EP4261310B1 - Acier pour génie maritime doté de résistance à la corrosion sous atmosphère marine hautement humide et chaude et procédé de fabrication associé - Google Patents

Acier pour génie maritime doté de résistance à la corrosion sous atmosphère marine hautement humide et chaude et procédé de fabrication associé

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Publication number
EP4261310B1
EP4261310B1 EP22738986.3A EP22738986A EP4261310B1 EP 4261310 B1 EP4261310 B1 EP 4261310B1 EP 22738986 A EP22738986 A EP 22738986A EP 4261310 B1 EP4261310 B1 EP 4261310B1
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European Patent Office
Prior art keywords
steel
marine engineering
present disclosure
inclusions
marine
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EP22738986.3A
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German (de)
English (en)
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EP4261310A4 (fr
EP4261310A1 (fr
Inventor
Xiaohui Lu
Shan Gao
Caiyi ZHANG
Yan Shen
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/021—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving particular fabrication steps or treatments of ingots or slabs
    • 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0263—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following 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 of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/04—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for drawing, e.g. for deep-drawing
    • C21D8/0421—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for drawing, e.g. for deep-drawing characterised by the working steps
    • C21D8/0426—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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • 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
    • C22C38/002—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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • 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
    • C21D2211/001—Austenite
    • 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

Definitions

  • the present disclosure relates to steel and a manufacturing method therefor, and particularly relates to steel for marine engineering and a manufacturing method therefor.
  • Chinese patent publication No. CN103741056A which is published on Apr. 23, 2014 , and entitled "Corrosion-Resistant Steel Plate for Marine Environment in the South China Sea and Manufacturing Process Therefor” discloses a corrosion-resistant steel plate for a marine environment in the South China Sea, which adopts a low-carbon composition, and is added with much Si, Mn, Cu, Cr and Ni, and some element Sn.
  • the steel plate has a single-phase polygonal ferrite structure, an average grain size of 10.17 ⁇ m, a steel grade yield strength of 355 MPa, a tensile strength of 490-630 MPa, and a Charpy impact energy at -40 °C of greater than 34 J.
  • EP 3120941 B1 discloses a thick steel plate used in ships and offshore structures.
  • One of the objectives of the present disclosure is to provide steel for marine engineering, which has not only excellent strength toughness, but also excellent anti-fracture and anti-crack properties and corrosion resistance to highly humid and hot marine atmosphere.
  • the steel for marine engineering of the present disclosure can be applied to boats and marine engineering structures, especially marine atmospheric structural components of marine engineering structures, and can serve in different sea regions, especially suitable for highly humid and hot sea regions such as the South China Sea, which has broad application prospects.
  • the present disclosure provides steel for marine engineering, comprising the following chemical elements by mass percentage: C: 0.01-0.05%, Si: 0.05-0.60%, Mn: 0.50-1.30%, Cr: 0.6-1.20%, Ni: 2.0-3.0%, Al: 0.01-0.06%, Ti: 0.005-0.012%, and Mg: 0.0005-0.0015%, 0 ⁇ Ca ⁇ 0.0045%, 0 ⁇ Cu ⁇ 0.5%, and 0 ⁇ Mo ⁇ 0.40%; at least one of the following chemical elements: 0 ⁇ Nb ⁇ 0.04%, 0 ⁇ V ⁇ 0.05%, and 0 ⁇ B ⁇ 0.0005%, and the remainder of Fe and inevitable impurities, wherein in the inevitable impurities P ⁇ 0.015%, and/or S ⁇ 0.0040%, wherein the steel has a microstructure of tempered bainite with a phase ratio of 95% or more and the austenite grain size is 20-25 ⁇ m.
  • the mass percentages of the chemical elements in the steel for marine engineering of the present disclosure are as follows: C: 0.015-0.04%, Si: 0.15-0.60%, Mn: 0.50-1.30%, Cr: 0.6-0.90%, Ni: 2.0-2.85%, Al: 0.01-0.06%, Ti: 0.005-0.012%, and Mg: 0.0005-0.0015%, 0 ⁇ Ca ⁇ 0.0045%, 0 ⁇ Cu ⁇ 0.5%, and 0 ⁇ Mo ⁇ 0.40%; and the remainder of Fe and inevitable impurities.
