WO2022161048A1 - Strongly magnetic oriented high-silicon steel ultrathin strip and preparation method therefor - Google Patents

Strongly magnetic oriented high-silicon steel ultrathin strip and preparation method therefor Download PDF

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WO2022161048A1
WO2022161048A1 PCT/CN2021/140773 CN2021140773W WO2022161048A1 WO 2022161048 A1 WO2022161048 A1 WO 2022161048A1 CN 2021140773 W CN2021140773 W CN 2021140773W WO 2022161048 A1 WO2022161048 A1 WO 2022161048A1
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silicon steel
thin strip
annealing
ferromagnetic
oriented high
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PCT/CN2021/140773
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French (fr)
Chinese (zh)
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王波
张迪
孙会兰
郭志红
朱立光
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河北科技大学
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Priority to JP2022543607A priority Critical patent/JP7324549B2/en
Publication of WO2022161048A1 publication Critical patent/WO2022161048A1/en

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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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/773—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material under reduced pressure or vacuum
    • 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
    • C21D8/1227—Warm 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
    • 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
    • C21D8/1277—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
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper

Definitions

  • the application belongs to the field of electrical steel manufacturing, and more particularly, relates to a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method thereof.
  • Oriented silicon steel is an important soft magnetic material, an important raw material for the preparation of transformer cores, and one of the indispensable materials for the development of the power industry.
  • the low iron loss and low magnetostriction characteristics of high silicon steel show outstanding advantages in high frequency equipment such as high-speed high-frequency motors, audio, high-frequency transformers, choke coils and magnetic shielding at high frequencies.
  • the use of high-silicon steel instead of ordinary cold-rolled oriented silicon steel can not only improve the operating frequency and sensitivity of electronic and electrical components, but also greatly reduce the weight and volume of electrical equipment, making electrical equipment clean and noiseless during operation, saving energy It effectively solves the contradiction between high efficiency, energy saving, portability and cleanliness without noise.
  • the thin strip continuous casting method can directly produce thin strips by using liquid alloys. It is a very potential short-flow metal thin strip preparation process.
  • the casting process uses the casting roll as the mold, and the alloy liquid is in direct contact with the casting roll.
  • the solidification structure and texture of the obtained oriented silicon steel are significantly different from those of the traditional continuous casting billet.
  • the obtained oriented silicon steel has the characteristics of sub-rapid solidification, which can fully suppress the coarsening process of the second phase particles, and fundamentally solve the problem of the oriented silicon steel.
  • the disadvantages of high-temperature heating of casting slabs provide favorable conditions for the preparation of grain-oriented silicon steel with fine, uniform and dispersed distribution of inhibitors. This technology has been successfully applied to the production of low-carbon steel, high-speed steel and other processes.
  • the present application provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method thereof.
  • an embodiment of the present application provides a ferromagnetic oriented high silicon steel ultra-thin strip, which contains the following elements by mass percentage:
  • adding a ferromagnetic oriented high silicon steel ultra-thin strip in the form of a multi-nuclear complex containing sulfur, nitrogen and copper refers to adding sulfur, nitrogen and copper elements to the alloy raw materials during the preparation process. coordination compounds.
  • the ferromagnetic oriented high silicon steel ultra-thin strip can be understood as the oriented high-silicon steel strip obtained by the above-mentioned mass percentage elements is an ultra-thin strip with a small thickness and has good strong magnetic properties.
  • mass percentage of each element can be any value in the above range interval.
  • the embodiments of the present application also provide a method for preparing the above-mentioned ferromagnetic oriented high silicon steel ultra-thin strip, which specifically includes the following steps:
  • the stripping machine is used to control the linear speed of the rollers to ensure the high-speed operation of the stripping process.
  • Undercooling refers to the inhibition of nucleation, so that the ferrosilicon master alloy solution remains liquid under a large degree of undercooling.
  • the alloy solution is obtained after the alloy raw material is completely melted, and the alloy raw material here refers to other raw materials other than Bi element, multinuclear complex containing sulfur nitrogen and copper.
  • high-purity nitrogen is introduced into the surface of the alloy solution, and in S2, it is also in an atmosphere of high-purity nitrogen.
  • the silicon steel thin strip is first taken out from the strip machine, and then the rolled silicon steel thin strip is subjected to water cooling treatment, warm rolling treatment, heating and vacuum annealing treatment, cold rolling treatment, heating and pure hydrogen secondary annealing treatment in sequence , air cooling treatment, coating treatment, heating and purge gas annealing treatment, wherein air cooling refers to cooling in the atmosphere.
  • the smelting of the alloy raw materials in S1 is performed in a melting furnace, and a high-temperature arc melting furnace can be selected.
  • the temperature of the mixed smelting in S1 is 1300-1500°C.
  • the melting temperature in this range can fully melt the alloy raw materials and mix them evenly, and form a silicon steel strip with uniform structure and properties during the stripping process. It can be understood that the melting temperature can be any value within the above range. Of course, in other possible implementation manners, other smelting temperatures may also be used, but not limited to this.
  • the temperature of the vacuum annealing in S3 is 850-1050° C., and the time of the vacuum annealing is 2-5 min.
  • the vacuum annealing temperature and annealing time in this range can make the excess C element and Si element oxide in the silicon steel strip precipitate to the surface of the silicon steel strip to form an oxide layer, which can be removed during the cold rolling process to further improve the silicon steel strip.
  • Belt machinability and toughness It can be understood that, the above-mentioned annealing temperature and annealing time may be any value within the above-mentioned range. Of course, in other possible implementation manners, other annealing temperatures and annealing times may also be used, but are not limited thereto.
  • the warm-rolled silicon steel strip is heated to an annealing temperature at a heating rate of 20-25° C./h.
  • the annealing temperature here refers to the annealing temperature of vacuum annealing.
  • the heating rate in this range can reduce the temperature gradient between the layers of the silicon steel strip, help the formation of oxides of C and Si on the surface of the silicon steel strip, improve the uniformity of the surface oxide layer, and also help the weave in the vacuum annealing process. provide optimal kinetic conditions for the formation of structures and tissues. It can be understood that the above-mentioned heating rate may be any value within the above-mentioned range. Of course, in other possible implementation manners, other heating rates may also be used, which are not limited thereto.
  • the temperature of the secondary annealing of pure hydrogen in S3 is 1000-1150° C.
  • the time of secondary annealing of pure hydrogen is 2-5 min.
  • the pure hydrogen secondary annealing temperature and annealing time in this range can ensure that the Goss grains in the silicon steel strip can fully absorb other grains, abnormal growth occurs, and a perfect secondary recrystallization texture is formed. Magnetic properties of the belt.
  • the above-mentioned annealing temperature and annealing time may be any value within the above-mentioned range.
  • other annealing temperatures and annealing times may also be used, but are not limited thereto.
  • the cold-rolled silicon steel strip is heated to the annealing temperature at a heating rate of 20-25° C./h.
  • the annealing temperature here refers to the annealing temperature of the secondary annealing with pure hydrogen.
  • the heating rate in this range can reduce the temperature gradient between the layers of the silicon steel strip, provide suitable conditions for the Goss grains in the structure to swallow other grains, improve the uniformity of the structure in the silicon steel strip, and improve the magnetic properties of the silicon steel strip. It can be understood that the above-mentioned heating rate may be any value within the above-mentioned range. Of course, in other possible implementation manners, other heating rates may also be used, which are not limited thereto.
  • the temperature of the purification gas annealing in S3 is 950-1200° C.
  • the time of the purification gas annealing is 3 to 5 minutes.
  • the above-mentioned annealing temperature and annealing time may be any value within the above-mentioned range.
  • other annealing temperatures and annealing times may also be used, but are not limited thereto.
  • the silicon steel thin strip coated with the annealing isolation layer is heated to an annealing temperature at a heating rate of 35-40° C./h before the annealing of the purification gas.
  • the annealing temperature here refers to the annealing temperature of the purge gas annealing. It can be understood that the above-mentioned heating rate may be any value within the above-mentioned range. Of course, in other possible implementation manners, other heating rates may also be used, which are not limited thereto.
  • the composition of the annealing isolation layer described in S3 is a mixture of aluminum dihydrogen phosphate, styrene-acrylic emulsion, glycerin and a silane coupling agent, and the mass percentage of each composition in the mixture is: Aluminum dihydrogen phosphate: 10 ⁇ 15%, styrene-acrylic emulsion: 20 ⁇ 40%, glycerin: 25 ⁇ 35%, silane coupling agent: 10 ⁇ 30%. It should be noted that the initial value is abbreviated in the above mass percentage.
  • the annealing isolation layer can maximize the oxidation resistance of the silicon steel thin strip surface and the punching performance of the silicon steel thin strip, prevent the bonding between layers in the subsequent product preparation process, and improve the quality.
  • the above-mentioned mass percentage can be any value in the above-mentioned range interval.
  • other components and mass percentages may also be used, but not limited to this.
  • S3 specifically includes the steps of: water-cooling the silicon steel thin strip to 500-600° C. after being taken out of the roll to obtain a first thin strip, and warmly rolling the first thin strip to 0.14-0.17 mm , obtain a second thin strip, heat the second thin strip for vacuum annealing to obtain a third thin strip, and then cold-roll the third thin strip to 0.09 ⁇ 0.12mm to obtain a fourth thin strip.
