CN112962028B - Strong magnetic orientation high-silicon steel ultra-thin strip and preparation method thereof - Google Patents

Strong magnetic orientation high-silicon steel ultra-thin strip and preparation method thereof Download PDF

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CN112962028B
CN112962028B CN202110137389.4A CN202110137389A CN112962028B CN 112962028 B CN112962028 B CN 112962028B CN 202110137389 A CN202110137389 A CN 202110137389A CN 112962028 B CN112962028 B CN 112962028B
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silicon steel
thin strip
annealing
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ferromagnetic
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CN112962028A (en
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王波
张迪
孙会兰
郭志红
朱立光
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Hebei University of Science and Technology
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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
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    • 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
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    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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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
    • 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
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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
    • C21D8/1216—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
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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
    • C21D8/1216—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
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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
    • C21D8/1244—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
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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
    • C22C38/002—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

Abstract

The invention provides a ferromagnetic oriented high-silicon steel ultra-thin strip and a preparation method thereof, belonging to the field of electrical steel manufacturing, wherein the ferromagnetic oriented high-silicon steel ultra-thin strip comprises the following elements in percentage by mass: 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 is less than 0.005%, and the balance is iron, wherein the Cu, S and N elements are added into the high-silicon steel in a way of a polynuclear coordination compound containing sulfur, nitrogen and copper during smelting; according to the invention, through designing the raw material components of the oriented high silicon steel and adopting the polynuclear coordination compound containing sulfur, nitrogen and copper and the Bi element as alloy inhibitors, the prepared ferromagnetic oriented high silicon steel ultra-thin strip has fine grains, uniform tissues, high magnetic induction intensity and excellent magnetic performance of low iron loss.

Description

Strong magnetic orientation high-silicon steel ultra-thin strip and preparation method thereof
Technical Field
The invention belongs to the field of electrical steel manufacturing, and particularly relates to a ferromagnetic oriented high-silicon steel ultra-thin strip and a preparation method thereof.
Background
Oriented silicon steel is an important soft magnetic material, is an important preparation raw material of a transformer iron core, and is one of indispensable materials for the development of the power industry. The characteristics of high silicon steel, low iron loss and low magnetostriction coefficient, show outstanding superiority in high frequency devices such as high speed high frequency motors, audio and high frequency transformers, choke coils, magnetic shields at high frequencies, and the like. In addition, the high silicon steel is adopted to replace the common cold-rolled oriented silicon steel, so that the working frequency and the sensitivity of electronic and electrical components can be improved, the weight and the volume of electrical equipment can be greatly reduced, the high silicon steel is clean and noiseless, the energy consumption is saved, and the contradiction between high efficiency, energy conservation, portability and cleanness and noiseless is effectively solved.
The thin strip continuous casting method can directly produce thin strips by using liquid alloy, is a short-process metal thin strip preparation process with great potential, the casting process takes a casting roller as a crystallizer, alloy liquid is in direct contact with the casting roller, the solidification structure and the texture of the prepared oriented silicon steel are obviously different from those of the traditional continuous casting billet, the sub-rapid solidification characteristic can fully inhibit the coarsening process of second-phase particles, the defect of high-temperature heating of the oriented silicon steel billet is fundamentally solved, favorable conditions are provided for the fine, uniform and dispersed distribution of an inhibitor required by the preparation of the oriented silicon steel, the technology is successfully applied to the production of processes of low-carbon steel, high-speed steel and the like, but in the production of the oriented high-silicon steel, the requirements on the solidification structure, the precipitation of the inhibitor, the cold processing plasticity and the like are higher, and the problems are difficult to overcome, so that the oriented high-silicon steel in the prior art still has low purity, Poor stability, low magnetic induction and high iron loss.
Disclosure of Invention
Aiming at the defects of low purity, poor stability and poor magnetic performance of the strong magnetic orientation high silicon steel in the prior art, the invention provides a strong magnetic orientation high silicon steel ultra-thin strip and a preparation method thereof. The high silicon steel ultra-thin strip has the advantages of fine crystal grains, uniform structure, high magnetic induction intensity, low iron loss and excellent magnetic performance.
