WO2022017545A1 - V-n微合金钢及v-n微合金化的无表面裂纹连铸坯的生产方法 - Google Patents

V-n微合金钢及v-n微合金化的无表面裂纹连铸坯的生产方法 Download PDF

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Publication number
WO2022017545A1
WO2022017545A1 PCT/CN2021/118337 CN2021118337W WO2022017545A1 WO 2022017545 A1 WO2022017545 A1 WO 2022017545A1 CN 2021118337 W CN2021118337 W CN 2021118337W WO 2022017545 A1 WO2022017545 A1 WO 2022017545A1
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Prior art keywords
continuous casting
steel
water volume
blowing
refining
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English (en)
French (fr)
Inventor
王中学
霍孝新
杜林秀
麻衡
陈爱娇
杜传治
宁伟
刘悦
吴红艳
何康
赵立峰
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Laiwu Steel Group Yinshan Section Steel Co Ltd
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Laiwu Steel Group Yinshan Section Steel Co Ltd
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Priority to US18/258,439 priority Critical patent/US20240327963A1/en
Priority to EP21847037.5A priority patent/EP4227431A4/en
Publication of WO2022017545A1 publication Critical patent/WO2022017545A1/zh
Anticipated expiration legal-status Critical
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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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/16—Controlling or regulating processes or operations
    • B22D11/22—Controlling or regulating processes or operations for cooling cast stock or mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/16—Controlling or regulating processes or operations
    • B22D11/22—Controlling or regulating processes or operations for cooling cast stock or mould
    • B22D11/225—Controlling or regulating processes or operations for cooling cast stock or mould for secondary cooling
    • 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
    • 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
    • C21C7/06—Deoxidising, e.g. killing
    • 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
    • C21C7/072—Treatment with gases
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys

Definitions

  • the invention belongs to the field of continuous casting technology, in particular to a method for producing a V-N microalloyed continuous casting billet without surface cracks.
  • Microalloyed steel is a steel for engineering structures that has developed rapidly in the past half century. By adding various alloying elements (Nb, V, Ti, etc.) It is widely used in various fields such as bridges, buildings, ships, automobiles, high-pressure vessels, etc. It has good application prospects and is the main product in the modern steel industry. China has abundant reserves of microalloying elements and has significant advantages in the development of microalloyed steels. Typical Q550 and Q460 grades of low alloy high strength steel have good market applications.
  • micro-alloying is widely used due to the strengthening effect of micro-alloying elements, but in the process of continuous casting, due to the precipitation of carbonitrides of micro-alloying elements, the plasticity of steel is reduced, and the surface cracks of continuous casting billets are reduced.
  • the occurrence rate is significantly higher than that of ordinary carbon steel billets, and problems such as transverse cracks, longitudinal cracks, and shape cracks occur, which affect the quality of continuous casting billets and are not conducive to large-scale production. This is a typical problem of microalloyed billets.
  • Niobium, vanadium, and titanium are the three elements that are relatively widely used in microalloyed steels.
  • niobium has the greatest effect on the plasticity of steel and the most obvious effect on the reduction of thermoplasticity of steel.
  • the present invention provides a VN microalloyed steel without surface cracks in the continuous casting billet.
  • the exit section is (150 ⁇ 350)mm*(1250 ⁇ 2400)mm without surface cracks, which improves the surface quality of the continuous casting.
  • a VN microalloyed steel which is composed of the following chemical components in percentage by mass: C: 0.09-0.13%, Si: 0.1-0.4%, Mn: 1.0-3.0%, P: ⁇ 0.05%, S: ⁇ 0.05%, V: 0.1 to 0.4%, N: 0.011 to 0.2%, and the balance is Fe and inevitable impurity elements.
  • the chemical composition of the microalloyed steel is rationally designed by utilizing the low thermoplastic trough point of the vanadium-containing steel, so as to reduce the occurrence of surface cracks on the slab surface of the microalloyed steel during continuous casting.
  • the V element has a strong affinity with the N element, and the combination of the TMCP method in the later stage can increase the strength and toughness of the tissue through the two typical strengthening mechanisms of fine-grain strengthening and precipitation strengthening.
  • V-N microalloying is beneficial to reduce the production cost of continuous casting slabs.
  • the invention also provides a method for producing a VN microalloyed continuous casting billet without surface cracks.
  • the continuous casting billet is produced according to the chemical composition of the VN microalloyed steel; the method sequentially includes: converter smelting, LF refining and continuous casting. casting process.
  • the section specification of the continuous casting slab is (150-350) mm*(1250-2400) mm.
  • the molten iron ratio is controlled at 88.0% to 91.0% (for example, 88.0%, 89.0%, 90.0%, 91.0%), and the top-bottom double blowing mode is adopted throughout the whole process. , and blow nitrogen first and then argon during the blowing process to stir the molten steel to promote the chemical reaction in the furnace.
  • the argon blowing time is not less than 3min (for example, 3min, 5min, 10min, 15min).
  • the blowing process adopts the form of one shot to the end, and there is no supplementary blowing process, so as to avoid superoxidation of molten steel in the supplementary blowing process and increase the number of inclusions. .
  • the C content at the smelting end point is controlled at 0.09-0.13% (for example, 0.09%, 0.10%, 0.11%, 0.12%, 0.13%), the tapping temperature is 1625-1645°C (for example, 1625°C, 1630°C, 1635°C, 1640°C, 1645°C).
