Fluorination Technique Research Articles

Enhanced DC surface discharge characteristics of epoxy composites treated by dielectric barrier discharge plasma fluorination and its mechanisms

Surface flashover is a destructive high-voltage discharge phenomenon greatly limiting the update of modern power electronic and electrical equipment. Surface plasma treatment is a high-energy, eco-friendly, and convenience method, it changes the surface properties and owns potential to improve flashover voltage. In the present work, plasma fluorination (PF) technique are used to treat EP/Al2O3 composites, surface morphology, element and bonds content, surface trap, conductivity, charging, and DC flashover voltage are tested and simulated, the effects of plasma on surface discharge are explained through the investigation from microscopic molecular reactions to macroscopic flashover characteristics. It indicates the 20 min PF modified sample exhibits the superior DC flashover performance, increasing by 17 % compare to untreated sample. During PF modification, the epoxy chains are degraded and fluorinated, the degradation rather than fluorination of molecular chains introduce large amounts of shallow traps into the composites, accelerating carriers’ migration and improving surface conductivity, causing surface charges to dissipate through surface conductance. Consequently, the surface electric field distortion degree reduces, and the subsequent gas ionization and plasma formation in the gas phase is suppressed, leading to the improvement of DC flashover voltage after PF modifications.

Understanding the Selective Removal of Perfluoroalkyl and Polyfluoroalkyl Substances via Fluorine-Fluorine Interactions: A Critical Review.

As regulatory standards for per- and polyfluoroalkyl substances (PFAS) become increasingly stringent, innovative water treatment technologies are urgently demanded for effective PFAS removal. Reported sorbents often exhibit limited affinity for PFAS and are frequently hindered by competitive background substances. Recently, fluorinated sorbents (abbreviated as fluorosorbents) have emerged as a potent solution by leveraging fluorine-fluorine (F···F) interactions to enhance selectivity and efficiency in PFAS removal. This review delves into the designs and applications of fluorosorbents, emphasizing how F···F interactions improve PFAS binding affinity. Specifically, the existence of F···F interactions results in removal efficiencies orders of magnitude higher than other counterpart sorbents, particularly under competitive conditions. Furthermore, we provide a detailed analysis of the fundamental principles underlying F···F interactions and elucidate their synergistic effects with other sorption forces, which contribute to the enhanced efficacy and selectivity. Subsequently, we examine various fluorosorbents and their synthesis and fluorination techniques, underscore the importance of accurately characterizing F···F interactions through advanced analytical methods, and emphasize the significance of this interaction in developing selective sorbents. Finally, we discuss challenges and opportunities associated with employing advanced techniques to guide the design of selective sorbents and advocate for further research in the development of sustainable and cost-effective treatment technologies leveraging F···F interactions.

Double-Shelled Fe-Fe3C Nanoparticles Embedded on a Porous Carbon Framework for Superior Lithium-Ion Half/Full Batteries.

Cost-effective and environmentally friendly Fe-based active materials offer exceptionally high energy capacity in lithium-ion batteries (LIBs) due to their multiple electron redox reactions. However, challenges, such as morphology degradation during cycling, cell pulverization, and electrochemical stability, have hindered their widespread use. Herein, we demonstrated a simple salt-assisted freeze-drying method to design a double-shelled Fe/Fe3C core tightly anchored on a porous carbon framework (FEC). The shell consists of a thin Fe3O4 layer (≈2 nm) and a carbon layer (≈10 nm) on the outermost part. Benefiting from the complex nanostructuring (porous carbon support, core-shell nanoparticles, and Fe3C incorporation), the FEC anode delivered a high discharge capacity of 947 mAh g-1 at 50 mA g-1 and a fast-rate capability of 305 mAh g-1 at 10 A g-1. Notably, the FEC cell still showed 86% reversible capacity retention (794 mAh g-1 at 50 mA g-1) at a high cycling temperature of 80 °C, indicating superior structural integrity during cycling at extreme temperatures. Furthermore, we conducted a simple solid-state fluorination technique using the as-prepared FEC sample and excess NH4F to prepare iron fluoride-carbon composites (FeF2/C) as the positive electrode. The full cell configuration, consisting of the FEC anode and FeF2/C cathode, reached a remarkable capacity of 200 mAh g-1 at a 20 mA g-1 rate or an energy density of approximately 530 Wh kg-1. Thus, the straightforward and simple experimental design holds great potential as a revolutionary Fe-based cathodic-anodic pair candidate for high-energy LIBs.

