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At least 1,441 records · Page 80

Lignin-First Biorefinery Development

Cost-effective biomass fractionation is an enabling, grand challenge for biorefining, especially when both carbohydrates and lignin are targeted for valorization. The advent of Reductive Catalytic Fractionation (RCF) - an active stabilization approach that solubilizes lignin from biomass and catalytically depolymerizes it into a narrow slate of monomers and oligomers - represents a potential step forward for this important goal. In the Lignin-First Biorefinery Development project, we are employing techno-economic analysis (TEA) and life cycle assessment (LCA) to guide bench-scale R&D efforts towards cost-effective RCF-based biorefining. This project is critical to lignin valorization efforts and could enable the use of woody feedstocks in a traditional biochemical conversion context. To date, we have conducted the first rigorous TEA and LCA study of the RCF process, developed a flow-through system to separate biomass and the chemical catalyst in RCF chemistry, developed models for solvolysis chemistry and transport phenomena for poplar, and co-led an international, authoritative perspective on guidelines for the research community on how to best practice lignin-first biorefining. The primary challenges for the lignin-first RCF process going forward are catalyst stability, the need to utilize, recover, and recycle high boiling point solvents to lower RCF reactor pressure, and the challenge of operating RCF continuously - all of which are being directly tackled by this project.

biomass↗

Stimulus-response compatibility and psychological refractory period effects: implications for response selection

The purpose of this paper was to provide insight into the nature of response selection by reviewing the literature on stimulus-response compatibility (SRC) effects and the psychological refractory period (PRP) effect individually and jointly. The empirical findings and theoretical explanations of SRC effects that have been studied within a single-task context suggest that there are two response-selection routes-automatic activation and intentional translation. In contrast, all major PRP models reviewed in this paper have treated response selection as a single processing stage. In particular, the response-selection bottleneck (RSB) model assumes that the processing of Task 1 and Task 2 comprises two separate streams and that the PRP effect is due to a bottleneck located at response selection. Yet, considerable evidence from studies of SRC in the PRP paradigm shows that the processing of the two tasks is more interactive than is suggested by the RSB model and by most other models of the PRP effect. The major implication drawn from the studies of SRC effects in the PRP context is that response activation is a distinct process from final response selection. Response activation is based on both long-term and short-term task-defined S-R associations and occurs automatically and in parallel for the two tasks. The final response selection is an intentional act required even for highly compatible and practiced tasks and is restricted to processing one task at a time. Investigations of SRC effects and response-selection variables in dual-task contexts should be conducted more systematically because they provide significant insight into the nature of response-selection mechanisms.

Review Literature↗

Cruise-Efficient Short Takeoff and Landing (CESTOL): Potential Impact on Air Traffic Operations