  • the tapping temperature is 1625-1645°C (for example, 1625°C, 1630°C, 1635°C, 1640°C, 1645°C).
  • LF refining is performed after tapping, without vacuum degassing refining; the purpose of not performing vacuum degassing is to ensure the N content in the molten steel.
  • the continuous casting process adopts a weak water cooling method to effectively reduce the occurrence of cracks in the slab.
  • the continuous casting process adopts protective pouring, the large ladle alarms and immediately closes the nozzle at the end of the pouring stage, and it is strictly forbidden to open it again after the nozzle is closed, and the tundish is carried out with an alkaline covering agent. Cover to ensure that the liquid level is well covered, and the mold is made of low-carbon steel mold slag.
  • the specific water amount in the continuous casting process is 0.7-1.25L/kg (for example, 0.7L/kg, 0.8L/kg, 1.0L/kg, 1.2 L/kg, 1.25L/kg).
  • the degree of superheat of the continuous casting furnace is strictly controlled, and the degree of superheat of molten steel is 10 to 25°C (for example, 10°C, 15°C, 20°C, 25°C).
  • the pulling speed is 1.0-1.3m/min (for example, 1.0m/min, 1.1m/min, 1.2m/min, 1.3 m/min).
  • the low superheat degree is controlled, which is beneficial to increase the drawing speed, shorten the pouring time, and reduce the energy consumption;
  • the tundish adopts an alkaline covering agent to keep the ladle warm and remove the inclusions in the ladle.
  • the mold slag is divided into a powder slag layer, a sintered layer and a liquid slag layer during the dissolving process.
  • the specific operation method of the deoxidation alloying is: in the tapping process, a silicon-containing material is selected for deoxidation, and the addition amount is: 3.5 ⁇ 4.0kg/ton steel (for example, 3.5kg/ton steel, 3.6kg/ton steel, 3.8kg/ton steel, 4.0kg/ton steel); use silicon manganese and vanadium-nitrogen alloy for alloying, among which vanadium-nitrogen alloy (V content is not less than 75%) the addition amount is 1 ⁇ 2kg/ton steel (for example, 1kg/ton steel, 1.2kg/ton steel, 1.4kg/ton steel, 1.6kg/ton steel, 1.8kg/ton steel, 2kg/ton steel).
  • the present invention does not use aluminum for deoxidation.
  • the slag washing is carried out with a CaO-containing material (the CaO content is not less than 90%), and the addition amount is 3.5 ⁇ 4.0kg/ton of steel (for example, 3.5kg/ton of steel, 3.6kg/ton of steel, 3.8kg/ton of steel, 4.0kg/ton of steel), the CaO-containing substance needs to be added before the molten steel reaches 3/4 .
  • the argon blowing amount for argon blowing and stirring is 400 to 1000L/min (for example, 500L/min, 600L/min, 700L/min, 800L/min, 900L/min), the stirring time of blowing argon is 3 ⁇ 4min (for example, 3min, 3.2min, 3.5min, 3.8min, 4min), while stirring, be careful not to expose molten steel, and then use silicon-containing material to deoxidize, The composition was fine-tuned under stirring with argon.
  • weak argon gas is used for stirring in the middle and final stages of LF refining, and the flow rate of argon blowing is the same.
  • the amount of argon blowing for argon blowing and stirring is 100-200L/min (for example, 120L/min, 140L/min, 160L/min).
  • the time of argon blowing and stirring is ⁇ 5min; the total refining time is controlled at 40-50min (for example, 40min, 42min, 45min, 48min, 50min), and the N content obtained is 100-2000ppm (for example, 100ppm) , 500ppm, 1000ppm, 1500ppm, 2000ppm), and the content of other components meets the molten steel component content required in the smelting process.
  • the specific distribution of water in the continuous casting process is as follows: , 8.5%, 9.0%, 9.5%, 10.0%), the water volume of the narrow surface foot roll accounts for 3.4 to 4.5% of the total water volume (for example, 3.4%, 3.8%, 4.0%, 4.2%, 4.5%), the vertical bending section
  • the inner and outer arc water in the second zone accounts for 11.0-15.9% of the total water (for example, 11.0%, 12.0%, 13.0%, 14.0%, 15.0%, 15.5%, 15.9%), and the inner and outer arc water in the third zone accounts for 13.0-15.9% of the total water.
  • the internal and external arc water in the four zones accounts for 12.0 to 13.0% of the total water (for example, 12.0%, 12.2%, 12.5%, 12.6%, 12.8% , 13.0%), the inner and outer arc water in the five zones of arc 1 section accounts for 8.5 to 9.5% of the total water (for example, 8.0%, 8.5%, 9.0%, 9.5%), and the inner and outer arc water in the six zones corresponding to arc 2 and 3 sections
  • the arc water volume accounts for 12.0-14.0% of the total water volume (for example, 12.0%, 12.5%, 13.0%, 13.5%, 13.8%, 13.0%), and the inner and outer arc water volume of the seven zones in the 4th to 5th stage accounts for 8.0-11.5% of the total water volume (For example, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, 11.0%, 11.5%, 10.0%), the internal and external arc water in the eight zones of straightening 6, 7 and 8 accounts for 8.0 ⁇ 8
  • the method for producing a VN microalloyed continuous casting billet without surface cracks improves the thermoplasticity of the continuous casting billet through reasonable component design of the VN microalloying and combined with a suitable smelting and continuous casting process, so that the billet can be straightened in the casting billet.
