POWERING THE FUTURE

COAL-FIRED POWER MATERIALS

Major advances in materials technology over the last decade have enabled building coal-fired power plants with much higher efficiencies than the current generation. Vis Viswanathan*
Electric Power Research Institute PaloAlto, California

Robert Purgert*
Energy Industries of Ohio

Patricia Rawls
National Energy Technology Laboratory

ery high-efficiency pulverized-coal power plants capable of operating at steam pressures and temperatures much higher than possible today are under development to provide relatively low-cost power with much less pollution. Projects sponsored by the U.S. Department of Energy and the Ohio Coal Development Office have set 1400F/5000 psi as the goal for what might be termed Advanced UltraSuperCritical (AUSC) coal-fired power plants. Europeans have carried out substantial research along the same lines under the AD 700 program. It is estimated that efficiency under these conditions will improve from 35% to nearly 46%, a 31% increase. This results not only in reduced fuel costs, but also in reduced balance-ofplant costs, due to less pulverizing, transportation, waste disposal, emission controls, and cooling-water consumption. It can also lead to a decrease in all waste products and emissions. The major enabling technology for these AUSC plants is the availability of materials with high creep strength, corrosion resistance, and fabricability. This article reviews some of these alloys, with special reference to recent activities of a consortium of companies including Alstom Power, Babcock & Wilcox, Foster Wheeler, Riley Power, Electric Power Research Institute, Oak Ridge National Lab, and Energy Industries of Ohio. The consortium is under the sponsorship of the National Energy Technology Laboratory of the Department of Energy and the Ohio Coal Development Office. Boiler materials The function of a boiler is to convert water into superheated steam, which is then delivered to a steam turbine. Fuel with preheated air is burned

Fig. 1 View of a typical header. Headers are thick-walled extruded pipes in which the fluids carried by the tubes are mixed and homogenized. They serve either as receptacles(Inlet header) or dischargers(Outlet header.) Image courtesy Dr. F. Masuyama

*Member of ASM International

in the furnace, which is constructed with a wall of welded tube panels known as the waterwall. The combustion gases flow through the furnace and evaporate the water into steam inside the furnace waterwall tubes. The steam is then further superheated in the superheater section, and delivered to the turbine via main steam pipes. The low-pressure steam exhausted from the high-pressure turbine is again reheated in a reheater section, and is delivered to the low-pressure turbines via the reheat pipes. The fluids in the system include combustion gases on the outside and water/steam on the inside of tubes and pipes. The key components of a boiler carrying hightemperature, high-pressure steam can therefore be broadly classified into two configurations: tubes and thick-wall pipes. The pipes are generally known as headers or steam pipes, while the tubes are categorized into furnace-wall tubes and superheater/ reheater tubes. Headers: An example of a header is shown in Fig. 1. It is a thick-wall pipe penetrated by a number of tubes. These heavy-section components have to meet creep strength and fatigue strength requirements based on thermal fatigue. Ferritic and martensitic steels are preferred for this application because of their lower coefficient of thermal expansion and higher thermal conductivity compared to austenitic steels. Many of the early problems in the AUSC plants in thick-section austenitic steel components were traceable to their susceptibility to thermal fatigue. Therefore, research during the last decade has focused on cost-effective, high-strength ferritic steels 47

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Table 1 Bill of Materials for various components of Ultra Supercritical and Advanced Ultra Supercritical coal-fired power plant boiler steam conditions (1)
Component SH Outlet Header/ Main steam pipe RH Outlet Header/RH pipe SH panels (4) 1100oF/1100oF P91, P92, E911 P91, P92, E911 Super304H, HR3C, 347HFG Super 304H, HR3C, 347HFG Super304H, HR3C, 347HFG Super304H, HR3C, 347HFG SA 210C T11, T12, T22 T 23, HCM12 1150oF/1150oF P92, P122, E911, SAVE 12 P91, P92, E911 Super304H, HR3C, 347HFG HR6W, HR120, HR3C Super304H, H R3C, 347HFG Super304H, HR3C, 47HFG SA 210C T22 T23, HCM12 1200oF/1200oF NF12, CCA617 Same as above NF 709, Cr 30A 1300oF/1300oF (2) Nimonic263, CCA617 Nimonic263 Super304H, Sanicro25, HR3C, Super304H, 310N IN617, IN740 Sanicro 25, HR 3C, Super304H IN617, IN740 1350oF/1400oF (3) IN740 IN740 IN617 347HFG IN740 304H, 347HFG Haynes 230, Super304H, HR120 SA 210C T23 T92, HCM12

