Iron-based nanocrystalline strip and preparation method thereof

Abstract

The invention discloses an iron-based nanocrystalline strip and a preparation method thereof, and belongs to the technical field of magnetic functional materials. In order to solve the technical problem that the soft magnetic performance of an iron-based nanocrystalline strip synthesized in the prior art is reduced in high-temperature and low-temperature environments, the preparation method of the iron-based nanocrystalline strip comprises the following steps that iron, copper, ferroniobium, silicon and ferroboron serve as raw materials to be mixed, and prepared raw materials are obtained; melting the prepared raw materials in vacuum to obtain a master alloy sample; and carrying out secondary smelting on the mother alloy sample to obtain the amorphous ribbon. Laser cladding is carried out on the surface of the amorphous ribbon with auxiliary agent powder to form an encapsulated amorphous ribbon; and the encapsulated amorphous ribbon is subjected to a heat treatment process, coated with an epoxy resin adhesive and cured, and the iron-based nanocrystalline ribbon is prepared. The epoxy resin adhesive is obtained by modifying bisphenol A epoxy resin with the prepared polyfluoroaniline. The iron-based nanocrystalline strip prepared by the method still has better soft magnetic performance in high and low temperature environments.

Description

Technical Field

[0001] The present invention relates to the technical field of magnetic functional materials, and in particular to an iron-based nanocrystalline strip and a preparation method thereof. Background Art

[0002] Nanocrystalline alloys are alloys formed by crystallizing amorphous materials through annealing at a certain temperature, resulting in the precipitation of fine grains. Iron-based nanocrystalline ribbons use ferromagnetic elements as the primary component of the nanocrystalline alloy. Through appropriate heat treatment, nanoscale grains are grown on the existing amorphous matrix, creating excellent soft magnetic properties. Iron-based nanocrystalline materials exhibit high magnetic permeability, low loss, and high saturation magnetic induction, making them suitable for applications in electronic devices such as filters, transformers, and precision current transformers.

[0003] Patent application CN117265398A discloses an iron-based nanocrystalline ribbon, its preparation method, and its application. The iron-based nanocrystalline ribbon comprises halogen elements, rare earth metals, and other elements. By selecting specific components and limiting their content, the ribbon exhibits excellent soft magnetic properties. However, conventional iron-based nanocrystalline ribbons lack inherent thermal stability. At low temperatures, the soft magnetic properties of the synthesized iron-based nanocrystalline ribbon decrease, making the resulting ribbon unsuitable for harsh environments such as high and low temperatures.

[0004] In view of the technical defects in this aspect, a solution is now proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide an iron-based nanocrystalline ribbon and a preparation method thereof, so as to solve the technical problem in the prior art that the soft magnetic properties of the iron-based nanocrystalline ribbon synthesized in the prior art decrease under high and low temperature environments.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing an iron-based nanocrystalline ribbon comprises the following steps: The surface of the amorphous ribbon is laser clad with auxiliary powder to form an encapsulated amorphous ribbon; the encapsulated amorphous ribbon is subjected to a heat treatment process, coated with an epoxy resin adhesive, and then cured to prepare an iron-based nanocrystalline ribbon.

[0007] Furthermore, the preparation method of the auxiliary agent powder comprises the following steps: B1. In parts by mass, 3-9 parts of aluminum, 30.33 parts of chromium, 30.33 parts of iron and 30.33 parts of nickel were uniformly mixed to obtain a mixed raw material; B2. The mixed raw materials are transferred to a vacuum induction melting gas atomization device. The pressure in the furnace is evacuated to 0.001-0.003 Pa, and then washed with inert gas. The raw materials are smelted at 1900-1950°C for 60-100 minutes to obtain molten metal. The molten metal flows into the atomization chamber through a guide tube at an atomization pressure of 5-5.5 MPa to obtain additive powder.

[0008] The vacuum melting gas mist method is used to prepare high entropy alloys doped with different aluminum contents, namely the prepared auxiliary powder.

