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At least 775 records · Page 43

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NASA NTRS1976

Prospects for pipeline delivery of hydrogen as a fuel and as a chemical feedstock

The possibility of using hydrogen for storing and carrying energy obtained from nonfossil sources such as nuclear and solar energy is examined. According to the method proposed, these nonfossil raw energy sources will be used to obtain hydrogen from water by three basically distinct routes: (1) electrical generation followed by electrolysis; (2) thermochemical decomposition; and (3) direct neutron or ultraviolet irradiation of hydrogen bearing molecules. The hydrogen obtained will be transmitted in long-distance pipelines, and distributed to all energy-consuming sectors. As a fuel gas, hydrogen has many qualities similar to natural gas and with only minor modifications, it can be transmitted and distributed in the same equipment, and can be burned in the same appliances as natural gas. Hydrogen can also be used as a clean fuel (water is the only combustion product) for automobiles, fleet vehicles, and aircraft.

Gregory, D. P.↗

DOE OSTI2024

Synergistic Combination of Living Ring-Opening Metathesis Polymerization and Atom Transfer Radical Polymerization to Synthesize Structurally Tailored and Engineered Macromolecular Networks

Structurally tailored and engineered macromolecular (STEM) networks are attractive materials for soft robotics, stretchable electronics, tissue engineering, and 3D printing due to their tunable properties. To date, STEM networks have been synthesized by atom transfer radical polymerization (ATRP) or the combination of reversible addition–fragmentation chain-transfer (RAFT) polymerization and ATRP. RAFT polymerization could have limited selectivity with ATRP inimer sites that can participate in radical-transfer processes. On the other hand, living ring-opening metathesis polymerization (ROMP) can produce a polymeric network with latent ATRP initiator sites in high selectivity. Herein, for the first time, we report the syntheses of STEM zero-generation (STEM-0) networks using a monomer, a cross-linker, and an ATRP/ROMP inimer via living ROMP, followed by their modification using a second monomer via ATRP to synthesize STEM first-generation (STEM-1) networks. The mechanical property and swelling capacity analyses of these networks were carried out. A change in mechanical properties and swelling capacity of these networks was observed due to their structural modification.

Absorption↗

NASA NTRS1983

Photochemistry of N2(+) in the daytime F region

The photochemistry of N2(+) in the daytime F region continues to be a source of concern due primarily to the uncertain roles of the metastable O+(2D) ion and possible vibrational excitation. This investigation adopts a unique subset of data from the Atmospheric Explorer C satellite that spans distinct regions near the low-latitude F peak wherein either chemical reactions or electron processes alternatively control the N2(+) abundances. Concentrations of N2(+) calculated according to current theory and including recent laboratory data for O+(2D) losses via N2 are found to exceed ionospheric observations between 220 and 400 km by a factor near 2. Relevant characteristics of the basic molecular ion concentration measurements are described, along with an analysis for select orbits conducted according to current photochemical equilibrium theory. Possible simple modifications of this theory are discussed in terms of the constraints suggested by the nature of the observations.

Breig, E. L.↗

DOE OSTI2022

Precision genome editing in plants using gene targeting and prime editing: existing and emerging strategies

Precise modification of plant genomes, such as seamless insertion, deletion, or replacement of DNA sequences at a predefined site, is a challenging task. Gene targeting (GT) and prime editing are currently the best approaches for this purpose. However, these techniques are inefficient in plants, which limits their applications for crop breeding programs. Recently, substantial developments have been made to improve the efficiency of these techniques in plants. Several strategies, such as RNA donor templating, chemically modified donor DNA template, and tandem-repeat homology-directed repair, are aimed at improving GT. Additionally, improved prime editing gRNA design, use of engineered reverse transcriptase enzymes, and splitting prime editing components have improved the efficacy of prime editing in plants. These emerging strategies and existing technologies are reviewed along with various perspectives on their future improvement and the development of robust precision genome editing technologies for plants.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1978

