The failure of a boiler operating at 540 °C and 9.4 MPa was investigated by examining material samples from the near-failure region and by thermodynamic analysis. A scanning Auger microprobe, SEM, and commercial thermodynamic software codes were used in the investigation. Results indicated that the boiler failure was caused by grain-boundary segregation of phosphorous, tin, and nitrogen and the in-service formation of carbide films and granules on the grain boundaries.