Multilayered metal oxide coated substrates are disclosed comprising a three dimensional inorganic substrate having a coating of metal oxide and a thermally associated barrier coating on at least a portion of all three dimensions thereof, produced by a unique process having particular applicability to the manufacture of tin oxide coated three dimensional substrates. Certain novel coated substrates, such as flakes, spheres and porous substrates are disclosed. The coated substrates are useful in polymer, catalysis, heating and shielding applications.