  • the steel for marine engineering of the present disclosure has ultra-low C, and is designed with a Mn, Nb, V and Ti micro-alloying and Cr-Ni-Mo-Cu alloying composition system.
  • the design principles of the chemical elements are specifically described as follows:
  • C the steel for marine engineering of the present disclosure adopts an ultra-low carbon design, which not only uses the interstitial strengthening effect of carbon to ensure suitable strength of the invented steel plate, but also can effectively prevent precipitation of excessive carbides and reduce the potential difference between the matrix and the carbide phase to obtain good corrosion resistance, while the steel plate has good low-temperature toughness and welding property. Therefore, in the steel for marine engineering of the present disclosure, the mass percentage of C is controlled to 0.01-0.05%.
  • the element Si in the steel for marine engineering of the present disclosure, the element Si is a common weak deoxidizing element in steelmaking, and has certain solid solution strengthening effect. It is to be noted that under Cl - conditions, element Si can form complex oxides of FeAlSiO in the rust layer of the steel and clog cavities and cracks, thereby playing a protective role for the steel. On this basis, in the steel for marine engineering of the present disclosure, the mass percentage of Si is controlled to 0.05-0.60%.
  • Mn in the steel for marine engineering of the present disclosure, Mn is the most basic alloying element for a low-alloy high-strength steel type, and can improve the strength of the steel by solid solution strengthening and compensate for the loss of strength caused by the reduced content of the element C in the steel.
  • the content of the element Mn in the steel should not be too high. If the content of element Mn in the steel is too high, segregation is liable to occur in the center of the steel plate, which reduces the low-temperature toughness of the steel.
  • the mass percentage of Mn is controlled to 0.50-1.30%.
  • the element Cr in the steel for marine engineering of the present disclosure, can improve the passivation performance of the steel to facilitate the formation of a compact oxide film on the steel surface, and is likely to be enriched in the inner rust layer to refine alpha hydroxy iron oxide.
  • the content of the element Cr in the steel should not be too high. If too much Cr is added, under the Cl - environment, the corrosion resistance of the steel will be worsened seriously in the late stage of corrosion. Therefore, considering the beneficial effects and adverse effects of the element Cr in combination, in the steel for marine engineering of the present disclosure, the mass percentage of the element Cr is controlled to 0.6-1.20%.
  • the element Ni in the steel for marine engineering of the present disclosure, can infinitely solid-solubilize with the iron matrix, which can improve the low-temperature toughness of the steel, especially the impact toughness of the central part of a thick steel plate, and can improve the anti-fracture and anti-crack properties of the steel plate. Furthermore, the increase of the content of the element Ni in the steel plays a great role in improving the corrosion resistance of the steel in the marine environment. Ni can slow down the corrosion development trend of the material over time, and inhibit the inverse effect of corrosion and the tendency of pitting corrosion. However, it is to be noted that the content of the element Ni in the steel should not be too high.
  • the mass percentage of Ni is controlled to 2.0-3.0%.
  • Al belongs to a grain refining element.
  • the element Al is added to the steel for deoxidation. After complete deoxidation, the content of O in the material is reduced so that the aging property is improved.
  • adding an appropriate amount of Al in the steel is also conducive to refining grains and improving the strength and toughness property of the steel. Therefore, in the steel for marine engineering of the present disclosure, the mass percentage of the element Al is controlled to 0.01-0.06%.
  • the element Ti in the steel for marine engineering of the present disclosure, is a strong N-fixing element, which can effectively suppress the content of the element N in the steel and prevent adverse effects on the properties of the steel due to an excessively high content of N. Furthermore, a TiN precipitation phase formed by the elements Ti and N can inhibit excessive growth of grains in slabs and steel plates during heating. Therefore, in the steel for marine engineering of the present disclosure, the mass percentage of the added element Ti is controlled to 0.005-0.012%.
