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Results for “HYDROFLUORIC ACID”

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 109 records · Page 6

Rare earth metals production using alternative feedstock that eliminates HF

This work reports the successful production of rare earth (RE) metal using Na-RE-F. Presently, RE metals are primarily produced using RE-fluoride due to its higher air and moisture stability compared to RE-chloride. However, its preparation requires the use of corrosive and hazardous chemicals, such as hydrofluoric acid (HF) or ammonium bifluoride (NH 4 HF 2 ). The present study demonstrates that Na-RE-F is an alternative salt to the typically used RE-fluoride. The Na-RE-F for this work is produced via a scalable hydrometallurgical approach using three different RE salts as feedstock, including acetate, nitrate, and chloride. HF is neither used nor generated during the salt preparation process. Furthermore, the Na-RE-F powder dries in air (without dry HF), and only water evolves during the drying process. Analyses of the Na-RE-F show that NaF liberates as a flux during the heating process, which lowers the salt reduction temperature to <900 °C, thus minimizing or eliminating the need for additional flux. Calciothermic reduction of the Na-RE-F salt is successfully employed to obtain RE metal. This work represents a safer, greener, and more widely deployable approach for producing the RE metals needed for permanent magnets which support the transition to a cleaner society through the decarbonization of the transportation industry.

36 MATERIALS SCIENCE↗

Electronically transparent graphene replicas of diatoms: a new technique for the investigation of frustule morphology

The morphogenesis of the silica cell walls (called frustules) of unicellular algae known as diatoms is one of the most intriguing mysteries of the diatoms. To study frustule morphogenesis, optical, electron and atomic force microscopy has been extensively used to reveal the frustule morphology. However, since silica frustules are opaque, past observations were limited to outer and fracture surfaces, restricting observations of interior structures. Here we show that opaque silica frustules can be converted into electronically transparent graphene replicas, fabricated using chemical vapor deposition of methane. Chemical vapor deposition creates a continuous graphene coating preserving the frustule’s shape and fine, complicated internal features. Subsequent dissolution of the silica with hydrofluoric acid yields a free-standing replica of the internal and external native frustule morphologies. Electron microscopy renders these graphene replicas highly transparent, revealing previously unobserved, complex, three-dimensional, interior frustule structures, which lend new insights into the investigation of frustule morphogenesis.

36 MATERIALS SCIENCE↗

Fluoride-free synthesis of a Sn-BEA catalyst by dry gel conversion

Sn containing molecular sieves with BEA topology (Sn-BEA) are active Lewis catalysts for a large variety of redox reactions. However, the synthesis of Sn-BEA often requires the use of toxic chemicals (e.g. hydrofluoric acid). In this study, we demonstrated that an active Sn-BEA catalyst can be directly synthesized in a non-fluoride medium via a dry gel conversion method with the aid of seed crystals. It was shown that seeding of zeolite BEA crystals can facilitate crystal growth and lead to BEA topology with framework Sn. Furthermore, it was found that ion-exchange with ammonium ions is indispensable to retain the crystal structure during calcination. The catalytic activity of the Sn-BEA catalyst was evaluated by the isomerization of glucose and reaction of pyruvaldehyde in the aqueous phase, and compared with the conventional hydrophobic Sn-BEA synthesized in a fluoride medium. The catalytic activity of the Sn-BEA synthesized in the absence of fluoride was found to be lower than that of the conventional Sn-BEA for catalyzing the isomerization of glucose in the aqueous phase, which could be attributed to its hydrophilic surface. For the reaction of pyruvaldehyde in the aqueous phase, the Sn-BEA synthesized in this study showed similar activity to the conventional hydrophobic Sn-BEA, indicating that the catalytic activity of Sn-BEA catalysts largely depends on the type of reactions. The current work provides the first example of direct preparation of a Sn-BEA catalyst in a caustic medium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the hydrolysis of cryogenically layered molybdenum hexafluoride through a disordered hydrogen-bonded network

