CN115261714A - Steel for pressure container and preparation method thereof - Google Patents

Steel for pressure container and preparation method thereof Download PDF

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Publication number
CN115261714A
CN115261714A CN202110472944.9A CN202110472944A CN115261714A CN 115261714 A CN115261714 A CN 115261714A CN 202110472944 A CN202110472944 A CN 202110472944A CN 115261714 A CN115261714 A CN 115261714A
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steel
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pressure vessels
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王宪军
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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
    • 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
    • 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
    • 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
    • C22C38/002—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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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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 discloses steel for a pressure container, which comprises the following chemical components in percentage by mass: c:0.12 to 0.20%, si:0.30 to 0.85%, mn: 1.10-1.80%, P is less than or equal to 0.012%, S is less than or equal to 0.011%, al: 0.015-0.035%, V:0.075 to 0.13%, nb: 0.020-0.050%, N is less than or equal to 0.0045%, cu is less than or equal to 0.13%, sn is less than or equal to 0.002%, sb is less than or equal to 0.003%, and Mg:0.0008 to 0.010 percent. The invention also provides a preparation method of the steel for the pressure container, which comprises the following steps: smelting and casting; heating; rolling; thermoforming; and (6) heat treatment. The steel for the pressure container manufactured by the technical scheme of the invention can meet the requirements of high strength, light weight and high parameter, and the performance of the steel plate after hot forming is kept equivalent to that of the steel plate in a delivery state.

Description

Steel for pressure container and preparation method thereof
Technical Field
The invention belongs to the technical field of steel materials, and particularly relates to steel for a pressure container and a preparation method thereof.
Background
The mobile pressure vessels can be classified into car tankers, railway tankers, and road or marine tank containers. The main body of the movable pressure container is a tank body, the tank body is composed of a cylinder body and a sealing head, and the sealing head of the movable pressure container is manufactured by hot stamping and forming a steel plate. Before manufacturing and installing steel for pressure vessels used for large-scale fixed spherical storage tanks, movable pressure vessel cylinder sealing heads and the like, hot stamping forming is carried out on steel plates, and the steel plates are assembled into spherical tanks by tailor welding. The hot stamping process of the pressure container requires that the delivery steel plate has good hot processing manufacturability and has good strength and low-temperature toughness after hot forming, thereby ensuring the safe use of the pressure container in a service environment. At present, the steel plate for the container with the yield strength of 345MPa and 370MPa is generally adopted in the market to manufacture the hot forming pressure container, and under the condition of lower strength of the steel plate, the thicker tank body wall is needed to ensure the safety in the use process, so the comprehensive requirements of large-scale, high-strength thinning and light-weight and high parameter of the spherical tank or the movable container cannot be realized.
Although steel plates for container hot forming or other purposes of hot forming process exist in the prior art, good hot forming process parameters and performance requirements after forming cannot be met.
For example, chinese invention patent CN201810557074.3 discloses a pressure vessel end enclosure steel plate for hydrogen sulfide environment and a thermal treatment method after thermal forming thereof, nb microalloying is adopted, which has the problem that excessive Al is added to the steel plate, and oversized alumina inclusions are formed in the finished steel plate, so that micro cracks are easily formed inside the steel plate when the steel plate is subjected to a thermal forming process, and the safety of the vessel steel under a long-term service condition is seriously affected; and the steel plate is subjected to the production process of normalizing and tempering and then the hot forming process, so that the production cost and the energy consumption of the steel plate are increased.
China invention patent CN201410110348.6 describes a high fatigue strength hot forming heavy truck axle housing steel plate and a manufacturing method thereof, and the Nb-V alloy design is adopted to refine grains and strengthen toughness. The hot rolled steel sheet is directly subjected to a hot forming process after hot rolling without a subsequent heat treatment process, and therefore, the hot rolled steel sheet after hot forming cannot be used for safely manufacturing pressure vessel parts.
