CN111575581B - Acid corrosion resistant martensite wear-resistant steel plate and manufacturing method thereof - Google Patents

Acid corrosion resistant martensite wear-resistant steel plate and manufacturing method thereof Download PDF

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CN111575581B
CN111575581B CN202010387564.0A CN202010387564A CN111575581B CN 111575581 B CN111575581 B CN 111575581B CN 202010387564 A CN202010387564 A CN 202010387564A CN 111575581 B CN111575581 B CN 111575581B
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acid corrosion
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CN111575581A (en
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梁亮
严立新
李光辉
邓想涛
王昭东
刘宁
董常福
郑庆
刘旭辉
汪宏兵
温长飞
肖爱达
徐德强
谢世正
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Hunan Valin Lianyuan Iron & Steel Co Ltd
Hunan Valing Energy Saving Power Generation Co ltd
Northeastern University China
Lysteel Co Ltd
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Hunan Valing Energy Saving Power Generation Co ltd
Hunan Valin Lianyuan Iron & Steel Co Ltd
Lysteel Co Ltd
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    • 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
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    • 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
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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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C33/00—Making ferrous alloys
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    • 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
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    • 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
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations
    • 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
    • C21D2211/008—Martensite

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Abstract

The application discloses an acid corrosion resistant martensite wear-resistant steel plate, which comprises 0.14 wt% to 0.22 wt% of C; si is more than or equal to 0.30 wt% and less than or equal to 0.60 wt%; mn is more than or equal to 0.30 wt% and less than or equal to 1.00 wt%; ti is more than or equal to 0.010 wt% and less than or equal to 0.020 wt%; nb is more than or equal to 0.02 wt% and less than or equal to 0.04 wt%; ni is more than or equal to 0.50 wt% and less than or equal to 1.0 wt%; cu is more than or equal to 0.20 weight percent and less than or equal to 0.50 weight percent; cr is between 0.9 and 1.3 weight percent; sb accounts for 0.08-0.12 wt%; b is more than or equal to 0.0010 wt% and less than or equal to 0.0020 wt%; s is more than 0 and less than or equal to 0.003 weight percent; p is more than 0 and less than or equal to 0.012wt percent; the acid corrosion resistant martensite wear-resistant steel plate can solve the problems of hardness, plasticity, toughness, wear resistance and corrosion resistance of the steel plate.

Description

Acid corrosion resistant martensite wear-resistant steel plate and manufacturing method thereof
Technical Field
The application belongs to the technical field of steel smelting, and particularly relates to an acid corrosion resistant martensite wear-resistant steel plate and a manufacturing method thereof.
Background
The wear-resistant steel plate is widely used for equipment in the fields of mines, coal mines, metallurgy and the like as common steel for engineering machinery, and the corrosion resistance and the wear resistance of the wear-resistant steel plate are required to be high because the working environment in the fields of mines, coal mines, metallurgy and the like is severe.
However, in order to increase the wear resistance of the steel sheet, the conventional wear-resistant steel sheet is generally manufactured by increasing the carbon content or Ti content, which cannot ensure the corrosion resistance of the steel sheet although increasing the wear resistance of the steel sheet, and which satisfies the requirement for high wear resistance at the expense of hardness, plasticity, or toughness of the steel sheet.
Therefore, how to greatly improve the wear resistance and the corrosion resistance of the steel plate on the premise of not influencing the hardness, the plasticity and the toughness of the steel plate becomes a key technical problem to be solved urgently in the current metallurgy and wear-resistant industries.
Disclosure of Invention
In view of the above, the present invention aims to provide an acid corrosion resistant martensitic wear resistant steel plate and a manufacturing method thereof, so as to solve the problem that hardness, plasticity, toughness, wear resistance and corrosion resistance of the steel plate cannot be simultaneously considered in the prior art.
