WO2022011935A1 - 一种具有优良心部韧性的高强度容器用厚板及制造方法 - Google Patents

一种具有优良心部韧性的高强度容器用厚板及制造方法 Download PDF

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WO2022011935A1
WO2022011935A1 PCT/CN2020/133464 CN2020133464W WO2022011935A1 WO 2022011935 A1 WO2022011935 A1 WO 2022011935A1 CN 2020133464 W CN2020133464 W CN 2020133464W WO 2022011935 A1 WO2022011935 A1 WO 2022011935A1
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strength
thick plate
excellent core
rolling
temperature
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PCT/CN2020/133464
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English (en)
French (fr)
Chinese (zh)
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谢章龙
吴俊平
席连云
方磊
李庆春
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南京钢铁股份有限公司
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Priority to KR1020237004339A priority Critical patent/KR20230037040A/ko
Publication of WO2022011935A1 publication Critical patent/WO2022011935A1/zh

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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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/001—Heat treatment of ferrous alloys containing 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • 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
    • C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
    • 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
    • C22C38/04—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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C21D2211/009—Pearlite

Definitions

  • the invention relates to the technical field of iron and steel production, in particular to a thick plate for high-strength containers with excellent core toughness and a manufacturing method.
  • the Chinese invention patent with publication number CN104911319B proposes a steel plate for low-temperature spherical tank containers and a production method thereof, using Nb microalloying, two-stage controlled rolling, quenching + tempering or normalizing + quenching + tempering process heat treatment,
  • the 1/2 thickness impact can be used at -70°C, but the yield strength of the thick plate is about 400MPa, and the tensile strength is less than 560MPa.
  • the present invention provides a high-strength container thick plate with excellent core toughness, and its chemical composition and mass percentage are as follows: C: 0.08%-0.12%, Si: 0.10%-0.30%, Mn: 1.10% ⁇ 1.50%, Ni: 0.50% ⁇ 0.80%, Mo: 0.08% ⁇ 0.15%, V: 0.03% ⁇ 0.06%, P ⁇ 0.006%, S ⁇ 0.002%, the balance is Fe and inevitable impurities.
  • the full-thickness low-temperature impact toughness of the product of the present invention meets the requirements for use at -70°C, and on the basis of the existing 0.5Ni low-temperature steel, the yield strength and tensile strength are greatly improved, and material properties are upgraded.
  • the chemical composition and mass percentage of the aforementioned thick plate for high-strength containers with excellent core toughness are as follows: C: 0.08%-0.09%, Si: 0.10%-0.21%, Mn: 1.10%-1.45% , Ni: 0.50% ⁇ 0.62%, Mo: 0.08% ⁇ 0.10%, V: 0.03% ⁇ 0.037%, P ⁇ 0.006%, S ⁇ 0.0005%, the balance is Fe and inevitable impurities.
  • the chemical composition and mass percentage of the aforementioned thick plate for high-strength containers with excellent core toughness are as follows: C: 0.10%-0.11%, Si: 0.14%-0.20%, Mn: 1.18%-1.37% , Ni: 0.50% ⁇ 0.74%, Mo: 0.096% ⁇ 0.12%, V: 0.039% ⁇ 0.047%, P ⁇ 0.005%, S ⁇ 0.001%, the balance is Fe and inevitable impurities.
  • the aforementioned thick plate for high-strength containers with excellent core toughness has a thickness of 50-80 mm.
  • Another object of the present invention is to provide a method for manufacturing a high-strength thick plate for a container with excellent core toughness, comprising:
  • the slab is heated to 1150 ⁇ 1180°C, the total time of the slab in the furnace is ⁇ 240min, the holding time of the soaking section is 30 ⁇ 60min, and the temperature uniformity of the whole slab is ⁇ 10°C;
  • Controlled rolling and controlled cooling After the slab is released from the furnace, high-pressure water is used for descaling, and the descaling water pressure is ⁇ 18MPa. Two-stage controlled rolling is adopted. The first stage is rolled in the austenite recrystallization zone, and the second stage is rolled in the austenite unprocessed Finish rolling in the recrystallization zone, and control cooling after rolling;
  • Heat treatment adopt off-line quenching + tempering process for heat treatment.
  • the aforementioned method for manufacturing a high-strength container thick plate with excellent core toughness, steelmaking and continuous casting pretreatment of molten iron, S content in molten iron ⁇ 0.002wt%, converter steelmaking, deep deoxidation in LF furnace and desulfurization, adjust the alloy composition to reach the target range, degas the RH furnace, vacuum degree ⁇ 0.3torr; adopt the second cold water weak cooling, low drawing speed scheme for continuous casting, the drawing speed is 0.8 ⁇ 1.2m/min, the thickness of the continuous casting billet It is 260mm, and the casting billet is subjected to stack cooling treatment, and the stack cooling time is ⁇ 48 hours.
  • the aforementioned method for manufacturing a high-strength container thick plate with excellent core toughness adopts two-stage controlled rolling: the first stage is rolling in the austenite recrystallization zone, and the total reduction is 30% ⁇ 50%; in the second stage, finish rolling is carried out in the austenite unrecrystallized area, the rolling temperature is lower than 850 °C, the reduction is 45% to 65%, and the final rolling temperature is 780 to 820 °C; after rolling, controlled cooling, The temperature of returning to red is controlled between 580 and 620 °C.
  • the heat treatment adopts off-line quenching: the quenching temperature is 870-890 ° C, the holding time is 30-60 minutes, and the maximum cooling capacity of the equipment is used to directly quench to room temperature.
