Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “chemical specificity”

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

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

At least 667 records · Page 37

Modeling prebiotic chemistries with quantum accuracy at classical costs

Molecular Dynamics (MD) simulations using classical force-fields are commonly employed in numerous scientific investigations. However, many natural processes involve bond breaking and quantum forces. This complexity is compounded by the presence of multiple competing length and timescales. For example, accurately modeling the thermodynamics and dynamics of a chemical reaction requires accounting for the concerted movements of numerous solvent molecules and ions with their own fast or slow timescales. While widely used static Density Functional Theory (DFT) calculations at 0 temperature can be beneficial for such investigations, they do not account for dynamics, and lack precision in describing the molecular environments. They particularly fail at correct, rigorous treatments of finite-temperature fluctuations, and thus generalization to experimentally relevant conditions. In PNAS Benayad et al develop a scalable, generalizable approach for designing Neural Network Potentials (NNPs) that can handle chemical reactivity in solvated systems with quantum accuracy at classical costs. Specifically, they study phosphoester bond formation and rupture, which is fundamentally relevant to the Phosphorus-Oxygen bond formation central to life, and especially for the RNA world hypothesis. The framework developed here has the potential to generalize to different chemical reactions of energy and biological relevance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust Exploration and Commercial Missions to the Moon Using LANTR Propulsion and In-Situ Propellants Derived from Lunar Polar Ice (LPI) Deposits

The nuclear thermal rocket (NTR) has frequently been identified as a key space asset required for the human exploration of Mars. This proven technology can also provide the affordable access through cislunar space necessary for commercial development and sustained human presence on the Moon. It is a demonstrated technology capable of generating both high thrust and high specific impulse (Isp 900 s) twice that of todays best chemical rockets. Nuclear lunar transfer vehicles consisting of a propulsion stage using three approx.16.5 klbf "Small Nuclear Rocket Engines (SNREs)", an in-line propellant tank, plus the payload can enable a variety of reusable lunar missions. These include cargo delivery and crewed lunar landing missions. Even weeklong "tourism" missions carrying passengers into lunar orbit for a day of sightseeing and picture taking are possible. The NTR can play an important role in the next phase of lunar exploration and development by providing a robust in-space lunar transportation system (LTS) that can allow initial outposts to evolve into settlements supported by a variety of commercial activities such as in-situ propellant production used to supply strategically located propellant depots and transportation nodes. The processing of LPI deposits (estimated to be approx. 2 billion metric tons) for propellant production - specifically liquid oxygen (LO2) and hydrogen (LH2) can significantly reduce the launch mass requirements from Earth and can enable reusable, surface-based lunar landing vehicles (LLVs) using LO2/LH2 chemical rocket engines. Afterwards, LO2/LH2 propellant depots can be established in lunar polar and equatorial orbits to supply the LTS. At this point a modified version of the conventional NTR called the LO2-augmented NTR, or LANTR would be introduced into the LTS allowing bipropellant operation and leveraging the mission benefits of refueling with lunar-derived propellants (LDPs) for Earth return. The bipropellant LANTR engine utilizes the large divergent section of its nozzle as an afterburner into which oxygen is injected and supersonically combusted with nuclear preheated hydrogen emerging from the engines choked sonic throat essentially scramjet propulsion in reverse. By varying the oxygen-to-hydrogen mixture ratio, LANTR engines can operate over a range of thrust and Isp values while the reactor core power level remains relatively constant. A LANTR-based LTS offers unique mission capabilities including short transit time crewed cargo transports. Even a commuter shuttle service may be possible allowing one-way trip times to and from the Moon on the order of 36 hours or less. If only 1 of the postulated water ice trapped in deep shadowed craters at the lunar poles were available for use in lunar orbit, such a supply could support daily commuter flights to the Moon for many thousands of years! The proposed paper outlines an evolutionary mission architecture and examines a variety of mission types and transfer vehicle designs, along with the increasing demands on LDP production as mission complexity and delta V requirements increase. A comparison of vehicle features and engine operating characteristics are also provided together with a discussion of the propellant production and mining requirements, and issues, associated with using LPI as the source material.

