Seeking to reduce CO 2 emissions and improve power generation efficiency, a project to develop a 700°C A-USC (advanced ultra super critical) power plant has been under way in Japan since 2008. HR6W (44Ni-23Cr-7W) is a candidate material for application in the maximum temperature areas of A-USC boilers. In this study, the creep rupture properties of plastic deformed material were investigated in comparison with those of solution treated material, in order to clarify the capability of HR6W as a material for use in A-USC plants. The creep strength of 20% pre-strained HR6W was found to increase substantially as compared with the solution treated material. 20% pre-strained material is in a state where high dislocation density has been introduced by plastic forming strain, with M 23 C 6 and Laves phase precipitating preferentially by dislocation diffusion from the early stages of creep. In particular, since high dislocation density is accumulated in connection with creep deformation near the grain boundaries, precipitation is accelerated and the grain boundaries are covered with M 23 C 6 from the early stages of creep. Then, even though the intragranular precipitate density decreases, given that the fraction of grain boundaries affected by precipitation is maintained in a high state, it is presumed that a high density of dislocation is maintained in the long-term region. This was considered to be the reason why the creep rupture strength of the 20% pre-strained material increased so remarkably in comparison with the solution treated material.

The susceptibilities of hot cracking and reheat cracking of A-USC candidate Ni-based alloys were evaluated relatively by Trans-Varestraint testing and Slow Strain Rate Tensile (SSRT) testing. In addition, semi-quantitative evaluation of the stress relaxation cracking susceptibility of Alloy 617 was conducted, because stress relaxation cracking in the heat affected zone (HAZ) has actually been reported for repair welds in Alloy 617 steam piping in European A-USC field-testing. Solidification cracking susceptibilities of Alloy 617 were the highest; followed by HR35, Alloy 740 and Alloy 141, which were all high; and then by HR6W and Alloy 263, which were relatively low. In addition, liquation cracking was observed in the HAZ of Alloy 617. The reheat cracking susceptibilities of Alloy 617, Alloy 263, Alloy 740 and Alloy 141 were somewhat higher than those of HR6W and HR35 which have good creep ductility due to the absence of γ’ phase precipitates. A method to evaluate stress relaxation cracking susceptibility was developed by applying a three-point bending test using a specimen with a V-notch and finite element analysis (FEA), and it was shown that stress relaxation cracking of aged Alloy 617 can be experimentally replicated. It was proposed that a larger magnitude of creep strain occurs via stress relaxation during the three-point bending test due to a higher yield strength caused by γ’ phase strengthening, and that low ductility due to grain boundary carbides promoted stress relaxation cracking. The critical creep strain curve of cracking can be created by means of the relationship between the initial strain and the creep strain during the three-point bending tests, which were calculated by FEA. Therefore, the critical conditions to cause cracking could be estimated from the stress relaxation cracking boundary from of the relationship between the initial strain and the creep strain during the three-point bending test.

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.

In recent years continuous and extensive research and development activities have been being done worldwide on 700°C A-USC (Advanced Ultra Super Critical) power plants to achieve higher efficiency and reduce the CO 2 emission. Increasing steam temperature and pressure of such A-USC boilers under consideration require the adoption of Ni based alloys. In the Japanese national project launched in 2008, Ni based alloy HR6W (45Ni-23Cr-7W-Ti, ASME Code Case 2684) is one of the candidate materials for boiler tube and pipe as well as Alloy617, Alloy263 and Alloy740H. The most important issues in A-USC boiler fabrication are the establishment of proper welding process for thick wall components of these alloys and verification of the long term reliability of their weldments. In our previous study, the weldability of HR6W was investigated and the welding process for Ni based thick wall pipe was established with the narrow gap HST (Hot wire Switching TIG) welding procedure originally developed by Babcock-Hitachi K.K. In this paper, creep rupture strengths of HR6W weldment were verified by the long term test up to 60,000 hours for tube and 40,000 hours for pipe. In Japanese national project, narrow gap HST welding process was also applied to the welding test for the other Ni based candidate pipe materials. Furthermore, as the practical A-USC boiler manufacturing trials, header mockup test was conducted and qualified for HR6W.

The addition of boron without the formation of any boron nitrides during normalizing heat treatment at high temperature minimizes the degradation in creep strength of both base metal and welded joints of 9Cr steel at 650 °C and long times. The enrichment of soluble boron near prior austenite grain boundaries (PAGBs) by the segregation is essential for the reduction of coarsening rate of M 23 C 6 carbides in the vicinity of PAGBs, enhancing boundary and subboundary hardening, and also for the production of same microstructure between the base metal and heat-affected-zone (HAZ) in welded joints, indicating no Type IV fracture in HAZ. Excess addition of boron and nitrogen promotes the formation of boron nitrides during normalizing, which reduces the soluble boron concentration and accelerates the degradation in creep rupture ductility at long times. 9Cr- 3W-3Co-VNb steel with 120 - 150 ppm boron and 60 - 90 ppm nitrogen (MARBN) exhibits not only much higher creep strength of base metal than Gr.92 but also substantially no degradation in creep strength due to Type IV fracture at 650 °C. The pre-oxidation treatment in Ar gas promotes the formation of protective Cr 2 O 3 scale on the surface of 9Cr steel, which significantly improves the oxidation resistance in steam at 650 °C.

