A combination of creep tests, ex-service blade samples, thermodynamic equilibrium calculations, combined thermodynamic and kinetic calculations, image analysis, chemical composition mapping and heat treatments have been conducted on PWA1483 to determine if microstructural rejuvenation can be achieved when taking the presence of oxidation coatings into account as part of a blade refurbishment strategy. The work has shown that the γ′ morphology changes during creep testing, and that through subsequent heat treatments the γ′ microstructure can be altered to achieve a similar γ′ size and distribution to the original creep test starting condition. Thermodynamic equilibrium calculations have been shown to be helpful in determining the optimum temperatures to be used for the refurbishment heat treatments. The interaction of oxidation resistant coatings with the alloy substrate and refurbishment process have been explored with both experimental measurements and coupled thermodynamic and kinetic calculations. The predictive nature of the coupled thermodynamic and kinetic calculations was evaluated against an ex-service blade sample which had undergone refurbishment and further ageing. In general there was good agreement between the experimental observations and model predictions, and the modelling indicated that there were limited differences expected as a result of two different refurbishment methodologies. However, on closer inspection, there were some discrepancies occurring near the interface location between the coating and the base alloy. This comparison with experimental data provided an opportunity to refine the compositional predictions as a result of both processing methodologies and longer term exposure. The improved model has also been used to consider multiple processing cycles on a sample, and to evaluate the coating degradation between component service intervals and the consequences of rejuvenation of the blade with repeated engine exposure. The results from the experimental work and modelling studies potentially offer an assessment tool when considering a component for refurbishment.

A global movement is pushing for improved efficiency in power plants to reduce fossil fuel consumption and CO 2 emissions. While raising operating temperatures and pressures can enhance thermal efficiency, it necessitates materials with exceptional high-temperature performance. Currently, steels used in power plants operating up to 600°C achieve efficiencies of 38-40%. Advanced Ultra Supercritical (A-USC) designs aim for a significant leap, targeting steam temperatures of 700°C and pressures of 35 MPa with a lifespan exceeding 100,000 hours. Ni-based superalloys are leading candidates for these extreme conditions due to their superior strength and creep resistance. Haynes 282, a gamma prime (γ′) precipitation-strengthened alloy, is a promising candidate for A-USC turbine engines, exhibiting excellent creep properties and thermal stability. This research investigates the microstructural evolution in large, sand-cast components of Haynes 282. Microstructure, referring to the arrangement of grains and phases within the material, significantly impacts its properties. The research examines the alloy in its as-cast condition and after various pre-service heat treatments, aiming to fully identify and quantify the microstructural changes. These findings are then compared with predictions from thermodynamic equilibrium calculations using a dedicated Ni alloy database. The research reveals that variations in heat treatment conditions can significantly affect the microstructure development in Haynes 282, potentially impacting its mechanical properties.

Materials are developed and improved by adjusting both the alloy chemistry and the processing conditions to achieve desired microstructures and properties. Traditionally, these improvements have been made by a slow and labor-intensive series of experiments. But it is now possible to replace this expensive trial and error process by carrying out only a few ‘key’ experiments in conjunction with thermodynamic calculations. These calculations are powerful tools for alloy design, enabling improvement in the selection of alloy chemistry and the parameters used for fabrication steps such as heat treatments. In order to have the utmost confidence in the results obtained from the calculations, it is essential to have high quality thermodynamic databases. Such databases can be used not only in phase equilibrium calculations but also as the critical input for further kinetic simulations. In the present paper, we present our work on the development of reliable thermodynamic databases for nickel-based superalloys and iron alloys. We first briefly describe the methodology of developing these databases and then discuss some specific examples using the databases. With the aid of these examples, the usefulness of thermodynamic databases in aiding the development of advanced materials is discussed.

A new nickel-base superalloy GH750 has been developed as boiler tube of advanced ultrasupercritical (A-USC) power plants at temperatures about and above 750°C in China. This paper researched the weld solidification of GH750 filler metal, microstructure development and property of GH750 welded joint by gas tungsten arc weld. Liquid fraction and liquid composition variation under non-equilibrium state were calculated by thermo-dynamic calculation. The weld microstructure and the composition in the dendrite core and interdendritic region were analyzed by SEM(EDX) in detail. The investigated results show that there is an obvious segregation of precipitation-strengthening elements during the weld solidification. Titanium and Niobium are the major segregation elements and segregates in the interdendritic region. It was found that the changing tendency of the elements’ segregation distribution during the solidification of GH750 deposit metal is agree with the thermodynamic calculation results. Till to 3,000hrs’ long exposure at 750°C and 800°C, in comparison with the region of dendrite core of solidification microstructure, not only the coarsening and the accumulation of γʹ particles are remarkable in the interdendritic region, but also the small quantity of the blocky and needle like η phases from. The preliminary experimental results indicate that the weakening effect of creep-rupture property of the welded joint is not serious compared with GH750 itself.

