JP7324549B2 - Ferromagnetic grain-oriented high-silicon steel ultra-thin strip and its production method - Google Patents

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims priority from Chinese Patent Application No. CN202110137389.4, filed on Feb. 01, 2021. The disclosure of the prior application is incorporated herein by reference in its entirety.

The present application belongs to the field of electromagnetic steel production, and more specifically relates to a ferromagnetic oriented high silicon steel ultra-thin strip and its production method.

Grain-oriented silicon steel is an important soft magnetic material, an important manufacturing raw material for transformer cores, and also one of the essential materials for the development of the power industry. The low iron loss and low magnetostriction coefficient characteristics of high silicon steel show significant advantages in high-frequency equipment such as high-speed high-frequency motors, audio equipment, high-frequency transformers, choke coils and high-frequency magnetic shields. In addition, the use of high silicon steel instead of the common cold rolled oriented silicon steel can not only improve the operating frequency and sensitivity of electronic and electrical elements, but also greatly reduce the weight and volume of electrical equipment. The electrical equipment is quiet and noiseless when working, saving energy consumption, effectively solving the contradiction between efficiency, energy saving, light weight and quietness.

The continuous ribbon casting method can directly produce ribbon materials using a liquid alloy, and is a very potential short-flow metal ribbon manufacturing process. The alloy liquid is in direct contact with the casting roll, the solidification structure and texture of the produced oriented silicon steel are significantly different from the traditional continuous cast slab, and the produced oriented silicon steel is sub-rapidly solidified. It can sufficiently suppress the coarsening process of the second phase particles, fundamentally solve the harmful effects of high-temperature heating of grain-oriented silicon steel cast pieces, and is necessary for the production of grain-oriented silicon steel It provides favorable conditions for fine, uniform, and dispersed distribution of inhibitors, and the technology has already been successfully applied to the production of low-carbon steel, high-speed steel, and other processes, but not for oriented high-silicon steel. In the production, the solidification structure control, inhibitor precipitation, cold working plasticity and other aspects are more demanding, and these problems are difficult to overcome. There are defects of poor stability, low magnetic induction strength and high iron loss.

In view of the technical problems of low purity, poor stability, and poor magnetic properties of ferromagnetic grain-oriented high silicon steel in the prior art, the present application provides a ferromagnetic grain-oriented high silicon steel ultra-thin strip and its A manufacturing method is provided.

To achieve the above objectives, the embodiments of the present application adopt the following technical solutions.

In a first aspect, embodiments of the present application provide ferromagnetic grain-oriented high silicon steel ultrathin strips comprising the following mass percentage elements:
C: 0.0045% to 0.0060%, Si: 4.5% to 5.0%, Mn: 0.23% to 0.32%, S: 0.02% to 0.03%, Bi: 0.03% to 0.08%, Als: 0.027% to 0.035%, Cu: 0.02% to 0.03%, N: 0.008% to 0.010%, P<0. 005%, the balance of which contains iron, of which the Cu element, the S element, and the N element are formed into the ferromagnetic grain-oriented high-silicon steel ultra-thin in the form of polynuclear coordination compounds containing sulfur, nitrogen, and copper during smelting Add to band.

As can be understood, Als is acid-soluble aluminum, and adding it to the ferromagnetic grain-oriented high silicon steel ultrathin strip in the form of a polynuclear coordination compound containing sulfur nitrogen and copper means that the manufacturing process In the above, a coordination compound composed of sulfur element, nitrogen element, and copper element is added to the alloy raw material. It is understood that the ferromagnetic grain-oriented high-silicon steel ultra-thin strip is a thin-thick grain-oriented high-silicon steel strip obtained with the above mass percentage of elements and has good ferromagnetism.

As will be appreciated, the mass percentage of each element can be any value in the above range interval.

