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

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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Vapor-Cell-Based Atomic Electrometry for Detection Frequencies below 1 kHz

Rydberg-assisted atomic electrometry using alkali-metal atoms contained inside a vacuum environment for detecting external electric fields at frequencies below a few kilohertz has been quite challenging due to the low-frequency electric-field-screening effect that is caused by the alkali-metal atoms adsorbed on the inner surface of the container. In this work, we report a very slow electric-field-screening phenomenon with a timescale up to the order of seconds on a rubidium-vapor cell that is made of monocrystalline sapphire. Furthermore, using this sapphire rubidium-vapor cell with an optically induced, internal bias electric field, we demonstrate vapor-cell-based, low-frequency atomic electrometry that responds to the electric field strength linearly. Limited by the given experimental conditions, this demonstrated atomic electrometer uses an active volume of 11 mm 3 and delivers a spectral noise floor of around 0.34 mV/m √Hz and a 3-dB low cutoff frequency of around 770 Hz inside the vapor cell. This work investigates a regime of vapor-cell-basedatomic electrometry that was seldom studied before, which may enable more applications that use atomicelectric-field-sensing technology.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Graph theory approach to determine configurations of multidentate and high coverage adsorbates for heterogeneous catalysis

Abstract Heterogeneous catalysts constitute a crucial component of many industrial processes, and to gain an understanding of the atomic-scale features of such catalysts, ab initio density functional theory is widely employed. Recently, growing computational power has permitted the extension of such studies to complex reaction networks involving either high adsorbate coverages or multidentate adsorbates, which bind to the surface through multiple atoms. Describing all possible adsorbate configurations for such systems, however, is often not possible based on chemical intuition alone. To systematically treat such complexities, we present a generalized Python-based graph theory approach to convert atomic scale models into undirected graph representations. These representations, when combined with workflows such as evolutionary algorithms, can systematically generate high coverage adsorbate models and classify unique minimum energy multidentate adsorbate configurations for surfaces of low symmetry, including multi-elemental alloy surfaces, steps, and kinks. Two case studies are presented which demonstrate these capabilities; first, an analysis of a coverage-dependent phase diagram of absorbate NO on the Pt 3 Sn(111) terrace surface, and second, an investigation of adsorption energies, together with identifying unique minimum energy configurations, for the reaction intermediate propyne (CHCCH 3 *) adsorbed on a PdIn(021) step surface. The evolutionary algorithm approach reproduces high coverage configurations of NO on Pt 3 Sn(111) using only 15% of the number of simulations required for a brute force approach. Furthermore, the screening of potentially hundreds of multidentate adsorbates is shown to be possible without human intervention. The strategy presented is quite general and can be applied to a spectrum of complex atomic systems.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Understanding Transient Combustion Phenomena in Low-NO x Gas Turbines

The goal of this work was to understand, quantify, and eventually predict combustion instability during operational transients in low-NO x gas turbine combustors. Transient operation is defined as a mode where one or more key operating parameters, including equivalence ratio, fuel composition, or fuel splitting between nozzles in a combustor, are varying in time. The timescale over which this variation occurs will be referred to as the transient timescale, the magnitude of the change in the transient parameter will be referred to as the transient amplitude, and the direction of the variation will be referred to as the transient direction. Transients occur regularly in power generation gas turbine operation. For example, load-following gas turbines vary load to meet power demands while accounting for variation in unsteady grid contributors like wind and solar power. Operators achieve this by varying equivalence ratio and fuel splitting inside the combustors to produce more or less power. Another example of transient operation is during fuel-switching operations, a particular issue for turbines operating with syngas fuels in a co-generation facility. In this case, the composition of the fuel stream may vary in time either as a result of fluctuations in the pipeline, or in the case of a co-generation plant, variations in feedstock or gasification processes. This fluctuation in fuel composition can have significant implications for combustion processes, particularly with high-hydrogen fuels. A small number of studies have investigated transient behavior in gas turbine combustors, particularly in the context of flame blow-off; here, investigators have typically focused on issues of transient amplitude, though without the depth and physics-based experimental design that is proposed in this program. To our knowledge, there have been no studies that have quantified the impact of the transient timescale on combustion. The work helped us understand the impact of several types of transients on combustion stability. Both static and dynamic combustion stability will be considered. The transients will be quantified using their amplitude, direction, and timescale, and we will consider transients in equivalence ratio, fuel composition, and fuel splitting. There were two main objectives of this work: 1. Provide a fundamental understanding of combustion stability during transient operation using data obtained from a number of high-speed diagnostic techniques on experimental configurations that capture important gas turbine combustor features and operating conditions. This goal was met in conjunction with our industrial partner, GE Global Research, with whom we worked closely throughout the program. 2. Develop a stability prediction framework that will allow for the prediction, and possible control, of instabilities as a function of the transient amplitude, direction, and timescale. This input/output model should be physics-based and allow for screening of operating conditions and prediction of unstable behavior at the end of a transient by monitoring combustor health and precursor signals during operation.

