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At least 253 records · Page 14

Oxidation of Copper Alloy Candidates for Rocket Engine Applications

The gateway to affordable and reliable space transportation in the near future remains long-lived rocket-based propulsion systems; and because of their high conductivities, copper alloys remain the best materials for lining rocket engines and dissipating their enormous thermal loads. However, Cu and its alloys are prone to oxidative degradation -- especially via the ratcheting phenomenon of blanching, which occurs in situations where the local ambient can oscillate between oxidation and reduction, as it does in a H2/02- fuelled rocket engine. Accordingly, resistance to blanching degradation is one of the key requirements for the next generation of reusable launch vehicle (RLV) liner materials. Candidate copper alloys have been studied with a view to comparing their oxidation behavior, and hence resistance to blanching, in ambients corresponding to conditions expected in rocket engine service. These candidate materials include GRCop-84 and GRCop-42 (Cu - Cr-8 - Nb-4 and Cu - Cr-4 - Nb-2 respectively); NARloy-Z (Cu-3%Ag-0.5%Y), and GlidCop (Cu-O.l5%Al2O3 ODS alloy); they represent different approaches to improving the mechanical properties of Cu without incurring a large drop in thermal conductivity. Pure Cu (OFHC-Cu) was included in the study to provide a baseline for comparison. The samples were exposed for 10 hours in the TGA to oxygen partial pressures ranging from 322 ppm to 1.0 atmosphere and at temperatures of up to 700 C, and examined by SEM-EDS and other techniques of metallography. This paper will summarize the results obtained.

Ogbuji, Linus U. Thomas↗

VPS Process for Copper Components in Thrust Chamber Assemblies

For several years, NASA's Marshall Space Flight Center (MSFC) has been working with Plasma Processes, Inc., (PPI) to fabricate thrust chamber liners with GRCop-84. Using the vacuum plasma spray (VPS) process, chamber liners of a variety of shapes and sizes have been created. Each has been formed as a functional gradient material (FGM) that creates a unique protective layer of NiCrAlY on the GRCop-84 liner s hot wall surface. Hot-fire testing was successfully conducted on a subscale unit to demonstrate the liner's durability and performance. Similar VPS technology has also been applied to create functional gradient coatings (FGC) on copper injector faceplates. Protective layers of NiCrAlY and zirconia were applied to both coaxial and impinging faceplate designs. Hot-fire testing is planned for these coated injectors in April 2005. The resulting material systems for both copper alloy components allows them to operate at higher temperatures with improved durability and operating margins.

Elam, Sandra↗

Comparison of the Fatigue Behavior of Copper Alloys

This presentation is about the development of advanced copper alloys with high thermal conductivity, good creep strength, and adequate fatigue strength for rocket engine applications. It also focuses on the commercial availability of the advanced alloy-GRCop-84 developed at NASA-GRC. The presentation's conclusions are that GRCop-84 has equivalent or better isothermal fatigue lives compared to other commercially available copper alloys, that GRCop-84 can be fabricated in various forms with minimal change in the fatigue lives, that it is equivalent in sothermal, fatigue to AMZIRC at moderate temperatures, and that Narloy-Z is equivalent in fatigue capabilities to GRCop-84 at 400C and below.

Lerch, Brad↗

Synthesis, Characterization, and Processing of Copper, Indium, and Gallium Dithiocarbamates for Energy Conversion Applications