  • the fourth thin strip is heated for secondary annealing with pure hydrogen to obtain a fifth thin strip, the fifth thin strip is then air-cooled to room temperature to obtain a sixth thin strip, and the sixth thin strip is coated with an annealing isolation layer to obtain For the seventh thin strip, the seventh thin strip is heated for purification gas annealing to obtain the ferromagnetic oriented high silicon steel ultra-thin strip.
  • the present application designs the raw material components of the ferromagnetic oriented high-silicon steel ultra-thin strip, and adopts the multi-nuclear coordination compound containing sulfur, nitrogen and copper and the Bi element as the alloy inhibitor.
  • the multi-nuclear coordination compound of the alloy can ensure a high element absorption rate while introducing Cu element, S element and N element into the alloy, and can also react with other metals in the alloy to form CuS, AlN, MnS and other substances.
  • the substance can be precipitated during the solid-liquid solidification process in the initial stage of casting, and together with the Bi element distributed at the grain boundary, suppress the growth of the primary recrystallized grains, thereby promoting the secondary crystallization of the Goss grains and making the obtained strong magnetic orientation.
  • the ultra-thin strip of high silicon steel has fine grains and uniform texture, and has excellent magnetic properties with high magnetic induction intensity and low iron loss.
  • the preparation method of the ferromagnetic oriented high-silicon steel ultra-thin strip introduces high-purity nitrogen during the smelting and stripping process of the alloy, which can not only promote the AlN inhibitor through high-temperature nitriding. It can improve the formation of texture and the uniformity of the alloy structure, and can also prevent the oxidation of the alloy surface.
  • polynuclear coordination compounds containing sulfur, nitrogen and copper and bismuth elements are added to ensure the recovery of copper and bismuth elements. yield.
  • High-purity nitrogen can also be used as a cooling gas to rapidly cool the free surface of the silicon steel strip during the stripping process and accelerate the formation of grains.
  • after three different recrystallization annealing processes, combined with the coating of the surface annealing isolation layer further stability The structure of silicon steel strip improves the magnetic properties, purity, surface oxidation resistance and punching performance of silicon steel strip.
  • the preparation method of the ferromagnetic oriented high silicon steel ultra-thin strip provided by the present application further utilizes the advantages of deep undercooling and rapid solidification through the integrated process route of continuous casting, rolling, high temperature annealing, surface modification, etc.
  • the ultra-thin high silicon steel strip has the characteristics of high purity, good stability and excellent magnetic properties.
  • This embodiment provides a ferromagnetic oriented high silicon steel ultra-thin strip, which includes the following elements by mass percentage: C: 0.0045%, Si: 4.5%, Mn: 0.23%, S: 0.02%, Bi: 0.03%, Als: 0.027%, Cu: 0.02%, N: 0.008%, P: 0.004%, and the rest is Fe.
  • Cu element, S element, and N element are ferromagnetically added in the form of multi-nuclear complexes containing sulfur, nitrogen and copper during smelting
  • Oriented high silicon steel ultra-thin strip specifically N,N-di-n-butyldithiocarbamate can be selected.
  • the present embodiment also provides a method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip, which specifically includes the following steps:
  • S1 Prepare alloy raw materials according to the mass percentage of each element in the ferromagnetic oriented high silicon steel ultra-thin strip, mix the raw materials except Bi element and polynuclear complexes containing sulfur, nitrogen and copper, and place them in a high-temperature arc melting furnace.
  • S3 First take out the silicon steel thin strip from the roll of the stripping machine, then water-cool the silicon steel thin strip after the roll to 500°C, warmly roll it to 0.17mm, and heat it to 850°C at a heating rate of 20°C/h. Vacuum annealed for 2 minutes, then cold rolled to 0.12mm thick, then heated to 1000°C at a heating rate of 20°C/h, followed by secondary annealing with pure hydrogen for 2 minutes, and then air-cooled to room temperature. The heating rate of /h is heated to 950 °C, and then purified gas annealing is carried out. After 3 minutes of purification gas annealing, a ferromagnetic oriented high silicon steel ultra-thin strip is obtained.
  • the composition of the annealing isolation layer is 10% by mass of aluminum dihydrogen phosphate. , 40% styrene-acrylic emulsion, 35% glycerol and 15% silane coupling agent.
  • This embodiment provides a ferromagnetic oriented high silicon steel ultra-thin strip, including the following elements by mass percentage: C: 0.0060%, Si: 5.0%, Mn: 0.32%, S: 0.03%, Bi: 0.08%, Als: 0.035%, Cu: 0.03%, N: 0.0010%, P: 0.002%, and the rest is Fe.
  • Cu element, S element, and N element are ferromagnetically added in the form of multi-nuclear complexes containing sulfur, nitrogen and copper during smelting
  • bis(1-aza-heterocyclyl)dithiocarbamate (II) can be specifically selected.
  • the present embodiment also provides a method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip, which specifically includes the following steps:
  • S3 First take out the silicon steel thin strip from the roll of the strip machine, and then water-cool the silicon steel thin strip after the roll to 600°C, warmly roll it to 0.14mm, and heat it to 1050°C at a heating rate of 20°C/h. Vacuum annealed for 5 minutes, then cold rolled to 0.09mm thick, then heated to 1150°C at a heating rate of 25°C/h, followed by secondary annealing with pure hydrogen for 5 minutes, and then air-cooled to room temperature. °C/h speed heating to 1200 °C, and then annealing with purification gas. After annealing in purification gas for 5 minutes, a ferromagnetic oriented high silicon steel ultra-thin strip is obtained.
  • the composition of the annealing isolation layer is 15% by mass of aluminum dihydrogen phosphate. , 30% styrene-acrylic emulsion, 25% glycerin and 30% silane coupling agent.
  • This embodiment provides a ferromagnetic oriented high silicon steel ultra-thin strip, including the following elements by mass percentage: C: 0.0050%, Si: 4.5%, Mn: 0.28%, S: 0.02%, Bi: 0.05%, Als: 0.030%, Cu: 0.02%, N: 0.008%, P: 0.004%, and the rest is Fe.
  • Cu element, S element, and N element are ferromagnetically added in the form of multinuclear complexes containing sulfur, nitrogen and copper during smelting Oriented silicon steel ultra-thin strip, specifically, ⁇ Cu(NH 3 ) 4 ⁇ SO 4 can be selected.
  • the present embodiment also provides a method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip, which specifically includes the following steps:
  • S3 First take out the silicon steel thin strip from the roll of the strip machine, then water-cool the silicon steel thin strip after the roll to 500°C, warmly roll it to a thickness of 0.15mm, and heat it to 950°C at a heating rate of 20°C/h. Vacuum annealed for 2 min, then cold rolled to 0.10mm thick, then heated to 1080°C at a heating rate of 25°C/h, followed by secondary annealing with pure hydrogen for 2min, and then air-cooled to room temperature. °C/h speed heating to 1080 °C, and then annealing with purification gas. After annealing in purification gas for 3 minutes, a ferromagnetic oriented high silicon steel ultra-thin strip is obtained.
  • the composition of the annealing isolation layer is 15% by mass of aluminum dihydrogen phosphate. , 20% styrene-acrylic emulsion, 35% glycerol and 30% silane coupling agent.
  • This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip.
  • the other components and preparation process are the same as those in Example 3, except that the ferromagnetic oriented high silicon steel ultra-thin strip is added in the form of ordinary alloy raw materials.
  • This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip.
  • Example 3 is the same.
  • This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip. Except that the secondary annealing temperature of pure hydrogen is 1200°C, and the annealing temperature of purified gas is 1250°C, other components and preparation processes are the same as those in Example 3.
  • This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip, except that in the preparation method of the ferromagnetic oriented high-silicon steel ultra-thin strip, the The heating rate is 35°C/h, and the heating rate of the silicon steel strip before the secondary annealing with pure hydrogen is 35°C/h, and other components and preparation processes are the same as those in Example 3.
  • This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip. Except that the component of the isolation layer is magnesium oxide, other components and preparation process are the same as those in Example 3.
  • Test example The saturation magnetic induction intensity and iron loss of the high silicon steel ultra-thin strip obtained in the embodiment and the comparative example are respectively tested, and the test results are shown in Table 1:
  • the ultra-thin ferromagnetic oriented high-silicon steel strips obtained in the examples of the present application have fine grains, uniform structure, magnetic induction performance B800 >1.90T, and iron loss P1.7/50 value Less than 0.90W/kg, P1.0/400 value less than 8.5W/kg, with excellent magnetic induction performance.

