Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Chemical modification”

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 1,027 records · Page 57

Jupiter Icy Moons Orbiter (JIMO) Electrical Systems Testbed

The Jupiter Icy Moons Orbiter (JIMO) mission will send a spacecraft to explore three of Jupiter s moons (Callisto, Ganymede, and Europa), all of which show evidence of containing vast subterranean oceans beneath their icy surfaces. The evidence of these oceans was discovered by Galileo, and the moons are believed to have the three essential ingredients for life: water, energy, and the necessary chemical elements. Galileo has shown that melted water on Europa has been in contact with the surface of the moon in geologically recent times, and may still lie relatively close to the surface. This project will also introduce a revolutionary new form of electric propulsion powered by a nuclear fission reactor. This electric propulsion is called ion propulsion. It was used on a previous mission called Deep Space 1, proving that ion propulsion works for interplanetary travel. Since JIMO will be traveling farther from the sun, solar power will be difficult to supply the electric energy demanded by the mission. Therefore a nuclear reactor and a thermo-electric converter system will be necessary. Besides making the trip to three of Jupiter's moons - one after the other - a realistic possibility, this new form of power and propulsion opens up the rest of the outer solar system for future exploration. JIMO will fulfill its goals by exploring Europa first, with subsequent trips to the moons Callisto and Ganymede in order to provide comparisons key to understanding the evolution of all three. In order to ensure the stability and proper preparation of the electrical system on JIMO, the High Power AC Power Management and Distribution (PMAD) Test Bed is being developed. The testing on.this AC PMAD will consist of electrical performance verification of candidate power system components. Examples of these components are: high power AC switchgear, high power ACDC converters, AC power distribution units, DC power distribution units, etc. Throughout the course of the summer the over-current control circuit for the five different size relays will be constructed and tested. This circuit will sense the current input to the spacecraft loads and automatically switch off power if the current is too high. Once the circuit is verified to function properly and all necessary modifications have been made, a circuit schematic and board layout will have to be drawn using OrCAD, and the circuits will have to be built.

Trapp, Scott J.↗

Human Coronavirus 229E Infection Alters Histone Proteoforms

Viruses rely on host machinery to replicate, and growing evidence demonstrates that they utilize host epigenetic regulation, including histone modification, to modulate host gene expression for their benefit. Herein, we employed top-down proteomics to quantify histone proteoforms in a model human lung cell line following human coronavirus 229E (HCoV-229E) infection and compared them to mock-infected controls. A total of 572 proteoforms from mock-infected and HCoV-229E infected human lung fibroblast (MRC5) cells (N = 5 per condition) were identified; this included 461 histone proteoforms that were assigned to H2A, H2B, H3, or H4. 200 histone proteoforms were quantifiable, and differential abundance analysis revealed several statistically significant changes in both reversible post-translational modifications (e.g. phosphorylation, acetylation) and the truncation states of core histones. Notably, we found decreased abundance of C-terminally truncated histone H2A and N-terminally truncated histone H3 in HCoV-229E-infected samples. These findings underscore the power of top-down proteomics to resolve unique truncation states of proteoforms and support the hypothesis that viruses alter histone length (removing regulatory sites) to influence host gene expression.

60 APPLIED LIFE SCIENCES↗

Dimensional Control in Phase-Pure Coevaporated Quasi-2D Ruddlesden–Popper Structures

Fast, uncontrolled crystallization with several competing pathways makes solution-processing of phase-pure quasi-two-dimensional (quasi-2D) metal halide Ruddlesden–Popper thin films challenging. Typically, solution-processing results in the formation of different structural phases with varying dimensionality ranging from 2D, to quasi-2D, and 3D, introducing bandgap disorder and inhibiting charge transport. In this work, we eliminate interactions between precursor salts and solvents by using controlled thermal coevaporation to grow quasi-2D thin films that show high phase purity and narrow phase distribution. We study the structural landscape using synchrotron-based X-ray scattering and charge-carrier dynamics using ultrafast pump–probe spectroscopy. We then demonstrate a strategy to control the crystallographic phase of the film through phosphonic acid-based surface modification. We use density functional theory to study the interactions between propylphosphonic acid and the organic precursors and find that the interactions of loosely bound phosphonic acid molecules with evaporated precursors, followed by the migration of phosphonic acids through the deposited thin film, dictate the film structure between 2D and quasi-2D phases. These findings introduce new solvent-free methods for the fabrication of phase-pure quasi-2D Ruddlesden–Popper thin films and control phase selectivity across different dimensional (2D and quasi-2D) structures.