  • the interval avoids the high temperature brittle zone or the thermoplasticity is good enough so that no surface cracks occur, the surface quality of the billet is good, and the billet cleaning is not required, which improves the production efficiency.
  • VN microalloyed steel with no surface crack continuous casting billet.
  • the VN microalloyed steel is composed of the following chemical components by mass percentage: C: 0.09-0.13%, Si: 0.1-0.4 %, Mn: 1.0-3.0%, P: ⁇ 0.05%, S: ⁇ 0.05%, V: 0.1-0.4%, N: 0.011-0.2%, the balance is Fe and a small amount of unavoidable impurity elements.
  • the invention also provides a production method for preparing the micro-alloyed steel with the above chemical composition without surface crack continuous casting billet, which sequentially includes the following steps: converter smelting, LF refining and continuous casting.
  • the alkaline covering agent and the low carbon steel mold flux used in the production process of the continuous casting slab of the present invention are commercially available products commonly used in the production of microalloyed steel.
  • the present embodiment provides a V-N microalloyed continuous casting billet and a production method thereof.
  • the chemical composition of the continuous casting billet by mass percentage is shown in Table 1.
  • the production method includes the following steps in sequence: converter smelting, LF refining and continuous casting.
  • the converter smelting process uses a 120t converter for smelting.
  • the smelting raw materials are molten iron and scrap steel, and the ratio of molten iron is controlled at 90%.
  • Nitrogen is used for blowing in the early stage, and argon is used in the later stage.
  • the argon blowing time is 4min, and the blowing process uses one shot.
  • the supplementary blowing process is resolutely eliminated, thereby preventing the overoxidation of molten steel and improving the cleanliness of molten steel.
  • the C content at the end of smelting is controlled at 0.10wt%, and the tapping temperature is 1632°C; deoxidation alloying and slag washing are carried out during the tapping process, and the deoxidizer is selected from silicon-containing substances, and the addition amount is about 3.6kg/ton steel; the alloying raw material is vanadium Nitrogen alloy (V content is 77wt%), the addition is about 1.6kg/ton steel; CaO-containing material (CaO content is 90wt%) is selected for slag washing, and the addition amount is 3.8kg/ton steel.
  • the ladle After tapping, the ladle is directly transferred to the LF refining station for argon blowing refining.
  • the amount of argon blowing in the early stage of refining is 400 L/min for argon blowing and stirring for 3 minutes.
  • silicon-containing substances are added for deoxidation, and a small amount of silicon manganese is added to adjust the Mn content; at the end of refining, argon blowing is performed.
  • the amount was adjusted to 150L/min and stirred for 6min; the total refining time was controlled at 45min, the N content obtained was 120ppm, and the content of other components met the molten steel component content required in the component control process.
  • the large package is protected by a long nozzle, and a conical asbestos pad is added to ensure the tightness of the connection.
  • the gas flame After the casting starts, first use the gas flame to test the tightness of the ladle shroud and the bowl of the long shroud. If the flame is inhaled, it means that the tightness of the place is not good, and the long shroud should be re-covered. If the airtightness meets the requirements, during the pouring process, argon gas is introduced into the connection of the bowl of the long nozzle to form an argon-sealed state, which further prevents the connection between the bowl of the long nozzle and the ladle outlet from being loose and caused by air inhalation. Addition of oxygen and nitrogen to molten steel.
  • the big bag alarms at the end of pouring and closes the nozzle immediately. After the nozzle is closed, it is strictly forbidden to open it again.
  • the tundish is covered with alkaline covering agent, and the mold is protected with mild steel mold slag (P0050 for Shinagawa 250).
  • This example is the third heat of pouring, that is, the third heat of steel poured after continuous casting starts, the superheat degree is 20°C, and the actual pulling speed is 1.1m/min.
  • the specific distribution of water with a specific water volume of 1.2L/kg is as follows: the water volume of the inner and outer arcs of the wide-faced foot rolls accounts for about 8.6% of the total water volume, the narrow-faced foot rolls accounted for 3.5% of the total water volume, and the vertical bending section
  • the inner and outer arc water volume of the second zone accounts for 15.8% of the total water volume
  • the third zone inner and outer arc water volume accounts for 15.6% of the total water volume
  • the fourth zone inner and outer arc water volume accounts for 12.9% of the total water volume
  • the fifth zone inner and outer arc water volume of the first arc section accounts for the total water volume.
  • the present invention adopts the continuous casting billet obtained from the multi-furnace steel poured by the above method, the cross section is 200mm*2000mm, the surface quality is good, there is no crack in the low magnification inspection, and the surface of the billet is observed in the hot state without cracks, and no billet cleaning is required.
  • V-N microalloyed continuous casting billet without surface cracks is produced, and its chemical composition is shown in Table 2 by mass percentage.
  • the production method includes the following steps in sequence: converter smelting, LF refining and continuous casting.
  • the smelting process uses a 120t converter for smelting.
  • the raw materials for smelting are molten iron and scrap steel.
  • the ratio of molten iron to molten iron is controlled at 89%.
