WO2021036974A1 - Procédé de régulation d'un défaut d'acier laminé à froid d'un acier à ultra faible teneur en carbone contenant du titane - Google Patents

Procédé de régulation d'un défaut d'acier laminé à froid d'un acier à ultra faible teneur en carbone contenant du titane Download PDF

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Publication number
WO2021036974A1
WO2021036974A1 PCT/CN2020/110757 CN2020110757W WO2021036974A1 WO 2021036974 A1 WO2021036974 A1 WO 2021036974A1 CN 2020110757 W CN2020110757 W CN 2020110757W WO 2021036974 A1 WO2021036974 A1 WO 2021036974A1
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Prior art keywords
steel
titanium
low carbon
containing ultra
added
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PCT/CN2020/110757
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English (en)
Chinese (zh)
Inventor
胡汉涛
马志刚
王俊凯
胡会军
林顺财
薛菲
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宝山钢铁股份有限公司
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Priority to DE112020004170.0T priority Critical patent/DE112020004170T5/de
Publication of WO2021036974A1 publication Critical patent/WO2021036974A1/fr

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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
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • 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
    • 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
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium

Definitions

  • the invention relates to steelmaking technology, in particular to a method for controlling cold-rolled steel defects of titanium-containing ultra-low carbon steel.
  • the immersion nozzle is very likely to be blocked during the continuous casting process, and the mold level fluctuates.
  • the fluctuation range of the crystallizer liquid level increases with the increase of the titanium content in the steel, which reduces the qualification rate of the slab and increases the incidence of subsequent cold-rolled steel defects.
  • the amount of FeO or FeO ⁇ Al 2 O 3 between adjacent Al 2 O 3 particles can inhibit the agglomeration of Al 2 O 3 particles and ultimately improve the quality of the finished product.
  • the theoretical basis of the patent is: FeO or FeO ⁇ Al 2 O exists between adjacent Al 2 O 3 particles in steel. However, the inventor found that the two are liquid in the molten steel, causing the Al 2 O 3 inclusions in the steel to agglomerate into large-sized particles. These large-sized inclusion particles are an important reason for the deterioration of the subsequent finished product quality.
  • Chinese Patent Publication No. CN1218839A relates to the use of Ti for deoxidation, alloying, adding CaSi alloy or CaSi-REM alloy, and controlling the final oxide inclusion composition to Ti 2 O 3 -CaO or REM oxide-Al 2 after the decarburization of molten steel is completed.
  • the composite inclusion of O 3 contains a small amount of SiO 2 or MnO, in which the mass percentage of CaO+REM oxide is in the interval [5, 50], so as to obtain a steel plate with improved surface corrosion rate.
  • the theoretical basis of this application is that the oxide-based inclusions remaining in the steel will not cause nozzle clogging within a specific composition range, and the inclusions can be finely dispersed (proposed by the inventor) to produce a steel sheet with good surface properties.
  • This application emphasizes that the process effect of its invention is due to the control of the Ti content (Ti/Al ratio) added for deoxidation, the amount of Ca or REM added, so that the final inclusion composition is an oxidation containing Ti, Ca/REM and Al Things.
  • the purpose of the present invention is to provide a method for controlling cold-rolled steel defects of titanium-containing ultra-low carbon steel, in order to reduce the hazards of inclusions remaining in the steel, while ensuring the stability of the casting process during smelting, and improving the surface of the cold-rolled product Quality, improve the blockage rate of cold-rolled finished steel, so that it can be used to smelt cold-rolled steel plates with good surface and internal quality.
  • a method for controlling cold-rolled steel defects of titanium-containing ultra-low carbon steel includes: after the RH vacuum decarburization is completed, Ti is added first, the addition amount of Ti is the lower limit of the Ti content range of the finished product specifications, and then Al, the addition amount of Al is the Al content range of the finished product specifications Intermediate value, then molten steel circulation, time ⁇ 3min; add other alloying elements and/or adjust the composition of molten steel according to the finished product specifications, molten steel circulation, time ⁇ 2min; add rare earth metal Ce and/or La to molten steel, add amount Controlled as REM
  • the composition of the rare earth metal is Ce and optionally La.
  • the mass percentage of the rare earth metal is: Ce 60-70%, La 30-40%.
  • the molten steel circulation time is ⁇ 5 min.
  • the molten steel circulation time is ⁇ 3 min.
  • REM/T.O 0.8-2.6.
  • the method of the present invention further includes one or more steps of molten iron desulfurization, dephosphorization, converter decarburization, ladle top slag modification, continuous casting, hot rolling, pickling and cold rolling.
  • the rare earth metals Ce and/or La are added to the molten steel, and the final oxide composition is controlled to Ce 2 O 3 ⁇ Al 2 O 3 and/or La 2 O 3 ⁇ Al 2 O 3 , achieve the purpose of pouring forward, improve the performance of oxide inclusions, and reduce the defects of cold-rolled steel of titanium-containing ultra-low carbon steel.
  • the inventors have discovered through research that in the late refining stage after deoxidation, when rare earth metals (especially CeLa alloys) are added to molten steel, the rare earth metals react with the deoxidation product Al 2 O 3 that does not exclude molten steel as follows:
  • n 11, 1, and 0.
  • the resulting reaction products are: Re 2 O 3 ⁇ 11Al 2 O 3 (also known as ⁇ Al 2 O 3 ), Re 2 O 3 ⁇ Al 2 O 3 and Re 2 O 3 .
  • the product, CeO 2 ⁇ Al 2 O 3 is in the liquid phase at the temperature of molten steel at 1600°C, and the edges are smooth in the solid phase without obvious acute angles, and the hardness is close to that of the steel matrix.
  • the Al 2 O 3 crystals generated in conventional aluminum deoxidized steel belong to the ⁇ crystal type, with a hexagonal cell structure, and are solid at the temperature of molten steel, with sharp edges, and a Mohs hardness of 9, which is much larger than other common materials.