Ten dithiocarbamate complexes of indium(III) and gallium(III) have been prepared and characterized by elemental analysis, infrared spectra and melting point. Each complex was decomposed thermally and its decomposition products separated and identified with the combination of gas chromatography/mass spectrometry. Their potential utility as photovoltaic materials precursors was assessed. Bis(dibenzyldithiocarbamato)- and bis(diethyldithiocarbamato)copper(II), Cu(S2CN(CH2C6H5)2)2 and Cu(S2CN(C2H5)2)2 respectively, have also been examined for their suitability as precursors for copper sulfides for the fabrication of photovoltaic materials. Each complex was decomposed thermally and the products analyzed by GC/MS, TGA and FTIR. The dibenzyl derivative complex decomposed at a lower temperature (225-320 C) to yield CuS as the product. The diethyl derivative complex decomposed at a higher temperature (260-325 C) to yield Cu2S. No Cu containing fragments were noted in the mass spectra. Unusual recombination fragments were observed in the mass spectra of the diethyl derivative. Tris(bis(phenylmethyl)carbamodithioato-S,S'), commonly referred to as tris(N,N-dibenzyldithiocarbamato)indium(III), In(S2CNBz2)3, was synthesized and characterized by single crystal X-ray crystallography. The compound crystallizes in the triclinic space group P1(bar) with two molecules per unit cell. The material was further characterized using a novel analytical system employing the combined powers of thermogravimetric analysis, gas chromatography/mass spectrometry, and Fourier transform infrared (FT-IR) spectroscopy to investigate its potential use as a precursor for the chemical vapor deposition (CVD) of thin film materials for photovoltaic applications. Upon heating, the material thermally decomposes to release CS2 and benzyl moieties in to the gas phase, resulting in bulk In2S3. Preliminary spray CVD experiments indicate that In(S2CNBz2)3 decomposed on a Cu substrate reacts to produce stoichiometric CuInS2 films.

Duraj, S. A.↗

Copper Nanowire Production for Interconnect Applications

A method of fabricating metallic Cu nanowires with lengths up to about 25 micrometers and diameters in a range 20-100 nanometers, or greater if desired. Vertically oriented or laterally oriented copper oxide structures (CuO and/or Cu2O) are grown on a Cu substrate. The copper oxide structures are reduced with 99+ percent H or H2, and in this reduction process the lengths decrease (to no more than about 25 micrometers), the density of surviving nanostructures on a substrate decreases, and the diameters of the surviving nanostructures have a range, of about 20-100 nanometers. The resulting nanowires are substantially pure Cu and can be oriented laterally (for local or global interconnects) or can be oriented vertically (for standard vertical interconnects).

Han, Jin-Woo↗

Design, Development and Hotfire Testing of Monolithic Copper and Bimetallic Additively Manufactured Combustion Chambers

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) otherwise commonly referred to as additive manufacturing. The NASA Low Cost Upper Stage Propulsion (LCUSP) program was designed to develop processes and material characterization for the GRCop-84 copper-alloy commensurate with powder bed additive manufacturing, 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. As a direct spin off of this program, NASA is working with industry partners to further develop the printing process for the GRCop-84 material in addition to the C-18150 (CuCrZr) material. To advance the process further and allow for optimization with multiple materials, NASA is also investigating the feasibility of bimetallic additively manufactured chambers. A 1.2k sized thrust-chamber was designed and developed to compare the printing process of the GRCop-84 and C-18150 SLM materials. A series of similar MCC liners also completed development with an Inconel 625 jacket bonded to the GRcop-84 liner evaluating direct metal deposition (DMD) laser and arc-based techniques. This paper describes the design, development, manufacturing and testing of these combustion chambers and associated lessons learned throughout the design and development process.

Gradl, Paul↗

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.↗

Improved thermoelectric performance of α- and β- Cu 2 Se through suppression of hole density using extrinsic copper vacancies