Surface waves generated by shallow underwater explosions

Surface water waves generated by surface and near surface point explosions are calculated. Taking the impulse distribution imparted at the water surface by the explosion as the overriding mechanism for transferring energy of the explosive to surface wave motion, the linearized theory of Kranzer and Keller is used to obtain the wave displacement in the far field. The impulse distribution is obtained by integrating the pressure wave over an appropriate time interval on a horizontal surface just beneath the undisturbed water surface. For surface explosions, a modified form of the similarity method first used by Collins and Holt is used to obtain the flow field. In the case of submerged explosions, the flow field is estimated by making necessary modifications to Sedov's similarity solution to account for the venting that accompanies the interaction of the leading (blast) wave with the ocean surface. Surface waves generated by a charge at six depths of placement (0.15 m, 0.30 m, 0.61 m, 0.91 m, 1.37 m, 3.05 m) are considered in addition to surface explosions. The results seem to support the existence of an upper critical depth phenomenon (of the type already established for chemical explosions) for point (nuclear) explosions.

Falade, A.↗

DOE OSTI2023

Structure of the Bastnäsite (001) Surface by Crystal Truncation Rod X-ray Diffraction and Ab Initio Molecular Dynamics: Implications for Separations of a Rare Earth Ore Mineral

Bastnäsite ((Ce,La)FCO 3 ) is the primary mineral source of light rare earth elements, but its surface structure is not well understood. This presents a major challenge in improving beneficiation strategies. In this work, a synergistic combination of X-ray scattering and ab initio molecular dynamics (AIMD) was used to gain atomistic insight into the interfacial structure of bastnäsite. Surface X-ray scattering was used to measure crystal truncation rods (CTRs) of the bastnäsite (001) surface, a significant crystal face with a previously unknown termination. The best-fit atomic-scale model of the CTR data features a carbonate layer at the surface, which is stabilized by the relaxation of carbonate groups from their bulk structural positions. AIMD simulations predict similar surface relaxations, which are shown to be influenced by the protonation of oxygen atoms at the surface. Evidence of ordered water at the interface is also observed in the best-fit model and AIMD simulations. Further, the presence of a carbonate layer at this dominant crystal surface is significant for improving separation technologies because most commonly used ligands utilize anionic functional groups to chelate metal cations at particle surfaces. Without modification, anionic ligands are expected to have poor affinity for the carbonate-terminated (001) surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1989

Environmental Projects. Volume 8: Modifications of wastewater evaporation ponds

The Goldstone Deep Space Communications Complex (GDSCC), located in the Mojave Desert about 45 miles north of Barstow, California, and about 160 miles northeast of Pasadena, is part of NASA's Deep Space Network, one of the world's largest and most sensitive scientific telecommunications and radio navigation networks. The Goldstone Complex is managed, technically directed, and operated for NASA by the Jet Propulsion Laboratory (JPL) of the California Institute of Technology in Pasadena, California. Activities at the GDSCC are carried out in support of seven parabolic dish antennas. These activities may give rise to environmental hazards: use of hazardous chemicals, asbestos, and underground storage tanks as well as the generation of hazardous wastes and the disposal of wastewater. Federal, state, and local laws governing the management of hazardous substances, asbestos, underground storage tanks and wastewater disposal have become so complex there is a need to devise specific programs to comply with the many regulations that implement these laws. In support of the national goal of the preservation of the environment and the protection of human health and safety, NASA, JPL, and the GDSCC have adopted a position that their operating installations shall maintain a high level of compliance with these laws. One of the environmental problems at the GDSCC involved four active, operational, wastewater evaporation ponds designed to receive and evaporate sewage effluent from upstream septic tank systems. One pair of active wastewater evaporation ponds is located at Echo Site, while another operational pair is at Mars Site.

Source record↗

DOE OSTI2023

Subsurface Characteristics of Metal-Halide Perovskites Polished by an Argon Ion Beam

Focused ion beam (FIB) techniques have been frequently used to section metal-halide perovskites for microstructural investigations. However, the ion beams directly irradiating the sample surface may alter its properties far different from those of pristine, potentially leading to modified deterioration mechanisms under aging stressors. Here, we combine complementary approaches to measure the subsurface characteristics of polished perovskites and identify the chemical species responsible for the measured properties. Analysis of the experimental results in conjunction with Monte Carlo simulations indicates that atomic displacements and local heating occur in the first ≈15 nm of the subsurface of methylammonium lead iodide (MAPbI 3 ) by glancing-angle Ar + beam irradiation (4 kV at 3°). The lead-rich, iodine-deficient surface promotes rapid phase segregation under thermal aging conditions. On the other hand, despite the subsurface modification, our experiments confirm that the rest of the MAPbI 3 bulk retains the material integrity. Our observation supports that polished perovskites could serve in studying the properties of bulk or buried junctions far away from the altered subsurface with care.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Application of functional genomics for domestication of novel non-model microbes

