CN115094303A - Steel plate for advanced nuclear power unit superheater and manufacturing method thereof - Google Patents

Steel plate for advanced nuclear power unit superheater and manufacturing method thereof Download PDF

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CN115094303A
CN115094303A CN202210487754.9A CN202210487754A CN115094303A CN 115094303 A CN115094303 A CN 115094303A CN 202210487754 A CN202210487754 A CN 202210487754A CN 115094303 A CN115094303 A CN 115094303A
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steel plate
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CN115094303B (en
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王储
段江涛
王勇
艾芳芳
李侠
胡昕明
严平沅
邢梦楠
姚震
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Angang Steel Co Ltd
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • 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
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
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    • 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
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
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    • 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
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    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • 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
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    • 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
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    • 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
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
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  • Physics & Mathematics (AREA)
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  • Heat Treatment Of Steel (AREA)

Abstract

The invention provides a steel plate for an advanced nuclear power unit superheater and a manufacturing method thereof, wherein the steel plate comprises the following components in percentage by weight: 0.13 to 0.16 percent of C, 0.10 to 0.25 percent of Si, 0.25 to 0.50 percent of Mn, less than or equal to 0.006 percent of P, less than or equal to 0.002 percent of S, 2.35 to 2.55 percent of Cr, 1.30 to 1.60 percent of Mo, 0.80 to 1.20 percent of Ni, 0.04 to 0.08 percent of Nb, 0.05 to 0.10 percent of V, 0.03 to 0.06 percent of Ti, less than or equal to 0.02 percent of Alt, 0.001 to 0.004 percent of Ca0.01 to 0.03 percent of N, less than or equal to 0.001 percent of Sn, less than or equal to 0.0001 percent of H, less than or equal to 0.0020 percent of O, the balance of Fe and inevitable impurities, and a high-temperature tempering embrittlement resistance coefficient J of less than or equal to 50; the manufacturing method comprises smelting, continuous casting, electroslag remelting, heating, controlled rolling and controlled cooling and heat treatment; the steel plate has excellent high-temperature strength at 550 ℃, high-temperature fatigue performance and low-temperature toughness after postweld heat treatment at 700 ℃ for 16h, and meets the requirements of manufacturing and using a four-generation nuclear power station superheater.

Description

Steel plate for advanced nuclear power unit superheater and manufacturing method thereof
Technical Field
The invention belongs to the field of metal materials, and particularly relates to a steel plate for an advanced nuclear power unit superheater and a manufacturing method thereof.
Background
Nuclear power, one of the world's clean and efficient energy sources, has been utilized by mankind for more than 70 years. Since the twenty-first century, the contradiction between the frequent activities of human beings and the development of global economy and the shortage of energy and extreme climate has been increasingly highlighted, and the advantages of nuclear energy have been more prominent in the context of such global integration. Therefore, the peaceful development of more advanced nuclear energy is still the trend of the times. At present, after the development of a first-generation experimental prototype reactor, a second-generation pressurized water reactor and a third-generation advanced light water reactor, a fourth-generation advanced nuclear technology comprising a sodium liquid cooling fast reactor, a gas cooling fast reactor, a lead liquid cooling fast reactor, an ultra-high temperature gas cooled reactor, a molten salt reactor, a supercritical water cooled reactor and the like is proposed by global nuclear energy experts and becomes the development direction of future nuclear power technology.
The fourth generation nuclear energy technology has the main characteristics of better safety, better economy, less nuclear waste and effective prevention of nuclear diffusion. Therefore, very high requirements are put forward on nuclear technology and nuclear equipment, for example, the four-generation nuclear power efficiency is higher, the outlet temperature of the superheater reaches the high temperature of 550 ℃, and very high technical index requirements are put forward on the superheater material at the temperature.
The main problems of the previous three-generation nuclear power technology are low nuclear fuel cyclic utilization rate, large nuclear waste generation amount, poor safety and the like. The fourth generation nuclear power concept is put forward formally based on the reasons, and in order to improve the nuclear fuel recycling rate and minimize nuclear waste, a new nuclear power technology can be used for producing process heat and steam for other commercial purposes such as hydrogen production, oil refining and the like. Therefore, the temperature of the reactor core of the fourth-generation nuclear power reaches 550 ℃ which is far higher than the outlet temperature of 350 ℃ of the third-generation nuclear power, very high requirements on the internal purity, the difference of each direction, the high-temperature strength and toughness after postweld heat treatment, the fatigue fracture resistance and the like of the corresponding steam superheater and the manufacturing steel thereof are provided, and the materials required by the strict technical indexes are not related inventions and reports temporarily.
