CN102266868B - Production method for pickling steel with reduced acid - Google Patents
Production method for pickling steel with reduced acid Download PDFInfo
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- CN102266868B CN102266868B CN 201110223714 CN201110223714A CN102266868B CN 102266868 B CN102266868 B CN 102266868B CN 201110223714 CN201110223714 CN 201110223714 CN 201110223714 A CN201110223714 A CN 201110223714A CN 102266868 B CN102266868 B CN 102266868B
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Abstract
The invention relates to a production method for pickling steel with reduced acid and belongs to the technical field of metal rolling. The technical scheme is that: a FeO eutectoid reaction curve in a scale microstructure in the hot rolling process of target steel is formed; a rolling process is controlled, optimized and adjusted according to the FeO eutectoid reaction curve in the scale microstructure in the hot rolling process of the target steel; and the scale microstructure is changed, the generation of Fe2O3 which is difficult to pickle is reduced, the pickling speed is improved in the pickling process, and acid consumption of each ton of steel is reduced to pickle steel with acid. The invention has the advantages that: the scale is well controlled in the hot rolling process, and the surface quality of a hot rolled strip coil and labor productivity are greatly improved; and the scale microstructure is changed, the generation of Fe2O3 which is difficult to pickle is reduced, the pickling speed is improved by 10 percent in the subsequent pickling process, and the acid consumption of each ton of steel is reduced by 7.5 percent. The pressure of excessive waste acid emission on the environment is greatly lightened, and the method has the advantages of energy conservation, emission reduction and great social benefit.
Description
Technical field
The present invention relates to a kind of production method that subtracts the pickling steel, belong to metal rolled technical field.
Background technology
At present, when iron and steel enterprise produces cold rolling getting the raw materials ready, reach by controlling follow-up acid cleaning process the purpose that improves the pickled steel strip surface quality, cause in follow-up acid cleaning process with acid measure too high, environment is caused heavy load.The typical scale structure of hot-strip is by the thinner Fe of outermost layer
2O
3Layer, middle Fe
3O
4The FeO layer of layer and close matrix side forms.According to the Fe-O equilbrium phase diagram, in the time of 570-1371 ℃, FeO is in stable state; Below 570 ℃ the time, eutectoid reaction 4FeO → a-Fe+Fe occurs in FeO
3O
4In acid cleaning process, FeO the most easily is reduced decomposition, Fe
3O
4Take second place, Fe
2O
3The sour reduction decomposition of the most difficult quilt.Therefore, the scale structure of control hot rolled strip makes it to generate more FeO and avoids simultaneously generating Fe
2O
3, be the important channel of reducing the spent pickling acid amount, improving pickling efficient, be also one of technical problem of needing to be resolved hurrily of this area.
Summary of the invention
The invention provides a kind of production method that subtracts the pickling steel, optimize hot rolling technology, On-line Control hot rolling iron scale microstructure realizes the purpose of the cold rolling follow-up easy pickling of steel grade of getting the raw materials ready,
This technology reaches to control and generates FeO and Fe in the iron scale microstructure
3O
4The purpose of percentage composition makes pickling speed raising 10% in follow-up acid cleaning process, reduces a ton steel acid consumption 7.5%.
Technical solution of the present invention is:
A kind of production method that subtracts the pickling steel, at first, determine in target steel grade course of hot rolling FeO eutectoid reaction curve in the iron scale microstructure, concrete steps are as follows: 1. measure the experiment of target steel grade oxidation kinetics, estimate the oxidation rate of each steel grade, measure oxidation weight gain and the relation curve of time, for estimation oxide skin growing state provides basic data; 2. carry out FeO eutectoid reaction research, by the thermal simulation experiment means, the isothermal transformation behavior of the FeO layer that under research different temperatures and isothermal time condition, surface of low-carbon steel forms draws FeO eutectoid reaction curve in the iron scale microstructure; Then, according to FeO eutectoid reaction curve in iron scale microstructure in target steel grade course of hot rolling, control and optimize and revise rolling mill practice; By changing the microstructure of iron scale, reduce the Fe that is difficult to pickling
2O
3Growing amount, improve pickling speed in acid cleaning process, reduce a ton steel acid consumption, realize subtracting the pickling steel.
