EP3109331B1 - High-temperature nickel-based alloy for 700°c grade ultra-supercritical coal-fired power station and preparation thereof - Google Patents

High-temperature nickel-based alloy for 700°c grade ultra-supercritical coal-fired power station and preparation thereof Download PDF

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EP3109331B1
EP3109331B1 EP14883147.2A EP14883147A EP3109331B1 EP 3109331 B1 EP3109331 B1 EP 3109331B1 EP 14883147 A EP14883147 A EP 14883147A EP 3109331 B1 EP3109331 B1 EP 3109331B1
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temperature
nickel
ultra
alloy
fired power
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EP3109331A4 (en
EP3109331A1 (en
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Fusheng Lin
Shuangqun Zhao
Rui FU
Xishan XIE
Chengyu CHI
Yaohe HU
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University of Science and Technology Beijing USTB
Shanghai Power Equipment Research Institute Co Ltd
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University of Science and Technology Beijing USTB
Shanghai Power Equipment Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

Definitions

  • the present invention belongs to the technical field of nickel-based superalloy, in particular to a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant.
  • This new superalloy can be applied as the high-temperature components in advanced ultra-supercritical coal-fired power plants at the steam temperature rating of 700°C.
  • the highest service temperatures of the new alloy can be reached at 800°C.
  • EU is the first one that started this project in 1998, enhancing the steam temperature to 700°C /720°C/35MPa, with the expected power generation efficiency increasing from the current 45% to over 50%. USA and Japan then started similar study projects at the beginning of the 21st century. In 2011, China also started to research and develop the 700°C ultra-supercritical coal-fired power generation technologies.
  • thermal power units take position up to 80%, while the mean coal consumption of the power plants is far higher than that of the developed countries in the world.
  • To reduce the coal consumption by increasing the steam parameter of the coal-fired power plants not only will be savings on coal resources and a reduced emission of CO 2 , etc, but also will be significant for the sustainable development of the economy, society and the environment.
  • the temperature and pressure of the coal-fired power generation units are increased to the rating of 700°C /720°C /35MPa, higher requirements are imposed on the strength and corrosion resistance of key high-temperature components of the power plants, for example, the HP and IP rotors, cylinders and valve shells in the turbines, superheaters and reheaters in boilers, headers and steam pipes, etc.
  • the outer wall temperature of the superheater and reheater tubes in the boilers is about 50°C higher than the inner steam temperature. Therefore, when the steam temperature in the superheater and reheater tubes reaches 700°C and 720°C, the maximum temperature of the outer walls of the tubes may reach about 770°C and even higher.
  • the steam pressure in the tubes is also increased.
  • the 9 ⁇ 12 Cr% steel and austenitic steels such as Super304H and HR3C, which are widely applied to the ultra-supercritical coal-fired power plants, fail to meet the requirements for the strength and the corrosion resistance, therefore the nickel-based superalloys must be used.
  • the corrosion resistance and high temperature properties are required to be considered in the oxidation or reduction environment.
  • the service duration of the alloys is relative short and the requirements of high-temperature strength are more important.
  • the current nickel-based superalloys Due to the great difference in the purposes, in particular the prominent characteristics of long operating time (30-40 years) of the ultra-supercritical power plants, the current nickel-based superalloys usually fail to meet the requirements for high-temperature strength, maximum service temperature, structure stability and resistance to oxidation/sulfuration at the same time and thus fail to meet the requirements for long-term use by the high-temperature components of the 700°C ultra-supercritical coal-fired power plants.
  • EU studied nickel-based alloys Inconel 617 and Nimonic 263 in the 700°C ultra-supercritical power generation program obtained the 617B alloy through optimizing the composition of the 617 alloy and now is optimizing the 263 alloy.
  • Japanese company Sumitomo has developed the Fe-Ni-based alloy HR6W.
  • the Swedish company Sandvik has also developed the Fe-Ni-based Sanicro25 austenitic alloy. Those alloys all fail to meet the requirements of the highest temperature components.
  • SMC has developed Inconel 740 alloy which possess obvious characteristics of high strength and high corrosion resistance and has thus become the main candidate materials of the high-temperature parts of the power units.
  • China also actively exploits alloys for use at higher temperatures on the basis of the nickel-iron-based alloy GH2984 which is originally used as the superheater of the marine boilers. So far, the above-mentioned alloys are still under development.