Abstract

The present application belongs to the field of electrical steel fabrication, and provides a strongly magnetic oriented high-silicon steel ultrathin strip and a preparation method therefor. The strongly magnetic oriented high-silicon steel ultrathin strip comprises the following elements in percentage by mass: 0.0045 to 0.0060% C; 4.5% to 5.0% Si; 0.23% to 0.32% Mn; 0.02% to 0.03% S; 0.03% to 0.08% Bi; 0.027% to 0.035% Als; 0.02% to 0.03% Cu; 0.008% to 0.010% N; P<0.005%; and the remainder is iron, wherein the Cu, S and N elements are added into a strongly magnetic oriented high-silicon steel ultrathin strip in the form of a polynuclear coordination compound containing sulfur, nitrogen and copper during smelting. In the present application, by means of designing the raw material components of oriented high-silicon steel, and using the polynuclear coordination compound containing sulfur, nitrogen and copper, and a Bi element as alloy inhibitors, the prepared strongly magnetic oriented high-silicon steel ultrathin strip has fine grains, a uniform structure, and excellent magnetic properties having high magnetic induction intensity and low iron loss.

Description

一种强磁性取向高硅钢极薄带及其制备方法A kind of ferromagnetic oriented high silicon steel ultra-thin strip and preparation method thereof
本专利申请要求于2021年2月1日提交的中国专利申请No.    CN202110137389.4的优先权。在先申请的公开内容通过整体引用并入本申请。This patent application claims the priority of Chinese Patent Application No. CN202110137389.4 filed on February 1, 2021. The disclosures of the earlier applications are incorporated by reference into this application in their entirety.
技术领域technical field
本申请属于电工钢制造领域，更具体地说，涉及一种强磁性取向高硅钢极薄带及其制备方法。The application belongs to the field of electrical steel manufacturing, and more particularly, relates to a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method thereof.
背景技术Background technique
取向硅钢是一种重要的软磁材料，是变压器铁芯的重要制备原料，也是电力行业发展不可或缺的材料之一。高硅钢的低铁损和低磁致伸缩系数特性在高速高频电机、音频、高频变压器、扼流线圈和高频下的磁屏蔽等高频率设备中显示出突出的优越性。此外，采用高硅钢替代普通的冷轧取向硅钢，不仅能提高电子和电器元件的工作频率和灵敏度，同时可以大幅度减轻电器设备的重量和体积，使得电器设备在运行时清净无噪音，节约能耗，有效解决了高效化、节能化、轻便化及清净无噪音化之间的矛盾。Oriented silicon steel is an important soft magnetic material, an important raw material for the preparation of transformer cores, and one of the indispensable materials for the development of the power industry. The low iron loss and low magnetostriction characteristics of high silicon steel show outstanding advantages in high frequency equipment such as high-speed high-frequency motors, audio, high-frequency transformers, choke coils and magnetic shielding at high frequencies. In addition, the use of high-silicon steel instead of ordinary cold-rolled oriented silicon steel can not only improve the operating frequency and sensitivity of electronic and electrical components, but also greatly reduce the weight and volume of electrical equipment, making electrical equipment clean and noiseless during operation, saving energy It effectively solves the contradiction between high efficiency, energy saving, portability and cleanliness without noise.
薄带连铸法可以利用液态合金直接生产薄带材，是一种极具潜力的短流程金属薄带材制备工艺，浇铸过程以浇铸辊作为结晶器，合金液与浇铸辊直接接触，所制得的取向硅钢的凝固组织、织构显著不同于传统连铸坯，所制得的取向硅钢具有亚快速凝固的特性，可充分抑制第二相粒子的粗化过程，从根本上解决了取向硅钢铸坯高温加热的弊端，为制备取向硅钢所需的抑制剂细小、均匀、弥散分布提供有利条件，该技术已成功应用于低碳钢、高速钢等工艺的生产，但是在取向高硅钢的生产中，对凝固组织的控制，抑制剂的析出，冷加工塑性等方面的要求更高，这些问题难以克服，导致现有技术中的取向高硅钢仍存在纯净度低、稳定性差、磁感应强度低和铁损高的缺陷。The thin strip continuous casting method can directly produce thin strips by using liquid alloys. It is a very potential short-flow metal thin strip preparation process. The casting process uses the casting roll as the mold, and the alloy liquid is in direct contact with the casting roll. The solidification structure and texture of the obtained oriented silicon steel are significantly different from those of the traditional continuous casting billet. The obtained oriented silicon steel has the characteristics of sub-rapid solidification, which can fully suppress the coarsening process of the second phase particles, and fundamentally solve the problem of the oriented silicon steel. The disadvantages of high-temperature heating of casting slabs provide favorable conditions for the preparation of grain-oriented silicon steel with fine, uniform and dispersed distribution of inhibitors. This technology has been successfully applied to the production of low-carbon steel, high-speed steel and other processes. In addition, the control of the solidification structure, the precipitation of inhibitors, and the cold working plasticity have higher requirements. These problems are difficult to overcome, resulting in low purity, poor stability, low magnetic induction and iron in the oriented high-silicon steel in the prior art. High damage defect.
技术问题technical problem
针对现有技术中强磁性取向高硅钢存在的纯净度低、稳定性差、磁性能差的技术问题，本申请提供一种强磁性取向高硅钢极薄带及其制备方法。Aiming at the technical problems of low purity, poor stability and poor magnetic properties of the ferromagnetic oriented high silicon steel in the prior art, the present application provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method thereof.
技术解决方案technical solutions
为实现上述目的，本申请实施例采用了如下技术方案：To achieve the above purpose, the embodiment of the present application adopts the following technical solutions:
第一方面，本申请实施例提供一种强磁性取向高硅钢极薄带，包含以下质量百分比的元素：In the first aspect, an embodiment of the present application provides a ferromagnetic oriented high silicon steel ultra-thin strip, which contains the following elements by mass percentage:
C：0.0045%~0.0060%，Si：4.5%~5.0%，Mn：0.23%~0.32%，S：0.02%~0.03%，Bi：0.03%~0.08%，Als：0.027%~0.035%，Cu：0.02%~0.03%，N：0.008%~0.010%，P＜0.005%，其余为铁，其中所述Cu元素、所述S元素、所述N元素在熔炼时以含硫氮和铜的多核配位化合物的方式加入所述强磁性取向高硅钢极薄带。C: 0.0045%~0.0060%, Si: 4.5%~5.0%, Mn: 0.23%~0.32%, S: 0.02%~0.03%, Bi: 0.03%~0.08%, Als: 0.027%~0.035%, Cu: 0.02%~0.03%, N: 0.008%~0.010%, P<0.005%, and the rest is iron, wherein the Cu element, the S element, and the N element are smelted in a multi-nuclear mixture containing sulfur, nitrogen and copper. The ferromagnetic oriented high silicon steel ultra-thin strip is added in the way of site compound.
可以理解的是，以含硫氮和铜的多核配位化合物的方式加入强磁性取向高硅钢极薄带指的是在制备过程中向合金原料中加入硫元素、氮元素、铜元素所组成的配位化合物。强磁性取向高硅钢极薄带可以理解为，上述质量百分比元素所得到的取向高硅钢带为厚度较小的极薄带，并且具有良好的强磁性。It can be understood that adding a ferromagnetic oriented high silicon steel ultra-thin strip in the form of a multi-nuclear complex containing sulfur, nitrogen and copper refers to adding sulfur, nitrogen and copper elements to the alloy raw materials during the preparation process. coordination compounds. The ferromagnetic oriented high silicon steel ultra-thin strip can be understood as the oriented high-silicon steel strip obtained by the above-mentioned mass percentage elements is an ultra-thin strip with a small thickness and has good strong magnetic properties.
可以理解的是，各元素的质量百分比可以是上述范围区间的任意值。It can be understood that the mass percentage of each element can be any value in the above range interval.
第二方面，本申请实施例还提供上述强磁性取向高硅钢极薄带的制备方法，具体包括以下步骤：In the second aspect, the embodiments of the present application also provide a method for preparing the above-mentioned ferromagnetic oriented high silicon steel ultra-thin strip, which specifically includes the following steps:
S1：按照所述强磁性取向高硅钢极薄带中各元素的质量百分比准备原料，将除所述Bi元素及所述含硫氮和铜的多核配位化合物以外的原料混合熔炼，待合金原料完全熔化后得到合金溶液，向所述合金溶液表面通入高纯氮气，同时加入所述含硫氮和铜的多核配位化合物，然后再加入所述Bi元素，制得硅铁母合金溶液，其中所述Bi元素可通过Bi粉的方式加入所述合金溶液；S1: Prepare raw materials according to the mass percentage of each element in the ferromagnetic oriented high silicon steel ultra-thin strip, mix and smelt the raw materials except the Bi element and the multi-nuclear complex containing sulfur, nitrogen and copper, and prepare the alloy raw materials. After complete melting, an alloy solution is obtained, high-purity nitrogen gas is introduced into the surface of the alloy solution, and the polynuclear complex containing sulfur, nitrogen and copper is added at the same time, and then the Bi element is added to prepare a ferrosilicon master alloy solution, Wherein the Bi element can be added to the alloy solution by means of Bi powder;
S2：将所述硅铁母合金溶液的温度控制在1100~1200℃，在持续流动的高纯氮气中进行高速单辊甩带，控制所述高速单辊甩带过程中辊的线速度为20~30m/s，制备出0.20~0.25mm厚的硅钢薄带；S2: control the temperature of the ferrosilicon mother alloy solution at 1100-1200°C, carry out high-speed single-roller stripping in a continuous flow of high-purity nitrogen, and control the linear speed of the roller during the high-speed single-roller stripping process to be 20 ~30m/s, prepare 0.20~0.25mm thick silicon steel strip;
S3：将所述硅钢薄带出辊后水冷至500~600℃，温轧至0.14~0.17mm，加热进行真空退火；再冷轧至 0.09~0.12mm，加热进行纯氢气二次退火，再空冷至室温，涂覆退火隔离层后加热进行净化气体退火，即得所述强磁性取向高硅钢极薄带。S3: After the thin silicon steel strip is taken out of the roll, water-cooled to 500-600°C, warm-rolled to 0.14-0.17mm, heated for vacuum annealing; cold-rolled to 0.09-0.12mm, heated for secondary annealing with pure hydrogen, and then air-cooled When the temperature is reached to room temperature, the annealing isolation layer is coated and then heated for purification gas annealing to obtain the ferromagnetic oriented high silicon steel ultra-thin strip.
