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.

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.

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.

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.

Utilities worldwide are facing increased demand for additional electricity, reduced plant emissions and greater efficiency. Part of the solution is achieved by increasing boiler temperature, pressure and coal ash corrosion resistance of the materials of boiler construction. In this paper, a new nickel-base tube alloy, INCONEL alloy 740, meeting this challenge is characterized with emphasis on mechanical properties, coal ash and steam corrosion resistance as well as weldability. Microstructural stability as a function of temperature and time is addressed as well as some of the early methodology employed to arrive at the current chemical composition. Brief mention is made of certain current and future alloy characterization efforts and potential environmental benefits to be expected should the boiler technology utilizing INCONEL alloy 740 be adopted.

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.

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.

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.

Using oxygen, rather than air, in coal-fired boilers has been studied for several years as a strategy to reduce NOx and concentrate CO 2 for capture. In combination with flue gas recirculation, higher levels of CO 2 are expected but increased H 2 O and SO 2 levels also may occur. In order to understand the role of substrate composition on corrosion, a combination of commercial and model alloys were investigated with synthetic coal ash and gas compositions simulating air- and oxyfiring environments. Exposure temperatures ranged from 600°-800°C to cover current operating temperatures up to advanced ultrasupercritical conditions. Using 500h exposures, no consistent negative effect was found for switching to the oxy-firing environment with the same synthetic ash. For model Fe-Cr alloys, 30%Cr was needed to form a thin protective reaction product across this temperature range. Among the commercial stainless steels, 310-type stainless steel showed low reaction rates with the maximum attack at 650°C. At higher temperatures, the depth of attack on Fe-base type 310 stainless steel was less than for Ni-base alloy 740. Initially, this difference was attributed to the Al and Ti additions in alloy 740. However, cast and hot rolled model Ni-18Cr and -22Cr alloys with various Al and Ti additions showed decreased metal loss with increasing Al and Ti additions in the oxy-firing environment at 700° and 800°C. As expected, metal loss was very sensitive to Cr content. A second set of model alloys also examined the effect of Co and Mo.

A new nickel-based superalloy, designated as GH750, was developed to meet the requirements of high temperature creep strength and corrosion resistance for superheater/reheater tube application of A-USC power plants at temperatures above 750°C. This paper introduces the design of chemical composition, the process performance of tube fabrication, microstructure and the properties of alloy GH750, including thermodynamic calculation, room temperature and high temperature tensile properties, stress rupture strength and thermal stability. The manufacturing performance of alloy GH750 is excellent and it is easy to forge, hot extrusion and cold rolling. The results of the property evaluation show that alloy GH750 exhibits high tensile strength and tensile ductility at room and high temperatures. The 760°C/100,000h creep rupture strength of this alloy is larger than 100MPa clearly. Microstructure observation indicates that the precipitates of GH750 consist of the precipitation strengthening phase γ’, carbides MC and M 23 C 6 and no harmful and brittle TCP phases were found in the specimens of GH750 after long term exposure at 700~850°C. It can be expected for this new nickel-based superalloy GH750 to be used as the candidate boiler tube materials of A-USC power plants in the future.

High-temperature corrosion occurs in different sections of energy production plants due to a number of factors: ash deposition, coal impurities, thermal gradients, and low NO x conditions, among others. High-temperature electrochemical corrosion rate (ECR) probes are rarely used at the present time, but if they were more fully understood, corrosion could become a process variable at the control of plant operators. Research is being conducted to understand the effects of probe composition, ash composition, environment chemistry, and measurement technique on the accuracy, response, and longevity of electrochemical corrosion rate probes. The primary goal is to understand when ECR probes accurately measure corrosion rates and when they are simply qualitative indicators of changes in the corrosion processes. Research to date has shown that ECR probe corrosion rates and corrosion rates from mass loss coupons agree within a factor of 2. This good agreement was found to depend on the composition of the sensors, with the best results coming from more highly alloyed materials such as 316L stainless steel and poorer results from carbon steel sensors. Factors being considered to help explain the good or poor agreement between mass loss and ECR probe corrosion rates are: values selected for the Stern-Geary constant, the effect of internal corrosion, and the presence of conductive corrosion scales and ash deposits.

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 combustion of coal and biomass fuels in power plants generates deposits on the surfaces of superheater / reheater tubes that can lead to fireside corrosion. This type of materials degradation can limit the lives of such tubes in the long term, and better methods are needed to produce predictive models for such damage. This paper reports on four different approaches that are being investigated to tackle the challenge of modelling fireside corrosion damage on superheaters / reheaters: (a) CFD models to predict deposition onto tube surfaces; (b) generation of a database of available fireside corrosion data; (c) development of mechanistic and statistically based models of fireside corrosion from laboratory exposures and dimensional metrology; (d) statistical analysis of plant derived fireside corrosion datasets using multi-variable statistical techniques, such as Partial Least Squares Regression (PLSR). An improved understanding of the factors that influence fireside corrosion is resulting from the use of a combination of these different approaches to develop a suite of models for fireside corrosion damage.

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.

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 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.

Oxyfuel combustion is considered as one of the most promising technologies to facilitate CO 2 capture from flue gases. In oxyfuel combustion, the fuel is burned in a mixture of oxygen and recirculated flue gas. Flue gas recirculation increases the levels of fireside CO 2 , SO 2 , Cl and moisture, and thus promotes fouling and corrosion. In this paper the corrosion performance of two superheater austenitic stainless steels (UNS S34710 and S31035) and one Ni base alloy (UNS N06617) has been determined in laboratory tests under simulated oxyfuel conditions with and without a synthetic carbonate based deposits (CaCO 3 - 15 wt% CaSO 4 , CaCO 3 - 14wt% CaSO 4 - 1 KCl) at 650 and 720°C up to 1000 hours. No carburization of the metal substrate was observed after exposure to simulated oxyfuel gas atmospheres without deposit, although some carbon enrichment was detected near the oxide metal interface. At 720°C a very thin oxide formed on all alloy surfaces while the weight changes were negative. This negative weight change observed is due to chromium evaporation in the moist testing condition. At the presence of deposits, corrosion accelerated and considerable metal loss of austenitic alloys was observed at 720°C. In addition, clear carburization of austenitic steel UNS S34710 occurred.

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.

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.

Increasing the steam temperature of a coal-fired pulverized coal (PC) power plant increases its efficiency, which decreases the amount of coal required per MW of electrical output and therefore decreases the emissions from the plant, including CO 2 . However, increasing the steam temperature requires that the materials for the boiler pressure parts and steam turbine be upgraded to high-nickel alloys that are more expensive than alloys typically used in existing PC units. This paper explores the economics of A-USC units operating between 595°C and 760°C (1100°F to 1400°F) with no CO 2 removal and with partial capture of CO 2 at an emission limit of 454 kg CO 2 /MW-hr (1000 lb CO 2 /MW-hr) on a gross power basis. The goal of the paper is to understand if the improved efficiency of A-USC would reduce the cost of electricity compared to conventional ultra-supercritical units, and estimate the economically “optimal” steam temperature with and without CO 2 removal.