A manufacturing process for preparing amorphous ribbons

Abstract

This invention relates to the field of amorphous alloy smelting technology, specifically a manufacturing process for preparing amorphous ribbon. The process includes the following steps: precise batching, movable furnace top, top charging, electric arc furnace melting, strong oxidation, slag removal, reduction, eccentric EBT tapping (or VOD vacuum treatment), LF deoxidation and desulfurization, precise LF composition control, LF inclusion control (or VD vacuum treatment), LF temperature control, and ribbon spraying. The amorphous ribbon produced by this invention not only has fewer impurities and higher purity but also possesses excellent magnetic properties, effectively ensuring its quality and meeting the needs of high-end applications. The manufacturing process provided by this invention is the first in China to integrate smelting and ribbon spraying. Compared to existing technologies, it adopts a short-process electric arc furnace green production process, significantly reducing pollutant emissions, while also offering advantages such as high production efficiency, low cost, and superior quality.

Description

Technical Field

[0001] This invention relates to the field of amorphous alloy smelting technology, specifically a manufacturing process for preparing amorphous ribbons. Background Technology

[0002] Amorphous ribbon, as a new type of alloy material, possesses many advantages due to its unique atomic arrangement structure, such as high strength and hardness, superplastic deformation ability, excellent corrosion resistance, and outstanding energy-saving effect. It is widely used in transformer cores, sensors, precision instrument parts and other fields.

[0003] Currently, the mainstream preparation method for amorphous ribbon is induction furnace melting, which faces several bottlenecks in actual production. On the one hand, raw material utilization is low. Traditional processes often use expensive virgin raw materials such as pure iron and pure silicon, resulting in high costs. Using silicon steel scrap as raw material is problematic because the impurity content in the scrap is difficult to control, leading to large fluctuations in ribbon performance. Furthermore, incomplete slag treatment during melting further affects product purity. On the other hand, existing functional additives are mostly single-component or simple mixtures, offering limited desulfurization, deoxidation, and impurity removal effects. This fails to effectively improve the fluidity and cleanliness of molten steel, easily causing defects such as porosity and cracks in the ribbon, affecting its microstructure and inevitably impacting its magnetic and mechanical properties. In actual production, existing equipment and technology still have many shortcomings in promoting high-quality development in the amorphous industry.

[0004] In recent years, with the rapid development of industries such as new energy and electronic information, the market's performance requirements for amorphous ribbon have been continuously increasing, forcing the upgrading of its smelting processes and equipment. At the same time, higher standards have been set for cost control, environmental protection, and quality stability in preparation and processes.

[0005] In summary, the present invention provides a manufacturing process for preparing amorphous ribbons to solve the aforementioned technical problems. Summary of the Invention