Nuclear Thermal Propulsion↗

Position-specific carbon isotope analysis of serine by gas chromatography/Orbitrap mass spectrometry, and an application to plant metabolism

Position-specific 13 C/ 12 C ratios within amino acids remain largely unexplored in environmental samples due to methodological limitations. We hypothesized that natural-abundance isotope patterns in serine may serve as a proxy for plant metabolic fluxes including photorespiration. Here we describe an Orbitrap method optimized for the position-specific carbon isotope analysis of serine to test our hypothesis and discuss the generalizability of this method to other amino acids. Position-specific carbon isotope ratios of serine were measured using a Thermo Scientific™ Q Exactive™ GC Orbitrap™. Amino acids were hydrolyzed from Arabidopsis biomass, purified from potential matrix interferences, and derivatized alongside standards. Derivatized serine (N,O-bis(trifluoroacetyl)methyl ester) was isolated using gas chromatography, trapped in a reservoir, and purged into the electron ionization source over tens of minutes, producing fragment ions containing different combinations of atoms from the serine-derivative molecule. The 13 C/ 12 C ratios of fragments with monoisotopic masses of 110.0217, 138.0166, and 165.0037 Da were monitored in the mass analyzer and used to calculate position-specific δ 13 C values relative to a working standard. This methodology constrains position-specific δ 13 C values for nanomole amounts of serine isolated from chemically complex mixtures. The δ 13 C values of fragment ions of serine were characterized with ≤1‰ precisions, leading to propagated standard errors of 0.7–5‰ for each carbon position. Position-specific δ 13 C values differed by up to ca 28 ± 5‰ between serine molecules hydrolyzed from plants grown under contrasting pCO 2 , selected to promote different fluxes through photosynthesis and photorespiration. The method was validated using pure serine standards characterized offline. Here this study presents the first Orbitrap-based measurements of natural-abundance, position-specific carbon isotope variation in an amino acid isolated from a biological matrix. We present a method for the precise characterization of isotope ratios in serine and propose applications probing metabolism in plants. We discuss the potential for extending these approaches to other amino acids, paving the way for novel applications.

59 BASIC BIOLOGICAL SCIENCES↗

Experimental and fuel-surrogates modeling study of the high-pressure pyrolysis of specialty cetane number fuels: implications for fall-off in ethylene unimolecular dissociation

Single pulse shock tube experiments were conducted at 50 atm nominal pressure and 4 ms nominal reaction time over a temperature range of 900–1800 K, to study the pyrolysis speciation of a multi-component jet fuel, F-24, and six cetane number (CN) specialty fuels - CN30, CN35, CN40, CN45, CN50, and CN55. Gas chromatography (GC) was used to qualitatively and quantitatively analyze the post shock gases. The relationship between the formation of key pyrolysis species and the chemically controlled combustion propensity as reflected by the cetane number of each fuel was examined. A surrogate-based mechanism from the CRECK Modelling Group and chemical-functional group based optimized surrogates (CFGO) were used to simulate the pyrolysis speciation results. The model was able to capture the chemistry of most species except two important pyrolysis intermediates – ethylene and acetylene. Chemical kinetic analyses were performed to identify the important reactions which affect the chemistry of these species; however, the rate parameters of critical reactions were found to be unsuitable for simulating the present high-pressure studies. Here, to address this unsuitability, a theory-based fall-off analysis for three reactions representing the decomposition of ethylene and subsequent formation of acetylene was performed, and these are included in an updated version of the CRECK mechanism. This update resolves discrepancies between the experimental results and simulations for ethylene and acetylene. Reaction flux analyses using the updated surrogate model were also performed to identify the important reaction pathways responsible for the formation of crucial species and to provide an analysis of the chemistry of complex multi-component fuel systems. The fundamental reactions responsible for driving pyrolysis chemistry were greatly influenced by the chemical functional groups present in these fuels. In addition to updating the rate parameters of specific reactions to improve modeling, this study also emphasizes the effectiveness of the fuel-surrogate approach, where surrogates representing the chemical functional group composition of the parent fuel serve as a valuable tool for predicting the combustion chemistry of novel fuels.

