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Evaluated spectroscopic data and level schemes from radioactive decay and nuclear reaction studies are presented for {sup 22}C, {sup 22}N, {sup 22}O, {sup 22}F, {sup 22}Ne, {sup 22}Na, {sup 22}Mg, {sup 22}Al, and {sup 22}Si. This evaluation for A = 22 supersedes the earlier one by R. B. Firestone (2005Fi16)
Fluorinated porous organic networks (F-PONs) have demonstrated unique properties and applications, but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported. Herein, using polydivinylbenzene (PDVB) as an easily available precursor, a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Brønsted acid (trifluoromethanesulfonic acid. Furthermore, the afforded material (F-PDVB) featured high fluorine content (22 at.%), large surface area (771 m 2 ∙g -1 ), and good chemical/thermal stability, rendering them as promising candidates for the adsorption of CO 2 , hydrocarbons, fluorocarbons, and chlorofluorocarbons, with weight capacities up to 520 wt% being achieved. This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers (F-HCPs) from rigid aromatic monomers. The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications.
The observational {sup 19}F abundance in stellar environments systematically exceeds the predicted one, thus representing one of the unsolved challenges for stellar modeling. It is therefore clear that further investigation is needed in this field. In this work, we focus our attention on the measurement of the {sup 19}F(α,p){sup 22}Ne reaction in the astrophysical energy range, between 0.2 and 0.8 MeV (far below the Coulomb barrier, 3.8 MeV), as it represents the main destruction channel in He-rich environments. The lowest energy at which this reaction has been studied with direct measurements is ∼0.66 MeV, covering only the upper tail of the Gamow window, causing the reaction-rate evaluation to be based on extrapolation. To investigate lower energies, the {sup 19}F(α,p){sup 22}Ne reaction has been studied by means of the Trojan horse method, applied to the quasi-free {sup 6}Li({sup 19}F,p{sup 22}Ne){sup 2}H reaction at E {sub beam} = 6 MeV. The indirect cross section of the {sup 19}F(α,p){sup 22}Ne reaction at energies ≲1 MeV was extracted, fully covering the astrophysical region of interest and overlapping existing direct data for normalization. Several resonances have been detected for the first time inside the Gamow window. The reaction rate has been calculated, showing an increase up to a factor of 4 with respect to the literature at astrophysical temperatures. This might lead to potential major astrophysical implications.
22 Na ingrowth originating from fluorine-alpha interactions has been proposed as a chronometer for UF 6 cylinders. Furthermore, these proposals have ignored the prompt 1274 keV gamma-ray contribution from 19 F(α, p). We have shown that this contribution is significant and cannot be ignored when using this as a chronometer for UF 6 .
Several previous reports on undoped AEFe 2 As 2 (AE = alkaline earth metal) point to drops in resistivity indicative of possible superconductivity and some degree of Meissner effect in the magnetic susceptibility. Also, based on both resistivity and magnetic susceptibility measurements, controlled exposure to water vapor has been shown to induce superconductivity in AEFe 2 As 2 . In our study, BaFe 2 As 2 single crystals grown using the self-flux method showed a full resistive drop around 22 K and magnetic shielding, when exposed to fluorine gas postgrowth. Our measurements indicate electron (donor) doping via atomic substitution of F for As is concurrent with the observed superconductivity, which sheds light on the likely effect of exposure to water vapor in previous work. Like doping experiments (such as substitution of Co for Fe, P for As, or K for Ba) in AEFe 2 As 2 to date, the present work is consistent with suppression of the spin density wave transition coincident with the appearance of T c . In addition to answering the puzzle of superconductivity in undoped or water vapor exposed AEF 2 As 2 , our results also represent a fast (20 min exposure to 5% F in He) and reliable method suitable for inducing superconductivity in thin films of AEFe 2 As 2 . As a result, some supportive work on BaFe 2 As 2 exposed to Cl 2 is also presented.