  • the above-mentioned manufacturing method of a high-strength container thick plate with excellent core toughness, tempering the quenched steel plate is heated to 605-625 ° C, tempered for 40-70 minutes, and air-cooled to obtain uniform and fine tempered Soxhlet body tissue.
  • Ni It can form ⁇ and ⁇ phase solid solutions with Fe, and can be infinitely dissolved in the ⁇ phase. It can expand the ⁇ phase region. It is austenite forming and stabilizing element, making the screw dislocation difficult to decompose and ensuring cross slip. Ni is also a precious metal element and should be added as little as possible under the premise of ensuring performance;
  • Mn It is an austenite stabilizing element and a matrix strengthening element. It can improve the strength through solid solution strengthening and precipitation strengthening, and significantly improve the hardenability of the material. Mn element is prone to core segregation during continuous casting, so it should not be too high;
  • Si a deoxidizing element, which can inhibit the segregation of P at the grain boundary, but too high Si content is not conducive to the low temperature toughness of the welding heat affected zone (HAZ);
  • S and P S is easy to form precipitate MnS with Mn, which reduces the low temperature toughness; P is easy to segregate at the grain boundary, which reduces the crack growth resistance of the grain boundary and deteriorates the low temperature toughness;
  • Mo It can improve the hardenability, thereby improving the strength and the tempering stability of the steel. When coexisting with chromium or manganese, it can reduce or suppress the tempering brittleness caused by other elements;
  • V It can improve the hardenability and is a strong carbonitride forming element. It can improve the material strength through solid solution and precipitation. When V coexists with Cr and Mo, complex carbonization will be formed during the tempering process. In order to ensure the plastic toughness, the amount of V must be controlled, and the grain refinement effect of V and its beneficial effect on strength are considered;
  • the thickness of the high-strength container plate for low temperature prepared by the present invention is 50-80 mm, the thickness of 1/4 and the KV 2 value of the core part under the condition of -70 ° C is ⁇ 150 J, the yield strength is ⁇ 420 MPa, and the tensile strength is ⁇ 560 MPa;
  • the product of the present invention can replace 0.5Ni steel grades at home and abroad such as 09MnNiDR, and is used for the construction of containers such as propane, butane, ethane and ethylene, realizes material performance upgrade, and provides material guarantee for the large-scale development of containers.
  • Fig. 1 is the 1/4 thickness tempered microstructure photo of 80mm steel plate corroded with 4% nitric acid alcohol solution in Example 1;
  • FIG. 1 is a photo of the tempered microstructure of an 80mm steel plate with a thickness of 1/2 etched with a 4% nitric acid alcohol solution in Example 1.
  • the following examples provide a high-strength container thick plate with excellent core toughness and its manufacturing method.
  • the chemical composition is shown in Table 1, the smelting and rolling process parameters are shown in Table 2, and the heat treatment process parameters are shown in Table 3.
  • the specific steps are:
  • Steelmaking and continuous casting pretreatment of molten iron, S content in molten iron ⁇ 0.002wt%, converter steelmaking, deep deoxidation and desulfurization in LF furnace, adjusting alloy composition to reach the target range, degassing in RH furnace, vacuum degree ⁇ 0.3torr;
  • Continuous casting is carried out with the second cold water weak cooling and low drawing speed scheme, the drawing speed is 0.8 ⁇ 1.2m/min, the thickness of the continuous casting billet is 260mm, and the casting billet is subjected to stack cooling treatment, and the stack cooling time is ⁇ 48 hours;
  • the slab is heated to 1150 ⁇ 1180°C, the total time of the slab in the furnace is ⁇ 240min, the holding time of the soaking section is 30 ⁇ 60min, and the temperature uniformity of the whole slab is ⁇ 10°C;
  • Two-stage controlled rolling is adopted: the first stage is rolled in the austenite recrystallization zone, and the total reduction is 30% to 50%; the second stage is finish rolling in the austenite unrecrystallized zone, and the rolling temperature is low At 850 °C, the reduction is 45% to 65%, and the final rolling temperature is 780 to 820 °C; after rolling, the cooling is controlled, and the red temperature is controlled between 580 to 620 °C;
  • the heat treatment adopts off-line quenching: the quenching temperature is 870 ⁇ 890°C, the holding time is 30 ⁇ 60min, and the maximum cooling capacity of the equipment is used to directly quench to room temperature after being released;
  • Tempering The quenched steel plate is heated to 605 ⁇ 625°C, tempered for 40 ⁇ 70min and air cooled to obtain a uniform and fine tempered sorbite structure.
  • Example 1 0.09 1.45 0.21 0.0005 0.006 0.62 0.08 0.037
  • Example 2 0.10 1.37 0.20 0.0006 0.005 0.50 0.096 0.039
  • Example 3 0.11 1.18 0.14 0.0010 0.004 0.74 0.12 0.047
  • the structure obtained by the product of the present invention is a tempered sorbite structure, and good comprehensive mechanical properties can be obtained.
  • the maximum thickness is up to 80mm, which meets the requirements of high-strength and low-temperature container plates used at -70°C.
  • the KV 2 value of 1/4 thickness and the core at -70°C is greater than or equal to 150J, the yield strength is greater than or equal to 420MPa, and the tensile strength is greater than or equal to 560MPa.
  • Ni low temperature steel On the basis of Ni low temperature steel, the yield strength and tensile strength are greatly improved, and it can replace 0.5Ni steel grades at home and abroad such as 09MnNiDR for the construction of propane, butane, ethane and ethylene containers, and realize material performance upgrade. Provide material guarantee for chemical development.

