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.

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.

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.

T24 tube material (7CrMoVTiB10-10), with its combination of high creep strength and potential to be welded without using preheat, is regarded as a candidate waterwall material for Ultra Supercritical (USC) boilers. However, its reputed sensitivity to hydrogen and potential for secondary hardening may have adverse impacts on construction of waterwall panels. Doosan Babcock Ltd have investigated the response of welds made in T24 tubing to secondary hardening via changing hardness in a series of ageing heat treatment trials. Also, the response of the material to hydrogen infusion has been investigated

The use of the bainitic class of creep strength enhanced ferritic steels T/P23 and T24 has increased over the last decade in a wide range of applications including replacement headers, superheater and reheater tubing and in waterwall tubing. Many issues have been reported in one or both of these materials including hydrogen induced cracking, reheat cracking and stress corrosion cracking. To appropriately address these issues, work has been initiated that includes a literature review, development of a database of phase transformation temperatures, investigation of tempering behavior, and an analysis of the effect of phase transformation on residual stresses. Such information will be provided in the context of understanding why these two materials appear highly susceptible to these cracking mechanisms.

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.

The efficiency of power plants is depending on the steam temperature and/or the steam pressure. Efficiency increasing from 35% to 42-45% require increasing of the steam temperature over 600°C and the pressure over 26 MPa. According to the designer opinion it is not profitable to use classical low alloy creep resistant steels 16Mo3, 13CrMo4-5 or 10CrMo9-10 for membrane waterwall construction for these service condition. New modified low alloy creep resistance T23 and T24 (7CrMoVTiB10-10) steels were developed for membrane waterwalls. Welding of these steels with small thickness (around 6.3 mm) should be enabled without preheating and post weld heat treatment (PWHT) due to the lower carbon content below 0.1%. High creep rupture strength (CRS) values are achieved by Ti, N and B elements alloyed to T24 steel. The original expectation that the welding small thickness without preheating was early overcome and was wrong. According to the present experience the T24 steel is welded with preheating at 150-250°C depending on the wall thickness and welded joint toughness in order to achieve required hardness and impact toughness values. Opinions on the T24 welded joints post weld heat treatment (PWHT) requirements are still inconsistent. Especially the membrane waterwalls of the supercritical power plants are still produced without PWHT.

Preface for the 2004 Advances in Materials Technology for Fossil Power Plants conference.

Early supercritical units such as American Electric Power (AEP) Philo U6, the world’s first supercritical power plant, and Eddystone U1 successfully operated at ultrasupercritical (USC) levels. However due to the unavailability of metals that could tolerate these extreme temperatures, operation at these levels could not be sustained and units were operated for many years at reduced steam (supercritical) conditions. Today, recently developed creep strength enhanced ferritic (CSEF) steels, advanced austenitic stainless steels, and nickel based alloys are used in the components of the steam generator, turbine and piping systems that are exposed to high temperature steam. These materials can perform under these prolonged high temperature operating conditions, rendering USC no longer a goal, but a practical design basis. This paper identifies the engineering challenges associated with designing, constructing and operating the first USC unit in the United States, AEP’s John W. Turk, Jr. Power Plant (AEP Turk), including fabrication and installation requirements of CSEF alloys, fabrication and operating requirements for stainless steels, and life management of high temperature components

Along with rapid development of thermal power industry in mainland China, problems in metal materials of fossil power units also change quickly. Through efforts, problems such as bursting due to steam side oxide scale exfoliation and blocking of boiler tubes, and finned tube weld cracking of low alloy steel water wall have been solved basically or greatly alleviated. However, with rapid promotion of capacity and parameters of fossil power units, some problems still occur occasionally or have not been properly solved, such as weld cracks of larger-dimension thick-wall components, and water wall high temperature corrosion after low-nitrogen combustion retrofitting.

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.

In Europe between 2006 and 2012 several ultra-super-critical (USC) coal-fired power plants were built employing T24 (7CrMoVTiB10-10 / DIN EN 10216-2:2014-03 / VdTÜV sheet 533/2) in membrane walls. During commissioning stress corrosion cracking (SCC) on the tube-to-tube butt welds appeared. The widespread damages required the development of a new patented commissioning procedure to avoid recurring damages. Although this commissioning procedure was employed successfully and the power plants are in operation since then, a debate about the implementation of a hardness limit for such butt welds was initiated. According to the European standards butt welds of T24 boiler tubes with wall thickness < 10 mm (0.3937 in) do not require any post-weld heat treatment (PWHT) and no hardness limits are given. When looking at manufacturing related issues such as an imminent risk of cold cracking after welding of micro-alloyed steels a widely applied but coarse hardness limit is 350 HV. Based on laboratory tests, some authors reallocated this 350 HV hardness limit for addressing SCC susceptibility of low-alloyed steels. This article describes typical hardness levels of T24 boiler tube TIG butt welds and the SCC behavior in high temperature water. Further the effect of the stress relief heat treatment (SRHT) of the boiler membrane walls between 450 °C and 550 °C (842 °F and 1022 °F) on its hardness values and on the SCC behavior is discussed, showing that the hardness values should not be used as an indicator for SCC susceptibility of T24 boiler tube butt welds.