[0009] Furthermore, the method for preparing the amorphous ribbon comprises the following steps: A1. Iron, copper, ferroniobium, silicon, and ferroboron are mixed as raw materials to obtain prepared raw materials; the prepared raw materials are transferred to a vacuum melting furnace with a vacuum degree of 0.05-0.1 Pa; the air in the vacuum melting furnace is then replaced with nitrogen, and the prepared raw materials are melted at 2200-2300°C. After complete melting, the raw materials are kept warm, removed from the furnace, and cooled to room temperature to prepare a master alloy sample; A2. The master alloy sample is placed in a melting ladle and melted at a melting temperature of 1350-1450°C to obtain an alloy melt; the alloy melt is placed in a quartz tube and sprayed at 35-45 kPa to prepare an amorphous thin ribbon.

[0010] Furthermore, in step A1, the mass ratio of iron, copper, ferroniobium, silicon and ferroboron is 70-73.5:0.5-1.5:2-3:13-15:8-9, and the insulation time is 5-10 minutes.

[0011] Furthermore, the preparation method of the epoxy resin adhesive comprises the following steps: S1, 3-(fluoromethyl)benzamide, ethanol and deionized water are mixed, and then 10-15%wt NaOH solution and sodium hypochlorite are added, and stirred until the sodium hypochlorite is completely dissolved; then the temperature is raised to 75-85°C and the reaction is carried out for 2-3 hours to obtain the product; the product is subjected to post-processing to prepare polyfluoroaniline; Using sodium hypochlorite as an oxidant, 3-(fluoromethyl)benzamide undergoes a decarboxylation reaction to synthesize polyfluoroaniline. The reaction formula is as follows:

[0012] S2. Blend bisphenol A epoxy resin, polyfluoroaniline and propylene glycol methyl ether, and reflux for reaction at 135-145° C. for 3-5 hours to obtain a product; wash the product with ethanol to obtain an organic viscous liquid after washing, which is the prepared epoxy resin adhesive.

[0013] Furthermore, in step S1, the usage ratio of 3-(fluoromethyl)benzamide, ethanol, deionized water, NaOH solution and sodium hypochlorite is 10-20 g:100-120 mL:100 mL:5-10 mL:16-32 g; the post-processing steps are: extracting the product with ethyl acetate 3-5 times, combining the organic phases; washing the organic phase with deionized water to obtain the prepared polyfluoroaniline; in step S2, the usage ratio of bisphenol A epoxy resin, polyfluoroaniline and propylene glycol methyl ether is 10-20 g:5-10 g:500 mL; the volume ratio of the product to anhydrous ethanol is 1-2:5, and the product is washed 2-3 times.

[0014] Furthermore, the specific steps of the heat treatment process are: The amorphous ribbon is cut into strips of 5-10 cm to obtain an amorphous ribbon sample; the amorphous ribbon sample is transferred to a heat treatment furnace, and the quartz tube is vacuumed to 0.5-1 Pa; the temperature of the heat treatment furnace is 500-550° C., and the temperature is maintained at this temperature for 80-100 minutes.

[0015] Furthermore, during laser cladding, the laser power is 1200-1400W, the scanning speed is 5-8mm / s, the powder feeding speed is 15.5-16.5g / min, and the cladding thickness is 0.5-1mm; the coating thickness of the epoxy resin adhesive is 1-2mm, the curing temperature is 80-100℃, and the curing time is 60-100min.

[0016] As another aspect of the present invention, a method for preparing an iron-based nanocrystalline ribbon provides an iron-based nanocrystalline ribbon prepared.