03 NATURAL GAS↗
DOE OSTI2021

High-throughput characterization of Lu-doped zirconia

Lu-doped zirconia (LuDZ) was reported in the 1960s to be a poor oxygen ion conductor. However, we identified this system as worthy of reexamination based on the results of a machine learning-based screen for promising oxygen ion conductors, further supported by a physical argument: because Lu is the heaviest and smallest of the lanthanides, it should offer the possibility of high conductivity due to its high polarizability and size compatibility with the zirconia structure. Here the relationship between dopant concentration and conductivity in the LuDZ system was determined using a high throughput experimental methodology in which spatially resolved conductivity was measured across a compositionally graded film, spanning from Zr 0.93 Lu 0.07 O 1.965 to Zr 0.82 Lu 0.18 O 1.91 . The conductivity broadly peaks with composition at 15 cation % Lu, coinciding with the approximate phase boundary of the fully stabilized cubic phase. The composition-dependent conductivity measurements reveal a surprising increase in activation energy for ion transport with increasing Lu content with no change in this trend at the composition of the conductivity maximum. The pre-exponential factor increases sharply with Lu content, but displays a distinct plateau once the conductivity maximum composition is attained. At 500 °C, the conductivity of Zr 0.85 Lu 0.15 O 1.925 is 2 × 10 –3 S cm –1 , approaching that of optimally doped Sc-stabilized zirconia, which has the highest reported conductivity among zirconia compounds. In comparison to other oxide ion conductors, Lu-stabilized zirconia offers the advantage over ceria of negligible electronic conductivity and is easier to process than (La,Sr)(Ga,Mg)O 3-δ .

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

Competition within low-density bacterial populations as an unexpected factor regulating carbon decomposition in bulk soil

Bacterial decomposition of organic matter in soils is generally believed to be mainly controlled by the access bacteria have to organic substrate. The influence of bacterial traits on this control has, however, received little attention. Using the substrate-dependent Monod growth model, we develop a bioreactive transport model to screen the interactive impacts of spatial dispersion and bacterial traits on mineralization. Bacterial traits primarily involved in the bacterial response to the substrate concentration, such as the maximum specific uptake rate and efficiency, the adaptation time of the uptake rate and the initial population density, are considered. We compare the model results with two sets of previously performed cm-scale soil-core experiments in which the mineralization of the pesticide 2,4-D was measured under well-controlled initial distributions and transport conditions. Bacterial dispersion away from the initial substrate location induced a significant increase in 2,4-D mineralization. Additionally, it reveals an increase of specific uptake rates at lower bacterial densities, more than compensating the decrease of specific uptake rates caused by substrate dilution. This regulation of bacterial activities by density, caused by the local depletion of substrate by competing bacteria, becomes dominant for bacteria with an efficient uptake of substrate at low substrate concentrations (a common feature of oligotrophs). Such oligotrophs, commonly found in soils, compete with each other for substrate even at remarkably low population densities. The ratio-dependent Contois growth model, which includes a density regulation in the expression of the uptake efficiency, is more accurate and convenient to calibrate than the substrate-dependent Monod model, at least under these conditions. In view of their strong interactions, bioreactive and transport processes cannot be handled independently but should be integrated, in particular when reactive processes of interest are carried out by oligotrophs.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

From molecular to macroscopic: predicting liquid–liquid phase equilibria and small-angle scattering of mixtures of organic liquids from atomistic simulation using Kirkwood–Buff theory