可以理解的是，高速单辊甩带过程中利用甩带机进行，控制辊的线速度，保证甩带过程的高速操作，并且，在该过程中，能够实现深过冷快速凝固的效果，深过冷指的是通过抑制形核，使得硅铁母合金溶液在很大过冷度下仍维持为液态。S1中待合金原料完全熔化后得到合金溶液，此处的合金原料指的是除Bi元素、含硫氮和铜的多核配位化合物以外的其他原料。S1中向合金溶液表面通入高纯氮气，S2中也处于高纯氮气的氛围中。S3中，首先将硅钢薄带从甩带机中取出，然后对出辊的硅钢薄带依次进行水冷处理、温轧处理、加热且真空退火处理、冷轧处理、加热且纯氢气二次退火处理、空冷处理、涂覆处理、加热且净化气体退火处理，其中，空冷指的是在大气中冷却。It is understandable that, in the process of high-speed single-roller stripping, the stripping machine is used to control the linear speed of the rollers to ensure the high-speed operation of the stripping process. Undercooling refers to the inhibition of nucleation, so that the ferrosilicon master alloy solution remains liquid under a large degree of undercooling. In S1, the alloy solution is obtained after the alloy raw material is completely melted, and the alloy raw material here refers to other raw materials other than Bi element, multinuclear complex containing sulfur nitrogen and copper. In S1, high-purity nitrogen is introduced into the surface of the alloy solution, and in S2, it is also in an atmosphere of high-purity nitrogen. In S3, the silicon steel thin strip is first taken out from the strip machine, and then the rolled silicon steel thin strip is subjected to water cooling treatment, warm rolling treatment, heating and vacuum annealing treatment, cold rolling treatment, heating and pure hydrogen secondary annealing treatment in sequence , air cooling treatment, coating treatment, heating and purge gas annealing treatment, wherein air cooling refers to cooling in the atmosphere.
可以理解的是，S2、S3中的数值可以是上述范围区间的任意值。It can be understood that the numerical values in S2 and S3 can be any values in the above range.
在一种可能的实现方式中，S1中合金原料的熔炼在熔炼炉中进行，可选用高温电弧熔炼炉。In a possible implementation manner, the smelting of the alloy raw materials in S1 is performed in a melting furnace, and a high-temperature arc melting furnace can be selected.
在一种可能的实现方式中，S1中所述混合熔炼的温度为1300~1500℃。该范围的熔炼温度可以使合金原料充分熔化，并混合均匀，在甩带过程中形成结构和性质均一的硅钢薄带。可以理解的是，熔炼温度可以是上述范围区间的任意值。当然，在其他可能的实现方式中，还可以采用其他熔炼温度，并不局限于此。In a possible implementation manner, the temperature of the mixed smelting in S1 is 1300-1500°C. The melting temperature in this range can fully melt the alloy raw materials and mix them evenly, and form a silicon steel strip with uniform structure and properties during the stripping process. It can be understood that the melting temperature can be any value within the above range. Of course, in other possible implementation manners, other smelting temperatures may also be used, but not limited to this.
在一种可能的实现方式中，S3中所述真空退火的温度为850~1050℃，所述真空退火的时间为2~5min。该范围的真空退火温度和退火时间，可以使硅钢薄带中多余的C元素、Si元素的氧化物析出至硅钢薄带表面而形成氧化物层，并在冷轧过程中去除，进一步提升硅钢薄带的可加工性和韧性。可以理解的是，上述退火温度和退火时间可以是上述范围区间的任意值。当然，在其他可能的实现方式中，还可以采用其他退火温度和退火时间，并不局限于此。In a possible implementation manner, the temperature of the vacuum annealing in S3 is 850-1050° C., and the time of the vacuum annealing is 2-5 min. The vacuum annealing temperature and annealing time in this range can make the excess C element and Si element oxide in the silicon steel strip precipitate to the surface of the silicon steel strip to form an oxide layer, which can be removed during the cold rolling process to further improve the silicon steel strip. Belt machinability and toughness. It can be understood that, the above-mentioned annealing temperature and annealing time may be any value within the above-mentioned range. Of course, in other possible implementation manners, other annealing temperatures and annealing times may also be used, but are not limited thereto.
在一种可能的实现方式中，所述真空退火前将完成温轧的所述硅钢薄带以20~25℃/h的升温速度升温至退火温度。此处退火温度指的是真空退火的退火温度。该范围的的升温速度，可以降低硅钢薄带层间的温度梯度，有助于硅钢薄带表面C、Si的氧化物的生成，提高表面氧化物层的均匀性，也为真空退火过程中织构和组织的形成提供最佳的动力学条件。可以理解的是，上述升温速度可以是上述范围区间的任意值。当然，在其他可能的实现方式中，还可以采用其他升温速度，并不局限于此。In a possible implementation manner, before the vacuum annealing, the warm-rolled silicon steel strip is heated to an annealing temperature at a heating rate of 20-25° C./h. The annealing temperature here refers to the annealing temperature of vacuum annealing. The heating rate in this range can reduce the temperature gradient between the layers of the silicon steel strip, help the formation of oxides of C and Si on the surface of the silicon steel strip, improve the uniformity of the surface oxide layer, and also help the weave in the vacuum annealing process. provide optimal kinetic conditions for the formation of structures and tissues. It can be understood that the above-mentioned heating rate may be any value within the above-mentioned range. Of course, in other possible implementation manners, other heating rates may also be used, which are not limited thereto.
在一种可能的实现方式中，S3中所述纯氢气二次退火的温度为1000~1150℃，所述纯氢气二次退火的时间为2~5min。该范围的纯氢气二次退火温度和退火时间可以保证硅钢薄带中的Goss晶粒充分吞并其他晶粒，发生异常长大，形成完善的二次再结晶织构，提高二次退火之后硅钢薄带的磁性能。可以理解的是，上述退火温度和退火时间可以是上述范围区间的任意值。当然，在其他可能的实现方式中，还可以采用其他退火温度和退火时间，并不局限于此。In a possible implementation manner, the temperature of the secondary annealing of pure hydrogen in S3 is 1000-1150° C., and the time of secondary annealing of pure hydrogen is 2-5 min. The pure hydrogen secondary annealing temperature and annealing time in this range can ensure that the Goss grains in the silicon steel strip can fully absorb other grains, abnormal growth occurs, and a perfect secondary recrystallization texture is formed. Magnetic properties of the belt. It can be understood that, the above-mentioned annealing temperature and annealing time may be any value within the above-mentioned range. Of course, in other possible implementation manners, other annealing temperatures and annealing times may also be used, but are not limited thereto.
在一种可能的实现方式中，所述纯氢气二次退火前将完成冷轧的所述硅钢薄带以20~25℃/h的升温速度升温至退火温度。此处退火温度指的是纯氢气二次退火的退火温度。该范围的升温速度可以降低硅钢薄带层间的温度梯度，为组织中的Goss晶粒吞并其他晶粒提供合适的条件，提高硅钢薄带内组织的均匀性，提高硅钢薄带的磁性能。可以理解的是，上述升温速度可以是上述范围区间的任意值。当然，在其他可能的实现方式中，还可以采用其他升温速度，并不局限于此。In a possible implementation manner, before the pure hydrogen secondary annealing, the cold-rolled silicon steel strip is heated to the annealing temperature at a heating rate of 20-25° C./h. The annealing temperature here refers to the annealing temperature of the secondary annealing with pure hydrogen. The heating rate in this range can reduce the temperature gradient between the layers of the silicon steel strip, provide suitable conditions for the Goss grains in the structure to swallow other grains, improve the uniformity of the structure in the silicon steel strip, and improve the magnetic properties of the silicon steel strip. It can be understood that the above-mentioned heating rate may be any value within the above-mentioned range. Of course, in other possible implementation manners, other heating rates may also be used, which are not limited thereto.
在一种可能的实现方式中，S3中所述净化气体退火的温度为950~1200℃，所述净化气体退火的时间为3~5min。可以理解的是，上述退火温度和退火时间可以是上述范围区间的任意值。当然，在其他可能的实现方式中，还可以采用其他退火温度和退火时间，并不局限于此。In a possible implementation manner, the temperature of the purification gas annealing in S3 is 950-1200° C., and the time of the purification gas annealing is 3 to 5 minutes. It can be understood that, the above-mentioned annealing temperature and annealing time may be any value within the above-mentioned range. Of course, in other possible implementation manners, other annealing temperatures and annealing times may also be used, but are not limited thereto.
