CN115094319A - Pickled sheet material, method of making same, and articles made therefrom - Google Patents
Pickled sheet material, method of making same, and articles made therefrom Download PDFInfo
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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
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- 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
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
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Abstract
The application provides a pickled plate material, a manufacturing method thereof and a product, wherein the pickled plate material has the following chemical composition in percentage by mass: carbon: 0.20 to 0.24 percent; silicon: 0.20 to 0.40 percent; manganese: 1.00% -1.30%; phosphorus: less than 0.015 percent; sulfur: 0.005% or less; chromium: 0.15 to 0.35 percent; titanium: 0.02% -0.04%; boron: 0.0025-0.004%; nitrogen: less than 0.004%, preferably 0.0021% -0.0038%; acid-soluble aluminum: 0.01 to 0.06 percent, and the balance of iron and impurities; wherein, 5.72% is less than or equal to 19.4 [% carbon ] +0.88 [% manganese ] + [% chromium ] +88.4 [% boron ] < 5.91%. The chemical component content of the acid-washing plate material provided by the application is low, and a product manufactured by using the acid-washing plate material is high in strength, free of color difference and low in production cost.
Description
Technical Field
The application relates to the technical field of acid-washing plates, in particular to an acid-washing plate material and a manufacturing method and a product thereof.
Background
With the approaching of the aim of 'double carbon', the light weight requirement of automobiles puts forward higher weight reduction requirement on steel materials, and the application range of the steel materials as hot forming steel which has high strength and easy forming is wider and wider. The hot-rolled pickled hot-formed steel has good surface quality, wide thickness specification range and higher cost performance, but the surface quality of the steel plate is reduced due to the phenomenon of blackening or chromatic aberration of the surface of the steel plate after pickling in the actual production process.
Disclosure of Invention
The application provides a pickled plate material, a manufacturing method thereof and a product, which can effectively reduce the color difference existing on the surface of the pickled plate material.
In a first aspect, the present application provides a pickled sheet material having a chemical composition, in mass percent, as shown below:
carbon: 0.20 to 0.24 percent;
silicon: 0.20 to 0.40 percent;
manganese: 1.00% -1.30%;
phosphorus: less than 0.015%, preferably 0.006% to 0.013%;
sulfur: less than 0.005%, preferably 0.0018% to 0.0038%;
chromium: 0.15 to 0.35 percent;
titanium: 0.02 to 0.04 percent;
boron: 0.0025-0.004%;
nitrogen: less than 0.004%, preferably 0.0021% -0.0038%;
acid-soluble aluminum: 0.01% -0.06%, and
balance iron and impurities;
wherein the carbon content [% carbon ], the manganese content [% manganese ], the chromium content [% chromium ], and the boron content [% boron ] satisfy the following relationships:
5.72 percent to 19.4 [% carbon ] +0.88 [% manganese ] + [% chromium ] +88.4 [% boron ] < 5.91%.
According to the technical scheme, the surface roughness of the acid pickling plate material and the thickness of the intercrystalline oxide layer can be effectively reduced by reasonably selecting the chemical composition and the content, so that the color difference existing on the surface of the acid pickling plate material is effectively reduced, and the purpose of improving the surface quality of the acid pickling plate material is achieved.
In some embodiments of the present application, the pickled plate material has a surface roughness of 1.4 μm to 1.7 μm.
In some embodiments of the present application, the intergranular oxide layer of the pickled plate material has a thickness of 1.5 μm to 3 μm.
In a second aspect, the present application provides a method of manufacturing a pickled plate material, the method comprising the steps of:
providing a billet having the chemical composition of any of the embodiments described above;
feeding the casting blank into a heating furnace at 800-950 ℃;
rolling the heated casting blank to obtain a steel belt;
cooling the steel strip at a first stage cooling rate R 1 ＝v 1 +k 1 ×a 1/2 Cooling to a temperature of 580-600 ℃, and then cooling at a second stage cooling rate R 2 ＝v 2 +k 2 ×a 1/2 Cooling to coiling temperature T Coiling ＝T+k×a 1/2 X b and is in T Coiling Coiling under the condition to obtain a hot rolled steel plate material;
pickling, rinsing, drying and oiling the hot-rolled steel plate material to obtain a pickled plate material;
wherein R is 1 Represents the first stage cooling rate in ℃/s;
v 1 60-80 ℃/s;
a represents the thickness of the hot-rolled steel plate material in mm;
k 1 correction factor, k, representing the first stage cooling rate 1 Is 29.4 ℃/s mm 1/2 ；
R 2 Represents the second stage cooling rate in ℃/s;
v 2 10 ℃/s-30 ℃/s;
k 2 correction factor, k, representing the second stage cooling rate 2 Is 8.6 ℃/s.mm 1/2 ；
T Coiling Represents the coiling temperature in ℃/s;
t is between 410 and 430 ℃;
k represents a correction coefficient of the coiling temperature, and k is 26.2X 10 -3 ℃/mm 3/2
b represents the width of the hot rolled steel sheet material in mm.
According to the technical scheme, the manufacturing method is simple in process, and the pickled plate which is low in strength, high in elongation and free of color difference is obtained by adopting rapid cooling and slow cooling, low-temperature coiling, pickling, rinsing, drying and oiling, so that the pickled plate is easy to machine and form and uniform in color.
In some embodiments of the present application, the providing a casting slab comprises:
providing a raw material having the chemical composition described in the above examples;
sequentially smelting, refining and continuously casting the raw materials to obtain a casting blank, wherein the mass ratio of calcium to sulfur in the refining silicon-calcium treatment process is 1.0-3.0;
optionally, in the continuous casting treatment process of the casting blank, the reduction of the casting blank is 5mm to 15 mm.