In order to achieve the purpose, the embodiment of the invention adopts the following technical scheme:
a ferromagnetic orientation high silicon steel ultra-thin strip comprises the following elements in percentage by mass:
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 is less than 0.005%, and the balance is iron, wherein the Cu element is added into the ferromagnetic oriented silicon steel ultra-thin strip in a way of a multi-core coordination compound containing sulfur, nitrogen and copper during smelting.
Compared with the prior art, the raw material components of the oriented high-silicon steel ultra-thin strip are designed, the multi-core coordination compound containing sulfur, nitrogen and copper and the Bi element are used as alloy inhibitors, the multi-core coordination compound containing sulfur, nitrogen and copper ensures high element absorption rate while introducing Cu, S and N elements into the alloy, and can react with other metals in the alloy to generate substances such as CuS, AlN, MnS and the like, the substances can be separated out in the solid-liquid solidification process at the initial casting stage and inhibit the growth of primary recrystallized grains together with the Bi element distributed at the grain boundary, so that secondary crystallization of Goss grains is promoted, and the prepared oriented high-silicon steel ultra-thin strip has fine grains, uniform texture, high magnetic induction strength and excellent magnetic performance of low iron loss.
The embodiment of the invention also provides a preparation method of the ferromagnetic oriented high-silicon steel ultra-thin strip, which comprises the following steps:
s1: preparing raw materials according to the mass percentage of each element in the ferromagnetic orientation high-silicon steel ultra-thin strip, mixing and smelting the raw materials except for Bi element and a polynuclear coordination compound containing sulfur, nitrogen and copper, obtaining an alloy solution after the alloy is completely melted, introducing high-purity nitrogen to the surface of the alloy solution, simultaneously adding the polynuclear coordination compound containing sulfur, nitrogen and copper, and then adding Bi element to prepare the ferrosilicon master alloy solution, wherein the Bi element can be added into the alloy solution in a Bi powder mode;
s2: controlling the temperature of the ferrosilicon master alloy solution at 1100-1200 ℃, carrying out high-speed single-roller melt spinning in continuously flowing high-purity nitrogen, and controlling the linear speed of rollers at 20-30 m/s to prepare a silicon steel thin strip with the thickness of 0.20-0.25 mm;
s3: taking the silicon steel thin strip out of the roller, cooling the silicon steel thin strip to 500-600 ℃ with water, warm rolling the silicon steel thin strip to 0.14-0.17 mm, and heating the silicon steel thin strip for vacuum annealing; and then rolling to 0.09-0.12 mm, heating for secondary annealing with pure hydrogen, air cooling to room temperature, coating an annealing isolation layer, heating for purifying gas and annealing to obtain the ferromagnetic oriented high-silicon steel ultra-thin strip.
Compared with the prior art, the preparation method of the ferromagnetic orientation high-silicon steel strip provided by the invention has the advantages that high-purity nitrogen is introduced in the alloy smelting and strip throwing processes, the generation of an AlN inhibitor can be promoted through the high-temperature nitriding effect, the generation of the texture and the uniformity of the alloy structure are improved, the oxidation of the alloy surface can be prevented, and meanwhile, the multi-core coordination compound containing sulfur, nitrogen and copper and bismuth element are added, so that the yield of the copper and bismuth element is ensured. The high-purity nitrogen can also be used as cooling gas to rapidly cool the free surface of the thin strip in the strip throwing process so as to accelerate the formation of crystal grains, and meanwhile, the structure of the thin strip is further stabilized by three different recrystallization annealing processes and the coating of the surface isolating layer, so that the magnetic property, the purity, the surface oxidation resistance and the punching performance of the thin strip are improved.
The preparation method of the ferromagnetic oriented high-silicon steel ultra-thin strip further exerts the advantage of deep super-cooling rapid solidification through the integrated process routes of continuous casting, rolling, high-temperature annealing, surface modification and the like, and the produced oriented silicon steel ultra-thin strip has high purity, good stability and excellent magnetic performance.
Preferably, the smelting of the alloy raw material in S1 is performed in a smelting furnace, optionally a high temperature arc smelting furnace.
Preferably, the temperature of the mixed smelting in S1 is 1300-1500 ℃.
