The presence of sulfur at an impurity level in heat resistant steels could improve remarkably the steam oxidation resistance. As is well known, sulfur tends to form sulfides, in particular, chromium sulfides when the steel contains chromium. Therefore, there are two possibilities of sulfur states in the steel. One is in atomic sulfur state as a solid solution, and the other is in sulfide state as a precipitate. However, it still remains unclear which sulfur state contributes largely to the improvement of the steam oxidation resistance of the steels. In order to elucidate the sulfur state operated more effectively in improving the oxidation resistance, the steam oxidation resistance was investigated with high chromium ferritic steels, Fe-10mass%Cr-0.08mass%C-(0~0.015)mass%S, with controlling the sulfur states in them by proper heat treatments. From a series of experiments, it was found that the sulfide state played a more important role in improving the steam oxidation resistance than the atomic sulfur state. Furthermore, this sulfur effect worked significantly in the steam oxidation test performed at the temperatures above 873K which corresponded to the temperature for the chromium sulfide to dissolve and instead for the chromium oxide to form in the steels. This result indicates that the beneficial effect of sulfur in improving the steam oxidation resistance is related closely to the sulfide stability against the oxide in the steels.

A comprehensive fireside corrosion study was undertaken to better understand the corrosion mechanisms operating on the superheaters and lower furnace walls of advanced coal- fired utility boilers. The study intended to evaluate the fireside conditions generated from burning eight U.S. coals individually in a pilot-scale combustion facility. These coals consisted of a wide range of compositions that are of interest to the utility industry. The combustion facility was capable of producing the realistic conditions of staged combustion existing in coal-fired utility boilers. During each of the combustion tests, gas and deposit samples were collected and analyzed via in-furnace probing at selected locations corresponding to the waterwalls and superheaters. Testing of five of the eight coal groups has been completed to date. Results of these online measurements helped reveal the dynamic nature of the combustion environments produced in coal-fired boilers. Coexistence of reducing and oxidizing species in the gas phase was evident in both combustion zones, indicating that thermodynamic equilibrium of the overall combustion gases was generally unattainable. However, the amount of sulfur released from coal to form sulfur-bearing gaseous species in both the reducing and oxidizing zones was in a linear relationship with the amount of the total sulfur in coal, independent of the original sulfur forms. Such a linear relationship was also observed for the measured HCl gas relative to the coal chlorine content. However, the release of sulfur from coal to the gas phase appeared to be slightly faster and more complete than that of chlorine in the combustion zone, while both sulfur and chlorine were completely released and reacted to form respective gaseous species in the oxidizing zone. The information of sulfur and chlorine release processes in coal combustion generated from this study is considered new to the industry and provides valuable insight to the understanding of fireside corrosion mechanisms.

It is required to reduce the lifetime cost of turbine blades. To achieve the cost reduction, a refining and recycling method of scrapped turbine blades is proposed. For the establishment of the method, desulfurization mechanism of Ni-base superalloy by solid CaO was studied. 500 g of superalloy containing sulfur was heated in a vacuum induction furnace and kept at 1600 °C. A CaO rod was inserted into the molten alloy and held for 600 s. After the experiment, sulfur content in the alloy decreased from 200 ppm to 54 ppm. On the surface of the CaO rod after the experiment, only Ca, O, Al, and S were found by EPMA analysis. Especially, Al and S were distributed at the surface and grain boundaries of the rod. By powder XRD analysis, CaO, CaS and 3CaO･Al 2 O 3 were identified as constituent phases on the rod. The desulfurization mechanism of superalloy at 1600 °C is supposed to be three steps: (1) Al and S in the alloy react with CaO to generate CaS and Al 2 O 3 , respectively. (2) Al 2 O 3 melts with CaO as liquid slag. (3) CaS is captured by the slag, therefore, sulfur is removed from the alloy.