在一种可能的实现方式中，所述净化气体退火前将涂敷所述退火隔离层的所述硅钢薄带以35~40℃/h的升温速度升温至退火温度。此处退火温度指的是净化气体退火的退火温度。可以理解的是，上述升温速度可以是上述范围区间的任意值。当然，在其他可能的实现方式中，还可以采用其他升温速度，并不局限于此。In a possible implementation manner, the silicon steel thin strip coated with the annealing isolation layer is heated to an annealing temperature at a heating rate of 35-40° C./h before the annealing of the purification gas. The annealing temperature here refers to the annealing temperature of the purge gas annealing. It can be understood that the above-mentioned heating rate may be any value within the above-mentioned range. Of course, in other possible implementation manners, other heating rates may also be used, which are not limited thereto.
在一种可能的实现方式中，S3中所述退火隔离层的成分为磷酸二氢铝、苯丙乳液、甘油和硅烷偶联剂的混合物，所述混合物中各成分的质量百分含量为：磷酸二氢铝：10~15%，苯丙乳液：20~40%，甘油：25~35%，硅烷偶联剂：10~30%。需要说明的是，上述质量百分含量中简写了起始值，实际上，磷酸二氢铝：10%~15%，苯丙乳液：20%~40%，甘油：25%~35%，硅烷偶联剂：10%~30%。该退火隔离层所采用的混合物可以最大限度地提高硅钢薄带表面的抗氧化性以及硅钢薄带的冲片性能，防止后续产品制备过程中各层别之间的粘结，提高质量。可以理解的是，上述质量百分比可以是上述范围区间的任意值。当然，在其他可能的实现方式中，还可以采用其他成分和质量百分比，并不局限于此。In a possible implementation, the composition of the annealing isolation layer described in S3 is a mixture of aluminum dihydrogen phosphate, styrene-acrylic emulsion, glycerin and a silane coupling agent, and the mass percentage of each composition in the mixture is: Aluminum dihydrogen phosphate: 10~15%, styrene-acrylic emulsion: 20~40%, glycerin: 25~35%, silane coupling agent: 10~30%. It should be noted that the initial value is abbreviated in the above mass percentage. In fact, aluminum dihydrogen phosphate: 10%~15%, styrene-acrylic emulsion: 20%~40%, glycerin: 25%~35%, silane Coupling agent: 10%~30%. The mixture used in the annealing isolation layer can maximize the oxidation resistance of the silicon steel thin strip surface and the punching performance of the silicon steel thin strip, prevent the bonding between layers in the subsequent product preparation process, and improve the quality. It can be understood that the above-mentioned mass percentage can be any value in the above-mentioned range interval. Of course, in other possible implementation manners, other components and mass percentages may also be used, but not limited to this.
在一种可能的实现方式中，S3具体包括步骤：将所述硅钢薄带出辊后水冷至500~600℃，得到第一薄带，将所述第一薄带温轧至0.14~0.17mm，得到第二薄带，将所述第二薄带加热进行真空退火，得到第三薄带，将所述第三薄带再冷轧至0.09~0.12mm，得到第四薄带，将所述第四薄带加热进行纯氢气二次退火，得到第五薄带，将所述第五薄带再空冷至室温，得到第六薄带，将所述第六薄带涂覆退火隔离层，得到第七薄带，将所述第七薄带加热进行净化气体退火，即可得所述强磁性取向高硅钢极薄带。In a possible implementation manner, S3 specifically includes the steps of: water-cooling the silicon steel thin strip to 500-600° C. after being taken out of the roll to obtain a first thin strip, and warmly rolling the first thin strip to 0.14-0.17 mm , obtain a second thin strip, heat the second thin strip for vacuum annealing to obtain a third thin strip, and then cold-roll the third thin strip to 0.09~0.12mm to obtain a fourth thin strip. The fourth thin strip is heated for secondary annealing with pure hydrogen to obtain a fifth thin strip, the fifth thin strip is then air-cooled to room temperature to obtain a sixth thin strip, and the sixth thin strip is coated with an annealing isolation layer to obtain For the seventh thin strip, the seventh thin strip is heated for purification gas annealing to obtain the ferromagnetic oriented high silicon steel ultra-thin strip.
有益效果beneficial effect
相对于现有技术，本申请通过对强磁性取向高硅钢极薄带的原料组分进行设计，采用含硫氮和铜的多核配位化合物和Bi元素作为合金抑制剂，其中含硫氮和铜的多核配位化合物在向合金中引入Cu元素、S元素和N元素的同时，保证了较高的元素吸收率，还能与合金中的其他金属反应生成CuS，AlN，MnS等物质，该类物质可以在浇注初期固液凝固过程中析出，与分布在晶界处的Bi元素共同抑制初次再结晶晶粒的长大，从而促进Goss晶粒发生二次结晶，使所制得的强磁性取向高硅钢极薄带晶粒细小，织构均匀，具有高磁感应强度高、低铁损的优良磁性能。Compared with the prior art, the present application designs the raw material components of the ferromagnetic oriented high-silicon steel ultra-thin strip, and adopts the multi-nuclear coordination compound containing sulfur, nitrogen and copper and the Bi element as the alloy inhibitor. The multi-nuclear coordination compound of the alloy can ensure a high element absorption rate while introducing Cu element, S element and N element into the alloy, and can also react with other metals in the alloy to form CuS, AlN, MnS and other substances. The substance can be precipitated during the solid-liquid solidification process in the initial stage of casting, and together with the Bi element distributed at the grain boundary, suppress the growth of the primary recrystallized grains, thereby promoting the secondary crystallization of the Goss grains and making the obtained strong magnetic orientation. The ultra-thin strip of high silicon steel has fine grains and uniform texture, and has excellent magnetic properties with high magnetic induction intensity and low iron loss.
与现有技术相比，本申请提供的强磁性取向高硅钢极薄带的制备方法在合金的熔炼和甩带过程中均通入了高纯氮气，不仅可以通过高温渗氮作用促进AlN抑制剂的生成，提高织构的生成及合金组织的均匀性，还能阻止合金表面的氧化，与此同时加入含硫氮和铜的多核配位化合物和铋元素，以保证铜元素和铋元素的收得率。高纯氮气在甩带过程中还能作为冷却气体对硅钢薄带的自由面快速降温，加速晶粒的形成，同时经过三次不同的再结晶退火过程，结合表面退火隔离层的涂覆，进一步稳定硅钢薄带的结构，提高硅钢薄带的磁性能、纯净度、表面抗氧化性和冲片性能。Compared with the prior art, the preparation method of the ferromagnetic oriented high-silicon steel ultra-thin strip provided by the present application introduces high-purity nitrogen during the smelting and stripping process of the alloy, which can not only promote the AlN inhibitor through high-temperature nitriding. It can improve the formation of texture and the uniformity of the alloy structure, and can also prevent the oxidation of the alloy surface. At the same time, polynuclear coordination compounds containing sulfur, nitrogen and copper and bismuth elements are added to ensure the recovery of copper and bismuth elements. yield. High-purity nitrogen can also be used as a cooling gas to rapidly cool the free surface of the silicon steel strip during the stripping process and accelerate the formation of grains. At the same time, after three different recrystallization annealing processes, combined with the coating of the surface annealing isolation layer, further stability The structure of silicon steel strip improves the magnetic properties, purity, surface oxidation resistance and punching performance of silicon steel strip.
本申请提供的强磁性取向高硅钢极薄带的制备方法通过连铸、轧制、高温退火、表面改性等一体化工艺路线，进一步发挥了深过冷快速凝固的优势，生产的强磁性取向高硅钢极薄带具有纯净度高、稳定性好、优良的磁性能的特点。The preparation method of the ferromagnetic oriented high silicon steel ultra-thin strip provided by the present application further utilizes the advantages of deep undercooling and rapid solidification through the integrated process route of continuous casting, rolling, high temperature annealing, surface modification, etc. The ultra-thin high silicon steel strip has the characteristics of high purity, good stability and excellent magnetic properties.
本申请的实施方式Embodiments of the present application
为了使本申请所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clear, the present application will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, but not to limit the present application.
实施例1Example 1
本实施例提供了一种强磁性取向高硅钢极薄带，包括以下质量百分比的元素：C：0.0045%、Si：4.5%、Mn：0.23%、S：0.02%、Bi：0.03%、Als：0.027%、Cu:0.02%，N：0.008%，P：0.004%，其余为Fe，其中Cu元素、S元素、N元素在熔炼时以含硫氮和铜的多核配位化合物的方式加入强磁性取向高硅钢极薄带，具体可选用N,N-二正丁基二硫代氨基甲酸铜。This embodiment provides a ferromagnetic oriented high silicon steel ultra-thin strip, which includes the following elements by mass percentage: C: 0.0045%, Si: 4.5%, Mn: 0.23%, S: 0.02%, Bi: 0.03%, Als: 0.027%, Cu: 0.02%, N: 0.008%, P: 0.004%, and the rest is Fe. Among them, Cu element, S element, and N element are ferromagnetically added in the form of multi-nuclear complexes containing sulfur, nitrogen and copper during smelting Oriented high silicon steel ultra-thin strip, specifically N,N-di-n-butyldithiocarbamate can be selected.
