WO2022021816A1 - Heat-resistant steel for steel pipe and casting - Google Patents

Heat-resistant steel for steel pipe and casting Download PDF

Info

Publication number
WO2022021816A1
WO2022021816A1 PCT/CN2021/072875 CN2021072875W WO2022021816A1 WO 2022021816 A1 WO2022021816 A1 WO 2022021816A1 CN 2021072875 W CN2021072875 W CN 2021072875W WO 2022021816 A1 WO2022021816 A1 WO 2022021816A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat
casting
resistant steel
steel
steel pipe
Prior art date
Application number
PCT/CN2021/072875
Other languages
French (fr)
Chinese (zh)
Inventor
梅林波
孙林根
安春香
王煜
Original Assignee
上海电气电站设备有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 上海电气电站设备有限公司 filed Critical 上海电气电站设备有限公司
Priority to JP2022557133A priority Critical patent/JP7428822B2/en
Priority to DE112021001054.9T priority patent/DE112021001054T5/en
Publication of WO2022021816A1 publication Critical patent/WO2022021816A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C21D1/28—Normalising
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/007—Heat treatment of ferrous alloys containing Co
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C21D9/085—Cooling or quenching
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C21D9/14—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes wear-resistant or pressure-resistant pipes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur

Definitions

  • the invention belongs to the technical field of metal materials, and relates to a heat-resistant steel for steel pipes and castings.
  • the boiler in the pressure vessel is an energy conversion device.
  • the energy input to the boiler includes chemical energy and electrical energy in the fuel, and the boiler outputs steam, high-temperature water or organic heat carrier with certain thermal energy.
  • the steam turbine in the power machinery also known as the steam turbine, is a rotary steam power device.
  • the high-temperature and high-pressure steam passes through the fixed nozzle to become an accelerated airflow and then sprays onto the blades, so that the rotor equipped with the blade row rotates and does external work at the same time.
  • Boilers and steam turbines are the main equipment of modern thermal power plants.
  • Improving the steam temperature parameters of thermal power and coal-fired units can improve unit efficiency, reduce fossil fuel consumption, and achieve energy conservation and emission reduction.
  • the operating temperature of boilers and steam turbines is limited by the maximum service temperature of key components such as steel pipes such as boiler pipes, castings such as cylinders and valves in steam turbines.
  • High-temperature materials for boiler pipes, cylinders and valves in steam turbines have been developed from Cr-Mo steel to various 9% to 12% Cr ferritic steels.
  • T92/P92, etc. are currently available for high-temperature materials of existing steel pipes such as boiler pipes;
  • ZG13Cr9Mo2Co1NiVNbNB, etc. are currently available for high-temperature materials of existing castings such as cylinders and valves in steam turbines.
  • the maximum working temperature of these steel grades cannot exceed 630°C, and there is currently no heat-resistant steel for steel pipes and castings that can meet the working temperature of 650°C.
  • the purpose of the present invention is to provide a heat-resistant steel for steel pipes and castings, which can be made into boiler pipes and steam turbine castings, and can meet the requirements of pressure vessels or power machinery zero at 650°C and below. Component usage requirements.
  • a first aspect of the present invention provides a kind of heat-resistant steel for steel pipes and castings, which is composed of the following elements by mass percentage:
  • the impurities are selected from P (phosphorus), S (sulfur), Al (aluminum), Ti (titanium), Zr (zirconium), Cu (copper), Sn (tin), As (arsenic), Sb ( one or more elements of antimony).
  • the mass percentage content of the elements in the impurities meets the following requirements: P: ⁇ 0.020wt%, S: ⁇ 0.010wt%, Al: ⁇ 0.02wt%, Ti: ⁇ 0.02wt%, Zr: ⁇ 0.02wt%, Cu: ⁇ 0.15wt%, Sn: ⁇ 0.02wt%, As: ⁇ 0.02wt%, Sb: ⁇ 0.005wt%.
  • the Cr (chromium) equivalent should be ⁇ 8.5% according to Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N, and all The mass ratio of the B element to the N element is 0.65-2.40:1.
  • the heat-resistant steel for steel pipes and castings is composed of the following elements by mass percentage:
  • the mass percentage content of the elements in the impurities meets the following requirements: P: ⁇ 0.020wt%, S: ⁇ 0.005wt%, Al: ⁇ 0.01wt%, Ti: ⁇ 0.01wt%, Zr: ⁇ 0.01wt% %, Cu: ⁇ 0.10wt%, Sn: ⁇ 0.01wt%, As: ⁇ 0.01wt%, Sb: ⁇ 0.003wt%.
  • the Cr (chromium) equivalent should be ⁇ 8.0% according to Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N, and The mass ratio of the B element to the N element is 0.75-2.10:1.
  • element C ensures hardenability.
  • C combines with other elements to form M23C6 carbides at the grain boundaries and martensitic lath boundaries, and form MX-type carbonitrides inside the martensitic laths, which can improve the high temperature strength.
  • C is also an indispensable element to suppress the formation of harmful phases ⁇ -ferrite and BN.
  • the C content should be limited to 0.08 to 0.14%. Further, the optimum content of element C should be limited to 0.08-0.13%.
  • Si acts as a deoxidizer for molten steel, and works together with Cr to improve the oxidation resistance of the steel.
  • the amount of Si added is too large, the deoxidized product SiO2 will remain in the steel, reducing the purity and toughness of the molten steel.
  • Si also promotes the precipitation of the intermetallic compound Laves phase and reduces the creep plasticity. Si increases temper brittleness when used at high temperatures. Therefore, the Si content should be limited to 0.20 to 0.40%. Further, the optimum content of Si element should be limited to 0.20-0.30%.
  • Mn element can remove oxygen and sulfur elements in molten steel, improve the hardenability and strength of steel, inhibit the formation of ⁇ -ferrite and BN, and promote M23C6 Carbide precipitation. But with the increase of Mn content, the creep rupture strength decreases. Therefore, the content of Mn element should be limited to 0.30-0.60%. Further, the optimum content of Mn element should be limited to 0.40-0.50%.
  • Ni element can increase the hardenability of the steel, inhibit the formation of ⁇ -ferrite and BN, and improve the strength and toughness at room temperature.
  • the addition of Ni element is not conducive to the high temperature creep properties of the steel and increases the temper brittleness of the steel.
  • the addition amount of Ni should be as low as possible, preferably not more than 0.20%, and preferably not more than 0.10%.
  • Cr element can improve oxidation resistance and corrosion resistance, and improve high-temperature strength by precipitating M23C6 carbides.
  • the content of Cr element in the heat-resistant steel of the present invention is at least 9.00%. However, if it exceeds 10.00%, ⁇ -ferrite is easily formed, and the high-strength temperature and toughness are lowered. Therefore, the content of Cr element should be limited to 9.00-10.00%. Further, the optimum content of Cr element should be limited to 9.00-9.60%.
  • the Cr equivalent (Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N) of the heat-resistant steel of the present invention is limited to less than 8.5%, more preferably less than 8.0%. Precipitation of delta-ferrite can be avoided.
  • Mo element can improve the hardenability, suppress temper brittleness, promote the dispersion and precipitation of M23C6 carbides, and improve the tensile strength and creep rupture strength of the steel.
  • excessive Mo element will promote the precipitation of ⁇ -ferrite and intermetallic compound Laves phase, and significantly reduce the toughness. Therefore, the content of Mo element is limited to 0.55 to 0.80%. Further, the optimum content of Mo element should be limited to 0.60-0.75%.
  • W element is very effective in suppressing the coarsening of M23C6 carbides, and its effect exceeds that of Mo element, which can significantly improve the creep rupture strength.
  • the Co element can suppress the precipitation of ⁇ -ferrite while solid solution strengthening.
  • Co element interacts with Mo element and W element, which obviously improves the high temperature strength and improves the toughness of the steel.
  • the content of Co element should not be too high.
  • the content of Co element should be limited to 2.80-3.30%. Further, the optimum content of Co element should be limited to 2.90-3.20%.
  • the V element can improve the tensile strength.
  • fine carbonitrides of the V element are formed inside the martensitic lath to increase the creep rupture strength. Adding a certain amount of V element can refine the grains and improve the toughness. However, if the addition amount is too large, the toughness will be lowered, and the carbon will be fixed excessively, resulting in a decrease in the precipitation amount of M23C6 carbides. Therefore, its content is 0.15 to 0.25%. The expected value should be 0.18-0.25%.
