The paper presents the effect of He+ ion irradiation of selected polymeric materials: poly(tetrafloroethylene), poly(vinyl chloride), ethylene-propylene-diene monomer rubber, nitrile-butadiene rubber, styrene-butadiene rubber, and natural rubber, on their chemical composition, physical structure, and surface topography. The modification was studied by scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, and differential scanning calorimetry. Irradiation with a high-energy ion beam leads to the release of significant amounts of hydrogen from the surface layer, resulting in an increase in cross-linking that manifests itself by shrinkage of the surface layer, which in turn causes significant stresses leading to the formation of a crack pattern on the polymer surface. The development of microroughness is combined with oxidation. Shallow range of the ions makes the modified layer “anchored” in the substrate via bulk macromolecules, assuring its good durability and adhesion to elasto-plastic substrates. Changes in the surface layer were manifested by the modification of functional properties of the polymers. The hardness of the layer subjected to the ion irradiation process increases even up to 10 times. After modification with the ion beam, a significant decrease in frictional forces was also observed, even up to 5–6 times. The microscopic analysis of wear traces confirmed that the wear resistance also significantly increased. However, ion bombardment of polymeric materials caused a reduction in their mechanical strength (despite the range limited to the surface layer of the order of micrometers) and electrical resistance, which has a negative impact on the possibility of using the materials in some applications.
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