CN116043124B - Cold-rolled weather-resistant steel plate with enamelable performance and preparation method thereof - Google Patents

Cold-rolled weather-resistant steel plate with enamelable performance and preparation method thereof Download PDF

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CN116043124B
CN116043124B CN202310091917.6A CN202310091917A CN116043124B CN 116043124 B CN116043124 B CN 116043124B CN 202310091917 A CN202310091917 A CN 202310091917A CN 116043124 B CN116043124 B CN 116043124B
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steel plate
percent
enamelable
performance
steel
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CN116043124A (en
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俞波
张宜
李凯旋
陈壮
汪建威
汤亨强
吴浩
王占业
李进
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Maanshan 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/773—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material under reduced pressure or vacuum
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
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    • 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
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—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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    • 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
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23D5/00—Coating with enamels or vitreous layers
    • C23D5/02—Coating with enamels or vitreous layers by wet methods
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/005—Ferrite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/009—Pearlite
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

The invention discloses a cold-rolled weather-resistant steel plate with enamelable performance and a preparation method thereof, and belongs to the technical field of metal materials. The cold-rolled weather-resistant steel plate with enamelable performance comprises the following main chemical components in percentage by weight: c:0.07 to 0.15 percent of Si:0.10 to 0.60 percent of Mn:0.20 to 0.60 percent, P:0.035 to 0.080 percent, S: 0.005-0.025%, cu:0.30 to 0.55 percent of Ni:0.20 to 0.70 percent of Cr:0.10 to 0.45 percent, als:0.008 to 0.030 percent of Ti:0.015 to 0.055 percent, B:0.0008 to 0.0014 percent, and the balance of Fe and unavoidable impurity. The cold-rolled weather-resistant steel plate with the component proportion can solve the problem of enamel scale explosion and can ensure that the steel plate has excellent corrosion resistance.

Description

Cold-rolled weather-resistant steel plate with enamelable performance and preparation method thereof
Technical Field
The invention relates to the technical field of metal materials, in particular to a cold-rolled weather-resistant steel plate with enamelable performance and a preparation method thereof.
Background
The enamel product is a product coated with enamel on the surface of metal, and is burnt by high Wen Tang, so that the enamel is tightly adhered to the surface of the steel plate, and the enamel has strong stability, strong corrosion resistance and high temperature resistance and is widely applied to various industries. However, the enamel product has a remarkable disadvantage that the enamel layer is very hard and very brittle, and the expansion coefficient of the enamel layer and the expansion coefficient of the steel plate are quite different, so that the enamel layer is easy to crack in the actual processing process, and once the enamel layer is cracked, a corrosive medium can rapidly enter the steel plate to corrode the steel plate and be sent to spread, so that the whole steel plate at the inner layer is corroded, and finally the whole part is scrapped.
The current steel sheet for enamel products is a special steel sheet which is required to have a certain strength and is required to have anti-scaling performance, because enamel products can generate a large amount of [ H ] atoms in the steel sheet in the enamel firing process, and the [ H ] atoms exist at the interface of an enamel layer and the steel sheet in the form of hydrogen in the subsequent cooling process, so that the anti-scaling performance is finally caused. When the enamel product is subjected to scale explosion, the sample is scrapped. The special plate for enamel products (namely enamel steel) mainly solves the problem of scale explosion by introducing hydrogen traps into a steel plate, namely S, C, ti, N, B and other elements are added, and a large number of hydrogen traps are obtained through a production process, so that the scale explosion resistance of the steel plate is improved. However, when some enamel structural parts are used, especially in complex corrosion environments, when parts encounter high and low temperature environments and some unavoidable factors, especially in the heat exchanger industry, enamel layers are broken due to expansion and contraction, the whole parts can be corroded rapidly, and the steel plate is a common carbon steel plate without secondary corrosion resistance, so that the whole parts are scrapped.
