The presence of sulfur at an impurity level in heat resistant steels could improve remarkably the steam oxidation resistance. As is well known, sulfur tends to form sulfides, in particular, chromium sulfides when the steel contains chromium. Therefore, there are two possibilities of sulfur states in the steel. One is in atomic sulfur state as a solid solution, and the other is in sulfide state as a precipitate. However, it still remains unclear which sulfur state contributes largely to the improvement of the steam oxidation resistance of the steels. In order to elucidate the sulfur state operated more effectively in improving the oxidation resistance, the steam oxidation resistance was investigated with high chromium ferritic steels, Fe-10mass%Cr-0.08mass%C-(0~0.015)mass%S, with controlling the sulfur states in them by proper heat treatments. From a series of experiments, it was found that the sulfide state played a more important role in improving the steam oxidation resistance than the atomic sulfur state. Furthermore, this sulfur effect worked significantly in the steam oxidation test performed at the temperatures above 873K which corresponded to the temperature for the chromium sulfide to dissolve and instead for the chromium oxide to form in the steels. This result indicates that the beneficial effect of sulfur in improving the steam oxidation resistance is related closely to the sulfide stability against the oxide in the steels.

In downstream oil industry applications, high-temperature sulfidation corrosion is generally caused by sulfur species coming from the crude; additionally, naphthenic acids or hydrogen can considerably worsen the corrosivity of the environment. During plant operations, several events may occur that boost the severity of corrosion: high feedstock turnover, with increasing “active” sulfur species; skin temperature rise due to the increasing insulation effect of the scale, generating an over-tempering of the material and possible degeneration into creep conditions. Thor115 is a ferritic steel with 11% chromium content to resist sulfidation. It has excellent creep properties for high temperature environments: higher allowable stresses than grade 91, keeping the same manufacturing and welding procedures. At the same time, it has the characteristics of ferritic steel, ensuring enhanced thermal conductivity and lower thermal expansion compared to austenitic steels. Comparative corrosion tests between Thor115 and other ferritic steels typically used in this industry (e.g., grade T/P5 and grade T/P9) have been carried out to simulate different corrosive conditions, confirming the superior properties of Thor115 relative to other ferritic grades. For these reasons, Thor 115 is a suitable replacement material for piping components that need an upgrade from grade T/P9 or lower, in order to reduce corrosion rate or frequency of maintenance operations.

The INCONEL filler metals 72 and 72M have been utilized significantly for weld overlay protection of superheaters and reheaters, offering enhanced corrosion and erosion resistance in this service. Laboratory data conducted under simulated low-NOx combustion conditions, field exposure experience, and laboratory analysis (microstructure, chemical composition, overlay thickness measurements, micro-hardness) of field-exposed samples indicate that these overlay materials are also attractive options as protective overlays for water wall tubes in low-NOx boilers. Data and field observations will be compared for INCONEL filler metals 72, 72M, 625 and 622.

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.

Alloy 33 is a weld overlay material that has generated a lot of interest in the fossil boiler industry. The high chromium content of Alloy 33 has been shown to provide excellent corrosion protection in both waterwall and superheater/reheater tube applications. For waterwall applications, the corrosion resistance has been demonstrated in both laboratory and field tests conducted over the last 5 years. In addition to corrosion resistance, the Alloy 33 has also shown that it is also resistant to cracking (although no material is 100% immune). In the superheater/reheater, the use of spiral clad weld overlay tubes is able to provide resistance to excellent coal ash corrosion. Laboratory and field tests have shown Alloy 33 to have among the best corrosion resistance of all materials studied. The application of Alloy 33 is also easier than other more highly alloyed materials (such as FM-72) and is less expensive. As a result of these favorable experiences, Alloy 33 is now being used commercially to weld overlay both waterwall and superheater/reheater tubes on fossil boilers.

