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The surface properties of fibers can be regarded as instrumental toward innovative functional textiles as applied in many high-end industries. Accordingly, not only the modification of surface chemistry, but also of the physical and morphological properties is an important objective in modern materials science and technology. Besides other powerful chemical and physical techniques, UV-induced graft copolymerization and photopolymerization are interesting ways to improve or introduce surface functionalities of the fiber. While the majority of reported work focused on the surface of the deposited thin layer itself and its potential effect on – for example, wettability, adhesion, protein adsorption and microbial activity, this paper reviews earlier studies by the authors which were devoted to bulk properties of these thin, less than 500-nm thick layers and the resulting effect on fiber properties. One major factor is the high and controllable cross-linking of polymerized layers, which affects mechanical, thermal and chemical stability. This results in interesting applications as thin barrier coating in view of improved fiber stability in critical environments and stress conditions, examples of which are reported in this paper. A recent observation is the effect of the controlled cross-linking on the mobility of monomers and electrical charges in the thin layer, which could open an avenue toward thin-layer capacitors and energy storage on textiles.

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