  • the inclusions Re 2 O 3 ⁇ Al 2 O 3 in the steel of the present invention have a greatly reduced probability of mechanical damage to the steel plate substrate, thereby reducing The degree of damage to the steel plate substrate improves the surface and internal quality of the finished product.
  • the present invention believes that the reason why the titanium-containing ultra-low carbon steel is easy to nodule and difficult to cast is: on the one hand, the Ti in the molten steel improves the wettability of the interface between the Al 2 O 3 surface layer and the molten steel, thereby reducing Al The size of 2 O 3 inclusions, and the smaller the alumina inclusion particles, the easier it is to nodule; on the other hand, better wettability makes the heat transfer effect between nodule and refractory material better, resulting in cold steel The formation of the nodule position promotes the aggravation of the nodule.
  • test results carried out by the present invention show that:
  • the crystallizer liquid level fluctuation qualification rate of the conventional process for producing titanium-containing ultra-low carbon steel, and the crystallizer level fluctuation rate of the conventional deoxidation process (Al first and Ti deoxidation process) combined with rare earth treatment are shown in the figure. After adopting the technology of the present invention, the liquid level fluctuation of the crystallizer is at the same level as that of the conventional process.
  • the steel grades applicable to the present invention are ultra-low carbon steel products, that is, the carbon content is less than or equal to 0.005wt%, and the Al content in the molten steel component is greater than or equal to the Ti content to ensure that the final deoxidation of the molten steel before the addition of rare earths is affected by the Al in the molten steel. control.
  • the present invention requires vacuum decarburization treatment so that the carbon in the molten steel is below the required value of the finished product.
  • a certain amount of Ti is added to deoxidize the molten steel, followed by a certain amount of Al.
  • Final deoxidation molten steel circulates for a certain period of time; adjustment and addition of other alloying elements, molten steel circulates for a certain period of time; finally adding rare earth metal Ce/La, molten steel continues to circulate for a certain period of time, and the molten steel vacuum treatment ends.
  • the molten steel circulation time is ⁇ 2min, so that the number of residual inclusions in the steel is as small as possible.
  • the amount of rare earth added exceeds a certain value, the Al 2 O 3 in the molten steel can be completely reduced, and the oxygen in the molten steel is all in the form of Re 2 O 3 , and there are two possible adverse consequences: 1) a single rare earth produced The oxide Re 2 O 3 has a high specificity and is not easy to float; 2) The free Re content in the steel rises sharply, reacts with the refractory material and contaminates the molten steel. In severe cases, it will cause the stopper or nozzle to melt and cause the casting to be abnormal or interrupted.
  • the pure circulation time of the molten steel is required to be ⁇ 3min to ensure that the deoxidized product Al 2 O 3 in the steel fully floats to the top slag of the ladle, so that most of the generated inclusions float to the top slag of the ladle.
  • the addition amount is based on the lower limit of Ti in the finished steel of the specification to be manufactured as the addition standard.
  • the Ti content is in the range of 0.02-0.03%
  • the amount of Ti added after vacuum treatment decarburization is the lower limit of the Ti content range (ie 0.02-0.03%) Value, which is 0.02%.
  • the addition amount is based on the middle value of the Al content range in the finished steel of the specification to be manufactured as the addition standard.
  • the Al content of a certain specification of titanium-containing ultra-low carbon steel is 0.06-0.09%
  • the amount of Al added after vacuum treatment decarburization is the middle value of the Al content range (ie 0.06-0.09%), that is, 0.075 %.
  • the method for controlling cold-rolled steel defects of titanium-containing ultra-low carbon steel provided by the present invention has the following process effects:
  • composition of oxide inclusions in steel changes from pure Al 2 O 3 to Re 2 O 3 ⁇ Al 2 O 3 ;
  • Figure 1 shows typical inclusions in cold-rolled finished steel under conventional processes.
  • Figure 2 shows typical inclusions in the cold-rolled finished steel of the present invention.
  • Figure 3 is a schematic diagram of the coincidence rate of crystallizer liquid level fluctuation.
  • the method for controlling oxide inclusions in titanium-containing ultra-low-carbon steel invented by the present invention can ensure stable and anterograde steelmaking production, change the physical properties of oxide inclusions in the steel, and reduce the blocking rate of cold-rolled steel defects in the final product. Improve the quality of ultra-low carbon steel products.
  • the process path adopted by the present invention is: hot metal desulfurization, dephosphorization-converter decarburization-steel tapping, ladle top slag modification-vacuum decarburization, Ti deoxidation, Al addition and fine adjustment of composition -Add rare earth metal-continuous casting-hot rolling-pickling-cold rolling.
  • the typical furnaces smelted by the present invention are as follows:
  • the cold-rolled steel defect blocking rate of the embodiment of the present invention is 1.55%, among which the steel caused by Al 2 O 3
  • the quality defect is 0, the blocking rate of the cold-rolled steel defects of the adjacent heats is 3.25% and 2.95%, respectively, and the defects caused by Al 2 O 3 are 1.55% and 0.75% respectively.
  • Table 1 is a comparison of some cases of applying the method of the present invention in actual production.
  • the present invention has developed a cold-rolled steel defect control method, which effectively improves the performance of deoxidizing inclusions in the steel, and at the same time can stabilize the pouring of molten steel in order, thereby reducing the cold rolling
  • the incidence of defects in finished steel is suitable for the improvement of the quality of cold-rolled products of ultra-low carbon steel containing titanium, and has promotion and application value in steel plants.

