The steam oxidation behaviour of boiler tubes and steam piping components is a limiting factor for improving the efficiency of the current power plants. Spallation of the oxide scales formed during service can cause serious damage to the turbine blades. Vallourec has implemented an innovative solution based on an aluminum diffusion coating applied on the inner surface of the T/P92 steel. The functionality of this coating is to protect the tubular components against spallation and increase the actual operating temperature of the metallic components. In the present study, the newly developed VALIORTM T/P92 product was tested at the EDF La Maxe power plant (France) under 167b and 545°C (steam temperature). After 3500h operation, the tubes were removed and characterized by Light Optical Metallography (LOM), Scanning Electron Microscopy (SEM), with Energy Dispersive X-ray spectrometry (EDX) and X-Ray Diffraction (XRD). The results highlight the excellent oxidation resistance of VALIORTM T/P92 product by the formation of a protective aluminum oxide scale. In addition, no enhanced oxidation was observed on the areas close to the welds. These results are compared with the results obtained from laboratory steam oxidation testing performed on a 9%Cr T/P92 steel with and without VALIORTM coating exposed in Ar-50%H 2 O at 650°C.

This paper investigates the cause of premature failures in certain Grade 91 steel components used in UK power plants. The failures were linked to both low material hardness and specific chemical compositions that fell within ASTM specifications but had a low nitrogen-to-aluminum ratio (N:Al). The investigators examined eight material batches, including those involved in failures, new stock, and in-service components with similar properties. Testing confirmed these materials had lower creep resistance compared to standard Grade 91 steel. Microscopic analysis revealed the presence of large aluminum nitride precipitates, which limited the formation of beneficial vanadium nitride precipitates, leading to reduced creep strength. These findings suggest that even within the ASTM specification limits, a low N:Al ratio can negatively impact the performance of Grade 91 steel.

The effect of boron nitrides (BN) and aluminum nitrides (AlN) on long-term creep life and rupture ductility has been investigated for martensitic 9 to 12Cr steels at 550 to 700 °C. The BN particles form in 9 to 12Cr steels during normalizing heat treatment at 1050 to 1150 °C, suggesting no change in the amount of BN particles during creep. On the other hand, the AlN particles gradually form during creep at 550 to 700 °C, decreasing the concentration of nitrogen free from the AlN particles. The degradation in creep life takes place more significantly with test duration in the steels containing high Al but not in those containing the BN particles. The rupture ductility is evaluated by using a semi-logarithmic diagram of the RA and total elongation, showing the necking dominant and void swelling dominant regions. The BN and AlN particles are responsible for the degradation in RA at low stresses and long times by accelerating the formation of creep voids at interfaces between the BN and AlN particles and alloy matrix.

Laboratory-scale tests are frequently used to generate understanding of high-temperature oxidation phenomena, to characterise and rank the performance of existing, future materials and coatings. Tests within the laboratory have the advantage of being well controlled, monitored and offer the opportunity of simplification which enables the study of individual parameters through isolating them from other factors, such as temperature transients. The influence of pressure on the oxidation of power plant materials has always been considered to be less significant than the effects of temperature and Cr content, but still remains a subject of differing opinions. Experimental efforts, reported in the literature, to measure the influence of steam pressure on the rate of oxidation have not produced very consistent or conclusive results. To examine this further a series of high pressure steam oxidation exposures have been conducted in a high pressure flowing steam loop, exposing a range of materials to flowing steam at 650 and 700 °C and pressure of 25, 50 and 60 bar. Data is presented for ferritic-martensitic alloys showing the effect of increasing pressure on the mass change and oxide thickness of these alloys in the flowing steam loop. In addition the effect observed on the diffusion of aluminium from an aluminised coating in these alloys is also presented and the differences in the extent of diffusion discussed.

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.