Chemical Kinetics↗

Artificial Intelligence for Conjugated Polymers

Conjugated polymers have garnered significant attention due to their diverse applications in electronics, photonics, and energy storage. However, realizing their full potential poses a formidable challenge, as their design has historically relied on iterative adjustments and continuous inspiration from researchers. Traditional methods often struggle to efficiently navigate their vast chemical landscape. In this work, the application of artificial intelligence (AI), specifically machine learning (ML), needs to be discussed in the realm of conjugated polymers. Our paper emphasizes the importance of understanding the structure–property relationships of these polymers and how ML can facilitate property prediction and inverse-design. We delve into various chemical fingerprints, structural descriptors, and ML algorithms, showcasing their utility across a spectrum of applications, including simulations, glass transition temperature determination, photovoltaics, reorganization energy for charge transport, photocatalysts, and sensors. Finally, we give some outlooks in this filed and propose unexplored areas within the field that hold the potential to benefit from ML techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvated Electrons Have Multiple Personalities in Molten Salts

P-Crosscut: Solvated Electrons Have Multiple Personalities in Molten Salts [EFRC – MSEE] Alejandro Ramos-Ballesteros;1 Hung H. Nguyen;2 Kazuhiro Iwamatsu;3 Santanu Roy;4 Vyacheslav Bryantsev;4 Michael E. Woods;1 Ruchi Gakhar;1 Phillip Halstenberg;4 Bobby Layne;5 Jay A. LaVerne;6 Claudio J. Margulis:2* and James F. Wishart5* 1Idaho National Laboratory; 2The University of Iowa; 3Hunter College; 4Oak Ridge National Laboratory; 5Brookhaven National Laboratory; 6University of Notre Dame Abstract: The solvated (eS–) is a powerful reducing agent and one of the primary products of molten salt radiolysis. In these extreme high-temperature environments, the eS– can initiate cascades of redox processes that significantly alter the physical and chemical properties of a molten salt, posing challenges for molten salt reactor (MSR) performance and longevity. Consequently, mastering the fundamental behavior of the eS– could enable the design of specific molten salt mixtures with tailored Lewis acidities for controlling the speciation and chemical reactivity of the eS–, thereby mitigating its overall impact on MSR technologies. Here, we use time-resolved electron pulse radiolysis techniques for determining chemical kinetics and transient absorption spectra, combined with ab initio molecular dynamics simulations to explore the influence of multivalent metal cations on the fundamental speciation and distribution of eS– coordination environments.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

A mass spectrometry-based high-throughput screening method for engineering fatty acid synthases with improved production of medium-chain fatty acids

Microbial cell factories have been extensively engineered to produce free fatty acids (FFAs), key components of crucial nutrients, soaps, industrial chemicals, and fuels. Yet, our ability to control the specificity of microbially synthesized FFAs is still limited for medium-chain fatty acids (MCFAs), which is mainly due to lack of high-throughput approaches for FFA analysis. Here we report a mass spectrometry (MS)-based method for rapid profiling of MCFAs in Saccharomyces cerevisiae by using membrane lipids as a proxy. Specially, matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) MS was used to detect shorter acyl chain phosphatidylcholines from membrane lipids and the m/z peak ratio at 730 and 758 was used as an index for improved MCFA production. This yeast colony-based method can be performed at a rate of ~2 second per sample, which is much faster than the gold standard gas chromatography (GC)-MS (typically > 30 min per sample). To demonstrate the power of this method, we performed site-saturation mutagenesis of the yeast fatty acid synthase and identified 9 mutants that resulted in improved MCFA production relative to the wild-type strain. This colony-based MALDI-ToF MS screening method offers an alternative way for engineering microbial fatty acid compositions in a high-throughput manner.

59 BASIC BIOLOGICAL SCIENCES↗

The influence of thermochemistry on the reactivity of propane, the pentane isomers and $n$-heptane in the low temperature regime