36 MATERIALS SCIENCE↗

Boosting Photoelectric Conductivity in Porphyrin-Based MOFs Incorporating C 60

Electronic structure calculations show that guest C60 in the porphyrin-containing metal organic frameworks Zn 2 (TCPB)(DA-ZnP) (DA-MOF; H 4 TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, DA-ZnP = [5,15-bis[(4-pyridyl)ethynyl]-10,20-diphenylporphinato]zinc(II)) and Zn 2 (TCPB)(F-ZnP) (F-MOF; F-ZnP = [5,15-di(4-pyridyl)-10,20-bis(pentafluorophenyl)porphinato]zinc(II)) engenders high photoelectrical conductivity due to efficient donor–acceptor charge-transfer (CT) interactions. Structural modifications at the meso position of the porphyrin influence the preferred positions of C 60 within the frameworks, giving rise to host–guest interactions with different anisotropic structural, electronic, and optoelectronic properties. A preferred slipped-parallel π-stacked interaction of C 60 that is predicted for NH 2 -substituted DA-MOF and F-MOF fosters strong CT transitions and lowers band gaps by ~1.0 eV compared to the pristine DA-MOF and F-MOF. Hopping rates computed using Marcus theory are found to be anisotropic and accelerated by multiple orders of magnitude across π-stacked interfaces created by C 60 incorporation, a consequence of strong electronic coupling between initial and final diabatic states. Calculations indicate that photoinduced electron transfer, as well as direct CT from porphyrin to C 60 upon irradiation, triggers a charge separation process that leads to the formation of what should be long-lived electron-trapped states at the heterojunctions. Lastly, design principles revealed here for the control of photophysical and electron-transfer processes will be useful for constructing new MOF-derived visible- and infrared-based optoelectronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Effects of Buoyancy and Dilution on the Structure and Lift-off of Coflow Laminar Diffusion Flames

The ability to predict the coupled effects of complex transport phenomena with detailed chemical kinetics in diffusion flames is critical in the modeling of turbulent reacting flows and in understanding the processes by which soot formation and radiative transfer take place. In addition, an understanding of the factors that affect flame extinction in diffusion flames is critical in the suppression of fires and in improving engine efficiency. The goal of our characterizations of coflow laminar diffusion flames is to bring to microgravity the multidimensional diagnostic tools available in normal gravity, and in so doing provide a broader understanding of the successes and limitations of current combustion models. This will lead to a more detailed understanding of the interaction of convection, diffusion and chemistry in both buoyant and nonbuoyant environments. As a sensitive marker of changes in the flame shape, the number densities of excited-state CH (A(exp 2)delta, denoted CH*), and excited-state OH (A(exp 2)Sigma, denoted OH*) are measured in mu-g and normal gravity. Two-dimensional CH* and OH* number densities are deconvoluted from line-of-sight chemiluminescence measurements made on the NASA KC-135 reduced-gravity aircraft. Measured signal levels are calibrated, post-flight, with Rayleigh scattering. Although CH* and OH* kinetics are not well understood, the CH*, OH*, and ground-state CH distributions are spatially coincident in the flame anchoring region. Therefore, the ground-state CH distribution, which is easily computed, and the readily measured CH*/OH* distributions can be used to provide a consistent and convenient way of measuring lift-off height and flame shape in the diffusion flame under investigation. Given that the fuel composition affects flame chemistry and that buoyancy influences the velocity profile of the flow, we have the opportunity to computationally and experimentally study the roles of fluids and chemistry. In performing this microgravity study, improvements to the computational model have been made and new calculations performed for a range of gravity and flow conditions. Furthermore, modifications to the experimental approach were required as a consequence of the constraints imposed by existing microgravity facilities. Results from the computations and experiments are presented in the following sections.

Walsh, Kevin T.↗

Metabolic engineering to improve production of 3-hydroxypropionic acid from corn-stover hydrolysate in Aspergillus species