  • Nb element like V element, can improve tensile strength and creep rupture strength.
  • Nb element and C element generate fine NbC, which can refine grains and improve toughness.
  • the MX carbonitride formed by Nb element and V element has the effect of improving high temperature strength, and its minimum content should be 0.03%.
  • carbon is excessively fixed to reduce the precipitation amount of M23C6 carbides, resulting in a decrease in high temperature strength. Therefore, it needs to be limited to 0.03 to 0.08%.
  • the expected value should be 0.04-0.07%.
  • N element can precipitate VN nitride with V element, and the solid solution state is combined with Mo element and W element to improve high temperature strength, and the minimum content should be 0.005%.
  • the addition exceeds 0.015%, the plasticity will be impaired.
  • B element it is easy to form eutectic Fe2B and BN, which damages the creep performance and toughness of steel. Therefore, the N element content is limited to 0.006 to 0.015%. Further, the optimum content of N element should be limited to 0.007-0.014%.
  • element B has the effect of strengthening grain boundaries, has the effect of inhibiting the coarsening of M23C6 carbides, and improves high-temperature strength.
  • the B element content is limited to 0.009 to 0.015%.
  • the optimum content of element B should be limited to 0.010-0.015%.
  • the mass ratio of B element to N element should be controlled to be 0.65-2.40:1, more preferably, 0.75-2.10:1.
  • the above-mentioned unavoidable impurities are inclusion elements that are inevitably contaminated in the steel smelting process.
  • the content of these elements should be as low as possible. If the steelmaking raw materials are strictly screened, the cost will rise. Therefore, the P content should be limited to not higher than 0.020%, the S content to be not higher than 0.010%, and the Cu content to be not higher than 0.15%.
  • other inclusion elements such as Al, Ti, Zr, Sn, As, Sb, etc. have adverse effects on the mechanical properties of this heat-resistant steel, and their content should be reduced as much as possible.
  • the second aspect of the present invention provides a method for preparing a steel pipe.
  • the heat-resistant steel is mixed with raw materials according to the element ratio, and then smelted, and firstly prepared by any one of continuous casting, die casting, hot rolling or hot forging.
  • the tube blank is then made into a steel tube by any one of hot rolling, hot extrusion, hot expansion, cold drawing, cold rolling or forging and boring, and then the steel tube is normalized or quenched and then tempered to obtain .
  • the temperature of the normalizing or quenching is 1070-1160°C.
  • the tempering includes at least one time, and the tempering temperature is 740-790°C.
  • a third aspect of the present invention provides a method for preparing a casting.
  • the heat-resistant steel is mixed with raw materials according to the element ratio, smelted and casted to obtain a casting, and then the casting is normalized or quenched and then tempered.
  • the temperature of the normalizing or quenching is 1070-1160°C.
  • the tempering includes at least one time, and the tempering temperature is 730-780°C.
  • a fourth aspect of the present invention provides the use of the above heat-resistant steel or steel pipe in a pressure vessel.
  • the pressure vessel is a boiler tube.
  • a fifth aspect of the present invention provides the use of the above-mentioned heat-resistant steel or casting in a power machine.
  • the power machine is a steam turbine.
  • the smelting includes alloy smelting and refining processes.
  • the alloy smelting and refining processes in the above-mentioned smelting are all well-known technical processes in the field of steel manufacturing.
  • the heat-resistant steel for steel pipes and castings provided by the present invention can obtain steel pipes and castings with excellent performance through the preferred element components and preparation steps thereof.
  • Co element is added, the ratio of B and N is adjusted, the content of Cr, Mo and B elements is increased, and the content of Nb, N and Ni elements is reduced.
  • the content of Si and W elements has been more strictly limited, and the limit of impurity elements Cu, Sn, As, and Sb has been increased; compared with the existing casting material ZG13Cr9Mo2Co1NiVNbNB, W element has been added, and the ratio of B and N has been adjusted.
  • the contents of Co and B elements are increased, the contents of Mn, Mo, N and Ni elements are decreased, and the limits of impurity elements Ti, Zr, Cu, Sn, As, and Sb are increased.
  • the invention provides a heat-resistant steel for steel pipes and castings, which improves the high-temperature creep rupture strength and oxidation resistance, which will increase the operating temperature, thereby improving the thermal efficiency of the generator set and reducing coal consumption and carbon dioxide emissions.
  • the material grade is abbreviated as TB4 (small-diameter pipe)/PB4 (large-diameter pipe), and the material grade is abbreviated as CB4 when used as a casting material.
  • the heat-resistant steel for steel pipes and castings provided by the present invention can be used to prepare pressure vessels and power machinery, especially boiler pipes and steam turbine castings. It has good high temperature creep rupture strength and oxidation resistance in the environment, and can meet the requirements of boilers and steam turbines with a working temperature of 650 °C and below.
  • each component is composed of the following elements by mass percentage:
  • the mass percentage contents of the elements in the impurities are: P: 0.008wt%, S: 0.003wt%, Al: 0.01wt%, Ti: 0.003wt%, Zr: 0.001wt%, Cu: 0.05wt% , Sn: 0.001wt%, As: 0.001wt%, Sb: 0.001wt%.
  • the Cr equivalent is 7.62%.
  • the mass ratio of B element to N element is 1:1.
  • smelting is carried out, that is, alloy smelting and refining are carried out in sequence, and then die-casting into a tube blank. That is, the steel pipe sample 1# is obtained.
  • the normalizing temperature is 1100°C
  • the tempering includes one time
  • the tempering temperature is 780°C.
  • Steel tube sample 1# is a boiler tube.
  • each component is composed of the following elements by mass percentage:
  • the mass percentage contents of the elements in the impurities are: P: 0.012wt%, S: 0.005wt%, Al: 0.01wt%, Ti: 0.005wt%, Zr: 0.001wt%, Cu: 0.06wt% , Sn: 0.001wt%, As: 0.002wt%, Sb: 0.0015wt%.
  • the Cr equivalent is 6.7%.
  • the mass ratio of B element to N element is 1.4:1.
  • smelting is carried out, that is, alloy smelting and refining are carried out in sequence, and then cast into castings.
  • the castings are normalized and tempered to obtain casting sample 1*.
  • the normalizing temperature is 1140°C
  • the tempering includes 2 times
  • the tempering temperature is 755°C.
  • Casting sample 1* is a steam turbine valve casing casting.
  • Example 1 Example 2 C 0.10 0.12 Si 0.30 0.25 Mn 0.50 0.45 Cr 9.30 9.60
  • Example 1 Example 2 P 0.008 0.012 S 0.003 0.005 Al 0.01 0.01 Ti 0.003 0.005 Zr 0.001 0.001 Cu 0.05 0.06 Sn 0.001 0.001 As 0.001 0.002 Sb 0.001 0.0015
  • the steel pipe sample 1# obtained in Example 1 and the casting sample 1* obtained in Example 2 were tested for creep rupture strength according to the national standard GB/T 2039, and then extrapolated according to the national standard GB/T 2039.
  • the method deduces the creep rupture strength limit R u100000h/650°C at 650°C/100,000 hours, and compares it with the creep rupture strength of T92/P92 and ZG13Cr9Mo2Co1NiVNbNB at 650°C/100,000 hours respectively.
  • the results are as follows shown in Table 4.
  • the samples were placed in a water vapor environment of 620°C/650°C and 27MPa flowing for a maximum time of 2000h, and the weight gain of each sample during this period was tested. The smaller the oxidation weight gain, the better the oxidation resistance of the material.
  • test results show that at the same temperature, the oxidation resistance of steel pipe sample 1# is significantly better than that of T92/P92, and the oxidation resistance of casting sample 1* is significantly better than that of ZG13Cr9Mo2Co1NiVNbNB.
  • the oxidation weight gain of steel pipe sample 1# is similar to that of T92/P92 at 620°C, and the oxidation weight gain of casting sample 1* is similar to that of ZG13Cr9Mo2Co1NiVNbNB at 620°C similar. It shows that the steel pipes and castings prepared from the heat-resistant steel of the present invention can basically meet the needs of long-term use under the working condition of 650°C without using a surface protective coating to resist oxidation.
  • the present invention effectively overcomes various shortcomings in the prior art and has high industrial application value.