In a second aspect, the embodiments of the present application further provide a method for producing the ferromagnetic grain-oriented high-silicon steel ultrathin strip, specifically comprising:
In S1, raw materials are prepared according to the mass percentage of each element in the ferromagnetic grain-oriented high-silicon steel ultrathin strip, and the raw materials other than the Bi element and the polynuclear coordination compound containing sulfur, nitrogen, and copper are mixed. After the alloy raw material is completely melted, an alloy solution is obtained, and at the same time high-purity nitrogen gas is flowed over the surface of the alloy solution, the polynuclear coordination compound containing sulfur nitrogen and copper is added, followed by adding the element Bi to form a silicon-iron master alloy solution, wherein the element Bi can be added to the alloy solution in the form of Bi powder;
In S2, the temperature of the silicon-iron master alloy solution is controlled to 1100-1200° C., high-speed single-roller melt-spinning is performed in continuously flowing high-purity nitrogen gas, and the high-speed single roll is A step of controlling the linear velocity of the roll in the melt spinning process to 20 to 30 m / s to produce a silicon steel ribbon with a thickness of 0.20 to 0.25 mm;
In S3, the silicon steel ribbon is out-rolled, water-cooled to 500 to 600° C., warm-rolled to 0.14 to 0.17 mm, heated and vacuum annealed, and further 0.09 to 0.12 mm. Then, the steel is cold-rolled, heated to perform pure hydrogen gas secondary annealing, further air-cooled to room temperature, coated with an annealing separation layer, heated and subjected to purification gas annealing, and the ferromagnetic grain-oriented high silicon steel ultrathin obtaining a strip.

It is understood that the high-speed single-roll melt spinning process is carried out using melt spinning equipment to control the linear velocity of the rolls, to ensure high speed operation of the melt spinning process, and in the process, deep supercooling rapid The effect of solidification can be realized, and deep supercooling means that the silicon-iron master alloy solution remains liquid at a large degree of supercooling by suppressing nucleation. An alloy solution is obtained after the alloying raw materials are completely melted in S1, where the alloying raw materials are other raw materials other than polynuclear coordination compounds containing Bi element, sulfur nitrogen and copper. In S1, high-purity nitrogen gas is flowed over the surface of the alloy solution, and in S2, the atmosphere is of high-purity nitrogen gas. In S3, first, the silicon steel ribbon is taken out from the melt spinning apparatus, and then the silicon steel ribbon after outrolling is subjected to water cooling treatment, warm rolling treatment, heating and vacuum annealing treatment, cold rolling treatment, heating and Pure hydrogen gas secondary annealing treatment, air cooling treatment, coating treatment, heating, and purification gas annealing treatment are sequentially performed. Therefore, in the annealing process, a small amount of hydrogen elements will be mixed in the steel strip, affecting the quality of the steel. The layer protects the surface of the steel strip and prevents the gas overflowing from the steel strip from further reacting with the surface of the steel strip, thereby ensuring the quality of the surface of the steel strip. The annealing step performed to purify the small amount of gas doped into the steel strip structure is a purge gas anneal, which is usually performed in a vacuum or negative pressure environment and is commonly used in the field. Belong to a process. Air cooling is cooling in the air.

It will be appreciated that in S2, S3 the numerical values can be any value in the range interval above.

In a possible implementation, in S1, the smelting of the alloy raw material is carried out in a smelting furnace, and a high temperature arc smelting furnace can be selected.

In a possible implementation, in S1, the temperature of said mixed smelting is 1300-1500°C. If the melting temperature is within this range, the alloy raw materials can be sufficiently melted and uniformly mixed, and a silicon steel ribbon having a uniform structure and properties can be formed in the melt spinning process. As will be appreciated, the smelting temperature may be any value in the above range interval. Of course, still other smelting temperatures can be employed in other possible implementations, and are not limited to this.

In a possible implementation, in S3, the vacuum annealing temperature is 850-1050° C., and the vacuum annealing time is 2-5 min. The vacuum annealing temperature and annealing time within the above ranges are such that excess oxides of C element and Si element in the silicon steel ribbon are precipitated on the surface of the silicon steel ribbon to form an oxide layer, which is removed during the cold rolling process. This further enhances the workability and toughness of the silicon steel ribbon. As will be appreciated, the annealing temperature and annealing time may be any value in the range interval. Of course, still other annealing temperatures and annealing times may be employed in other possible embodiments, and are not limited to this.