  • Nitrogen is used for blowing in the early stage, and argon is used in the later stage.
  • the argon blowing time is 3 minutes. Form blowing, resolutely put an end to the supplementary blowing process.
  • the C content at the smelting end is controlled at 0.09wt%, and the tapping temperature is 1630°C.
  • the deoxidizer is selected from silicon-containing substances (ie silicon carbide), and the addition amount is about 3.8kg/ton steel; It is 1.3kg/ton steel; CaO-containing material (CaO content is 90wt%) is selected for slag washing, and the addition amount is 3.6kg/ton steel.
  • the ladle After tapping, the ladle is directly transferred to the LF refining station for argon blowing refining.
  • the amount of argon blowing in the early stage of refining is 400L/min for argon blowing and stirring for 4 minutes, and then silicon-containing substances are added for deoxidation; the amount of argon blowing in the final stage of refining is adjusted to 150L/min. ;
  • the total refining time is controlled at 48min, the N content obtained is 100ppm, and the content of other components meets the content of molten steel required in the component control process.
  • the large package is protected by a long nozzle, and a conical asbestos pad is added to ensure the tightness of the connection.
  • a conical asbestos pad is added to ensure the tightness of the connection.
  • the gas flame After the casting starts, first use the gas flame to test the tightness of the ladle shroud and the bowl of the long shroud. If the flame is inhaled, it means that the tightness of the place is not good, and the long shroud should be re-covered. If the airtightness meets the requirements, during the pouring process, argon gas is introduced into the connection of the bowl of the long nozzle to form an argon-sealed state, which further prevents the connection between the bowl of the long nozzle and the ladle outlet from being loose and caused by air inhalation.
  • This example is the fourth heat of steel poured by continuous casting after open casting, the superheat degree is 15°C, and the actual pulling speed is 1.2m/min.
  • the specific distribution of water with a specific water volume of 1.0L/kg is as follows: the water volume of the inner and outer arcs of the wide-faced foot rolls accounts for about 8.1% of the total water, and the narrow-faced foot rolls account for 4.3% of the total water.
  • the inner and outer arc water volume in the second zone accounts for 11.4% of the total water volume
