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.

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.

Using oxygen, rather than air, in coal-fired boilers has been studied for several years as a strategy to reduce NOx and concentrate CO 2 for capture. In combination with flue gas recirculation, higher levels of CO 2 are expected but increased H 2 O and SO 2 levels also may occur. In order to understand the role of substrate composition on corrosion, a combination of commercial and model alloys were investigated with synthetic coal ash and gas compositions simulating air- and oxyfiring environments. Exposure temperatures ranged from 600°-800°C to cover current operating temperatures up to advanced ultrasupercritical conditions. Using 500h exposures, no consistent negative effect was found for switching to the oxy-firing environment with the same synthetic ash. For model Fe-Cr alloys, 30%Cr was needed to form a thin protective reaction product across this temperature range. Among the commercial stainless steels, 310-type stainless steel showed low reaction rates with the maximum attack at 650°C. At higher temperatures, the depth of attack on Fe-base type 310 stainless steel was less than for Ni-base alloy 740. Initially, this difference was attributed to the Al and Ti additions in alloy 740. However, cast and hot rolled model Ni-18Cr and -22Cr alloys with various Al and Ti additions showed decreased metal loss with increasing Al and Ti additions in the oxy-firing environment at 700° and 800°C. As expected, metal loss was very sensitive to Cr content. A second set of model alloys also examined the effect of Co and Mo.

Modern polycrystalline Ni-base superalloys for advanced gas turbine engines have been a key component that has contributed to technological advances in propulsion and power generation. As advanced turbine engine designs are beginning to necessitate the use of materials with temperature and strength capabilities beyond those exhibited by existing materials, new alloying concepts are required to replace conventional Ni-base superalloys with conventional γ-γ’ microstructures. The phase stability of various high Nb content Ni-base superalloys exhibiting γ-γ’-δ -η microstructures have been the subject of a number of recent investigations due to their promising physical and mechanical properties at elevated temperatures. Although high overall alloying levels of Nb, Ta and Ti are desirable for promoting high temperature strength in γ-γ’ Ni-base superalloys, excessive levels of these elements induce the formation of δ and η phases. The morphology, formation, and composition of precipitate phases in a number of experimental alloys spanning a broad range of compositions were explored to devise compositional relationships that can be used to predict the microstructural phase stability and facilitate the design of Ni-base superalloys.

Nitridation is a high-temperature material degradation issue that can occur in air and in environments containing nitrogen, ammonia, etc., and in a variety of industrial processes. The nitridation behavior of several commercial nickel- and cobalt-based alloys is reviewed in this paper. The alloys include Haynes 230, Haynes 188, Haynes 625, Haynes 617, Haynes 214, Hastelloy X, and Haynes 233. The environments discussed are high-purity nitrogen gas between 871°C and 1250°C, 100% ammonia gas at 982°C and 1092°C, and a simulated combustion atmosphere at 982°C. The results showed that nitridation occurred in all the environments containing nitrogen. The nitridation attack was strongly influenced by the alloy compositions and the type of oxide formed (i.e., chromia or alumina), as some degree of oxidation was expected in the environments in which residual oxygen was present. Thermal cycling is briefly discussed because the integrity of protective oxides is also an important factor in resisting high-temperature oxidation and nitridation attack.

This study investigates the growth kinetics and spallation behavior of oxide scales formed under steam environments on alloys used in high-temperature plants. The influence of alloy composition is analyzed using two approaches: an empirical model based on the concept of “chromium equivalent” and a neural network model. Both models demonstrate a good correlation with experimental results when sufficient data is available to generate the model parameters. However, there is insufficient data on scale spallation to develop similar models describing the influence of alloy composition on this phenomenon.

Solidification cracking (SC) is a defect that occurs in the weld metal at the end of the solidification. It is associated with the presence of mechanical and thermal stresses, besides a susceptible chemical composition. Materials with a high solidification temperature range (STR) are more prone to the occurrence of these defects due to the formation of eutectic liquids wetting along the grain boundaries. The liquid film collapses once the structure shrinks and stresses act during the solidification. Thus, predicting the occurrence of SC before the welding process is important to address the problem and avoid the failure of welded components. The nuclear power industry has several applications with dissimilar welding and SC-susceptible materials, such as austenitic stainless steels, and Ni-based alloys. Compositional optimization stands out as a viable approach to effectively mitigate SC in austenitic alloys. The integration of computational modeling into welding has significantly revolutionized the field of materials science, enabling the rapid and cost-effective development of innovative alloys. In this work, a SC resistance evaluation is used to sort welding materials based on a computational fluid dynamic (CFC) model and the alloy's chemical composition. An index named Flow Resistance Index (FRI) is used to compare different base materials and filler metals as a function of dilution. This calculation provides insights into the susceptibility to SC in dissimilar welding, particularly within a defined dilution range for various alloys. To assess the effectiveness of this approach, the relative susceptibility of the materials was compared to well-established experimental data carried out using weldability tests (Transvarestraint and cast pin tear test). The FRI calculation was programmed in Python language and was able to rank different materials and indicate the most susceptible alloy combination based on the dilution and chemical composition.

