The given article presents some results of the scientific research devoted to the development of a new class of scale-resistant powder materials of the Si-Ti-Mo-B system for thermal spraying and using these materials for the creation of heat-resistant coatings on the niobium base alloys by means of various methods of thermal spraying. Also under consideration are problems relating to the theory and practice of obtaining reliable protective coatings on high-melting metals and their alloys, niobium ones included, intended for operation in high-enthalpy oxygen-containing gas flows. Hazard in commencing an oxidation reaction of the base material under coating is connected with density of open pores and cracks, and partial pressure of the oxidizer. Powdered multicomponent heterophase materials for gas-thermal spraying of protective coating with a self-healing ability and controlled properties are proposed. Finally the results of some properties of new silicide-type heterophase powders containing silicide and boride phases for a thermal spraying process and some properties of protective coating deposited on the niobium base alloys by means of a thermal spraying technique are presented.