Disclosure of Invention
The invention aims to overcome the problems and the defects and provide the steel plate for the superheater of the advanced nuclear power unit, which has excellent high-temperature strength, high-temperature fatigue performance and low-temperature toughness at 550 ℃ after postweld heat treatment of 700 ℃ for 16h and high purity and homogenization degree, and meets the manufacturing and using requirements of the superheater of the fourth-generation nuclear power station, and the manufacturing method thereof.
The purpose of the invention is realized as follows:
the invention aims to develop high-performance steel meeting the requirements of a fourth-generation nuclear power station superheater by adopting brand-new chemical component design and a proper production process, adding Cr, Mo, Ni, Nb, V, Ti and N alloy elements in a compounding manner on the basis of medium-low C, Si and Mn components, strictly controlling the content of harmful element P, S, Sn and gas O, H and matching with a unique smelting, rolling and heat treatment production process.
The steel plate for the advanced nuclear power unit superheater comprises the following components in percentage by weight: 0.13 to 0.16 percent of C,0.10 to 0.25 percent of Si, 0.25 to 0.50 percent of Mn, less than or equal to 0.006 percent of P, less than or equal to 0.002 percent of S, 2.35 to 2.55 percent of Cr, 1.30 to 1.60 percent of Mo, 0.80 to 1.20 percent of Ni, 0.04 to 0.08 percent of Nb, 0.05 to 0.10 percent of V, 0.03 to 0.06 percent of Ti, less than or equal to 0.02 percent of Alt, 0.001 to 0.004 percent of Ca, 0.01 to 0.03 percent of N, less than or equal to 0.001 percent of Sn, less than or equal to 0.0001 percent of H, less than or equal to 0.0020 percent of O, the balance of Fe and inevitable impurities, and the high-temperature embrittlement resistance coefficient J (Si + Mn) × (P + Sn) × 10 ≦ 10 4 ≤50。
The Mo/Si content in the steel plate is 6.0-14; the ratio of (Cr + Mn)/Mo is 1.7-2.2.
The thickness of the steel plate is 50-80 mm; the microstructure of the steel plate is a bainite and martensite complex phase structure, the volume percentage of the bainite is 20-30%, and the volume percentage of the martensite is 70-80%.
The mechanical property of the steel plate is that R is more than or equal to 421MPa el ≤436MPa、585MPa≤R m Not more than 599 Mpa; the (A + B + C + D) fine non-metallic inclusion is less than or equal to 1.0 grade, the (A + B + C + D) coarse non-metallic inclusion is 0 grade, and the R of the steel plate is less than or equal to 420MPa at 550 DEG C m Less than or equal to 435 MPa; 374MPa or less at 550 ℃ and R at 374MPa or more of steel plate after 700 ℃ multiplied by 16h post-weld heat treatment state m Less than or equal to 388MPa, more than or equal to 1000 times of circulation when R is-1 at 550 ℃, more than or equal to 120 ten thousand times of circulation when R is 0 at 550 ℃, and more than or equal to 120 ten thousand times of circulation when KV is at-20 DEG 2 ≥300J、HBW≤185。
The invention has the following design reasons:
c the C in the main solid solution state and the C in the compound state in the invention ensure the high-temperature strength tensile strength of the heat treatment state and the post-welding heat treatment state of the steel, and are also main elements for improving the fatigue strength, but the excessive carbon content is unfavorable for the toughness and the welding performance of the steel, so the C content range is set to be 0.13-0.16 percent.
