In order to study the effect of precipitation strengthening by MX precipitates on the restriction of microstructure degradation in 9 mass% Cr ferritic heat-resistant steels, V, Nb additioned model steels were evaluated by microstructure analysis through TEM and EBSD with reference to the creep test and creep interrupting test. VN precipitation increased the creep strength if the content was higher than 0.02%. Simultaneous addition of Nb and V in the specimen resulted in the complex NbC-VN precipitates even in the as-heat-treated specimens. The coherent and fine-needle-type VN was also detected in the steel. These precipitates are expected to increase the creep strength according to the creep strain curves. V variation up to 0.02% did not affect the crystallographic character of the grain boundary in the as-heat-treated specimens. Nb variation affected the crystallographic character of the grain boundary significantly because of the grain refinement effect of NbC. VN precipitation during the creep test restricted the crystallographic misorientation-angle-profile degradation. Integrating all intragranular precipitates, VN, restricts the crystallographic degradation significantly. The long-term creep test results and the precise precipitation analysis will be disclosed by the presentation.

To save fossil fuel resources and to reduce CO 2 emissions, considerable effort has been directed toward researching and developing heat-resistant materials that can help in improving the energy efficiency of thermal power plants by increasing their operational temperature and pressure conditions. Instead of conventional 9-12Cr ferritic heat-resistant steels with a tempered martensitic microstructure, we developed “Precipitation Strengthened 15Cr Ferritic Steel” based on a new material design concept: a solid-solution treated ferrite matrix strengthened by precipitates. Creep tests for 15Cr-1Mo-6W-3Co-V-Nb steels with ferrite matrix strengthened by a mainly Laves phase (Fe 2 W) showed that the creep strengths of 15Cr ferritic steel at temperatures ranging from 923 K to 1023 K were twice as high as those of conventional 9Cr ferric heat-resistant steel. 15Cr steels have higher steam oxidation resistance than that of conventional steel in the same temperature range as the creep tests. Thus, the new material design concept of heat-resistant steel pro- vides improved creep strength and steam oxidation resistance. We are attempting to determine the optimum compositions, especially that of carbon, in order to improve the high-temperature creep strength.

700°C advanced ultra-supercritical system and supercritical CO 2 turbine system are developed for high efficiency turbine systems for next generation. This study covered the feasibility of creep life assessment of γ’-Ni 3 (Al,Ti) precipitation strengthened Ni-based superalloy rotor material, TOS1X-2, a modified alloy of UNS N06617 for these systems, based on hardness measurement method. It was found that the hardness of TOS1X-2 was governed by the change in precipitation strengthening and strain hardening during creep. The clear relationship between hardness increase in crept portion and macroscopic creep strain was observed, suggesting that it might be possible to estimate the creep strain or initiation of acceleration from hardness measurement. Microstructure inhomogeneity and microstructure evolutions during creep especially focused on dispersion of creep strain were characterized by EBSD quantitative analysis. It was found that creep strain was accumulated along the grain boundary, while it was relatively absent in coarse grains with low Schmid factor of {111} <110> slip system in fcc structure. The upper limit of hardness scatter band is thought to be important, since it represents the local and critical creep damage of the alloy.

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.

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 Cr and W effect on the creep strength of ferritic steels were studied using the new strengthening hypothesis, precipitation strengthening mechanism, by examining the residual aligned precipitates consisting of W and Cr. In 2 mass% W-containing steel, the increase in Cr content up to 10 mass% resulted in the creep life extension. However, the Cr content higher than 11 mass% decreased the creep life. In 9 mass% Cr-containing steel, the increase in W content decreased the creep deformation rate with creep time. However, it also shortened the time to reach the minimum creep rate. Therefore, optimum Cr and W contents possibly resulted in the optimum alloy design. To understand the effect of W and Cr contents on creep strength, the precipitation strengthening hypothesis by the precipitates at the block boundary must be introduced. The residual aligned precipitation line is supposedly an effective obstacle for the dislocation motion at the interparticle space of the aligned precipitates. The new hypothesis will be activated after block boundary migration. It occurs during the acceleration creep period. On the basis of the hypothesis, creep strength was expressed as the summation of threshold creep stress and effective internal creep stress. According to the experimental data of microstructure recovery, the effective internal stress decreased with creep deformation and consequently vanished. In such cases, creep strength is decided only by the threshold stress of creep. Integrating all, we concluded that the creep deformation mechanism of ferritic creep-resistant steel possibly transits from the viscous dislocation gliding mode to the microstructure recovery driven type mode during the acceleration creep.

