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Ternary coatings Fe-Co-W with an iron content of 40–55 at.%, cobalt 39–44 at.%, and tungsten 4–12 at.% and Fe-Co-Mo with an iron content of 40–55 at.%, cobalt 39–44 at.%, and tungsten 4–12 at.% were obtained by galvanostatic and pulse electrolysis on the mild steel substrate from iron(III) citrate-based electrolyte. The influence of electrolysis mode and parameters on composition of deposited alloys was studied. The competing reduction of iron and tungsten in Fe-Co-W coatings as well as the competitive deposition of iron and cobalt in Fe-Co-Mo coatings at various current densities were defined. Simultaneously, the alloy enrichment with molybdenum is more marked at a pulse mode. Atomic force microscope analysis of the Fe-Co-W alloy coating morphology and surface topography indicates their globular structure with spherical grains in the range of 2.5–3.5 μm. The surface of Fe-Co-Mo is characterized by parts of a globular structure with an average conglomerate size of 0.3–0.5 μm and singly located cone-shaped hills with a base diameter of 3 μm. Sites with a developed surface were detected within the same scan area which topography is identical to the crystal lattice of cobalt with the crystalline conglomerate sizes in the range of 0.2–1.75 μm.

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