Fuels and chemicals derived from non-fossil sources are needed to lessen human impacts on the environment while providing a healthy and growing economy. 3-hydroxypropionic acid (3-HP) is an important chemical building block that can be used for many products. Biosynthesis of 3-HP is possible; however, low production is typically observed in those natural systems. Biosynthetic pathways have been designed to produce 3-HP from a variety of feedstocks in different microorganisms. In this study, the 3-HP β-alanine pathway consisting of aspartate decarboxylase, β-alanine-pyruvate aminotransferase, and 3-hydroxypropionate dehydrogenase from selected microorganisms were codon optimized for Aspergillus species and placed under the control of constitutive promoters. The pathway was introduced into Aspergillus pseudoterreus and subsequently into Aspergillus niger, and 3-HP production was assessed in both hosts. A. niger produced higher initial 3-HP yields and fewer co-product contaminants and was selected as a suitable host for further engineering. Proteomic and metabolomic analysis of both Aspergillus species during 3-HP production identified genetic targets for improvement of flux toward 3-HP including pyruvate carboxylase, aspartate aminotransferase, malonate semialdehyde dehydrogenase, succinate semialdehyde dehydrogenase, oxaloacetate hydrolase, and a 3-HP transporter. Overexpression of pyruvate carboxylase improved yield in shake-flasks from 0.09 to 0.12 C-mol 3-HP C-mol -1 glucose in the base strain expressing 12 copies of the β-alanine pathway. Deletion or overexpression of individual target genes in the pyruvate carboxylase overexpression strain improved yield to 0.22 C-mol 3-HP C-mol -1 glucose after deletion of the major malonate semialdehyde dehydrogenase. Further incorporation of additional β-alanine pathway genes and optimization of culture conditions (sugars, temperature, nitrogen, phosphate, trace elements) for 3-HP production from deacetylated and mechanically refined corn stover hydrolysate improved yield to 0.48 C-mol 3-HP C-mol -1 sugars and resulted in a final titer of 36.0 g/L 3-HP. The results of this study establish A. niger as a host for 3-HP production from a lignocellulosic feedstock in acidic conditions and demonstrates that 3-HP titer and yield can be improved by a broad metabolic engineering strategy involving identification and modification of genes participated in the synthesis of 3-HP and its precursors, degradation of intermediates, and transport of 3-HP across the plasma membrane.

09 BIOMASS FUELS↗

Revisiting the Origin of Macromolecular Carbon (MMC) in Lunar Basalts 15556 & 10044

Volatile elements influence the geo-chemical evolution of planetary bodies and they are in magmas at every stage, from melting within planetary interiors to eruption at the surface. Analyses of lunar mare basalts supported the hypothesis that lunar mag-mas were depleted in volatiles (H-C-F-Cl-S), relative to their terrestrial analogs [1]. Nevertheless, several early studies of samples returned during the Apollo program proposed that the mare basalt eruptions, including the “fire fountain” eruptions, were propelled by the oxidation of magmatic graphite to CO (and/or CO2) gas [2, 3]. Seminal studies during the 1970’s measured the bulk concentration and isotopic compositions of C from Apollo 11 samples, and identified several carbonaceous compounds, including: (a) gaseous (CO, CO2, and traces of CH4), (b) metallic carbide, and (c) potentially elemental carbon [4-6]. These studies reported a relatively broad range of C contents (~100-400 μg/g) and isotopic values (δC13 = -30 to +20), and suggested that these heterogeneities can be explained by contribution from multiple factors, including: (a) indigenous carbon, (b) solar wind implantation, (c) bombardment and/or meteorite impact, and (d) terrestrial contamination [5,6]. However, unequivocal observations of magmatic graphite in lunar basalts have never been made. Macromolecular carbon (MMC)—graphitic carbon varying from nearly amorphous to highly crystalline varieties—was identified as inclusions hosted by igneous pyroxenes from Martian meteorites and were attributed to being indigenous to Mars [8]. The authors carefully considered the textural and mineralogical relationship of the MMC phases, and concluded that the subset of MMC located within and/or adjacent to cracks, or at a disrupted surface (e.g., cut) were most consistent with terrestrial contamination. The near absence of con-firmed instances of lunar magmatic MMC within the literature [9], combined with the wide range of isotopic values and bulk carbon contents measured in lunar bas-alts begs the question as to whether previously measured carbon is of an indigenous origin, or the result of terrestrial contamination. Using Raman spectroscopy, we have observed MMC in lunar basalts subjected to different forms of anthropogenic modification related to sample preparation including polished sections, sawn surfaces, and fractured surfaces adjacent to sawn sur-faces. We have observed MMC of unknown origin in all of these settings. Here we report the preliminary textural and spectroscopic characteristics of MMC hosted within the groundmass of Apollo 15 (15556) and Apollo 11 basalts (10044) as part of our ongoing investigation of the origin of these carbonaceous materials.

lunar↗

Modification and analysis of context-specific genome-scale metabolic models: methane-utilizing microbial chassis as a case study

