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DOE OSTI2022

Solar reduction of carbon dioxide on copper-tin electrocatalysts with energy conversion efficiency near 20%

Abstract Copper catalysts modified with tin have been demonstrated to be selective for the electroreduction of carbon dioxide to carbon monoxide. However, such catalysts require the precise control of tin loading amount. Here, we develop a copper/tin-oxide catalyst with dominant tin oxide surface being formed via a spontaneous exchange reaction between sputtered tin and copper oxide. Even though the surface of this catalyst is tin-rich, it achieves an excellent performance towards carbon monoxide production in a flow cell. This contrasts with copper/tin-oxide prepared via atomic layer deposition since it yields selectivity towards carbon monoxide only on a copper-rich surface. Mechanism studies reveal that the tin sites on the tin-rich copper/tin-oxide surface achieve a suitable binding with adsorbed carbon monoxide under the presence of copper. Powered by a triple-junction solar cell, the copper/tin-oxide based electrolyzer sets a new benchmark solar-to-chemical energy conversion efficiency of 19.9 percent with a Faradaic efficiency of 98.9 percent towards carbon monoxide under simulated standard air mass 1.5 global illumination.

14 SOLAR ENERGY↗

DOE OSTI2024

Scaling Up: Demonstrating Risk Reduction and Cost Compression for Commercial Heat Pump Water Heaters - CRADA 625 (Abstract)

Commercial heat pump water heater (CHPWH) systems significantly decarbonize the commercial and multifamily sectors by eliminating the reliance on gas-fired water heating. CHPWH systems are also well suited to include load shift controls that enable load-up and shed commands for supporting grid reliability and time-of-use pricing structure. However, they have not had wide adoption due to factors including price, complexity, and perceived risk. Although CHPWHs have been available in the US for decades, they have not made significant market gains in part because the systems have required significant and costly engineering design expertise and proved lackluster performance. Successful widespread market adoption requires a different approach; a shift from the current custom specialized expertise project design and installation to a repeatable approach that requires little specialized knowledge or expertise and can deliver persistent performance. Using this type of holistic systems approach requires effectively integrating four CHPWH system key components: primary air-to-water heat pumps; primary thermal storage tanks, a temperature maintenance system, and a control system which has capabilities to manage the primary heat pump cycles, any back-up, supplemental, or temperature maintenance heating, alarms, and grid connectivity allowing for demand response (DR), and/or load shifting. The project team has developed and will implement a suite of tools to support faster, less expensive, and more reliable field installations of CHPWH technology and with the resulting data used to further improve the tool set. These tools include: (1) A tool for optimizing system size and costs. (2) A tool that predicts annual energy use and overall system efficiency. (3) The Advanced Water Heater Specification (AWHS 8.0) defining the components of a full CHPWH system addressing performance requirements by climate zone. (4) The Qualified Products List: (QPL) of approved products that meet the specifications requirements. (5) Training materials including online on-demand modules, instructor-led training, and virtual interactive video tours of CHPWH installations in multifamily buildings. Demonstration site identification in low-income buildings in underserved communities is currently underway. Preliminarily, the team anticipates having three demonstrations in the Pacific Northwest and three in the Northeast for a total of six sites. After the demonstration sites are finalized, and M&V instrumentation installations are complete, the team will gather performance data and confirm whether the CHPWH systems perform as predicted and use the data to improve the existing tools.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

NASA NTRS1999

Actively Controlled Landing Gear for Aircraft Vibration Reduction

Concepts for long-range air travel are characterized by airframe designs with long, slender, relatively flexible fuselages. One aspect often overlooked is ground induced vibration of these aircraft. This paper presents an analytical and experimental study of reducing ground-induced aircraft vibration loads using actively controlled landing gears. A facility has been developed to test various active landing gear control concepts and their performance. The facility uses a NAVY A6-intruder landing gear fitted with an auxiliary hydraulic supply electronically controlled by servo valves. An analytical model of the gear is presented including modifications to actuate the gear externally and test data is used to validate the model. The control design is described and closed-loop test and analysis comparisons are presented.

