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At least 163 records · Page 9

Graphite fluoride fibers and their applications in the space industry

Characterization and potential space applications of graphite fluoride fibers from commercially available graphitized carbon fibers are presented. Graphite fluoride fibers with fluorine to carbon ratios of 0.65 and 0.68 were found to have electrical resistivity values of 10(exp 4) and 10(exp 11) Ohms-cm, respectively, and thermal conductivity values of 24 and 5 W/m-K, respectively. At this fluorine content range, the fibers have tensile strength of 0.25 + or - 0.10 GPa (36 + or - 14 ksi), Young's modulus of 170 + or - 30 GPa (25 + or - 5 Msi). The coefficient of thermal expansion value of a sample with fluorine to carbon ratio of 0.61 was found to be 7 ppm/C. These properties change and approach the graphite value as the fluorine content approach 0. Electrically insulative graphite fluoride fiber is at least five times more thermally conductive than fiberglass. Therefore, it can be used as a heat sinking printed circuit board material for low temperature, long life power electronics in spacecraft. Also, partially fluorinated fiber with tailor-made physical properties to meet the requirements of certain engineering design can be produced. For example, a partially fluorinated fiber could have a predetermined CTE value in -1.5 to 7 ppm/C range and would be suitable for use in solar concentrators in solar dynamic power systems. It could also have a predetermined electrical resistivity value suitable for use as a low observable material. Experimental data indicate that slightly fluorinated graphite fibers are more durable in the atomic oxygen environment than pristine graphite. Therefore, fluorination of graphite used in the construction of spacecraft that would be exposed to the low Earth orbit atomic oxygen may protect defect sites in atomic oxygen protective coatings and therefore decrease the rate of degradation of graphite.

Hung, Ching-Chen↗

Observations of the freeze/thaw performance of lithium fluoride by motion picture photography

To gain direct observation of the molten salt phase change, a novel containerless technique was developed where the high surface tension of lithium fluoride was used to suspend a bead of the molten salt inside a specially designed wire cage. By varying the current passing through the wire, the cage also served as a variable heat source. In this way, the freeze/thaw performance of the lithium fluoride could be photographed by motion picture photography without the influence of container walls. The motion picture photography of the lithium fluoride sample revealed several zones during the phase change, a solid zone and a liquid zone, as expected, and a slush zone that was predicted by thermal analysis modeling.

Jaworske, D. A.↗

Exotic fluoride molecules in IRC +10216: Confirmation of AlF and searches for MgF and CaF

Three new rotational transitions of aluminum fluoride (AlF) at 0.8 and 1.2 mm have been observed. The J = 10-9, J = 8-7, and J = 7-6 lines of AlF at 230, 263, and 329 GHz, respectively, were seen toward IRC +10216 using the Caltech Submillimter Observatory (CSO). Combined with the earlier data obtained for this species at IRAM at 2 and 3 mm, these measurements confirm the presence of the metal halide in this carbon-rich circumstellar shell. Analysis of the CSO and IRAM data suggests that AlF arises from a source with a diameter of theta(sub s) approximately = 5-10 sec and hence is present chiefly in the inner envelope of IRC +10216. In this region, the molecule has a column density of (0.3-1.1) x 10(exp 15)/sq cm, which indicates a fractional abundance of at least approximately 10(exp -9), relative to H2. Searches for the metal fluoride species CaF and MgF have also been conducted toward IRC +10216, but with negative results. The column density upper limits for MgF and CaF are N(sub tot) less than (1-4) x 10(exp 14)/sq cm. Relative abundances of these metal fluoride molecules can be understood in terms of chemical thermodynamic equilibrium. The presence of AlF in IRC +10216 also indicates that large quantities of fluorine must be present in the inner stellar envelope, suggesting that this element may be produced not primarily in explosive nucleosynthesis but rather in helium shell flashes, as indicated also by HF spectroscopy of red giant stars.