Alpha particles emitted from the decay of uranium in a UF 6 matrix can interact with fluorine and generate neutrons via the 19 F(α,n) 22 Na reaction. These neutrons can be used to determine the uranium content in a UF 6 storage cylinder. The accuracy of this self-interrogating, non-destructive assay (NDA) technique is, however, limited by the uncertainty of the 19 F(α,n) 22 Na cross section. We have performed complementary measurements of the 19 F(α,n) 22 Na reaction with both 4 He and 19 F beams to improve the precision of the 19 F(α,n) 22 Na cross section over the alpha energy range that encompasses common actinide alpha decay needed for NDA studies. We have determined an absolute cross section for the 19 F(α,n) 22 Na reaction to an average precision of 7.6% over the alpha energy range of 3.9 – 6.7 MeV. We utilized this cross section in a simulation of a 100 g spherical UF 6 assembly and obtained a change in neutron emission rate values of approximately 10-12%, and a significant (factor of 3.6) decrease in the neutron emission rate uncertainty (from 50-51% to 13-14%), compared to simulations using the old cross section. Our new absolute cross section enables improved interpretations of NDAs of containers of arbitrary size and configuration.
Here, research on molten salt reactor (MSR) neutronics continues in Research Centre Rez (Czech Republic) with experimental work being conducted using fluoride salt that was originally used in the Molten Salt Reactor Experiment (MSRE). Previous results identified significant variations in the neutron spectrum measured in LiF-NaF salt. These variations could originate from the fluorine description in current nuclear data sets. Subsequent experiments were performed to try to confirm this phenomenon. Therefore, another fluorine-rich compound, Teflon, was used for testing. Critical experiments showed slight discrepancies in C/E-1 for both compounds, Teflon and FLIBE, and systematic overestimation of criticality was observed in calculations. Different nuclear data libraries were used for data set testing. For Teflon, the overestimation is higher when using JENDL-3.3, JENDL-4, and RUSFOND-2010 libraries, all three of which share the same inelastic-to-elastic scattering cross section ratio. Calculations using other libraries (ENDF/B-VII.1, ENDF/B-VII.0, JEFF-3.2, JEFF-3.1, and CENDL-3.1) tend to be closer to the experimental value. Neutron spectrum measurement in both substances revealed structure similar to that seen in previous measurements using LiF-NaF salt, which indicates that the neutron spectrum seems to be strongly shaped by fluorine. Discrepancies between experimental and calculational results seem to be larger in the neutron energy range of 100–1300 keV than in higher energies. In the case of neutron spectrum calculation, none of the tested libraries gives overall better results than the others.
Per- and poly-fluoroalkyl substances (PFAS) have substantial environmental and health hazards. Unfortunately, current degradation routes require high temperatures or corrosive conditions and/or lead to incomplete defluorination and the generation of shorter alkyl chains. Inspired by the lithium-metal battery literature, here we develop an electrochemical degradation process that leverages reactive metals and highly reducing environments. Here, we show that electrodeposited lithium metal can enable 95% degradation and 94% defluorination of perfluorooctanoic acid to LiF without forming any shorter C 2 –C 6 PFAS as end products. Using computational simulations, we find that electron transfer from lithium to perfluorooctanoic acid leads to rapid C–F bond cleavage, fluoride formation and carbon chain fragmentation. We expand the scope to other PFAS compounds and demonstrate substantial degrees of degradation on over 22 different PFAS, plus complete mineralization to inorganic fluorides. Finally, we use the mineralized F − as a fluorine source for the synthesis of fluorinated non-PFAS compounds to complete a circular fluorine loop from waste to valuable product.
Dental enamel is subjected to a lifetime of de- and re-mineralization cycles in the oral environment, the cumulative effects of which cause embrittlement with age. However, the understanding of atomic scale mechanisms of dental enamel aging is still at its infancy, particularly regarding where compositional differences occur in the hydroxyapatite nanocrystals and what underlying mechanisms might be responsible. Here, we use atom probe tomography to compare enamel from a young (22 years old) and a senior (56 years old) adult donor tooth. Findings reveal that the concentration of fluorine is elevated in the shells of senior nanocrystals relative to young, with less significant differences between the cores or intergranular phases. It is proposed that the embrittlement of enamel is driven, at least in part, by the infusion of fluorine into the nanocrystals and that the principal mechanism is de- and re-mineralization cycles that preferentially erode and rebuild the nanocrystals shells.