  • WO 2009/158332 discloses a nickel (Ni), chromium (Cr), cobalt (Co), iron (Fe), molybdenum (Mo), manganese (Mn), aluminum (Al), titanium (Ti), niobium (Nb), silicon (Si) welding alloy that contains in % by weight about: 23.5 to 25.5% Cr, 15 to 22% Co, up to 3% Fe, up to 1% Mo, up to 1% Mn, 1.1 to 2.0% Al, 0.8 to 1.8% Ti, 0.8 to 2.2% Nb, 0.05 to 0.28% Si, up to 0.3% Ta, up to 0.3% W, 0.005 to 0.08% C, 0.001 to 0.3% Zr, 0.0008 to 0.006% B, up to 0.05% rare earth metals, up to 0.025% Mg plus optional Ca and the balance Ni including trace additions and impurities.
  • the welding alloy is proposed for joining boiler tubing to the header pipe in supercritical, ultra-supercritical and advanced ultra-supercritical boiler applications.
  • the present invention obtains a nickel-based alloy capable of being used for the long term at a temperature below 800°C. It has the high room temperature and high temperatures tensile properties, creep-rupture properties at high temperatures and excellent corrosion resistance. It has the great prospects in the application of the 700°C-class ultra-supercritical coal-fired power plants.
  • the objective of the present invention is to provide a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants and a fabrication method thereof.
  • the new nickel-based superalloy has advantages of reasonable combination of chemical compositions, hot deformation property, excellent high-temperature mechanical properties and corrosion resistance, and good structure stability also.
  • the present invention provides a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants, characterized by comprising: C 0.01 ⁇ 0.07wt%, Cr 23 ⁇ 25.5wt%, Co 10 ⁇ 14.6wt%, Mo 0.3 ⁇ 3.5wt%, W 0.5 ⁇ 2.5wt%, Nb 0.8 ⁇ 2.2wt%, Ti 1.0 ⁇ 2.5wt%, Al 1.0 ⁇ 2.5wt%, B 0.001 ⁇ 0.005wt%, Zr 0.01 ⁇ 0.3wt%, Mg 0.002 ⁇ 0.015wt%, V 0.01 ⁇ 0.5wt%, La 0.001 ⁇ 0.005wt%, balance of Ni and inevitable impurity elements including S ⁇ 0.010wt%, P ⁇ 0.015wt%, Si ⁇ 0.3wt% and Mn ⁇ 0.5wt%, wherein the ratio (Al/(Ti+Nb)) of the atomic percentage of Al to the sum of the atomic percentages of Ti and Nb is
  • the percentage of age-precipitated strengthening phase ⁇ ' of the nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants is 14 ⁇ 19wt%.
  • the present invention also provides a fabrication method of the nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants, characterized by including the following steps of:
  • the temperature of the diffusion annealing is implemented at 1,150 ⁇ 1,220°C, and the duration is 16 ⁇ 48h.
  • the temperature of the billet forging is not lower than 1,050°C.
  • the temperature of the solid solution treatment is implemented at 1,100 ⁇ 1,200°C and the duration is 0.5 ⁇ 2h.
  • the temperature of the aging treatment is implemented at 800°C and the duration is 4 ⁇ 16h.
  • step 2 before diffusion annealing, the alloy ingot are refined again by vacuum arc re-melting or by electro-slag re-melting in a protective gas atmosphere.
  • the re-melting rate shall be strictly controlled to be less than 300kg/h.
  • a complex quinary slag purified system comprises 40 ⁇ 45wt% of CaF 2 , 20 ⁇ 30wt% of Al 2 O 3 , 15 ⁇ 20wt% of CaO, 5 ⁇ 10wt% of MgO and 5-10wt% of TiO 2 .
  • the complex quinary slag purified system should be extracted to ensure SiO 2 ⁇ 0.5%, and should be baked for 4h at a temperature of 800°C before usage. Using (40 ⁇ 45%CaF 2 + 20 ⁇ 30%Al 2 O 3 + 15 ⁇ 20%CaO + 5 ⁇ 10%MgO + 5 ⁇ 10%TiO 2 ) can ensure stable Al, Ti and Mg ingredients.
