CN117265382A - Weather-resistant steel for railway vehicle and manufacturing method thereof - Google Patents

Weather-resistant steel for railway vehicle and manufacturing method thereof Download PDF

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CN117265382A
CN117265382A CN202210677518.3A CN202210677518A CN117265382A CN 117265382 A CN117265382 A CN 117265382A CN 202210677518 A CN202210677518 A CN 202210677518A CN 117265382 A CN117265382 A CN 117265382A
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percent
steel
equal
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corrosion
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宋凤明
温东辉
周庆军
华骏山
陆敏
刘涛
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
    • 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
    • C21D11/00—Process control or regulation for heat treatments
    • C21D11/005—Process control or regulation for heat treatments for cooling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • 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
    • 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
    • C21D2211/002—Bainite
    • 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

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Abstract

A weather-resistant steel for railway vehicles and a manufacturing method thereof are provided, wherein the weather-resistant steel comprises the following components in percentage by weight: 0.04 to 0.09 percent of C, 0.12 to 0.24 percent of Si, 0.6 to 0.9 percent of Mn, less than or equal to 0.015 percent of P, less than or equal to 0.006 percent of S, 0.02 to 0.04 percent of Al, 0.15 to 0.35 percent of Cu, 0.60 to 0.95 percent of Cr, 0.05 to 0.12 percent of Ni, 0.03 to 0.12 percent of Mo, 0.01 to 0.02 percent of Ti, 0.01 to 0.02 percent of Nb, less than or equal to 0.006 percent of N, less than or equal to 5 and less than or equal to 25 percent of Cr/Mo, and the balance of Fe and unavoidable impurities. The yield strength is 450-620MPa, the tensile strength is more than or equal to 600MPa, the elongation A is more than or equal to 18 percent, and the impact energy value at minus 40 ℃ is more than or equal to 100J; the corrosion resistance of the steel plate in the corrosion environment simulating the environment of the coal car meets the weight loss of less than or equal to 0.8g/m in unit area 2 H requirement; the corrosion rate of the relatively common carbon steel in the industrial atmospheric environment is less than or equal to 55 percent, and the method is particularly suitable for various cold forming processes in the production process of railway vehicles, and can be used for equipment with acid medium corrosion such as gas pipelines, boiler preheating pipelines and the like.

Description

Weather-resistant steel for railway vehicle and manufacturing method thereof
Technical Field
The invention relates to the field of low alloy steel manufacturing, in particular to weather-resistant steel for railway vehicles and a manufacturing method thereof.
Background
The steel is mainly used for manufacturing steel structures with corrosion resistance requirements such as containers, railway vehicles, bridges, outdoor towers and the like. The railway vehicle manufactured by adopting the weather-resistant steel can effectively prolong the service life of the vehicle body and the maintenance period, thereby reducing the cost. In order to further extend the life of the car body and to carry out high-speed heavy load, the steel for railway vehicles is required to have high strength and atmospheric corrosion resistance, particularly for coal-carrying vehicles, and in addition to the properties of high strength, high toughness, easy forming and the like, the steel is required to have the acid medium corrosion resistance of coal leaching solution, at 10% H 2 SO 4 The corrosion weight loss required under the condition of 24 hours uniform corrosion in a +3.5% NaCl solution medium is less than or equal to 0.8g/m 2 ·h。
The weather-resistant steel for railway vehicles is developed from the early 09CuP of 345MPa grade to 450MPa grade high-strength weather-resistant steel and high corrosion-resistant steel with better corrosion resistance, and a plurality of related steel patents are also generated. Such as:
the Chinese patent CN101033520A discloses an A1Si type economic weathering steel which is based on C-Si-Mn, and meanwhile, up to 8% of A1 is added to realize corrosion resistance. The patent does not mention the strength of the steel grade, only discloses the electrochemical test result of the steel grade, and does not provide more specific corrosion resistance performance data; rare earth is also required to be added in the components to ensure the corrosion resistance, so that the production difficulty is high, the cost is increased by 8 percent of A1, and the Si content of 0.3 to 0.8 percent is unfavorable for the impact toughness.
The yield strength of the high-strength low-alloy hot-rolled ferrite bainite weathering steel disclosed in China patent CN101660099B and a production method thereof reaches 450MPa, and the corrosion resistance is the level of conventional weathering steel by adopting a design with higher Mn content.
The high-strength low-alloy atmospheric corrosion resistant steel and the production method thereof disclosed in Chinese patent No. CN1986864, the weather resistant steel plate and the production method thereof disclosed in Chinese patent No. CN102168229B, the atmospheric corrosion resistant hot rolled steel strip with 700 MPa-grade yield strength and the production method thereof disclosed in Chinese patent No. CN107779740A and the like.
The steel sheet according to the above patent realizes a higher strength of 450MPa or more, but adopts a higher Mn in terms of components, and the cost is higher by the composite addition of reinforcing elements such as Mo, nb, V, ti; the weather-proof level is equal to that of the traditional weather-proof steel, namely, the relative corrosion rate is less than or equal to 55 percent. But do not meet the corrosion resistance requirements of coal-carrying vehicles to acidic media.
