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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Fabrication of ceramic substrate-reinforced and free forms by mandrel plasma spraying metal-ceramic composites

Components fabricated of, or coated with, ceramics have lower parasitic cooling requirements. Techniques are discussed for fabricating thin-shell ceramic components and ceramic coatings for applications in rocket or jet engine environments. Thin ceramic shells with complex geometric forms involving convolutions and reentrant surfaces were fabricated by mandrel removal. Mandrel removal was combined with electroplating or plasma spraying and isostatic pressing to form a metal support for the ceramic. Rocket engine thrust chambers coated with 0.08 mm (3 mil) of ZrO2-8Y2O3 had no failures and a tenfold increase in engine life. Some measured mechanical properties of the plasma-sprayed ceramic are presented.

Quentmeyer, R. J.↗
NASA NTRS1985

Real-time SEM studies in controlled reactive atmospheres

A unique scanning electron accessory has been developed that allows the observation of specimens under partial pressures of any gas. The sample is placed in a metal support boat inside a special sample holder. The sample in the boat is imaged on a CRT and is simultaneously recorded on a videotape, allowing the reaction between the sample and the gas to be observed in real time. Sample changes can be seen continuously as the sample is being heated or cooled. This process allows the observation of material transformations such as phase changes as they happen. Temperatures as high as 1000 C have been used and are continuously monitored using a thermocouple with a digital display on the CRT and videotape. X-ray analyses can also be run before and after any reactions. In the study described here, thick-film screen-printing inks using molybdenum/tin compositions as a replacement for silver were developed to be used on terrestrial photovoltaic cells. Pieces were placed on the sample stage and heated in both O2 and H2 atmospheres. The results were used to determine the most effective frits to be used in the thick-film inks.

Gallagher, B. D.↗
NASA NTRS1991

THz dichroic plates for use at high angles of incidence

The design of a high frequency dichroic plate consisting of an electrically thick self supporting metallic mesh that can be used in a linearly polarized quasi-optical system at high angles of incidence is described. The measured and computed performance of a 2.5-inch aperture mesh is given. This mesh has a 3-dB cutoff frequency of 875 GHz and less than 0.75 dB of transmission loss from 950-1350 GHz at incidence angles of 0, 30, and 45 degrees. The results of a multimode waveguide analysis corroborate the measured data.

Siegel, Peter H.↗
NASA NTRS2005

High-Temperature Polymer Composites Tested for Hypersonic Rocket Combustor Backup Structure

Significant component weight reductions are required to achieve the aggressive thrust-toweight goals for the Rocket Based Combined Cycle (RBCC) third-generation, reusable liquid propellant rocket engine, which is one possible engine for a future single-stage-toorbit vehicle. A collaboration between the NASA Glenn Research Center and Boeing Rocketdyne was formed under the Higher Operating Temperature Propulsion Components (HOTPC) program and, currently, the Ultra-Efficient Engine Technology (UEET) Project to develop carbon-fiber-reinforced high-temperature polymer matrix composites (HTPMCs). This program focused primarily on the combustor backup structure to replace all metallic support components with a much lighter polymer-matrixcomposite- (PMC-) titanium honeycomb sandwich structure.

Sutter, James K.↗
DOE OSTI2022

Method of making an electrochemical cell

Disclosed is a method of making an electrochemical cell, comprising: depositing an anode layer on a surface of a porous metal support layer; depositing an electrolyte layer on a surface of the anode layer, wherein the electrolyte layer is deposited via suspension plasma spray, wherein the electrolyte layer conducts protons; and depositing a cathode layer on a surface of the electrolyte layer. Also disclosed is a stack comprising two or more of the electrochemical cell.

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

Chemical looping conversion of CH4/CO2 to syngas on 5wt.%Ni@Ce0.6Zr0.4O2 catalyst: Impact of dynamic accumulation of surface carbon and oxygen vacancies

Syngas, a combination of carbon monoxide (CO) and hydrogen (H2), is a precursor to many chemicals and fuels, contributing to the billion-dollar global hydrocarbon industry. Chemical looping reforming (CLR) of the greenhouse gases methane (CH4) and carbon dioxide (CO2) allows for energy-efficient production of syngas. 5wt.% nickel (Ni) on ceria-zirconia (5wt%Ni@Ce0.6Zr0.4O2) mixed metal oxide catalyst was investigated here to explore pathways for enhanced syngas production on sustainable earth-abundant transition metal supported catalysts. The role of reduction-oxidation (redox) state of the catalyst, and carbon formation on the catalyst surface during chemical looping is explored to drive superior reaction kinetics, conversions, selectivity, and syngas ratios (H2/CO). The bulk and surface structure of the catalyst, along with carbon deposition features were characterized by electron microscopy, X-Ray diffraction, and ex situ Raman spectroscopy. The dynamic evolution of catalysts under CLR reaction conditions and the intrinsic reaction mechanisms were probed with in situ Raman spectroscopy, in situ Fourier transform spectroscopy, dynamic oxygen storage capacity (DOSC), and the Temporal Analysis of Products (TAP) reactor studies. Intrinsic kinetics of syngas production via CLR was correlated to the redox state of catalyst and the participation of nickel-catalyzed multiwalled carbon nanotube (CNT) growth, allowing enhanced CLR reaction performance.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2024