A combined pilot-scale combustion test and long-term laboratory study investigated the impact of oxy-firing on corrosion in coal-fired boilers. Four coals were burned under both air and oxy-firing conditions with identical heat input, with oxy-firing using flue gas recirculation unlike air-firing. Despite higher SO 2 and HCl concentrations in oxy-firing, laboratory tests showed no increase in corrosion rates compared to air-firing. This is attributed to several factors: (1) Reduced diffusion: High CO 2 in oxy-firing densified the gas phase, leading to slower diffusion of corrosive species within the deposit. (2) Lower initial sulfate: Oxy-fired deposits initially contained less sulfate, a key hot corrosion culprit, due to the presence of carbonate. (3) Reduced basicity: CO 2 and HCl reduced the basicity of sulfate melts, leading to decreased dissolution of metal oxides and mitigating hot corrosion. (4) Limited carbonate/chloride formation: The formation of less corrosive carbonate and chloride solutes was restricted by low O 2 and SO 3 near the metal surface. These findings suggest that oxy-firing may not pose a greater corrosion risk than air-firing for boiler materials.

Six types of solution treated Ni-based alloy plates having a thickness of 25mm, namely Alloy 617, Alloy 263, Alloy 740, Alloy 141, HR6W (45Ni-23Cr-7W) and HR35 (50Ni-30Cr-4W-Ti) for advanced-USC boilers, were subjected to corrosion testing. In addition, three types of conventional ferritic and five types of conventional austenitic stainless tubes were also tested to compare their corrosion properties. Hot corrosion tests were conducted in order to assess the effects of temperature, material composition and coal ash composition on hot corrosion. The maximum average metal loss and the maximum corrosion rate were observed under 700°C test conditions. Cr content in the materials played an important role in the corrosion rate, with higher Cr content materials tending to show lower rates. However, Ni-based alloy materials showed slightly greater corrosion rates than those of stainless steels having equivalent Cr content in the over-700°C test condition. It was considered that rich Ni in the alloys easily reacted with sulfur, thus forming corrosion products having low melting points, such that corrosion was accelerated. The concentration of Fe 2 O 3 and NiO in the synthetic coal ash was also observed to affect the corrosion rate.

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.

Recently, boiler waterwall tube damage such as fireside corrosion and circumferential cracking in low NOx environments has become a serious issue in Japan, despite the typical use of relatively lower sulfur content coal is typically being used than in US. Thermal spray coating has been the most popular method for tube protection in Japan, and thermal spray coated tubes have been used for this purpose. However, extensive damage to thermal spray coating tubes from cracking and exfoliation has been recently experienced. It has been reported that the thermal fluctuations occurring due to operational changes create alternating stress, leading to cracking and exfoliation of the thermal sprayed thin coating. Corrosion-resistant weld overlays, such as Type 309 stainless steel (in sub-critical boilers) and Alloy 622 (in sub-critical and super-critical boilers), are commonly used to protect boiler tubes from corrosion in low NOx coal fired boilers in U.S. In order to develop a fundamental understanding of the high temperature corrosive behavior of Alloy 622 weld overlay, gaseous corrosion testing and certain mechanical tests for consideration of long-term aging were undertaken. After four years of service in the low NOx combustion environment of a coal fired supercritical boiler, field tests on Alloy 622 weld overlay panels are in continuation. This paper describes the field test behavior of Alloy 622 weld overlay panels installed in a Japanese supercritical boiler, the laboratory results of weight loss corrosion testing, and the results of cyclic bend tests with overlay welded tubes related to aging.

Inconel Filler Metal 72 (FM 72) and Incoclad 671/800H co-extruded tubing have been successfully used for over 20 years to protect boiler tubing from high-temperature degradation. A newer alloy, FM 72M, offers superior weldability and the lowest corrosion rate in simulated low NOx environments. Both FM 72 and 72M show promise in addressing challenges like circumferential cracking and corrosion fatigue in waterwall tubing overlays. Additionally, 72M’s superior wear resistance makes it ideal for replacing erosion shields in superheater and reheater tubing. Beyond improved protection, these alloys exhibit increased hardness and thermal conductivity over time, leading to reduced temperature difference across the tube wall and consequently, enhanced boiler efficiency and lower maintenance costs. This paper discusses the historical selection of optimal alloys for waterwall and upper boiler tubing overlays, analyzes past failure mechanisms, and highlights the key properties of successful choices like FM 72 and 72M.

