WO2012041054A1 - Production method of grain-oriented silicon steel with high magnetic flux density - Google Patents

Production method of grain-oriented silicon steel with high magnetic flux density Download PDF

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WO2012041054A1
WO2012041054A1 PCT/CN2011/072768 CN2011072768W WO2012041054A1 WO 2012041054 A1 WO2012041054 A1 WO 2012041054A1 CN 2011072768 W CN2011072768 W CN 2011072768W WO 2012041054 A1 WO2012041054 A1 WO 2012041054A1
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temperature
annealing
oriented silicon
silicon steel
steel
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PCT/CN2011/072768
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French (fr)
Chinese (zh)
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徐琪
沈侃毅
李国保
靳伟忠
金冰忠
宿德军
张仁彪
刘海
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宝山钢铁股份有限公司
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Priority to RU2013114861/02A priority Critical patent/RU2552562C2/en
Priority to EP11827950.4A priority patent/EP2623621B1/en
Priority to MX2013003367A priority patent/MX350000B/en
Priority to KR1020137008095A priority patent/KR101451824B1/en
Priority to JP2013530534A priority patent/JP5864587B2/en
Priority to US13/823,424 priority patent/US20130233450A1/en
Publication of WO2012041054A1 publication Critical patent/WO2012041054A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1222—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1233—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C21D8/1255—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest with diffusion of elements, e.g. decarburising, nitriding
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C21D8/1261—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest following hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C21D8/1272—Final recrystallisation annealing
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    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283—Application of a separating or insulating coating
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    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets

Definitions

  • the present invention relates to a method of producing oriented silicon steel, and more particularly to a method of producing a high magnetic flux density oriented silicon steel product. Background technique
  • the production method of the traditional high magnetic flux density oriented silicon steel is as follows: steelmaking by converter (or electric furnace), secondary refining and alloying, continuous casting into slab, the basic chemical composition is: s so / C 0.06 ⁇ 0.10%, Mn 0.03 to 0.1%, S 0.012 to 0.050%, Als 0.02 to 0.05%, N 0.003 to 0.012%, and some component systems further contain one or more of elements such as Cu, Mo, Sb, B, and Bi, and the rest. It is an element of iron and inevitable impurities.
  • the slab is heated to a temperature above 1350 °C in a special high-temperature heating furnace, and is kept for more than 45 minutes, so that the favorable inclusions MnS or A1N are fully dissolved, and then rolled, and the finishing temperature reaches 950 ° C or higher.
  • pickling is performed to remove the surface iron oxide scale; cold rolling is performed to roll the sample to the finished product thickness.
  • the [C] in the steel sheet is removed to the extent that it does not affect the magnetic properties of the finished product (generally should be less than 30 ppm); during the high temperature annealing, the steel sheet occurs twice. Recrystallization, formation and purification of magnesium silicate underlayer (removing elements such as S and N in steel which are harmful to magnetic properties), etc., obtaining high magnetic induction oriented silicon steel with high degree of orientation and low iron loss; Insulating coatings and stretch annealing provide oriented silicon steel products in commercial applications.
  • the heating temperature is up to 1400 ° C, which is the limit level of the conventional furnace.
  • the heating temperature is high, the burning is large, the heating furnace needs frequent repair, and the utilization rate is low.
  • high energy consumption and large edge cracking of the hot rolled coil make the cold rolling process difficult to produce, the finished product rate is low, the magnetic properties of the finished product are not ideal, and the cost is high.
  • the slab heating temperature is between 1250 and 1320 °. C, using A1N and Cu inhibitors; the other is the slab heating temperature of 1100 ⁇ 1250 ° C, mainly using decarburization after nitriding formation inhibitors to obtain inhibition ability.
  • the low temperature slab heating technology has developed rapidly.
  • US Patent No. 5,049,205 and Japanese Patent Laid-Open No. 5-112827 use slab heating below 1200 °C for final cold rolling.
  • Chinese patent CN 200510110899 describes a new process for slab heating below 1200 ° C, and decarburization annealing of the cold rolled sheet that has been rolled to the finished thickness, but requires strict control of the dew point during the nitriding process. At the same time, new problems of difficulty in decarbonization will be introduced.
  • Korean patent KR 2002074312 proposes a method of decarburization and nitriding with slab heating after slab heating below 1200 °C. Although this can solve the problem of post-decarburization difficulty or post-nitriding difficulty, it is still unavoidable. Uneven nitriding causes problems such as uneven magnetic properties and high cost of the product.
  • Nb element is added to steelmaking.
  • 0.02 to 0.20% of Nb is added to the steelmaking component for the purpose of recrystallizing the hot rolled sheet by forming precipitates such as tantalum carbide and tantalum nitride.
  • the microstructure is refined to improve the grain distribution and aggregate structure of the decarburization annealed sheet, and acts as an auxiliary inhibitor in the high temperature annealing process to suppress the growth of normal grains, thereby improving the magnetic properties of the oriented silicon steel.
  • the problem with this patent is that in order to obtain precipitates such as tantalum nitride before hot rolling, high temperature slab heating technology must be employed, which inevitably leads to problems such as large burning loss, high energy consumption, low yield, and high cost.
  • Nitride added to the MgO release agent as proposed in Japanese Patent No. 51106622 and U.S. Patent No. 417,1994, the addition of nitrates of Al, Fe, Mg and Zn to the MgO release agent, which are decomposed during high temperature annealing and infiltrated into the plate. nitrogen.
  • the products of decomposition of these nitrides are nitrogen oxides, oxygen, and the like, there is a danger of explosion in actual production.
  • Japanese patents JP61096080 and JP62004881 respectively propose to add Mn and Si Nitride to meet nitriding during high temperature annealing.
  • this method has a problem in that since the above-mentioned nitride has high thermal stability, its decomposition efficiency is low, and it is necessary to lengthen the annealing time or increase the amount of nitride to satisfy the nitriding requirement.
  • the control of the temperature rise rate of the high-temperature annealing can be achieved by lowering the temperature increase rate in the high-temperature annealing process to obtain the high-flux density oriented silicon steel.
  • simply lowering the rate of temperature rise will result in a significant drop in production efficiency.
  • the object of the present invention is to provide a method for producing a high magnetic flux density oriented silicon steel product, which solves the problem of nitriding difficulty in producing high magnetic induction oriented silicon steel by low temperature slab heating technology, and at the same time adopts low temperature heating technology to effectively ensure a series of equipment such as a steelmaking furnace. It is safe, stable and has a long service life. Since the steel sheet is nitrided during the high-temperature annealing process, it can ensure the secondary recrystallization is perfect, and finally obtain a high magnetic flux density oriented silicon steel product with excellent magnetic properties.
  • the steel sheet is more susceptible to nitrogen absorption during the high temperature annealing process because the nitrogen content determines whether the magnetic properties of the final finished sheet are up to standard.
  • a nitrogen-containing compound to the MgO release agent, it is applied to the surface of the steel sheet, and is thermally decomposed during the high-temperature annealing process, thereby achieving a uniform purpose of nitriding into the steel sheet.
  • the nitrogen content before the second temperature rise, and the secondary temperature rise temperature different heating rates are adjusted to ensure the secondary recrystallization is perfect, and finally a high magnetic flux density excellent in magnetic properties is obtained.
  • Oriented silicon steel products according to the Nb content in the steel, the nitrogen content before the second temperature rise, and the secondary temperature rise temperature, different heating rates are adjusted to ensure the secondary recrystallization is perfect, and finally a high magnetic flux density excellent in magnetic properties is obtained.
