The “Coal Ash Corrosion Resistant Materials Testing Program” by The Babcock & Wilcox Company (B&W), the U.S. Department of Energy (DOE), and the Ohio Coal Development Office (OCDO) at Reliant Energy's Niles plant provides full-scale in-situ testing of advanced boiler superheater materials to address fireside corrosion, a key issue for improving efficiency in new coal-fired plants and service life in existing ones. In 1998, B&W developed a system with three identical sections containing multiple segments of twelve different materials from contributors like Oak Ridge National Laboratory (ORNL), cooled by reheat steam and installed in 1999 above the furnace entrance in the Niles Plant 110 MWe Unit #1 firing high-sulfur Ohio coal to test materials at advanced supercritical steam temperatures (1100°F+) in corrosive conditions. The first section was evaluated after 29 months in 2001, the second in 2003, and the final section is expected for removal in 2005. This paper outlines the program, test system, and materials, and it presents the evaluation results for the first two sections.

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.

Ni-38Cr-3.8Al has high hardness and high corrosion resistance with good hot workability, and therefore, it has been applied on various applications. However, in order to expand further application, it is important to understand the high temperature properties. Then, this study focused on the high temperature properties such as thermal phase stability, hardness, tensile property, creep property and hot corrosion resistance. As the result of studies, we found that the thermal phase stability of (γ/α-Cr) lamellar structure and the high temperature properties were strongly influenced by the temperature. Although the high temperature properties, except for creep property, of Ni-38Cr-3.8Al were superior to those of conventional Ni-based superalloys, the properties were dramatically degraded beyond 973 K. This is because the lamellar structure begins to collapse around 973 K due to the thermal stability of the lamellar structure. The hot corrosion resistance of Ni-38Cr-3.8Al was superior to that of conventional Ni-based superalloys, however, the advantage disappeared around 1073 K. These results indicate that Ni-38Cr-3.8Al is capable as a heat resistant material which is required the hot corrosion resistance rather than a heat resistant material with high strength at high temperature.

Energy requirements and environmental concerns have promoted a development in higher-efficiency coal fired power technologies. Advanced ultra-super critical power plant with an efficiency of higher than 50% is the target in the near future. The materials to be used due to the tougher environments become therefore critical issues. This paper provides a review on a newly developed advanced high strength heat resistant austenitic stainless steel, Sandvik Sanicro 25, for this purpose. The material shows good resistance to steam oxidation and flue gas corrosion, and has higher creep rupture strength than any other austenitic stainless steels available today, and has recently obtained two AMSE code cases. This makes it an interesting option in higher pressures/temperature applications. In this paper, the material development, structure stability, creep strength, steam oxidation and hot corrosion behaviors, fabricability and weldability of this alloy have been discussed. The conclusion is that the Sanicro 25 is a potential candidate for superheaters and reheaters in higher-efficiency coal fired boilers i.e. for applications seeing up to 700°C material temperature.

For higher efficiency and competitive overall performance, it would be an advantage to be able to safely exceed the highest operational values, currently up to about 600-620°C/25-30 MPa in supercritical (SC) boiler plants. Under such operating conditions the oxidation resistance in SC water tends to limit the potential for further improvement of efficiency. The way to increase the oxidation resistance of traditional austenitic boiler tubes e.g. TP 347H is to do additional cold work on the boiler tube inner surface. In the current paper the effect of cold work on the oxidation resistance of TP347H and TP347HFG has been evaluated by shot peened samples with different parameters and subjecting those samples to supercritical oxidation exposure. The results show an improvement in the oxidation resistance of the alloys, especially in the large grained alloy TP347H. Also the uniformity of the deformation layer was seen to have an influence on the oxidation resistance, since the oxide nodules start to grow at locations with the thinnest or no deformation layer.

A consortium which includes Energy Industries of Ohio, the Electric Power Research Institute, Inc., and four major US boiler manufacturers (the Babcock & Wilcox Company, Riley Power, Foster Wheeler, and Alstom Power) is conducting a 5-year materials development program to advance the technology in coal-fired power generation. As part of this development effort, new high temperature, corrosion resistant alloys must be evaluated and qualified for dependable operation in a corrosive coal-fired environment to produce steam for Ultra Supercritical (USC) cycle operation up to 760°C (1400°F) and 35 MPa (5000 psi.) To evaluate the fireside corrosion resistance of candidate materials for USC power generation, two superheater test loops comprised of seven different advanced alloys were designed and fabricated by the Babcock and Wilcox Company (B&W) in Barberton, Ohio. These loops were installed at the Reliant Energy power plant located in Niles, OH, and testing of these loops was initiated in December, 2003. Following a minimum of 18 months of testing, the loops will be removed for metallurgical examination and assessment by B&W. This paper describes some of the considerations in designing, fabricating, and installing the two USC test loops, as well as the methodology for monitoring their performance during operation.