Macroscopic phase equilibria between solutions define the functionality of many biological and industrial processes, yet they are challenging to predict due to the inherent complexity of liquids containing large molecules. This work introduces an approach for the purely predictive calculation of such phase equilibria in temperature-composition space from molecular dynamics (MD) simulations at one temperature in the single-phase region. We use an approach developed previously to obtain the entropic and enthalpic contributions to the free energy of mixing from the atomic-scale information given by MD simulations via Kirkwood–Buff theory. This allows us to accurately estimate the free energy of mixing as a function of temperature, and thus obtain liquid–liquid phase equilibria, including liquid–liquid critical points, associated binodal and spinodal lines, and composition fluctuations across a region of temperature and composition. Results for binary malonamide–alkane systems are validated by comparison to a direct experimental probe of the fluctuations: the small angle X-ray scattering intensity near zero wavenumber. The MDKB → Phase method demonstrated here provides a significant improvement in predicting liquid–liquid equilibria and free energy as a function of temperature for our systems of interest compared to conventional thermodynamic models. The accurate performance of this purely predictive approach lies in its preservation of atomistic details when determining thermodynamic properties. Furthermore, its inherent extensibility to multi-component systems will likely make the MDKB → Phase approach a valuable general tool for connecting molecular interactions to macroscopic phase equilibria and for the computational screening of materials for targeted thermodynamic behavior.

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

Approaching disorder-tolerant semiconducting polymers

Doping has been widely used to control the charge carrier concentration in organic semiconductors. However, in conjugated polymers, n-doping is often limited by the tradeoff between doping efficiency and charge carrier mobilities, since dopants often randomly distribute within polymers, leading to significant structural and energetic disorder. Here, we screen a large number of polymer building block combinations and explore the possibility of designing n-type conjugated polymers with good tolerance to dopant-induced disorder. We show that a carefully designed conjugated polymer with a single dominant planar backbone conformation, high torsional barrier at each dihedral angle, and zigzag backbone curvature is highly dopable and can tolerate dopant-induced disorder. With these features, the designed diketopyrrolopyrrole (DPP)-based polymer can be efficiently n-doped and exhibit high n-type electrical conductivities over 120 S cm -1 , much higher than the reference polymers with similar chemical structures. This work provides a polymer design concept for highly dopable and highly conductive polymeric semiconductors.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Toward Guided Mutagenesis: Gaussian Process Regression Predicts MHC Class II Antigen Mutant Binding

Antigen-specific immunotherapies (ASI) require successful loading and presentation of antigen peptides into the major histocompatibility complex (MHC) binding cleft. One route of ASI design is to mutate native antigens for either stronger or weaker binding interaction to MHC. Exploring all possible mutations is costly both experimentally and computationally. To reduce experimental and computational expense, here we investigate the minimal amount of prior data required to accurately predict the relative binding affinity of point mutations for peptide-MHC class II (pMHCII) binding. Using data from different residue subsets, we interpolate pMHCII mutant binding affinities by Gaussian process (GP) regression of residue volume and hydrophobicity. We apply GP regression to an experimental data set from the Immune Epitope Database, and theoretical data sets from NetMHCIIpan and Free Energy Perturbation calculations. We find that GP regression can predict binding affinities of nine neutral residues from a six-residue subset with an average R 2 coefficient of determination value of 0.62 ± 0.04 (±95% CI), average error of 0.09 ± 0.01 kcal/mol (±95% CI), and with an receiver operating characteristic (ROC) AUC value of 0.92 for binary classification of enhanced or diminished binding affinity. Similarly, metrics increase to an R2 value of 0.69 ± 0.04, average error of 0.07 ± 0.01 kcal/mol, and an ROC AUC value of 0.94 for predicting seven neutral residues from an eight-residue subset. Our work finds that prediction is most accurate for neutral residues at anchor residue sites without register shift. This work holds relevance to predicting pMHCII binding and accelerating ASI design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Editorial: Using high energy density plasmas for nuclear experiments relevant to nuclear astrophysics

Thermonuclear reaction rates and nuclear processes have traditionally been explored by means of accelerator experiments, which are difficult to execute at conditions relevant to nucleosynthesis. High energy density (HED) plasmas generated using lasers, such as the inertial confinement fusion (ICF) platform, more closely mimic astrophysical environments in several ways, including with thermal distributions of reacting ions as opposed to mono-energetic ions impinging on a cold target; stellar-relevant plasma temperatures and densities; and neutron flux densities not found anywhere else on earth. The most extreme conditions can currently be achieved at the National Ignition Facility (NIF) laser in the US, where densities of 10 3 g/cm 3 and neutron fluxes up to 5∙10 27 neutrons/cm/s have been demonstrated over a time period of a few tens of picoseconds. The HED platform is emerging as an interesting complement to accelerator experiments.

