High Durability Plasma Facing Composites
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Bishop, Sean Robert [Sandia National Laboratories ↗
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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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A highly durable injector faceplate design concept for O2/H2 propellants
Two different O2/H2 injector faceplate designs were used in a test bed rocket engine at the NASA Lewis Research Center facility. This test bed was operated in a pulsing mode to evaluate thrust chamber wall materials and coatings. Degradation of the sintered mesh injector face plates resulted in the substitution of a photoetched diffusion-bonded platelet faceplate. This faceplate accumulated over 4200 thermal cycles without damage or degradation. Prior testing for a total of 17,446 cycles required 19 sintered mesh faceplates. This average of 918 cycles per unit showed the diffusion bonded faceplate to have a thermal cycle capability ranging from 150 to 500 percent of that of the sintered wire unit. The test data also showed that the diffusion-bonded faceplate provided a more uniform flow of gaseous H2 through its discrete and uniformly spaced propellant orifices resulting in enhanced face cooling (no local hot spots) and increased performance. The injector faceplate designs are described and the results of the injector comparison test data are presented.
Mueggenburg, H. H.↗
Durable High Efficiency Membrane and Electrode Assemblies for Heavy Duty Fuel Cell Vehicles
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Macauley, Natalia↗
Durable High Efficiency Membrane and Electrode Assemblies for Heavy Duty Fuel Cell Vehicles
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Bencomo, Natalia [Giner, Inc.]↗
Highly-Accessible Catalysts for Durable High-Power Performance (Final Technical Report)
Reduction of costly Pt usage in proton exchange membrane fuel cell (PEMFC) electrodes is one of the major challenges towards development and commercialization of fuel cell electric vehicles (FCEV). However, reducing the Pt loading results in increasing local mass transport fluxes, and eventual performance loss, especially at high power. In this project, a team of 4 universities, 2 companies, and a national lab came together to develop fuel cell catalysts and electrodes with high performance and durability. The were several key concepts addressed in this project. The first concept is to develop a carbon support that possess internal porosity which are believed to enhance kinetic activity of the catalysts, and yet the pore morphology allows for good reactant transport. The second concept is to improve the Pt-electrolyte interface in hope to reduce the local transport resistance. This was done by using new ionomers and ionic liquids. The last concept involves improving the catalyst stability by introducing Pt alloy catalyst with ordered intermetallic phase. The collaborative platform provided by DOE funding enabled development of a highly active and durable catalyst with performance that exceeds previous catalysts and meets the DOE targets for light duty vehicle application.
08 HYDROGEN↗
A highly oxygen reduction reaction active and CO 2 durable high-entropy cathode for solid oxide fuel cells
One big obstacle for the oxygen reduction reaction (ORR) electrode in solid oxide fuel cells (SOFCs) is the poor reaction activity and fast degradations caused by CO 2 poisoning. Here, in this study, we report our design of an active A-site Ca-rich high-entropy Pr 0.1875 Ba 0.1875 Sr 0.1875 La 0.1875 Ca 0.25 CoO 3-δ (PBSLC 25 C) electrode, guided by the O p-band theory. Here, when applied as a cathode in solid oxide fuel cells (SOFCs), it demonstrates high ORR activity and excellent CO 2 tolerance under realistic operating conditions. Ni-YSZ-based anode-supported cells with PBSLC 25 C cathodes demonstrate excellent peak power densities of 1.14 W cm -2 , 1.04 W cm -2 , and 0.77 W cm -2 in the air with 1%, 5%, and 10% CO 2 , respectively, at 750 °C. The engineered high-entropy PBSLC 25 C effectively diminishes the CO 2 poisoning effect and maintains active surfaces for fast oxygen exchange, as confirmed by the cell durability test in air containing CO 2 (5 and 10 vol%), Raman spectroscopy, and density functional theory calculations.
30 DIRECT ENERGY CONVERSION↗
Effect of Sizings on the Durability of High Temperature Polymer Composites
To increase performance and durability of high-temperature composite for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high-temperature polyimide resins. Sizing commercially supplied on most carbon fiber are not compatible with polyimides. In this study, the chemistry of sizing on two high modulus carbon fiber (M40J and M60J, Tiray) was characterized. A continuous desizling system that uses an environmentally friendly chemical-mechanical process was developed for tow level fiber. Composites were fabricated with fibers containing the manufacturer's sizing, desized, and further treated with a reactive finish. Results of room-temperature tests after thermal aging show that the reactive finish produces a higher strength and more durable interface compared to the manufacturer's sizing. When exposed to moisture blistering tests, however, the butter bonded composite displayed a tendency to delaminate, presumably due to trapping of volatiles.