  • the contents of harmful trace impurity elements such as Pb, Sn, As, Sb and Bi are required to be strictly controlled according to the current industrial protection technologies because those trace elements are harmful to the forging process and the durability as well as the high-temperature plasticity of the alloy.
  • C as a strengthening element, is good for high-temperature stress-rupture strength of the alloy when M 23 C 6 carbide is formed at grain boundaries and when C with the content of less than 0.01 % is not enough to form a certain amount of M 23 C 6 .
  • C together with Ti and Nb can form a primary carbide MC, good for grain size control. In the case of excessive C content, more Ti and Nb will be consumed to form MC, so the C content should be kept below 0.06%.
  • C also has a function of ensuring mobility of the melted metal during pouring.
  • Cr is an important element for enhancing the resistance to oxidation and corrosion and the high-temperature strength of the nickel-based alloy and is also a main element for the formation of the carbides at grain boundaries.
  • Research has shown that, under the condition that the interior of the boiler tubes are full of high temperature steam, in the alloy, Cr with a content greater than 23% can form a protective Cr 2 O 3 oxide film on the inner wall of the tube and can ensure that the outer wall of the tube is resistant to flue gas corrosion at the same time. Excessive Cr content will affect the structure stability and workability of the alloy so that the Cr content is required to not exceed 25.5%.
  • Co is beneficial to strength of the nickel-based alloy at a high temperature and to the resistance of high-temperature corrosion.
  • Co in the Ni-Cr solid solution can reduce the stacking fault energy and plays a good solid solution strengthening role.
  • the Co content is lower than 10%, the high-temperature strength is reduced.
  • Co is a strategic element with a high price. Excessive Co prompts the formation of ⁇ phase in the alloy, which is harmful to the properties of the alloy and affects the forgeability of the alloy. Therefore, the Co content is limited in the range of 10.0 ⁇ 14.6%. For the present invention, it is an important factor for rationally controlling the strengthening elements and reducing the alloy cost.
  • Mo entering the ⁇ matrix of the nickel-based alloy plays an important role of solid solution strengthening.
  • the use of Mo to perform solid solution strengthening is also one of the strengthening element control features of the present invention.
  • the Mo content is controlled to be at 0.3 ⁇ 3.5%.
  • the W enters the ⁇ matrix and the ⁇ ' strengthening phase by half, respectively.
  • the W has a relatively large atom radius which is greater than the radius of the matrix element Ni by over ten percent and plays an obvious role of solid solution strengthening.
  • W and Mo added together perform a compound solid solution strengthening.
  • W is an element for speeding up thermal corrosion and therefore the W content is controlled to be at 0.5 ⁇ 2.5%.
  • the Nb content is controlled to be at 0.8 ⁇ 2.2%.
  • the difference between the radii of the Nb and Ni atoms is greater than that of the W and Ni atoms.
  • Nb is an important precipitation strengthening and solid solution strengthening element in the alloy of the present invention and together with Al and Ti are strengthening elements of the ⁇ ' phase.
  • Nb content must be controlled to be appropriate because excessive Nb will promote the formation of the ⁇ phase, reduce the protection properties of the oxide film and deteriorate the welding property due to promotion of liquation cracks.
  • Ti is controlled to be at 1.0 ⁇ 2.5%. It is an important strengthening element for forming ⁇ ' phase.
  • the Ti element is also an important grain size stabilizer, together with the Nb forming primary carbide (Ti, Nb)C.
  • Ti, Nb primary carbide
  • an excessive Ti content will promote the formation of the harmful ⁇ phase and cause internal oxidation, reducing the plasticity of the alloy.
  • Al is good for resisting oxidation and improving the structure of the oxide film, together with Ti and Nb forming the ⁇ ' strengthening phase with Ni.
  • Al is an important element for stabilizing the ⁇ ' phase and restraining the formation of the ⁇ phase.
  • a low Al content causes undesirable strengthening effect and reduces the high-temperature strength; while a high Al content obviously reduces the plasticity and toughness of the alloy and narrows the processing temperature scope of the alloy. Meanwhile, in a high-temperature sulfurization environment, a high Al content promotes the internal oxidation and internal sulfurization corrosion. Therefore, Al is limited in the range of 1.0 ⁇ 2.5%.
