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Structural and hyperfine interactions data of the as-milled samples. X-ray diffraction proved that during mechanical alloying process the solid solutions with b.c.c. lattice were obtained in the case of Co50Fe40Ni10, Co50Fe35Ni15 and Co60Fe30Ni10 alloys, while for Co40Fe40Ni20 composition the solid solution with f.c.c. lattice was formed. Result obtained for Co50Fe40Ni10 alloy is consistent with the phase diagram for the Co–Fe–Ni bulk alloys prepared by melting. On the other hand, the milling process of Co40Fe40Ni20, Co50Fe35Ni15 and Co60Fe30Ni10 alloys resulted in the formation of the single solid solution, while for these chemical concentrations the melted alloys are a mixture of b.c.c + f.c.c. phases. Mössbauer spectroscopy revealed hyperfine magnetic field distributions, which reflected the different surroundings of 57Fe isotopes by Co, Fe and Ni atoms, depending on the chemical composition of the alloy. The most probable atomic configurations were determined on the basis of the local environment model.