[0006] The purpose of this invention is to provide a manufacturing process for preparing amorphous ribbons, which is the first manufacturing process in China to integrate melting and ribbon spraying. The amorphous ribbons produced by this invention not only have fewer impurities and higher purity, but also have excellent magnetic properties. The product quality is highly consistent, and the performance of the finished product reaches the international leading level. The green production process greatly reduces environmental pollution, effectively ensures its quality, and can meet the needs of high-end applications.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A manufacturing process for preparing amorphous ribbon includes the following steps: Step 1: After precise batching, scrap steel is added to the electric arc furnace using a movable furnace top charging method. After heating and melting, oxygen is supplied through the furnace door and furnace wall oxygen lances for strong oxidation and decarburization. Then, a foam slag process is used to refine the steel at 1580-1620℃ for 10-15 minutes. After manually removing the slag layer from the surface of the molten steel, reduction treatment is carried out. The steel is tapped without slag using an eccentric EBT, leaving 10-20% steel. The scrap steel contains 10-100wt% social scrap steel. This system employs a top-loading, green, low-carbon, short-process electric arc furnace (EAF) for smelting, controlling steel temperature through precise current adjustment. High-efficiency oxygen supply via furnace door and wall oxygen lances ensures excellent decarburization and heating, while enhancing stirring within the molten pool. The foamed slag process increases furnace input power, improving power factor and thermal efficiency, while maintaining stable dephosphorization, degassing, and inclusion removal. Foamed slag also reduces power consumption, shortens smelting time, and increases productivity. It allows for precise control of oxygen consumption per ton of steel, power consumption, steel feedstock consumption, final carbon-oxygen product, final slag iron oxide content, and final molten steel quality. Achieving slag-free steel tapping reduces secondary oxidation and non-metallic inclusions in molten steel, lowers alloy costs, and facilitates LF and VOD refining; retaining 10%-20% of the steel shortens the preheating and melting time for the next heat, reducing power consumption by 5%-10%; the initial melting temperature of molten steel reaches 1580-1620℃, providing favorable conditions for alloying; the smelting cycle is shortened, and production capacity is significantly increased. By adopting the above technical solutions, production organization is flexible, scrap steel and alloying elements can be better reused, equipment stability is strong, process repeatability is good, the pace is faster, molten steel is purer, and energy consumption is lower. Step 2: If the carbon content of the finished amorphous ribbon is required to be <0.08% and the carbon content of the molten steel obtained in Step 1 is >0.08%, the molten steel is subjected to VOD vacuum treatment, and inert gas is blown into the molten steel through the bottom blowing ventilation element of the ladle to stir the molten steel and achieve deep decarburization and dehydrogenation; if the carbon content of the finished amorphous ribbon is required to be >0.08%, the molten steel obtained in Step 1 is directly entered into LF refining and then subjected to VD dehydrogenation treatment. Among them, the vacuum degree is ≤67Pa and the pressure is maintained for 15-20min; by adopting the above technical solution, the smelting requirements of low carbon or ultra-low carbon materials are met, O <20ppm, and H ≤1.2ppm after degassing; Step 3: The molten steel, silicon alloy, boron alloy, and niobium alloy processed in Step 2 are added to the LF ladle refining furnace for refining at a weight ratio of 10-15:1:0.2-0.5:0.8-0.9. Inert gas is blown into the slag through the bottom blowing permeable element of the ladle to stir it and ensure thorough mixing. Submerged arc heating is used to achieve long-term precise control of the molten temperature. Then, 0.3-0.8 wt% functional additives and 0.02-0.03 wt% rare earth elements are added to the surface of the molten steel to form a refining slag system to achieve good desulfurization and adsorption of inclusions. The contents of C, B, Si, and S are controlled during the refining process. By employing the above-mentioned technologies—deoxidation, desulfurization, degassing, removal of non-metallic inclusions, and adjustment of the steel melt composition and temperature within a suitable range—the purity of the solution is improved. This further addresses the issues of segregation and excessive gas content in amorphous alloys. Step 4: Transfer the composite melt obtained in Step 3 into a bottom-pouring furnace at 1400-1450℃ and keep it at that temperature; then pour the composite melt into a nozzle for spraying, and cool and throw it out under the rapid rotation of the copper roller to form a strip. Under the action of a transverse magnetic field, the strip is annealed at 500-600℃ for 20-30 minutes to obtain an amorphous strip.

[0008] Furthermore, the mass percentage content of each element in the composite melt is as follows: 1.01%≤Si≤2.43%, 1.67%≤B≤2.58%, 0.12%≤C≤0.28%, S≤0.008%.

[0009] Furthermore, the inert gas is selected from nitrogen or argon, and the flow rate of the inert gas is 15-20 L / min, and the pressure is 0.5-0.8 MPa.

[0010] Furthermore, the rare earth element is any one of yttrium, lanthanum, and cerium.

[0011] Furthermore, the functional additive has a three-layer concentric spherical structure, consisting of a core layer, an intermediate layer, and a surface layer from the inside out; the mass ratio of the core layer, intermediate layer, and surface layer is 1:0.8-1:0.5-0.8. The surface layer consists of the following components: 20-25 wt% calcium fluoride, 8-12 wt% refining slag, 3-5 wt% bentonite, 4-6 wt% water glass binder, and the balance being lime. The intermediate layer consists of the following components: 20-25 wt% aluminum powder, 10-15 wt% ferrosilicon, 5-10 wt% graphite, 5-8 wt% aluminum dihydrogen phosphate, and the balance being silicon-calcium alloy powder. The core layer consists of the following components: 30-40 wt% calcium carbonate, 10-15 wt% calcium fluoride, 5-10 wt% clay, and the balance being magnesium carbonate.

[0012] Furthermore, the preparation method of the functional additive includes the following steps: Step 1: Accurately weigh the raw materials for each layer of the functional additive, add water to the surface layer and intermediate layer raw materials respectively, mix and stir evenly to obtain surface layer slurry and intermediate layer slurry with a viscosity of 400-600 mPa·s; then add the core layer raw materials to the mixer, dry mix for 20-30 min, add 15-20 wt% of water to the resulting mixture, mix and stir until the moisture content of the material is 10-12 wt%, then extrude and granulate and dry and solidify in sequence to obtain core layer microspheres; The second step involves adding the core-layer microspheres to a fluidized bed granulator at an airflow rate of 400-600 m³ / h. 3 Under the conditions of / h and bed temperature of 80-100℃, first spray the intermediate layer slurry, then spray the surface layer slurry until the particle diameter reaches 3.0-3.5mm; The third step involves drying the core-coated microspheres obtained in the second step at 100-120℃ for 2-3 hours, then curing them at 200-250℃ for 3-4 hours. The particles are then surface-sprayed with a silane coupling agent solution and dried at 80-100℃ to obtain the functional additive.