The National Aeronautics and Space Administration (NASA) is investigating technological and operational concepts for introducing Cruise-Efficient Short Takeoff and Landing (CESTOL) aircraft into a future US National Airspace System (NAS) civil aviation environment. CESTOL is an aircraft design concept for future use to increase capacity and reduce emissions. CESTOL provides very flexible takeoff, climb, descent and landing performance capabilities and a high-speed cruise capability. In support of NASA, this study is a preliminary examination of the potential operational impact of CESTOL on airport and airspace capacity and delay. The study examines operational impacts at a subject site, Newark Liberty Intemational Airport (KEWR), New Jersey. The study extends these KEWR results to estimate potential impacts on NAS-wide network traffic operations due to the introduction of CESTOL at selected major airports. These are the 34 domestic airports identified in the Federal Aviation Administration's Operational Evolution Plan (OEP). The analysis process uses two fast-time simulation tools to separately model local and NAS-wide air traffic operations using predicted flight schedules for a 24-hour study period in 2016. These tools are the Sen sis AvTerminal model and NASA's Airspace Concept Evaluation System (ACES). We use both to simulate conventional-aircraft-only and CESTOL-mixed-with-conventional-aircraft operations. Both tools apply 4-dimension trajectory modeling to simulate individual flight movement. The study applies AvTerminal to model traffic operations and procedures for en route and terminal arrival and departures to and from KEWR. These AvTerminal applications model existing arrival and departure routes and profiles and runway use configurations, with the assumption jet-powered, large-sized civil CESTOL aircraft use a short runway and standard turboprop arrival and departure procedures. With these rules, the conventional jet and CESTOL aircraft are procedurally separated from each other geographically and in altitude during tenninal airspace approach and departure operations, and each use a different arrival runway. AvTeminal implements its unique Focal-point Scheduling Process to sequence, space and delay aircraft to resolve spacing and overtake conflicts among flights in the airspace and airport system serving KEWR. This Process effectively models integrated arrival and departure operations. AvTerminal assesses acceptance rates and delay magnitude and causality at selected locations, including en route outer boundary fixes, tenninal airspace arrival and departure boundary fixes, terminal airspace arrival merge and departure diverge fixes, and runway landing and takeoff runways. The analysis compares the resulting capacity impacts, flight delays and delay sources between CESTOL and conventional KEWR operations. AvTerminal quantitative results showed that CESTOL has significant capability to increase airport arrival acceptance rates (35-40% at KEWR) by taking advantage of otherwise underused airspace and runways where available. The study extrapolates the AvTerminal-derived KEWR peak arrival and departure acceptance rates to estimate capacity parameter values for each of the OEP airports in the ACES modeling of traffic through the entire NAS network. The extrapolations of acceptance rates allow full, partial or no achievement of CESTOL capacity gains at an OEP airport as determined by assessments of the degree to which local procedures allow leveraging of CESTOL capabilities. These assessments consider each OEP airport's runway geometries, runway system configurations, airport and airspace operations, and potential CESTOL traffic loadings. The ACES modeling, simulates airport and airspace spacing constraints imposed by airport runway system, terminal and en route air traffic control and traffic flow management operations using airport acceptance rates representing conventional-aircraft-only and CESTOL-mixed operations. CEOL aircraft are assumed to have Mach 0.8, and alternatively Mach 0.7, cruise speeds to examine compatibility with conventional aircraft operations in common airspace. The ACES results provides estimates of CESTOL delay impact NAS-wide and at OEP airports due to changes in OEP airport acceptance rates and changes in en route airspace potential conflict rates. Preliminary results show meaningful nationwide delay reductions (20%) due to CESTOL operations at 34 major domestic airports.

Couluris, G. J.↗

Versatile Sequential Casting Processing for Highly Efficient and Stable Binary Organic Photovoltaics

Forming an ideal bulk heterojunction (BHJ) morphology is a critical issue governing the photon to electron process in organic solar cells (OSCs). Complementary to the widely-used blend casting (BC) method for BHJ construction, sequential casting (SC) can also enable similar or even better morphology and device performance for OSCs. Here, BC and SC methods on three representative donor:acceptor (D:A) blends are utilized, that is, PM6:PC 71 BM, PM6:IT-4F and PM6:L8-BO. Higher power conversion efficiencies (PCEs) in all cases by taking advantage of beneficial morphology from SC processing are achieved, and a champion PCE of 18.86% (certified as 18.44%) based on the PM6:L8-BO blend is reached, representing the record value among binary OSCs. The observations on phase separation and vertical distribution inspire the proposal of the swelling–intercalation phase-separation model to interpret the morphology evolution during SC processing. Further, the vertical phase segregation is found to deliver an improvement of device performance via affecting the charge transport and collection processes, as evidenced by the D:A-ratio-dependent photovoltaic properties. Besides, OSCs based on SC processing show advantages on device photostability and upscale fabrication. Finally, this work demonstrates the versatility and efficacy of the SC method for BHJ-based OSCs.

14 SOLAR ENERGY↗

Technology for Solar Array Production on the Moon

Silicon, aluminum, and glass are the primary raw materials that will be required for production of solar arrays on the moon. A process sequence is proposed for producing these materials from lunar regolith is proposed, consisting of separating the required materials from lunar rock with fluorine. Fluorosilane produced by this process is reduced to silicon; the fluorine salts are reduced to metals by reaction with metallic potassium. Fluorine is recovered from residual MgF and CaF2 by reaction with K2O. Aluminum, calcium oxide, and magnesium oxide are recovered to manufacture structural materials and glass.

