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At least 109 records · Page 6

Ionic Precursors Transformed Into Vinyl Acetate Synthesis Catalyst via Reaction-Driven Restructuring

Conventional preparation of supported bimetallic catalysts relies on solution-mediated metal salt immobilization and pre-formation of alloy nanoparticles before reaction. Here, we report a fundamentally different synthesis strategy of using a physical mixture of salt precursors to generate an active catalyst during reaction. The catalytic structure is generated in situ from Pd3(OAc)6, Au(OH)3, and KOAc through H2 treatment and reaction-driven restructuring under vinyl acetate monomer (VAM) synthesis conditions. Ascertained from in situ X-ray diffraction and operando infrared spectroscopy analyses, reduction treatment produces segregated Pd and Au domains, and subsequent exposure to a VAM reaction mixture triggers dynamic extraction of Pd from the metal surface. This latter process, mediated by acetate-assisted redox cycles, facilitates Pd migration toward Au domains to form a near-surface localized Pd50Au50 alloy phase. Monometallic Pd domains serve as a reservoir of Pd to the alloy phase, leading to and sustaining a more Pd-enriched active surface and a higher population of accessible Pd sites, compared to a conventionally prepared K-PdAu/SiO2 catalyst. Consequently, this leads to a twofold increase in the VAM formation rate, demonstrating highly active bimetallic catalysts can be generated through the gas-phase treatment of physically mixed ionic precursors.

Cha, Byeong Jun [Rice University]↗

Maximizing machine learning interatomic potential transferability for the discovery of the novel stellated octadecagon Bi18-Pt24 cage structure

Achieving true transferability remains the central challenge for Machine Learning Interatomic Potentials (ML-IAPs) in modeling complex bimetallic nanoclusters across their vast potential energy surfaces. We systematically investigate data selection strategies to optimize the Chebyshev Interaction Model for Efficient Simulation (ChIMES) potential for the Bi-Pt nanoclusters by comparing three innovative sampling methods: Principal Component Analysis (PCA)/k-means (structural diversity), t-distributedStochasticNeighborEmbedding (t-SNE)/k-means (force-space diversity), and hierarchical clustering. Quantitatively, the PCA/k-means strategy proved most effective for global accuracy, yielding the lowest force errors and achieving energy root mean square errors (RMSE) values competitive with Density Functional Theory (DFT), demonstrating excellent accuracy (19.16meV/atom). Structural validation on 34 unique DFT-optimized isomers further confirmed the potential’s high fidelity, with the best model PCA/k-means reproducing structures with an average root mean square deviation (RMSD) of 0.10 Å. However, the t-SNE methods, by maximizing diversity in the force space, demonstrated superior extrapolative power, leading to the more precise prediction of a novel stellated octadecagon Bi18⁢Pt24 cage structure, demonstrating the potential for exploring previously unseen morphologies. Our results establish a clear methodology for strategic data sampling that successfully maximizes ML-IAP transferability, providing an accurate and computationally efficient tool that accelerates the theoretical discovery of complex bimetallic architectures.

Vangheluwe, Raphaël [Université Paris-Saclay, CNRS↗

Dual atom catalysts for rapid electrochemical reduction of CO to ethylene

Strong CO adsorption and facile CO dimerization are the key challenges in electrochemical CO2 reduction towards multi-carbon (C2+) products. We recently showed that CoPc immobilized on a single-walled carbon nanotube can selectively reduce CO2 to methanol. This is enabled through molecular strain, which dramatically improves the CO adsorption energy to CoPc, which in turn facilitates methanol formation. We now examine the extended Phthalocyanine (PcEx) dual atom catalyst (DAC), which is intrinsically strained and contains two catalyst centers, making it a candidate for reducing CO to C2+ products. Using Quantum Mechanics (QM), we screened 20 elements embedded in the PcEx, seeking catalysts with weak hydrogen binding, strong CO binding, and facile CO dimerization. We identi>ied Fe, Ru, Co, and Ir as the best performers and subsequently evaluated the entire CO to C2H4 mechanism (9 steps) using each of these elements as catalysts. In terms of limiting potential and overall exergonicity, we identi>ied CoPcEx as the best catalyst, followed by IrPcEx. We then examined the full CO to C2H4 mechanism on the bimetallic IrCoPcEx catalyst using grand canonical QM to obtain the reaction energetics as a function of applied potential. We conclude that the bimetallic IrCoPcEx is most promising for ef>iciently converting CO to ethylene.