Molybdenum hexafluoride (MoF6) is used as a non-radioactive substitute for uranium to study the hydrolysis of metal hexafluorides. Molybdenum hexafluoride gas and water vapor, from the air, were sequentially layered onto a diamond substrate kept at liquid nitrogen temperature using a custom designed cryogenic cell with a copper cold finger. Reaction progress was monitored by transmission Fourier Transform Infrared Spectroscopy (FTIR) through the layers and diamond substrate over several hours while allowing the substrate to warm. Changes in the modes in the 500–1000 cm -1 region are tracked as the reaction progresses in order to identify intermediate species. Strong absorption features are also observed in the 1000–3000 cm -1 range, suggesting the presence of ionic dissociation intermediates trapped in a disordered H-bonded network of cryogenic hydrofluoric acid. Here, a possible reaction pathway is proposed and the final hydrolysis product is characterized by FTIR, UV-vis, and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface electronic structure for various surface preparations of Nb-doped SrTiO{sub 3} (001)

High-resolution angle-resolved photoemission spectroscopy (ARPES) was used to study the surface electronic structure of Nb-doped SrTiO{sub 3} (STO) single crystals prepared using a variety of surface preparations. ARPES measurements show that simple degreasing with subsequent anneal in vacuum is not an adequate surface preparation of STO, rather, preparations consisting of etching with buffered HF or HCl, and to a lesser extent, simple water leaching resulted in surfaces with much less disorder. A non-dispersing, mid-gap state was found ∼800 meV above the top of the valence band for samples which underwent etching. This mid-gap state is not present for vacuum-annealed and water-leached samples, as well as for STO thin films grown using molecular beam epitaxy. Theoretical modeling using density functional theory suggests that this mid-gap state is not related to the SrO- and TiO{sub 2}-terminated surfaces, but rather, is due to a partial hydrogenation of the STO surface that occurs during etching.

36 MATERIALS SCIENCE↗

Improved metal-insulator-transition characteristics of ultrathin VO{sub 2} epitaxial films by optimized surface preparation of rutile TiO{sub 2} substrates

Key to the growth of epitaxial, atomically thin films is the preparation of the substrates on which they are deposited. Here, we report the growth of atomically smooth, ultrathin films of VO{sub 2} (001), only ∼2 nm thick, which exhibit pronounced metal-insulator transitions, with a change in resistivity of ∼500 times, at a temperature that is close to that of films five times thicker. These films were prepared by pulsed laser deposition on single crystalline TiO{sub 2}(001) substrates that were treated by dipping in acetone, HCl and HF in successive order, followed by an anneal at 700–750 °C in flowing oxygen. This pretreatment removes surface contaminants, TiO{sub 2} defects, and provides a terraced, atomically smooth surface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Silicon nanocrystals with high boron and phosphorus concentration hydrophilic shell—Raman scattering and X-ray photoelectron spectroscopic studies

Boron (B) and phosphorus (P) codoped silicon (Si) nanocrystals, which exhibit very wide range tunable luminescence due to the donor to acceptor transitions and can be dispersed in polar liquids without organic ligands, are studied by Raman scattering and X-ray photoelectron spectroscopies. Codoped Si nanocrystals exhibit a Raman spectrum significantly different from those of intrinsic ones. First, the Raman peak energy is almost insensitive to the size and is very close to that of bulk Si crystal in the diameter range of 2.7 to 14 nm. Second, the peak is much broader than that of intrinsic ones. Furthermore, an additional broad peak, the intensity of which is about 20% of the main peak, appears around 650 cm{sup −1}. The peak can be assigned to local vibrational modes of substitutional B and B-P pairs, B clusters, B-interstitial clusters, etc. in Si crystal. The Raman and X-ray photoelectron spectroscopic studies suggest that a crystalline shell heavily doped with these species is formed at the surface of a codoped Si nanocrystal and it induces the specific properties, i.e., hydrophilicity, high-stability in water, high resistance to hydrofluoric acid, etc.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effects of electrode distance and nature of electrolyte on the diameter of titanium dioxide nanotube

The titanium nanotubes were synthesized using viscous electrolytes consisting of ethylene glycol and non-viscous electrolytes consisting of aqueous solution of hydrofluoric acid. Sodium fluoride and ammonium fluoride were utilized as the source of fluorine ions. The samples were then characterized by field emission scanning electron microscope (FE-SEM). Their morphologies were investigated under different anodic potentials and various electrolyte compositions. It was found out that nanotubes can be obtained in fluoride ions and morphology is dependent on various parameters like anodic potential, time, electrolyte composition and the effects by varying the distance between the electrodes on the morphology was also investigated. It was found that by altering the distance between the electrodes, change in the diameter and the porosity was observed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Distribution of free carriers near heavily-doped epitaxial surfaces of n-type Ge(100) upon HF and HCl treatments