Abstract With the expansion of domesticated microbes producing biomaterials and chemicals to support a growing circular bioeconomy, the variety of waste and sustainable substrates that can support microbial growth and production will also continue to expand. The diversity of these microbes also requires a range of compatible genetic tools to engineer improved robustness and economic viability. As we still do not fully understand the function of many genes in even highly studied model microbes, engineering improved microbial performance requires introducing genome-scale genetic modifications followed by screening or selecting mutants that enhance growth under prohibitive conditions encountered during production. These approaches include adaptive laboratory evolution, random or directed mutagenesis, transposon-mediated gene disruption, or CRISPR interference (CRISPRi). Although any of these approaches may be applicable for identifying engineering targets, here we focus on using CRISPRi to reduce the time required to engineer more robust microbes for industrial applications. One-Sentence Summary The development of genome scale CRISPR-based libraries in new microbes enables discovery of genetic factors linked to desired traits for engineering more robust microbial systems.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Metabolic engineering of Caldicellulosiruptor bescii for 2,3-butanediol production from unpretreated lignocellulosic biomass and metabolic strategies for improving yields and titers

ABSTRACT The platform chemical 2,3-butanediol (2,3-BDO) is used to derive products, such as 1,3-butadiene and methyl ethyl ketone, for the chemical and fuel production industries. Efficient microbial 2,3-BDO production at industrial scales has not been achieved yet for various reasons, including product inhibition to host organisms, mixed stereospecificity in product formation, and dependence on expensive substrates (i.e., glucose). In this study, we explore engineering of a 2,3-BDO pathway inCaldicellulosiruptor bescii, an extremely thermophilic (optimal growth temperature = 78°C) and anaerobic bacterium that can break down crystalline cellulose and hemicellulose into fermentable C 5 and C 6 sugars. In addition, C. besciigrows on unpretreated plant biomass, such as switchgrass. Biosynthesis of 2,3-BDO involves three steps: two molecules of pyruvate are condensed into acetolactate; acetolactate is decarboxylated to acetoin, and finally, acetoin is reduced to 2,3-BDO.C. besciinatively produces acetoin; therefore, in order to complete the 2,3-BDO biosynthetic pathway,C. besciiwas engineered to produce a secondary alcohol dehydrogenase (sADH) to catalyze the final step. Two previously characterized, thermostable sADH enzymes with high affinity for acetoin, one from a bacterium and one from an archaeon, were tested independently. When either sADH was present inC. bescii,the recombinant strains were able to produce up to 2.5-mM 2,3-BDO from crystalline cellulose and xylan and 0.2-mM 2,3-BDO directly from unpretreated switchgrass. This serves as the basis for higher yields and productivities, and to this end, limiting factors and potential genetic targets for further optimization were assessed using the genome-scale metabolic model ofC. bescii. IMPORTANCE Lignocellulosic plant biomass as the substrate for microbial synthesis of 2,3-butanediol is one of the major keys toward cost-effective bio-based production of this chemical at an industrial scale. However, deconstruction of biomass to release the sugars for microbial growth currently requires expensive thermochemical and enzymatic pretreatments. In this study, the thermo-cellulolytic bacteriumCaldicellulosiruptor besciiwas successfully engineered to produce 2,3-butanediol from cellulose, xylan, and directly from unpretreated switchgrass. Genome-scale metabolic modeling ofC. besciiwas applied to adjust carbon and redox fluxes to maximize productivity of 2,3-butanediol, thereby revealing bottlenecks that require genetic modifications.