  • the element Mg in the steel for marine engineering of the present disclosure, the element Mg can effectively improve sulfide morphology, refine inclusions, and enhance the corrosion resistance of the steel plate.
  • the element Mg is an important element for implementing beneficial modification technology of inclusions in the present disclosure. If the content of the element Mg in the steel is too low, modification of inclusions cannot be realized. If the content of the element Mg in the steel is too high, it is liable to form MgO and MgS, which would clog the tundish nozzle. Therefore, in the steel for marine engineering described in the present invention, the mass percentage of the added element Mg is controlled to 0.0005-0.0015%.
  • the mass percentage of the added element Ca is controlled to 0 ⁇ Ca ⁇ 0.0045%.
  • the element Cu in the steel for marine engineering of the present disclosure, can appropriately improve the hardenability of the steel, and can improve the atmospheric corrosion resistance of the steel.
  • the content of the element Cu in the steel should not be too high. If the content of Cu in the steel is too high, the welding property of the steel will deteriorate. Therefore, in the steel for marine engineering of the present disclosure, the mass percentage of Cu is controlled to 0 ⁇ Cu ⁇ 0.5%.
  • the element Mo in the steel for marine engineering of the present disclosure, the element Mo can effectively improve the pitting corrosion resistance of the steel, but too high a content of Mo increases the cold cracking tendency of the steel plate. Therefore, in the steel for marine engineering of the present disclosure, the mass percentage of the element Mo is controlled to 0 ⁇ Mo ⁇ 0.40%.
  • the steel for marine engineering of the present disclosure further comprises at least one of the following chemical elements: 0 ⁇ Nb ⁇ 0.04%, 0 ⁇ V ⁇ 0.05%, and 0 ⁇ B ⁇ 0.0005%.
  • the elements Cu, Mo, Nb, V and B can all further improve the performance of the steel for marine engineering of the present disclosure.
  • Nb in the steel for marine engineering of the present disclosure, Nb is a strong carbonitride forming element with a strong grain refining effect. Adding an appropriate amount of Nb to the steel to obtain a uniform grain size can effectively prevent some of the grains from excessive growth and form mixed crystal structure during heating, which would otherwise deteriorate the strength and toughness properties and the corrosion performance. Therefore, when present in the steel for marine engineering of the present disclosure, the mass percentage of the element Nb is controlled to 0 ⁇ Nb ⁇ 0.04%.
  • the element V in the steel for marine engineering of the present disclosure, can contribute to the strengthening of the steel by forming VN or V(CN) fine precipitated particles with C and N. Furthermore, the element V is beneficial to improving the stability of hardness after quenching and tempering. However, it is to be noted that the content of the element V in the steel should not be too high. If the content of the element V in the steel is too high, the cost will be increased significantly. Therefore, when present in the steel for marine engineering of the present disclosure, the mass percentage of the element V is controlled to 0 ⁇ V ⁇ 0.05%.
  • the element B in the steel for marine engineering of the present disclosure, the element B can improve the hardenability of the steel and influence the cold cracking property of the steel. Therefore, when present in the steel for marine engineering of the present disclosure, the mass percentage of the element B is controlled to 0 ⁇ B ⁇ 0.0005%.
  • both P and S are impurity elements in the steel. Therefore, in order to achieve better performance and better quality of the steel, the content of impurity elements in the steel should be reduced as much as possible where technical conditions permit. If the content of the elements P and S in the steel is too high, defects such as segregation and inclusion are liable to occur, which deteriorate the welding property, impact toughness and HIC resistance of the steel plate.
  • the mass percentages of the chemical elements in the steel for marine engineering of the present disclosure further satisfy at least one of:
  • the microstructure of the steel for marine engineering of the present disclosure is tempered bainite with a phase ratio of greater than or equal to 95%.
  • the microstructure of the steel for marine engineering of the present disclosure is a tempered bainite structure, and the phase ratio of the tempered bainite is 95% or more, so that the steel has more balanced and improved strength and toughness.