Ziurys, L. M.↗

Lubricating Properties of Some Bonded Fluoride and Oxide Coatings for Temperature to 1500 F

The lubricating properties of some experimental ceramic coatings, diffusion-bonded fluoride coatings, and ceramic-bonded fluoride coatings were determined. The experiments were conducted in an air atmosphere at a sliding velocity of 430 feet per minute and at temperatures from 75 to 1500 F. Several ceramic coatings provided substantial reductions in friction coefficient and rider wear (compared with the unlubricated metals). For example, a cobaltous oxide (CoO) base coating gave friction coefficients of 0.24 to 0.36 within the temperature range of 75 to 1400 F; serious galling and welding of the metal surfaces were prevented. The friction coefficients were higher than the arbitrary maximum (0.2) usually considered for effective boundary lubrication. However, when a moderately high friction coefficient can be tolerated, this type of coating may be a useful antiwear composition. Diffusion-bonded calcium fluoride (CaF2) on Haynes Stellite 21 and on Inconel X gave friction coefficients of 0.1 to 0.2 at 1500 F. Endurance life was dependent on the thermal history of the coating; life improved with increased exposure time at elevated temperatures prior to running. Promising results were obtained with ceramic-bonded CaF2 on Inconel X. Effective lubrication and good adherence were obtained with a 3 to 1 ratio of CaF2 to ceramic. A very thin sintered and burnished film of CaF2 applied to the surface of this coating further improved lubrication, particularly above 1350 F. The friction coefficient was 0.2 at 500 F and decreased with increasing temperature to 0.06-at 1500 F. It was 0.25 at 75 F and 0.22 at 250 F.

Sliney, Harold E.↗

ESCA Study of Poly (Vinylidene Fluoride) Tetrafluoroethylene - Ethylene Copolymer and Polyethylene Exposed to Atomic Oxygen

The ESCA (electron spectroscopy for chemical analysis) spectra of films of poly(vinylidene fluoride) (PVDF), tetrafluoroethylene-ethylene copolymer (TFE/ET) and polyethylene (PE) exposed to atomic oxygen (O(P-3)), in or out of the glow of a radio-frequency O2 plasma, were compared. ESCA spectra of PE films exposed to (O(P-3)) in low Earth orbit (LEO) on the STS-8 Space Shuttle were also examined. Apart from O(P-3)-induced surface recession (etching), the various polymer films exhibited surface oxidation, which proceeded towards equilibrium saturation oxygen levels. The maximum surface oxygen uptakes for in-glow or out-of-glow exposures were in the order: PE greater than TFE/ET greater than PVDF; for PE itself, the oxygen uptakes were in the order: in glow greater than out of glow greater than LEO. Given prior ESCA data on poly(vinyl fluoride) and polytetrafluoroethylene films exposed to O(P-3), the extent of surface oxidation is seen to decrease regularly with increase in fluorine substitution in a family of ethylene-type polymers. (Keywords: ESCA; poly(vinylidene fluoride); tetrafluoroethylene ethylene copolymer; polyethylene; atomic oxygen; radio-frequency oxygen plasma; low Earth orbit)

Golub, Morton A.↗

Discovery of Interstellar Hydrogen Fluoride

We report the first detection of interstellar hydrogen fluoride. Using the Long Wavelength Spectrometer of the Infrared Space Observatory (ISO), we have detected the 121.6973 micron J = 2-1 line of HF in absorption toward the far-infrared continuum source Sagittarius B2. The detection is statistically significant at the 13 sigma level. On the basis of our model for the excitation of HF in Sgr B2, the observed line equivalent width of 1.0 nm implies a hydrogen fluoride abundance of about 3 x 10 (exp -10) relative to H, If the elemental abundance of fluorine in Sgr B2 is the same as that in the solar system, then HF accounts for about 2% of the total number of fluorine nuclei. We expect hydrogen fluoride to be the dominant reservoir of gas-phase fluorine in Sgr B2, because it is formed rapidly in exothermic reactions of atomic fluorine with either water or molecular hydrogen; thus, the measured HF abundance suggests a substantial depletion of fluorine onto dust grains. Similar conclusions regarding depletion have previously been reached for the case of chlorine in dense interstellar clouds. We also find evidence at a lower level of statistical significance (about 5 sigma) for an emission feature at the expected position of the 4(sub 32)-4(sub 23) 121.7219 micron line of water. The emission-line equivalent width of 0.5 mm for the water feature is consistent with the water abundance of 5 x 10(exp -6) relative to H, that has been inferred previously from observations of the hot core of Sgr B2.