Modulating Cu + ion disorder in Cu 2 Se can enable control over the polymorphism and the carrier density leading to enhanced thermoelectric properties for both α- and β-Cu 2 Se. Here we report that the incorporation of Cr 3+ into the Cu 2 Se crystal lattice facilitates the stabilization of α-Cu 2 Se at 300 K leading to a large (~140%) reduction in the carrier density both below and above the phase transition. This is attributed to the reduction in the density of intrinsic copper interstitials (Cu$^{•}_{i}$) within the Cu (2-δ-λ) (Cr$^{··}_{Cu}$)λ(V$^{'}_{Cu}$)δ(Cu$^{π}_{i}$) δ-2λ (h • ) δ-2λ Se crystal lattice. Such optimization of the carrier density led to a large (63%) increase in the thermopower and a drastic (46%) reduction in the total thermal conductivity for both α- and β-Cu 2 Se matrices. Consequently, a significant enhancement of the thermoelectric performance is observed in the entire temperature range from 300 K to 773 K. This results in high average ZT values for both α-Cu 2 Se (ZT ave = 0.60) and β-Cu 2 Se (ZT ave = 0.97), which paves the way for both near room temperature and high temperatures applications. Furthermore, this work provides a new approach to optimize the thermoelectric performance of Cu 2 Se-based materials by leveraging the interaction between mobile intrinsic Cu$^{·}_{i}$ and extrinsic V$^{'}_{Cu}$ to suppress the hole density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduction of vanadium diffusivity within copper grain boundaries due to enhanced binding

We investigate permeation of vanadium (V) through copper (Cu) layers in V/Cu/niobium (Nb) and molybdenum (Mo)/Cu/V tri-layer composites and compare it with the permeation behavior of Nb. Despite their low solubility in single-crystal Cu, both V and Nb permeate readily due to short-circuit transport through Cu grain boundaries (GBs). However, Nb permeates preferentially to V. Atomistic simulations suggest that this difference is due to lower V diffusivity at general GBs in Cu, compared to Nb. Here, the lower V diffusivity, in turn, arises from stronger V binding to the boundary, which manifests as a greater equilibrium GB concentration as well as a higher activation energy for GB diffusion.

36 MATERIALS SCIENCE↗

Dependence of the elastic strain coefficient of copper on the pre-treatment

The effect of various pre-treatments on the elastic strain coefficient (alpha) (defined as the reciprocal of the modulus of elasticity E) (Epsilon) and on the mechanical hysteresis of copper has been investigated. Variables comprising the pre-treatments were pre-straining by stretching in a tensile testing machine and by drawing through a die, aging at room and elevated temperatures and annealing. The variation of the elastic strain coefficient with test stress was also investigated.

RODS - TENSION↗

Dual Chemical Looping/Catalytic Process for Alkylation of Benzene With Ethane and Propane Yielding Ethylbenzene and Cumene Over Copper‐Containing Mordenite

Given the sustained demand for alkylated aromatics and the strained olefin market, there is an urgent need to develop efficient one‐step processes for the direct alkylation of aromatics using alkanes instead of olefins. Such technologies offer greater energy efficiency and sustainability by eliminating the need for separate, energy‐intensive alkane dehydrogenation steps. In this work, we report a dual chemical looping / catalytic process that couples alkane dehydrogenation with aromatic alkylation over a copper‐containing mordenite yielding up to 25% of alkylated aromatics with >97% selectivity per cycle. In situ MAS NMR and FTIR spectroscopies combined with DFT calculations showed that the alkylation of benzene with alkanes proceeds via a π‐bounded Cu(I)‐olefin intermediate, which subsequently interacts with benzene, catalyzed by Brønsted acid sites, leading to alkylated products that readily desorb from the active material into the gas phase. DFT calculations show that alkylation mediated solely by Cu(I) has prohibitively high barriers (>1.8 eV), whereas a bi‐functional pathway involving both Cu(I) and Brønsted acid sites can proceed with significantly lower barrier (0.8 eV) through a concerted C–C bond formation and proton transfer step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Process parameter translation strategies for variable directed energy deposition spot size using 316L, copper, and Inconel 625

Directed energy deposition (DED) is a form of additive manufacturing available across a variety of laser spot diameter values, often referred to as spot sizes. However, there is no method to easily transfer process parameters across discrete spot sizes, leading to DED process parameters that are equipment specific and not widely applicable. In this study, a strategy is proposed and investigated for five spot sizes that keep the areal energy density constant while varying power, feed rate, and powder flow during the deposition of 316L stainless steel. An assessment of trends in hardness and microstructure is possible due to the novel production of components of a single material across several spot sizes using a single nozzle on a single DED system. The proposed strategy was used to nullify the hardness drop during functional grading of Inconel 625 and pure copper, enabling fabrication of multi-material sample that does not compromise desirable properties. This application shows the value in establishing more efficient process parameter development and understanding spot size influences on geometric and material property flexibility, to enable a more diverse powder-based DED design space and to increase the industry adoption of DED systems.

