WO2023093798A1 - Plaque d'acier laminée à froid à haute résistance pour revêtement d'émail double face et son procédé de fabrication - Google Patents

Plaque d'acier laminée à froid à haute résistance pour revêtement d'émail double face et son procédé de fabrication Download PDF

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WO2023093798A1
WO2023093798A1 PCT/CN2022/133985 CN2022133985W WO2023093798A1 WO 2023093798 A1 WO2023093798 A1 WO 2023093798A1 CN 2022133985 W CN2022133985 W CN 2022133985W WO 2023093798 A1 WO2023093798 A1 WO 2023093798A1
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steel plate
double
rolled steel
sided
strength cold
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PCT/CN2022/133985
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English (en)
Chinese (zh)
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魏娇
孙全社
曲李能
蒋小明
王俊凯
王金涛
王木
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宝山钢铁股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/46—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling metal immediately subsequent to continuous casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/46—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling metal immediately subsequent to continuous casting
    • B21B1/463—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling metal immediately subsequent to continuous casting in a continuous process, i.e. the cast not being cut before rolling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/58—Roll-force control; Roll-gap control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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    • C21D6/00—Heat treatment of ferrous alloys
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    • C21D7/00—Modifying the physical properties of iron or steel by deformation
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    • C21D7/00—Modifying the physical properties of iron or steel by deformation
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0242—Flattening; Dressing; Flexing
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    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—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
    • 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
    • C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
    • 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
    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • C—CHEMISTRY; METALLURGY
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
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    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/009—Pearlite

Definitions

  • the invention relates to a metal material and a manufacturing method thereof, in particular to a high-strength cold-rolled steel for a double-sided enamel inner container and a manufacturing method thereof.
  • the common manufacturing process of the enamel liner is as follows: the steel plate is stamped and rolled into an end cover and a barrel body, and then welded to form the bottom embryo of the liner, followed by pretreatment to remove surface residual oil and iron oxide scale and other impurities to obtain a surface suitable for enamelling, and finally carry out wet enamelling and high-temperature sintering to obtain a finished enamel inner container.
  • Steel plate is one of the key materials for making enamel liner. It not only determines the compressive strength of the whole liner, but also determines the enamel quality and service life of the whole liner to a large extent. Therefore, the market generally has higher performance requirements for steel for enamel inner tanks, which need to have higher yield strength, excellent formability, excellent weldability and enamelling performance.
  • the main concern is the strength of the steel plate.
  • the yield strength of the steel plate is above 350MPa, but there are still some shortcomings: these steel plates are mainly suitable for single-sided enamelling process, and cannot meet the double-sided enamelling process. The surface enamel is not scaled and exploded.
  • One of the objectives of the present invention is to provide a high-strength cold-rolled steel plate for double-sided enamelled inner tanks, which not only has high strength, good plasticity and excellent enamelling performance , which can also meet the requirements of double-sided enamelling.
  • the high-strength cold-rolled steel plate for the double-sided enamel inner tank has good comprehensive performance in forming, enamelling, welding and pressure resistance, especially excellent welding performance, excellent anti-scale explosion performance, adhesion performance and needle resistance. Pores, bubble defects and high strength after high-temperature enamelling, it is especially suitable for making double-sided enamel liners.
  • the present invention provides a kind of high-strength cold-rolled steel plate for double-sided enamel liner, which contains Fe and unavoidable impurities, and it also contains the following chemical elements in mass percentage:
  • the mass percentage of each chemical element is:
  • C, Mn and P elements are mainly used for strengthening, and an appropriate amount of Ti and B elements are added to appropriately increase the content of S elements, and alloy elements such as Cu, Cr, and Mg are also added auxiliary.
  • Ti and B elements are added to appropriately increase the content of S elements
  • alloy elements such as Cu, Cr, and Mg are also added auxiliary.
  • Ti, C, S, and N can form fine, dispersed second-phase particles, which not only help to improve the anti-scale explosion performance, but also can control During sintering, the ferrite grains grow up, which improves the high temperature softening ability of the steel plate.
  • an appropriate amount of B element can alleviate the secondary brittleness problem caused by P, and at the same time, it can further improve the scale explosion resistance and increase the high temperature strength of the steel plate.
  • C In the high-strength cold-rolled steel plate for double-sided enamelled inner tank according to the present invention, C is the most basic strengthening element. With the increase of the content of C element in the steel, the strength of the steel plate will also increase, but Plasticity and toughness will decrease accordingly.
  • Adding an appropriate amount of C element to the steel can not only ensure the basic strength of the steel plate, but also combine with the Ti element in the steel to form TiC particles, so that C can exist in the form of pearlite and TiC particles; correspondingly, the use of process control can
  • the formed TiC particles are uniformly and dispersedly distributed on the ferrite matrix, which can not only improve the strength of the steel plate through precipitation strengthening, but also serve as an effective hydrogen trap to improve the anti-scale explosion performance of the steel plate, and can also control the oxidation resistance of the steel plate during high-temperature sintering. Coarsening of tensite grains and growth of ferrite grains can effectively prevent the steel plate from softening after sintering.