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.

Development of the advanced USC (A-USC) boiler technology has been promoted in recent years, which targets 700°C steam condition. HR6W (Ni-23Cr-7W-Ti-Nb-25Fe) and HR35 (Ni-30Cr-6W-Ti-15Fe) have been developed for A-USC boiler tubes and pipes. The former alloy is mainly strengthened by Fe 2 W type Laves phase. The latter one employs precipitation strengthening of α-Cr phase in addition to Laves phase. Characteristic alloy design of both alloys, which does not use precipitation strengthening of γ′ phase (Ni 3 Al), leads to superior ductility and resistance to stress-relaxation cracking. Stability of creep strength and microstructure has been confirmed by long-term creep rupture tests. The 100,000h average creep rupture strength of HR6W is 85MPa at 700C. That of HR35 is 126MPa at 700°C which is comparable with conventional Alloy617. Tubes of both alloys have been evaluated by the component test in Japanese national A-USC project with γ′ hardened Alloy617 and Alloy263. Detailed creep strength, deformation behavior and microstructural evolution of these alloys are described from the viewpoint of the difference in strengthening mechanisms. Capability of these alloys for A-USC boiler materials has been demonstrated by the component test in the commercial coal fired boiler as the part of the A-USC project.

Effects of Ni content and heat treatment condition on impact toughness and creep strength of precipitation strengthened 15Cr ferritic steels were investigated in order to discuss a possibility of improvement in both mechanical properties. Both creep strength and impact toughness of the developing steels were improved drastically by solid solution treatment with water quenching. However, an addition of Ni reduced the long-term creep strength of the steels, though Ni was effective in improvement in impact toughness. It was found that water quenching suppressed formation of coarse block type particles and precipitate free zones around them, and precipitation of plate type fine particles and thermal stability of them within ferrite phase were promoted by solid solution treatment with water quenching. However, martensite phase with sparsely distributed coarse block type particles were formed in the Ni added steels, and such microstructure reduced the precipitation strengthening effect slightly. On the other hand, increase in impact values of the steel indicated no relation to volume fraction of martensite phase. It was supposed that the impact toughness of ferrite phase itself was improved by solid solution treatment and addition of Ni.

Precipitation of Z-phase, Cr(V,Nb)N, is known to negatively affect creep properties of 9-12%Cr steels for power plant applications as it dissolves finely distributed MX particles, (V,Nb)N, especially in high Cr steels. As the Z-phase precipitates slowly as large particles, this causes a net drop in precipitation strengthening. Two model alloys containing 9 and 12%Cr, but otherwise having similar composition, were produced in order to quantify the difference in Z-phase precipitation speed at different Cr levels. The nitride precipitation behavior was followed at different temperatures using TEM and XRD, allowing for a quantification of the Z-phase precipitation. The Z-phase was found to precipitate 20-50 times faster in the 12%Cr steel compared to 9%Cr steel in the temperature range 600- 650°C. The transformation of MX into Z-phase was followed in a Ta containing alloy without V or Nb. In this alloy the Z-phase precipitates very quickly, and thus appears as finely distributed particles which have the same strengthening effect as MX particles. Investigations using atomic resolution microscopy showed how Cr diffuses from the matrix into the TaN MX particles and gradually transforms them both chemically and crystallographically into Z-phase CrTaN particles.