Si is used as a reducing agent and a deoxidizing agent in the invention, and the Si forms a layer of compact and oxidation-resistant SiO on the surface at high temperature 2 And (5) protecting the film. In addition, Si and Mo act together to form MoSi 2 The intermetallic compound has the characteristic that the atom combination in the crystal structure of the intermetallic compound presents the coexistence of a metal bond and a covalent bond and has excellent high-temperature oxidation resistance, so the Mo/Si ratio of the invention is limited to 6.0-14, and certain formation is ensuredAmount of MoSi 2 And (5) structure. However, in the tempering embrittlement temperature range of 350-550 ℃, the too high silicon content can cause the tempering embrittlement sensitivity of the steel to be increased, so the invention is not suitable for adding too much silicon element, and the Si content range is set to be 0.10-0.25%.
In the invention, because the addition amount of deoxidizing agents such as Si, Alt and the like is small, the addition of Mn compensates for the insufficient deoxidizing effect, and in addition, Mn is used as an alloy element with strong solid solution strengthening capability to improve the matrix strength, but Mn is a sensitive element for improving the tempering brittleness, and the Mn content is strictly controlled, so the Mn content range is set to be 0.25-0.50 percent.
S, P As a harmful element in steel, the comprehensive indexes such as purity, J coefficient and fatigue property of steel must be strictly controlled, so it is limited to S less than 0.002% and P less than 0.006%.
Cr as a strong carbide forming element which forms stable M in combination with Fe, Mn and Mo in steel 23 C 6 The alloy carbide with the structure ensures the high-temperature performance of the long-term post-welding heat treatment state, and simultaneously plays the high-temperature oxidation resistance of Cr, and the Cr content range is set to be 2.35-2.55 percent.
Mo improves the hardenability of the steel and ensures the matrix strength of the steel, and meanwhile, Mo is a strong carbide forming element and forms stable Mo with carbon element 2 In addition, the steel is added with more Cr elements and certain Mn elements, which are easy to generate the co-segregation phenomenon with impurity elements such as P, Sn and the like at the grain boundary, so that the high-temperature tempering embrittlement is caused, and the high-temperature performance of the steel is influenced. The action of Mo is opposite to that of P, and P is promoted to precipitate in the crystal to prevent grain boundary segregation, so that the (Cr + Mn)/Mo is limited to be 1.7-2.2, the structural and performance stability of the superheater steel at the working temperature of 550 ℃ is ensured, and the content range of Mo is set to be 1.30-1.60%.
Ni in the invention, Ni element mainly improves the ductility and toughness of steel, but too high Ni content can reduce the radiation resistance of the material, so the invention sets the Ni content range at 0.80-1.20%.
Nb plays a role in refining grains in the invention, and the toughness of the steel is improved through grain refinement. Therefore, the Nb content is limited to 0.04% to 0.08%.
V is added in a large amount in the invention, and one of the main functions is that the carbon and nitrogen compound formed with C, N element in the long-time high-temperature postweld tempering treatment process is very stable, so that the high-temperature strength of the high-temperature postweld heat treatment state is ensured. In addition, the addition of the V alloy effectively inhibits the segregation of Cr and Mn elements induced by irradiation in grain boundaries, so that the content of V is limited to 0.05-0.10%.
Ti is one of the strong ferrite-forming elements and strongly increases A of the steel 1 And A 3 And (3) temperature. Titanium can improve the plasticity and toughness of steel. The titanium fixes carbon and nitrogen and forms carbon and titanium nitride, so that the strength of the steel is improved. After normalizing heat treatment, the crystal grains are refined, and carbide is precipitated to obviously improve the plasticity and impact toughness of the steel, so that the content of Ti is limited to 0.03-0.06%.
Sn is a residual element in steel, not only influences the purity of the steel, but also is an important element influencing the J coefficient of the temper brittleness and must be strictly controlled, so that the content of Sn is limited to be less than or equal to 0.001 percent.
The Alt is embodied as participating or adding a small amount of Alt element in the invention, plays the role of a deoxidizer, and the non-addition or small amount of Alt mainly ensures the purity of steel and prevents the non-metallic oxide of the generated aluminum from influencing the fatigue performance, so the content of Alt is limited to be less than or equal to 0.02 percent.