After retrieval, the domestic patent: publication number: CN108950423B "high-strength steel for hot-rolled double-sided enamel, double-sided enamel steel and manufacturing method thereof" comprises the following chemical components (mass percent): c0.08-0.15, si:0.15 to 0.5, mn:1.2 to 2.5, al:0.006 to 0.08, cr:0.15 to 0.65 percent, ti:0.01 to 0.06, nb:0.01 to 0.10 percent, cu:0.10 to 0.35, mo:0.03 to 0.15, V: 0.02-0.10, P is less than or equal to 0.03, S is less than or equal to 0.006, N is less than or equal to 0.006, and the balance is iron and other unavoidable impurities. Disclosed is a hot rolled double-sided enameled steel sheet, not a cold rolled double-sided enameled steel sheet, the structure of which is ferrite + pearlite in the examples of the patent, wherein the pearlite ratio is 25-50%. The patent adopts Ti, nb, V and C, N component systems, and precipitates such as Ti (C, N), nb (C, N), V (C, N) and the like are obtained through a process to solve the problem of double-sided scaling. Although the patent also adopts Cr, the patent also adopts a trace amount of Cr, and the patent also adopts Cr to improve the hardenability of the steel plate, so that the strength of the experimental steel is improved, and the problem that the anti-scaling performance cannot be solved.
Domestic patent publication No.: CN112301276a, "a high-strength high-weather-resistance cold-rolled dual-phase weather-resistant steel and its production method", discloses a cold-rolled weather-resistant steel plate. The chemical composition of the catalyst is C:0.008 to 0.04 percent of Si:0.15 to 0.30 percent of Mn:0.20 to 0.50 percent, P: less than or equal to 0.020 percent, S: less than or equal to 0.01 percent, cu:0.35 to 0.45 percent of Ni:0.25 to 0.40 percent of Cr:3.5 to 5.0 percent of Als:0.025 to 0.050 percent of Ti:0.010 to 0.025, N: less than or equal to 0.0080 percent, ca:0.0015 to 0.0035. The object of this patent is to obtain cold rolled weathering steel plates with high weathering resistance which is doubled compared to conventional weathering steel, but the patent does not disclose enamelable properties.
Domestic patent publication No.: CN106636897a, "a low alloy weathering steel, its preparation method and application," discloses a low alloy weathering steel plate, comprising the following chemical components: c:0.02 to 0.05 percent; mn:0.6 to 1.00 percent; cu:0.20 to 0.40 percent; ni:0.15 to 0.50 percent; nb:0.04 to 0.07 percent; ti: 0.005-0.015%; si:0.30 to 0.60 percent; al is less than or equal to 0.02 percent; p is less than or equal to 0.02 percent; s is less than or equal to 0.08 percent, and the other is Fe and unavoidable impurities. The patent mainly reduces Cr and Ni which are alloy elements with higher cost by improving Si element with low cost, and achieves good corrosion resistance and mechanical property through a hot rolling process. The patent adopts micro-alloy to reduce the manufacturing cost of the steel plate, but the chemical components of the steel plate use Nb, ti and other alloys to change the structure performance, the production cost of the steel plate is still higher, and the patent also only provides a manufacturing method of a hot-rolled weather-resistant steel plate, which is not suitable for cold-rolling weather resistance. Meanwhile, the product is not suitable for enamelled steel sheets, and the anti-scaling performance is not described.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problems that an enamel layer of an enamel product is easy to break after scale explosion and the corrosion resistance is poor after scale explosion in the prior art, and provides a cold-rolled weather-resistant steel plate with enamel performance and a preparation method thereof.
2. Technical proposal
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the invention relates to a cold-rolled weather-resistant steel plate with enamelable performance, which comprises the following main chemical components in percentage by weight: c:0.07 to 0.15 percent of Si:0.10 to 0.60 percent of Mn:0.20 to 0.60 percent, P:0.035 to 0.080 percent, S: 0.005-0.025%, cu:0.30 to 0.55 percent of Ni:0.20 to 0.70 percent of Cr:0.10 to 0.45 percent, als:0.008 to 0.030 percent of Ti:0.015 to 0.055 percent, B:0.0008 to 0.0014 percent, and the balance of Fe and unavoidable impurity. The steel plate is a weather-resistant steel plate with corrosion resistance, and the cold-rolled weather-resistant steel is a special corrosion-resistant steel plate, and the corresponding percentage of P, cu, cr, ni and other alloys are added into the steel plate to enhance the corrosion resistance of the steel plate. The cold-rolled weather-resistant steel plate with enamel performance, provided by the invention, has the advantages that the prepared steel plate has enamel performance and weather resistance by utilizing the characteristics of the two special steel plates, and the corrosion resistance and the durability of the product in a complex environment can be obviously improved. Aiming at the important defects of the prior two steel plates, for enamel steel plates, the anti-scaling performance of the steel plates is most important, once the scaling occurs, the anti-scaling performance of the steel plates is seriously influenced, the beauty is seriously influenced, the corrosion resistance is rapidly reduced, and the service life of products is seriously influenced; for the cold-rolled weather-resistant steel plate, the alloy element is utilized to compact the oxide layer, further corrosion is prevented, a corrosion-resistant layer is formed on the surface of the steel plate, and the steel plate is protected from continuous corrosion. However, cold-rolled weather-resistant steel plates do not have the anti-scaling performance, have poor hydrogen storage capacity and do not belong to special enamel steel. Therefore, the cold-rolled weather-resistant steel plate with the component proportion can solve the problem of enamel scale explosion and can ensure that the steel plate has excellent corrosion resistance.