The use of the bainitic creep strength enhanced ferritic steel T/P23 has increased over the last decade in a wide range of applications including headers, superheater and reheater tubing and in waterwall tubing. Many issues have been reported in weldments of this material, such as hydrogen induced cracking, reheat cracking and stress corrosion cracking. In order to help characterize high temperature cracking phenomena, including reheat cracking, a limited number of laboratory creep crack growth tests are being conducted as part of an ongoing project. Tests were run on as-welded sections with the test specimen crack-tip located in select zones of the weldment. Test temperatures are intended to bookend the range of applications from a waterwall condition of ~482°C (900°F) to the superheat/reheat condition of 565°C (1050°F). This paper describes the results of some early testing at 482°C (900°F). The tests provided useful insight into the cracking susceptibility of the material at this temperature with respect to not only time-dependent cracking, but also fatigue crack growth and fracture toughness. The paper includes details of the test method and results, as well as findings from post-test metallographic examinations of the tested specimens.

Because of the problems experienced with steam-side oxide scale exfoliation in commercial power plants, there has been increased interest in understanding the steam oxidation resistance of 300- series stainless steels such as 347H and 304H. Model alloys were used in an attempt to understand the effect of varying Ni (9-12%) and Cr (16-20%) on steam oxidation resistance at 650°C. However, the model alloys generally showed superior oxidation resistance than commercial alloys of similar composition. Several surface engineering solutions also were investigated. The commercially favored solution is shot peening. Laboratory steam testing at 650°C found that annealing temperatures of ≥850°C eliminated the benefit of shot peening and a correlation was observed with starting hardness in the peened region. This effect of annealing has implications for the fabrication of shot peened tubing. Another route to improving oxidation resistance is the use of oxidation resistant diffusion coatings, which can be deposited inexpensively by a vapor slurry process. Uniform coatings were deposited on short tube sections and annealed at 1065°C to retain good 650°C creep properties. The coating was thicker than has been investigated in laboratory processes resulting in increased brittleness when the coating was assessed using 4-point bending.

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.

The objective of this study was to determine the typical range of weld metal cooling rates and phase transformations during multipass gas-tungsten arc (GTA) welding of Grade 23 (SA-213 T23) tubing, and to correlate these to the microstructure and hardness in the weld metal and heat affected zone (HAZ). The effect of microstructure and hardness on the potential susceptibility to cracking was evaluated. Multipass GTA girth welds in Grade 23 tubes with outside diameter of 2 in. and wall thicknesses of 0.185 in. and 0.331 in. were produced using Grade 23 filler wire and welding heat input between 18.5 and 38 kJ/in. The weld metal cooling histories were acquired by plunging type C thermocouples in the weld pool. The weld metal phase transformations were determined with the technique for single sensor differential thermal analysis (SS DTA). The microstructure in the as-welded and re-heated weld passes was characterized using light optical microscopy and hardness mapping. Microstructures with hardness between 416 and 350 HV 0.1 were found in the thick wall welds, which indicated potential susceptibility to hydrogen induced cracking (HIC) caused by hydrogen absorption during welding and to stress corrosion cracking (SSC) during acid cleaning and service.

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.

Starting in 2010 a new generation of coal fired power plants in Europe operating at a steam temperature of up 620°C was commissioned. During that commissioning process many cracks occurred in welds of T24 material which was extensively used as membrane wall material in nearly all of the new boilers. The cracks were caused by stress corrosion cracking (SCC) only occurring in the areas of the wall being in contact to high temperature water during operation. The question which step of the commissioning process really caused the cracking was not answered completely even several years after the damage occurred. To answer this question and to define parameters which will lead to cracking in high temperature water many tests were conducted. Generally it was found that slow tensile tests in controlled environment are well suited to get information about materials SCC sensitivity in the laboratory. In the present paper, first the influence of the cracking of welded T24 material in acidic environment containing well-defined amounts of H2S is investigated to address the question if a chemical cleaning process prior to the testing might lead to hydrogen induced SCC. As a second step, cracking behaviour in high temperature water is being investigated. Here the influence of the temperature, the oxygen concentration of the water, the deformation speed of the sample, the heat treatment and the condition of the material on the SCC is analysed.