CN109402321B - Method for controlling oxide inclusions in ultra-low carbon steel - Google Patents
Method for controlling oxide inclusions in ultra-low carbon steel Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/30—Regulating or controlling the blowing
- C21C5/35—Blowing from above and through the bath
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/10—Handling in a vacuum
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
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- C—CHEMISTRY; METALLURGY
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- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/068—Decarburising
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Abstract
Method for controlling oxide inclusions in ultra-low carbon steelThe method comprises the following steps: 1) smelting in a converter to ensure that molten steel [ O ] is not blown]＝450～600ppm，[C]0.01-0.05%; tapping to ensure that the thickness of the ladle slag is less than or equal to 50mm, adding 2.0-5.0kg/t of steel with lime and 0.5-2 kg/t of steel with Al modifier at the final stage in the early stage of tapping, modifying and deoxidizing the ladle top slag to ensure that the ladle top slag contains [ (wt% CaO) + (wt% MgO)]/(wt％Al2O3) 1.4-1.9, oxidizing component (FeO) + (MnO) is less than or equal to 8; 2) vacuum decarburization treatment, namely vacuum decarburization treatment in an RH furnace; after the vacuum decarburization treatment is finished, Al is added to deoxidize and alloy the molten steel, and the pure circulation time of the molten steel is more than 6 min; then rare earth metal Ce is added, the molten steel is purely circulated for 2-10min, and the vacuum treatment is finished. The control method of the invention reduces the harm of inclusions remained in steel, improves the surface quality of cold-rolled finished products and improves the steel locking rate of the cold-rolled finished products.
Description
Technical Field
The invention relates to a steelmaking process, in particular to a method for controlling oxide inclusions in ultra-low carbon steel.
Background
With the progress of the technology, the requirements of users on the quality of steel are higher and higher. For ultra-low carbon steel, a need has arisen for cold rolled finished plates as thin as 0.05mm in thickness. From the viewpoint of smelting, it is necessary to reduce the total amount of inclusions in steel to an extremely low level and to control the presence of no large-particle inclusions in the matrix. From the viewpoint of inclusion property control, it is necessary to reduce the damage of inclusions remaining in steel as much as possible. At present, the LD-RH-CC process flow is widely adopted to produce the ultra-low carbon steel, the oxygen of the finished product can be controlled to be lower than 20ppm or even lower, the total amount of inclusions in the corresponding steel reaches an extremely low level, but a large amount of residual Al in the steel still exists in the cold-rolled finished product2O3Inclusion of resulting steel blockages. Therefore, the final generation of inclusions (Al) is controlled2O3) Thus reducing the harm to the finished product, becomes a necessary choice. Compared with other links in smelting, the RH furnace has good vacuum environment, reaction and flow dynamic conditions, and is the most ideal oxide inclusion control place。
In the technical scheme disclosed in the Chinese patent publication No. CN1678761B, after Al deoxidation is emphasized, one or more rare earth elements of Ce, La, Pr and Nd are added into molten steel, the rare earth oxide/(rare earth oxide + alumina) in the steel is 0.5-15%, and REM/T.O is 0.05-0.5, and Al deoxidation products Al are reduced2O3The cluster of the steel is formed, so that the size of inclusions in the steel is reduced, and the product quality is improved. The patent emphasizes that the process effect is that the Al in the molten steel is inhibited because the molten steel deoxidized by Al is added with trace rare earth2O3Reducing the agglomeration of large-particle Al2O3The inclusion is generated.
Disclosure of Invention
The invention aims to provide a method for controlling oxide inclusions in ultra-low carbon steel, which aims to reduce the harm of inclusions remained in steel, improve the surface quality of a cold-rolled finished product and improve the steel blockade rate of the cold-rolled finished product.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for controlling oxide inclusions in ultra-low carbon steel comprises the following steps:
1) smelting, namely smelting the raw materials,
smelting in a converter, adopting top-bottom combined blowing, keeping bottom blowing operation and ensuring molten steel [ O ] when blowing is stopped]＝450～600ppm，[C]0.01-0.05%; meanwhile, tapping to ensure that the thickness of the ladle slag is less than or equal to 50mm, adding 2.0-5.0kg/t of steel with lime and 0.5-2 kg/t of steel with Al modifier at the final stage in the early stage of tapping, modifying and deoxidizing the ladle top slag to ensure that the ladle top slag contains [ (wt% CaO) + (wt% MgO)]/(wt％Al2O3) 1.4-1.9, oxidizing component (FeO) + (MnO) is less than or equal to 8;
2) vacuum decarburization treatment
Carrying out vacuum decarburization treatment in an RH furnace to ensure that carbon in the molten steel is below a required value of a finished product; after the vacuum decarburization treatment is finished, Al is added to deoxidize and alloy the molten steel, and the pure circulation time of the molten steel is more than 6 min; then rare earth metal Ce is added, the molten steel is purely circulated for 2-10min, and the vacuum treatment is finished.
Preferably, the ultra-low carbon steel product comprises the following components in percentage by weight: less than or equal to 0.005 percent of C, less than or equal to 0.05 percent of Si, 0.4 to 0.9 percent of Mn, 0.02 to 0.1 percent of Al, less than or equal to 0.01 percent of Ti, less than or equal to 0.05 percent of P, less than or equal to 0.02 percent of S, less than or equal to 0.003 percent of N and the balance of Fe.
Preferably, the upper limit of the addition amount of the rare earth metal Ce is the ratio of the addition mass of the rare earth to the total oxygen in the steel, and the lower limit of the addition amount of the rare earth metal is determined to be 0.80 of the addition mass of the rare earth metal REM/T.O.
Preferably, the rare earth metal Ce comprises the following components in percentage by mass: ce > 90%, La < 5%, O < 0.015%.
Preferably, the sliding plate slag blocking operation is adopted in the tapping process in the step 1), so that the ladle slag thickness is ensured to be less than or equal to 50 mm.
In the control method of the present invention:
during the smelting of the ultra-low carbon steel, oxygen (free oxygen and combined oxygen) added in the converter smelting is the most main oxygen source in the whole smelting process, and then in the tapping process, molten steel containing a large amount of oxygen and steel slag enter a steel ladle. Oxygen in molten steel is used for vacuum cycle refining decarburization, and oxide inclusions are formed in the subsequent deoxidation process, so that the oxygen is harmful to the quality of steel. Therefore, the present invention requires the converter to maintain good bottom blowing operation (top-bottom combined blowing) to ensure the molten steel [ O ] at the time of blowing stop]＝450～600ppm([C]0.01-0.05). Meanwhile, the steel tapping process adopts a sliding plate slag blocking operation to ensure that the thickness of the ladle slag is less than or equal to 50mm (no slag charge is added), 2.0-5.0kg/t of steel of lime and 0.5-2 kg/t of steel of Al modifier at the last stage are added in the early stage of steel tapping, and the ladle top slag is modified and deoxidized to ensure that the ladle top slag contains [ (wt% CaO) + (wt% MgO) before vacuum treatment]/(wt％Al2O3) 1.4-1.9, and the oxidizing component (wt% FeO) + (wt% MnO) is less than or equal to 8.
And (3) carrying out vacuum decarburization treatment in an RH furnace so that the carbon in the molten steel is below a required value of a finished product. And after the vacuum treatment and decarburization are finished, Al is added to deoxidize and alloy the molten steel. The pure circulation time of the molten steel is more than 6min to ensure that a deoxidation product Al in the steel2O3Fully floating to the top slag of the ladle. Adding rare earth metal Ce, pure circulating the molten steel for 2-10min, and finishing the vacuum treatment.
Al2O3The crystal has a multi-crystal structure, wherein alpha-Al2O3Is Al2O3High temperature ofThe crystal form with the most compact structure and low activity is the most stable crystal form in various allotypic crystals. Al formed by deoxidation in steel2O3Belongs to an alpha crystal form, has a hexagonal unit cell structure, and has very high hardness, and Mohs hardness of 9 grade. CeO (CeO)2Is cubic system and has CaF2Form crystal structure, Mohs hardness 6. The hardness of several typical materials is shown in table 1.
TABLE 1
| Material | Mohs hardness |
| α-Al2O3 | 9 |
| Cooked iron | 4 |
| Cast iron | 〉7 |
| CeO2 | 6 |
It can be seen that Al is compared with ultra-low carbon steel2O3Is much greater than that of CeO2It is close to it.
Adding rare earth metal Ce in the molten steel and deoxidation product Al not discharging the molten steel2O3The following reaction was sent:
3[Ce]+2(A2O3)＝3(CeO2)+2[Al]
a part of Al2O3Part of particles or clustersIs reduced to generate rare earth oxide coated Al2O3(ii) a A part of Al2O3Particles (A)<3 μm) is completely reduced, and [ Ce ] in the molten steel is obtained along with the homogenization of the Ce alloy concentration]、[Al]、(Al2O3) And (CeO)2) Chemical equilibrium again, small particle Al2O3Formed CeO being completely reduced2The following reactions occur:
3(CeO2)+2[Al]＝3[Ce]+2(A2O3)
thereby forming a solid solution mAl2O3·nCeO2. Referring to FIG. 1, a typical coated CeO is shown2And semi-coating the composite inclusion.
With the original Al2O3In contrast, the resulting composite inclusion solid solution or Al coated with rare earth oxide2O3The surface hardness decreases and the plasticity increases. During subsequent rolling, the solid solution of the inclusion containing rare earth has the tendency of extending along the rolling direction, and the probability of scratching the steel plate matrix is reduced (corresponding to pure Al in the original inclusion)2O3) Thereby reducing the loss degree of the steel plate matrix and improving the surface quality of the finished product.
There is a reasonable interval with respect to the amount of rare earth added. The upper limit of the rare earth addition amount is determined as the ratio of the rare earth addition mass to the total oxygen in the steel, and REM/T.O is 3.40. There are two possible adverse consequences of too high a rare earth metal addition:
1) the rare earth has higher specific gravity, and the generated oxide is not easy to float upwards in the following molten steel standing and casting processes;
2) the rare earth in the molten steel reacts with refractory materials to pollute the molten steel, and the stopper rod or the nozzle can be melted and damaged under severe conditions, so that the casting is abnormal or interrupted.
The lower limit of the amount of rare earth added is defined as REM/t.o 0.80. Low rare earth addition, Al2O3The content of rare earth oxide in the converted rare earth-containing composite inclusions is not enough, the hardness of oxide inclusions is still too high, the modification effect of rare earth on oxide inclusions is further influenced, and the metallurgical effect of improving the quality of cold-rolled products cannot be fully reflected.
Compared with the Chinese patent CN 1678761B:
the mechanism of the comparative patent for improving the product quality by trace rare earth is as follows: adding trace rare earth into molten steel after Al deoxidation to inhibit Al in molten steel2O3Reducing the agglomeration of large-particle Al2O3Generating impurities; the added rare earth is one or more than two of Ce/La/Pr/Nd, and the addition amount is as follows: 1. rexOy/(RexOy+Al2O3)＝0.5-15％；2、REM/T.O＝0.05-0.5。
The mechanism of the trace rare earth for improving the product quality is as follows: rare earth and Al2O3Reaction to form mCeO2·nAl2O3Solid solution with hardness close to that of steel matrix and far lower than that of pure Al2O3Thereby greatly reducing Al in cold rolling and subsequent cold processing2O3And mechanical damage to the steel plate matrix is included. The rare earth effective component Ce: (>90%), the higher the content, the better; the addition amount of rare earth REM/T.O is 0.8-3.40.
The invention has the beneficial effects that:
in the control method of the invention, rare earth metal Ce is added into the molten steel after Al deoxidation, and the improvement effect on the steel quality of the cold-rolled sheet is realized by rare earth and Al2O3Reaction to form mCeO2·nAl2O3Solid solution with hardness close to that of steel matrix and far lower than that of pure Al2O3Thereby greatly reducing Al in cold rolling and subsequent cold processing2O3And mechanical damage to the steel plate matrix is included.
1) Effectively reducing the cold rolling steel defect blocking rate by more than 35 percent;
2) effectively reduce Al2O3The defect blocking rate of the cold rolled steel is reduced>25％；
3) The quality of the final finished product is obviously improved.
Drawings
FIG. 1 shows a coated CeO2Photo of semi-coated composite inclusions.
Detailed Description
The invention is further illustrated by the following examples:
the production process route of the ultra-low carbon steel is as follows: the method comprises the following steps of molten iron desulphurization, dephosphorization, converter decarburization, steel tapping, ladle top slag modification, RH decarburization, deoxidation and component fine adjustment, continuous casting, hot rolling, acid pickling and cold rolling.
Example 1
After the converter blowing is finished, [ C ]]＝280ppm，[O]550 ppm; slag stopping and tapping, wherein 3.32kg/t of steel is added in the early stage of tapping, and 0.87kg/t of steel is added in the later stage of tapping; the components of the ladle top slag (wt% FeO) + (wt% MnO) before vacuum treatment are less than or equal to 7.40, [ (wt% CaO) + (wt% MgO)]/(wt％Al2O3) The thickness of the slag is 118mm, which is 1.72. After the vacuum decarburization is finished, Al is added to deoxidize and alloy the molten steel, and the components of the molten steel are adjusted to the specification range, [ C ]]＝20ppm，[Si]＝0.01，[Mn]＝0.65，[S]＝120ppm，[Al]＝0.045，[Ti]When the temperature is equal to 0.004, the molten steel circulates for 6.8 min; after the rare earth is added, the molten steel is circulated for 4.2min, the refining is finished, and the continuous casting, the hot rolling, the acid cleaning and the cold rolling are carried out. And (3) counting inclusions in the casting blank by adopting an Apex-Utral55 scanning electron microscope, wherein REM/T.O is 1.75.
Example 1 process effect: for the judgment of the final process effect, the conventional heat adjacent to the tundish is taken as a comparison object, the cold rolling steel blocking rate of the embodiment of the invention is 1.75 percent, wherein Al is2O3The steel blocking rate is 0, the cold rolling steel blocking rates of adjacent front and back heats are 3.51 percent and 3.22 percent respectively, and Al is2O3The resulting are 1.21% and 0.72%, respectively.
Table 2 shows a comparison of some practical examples of the process according to the invention.
TABLE 2
The method for controlling oxide inclusions developed aiming at ultra-low carbon steel cold-rolled products effectively improves the performance of deoxidation inclusions in steel, further reduces the incidence rate of steel defects of cold-rolled finished products, is suitable for improving the quality of the ultra-low carbon steel cold-rolled products, and has popularization and application values in steel mills.
Claims (4)
1. A method for controlling oxide inclusions in ultra-low carbon steel is characterized by comprising the following steps:
1) smelting, namely smelting the raw materials,
smelting in a converter, adopting top-bottom combined blowing, keeping bottom blowing operation and ensuring molten steel [ O ] when blowing is stopped]＝450～600ppm，[C]0.01-0.05%; meanwhile, tapping to ensure that the thickness of the ladle slag is less than or equal to 50mm, adding 2.0-5.0kg/t of steel with lime and 0.5-2 kg/t of steel with Al modifier at the final stage in the early stage of tapping, modifying and deoxidizing the ladle top slag to ensure that the ladle top slag contains [ (wt% CaO) + (wt% MgO)]/(wt％Al2O3) 1.4-1.9, oxidizing component (FeO) + (MnO) is less than or equal to 8;
2) vacuum decarburization treatment
Carrying out vacuum decarburization treatment in an RH furnace to ensure that carbon in the molten steel is below a required value of a finished product; after the vacuum decarburization treatment is finished, Al is added to deoxidize and alloy the molten steel, and the pure circulation time of the molten steel is more than 6 min; adding rare earth metal Ce, pure circulating the molten steel for 2-10min, and finishing vacuum treatment; wherein, the upper limit of the addition amount of the rare earth metal Ce is the ratio of the addition mass of the rare earth to the total oxygen in the steel, REM/T.O is 3.40, and the lower limit of the addition amount of the rare earth is 0.80.
2. The method for controlling oxide inclusions in ultra low carbon steel as claimed in claim 1, wherein the ultra low carbon steel product comprises the following components in percentage by weight: less than or equal to 0.005 percent of C, less than or equal to 0.05 percent of Si, 0.4 to 0.9 percent of Mn, 0.02 to 0.1 percent of Al, less than or equal to 0.01 percent of Ti, less than or equal to 0.05 percent of P, less than or equal to 0.02 percent of S, less than or equal to 0.003 percent of N and the balance of Fe.
3. The method for controlling oxide inclusions in ultra-low carbon steel according to claim 1, wherein the rare earth metal Ce comprises the following components in percentage by mass: ce > 90%, La < 5%, O < 0.015%.
4. The method for controlling oxide inclusions in ultra-low carbon steel as claimed in claim 1, wherein a sliding plate slag stopping operation is adopted in the tapping process in step 1) to ensure that the ladle slag thickness is less than or equal to 50 mm.
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| CN201811146115.6A CN109402321B (en) | 2018-09-29 | 2018-09-29 | Method for controlling oxide inclusions in ultra-low carbon steel |
| PCT/CN2019/108924 WO2020063948A1 (en) | 2018-09-29 | 2019-09-29 | Ultra-low carbon steel and method for controlling oxide inclusions in ultra-low carbon steel |
| DE112019004848.1T DE112019004848T5 (en) | 2018-09-29 | 2019-09-29 | Ultra-low carbon steel and method of controlling oxide inclusions in ultra-low carbon steel |
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| CN109402321B (en) * | 2018-09-29 | 2020-11-17 | 宝山钢铁股份有限公司 | Method for controlling oxide inclusions in ultra-low carbon steel |
| CN112442631B (en) * | 2019-08-30 | 2022-03-18 | 宝山钢铁股份有限公司 | Control method for titanium-containing ultra-low carbon steel cold-rolled steel defects |
| CN111411197A (en) * | 2020-04-30 | 2020-07-14 | 包头钢铁（集团）有限责任公司 | Rare earth treated refined ultra-low carbon IF steel casting-rolling overall process Al2O3Method for inclusion |
| CN112094987A (en) * | 2020-10-14 | 2020-12-18 | 马鞍山钢铁股份有限公司 | Method for controlling carbon content of molten steel |
| CN113333701B (en) * | 2021-06-03 | 2022-11-22 | 北京首钢股份有限公司 | Control method for linear slag winding defect on surface of cold-rolled sheet steel |
| CN115537504A (en) | 2021-06-29 | 2022-12-30 | 宝山钢铁股份有限公司 | Preparation method of titanium-containing ultra-low carbon steel |
| CN114262766A (en) * | 2021-11-30 | 2022-04-01 | 邯郸钢铁集团有限责任公司 | Method for quickly decarbonizing RH refined ultra-low carbon steel |
| CN115323119B (en) * | 2022-07-13 | 2023-12-22 | 首钢京唐钢铁联合有限责任公司 | Preparation method of high-purity IF steel |
| CN116814890B (en) * | 2023-07-18 | 2024-06-04 | 辛集市澳森特钢集团有限公司 | Shaping control method for inclusion of cord steel |
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| JPH01301815A (en) * | 1988-05-30 | 1989-12-06 | Sumitomo Metal Ind Ltd | Smelting method of low carbon steel |
| US5152831A (en) * | 1991-06-27 | 1992-10-06 | Kawasaki Steel Corporation | Method of producing ultra-low-carbon steel |
| JP3626278B2 (en) * | 1996-03-25 | 2005-03-02 | Ｊｆｅスチール株式会社 | Method for producing Al-killed steel without clusters |
| JP4430284B2 (en) * | 2002-07-23 | 2010-03-10 | 新日本製鐵株式会社 | Steel material with few alumina clusters |
| CN101215618A (en) * | 2007-12-27 | 2008-07-09 | 本钢板材股份有限公司 | Method for smelting ultra-low-carbon steel |
| CN102719600A (en) * | 2012-03-29 | 2012-10-10 | 鞍钢股份有限公司 | Production method of ultra low carbon steel |
| CN103451349B (en) * | 2013-08-16 | 2015-07-22 | 河北钢铁股份有限公司邯郸分公司 | Control method for preventing nozzle clogging in casting process of ultra-low carbon-aluminium deoxidized molten steel |
| CN105821178B (en) * | 2016-03-24 | 2018-03-06 | 首钢总公司 | The smelting process of ultra-low-carbon steel |
| CN107354269A (en) * | 2017-05-26 | 2017-11-17 | 内蒙古包钢钢联股份有限公司 | The method that RH complex deoxidizations produce ultra-low-carbon steel |
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