[0013] Furthermore, in the first step, the extrusion pressure is 5-8 MPa and the discharge rate is 20-25 kg / h.

[0014] Furthermore, in the first step, the drying and curing temperature is set to 80-100℃, and the drying is carried out until the moisture content of the core layer microspheres is ≤1.5wt%, and the particle size of the core layer microspheres is 1.6-2.0mm.

[0015] Furthermore, the concentration of the silane coupling agent solution is 5-8 wt%, and the solvent used for the silane coupling agent solution is a 70-85 wt% aqueous ethanol solution; the amount of the silane coupling agent is 3-5 wt% of the core layer microspheres.

[0016] Furthermore, the silane coupling agent is any one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, and 3-aminopropylmethyldiethoxysilane. Compared with the prior art, the beneficial effects of the present invention are: This invention abandons the separate melting and impurity removal pretreatment process, adopting a step-by-step feeding method combined with specialized functional additives. Through the multiple purification effects of slag and manual slag removal, it can efficiently remove waste materials and inherent impurities in the refractory material itself, solving the problem of unstable raw material purity from the source. Furthermore, this invention reduces both smelting energy consumption and raw material loss during the process. Simultaneously, it utilizes scrap steel from the market, making it an environmentally friendly manufacturing process that significantly saves on raw material procurement costs and production energy costs. At the same time, the alloy ingot strictly controls the content of impurities such as carbon, nitrogen, oxygen, and phosphorus to extremely low levels, laying a solid foundation for the purity of the subsequent master alloy melt and the stability of the strip's performance.

[0017] 2. The functional additive with a three-layer concentric spherical structure prepared in this invention achieves multiple purification effects through the synergistic effect of each layer. The surface layer, composed of calcium fluoride, refining slag, and lime, can quickly form a slag layer with good fluidity, adsorbing impurities on the surface of molten steel. The middle layer, composed of aluminum powder and ferrosilicon, has strong deoxidation and desulfurization capabilities, while the silicon-calcium alloy powder further enhances the deoxidation effect, and graphite optimizes the slag-steel reaction kinetics. The core layer, composed of calcium carbonate and magnesium carbonate, decomposes at high temperatures to generate gas, stirring the molten steel and promoting the flotation of impurities, while calcium fluoride optimizes the fluidity of the molten slag.

[0018] 3. This invention precisely proportions the weight of alloy ingots, elemental silicon, boron, and niobium, along with trace amounts of rare earth elements. These rare earth elements refine grains and inhibit crystallization, while boron and niobium, as amorphous forming elements, significantly enhance the alloy's amorphous forming ability, preventing crystallization defects in the strip. The introduction of argon gas effectively isolates the strip from air, preventing secondary oxidation, and achieves uniform temperature control, ensuring a stable melting process. Strict control of impurities such as carbon, nitrogen, oxygen, phosphorus, and sulfur to extremely low levels lays a solid foundation for the subsequent stability of the strip's performance.

[0019] 4. The combination of VD vacuum smelting and electromagnetic stirring can completely remove gaseous impurities in the molten metal, making the composition more uniform; the bottom-pouring furnace holding temperature is precisely matched with the fluidity requirements of the molten metal; the synergistic effect of copper roller rapid cooling and transverse magnetic field annealing can eliminate internal stress in the strip, improve the degree of amorphization, and give the strip excellent magnetic properties, high strength and high hardness, meeting the application requirements of high-end fields.

[0020] 5. This invention reduces smelting energy consumption and increases production capacity by significantly improving production efficiency. Secondly, the process of this invention is flexible and controllable. The electric arc furnace can be started and stopped quickly according to production organization and market fluctuations, making it suitable for the manufacturing of high-end materials in small batches of multiple varieties.

[0021] 6. This invention utilizes 10-100% recycled steel, making it an environmentally friendly manufacturing process that significantly reduces procurement and production energy costs. Furthermore, this invention not only improves the technical and economic indicators of amorphous alloy production but also provides an innovative solution for manufacturing high-quality amorphous ribbons, thus driving technological progress in the industry.

