity and the cycling stability. In addition, the site of the pre-intercalated Li-ions is found via comprehensive physical characterizations and the density functional theory (DFT) calculations. Furthermore, these findings open a new avenue for elevating the energy density and/or prolonging the lifetime of the high-energy-density batteries.

36 MATERIALS SCIENCE↗
NASA NTRS1994

Biomass Burning and the Production of Greenhouse Gases

Biomass burning is a source of greenhouse gases, carbon dioxide, methane, and nitrous oxide. In addition, biomass burning is a source of chemically active gases, including carbon monoxide, nonmethane hydrocarbons, and nitric oxide. These gases, along with methane, lead to the chemical production of tropospheric ozone (another greenhouse gas) as well as control the concentration of the hydroxyl radical, which regulates the lifetime of almost every atmospheric gas. Following biomass burning, biogenic emissions of nitrous oxide, nitric oxide, and methane are significantly enhanced. It is hypothesized that enhanced postburn biogenic emissions of these gases are related to fire-induced changes in soil chemistry and/or microbial ecology. Biomass burning, once believed to be a tropical phenomenon, has been demonstrated by satellite imagery to also be a regular feature of the world's boreal forests. One example of biomass burning is the extensive 1987 fire that destroyed more than 12 million acres of boreal forest in the People's Republic of China and across its border in the Soviet Union. Recent estimates indicate that almost all biomass burning is human-initiated and that it is increasing with time. With the formation of greenhouse and chemically active gases as direct combustion products and a longer-term enhancement of biogenic emissions of gases, biomass burning may be a significant driver for global change.

Levine, Joel S.↗
NASA NTRS2017

Space Weathering Experiments on Spacecraft Materials

A project to investigate space environment effects on specific materials with interest to remote sensing was initiated in 2016. The goal of the project is to better characterize changes in the optical properties of polymers found in multi-layered spacecraft insulation (MLI) induced by electron bombardment. Previous analysis shows that chemical bonds break and potentially reform when exposed to high energy electrons like those seen in orbit. These chemical changes have been shown to alter a material's optical reflectance, among other material properties. This paper presents the initial experimental results of MLI materials exposed to various fluences of high energy electrons, designed to simulate a portion of the geosynchronous Earth orbit (GEO) space environment. It is shown that the spectral reflectance of some of the tested materials changes as a function of electron dose. These results provide an experimental benchmark for analysis of aging effects on satellite systems which can be used to improve remote sensing and space situational awareness. They also provide preliminary analysis on those materials that are most likely to comprise the high area-to-mass ratio (HAMR) population of space debris in the geosynchronous orbit environment. Finally, the results presented in this paper serve as a proof of concept for simulated environmental aging of spacecraft polymers that should lead to more experiments using a larger subset of spacecraft materials.

Engelhart, D. P.↗
DOE OSTI2023

Qualification of Commercially Available Silicon Carbide for Passive Thermometry in Reactor Experiments – FY23 Status Report

Silicon carbide (SiC) is often used as a passive temperature indicator for uninstrumented in-core nuclear experiments. For the past several decades, Oak Ridge National Laboratory has relied primarily on SiC thermometry manufactured by Dow Chemical Company, formerly Rohm and Haas because of the material’s high density and reduced grain boundary elements. Although Dow SiC has performed well in this application, this material is no longer commercially available, and a new supplier is needed for future experiments. To determine a suitable replacement, a study was initiated on five types of SiC from four commercial vendors. Several critical properties, including density, electrical resistivity, chemical purity, grain structure, crystal structure, and strength were measured in samples from each material. Additionally, thermometry specimens were manufactured for irradiation in the High Flux Isotope Reactor at nominal temperatures of 300°C, 600°C, and 900°C, which will be measured using continuous dilatometry at a later date. This report provides an update of commercially available SiC material characterization and the irradiation capsule design.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2025

Nanoscale structural evolution and phase transformation of geopolymers: In situ SAXS/WAXS investigation under uniaxial tension at elevated temperatures

This investigation delves into the degradation mechanisms of high-density polyethylene geomembranes (PE GMXs) under a spectrum of conditions, replicating real-world scenarios within a rigorously controlled laboratory setting. The treatment protocols applied induced a notable increase in the crystallinity of the treated specimens relative to the untreated controls. Small-angle x-ray scattering (SAXS) analysis identified an initial long period (interlamellar distance) of 16.9 nm for the untreated polymer, which expanded by 19.5% at a strain of 16.7 percent. Conversely, the treated PE GMXs exhibited a more gradual elongation of the long period, with an increase of merely 10.6% at a strain of 23.3 percent. At an elevated temperature of 65°C, both samples exhibited pronounced strain hardening, with the treated PE GMXs demonstrating superior stability even at a strain of 150 percent. Wide-angle x-ray scattering (WAXS) experiments corroborated these observations, revealing that the diffraction patterns of the untreated PE remained stable up to a strain of 16.7%, whereas those of the treated PE remained distinct up to a strain of 46.1 percent. Scanning electron microscopy (SEM) images substantiated the formation of a shish–kebab structure in the treated samples. The study concludes that the geopolymer underwent oxidation and material degradation as a result of the chemical and mechanical treatments, transitioning to a more crystalline state and concomitantly losing its initial elasticity.