Musgrave, Charles B.↗

Impact of Particle Size on the Vapor-Phase Oxidative Coupling of Methanol and Dimethylamine over Palladium–Gold Nanoparticles

Oxidative coupling of methanol and dimethylamine in the presence of O 2 in the vapor phase over dilute Pd in Au bimetallic catalysts occurs via the dissociation of O 2 on Pd and selective oxidation of methanol on Au. Here, we synthesize a series of silica-supported PdAu alloy nanoparticle catalysts of varied Pd:Au ratios with ~5 nm particle diameter and show that these catalysts have increased selectivity to dimethylformamide across all Pd:Au ratios (~95%), distinct from observations over larger PdAu nanoparticles (~15–25 nm diameter) of similar Pd:Au ratios. Small monometallic Pd particles are more selective than large monometallic Pd particles, and small Au nanoparticles are reactive and selective for oxidative coupling (while large Au nanoparticles are inactive). Rates per surface metal atom were similar over PdAu nanoparticles of all sizes and increased monotonically with increasing Pd content for the small nanoparticles. Further, apparent reaction kinetics demonstrate distinct apparent methanol reaction order and apparent activation energy relative to those reported over larger nanoparticles of similar Pd:Au ratios. Unlike larger PdAu nanoparticles, the rate of dimethylformamide formation is not promoted by cofed water over small PdAu nanoparticles. The results of the kinetic studies are used to propose a series of elementary steps, derive a plausible rate expression, and regress rate and equilibrium constants. These results suggest high coverages of surface methoxy species and low coverages of adsorbates derived from dimethylamine. Taken together, these results demonstrate the sensitivity of the rates, selectivities, and kinetics of oxidative coupling reactions to the size of bimetallic nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale wetting controls reactive Pd ensembles in synthesis of dilute PdAu alloy catalysts

The performance of bimetallic dilute alloy catalysts is largely determined by the size of minority metal ensembles on the nanoparticle surface. By analyzing the synthesis of catalysts comprising Pd 8 Au 92 nanoparticles supported on silica using surface-sensitive techniques, we report that whether Pd overgrowth occurs before or after Au nanoparticle deposition onto the support controls the surface Pd ensemble size and abundance. These differences in Pd ensembles influence catalytic reactivity in H 2 –D 2 isotope exchange and benzaldehyde hydrogenation, which, in correlation with theoretical calculations, is used to elucidate the active site(s) in each reaction. To clarify how the synthetic sequence controls the formation of Pd ensembles, we combine numerical wetting calculations and molecular dynamics simulations (with a machine-learned force field) to visualize Pd deposition and migration on the nanoparticle surface, respectively. Our results suggest that the nanoparticle–support interface restricts nanoparticle accessibility to Pd deposition, which consequently controls the Pd ensemble size, illustrating the critical role of nanoscale wetting phenomena during bimetallic catalyst preparation.