ABSTRACT Context-specific genome-scale model (CS-GSM) reconstruction is becoming an efficient strategy for integrating and cross-comparing experimental multi-scale data to explore the relationship between cellular genotypes, facilitating fundamental or applied research discoveries. However, the application of CS modeling for non-conventional microbes is still challenging. Here, we present a graphical user interface that integrates COBRApy, EscherPy, and RIPTiDe, Python-based tools within the BioUML platform, and streamlines the reconstruction and interrogation of the CS genome-scale metabolic frameworks via Jupyter Notebook. The approach was tested using -omics data collected for Methylotuvimicrobium alcaliphilum 20Z R , a prominent microbial chassis for methane capturing and valorization. We optimized the previously reconstructed whole genome-scale metabolic network by adjusting the flux distribution using gene expression data. The outputs of the automatically reconstructed CS metabolic network were comparable to manually optimized i IA409 models for Ca-growth conditions. However, the CS model questions the reversibility of the phosphoketolase pathway and suggests higher flux via primary oxidation pathways. The model also highlighted unresolved carbon partitioning between assimilatory and catabolic pathways at the formaldehyde-formate node. Only a very few genes and only one enzyme with a predicted function in C1 metabolism, a homolog of the formaldehyde oxidation enzyme ( fae1-2 ), showed a significant change in expression in La-growth conditions. The CS-GSM predictions agreed with the experimental measurements under the assumption that the Fae1-2 is a part of the tetrahydrofolate-linked pathway. The cellular roles of the tungsten (W)-dependent formate dehydrogenase ( fdhAB ) and fae homologs ( fae1-2 and fae3 ) were investigated via mutagenesis. The phenotype of the f dhAB mutant followed the model prediction. Furthermore, a more significant reduction of the biomass yield was observed during growth in La-supplemented media, confirming a higher flux through formate. M. alcaliphilum 20Z R mutants lacking fae1-2 did not display any significant defects in methane or methanol-dependent growth. However, contrary to fae1, the fae1-2 homolog failed to restore the formaldehyde-activating enzyme function in complementation tests. Overall, the presented data suggest that the developed computational workflow supports the reconstruction and validation of CS-GSM networks of non-model microbes. IMPORTANCE The interrogation of various types of data is a routine strategy to explore the relationship between genotype and phenotype. An efficient approach for integrating and cross-comparing experimental multi-scale data in the context of whole-genome-based metabolic network reconstruction becomes a powerful tool that facilitates fundamental and applied research discoveries. The present study describes the reconstruction of a context-specific (CS) model for the methane-utilizing bacterium, Methylotuvimicrobium alcaliphilum 20Z R . M. alcaliphilum 20Z R is becoming an attractive microbial platform for the production of biofuels, chemicals, pharmaceuticals, and bio-sorbents for capturing atmospheric methane. We demonstrate that this pipeline can help reconstruct metabolic models that are similar to manually curated networks. Furthermore, the model is able to highlight previously overlooked pathways, thus advancing fundamental knowledge of non-model microbial systems or promoting their development toward biotechnological or environmental implementations.

Kulyashov, M. A.↗

The Moderately (D)efficient Enzyme: Catalysis-Related Damage In Vivo and Its Repair

Enzymes have in vivo life spans. Analysis of life spans, i.e., lifetime totals of catalytic turnovers, suggests that nonsurvivable collateral chemical damage from the very reactions that enzymes catalyze is a common but underdiagnosed cause of enzyme death. Analysis also implies that many enzymes are moderately deficient in that their active-site regions are not naturally as hardened against such collateral damage as they could be, leaving room for improvement by rational design or directed evolution. Enzyme life span might also be improved by engineering systems that repair otherwise fatal active-site damage, of which a handful are known and more are inferred to exist. Unfortunately, the data needed to design and execute such improvements are lacking: there are too few measurements of in vivo life span, and existing information about the extent, nature, and mechanisms of active-site damage and repair during normal enzyme operation is too scarce, anecdotal, and speculative to act on. Fortunately, advances in proteomics, metabolomics, cheminformatics, comparative genomics, and structural biochemistry now empower a systematic, data-driven approach for identifying, predicting, and validating instances of active-site damage and its repair. These capabilities would be practically useful in enzyme redesign and improvement of in-use stability and could change our thinking about which enzymes die young in vivo, and why.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Influence of Ozone: Superstoichiometric Oxygen in Atomic Layer Deposition of Fe 2 O 3 Using tert -Butylferrocene and O 3

Understanding the chemical mechanisms at play in atomic layer deposition (ALD) is critical for effective process development and expansion of ALD into more complex classes of materials. In this work, a mechanistic study of iron oxide deposited by ALD using tert-butylferrocene and ozone as reactants is performed. Iron oxide ALD using ozone is a useful model system for mechanistic studies due to the prevalence of ozone-based ALD processes and the uses of iron oxide in ternary and quaternary metal oxides. Results show that saturation conditions require significantly greater exposures of both reactants than is typically reported in the literature, and growths per cycle of greater than one monolayer of Fe 2 O 3 per cycle are observed and explained. A growth mechanism is proposed whereby increased ozone exposure results in uptake of superstoichiometric oxygen into the film. X-ray characterizations reveal the presence of excess oxygen stored near the surface of films deposited with larger ozone exposures and show that increased ozone exposures cause crystalline domain rearrangement and conversion of the film from the γ-maghemite phase to the α-hematite phase. The mechanism described here has implications for the wider class of ozone-based ALD processes, and potential applications of this growth phenomenon are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Real-Time In Situ Observation of CsPbBr 3 Perovskite Nanoplatelets Transforming into Nanosheets