The Chinese patent of invention CN201710695540.X describes a hot-formed high-strength steel and a processing method thereof, the hot-formed high-strength steel is used for manufacturing automobile high-strength steel, the defects of low fatigue strength and poor impact toughness of cold-formed materials are overcome, a Cr-Nb-Ti-Al alloy system is adopted, the supply state is a hot rolling state or a cold rolling state, after hot stamping, the yield strength of processed parts is uniform, the deformation is uniform, the service bearing capacity of the parts is improved, but the requirements of large-scale, high-strength thinning and light-weight, high parameter and the like of spherical tanks or moving containers cannot be met.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a steel for a pressure vessel and a method for manufacturing the same, so as to solve the problems that the steel for a pressure vessel in the prior art cannot meet the comprehensive requirements of large-scale spherical tank or movable vessel, high strength, thin, lightweight and high parameter, and cannot achieve good thermal formability during the vessel manufacturing process. When the high-strength steel for the pressure container is used for the hot forming process, in order to ensure that the hot forming process is carried out smoothly and the shape and the performance of the formed steel plate meet the use requirements at the same time, the steel for the pressure container can be finely controlled from the aspects of the components of the steel plate, the preparation process of the steel plate, the parameter design and the like, so that the steel for the pressure container can achieve the purposes of qualified manufacture of finished products from the smooth production of factories to downstream users and finally safe use of the products. The steel for the pressure vessel manufactured by the technical scheme of the invention can meet the requirements of high strength, light weight and high parameter of the vessel steel, and the performance of the steel plate after hot forming is kept equivalent to that of the steel plate in a delivery state. According to the invention, the steel for the pressure container is prepared by accurately controlling the chemical components in the steel in the production process of the steel plate, and has good comprehensive mechanical properties: the yield strength is more than or equal to 420MPa, the tensile strength is 570-710 MPa, the elongation is more than or equal to 25 percent, and the steel plate is transversely arranged at minus 60 ℃ and KV2185J or more, the NDTT transition temperature of a welding heat affected zone is less than or equal to minus 75 ℃, the metallographic structure is ferrite and pearlite, the ferrite and the pearlite are uniformly distributed, the volume percent of the ferrite is 63-72%, the volume percent of the pearlite is 28-37%, and the grain size of the ferrite reaches 10-12.5 grades.
In order to achieve the object of the invention, in one aspect, the invention provides steel for a pressure vessel, which comprises the following chemical components in percentage by mass:
C：0.12～0.20％、Si：0.30～0.85％、Mn：1.10～1.80％、P≤0.012％、S≤0.011％、Al：0.015～0.035％、V：0.075～0.13％，Nb：0.020～0.050％，N≤0.0045％，Cu≤0.13％，Sn≤0.002％，Sb≤0.003％，Mg：0.0008～0.010％。
in the chemical composition design of the steel for the pressure container, a new steel grade is designed by adopting a V-Nb alloy system, and on one hand, the obdurability of a VC precipitated phase is utilized, so that the effects of grain refinement and precipitation strengthening of V microalloy are improved; on the other hand, nbC precipitated phase is used for further refining grains, so that the low-temperature fracture toughness of the steel is improved, and the ductile-brittle transition temperature is reduced. Meanwhile, the contents of Cu, sn, sb and other elements in the steel are controlled, and the single or composite action of the elements is prevented from damaging the toughness of the steel, because the elements can generate a segregation action in a continuous casting process and a hot forming process cooling process, particularly in the process of cooling the steel from high temperature to low temperature (cooling from 980 ℃ to 700 ℃), so that hot cracks are generated in the process of cooling the continuous casting billet from solidification to low temperature or hot forming deformation.
In the steel for a pressure vessel of the present invention, the design principle of each chemical element is as follows:
c: in the steel for a pressure vessel of the present invention, C is one of the elements essential for improving the strength of the steel material in the steel. Fe in steel grade along with the increase of C element content in steel3C increases, hardenability also increases, the yield strength and tensile strength of the steel increases, and the elongation notch impact toughness decreases. Wherein, the tensile strength is improved by about 90MPa and the yield strength is improved by about 40-50MPa when the content of the C element in the steel is increased by 0.1 percent. However, it should be noted that as the content of C element in the steel increases, the elongation and impact toughness of the steel decrease, and particularly the low temperature toughness decreases to a greater extent. Furthermore, when a steel material having a high C content is welded, hardening occurs in the weld heat affected zone, which increases the tendency of the steel material to cold crack during welding. Therefore, examineConsidering the influence of the element C on the performance of the steel for the pressure container, the mass percent of the element C is controlled to be 0.12-0.20%, so that the strength stability of the steel is ensured to be in a proper range, the steel is suitable for production operation, and the applicability and the feasibility of the steel in industrial production can be improved.
Si: in the steel for pressure vessels of the present invention, si reduces the graphitization tendency of carbon in the steel and increases the strength of the steel in the form of solid solution strengthening, and when the Si content is increased from 0.30% to 0.85%, the strength of the steel is substantially unchanged or slightly increased, while the toughness is greatly improved. Properly increasing the content of Si increases the volume fraction of ferrite in the structure and makes the crystal grains thinner, thereby being beneficial to improving the toughness of the steel; on the other hand, however, when the Si content is too high, siO is easily formed in the steel-making process2Therefore, the mass percentage of Si in the steel is controlled to be 0.30 to 0.85% in the present invention.
For example, the content of Si in the steel for a pressure vessel may be further limited to 0.37 to 0.75% by mass.
Mn: in the steel for a pressure vessel of the present invention, mn element has a significant effect on improving the strength of low-carbon and medium-carbon pearlite steels. The tensile strength of the steel can be improved by about 100MPa by adding 1% of Mn element into the steel. Generally, it is advantageous to improve the toughness of weld metal to control the mass percent of Mn element in steel to be less than 1.70%, and the Mn element content in low-carbon high-strength steel can reach up to 1.80%. In addition, mn also improves the solubility of Nb, V, etc. in steel. Therefore, in the present invention, the mass percentage of the Mn element is controlled to be 1.10 to 1.80%.
