In a European ultra-supercritical (USC) power station repaired reheater bundle tubes made out of 25% Chromium stainless steels developed stress relief damages at the tube-to-tube butt welds, leading to leakages after only 8.500 hours of operation. Laboratory investigations of the leakages revealed common features of stress relief cracking (SRC) such as highly localized intergranular cracking in the heat affected zone (HAZ) near the fusion line, creep void formation at the crack tip and around the crack. At that time no other SRC damages were known for the employed 25% Chromium stainless steel boiler tubes. This article briefly describes the SRC damage found on the repaired reheater bundle tubes. It further provides insight on the several laboratory tests employed to assess the SRC behavior of welded joints of different creep resistant stainless steels. Among the selected test methods were Slow-Strain-Rate-Tests (SSRT), static 3-point bending tests derived from the Van Wortel approach and component tests. The results provided by the described tests methods have shown that the SRC behavior of a given material combination must be assessed by different techniques. This is especially the case for the evaluation of potential countermeasures and for the determination of the service conditions leading to the highest susceptibility.

Steam-side oxidation and the resultant exfoliation of iron-based scales cause unplanned shutdowns at coal-fired power generation plants. Exfoliate removal is currently limited to frequent unit cycling to minimize the volume of exfoliated scale, upgrading a plant with a “blow down” system, or installing a higher alloy. This paper discusses the rate of steam-side oxidation on Type 304H stainless steel (304H) tube after shot peening the internal surface with commercially available techniques. Shot peening the ID of Type 304H austenitic stainless steel superheater tubes has been shown to improve the overall oxidation resistance in steam. Decreasing the oxidation rate directly impacts the volume of exfoliated scale. The adherent spinel scales are thinner and more robust than non-shot peened tubes of the same alloy. Most of the improved oxidation resistance can be attributed to the presence of a spinel oxide layer combined with a continuous chromia layer formed near the steam-touched surfaces. The presence of a continuous chromia layer vastly reduces the outward diffusion of iron and minimizes the formation of iron-based scales that exfoliate. This work showed that a uniform cold-worker layer along the tube ID has a profound effect on oxidation resistance. Incomplete coverage allows oxidation to proceed in the non-hardened regions at a rate comparable to the oxidation rate on unpeened Type 304H.

Austenitic stainless steels have been used for boiler tubes in power plants. Since austenitic stainless steels are superior to ferritic steels in high temperature strength and steam oxidation resistance, austenitic stainless steel tubes are used in high temperature parts in boilers. Dissimilar welded joints of austenitic steel and ferritic steel are found in the transition regions between high and low temperature parts. In dissimilar welded parts, there is a large difference in the coefficient of thermal expansion between austenitic and ferritic steel, and thus, thermal stress and strain will occur when the temperature changes. Therefore, the dissimilar welded parts require high durability against the repetition of the thermal stresses. SUPER304H (18Cr-9Ni-3Cu-Nb-N) is an austenitic stainless steel that recently has been used for boiler tubes in power plants. In this study, thermal fatigue properties of a dissimilar welded part of SUPER304H were investigated by conducting thermal fatigue tests and finite element analyses. The test sample was a dissimilar welded tube of SUPER304H and T91 (9Cr-1Mo-V-Nb), which is a typical ferritic heat resistant boiler steel.

The microstructural evolution has been investigated for an 18Cr-12Ni stainless steel (347HFG) that has been subject to a thermo-mechanical treatment to obtain a fine grain size (ASTM 7-10). In particular, sigma phase precipitation and growth has been evaluated. Samples of 347HFG stainless steel have been isothermally heat treated to reproduce and accelerate the ageing conditions experienced in-service at temperatures between 600 and 750 °C for up to 10,000 hours. Results have shown that sigma phase is precipitated at triple points and along grain boundaries after as little as 1000 hours which is contrary to thermodynamic predictions. In addition X-ray diffraction (XRD) and image analysis has been carried out to semi-quantitatively measure the amount of sigma phase present. The area fraction of sigma has been found to be 2.77 and 2.23 percent at 700 and 750 °C respectively. This is a higher volume fraction of sigma phase than has been previously observed in regular 347H at these conditions. It is thought that this is due to the reduced grain size that has provided an increase in nucleation sites and diffusion paths that can enhance the precipitation and growth of sigma phase. The results from this study are discussed with regards to the effect of precipitation on the service life of a 347HFG stainless steel tube operating in advanced supercritical boilers.

