Effect Of Fluorine Research Articles

The behaviour of scandium during crustal anatexis: Implications for the petrogenesis of Sc-enriched granitic magma

Scandium (Sc) is a compatible element in mafic silicate minerals, in particular amphibole, garnet and clinopyroxene, and is enriched in ultramafic rocks. Nevertheless, its concentration is also sufficiently high in some evolved granites and granite pegmatites to form minerals with essential Sc. In some granitic occurrences, Sc-bearing minerals occur in miarolitic cavities, indicating the importance of late- to post-magmatic fluids. In contrast, some granite pegmatites have thortveitite (Sc2Si2O7) and other Sc-rich minerals, including Sc-enriched garnet as part of evolved magmatic mineral assemblages. The maximum Sc concentration in garnet in thortveitite-bearing, Mesoproterozoic granite pegmatites of probable anatectic origin in South Norway is ca. 2000 ppm, corresponding to ca. 100 ppm in a coexisting silicate melt. As for any trace element, the behaviour of Sc during crustal anatexis is controlled by the amount of melt formed and the mineralogy of the solid residue. The melting process can be modelled from thermodynamical data on solids and melts for given protolith compositions, temperature and pressure. Simulations in a range of mafic/ultramafic to felsic systems show that mafic protoliths will form Sc-depleted anatectic melts, and correspondingly Sc-enriched solid residues under relevant pressure and temperature conditions (2-10 kbar, 700-800 °C). Limited enrichment in melt relative to protolith is only seen in granodioritic-tonalitic bulk compositions, reaching maximum concentrations of 30–60 ppm. The effect of fluorine during melting and subsequent fractionation is to lower the solidus temperature, depolymerise the silicate melt, and lower partition coefficients for Sc between mafic silicate minerals and felsic melt. Contamination with mafic material has only limited effect, as it will eventually sequester Sc into hybrid mafic silicate mineral assemblages and lead to reduction of the Sc concentration of the remaining melt fraction. Further increase of the Sc concentration requires fractional crystallisation of minerals with low KD, i.e. mainly feldspar minerals and quartz, which may be facilitated by selective, local contamination by quartz and feldspar from granitic country rocks.

CoFe Hydroxide Nanospheres for Enhanced Alkaline Water Splitting and Seawater Oxidation:Anion Doping Effects of Fluorine and Carbonate.

Green hydrogen production can be achieved through electrolysis of fresh water or the use of renewable energy to electrolyze seawater. However, due to the low activity and poor stability of oxygen evolution reaction catalysts, direct electrolysis of alkaline seawater faces significant challenges. Herein, The catalyst F-CoFe(OH)-CO3/NF with three-dimensional nanosphere structure was prepared, The introduction of CO3 2- into the intermediate layer of CoFe hydroxide improves the corrosion resistance of alkaline electrolyte and the doping of F- is to design three-dimensional layered nanostructures, increase the active site, and accelerate the diffusion of the electrolyte. By in situ Raman analysis, partial oxidation of CoFe hydroxide to CoFe (oxy)hydroxide as the active center can accelerating the adsorption of oxygen-related intermediates. In 1 M KOH, it requires overpotentials of 210 mV and 251 mV to drive current densities of 10 and 100 mA cm-2, respectively. And it remained stable at the current density of 100 mA cm-2 for 120 h in 1 M KOH. F-CoFe(OH)-CO3/NF can also catalyzes the decomposition of electrolytic seawater. Compared with hydroxide, anion-doped carbonate hydroxide is more efficient and stable in electrolyte solution, which is of great importance for the development of a new stable electrocatalyst for water decomposition.

High-Pressure Behaviors of Hydrogen Bonds in Fluorine-Doped Brucite.