[0017] The present invention has the following beneficial effects: 1. Ferromagnetic elements, amorphous-forming elements, and nanocrystal-forming elements are melted as raw materials to produce a master alloy sample. This master alloy sample is then sprayed to form an amorphous ribbon. The amorphous ribbon is then laser-clad with a high-entropy alloy-like powder additive to form an encapsulation layer, producing an encapsulated amorphous ribbon. The encapsulated amorphous ribbon is then heat-treated to produce an amorphous ribbon sample. The additive powder is then laser-melted onto the surface of the amorphous ribbon, and then heat-treated to refine the grain size, producing an iron-based nanocrystalline ribbon with a nanocrystalline structure. The severe lattice deformation in the high-entropy alloy hinders atomic diffusion and dislocation movement, resulting in an encapsulation layer on the surface of the prepared amorphous ribbon, enhancing its hardness and strength.

[0018] 2. After heat treatment, the amorphous ribbon sample partially transforms into a crystalline state. However, the amorphous ribbon sample is highly brittle, and its soft magnetic properties degrade under external stress. The present invention uses epoxy resin to encapsulate the sample. Because the mechanical properties of the encapsulated epoxy resin in a low-temperature environment are crucial to the stable operation of the superconducting magnet, the present invention modifies bisphenol A epoxy resin with prepared polyfluoroaniline and then cures it at high temperature to produce an iron-based nanocrystalline ribbon. The iron-based nanocrystalline ribbon produced by the present invention exhibits high strength and hardness, and maintains excellent soft magnetic properties even in low-temperature environments. DETAILED DESCRIPTION

[0019] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0020] The ferroniobium and ferroboron used in Examples 4-6 of the present invention were purchased from Nangong Xiangfan Alloy Materials Co., Ltd.; the product number of ferroniobium is 1790, and the brand is NB1; the product number of ferroboron is 1574, and the brand is XF-B; the bisphenol A epoxy resin used in Examples 7-9 of the present invention is specifically bisphenol A epoxy resin E44, which was purchased from Shanghai Huayuan Century Trading Co., Ltd.

[0021] Example 1 This embodiment provides a method for preparing an additive powder for an iron-based nanocrystalline ribbon, comprising the following steps: B1. By weight, 3 parts of aluminum, 30.33 parts of chromium, 30.33 parts of iron and 30.33 parts of nickel were uniformly mixed to obtain a mixed raw material.

[0022] B2. The mixed raw materials were transferred to a vacuum induction melting gas atomization device, the pressure of which was evacuated to 0.003 Pa, and then the vacuum melting gas atomization device was purged with high-purity nitrogen (99% wt) at a gas flow rate of 10 m / s and a single purge time of 50 minutes. Continuous replacement was performed. When O2 ≤ 1 ppm, H2O ≤ 2 ppm, and H2 ≤ 0.1 ppm and there was no fluctuation for 5 consecutive minutes, the purge was considered complete. The mixed raw materials were smelted at 1900°C for a total of 60 minutes to obtain smelted metal liquid. The smelted metal liquid flowed into the atomization chamber through a draft tube at an atomization pressure of 5 MPa, and was then collected by a cyclone separator to obtain additive powder.

[0023] Example 2 This embodiment provides a method for preparing an additive powder for an iron-based nanocrystalline ribbon, comprising the following steps: B1. By weight, 6 parts of aluminum, 30.33 parts of chromium, 30.33 parts of iron and 30.33 parts of nickel were uniformly mixed to obtain a mixed raw material.

[0024] B2. The mixed raw materials were transferred to a vacuum induction melting gas atomization device, the pressure of which was evacuated to 0.0021 Pa, and then the vacuum melting gas atomization device was purged with high-purity nitrogen (99% wt) at a gas flow rate of 10 m / s and a single purge time of 50 minutes. Continuous replacement was performed. When O2 ≤ 1 ppm, H2O ≤ 2 ppm, and H2 ≤ 0.1 ppm and there was no fluctuation for 5 consecutive minutes, the purge was considered complete. The mixed raw materials were smelted at 1930°C for a total of 80 minutes to obtain smelted metal liquid. The smelted metal liquid flowed into the atomization chamber through a guide tube at an atomization pressure of 5.2 MPa, and was then collected by a cyclone separator to obtain additive powder.