In order to meet the application requirements under more conditions, weathering steel is also being developed towards high corrosion resistance and high toughness in addition to high strength, and is required to have good workability and lower cost. Such as: "CORROSION RESISTANT STEEL" disclosed in japanese patent No. 10025550a, "CORROSION RESISTENT STEEL HAVING EXCELLENT TOUGHNESS IN BASE MATERIAL AND HEAT AFFECTED ZONE" disclosed in japanese patent No. 2002363704, and "high CORROSION resistance Cr-containing weathering steel excellent in toughness" disclosed in chinese patent No. CN102127717 a.
The steel types related to the patent have better atmospheric corrosion resistance and lower relative corrosion rate, but do not relate to the acid medium corrosion resistance of the coal-carrying vehicle; the steel contains high Cr, al, ni and other elements, and has high steelmaking difficulty and high manufacturing cost.
It has been found that the corrosion of the middle and bottom of the wagon is serious, and is electrochemical corrosion, but not in a conventional dry-wet alternate atmospheric corrosion mode, and the corrosion is mainly caused by chloride ions and sulfate ions contained in the coal leaching solution, and belongs to acid medium corrosion. Such acidic medium corrosion is common in power generation boilers and various boiler combustion exhaust gas pipelines of factories. These exhaust gases contain S0 generated by combustion of sulfur 2 And S0 3 And contains water vapor (5-18%). Sulfuric acid dew point corrosion is formed when the exhaust gas temperature drops below the dew point or the flue gas contacts the lower temperature flue tube wall or metal equipment. The early use of chromium-copper steel improves the corrosion resistance of the flue gas pipeline in such an environment, but the application effect is not satisfactory. For this purpose, sb-containing alloys such as S-TEN3 steel are used, so that a further improvement of the dew point corrosion resistance of the overall process is achieved (see for details "sulfuric acid dew point corrosion resistance of S-TEN3 and CRIA series steels, et al, huang Zhenzhong", university of Beijing science and technology 1996, 16:87-91); there are also several related patent publications such as:
japanese patent JP2001164335A discloses "HIGH WORKABILITY AND GOOD WELDABILITY SULFURIC ACID DEW POINT CORROSION RESISTANT STEEL SHEET".
Chinese patent CN102268613a discloses "an atmospheric corrosion resistant hot rolled steel sheet for railway vehicles and a method for manufacturing the same".
Both of the above patents are directed to acid media corrosion resistant steels for such corrosive environments. The former steel contains 0.01-0.15% of Sb, and is mainly used for equipment and power plants for burning heavy oil; the latter contains, in addition to 0.01-0.04% P, 1.0-2.15% Cr, 0.15-0.65% Ni and 0.25-0.65% Si, and requires addition of appropriate amounts of Ca, mg, ce and Sb. The design of higher Si and P is unfavorable for low-temperature toughness and forming performance, while the higher Cr and Ni increase the production cost, and the addition of Mg and Ce increase the production difficulty.
The weathering steel S450AW for railway freight cars, which was introduced in 2012 of the saddle steel, likewise contained about 0.1% of Sb to ensure the corrosion resistance in acidic corrosive media (see for details "Steel development Process for saddle Steel railway freight cars bodies", saddle steel technology.2018, (4): 9-14). Sb and Cu are combined to form Cu on the surface 2 Sb protective film, thereby improving sulfuric acid dew point corrosion performance. But the addition of Sb is clearly detrimental to the environment and the human body. Sb is a typical toxic and harmful heavy metal element, and has chronic toxicity and potential carcinogenicity to human and animal bodies. With the improvement of environmental protection consciousness and the tightening of environmental protection policies in the whole society, the production and application of Sb-containing steel are necessarily more limited.
As can be found from comparison with the prior patent, the corrosion resistance of the current weathering steel, whether the weathering steel is of a conventional level or high corrosion resistance, is against the atmospheric corrosion environment and is not suitable for the acid medium corrosion environment of the coal truck; the existing weathering steel capable of improving the corrosion environment of the acid medium is generally higher in alloy cost, or Sb element is added, and Sb is not beneficial to the environment and human health.
