Development of steels used in the power generation industry for the production of boilers characterized by supercritical parameters poses new challenges. The introduction of new combinations of alloying agents aimed at obtaining the best possible mechanical properties, including creep resistance, affects the weldability of new steels. Each of the latter has to undergo many tests, particularly as regards bending and welding, in order to enable the development of technologies ensuring failure-free production and assembly of boiler systems. Martensitic steels containing 9% Cr, used in the manufacturing of steam superheaters, are characterized by excellent creep resistance and, at the same time, low oxidation resistance at a temperature in excess of 600°C. In turn, steels with a 12% Cr content, i.e., VM12-SHC or X20CrMoV12-1 are characterized by significantly higher oxidation resistance but accompanied by lower strength at higher temperatures, which translates to their limited application in the production of boilers operating at the most top parameters.X20CrMoV12-1 was withdrawn from most of the power plants, and VM12-SHC was supposed to replace it, but unfortunately, it failed in regards to creep properties. To fulfill the gap a new creep strength-enhanced ferritic steel for service in supercritical and ultra-supercritical boiler applications was developed by Tenaris and it is designated as Thor115 (Tenaris High Oxidation Resistance). This paper covers the experience gained during the first steps of fabrication, which includes cold bending and welding of homogenous joints.

A creep resistant martensitic steel, CPJ7, was developed with an operating temperature approaching 650°C. The design originated from computational modeling for phase stability and precipitate strengthening using fifteen constituent elements. Approximately twenty heats of CPJ7, each weighing ~7 kg, were vacuum induction melted. A computationally optimized heat treatment schedule was developed to homogenize the ingots prior to hot forging and rolling. Overall, wrought and cast versions of CPJ7 present superior creep properties when compared to wrought and cast versions of COST alloys for turbines and wrought and cast versions of P91/92 for boiler applications. For instance, the Larson Miller Parameter curve for CPJ7 at 650°C almost coincides with that of COST E at 620°C. The prolonged creep life was attributed to slowing down the process of the destabilization of the MX and M 23 C 6 precipitates at 650°C. The cast version of CPJ7 also revealed superior mechanical performance, well above commercially available cast 9% Cr martensitic steel or derivatives. The casting process employed slow cooling to simulate the conditions of a thick wall full-size steam turbine casing but utilized a separate homogenization step prior to final normalization and tempering. To advance the development of CPJ7 for commercial applications, a process was used to scale up the production of the alloy using vacuum induction melting (VIM) and electroslag remelting (ESR), and underlined the importance of melt processing control of minor and trace elements in these advanced alloys.

The newly developed 12%Cr steel Super VM12 is characterized by excellent creep rupture strength properties (better than Grade 92) and enhanced steam oxidation resistance of 12%Cr steels such as VM12-SHC. Balanced properties profile of the new steel development in comparison to the existing well-established steels such as Grade 91 and Grade 92, opens opportunities for its application as construction material for components in existing or future high-efficiency power plants. In this study the oxidation behavior of typical 9%Cr steels was compared with the new steel development. The oxide scale morphologies and compositions of different oxide layers as function of temperature and exposure time in steam-containing atmospheres were characterized using light optical metallography, Scanning Electron Microscopy (SEM). Creep testing has been carried out in the temperature range between 525°C and 700°C. Selected creep specimens were investigated using the Transmission Electron Microscopy and the Atom Probe Tomography techniques.

The microstructures and mechanical properties of T122 steel used for superheater tube of the boiler in a 1000 MW ultra supercritical power plant after service for 83,000h at 590℃ were investigated, and compared with data of that served for 56,000h in previous studies. The results show that compared with T122 tube sample service for 56,000h, the tensile properties at room temperature and the size of precipitated phase exhibit few differences, but the lath martensites features are apparent, and the Brinell hardness value are obviously higher. SEM and TEM experiments show that the substructure is still dominated by lath martensite. A few lath martensites recover, subgrains appear and equiaxe, and the dislocation density in grains is relatively low. A large number of second-phase particles precipitated at boundaries of original austenite grains and lath martensite phases, which are mainly M 23 C 6 and Laves phases.

Extensive research and development has been undertaken in the UK on MarBN steels. These were first proposed by Professor Fujio Abe from NIMS in Japan. Within the UK, progress has been made towards commercialisation of MarBN-type steel through a series of Government funded industrial collaborative projects (IMPACT, IMPEL, INMAP and IMPULSE). As part of the IMPACT project, which was led by Uniper Technologies, boiler tubes were manufactured from the MarBN steel developed within the project, IBN1, and installed on the reheater drums of Units 2 and 3 of Ratcliffe-on-Soar Power Station. The trial tubes were constructed with small sections of Grade 91 tubing on either side of the IBN1 to allow direct comparison after the service exposure. This is the world’s first use of a MarBN steel on a full-scale operational power plant. In September 2018 the first tube was removed having accumulated 11,727 hours operation and 397 starts. This paper reports microstructural and oxidation analysis, that has been undertaken by Loughborough University as part of IMPULSE project, and outlines future work to be carried out.