Ca the inclusions of the invention are spheroidized by Ca, and the MnS inclusions are changed into CaS or composite inclusions containing CaS, so that Al 2 O 3 The inclusions are spherical, are distributed in a dispersion manner, basically do not deform at the rolling temperature of the steel, and are still spherical after rolling. Therefore, the Ca treatment can reduce the hydrogen induced cracking sensitivity of the steel. However, since Ca is added excessively, the size of formed Ca (O, S) is excessively large, the brittleness is increased, the Ca can be used as a fracture crack starting point, the low-temperature toughness, the extensibility and the weldability of the steel are reduced, and the purity of the steel is reduced, the content range of Ca is set to be 0.001-0.004%.
N forms nitride with elements such as Nb, V and the like, precipitates in the grain boundary, pins the grain boundary refined grains and plays a role in improving the high-temperature strength of the grain boundary, so that the content of N is limited to 0.01-0.03 percent.
H. O as a harmful gas can cause a plurality of defects, such as H causes the defects of white spots or hydrogen embrittlement and the like in steel, and the service life of the material and the equipment safety are seriously influenced; o, Al and Si form brittle non-metallic oxides which affect the purity and fatigue limit performance of steel and must be strictly controlled, so that the content of O is limited to be less than or equal to 0.0020 percent and the content of H is limited to be less than or equal to 0.0001 percent.
The second technical scheme of the invention provides a method for manufacturing the steel plate for the advanced nuclear power unit superheater, which comprises the following steps: smelting, continuous casting, electroslag remelting, heating, rolling and cooling control and heat treatment;
(1) smelting:
smelting molten steel in a converter, preferably adopting high-quality scrap steel and molten iron as raw materials, and controlling the content of the molten iron to be 70-80%; simultaneously, in order to effectively reduce the content of harmful elements P, a converter is adopted for separate smelting for dephosphorization and decarburization, wherein dephosphorization oxygen blowing is controlled to be 7-10 min, and decarburization oxygen blowing is controlled to be 8-12 min;
carrying out deep desulfurization treatment in an LF refining furnace, and simultaneously feeding CaSi wires into steel for calcium treatment, wherein the wire feeding speed is 200-350 m/min, and the part below a slag layer at the wire feeding depth is 1.0-2.0 m, the treatment changes the form of non-metallic inclusions to form fine CaS or calcium aluminate spherical inclusion particles, so that the steel quality is purified while the steel billet equiaxial rate is increased, the purity is improved, the low-temperature toughness and the high-temperature fatigue performance of the steel are improved, the thickness of the slag layer is 60-90 mm, and the inclusions are ensured to float sufficiently;
degassing is finished in an RH furnace, the net cycle time is 10-15 min, and the sedation time before casting is 3-5 min.
(2) Continuous casting: and (3) casting by adopting a continuous casting machine after vacuum breaking, wherein the superheat degree is 20-30 ℃, the casting process needs to be stable and constant, the casting blank is inserted into a stack for slow cooling, the stack slow cooling time is 24-48 h, and unstacking is carried out at the temperature below 400 ℃, so that cracks in the casting blank caused by quenching are prevented.
(3) Electroslag remelting: in order to further improve the purity of steel, homogenize cast structure and reduce non-metallic inclusions, the addition of the electroslag remelting process is important for high-temperature fatigue performance and low-temperature toughness. According to the invention, an electroslag steel ingot with the thickness specification of 400-500 mm is adopted to roll finished steel plates with the specification of 80mm or below, the stacking and slow cooling time is 42-72 h after the electroslag ingot is demoulded, and unstacking and air cooling are carried out at the temperature below 400 ℃.
(4) Heating: by controlling the heating process of the steel billet, the alloy elements are ensured to be fully dissolved in a solid state, the growth of original austenite grains is effectively inhibited, the heating temperature of the electroslag ingot is controlled to 1180-1250 ℃, the heating time is 6-8 hours, and the soaking time is 0.5-1.0 hour.
(5) Controlled rolling and controlled cooling: the recrystallization controlled rolling starting temperature is 1050-1150 ℃, the single-pass deformation rate of a recrystallization zone is 10-15%, the reduction rate of each pass of the first three passes is 12-15%, the total deformation rate is more than or equal to 50%, and the thickness of the intermediate blank is 3.0-4.5 times that of the finished steel plate; the initial rolling temperature of non-recrystallization is 850-880 ℃, the final rolling temperature of non-recrystallization is 810-840 ℃, the rolling time of a non-recrystallization area is not less than 6 times, and the cumulative deformation rate is not less than 67%. And (3) performing ACC controlled cooling after rolling, wherein the starting cooling temperature is 770-800 ℃, the red returning temperature is 350-450 ℃, and the cooling speed is 20-25 ℃/s. The Nb, V and Ti microalloy elements added into the steel are organically combined with C, N elements to exert the dispersion strengthening and grain refining effects to the maximum extent, the rolled structure is refined, and the thickness of a finished product is 50-80 mm.