Carrier distributions near n-type epitaxially-grown Ge(100) surfaces with high impurity concentrations (1 × 10{sup 20} cm{sup −3}) were studied using high resolution electron energy loss spectroscopy (HREELS) upon surface treatments in aqueous solutions of HF and HCl. After surface treatments with HCl and HF, the molecular vibration modes distinctly showed either chloride or hydride terminations of Ge surfaces with negligible oxidation. The free-carrier concentration profile was inferred from the conduction band plasmon measurements as a function of the incident electron energies employing a dielectric theory simulation with a 4-layer structure and an effective electron mass of 0.02m{sub 0}. A carrier-free layer of 40 and 24 Å were derived for HCl- and HF-treated Ge(100), respectively. The surface band bending was estimated to be 0.32 eV for HF-treated Ge. HCl-treated Ge surfaces showed a band bending of 0.91 eV attributed to the strong effect of the surface Cl-Ge dipole.

36 MATERIALS SCIENCE↗

Helium ion beam enhanced local etching of silicon nitride

We investigated the effect of the helium ion implantation on the etching rate of silicon nitride in hydrofluoric acid. Helium ions were implanted into 500-nm-thick silicon nitride film with energies from 15 keV to 35 keV. The ion fluence from 10{sup 14} cm{sup −2} to 10{sup 17} cm{sup −2} was used. All samples were investigated with a scanning electron microscope and atomic force microscope. The dependence of the etching rate on the concentration of ion-induced defects is obtained.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

On the characteristics of N-polar GaN Schottky barrier contacts with LPCVD SiN interlayers

In this work, we study the behavior of N-polar GaN Schottky diodes with low-pressure chemical vapor deposited (LPCVD) SiN interlayers and unveil the important role of an amphoteric miniband formed in this interlayer due to a previously identified and dominating Si dangling bond defect. Through analysis of temperature-dependent current–voltage (I–V–T), capacitance–voltage (C–V), and x-ray photoelectron spectroscopy measurements, we observe that when nickel is deposited on LPCVD SiN pretreated with hydrofluoric acid, the SiN/GaN interface is responsible for determining the overall system's barrier height. By contrast, contact formation on oxidized LPCVD SiN leads to a metal/SiN-dominant barrier. We, consequently, propose band diagrams that account for an amphoteric miniband in LPCVD SiN, leading to a new understanding of LPCVD SiN as a lossy dielectric with surface barrier-dependent behavior.

42 ENGINEERING↗

Enhancing the electron mobility in Si-doped (010) β-Ga 2 O 3 films with low-temperature buffer layers

We demonstrate a new substrate cleaning and buffer growth scheme in β-Ga 2 O 3 epitaxial thin films using metal–organic vapor phase epitaxy (MOVPE). For the channel structure, a low-temperature (LT, 600 °C) un-doped Ga 2 O 3 buffer was grown, followed by a transition layer to a high-temperature (HT, 810 °C) Si-doped Ga 2 O 3 channel layers without growth interruption. The (010) Ga 2 O 3 Fe-doped substrate cleaning uses solvent cleaning, followed by additional hydrofluoric acid (49% in water) treatment for 30 min before the epilayer growth. This step is shown to compensate the parasitic Si channel at the epilayer–substrate interface that originates from the substrate polishing process or contamination from the ambient. From secondary ion mass spectroscopy (SIMS) analysis, the Si peak atomic density at the substrate interface is found to be several times lower than the Fe atomic density in the substrate—indicating full compensation. The elimination of the parasitic electron channel at the epi–substrate interface was also verified by electrical (capacitance–voltage profiling) measurements. In the LT-grown (600 °C) buffer layers, it is seen that the Fe forward decay tail from the substrate is very sharp, with a decay rate of ∼9 nm/dec. X-ray off-axis rocking curve ω-scans show very narrow full width at half maximum (FWHM) values, similar to the as-received substrates. These channels show record high electron mobility in the range of 196–85 cm 2 /V⋅s in unintentionally doped and Si-doped films in the doping range of 2 × 10 16 –1 × 10 20 cm −3 . Si delta-doped channels were also grown utilizing this substrate cleaning and the hybrid LT buffers. Record high electron Hall mobility of 110 cm 2 /V⋅s was measured for sheet charge density of 9.2 × 10 12 cm −2 . This substrate cleaning, combined with the LT buffer scheme, shows the potential of designing Si-doped β-Ga 2 O 3 channels with exceptional transport properties for high-performance Ga 2 O 3 -based electron devices.