Sanicro 25 material is approved for use in pressure vessels and boilers according ASME code case 2752, 2753 and VdTUV blatt 555. It shows higher creep rupture strength than any other austenitic stainless steels available today. It is a material for superheater and reheaters, enabling higher steam parameters of up to about 650 °C steam (ie about max 700 °C metal) without the need for expensive nickel based alloys. The aim of the present study is the investigation of the steam oxidation resistance of the Sanicro 25. The long term test was conducted in the temperature range 600 -750 °C up to 20 000 hours. The morphology of the oxide scale and the microstructure of the bulk material were investigated. In addition, the effect of surface finish and pressure on the steam oxidation were also studied.

The Advanced Ultrasupercritical (A-USC) power plants are aimed to operate at steam inlet temperatures greater than 700°C; consequently, a complete materials overhaul is needed for the next-generation power plants. HAYNES 282, a gamma-prime strengthened alloy, is among the leading candidates because of its unique combination of properties, superior creep and LCF strength, fabricability and thermal stability. It is currently being evaluated in wrought and cast forms for A-USC turbine rotors, casings, boiler tubings, header, and valves. The candidate materials for A-USC applications not only require oxidation resistance for steam cycles but fireside corrosion resistance to coal ash is also of an extreme importance. In order to study the effect of both environments on the performance of 282 alloy, the alloy was exposed for extended periods in various oxidizing environments, such as air, air plus water vapor (10%), and 17bar steam up to 900°C. The fireside corrosion resistance of 282 alloy was evaluated at 700°C in synthetic coal ash and at 843°C in alkali salt deposits in a controlled gaseous 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 power generation industry worldwide aims to develop coal-fired boilers operating at much higher efficiencies than current supercritical plants. This increased efficiency is expected through ultrasupercritical steam conditions, requiring new materials for critical components. To limit the use of expensive alloying materials, it is necessary to maximize the strength and corrosion capabilities across the material spectrum from ferritic to austenitic and nickel-based alloys. Sandvik Materials Technology has developed an austenitic alloy, Sanicro 25, with excellent high-temperature strength and corrosion resistance using an economical alloy composition. The alloy is designed for use within 700°C (1300°F)/300 bar (4500 psi) steam conditions and is a leading candidate material for such high-temperature applications. This paper introduces Sanicro 25, its development status, and properties.

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.

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

To improve the efficiency of fossil fuel power plants the operating temperatures and pressures need to be increased. However, at high temperatures the steam side oxidation resistance becomes a critical issue for the steels used especially at the final stages of superheaters and reheaters. Apart from the chemical composition of the material, surface condition is a major factor affecting the oxidation resistance in steam and supercritical water. In this paper, stainless boiler steels (UNS S34710, S31035, S31042, and S30942) are investigated for oxidation resistance in flowing supercritical water. Tests were conducted in an autoclave environment (250 bar, with 125 ppb dissolved oxygen and a pH of 7) at 625°C, 650°C and 675°C for up to 1000 h. Materials were tested with as-delivered, shot peened, milled or spark eroded and ground surface finish. The results show a strong influence of surface finish at the early stages of oxidation. Oxides formed on cold worked surfaces were more adherent and much thinner than on a spark eroded and ground surface. This effect was stronger than the influence of temperature or alloy composition within the tested ranges.

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.

Structural alloy corrosion is a major concern for the design and operation of supercritical carbon dioxide (sCO 2 ) power cycles. Looking towards the future of sCO 2 system development, the ability to measure real-time alloy corrosion would be invaluable to informing operation and maintenance of these systems. Sandia has recently explored methods available for in-situ alloy corrosion monitoring. Electrical resistance (ER) was chosen for initial tests due the operational simplicity and commercial availability. A series of long duration (>1000 hours) experiments have recently been completed at a range of temperatures (400-700°C) using ER probes made from four important structural alloys (C1010 Carbon Steel, 410ss, 304L, 316L) being considered for sCO 2 systems. Results from these tests are presented, including correlations between the probe measured corrosion rate to that for witness coupons of the same alloys.