36 MATERIALS SCIENCE↗

Solid-state thermometry via ionic–electronic coupling in two-dimensional heterostructures

The coupling of ionic and electronic transport in solid-state systems offers new opportunities for realizing compact, energy-efficient sensing technologies, yet practical implementations remain limited. In this article, we introduce a two-dimensional iontronic platform based on field-effect transistors that integrate monolayer MoS 2 channels with van der Waals bimetallic thiophosphates ( AB P 2 X 6 , A = Li, Cu, Ag and so on; B = In, Sc and so on; and X = S and Se) as ionic gate dielectrics to realize on-chip thermometry. Specifically, we exploit thermally activated ion migration within the gate dielectric leading to conductance modulation in the MoS 2 channel for temperature sensing. We achieve ~1–2 °C resolution, fast electronic readout and subpicojoule energy consumption in an ultracompact footprint (~1 µm 2 ). Beyond thermometry, these results establish bimetallic thiophosphates as a versatile platform for solid-state iontronics and broaden the functional design space of van der Waals heterostructures for sensing, actuation and adaptive electronics.

42 ENGINEERING↗

Thermal heliotrope - A passive sun-tracker

Continuous sun tracking device consists of helical bimetallic coil and control mechanism. Coil produces torque and angular displacement with temperature change, and acts as device's driving element. Control mechanism, concentric shading mechanism containing bimetallic sensor coil, controls tracking rate and provides for reset cycle.

Byxbee, R. C.↗

Theoretical determination of cesiated work functions

A computer program based on the theoretical work of Gyftopoulos, Steiner, and Levine on bimetallic systems and using a modified version of Wilkins' SIMCON subroutine SURFAS was written for the Univac 1108. This program, WFGSL, accepts the operating conditions and the physical parameters pertinent to the substrate and adsorbate, and outputs the field-free work function, electron current (Richardson equation), ion current (Saha equation), and fractional substrate coverage by the adsorbate. A brief description of the theory is presented together with a program description and listing. An application of the program to a bimetallic system of cesium (adsorbate) and rhenium (substrate) is also described.

Szejn, R. M.↗

A new approach for vibration control in large space structures

An approach for augmenting vibration damping characteristics in space structures with large panels is presented. It is based on generation of bending moments rather than forces. The moments are generated using bimetallic strips, suitably mounted at selected stations on both sides of the large panels, under the influence of differential solar heating, giving rise to thermal gradients and stresses. The collocated angular velocity sensors are utilized in conjunction with mini-servos to regulate the control moments by flipping the bimetallic strips. A simple computation of the rate of dissipation of vibrational energy is undertaken to assess the effectiveness of the proposed approach.

Kumar, K.↗

Removal of PCB and other halogenated organic contaminants found in ex situ structures

Emulsified systems of a surfactant-stabilized, biodegradable water-in-solvent emulsion with bimetallic particles contained with the emulsion droplets are useful at removing PCBs from ex situ structures. The hydrophobic emulsion system draws PCBs through the solvent/surfactant membrane. Once inside the membrane, the PCBs diffuse into the bimetallic particles and undergo degradation. The PCBs continue to enter, diffuse, degrade, and biphenyl will exit the particle maintaining a concentration gradient across the membrane and maintaining a driving force of the reaction.

Quinn, Jacqueline↗

Removal of PCB and Other Halogenated Organic Contaminants found in Ex Situ Structures

Emulsified systems or a surfactant-stabilized, biodegradable water-in-solvent emulsion with bimetallic particles contained with the emulsion droplets are useful at removing PCBs from ex situ structures. The hydrophobic emulsion system draws PCBs through the solvent/surfactant membrane. Once inside the membrane, the PCBs diffuse into the bimetallic particles and undergo degradation. The PCBs continue to enter, diffuse, degrade, and biphenyl will exit the particle maintaining a concentration gradient across the membrane and maintaining a driving force of the reaction.

Quinn, Jacqueline↗

Removal of PCB and other halogenated organic contaminants found in ex situ structures

Emulsified systems of a surfactant-stabilized, biodegradable water-in-solvent emulsion with bimetallic particles contained with the emulsion droplets are useful at removing PCBs from ex situ structures. The hydrophobic emulsion system draws PCBs through the solvent/surfactant membrane. Once inside the membrane, the PCBs diffuse into the bimetallic particles and undergo degradation. The PCBs continue to enter, diffuse, degrade, and biphenyl will exit the particle maintaining a concentration gradient across the membrane and maintaining a driving force of the reaction.