In this work, the effects of phosphorus addition on the creep properties and microstructural changes of wrought γ’-strengthened Ni-based superalloys (Haynes 282) were investigated, focusing on the effects of carbides precipitation. In an alloy with a phosphorus content of 8 ppm, precipitation of M 23 C 6 carbides was observed in both grain boundaries and the grain interior prior to the creep tests. Grain boundary coverage by carbide increased with phosphorus content up to approximately 30 ppm. On the other hand, the amount of M 23 C 6 in the grain interior decreased with phosphorus content. The results of the creep tests revealed the relationship between the time to rupture and the grain boundary coverage by carbides. The microstructure of the crept specimens showed the existence of misorientation at the vicinity of grain boundaries without carbides, as demonstrated via electron backscattered diffraction (EBSD) analysis. These results suggest that the observed improvement in the time to rupture is due to a grain-boundary precipitation strengthening mechanism caused by grain boundary carbides and that phosphorus content affects the precipitation behavior of M 23 C 6 carbides in the grain interior and grain boundaries. These behaviors were different between alloys with the single addition of phosphorus and alloys with the multiple addition of phosphorus and niobium.

Large heat-to-heat variation of creep rupture strength in weldments of mod.9Cr-1Mo steels was observed in the creep rupture tests conducted for two different heats at 600°C and 650°C. One heat showed consistently lower time-to-rupture than the other for 130-60MPa at 600°C. Detailed microstructural investigations revealed that the number density of precipitates in the weaker heat was remarkably lower than that associated with the stronger heat through most of the creep region. Accordingly, heat-to-heat variation of creep rupture strength was attributed to the difference in the precipitate strengthening effects throughout creep. Equilibrium calculation predicted that the smaller phase fraction of M 23 C 6 and VN precipitates due to the lower content of chromium and lower ratio of nitrogen/aluminum in the weaker heat. However, given that long-term creep rupture strength at 650°C converged for the two heats, the microstructure including precipitates may settle into a similar level for subsequent longer hours even at 600°C.

For future carbon neutral society, a novel thermal power generation system with no CO 2 emission and with extremely high thermal efficiency (~ 70 %) composed of the oxygen/hydrogen combustion gas turbine combined with steam turbine with the steam temperature of 700°C is needed. The key to realize the thermal power plant is in the developments of new wrought alloys applicable to both gas turbine and steam turbine components under higher temperature operation conditions. In the national project of JST-Mirai program, we have constructed an innovative Integrated Materials Design System , consisting of a series of mechanical property prediction modules (MPM) and microstructure design modules (MDM). Based on the design system, novel austenitic steels strengthened by Laves phase with an allowable stress higher than 100 MPa for 10 5 h at 700°C was developed for the stream turbine components. In addition, for gas turbine components, novel solid-solution type Ni-Cr-W superalloys were designed and found to exhibit superior creep life longer than 10 5 h under 10 MPa at 1000°C. The superior long-term creep strengths of these alloys are attributed to the “grain-boundary precipitation strengthening (GBPS)” effect due to C14 Fe 2 Nb Laves phase and bcc α 2 -W phase precipitated at the grain boundaries, respectively.

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.

Boron and nitride additions are emerging as a promising design concept for stabilizing the microstructure of creep-resistant martensitic high-chromium steels. This approach, known as MarBN steel (martensitic steel strengthened by boron and nitrogen), combines the benefits of solid solution strengthening from boron with precipitation strengthening from nitrides. However, initial welding trials revealed challenges in achieving a uniform fine-grained region in the heat-affected zone (HAZ), which is crucial for mitigating Type IV cracking and ensuring creep strength. Despite these initial hurdles, preliminary creep test results for welded joints have been encouraging. This study presents an improved MarBN steel formulation and its investigation through uniaxial creep tests. Base material and welded joints were subjected to creep tests at 650°C for up to 25,000 hours under varying stress levels. The analysis focused not only on the creep strength of both the base material and welded joints but also on the evolution of damage. Advanced techniques like synchrotron micro-tomography and electron backscatter diffraction were employed to understand the underlying creep damage mechanisms. By combining long-term creep testing data with 3D damage investigation using synchrotron micro-tomography, this work offers a novel perspective on the fundamental failure mechanisms occurring at elevated temperatures within the HAZ of welded joints in these advanced steels.

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.