To achieve the above object, according to an aspect of the present invention, there is provided an acid corrosion resistant martensitic wear resistant steel sheet comprising, in mass%: c is between 0.14 and 0.22 percent by weight; si is more than or equal to 0.30 wt% and less than or equal to 0.60 wt%; mn is more than or equal to 0.30 wt% and less than or equal to 1.00 wt%; ti is more than or equal to 0.010 wt% and less than or equal to 0.020 wt%; nb is more than or equal to 0.02 wt% and less than or equal to 0.04 wt%; ni is more than or equal to 0.50 wt% and less than or equal to 1.0 wt%; cu is more than or equal to 0.20 weight percent and less than or equal to 0.50 weight percent; cr is between 0.9 and 1.3 weight percent; sb accounts for 0.08-0.12 wt%; b is more than or equal to 0.0010 wt% and less than or equal to 0.0020 wt%; s is more than 0 and less than or equal to 0.003 weight percent; p is more than 0 and less than or equal to 0.012wt percent; the balance of iron and other inevitable impurities, wherein the acid corrosion resistance index I of the acid corrosion resistance martensite wear-resistant steel plate is 7.0-15; wherein the calculation formula of the acid corrosion resistance index is as follows:
I＝26.01(％Cu)+3.88(％Ni)+1.20(％Cr)+1.49(％Si)+17.28(％P)-7.29(％Cu)(％Ni)-9.10(％Ni)(％P)-33.39(％Cu)2
wherein, the element symbol in parentheses is the mass percentage of the corresponding element, and the% element symbol represents the mass percentage of the corresponding element multiplied by 100.
Optionally, the acid corrosion resistant martensitic wear resistant steel sheet comprises in mass percent: c is between 0.14 and 0.18 percent by weight; si is more than or equal to 0.30 weight percent and less than or equal to 0.50 weight percent; mn is more than or equal to 0.30 wt% and less than or equal to 0.60 wt%; ti is more than or equal to 0.012 wt% and less than or equal to 0.018 wt%; nb is more than or equal to 0.02 wt% and less than or equal to 0.03 wt%; ni is more than or equal to 0.50 wt% and less than or equal to 0.8 wt%; cu is more than or equal to 0.25 weight percent and less than or equal to 0.45 weight percent; cr is between 0.9 and 1.3 weight percent; sb accounts for 0.08-0.10 wt%; b is more than or equal to 0.0015 weight percent and less than or equal to 0.0020 weight percent; s is more than 0 and less than or equal to 0.003 weight percent; p is more than 0 and less than or equal to 0.012wt percent; the balance of iron and other inevitable impurities.
Optionally, the acid corrosion resistant martensitic wear resistant steel sheet comprises in weight percent: c: 0.15 wt%; si: 0.40 wt%; mn: 0.45 wt%; ti: 0.014 wt%; nb: 0.02 wt%; ni: 0.65 wt%; cu: 0.38 wt%; cr: 1.1 wt%; sb: 0.10 wt%; b: 0.0018 wt%; s: 0.001 wt%; p: 0.0005 wt%; the balance of iron and other inevitable impurities.
Optionally, the acid corrosion resistant martensitic wear resistant steel plate has an acid corrosion resistance index I of 7-10.
Optionally, the martensitic wear resistant steel sheet structure resistant to acid corrosion comprises tempered martensite and carbides.
Optionally, the yield strength of the acid corrosion resistant martensite wear-resistant steel plate is 1100 MPa-1300 MPa, the tensile strength is 1300 MPa-1500 MPa, the hardness of the steel plate is HBW 420-480, the elongation is 8% -15%, and the impact energy at-40 ℃ is 27J-70J.
On the other hand, the embodiment of the application provides a manufacturing method of an acid corrosion resistant martensitic wear-resistant steel plate, which specifically comprises the following steps: smelting the molten steel into a plate blank, hot-rolling the plate blank to form a steel coil, and sequentially flattening, quenching and tempering the steel coil to obtain the acid corrosion resistant martensite wear-resistant steel plate.
Optionally, the smelting molten steel into a slab comprises: and continuously casting the molten steel into a plate blank after KR method desulfurization, converter steelmaking and RH method refining treatment in sequence, wherein the continuous casting step comprises that the continuous casting drawing speed is 0.8-1.3 m/min.
Optionally, the hot rolled slab forming a coil of steel comprises: the method comprises the following steps of sequentially reheating the plate blank, rough rolling, finish rolling and laminar cooling, and then coiling to form a steel coil, wherein the reheating step comprises reheating the plate blank, the heating temperature is 1200-1300 ℃, and the heat preservation time is 20-30 min; and/or
The rough rolling step comprises: the total reduction rate of rough rolling is 75-85%, and the single-pass reduction rate of rough rolling is 15-25%; the surface temperature of the rough rolled plate blank is 1050-1100 ℃; and/or
The finish rolling step comprises: the total reduction rate of finish rolling is 60-80%, and the single-pass reduction rate of finish rolling is 12-20%; the finish rolling temperature of finish rolling is 840-890 ℃; and/or
The laminar cooling step comprises the step that the cooling speed of the laminar cooling is 10-25 ℃/s; and/or
The coiling step comprises the coiling temperature of 560-650 ℃.