  • the content of C element in the steel should not be too high.
  • the content of C element in the steel is too high, a large amount of pearlite will be formed in the steel, which will not only damage the formability of the steel plate, but also cause damage to the steel during firing. More CO gas is generated, and bubbles and pinhole defects are formed on the surface of the enamel. Therefore, in the high-strength cold-rolled steel plate for double-sided enamelled inner container of the present invention, the mass percentage of C element is controlled between 0.06-0.12%.
  • Si element can dissolve in ferrite and austenite, and improve the hardness and strength of steel, but if the content is too high, it will significantly reduce Plasticity and toughness of steel.
  • adding an appropriate amount of Si to the steel will not affect the adhesion of the steel plate, but when the content of Si in the steel is too high, a SiO 2 film will be formed on the surface of the steel plate when it is heated, which hinders the infiltration of the enamel on the steel plate and the second The chemical reaction between them reduces the adhesion strength between the steel plate and the enamel.
  • the mass percentage of Si is controlled to satisfy: 0 ⁇ Si ⁇ 0.08 %. In some embodiments, the mass percentage of Si is 0.005-0.08%.
  • Mn In the high-strength cold-rolled steel plate for double-sided enameled inner tanks of the present invention, Mn is a commonly used strengthening element, which can exist in a solid solution state and play a role in strengthening the ferrite matrix. At the same time, Mn element can also react with S element to form MnS, which can not only overcome the thermal embrittlement caused by sulfur, but also act as an effective hydrogen trap, playing an important role in the resistance to scale explosion. However, MnS is a strip-shaped inclusion, which will be detrimental to the transverse properties of the steel plate.
  • the mass percentage of Mn is controlled between 0.5-1.2%.
  • P In the high-strength cold-rolled steel plate for double-sided enamelled inner tank according to the present invention, adding an appropriate amount of P element in the steel can effectively improve the ability of the steel plate to resist scale explosion; in addition, P solid solution in ferrite can also increase strength and hardness of the steel plate; however, P segregation is serious, which not only increases the cold brittleness of steel, but also significantly reduces plasticity and toughness. Secondary processing brittleness. Therefore, in the high-strength cold-rolled steel plate for the double-sided enameled inner container of the present invention, the mass percentage of P element is controlled between 0.01-0.05%.
  • S In the high-strength cold-rolled steel plate for double-sided enamel inner tank according to the present invention, if the content of S element is increased appropriately, it can form complex inclusions with titanium and manganese, which plays a beneficial role in preventing scale explosion during enamelling; In the present invention, by reasonably controlling the matching amount and process, it is possible to further prevent these composite inclusions from being too large, otherwise affecting the scale explosion resistance and formability of the steel plate. Therefore, in order to realize the beneficial effect of S element in steel, in the high-strength cold-rolled steel plate for double-sided enameled inner container of the present invention, the mass percentage of S is controlled between 0.005-0.05%.
  • the Al element can not only play the role of deoxidation and grain refinement, but also fix the nitrogen in the steel and reduce the aging tendency of the steel. Improve the low temperature toughness of steel.
  • the content of Al element in the steel should not be too high. When the content of Al element in the steel is too high, it will bring difficulties in smelting and pouring. Based on this, in the high-strength cold-rolled steel plate for the double-sided enameled inner container of the present invention, the mass percentage of the Al element is controlled between 0.008-0.06%.
  • N In the high-strength cold-rolled steel plate for double-sided enamelled inner tank according to the present invention, nitrogen is the same as carbon. The higher the content of N element in the steel, the worse the formability of the steel plate and cause aging. The upper limit of the content is limited; in addition, in the present invention, the N element can combine with Ti to form corresponding nitrides, which can improve the anti-scale explosion performance of the steel plate. It should be noted that the content of N element in the steel should not be too high. When the content of N element in the steel is too high, the size of the formed nitride is too large, the effect of improving the resistance to scale explosion is very limited, and the plasticity of the steel is damaged. Therefore, in the high-strength cold-rolled steel plate for double-sided enamelled inner container according to the present invention, the mass percentage of N element is N ⁇ 0.006%.
  • Ti In the high-strength cold-rolled steel plate for double-sided enamel inner tank according to the present invention, Ti is an extremely active metal element, which can produce stable compounds with carbon, nitrogen, and sulfur, and these compounds can be uniformly dispersed through process control Distributed in the ferrite matrix to play their role in preventing scale explosion and strengthening the matrix.
  • Ti element also has certain benefits for adhesion. Tim O n formed by the oxidation of Ti element can be enriched on the surface of the steel plate, so that the adhesion layer between the steel plate and the enamel is obviously widened, but if the amount of Tim O n is too large, It will hinder the physical and chemical reaction between the steel plate and the enamel. Therefore, in order to exert the beneficial effect of the Ti element, in the high-strength cold-rolled steel plate for the double-sided enameled inner container of the present invention, the mass percentage of the Ti element is controlled between 0.03-0.1%.