The manipulation of nano-objects through heating is an effective strategy for inducing structural modifications and therefore changing the optoelectronic properties of semiconducting materials. Despite its potential, the underlying mechanism of the structural transformations remains elusive, largely due to the challenges associated with their in situ observations. To address these issues, we synthesize temperature-sensitive CsPbBr 3 perovskite nanoplatelets and investigate their structural evolution at the nanoscale using in situ heating transmission electron microscopy. We observe the morphological changes that start from the self-assembly of the nanoplatelets into ribbons on a substrate. We identify several paths of merging nanoplates within ribbons that ultimately lead to the formation of nanosheets dispersed randomly on the substrate. These observations are supported by molecular dynamics simulations. We correlate the various paths for merging to the random orientation of the initial ribbons along with the ligand mobility (especially from the edges of the nanoplatelets). This leads to the preferential growth of individual nanosheets and the merging of neighboring ones. These processes enable the creation of structures with tunable emission, ranging from blue to green, all from a single material. Our real-time observations of the transformation of perovskite 2D nanocrystals reveal a route to achieve large-area nanosheets by controlling the initial orientation of the self-assembled objects with potential for large-scale applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying Membrane Structure and Dynamics during Bioproduct Production in Zymomonas mobilis by Molecular Simulation

The conversion of lignocellulosic biomass into biofuels and bioproducts by microbial biorefineries is central to a sustainable chemical industry. Zymomonas mobilis is one such biorefinery chassis and is resistant to ethanol stress, leading to its use in biomass conversion to biofuels and bioproducts. However, Z. mobilis growth is often inhibited by organic acids, aldehydes, alcohols, ketones, and amides found in biomass hydrolysate. The resulting slow growth inhibits production and as a result drives up the price for the resulting products. One hypothesis is that these molecules interact with or disrupt the bacterial membrane, triggering stress responses and hindering growth. To test this hypothesis at the molecular level, we employ all-atom molecular dynamics (MD) simulations to investigate lignocellulose-derived small molecules and their impact on a biologically relevant Z. mobilis membrane model. Simulations were conducted across a range of inhibitor concentrations from 0 to 2.5 mol %, analyzing key membrane properties such as area per lipid (APL), membrane thickness, lipid-order parameter (−S CH ), lateral diffusion coefficient (D xy ), and permeability coefficient (Pm). From simulation, we observed altered membrane structure and dynamics at these modest small molecule concentrations commonly found in hydrolysates. Generally, the membranes become thinner, with a higher area per lipid and lower-order parameter as the small molecule concentration increases. These trends are stronger for more hydrophobic molecules with greater hydrophobic bulk, as isobutanol, propanol, and propanoic acid showed greater membrane perturbations as the concentration increased compared to other small molecules. Tracking small molecule distributions directly in our equilibrium simulations allows us to determine concentration-dependent free energy profiles for these molecules. While the trends are noisy, generally the barriers to crossing the membrane decrease as the concentration increases, indicating that the membranes become leakier as small molecule concentrations rise. Comparing between native Z. mobilis membranes with hopanoids and membranes sharing the same phospholipid composition but without hopanoids, hopanoids stabilize and order the membrane for smaller molecules to maintain membrane structure but appear insufficient for larger hydrophobic molecules like isobutanol. These findings provide a mechanistic understanding of how small molecules found in biomass degradation streams interact with the Z. mobilis membrane, offering valuable insights for future strain engineering efforts to optimize biofuel and bioproduct synthesis from biomass feedstocks by highlighting limits to small molecule tolerance. This knowledge can guide the modification of membrane composition to develop more robust microbes, thereby improving microbial survival and yields in industrial contexts.