(6) And (3) heat treatment: in order to obtain the tissue form meeting the harsh performance requirements of the invention, the final heat treatment process is needed to complete, the invention adopts a multiple heat treatment process of high-temperature normalizing, quenching and high-temperature tempering, and A of the steel grade of the invention C3 The temperature is approximately 850 ℃, and the high-temperature normalizing temperature is A C3 The design is 100-150 ℃, namely the high-temperature normalizing temperature is 950-1000 ℃, the heat preservation time is 0.5-1.0 min/mm, and the air cooling is carried out until the room temperature. The process eliminates the grain difference and the structure segregation generated in the rolling process due to the overlarge rolled piece, and ensures the performances of homogenization, hydrogen induced cracking resistance and the like of the product; the quenching temperature is 930-960 ℃, the heat preservation time is 0.5-1.5 min/mm, and the steel plate is cooled to room temperature to obtain a dual-phase structure of 20-30% of lower bainite and 70-80% of lath martensite, so that the high-temperature strength and the high-temperature fatigue performance are met.
In addition, in order to obtain excellent processing performance and service performance of the product, the upper limit of the heat treatment state tensile strength of the material is estimated to be not more than 600MPa according to the design allowable stress, and meanwhile, the post-welding heat treatment state tensile strength at 550 ℃ is also ensured to be more than 370MPa, therefore, the product needs to be further subjected to organization and performance regulation and control through a tempering heat treatment process, the invention designs a tempering temperature of 730-760 ℃, the heat preservation time is 120min + 1.0-2.0 min/mm multiplied by T, T is the thickness of a steel plate and the unit is mm, a composite organization structure of 20-30% of tempered bainite + 70-80% of tempered martensite is obtained under the process, a large amount of dislocation substructures and dispersed carbide existing in the organization prevent the growth tendency and the slippage of crystal grains under the high-temperature service environment, particularly, the organization structure and the internal structure do not generate essential change after the post-welding heat treatment at 700 ℃ multiplied by 16h, the stability is extremely strong, and the comprehensive performance after long-time welding, especially the high-temperature toughness and high-temperature fatigue performance, is ensured.
The invention has the beneficial effects that:
(1) on the basis of medium-low C, Si and Mn components, the content of a harmful element P, S, Sn and a gas O, H are strictly controlled, the high-temperature tempering embrittlement coefficient is controlled to be below 50, a 20-30% tempered bainite and 70-80% tempered martensite dual-phase structure is obtained by compositely adding Cr, Mo, Ni, Nb, V, Ti and N alloy elements and combining a manufacturing process, and the comprehensive performance requirement of the superheater steel plate is guaranteed.
(2) The mechanical property of the advanced nuclear power unit superheater steel plate obtained by the special production process is represented by R being more than or equal to 421MPa and R being in the supply state el ≤436MPa、585MPa≤R m Not more than 599 Mpa; the (A + B + C + D) fine non-metallic inclusion is less than or equal to 1.0 grade, the (A + B + C + D) coarse non-metallic inclusion is 0 grade, and the R of the steel plate is less than or equal to 420MPa at 550 DEG C m 435MPa or less and HBW or 185 or less; 374MPa or less at 550 ℃ and R at 374MPa or more of steel plate after 700 ℃ multiplied by 16h post-weld heat treatment state m Less than or equal to 388MPa, more than or equal to 1000 times of cycle at 550 ℃ when R is equal to-1, more than or equal to 120 ten thousand times of cycle at 550 ℃ when R is equal to 0, and more than or equal to 20 KV 2 The thickness is more than or equal to 300J. The superheater steel plate with the thickness specification of 50-80 mm is obtained, and the superheater steel plate is filled in both excellent comprehensive performance and excellent size specificationSimilar products are blank.
Detailed Description
The present invention is further illustrated by the following examples.