  • the third zone inner and outer arc water volume accounts for 13.1% of the total water volume
  • the fourth zone inner and outer arc water volume accounts for 12% of the total water volume
  • the fifth zone inner and outer arc water volume in the arc 1 section accounts for the total water volume.
  • the inner and outer arc water in the six zones corresponding to the arc 2 and 3 sections accounts for 13.6% of the total water volume, and the inner and outer arc water in the seven zones in the 4-5 sections accounts for 11.2% of the total water volume.
  • Straightening sections 6, 7 and 8 The inner and outer arc water in the eight zones of the section accounts for 11.3% of the total water, and the rest is allocated to the horizontal section.
  • the continuous casting billet obtained from the multi-furnace steel poured by the above method has a specification of 250mm*1800mm, the surface quality is good, there is no obvious crack in the low-power inspection, and the surface of the billet is observed in the hot state. There is no obvious crack, and no billet cleaning is required. .

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Abstract

本发明公开了一种V-N微合金钢及V-N微合金化的无表面裂纹连铸坯的生产方法。该V-N微合金钢按质量百分比由以下化学成分组成：C：0.09～0.13％，Si：0.1～0.4％，Mn：1.0～3.0％，P：≤0.05％，S：≤0.05％，V：0.1～0.4％，N：0.011～0.2％，余量为Fe和不可避免的杂质元素。该连铸坯根据上述V-N微合金钢的化学成分进行成分控制；其生产方法依次包括：转炉冶炼、LF精炼和连铸工序。本发明通过合理的成分设计和冶炼连铸工艺，提高连铸坯热塑性，使其在铸坯矫直区间避开高温脆性区或热塑性足够好使其无表面裂纹产生，铸坯表面质量良好，无需铸坯清理，提高了生产效率。

Description

V-N微合金钢及V-N微合金化的无表面裂纹连铸坯的生产方法 技术领域
本发明属于连铸工艺领域，具体涉及一种V-N微合金化无表面裂纹连铸坯生产方法。
背景技术
微合金钢是近半个世纪以来迅速发展起来的工程结构用钢，其通过添加各种合金元素(Nb、V、Ti等)在钢中起到细晶强化和沉淀强化的效果，提高了钢材的强度与韧性，广泛应用于桥梁、建筑、船舶、汽车、高压容器等各个领域，具有较好的应用前景，是现代钢铁工业中的主要产品。中国的微合金元素的储量丰富，在发展微合金钢方面具有显著的优势。典型的Q550和Q460级低合金高强度钢都具有较好的市场应用。
在工业化生产过程中，由于微合金元素的强化作用，使微合金化得到广泛应用，但是在连铸过程中由于微合金元素的碳氮化物析出，使钢的塑性降低，连铸坯表面裂纹的发生率显著高于普碳钢铸坯，出现横裂、纵裂、形状裂纹等问题，连铸坯质量受到影响，不利于大规模生产，这是微合金化铸坯的典型问题。铌、钒、钛这三种元素是在微合金钢中应用相对广泛的三种元素，其中铌元素对钢的塑性影响最大，对钢的热塑性降低作用最明显。有研究表明Ti元素的添加能够减轻铌、钒微合金钢的脆性，但是不易控制成本。
因此，综合考虑成本和微合金钢铸坯裂纹的问题，开发一种成本较低，无铸坯裂纹的铸坯生产工艺，既保证微合金钢的性能、确保连铸过程的正常进行，又改善铸坯的表面质量是一种典型的工艺难点。
发明内容
针对现有技术中微合金钢在连铸期间铸坯表面容易出现裂纹的问题，本发明提供一种无表面裂纹连铸坯的V-N微合金钢，通过合理的成分设 计和冶炼连铸工艺，生产出断面为(150～350)mm*(1250～2400)mm无表面裂纹连铸坯，提高了连铸坯的表面质量。
为实现上述目的，本发明采用的技术方案如下：
一种V-N微合金钢，其按质量百分比由以下化学成分组成：C：0.09～0.13％，Si：0.1～0.4％，Mn：1.0～3.0％，P：≤0.05％，S：≤0.05％，V：0.1～0.4％，N：0.011～0.2％，余量为Fe和不可避免的杂质元素。
本发明中，利用含钒钢的热塑性低谷点较低的特点，对微合金钢的化学成分进行合理设计，减少微合金钢在连铸期间铸坯表面裂纹的发生。
本发明中，V元素与N元素有极强的亲和力，后期结合TMCP方法可通过细晶强化和析出强化这两种典型的强化机制起到增加组织强韧性的作用。