A molding study of compounds based on copolymers of highly fluorinated olefins and of flame retardant silicone is reported. Both single cavity and four cavity molds having size 22 and 24 holes with three webs in each hole were used. Also covered are dielectric strength, arc resistance, Bashore rebound, and maintenance aging tests on the various materials that have been successfully molded.
The significance of oxygen isotope ratios in Archean chert has long been debated. Cherts from the c. 3.4 Ga Strelley Pool Formation (SPF) (Pilbara Craton, Western Australia) host some of the oldest stromatolite and microfossil evidence for life, but the genesis and timing of silica cements has been unclear. Field relations, petrography and a combination of laser fluorination and in-situ SIMS measurements of δ 18 O in quartz show that bedded cherts of the SPF were originally precipitated as carbonates and were later widely replaced by quartz. Three localities were studied and analyzed for δ 18 O(Qz) in chert: 1) Camel Creek: foliated, metamorphosed, bedded cherts and meter-scale black chert veins; 2) Unconformity Ridge and ABDP8 drill core: stromatolitic and bedded chert overlying basal detrital quartz sandstone; and 3) the Trendall locality: “bedded” stromatolitic chert replacing original dolomite, low temperature hydrothermal quartz, and mm- to decimeter-scale chert-quartz veins. Laser fluorination (mm-scale) values of δ18O(Qz) range from: 14.2 to 18.2‰ VSMOW at Camel Creek; 9.3 to 18.9‰ at Unconformity Ridge; and 13.7 to 25.7‰ at Trendall. Values of δ 18 O(Qz) in cm to decimeter-scale hydrothermal chert veins cutting bedded carbonates at Trendall range from ca. 15 to 16‰, whereas “bedded cherts” are 17 to 26‰. These laser data include the highest δ 18 O values reported for cherts in Paleoarchean sediments and are up to 4‰ higher than the upper limit of ~22‰ reported in other studies, in apparent contrast to the long-standing secular-temporal trend which shows such high δ 18 O only in younger chert. However, analysis by laser fluorination at the 1-mm scale cannot resolve microtextures seen petrographically. In contrast, in-situ SIMS analyses can resolve petrographic microtextures and show δ 18 O(Qz) at 10-μm scale have an even greater range of 7–31‰ in “bedded” cherts at the Trendall locality, up to 9‰ above the secular-temporal trend. Textures observed optically at the Trendall locality were classified as: microquartz, mesoquartz, chalcedony, megaquartz veins, and cavity megaquartz. SEM-CL imaging shows two generations of meso- and megaquartz; bright CL with well-developed growth zoning, and dark CL with massive or mottled texture. Microquartz is the earliest textural generation of quartz and has a maximum δ 18 O(Qz) of ~22‰ by SIMS. Dark-CL mesoquartz has similar δ 18 O to microquartz and is interpreted to also be early. Bright-zoned-CL mesoquartz, which formed post-Archean, has even higher δ 18 O, up to 29‰. Vein megaquartz crosscuts most quartz generations and has a restricted range of δ 18 O, mostly from 16 to 19‰. Chalcedony pseudomorphs rhombic cavities and fractures, lines the edges of veins, and has similar δ 18 O to veins (16–19‰). Late cavity megaquartz is bright and zoned by CL, grows into late open cavities, and has the highest δ 18 O(Qz) values reported from the Pilbara, up to 31.3‰. Thus, the highest-δ 18 O quartz cements at the Trendall locality are the youngest and may be related to weathering. Early silicification and the formation of microquartz, chalcedony and low δ 18 O mesoquartz occurred during low temperature hydrothermal activity in the Archean. None of the SPF quartz examined is interpreted to have formed as a direct precipitate from Paleoarchean seawater. Thus, values of δ 18 O(Qz) do not record either water chemistry or temperature of Archean oceans. In-situ SIMS analysis shows that high-δ 18 O(Qz) values above 22‰ are only found in late-forming cavity megaquartz and bright-zoned-CL mesoquartz at the Trendall locality. The SPF results from our sample suite demonstrate the ability to resolve complex history using detailed petrography and SIMS analysis. Similar studies may show equal complexity of δ 18 O(Qz) data for other localities that are interpreted to show secular-temporal trends for chert. The apparent increase of δ 18 O(Qz) through time may reflect differences in diagenesis, and/or an inherent and previously unrecognized sampling bias that compares fundamentally different populations of quartz, such as Archean hydrothermal chert from volcanic greenstone belts, with unrelated Phanerozoic biogenic quartz.