According to the technical scheme, the embodiment of the invention carries out smelting, continuous casting, electroslag remelting, heating, controlled rolling and controlled cooling and heat treatment according to the component proportion.
(1) Continuous casting: the continuous casting superheat degree is 20-30 ℃;
(2) heating: the heating temperature is 1180-1250 ℃, the heating time is 6-8 hours, and the soaking time is 0.5-1.0 hour;
(3) rolling and cooling control:
the initial rolling temperature of the recrystallization zone is 1050-1150 ℃, the single-pass deformation rate of the recrystallization zone is 10-15%, the reduction rate of each pass of the first three passes is 12-15%, and the total deformation rate is more than or equal to 50%; the thickness of the intermediate blank is 3.0-4.5 times that of the finished steel plate; rolling at the non-recrystallized region for 850-880 ℃, rolling at the final temperature of 810-840 ℃, rolling at the non-recrystallized region for not less than 6 times, and keeping the accumulated deformation rate to be not less than 67%;
and (3) after rolling, adopting an ACC controlled cooling process, wherein the start cooling temperature is 770-800 ℃, the re-reddening temperature is 350-450 ℃, and the cooling speed is 20-25 ℃/s.
(3) And (3) heat treatment: adopting high-temperature normalizing, quenching and high-temperature tempering;
high-temperature normalizing: normalizing temperature of A C3 + (100-150) DEG C; namely 950 ℃ to 1000 ℃, the heat preservation time is 0.5min/mm to 1.0min/mm, and the air cooling is carried out to the room temperature.
Quenching: the quenching temperature is 930-960 ℃, the heat preservation time is 0.5-1.5 min/mm, and the steel plate is cooled to room temperature to obtain a dual-phase structure of 20-30% of lower bainite and 70-80% of lath martensite, so that the high-temperature strength and the high-temperature fatigue performance are met.
Tempering: the tempering temperature is 730-760 ℃, the heat preservation time is 120min + 1.0-2.0 min/mm multiplied by T, T is the thickness of the steel plate, the unit is mm, and the final 20-30% of tempered bainite + 70-80% of tempered martensite dual-phase structure is obtained.
Further, the method comprises the following steps of; smelting: comprises converter smelting, LF refining and RH refining
Smelting molten steel in a converter, adopting high-quality scrap steel and molten iron as raw materials, controlling the content of the molten iron to be 70% -80%, and separately smelting dephosphorization and decarburization in the converter, wherein dephosphorization oxygen blowing is controlled to be 7-10 min, and decarburization oxygen blowing is controlled to be 8-12 min; carrying out deep desulfurization treatment in an LF refining furnace, and simultaneously feeding a CaSi wire into steel for calcium treatment, wherein the wire feeding speed is 200-350 m/min, the wire feeding depth is 1.0-2.0 m below a slag layer, and the thickness of the slag layer is 60-90 mm, so that impurities are ensured to float sufficiently; degassing is finished in an RH furnace, the net cycle time is 10-15 min, and the sedation time before casting is 3-5 min.
Further, the method comprises the following steps of; and (3) continuous casting: after vacuum breaking, casting by adopting a continuous casting machine, wherein the superheat degree is 20-30 ℃, and the casting process needs to be stable and constant; preferably, the casting blank is inserted into a stack and slowly cooled, the stacking slow cooling time is 24-48 h, and the stack is unstacked below 400 ℃, so that cracks in the casting blank caused by quenching are prevented.
Further, the method comprises the following steps of; electroslag remelting: and after the electroslag ingot is demoulded, stacking and slow cooling are carried out for 42-72 h, and unstacking and air cooling are carried out at the temperature of below 400 ℃.
The compositions of the steels of the examples of the invention are shown in table 1. The main process parameters for smelting steel in the embodiment of the invention are shown in Table 2. The main technological parameters of continuous casting and heating of the steel of the embodiment of the invention are shown in Table 3. The main process parameters of the controlled rolling of the steel of the embodiment of the invention are shown in Table 4. The main process parameters of the controlled cooling and the heat treatment of the steel of the embodiment of the invention are shown in Table 5. The properties of the steels of the examples of the invention are shown in Table 6. The evaluation results of nonmetallic inclusions in steels according to examples of the present invention are shown in Table 7. The fatigue properties of the steels of the examples of the present invention are shown in Table 8.