Said according to FeO eutectoid reaction curve in iron scale microstructure in target steel grade course of hot rolling, rolling mill practice is optimized and revised in control, concrete steps are as follows: 1. obtain pure molten steel by smelting, after become strand through the conticaster continuous casting, its composition weight percentage ranges is: C:0.025%-0.065%, Si :≤0.045%, Mn:0.15%-0.25%, P :≤0.025, S :≤0.01, Als:0.015%-0.025%; 2. strand is heated to 1180-1220 ℃, insulation 20-60min, then the de-scaling water under high pressure is all opened, and the de-scaling water pressure is 18-20 Mpa, removes thorough surperficial stove and gives birth to oxide skin; 3. carry out roughing through the strand after de-scaling, the roughing start rolling temperature is 1150-1250 ℃, and the roughing finishing temperature is 1000-1070 ℃, guarantees that the secondary descaling steel water pressure is greater than 18-20Mpa; After going out roughing mill, stay-warm case is all opened, and the desired temperature of finish rolling entrance is 1030-980 ℃, and between frame, cooling water is opened the 3-4 group, and the temperature fluctuation range of finish rolling outlet is 870-890 ℃, avoids hot stage to generate too much iron scale; 4. improve the finish rolling muzzle velocity, through after adding speed rolling, reach 7-14m/s with the maximum speed of steel afterbody; 5. cooling and batch, the cooling and even cooling dual mode of cooling employing front end, coiling temperature is 600 ℃-650 ℃.
Adopt technique of the present invention, hot rolling strip steel scale structure is with eutectoid structure Fe
3O
4+ Fe is main, and percentage composition reaches 80-95%, and only in matrix and the local at the interface FeO existence that minute quantity is arranged of iron scale, its content is between 5-20%.The iron scale Thickness Ratio at cold rolling get the raw materials ready steel edge portion and middle part is more even, and structure is basically identical, and iron scale thickness basic controlling is in 6-10 μ m scope, and limit section iron scale is thinner, and the iron scale average thickness drops to 8 μ m by 14 μ m.
Technical characterstic of the present invention: (1) finish rolling muzzle velocity of the present invention is compared with common process and is improved 5%-10%, iron scale thickness obviously reduces, in addition, detection by scale structure, scale structure and the thickness of limit section, 1/4 place, center are all more even, this is to improve pickling speed, the obvious main thought of improving in pickling rear surface.(2) control the more FeO of generation and Fe
3O
4The key process technology of content is rationally to utilize TMCP technique, comprise that heating, de-scaling, roughing, finish-rolling process (rolling temperature, deflection, mill speed), laminar flow are cooling, effective combination of technology, but most crucial technique is controlled curling temperature exactly, in order to make the band steel after curling that FeO oxidation eutectoid reaction occur, making final iron scale microstructure On-line Control is the structure of easy pickling.
Good effect of the present invention: the present invention makes that in course of hot rolling, iron scale has obtained good control, has greatly improved surface quality and labor productivity that the roll coil of strip is produced in hot rolling; By changing the microstructure of iron scale, reduce the Fe that is difficult to pickling simultaneously
2O
3Growing amount, in follow-up acid cleaning process, pickling speed improves 10%, reduces a ton steel acid consumption 7.5%.The present invention has alleviated the pressure that too much spent acid discharging causes environment greatly, energy-saving and emission-reduction, and social benefit is huge.
Description of drawings
Fig. 1 is the oxidation weight gain curve of embodiment of the present invention SPHC;
Isothermal transformation cross-section morphology (a) 100s (b) 1000s (c) 10000s of FeO layer when Fig. 2 is 350 ℃ of the embodiment of the present invention;
Isothermal transformation cross-section morphology (a) 100s (b) 1000s (c) 10000s of FeO layer when Fig. 3 is 450 ℃ of the embodiment of the present invention;
Isothermal transformation cross-section morphology (a) 100s (b) 1000s (c) 10000s of FeO layer when Fig. 4 is 500 ℃ of the embodiment of the present invention;
Isothermal transformation cross-section morphology (a) 100s (b) 1000s (c) 10000s of FeO layer when Fig. 5 is 550 ℃ of the embodiment of the present invention;
Isothermal transformation cross-section morphology (a) 100s (b) 1000s (c) 10000s of FeO layer when Fig. 6 is 600 ℃ of the embodiment of the present invention;
Isothermal transformation cross-section morphology (a) 100s (b) 1000s (c) 10000s of FeO layer when Fig. 7 is 650 ℃ of the embodiment of the present invention;
Fig. 8 is the isothermal transformation curve of embodiment of the present invention FeO layer, (a) upper surface after the pickling of common process SPHC plate, (b) lower surface after the pickling of common process SPHC plate, (c) SPHC of the present invention subtracts after the pickling of pickling steel upper surface (d) SPHC of the present invention and subtracts lower surface after the pickling of pickling steel.