  • B is a micro-alloying element, rich at grain boundaries, strengthening the bonding force of grain boundaries. Boride at grain boundary can prevent the grain boundary sliding, cavities connection and crack propagation, it has an obvious effect of enhancing the creep property of the alloy. There is an optimum B content. In the present invention, the B content in the alloy is controlled to be at 0.001 ⁇ 0.005%.
  • Zr is controlled to be at 0.01-0.3%, good for purifying the grain boundaries and strengthening the bonding force of grain boundaries and together with B is good for keeping the high-temperature strength and endurance plasticity of the alloy. An excessive Zr will reduce the hot workability. Another effect of the Zr is obviously to increase the adhesion property of the protective oxide film on the surface of the alloy.
  • Mg is added as a micro-alloying element. Proper Mg is good for improving the creep-rupture life and plasticity of the alloy. Segregation of Mg at the grain boundary and phase boundaries can reduce the grain boundary energy and inter-phase boundary energy, improve the precipitation morphology of the second phase and reduce the local stress concentration. Besides, Mg can also be combined with impurity elements to purify the grain boundaries. Mg is controlled to be at 0.004 ⁇ 0.015%.
  • V when distributed in the ⁇ matrix, can effectively increase the lattice deformation and enhance solid solution strengthening. Meanwhile, a part of the V also enters the strengthening phase ⁇ ' to replace Al. V can also easily form precipitates, fine and dispersive VC during solidification, is good for refining grains. Besides, V can improve the thermal working plasticity of the alloy and is controlled to be at 0.001 ⁇ 0.5wt%.
  • La is added as a micro-alloying element and can be combined with the impurity elements, in particular the harmful element S, to play the role of purifying and strengthening grain boundaries. Besides, La is good for oxidation resistance. La is controlled to be at 0.001 ⁇ 0.005%.
  • S is a harmful impurity element, prompting the segregation of elements and the formation of a harmful phase during solidification.
  • S is segregated at grain boundaries and the inter-phase boundaries, seriously affecting the thermal plasticity and high-temperature creep-rupture properties of the alloy.
  • S is controlled at below 0.010% and should be controlled to be as low as possible.
  • P has dual effects, prompting the segregation of elements and the precipitation of harmful phases during solidification.
  • Proper P content can improve creep property.
  • Excessive P is seriously segregated at grain boundaries to reduce the grain boundary strength and affects the toughness.
  • P shall be controlled to be at below 0.015%.
  • Si is a common impurity element, rich at the grain boundaries. Si can reduce the grain boundary strength and promote the formation of TCP phase.
  • the research results of the present invention indicate that a high Si content can promote the precipitation of the Si-riched G phase at the grain boundary to obviously affect the plasticity, toughness and workability of the alloy. Thus Si must be controlled below 0.3%.
  • Mn like other impurities, is segregated at grain boundaries. Mn can weaken the grain boundary bonding force, reduce creep strength and promote the formation of the harmful phase at grain boundaries. Mn should be controlled below 0.5%.
  • Ni is the most important element of ⁇ matrix and the main formation element of ⁇ ' precipitation strengthening phase. To ensure the stability of the structure, obtain the high-temperature strength and toughness and ensure that the alloy has good workability, the Ni content must be kept about 50%.
  • Figure 1 is a diagram of the research result on the relationship of the precipitation amount and the Al+Ti+Nb content.
  • the principles of controlling the precipitation strengthening phase Al, Ti and Nb focus on: the ratio Al/(Ti+Nb) is in the range of 1.0-1.3, and the sum of Al+Ti+Nb is 5.5 ⁇ 6.2at%, so that the precipitation amount of the strengthening phase is in the range of 14 ⁇ 19wt%.
  • Forming proper precipitation strengthening effect is the first guarantee factor for obtaining a proper high strength and without ⁇ ' phase to ⁇ phase transformation.
  • the structure of the strengthened precipitation phase of the alloy is stable.
  • the ⁇ ' phase of this alloy for the present invention is of the Ni 3 (Al,Ti,Nb) type.
  • the Nb and Ti have good strengthening effects at a temperature of 700-800°C, a large coherent strain field is generated due to a large mismatch degree of ⁇ '/ ⁇ , so this ⁇ ' phase is metastable. It is also easy to form Ni 3 (Ti,Nb) type ⁇ phase.
  • the present invention ensures that the ⁇ ' phase is precipitated at a favorable position in the grains and at grain boundaries during the heat treatment.