Necessary for safe and proper functioning of equipment. Mainly halogenated solvents. Tetrachloride, Trichloroethylene (TCE), CFC-113. No longer used due to regulatory/safety concerns. Precision Cleaning at KSC: Small % of total parts. Used for liquid oxygen (LOX) systems. Dual solvent process. Vertrel MCA (decafluoropentane (DFP) and trons-dichloroethylene) HFE-7100. DFP has long term environmental concerns. Project Goals: a) Identify potential replacements. b) 22 wet chemical processes. c) 3 alternative processes. d) Develop test procedures. e) Contamination and cleaning. f) Analysis. g) Use results to recommend alternative processes. Conclusions: a) No alternative matched Vertrel in this study. b) No clear second place solvent. c) Hydrocarbons- easy; Fluorinated greases- difficult. d) Fluorinated component may be needed in replacement solvent. e) Process may need to make up for shortcoming of the solvent. f) Plasma and SCC02 warrant further testing.
The separation of xenon/krypton (Xe/Kr) mixtures is a challenging process. Many porous materials allow the adsorption of both Xe and Kr but only with low selectivity. Anion-pillared metal–organic frameworks (MOFs), featuring the anion groups as structural pillars, show potential in gas separations, but only a limited number of them have been synthesized. Here, we describe a collection of 936 anion-pillared MOFs based on 22 experimentally available structures. We performed density functional theory (DFT) optimization and then assigned density-derived electrostatic and chemical (DDEC) charges for each MOF to make them well suited to molecular simulations. The structural properties of the MOFs vary more strongly with the choice of the organic ligand than with other aspects like fluorine groups and metal centers. We then screened the entire collection of MOFs in the context of Xe/Kr separation at room temperature. Compared with previously reported MOFs, the interpenetrated MOF SIFSIX-6-Cd-i is predicted to perform better for Xe/Kr separations, with a good balance between working capacity (1.62 mmol/g) and separation selectivity (16.4) at 298 K and 100 kPa. Here, we also found that the heterogeneity of fluorine groups within a MOF can help to enhance Xe working capacity without reducing the Xe/Kr selectivity, suggesting that synthesis of anion-pillared MOFs with mixed fluorine groups may lead to improved Xe/Kr separation performance.
Halogenated CBr(sub x)I(sub y) (1 less than y/x less than 10) was made by exposing graphite materials with interplanar spacing in the 3.35 to 3.41 A range to either pure Br2 or an I2-Br2 mixture, and then to iodine vapor containing a small amount of Br2. The electrical resistivity of this product is from 3 to 6.5 times the pristine value. The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine to bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to fluorine attack during subsequent fluorination to fabricate graphite fluoride fibers.
Halogenated graphite CBr(x)I(y) (I less than y/x less than 10) was made by exposing graphite materials to either pure Br2 or an I2/Br2/HBr mixture to initiate the reaction, and then to iodine vapor containing a small amount of Br2/HBr/IBr to complete the intercalation reaction. Wetting of the graphite materials by the I2/Br2/HBr mixture is needed to start the reaction, and a small amount of Br2/HBr/IBr is needed to complete the charge transfer between iodine and carbon. The interplanar spacings for the graphite materials need to be in the 3.35 to 3.41 A range. The X-ray diffraction data obtained from the halogenated HOPG indicate that the distance between the two carbon layers containing intercalate is 7.25 A. Electrical resistivity of the fiber product is from 3 to 6.5 times the pristine value, The presence of a small amount of isoprene rubber in the reaction significantly increased the iodine-to-bromine ratio in the product. In this reaction, rubber is known to generate HBr and to slowly remove bromine from the vapor. The halogenation generally caused a 22 percent to 25 percent weight increase. The halogens were found uniformly distributed in the product interior. However, although the surface contains very little iodine, it has high concentrations of bromine and oxygen. It is believed that the high concentrations of bromine and oxygen in this surface cause the halogenated fiber to be more resistant to structural damage during subsequent fluorination to fabricate graphite fluoride fibers.