[0022] 7. The manufacturing process provided by this invention is the first in China to integrate smelting and ribbon spraying. Compared with existing technologies, it adopts a green production process using a short-process electric arc furnace, significantly reducing pollutant emissions. It also boasts advantages such as high production efficiency, low cost, and superior quality. Furthermore, the amorphous ribbon manufactured using this invention not only has fewer impurities and higher purity, but also exhibits strong product quality consistency, with finished product performance reaching international leading levels. In addition, this invention provides new ideas for the high-quality development of amorphous alloys, promoting technological progress in the industry. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0024] The social scrap steel mentioned in the following examples and comparative examples refers to scrap steel recycled from various sectors of society after use, excluding self-produced scrap steel generated within steel mills; while scrap steel is a general term for both social scrap steel and self-produced scrap steel.

[0025] Example 1 A manufacturing process for preparing amorphous ribbon includes the following steps: Step 1: After precise batching, scrap steel is added to the electric arc furnace using a movable furnace top charging method. After heating and melting, oxygen is supplied through the furnace door and furnace wall oxygen lances for strong oxidation and decarburization. Then, the steel is refined at 1580℃ for 15 minutes using a foam slag process. After manually removing the slag layer from the surface of the molten steel, reduction treatment is carried out. The steel is then tapped without slag using an eccentric EBT, leaving 10% of the steel. The scrap steel contains 10wt% social scrap steel. Step 2: If the carbon content of the finished amorphous ribbon is required to be <0.08% and the carbon content of the molten steel obtained in Step 1 is >0.08%, the molten steel is subjected to VOD vacuum treatment, and inert gas is blown into the molten steel through the bottom blowing ventilation element of the ladle to stir the molten steel and achieve deep decarburization and dehydrogenation; if the carbon content of the finished amorphous ribbon is required to be >0.08%, the molten steel obtained in Step 1 is directly entered into LF refining and then subjected to VD dehydrogenation treatment; the vacuum degree is 67 Pa and the pressure is held for 15 min. Step 3: The molten steel, silicon alloy, boron alloy, and niobium alloy processed in Step 2 are added to the LF ladle refining furnace in a weight ratio of 10:1:0.2:0.8 for refining. Inert gas is blown into the slag through the bottom blowing permeable element of the ladle to stir the slag and ensure thorough mixing. Submerged arc heating is used to achieve long-term precise control of the molten temperature. Then, 0.3 wt% functional additives and 0.02 wt% rare earth yttrium are added to the surface of the molten steel to form a refining slag system to achieve good desulfurization and adsorption of inclusions. The contents of C, B, Si, and S are controlled during the refining process. Step 4: Transfer the composite melt obtained in Step 3 into a bottom-pouring furnace at 1400℃ and keep it at that temperature; then pour the composite melt into a nozzle for spraying, and cool and throw it out under the rapid rotation of the copper roller to form a strip. Under the action of a transverse magnetic field, the strip is annealed at 500℃ for 30 minutes to obtain an amorphous strip.

[0026] The mass percentage content of each element in the composite melt is as follows: 1.01%≤Si≤2.43%, 1.67%≤B≤2.58%, 0.12%≤C≤0.28%, S≤0.008%.

[0027] Nitrogen or argon is used as the inert gas, and the flow rate of the inert gas is 15 L / min and the pressure is 0.5 MPa.

[0028] The functional additive has a three-layer concentric spherical structure, consisting of a core layer, an intermediate layer, and a surface layer from the inside out; the mass ratio of the core layer, intermediate layer, and surface layer is 1:0.8:0.5. The surface layer consists of the following components: 20 wt% calcium fluoride, 8 wt% refining slag, 3 wt% bentonite, 4 wt% water glass binder, and the balance being lime. The intermediate layer consists of the following components: 20wt% aluminum powder, 10wt% ferrosilicon, 5wt% graphite, 5wt% aluminum dihydrogen phosphate, and the balance being silicon-calcium alloy powder. The core layer consists of the following components: 30 wt% calcium carbonate, 10 wt% calcium fluoride, 5 wt% clay, and the balance being magnesium carbonate.

