Layered metal non-oxide coated substrates are disclosed comprising a three dimensional inorganic substrate having a coating of metal non-oxide derived from a pre-associated coating on at least a portion of all three dimensions thereof, produced by a unique process having particular applicability to the manufacture of metal boride, carbide and nitride coated three dimensional substrates. Certain novel coated substrates, such as flakes, spheres and porous substrate are disclosed. The coated substrates are useful in polymer catalysis, heating and shielding applications.