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Electrodeposition, structure, and properties of Fe–W alloys are studied. The W content depends on current density. The current efficiency is about 40%. Alloys obtained at ibelow 2 A dm–2are crystalline oversaturated solid solutions of W in Fe and are magnetic. Higher current densities yield amorphous nonmagnetic alloys of the same composition. Either alloy has a very high resistivity (nearly 300 ohm cm) and, after a treatment at 500–600C, transforms into a more equilibrium binary system comprising a saturated solid solution and an intermetallic compound.