The specific embodiment
By the following examples, the invention will be further described.
At first a kind of production method that subtracts the pickling steel, determines in target steel grade course of hot rolling FeO eutectoid reaction curve in the iron scale microstructure, and concrete steps are as follows:
Step 1: measure the experiment of target steel grade oxidation kinetics
The purpose of carrying out oxidation kinetics experiment is to estimate the oxidation rate of each steel grade, measures oxidation weight gain and the relation curve of time, and for estimation oxide skin growing state provides basic data, to test steel grade be that SPHC is cold rolling gets the raw materials ready; The isothermal oxidation temperature is 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, and oxidization time is 60min;
Oxidation weight gain and the relation curve of time be as shown in Figure 1 in air with steel in the SPHC hot rolling.As can be seen from the figure, SPHC presents linear relation substantially in the time of 700 ℃; Present parabolic relation in time more than 700 ℃;
Oxidation rate is by the Fe between iron scale and matrix
2+And O
2-DIFFUSION CONTROLLED; When oxidation when high temperature occurs, when perhaps iron scale is thinner, Fe
2+And O
2-Diffusion velocity higher.；
Therefore, more than 700 ℃ the time, oxidation rate is very fast; Along with the carrying out of oxidation, because iron scale thickens, the oxidation curve is presented parabola shaped in the later stage; So follow-up rolling mill practice is avoided the too high and blocked up phenomenon of iron scale that bring of final cooling temperature as far as possible;
Step 2:FeO eutectoid reaction research
By the thermal simulation experiment means, the isothermal transformation behavior of the FeO layer that under research different temperatures and isothermal time condition, surface of low-carbon steel forms, to be that SPHC is cold rolling get the raw materials ready the experiment steel grade.In order to be consistent with on-site actual situations, inside, thermal simulation experiment storehouse is air atmosphere, and wherein isothermal temperature is 650,600,550,500,450 and 350 ℃, and isothermal time is respectively 100 s, 1000 s and 10000s.At each temperature, the isothermal transformation cross-section morphology of FeO layer is as shown in Fig. 2 ~ 7;
During 350 ℃ of isothermal 100s, too large variation does not occur in iron scale substantially, and evolution reaction not yet occurs; Separated out the Fe of a large amount of pro-eutectoids during 450 ℃ of isothermal 100s in the FeO layer
3O
4, and iron scale and matrix one deck cenotype appearred at the interface, when isothermal 10000s, the mixture of sheet has extended to iron scale and matrix at the interface, illustrates that eutectoid has almost all occured the FeO layer anti-; During 500 ℃ of isothermal 1000s, the large when degree of FeO eutectoid reaction does not have 450 ℃ just having the FeO of minute quantity residual near the matrix side; During 550 ℃ of isothermal 10000s, many when measuring obviously than 500 ℃ near the residual FeO of matrix side.During 600 ℃ of isothermals, precipitate does not appear in iron scale, only by the Fe in the outside
3O
4Layer and inboard FeO layer form; During 650 ℃ of isothermal 10000s, do not produce yet and separate out, just Fe
3O
4Layer and Fe
2O
3The thickness of layer all increases significantly;
According to scale structure and eutectoid reaction situation that experiment obtains, isothermal transformation curve such as Fig. 8 of obtaining FeO layer in the iron oxide cortex illustrate; Can find out that 450 ℃-550 ℃ is " nose temperature " scope of FeO layer; In this temperature range, the speed that the FeO layer changes is the fastest.