  • element B In the high-strength cold-rolled steel plate for double-sided enamelled inner tank according to the present invention, element B can effectively improve the secondary brittleness problem caused by P segregation; in addition, B forms boron carbide in the steel, and part of it is in solid solution Form exists, which can further improve the scale explosion resistance of the material; but if the B content is too high, it will also cause transverse cracks at the corners of the continuous casting slab. In addition, B elements can also segregate at austenite grain boundaries, and prevent element diffusion and grain boundary migration during high-temperature sintering, thereby improving the high-temperature strength of the steel plate.
  • the mass percentage of the B element is controlled between 0.0002-0.0035%. In some embodiments, the mass percentage of element B is 0.0005-0.0035%.
  • the Cr element in the high-strength cold-rolled steel plate for double-sided enamel inner tank according to the present invention, the Cr element can effectively enhance the strength of the steel and reduce the toughness of the steel; an appropriate amount of Cr is beneficial to improve the adhesion performance of the steel; but it is necessary to pay attention Yes, the content of Cr element in steel should not be too high, when the content of Cr element in steel is too high, it will cause scale explosion. Therefore, in the high-strength cold-rolled steel plate for the double-sided enameled inner container of the present invention, the mass percentage of Cr element is controlled between 0.01-0.06%. In some embodiments, the mass percentage of Cr element is 0.01-0.05%.
  • Cu in the high-strength cold-rolled steel plate for double-sided enamel inner tank according to the present invention, under the pretreatment process including pickling, a small amount of Cu is beneficial to the enamel adhesion performance;
  • the Cu element in the steel mainly consists of Cu 2+ dissolved in the acid solution during pickling will form metal Cu or Cu 2 S compound on the surface of the steel plate again through the replacement reaction, and the residue Cu or Cu 2 S after pickling is a porous
  • the thin film acts as a cathode to generate galvanic corrosion during high-temperature enamel firing, which increases the roughness of the steel plate surface, thereby improving the adhesion performance of the enamel.
  • copper is locally enriched, a large number of air bubbles will be generated in the enamel layer.
  • the mass percentage of Cu element is controlled between 0.01-0.06%. In some embodiments, the mass percentage of Cu element is 0.01-0.05%.
  • Mg In the high-strength cold-rolled steel plate for double-sided enamelled inner tank of the present invention, adding an appropriate amount of Mg element can effectively improve the shape of inclusions in the steel, and improve the plasticity and toughness of the steel. Therefore, in the present invention, the mass percentage of the Mg element is controlled between 0.0005-0.03%.
  • the high-strength cold-rolled steel sheet for double-sided enameled inner container according to the present invention among the unavoidable impurities, O ⁇ 0.008%, Ni ⁇ 0.1%, and Mo ⁇ 0.1%.
  • O, Ni, and Mo are unavoidable impurity elements in steel, and the content of impurity elements in steel needs to be controlled as low as possible under the premise of technical conditions and production costs.
  • the O element will affect the processability and enameling performance of the steel plate.
  • too high O element content will lead to excessive oxide inclusions in the steel, which will deteriorate the plasticity and toughness of the steel plate; on the other hand, too high O element content will consume a large amount of Ti, forming too much Tim O n is not conducive to the adhesion performance, but also reduces the formation of the second phase particles TiN, Ti 4 C 2 S 2 and TiC that are beneficial to the anti-scale explosion performance.
  • Ni and Mo elements are beneficial to improve the adhesion performance of enamel. This is because Ni and Mo elements can promote the infiltration and penetration of enamel to the steel plate during high-temperature enamel firing, and promote the ionization of enamel in the enamel. Mutual dissolution and diffusion with iron ions. In addition, Ni also has the effect of preventing the diffusion of hydrogen in the steel, which can improve the anti-scale explosion performance of the steel plate. However, both Ni and Mo elements are precious alloys. If the content of Ni and Mo elements is too high, it will not only increase the cost, but also reduce the adhesion performance. In general, the adverse effects of impurity elements Ni and Mo are greater than the beneficial effects.
  • the content of impurity elements Ni and Mo must be strictly controlled, and the mass percentage of Ni and Mo elements must be controlled to meet: Ni ⁇ 0.1%, Mo ⁇ 0.1% %. In some embodiments, the mass percentages of Ni and Mo elements are controlled to satisfy: Ni ⁇ 0.02%, Mo ⁇ 0.04%.
  • each chemical element also satisfies at least one of the following formulas:
  • the mass percentages of C, Ti, N and S are further controlled to meet: 0.05% ⁇ C-(Ti-3.43N-1.5S)/4 ⁇ 0.1%.