316L↗

Stabilization and manipulation of highly concentrated copper single atoms by high entropy oxides

Facile and controllable methodologies capable of providing single atom catalysts (SACs) with high-density active metal sites and sintering-resistance under harsh conditions are highly desired and grand challenges in heterogeneous catalysis. Herein, the entropy effect was leveraged to stabilize and manipulate the electronic properties of copper SACs. The as-developed ultrasonication-driven approach could integrate highly concentrated Cu SAs within the lattice of fluorite-structured high entropy oxide (HEFO) under ambient conditions (CuO-HEFO). The dual benefits from the high entropy effect of the support and the in-situ lattice engineering led to the generation of abundant Cu 1+ species and oxygen defects, together with ultra-high stability and sintering-resistance under extremely harsh conditions. This was confirmed by deploying non-high entropy support (CuO-CeO 2 ) or Cu sites located on the surface of HEFO (CuO@HEFO). In conclusion, the catalytic activity of CuO-HEFO surpassed that of CuO-CeO 2 and CuO@HEFO in CO oxidation together with well-maintained long-term stability and resistance to gas impurities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen activation by rhodium under the cover of a copper oxide thin film

Here, the activation of reactants by catalytically active metal sites at metal-oxide interfaces is important for understanding the effect of metal-support interactions on nanoparticle catalysts and for tuning activity and selectivity. Using a combined experimental and theoretical approach, we studied the activation of H 2 and the effect of CO poisoning on isolated Rh atoms completely or partially covered by a copper oxide (Cu 2 O) thin film. Temperature-programmed desorption (TPD) experiments conducted in ultra-high vacuum (UHV) show that neither a partially nor a fully oxidized Cu 2 O layer grown on a Rh/Cu(111) single-atom alloy can activate hydrogen in UHV. However, in situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments performed at elevated H 2 pressures reveal that Rh significantly accelerates the reduction of these Cu 2 O thin films by hydrogen. Remarkably, the fastest reduction rate is observed for the fully oxidized sample with all Rh sites covered by Cu 2 O. Both TPD and AP-XPS data demonstrate that these covered Rh sites are inaccessible to CO, indicating that Rh under Cu 2 O is active for H 2 dissociation but cannot be poisoned by CO. In contrast, an incomplete oxide film leaves some of the Rh sites exposed and accessible to CO, and hence prone to CO poisoning. Density functional theory calculations demonstrate that unlike many reactions in which hydrogen activation is rate limiting, the rate-determining step in the dissociation of H 2 on thin-film Cu 2 O with Rh underneath is the adsorption of H 2 on the buried Rh site, and once adsorbed, the dissociation of H 2 is barrierless. These calculations also explain why H 2 can only be activated at higher pressures. Together, these results highlight how different the reactivity of atomically dispersed Rh in Cu can be depending on its accessibility through the oxide layer, providing a way to engineer Rh sites that are active for hydrogen activation but resilient to CO poisoning.

36 MATERIALS SCIENCE↗

Abiotic manganese oxide formation induced by light and copper-driven Fenton chemistry

Redox-active transition metals such as manganese (Mn) and copper (Cu) frequently coexist in surface water systems, where their interactions can significantly influence contaminant fate and water quality. It is widely known that the oxidation of Mn 2+ (aq) to Mn(IV) oxide solids is driven mainly by biotic processes in which Cu 2+ serves as an inhibitor of Mn oxidation. However, Cu 2+ can also trigger Fenton reactions to produce reactive oxygen species (ROS) capable of promoting the abiotic Mn oxidation (i.e., without the involvement of biological organisms), through an alternative natural pathway that remains overlooked in water. In this study, we found that the abiotic oxidation of Mn 2+ can be facilitated by the co-existence of sunlight and Cu 2+ . By contrasting Cu 2+ with other divalent cations, such as Ca 2+ , Mg 2+ , and Zn 2+ , this investigation highlights the distinct role of Cu 2+ in promoting Mn oxidation. Moreover, the study elucidated how light induces ROS to trigger Cu-driven photo-Fenton reactions and identified the roles of ROS in Mn oxidation. Chemical-Fenton reactions (i.e., the interaction between Cu and H 2 O 2 in the absence of light) were also examined for their contribution to the Cu-driven Mn photo-oxidation, supporting the involvement of Fenton chemistry in Mn oxidation. By elucidating the novel photochemical mechanism of Mn oxide formation, our findings advance the understanding of heavy metal interactions in aqueous environments and highlight the intricate roles of Cu 2+ in affecting elemental cycling and the evaluation of heavy metal contamination in water resources. This discovery also underscores the critical contribution of co-existing Fenton-active metals in forming Mn oxide solids.

Abiotic Mn oxidation↗

Reconstruction and Dissolution of Copper Catalysts during Electrocatalytic Nitrate Reduction

Copper-based electrocatalysts are widely explored for electrochemical nitrate remediation, yet their stability under operating conditions remains poorly understood. While nanoscale and subnanoscale Cu motifs are known to restructure during the nitrate reduction reaction (NO 3 RR), how these transformations translate into irreversible material loss remains unclear. Here, we quantify Cu dissolution during NO 3 RR as a function of catalyst architecture and electrolyte chemistry using two model systems: single-atom Cu (Cu 1 ) and Cu nanoparticles (Cu NP ). Time-resolved leaching measurements, integrated with in situ X-ray absorption spectroscopy (XAS), reveal measurable Cu loss for both catalysts during NO 3 RR. Dissolution is concentrated at the initiation of electrolysis, coinciding with rapid restructuring, and depends strongly on morphology, with Cu NP consistently exhibiting greater Cu loss than Cu 1 . In situ XAS reveals that Cu 1 forms transient metallic clusters under reduction that largely redisperse upon returning to open-circuit voltage, whereas Cu NP undergoes reduction of an oxidized surface layer accompanied by sustained Cu loss during electrolysis. Notably, the presence of nitrate significantly intensifies restructuring and Cu loss, highlighting the critical role of electrolyte composition. Furthermore, these findings establish a direct link between electrochemical restructuring and Cu dissolution, unveiling electrolyte-dependent interactions as key determinants of catalyst durability in electrochemical nitrate conversion.

36 MATERIALS SCIENCE↗

Domain-Dependent Electronic Properties of 2D Copper Boride Synthesized from Reversible Subsurface Diffusion on Cu(111)

Emerging boron-based 2D materials hold properties with potential applications ranging from electronic devices to catalysis and energy storage. Using physical vapor deposition, 2D copper borides are formed on Cu(111) at elevated temperatures. However, the as-prepared surfaces often contain boron clusters that compromise structural homogeneity, and the dynamics of their formation is not yet fully understood. Through in situ low-energy electron microscopy (LEEM), Auger electron spectroscopy (AES), and scanning tunneling microscopy/spectroscopy (STM/STS), we show that cluster-free 2D CuB x is synthesized via reversible subsurface diffusion of boron atoms. The resolved regular atomic structure aligns with the previously calculated Cu 8 B 14 model. In a rare case, possibly due to surface strain and a change of orientation, a second domain of CuB x was observed with a pronounced change in electronic properties, yet electronic states remain delocalized in both domains. In conclusion, these findings demonstrate the sensitivity of electronic properties to domain structure and highlight a potential opportunity to tune 2D CuB x for diverse applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