Illustratively, the content of Mn in the steel for a pressure vessel may be further limited to 1.40 to 1.75% by mass, and it is ensured that the low-temperature impact toughness and the elongation of the steel are not impaired when the tensile strength of the steel is appropriate.
Al, N: in the steel for the pressure container, al is added as a deoxidation balance element in a steelmaking process, the mass percent of Al in molten steel can be controlled within 0.035% in the early stage of refining, the oxygen content in the steel is low in the later stage of refining, if Al is added, large-size chain-shaped alumina inclusions can be formed in the molten steel, the low-temperature toughness of a finished steel plate is seriously damaged, and a large amount of AlN can be formed in the steel by adding Al in the later stage of refining, the AlN is easy to precipitate in the range of 800-950 ℃ of continuous casting billet cooling, the thermoplasticity of the continuous casting billet is reduced, and corner cracks or intercrystalline cracks can also be formed on the surface or corners of the continuous casting billet. N in steel is as small as possible as a residual element, and if the content of N in steel exceeds 0.0045%, N and Al form AlN in steel, which deteriorates the thermoplasticity of the cast steel slab. When the N content is controlled to be less than 0.0045%, alN is formed in the steel in a very small amount, and the thermoplasticity of the cast slab is not remarkably influenced. Therefore, in the present invention, the mass percent of the Al element is controlled to be 0.015 to 0.035%, and the mass percent of the N element is controlled to be within 0.0045%.
Illustratively, the content of Al in the steel for a pressure vessel may be further limited to 0.015 to 0.032% by mass.
V: in the steel for pressure vessels of the present invention, V is a strong carbonitride forming element which can improve the normal temperature and high temperature strength of the steel by forming carbides to prevent austenite grains from growing large to refine the grains. The element V not only promotes the formation of pearlite but also refines ferrite. In the case of normalized steels, V is often added together with N, and the precipitation of V (CN) by adding N achieves the effect of refining crystal grains during rolling and normalizing treatment. It should be noted that although the strength of steel can be greatly improved by adding V element to steel, the content of V element in steel should not be too high, and when the content of V element is too high, the number of precipitates increases, the size increases, and the toughness of steel decreases. In addition, addition of V element to steel causes Fe as cementite in steel3The C regular lamellar and the pearlite colony are separated by the V carbonitride precipitate, so that the cementite breakpoints in the pearlite lamellar are increased, the area of the pearlite colony is reduced, the pearlite colony positions are distributed in a staggered mode, the length of the pearlite lamellar is smaller, the pearlite lamellar is thinner, and the fragmentation degree is increased. Comprehensively considering various strengthening and toughening effects of the V element in the steel, the weight percentage of V in the steel for the pressure container is controlled to be 0.075-0.13% of the total weight of the composition.
For example, the content of V in the steel for a pressure vessel may be further limited to 0.075 to 0.12% by mass.
Nb: in the steel for pressure vessels of the present invention, nb can promote grain refinement of the rolled microstructure of the steel, and improve the strength and toughness of the steel. In the controlled rolling process, nb can effectively refine the microstructure by inhibiting austenite recrystallization and can reduce the overheating sensitivity and the temper brittleness of steel; in the welding process, segregation and precipitation of Nb can prevent austenite grains from coarsening during heating, and a fine heat affected zone structure is obtained after welding, so that the welding performance is improved. Therefore, in the steel for a pressure vessel of the present invention, the mass percentage of Nb is controlled to be 0.020 to 0.050%.
Illustratively, the content of Nb in the steel for a pressure vessel may be further limited to 0.024 to 0.043% by mass.
Cu: in the steel for the pressure container, the Cu element mainly plays a role in precipitation strengthening in the steel, so that the steel is favorable for obtaining good low-temperature toughness and improving the corrosion resistance of the steel. When the content of Cu element in steel is too high, not only toughness of a weld heat affected zone of a steel plate is reduced, but also a network crack is generated during rolling of the steel plate. Therefore, in the present invention, the mass percentage of the Cu element is controlled to be 0.13% or less.
For example, the Cu content in the steel for a pressure vessel may be further limited to 0.015 to 0.13% by mass.
P, S: in the steel for a pressure vessel of the present invention, P, S is an impurity element in the steel. The performance of the steel of the invention can be ensured only by smelting pure steel, so that the content of P, S in the steel must be controlled in a lower range. Based on this, in the steel for a pressure vessel of the present invention, the mass percentage of the P element is controlled to be 0.012% or less, and the mass percentage of the S element is controlled to be 0.011% or less.
For example, the content of P in the steel for a pressure vessel may be further limited to 0.0008 to 0.010% by mass. The content of P is not less than 0.0008 percent, which is mainly used for ensuring the operability of the steel in the steelmaking process control link and comprehensively considering the process cost and the steel plate performance.