  • FIG. 2 is a microstructure diagram of the alloy of the present invention after heat-treatment.
  • the principle of controlling Mo and Cr element is as follows: the atom ratio Cr/(Mo+W) is greater than 12, and the sum of Mo+Cr+W does not exceed 30at%.
  • the atom ratio Cr/(Mo+W) is greater than 12, and the sum of Mo+Cr+W does not exceed 30at%.
  • no ⁇ phase and ⁇ phase is formed in this alloy and the content of the impurity element Si is controlled below 0.3wt% to restrain the precipitation of the G phase.
  • the microstructures at standard heat-treatment state and after long-term aging of the ally can be seen in figure attached to abstract and figure 2 , respectively.
  • the present invention takes into consideration not only the rational combinations of compound solid solution strengthening of a proper amount of W in the Ni-Cr-Co-Mo matrix combined with Al, Ti and Nb precipitation strengthening, but also the addition of a small amount of vanadium to enhance the strengthening and the optimization of the micro-alloying elements B, Zr and Mg.
  • This invention is to strictly control the contents of the conventional harmful elements S, P, Si and Mn, in particular, and adding a trace of La in the melting process, and thus it plays the role of purifying and strengthening grain boundaries.
  • the chemical composition design of the alloy is more rational; the microstructure has a high stability during long-term aging.
  • the 14 ⁇ 19wt% ⁇ ' phase precipitation strengthening is generated, and the precipitation of harmful phases such as the ⁇ phase, G phase and ⁇ phase are restrained in the aging process.
  • the ⁇ ' phase in the alloy is of the Ni 3 (Al, Ti, Nb) type and the sum of the Al, Ti and Nb, and the ratio Al/(Ti+Nb) are rationally controlled to obtain the proper amount of the stable strengthening phases.
  • the ⁇ ' phases are precipitated in the grains and also at favorable positions of grain boundaries, capable of effectively preventing the propagation of intergranular cracks and improving the impact toughness and creep property thereof.
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants comprises with C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical compositions and the weight percentages of the impurities S, P, Si and Mn can be seen in table 1.
  • the ratio (Al/(Ti+Nb)) of the atomic percentage of Al to the sum of the atomic percentage of Ti and Nb, the sum (Nb+Ti+Al) of the atomic percentages of Al, Ti and Nb, the ratio (Cr/(Mo+W)) of the atomic percentage of Cr and the sum of Mo and W atoms, and the sum (Cr+Mo+W) of the atomic percentages of Cr, Mo and W can be seen in Table 1.
  • a fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants comprises with the following steps of: Selecting high quality raw materials, placing 0.05wt% of C, 24.3wt% of Cr, 14.2wt% of Co, 0.32wt% of Mo,1.05wt% of W, 1.48wt% of Nb, 1.52wt% of Ti, 1.61wt% of Al, 0.003wt% of B, 0.02wt% of Zr, 0.18wt% of V, 55wt% of Ni and 5wt% of the dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace, the auxiliary materials consisting of 40wt% of the CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 .
  • the weight fraction of the ⁇ ' strengthening phase of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants is at 16.8wt%.
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants comprises C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical composition and the weight percentages of the impurities S, P, Si and Mn can be seen in Table 1.
  • the fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants comprises the following steps: Select high quality raw materials and place 0.05wt% of C, 24.5wt% of Cr, 10.2wt% of Co, 1.35wt% of Mo,1.05wt% of W, 1.67wt% of Nb, 1.49wt% of Ti, 1.72wt% of Al, 0.003wt% of B, 0.02wt% of Zr, 0.17wt% of V, 57wt% of Ni and 5wt% of the dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace.
  • the auxiliary materials consist of 40wt% of CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 . Smelt these raw materials in vacuum induction furnace at the vacuum condition of 1O -3 Bar. After the raw materials are completely melted, refine the metal for 10min to remove gases while keeping the vacuum not lower than 10 -3 Bar. After refining is complete, charge with Argon gas until the pressure reaches 0.4bar, adding 0.5wt% Ni-20Ca alloy at the same time to remove the harmful impurity element S. When the temperature of the molten metal is at 1,520°C before pouring, add 0.015wt% Ni-20Mg alloy and 0.005 wt% metal La in turn to perform desulfurization and purification. Fully melting the materials, mixing the molten metal well, filtering the molten metal and pouring the molten metal into moulds, the alloy ingot will form in an argon atmosphere.