Further, the component proportioning system needs to satisfy: the first proportioning system is as follows: 1. not less than (6 x [ Ti ])/(22 [ C ]) not less than 0.01, tiN, tiC, ti (C, N) and Ti (C, S) precipitates can be formed more, the anti-scaling performance of the steel plate is further improved, and the proportioning system II is satisfied: [B] the proportion of B element can increase the second phase nucleation point more and promote other second phase particles to be separated out, and the proportion of B element is easy to separate out C, N, so that the anti-scaling performance of the steel plate is further improved, wherein the proportion of [ P ], [ Ti ], [ C ] and [ B ] are weight percentages of corresponding elements, P, cu elements can effectively improve the corrosion resistance of the base plate, the addition of P is easy to gather at a grain boundary, cu is easy to gather on the surface to form Cu small particles, the distribution and separation behavior of separated particles in a tissue and the adhesiveness in the enamel process are influenced, and trace B element is added, so that the problem of local gathering of P and Cu can be effectively improved at the grain boundary and the curve, on one hand, and the corrosion resistance of the base plate is improved on the other hand.
Further technical scheme, wherein the component proportioning system also needs to satisfy proportioning system III: (0.071 [ Si ] +0.217 [ P ] +0.119 [ Cu ] +0.107 [ Cr ] +0.703 [ Ti ]) is not less than 0.1, wherein [ Si ], [ P ], [ Cu ], [ Cr ] and [ Ti ] are the weight percentages of the corresponding elements, the ratio is combined, cu, P, cr and other alloys are matched with trace Ti, B and other elements, the number of hydrogen traps in a structure can be effectively increased, the scale explosion resistance of the steel plate is improved, the steel plate has weather resistance, and finally the prepared steel plate can be used for enamel, so that the steel plate has double corrosion resistance and the service life of a workpiece can be greatly prolonged.
A preparation method of a cold-rolled weather-resistant steel plate with enamelable performance comprises the following steps:
s1, smelting molten steel: smelting molten steel according to the component requirements of the molten steel;
s2, a rolling process: slab tapping temperature: 1180-1220 ℃; finishing temperature: 850-880 ℃; coiling temperature: 560-620 ℃; rolling into a steel plate; the dislocation and deformation energy in the tissue can be effectively increased by adopting opposite low-temperature finish rolling and low-temperature coiling, the number of hydrogen traps is increased, meanwhile, the low finish rolling temperature and coiling temperature avoid long-range diffusion of elements, and the solid solution quantity of elements such as P, cr, cu and the like in the steel plate is increased.
S3, continuous annealing: the annealing temperature is 700-780 ℃, and the annealing speed is as follows: 80-140 m/min, cooling rate of 40-70 deg.C/s, and protecting atmosphere (N) 2 -H 2 ) Annealing under the environment; the continuous annealing is favorable for the complete recrystallization of crystal grains, improves the forming performance of the material, simultaneously B, cr improves the hardenability of the material, promotes the formation of pearlite and carbide, and is used as a hydrogen trap, so that the anti-scaling performance of the steel plate is greatly improved, meanwhile, the annealing temperature is not too high, the diffusion and the segregation of weather-resistant elements are increased, and the hydrogen storage capacity of the steel plate is reduced.
S4, leveling: and flattening the steel plate.
In the further preparation method, in the step S2, the finishing temperature and the coiling temperature are as follows: within 5-10 s, the finishing temperature-coiling temperature=250-300 ℃, so that the phase change supercooling degree can be effectively increased, the phase change of the tissue is promoted, elements are enabled to be solid-dissolved in the tissue, and the number of hydrogen traps in the tissue is increased.
In the further preparation method, in the step S2, the total rolling reduction is 60% -80%, and the target thickness is 0.5-2.5 mm. The method can ensure that the steel plate has high work hardening degree and more tissue dislocation, promotes the formation of precipitates in the annealing process, simultaneously has more high dislocation tissue to dissolve Cu, ni and other alloys, and increases the number of hydrogen traps.