  • the present invention can further control the quality of Ti, C, N and S elements while controlling the content of a single element
  • the percentage satisfies: 0.65 ⁇ 2.5Ti/(1.2C+8.57N+3.75S) ⁇ 1.35, the purpose of which is to ensure that the carbon, nitrogen, and sulfide particles of titanium are finely and uniformly dispersed in the ferrite matrix, and not only It can improve the anti-scaling performance of the steel plate, and can also play a role in precipitation strengthening, and can inhibit the growth of ferrite grains during high-temperature sintering, and improve the strength of the steel plate and the strength after sintering. If the relational expression is not satisfied, the size of the second phase particles formed in the steel plate will be too large, which will reduce the formability and scale explosion resistance of the steel plate.
  • the high-strength cold-rolled steel plate for double-sided enamel inner container according to the present invention, it also contains: Nb: 0.005-0.04%.
  • Nb element can be further added to the steel.
  • Nb like Ti, is a strong carbon and nitride forming element, and part of Nb exists in a solid solution state.
  • the Nb element can increase the recrystallization temperature of steel, inhibit the recrystallization of austenite, effectively maintain the deformation effect of austenite, and thus refine the ferrite grains; the grain refinement effect of Nb can prevent The steel plate softens after sintering and prevents grain coarsening in the heat-affected zone during welding.
  • carbon and nitride precipitates of Nb also contribute to the hydrogen storage capacity of the steel sheet. Therefore, considering the beneficial effect of Nb element, in the high-strength cold-rolled steel plate for double-sided enamel inner container according to the present invention, it is preferable to add an appropriate amount of Nb element, and control the mass percentage of Nb element at 0.005 Between -0.04%.
  • the matrix of its microstructure is uniform and fine ferrite+pearlite, wherein the proportion of pearlite is less than 8% by volume ; Among them, pearlite is located at the ferrite trifurcation grain boundary. In some embodiments, the phase proportion of pearlite is 2.0-6.5% by volume.
  • its microstructure includes second-phase particles, and the second-phase particles include fine, dispersed Ti second-phase particles.
  • the second phase particles of Ti include TiN, Ti 4 C 2 S 2 and TiC, wherein the diameter of the TiN precipitate is 50-300nm, the diameter of Ti 4 C 2 S 2 precipitates is 30-200nm, and the diameter of TiC precipitates is 1-15nm.
  • the ferrite grain size is 10-11.
  • the high-strength cold-rolled steel plate for double-sided enamel inner tank meets at least one of the following items: yield strength is ⁇ 360 MPa, and elongation at break when the gauge length is 80 mm ⁇ 28.0%, yield strength ⁇ 330MPa after 850°C high-temperature firing for 12 minutes. Furthermore, the tensile strength of the high-strength cold-rolled steel plate for the double-sided enamelled inner container of the present invention is ⁇ 440 MPa.
  • the yield strength of the high-strength cold-rolled steel plate for the double-sided enamel liner of the present invention is 360-415 MPa
  • the tensile strength is 440-510 MPa
  • the elongation at break A 80 is 28.0-33.0%
  • the high temperature of 850 ° C The yield strength after sintering for 12 minutes is 330-370MPa.
  • the present invention provides a double-sided enamelled steel comprising a substrate and an enamel layer on both surfaces of the substrate, wherein the elemental composition of the substrate is the same as that of the double-sided enamelled steel described in any embodiment of the present invention.
  • the surface enamel liner is made of high-strength cold-rolled steel plate with the same elemental composition.
  • the enamelled steel has a yield strength ⁇ 330 MPa (preferably 330-370 MPa), a tensile strength ⁇ 400 MPa (preferably 400-460 MPa), and a hydrogen permeation value ⁇ 7.5 min/mm 2 .
  • the enamelled steel has a hydrogen permeation value of 7.5-16.0 min/mm 2 .
  • the matrix of the microstructure of the substrate is uniform and fine ferrite+pearlite, wherein the phase ratio of pearlite by volume is ⁇ 8% (preferably 1.5-6.5%), wherein pearlite is located in the ferrite At the trifurcation grain boundary of the element body.
  • the microstructure of the substrate further includes second phase particles comprising fine, dispersed second phase particles of Ti.
  • the Ti second phase particles include TiN, Ti 4 C 2 S 2 and TiC, wherein the diameter of TiN precipitates is 50-300 nm, and the diameter of Ti 4 C 2 S 2 precipitates is 30-200 nm, The diameter of the TiC precipitate is 3 to 25 nm.
  • the material used for the enamel layer may be enamel glaze known in the art.
  • An exemplary material is Flow EMP6515 high temperature glaze.
  • another object of the present invention is to provide a kind of manufacturing method of high-strength cold-rolled steel plate for double-sided enamelled inner tank, the manufacturing method is simple and feasible, and the yield of the high-strength cold-rolled steel plate for double-sided enameled inner tank made is
  • the strength is ⁇ 360MPa
  • the elongation at break at a gauge length of 80mm is ⁇ 28.0%
  • the hydrogen permeation value is ⁇ 7.5min/mm 2
  • the yield strength is ⁇ 330MPa after at least 850°C high-temperature firing for at least 12 minutes, which can meet the requirements of double-sided coating. Tang's request.