[0025] Example 3 This embodiment provides a method for preparing an additive powder for an iron-based nanocrystalline ribbon, comprising the following steps: B1. 9 parts of aluminum, 30.33 parts of chromium, 30.33 parts of iron and 30.33 parts of nickel were uniformly mixed in parts by mass to obtain a mixed raw material.

[0026] B2. The mixed raw materials were transferred to a vacuum induction melting gas atomization device, the air pressure of which was evacuated to 0.001 Pa, and then the vacuum melting gas atomization device was purged with high-purity nitrogen (99% wt) at a gas flow rate of 10 m / s and a single purge time of 50 minutes. Continuous replacement was performed. When O2 ≤ 1 ppm, H2O ≤ 2 ppm, and H2 ≤ 0.1 ppm and there was no fluctuation for 5 consecutive minutes, the purge was considered complete. The mixed raw materials were smelted at 1950°C for a total of 100 minutes to obtain smelted metal liquid. The smelted metal liquid flowed into the atomization chamber through a draft tube at an atomization pressure of 5.5 MPa, and was then collected by a cyclone separator to obtain additive powder.

[0027] Example 4 This embodiment provides a method for preparing an amorphous ribbon sample, comprising the following steps: A1. Mix 70 parts by mass of iron, 0.5 parts of copper, 2 parts of ferroniobium, 13 parts of silicon, and 8 parts of ferroboron to obtain a prepared raw material. Place the prepared raw material into a boron nitride crucible, transfer the crucible to an induction vacuum melting furnace, and replace the air in the furnace with nitrogen when the vacuum level reaches 0.05 Pa. Then, melt the prepared raw material at 2200°C. After the prepared raw material is completely melted, hold the temperature for 5 minutes, remove from the furnace, and cool to room temperature to prepare a master alloy sample.

[0028] A2. The master alloy sample was placed in a melting ladle for secondary melting at 1350°C to produce an alloy melt. The alloy melt was placed in a quartz tube, and the injection pressure was set to 35 kPa. The pressure valve was pressed, and the pressure difference between the quartz tube and the strip-spinning equipment cavity was used to eject the alloy melt from the quartz tube, producing an amorphous ribbon with a thickness of 20 μm.

[0029] A3. The powdered additive prepared in Example 1 is laser clad on the surface of the amorphous ribbon to form a cladding layer; wherein, the laser power is 1200 W, the scanning speed is 5 mm / s, and the powder feeding speed is 15.5 g / min. The ribbon is then naturally cooled to room temperature to obtain an encapsulated amorphous ribbon. The thickness of the additive on the surface of the amorphous ribbon is 0.5 mm.

[0030] A4. The encapsulated amorphous ribbon was cut into 5 cm strips and then added to a quartz tube. The quartz tube was transferred to a heat treatment furnace. The quartz tube was evacuated to 0.5 Pa. The heat treatment furnace was heated to 500°C at a rate of 20°C / min and kept warm for 80 minutes. The quartz tube was then pushed out of the furnace and allowed to cool naturally. The vacuum state was maintained during the cooling process to obtain an amorphous ribbon sample.

[0031] Example 5 This embodiment provides a method for preparing an amorphous ribbon sample, comprising the following steps: A1. Mix 72 parts by mass of iron, 1 part of copper, 2 parts of ferroniobium, 15 parts of silicon, and 8 parts of ferroboron to obtain a prepared raw material. Place the prepared raw material into a boron nitride crucible, transfer the crucible to an induction vacuum melting furnace, and replace the air in the furnace with nitrogen when the vacuum level reaches 0.08 Pa. Then, melt the prepared raw material at 2250°C. After the prepared raw material is completely melted, hold the temperature for 8 minutes, remove from the furnace, and cool to room temperature to prepare a master alloy sample.

[0032] A2. The master alloy sample was placed in a melting ladle for secondary smelting at 1400°C to produce an alloy melt. The alloy melt was placed in a quartz tube, and the injection pressure was set to 40 kPa. The pressure valve was pressed, and the pressure difference between the quartz tube and the strip-spinning equipment cavity was used to eject the alloy melt from the quartz tube, producing an amorphous ribbon with a thickness of 22 μm.

