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.

A new alloy design concept for creep- and corrosion-resistant, fully ferritic alloys was proposed for high-temperature structural applications in current/future fossil-fired power plants. The alloys, based on the Fe-30Cr-3Al (in weight percent) system with minor alloying additions of Nb, W, Si, Zr and/or Y, were designed for corrosion resistance though high Cr content, steam oxidation resistance through alumina-scale formation, and high-temperature creep performance through fine particle dispersion of Fe 2 (Nb,W)-type Laves phase in the BCC-Fe matrix. Theses alloys are targeted for use in harsh environments such as combustion and/or steam containing atmospheres at 700°C or greater. The alloys, consisting of Fe-30Cr-3Al-1Nb-6W with minor alloying additions, exhibited a successful combination of oxidation, corrosion, and creep resistances comparable or superior to those of commercially available heat resistant austenitic stainless steels. An optimized thermo-mechanical treatment combined with selected minor alloying additions resulted in a refined grain structure with high thermal stability even at 1200°C, which improved room-temperature ductility without sacrificing the creep performance. The mechanism of grain refinement in the alloy system is discussed.

This paper presents an overview of China’s electric power development and the National 700°C Ultra-Supercritical (USC) Coal-Fired Power Generation Technology Innovation Consortium. Besides, the R&D plan and latest progress of China 700°C USC coal-fired power generation technology is also introduced in this paper.

Ultrasupercritical (USC) steam boiler and heat recovery steam generator (HRSG) technology is constantly evolving to improve efficiency and reduce emissions. Currently, temperatures are pushing beyond the capabilities of even the most advanced ferritic steels with some applications requiring nickel-based superalloys. Cost-effective design of these systems requires the application of a variety of alloys representing a range of cost/property trade-offs. CF8C-Plus is a cast austenitic stainless steel recently developed for application in high temperatures similar to those in power plants (600 - 900 °C) with creep strength comparable to several superalloys. This makes it an attractive alternative for those expensive alloys. EPRI, with assistance from PCC subsidiaries Special Metals and Wyman Gordon Pipes and Fittings, has produced and characterized two pipe extrusions nominally 5.25 inch OD x 0.5 inch wall thickness and 6 inch OD x 0.75 inch wall (13.3 x 1.3 cm and 15.2 x 1.9 cm), each about 1000 lbs, to continue to assess the feasibility of using a wrought version of the alloy in power piping and tubing applications. The mechanical properties from these extrusions show performance in the same population as earlier forging trials demonstrating capability exceeding several austenitic stainless steels common to the industry. Creep-rupture performance in these extrusions continues to be competitive with nickel-based superalloys.

For raising thermal efficiency and decreasing CO 2 emission, China had constructed the first 600°C ultra-supercritical(USC) fossil power plant in 2006. Now more than a hundred 600°C, 1000MW USC electric power units have been put in service. Recently, China has also developed 620°C USC power units and some of them have been put in service already. Meanwhile, more than fifty 620°C USC boilers will be produced by various China boiler companies. The austenitic steels TP347H, Super304H and HR3C are routinely used for 600°C USC boilers. Among these steels, a big amount of Super304H has been used for boiler superheater/reheater components application. However, Super304H is characterized by good stress-rupture strength but poor corrosion/oxidation resistance. On the other side, HR3C is characterized by very good corrosion/oxidation resistance but lower stress-rupture strength than Super304H. Now, the China 620°C USC project needs a new austenitic heat resisting steel with high stress-rupture strength and good corrosion/oxidation resistance to fulfill the superheater/reheater tube components application requirement. A new austenitic heat resisting steel SP2215 is based on 22Cr-15Ni with certain amount of Cu and also Nb and N for multiphase precipitation (MX, Cu-rich phase, NbCrN) strengthening in Fe-Cr-Ni austenitic matrix and M 23 C 6 carbide precipitation at grain boundaries. This SP2215 new austenitic steel is characterized by high stress-rupture strength (650°C, 105h>130MPa) and good corrosion/oxidation resistance. SP2215 austenitic steel has been commercially produced in tube product form. This SP2215 new austenitic heat-resisting steel is recommended to be used as superheater/reheater components for 620°C USC boiler application.

