Coatings are an essential part of the materials system to protect the turbine blades from oxidation and corrosive attack during service. Inter-diffusion of alloying elements between a turbine blade substrate and their coatings is a potential concern for coated turbine blades at ever increasing operating temperatures because this can cause the formation of undesirable Secondary Reaction Zones (SRZs), which may degrade the mechanical properties of coated Ni-based superalloys. Understanding the effects of each element on the SRZ formation is essential in order to understand both the mechanism and inter-diffusion behaviour between coatings and substrates. In this research, a number of simpler aluminized ternary Ni-Al-X (where X is Co, Cr, Re, Ru or Ta) alloys were investigated in order to elucidate the separate effects of each element on the microstructural evolution, especially at the coating/substrate interface. The aluminized ternary alloys developed distinctive diffusion zones, depending on the third alloy element, ‘X’. Specifically, it has been found that both Ni-Al-Re and Ni-Al-Ta alloys developed a continuous SRZ-like diffusion layer. This diffusion zone persisted in the Ni-Al-Re alloys after high temperature exposure, indicating that Re has a stronger effect on SRZ formation than Ta.

Supercritical CO 2 (sCO 2 ) is of interest as a working fluid for several concepts including the direct- fired Allam cycle as a low-emission fossil energy power cycle. Over the past 10 years, laboratory exposures at 300 bar sCO 2 have found reasonably good compatibility for Ni-based alloys at <800°C, including an assessment of the sCO 2 impact on room temperature mechanical properties after 750°C exposures. However, initial screening tests at 1 and 20 bar CO 2 at 900°-1100°C showed poor compatibility for Ni-based alloys. In an open cycle, the introduction of 1%O 2 and 0.1- 0.25%H 2 O impurities at 300 bar increased the reaction rates ≥2X at 750°C. At lower temperatures, steels are susceptible to C ingress and embrittlement. Creep-strength enhanced ferritic steels may be limited to <550°C and conventional stainless steels to <600°C. Two strategies to increase those temperatures are higher Ni and Cr alloying additions and Al- or Cr-rich coatings. Alloy 709 (Fe- 20Cr-25Ni) shows some promising results at 650°C in sCO 2 but reaction rates were accelerated with the addition of O 2 and H 2 O impurities. Pack aluminized and chromized Gr.91 (Fe-9Cr-1Mo) and type 316H stainless steel show some promise at 600°-650°C but further coating optimization is needed.

Because of the problems experienced with steam-side oxide scale exfoliation in commercial power plants, there has been increased interest in understanding the steam oxidation resistance of 300- series stainless steels such as 347H and 304H. Model alloys were used in an attempt to understand the effect of varying Ni (9-12%) and Cr (16-20%) on steam oxidation resistance at 650°C. However, the model alloys generally showed superior oxidation resistance than commercial alloys of similar composition. Several surface engineering solutions also were investigated. The commercially favored solution is shot peening. Laboratory steam testing at 650°C found that annealing temperatures of ≥850°C eliminated the benefit of shot peening and a correlation was observed with starting hardness in the peened region. This effect of annealing has implications for the fabrication of shot peened tubing. Another route to improving oxidation resistance is the use of oxidation resistant diffusion coatings, which can be deposited inexpensively by a vapor slurry process. Uniform coatings were deposited on short tube sections and annealed at 1065°C to retain good 650°C creep properties. The coating was thicker than has been investigated in laboratory processes resulting in increased brittleness when the coating was assessed using 4-point bending.

A paste, which contains Pt or Pt-xIr (x = 0-30 at%) alloy nano-powder was sprayed on some Ni-based single crystal superalloys. Then the annealing diffusion treatment at 1100 °C for 1 h in flowing Ar atmosphere was conducted to develop Pt and Pt-Ir diffusion coatings. Cyclic oxidation tests were carried out at 1150 °C in still air in order to investigate the thermal stability and oxidation behavior of the coatings and they were compared with electroplated diffusion coatings. It was found that Ir can retard the formation of voids in both the coatings and substrates. In addition, by replacing the electroplating method to the paste coating method, the crack problem due to the brittle feature of electroplated Pt-Ir coatings could be solved. Therefore, the Pt-Ir diffusion coating prepared by the paste- coating method is promising as the bond-coat material due to suppression of voids, cracks and stable Al 2 O 3 on the surface. The Pt-Ir paste diffusion coatings introduced above have several further advantages: they are easy to recoat, cause less damage to substrates, and offer comparable oxidation resistance. Thus, the method can be applicable to the remanufacturing of blades, which may extend the life of components. The future aspect of the paste coating will also be discussed.

