In order to enable a compact design for boiler superheaters in modern thermal power plants, cold-worked tube bending is an economical option. For service metal temperatures of 700 °C and above, nickel-based alloys are typically employed. To ensure a safe operation of such cold-worked alloys, their long-term mechanical behavior has to be investigated. In general, superheater tube materials in a cold-worked state are prone to a degradation of their long-term creep behavior. To predict this degradation, sensitive experiments have to be conducted. In this publication, the effects of cold working on the long-term creep behavior of three currently used nickel-based alloys are examined. Creep and creep rupture experiments have been conducted at typical service temperature levels on nickel-based alloys, which have been cold worked to various degrees. As a result, Alloy 263 exhibits no significant influence of cold working on the creep rupture strength. For Alloy 617, an increase of creep strength due to cold working was measured. In contrast, Alloy 740 showed a severe degradation of the creep strength due to cold working. The mechanism causing the sensitivity to cold working is not yet fully understood. Various formations of carbide precipitates at the grain boundaries are believed to have a major influence. Nevertheless, the experimentally observed sensitivity should always be considered in material selection for boiler tube design.

This study aims to examine the effects of grain boundary oxidation and creep on crack initiation and fracture behaviors in cold worked surface layer, under static tensile stresses in air. To determine these effects in relation to percent cold work and hardness scale, cold-rolled plates with a reduction ratios between 10% and 50% were prepared. Uniaxial constant load (UCL) tests were conducted at elevated temperature in air using smooth round bar specimen. UCL tests with a load of 0.9σy (926MPa) at 550°C show that rupture time for all cold- rolled materials were shorter than that of as-received material. From cross-sectional observation after UCL testing, surface crack at grain boundary and voids were observed in as-received material, whereas creep cracks were also observed in cold-rolled materials. This implied that crack initiation was assisted by cold working. Comparing test results with a load reduced to 0.8σy (823MPa), difference of rupture time was expected as a factor of 5 for as-received material, and measured as 2-3 for cold-rolled materials. It was suggested that cold worked layer was more sensitive to creep than base metal.

For higher efficiency and competitive overall performance, it would be an advantage to be able to safely exceed the highest operational values, currently up to about 600-620°C/25-30 MPa in supercritical (SC) boiler plants. Under such operating conditions the oxidation resistance in SC water tends to limit the potential for further improvement of efficiency. The way to increase the oxidation resistance of traditional austenitic boiler tubes e.g. TP 347H is to do additional cold work on the boiler tube inner surface. In the current paper the effect of cold work on the oxidation resistance of TP347H and TP347HFG has been evaluated by shot peened samples with different parameters and subjecting those samples to supercritical oxidation exposure. The results show an improvement in the oxidation resistance of the alloys, especially in the large grained alloy TP347H. Also the uniformity of the deformation layer was seen to have an influence on the oxidation resistance, since the oxide nodules start to grow at locations with the thinnest or no deformation layer.

To improve the efficiency of fossil fuel power plants the operating temperatures and pressures need to be increased. However, at high temperatures the steam side oxidation resistance becomes a critical issue for the steels used especially at the final stages of superheaters and reheaters. Apart from the chemical composition of the material, surface condition is a major factor affecting the oxidation resistance in steam and supercritical water. In this paper, stainless boiler steels (UNS S34710, S31035, S31042, and S30942) are investigated for oxidation resistance in flowing supercritical water. Tests were conducted in an autoclave environment (250 bar, with 125 ppb dissolved oxygen and a pH of 7) at 625°C, 650°C and 675°C for up to 1000 h. Materials were tested with as-delivered, shot peened, milled or spark eroded and ground surface finish. The results show a strong influence of surface finish at the early stages of oxidation. Oxides formed on cold worked surfaces were more adherent and much thinner than on a spark eroded and ground surface. This effect was stronger than the influence of temperature or alloy composition within the tested ranges.

