Alumina-forming austenitic stainless steels (AFAs) are potential materials for boiler/steam turbine applications in next generation fossil fuel power plants. They display a combination of good high temperature creep strength, excellent oxidation resistance and low cost. A recently-developed AFA alloy based on Fe-14Cr-32Ni-3Nb-3Al-2Ti (wt.%) shows better creep performance than a commercially-available Fe-based superalloy. In this paper we used scanning electron microscopy and transmission electron microscopy to study the fracture surfaces and cracking behavior in relation to the precipitates present in creep failure samples of this alloy tested at either 750°C/100 MPa or 700°C/170 MPa. It was found that most cracks are formed along the grain boundaries with precipitate-free zones beside the grain boundaries potentially providing the path for propagation of cracks.

Diffusion aluminide coatings have been evaluated as a strategy for improving the oxidation resistance of austenitic and ferritic-martensitic (FM) steels, particularly in the presence of steam or water vapor. The objective was to evaluate the strengths and weaknesses of these coatings and quantify their performance and lifetime. Long-term diffusion and oxidation experiments were conducted to study the behavior of various model diffusion coatings and produce a better data set for lifetime predictions. The key findings are that (1) thin coatings (<50μm) with relatively low Al contents appear to be more effective because they avoid high thermal expansion intermetallic phases and have less strain energy to nucleate a crack; and (2) the low Al reservoir in a thin coating and the loss of Al due to interdiffusion are not problematic because the low service temperatures of FM steels (<600°C) and, for austenitic steels at higher temperatures, the phase boundary between the ferritic coating-austenitic substrate inhibits Al interdiffusion. Unresolved issues center on the effect of the coating on the mechanical properties of the substrate including the reaction of N in the alloy with Al.

Because of the problems experienced with steam-side oxidation in commercial power plants, there has been continuing interest in better understanding the steam oxidation behavior of creep strength enhanced ferritic steels such as grades 23, 24 and 91 as well as 300-series stainless steels such as 347H and 304H. Analysis of field-exposed tubes has provided information on the oxidation reaction products but relatively few specimens are available and there is limited information about the kinetics. Specimens have included tube sections with a shot peened surface, a treatment that is now widely used for austenitic boiler tubes. To complement this information, additional laboratory studies have been conducted in 1bar steam at 600°-650°C on coupons cut from conventional and shot-peened tubing. Exposures of 1-15 kh provide some information on the steam oxidation kinetics for the various alloys classes. While shot-peened type 304H retained its beneficial effect on oxidation resistance past 10,000 h at 600° and 625°C, the benefit appeared to decline after similar exposures at 650°C.

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.

In this study, the role of minor alloying additions in 347H stainless steels (UNS34709, ASTM A240/240M) on creep-rupture properties at 650-750°C and microstructure evolution during isothermal exposure at 750°C has been investigated, aiming to provide the experimental dataset as boundary conditions of physics-based modeling for material/component life prediction. Four different 347H heats containing various amounts of boron and nitrogen additions were prepared and evaluated. The combined additions of B and N are found to stabilize the strengthening secondary M 23 C 6 carbides and retarding the transition from M 23 C 6 to sigma phase precipitates during thermal exposure. The observed kinetics of microstructure evolution reasonably explains the improvement of creep-rupture properties of 347H stainless steels with the B and N additions.

Traditional laboratory steam experiments are conducted at ambient pressure with water of variable chemistry. In order to better understand the effect of steam pressure and water chemistry, a new recirculating, controlled chemistry water loop with a 650°C autoclave was constructed. The initial experiments included two different water chemistries at 550° and 650°C. Two 500-h cycles were performed using oxygenated (OT, pH ~9 and ~100 ppb O 2 ) or all-volatile treated (AVT, pH ~9 and <10 ppb O 2 ) water conditions at each temperature. Coupons exposed included Fe-(9-11)%Cr and conventional and advanced austenitic steels as well as shot peened type 304H stainless steel. Compared to ambient steam exposures, the oxides formed after 1,000 h were similar in thickness for each of the alloy classes but appeared to have a different microstructure, particularly for the outer Fe-rich layer. An initial attempt was made to quantify the scale adhesion in the two environments.

Most effective method to increase the boiler efficiency and decrease emissions is to increase the steam temperature of modern coal-fired power plants. The increase in the steam temperature of the AUSC power plants will require higher grade heat-resistant materials to support the long-term safety and service reliability of power plants. The corrosion resistance of alloys is one of the most important factors for the application in AUSC power plants.

Creep-resistant austenitic stainless steels are known to be the potential candidate materials for use as super- and re-heater tubes in ultra-super critical (USC) power plants. Among them, ASTM A213/A213M S30432, a novel 18-8 stainless steel (18Cr- 9Ni-3Cu-Nb-N), has attracted considerable attention from electric industry due to its combined lower cost and more excellent performance in contrast to traditional TP347H steel. More than 10 years of service in Japan laid a solid foundation for the steel being selectable USC boiler materials. Steels of S30432 have been recently developed in China during the past few years. This paper presents the evaluation results of S30432 tubes manufactured by four steel plants in China as well as Sumitomo super304H tubes for comparison. A detailed microstructural analysis of the tubes has been performed by using optical and electron microscope, and mechanical properties of the tubes have been evaluated using hardness testing as well as tensile testing up to 700°C. It was found that the impurity elements, nonmetallic inclusions and grain size of the S30432 tubes were well controlled. TEM observation revealed the microstructural changes for a selected batch of S30432 specimens in condition of hot rolled material, as-extruded tube, solution treated tube and 650°C/1000h aged tube. Most attention was paid to the morphology and distribution of precipitates in the microstructure which should be responsible for the enhanced performance of the steel. Although the hardness of all the evaluated tubes was measured to be similar, they showed more or less differences in tensile properties between each other. Creep rupture testing is still in progress, and the steel might exhibit excellent long-term creep rupture strength at 650°C as was predicted from the currently available testing results.