Inconel Filler Metal 72 (FM 72) and Incoclad 671/800H co-extruded tubing have been successfully used for over 20 years to protect boiler tubing from high-temperature degradation. A newer alloy, FM 72M, offers superior weldability and the lowest corrosion rate in simulated low NOx environments. Both FM 72 and 72M show promise in addressing challenges like circumferential cracking and corrosion fatigue in waterwall tubing overlays. Additionally, 72M’s superior wear resistance makes it ideal for replacing erosion shields in superheater and reheater tubing. Beyond improved protection, these alloys exhibit increased hardness and thermal conductivity over time, leading to reduced temperature difference across the tube wall and consequently, enhanced boiler efficiency and lower maintenance costs. This paper discusses the historical selection of optimal alloys for waterwall and upper boiler tubing overlays, analyzes past failure mechanisms, and highlights the key properties of successful choices like FM 72 and 72M.

Energy requirements and environmental concerns have promoted a development in higher-efficiency coal fired power technologies. Advanced ultra-super critical power plant with an efficiency of higher than 50% is the target in the near future. The materials to be used due to the tougher environments become therefore critical issues. This paper provides a review on a newly developed advanced high strength heat resistant austenitic stainless steel, Sandvik Sanicro 25, for this purpose. The material shows good resistance to steam oxidation and flue gas corrosion, and has higher creep rupture strength than any other austenitic stainless steels available today, and has recently obtained two AMSE code cases. This makes it an interesting option in higher pressures/temperature applications. In this paper, the material development, structure stability, creep strength, steam oxidation and hot corrosion behaviors, fabricability and weldability of this alloy have been discussed. The conclusion is that the Sanicro 25 is a potential candidate for superheaters and reheaters in higher-efficiency coal fired boilers i.e. for applications seeing up to 700°C material temperature.

Haynes 282 alloy is a relatively new Ni-based superalloy that is being considered for advanced ultrasupercritical (A-USC) steam turbine casings for steam temperatures up to 760°C. Weld properties are important for the turbine casing application, so block ingots of Haynes 282 alloy were cast for properties studies. Good, sound welds were produced using Haynes 282 weld-wire and a hot gas-tungsten-arc welding method, and tensile and creep-rupture properties were measured on cross-weld specimens. In the fully heat-treated condition (solution annealed + aged), the tensile properties of the welded specimens compare well with as-cast material. In the fully heat-treated condition the creep-rupture life and ductility at 750°C/250MPa and 800°C/200MPa of the cross-weld specimens are similar to the as-cast base metal, and repeat creep tests show even longer rupture life for the welds. However, without heat-treatment or with only the precipitate age-hardening heat-treatment, the welds have only about half the rupture life and much lower creep ductility than the as-cast base metal. These good properties of weldments are positive results for advancing the use of cast Haynes 282 alloy for the A-USC steam turbine casing application.

Inconel alloy 740H is designated for boiler sueprheater/reheater tubes and main steam/header pipes application of advanced ultra-supercritical (A-USC) power plant at operating temperatures above 750°C. Microstructure evolution and precipitates stability in the samples of alloy 740H after creep-rupture test at 750°C, 800°C and 850°C were characterized in this paper by scanning electron microscopy, transmission electron microscopy and chemical phase analysis in details. The phase compositions of alloy 740H were also calculated by thermodynamic calculation. The research results indicate that the microstructure of this alloy keeps good thermal stability during creep-rupture test at 750°C, 800°C and 850°C. The precipitates are MC, M 23 C 6 and γ′ during creep-rupture test. The temperature of creep test has an important effect on the growth rate of γ′ phase. No harmful and brittle σ phase was found and also no γ′ to η transformation happened during creep. Thermodynamic calculations reveal almost all the major phases and their stable temperatures, fractions and compositions in the alloy. The calculated results of phase compositions are consistent with the results of chemical phase analysis. In brief, except of coarsening of γ′, Inconel alloy 740H maintains the very good structure stability at temperatures between 750°C and 850°C.

