Principles of three component Iron-Cobalt-Tungsten alloys electrodeposition from complex Fe (III) based citrate electrolytes are discussed. It is shown, that deposition of ternary alloys proceeds through competitive reduction of cobalt and tungsten with iron. With increasing ligand concentration coatings are enriched with a refractory component; however, increasing current density favors a reverse trend. The effect of both current density and pulse on/off time on the quality, content of alloying metals and surface topography of electrolytic coatings were determined. The application of pulsed electrolysis provides increasing tungsten content up to 13 at.%, at current efficiency of 70–75%. Globular relief of Fe-Co-W coatings is caused by refractory metals incorporation, and crystalline and amorphous parts of structure are visualized by X-ray spectroscopy, including inter-metallic phases Co7W6, Fe7W6 along with α-Fe and Fe3C. The crystallite size of the amorphous part is near 7–8 nm. Corrosion resistance of the coatings is 1.3–2.0 orders of magnitude higher than the substrate parameters as follows from data of polarization resistance method and electrode impedance spectroscopy