Said according to FeO eutectoid reaction curve in iron scale microstructure in target steel grade course of hot rolling, to control and optimize and revise rolling mill practice, concrete steps are as follows:
1, obtain purer molten steel by smelting, after become strand through the conticaster continuous casting, its composition weight percentage ranges is: C:0.025%-0.065%, Si :≤0.045%, Mn:0.15%-0.25%, P :≤0.025, S :≤0.01, Als:0.015%-0.025%;
2, strand is heated to 1180-1220 ℃, insulation 20-60min, then the de-scaling water under high pressure is all opened, and original technique is 15Mpa, and new technology de-scaling water pressure is 18-20 Mpa, guarantees to remove thorough surperficial stove and gives birth to oxide skin;
3, carry out roughing through the strand after de-scaling, the roughing start rolling temperature is 1150-1250 ℃, and the roughing finishing temperature is 1000-1070 ℃, guarantees that the secondary descaling steel water pressure is greater than 18-20Mpa; After going out roughing mill, stay-warm case is all opened, and the desired temperature of finish rolling entrance is 1030-980 ℃, and between frame, cooling water is opened the 3-4 group.The temperature fluctuation range of finish rolling outlet is 870-890 ℃, guaranteed performance in advance under reduce 10-25 ℃ than original technological temperature, avoid hot stage to generate too much iron scale;
4, finish rolling muzzle velocity
According to the experimental program requirement, need to improve the muzzle velocity of finish rolling F7 as far as possible.On-the-spot by manual operation, the finish rolling muzzle velocity has improved 5-15% than original technique.Through after adding speed rolling, reach 7-14m/s with the maximum speed of steel afterbody;
5, cooling and batch
Cooling and the even cooling dual mode of cooling employing front end, the cooling purpose of front end are mainly to reduce high-temperature residence time, reduce thickening of cooling section iron scale.Coiling temperature is 600 ℃-650 ℃, reduces 30-70 ℃ than original technique on the basis of guaranteed cost, guarantee the band steel can be in 450-550 ℃ of scope of FeO eutectoid reaction nose Wen Wendu after curling Slow cooling;
It is as follows that rolling mill practice embodiment is optimized and revised in field control more specifically:
Embodiment 1:: obtain purer molten steel by smelting, after become strand through the conticaster continuous casting, its composition percentage by weight is: C:0.045%, Si :≤0.023%, Mn:0.21%, P :≤0.015%, S :≤0.004%, Als:0.02%.
Strand is heated to 1190 ℃, insulation 30min, then the de-scaling water under high pressure is all opened, and pressure is 19Mpa; Carry out 3+3 roughing through the strand after de-scaling, the roughing start rolling temperature is 1170 ℃, and finishing temperature is 1020 ℃, guarantees that the secondary descaling steel water pressure is not less than 18Mpa; After going out roughing mill, stay-warm case is all opened, and the desired temperature of finish rolling entrance is 990 ℃, and between frame, cooling water is opened the 3-4 group.The desired temperature of finish rolling outlet is 880 ℃, thickness range 4.5-3.5mm, the finish rolling muzzle velocity improves 6% with original technique, through adding speed rolling after, reach 8.1m/s with the maximum speed of steel afterbody; The laminar flow type of cooling is taked evenly cooling, and coiling temperature is 600 ℃.The hot rolling strip steel scale structure that obtains is take eutectoid structure Fe3O4+Fe as main, and its percentage composition is 87%, and all the other are FeO, belong to easy pickling tissue, and the iron scale average thickness at steel edge portion and middle part is 6.7 μ m.In follow-up acid cleaning process, pickling speed is compared with original technique and is improved 12.4%, and ton steel acid consumption reduces by 8.2%.
Embodiment 2:: obtain purer molten steel by smelting, after become strand through the conticaster continuous casting, its composition percentage by weight is: C:0.033%, Si:0.015%, Mn:0.22%, P :≤0.0104%, S :≤0.0156%, Als:0.0189%.
Strand is heated to 1180 ℃, insulation 40min, then the de-scaling water under high pressure is all opened, and pressure is 20bar; Carry out 3+3 roughing through the strand after de-scaling, the roughing start rolling temperature is 1170 ℃, and finishing temperature is 1010 ℃, guarantees that the secondary descaling steel water pressure is not less than 19Mpa; After going out roughing mill, stay-warm case is all opened, and the desired temperature of finish rolling entrance is 990 ℃, and between frame, cooling water is opened the 3-4 group.The desired temperature of finish rolling outlet is 874 ℃, and the desired temperature of finish rolling outlet is 880 ℃, thickness range 3.5-3.01 mm, the finish rolling muzzle velocity improves 8% with original technique, through adding speed rolling after, reach 10.3m/s with the maximum speed of steel afterbody; The laminar flow type of cooling is taked evenly cooling, and coiling temperature is 617 ℃.The hot rolling strip steel scale structure that obtains is take eutectoid structure Fe3O4+Fe as main, and its percentage composition is 82%, and all the other are FeO, belong to easy pickling tissue, and the iron scale average thickness at steel edge portion and middle part is 7.5 μ m.In follow-up acid cleaning process, pickling speed is compared with original technique and is improved 11.9%, and ton steel acid consumption reduces by 8.0%.