charged-particle-induced reactions↗
DOE OSTI2022

3D analysis of TRISO fuel compacts via X-ray computed tomography

In this study, low-enriched uranium oxycarbide (LEUCO) and surrogate tristructural isotropic (TRISO)- coated-particle compacts with particle volumetric packing fractions of 25%, 40%, and 48% were imaged utilizing X-ray-computed tomography. Subsequent 3D image analysis identified and further quantified kernel size, sphericity, and observed porosity. In addition, the spatial distribution, coordination number, and kernel-nearest neighbors were analyzed and compared for the different packing fractions. Metrics such as observed porosity and sphericity enabled quantification and screening for abnormal kernels within TRISO compacts. Assessment of TRISO particle location confirmed and further quantified a non-uniform distribution of TRISO particles with the spatial distribution in the radial direction being roughly described as a dampened sinusoidal function. The amplitude and frequency of this non-uniform distribution increased with increasing packing fraction. Measured kernel-nearest neighbor distances indicated two regions along the radial surfaces of compacts where TRISO particles are more likely to be in intimate contact with one another. These regions were found: (1) at upper and lower faces of compacts (i.e., corners); (2) offset ~10% of a compact's length from the axial center near the exterior surface. Within these regions, small quantities of defective TRISO surrogate particles (48% packing fraction) and defective LEUCO TRISO particles (40% packing fraction) were found. No defective particles were found within 25% packing fraction LEUCO TRISO compacts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Quantum Chemical Simulations of CO 2 and N 2 Capture in Reline, a Prototypical Deep Eutectic Solvent

Deep eutectic solvents such as reline are an emerging class of low-cost, environmentally friendly solvents with tunable properties that are potentially applicable for the capture and separation of CO 2 . Experimental measurements showed that a reline-based membrane contactor can capture and separate CO 2 via physisorption through a dissolution process with 96.7% purity from a mixed gas containing CO 2 and N 2 (50:50% molar ratio). Here, we examine the nature of the interaction of CO 2 and N 2 with reline employing quantum chemical methods. We focus on explaining the mechanism by which CO 2 and N 2 bind to reline and the reason for the high selectivity for absorption of CO 2 compared to N 2 . We analyze the dynamics, energetics, and binding motifs for CO 2 and N 2 in reline employing density functional theory, density functional tight binding, and ab initio molecular dynamics. We also investigate the effect of reline on the vibrational spectra of CO 2 and reline. Our simulations indicate that the selective capture of CO 2 from the mixture of CO 2 and N 2 is due to the interplay between attractive electrostatic and charge polarization forces with opposing entropic effects, which shift the energetic balance and make the N 2 absorption unfavorable in reline.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Erratum: Production and validation of scintillating structural components from low-background Poly(ethylene naphthalate)

Regretfully, the author list of the original paper did not contain the members of the groups being responsible for the HPGe screening, Radon emanation measurement and ICPMS surface characterization works. As the work performed is to be considered more than “just service work”, the authors together with the members of these groups have decided to amend the authors list. At publication the following authors were not included in the author list: • From Pacific Northwest National Laboratory, Richland, WA, U.S.A.: E.W. Hoppe, I.J. Arnquist, K.P. Hobbs, A.D. French, M.L. diVacri • From INFN, Laboratori Nazionali del Gran Sasso, 67100 Assergi, Italy: M. Laubenstein • From M. Smoluchowski Institute of Physics, Jagiellonian University, 30-348 Krakow, Poland: G. Zuzel The metadata of the present erratum are already correct.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2022

Emissions mitigation technology for advanced water-lean solvent-based CO 2 capture processes