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises with C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical composition and the weight percentages of the impurities S, P, Si and Mn can be seen in Table 1.
  • the fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises the following steps: Select high quality raw materials, placing 0.05wt% of C, 24.7wt% of Cr, 14.5wt% of Co, 2.43wt% of Mo,1.15wt% of W, 1.62wt% of Nb, 1.56wt% of Ti, 1.56wt% of Al, 0.002wt% of B, 0.04wt% of Zr, 0.10wt% of V, 52wt% of Ni and 5wt% of the dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace.
  • the auxiliary materials consist of 40wt% of CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 .
  • Those raw materials are melted in the vacuum induction furnace at a vacuum condition of 10 -3 Bar. After the raw materials are completely melted, refine the materials for 10min to remove gases while keeping the vacuum at not lower than 10 -3 Bar. After refining is completed, charge with Argon gas until the pressure reaches 0.4bar, adding 0.5wt% Ni-20Ca alloy at the same time to remove the harmful impurity element S.
  • the temperature of the molten metal is at 1,520 ⁇ before pouring; add 0.015wt% Ni-20Mg alloy and 0.005 wt% metal La in turn to perform desulfurization and purification. Fully melting the materials, mixing the molten metal well, filtering the molten metal and pouring the molten metal into the moulds, the alloy ingot will form at an Argon atmosphere.
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises with C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical composition and the weight percentages of the impurities S, P, Si and Mn can be seen in Table 1.
  • the ratio (Al/(Ti+Nb)) of the atomic percentage of Al to the sum of the atomic percentage of Ti and Nb, the sum (Nb+Ti+Al) of the atomic percentages of Al, Ti and Nb, the ratio (Cr/(Mo+W)) of the atomic percentage of Cr and the sum of Mo and W atoms and the sum (Cr+Mo+W) of the atomic percentages of Cr, Mo and W can be seen in Table 1, too.
  • the fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants comprises the following steps: Select high quality raw materials and place 0.07wt% of C, 25.0wt% of Cr, 14.6wt% of Co, 2.87wt% of Mo,1.20wt% of W, 1.56wt% of Nb, 1.60wt% of Ti, 1.58wt% of Al, 0.002wt% of B, 0.04wt% of Zr, 0.15wt% of V, 51wt% of Ni and 5wt% of the dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace and the auxiliary materials consisting of 40wt% of CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 .
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises with C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical composition and the weight percentages of the impurities S, P, Si and Mn can be seen in table 1.
  • the ratio (Al/(Ti+Nb)) of the atomic percentage of Al to the sum of the atomic percentage of Ti and Nb, the sum (Nb+Ti+Al) of the atomic percentages of Al, Ti and Nb, the ratio (Cr/(Mo+W)) of the atomic percentage of Cr and the sum of the Mo and W, and the sum (Cr+Mo+W) of the atomic percentages of Cr, Mo and W can be seen in Table 1, too.
  • the fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants comprises the following steps: Selecting high quality raw materials and place 0.06wt% of C, 24.4wt% of Cr, 13.6wt% of Co, 3.04wt% of Mo,1.16wt% of W, 1.51wt% of Nb, 1.51wt% of Ti, 1.51wt% of Al, 0.003wt% of B, 0.05wt% of Zr, 0.16wt% of V, 52wt% of Ni and 0.5wt% of the dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace with the auxiliary materials consisting of 40wt% of CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 .
  • the temperature of the molten metal is at 1,520°C before pouring, add 0.020wt% of the Ni-20Mg alloy and 0.005 wt% metal La in turn to perform desulfurization and purification; Fully melting the materials, mixing the molten metal well, filtering the molten metal and pouring the molten metal into moulds, the alloy ingot will form at an Argon atmosphere.
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises with C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical composition and the weight percentages of the impurities S, P, Si and Mn can be seen in Table 1.
  • the ratio (Al/(Ti+Nb)) of the atomic percentage of Al to the sum of the atomic percentage of Ti and Nb, the sum (Nb+Ti+Al) of the atomic percentages of Al, Ti and Nb, the ratio (Cr/(Mo+W)) of the atomic percentage of Cr and the sum of Mo and W atoms, and the sum (Cr+Mo+W) of the atomic percentages of Cr, Mo and W can be seen in Table 1, too.
