Steels have a proven track record of safe operation in steam power plants for decades. Interest in developing supercritical CO 2 power cycles as a more efficient and sustainable alternative to steam cycles has driven a need to understand steel performance in these new environments. In particular, the potential of the high temperature CO 2 environment to influence the creep behavior of the steel must be determined. Prior research on this topic between the 1960s and 1980s found conflicting conclusions, but nevertheless raised the possibility that carburization during CO 2 exposure may strongly affect the creep behavior. This raises concerns particularly for thin-sectioned components such as compact heat exchangers, where even small rates of carburization can become problematic over long operating lifetimes. To shed light on this issue, this research investigates the creep behavior of austenitic stainless steel 347H and 309H (a higher Cr alternative) at 650°C. Specimens of 0.5, 1.0, and 2.0 mm thickness were tested to further assess the effect of steel thickness. Both steels show a reduction in creep life in CO 2 relative to air, with 309H showing slightly better performance than 374H. Analysis is ongoing to determine the reason for degraded creep properties.

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.

A FeCrMnNi concentrated solid-solution alloy was irradiated with a 2 MeV proton beam up to 1 dpa and 6 dpa at temperatures of 400 °C and 600 °C. The microstructural changes induced by irradiation were characterized using Transmission Electron Microscopy (TEM). In samples irradiated at 400 °C, Frank loops were the predominant form of lattice damage at 1 dpa, whereas small defect clusters were more prevalent at 6 dpa. For the sample irradiated to 1 dpa at 600 °C, both Frank loops and small defect clusters were present in similar density. Nanoindentation was employed to assess the changes in mechanical properties (hardness) post-irradiation, revealing significant hardening in all irradiated samples. The results indicated that the hardening effect began to saturate at 1 dpa or earlier. Additionally, nanoindentation creep tests with a 1200-second dwell period produced stress exponents comparable to those obtained from conventional creep testing. The findings suggest a shift in the deformation mechanism from dislocation glide to dislocation climb in the sample irradiated to 6 dpa at 400 °C.

A novel salt-bath nitrocarburizing process recently developed forms a lithium-iron compound-oxide layer on the surface of steel in concurrence with a nitride layer by adding lithium ions to the molten salt. This process has already been successfully applied to mass-produced products. However, the microstructure and its formation process of the surface layer in alloyed steels during the nitrocarburizing process have not yet been fully understood. In this study, we focus on the effect of Si and Cr, which are included in a common die steel, on the microstructure of an oxide layer of a nitrocarburized alloy. The alloys used in this study are Fe-0.4wt%C, Fe-0.4wt%C-2.0wt%Si, and Fe-0.4wt%C-2.0wt%Cr. These alloys were arc melted into button ingots under an Ar atmosphere. The ingots were annealed at 1123 K for 1.0 h, followed by air cooling and double tempering at 873 K, similar to the heat treatments employed to hot-die steels. Salt-bath nitrocarburizing was carried out at 823 K for 0.1-10 h. The microstructures of the cross-sectional surface layers of the samples were examined using an optical microscope and FE-SEM. Elemental mapping as well as phase identification of the surface layers were done by EDS, XRD, and GD-OES. In the Fe-C binary alloy, a thin continuous oxide layer of α-LiFeθ 2 formed first on the outermost surface, and a thick iron nitride layer developed underneath the oxide layer, with aligned oxide particles along the grain boundaries of the nitrogen compound layer. In the case of Si addition, the outermost oxide layer became thinner and an additional oxide layer consisting of α-LiFeθ 2 and (Li,Fe) 3 Siθ 4 formed between the outer oxide layer and nitrogen compound layer, and the formation of the oxide particles in the nitrogen compound layer was fully suppressed. In the case of Cr addition, internal oxide particles formed in the nitrogen compound layer, similar to those in the binary steel, although an continuous oxide layer of CrfN,O) formed in between those layers. On the basis of these results, the inner oxide layer formed with Si addition contributes to improving the frictional wear characteristics in die steels.

Both of high pressure main throttle valves and one governing valves were jammed during the cold start of steam turbine served for 8541 hours at 600 °C in an ultra supercritical power plant. Other potential failure mechanisms were ruled out through a process of elimination, such as low oil pressure of digital electro-hydraulic control system, jam of orifice in the hydraulic servo-motor, and the severe bending of valve stem. The root cause was found to be oxide scales plugged in clearances between the valve disc and its bushing. These oxide scales are about 100~200 μm in thickness while the valve clearances are about 210~460 μm at room temperature. These oxide scales are mainly composed of Fe 3 O 4 and Fe 2 O 3 with other tiny phases. Both of valve disc and its bushing were treated with surface nitriding in order to improve its fatigue resistance, which unexpectedly reduces the steam oxidation resistance. On the other hand, significant fluctuation of valve inner wall temperature during operation accelerated the exfoliation of oxide scales, and the absence of full stroke test induced the gradual accumulation of scales in valve clearances. In light of the steam valve jam mechanism in the present case, treatments in aspects of operation and resistance to steam oxidation are recommended.