This technical final report submitted to DOE/NETL presents all the research activities performed during the entirety of DE-FE0031660 project-Emissions Mitigation Technology for Advanced Water-Lean Solvent-Based CO 2 Capture Processes which spans from October 2018 through March 2022. RTI International has been conducting studies from fundamental and operational aspects to reduce the overall amine emissions from the advanced Water-Lean Solvent (WLS) systems, specifically RTI’s Non-Aqueous Solvent (NAS). This technical final report will highlight the key findings from project which align closely to the project objectives which are: Identify the contribution of vapor loss, entrainment, and aerosols to the overall emissions of water-lean systems; Determine the significance of CO 2 capture system operating parameters to the amine emissions; Develop an emissions model based on critical operating parameters; Evaluate the effectiveness of emissions mitigation devices to reduce the amine emissions to <1 ppm under flue coal-fired flue gas; and, Determine the contribution of the ECTs to the overall CO 2 capture cost. The following are the key findings based on numerous tests using both lab-scale setups and parametric testing performed at RTI’s Bench-scale Gas Absorption System (BsGAS). During the BP1, the aerosol generation system and monitoring equipment were installed at BsGAS to produce and determine the aerosol characteristics during the NAS CO 2 capture process. The aerosol produced by this setup produced aerosols with the peak diameter and concentration of 50 micron and 1.2E10 7 cm -3 , respectively. These particle sizes and concentrations are matched to those observed in the actual coal-fired power plant flue gases and expected to be found at the absorber inlet of the CO 2 capture system. Over 1,300 hours of parametric testing have been conducted to evaluate the impact of the aerosols and operating conditions during the CO 2 capture with NAS on the overall amine emissions in the treated flue gas. At the worse condition tested, the presence of the aerosols in the flue gas could increase the overall emissions by 10X compared to the baseline emissions from NAS’s vapor pressure. CO 2 capture rate was found to be a main factor impacting the overall emissions as well as aerosol size and concentrations in the absorber off-gas. The higher CO 2 capture rate, the higher amine emissions in the treated gas. The temperature difference between the temperature bulge seen in the absorber and the water wash temperature also impacts the particle growth where the larger the temperature difference, the more amine emissions from aerosols in the treated gas. The majority of the aerosols did not grow substantially in the system, and the particle concentrations remained nearly constant between the absorber inlet and wash outlet. Only a small portion of the particles were found to grow significantly. The high efficiency demister with mesh size of 5-10 micron can be installed to remove a portion of the aerosols from the gas stream leaving the water wash. Overall, these results from parametric testing have established the emission baseline and validate our assumption on the need of emission control technologies (ECT) in order to minimize the emissions from the baseline NAS CO 2 capture process. Over 2,000 of BsGAS operating hours was used to investigate a handful of process improvements which led to a selection of the vital few changes that effectively control the amine emissions. These process improvements are lime-coated-filters for absorber gas inlet, advanced demister at the top of the absorber, a second water wash with amine recovery unit were designed, installed, and tested at BsGAS at the end of BP1. The result showed that the NAS CO 2 capture process with these additional emission control devices could lower the amine emission in the treated gas to about 1 ppm using a simulated coal-fire flue gas stream. The main contributor in lowering the amine emission came from the second water wash with amine recovery unit where the amine concentration in the scrubbing water was kept below 2 wt% through a continuous amine removal via an adsorbent bed, resulting in a low amine vapor pressure. The adsorbent bed was regenerated via a direct steam regeneration and the recover amine was returned to the absorber to minimize wastewater and makeup amine. A flue gas generation system was designed and installed during the first half of BP2 to support the emission testing using a real coal-derived flue gas. The system is capable of generating both coal- and natural gas- derived flue gases with the composition of the gaseous species highly resemble to that of the power plant flue gases. The particulates detected in the coal-derived flue gas showed the mean diameter of 1 micron. The CO 2 capture operating was then proceed using the real coal-derived flue gas where the amine emission was controlled to be about 0-3 ppm for the total run time of about 200 hours. Similar testing was conducted with natural gas-derived flue gas and the result showed a highly amine emission of 30 ppm under the total run time of 200 hours. The Principal Component Analysis (PCA) and the Partial Least Squares Projection to Latent Structures (PLS) techniques were applied to the parametric testing data to derive a multivariate statistical model. The model was validated and trained with half of the data collected, and the predictive ability of the model was evaluated using the remaining half of the data. The resulting empirical model was capable of predicting the overall emissions from the NAS process without the ECTs with ±15% accuracy (average absolute deviation, AAD) in BP1. As more emission data were obtained under the real coal-flue gas in the BP2, the model incorporated these new set of data to reflect the final process configuration, operating parameters, and amine emission. This results in the updated empirical model predicting the amine emission from the NAS CO 2 capture process with 84% goodness-of-fit (R 2 ), 85% predictability (Q 2 ), and 15% AAD. The study evaluates the use of RTI’s Non-Aqueous Solvent technology for 90% CO 2 capture from a net 650 MWe pulverized coal power plant, downstream of the flue-gas desulfurization unit. The captured CO 2 has a purity of > 95% CO 2 , and is dried, compressed to 15.3 MPa (2,215 psia), ready for sequestration. The analysis uses Case B12B from the DOE Baseline study on Bituminous Coal, Revision 4 where the Cansolv CO 2 capture plant is replaced by the RTI CO 2 Capture plant. The CO 2 capture plant has been sized to capture >90% CO 2 from flue gas derived from a net 650 MWe supercritical pulverized coal power plant. The CO 2 capture plant is equipped with emission control technologies that limits the amine emissions to < 1 ppm. Two different cases were evaluated for the technoeconomic study. The key difference between the two cases is the regenerator pressure. In Case 1, the regenerator operates at 0.195 MPa (28.3 psia), whereas in Case 2, the regenerator pressure is 0.44 MPa (64 psia) thus removing the need for the first stage of compression of the eight-stage compression train. Results from the TEA are compared against the DOE reference cases for SCPC plant with and without CO 2 Capture (Case B12A and Case B12B of the DOE Baseline study, respectively). Case 2 with CO 2 regeneration at higher pressure results in the lower cost of CO 2 capture. The total capital cost of the capture process has been estimated using 2018 dollars in Aspen Process Economic Analyzer and was estimated to be $579 MM. The capture plant operation leads to a total parasitic power loss rate of 96 MWe, resulting in a decrease in pulverized coal power plant efficiency of 7.8% points. The resulting cost of electric power increases from 64.4 mills/kWh, for no capture, to 97.5 mills/kWh, with 90% capture, an increase of 51% in the COE. The cost of capturing 90% CO 2 was estimated to be $38.2/tonne-CO 2 , and meets the DOE target of $40/t-CO 2 . Emission control technologies (ECT) investigated in this project includes a second water wash with use of activated carbon beds for removal of amine from the wash water prior to recirculation in the water wash. These ECT allow operation of the CO 2 capture plant with < 1 ppm amine emissions with the treated flue gas and contributes to $2.4/t-CO 2 captured. Amine emissions derived from thermal and oxidative degradations were investigated under this project along with the emissions derived from aerosols for the NAS system. The thermally degraded of the lean NAS showed less than 4% decreased of the original total amine content in the NAS at 150 °C while the result obtained at 120 °C showed no drop in total amine content, suggesting that thermal degradation of the NAS is minimal. These results also suggested that the thermally degraded species are not likely formed and contributed to the emissions due to the low regeneration temperature of the NAS at 90-105 °C. The oxidative degradation, on the other hand, could become problematic as some of these oxidative degraded species were observed during the NAS-5 testing at National Carbon Capture Center (NCCC) and SINTEF in our previous project. The rapid screening of selected inhibitors suggested that oxidative degradation of NAS can be suppressed using thiol containing compounds in amounts of at least 1 mol%. The detailed mechanistic degradation pathway was conceived for a specific amine used in NAS formulation during BP2. he reduction of the nitrosamines caused by the NO x present in the flue gas was also examined. The study suggested that the thermo-chemical treatment of the NAS solvent would be a more effective and economically viable compared to removing NO x at the DCC.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Degradable Biocomposite Thermoplastic Polyurethanes