Neufeld, David A.↗

Discovery of Interstellar Hydrogen Fluoride

We report the first detection of interstellar hydrogen fluoride. Using the Long Wavelength Spectrometer of the Infrared Space Observatory (ISO), we have detected the 121.6973 micron J = 2-1 line of HF in absorption toward the far-infrared continuum source Sagittarius B2. The detection is statistically significant at the 13 sigma level. On the basis of our model for the excitation of HF in Sgr B2, the observed line equivalent width of 1.0 nm implies a hydrogen fluoride abundance of approximately 3 x 10(exp -10) relative to H2. If the elemental abundance of fluorine in Sgr B2 is the same as that in the solar system, then HF accounts for approximately 2% of the total number of fluorine nuclei. We expect hydrogen fluoride to be the dominant reservoir of gas-phase fluorine in Sgr B2, because it is formed rapidly in exothermic reactions of atomic fluorine with either water or molecular hydrogen; thus, the measured HF abundance suggests a substantial depletion of fluorine onto dust grains. Similar conclusions regarding depletion have previously been reached for the case of chlorine in dense interstellar clouds. We also find evidence at a lower level of statistical significance (approximately 5 sigma) for an emission feature at the expected position of the 4(sub 32)-4(sub 23) 121.7219 micron line of water. The emission-line equivalent width of 0.5 nm for the water feature is consistent with the water abundance of 5 x 10(exp -6) relative to H2 that has been inferred previously from observations of the hot core of Sgr B2.

Neufeld, David A.↗

Effect of oral calcium and calcium + fluoride treatments on mouse bone properties during suspension

The bone effects of oral dosages of calcium chloride with or without supplementary sodium fluoride were assessed in antiorthostatically suspended mice. Two calcium dosages were used to replace half (3.1 mM) or all(6.3 mM) of the dietary calcium lost due to reduced food intake by the suspended mice. Two groups of 6.3 mM CaCl2-treated mice were additionally treated with 0.25 or 2.5 mM NaF. The results indicate that supplementation of the mouse drinking water with calcium salts prevents bone changes induced by short-term suspension, while calcium salts in combination with fluoride are less effective as fluoride dosage increases. However, the calcium supplements change the relationship between the femur mechanical properties and the mineral composition of the bone. Because of this, it appears that oral calcium supplements are effective through a mechanism other than simple dietary supplementation and may indicate a dependence of bone consistency on systemic and local fluid conditions.

Non-NASA Center↗

Advanced Environmentally Resistant Lithium Fluoride Mirror Coatings for the Next Generation of Broadband Space Observatories

Recent advances in the physical vapor deposition (PVD) of protective fluoride films have raised the far-ultraviolet (FUV: 912-1600 A) reflectivity of aluminum-based mirrors closer to the theoretical limit. The greatest gains, at more than 20%, have come for lithium fluoride-protected aluminum, which has the shortest wavelength cutoff of any conventional overcoat. Despite the success of the NASA FUSE mission, the use of lithium fluoride (LiF)-based optics is rare, as LiF is hygroscopic and requires handling procedures that can drive risk. With NASA now studying two large mission concepts for astronomy, Large UV-Optical-IR Surveyor (LUVOIR) and the Habitable Exoplanet Imaging Mission (HabEx), which mandate throughput down to 1000 , the development of LiF-based coatings becomes crucial. This paper discusses steps that are being taken to qualify these new enhanced LiF-protected aluminum (eLiF) mirror coatings for flight. In addition to quantifying the hygroscopic degradation, we have developed a new method of protecting eLiF with an ultrathin (10-20 A) capping layer of a nonhygroscopic material to increase durability. We report on the performance of eLiF-based optics and assess the steps that need to be taken to qualify such coatings for LUVOIR, HabEx, and other FUV-sensitive space missions.

