CN114892085A - Wide and thick steel plate for advanced nuclear power unit positioning and manufacturing method thereof - Google Patents

Wide and thick steel plate for advanced nuclear power unit positioning and manufacturing method thereof Download PDF

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CN114892085A
CN114892085A CN202210487538.4A CN202210487538A CN114892085A CN 114892085 A CN114892085 A CN 114892085A CN 202210487538 A CN202210487538 A CN 202210487538A CN 114892085 A CN114892085 A CN 114892085A
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percent
temperature
rolling
steel plate
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CN114892085B (en
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王储
王勇
段江涛
艾芳芳
欧阳鑫
李侠
严平沅
贾春堂
李黎明
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Angang Steel Co Ltd
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Angang Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • 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
    • 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
    • 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
    • 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
    • C21D8/02—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
    • 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
    • C21D8/02—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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • C22C38/04—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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • 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
    • C21D2211/004—Dispersions; Precipitations
    • 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
    • C21D2211/005—Ferrite
    • 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
    • Y02E30/30—Nuclear fission reactors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

The invention provides an advanced wide and thick steel plate for nuclear power unit positioning 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, 0.20 to 0.30 percent of Si, 0.30 to 0.60 percent of Mn, less than or equal to 0.006 percent of P, less than or equal to 0.002 percent of S, 2.55 to 2.85 percent of Cr, 0.80 to 1.20 percent of Mo, 1.20 to 1.50 percent of Ni, 0.04 to 0.08 percent of Nb, 0.10 to 0.20 percent of V, less than or equal to 0.03 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 tempering embrittlement resistance coefficient J ═ Si + Mn (P + Sn) x 10 4 Less than or equal to 50; the manufacturing method comprises smelting, continuous casting, electroslag remelting, controlled rolling, controlled cooling and heat treatment; the specification of the steel plate is (100-130) mmX (4500-5100) mmX Lmm, and the performance of the steel plate meets the manufacturing and using requirements of a four-generation nuclear power station positioning plate.

Description

Wide and thick steel plate for advanced nuclear power unit positioning and manufacturing method thereof
Technical Field
The invention belongs to the field of metal materials, and particularly relates to a wide and thick steel plate for positioning an advanced nuclear power unit and a manufacturing method thereof.
Background
Nuclear energy has been utilized by humans for over 70 years as one of clean and efficient energy sources in the world. 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-cooled 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, the method has very high requirements on nuclear technology and nuclear equipment, for example, structural steel for positioning nuclear-grade parts is not only in a high-temperature and hydrogen environment, but also is subjected to strong fast neutron irradiation, the risk of matrix embrittlement and water decomposition hydrogen corrosion is several times that of the previous generations of nuclear power technology, the equipment size is large, and great challenges are provided for the development of large-scale steel. Therefore, the development of key nuclear equipment and key nuclear materials meeting the requirements of the fourth-generation advanced nuclear power station becomes a core problem which needs to be solved urgently in the world nuclear energy countries nowadays.
The disclosed invention patent 'a quenching heat treatment manufacturing method of ultra-wide and ultra-thick steel containment nuclear power steel' (publication number CN201811165268.5), from the disclosed patent information, the maximum thickness of the patent is 101mm, the maximum width is 4600mm, the thickness and width specifications required by the fourth generation nuclear power cannot be covered, and the heat treatment mode only introduces a quenching process.
The invention discloses a method for producing ultrathin and ultra-wide limit specification nuclear power steel by a wide and thick plate rolling mill (publication number CN 202010240194.8). according to published patent information, the maximum thickness of the method is 6mm, the maximum width of the method is 4700mm, and the method is mainly used for manufacturing nuclear power containment vessels and cannot meet the requirements of reactor core positioning plates.
The invention relates to a wide and thick nuclear power steel plate and a manufacturing method thereof (publication No. CN201910725047.7), and from the disclosed components, production method and beneficial effects, the steel can be developed into wide and thick nuclear power steel, in the embodiment, the maximum thickness is 101mm and the maximum width is 4300mm, the related mechanical properties can only ensure the use requirement at the working environment temperature of 150 ℃, the higher use temperature is not explained or guaranteed, and the steel is definitely used for manufacturing the third-generation nuclear power containment steel SA738Gr.B.