同时，我国部分地区钒矿的储量丰富，如承德、攀枝花等地，具有不错的成本优势，而且，N的价格相对低廉。因此，采用V-N微合金化，有利于降低连铸坯的生产成本。
本发明还提供了一种V-N微合金化的无表面裂纹连铸坯的生产方法，按照上述V-N微合金钢的化学成分组成生产连铸坯；所述方法依次包括：转炉冶炼、LF精炼和连铸工序。
上述生产方法中，作为一种优选方式，所述连铸坯的断面规格为(150～350)mm*(1250～2400)mm。
上述生产方法中，作为一种优选方式，所述转炉冶炼工序中，铁水比控制在88.0％～91.0％(例如，88.0％、89.0％、90.0％、91.0％)，全程采用顶底复吹模式，并在吹炼过程中先吹氮气后吹氩气，对钢水进行搅拌，促进炉内化学反应的进行。其中，吹氩时间不小于3min(例如，3min、5min、10min、15min)。
上述生产方法中，作为一种优选方式，所述转炉冶炼工序中，所述吹炼过程采用一枪到底形式吹炼，无补吹工艺，以避免补吹过程中造成钢水过氧化，使夹杂物增多。
上述生产方法中，作为一种优选方式，所述转炉冶炼工序中，冶炼终点C含量控制在0.09～0.13％(例如，0.09％、0.10％、0.11％、0.12％、0.13％)，出钢温度为1625～1645℃(例如，1625℃、1630℃、1635℃、1640℃、 1645℃)，所述出钢温度根据钢水凝固温度、连铸过程中过热度和过程温降进行确定，确保连铸能够顺利浇注。
上述生产方法中，作为一种优选方式，出钢后进行LF精炼，无真空脱气精炼；不进行真空脱气的目的在于保证钢水中的N含量。
上述生产方法中，作为一种优选方式，所述连铸工序中，连铸过程采用弱水冷方式，以有效降低铸坯裂纹的发生。
上述生产方法中，作为一种优选方式，所述连铸工序中，连铸过程采用保护浇注，大包在浇注末期报警立即关闭水口，水口关闭后严禁再次打开，中间包采用碱性覆盖剂进行覆盖，保证液面覆盖良好，结晶器采用低碳钢保护渣。
上述生产方法中，作为一种优选方式，所述连铸工序中，连铸过程的比水量为0.7～1.25L/kg(例如，0.7L/kg、0.8L/kg、1.0L/kg、1.2L/kg、1.25L/kg)。
上述生产方法中，作为一种优选方式，所述连铸工序中，严格控制连浇炉次过热度，钢水过热度为10～25℃(例如10℃、15℃、20℃、25℃)。
上述生产方法中，作为一种优选方式，所述连铸工序中，连铸过程中，拉速为1.0～1.3m/min(例如1.0m/min、1.1m/min、1.2m/min、1.3m/min)。
本发明中控制低的过热度，有利于提高拉速，缩短浇注时间，降低能耗；中间包采用碱性覆盖剂，用以对钢包保温并去除钢包中的夹杂物。
上述生产方法中，作为一种优选方式，所述连铸工序中，所述保护渣在溶解过程中分为粉渣层、烧结层和液渣层。
上述生产方法中，作为一种优选方式，所述转炉冶炼工序中，在出钢过程中进行脱氧合金化，同时进行渣洗。
上述生产方法中，作为一种优选方式，所述转炉冶炼工序中，所述出钢过程中，所述脱氧合金化的具体操作方法是：出钢过程选用含硅的物质进行脱氧，加入量为3.5～4.0kg/吨钢(例如，3.5kg/吨钢、3.6kg/吨钢、3.8kg/吨钢、4.0kg/吨钢)；选用硅锰、钒氮合金进行合金化，其中钒氮合金(V含量不低于75％)添加量为1～2kg/吨钢(例如，1kg/吨钢、1.2kg/吨钢、1.4kg/吨钢、1.6kg/吨钢、1.8kg/吨钢、2kg/吨钢)。本发明不采用铝进行脱氧。
上述生产方法中，作为一种优选方式，所述转炉冶炼工序中，所述出钢过程中，所述渣洗选用含CaO的物质(CaO含量不低于90％)进行，添加量为3.5～4.0kg/吨钢(例如，3.5kg/吨钢、3.6kg/吨钢、3.8kg/吨钢、4.0kg/吨钢)，所述含CaO的物质需在钢水出至3/4前加完。
上述生产方法中，作为一种优选方式，所述LF精炼中，LF精炼前期，进行吹氩搅拌的吹氩量为400～1000L/min(例如，500L/min、600L/min、700L/min、800L/min、900L/min)，吹氩搅拌的时间为3～4min(例如，3min、3.2min、3.5min、3.8min、4min)，搅拌的同时注意不得裸露钢水，然后采用含硅物质脱氧，在吹氩搅拌条件下，对成分进行微调。
上述生产方法中，作为一种优选方式，所述LF精炼中，LF精炼中期和末期采用弱氩气搅拌，吹氩流量相同。
上述生产方法中，作为一种优选方式，所述LF精炼中，所述LF精炼的末期，进行吹氩搅拌的吹氩量为100-200L/min(例如，120L/min、140L/min、160L/min、180L/min)，吹氩搅拌的时间≥5min；总精炼时间控制在40～50min(例如，40min、42min、45min、48min、50min)，获得的N含量为100～2000ppm(例如，100ppm、500ppm、1000ppm、1500ppm、2000ppm)，其他成分含量满足所述冶炼工序中要求的钢水成分含量。
本发明中，所述连铸工序中，连铸过程中，根据铸坯规格、钢种成分的不同选择不同的的水量分布。
上述生产方法中，作为一种优选方式，所述连铸工序中，连铸过程的水量具体分布如下：铸坯宽面足辊内外弧水量约占总水量的8.0～10.0％(例如，8.0％、8.5％、9.0％、9.5％、10.0％)，窄面足辊水量占总水量的3.4～4.5％(例如，3.4％、3.8％、4.0％、4.2％、4.5％)，立弯段的二区内外弧水量占总水量的11.0～15.9％(例如，11.0％、12.0％、13.0％、14.0％、15.0％、15.5％、15.9％)，三区内外弧水量占总水量的13.0～15.9％(例如，13.0％、14.0％、15.0％、15.5％、15.9％)，四区内外弧水量占总水量的12.0～13.0％(例如，12.0％、12.2％、12.5％、12.6％、12.8％、13.0％)，弧形1段的五区内外弧水量占总水量的8.5～9.5％(例如，8.0％、8.5％、9.0％、9.5％)，弧形2、3段对应的六区内外弧水量占总水量的12.0～14.0％(例如，12.0％、12.5％、13.0％、13.5％、13.8％、13.0％)，4～5段的七区内外弧水量占总 水量的8.0～11.5％(例如，8.0％、8.5％、9.0％、9.5％、10.0％、11.0％、11.5％、10.0％)，矫直6段、7段与8段的八区内外弧水量占总水量的8.0～11.5％(例如，8.0％、8.5％、9.0％、9.5％、10.0％、11.0％、11.5％、10.0％)，其余水量分配至水平段。