25Cr-20Ni-Nb-N (Tp310HCbN) steel is a promising austenitic steel for applications in superheater tubes in coal fired thermal power plants due to the high creep strength and oxidation resistance. In this work, the microstructural evolution of this material during heat treatment and thermal ageing has been investigated. The investigations were carried out by Light Optical Microscopy (LOM), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Energy Dispersive Spectroscopy (EDS). Besides, equilibrium and Scheil calculations were carried out using the thermodynamic software MatCalc to analyse the stable phases and the solidification process, respectively. Precipitation calculations during solution annealing and subsequent ageing at 650 and 750°C were performed to predict the phase fraction and precipitates radius up to 10.000h ageing time. SEM and TEM investigations of aged specimens revealed the presence of six different precipitates: M 23 C 6 , Cr 2 N, sigma, Z-phase, eta-phase (Cr 3 Ni 2 Si(C,N)) and Nb(C,N). These precipitates were predicted and confirmed by MatCalc simulations. The calculated phase fraction and mean radius show good agreement with experimental data. Finally, simulations of different Cr-, C- and N-content in Tp310HCbN were performed.

For VM12-SHC 11-12 wt. % Cr steel, there have been no systematic investigations to define the regions or characterise the microstructures within the heat-affected zone (HAZ) of weldments. In similar steels, these regions relate to the Ac 1 and Ac 3 transformation temperatures and can affect weldment performance. In this study, controlled thermal cycles were applied to VM12-SHC parent metal using a dilatometer and the Ac 1 and Ac 3 temperatures were measured for various heating rates. The Ae 1 and Ae 3 temperatures were also calculated by thermodynamic equilibrium modeling. Through dilatometry, thermal cycles were then applied to simulate the microstructures of the classically defined HAZ regions. The microstructural properties of each simulated material were investigated using advanced electron microscopy techniques and micro-hardness testing. It was found that the simulated HAZ regions could be classified as; (1) the completely transformed (CT) region, with complete dissolution of pre-existing precipitates and complete reaustenitisation; (2) the partially transformed (PT) region, exhibiting co-existing original martensite with nucleating austenite microstructures with partial dissolution of precipitates; and (3) the over tempered (OT) region, with no phase transformation but precipitate coarsening and decreased hardness.

The precipitation behavior of various phases in austenitic heat-resistant model steels, including the Fe 2 Nb Laves phase (C14 structure) on grain boundaries (GB) and grain interiors (GI), and the Ni 3 Nb metastable γ“ phase and stable δ phase on GI, was investigated through experimental study at different temperatures and thermokinetic calculation. The steel samples were prepared by arc melting followed by 65% cold rolling. Subsequently, the samples were solution treated within the γ single-phase region to control the grain size to approximately 150 μm. Aging of the solution-treated samples was carried out at temperatures ranging from 973 K to 1473 K for up to 3600 hours. Microstructural observations were conducted using FE-SEM, and the chemical compositions of the γ matrix and precipitates of Laves and δ phases were analyzed using EPMA. The precipitation modeling was performed using MatCalc software, utilizing a thermodynamic database constructed by our research group to calculate the chemical potential of each phase. Classical nucleation theory was applied for nucleation, while the SFFK model was employed for the growth and coarsening stages. Distinct phases were defined for grain boundary and grain interior Laves phase, with all precipitates assumed to have spherical morphology in the calculations. The precipitation start time was defined as the time when the precipitate fraction reached 1%. Experimental results indicated that above 973 K, Laves phase nucleation primarily occurred on grain boundaries before extending into the grain interior, with the nose temperature located around 1273 K. To replicate the experimentally determined Time-Temperature-Precipitation (TTP) diagram, interaction parameters among elements were adjusted. Additionally, by introducing lower interfacial energy between the γ matrix and Laves phase, the TTP diagram was successfully reproduced via calculation, suggesting relative stability at the interface.

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.

In order to develop an Fe/Ni dissimilar-weld rotor structure for an Advanced Ultra Super Critical turbine, fundamental studies on the metallurgical properties of Fe/Ni welds are needed. In the work reported in this paper, we studied the microstructure evolution and creep rupture properties of Fe/Ni weld joints with different compositions. Investigation of thermally aged Fe/Ni diffusion couples revealed that Fe-based ferritic steel and Alloy 617 weld joints with a large difference in Cr content showed strong C diffusion at the weld interface. This decreased the creep rupture life of the weld joint, caused by coarsening of a martensitic structure near the interface. Analysis using Fe/Ni diffusion couples and thermodynamic calculations suggested that the driving force of C diffusion is the chemical potential gradient at the interface, and the difference in Cr content between Fe and Ni accelerates the C diffusion.