In some embodiments of the present application, the heating furnace comprises a preheating section, a first heating section, a second heating section and a soaking section, wherein the temperatures of the second heating section and the soaking section are 1160 ℃ to 1220 ℃.
In some embodiments of the present application, the rolling the heated cast slab to obtain a steel strip includes:
and sequentially carrying out rough rolling and finish rolling treatment on the heated casting blank, wherein the finish rolling finishing temperature is 840-900 ℃.
In some embodiments of the present application, the acid washing comprises a first stage acid washing, a second stage acid washing, a third stage acid washing, a fourth stage acid washing and a fifth stage acid washing, wherein in the fourth stage acid washing and the fifth stage acid washing, a corrosion inhibitor is added to cooperate with the acid liquor for acid washing;
optionally, the pickling temperature is 70-85 ℃;
optionally, in the first-stage acid washing, the concentration of the acid solution is 30 g/L-40 g/L;
optionally, in the second-stage acid washing, the third-stage acid washing and the fourth-stage acid washing, the concentration of the acid solution is 70 g/L-90 g/L;
optionally, in the fifth stage of acid washing, the concentration of the acid solution is 130g/L to 150 g/L;
optionally, the concentration of the corrosion inhibitor in the fourth pickling section is 30 to 40 percent of that of the corrosion inhibitor in the fifth pickling section;
optionally, in the fifth stage of acid washing, the concentration of the corrosion inhibitor is 0.03g/L to 0.04 g/L.
In some embodiments of the present application, in the fourth and fifth stage picklingAcid pickling speed R 3 ＝v 3 +k 3 ×C Acid liquor /C Corrosion inhibitor 3/2 ；
Wherein R is 3 The pickling speed is expressed in the unit of m/min;
v 3 40m/min to 50 m/min;
k 3 correction coefficient, k, representing pickling speed 3 Is 3.18X 10 -3 m·g 1/2 /s·L 1/2 ；
C Acid liquor The concentration of the acid liquor is expressed in g/L;
C corrosion inhibitor The concentration of the corrosion inhibitor is expressed in g/L.
In a third aspect, the present application also provides an article made from the pickled sheet material described in any of the above embodiments.
According to the technical scheme, the product is high in strength, free of color difference and low in production cost.
Optionally, the yield strength of the article is above 500 MPa;
optionally, the article has a tensile strength above 650 MPa;
optionally, the elongation of the article is above 17%.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and together with the description, serve to explain the principles of the application.
FIG. 1 is a surface quality of hot rolled steel sheet after pickling according to some examples of the present application;
FIG. 2 is a surface quality of a hot rolled steel sheet after pickling according to some comparative examples of the present application;
FIG. 3 illustrates the hot rolled scale thickness in some embodiments of the present application;
FIG. 4 shows the hot rolled scale thickness in some comparative examples of the present application;
FIG. 5 illustrates the thickness of the intergranular oxide layer after acid washing in some embodiments of the present application;
FIG. 6 shows the thickness of the intergranular oxide layer after pickling in some comparative examples of the present application.
Specific embodiments of the present application have been shown by way of example in the drawings and will be described in more detail below. These drawings and written description are not intended to limit the scope of the inventive concepts in any manner, but rather to illustrate the inventive concepts to those skilled in the art by reference to specific embodiments.
Detailed Description
The examples or embodiments are described in a progressive arrangement throughout this specification, each with emphasis on illustrating differences from the other examples.
In the description of the present specification, references to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
The application provides a pickled plate material which comprises the following chemical compositions in percentage by mass:
carbon: 0.20 to 0.24 percent;
silicon: 0.20 to 0.40 percent;
manganese: 1.00% -1.30%;
phosphorus: less than 0.015%, preferably 0.006% to 0.013%;
sulfur: less than 0.005%, preferably 0.0018% to 0.0038%;
chromium: 0.15 to 0.35 percent;
titanium: 0.02% -0.04%;
boron: 0.0025-0.004%;
nitrogen: less than 0.004%, preferably 0.0021% -0.0038%;
acid-soluble aluminum: 0.01% -0.06%, and
the balance iron and impurities;
wherein the carbon content [% carbon ], the manganese content [% manganese ], the chromium content [% chromium ], and the boron content [% boron ] satisfy the following relationships:
5.72 percent to 19.4 [% carbon ] +0.88 [% manganese ] + [% chromium ] +88.4 [% boron ] < 5.91%.
The chemical composition and content in the technical scheme of the application are explained in detail below.
(carbon: 0.20% -0.24%)
Carbon (C): the content of C as interstitial atoms in the steel plate material plays a crucial role in improving the strength of the steel plate material, especially the yield strength and tensile strength of the steel plate material. If the C content is set too low, the effect of enhancing the yield strength and tensile strength of the steel sheet material is insufficient, and if the C content is set too high, the weldability of the steel sheet material is affected. Therefore, in the examples of the present application, the C content is set to 0.20% to 0.24%.
(silicon: 0.20% -0.40%)
Silicon (Si): si is a solid solution strengthening element and can improve the strength of the steel. If the Si content is too low, the effect of enhancing the strength of the steel is insufficient, and if the Si content is too high, the high melting point oxide formed on the surface of the steel sheet affects the surface quality of the steel sheet, so the Si content is set to 0.20% to 0.40% in the present invention.
(manganese 1.00% -1.30%)
Manganese (Mn): mn belongs to a replacement type element and plays a role in solid solution strengthening; it can stabilize austenite, refine crystal grains and delay the transformation from austenite to pearlite. If the Mn content is too low, the steel is likely to be transformed into a pearlite-type structure during quenching; if the Mn content is too high, center segregation is likely to occur and the alloy cost is affected, so the Mn content is set to 1.00% to 1.30% in the present invention.