Allred, Ronald E.↗
Revealing the Nanostructure of Mesoporous Fuel Cell Catalyst Supports for Durable, High-Power Performance
Achieving high power performance and durability with low Pt loadings are critical challenges for proton exchange membrane fuel cells. PtCo catalysts developed on new carbon black supports show promise by simultaneously providing good oxygen reduction kinetics and local oxygen transport. We investigate the role of nanoscale morphology in the performance of these catalysts supported on accessible (HSC-e and HSC-f) and conventional (Ketjen Black) porous carbons using 3D electron tomography, nitrogen sorption, and electrochemical performance measurements. We find that the accessible porous carbons have hollow interiors with mesopores that are larger and more numerous than conventional porous carbons. However, mesopore-sized openings (>2 nm width) are too rare to account for significant oxygen transport. Instead we propose the primary oxygen transport pathway into the interior is through 1–2 nm microporous channels permeating the carbon. The increased mesoporosity in the accessible porous carbons results in a shorter diffusion pathlength through constrictive, tortuous micropores in the support shell leading to lower local oxygen transport resistance. In durability testing, the accessible porous carbons show faster rates of electrochemical surface area loss, likely from fewer constrictive pores that would mitigate coarsening, but maintain superior high current density performance at end of test from the improved local oxygen transport.
Electrochemistry↗
Performance and durability of high emittance heat receiver surfaces for solar dynamic power systems
Haynes 188, a cobalt-based superalloy, will be used to make thermal energy storage (TES) containment canisters for a 2 kW solar dynamic ground test demonstrator (SD GTD). Haynes 188 containment canisters with a high thermal emittance (epsilon) are desired for radiating heat away from local hot spots, improving the heating distribution, which will in turn improve canister service life. In addition to needing a high emittance, the surface needs to be durable in an elevated temperature, high vacuum environment for an extended time period. Thirty-five Haynes 188 samples were exposed to 14 different types of surface modification techniques for emittance and vacuum heat treatment (VHT) durability enhancement evaluation. Optical properties were obtained for the modified surfaces. Emittance enhanced samples were exposed to VHT for up to 2692 hours at 827 C and less than or equal to 10(exp -6) torr with integral thermal cycling. Optical properties were taken intermittently during exposure, and after final VHT exposure. The various surface modification treatments increased the emittance of pristine Haynes 188 from 0.11 up to 0.86. Seven different surface modification techniques were found to provide surfaces which met the SD GTD receiver VHT durability requirement. Of the 7 surface treatments, 2 were found to display excellent VHT durability: an alumina based (AB) coating and a zirconia based coating. The alumina based coating was chosen for the epsilon enhancement surface modification technique for the SD GTD receiver. Details of the performance and vacuum heat treatment durability of this coating and other Haynes 188 emittance surface modification techniques are discussed. Technology from this program will lead to successful demonstration of solar dynamic power for space applications, and has potential for application in other systems requiring high emittance surfaces.
Degroh, Kim K.↗
Performance and Durability of High Temperature Foil Air Bearing for Oil-Free Turbomachinery
The performance and durability of advanced, high temperature foil air bearings are evaluated under a wide range (10-50 kPa) of loads at temperatures from 25 to 650 C. The bearings are made from uncoated nickel based superalloy foils. The foil surface experiences sliding contact with the shaft during initial start/stop operation. To reduce friction and wear, the solid lubricant coating, PS304, is applied to the shaft by plasma spraying. PS304, is a NiCr based Cr2O3 coating with silver and barium fluoride/calcium fluoride solid lubricant additions. The results show that the bearings provide lives well in excess of 30,000 cycles under all of the conditions tested. Several bearings exhibited lives in excess of 100,000 cycles. Wear is a linear function of the bearing load. The excellent performance measured in this study suggests that these bearings and the PS304 coating are well suited for advanced high temperature, oil-free turbomachinery applications.
DellaCorte, C.↗
Performance and Durability of High Temperature Foil Air Bearings for Oil-Free Turbomachinery
The performance and durability of advanced, high temperature foil air bearings are evaluated under a wide range (10-50 kPa) of loads at temperatures from 25 to 650 C. The bearings are made from uncoated nickel based superalloy foils. The foil surface experiences sliding contact with the shaft during initial start/stop operation. To reduce friction and wear, the solid lubricant coating, PS304, is applied to the shaft by plasma spraying. PS304 is a NiCr based Cr2O3 coating with silver and barium fluoride/calcium fluoride solid lubricant additions. The results show that the bearings provide lives well in excess of 30,000 cycles under all of the conditions tested. Several bearings exhibited lives in excess of 100,000 cycles. Wear is a linear function of the bearing load. The excellent performance measured in this study suggests that these bearings and the PS304 coating are well suited for advanced high temperature, oil-free turbomachinery applications.