Quinn, Jacqueline W.↗

Development and Hot-fire Testing of Additively Manufactured Copper Combustion Chambers for Liquid Rocket Engine Applications

NASA and industry partners are working towards fabrication process development to reduce costs and schedules associated with manufacturing liquid rocket engine components with the goal of reducing overall mission costs. One such technique being evaluated is powder-bed fusion or selective laser melting (SLM), commonly referred to as additive manufacturing (AM). The NASA Low Cost Upper Stage Propulsion (LCUSP) program was designed to develop processes and material characterization for GRCop-84 (a NASA Glenn Research Center-developed copper, chrome, niobium alloy) commensurate with powder-bed AM, evaluate bimetallic deposition, and complete testing of a full scale combustion chamber. As part of this development, the process has been transferred to industry partners to enable a long-term supply chain of monolithic copper combustion chambers. To advance the processes further and allow for optimization with multiple materials, NASA is also investigating the feasibility of bimetallic AM chambers. In addition to the LCUSP program, NASA has completed a series of development programs and hot-fire tests to demonstrate SLM GRCop-84 and other AM techniques. NASA's efforts include a 4K lbf thrust liquid oxygen/methane (LOX/CH4) combustion chamber and subscale thrust chambers for 1.2K lbf LOX/hydrogen (H2) applications that have been designed and fabricated with SLM GRCop-84. The same technologies for these lower thrust applications are being applied to 25-35K lbf main combustion chamber (MCC) designs. This paper describes the design, development, manufacturing and testing of these numerous combustion chambers, and the associated lessons learned throughout their design and development processes.

Gradl, Paul R.↗

Development and Hotfire Testing of Additively Manufactured Copper Combustion Chambers for Liquid Rocket Engine Applications

NASA and industry partners are working towards fabrication process development to reduce costs and schedules associated with manufacturing liquid rocket engine components with the goal of reducing overall mission costs. One such technique being evaluated is powder-bed fusion or selective laser melting (SLM), commonly referred to as additive manufacturing (AM). The NASA Low Cost Upper Stage Propulsion (LCUSP) program was designed to develop processes and material characterization for GRCop-84 (a NASA Glenn Research Center-developed copper, chrome, niobium alloy) commensurate with powder bed AM, evaluate bimetallic deposition, and complete testing of a full scale combustion chamber. As part of this development, the process has been transferred to industry partners to enable a long-term supply chain of monolithic copper combustion chambers. To advance the processes further and allow for optimization with multiple materials, NASA is also investigating the feasibility of bimetallic AM chambers. In addition to the LCUSP program, NASA’s Marshall Space Flight Center (MSFC) has completed a series of development programs and hot-fire tests to demonstrate SLM GRCop-84 and other AM techniques. MSFC’s efforts include a 4,000 pounds-force thrust liquid oxygen/methane (LOX/CH4) combustion chamber. Small thrust chambers for 1,200 pounds-force LOX/hydrogen (H2) applications have also been designed and fabricated with SLM GRCop-84. Similar chambers have also completed development with an Inconel 625 jacket bonded to the GRCop-84 material, evaluating direct metal deposition (DMD) laser- and arc-based techniques. The same technologies for these lower thrust applications are being applied to 25,000-35,000 pounds-force main combustion chamber (MCC) designs. This paper describes the design, development, manufacturing and testing of these numerous combustion chambers, and the associated lessons learned throughout their design and development processes.