本实施例还提供一种强磁性取向高硅钢极薄带的制备方法，具体包括以下步骤：The present embodiment also provides a method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip, which specifically includes the following steps:
S1：按照强磁性取向高硅钢极薄带中各元素的质量百分比准备合金原料，将除Bi元素及含硫氮和铜的多核配位化合物以外的原料混合，置于高温电弧熔炼炉中，加热至1300℃进行熔炼，待合金原料充分熔化后得到合金溶液，向合金溶液表面通入高纯氮气，同时加入N,N-二正丁基二硫代氨基甲酸铜，然后再加入Bi元素，即得硅铁母合金溶液，整个熔炼过程持续30min，其中Bi元素可通过Bi粉的方式加入合金溶液；S1: Prepare alloy raw materials according to the mass percentage of each element in the ferromagnetic oriented high silicon steel ultra-thin strip, mix the raw materials except Bi element and polynuclear complexes containing sulfur, nitrogen and copper, and place them in a high-temperature arc melting furnace. Smelting at 1300 ℃, after the alloy raw materials are fully melted, an alloy solution is obtained, and high-purity nitrogen gas is introduced into the surface of the alloy solution, and N,N-di-n-butyldithiocarbamate is added at the same time, and then Bi element is added, namely The ferrosilicon master alloy solution is obtained, and the whole smelting process lasts for 30 minutes, in which the Bi element can be added to the alloy solution by means of Bi powder;
S2：将硅铁母合金溶液的温度控制在1100℃，在持续流动的高纯氮气氛围中进行高速极冷单辊甩带，控制高速极冷单辊甩带过程中辊的线速度为20m/s，制备出厚度为0.25mm的硅钢薄带；S2: Control the temperature of the ferrosilicon master alloy solution at 1100°C, carry out high-speed extremely cold single roll stripping in a continuously flowing high-purity nitrogen atmosphere, and control the linear speed of the roller during the high-speed extremely cold single roll stripping process to 20m/ s, to prepare a silicon steel strip with a thickness of 0.25mm;
S3：先将硅钢薄带从甩带机的辊上取出，然后将出辊后的硅钢薄带水冷至500℃，温轧至0.17mm，以20℃/h的加热速度加热至850℃后进行真空退火2min，再冷轧至0.12mm厚，然后以20℃/h的加热速度加热至1000℃后进行纯氢气二次退火2min，再空冷至室温，在涂覆退火隔离层后，以35℃/h的加热速度加热至950℃，然后进行净化气体退火，在净化气体退火3min后即得强磁性取向高硅钢极薄带，退火隔离层的成分为由质量百分比为10%的磷酸二氢铝、40%的苯丙乳液、35%的甘油和15%的硅烷偶联剂组成的混合物。S3: First take out the silicon steel thin strip from the roll of the stripping machine, then water-cool the silicon steel thin strip after the roll to 500°C, warmly roll it to 0.17mm, and heat it to 850°C at a heating rate of 20°C/h. Vacuum annealed for 2 minutes, then cold rolled to 0.12mm thick, then heated to 1000°C at a heating rate of 20°C/h, followed by secondary annealing with pure hydrogen for 2 minutes, and then air-cooled to room temperature. The heating rate of /h is heated to 950 ℃, and then purified gas annealing is carried out. After 3 minutes of purification gas annealing, a ferromagnetic oriented high silicon steel ultra-thin strip is obtained. The composition of the annealing isolation layer is 10% by mass of aluminum dihydrogen phosphate. , 40% styrene-acrylic emulsion, 35% glycerol and 15% silane coupling agent.
实施例2Example 2
本实施例提供了一种强磁性取向高硅钢极薄带，包括以下质量百分比的元素：C：0.0060%、Si：5.0%、Mn：0.32%、S：0.03%、Bi：0.08%、Als：0.035%、Cu:0.03%，N：0.0010%，P：0.002%，其余为Fe，其中Cu元素、S元素、N元素在熔炼时以含硫氮和铜的多核配位化合物的方式加入强磁性取向高硅钢极薄带，具体可选用双(1-氮杂环基)二硫代氨基甲酸铜(Ⅱ)。This embodiment provides a ferromagnetic oriented high silicon steel ultra-thin strip, including the following elements by mass percentage: C: 0.0060%, Si: 5.0%, Mn: 0.32%, S: 0.03%, Bi: 0.08%, Als: 0.035%, Cu: 0.03%, N: 0.0010%, P: 0.002%, and the rest is Fe. Among them, Cu element, S element, and N element are ferromagnetically added in the form of multi-nuclear complexes containing sulfur, nitrogen and copper during smelting For the ultra-thin strip of oriented high-silicon steel, bis(1-aza-heterocyclyl)dithiocarbamate (II) can be specifically selected.
本实施例还提供一种强磁性取向高硅钢极薄带的制备方法，具体包括以下步骤：The present embodiment also provides a method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip, which specifically includes the following steps:
S1：按照强磁性取向高硅钢极薄带中各元素的质量百分比准备合金原料，将除Bi元素及含硫氮和铜的多核配位化合物以外的原料混合，置于高温电弧熔炼炉中，加热至1500℃进行熔炼，待合金原料充分熔化后得到合金溶液，向合金溶液表面通入高纯氮气，同时加入双(1-氮杂环基)二硫代氨基甲酸铜(Ⅱ)，然后再加入Bi元素，即得硅铁母合金溶液，整个熔炼过程持续120min，其中Bi元素可通过Bi粉的方式加入合金溶液；S1: Prepare alloy raw materials according to the mass percentage of each element in the ferromagnetic oriented high silicon steel ultra-thin strip, mix the raw materials except Bi element and polynuclear complexes containing sulfur, nitrogen and copper, and place them in a high-temperature arc melting furnace. Smelting at 1500°C. After the alloy raw materials are fully melted, an alloy solution is obtained. High-purity nitrogen gas is introduced into the surface of the alloy solution. Bi element, that is, the master alloy solution of ferrosilicon is obtained, and the whole smelting process lasts for 120min, in which Bi element can be added to the alloy solution by means of Bi powder;
S2：将硅铁母合金溶液的温度控制在1200℃，在持续流动的高纯氮气氛围中进行高速极冷单辊甩带，控制高速极冷单辊甩带过程中辊的线速度为30m/s，制备出厚度为0.20mm的硅钢薄带；S2: Control the temperature of the ferrosilicon master alloy solution at 1200°C, and carry out high-speed extremely cold single roll stripping in a continuous flow of high-purity nitrogen atmosphere. s, to prepare a silicon steel strip with a thickness of 0.20 mm;
S3：先将硅钢薄带从甩带机的辊上取出，然后将出辊后的硅钢薄带水冷至600℃，温轧至0.14mm，以20℃/h的加热速度加热至1050℃后进行真空退火5min，再冷轧至0.09mm厚后，然后以25℃/h的加热速度加热至1150℃后进行纯氢气二次退火5min，再空冷至室温，在涂覆退火隔离层后，以40℃/h的速度加热至1200℃，然后进行净化气体退火，在净化气体退火5min后即得强磁性取向高硅钢极薄带，退火隔离层的成分为由质量百分比为15%的磷酸二氢铝、30%的苯丙乳液、25%的甘油和30%的硅烷偶联剂组成的混合物。S3: First take out the silicon steel thin strip from the roll of the strip machine, and then water-cool the silicon steel thin strip after the roll to 600°C, warmly roll it to 0.14mm, and heat it to 1050°C at a heating rate of 20°C/h. Vacuum annealed for 5 minutes, then cold rolled to 0.09mm thick, then heated to 1150°C at a heating rate of 25°C/h, followed by secondary annealing with pure hydrogen for 5 minutes, and then air-cooled to room temperature. ℃/h speed heating to 1200 ℃, and then annealing with purification gas. After annealing in purification gas for 5 minutes, a ferromagnetic oriented high silicon steel ultra-thin strip is obtained. The composition of the annealing isolation layer is 15% by mass of aluminum dihydrogen phosphate. , 30% styrene-acrylic emulsion, 25% glycerin and 30% silane coupling agent.
实施例3Example 3
本实施例提供了一种强磁性取向高硅钢极薄带，包括以下质量百分比的元素：C：0.0050%、Si：4.5%、Mn：0.28%、S：0.02%、Bi：0.05%、Als：0.030%、Cu:0.02%，N：0.008%，P：0.004%，其余为Fe，其中Cu元素、S元素、N元素在熔炼时以含硫氮和铜的多核配位化合物的方式加入强磁性取向硅钢极薄带，具体可选用{Cu(NH 3) 4}SO 4。 This embodiment provides a ferromagnetic oriented high silicon steel ultra-thin strip, including the following elements by mass percentage: C: 0.0050%, Si: 4.5%, Mn: 0.28%, S: 0.02%, Bi: 0.05%, Als: 0.030%, Cu: 0.02%, N: 0.008%, P: 0.004%, and the rest is Fe. Among them, Cu element, S element, and N element are ferromagnetically added in the form of multinuclear complexes containing sulfur, nitrogen and copper during smelting Oriented silicon steel ultra-thin strip, specifically, {Cu(NH 3 ) 4 }SO 4 can be selected.
