A thermal barrier coating for an underlying metal substrate of articles that operate at, or are exposed to, high temperatures, as well as being exposed to environmental contaminant compositions. This coating comprises an optional inner layer nearest to the underlying metal substrate comprising a non-alumina ceramic thermal barrier coating material in an amount up to 100%, and an outer layer having an exposed surface and comprising at least about 50% of a non-alumina ceramic thermal barrier coating material and alumina in an amount up to about 50% and sufficient to protect the thermal barrier coating at least partially against environmental contaminants that become deposited on the exposed surface. This coating can be used to provide a thermally protected article having a metal substrate and optionally a bond coat layer adjacent to and overlaying the metal substrate. The thermal barrier coating can be prepared by optionally forming the inner layer of the non-alumina ceramic thermal barrier coating material, and then codepositing the alumina and non-alumina ceramic thermal barrier coating material to form the outer layer.