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.

An attempt is being made to develop novel Ni-Mo-W-Cr-Al-X alloys with ICME approach with critical experimental/simulations and processing/microstructural characterization/property evaluation and performance testing has been adopted. In this work, based on thermodynamic modeling five alloy compositions with varying Mo/W and two alloys with high tungsten modified with the addition of Al or Ti were selected and prepared. The newly developed alloys were evaluated for their response to thermal aging in the temperature range of 700 to 850 °C and corrosion in the KCl-NaCl-MgCl 2 salt under suitable conditions. Thermally aged and post-corrosion test samples were characterized to ascertain phase transformations, microstructural changes and corrosion mechanisms. Al/Ti modified alloys showed significant change in hardness after 400 hours aging at 750°C, which was found to be due to the presence of fine γ’/γ” precipitates along with plate-shaped W/Mo-rich particles. These alloys show comparable molten salt corrosion resistance as commercial alloys at 750°C for 200-hour exposures. The good corrosion behavior of these alloys may be attributed to the formation of a protective multicomponent Al-or Ti-enriched oxide as well as the unique microstructure.

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 power generation industry worldwide aims to develop coal-fired boilers operating at much higher efficiencies than current supercritical plants. This increased efficiency is expected through ultrasupercritical steam conditions, requiring new materials for critical components. To limit the use of expensive alloying materials, it is necessary to maximize the strength and corrosion capabilities across the material spectrum from ferritic to austenitic and nickel-based alloys. Sandvik Materials Technology has developed an austenitic alloy, Sanicro 25, with excellent high-temperature strength and corrosion resistance using an economical alloy composition. The alloy is designed for use within 700°C (1300°F)/300 bar (4500 psi) steam conditions and is a leading candidate material for such high-temperature applications. This paper introduces Sanicro 25, its development status, and properties.

The competitive effect of Nb and V additions on the high-temperature oxidation behavior of Ti- 30Al alloys were studied at 800°C in air. Oxidation performance increased with increasing Nb content, however, V additions eliminated the beneficial effect of Nb on oxidation performance, causing higher oxidation mass gains. In-situ high-temperature XRD by means of synchrotron source suggested dissolution of Nb 5+ but lower valence of vanadium ions in the TiO 2 oxide scale during oxidation. Dissolution of Nb and V ions with different valence in TiO 2 during oxidation could cause the beneficial and detrimental effects observed on the performance of high-temperature oxidation of Ti-30Al.

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.

The advancement of additive manufacturing (AM) technology has heightened interest in producing components from nickel-based superalloys for high-temperature applications; however, developing high gamma prime (γ’) strengthened alloys suitable for AM at temperatures of 1000°C or higher poses significant challenges due to their “non-weldable” nature. Traditional compositions intended for casting or wrought processes are often unsuitable for AM due to their rapid heating and cooling cycles, leading to performance compromises. This study introduces ABD-1000AM, a novel high gamma prime Ni-based superalloy designed using the Alloys-by-Design computational approach to excel in AM applications at elevated temperatures. Tailored for AM, particularly powder bed fusion, ABD-1000AM demonstrates exceptional processing capability and high-temperature mechanical and environmental performance at 1000°C. The study discusses the alloy design approach, highlighting the optimization of key performance parameters, composition, and process-microstructure-performance relationships to achieve ABD-1000AM’s unique combination of processability and creep resistance. Insights from ABD-1000AM’s development inform future directions for superalloy development in complex AM components.

This work concerns a study into the design of creep resistant precipitation hardened austenitic steels for fossil fuel power plants using an integrated thermodynamics based model in combination with a genetic algorithm optimization routine. The key optimization parameter is the secondary stage creep strain at the intended service temperature and time, taking into account the coarsening rate of MX carbonitrides and its effect on the threshold stress for secondary creep. The creep stress to reach a maximal allowed creep strain (taken as 1%) at a given combination of service temperature and time is formulated and maximized. The model was found to predict the behavior of commercial austenitic creep resistant steels rather accurately. Using the alloy optimization scheme three new steel compositions are presented yielding optimal creep strength for various intended service times up to 105 hours. According to the evaluation parameter employed, the newly defined compositions will outperform existing precipitate strengthened austenitic creep resistant steels.