Landis, Geoffrey A.↗

Stakeholder-Engaged Structured Decision Making for the Los Alamos Legacy Cleanup Mission - 20501

The Los Alamos National Laboratory (LANL) environmental legacy cleanup program requires decisions to be made for environmental remediation, decommissioning and disposal or management of radioactive waste. This legacy cleanup program was established to address groundwater contamination, material disposal areas (MDAs) that have been used to dispose of radioactive and other waste material, and 'aggregate areas' that might produce radioactive or other chemical waste as a result of remediation activities. The LANL site is regulated for environmental concerns under the Resource Conservation and Recovery Act (RCRA). However, some parts of LANL, such as material disposal area G (MDA G), have disposed of radioactive waste under DOE Order 435.1, and are subject to other regulations. For example, decommissioning the remote-handled TRU material stored in 33 shafts at MDA G falls under EPA's 40 CFR 191. Collectively, the regulations are all aimed in the same direction of finding the best solution, either through constructs such as 'as low as reasonably achievable' (ALARA), considering balancing factors as opposed to only cost and human health risk, and, under EPA regulations such as RCRA and NEPA, evaluating impact from all chemicals and both human health and ecological endpoints. Despite the basic goals and objectives of the regulations or their guidance, the main challenge is in their implementation. Arguably perhaps, but really in principle, all of these (and similar) regulations are asking for a decision analysis to be performed. Implementation challenges encountered have included lack of understanding of decision analysis in the industry, lack of effective stakeholder engagement in the decision analysis process, and lack of appreciation of the need to separate value judgments from science, the latter leading to developing conservative, or protective, science-based models. Conservative models lead to poor solutions, lack of effective stakeholder engagement leads to long drawn out protracted approaches to finding a solution (which also might never be found with this approach), and lack of understanding of decision analysis and Bayesian statistics causes poor models to be built, which creates unfortunate situations of 'garbage in, garbage out' becoming the basis for decision making. Stakeholder-engaged structured decision making (SDM) is an approach to solving problems that relies on the theory of decision science to involve stakeholders in the decision-making process. This approach incorporates stakeholder values using a scientifically rigorous methodology that separates value judgments from science in a way that helps avoid the pitfalls of biased, protective, or conservative modeling. This approach has its foundation in Keeney's 1992 treatise on value-focused thinking [1]. Keeney advocated a paradigm shift in decision making based on the idea that the standard way of thinking about decisions is backwards. The standard approach of focusing first on identifying alternatives rather than on articulating values results in a reactive approach with the emphasis on mechanics and fixed choices instead of the core values that have meaning to stakeholders. This paradigm shift effectively engages all stakeholders in the decision-making process while using a values focused thinking approach that can lead to the identification of decision opportunities and the creation of better alternatives. The intent is to be proactive and generate solutions that are related directly to values and objectives as identified by stakeholders. There are, perhaps, two overarching reasons why SDM can be used to benefit LANL's environmental legacy cleanup. Some of LANL's remaining waste management and environmental management problems are challenging and complex (for example, the Cr and RDX plumes, and MDAs) and while the traditional approach has, arguably, worked well for relatively simple risk-based problems, it cannot, or should not, be applied to more complex problems if the most effective and efficient solutions are desired. The second reason is cost. This has perhaps become more critical since publication of the Government Accountability Office (GAO) reports that DoE's environmental liability is considered a high-risk concern for the nation [2]. The focus of SDM is on structuring solutions to decision risk problems by first addressing stakeholder and decision maker values and subsequently developing decision objectives and ways to measure those objectives, preference weighting across objectives, identifying decision alternatives that best achieve those values, and characterizing uncertainty in predictions of the measures. Because a complete decision model is created using SDM, it can be evaluated to find the main elements of the model that drive, or predict, the best solution. This approach creates complete decision models that are transparent, traceable, reproducible and technically defensible. The science behind SDM, or decision analysis, is well founded, yet it is not unusual to see ad hoc approaches to decision making implemented under various environmental regulations that are pertinent to the LANL site, including NEPA, RCRA and DOE Order 435.1. Such ad hoc approaches are often not transparent or traceable, and lack reproducibility and technical defensibility. The LANL legacy cleanup program has embarked on using SDM to address the complex problems that remain. Stakeholder meetings have been held, and a prototype version of the stakeholder value system has been developed. Further meetings are expected in the future to address specific project needs. This is a long-term endeavor considering the complex environmental problems faced by DOE EM in Los Alamos (EM-LA), and careful planning, consideration of stakeholder value systems, and engagement with stakeholders throughout the SDM process is expected to lead to a successful endpoint. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Step-by-step state-selective tracking of fragmentation dynamics of water dications by momentum imaging