Brucite, Mg(OH)2 (P3̅m1, Z = 1), is a prototype material for studying hydrogen bonds in solid hydroxides. In this study, substitutional effects of fluorine (F) on the hydrogen-bonding geometries of hydrogenated and deuterated brucite were investigated under ambient conditions and at high pressure using combined experimental methods of neutron powder diffraction, Raman spectroscopy, and infrared (IR) spectroscopy. Under ambient conditions, neutron powder diffraction results showed that F substitution decreased the donor-acceptor distance and increased the hydroxyl covalent bond lengths of both hydrogenated and deuterated brucite, strengthening the hydrogen bond. Red shifts of the hydroxyl stretching modes also indicated an elongation of d(O-H) and d(O-D). High-pressure neutron diffraction experiments were performed on Mg(OH)1.81F0.19 and Mg(OD)1.74F0.26 up to 7.04 and 10.02 GPa, respectively. For both samples, changes in the hydrogen-bonding geometries did not indicate hydrogen-bond strengthening under high pressure. Compared with Mg(OD)2, the doping of F suppressed the increase of the hydroxyl covalent bond length, the hydrogen-bond angle, and the cone angle, inhibiting pressure-induced hydrogen-bond strengthening. High-pressure Raman and IR absorption spectroscopic measurements on Mg(OD)2 and Mg(OD)1.79F0.21 up to 9.7 and 13.7 GPa confirmed that F substitution restrains pressure-induced hydroxyl elongation.

Effects of fluorine and phosphorus-based flame retardants addition on the lower flammability limit of dimethyl carbonate

This study initially examines the alteration pattern of the lower flammable limit (LFL) of dimethyl carbonate (DMC), a typical electrolyte component in lithium batteries, under the influence of inhibitors, namely di(2,2,2trifluoroethyl) carbonate (DtFEC), perfluorohexanone (C6F12O), and trimethylphosphate (TMP), through experimental investigation. Additionally, the critical inhibitory concentration required for complete inhibition is investigated. Subsequently, numerical simulations and chemical kinetic path analyses reveal how these inhibitors control combustion. Results show that C6F12O and DtFEC initially decrease and then increase the LFL of DMC, while TMP causes a monotonic increase. This is due to the competition between reaction-thermal and reaction-radical effects. Reaction kinetic analysis reveal that when small amounts of C6F12O and DtFEC are added, the fluorine-containing components decomposed by the reaction undergo oxidation, thereby promoting combustion. However, with increased amounts, these components combine with H and OH radicals to form stable substances like HF, inhibiting the combustion process. In the case of TMP, the phosphorus-containing intermediate components produced by cleavage catalyze the recombination of H and OH radicals, thereby inhibiting DMC combustion. The research findings offer a theoretical foundation for the development of safer lithium batteries and provide crucial data references for enhancing battery safety and prevention measures.

The Effect of Fluorine and Hydrogen Concentrations on the Chain Reaction of HF Chemical Laser

A numerical investigation has been performed to examine the effect of fluorine concentration on the chain reaction mechanisms and parameters of hydrogen fluoride (HF) chemical laser. The practical difficulties associated with this type of lasers impose that an alternative route might be quite useful. Thus, particular attention was paid to develop a computer program to investigate various processes. The results of this computer simulation program proved their credibility when compared with the little published data. This computer program is called Reaction Rate Simulation Model (RRSM). An entirely new approach to emulate the reaction mechanisms has been followed. The effectiveness of reaction rates in the processes of HF laser production has been investigated. This simulation program dealt with the percentages of the forward and reverse reactions, when a large number of reactions have been considered. In addition a large number of species have been taken into account in these reactions. From the computer program (RRSM), some valuable results could be predicted with regard to the hydrogen fluoride chemical laser.

Humidity-independent NO2 gas sensors based on ZnO-NiOFx nanocomposites and the synergistic humidity-immune effect of fluorine doped NiO

Clean, alternative energy sources, especially fuel cells, are gradually attracting global attentions while the produced toxic nitrogen dioxide (NO2) is a greatly hazardous chemical impacting their energy efficiencies. Metal oxide semiconductors (MOS) hold significant promise as NO2 sensors. However, intensive humidity interaction intensifies signal drifts and reliable response inhibitions under variable humidity conditions. In this study, we present a novel approach to address this issue by engineering in-situ F-doped NiO nanocomposites (NiOFx) decorated on ZnO snowflakes achieved through decomposition modulation of ZnOHF precursors. The optimized NO2 sensor demonstrates unparalleled humidity-independence across a wide operating temperature range with prime sensitivity, low detection limit and rapid response/recovery. Matrix algorithm is also implemented in highly precise NO2 identification under complicated atmospheric and humid conditions. Mechanism studies based on temperature programmed desorption (TPD), quasi in-situ X-ray photoelectron spectroscopy (Quasi in-situ XPS) reveal that F− dopants facilitate interfacial electron transferring and inhibit oxygen activity. In-situ diffuse reflectance infrared Fourier transform spectroscopy (In-situ DRIFTS) demonstrates that hygroscopic NiO and electronegative F− synergistically obstruct hydroxyl adsorptions on sensing materials. The innovative approach offers a promising solution for enhancing moisture resistance of MOS sensors for real-time NO2 concentration monitoring in fuel cells and provides valuable insights into anti-humidity mechanisms.