The invention disclosed by the patent mainly relates to a metal material required by third-generation nuclear power equipment, and compared with a key material required by fourth-generation nuclear power technology, the metal material is characterized by relatively low high-temperature use temperature, no hydrogen in contact environment, short post-welding heat treatment time and relatively single material mechanical property index. The steel for manufacturing the positioning plate needs high homogenization degree, high-temperature fracture toughness resistance, lower NDT temperature, excellent hydrogen induced cracking resistance and the like. In addition, in order to improve the operation safety of a large-parameter unit, a large-scale plate is required to manufacture key equipment through a welding-free one-step forming process, so that the design specification of the plate reaches (100-130) mmx (4500-5100) mmx Lmm, the high-temperature performance and the performance state after the postweld heat treatment at 700 ℃ x 20h are required to be the same, and the materials required by the strict technical indexes are not disclosed and reported temporarily.
Disclosure of Invention
The invention aims to overcome the problems and the defects and provides an advanced wide and thick steel plate for positioning a nuclear power unit, which has the specification of L x (4500-5100) mm x (100-130) mm, has the high-temperature strength at 370 ℃, the high-temperature strength, the high-temperature toughness, the low-temperature drop hammer and the hydrogen-induced cracking resistance after 700 ℃ x 20h postweld heat treatment, and a manufacturing method thereof, and meets the manufacturing and using requirements of a positioning plate for a fourth-generation nuclear power station.
The purpose of the invention is realized as follows:
the invention aims to adopt a brand-new chemical component design and a proper production process, on the basis of medium-low C, Si and Mn components, Cr, Mo, Ni, Nb, V, Ti and N alloy elements are added in a compounding way, the content of harmful element P, S, Sn and gas O, H are strictly controlled, and a unique smelting, rolling and heat treatment production process is matched to develop a high-performance nuclear energy key material meeting the requirements of fourth-generation nuclear power station key equipment, so that the embarrassing situation of 'a rice-below-the-meter pot' of an advanced nuclear power unit in China is solved.
The wide and thick steel plate for positioning the advanced nuclear power unit comprises the following components in percentage by weight: 0.13 to 0.16 percent of C, 0.20 to 0.30 percent of Si, 0.30 to 0.60 percent of Mn, less than or equal to 0.006 percent of P, less than or equal to 0.002 percent of S, 2.55 to 2.85 percent of Cr2, 0.80 to 1.20 percent of Mo, 1.20 to 1.50 percent of Ni, 0.04 to 0.08 percent of Nb, 0.10 to 0.20 percent of V, less than or equal to 0.03 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 (P + Sn) x 10 4 ≤50。
The steel sheet has a Mo/Si ratio of 3 to 5 and a Cr + Mn/Mo ratio of 2.5 to 4.0.
The microstructure of the steel plate is a composite structure of undissolved ferrite and tempered lower bainite, wherein the bainite structure contains a large amount of (Fe, Mn, Cr and Mo) dispersed and precipitated 23 C 6 The volume percentage of un-dissolved ferrite of the alloy carbide with the structure is 10-15%.
The normal temperature mechanical property of the steel plate is 497MPa or less eL ≤512MPa、605MPa≤R m R is less than or equal to 620MPa and 460MPa at 370 DEG C m Less than or equal to 480 MPa; r is more than or equal to 450MPa in a thermal state after welding at 700 ℃ for 20h m(370℃) ≤470MPa、KV 2(80℃) ≥400J、T NDT At a temperature of-40 ℃ or lower, the CSR of HIC (solution A) is 0%, 264 MPa.m 1/2 ≤KIC≤269MPa·m 1/2 (ii) a The size of the steel plate is (100-130) mm multiplied by (4500-5100) mm multiplied by Lmm.
The invention has the following design reasons:
c the main solid solution state C and the chemical combination state C in the invention ensure the high-temperature strength performance of the steel in the heat treatment state and the post-welding heat treatment state, the thickness specification of the invention is larger, so the lower limit of the carbon content is set to be 0.13%, but the excessively high carbon content can influence the welding performance of the steel, so the C content range is set to be 0.13-0.16%.
