The AFM method was used to investigate the phase structure of the coatings, which have been obtained after application of polyurethane cationomers, synthesized in the reaction of 4,4'-methylenebis(phenyl isocyanate) or isophorone diisocyanate with polyoxyethylene glycol (M = 600) and N-methyl or N-butyldiethanolamine with 2,2,3,3-tetrafluoro-1,4-butanediol. Changes were discussed in the surface-free energy (SFE) and its components, as calculated independently according to the method suggested by van Owens-Wendt, in relation to chemical structures of cationomers, as well as morphology of coating surfaces obtained from those cationomers. Fluorine incorporated into cationomers (about 2-5%) contributed to lower SFE values, down to about 30 mJ/m(2). An attempt was made to use H-1-NMR spectroscopy to provide more extensive grounds for the effect of polyurethane chemical structures (by parameters kappa) on the SFE of coatings obtained from such polyurethanes, with the values of SFE (gamma(S), gamma(p)(s)) and determined by the Owens-Wendt method. (C) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 127: 2508-2519, 2013