Abstract

A heat-resistant steel for a steel pipe and a casting, consisting of elements: 0.08-0.14wt% of C, 0.20-0.40wt% of Si, 0.30-0.60wt% of Mn, 9.00-10.00wt% of Cr, 2.80-3.30wt% of Co, 1.65-1.90wt% of W, 0.55-0.80wt% of Mo, 0.15-0.25wt% of V, 0.03-0.08wt% of Nb, 0.006-0.015wt% of N, 0.009-0.015wt% of B, ≤0.20wt% of Ni, and the balance being Fe and inevitable impurities. A preparation method for the steel pipe comprises: for the heat-resistant steel, taking raw materials according to an element ratio, mixing, and then smelting; firstly, making a pipe blank by using any one of continuous casting, die casting, hot rolling, or hot forging; then making the pipe blank into a steel pipe by using any one of hot rolling, hot extrusion, hot expansion, cold drawing, cold rolling, or forging boring; and then normalizing or quenching the steel pipe and then tempering same to obtain a finished steel pipe. A preparation method for the casting comprises: for the heat-resistant steel, taking raw materials according to an element ratio, mixing, and then smelting; casting then to obtain a casting; and then normalizing or quenching the casting and then tempering same to obtain a finished casting.

Description

一种钢管和铸件用耐热钢A heat-resistant steel for steel pipes and castings 技术领域technical field
本发明属于金属材料的技术领域，涉及一种钢管和铸件用耐热钢。The invention belongs to the technical field of metal materials, and relates to a heat-resistant steel for steel pipes and castings.
背景技术Background technique
压力容器中的锅炉，是一种能量转换设备，向锅炉输入的能量有燃料中的化学能、电能，锅炉输出具有一定热能的蒸汽、高温水或有机热载体。动力机械中的汽轮机也称蒸汽透平，是一种旋转式蒸汽动力装置，高温高压蒸汽穿过固定喷嘴成为加速的气流后喷射到叶片上，使得装有叶片排的转子旋转，同时对外做功。锅炉和汽轮机是现代火力发电厂的主要设备。The boiler in the pressure vessel is an energy conversion device. The energy input to the boiler includes chemical energy and electrical energy in the fuel, and the boiler outputs steam, high-temperature water or organic heat carrier with certain thermal energy. The steam turbine in the power machinery, also known as the steam turbine, is a rotary steam power device. The high-temperature and high-pressure steam passes through the fixed nozzle to become an accelerated airflow and then sprays onto the blades, so that the rotor equipped with the blade row rotates and does external work at the same time. Boilers and steam turbines are the main equipment of modern thermal power plants.
提高火电燃煤机组的蒸汽温度参数可以提高机组效率，减少化石燃料的消耗，实现节能减排。而锅炉和汽轮机运行温度受限于钢管如锅炉管道、铸件如汽轮机中的汽缸和阀门等关键部件材料的最高使用温度。Improving the steam temperature parameters of thermal power and coal-fired units can improve unit efficiency, reduce fossil fuel consumption, and achieve energy conservation and emission reduction. The operating temperature of boilers and steam turbines is limited by the maximum service temperature of key components such as steel pipes such as boiler pipes, castings such as cylinders and valves in steam turbines.
锅炉管道、汽轮机中的汽缸和阀门等部件用高温材料从Cr-Mo钢发展成各类9％～12％Cr铁素体钢。其中，现有钢管如锅炉管道的高温材料中，目前可供选用的有T92/P92等；现有铸件如汽轮机中汽缸和阀门的高温材料中，目前可供选用的有ZG13Cr9Mo2Co1NiVNbNB等。但是，这些钢种的最高工作温度不能超过630℃，目前没有能够满足工作温度为650℃的钢管和铸件用耐热钢。High-temperature materials for boiler pipes, cylinders and valves in steam turbines have been developed from Cr-Mo steel to various 9% to 12% Cr ferritic steels. Among them, T92/P92, etc. are currently available for high-temperature materials of existing steel pipes such as boiler pipes; ZG13Cr9Mo2Co1NiVNbNB, etc. are currently available for high-temperature materials of existing castings such as cylinders and valves in steam turbines. However, the maximum working temperature of these steel grades cannot exceed 630°C, and there is currently no heat-resistant steel for steel pipes and castings that can meet the working temperature of 650°C.
发明的公开disclosure of invention
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种钢管和铸件用耐热钢，其能制成锅炉管道和汽轮机铸件，可以满足650℃及650℃以下压力容器或动力机械零部件的使用要求。In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a heat-resistant steel for steel pipes and castings, which can be made into boiler pipes and steam turbine castings, and can meet the requirements of pressure vessels or power machinery zero at 650°C and below. Component usage requirements.
为实现上述目的及其他相关目的，本发明第一方面提供一种钢管和铸件用耐热钢，由以下质量百分比的元素组成：In order to achieve the above-mentioned purpose and other related purposes, a first aspect of the present invention provides a kind of heat-resistant steel for steel pipes and castings, which is composed of the following elements by mass percentage:
C(碳)：0.08～0.14wt％，Si(硅)：0.20～0.40wt％，Mn(锰)：0.30～0.60wt％，Cr(铬)：9.00～10.00wt％，Co(钴)：2.80～3.30wt％，W(钨)：1.65～1.90wt％，Mo(钼)：0.55～0.80wt％，V(钒)：0.15～0.25wt％，Nb(铌)：0.03～0.08wt％，N(氮)：0.006～0.015wt％，B(硼)：0.009～0.015wt％，Ni(镍)：≤0.20wt％，余量为Fe(铁)和不可避免的杂质。C (carbon): 0.08-0.14wt%, Si (silicon): 0.20-0.40wt%, Mn (manganese): 0.30-0.60wt%, Cr (chromium): 9.00-10.00wt%, Co (cobalt): 2.80 ～3.30wt%, W (tungsten): 1.65～1.90wt%, Mo (molybdenum): 0.55～0.80wt%, V (vanadium): 0.15～0.25wt%, Nb (niobium): 0.03～0.08wt%, N (Nitrogen): 0.006-0.015wt%, B (boron): 0.009-0.015wt%, Ni (nickel): ≤0.20wt%, the balance is Fe (iron) and inevitable impurities.
优选地，所述杂质选自P(磷)、S(硫)、Al(铝)、Ti(钛)、Zr(锆)、Cu(铜)、Sn(锡)、As(砷)、Sb(锑)中的一种或多种元素。其中，所述杂质中元素的质量百分比含量符合以下要求：P：≤0.020wt％，S：≤0.010wt％，Al：≤0.02wt％，Ti：≤0.02wt％，Zr：≤0.02wt％，Cu：≤0.15wt％，Sn：≤0.02wt％，As：≤0.02wt％，Sb：≤0.005wt％。Preferably, the impurities are selected from P (phosphorus), S (sulfur), Al (aluminum), Ti (titanium), Zr (zirconium), Cu (copper), Sn (tin), As (arsenic), Sb ( one or more elements of antimony). Wherein, the mass percentage content of the elements in the impurities meets the following requirements: P: ≤0.020wt%, S: ≤0.010wt%, Al: ≤0.02wt%, Ti: ≤0.02wt%, Zr: ≤0.02wt%, Cu:≤0.15wt%, Sn:≤0.02wt%, As:≤0.02wt%, Sb:≤0.005wt%.
优选地，所述钢管和铸件用耐热钢中，Cr(铬)当量按Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N计应≤8.5％，且所述B元素与N元素的质量之比为0.65～2.40：1。Preferably, in the heat-resistant steel for steel pipes and castings, the Cr (chromium) equivalent should be ≤8.5% according to Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N, and all The mass ratio of the B element to the N element is 0.65-2.40:1.
优选地，所述钢管和铸件用耐热钢，由以下质量百分比的元素组成：Preferably, the heat-resistant steel for steel pipes and castings is composed of the following elements by mass percentage:
C：0.08～0.13wt％，Si：0.20～0.30wt％，Mn：0.40～0.50wt％，Cr：9.00～9.60wt％，Co：2.90～3.20wt％，W：1.70～1.85wt％，Mo：0.60～0.75wt％，V：0.18～0.25wt％，Nb：0.04～0.07wt％，N：0.007～0.014wt％，B：0.010～0.015wt％，Ni：≤0.10wt％，余量为Fe和不可避免的杂质。C: 0.08-0.13wt%, Si: 0.20-0.30wt%, Mn: 0.40-0.50wt%, Cr: 9.00-9.60wt%, Co: 2.90-3.20wt%, W: 1.70-1.85wt%, Mo: 0.60～0.75wt%, V: 0.18～0.25wt%, Nb: 0.04～0.07wt%, N: 0.007～0.014wt%, B: 0.010～0.015wt%, Ni: ≤0.10wt%, the balance is Fe and inevitable impurities.
更优选地，所述杂质中元素的质量百分比含量符合以下要求：P：≤0.020wt％，S：≤0.005wt％，Al：≤0.01wt％，Ti：≤0.01wt％，Zr：≤0.01wt％，Cu：≤0.10wt％，Sn：≤0.01wt％，As：≤0.01wt％，Sb：≤0.003wt％。More preferably, the mass percentage content of the elements in the impurities meets the following requirements: P:≤0.020wt%, S:≤0.005wt%, Al:≤0.01wt%, Ti:≤0.01wt%, Zr:≤0.01wt% %, Cu:≤0.10wt%, Sn:≤0.01wt%, As:≤0.01wt%, Sb:≤0.003wt%.
更优选地，所述钢管和铸件用耐热钢中，Cr(铬)当量按Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N计应≤8.0％，且所述B元素与N元素的质量之比为0.75～2.10：1。More preferably, in the heat-resistant steel for steel pipes and castings, the Cr (chromium) equivalent should be ≤8.0% according to Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N, and The mass ratio of the B element to the N element is 0.75-2.10:1.
在本发明所提供的钢管和铸件用耐热钢中，C元素确保淬透性。在回火过程中，C与其他元素结合，在晶界和马氏体板条边界形成M23C6碳化物，在马氏体板条内部形成MX型碳氮化物，可提高高温强度。除了确保强度和韧性外，C也是抑制有害相δ-铁素体和BN生成的不可或缺的元素。但是，如果添加过量，反而会降低韧性和强度，损害长时蠕变断裂强度。所以，C含量应限定在0.08～0.14％。进一步来说，C元素的最佳含量应限定在 0.08～0.13％。In the heat-resistant steel for steel pipes and castings provided by the present invention, element C ensures hardenability. During the tempering process, C combines with other elements to form M23C6 carbides at the grain boundaries and martensitic lath boundaries, and form MX-type carbonitrides inside the martensitic laths, which can improve the high temperature strength. In addition to ensuring strength and toughness, C is also an indispensable element to suppress the formation of harmful phases δ-ferrite and BN. However, if it is added in excess, it will reduce the toughness and strength, and damage the long-term creep rupture strength. Therefore, the C content should be limited to 0.08 to 0.14%. Further, the optimum content of element C should be limited to 0.08-0.13%.