DellaCorte, C.↗
In Situ Formation of Nano Ni?Co Oxyhydroxide Enables Water Oxidation Electrocatalysts Durable at Hig
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Abed, Jehad↗
Durability of Highly Active PGM Catalyst MEA Tested Via Nitrogen and Air AST Cycling Under HDV Condition
PEMFCs are widely considered as the most promising power sources, particularly for heavy-duty vehicles (HDVs). Unfortunately, the degradation of MEAs under HDV condition remains insufficiently studied. In this work, we systematically investigated two MEAs with catalysts of Pt nanoparticles (NPs) supported over high surface area carbon black. These MEAs were tested for durability under HDV condition in nitrogen using a DOE AST protocol for 180,000 cycles, which is equivalent to 30,000 hours or 1 million miles of operation. The commercial Catalyst MEA also underwent 6,000 AST cycles in air under M2FCT condition. We comprehensively investigated the degradation of catalysts. Our results indicate that both MEAs undergo continuous performance degradation in H 2 /air and H 2 /O 2 during the AST cycling in nitrogen, where analysis employing scanning transmission electron microscopy (STEM) and inductively coupled plasma mass spectrometry (ICP-MS) reveal significant degradation behavior for Pt catalysts. The MEA exhibits more significant degradation, especially within mass transfer region, during the AST process in air. In conclusion, this study describes the long-term degradation behavior and mechanism with AST cycling in nitrogen or air governing highly efficient and durable PGM-catalyst MEA design under HDV conditions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Durable High-Power Membrane Electrode Assemblies with Low Pt Loading
Recent progress in developing and implementing Pt-alloy cathode catalysts and thin (10-15 micron) low resistance membranes has enabled high performance state of art (SOA) membrane electrode assembly (MEA) with low Pt loading. However, these high performing MEAs do not meet durability requirements, especially at peak power, because of complex degradation mechanisms that are sensitive to the materials, MEA design, and fuel cell operating strategy. Specifically, power degradation of the cathode occurs via Pt and Co dissolution as well as deterioration of O 2 transport properties. Additionally, thin membranes are subject to failure due to manufacturing defects in the adjacent gas diffusion media and electrodes and the formation of membrane-attacking radical species caused by high gas crossover. In this project led by General Motors LLC (GM), the objective was to enhance the durability of SOA MEA through optimization of operating conditions, instead of new materials development. Along with our project partners, we have mapped the impact of operating conditions on the durability of SOA MEA. Output of the project include a low Pt loading SOA MEA that exceeds Department of Energy (DOE) 2020 target of >1 W/cm 2 at rated power and pathway to achieve >5000 h of durability. Durability studies in the project provide a detailed understanding of failure modes and operating condition sensitivity on cathode and membrane failure, critical for defining operating conditions and hybridization strategies that can guide system controls to maximize low-Pt MEA life. The project also generated and validated degradation models that will provide future research direction, critical for guiding future cycles of automotive MEA development.
08 HYDROGEN↗
Slightly Conductive Transparent Films for Space Applications: Manufacturability and Durability
Highly transparent, slightly conductive films of co-deposited indium tin oxide (ITO) and MgF, have possible applications for environmental protection of exterior surfaces of spacecraft. Reliable preparation of films with the desired sheet resistivity (approximately 10(exp 8) ohms/square) is difficult because the electrical properties of ITO-Mg F, are highly dependent on film composition. We have investigated the use of plasma emission monitoring to improve the reproducibility of films prepared by RF magnetron sputtering. While considerable improve ment was observed, it appears that some in-situ electrical or optica l characterization will be needed for reliable production coating wit h ITO-MgF,. We have also done further evaluation of a possibly undesi rable photoconductive effect previously observed in these films.
