Copper roller material for iron-based amorphous strip and gradient heat treatment process

Abstract

The invention discloses a copper roller material for an iron-based amorphous strip and a gradient heat treatment process, and belongs to the technical field of amorphous alloy material preparation, the material comprises the following elements in percentage by weight: 0.02%-0.10% of Si, 0.02%-0.05% of W, 0.05%-0.08% of Zr, 0.05%-0.1% of Al, 0.02%-0.04% of Mg, 0.04%-0.13% of ZrO2-WC-coated Al2O3 core-shell particles and the balance of Cu, and the total amount is 100%. By optimizing the components of the copper roller material and adopting the unique gradient heat treatment process, the comprehensive performance of the copper roller can be effectively improved, the copper roller can still keep good cooling effect, wear resistance and heat conductivity in the long-time continuous production process, and therefore the quality of the iron-based amorphous strip and the stability of the production efficiency are guaranteed. Therefore, the quality and the production efficiency of the iron-based amorphous strip are improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of amorphous alloy material preparation, and in particular relates to a copper roller material for iron-based amorphous strip and a gradient heat treatment process. Background Art

[0002] Amorphous alloys, also known as metallic glasses, were first discovered in the 1970s. They utilize rapid cooling technology to form molten steel into micron-thick ribbons in a single step. The resulting solid alloy (ribbon) exhibits a different structure from the regularly arranged crystalline structure of cold-rolled silicon steel. The irregular arrangement of atoms in this alloy, known as amorphous, gives it narrow B-H circuits, resulting in high magnetic permeability and low losses. Furthermore, the irregular arrangement of atoms in amorphous alloys restricts the free flow of electrons, resulting in a higher resistivity than crystalline alloys, which also helps reduce eddy current losses. Transformer cores made from amorphous alloys exhibit lower no-load losses than conventional transformers made from silicon steel sheets, making amorphous alloy transformers significantly energy-efficient and environmentally friendly. When used in oil-immersed transformers, amorphous alloy transformer cores can significantly reduce emissions of various harmful gases. Consequently, an increasing number of manufacturers are adopting amorphous alloys as raw materials for transformer cores.

[0003] Iron-based amorphous alloys have attracted considerable attention from researchers due to their excellent soft magnetic properties and corrosion resistance. Currently, iron-based amorphous strips are primarily produced using the single-roll rapid quenching method, which involves spraying a stream of molten alloy onto the surface of a high-speed rotating copper roll. Rapid cooling by the roll causes the alloy to rapidly solidify into an amorphous strip. For example, Chinese patent application CN201410469941.X describes a method for preparing iron-based amorphous alloys. This method is cost-effective and simple to implement, significantly improving the glass-forming ability without reducing saturation magnetization. The invention utilizes single-roll rapid quenching or copper mold casting to prepare both strip and bulk iron-based amorphous alloy samples, respectively. Specifically, under argon protection, trace elements are added to the iron-based amorphous alloy, which is then melted in a reactor in a stoichiometric ratio and rapidly cooled and solidified. The added element is copper, constituting 0.1% to 1.0% atomic percent of the total iron-based amorphous alloy. This results in an iron-based amorphous alloy with both high saturation magnetization and high glass-forming ability.

[0004] In this process, cooling copper rollers are key components in industrial amorphous strip production equipment. Their cooling efficiency directly impacts changes in the amorphous grain structure and magnetic properties. These rollers must not only provide a sufficient cooling rate to ensure the formation of the amorphous strip, but also possess excellent wear resistance and thermal conductivity to ensure strip quality and production efficiency. However, existing copper roller materials have performance limitations, such as limited cooling rates and poor wear resistance, which, to a certain extent, impact the quality and production efficiency of iron-based amorphous strip.

[0005] Therefore, it is of great practical significance to develop a copper roller material with excellent performance for iron-based amorphous strip and the corresponding processing technology. Summary of the Invention

[0006] This invention addresses the challenges of the prior art by providing a copper roller material and gradient heat treatment process for iron-based amorphous strip, addressing deficiencies in existing copper roller materials in cooling rate and wear resistance. The copper roller material for iron-based amorphous strip of the present invention, through a rational element ratio and unique preparation process, achieves superior copper roller performance, better meeting the demands of amorphous strip production. The gradient heat treatment process further optimizes the copper roller material's structure and properties, significantly enhancing its cooling efficiency, wear resistance, and thermal conductivity, thereby improving the quality and production efficiency of iron-based amorphous strip.