Porous MnF2 with micro-nanostructures coated by a nitrogen doped carbon shell as an anode for enhanced lithium storage

MnF2, an intriguing anode material for lithium-ion batteries (LIBs), has garnered significant attention due to its high theoretical capacity. However, its commercial viability is impeded by issues such as volume expansion and poor conductivity. In this study, we present the development and fabrication of MnF2@NC microspheres with micro-nanostructured pores, comprising MnF2 nanoparticles encapsulated within a nitrogen-doped carbon shell. This was achieved through a combination of hydrothermal synthesis and fluorination techniques. The MnF2@NC composite exhibits a high level of porosity, effectively mitigating the significant volume expansion of MnF2 and facilitating efficient charge transport. Moreover, the incorporation of nitrogen-doped carbon shell enhances the overall structural and promotes electrical conductivity. Leveraging these inherent characteristics, the MnF2@NC electrode demonstrates exceptional electrical conductivity and superior long-term stability. The MnF2@NC electrode serves as an anode for LIBs, exhibiting a remarkable reversible capacity of 991.2 mAh/g at 0.1 A/g, exceptional cycle performance with a capacity retention of 872.2 mAh/g after 700 cycles at 1.0 A/g, and outstanding rate capability surpassing the reported outcomes of MnF2-based composite anodes. These results unequivocally demonstrate the suitability and potential applicability of MnF2@NC as high-capacity anodes for LIB.

A New Method for Silicon Triple Isotope Analysis With Application to Siliceous Sponge Spicules

AbstractMultiple isotope ratios of elements disclose information on the fractionation mechanism that cannot be obtained from a single isotope ratio alone. We describe a laser fluorination technique in combination with gas source mass spectrometry for the measurement of triple Si isotope ratios with high precision that allows resolving ppm‐level variability in triple silicon isotope ratios (29Si/28Si, 30Si/28Si) Δ‘29Si due to purely mass‐dependent fractionation in Si isotopes. We demonstrate how the triple silicon isotope ratios can be used to characterize different mass‐dependent processes that fractionate silicon isotopes. We report new data on reference materials (NBS‐28 [RM8546], Diatomite, BigBatch) and on siliceous sponges. Our triple silicon isotope data resolve that kinetic fractionation, possibly related to breaking Si(OH)4 molecules, causes the low δ30Si of sponges. The data further suggest that the cause for fractionation may be the same for the groups of Demospongiae, Homoscleromorpha, and Hexactinellida and that triple silicon isotope ratios of sponges have potential as seawater silicon isotope proxy.

A simple photochemical method for surface fluorination using perfluoroketones

Surface fluorination of conventional polymers can give them desirable surface properties similar to the expensive and difficult-to-process fluoropolymers. However, traditional surface fluorination techniques often require toxic reagents and special equipment. Here, we report a simple and effective polymer surface fluorination method by using safe and inexpensive perfluoro-2-methyl-3-pentanone (PFMP, C2F5C(O)CF(CF3)2) and UV irradiation. This method is applicable to various polymer materials, and generates nanometer-thick fluorinated layer on the outermost surface, significantly changing their surface properties without changing the surface morphology.

Modular Synthesis of Fluoro-Substituted Furan Compounds via Controllable Fluorination of Biomass-Based 5-HMF and Its Derivatives.

5-Hydroxymethylfurfural (5-HMF) is regarded as one of the most promising platform feedstocks for producing valuable chemicals, fuels, and materials. In this study, we present a controllable fluorination technique for biomass-based 5-HMF and its oxygenated derivatives. This technique allows us to synthesize mono-fluoromethyl, difluoromethyl, and acylfluoro-substituted furan compounds by adjusting experimental conditions such as different fluorine sources and mole ratio. To gain a deeper understanding the reactivity order, we conducted intermolecular and intramolecular competition experiments. The results revealed that the hydroxyl group exhibited the highest reactivity, followed by the aldehyde group. This finding provides important theoretical support and opens up the possibility of selective fluorination. The reaction offers several advantages, including mild conditions, no need for inert gas protection, and easy operation. Furthermore, the fluoro-substituted furan compounds can be further transformed for the preparation of drug analogs, offering a new route for the high-value utilization of biomass molecules.

Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery

Abstract Lithium/fluorinated carbon (Li/CF x ) primary battery is a promising energy supply device with high energy density. However, poor electrochemical capabilities such as the initial voltage delay phenomenon and the large polarization have obstructed their applications. The electrochemical performance of CF x primarily depends on the feature of the carbon source and the corresponding fluorination technique. Herein, we developed a high energy density Li/CF x battery by employing helical carbon nanotubes (HCNTs) as the carbon source. In detail, the precise control of the fluorination temperature was designed at the range of 250–400°C to tune the F/C ratio of CF x . Furthermore, the high F/C ratio of fluorinated HCNTs (F-HCNTs) reaches about 1.43, which surpasses the highest theoretical value in fluorinated crystalline carbon materials. Due to the active rich fluorination sites provided by the periodical insertion of the carbon pentacyclic (C5) and heptacyclic (C7) rings, HCNTs exhibited a defect-rich feature and F-HCNTs have a nodular shape. These features favor to enhance the transport of lithium ions and allow more C–F bonds to react with lithium ions, leading to a high energy density of 2133.13 W h/kg. This novel material offers an alternative approach for lithium primary battery being great potential in actual applications.

Simultaneous fluorination and carbonation to approach a high infrared transparent magnesium fluoride

In this research study, magnesium fluoride nanoparticles were successfully produced by the fluorination and carbonation method. MgF2 nanoparticles were calcined at temperature of 100, 300, 400, 500, 600, 640, and 680 °C. Also, polycrystalline magnesium fluoride ceramics were prepared using a hot-pressing process from calcined powders. The optical, structural, and mechanical characteristics of the magnesium fluoride samples were then investigated. The X-ray diffraction proved that magnesium fluoride nanoparticles were formed with a single-phase structure and no impurities. By using simultaneous fluorination and carbonation technique, crystalline MgF2 nanoparticles with a particle size of 50–60 nm were synthesized at a minimum temperature of 100 °C. Increasing the calcination temperature led to the evaporation of the volatile products and increased the crystallinity and particle size of MgF2 nano-particles. The optimal calcination temperature of 640 °C created a ceramic MgF2 with a hardness of 560 HV, and considerable relative density of 100%, and a high transmittance of over 90% in the 3.2–5.5 μm range. The obtained results, thus, revealed that the transparency of MgF2 ceramics was a function of the porosity and the grain size distribution. The microstructure of hot-pressed MgF2 confirmed a Gaussian grain size distribution in the range of 100–1000 nm, contributing to the enhancement of densification. An intra-granular fracture occurred in magnesium fluoride, which was related to the fine-grained structure of MgF2.

Facile and Environment-friendly Fluorinations using Ionic Liquids.

Significant advancement in the preparation of fascinating fluoroorganics is highly desirable in view of their limited natural occurrence and ever-increasing applications in medicinal and material sciences. Ionic liquids act as the most promising green media for a variety of nucleophilic and electrophilic fluorinations in terms of chemoselectivity, reaction yields, reusability, operational simplicity and scalability. The use of these designer solvents in stimulating the electrified synthesis of fluorinated compounds is also appreciable due to their tuneable electrochemical characteristics. Recent innovations in fluorination techniques depict the substantial role of ionic liquids in fluorotransformations such as the use of tagged ionic liquids in nucleophilic fluorinations, ionic liquid assisted biological fluorination, enantioselective fluorinations using chiral electrophilic reagents along with ionic liquid media, use of task-specific ionic liquids with mediators in electrochemical fluorinations and ionic liquid promoted electrifying synthesis of medicinally important fluorinated heteroaromatics and radiopharmaceuticals.

Hydrophobic-Hydrophilic Properties and Characterization of PIM-1 Films Treated by Elemental Fluorine in Liquid Perfluorodecalin.

A direct fluorination technique was applied for the surface treatment of PIM-1 films in a liquid phase (perfluorodecalin). The fluorinated samples were analyzed by various instrumental techniques. ATR-IR spectroscopy showed that the fluorination predominantly takes place in methylene- and methyl-groups. Cyano-groups, aromatic hydrogens and the aromatic structure of the PIM-1 repeat unit were shown to be relatively stable at the fluorination conditions. XPS confirmed that the concentration of fluorine, as well as oxygen, in the near surface layer (~1 nm) increases with fluorination time. C1s and O1s surface spectra of the fluorinated PIM-1 samples indicated an appearance of newly-formed C-F and C-O functional groups. Scanning electron microscopy and X-ray energy-dispersive spectroscopy of the fluorinated PIM-1 samples showed an increase of the fluorine concentration at the surface (~0.1-1 μm) with the treatment duration. Analysis of the slices of the PIM-1 films demonstrated a decline of the fluorine content within several microns of the film depth. The decline increased with the fluorination time. A model of fluorine concentration dependence on the film depth and treatment duration was suggested. A change in the specific free surface energy as a result of PIM-1 fluorination was revealed. The fluorination time was shown to affect the surface energy (γSV), providing its shift from a low value (25 mJ∙m-2), corresponding to tetrafluoroethylene, up to a relatively high value, corresponding to a hydrophilic surface.