The broken elbow of the final superheater tube (ASME SA213 TP304H) from a coal-fired power plant was evaluated. The root causes were identified by metallographic observation, sensitization evaluation, hardness measurement, and EBSD analysis. The analysis results reached the following conclusions. (1) The tube bending was not performed in accordance with ASME Code requirements—a solid-solution heat treatment was not performed after cold working. (2) The hardness at the elbow is greater than 260 HV, exceeding the ASME code limit. (3) The sensitization was 19%, showing a performance degradation. (4) There are no obvious corrosion elements in the oxide layers of the cracks. (5) Metallographic microstructure analysis shows that there are many intergranular cracks and carbides such as Cr-rich phase and Fe-Cr are precipitated at the grain boundaries, ultimately resulting in strain-induced precipitation hardening damage.

Cold working and bending during boiler manufacturing can induce strain hardening in austenitic stainless steel, potentially compromising creep ductility and leading to premature failures during operation. While design codes like ASME I, PG 19 provide guidelines for maximum strain levels before solution treating is required, industry concerns suggest these limits may be too high, prompting some boiler manufacturers to implement more conservative thresholds. This study examined the creep ductility of four austenitic stainless steels (TP310HCbN, XA704, TX304HB, and Sanicro 25) at prior strain levels of 12% and 15%, with Sanicro 25 demonstrating the highest ductility, followed by TX304HB, XA704, and TP310HCbN. Solution annealing successfully restored creep ductility to exceed 10% elongation in all materials, though this treatment may be necessary at strains of 12% and 15% for all materials except Sanicro 25 to ensure adequate creep ductility. The findings suggest that ASME I PG 19 guidelines for austenitic stainless steels containing Cb, V, and N should be reviewed, as lower strain limits could help reduce strain-induced precipitation hardening failures.

Low thermal expansion precipitation strengthening Ni-base superalloy, Ni-20Cr-10Mo-1.2Al-1.6Ti alloy (USC141TM), was developed for 700°C class A-USC steam turbine material by Hitachi, Ltd and Hitachi Metals, Ltd. USC141 is usually solution treated and then aged to increase high temperature strength for turbine blades and bolts. As the estimated 105h creep rupture strength at 700°C is about 180MPa, USC141 could also be expected to apply for boiler tubes. On the other hand, this alloy seems to be only solution treated to apply for boiler tubes because tubes are usually jointed by welding and bended by cold working and thus tube alloys should have low hardness before welding and bending and should be used as solution treated. In this study, the creep properties of USC141 as solution treated was evaluated, and the results and microstructures after creep tests were compared with those as aged. As a result, USC141 as solution treated exhibited almost as same creep rupture properties as that as aged because precipitation at grain boundaries and in grains gradually increased at testing temperatures around 700°C. Furthermore seamless tubes of USC141 were produced and various properties including creep properties are now being evaluated.

Advances in materials for power plants include not only new materials with higher-temperature capabilities, but also the use of current materials at increasingly higher temperatures. This latter activity builds on extensive experience of the performance of the various alloys, and provides a basis for identifying changes in alloy behavior with increasing temperature as well as understanding the factors that ultimately determine the maximum use temperatures of the different alloy classes. This paper presents results from an effort to model the exfoliation processes of steam-side oxide scales in a manner that describes as accurately as possible the evolution of strains in oxides growing inside small-diameter tubes subjected to large thermal gradients and to thermal transients typical of normal steam boiler operation. One way of portraying the results of such calculations is by plotting the evolving strains in a given oxide scale on an ‘Exfoliation Diagram’ (of the type pioneered by Manning et al. of the British Central Electricity Research Laboratory) to determine the earliest time at which the trajectory of these strains intersects a criterion for scale failure. Understanding of how such ‘strain trajectories’ differ among different alloys and are affected by the major variables associated with boiler operation has the potential to suggest boiler operating strategies to manage scale exfoliation, as well as to highlight the mode of scale failure and the limitations of each alloy. Preliminary results are presented of the strain trajectories calculated for alloys T22, T91, and TP347 subjected to the conditions experienced by superheaters under assumed boiler operating scenarios. For all three alloys the earliest predicted scale failures were associated with the increased strains developed during a boiler shut-down event; indeed, in the cases considered it appeared unlikely that scale failure would occur in any practically meaningful time due to strains accumulated during operation in a load-following mode in the absence of a shut down. The accuracy of the algorithms used for the kinetics of oxide growth appeared to be a very important consideration, especially for alloy TP347 for which large effects on oxide growth rate are known to occur with changes in alloy grain size and surface cold work.