The article gives a brief overview of the newly developed austenitic material “Power Austenite”. The microstructure of the Power Austenite is characterized by grain boundary strengthening with boron stabilized M23(C,B)6 and secondary Nb(C,N) in combination with sigma phase and Nb(C,N) as the major grain strengthening precipitates. The material shows a significant creep strength at 700 °C (1292 °F) and 650 °C (1202 °F) as well as fireside corrosion resistance which makes it a possible candidate for 700 °C (1292 °F) power plants.

The U.S. Department of Energy (DOE) and the Ohio Coal Development Office (OCDO) are co-sponsoring a multi-year project managed by Energy Industries of Ohio (EIO) to evaluate materials for ultra-supercritical (USC) coal-fired boilers. USC technology improves cycle efficiency and reduces CO 2 and pollutant emissions. With turbine throttle steam conditions reaching 732°C (1350°F) at 35 MPa (5000 psi), current boiler materials, which operate below 600°C (1112°F), lack the necessary high-temperature strength and corrosion resistance. This study focuses on the fireside corrosion resistance of candidate materials through field testing. Evaluated materials include ferritic steels (SAVE12, P92, HCM12A), austenitic stainless steels (Super304H, 347HFG, HR3C), and high-nickel alloys (Haynes 230, CCA617, Inconel 740, HR6W), along with protective coatings (weld overlays, diffusion coatings, laser claddings). Prior laboratory tests assessed corrosion under synthesized coal-ash and flue gas conditions for three North American coal types (Eastern bituminous, Midwestern high-sulfur bituminous, and Western sub-bituminous), with temperatures ranging from 455°C (850°F) to 870°C (1600°F). Promising materials were installed on retractable corrosion probes in three utility boilers burning different coal types. The probes maintained metal temperatures between 650°C (1200°F) and 870°C (1600°F). This paper presents new fireside corrosion probe results after approximately one year of exposure for Midwestern and Western coal types.

Advanced chromium-molybdenum-vanadium steels 9CrMoV [P(T)91] have seen extensive global adoption across power, petrochemical, and other industrial sectors over the past decade, driven by the demand for materials with superior high-temperature properties to improve efficiency. Experience with P(T)91 base metals and weldments has revealed that these steels require substantially more attention than the commonly used P(T)22 grade and similar materials. This presentation examines Grade 91's various design code requirements across power, petroleum, and nuclear industries, focusing on fabrication and welding considerations. The discussion covers critical material properties and heat treatment parameters, including the significance of maintaining proper preheat and interpass temperatures, while highlighting the risks associated with interrupted heating cycles and improper postweld heat treatment. The paper also addresses factors influencing the use, development, and procurement of Modified Grade 91 welding consumables for heavy wall applications, and explores the subtle technical differences between North American and European approaches to production and utilization, ultimately emphasizing the considerable care required during joining processes to ensure acceptable long-term properties.

Inconel alloy 740H was specifically developed for use in coal-fired AUSC boilers. This alloy displays a unique combination of steam and coal-ash corrosion resistance, microstructure stability, creep strength and heavy section weldability. During the past two years Special Metals and Wyman-Gordon have undertaken an intense effort to demonstrate their capability to manufacture full-size boiler components, characterize their properties and simulate field assembly welds. This work was performed according to the requirements of ASME Boiler Code Case 2702 that was recently issued. This paper covers manufacturing of tube and pipe products and property characterization including recent data on the effect of long time exposure on impact toughness of base and weld metal. New data will also be reported on coal ash corrosion of base metal and weld metal. An overview of welding studies focused on integrity of circumferential pipe joints and a discussion of remaining technical issues will be presented.