Understanding the solubility of metal salts and supporting electrolytes in Deep Eutectic Solvents [Slides]

Our objective is to determine how alterations in these parameters affect solubility in order to identify the optimal conditions for Zirconium electrodeposition. Create a variety of Deep Eutectic Solvents by combining different combinations and molar ratios of both hydrogen bond donors and hydrogen bond acceptors. Investigate the solubility of different Zirconium metal sources and supporting electrolytes individually, as well as in combination of both. Analyze various parameter conditions including temperature, pH, and conductivity. Determine the optimal composition and parameter setup for Zirconium electrodeposition. Obtain Zirconium coating through various methods and parameter adjustments.

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

Metal-organic framework supported single-site nickel catalysts for butene dimerization

Homotopic sites in a well-controlled environment are not only ideal systems for mechanistic studies, but also allow optimal control of catalytic transformations. Sites having only a single metal cation and sites consisting of metal oxo complexes with few nickel (Ni) cations supported on the nodes of UiO-66 metal-organic framework (Ni-UiO-66) are studied for 1-butene dimerization. Monomeric Ni sites, which bind to the Zr 6 node via two Zr-OH(µ3) linkages, are active and selective for the dimerization of 1-butene to linear and mono-branched C 8 isomers. Ni oxo complexes with few Ni cations show lower activity and promote the oligomerization of transiently formed C 8 isomers. In conclusion, Kohn-Sham density function theory calculations combined with spectroscopic measurements and kinetic analyses indicate that dimerization follows a Cossee-Arlman reaction mechanism.

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

Computational and Experimental Characterization of the Ligand Environment of a Ni-Oxo Catalyst Supported in the Metal–Organic Framework NU-1000

Heterogeneous catalysts exhibit significant changes in composition due to the influence of operating conditions, and these compositional changes can have dramatic effects on catalytic performance. For traditional bulk metal heterogeneous catalysts, relationships between composition and catalytic operating conditions are well documented. However, the influence of operating conditions on the compositions of single-site heterogeneous catalysts remains largely unresolved. To address this, we report a combined computational and experimental characterization of a Ni oxo catalyst under catalytic hydrogenation conditions. Specifically, pair distribution function (PDF) analysis is combined with ab initio thermodynamic modeling to investigate ligand environments present on a Ni oxo cluster supported in the metal–organic framework NU-1000. Comparisons of the experimentally observed and simulated Ni–O coordination numbers and Ni–O, Ni···Ni, and Ni···Zr distances provide insight into the Ni ligand environment under H 2 (g). These comparisons suggest significant OH and H 2 O content and, further, that different Ni ions within the cluster and/or NU-1000 structure may comprise subtly different numbers of these ligands. Further, the observation of significant H 2 O content under H 2 (g) suggests that the NU-1000 support supplies H 2 O to the cluster. Examples of ligand environments that could lead to the observed PDFs are provided. Furthermore, the combination of simulations and experiments provides new insights into the ligand environment for Ni-NU-1000 catalysts that will be useful for understanding the ligand environments of other single-site Ni catalysts as well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Controlling the Ru Island Decoration on Ni Nanoparticles to Tune the Activity for 5-Hydroxylmethylfurfural (HMF) Oxidation

Controlling the island decoration on metal nanoparticle supports is a major opportunity for improving the catalytic activity and an attractive synthetic challenge. The structure of the decorating metal determines how it interacts with the metal support and how it effectively catalyzes the reactants and the intermediates. In this work, we demonstrate that a slow-growth method maximizes the formation of Ru islands on faceted, branched Ni nanoparticles, thereby controlling the number of Ru–Ni atomic interactions and improving the catalytic activity. The Ru islands on branched Ni nanoparticles with the highest loading of Ru (9%) exhibited the highest activity for the electro-oxidation of biomass-derived 5-hydroxymethylfurfural (HMF). In conclusion, these results demonstrate the ability to synthetically control the second metal decoration to tune metal–support interactions, thereby enhancing the catalytic activity.