Gradl, Paul R.↗

Hybrid Additive Manufacturing Deposition and Selective Laser Melting Techniques Applied to Copper-Alloy Liquid Rocket Engine Combustion Chambers

Virgin Orbit and the NASA Marshall Space Flight Center have partnered to fabricate a small, multi-metallic, regeneratively cooled thrust chamber by leveraging the strengths of two different types of additive manufacturing: Direct Metal Laser Sintering (DMLS) for the copper alloy liner and blown powder Directed Energy Deposition (DED) for the Inconel structural jacket. The DED is being developed using Virgin Orbit's DMG Mori Seiki hybrid additive/subtractive machining center to further enable unique processing and further cost savings. The materials chosen are preferred for high performance thrust chamber applications, representing a significant advancement from the compromises typically made in the production of metal 3D printed thrust chambers for rocket engines. The 1.2K-lbf thrust article is a 16" tall, 3" diameter design modified for this effort to be regeneratively cooled with water and hot fired using a RP-1/LOX pintle-style development injector from Virgin Orbit's NewtonFour upper stage engine. The thrust chamber was tested at Virgin Orbit's Necker test site in Mojave, California. Results from this test campaign are reported in addition to information characterizing the liner, jacket, and bimetallic diffusion layer materials. This paper will also highlight some of the future bimetallic thrust chamber developments that MSFC and Virgin Orbit will complete under a recently awarded NASA contract.

Zagorski, Kevin↗

Lightweight Thrust Chamber Assemblies using Multi-Alloy Additive Manufacturing and Composite Overwrap

Additive Manufacturing (AM) has brought significant design and fabrication opportunities for complex components with internal features such as liquid rocket engine thrust chambers not previously possible. This technology allows for significant cost savings and schedule reductions in addition to new performance optimization through weight reduction and increased margins. Specific to regeneratively-cooled combustion chambers and nozzles for liquid rocket engines, additive manufacturing offers the ability to form the complex internal coolant channels and the closeout of the channels to contain the high pressure liquid propellants with a single operation. Much of additive manufacturing development has focused on monolithic alloys using Laser Powder Bed Fusion (L-PBF), which do not allow for complete optimization of the structure. The National Aeronautics and Space Administration (NASA) completed feasibility of an AM bimetallic L-PBF GRCop-84 copper-alloy combustion chamber with an AM electron beam freeform Inconel 625 structural jacket under the Low Cost Upper Stage Propulsion (LCUSP) Project. A follow-on project called Rapid Analysis and Manufacturing Propulsion Technology (RAMPT) is under development to further expand large-scale multi-alloy thrust chambers while maturing composite overwrap technology for significant weight savings opportunities. The RAMPT project has three primary objectives: 1) Advancing blown powder Directed Energy Deposition (DED) to fabricate integral-channel large scale nozzles, 2) Develop composite overwrap technology to reduce weight and provide structural capability for thrust chamber assemblies, and 3) Develop bimetallic and multi-metallic additively manufactured radial and axial joints to optimize material performance. In addition to these primary manufacturing developments, analytical modeling efforts compliment the process development to simulate the AM processes to reduce build failures and distortions. The RAMPT project is also maturing the supply chain for various manufacturing processes described above in addition to L-PBF of GRCop-42. This paper will present an overview of the RAMPT project, the process development and hardware progress to date, material and hot-fire testing results, along with future developments.

Additive Manufacturing↗

Spacecraft Radiator Protection from Ionizing Radiation, Dust, and Excessive Heat Loss