(phosphorus: 0.015% or less) and (sulfur: 0.005% or less)
Phosphorus (P) and sulfur (S): p and S as harmful inclusions in steel have great damage effects on the cold formability, low-temperature toughness, weldability and fatigue crack propagation resistance of the steel; the invention controls the content of P to be less than or equal to 0.015 percent and the content of S to be less than or equal to 0.005 percent from the aspects of reducing the production cost and improving the product quality, so that the influence of P and S on the forming performance is reduced to the lowest level.
In some embodiments of the present application, the P content can also be set in the range of 0.006% to 0.013%; and the S content can be set to 0.0018% -0.0038%.
(chromium: 0.15% -0.35%)
Chromium (Cr): the Cr element can improve the hardenability of steel, simultaneously reduce the caking property of iron scale on the surface of strip steel, reduce the pulverization of the iron scale and improve the surface quality of a steel plate, but the Cr content is too high, the center segregation can occur, and the cost is higher, so the Cr content is set to be 0.15-0.35 percent in the invention.
(titanium: 0.02% -0.04%)
Titanium (Ti): the Ti element has certain fine grain strengthening and precipitation strengthening effects. The small amount of Ti can also improve the welding performance, and the invention mainly exerts the fine grain strengthening and welding performance of Ti, so the Ti content is set to be 0.020-0.040%.
(boron: 0.0025 to 0.004%)
Boron (B): the B element is an element with strong through-hardening effect in the steel, and the micro B can greatly improve the through-hardening effect in the steel. If the content of B is too low, the quenching cannot be achieved, and if the content of B is too high, the intercrystalline bonding force is deteriorated, and the probability of intercrystalline oxidation is increased. Therefore, the B content is set to 0.002% to 5-0.0040% in the present invention.
(Nitrogen: 0.004% or less)
Nitrogen (N): n belongs to harmful elements in steel, the content of N is controlled to be less than or equal to 0.004 percent, and the risk of generating TiN inclusions can be reduced.
In some embodiments of the present application, the N content may be set in the range of 0.0021% to 0.0038%.
(acid-soluble aluminum: 0.01% -0.06%)
Acid-soluble aluminum (Als): als has a deoxidizing effect in the steelmaking process, and can improve the purity of molten steel. In addition, Als can fix N in the steel and form a stable compound with N to effectively refine crystal grains, but if the content of Als is too high, the crystal grain coarsening temperature of the steel is obviously influenced, and the temper brittleness is increased. Therefore, the content of Als in the present invention is set to 0.010% to 0.060%.
Further, the carbon content, manganese content, chromium content, and boron content satisfy the following relationship:
5.72-19.4 [% carbon ] +0.88 [% manganese ] + [% chromium ] +88.4 [% boron ] < 5.91%
If the relational expression is more than 5.91 percent, the tensile strength of the hot rolled steel coil is too high, and the further processing of the steel coil is influenced; if the relation is less than 5.72%, the material is not hardened enough after hot forming, and the tensile strength of the material cannot meet the use requirement.
In some embodiments of the present application, the pickled sheet material comprising the above-described ingredients has a roughness of 1.4 μm to 1.7 μm as measured.
In some of the above embodiments, the rougher the surface of the pickled plate material, the deeper the valleys are, the smaller the radius of curvature of the valleys is, the more sensitive to stress concentration, and thus the greater the surface roughness of the material, the more sensitive it is to stress concentration, and the lower its fatigue resistance is; meanwhile, the larger the roughness is, the more easily dust, deteriorated lubricating oil, acidic and basic corrosive substances are deposited at the wave trough and permeate into the inner layer of the material to aggravate the corrosion of parts, and the smaller the roughness is, the better the wear resistance of the material is; however, the roughness is too low, and the lubricating oil is not easy to store, so that molecular adhesion is easy to occur on the contact surface, and the friction force is increased. Therefore, the pickled plate material has good fatigue strength, corrosion resistance and wear resistance when the roughness is 1.4 to 1.7 μm.
In some embodiments of the present application, the pickled plate material containing the above components has an intergranular oxide layer thickness of 1.5 μm to 3 μm, as measured.
In some of the above embodiments, the thickness of the intergranular oxide layer of the material is too large, and the thickness of the intergranular oxide layer differs in the width direction of the steel sheet because the severity of intergranular oxidation is related to the oxidizing atmosphere. Acid liquor can corrode the surface of the strip steel through intercrystalline oxidation during acid cleaning, so that the effect is intensified, the roughness in the width direction of the strip steel is different, and color difference occurs. Therefore, the thickness of the intergranular oxide layer of the acid-washing plate material is 1.5-3 μm, and the material can be ensured to avoid color difference.
According to the technical scheme, the surface roughness of the acid pickling plate material and the thickness of the intercrystalline oxide layer can be effectively reduced by reasonably selecting the chemical composition and the content, so that the color difference existing on the surface of the acid pickling plate material is effectively reduced, and the purpose of improving the surface quality of the acid pickling plate material is achieved.
The following describes in detail a method for producing a hot-rolled steel sheet material provided by the present application.
The application provides a manufacturing method of a pickled plate material, which comprises the following steps:
s10: providing a cast slab having the chemical composition of any one of the embodiments above, wherein the chemical composition is as follows: carbon: 0.20 to 0.24 percent; silicon: 0.20 to 0.40 percent; manganese: 1.00% -1.30%; phosphorus: less than 0.015%, preferably 0.006% to 0.013%; sulfur: less than 0.005%, preferably 0.0018% to 0.0038%; chromium: 0.15 to 0.35 percent; titanium: 0.02% -0.04%; boron: 0.0025-0.004%; nitrogen: less than 0.004%, preferably 0.0021% -0.0038%; acid-soluble aluminum: 0.01 to 0.06 percent, and the balance of iron and impurities; wherein the carbon content [% carbon ], the manganese content [% manganese ], the chromium content [% chromium ], and the boron content [% boron ] satisfy the following relationships: 5.72 percent to 19.4 [% carbon ] +0.88 [% manganese ] + [% chromium ] +88.4 [% boron ] < 5.91%.