[0029] The preparation method of functional additives includes the following steps: Step 1: Accurately weigh the raw materials for each layer of the functional additive, add water to the surface layer and intermediate layer raw materials respectively, mix and stir evenly to obtain surface layer slurry and intermediate layer slurry with a viscosity of 400 mPa·s; then add the core layer raw materials to the mixer, dry mix for 20 minutes, add 15 wt% of water to the resulting mixture, mix and stir until the moisture content of the material is 10 wt%, then extrude and granulate and dry and solidify in sequence to obtain core layer microspheres; The extrusion pressure is 5 MPa, and the discharge speed is 20 kg / h. The drying and curing temperature was set to 80℃, and the drying was carried out until the moisture content of the core layer microspheres was 1.5wt% and the particle size of the core layer microspheres was 1.6mm. The second step involves adding the core-layer microspheres to a fluidized bed granulator at an airflow rate of 400 m³ / h. 3 Under the conditions of / h and bed temperature of 80℃, first spray the intermediate layer slurry, then spray the surface layer slurry until the particle diameter reaches 3.0mm; The third step is to dry the core layer microspheres obtained in the second step at 100°C for 3 hours, then cure them at 200°C for 4 hours, and then spray the particles with a silane coupling agent solution. After drying at 80°C, the functional additive is obtained. The concentration of the silane coupling agent solution is 5 wt%, and the solvent used for the silane coupling agent solution is a 70 wt% aqueous ethanol solution; the amount of silane coupling agent is 3 wt% of the core microspheres; and the silane coupling agent is 3-aminopropyltrimethoxysilane.

[0030] Example 2 A manufacturing process for preparing amorphous ribbon includes the following steps: Step 1: After precise batching, scrap steel is added to the electric arc furnace using a movable furnace top charging method. After heating and melting, oxygen is supplied through the furnace door and furnace wall oxygen lances for strong oxidation and decarburization. Then, the steel is refined at 1600℃ for 15 minutes using a foam slag process. After manually removing the slag layer from the surface of the molten steel, reduction treatment is carried out. The steel is then tapped without slag using an eccentric EBT, leaving 15% of the steel. The scrap steel contains 50wt% social scrap steel. Step 2: If the carbon content of the finished amorphous ribbon is required to be <0.08% and the carbon content of the molten steel obtained in Step 1 is >0.08%, the molten steel is subjected to VOD vacuum treatment, and inert gas is blown into the molten steel through the bottom blowing ventilation element of the ladle to stir the molten steel and achieve deep decarburization and dehydrogenation; if the carbon content of the finished amorphous ribbon is required to be >0.08%, the molten steel obtained in Step 1 is directly entered into LF refining and then subjected to VD dehydrogenation treatment; the vacuum degree is 65Pa and the pressure is held for 20min. Step 3: The molten steel, silicon alloy, boron alloy, and niobium alloy processed in Step 2 are fed into the LF ladle refining furnace in a weight ratio of 15:1:0.3:0.9 for refining. Inert gas is blown into the slag through the bottom blowing permeable element of the ladle to stir the slag and ensure thorough mixing. Submerged arc heating is used to achieve long-term precise control of the molten temperature. Then, 0.6 wt% functional additives and 0.03 wt% rare earth lanthanum are added to the surface of the molten steel to form a refining slag system to achieve good desulfurization and adsorption of inclusions. The contents of C, B, Si, and S are controlled during the refining process. Step 4: Transfer the composite melt obtained in Step 3 into a bottom-pouring furnace at 1450℃ and keep it warm; then pour the composite melt into a nozzle for spraying, and cool and throw it out under the rapid rotation of the copper roller to form a strip. Under the action of a transverse magnetic field, the strip is annealed at 550℃ for 25 minutes to obtain an amorphous strip.

[0031] The mass percentage content of each element in the composite melt is as follows: 1.01%≤Si≤2.43%, 1.67%≤B≤2.58%, 0.12%≤C≤0.28%, S≤0.008%.

[0032] Nitrogen or argon is used as the inert gas, and the flow rate of the inert gas is 20 L / min and the pressure is 0.8 MPa.

[0033] The functional additive has a three-layer concentric spherical structure, consisting of a core layer, an intermediate layer, and a surface layer from the inside out; the mass ratio of the core layer, intermediate layer, and surface layer is 1:1:0.8. The surface layer consists of the following components: 25 wt% calcium fluoride, 10 wt% refining slag, 4 wt% bentonite, 5 wt% water glass binder, and the balance being lime. The intermediate layer consists of the following components: 25 wt% aluminum powder, 15 wt% ferrosilicon, 8 wt% graphite, 6 wt% aluminum dihydrogen phosphate, and the balance being silicon-calcium alloy powder. The core layer consists of the following components: 35 wt% calcium carbonate, 12 wt% calcium fluoride, 8 wt% clay, and the balance being magnesium carbonate.