Si is a good reducing agent and a good deoxidizing agent in the steel-making process, and particularly can be used together with Alt, so that the deoxidizing capacity of Alt can be obviously improved. Si forms a layer of compact, oxidation-resistant SiO on the surface at high temperature 2 Protective film, in addition, Si and Mo act together to form MoSi 2 The intermetallic compound has the characteristic that the atomic combination in the crystal structure 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 intermetallic compound is limited to 3-5, and a certain amount of MoSi formed in the steel plate is ensured 2 And (5) structure. However, in the range of the tempering embrittlement temperature of 350-550 ℃, the too high silicon content causes the tempering embrittlement sensitivity of the steel to be increased, so the excessive addition of silicon element is not suitable in the invention, and the Si content range is set to be 0.20-0.30 percent in the invention.
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 0.30-0.60 percent.
S, P As a harmful element in steel, the comprehensive indexes such as purity, J coefficient and fracture toughness 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 2.55-2.85 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 crystal to prevent grain boundary segregation, so that the (Cr + Mn)/Mo is limited to be 2.5-4.0, the structural stability and the performance stability of the positioning plate steel at the working temperature of 370 ℃ are ensured, and the content range of Mo is set to be 0.80-1.20%.
Ni in the invention, Ni element mainly improves the hydrogen corrosion resistance and the plasticity and toughness of steel, reduces the non-plastic transformation temperature of ferrite, prevents the non-ductile transformation temperature from increasing due to the nuclear irradiation effect, but the Ni content is too high to reduce the irradiation resistance of the material, so the invention sets the Ni content range at 1.20-1.50%.
Nb plays a role in refining grains, the strength and toughness of the steel and the hydrogen induced cracking resistance are improved through grain refinement, and in addition, the steel can also have good hydrogen resistance through a mode of consuming carbon by forming carbide. 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; secondly, V fixes C in vanadium-carbon compound, thus greatly improving the hydrogen resistance stability of the steel under high temperature and high pressure; 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 0.10-0.20%.
Ti is one of the strong ferrite forming elements and strongly raises the a1 and A3 temperatures of steel. 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 the carbide is precipitated to obviously improve the plasticity and impact toughness of the steel, so that the content of Ti is limited to be less than or equal to 0.03 percent.
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 the Sn content is limited to be less than or equal to 0.001 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 become calcium aluminate type oxide inclusions, are spherical and are distributed in a dispersion mode, basically do not deform at the rolling temperature of the steel, and are spherical after rolling, so that the hydrogen induced cracking sensitivity of the steel can be reduced by Ca treatment. However, since the addition of Ca is excessive, the size of formed Ca (O, S) is too large, the brittleness is increased, the Ca can be used as a starting point of fracture crack, 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%.
Alt is shown as a participating or small amount of added element in the invention, plays a role of a deoxidizer, and the added Alt is mainly used for ensuring the purity of steel, so the content of Alt is limited to be less than or equal to 0.02 percent.
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 non-metallic oxide, which affects the purity of steel and the mechanical property of material, and must be strictly controlled, so 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 manufacturing method of a wide and thick steel plate for advanced nuclear power unit positioning, which comprises smelting, continuous casting, electroslag remelting, controlled rolling and heat treatment;
(1) the smelting process comprises the following steps: comprises converter smelting, LF furnace refining and RH refining;
in the smelting process of the converter, in order to effectively reduce the content of harmful elements P, the 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;
preferably, high-quality steel scraps and molten iron are adopted as raw materials, and the content of the molten iron is controlled to be 70-80%;
deep desulfurization treatment is carried out in the LF refining process, 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 treatment changes the form of non-metallic inclusions, fine CaS or calcium aluminate spherical inclusion particles are formed, the steel quality is purified while the steel billet equiaxial rate is increased, the purity is improved, the hydrogen resistance of the steel is improved, the thickness of the generated slag layer is 60-90 mm, and the inclusions are ensured to float upwards sufficiently;
degassing in the furnace is completed in the RH refining process, the net cycle time is 10-15 min, and the sedation time before casting is 3-5 min.
(2) Continuous casting: the degree of superheat is 20-30 ℃; preferably, the casting blank is inserted into a stack and slowly cooled, the stacking and slowly cooling time is 48-72h, and the stack is unstacked below 300 ℃, so that cracks in the casting blank caused by quenching are prevented.
(3) Electroslag remelting: in order to further improve the purity of steel, eliminate internal defects such as segregation and porosity, reduce non-metallic inclusions, homogenize cast structure, the addition of the electroslag remelting process is important for high-temperature performance and hydrogen-induced cracking resistance. The method adopts an electroslag ingot with a section of 500-700 mm thickness and ensuring a sufficient compression ratio to roll finished steel plates with the specification of 100mm or above, the stacking and slow cooling time is 48-72h after the electroslag ingot is demoulded, and unstacking and air cooling are carried out below 300 ℃.