In downstream oil industry applications, high-temperature sulfidation corrosion is generally caused by sulfur species coming from the crude; additionally, naphthenic acids or hydrogen can considerably worsen the corrosivity of the environment. During plant operations, several events may occur that boost the severity of corrosion: high feedstock turnover, with increasing “active” sulfur species; skin temperature rise due to the increasing insulation effect of the scale, generating an over-tempering of the material and possible degeneration into creep conditions. Thor115 is a ferritic steel with 11% chromium content to resist sulfidation. It has excellent creep properties for high temperature environments: higher allowable stresses than grade 91, keeping the same manufacturing and welding procedures. At the same time, it has the characteristics of ferritic steel, ensuring enhanced thermal conductivity and lower thermal expansion compared to austenitic steels. Comparative corrosion tests between Thor115 and other ferritic steels typically used in this industry (e.g., grade T/P5 and grade T/P9) have been carried out to simulate different corrosive conditions, confirming the superior properties of Thor115 relative to other ferritic grades. For these reasons, Thor 115 is a suitable replacement material for piping components that need an upgrade from grade T/P9 or lower, in order to reduce corrosion rate or frequency of maintenance operations.

The aim of this work was to reveal the effects of trace elements on the creep properties of nickel-iron base superalloys, which are the candidate material for the large components of the advanced-ultrasupercritical (A-USC) power generation plants. High temperature tensile and creep properties of forged samples with seven different compositions were examined. No significant differences were observed in the creep rate versus time curves of the samples, of which contents of magnesium, zirconium, manganese and sulfur were varied. In contrast, the curves of phosphorus-added samples showed very small minimum creep rates compared to the other samples. The creep rupture lives of phosphorus-added samples were obviously longer than those of the other samples. Microstructure observation in the vicinity of grain boundaries of phosphorus-added samples after aging heat treatment revealed that there were fine precipitates consisting of phosphorus and niobium at the grain boundaries. The significant suppression of the creep deformation of phosphorus-added sample may be attributed to the grain boundary strengthening caused by the fine grain boundary precipitates.

Modern gas turbines are operated with fuels that are very clean and within the allowances permitted by fuel specifications. However, the fuels that are being considered contain vanadium, sulfur, sodium and calcium species that could significantly contribute to the degradation of components in hot gas flow path. The main potential risk of material degradation from these fuels is “hot corrosion” due to the contaminants listed above combined with alkali metal salts from ambient air. Depending on the temperature regime hot corrosion can damage both TBC coatings and bond coat/substrate materials. Deposit-induced or hot corrosion has been defined as “accelerated oxidation of materials at elevated temperatures induced by a thin film of fused salt deposit”. For the initiation of hot corrosion, deposition of the corrosive species, e.g. vanadates or sulfates, is necessary. In addition to the thermodynamic stability, the condensation of the corrosive species on the blade/vane material is necessary to first initiate and then propagate hot corrosion. Operating temperatures and pressures both influence the hot corrosion damage. The temperature ranges over which the hot corrosion occurs depend strongly on following three factors: deposit chemistry, gas constituents and metal alloy (or bond coating/thermal barrier coating) composition. This paper reports the activities involved in establishing modeling and simulation followed by testing/characterization methodologies in relevant environments to understand the degradation mechanisms essential to assess the localized risk for fuel flexible operation. An assessment of component operating conditions and gas compositions throughout the hot gas paths of the gas turbines, along with statistical materials performance evaluations of metal losses for particular materials and exposure conditions, are being combined to develop and validate life prediction methods to assess component integrity and deposition/oxidation/corrosion kinetics.

Increasing the efficiency of the Rankine regenerative-reheat steam cycle to improve the economics of electric power generation and to achieve lower cost of electricity has been a long sought after goal. Advanced ultra-supercritical (A-USC) development for materials to reach 760C (1400F) is a goal of the U.S. Program on Materials Technology for Ultrasupercritical Coal-Fired Boilers sponsored by the United States (U.S.) Department of Energy and the Ohio Coal Development Office (OCDO). As part of the development of advanced ultra-supercritical power plants in this program and internally funded programs, a succession of design studies have been undertaken to determine the scope and quantity of materials required to meet 700 to 760C (1292 to 1400F) performance levels. At the beginning of the program in 2002, the current design convention was to use a “two pass” steam generator with a pendant and horizontal tube bank arrangement as the starting point for the economic analysis of the technology. The efficiency improvement achieved with 700C (1292F) plus operation over a 600C (1112F) power plant results in about a 12% reduction in fuel consumption and carbon dioxide emissions. The reduced flue gas weight per MW generated reduces clean up costs for the lower sulfur dioxide, nitrogen oxides and particulate emissions. The operation and start up of the 700C (1292F) plant will be similar in control methods and techniques to a 600C (1112F) plant. Due to arrangement features, the steam temperature control range and the once through minimum circulation flow will be slightly different. The expense of nickel alloy components will be a strong economic incentive for changes in how the steam generator is configured and arranged in the plant relative to the steam turbine. To offer a view into the new plant concepts this paper will discuss what would stay the same and what needs to change when moving up from a 600C (1112F) current state-of-the-art design to a plant design with a 700C (1292F) steam generator and turbine layout.