Finish SH (4) Primary RH (4) Finish RH (4)

IN617 NF709, Cr 30A, Super304H IN617

Economizer Lower waterwall Upper waterwall

SA 210C T22 HCM12, T23

SA 210C T23 TI B1010, 7Cr Mo V T23, HCM12

1: Steam pressure of 4500 psi is assumed for this table; 2: Based on European AD700 Project; 3: Based on DOE/OCDO Project; 4: For corrosive, high sulfur /low NOx conditions SH/RH and waterwall tubes may require weld overlay or cladding with IN72 (42% Cr). Table 1 is for general information only, and does not include all the nuances considered by the designer. The service condition listed in each column represents the maximum conditions of exposure.

Table 2 Candidate alloys for USC and AUSC plant boilers

Alloy Haynes 230* INCO740* CCA 617* HR6W* Super304H* Save12* NF 616 (P-92) HCM2S (P-23) HCM12 347HFG NF 709 HR3C HCM12A (P122) NF12 IN625 HR120 E911 Sanicro25 Nominal Composition 57 Ni-22Cr-14W-2Mo-La 50Ni-25Cr-20Co-2Ti-2Nb-V-Al 55Ni-Cr-.3W-8Mo-11Co-Al 43Ni-23Cr-6W-NB-Ti-B 18Cr-8Ni-W-Nb-N 12Cr-W-Co-V-Nb-N 9Cr-2W-Mo-V-Nb-N 2-1/4Cr-1.5W-V 12Cr-1Mo-1W-V-Nb 18Cr-10Ni-Nb 20Cr-25Ni-NB-Ti-N 25Cr-20Ni-Nb-N 12Cr-1.5W-Mo-V-Nb_N 11Cr-2.6W-2.5Co-V-Nb-N 21.5Cr-9Mo-5Fe-3.6Nb-AI-Ti Ni-33Fe-25Cr-N 9Cr-1Mo-1W-V-Nb-N 22Cr-25Ni-3.5W-3Cu-Nb-N Application P, SH/RH Tubes P, SH/RHTubes P, SH/RH Tubes SH/RH Tubes SH/RH Tubes P WW Tubes WW Tubes WW Tubes SH/RH Tubes SH/RH Tubes SH/RH Tubes P P P, T T P 1409 2315 2113 2180 2159 2179 2199 1956 ASME Code 2063

* Alloys studied in the DOE/OCDO Project; P-Pipe; SH - Superheater; RH - Reheater; WW - Waterwall

that could help avoid austenitic stainless steels in heavy-section components. This has resulted in ferritic steels capable of operating at metal temperatures up to 620C (1150F), with good weldability and fracture toughness. Nickel-base alloys are chosen for higher temperatures, thus bypassing the need for austenitic stainless steel components. Tubes: For tubing applications, thermal fatigue is not a key issue because of the smaller section size. Austenitic steels are suitable up to about 1250F (680C). However, nickelbase alloys are needed at higher temperatures, because they provide more creep resistance. Developments are also underway to extend the limiting temperature for austenitic steels as a cost-effective means of replacing the nickel tubing. A sample list of boiler materials for plants operating with various steam conditions is provided in Table 1. The basic compositions of the alloys are shown in Table 2. In addition to creep strength, resistance is needed to hot corrosion from the fireside, and to oxidation corrosion from the steam-side of tubes. Fireside corrosion can lead to premature failures due to the increase in stresses caused by reduced cross section. Steam-side oxidation promotes accelerated creep due to reduction of cross section, progressive increase in tube metal temperature, and blockage of tubes by spalled oxides. In addition, it causes erosion of turbine steam path components by exfoliated oxide particles. To minimize

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Maximum midwall temperature, F

corrosion while keeping costs down, austenitic steel tubes serve in the SH/RH portions of the boiler. Property requirements for waterwall tubes are similar, with the caveat that the fireside corrosion mechanisms are somewhat different. Since the temperatures are lower than for superheaters, ferritic steels with claddings or coatings possess adequate creep strength and corrosion resistance.