(4) Controlling rolling: the controlled rolling is carried out in two stages;
the first stage is as follows: heating and cogging rolling;
because the thickness specification of the electroslag steel ingot is overlarge, the rolling of the steel plate with the final specification cannot be completed by one-time rolling, a cogging process is required in advance, the specific process is to control the heating temperature to be 1180-1250 ℃, the total heating time to be 24-30 h, the internal heating of the electroslag steel ingot is ensured to be sufficient and uniform, and the rolling of black steel is prevented.
And a longitudinal-transverse rolling strategy is adopted when the steel ingot is cogging, the longitudinal rolling stage is less than or equal to 4, the steel is rotated for 90 degrees, widening rolling is carried out, the transverse rolling stage is less than 3, the total cogging pass is not more than 7, the single-pass reduction is not less than 40mm, the thickness of the billet after cogging is 300-350 mm, the whole process of large-reduction rolling is ensured, and the core tissue of the steel ingot is fully crushed.
Preferably, in order to ensure the internal quality of the steel plate, the steel billets are off-line stacked and slowly cooled, the slow cooling temperature is more than or equal to 400 ℃, and the slow cooling time is 48-72 hours. And after unstacking, cleaning the surface of the steel billet to ensure the surface quality of the rolled steel plate.
And a second stage: heating and rolling;
by controlling the heating process of the steel billet, the alloy elements are ensured to be fully dissolved in the solid state, the growth of original austenite grains is effectively inhibited, the heating temperature is controlled to 1180-1250 ℃, the heating time is 6-8 hours, and the soaking time is 1.0-2.0 hours. And finishing rolling in a high-temperature recrystallization zone, adopting a transverse-longitudinal rolling strategy, directly rolling the steel plate to a target width of 4800mm or more during transverse rolling, turning the steel to 90 degrees, longitudinally rolling the steel plate to a target thickness, ensuring the final plate shape of the steel plate, wherein the cumulative reduction rate reaches 60% or more, and rolling the steel plate to a specification of length, width and height of Lx (4500-5100) mmx (100-130) mm, wherein L is the length of the steel plate.
(5) 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, and the invention adopts a multiple heat treatment process of high-temperature normalizing, sub-temperature quenching and high-temperature tempering;
a of the Steel grade of the invention C3 The temperature is approximately 850 ℃, and the high-temperature normalizing temperature is according to A C3 Plus (100-150) DEG C, namely 950-1000 ℃, the heat preservation time is 0.5-1.0 min/mm, and the air is cooled to 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 sub-temperature quenching temperature is 800-850 ℃, the heat preservation time is 0.5-1.5 min/mm, and the following process parameters are obtained by adjusting the water quantity and the water pressure of a quenching unit, wherein the water quantity is 120-150 m 3 The water pressure is 4-7 bar, the ratio of water to water is 1 (1.5-2.5), the steel plate is watered in a swinging mode, the roller speed is 0.5-1.0 m/s, the temperature of the red returning is 350-450 ℃, then the steel plate is cooled to room temperature along with air, the undissolved ferrite is heated in a two-phase region, crystal grains are more easily refined, and the full-thickness undissolved ferrite and lower bainite two-phase structure of the steel plate is obtained.
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 calculated according to the design allowable stress and is not more than 620MPa, and meanwhile, the post-welding heat treatment state tensile strength at 370 ℃ is not less than 450MPa, so that the organization and performance regulation and control need to be further carried out through precise tempering heat treatment, the invention designs the tempering temperature at 710-730 ℃, the heat preservation time is 60min + 1.0-2.0 min/mm multiplied by T, T is the thickness of a steel plate, and the unit is mm, and the lower bainite is fully recovered and softened (Fe, Mn, Cr and Mo) under the process 23 C 6 The alloy carbide with the structure is not aggregated and grown up, is dispersed and distributed at a bainite ferrite matrix or a crystal boundary in a highly spheroidized state, and has the characteristics of extremely high-temperature stability, no essential change after 700 ℃ multiplied by 20h postweld heat treatment, and guarantee of comprehensive properties after long-term welding, particularly high-temperature toughness, fracture toughness and low-temperature drop hammer performance.
