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.

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.

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.

The steam oxidation behaviour of boiler tubes and steam piping components is a limiting factor for improving the efficiency of the current power plants. Spallation of the oxide scales formed during service can cause serious damage to the turbine blades. Vallourec has implemented an innovative solution based on an aluminum diffusion coating applied on the inner surface of the T/P92 steel. The functionality of this coating is to protect the tubular components against spallation and increase the actual operating temperature of the metallic components. In the present study, the newly developed VALIORTM T/P92 product was tested at the EDF La Maxe power plant (France) under 167b and 545°C (steam temperature). After 3500h operation, the tubes were removed and characterized by Light Optical Metallography (LOM), Scanning Electron Microscopy (SEM), with Energy Dispersive X-ray spectrometry (EDX) and X-Ray Diffraction (XRD). The results highlight the excellent oxidation resistance of VALIORTM T/P92 product by the formation of a protective aluminum oxide scale. In addition, no enhanced oxidation was observed on the areas close to the welds. These results are compared with the results obtained from laboratory steam oxidation testing performed on a 9%Cr T/P92 steel with and without VALIORTM coating exposed in Ar-50%H 2 O at 650°C.

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.

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.

A combination of creep tests, ex-service blade samples, thermodynamic equilibrium calculations, combined thermodynamic and kinetic calculations, image analysis, chemical composition mapping and heat treatments have been conducted on PWA1483 to determine if microstructural rejuvenation can be achieved when taking the presence of oxidation coatings into account as part of a blade refurbishment strategy. The work has shown that the γ′ morphology changes during creep testing, and that through subsequent heat treatments the γ′ microstructure can be altered to achieve a similar γ′ size and distribution to the original creep test starting condition. Thermodynamic equilibrium calculations have been shown to be helpful in determining the optimum temperatures to be used for the refurbishment heat treatments. The interaction of oxidation resistant coatings with the alloy substrate and refurbishment process have been explored with both experimental measurements and coupled thermodynamic and kinetic calculations. The predictive nature of the coupled thermodynamic and kinetic calculations was evaluated against an ex-service blade sample which had undergone refurbishment and further ageing. In general there was good agreement between the experimental observations and model predictions, and the modelling indicated that there were limited differences expected as a result of two different refurbishment methodologies. However, on closer inspection, there were some discrepancies occurring near the interface location between the coating and the base alloy. This comparison with experimental data provided an opportunity to refine the compositional predictions as a result of both processing methodologies and longer term exposure. The improved model has also been used to consider multiple processing cycles on a sample, and to evaluate the coating degradation between component service intervals and the consequences of rejuvenation of the blade with repeated engine exposure. The results from the experimental work and modelling studies potentially offer an assessment tool when considering a component for refurbishment.

This study investigates the impact of adding small amounts of rare earth (RE) elements on the properties and microstructures of SA335P91 steel welds. The RE elements were incorporated into the weld metal using a coating process. The researchers then proposed an optimal RE formula aimed at achieving improved properties and microstructures. To evaluate the effectiveness of this approach, various tests were conducted on both welds with and without RE additions. These tests included tensile testing (both at room and high temperatures), impact testing, metallographic analysis to examine the microstructure, determination of phase transformation points, scanning electron microscopy, and X-ray diffraction. The results revealed that the addition of RE elements has the potential to enhance the properties and modify the microstructure of SA335P91 welds.

Hardfacing alloys are commonly used for wear- and galling-resistant surfaces for mechanical parts under high loads, such as valve seats. Cobalt-based Stellite, as well as, stainless-steel-based Norem02 and Tristelle 5183 alloys show similar microstructural features that correlate with good galling resistance. These microstructures contain hard carbides surrounded by a metastable austenite (fcc) phase that transform displacively to martensite (hcp or bcc or bct) under deformation. As a result, the transformed wear surface forms a hard layer that resists transition to a galling wear mechanism. However, at elevated temperature (350°C), the stainless steel hardfacing alloys do not show acceptable galling behavior, unlike Stellite. This effect is consistent with the loss of fcc to bcc/bct phase transformation and the increase in depth of the heavily deformed surface layer. Retention of high hardness and low depth of plastic strain in the surface tribolayer is critical for retaining galling resistance at high temperature.

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.

Steam turbine is one of the critical equipments in coal-fired power plants, steel P91 is a common material of its control valves. CoCr-based hardfacing on valve seats can resist long time exposure to water vapor with high temperature, thermal fatigue and solid particles erosion under high pressure. However, these hardfacing can crack and disbond during operation, which generates high risks for turbine systems and power plants. This article discussed the failure reasons of CoCr-based hardfacing, and introduced a method and practical experience of on-site repairing steam turbine valve seats with laser cladding NiCr coating.