S20: feeding the casting blank into a heating furnace at 800-950 ℃;
s30: rolling the heated casting blank to obtain a steel belt;
S40：cooling the steel strip at a first stage cooling rate R 1 ＝v 1 +k 1 ×a 1/2 Cooling to a temperature of 580-600 ℃, and then cooling at a second stage cooling rate R 2 ＝v 2 +k 2 ×a 1/2 Cooling to coiling temperature T Coiling ＝T+k×a 1/2 X b and is in T Coiling Coiling under the condition to obtain a hot rolled steel plate material;
s50: and (3) pickling, rinsing, drying and oiling the hot-rolled steel plate material to obtain a pickled plate material.
Wherein R is 1 Represents the first stage cooling rate in ℃/s;
v 1 60-80 ℃/s;
a represents the thickness of the hot rolled steel sheet material in mm;
k 1 correction factor, k, representing the first stage cooling rate 1 Is 29.4 ℃/s mm 1/2 ；
R 2 Represents the second stage cooling rate in ℃/s;
v 2 10 ℃/s-30 ℃/s;
k 2 correction factor, k, representing the second stage cooling rate 2 Is 8.6 ℃/s.mm 1/2 ；
T Coiling Represents the coiling temperature in ℃/s;
t is 410-430 ℃;
k represents a correction coefficient of the coiling temperature, and k is 26.2X 10 -3 ℃/mm 3/2 ；
b represents the width of the hot rolled steel sheet material in mm.
In some embodiments of the present application, S10 specifically includes the following steps:
s11: providing a starting material having the chemical composition of the above example, the chemical composition of the starting material being as follows: carbon: 0.20 to 0.24 percent; silicon: 0.20 to 0.40 percent; manganese: 1.00% -1.30%; phosphorus: less than 0.015%, preferably 0.006% to 0.013%; sulfur: less than 0.005%, preferably 0.0018% to 0.0038%; chromium: 0.15 to 0.35 percent; titanium: 0.02% -0.04%; boron: 0.0025-0.004%; nitrogen: less than 0.004%, preferably 0.0021% -0.0038%; acid-soluble aluminum: 0.01 to 0.06 percent, and the balance of iron and impurities; wherein the carbon content [% carbon ], the manganese content [% manganese ], the chromium content [% chromium ], and the boron content [% boron ] satisfy the following relationships: 5.72 percent to 19.4 [% carbon ] +0.88 [% manganese ] + [% chromium ] +88.4 [% boron ] < 5.91%;
s12: the raw materials are sequentially subjected to smelting, refining and continuous casting treatment to obtain a casting blank, wherein the mass ratio of calcium to sulfur in the refining silicon-calcium treatment process is 1.0-3.0. In the continuous casting treatment process of the casting blank, the reduction of the casting blank is 5 mm-15 mm.
In some embodiments, the refining treatment with silicon-calcium can not only purify molten steel, but also denature sulfides in the steel to convert the sulfides into non-deformable, stable and fine spherical sulfides, thereby being beneficial to improving the formability of products.
In the continuous casting treatment process of the casting blank, the reduction of the casting blank is 5 mm-15 mm. The segregation degree of elements at the final stage of solidification can be obviously reduced, so that the center segregation of a casting blank is reduced.
In some embodiments of the present application, the ingot blank is fed into the furnace at 800 ℃ to 950 ℃ in the step S20, since the intercrystalline oxidation is also temperature dependent. Experiments prove that the hot forming steel has serious intergranular oxidation within the range of 580-800 ℃ and reaches the maximum value at 680 ℃. On the basis, the temperature is increased and decreased, and the degree of intergranular oxidation is reduced. When the temperature is higher than 800 ℃, because a thicker oxide layer is generated on the surface of the steel plate, the contact between oxygen in the air and the iron base is weakened, and thus the intergranular oxidation is greatly relieved. Therefore, the casting blank enters the heating furnace at the temperature of 800-950 ℃, and the casting blank can be prevented from being subjected to intercrystalline oxidation at high temperature, so that the casting blank is further deteriorated in the heating furnace.
In some embodiments of the present application, the heating furnace in S20 includes a preheating section, a first heating section, a second heating section, and a soaking section, wherein the temperatures of the second heating section and the soaking section are 1160-1220 ℃.
In some embodiments, the reasonable heating temperature is designed to ensure that Ti is fully dissolved, which is further beneficial to improving the precipitation strengthening effect.
In some embodiments of the present application, S30 specifically includes the following steps:
and (3) sequentially carrying out rough rolling and finish rolling treatment on the heated casting blank, wherein the finish rolling finishing temperature is 840-900 ℃.
The finish rolling finishing temperature is too low, which causes mixed crystals in the two-phase region, so the finish rolling finishing temperature is controlled in the range of 840-900 ℃ in the application.
In the step S40, the first stage cooling is rapid cooling, and the finishing temperature of the rapid cooling temperature is 580 to 600 ℃, mainly in a temperature range where intergranular oxidation is easily generated by rapidly passing through a steel sheet. Therefore, the first stage cooling rate satisfies the following relationship: r 1 ＝v 1 +k 1 ×a 1/2 Wherein R is 1 Represents the first stage cooling rate in ℃/s; v. of 1 60 ℃/s-80 ℃/s; k is a radical of formula 1 Correction factor, k, representing the first stage cooling rate 1 Is 29.4 ℃/s mm 1/2 (ii) a a represents the thickness of the hot rolled steel sheet material in mm.