New Monte Carlo models have recently been developed to predict microstructural evolution in steels and aluminum alloys during heat treatment and high-temperature service. These models can control precipitate type and size distribution, distinguishing between pure lattice and grain boundaries. Consequently, they can forecast the precipitate size distribution within grains and on grain boundaries as a function of time. This paper describes the model validation for ferritic Fe-9Cr P92 steels. The model provides new information over a range of time intervals adding up to the total plant lifetime in an ultra-supercritical plant. This information can be incorporated into continuum damage mechanics models for predicting creep rate and stress rupture life. The paper discusses how this technique is used as a materials development tool to forecast necessary compositional modifications for improving creep properties in ferritic steels.

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.

This study investigates the steam oxidation behavior of Alloy 699 XA, a material containing 30 wt.% chromium and 2 wt.% aluminum that forms protective oxide scales in low-oxygen conditions. The research compares four variants of the alloy: conventional bulk material, a laser powder bed fusion (LPBF) additively manufactured version, and two modified compositions. The modified versions include MAC-UN-699-G, optimized for gamma-prime precipitation, and MAC-ISIN-699, which underwent in-situ internal nitridation during powder atomization. All variants were subjected to steam oxidation testing at 750°C and 950°C for up to 5000 hours, with interim analyses conducted at 2000 hours. The post-exposure analysis employed X-ray diffraction (XRD) to identify phase development and scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) to examine surface morphology, cross-sectional microstructure, and chemical composition. This study addresses a significant knowledge gap regarding the steam oxidation behavior of 699 XA alloy, particularly in its additively manufactured state.

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.

Coal burning power companies are currently considering FeAlCr weld overlay claddings for corrosion protection of waterwall boiler tubes located in their furnaces. Previous studies have shown that these FeAlCr coatings exhibit excellent high-temperature corrosion resistance in several types of low NOx environments. In the present study, the susceptibility of FeAlCr weld overlay claddings to hydrogen cracking was evaluated using a gas-tungsten arc welding (GTAW) process. Microsegregation of alloying elements was determined for the FeAlCr welds and compared to a currently used Ni-based superalloy. Long-term gaseous corrosion testing of select weld overlays was conducted along with the Ni-based superalloy in a gaseous oxidizing/sulfidizing corrosion environment at 500°C. The sample weight gains were used along with analysis of the corrosion scale morphologies to determine the corrosion resistance of the coatings. It was found that although there were slight differences in the corrosion behavior of the selected FeAlCr weld coatings, all FeAlCr based alloys exhibited superior corrosion resistance to the Ni-based superalloy during exposures up to 2000 hours.

Recent evidence suggests that using hardness as the sole acceptance criterion for Grade 91 steels is inadequate for predicting service performance. Components can achieve acceptable initial hardness values through heat treatment despite suboptimal elemental composition, leading to poor tempering resistance and unexpectedly low creep strength during service. Paradoxically, some components with lower initial hardness may perform better due to slower degradation rates. While the relationship between parent material properties and Type IV cracking susceptibility remains under investigation, heat-affected zones (HAZ) in welds are emerging as primary locations for service failures. This complexity emphasizes the need for comprehensive evaluation criteria incorporating stress, temperature, and material properties when assessing component serviceability.

In this paper, the microstructural evolution of P92 steel were studied in the viewpoint of degradation mechanism based on the creep rupture experiment results obtained at elevated temperature by means of macroscopic, metallographic, electronic microscope, energy spectrum, XRD and TEM examination. The results show that the decrease of mechanical properties of P92 steel is mainly due to the change of microstructure and the transformation of carbides, and there is definite relationship between microstructure evolution, mechanical properties and life loss of P92 steel. The results are beneficial to the further study of mechanism of high temperature creep rupture strength and microstructural evolution of heat-resistant steel. It also has important instructive significance to quantitative identification of scientific selection of materials.