  • a method for producing a high magnetic flux density oriented silicon steel product of the present invention includes the following steps:
  • the weight percentage of the oriented silicon steel composition is: C 0.035-0.065%, Si 2.9-4.0%, Mn 0.05-0.20%, S 0.005-0.012%, Als 0.015-0.035%, N 0.004-0.009%,
  • the slab is heated in the heating furnace to 1090 ⁇ 1200 °C, rolling below 1180 °C, finishing at 860 °C or more, laminar cooling after rolling, and coiling below 650 °C; Normalization process: normalizing temperature is 1050 ⁇ 1180. C, time l ⁇ 20sec, normalization temperature 850-950 V, time 30 ⁇ 200sec; then cooling, cooling rate 10 ⁇ 60 °C/sec;
  • the steel plate After normalization, the steel plate is rolled to the thickness of the finished plate, and the cold rolling reduction rate is ⁇ 75% ;
  • the surface of the steel plate is coated with MgO as the main component, 0.1 ⁇ 10% NH 4 C1 and 0.5 ⁇ 30% P 3 N 5 , and the balance is MgO, in weight percentage;
  • An insulating coating is applied on the surface of the high temperature annealed sheet, and a high magnetic flux density oriented silicon steel excellent in magnetic properties is obtained by hot drawing flat annealing.
  • the present invention adds an appropriate amount of Nb to the steelmaking composition. The purpose is to have two points: On the one hand, when Nb is contained in the oriented silicon steel, it is easier to complete the nitriding at high temperature annealing. This is because the electron filling of the sub-dilayer sub-layer of the Nb atom is less saturated with respect to Fe and Mn, so that nitride formation is easier and the nitride is more stable.
  • this part of the nitrogen atoms which are infiltrated during high-temperature annealing can form the main inhibitor A1N necessary for high magnetic flux density oriented silicon steel with Als, and can simultaneously obtain precipitates in the form of Nb 2 N and NbN.
  • This part of Nb nitride can act as an auxiliary suppression (J, which enhances the effect of suppressing the growth of normal grains, and finally improves the magnetic properties of the oriented silicon steel finished board.
  • an appropriate amount of NH 4 C1 and P 3 N 5 is added to the MgO coating liquid.
  • the purpose is to use nitriding in the high temperature annealing process to complete nitriding into the plate, thereby replacing the nitriding by ammonia decomposition during the decarburization annealing process, and the greatest benefit is to ensure more uniform nitriding in the plate.
  • the two inorganic nitrides, NH 4 C1 and P 3 N 5 are selected as the nitriding raw material for pyrolysis. Because the decomposition temperature of NH 4 C1 is 330 ⁇ 340 °C, and the decomposition temperature of P 3 N 5 is about 760 °C.
  • Different nitride decomposition temperature regions ensure that the active nitrogen atoms are uniformly released over a long period of time during high-temperature annealing, thereby completing nitriding into the steel sheet and maintaining the nitrogen content [N] at 200-250 ppm. Within the standard range.
  • the present invention requires control of the secondary heating rate during high temperature annealing.
  • the purpose is to ensure excellent magnetic properties of the final product by setting an appropriate secondary heating rate. This is because the temperature range of secondary recrystallization of oriented silicon steel is covered during the secondary heating of high temperature annealing. Therefore, a suitable heating rate can make the Gaussian grain orientation which grows in the secondary recrystallization process better, the off angle is ⁇ 3 °, and the magnetic properties are better.
  • the relatively slow temperature rise ensures the secondary recrystallization is perfect, and the finished product has good magnetic properties. This is because secondary recrystallization occurs during the secondary temperature rise of the high temperature annealing, and this is also the process in which the A1N inhibitor is coarsened and decomposed, and the inhibition force disappears. If it is within this temperature range, if the heating rate is too fast, the secondary recrystallization will not be completed, but the inhibitor will be decomposed and failed, the secondary recrystallization of the finished product is imperfect, and the magnetic deterioration is serious.
  • the chemical compositions described in Table 1 were smelted and cast.
  • the slabs of different compositions were placed in a heating furnace at 1155 ° C for 1.5 hours and then hot rolled to a hot rolled sheet having a thickness of 2.3 mm.
  • the rolling and finishing temperatures were 1062 ° C and 937 ° C, respectively.
  • a two-stage normalization is applied to the hot rolled sheet: (1120 °C xl 5sec) + (870 °C xl 50sec), followed by cooling at -15 °C/sec. After pickling, it is cold rolled to a thickness of 0.30 mm.
  • decarburization annealing was carried out at a heating rate of 25 ° C/sec, a decarburization temperature of 820 ° C, and an average temperature of 140 s.
  • a separator containing MgO as a main component and containing 4.5% NH 4 C1 and 15% P 3 N 5 was applied.
  • the temperature is first raised to 800 ° C to obtain a nitrogen content b before the second temperature rise; the temperature is further raised to 1200 ° C, and then the temperature is maintained for 20 hours for purification annealing. After unwinding, it is coated with an insulating coating and stretched and flattened. Among them, the nitrogen content b before the second temperature rise and the magnetic properties of the finished product are shown in Table 1.
  • the composition and weight percentage of the oriented silicon steel slab are C: 0.050%, Si: 3.25%, Mn: 0.15%, S: 0.009%, Als: 0.032%, N: 0.005%, Sn: 0.02%, Nb: 0.5%
  • the rest are Fe and inevitable impurities.
  • the slab was placed in a heating furnace at 1155 ° C for 1.5 hours and then hot rolled to a hot rolled sheet having a thickness of 2.3 mm.
  • the rolling and finishing temperatures were 1080 ° C and 910 ° C, respectively.
  • Two-stage normalization is applied to the hot rolled sheet: (1110 °C x l0sec) + (910 °C x l20sec), followed by cooling at -35 °C / sec.
  • decarburization annealing was carried out at a heating rate of 25 ° C / sec, a decarburization temperature of 840 ° C, and an average temperature of 130 s.
  • the coating is mainly composed of MgO, and different contents of NH 4 C1 and P 3 N 5 are added .
  • annealing at a high temperature the temperature is first raised to 800 ° C to obtain a nitrogen content b before the second temperature rise; the temperature is further raised to 1200 ° C, and then the temperature is kept for 20 hours for purification annealing. After unwinding, it is coated with an insulating coating and stretched and flattened. Among them, the nitrogen content b before the second temperature rise and the magnetic properties of the finished product are shown in Table 2.
  • composition and weight percentage of the oriented silicon steel slab are C: 0.050%, Si: 3.25%, Mn: 0.15%, S: 0.009%, Als: 0.032%, N: 0.005%, Sn: 0.02%, Nb content (a ) : 0.2-0.8%, the rest is Fe and unavoidable impurities.
  • the slab was placed in a heating furnace at 1115 ° C for 2.5 hours and then hot rolled to a hot rolled sheet having a thickness of 2.3 mm, and the rolling and finishing temperatures were 1050 and 865 ° C, respectively.
  • the two-stage normalization was applied to the hot rolled sheet: (1120 ° C x 15 sec) + (900 ° C x l20 sec), followed by cooling at -25 ° C / sec. After pickling, it is cold rolled to a thickness of 0.30 mm. Then, decarburization annealing was carried out at a heating rate of 25 ° C / sec, a decarburization temperature of 850 ° C, and an average temperature of 115 s.
  • the coating was mainly composed of MgO, and 7.5% NH 4 C1 and 12.5% P 3 N 5 were added .