A novel approach to directly achieve SiO2 hollow nanofibers via mono-axis electrospinning united with fluorination technique

A facile and low-cost technique of simple mono-axis electrospinning united with fluorination technique is devised and employed to directly prepare SiO2 hollow nanofibers for the first time. SiO2 hollow nanofibers have regular morphology and uniform size, and the diameter and wall thickness can be adjusted by changing the sintering temperatures and tetraethyl orthosilicate (TEOS) amounts. As the calcination temperature increases from 600 to 800 °C, the diameter of fibers decreases gradually from 470.27 ± 10.89 to 427.60 ± 12.85 nm, and the wall thickness decreases from 75.87 to 65.21 nm. With increasing TEOS amounts from 8 % to 20 %, the diameter of the fibers progressively increases from 470.27 ± 10.89 to 628.03 ± 2.51 nm and the wall thickness increases from 75.87 to 112.10 nm. Particularly, hollow nanostructure is achieved only by fluorination among halogenation, and the formation mechanism of SiO2 hollow nanofibers is proposed and verified. The technology has the characteristics of simple preparative process, cost effectiveness and good reproducibility, and lays a certain foundation for the wide applications of SiO2 hollow nanofibers.

The oxygen stable isotope composition of CRM 125-A UO2 standard reference material

While there is a clear need for standardized reference materials for analytical calibrations and for inter-laboratory comparisons, there are not currently any for the oxygen stable isotopic composition of uranium oxides. In this paper we summarize the results from four laboratories by seven different methods of oxygen stable isotope analyses using fluorination techniques of CRM 125-A UO2 Standard Reference Material. We synthesize these data and methods to arrive at a consensus oxygen stable isotope composition for CRM 125-A δ18O = −9.63‰ (±0.29‰) VSMOW. We discuss methodological differences between analytical approaches, including furnace vs laser heating, fluorination using BrF5 or ClF3, as well as calibration strategies. We highlight the potential effects of calibration scale compression from single-point calibrations using reference material with δ18O values having a large relative difference from the sample being analyzed. We demonstrate how calibration scale compression can yield differences in calibrated δ18O values up to ∼2‰ for samples with ∼20‰ difference from a single reference material, if the calibration slope of different analytical systems differs by 0.1. We suggest the use of liquid water calibration standards sealed in silver capillary tubes for multi-point calibrations of fluorination analysis systems.

Oxygen Isotopes in Carbonate and Phosphate of Modern Mammal Bioapatite: New Data and Critical Revision after about 25 Years from the First Recognitions

Oxygen and carbon isotopes of well-preserved skeletal remains give relevant support to archaeological and environmental reconstructions. However, the preservation of the skeletal remains must be preliminarily checked. About twenty-five years ago, a diagnostic method based on the oxygen isotope ratio in the phosphate, δ(O18/O16)Ph, and carbonate, δ(O18/O16)Carb, of bioapatite of modern mammals was proposed: for well-preserved samples, the δ(O18/O16)Ph and δ(O18/O16)Carb should plot near the regression line δ(O18/O16)Ph on δ(O18/O16)Carb obtained for modern mammals. In the last twenty years, techniques of analysis have changed. In the past, BiPO4 or Ag3PO4 were precipitated from dissolved bioapatite and analysed with the fluorination technique, whereas at present, temperature reduction (HTR) in a glassy carbon reactor with CO release is commonly used. Taking into account the HTR technique, for some modern mammals, we report a new δ(O18/O16)Ph + 1 on δ(O18/O16)Carb + 1 regression line, and related dispersion of the data that, in addition to mineralogical and structural methods, may be used to select samples reliable for archaeological use. In the past, other similar regression lines on modern mammals were defined by several authors. However, statistical results indicate that data used for these regression lines cannot be pooled because the hypothesis of a similar elevation is rejected.