In a possible realization, the silicon steel ribbon, which has been warm-rolled, is heated to the annealing temperature at a heating rate of 20-25° C./h before the vacuum annealing. Here, the annealing temperature is the annealing temperature for vacuum annealing. A heating rate within this range reduces the temperature gradient between the silicon steel ribbon layers, contributes to the generation of oxides on the silicon steel ribbon surface C and Si, improves the uniformity of the surface oxide layer, and vacuum annealing. It also provides optimal kinetic conditions for texture and tissue formation in the process. As will be appreciated, the heating rate may be any value in the range interval. Of course, still other heating rates can be employed in other possible implementations, and are not limited to this.

In a possible implementation mode, in S3, the temperature of the pure hydrogen gas secondary annealing is 1000-1150° C., and the time of the pure hydrogen gas secondary annealing is 2-5 min. When the pure hydrogen gas secondary annealing temperature and annealing time are within the above ranges, the Goss grains in the silicon steel ribbon sufficiently swallow other grains, abnormal growth occurs, and a complete secondary recrystallized texture is formed. It can be ensured that the magnetic properties of the silicon steel ribbon after secondary annealing are improved. As will be appreciated, the annealing temperature and annealing time may be any value in the range interval. Of course, still other annealing temperatures and annealing times may be employed in other possible embodiments, and are not limited to this.

In a possible embodiment, the cold-rolled silicon steel ribbon is heated to the annealing temperature at a rate of 20-25° C./h before the pure hydrogen gas secondary annealing. Here, the annealing temperature is the annealing temperature of pure hydrogen gas secondary annealing. A heating rate within this range reduces the temperature gradient between the layers of the silicon steel ribbon, provides suitable conditions for the Goss grains in the structure to swallow other grains, and makes the structure in the silicon steel ribbon uniform. improve the magnetic properties of the silicon steel ribbon. As will be appreciated, the heating rate may be any value in the range interval. Of course, still other heating rates can be employed in other possible implementations, and are not limited to this.

In a possible implementation, in S3, the temperature of said purge gas anneal is 950-1200° C. and the time of said purge gas anneal is 3-5 min. As will be appreciated, the annealing temperature and annealing time may be any value in the range interval. Of course, still other annealing temperatures and annealing times may be employed in other possible embodiments, and are not limited to this.

In a possible implementation, the silicon steel ribbon coated with the annealing separation layer is heated to the annealing temperature at a heating rate of 35-40° C./h before the purge gas annealing. Here, the annealing temperature is the annealing temperature for purification gas annealing. As will be appreciated, the heating rate may be any value in the range interval. Of course, still other heating rates can be employed in other possible implementations, and are not limited to this.

In a possible implementation, in S3, the components of the annealed separation layer are a mixture of aluminum dihydrogen phosphate, styrene acrylic emulsion, glycerin and a silane coupling agent, and the mass percentage content 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%. In addition, the initial value is abbreviated in the above percentage content by mass, and in fact, aluminum dihydrogen phosphate: 10% to 15%, styrene acrylic emulsion: 20% to 40%, glycerin: 25% to 35%, silane Coupling agent: 10% to 30%. The mixture used for the annealed separation layer maximizes the oxidation resistance of the silicon steel strip surface and the punching performance of the silicon steel strip, prevents adhesion between layers in the manufacturing process of subsequent products, and improves quality. can be improved. As will be appreciated, the weight percentage may be any value in the range interval. Of course, still other components and weight percentages can be employed in other possible implementations, and are not limited to this.

In a possible implementation, in S3, specifically including the following steps, water cooling to 500-600° C. after outrolling the silicon steel ribbon to obtain a first ribbon; is warm-rolled to 0.14 to 0.17 mm to obtain a second ribbon, the second ribbon is heated and vacuum annealed to obtain a third ribbon, and the third ribbon is obtained. The ribbon is cold-rolled to 0.09 to 0.12 mm to obtain a fourth ribbon, and the fourth ribbon is heated and subjected to pure hydrogen gas secondary annealing to obtain a fifth ribbon. Furthermore, the fifth ribbon is air-cooled to room temperature to obtain a sixth ribbon, the annealing separation layer is applied to the sixth ribbon, the seventh ribbon is obtained, and the seventh ribbon is obtained. is heated to carry out purification gas annealing to obtain the ferromagnetic grain-oriented high silicon steel ultra-thin strip.