  • the temperature is first raised to 700 ° C to 900 ° C, as the initial temperature (c) of the second temperature rise, and the nitrogen content before the second temperature rise (b) is obtained. Then heat up to 1200 with a certain secondary heating rate (V) . C, and then heat-treating for 20 hours for purification annealing. After unwinding, it is coated with an insulating coating and stretched and flattened.
  • the Nb content (a), the pre-heating pre-nitrogen content (b), and the secondary heating initiation temperature (c) are the same;
  • the actual secondary heating rate in the embodiment is 9 °C/hr 17 °C/hr, and the difference between the theoretical value and the actual value is positive, the magnetic properties of the finished product are better;
  • the comparative example is reversed, so the magnetic properties of the finished board are poor.
  • the high magnetic induction oriented silicon steel produced by the low temperature slab heating technology has the advantages of long life of the heating furnace, low energy consumption and low cost.
  • the present invention is a novel high magnetic flux density oriented silicon steel production method based on a low temperature slab heating process, which effectively solves the above problems. It is characterized in that by adding a suitable Nb content in the steel making, the steel sheet is more likely to absorb nitrogen during the high-temperature annealing process; by adding a nitrogen-containing compound to the MgO separating agent, it is thermally decomposed during the high-temperature annealing process to reach the steel sheet. The purpose of uniform nitriding.
  • the temperature rise rate is controlled according to the Nb content, the nitrogen content, and the secondary temperature rise temperature in the steel, thereby ensuring the secondary recrystallization is completed, and finally obtaining a high magnetic flux density oriented silicon steel product excellent in magnetic properties.

Abstract

A production method of grain-oriented silicon steel with high magnetic flux density includes the following steps: 1) smelting and casting, wherein the components of molten steel are: C 0.035-0.065wt%, Si 2.9-4.0wt%, Mn 0.05-0.20wt%, S 0.005-0.012wt%, Als 0.015-0.035wt%, N 0.004-0.009wt%, Sn 0.005-0.090wt%, Nb 0.200-0.800wt%, and balance Fe; 2) hot rolling; 3) normalization; 4) cold rolling; 5) decarburization annealing; 6) coating MgO; 7) high-temperature annealing, wherein the temperature is raised to 700-900 ℃ firstly, and then to 1200 ℃ at a velocity V2nd heating of 9-17 ℃ / hr, and holding for 20 hours; 8) applying insulation coating.

Description

一种高磁通密度取向硅钢产品的生产方法 发明领域  Method for producing high magnetic flux density oriented silicon steel product
本发明涉及取向硅钢的制造方法，特别涉及一种高磁通密度取向硅钢 产品的生产方法。 背景技术  The present invention relates to a method of producing oriented silicon steel, and more particularly to a method of producing a high magnetic flux density oriented silicon steel product. Background technique
传统高磁通密度取向硅钢的生产方法如下： 用转炉 （或电炉） 炼钢， 进行二次精炼及合金化， 连铸成板坯， 其基本化学成分为： s so/ C 0.06〜0.10%、 Mn 0.03〜0.1%、 S 0.012〜0.050%、 Als 0.02〜0.05%、 N 0.003〜0.012%， 有的成分体系还含有 Cu、 Mo、 Sb、 B、 Bi等元素中的一 种或多种， 其余为铁及不可避免的杂质元素。板坯在专用高温加热炉内加 热到 1350°C以上的温度， 并进行 45min以上的保温， 使有利夹杂物 MnS 或 A1N充分固溶， 然后进行轧制， 终轧温度达到 950°C以上， 进行快速喷 水冷却到 500°C以下， 然后卷取。 以便在随后的常化过程中在硅钢基体内 析出细小、 弥散的第二相质点， 即抑制剂； 热轧板常化后， 进行酸洗， 除 去表面氧化铁皮；冷轧将样品轧到成品厚度，进行脱碳退火和涂布以 MgO 为主要成分的退火隔离剂，把钢板中的 [C]脱到不影响成品磁性的程度（一 般应在 30ppm 以下） ； 高温退火过程中， 钢板发生二次再结晶、 硅酸镁 底层形成及净化 （除去钢中的 S、 N等对磁性有害的元素） 等物理化学变 化， 获得取向度高、 铁损低的高磁感取向硅钢； 最后， 经过涂布绝缘涂层 和拉伸退火， 得到商业应用形态的取向硅钢产品。  The production method of the traditional high magnetic flux density oriented silicon steel is as follows: steelmaking by converter (or electric furnace), secondary refining and alloying, continuous casting into slab, the basic chemical composition is: s so / C 0.06~0.10%, Mn 0.03 to 0.1%, S 0.012 to 0.050%, Als 0.02 to 0.05%, N 0.003 to 0.012%, and some component systems further contain one or more of elements such as Cu, Mo, Sb, B, and Bi, and the rest. It is an element of iron and inevitable impurities. The slab is heated to a temperature above 1350 °C in a special high-temperature heating furnace, and is kept for more than 45 minutes, so that the favorable inclusions MnS or A1N are fully dissolved, and then rolled, and the finishing temperature reaches 950 ° C or higher. Quickly spray water to below 500 ° C, then take up. In order to precipitate a small, dispersed second phase particle, ie, an inhibitor, in the silicon steel matrix during the subsequent normalization process; after the hot-rolled plate is normalized, pickling is performed to remove the surface iron oxide scale; cold rolling is performed to roll the sample to the finished product thickness. Decarburization annealing and coating of an annealing separator with MgO as the main component, the [C] in the steel sheet is removed to the extent that it does not affect the magnetic properties of the finished product (generally should be less than 30 ppm); during the high temperature annealing, the steel sheet occurs twice. Recrystallization, formation and purification of magnesium silicate underlayer (removing elements such as S and N in steel which are harmful to magnetic properties), etc., obtaining high magnetic induction oriented silicon steel with high degree of orientation and low iron loss; Insulating coatings and stretch annealing provide oriented silicon steel products in commercial applications.
上述生产方法的不足在于： 为了使抑制剂充分固溶， 加热温度最高需 达到 1400°C， 这是传统加热炉的极限水平。 此外， 由于加热温度高， 烧 损大、 加热炉需频繁修补， 利用率低。 同时， 能耗高， 热轧卷的边裂大， 致使冷轧工序生产困难， 成材率低， 成品磁性能 不理想， 成本也高。  The disadvantages of the above production methods are: In order to fully dissolve the inhibitor, the heating temperature is up to 1400 ° C, which is the limit level of the conventional furnace. In addition, since the heating temperature is high, the burning is large, the heating furnace needs frequent repair, and the utilization rate is low. At the same time, high energy consumption and large edge cracking of the hot rolled coil make the cold rolling process difficult to produce, the finished product rate is low, the magnetic properties of the finished product are not ideal, and the cost is high.
正是鉴于上述这些问题，国内外的研发人员开展了大量降低取向硅钢 加热温度的研究， 其主要改进的趋势按照加热温度范围来区分有两种， 一 种是板坯加热温度在 1250~1320°C， 采用 A1N和 Cu的抑制剂； 另一种是 板坯加热温度在 1100~1250°C， 主要采用脱碳后渗氮形成抑制剂的方法来 获得抑制能力。 现阶段低温板坯加热技术发展较快， 例如美国专利 US 5049205和日 本专利特开平 5-112827采用在 1200 °C以下进行板坯加热， 最终冷轧采用In view of the above problems, researchers at home and abroad have carried out a large number of studies to reduce the heating temperature of oriented silicon steel. The main improvement trend is divided into two according to the heating temperature range. One is that the slab heating temperature is between 1250 and 1320 °. C, using A1N and Cu inhibitors; the other is the slab heating temperature of 1100 ~ 1250 ° C, mainly using decarburization after nitriding formation inhibitors to obtain inhibition ability. At this stage, the low temperature slab heating technology has developed rapidly. For example, US Patent No. 5,049,205 and Japanese Patent Laid-Open No. 5-112827 use slab heating below 1200 °C for final cold rolling.