The invention has the beneficial effects that:
(1) strictly controlling the contents of harmful element P, S, Sn and gas O, H on the basis of medium-low C, Si and Mn components, controlling the tempering embrittlement coefficient to be below 50, and combining by compositely adding Cr, Mo, Ni, Nb, V, Ti and N alloy elementsThe manufacturing process obtains a composite structure containing 10-15% of undissolved ferrite and tempered lower bainite, wherein the bainite structure contains a large amount of (Fe, Mn, Cr and Mo) which are dispersed and precipitated 23 C 6 The alloy carbide of the structure ensures the comprehensive performance requirement of the large-size positioning plate.
(2) The mechanical property of the advanced wide and thick steel plate for positioning the nuclear power unit, which is obtained by the special production process, is represented by R being not less than 497MPa at normal temperature in a supply state eL ≤512MPa、605MPa≤R m R is less than or equal to 620MPa and 460MPa at 370 DEG C m Less than or equal to 480 MPa; r is more than or equal to 450MPa in a postweld heat treatment state of 700 ℃ multiplied by 20h m(370℃) ≤470Mpa、KV 2(80℃) ≥400J、T NDT At a temperature of-40 ℃ or lower, the CSR of HIC (solution A) is 0%, 264 MPa.m 1/2 ≤K IC ≤269MPa·m 1/2 The positioning plate with the large size of (100-130) mmX (4500-5100) mmX Lmm is obtained, and the blank of the product is filled in both excellent comprehensive performance and size specification.
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 heat treatment according to the component proportion.
(1) Controlling rolling: the controlled rolling is carried out in two stages;
the first stage is as follows: heating and cogging rolling;
heating before cogging and rolling, wherein the heating temperature is controlled to be 1180-1250 ℃, and the heating time is 24-30 hours;
the steel ingot cogging rolling adopts a longitudinal-transverse rolling strategy, the rolling pass at the longitudinal rolling stage is less than or equal to 4, the steel is turned for 90 degrees, the widening rolling is carried out, the rolling pass at the transverse rolling stage is less than 3, the total cogging pass is not greater than 7, the single-pass reduction is not less than 40mm, and the billet after cogging is 300-350 mm;
and a second stage: heating and rolling;
heating the steel billet before rolling in the second stage, wherein the heating temperature of the steel billet is controlled to be 1180-1250 ℃, and the heating time is 6-8 hours, wherein the soaking time is 1.0-2.0 hours;
the second stage of rolling is finished in a high-temperature recrystallization zone, a transverse-longitudinal rolling strategy is adopted, the target width is directly rolled when the transverse rolling is carried out, the steel is rotated for 90 degrees, the longitudinal rolling is carried out until the target thickness is reached, the cumulative reduction rate reaches more than 60 percent, and the rolling is carried out until the specification is (100-130) mmx (4500-5100) mmx Lmm;
(2) and (3) heat treatment: adopting a multiple heat treatment process of high-temperature normalizing, sub-temperature quenching and high-temperature tempering;
high-temperature normalizing: the high-temperature normalizing temperature is A C3 Cooling to room temperature at 100-150 deg.C for 0.5-1.0 min/mm;
and (3) sub-temperature quenching: the sub-temperature quenching temperature is 800-850 ℃, the heat preservation time is 0.5-1.5 min/mm, then water cooling is carried out, the temperature of the red returning is 350-450 ℃, and then air cooling is carried out to the room temperature;
high-temperature tempering: the tempering temperature is 710-730 ℃, the heat preservation time is 60min + 1.0-2.0 min/mm multiplied by T, T is the thickness of the steel plate, and the unit is mm.
Further, the method comprises the following steps of; after the first-stage cogging rolling in the step (1), the steel billets are stacked off the line and slowly cooled, the slow cooling temperature is more than or equal to 400 ℃, and the slow cooling time is 48-72 hours.
Further, the method comprises the following steps of; the high-temperature tempering temperature in the step (2) is 950-1000 ℃.
Further, the method comprises the following steps of; the water cooling process in the sub-temperature quenching process in the step (2) comprises the following steps:
the water amount of the quenching unit is 120-150 m 3 The water pressure is 4-7 bar, the ratio of water to water is 1 (1.5-2.5), the watering is carried out in a swinging mode, and the roller speed is 0.5-1.0 m/s.