Further, in the preparation method, in step S4, the elongation is flattened: 0.8% -1.4%, preferably 1.2%, can effectively improve the shape of the plate, eliminate the yield platform, increase the tissue non-occurrence and improve the hydrogen melting capability.
The preparation method further comprises the following steps of S5, wet enameling: cleaning the sample, spraying, baking at 100 ℃ and enamelling at 850 ℃ for 10min to obtain the enamel steel.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) According to the cold-rolled weather-resistant steel plate with enamelable performance and the preparation method thereof, based on the corrosion resistance of the weather-resistant steel, the enamelable performance of the enamel steel is achieved, the alloy such as Cu, P, cr, ni is added to the cold-rolled enamel steel, trace Ti, B and other elements are matched, meanwhile, the number of hydrogen traps in a structure is increased through a rolling process, the anti-scaling property of the steel plate is improved, meanwhile, the steel plate has weather resistance, and finally the prepared steel plate can be used for enamel, so that a sample piece has double corrosion resistance, the service life of a workpiece can be greatly prolonged, and the excellent double corrosion resistance is achieved.
(2) The cold-rolled weather-resistant steel plate with enamel performance has the yield strength of 300-450 MPa, the tensile strength of more than or equal to 450MPa, the elongation of more than or equal to 28 percent, good forming performance and no fishscale of enamel, and is mainly used in the industries of waste incineration and heat exchangers.
Drawings
FIG. 1 is a golden phase diagram of example 1;
FIG. 2 is a golden phase diagram of example 3;
FIG. 3 is a golden phase diagram of example 5;
FIG. 4 is a golden phase diagram of comparative example 1;
FIG. 5 is a golden phase diagram of comparative example 2;
FIG. 6 is a photograph of a sample of example 1;
FIG. 7 is a photograph of a sample of example 3;
FIG. 8 is a photograph of a sample of example 5;
FIG. 9 is a photograph of a sample of example 6;
FIG. 10 is a photograph of a sample of comparative example 1;
fig. 11 is a photograph of the sample of comparative example 2.
Detailed Description
For a further understanding of the present invention, the present invention will be described in detail with reference to the drawings.
The invention is further described below with reference to examples.
Examples
The cold-rolled weather-resistant steel plate with enamelable performance in the embodiment comprises the following main chemical components in percentage by weight: c:0.07 to 0.15 percent of Si:0.10 to 0.60 percent of Mn:0.20 to 0.60 percent, P:0.035 to 0.080 percent, S: 0.005-0.025%, cu:0.30 to 0.55 percent of Ni:0.20 to 0.70 percent of Cr:0.10 to 0.45 percent, als:0.008 to 0.030 percent of Ti:0.015 to 0.055 percent, B:0.0008 to 0.0014 percent, and the balance of Fe and unavoidable impurity. The steel plate is a weather-resistant steel plate with corrosion resistance, and the cold-rolled weather-resistant steel is a special corrosion-resistant steel plate, and the corresponding percentage of P, cu, cr, ni and other alloys are added into the steel plate to enhance the corrosion resistance of the steel plate. The cold-rolled weather-resistant steel plate with enamel performance, provided by the invention, has the advantages that the prepared steel plate has enamel performance and weather resistance by utilizing the characteristics of the two special steel plates, and the corrosion resistance and the durability of the product in a complex environment can be obviously improved. Aiming at the important defects of the prior two steel plates, for enamel steel plates, the anti-scaling performance of the steel plates is most important, once the scaling occurs, the anti-scaling performance of the steel plates is seriously influenced, the beauty is seriously influenced, the corrosion resistance is rapidly reduced, and the service life of products is seriously influenced; for the cold-rolled weather-resistant steel plate, the alloy element is utilized to compact the oxide layer, further corrosion is prevented, a corrosion-resistant layer is formed on the surface of the steel plate, and the steel plate is protected from continuous corrosion. However, cold-rolled weather-resistant steel plates do not have the anti-scaling performance, have poor hydrogen storage capacity and do not belong to special enamel steel. Therefore, the cold-rolled weather-resistant steel plate with the component proportion can solve the problem of enamel scale explosion and can ensure that the steel plate has excellent corrosion resistance.