Optionally, the quenching step comprises quenching heating at 850-900 ℃ for 20-60 min; and/or
The tempering step comprises the steps of tempering at the temperature of 150-200 ℃ and tempering heat preservation for 30-60 min.
Compared with the prior art, the method has the following beneficial effects:
the acid corrosion resistant martensite wear-resistant steel plate comprises high corrosion resistant elements Cr, Ni, Sb and Cu, so that on one hand, the corrosion resistance of the steel plate can be ensured, and the acid corrosion resistant index I can reach more than 7.0; on the other hand, the higher Cr content can ensure higher hardness under the relatively lower C content, and the Sb and Cr are compositely added to be synergistically enriched in the rust layer, so that a compact oxide film which is higher than the matrix by a plurality of times and is rich in elements such as Sb, Cr and the like is formed, the transmission of corrosive ions is obviously hindered, and the corrosion environment with coexisting sulfate radicals and chloride ions is more resistant. Sb has an effect on the resistance to sulfuric acid, hydrochloric acid, and acid corrosion containing chloride, and the greater the amount of Sb, the higher the sulfuric acid resistance, but the lower the hot workability, the toughness of the steel plate, and the welded joint. The higher Ni content can ensure that the material has higher strength and better low-temperature impact toughness. The embodiment of the application properly controls each chemical element, and the steel plate has better comprehensive properties of mechanics, welding, acid corrosion resistance and the like by simple steelmaking, rolling and cooling processes.
The acid corrosion resistant martensite wear-resistant steel plate disclosed by the embodiment of the application has the yield strength of 1100 MPa-1300 MPa, the tensile strength of 1300 MPa-1500 MPa, the hardness of the steel plate HBW 420-480, the elongation of 8% -15%, the impact energy at-40 ℃ of 27J-70J, and the service life of the steel plate under the acid corrosion condition can reach more than 2.5 times of that of Hardox 450.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is a metallographic structure diagram of a martensitic wear-resistant steel plate resistant to acid corrosion according to an embodiment of the present application.
Fig. 2 is a metallographic structure diagram of a martensitic wear-resistant steel plate resistant to acid corrosion according to another embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, the embodiments of the present application provide a martensitic wear-resistant steel sheet resistant to acid corrosion.
In the embodiment of the application, the acid corrosion resistant martensitic wear resistant steel plate comprises the following components in percentage by mass: c is between 0.14 and 0.22 percent by weight; si is more than or equal to 0.30 wt% and less than or equal to 0.60 wt%; mn is more than or equal to 0.30 wt% and less than or equal to 1.00 wt%; ti is more than or equal to 0.010 wt% and less than or equal to 0.020 wt%; nb is more than or equal to 0.02 wt% and less than or equal to 0.04 wt%; ni is more than or equal to 0.50 wt% and less than or equal to 1.0 wt%; cu is more than or equal to 0.20 weight percent and less than or equal to 0.50 weight percent; cr is between 0.9 and 1.3 weight percent; sb accounts for 0.08-0.12 wt%; b is more than or equal to 0.0010 wt% and less than or equal to 0.0020 wt%; s is more than 0 and less than or equal to 0.003 weight percent; p is more than 0 and less than or equal to 0.012wt percent; the balance of iron and other inevitable impurities, and the acid corrosion resistant index I of the acid corrosion resistant martensitic wear-resistant steel plate is 7.0-15.
In one embodiment, the acid corrosion resistant index I of the acid corrosion resistant martensitic wear resistant steel plate is 10-15.
In one embodiment, the acid corrosion resistant index I of the acid corrosion resistant martensitic wear resistant steel plate is 12-15.
Wherein the calculation formula of the acid corrosion resistance index I is shown as follows,
I＝26.01(％Cu)+3.88(％Ni)+1.20(％Cr)+1.49(％Si)+17.28(％P)-7.29(％Cu)(％Ni)-9.10(％Ni)(％P)-33.39(％Cu)2
wherein, the element symbol in parentheses is the mass percentage of the corresponding element, and the% element symbol represents the mass percentage of the corresponding element multiplied by 100.
In the embodiment of the application, high corrosion resistant elements Cr, Ni, Sb and Cu are added, so that on one hand, the corrosion resistance of the steel plate can be ensured, and the acid corrosion resistance index I can reach more than 7.0; on the other hand, the higher Cr content can ensure higher hardness under the relatively lower C content, and the Sb and Cr are compositely added to be synergistically enriched in the rust layer, so that a compact oxide film which is higher than the matrix by a plurality of times and is rich in elements such as Sb, Cr and the like is formed, the transmission of corrosive ions is obviously hindered, and the corrosion environment with coexisting sulfate radicals and chloride ions is more resistant. Sb has an effect on the resistance to sulfuric acid, hydrochloric acid, and acid corrosion containing chloride, and the greater the amount of Sb, the higher the sulfuric acid resistance, but the lower the hot workability, the toughness of the steel plate, and the welded joint. The higher Ni content can ensure that the material has higher strength and better low-temperature impact toughness.