Singh, Nitin Kumar [Michigan State Univ., East Lan↗

Response of ZrC to swift heavy ion irradiation

Zirconium carbide (ZrC) is commonly used for energy sector research, as well as a surrogate for the proposed advanced nuclear fuel candidate uranium carbide. Here this study investigates structural modifications to nanocrystalline and microcrystalline ZrC resulting from dense electronic excitations induced by swift heavy ion exposure. Samples were irradiated with 946 MeV Au ions to various fluences up to 6 × 10 13 ions cm –2 and characterized using synchrotron-based x-ray diffraction. The evolution of the unit-cell parameter and heterogeneous microstrain were evaluated as a function of fluence and compared with those of nanocrystalline and microcrystalline CeO 2 (a surrogate for UO 2 fuel) irradiated under identical conditions. Distinct differences were observed in the radiation responses of the carbide and oxide across both grain sizes. Most notably, microcrystalline ZrC exhibits swelling characterized by two distinct regimes, which does not result in saturation at the ion fluences achieved. This contrasts with CeO 2 , which exhibits the well-documented direct-impact defect accumulation mechanism, reaching a steady-state saturation of swelling at higher fluences. Nanocrystalline CeO 2 undergoes more pronounced swelling compared with microcrystalline CeO 2 , in contrast to nanocrystalline ZrC, which exhibits only minimal unit-cell changes. These results demonstrate that swift heavy ion-induced structural changes can be quite different in carbides and oxides, which must be considered when extrapolating fission-fragment type damage in current fuels to advanced fuels.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Can a Nuclear-Assisted Biofuels System Enable Liquid Biofuels as the Economic Low-carbon Replacement for All Liquid Fossil Fuels and Hydrocarbon Feedstocks and Enable Negative Carbon Emissions?

This report integrates the results of a series of studies and workshops to address the question: Can a nuclear-assisted biofuels system enable liquid biofuels as the economic low-carbon replacement for all liquid fossil fuels and hydrocarbon feedstocks and simultaneously enable negative carbon emissions? “Economic” is defined as economically competitive relative to other low-carbon replacement options for crude oil. “All” refers to the capability to replace the 18 million barrels of oil per day used by the United States. “Nuclear-assisted” refers to the provision of massive quantities of low-carbon heat and hydrogen at the refinery to fully utilize the carbon content of the cellulosic biomass feedstocks for liquid hydrocarbon production. A system is proposed that decarbonizes about half of the U.S. economy while improving long-term soil productivity and sequestering carbon from the atmosphere. In the U.S. almost half the energy consumed by the final customer is in the form of liquid hydrocarbons produced from crude oil. Liquid hydrocarbons are used as (1) an energy source, (2) a method for daily-to-seasonal energy storage, (3) a chemical feedstock, (4) a chemical reducing agent, (5) a method to enhance high-temperature heat transfer in many furnaces and industrial processes and (6) other purposes. As a consequence, the U.S. consumes ~18 million barrels of crude oil per day to produce liquid hydrocarbons. While there are substitutes for liquid hydrocarbons for some applications, our assessment is that the costs and difficulty will dramatically increase if liquid hydrocarbon use goes much below the equivalent of 10 million barrels per day of crude oil. New uses of liquid hydrocarbons to partly replace coal and natural gas could increase demand beyond the equivalent of 10 million barrels of oil per day. One can produce and burn liquid hydrocarbons from biomass without any net addition of carbon dioxide to the atmosphere. Plants grow by removing carbon dioxide from the atmosphere; thus, burning biomass does not result in any net addition of carbon dioxide to the atmosphere. Biomass is typically 40% oxygen. To remove this oxygen to create hydrocarbon liquids, there are two options. The first option is to use biomass as (1) a feedstock, (2) an energy source to operate the process and (3) a supply of carbon to remove the biomass oxygen as carbon dioxide. The second option is to use external heat and hydrogen to remove the oxygen as water and produce liquid hydrocarbons. The use of massive quantities of external heat and hydrogen for hydrocarbon liquid fuels production reduces the biomass feedstock per unit of liquid hydrocarbon product by more than a factor of two reducing land use by more than a factor of two. Many cellulosic feedstocks unsuitable for liquid hydrocarbon production are viable feedstocks with external heat and hydrogen inputs. As a result, there is sufficient cellulosic feedstocks to meet U.S. and global liquid fuels hydrocarbon demand without significant impacts on food and fiber prices. The heat and hydrogen (heat plus electricity) are produced using base-load nuclear power plants—the most economic form of nuclear energy. If low-price natural gas, there is also the option of producing hydrogen from natural gas with sequestration of the carbon dioxide. The biomass is locally processed in depots to produce commodity feedstocks that can be shipped long distances to large biorefineries (250,000 barrels per day, oil equivalent) similar to existing refineries except modifications of front-end processes. The depot system enables local recycle of nutrients back to the soil. The biorefinery can produce variable quantities of liquid hydrocarbon fuels and carbon dioxide for sequestration enabling removal of carbon dioxide from the atmosphere. Preliminary estimates are that the liquid hydrocarbon costs are equivalent to crude oil at between $60 and $70 per barrel. The largest cost is for hydrogen with biomass feedstocks and refinery costs a smaller fraction of the total cost.