For raising thermal efficiency and decreasing CO 2 emission, China had constructed the first 600°C ultra-supercritical(USC) fossil power plant in 2006. Now more than a hundred 600°C, 1000MW USC electric power units have been put in service. Recently, China has also developed 620°C USC power units and some of them have been put in service already. Meanwhile, more than fifty 620°C USC boilers will be produced by various China boiler companies. The austenitic steels TP347H, Super304H and HR3C are routinely used for 600°C USC boilers. Among these steels, a big amount of Super304H has been used for boiler superheater/reheater components application. However, Super304H is characterized by good stress-rupture strength but poor corrosion/oxidation resistance. On the other side, HR3C is characterized by very good corrosion/oxidation resistance but lower stress-rupture strength than Super304H. Now, the China 620°C USC project needs a new austenitic heat resisting steel with high stress-rupture strength and good corrosion/oxidation resistance to fulfill the superheater/reheater tube components application requirement. A new austenitic heat resisting steel SP2215 is based on 22Cr-15Ni with certain amount of Cu and also Nb and N for multiphase precipitation (MX, Cu-rich phase, NbCrN) strengthening in Fe-Cr-Ni austenitic matrix and M 23 C 6 carbide precipitation at grain boundaries. This SP2215 new austenitic steel is characterized by high stress-rupture strength (650°C, 105h>130MPa) and good corrosion/oxidation resistance. SP2215 austenitic steel has been commercially produced in tube product form. This SP2215 new austenitic heat-resisting steel is recommended to be used as superheater/reheater components for 620°C USC boiler application.

Constricted steam oxidation resistance and finite microstructural stability limits the use of 9 - 12 wt.-% chromium ferritic-martensitic steels to steam temperatures of about 620 °C. Newly developed 12 wt.-% Cr steels are prone to Z-phase precipitation, which occurs at the expense of the strengthening precipitates, and therefore suffer an accelerated decline in strength during longterm operation. While the concept of ferritic-martensitic chromium steels thus seems to hit technological limitations, further improvement in steam power plant efficiency necessitates a further increase of steam pressure and temperature. Furthermore increasing integration of intermitting renewable energy technologies in electrical power generation poses a great challenge for supply security, which has to be ensured on the basis of conventional power plant processes. Besides improved efficiency for resource preservation, load flexibility, thermal cycling capability and downtime corrosion resistance will play key roles in the design of tailored materials for future energy technology. Under these preconditions a paradigm shift in alloy development towards improvement of cyclic steam oxidation and downtime corrosion resistance in combination with adequate creep and thermomechanical fatigue strength seems to be mandatory. The steam oxidation, mechanical and thermomechanical properties of fully ferritic 18 - 24 wt.-% chromium model alloys, strengthened by the precipitation of intermetallic (Fe,Cr,Si)2(Nb,W) Laves phase particles, indicate the potential of this type of alloys as candidate materials for application in highly efficient and highly flexible future supercritical steam power plants.

The EU NextGenPower-project aims at demonstrating Ni-alloys and coatings for application in high-efficiency power plants. Fireside corrosion lab and plants trials show that A263 and A617 perform similar while A740H outperforms them. Lab tests showed promising results for NiCr, Diamalloy3006 and SHS9172 coatings. Probe trials in six plants are ongoing. A617, A740H and A263 performed equally in steamside oxidation lab test ≤750°C while A617 and A740H outperformed A263 at 800°C; high pressure tests are planned. Slow strain rate testing confirmed relaxation cracking of A263. A creep-fatigue interaction test program for A263 includes LCF tests. Negative creep of A263 is researched with gleeble tests. A263 Ø80 - 500mm trial rotors are forged with optimized composition. Studies for designing and optimizing the forging process were done. Segregation free Ø300 and 1,000mm rotors have been forged. A263 – A263 and A293 – COST F rotor welding show promising results (A263 in precipitation hardened condition). Cast step blocks of A282, A263 and A740H showed volumetric cracking after heat treatment. New ‘as cast’ blocks of optimized composition are without cracks. A 750°C steam cycle has been designed with integrated CO 2 capture at 45% efficiency (LHV). Superheater life at ≤750°C and co-firing is modeled.

Ultrasupercritical (USC) coal-fired boilers, currently under study, will be required to utilize a variety of new, high strength alloys. These alloys will have improved mechanical properties compared with more traditional boiler materials and so will be suitable for operation in higher temperature service. However, environmental resistance, i.e. internal steam oxidation and external coal-ash corrosion, will be a factor limiting application of some materials under consideration. In those cases, the operating range of lower-cost alloys can be significantly extended by the use of surface modification techniques. This paper will review potential surface modification techniques and report on early test results of some laboratory evaluations.