36 MATERIALS SCIENCE↗
NASA NTRS2022

A Primordial Atmospheric Origin of Hydrospheric Deuterium Enrichment on Mars

The deuterium-to-hydrogen (D/H or 2H/1H) ratio of Martian atmospheric water (~6× standard mean ocean water, SMOW) is higher than that of known sources, requiring planetary enrichment. A recent measurement by NASA’s Mars Science Laboratory rover Curiosity of Hesperian-era (>3 Ga) clays yields a D/H ratio ~3×SMOW, demonstrating that most of the enrichment occurs early in Mars’s history, reinforcing the conclusions of Martian meteorite studies. As on Venus, Mars’s D/H enrichment is widely thought to reflect preferential loss to space of 1H (protium) relative to 2H (deuterium), but both the cause and the global environmental context of large and early hydrogen losses remain to be determined. Here, we apply a recent model of primordial atmosphere evolution to Mars, link the magma ocean of the accretion epoch with a subsequent water-ocean epoch, and calculate the behavior of deuterium for comparison with the observed record. In contrast to earlier works that consider Martian D/H fractionation in atmospheres in which hydrogen reservoirs are present exclusively as H2O or H2, here we consider 2-component (H2O-H2) outgassed atmospheres in which both condensed (H2O) and escaping (H2) components – and their interaction – are explicitly calculated. We find that a a ≈2-3× hydrospheric deuterium-enrichment is produced rapidly if the Martian magma ocean is chemically reducing at last equilibration with the primordial atmosphere, making H2 and CO the initially dominant species, with minor abundances of H2O and CO2. Reducing gases – in particular H2 – can cause substantial greenhouse warming and prevent a water ocean from freezing immediately after the magma ocean epoch. We find that greenhouse warming due to plausible H2 inventories (pH2=1-102 bars) yields surface temperatures high enough (Ts=290-560 K) to stabilize a water ocean and produce an early hydrological cycle through which surface water can be circulated. Moreover, the pressure-temperature conditions are high enough to produce ocean-atmosphere H2O-H2 isotopic equilibrium through gas-phase deuterium exchange such that surface H2O strongly concentrates deuterium relative to H2, which preferentially takes up protium and escapes from the primordial atmosphere. The efficient physical separation of deuterium-rich (H2O) and deuterium-poor (H2) species via condensation permits equilibrium isotopic partitioning and early atmospheric escape to be recorded in modern crustal reservoirs. The proposed scenario of primordial H2-CO-rich outgassing and escape suggests significant durations (>Myr) of chemical conditions on the Martian surface conducive to prebiotic chemistry immediately following magma ocean crystallization.

Mars↗
NASA NTRS2024

Preliminary Measurements of Partial Discharge Inception Voltage Degradation with Constant Temperature Aging of Magnet Wire Twisted Pairs for Electric Aircraft Motors

Electric aircraft require high reliability electric motors to meet the stringent safety standards of the aviation industry. Motor winding insulation lifetime and reliability models for electric aircraft applications are needed to enable design of high reliability and high-performance electric motors for aviation applications. Three primary stresses effect the lifetime of motor winding insulation: thermochemical, mechanical, and electrical. This paper presents preliminary experiments on twisted pairs of magnet wire targeting understanding the thermo-chemical degradation of motor winding insulation through constant temperature thermal aging. Three types of magnet wire twisted pairs where tested: polyimide insulated magnet wire, epoxy coated polyimide insulated magnet wire, and epoxy potted polyimide magnet wire. The degradation of the samples over time at temperature was tracked using partial discharge inception voltage measurements. These initial experiments were used for development of procedures and expertise in partial discharge testing and thermo-chemical aging to inform future testing. The preliminary nature of these experiments should be noted when viewing the results. Lessons learned from the experiments are documented.

