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.

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 necessity to reduce carbon dioxide emissions of new fossil plant, while increasing net efficiency has lead to the development of not only new steels for potential plant operation of 650°C, but also cast nickel alloys for potential plant operation of up to 700°C and maybe 750°C. This paper discusses the production of prototype MarBN steel castings for potential plant operation up to 650°C, and gamma prime strengthened nickel alloys for advanced super critical plant (A-USC) operation up to 750°C. MarBN steel is a modified 9% Cr steel with chemical concentration of Cobalt and tungsten higher than that of CB2 (GX-13CrMoCoVNbNB9) typically, 2% to 3 Co, 3%W, with controlled B and N additions. The paper will discuss the work undertaken on prototype MarBN steel castings produced in UK funded research projects, and summarise the results achieved. Additionally, within European projects a castable nickel based super alloy has successfully been developed. This innovative alloy is suitable for 700°C+ operation and offers a solution to many of the issues associated with casting precipitation hardened nickel alloys.

The need to reduce carbon dioxide emissions of new fossil power plants is one of the biggest challenges of mankind in the next decades. In this context increasing net efficiency is the most important aspect which has led to the development of not only new steels for potential plant operation up to 650°C, but also to forged nickel alloys for 700°C and maybe 750°C. For steam temperatures of 700°C Alloy 617 and variants like TOS1x have been already intensively investigated, and manufacturability of large rotor parts was demonstrated. For operation temperatures of 750°C, only the use of γ‘ age-hardenable nickel base alloys is possible. Alloy 263 is one of the most promising alloys for manufacturing large forged components. For this material grade Saarschmiede has produced successfully a large rotor forging for the first time. Considering the complexity in manufacturing large nickel base alloy forgings, the implementation of simulation tools for calculation and optimization of production parameters becomes especially important. Numerical simulation methods are essential to predict material behavior and to optimize material quality-related manufacturing steps. In reference to mechanical properties, microstructure, uniformity of chemical composition FEM computer simulations for the key manufacturing processes re-melting, forging and heat treatment are in application. This paper will present the current status of production of very large prototype nickel base alloy rotor forgings for 700°C and 750°C A-USC power plants. Test results of an Alloy 617 large full scale turbine rotor component recently with improved properties produced will be highlighted. Experiences and results in applying numeric simulation models to ingot manufacturing and forging will also be reported.

The drive for reduced carbon dioxide emissions and improved efficiency in coal fire power plant has led to much work being carried out around the world with regards to material development to enable 700+°C steam temperature operation. At these elevated temperatures and pressures steels just don’t have enough strength, and typically have a temperature limit of around 620°C (possibly up to 650°C in the near future) in the HP environment. Therefore, material development has focused on nickel alloys. European programs such as AD700, COMTES, European 50+ and more recently, NextGen Power and Macplus, have investigated the use of nickel alloys in the steam turbine. Large castings have an important role within the steam turbine, because valves bodies and turbine casings are nearly always produced from a cast component. The geometry of these components is often complex, and therefore, the advantage of using castings for such items is that near net shapes can be produced with minimal machining. This is important, as nickel alloys are expensive, and machining is difficult, so castings offer an attractive cost benefit. Cast shapes can be more efficiently designed with regards to stress management. For example, contouring of fillet regions can help to reduce stress concentrations leads to reduced plant maintenance and casting complex shapes reduces the number of onsite fabrication welds to inspect during outage regimes.

This paper examines the ongoing significance of pulverized coal-fired steam plants in global power generation, focusing on technological advancements and strategies for improving efficiency and reducing CO 2 emissions. It traces the development of Ultra-Supercritical (USC) plants with steam temperatures around 600°C and explores immediate opportunities for further efficiency enhancements, including the innovative Master Cycle. The potential for increasing steam temperatures to 650°C using new steels and to 700°C with nickel-based AD 700 technology is discussed. The paper outlines a comprehensive strategy for CO 2 emission reduction: maximizing plant efficiency, co-firing with CO 2 -neutral fuels, and integrating with district heating/cooling or industrial heat consumers. Carbon capture and storage techniques are presented as a final step in this multi-faceted approach to sustainable power generation.

