Electrodeposition of Ni-Mo and Fe-Mo alloy coatings from acid citrate electrolyte was investigated over a wide range of cathode potentials and under various hydrodynamic conditions. Such alloys had been found to be deposited with substantial depolarization against iron group metals. With the same electrodeposition conditions, the molybdenum percentage in Fe-Mo coatings is much higher than in Ni-Mo. The molybdenum presence results in a lower overvoltage of hydrogen evolution, so that these alloys are deposited with a current efficiency much lower than that in the separate reduction of iron group metals. For a Ni-Mo system, the Mo percentage in the coating is increased together with increase of the transport rate of ions towards the cathode and with decrease of the cathode potential value being reduced; while for Fe-Mo alloy an inverse relation is observed. When passing from the Ni-Mo to the Fe-Mo system, the control of the molybdenum reduction reaction is changed. In codeposition with nickel it shows a diffusion control, while in discharging with iron its control is of the activation type. The Ni-Mo coatings obtained contained from 1.5–6% molybdenum whereas Fe-Mo deposits contained from 12–40% depending on electrolysis conditions. The quality of the coatings containing more than 20% Mo deteriorated and in these deposits some nonmetallic inclusions were present.
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