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PCT/CN2020/133464 2020-07-17 2020-12-02 一种具有优良心部韧性的高强度容器用厚板及制造方法 WO2022011935A1 (zh)

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CN114875309A (zh) * 2022-04-08 2022-08-09 鞍钢股份有限公司 一种厚规格高强度核反应堆安全壳用钢及其制造方法
CN115094331A (zh) * 2022-07-18 2022-09-23 柳州钢铁股份有限公司 一种低成本的q690钢板及其生产方法
CN115125380A (zh) * 2022-06-24 2022-09-30 舞阳钢铁有限责任公司 台车炉与连续炉配合高效加热轧制合金钢的方法
CN115181911A (zh) * 2022-08-04 2022-10-14 江苏省沙钢钢铁研究院有限公司 特厚Q500qE桥梁钢板及其生产方法
CN115433873A (zh) * 2022-08-31 2022-12-06 鞍钢股份有限公司 一种经济型且强韧性优异的e级球扁钢及其生产方法

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CN115216589A (zh) * 2022-07-28 2022-10-21 湖南华菱湘潭钢铁有限公司 一种改善大厚度高强海洋工程用钢心部韧性的热处理方法

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CN111020409A (zh) * 2019-12-31 2020-04-17 苏州雷格姆海洋石油设备科技有限公司 一种高强度微合金钢、水下油气管线快速连接器及制造方法
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114875309A (zh) * 2022-04-08 2022-08-09 鞍钢股份有限公司 一种厚规格高强度核反应堆安全壳用钢及其制造方法
CN115125380A (zh) * 2022-06-24 2022-09-30 舞阳钢铁有限责任公司 台车炉与连续炉配合高效加热轧制合金钢的方法
CN115125380B (zh) * 2022-06-24 2023-08-22 舞阳钢铁有限责任公司 台车炉与连续炉配合高效加热轧制合金钢的方法
CN115094331A (zh) * 2022-07-18 2022-09-23 柳州钢铁股份有限公司 一种低成本的q690钢板及其生产方法
CN115181911A (zh) * 2022-08-04 2022-10-14 江苏省沙钢钢铁研究院有限公司 特厚Q500qE桥梁钢板及其生产方法
CN115181911B (zh) * 2022-08-04 2023-05-05 江苏省沙钢钢铁研究院有限公司 特厚Q500qE桥梁钢板及其生产方法
CN115433873A (zh) * 2022-08-31 2022-12-06 鞍钢股份有限公司 一种经济型且强韧性优异的e级球扁钢及其生产方法
CN115433873B (zh) * 2022-08-31 2024-04-19 鞍钢股份有限公司 一种经济型且强韧性优异的e级球扁钢及其生产方法

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