  • the present invention proposes the manufacture method of above-mentioned double-sided enamel liner high-strength cold-rolled steel plate, which comprises steps:
  • Hot rolling and coiling the final rolling temperature of hot rolling is controlled to be 810-880°C, and the coiling temperature is controlled to be 620-680°C;
  • the soaking temperature is 780-850°C
  • the soaking time is 120-200s
  • the overaging temperature is between 165-450°C
  • the overaging time is 250-350s
  • step (1) the basic requirements can be obtained through pre-desulfurization of molten iron, compound blowing at the top and bottom of the converter, and tapping alloying.
  • the composition of molten steel can be obtained by CAS refining treatment to obtain uniform and stable molten steel with uniform temperature and composition, and finally the continuous casting slab with the above composition can be formed through continuous casting.
  • the hot continuous rolling process is all carried out in the austenite single-phase region, and the final rolling temperature is set at the Ar3 transformation temperature (the transition from austenite to ferrite during cooling) Transformation temperature) and close to this temperature, the purpose is to accumulate sufficient deformation in the austenite non-recrystallized zone, the austenite grain boundary and the "deformation zone" inside the grain together serve as the nucleation core of ferrite, so that the hot
  • the rolling plate obtains a refined ferrite structure, so the present invention controls the final rolling temperature between 810-880°C; correspondingly, in the coiling process, the coiling temperature has a significant impact on the structure and properties of the steel plate, in order to To ensure that the steel plate has a high strength, and at the same time, the pearlite and TiC particles are fully separated.
  • the present invention controls the coiling temperature between 620-680°C. When the coiling temperature is too low, the yield ratio of the material increases, which is not conducive to Formability
  • step (4) descaling can effectively remove the iron oxide scale on the surface of the hot-rolled steel strip, so as to facilitate subsequent operations.
  • the cold rolling reduction rate has an influence on the mechanical properties and anti-scaling performance of the steel plate.
  • the reduction rate affects the strength of the steel plate.
  • the greater the cold rolling reduction rate the greater the elongation of the microstructure along the rolling direction, resulting in an increase in the nucleation rate during the recrystallization process.
  • the ferrite crystals The finer the grain, the higher the yield strength of the steel plate.
  • the normal-temperature structure of the high-strength cold-rolled steel plate for double-sided enamel inner tanks of the present invention contains hard phases such as cementite and titanium carbon, nitrogen, and sulfide.
  • the cold rolling reduction rate is controlled to 60-70%.
  • step (6) a high-temperature rapid continuous annealing process is adopted, and the specific control soaking temperature is 780-850°C, the soaking time is 120-200s, and the overaging temperature is 165-450°C Between, the control overaging time is 250-350s.
  • the recrystallization process can be completed in a short time at high temperature, and the coarseness of ferrite grains can be avoided, so as to obtain high-strength cold-rolled steel sheets with good strength and plasticity;
  • the low-temperature precipitated TiC particles of carbon and titanium are fully precipitated, which effectively improves the anti-scaling performance of the steel plate.
  • step (2) the heating temperature is 1100-1230° C., and the time in the furnace is ⁇ 360 minutes.
  • the heating temperature is preferably controlled to be 1100-1230° C., and the furnace time ⁇ 360 minutes, the following can be obtained.
  • the heating temperature is 1130-1230° C., and the time in the furnace is 370-420 minutes.
  • step (2) if the heating temperature or time is lower than the set value, the above two purposes will not be achieved; if the heating temperature is too high or the time is too long, it will cause oxidation and Decarburization causes severe burning loss of the billet, which affects the yield.
  • step (7) the leveling reduction rate is controlled to 0.6-1.2%.
  • the flattening reduction rate is controlled to 0.6-1.2%, and the cold-rolled strip after annealing is carried out to the secondary cold rolling with a small reduction rate, and the following two benefits can be obtained Effects: First, it can reduce or eliminate the "yield platform" on the stress-strain curve, avoiding the appearance of "Lüders band” during stamping; second, it can improve the flatness of the steel plate and the smoothness of the plate surface.
  • the present invention also provides a method for preparing double-sided enamelled steel, which includes the steps of preparing the high-strength cold-rolled steel plate for double-sided enameled inner container of the present invention by the method described above, and A step of enamelling the prepared double-sided enamel liner with a high-strength cold-rolled steel plate.
  • a step of enamelling the prepared double-sided enamel liner with a high-strength cold-rolled steel plate in the simmering step, 840-900° C. is simmered for 8-15 minutes.
  • the enamelling treatment is performed using a one-enameling-one-firing process or a two-enameling-two-firing process.
  • the glaze used for the enamel layer can be various glazes well known in the art.