Making monolayer graphene photoluminescent by electron-beam-activated fluorination approach

The past one and half decades have witnessed a tremendous development of graphene electronics, and the key to the success of graphene is its exceptional properties. The lacking of an inherent bandgap endows graphene with excellent electrical properties but considerably limits its applications in light-emitting and high-performance graphene-based devices. Herein, an approach for the direct writing of semiconducting and photoluminescent fluorinated graphene (C4F) patterns on monolayer graphene by an optimized electron-beam-activated fluorination technique is reported. A series of characterization approaches, such as atomic force microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were used to demonstrate the successful preparation of C4F for maskless lithography. Specially, a sharp and strong photoluminescence located at the purple light range of ∼380 nm was observed in C4F, demonstrating a desirable semiconducting nature, and the bandgap was further confirmed by follow-up electrical measurements, where the C4F filed-effect transistor exhibited a p-type semiconductor behavior and significantly enhanced on/off ratio. Therefore, this work provides a novel technique for the fabrication of graphene devices for promising electronic and optoelectronic applications, but also opens a route towards the tailoring and engineering of electronic properties of graphene.

Microporosity effect of intrinsic microporous polyimide membranes on their helium enrichment performance after direct fluorination

The efficient enrichment of Helium (He) from low concentrated natural gas seems the only way to balance the He shortage. However, to reinforce this process, one of the biggest challenges is the membrane with both high He permeability and He/CH4 selectivity. Here, we applied a direct fluorination technique to in-situ modify two intrinsic microporous polyimides (SPI and TPI) with different surface areas. The fluorine reacted with the polyimide backbone at the membrane skin and inner surface that were proved by FT-IR, XPS and EDS analysis. The resulting fluorinated SPI (FSPI) and TPI (FTPI) manifested significantly enhanced He/CH4 separation properties by huge improved He/CH4 diffusion selectivity. The overall performance of He/CH4, He/CO2, H2/CO2 and H2/CH4 were much better than their precursor membranes. In which, the FSPI-60 demonstrated a state-of-the-art He permeability of 590 Barrer combined with He/CH4 selectivity of 634. This figure-of-merit outperformed most of polymer membranes and beat the latest perfluorinated trade-off line. Notably, the FSPI-60 with higher BET surface area precursor demonstrated simultaneously larger He permeability and He/CH4 selectivity than the corresponding FTPI-60 from low surface area precursor. The higher permeability of FSPI originated from its larger concentration of micropores that provides more pathways for He transport. The higher selectivity of FSPI-60 derived from its much larger He/CH4 diffusion selectivity, that is, 6375 vs 2334. Additionally, this FSPI-60 membrane also showed plasticization resistant and excellent He/CH4 (1/99) mixed-gas separation performance, which provides great perspective in He recovery from natural gas applications.

Fluorination Promotes the Cytosolic Delivery of Genes, Proteins, and Peptides.

The cytosolic delivery of biomolecules such as genes, proteins, and peptides is of great importance for biotherapy but usually limited by multiple barriers during the process. Cell membrane with high hydrophobic character is one of the representative biological barriers for cytosolic delivery. The introduction of hydrophobic ligands such as aliphatic lipids onto materials or biomolecules could improve their membrane permeability. However, these ligands are lipophilic and tend to interact with the phospholipids in the membrane as well as serum proteins, which may hinder efficient intracellular delivery. To solve this issue, our research group proposed the use of fluorous ligands with both hydrophobicity and lipophobicity as ideal alternatives to aliphatic lipids to promote cytosolic delivery.In our first attempt, fluorous ligands were conjugated onto cationic polymers to increase their gene delivery efficacy. The fluorination dramatically increased the gene delivery performance at low polymer doses. In addition, the strategy greatly improved the serum tolerance of cationic polymers, which is critical for efficient gene delivery in vivo. Besides serum tolerance, mechanism studies revealed that fluorination increases multiple steps such as cellular uptake and endosomal escape. Fluorination also allowed the assembly of low-molecular-weight polymers and achieved highly efficient gene delivery with minimal material toxicity. The method showed robust efficiency for polymers, including linear polymers, branched polymers, dendrimers, bola amphiphilies, and dendronized polymers.Besides gene delivery, fluorinated polymers were also used for intracellular protein delivery via a coassembly strategy. For this purpose, two lead fluoropolymers were screened from a library of amphiphilic materials. The fluoropolymers are greatly superior to their nonfluorinated analogues conjugated with aliphatic lipids. The fluorous lipids are beneficial for polymer assembly and protein encapsulation, reduced protein denaturation, facilitated endocytosis, and decreased polymer toxicity compared to nonfluorinated lipids. The materials exhibited potent efficacy in therapeutic protein and peptide delivery to achieve cancer therapy and were able to fabricate a personalized nanovaccine for cancer immunotherapy. Finally, the fluorous lipids were directly conjugated to peptides via a disulfide bond for cytosolic peptide delivery. Fluorous lipids drive the assembly of cargo peptides into uniform nanoparticles with much improved proteolytic stability and promote their delivery into various types of cells. The delivery efficacy of this strategy is greatly superior to traditional techniques such as cell-penetrating peptides both in vitro and in vivo. Overall, the fluorination techniques provide efficient and promising strategies for the cytosolic delivery of biomolecules.

