The outstanding characteristics of fluorine gas, e.g., extreme reactivity and oxidizing power, and the utmost electronegativity of F À ion, lead to very strong bonds between fluorine and most of the other elements of the periodical table. Treatments involving F 2 , fluorinated gases and rf plasmaenhanced fluorination (PEF) constitute exceptional tools for modifying the surface properties of materials. Many advantages of these techniques can be indeed outlined, when compared to more conventional methods: low-temperature reactions (even at room temperature), chemical modifications limited to surface only without changing the bulk properties, possible non-equilibrium reactions. Depending on the type of starting materials and employed techniques, the improved properties may concern wettability, adhesion, chemical stability, barrier properties, biocompatibility, grafting, mechanical behavior. Several examples of surface fluorination will be given on various types of carbon-based materials, elastomers and polymers. #

The fundamental features and industrial applications of the direct fluorination of polymers are reviewed. Direct fluorination of polymers (i.e., treatment of a polymer surface with gaseous fluorine mixtures) proceeds spontaneously at room temperature and is a surface modification process. More than 25 polymers have been studied with the aid of a variety of analytical and spectroscopic techniques. The fundamental features of the direct fluorination, such as influence of treatment conditions (composition of the fluorinating mixture, fluorine partial pressure, temperature, and fluorination duration) on the rate of formation, chemical composition, density, refraction index, and surface energy of the fluorinated layer, kinetics of formation of radicals during fluorination and their termination, texture of fluorinated layer, etc. were studied. It was demonstrated experimentally that direct fluorination can be effectively used to enhance commercial properties of polymer articles, such as barrier properties of polymer vessels, bottles, and packaging films and envelopes; gas-separation properties of polymer membranes; adhesion and printability properties of polymer articles; and mechanical properties of polymer-based composites.

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