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.

Nickel-based alloys and stainless steel Super304H, along with various coatings, are undergoing testing in a steam loop at Alabama Power’s Plant Barry. These materials are being evaluated for use in advanced ultra-supercritical (A-USC) fossil-fired power plants at temperatures ranging from 538°C to 815°C. The loop has been operational for over 18 months, with the alloys exceeding 6,300 hours above 538°C. An additional 7,000 hours at high temperatures are planned before the loop’s removal in 2014. Initial inspections show minimal material corrosion, suggesting their suitability for A-USC applications. This paper details the loop’s design, materials, manufacturing, operation, and inspection findings. Additionally, it describes a methodology for predicting steam-side oxidation and fireside corrosion rates and highlights the significance of this testing for A-USC development and commercialization.

The current research adopts a novel approach by integrating correlative microscopy and machine learning in order to study creep cavitation in an ex-service 9%Cr 1%Mo Grade 91 ferritic steel. This method allows for a detailed investigation of the early stages of the creep life, enabling identification of features most prone to damage such as precipitates and the ferritic crystal structure. The microscopy techniques encompass Scanning Electron Microscopy (SEM) imaging and Electron Back-scattered Diffraction (EBSD) imaging, providing insights into the two-dimensional distribution of cavitation. A methodology for acquiring and analysing serial sectioning data employing a Plasma Focused Ion Beam (PFIB) microscope is outlined, complemented by 3D reconstruction of backscattered electron (BSE) images. Subsequently, cavity and precipitate segmentation was performed with the use of the image recognition software, DragonFly and the results were combined with the 3D reconstruction of the material microstructure, elucidating the decoration of grain boundaries with precipitation, as well as the high correlation of precipitates and grain boundaries with the initiation of creep cavitation. Comparison between the 2D and 3D results is discussed.

The time-dependent behavior of 9Cr creep strength enhanced ferritic (CSEF) steels has long fixated on the creep life recorded in uniaxial constant load creep tests. This focus is a consequence of the need to develop stress allowable values for use in the design by formulae approach of rules for new construction. The use of these simple rules is justified in part by the assumption that the alloys used will invariably demonstrate high creep ductility. There appears to be little awareness regarding the implication(s) that creep ductility has on structural performance when mechanical or metallurgical notches (e.g., welds) are present in the component design or fabricated component. This reduced awareness regarding the role of ductility is largely because low alloy CrMo steels used for very many years typically were creep ductile. This paper focuses on the structural response from selected tests that have been commissioned or executed by EPRI over the last decade. The results of these tests demonstrate unambiguously the importance that creep ductility has on long-term, time-dependent behavior. This is the second part of a two-part paper; Part I reviewed the selected tests and discussed them from a mechanical perspective. The association of performance with specific microstructural features is briefly reviewed in this paper and the remaining gaps are highlighted for consideration among the international community.

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 use of high-nickel superalloys has greatly increased among many industries. This is especially the case for advanced coal-fired boilers, where the latest high temperature designs will require materials capable of withstanding much higher operating temperatures and pressures than current designs. Inconel alloy 740H (UNS N07740) is a new nickel- based alloy that serves as a candidate for steam header pipe and super-heater tubing in coal-fired boilers. Alloy 740H has been shown to be capable of withstanding the extreme operating conditions of an advanced ultra-super-critical (AUSC) boiler, which is the latest boiler design, currently under development. As with all high nickel alloys, welding of alloy 740H can be very challenging, even to an experienced welder. Weldability challenges are compounded when considering that the alloy may be used in steam headers, where critical, thick-section and stub-to-header weld joints are present. This paper is intended to describe the proper procedures developed over years of study that will allow for ASME code quality welds in alloy 740H with matching composition filler metals.