Disclosure of Invention
The invention aims to provide weather-resistant steel for railway vehicles and a manufacturing method thereof, wherein the weather-resistant steel for railway vehicles is environment-friendly, and the Sb-containing component system design of the conventional weather-resistant steel is abandoned; the yield strength is 450-620MPa, the tensile strength is more than or equal to 600MPa, the elongation A is more than or equal to 18 percent, and the impact energy value at minus 40 ℃ is more than or equal to 100J; the corrosion resistance of the steel plate in the corrosion environment simulating the coal car environment is equivalent to or even better than that of the existing Sb-containing sulfuric acid dew point resistant steel, and the weight loss per unit area is less than or equal to 0.8g/m 2 H requirement; meanwhile, the steel has good atmospheric corrosion resistance, the corrosion rate of the steel relative to common carbon steel in an industrial atmospheric environment is less than or equal to 55 percent, thereby meeting the corrosion resistance requirement in various environments, and besides, the steel has high strength, high toughness, good corrosion resistance, good welding, cold bending and other processing performances, and good elongation, is particularly suitable for various cold forming processes in the railway vehicle production process, and can be applied to equipment with acid medium corrosion such as gas pipelines, boiler preheating pipelines and the likeThe method comprises the steps of carrying out a first treatment on the surface of the In addition, the steel plate is produced in a rolling and cooling control mode, so that a wider process window is provided, and the production method is simple; the heat treatment is not needed, the production period is short, and the steel cost is low.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the weather-resistant steel for the railway vehicle is environment-friendly, abandons the Sb-containing component system design of the existing weather-resistant steel, adopts trace Ti and Nb precipitation strengthening to obtain high strength and good low-temperature toughness on the basis of lower C-Si-Mn, and realizes good corrosion resistance in an acidic medium corrosion environment by Cr-Mo component design, thereby realizing the combination of corrosion resistance, high strength and high toughness on the basis of low cost.
Specifically, the weather-resistant steel for railway vehicles comprises the following components in percentage by weight: c:0.04 to 0.09 percent, si:0.12 to 0.24 percent, mn:0.6 to 0.9 percent, P is less than or equal to 0.015 percent, S is less than or equal to 0.006 percent, al: 0.02-0.04%, cu:0.15 to 0.35 percent, cr:0.60 to 0.95 percent, ni:0.05 to 0.12 percent, mo:0.03 to 0.12 percent of Ti:0.01 to 0.02 percent, nb:0.01 to 0.02 percent, N is less than or equal to 0.006 percent, and the balance of Fe and other unavoidable impurities; and, need satisfy simultaneously: cr/Mo is more than or equal to 5 and less than or equal to 25.
Further, the weathering steel for railway vehicles according to the present invention may further include one or more of Sn.ltoreq.0.15%, RE.ltoreq.0.15%, V.ltoreq.0.05% and Ca.ltoreq.0.005%.
In the composition design of the weathering steel of the invention:
c is an effective strengthening element in the steel, is dissolved into a matrix to have solid solution strengthening effect, exists in the form of carbide in the steel, and combines with alloy elements to play roles of precipitation strengthening and grain refinement, so that the addition amount is not less than 0.04 percent; and excessive C forms more carbide in the steel to play a role of a primary cell, promotes corrosion to reduce corrosion resistance of the steel, and is unfavorable for welding, so that the content of C is limited to be not higher than 0.09%.
Since Si is an element added for deoxidizing steel and is also a corrosion resistant element and has a solid solution strengthening effect, the lower limit of the content is controlled to 0.12%, and a higher Si content results in deterioration of weldability and toughness of a weld heat affected zone, and the upper limit thereof is set to 0.24%.
Mn is an important strengthening element, plays a role of solid solution strengthening, improves the strength and toughness of steel, enlarges austenite element, can reduce supercooled austenite transformation temperature, promotes transformation of medium-low temperature strengthening structure in steel, and is beneficial to improving the strength of steel. However, too much Mn increases hardenability, resulting in deterioration of weldability and toughness of a weld heat affected zone, while higher Mn also increases costs. Therefore, the range of the prescribed Mn content is limited to 0.6 to 0.9%.
P is a main corrosion resistant element in the traditional atmospheric corrosion resistant steel, can promote the formation of a surface protective rust layer, and effectively improves the atmospheric corrosion resistant performance of the steel, but meanwhile, P is easy to generate segregation at a grain boundary, so that the grain boundary bonding energy and the toughness and the plasticity of the steel are reduced; and the coexistence of P and Mn can aggravate the tempering brittleness of the steel, and the segregation of P can easily cause the steel plate to break along crystals, so that the impact toughness of the steel plate is reduced. And P is detrimental to welding performance. The steel of the invention requires high toughness, so P is controlled as an impurity element, and the content of P in the steel is reduced as much as possible. The P content is defined to be not more than 0.015%.
S in steel is controlled as a detrimental impurity element. S not only reduces the low-temperature toughness of the steel, but also promotes the anisotropy of the steel plate, is unfavorable for cold forming performance, and sulfide inclusion can obviously reduce the weather resistance of the steel. Therefore, the steel grade design of the invention adopts extremely low S content, and is controlled below 0.006 percent.
Al is an element added into steel for deoxidization, and proper amount of Al is added to facilitate grain refinement and improve the toughness of the steel, while higher Al is not beneficial to casting during continuous casting, so the control range is 0.02-0.04%.