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.

The efficiency of power plants is depending on the steam temperature and/or the steam pressure. Efficiency increasing from 35% to 42-45% require increasing of the steam temperature over 600°C and the pressure over 26 MPa. According to the designer opinion it is not profitable to use classical low alloy creep resistant steels 16Mo3, 13CrMo4-5 or 10CrMo9-10 for membrane waterwall construction for these service condition. New modified low alloy creep resistance T23 and T24 (7CrMoVTiB10-10) steels were developed for membrane waterwalls. Welding of these steels with small thickness (around 6.3 mm) should be enabled without preheating and post weld heat treatment (PWHT) due to the lower carbon content below 0.1%. High creep rupture strength (CRS) values are achieved by Ti, N and B elements alloyed to T24 steel. The original expectation that the welding small thickness without preheating was early overcome and was wrong. According to the present experience the T24 steel is welded with preheating at 150-250°C depending on the wall thickness and welded joint toughness in order to achieve required hardness and impact toughness values. Opinions on the T24 welded joints post weld heat treatment (PWHT) requirements are still inconsistent. Especially the membrane waterwalls of the supercritical power plants are still produced without PWHT.

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.

High nitrogen steel was manufactured by solid state nitriding and Laminate- rolling at laboratory to study the nitride morphology and creep properties through the TEM, EPMA and creep strain test. Nitriding made the nitride dispersing steels possible. Solid state nitriding of thin plates and those laminate rolling enabled the high nitrogen containing thick plate steel. Precipitated coarse nitrides during the nitriding resolved by normalizing and re-precipitated by tempering finely. Needle type VN was detected in V containing high nitrogen steels. Its coherency seems to affect the creep strength significantly. V precipitated steels indicated the higher creep strength than the steels without VN precipitation. Thermodynamically stable precipitates like VN increases the creep rupture strength. Ti and Zr containing high nitrogen steels also will be evaluated and discussed by the presentation.

The creep enhanced low alloy steel with 2.25Cr-1.6W-V-Nb (HCM2S; Gr.23, ASME CC2199) has been originally developed by Mitsubishi Heavy Industries, Ltd. and Sumitomo Metal Industries, Ltd. The steel tubes and pipe (T23/P23) are now widely used for fossil fired power plants all over the world. Recently, the chemical composition requirements for ASME Code of the steel have been changed and a new Code Case 2199-4 has been issued with the additional restriction regarding Ti, B, N and Ni, and the Ti/N ratio incorporated. In this study, the effects of additional elements of Ti, N and B on the mechanical properties and microstructure of T23/P23 steels have been evaluated. It is found that N decreases the hardenability of the steel by forming BN type nitride and thus consuming the effective B, which is a key element for hardening of the steel. The addition of Ti, on the other hand, enhances the hardenability of the steel by precipitating TiN and thus increasing the effective B. It is also found that too much addition of Ti degrades the Charpy impact property and creep ductility of the steel to a great extent. This phenomenon might affect the steel's long-term creep rupture properties, although a steel with the original chemical composition has demonstrated high creep strength at temperatures up to 600°C for more than 110,000 h.

In advanced ultra-supercritical (A-USC) power plants, which operate at steam temperatures of 700 °C or higher, there is a need to replace 9 to 12Cr martensitic steels with high-strength nickel-base superalloys or austenitic steels for components exposed to the highest temperatures. However, due to the high cost of nickel-base superalloys, it is desirable to use 9 to 12% Cr martensitic steels for components exposed to slightly lower temperatures, ideally expanding their use up to 650 °C. Key challenges in developing ferritic steels for 650 °C USC boilers include enhancing oxidation resistance and long-term creep rupture strength, particularly in welded joints where resistance to Type IV cracking is critical for constructing thick-section boiler components. The current research aims to investigate the creep deformation behavior and microstructure evolution during creep for base metals and heat-affected-zone (HAZ) simulated specimens of tempered martensitic 9Cr steels, including 9Cr-boron steel and conventional steels like grade 91 and 92. The study discusses the creep strengthening mechanisms and factors influencing creep life. It proposes an alloy design strategy that combines boron strengthening and MX nitride strengthening, avoiding the formation of boron nitrides during normalizing heat treatment, to improve the creep strength of both base metal and welded joints.