[0034] The preparation method of functional additives includes the following steps: Step 1: Accurately weigh the raw materials for each layer of the functional additive, add water to the surface layer and intermediate layer raw materials respectively, mix and stir evenly to obtain surface layer slurry and intermediate layer slurry with a viscosity of 500 mPa·s; then add the core layer raw material to the mixer, dry mix for 25 min, add 20 wt% of water to the obtained mixture, mix and stir until the moisture content of the material is 12 wt%, then extrude and granulate and dry and solidify in sequence to obtain core layer microspheres; The extrusion pressure is 6 MPa and the discharge speed is 25 kg / h. The drying and curing temperature was set to 90℃, and the drying was carried out until the moisture content of the core layer microspheres was 1.4wt% and the particle size of the core layer microspheres was 1.8mm. The second step involves adding the core-layer microspheres to a fluidized bed granulator at an airflow rate of 500 m³ / h. 3 Under the conditions of / h and bed temperature of 90℃, first spray the intermediate layer slurry, then spray the surface layer slurry until the particle diameter reaches 3.5mm; The third step is to dry the core layer microspheres obtained in the second step at 110℃ for 3 hours, then cure them at 230℃ for 4 hours, and then spray the surface of the particles with a silane coupling agent solution and dry them at 90℃ to obtain the functional additive. The concentration of the silane coupling agent solution is 6 wt%, and the solvent used for the silane coupling agent solution is an 80 wt% aqueous ethanol solution; the amount of silane coupling agent used is 4 wt% of the core microspheres; and the silane coupling agent is 3-aminopropyltriethoxysilane.

[0035] Example 3 A manufacturing process for preparing amorphous ribbon includes the following steps: Step 1: After precise batching, scrap steel is added to the electric arc furnace using a movable furnace top charging method. After heating and melting, oxygen is supplied through the furnace door and furnace wall oxygen lances for strong oxidation and decarburization. Then, a foam slag process is used to refine the steel at 1620℃ for 10 minutes. After manually removing the slag layer from the surface of the molten steel, reduction treatment is performed. The steel is then tapped without slag using an eccentric EBT, leaving 20% ​​of the steel. Step 2: If the carbon content of the finished amorphous ribbon is required to be <0.08% and the carbon content of the molten steel obtained in Step 1 is >0.08%, the molten steel is subjected to VOD vacuum treatment, and inert gas is blown into the molten steel through the bottom blowing ventilation element of the ladle to stir the molten steel and achieve deep decarburization and dehydrogenation; if the carbon content of the finished amorphous ribbon is required to be >0.08%, the molten steel obtained in Step 1 is directly entered into LF refining and then subjected to VD dehydrogenation treatment; wherein, the vacuum degree is ≤65Pa and the pressure is held for 20min; Step 3: The molten steel, silicon alloy, boron alloy, and niobium alloy processed in Step 2 are added to the LF ladle refining furnace in a weight ratio of 15:1:0.5:0.9 for refining. Inert gas is blown into the slag through the bottom blowing permeable element of the ladle to stir the slag and ensure thorough mixing. Submerged arc heating is used to achieve long-term precise control of the molten temperature. Then, 0.8 wt% functional additives and 0.03 wt% rare earth cerium are added to the surface of the molten steel to form a refining slag system to achieve good desulfurization and adsorption of inclusions. The contents of C, B, Si, and S are controlled during the refining process. Step 4: Transfer the composite melt obtained in Step 3 into a bottom-pouring furnace at 1450℃ and keep it warm; then pour the composite melt into a nozzle for spraying, and cool and throw it out under the rapid rotation of the copper roller to form a strip. Under the action of a transverse magnetic field, the strip is annealed at 600℃ for 20 minutes to obtain an amorphous strip.

[0036] The mass percentage content of each element in the composite melt is as follows: 1.01%≤Si≤2.43%, 1.67%≤B≤2.58%, 0.12%≤C≤0.28%, S≤0.008%.

[0037] Nitrogen or argon is used as the inert gas, and the flow rate of the inert gas is 20 L / min and the pressure is 0.8 MPa.