The aspiration to deploy Nb-based alloys as viable upgrade for Ni-based superalloys is rooted in their potential for superior performance in high-temperature applications, such as rocket nozzles and next-generation turbines. However, realizing this goal requires overcoming formidable design hurdles, including achieving high specific strength, creep resistance, fatigue, and oxidation resistance at elevated temperatures, while preserving ductility at lower temperatures. Additionally, the requisite for alloy bond-coatings, to ensure compatibility with coating materials, further complicates the design process. QuesTek Innovations has its Integrated Computational Materials Engineering (ICME) technologies to design a superior performance high-temperature Nb-based superalloy based on solid solution and precipitation strengthening. Additionally, utilizing a statistical learning method from very limited available data, QuesTek engineers were able to establish physics-based material property models, enabling accurate predictions of equilibrium phase fraction, DBTT, and creep properties for multicomponent Nb alloys. With the proven Materials by Design methodology under the ICME framework, QuesTek successfully designed a novel Nb superalloy that met the stringent design requirements using its advanced ICMD materials modeling and design platform.

Recently, a γ’ precipitation strengthened Ni-base superalloy, USC141, was developed for 700°C class A-USC boiler tubes as well as turbine blades. In boiler tube application, the creep rupture strength of USC141 was much higher than that of Alloy617, and the 105 hours’ creep rupture strength of USC141 was estimated to be about 180MPa at 700°C. This is because fine γ’ particles precipitate in austenite grains and some kinds of intermetallic compounds and carbides precipitate along austenite grain boundaries during creep tests. Good coal ash corrosion resistance is also required for tubes at around 700°C. It is known that coal ash corrosion resistance depends on the contents of Cr and Mo in Ni-base superalloys. Therefore the effect of Cr and Mo contents in USC141 on coal ash corrosion resistance, tensile properties, and creep rupture strengths were investigated. As a result, the modified USC141 containing not less than 23% Cr and not more than 7% Mo showed better hot corrosion resistance than the original USC141. This modified alloy also showed almost the same mechanical properties as the original one. Furthermore the trial production of the modified USC141 tubes is now in progress.

This study investigates the role of grain-boundary precipitates in enhancing creep rupture strength of Ni-based alloys through analysis of Ni-15Cr-15Mo and Ni-15Cr-17Mo (at.%) model alloys. The investigation focused on the “Grain-boundary Precipitation Strengthening (GBPS)” effect from the thermally stable TCP phase, a phenomenon previously observed in Fe-Cr-Ni-Nb austenitic heat-resistant steels. Through multi-step heat treatments, specimens were prepared with varying grain boundary coverage ratios (ρ) of TCP P phase (oP56) and consistent grain-interior hardness from GCP Ni2(Cr, Mo) phase (oP6). In the 15 at.% Mo alloy, specimens with a higher coverage ratio (~80%) demonstrated significantly improved creep performance, achieving nearly four times longer rupture time (3793 h vs. 1090 h) at 300 MPa and 973 K compared to specimens with lower coverage (~35%). However, the 17 at.% Mo alloy showed unexpectedly lower performance despite high coverage ratios, attributed to preferential cavity formation at bare grain boundaries. These findings confirm that GBPS via thermally stable TCP phase effectively enhances creep properties in Ni-based alloys, with grain boundary coverage ratio being more crucial than intragranular precipitation density.

Haynes 282 is a great candidate to meet advanced ultra-super-critical (A-USC) steam conditions in modern coal-fired power plants. The standard 2-step aging treatment has been designed for optimizing microstructure therefore providing excellent mechanical properties. We studied an alternative, more economical, 1-step aging treatment and compared microstructure, tensile properties at 750˚C and deformation behavior. Moreover, three cooling rates from the solution temperature were studied to simulate large-scale components conditions. We found that as much as about 20% of fine spherical intragranular γ' particles were successfully precipitated in all cases. Their average size increased as the cooling rate decreased. All four heat-treated alloys exhibited good mechanical properties at 750˚C with a yield strength well over 620MPa. As expected, the yield strength increased and the ductility decreased as the average γ' size decreased. The alloys exhibited a mixed mode of deformation, though the dominant deformation mechanism depended on the different γ' characteristics. The major operative deformation mechanism could be well predicted by strength increment calculations based on the precipitation strengthening model. Our results suggest that wrought Haynes 282 produced by a more economical 1-step aging treatment may be a reliable candidate for high temperature applications under A-USC conditions.