Sn, sb: in the steel for the pressure container, sn and Sb are residual impurity elements in the steel, and the elements can form a low-melting-point enrichment phase in the steel in the processes of casting blank solidification and cooling, casting blank heating, rolling and steel plate hot forming, so that cracks and hot brittleness on the surface of the steel and defects on the surface of the steel or in the metallurgical quality are easily caused. In the invention, the mass percentage of Sn and Sb is controlled within 0.002 percent and 0.003 percent respectively.
Mg: in the steel for a pressure vessel of the present invention, mg can be used for desulfurization in the refining of molten steel due to its affinity for S element. The sulfide inclusions easily cause steel to form a defective structure, mg can refine the sizes of the inclusions in the steel, and the fine inclusions are uniformly distributed, so that the metallurgical quality and the low-temperature impact resistance of the steel are improved. In the invention, the Mg is matched with the Al, so that the effect of deoxidizing the molten steel in steelmaking can be achieved, and the Mg can ensure that a deoxidation product Al of the Al remained in the steel2O3Is finely dispersed in the steel, and is not easy to form aggregated alumina inclusions. In the invention, the mass percentage of Mg is controlled to be 0.0008-0.010%.
Further, the balance of Fe and inevitable impurities is contained in the steel for a pressure vessel.
Furthermore, in the steel for the pressure vessel, the mass percentage of the single chemical element in the steel can be controlled to be less than or equal to 0.15 of Cu +6 (Sn + Sb) at the same time; 0.90 < 4Mg/3S < 10; one of three relations that Mg/Al is more than 0.05 and less than 0.49, wherein the elements are substituted into the numerical value before the percentage content of the mass percent of the element. Cu, sb and Sn, which are singly or simultaneously present in the steel, cause surface cracks and hot brittleness of the steel, and the quantitative analysis of the combined action of the elements is difficult, wherein Cu is used as a reference substance for measuring the hot brittleness, so that the severity of the hot brittleness defect of the steel caused by residual elements in the steel can be more accurately evaluated.
In the steel for a pressure vessel of the present invention, it is also possible to control the elements in the steel to satisfy the relation of 0.90 < 4Mg/3S < 10. In the limited relation, 4Mg/3S is more than 0.90, the Mg added into the steel is ensured to be the minimum content, and the residual element S in the steel is ensured to be reduced to the minimum value; and 4Mg/3S is less than 10, so that the harmful influence of the residual elements on the steel performance can be effectively reduced by Mg added into the steel, the S does not form large-quantity inclusion in the steel, and the metallurgical quality and the low-temperature impact resistance of the steel are improved.
In the steel for a pressure vessel of the present invention, the elements in the steel sheet may be controlled so as to satisfy the relation of 0.05 < Mg/Al < 0.49. In the limited relation, mg/Al is more than 0.05, so that the minimum addition of Al in the steel is ensured, the aluminum can play a good deoxidation effect, and the total oxygen content in the steel is reduced to the minimum; and the Mg/Al ratio is less than 0.49, so that deoxidation products of Mg and Al added in the steel, such as alumina and the like, can be ensured to form fine beneficial inclusions, and the metallurgical quality and the low-temperature impact resistance of the steel are further improved.
Furthermore, the metallographic structure of the steel for the pressure container is ferrite and pearlite, the ferrite and the pearlite are uniformly distributed, the volume percentage range of the ferrite is 63% -72%, the volume percentage of the pearlite is 28% -37%, and the grain size of the ferrite reaches 10-12.5 levels.
Furthermore, the yield strength of the steel for the pressure container is more than or equal to 420MPa, the tensile strength is 570-710 MPa, the elongation is more than or equal to 25 percent, and the steel plate is transversely KV at 60 ℃ below zero2More than or equal to 185J, and the NDTT transition temperature of a welding heat affected zone is less than or equal to-75 ℃.
On the other hand, the invention also provides a manufacturing method of the steel for the pressure container, and the steel for the pressure container obtained by the manufacturing method has high strength, good hot forming capability, welding cold and hot crack resistance, good welding manufacturability and good welding performance.
In order to achieve the above object, the present invention provides a method for producing the steel for a pressure vessel, comprising the steps of:
smelting and casting;
heating;
rolling;
thermoforming;
and (6) heat treatment.
In the invention, after the hot forming process, the formed steel plate may have the phenomena of uneven ferrite grain size and higher internal stress, and the subsequent heat treatment process can obviously improve the ferrite grain uniformity of the previous process and reduce the internal stress of the steel plate, thereby ensuring that the steel plate has good material uniformity and stability after being manufactured into a pressure container finished product, and simultaneously eliminating the internal stress in the welding process, so that the steel plate and a welding joint have better performance uniformity, and the safety and the stability of the pressure container in service can be effectively improved.
Further, in the casting step, the dynamic soft reduction of the casting blank in the continuous casting secondary cooling water area is controlled to be 0.5-2%, the heavy reduction of the casting blank in the continuous casting secondary cooling water area is controlled to be 4-7%, and the ferrite grain size range of the obtained continuous casting blank is in the range of 90-215 μm.