Further, the method comprises the following steps of; the smelting process comprises converter smelting, LF furnace 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;
deep desulfurization treatment is carried out in the LF refining process, and 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 generated slag layer is 60-90 mm, and impurities are ensured to float sufficiently;
degassing in the furnace is completed in the RH refining process, 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; in the smelting process of the converter, scrap steel and molten iron are used as raw materials, and the content of the molten iron is controlled to be 70-80%.
Further, the method comprises the following steps of; and (3) continuous casting: and the superheat degree is 20-30 ℃, the casting blank is inserted into a stack for slow cooling, the stack slow cooling time is 48-72h, and unstacking is carried out at the temperature below 300 ℃.
Further, the method comprises the following steps of; electroslag remelting: the thickness section of the electroslag remelting steel ingot is 500-700 mm, the stacking and slow cooling time is 48-72h after the electroslag ingot is demoulded, and unstacking and air cooling are carried out below 300 ℃.
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 rolling process parameters of the steels of the examples of the invention are shown in Table 3. The heat treatment process parameters of the steels of the examples of the invention are shown in Table 4. The final effect of the steel structure performance of the embodiment of the invention is shown in Table 5. The results of the hydrogen induced cracking resistant HIC test (solution A) of the steel examples of the invention are shown in Table 6. The fracture toughness test results of the inventive examples are shown in Table 7.
TABLE 1 composition of inventive example steels (wt%)
Figure BDA0003629778990000101
TABLE 2 smelting Process parameters of steels of examples of the present invention
Figure BDA0003629778990000102
TABLE 3 Rolling Process parameters of steels of examples of the invention
Figure BDA0003629778990000111
Note: l is the length of the steel plate.
TABLE 4 Heat treatment Process parameters of steels of examples of the present invention
Figure BDA0003629778990000112
TABLE 5 Steel Structure and Properties of examples of the invention
Figure BDA0003629778990000121
TABLE 6 examples HIC test results for hydrogen induced cracking resistance (A solution)
Figure BDA0003629778990000131
Table 7 examples fracture toughness test results
Figure BDA0003629778990000132
According to the results, the advanced nuclear power unit positioning steel plate provided by the invention has high internal purity, extremely low control of P, S harmful element content, tempering embrittlement resistance coefficient J less than 50, and normal temperature 497 MPa-R in a supply state eL ≤512MPa、605MPa≤R m R is less than or equal to 620MPa and 460MPa at 370 DEG C m Less than or equal to 480 MPa; r is more than or equal to 450MPa in the post-welding hot state steel plate m(370℃) ≤470MPa、KV 2(80℃) ≥400J、T NDT At a temperature of-40 ℃ or lower, the CSR of HIC (solution A) is 0%, 264 MPa.m 1/2 ≤KIC≤269MPa·m 1/2 。
In order to express the present invention, the above embodiments are properly and fully described by way of examples, and the above embodiments are only used for illustrating the present invention and not for limiting the present invention, and those skilled in the relevant art can make various changes and modifications without departing from the spirit and scope of the present invention, and any modifications, equivalent substitutions, improvements, etc. made by the persons skilled in the relevant art should be included in the protection scope of the present invention, and the protection scope of the present invention should be defined by the claims.

Claims (10)

1. Advanced nuclear power unitThe wide and thick steel plate for positioning is characterized by comprising the following components in percentage by weight: 0.13 to 0.16 percent of C, 0.20 to 0.30 percent of Si, 0.30 to 0.60 percent of Mn, less than or equal to 0.006 percent of P, less than or equal to 0.002 percent of S, 2.55 to 2.85 percent of Cr, 0.80 to 1.20 percent of Mo, 1.20 to 1.50 percent of Ni, 0.04 to 0.08 percent of Nb, 0.10 to 0.20 percent of V, less than or equal to 0.03 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 tempering embrittlement resistance coefficient J ═ Si + Mn (P + Sn) x 10 4 ≤50。
2. The wide and thick steel plate for the advanced nuclear power unit positioning as claimed in claim 1, wherein Mo/Si in the steel plate is 3-5, (Cr + Mn)/Mo is 2.5-4.0, the length, width and height of the steel plate are Lx (4500-5100) mm x (100-130) mm, and L is the length of the steel plate.