本实施例还提供一种强磁性取向高硅钢极薄带的制备方法，具体包括以下步骤：The present embodiment also provides a method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip, which specifically includes the following steps:
S1：按照强磁性取向高硅钢极薄带中各元素的质量百分比准备合金原料，将除Bi元素及含硫氮和铜的多核配位化合物以外的原料混合，置于高温电弧熔炼炉中，加热至1400℃进行熔炼，待合金原料充分熔化后得到合金溶液，向合金溶液表面通入高纯氮气，同时加入{Cu(NH 3) 4}SO 4，然后再加入Bi元素，即得硅铁母合金溶液，整个熔炼过程持续60min，其中Bi元素可通过Bi粉的方式加入合金溶液； S1: Prepare alloy raw materials according to the mass percentage of each element in the ferromagnetic oriented high silicon steel ultra-thin strip, mix the raw materials except Bi element and polynuclear complexes containing sulfur, nitrogen and copper, put them in a high temperature arc melting furnace, heat Smelting at 1400°C, after the alloy raw materials are fully melted, an alloy solution is obtained, high-purity nitrogen is introduced into the surface of the alloy solution, {Cu(NH 3 ) 4 }SO 4 is added at the same time, and then Bi element is added to obtain ferrosilicon mother Alloy solution, the whole smelting process lasts 60min, in which Bi element can be added to the alloy solution by way of Bi powder;
S2：将硅铁母合金溶液的温度控制在1150℃，在持续流动的高纯氮气氛围中进行高速极冷单辊甩带，控制高度极冷单辊甩带过程中辊的线速度为25m/s，制备出厚度为0.22mm的硅钢薄带；S2: Control the temperature of the ferrosilicon master alloy solution at 1150°C, and carry out high-speed extremely cold single roll stripping in a continuous flow of high-purity nitrogen atmosphere, and control the linear speed of the roll during the process of highly extremely cold single roll stripping to 25m/ s, to prepare a silicon steel strip with a thickness of 0.22 mm;
S3：先将硅钢薄带从甩带机的辊上取出，然后将出辊后的硅钢薄带水冷至500℃，温轧至0.15mm厚，以20℃/h的加热速度加热至950℃后进行真空退火2min，再冷轧至0.10mm厚，然后以25℃/h的加热速度加热至1080℃后进行纯氢气二次退火2min，再空冷至室温，在涂覆退火隔离层后，以35℃/h的速度加热至1080℃，然后进行净化气体退火，在净化气体退火3min后即得强磁性取向高硅钢极薄带，退火隔离层的成分为由质量百分比为15%的磷酸二氢铝、20%的苯丙乳液、35%的甘油和30%的硅烷偶联剂组成的混合物。S3: First take out the silicon steel thin strip from the roll of the strip machine, then water-cool the silicon steel thin strip after the roll to 500°C, warmly roll it to a thickness of 0.15mm, and heat it to 950°C at a heating rate of 20°C/h. Vacuum annealed for 2 min, then cold rolled to 0.10mm thick, then heated to 1080°C at a heating rate of 25°C/h, followed by secondary annealing with pure hydrogen for 2min, and then air-cooled to room temperature. ℃/h speed heating to 1080 ℃, and then annealing with purification gas. After annealing in purification gas for 3 minutes, a ferromagnetic oriented high silicon steel ultra-thin strip is obtained. The composition of the annealing isolation layer is 15% by mass of aluminum dihydrogen phosphate. , 20% styrene-acrylic emulsion, 35% glycerol and 30% silane coupling agent.
对比例1Comparative Example 1
本对比例提供一种强磁性取向高硅钢极薄带和一种强磁性取向高硅钢极薄带的制备方法，除强磁性取向高硅钢极薄带中的Cu元素、S元素、N元素在熔炼时以普通合金原料的方式加入强磁性取向高硅钢极薄带外，其他成分和制备工艺与实施例3相同。This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip. The other components and preparation process are the same as those in Example 3, except that the ferromagnetic oriented high silicon steel ultra-thin strip is added in the form of ordinary alloy raw materials.
对比例2Comparative Example 2
本对比例提供一种强磁性取向高硅钢极薄带和一种强磁性取向高硅钢极薄带的制备方法，除强磁性取向高硅钢极薄带不含Bi元素外，其他成分和制备工艺与实施例3相同。This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip. Example 3 is the same.
对比例3Comparative Example 3
本对比例提供一种强磁性取向高硅钢极薄带和一种强磁性取向高硅钢极薄带的制备方法，除强磁性取向高硅钢极薄带的制备方法中，真空退火温度为1100℃，纯氢气二次退火温度为1200℃，净化气体退火温度为1250℃外，其他成分和制备工艺与实施例3相同。This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip. Except that the secondary annealing temperature of pure hydrogen is 1200°C, and the annealing temperature of purified gas is 1250°C, other components and preparation processes are the same as those in Example 3.
对比例4： Comparative Example 4:
本对比例提供一种强磁性取向高硅钢极薄带和一种强磁性取向高硅钢极薄带的制备方法，除强磁性取向高硅钢极薄带的制备方法中，真空退火前硅钢薄带的加热速度为35℃/h，纯氢气二次退火前硅钢薄带的加热速度为35℃/h外，其他成分和制备工艺与实施例3相同。This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip, except that in the preparation method of the ferromagnetic oriented high-silicon steel ultra-thin strip, the The heating rate is 35°C/h, and the heating rate of the silicon steel strip before the secondary annealing with pure hydrogen is 35°C/h, and other components and preparation processes are the same as those in Example 3.
对比例5 Comparative Example 5
本对比例提供一种强磁性取向高硅钢极薄带和一种强磁性取向高硅钢极薄带的制备方法，除强磁性取向高硅钢极薄带的制备方法中，S3中所涂覆的退火隔离层成分为氧化镁外，其他成分和制备工艺与实施例3相同。This comparative example provides a ferromagnetic oriented high silicon steel ultra-thin strip and a preparation method of a ferromagnetic oriented high-silicon steel ultra-thin strip. Except that the component of the isolation layer is magnesium oxide, other components and preparation process are the same as those in Example 3.
检测例：分别对实施例和对比例中所得的高硅钢极薄带的饱和磁感应强度和铁损进行检测，测试结果如表1所示：Test example: The saturation magnetic induction intensity and iron loss of the high silicon steel ultra-thin strip obtained in the embodiment and the comparative example are respectively tested, and the test results are shown in Table 1:
表1Table 1
Figure dest_path_image001
Figure dest_path_image001
从表1中的检测数据可以看出，本申请实施例得到的强磁性取向高硅钢极薄带的晶粒细小，组织均匀，磁感性能B800为＞1.90T，铁损P1.7/50值小于0.90W/kg、P1.0/400值小于8.5W/kg，具有优良的磁感性能。From the test data in Table 1, it can be seen that the ultra-thin ferromagnetic oriented high-silicon steel strips obtained in the examples of the present application have fine grains, uniform structure, magnetic induction performance B800 >1.90T, and iron loss P1.7/50 value Less than 0.90W/kg, P1.0/400 value less than 8.5W/kg, with excellent magnetic induction performance.
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。The above descriptions are only preferred embodiments of the present application, and are not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the protection of the present application. within the range.

Claims (11)

  1. 一种强磁性取向高硅钢极薄带，其特征在于，所述强磁性取向高硅钢极薄带包含以下质量百分比的元素：C：0.0045%~0.0060%，Si：4.5%~5.0%，Mn：0.23%~0.32%，S：0.02%~0.03%，Bi：0.03%~0.08%，Als：0.027%~0.035%，Cu：0.02%~0.03%，N：0.008%~0.010%，P＜0.005%，其余为铁，其中所述Cu元素、所述S元素、所述N元素在熔炼时以含硫氮和铜的多核配位化合物的方式加入所述强磁性取向高硅钢极薄带。An ultra-thin strip of ferromagnetically oriented high-silicon steel, characterized in that the ultra-thin strip of ferromagnetically oriented high-silicon steel contains the following elements by mass percentage: C: 0.0045%-0.0060%, Si: 4.5%-5.0%, Mn: 0.23%~0.32%, S: 0.02%~0.03%, Bi: 0.03%~0.08%, Als: 0.027%~0.035%, Cu: 0.02%~0.03%, N: 0.008%~0.010%, P＜0.005% , and the rest is iron, wherein the Cu element, the S element, and the N element are added to the ferromagnetic oriented high silicon steel ultra-thin strip in the form of a multi-nuclear complex containing sulfur, nitrogen and copper during smelting.