  • the high-strength cold-rolled steel plate for the double-sided enamel inner container of the present invention and its manufacturing method have the following advantages and beneficial effects:
  • the present invention is based on the design idea of low alloy cost and low processing technology cost.
  • composition design it is based on carbon, manganese and phosphorus strengthening, adding relatively low-cost titanium and boron elements, and assisting the addition of copper and chromium and magnesium and other alloying elements; in terms of processing technology, by controlling the heating temperature of the continuous casting slab, the finishing temperature of hot rolling, the coiling temperature and the reduction rate of cold rolling, and adopting a high-temperature rapid continuous annealing process with high efficiency, it is ensured that the steel plate has Excellent surface quality, mechanical properties and enamelling properties.
  • the matrix of the microstructure of the high-strength cold-rolled steel plate for the double-sided enamel liner of the present invention is even and small ferrite+pearlite, the phase ratio of its pearlite ⁇ 8%, and the ferrite grain size is between Between grades 10-11.
  • the invention mainly uses solid solution strengthening, precipitation strengthening and fine grain strengthening to improve the strength of the steel plate to ensure that the yield strength of the steel plate is ⁇ 360MPa, and the elongation at break is ⁇ 28.0% at a gauge length of 80mm; , the fine, dispersed titanium second phase particles can effectively control the growth of ferrite grains, and the boron element can improve the high temperature strength of the steel, ensuring that the yield strength of the steel plate remains above 330MPa after sintering, which is better Fully meet the withstand voltage requirements of the electric heating liner.
  • the pearlite at the ferrite trifurcation grain boundary, the fine and dispersed second-phase particles of titanium are used to improve the scale explosion resistance of the steel plate
  • boron can further improve the anti-scale explosion performance
  • the refined ferrite grains can also improve the anti-scale explosion performance, because the grain boundary plays the role of storing hydrogen, and the finer the grain, the larger the grain boundary area The higher the hydrogen storage capacity.
  • the hydrogen permeation value of the high-strength cold-rolled steel plate for the double-sided enamelled inner container of the invention is ⁇ 7.5min/mm 2 , which meets the anti-scaling requirement of double-sided enameling.
  • the content of free carbon forming pearlite is limited, which suppresses the occurrence of poor air bubbles and pinhole defects during the sintering process.
  • Figure 1 shows the metallographic microstructure of the high-strength cold-rolled steel plate for double-sided enameled inner container of Example 1.
  • Figure 2 and Figure 3 show the distribution state of the second phase particles observed under the transmission electron microscope of the high-strength cold-rolled steel plate for the double-sided enameled inner container of Example 1.
  • Fig. 4 shows the metallographic microstructure of the high-strength cold-rolled steel plate for the double-sided enamel inner container of Example 1 after simulated high-temperature sintering.
  • Figure 5 and Figure 6 show the distribution state of the second phase particles observed under the transmission electron microscope after the high-strength cold-rolled steel plate for the double-sided enameled inner container of Example 1 is sintered at a simulated high temperature.
  • Figure 7 shows the bubble structure of the enamel layer after double-sided glazing and high-temperature sintering of the high-strength cold-rolled steel plate for the double-sided enamel inner container of Example 1.
  • Fig. 8 shows the bubble structure of the enamel layer after double-sided glazing and high-temperature sintering of the comparative steel plate of Comparative Example 1.
  • Table 1-1 and Table 1-2 list the mass percentage of each chemical element in the high-strength cold-rolled steel plate for double-sided enameled inner container of Example 1-6 and the comparative steel plate of Comparative Example 1-2.
  • Table 1-1 (wt%, the balance is Fe and other unavoidable impurities other than O, Ni, Mo)
  • the high-strength cold-rolled steel plate for the double-sided enamel inner container of the embodiment 1-6 of the present invention and the contrast steel plate of the comparative example 1-2 all adopt the following steps to make:
  • Billet heating control the heating temperature to 1100-1230°C, and control the heating time in the furnace for ⁇ 360min, so that the slab cast slab is fully austenitized, obtains an austenite structure with uniform composition, and reduces the deformation of the steel resistance.
  • Hot rolling and coiling The final rolling temperature of hot rolling is controlled to be 810-880°C, after rolling, it is cooled to the coiling temperature by laminar flow, and then coiled, and the coiling temperature is controlled to be 620-680°C.
  • the soaking temperature is 780-850°C
  • the soaking time is 120-200s
  • the overaging temperature is between 165-450°C
  • the overaging time is 250-350s.
  • the high-strength cold-rolled steel plates for double-sided enamel liners in Examples 1-6 are all prepared by the above steps, and their chemical composition and related process parameters all meet the control requirements of the design specifications of the present invention .
  • the comparative steel plates of Comparative Examples 1-2 were also prepared by the above-mentioned steps and processes, there were parameters in the chemical composition that did not meet the control requirements of the design specifications of the present invention.
  • Table 2-1 and Table 2-2 list the specific process parameters of the high-strength cold-rolled steel plate for the double-sided enameled inner container of Example 1-6 and the comparative steel material of Comparative Example 1-2.