Further, in the step S40, the second stage cooling is performed by weak cooling, and since the temperature of the steel plate has dropped below the severe range of intercrystalline oxidation, the cooling rate is reduced, and the internal stress generated during the first stage rapid cooling process can be uniformed. Thus, the second stage cooling rate satisfies the following relationship: r 2 ＝v 2 +k 2 ×a 1/2 Wherein R is 2 Represents the second stage cooling rate in ℃/s; v. of 2 10 ℃/s-30 ℃/s; k is a radical of 2 Correction factor, k, representing the cooling rate in the second stage 2 Is 8.6 ℃/s.mm 1/2 (ii) a a represents the thickness of the hot rolled steel sheet material in mm.
In addition, in step S40, since a large amount of heat is generated by the phase transition, low-temperature coiling is adopted to mainly prevent the temperature from being too high and intergranular oxidation from being generated in the cooling process of the steel coil. And the coiling temperature is too low, a large amount of bainite and even martensite structures can be generated in the structures, so that the problems of too high strength, too large internal stress and the like are caused. Therefore, the coiling temperature satisfies the following relationship:T coiling ＝T+k×a 1/2 X b, wherein, T Coiling Represents the coiling temperature in ℃/s; t is 410-430 ℃; k represents a correction coefficient of the coiling temperature, and k is 26.2X 10 -3 ℃/mm 3/2 (ii) a a represents the thickness of the hot rolled steel sheet material in mm; b represents the width of the hot rolled steel sheet material in mm.
As can be seen from comparison between FIG. 3 and FIG. 4, the surface roughness and the scale thickness of the hot rolled steel sheet prepared under the above conditions are significantly lower than those of the comparative example, so that the pickled sheet obtained after the subsequent acid washing has higher quality.
In some embodiments of the present application, in the step S40, the acid washing includes a first acid washing, a second acid washing, a third acid washing, a fourth acid washing, and a fifth acid washing, wherein in the fourth acid washing and the fifth acid washing, a corrosion inhibitor is added to cooperate with the acid washing.
The pickling is mainly used for washing away the iron scales on the surface of the hot-rolled steel plate, and is used for preventing the color difference of the pickled plate caused by the over-pickling of the steel plate and influencing the quality of the pickled plate, so that the corrosion inhibitor is added in the fourth pickling and the fifth pickling to prevent the over-pickling of the steel plate under the condition that most of the iron scales are washed away by the pickling in the first, second and third pickling tanks.
Further, the pickling efficiency is temperature dependent, the temperature is too low, the reaction rate is too slow, and the production efficiency is affected, while too high temperature may cause the reaction to be too severe, and the steel plate is over-pickled, and the quality of the steel plate is affected. Therefore, the pickling temperature is controlled within the range of 70-85 ℃.
Furthermore, in the first-stage acid washing, the concentration of the acid liquor is 30-40 g/L; in the second-stage acid washing, the third-stage acid washing and the fourth-stage acid washing, the concentration of the acid liquor is 70-90 g/L; in the fifth stage of acid washing, the concentration of the acid liquor is 130 g/L-150 g/L.
In the five-stage pickling process, the concentration of the acid liquor is from low to high, so that the iron scale on the surface of the steel plate can be uniformly removed, the iron loss can be reduced, and the problems of over-corrosion, hydrogen embrittlement and the like can be prevented.
In addition, the concentration of the corrosion inhibitor in the fourth pickling section is 30-40% of that in the fifth pickling section; in the fifth stage of acid washing, the concentration of the corrosion inhibitor is 0.03 g/L-0.04 g/L.
Because the main iron scale on the surface of the steel plate is washed after three-stage pickling, in order to reduce the dissolution of a metal matrix and prevent the steel plate from being over-corroded and hydrogen embrittlement, the corrosion inhibitor is added into the acid liquor of the fourth-stage and fifth-stage pickling, the corrosion inhibitor can be adsorbed by the surface of the steel plate, and a double electric layer at the interface of the steel plate and the acid liquor is changed, so that the discharge of hydrogen ions is hindered, the corrosion of the acid liquor on the steel plate can be isolated, and the hydrogen embrittlement can be prevented.
In some embodiments of the present application, the acid pickling rate R is in the fourth stage acid pickling and the fifth stage acid pickling 3 ＝v 3 +k 3 ×C Acid liquor /C Corrosion inhibitor 3/2 (ii) a Wherein R is 3 The pickling speed is expressed in the unit of m/min; v. of 3 Is 40m/min to 50 m/min; k is a radical of formula 3 Correction coefficient, k, representing pickling speed 3 Is 3.18X 10 -3 m·g 1/2 /s·L 1/2 ；C Acid liquor The concentration of the acid liquor is expressed in g/L; c Corrosion inhibitor The concentration of the corrosion inhibitor is expressed in g/L.
In some embodiments, the steel plate with the main scale removed is subjected to the fourth and fifth pickling processes, and the proper pickling speed is determined by the concentrations of the acid solution and the corrosion inhibitor, so that the steel plate with no color difference, low roughness and small intergranular oxidation thickness can be obtained.
As can be seen from a comparison of FIGS. 1 and 2, the steel sheet after pickling does not show any significant color difference under the above pickling conditions. And by comparing fig. 5 and 6, the roughness and intergranular oxidation thickness of the surface of the steel sheet after pickling are significantly lower than those of the comparative example by using the above pickling conditions, and the quality of the obtained steel sheet is higher.
According to the technical scheme, the manufacturing method is simple in process, and the pickled plate which is low in strength, high in elongation and free of color difference is obtained by adopting fast cooling and slow cooling, coiling at low temperature, pickling, rinsing, drying and oiling, so that the pickled plate is easy to machine and form and uniform in color.
The present application also provides an article made from the pickled sheet material of any of the embodiments described above. Therefore, the product has high strength, no color difference and low production cost.
In some embodiments of the present application, the properties of the above product materials are tested, and the product has a yield strength of 500MPa or more, a tensile strength of 650 MPa-760 MPa, and an elongation of 17% or more.