Recently, boiler waterwall tube damage such as fireside corrosion and circumferential cracking in low NOx environments has become a serious issue in Japan, despite the typical use of relatively lower sulfur content coal is typically being used than in US. Thermal spray coating has been the most popular method for tube protection in Japan, and thermal spray coated tubes have been used for this purpose. However, extensive damage to thermal spray coating tubes from cracking and exfoliation has been recently experienced. It has been reported that the thermal fluctuations occurring due to operational changes create alternating stress, leading to cracking and exfoliation of the thermal sprayed thin coating. Corrosion-resistant weld overlays, such as Type 309 stainless steel (in sub-critical boilers) and Alloy 622 (in sub-critical and super-critical boilers), are commonly used to protect boiler tubes from corrosion in low NOx coal fired boilers in U.S. In order to develop a fundamental understanding of the high temperature corrosive behavior of Alloy 622 weld overlay, gaseous corrosion testing and certain mechanical tests for consideration of long-term aging were undertaken. After four years of service in the low NOx combustion environment of a coal fired supercritical boiler, field tests on Alloy 622 weld overlay panels are in continuation. This paper describes the field test behavior of Alloy 622 weld overlay panels installed in a Japanese supercritical boiler, the laboratory results of weight loss corrosion testing, and the results of cyclic bend tests with overlay welded tubes related to aging.

Six types of solution treated Ni-based alloy plates having a thickness of 25mm, namely Alloy 617, Alloy 263, Alloy 740, Alloy 141, HR6W (45Ni-23Cr-7W) and HR35 (50Ni-30Cr-4W-Ti) for advanced-USC boilers, were subjected to corrosion testing. In addition, three types of conventional ferritic and five types of conventional austenitic stainless tubes were also tested to compare their corrosion properties. Hot corrosion tests were conducted in order to assess the effects of temperature, material composition and coal ash composition on hot corrosion. The maximum average metal loss and the maximum corrosion rate were observed under 700°C test conditions. Cr content in the materials played an important role in the corrosion rate, with higher Cr content materials tending to show lower rates. However, Ni-based alloy materials showed slightly greater corrosion rates than those of stainless steels having equivalent Cr content in the over-700°C test condition. It was considered that rich Ni in the alloys easily reacted with sulfur, thus forming corrosion products having low melting points, such that corrosion was accelerated. The concentration of Fe 2 O 3 and NiO in the synthetic coal ash was also observed to affect the corrosion rate.

The “Coal Ash Corrosion Resistant Materials Testing Program” by The Babcock & Wilcox Company (B&W), the U.S. Department of Energy (DOE), and the Ohio Coal Development Office (OCDO) at Reliant Energy's Niles plant provides full-scale in-situ testing of advanced boiler superheater materials to address fireside corrosion, a key issue for improving efficiency in new coal-fired plants and service life in existing ones. In 1998, B&W developed a system with three identical sections containing multiple segments of twelve different materials from contributors like Oak Ridge National Laboratory (ORNL), cooled by reheat steam and installed in 1999 above the furnace entrance in the Niles Plant 110 MWe Unit #1 firing high-sulfur Ohio coal to test materials at advanced supercritical steam temperatures (1100°F+) in corrosive conditions. The first section was evaluated after 29 months in 2001, the second in 2003, and the final section is expected for removal in 2005. This paper outlines the program, test system, and materials, and it presents the evaluation results for the first two sections.