Up to now, the amount of supercritical boilers in China has ranked number one in the world. Many supercritical boilers have run for more than 100,000 hours. Creep becomes one of the main reasons for supercritical boiler tubes failure. In this article, the failure of superheater tubes in a supercritical boiler was analyzed, the microstructural evolution of austenitic stainless steel tubes were studied, a full investigation into the failure cause was carried out involving in visual examination, optical microscope, SEM, TEM and XRD. The results show, sigma phase precipitates in this austenitic steel with the extension of service time, sigma precipitates form at grain boundaries by continuous chain. Sigma precipitates are hard and brittle, weaken grain boundaries and cause microscopic damage, eventually lead to boiler tubes failure.

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.

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

A longitudinal crack and window opening type failure occurred in neutral zone that is applied to least plastic deformation in the bent TP347H tube during operation. From the analysis of residual stress and plastic deformation during the tube bending, there is low creep strength and high residual stress in neutral zone as compared other regions like intrados and extrados. Therefore, failure occurred in neutral zone due to stress relaxation concentrated in grain boundary during operation.

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.

The spalling of oxide scales at the steam side of superheater and reheater of ultra-supercritical unit is increasingly serious, which threatens the safe and economic operation of the boiler. However, no effective monitoring method is proposed to provide an on-line real-time detection on the spalling of oxide scales. This paper proposes an on-line magnetic non-destructive testing method for oxide granules. The oxide scale-vapor sample from the main steam pipeline forms liquid-solid two-phase flow after the temperature and pressure reduction, and the oxide granules are separated by a separator and piled in the austenitic pipe. According to the difference of the magnetic features of the oxide scales and the austenitic pipe, the oxide granule accumulation height can be detected through the spatial gradient variations of the magnetic induction. The laboratory test results show that the oxide scale accumulation can be accurately calculated according to the spatial gradient changes around the magnetized oxide granules, with the detection error not exceeding 2%.

The steam oxidation behaviour of boiler tubes and steam piping components is a limiting factor for improving the efficiency of the current power plants. Spallation of the oxide scales formed during service can cause serious damage to the turbine blades. Vallourec has implemented an innovative solution based on an aluminum diffusion coating applied on the inner surface of the T/P92 steel. The functionality of this coating is to protect the tubular components against spallation and increase the actual operating temperature of the metallic components. In the present study, the newly developed VALIORTM T/P92 product was tested at the EDF La Maxe power plant (France) under 167b and 545°C (steam temperature). After 3500h operation, the tubes were removed and characterized by Light Optical Metallography (LOM), Scanning Electron Microscopy (SEM), with Energy Dispersive X-ray spectrometry (EDX) and X-Ray Diffraction (XRD). The results highlight the excellent oxidation resistance of VALIORTM T/P92 product by the formation of a protective aluminum oxide scale. In addition, no enhanced oxidation was observed on the areas close to the welds. These results are compared with the results obtained from laboratory steam oxidation testing performed on a 9%Cr T/P92 steel with and without VALIORTM coating exposed in Ar-50%H 2 O at 650°C.

Coal ash corrosion testing was conducted on six solution-treated nickel-based alloy plates (Alloy 617, Alloy 263, Alloy 740, Alloy 141, HR6W [45Ni-23Cr-7W], and HR35 [50Ni-30Cr-4W-Ti]) intended for advanced-USC boilers, along with conventional ferritic and austenitic stainless tubes for comparison. Tests used synthetic coal ash (Na 2 SO 4 , K 2 SO 4 , Fe 2 O 3 ) with varying SO 2 concentrations (0.02-1.00 vol%). Results showed maximum metal loss at 700°C, with higher SO 2 levels causing increased corrosion. Materials with higher chromium content demonstrated better corrosion resistance, suggesting chromium content is a crucial factor in material selection for these applications.

The long-term performance of superheater super 304h tube during the normal service of an ultra-supercritical 1000mw thermal power unit was tracked and analyzed, and the metallographic structure and performance of the original tube sample and tubes after 23,400h, 56,000h, 64,000 h, 70,000 h and 80,000 h service were tested. The results show that the tensile strength, yield strength and post-break elongation meet the requirements of ASME SA213 S30432 after long-term service, but the impact toughness decreases significantly. The metallographic organization is composed of the original complete austenite structure and gradually changes to the austenite + twin + second phase precipitates. With the extension of time, the number of second phases of coarseness in the crystal and the crystal boundary increases, and the degree of chain distribution increases. The precipitation phase on the grain boundary is dominated by M 23 C 6 , and there are several mx phases dominated by NbC and densely distributed copper phases in the crystal. The service environment produces a high magnetic equivalent and magnetic induction of the material, the reason is that there are strips of martensite on both sides of the grain boundary, and the number of martensite increases with the length of service.