In the manufacturing method of the steel for the pressure container, in the smelting and casting processes, vanadium-niobium microalloying can be realized through converter smelting, then ladle furnace deep desulphurization is carried out (S is less than or equal to 0.011 percent), gas inclusions are removed through vacuum, the dynamic soft reduction of a casting blank in a continuous casting secondary cooling water area is controlled to be 0.5-2 percent, then a cumulative weight reduction parameter is adopted to control the continuous casting blank, the reduction is 4-7 percent, and the ferrite grain size range of the continuous casting blank is controlled to be within the range of 90-215 mu m. The operation can not only ensure the stable formation of the continuous casting surface layer blank shell of the continuous casting blank, but also ensure that the continuous casting blank reaching the solidifying point from the surface layer to the core part further reduces the center segregation and the looseness of the continuous casting blank through certain reduction, thereby improving the homogeneity and the density of the continuous casting blank and further improving the metallurgical quality of the continuous casting blank.
Further, in the manufacturing method of the steel for the pressure vessel, the heating temperature is controlled to 1150-1280 ℃ in the heating process, and the heating rate is 7-14 min/cm. The heating temperature is controlled to be 1150-1280 ℃, so that the energy conservation and the consumption reduction can be realized, and the austenite grain coarsening degree can be reduced under the condition of ensuring the full re-austenitization of the casting blank.
Further, in the manufacturing method of the steel for the pressure container, the rough rolling initial rolling temperature is controlled to be not lower than 1000 ℃, the finish rolling temperature is controlled to be 800-940 ℃, the final three-pass accumulated reduction rate is controlled to be not lower than 30%, the cooling speed is controlled to be 2.5-10 ℃/s, and the final cooling temperature is controlled to be 580-710 ℃ in the rolling process.
In the rolling process, a recrystallization controlled rolling technology can be adopted for rolling, namely the finish rolling temperature is controlled to be 800-940 ℃, and the rolling force is fully reduced. Under the condition of reasonably distributing the pass reduction rate, the deformed austenite is ensured to be recrystallized above the recrystallization temperature so as to ensure the grain refinement of the steel plate, and when the austenite is transformed to the ferrite, the ferrite grain refinement after the phase transformation is ensured by adopting rapid cooling (the cooling speed is 2.5 ℃/s-10 ℃/s), so that precipitates with enough quantity and proper size can be formed in the steel at the recrystallization temperature under the rapid cooling action, and the ferrite grains are further refined. It should be noted that the heat preservation process after controlled cooling has the functions of adjusting the size of the precipitated phase and improving the toughness of the material.
Further, in the manufacturing method of the steel for the pressure vessel, the steel plate is heated from room temperature in the hot forming process, and the heating rate is controlled within the range of 150 ℃/h-300 ℃/h in order to ensure that the steel plate is heated uniformly and slowly; the basis of selecting the parameters of the thermal forming and heat preservation temperature is that the steel plate is completely austenitized, crystal grains are not coarsened, and the small deformation resistance of the forming is ensured in the forming process, and the processing is easy, so the temperature is controlled to be 900-980 ℃ when the steel plate is heated to the heat preservation temperature; on the premise of ensuring a good hot forming process, comprehensively selecting the heat preservation time according to the size of the steel plate and the soaking time, so that the heat preservation time is set to be 20-75 min; the strain of hot forming ensures that the steel plate deforms uniformly without generating plastic instability, so the strain range of the steel plate deformation in the hot forming process is controlled to be 0.3-1.3 percent, and the strain rate of the steel plate deformation is controlled to be 1.5 multiplied by 10-1/s～8×10-1And s. The cooling rate after forming is controlled to 2 ℃/s to 6 ℃/s in order to ensure that the steel sheet structure after forming is still ferrite and pearlite. Become intoThe final temperature after molding is more than or equal to 70 ℃.
Further, the steel of the present invention is subjected to a heat treatment process after the hot forming process. The heat treatment process may be normalizing. The normalizing temperature is 850-950 ℃, and the proper heat treatment can eliminate the uneven deformation generated in the hot forming process and the internal stress of the formed steel plate. The heat preservation time is (5-25) min + t multiplied by 1min/mm, wherein t represents the plate thickness and the unit parameter is mm.
According to the invention, through accurately controlling chemical components in steel in the production process of the steel plate and controlling technological parameters of the secondary cooling water production stage of the continuous casting billet of the steel for the pressure container, the thermoplasticity of the continuous casting billet on the surface and inside of the casting billet is ensured, and the production of the continuous casting billet with defects is avoided. In the rolling step, the finish rolling temperature is controlled within the range of 800-940 ℃ so as to avoid edge cracking of the edge of the steel plate. When the heat preservation temperature in the hot forming process is in the range of 900-980 ℃, elements for reducing thermoplasticity such as Cu, sn, sb and the like contained in the steel are controlled, so that the reduction of high-temperature plasticity, surface cracks or hot brittleness of the steel plate in the hot forming process can be avoided.