Cr is a noble alloy element and is also an effective element for improving the corrosion resistance of the steel plate. Cr forms a continuous solid solution with Fe in the steel, and has a solid solution strengthening effect. Cr has remarkable effect of improving the passivation capability of steel, can promote the formation of a compact passivation film or protective rust layer on the surface of steel, and simultaneously improves the self-corrosion potential of the steel and the atmospheric corrosion resistance of the steel. In the invention, cr is matched with Mo and Cu, so that the sulfuric acid dew point corrosion resistance of steel is improved, but the addition of more Cr increases the manufacturing cost, so that the invention is limited to 0.60-0.95% of Cr in view of reducing the cost.
Cu mainly plays roles of solid solution and precipitation strengthening in steel, and meanwhile, the electrochemical potential of Cu is higher than that of Fe, so that the formation of a compact rust layer on the surface of the steel can be promoted, the passivation of the steel is promoted by the cooperation of Cu and Cr, the improvement of corrosion resistance is facilitated, and meanwhile, a proper amount of Cu is combined with residual S in the steel to form Cu 2 And S protecting film for relieving corrosion in acidic medium corrosion environment. However, too high Cu not only deteriorates toughness of a weld heat affected zone, but also is susceptible to occurrence of net cracking during hot rolling, deteriorating surface properties of the steel sheet, and increasing costs. Therefore, the Cu content is limited to 0.15 to 0.35%.
Ni is an enlarged austenite forming element. Ni improves low-temperature impact toughness by refining grains and reducing stacking fault energy; meanwhile, the grain refinement also has the fine grain strengthening effect. In addition, ni is also an important element for improving the corrosion resistance of steel, and can promote the stability of rust layers and improve the problem of hot working brittleness caused by Cu. But Ni is a noble element, and the content of Ni is limited to be 0.05-0.12% in order to reduce the cost.
Ti is a strong ferrite forming element and a carbonitride forming element, and is easily combined with C, N, O, S and the like. Ti exists mainly in the form of TiC or Ti (C, N) in steel. In the invention, ti is added mainly by utilizing TiN to inhibit the growth of austenite grains, thereby playing a role in refining the structure; and simultaneously, precipitation strengthening effect is generated in the cooling process. In addition, ti has the functions of preventing the deformed austenite from recrystallization and promoting the formation of granular bainite, and the precipitated carbonitride particles of Ti can prevent coarsening of grains in a weld heat affected zone and improve welding performance. When the Ti content is too high, titanium nitride particles are easy to grow up and agglomerate at high temperature, and the plasticity and toughness of the steel are damaged. Therefore, the Ti content is limited to 0.01 to 0.02%.
Nb is a strong nitrogen carbide forming element, and can combine with carbon and nitrogen in steel to form intermediate phases such as NbC, nb (CN), nbN and the like in the cooling process after rolling, and the formed fine carbide particles can refine the structure, generate fine grain strengthening and precipitation strengthening effects, and remarkably improve the strength of the steel plate. Meanwhile, the refinement of the structure is beneficial to the improvement of the toughness of the steel plate. In addition, nb can inhibit the expansion of an austenite interface, raise the recrystallization temperature of steel, and realize rolling in a non-recrystallization zone at a higher temperature. Therefore, adding an appropriate amount of Nb to the steel is advantageous in improving the strength, and when the Nb content is high, coarse carbonitride particles are formed at grain boundaries, deteriorating the impact toughness. Nb is a noble alloy element and the content thereof is limited to be 0.01-0.02 percent.
Mo may exist in steel in solid solution form, producing solid solution strengthening. Mo promotes the formation of bainite and martensite structures during quenching heat treatment. Has phase change strengthening and dislocation strengthening effects. Meanwhile, mo can improve the solubility of Nb, V and Ti and promote precipitation strengthening. In low alloy high strength steels, the strength of the steel increases significantly with increasing Mo content. The addition of Mo can improve the film structure of corrosion products, the local corrosion resistance of steel such as pitting corrosion, crevice corrosion and the like, especially the adhesive force of a surface protective rust layer is increased, and the corrosion resistance is further improved. In the invention, the corrosion resistance of the acidic medium in the corrosive environment is obviously improved by utilizing the matching of Cr and Mo. However, since higher Mo is disadvantageous in terms of welding performance and high in cost, the Mo content is limited to 0.03 to 0.12%, and the Cr and Mo contents satisfy the relation: cr/Mo is more than or equal to 5 and less than or equal to 25.
N can form nitrides with Al and Ti in steel, and fine precipitates have a role of pinning grain boundaries to refine austenite grains. Higher N combines with Al in the steel to easily form AlN, thereby significantly increasing the amount of nitride in the steel. When AlN is independently present in steel as a nonmetallic inclusion, the continuity of a steel matrix is damaged, especially when the AlN is formed in a large quantity and in aggregation distribution when the Al content is high, the AlN is more harmful, and meanwhile, oxide with poor plasticity is formed; and the higher N tends to be concentrated in the defect, deteriorating the low-temperature impact toughness, so that the N content must be controlled below 0.0060%.
In addition to the above elements, one or more of Sn, RE, V, and Ca may be further optionally added to the weathering steel composition of the present invention in order to further improve the performance.