A new aspect of the effect of fluorine doping on structural and superconducting properties in the Bi2Sr1.6La0.4CuO5+δ(O1-xFx) ceramic system

In this study, ceramic samples with the nominal composition Bi2Sr1.6La0.4CuO5+δ(O1-xFx) (where x = 0, 0.2 and 0.4) were synthesized using the solid-state reaction method to investigate the effects of fluorine anionic doping on the Bi-2201 system's structural, microstructural, and superconducting properties. X-ray diffraction analysis (XRD) confirmed the Bi-2201 phase in all samples and total incorporation of fluorine. Doping with fluorine reduced orthorhombicity, leading to an orthorhombic-tetragonal transition. Scanning electron microscopy (EDS) revealed changes in grain shape and size, while energy dispersive x-ray analysis (EDAX) confirmed fluorine incorporation. DC-electrical resistivity measurements showed that fluorine doping decreased the critical transition temperature TC (Onset), with a greater decrease observed at higher fluorine concentrations. The resistivity increase in the normal state of the sample with x = 0.4 was also noted. The conduction mechanism above TC (Onset) = 26.10 K followed the Arrhenius law, indicating thermally activated behavior due to a band gap.

Unmasking Fluorinated Moieties on the Surface of Hydride-Terminated Silicon Nanoparticles.

Despite the widespread use of hydrofluoric acid (HF) in the preparation of silicon surfaces, the true nature of fluorinated surface species remains unclear. Here, we employ an array of characterization techniques led by solid-state nuclear magnetic resonance spectroscopy to uncover the nature of fluorinated moieties on the surface of hydride-terminated silicon nanoparticles (H-SiNPs). A structural model that explains the observed trends in 19F and 29Si magnetic shielding is proposed and further supported by quantum chemical computations. Fluorine is incorporated into local oxidation domains on the surface and clustered at the interface of the oxide and surrounding hydride-terminated surface. Silicon sites capped by a single fluorine are also identified by their distinct 19F and 29Si chemical shifts, providing insight into how fluorine termination influences the electronic structure. The extent of fluorine passivation and the effects of fluorine on the optical properties of SiNPs are also discussed. Finally, challenges associated with Teflon contamination are highlighted that future explorations of nanomaterials may have to contend with.

The Impact of Exposure to Iodine and Fluorine in Drinking Water on Thyroid Health and Intelligence in School-Age Children: A Cross-Sectional Investigation.