本发明中，在不互相冲突的情况下，上述技术特征可以自由组合形成新的技术方案。
本发明提供的生产方法中未详细描述的步骤和工艺为本领域常规工艺。
与现有技术相比，本发明的有益效果为：
本发明提供的V-N微合金化无表面裂纹连铸坯生产方法，通过合理的V-N微合金化的成分设计，结合合适的冶炼连铸工艺，提高了连铸坯热塑性，使其在铸坯矫直区间避开了高温脆性区或热塑性足够好使其无表面裂纹产生，铸坯表面质量良好，无需铸坯清理，提高了生产效率。
具体实施方式
下面将结合实施例来详细说明本发明的技术方案。各个示例通过本发明的解释的方式提供而非限制本发明。实际上，本领域的技术人员将清楚，在不脱离本发明的范围或精神的情况下，可在本发明中进行修改和变型。例如，示为或描述为一个实施例的一部分的特征可用于另一个实施例，以产生又一个实施例。因此，所期望的是，本发明包含归入所附权利要求及其等同物的范围内的此类修改和变型。
根据本发明的实施例，提供了一种无表面裂纹连铸坯的V-N微合金钢，所述V-N微合金钢按质量百分比由以下化学成分组成：C：0.09～0.13％，Si：0.1～0.4％，Mn：1.0～3.0％，P：≤0.05％，S：≤0.05％，V：0.1～0.4％，N：0.011～0.2％，余量为Fe和少量不可避免的杂质元素。
本发明还提供了一种制备上述化学成分的无表面裂纹连铸坯的微合金钢的生产方法，依次包括如下工序：转炉冶炼、LF精炼和连铸。
本发明连铸坯生产过程中使用的碱性覆盖剂、低碳钢保护渣为生产微合金钢常用的市售产品。
由于在连铸过程中碳氮化物析出，使钢的塑性降低，连铸坯表面裂纹 的发生率显著高于普碳钢铸坯，出现横裂、纵裂、形状裂纹等问题，本发明在冶炼工艺上采取了控制C含量、降S、控制脱氧剂的使用、改变夹杂物形态、提高钢的纯净度，搭配LF精炼、合理的连铸工艺，获得细化晶粒和塑性良好的微合金钢，从而降低微合金钢连铸坯表面裂纹的产生，提高连铸坯的表面质量。
实施例1
本实施例提供的一种V-N微合金化连铸坯及其生产方法，连铸坯化学成分按质量百分比如表1所示。
表1 实施例1中V-N微合金钢连铸坯的化学成分
Figure PCTCN2021118337-appb-000001
其生产方法，依次包括如下工序：转炉冶炼、LF精炼和连铸。
(1)转炉冶炼：
转炉冶炼过程采用120t转炉进行冶炼，冶炼原料为铁水和废钢，铁水比控制在90％，吹炼前期采用氮气吹炼，后期采用氩气吹炼，吹氩时间为4min，吹炼过程采用一枪到底形式吹炼，坚决杜绝补吹工艺，从而防止钢水过氧化，提高了钢水洁净度。
冶炼终点C含量控制在0.10wt％，出钢温度为1632℃；出钢过程进行脱氧合金化和渣洗，脱氧剂选用含硅物质，添加量约为3.6kg/吨钢；合金化原料选用钒氮合金(V含量为77wt％)，添加约为1.6kg/吨钢；渣洗选用含CaO的物质(CaO含量为90wt％)，添加量为3.8kg/吨钢。
(2)LF精炼：
出钢后将钢包直接转入LF精炼站进行吹氩精炼，精炼前期吹氩量选用400L/min进行吹氩搅拌3min后加入含硅物质进行脱氧，添加少量硅锰调整Mn含量；精炼末期吹氩量调整为150L/min搅拌6min；总精炼时间 控制在45min，获得的N含量为120ppm，其他成分含量满足成分控制工艺中要求的钢水成分含量。
(3)连铸：
在保护浇铸环节，大包选用长水口进行保护，并加锥形石棉垫确保连接处的密闭性。
浇铸开始后，首先利用煤气火焰进行钢包下水口与长水口碗部密闭性检验，如火焰被吸入，则表明该处密封性不佳，进行重新套长水口。若密闭性满足要求，则在开浇过程，往长水口碗部连接处通入氩气，对其形成氩封状态，进一步防止长水口碗部与钢包下水口之间连接不严而吸入空气造成钢水增氧增氮。
大包在浇注末期报警立即关闭水口，水口关闭后严禁再次打开。中间包采用碱性覆盖剂进行覆盖，结晶器采用低碳钢保护渣(品川250专用P0050)进行保护。
本实例为浇次第3炉，即连铸开浇后，浇注的第3炉钢，过热度为20℃，实际拉速为1.1m/min。
连铸过程中，比水量为1.2L/kg的水量具体分布为：铸坯宽面足辊内外弧水量约占总水量的8.6％，窄面足辊水量占总水量的3.5％，立弯段的二区内外弧水量占总水量的15.8％，三区内外弧水量占总水量的15.6％，四区内外弧水量占总水量的12.9％，弧形1段的五区内外弧水量占总水量的9.3％，弧形2、3段对应的六区内外弧水量占总水量的12.4％，4～5段的七区内外弧水量占总水量的8.1％，矫直6段、7段、8段的八区内外弧水量占总水量的8.9％，其余水量分配至水平段。
实施效果：本发明采用上述方法浇注的多炉钢得到的连铸坯，断面为200mm*2000mm，表面质量均良好、低倍检测无裂纹，热态观察铸坯表面无裂纹，无需铸坯清理。
实施例2
本实施例生产一种V-N微合金化的无表面裂纹连铸坯，其化学成分按质量百分比如表2所示。
表2 实施例2中V-N微合金钢连铸坯的化学成分
Figure PCTCN2021118337-appb-000002
其生产方法依次包括如下工序：转炉冶炼、LF精炼和连铸。
(1)转炉冶炼：
冶炼过程采用120t转炉进行冶炼，冶炼原料为铁水和废钢，铁水比控制在89％，吹炼前期采用氮气吹炼，后期采用氩气吹炼，吹氩时间为3min，吹炼过程采用一枪到底形式吹炼，坚决杜绝补吹工艺。