  • the steel for marine engineering of the present disclosure has a yield strength of 355 MPa or more, a tensile strength of 500-650 MPa, an elongation rate of 22% or more, an impact energy at -60°C of 100 J or more, a crack tip opening displacement (CTOD) at -60°C of 0.8 mm or more, a nil ductility transition temperature (NDTT) of -65°C or less, and a corrosion rate in a highly humid and hot atmospheric environment of 0.85 g/(m 2 *h) or less.
  • COD crack tip opening displacement
  • NDTT nil ductility transition temperature
  • another objective of the present disclosure is to provide a manufacturing method for steel for marine engineering.
  • the manufacturing method is simple to perform.
  • Steel for marine engineering manufactured by the method has not only excellent strength and toughness, but also excellent anti-fracture and anti-crack properties as well as corrosion resistance to highly humid and hot marine atmosphere.
  • the steel for marine engineering prepared by the manufacturing method of the present disclosure has a yield strength of 355 MPa or more, a tensile strength of 500-650 MPa, an elongation rate of 22% or more, an impact energy at -60°C of 100 J or more, a CTOD at -60°C of 0.8 mm or more, an NDTT of -65°C or more, and a corrosion rate in a highly humid and hot atmospheric environment of 0.85 g/(m 2 *h) or less.
  • the steel for marine engineering manufactured by the method of the present disclosure can be used for boats and marine engineering structures and has broad application prospects.
  • the present disclosure provides a manufacturing method for steel for marine engineering, comprising the following steps:
  • step (1) hot metal pretreatment, converter smelting, LF refining, RH refining, inclusions beneficial treatment and continuous casting are performed successively, wherein in the inclusions beneficial treatment stage, composite inclusions with MgO+Al 2 O 3 as the core which coated with CaS and MnS are formed, the size of the composite inclusions is 0.2 to 2.5 ⁇ m, and the number of composite inclusions in this size range accounts for more than 95% of the total number of inclusions.
  • step (1) in the stage of converter smelting, slag cutoff tapping is performed, with the thickness of a slag layer being controlled to be smaller than 30 mm; in the stage of LF refining, the sum of the mass percentages of FeO and MnO in the slag is controlled to be smaller than 1%, and a formula is satisfied: (CaO+MgO+MnO)/(SiO 2 +P 2 O 5 ) ⁇ 9, with the mass percentages of the substances being substituted into the formula; in the stage of inclusions beneficial treatment, Mg treatment or Mg and Ca composite treatment is performed; and when Mg and Ca composite treatment is performed, Ca and Mg need to be fed at the same time with a wire feeding speed of 150-250 m/min.
  • step (1) of the manufacturing method of the present disclosure in the stage of converter smelting, performing slag cutoff tapping, with the thickness of a slag layer being controlled to be smaller than 30 mm, can reduce the oxidation of slag in the ladle, prevent the increase of oxygen activity and rephosphorization of molten steel, and is conducive to subsequent production of white slag and inclusions modification treatment.
  • controlling (CaO+MgO+MnO)/(SiO 2 +P 2 O 5 ) to be greater than 9 in the stage of LF refining can ensure good dephosphorization and desulfurization ability of the slag.
  • the sum of the mass percentages of FeO and MnO in the slag is controlled to be smaller than 1% so as to ensure the reduction of the slag and full desulfurization, reducing the content of inclusions in molten steel, and improving the strength and toughness as well as corrosion resistance of the steel.
  • step (2) of the manufacturing method of the present disclosure the purpose of controlling the slab heating temperature to the above value is to ensure sufficient solid solution of micro-alloyed carbonitrides, and facilitate homogenization of alloying elements, mitigate macroscopic and microscopic segregation in the steel, reduce the formation of corrosion primary cells due to different phases and potential differences between components, and improve the corrosion resistance of the steel plate.
  • step (3) rolling reduction in a single pass is 8-12%, and cumulative rolling reduction is 60% or more.
  • the purpose of controlling rolling reduction of a single pass to 8-12% is mainly to ensure that the steel plate has sufficient recrystallization driving force in each pass, while the number of the rolling passes are sufficient enough to achieve grain homogenization of the steel plate, so as to maintain the original austenite grain size after rolling to 20-25 ⁇ m.
