Ceramic materials provide an innovative opportunity for corrosion-resistant coatings for nuclear waste containers. Their suitability can be derived from the fully oxidized state for selected metal oxides. Ceramic coatings applied to plain carbon steel substrates by several thermal spray techniques have been exposed to 90 °C simulated ground water (at 10 times typical concentration) for nearly 6 years. Thermal spray processes examined in this work included plasma spray, high-velocity oxy fuel (HVOF), and detonation gun. Some thermal spray coatings have demonstrated superior corrosion protection for the plain carbon steel substrate. In particular, the HVOF and detonation gun thermal spray processes produced coatings with low connected porosity, which limited the growth rate of corrosion products. It was also demonstrated that these coatings resisted spallation of the coating even when an intentional flaw (which allowed for corrosion of the carbon steel substrate underneath the ceramic coating) was placed in the coating. An approach for a theoretical basis for prediction of the corrosion protection provided by ceramic coatings is also presented. The theoretical development includes the effect of the morphology and amount of the porosity within the thermal spray coating and provides a prediction of the exposure time needed to produce a crack in the ceramic coating.