To achieve the necessary creep-rupture lifetimes at the temperatures and pressures associated with advanced ultrasupercritical (A-USC) steam conditions (100,000 h at 100 MPa and 760°C), precipitation-strengthened nickel-based alloys are required for the superheater and reheater tubing in A-USC boilers. Two alloys were considered to have potential for this application: Inconel 740 and Haynes 282 alloy. In support of this application, creep-rupture testing of several heats of Inconel 740 was conducted over a range of temperatures and stresses to develop confidence in qualitatively predicting creep lifetimes under conditions relevant to A-USC steam conditions, with the longest rupture times exceeding 30,000 h. For comparison, the creep-rupture behavior of Haynes 282 alloy was mapped as a function of temperature and stress, but with a significantly smaller dataset. Only a small difference in creep-rupture results between Inconel 740 and Inconel 740H was found although the latter alloy showed significantly greater resistance to η phase formation during testing. Little effect of prior aging treatments (for setting the γ′ precipitate structure) on creep-rupture behavior was observed. Results from a modified power law analysis showed that, while both Inconel 740 and Haynes 282 are projected to meet the A-USC lifetime requirements, the latter offered the potential for better long-term creep resistance.

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.

The presented work summarizes the results of more than 10 years of research at TU Graz and TU Chemnitz and partners on a martensitic boron and nitrogen stabilized 9Cr3W3Co (MARBN) steel grade. The design philosophy of MARBN steels is presented and critical issues regarding boron and nitrogen balance are discussed. Microstructural characterization of two different laboratory heats, is presented and efforts in European projects towards an upscaling of melts are presented. Base material creep testing data at 650 °C up to 50.000 hours is presented and assessed to commercial alloys such as ASTM grades P91 and P92. An increase of creep rupture stress of more than +20% was recorded. Oxidation tests in steam at 650°C revealed an anomalous response of the material. Several specimens exhibited excellent oxidation resistance commonly only seen for grades of higher chromium content. The anomalous oxidation behaviour is identified and discussed, although the causes remain yet unclear. Results of manufacturing, characterization and testing of different MARBN welds, including gas-tungsten-arc-, gas-metal-arc-, friction stir and electron beam welds reveal a microstructure memory effect in the heat affected zone, so that no uniform fine-grained zone is present. The behaviour of crosswelds during long-term creep testing at 650 °C up to more than 32.000 hours is assessed and the susceptibility to Type IV cracking is discussed. The manuscript summarizes research of more than 10 years, presents current research activities on MARBN and describes open questions for an alloy identified as a promising martensitic steel grade for elevated temperature components.

In order to evaluate long term creep strength of modified 9Cr ferritic steels, the system free energy of creep ruptured specimens at both 650 and 700 °C is evaluated as the sum of chemical free energy, strain energy and surface energy, which are obtained by a series of experiments, i.e., chemical analysis using extracted residues, X-ray diffraction, and scanning transmission electron microscopy. Change ratio of the system free energy and creep stress showed the relationship with one master curve irrespective of creep conditions, indicating that the steel ruptures when the applied stress exceeds a limited stress depending on the microstructural state expressed by the change ratio of system free energy. Furthermore, it was found that dominant factor of the change ratio was the chemical free energy change. On the basis of these results, long term creep strength of the steel was evaluated at 700 °C, for example, 19MPa at 700 °C after 10 5 h. It is concluded that long term creep strength of modified 9Cr ferritic steels can be predicted by the system free energy concept using the ruptured specimens with various creep conditions.