09 BIOMASS FUELS↗

A comprehensive experimental and kinetic modeling study of di-isobutylene isomers: Part 1

We report di-isobutylene has received significant attention as a promising fuel blendstock, as it can be synthesized via biological routes and is a short-listed molecule from the Co-Optima initiative. Di-isobutylene is also popularly used as an alkene representative in multi-component surrogate models for engine studies of gasoline fuels. However, there is limited experimental data available in the literature for neat di-isobutylene under engine-like conditions. Hence, most existing di-isobutylene models have not been extensively validated, particularly at lower temperatures (< 1000 K). Most gasoline surrogate models include the di-isobutylene sub-mechanism published by Metcalfe et al. with little or no modification. The current study is undertaken to develop a detailed kinetic model for di-isobutylene and validate the model using a wide range of relevant experimental data. Part 1 of this study exclusively focuses on the low- to intermediate temperature kinetics of di-isobutylene. An upcoming part 2 discusses the high-temperature model development and validation of the relevant experimental targets. Ignition delay time measurements for the di-isobutylene isomers were performed at pressures ranging from 15 - 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 diluted in air and in the temperature range 650 - 900 K using two independent rapid compression machine facilities. In addition, measurements of species identified during the oxidation of these isomers were performed in a jet-stirred reactor and in a rapid compression machine. A detailed kinetic model for the di-isobutylene isomers is developed to capture the wide range of new experimental targets. For the first time, a comprehensive low-temperature chemistry submodel is included. The differences in the important reaction pathways for the accurate prediction of the oxidation of the two DIB isomers are compared using reaction path analysis. In conclusion, the most sensitive reactions controlling the ignition delay times of the DIB isomers under the pressure and temperature conditions necessary for autoignition in engines are identified.

09 BIOMASS FUELS↗

Synthetic Accessibility and Sodium Ion Conductivity of the Na8–x A x P2O9 (NAP) High-Temperature Sodium Superionic Conductor Framework

Advancement of solid-state electrolytes (SSEs) for all solid-state batteries typically focuses on modification of a known structural framework to improve conductivity, e.g., cation substitution for an immobile ion or varying the concentration of the mobile ions. Novel frameworks can be disruptive by enabling fast ion conduction aided by different structure and diffusion mechanisms, thereby unlocking optimal conductors with different properties. Herein, we perform a high-throughput survey of a structural framework for sodium ion conduction, Na8–x A x P2O9 (NAP), to understand the family’s thermodynamic stability, synthesizability, and ionic conduction. We show that the parent phase Na4TiP2O9 (NTP) undergoes a structural distortion (with accompanying conductivity transition) due to unstable phonons arising from pseudo-Jahn–Teller mode in the 1D titanium chains. Screening compounds in which Ti is substituted by other metals computationally reveal a number of candidates that are predicted to be low in formation energy and have high predicted ionic conductivities. High-throughput experimental and subsequent methodology optimization trials deliver one new compound, Na4SnP2O9 (NSP). X-ray diffraction (XRD), microscopy, and spectroscopy characterization indicate that the room-temperature structure of NSP is similar to the high-temperature, orthorhombic NTP phase but with some small unresolved structural differences. These uncharacterized structural details are speculated to limit the ion conductivity. Temperature-dependent XRD and electrochemical impedance spectroscopy indicate multiple coupled conductivity–structure transitions at a high temperature. We demonstrate the challenges with synthesis development and a priori identification of promising SSE phases as a major bottleneck in new (energy) materials development.

Chemical reactions↗

Tunable Atomic Layer Deposition into Ultra-High-Aspect-Ratio (>60000:1) Aerogel Monoliths Enabled by Transport Modeling

Atomic layer deposition (ALD) modification of ultra-high-aspect-ratio structures (>10,000:1) is a powerful platform with applications in catalysis, filtration, and energy conversion. However, the deposition of conformal and tunable ALD coatings at these aspect ratios remains challenging, resulting in empirical tradeoffs between precursor utilization and reaction time. Here, we demonstrate tunable control of the ALD infiltration depth into an aerogel monolith (AM) and develop a reaction-diffusion model to accurately describe the coating process. Specifically, we investigate the ALD exposure time and precursor dose needed to conformally coat a silica AM with pore sizes of ~20 nm, a monolith thickness of ~2.5 mm, and aspect ratios exceeding 60,000:1. We demonstrate complete infiltration into the AM, which is quantified by elemental mapping. A reaction-diffusion model is developed, which accounts for multiple doses and precursor depletion in the ALD chamber during an exposure step. The experimentally validated model enables the prediction and tuning of infiltration depth into a tortuous, high-aspect-ratio structure such as an AM, allowing for the synthesis of rationally designed material architectures. Additionally, the model allows for co-optimization of the total deposition time and percentage of unreacted precursor, which are important for the manufacturability and sustainability of ALD processing. Lastly, we demonstrate that ultra-thin ALD Al 2 O 3 coatings can be used to stabilize silica AMs against structural degradation under high-temperature annealing conditions (700-800 °C), by limiting changes in surface area and monolith volume. As a result, this improved high-temperature stability has implications for numerous aerogel applications, including catalysis and thermal insulation.