在本发明所提供的钢管和铸件用耐热钢中，Si作为钢水脱氧剂，与Cr共同作用还可提高钢的抗氧化性。但是，若Si添加量过多，则会在钢中残留脱氧产物SiO2，降低钢水的纯净度和韧性。另外，Si还会促进金属间化合物Laves相析出，降低蠕变塑性。在高温使用时，Si会增加回火脆性。所以，Si含量应限定在0.20～0.40％。进一步来说，Si元素的最佳含量应限定在0.20～0.30％。In the heat-resistant steel for steel pipes and castings provided by the present invention, Si acts as a deoxidizer for molten steel, and works together with Cr to improve the oxidation resistance of the steel. However, if the amount of Si added is too large, the deoxidized product SiO2 will remain in the steel, reducing the purity and toughness of the molten steel. In addition, Si also promotes the precipitation of the intermetallic compound Laves phase and reduces the creep plasticity. Si increases temper brittleness when used at high temperatures. Therefore, the Si content should be limited to 0.20 to 0.40%. Further, the optimum content of Si element should be limited to 0.20-0.30%.
在本发明所提供的钢管和铸件用耐热钢中，Mn元素可以脱除钢水中的氧和硫元素，提高钢的淬透性和强度，抑制δ-铁素体和BN的生成，促进M23C6碳化物析出。但随Mn元素含量增加，蠕变断裂强度降低。所以Mn元素含量应限定在0.30～0.60％。进一步来说，Mn元素的最佳含量应限定在0.40～0.50％。In the heat-resistant steel for steel pipes and castings provided by the present invention, Mn element can remove oxygen and sulfur elements in molten steel, improve the hardenability and strength of steel, inhibit the formation of δ-ferrite and BN, and promote M23C6 Carbide precipitation. But with the increase of Mn content, the creep rupture strength decreases. Therefore, the content of Mn element should be limited to 0.30-0.60%. Further, the optimum content of Mn element should be limited to 0.40-0.50%.
在本发明所提供的钢管和铸件用耐热钢中，Ni元素可以增加钢的淬透性，抑制δ-铁素体和BN生成，提高室温强度和韧性。但是，添加Ni元素不利于钢的高温蠕变性能，增加钢的回火脆性。为了保证本发明耐热钢获得需要的高温蠕变强度，Ni元素添加量应尽可能低，期望不超过0.20％，不超过0.10％为最佳。In the heat-resistant steel for steel pipes and castings provided by the present invention, Ni element can increase the hardenability of the steel, inhibit the formation of δ-ferrite and BN, and improve the strength and toughness at room temperature. However, the addition of Ni element is not conducive to the high temperature creep properties of the steel and increases the temper brittleness of the steel. In order to ensure the required high-temperature creep strength of the heat-resistant steel of the present invention, the addition amount of Ni should be as low as possible, preferably not more than 0.20%, and preferably not more than 0.10%.
在本发明所提供的钢管和铸件用耐热钢中，Cr元素可以提高抗氧化性和耐腐蚀性，通过析出M23C6碳化物提高高温强度。为取得上述效果，本发明耐热钢的Cr元素含量最低为9.00％。但是，如果超过10.00％，则易生成δ-铁素体，降低高强温度和韧性。因而，Cr元素含量应限定在9.00～10.00％。进一步来说，Cr元素的最佳含量应限定在9.00～9.60％。同时，本发明耐热钢的Cr当量(Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N)限定在8.5％以下，更优选地限定在8.0％以下，就能避免析出δ-铁素体。In the heat-resistant steel for steel pipes and castings provided by the present invention, Cr element can improve oxidation resistance and corrosion resistance, and improve high-temperature strength by precipitating M23C6 carbides. In order to achieve the above effects, the content of Cr element in the heat-resistant steel of the present invention is at least 9.00%. However, if it exceeds 10.00%, δ-ferrite is easily formed, and the high-strength temperature and toughness are lowered. Therefore, the content of Cr element should be limited to 9.00-10.00%. Further, the optimum content of Cr element should be limited to 9.00-9.60%. At the same time, the Cr equivalent (Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N) of the heat-resistant steel of the present invention is limited to less than 8.5%, more preferably less than 8.0%. Precipitation of delta-ferrite can be avoided.
在本发明所提供的钢管和铸件用耐热钢中，Mo元素可提高淬透性，抑制回火脆性，促进M23C6碳化物弥散析出，提高钢的拉伸强度和蠕变断裂强度。但Mo元素过量，则会促进δ-铁素体和金属间化合物Laves相的析出，明显降低韧性。所以Mo元素含量限定在0.55～0.80％。进一步来说，Mo元素的最佳含量应限定在0.60～0.75％。In the heat-resistant steel for steel pipes and castings provided by the present invention, Mo element can improve the hardenability, suppress temper brittleness, promote the dispersion and precipitation of M23C6 carbides, and improve the tensile strength and creep rupture strength of the steel. However, excessive Mo element will promote the precipitation of δ-ferrite and intermetallic compound Laves phase, and significantly reduce the toughness. Therefore, the content of Mo element is limited to 0.55 to 0.80%. Further, the optimum content of Mo element should be limited to 0.60-0.75%.
在本发明所提供的钢管和铸件用耐热钢中，W元素对于抑制M23C6碳 化物的粗化很有效，其作用超过Mo元素，可显著提高蠕变断裂强度。添加W元素取代部分Mo元素，保证Mo元素当量(Mo+1/2W)为1.5％左右，强化效果最明显，且不至于形成过多δ-铁素体和金属间化合物Laves相。若W元素添加量超过1.90％时，会损害塑性、韧性和蠕变断裂强度，且钢中容易出现偏析。因此，W元素的含量应限定在1.65～1.90％。进一步来说，W元素的最佳含量应限定在1.70～1.85％。In the heat-resistant steel for steel pipes and castings provided by the present invention, W element is very effective in suppressing the coarsening of M23C6 carbides, and its effect exceeds that of Mo element, which can significantly improve the creep rupture strength. Adding W element to replace part of Mo element to ensure that the Mo element equivalent (Mo+1/2W) is about 1.5%, the strengthening effect is the most obvious, and it will not form too much δ-ferrite and intermetallic compound Laves phase. If the addition amount of W element exceeds 1.90%, the plasticity, toughness and creep rupture strength will be impaired, and segregation will easily occur in the steel. Therefore, the content of element W should be limited to 1.65-1.90%. Further, the optimum content of W element should be limited to 1.70-1.85%.
在本发明所提供的钢管和铸件用耐热钢中，Co元素在固溶强化的同时，能抑制δ-铁素体的析出。Co元素与Mo元素和W元素相互作用，明显改善高温强度，提高钢的韧性。同时，为了控制成本，Co元素含量不宜过高。Co元素含量应限定在2.80～3.30％。进一步来说，Co元素的最佳含量应限定在2.90～3.20％。In the heat-resistant steel for steel pipes and castings provided by the present invention, the Co element can suppress the precipitation of δ-ferrite while solid solution strengthening. Co element interacts with Mo element and W element, which obviously improves the high temperature strength and improves the toughness of the steel. At the same time, in order to control the cost, the content of Co element should not be too high. The content of Co element should be limited to 2.80-3.30%. Further, the optimum content of Co element should be limited to 2.90-3.20%.
在本发明所提供的钢管和铸件用耐热钢中，V元素可提高拉伸强度。而且，在马氏体板条内部生成V元素的细小碳氮化物，提高蠕变断裂强度。添加一定量的V元素，可以细化晶粒，提高韧性。但是，若添加量过多，则会降低韧性，碳被过度固定从而造成M23C6碳化物析出量减少。因此，其含量为0.15～0.25％。期望值应是0.18～0.25％。In the heat-resistant steel for steel pipes and castings provided by the present invention, the V element can improve the tensile strength. In addition, fine carbonitrides of the V element are formed inside the martensitic lath to increase the creep rupture strength. Adding a certain amount of V element can refine the grains and improve the toughness. However, if the addition amount is too large, the toughness will be lowered, and the carbon will be fixed excessively, resulting in a decrease in the precipitation amount of M23C6 carbides. Therefore, its content is 0.15 to 0.25%. The expected value should be 0.18-0.25%.
在本发明所提供的钢管和铸件用耐热钢中，Nb元素与V元素一样，可以提高拉伸强度和蠕变断裂强度。Nb元素与C元素生成细小的NbC，可以细化晶粒，提高韧性。而且，Nb元素与V元素形成的MX碳氮化物，具有提高高温强度的作用，其最低含量应是0.03％。但是，其含量在0.08％以上时，则与V元素一样，过度固定碳从而减少M23C6碳化物的析出量，引起高温强度下降。因而，需限定在0.03～0.08％。期望值应是0.04～0.07％。In the heat-resistant steel for steel pipes and castings provided by the present invention, Nb element, like V element, can improve tensile strength and creep rupture strength. Nb element and C element generate fine NbC, which can refine grains and improve toughness. Moreover, the MX carbonitride formed by Nb element and V element has the effect of improving high temperature strength, and its minimum content should be 0.03%. However, when its content is 0.08% or more, as with the V element, carbon is excessively fixed to reduce the precipitation amount of M23C6 carbides, resulting in a decrease in high temperature strength. Therefore, it needs to be limited to 0.03 to 0.08%. The expected value should be 0.04-0.07%.
在本发明所提供的钢管和铸件用耐热钢中，N元素可与V元素析出VN氮化物，固溶状态与Mo元素和W元素组合，提高高温强度，含量最低应为0.005％。但若添加超过0.015％，则损害塑性。并且与B元素共存时，易生成共晶Fe2B和BN，损害钢的蠕变性能和韧性。所以N元素含量限定在0.006～0.015％。进一步来说，N元素的最佳含量应限定在0.007～0.014％。In the heat-resistant steel for steel pipes and castings provided by the present invention, N element can precipitate VN nitride with V element, and the solid solution state is combined with Mo element and W element to improve high temperature strength, and the minimum content should be 0.005%. However, if the addition exceeds 0.015%, the plasticity will be impaired. And when it coexists with B element, it is easy to form eutectic Fe2B and BN, which damages the creep performance and toughness of steel. Therefore, the N element content is limited to 0.006 to 0.015%. Further, the optimum content of N element should be limited to 0.007-0.014%.