Long-term performance of high temperature alloys is critically linked to the oxidation behavior in power generation applications in wet air and steam. As power generation systems move towards higher efficiency operation, nextgeneration fossil, nuclear and concentrating solar power plants are considering supercritical CO 2 cycle above 700°C. Wrought solid solution strengthened and precipitations strengthened alloys are leading candidates for both steam and Supercritical CO 2 power cycles. This study evaluates the cyclic oxidation behavior of HAYNES 230, 282, and 625 alloys in wet air, flowing laboratory air, steam and in 1 and 300 bar Supercritical CO 2 at ~750°C for duration of 1000 -10,000h. Test samples were thermally cycled for various times at temperature followed by cooling to room temperature. Alloy performances were assessed by analyzing the weight change behavior and extent of attack. The results clearly demonstrated the effects of alloy composition and environment on the long-term cyclic oxidation resistance. The extents of attack varied from alloy to alloy but none of the alloys underwent catastrophic corrosion and no significant internal carburization was observed in supercritical CO 2 . The performance of these alloys indicates that these materials are compatible not only in oxidizing environments, but also in Supercritical CO 2 environments for extended service operation.

By utilizing computational thermodynamics in a Design of Experiments approach, it was possible to design and manufacture nickel-base superalloys that are strengthened by the eta phase (Ni3Ti), and that contain no gamma prime (Ni3Al,Ti). The compositions are similar to NIMONIC 263, and should be cost-effective, and have more stable microstructures. By varying the aging temperature, the precipitates took on either cellular or Widmanstätten morphologies. The Widmanstätten-based microstructure is thermally stable at high temperatures, and was found to have superior ductility, so development efforts were focused on that microstructure. High temperature tensile test and creep test results indicated that the performance of the new alloys was competitive with NIMONIC 263. SEM and TEM microscopy were utilized to determine the deformation mechanisms during creep.

New Fe-base ferritic alloys based on Fe-30Cr-3Al-Nb-Si (wt.%) were proposed with alloy design concepts and strategies targeted at improved performance of tensile and creep-rupture properties, environmental compatibilities, and weldability, compared to Grade 91/92 type ferritic-martensitic steels. The alloys were designed to incorporate corrosion and oxidation resistance from high Cr and Al additions and precipitate strengthening via second-phase intermetallic precipitates (Fe2Nb Laves phase), with guidance from computational thermodynamics. The effects of alloying additions, such as Nb, Zr, Mo, W, and Ti, on the properties were investigated. The alloys with more than 1 wt.% Nb addition showed improved tensile properties compared to Gr 91/92 steels in a temperature range from 600-800°C, and excellent steam oxidation at 800°C as well. Creep-rupture properties of the 2Nb-containing alloys at 700°C were comparable to Gr 92 steel. The alloy with a combined addition of Al and Nb exhibited improved ash-corrosion resistance at 700°C. Additions of W and Mo were found to refine the Laves phase particles, although they also promoted the coarsening of the particle size during aging. The Ti addition was found to reduce the precipitate denuded zone along the grain boundary and the precipitate coarsening kinetics.

Austenitic heat resistant steels are one of the most promising materials to be applied around 650°C, due to its superior creep strength than conventional ferritic steels and lower material cost than Ni based superalloys. The problem of austenitic steels is its high thermal expansion coefficient (CTE), which leads to high deformation and stress when applied in rotors, casings, blades and bolts. To develop low CTE austenitic steels together with high temperature strength, we chose the gamma-prime strengthened austenitic steel, A-286, as the base composition, and decreased the CTE by introducing the invar effect. The developed alloy, Fe-40Ni-6Cr-Mo-V-Ti-Al-C-B, showed low CTE comparable to conventional ferritic steels. This is mainly due to its high Ni and low Cr composition, which the invar effect is prone even at high temperature region. This alloy showed higher yield strength, higher creep rupture strength and better oxidation resistance than conventional high Cr ferritic steels and austenitic steels. The 2 ton ESR ingot was forged or hot rolled without defects, and the blade trial manufacturing was successfully done. This alloy is one of the best candidates for USC and A-USC turbine components.

MoSiBTiC alloy is a promising material for advanced aerospace applications and next generation high pressure turbine blades in jet engines and gas turbines. It mainly consists of Mo solid solution, TiC and Mo 5 SiB 2 phases and has creep strength much stronger than Ni-base superalloys and better than SiC/SiC ceramic matrix composites. Furthermore, the fracture toughness of the alloy is much better (>15 MPa(m) 1/2 ) than Mo-Si-B ternary alloys (<10 MPa(m) 1/2 ) even if the volume fraction of Mo solid solution is less than 50 %. The improvement of fracture toughness would be caused not only by the continuity of Mo solid solution in solidification microstructure but also by TiC phase affecting as a fracture-resistant phase. In order to understand the microstructure evolution during solidification and the effect of TiC phase on the fracture toughness of the MoSiBTiC alloy, Mo-Ti-C ternary model alloys are dealt with in this study. Then, (1) liquidus surface projection and (2) isothermal section and the elastic moduli of TiC phase in equilibrium with Mo solid solution were focused on. The obtained liquidus surface projection suggests that the ternary transition peritectic reaction (L+ Mo 2 C->Mo+TiC) takes place in Mo-rich region. At 1800 °C, TiC phase in equilibrium with Mo phase contains at least 20.2 at% Mo and the Mo/TiC/Mo 2 C three phase region should exist around Mo-15Ti-10C.