In one embodiment, the acid corrosion resistant martensitic wear resistant steel sheet comprises in mass percent: c is between 0.14 and 0.18 percent by weight; si is more than or equal to 0.30 weight percent and less than or equal to 0.50 weight percent; mn is more than or equal to 0.30 wt% and less than or equal to 0.60 wt%; ti is more than or equal to 0.012 wt% and less than or equal to 0.018 wt%; nb is more than or equal to 0.02 wt% and less than or equal to 0.03 wt%; ni is more than or equal to 0.50 wt% and less than or equal to 0.8 wt%; cu is more than or equal to 0.25 weight percent and less than or equal to 0.45 weight percent; cr is between 0.9 and 1.3 weight percent; sb accounts for 0.08-0.10 wt%; b is more than or equal to 0.0015 weight percent and less than or equal to 0.0020 weight percent; s is more than 0 and less than or equal to 0.003 weight percent; p is more than 0 and less than or equal to 0.012wt percent; the balance of iron and other inevitable impurities.
In one embodiment, the acid corrosion resistant martensitic wear resistant steel sheet comprises in mass percent: c is between 0.15 and 0.16 percent by weight; si is more than or equal to 0.35 wt% and less than or equal to 0.45 wt%; mn is more than or equal to 0.40 weight percent and less than or equal to 0.50 weight percent; ti is more than or equal to 0.013 wt% and less than or equal to 0.015 wt%; nb is more than or equal to 0.02 wt% and less than or equal to 0.25 wt%; ni is more than or equal to 0.6 wt% and less than or equal to 0.7 wt%; cu is more than or equal to 0.35 weight percent and less than or equal to 0.40 weight percent; cr is between 0.9 and 1.1 weight percent; sb accounts for 0.08-0.10 wt%; b is more than or equal to 0.0016 and less than or equal to 0.0018 percent by weight; s is more than 0 and less than or equal to 0.002 wt%; p is more than 0 and less than or equal to 0.010 wt%; the balance of iron and other inevitable impurities.
As a specific example, the acid corrosion resistant martensitic wear resistant steel sheet comprises, in mass percent, C: 0.15 wt%; si: 0.40 wt%; mn: 0.45 wt%; ti: 0.014 wt%; nb: 0.02 wt%; ni: 0.65 wt%; cu: 0.38 wt%; cr: 1.1 wt%; sb: 0.10 wt%; b: 0.0018 wt%; s: 0.001 wt%; p: 0.0005 wt%; the balance of iron and other inevitable impurities.
In the embodiment of the application, the addition principle of each chemical element is as follows:
c, carbon C: the carbon can improve the hardenability of the steel plate, has strong solid solution strengthening effect, and obviously improves the strength and hardness of the martensite wear-resistant steel plate; however, when the carbon content is too high, the elongation and impact energy performance of the wear-resistant steel plate are reduced, and the welding performance is poor; considering other aspects of mechanical property, processability and the like, the content of C is controlled to be 0.14-0.22 wt% in the examples of the application.
Silicon Si: si element is solid-dissolved in the steel sheet, and has a certain solid-solution strengthening effect, and the strength of the steel sheet can be improved. Too high a Si content inhibits the formation of cementite, while a higher Si content amplifies the formation of ferrite phase. Therefore, the Si content in the examples of the present application is controlled to 0.30 wt% to 0.60 wt%.
Manganese Mn: mn element is a weak carbide-forming element, and is usually dissolved in a steel sheet to exert a solid solution strengthening effect; the high Mn content can increase the cracking tendency of the plate blank, easily form longitudinal cracks and other defects in the plate blank production process, and the low Mn content has small contribution to the strength, so that C element or other precious alloy elements such as Mo element and the like need to be added to ensure the strength of the steel plate. However, the addition of C element deteriorates the weldability of the steel plate, and the addition of other noble elements increases the cost of the steel plate. Therefore, in order to provide a steel sheet with good toughness, the content of the Mn element in the examples of the present application is controlled to be 0.30 wt% to 1.00 wt%.