  • the fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises the following steps: Selecting high quality raw materials and place 0.06wt% of C, 24.7wt% of Cr, 12.9wt% of Co, 0.53wt% of Mo,2.23wt% of W, 1.59wt% of Nb, 1.62wt% of Ti, 1.54wt% of Al, 0.004wt% of B, 0.005wt% of Zr, 0.15wt% of V, 54wt% of Ni and 5wt% of the dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace and the auxiliary materials consisting of 40wt% of CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 .
  • Remelt the alloy ingot by electroslag remelting under a protective atmosphere Remove the oxide scale from the surface of the alloy ingot, then being welded with the electrode, Perform electroslag remelting by using (40% CaF 2 + 25%Al 2 O 3 + 15%CaO + 10%MgO + 10%TiO 2 ) complex quinary slag purified system, wherein the slag is extracted while the SiO 2 is ensured to be less than 0.5%.
  • the electroslag ingot are baked for 4h at a temperature of 800°C, keeping the smelting voltage of ESR furnace at 50V and the smelting at remelting rate of 250kg/h; and finally annealing the electro-slag remelted ingot for 1h at a temperature of 900°C.
  • the weight fraction of ⁇ ' precipitation strengthening phase of the nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants is at 17.2wt%.
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises with C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical compositions and the weight percentages of the impurities S, P, Si and Mn can be seen in Table 1.
  • the ratio (Al/(Ti+Nb)) of the atomic percentage of Al to the sum of the atomic percentage of Ti and Nb, the sum (Nb+Ti+Al) of the atomic percentages of Al, Ti and Nb, the ratio (Cr/(Mo+W)) of the atomic percentage of Cr and the sum of Mo and W atoms, and the sum (Cr+Mo+W) of the atomic percentages of Cr, Mo and W can be seen in Table 1, too.
  • the fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises the following steps: Selecting high quality raw materials and place 0.05wt% of C, 24.98wt% of Cr, 14.6wt% of Co, 1.36wt% of Mo,1.19wt% of W, 1.54wt% of Nb, 1.53wt% of Ti, 1.51wt% of Al, 0.002wt% of B, 0.04wt% of Zr, 53wt% of Ni and 0.5wt% of the dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace and the auxiliary materials consisting of 40wt% of CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 .
  • VAR vacuum arc remelting
  • Annealing the electrode for 1h at a temperature of 900°C removes the oxide scale from the surface; welding the electrode of the alloy ingots at a vacuum of 10 -3 mmHg; then melting both of them at a voltage of 25V; controlling the vacuum at 10 -3 mmHg; keeping the melting rate 250kg/h; and finally annealing the VAR alloy ingot for 1h at a temperature of 900°C; perform diffusion annealing on the re-melted VAR alloy ingot at a temperature of 1,190°C and forging the alloy ingot at 1,200°C, into ⁇ 15mm bar product through three times reheating, implementing solid solution annealing on the bar product for 1h at a temperature of 1,150°C, water cooling and aging the bar product for 16h at a temperature of 800°C, air cooling.
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises with C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical composition and the weight percentages of the impurities S, P, Si and Mn can be seen in Table 1.
  • the ratio (Al/(Ti+Nb)) of the atomic percentage of Al to the sum of the atomic percentage of Ti and Nb, the sum (Nb+Ti+Al) of the atomic percentages of Al, Ti and Nb, the ratio (Cr/(Mo+W)) of the atomic percentage of Cr and the sum of Mo and W atoms, and the sum (Cr+Mo+W) of the atomic percentages of Cr, Mo and W can be seen in Table 1, too.
  • the fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises the following steps: Select high quality raw materials and place 0.05wt% of C, 24.4wt% of Cr, 13.6wt% of Co, 1.19wt% of Mo,1.06wt% of W, 1.81wt% of Nb, 1.73wt% of Ti, 1.14wt% of Al, 0.003wt% of B, 0.05wt% of Zr, 0.16wt% of V,54wt% of Ni and 0.5wt% of the dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace and the auxiliary materials consisting of 40wt% of CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 .
  • a nickel-based superalloy for 700°C ultra-supercritical coal-fired power plant comprises with C, Cr, Co, Mo, W, Nb, Ti, Al, B, Zr, Mg, V, La, Ni and the inevitable impurity elements.