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.

Nickel-base alloys were exposed to flowing supercritical CO 2 (P = 20MPa) at temperatures of 700 to 1000°C for up to 1000 h. For comparison, 316L stainless steel was similarly exposed at 650°C. To simulate likely service conditions, tubular samples of each alloy were internally pressurised by flowing CO 2 , inducing hoop stresses up to 35 MPa in the tube walls. Materials tested were Haynes alloys 188, 230 and 282, plus HR120 and HR160. These alloys developed chromia scales and, to different extents, an internal oxidation zone. In addition, chromium-rich carbides precipitated within the alloys. Air aging experiments enabled a distinction between carburisation reactions and carbide precipitation as a result of alloy equilibration. The stainless steel was much less resistant to CO 2 attack, rapidly entering breakaway corrosion, developing an external iron-rich oxide scale and internal carburisation. Results are discussed with reference to alloy chromium diffusion and carbon permeation of oxide scales.

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 effect of gas impurities on corrosion behavior of candidate Fe- and Ni-base alloys (SS 316LN, Alloy 800HT, Alloy 600) in high temperature CO 2 environment was investigated in consideration of actual S-CO 2 cycle applications. Preliminary testing in research and industrial grade S-CO 2 at 600 °C (20 MPa) for 1000 h showed that oxidation rates were significantly reduced in industrial-grade S-CO 2 environment. Meanwhile, controlled tests with individual impurity additions such as CH 4 , CO, and O 2 in research-grade CO 2 were performed. The results indicated that CH 4 and CO additions did not seem to significantly affect oxidation rates. On the other hand, O 2 addition resulted in lower weight gains for all alloys, suggesting that O 2 may be primarily affecting corrosion behavior.

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.

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.

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.

High-performance Ferritic (HiperFer) steels represent a promising materials innovation for next-generation thermal energy conversion systems, particularly in cyclically operating applications like concentrating solar thermal plants and heat storage power plants (Carnot batteries), where current market adoption is hindered by the lack of cost-effective, high-performance materials. HiperFer steels demonstrate superior fatigue resistance, creep strength, and corrosion resistance compared to conventional ferritic-martensitic 9-12 Cr steels and some austenitic stainless steels, making them potentially transformative for future energy technologies. This paper examines the microstructural mechanisms underlying HiperFer’s enhanced fatigue resistance in both short and long crack propagation, while also presenting current findings on salt corrosion properties and exploring potential alloying improvements for fusion reactor applications, highlighting the broad technical relevance of these innovative materials.

The A-USC technology is still under development due to limited number of materials complying with the requirements of high creep strength and high performance in highly aggressive corrosion environments. Development of power plant in much higher temperatures than A-USC is currently impossible due to the materials limitation. Currently, nickel-based superalloys besides advanced austenitic steels are the viable candidates for some of the A-USC components in the boiler, turbine, and piping systems due to higher strength and improved corrosion resistance than standard ferritic or austenitic stainless steels. The paper, presents the study performed at 800 °C for 3000 hours on 3 advanced austenitic steels; 309S, 310S and HR3C with higher than 20 Cr wt% content and 4 Ni-based alloys including: two solid-solution strengthened alloys (Haynes 230), 617 alloy and two (γ’) gamma - prime strengthened materials (263 alloy and Haynes 282). The high temperature oxidation tests were performed in water to steam close loop system, the samples were investigated analytically prior and after exposures using Scanning Electron Microscopy (SEM) coupled with Energy Dispersive Spectrometry (EDS), and X-Ray Diffractometer (XRD). Mass change data have been examined every 250 hours.

Hitachi and Hitachi Metals have developed low thermal expansion Ni-base superalloy, Ni-20Cr-10Mo-1.2Al-1.6Ti alloy (USC141) for use as A-USC steam turbine material. The approximate 10 5 h creep rupture strength at 740° C is 100MPa, so USC141 can be expected to apply for blades and bolts. Now we have been studying to get better creep properties by microstructure controlling such as grain size or grain boundary morphology. In addition, the segregation test of USC141 shows good Freckle tendencies, it means that it would be easy to make a large ingot which could be used as rotors or pipes. From these calculation results, we have been tried to make an 850mmϕ ESR ingot of USC141.

Contrary to expectations, long-term performance of creep stress enhanced ferritic steels (CSEF) falls short of predictions based on short-term data. This discrepancy is attributed to the formation and growth of creep voids, leading to reduced ductility. This study investigates cavities in creep-tested P92 steel, revealing an association with large ceramic particles (1-2 μm) in standard samples. Three distinct particle compositions were identified: boron nitride (BN), manganese sulfide, and γ-Al 2 O 3 . Statistical analysis showed a strong correlation between BN particles and cavity formation. Using a 3D “slice and view” technique with a focused ion beam/field emission gun scanning electron microscope (FIB-FEGSEM), the study revealed irregular shapes for both cavities and associated particles. Furthermore, analysis of the head-gauge transition area (lower stress exposure) showed small cavities near BN particles, suggesting preferential nucleation on these hard, irregular features. These findings strongly support the hypothesis that BN particles play a key role in cavity nucleation, impacting the long-term performance of P92 steel.

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.