Air plasma sprayed (APS) thermal barrier coatings (TBCs) are used to provide thermal insulation for the hottest components in gas turbines. Zirconia stabilized with 7wt% yttria (7YSZ) is the most common ceramic top coat used for turbine blades. The 7YSZ coating can be degraded from the buildup of fly-ash deposits created in the power-generation process. Fly ash from an integrated gasification combined cycle (IGCC) system can result from coal-based syngas. TBCs are also exposed to harsh gas environments containing CO<
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, SO<
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, and steam. Degradation from the combined effects of fly ash and harsh gas atmospheres has the potential to severely limit TBC lifetimes. The main objective of this study was to use lab-scale testing to systematically elucidate the interplay between prototypical deposit chemistries (i.e., ash and its constituents, K<
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SO<
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4<
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, and FeS) and environmental oxidants (i.e., O<
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, H<
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O and CO<
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) on the degradation behavior of advanced TBC systems. Several mechanisms of early TBC failure were identified, as were the specific fly-ash constituents responsible for degradation. The reactivity of MCrAlY bondcoats used in TBC systems was also investigated. The specific roles of oxide and sulfate components were assessed, together with the complex interplay between gas composition, deposit chemistry and alloy reactivity. Bondcoat composition design strategies to mitigate corrosion were established, particularly with regard to controlling phase constitution and the amount of reactive elements the bondcoat contains in order to achieve optimal corrosion resistance.