HR6W (23Cr-44Ni-7W) is a candidate material for application in the maximum temperature locations of A-USC boilers. In this study the creep rupture properties of plastic deformed, notched, and weldment materials were investigated in comparison with those of solution treated material, in order to clarify the capability of HR6W as a material for A-USC plant application. The deterioration of long term creep rupture strength has been reported with respect to metastable authentic stainless steel due to cold working. However the creep strength of the 20% pre-strained HR6W increased. HR6W creep strength showed notch strengthening behavior. The creep ruptured strength of the GTAW joints was nearly the same as that of the solution treated material, and all specimens fractured within the base metal. The creep ductility of the solution treated materials decreased under low stress conditions. The intergranular fracture is considered to be caused of ductility drop. This tendency is the same as for austenitic stainless steel. The potential of HR6W as a material for A-USC was revealed from the standpoint of creep rupture properties.

Advanced power generation systems, including advanced ultrasupercritical (A-USC) steam and supercritical carbon dioxide (sCO 2 ) plants operating above 700°C, are crucial for reducing carbon dioxide emissions through improved efficiency. While nickel superalloys meet these extreme operating conditions, their high cost and poor weldability present significant challenges. This study employs integrated computational materials engineering (ICME) strategies, combining computational thermodynamics and kinetics with multi-objective Bayesian optimization (MOBO), to develop improved nickel superalloy compositions. The novel approach focuses on utilizing Ni 3 Ti (η) phase strengthening instead of conventional Ni 3 (Ti,Al) (γ’) strengthening to enhance weldability and reduce costs while maintaining high-temperature creep strength. Three optimized compositions were produced and experimentally evaluated through casting, forging, and rolling processes, with their microstructures and mechanical properties compared to industry standards Nimonic 263, Waspaloy, and 740H. Weldability assessment included solidification cracking and stress relaxation cracking tests, while hot hardness measurements provided strength screening. The study evaluates both the effectiveness of the ICME design methodology and the practical potential of these cost-effective η-phase strengthened alloys as replacements for traditional nickel superalloys in advanced energy applications.

INCONEL alloy 740H has been specified for tube and pipe for the boiler and heat exchanger sections of AUSC and sCO 2 pilot plants currently designed or under construction. These systems also require fittings and complex formed components such as flanges, saddles, elbows, tees, wyes, reducers, valve parts, return bends, thin-wall cylinders and tube sheets. The initial evaluation of alloy 740H properties, leading to ASME Code Case 2702, was done on relatively small cross-section tube and plate. The production of fittings involves the use of a wide variety of hot or cold forming operations. These components may have complex geometric shapes and varying wall thickness. The utility industry supply chain for fittings is largely unfamiliar with the processing of age-hardened nickel-base alloys. Special Metals has begun to address this capability gap by conducting a series of trials in collaboration with selected fittings manufacturers. This paper describes recent experiences in first article manufacture of several components. The resulting microstructure and properties are compared to the published data for tubular products. It is concluded that it will be possible to manufacture most fittings with properties meeting ASME Code minima using commercial manufacturing equipment and methods providing process procedures appropriate for this class of alloy are followed. INCONEL and 740H are registered trademarks of Special Metals Corporation.