14 SOLAR ENERGY↗

Missile impact craters (White Sands Missile Range, New Mexico) and applications to lunar research: Contributions to astrogeology

Craters in natural materials at White Sands Missile Range, N. Mex., were produced by the impact of high-velocity to hypervelocity missiles traveling along oblique trajectories with kinetic energies between 2.1 and 81 × 1014 ergs. The oblique impacts produce craters 2 to 10 m across with morphologies and ejecta that are bilaterally symmetrical with respect to the plane of the missile trajectory. Rims are high and the amount of ejecta large in down-trajectory and lateral directions, whereas rims are low to nonexistent and ejecta thin to absent up-trajectory. Symmetry development and modifications of the symmetry are a function of target material, local topography, and angle of impact. Seven mappable units can be recognized in and around the craters. Three of these are ejecta: thick ejecta near the crater, thin to discontinuous ejecta at greater distances, and scattered ejecta at the greatest distances to the limit of throwout. These ejecta units may be absent on the up-trajectory side; if present, they are rarely as thick or continuous as on other sides of the crater. Three units are target materials: undeformed target material exposed in local patches through thin to discontinuous ejecta and everywhere between the fragments of scattered ejecta, tilted and broken target material exposed in upper crater walls, and shattered and fractured target material exposed on the up-trajectory crater wall. The seventh unit is slope material composed of talus and fallback within the crater. Development, character, and exposure of these units varies chiefly with the target material. Ejecta from the craters is chiefly broken but relatively undeformed target material that may range in size from very fine grained debris to large blocks. Where the target is porous, significant amounts of the ejecta are composed of sheared and compressed fragments, some coated with dark layers of mixed projectile pieces, powder, and fused metal mixed with crushed target material. For layered targets, the original stratigraphic sequence is crudely preserved and in inverted order in thick ejecta. Secondary impact craters are produced by the impact of ejected fragments when the surrounding surface materials are sufficiently weak. A wide variety of secondary impact crater relations may result. Secondary craters nearest the primary crater have blocks in them that are larger than or the same size as the crater they produced. Farther from the primary crater, the fragments are generally smaller than the secondary crater and are ejected from it. Excavation of four craters revealed a mixed breccia beneath the crater floor composed of missile pieces, sheared and compressed target material, and crushed debris. Banded, disaggregated target material and nonmixed breccia surrounded the mixed breccia, and these breccias were surrounded by a zone of conjugate fractures. Beneath the ejecta on the lateral and down-trajectory crater flanks, the target materials were tilted upward and broken. Up-trajectory, open fractures and downward displacement occurred in two of the craters. No displacement was observed for the other two. Beneath the down-trajectory rims of craters with distinct layering, overturned synclines were observed. Missile breakup and behavior during cratering are a function of target and missile properties. Missile breakup depends on missile velocity and is most extensive at high velocities, where the missile is fragmented, powdered, and partly fused. Burial of missile or its fragmented, powdered, and fused remains is greatest for porous targets and least for dense cohesive targets. For very porous targets, camouflet structures containing the fragmented missile may form. Least squares fit to the data on craters in dry to moist targets indicate V(a) = 10^(-11.433)E(p)^(1.205) where V(a) is the volume of the apparent crater and E(p) is the kinetic energy of the missile. This equation is consistent with expectations of the equations relating apparent depth and radius to kinetic energy. Extrapolation of displaced masses and kinetic energies for laboratory impacts with sand and rock converge near 10^(15) to 10^(16) ergs, where the extrapolations are near the data on missile impact craters, corrected for impact angle. Displaced masses of craters produced by missile impacts and by chemical explosives with small scaled depths of burial are about the same when the kinetic energies of the missiles (corrected for angle of impact) are equal to the TNT equivalent energy of the explosive. The problem of equivalent scaled depth of burst for an impact crater is complicated and not entirely resolved, however. Both missile impact craters and chemical explosive craters in water-saturated targets are larger than their counterparts in dry to moist materials. Data collected during the study of missile impact craters have helped resolve a number of problems in lunar research: (1) the soillike nature of lunar surface materials was predicted, (2) sizes of craters produced by artificial impacts were correctly predicted, (3) certain features imaged by Surveyor were found to be analogous to features associated with missile impact craters, {4) missile impacts were used in support of the Apollo passive seismic experiment, (5) craters seen in Apollo orbital photographs were found to be similar to some missile impact craters, (6) missile impact craters supplied data on sample collection and crater phenomenology used in training astronauts, and (7) some returned lunar samples are similar to coated, sheared, and compressed fragments ejected from missile impact craters.

H. J. Moore↗