The optimized melting temperature and melting time can ensure that the alloy raw materials are fully melted and uniformly mixed, and a silicon steel thin strip with uniform structure and property is formed in the strip throwing process.
Preferably, the vacuum annealing temperature in S3 is 850-1050 ℃, and the vacuum annealing time is 2-5 min.
The optimized vacuum annealing temperature and annealing time can make the redundant C, Si element oxide in the silicon steel precipitate to the surface of the silicon steel to form an oxide layer and remove the oxide layer in the cold rolling process, thereby further improving the workability and toughness of the silicon steel strip.
Preferably, before the vacuum annealing, the temperature of the silicon steel ultra-thin strip subjected to warm rolling is increased to the annealing temperature at a temperature increasing speed of 20-25 ℃/H.
The optimal temperature rise speed can reduce the temperature gradient between the silicon steel thin strip layers, is beneficial to the generation of oxide on the surface C, Si of the steel strip, improves the uniformity of the surface oxide layer, and also provides the optimal dynamic condition for the formation of texture and structure in the vacuum annealing process.
Preferably, the temperature of the pure hydrogen secondary annealing in S3 is 1000-1150 ℃, and the time of the pure hydrogen secondary annealing is 2-5 min.
The optimized secondary annealing temperature and annealing time of pure hydrogen can ensure that Goss crystal grains in the strip steel are fully swallowed and other crystal grains grow abnormally, a perfect secondary recrystallization texture is formed, and the magnetic performance of the obtained secondary annealing plate is improved.
Preferably, before the secondary annealing of the pure hydrogen, the temperature of the silicon steel ultra-thin strip subjected to the cold rolling is increased to the annealing temperature at a temperature increasing speed of 20-25 ℃/H.
The preferable temperature rise speed can reduce the temperature gradient among the thin strip layers, provide proper conditions for Goss crystal grains in the structure to swallow other crystal grains, improve the uniformity of the structure in the thin strip and improve the magnetic performance of the thin strip.
Preferably, the temperature of the purge gas annealing in S3 is 950-1200 ℃, and the purge gas annealing time is 3-5 min.
Preferably, before the purge gas annealing, the silicon steel ultra-thin strip coated with the annealing isolation layer is heated to the annealing temperature at a heating rate of 35-40 ℃/H.
Preferably, the isolating layer in S3 is a mixture of aluminum dihydrogen phosphate, styrene-acrylic emulsion, glycerin, and a silane coupling agent, and the mass percentages of the components are: aluminum dihydrogen phosphate: 10-15%, styrene-acrylic emulsion: 20-40%, glycerin: 25-35%, silane coupling agent: 10 to 30 percent.
The preferable isolating layer mixture can improve the oxidation resistance of the surface of the silicon steel and the punching performance of the silicon steel to the maximum extent, prevent the adhesion among layers in the subsequent product preparation process and improve the quality.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a ferromagnetic oriented high-silicon steel ultra-thin strip which comprises the following elements in percentage by mass: 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 percent of the alloy, and the balance of Fe, wherein Cu, S and N elements are added into the ferromagnetic oriented silicon steel ultra-thin strip in a way of a polynuclear coordination compound containing sulfur, nitrogen and copper during smelting, and particularly, N-di-N-butyl copper dithiocarbamate can be selected.