Japanese USC-PC units successfully operate with steam temperatures of 610°C (1130°F). IHI is developing the next generation of USC-PC boilers, targeting 620°C (1150°F) for improved efficiency. Investigations are underway for even higher 700°C (1290°F) steam temperatures. IHI collaborates with turbine manufacturers to create reliable and efficient boiler-turbine packages for both new and existing power plants.

This paper focuses on the key properties of newly developed high-strength, heat-resistant steels for application in ultra-supercritical (USC) boilers. For some ferritic steels, improvements made to enhance their resistance to steam oxidation are highlighted. The latest welding techniques employed for these steels are introduced. Additionally, the high-temperature strength and weldability of Alloy 617 (52Ni-22Cr-13Co-9Mo-Ti-Al), a potential candidate material for the next generation of 700°C USC boilers, are described. The paper provides insights into the materials and welding technologies crucial for the development of advanced USC boilers operating at higher temperatures.

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.

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.

This paper reports the performance of HR6W iron-nickel based alloy and 617B nickel based alloy which are the candidate material for high temperature reheater outlet header of advanced secondary reheat ultra-supercritical unit boiler with reheat steam 653 °C, and analysis the applicable temperature range of the material. As a result, HR6W is the appropriate material to manufacture high temperature reheater outlet header of A-USC boiler with parameters 620°C /653°C/653°C.

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.

In order to reduce CO 2 emissions and improve power generation efficiency, a development project involving an advanced USC (A-USC) plant has been carried out in Japan since 2008. Nibased alloys are candidate materials for boiler components with high temperature steam conditions, which are much stronger than conventional heat resistant steel. However, Ni-based alloys have never been applied with respect to the high pressure parts and thick walled components of USC coal-fired power plants. In this study, therefore, fabrication and characteristic properties, such as weldability, the weld joint and bent part properties, and weld cracking susceptibilities of Ni-based alloys such as HR6W, HR35 and two types of Alloy617 (High B and Low B) pipes were evaluated. Additionally, two types of HR6W header mock-ups and a HR6W tube element mock-up were fabricated. With the exception of Alloy617 (High B), the fabrication trials of Ni-based alloy pipes were conducted successfully, and the long-term creep strength of weldments and bends of Ni-based alloy pipes were found to be nearly equivalent to those of base metal. In the case of Alloy617 (High B), hot cracking was observed.

Delivered condition of Inconel740H specified in ASME Code Case 2702 is solution heat treated and aged condition, fabricating performances are also based on the condition, and a re-annealing and aging shall be performed if cold forming to strains is over 5%. These almost harsh requirements bring great inconvenience for its engineering practice and utilization. The comparative bending tests on 740H tubes in solution heat treated + aged condition and solution heat treated condition were performed, and the rules’ reasonability of the specification on delivered condition was discussed and analyzed from point view of deformability and weldability in the paper. The bending test results showed that tube bent was difficult because of its high strength and limited deforming capacity in solution heat treated + aged condition. Therefore, the material supplied in the solution condition may be better from fabricating points. Whether re-solution for the bent tube is performed after bending depends on its bending radius, followed by welding and post weld heat treatment of component (this treatment can also be the aging treatment for annealed sector at the same time), this treating manner can meet regulatory requirements. For solution tubes, however, there are some inconveniences to its engineering application because fewer research studies were carried out on its properties up to now, and no regulations on them were given for the material in the specification. Suggestions are: 1) deeply investigating the properties of tubes in solution condition, including mechanical and fabricating performances, 2) adding the mechanical properties, maximum allowable cold forming to stain without performing re-solution and weld strength reduction factor of solution material to the code case.

As part of the Boiler Materials for Ultrasupercritical Coal Power Plants program, sponsored by the United States (U.S.) Department of Energy (DOE) and the Ohio Coal Development Office (OCDO), the steamside oxidation and oxide exfoliation behavior of candidate alloys have been thoroughly evaluated in steam at temperatures between 620°C and 800°C (1148°F and 1472°F) for times up to 10,000 hours. The results from this test program indicate that the oxidation rates and oxide morphologies associated with steamside oxidation are a strong function of the crystallographic lattice structure and the chromium content of the material. Oxide exfoliation correlates to oxide thickness. The time required to reach the critical oxide thickness for exfoliation can be estimated based on oxidation kinetic relationships. For austenitic stainless steels, shot peening is effective in reducing steamside oxidation/exfoliation, but the efficacy of this technique is limited by the operating temperature. Nickel-based alloys exhibit very low oxidation/exfoliation rates, but have a propensity to form aluminum/titanium oxides along near surface grain boundaries.