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

The “Cool Earth-Innovative Energy Technology Program,” launched by the Japanese government in March 2008, aims to significantly reduce global greenhouse gas emissions. Among the 21 selected technologies is the Advanced Ultra Super Critical (A-USC) pressure power generation, which targets the commercialization of a 700°C class pulverized coal power system with a power generation efficiency of 46% by around 2015. As of 2004, Japan's pulverized coal power plant capacity reached 35 GW, with the latest plants achieving a steam temperature of 600°C and a net thermal efficiency of approximately 42% (HHV). Older plants from the 1970s and early 1980s, with steam temperatures of 538°C or 566°C, are nearing the need for refurbishment or rebuilding. A case study on retrofitting these older plants with A-USC technology, which uses a 700°C class steam temperature, demonstrated that this technology is suitable for such upgrades and can reduce CO 2 emissions by about 15%. Following this study, a large-scale development of A-USC technology began in August 2008, focusing on developing 700°C class boiler, turbine, and valve technologies, including high-temperature material technology. Candidate materials for boilers and turbine rotor and casing materials are being developed and tested. Two years into the project, useful test results regarding these candidate materials have been obtained, contributing to the advancement of A-USC technology.

Following the successful completion of a 14-year effort to develop and test materials which would allow advanced ultra-supercritical (A-USC) coal-fired power plants to be operated at steam temperatures up to 760°C, a United States-based consortium has started on a project to build an A-USC component test facility, (A-USC ComTest). Among the goals of the facility are to validate that components made from the advanced alloys can perform under A-USC conditions, to accelerate the development of a U.S.-based supply chain for the full complement of A-USC components, and to decrease the uncertainty for cost estimates of future commercial-scale A-USC power plants. The A-USC ComTest facility will include a gas fired superheater, thick-walled cycling header, steam piping, steam turbine (11 MW nominal size) and valves. Current plans call for the components to be subjected to A-USC operating conditions for at least 8,000 hours by September 2020. The U.S. consortium, principally funded by the U.S. Department of Energy and the Ohio Coal Development Office with co-funding from Babcock & Wilcox, General Electric and the Electric Power Research Institute, is currently working on the Front-End Engineering Design phase of the A-USC ComTest project. This paper will outline the motivation for the project, explain the project’s structure and schedule, and provide details on the design of the facility.

Increasing the steam temperature of a coal-fired pulverized coal (PC) power plant increases its efficiency, which decreases the amount of coal required per MW of electrical output and therefore decreases the emissions from the plant, including CO 2 . However, increasing the steam temperature requires that the materials for the boiler pressure parts and steam turbine be upgraded to high-nickel alloys that are more expensive than alloys typically used in existing PC units. This paper explores the economics of A-USC units operating between 595°C and 760°C (1100°F to 1400°F) with no CO 2 removal and with partial capture of CO 2 at an emission limit of 454 kg CO 2 /MW-hr (1000 lb CO 2 /MW-hr) on a gross power basis. The goal of the paper is to understand if the improved efficiency of A-USC would reduce the cost of electricity compared to conventional ultra-supercritical units, and estimate the economically “optimal” steam temperature with and without CO 2 removal.

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.

Hydrogen as a clean fuel is increasingly being used to propel gas turbines and to power combustion engines. Metallic materials including Ni-based alloys are commonly used in conventional gas turbines and combustion engines. However, hydrogen may cause embrittlement in these materials, depending on their chemical composition. In this work, the hydrogen embrittlement behavior of Ni-based alloys containing up to 50 wt.% Fe has been investigated using slow strain rate tensile testing, under cathodic hydrogen charging at room temperature. It was found that the larger the Ni equivalent concentration in an alloy, the more severe the hydrogen embrittlement. It was also found that solid solution alloys have less severe hydrogen embrittlement than precipitation alloys of the same Ni equivalent concentration. In solid solution alloys, hydrogen embrittlement led to cleavage type fracture, which is in line with literature where hydrogen enhanced planar deformation. In precipitation alloys, hydrogen embrittlement resulted in a typical intergranular fracture mode.