Horta, Lucas G.↗

NASA NTRS1999

Control Design Strategies to Enhance Long-Term Aircraft Structural Integrity

Over the operational lifetime of both military and civil aircraft, structural components are exposed to hundreds of thousands of low-stress repetitive load cycles and less frequent but higher-stress transient loads originating from maneuvering flight and atmospheric gusts. Micro-material imperfections in the structure, such as cracks and debonded laminates, expand and grow in this environment, reducing the structural integrity and shortening the life of the airframe. Extreme costs associated with refurbishment of critical load-bearing structural components in a large fleet, or altogether reinventoring the fleet with newer models, indicate alternative solutions for life extension of the airframe structure are highly desirable. Increased levels of operational safety and reliability are also important factors influencing the desirability of such solutions. One area having significant potential for impacting crack growth/fatigue damage reduction and structural life extension is flight control. To modify the airframe response dynamics arising from command inputs and gust disturbances, feedback loops are routinely applied to vehicles. A dexterous flight control system architecture senses key vehicle motions and generates critical forces/moments at multiple points distributed throughout the airframe to elicit the desired motion characteristics. In principle, these same control loops can be utilized to influence the level of exposure to harmful loads during flight on structural components. Project objectives are to investigate and/or assess the leverage control has on reducing fatigue damage and enhancing long-term structural integrity, without degrading attitude control and trajectory guidance performance levels. In particular, efforts have focused on the effects inner loop control parameters and architectures have on fatigue damage rate. To complete this research, an actively controlled flexible aircraft model and a new state space modeling procedure for crack growth have been utilized. Analysis of the analytical state space model for crack growth revealed the critical mathematical factors, and hence the physical mechanism they represent, that influenced high rates of airframe crack growth. The crack model was then exercised with simple load inputs to uncover and expose key crack growth behavior. To characterize crack growth behavior, both "short-term" laboratory specimen test type inputs and "long-term" operational flight type inputs were considered. Harmonic loading with a single overload revealed typical exponential crack growth behavior until the overload application, after which time the crack growth was retarded for a period of time depending on the overload strength. An optimum overload strength was identified which leads to maximum retardation of crack growth. Harmonic loading with a repeated overload of varying strength and frequency again revealed an optimum overload trait for maximizing growth retardation. The optimum overload strength ratio lies near the range of 2 to 3 with dependency on frequency. Experimental data was found to correlate well with the analytical predictions.

Newman, Brett A.↗

NASA NTRS2018

Overview of the Mars 2020 Parachute Risk Reduction Activity

In 2012, the Mars Science Laboratory (MSL) landed safely on the surface of Mars using a supersonic Disk-Gap-Band (DGB) parachute, which was structurally qualiﬁed for ﬂight via a subsonic wind tunnel test program. Results of the Low Density Supersonic Decelerators (LDSD) program have called into question the methodology and principles that form the foundation of the MSL subsonic test program. LDSD discovered that quasi-static subsonic proof loading a parachute via ground testing may not provide canopy stresses that sufﬁciently bound the stresses experienced during a rapid supersonic inﬂation at Mars. Additionally, deeper scrutiny of the materials and structural margins present in previously successful supersonic DGBs indicated that the MSL parachute ﬂew with lowest margins of any previous parachute. These factors have increased the perceived risk of reusing a heritage MSL DGB parachute design with a subsonic test program for Mars 2020. To reduce this risk,a series of risk reduction steps were initiated starting in 2016. First, two parachute assemblies have been pursued in parallel: a Build-to-Print (BTP) MSL parachute, designed and manufactured by Pioneer Aerospace Corporation, which maintains the heritage of the successful MSL parachute, and a strengthened parachute, designed and manufactured by Airborne Systems North America, which uses higher strength materials throughout the parachute assembly but maintains the same overall size as the MSL parachute. Second, each parachute system was tested in a subsonic wind tunnel to examine the canopies in their fully inﬂated state and assess the workmanship of each canopy. Finally, full-scale parachutes from each vendor will experience at least one supersonic inﬂation at Mars relevant Mach numbers and atmospheric densities at Earth via a supersonic sounding rocket test campaign. This paper presents high-level details regarding the risk reduction strategy, the two candidate parachute conﬁgurations, the ground test program, and the supersonic ﬂight test program, and brief results from each of the test programs.

Chen, Allen↗

NASA NTRSDate not supplied

Launch Vehicle Loads Analysis Using Pressure-Sensitive Paint

Pressure transducers have been the instrumentation of choice for measuring unsteady flow phenomena. With recent advances in high-speed cameras, high-powered LEDs, and fast-response, pressure-sensitive paint, the unsteady pressure-sensitive paint (uPSP) technique has become a valuable alternative for production wind tunnel facilities, enabling time-resolved measurements of unsteady pressure fluctuations over a dense spatial grid on a wind tunnel model. Launch vehicle ground tests have proven to be a particularly well-matched application for uPSP due to the high signal level relative to tunnel background acoustics, relatively simple camera optical access, and rigidity of the model in wind-on test conditions. This presentation will highlight recent advances in data reduction of uPSP measurement data from recent launch vehicle wind tunnel tests at the NASA Ames Unitary Plan Wind Tunnel Complex (UPWT). The system can provide both localized surface pressure spectra as well as regional or zonal estimates of turbulence correlation model parameters. In addition, integrated vehicle-scale loads can be provided for buffet analysis. Data is reduced at the on-premise NASA Advanced Supercomputer (NAS) Division for just-in-time delivery of results during an ongoing wind tunnel test.