We have analyzed the rate of C(sp 2 )–C(sp 2 ) reductive elimination from nickel(II) bis(2,4,6-trifluorophenyl) complex-es (P–P)Ni(2,4,6-C 6 H 2 F 3 ) 2 containing either MeOBiPhep (3a) or macrocyclic bisphosphine ligand (3b-3e) as a func-tion of force applied to the biaryl backbone of these ligands through intramolecular tension generated by a molecular force probe. Nickel complexes 3 were isolated in 22-60% yield from reaction of bisphosphine with the bis(tetrahydrofuranyl) complex (THF) 2 Ni(2,4,6-C 6 H 2 F 3 ) 2 followed by chromatography. Thermolysis of complexes 3 in C 6 D 6 at 68 °C leads to first-order decay through > 3 half-lives to form 2,2',4,4',6,6'-hexaflurorobiphenyl as the exclusive fluorine-containing product in ≥93% yield. Whereas compressive forces up to –65 pN have no significant effect on the rate of reductive elimination, extension forces increase the rate of reductive elimination by a factor of three over a ~230 pN range of restoring forces relative to the strain-free MeOBiphep complex. Furthermore, the rate response of reductive elimination from nickel(II) bis(trifluorophenyl) complexes as a function of extension force is similar to the previously reported 2.8-fold increase in the rate of reductive elimination from platinum diaryl complexes (P–P)Pt(4-C 6 H 4 NMe 2 ) 2 over the same range of forces
Uranyl fluoride (UO 2 F 2 ) particles (<20 μm) were subjected to first-of-its-kind analysis via simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation multi-collector inductively coupled plasma–mass spectrometry (LA–MC–ICP–MS). Briefly, a nanosecond pulsed high-energy laser was focused onto the sample (particle) surface. In a single laser pulse, the UO 2 F 2 particle was excited/ionized within the microplasma volume, and the emission of light was collected via fiber optics such that emission spectroscopy could be employed for the detection of uranium (U) and fluorine (F). The ablated particle was simultaneously transported into the MC–ICP–MS for high precision isotopic (i.e., 234 U, 235 U, and 238 U) analysis. This method, LIBS/LA–MC–ICP–MS was optimized and employed to rapidly measure 80+ UO 2 F 2 particles, which were subjected to different calcination processes, which results in varying degrees of F loss from the individual particles. In measuring the particles, the average F/U ratios for the populations treated at 100 and 500 °C were 2.78 ± 1.28 and 1.01 ± 0.50, respectively, confirming loss of F through the calcination process. The average 235 U/ 238 U on the particle populations for the 100 and 500 °C were 0.007262 (22) and 0.007231 (23), which was determined to be <0.2% from the expected value. The 234 U/ 238 U ratios on the same particles were 0.000053 (11) and 0.000050 (10) for the 100 and 500 °C, respectively, <10% from the expected value. Notably, each population was analyzed in under 5 min, demonstrating the truly rapid analysis technique presented here in this paper.
Nuclear graphite has historically been a key component of many nuclear reactor designs and has emerged as key to numerous advanced nuclear reactor design concepts. Molten salt reactors (MSRs) are one broad group of advanced reactor designs currently being pursued by industry for commercialization. Several MSR designs under consideration use graphitic materials that directly interface with a molten salt, whether it is a fuel salt, coolant salt, or both. Therefore, the interaction of graphite materials with molten salts must be understood. To gain this required understanding, a range of data is needed including porosity, strength, and composition as a function of different salt exposure parameters. In this study, a laser-induced breakdown spectroscopy (LIBS) measurement and data analysis methodology was developed to obtain spatially resolved elemental composition information for graphite samples exposed to a molten fluoride salt. Traditional univariate emission line analysis of atomic, ionic, and molecular optical emission signals was coupled via correlation analysis with spectral decomposition of the data using principal component analysis. Elemental depth profiling and elemental mapping were also performed to visualize salt–graphite interactions. LIBS was demonstrated to be useful for measuring key analytes such as fluorine and hydrogen, which are troublesome for other analysis techniques. Evidence for complex behavior was found, thereby demonstrating the usefulness of the developed approach for future systematic studies.