In contrast to the prior art, the present application adopts polynuclear coordination compounds containing sulfur nitrogen and copper and Bi elements as alloy inhibitors by designing raw material components for ferromagnetic grain-oriented high-silicon steel ultra-thin strips. A polynuclear coordination compound containing sulfur nitrogen and copper introduces Cu, S and N elements into the alloy, guarantees high element absorption, and reacts with other metals in the alloy to form CuS, AlN , MnS, etc., which can be precipitated during the initial solid-liquid solidification process of casting. The growth can be suppressed, thereby promoting the occurrence of secondary crystals of Goss grains, and the produced ferromagnetic oriented high silicon steel ultrathin ribbon has fine grains, uniform texture, and high magnetism. It has excellent magnetic properties of inductive strength and low iron loss.

Compared with the prior art, the manufacturing method of the ferromagnetic oriented high silicon steel ultra-thin strip provided by the present application is characterized by flowing high-purity nitrogen gas in both the smelting and melt spinning processes of the alloy, and inhibiting AlN by high-temperature nitriding. A polynuclear coordination compound containing sulfur nitrogen and copper, which can not only promote the formation of agents, improve the formation of texture and the uniformity of alloy structure, but also prevent the oxidation of the alloy surface. and elemental bismuth are added to ensure the yield of elemental copper and elemental bismuth. High-purity nitrogen gas can be used as a cooling gas in the melt spinning process to rapidly lower the temperature of the free surface of the silicon steel ribbon and accelerate the formation of crystal grains. Combining the application of the surface annealing separation layer, further stabilize the structure of the silicon steel ribbon, and improve the magnetic properties, purity, surface oxidation resistance and punching performance of the silicon steel ribbon.

The manufacturing method of the ferromagnetic grain-oriented high silicon steel ultra-thin strip provided in the present application has the superiority of deep supercooling and rapid solidification through integrated process routes such as continuous casting, rolling, high temperature annealing, and surface modification. The produced ferromagnetic oriented high-silicon steel ultra-thin strip has the characteristics of high purity, good stability and excellent magnetic properties.

In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application clearer, the following will combine examples to describe the present application in more detail. It should be understood that the specific examples described herein are used only for the purpose of interpreting the present application and are not intended to limit the present application.

[Example 1]
This example provides a ferromagnetic grain-oriented high silicon steel ultra-thin strip, with the following mass percentage elements: 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%, the balance containing Fe, of which Cu element, S The element N element is added to the ferromagnetic grain-oriented high silicon steel ultrathin strip in the form of a polynuclear coordination compound containing sulfur nitrogen and copper during smelting, specifically N,N-di-n-butyl. Copper dithiocarbamate can be selected.

This embodiment further provides a method for producing a ferromagnetic oriented high-silicon steel ultra-thin strip, specifically:
In S1, alloy raw materials are prepared according to the mass percentage of each element in the ferromagnetic grain-oriented high-silicon steel ultra-thin strip, mixed with raw materials other than polynuclear coordination compounds containing Bi element, sulfur nitrogen and copper, and heated at high temperature. It is placed in an arc smelting furnace, heated to 1300° C. and smelted to obtain an alloy solution after the alloy raw materials are completely melted. Add copper n-butyldithiocarbamate, then add Bi element to obtain silicon-iron master alloy solution, the whole smelting process continues for 30min, in which Bi element is added to the alloy solution in the form of Bi powder. a step that can
In S2, the temperature of the silicon-iron mother alloy solution is controlled to 1100° C., melt spinning is performed with a high-speed extremely cold single roll in an atmosphere of continuously flowing high-purity nitrogen gas, and the roll in the melt spinning process with a high-speed extremely cold single roll A step of controlling the linear velocity of 20 m / s to produce a silicon steel ribbon with a thickness of 0.25 mm;
In S3, first, the silicon steel ribbon is taken out from the roll of the melt spinning apparatus, then the silicon steel ribbon after being out-rolled is water-cooled to 500°C, warm-rolled to 0.17 mm, and heated at 20°C/h. After heating to 850 ° C. at a speed of 850 ° C., vacuum annealing is performed for 2 minutes, and cold rolling is performed to a thickness of 0.12 mm. After further air cooling to room temperature, after coating the annealing separation layer, heating to 950° C. at a heating rate of 35° C./h, followed by purification gas annealing, after 3 minutes of purification gas annealing, ferromagnetic grain oriented high silicon steel An ultrathin strip is obtained, and the components of the annealed separating layer are a mixture composed of 10% by weight aluminum dihydrogen phosphate, 40% styrene-acrylic emulsion, 35% glycerin and 15% silane coupling agent. and a step.