Titanium Ti: ti is mainly used for fixing N, Ti and N form TiN at high temperature, and TiN can inhibit austenite grains from growing when a plate blank is heated to austenitize. In the hot rolling process, Ti and C are formed in a lower temperature range and TiC, and fine TiC particles are beneficial to improving the low-temperature impact property of the steel plate. However, when the Ti content is too high, coarse square TiN is precipitated, and stress concentrates near TiN particles when the steel plate is stressed, so that the stress becomes a nucleation growth source of micro-cracks, and the fatigue performance of the steel plate is reduced. In summary, the content of Ti element in the embodiment of the present application is controlled to be 0.010 wt% to 0.020 wt%.
Niobium Nb: niobium is a compound forming element of strong carbon and nitrogen, and has a very obvious effect on grain refinement. NbC strain is induced and precipitated in the hot rolling process to hinder recovery and recrystallization of deformed austenite, and the deformed austenite structure rolled in a non-recrystallization area in the finish rolling stage is converted into a fine phase change product during phase change through controlled rolling and controlled cooling, so that the steel has high strength and high toughness, and the proper content fully plays a role in controlling rolling. And the higher Nb content can form coarse NbC precipitation in the tempering process, thereby reducing the low-temperature impact energy of the steel plate. Therefore, in order to control the microstructure and the mechanical property of the steel plate, the content of the Nb element is controlled to be 0.020 wt% to 0.040 wt% in the embodiment of the application.
Chromium Cr: the Cr element and the Fe element can form a continuous solid solution and form a plurality of carbides with the C element. Cr element can replace Fe element in cementite to form M3C, and can form M7C3And M23C6，M3C、M7C3And M23C6These phases can significantly improve the hardness and wear resistance of the steel sheet, and Cr elements and Cr carbides dissolved in the steel improve the strength of the steel sheet. In addition, Cr can obviously improve the corrosion resistance of the steel plate, so that the acid corrosion resistance of the steel plate can be obviously improved after high content of Cr is added. However, a higher content of Cr forms coarser carbides, thereby deteriorating the impact properties of the steel sheet. Therefore, in order to ensure the corrosion resistance and strength of the steel plate, the content of the Cr element is controlled to be 0.9 wt% to 1.3 wt% in the embodiments of the present application.
Antimony Sb: sb is often continuously enriched in steel as a harmful element, and seriously affects the quality of steel. In the embodiment of the application, Sb is an effective element for improving corrosion resistance, and is synergistically enriched in the rust layer through the compound addition of Sb and Cr, and a compact oxide film which is higher than a matrix by several times and rich in elements such as Sb, Cr and the like is formed, so that the transmission of corrosive ions is obviously hindered, and the corrosion environment with coexistence of sulfate radicals and chloride ions is more resistant. In order to ensure the desired corrosion resistance, it is necessary to exert the effect of both elements. Meanwhile, Ti and Sb attract each other, and when Ti is deviated to a grain boundary, Sb is dragged to the grain boundary, so that Sb is separated out in the form of fine second-phase particles instead of inclusions, and the particle size is 10-30 nm, so that the strength of the steel plate is improved. Sb has an effect on the resistance to sulfuric acid, hydrochloric acid, and acid corrosion containing chloride, and the greater the amount of Sb, the higher the sulfuric acid resistance, but the lower the hot workability, the toughness of the steel plate, and the welded joint. Therefore, the content of the Sb element is controlled to be 0.08-0.10 wt% in the embodiment of the application.
Copper Cu: cu is an essential element for improving the corrosion resistance of the steel plate, a compact sulfide film is formed on the surface of the steel plate, the uniform corrosion resistance and the local corrosion resistance of the steel plate can be improved, and the Cu content is higher than 0.2% in order to achieve the corrosion resistance protection effect. However, if the Cu content exceeds 0.5%, hot workability and weldability of the steel deteriorate. Therefore, the content of Cu element in the embodiment of the application is controlled to be 0.20 wt% to 0.50 wt%.
Nickel Ni: ni is also an element for improving corrosion resistance, and is usually used in combination with Cu. In order to achieve the protection effect of corrosion resistance, the Ni content should be more than 0.05%. However, if the Ni content exceeds 2.0%, the effect is saturated, which not only increases the cost but also deteriorates the workability and weldability of the steel sheet. Ni can obviously improve the low-temperature toughness of steel and has favorable effect on impact toughness and ductile-brittle transition temperature, but in consideration of cost factors, the content of Ni element is controlled to be 0.50 wt% -1.0 wt% in the embodiment of the application.