[0033] A3. The powdered additive prepared in Example 2 is laser clad on the surface of the amorphous ribbon to form a cladding layer; wherein, the laser power is 1300 W, the scanning speed is 6 mm / s, and the powder feeding speed is 16 g / min. The layer is then naturally cooled to room temperature to obtain an encapsulated amorphous ribbon; the thickness of the additive on the surface of the amorphous ribbon is 0.8 mm.

[0034] A4. The encapsulated amorphous ribbon was cut into 8 cm strips and then placed in a quartz tube. The quartz tube was transferred to a heat treatment furnace. The quartz tube was evacuated to 0.8 Pa. The heat treatment furnace was heated to 545°C at a rate of 23°C / min and kept warm for 90 minutes. The quartz tube was then pushed out of the furnace and allowed to cool naturally. The vacuum state was maintained throughout the cooling process to obtain an amorphous ribbon sample.

[0035] Example 6 This embodiment provides a method for preparing an amorphous ribbon sample, comprising the following steps: A1. Mix 73.5 parts of iron, 1.5 parts of copper, 3 parts of ferroniobium, 15 parts of silicon, and 9 parts of ferroboron, by weight, to obtain a prepared raw material. Place the prepared raw material into a boron nitride crucible, transfer the crucible to an induction vacuum melting furnace, and replace the air in the furnace with nitrogen when the vacuum level reaches 0.1 Pa. The prepared raw material is then melted at 2300°C. After the prepared raw material is completely melted, it is held at this temperature for 10 minutes, removed from the furnace, and cooled to room temperature to prepare a master alloy sample.

[0036] A2. The master alloy sample was placed in a melting ladle for secondary melting at 1450°C to produce an alloy melt. The alloy melt was placed in a quartz tube, and the injection pressure was set to 45 kPa. The pressure valve was pressed, and the pressure difference between the quartz tube and the strip-spinning equipment cavity was used to eject the alloy melt from the quartz tube, producing an amorphous ribbon with a thickness of 25 μm.

[0037] A3. The powdered additive prepared in Example 3 is laser clad on the surface of the amorphous ribbon to form a cladding layer; wherein, the laser power is 1400 W, the scanning speed is 8 mm / s, and the powder feeding speed is 16.5 g / min. The layer is then naturally cooled to room temperature to obtain an encapsulated amorphous ribbon; the thickness of the additive on the surface of the amorphous ribbon is 0.1 mm.

[0038] A4. The encapsulated amorphous ribbon was cut into 10 cm strips and then added to a quartz tube. The quartz tube was transferred to a heat treatment furnace. The quartz tube was evacuated to 1 Pa. The heat treatment furnace was heated to 550°C at a rate of 25°C / min and kept warm for 100 minutes. The quartz tube was then pushed out of the furnace and allowed to cool naturally. The vacuum state was maintained during the cooling process to obtain an amorphous ribbon sample.

[0039] Example 7 This embodiment provides a method for preparing an iron-based nanocrystalline ribbon, comprising the following steps: S1. Add 10 g of 3-(fluoromethyl)benzamide, 100 mL of ethanol, and 100 mL of deionized water to a 500 mL three-necked flask and stir at 200 rpm for 20 minutes. Then, add 5 mL of a 10% wt NaOH solution and 16 g of sodium hypochlorite. Stir until the sodium hypochlorite is completely dissolved. Then, heat to 75°C and react for 2 hours to obtain the product. The product is extracted three times with ethyl acetate, and the organic phases are combined and washed with deionized water to obtain the prepared polyfluoroaniline.