在本发明所提供的钢管和铸件用耐热钢中，B元素具有晶界强化作用，具有抑制M23C6碳化物粗化的作用，提高高温强度。但是，若在0.015％以上时，则对锻造性能和焊接性能不利。因而，B元素含量限定在0.009～0.015％。 进一步来说，B元素的最佳含量应限定在0.010～0.015％。为了防止B元素和N元素结合生成BN，应控制B元素与N元素的质量之比为0.65～2.40：1，更优选地，应控制在0.75～2.10：1。In the heat-resistant steel for steel pipes and castings provided by the present invention, element B has the effect of strengthening grain boundaries, has the effect of inhibiting the coarsening of M23C6 carbides, and improves high-temperature strength. However, if it is 0.015% or more, it is disadvantageous for forging performance and welding performance. Therefore, the B element content is limited to 0.009 to 0.015%. Further, the optimum content of element B should be limited to 0.010-0.015%. In order to prevent B element and N element from combining to form BN, the mass ratio of B element to N element should be controlled to be 0.65-2.40:1, more preferably, 0.75-2.10:1.
上述不可避免的杂质是钢铁冶炼过程中不可避免沾染的夹杂物元素。这些元素含量应尽可能低。如果严格筛选炼钢原料，则造成成本上升。因而，应限定P含量不高于0.020％，S含量不高于0.010％，Cu含量不高于0.15％。同时，其他夹杂物元素有Al、Ti、Zr、Sn、As、Sb等对本耐热钢的力学性能有不利影响，应尽量降低其含量。The above-mentioned unavoidable impurities are inclusion elements that are inevitably contaminated in the steel smelting process. The content of these elements should be as low as possible. If the steelmaking raw materials are strictly screened, the cost will rise. Therefore, the P content should be limited to not higher than 0.020%, the S content to be not higher than 0.010%, and the Cu content to be not higher than 0.15%. At the same time, other inclusion elements such as Al, Ti, Zr, Sn, As, Sb, etc. have adverse effects on the mechanical properties of this heat-resistant steel, and their content should be reduced as much as possible.
本发明第二方面提供一种钢管的制备方法，将所述耐热钢按元素配比取原料混合后进行冶炼，先采用连铸、模铸、热轧或热锻中的任一种制成管坯，然后将管坯采用热轧、热挤压、热扩、冷拔、冷轧或锻造镗孔中的任一种制成钢管，再将钢管进行正火或淬火后回火，即得。The second aspect of the present invention provides a method for preparing a steel pipe. The heat-resistant steel is mixed with raw materials according to the element ratio, and then smelted, and firstly prepared by any one of continuous casting, die casting, hot rolling or hot forging. The tube blank is then made into a steel tube by any one of hot rolling, hot extrusion, hot expansion, cold drawing, cold rolling or forging and boring, and then the steel tube is normalized or quenched and then tempered to obtain .
优选地，所述正火或淬火的温度为1070～1160℃。Preferably, the temperature of the normalizing or quenching is 1070-1160°C.
优选地，所述回火包括至少一次，所述回火的温度为740～790℃。Preferably, the tempering includes at least one time, and the tempering temperature is 740-790°C.
上述连铸、模铸、热轧、热锻、热挤压、热扩、冷拔、冷轧或锻造镗孔均为钢铁制造领域公知的技术工序。The above-mentioned continuous casting, die casting, hot rolling, hot forging, hot extrusion, hot expansion, cold drawing, cold rolling or forging boring are all well-known technical processes in the field of steel manufacturing.
上述钢管的技术工序符合国家标准GB5310的规定。The technical process of the above steel pipe conforms to the provisions of the national standard GB5310.
本发明第三方面提供一种铸件的制备方法，将所述耐热钢按元素配比取原料混合后进行冶炼、浇铸后得到铸件，再将铸件进行正火或淬火后回火，即得。A third aspect of the present invention provides a method for preparing a casting. The heat-resistant steel is mixed with raw materials according to the element ratio, smelted and casted to obtain a casting, and then the casting is normalized or quenched and then tempered.
优选地，所述正火或淬火的温度为1070～1160℃。Preferably, the temperature of the normalizing or quenching is 1070-1160°C.
优选地，所述回火包括至少一次，所述回火的温度为730～780℃。Preferably, the tempering includes at least one time, and the tempering temperature is 730-780°C.
上述浇铸为钢铁制造领域公知的技术工序。The above-mentioned casting is a well-known technical process in the field of steel manufacturing.
本发明第四方面提供上述耐热钢、或钢管在压力容器中的用途。A fourth aspect of the present invention provides the use of the above heat-resistant steel or steel pipe in a pressure vessel.
优选地，所述压力容器为锅炉管道。Preferably, the pressure vessel is a boiler tube.
本发明第五方面提供上述耐热钢、或铸件在动力机械中的用途。A fifth aspect of the present invention provides the use of the above-mentioned heat-resistant steel or casting in a power machine.
优选地，所述动力机械为汽轮机。Preferably, the power machine is a steam turbine.
上述钢管和/或铸件的制备方法中，所述冶炼包括有合金熔炼及精炼工序。上述冶炼中的合金熔炼、精炼工序均为钢铁制造领域公知的技术工序。In the above-mentioned preparation method of steel pipes and/or castings, the smelting includes alloy smelting and refining processes. The alloy smelting and refining processes in the above-mentioned smelting are all well-known technical processes in the field of steel manufacturing.
如上所述，本发明提供的一种钢管和铸件用耐热钢，通过优选的元素组 分及其制备步骤，能够制备获得性能优异的钢管和铸件。其与现有的锅炉管道材料T/P92相比，添加了Co元素，调整了B和N的比例，提高了Cr、Mo、B元素的含量，降低了Nb、N和Ni元素的含量，对Si、W元素含量做了更严格的限定，增加了对杂质元素Cu、Sn、As、Sb的限定；与现有的铸件材料ZG13Cr9Mo2Co1NiVNbNB相比，添加了W元素，调整了B和N的比例，提高了Co和B元素的含量，降低了Mn、Mo、N和Ni元素的含量，增加了对杂质元素Ti、Zr、Cu、Sn、As、Sb的限定。As described above, the heat-resistant steel for steel pipes and castings provided by the present invention can obtain steel pipes and castings with excellent performance through the preferred element components and preparation steps thereof. Compared with the existing boiler pipe material T/P92, Co element is added, the ratio of B and N is adjusted, the content of Cr, Mo and B elements is increased, and the content of Nb, N and Ni elements is reduced. The content of Si and W elements has been more strictly limited, and the limit of impurity elements Cu, Sn, As, and Sb has been increased; compared with the existing casting material ZG13Cr9Mo2Co1NiVNbNB, W element has been added, and the ratio of B and N has been adjusted. The contents of Co and B elements are increased, the contents of Mn, Mo, N and Ni elements are decreased, and the limits of impurity elements Ti, Zr, Cu, Sn, As, and Sb are increased.
本发明提供的一种钢管和铸件用耐热钢，提高了高温蠕变断裂强度和抗氧化性能，这将使得使用温度提高，从而提高发电机组的热效率，降低煤炭消耗和二氧化碳排放。该新型耐热钢用作钢管材料时材料牌号简称TB4(小口径管)/PB4(大口径管)，用于铸件材料时材料牌号简称CB4。The invention provides a heat-resistant steel for steel pipes and castings, which improves the high-temperature creep rupture strength and oxidation resistance, which will increase the operating temperature, thereby improving the thermal efficiency of the generator set and reducing coal consumption and carbon dioxide emissions. When the new heat-resistant steel is used as a steel pipe material, the material grade is abbreviated as TB4 (small-diameter pipe)/PB4 (large-diameter pipe), and the material grade is abbreviated as CB4 when used as a casting material.
本发明提供的一种钢管和铸件用耐热钢，可以被用于制备压力容器和动力机械，尤其是锅炉管道和汽轮机铸件，制备获得的锅炉管道和汽轮机铸件在650℃及650℃以下的高温环境中具有良好的高温蠕变断裂强度和抗氧化性能，可以满足工作温度为650℃及650℃以下的锅炉和汽轮机的使用要求。The heat-resistant steel for steel pipes and castings provided by the present invention can be used to prepare pressure vessels and power machinery, especially boiler pipes and steam turbine castings. It has good high temperature creep rupture strength and oxidation resistance in the environment, and can meet the requirements of boilers and steam turbines with a working temperature of 650 °C and below.
实现本发明的最佳方式Best Mode for Carrying Out the Invention
下面结合具体实施例进一步阐述本发明，应理解，这些实施例仅用于说明本发明而不用于限制本发明的保护范围。The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the protection scope of the present invention.
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。The embodiments of the present invention are described below through specific specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.
实施例1Example 1
按配比取各元素组分，如表1所示，各组分由以下质量百分比的元素组成：Take each element component according to the proportion, as shown in Table 1, each component is composed of the following elements by mass percentage:
C：0.10wt％，Si：0.30wt％，Mn：0.50wt％，Cr：9.30wt％，Co：3.00wt％，W：1.80wt％，Mo：0.65wt％，V：0.23wt％，Nb：0.05wt％，N：0.012wt％，B：0.012wt％，Ni：0.05wt％，余量为Fe和不可避免的杂质。C: 0.10wt%, Si: 0.30wt%, Mn: 0.50wt%, Cr: 9.30wt%, Co: 3.00wt%, W: 1.80wt%, Mo: 0.65wt%, V: 0.23wt%, Nb: 0.05wt%, N: 0.012wt%, B: 0.012wt%, Ni: 0.05wt%, and the balance is Fe and inevitable impurities.
如表2所示，杂质中元素的质量百分比含量为：P：0.008wt％，S：0.003wt％，Al：0.01wt％，Ti：0.003wt％，Zr：0.001wt％，Cu：0.05wt％，Sn：0.001wt％，As：0.001wt％，Sb：0.001wt％。As shown in Table 2, the mass percentage contents of the elements in the impurities are: P: 0.008wt%, S: 0.003wt%, Al: 0.01wt%, Ti: 0.003wt%, Zr: 0.001wt%, Cu: 0.05wt% , Sn: 0.001wt%, As: 0.001wt%, Sb: 0.001wt%.
其中，按Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N计，Cr当量为7.62％。B元素与N元素的质量之比为1：1。Among them, based on Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N, the Cr equivalent is 7.62%. The mass ratio of B element to N element is 1:1.
按上述各元素配比取原料混合后，进行冶炼，即依次进行合金熔炼、精炼，再模铸成管坯，将管坯进行热挤压后得到钢管，再将钢管进行正火后回火，即得钢管样品1#。其中，正火的温度为1100℃，回火包括1次，回火的温度为780℃。钢管样品1#为锅炉管。After mixing the raw materials according to the proportions of the above elements, smelting is carried out, that is, alloy smelting and refining are carried out in sequence, and then die-casting into a tube blank. That is, the steel pipe sample 1# is obtained. Among them, the normalizing temperature is 1100°C, the tempering includes one time, and the tempering temperature is 780°C. Steel tube sample 1# is a boiler tube.
实施例2Example 2