Wherein, sn has better corrosion inhibition effect in steel, and simultaneously, sn ions can be dissolved in an anode so as to inhibit anode reaction, thereby reducing the formation of beta-FeOOH with unfavorable corrosion resistance, and limiting the content thereof to be less than or equal to 0.12 percent; RE forms RE compound, RE/Fe intermetallic compound, solid solution RE, etc. in steel, and is hydrolyzed in the corrosive thin liquid film and deposited in cathode with relatively high pH value to inhibit corrosion with limit content less than or equal to 0.12%. V is a strong carbon-nitrogen compound forming element, can be precipitated in the phase change process, has the functions of solid solution strengthening and carbon nitride precipitation strengthening in steel, and increases tempering stability, thereby improving strength, and limiting the content of the V to be less than or equal to 0.05 percent. Ca can change the shape of sulfide when being added into steel, inhibit the hot brittleness of S, improve the toughness and limit the addition amount to be less than or equal to 0.005 percent.
As described above, the invention abandons the Sb-containing component system design of the existing weathering steel, and realizes the remarkable improvement of the corrosion resistance in the acidic medium corrosion environment by matching Cr and Mo on the basis of a proper amount of Cu-Ni. Cu in the steel with residual S can form Cu 2 S protective film prevents cathode and anode reaction, thereby improving the atmospheric corrosion resistance and sulfuric acid dew point corrosion resistance of steel. However, S is disadvantageous in low-temperature toughness and formability, so that S is controlled as an impurity element in the present invention, and only a small amount of Cu is formed by Cu and residual S 2 S realizes the supplement of the corrosion resistance of the acid-resistant medium, and the excellent corrosion resistance of the acid-resistant medium is mainly obtained through the combination of Cr-Mo. Wherein the addition of Cr improves the self-corrosion potential of the steel, promotes the formation of a compact passivation film or protective rust layer on the surface of the steel, and forms FeCr with good corrosion prevention function in the rust layer 2 O 4 While significantly improving the passivation capability of the steel. Under the corrosive environment of an acidic medium, cr enables a CrO passivation film to be formed on the surface of the steel rapidly, and meanwhile, the polarization potential of a passivation area is improved. The passivation film is a reactant for sulfuric acid corrosion, and as reaction products accumulate, the anode potential gradually rises, so that the anode is polarized, corrosion is reduced, and the corrosion speed is reduced. The addition of Cu further promotes the passivation effect of the steel. The addition of Mo can improve the film structure of corrosion products, improve the local corrosion resistance of steel to pitting corrosion, crevice corrosion and the like, and especially increase the adhesion of a surface protective rust layerForce is favorable for improving corrosion resistance in an acidic medium environment. According to the invention, mo and Cr are selected to be matched, so that the corrosion resistance in an acidic medium environment is further improved, and the content of Cr and Mo is limited to satisfy the relation: cr/Mo is more than or equal to 5 and less than or equal to 25.
On the basis of Cu-Ni, the steel plate has good corrosion resistance by the design of the corrosion resistant component of Cr-Mo, and is 10 percent of H 2 SO 4 Weight loss per unit area under the condition of uniform corrosion test of +3.5% NaCl solution is less than or equal to 0.8g/m 2 The h requirement is equivalent to or even better than the existing Sb-containing sulfuric acid dew point resistant steel; and the corrosion resistance of the steel is equal to that of the conventional weathering steel, and the corrosion rate of the steel is less than or equal to 55 percent relative to that of common carbon steel, so that the corrosion resistance requirement in various environments is met. The novel corrosion-resistant component system avoids toxic pollution of Sb to the environment and human bodies, obtains good corrosion resistance, and belongs to an environment-friendly product.
Meanwhile, the invention utilizes the effects of solid solution strengthening, precipitation strengthening and fine grain strengthening of Mo, nb and Ti, on one hand, the yield strength of 450-620MPa is obtained, meanwhile, the high low-temperature impact toughness is achieved, the low-temperature impact work value exceeds 100J at minus 40 ℃, the matching of high strength and high toughness is realized, and the requirement of high-strength light-weight steel for railway vehicles is met. The steel plate has good forming property and meets the use and processing requirements of the steel for railway vehicles.
The method for manufacturing weather-resistant steel for railway vehicles according to the present invention comprises the steps of:
1) Smelting and casting
Smelting and casting into blanks according to the components;
2) Heating of cast blanks
The heating furnace is in a reducing atmosphere, and the tapping temperature of the casting blank is controlled to be more than or equal to 1230 ℃;
3) Rolling
The rough rolling finishing temperature of the billet is more than or equal to 1050 ℃, and the accumulated rolling reduction rate of the rough rolling stage is more than or equal to 80%; the finish rolling starting temperature is more than or equal to 980 ℃, and the finish rolling finishing temperature is 880+/-30 ℃;
4) Cooling
The cooling adopts a laminar cooling process, and the cooling speed is more than or equal to 8 ℃/s, the cooling speed is cooled to 460-580 ℃ and the coiling is carried out.