Iodine and fluorine, as halogen elements, are often coexisting in water environments, with nearly 200 million people suffering from fluorosis globally, and, in 11 countries and territories, adolescents have iodine intakes higher than that required for the prevention of iodine deficiency disorders. It has been suggested that excess iodine and/or fluorine can affect thyroid health and intellectual development, especially in children, but their combined effect has been less studied in this population. This study investigated 399 school-age children in Tianjin, China, collected drinking water samples from areas where the school-age children lived, and grouped the respondents according to iodine and fluorine levels. Thyroid health was measured using thyroid hormone levels, thyroid volume, and the presence of thyroid nodules; intelligence quotient (IQ) was assessed using the Raven's Progressive Matrices (CRT) test; and monoamine neurotransmitter levels were used to explore the potential relationship between thyroid health and intelligence. Multiple linear regression and restricted cubic spline (RCS) analyses showed that iodine and fluorine were positively correlated with thyroid volume and the incidence of thyroid nodules in school-age children, and negatively correlated with IQ; similar results were obtained in the secondary subgroups based on urinary iodine and urinary fluoride levels. Interaction analyses revealed a synergistic effect of iodine and fluorine. A pathway analysis showed that iodine and fluorine were negatively associated with the secretion of free triiodothyronine (FT3) and free tetraiodothyronine (FT4), which in turn were negatively associated with the secretion of thyroid-stimulating hormone (TSH). Iodine and fluorine may affect IQ in school-aged children through the above pathways that affect thyroid hormone secretion; of these, FT3 and TSH were negatively correlated with IQ, whereas FT4 was positively correlated with IQ. The relationship between thyroid hormones and monoamine neurotransmitters may involve the hypothalamic-pituitary-thyroid axis, with FT4 hormone concentrations positively correlating with dopamine (DA), norepinephrine (NE), and 5-hydroxytryptophan (5-HT) concentrations, and FT3 hormone concentrations positively correlating with DA concentrations. Monoamine neurotransmitters may play a mediating role in the effects of iodine and fluoride on intelligence in schoolchildren. However, this study has some limitations, as the data were derived from a cross-sectional study in Tianjin, China, and no attention was paid to the reciprocal effects of iodine and fluorine at different doses on thyroid health and intelligence in schoolchildren in other regions.

The effect of fluorine doped diamond-like carbon coatings on the corrosion behaviour of cobalt chromium molybdenum substrates

The effect of fluorine doped diamond-like carbon coatings on the corrosion behaviour of cobalt chromium molybdenum substrates

High-temperature stable chromium complexes bearing fluorinated PNP ligands for selective ethylene tetramerization toward 1-octene

A series of new fluorinated PNP ligands of bis(ortho-fluorophenyl)-type (L1-L2) and ortho-fluorophenyl-type (L3-L4) have been synthesized and assessed for the selectivity of ethylene oligomerization. Compared to the non-fluorinated analogue ligand L6, the fluorinated ligand L1 exhibited approximately three times high catalytic activity. The bis(ortho-fluorophenyl)-type ligand L2 with a diethylphosphine substituent offered the highest catalytic performance of 3548 kg∙g−1∙h−1 and the 1-octene selectivity is 67.6 %. Both the L1 and L2 ligands exhibited excellent the activity of catalyst at a high temperature of 100 ℃, with ligand L2 providing the catalytic performance of 1587 kg∙g−1∙h−1 and good selectivity of 47.5 % for 1-C8=. The ortho-fluorophenyl substituent enhances the catalytic activity, while the para-fluorophenyl substituent reduces the catalytic activity. In addition, density functional theory (DFT) calculations and UV–vis spectroscopy have been used to rationalize the role of the fluorine effect in promoting catalytic performance. Our results indicated that the strong inductive effect of fluorine atoms and the non-covalent interaction between fluorine atoms and active centers jointly enhance the stability of the ortho-fluorophenyl-based catalyst and promote its overall activity.

Solidification and Stabilization of Fluorine and Phosphorus in Phosphate Mine Tailings and the Mechanism of F and P Fixation During Soilization

AbstractResearching methods for harmless and resourceful utilization of phosphate mine tailings presents a new approach to addressing phosphate mine tailings pollution. This study selected a formulation of agents for solidifying fluorine and phosphorus in phosphate mine tailings, investigating the solidification effects of phosphorus and fluorine under different temperatures and time, as well as the changes in the physicochemical properties of phosphate mine tailings. Solidified phosphate mine tailings soilization results showed that phosphate mine tailings: polymerized aluminum sulfate: ferrous sulfate=96.5 : 1.75 : 1.75 worked well, with a leaching toxicity of fluorine of 0.9569 mg/L, a fixation rate of 74.92 %, and a retention of water‐soluble phosphorus of up to 82.75 %. At 25 °C and 28 days of cultivation, the leaching toxicity of phosphate mine tailings treated with the solidifying agent was less. Solidified phosphate mine tailings were again added with solidifying agent to solidify phosphorus and fluorine, and the stabilization rate of fluorine reached 90.08 %. The “soil” cultivated for 28 days had an optimal structure of nutrients, and the germination rate of cabbage seeds was 83.33 %. This study demonstrates the possibility of using phosphate mine tailings as planting soil, and provides a useful theoretical basis for the fluoride fixation mechanism in phosphate mine tailings.