[Example 2]
This example provides a ferromagnetic oriented high-silicon steel ultra-thin strip, with the following mass percentage elements: C: 0.0060%, Si: 5.0%, Mn: 0.32%, S: 0 0.03%, Bi: 0.08%, Als: 0.035%, Cu: 0.03%, N: 0.0010%, P: 0.002%, the balance containing Fe, of which Cu element, S The element N element is added to the ferromagnetic oriented high silicon steel ultrathin strip in the form of a multinuclear coordination compound containing sulfur nitrogen and copper during smelting, specifically bis(1-nitrogen heterocyclic group). Copper (II) dithiocarbamate can be selected.

This embodiment further provides a method for producing a ferromagnetic oriented high-silicon steel ultra-thin strip, specifically:
In S1, alloy raw materials are prepared according to the mass percentage of each element in the ferromagnetic grain-oriented high-silicon steel ultra-thin strip, mixed with raw materials other than polynuclear coordination compounds containing Bi element, sulfur nitrogen and copper, and heated at high temperature. Place it in an arc smelting furnace, heat it to 1500 ° C. and smelt it, obtain an alloy solution after the alloy raw material is melted, flow high-purity nitrogen gas on the surface of the alloy solution, and at the same time, bis(1-nitrogen heterocyclic group ) Add copper (II) dithiocarbamate, then add Bi element to obtain silicon-iron mother alloy solution, the whole smelting process lasts 120min, during which Bi element is added to the alloy solution in the form of Bi powder. a step that can be
In S2, the temperature of the silicon-iron master alloy solution is controlled to 1200° C., melt spinning is performed with a high-speed extremely cold single roll in an atmosphere of continuously flowing high-purity nitrogen gas, and the roll in the melt spinning process with a high-speed extremely cold single roll A step of controlling the linear velocity of 30 m / s to produce a silicon steel ribbon with a thickness of 0.20 mm;
In S3, first, the silicon steel ribbon is taken out from the roll of the melt spinning apparatus, then the silicon steel ribbon after being out-rolled is water-cooled to 600°C, warm-rolled to 0.14 mm, and heated at 20°C/h. After heating to 1050° C. at a speed of 1050° C., vacuum annealing is performed for 5 minutes, followed by cold rolling to a thickness of 0.09 mm. Then air-cool to room temperature, apply an annealed separation layer, heat to 1200° C. at a rate of 40° C./h, and then perform purification gas annealing. obtaining a ribbon, the components of the annealed separation layer being a mixture composed of 15% aluminum dihydrogen phosphate, 30% styrene-acrylic emulsion, 25% glycerin and 30% silane coupling agent in mass percentages; and including.

[Example 3]
This example provides a ferromagnetic oriented high-silicon steel ultrathin strip with the following mass percentage elements: C: 0.0050%, Si: 4.5%, Mn: 0.28%, S: 0 0.02%, Bi: 0.05%, Als: 0.030%, Cu: 0.02%, N: 0.008%, P: 0.004%, the balance containing Fe, of which Cu element, S The element, N element, is added to the ferromagnetic grain-oriented high silicon steel ultrathin ribbon in the form of a polynuclear coordination compound containing sulfur nitrogen and copper during smelting, specifically {Cu(NH ₃ ) ₄ }SO ₄ can be selected.