This paper investigates the combined effect of shot peening and pre-oxidation treatment in air on the subsequent steam oxidation resistance of Modified 9Cr-1Mo steel with different sulfur contents. Cast steel balls (50-180 μm diameter) and pure Cr (50-230 μm diameter) were used for shot peening durations of 5-50 seconds. After shot peening, pre-oxidation was performed in air at 973K for 3.6ks. Then, oxidation testing was conducted in steam at 923K for up to 3.6Ms. Only the combination of Cr shot peening and pre-oxidation treatment facilitated the formation of a protective Cr-rich oxide scale on the specimen surface during pre-oxidation. This Cr-rich oxide scale remained stable during subsequent steam oxidation, resulting in excellent oxidation resistance of the steel.

The Department of Energy and Ohio Coal Development Office jointly sponsored research to evaluate materials for advanced ultrasupercritical (A-USC) coal power plants, testing both monolithic tube materials and weld overlay combinations under real operating conditions. Testing was conducted in the highly corrosive, high-sulfur coal environment of Reliant Energy's Niles Plant Unit 1 boiler in Ohio. After 12 months of exposure, researchers evaluated six monolithic tube materials and twelve weld overlay/tube combinations for their high-temperature strength, creep resistance, and corrosion resistance in both steam-side and fire-side environments. Among the monolithic materials, Inconel 740 demonstrated superior corrosion resistance with the lowest wastage rate, while EN72 emerged as the most effective weld overlay material across various substrates, offering consistent protection against corrosion.

This paper outlines a comprehensive UK-based research project (2007-2010) focused on developing fireside corrosion models for heat exchangers in ultra-supercritical plants. The study evaluates both conventional materials like T22 and advanced materials such as Super 304H, examining their behavior under various test environments with metal skin temperatures ranging from 425°C to 680°C. The research aims to generate high-quality data on corrosion behavior for materials used in both furnace and convection sections, ultimately producing reliable corrosion prediction models for boiler tube materials operating under demanding conditions. The project addresses some limitations of existing models for these new service conditions and provides a brief review of the fuels and test environments used in the program. Although modeling is still limited, preliminary results have been presented, focusing on predicting fireside corrosion rates for furnace walls, superheaters, and reheaters under various service environments. These environments include those created by oxyfuel operation, coal-biomass co-firing, and more traditional coal firing.

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.

Oxyfuel combustion is considered as one of the most promising technologies to facilitate CO 2 capture from flue gases. In oxyfuel combustion, the fuel is burned in a mixture of oxygen and recirculated flue gas. Flue gas recirculation increases the levels of fireside CO 2 , SO 2 , Cl and moisture, and thus promotes fouling and corrosion. In this paper the corrosion performance of two superheater austenitic stainless steels (UNS S34710 and S31035) and one Ni base alloy (UNS N06617) has been determined in laboratory tests under simulated oxyfuel conditions with and without a synthetic carbonate based deposits (CaCO 3 - 15 wt% CaSO 4 , CaCO 3 - 14wt% CaSO 4 - 1 KCl) at 650 and 720°C up to 1000 hours. No carburization of the metal substrate was observed after exposure to simulated oxyfuel gas atmospheres without deposit, although some carbon enrichment was detected near the oxide metal interface. At 720°C a very thin oxide formed on all alloy surfaces while the weight changes were negative. This negative weight change observed is due to chromium evaporation in the moist testing condition. At the presence of deposits, corrosion accelerated and considerable metal loss of austenitic alloys was observed at 720°C. In addition, clear carburization of austenitic steel UNS S34710 occurred.