  • the purpose of controlling cumulative rolling reduction to be 60% or more is mainly to achieve sufficient recrystallization and sufficient homogenization at the core of the steel plate to ensure the strength and toughness, and anti-fracture and anti-crack properties of the core.
  • the purpose of setting the above-mentioned quenching temperature is firstly to ensure complete austenitization of the steel plate; and secondly, by austenitization at a relatively high temperature, sufficient solid solution of carbonitrides can be achieved, uniform distribution of alloy in the steel can be facilitated, and microscopic electrochemical corrosion caused by segregation can be mitigated. Furthermore, the quenching temperature will not be too high, which would otherwise cause part of austenite grains to grow rapidly, resulting in mixed crystals. Subsequently, water quenching can be performed, the purpose of which is to obtain a high cooling rate and form a unitary martensitic structure, so as to ensure that the austenite grain size after quenching is maintained at 20-25 ⁇ m.
  • step (5) of the present disclosure the purpose of setting the above-mentioned tempering temperature is firstly to ensure that the steel plate has good mechanical properties and anti-fracture and anti-crack properties, secondly to eliminate quenching stress within the steel plate by tempering, so as to prevent corrosion caused by different forces at various positions inside the steel plate, and finally to obtain tempered bainite structure after the steel plate is tempered, thereby reducing microscopic galvanic corrosion caused by multiple phases.
  • the tempering temperature is too high, a ferrite structure will be formed in the steel, which will reduce the strength and impact property of the steel plate; and if the tempering temperature is too low, the strength of the steel plate is too high and the impact toughness is relatively low.
  • the steel for marine engineering and the manufacturing method therefor of the present disclosure have the following advantages and beneficial effects as described below: by composition design, structure regulation, and condition control of production process and the like, the steel plate of the present disclosure achieves suitable strength property, excellent impact toughness, good anti-fracture and anti-crack properties, and excellent corrosion resistance to highly humid and hot marine atmosphere.
  • the manufacturing method of the present disclosure uses unique composition design technology, pure steel smelting technology, inclusions beneficial control technology, steel homogenization technology, grain size control and microstructure regulation technology, so as to produce steel types with strength requirements of 355 MPa level, good low-temperature impact toughness, good anti-fracture and anti-crack properties and excellent resistance to highly humid and hot atmospheric corrosion.
  • the steel plate manufactured by the method of the present disclosure differs greatly from the existing steel plates in structure, composition and process design.
  • the steel for marine engineering of the present disclosure can achieve: a yield strength of 355 MPa or more, a tensile strength of 500-650 MPa, an elongation rate of 22% or more, an impact energy at -60°C of 100 J or more, a CTOD at -60°C of 0.8 mm or more, an NDTT of -65°C or less, and a corrosion rate in a highly humid and hot atmospheric environment of 0.85 g/(m 2 *h) or less.
  • the steel for marine engineering of the present disclosure can be used for key components of boats and marine engineering structures, meets the current development demand for steel for boats and marine engineering equipment in China, and has broad application prospects.
  • slag cutoff tapping is performed, with the thickness of a slag layer being controlled to be smaller than 30 mm; at the stage of LF refining, the sum of the mass percentages of FeO and MnO in the slag is controlled to be smaller than 1%, and (CaO+MgO+MnO)/(SiO 2 +P 2 O 5 ) is controlled to be greater than 9, with the mass percentages of the substances being substituted into the relationship; at the stage of inclusions beneficial treatment, Mg treatment or Mg and Ca composite treatment is performed; and when Mg and Ca composite treatment is performed, Ca and Mg need to be fed at the same time with a wire feeding speed of 150-250 m/min.
  • Examples 1-6 of the present disclosure 6 different chemical compositions are designed and combined with suitable production processes to manufacture steel plates having different thickness specifications.
  • the chemical composition designs of the steel for marine engineering in Examples 1-6 and the related processes all meet the design specification requirements of the present disclosure.