  • the actually tested weight percentages of chemical composition and the weight percentages of the impurities S, P, Si and Mn can be seen in Table 1.
  • the ratio (Al/(Ti+Nb)) of the atomic percentage of Al to the sum of the atomic percentage of Ti and Nb, the sum (Nb+Ti+Al) of the atomic percentages of Al, Ti and Nb, the ratio (Cr/(Mo+W)) of the atomic percentage of Cr and the sum of Mo and W atoms, and the sum (Cr+Mo+W) of the atomic percentages of Cr, Mo and W can be seen in Table 1, too.
  • the fabrication method of this nickel-based superalloy for 700°C ultra-supercritical coal-fired power plants comprises the following steps: Select high quality raw materials and place 0.06wt% of C, 24.4wt% of Cr, 12.91wt% of Co, 3.41wt% of Mo,2.33wt% of W, 1.59wt% of Nb, 1.63wt% of Ti, 1.53wt% of Al, 0.004wt% of B, 0.005wt% of Zr, 0.15wt% of V,51wt% of Ni and 5wt% of dry auxiliary materials with a purity of 99.5% into a vacuum induction furnace and the auxiliary materials consisting of 40wt% of CaF 2 , 40wt% of CaO and 20wt% of Al 2 O 3 .
  • the chemical compositions of the alloys in embodiments 1-6 are fully in accordance with the composition scope of the alloy of the present invention and within the requirements of the limiting conditions.
  • the alloy in the comparative example 1 is not added with V and La during smelting.
  • the atom ratio of Al/(Ti+Nb) and the sum of the Nb+Ti+Al of the alloy in comparative example 2 do not conform to the limiting conditions of the alloy of the present invention.
  • the atomic ratio Cr/(Mo+W) in comparative example 3 does not conform to the limiting conditions of the alloy of the present invention.
  • the nickel-based superalloys for 700°C ultra-supercritical coal-fired power plant in embodiments 1-6 and comparative examples 1-3 are forged to round bars for implementation of the tensile tests at room temperature and at 700°C and 800°C, respectively.
  • the tensile test results can be seen in Table 2. Table 2.
  • the room temperature tensile test shows that the yield strength of the nickel-based alloys of the embodiments and comparative examples is greater than 780MPa, the tensile strength is greater than 1,200MPa, the elongation is greater than 24.0%, and the area reduction is greater than 32.0%.
  • the yield strength is greater than 640MPa, the tensile strength is greater than 980MPa, the elongation is greater than 23.0%, and the area reduction is greater than 30.0%.
  • the yield strength is greater than 600MPa
  • the tensile strength is greater than 800MPa
  • the elongation is greater than 17.0%
  • area reduction is greater than 25.0%
  • the alloys have high tensile strength and tensile ductility at both room temperature and high temperatures.
  • the nickel-based superalloys for 700°C ultra-supercritical coal-fired power plant in embodiments 1-6 is forged into bar product for stress-rupture tests at 750°C, 800°C and 850°C, respectively.
  • the stress-rupture life of the alloy in embodiments 1-6 is greater than 5,000h, the elongation is greater than 12.0%, the area reduction is greater than 16.0%; at the condition of 800°C /125MPa the stress-rupture life is greater than 5,000h, the elongation is greater than 14.0%, the area reduction is greater than 18.0%; at the condition of 850°C /100MPa, the stress-rupture life is greater than 1,500h, the elongation is greater than 20.0%, and the area reduction is greater than 25.0%.
  • the stress-rupture life of the alloy in comparative examples 1-3 is less than 3,000h, the elongation is less than 8.0%, the area reduction is less than 11.0%; at the condition of 800°C /125MPa the stress-rupture life is less than 2,500h, the elongation is less than 10.0%, the area reduction is less than 14.0%; at the condition of 850°C /100MPa, the stress-rupture life is less than 750h, the elongation is less than 12.0%, and the area reduction is less than 17.0%.
  • the nickel-based alloy of the present invention characterizes with high forgeability, can be used to manufacture the highest-temperature parts of the turbines and boilers of the 700°C ultra-supercritical coal-fired power plants and also can be applied to other fields where it needs a material with high ability of oxidation resistance, corrosion resistance, and with high tensile strength and creep strength as well.

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