B, boron B: the addition of B element to steel increases the hardenability of the steel sheet, and forms a bainite or martensite structure. When the content of B is high, B atoms are enriched in grain boundaries, so that the bonding energy of the grain boundaries is reduced, and the intergranular fracture can occur under the impact action. Therefore, in the embodiment of the application, the content of the element B is controlled to be 0.0010 wt% to 0.0020 wt%.
P, S, O, N: harmful impurity elements in the steel significantly reduce the ductility and weldability of the steel, and therefore the content of the impurity elements should be reduced as much as possible.
In the embodiment of the application, the combination properties of better mechanics, welding, acid corrosion resistance and the like of the steel plate are obtained by properly controlling the elements, accurately proportioning the components and adopting simple steelmaking, rolling and cooling processes.
The acid corrosion resistant martensite wear-resistant steel plate comprises a martensite phase and carbides, wherein the carbides are mainly chromium carbides, the yield strength of the acid corrosion resistant martensite wear-resistant steel plate is 1100 MPa-1300 MPa, the tensile strength is 1300 MPa-1500 MPa, the steel plate hardness is HBW 420-480, the elongation is 8% -15%, the impact work at-40 ℃ is 27J-70J, and the service life of the acid corrosion resistant martensite wear-resistant steel plate under an acid corrosion condition can reach more than 2.5 times of that of Hardox 450.
On the other hand, the embodiment of the application provides a manufacturing method of the martensite wear-resistant steel plate resistant to acid corrosion.
In the embodiment of the application, the method for manufacturing the acid corrosion resistant martensitic wear-resistant steel plate comprises the following steps:
s100, smelting molten steel into a plate blank;
the smelting of the molten steel into the plate blank comprises the following steps: and continuously casting the molten steel into a plate blank after KR method desulfurization, converter steelmaking and RH method refining treatment in sequence, wherein the continuous casting step comprises that the continuous casting drawing speed is 0.8-1.3 m/min.
S200, hot rolling the plate blank to form a steel coil;
the hot rolled slab forming a coil of steel includes: the plate blank is sequentially reheated, roughly rolled, finely rolled and cooled by laminar flow, and then coiled to form a steel coil,
the reheating step comprises the steps of feeding continuously cast steel billets into a soaking pit furnace or a heating furnace for heating, and keeping the temperature for 20-30 min after the steel billets are heated to 1200-1300 ℃. The heating temperature and the holding time can homogenize the austenite structure in the billet, the carbides of Nb, Ti and the like in the billet are fully dissolved, and TiN is partially dissolved to prevent the growth of original austenite grains.
The rough rolling step comprises: the heated steel billet is sent into a rough rolling mill group for rough rolling, the rough rolling can be carried out for 5 or 7 passes, the single-pass reduction rate of the rough rolling mill is more than or equal to 15 percent, and the total reduction rate of the steel billet on the rough rolling mill is 75 to 85 percent; the final rolling temperature of rough rolling is 1080 ℃; the steel billet becomes an intermediate billet after rough rolling. Preferably, the single pass reduction of the roughing mill is between 15% and 25%.
The finish rolling step comprises: the intermediate billet is sent into a finishing mill group for finish rolling, the finish rolling can be performed for 5 or 7 times, the single-pass reduction rate of the finishing mill is more than or equal to 12 percent, and the total reduction rate of the billet on the finishing mill is more than 60 percent; the finish rolling temperature of finish rolling is 840-890 ℃; preferably, the single-pass reduction rate of the finishing mill is 12-20%, and the total reduction rate of the finishing mill is 60-80%.
The laminar cooling and coiling steps comprise that the intermediate blank after finish rolling can be cooled at a cooling speed of 10 ℃/S-25 ℃/S, and the steel plate is cooled to 560-650 ℃; and coiling the steel plate into a steel coil at the temperature of 560-650 ℃.
S300, sequentially flattening, quenching and tempering the steel coil to obtain the acid corrosion resistant martensite wear-resistant steel plate.
Stacking and cooling the coil of the coil which is off-line or slowly cooling the coil of the coil to room temperature; then flattening the steel plate at the temperature lower than 70 ℃,
quenching the steel plate after flattening, wherein the quenching heating temperature is 850-900 ℃, and the quenching heat preservation time is 20-60 min; and tempering treatment is carried out after quenching, the tempering temperature is 150-200 ℃, and the tempering heat preservation time is 30-60 min.
And air cooling after tempering and heat preservation.
The invention is further illustrated by the following specific examples:
the components of the acid corrosion resistant martensite wear-resistant steel plates and the comparative examples in the embodiments 1-2 are shown in table 1, the controlled rolling and controlled cooling process parameters are shown in table 2, the mechanical properties are shown in table 3, the periodic infiltration test results are shown in table 4, and the comparative steel type adopts Hardox 450.