  • Tables 1-1 and 1-2 list the mass percentages of the chemical elements of the steel for marine engineering in Examples 1-6 and the comparative steel in Comparative Example 1.
  • Table 1-1 (wt.%, the remainder being Fe and other inevitable impurities except P and S)
  • Example 1 0.015 0.55 1.3 0.015 0.003 0.60 2.20 0.01 0.008 0.0010 0.0001 0.5 0.4 0.01 0.05 0.0003
  • Example 2 0.020 0.45 1.2 0.012 0.002 0.90 2.40 0.05 0.009 0.0005 0.0006 0.4 0.1 0.015 0.03 0.0002
  • Example 3 0.030 0.35 1.1 0.012 0.003 0.90 2.25 0.04 0.012 0.0012 0.0001 0.4 0 0.016 0.01 0.0001
  • Example 4 0.030 0.45 1.0 0.010 0.002 0.70 2.50 0.03 0.012 0.0008 0.0002 0.3 0.4
  • Table 2 lists specific process parameters for fabricating the steel for marine engineering in Embodiments 1-6 and the comparative steel in Comparative Example 1.
  • Table 2 Serial Number Plate thickness Step (1) Step (2) Step (3) Step (5) Wire feeding speed (m/min) Slab heating temperature (°C) Initial rolling temperature (°C) Final rolling temperature (°C) Rolling reduction of a single pass (%) Cumulative rolling reduction (%) Quenching temperature (°C) Tempering temperature (°C)
  • Example 2 40 170 1190 1118 905 9 89 927 671
  • Example 3 60 190 1191 1120 909 10 83 923 657
  • Example 5 100 230 1195 1123 922 12 72 939 644
  • Example 6 120 250 1173 1102 939 12 67 940 671 Comparative Example 1 60 - 1120 1020 760 5-13 83 - - -
  • the obtained steel for marine engineering in Examples 1-6 and the obtained comparative steel in Comparative Example 1 are sampled, respectively, a tensile test, a Charpy V-notch impact test, a CTOD test (an index to check the fracture toughness of steel plates), an NDTT property checking test (an important index to measure the crack arrest properties of steel plates) and a corrosion test under highly humid and hot conditions are performed on finished plates in the Examples and the Comparative Example, respectively.
  • the test results of the Examples and the Comparative Example are listed in Table 3, respectively.
  • Tensile test according to GB/T 228.1, full-thickness plate-like tensile test specimens are used for steel plates with a thickness of smaller than 50 mm, and rod-like tensile test specimens are used for steel plates with a thickness of greater than 50 mm, then the room-temperature tensile properties of the steel plates are measured.
  • Charpy V-notch impact test according to GB/T 229, Charpy V-notch impact test specimens are used to measure the impact properties of the material plates at a position of t/4 of thicknesses at -60°C.
  • CTOD test according to BS7448-1, full-thickness CTOD test specimens are used to measure the fracture toughness of the materials at -60°C.
  • NDTT property checking test according to GB/T 6803-2008, P3 test specimens are used to measure the nil-ductility transition temperature of the materials.
  • Corrosion test under highly humid and hot conditions it is controlled that the test process uses 5% NaCl solution with a temperature of 35 °C, and a pH of 6.5-7.2, an average sedimentation rate of salt spray is controlled to 1.5mL/(80cm 2 ⁇ h), and an RH (relative humidity) is controlled to 95%-100%.
  • Table 3 lists the test results of the steel for marine engineering in Embodiments 1-6 and the comparative steel in Comparative Example 1.
  • Table 3 Serial Number Yield Strength ReH (MPa) Tensile strength RM (MPa) Elongation rate A (%) Impact energy KV2 at -60°C (J) CTOD value at -60°C (J) NDTT (°C) Corrosion rate under highly humid and hot conditions g/(m 2 *h)
  • Example 1 541 595 25 300 2.0 -80 0.83
  • Example 2 532 587 24 305 1.8 -75 0.72
  • Example 3 508 580 25 298 1.6 -75 0.79
  • Example 6 423 532 22 270 0.8 -65 0.78 Comparative Example 1 420 523 22 220 0.5 -45 1.21
  • the overall performance of the steel for marine engineering in Examples 1-6 is significantly superior to that of the comparative steel in Comparative Example 1.