Fleming, Brian↗

Thermal Desorption of Tritium from Fluoride Salt-Cooled Reactor Materials

The fluoride-salt-cooled high-temperature reactor (FHR) is a high-temperature fission reactor concept involving a liquid fluoride salt coolant, coated particle fuel, and enhanced passive safety mechanisms. Utilizing a low-pressure coolant and high temperature fuel allows for smaller reactor buildings and use of gas Brayton power cycles for higher efficiency in electricity production. One of the fluoride salts being considered for the FHR coolant is 2LiF - BeF{sub 2} (flibe). Tritium is generated frequently in flibe from thermal neutron transmutation of Li-6 and Be-9. Tritium retention in irradiated structural materials presents a challenge to the design of the FHR; high neutron fluence can induce significant material damage and alteration of microstructures to trap tritium in the structure, particularly in carbon-based materials (such as steels). Investigation of tritium transport in flibe salt and structural materials is also critical to evaluating mass balance of tritium in a system for quantifying leakage of tritium to the environment. It is important to understand the uptake of tritium in these proposed core materials since the transport of tritium within an FHR is of critical concern for operational safety due to corrosion, and to prevent tritium release into the environment. The presence of TF corrodes stainless steel by oxidizing chromium. Tritium gas (T{sub 2}) easily diffuses through reactor materials and can be released into the environment through the primary piping and heat exchangers. There is great interest in identifying materials that are compatible with the FHR environment that can be used to getter tritium from the salt, or to inhibit the diffusion of tritium to prevent its release into the environment. As part of the FHR Integrated Research Project (IRP), capsules containing proposed core materials immersed in flibe salt were irradiated at 700 deg. C for 1000 hours (FS-1) and 300 hours (FS-2) in the MIT Research Reactor (MITR). During irradiation, tritium is produced in the salt, and then interacts with the other materials in the capsule. Measurements of the effluent gas during the FHR IRP irradiation experiments indicated that less than 1% of the tritium generated in the salt escaped in the gas phase. It is assumed that most of the tritium was captured, either via diffusion or surface adsorption, on the materials inside the capsule. Tritium frequently adsorbs to sample surfaces in the form of HTO, which requires relatively low temperatures to release (on the order of 100 deg. C). In certain cases, tritium can be bound in the bulk of materials from diffusion or neutron transmutation of lithium and beryllium in the structural materials. Accurate measurement of very small concentrations of hydrogen is difficult; by taking advantage of the radioactive decay of tritium (which emits low-energy beta radiation), several methods become available to detect and quantitatively measure the tritium. The most sensitive method is liquid scintillation counting (LSC), which requires the tritium to be suspended in optically-transparent liquid media that is compatible with scintillating solution, such as water. This measurement technique requires the tritium to be extracted from the material, which can be achieved through leaching into water, thermal desorption, or complete destruction of the sample by acid digestion or pyrolysis. A less destructive method is preferred in order to preserve the specimens, reduce the generation of radioactive mixed wastes, and minimize the carryover of other activation products. For total thermal desorption of tritium from the materials, the tritiated materials must be heated to temperatures in excess of 300 deg. C. Heating the specimens above the irradiation temperature will re-mobilize the tritium and allow it to be captured from the gas stream directly into LSC media. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

The preparation and characterization of iron fluorides polymorphs FeF{sub 3}·0.33H{sub 2}O and β-FeF{sub 3}∙3H{sub 2}O as cathode materials for lithium-ion batteries