Under a Phase II SBIR project funded by NASA Johnson Space Center (Contract No. 80NSSC25C0088), Analytical Scientific Products LLC (ASP) has been developing an actively controlled louver to protect spacecraft radiators from degradation due to exposure to various types of environmental conditions. Of particular interest are ionizing radiation during spacecraft transit through the Van Allen belts, dust during spacecraft landing and surface operations on the moon, and excessive heat loss during the long lunar night especially near the poles where the local ambient temperatures can drop below -200°C. Exposure to ionizing radiation and dust can degrade the optical properties of the radiator coating that in turn reduces its ability to reject excess heat from the spacecraft into the environment. Exposure to the extremely low temperature conditions during the lunar night near the poles can freeze the radiator fluids that can compromise the integrity of the radiator. Passive louvers constructed using thick aluminum vanes are used currently to protect spacecraft radiators from some of the above effects, but they have several drawbacks: (i) their high aerial density makes it impractical to scale them to protect the much larger spacecraft radiators needed for future manned missions to the moon and beyond, (ii) the bimetallic actuators used to open and close the vanes in passive louvers rely on external temperature alone and so the louver cannot offer protection from dust and ionizing radiation when the ambient temperatures are high, and (iii) the bimetallic actuators need time scales of the order of hours to open and close. We have addressed the above limitations of passive louvers through the development of a low aerial density and rapidly actuating actively controlled louver. It is constructed from a custom alloy that offers much higher levels of protection against the ionizing radiation, dust and excessive heat loss at a fraction of weight compared to passive louvers while providing opening and closing time scales of the order of a second. Our modular design makes it easy to scale the system up or down depending on the application. We have recently constructed a 31 inch × 31 inch module of this louver and tested its functionality and effectiveness. These tests have shown that the louver can be opened and closed in less than 2 s. It reduces the transmission of ionizing radiation by 78% to 100% (depending on the radiation source), dust transmission by more than 93%, and heat loss by more than 97%. We are currently preparing to evaluate this device at the Johnson Space Center’s cryogenic vacuum chamber where it can be subjected to simulated lunar surface conditions. This paper provides a detailed discussion of the test designs as well as the data from tests that demonstrate the effectiveness in reducing the transmission of ionizing radiation, dust, and heat under laboratory conditions.

Radiator↗

Spacecraft Radiator Protection from Ionizing Radiation, Dust, and Excessive Heat Loss

Under a Phase II SBIR project funded by NASA Johnson Space Center (Contract No. 80NSSC25C0088), Analytical Scientific Products LLC (ASP) has been developing an actively controlled louver to protect spacecraft radiators from degradation due to exposure to various types of environmental conditions. Of particular interest are ionizing radiation during spacecraft transit through the Van Allen belts, dust during spacecraft landing and surface operations on the moon, and excessive heat loss during the long lunar night especially near the poles where the local ambient temperatures can drop below -200°C. Exposure to ionizing radiation and dust can degrade the optical properties of the radiator coating that in turn reduces its ability to reject excess heat from the spacecraft into the environment. Exposure to the extremely low temperature conditions during the lunar night near the poles can freeze the radiator fluids that can compromise the integrity of the radiator. Passive louvers constructed using thick aluminum vanes are used currently to protect spacecraft radiators from some of the above effects, but they have several drawbacks: (i) their high aerial density makes it impractical to scale them to protect the much larger spacecraft radiators needed for future manned missions to the moon and beyond, (ii) the bimetallic actuators used to open and close the vanes in passive louvers rely on external temperature alone and so the louver cannot offer protection from dust and ionizing radiation when the ambient temperatures are high, and (iii) the bimetallic actuators need time scales of the order of hours to open and close. We have addressed the above limitations of passive louvers through the development of a low aerial density and rapidly actuating actively controlled louver. It is constructed from a custom alloy that offers much higher levels of protection against the ionizing radiation, dust and excessive heat loss at a fraction of weight compared to passive louvers while providing opening and closing time scales of the order of a second. Our modular design makes it easy to scale the system up or down depending on the application. We have recently constructed a 31 inch × 31 inch module of this louver and tested its functionality and effectiveness. These tests have shown that the louver can be opened and closed in less than 2 s. It reduces the transmission of ionizing radiation by 78% to 100% (depending on the radiation source), dust transmission by more than 93%, and heat loss by more than 97%. We are currently preparing to evaluate this device at the Johnson Space Center’s cryogenic vacuum chamber where it can be subjected to simulated lunar surface conditions. This paper provides a detailed discussion of the test designs as well as the data from tests that demonstrate the effectiveness in reducing the transmission of ionizing radiation, dust, and heat under laboratory conditions.

Radiator↗