Uppala, N.↗
Fabrication and durability characterization of superhydrophobic and lubricant-infused surfaces
Hypothesis: Practical applications of non-wetting surfaces require good mechanical durability in the wet environments for which they are intended to be used. Durability of non-wetting surfaces is influenced by the surface features, interaction with the functionalization agent, and the lubricant properties that can be tuned independently to identify optimal combination. Experiments: In this study, superhydrophobic and lubricant-infused surfaces are fabricated on copper tubes using chemical etching and electrodeposition texturing techniques, six different functionalizing agents, and five different infused lubricants. Through 180 fabrication combinations and 102 durability tests, each parameter is systematically studied for contributions to initial non-wetting behavior and its durability in heated, wet environment, under high-energy water jet impingement, and under accelerated flow conditions. Findings: Among the adsorbing and curing functionalization agents investigated, n-Hexadecyl mercaptan that belongs to the sulfhydryl group and Sylgard-184, respectively, showed high durability in heated water immersion and under jet impingement tests. For lubricant-infused surfaces, lubricants with high surface tension demonstrated high durability in heated water immersion test, whereas durability in hydrodynamic conditions is closely correlated to lubricant viscosity. Results showed that a lubricant-infused surface will maintain its non-wetting properties in dropwise condensation conditions for approximately 1.5 years.
36 MATERIALS SCIENCE↗
Ordered CoPt oxygen reduction catalyst with high performance and durability
A high-performance and durable polymer electrolyte membrane fuel cell cathode catalyst composed of an ordered L10–CoPt core and a thin Pt shell was designed and prepared. Under practical fuel cell membrane electrode assembly testing conditions, the cathode catalyst showed an outstanding initial mass activity of 0.6 A/mgPt, which satisfies the U.S. Department of Energy performance target while also meeting the durability target of less than 40% loss in mass activity after 30,000 accelerated stress test voltage cycles. The high structural stability of the L10–CoPt@Pt-shell catalyst was confirmed by postmortem materials characterization, and the origin of this robustness was revealed by density functional theory calculations, where the barriers for diffusion of Co atoms were observed to be significantly increased in the ordered intermetallic core.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Building Durable Multimetallic Electrocatalysts from Intermetallic Seeds
When combined with earth-abundant metals, Pt-based alloy nanoparticles (NPs) can be cost-effective electrocatalysts. However, these NPs can experience leaching of non-noble-metal components under harsh electrocatalytic conditions. In this work, the Skrabalak group has demonstrated a novel NP construct in which Pt-based random alloy surfaces are stabilized against non-noble-metal leaching by their deposition onto intermetallic seeds. These core@shell NPs are highly durable electrocatalysts, with the ability to tune catalytic performance by the core@shell architecture, surface alloy composition, and NP shape. This versatility was demonstrated in a model system in which random alloy (ra-) PtM surfaces were deposited onto ordered intermetallic (i-) PdCu seeds using seed-mediated co-reduction (SMCR). In the initial demonstration, ra-PtCu shells were deposited on i-PdCu seeds, with these core@shell NPs exhibiting higher specific and mass activities for the oxygen reduction reaction (ORR) when compared to similarly sized ra-PtCu NPs. These NPs also showed outstanding durability, maintaining ~85% in specific activity after 5000 cycles. Characterization of the NPs after use revealed minimal loss of Cu. The activity enhancement was attributed to the strained surface that arises from the lattice mismatch between the intermetallic core and random alloy surface. The outstanding durability was attributed to the ordered structure of the intermetallic core. The origin of this durability enhancement was investigated by classical molecular dynamics simulations, where Pt atoms were found to have a lower potential energy when deposited on an intermetallic core than when deposited on a random alloy core. Also, ordering of Cu atoms at the core@shell interface appears to enhance the overall binding between the core and the shell materials. Inspired by this initial demonstration, SMCR has been used to achieve shells of different random alloy compositions, PtM (M = Ni, Co, Cu, or Fe). This advance is significant because ligand effects vary as a function of PtM identity and Pt/M ratio. These features also influence the degree of surface strain imparted from the lattice mismatch between the core and shell materials. Like the initial demonstration, standout features of these core@shell NPs were high durability and resistance to non-noble metal leaching. Moving forward, efforts have been directed toward integrating shape-control to this core@shell NP construct. This integration is motivated by the shape-dependent catalytic performance of NPs derived from the selective expression of specific facets. Considering the initial i-PdCu@ra-PtCu system, NPs with a cubic shape have been achieved by judicious selection of capping ligands during SMCR. Evaluation of these NPs as catalysts for the electrooxidation of formic acid found that the nanocubic shape enhances catalytic performance compared to similar core@shell NPs with a spherical morphology. We envision that SMCR can be applied to other NP systems to achieve highly durable catalysts as the syntheses of monodisperse and shape-controlled intermetallic seeds are advanced. This Account highlights the role of intermetallic cores in providing more durable electrocatalysts. More broadly, the versatility of SMCR is highlighted as a route to integrate architecture, alloy surfaces, and shape within one NP system, and how this achievement is inspiring new high-performance and robust catalysts is discussed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