TABLE 1
Component (%) C Si Mn Ti Nb Ni Cu Cr B S P Sb
Example 1 0.17 0.40 0.45 0.014 0.02 0.65 0.38 1.0 0.0018 0.001 0.0005 0.09
Example 2 0.17 0.50 0.50 0.018 0.03 0.70 0.45 1.2 0.0020 0.003 0.0004 0.11
Comparative example 1 0.18 0.49 1.20 0.004 0.016 0.08 0.01 0.62 0.0012 0.001 0.007 /
Examples 1-2 and comparative examples a method of making a steel sheet comprising the steps of:
the steel liquid is desulfurized by KR, then smelted by a 210-ton converter, desulfurized by the KR method, smelted by the converter, refined by an RH method, continuously cast into a plate blank, the plate blank is reheated, roughly rolled, finish rolled, laminar cooled and coiled into a steel coil, the steel coil is sequentially subjected to flattening, quenching and tempering to form the acid corrosion resistant martensite wear-resistant steel plate, and the acid corrosion resistant martensite wear-resistant steel plate can be subjected to spray printing, packaging and warehousing.
TABLE 2
Figure BDA0002484610430000101
The thickness of the martensitic wear-resistant steel plate resistant to acid corrosion and described in example 1 is 8mm, its metallographic structure diagram is shown in fig. 1, and the metallographic structure of the steel plate in fig. 1 is a tempered martensitic structure with a small amount of carbides.
The thickness of the martensitic wear-resistant steel plate resistant to acid corrosion and described in example 2 is 8mm, the metallographic structure diagram of the steel plate is shown in fig. 2, and the metallographic structure of the steel plate in fig. 2 is a tempered martensitic structure with a small amount of carbide.
The specific mechanical properties of the examples and comparative examples are shown in Table 3.
TABLE 3
Figure BDA0002484610430000111
The martensitic wear-resistant steel plates resistant to acid corrosion described in examples 1-2 all have yield strengths of more than 1100MPa and tensile strengths of more than 1400 MPa. The elongation after fracture is more than 10 percent, and the impact energy at minus 40 ℃ is more than 27J.
Periodic infiltration test: the results of the immersion in 20 wt% sulfuric acid at 20 ℃ for 24h are shown in Table 4:
TABLE 4
Numbering Hourly weight loss (g m)-2·h) Relative corrosion rate of 24 hours
Example 1 5.037 9.04％
Example 2 3.498 6.28％
Comparative example 55.722 100％
As can be seen from Table 4, compared with the comparative example, the relative corrosion rate of the examples 1-2 is less than 10%, the weather resistance is greatly improved, and the relative corrosion rate is less than 10% of Hardox450 of the martensite wear-resistant steel of the same grade. The examples 1-2 ensure the hardness, plasticity and toughness of the steel plate and obviously improve the acid corrosion resistance of the steel plate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (9)

1. An acid corrosion resistant martensitic wear resistant steel sheet characterized in that it comprises in mass percent: c is between 0.14 and 0.22 percent by weight; si is more than or equal to 0.30 wt% and less than or equal to 0.60 wt%; mn is more than or equal to 0.30 wt% and less than or equal to 1.00 wt%; ti is more than or equal to 0.010 wt% and less than or equal to 0.020 wt%; nb is more than or equal to 0.02 wt% and less than or equal to 0.04 wt%; ni is more than or equal to 0.50 wt% and less than or equal to 1.0 wt%; cu is more than or equal to 0.20 weight percent and less than or equal to 0.50 weight percent; cr is between 0.9 and 1.3 weight percent; sb accounts for 0.08-0.12 wt%; b is more than or equal to 0.0010 wt% and less than or equal to 0.0020 wt%; s is more than 0 and less than or equal to 0.003 weight percent; p is more than 0 and less than or equal to 0.012wt percent; the balance of iron and other inevitable impurities, wherein the acid corrosion resistance index I of the acid corrosion resistance martensite wear-resistant steel plate is 7.0-15; wherein the calculation formula of the acid corrosion resistance index is as follows:
I＝26.01(％Cu)+3.88(％Ni)+1.20(％Cr)+1.49(％Si)+17.28(％P)-7.29(％Cu)(％Ni)-9.10(％Ni)(％P)-33.39(％Cu)2
wherein, the element symbol in the brackets is the mass percent of the corresponding element, the% element symbol represents the mass percent of the corresponding element multiplied by 100,
the yield strength of the acid corrosion resistant martensite wear-resistant steel plate is 1100 MPa-1300 MPa, the tensile strength is 1300 MPa-1500 MPa, the hardness of the steel plate is HBW 420-480, the elongation is 8% -15%, and the impact energy at minus 40 ℃ is 27J-70J;
the acid corrosion resistant martensite wear-resistant steel plate is prepared by the following steps: smelting the molten steel into a plate blank, hot-rolling the plate blank to form a steel coil, and sequentially flattening, quenching and tempering the steel coil to obtain the acid corrosion resistant martensite wear-resistant steel plate.