[0038] The functional additive has a three-layer concentric spherical structure, consisting of a core layer, an intermediate layer, and a surface layer from the inside out; the mass ratio of the core layer, intermediate layer, and surface layer is 1:1:0.8. The surface layer consists of the following components: 25 wt% calcium fluoride, 12 wt% refining slag, 5 wt% bentonite, 6 wt% water glass binder, and the balance being lime. The intermediate layer consists of the following components: 25 wt% aluminum powder, 15 wt% ferrosilicon, 10 wt% graphite, 8 wt% aluminum dihydrogen phosphate, and the balance being silicon-calcium alloy powder. The core layer consists of the following components: 40 wt% calcium carbonate, 15 wt% calcium fluoride, 10 wt% clay, and the balance being magnesium carbonate.

[0039] The preparation method of functional additives includes the following steps: Step 1: Accurately weigh the raw materials for each layer of the functional additive, add water to the surface layer and intermediate layer raw materials respectively, mix and stir evenly to obtain surface layer slurry and intermediate layer slurry with a viscosity of 600 mPa·s; then add the core layer raw material to the mixer, dry mix for 30 min, add 20 wt% of water to the obtained mixture, mix and stir until the material moisture content is 12 wt%, then extrude and granulate and dry and solidify in sequence to obtain core layer microspheres; The extrusion pressure is 8 MPa, and the discharge speed is 25 kg / h. The drying and curing temperature was set to 100℃, and the core layer microspheres were dried until the moisture content was 1.4wt% and the particle size was 2.0mm. The second step involves adding the core-layer microspheres to a fluidized bed granulator at an airflow rate of 600 m³ / h. 3 Under the conditions of / h and bed temperature of 100℃, first spray the intermediate layer slurry, then spray the surface layer slurry until the particle diameter reaches 3.5mm; The third step is to dry the core layer microspheres obtained in the second step at 120°C for 2 hours, then cure them at 250°C for 3 hours, and then spray the particles with a silane coupling agent solution. After drying at 80°C, the functional additive is obtained. The concentration of the silane coupling agent solution is 8 wt%, and the solvent used for the silane coupling agent solution is an 85 wt% aqueous ethanol solution; the amount of silane coupling agent used is 5 wt% of the core microspheres; and the silane coupling agent is 3-aminopropyldimethylethoxysilane.

[0040] Comparative Example 1: The difference from Example 1 is that no functional additives were used in this comparative example.

[0041] Comparative Example 2: The difference from Example 1 is that rare earth elements were not used in this comparative example.

[0042] Comparative Example 3: The difference from Example 1 is that the strip was not annealed under a transverse magnetic field in this comparative example; that is, the composite melt in this comparative example was directly made into an amorphous strip after being sprayed, cooled and thrown out under the rapid rotation of the copper roller.

[0043] Performance testing The relevant properties of the amorphous ribbon samples prepared in Examples 1-3 and Comparative Examples 1-3 were tested, and the experimental data are recorded in the table below:

[0044] By comparing and analyzing the relevant data in the table, it can be seen that the amorphous ribbon produced by this invention not only has fewer impurities and higher purity, but also possesses excellent magnetic properties, effectively ensuring its quality and meeting the needs of high-end applications. This indicates that the manufacturing process for preparing amorphous ribbons provided by this invention has a broader market prospect and is more suitable for widespread application.

[0045] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above 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 one or more embodiments or examples.

[0046] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A manufacturing process for preparing amorphous ribbons, characterized in that, Includes the following steps: Step 1: After precise batching, scrap steel is added to the electric arc furnace using a movable furnace top charging method. After heating and melting, oxygen is supplied through the furnace door and furnace wall oxygen lances for strong oxidation and decarburization. Then, a foam slag process is used to refine the steel at 1580-1620℃ for 10-15 minutes. After manually removing the slag layer from the surface of the molten steel, reduction treatment is carried out. The steel is tapped without slag using an eccentric EBT, leaving 10-20% steel. The scrap steel contains 10-100wt% social scrap steel. Step 2: If the carbon content of the finished amorphous ribbon is required to be <0.08% and the carbon content of the molten steel obtained in Step 1 is >0.08%, the molten steel is subjected to VOD vacuum treatment, and inert gas is blown into the molten steel through the bottom blowing ventilation element of the ladle to stir the molten steel and achieve deep decarburization and dehydrogenation; if the carbon content of the finished amorphous ribbon is required to be >0.08%, the molten steel obtained in Step 1 is directly entered into LF refining and then subjected to VD dehydrogenation treatment. Step 3: The molten steel, silicon alloy, boron alloy, and niobium alloy processed in Step 2 are added to the LF ladle refining furnace for refining at a weight ratio of 10-15:1:0.2-0.5:0.8-0.