In the context of research of lighter and/or stronger high temperature materials in order to improve aeroengines, the present work shows an example of a powder metallurgy (PM) manufacturing route for TiAl alloys that could be used for low pressure turbine (LPT) blades processing. In this frame, two different alloys, Ti-47Al-1Fe-1Zr-1Mo-0.2Si (at. %) FZM and Ti- 43.5A1-4Nb-1Mo-0.1B (at.%) TNM-B1, were gas-atomized into powders, extruded, heat-treated and mechanically tested.

The drive for reduced carbon dioxide emissions and improved efficiency in coal fire power plant has led to much work being carried out around the world with regards to material development to enable 700+°C steam temperature operation. At these elevated temperatures and pressures steels just don’t have enough strength, and typically have a temperature limit of around 620°C (possibly up to 650°C in the near future) in the HP environment. Therefore, material development has focused on nickel alloys. European programs such as AD700, COMTES, European 50+ and more recently, NextGen Power and Macplus, have investigated the use of nickel alloys in the steam turbine. Large castings have an important role within the steam turbine, because valves bodies and turbine casings are nearly always produced from a cast component. The geometry of these components is often complex, and therefore, the advantage of using castings for such items is that near net shapes can be produced with minimal machining. This is important, as nickel alloys are expensive, and machining is difficult, so castings offer an attractive cost benefit. Cast shapes can be more efficiently designed with regards to stress management. For example, contouring of fillet regions can help to reduce stress concentrations leads to reduced plant maintenance and casting complex shapes reduces the number of onsite fabrication welds to inspect during outage regimes.

In the “Boiler Materials for Ultrasupercritical Coal Power Plants” program, sponsored by the U.S. Department of Energy and the Ohio Coal Development Office, various materials are being assessed for their suitability in the high-temperature, high-pressure environment of advanced ultrasupercritical (A-USC) boilers. Beyond mechanical properties and fireside corrosion resistance, these materials must also exhibit adequate steamside oxidation and exfoliation resistance. A comprehensive database of steamside oxidation test results at temperatures relevant to A-USC conditions has been compiled over recent years. These tests have been conducted on ferritic and austenitic materials with chromium content ranging from 2 to 26%. The specimens were evaluated for oxidation kinetics and oxide morphology. The findings indicate that steamside oxidation behavior is significantly affected by temperature, the chromium content of the material, and the ability of chromium to diffuse through the material's crystallographic lattice structure. Additionally, surface treatments have been applied to enhance the steamside oxidation resistance of certain materials. While these treatments have shown potential, their effectiveness can be limited by the operational temperatures.

As conventional coal-fired power plants seek to reduce greenhouse gas emissions by increasing efficiency, the temperature limitations of traditional ferritic/martensitic steels used in high-temperature components present a significant challenge. With Advanced Ultra Supercritical (A-USC) power plants proposing steam temperatures of 760°C, attention has turned to nickel-based superalloys as potential replacements, since ferritic/martensitic steels cannot withstand such extreme conditions. However, the current absence of cast nickel-based superalloys combining high strength, creep-resistance, and weldability has led to the development of cast analogs of wrought nickel-based superalloys, including H263, H282, and N105. This paper examines the alloy design criteria, processing experiences, as-processed and heat-treated microstructures, and selected mechanical properties of these materials while also discussing their potential for full-scale development.

Grade 91 steel, while increasingly popular in high-temperature power plants for both retrofit and new construction applications, faces significant challenges with Type IV cracking at the outer parent side edge of the weld heat affected zone. This structural integrity issue has led to extensive weld inspection requirements and, in severe cases, the premature replacement of grade 91 retrofit headers before their intended design life. This paper presents a method for estimating Type IV cracking timelines in operating grade 91 components by analyzing crossweld Type IV data to determine when Type IV life deviates from parent life. By combining test results from various temperatures, the method generates a generalized prediction of Type IV life that can be extrapolated to any temperature of interest, providing a practical lower bound estimate for service life of the weakest grade 91 material. This approach, which can be applied to service operating conditions to establish realistic inspection timelines for plant components, has already successfully identified early-stage Type IV cracking in two retrofit headers and is being expanded to additional grade 91 components.