80%的大冷轧压下率， 并在脱碳退火后采用氨气进行连续渗氮处理， 获得 取向度较高的二次再结晶晶粒。但这种方法由于采用基板脱碳后渗氮形成 抑制剂的方法来获得抑制能力， 在实际控制中很难克服带钢表面氧化严 重、渗氮困难和不均匀等难题，因此造成获得型抑制剂在钢板内形成困难、 分布不均匀， 从而影响抑制能力和二次再结晶的均匀性， 引起最终产品磁 性能不均匀。 80% of the large cold rolling reduction rate, and after continuous denitrification treatment with ammonia gas after decarburization annealing, secondary recrystallized grains with higher orientation are obtained. However, this method can obtain the inhibition ability by using the method of nitriding formation inhibitor after decarburization of the substrate, and it is difficult to overcome the problems of serious oxidation of the surface of the steel strip, difficulty in nitriding and unevenness in the actual control, thereby causing the obtained inhibitor. Difficulties are formed in the steel sheet, and the distribution is uneven, thereby affecting the suppression ability and the uniformity of the secondary recrystallization, resulting in uneven magnetic properties of the final product.
中国专利 CN 200510110899描述了在 1200°C以下进行板坯加热， 并 对已经轧制到成品厚度的冷轧板进行先渗氮后脱碳退火的新工艺，但是在 渗氮过程中需要严格控制露点， 同时又会引入了脱碳困难的新问题。  Chinese patent CN 200510110899 describes a new process for slab heating below 1200 ° C, and decarburization annealing of the cold rolled sheet that has been rolled to the finished thickness, but requires strict control of the dew point during the nitriding process. At the same time, new problems of difficulty in decarbonization will be introduced.
近期韩国专利 KR 2002074312提出在 1200°C以下进行板坯加热后， 采用脱碳和渗氮同歩进行的方法，这虽然可以解决后脱碳困难或后渗氮困 难的问题，但仍无法避免因渗氮不均匀造成产品磁性能不均匀和成本昂贵 等问题。  Recently, Korean patent KR 2002074312 proposes a method of decarburization and nitriding with slab heating after slab heating below 1200 °C. Although this can solve the problem of post-decarburization difficulty or post-nitriding difficulty, it is still unavoidable. Uneven nitriding causes problems such as uneven magnetic properties and high cost of the product.
炼钢中添加 Nb元素， 如日本专利 JP6025747和 JP6073454中提出， 在炼钢成分中加入 0.02~0.20%的 Nb， 其目的是通过形成碳化铌和氮化铌 等析出物， 使热轧板再结晶组织细化， 改善脱碳退火板的晶粒分布和集合 组织，在高温退火过程中作为辅助抑制剂，起到抑制正常晶粒长大的作用， 从而提高取向硅钢磁性。然而， 该专利的问题是为了在热轧前获得氮化铌 等析出物， 必须采用高温板坯加热技术， 这势必会带来烧损大、 能耗高、 成材率低以及成本高等问题。  Nb element is added to steelmaking. As proposed in Japanese Patent No. JP6025747 and JP6073454, 0.02 to 0.20% of Nb is added to the steelmaking component for the purpose of recrystallizing the hot rolled sheet by forming precipitates such as tantalum carbide and tantalum nitride. The microstructure is refined to improve the grain distribution and aggregate structure of the decarburization annealed sheet, and acts as an auxiliary inhibitor in the high temperature annealing process to suppress the growth of normal grains, thereby improving the magnetic properties of the oriented silicon steel. However, the problem with this patent is that in order to obtain precipitates such as tantalum nitride before hot rolling, high temperature slab heating technology must be employed, which inevitably leads to problems such as large burning loss, high energy consumption, low yield, and high cost.
MgO 隔离剂中添加的氮化物， 如日本专利 JP51106622 和美国专利 US4171994中提出， 在 MgO隔离剂中添加 Al、 Fe、 Mg和 Zn的硝酸盐， 使其在高温退火过程中分解后向板内渗入氮。然而， 由于这些氮化物分解 的产物为氮氧化合物和氧气等， 因此在实际生产中存在***的危险。  Nitride added to the MgO release agent, as proposed in Japanese Patent No. 51106622 and U.S. Patent No. 417,1994, the addition of nitrates of Al, Fe, Mg and Zn to the MgO release agent, which are decomposed during high temperature annealing and infiltrated into the plate. nitrogen. However, since the products of decomposition of these nitrides are nitrogen oxides, oxygen, and the like, there is a danger of explosion in actual production.
日本专利 JP52039520和美国专利 US4010050中提出， 在 MgO隔离 剂中添加磺胺酸， 作为高温分解时渗氮原料。 但是， 作为有机物， 磺胺酸 分解温度较低（约 205 °C ) ， 实际生产中分解出来的 [N]在低温下很难渗入 到钢板中。  It is proposed in Japanese Patent No. JP52039520 and U.S. Patent No. 4,010,050 to add a sulfamic acid as a nitriding raw material for pyrolysis. However, as an organic substance, the decomposition temperature of sulfamic acid is low (about 205 ° C), and [N] which is decomposed in actual production is difficult to penetrate into the steel sheet at a low temperature.
日本专利 JP61096080和 JP62004881中分别提出，通过添加 Mn和 Si 的氮化物来满足高温退火时的渗氮。 但是， 该方法的问题在于， 由于上述 氮化物热稳定性高， 因此其分解的效率低， 需要延长退火时间或增加氮化 物量来满足渗氮要求。 Japanese patents JP61096080 and JP62004881 respectively propose to add Mn and Si Nitride to meet nitriding during high temperature annealing. However, this method has a problem in that since the above-mentioned nitride has high thermal stability, its decomposition efficiency is low, and it is necessary to lengthen the annealing time or increase the amount of nitride to satisfy the nitriding requirement.
高温退火升温速度的控制， 如日本专利 JP54040227和 JP200119751 中提出，在高温退火过程中可以通过降低升温速度来获得高磁通密度的取 向硅钢。 但是， 单纯的降低升温速度会造成生产效率的大幅下降。 发明概述  The control of the temperature rise rate of the high-temperature annealing, as proposed in Japanese Patent No. JP54040227 and JP200119751, can be achieved by lowering the temperature increase rate in the high-temperature annealing process to obtain the high-flux density oriented silicon steel. However, simply lowering the rate of temperature rise will result in a significant drop in production efficiency. Summary of invention
本发明的目的在于提供一种高磁通密度取向硅钢产品的生产方法，解 决低温板坯加热技术生产高磁感取向硅钢时渗氮难点，同时采用低温加热 技术有效确保炼钢炉等一系列设备安全、 稳定、 使用寿命长； 由于钢板在 高温退火过程中完成渗氮； 所以能确保二次再结晶完善， 最终获得磁性能 优异的高磁通密度取向硅钢产品。  The object of the present invention is to provide a method for producing a high magnetic flux density oriented silicon steel product, which solves the problem of nitriding difficulty in producing high magnetic induction oriented silicon steel by low temperature slab heating technology, and at the same time adopts low temperature heating technology to effectively ensure a series of equipment such as a steelmaking furnace. It is safe, stable and has a long service life. Since the steel sheet is nitrided during the high-temperature annealing process, it can ensure the secondary recrystallization is perfect, and finally obtain a high magnetic flux density oriented silicon steel product with excellent magnetic properties.