按配比取各元素组分，如表1所示，各组分由以下质量百分比的元素组成：Take each element component according to the proportion, as shown in Table 1, each component is composed of the following elements by mass percentage:
C：0.12wt％，Si：0.25wt％，Mn：0.45wt％，Cr：9.60wt％，Co：3.20wt％，W：1.75wt％，Mo：0.70wt％，V：0.20wt％，Nb：0.07wt％，N：0.009wt％，B：0.013wt％，Ni：0.10wt％，余量为Fe(铁)和不可避免的杂质。C: 0.12wt%, Si: 0.25wt%, Mn: 0.45wt%, Cr: 9.60wt%, Co: 3.20wt%, W: 1.75wt%, Mo: 0.70wt%, V: 0.20wt%, Nb: 0.07wt%, N: 0.009wt%, B: 0.013wt%, Ni: 0.10wt%, and the balance is Fe (iron) and inevitable impurities.
如表2所示，杂质中元素的质量百分比含量为：P：0.012wt％，S：0.005wt％，Al：0.01wt％，Ti：0.005wt％，Zr：0.001wt％，Cu：0.06wt％，Sn：0.001wt％，As：0.002wt％，Sb：0.0015wt％。As shown in Table 2, the mass percentage contents of the elements in the impurities are: P: 0.012wt%, S: 0.005wt%, Al: 0.01wt%, Ti: 0.005wt%, Zr: 0.001wt%, Cu: 0.06wt% , Sn: 0.001wt%, As: 0.002wt%, Sb: 0.0015wt%.
其中，按Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N计，Cr当量为6.7％。B元素与N元素的质量之比为1.4：1。按上述各元素配比取原料混合后，进行冶炼，即依次进行合金熔炼、精炼，再浇铸成铸件，将铸件进行正火后回火，即得铸件样品1*。其中，正火的温度为1140℃，回火包括2次，回火的温度为755℃。铸件样品1*为汽轮机阀壳铸件。Among them, based on Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N, the Cr equivalent is 6.7%. The mass ratio of B element to N element is 1.4:1. After mixing the raw materials according to the above-mentioned element ratios, smelting is carried out, that is, alloy smelting and refining are carried out in sequence, and then cast into castings. The castings are normalized and tempered to obtain casting sample 1*. Among them, the normalizing temperature is 1140°C, the tempering includes 2 times, and the tempering temperature is 755°C. Casting sample 1* is a steam turbine valve casing casting.
表1实施例1-2的样品中必要元素含量(wt％)Table 1 Essential element content (wt%) in the samples of Example 1-2
元素element 实施例1Example 1 实施例2Example 2
CC 0.100.10 0.120.12
SiSi 0.300.30 0.250.25
MnMn 0.500.50 0.450.45
CrCr 9.309.30 9.609.60
CoCo 3.003.00 3.203.20
WW 1.801.80 1.751.75
MoMo 0.650.65 0.700.70
VV 0.230.23 0.200.20
NbNb 0.050.05 0.070.07
NN 0.0120.012 0.0090.009
BB 0.0120.012 0.0130.013
NiNi 0.050.05 0.100.10
表2实施例1-2的样品中杂质元素含量(wt％)Table 2 Impurity element content (wt%) in the samples of Example 1-2
元素element 实施例1Example 1 实施例2Example 2
PP 0.0080.008 0.0120.012
SS 0.0030.003 0.0050.005
AlAl 0.010.01 0.010.01
TiTi 0.0030.003 0.0050.005
ZrZr 0.0010.001 0.0010.001
CuCu 0.050.05 0.060.06
SnSn 0.0010.001 0.0010.001
AsAs 0.0010.001 0.0020.002
SbSb 0.0010.001 0.00150.0015
对比例1Comparative Example 1
选择现有钢管材料T92/P92及铸件材料ZG13Cr9Mo2Co1NiVNbNB，现有钢管材料T92/P92及铸件材料ZG13Cr9Mo2Co1NiVNbNB与本发明耐热钢中所含元素组成见表3。Select the existing steel pipe material T92/P92 and the casting material ZG13Cr9Mo2Co1NiVNbNB, the existing steel pipe material T92/P92 and the casting material ZG13Cr9Mo2Co1NiVNbNB and the elements contained in the heat-resistant steel of the present invention are shown in Table 3.
表3组成元素对比(wt.％)Table 3 Comparison of constituent elements (wt.%)
Figure PCTCN2021072875-appb-000001
Figure PCTCN2021072875-appb-000001
Figure PCTCN2021072875-appb-000002
Figure PCTCN2021072875-appb-000002
测试例1Test Example 1
根据标准ASTM A213/A335和JB/T 11018，将现有钢管材料T92/P92及铸件材料ZG13Cr9Mo2Co1NiVNbNB的力学性能指标列出，具体数据见表4。表4中Rp0.2为屈服强度，Rm为抗拉强度，A为延伸率，Z为断面收缩率，KV2为冲击吸收功。同时，将实施例1获得的钢管样品1#和实施例2获得的铸件样品1*，按照国家标准GB/T228.1进行了室温拉伸试验，按照国家标准GB/T229进行了室温冲击试验，测试结果见表4。According to the standard ASTM A213/A335 and JB/T 11018, the mechanical properties of the existing steel pipe material T92/P92 and the casting material ZG13Cr9Mo2Co1NiVNbNB are listed. The specific data are shown in Table 4. In Table 4, Rp0.2 is the yield strength, Rm is the tensile strength, A is the elongation, Z is the area shrinkage, and KV2 is the impact absorption energy. At the same time, the steel pipe sample 1# obtained in Example 1 and the casting sample 1* obtained in Example 2 were subjected to a room temperature tensile test according to the national standard GB/T228.1, and a room temperature impact test according to the national standard GB/T229. The test results are shown in Table 4.
由表4所示，现有钢管材料T92/P92与实施例1获得的钢管样品1#比较可知，钢管样品1#获得的室温力学性能满足T92/P92的指标要求。As shown in Table 4, the comparison between the existing steel pipe material T92/P92 and the steel pipe sample 1# obtained in Example 1 shows that the room temperature mechanical properties obtained by the steel pipe sample 1# meet the index requirements of T92/P92.
由表4所示，现有铸件材料ZG13Cr9Mo2Co1NiVNbNB与实施例2获得 的铸件样品1*比较可知，铸件样品1*获得的室温力学性能满足ZG13Cr9Mo2Co1NiVNbNB的指标要求。As shown in Table 4, the comparison between the existing casting material ZG13Cr9Mo2Co1NiVNbNB and the casting sample 1* obtained in Example 2 shows that the room temperature mechanical properties obtained by the casting sample 1* meet the index requirements of ZG13Cr9Mo2Co1NiVNbNB.
测试例2Test case 2
将实施例1获得的钢管样品1#和实施例2获得的铸件样品1*，按照国家标准GB/T 2039标准进行了蠕变断裂强度试验，然后按照国家标准GB/T 2039中规定的外推方法推导出650℃/10万小时条件下的蠕变断裂强度极限R u100000h/650℃，并分别与T92/P92及ZG13Cr9Mo2Co1NiVNbNB在650℃/10万小时条件下的蠕变断裂强度进行比较，结果如表4所示。 The steel pipe sample 1# obtained in Example 1 and the casting sample 1* obtained in Example 2 were tested for creep rupture strength according to the national standard GB/T 2039, and then extrapolated according to the national standard GB/T 2039. The method deduces the creep rupture strength limit R u100000h/650℃ at 650℃/100,000 hours, and compares it with the creep rupture strength of T92/P92 and ZG13Cr9Mo2Co1NiVNbNB at 650℃/100,000 hours respectively. The results are as follows shown in Table 4.
由表4可知，实施例1获得的钢管样品1#的蠕变断裂强度外推值，相比现有钢管材料T92/P92提高了50％以上，强化效果明显，可满足650℃下锅炉管道的使用要求。It can be seen from Table 4 that the extrapolated value of creep rupture strength of steel pipe sample 1# obtained in Example 1 is more than 50% higher than that of the existing steel pipe material T92/P92, and the strengthening effect is obvious, which can meet the requirements of boiler pipes at 650 °C. Requirements.
由表4可知，实施例2获得的铸件样品1*的蠕变断裂强度外推值，相比现有铸件材料ZG13Cr9Mo2Co1NiVNbNB提高了40％以上，强化效果明显，可满足650℃下汽轮机铸件的使用要求。It can be seen from Table 4 that the extrapolated value of creep rupture strength of the casting sample 1* obtained in Example 2 is increased by more than 40% compared with the existing casting material ZG13Cr9Mo2Co1NiVNbNB, and the strengthening effect is obvious, which can meet the use requirements of steam turbine castings at 650 °C. .
表4力学性能和蠕变断裂强度对比Table 4 Comparison of mechanical properties and creep rupture strength
Figure PCTCN2021072875-appb-000003
Figure PCTCN2021072875-appb-000003
测试例3Test case 3
对实施例1获得的钢管样品1#和实施例2获得的铸件样品1*，以及现有钢管材料T92/P92及铸件材料ZG13Cr9Mo2Co1NiVNbNB，分别进行620℃和650℃下的氧化增重试验。将试样置于620℃/650℃和27MPa流动的水蒸 汽环境中，时间最长至2000h，测试这个时间段内各试样增重变化，氧化增重越小说明材料抗氧化性越好。The steel pipe sample 1# obtained in Example 1 and the casting sample 1* obtained in Example 2, as well as the existing steel pipe material T92/P92 and casting material ZG13Cr9Mo2Co1NiVNbNB, were subjected to oxidation weight gain tests at 620°C and 650°C, respectively. The samples were placed in a water vapor environment of 620°C/650°C and 27MPa flowing for a maximum time of 2000h, and the weight gain of each sample during this period was tested. The smaller the oxidation weight gain, the better the oxidation resistance of the material.
试验结果显示，同一温度下，钢管样品1#的抗氧化性明显好于T92/P92，铸件样品1*的抗氧化性明显好于ZG13Cr9Mo2Co1NiVNbNB。The test results show that at the same temperature, the oxidation resistance of steel pipe sample 1# is significantly better than that of T92/P92, and the oxidation resistance of casting sample 1* is significantly better than that of ZG13Cr9Mo2Co1NiVNbNB.
在不同温度下，如650℃下，钢管样品1#的氧化增重与T92/P92在620℃下的氧化增重相近，铸件样品1*的氧化增重与ZG13Cr9Mo2Co1NiVNbNB在620℃下的氧化增重相近。表明本发明耐热钢制备的钢管和铸件，在不采用表面防护涂层来抗氧化的前提下，基本可以满足650℃工作条件下长期使用的需要。At different temperatures, such as 650℃, the oxidation weight gain of steel pipe sample 1# is similar to that of T92/P92 at 620℃, and the oxidation weight gain of casting sample 1* is similar to that of ZG13Cr9Mo2Co1NiVNbNB at 620℃ similar. It shows that the steel pipes and castings prepared from the heat-resistant steel of the present invention can basically meet the needs of long-term use under the working condition of 650°C without using a surface protective coating to resist oxidation.
所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。Therefore, the present invention effectively overcomes various shortcomings in the prior art and has high industrial application value.
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。The above-mentioned embodiments merely illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can make modifications or changes to the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed in the present invention should still be covered by the claims of the present invention.