Preferably, in the smelting process of the step 1), an LF refining process is adopted.
Preferably, step 3) the coiling temperature is 480 to 580 ℃.
Preferably, the cooling rate of step 4) is not less than 20 ℃/s.
In the method for manufacturing weather-resistant steel for railway vehicles according to the present invention:
the casting blank is heated in the step 2) of the invention: the heating furnace is required to be in a reducing atmosphere, and the tapping temperature of the casting blank is controlled to be more than 1230 ℃. Cu has a low melting point, copper embrittlement easily occurs in the high-temperature heating process, and 0.05-0.12% of Ni is added into steel, so that the problem of copper embrittlement is solved. Therefore, the casting blank of the steel grade is heated without considering the problem of copper embrittlement, the temperature and time control range is wider, and the structure production is convenient.
And 3) rolling adopts a hot continuous rolling process, and in the invention, the addition of trace Nb enables the austenitizing temperature Ac3 of the steel to be above 915 ℃. As can be seen from fig. 1, the ferrite formation start temperature under continuous cooling conditions is about 849 ℃; in consideration of refinement of the structure after water cooling, the water cooling starting temperature is required to be as high as possible, but the excessively high finish rolling ending temperature also correspondingly requires the billet tapping temperature to be higher, so that the production energy consumption and the production cost are increased. Meanwhile, in order to avoid abrupt change of rolling force caused by rolling in a two-phase zone, the finish rolling temperature of 880+/-30 ℃ is set, the rough rolling finishing temperature of a billet is over 1050 ℃, and the accumulated rolling reduction rate in the rough rolling stage is more than or equal to 80%; the finish rolling starting temperature is more than or equal to 980 ℃.
In order to ensure mechanical properties, the steel of the present invention requires a matrix structure with bainite+ferrite. In order to achieve fine grain strengthening, it is required to use as high finish rolling finish temperature as possible, and immediately water-cooling after rolling. Pearlite in the matrix is a high C component, so that a primary cell is easily formed in the matrix, and corrosion is promoted. To improve the corrosion resistance of the steel, the formation of pearlite in the matrix should be minimized. From the CCT curve of FIG. 1, the pearlite formation in the cooling process can be avoided by controlling the cooling speed after rolling to be more than 8 ℃/s (preferably more than or equal to 20 ℃/s), so that the control difficulty of laminar cooling in the strip steel production process is reduced, and the on-site production is facilitated.
To obtain a high yield strength, more bainite strengthening phase is required to be formed in the matrix. According to the invention, a Cr-Mo corrosion-resistant component system design is adopted, so that on one hand, better corrosion resistance is obtained, meanwhile, an austenite region is reduced through Cr and Mo, wherein Cr reduces the diffusion speed of C in austenite, reduces the critical cooling speed, and improves the hardenability of the steel plate. The addition of 0.60-0.95% Cr can separate pearlite and bainite transformation curves, so that the transformation curves of proeutectoid ferrite and pearlite are shifted to the right, and the critical cooling speed is reduced; and Bs is reduced more, and Ms point is reduced less, which is beneficial to reducing welding crack tendency, thinning structure and reducing ductile-brittle transition temperature. 0.03 to 0.12% of Mo suppresses the formation of polygonal ferrite and pearlite in steel, and promotes the formation of bainite having a large dislocation distribution in the crystal formed in a large cooling rate range, thereby improving strength. Referring to fig. 2, from the TTT temperature profile of the steel, about 542 ℃ is the fastest temperature for bainite formation, and to ensure sufficient bainite formation in the matrix, it is desirable to control the coiling temperature from 460 to 580 ℃, preferably from 480 to 580 ℃. The weathering steel provided by the invention does not need post-rolling heat treatment, so that the production period is shortened, and the production cost is reduced.
The invention has the following advantages:
the weathering steel provided by the invention abandons the existing Sb component design, avoids the harm to the environment and human health, and belongs to an environment-friendly product.
The steel has excellent corrosion resistance and meets the requirement of a coal truck on the corrosion resistance. The Cr-Mo component is adopted to design and replace the prior Sb, the corrosion resistance in the corrosive environment of an acid medium is equivalent to or even better than that of the prior Sb-containing steel, and the corrosion resistance is 10 percent of H 2 SO 4 Weight loss per unit area under the condition of uniform corrosion test of +3.5% NaCl solution is less than or equal to 0.8g/m 2 H requirement; the atmospheric corrosion resistance also reaches the level of the conventional weathering steel, and the corrosion rate relative to Q345B is lower than 55 percent, thereby meeting the corrosion resistance requirements in various environments.
The steel has excellent mechanical properties, the yield strength is more than 450-620MPa, the tensile strength is more than or equal to 600MPa, the elongation A is more than or equal to 18%, the low-temperature impact power value at minus 40 ℃ is more than 100J, and meanwhile, the steel has good cold processing performance, meets the cold bending requirements of D=1a and 180 degrees, and is easy to weld and process. This is not the case with all weathering steels.