In this study, the influence of thermochemistry on the reactivity of fuels at low temperatures (600–1000 K) is studied here. Specifically, the effect of different sets of thermochemistry on chemical model predictions is explored, where various sets are calculated at different levels of theory in addition to recently updated group additivity values. Experimentally measured ignition delay times for propane, the pentane isomers and n-heptane are simulated using NUIGMech1.2 and replacing the thermochemistry of the low-temperature species with the calculated values. For propane, three different thermochemistry sets were calculated, namely CCSD(T)-F12/TZ-F12//B2PLYP-D3/TZ//B2PLYP-D3/TZ (QM1), CCSD(T)-F12/TZ-F12//B2PLYP-D3/TZ//ωB97X-D/TZ (QM2) and B2PLYP-D3/TZ/ωB97X-D/6-31G*//ωB97X-D/6-31G* (QM3). The QM2 results provide parameters to optimize new group additivity (NGA) values which are used to calculate the fourth set of thermochemistry. The model predictions using these four sets are compared to those using NUIGMech1.2 for propane. As the QM1 and QM2 calculations are expensive, the thermochemistry calculated from the QM3 and NGA calculations are used in the pentane isomer and n-heptane models. For all of the models, it is found that the thermochemistry of the species involved in the low-temperature reaction sequence ($RH$, $\dot{R}$, $RO_2H$, $R\dot{O}_2$, $\dot{Q}OOH$ and $\dot{O}_2QOOH$ species) significantly affect fuel reactivity. The NGA values were developed based on all of these species except $\dot{O}_2QOOH$ radicals. The thermochemistry of $\dot{O}_2QOOH$ species cannot be accurately calculated with the NGA representations due to the importance of non-next-nearest neighbor interactions of –OOH substitution. Further development of the NGA method to capture such interactions is in progress. Overall, the model developed using the NGA thermochemistry shows better agreement with experimental data than the model using thermochemistry from affordable and prominent QM methods, such as QM3. Based on the results presented for propane, the pentane isomers and n-heptane, the thermochemistry calculated using the NGA method can be used to model the oxidation of higher order hydrocarbons at low temperatures.

33 ADVANCED PROPULSION SYSTEMS↗

Electron Microscopy Studies of Soft Nanomaterials

This review highlights recent efforts on applying electron microscopy (EM) to soft (including biological) nanomaterials. We will show how developments of both the hardware and software of EM have enabled new insights into the formation, assembly, and functioning (e.g., energy conversion and storage, phonon/photon modulation) of these materials by providing shape, size, phase, structural, and chemical information at the nanometer or higher spatial resolution. Specifically, we first discuss standard real-space two-dimensional imaging and analytical techniques which are offered conveniently by microscopes without special holders or advanced beam technology. The discussion is then extended to recent advancements, including visualizing three-dimensional morphology of soft nanomaterials using electron tomography and its variations, identifying local structure and strain by electron diffraction, and recording motions and transformation by in situ EM. On these advancements, we cover state-of-the-art technologies designed for overcoming the technical barriers for EM to characterize soft materials as well as representative application examples. Here, the even more recent integration of machine learning and its impacts on EM are also discussed in detail. With our perspectives of future opportunities offered at the end, we expect this review to inspire and stimulate more efforts in developing and utilizing EM-based characterization methods for soft nanomaterials at the atomic to nanometer length scales in academic research and industrial applications.

Imaging↗

How Selective Transport Layer Improves Efficiency and Durability of Proton Exchange Membrane Fuel Cells

In any electrochemical device, the separator or membrane allows specific ions to transport but blocks electrons and other chemical species, enabling the electrochemical energy to be harvested. However, small amounts of undesired species are known to permeate through the membrane, reducing overall system efficiency and lifetime. An emerging concept called the “Selective Transport Layer” preferentially allows only protons to pass through but reduces the permeance of other species by a meaningful degree. Here, in this study, we demonstrate that a 60 nm thick graphene oxide composite layer can be very effective in reducing gas and ion permeation, even for a gas as small as H 2 , while not noticeably increasing proton transport resistance. In electrode and membrane accelerated stability tests, we show that both electrode and membrane durability are improved by a factor of two. Microscopy and mathematic simulations confirm that the graphene oxide composite is effective in blocking transport of dissolved Pt 2+ . The improved durability and reduced H 2 fuel crossover are expected to substantially reduce initial and operating costs of the fuel cell system. How this technology may affect other membrane-based electrochemical devices is also discussed.

Ngo, Phuong Quynh [General Motors, Pontiac, MI (Un↗

Radionuclide Waste Disposal: Development of Multi-scale Experimental and Modeling Capabilities (Final Report)