  • the corrosion rates of the steel for marine engineering in Examples 1-6 are significantly smaller than the corrosion rate of the steel in Comparative Example 1.
  • the steel for marine engineering in Examples 1-6 has better resistance to highly humid and hot corrosion, compared with the comparative steel in Comparative Example 1.
  • the steel for marine engineering in Examples 1-6 has excellent strength and toughness properties, anti-fracture and anti-crack properties, and resistance to highly humid and hot corrosion, compared with the comparative steel in Comparative Example 1.
  • the steel for marine engineering in Examples 1-6 all has a yield strength of 423 MPa or more, a tensile strength of 532-595 MPa, an impact energy at -60°C of 270 J or more, an elongation rate of 22% or more, a CTOD at -60°C of 0.8 mm or more, an NDTT of -65°C or less, and a corrosion rate in a highly humid and hot atmospheric environment of 0.83 g/(m 2 *h) or less.
  • the steel for marine engineering of the present disclosure achieves suitable strength properties, excellent impact toughness, good anti-fracture and anti-crack properties and excellent corrosion resistance to highly humid and hot marine atmosphere at the same time.
  • the steel for marine engineering of the present disclosure can be effectively used for manufacturing key components of boats and marine engineering structures, offshore wind power platforms, sea island buildings, etc.
  • the steel meets the current development demand for steel for boats and marine engineering equipment in China, and has broad application prospects.

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Claims (8)

  1. Acier pour génie maritime, comprenant les éléments chimiques suivants en pourcentage massique :
    C : 0,01 à 0,05 %, Si : 0,05 à 0,60 %, Mn : 0,50 à 1,30 %, Cr : 0,6 à 1,20 %, Ni : 2,0 à 3,0 %, Al : 0,01 à 0,06 %, Ti : 0,005 à 0,012 %, et Mg : 0,0005 à 0,0015 % ; 0 < Ca ≤ 0,0045 %, 0 < Cu ≤ 0,5 % et 0 < Mo ≤ 0,40 % ; au moins l'un des éléments chimiques suivants : 0 < Nb ≤ 0,04 %, 0 < V ≤ 0,05 %, et 0 < B ≤ 0,0005 %, et le reste étant du Fe et des impuretés inévitables, dans lequel dans les impuretés inévitables, P ≤ 0,015 %, et/ou S ≤ 0,0040 %,
    dans lequel l'acier présente une microstructure de bainite revenue avec un rapport de phase de 95 % ou plus et la taille de grain d'austénite est de 20 à 25 µm.
  2. Acier pour génie maritime selon la revendication 1, dans lequel les pourcentages massiques des éléments chimiques sont les suivants :
    C : 0,015 à 0,04 %, Si : 0,15 à 0,60 % ; Mn : 0,50 à 1,30 %, Cr : 0,6 à 0,90 %, Ni : 2,0 à 2,85 %, Al : 0,01 à 0,06 %, Ti : 0,005 à 0,012 %, et Mg : 0,0005 à 0,0015 % ; 0 < Ca ≤ 0,0045 %, 0 < Cu ≤ 0,5 % et 0 < Mo ≤ 0,40 % ; et le reste étant du Fe et des impuretés inévitables.
  3. Acier pour génie maritime selon la revendication 1 ou 2, dans lequel les pourcentages massiques des éléments chimiques satisfont en outre au moins l'une des relations suivantes :
    1 , 8 ≤ α ≤ 2 , 0 , dans lequel α = 1,2 Cr + 5 Ni - Cr2 - Ni2 - 4,61 ; et
    35 ≤ γ ≤ 65 , dans lequel γ = 10 Si + 30 Mo + 57 Cu
  4. Acier pour génie maritime selon la revendication 1 ou 2, dans lequel les pourcentages massiques des éléments chimiques satisfont en outre : 4,2 ≤ β ≤ 7,9, dans lequel β = 40 Al + 60 Ti + 20 Nb + V + Ti .