Most effective method to increase the boiler efficiency and decrease emissions is to increase the steam temperature of modern coal-fired power plants. The increase in the steam temperature of the AUSC power plants will require higher grade heat-resistant materials to support the long-term safety and service reliability of power plants. The corrosion resistance of alloys is one of the most important factors for the application in AUSC power plants.

Solar salts are used as an energy storage media and heat transfer fluid in power plants. The salts can cause significant corrosion to various steels that are in contact with the salt. Static corrosion tests performed with different steels show, that the corrosive attack by industrial grade salt melts is more severe than by defined grade salt melts and the sample corrosion is faster (i.e. the weight gain is larger) for higher temperatures. Slow strain rate (SSR) tests in salt are difficult to conduct due to the corrosive attack of the salt also on the test setup. The SSRT setup in salt could be realized and tests could be conducted successfully. No clear evidence for an accelerated failure of samples tested in salt compared to samples tested in air could be found on Alloy 347 Nb. Comparative low cycle fatigue (LCF) tests at air and in molten salt atmosphere were successfully performed and showed similar results on tubes out of Sanicro 25. No evidence of accelerated crack growth in molten salt could be found.

The EU NextGenPower-project aims at demonstrating Ni-alloys and coatings for application in high-efficiency power plants. Fireside corrosion lab and plants trials show that A263 and A617 perform similar while A740H outperforms them. Lab tests showed promising results for NiCr, Diamalloy3006 and SHS9172 coatings. Probe trials in six plants are ongoing. A617, A740H and A263 performed equally in steamside oxidation lab test ≤750°C while A617 and A740H outperformed A263 at 800°C; high pressure tests are planned. Slow strain rate testing confirmed relaxation cracking of A263. A creep-fatigue interaction test program for A263 includes LCF tests. Negative creep of A263 is researched with gleeble tests. A263 Ø80 - 500mm trial rotors are forged with optimized composition. Studies for designing and optimizing the forging process were done. Segregation free Ø300 and 1,000mm rotors have been forged. A263 – A263 and A293 – COST F rotor welding show promising results (A263 in precipitation hardened condition). Cast step blocks of A282, A263 and A740H showed volumetric cracking after heat treatment. New ‘as cast’ blocks of optimized composition are without cracks. A 750°C steam cycle has been designed with integrated CO 2 capture at 45% efficiency (LHV). Superheater life at ≤750°C and co-firing is modeled.

A combined pilot-scale combustion test and long-term laboratory study investigated the impact of oxy-firing on corrosion in coal-fired boilers. Four coals were burned under both air and oxy-firing conditions with identical heat input, with oxy-firing using flue gas recirculation unlike air-firing. Despite higher SO 2 and HCl concentrations in oxy-firing, laboratory tests showed no increase in corrosion rates compared to air-firing. This is attributed to several factors: (1) Reduced diffusion: High CO 2 in oxy-firing densified the gas phase, leading to slower diffusion of corrosive species within the deposit. (2) Lower initial sulfate: Oxy-fired deposits initially contained less sulfate, a key hot corrosion culprit, due to the presence of carbonate. (3) Reduced basicity: CO 2 and HCl reduced the basicity of sulfate melts, leading to decreased dissolution of metal oxides and mitigating hot corrosion. (4) Limited carbonate/chloride formation: The formation of less corrosive carbonate and chloride solutes was restricted by low O 2 and SO 3 near the metal surface. These findings suggest that oxy-firing may not pose a greater corrosion risk than air-firing for boiler materials.

The recently developed 12%Cr steel VM12-SHC is characterized by very good creep properties at temperatures up to 620°C. This new material development exhibits an excellent oxidation resistance in steam atmospheres at the typical application temperature but also at temperatures up to 650°C. In comparison to the existing 9% Cr grades T/P91 and T/P92, VM12-SHC steel opens due to its excellent oxidation behavior, new possibilities for its application as a heat exchanger boiler component. It was found that outside its application temperature range VM12-SHC also shows, as all 9-12%Cr steels, the appearance of the so called Z-phase. This effect was investigated to understand its influence on creep properties of this class of ferritic/martensitic steels aiming at controlling the microstructure stabilities for future grade developments. Creep testing has been carried out in the temperature range between 525°C and 700°C. Selected crept specimens have been investigated using light optical microscopy, SEM with EDX and TEM. In this study, the oxidation behavior of a number of typical martensitic 9-12%Cr steels was compared with the newly developed 12% Cr steel VM12-SHC. The compositions and morphologies of oxide scales formed after 5000 h exposure steels in simulated steam environments as function of temperature were characterized by light optical metallography and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX).