The embodiment also provides a preparation method of the ferromagnetic orientation high-silicon steel ultra-thin strip, which specifically comprises the following steps:
s1: preparing alloy raw materials according to the mass percentage of each element in the ferromagnetic orientation high-silicon steel, mixing the raw materials except for Bi element and a polynuclear coordination compound containing sulfur, nitrogen and copper, placing the mixture in a high-temperature electric arc melting furnace, heating the mixture to 1300 ℃ for melting, obtaining an alloy solution after the alloy raw materials are fully melted, introducing high-purity nitrogen to the surface of the alloy solution, simultaneously adding N, N-di-N-butyl copper dithiocarbamate, and then adding Bi element to obtain the ferrosilicon master alloy, wherein the whole melting process lasts for 30min, and the Bi element can be added into the alloy solution in a Bi powder mode;
s2: controlling the temperature of the ferrosilicon master alloy liquid at 1100 ℃, carrying out high-speed ultra-cold single-roller melt spinning in a continuously flowing high-purity nitrogen atmosphere, controlling the linear speed of a roller to be 20m/s, and preparing a silicon steel thin strip with the thickness of 0.25 mm;
s3, taking the silicon steel thin strip out of a roller, cooling the silicon steel thin strip to 500 ℃ by water, warm rolling the silicon steel thin strip to 0.17mm, heating the silicon steel thin strip to 850 ℃ at a heating speed of 20 ℃/H, carrying out vacuum annealing for 2min, rolling the silicon steel thin strip to 0.12mm thick, heating the silicon steel thin strip to 1000 ℃ at a heating speed of 20 ℃/H, carrying out pure hydrogen secondary annealing for 2min, air cooling the silicon steel thin strip to room temperature, coating an annealing isolation layer, heating the silicon steel thin strip to 950 ℃ at a speed of 35 ℃/H, carrying out purified gas annealing for 3min, and thus obtaining the ferromagnetic oriented silicon steel thin strip, wherein the annealing isolation layer is a mixture composed of 10% of aluminum dihydrogen phosphate, 40% of styrene-acrylic emulsion, 35% of glycerol and 15% of silane coupling agent in percentage by mass.
Example 2
The embodiment provides a ferromagnetic oriented high-silicon steel ultra-thin strip which comprises the following elements in percentage by mass: 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 balance Fe, wherein Cu, S and N are added into the ferromagnetic oriented silicon steel strip in the form of a polynuclear coordination compound containing sulfur, nitrogen and copper during smelting, and particularly, copper (II) bis (1-azaheterocyclyl) dithiocarbamate can be selected.
The embodiment also provides a preparation method of the ferromagnetic orientation high-silicon steel ultra-thin strip, which specifically comprises the following steps:
s1: preparing alloy raw materials according to the mass percentage of each element in the ferromagnetic oriented high-silicon steel, mixing the raw materials except for Bi element and a polynuclear coordination compound containing sulfur, nitrogen and copper, placing the mixture in a high-temperature electric arc melting furnace, heating the mixture to 1500 ℃ for melting, obtaining an alloy solution after the alloy raw materials are fully melted, introducing high-purity nitrogen to the surface of the alloy solution, simultaneously adding copper (II) bis (1-azaheterocyclyl) dithiocarbamate, and then adding Bi element to obtain the ferrosilicon master alloy, wherein the whole melting process lasts for 120min, and the Bi element can be added into the alloy solution in a Bi powder mode;
s2: controlling the temperature of the ferrosilicon master alloy liquid at 1200 ℃, carrying out high-speed ultra-cold single-roller melt spinning in a continuously flowing high-purity nitrogen atmosphere, controlling the linear speed of a roller at 30m/s, and preparing a silicon steel thin strip with the thickness of 0.20 mm;
s3: taking the silicon steel thin strip out of a roller, cooling the silicon steel thin strip to 600 ℃ by water, warm rolling the silicon steel thin strip to 0.14mm, heating the silicon steel thin strip to 1050 ℃ at a heating speed of 20 ℃/H, carrying out vacuum annealing for 5min, then carrying out cold rolling to 0.09mm thick, heating the silicon steel thin strip to 1150 ℃ at a heating speed of 25 ℃/H, carrying out pure hydrogen secondary annealing for 5min, then carrying out air cooling to room temperature, coating an annealing isolation layer, heating the silicon steel thin strip to 1200 ℃ at a speed of 40 ℃/H, carrying out purified gas annealing for 5min, and thus obtaining the ferromagnetic oriented silicon steel thin strip, wherein the annealing isolation layer is a mixture consisting of 15 mass percent of aluminum dihydrogen phosphate, 30 mass percent of styrene-acrylic emulsion, 25 mass percent of glycerol and 30 mass percent of silane coupling agent.