Laboratory-scale tests are frequently used to generate understanding of high-temperature oxidation phenomena, to characterise and rank the performance of existing, future materials and coatings. Tests within the laboratory have the advantage of being well controlled, monitored and offer the opportunity of simplification which enables the study of individual parameters through isolating them from other factors, such as temperature transients. The influence of pressure on the oxidation of power plant materials has always been considered to be less significant than the effects of temperature and Cr content, but still remains a subject of differing opinions. Experimental efforts, reported in the literature, to measure the influence of steam pressure on the rate of oxidation have not produced very consistent or conclusive results. To examine this further a series of high pressure steam oxidation exposures have been conducted in a high pressure flowing steam loop, exposing a range of materials to flowing steam at 650 and 700 °C and pressure of 25, 50 and 60 bar. Data is presented for ferritic-martensitic alloys showing the effect of increasing pressure on the mass change and oxide thickness of these alloys in the flowing steam loop. In addition the effect observed on the diffusion of aluminium from an aluminised coating in these alloys is also presented and the differences in the extent of diffusion discussed.

Because of the problems experienced with steam-side oxidation in commercial power plants, there has been continuing interest in better understanding the steam oxidation behavior of creep strength enhanced ferritic steels such as grades 23, 24 and 91 as well as 300-series stainless steels such as 347H and 304H. Analysis of field-exposed tubes has provided information on the oxidation reaction products but relatively few specimens are available and there is limited information about the kinetics. Specimens have included tube sections with a shot peened surface, a treatment that is now widely used for austenitic boiler tubes. To complement this information, additional laboratory studies have been conducted in 1bar steam at 600°-650°C on coupons cut from conventional and shot-peened tubing. Exposures of 1-15 kh provide some information on the steam oxidation kinetics for the various alloys classes. While shot-peened type 304H retained its beneficial effect on oxidation resistance past 10,000 h at 600° and 625°C, the benefit appeared to decline after similar exposures at 650°C.

Diffusion aluminide coatings have been evaluated as a strategy for improving the oxidation resistance of austenitic and ferritic-martensitic (FM) steels, particularly in the presence of steam or water vapor. The objective was to evaluate the strengths and weaknesses of these coatings and quantify their performance and lifetime. Long-term diffusion and oxidation experiments were conducted to study the behavior of various model diffusion coatings and produce a better data set for lifetime predictions. The key findings are that (1) thin coatings (<50μm) with relatively low Al contents appear to be more effective because they avoid high thermal expansion intermetallic phases and have less strain energy to nucleate a crack; and (2) the low Al reservoir in a thin coating and the loss of Al due to interdiffusion are not problematic because the low service temperatures of FM steels (<600°C) and, for austenitic steels at higher temperatures, the phase boundary between the ferritic coating-austenitic substrate inhibits Al interdiffusion. Unresolved issues center on the effect of the coating on the mechanical properties of the substrate including the reaction of N in the alloy with Al.

While the water vapor content of the combustion gas in natural gas-fired land based turbines is ~10%, it can be 20-85% with coal-derived (syngas or H 2 ) fuels or innovative turbine concepts for more efficient carbon capture. Additional concepts envisage working fluids with high CO 2 contents to facilitate carbon capture and sequestration. To investigate the effects of changes in the gas composition on thermal barrier coating (TBC) lifetime, furnace cycling tests (1h cycles) were performed in air with 10, 50 and 90 vol.% water vapor and in CO 2 -10%H 2 O and compared to prior results in dry air or O 2 . Two types of TBCs were investigated: (1) diffusion bond coatings (Pt diffusion or simple or Pt-modified aluminide) with commercially vapor-deposited yttria-stabilized zirconia (YSZ) top coatings on second-generation superalloy N5 and N515 substrates and (2) high velocity oxygen fuel (HVOF) sprayed MCrAlYHfSi bond coatings with air-plasma sprayed YSZ top coatings on superalloy X4 or 1483 substrates. In both cases, a 20-50% decrease in coating lifetime was observed with the addition of water vapor for all but the Pt diffusion coatings which were unaffected by the environment. However, the higher water vapor contents in air did not further decrease the coating lifetime. Initial results for similar diffusion bond coatings in CO 2 -10%H 2 O do not show a significant decrease in lifetime due to the addition of CO 2 . Characterization of the failed coating microstructures showed only minor effects of water vapor and CO 2 additions that do not appear to account for the observed changes in lifetime. The current 50°-100°C de-rating of syngas-fired turbines is unlikely to be related to the presence of higher water vapor in the exhaust.