Claims (12)

  1. 一种耐热钢，由以下质量百分比的元素组成：A heat-resistant steel consisting of the following elements by mass:
    C：0.08～0.14wt％，Si：0.20～0.40wt％，Mn：0.30～0.60wt％，Cr：9.00～10.00wt％，Co：2.80～3.30wt％，W：1.65～1.90wt％，Mo：0.55～0.80wt％，V：0.15～0.25wt％，Nb：0.03～0.08wt％，N：0.006～0.015wt％，B：0.009～0.015wt％，Ni：≤0.20wt％，余量为Fe和不可避免的杂质。C: 0.08-0.14wt%, Si: 0.20-0.40wt%, Mn: 0.30-0.60wt%, Cr: 9.00-10.00wt%, Co: 2.80-3.30wt%, W: 1.65-1.90wt%, Mo: 0.55～0.80wt%, V: 0.15～0.25wt%, Nb: 0.03～0.08wt%, N: 0.006～0.015wt%, B: 0.009～0.015wt%, Ni: ≤0.20wt%, the balance is Fe and inevitable impurities.
  2. 根据权利要求1所述的耐热钢，其特征在于，所述杂质选自P、S、Al、Ti、Zr、Cu、Sn、As、Sb中的一种或多种元素；所述杂质中元素的质量百分比含量符合以下要求：P：≤0.020wt％，S：≤0.010wt％，Al：≤0.02wt％，Ti：≤0.02wt％，Zr：≤0.02wt％，Cu：≤0.15wt％，Sn：≤0.02wt％，As：≤0.02wt％，Sb：≤0.005wt％。The heat-resistant steel according to claim 1, wherein the impurities are selected from one or more elements selected from the group consisting of P, S, Al, Ti, Zr, Cu, Sn, As, and Sb; The mass percentage content of the elements meets the following requirements: P: ≤0.020wt%, S: ≤0.010wt%, Al: ≤0.02wt%, Ti: ≤0.02wt%, Zr: ≤0.02wt%, Cu: ≤0.15wt% , Sn:≤0.02wt%, As:≤0.02wt%, Sb:≤0.005wt%.
  3. 根据权利要求1所述的耐热钢，其特征在于，所述耐热钢中，Cr当量按Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N计应≤8.5％，且所述B元素与N元素的质量之比为0.65～2.40：1。The heat-resistant steel according to claim 1, wherein, in the heat-resistant steel, the Cr equivalent is calculated as Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N≤ 8.5%, and the mass ratio of the B element to the N element is 0.65-2.40:1.
  4. 根据权利要求1所述的耐热钢，其特征在于，所述耐热钢由以下质量百分比的元素组成：The heat-resistant steel according to claim 1, wherein the heat-resistant steel is composed of the following elements by mass percentage:
    C：0.08～0.13wt％，Si：0.20～0.30wt％，Mn：0.40～0.50wt％，Cr：9.00～9.60wt％，Co：2.90～3.20wt％，W：1.70～1.85wt％，Mo：0.60～0.75wt％，V：0.18～0.25wt％，Nb：0.04～0.07wt％，N：0.007～0.014wt％，B：0.010～0.015wt％，Ni：≤0.10wt％，余量为Fe和不可避免的杂质。C: 0.08-0.13wt%, Si: 0.20-0.30wt%, Mn: 0.40-0.50wt%, Cr: 9.00-9.60wt%, Co: 2.90-3.20wt%, W: 1.70-1.85wt%, Mo: 0.60～0.75wt%, V: 0.18～0.25wt%, Nb: 0.04～0.07wt%, N: 0.007～0.014wt%, B: 0.010～0.015wt%, Ni: ≤0.10wt%, the balance is Fe and inevitable impurities.
  5. 根据权利要求4所述的耐热钢，其特征在于，所述杂质中元素的质量百分比含量符合以下要求：P：≤0.020wt％，S：≤0.005wt％，Al：≤0.01wt％，Ti：≤0.01wt％，Zr：≤0.01wt％，Cu：≤0.10wt％，Sn：≤0.01wt％，As：≤0.01wt％，Sb：≤0.003wt％。The heat-resistant steel according to claim 4, wherein the mass percentage content of the elements in the impurities meets the following requirements: P: ≤0.020wt%, S: ≤0.005wt%, Al: ≤0.01wt%, Ti :≤0.01wt%, Zr:≤0.01wt%, Cu:≤0.10wt%, Sn:≤0.01wt%, As:≤0.01wt%, Sb:≤0.003wt%.
  6. 根据权利要求4所述的耐热钢，其特征在于，所述耐热钢中，Cr当量按Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N计应≤8.0％，且所述B元素与N元素的质量之比为0.75～2.10：1。The heat-resistant steel according to claim 4, characterized in that, in the heat-resistant steel, the Cr equivalent is calculated as Cr+6Si+4Mo+1.5W+11V+5Nb-40C-2Mn-4Ni-2Co-30N≤ 8.0%, and the mass ratio of the B element to the N element is 0.75 to 2.10:1.
  7. 一种钢管的制备方法，将根据权利要求1-6任一所述的耐热钢按元素配 比取原料混合后进行冶炼，先采用连铸、模铸、热轧或热锻中的任一种制成管坯，然后将管坯采用热轧、热挤压、热扩、冷拔、冷轧或锻造镗孔中的任一种制成钢管，再将钢管进行正火或淬火后回火，即得。A preparation method of a steel pipe, the heat-resistant steel according to any one of claims 1-6 is mixed with raw materials according to the element ratio, and then smelted, and any one of continuous casting, die casting, hot rolling or hot forging is first used. It is made into a tube blank, and then the tube blank is made into a steel pipe by any one of hot rolling, hot extrusion, hot expansion, cold drawing, cold rolling or forging and boring, and then the steel pipe is normalized or quenched and then tempered. , that is.
  8. 根据权利要求7所述的钢管的制备方法，其特征在于，所述正火或淬火的温度为1070～1160℃；所述回火包括至少一次，所述回火的温度为740～790℃。The method for preparing a steel pipe according to claim 7, wherein the normalizing or quenching temperature is 1070-1160°C; the tempering includes at least one time, and the tempering temperature is 740-790°C.
  9. 一种铸件的制备方法，将根据权利要求1-6任一所述的耐热钢按元素配比取原料混合后进行冶炼、浇铸后得到铸件，再将铸件进行正火或淬火后回火，即得。A method for preparing a casting, the heat-resistant steel according to any one of claims 1-6 is mixed with raw materials according to the element ratio, smelted and casted to obtain a casting, and then the casting is normalized or quenched and then tempered, That's it.
  10. 根据权利要求9所述的铸件的制备方法，其特征在于，所述正火或淬火的温度为1070～1160℃；所述回火包括至少一次，所述回火的温度为730～780℃。The method for manufacturing a casting according to claim 9, wherein the normalizing or quenching temperature is 1070-1160°C; the tempering includes at least one time, and the tempering temperature is 730-780°C.
  11. 根据权利要求1-6任一所述的耐热钢、或根据权利要求7-8任一所述的钢管在压力容器中的用途。Use of the heat-resistant steel according to any one of claims 1-6 or the steel pipe according to any one of claims 7-8 in a pressure vessel.
  12. 根据权利要求1-6任一所述的耐热钢、或根据权利要求9-10任一所述的铸件在动力机械中的用途。Use of the heat-resistant steel according to any one of claims 1-6 or the casting according to any one of claims 9-10 in power machinery.
PCT/CN2021/072875 2020-07-30 2021-01-20 Heat-resistant steel for steel pipe and casting WO2022021816A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2022557133A JP7428822B2 (en) 2020-07-30 2021-01-20 Heat-resistant steel for steel pipes and castings
DE112021001054.9T DE112021001054T5 (en) 2020-07-30 2021-01-20 Heat-resistant steel for steel pipes and castings