CWT (combined water treatment) was introduced in Japan in 1990 and over 50 power generation boilers are now in operation. However, the effect of oxygenated treatment on the steam oxidation of the ferritic-martensitic steels and austenitic stainless steels that are used for superheaters and reheaters is currently far from clear. In this study, laboratory tests were used to examine the effect of the oxygen level of the feed water on the scale growth and the scale exfoliation propensity of T91 ferritic-martensitic steel and 300-series austenitic stainless steels, as represented by TP316H and TP347H (coarse- and fine-grained, respectively). The oxygen level of the feed water had little effect on the steam oxidation rates of all the steels tested. Hematite (Fe 2 O 3 ) formed in the outer layer of the oxide scales on both the ferritic and austenitic steels and is considered to have been encouraged in the simulated CWT atmosphere. The adhesion strength of the oxide scale formed on T91 in the simulated CWT atmosphere, that is, scale in which hematite was present, was lower than that of the oxide scale formed in the simulated AVT (all volatile treatment) atmosphere. The oxidation rate of fine-grained TP347H was confirmed to be slower than that of coarse-grained TP316H. Hematite significantly influenced the scale exfoliation of the austenitic steels and the critical oxide thickness for exfoliation decreased with increasing proportion of hematite in the outer scale.

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.

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.

A new martensitic steel for power generation applications was developed: Tenaris High Oxidation Resistance (Thor) is an evolution of the popular ASME grade 91, offering improved steam oxidation resistance and better long-term microstructural stability, with equal or better creep strength. Thanks to its design philosophy, based on consolidated metallurgical knowledge of microstructural evolution mechanisms, and an extensive development performed in the last decade, Thor was engineered to overcome limitations in the use of ASME grade 91, yet allow being processed in the same fashion, permitting the re-use of consolidated best practices for boiler fabrication. In order to evaluate the possibility to produce complete pressure part systems, various tests to manufacture components have been performed on Thor pipes and tubes (i.e. finning, bending, welding) and on Thor forged material (i.e. flanges). In all cases consolidated industrial best practices used on ASME grade 91 were applied, and resulting properties met ASME requirements.

In the “Boiler Materials for Ultrasupercritical Coal Power Plants” program, sponsored by the U.S. Department of Energy and the Ohio Coal Development Office, various materials are being assessed for their suitability in the high-temperature, high-pressure environment of advanced ultrasupercritical (A-USC) boilers. Beyond mechanical properties and fireside corrosion resistance, these materials must also exhibit adequate steamside oxidation and exfoliation resistance. A comprehensive database of steamside oxidation test results at temperatures relevant to A-USC conditions has been compiled over recent years. These tests have been conducted on ferritic and austenitic materials with chromium content ranging from 2 to 26%. The specimens were evaluated for oxidation kinetics and oxide morphology. The findings indicate that steamside oxidation behavior is significantly affected by temperature, the chromium content of the material, and the ability of chromium to diffuse through the material's crystallographic lattice structure. Additionally, surface treatments have been applied to enhance the steamside oxidation resistance of certain materials. While these treatments have shown potential, their effectiveness can be limited by the operational temperatures.

18Cr-9Ni-3Cu-Nb-N steel is widely used for heat exchanger tubes such as super-heaters and reheaters of ultra-super critical power generation boilers. In this study, long-term creep rupture tests were carried out on 18Cr-9Ni-3Cu-Nb-N seamless steel tubes of 7 heat materials, and the specimens of 2 heat materials with different creep rupture strengths were observed by ultra-low voltage scanning electron microscope after creep rupture tests. The results of the investigation of the creep rupture specimens and the coverage ratios of M 23 C 6 on grain boundary were different. The cause of this was estimated to be the difference in B content between the 2 heat materials. Creep rupture tests with different final ST temperatures were also carried out using the same heat material, and it was revealed that the higher final ST temperature, the higher the creep rupture strength. As the final ST temperature is higher, the amount of Nb(C, N) solid solution in the matrix increases, and the amount of precipitation of NbCrN and M 23 C 6 increases during creep, therefore it is assumed that the creep rupture strength increases.

Super 304H is a new generation of advanced austenitic stainless steels that is increasingly being used in superheater/ reheater (SH/RH) sections of thermal ultra-supercritical steam power plants due to its high creep strength combined with good oxidation resistance and microstructure stability. However, recent studies have shown significant microstructural changes and associated degradation in creep performance during long-term service exposure in this alloy. Microstructure evolution during service and its effect on the long-term creep performance has not been comprehensively assessed. In this work, variations in the microstructure of long-term service exposed Super 304H RH tubes (~99,600 hours at 596°C steam temperature) are documented. The results for the ex-service material are compared to well-documented laboratory studies to provide perspective on improved life management practices for this mainstay advanced stainless steel.