Hereinafter, the method for producing the pickled plate material and the product of the present application will be described in more detail with reference to examples, but the present application is not limited to these examples at all.
In the following examples and comparative examples, the pickled plate materials and articles according to the embodiments of the present application were manufactured under various conditions, and mechanical properties of the obtained pickled plate materials and articles were tested, wherein the mechanical properties were required according to the test method in GB/T228.1-2010, and the results of performance test of the products obtained in the respective examples and comparative examples are shown in table 4.
Example 1
The embodiment provides a manufacturing method of a pickled plate material, which comprises the following steps:
s10: providing a cast slab having the chemical composition of any one of the embodiments above, wherein the chemical composition is as follows: carbon: 0.202 percent; silicon: 0.38 percent; manganese: 1.26 percent; phosphorus: 0.011; sulfur: 0.0024%; chromium: 0.35 percent; titanium: 0.021%; boron: 0.0039%; nitrogen: 0.0021%; acid-soluble aluminum: 0.022%, and the balance iron and impurities; wherein the carbon content [% carbon ], the manganese content [% manganese ], the chromium content [% chromium ], and the boron content [% boron ] satisfy the following relationships: 19.4 [% carbon ] +0.88 [% manganese ] + [% chromium ] +88.4 [% boron ] ═ 5.72236%;
the raw materials are sequentially subjected to smelting, refining and continuous casting treatment to obtain a casting blank, wherein the mass ratio of calcium to sulfur in the refining silicon-calcium treatment process is 1.86. In the continuous casting treatment process of the casting blank, the reduction of the casting blank is 12 mm;
s20: feeding the casting blank into a heating furnace at 825 ℃, wherein the heating furnace specifically comprises a preheating section, a first heating section, a second heating section and a soaking section, and the temperatures of the second heating section and the soaking section are 1160 ℃;
s30: carrying out rough rolling and finish rolling treatment on the heated casting blank in sequence, wherein the finish rolling finishing temperature is 886 ℃, and obtaining a steel strip;
s40: cooling the steel strip to 600 ℃ at a first section cooling rate of 141 ℃/s, then cooling to 533 ℃ at a second section cooling rate of 48 ℃/s, and coiling at 533 ℃ to obtain a hot rolled steel plate material;
s50: pickling, rinsing, drying and oiling a hot-rolled steel plate material to obtain a pickled plate material;
the pickling specifically comprises a first section of pickling, a second section of pickling, a third section of pickling, a fourth section of pickling and a fifth section of pickling, wherein in the fourth section of pickling and the fifth section of pickling, a corrosion inhibitor is added to be matched with acid liquor for pickling;
wherein the pickling temperature is 78 ℃;
in the first stage of acid washing, the concentration of the acid liquor is 33 g/L; in the second-stage acid washing, the third-stage acid washing and the fourth-stage acid washing, the concentration of the acid liquor is 71 g/L; in the fifth stage of acid washing, the concentration of the acid liquor is 132 g/L;
the concentration of the corrosion inhibitor in the fourth-stage acid washing is 0.01085 g/L; the concentration of the corrosion inhibitor in the fifth section of acid washing is 0.031 g/L;
in the fourth pickling and the fifth pickling, the pickling speed was 124 m/min.
Example 2
The present example differs from example 1 in that: for the differences of the reaction parameters, please refer to tables 1-3.
Example 3
This example differs from example 1 in that: for the differences of the reaction parameters, please refer to tables 1-3.
Example 4
This example differs from example 1 in that: for the different reaction parameters, please refer to table 1-table 3.
Example 5
The present example differs from example 1 in that: for the different reaction parameters, please refer to table 1-table 3.
Example 6
This example differs from example 1 in that: for the differences of the reaction parameters, please refer to tables 1-3.
Example 7
This example differs from example 1 in that: for the differences of the reaction parameters, please refer to tables 1-3.
Example 8
The present example differs from example 1 in that: for the differences of the reaction parameters, please refer to tables 1-3.
Comparative example 1
The chemical components and contents of the comparative example are the same as those of the example 5, and the difference is that: for the different reaction parameters, please refer to tables 2 and 3.
Comparative example 2
The comparative example has the same chemical components and contents as example 2, and is different from the comparative example in that: for the differences of the reaction parameters, please refer to tables 2 and 3.
Comparative example 3
The chemical components and contents of the comparative example are the same as those of the example 8, and the difference is that: for the differences of the reaction parameters, please refer to tables 2 and 3.
TABLE 1
| C | Si | Mn | P | S | B | Cr | Ti | Als | N | |
| Example 1 | 0.202 | 0.38 | 1.26 | 0.011 | 0.0024 | 0.0039 | 0.35 | 0.021 | 0.022 | 0.0021 |
| Example 2 | 0.208 | 0.33 | 1.28 | 0.008 | 0.0032 | 0.0036 | 0.33 | 0.023 | 0.034 | 0.0034 |
| Example 3 | 0.211 | 0.29 | 1.22 | 0.013 | 0.0018 | 0.0033 | 0.31 | 0.025 | 0.043 | 0.0038 |
| Example 4 | 0.216 | 0.25 | 1.18 | 0.006 | 0.0022 | 0.0031 | 0.29 | 0.028 | 0.026 | 0.0029 |
| Example 5 | 0.220 | 0.21 | 1.15 | 0.010 | 0.0029 | 0.0029 | 0.26 | 0.031 | 0.031 | 0.0021 |
| Example 6 | 0.225 | 0.27 | 1.11 | 0.012 | 0.0034 | 0.0025 | 0.22 | 0.033 | 0.038 | 0.0026 |
| Example 7 | 0.229 | 0.33 | 1.08 | 0.009 | 0.0038 | 0.0035 | 0.18 | 0.035 | 0.041 | 0.0032 |
| Example 8 | 0.238 | 0.39 | 1.03 | 0.013 | 0.0035 | 0.0026 | 0.15 | 0.039 | 0.035 | 0.0033 |
Note: c represents the mass content of carbon, in%;
si represents the mass content of silicon in units of%;
mn represents the mass content of manganese in units of%;
p represents the mass content of phosphorus in units of%;
s represents the mass content of sulfur, and the unit is%;
b represents the mass content of boron, and the unit is%;
cr represents the mass content of chromium in%;
ti represents the mass content of titanium, in%;
als represents the mass content of acid-soluble aluminum, and the unit is percent;
n represents the mass content of nitrogen in%.