Compared with the prior art, the invention can at least realize the following beneficial effects:
1) The steel for the pressure container adopts a medium-low C-Mn-V-Nb alloy system. The V-Nb alloy design can not only achieve the purposes of precipitation strengthening and ferrite grain refinement of V, nb carbonitride precipitated in the cooling process after rolling of a steel plate, but also play a role in inhibiting the growth of ferrite grains in a proper hot forming process and continuously play a precipitation strengthening role during heat treatment of a finished product; the strength and toughness of the steel can be further improved by controlling the contents of elements such as Cu, sn, sb and the like in the steel, and the hot brittleness of the steel and the cracking of a steel plate in the rolling process are avoided; mg and Al elements are utilized to form fine beneficial inclusions, so that the harmful influence on the performance of the steel is effectively reduced, and the metallurgical quality and the low-temperature impact resistance of the steel are improved.
2) The invention can lead the steel production factory to adopt the controlled rolling state steel plate to deliver to the downstream users by carrying out the heat treatment process after the hot forming process, thereby reducing the production cost of the steel production factory, and the steel production factory can further guide the downstream container equipment manufacturer to carry out finer material processing on the steel by combining the production process parameters and characteristics of the downstream pressure container equipment manufacturer, thereby achieving the material performance finally expected by the users, reducing the energy consumption of the upstream steel factory and the downstream pressure container manufacturer, and realizing the win-win effect of the steel factory and the downstream users.
3) The invention obtains the steel for the pressure container with excellent comprehensive mechanical property by comprehensively regulating and controlling the alloy components and the manufacturing process, the yield strength is more than or equal to 420MPa, the tensile strength is 570-710 MPa, the elongation is more than or equal to 25 percent, and the steel plate is transversely arranged at 60 ℃ below zero and KV2More than or equal to 185J, the NDTT transition temperature of a welding heat affected zone is less than or equal to-75 ℃, and the size of ferrite grains in the steel can be thinned by matching with a rolling and cooling control process and a heat treatment process, so that the steel plate with good hot forming capability, welding cold and hot crack resistance, good welding manufacturability and welding performance can be obtained, and the comprehensive requirements of large-scale, high-strength thinning and light-weight and high parameter of the spherical tank or the movable container can be met.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention may be realized and attained by the features particularly pointed out in the written description.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention.
FIG. 1 is a photograph showing the metallographic structure of a steel for a pressure vessel in example 3 of the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. While the invention will be described in conjunction with the preferred embodiments, it is not intended that features of the invention be limited to these embodiments. On the contrary, the invention is described in connection with the embodiments for the purpose of covering alternatives or modifications that may be extended based on the claims of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been left out of the description in order to avoid obscuring or obscuring the focus of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Examples 1 to 9 and comparative examples 1 to 4
A steel for a pressure vessel according to examples 1 to 9 of the present invention and comparative steel sheets according to comparative examples 1 to 4 were each manufactured by the following steps:
step 1: smelting and casting were carried out according to the chemical compositions shown in tables 1-1 and 1-2: vanadium microalloying is realized through converter smelting, nitrogen gas is blown at the bottom of a ladle furnace for heating, gas inclusions are removed in vacuum, the level of N content in steel is controlled to realize vanadium-nitrogen microalloying, the dynamic soft reduction of a casting blank in a secondary cooling water area of continuous casting is controlled to be 0.5-2%, then a continuous casting blank is controlled by accumulative weight reduction parameters, the reduction is 4-7%, and the ferrite grain size range of the casting blank is controlled to be within the range of 90-215 micrometers.
And 2, step: heating: the heating temperature is controlled to 1150-1280 ℃, and the heating rate is controlled to 7-14 min/cm.
And step 3: rolling: controlling the initial rolling temperature of rough rolling to be not lower than 1000 ℃, controlling the final rolling temperature of finish rolling to be 800-940 ℃, and controlling the cumulative reduction rate of the last three passes to be not lower than 30%; cooling after finishing controlled rolling, wherein the cooling speed is controlled to be 2.5-10 ℃/s, and the final cooling temperature is controlled to be 580-710 ℃.
And 4, step 4: thermoforming: starting from room temperature, heating at a rate of 150-300 ℃/h, heating to a holding temperature of 900-980 ℃, holding for 20-75 min, wherein the strain of steel plate deformation in the hot forming process is in a range of 0.3-1.3%, and the strain rate of steel plate deformation is 1.5 multiplied by 10-1/s～8×10-1And/s, the cooling rate after forming is 2-6 ℃/s, and the termination temperature after forming is more than or equal to 70 ℃.
And 5: normalizing: the heat treatment is carried out by adopting a normalizing process, the normalizing temperature is controlled to be 850-950 ℃, the heat preservation time is (5-25 minutes) + tx1 minute/mm, wherein t represents the plate thickness, and the unit parameter is mm.