In order to ensure that the sample steel plate of the embodiment has enamel performance and corrosion resistance, the sample steel plate is mainly based on the following principle:
1) Carbon C: carbon is an economic strengthening element for steel grade, the strength of the steel can be improved through solid solution strengthening and precipitation strengthening, pearlite and bainite tissues are easy to form in the tissues, and the hydrogen-melting capacity of the steel plate is improved. In addition, carbon and Ti, nb and other elements form second phase particles, including TiC, ti (C, N), nbC, nb (C, N) and other composite particles, and the particles are uniformly distributed in a tissue, so that a large number of hydrogen atoms can be stored, and the anti-scaling performance of the steel plate is improved. However, the element C is not too high, and C and H can be mixed during enamel firing 2 O reacts to form CO and CO 2 Resulting in a large number of voids in the glaze. Therefore, the content of C element is controlled to be 0.07-0.15%.
2) Silicon Si: the alloy can be used as a reducing agent and a deoxidizing agent to be added into steel, meanwhile, the silicon element can improve the hardenability and tempering resistance of the steel, the increase of the Si element can reduce the overall corrosion resistance rate of the steel plate, and the alloy can be matched with Cu and Cr in the steel to effectively improve the weather resistance of the steel, but the plasticity of the steel plate and the surface adhesion performance are affected by the excessively high Si content, so that the Si content is not easy to be too high, and the alloy is required to be 0.10-0.60%.
3) Manganese Mn: manganese is one of important elements for strengthening the steel plate, effectively improves the strength of the steel plate, is a common desulfurization and deoxidization element, has better economical efficiency, is widely added into the steel plate, but can enlarge the austenite phase region, improve the hardenability and reduce A C3 The wire can promote the diffusion of C element to form local pearlite anda bainitic structure. However, excessive Mn element coarsens crystal grains, tempers brittleness is generated, and overheat sensitivity of steel is increased. Meanwhile, the hydrogen content of austenite dissolution is increased in the enameling process, the possibility of scale explosion is increased in the subsequent cooling process, and the method is controlled to be 0.20-0.60%.
4) Phosphorus P: the alloy is one of common elements of a weather-resistant steel plate, can improve the weather resistance of the steel plate, can be in solid solution in a structure, or FeTiP and the like exist as precipitates, and can be used as hydrogen traps to improve the anti-scaling performance. Meanwhile, the structural distortion caused by solid solution of P can also increase the hydrogen storage capacity of the tissue and improve the anti-scaling performance. However, P is easy to segregate, so that the plasticity, low-temperature toughness and welding performance of steel are reduced, meanwhile, the segregation of P element influences the precipitation behavior of second phase particles in a tissue, the second phase particles are preferentially precipitated at the position, and the anti-fishscale performance of a substrate is influenced, therefore, the invention adds trace B element, can reduce the segregation of P element, ensures that the precipitated particles which are subsequently precipitated in the tissue can be uniformly distributed, and improves the anti-fishscale performance of the substrate, and controls the content of P element to be 0.035-0.080%.
5) Sulfur S: the Mn element is easy to form MnS inclusion, so that the mechanical property of steel is deteriorated, meanwhile, the potential difference is easy to form between the large-size inclusion part and the steel plate, the pitting corrosion part is preferentially formed, the corrosion performance is deteriorated, and meanwhile, the Ti element of the steel type is easy to form Ti (C, S). The MnS composite precipitate can improve the anti-scaling performance of the steel plate, so the invention needs to control the content of S element to be 0.005-0.025%.
5) Copper Cu: the corrosion resistance of the steel plate can be improved, a barrier layer mainly containing Cu is formed between the steel plate and the rust layer, the barrier layer is firmly combined with the steel plate to well protect the steel plate, the corrosion resistance of the steel plate is improved, cu element is easy to gather on the surface to form Cu particles, the existence of the particles seriously affects the enamel adhesion performance of the steel plate in the subsequent process, the Cu enrichment can be avoided by adding trace B in a structure and reasonable process control, so that the Cu steel plate exists in the steel plate in a solid solution state form, the lattice distortion of the steel plate is caused, a large number of dislocation exists in the structure, the dissolving [ H ] capability is further improved, but Cu is easy to generate Cu embrittlement phenomenon, the material performance is deteriorated, and the Cu content is controlled: 0.30 to 0.55 percent.
6) Chromium Cr: can improve the weather resistance of the steel plate, the passivation performance of the steel plate and the corrosion resistance, and Cr exists in the form of precipitate by using an annealing process to form a large amount of fine (Cr and Fe) 23 C 6 And (Cr, fe) 7 C 3 And the like, and the Cr element is added to be used as a hydrogen trap, so that the hardenability of the steel plate can be improved, carbide and pearlite in a tissue can be promoted to form in the subsequent annealing process, the positions can also be used as the hydrogen traps, the anti-scaling performance can be effectively improved, and the Cr content is controlled to be 0.10-0.45%.