本发明的技术方案是，  The technical solution of the present invention is
通过在炼钢中添加合适的 Nb含量， 使钢板在高温退火过程中更易吸 氮， 因为氮含量决定着最终成品板磁性能是否达标。 通过在 MgO隔离剂 中添加含氮化合物，使之涂覆于钢板表面，并在高温退火过程中受热分解， 起到向钢板内渗氮均匀目的。 在高温退火过程中， 根据钢中 Nb含量、 二 次升温前氮含量和二次升温起始温度， 调整不同的升温速度， 从而确保二 次再结晶完善， 最终获得磁性能优异的高磁通密度取向硅钢产品。  By adding a suitable Nb content to the steelmaking, the steel sheet is more susceptible to nitrogen absorption during the high temperature annealing process because the nitrogen content determines whether the magnetic properties of the final finished sheet are up to standard. By adding a nitrogen-containing compound to the MgO release agent, it is applied to the surface of the steel sheet, and is thermally decomposed during the high-temperature annealing process, thereby achieving a uniform purpose of nitriding into the steel sheet. In the high-temperature annealing process, according to the Nb content in the steel, the nitrogen content before the second temperature rise, and the secondary temperature rise temperature, different heating rates are adjusted to ensure the secondary recrystallization is perfect, and finally a high magnetic flux density excellent in magnetic properties is obtained. Oriented silicon steel products.
具体地， 本发明的一种高磁通密度取向硅钢产品的生产方法， 包括如 下歩骤：  Specifically, a method for producing a high magnetic flux density oriented silicon steel product of the present invention includes the following steps:
1) 冶炼及浇铸  1) Smelting and casting
取向硅钢成分重量百分比为： C 0.035-0.065%, Si 2.9-4.0%, Mn 0.05-0.20%, S 0.005-0.012%, Als 0.015-0.035%, N 0.004-0.009%, The weight percentage of the oriented silicon steel composition is: C 0.035-0.065%, Si 2.9-4.0%, Mn 0.05-0.20%, S 0.005-0.012%, Als 0.015-0.035%, N 0.004-0.009%,
Sn 0.005-0.090%, Nb 0.200-0.800%, 其余为 Fe及不可避免的夹杂 物； 采用转炉或电炉炼钢， 钢水经二次精炼和连铸后， 获得板坯；Sn 0.005-0.090%, Nb 0.200-0.800%, the rest is Fe and unavoidable inclusions; steel is produced by converter or electric furnace, and molten steel is obtained by secondary refining and continuous casting to obtain slab;
2) 热轧 2) Hot rolling
板坯在加热炉内加热到 1090~1200 °C， 1180 °C以下开轧， 860 °C以 上终轧， 轧后层流冷却， 650 °C以下卷取； 常化工艺：常化温度 1050~1180。C，时间 l~20sec ,常化温度 850-950 V， 时间 30~200sec; 随后进行冷却， 冷却速度 10~60 °C/sec; The slab is heated in the heating furnace to 1090~1200 °C, rolling below 1180 °C, finishing at 860 °C or more, laminar cooling after rolling, and coiling below 650 °C; Normalization process: normalizing temperature is 1050~1180. C, time l~20sec, normalization temperature 850-950 V, time 30~200sec; then cooling, cooling rate 10~60 °C/sec;
4) 冷轧  4) Cold rolling
常化后， 将钢板轧制到成品板厚度， 冷轧压下率≥75%; After normalization, the steel plate is rolled to the thickness of the finished plate, and the cold rolling reduction rate is ≥75% ;
5) 脱碳退火  5) Decarburization annealing
升温速度 15~35 °C/sec， 脱碳温度 800 860 °C， 保温 90~160sec; 由于 在高温退火时才进行渗氮， 所以在脱碳退火时只要达到脱碳要求即可， 简 化了脱碳工艺。  Heating rate 15~35 °C/sec, decarburization temperature 800 860 °C, holding temperature 90~160sec; Since nitriding is carried out during high temperature annealing, as long as the decarburization requirement is reached during decarburization annealing, the detachment is simplified Carbon process.
6) MgO涂层  6) MgO coating
在钢板表面涂覆以 MgO 为主要成分， 0.1~10%NH4C1和 0.5~30% P3N5， 余量为 MgO , 以重量百分比计； The surface of the steel plate is coated with MgO as the main component, 0.1~10% NH 4 C1 and 0.5~30% P 3 N 5 , and the balance is MgO, in weight percentage;
7) 高温退火  7) High temperature annealing
一次升温，先升温至 700 °C~900°C， 再以升温速度 V 温二次升温 至 1200 °C，而后保温 20小时进行净化退火；其中， V ΜΆ= 9 °C/hr〜 17。C/hr; The temperature is raised once, firstly heated to 700 °C ~ 900 °C, and then heated to 1200 °C twice at the temperature increase rate V, and then kept for 20 hours for purification annealing; wherein, V ΜΆ = 9 °C / hr~17. C/hr;
8) 绝缘涂层  8) Insulation coating
在高温退火板表面涂敷绝缘涂层， 并经热拉伸平整退火得到磁性优 良的高磁通密度取向硅钢。 本发明在炼钢成分中加入适量的 Nb。 其目的是有两点： 一方面， 当 取向硅钢中含有 Nb时，更易于在高温退火完成渗氮。这是因为相对于 Fe、 Mn而言， Nb原子的次外层 d亚层的电子填充更不饱和， 因此更容易形成 氮化物，且氮化物更稳定。另一方面，这部分在高温退火时渗入的氮原子， 既能和 Als形成高磁通密度取向硅钢所必须的主抑制剂 A1N, 又能同时获 取以 Nb2N和 NbN形式的析出物。这部分 Nb的氮化物的可作为辅助抑制 齐 (J , 起到增强抑制正常晶粒长大的效果， 最终提高取向硅钢成品板磁性能 的作用。 An insulating coating is applied on the surface of the high temperature annealed sheet, and a high magnetic flux density oriented silicon steel excellent in magnetic properties is obtained by hot drawing flat annealing. The present invention adds an appropriate amount of Nb to the steelmaking composition. The purpose is to have two points: On the one hand, when Nb is contained in the oriented silicon steel, it is easier to complete the nitriding at high temperature annealing. This is because the electron filling of the sub-dilayer sub-layer of the Nb atom is less saturated with respect to Fe and Mn, so that nitride formation is easier and the nitride is more stable. On the other hand, this part of the nitrogen atoms which are infiltrated during high-temperature annealing can form the main inhibitor A1N necessary for high magnetic flux density oriented silicon steel with Als, and can simultaneously obtain precipitates in the form of Nb 2 N and NbN. This part of Nb nitride can act as an auxiliary suppression (J, which enhances the effect of suppressing the growth of normal grains, and finally improves the magnetic properties of the oriented silicon steel finished board.
