Search Results for sulfidizing

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.

An iron aluminide (Fe 3 Al) intermetallic coating was deposited onto F22 (2.25Cr-1Mo) steel substrate using a JP-5000 high velocity oxy-fuel (HVOF) thermal spray system. The as-sprayed coating was characterized by electron microscopy, X-ray diffraction, oxidation, and adhesion. Fe 3 Al coated steel specimens were exposed to a mixed oxidizing/sulfidizing environment of N 2 -10%CO-5%CO 2 -2%H 2 O-0.12%H 2 S (by volume) at 500, 600, 700, and 800°C for approximately seven days. All specimens gained mass after exposure, inversely proportional to temperature increases. Representative cross-sectioned specimens from each temperature underwent scanning electron microscopy (SEM) and X-ray mapping examination. Results are presented in terms of corrosion weight gain and product formation. The research evaluated the effectiveness of an HVOF-sprayed Fe 3 Al coating in protecting a steel substrate exposed to a fossil energy environment.

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 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.

Contrary to expectations, long-term performance of creep stress enhanced ferritic steels (CSEF) falls short of predictions based on short-term data. This discrepancy is attributed to the formation and growth of creep voids, leading to reduced ductility. This study investigates cavities in creep-tested P92 steel, revealing an association with large ceramic particles (1-2 μm) in standard samples. Three distinct particle compositions were identified: boron nitride (BN), manganese sulfide, and γ-Al 2 O 3 . Statistical analysis showed a strong correlation between BN particles and cavity formation. Using a 3D “slice and view” technique with a focused ion beam/field emission gun scanning electron microscope (FIB-FEGSEM), the study revealed irregular shapes for both cavities and associated particles. Furthermore, analysis of the head-gauge transition area (lower stress exposure) showed small cavities near BN particles, suggesting preferential nucleation on these hard, irregular features. These findings strongly support the hypothesis that BN particles play a key role in cavity nucleation, impacting the long-term performance of P92 steel.

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.

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.

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.

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.

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.

A comprehensive fireside corrosion study was undertaken to better understand the corrosion mechanisms operating on the superheaters and lower furnace walls of advanced coal- fired utility boilers. The study intended to evaluate the fireside conditions generated from burning eight U.S. coals individually in a pilot-scale combustion facility. These coals consisted of a wide range of compositions that are of interest to the utility industry. The combustion facility was capable of producing the realistic conditions of staged combustion existing in coal-fired utility boilers. During each of the combustion tests, gas and deposit samples were collected and analyzed via in-furnace probing at selected locations corresponding to the waterwalls and superheaters. Testing of five of the eight coal groups has been completed to date. Results of these online measurements helped reveal the dynamic nature of the combustion environments produced in coal-fired boilers. Coexistence of reducing and oxidizing species in the gas phase was evident in both combustion zones, indicating that thermodynamic equilibrium of the overall combustion gases was generally unattainable. However, the amount of sulfur released from coal to form sulfur-bearing gaseous species in both the reducing and oxidizing zones was in a linear relationship with the amount of the total sulfur in coal, independent of the original sulfur forms. Such a linear relationship was also observed for the measured HCl gas relative to the coal chlorine content. However, the release of sulfur from coal to the gas phase appeared to be slightly faster and more complete than that of chlorine in the combustion zone, while both sulfur and chlorine were completely released and reacted to form respective gaseous species in the oxidizing zone. The information of sulfur and chlorine release processes in coal combustion generated from this study is considered new to the industry and provides valuable insight to the understanding of fireside corrosion mechanisms.

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.

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 development of oxy-fuel combustion technology for coal-based power generation may produce combustion products different from those typically found in traditional boilers. In particular, the enrichment of CO 2 and perhaps SO3 could alter the chemical equilibrium to favor the formation of certain carbonates and sulfates in the deposit. Higher concentrations of these gases would also increase the potential for condensation of carbonic and sulfuric acids in lower-temperature areas of the boiler. To address these concerns, B&W has instituted a comprehensive research program to better understand the effect of oxy-coal combustion on fireside corrosion. The scope of this program includes gas and deposit analyses of actual combustion products sampled from B&W's Clean Environment Development Facility (CEDF) during the oxy-coal combustion of three commercial coals. The sampling locations consist of regions representing the lower furnace, superheater bank, and pulverizer outlet. Following the gas and deposit analyses, a series of laboratory corrosion tests will be performed to expose candidate alloys and coatings to conditions simulating the oxy-coal combustion environments. The technical approaches and results of the fireside corrosion program obtained to date are discussed.

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.

The A286 is one of the earliest superalloys developed. It has been used for manufacturing different components of turbo machineries because of its balanced high temperature properties. These components include shafts, discs, spacers, blades and fasteners. This paper reviews some of the issues and recent field experiences related to metallurgy, fabrication, in-service evaluation and failure of some of these components. The fabrication aspects including the effects of alloy melting processes, forging parameters and different types of heat treatments on the processed parts are discussed. The importance of these factors on the microstructure and properties of A286 are highlighted. The effects of service exposure on some of these parts are also discussed. In service evaluation involves checking for service induced damage or changes in microstructures and properties so that the suitability of the part for continued service can be determined. The failure analysis section of the paper briefly discusses failures of two expander wheels and an expander disc made out of A286 to pinpoint some of the salient features of damage accumulation and fracture during service.

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.

Creep-resistant austenitic stainless steels are known to be the potential candidate materials for use as super- and re-heater tubes in ultra-super critical (USC) power plants. Among them, ASTM A213/A213M S30432, a novel 18-8 stainless steel (18Cr- 9Ni-3Cu-Nb-N), has attracted considerable attention from electric industry due to its combined lower cost and more excellent performance in contrast to traditional TP347H steel. More than 10 years of service in Japan laid a solid foundation for the steel being selectable USC boiler materials. Steels of S30432 have been recently developed in China during the past few years. This paper presents the evaluation results of S30432 tubes manufactured by four steel plants in China as well as Sumitomo super304H tubes for comparison. A detailed microstructural analysis of the tubes has been performed by using optical and electron microscope, and mechanical properties of the tubes have been evaluated using hardness testing as well as tensile testing up to 700°C. It was found that the impurity elements, nonmetallic inclusions and grain size of the S30432 tubes were well controlled. TEM observation revealed the microstructural changes for a selected batch of S30432 specimens in condition of hot rolled material, as-extruded tube, solution treated tube and 650°C/1000h aged tube. Most attention was paid to the morphology and distribution of precipitates in the microstructure which should be responsible for the enhanced performance of the steel. Although the hardness of all the evaluated tubes was measured to be similar, they showed more or less differences in tensile properties between each other. Creep rupture testing is still in progress, and the steel might exhibit excellent long-term creep rupture strength at 650°C as was predicted from the currently available testing results.

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.

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.