TABLE 1 composition (wt%) of steels of examples of the present invention
Figure BDA0003629888130000081
TABLE 2 Main Process parameters for smelting steel of the examples of the present invention
Figure BDA0003629888130000082
TABLE 3 main process parameters for continuous casting and heating of steels according to examples of the present invention
Figure BDA0003629888130000091
TABLE 4 Main Process parameters for controlled Rolling of steels according to the examples of the invention
Figure BDA0003629888130000092
Note: t is the thickness of the finished product
TABLE 5 main Process parameters for controlled Cooling and Heat treatment of steels according to examples of the invention
Figure BDA0003629888130000101
TABLE 6 Steel Structure Properties of examples of the invention
Figure BDA0003629888130000102
TABLE 7 evaluation results of nonmetallic inclusions in steels according to examples of the present invention
Figure BDA0003629888130000111
TABLE 8 fatigue properties of steels according to examples of the invention
Figure BDA0003629888130000112
According to the results, the steel plate for the advanced nuclear power unit superheater, provided by the invention, has high internal purity, extremely low control of P, S harmful element content and tempering embrittlement resistance coefficient J less than 50; the mechanical property of the steel plate is more than or equal to R of 421MPa el ≤436MPa、585MPa≤R m Not more than 599 Mpa; the (A + B + C + D) fine nonmetallic inclusion is less than or equal to 1.0 grade, the (A + B + C + D) coarse nonmetallic inclusion is 0 grade, and R is less than or equal to 420MPa of the steel plate at 550 DEG C m 435MPa or less; the diameter of large-size D-type inclusion is less than or equal to 23 mum, HBW is less than or equal to 185; r is not less than 374MPa at 550 ℃ and not more than R after 700 ℃ multiplied by 16h post-weld heat treatment state of steel plate m(550℃) Less than or equal to 388MPa, more than or equal to 1000 times of cycle at 550 ℃ when R is equal to-1, more than or equal to 120 ten thousand times of cycle at 550 ℃ when R is equal to 0, and more than or equal to 20 KV 2 ≥300J。
The present invention has been described in detail with reference to the foregoing embodiments, and the embodiments are only for illustrating the invention and not for limiting the invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention, and any modifications, equivalents, improvements, etc. made therein shall be included in the scope of the invention, and the scope of the invention shall be defined by the claims.

Claims (9)

1. The steel plate for the advanced nuclear power unit superheater is characterized by comprising the following components in percentage by weight: 0.13 to 0.16 percent of C, 0.10 to 0.25 percent of Si, 0.25 to 0.50 percent of Mn, less than or equal to 0.006 percent of P, less than or equal to 0.002 percent of S, 2.35 to 2.55 percent of Cr, 1.30 to 1.60 percent of Mo, 0.80 to 1.20 percent of Ni, 0.04 to 0.08 percent of Nb, 0.05 to 0.10 percent of V, 0.03 to 0.06 percent of Ti, less than or equal to 0.02 percent of Alt, 0.001 to 0.004 percent of Ca, 0.01 to 0.03 percent of N, less than or equal to 0.001 percent of Sn, less than or equal to 0.0001 percent of H, less than or equal to 0.0020 percent of O, the balance of Fe and inevitable impurities, and a high-temperature tempering embrittlement resistance coefficient J (Si + Mn) x (P + Sn) x 10 4 ≤50。
2. The steel plate for the superheater of the advanced nuclear power unit according to claim 1, wherein the Mo/Si ratio of the steel plate is 6.0-14; the ratio of (Cr + Mn)/Mo is 1.7-2.2.
3. The steel plate for the advanced nuclear power unit superheater according to claim 1, wherein the thickness of the steel plate is 50-80 mm, the microstructure of the steel plate is a bainite and martensite complex phase structure, the volume percentage of bainite is 20-30%, and the volume percentage of martensite is 70-80%.