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010749897.3A CN114058939A (en) 2020-07-30 2020-07-30 Steel pipe and heat-resistant steel for casting
CN202010749897.3 2020-07-30

Publications (1)

Publication Number Publication Date
WO2022021816A1 true WO2022021816A1 (en) 2022-02-03

Family

ID=80037092

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/072875 WO2022021816A1 (en) 2020-07-30 2021-01-20 Heat-resistant steel for steel pipe and casting

Country Status (4)

Country Link
JP (1) JP7428822B2 (en)
CN (1) CN114058939A (en)
DE (1) DE112021001054T5 (en)
WO (1) WO2022021816A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114836689A (en) * 2022-04-25 2022-08-02 宁国东方碾磨材料股份有限公司 High-chromium wear-resistant steel ball and preparation method thereof
CN114959431A (en) * 2022-06-02 2022-08-30 邯郸慧桥复合材料科技有限公司 Large-scale semi-autogenous mill lining plate and manufacturing method thereof
CN116676470A (en) * 2023-08-03 2023-09-01 成都先进金属材料产业技术研究院股份有限公司 Heat-resistant steel seamless steel pipe and heat treatment method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0828010A2 (en) * 1996-09-10 1998-03-11 Mitsubishi Heavy Industries, Ltd. High strength and high-toughness heat-resistant cast steel
EP1001044A2 (en) * 1997-07-16 2000-05-17 Mitsubishi Heavy Industries, Ltd. Heat-resisting cast steel
JP2009293063A (en) * 2008-06-03 2009-12-17 Sumitomo Metal Ind Ltd METHOD FOR MANUFACTURING HIGH-Cr HEAT-RESISTANT FERRITIC STEEL MATERIAL
CN102560275A (en) * 2010-12-28 2012-07-11 株式会社东芝 Heat resistant cast steel, manufacturing method thereof, cast parts of steam turbine, and manufacturing method of cast parts of steam turbine
CN110106436A (en) * 2019-03-18 2019-08-09 东北大学 Corrosion-resistant boiler steel of a kind of resistance to steam of high temperature resistant and preparation method thereof
CN111139409A (en) * 2020-01-21 2020-05-12 上海电气电站设备有限公司 Heat-resistant cast steel and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5759304B2 (en) 2011-08-17 2015-08-05 株式会社日本製鋼所 Multi-layer overlay weld of high Cr steel turbine rotor by TIG welding or submerged arc welding and method for manufacturing the same
CN104726779B (en) 2015-04-21 2016-09-14 武汉科技大学 A kind of high Cr jessop and preparation method thereof
JP6575392B2 (en) 2015-05-19 2019-09-18 日本製鉄株式会社 High Cr ferritic heat resistant steel
CN105695881B (en) * 2016-04-18 2017-06-16 东北大学 A kind of 650 DEG C of ultra supercritical casting heat resisting steel

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0828010A2 (en) * 1996-09-10 1998-03-11 Mitsubishi Heavy Industries, Ltd. High strength and high-toughness heat-resistant cast steel
EP1001044A2 (en) * 1997-07-16 2000-05-17 Mitsubishi Heavy Industries, Ltd. Heat-resisting cast steel
JP2009293063A (en) * 2008-06-03 2009-12-17 Sumitomo Metal Ind Ltd METHOD FOR MANUFACTURING HIGH-Cr HEAT-RESISTANT FERRITIC STEEL MATERIAL
CN102560275A (en) * 2010-12-28 2012-07-11 株式会社东芝 Heat resistant cast steel, manufacturing method thereof, cast parts of steam turbine, and manufacturing method of cast parts of steam turbine
CN110106436A (en) * 2019-03-18 2019-08-09 东北大学 Corrosion-resistant boiler steel of a kind of resistance to steam of high temperature resistant and preparation method thereof
CN111139409A (en) * 2020-01-21 2020-05-12 上海电气电站设备有限公司 Heat-resistant cast steel and preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114836689A (en) * 2022-04-25 2022-08-02 宁国东方碾磨材料股份有限公司 High-chromium wear-resistant steel ball and preparation method thereof
CN114959431A (en) * 2022-06-02 2022-08-30 邯郸慧桥复合材料科技有限公司 Large-scale semi-autogenous mill lining plate and manufacturing method thereof
CN114959431B (en) * 2022-06-02 2023-02-28 邯郸慧桥复合材料科技有限公司 Large-scale semi-autogenous mill lining plate and manufacturing method thereof
CN116676470A (en) * 2023-08-03 2023-09-01 成都先进金属材料产业技术研究院股份有限公司 Heat-resistant steel seamless steel pipe and heat treatment method thereof
CN116676470B (en) * 2023-08-03 2023-12-01 成都先进金属材料产业技术研究院股份有限公司 Heat-resistant steel seamless steel pipe and heat treatment method thereof

Also Published As

Publication number Publication date
CN114058939A (en) 2022-02-18
JP7428822B2 (en) 2024-02-06
JP2023530808A (en) 2023-07-20
DE112021001054T5 (en) 2023-02-02

Similar Documents

Publication Publication Date Title
JP4561834B2 (en) Low alloy steel
WO2022021816A1 (en) Heat-resistant steel for steel pipe and casting
KR20150023935A (en) Austenitic steel alloy having excellent creep strength and resistance to oxidation and corrosion at elevated use temperatures
JPH0621323B2 (en) High strength and high chrome steel with excellent corrosion resistance and oxidation resistance
WO2021147810A1 (en) Heat resistant cast steel, preparation method therefor, and use thereof
JP2001073066A (en) LOW Cr FERRITIC HEAT RESISTANT STEEL EXCELLENT IN HIGH TEMPERATURE STRENGTH AND TOUGHNESS AND ITS PRODUCTION
JP5137934B2 (en) Ferritic heat resistant steel
JP3982069B2 (en) High Cr ferritic heat resistant steel
CN114622133B (en) Heat-resistant steel for ultra-supercritical steam turbine rotor forging and preparation method thereof
JPH11209851A (en) Gas turbine disk material
JPS616256A (en) 12% cr heat resisting steel
JP5793556B2 (en) 862 MPa class low C high Cr steel pipe having high corrosion resistance and manufacturing method thereof
JP3531228B2 (en) High Cr ferritic heat resistant steel
JPH1161342A (en) High chromium ferritic steel
JPS6013056A (en) Heat resistant martensitic steel
JP3662151B2 (en) Heat-resistant cast steel and heat treatment method thereof
JP3775371B2 (en) Low alloy steel
JPH11350076A (en) Precipitation strengthening type ferritic heat resistant steel
JP4284010B2 (en) Heat resistant steel
JP2001152293A (en) HIGH Cr FERRITIC HEAT RESISTING STEEL
JPH07166303A (en) High strength martensitic stainless steel excellent in stress corrosion cracking resistance and production thereof
JP3254098B2 (en) Low alloy steel for rotating body
KR100290653B1 (en) 15Cr 26Ni 1.25Mo Heat Resistant Steel for 650 ℃ Class Steam Turbine Rotor
JP6289873B2 (en) Precipitation strengthened ferritic heat resistant steel, turbine high temperature member using the heat resistant steel, and turbine using the turbine high temperature member
JP3367216B2 (en) High Cr ferritic heat resistant steel

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21848145

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 17909826

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2022557133

Country of ref document: JP

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 21848145

Country of ref document: EP

Kind code of ref document: A1