In the “Boiler Materials for Ultrasupercritical Coal Power Plants” program, sponsored by the U.S. Department of Energy and the Ohio Coal Development Office, various materials are being assessed for their suitability in the high-temperature, high-pressure environment of advanced ultrasupercritical (A-USC) boilers. Beyond mechanical properties and fireside corrosion resistance, these materials must also exhibit adequate steamside oxidation and exfoliation resistance. A comprehensive database of steamside oxidation test results at temperatures relevant to A-USC conditions has been compiled over recent years. These tests have been conducted on ferritic and austenitic materials with chromium content ranging from 2 to 26%. The specimens were evaluated for oxidation kinetics and oxide morphology. The findings indicate that steamside oxidation behavior is significantly affected by temperature, the chromium content of the material, and the ability of chromium to diffuse through the material's crystallographic lattice structure. Additionally, surface treatments have been applied to enhance the steamside oxidation resistance of certain materials. While these treatments have shown potential, their effectiveness can be limited by the operational temperatures.

Steam-side oxidation and the resultant exfoliation of iron-based scales cause unplanned shutdowns at coal-fired power generation plants. Exfoliate removal is currently limited to frequent unit cycling to minimize the volume of exfoliated scale, upgrading a plant with a “blow down” system, or installing a higher alloy. This paper discusses the rate of steam-side oxidation on Type 304H stainless steel (304H) tube after shot peening the internal surface with commercially available techniques. Shot peening the ID of Type 304H austenitic stainless steel superheater tubes has been shown to improve the overall oxidation resistance in steam. Decreasing the oxidation rate directly impacts the volume of exfoliated scale. The adherent spinel scales are thinner and more robust than non-shot peened tubes of the same alloy. Most of the improved oxidation resistance can be attributed to the presence of a spinel oxide layer combined with a continuous chromia layer formed near the steam-touched surfaces. The presence of a continuous chromia layer vastly reduces the outward diffusion of iron and minimizes the formation of iron-based scales that exfoliate. This work showed that a uniform cold-worker layer along the tube ID has a profound effect on oxidation resistance. Incomplete coverage allows oxidation to proceed in the non-hardened regions at a rate comparable to the oxidation rate on unpeened Type 304H.

Advanced power systems that operate at temperatures higher than about 650°C will require nickel-base alloys in critical areas for pressure containment. Age-hardened alloys offer an additional advantage of reduced volume of material compared with lower strength solid solution-strengthened alloys if thinner tube wall can be specified. To date, the only age-hardened alloy that has been approved for service in the time dependent temperature regime in the ASME Boiler and Pressure Vessel Code is INCONEL alloy 740H. Extensive evaluation of seamless tube, pipe, and forged fittings in welded construction, including implant test loops and pilot plants, has shown the alloy to be fit for service in the 650-800°C (1202-1472°F) temperature range. Since, nickel-base alloys are much more expensive than steel, manufacturing methods that reduce the cost of material for advanced power plants are of great interest. One process that has been extensively used for stainless steels and solution-strengthened nickel-base alloys is continuous seam welding. This process has rarely been applied to age-hardened alloys and never for use as tube in the creep-limited temperature regime. This paper presents the initial results of a study to develop alloy 740H welded tube, pipe and fittings and to generate data to support establishment of ASME code maximum stress allowables.

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.

The effects of pre-strain on creep properties of Alloy 740 have been investigated. Tensile strain was 7.5% and introduced by room temperature tensile test. Creep tests were conducted under 750 degree C, 275-350MPa. Creep rupture life of pre-strained sample decreased by half compared with as-heat treated sample. Creep behaviors of both samples were almost similar in primary creep stage, but onset of creep rate acceleration of pre-strained sample was faster than those of as-heat treated sample. As a result, minimum creep rate of pre-strained sample were two times larger than that of as-heat treated sample. From the observation of ruptured specimen, pre-strained sample had much more sub cracks than as-heat treated sample. On the other hand, microstructure of both samples was also different. There were MC precipitates on grain boundary in both ruptured specimens, but both size and number of MC precipitates were larger in pre-strained sample although creep life of pre-strained sample was shorter than that of as-heat treated sample. In this paper, the difference of creep behavior will be discussed in terms of both the microstructural change and mechanical damage.