5-hydroxymethylfurfural↗
DOE OSTI2021

Insights into the Structure–Activity Relationship in Aerobic Alcohol Oxidation over a Metal–Organic-Framework-Supported Molybdenum(VI) Catalyst

The understanding of structure–activity relationships at the atomic level has played a profound role in heterogeneous catalysis, providing valuable insights into designing suitable heterogeneous catalysts. However, uncovering the detailed roles of how such active species’ structures affect their catalytic performance remains a challenge owing to the lack of direct structural information on a specific active species. Herein, we deposited molybdenum(VI), an active species in oxidation reactions, on the Zr 6 node of a mesoporous zirconium-based metal–organic framework (MOF) NU-1200, using solvothermal deposition in MOFs (SIM). Due to the high crystallinity of the NU-1200 support, the precise structure of the resulting molybdenum catalyst, Mo-NU-1200, was characterized through single-crystal X-ray diffraction (SCXRD). Two distinct anchoring modes of the molybdenum species were observed: one mode (Mo1), displaying an octahedral geometry, coordinated to the node through one terminal oxygen atom and the other mode (Mo2) coordinated to two adjacent Zr 6 node oxygen atoms in a tetrahedral geometry. To investigate the role of base in the catalytic activity of these Mo centers, we assessed the activity of Mo-NU-1200 for the aerobic oxidation of 4-methoxybenzyl alcohol as a model reaction. The results revealed that Mo-NU-1200 exhibited remarkably higher catalytic reactivity under base-free conditions, while the presence of base inhibited the catalytic reactivity of this species. SCXRD studies revealed that the molybdenum binding motifs (structures of the supported metal on the Zr 6 node in the MOF) changed over the course of the reactions. Following the oxidation without base, both pristine coordination modes (Mo1 and Mo2) evolved into a new coordination mode (Mo3), in which the molybdenum atom coordinated to two adjacent oxygen atoms from the Zr 6 node in an octahedral geometry, while in the presence of base, the pristine Mo1 coordination mode evolved entirely into the pristine Mo2. Here, this study demonstrates the direct observation of an active species’ structural evolution from metal installation to subsequent catalytic reaction. As a result, these subtle structural changes in catalyst binding motifs led to distinct differences in catalytic activities, providing a compelling strategy for elucidating structure–activity relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Formation of (Rh–Fe)–FeO x Complex Sites Enables Methanol Synthesis from CO 2

Here, we addressed the challenges of designing catalysts for selective CO 2 hydrogenation by incorporating oxide Fe species onto Rh nanoparticles. Nanoscopic FeO x domains created a “reverse catalyst” structure (i.e., a metal oxide supported on a metal) that increased the density of interfacial sites compared to traditional supported catalysts. The contact between the metal nanoparticle and the oxide overlayer induced the formation of a surface Rh-Fe alloy that stabilize methoxy groups while suppressing hydrogenolysis to methane. Sites at FeO x -metal interfaces interact with CO 2 sevenfold stronger than sites on metal surfaces, show larger energy barriers to cleave the C-O bonds, and offer a barrierless pathway for hydrogenation of methoxy species to methanol. Consequently, the multifunctional sites over FeO x /Rh-Fe catalysts highlight and meet the requirements of a selective methanol catalyst: strong interaction with CO 2 to ensure high density of transition states; metal sites to activate and make hydrogen available to surface intermediates; and high energy barriers for C-O bond cleavage to form carbides. These synthesis and catalytic chemistries, demonstrated for Rh-Fe-FeO x interfaces, enable us to overcome the limitations to the design of methanol production catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

Electrochemical, Polarization, and Crevice Corrosion Testing of Inconel X750: A Supplement to the Environmental Control and Life Support System Sustaining Metal Materials Compatibility Study