Biotechnology & Applied Microbiology↗

DOE OSTI2023

Unleashing the capacity of Rhodococcus for converting lignin into lipids

Bioconversion of bioresources/wastes (e.g., lignin, chemical pulping byproducts) represents a promising approach for developing a bioeconomy to help address growing energy and materials demands. Rhodococcus, a promising microbial strain, utilizes numerous carbon sources to produce lipids, which are precursors for synthesizing biodiesel and aviation fuels. However, compared to chemical conversion, bioconversion involves living cells, which is a more complex system that needs further understanding and upgrading. Various wastes amenable to bioconversion are reviewed herein to highlight the potential of Rhodococci for producing lipid-derived bioproducts. In light of the abundant availability of these substrates, Rhodococcus’ metabolic pathways converting them to lipids are analyzed from a “beginning-to-end” view. Based on an in-depth understanding of microbial metabolic routes, genetic modifications of Rhodococcus by employing emerging tools (e.g., multiplex genome editing, biosensors, and genome-scale metabolic models) are presented for promoting the bioconversion. Co-solvent enhanced lignocellulose fractionation (CELF) strategy facilitates the generation of a lignin-derived aromatic stream suitable for the Rhodococcus’ utilization. Novel alkali sterilization (AS) and elimination of thermal sterilization (ETS) approaches can significantly enhance the bioaccessibility of lignin and its derived aromatics in aqueous fermentation media, which promotes lipid titer significantly. In order to achieve value-added utilization of lignin, biodiesel and aviation fuel synthesis from lignin and lipids are further discussed. In conclusion, the possible directions for unleashing the capacity of Rhodococcus through synergistically modifying microbial strains, substrates, and fermentation processes are proposed toward a sustainable biological lignin valorization.

09 BIOMASS FUELS↗

DOE OSTI2021

Modelling a compressible packed bed flow-through washing and deacetylation reactor for corn stover pretreatment

The deacetylation process is a key step in the lignocellulosic biomass pretreatment process that currently is done in batch reactors. A flow-through diffuser type reactor is a promising approach to make the process more efficient and economically favorable. A washing step before deacetylation can further reduce chemical usage and increase the process efficiency. However, the highly compacted biomass particles can cause significant pressure-drop for fluid flow through the bed, which in the worst case can cause self-enhancing pressure-drop leading to reactor blocking. Detailed understanding of the fundamentals of flow through a compressible packed bed is necessary to scale up the washing and deacetylation process. This work closely examines the classical Kozeny Carman equation and proposes modifications to accurately predict the pressure-drop at different compaction states. Here, a compressible packed bed model is further developed based on the interaction between solid mechanics and fluid dynamics. Experimental measurements of water flow through a packed bed of corn stover show good agreement with the developed model. Corn stover washing process scale up simulations show that smaller reactor diameter, higher friction lining material, lower process throughput, and higher process temperature is favorable in stabilizing the bed from extensive compression when the bed height is fixed.

09 BIOMASS FUELS↗

DOE OSTI2021

Synthesis and characterisation of alites from reduced basic oxygen furnace slags

Basic oxygen furnace slags (BOFS) are by-products of the steelmaking process. Several researchers have studied the production of Portland cement clinker and metallic iron from BOFS via a reductive treatment. }In this study, we applied a carbothermal reduction of BOFS in a technical-scale electric arc furnace and characterised the clinker-like products. Those clinker-like non-metallic products (NMPs) had a chemical and mineralogical composition comparable to clinker for ordinary Portland cement (OPC) and contained large elongated alite crystals as major component. The pure NMPs reacted more slowly and achieved a lower degree of hydration compared with commercial OPC. }If the reactivity of the products can be further increased by employing specific adaptations, it can be used as a full clinker substitute for OPC. Nevertheless, it is also an option to use the material without further modifications as a cement component or concrete addition, which contributes to the strength development in both cases.

36 MATERIALS SCIENCE↗

NASA NTRS1982

Development of a polysilicon process based on chemical vapor deposition, phase 1

The goal of this program is to demonstrate that a dichlorosilane-based reductive chemical vapor deposition (CVD) process is capable of producing, at low cost, high quality polycrystalline silicon. Physical form and purity of this material will be consistent with LSA material requirements for use in the manufacture of high efficiency solar cells. Four polysilicon deposition runs were completed in an intermediate size reactor using dichlorosilane fed from 250 pound cylinders. Results from the intermediate size reactor are consistent with those obtained earlier with a small experimental reactor. Modifications of two intermediate size reactors were completed to interface with the dichlorosilane process demonstration unit (PDU).