Review on the toxic effect of fluorine and lead on lichen metabolism

Thanks to their ability to absorb large amounts of trace elements from the atmosphere, lichens are widely used as bioaccumulators and bioindicators of air pollution. Among air pollutants, heavy metals represented by lead are the most important contributors to the deterioration of ecosystems. Fluorine is prevalent in a wide range of environmental matrices, even in trace amounts, and is one of the most phytotoxic halogens to plants. When lichens are exposed to air pollution, they frequently undergo structural, morphological and physiological alterations, and exhibit several coping strategies to combat and tolerate stressful situations. This manuscript presents general information about lichens, fluorine, and lead as well as the toxic effect of these two air pollutants on lichens, and the means of combat used by lichens to respond to fluorine and lead-induced stress.

Acidity of saturated (hetero)cyclic α-fluoro carboxylic acids and lipophilicity of their amide derivatives

Analysis of the physicochemical parameters of saturated (hetero)cyclic carboxylic acids and their α-fluorinated analogues is described. Measured pKa values revealed a significant influence of the single fluorine substituent on the compound's acidity (pKa decreased by 1.3–2.4 units). This effect did not demonstrate additivity with electronic effects of other heteroatom (i.e., cyclic ether moiety). On the contrary, lipophilicity (LogP) of the corresponding anilides was almost unaffected upon α-substitution with a fluorine atom and mainly governed by the nature of the (hetera)cycloalkyl substituent. The obtained results suggest that polarization of the C–F bonds themselves does not define the fluorine effect on the compound's lipophilicity.

Thermoelectric properties of reduced TiO2 -SrF2 composites

Highly stable thermoelectric materials based on inexpensive elements have great potential for heat recovery in high temperature applications. TiO2-d and SrTiO3 based thermoelectric materials are of great interest due to this reason. In this study TiO2–SrF2 based compounds were produced, to study the effect of fluorine on the thermoelectric properties of TiO2 type materials. From XPS measurements it is clear that some exchange from the TiO2–SrF2 happens forming a TiOxFy type phase. The electronic properties of the compound are very similar to the electronic properties of reduced TiO2 while some improvement is seen in the reduction of the thermal conductivity. A higher activation energy in the SrF2 rich samples might allow for increased electronic conductivity at higher temperatures interesting for further studies.

Fluorine‐Effect‐Enabled Photocatalytic 4‐Exo‐Trig Cyclization Cascade to Access Fluoroalkylated Cyclobutanes

AbstractCyclobutanes are popular structural units in bioactive compounds and versatile intermediates in synthetic chemistry, but their synthesis is challenging owing to high ring strain. In this study, a novel method for highly regio‐ and diastereoselective synthesis of fluoroalkylcyclobutanes bearing vicinal quaternary and tertiary stereocenters is realized by a photocatalytic 4‐exo‐trig cyclization cascade of thioalkynes or trifluoromethylalkenes. Density functional theory calculations reveal that a unique fluorine effect, arising from hyperconjugative π→σ*C‐F interactions, accounts for the regio‐reversed radical addition at the sterically hindered alkene carbon, which facilitates an unprecedented 4‐exo‐trig ring closure. This chemistry enables the direct and controllable construction of medicinally valuable quaternary‐carbon‐containing cyclobutanes from readily available raw materials, nicely complementing the existing methods.

Fluorine-Effect-Enabled Photocatalytic 4-Exo-Trig Cyclization Cascade to Access Fluoroalkylated Cyclobutanes.

Cyclobutanes are popular structural units in bioactive compounds and versatile intermediates in synthetic chemistry, but their synthesis is challenging owing to high ring strain. In this study, a novel method for highly regio- and diastereoselective synthesis of fluoroalkylcyclobutanes bearing vicinal quaternary and tertiary stereocenters is realized by a photocatalytic 4-exo-trig cyclization cascade of thioalkynes or trifluoromethylalkenes. Density functional theory calculations reveal that a unique fluorine effect, arising from hyperconjugative π→σ*C-F interactions, accounts for the regio-reversed radical addition at the sterically hindered alkene carbon, which facilitates an unprecedented 4-exo-trig ring closure. This chemistry enables the direct and controllable construction of medicinally valuable quaternary-carbon-containing cyclobutanes from readily available raw materials, nicely complementing the existing methods.