In this project, the team developed tough and degradable biocomposite thermoplastic polyurethanes (TPUs) by incorporating bacterial spores into TPUs as a biofunctional living filler. The team screened various bacteria and selected the Bacillus subtilis ATCC 6633 strain as the final candidate, primarily due to its genomic availability, sporulation ability and TPU assimilation activity. The heat-shock tolerance of ATCC 6633 spores was further improved through evolutionary engineering via Adaptive Laboratory Evolution (ALE), demonstrating a 17.7-fold enhanced germination efficiency post heat-shock treatment compared to the wild-type strain (WT). The team fabricated biocomposite TPUs by incorporating lyophilized powder of heat-shock tolerized (HST) spores during the hot melt extrusion (HME) of TPU at 135 °C. The baseline TPU used in this project is a commercially available soft-grade TPU (BCF45) manufactured by BASF. Colony forming unit (CFU) assays quantified that WT and HST spores in the TPU matrix retained approximately 20% and 100% survivability, respectively, after HME. Tensile testing demonstrated that the spores behaved as a polymer-reinforcing filler, positively affecting the overall tensile properties of the biocomposite TPU. For example, biocomposite TPU with WT and HST spores (BC TPU WT and BC TPU HST , respectively) exhibited up to 25% and 37% improved toughness, respectively, compared to TPU without spores. BC TPU HST showed remarkably improved disintegration in autoclaved compost (92% mass loss in 5 months), which simulated a microbially poor environment for TPU degradation. When compared to TPU without spores (44% mass loss in 5 months) the acceleration of degradation is marked. Respirometry confirmed that 72% of BC TPU HST was biomineralized into CO2 within 6 months, indicating that spores in the biocomposite TPU were germinated by utilizing nutrients in the autoclaved compost, facilitating TPU degradation at the end of the material's life. The team demonstrated the scale-up of biocomposite TPU fabrication using continuous extrusion and injection molding techniques. Processing conditions optimized in a lab-scale microcompounder were successfully transferred to a continuous extruder with a 30-fold increased throughput. Biocomposite TPUs prepared using these industry-relevant processes showed comparable toughness improvements to samples prepared in the lab-scale extruder. Excitingly, following compounding in the pilot-extruder the composite material could be injection molded, while retaining high spore viability and similar toughness improvements. The team also found that spores in biocomposite TPU served as antioxidants, preventing toughness decay during the recycled extrusion of BC TPU HST . Long-term storage tests over one year showed that the addition of spores had no negative effect on the longevity of the TPU. Furthermore, the team demonstrated the fabrication of spore-bearing biocomposite polymers with other polyesters such as PBAT, PLA, and PCL. We obtained promising preliminary data that showed overall toughness improvements for all polymers with spore addition. Finally, life cycle assessment (LCA) and techno-economic analysis (TEA) were carried out, which indicated minimal additional cost of fabrication. Overall, a tough and degradable biocomposite thermoplastic was successfully developed through this project, with all tasks completed successfully, achieving >100% of the objectives.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Discovery of a Peptoid-Based Nanoparticle Platform for Therapeutic mRNA Delivery via Diverse Library Clustering and Structural Parametrization