As long term laboratory creep data became available the original estimates of the allowable stresses for creep strength enhanced ferritic steels (CSEF) had to be reduced. Thus, even in properly processed steel, the long term performance and creep rupture strength is below that originally predicted from a simple extrapolation of short term data. One of the microstructural degradation mechanisms responsible for the reduction in strength is the development of creep voids. Nucleation, growth and inter linkage of voids also result in a significant loss of creep ductility. Indeed, elongations to rupture of around 5% in 100,000 hours are now considered normal for long term creep tests on many CSEF steels. This relatively brittle behaviour, and the associated creep void development, promotes burst rather than leak type fracture in components. Moreover, the existence of significant densities of voids further complicates in-service assessment of condition and weld repair of these steels. The present paper examines background on the nucleation and development of creep voids in 9 to 12%Cr martensitic steels and discusses factors affecting brittle behavior.

The global electric power production is largely dependent on the operation of fossil-fired generation units. Many coal-fired units are exceeding 300,000 hours, which is beyond the expected design life. This has caused a continuous need to inspect steam touched components operating at high temperature and pressure. State-of-the-art coal and combined cycle gas units are specifying ever-greater amounts of the Creep Strength Enhanced Ferritic (CSEF) steels such as Grade 91 or Grade 92. The martensitic 9%Cr CSEF steels were developed to provide greater strength than traditional low alloy power plant steels, such as Grades 11, 12 and 22. The enhanced strength allows for a reduction in overall wall thickness in new or replacement components. Extensive research in both service failures and laboratory testing has shown that time-dependent creep damage can develop differently in Grade 91 steel when compared to low alloy steels. Furthermore, the creep strength in Grade 91 can vary by more than a factor of 10 between different heats. This wide variation of creep strength has led to extensive research in understanding the damage mechanisms and progression of damage in this steel. In this study, large cross weld samples were fabricated from thick wall piping in Grade 91 steel using two different heats of material. One weld was fabricated in a ‘damage tolerant’ heat and another weld was fabricated in a ‘damage intolerant’ heat of material. The samples were subjected to a post-weld heat treatment (PWHT) at a temperature of 745°C (1375°F) for 1.50 hours. Hardness maps were collected on the cross-welds in the as-welded and PWHT condition for both weldments. Cross-weld creep test conditions were selected to develop accelerated damage representative of in-service behavior. The test samples were interrupted at multiple stages and nondestructively evaluated (NDE) with advanced phased-array ultrasonic techniques. Samples were developed to variable levels of damage (50% to 100% life fraction) in both weldments. Metallographic sections were extracted at specific locations to validate the NDE findings using light emitting diode, laser and scanning electron microscopy. This research is being used to help validate the level of damage that can be reliably detected using conventional and advanced NDE techniques.

Cast nickel-based superalloys used as structural materials for gas turbine parts need to withstand high temperatures and dynamic mechanical loads. When in contact with ambient air, the formation of protective oxide scales causes a depletion of γ’-precipitates in the surface-near region and leaves a weakened microstructure. This environmentally based degradation of the material might be accelerated under cyclic thermal exposure. In this paper, the cyclic oxidation behavior of two cast nickel-based superalloys and one single crystalline variant are investigated: C1023, CM-247 LC and M-247 SX. Exposure tests were carried out under both isothermal and cyclic conditions in air at 850 °C, 950 °C and 1050 °C for times up to 120 h to investigate the impact of thermal cycling. The differences in oxidation mechanisms are analyzed phenomenologically via light and electron microscopy and brought in correlation with the oxidation kinetics, determined based on net mass change and depletion zone growth. An assessment of the impact of precipitation loss on local mechanical strength is attempted via nano-indentation method. The found relations can be transferred onto an acceleration of crack growth under creep-fatigue and thermo-mechanical fatigue conditions.