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Commercially available mullite (3Al₂O₃·2SiO₂) powders containing oxides of calcium and iron as impurities, have been made suitable for plasma spraying by using an organic binder. Stainless steel substrates covered with Ni-22Cr-10Al-1.0Y bond coat were spray coated with mullite. The 425 µm thick coatings were subjected to thermal shock cycling under burner rig conditions between 1000 and 1200 °C and less than 200 °C with holding times of 1, 5, and 30 min. While the coatings withstood as high as 1000 shock cycles without failure between 1000 and 200 °C, spallation occurred early at 120 cycles when shocked from 1200 °C. The coatings appeared to go through a process of self erosion at high temperatures resulting in loss of material. Also observed were changes attributable to melting of the silicate grains, which smooth down the surface. Oxidation of the bond coat did not appear to influence the …