It should be noted that the design of the chemical composition of the steels for pressure vessels of examples 1 to 9 and the related processes meet the design specifications of the present invention. The chemical composition design of the comparative steel sheets of comparative examples 1 to 4 and the related processes have parameters that do not satisfy the design requirements of the present invention.
Tables 1 to 1 and tables 1 to 2 show the mass percentages of the chemical elements of the steel for pressure vessels of examples 1 to 9 and the comparative steel sheets of comparative examples 1 to 4.
TABLE 1-1 (%, balance Fe and unavoidable impurities other than P, S)
Figure BDA0003046064570000101
Tables 1 to 2
Numbering Sn Sb Mg O 4Mg/3S Mg/Al Cu+6(Sn+Sb)
Example 1 0.0015 0.0018 0.001 0.0016 1.026 0.067 0.035
Example 2 0.0008 0.0005 0.0009 0.0012 1.000 0.053 0.130
Example 3 0.0015 0.0025 0.005 0.0017 9.524 0.167 0.104
Example 4 0.0007 0.0015 0.009 0.0015 6.000 0.45 0.143
Example 5 0.0005 0.0001 0.0068 0.0006 9.067 0.272 0.044
Example 6 0.0005 0.0003 0.0048 0.0010 5.333 0.253 0.065
Example 7 0.0018 0.0028 0.0076 0.0018 6.333 0.217 0.098
Example 8 0.0002 0.0015 0.0086 0.0007 8.821 0.478 0.110
Example 9 0.0006 0.0013 0.0078 0.0014 8.667 0.289 0.0914
Comparative example 1 0.0500 0.008 0 0.0025 0 0 0.398
Comparative example 2 0.0800 0.016 0 0.0018 0 0 0.656
Comparative example 3 0.0500 0.011 0 0.0016 0 0 0.376
Comparative example 4 0.0050 0.007 0 0.0007 0 0 0.122
Tables 2-1 and 2-2 show specific process parameters of the steels for pressure vessels of examples 1-9 and comparative examples 1-4.
TABLE 2-1
Figure BDA0003046064570000102
Figure BDA0003046064570000111
Tables 2 to 2
Figure BDA0003046064570000112
Tables 2 to 3
Figure BDA0003046064570000113
The finished steel products for pressure vessels of examples 1 to 9 and the comparative steel sheets of comparative examples 1 to 4 obtained through the above process steps were sampled, respectively, and observed and mechanically tested, and the observed results and the mechanically tested results are shown in table 3.
Table 3 shows the observation results and the mechanical property test results of the steels for pressure vessels of examples 1 to 9 and comparative examples 1 to 4. The yield strength, tensile strength and elongation in the tensile property are tested by GB/T228.1 part 1 of the metal material tensile test: room temperature Experimental method, ballistic work KV2The indexes are GB/T229 'metallic material Charpy pendulum impact test method', and the reference standard for metallographic structure evaluation in steel is GB/T6394 'method for determining average grain size of metal'.
TABLE 3
Figure BDA0003046064570000121
To further illustrate the good weldability and weldability of the steels for pressure vessels according to examples 1 to 9 given in the present invention, the steels according to examples 1 to 9 according to the present invention and the comparative steels according to comparative examples 1 to 4 were subjected to welding process tests, respectively, and the test results are shown in Table 4. The relevant welding process test conditions are as follows: controlling the welding line energy to be 17-40 kJ/cm, and the time t for reducing the temperature of a welding pool from 800 ℃ to 5008/5The cooling time is controlled within the range of 10 to 38 s.
Table 4 shows the mechanical properties of the welded joints of the steels for pressure vessels of examples 1 to 9 and comparative examples 1 to 4. In the tensile property, GB/T228.1 part 1 of the metal material tensile test is adopted for testing the tensile strength and the elongation percentage: room temperature Experimental method, impact Power KV2The indexes are tested by GB/T229 method for testing impact of metal material Charpy pendulum bob, and the test of weld heat affected zone non-plastic transition temperature (NDTT) is tested by GB/T6803 method for testing ferrite steel non-plastic transition temperature drop hammer. The highest hardness test of the welding joint adopts standard GB 4675.5 welding heat affected zone highest hardness testDegree test method.
TABLE 4
Figure BDA0003046064570000131
It can be seen from a combination of tables 3 and 4 that the steels for pressure vessels of examples 1 to 9 are significantly superior in overall mechanical properties to the comparative steel sheets of comparative examples 1 to 4. The steels of examples 1 to 9 for pressure vessels have not only excellent comprehensive mechanical properties and weld cold and hot crack resistance, but also good welding manufacturability and good welding performance.
Fig. 1 is a photograph showing the metallographic structure of the steel for a pressure vessel in example 3, and it can be seen that the metallographic structure of the steel for a pressure vessel in example 3 was ferrite + pearlite, and the ferrite grain size was 11 th order.