  • the overaging temperature changes during the actual operation, and it is not stable at a fixed value, but during the overaging period, the temperature gradually decreases, so in step (6) of Table 2-2
  • the overaging temperature is presented as a range value rather than a point value in each example and comparative example.
  • the special feature of steel for enamelling is that it will be served after high-temperature sintering. Therefore, in order to verify the yield strength changes of the steel plates of each embodiment and comparative example before and after high-temperature sintering, the present invention aims at the implementation after continuous annealing.
  • the steel plates of examples 1-6 and comparative examples 1-2 are directly subjected to tensile tests, which are sampled along the rolling direction of the annealed steel plates, processed into tensile samples with a gauge length of 80mm according to the JIS13A standard, and then each embodiment and comparative example The conventional mechanical properties of the tensile sample were tested to obtain the yield strength, tensile strength and elongation at break A 80 at a gauge length of 80 mm.
  • the simulated high-temperature sintering test was carried out on the steel plates of Examples 1-6 and Comparative Example 1-2, and the sintering temperature was controlled to be 850 ° C, and the time in the furnace was 12 minutes; The samples were taken from the rolling direction, and the tensile test was carried out to obtain the yield strength of the steel materials of each embodiment and comparative example after simulated sintering (850° C. ⁇ 12 min).
  • Table 3-1 and Table 3-2 list the performance test results of the high-strength cold-rolled steel sheets for double-sided enamelled inner containers of Examples 1-6 and the enamelled steels of Comparative Examples 1-2.
  • the yield strength of the high-strength cold-rolled steel plate for the double-sided enamel liner of embodiment 1-6 is higher, and its yield strength is between 363-409MPa, and the tensile strength is between 447-409MPa.
  • Between 502MPa and the elongation at break A 80 at a gauge length of 80mm is between 28.5-32.5%, which can meet the forming requirements of the three-stage liner body rolling or head stamping.
  • the phase ratio of pearlite is between 2.17-6.03%, and the ferrite grain size is 10.5.
  • the high-strength cold-rolled steel sheets for double-sided enamel inner tanks in Examples 1-6 still maintain a high yield strength, and their yield strengths are all greater than 330MPa, and the yield strength is between 332-368MPa. Between, the tensile strength is greater than 400MPa, in the range of 400 ⁇ 460MPa. This shows that the cold-rolled steel for enameling of Examples 1-6 of the present invention has good high temperature softening resistance, can effectively improve the pressing ability of the enameled inner container, and prolong the service life of the inner container.
  • the enamel plate obtained after double-sided glazing has a good bubble structure of the enamel layer, and the bubbles are small and evenly dispersed; the hydrogen penetration time of the steel plate All of them exceed the threshold value of 6.7min/mm 2 stipulated in the European standard EN 10209-2013, meeting the anti-scaling requirements for double-sided enamelling.
  • Comparative Example 1 is within the control range of the design of the present invention, it is calculated that Ti-3.43N-1.5S ⁇ 0, indicating that the combination with N and S has consumed all Ti, and there is no remaining Ti and C combined.
  • the C element content of Comparative Example 1 exceeds the control range, that is to say, C is all used to form pearlite, and the content of pearlite structure exceeds the limit range of the present invention, resulting in a large amount of gas generated during firing, and the porcelain layer has not yet been fused. Fully released, resulting in dense bubbles and different sizes in the porcelain layer, resulting in poor bubble structure.
  • the contents of C and Ti in Comparative Example 2 are all lower than the control range of the present invention, and a sufficient amount of pearlite and titanium carbon, sulfur and nitride cannot be formed, thereby reducing the strength and hydrogen absorption capacity of the steel plate.
  • the strength of the comparative steel plate in Comparative Example 2 will be further reduced, which cannot meet the requirements of high-pressure water circulation and pressure, and cannot meet the requirements of double-sided enamelling without scaling.
  • Figure 1 shows the metallographic microstructure of the high-strength cold-rolled steel plate for double-sided enameled inner container of Example 1.
  • Figure 2 and Figure 3 show the distribution state of the second phase particles observed under the transmission electron microscope of the high-strength cold-rolled steel plate for the double-sided enameled inner container of Example 1.
  • the matrix of the microstructure of the high-strength cold-rolled steel plate for double-sided enamel liner in Example 1 is uniform and fine ferrite+pearlite, wherein the average grain size of ferrite is The particle diameter was 8.14 ⁇ m.
  • the high-strength cold-rolled steel plate for the double-sided enameled inner container of Example 1 has TiN, Ti 4 C 2 S 2 , and TiC particles dispersed in the ferrite matrix , wherein the diameter of the TiN precipitated phase is 76nm, the diameter of the Ti 4 C 2 S 2 precipitated phase is 41nm, and the size of the TiC precipitated phase is mainly between 1-7nm.
  • Fig. 4 shows the metallographic microstructure of the high-strength cold-rolled steel plate for the double-sided enamel inner container of Example 1 after simulated high-temperature sintering.