Changes in Metabolism and Content of Chlorophyll in Common Duckweed (Lemna minor L.) Caused by Environmental Contamination with Fluorides.

The impact of fluorine on plants remains poorly understood. We examined duckweed growth in extracts of soil contaminated with fluorine leached from chicken manure. Additionally, fluorine levels were analyzed in fresh manure, outdoor-stored manure, and soil samples at varying distances from the manure pile. Fresh manure contained 37-48 mg F- × kg-1, while soil extracts contained 2.1 to 4.9 mg F- × kg-1. We evaluated the physiological effects of fluorine on duckweed cultured on soil extracts or in 50% Murashige-Skoog (MS) medium supplemented with fluorine concentrations matching those in soil samples (2.1 to 4.9 mg F- × L-1), as well as at 0, 4, and 210 mg × L-1. Duckweed exposed to fluorine displayed similar toxicity symptoms whether in soil extracts or supplemented medium. Fluoride at concentrations of 2.1 to 4.9 mg F- × L-1 reduced the intact chlorophyll content, binding the porphyrin ring at position 32 without affecting Mg2+. This reaction resulted in chlorophyll a absorption peak shifted towards shorter wavelengths and formation of a new band of the F--chlorophyll a complex at λ = 421 nm. Moreover, plants exposed to low concentrations of fluorine exhibited increased activities of aminolevulinic acid dehydratase and chlorophyllase, whereas the activities of both enzymes sharply declined when the fluoride concentration exceeded 4.9 mg × L-1. Consequently, fluorine damages chlorophyll a, disrupts the activity of chlorophyll-metabolizing enzymes, and diminishes the plant growth rate, even when the effects of these disruptions are too subtle to be discerned by the naked human eye.

Effect of fluorine on the viscosity and structure of non-reactive mold fluxes for high-Mn high-Al steel

The impact of varying F content from 4 wt% to 10 wt% on the structure and properties of non-reactive mold slag for high-Mn high-Al steel was investigated in this study. Employing a combination of techniques including a rotary viscometer, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy, the viscosity and structure of mold slag were analyzed. The findings revealed that increasing F content led to a gradual reduction in viscosity, activation energy for viscous flow, and the internal friction within the mold fluxes, consequently enhancing its fluidity. The Al–O–Al structure remained stable throughout the experimental range. The decrease in QAl2 content indicated a continuous depolymerization process, leading to the formation of free [Al2OF6] and [AlO6] structures as F content increased. At the same time, the replaced O2− ions were assimilated by [AlO4] tetrahedron, facilitating the formation [AlO6] octahedron. Consequently, the slag structure was simplified, resulting in a reduction in the degree of polymerization and viscosity.

The effects of fluorine doping on the structure, interface and electrochemical properties of lithium titanate

Enhancing the electronic and ionic conductivity of Li4Ti5O12 electrode materials, as well as suppressing the interface reaction between Ti4+ on the surface of Li4Ti5O12 and the electrolyte, is one of the key factors in preparing high-power and long-life Li4Ti5O12 lithium-ion batteries. To tackle these challenges, fluorine ions with strong electronegativity was chosen as dopants to engineer fluorine-doped Li4Ti5O12 electrode materials. Fluorine ion doping changes the surface state of Li4Ti5O12, increases the interface compatibility, suppresses the reactivity between Li4Ti5O12 and the electrolyte, and forms a uniform SEI film during cycling. Moreover, fluorine ion doping induces the generation of oxygen vacancies and improves the crystallinity of Li4Ti5O12, thereby fostering improved electronic and ionic transport kinetics. The above appealing features enables the prepared fluorine-doped Li4Ti5O12 material demonstrates exceptional high-rate performance, delivering specific capacities of 175 mAh·g−1/0.5C, 159 mAh·g−1/10C, and 138 mAh·g−1/50C. In essence, the fluoride ion doping strategy holds profound implications for enhancing electrode interface characteristics, transport kinetics, and the fabrication of high-power lithium-ion batteries.