The DOE EPSCoR Implementation project “Radioactive waste management: Development of multi-scale experimental and modeling capabilities” helped to develop a team of scientists and engineers from Clemson University, South Carolina State University, and the University of South Carolina to address the disposition of nuclear wastes and study the transport of radioisotopes from a waste repository in the near and far field. The project involved 20 faculty from the three institutions as well as 13 postdoctoral fellows, 32 graduate students, and 32 undergraduate students and was active from 2014-2019. Additionally, we forged new collaborations with nine researchers from DOE laboratories SRNL, LLNL, and ANL as well as the University of Manchester and the China Academy of Engineering Physics. The overarching goal of the project was to understand the conditions under which important classes of co-reactants, ranging from counter ions in crystal lattices to dissolved oxygen in pores, control the chemistry and transport characteristics of radionuclides in engineered waste forms and natural soils. Our approach was to characterize the time and length scales over which non-equilibrium states are maintained by rate-limiting, or rate-enhancing, reactions between radionuclides and co-reactants due to interactions between physical mass-transfer processes (i.e., advection, diffusion) and (biogeo) chemical reactions. We have focused our project on three specific classes of reactions relevant to radionuclide transport at DOE legacy sites: ion exchange/substitution, ligand complexation, and redox-mediated reactions. Understanding radionuclide migration requires detailed knowledge of how changes to a system – whether engineered or natural – drive the behavior of co-reactants, which in turn provide the geochemical context controlling radionuclide transport. Student engagement and training were a primary focus of the project in order to create a pipeline of researchers who could work in the area of nuclear waste disposition to support the state and the nation. Over the duration of the project we worked with 32 undergraduate, graduated 18 M.S. students and 14 Ph.D. students, and advised 13 postdoctoral fellows. The Ph.D students and postdocs have primarily taken positions at DOE laboratories, academia, and industry. Through our collaborative team, numerous follow on projects have been started with over $5M in sponsored research. Additionally, thus far the team has published 53 peer reviewed papers and given over 75 technical presentations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA Office of Aeronautics and Space Technology Summer Workshop. Volume 5: Propulsion technology panel, part 1

Payload experiments which could be carried out in near earth space using the shuttle orbiter, its payload bay, the Spacelab, and/or some free-flying device that might be used for long duration testing were identified. Specific areas examined in terms of user requirements include: chemical propulsion, nuclear propulsion (fission, fussion, radioisotopes), and collected energy (coherent energy and solar electromagnetic energy). Cost reduction objectives for advanced propulsion technology development were also developed.

Source record↗

Current aspects of occupational chemical carcinogenesis

The history of measures to control occupational exposure to carcinogenic substances is reviewed. Health hazards associated with exposure to a certain chemical substance must be considered not only from the aspects of its acute or chronic toxicity, but also from its potential to produce tumors (latent effect). There can be no clear distinction between classic toxicity and oncogenesis until the mechanisms of both are completely understood for a given chemical substance. The assessment of carcinogenic potential for a specific substance must include the consideration of published information, monitoring and control data from the affected industry, and the in-depth epidemiologic experience of affected employees.

Lassiter, D.↗

A new concept in laser-assisted chemistry - The electronic-field representation

Electronic-field representation is proposed as a technique for laser-assisted chemistry. Specifically, it is shown that several field-assisted chemical processes can be described in terms of mixed matter-field quantum states and their associated energies. The technique may be used to analyze the effects exerted by an intense laser on both bound and unbound molecular systems, and to investigate other field-induced effects including multiphoton processes, emission, and photodissociation.

George, T. F.↗

Thermal Storage Applications Workshop. Volume 2: Contributed Papers

The solar thermal and the thermal and thermochemical energy storage programs are described as well as the technology requirements for both external (electrical) and internal (thermal, chemical) modes for energy storage in solar power plants. Specific technical issues addressed include thermal storage criteria for solar power plants interfacing with utility systems; optimal dispatch of storage for solar plants in a conventional electric grid; thermal storage/temperature tradeoffs for solar total energy systems; the value of energy storage for direct-replacement solar thermal power plants; systems analysis of storage in specific solar thermal power applications; the value of seasonal storage of solar energy; criteria for selection of the thermal storage system for a 10 MW(2) solar power plant; and the need for specific requirements by storage system development teams.

Source record↗

New polymers for phase partitioning

The synthesizing of several polyethylene glycols having crown ethers attached is reported. This work led to the identification of three new polymer types which promise to be more effective at selectively binding specific cell types. Work was completed on identification of chemical properties of the new polymer crowns and on development of new techniques for determination of polymer-phase composition.

Harris, J. M.↗

Evaluating Energy Conversion Efficiency

Devices that convert solar radiation directly into storable chemical or electrical energy, have characteristic energy absorption spectrum; specifically, each of these devices has energy threshold. The conversion efficiency of generalized system that emcompasses all threshold devices is analyzed, resulting in family of curves for devices of various threshold energies operating at different temperatures.

Byvik, C. E.↗