The reasonable procedures for estimation of 100,000 h creep rupture strength have been investigated for Alloy 617 and Alloy 740 for A-USC power plants by Larson Miller method. The creep rupture data of longer duration than 500 h in the temperature range between 593 and 816 °C and between 600 and 850 °C were used for the analysis on Alloy 617 and Alloy 740, respectively. The data were obtained by Special Metals. In these temperature ranges, Ni3Al-γ’ can precipitate in Alloy 617 and Alloy 740 during creep. The maximum time to rupture was 40,126.7 and 24,066 h for Alloy 617 and Alloy 740, respectively. The rupture data for Alloy 617 exhibit large scattering, especially at 760 °C, showing a split into two groups. After eliminating the shorter time to rupture data at 760 °C, the regression analysis using the second order equation of Larson-Miller parameter gives us the Larson-Miller constant C of 12.70 and the 100,000 h creep rupture strength of 100 MPa at 700 °C. The regression analysis underestimates the constant C and corresponding 100,000 h creep rupture strength of Alloy 617, as shown by the regression curves locating below the rupture data at long times, while those locating above the rupture data at short times. The underestimation of constant C is caused by large data scattering. The linear extrapolation of log tr versus reciprocal temperature 1/T plot to 1/T = 0 at constant stresses gives us the constant C of 18.5, which is much larger than that by the regression analysis. Using an appropriate constant C of 18.45, the 100,000 h creep rupture strength of Alloy 617 is estimated to be 123 MPa at 700 °C. On the other hand, the rupture data for Alloy 740 exhibit only a little bit scattering. The regression analysis gives us C = 18.45, which agrees very well with that by the linear extrapolation of log tr versus 1/T plot to 1/T = 0. The 100,000 h creep rupture strength of Alloy 740 is estimated to be 214 and 109 MPa at 700 and 760 °C, respectively.

Coal ash corrosion testing was conducted on six solution-treated nickel-based alloy plates (Alloy 617, Alloy 263, Alloy 740, Alloy 141, HR6W [45Ni-23Cr-7W], and HR35 [50Ni-30Cr-4W-Ti]) intended for advanced-USC boilers, along with conventional ferritic and austenitic stainless tubes for comparison. Tests used synthetic coal ash (Na 2 SO 4 , K 2 SO 4 , Fe 2 O 3 ) with varying SO 2 concentrations (0.02-1.00 vol%). Results showed maximum metal loss at 700°C, with higher SO 2 levels causing increased corrosion. Materials with higher chromium content demonstrated better corrosion resistance, suggesting chromium content is a crucial factor in material selection for these applications.

In order to improve thermal efficiency of fossil-fired power plants through increasing steam temperature and pressure high strength martensitic 9-12%Cr steels have extensively been used, and some power plants have experienced creep failure in high temperature welds after several years operations. The creep failure and degradation in welds of longitudinally seam-welded Cr- Mo steel pipes and Cr-Mo steel tubes of dissimilar metal welded joint after long-term service are also well known. The creep degradation in welds initiates as creep cavity formation under the multi-axial stress conditions. For the safety use of high temperature welds in power plant components, the complete understanding of the creep degradation and establishment of creep life assessment for the welds is essential. In this paper creep degradation and initiation mechanism in welds of Cr-Mo steels and high strength martensitic 9-12%Cr steels are reviewed and compared. And also since the non-destructive creep life assessment techniques for the Type IV creep degradation and failure in high strength martensitic 9-12%Cr steel welds are not yet practically established and applied, a candidate way based on the hardness creep life model developed by the authors would be demonstrated as well as the investigation results on the creep cavity formation behavior in the welds. Additionally from the aspect of safety issues on welds design an experimental approach to consider the weld joint influence factors (WJIF) would also be presented based on the creep rupture data of the large size cross-weld specimens and component welds.

Along with rapid development of thermal power industry in mainland China, problems in metal materials of fossil power units also change quickly. Through efforts, problems such as bursting due to steam side oxide scale exfoliation and blocking of boiler tubes, and finned tube weld cracking of low alloy steel water wall have been solved basically or greatly alleviated. However, with rapid promotion of capacity and parameters of fossil power units, some problems still occur occasionally or have not been properly solved, such as weld cracks of larger-dimension thick-wall components, and water wall high temperature corrosion after low-nitrogen combustion retrofitting.

The INCONEL filler metals 72 and 72M have been utilized significantly for weld overlay protection of superheaters and reheaters, offering enhanced corrosion and erosion resistance in this service. Laboratory data conducted under simulated low-NOx combustion conditions, field exposure experience, and laboratory analysis (microstructure, chemical composition, overlay thickness measurements, micro-hardness) of field-exposed samples indicate that these overlay materials are also attractive options as protective overlays for water wall tubes in low-NOx boilers. Data and field observations will be compared for INCONEL filler metals 72, 72M, 625 and 622.