The invention adopts controlled rolling and controlled cooling production, and rolling delivery is realized without heat treatment; the bainite critical cooling speed of the steel plate is low, the steel grade has a larger process control window, the production process is simple, the production period is short, and the steel rolling can be implemented by using the existing steel rolling equipment.
Compared with the prior art, the invention has the following differences:
the comparative patent 1 (Chinese patent CN102127717A 'high corrosion resistance Cr-containing weathering steel with excellent toughness') is designed for high Cr-Ni component, wherein the Cr content is 2.5-7.0% and the Ni content is 0.2-1.2% which are far higher than the steel type.
The steel grade of the invention is obviously different from the chemical composition of the comparative patent 1, and the steel grade of the invention obtains excellent corrosion resistance through Cr and Mo on the basis of Cu-Ni.
Comparative patent 2 (chinese patent CN102268613a, "an atmospheric corrosion resistant hot rolled steel sheet for railway vehicles and method for manufacturing the same"), contains not only Sb but also higher Si, P, cr, ni and Ti, and also V, ca, mg and Ce need to be added simultaneously. The design of higher Si and P is unfavorable for low-temperature toughness and forming performance, the production cost is increased by higher Cr and Ni, and the production difficulty is increased by adding Mg and Ce. Especially, sb belongs to a typical poisonous and harmful heavy metal element, and has chronic toxicity and potential carcinogenicity to human bodies and animal bodies.
The content of Si and Ni is also high in addition to Sb in comparative patent 3 (Japanese patent No. 2001164335A "HIGH WORKABILITY AND GOOD WELDABILITY SULFURIC ACID DEW POINT CORROSION RESISTANT STEEL SHEET").
The performance requirements of the steel are completely different from those of the steel of the comparative patents 1 to 3, the yield strength of the steel of the invention is above 450-620MPa, the elongation exceeds 18%, the impact power value at minus 40 ℃ is above 100J, and the steel has good corrosion resistance in acidic corrosive media and industrial atmospheric environment.
The yield strength of the steel grades of the comparative patents 1 to 3 is generally lower than that of the invention, and the low-temperature impact toughness is not as good as that of the invention. The comparative patent 1 has good corrosion resistance only in the atmospheric environment, and does not meet the requirement of corrosion resistance in an acidic medium.
The invention adopts the hot continuous rolling process to produce, only the control cooling speed is required to be above 8 ℃/s in the layer cooling process after rolling, the process window is wider, the production difficulty is reduced, and the on-site production is convenient.
Compared with the patent 1, the control of the cooling speed after rolling is required to be 5-20 ℃/s, namely, the upper limit is required, and the lower limit is required, so that the control difficulty of water cooling is obviously increased; compared with the patent 2, the cooling process of cooling to 550-690 ℃ at a cooling speed of more than 10 ℃/s after finishing rolling at 880-950 ℃ and cooling to 550-690 ℃ for coiling is required, the production difficulty is obviously increased by the cooling process of cooling after rolling, and particularly the production time is prolonged due to air cooling, so that the production rhythm is influenced. And the final rolling temperature of 880-950 ℃ finish rolling, such as the requirement of higher casting blank heating temperature, increases the energy consumption and the production cost.
Drawings
FIG. 1 is a graph showing the transformation temperature (CCT) curve of weathering steel according to the present invention;
FIG. 2 is a graph showing the transformation temperature TTT of weathering steel according to the present invention;
FIG. 3 is a photograph showing a microstructure of example 2 of weathering steel according to the present invention.
Detailed Description
The invention is further described below with reference to examples and figures.
The chemical compositions of the weathering steel examples of the invention are shown in Table 1, the production process parameters are shown in Table 2, and the mechanical properties and corrosion resistance of the weathering steel of the invention are shown in Table 3.
Example A
According to the requirements of chemical components of the steel, the invention adopts a converter for smelting, and then carries out post-furnace refining to obtain chemical components shown in table 1, the continuous casting and slab cutting are sent to a hot rolling production line, the billet heating temperature is 1234 ℃, the final rolling temperature is 904 ℃, and the coiling temperature is 579 ℃.
Example B
According to the composition requirements of the invention, the steel of the invention is smelted in a laboratory 500kg vacuum induction furnace. The chemical composition is shown in Table 2. The heating temperature of the billet is 1237 ℃, the final rolling temperature is 909 ℃, the billet is cooled to 563 ℃ in an accelerating way after rolling, and then coiled, and the billet is air-cooled to room temperature. The microstructure of the steel sheet prepared was a bainite+ferrite structure (see fig. 3).