Creep strength enhanced ferritic steels like T/P 91 and T/P 92 are widely used for the fabrication of pressure vessel components in the petro-chemical and thermal power industry. Today, a new generation of 9-12% Cr CSEF steels like MARBN, Save12AD, G115 and Super VM12 are entering into the market. All CSEF steels require an accurate post-weld heat treatment after welding. This paper discusses the impact of chemical composition on Ac1 as well as the transformation behavior during post-weld heat treatment in a temperature range below and above Ac1. The Ac1 temperature of weld metals with variations in chemical composition has been determined and thermodynamic calculations has been carried out. Simulations of heat treatment cycles with variations in temperature have been carried out in a quenching dilatometer. The dilatation curves have been analyzed in order to detect any phase transformation during heating or holding at post weld heat treatment. Creep rupture tests have been carried out on P91 and Super VM12 type weld metals in order to investigate the effect of sub- and intercritical post weld heat treatment on creep rupture strength.

Metallurgical factors affecting the fusion boundary failure and damage mechanism of DMWs (Dissimilar Metal Welds) between the CSEF (Creep Strength Enhanced Ferritic) steels and austenitic steels were experimentally and theoretically investigated and discussed. Long-term exservice DMWs up to 123,000 hours were investigated; the precipitates near the fusion boundary were identified and quantitatively evaluated. Comparing with the other generic Ni-based weld material, MHPS original filler metal HIG370 (Ni bal.-16Cr-8Fe-2Nb-1Mo) showed superior suppression effect on fusion boundary damage of DMWs, which was verified by both of the microstructure observation and thermodynamic calculation. Based on the microstructure observation of crept specimen and ex-service samples of DMWs, temperature, time and stress dependence of fusion boundary damage of DMWs were clarified. Furthermore, fusion boundary damage morphology and mechanism due to precipitation and local constituent depletion was discussed and proposed from metallurgical viewpoints.

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.

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.

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.

Prediction of long-term creep strength is an important issue for industrial plants operated at elevated temperatures, although the creep strength of high Cr ferritic steels depends on their microstructural evolution during creep. The state of microstructure in metallic materials can be expressed as numerical values based on a concept of system free energy. In this study, in order to evaluate long term creep strength of 9Cr ferritic steel containing B, change in the system free energy during creep of the steel 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. The system free energy decreases with creep time. Change in the energy is expressed quantitatively as a numerical formula using the rate constants which depend on applied stress. On the basis of these facts, long term creep strength of the steel can be evaluated at both 948K(675°C) and 973K(700 °C).

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.

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.

Due to a high degree of mixing between substrate and weld deposit, fusion welding of dissimilar metal joints functionally produce new, uncharacterized alloys. In the power generation industry, such mixing during the application of cobalt-based hardfacing has led to a disconcerting number of failures characterized by the hard overlay welds disbonding. Investigations into this failure mechanism point to the unknown alloy beneath the surface of the hardfacing layer transforming, hardening, and becoming brittle during service. This research describes a methodology for exploring a chemical space to identify alloy combinations that are expected to be safe from deleterious phase formation. Using thermodynamic modeling software and a stepped approach to potential chemistries, the entire phase stability space over the full extent of possible mixing between substrate and weld material can be studied. In this way diffusion effects – long term stability – can also be accounted for even in the case where mixing during application is controlled to a low level. Validation of predictions specific to the hardfacing system in the form of aged weld coupons is also included in this paper. Though the application of this methodology to the hardfacing problem is the focus of this paper, the method could be used in other weld- or diffusion- combinations that are expected to operate in a high temperature regime.

Martensitic 9Cr steels have been developed which are strengthened by boron in order to stabilize the microstructure and improve their long-term creep strength. Boron plays a key role in these steels by stabilising the martensitic laths by decreasing the coarsening rate of M 23 C 6 carbides, which act as pinning points in the microstructure. In this work two modified FB2 steel forgings are compared. Both forgings have similar compositions but one underwent an additional remelting process during manufacture. Creep tests showed that this additional processing step resulted in a significant increase in time to failure. In order to investigate the effect of the processing route on microstructural evolution during aging and creep, a range of advanced electron microscopy techniques have been used including ion beam induced secondary electron imaging and High Angle Annular Dark Field (HAADF) imaging in the Scanning Transmission Electron Microscope. These techniques have enabled the particle population characteristics of all the second phase particles (M 23 C 6 , Laves phase, BN and MX) to be quantified for materials from both forging processes. These quantitative data have enabled a better understanding of how the processing route affects the microstructural evolution of FB2 steels.

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.