[0040] S2. Add 10g of bisphenol A epoxy resin and 5g of polyfluoroaniline to a 500mL three-necked flask equipped with a reflux condenser and purged with nitrogen. Then add 40mL of propylene glycol methyl ether. Reflux at 135°C for 3 hours to obtain the product. The product is then poured into anhydrous ethanol in a volume ratio of 1:5. The product is washed twice with ethanol to remove unreacted monomers. This washed organic viscous liquid is the prepared epoxy resin adhesive.

[0041] S3. Coat the surface of the amorphous thin ribbon sample prepared in Example 4 with epoxy resin adhesive to a thickness of 1 mm, and cure at 80° C. for 60 min to prepare an iron-based nanocrystalline ribbon.

[0042] Example 8 This embodiment provides a method for preparing an iron-based nanocrystalline ribbon, comprising the following steps: S1. Add 15 g of 3-(fluoromethyl)benzamide, 110 mL of ethanol, and 100 mL of deionized water to a 500 mL three-necked flask and stir at 260 rpm for 25 min. Then, add 80 mL of a 12% wt NaOH solution and 26 g of sodium hypochlorite. Stir until the sodium hypochlorite is completely dissolved. Then, heat to 80°C and react for 2.5 h to obtain the product. Extract the product four times with ethyl acetate, combine the organic phases, and wash with deionized water to obtain the prepared polyfluoroaniline.

[0043] S2. Add 14 g of bisphenol A epoxy resin and 7 g of polyfluoroaniline to a 500 mL three-necked flask (equipped with a reflux condenser and purged with nitrogen). Then add 45 mL of propylene glycol methyl ether. Reflux at 140°C for 3.5 hours to obtain the product. The product is then poured into anhydrous ethanol in a volume ratio of 2:5. The product is washed three times with ethanol to remove unreacted monomers. This washed organic viscous liquid is the prepared epoxy resin adhesive.

[0044] S3. Coat the surface of the amorphous thin ribbon sample prepared in Example 5 with epoxy resin adhesive to a thickness of 2 mm, and cure at 90° C. for 80 min to prepare an iron-based nanocrystalline ribbon.

[0045] Example 9 This embodiment provides a method for preparing an iron-based nanocrystalline ribbon, comprising the following steps: S1. Add 20 g of 3-(fluoromethyl)benzamide, 120 mL of ethanol, and 100 mL of deionized water to a 500 mL three-necked flask and stir at 300 rpm for 30 minutes. Then, add 10 mL of a 15% wt NaOH solution and 32 g of sodium hypochlorite. Stir until the sodium hypochlorite is completely dissolved. Then, heat to 85°C and react for 3 hours to obtain the product. The product is extracted five times with ethyl acetate, and the organic phases are combined and washed with deionized water to obtain the prepared polyfluoroaniline.

[0046] S2. Add 20 g of bisphenol A epoxy resin and 10 g of polyfluoroaniline to a 500 mL three-necked flask equipped with a reflux condenser and purged with nitrogen. Then add 50 mL of propylene glycol methyl ether. Reflux at 145°C for 5 hours to obtain the product. The product is then poured into anhydrous ethanol in a volume ratio of 2:5. The product is washed three times with ethanol to remove unreacted monomers, resulting in an organic viscous liquid, which is the prepared epoxy resin adhesive.

[0047] S3. Coat the surface of the amorphous thin ribbon sample prepared in Example 6 with epoxy resin adhesive to a thickness of 2 mm, and cure it at 100° C. for 100 min to prepare an iron-based nanocrystalline ribbon.

[0048] Comparative Example 1 The difference between this comparative example and Example 9 is that no aluminum was added to the mixed raw materials when preparing the auxiliary agent powder.

[0049] Comparative Example 2 This comparative example differs from Example 9 in that step A3 was omitted during the preparation of the amorphous ribbon sample, and the additive was not melt-coated on the surface of the amorphous ribbon. In step A2, the additive and the master alloy sample were added to a melting ladle at a mass ratio of 1:20 for secondary melting to produce an alloy melt. This alloy melt was then injected into a quartz tube at a pressure of 40 kPa to produce the resulting amorphous ribbon sample.