This embodiment further provides a method for producing a ferromagnetic oriented high-silicon steel ultra-thin strip, specifically:
In S1, alloy raw materials are prepared according to the mass percentage of each element in the ferromagnetic grain-oriented high-silicon steel ultra-thin strip, mixed with raw materials other than polynuclear coordination compounds containing Bi element, sulfur nitrogen and copper, and heated at high temperature. Placed in an arc smelting furnace, heated to 1400 ° C. to smelt, obtain an alloy solution after the alloy raw materials are sufficiently melted, flow high-purity nitrogen gas on the surface of the alloy solution, and at the same time {Cu(NH ₃ ) ₄ } _SO4 is added, followed by Bi element, to obtain silicon-iron mother alloy solution, the whole smelting process lasts 60min, during which Bi element can be added to the alloy solution in the form of Bi powder. possible steps and
In S2, the temperature of the silicon-iron master alloy solution is controlled to 1150° C., melt spinning is performed with a high-speed extremely cold single roll in an atmosphere of continuously flowing high-purity nitrogen gas, and the roll in the melt spinning process with a high-speed extremely cold single roll A step of controlling the linear velocity of 25 m / s to produce a silicon steel ribbon with a thickness of 0.22 mm;
In S3, first, the silicon steel ribbon is taken out from the roll of the melt spinning device, then the silicon steel ribbon after being out-rolled is water-cooled to 500°C, warm-rolled to a thickness of 0.15 mm, and rolled at 20°C/h. After heating to 950 ° C. at a heating rate of 2 minutes, vacuum annealing is performed for 2 minutes, cold rolling to a thickness of 0.10 mm, followed by heating to 1080 ° C. at a heating rate of 25 ° C./h, and pure hydrogen gas secondary annealing. was further air-cooled to room temperature, and after coating the annealed separation layer, it was heated to 1080° C. at a heating rate of 35° C./h, followed by purification gas annealing. A silicon steel ultra-thin strip is obtained, and the components of the annealed separation layer are a mixture composed of 15% by weight aluminum dihydrogen phosphate, 20% styrene acrylic emulsion, 35% glycerin and 30% silane coupling agent. and

[Control Example 1]
This comparative example provides a ferromagnetic grain-oriented high silicon steel ultra-thin strip and a method for producing a ferromagnetic grain-oriented high-silicon steel ultra-thin strip. Except that the N element is added to the ferromagnetic grain-oriented high silicon steel ultrathin strip in the usual way of alloying raw materials during smelting, the other components and manufacturing process are the same as those in Example 3.

[Control Example 2]
This comparative example provides a ferromagnetic grain-oriented high silicon steel ultra-thin strip and a method for producing a ferromagnetic grain-oriented high-silicon steel ultra-thin strip, except that the ferromagnetic grain-oriented high-silicon steel ultra-thin strip does not contain the element Bi. , other ingredients and manufacturing process are the same as in Example 3.

[Control Example 3]
This comparative example provides a ferromagnetic grain-oriented high silicon steel ultra-thin strip and a method for producing a ferromagnetic grain-oriented high silicon steel ultra-thin strip. Other components and manufacturing processes are the same as in Example 3, except that the temperature is 1100°C, the pure hydrogen gas secondary annealing temperature is 1200°C, and the purge gas annealing temperature is 1250°C.

[Control Example 4]
This comparative example provides a ferromagnetic grain-oriented high silicon steel ultra-thin strip and a method for producing a ferromagnetic grain-oriented high silicon steel ultra-thin strip. Except that the heating rate of the silicon steel ribbon before is 35° C./h, and the heating rate of the silicon steel ribbon before the pure hydrogen gas secondary annealing is 35° C./h, the other ingredients and manufacturing process are Same as example 3.