冶炼终点C含量控制在0.09wt％，出钢温度为1630℃。
出钢过程进行脱氧合金化和渣洗，脱氧剂选用含硅物质(即碳化硅)，添加量约为3.8kg/吨钢；合金化原料选用钒氮合金(V含量为77wt％)，添加约为1.3kg/吨钢；渣洗选用含CaO的物质(CaO含量为90wt％)，添加量为3.6kg/吨钢。
(2)LF精炼：
出钢后将钢包直接转入LF精炼站进行吹氩精炼，精炼前期吹氩量选用400L/min进行吹氩搅拌4min后加入含硅物质进行脱氧；精炼末期吹氩量调整为150L/min搅拌7min；总精炼时间控制在48min，获得的N含量为100ppm，其他成分含量满足成分控制工艺中要求的钢水成分含量。
(3)连铸：
在保护浇铸环节，大包选用长水口进行保护，并加锥形石棉垫确保连接处的密闭性。浇铸开始后，首先利用煤气火焰进行钢包下水口与长水口碗部密闭性检验，如火焰被吸入，则表明该处密封性不佳，进行重新套长水口。若密闭性满足要求，则在开浇过程，往长水口碗部连接处通入氩气，对其形成氩封状态，进一步防止长水口碗部与钢包下水口之间连接不严而吸入空气造成钢水增氧增氮。大包在浇注末期报警立即关闭水口，水口关闭后严禁再次打开。中间包采用碱性覆盖剂进行覆盖，结晶器采用低碳钢保护渣(品川250专用P0027-3)进行保护。
本实例为开浇后连铸浇注的第4炉钢，过热度为15℃，实际拉速为1.2m/min。
连铸过程中，比水量为1.0L/kg的水量具体分布为：铸坯宽面足辊内外弧水量约占总水量的8.1％，窄面足辊水量占总水量的4.3％，立弯段的二区内外弧水量占总水量的11.4％，三区内外弧水量占总水量的13.1％，四区内外弧水量占总水量的12％，弧形1段的五区内外弧水量占总水量的9.0％，弧形2、3段对应的六区内外弧水量占总水量的13.6％，4～5段的七区内外弧水量占总水量的11.2％，矫直6段、7段与8段的八区内外弧水量占总水量的11.3％，其余水量分配至水平段。
实施效果：采用上述方法浇注的多炉钢得到的连铸坯，规格为250mm*1800mm，表面质量良好、低倍检测无明显裂纹，热态观察铸坯表面无明显裂纹，不需进行铸坯清理。
以上所述仅为本发明的优选实施例，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种V-N微合金钢，其特征在于，所述V-N微合金钢按质量百分比由以下化学成分组成：C：0.09～0.13％，Si：0.1～0.4％，Mn：1.0～3.0％，P：≤0.05％，S：≤0.05％，V：0.1～0.4％，N：0.011～0.2％，余量为Fe和不可避免的杂质元素。
  2. 一种V-N微合金化的无表面裂纹连铸坯的生产方法，其特征在于，根据权利要求1所述的V-N微合金钢的化学成分组成生产连铸坯；所述方法依次包括：转炉冶炼、LF精炼和连铸工序。
  3. 根据权利要求2所述的生产方法，其特征在于，所述连铸坯的断面规格为(150～350)mm*(1250～2400)mm。
  4. 根据权利要求2或3所述的生产方法，其特征在于，所述转炉冶炼工序中，铁水比控制在88.0wt％～91.0wt％，全程采用顶底复吹模式，并在吹炼过程中先吹氮气后吹氩气；其中，吹氩时间不小于3min；
    优选地，所述吹炼过程采用一枪到底形式吹炼，无补吹工艺；
    优选地，冶炼终点C含量控制在0.09～0.13wt％，出钢温度为1625～1645℃。
  5. 根据权利要求4所述的生产方法，其特征在于，出钢后进行LF精炼，无真空脱气精炼工序。
  6. 根据权利要求5所述的生产方法，其特征在于，所述连铸工序中，连铸过程采用弱水冷方式；连铸过程采用保护浇注，大包在浇注末期报警立即关闭水口，水口关闭后严禁再次打开，中间包采用碱性覆盖剂进行覆盖，结晶器采用低碳钢保护渣；
    优选地，连铸过程的比水量为0.7～1.25L/kg；
    优选地，钢水过热度为10～25℃；
    再优选地，连铸过程中，拉速为1.0～1.3m/min。
  7. 根据权利要求4所述的生产方法，其特征在于，所述转炉冶炼工序中，在出钢过程中进行脱氧合金化，同时进行渣洗；
    优选地，所述脱氧合金化的具体操作方法是：出钢过程选用含硅的物质进行脱氧，加入量为3.5～4.0kg/吨钢；选用硅锰、钒氮合金进行合金化，其中钒氮合金添加量为1～2kg/吨钢；
    优选地，所述渣洗选用含CaO的物质进行，添加量为3.5～4.0kg/吨钢，所述含CaO的物质需在钢水出至3/4前加完。
  8. 根据权利要求5所述的生产方法，其特征在于，所述LF精炼工序中，LF精炼前期，进行吹氩搅拌的吹氩量为400～1000L/min，吹氩搅拌的时间为3～4min，采用含硅物质脱氧，在吹氩搅拌条件下，对成分进行微调。
  9. 根据权利要求8所述的生产方法，其特征在于，所述LF精炼工序中，所述LF精炼的末期，进行吹氩搅拌的吹氩量为100-200L/min，吹氩搅拌的时间≥5min；总精炼时间控制在40～50min，获得的N含量为100～2000ppm。
  10. 根据权利要求6所述的生产方法，其特征在于，所述连铸工序中，连铸过程的水量具体分布如下：铸坯宽面足辊内外弧水量约占总水量的8.0～10.0％，窄面足辊水量占总水量的3.4～4.5％，立弯段的二区内外弧水量占总水量的11.0～15.9％，三区内外弧水量占总水量的13.0～15.9％，四区内外弧水量占总水量的12.0～13.0％，弧形1段的五区内外弧水量占总水量的8.5～9.5％，弧形2、3段对应的六区内外弧水量占总水量的12.0～14.0％，4～5段的七区内外弧水量占总水量的8.0～11.5％，矫直6段、7段与8段的八区内外弧水量占总水量的8.0～11.5％，其余水量分配至水平段。
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