As part of the Boiler Materials for Ultrasupercritical Coal Power Plants program, sponsored by the United States (U.S.) Department of Energy (DOE) and the Ohio Coal Development Office (OCDO), the steamside oxidation and oxide exfoliation behavior of candidate alloys have been thoroughly evaluated in steam at temperatures between 620°C and 800°C (1148°F and 1472°F) for times up to 10,000 hours. The results from this test program indicate that the oxidation rates and oxide morphologies associated with steamside oxidation are a strong function of the crystallographic lattice structure and the chromium content of the material. Oxide exfoliation correlates to oxide thickness. The time required to reach the critical oxide thickness for exfoliation can be estimated based on oxidation kinetic relationships. For austenitic stainless steels, shot peening is effective in reducing steamside oxidation/exfoliation, but the efficacy of this technique is limited by the operating temperature. Nickel-based alloys exhibit very low oxidation/exfoliation rates, but have a propensity to form aluminum/titanium oxides along near surface grain boundaries.

Large scale components of the conventional 600°C class steam turbine were made of the ferritic steel, but the steam turbine plants with main steam temperatures of 700°C or above (A-USC) using the Ni-base superalloys are now being developed in order to further improve the thermal efficiency. The weight of the turbine rotor for the A-USC exceeds 10ton. A lot of high strength superalloys for aircraft engines or industrial gas turbines have been developed up to now. But it is difficult to manufacture the large-scale parts for the steam turbine plants using these conventional high strength superalloys because of their poor manufacturability. To improve high temperature strength without losing manufacturability of the large scale components for the A-USC steam turbine plants, we developed Ni-base superalloy USC800(Ni-23Co-18Cr-8W-4Al-0.1C [mass %]) which has temperature capability of 800°C with high manufacturability achieved by controlling microstructure stability and segregation property. The 700°C class A-USC materials are the mainstream of current development, and trial production of 10 ton-class forged parts has been reported. However, there have been no reports on the development and trial manufacturing of the A-USC materials with temperature capability of 800°C. In this report, results of trial manufacturing and its microstructure of the developed superalloy which has both temperature capability 800°C and good manufacturability are presented. The trial manufacturing of the large forging, boiler tubes and turbine blades using developed material were successfully achieved. According to short term creep tests of the large forging and the tube approximate 100,000h creep strength of developed material was estimated to be 270MPa at 700 °C and 100MPa at 800°C.

Inconel alloy 740 was initially developed to enable the design of coal-fired boilers capable of operating at 700°C steam temperature and high pressure. The alloy successfully met the European program's targets, including 100,000-hour rupture life at 750°C and 100 MPa stress, and less than 2 mm metal loss in 200,000 hours of superheater service. However, thick section fabrication revealed weldability challenges, specifically grain boundary microfissuring in the heat affected zone (HAZ) of the base metal. This paper describes the development of a modified variant with significantly improved resistance to HAZ microfissuring and enhanced thermal stability, while maintaining desirable properties. The formulation process is detailed, and properties of materials produced within the new composition range are presented. Additionally, the microstructural stability of the original and modified alloy compositions is compared, demonstrating the advancements achieved in this critical material for next-generation power plants.

The application of cold weld repair techniques in the power industry has been well documented. This type of repair is only considered when a conventional repair (involving post-weld heat treatment) is impracticable or the penalties of time and cost for conventional repair are sufficiently high. A typical cold weld repair in the UK has involved low alloy ferritic steel (½Cr½Mo¼V, 2¼Cr1Mo) components welded with nickel based SMAW consumables or ferritic FCAW consumables. Modified 9Cr steel components have been used in UK power plant since the late 1980’s for a number of applications, such as superheater outlet headers, reheat drums and main steam pipework. The problems associated with this material have also been well documented, particularly premature type IV cracking of welds on creep weakened modified 9Cr steel. RWE Generation UK have developed modified 9Cr cold weld repairs on headers, pipework and tubes. These repairs have been underwritten with extensive testing. This paper will describe the work performed on developing T91 cold weld repairs and where they have been applied on power plant.