4. The steel plate for the advanced nuclear power unit superheater according to claim 1, wherein the mechanical property of the steel plate is that R is greater than or equal to 421MPa el ≤436MPa、585MPa≤R m Not more than 599 Mpa; the (A + B + C + D) fine nonmetallic inclusion is less than or equal to 1.0 grade, the (A + B + C + D) coarse nonmetallic inclusion is 0 grade, and R is less than or equal to 420MPa of the steel plate at 550 DEG C m 435MPa or less; r is not less than 374MPa at 550 ℃ and not more than R after 700 ℃ multiplied by 16h post-weld heat treatment state of steel plate m Less than or equal to 388MPa, more than or equal to 1000 times of cycle at 550 ℃ when R is equal to-1, more than or equal to 120 ten thousand times of cycle at 550 ℃ when R is equal to 0, and more than or equal to 20 KV 2 ≥300J、HBW≤185。
5. The manufacturing method of the steel plate for the advanced nuclear power unit superheater, which is disclosed by claims 1-4, is characterized by comprising the following steps of: comprises smelting, continuous casting, electroslag remelting, heating, controlled rolling and controlled cooling and heat treatment;
(1) and (3) continuous casting: the superheat degree of continuous casting is 20-30 ℃;
(2) heating: heating at 1180-1250 ℃ for 6-8 h, wherein the soaking time is 0.5-1.0 h;
(3) rolling and cooling control:
the initial rolling temperature of the recrystallization zone is 1050-1150 ℃, the single-pass deformation rate of the recrystallization zone is 10-15%, the reduction rate of each pass of the first three passes is 12-15%, and the total deformation rate is more than or equal to 50%; the thickness of the intermediate blank is 3.0-4.5 times that of the finished steel plate; rolling at 850-880 ℃ in a non-recrystallization region, rolling at 810-840 ℃ in a final rolling temperature, rolling at no less than 6 times in the non-recrystallization region, and enabling the accumulated deformation rate to be more than or equal to 67%;
and (3) after rolling, adopting an ACC controlled cooling process, wherein the start cooling temperature is 770-800 ℃, the re-reddening temperature is 350-450 ℃, and the cooling speed is 20-25 ℃/s.
(3) And (3) heat treatment: adopting high-temperature normalizing, quenching and high-temperature tempering;
high-temperature normalizing: normalizing temperature of A C3 Cooling to room temperature at 100-150 deg.C for 0.5-1.0 min/mm;
quenching: quenching at 930-960 ℃, keeping the temperature for 0.5-1.5 min/mm, and cooling to room temperature;
tempering: the tempering temperature is 730-760 ℃, the heat preservation time is 120min + 1.0-2.0 min/mm multiplied by T, T is the thickness of the steel plate, and the unit is mm.
6. The manufacturing method of the steel plate for the superheater of the advanced nuclear power unit according to claim 5, characterized by comprising the following steps of: and after the electroslag remelting, the electroslag ingot is demoulded, stacked and slowly cooled for 42-72 h, and unstacked and air-cooled below 400 ℃.
7. The manufacturing method of the steel plate for the superheater of the advanced nuclear power unit according to claim 5, characterized by comprising the following steps of: after continuous casting in the step (1), the casting blank is discharged into a stack for slow cooling, the stack slow cooling time is 24-48 h, and the stack is unstacked below 400 ℃.
8. The manufacturing method of the steel plate for the superheater of the advanced nuclear power unit according to claim 5, characterized by comprising the following steps of:
smelting: comprises converter smelting, LF refining and RH refining;
in the converter smelting process, the dephosphorization and the decarburization are separately smelted by adopting a converter, wherein the dephosphorization oxygen blowing is controlled to be 7-10 min, and the decarburization oxygen blowing is controlled to be 8-12 min;
in the LF refining process, deep desulfurization treatment is carried out in an LF refining furnace, meanwhile, CaSi wires are fed into steel for calcium treatment, the wire feeding speed is 200-350 m/min, the wire feeding depth is 1.0-2.0 m below a slag layer, the thickness of the slag layer is 60-90 mm, and impurities are ensured to float sufficiently;
degassing is finished in the RH refining process, the net cycle time is 10-15 min, and the sedation time before casting is 3-5 min.
9. The method for manufacturing the steel plate for the superheater of the advanced nuclear power unit as claimed in claim 8, wherein the molten steel smelting is performed in a converter, high-quality scrap steel and molten iron are used as raw materials, and the content of the molten iron is controlled to be 70-80%.
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