1600

IN 740 Haynes 230 1400 IN 617

Super 304H

HR3C

Advanced alloys for 760C (1400F) In the high-temperature and 1200 stress environment envisaged for T92 304H T91 the AUSC steam boiler, the limiting T23 mechanical material property is long-term creep strength. A general criterion of an average stress of 100 MPa (14.5 ksi) to produce rupture T22 in 100,000 hours can serve as a guideline to set the temperature or 3000 4000 5000 6000 Pressure, psig stress limits. Based on the creep strength criterion, the program se- Fig. 2 Maximum usage pressure/temperature. The best ferritic steel can go up to 620C (1150F). lected six advanced alloys as can- Developmental ferritics can reach 650C (1200F), austenitics can function up to 675C (1250F), didate materials for the target plant and nickel alloys function above that, purely based on creep strength. Courtesy of Steve Goodstine, of 1400F (760C)/5000 psi (35 Alstom. MPa) steam conditions. Basic compositions of the candinumber of candidate AUSC nickel-base alloys (indate alloys are included in Table 2. Nickel-base alloy cluding Haynes 230), the weld metal is the weakest For more Haynes 230, Inco 740, and CCA 617 were selected link, and it fails at a shorter time interval or lower information: for heavy section, high-temperature headers, pipes, stress level than the base metal. Vis and SH/RH tubing. In the case of Haynes 230, the weld strength factor Viswanathan, The austenitic steels HR 6W and Super 304H has not been found to be a strong function of testing Electric Power Steel were considered for high-temperature tubing; time, so a general WSF of 0.8 is appropriate, which Research and the ferritic steel SAVE 12 was selected as a can- should not be a hindrance to current boiler design Institute, didate for both applications at lower temperatures. of component welds. However, for other AUSC Palo Alto, CA Figure 2 includes the stress ranges for the alloy materials, data indicate lower WSF. Therefore, re- 94304; tel: 650/855-2450; classes and shows that for temperatures above search is ongoing to improve weld performance rviswana@ ~700C (1290F), age hardenable alloys (Inconel 740 through changes to weld processes, filler metal epri.com; shown) and Haynes 230 will be necessary to meet chemistry, and post-weld heat treatment. www.epri.com. the 100 MPa criteria. Another consideration for boiler materials is that In support of the U.S. program, extensive long- cold strain due to fabrication processes (bending, Other project term creep-rupture testing (now beyond 38,000 swaging, etc.), may cause a degradation in creep contributors hours) is being conducted by Oak Ridge National strength. To understand this phenomenon, full- include Laboratory to understand how creep performance is scale pressurized creep tests are being conducted Dr. Romanosky, affected by microstructural changes, heat-to-heat on cold-bent boiler tubes (two inches O.D., 0.4-inch NETL; Mario material variability, fabrication processes, and wall thickness) in the as-bent condition and in the Maraacco and Bob Brown, welding. heat-treated condition. OCDO; and Utilizing the findings of these studies, the conAfter one year of testing on a nickel-base alloy, Paul Weitzel, sortium is gaining confidence in the performance metallographic examination revealed extensive Mark Palkes, of new materials, and is providing the groundwork creep damage (cavitation) and some recrystalliza- George Booras, for the development of ASME stress allowables, tion in a highly strained tube bend. However, a Robert developing improved fabrication rules, and deter- second bend with slightly less cold strain had no Swindeman, mining the applicability of weld materials/ creep damage even at 1/3 life. These data serve as John processes. Microstructural characterization, material the basis to set rational cold-work limits for the Shingledecker, Jeff Sarver, Ian modeling, and computational thermodynamics are guidelines in the ASME B&PV Code. key tools in the evaluation process. In addition to creep strength considerations, the Perrin,John In addition to the creep strength of the base metal, project consortium has also extensively evaluated Sanders, Mike Borden, Walt strength of the welds is also a major determining the steamside oxidation, fireside corrosion, and fab- Mohn, John factor. Weld-strength reduction factor (WSF) is de- ricability of the alloys selected for AUSC plant Fishburn, and fined as the ratio of the stress-to-rupture of the boilers. These studies will be discussed in Part 2 of many others. welded joint, to the stress-to-rupture of the base this paper next month. Review of turbine materials metal for a given time and temperature. For a will be included in a future issue. ADVANCED MATERIALS & PROCESSES/AUGUST 2008 49