[0050] Comparative Example 3 The difference between this comparative example and Example 9 is that, when preparing the epoxy resin adhesive, step S1 is omitted; and m-phenylenediamine of equal mass is used to replace the prepared polyfluoroaniline.

[0051] Performance testing: 1. The glass transition temperatures of the iron-based nanocrystalline ribbons prepared in Examples 7-9 and Comparative Examples 1-3 were measured using a DSC tester. The temperature was raised from room temperature to 800°C at a heating rate of 20 K / min. The primary and secondary crystallization temperatures were recorded, and the interval between the two crystallization temperatures was calculated.

[0052] 2. The DC soft magnetic properties of the iron-based nanocrystalline ribbons prepared in Examples 7-9 of the present invention and Comparative Examples 1-3 were tested using a DC hysteresis loop instrument. The measured data were the remanence values ​​of the iron-based nanocrystalline ribbons at 550°C. The iron-based nanocrystalline ribbons prepared in Examples 7-9 of the present invention and Comparative Examples 1-3 were then placed at -5°C for 30 minutes, and the remanence values ​​of the prepared ribbons were measured again. Specific test results are shown in the table below: Table 1. Sample performance test data

[0053] Data Analysis: Comparative analysis of the data in the table above shows that the iron-based nanocrystalline ribbons prepared in Examples 7-9 of the present invention all exhibited long crystallization temperature intervals and excellent thermal stability, demonstrating that the iron-based nanocrystalline ribbons prepared in the present invention possess excellent soft magnetic properties. However, in Comparative Example 1, aluminum was not added to the raw material mixture during the preparation of the additive powder, preventing the formation of a highly disordered solid solution structure and hindering dislocation motion, thereby reducing the thermal stability of the prepared iron-based nanocrystalline ribbon.

[0054] In Comparative Example 2, the additive powder was not clad on the surface of the amorphous ribbon, but was instead co-smelted with the master alloy sample to produce an iron-based nanocrystalline ribbon. When the additive powder is added to a master alloy sample composed of specific ratios of ferromagnetic elements, amorphous elements, and nanocrystalline elements, and then refined through a heat treatment process, the thermal stability of the resulting iron-based nanocrystalline ribbon is significantly reduced.

[0055] The iron-based nanocrystalline ribbons prepared in Examples 7-9 of the present invention all exhibited excellent soft magnetic properties, as evidenced by low remanence values ​​at both 550°C and -5°C. However, in Comparative Example 3, the use of m-phenylenediamine in the encapsulating epoxy resin adhesive instead of polyfluoroaniline reduced the high- and low-temperature resistance of the epoxy resin adhesive. This resulted in the iron-based nanocrystalline ribbons prepared in Comparative Example 3 exhibiting high remanence values ​​at both high and low temperatures, resulting in a decrease in soft magnetic properties.

[0056] The above contents are merely examples and explanations of the structure of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they shall fall within the scope of protection of the present invention.

[0057] Throughout this specification, references to terms such as "one embodiment," "example," and "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0058] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing an iron-based nanocrystalline ribbon, characterized in that: The following steps are involved: The surface of the amorphous ribbon is laser clad with auxiliary powder to form an encapsulated amorphous ribbon; the encapsulated amorphous ribbon is subjected to a heat treatment process, coated with an epoxy resin adhesive, and then cured to prepare an iron-based nanocrystalline ribbon.

2. The method for preparing an iron-based nanocrystalline ribbon according to claim 1, characterized in that: The preparation method of the auxiliary agent powder comprises the following steps: B1. In parts by mass, 3-9 parts of aluminum, 30.33 parts of chromium, 30.33 parts of iron and 30.33 parts of nickel were uniformly mixed to obtain a mixed raw material; B2. The mixed raw materials are transferred to a vacuum induction melting gas atomization device. The pressure in the furnace is evacuated to 0.001-0.003 Pa, and then washed with inert gas. The raw materials are smelted at 1900-1950°C for 60-100 minutes to obtain molten metal. The molten metal flows into the atomization chamber through a guide tube at an atomization pressure of 5-5.5 MPa to obtain additive powder.