Thomas Tallerico↗
DOE OSTI2020

Effects of dissipative baryon current in heavy-ion collisions at RHIC-BES energies

The CLVisc (3+1)D viscous hydrodynamic model is extended to include the equation of net baryon conservation and the Israel-Stewart-like equations for dissipative baryon current. Using the NEOSB equation of state, we simulate the dynamical evolution and collectivity of the quark-gluon plasma with finite chemical potential, assuming smooth energy density and net baryon density distributions at the initial proper time. Numerical results are shown for the impact of net-baryon dissipation on particle yields and p T spectra in heavy-ion collisions at beam energy scan energies.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Light-Induced Transformation of Virus-Like Particles on TiO 2

Titanium dioxide (TiO 2 ) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO 2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO 2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO 2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO 2 surface. The in situ GISAXS measurements under an N 2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Ultraviolet-Activated Solid-State Nitrene Cross-Linking: A Scalable Pathway to Prolonged Lifespan in Anion Exchange Membranes

Anion exchange membranes (AEMs) offer a cost-effective alternative to proton exchange membranes as alkaline fuel cells and electrolyzers permit the use of non-platinum group electrodes and components. Despite continued progress, the operational lifetime and stability of these membranes limit the widespread adoption of AEM-based electrochemical technologies. This study presents a flexible and easily implemented ultraviolet (UV)-initiated nitrene-based cross-linking method which uses a small, facile organic azide precursor. As a proof of concept, we demonstrate this approach on the well-studied poly(2,6-dimethyl-1,4-phenylene oxide) quaternary ammonium AEM (QPPO) polyelectrolyte. Further, a survey of cross-linker density (2.5–10 mol %) found that the addition of 10 mol % results in a 59% reduction in water uptake, a 58.8% decrease in the swell ratio, and a 31% increase in tensile strength vs the un-cross-linked material. Nitrene cross-linking also enhanced the membrane’s durability, enabling 1000 h of stable performance under electrochemical load. This UV-initiated cross-linking method may be easily integrated into production processes, allowing chemical cross-linking at any stage, including posthydration.

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

Topological controls on aluminosilicate glass dissolution: Complexities induced in hyperalkaline aqueous environments

Abstract Fly ash, an aluminosilicate composite consisting of disordered (major) and crystalline (minor) compounds, is a low‐carbon alternative that can partially replace ordinary portland cement (OPC) in the binder fraction of concrete. Therefore, understanding the reactivity of fly ash in the hyperalkaline conditions prevalent in concrete is critical to predicting concrete's performance; including setting and strength gain. Herein, temporal measurements of the solution composition (using inductively coupled plasma‐optical emission spectrometry: ICP‐OES) are used to assess the aqueous dissolution rate of monophasic synthetic aluminosilicate glasses analogous to those present in technical fly ashes, under hyperalkaline conditions (10 ≤ pH ≤ 13) across a range of temperatures (25°C ≤ T≤45°C). The dissolution rate is shown to depend on the average number of topological constraints per atom within the glass network (n c , unitless), but this dependence weakens with increasing pH (>10). This is postulated to be on account of: (a) time‐dependent changes in the glass’ surface structure, that is, the number of topological constraints; and/or (b) a change in the dissolution mechanism (eg from network hydrolysis to transport control). The results indicate that the topological description of glass dissolution is most rigorously valid only at very short reaction times (ie at high undersaturations), especially under conditions of hyperalkalinity. These findings provide an improved basis to understand the underlying factors that affect the initial and ongoing reactivity of aluminosilicate glasses such as fly ash in changing chemical environments, for example, when such materials are utilized in cementitious composites.

Oey, Tandré↗
DOE OSTI2022

Technoeconomic evaluation of recent process improvements in production of sugar and high-value lignin co-products via two-stage Cu-catalyzed alkaline-oxidative pretreatment

Abstract Background A lignocellulose-to-biofuel biorefinery process that enables multiple product streams is recognized as a promising strategy to improve the economics of this biorefinery and to accelerate technology commercialization. We recently identified an innovative pretreatment technology that enables of the production of sugars at high yields while simultaneously generating a high-quality lignin stream that has been demonstrated as both a promising renewable polyol replacement for polyurethane applications and is highly susceptible to depolymerization into monomers. This technology comprises a two-stage pretreatment approach that includes an alkaline pre-extraction followed by a metal-catalyzed alkaline-oxidative pretreatment. Our recent work demonstrated that H 2 O 2 and O 2 act synergistically as co-oxidants during the alkaline-oxidative pretreatment and could significantly reduce the pretreatment chemical input while maintaining high sugar yields (~ 95% glucose and ~ 100% xylose of initial sugar composition), high lignin yields (~ 75% of initial lignin), and improvements in lignin usage. Results This study considers the economic impact of these advances and provides strategies that could lead to additional economic improvements for future commercialization. The results of the technoeconomic analysis (TEA) demonstrated that adding O 2 as a co-oxidant at 50 psig for the alkaline-oxidative pretreatment and reducing the raw material input reduced the minimum fuel selling price from $1.08/L to $0.85/L, assuming recoverable lignin is used as a polyol replacement. If additional lignin can be recovered and sold as more valuable monomers, the minimum fuel selling price (MFSP) can be further reduced to $0.73/L. Conclusions The present work demonstrated that high sugar and lignin yields combined with low raw material inputs and increasing the value of lignin could greatly increase the economic viability of a poplar-based biorefinery. Continued research on integrating sugar production with lignin valorization is thus warranted to confirm this economic potential as the technology matures.

09 BIOMASS FUELS↗