In previous studies, electrochemical test results were experimentally acquired and then presented for several noble alloys in two specific solutions representative of waste liquids generated or present within the Environmental Control and Life Support System (ECLSS) aboard the International Space Station (ISS). Subsequently, another metal candidate, Inconel X750, has been submitted and was subjected to the same test routines in the same solutions and evaluated with the same statistical/analytical methodologies as those utilized in the earlier studies. Previous studies included three titanium grades, (Commercially Pure, 6Al-4V alloy, and 6Al-4V Low Interstitial alloy), two nickel-chromium alloys (Inconel® 625 and Hastelloy® C276), one high tier stainless steel (Cronidur® 30), and a nickel-titanium alloy (Nitinol 60). Thus far, all candidate alloys have exhibited excellent corrosion protection and galvanic compatibility attributes and have been deemed qualified materials for application within the ECLSS facility. Inconel X750 now joins that group. The titanium alloys gave the best results of all the metal candidates by demonstrating superior nobility and galvanic protection properties. It is worth noting that the corrosion performance properties for the three titanium alloys were essentially indistinguishable. As such and for expediency, this study and all future evaluations will refer only to the comparative properties already documented for Titanium 6Al-4V as this alloy is representative of all three alloys and considered to be more mainstream. Now the measured corrosion properties for Inconel X750 were very similar to those determined previously for Inconel 625 and Hastelloy C276 which were also determined to be very high performers. For the current effort, the results have clearly shown that Inconel X750 possesses exceptional anti-corrosion attributes comparable to metals in the highest tier of the galvanic series. Overall, one can conclude that Inconel X750 is quite noble, highly corrosion resistant and galvanically compatible with the other metal groups from both an electrochemical perspective and a long-term exposure scenario. This was clearly demonstrated after utilizing the same techniques as those applied in previous studies which included linear, Tafel and cyclic polarization, galvanic coupling with each of the other metal candidates, and pitting/crevicing assessments after one full year of immersion in the subject test solutions. Attributes defining the nobility and anti-corrosion capabilities for X750 appear to be on par with all the other candidates thus far and this alloy can now be classified as ‘excellent’ exhibiting very high resistance toward general, localized, and galvanic corrosion in the subject test media.

Lee, R. E.↗
DOE OSTI2024

Intercalative Redox Tuning for Cu/Li x Mn 2 O 4 -Catalyzed Oxidative Alkyne Coupling

Modulation of heterogeneous catalyst structure is ubiquitous within efforts to improve catalytic activity and selectivity at the molecular level. Herein, manganese oxide (MnO 2 ) is employed as a continuously tunable catalyst support through increasing extent of lithium intercalation and reduced surface potential. Oxidative grafting of an organocopper complex onto various lithium manganese oxides (Li x Mn 2 O 4 , x = 0-2.1) produced divalent and monovalent copper species on the partially reduced (0 ≤ x ≤ 1.2) and fully reduced (x = 2.1) surfaces, respectively, as determined by X-ray absorption fine structure (XAFS) analysis. In this study, the resultant materials are catalytically active for the oxidative coupling of terminal alkynes, with steady-state reaction rate data of oxidative propyne dimerization (200 °C, 0.6-2.4 kPa propyne, 2.4-9.9 kPa O 2 ) indicating that complete support lithiation (Li 2.1 Mn 2 O 4 ) provides increased catalytic performance and renders reoxidation steps less kinetically demanding compared to the unreduced parent material. Enacting a dual site (Cu and MnO x ) kinetic model can account for dimerization rates measured over Cu/Li 2.1 Mn 2 O 4 under various reactant concentrations, copper loadings, and surface coverages, providing supporting evidence for the synergistic role of the metal and support in facilitating the coupling reaction. Overall, results presented here provide an extension for general strategies of systematically controlling catalytic structure and function through lithium reduction of bulk oxides and subsequent electronic modulation of the metals supported thereon.

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

Self-Anchored Platinum-Decorated Antimony-Doped-Tin Oxide as a Durable Oxygen Reduction Electrocatalyst

The lifetime of commercial Proton Exchange Membrane Fuel Cells (PEMFCs) is circumscribed by the insufficient durability of commercial catalysts. The use of metal oxide supports in place of carbon significantly increases electrocatalyst durability. Herein, following density functional theory (DFT) predictions of improved Platinum (Pt) stability on antimony doped tin oxide (ATO) supports, we synthesized ATO whose morphology and crystal structure was engineered using a Pt anchoring technique. X-ray photoelectron spectroscopy (XPS) indicated that the Pt anchor sites aided in the reduction of Pt precursors to Pt on the ATO surface. X-ray absorption near-edge spectroscopy (XANES) revealed the existence of strong-metal-support interactions (SMSI) between Pt and ATO. The combination of SMSI and high control over Pt dispersion enabled the Pt/Pt-aerogel-ATO (Pt supported on aerogel ATO with Pt anchor sites) electrocatalyst to achieve 2x the area specific activity of Pt/C in ex-situ testing. In a H 2 /air PEMFC Pt/Pt-aerogel-ATO cathodes enabled 20% higher peak power density and <1/6 the loss of active surface area as compared to Pt/C. Notably, in a PEMFC under rigorous potential cycling, the Pt/Pt-aerogel-ATO retained its initial peak power density as opposed to a 58% loss for Pt/C. Further, cost models indicate that Pt/Pt-aerogel-ATO is 26% less expensive than Pt/C over its useful lifetime.

25 ENERGY STORAGE↗