3. The manufacturing method of the wide and thick steel plate for the advanced nuclear power unit positioning in claim 1 or 2 comprises smelting, continuous casting, electroslag remelting, controlled rolling, controlled cooling and heat treatment; the method is characterized in that:
(1) controlling rolling: the controlled rolling is carried out in two stages;
the first stage is as follows: heating and cogging rolling;
heating before cogging and rolling, wherein the heating temperature is controlled to be 1180-1250 ℃, and the heating time is 24-30 hours;
the steel ingot cogging rolling adopts a longitudinal-transverse rolling strategy, the rolling pass is not more than 4 in the longitudinal rolling stage, the steel is rotated by 90 degrees, the widening rolling is performed, the rolling pass in the transverse rolling stage is less than 3, the total cogging pass is not more than 7, the single-pass rolling reduction is not less than 40mm, and the cogging thickness of the billet is 300-350 mm;
and a second stage: heating and rolling;
heating the steel billet before rolling in the second stage, wherein the heating temperature of the steel billet is controlled to be 1180-1250 ℃, and the heating time is 6-8 hours, wherein the soaking time is 1.0-2.0 hours;
the second stage of rolling is finished in a high-temperature recrystallization area, a transverse-longitudinal rolling strategy is adopted, the target width is directly rolled to be more than 4800mm during transverse rolling, the steel is rotated to be 90 degrees, the longitudinal rolling is carried out to the target thickness, the cumulative reduction rate reaches more than 60 percent, and the rolling is carried out to the specification of (100-130) mmX (4500-5100) mmX Lmm;
(2) and (3) heat treatment: adopting a high-temperature normalizing, sub-temperature quenching and high-temperature tempering multiple heat treatment process;
high-temperature normalizing: the high-temperature normalizing temperature is A C3 Cooling to room temperature at 100-150 deg.C for 0.5-1.0 min/mm;
and (3) sub-temperature quenching: the sub-temperature quenching temperature is 800-850 ℃, the heat preservation time is 0.5-1.5 min/mm, then water cooling is carried out, the temperature of the red returning is 350-450 ℃, and then air cooling is carried out to the room temperature;
high-temperature tempering: the tempering temperature is 710-730 ℃, the heat preservation time is 60min + 1.0-2.0 min/mm multiplied by T, and T is the thickness of the steel plate and the unit is mm.
4. The manufacturing method of the wide and thick steel plate for the advanced nuclear power unit positioning as claimed in claim 3, wherein after the first-stage cogging rolling in the step (1), the steel billet is subjected to offline stacking and slow cooling, the slow cooling temperature is not less than 400 ℃, and the slow cooling time is 48-72 hours.
5. The manufacturing method of the advanced wide and thick steel plate for nuclear power unit positioning according to claim 3, wherein the high-temperature tempering temperature in the step (2) is 950-1000 ℃.
6. The manufacturing method of the wide and thick steel plate for the advanced nuclear power unit positioning according to claim 3, wherein the water cooling process in the sub-temperature quenching process in the step (2) comprises the following steps:
the water amount of the quenching unit is 120-150 m 3 The water pressure is 4-7 bar, the ratio of water to water is 1 (1.5-2.5), the watering is performed in a swinging way, and the roller speed is 0.5-1.0 m/s.
7. The manufacturing method of the wide and thick steel plate for the advanced nuclear power unit positioning according to claim 3, characterized in that the smelting process comprises converter smelting, LF furnace 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;
deep desulfurization treatment is carried out in the LF refining process, and 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 generated slag layer is 60-90 mm, and impurities are ensured to float sufficiently;
degassing in the furnace is completed in the RH refining process, the net cycle time is 10-15 min, and the sedation time before casting is 3-5 min.
8. The manufacturing method of the wide and thick steel plate for the advanced nuclear power unit positioning as claimed in claim 7, wherein scrap steel and molten iron are used as raw materials in a converter smelting process, and the molten iron content is controlled to be 70-80%.
9. The manufacturing method of the wide and thick steel plate for the advanced nuclear power unit positioning according to claim 3, characterized in that the continuous casting comprises the following steps: and (3) the superheat degree is 20-30 ℃, the casting blank is discharged, stacked and slowly cooled, the stacking and slow cooling time is 48-72 hours, and unstacking is carried out at the temperature below 300 ℃.
10. The manufacturing method of the wide and thick steel plate for the advanced nuclear power unit positioning as claimed in claim 3, wherein the electroslag remelting: the thickness section of the electroslag remelting steel ingot is 500-700 mm, the stacking and slow cooling time is 48-72h after the electroslag ingot is demoulded, and unstacking and air cooling are carried out below 300 ℃.
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