A Japanese national project has been undertaken since Aug. 2008 with the objective of developing an advanced ultra-supercritical power plant (A-USC) with a steam temperature of 700°C. Fe-Ni and Ni-based alloys, namely HR6W, HR35, Alloy617, Alloy740, Alloy263 and Alloy141, were taken as candidate materials for piping and superheater/reheater tubes in an A-USC boiler. Weldments of these alloys were manufactured by GTAW, after which long term creep rupture tests were conducted at 700°C, 750°C and 800°C. Weldments of HR6W, HR35 and Alloy617 showed similar creep strength as compared with these base metals. Weldments of Alloy740 tended to fail in the HAZ, and it is considered that voids and cracks preferentially formed in the small precipitation zone along the grain boundary in the HAZ. The creep strength of Alloy263 in weldments exhibited the highest level among all the alloys, although HAZ failure occurred in the low stress test condition. A weld strength reduction factor will be needed to avoid HAZ failure in Alloy740 and Alloy263. Also, to prevent premature failure in weld metal, optimization of the chemical composition of weld filler materials will be required.

Welding processes and fabrication techniques have been studied in the development of Advanced USC boilers. Advanced 9Cr steels, Fe-Ni alloy (HR6W) and Nickel base alloys (HR35, Alloy 617, Alloy 263, Alloy 740 and Alloy 740H) have been selected as candidate materials for the boiler. The weld joints of these alloys were prepared from plates, small diameter tubes and large pipes, and welding procedure tests were performed. In this study, TIG and SMAW were applied. Both welding process produced good weld joints, and they showed good results in bending tests, tensile tests and the Charpy impact test. To select the annealing conditions for stress relief, stress relaxation tests and hardness tests were conducted on the weld joints after various heat treatments. The microstructure was also evaluated by SEM and TEM. Creep rupture tests are being performed for the weld joints with and without heat treatment. The maximum creep rupture tests are expected to take over 100,000 hours. In the study of fabrication techniques, hot bending tests by high frequency induction heating for large pipes and cold/hot bending tests for small diameter tubes were established. After the bending tests, mechanical property tests such as tensile tests, impact tests and creep rupture tests were conducted. The effect of pre-strain on creep strength was studied to take the creep test results after bending into consideration. The creep rupture test will be continued for specimens from weld joints and bending pipes to show their long term reliability.

Low thermal expansion precipitation strengthening Ni-base superalloy, Ni-20Cr-10Mo-1.2Al-1.6Ti alloy (USC141TM), was developed for 700°C class A-USC steam turbine material by Hitachi, Ltd and Hitachi Metals, Ltd. USC141 is usually solution treated and then aged to increase high temperature strength for turbine blades and bolts. As the estimated 105h creep rupture strength at 700°C is about 180MPa, USC141 could also be expected to apply for boiler tubes. On the other hand, this alloy seems to be only solution treated to apply for boiler tubes because tubes are usually jointed by welding and bended by cold working and thus tube alloys should have low hardness before welding and bending and should be used as solution treated. In this study, the creep properties of USC141 as solution treated was evaluated, and the results and microstructures after creep tests were compared with those as aged. As a result, USC141 as solution treated exhibited almost as same creep rupture properties as that as aged because precipitation at grain boundaries and in grains gradually increased at testing temperatures around 700°C. Furthermore seamless tubes of USC141 were produced and various properties including creep properties are now being evaluated.

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 construction of highly efficient, coal-burning Ultra Supercritical (USC) boiler systems to operate with steam temperatures up to 760°C (1400°F) and with steam pressures up to 35 MPa (5000 psi) will require the use of advanced high temperature, high strength materials. As part of a 5-year project to develop boiler materials for advanced USC power plants, principally funded by the Department of Energy (U.S. DOE No. DE-FG26-01NT41175) and the Ohio Coal Development Office (OCDO No. D-00-20), six alloys have been selected for development and implementation in USC boiler systems. The selected alloys are Haynes 230 (produced by Haynes International), Inconel 740 (produced by Special Metals Corp.), CCA 617 (produced by Krupp VDM GMBH), HR6W, Super 304H, and SAVE 12 (all three produced by Sumitomo Metal Industries). In this project, one of the goals has been to establish boiler fabrication guidelines for the use of these alloys. The principal objectives have been 1) to understand the behavior of these materials when subjected to conventional boiler fabrication processes, 2) to determine the thermomechanical treatments or other actions necessary to restore material properties which might degrade due to fabrication operations, and 3) to investigate prototypical manufacturing operations for producing both thick wall components (such as headers) and thin wall components (such as superheaters) from the USC alloys. This paper discusses some of the characteristics of these alloys, describes the technical approach used to assess their fabricability, and presents some of the results that have thus far been generated in this task effort.

Components in ultrasupercritical steam (USC) boilers will operate under significantly more severe conditions than current subcritical and supercritical steam boilers. Existing construction rules for power boilers lack design guidance or criteria to assess the adequacy of designs for USC conditions. A Department of Energy (DOE) project addresses this by evaluating advanced materials under conditions similar to potential USC service environments. The project focuses on six tubing alloys and four thick-section alloys. Testing is underway for pressurized tube bends, notched thick-section bars, fatigue, and thermal shock on thick-section tubing made of materials like CCA617, Alloy 230, and Alloy 740. Further testing is planned for pressurized tubes, dissimilar metal welds, and thick-section weldments. This paper summarizes the status of this initial testing program aimed at enabling USC boiler material qualification.