9. Inert gas is blown into the slag through the bottom blowing permeable element of the ladle to stir it and ensure thorough mixing. Submerged arc heating is used to achieve long-term precise control of the molten temperature. Then, 0.3-0.8 wt% functional additives and 0.02-0.03 wt% rare earth elements are added to the surface of the molten steel to form a refining slag system to achieve good desulfurization and adsorption of inclusions. The contents of C, B, Si, and S are controlled during the refining process. Step 4: Transfer the composite melt obtained in Step 3 into a bottom-pouring furnace at 1400-1450℃ and keep it at that temperature; then pour the composite melt into a nozzle for spraying, and cool and throw it out under the rapid rotation of the copper roller to form a strip. Under the action of a transverse magnetic field, the strip is annealed at 500-600℃ for 20-30 minutes to obtain an amorphous strip.

2. The manufacturing process for preparing amorphous ribbons according to claim 1, characterized in that, The mass percentage content of each element in the composite melt is as follows: 1.01%≤Si≤2.43%, 1.67%≤B≤2.58%, 0.12%≤C≤0.28%, S≤0.008%.

3. The manufacturing process for preparing amorphous ribbons according to claim 1, characterized in that: The inert gas is selected from nitrogen or argon, and the flow rate of the inert gas is 15-20 L / min and the pressure is 0.5-0.8 MPa.

4. The manufacturing process for preparing amorphous ribbons according to claim 1, characterized in that: The rare earth element is any one of yttrium, lanthanum, and cerium.

5. The manufacturing process for preparing amorphous ribbons according to claim 1, characterized in that, The functional additive has a three-layer concentric spherical structure, consisting of a core layer, an intermediate layer, and a surface layer from the inside out; the mass ratio of the core layer, intermediate layer, and surface layer is 1:0.8-1:0.5-0.

8. The surface layer consists of the following components: 20-25 wt% calcium fluoride, 8-12 wt% refining slag, 3-5 wt% bentonite, 4-6 wt% water glass binder, and the balance being lime. The intermediate layer consists of the following components: 20-25 wt% aluminum powder, 10-15 wt% ferrosilicon, 5-10 wt% graphite, 5-8 wt% aluminum dihydrogen phosphate, and the balance being silicon-calcium alloy powder. The core layer consists of the following components: 30-40 wt% calcium carbonate, 10-15 wt% calcium fluoride, 5-10 wt% clay, and the balance being magnesium carbonate.

6. The manufacturing process for preparing amorphous ribbons according to claim 5, characterized in that, The preparation method of the functional additive includes the following steps: Step 1: Accurately weigh the raw materials for each layer of the functional additive, add water to the surface layer and intermediate layer raw materials respectively, mix and stir evenly to obtain surface layer slurry and intermediate layer slurry with a viscosity of 400-600 mPa·s; then add the core layer raw materials to the mixer, dry mix for 20-30 min, add 15-20 wt% of water to the resulting mixture, mix and stir until the moisture content of the material is 10-12 wt%, then extrude and granulate and dry and solidify in sequence to obtain core layer microspheres; The second step involves adding the core-layer microspheres to a fluidized bed granulator at an airflow rate of 400-600 m³ / h. 3 Under the conditions of / h and bed temperature of 80-100℃, first spray the intermediate layer slurry, then spray the surface layer slurry until the particle diameter reaches 3.0-3.5mm; The third step involves drying the core-coated microspheres obtained in the second step at 100-120℃ for 2-3 hours, then curing them at 200-250℃ for 3-4 hours. The particles are then surface-sprayed with a silane coupling agent solution and dried at 80-100℃ to obtain the functional additive.

7. A manufacturing process for preparing amorphous ribbons according to claim 6, characterized in that, In the first step, the extrusion pressure is 5-8 MPa and the discharge speed is 20-25 kg / h.

8. The manufacturing process for preparing amorphous ribbons according to claim 6, characterized in that, In the first step, the drying and curing temperature is set to 80-100℃, and the drying is carried out until the moisture content of the core layer microspheres is ≤1.5wt% and the particle size of the core layer microspheres is 1.6-2.0mm.

9. A manufacturing process for preparing amorphous ribbons according to claim 6, characterized in that, The concentration of the silane coupling agent solution is 5-8 wt%, and the solvent used for the silane coupling agent solution is a 70-85 wt% aqueous ethanol solution; the amount of the silane coupling agent is 3-5 wt% of the core layer microspheres.

10. A manufacturing process for preparing amorphous ribbons according to claim 6 or 9, characterized in that: The silane coupling agent is any one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylethoxysilane, and 3-aminopropylmethyldiethoxysilane.

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