本发明在 MgO涂液中填加了适量 NH4C1和 P3N5。其目的是， 用高温 退火过程中的氮化物分解来完成向板内渗氮，从而替代脱碳退火过程中氨 气分解实现的渗氮， 其最大的益处在于能确保板内渗氮更均匀。 此外， 之 所以选择 NH4C1和 P3N5这两种无机氮化物作为高温分解时的渗氮原料是 因为， NH4C1的分解温度在 330~340 °C，而 P3N5的分解温度在 760°C左右。 不同的氮化物分解温度区域可以确保在高温退火过程中相当长的时间内 都能均匀释放出活性氮原子， 从而完成向钢板内部渗氮， 并且使氮含量 【N】 保持在 200〜250ppm这一标准范围内。 In the present invention, an appropriate amount of NH 4 C1 and P 3 N 5 is added to the MgO coating liquid. The purpose is to use nitriding in the high temperature annealing process to complete nitriding into the plate, thereby replacing the nitriding by ammonia decomposition during the decarburization annealing process, and the greatest benefit is to ensure more uniform nitriding in the plate. In addition, the two inorganic nitrides, NH 4 C1 and P 3 N 5 , are selected as the nitriding raw material for pyrolysis. Because the decomposition temperature of NH 4 C1 is 330~340 °C, and the decomposition temperature of P 3 N 5 is about 760 °C. Different nitride decomposition temperature regions ensure that the active nitrogen atoms are uniformly released over a long period of time during high-temperature annealing, thereby completing nitriding into the steel sheet and maintaining the nitrogen content [N] at 200-250 ppm. Within the standard range.
本发明要求在高温退火过程中对二次升温速度进行控制。 其目的是， 通过设定合适的二次升温速度能够确保最终成品获得优异的磁性。这是因 为， 在高温退火的二次升温过程中， 涵盖了取向硅钢二次再结晶发展的温 度范围。 因此， 合适的升温速度能够使二次再结晶过程中长大的高斯晶粒 取向度更好， 偏离角 < 3 ° ， 磁性更优。  The present invention requires control of the secondary heating rate during high temperature annealing. The purpose is to ensure excellent magnetic properties of the final product by setting an appropriate secondary heating rate. This is because the temperature range of secondary recrystallization of oriented silicon steel is covered during the secondary heating of high temperature annealing. Therefore, a suitable heating rate can make the Gaussian grain orientation which grows in the secondary recrystallization process better, the off angle is < 3 °, and the magnetic properties are better.
本发明高温退火过程中， 相对的慢速升温能确保二次再结晶完善， 成 品磁性好。 这是因为， 在高温退火的二次升温过程中会发生二次再结晶， 此时也是 A1N抑制剂逐歩粗化和分解， 抑制力同歩消失的过程。 如果在 此温度范围内， 不对升温速度过快的话， 会导致二次再结晶尚未完成， 抑 制剂却已分解失效， 成品二次再结晶不完善， 磁性差的严重后果。 发明的详细说明  In the high-temperature annealing process of the present invention, the relatively slow temperature rise ensures the secondary recrystallization is perfect, and the finished product has good magnetic properties. This is because secondary recrystallization occurs during the secondary temperature rise of the high temperature annealing, and this is also the process in which the A1N inhibitor is coarsened and decomposed, and the inhibition force disappears. If it is within this temperature range, if the heating rate is too fast, the secondary recrystallization will not be completed, but the inhibitor will be decomposed and failed, the secondary recrystallization of the finished product is imperfect, and the magnetic deterioration is serious. Detailed description of the invention
下面结合实施例对本发明做进一歩说明。  The present invention will be further described below in conjunction with the embodiments.
实施例 1  Example 1
按照表 1所述的化学成分冶炼和浇铸。 将不同成分的板坯放在 1155 °C加热炉内保温 1.5小时后热轧至厚度为 2.3mm的热轧板，开轧和终轧温 度分别为 1062 °C和 937 °C。 对热轧板采用两段式常化： （ 1120 °C x l 5sec ) + ( 870 °C x l 50sec ) ， 随后以 -15 °C/sec速度进行冷却。 经酸洗后， 冷轧到 成品厚度 0.30mm。而后以升温速度 25 °C/sec， 脱碳温度 820 °C， 均温 140s 进行脱碳退火。 涂布以 MgO为主要成分， 并含 4.5%NH4C1和 15%P3N5 的隔离剂。 高温退火时， 先升温至 800 °C， 获得二次升温前氮含量 b; 再 二次升温至 1200 °C， 而后保温 20小时进行净化退火。 开卷后经过涂敷绝 缘涂层及拉伸平整退火。其中，二次升温前氮含量 b和成品磁性能见表 1。 The chemical compositions described in Table 1 were smelted and cast. The slabs of different compositions were placed in a heating furnace at 1155 ° C for 1.5 hours and then hot rolled to a hot rolled sheet having a thickness of 2.3 mm. The rolling and finishing temperatures were 1062 ° C and 937 ° C, respectively. A two-stage normalization is applied to the hot rolled sheet: (1120 °C xl 5sec) + (870 °C xl 50sec), followed by cooling at -15 °C/sec. After pickling, it is cold rolled to a thickness of 0.30 mm. Then, decarburization annealing was carried out at a heating rate of 25 ° C/sec, a decarburization temperature of 820 ° C, and an average temperature of 140 s. A separator containing MgO as a main component and containing 4.5% NH 4 C1 and 15% P 3 N 5 was applied. When annealing at a high temperature, the temperature is first raised to 800 ° C to obtain a nitrogen content b before the second temperature rise; the temperature is further raised to 1200 ° C, and then the temperature is maintained for 20 hours for purification annealing. After unwinding, it is coated with an insulating coating and stretched and flattened. Among them, the nitrogen content b before the second temperature rise and the magnetic properties of the finished product are shown in Table 1.