In conclusion, the steel for the pressure container provided by the invention is a steel for the pressure container with good hot formability and a medium-low C-Mn-V-Nb alloy system, and has excellent comprehensive mechanical properties: the yield strength is more than or equal to 420MPa, the tensile strength is 570-710 MPa, the elongation is more than or equal to 25 percent, and the steel plate is transversely arranged at minus 60 ℃ and KV2More than or equal to 185J, and the NDTT transition temperature of a welding heat affected zone is less than or equal to-75 ℃. The microstructure matrix of the steel for the pressure container is ferrite plus pearlite, wherein the volume percentage of the ferrite is 62-73%, and the grain size of the ferrite reaches 10-12.5 levels, so that the steel for the pressure container can effectively meet the engineering application requirements of the steel after the hot forming process.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more detailed description of the invention, taken in conjunction with the specific embodiments thereof, and that no limitation of the invention is intended thereby. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (16)

1. A steel for pressure vessels, characterized by comprising, in mass percent: c:0.12 to 0.20%, si:0.30 to 0.85%, mn: 1.10-1.80%, P is less than or equal to 0.012%, S is less than or equal to 0.011%, al: 0.015-0.035%, V:0.075 to 0.13%, nb: 0.020-0.050%, N is less than or equal to 0.0045%, cu is less than or equal to 0.13%, sn is less than or equal to 0.002%, sb is less than or equal to 0.003%, mg:0.0008 to 0.010 percent.
2. The steel for a pressure vessel according to claim 1, wherein the balance is Fe and inevitable impurities.
3. The steel for pressure vessels according to claim 1 or 2, wherein the content of the element in mass percent satisfies at least one of the following relationships:
cu +6 (Sn + Sb) is less than or equal to 0.15;0.90 < 4Mg/3S < 10; mg/Al is more than 0.05 and less than 0.49; the numerical values before the percentile of the particular element are substituted in the calculation.
4. The steel for pressure vessels according to claim 1 or 2, wherein the content of the Mn element is 1.40 to 1.75%.
5. The steel for pressure vessels according to claim 1 or 2, wherein the content of the Si element is 0.37 to 0.75%.
6. The steel for pressure vessels according to claim 1 or 2, wherein the content of the P element is 0.0008 to 0.010%.
7. The steel for pressure vessels according to claim 1 or 2, wherein the content of the V element is 0.075 to 0.12%.
8. The steel for pressure vessels according to claim 1 or 2, wherein the content of the Nb element is 0.024 to 0.043%.
9. The steel for the pressure vessel as claimed in claim 1 or 2, wherein the metallographic structure of the steel for the pressure vessel is ferrite + pearlite, the volume percentage of ferrite is 63-72%, the volume percentage of pearlite is 28-37%, and the grain size of ferrite is 10-12.5 grade.
10. The steel for pressure vessels according to claim 1 or 2, wherein the steel for pressure vessels has a yield strength of 420MPa or more, a tensile strength of 570-710 MPa, an elongation of 25% or more, and a steel plate KV at-60 ℃ in the transverse direction2More than or equal to 185J, and the NDTT transition temperature of a welding heat affected zone is less than or equal to-75 ℃.
11. A method for producing a steel for pressure vessels according to any one of claims 1 to 10, characterized by comprising the steps of:
smelting and casting;
heating;
rolling;
thermoforming;
and (6) heat treatment.
12. The method of manufacturing steel for a pressure vessel as claimed in claim 11, wherein in the casting step, the dynamic soft reduction of the cast slab in the secondary cooling water zone for continuous casting is controlled to be 0.5 to 2%, the heavy reduction of the cast slab in the secondary cooling water zone for continuous casting is controlled to be 4 to 7%, and the ferrite grain size of the obtained continuous cast slab is in the range of 90 to 215 μm.
13. The method for manufacturing steel for pressure vessels according to claim 11, wherein in the heating step, the heating temperature is controlled to 1150-1280 ℃ and the heating rate is 7-14 min/cm.
14. The method for preparing steel for pressure vessels according to claim 11, wherein in the rolling step, the rough rolling start temperature is controlled to be not less than 1000 ℃, the finish rolling temperature is controlled to be 800-940 ℃, the cumulative reduction rate of the last three passes is controlled to be not less than 30%, the cooling rate is controlled to be 2.5-10 ℃/s, and the finish cooling temperature is controlled to be 580-710 ℃.
15. The method for manufacturing steel for pressure vessels according to claim 11, wherein in the hot forming step, the heating rate is controlled to be 150 ℃/h to 300 ℃/h, the holding temperature is 900 ℃ to 980 ℃, and the strain amount of the steel plate during hot forming is 0.3% to 1.3%.
16. The method of producing steel for pressure vessels as claimed in claim 11, wherein in the heat treatment step, the normalizing temperature is 850 to 950 ℃ and the holding time is (5 to 25) min + t x 1min/mm, where t represents the plate thickness and the unit parameter is mm.
CN202110472944.9A 2021-04-29 2021-04-29 Steel for pressure container and preparation method thereof Pending CN115261714A (en)

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