According to the detection of the TB/T2375 'periodic infiltration corrosion test method of weather-resistant steel for railways', the relative Q345B corrosion rate is lower than 55%; under the corrosive environment of an acid medium, the full immersion test is carried out according to GB 10124-1988 "a method for testing uniform corrosion of metallic materials in a laboratory", and the test solution is 10.0% H 2 SO 4 +3.5% NaCl for 24 hours at 23+ -2deg.C, corrosion resistance comparable to or even better than existing materials such as S450AW at 10% H 2 SO 4 Weight loss per unit area under the condition of uniform corrosion test of +3.5% NaCl solution is less than or equal to 0.8g/m 2 H requirement; the atmospheric corrosion resistance also reaches the level of the conventional weathering steel, and the corrosion rate relative to Q345B is lower than 55 percent, thereby meeting the corrosion resistance requirements in various environments.
The embodiment steel obtained by the steel grade composition design range and rolling process control technology of the invention has good mechanical properties within the thickness range of 1.5-10mm (but is not limited to the range). The yield strength is 450-620MPa, the tensile strength is more than or equal to 600MPa, the elongation is more than 18 percent, and the impact energy value at-40 ℃ exceeds 100J (10 x 55mm standard size samples). The steel plate has a good process window, reduces the on-site production difficulty and is convenient for tissue production.
The weather-resistant steel provided by the invention has good corrosion resistance performance under the conditions of atmosphere and acid corrosion medium besides high strength and high toughness, and meets the severe corrosion environment of a coal truck; meanwhile, the elongation is excellent, the forming performance is good, and the method is particularly suitable for various cold forming processes in the railway wagon production process. In addition to coal transportation, the weathering steel of the invention has the corrosion resistance in the corrosive environment of acid medium which is equivalent to or even better than that of the prior materials such as S450AW, and is 10 percent H 2 SO 4 Weight loss per unit area under the condition of uniform corrosion test of +3.5% NaCl solution is less than or equal to 0.8g/m 2 H requirement; the atmospheric corrosion resistance also reaches the level of the conventional weathering steel, and the corrosion rate relative to Q345B is lower than 55 percentThereby meeting the requirement of corrosion resistance in various environments; the method can also be applied to equipment with acid medium corrosion such as gas pipelines, boiler preheating pipelines and the like and conventional steel structure manufacturing requiring industrial atmospheric corrosion performance.
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Claims (7)

1. A weather-resistant steel for railway vehicles comprises the following components in percentage by weight: c:0.04 to 0.09 percent, si:0.12 to 0.24 percent, mn:0.6 to 0.9 percent, P is less than or equal to 0.015 percent, S is less than or equal to 0.006 percent, al: 0.02-0.04%, cu:0.15 to 0.35 percent, cr:0.60 to 0.95 percent, ni:0.05 to 0.12 percent, mo:0.03 to 0.12 percent of Ti:0.01 to 0.02 percent, nb:0.01 to 0.02 percent, N is less than or equal to 0.006 percent, and the balance comprises Fe and unavoidable impurity elements; and, need satisfy simultaneously: cr/Mo is more than or equal to 5 and less than or equal to 25.
2. The weathering steel for railway vehicles according to claim 1, further comprising one or more of 0.15% or less of Sn, 0.15% or less of RE, 0.05% or less of V and 0.005% or less of Ca.
3. The weathering steel for railway vehicles according to claim 1 or 2, wherein the yield strength of the weathering steel plate is 450-620MPa, the tensile strength exceeds or exceeds 600MPa, the elongation a is or exceeds 18%, and the impact power value at-40 ℃ is or exceeds 100J; the unit area weight loss of the steel plate is less than or equal to 0.8g/m under the corrosive environment simulating the environment of the coal car 2 H; the corrosion rate of the steel is less than or equal to 55 percent relative to common carbon steel in the industrial atmospheric environment.
4. A method of producing weather resistant steel for railway vehicles according to claim 1, 2 or 3, comprising the steps of:
1) Smelting and casting
Smelting and casting into billets according to claim 1 or 2;
2) Heating of cast blanks
The heating furnace is in a reducing atmosphere, and the tapping temperature of the casting blank is controlled to be more than or equal to 1230 ℃;
3) Rolling
The rough rolling finishing temperature of the billet is more than or equal to 1050 ℃, and the accumulated rolling reduction rate of the rough rolling stage is more than or equal to 80%; the finish rolling starting temperature is more than or equal to 980 ℃, and the finish rolling finishing temperature is 880+/-30 ℃;
4) Cooling
The cooling adopts a laminar cooling process, and the cooling speed is more than or equal to 8 ℃/s, the cooling speed is cooled to 460-580 ℃ and the coiling is carried out.
5. The method for producing weathering steel for railway vehicles as claimed in claim 4, wherein in the step 1) of smelting, an LF refining process is used.
6. The method for producing weathering steel for railway vehicles as claimed in claim 4, wherein the coiling temperature in step 3) is 480 to 580 ℃.
7. The method for producing weathering steel for railway vehicles as claimed in claim 4, wherein the cooling rate in step 4) is not less than 20 ℃/s.
CN202210677518.3A 2022-06-15 2022-06-15 Weather-resistant steel for railway vehicle and manufacturing method thereof Pending CN117265382A (en)

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