Abstract The double photoionization of a molecule by one photon ejects two electrons and typically creates an unstable dication. Observing the subsequent fragmentation products in coincidence can reveal a surprisingly detailed picture of the dynamics. Determining the time evolution and quantum mechanical states involved leads to deeper understanding of molecular dynamics. Here in a combined experimental and theoretical study, we unambiguously separate the sequential breakup via D + + OD + intermediates, from other processes leading to the same D + + D + + O final products of double ionization of water by a single photon. Moreover, we experimentally identify, separate, and follow step by step, two pathways involving the b 1 Σ + and a 1 Δ electronic states of the intermediate OD + ion. Our classical trajectory calculations on the relevant potential energy surfaces reproduce well the measured data and, combined with the experiment, enable the determination of the internal energy and angular momentum distribution of the OD + intermediate.

74 ATOMIC AND MOLECULAR PHYSICS↗

Thermochemical production of hydrogen via multistage water splitting processes

This paper presents and reviews the fundamental thermodynamic principles underlying thermochemical water splitting processes. The overall system is considered first and the temperature limitation in process thermal efficiency is developed. The relationship to an ideal water electrolysis cell is described and the nature of efficient multistage reaction processes is discussed. The importance of the reaction entropy change and the relation of the reaction free energy change to the work of separation is described. A procedure for analyzing thermochemical water splitting processes is presented and its use to calculate individual stage efficiency is demonstrated. A number of processes are used to illustrate the concepts and procedures.

Funk, J. E.↗

Status and outlook of flow separation control

Under certain conditions, wall-bounded flows separate. To improve the performance of natural or man-made flow systems, it may be beneficial to delay or advance this detachment process. The present article reviews the status and outlook of separation control for both steady and unsteady flows. Both passive and active techniques to prevent or to provoke flow detachment are considered and suggestions are made for further research.

Gad-El-hak, Mohamed↗

Phase segregation mechanisms of small molecule-polymer blends unraveled by varying polymer chain architecture

As phase separation between the small-molecule semiconductor and the polymer binder is the key enabler of blend-based organic field-effect transistors (OFETs) fabricated by low-cost solution processing, it is crucial to understand the underlying phase separation mechanisms that determine the phase morphology, which significantly impacts device performance. Beyond the parameter space investigated in previous work, here we investigate the formation of blends by varying the branch architecture of the polymer binder and by shortening the solvent dry time using ultrasonic spray casting. The phase morphologies of the resulting blend films have been thoroughly characterized with a variety of techniques in three dimensions over multiple length scales, including AFM, energy-filtered transmission electron microscope, and neutron reflectivity, and have been correlated with electrical transport performance. From the results, we have inferred that the phase morphology is kinetically determined, limited by the inherent slow movement of polymer macromolecules. The kinetic picture, supported by molecular dynamics modeling, not only consistently explains our observations but also resolves inconsistencies in previous works. The achieved mechanistic understanding will guide further optimization of blend-based organic electronics, such as OFETs and organic photovoltaics.

36 MATERIALS SCIENCE↗

Ion separations with membranes

Ion separations are important for resource recovery, water treatment, and energy production and storage. Techniques such as chemical precipitation, selective adsorption, and solvent extraction are effective, but membranes may separate ions continuously with less waste and lower energy costs. Separation of monovalent and multivalent ions with nanofiltration or electrodialysis membranes already enables water softening and edible salt purification. Similar membranes are attractive as separators in vanadium redox flow batteries. Selective partitioning of divalent counter-ions into ion-exchange membranes even allows transport of these ions against their concentration gradients in salt mixtures. However, separations of ions with the same charge is more challenging. Recent research demonstrated highly selective ion “sieving” at small scales. Here, separations using electrical potentials and differences in ion electrophoretic mobilities are promising, but relatively unexplored. Carrier-mediated transport affords high selectivity in liquid membranes, but these systems are not very stable, and selective transport via hopping between anchored carriers has proven elusive. Finally, this paper discusses how concentration polarization decreases selectivities in many membrane processes. Although development of selective, inexpensive ion-separation membranes is a work in progress, successes in water softening and edible salt purification suggests that future selective membranes will serve as complementary methods to traditional purification techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