7) Nickel Ni: can densify the iron scale on the surface of the steel plate, and has effects of solid solution strengthening and improving hardenability of the steel plate. The addition of Ni can form stable compound with Cu to improve corrosion resistance, and Ni can make the combination of enamel layer and steel plate more compact, can increase adhesion and raise anti-scaling performance, so that it is controlled to 0.20-0.60%.
8) Ti: is easy to be compounded with C, N to form a plurality of TiN, tiC, ti (C, N) and Ti (C, S) precipitates, and can improve the anti-scaling performance of the steel plate and has great effect. The invention therefore provides Ti: 0.010-0.055%.
9) B: the moderate amount of B element can increase the second phase nucleation point, promote other second phase particles to separate out, B is easy to separate out with C, N, improve the anti-scaling performance of the steel plate, meanwhile, B element can be preferentially gathered at the crystal boundary, fill up the vacancy and defect, avoid P, cu element gathering at this position, cause the steel plate performance to be greatly reduced, make B element gather at this position, can improve the plasticity and toughness of the steel plate, the invention controls B:0.0008 to 0.0014 percent.
Wherein the component proportioning system needs to satisfy: the first proportioning system is as follows: 1. not less than (6 x [ Ti ])/(22 [ C ]) not less than 0.01, tiN, tiC, ti (C, N) and Ti (C, S) precipitates can be formed more, the anti-scaling performance of the steel plate is further improved, and the proportioning system II is satisfied: [B] the proportion of B element can increase the second phase nucleation point more and promote other second phase particles to be separated out, and the proportion of B element is easy to separate out with C, N, so that the anti-scaling performance of the steel plate is further improved, wherein the proportion of [ P ], [ Ti ], [ C ] and [ B ] are weight percentages of corresponding elements, P, cu elements can effectively improve the corrosion resistance of the base plate, the addition of P is easy to gather at a grain boundary, cu is easy to gather on the surface to form Cu small particles, the distribution and separation behavior of separated particles in a tissue and the adhesiveness in the enamel process are influenced, and trace B element is added, so that the problems of P and Cu local gathering can be effectively solved at the grain boundary and the curve, on one hand, the enamel performance is improved, and the corrosion resistance of the base plate is improved on the other hand; wherein the component proportioning system also needs to satisfy a proportioning system III:
(0.071 [ Si ] +0.217 [ P ] +0.119 [ Cu ] +0.107 [ Cr ] +0.703 [ Ti ]) is not less than 0.1, wherein [ Si ], [ P ], [ Cu ], [ Cr ] and [ Ti ] are the weight percentages of the corresponding elements, the ratio is combined, cu, P, cr and other alloys are matched with trace Ti, B and other elements, the hydrogen trap quantity in the structure can be effectively increased, the anti-scaling property of the steel plate is improved, the steel plate has weather resistance, the finally prepared steel plate can be used for enamel, the steel plate has double corrosion resistance, and the service life of a workpiece can be greatly prolonged
To describe in more detail the cold-rolled weathering steel plates having enamelable properties and the preparation thereof according to the present invention, comparison of the parameters was carried out with the cold-rolled weathering steel plates of examples 1 to 6 and comparative example 1 and the cold-rolled enamelled steel plates of comparative example 2:
1. the chemical composition used is shown in Table 1:
table 1 chemical composition table: the balance of Fe and inevitable impurities
2. The preparation method comprises the following specific steps:
after molten steel realizes continuous casting of molten steel according to the molten steel composition requirement, 1) rolling process control: slab tapping temperature: 1180-1220 ℃, firstly performing rough rolling by 2 rolls, and then performing hot continuous rolling by a 7-frame. Finishing temperature: 850-880 ℃; coiling temperature: 560 ℃ to 620 ℃ and the finishing temperature and the coiling temperature are required to satisfy: and in 5-10 s, the finishing temperature-coiling temperature=250-300 ℃, and the low-temperature finishing and low-temperature coiling are adopted, so that dislocation and deformation energy in a tissue can be effectively increased, the number of hydrogen traps is increased, meanwhile, the low finishing temperature and the low coiling temperature avoid long-range diffusion of elements, and the solid solution quantity of elements such as P, cr, cu and the like in the steel plate is increased. The temperature difference between the finishing temperature and the coiling temperature is kept within 5-10 seconds, so that the phase change supercooling degree can be effectively increased, the phase change of the tissue is promoted, elements are enabled to be solid-dissolved in the tissue, and the number of hydrogen traps in the tissue is increased.