Nanoparticle-mediated mRNA delivery has emerged as a promising therapeutic modality, but its growth is still limited by the discovery and optimization of effective and well-tolerated delivery strategies. Lipid nanoparticles containing charged or ionizable lipids are an emerging standard for in vivo mRNA delivery, so creating facile, tunable strategies to synthesize these key lipid-like molecules is essential to advance the field. Here, we generate a library of N-substituted glycine oligomers, peptoids, and undertake a multistage down-selection process to identify lead candidate peptoids as the ionizable component in our Nutshell nanoparticle platform. First, we identify a promising peptoid structural motif by clustering a library of >200 molecules based on predicted physical properties and evaluate members of each cluster for reporter gene expression in vivo. Then, the lead peptoid motif is optimized using design of experiments methodology to explore variations on the charged and lipophilic portions of the peptoid, facilitating the discovery of trends between structural elements and nanoparticle properties. We further demonstrate that peptoid-based Nutshells leads to expression of therapeutically relevant levels of an anti-respiratory syncytial virus antibody in mice with minimal tolerability concerns or induced immune responses compared to benchmark ionizable lipid, DLin-MC3-DMA. Through this work, we present peptoid-based nanoparticles as a tunable delivery platform that can be optimized toward a range of therapeutic programs.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Triacetic Acid Lactone and 4-Hydroxycoumarin as Bioprivileged Molecules for the Development of Performance-Advantaged Organic Corrosion Inhibitors

Biomass conversion, especially the development of bioprivileged molecules utilizing integration of biological and chemical processes, has shown potential to produce novel chemicals with enhanced properties. Here, organic corrosion inhibitors based on triacetic acid lactone and 4-hydroxycoumarin have been synthesized in good yield and tested for corrosion inhibition on mild steel in both sulfuric acid and hydrochloric acid. Sixteen novel corrosion inhibitors derived from triacetic acid lactone and 4-hydroxycoumarin were efficiently synthesized and twelve of them showed high corrosion inhibition efficiency as confirmed by electrochemical impedance spectroscopy (giving values greater than 78%) and polarization analysis. While triacetic acid lactone-based compounds showed good corrosion inhibition performance, the 4-hydroxycoumarin-based compounds showed further improvement in corrosion inhibition performance. Scanning electron microscopy (SEM) analysis of the mild steel coupon in the presence of selected inhibitors showed that corrosion was significantly diminished, with complementary X-ray photoelectron spectroscopy (XPS) analysis suggesting the inhibitor molecules strongly adsorbed on the steel surface. Quantum chemical calculations showed poor correlation between calculated parameters and the performance of these molecules. This large set of corrosion inhibitors containing a dozen promising corrosion inhibitors is useful for future rational design of corrosion inhibitors. In conclusion, the results demonstrate a new direction for the development of bioprivileged molecules.