In response to the strong needs for the life assessment of various components in fossil power plants, studies on Grade 91 and Grade 92 steels have been jointly performed by EPRI and CRIEPI for a last decade. These studies have been covering the effects of load variation (creep- fatigue) and stress multiaxiality as well as the behavior under uniaxial creep conditions. Based on abundant test data accumulated in this period and associated analytical evaluation, approaches based on inelastic strain energy have been developed for accurately assessing creep damage and failure lives under various conditions. The essence of these efforts is presented in this paper.

Inconel 740H is one of the most promising candidate Ni-base superalloys for the main steam pipe of 700 °C advanced ultra-supercritical (A-USC) coal-fired power plants. After processing and welding in manufacturing plant in solution-annealed state, large components was commonly suggested to have an extra aging treatment at 800 °C for 16 h, in order to obtain homogeneous γ′ precipitates. In this present work, creep tests and microstructure analyses were conducted on Inconel 740H pipe specimens under two different heat treatments to verify the necessity of aging process. Here we show that aging treatment has limited effect on the creep rupture life of Inconel 740H pipe. Both in grain interiors and along grain boundaries, crept specimens under two different heat treatments have the same precipitates. But the shape and distribution of γ′ in solution annealed sample is not as regular as the aged ones. Our results provide the underlying insight that aging treatment is not so necessary for the straight pipes if the on-site condition was hard to control. But for both groups of specimens, a small amount of h particles and some banded like M 23 C 6 were emerged during creep, which would be harmful to mechanical properties for the long run.

Development of the advanced USC (A-USC) boiler technology has been promoted in recent years, which targets 700°C steam condition. HR6W (Ni-23Cr-7W-Ti-Nb-25Fe) and HR35 (Ni-30Cr-6W-Ti-15Fe) have been developed for A-USC boiler tubes and pipes. The former alloy is mainly strengthened by Fe 2 W type Laves phase. The latter one employs precipitation strengthening of α-Cr phase in addition to Laves phase. Characteristic alloy design of both alloys, which does not use precipitation strengthening of γ′ phase (Ni 3 Al), leads to superior ductility and resistance to stress-relaxation cracking. Stability of creep strength and microstructure has been confirmed by long-term creep rupture tests. The 100,000h average creep rupture strength of HR6W is 85MPa at 700C. That of HR35 is 126MPa at 700°C which is comparable with conventional Alloy617. Tubes of both alloys have been evaluated by the component test in Japanese national A-USC project with γ′ hardened Alloy617 and Alloy263. Detailed creep strength, deformation behavior and microstructural evolution of these alloys are described from the viewpoint of the difference in strengthening mechanisms. Capability of these alloys for A-USC boiler materials has been demonstrated by the component test in the commercial coal fired boiler as the part of the A-USC project.

Detailed knowledge of the creep and creep crack behavior is essential for a safe operation of thick-walled components in thermal power plants. High mechanical loads and temperatures of more than 700 °C often require the application of nickel-based alloys, e.g. alloy C-263. Unfortunately, manufacturing and non-destructive evaluation (NDE) of thick-walled components (> 50 mm) made of nickel-based alloys are quite challenging. Tolerable critical flaw sizes, experimentally validated for long service durations, play an important role in the quality assurance of such components. It is commonly accepted that manufacturing parameters, e.g. heat treatment procedures, have a significant influence on creep ductility and time-dependent crack behavior. By means of adjusting the process parameters, the ductility and the creep life of notched specimen can be significantly improved in the case of alloy C-263. Essential root cause is the decoration of grain boundaries with carbides which drastically influences creep crack initiation and growth. This results in significant differences for allowable critical flaw sizes and thus, the potential use of the candidate material. On a first generation of alloy C-263 “G1”, a dense population of carbides on the grain boundaries was found, which resulted in an inadmissible creep crack behavior. The resulting critical flaw sizes were only a few tenths of a millimeter. On a second generation “G2”, the grain boundary occupation was positively influenced, so that a satisfactory creep crack behavior could be found. The critical flaw sizes are in the order of one millimeter or more. A critical or impermissible material behavior under creep conditions can be demonstrated by testing smooth and notched round specimens. For example, the first generation “G1” notched round specimens fails earlier than the smooth round specimens, indicating notch sensitivity. On the second generation “G2”, however, a notch insensitivity was found. The critical defect sizes can be determined by a method that takes into account a simultaneous examination of the crack tip situation and the ligament situation.