2) The total rolling reduction rate of the cold rolling is 60-80 percent. The method can ensure that the steel plate has high work hardening degree and more tissue dislocation, promotes the formation of precipitates in the annealing process, simultaneously has more high dislocation tissue to dissolve Cu, ni and other alloys, and increases the number of hydrogen traps. Rolling to obtain the target thickness of 0.5-2.5 mm.
3) Continuous annealing: the annealing temperature is 700-780 ℃, and the annealing speed is as follows: 80-140 m/min, cooling rate of 40-70 deg.C/s, and protecting atmosphere (N) 2 -H 2 ) Annealing under the environment; the continuous annealing is favorable for the complete recrystallization of crystal grains, improves the forming performance of the material, simultaneously B, cr improves the hardenability of the material, promotes the formation of pearlite and carbide, and is used as a hydrogen trap, so that the anti-scaling performance of the steel plate is greatly improved, meanwhile, the annealing temperature is not too high, the diffusion and the segregation of weather-resistant elements are increased, and the hydrogen storage capacity of the steel plate is reduced.
4) Leveling: leveling elongation: 0.8% -1.4%, target value: 1.2 percent, improves the shape of the plate, eliminates the yield platform, can increase the tissue unreliability and improves the hydrogen melting capability.
The main process parameters and product properties of each of the examples and comparative examples are shown in Table 2.
TABLE 2 production process parameters and product Properties
3. Further comprising the following steps of enamelling: enamel is coated by a certain paint manufacturer, enamel method and wet method: cleaning the test sample, spraying, baking at 100 ℃ and enamelling at 850 ℃ for 10min to obtain enamel steel, wherein the performance is shown in the enamelling result of Table 3.
TABLE 3 enameling results
Example 1 Enamelling at 850 ℃ for 10min No scale explosion and normal
Example 2 Enamelling at 850 ℃ for 10min No scale explosion and normal
Example 3 Enamelling at 850 ℃ for 10min No scale explosion and normal
Example 4 Enamelling at 850 ℃ for 10min No scale explosion and normal
Example 5 Enamelling at 850 ℃ for 10min No scale explosion and normal
Example 6 Enamelling at 850 ℃ for 10min No scale explosion and normal
Comparative example 1 Enamelling at 850 ℃ for 10min The occurrence of scale explosion
Comparative example 2 Enamelling at 850 ℃ for 10min No scale explosion and normal
The cold-rolled weather-resistant steel plate with enamel performance has the yield strength of 300-450 MPa, the tensile strength of more than or equal to 450MPa, the elongation of more than or equal to 28 percent, good forming performance and no fishscale enamel, and can be used in the industries of waste incineration and heat exchangers.
4. Corrosion resistance performance comparison of each example and comparative example, corrosion resistance performance test was performed as TB/T2375 for 72 hours.
The chemical composition of the comparative sample Q345B is shown in Table 4, and the corrosion resistance is shown in Table 5
Table 4 comparative sample chemistry
TABLE 5 Corrosion resistance Property results
Category(s) Relative corrosion rate%
Example 1 58.2
Example 2 43.9
Example 3 54.7
Example 4 48.2
Example 5 60.0
Example 6 56.7
Comparative example 1 46.5
Comparative example 2 98.7
Comparison sample Q345B 100
As shown in fig. 1 to 11, a large amount of carbide and pearlite exist in the tissue of example 1; the tissue of example 3 had a large amount of carbides and pearlite present; the tissue of example 5 had a large amount of carbides and pearlite present; the tissue of comparative example 1 had a large amount of carbide and pearlite present; the tissue of comparative example 2 was a pure ferrite.
Examples 1 to 6 and comparative example 1 had similar structures, ferrite+carbide+pearlite, while comparative example 2 was enamel steel, and had a pure ferrite structure. Since the structures of examples 1 to 6 contain a large amount of alloying elements, on the one hand, the hardenability of the steel sheet was improved, and on the other hand, the diffusion of C atoms was reduced, pearlite had been formed in the structures, and the hydrogen storage capacity of the steel sheet was improved. However, the comparative example 1 does not adopt elements such as Ti, B and the like, and the component system thereof does not satisfy the first proportioning system: 1. not less than 6 x [ Ti ]/22[ C ] not less than 0.01 and a proportioning system II: [B] the ratio of P to P is greater than or equal to 0.01, so that the problems of scale explosion and the like are easy to occur in the enamel process, and the corrosion resistance is extremely poor in the actual use process. In comparative example 2, although no scale explosion occurred, the component system did not satisfy the ratio system three: 0.071 [ Si ] +0.217 [ P ] +0.119 [ Cu ] +0.107 [ Cr ] +0.703 [ Ti ]. Gtoreq.0.1, the corrosion resistance is extremely poor in the circumferential immersion, and once the enamel layer of the sample piece cracks in the use process, the component can rapidly corrode the steel plate, so that the component is scrapped and the double corrosion resistance is not provided.