Bhattacharyya, Arkka↗

HERSCHEL-SPIRE IMAGING SPECTROSCOPY OF MOLECULAR GAS IN M82

We present new Herschel-SPIRE imaging spectroscopy (194-671 {mu}m) of the bright starburst galaxy M82. Covering the CO ladder from J = 4 {yields} 3 to J = 13 {yields} 12, spectra were obtained at multiple positions for a fully sampled {approx}3 Multiplication-Sign 3 arcmin map, including a longer exposure at the central position. We present measurements of {sup 12}CO, {sup 13}CO, [C I], [N II], HCN, and HCO{sup +} in emission, along with OH{sup +}, H{sub 2}O{sup +}, and HF in absorption and H{sub 2}O in both emission and absorption, with discussion. We use a radiative transfer code and Bayesian likelihood analysis to model the temperature, density, column density, and filling factor of multiple components of molecular gas traced by {sup 12}CO and {sup 13}CO, adding further evidence to the high-J lines tracing a much warmer ({approx}500 K), less massive component than the low-J lines. The addition of {sup 13}CO (and [C I]) is new and indicates that [C I] may be tracing different gas than {sup 12}CO. No temperature/density gradients can be inferred from the map, indicating that the single-pointing spectrum is descriptive of the bulk properties of the galaxy. At such a high temperature, cooling is dominated by molecular hydrogen. Photon-dominated region (PDR) models require higher densities than those indicated by our Bayesian likelihood analysis in order to explain the high-J CO line ratios, though cosmic-ray-enhanced PDR models can do a better job reproducing the emission at lower densities. Shocks and turbulent heating are likely required to explain the bright high-J emission.

79 ASTRONOMY AND ASTROPHYSICS↗

The atmospheres of earthlike planets after giant impact events

It is now understood that the accretion of terrestrial planets naturally involves giant collisions, the moon-forming impact being a well-known example. In the aftermath of such collisions, the surface of the surviving planet is very hot and potentially detectable. Here we explore the atmospheric chemistry, photochemistry, and spectral signatures of post-giant-impact terrestrial planets enveloped by thick atmospheres consisting predominantly of CO{sub 2} and H{sub 2}O. The atmospheric chemistry and structure are computed self-consistently for atmospheres in equilibrium with hot surfaces with composition reflecting either the bulk silicate Earth (which includes the crust, mantle, atmosphere, and oceans) or Earth's continental crust. We account for all major molecular and atomic opacity sources including collision-induced absorption. We find that these atmospheres are dominated by H{sub 2}O and CO{sub 2}, while the formation of CH{sub 4} and NH{sub 3} is quenched because of short dynamical timescales. Other important constituents are HF, HCl, NaCl, and SO{sub 2}. These are apparent in the emerging spectra and can be indicative that an impact has occurred. The use of comprehensive opacities results in spectra that are a factor of two lower brightness temperature in the spectral windows than predicted by previous models. The estimated luminosities show that the hottest post-giant-impact planets will be detectable with near-infrared coronagraphs on the planned 30 m class telescopes. The 1-4 μm will be most favorable for such detections, offering bright features and better contrast between the planet and a potential debris disk. We derive cooling timescales on the order of 10{sup 5-6} yr on the basis of the modeled effective temperatures. This leads to the possibility of discovering tens of such planets in future surveys.