Embodiment 3: obtain purer molten steel by smelting, after become strand through the conticaster continuous casting, its composition percentage by weight is: C:0.032%, Si :≤0.011%, Mn:0.177%, P:0.0087%, S:0.010%, Als:0.0209%.
Strand is heated to 1200 ℃, insulation 20min, then the de-scaling water under high pressure is all opened, and pressure is 20 Mpa; Carry out 3+5 roughing through the strand after de-scaling, the roughing start rolling temperature is 1180 ℃, and finishing temperature is 1020 ℃, guarantees that the secondary descaling steel water pressure is not less than 20Mpa; After going out roughing mill, stay-warm case is all opened, and the desired temperature of finish rolling entrance is 1100 ℃, and between frame, cooling water is opened the 3-4 group.The desired temperature of finish rolling outlet is 890 ℃, thickness range 3.0-2.5 mm, the finish rolling muzzle velocity improves 9% with original technique, through adding speed rolling after, reach 11.0m/s with the maximum speed of steel afterbody; The laminar flow type of cooling is taked evenly cooling, and coiling temperature is 630 ℃.The hot rolling strip steel scale structure that obtains is take eutectoid structure Fe3O4+Fe as main, and its percentage composition is 86%, and all the other are FeO, belong to easy pickling tissue, and the iron scale average thickness at steel edge portion and middle part is 7.9 μ m.In follow-up acid cleaning process, pickling speed is compared with original technique and is improved 11.2%, and ton steel acid consumption reduces by 7.8%.
Embodiment 4: obtain purer molten steel by smelting, after become strand through the conticaster continuous casting, its composition percentage by weight is: C:0.029%, Si:0.0098%, Mn:0.20%, P:0.00712%, S:0.0068%, Als:0.0343%.
Strand is heated to 1200 ℃, insulation 35min, then the de-scaling water under high pressure is all opened, and pressure is 20bar; Carry out 3+5 roughing through the strand after de-scaling, the roughing start rolling temperature is 1175 ℃, and finishing temperature is 1050 ℃, guarantees that the secondary descaling steel water pressure is not less than 19Mpa; After going out roughing mill, stay-warm case is all opened, and the desired temperature of finish rolling entrance is 990 ℃, and between frame, cooling water is opened the 3-4 group.The desired temperature of finish rolling outlet is 870 ℃, thickness range 2.5-2.01 mm, the finish rolling muzzle velocity improves 8% with original technique, through adding speed rolling after, reach 11.3m/s with the maximum speed of steel afterbody; The laminar flow type of cooling is taked evenly cooling, and coiling temperature is 630 ℃.The hot rolling strip steel scale structure that obtains is take eutectoid structure Fe3O4+Fe as main, and its percentage composition is 90%, and all the other are FeO, belong to easy pickling tissue, and the iron scale average thickness at steel edge portion and middle part is 8.0 μ m.In follow-up acid cleaning process, pickling speed is compared with original technique and is improved 10%, and ton steel acid consumption reduces by 7.4%.
Embodiment 5: obtain purer molten steel by smelting, after become strand through the conticaster continuous casting, its composition percentage by weight is: C:0.032%, Si:0.015%, Mn:0.192%, P:0.0103%, S:0.0083%, Als:0.0201%.
Strand is heated to 1200 ℃, insulation 30min, then the de-scaling water under high pressure is all opened, and pressure is 20bar; Carry out 3+5 roughing through the strand after de-scaling, the roughing start rolling temperature is 1170 ℃, and finishing temperature is 1050 ℃, guarantees that the secondary descaling steel water pressure is not less than 19Mpa; After going out roughing mill, stay-warm case is all opened, and the desired temperature of finish rolling entrance is 1000 ℃, and between frame, cooling water is opened the 3-4 group.The desired temperature of finish rolling outlet is 890 ℃, thickness range 2.0-1.2 mm, the finish rolling muzzle velocity improves 7% with original technique, through adding speed rolling after, reach 12.3m/s with the maximum speed of steel afterbody; The laminar flow type of cooling is taked evenly cooling, and coiling temperature is 645 ℃.The hot rolling strip steel scale structure that obtains is take eutectoid structure Fe3O4+Fe as main, and its percentage composition is 90%, and all the other are FeO, belong to easy pickling tissue, and the iron scale average thickness at steel edge portion and middle part is 8.3 μ m.In follow-up acid cleaning process, pickling speed is compared with original technique and is improved 9.5%, and ton steel acid consumption reduces by 7.4%.
Claims (2)
1. production method that subtracts the pickling steel, it is characterized in that at first, determine in target steel grade course of hot rolling FeO eutectoid reaction curve in the iron scale microstructure, concrete steps are as follows: 1. measure the experiment of target steel grade oxidation kinetics, estimate the oxidation rate of each steel grade, measure oxidation weight gain and the relation curve of time, for estimation oxide skin growing state provides basic data; 2. carry out FeO eutectoid reaction research, by the thermal simulation experiment means, the isothermal transformation behavior of the FeO layer that under research different temperatures and isothermal time condition, surface of low-carbon steel forms draws FeO eutectoid reaction curve in the iron scale microstructure; Then, according to FeO eutectoid reaction curve in iron scale microstructure in target steel grade course of hot rolling, control and optimize and revise rolling mill practice; By changing the microstructure of iron scale, reduce the Fe that is difficult to pickling
2O
3Growing amount, improve pickling speed in acid cleaning process, reduce a ton steel acid consumption, realize subtracting the pickling steel;
Said according to FeO eutectoid reaction curve in iron scale microstructure in target steel grade course of hot rolling, rolling mill practice is optimized and revised in control, concrete steps are as follows: 1. obtain pure molten steel by smelting, after become strand through the conticaster continuous casting, its composition weight percentage ranges is: C:0.025%-0.065%, Si :≤0.045%, Mn:0.15%-0.25%, P :≤0.025, S :≤0.01, Als:0.015%-0.025%; 2. strand is heated to 1180-1220 ℃, insulation 20-60min, then the de-scaling water under high pressure is all opened, and the de-scaling water pressure is 18-20 Mpa, removes thorough surperficial stove and gives birth to oxide skin; 3. carry out roughing through the strand after de-scaling, the roughing start rolling temperature is 1150-1250 ℃, and the roughing finishing temperature is 1000-1070 ℃, guarantees that the secondary descaling steel water pressure is greater than 18-20Mpa; After going out roughing mill, stay-warm case is all opened, and the desired temperature of finish rolling entrance is 1030-980 ℃, and between frame, cooling water is opened the 3-4 group, and the temperature fluctuation range of finish rolling outlet is 870-890 ℃, avoids hot stage to generate too much iron scale; 4. improve the finish rolling muzzle velocity, through after adding speed rolling, reach 7-14m/s with the maximum speed of steel afterbody; 5. cooling and batch, the cooling and even cooling dual mode of cooling employing front end, coiling temperature is 600 ℃-650 ℃.
2. subtract according to claim 1 the production method of pickling steel, it is characterized in that the finish rolling muzzle velocity is compared with common process improves 5%-10%.
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| CN102658301B (en) * | 2012-05-04 | 2014-11-12 | 武汉钢铁(集团)公司 | Control and modifying unit of scale of hot rolling strip steel |
| JP6139943B2 (en) * | 2013-03-29 | 2017-05-31 | 株式会社神戸製鋼所 | Steel material for soft magnetic parts with excellent pickling properties, soft magnetic parts with excellent corrosion resistance and magnetic properties, and manufacturing method thereof |
| CN107185969B (en) * | 2017-05-27 | 2019-10-29 | 内蒙古包钢钢联股份有限公司 | Medium carbon cold heading steel wire rod scale on surface component and method for controlling thickness |
| CN109097700B (en) * | 2018-09-26 | 2020-09-11 | 马鞍山钢铁股份有限公司 | Low-carbon steel plate easy to pickle in CSP process and manufacturing method thereof |
| CN111575465A (en) * | 2020-05-13 | 2020-08-25 | 武汉钢铁有限公司 | Production method for preventing surface of hot-rolled pickled steel from blackening |
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