  5. Acier pour génie maritime selon la revendication 1 ou 2, dans lequel l'acier présente une limite d'élasticité de 355 MPa ou plus, une résistance à la traction de 500 à 650 MPa, un taux d'allongement de 22 % ou plus, une énergie d'impact à -60 °C de 100 J ou plus, un CTOD à -60 °C de 0,8 mm ou plus, une NDTT de -65 °C ou moins et un taux de corrosion dans un environnement atmosphérique très humide et chaud de 0,85 g/(m2*h) ou moins.
  6. Procédé de fabrication de l'acier pour génie maritime selon l'une des revendications 1 à 5, comprenant les étapes suivantes :
    (1) une fusion et une coulée continue ;
    (2) un chauffage de telle sorte qu'une température de chauffage de brame Th satisfasse T h = 1150 + 600 C + 120 Nb + Ti + V avec une unité étant °C ;
    (3) un laminage commandé de telle sorte que la température de laminage initiale Tsr satisfasse Tsr = 0,92 Th - 0,96 Th, avec une unité étant °C, qu'une température de laminage finale Tfr satisfasse T fr = 1100 − 199 C − 98 Mn − 42 Ni − 21 Cr , avec une unité étant °C, qu'une réduction de laminage en une seule passe soit de 8 à 12 % et qu'une réduction de laminage cumulée soit de 60 % ou plus, de sorte qu'une taille de grain d'austénite d'origine après laminage soit de 20 à 25 µm ;
    (4) un refroidissement à l'air ; et
    (5) une trempe et un revenu de telle sorte qu'une température de trempe Tq satisfasse T q = 955 − 11 C − 14 Mn − 17 Cr + 16 Mo avec une unité étant °C, de sorte qu'une taille de grain d'austénite après trempe soit de 20 à 25 µm et qu'une température de revenu Tt satisfasse T t = 710 − 203 C − 15 , 2 Ni + 44 , 7 Si + 104 V + 31 , 5 Mo avec une unité étant °C.
  7. Procédé de fabrication selon la revendication 6, dans lequel, à l'étape (1), un prétraitement de métal à chaud, une fusion de convertisseur, un affinage LF, un affinage RH, un traitement bénéfique d'inclusions et une coulée continue sont réalisés successivement, dans lequel, au stade du traitement bénéfique d'inclusions, des inclusions composites d'une taille de 0,2 à 2,5 µm sont formées, et l'inclusion composite comprend du MgO+Al2O3 revêtu de CaS et de MnS en tant que noyau et un certain nombre d'inclusions composites dans la plage de taille représentant 95 % ou plus d'un nombre total d'inclusions.
  8. Procédé de fabrication selon la revendication 7, dans lequel, à l'étape (1), au stade de la fusion de convertisseur, une coulée de coupure de laitier est réalisée, avec une épaisseur d'une couche de laitier contrôlée pour être inférieure à 30 mm ; au stade de l'affinage LF, une somme des pourcentages massiques de FeO et de MnO dans le laitier est contrôlée pour être inférieure à 1 %, et une formule est satisfaite : (CaO + MgO + MnO)/(SiO2 + P2O5) > 9, dans la formule, chaque substance représente ses pourcentages massiques correspondants ; au stade du traitement bénéfique d'inclusions, un traitement par Mg ou un traitement composite par Mg et Ca est réalisé ; et lorsque le traitement composite par Mg et Ca est réalisé, le Ca et le Mg sont introduits en même temps avec une vitesse d'introduction de fil de 150 à 250 m/min.
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EP4261310A4 (fr) 2024-11-06
JP2024502849A (ja) 2024-01-23
JP7671355B2 (ja) 2025-05-01
SA523441577B1 (ar) 2024-11-11
KR20230113793A (ko) 2023-08-01
CN114763593A (zh) 2022-07-19
EP4261310A1 (fr) 2023-10-18
KR102898550B1 (ko) 2025-12-10
CN114763593B (zh) 2023-03-14

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