09 BIOMASS FUELS↗
DOE OSTI2021

High Throughput In-Line Coating Metrology Development for Solid Oxide Fuel Cell Manufacturing

Coatings play key roles in solid oxide fuel cell (SOFC) stack durability. For example, diffusion barrier coatings on Cr-containing interconnect and balance of plant (BOP) components protect electrodes from Cr poisoning over the long operational lifetimes (>10,000 hours) of the fuel cell stack. Common defects in coatings, such as cracks, pinholes, and porosity, result in a failure to protect the electrodes, resulting in shorter operational lifetime and thus higher cost. It is very unlikely, even in the best coating process, that all these defects can be mitigated, hence identifying critical defects in parts, and removing defective parts from production before they can damage the stack, becomes paramount. Furthermore, these quality control techniques must be operational in the production/assembly line (in-line), i.e., high throughput and non-destructive, and cost effective. Redox Power Systems, LLC (Redox) together with the National Renewable Energy Laboratory (NREL) developed much needed high throughput, in-line metrology techniques for protective coatings. The overall goal of the project is to lower cost while increasing robustness, reliability, and endurance of SOFC stacks. To accomplish this, we had several objectives, including: to identify key coating and substrate defects that lead to coating failure through the use of detailed characterization methods (e.g., microscopy, XRD, EDS, electrochemistry); to assess capabilities of in-line metrology techniques, e.g., optical profilometry (Redox) and thermography (NREL), to probe these defects, or evidence thereof; demonstrate long-term performance of “defect-free” protective coatings, as identified by in-line metrology, in solid oxide fuel cell (SOFC) stack operation. In the first part of this project, the ability to identify key defects expected to lead to coating and SOFC degradation using in-line metrology tools were evaluated. Coated interconnect samples with controlled defect types and populations were tested under conditions similar to SOFC operation, followed by detailed post-test analysis to reveal the defects responsible for observed degradation. In the second part of the project, the optimal in-line metrology techniques and methodologies were used to map the defect distribution in full-size interconnects with critical defects intentionally allowed to exist in some cases. These interconnects underwent SOFC testing for extended periods (up to ~3,000 hours) followed by post-test analysis to evaluate the effectiveness of in-line metrology techniques in mitigating MCO coating related degradation. Key accomplishments in this project included the following: Demonstrated ASR of < 0.05 ohm-cm 2 at 650 °C for 1,000 hours with low defect (determined by in-line metrology) interconnect samples (average ASR=37 milliohms-cm 2 after over 1,000 hours). Demonstrated that low defect coatings on interconnects (as screened using in-line metrology) have low volatilization of chromium at ~650 °C for 1,000 hours as detected using Cr-getter material (< 5 at% increase above baseline); 1022 hour duration tests under humidified, elevated temperature (750 °C rather than 650 °C) compared a base case against different coating thicknesses. Demonstrated capability to identify initial key defects of interest with in-line metrology techniques using up to 8 cm by 10 cm having coatings with and without intentional defects of interest using thermal imaging and optical profilometry. Correlated key defects identified using metrology techniques with observed coating performance (e.g., ASR and Cr volatility). Conducted several 4 cm by 4 cm cell tests using MCO-interconnects that were pre-screened using some of the metrology techniques developed in the project (e.g., optical profilometry). An analysis of ASR measurements were able to show that defect-free coatings resulted in the anticipated performance in the cell tests.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2026

Nickel Interlayer for Improved Silver Complex Inks Metallization in GaAs Photovoltaic Devices

Large areas of III-V photovoltaic panels are essential to supplying operational energy for a growing demand of satellites of strategic importance to the United States military, covering a range of applications. High fabrication costs and low manufacturing throughput are key barriers to meeting the necessary supply, which can in turn jeopardize mission success. At the device level, metallization based on printing of complex metal inks has attracted significant research interest due to its potential to substantially reduce processing costs and increase throughput while achieving electrical performance comparable to those of conventional metallization schemes. For GaAs photovoltaic devices, however, reliable electrical contacting remains challenging due to the formation of an interfacial oxide layer at the metal-semiconductor interface. This oxide barrier severely limits current extraction from the PV absorber, resulting in unacceptably high contact resistance. In this study, we report the introduction of a reactive nickel (Ni) interfacial layer between the silver metal fingers and the GaAs substrate to suppress oxide formation while maintaining a low-resistance electrical interface, and show performance data from fully fabricated GaAs devices incorporating the Ni interlayer. These results demonstrate the potential of reactive Ni ink as an effective interfacial layer for improved electrical contacting in low-cost PV metallization schemes.

14 SOLAR ENERGY↗