  2. 一种权利要求1所述的强磁性取向高硅钢极薄带的制备方法，具体包括以下步骤：A preparation method of the ferromagnetically oriented high silicon steel ultra-thin strip of claim 1, specifically comprising the following steps:
    S1：按照权利要求1所述强磁性取向高硅钢极薄带中各元素的质量百分比准备原料，将除所述Bi元素及所述含硫氮和铜的多核配位化合物的以外的原料混合熔炼，待合金原料完全熔化后得到合金溶液，向所述合金溶液表面通入高纯氮气，同时加入所述含硫氮和铜的多核配位化合物，然后再加入所述Bi元素，制得硅铁母合金溶液；S1: Prepare raw materials according to the mass percentage of each element in the ferromagnetic oriented high silicon steel ultra-thin strip according to claim 1, and mix and smelt raw materials other than the Bi element and the polynuclear complex containing sulfur, nitrogen and copper , after the alloy raw materials are completely melted, an alloy solution is obtained, high-purity nitrogen is introduced into the surface of the alloy solution, and the multi-nuclear complex containing sulfur, nitrogen and copper is added at the same time, and then the Bi element is added to obtain ferrosilicon. master alloy solution;
    S2：将所述硅铁母合金溶液的温度控制在1100~1200℃，在持续流动的高纯氮气氛围中进行高速单辊甩带，控制所述高速单辊甩带过程中辊的线速度为20~30m/s，制备出0.20~0.25mm厚的硅钢薄带；S2: control the temperature of the ferrosilicon mother alloy solution at 1100-1200°C, carry out high-speed single-roller stripping in a continuous flow of high-purity nitrogen atmosphere, and control the linear speed of the roller during the high-speed single-roller stripping process to be 20~30m/s, to prepare a silicon steel strip with a thickness of 0.20~0.25mm;
    S3：将所述硅钢薄带出辊后水冷至500~600℃，温轧至0.14~0.17mm，加热进行真空退火；再冷轧至0.09~0.12mm，加热进行纯氢气二次退火，再空冷至室温，涂覆退火隔离层后加热进行净化气体退火，即得所述强磁性取向高硅钢极薄带。S3: After the thin silicon steel strip is taken out of the roll, water-cooled to 500-600°C, warm-rolled to 0.14-0.17mm, heated for vacuum annealing; cold-rolled to 0.09-0.12mm, heated for secondary annealing with pure hydrogen, and then air-cooled When the temperature is reached to room temperature, the annealing isolation layer is coated and then heated for purification gas annealing to obtain the ferromagnetic oriented high silicon steel ultra-thin strip.
  3. 根据权利要求2所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，S1中所述混合熔炼的温度为1300~1500℃。The method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip according to claim 2, wherein the temperature of the mixed smelting in S1 is 1300-1500°C.
  4. 根据权利要求2所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，S3中所述真空退火的温度为850~1050℃，所述真空退火的时间为2~5min。The method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip according to claim 2, wherein the temperature of the vacuum annealing in S3 is 850-1050° C., and the time of the vacuum annealing is 2-5 min.
  5. 根据权利要求4所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，所述真空退火前将完成温轧的所述硅钢薄带以20~25℃/h的升温速度升温至退火温度。The method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip according to claim 4, characterized in that, before the vacuum annealing, the warm-rolled silicon steel strip is heated at a heating rate of 20-25°C/h to Annealing temperature.
  6. 根据权利要求2所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，S3中所述纯氢气二次退火的温度为1000~1150℃，所述纯氢气二次退火的时间为2~5min。The method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip according to claim 2, wherein the temperature of the secondary annealing with pure hydrogen in S3 is 1000-1150°C, and the secondary annealing time with pure hydrogen is 2~5min.
  7. 根据权利要求6所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，所述纯氢气二次退火前将完成冷轧的所述硅钢薄带以20~25℃/h的升温速度升温至退火温度。The method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip according to claim 6, characterized in that, before the pure hydrogen secondary annealing, the cold-rolled silicon steel strip is heated at a temperature of 20-25°C/h Speed up to annealing temperature.
  8. 根据权利要求2所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，S3中所述净化气体退火的温度为950~1200℃，所述净化气体退火的时间为3~5min。The method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip according to claim 2, wherein the temperature of the annealing in the purification gas in S3 is 950-1200° C., and the time of the annealing in the purification gas is 3-5 min.
  9. 根据权利要求8所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，所述净化气体退火前将涂敷所述退火隔离层的所述硅钢薄带以35~40℃/h的升温速度升温至退火温度。The method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip according to claim 8, wherein the silicon steel strip coated with the annealing isolation layer is heated at a temperature of 35-40° C./h before the purification gas annealing. The heating rate is increased to the annealing temperature.
  10. 根据权利要求2所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，S3中所述退火隔离层为磷酸二氢铝、苯丙乳液、甘油和硅烷偶联剂的混合物；The method for preparing a ferromagnetic oriented high silicon steel ultra-thin strip according to claim 2, wherein the annealing isolation layer described in S3 is a mixture of aluminum dihydrogen phosphate, styrene-acrylic emulsion, glycerin and a silane coupling agent;
    所述混合物中各成分的质量百分含量为：磷酸二氢铝：10~15%，苯丙乳液：20~40%，甘油：25~35%，硅烷偶联剂：10~30%。The mass percentage of each component in the mixture is: aluminum dihydrogen phosphate: 10-15%, styrene-acrylic emulsion: 20-40%, glycerin: 25-35%, silane coupling agent: 10-30%.
  11. 根据权利要求2所述的强磁性取向高硅钢极薄带的制备方法，其特征在于，S3具体包括步骤：The preparation method of the ferromagnetic oriented high silicon steel ultra-thin strip according to claim 2, characterized in that, S3 specifically comprises the steps:
    将所述硅钢薄带出辊后水冷至500~600℃，得到第一薄带，将所述第一薄带温轧至0.14~0.17mm，得到第二薄带，将所述第二薄带加热进行真空退火，得到第三薄带，将所述第三薄带再冷轧至0.09~0.12mm，得到第四薄带，将所述第四薄带加热进行纯氢气二次退火，得到第五薄带，将所述第五薄带再空冷至室温，得到第六薄带，将所述第六薄带涂覆退火隔离层，得到第七薄带，将所述第七薄带加热进行净化气体退火，即可得所述强磁性取向高硅钢极薄带。After the silicon steel thin strip is taken out of the roll, it is water-cooled to 500-600° C. to obtain a first thin strip, and the first thin strip is warmly rolled to 0.14-0.17 mm to obtain a second thin strip. The second thin strip is heating for vacuum annealing to obtain a third thin strip, cold rolling the third thin strip to 0.09-0.12 mm to obtain a fourth thin strip, heating the fourth thin strip to perform secondary annealing with pure hydrogen to obtain the first thin strip Five thin strips, the fifth thin strip is air-cooled to room temperature again to obtain a sixth thin strip, the sixth thin strip is coated with an annealing isolation layer to obtain a seventh thin strip, and the seventh thin strip is heated for Purifying gas annealing, the ferromagnetic oriented high silicon steel ultra-thin strip can be obtained.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07179942A (en) * 1993-12-24 1995-07-18 Nippon Steel Corp Production of grain-oriented silicon steel sheet
CN103911545A (en) * 2014-04-14 2014-07-09 国家电网公司 Preparation method of electrical steel strip with strong goss texture occupation rate and high magnetic induction orientation
JP2014167147A (en) * 2013-02-28 2014-09-11 Jfe Steel Corp Method for producing grain-oriented electromagnetic steel sheets
CN108456767A (en) * 2017-12-21 2018-08-28 东北大学 A kind of preparation method being orientated high silicon steel strip material
CN109097677A (en) * 2018-08-07 2018-12-28 东北大学 High magentic induction oriented high silicon steel plate strip of one kind and preparation method thereof
CN112962028A (en) * 2021-02-01 2021-06-15 河北科技大学 Strong magnetic orientation high-silicon steel ultra-thin strip and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0649542A (en) * 1992-07-29 1994-02-22 Nippon Steel Corp Production of high magnetic flux density grain-oriented silicon steel sheet
JPH07258737A (en) * 1994-03-18 1995-10-09 Nippon Steel Corp Production of grain-oriented magnetic steel sheet having high magnetic flux density
JPH08225842A (en) * 1995-02-15 1996-09-03 Nippon Steel Corp Production of grain-oriented silicon steel sheet
JP2001047194A (en) * 1999-08-12 2001-02-20 Kawasaki Steel Corp Production of high magnetic flux density grain oriented silicon steel sheet having extremely low iron loss

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07179942A (en) * 1993-12-24 1995-07-18 Nippon Steel Corp Production of grain-oriented silicon steel sheet
JP2014167147A (en) * 2013-02-28 2014-09-11 Jfe Steel Corp Method for producing grain-oriented electromagnetic steel sheets
CN103911545A (en) * 2014-04-14 2014-07-09 国家电网公司 Preparation method of electrical steel strip with strong goss texture occupation rate and high magnetic induction orientation
CN108456767A (en) * 2017-12-21 2018-08-28 东北大学 A kind of preparation method being orientated high silicon steel strip material
CN109097677A (en) * 2018-08-07 2018-12-28 东北大学 High magentic induction oriented high silicon steel plate strip of one kind and preparation method thereof
CN112962028A (en) * 2021-02-01 2021-06-15 河北科技大学 Strong magnetic orientation high-silicon steel ultra-thin strip and preparation method thereof

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