Graphical abstract: Better rate capability and cycling performance were observed for β-FeF{sub 3}·3H{sub 2}O/C prepared by mechano-chemical synthesis. - Highlights: • A novel mechano-chemical preparation method. • The use of NH{sub 4}F as starting material. • Better electro-chemical performance in the case of β-FeF{sub 3}·3H{sub 2}O/C. - Abstract: Two kinds of iron fluorides, FeF{sub 3}·0.33H{sub 2}O and β-FeF{sub 3}∙3H{sub 2}O, have been synthesized by different chemical routes using Fe(NO{sub 3}){sub 3}·9H{sub 2}O and NH{sub 4}F as precursors and investigated as cathode materials for secondary lithium batteries. β-FeF{sub 3}·3H{sub 2}O was obtained via a mechano-chemical process and FeF{sub 3}·0.33H{sub 2}O was obtained by a precipitation reaction from ethanol solution. To further improve their electrochemical properties, a ball milling process with carbon has been used to form composites. The fluorides were characterized by X-ray diffraction (XRD), thermal analysis, FTIR spectroscopy, galvanostatic charge/discharge and cyclic voltammetry measurements. The results showed that the as-prepared β-FeF{sub 3}·3H{sub 2}O/C exhibited better rate performance and cycling stability. It exhibited an initial discharge capacity of 199.6 mA h g{sup −1} at a current density of 20 mA g{sup −1} in a voltage range of 1.8–4.5 V and still reserved a discharge capacity of about 146.5 mA h g{sup −1} after 10 cycles. Only a capacity loss of 15 mA h g{sup −1} and 7 mA h g{sup −1} was observed when the current density was at 40 mA g{sup −1} and 80 mA g{sup −1}, respectively.

36 MATERIALS SCIENCE↗

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 2. Light Lanthanides (Ce–Eu)

This is the second part of the volume devoted to the evaluation of experimental solubility data for rare earth metal (REM) fluorides in water as well as in aqueous ternary and multicomponent systems. Fluorides of Ce, Pr, Nd, Pm, Sm, and Eu (so-called light lanthanides), as the main solutes, are covered in the present part, which has thorough coverage of the experimental literature through the end of 2012. The experimentally unknown solubility value for PmF{sub 3} in water was predicted by an interpolation of the solubility values for NdF{sub 3} and SmF{sub 3} at 298 K. General features of the systems, such as the nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, pH, mixed solvent medium on the solubility, quality of the solubility results, and solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

On the Eu{sup 2+} luminescence in some perovskite fluorides

In the recent years due to their various optical and technological applications fluoride materials have attracted attention of several researchers. When these materials are doped with rare earth ions they show properties favorable for many optical applications such as high quantum efficiencies. The perovskite type fluorides of formula ABF{sub 3} where A= Alkali earth metal (Li,Na,K,Rb,Cs) and B= Alkaline earth metal (Mg,Ca,Ba,Sr) are of special interest to the research workers because of their wide range of applications that includes these materials as thermoluminescence detector, laser material, scintillator, X-ray imaging and storage phosphor, quantum cutter for VUV applications etc. Due to the high symmetry and technological efficiency of the growth process these crystals are good model objects for fundamental studies and in some cases they are of great practical value. This paper reports photoluminescence properties of UV emitting KMgF{sub 3}, NaMgF{sub 3} and LiBaF{sub 3} phosphors prepared by reactive atomospheric process. X-ray diffraction and photoluminescence characteristics of these phosphors are also mentioned.

36 MATERIALS SCIENCE↗

Ultraviolet optical properties of aluminum fluoride thin films deposited by atomic layer deposition

Aluminum fluoride (AlF{sub 3}) is a low refractive index material with promising optical applications for ultraviolet (UV) wavelengths. An atomic layer deposition process using trimethylaluminum and anhydrous hydrogen fluoride has been developed for the deposition of AlF{sub 3} at substrate temperatures between 100 and 200 °C. This low temperature process has resulted in thin films with UV-optical properties that have been characterized by ellipsometric and reflection/transmission measurements at wavelengths down to 200 nm. The optical loss for 93 nm thick films deposited at 100 °C was measured to be less than 0.2% from visible wavelengths down to 200 nm, and additional microstructural characterization demonstrates that the films are amorphous with moderate tensile stress of 42–105 MPa as deposited on silicon substrates. X-ray photoelectron spectroscopy analysis shows no signature of residual aluminum oxide components making these films good candidates for a variety of applications at even shorter UV wavelengths.