TABLE 2
| T Casting blank | T Heating of | T Finish rolling | R 1 | R 2 | T Coiling | |
| Example 1 | 825 | 1160 | 886 | 141 | 48 | 533 |
| Example 2 | 887 | 1210 | 895 | 140 | 45 | 528 |
| Example 3 | 854 | 1180 | 879 | 135 | 41 | 511 |
| Example 4 | 863 | 1200 | 885 | 126 | 40 | 501 |
| Example 5 | 905 | 1220 | 844 | 128 | 37 | 496 |
| Example 6 | 837 | 1190 | 857 | 115 | 32 | 482 |
| Example 7 | 844 | 1170 | 862 | 104 | 28 | 471 |
| Example 8 | 872 | 1180 | 893 | 114 | 35 | 465 |
| Comparative example 1 | 615 | 1210 | 882 | 65 | 73 | 533 |
| Comparative example 2 | 840 | 1180 | 897 | 118 | 35 | 642 |
| Comparative example 3 | 863 | 1200 | 855 | 108 | 41 | 480 |
Note: t is a unit of Casting blank The temperature of the cast slab before heating in step S20 is expressed in units;
T heating of The temperatures of the second heating section and the soaking section in the step S20 are expressed in units of;
T finish rolling A finishing temperature in units of ° c representing finishing temperature in step S30;
R 1 expressed as the first stage cooling rate in step S40 in deg.c/S;
R 2 expressed as a second stage cooling rate in degrees c/S in step S40;
T coiling Expressed as the coiling temperature in step S40, in degrees c.
TABLE 3
Note: c Acid liquor 1 The acid liquor concentration in the first stage of acid washing is shown as g/L;
C 2-4% of acid liquor The acid liquor concentration in g/L when the second section, the third section and the fourth section are subjected to acid washing is shown;
C corrosion inhibitor 4 The concentration of the corrosion inhibitor in the fourth stage of acid washing is shown,the unit is g/L;
C acid liquor 5 The acid liquor concentration in the fifth stage of acid washing is expressed as g/L;
C corrosion inhibitor 5 The concentration of the corrosion inhibitor in the fifth stage of pickling is expressed in g/L;
R 3 the pickling speed in m/min was shown for the fourth pickling and the fifth pickling.
TABLE 4
Steel plate material thickness is a, unit is mm;
the width of the steel plate material is b, and the unit is mm;
R eL represents the yield strength in MPa;
R m expressed as tensile strength in MPa;
a is expressed as elongation in%;
R a expressed as roughness in μm;
L 1 expressed as the scale thickness in μm;
L 2 expressed as grain boundary oxidation thickness in μm.
As can be seen from tables 2 and 3, in the examples, compared with the comparative examples, the temperature of the casting blank before heating in the comparative example 1 is 615 ℃, the thickness of the intergranular oxidation layer is 7.8 μm, and the depth of the intergranular oxidation layer after acid cleaning is as high as 10.1 μm, so that the whole plate surface is blackened, and the normal use is influenced; at a coiling temperature of 642 ℃ in a comparative example 2, the depth of intergranular oxidation of the coiled steel plate in a high-temperature environment is 8.6 μm, and the thickness of the scale of the coiled steel plate is as high as 14.2 μm, so that in the acid washing process, in order to remove the scale on the surface of the steel plate, the acid washing speed is reduced to 80m/min, the crystal boundary of the acid washed steel plate is corroded, and the depth of the intergranular oxidation of the steel plate is increased to 12.5 μm; comparative example 3 the hot rolling process is substantially the same as the example, the thickness of the scale and the depth of the intergranular oxide layer of the hot rolled plate obtained by the hot rolling process are similar to the results of the example, but in the pickling process, the concentration of the corrosion inhibitor used is low, the pickling speed is slow, the intergranular oxide of the pickled hot rolled plate is corroded, the intergranular oxide of the pickled hot rolled plate is increased to 8.1 mu m, and meanwhile, the oxygen intrusion concentration is gradually reduced from the edge part to the central part, so the oxygen partial pressure of the edge part of the steel strip is higher, the external oxidation is generated to generate compact scale, the over pickling in the pickling process of the steel plate is protected, the corrosion to the intergranular oxide layer in the pickling process is reduced, and the intergranular oxidation degree in the width direction of the steel plate is different, and the chromatic aberration is formed.
To sum up, this application adopts casting blank high temperature to advance the stove through the chemical composition and the content of reasonable selection pickling plate material simultaneously, and the process of low temperature batching is cooled soon to below 600 ℃ after the layer is cold, avoids the temperature interval of easy intercrystalline oxidation, in the pickling process, takes acidizing fluid + corrosion inhibitor to and the pickling speed that matches with it, improved pickling efficiency, and avoided the face to cross the colour difference that the pickling leads to.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. A pickled plate material is characterized by comprising the following chemical compositions in percentage by mass:
carbon: 0.20 to 0.24 percent;
silicon: 0.20 to 0.40 percent;
manganese: 1.00% -1.30%;
phosphorus: less than 0.015%, preferably 0.006% to 0.013%;
sulfur: less than 0.005%, preferably 0.0018% to 0.0038%;
chromium: 0.15 to 0.35 percent;
titanium: 0.02% -0.04%;
boron: 0.0025 to 0.004%;
nitrogen: less than 0.004%, preferably 0.0021% -0.0038%;
acid-soluble aluminum: 0.01% to 0.06%, and
balance iron and impurities;
wherein the carbon content [% carbon ], the manganese content [% manganese ], the chromium content [% chromium ], and the boron content [% boron ] satisfy the following relationships:
5.72 percent to 19.4 [% carbon ] +0.88 [% manganese ] + [% chromium ] +88.4 [% boron ] < 5.91%.