D2NO: Efficient handling of heterogeneous input function spaces with distributed deep neural operators

Neural operators have been applied in various scientific fields, such as solving parametric partial differential equations, dynamical systems with control, and inverse problems. However, challenges arise when dealing with input functions that exhibit heterogeneous properties, requiring multiple sensors to handle functions with minimal regularity. To address this issue, discretization-invariant neural operators have been used, allowing the sampling of diverse input functions with different sensor locations. However, existing frameworks still require an equal number of sensors for all functions. We propose a novel distributed approach to further relax the discretization requirements and solve the heterogeneous dataset challenges. Our method involves partitioning the input function space and processing individual input functions using independent and separate neural networks. A centralized neural network is used to handle shared information across all output functions. This distributed methodology reduces the number of gradient descent back-propagation steps, improving efficiency while maintaining accuracy. Here, we demonstrate that the corresponding neural network is a universal approximator of continuous nonlinear operators and present three numerical examples to validate its performance.

97 MATHEMATICS AND COMPUTING↗

Search for the decay of the Higgs boson to a $Z$ boson and a light pseudoscalar particle decaying to two photons

A search for the decay of the Higgs boson to a Z boson and a light, pseudoscalar particle, a, decaying respectively to two leptons and to two photons is reported. The search uses the full LHC Run 2 proton–proton collision data at $\sqrt{s}$ = 13 TeV, corresponding to 139 fb –1 collected by the ATLAS detector. This is one of the first searches for this specific decay mode of the Higgs boson, and it probes unexplored parameter space in models with axion-like particles (ALPs) and extended scalar sectors. The mass of the $a$ particle is assumed to be in the range 0.1–33 GeV. The data are analysed in two categories: a merged category where the photons from the $a$ decay are reconstructed in the ATLAS calorimeter as a single cluster, and a resolved category in which two separate photons are detected. The main background processes are from Standard Model Z boson production in association with photons or jets. The data are in agreement with the background predictions, and upper limits on the branching ratio of the Higgs boson decay to $Za$ times the branching ratio $a → γγ$ are derived at the 95% confidence level and they range from 0.08% to 2% depending on the mass of the $a$ particle. The results are also interpreted in the context of ALP models.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Anions Enhance Rare Earth Adsorption at Negatively Charged Surfaces

Anions are expected to be repelled from negatively charged surfaces. At aqueous interfaces, however, ion-specific effects can dominate over direct electrostatic interactions. Using multiple in situ surface sensitive experimental techniques, we show in this study that surface affinities of SCN – anions are so strong that they can adsorb at a negatively charged floating monolayer at the air–aqueous interface. This extreme example of ion-specific effects may be very important for understanding complex processes at aqueous interfaces, such as chemical separations of rare earth metals. Adsorbed SCN – ions at the floating monolayer increase the overall negative charge density, leading to enhanced trivalent rare earth adsorption. Surface sensitive X-ray fluorescence measurements show that the surface coverage of Lu 3+ ions can be triple the apparent surface charge of the floating monolayer in the presence of SCN – . Comparison to NO 3 – samples shows that the effects are strongly dependent on the character of the anion, providing further evidence of ion-specific effects dominating over electrostatics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward Lithium Recovery Using Modular (and Membraneless) Phase Separation and Extraction (MPSE) Technology with Ionic Liquid (IL) Solvents: Effect of Coatings