36 MATERIALS SCIENCE↗

Enabling Conversion-Type Iron Fluoride Cathode by Halide-Based Solid Electrolyte

The practical application of low-cost and energy-dense iron fluoride cathodes has been hindered by the first cycle electrochemical irreversibility, cycling instability, and large voltage hysteresis. Here, we report that these challenges may be overcome by the utilization of halide-based solid electrolytes (SEs). The excellent electrochemical stability of halide-based SEs enables a complete conversion and deconversion of FeF 2 which cannot be achieved with sulfide-based SEs. Due to restricted and reversible decomposition of SE, prevention of Fe dissolution, mechanical confinement of active material, as well as improved electrode kinetics, solid-state FeF 2 cathode with halide-based SE demonstrated superior electrochemical performance compared with FeF 2 electrodes in liquid electrolytes, with a high 1st cycle coulombic efficiency (~100 %), high specific capacity (~600 mAh/g), long cycle life (>100 cycles) and high-rate performance (up to 2C). In conclusion, our results suggest solidifying the batteries may be a viable approach to addressing the long-standing key challenges of iron fluoride cathodes.

25 ENERGY STORAGE↗

SuFEx-Based Polysulfonate Formation from Ethenesulfonyl Fluoride-Amine Adducts

In this article, the SuFEx-based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis(t-butyldimethylsilyl) ethers (BB monomers) using [Ph 3 P=N-PPh 3 ] + [HF 2 ] - as the catalyst is described. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t-butyldimethylsilyl chloride. With these reactions, a remarkable diversity of monomeric building blocks was achieved by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx-based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of side chain functionalities in >99 % conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click-chemistry-based post-polymerization modification.

36 MATERIALS SCIENCE↗

Manufacturing of Dysprosium-Iron Alloys by Electrolysis in Fluoride-Based Electrolytes. Electrolysis in a Laboratory-Scale Cell

Electrolytic production of light rare earth elements and rare earth alloys with transition elements takes place in a fluoride-based electrolyte using rare earth oxides as raw material. The optimization of this method, mainly in terms of the energy efficiency and environmental impact control, is rather challenging. Anode effects, evolution of fluorine-containing compounds and side cathode reactions could largely be minimized by good control of the amount of rare earth oxide species dissolved in the fluoride-based electrolyte and their dissolution rate. The Dy{sub 2}O{sub 3} feed rate needed for stable cell operation was studied by following up the anode voltage and gas analysis. On-line analysis of the cell off-gases by FTIR showed that the electrochemical reaction for the formation of Dy-Fe alloy gives mainly CO gas and that CF{sub 4} is starting to evolve gradually at anode voltages of ca. 3.25 V. The limiting current density for the discharge of the oxide ions at the graphite anode was in the range of 0.1 to 0.18 A cm{sup −2} at dissolved Dy{sub 2}O{sub 3} contents of ca. 1 wt pct. Modeling of the laboratory cell reactor was also carried out by implementing two models, i.e., an electrical model simulating the current density distribution at the electrodes and a laminal bubbly flow model that explains the electrolyte velocity induced by gas bubble production at the anode.

36 MATERIALS SCIENCE↗

Calcium fluoride as a dominating matrix for quantitative analysis by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS): A feasibility study

Here, calcium fluoride formed by the reaction between ammonium bifluoride and calcium chloride was investigated as a dominating matrix for quantitative analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Transformation from a solid sample to the calcium fluoride-based matrix permitted quantitative analysis based on calibration standards made from elemental standards. A low abundance stable calcium isotope, i.e. 44 Ca + , was monitored as the internal standard for quantitative analysis by LA-ICP-MS. Correlation coefficient factors for multiple elements were obtained with values over 0.999. The results for multiple elements in a certified reference material of soil (NIST SRM 2710a) agreed with the certified values in the range of expanded uncertainty, indicating the present method was valid for quantitation of elements in solid samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