3. The method for preparing an iron-based nanocrystalline ribbon according to claim 1, wherein: The method for preparing the amorphous ribbon comprises the following steps: A1, iron, copper, ferroniobium, silicon and ferroboron are mixed as raw materials to obtain prepared raw materials; the prepared raw materials are transferred to a vacuum melting furnace with a vacuum degree of 0.05-0.1 Pa; the air in the vacuum melting furnace is replaced with an inert gas, and the prepared raw materials are melted at 2200-2300° C. After being completely melted, the raw materials are kept warm, removed from the furnace, and cooled to room temperature to prepare a master alloy sample; A2. The master alloy sample is placed in a melting ladle for secondary melting at a temperature of 1350-1450°C to obtain an alloy melt; the alloy melt is placed in a quartz tube and sprayed at 35-45 kPa to prepare an amorphous thin ribbon.

4. The method for preparing an iron-based nanocrystalline ribbon according to claim 3, characterized in that: In step A1, the mass ratio of iron, copper, ferroniobium, silicon and ferroboron is 70-73.5:0.5-1.5:2-3:13-15:8-9, and the insulation time is 5-10 minutes.

5. The method for preparing an iron-based nanocrystalline ribbon according to claim 1, characterized in that: The preparation method of the epoxy resin adhesive comprises the following steps: S1, 3-(fluoromethyl)benzamide, ethanol and deionized water are mixed, and then 10-15%wt NaOH solution and sodium hypochlorite are added, and stirred until the sodium hypochlorite is completely dissolved; then the temperature is raised to 75-85°C and the reaction is carried out for 2-3 hours to obtain the product; the product is subjected to post-processing to prepare polyfluoroaniline; S2. Blend bisphenol A epoxy resin, polyfluoroaniline and propylene glycol methyl ether, and reflux for reaction at 135-145° C. for 3-5 hours to obtain a product; wash the product with ethanol to obtain an organic viscous liquid after washing, which is the prepared epoxy resin adhesive.

6. The method for preparing an iron-based nanocrystalline ribbon according to claim 5, characterized in that: In step S1, the usage ratio of 3-(fluoromethyl)benzamide, ethanol, deionized water, NaOH solution and sodium hypochlorite is 10-20 g:100-120 mL:100 mL:5-10 mL:16-32 g; the post-processing steps are: extracting the product with ethyl acetate 3-5 times, combining the organic phases; washing the organic phase with deionized water to obtain the prepared polyfluoroaniline; in step S2, the usage ratio of bisphenol A epoxy resin, polyfluoroaniline and propylene glycol methyl ether is 10-20 g:5-10 g:500 mL; the volume ratio of the product to anhydrous ethanol is 1-2:5, and the product is washed 2-3 times.

7. The method for preparing an iron-based nanocrystalline ribbon according to claim 1, characterized in that: The specific steps of the heat treatment process are: The amorphous ribbon is cut into strips of 5-10 cm to obtain an amorphous ribbon sample; the amorphous ribbon sample is transferred to a heat treatment furnace, and the quartz tube is vacuumed to 0.5-1 Pa; the temperature of the heat treatment furnace is 500-550° C., and the temperature is maintained at this temperature for 80-100 minutes.

8. The method for preparing an iron-based nanocrystalline ribbon according to claim 1, characterized in that: During laser cladding, the laser power is 1200-1400W, the scanning speed is 5-8mm / s, the powder feeding speed is 15.5-16.5g / min, and the cladding thickness is 0.5-1mm; the coating thickness of the epoxy resin adhesive is 1-2mm, the curing temperature is 80-100℃, and the curing time is 60-100min.

9. An iron-based nanocrystalline ribbon, characterized in that: The iron-based nanocrystalline ribbon is prepared by the method for preparing an iron-based nanocrystalline ribbon according to any one of claims 1 to 8.

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