Pressure-Sensitive Paint↗

NASA NTRSDate not supplied

Launch Vehicle Loads Analysis Using Pressure-Sensitive Paint

pressure-sensitive paint↗

DOE OSTI2018

Electric Power Distribution System Model Simplification Using Segment Substitution

Quasi-static time-series (QSTS) simulation is used to simulate the behavior of distribution systems over long periods of time (typically hours to years). The technique involves repeatedly solving the load-flow problem for a distribution system model and is useful for distributed energy resource (DER) planning. When a QSTS simulation has a small time step and a long duration, the computational burden of the simulation can be a barrier to integration into utility workflows. One way to relieve the computational burden is to simplify the system model. The segment substitution method of simplifying distribution system models introduced in this paper offers model bus reduction of up to 98% with a simplification error as low as 0.2% (0.002 pu voltage). In contrast to existing methods of distribution system model simplification, which rely on topological inspection and linearization, the segment substitution method uses black-box segment data and an assumed simplified topology.

Reiman, Andrew P. (ORCID:0000000302042960)↗

DOE OSTI2021

A novel solid oxide electrolytic cell with reduced endothermic load for CO 2 electrolysis using (La 0.80 Sr 0.20 ) 0.95 MnO 3-δ cathode

CO 2 conversion to CO via solid oxide electrolysis provides a potentially efficient method for converting CO 2 into an industrially relevant product. A solid oxide electrolysis cell with (La 0.80 Sr 0.20 ) 0.95 MnO 3-δ (LSM) as the CO 2 reduction cathode, yttrium stabilized zirconia (YSZ) as electrolyte, and nickel as the H 2 oxidation anode was operated 800 °C and 850 °C. Thermogravimetric analysis of the LSM material showed no catalyst oxidation at operating temperatures allowing for CO 2 electrolysis without reducing safe gas. In addition, no cathode material mass gain was observed in the presence of CO suggesting little to no carbon deposition occurred above 750 °C. The formation rates of CO for the cell reached 1.15 mL∙min-1∙ cm -2 for an applied current of 150 mA∙cm -2 achieving a faradaic efficiency of 100 %. Furthermore, the cell displayed good stability in the short-term CO 2 electrolysis test with a nominal voltage drop of 4 mV h -1 for 10 h at 850°C. This study shows the feasibility of operating a solid oxide CO 2 electrolysis cell for CO production with H 2 at the anode to reduce endothermic process load.

(La0.80Sr0.20)0.95MnO3-δ↗

DOE OSTI2016

Molybdenum Carbides, Active and In Situ Regenerable Catalysts in Hydroprocessing of Fast Pyrolysis Bio-Oil

We assessed molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60-h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt% and 0.01 mg KOH g-1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60-h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are promising catalytic materials which could lead to a significant cost reduction in hydroprocessing bio-oils. This paper highlights areas for future research which will be needed to further understand carbide structure-function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.

Choi, Jae-Soon↗

DOE OSTI2022

Steady state thermo-mechanics and material property definition framework for analyzing DCLL blanket in the fusion nuclear science facility

In this work, a thermo-mechanics model that relies on creating the material property definition framework (MPDF) and multiphysics coupling of the heat transfer and the solid mechanics modules is developed to determine the structural integrity of the recently designed dual cooled lead lithium (DCLL) inboard blanket (IB) for the Fusion Nuclear Science Facility under steady state loads. The MPDF is called to supply fusion relevant neutron irradiation and temperature induced changes in material properties during multiphysics finite element runs, and PbLi temperature profiles are used to approximate Magnetohydrodynamics effect and the nuclear volumetric heating on the PbLi. Neutron irradiation and temperature induced reduction of the yield and ultimate strengths of F82H steel at the first wall (FW) are quantified for one year. A blanket in an assembly with gaps between blanket sectors and another blanket in an assembly with no gaps between blanket sectors, both exposed to radiation damage that lasted for one year are analyzed. Analysis using the elastic ITER structural design criteria for in-vessel components (ITER SDC-IC) design rules and a linear isotropic-hardening-type elastoplastic material model are used where most appropriate. The IB blanket with gaps between blanket sectors will withstand the steady state combined thermal and coolant loads for one year operational period but will fail if no gaps are allowed between blanket sectors. It is recommended that a gap of about 7.62 mm should be provided between IB blanket sectors during assembly which would close up during service, stop neutron streaming, reduce stresses and reduce bending of the FW into the scrape-off layer.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2020

Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N‐doped Carbon Catalysts

Abstract Ni,N‐doped carbon catalysts have shown promising catalytic performance for CO 2 electroreduction (CO 2 R) to CO; this activity has often been attributed to the presence of nitrogen‐coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO 2 reduction (CO 2 R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile‐derived Ni,N‐doped carbon electrocatalysts (Ni‐PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO 2 R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X‐ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square‐planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.

Koshy, David M.↗

DOE OSTI2018

Poly(lactic acid)/Cellulose Composites Obtained from Modified Cotton Fibers by Successive Acid Hydrolysis

This work is focused on the hydrolysis of cotton fibers from waste textiles to obtain micro and nanofibers to be used as reinforcements in polymer composites. To promote their compatibility with polymeric matrix, hydrolyzed cotton fibers were surface modified with various silane compounds. Thus, these fibers were mixed with commercial poly(lactic acid) (PLA) at 5% w/w loading by melt compounding. Acid treatments caused a decrease of the crystallinity index whereas the thermal stability was significantly improved, especially for cellulose fibers hydrolyzed in two steps. Morphological analysis revealed a reduction of the fibers diameter and a decrease of their length as a consequence of the hydrolysis. NMR analysis confirmed the silanization of the fibers by reaction with the silane agent. Tensile tests revealed that silanization treatments were able to increase the composite Young’s modulus and the stress at break with respect to the neat matrix, indicating that silanization improved the polymer/fiber compatibility interfacial adhesion. The overall results demonstrated that applying suitable surface modification strategies, waste cotton textiles can be effectively recycled as fillers in polymer based composites.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Influence of residual chlorine on Ru/TiO 2 active sites during CO 2 methanation

Titania-supported ruthenium (Ru/TiO 2 ) is an established catalyst for the hydrogenation of carbon dioxide to methane (Sabatier reaction). Chlorine contamination, owed to the RuCl 3 precursor, is demonstrated to have a detrimental impact on methanation activity. After calcination and reduction the catalyst contains residual chlorine, shown by XPS. An aqueous ammonia wash removes Cl without leaching Ru. The washed catalysts exhibit improvements in CH 4 site-time yields. Low Ru loading catalysts encounter the greatest activity enhancements after washing (~4.5-fold). DFT calculations indicate that chlorine and CO 2 directly compete for adsorption on Ru step sites, with Cl impeding the adsorption of CO 2 at under-coordinated sites and at higher Cl coverages. H 2 -chemisorption/TPR show that Cl removal lowers the onset of low temperature H 2 dissociation on Ru. Finally, DRIFTS provide evidence that the removal of Cl facilitates low temperature dissociative binding of CO 2 , indicated by the formation of surface bound linear CO species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Chemical effects on subcritical fracture in silica from molecular dynamics simulations

Fracture toughness of silicates is reduced in aqueous environments due to water-silica interactions at the crack tip. In this paper, to investigate this effect, classical molecular dynamics (MD) simulations using the bond-order based reactive force field (ReaxFF) were used to simulate silica fracture. The chemical and mechanical aspects were separated by simulating fracture in: (a) vacuum with dynamic loading, (b) an aqueous environment with dynamic loading, and (c) an aqueous environment with static subcritical mechanical loading to track silica dissolution. The addition of water to silica fracture reduced the silica fracture toughness by ~25%, a trend consistent with experimentally reported results. Analysis of Si-O bonds in the process zone and calculations of dissipation energy associated with fracture indicated that water relaxes the entire process zone, and not just the surface. Additionally, the crack tip sharpens during fracture in water and an increased number of microscopic propagation events occur. This results in earlier fracture in systems with increasing mechanical loading in aqueous conditions, despite the lack of significant silica dissolution. Finally and therefore, the threshold for Si-O bond breakage has been lowered in the presence of water and the reduction in fracture toughness is due to structural and energetic changes in the silica, rather than specific dissolution events.