2. The pickled plate material as defined in claim 1, wherein the pickled plate material has a surface roughness of 1.4 to 1.7 μm.
3. The pickled plate material as defined in claim 1, wherein the thickness of the intergranular oxide layer of the pickled plate material is 1.5 to 3 μm.
4. A method of manufacturing pickled plate material, comprising the steps of:
providing a billet having the chemical composition of claim 1;
feeding the casting blank into a heating furnace at 800-950 ℃;
rolling the heated casting blank to obtain a steel belt;
cooling the steel strip at a first stage cooling rate R 1 ＝v 1 +k 1 ×a 1/2 Cooling to a temperature of 580 ℃ to 600 ℃, followed by a second stage cooling rate R 2 ＝v 2 +k 2 ×a 1/2 Cooling to coiling temperature T Coiling ＝T+k×a 1/2 X b and is in T Coiling Coiling under the condition to obtain a hot rolled steel plate material;
pickling, rinsing, drying and oiling the hot-rolled steel plate material to obtain a pickled plate material;
wherein R is 1 Indicating the first stage cooling rateIn units of ℃/s;
v 1 60 ℃/s-80 ℃/s;
a represents the thickness of the hot-rolled steel sheet material in mm;
k 1 correction factor, k, representing the first stage cooling rate 1 Is 29.4 ℃/s mm 1/2 ；
R 2 Represents the second stage cooling rate in ℃/s;
v 2 is 10 ℃/s to 30 ℃/s;
k 2 correction factor, k, representing the cooling rate in the second stage 2 Is 8.6 ℃/s.mm 1/2 ；
T Coiling Represents the coiling temperature in ℃/s;
t is 410-430 ℃;
k represents a correction coefficient of the coiling temperature, and k is 26.2X 10 -3 ℃/mm 3/2 ；
b represents the width of the hot rolled steel sheet material in mm.
5. The method of manufacturing of claim 4, wherein the providing a billet comprises:
providing a raw material having the chemical composition of claim 1;
sequentially carrying out smelting, refining and continuous casting treatment on the raw materials to obtain a casting blank, wherein the mass ratio of calcium to sulfur in the refining silicon-calcium treatment process is 1.0-3.0;
optionally, in the continuous casting treatment process of the casting blank, the reduction of the casting blank is 5mm to 15 mm.
6. The manufacturing method according to claim 4, wherein the heating furnace comprises a preheating section, a first heating section, a second heating section and a soaking section, wherein the temperatures of the second heating section and the soaking section are 1160 ℃ to 1220 ℃.
7. The manufacturing method according to any one of claims 4 to 6, wherein the rolling of the heated cast slab to obtain a steel strip comprises:
and sequentially carrying out rough rolling and finish rolling treatment on the heated casting blank, wherein the finish rolling finishing temperature is 840-900 ℃.
8. The manufacturing method according to claim 4, wherein the pickling comprises a first stage pickling, a second stage pickling, a third stage pickling, a fourth stage pickling, and a fifth stage pickling, wherein in the fourth stage pickling and the fifth stage pickling, a corrosion inhibitor is added to cooperate with the acid pickling;
optionally, the pickling temperature is 70-85 ℃;
optionally, in the first-stage acid washing, the concentration of the acid liquor is 30-40 g/L;
optionally, in the second-stage acid washing, the third-stage acid washing and the fourth-stage acid washing, the concentration of the acid solution is 70 g/L-90 g/L;
optionally, in the fifth stage of acid washing, the concentration of the acid solution is 130 g/L-150 g/L;
optionally, the concentration of the corrosion inhibitor in the fourth pickling section is 30 to 40 percent of that of the corrosion inhibitor in the fifth pickling section;
optionally, in the fifth stage of acid washing, the concentration of the corrosion inhibitor is 0.03g/L to 0.04 g/L.
9. The method of claim 8, wherein in the fourth pickling and the fifth pickling, a pickling speed R is set to 3 ＝v 3 +k 3 ×C Acid liquor /C Corrosion inhibitor 3/2 ；
Wherein R is 3 The pickling speed is expressed in the unit of m/min;
v 3 is 40m/min to 50 m/min;
k 3 correction coefficient, k, representing pickling speed 3 Is 3.18X 10 -3 m·g 1/2 /s·L 1/2 ；
C Acid liquor The concentration of the acid liquor is expressed in g/L;
C corrosion inhibitor The concentration of the corrosion inhibitor is expressed in g/L.
10. An article produced using the pickled sheet material according to any one of claims 1 to 3 or the pickled sheet material produced by the production method according to any one of claims 4 to 9.
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| CN112442632A (en) * | 2020-10-26 | 2021-03-05 | 首钢集团有限公司 | High-bending-resistance hot-rolled hot-forming steel and preparation method thereof |
| CN114012056A (en) * | 2021-10-14 | 2022-02-08 | 首钢集团有限公司 | 1500 MPa-grade hot forming steel and preparation method thereof |
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| CN102031455A (en) * | 2009-09-30 | 2011-04-27 | 鞍钢股份有限公司 | Steel plate for stamping and quenching and manufacturing method thereof |
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| CN103320700A (en) * | 2013-06-26 | 2013-09-25 | 武汉钢铁(集团)公司 | 1500MPa steel for vehicle safety piece and production method of 1500MPa steel |
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