  • Figure 5 and Figure 6 show the distribution state of the second phase particles observed under the transmission electron microscope after the high-strength cold-rolled steel plate for the double-sided enameled inner container of Example 1 is sintered at a simulated high temperature.
  • the microstructure of the high-strength cold-rolled steel plate for the double-sided enameled inner container of Example 1 after simulated high-temperature enamelling is uniform and fine ferrite+pearlite, that is to say The microstructure is the same as that after cold rolling and annealing, and the average grain size of ferrite is 9.52 ⁇ m. It can be seen that the grain size of ferrite does not change significantly after high temperature sintering.
  • the volume ratio of pearlite is still ⁇ 8%, which is in the range of 1.5-6.5%.
  • Figure 7 shows the bubble structure of the enamel layer after double-sided glazing and high-temperature sintering of the high-strength cold-rolled steel plate for the double-sided enamel inner container of Example 1.
  • the high-strength cold-rolled steel plate for the double-sided enamelled inner container of Example 1 is glazed on both sides and sintered at high temperature, and the bubbles in the enamel layer are fine and uniformly dispersed, which belongs to a good bubble structure.
  • Fig. 8 shows the bubble structure of the enamel layer after double-sided glazing and high-temperature sintering of the comparative steel plate of Comparative Example 1.
  • the pearlite content in the comparative steel plate of Comparative Example 1 is too high, and a large amount of CO and other gases are generated during the enamel firing process. These gases are not fully released before the enamel layer is fused, and a large amount of Bubbles with large and uneven sizes, some of which have a diameter of up to 300 ⁇ m, almost penetrate the entire enamel layer, and easily form pinhole defects, which affect the performance of enamel products.

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Abstract

La présente divulgation concerne une plaque d'acier laminée à froid à haute résistance pour un revêtement d'émail double face, la plaque d'acier laminée à froid à haute résistance comprenant du Fe et des impuretés inévitables, et comprenant également les éléments chimiques suivants en pourcentage en masse : C : 0,06-0,12 %, 0 < Si ≤ 0,08 %, Mn : 0,5-1,2 %, P : 0,01-0,05 %, S : 0,005-0,05 %, Al : 0,008-0,06 %, N ≤ 0,006 %, Ti : 0,03-0,1 %, B : 0,0002-0,0035 %, Cr : 0,01-0,06 %, Cu : 0,01-0,06 %, et Mg : 0,0005-0,03 %. De manière correspondante, la présente divulgation concerne également un procédé de fabrication de la plaque d'acier laminée à froid à haute résistance pour un revêtement d'émail double face, le procédé comprenant les étapes de : (1) fusion, affinage et coulée continue ; (2) chauffage de billette ; (3) laminage à chaud et bobinage : régulation de la température finale de laminage du laminage à chaud à 810-880 °C et régulation de la température de bobinage à 620-680 °C ; (4) décalaminage ; (5) laminage à froid : régulation du taux de réduction de laminage à froid à 60-70 % ; (6) recuit continu : la température d'immersion étant de 780-850 °C, le temps d'immersion étant de 120-200 S, la température de sur-vieillissement étant de 165-450 °C, et le temps de sur-vieillissement étant de 250-350 s ; et (7) aplatissement.
PCT/CN2022/133985 2021-11-25 2022-11-24 Plaque d'acier laminée à froid à haute résistance pour revêtement d'émail double face et son procédé de fabrication WO2023093798A1 (fr)

Applications Claiming Priority (2)

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JP2006045580A (ja) * 2004-07-30 2006-02-16 Nippon Steel Corp ホーロー密着性が良好なホーロー用メッキ鋼板およびその製造方法並びにホーロー製品
CN105316579A (zh) * 2014-07-29 2016-02-10 上海梅山钢铁股份有限公司 热水器搪瓷内胆用薄规格热轧酸洗钢板及其制造方法
CN111996468A (zh) * 2020-09-18 2020-11-27 山西太钢不锈钢股份有限公司 一种搪瓷钢及其制备方法和应用
WO2021169937A1 (fr) * 2020-02-25 2021-09-02 宝山钢铁股份有限公司 Acier de revêtement de verre et procédé de production associé

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006045580A (ja) * 2004-07-30 2006-02-16 Nippon Steel Corp ホーロー密着性が良好なホーロー用メッキ鋼板およびその製造方法並びにホーロー製品
CN105316579A (zh) * 2014-07-29 2016-02-10 上海梅山钢铁股份有限公司 热水器搪瓷内胆用薄规格热轧酸洗钢板及其制造方法
WO2021169937A1 (fr) * 2020-02-25 2021-09-02 宝山钢铁股份有限公司 Acier de revêtement de verre et procédé de production associé
CN111996468A (zh) * 2020-09-18 2020-11-27 山西太钢不锈钢股份有限公司 一种搪瓷钢及其制备方法和应用

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