The invention and its embodiments have been described above by way of illustration and not limitation, and the invention is illustrated in the accompanying drawings and described in the drawings in which the actual structure is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.

Claims (5)

1. A cold rolled weather resistant steel sheet having enamelable properties, characterized in that: the chemical components and weight percentages are as follows: c: 0.07-0.15%, si: 0.10-0.60%, mn: 0.20-0.60%, P:0.035 to 0.080%, S: 0.005-0.025%, cu: 0.30-0.55%, ni: 0.20-0.70%, cr: 0.10-0.45%, als: 0.008-0.030%, ti: 0.015-0.055%, B: 0.0008-0.0014%, and the balance of Fe and unavoidable impurities;
wherein the composition ratio is required to satisfy: the ratio of [ P ], [ Ti ], [ C ] and [ B ] is not less than 0.01 and not more than 6 x [ Ti ])/(22 x [ C ]) is not less than 1, and the ratio of [ B ]/[ P ] is not less than 0.01, wherein, the weight percentages of the corresponding elements are;
wherein the component proportions also need to satisfy:
(0.071 x [ Si ] +0.217 x [ P ] +0.119 x [ Cu ] +0.107 x [ Cr ] +0.703 x [ Ti ]) is not less than 0.1, wherein [ Si ], [ P ], [ Cu ], [ Cr ] and [ Ti ] are weight percentages of the corresponding elements.
2. A method for producing cold rolled weathering steel plates with enamelable properties according to claim 1, characterized in that: the method comprises the following steps:
s1, smelting molten steel: smelting molten steel according to the component requirements of the molten steel;
s2, a rolling process: slab tapping temperature: 1180-1220 ℃; finishing temperature: 850-880 ℃; coiling temperature: 560 ℃ to 620 ℃; rolling into a steel plate;
s3, continuous annealing: the annealing temperature is 700-780 ℃, and the annealing speed is as follows: 80-140 m/min, and the cooling speed is 40-70 ℃/s;
s4, leveling: leveling the steel plate.
3. The method for producing cold rolled weathering steel plate having enamelable properties according to claim 2, characterized in that: in the step S2, the total rolling reduction is 60% -80%, and the target thickness is 0.5-2.5 mm.
4. A method for producing cold rolled weathering steel plates with enamelable properties according to any one of claims 2 to 3, characterized in that: in step S4, the elongation is flattened: 0.8% -1.4%.
5. The method for producing cold rolled weathering steel plates having enamelable properties of claim 4, characterized in that: and the method also comprises the step S5 of wet enameling: cleaning a sample, spraying, baking at 100 ℃, and enamelling at 850 ℃ for 10min.
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CN101370952A (en) * 2006-01-18 2009-02-18 新日本制铁株式会社 Enamelware and glaze
CN106282846A (en) * 2015-05-28 2017-01-04 鞍钢股份有限公司 Enamel steel with excellent fish scaling resistance and manufacturing method of steel plate thereof
CN110318006A (en) * 2019-07-31 2019-10-11 马鞍山钢铁股份有限公司 A kind of cold rolling weather resisting steel and preparation method thereof
CN113755747A (en) * 2021-08-02 2021-12-07 敬业钢铁有限公司 Steel plate matrix enamel material for chemical vessel and production method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06192727A (en) * 1992-12-24 1994-07-12 Sumitomo Metal Ind Ltd Production of aluminum killed cold rolled steel sheet for enameling

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101370952A (en) * 2006-01-18 2009-02-18 新日本制铁株式会社 Enamelware and glaze
CN106282846A (en) * 2015-05-28 2017-01-04 鞍钢股份有限公司 Enamel steel with excellent fish scaling resistance and manufacturing method of steel plate thereof
CN110318006A (en) * 2019-07-31 2019-10-11 马鞍山钢铁股份有限公司 A kind of cold rolling weather resisting steel and preparation method thereof
CN113755747A (en) * 2021-08-02 2021-12-07 敬业钢铁有限公司 Steel plate matrix enamel material for chemical vessel and production method thereof

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