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 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.

The fall-off of oxide scale with poor adhesion inside superheater/reheater tubes in boilers for (ultra) supercritical power unit is the main cause of accidents such as superheater/reheater blockage, tube explosion and solid particle erosion in the steam turbine which cause serious economic losses. However, there is still no method for testing and assessing the adhesion of oxide scale inside the tube. A method for testing the adhesion of corrosion products in tubes by spiral lines is proposed in this paper, and the accuracy of adhesion evaluation is improved by adopting the image recognition method.

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%.

Advanced austenitic stainless steels, such as Super 304H, have been used in reheater and superheater tubes in supercritical and ultra-supercritical power plants for many years now. It is important to characterize the microstructure of ex-service reheater and superheater tubes as this will help researchers understand the long-term microstructural evolution and degradation of the material, which can impact the performance and lifetime of the components that are in service. In this research, the microstructure of an ex-service Super 304H reheater tube that has been in service for 99,000 hours at an approximate metal temperature of 873K (600°C) has been characterized. The characterization techniques used were electron microscopy-based and included imaging and chemical analysis techniques. Seven phases were observed as a result of the characterization work. The phases observed were MX carbonitrides rich in niobium, copper-rich particles, M 23 C 6 , sigma phase, Z phase, a cored phase, and a BCC phase.

The broken elbow of the final superheater tube (ASME SA213 TP304H) from a coal-fired power plant was evaluated. The root causes were identified by metallographic observation, sensitization evaluation, hardness measurement, and EBSD analysis. The analysis results reached the following conclusions. (1) The tube bending was not performed in accordance with ASME Code requirements—a solid-solution heat treatment was not performed after cold working. (2) The hardness at the elbow is greater than 260 HV, exceeding the ASME code limit. (3) The sensitization was 19%, showing a performance degradation. (4) There are no obvious corrosion elements in the oxide layers of the cracks. (5) Metallographic microstructure analysis shows that there are many intergranular cracks and carbides such as Cr-rich phase and Fe-Cr are precipitated at the grain boundaries, ultimately resulting in strain-induced precipitation hardening damage.

Stress corrosion cracking (SCC) is a potential risk in structural steels used for steam boilers. To investigate the effect of dissolved oxygen (DO) on SCC susceptibility, three steels, T23, T24 and T91 were annealed at 1065°C and then quenched to create a susceptible microstructure and then exposed in a Jones test to stagnant and circulating water at 200°C with varying DO levels. The results indicated that among the tested steels, the SCC susceptibility was highest in T91 but lowest in T23 which did not exhibit crack initiation with 100 ppb DO. T24 showed no cracking with 50 ppb DO but cracked with 100 ppb DO under these conditions. Based on these results, the next planned step is to monitor crack growth in-situ and determine a critical DO content for each material.

The oxide exfoliation is one of the main problems that cause the explosion of superheater or reheater, which threaten the safety of power plant units, but there is no direct test method of the particle concentration of the scales in high temperature steam. Based on the study of ferromagnetic and optical characteristics of scales, the technology and equipment were developed for on-line measurement based on magnetic sensitivity and granularity behavior. Through numerical simulation and dynamic simulation experiments of scale movement under high temperature and high pressure steam, calculating method of the particle concertation of scales in the main steam or reheated steam pipeline was retrieved by local sampling concentration.

To stay competitive in today’s dynamic energy market, traditional thermal power plants must enhance efficiency, operate flexibly, and reduce greenhouse gas emissions. This creates challenges for material industries to provide solutions for harsh operating conditions and fluctuating loads. Higher efficiency demands steels with excellent steam oxidation resistance, favoring ferritic steels for cycling operation due to their limited thermal expansion. This paper presents a study modeling a combined cycle power plant using GE 9HA0.2 GT technology. The analysis compares different maximum live steam temperatures (585°C, 605°C, 620°C) and four alloys (grades 91 and 92, stainless S304H, and Thor 115) for heat exchangers exposed to steam oxidation. Results indicate that Thor 115, a creep strength enhanced ferritic (CSEF) steel, is a viable alternative to stainless steel for live steam temperatures above 600°C, offering improved oxidation resistance with minimal weight increase. Modern CSEF steels outperform stainless steel in power plants with lower capacity factors, reducing thermal fatigue during load changes. Increasing the live steam temperature boosts plant efficiency, leading to significant CO 2 savings for the same power output.

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.

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.