2. The acid corrosion resistant martensitic wear resistant steel sheet according to claim 1 comprising in weight percent: c is between 0.14 and 0.18 percent by weight; si is more than or equal to 0.30 weight percent and less than or equal to 0.50 weight percent; mn is more than or equal to 0.30 wt% and less than or equal to 0.60 wt%; ti is more than or equal to 0.012 wt% and less than or equal to 0.018 wt%; nb is more than or equal to 0.02 wt% and less than or equal to 0.03 wt%; ni is more than or equal to 0.50 wt% and less than or equal to 0.8 wt%; cu is more than or equal to 0.25 weight percent and less than or equal to 0.45 weight percent; cr is between 0.9 and 1.3 weight percent; sb accounts for 0.08-0.10 wt%; b is more than or equal to 0.0015 weight percent and less than or equal to 0.0020 weight percent; s is more than 0 and less than or equal to 0.003 weight percent; p is more than 0 and less than or equal to 0.012wt percent; the balance of iron and other inevitable impurities.
3. The acid corrosion resistant martensitic wear resistant steel sheet according to claim 1 comprising in weight percent: c: 0.15 wt%; si: 0.40 wt%; mn: 0.45 wt%; ti: 0.014 wt%; nb: 0.02 wt%; ni: 0.65 wt%; cu: 0.38 wt%; cr: 1.1 wt%; sb: 0.10 wt%; b: 0.0018 wt%; s: 0.001 wt%; p: 0.0005 wt%; the balance of iron and other inevitable impurities.
4. The acid corrosion resistant martensitic wear resistant steel sheet according to claim 1 wherein the acid corrosion resistant martensitic wear resistant steel sheet has an acid corrosion resistance index I of 7 to 10.
5. A method for manufacturing an acid corrosion resistant martensitic wear resistant steel sheet as claimed in any one of claims 1 to 4 comprising the steps of: smelting the molten steel into a plate blank, hot-rolling the plate blank to form a steel coil, and sequentially flattening, quenching and tempering the steel coil to obtain the acid corrosion resistant martensite wear-resistant steel plate.
6. The method of manufacturing an acid corrosion resistant martensitic wear resistant steel sheet as claimed in claim 5 wherein said smelting molten steel into a slab comprises: and continuously casting the molten steel into a plate blank after KR method desulfurization, converter steelmaking and RH method refining treatment in sequence, wherein the continuous casting step comprises that the continuous casting drawing speed is 0.8-1.3 m/min.
7. The method of manufacturing an acid corrosion resistant martensitic wear resistant steel sheet as claimed in claim 5 wherein said hot rolled slab forming a coil of steel comprises: the method comprises the following steps of sequentially reheating the plate blank, rough rolling, finish rolling and laminar cooling, and then coiling to form a steel coil, wherein the reheating step comprises reheating the plate blank, the heating temperature is 1200-1300 ℃, and the heat preservation time is 20-30 min; and/or
The rough rolling step comprises: the total reduction rate of rough rolling is 75-85%, and the single-pass reduction rate of rough rolling is 15-25%; the surface temperature of the rough rolled plate blank is 1050-1100 ℃; and/or
The finish rolling step comprises: the total reduction rate of finish rolling is 60-80%, and the single-pass reduction rate of finish rolling is 12-20%; the finish rolling temperature of finish rolling is 840-890 ℃; and/or
The laminar cooling step comprises the step that the cooling speed of the laminar cooling is 10-25 ℃/s; and/or
The coiling step comprises the coiling temperature of 560-650 ℃.
8. The method for manufacturing the acid corrosion resistant martensitic wear resistant steel sheet as claimed in claim 5 wherein the step of quenching comprises quenching heating at 850-900 ℃ for 20-60 min.
9. The method for manufacturing the acid corrosion resistant martensitic wear resistant steel sheet as claimed in claim 5 wherein the step of tempering comprises tempering at a temperature of 150 ℃ to 200 ℃ for a tempering holding time of 30 to 60 min.
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