[Control Example 5]
This comparative example provides a ferromagnetic grain-oriented high silicon steel ultra-thin strip and a method for producing a ferromagnetic grain-oriented high silicon steel ultra-thin strip. Other components and manufacturing processes are the same as in Example 3, except that the component of the applied annealed isolation layer is magnesium oxide.

In the detection example, the magnetic induction strength and iron loss of the high-silicon steel ultrathin strips obtained in the examples and the control examples were detected, respectively, and the test results are shown in Table 1.

As can be seen from the detection data in Table 1, the ferromagnetic oriented high-silicon steel ultrathin strips obtained in the examples of the present application have fine crystal grains, a uniform structure, and magnetic induction performance B800>1.90T. , the iron loss P1.7/50 value is less than 0.90 W/kg, the P1.0/400 value is less than 8.5 W/kg, and has excellent magnetic induction performance.

The above descriptions are only preferred embodiments of the present application, not limiting the present application, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present application shall all fall within the protection scope of the present application. should be included in

Claims (3)

The following mass percentage elements: C: 0.0045% to 0.0060%, Si: 4.5% to 5.0%, Mn: 0.23% to 0.32%, S: 0.02% to 0.03%, Bi: 0.03% to 0.08%, Als: 0.027% to 0.035%, Cu: 0.02% to 0.03%, N: 0.008% to 0.03% 010%, P<0.005%, the balance being iron and unavoidable impurities .
including the following steps S1 to S3;
In S1, raw materials are prepared according to the mass percentage of each element in the ferromagnetic grain-oriented high-silicon steel ultrathin strip, among which Cu element, S element and N element are polynuclear coordination containing sulfur nitrogen and copper A raw material prepared as a compound and other than the polynuclear coordination compound containing the Bi element and the sulfur nitrogen and copper is mixed and smelted to obtain an alloy solution after the alloy raw material is completely melted, and the surface of the alloy solution is obtained. At the same time, the polynuclear coordination compound containing sulfur nitrogen and copper is added, and then the Bi element is added to prepare a silicon-iron master alloy solution,
In S2, the temperature of the silicon-iron mother alloy solution is controlled to 1100 to 1200° C., melt spinning is performed with a high-speed single roll in an atmosphere of continuously flowing high-purity nitrogen gas, and the rolls in the melt spinning process with the high-speed single roll By controlling the linear velocity of 20 to 30 m / s, a silicon steel ribbon with a thickness of 0.20 to 0.25 mm is produced,
In S3, the silicon steel ribbon is out-rolled, water-cooled to 500 to 600° C., warm-rolled to 0.14 to 0.17 mm, heated to 850 to 1050° C., vacuum annealed for 2 to 5 minutes, Furthermore, it is cold rolled to 0.09 to 0.12 mm, heated to 1000 to 1150 ° C., subjected to pure hydrogen gas secondary annealing for 2 to 5 minutes, further air-cooled to room temperature, and after applying an annealed separation layer to 950 to 1200 The ferromagnetic grain-oriented high silicon steel ultra-thin ribbon is obtained by heating to 90° C. and performing purification gas annealing for 3 to 5 minutes. The temperature is raised to the vacuum annealing temperature at a heating rate of 20 to 25° C./h. The temperature is raised to the temperature of the next annealing, and the components of the annealing separation layer are a mixture of aluminum dihydrogen phosphate, styrene acrylic emulsion, glycerin and a silane coupling agent, and the mass percentage content of each component in the mixture is , aluminum dihydrogen phosphate: 10 to 15%, styrene acrylic emulsion: 20 to 40%, glycerin: 25 to 35%, silane coupling agent: 10 to 30%,
A method for producing a ferromagnetic grain-oriented high-silicon steel ultra-thin strip. In S1, the melting temperature is 1300 to 1500 ° C.
The method for producing a ferromagnetic grain-oriented high-silicon steel ultra-thin ribbon according to claim 1, characterized in that: Before the purification gas annealing, the silicon steel ribbon coated with the annealing separation layer is heated to the purification gas annealing temperature at a temperature rising rate of 35 to 40 ° C./h.
The method for producing a ferromagnetic grain-oriented high-silicon steel ultra-thin ribbon according to claim 1, characterized in that: