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At least 19 records

Single rhenium atoms on nanomagnetite: Probing the recharge process that controls the fate of rhenium in the environment

Understanding the redox transitions that control rhenium geochemistry is central to paleoredox and geochronology studies, as well as predicting the fate of chemically similar hazardous oxyanions in the environment such as pertechnetate. However, detailed mechanistic information regarding rhenium redox transitions in anoxic systems is scarce. Here, we performed a comprehensive laboratory study of rhenium redox transitions on variably oxidized magnetite nanoparticle surfaces. Through high-end spectroscopic and microscopic tools, we propose an abiotic transition pathway in which aqueous iron(II) ions in the presence of pure or preoxidized magnetite serve as an electron source to reduce rhenium(VII) to individual rhenium(IV) atoms or small polynuclear species on nanoparticle surfaces. Notably, iron(II) ions recharged preoxidized magnetite nanoparticles exhibit a maghemite core and a magnetite shell, challenging the traditional core-shell magnetite-maghemite model. This study provides a fundamental understanding of redox processes governing rhenium fate and transport in the environment and enables an improved basis for predicting its speciation in geochemical systems.

Science & Technology - Other Topics↗

Mechanical properties of electron-beam-melted molybdenum and dilute molybdenum-rhenium alloys

A study of molybdenum and three dilute molybdenum-rhenium alloys was undertaken to determine the effects of rhenium on the low temperature ductility and other mechanical properties of molybdenum. Alloys containing 3.9, 5.9, and 7.7 atomic percent rhenium exhibited lower ductile-brittle transition temperatures than did the unalloyed molybdenum. The maximum improvement in the annealed condition was observed for molybdenum - 7.7 rhenium, which had a ductile-brittle transition temperature approximately 200 C (360 F) lower than that for unalloyed molybdenum. Rhenium additions also increased the low and high temperature tensile strengths and the high temperature creep strength of molybdenum. The mechanical behavior of dilute molybdenum-rhenium alloys is similar to that observed for dilute tungsten-rhenium alloys.

Klopp, W. D.↗

Rhenium-Selenido Corroles: Reflections on 5d Metalloporphyrins and Metallocorroles as Triplet Emitters and Photosensitizers

Following the successful synthesis of rhenium-oxido, rhenium-imido, and rhenium-sulfido corroles, a series of para-X-substituted rhenium-selenido triarylcorroles (X = OCH 3 , CH 3 , H, F, CF 3 ) have been prepared in 70–76% yields. A one-pot, two-step procedure was used, analogous to that used for ReS corroles, involving rhenium insertion via high-temperature reaction of Re 2 (CO) 10 and free-base corroles in refluxing decalin, followed by exposure to PCl 3 (which is thought to deoxygenate ReO corroles formed under the reaction) and elemental selenium. An analogous procedure, however, failed to yield rhenium-tellurido corroles, presumably reflecting, according to DFT calculations, the limited stability of these species. Unlike ReO corroles, ReS and ReSe corroles were found not to exhibit phosphorescence in the NIR-I regime (600–1000 nm); nor did they sensitize singlet oxygen formation. In the hope of obtaining a broader perspective of this negative result, we also examined ReN porphyrins and found them not to phosphoresce or to sensitize singlet oxygen formation. These results were explained by DFT and TDDFT calculations in terms of low-energy triplet states, which are not energetic enough to excite molecular oxygen to its lowest singlet state. Whether some of the new Re corroles exhibit phosphorescence in the NIR-II regime remains an interesting question for future investigation.

Aromatic compounds↗

Development of chemically vapor deposited rhenium emitters of (0001) preferred crystal orientation

Rhenium thermionic emitters were prepared by the pyrolysis of rhenium chlorides formed by the chlorination of rhenium pellets. The impurity contents, microstructures, degrees of (0001) preferred crystal orientation, and vacuum electron work functions of these emitters were determined as a function of deposition parameters, such as substrate temperature, rhenium pellet temperature and chlorine flow rate. A correlation between vacuum electron work function and degree of (0001) preferred crystal orientation was established. Conditions for depositing porosity-free rhenium emitters of high vacuum electron work functions were defined. Finally, three cylindrical rhenium emitters were prepared under the optimum deposition conditions.

Yang, L.↗

Rhenium material properties

Tensile data were obtained from four different types of rhenium at ambient and elevated temperatures. The four types of rhenium included chemical vapor deposition (CVD) and three powder metallurgy (PM) types, i.e., rolled sheet and pressed and sintered bars, with and without hot isostatic pressure (HIP) treatment. Results revealed a wide range of values with ultimate strengths at ambient temperatures varying from 663 MPa for CVD rhenium to 943 MPa for rolled sheet. A similar spread was also obtained for material tested at 1088 K and 1644 K. The wide variance observed with the different materials indicated that the rhenium manufacturing process, material composition and prior handling strongly dictated its properties. In addition to tensile properties, CVD, pressed and sintered material and HIP rhenium successfully completed 100 cycles of low cycle fatigue. Creep data were also obtained showing that CVD and pressed and sintered rhenium could sustain five hours of testing under a tension of 27.5 MPa at 1922 K.

Biaglow, James A.↗

Ambient Aging of Epitaxial and Polycrystalline Rhenium Thin Films

Extending the lifetime of superconducting qubits requires materials that are resistant to surface oxide formation. Rhenium has emerged as one such promising material. Because grain boundaries can promote material degradation, this project compares epitaxial (single-crystal, no grain boundaries) and polycrystalline (many grain boundaries) rhenium thin films after three years of ambient environmental exposure. Epitaxial rhenium remained free of undesired particles, while polycrystalline rhenium developed higher-oxide surface particles. Epitaxial rhenium demonstrated greater resistance to aging and oxidation, making it a more promising candidate for superconducting qubits. Surface characterization using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy revealed localized oxygen and nitrogen enrichment together with a Re⁷⁺ oxidation state in the polycrystalline surface particles, consistent with the proposed formation of ammonium perrhenate. Ongoing cleaning and XPS depth profiling will further determine the identity and origin of the surface crystallites.

Wiacek, Wiktoria [William Rainey Harper Coll.]↗

Liquid fluorine/hydrazine rhenium thruster update

The status of a fluorine/hydrazine thruster development program is discussed. A solid rhenium metal sea-level thrust chamber was successfully fabricated and tested for a total run duration of 1075 s with 17 starts. Rhenium fabrication methods are discussed. A test program was conducted to evaluate performance and chamber cooling. Acceptable performance was reached and cooling was adequate. A flight-type injector was fabricated that achieved an average extrapolated performance value of 3608 N-s/kg (368 lbf-s/lbm). Altitude thrust chambers were fabricated. One chamber incorporates a rhenium combustor and nozzle with an area ratio of 15:1, and a columbium nozzle extension with area ratios from 15:1 to 60:1. The other chamber was fabricated completely with a carbon/carbon composite. Because of the attributes of rhenium for use in high-temperature applications, a program to provide the materials and processes technology needed to reliably fabricate and/or repair vapor-deposited rhenium parts of relatively large size and complex shape is recommended.

Appel, M. A.↗

Effect of rhenium on the structure and properties of the weld metal of a molybdenum alloy

The structure and properties of welds made in molybdenum alloy VM-1 as a function of rhenium concentrations in the weld metal were studied. Rhenium was introduced into the weld using rhenium wire and tape or wires of Mo-47Re and Mo-52Re alloys. The properties of the weld metal were studied by means of metallographic techniques, electron microscopy, X-ray analysis, and autoradiography. The plasticity of the weld metal sharply was found to increase with increasing concentration of rhenium up to 50%. During welding, a decarburization process was observed which was more pronounced at higher concentrations of rhenium.

Dyachenko, V. V.↗

Evaluation of Rhenium Joining Methods

Coupons of rhenium-to-Cl03 flat plate joints, formed by explosive and diffusion bonding, were evaluated in a series of shear tests. Shear testing was conducted on as-received, thermally-cycled (100 cycles, from 21 to 1100 C), and thermally-aged (3 and 6 hrs at 1100 C) joint coupons. Shear tests were also conducted on joint coupons with rhenium and/or Cl03 electron beam welded tabs to simulate the joint's incorporation into a structure. Ultimate shear strength was used as a figure of merit to assess the effects of the thermal treatment and the electron beam welding of tabs on the joint coupons. All of the coupons survived thermal testing intact and without any visible degradation. Two different lots of as-received, explosively-bonded joint coupons had ultimate shear strengths of 281 and 310 MPa and 162 and 223 MPa, respectively. As-received, diffusion-bonded coupons had ultimate shear strengths of 199 and 348 MPa. For the most part, the thermally-treated and rhenium weld tab coupons had shear strengths slightly reduced or within the range of the as-received values. Coupons with Cl03 weld tabs experienced a significant reduction in shear strength. The degradation of strength appeared to be the result of a poor heat sink provided during the electron beam welding. The Cl03 base material could not dissipate heat as effectively as rhenium, leading to the formation of a brittle rhenium-niobium intermetallic.

Reed, Brian D.↗

Near-Net Shape Powder Metallurgy Rhenium Thruster

This paper describes the development of a method to produce a near-net shape (NNS) powder metallurgy (PM) rhenium combustion chamber of the size 445 N (100 lbf) used in a high performance liquid apogee engine. These engines are used in low earth Orbit and geostationary orbit for satellite positioning systems. The developments in near-net shape powder metallurgy rhenium combustion chambers reported in this paper will reduce manufacturing cost of the rhenium chambers by 25 percent, and reduce the manufacturing time by 30 to 40 percent. The quantity of rhenium metal powder used to produce a rhenium chamber is reduced by approximately 70 percent and the subsequent reduction in machining schedule and costs is nearly 50 percent.

Leonhardt, Todd↗

Rhenium Redefined

Through a Small Business Innovation Research (SBIR) contract with NASA's Glenn Research Center, Rhenium Alloys, Inc., of Elyria, Ohio, developed a new method for producing rhenium combustion chambers. Using room temperature isostatic pressing, Rhenium Alloys, Inc., compacted rhenium powder to a high density and into the approximated end shape and dimension of the rocket thruster. The item was then subjected to sintering and containerless hot isostatic pressing, increasing the density of the powder metallurgy part. With the new manufacturing process, both production time and costs are reduced while quality is significantly increased. The method enabled the company to deliver two chemical rocket thrusters to Glenn Research Center. The company makes rhenium a practical choice in manufacturing fields, including the aerospace, nuclear, and electronic industries, with upcoming opportunities projected in medical instrumentation.

Source record↗

Ambient Aging of Epitaxial and Polycrystalline Rhenium Thin Films

Extending the lifetime of superconducting qubits requires materials that are resistant to surface oxidation. Rhenium has emerged as one such promising candidate that forms a sub-nanometer oxide. Grain boundaries are known to promote material degradation, and thus, we compare epitaxial (single crystal, no grain boundaries) and polycrystalline (many grain boundaries) rhenium thin films after three years of ambient environmental exposure. Epitaxial rhenium remained free of undesired particles, while polycrystalline rhenium developed surface oxide crystallites. Surface characterization using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy reveals localized oxygen and nitrogen enrichment, together with a Re⁷⁺ oxidation state in the polycrystalline surface particles, consistent with the proposed formation of ammonium perrhenate. Epitaxial rhenium demonstrated greater resistance to aging and oxidation, making it a more promising candidate for superconducting qubits. Ongoing cleaning and XPS depth profiling will further determine the identity and origin of the surface crystallites.

Wiacek, Wiktoria [Fermilab]↗

Ambient Aging of Epitaxial and Polycrystalline Rhenium Thin Films

Extending the lifetime of superconducting qubits requires materials that are resistant to surface oxidation. Rhenium has emerged as one such promising candidate that forms a sub-nanometer oxide. Grain boundaries are known to promote material degradation, and thus we compared epitaxial (single crystal, no grain boundaries) and polycrystalline (many grain boundaries) rhenium thin films after three years of ambient environmental exposure. Epitaxial rhenium remained free of undesired particles, while polycrystalline rhenium developed surface oxide crystallites. Surface characterization using scanning electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy reveals localized oxygen and nitrogen enrichment together with a Re⁷⁺ oxidation state in the polycrystalline surface particles, consistent with the proposed formation of ammonium perrhenate. Epitaxial rhenium demonstrated greater resistance to aging and oxidation, making it a more promising candidate for superconducting qubits. Ongoing cleaning and XPS depth profiling will further determine the identity and origin of the surface crystallites.

Wiacek, Wiktoria [William Rainey Harper Coll.]↗

Rhenium-Sulfido and -Dithiolato Corroles: Reflections on Chalcophilicity

The high-temperature (~180 °C) reaction between free-base meso-triarylcorroles and Re 2 (CO) 10 , followed by exposure to PCl 3 and thiols (or elemental sulfur), affords rhenium-sulfido (ReS) corroles in 67-76% yields. The use of shorter reaction times, lower temperatures (~130 °C), and a dithiol (e.g., ethane-1,2-dithiol) also allows the isolation of rhenium-dithiolato corroles, presumptive intermediates on the path to ReS corroles. The ReS corroles exhibit high thermal stability and two reversible oxidations and reductions in their cyclic voltammograms, with redox potentials nearly identical to those observed for analogous ReO corroles. The electrochemical HOMO-LUMO gaps of the complexes, at 2.2 eV, are consistent with ligand-centered oxidation and reduction. The UV-vis spectra of ReS corroles, on the other hand, differ significantly from those of their ReO counterparts. Scalar-relativistic DFT calculations suggest that this difference reflects low-energy LUMO+2 and LUMO+3 levels, consisting of Re-S π-antibonding interactions; the ReO corroles, in contrast, exhibit a larger LUMO+1/LUMO+2 gap, as expected for a relatively classical Gouterman-type metalloporphyrin analogue. The high stability of ReS corroles is consistent with geochemists' view of rhenium as a moderately chalcophilic element (i.e., one that partitions into sulfide melts) as well as with a recent quantitative analysis of thiophilicity, which indicates that rhenium's oxophilicity and thiophilicity are essentially evenly balanced.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lower-cost tungsten-rhenium alloys

Tungsten-rhenium alloys with a substantially more dilute rhenium content have ductilities and other mechanical properties which compare favorably with the tungsten-rhenium alloys having much higher concentrations of the costly rhenium.

Klopp, W. D.↗

Development of Improved Rhenium Coatings for Fluorine Engine Thrust Chambers

Coating trials were undertaken to evaluate the application of rhenium to carbon-carbon composite sheet by plasma spraying. Optimum spray parameters and coating thickness were identified for production of coatings free from continuous defects and with adequate adherence to the substrate. A tungsten underlayer was not beneficial and possibly detracted from coating integrity. Stress calculations indicated that the proposed operating cycle of the rocket engine would not cause spalling of the rhenium coating. Calculations indicated that permeation of gases through the coating would not be significant during the expected life of the thrust chamber. The feasibility of applying rhenium coatings by laser melting was also studied. Poor wetting of the composite surface by the liquid rhenium precluded production of uniform coatings. Borate/carborate fluxes did not improve wetting characteristics.

Barton, K. J.↗

Rhenium Rocket Manufacturing Technology

The NASA Lewis Research Center's On-Board Propulsion Branch has a research and technology program to develop high-temperature (2200 C), iridium-coated rhenium rocket chamber materials for radiation-cooled rockets in satellite propulsion systems. Although successful material demonstrations have gained much industry interest, acceptance of the technology has been hindered by a lack of demonstrated joining technologies and a sparse materials property data base. To alleviate these concerns, we fabricated rhenium to C-103 alloy joints by three methods: explosive bonding, diffusion bonding, and brazing. The joints were tested by simulating their incorporation into a structure by welding and by simulating high-temperature operation. Test results show that the shear strength of the joints degrades with welding and elevated temperature operation but that it is adequate for the application. Rhenium is known to form brittle intermetallics with a number of elements, and this phenomena is suspected to cause the strength degradation. Further bonding tests with a tantalum diffusion barrier between the rhenium and C-103 is planned to prevent the formation of brittle intermetallics.

Source record↗