Components such as tubes, pipes and headers used in power generation plants are operated in a creep regime and have a finite life. During partial replacement, creep exhausted materials are often welded to virgin materials with superior properties. The aim of this study was to identify a suitable weld filler material to join creep aged X20CrMoV12-1 to a virgin P91 (X10CrMoVNbV9-1) steel. Two dissimilar joints were welded using the gas tungsten arc welding (GTAW) process for the root passes, and manual metal arc (MMA) welding for filling and capping. The X20 and the P91 fillers were selected for joining the pipes. The samples were further heat treated at 755°C to stress relief the samples. Microstructural evolution and mechanical properties of the weld metals were evaluated. The average hardness of X20 weld metal (264 HV10) was higher than the hardness measurement of P91 weld metal (206 HV10). The difference in hardness was attributed to the high carbon content in X20 material. The characterisation results revealed that the use of either X20 or P91 weld filler for a butt weld of creep aged X20 and virgin P91 pipes material does not have a distinct effect on the creep life and creep crack propagation mechanism. Both weld fillers (X20 and P91) are deemed to be suitable because limited interdiffusion (<10 μm) of chromium and carbon at the dissimilar weld interface was observed across the fusion line. The presence of a carbon ‘denuded’ zone was limited to <10 μm in width, based on the results from local measurements of the precipitate phase fractions using image analysis and from elemental analysis using EDS. However the nanoindentation hardness measurements across the fusion line could not detect any ‘soft’ zone at the dissimilar weld interface. The effect of the minute denuded zone was also not evident when the samples were subjected to nanoindentation hardness testing, tensile mechanical testing, Small Punch Creep Test (SPCT) and cross weld uniaxial creep testing.

The newly developed 12%Cr steel Super VM12 is characterized by excellent creep rupture strength properties (better than Grade 92) and enhanced steam oxidation resistance of 12%Cr steels such as VM12-SHC. Balanced properties profile of the new steel development in comparison to the existing well-established steels such as Grade 91 and Grade 92, opens opportunities for its application as construction material for components in existing or future high-efficiency power plants. In this study the oxidation behavior of typical 9%Cr steels was compared with the new steel development. The oxide scale morphologies and compositions of different oxide layers as function of temperature and exposure time in steam-containing atmospheres were characterized using light optical metallography, Scanning Electron Microscopy (SEM). Creep testing has been carried out in the temperature range between 525°C and 700°C. Selected creep specimens were investigated using the Transmission Electron Microscopy and the Atom Probe Tomography techniques.

Nickel-based alloys and stainless steel Super304H, along with various coatings, are undergoing testing in a steam loop at Alabama Power’s Plant Barry. These materials are being evaluated for use in advanced ultra-supercritical (A-USC) fossil-fired power plants at temperatures ranging from 538°C to 815°C. The loop has been operational for over 18 months, with the alloys exceeding 6,300 hours above 538°C. An additional 7,000 hours at high temperatures are planned before the loop’s removal in 2014. Initial inspections show minimal material corrosion, suggesting their suitability for A-USC applications. This paper details the loop’s design, materials, manufacturing, operation, and inspection findings. Additionally, it describes a methodology for predicting steam-side oxidation and fireside corrosion rates and highlights the significance of this testing for A-USC development and commercialization.

A creep resistant martensitic steel, CPJ7, was developed with an operating temperature approaching 650°C. The design originated from computational modeling for phase stability and precipitate strengthening using fifteen constituent elements. Approximately twenty heats of CPJ7, each weighing ~7 kg, were vacuum induction melted. A computationally optimized heat treatment schedule was developed to homogenize the ingots prior to hot forging and rolling. Overall, wrought and cast versions of CPJ7 present superior creep properties when compared to wrought and cast versions of COST alloys for turbines and wrought and cast versions of P91/92 for boiler applications. For instance, the Larson Miller Parameter curve for CPJ7 at 650°C almost coincides with that of COST E at 620°C. The prolonged creep life was attributed to slowing down the process of the destabilization of the MX and M 23 C 6 precipitates at 650°C. The cast version of CPJ7 also revealed superior mechanical performance, well above commercially available cast 9% Cr martensitic steel or derivatives. The casting process employed slow cooling to simulate the conditions of a thick wall full-size steam turbine casing but utilized a separate homogenization step prior to final normalization and tempering. To advance the development of CPJ7 for commercial applications, a process was used to scale up the production of the alloy using vacuum induction melting (VIM) and electroslag remelting (ESR), and underlined the importance of melt processing control of minor and trace elements in these advanced alloys.