Improved refractory coatings are provided in processes involving the chemical vapor phase deposition of a refractory coating upon a substrate by initially coating the substrate with a continuous adherent layer of substantially pure elemental material. For example, in a process for the vapor deposition of titanium carbonitride on a substrate such as stainless steel, by the contact of vaporous reactants containing titanium, carbon, and nitrogen, the substrate is initially plated with a continuous adherent layer of pure nickel, and the titanium carbonitride coating is applied over the nickel.