Plahutnik, F.↗

NASA NTRS1977

Carrier generation, recombination, trapping, and transport in semiconductors with position-dependent composition

The spatial variation of the chemical composition of a semiconductor modifies the ideal one-electron energy band model as well as the Shockley equations for carrier recombination and transport in two important ways. The random component of the spatial variation introduces localized states in the energy gap by perturbing the band states. The nonrandom component gives rise to the position dependences of the conduction and valence band edges or the electron affinity and the energy gap. This paper gives the modifications of the Shockley equations from these two effects as well as an example of the steady-state recombination rate from distributed gap states in junction solar cells

Sah, C.-T.↗

NASA NTRS1990

Delay compensation in integrated communication and control systems. I - Conceptual development and analysis

A procedure for compensating for the effects of distributed network-induced delays in integrated communication and control systems (ICCS) is proposed. The problem of analyzing systems with time-varying and possibly stochastic delays could be circumvented by use of a deterministic observer which is designed to perform under certain restrictive but realistic assumptions. The proposed delay-compensation algorithm is based on a deterministic state estimator and a linear state-variable-feedback control law. The deterministic observer can be replaced by a stochastic observer without any structural modifications of the delay compensation algorithm. However, if a feedforward-feedback control law is chosen instead of the state-variable feedback control law, the observer must be modified as a conventional nondelayed system would be. Under these circumstances, the delay compensation algorithm would be accordingly changed. The separation principle of the classical Luenberger observer holds true for the proposed delay compensator. The algorithm is suitable for ICCS in advanced aircraft, spacecraft, manufacturing automation, and chemical process applications.

Luck, Rogelio↗

NASA NTRS2012

Modeling of Laser Vaporization and Plume Chemistry in a Boron Nitride Nanotube Production Rig

Flow in a pressurized, vapor condensation (PVC) boron nitride nanotube (BNNT) production rig is modeled. A laser provides a thermal energy source to the tip of a boron ber bundle in a high pressure nitrogen chamber causing a plume of boron-rich gas to rise. The buoyancy driven flow is modeled as a mixture of thermally perfect gases (B, B2, N, N2, BN) in either thermochemical equilibrium or chemical nonequilibrium assuming steady-state melt and vaporization from a 1 mm radius spot at the axis of an axisymmetric chamber. The simulation is intended to define the macroscopic thermochemical environment from which boron-rich species, including nanotubes, condense out of the plume. Simulations indicate a high temperature environment (T > 4400K) for elevated pressures within 1 mm of the surface sufficient to dissociate molecular nitrogen and form BN at the base of the plume. Modifications to Program LAURA, a finite-volume based solver for hypersonic flows including coupled radiation and ablation, are described to enable this simulation. Simulations indicate that high pressure synthesis conditions enable formation of BN vapor in the plume that may serve to enhance formation of exceptionally long nanotubes in the PVC process.

Gnoffo, Peter A.↗

DOE OSTI2022

Leaching Model of Radionuclides in Metal-Organic Framework Particles

Metal-organic frameworks (MOFs) have been used to sequester radionuclides and seal them inside of porous scaffolds using postsynthetic modification procedures. Experiments show that certain Zr-MOF with different capping linkers significantly affects the radionuclide release kinetics. In this work, we developed a leaching model of radionuclides in Zr-MOF particles. The model assumes that uranyl species occupy two energetically favored sites: the metal node and the MOF pores. For a given overall concentration of uranyl species, the partitions of uranyl species at the metal nodes and within the pores are determined by their chemical potentials. The model also considers the effect of particle surface and concentration on chemical potentials and diffusivity. The effects of spatial and structural dependent chemical potentials and diffusivity as well as particle sizes on leaching kinetics are investigated with the model. Predicted and measured uranyl leaching kinetics in Zr-MOF particles under batch experiments are compared. The results demonstrate the model’s capability for exploring the mechanisms of leaching and provide guidance for material design.

Metal-Organic Framework, Diffusion, uranyl, Leachi↗