Photo-fluorination of nanodiamonds catalyzing oxidative dehydrogenation reaction of ethylbenzene

Styrene is one of the most important industrial monomers and is traditionally synthesized via the dehydrogenation of ethylbenzene. Here, we report a photo-induced fluorination technique to generate an oxidative dehydrogenation catalyst through the controlled grafting of fluorine atoms on nanodiamonds. The obtained catalyst has a fabulous performance with ethylbenzene conversion reaching 70% as well as styrene yields of 63% and selectivity over 90% on a stream of 400 °C, which outperforms other equivalent benchmarks as well as the industrial K−Fe catalysts (with a styrene yield of 50% even at a much higher temperature of ca. 600 °C). Moreover, the yield of styrene remains above 50% after a 500 h test. Experimental characterizations and density functional theory calculations reveal that the fluorine functionalization not only promotes the conversion of sp3 to sp2 carbon to generate graphitic layers but also stimulates and increases the active sites (ketonic C=O). This photo-induced surface fluorination strategy facilitates innovative breakthroughs on the carbocatalysis for the oxidative dehydrogenation of other arenes.

Gas‐Phase Fluorination of Hexagonal Boron Nitride

Hexagonal boron nitride (hBN) has received much attention in recent years as a 2D dielectric material with potential applications ranging from catalysts to electronics. hBN is a stable covalent compound with a planar hexagonal lattice and is relatively unreactive to most chemical environments, making the chemical functionalization of hBN challenging. Here, a simple, scalable strategy to fluorinate hBN using a direct gas-phase fluorination technique is reported. The nature of fluorine bonding to the hBN lattice and their chemical coordination are described based on various characterization studies and theoretical models. The fluorine functionalized hBN shows a bandgap reduction and displays a semiconducting behavior due to the fluorination process. Additionally, the fluorinated hBN shows significant improvement in its thermal and friction properties, which could be substantial in applications such as lubricants and thermal fluids. Theory and simulations reveal that the enhanced friction properties of fluorinated hBN result from reduced inter-planar interaction energy by electrostatic repulsion of intercalated fluorine atoms between hBN layers without significant disruption of the in-plane lattice. This technique paves the way for the fluorination of several other 2D structures for various applications such as magnetism and functional nanoscale electronic devices.

Effect of Direct Fluorination on the Transport Properties and Swelling of Polymeric Materials: A Review

Fluorine-containing polymers occupy a peculiar niche among conventional polymers due to the unique combination of physicochemical properties. Direct surface fluorination of the polymeric materials is one of the approaches for the introduction of fluorine into the chemical structure that allows one to implement advantages of fluorinated polymers in a thin layer. Current review considers the influence of the surface interaction of the polymeric materials and membranes with elemental fluorine on gas, vapor and liquid transport as well as swelling and related phenomena. The increase in direct fluorination duration and concentration of fluorine in the fluorination mixture is shown to result mostly in a reduction of all penetrants permeability to a different extent, whereas selectivity of the selected gas pairs (He-H2, H2-CH4, He-CH4, CO2-CH4, O2-N2, etc.) increases. Separation parameters for the treated polymeric films approach Robeson’s upper bounds or overcome them. The most promising results were obtained for highly permeable polymer, polytrimethylsilylpropyne (PTMSP). The surface fluorination of rubbers in printing equipment leads to an improved chemical resistance of the materials towards organic solvents, moisturizing solutions and reduce diffusion of plasticizers, photosensitizers and other components of the polymeric blends. The direct fluorination technique can be also considered one of the approaches of fabrication of fuel cell membranes from non-fluorinated polymeric precursors that improves their methanol permeability, proton conductivity and oxidative stability.