Example 3
The embodiment provides a ferromagnetic oriented high-silicon steel ultra-thin strip which comprises the following elements in percentage by mass: 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 balance of Fe, wherein Cu, S and N elements are added into the ferromagnetic oriented silicon steel ultra-thin strip in a way of multi-core coordination compound containing sulfur, nitrogen and copper during smelting, and specifically { Cu (NH) can be selected3)4}SO4。
The embodiment also provides a preparation method of the ferromagnetic orientation high-silicon steel ultra-thin strip, which specifically comprises the following steps:
s1: preparing alloy raw materials according to the mass percent of each element in the ferromagnetic oriented high-silicon steel, mixing the raw materials except the Bi element and the polynuclear coordination compound containing sulfur, nitrogen and copper, putting the mixture into a high-temperature arc melting furnace, heating the mixture to 1400 ℃ for melting, obtaining alloy solution after the alloy raw materials are fully melted, introducing high-purity nitrogen to the surface of the alloy solution, and simultaneously adding { Cu (NH) into the alloy solution3)4}SO4Then adding Bi element to obtain the ferrosilicon master alloy, wherein the whole smelting process lasts for 60min, and the Bi element can be added into the alloy solution in a Bi powder mode;
s2: controlling the temperature of the ferrosilicon master alloy liquid at 1150 ℃, carrying out high-speed ultra-cold single-roller melt spinning in a continuously flowing high-purity nitrogen atmosphere, controlling the linear speed of rollers at 25m/s, and preparing a silicon steel thin strip with the thickness of 0.22 mm;
s3: the method comprises the steps of preparing a silicon steel ultra-thin strip, taking the silicon steel ultra-thin strip out of a roller, cooling the silicon steel ultra-thin strip by water to 500 ℃, warm rolling the silicon steel ultra-thin strip to 0.15mm thick, heating the silicon steel ultra-thin strip to 950 ℃ at a heating speed of 20 ℃/H, carrying out vacuum annealing for 2min, re-rolling the silicon steel ultra-thin strip to 0.10mm thick, heating the silicon steel ultra-thin strip to 1080 ℃ at a heating speed of 25 ℃/H, carrying out pure hydrogen secondary annealing for 2min, air cooling the silicon steel ultra-thin strip to room temperature, coating an annealing isolation layer, heating the silicon steel ultra-thin strip to 1080 ℃ at a speed of 35 ℃/H, carrying out gas purification annealing for 3min, and obtaining the ferromagnetic orientation silicon steel ultra-thin strip, wherein the annealing isolation layer comprises a mixture of 15% of aluminum dihydrogen phosphate, 20% of styrene-acrylic emulsion, 35% of glycerol and 30% of silane coupling agent in percentage by mass.
Comparative example 1
The comparative example provides a ferromagnetic oriented high-silicon steel ultra-thin strip and a preparation method thereof, except that elements of Cu, S and N in the ferromagnetic oriented high-silicon steel ultra-thin strip are added into the ferromagnetic oriented high-silicon steel ultra-thin strip in a common alloy raw material mode during smelting, and other components and preparation processes are the same as those in example 3.
Comparative example 2
This comparative example provides a ferromagnetic-oriented high-silicon extremely thin strip and a method for producing a ferromagnetic-oriented high-silicon extremely thin strip, the other components and production processes being the same as those in example 3 except that the ferromagnetic-oriented high-silicon extremely thin strip does not contain Bi element.
Comparative example 3
The comparative example provides a ferromagnetic oriented high-silicon steel strip and a method for preparing the ferromagnetic oriented high-silicon steel strip, except that in the method for preparing the ferromagnetic oriented high-silicon steel strip, the vacuum annealing temperature is 1100 ℃, the pure hydrogen secondary annealing temperature is 1200 ℃, and the purge gas annealing temperature is 1250 ℃, the other components and the preparation process are the same as those in example 3.
Comparative example 4:
the comparative example provides a ferromagnetic oriented high-silicon steel ultra-thin strip and a preparation method thereof, except that in the preparation method of the ferromagnetic oriented high-silicon steel ultra-thin strip, the heating speed of the silicon steel thin strip before vacuum annealing is 35 ℃/H, and the heating speed of the intermediate annealing plate before pure hydrogen secondary annealing is 35 ℃/H, and other components and preparation processes are the same as those in example 3.
Comparative example 5
The comparative example provides a ferromagnetic oriented high-silicon steel ultra-thin strip and a method for preparing the same, except that in the method for preparing the ferromagnetic oriented high-silicon steel ultra-thin strip, the component of the annealing isolation layer coated in S3 is magnesium oxide, and other components and preparation processes are the same as those in example 3.