58 GEOSCIENCES↗

DOE OSTI2022

A Half-Bridge On-State Voltage Sensor for In-Situ Measurements

Current prognostics for life expectancy of power semiconductors utilize off-line measurements of the on-state resistance. Presented is a half-bridge (HB) on-state voltage (VON) sensor capable of being utilized for in-situ measurements enabling continuous and real-time monitoring of the on-state resistance. The design provides a single VON measurement output that contains independent VON information of both high and low side devices in a HB leg. The measurement output is referenced from the middle point of the HB and combines the two complementary VON sensing outputs. This system reduces the number of components, required number of analog signal processing circuits, and ADC channels for in-situ health monitoring of a power electronics system. These reductions will facilitate integration of the VON sensor with the gate driver board and achieve low system profile. The experimental results demonstrate the proposed VON measurements while switching with inductive and resistive loads.

Roy, Chondon↗

DOE OSTI2022

Westinghouse advanced fuel management strategies leveraging high enrichment and high burnup fuel to optimize PWR economics

In the US, nuclear power plants have been focused on increasing electricity generation for over three decades via longer operating cycles, reduced number of outages and duration, and the implementation of power up-rates. The potential for zero-carbon emission credits and other carbon-reduction initiatives further makes nuclear power utilities to focus on increasing generation capability. Longer operating cycles provide increased energy generation and enable economic savings to nuclear utilities when the increase in fuel loading required to achieve the extended cycle energy target and resulting increase in total fuel cost is offset by the savings from outage avoidance and reduced replacement power costs. For the current licensed limits of 5 w/o {sup 235}U enrichment and 62 GWd/tU peak pin burnup, higher power density PWR plants, which are prevalent in the PWR fleet, require an excessively penalizing fraction of feed fuel assemblies to operate for the extended cycle duration, with inevitably poor fuel use and fuel cycle economics that cannot be counterbalanced by the savings on outage cost avoidance. To overcome this barrier, the nuclear industry is pursuing development of high enrichment/high burnup fuel technology ({sup 235}U enrichment up to 8 w/o and peak pin burnup up to 75 GWd/tU) which increases fuel energy generation capability and can enable high power density plants to achieve positive economics on 24-month cycle of operation. This paper presents advanced fuel management strategies developed by Westinghouse to enable transition of PWR reactors from 18-month to 24-month cycle of operation, with and without a core thermal power uprate, which are then used as basis to assess the economics of a direct transition from 18 to 24-month cycles with high enrichment/high burnup fuel. The results show that these fuel management strategies, especially if coupled with thermal power up-rates, present the opportunity for substantial economic benefits to utilities. The systematic review of fuel management strategies presented can provide an illustrative reference for decision makers as they consider how to maximize nuclear energy generation economically. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Laboratory Experiments Examining the Effect of Thermal and Mechanical Processes on Hydraulic Transmissivity Evolution

Using laboratory slide-hold-slide experiments, at temperatures from 22 to 200 degrees C, to examine effects of fracture reactivation and quasi-static loading on the evolution of fluid transport properties of simulated fractures in Westerly granite. At all temperatures, the in-plane hydraulic transmissivity consistently decays during hold periods resulting in an overall reduction in transmissivity. During the first three to fifteen hours of an experiment, transmissivity decreases rapidly due to the generation of wear products, development of a sliding surface, and compaction of the resulting gouge. Once the sliding surface has developed, the long-term transmissivity decay rate at 22 and 100 degrees C is significantly lower than the transmissivity decay rate during the initial 3-15 hours of the experiment. However, at 200 degrees C, the decay of hydraulic transmissivity remains high throughout the experiment. The long-term decay of hydraulic transmissivity can be fitted with a power law model with more rapid reduction of hydraulic transmissivity at higher temperature. Periods of sliding on the fracture surface result in transient increases in the transmissivity, due to shear dilation, as is expected for Coulomb materials. These transients are superimposed on the long-term decay. When sliding ceases and a new hold period commences, there is a rapid reduction in transmissivity and return to the long-term rate of transmissivity decay. The rate of decay of the transmissivity transients is inversely correlated with temperature, in contrast to the long-term decay and the expected behavior for processes like subcritical crack growth and indentation creep. The higher decay rates that are observed during the initial 3-15 hours of the tests and following sliding, are associated with times that the porosity of the gouge is expected to be high. The difference in decay rates suggests that when the gouge is driven far from equilibrium by active shearing, densification may be dominated by a different mechanism from long-term compaction.

15 GEOTHERMAL ENERGY↗

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