化学成分对  Chemical composition
实 二次升  Real second rise
C Si Mn S Als N Sn Nb B8 施 温前氮 C Si Mn S Als N Sn Nb B 8 pre-warming nitrogen
% % % % % % % % T W/kg 例 含量 b ( ppm)% % % % % % % % TW/kg Example content b (ppm)
1 0.035 3.2 0.20 0.010 0.015 0.009 0.090 0.20 202 1.92 0.971 0.035 3.2 0.20 0.010 0.015 0.009 0.090 0.20 202 1.92 0.97
2 0.041 2.9 0.10 0.005 0.025 0.006 0.070 0.36 21 1 1.92 0.992 0.041 2.9 0.10 0.005 0.025 0.006 0.070 0.36 21 1 1.92 0.99
3 0.052 4.0 0.05 0.008 0.035 0.004 0.005 0.64 234 1.93 0.973 0.052 4.0 0.05 0.008 0.035 0.004 0.005 0.64 234 1.93 0.97
4 0.065 3.5 0.15 0.012 0.022 0.007 0.035 0.80 244 1.92 0.98 比 4 0.065 3.5 0.15 0.012 0.022 0.007 0.035 0.80 244 1.92 0.98 ratio
较  More
0.046 3.0 0.08 0.006 0.028 0.008 0.072 0.18 173 1.87 1.1 1 例  0.046 3.0 0.08 0.006 0.028 0.008 0.072 0.18 173 1.87 1.1 1 case
1  1
比  Than
较  More
0.053 3.5 0.15 0.01 1 0.019 0.006 0.014 0.84 292 1.86 1.12 例  0.053 3.5 0.15 0.01 1 0.019 0.006 0.014 0.84 292 1.86 1.12 Example
2  2
从表 1可以看出，实施例中各项化学成分的选择符合发明生产歩骤中 [冶炼及浇铸]标准范围， 而比较例中 Nb 成分的选择不符合标准范围 0.200-0.800%,所以二次升温前经检测氮含量 [N]不在 200~250ppm标准范 围内， 最终导致取向硅钢成品板铁损 （P17/5。）和磁感 （B8 ) 性能较差。 实施例 2 It can be seen from Table 1 that the selection of the chemical components in the examples conforms to the standard range of [smelting and casting] in the production process, and the selection of the Nb component in the comparative example does not meet the standard range of 0.200-0.800%, so The nitrogen content [N] before the temperature rise is not within the standard range of 200~250ppm, which ultimately leads to poor performance of the iron loss (P 17/5 ) and magnetic induction (B 8 ) of the oriented silicon steel. Example 2
取向硅钢板坯的组分及重量百分比为 C: 0.050% , Si: 3.25% , Mn: 0.15%, S: 0.009%, Als: 0.032%, N: 0.005%, Sn: 0.02%, Nb: 0.5%, 其余 为 Fe及不可避免的杂质。 将板坯放在 1155 °C加热炉内保温 1.5小时后热 轧至厚度为 2.3mm的热轧板， 开轧和终轧温度分别为 1080 °C和 910°C。 对热轧板采用两段式常化： （1110 °C x l0sec ) + ( 910 °C x l20sec ) ， 随 后以 -35 °C /sec速度进行冷却。 经酸洗后， 冷轧到成品厚度 0.30mm。 而后 以升温速度 25 °C/sec， 脱碳温度 840 °C， 均温 130s进行脱碳退火。 涂布以 MgO为主要成分， 并添加不同含量的 NH4C1和 P3N5。 高温退火时， 先升 温至 800 °C， 获得二次升温前氮含量 b; 再二次升温至 1200°C， 而后保温 20小时进行净化退火。 开卷后经过涂敷绝缘涂层及拉伸平整退火。 其中， 二次升温前氮含量 b和成品磁性能见表 2。 The composition and weight percentage of the oriented silicon steel slab are C: 0.050%, Si: 3.25%, Mn: 0.15%, S: 0.009%, Als: 0.032%, N: 0.005%, Sn: 0.02%, Nb: 0.5% The rest are Fe and inevitable impurities. The slab was placed in a heating furnace at 1155 ° C for 1.5 hours and then hot rolled to a hot rolled sheet having a thickness of 2.3 mm. The rolling and finishing temperatures were 1080 ° C and 910 ° C, respectively. Two-stage normalization is applied to the hot rolled sheet: (1110 °C x l0sec) + (910 °C x l20sec), followed by cooling at -35 °C / sec. After pickling, it is cold rolled to a thickness of 0.30 mm. Then, decarburization annealing was carried out at a heating rate of 25 ° C / sec, a decarburization temperature of 840 ° C, and an average temperature of 130 s. The coating is mainly composed of MgO, and different contents of NH 4 C1 and P 3 N 5 are added . When annealing at a high temperature, the temperature is first raised to 800 ° C to obtain a nitrogen content b before the second temperature rise; the temperature is further raised to 1200 ° C, and then the temperature is kept for 20 hours for purification annealing. After unwinding, it is coated with an insulating coating and stretched and flattened. Among them, the nitrogen content b before the second temperature rise and the magnetic properties of the finished product are shown in Table 2.
表 2 NH4C1和 P3N5含量对二次升温前氮含量和磁性能的影响 二次升温前氮含量 B8 P17/50 实施例 丽 4C1 (%) P3N5 (%) Table 2 Effect of NH 4 C1 and P 3 N 5 content on nitrogen content and magnetic properties before secondary heating Nitrogen content before secondary heating B8 P17/50 Example Li 4 C1 (%) P 3 N 5 (%)
b (ppm) (T) ( w/kg ) b (ppm) (T) ( w/kg )
1 0.1 3.9 198 1.92 0.991 0.1 3.9 198 1.92 0.99
2 1.2 11.3 210 1.91 1.002 1.2 11.3 210 1.91 1.00
3 3.6 20.8 231 1.92 0.983 3.6 20.8 231 1.92 0.98
3 6.4 0.5 206 1.92 0.973 6.4 0.5 206 1.92 0.97
4 8.3 6.6 221 1.92 1.004 8.3 6.6 221 1.92 1.00
5 10 12.8 222 1.93 0.965 10 12.8 222 1.93 0.96
6 2.4 19.5 234 1.92 0.986 2.4 19.5 234 1.92 0.98
7 5.5 26.4 252 1.91 0.997 5.5 26.4 252 1.91 0.99
8 1.9 30 243 1.93 0.96 比较例 1 6.4 0.4 178 1.87 1.10 8 1.9 30 243 1.93 0.96 Comparative Example 1 6.4 0.4 178 1.87 1.10
2 2.4 30.2 268 1.88 1.06 2 2.4 30.2 268 1.88 1.06
3 10.5 30.5 283 1.83 1.16 从表 2可以看出， 实施例中 NH4C1、 P3N5的选择符合发明生产歩骤中 [MgO涂层]标准范围 0.1~10%、 0.5-30%, 而比较例 NH4C1、 P3N5的选择 中任何一项不符合要求则会造成二次升温前检测氮含量 [N]不在 200~250ppm标准内， 最终导致取向硅钢成品板铁损 （P17/5o)和磁感（B8) 性能较差。 实施例 3 3 10.5 30.5 283 1.83 1.16 As can be seen from Table 2, the choice of NH 4 C1, P 3 N 5 in the examples is in accordance with the standard range of [MgO coating] in the production process of the invention, 0.1~10%, 0.5-30%, and Comparative Example NH 4 C1, P 3 N 5 The selection does not meet the requirements, which will cause the nitrogen content before the second temperature rise [N] is not within the 200~250ppm standard, which will eventually lead to the iron loss of the oriented silicon steel finished board (P 17 / 5 o) and magnetic (B 8 ) performance is poor. Example 3
取向硅钢板坯的组分及重量百分比为 C: 0.050%, Si: 3.25%, Mn: 0.15%, S: 0.009%, Als: 0.032%, N: 0.005%, Sn: 0.02%, Nb含量 （a) ： 0.2-0.8%, 其余为 Fe及不可避免的杂质。 将板坯放在 1115°C加热炉内保 温 2.5小时后热轧至厚度为 2.3mm的热轧板，开轧和终轧温度分别为 1050 和 865°C。 对热轧板采用两段式常化： （1120°Cxl5sec) + (900°C xl20sec) ， 随后以 -25°C/sec速度进行冷却。 经酸洗后， 冷轧到成品厚度 0.30mm。 而后以升温速度 25°C/sec， 脱碳温度 850°C， 均温 115s进行脱 碳退火。 涂布以 MgO为主要成分， 并添加 7.5%NH4C1和 12.5%P3N5。 高 温退火过程中， 先升温至 700°C~900°C， 作为二次升温的起始温度 （c) ， 获得二次升温前氮含量（b)。 再以一定的二次升温速度（V)升温至 1200 。C， 而后保温 20小时进行净化退火。 开卷后经涂敷绝缘涂层及拉伸平整 退火。 The composition and weight percentage of the oriented silicon steel slab are C: 0.050%, Si: 3.25%, Mn: 0.15%, S: 0.009%, Als: 0.032%, N: 0.005%, Sn: 0.02%, Nb content (a ) : 0.2-0.8%, the rest is Fe and unavoidable impurities. The slab was placed in a heating furnace at 1115 ° C for 2.5 hours and then hot rolled to a hot rolled sheet having a thickness of 2.3 mm, and the rolling and finishing temperatures were 1050 and 865 ° C, respectively. The two-stage normalization was applied to the hot rolled sheet: (1120 ° C x 15 sec) + (900 ° C x l20 sec), followed by cooling at -25 ° C / sec. After pickling, it is cold rolled to a thickness of 0.30 mm. Then, decarburization annealing was carried out at a heating rate of 25 ° C / sec, a decarburization temperature of 850 ° C, and an average temperature of 115 s. The coating was mainly composed of MgO, and 7.5% NH 4 C1 and 12.5% P 3 N 5 were added . During the high-temperature annealing process, the temperature is first raised to 700 ° C to 900 ° C, as the initial temperature (c) of the second temperature rise, and the nitrogen content before the second temperature rise (b) is obtained. Then heat up to 1200 with a certain secondary heating rate (V) . C, and then heat-treating for 20 hours for purification annealing. After unwinding, it is coated with an insulating coating and stretched and flattened.