Detection example: the saturation magnetic induction and the iron loss of the high-silicon ultra-thin steel strips obtained in the examples and the comparative examples are respectively detected, and the test results are shown in table 1:
TABLE 1
Figure BDA0002927538120000081
Figure BDA0002927538120000091
As can be seen from the detection data in Table 1, the ferromagnetic oriented high-silicon steel ultra-thin strip obtained by the embodiment of the invention has the advantages of fine grains, uniform structure, magnetic induction performance B800 of more than 1.90T, iron loss P1.7/50 value of less than 0.90W/kg, P1.0/400 value of less than 8.5W/kg and excellent magnetic induction performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (6)

1. A method for preparing a strongly magnetically oriented high silicon steel ultra-thin strip, wherein the strongly magnetically oriented high silicon steel ultra-thin strip comprises the following elements in percentage by mass: 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 is less than 0.005%, and the balance is iron;
the method specifically comprises the following steps:
s1: preparing raw materials according to the mass percentage of each element in the ferromagnetic orientation high-silicon steel ultra-thin strip, wherein the Cu, S and N elements are prepared in a way of a multi-core coordination compound containing sulfur, nitrogen and copper, mixing and smelting the raw materials except the Bi element and the multi-core coordination compound containing sulfur, nitrogen and copper, obtaining an alloy solution after the alloy is completely melted, introducing high-purity nitrogen to the surface of the alloy solution, simultaneously adding the multi-core coordination compound containing sulfur, nitrogen and copper, and then adding the Bi element to prepare a ferrosilicon master alloy solution;
s2: controlling the temperature of the ferrosilicon master alloy solution at 1100-1200 ℃, carrying out high-speed single-roller strip throwing in a continuously flowing high-purity nitrogen atmosphere, controlling the linear speed of a roller at 20-30 m/s, and preparing a silicon steel thin strip with the thickness of 0.20-0.25 mm;
s3: taking the silicon steel thin strip out of the roller, cooling the silicon steel thin strip to 500-600 ℃ with water, warm rolling the silicon steel thin strip to 0.14-0.17 mm, heating the silicon steel thin strip to 850-1050 ℃, and then carrying out vacuum annealing for 2-5 min; and then rolling to 0.09-0.12 mm, heating to 1000-1150 ℃, performing pure hydrogen secondary annealing for 2-5 min, then air cooling to room temperature, coating an annealing isolation layer, heating to 950-1200 ℃, performing gas purification annealing for 3-5 min, and thus obtaining the ferromagnetic oriented high-silicon steel ultra-thin strip.
2. The method for manufacturing the ferromagnetic orientation high-silicon steel ultra-thin strip as claimed in claim 1, wherein the temperature of the mixed melting in S1 is 1300 to 1500 ℃.
3. The method for preparing the ferromagnetic orientation high silicon steel ultra-thin strip according to claim 1, wherein the silicon steel ultra-thin strip subjected to warm rolling is heated to the annealing temperature at a heating rate of 20-25 ℃/h before the vacuum annealing.
4. The method for preparing the ferromagnetic orientation high silicon steel ultra-thin strip according to claim 1, wherein the silicon steel ultra-thin strip subjected to cold rolling is heated to the annealing temperature at a heating rate of 20-25 ℃/h before the pure hydrogen secondary annealing.
5. The method for preparing the ferromagnetic orientation high silicon steel ultra-thin strip according to claim 1, wherein the silicon steel ultra-thin strip coated with the annealing isolation layer is heated to the annealing temperature at a heating rate of 35-40 ℃/h before the purge gas annealing.
6. The method of manufacturing a ferromagnetic-oriented high silicon steel ultra-thin strip as set forth in claim 1, wherein the annealing separator in S3 is a mixture of aluminum dihydrogen phosphate, styrene-acrylic emulsion, glycerin, and a silane coupling agent;
the mixture comprises the following components in percentage by mass: aluminum dihydrogen phosphate: 10-15%, styrene-acrylic emulsion: 20-40%, glycerin: 25-35%, silane coupling agent: 10 to 30 percent.
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