79 ASTRONOMY AND ASTROPHYSICS↗

HERSCHEL* FAR-INFRARED SPECTROSCOPY OF THE GALACTIC CENTER. HOT MOLECULAR GAS: SHOCKS VERSUS RADIATION NEAR Sgr A

We present a {approx}52-671 {mu}m spectral scan toward Sgr A* taken with the PACS and SPIRE spectrometers on board Herschel. The achieved angular resolution allows us to separate, for the first time at far-IR wavelengths, the emission toward the central cavity (gas in the inner central parsec of the galaxy) from that of the surrounding circumnuclear disk. The spectrum toward Sgr A* is dominated by strong [O III], [O I], [C II], [N III], [N II], and [C I] fine-structure lines (in decreasing order of luminosity) arising in gas irradiated by UV photons from the central stellar cluster. In addition, rotationally excited lines of {sup 12}CO (from J = 4-3 to 24-23), {sup 13}CO, H{sub 2}O, OH, H{sub 3}O{sup +}, HCO{sup +}, and HCN, as well as ground-state absorption lines of OH{sup +}, H{sub 2}O{sup +}, H{sub 3}O{sup +}, CH{sup +}, H{sub 2}O, OH, HF, CH, and NH are detected. The excitation of the {sup 12}CO ladder is consistent with a hot isothermal component at T{sub k} {approx_equal} 10{sup 3.1} K and n(H{sub 2}) {approx}< 10{sup 4} cm{sup -3}. It is also consistent with a distribution of temperature components at higher density with most CO at T{sub k} {approx}< 300 K. The detected molecular features suggest that, at present, neither very enhanced X-ray nor cosmic-ray fluxes play a dominant role in the heating of the hot molecular gas. The hot CO component (either the bulk of the CO column or just a small fraction depending on the above scenario) results from a combination of UV- and shock-driven heating. If irradiated dense clumps/clouds do not exist, shocks likely dominate the heating of the hot molecular gas. This is consistent with the high-velocity gas detected toward Sgr A*.

79 ASTRONOMY AND ASTROPHYSICS↗

Enhanced superconducting qubit performance through ammonium fluoride etch

The performance of superconducting qubits is often limited by dissipation and two-level systems (TLS) losses. The dominant sources of these losses are believed to originate from amorphous materials and defects at interfaces and surfaces, likely as a result of fabrication processes or ambient exposure. Here, we explore a novel wet chemical surface treatment at the Josephson junction-substrate and the substrate-air interfaces by replacing a buffered oxide etch (BOE) cleaning process with one that uses hydrofluoric acid followed by aqueous ammonium fluoride. We show that the ammonium fluoride etch process results in a statistically significant improvement in median $\text{T}_1$ by $\sim22\%$ (p = 0.002), and a reduction in the number of strongly-coupled TLS in the tunable frequency range. Microwave resonator measurements on samples treated with the ammonium fluoride etch after niobium deposition and etching also show $\sim33\%$ lower TLS-induced loss tangent compared to the BOE treated samples. As the chemical treatment primarily modifies the Josephson junction-substrate interface and substrate-air interface, we perform targeted chemical and structural characterizations to examine materials differences at these interfaces and identify multiple microscopic changes that could contribute to decreased TLS losses.

36 MATERIALS SCIENCE↗

Evidence of molecular hydrogen trapped in two-dimensional layered titanium carbide-based MXene

Two-dimensional transition metal carbides and nitrides (MXenes) are one of the largest and fastest growing families of materials. The presence of molecular hydrogen at ambient conditions in a MXene (Ti 3 C 2 T x , where T x represents a surface terminating species, including O, OH, and F) material is revealed here by inelastic and elastic neutron scatterings. The inelastic neutron-scattering spectrum measured at 5 K shows a peak at 14.6 meV, presenting a clear indication of the presence of parahydrogen in the MXene synthesized using 48% hydrofluoric acid and annealed at 110°C in vacuum prior to the measurement. An increase in the measurement temperature gradually reduces the peak intensity and increases the peak width due to the mobility of the molecular hydrogen in confinement. The presence of molecular hydrogen is confirmed further from the observed elastic intensity drop in a fixed energy-window scan of elastic intensity measurements in the temperature range of 10–35 K. Using milder etching conditions, ion intercalation, or an increase in the annealing temperature all result in the absence of the trapped hydrogen molecules in MXene. Here, the results of this paper can guide the development of MXene materials with desired properties and improve our understanding of the behavior of MXenes in applications ranging from supercapacitors to hydrogen evolution reaction catalysis and hydrogen storage.

36 MATERIALS SCIENCE↗