In this work, a single-channel slope-plate Modular and Membrane-less Phase Separation and Extraction (MPSE) device was fabricated using 3D printing. The slope-plate was designed with an insertable glass slide to enable surface modification with coatings. Self-assembled monolayers (SAMs) and perfluoropolyether (Zdol) coatings were applied to tailor surface wettability and enhance phase separation. Using a model biphasic system of water and hexadecane, both coatings significantly improved the separation efficiency compared to the uncoated device by promoting selective wetting. Building on these results, lithium extraction from a simulated saline solution was investigated using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf₂]) as the ionic liquid (IL) extractant. The IL effectively extracted Li⁺ from the aqueous phase in bulk extraction, demonstrating its potential for lithium recovery. However, the low interfacial tension between the IL and aqueous phases posed challenges for phase separation. The application of SAM and Zdol coatings effectively mitigated this issue. Overall, integrating tailored surface chemistry with the slope-plate MPSE design shows great promise as an efficient and scalable platform for studying liquid–liquid separation and optimizing ionic liquid–based extraction processes for lithium recovery from saline sources.

3D printing↗

3D-Printed Porous Supramolecular Sorbents for Cobalt Recycling

Electronic waste recycling is a recognized global challenge that requires new strategies to bind and release critical materials selectively, such as cobalt present in lithium-ion batteries. To address this challenge, hierarchical 3D-printed porous polymer scaffolds bearing supramolecular receptors were prepared using vat photopolymerization and their cobalt binding profiles were examined as a function of matrix polarity. By combining high-resolution digital light processing (DLP) with polymerization-induced phase separation (PIPS), functional acrylic copolymer networks with micrometer-level precision of geometry and nanometer-level pores were generated. Covalent integration of a methacrylate-functionalized bisdicyclohexyl acetamide (BDCA-MA) receptor enabled binding and release of cobalt(II) chloride (CoCl 2 ) via a solvent polarity switch mechanism involving a change in solvent from ethanol to water. The present structures proved reusable as shown by sustained high binding efficiency over five bind and release cycles. Finally, this platform represents a “green” and energy conscious method for future electronic waste recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanism of monovalent and divalent ion mobility in Nafion membrane: An atomistic simulation study

Polymer cation exchange membranes (CEMs) are widely used in water treatment processes. The fundamental factors that control the separation and selectivity of cations with different valences in CEMs are not fully understood. In this study, we use atomistic molecular dynamics simulations to investigate the underlying molecular mechanisms that control the mobility of cations with different valences in Nafion membranes. Our results indicate structural differences in binding of monovalent and divalent cations, which gives rise to differences in ion diffusion in Nafion. Monovalent cations are shown to be “territorially” bound, i.e., bound while partially hydrated, to the fixed charge groups whereas divalent cations are shown to be “site” bound, i.e., bound while fully dehydrated, to the charge groups on the polymer. This difference in binding structure gives rise to differences in transport characteristics of cations in Nafion.

Chemistry↗

Distinct vibrational motions promote disparate excited-state decay pathways in cofacial perylenediimide dimers

A complex interplay of structural, electronic, and vibrational degrees of freedom underpins the fate of molecular excited states. Organic assemblies exhibit a myriad of excited-state decay processes, such as symmetry-breaking charge separation (SB-CS), excimer (EX) formation, singlet fission, and energy transfer. Recent studies of cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) (PDI) multimers demonstrate that slight variations in core substituents and H- or J-type aggregation can determine whether the system follows an SB-CS pathway or an EX one. However, questions regarding the relative importance of structural properties and molecular vibrations in driving the excited-state dynamics remain. Here, we use a combination of two-dimensional electronic spectroscopy, femtosecond stimulated Raman spectroscopy, and quantum chemistry computations to compare the photophysics of two PDI dimers. The dimer with 1,7-bis(pyrrolidin-1′-yl) substituents (5PDI2) undergoes ultrafast SB-CS from a photoexcited mixed state, while the dimer with bis-1,7-(3′,5′-di-t-butylphenoxy) substituents (PPDI2) rapidly forms an EX state. Examination of their quantum beating features reveals that SB-CS in 5PDI2 is driven by the collective vibronic coupling of two or more excited-state vibrations. In contrast, we observe signatures of low-frequency vibrational coherence transfer during EX formation by PPDI2, which aligns with several previous studies. We conclude that key electronic and structural differences between 5PDI2 and PPDI2 determine their markedly different photophysics.

Chemistry↗