表 3 不同常化和渗氮工艺对成品磁性能的影响  Table 3 Effect of different normalization and nitriding processes on magnetic properties of finished products
Figure imgf000009_0001
从表 3可以看出：
Figure imgf000009_0001
As can be seen from Table 3:
实施例和比较例两者中 Nb含量 （a) 、 二次升温前氮含量 （b) 和二 次升温起始温度 （c ) 三个条件相同时； 实施例中二次升温速度实际值在 9°C/hr 17 °C/hr， 并且理论值与实际值之差为正数时成品磁性能较好； 反 之， 比较例情况相反， 所以成品板磁性能较差。 低温板坯加热技术生产的高磁感取向硅钢具有加热炉寿命长，能耗和 成本低等优势。但是长期以来， 由于存在着后工序脱碳渗氮不均匀以及在 生产过程中难以有效调整和控制等问题，从而影响到基板内局部或整体的 抑制能力， 导致二次再结晶不完善， 产品磁性能不稳定。 In the examples and the comparative examples, the Nb content (a), the pre-heating pre-nitrogen content (b), and the secondary heating initiation temperature (c) are the same; the actual secondary heating rate in the embodiment is 9 °C/hr 17 °C/hr, and the difference between the theoretical value and the actual value is positive, the magnetic properties of the finished product are better; However, the comparative example is reversed, so the magnetic properties of the finished board are poor. The high magnetic induction oriented silicon steel produced by the low temperature slab heating technology has the advantages of long life of the heating furnace, low energy consumption and low cost. However, for a long time, there are problems such as uneven decarburization and nitriding in the post-process and difficulty in effective adjustment and control in the production process, which affects the local or overall inhibition ability in the substrate, resulting in imperfect secondary recrystallization, product magnetic properties. Can be unstable.
综上所述，本发明是基于低温板坯加热工艺的一种新的高磁通密度取 向硅钢生产方法， 它有效地解决了上述问题。 其特点在于， 通过在炼钢中 添加合适的 Nb含量， 使钢板在高温退火过程中更易吸氮； 通过在 MgO 隔离剂中添加含氮化合物， 使之在高温退火过程中受热分解， 达到向钢板 均匀渗氮的目的。 在高温退火过程中， 根据钢中 Nb含量、 氮含量和二次 升温起始温度， 控制升温速度， 从而确保二次再结晶完善， 最终获得磁性 能优异的高磁通密度取向硅钢产品。  In summary, the present invention is a novel high magnetic flux density oriented silicon steel production method based on a low temperature slab heating process, which effectively solves the above problems. It is characterized in that by adding a suitable Nb content in the steel making, the steel sheet is more likely to absorb nitrogen during the high-temperature annealing process; by adding a nitrogen-containing compound to the MgO separating agent, it is thermally decomposed during the high-temperature annealing process to reach the steel sheet. The purpose of uniform nitriding. In the high-temperature annealing process, the temperature rise rate is controlled according to the Nb content, the nitrogen content, and the secondary temperature rise temperature in the steel, thereby ensuring the secondary recrystallization is completed, and finally obtaining a high magnetic flux density oriented silicon steel product excellent in magnetic properties.

Claims

权 利 要 求 书 一种高磁通密度取向硅钢产品的生产方法， 包括如下歩骤： The method for producing a high magnetic flux density oriented silicon steel product includes the following steps:
1) 冶炼及浇铸  1) Smelting and casting
取向硅钢成分重量百分比为： C 0.035-0.065%, Si 2.9-4.0%, Mn 0.05-0.20%, S 0.005-0.012%, Als 0.015-0.035%, N 0.004-0.009%, Sn 0.005-0.090%, Nb 0.200-0.800%, 其余为 Fe及不可避免的夹杂 物； 采用转炉或电炉炼钢， 钢水经二次精炼和连铸后， 获得板坯； The weight percentage of the oriented silicon steel composition is: C 0.035-0.065%, Si 2.9-4.0%, Mn 0.05-0.20%, S 0.005-0.012%, Als 0.015-0.035%, N 0.004-0.009%, Sn 0.005-0.090%, Nb 0.200-0.800%, the rest is Fe and inevitable inclusions; steel is produced by converter or electric furnace, and molten steel is obtained by secondary refining and continuous casting to obtain slab;
2) 热轧 2) Hot rolling
板坯在加热炉内加热到 1090~1200 °C， 1180 °C以下开轧， 860 °C以 上终轧， 轧后层流冷却， 650 °C以下卷取；  The slab is heated in a heating furnace to 1090~1200 °C, rolled below 1180 °C, rolled up at 860 °C, laminar cooling after rolling, and coiled below 650 °C;
3) 常化  3) Normalization
常化工艺：常化温度 1050~1180。C，时间 l~20sec ,常化温度 850-950 V， 时间 30~200sec; 随后进行冷却， 冷却速度 10~60 °C/sec;  Normalization process: normalizing temperature 1050~1180. C, time l~20sec, normalization temperature 850-950 V, time 30~200sec; then cooling, cooling rate 10~60 °C/sec;
4) 冷轧  4) Cold rolling
常化后， 将钢板轧制到成品板厚度， 冷轧压下率≥75%; After normalization, the steel plate is rolled to the thickness of the finished plate, and the cold rolling reduction rate is ≥75% ;
5) 脱碳退火  5) Decarburization annealing
升温速度 15~35 °C/sec， 脱碳温度 800 860 °C， 保温 90~160sec; Heating rate 15~35 °C/sec, decarburization temperature 800 860 °C, holding temperature 90~160sec;
6) MgO涂层 6) MgO coating
在钢板表面涂覆以 MgO 为主要成分， 0.1~10%NH4C1和 0.5~30% P3N5， 余量为 MgO , 以重量百分比计； The surface of the steel plate is coated with MgO as the main component, 0.1~10% NH 4 C1 and 0.5~30% P 3 N 5 , and the balance is MgO, in weight percentage;
7) 高温退火  7) High temperature annealing
一次升温，先升温至 700 °C~900°C， 再以升温速度 V 温二次升温 至 1200 °C，而后保温 20小时进行净化退火；其中， V ΜΆ= 9 °C/hr〜 17。C/hr; The temperature is raised once, firstly heated to 700 °C ~ 900 °C, and then heated to 1200 °C twice at the temperature increase rate V, and then kept for 20 hours for purification annealing; wherein, V ΜΆ = 9 °C / hr~17. C/hr;
8) 绝缘涂层  8) Insulation coating
在高温退火板表面涂敷绝缘涂层， 并经热拉伸平整退火得到磁性优 良的高磁通密度取向硅钢。  An insulating coating is applied on the surface of the high temperature annealed sheet, and subjected to hot drawing and flat annealing to obtain a magnetic high-strength magnetic flux-oriented silicon steel.
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