Abstract

L'invention concerne un procédé de régulation d'un défaut d'acier laminé à froid d'un acier à ultra faible teneur en carbone contenant du titane. L'acier à ultra faible teneur en carbone contenant du titane comprend les constituants suivants, exprimés en pourcentage en poids : C ≤ 0,005 %, Si ≤ 0,05 %, de 0,05 à 0,3 % de Mn, de 0,02 à 0,1 % d'Al, de 0,008 à 0,05 % de Ti, P ≤ 0,05 %, S ≤ 0,02 %, N ≤ 0,003 %, de 0,0010 à 40 % de T.O, et le reste étant du Fe et des impuretés inévitables, dans lequel la teneur en Al est supérieure ou égale à la teneur en Ti. Une fois la décarburation sous vide RH terminée, du Ti est ajouté en premier, et la quantité d'addition de Ti est régulée selon la valeur limite inférieure de la valeur de produit fini; de l'Al est ensuite ajouté, la quantité d'addition est régulée selon la médiane de la valeur de produit fini, et le temps de circulation de l'acier liquide est supérieur ou égal à 3 min; d'autres éléments d'alliage sont ajoutés et/ou les constituants d'acier fondu sont ajustés selon la spécification du produit fini, et le temps de circulation de l'acier fondu est supérieur ou égal à 2 min; des métaux des terres rares Ce et La sont ajoutés, pour lesquels la quantité d'addition équivaut à REM/T.O = 0,6 à 3,0 en rapport en masse, l'unité de masse de terres rares REM est le kg, et l'unité de l'oxygène total T.O dans l'acier) est le ppm; et le temps de circulation de l'acier fondu est supérieur ou égal à 2 min, et de l'oxyde de Ce2O3Al2O3 ou du La2O3Al2O3 est produit dans l'acier fondu.
PCT/CN2020/110757 2019-08-30 2020-08-24 Procédé de régulation d'un défaut d'acier laminé à froid d'un acier à ultra faible teneur en carbone contenant du titane WO2021036974A1 (fr)

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DE112020004170.0T DE112020004170T5 (de) 2019-08-30 2020-08-24 Verfahren zur defektkontrolle eines kaltgewalzten titanhaltigen stahls mit ultraniedrigem kohlenstoffgehalt

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CN201910818378.5A CN112442631B (zh) 2019-08-30 2019-08-30 一种含钛超低碳钢冷轧钢质缺陷的控制方法
CN201910818378.5 2019-08-30

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CN115418430A (zh) * 2022-07-17 2022-12-02 新疆八一钢铁股份有限公司 一种双联冶炼化钢包冷钢的操作方法
CN115478208A (zh) * 2021-05-31 2022-12-16 宝山钢铁股份有限公司 一种基于csp产线的薄规格高成形性冲压钢及其制备方法

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