Current demands of the power generation market require components with improved materials properties. The focus is not only on the higher operation temperatures and pressures but also more frequent cycling to accommodate the energy produced from renewable sources. Following the successful developments of steels within the COST 501, 522 and 536 programmes, further advances are being researched. As nickel superalloys remain an expensive option for coal power plants, there is a significant drive for improvements of 9-12% Cr steels to meet new demands. The most promising of the potential candidates identified for 650°C application is MarBN steel (9Cr-3Co-3W-V-Nb). This paper reviews the current state of European developments on MarBN steel. Work on this alloy has been carried out for the last 5 years. Initial projects focused on development of the cast components. UK IMPACT and following INMAP projects successfully demonstrated manufacturing capabilities of large casting components. More recent collaborations aim to develop full-size boiler components and large rotor forgings as well as further examine the properties in the operating conditions (i.e. corrosion and oxidation resistance, creep-fatigue behaviour). Additionally significant focus is placed on modelling the behaviour of MarBN components, in terms of both microstructural changes and the resulting properties.

This overview paper contains a part of structure stability study on advanced austenitic heat-resisting steels (TP347H, Super304H and HR3C) and Ni-base superalloys (Nimonic80A, Waspaloy and Inconel740/740H) for 600-700°C A-USC fossil power plant application from a long-term joint project among companies, research institutes and university in China. The long time structure stability of these advanced austenitic steel TP347H, Super304H, HR3C in the temperature range of 650-700 °C and Ni-base superalloys Nimonic80A, Waspaloy and Inconel740/740H in the temperature range of 600-800°C till 10,000h have been detailed studied in this paper.

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.

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.

SMST is producing Ni alloy Boiler tubes since more than 10 years with application in several test loops and R&D programs. This paper will give an overview about the experience with the common grades A617 as well as C263 plus some additional information on the new developed austenitic material “Power Austenite MoW”.

An innovative additively manufactured gradient composite transition joint (AM-GCTJ) has been designed to join dissimilar metals, to address the pressing issue of premature failure observed in conventional dissimilar metal welds (DMWs) when subjected to increased cyclic operating conditions of fossil fuel power plants. The transition design, guided by computational modeling, developed a gradient composite material distribution, facilitating a smooth transition in material volume fraction and physical properties between different alloys. This innovative design seeks to alleviate structural challenges arising from distinct material properties, including high thermal stress and potential cracking issues resulting from the thermal expansion mismatch typically observed in conventional DMWs. In this study, we investigated the creep properties of transition joints comprising Grade 91 steel and 304 stainless steel through a combination of simulations and creep testing experiments. The implementation of a gradient composite design in the plate transition joint resulted in a significant enhancement of creep resistance when compared to the baseline conventional DMW. For instance, the creep rupture life of the transition joint was improved by > 400% in a wide range of temperature and stress testing conditions. Meanwhile, the failure location shifted to the base material of Grade 91 steel. Such enhancement can be primarily attributed to the strong mechanical constraint facilitated by the gradient composite design, which effectively reduced the stresses on the less creep-resistant alloy in the transition zone. Beyond examining plate joints, it is crucial to assess the deformation response of tubular transition joints under pressure loading and transient temperature conditions to substantiate and demonstrate the effectiveness of the design. The simulation results affirm that the tubular transition joint demonstrates superior resistance compared to its counterpart DMW when subjected to multiaxial stresses in tubular structures. In addition, optimization of the transition joint’s geometry dimensions has been conducted to diminish the accumulated deformation and enhance the service life. Lastly, the scalability and potential of the innovative transition joints for large-diameter pipe applications are addressed.

Stress corrosion cracking (SCC) is a potential risk in structural steels used for steam boilers. To investigate the effect of dissolved oxygen (DO) on SCC susceptibility, three steels, T23, T24 and T91 were annealed at 1065°C and then quenched to create a susceptible microstructure and then exposed in a Jones test to stagnant and circulating water at 200°C with varying DO levels. The results indicated that among the tested steels, the SCC susceptibility was highest in T91 but lowest in T23 which did not exhibit crack initiation with 100 ppb DO. T24 showed no cracking with 50 ppb DO but cracked with 100 ppb DO under these conditions. Based on these results, the next planned step is to monitor crack growth in-situ and determine a critical DO content for each material.