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.

In both direct- and indirect-fired supercritical CO 2 (sCO 2 ) cycles, there is considerable interest in increasing the size and efficiency of such systems, perhaps by increasing the peak temperature to >700°C. However, relatively little experimental data are available under these conditions with pressures of 200-300 bar. Furthermore, impurities such as O 2 and H 2 O in the CO 2 may greatly alter the compatibility of structural alloys in these environments. While an experimental rig is being constructed that can measure and control the impurity levels in sCO 2 at 200-300 bar, initial 1 bar experiments at 700°-800°C for 500 h have been conducted in high-purity and industrial grade CO 2 , CO 2 +0.15O 2 and CO 2 +10%H 2 O and compared to exposures in dry air and 200 bar sCO 2 . These results, focusing on Fe- and Ni-base structural alloys and commercial chromia- and alumina-forming alloys, indicate that modifications in the environment did not strongly affect the reaction products at 700°-800°C.

Direct-fired supercritical CO 2 (sCO 2 ) cycles are expected to result in sCO 2 with higher impurity levels compared to indirect-fired cycles. Prior work at ambient pressure showed minimal effects of O 2 and H 2 O additions, however, a new experimental rig has been built to have flowing controlled impurity levels at supercritical pressures at ≤800°C. Based on industry input, the first experiment was conducted at 750°C/300 bar in CO 2 +1%O 2 -0.25%H 2 O using 500-h cycles for up to 5,000 h. Compared to research grade sCO 2 , the results indicate faster reaction rates for Fe-based alloys like 310HN and smaller increases for Ni-based alloys like alloys 617B and 282. It is difficult to quantify the 310HN rate increase because of scale spallation. Characterization of the 5,000 h specimens indicated a thicker reaction product formed, which has not been observed in previous impurity studies at ambient pressure. These results suggest that more studies of impurity effects are needed at supercritical pressures including steels at lower temperatures.

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.

Advanced austenitic stainless steels, such as Super 304H, have been used in reheater and superheater tubes in supercritical and ultra-supercritical power plants for many years now. It is important to characterize the microstructure of ex-service reheater and superheater tubes as this will help researchers understand the long-term microstructural evolution and degradation of the material, which can impact the performance and lifetime of the components that are in service. In this research, the microstructure of an ex-service Super 304H reheater tube that has been in service for 99,000 hours at an approximate metal temperature of 873K (600°C) has been characterized. The characterization techniques used were electron microscopy-based and included imaging and chemical analysis techniques. Seven phases were observed as a result of the characterization work. The phases observed were MX carbonitrides rich in niobium, copper-rich particles, M 23 C 6 , sigma phase, Z phase, a cored phase, and a BCC phase.

Structural alloy corrosion is a major concern for the design and operation of supercritical carbon dioxide (sCO 2 ) power cycles. Looking towards the future of sCO 2 system development, the ability to measure real-time alloy corrosion would be invaluable to informing operation and maintenance of these systems. Sandia has recently explored methods available for in-situ alloy corrosion monitoring. Electrical resistance (ER) was chosen for initial tests due the operational simplicity and commercial availability. A series of long duration (>1000 hours) experiments have recently been completed at a range of temperatures (400-700°C) using ER probes made from four important structural alloys (C1010 Carbon Steel, 410ss, 304L, 316L) being considered for sCO 2 systems. Results from these tests are presented, including correlations between the probe measured corrosion rate to that for witness coupons of the same alloys.

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.

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.