[0007] In order to achieve the above technical objectives, the technical solution adopted by the present invention is: A copper roller material for an iron-based amorphous strip comprises the following elements by weight: 0.02%-0.10% Si, 0.02%-0.05% W, 0.05%-0.08% Zr, 0.05%-0.1% Al, 0.02%-0.04% Mg, 0.04%-0.13% ZrO2-WC@Al2O3 core-shell particles, and the balance being copper (Cu), with a total weight percentage of 100%.

[0008] Preferably, the copper roller material for the iron-based amorphous strip contains the following elements by weight percentage: Si 0.10%, W 0.05%, Zr 0.08%, Al 0.1%, Mg 0.04%, ZrO2-WC@Al2O3 core-shell particles 0.13%, and the balance is copper Cu, with a total amount of 100%.

[0009] Preferably, the preparation method of the ZrO2-WC@Al2O3 core-shell particles is: (1) Preparation of the core layer: zirconium oxychloride ZrOCl2·8H2O was dissolved in deionized water to prepare a 0.5 mol / L solution. The pH of the system was adjusted to 9-10 with ammonia water. The solution was hydrothermally reacted at 75-80℃ for 6 h. The Zr(OH)4 colloid was centrifuged and calcined at 550-600℃ for 2 h to obtain monoclinic ZrO2 particles. The monoclinic ZrO2 particles were then mixed with ammonium metatungstate at a molar ratio of 1:1.2. Polyvinylpyrrolidone (5 wt% by weight of the mixture) was added and ball milled for 12 h. The mixture was calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles. (2) Shell preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, and aluminum isopropoxide was added. The mixture was refluxed at 85-90 °C for 3 h, and the Al / Zr molar ratio in the system was controlled to be 0.5:1. After centrifugal drying, the mixture was calcined at 750 °C under argon protection for 1 h to form a γ-Al2O3 coating layer, and finally ZrO2-WC@Al2O3 core-shell particles were obtained.

[0010] More preferably, the polyvinylpyrrolidone is PVP-K30.

[0011] More preferably, the solid-to-liquid ratio of ZrO2-WC composite nanoparticles to ethanol is 10 g:30-50 mL.

[0012] The final ZrO2-WC@Al2O3 core-shell particles have a particle size of no more than 100 nm and an average particle size of about 50 nm.

[0013] A copper roller material for iron-based amorphous strip includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Pure copper, Si, W, Zr, Al, and Mg raw materials were melted in a vacuum induction furnace under argon protection, with the oxygen content controlled to ≤50ppm, the temperature controlled to 1150-1200°C, and the holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles were prepared, the core-shell particles were added to the system, and ultrasonic dispersion was performed for 10-15min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 1-2 hours, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat to 980-1000℃ at 8-10℃ / min and keep warm for 1.5-2h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 5-8℃ / min and keep warm for 3-4h; c. Stress relief stage: slowly cool to 200-220℃ at 1-2℃ / min, keep warm for 1h, and air cool to room temperature to obtain a copper roller material with uniform fine grain structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling the iron-based amorphous strip.

[0014] More preferably, the heat treatment process is protected by argon throughout.

[0015] More preferably, the copper roller sleeve is a ring-shaped alloy with a thickness of 20-26 mm.

[0016] Currently, amorphous strip is primarily produced using a single-roll method. The basic process involves melting a master alloy in a vacuum induction furnace, then spraying the molten alloy onto the surface of a high-speed rotating copper roller. The roller rapidly cools the alloy, causing it to solidify quickly to form the amorphous strip. However, in actual production, as continuous production time increases, the copper roller surface gradually experiences wear and thermal fatigue, which reduces cooling effectiveness and impacts production efficiency.

[0017] At the same time, the different quality of copper rollers will lead to different cooling speeds, which will affect the atomic arrangement of the amorphous alloy and thus directly affect its performance, and then affect the quality of the amorphous strip. Therefore, improving the quality of copper rollers is crucial for improving production efficiency and product quality.

[0018] Beneficial effects: (1) Optimizing the elemental composition; adding Si, W, Zr, Al, Mg and other elements significantly improved the performance of the copper roller. Si can improve the strength and hardness of the copper alloy; W helps to enhance the wear resistance and high-temperature stability of the material; Zr can refine the grains and improve the strength and toughness of the material; Al can improve the corrosion resistance of the material; and Mg helps to improve the fluidity and casting properties of the alloy.

[0019] (2) Adding nanoparticles: ZrO2-WC@Al2O3 core-shell particles are prepared and added to form a uniform core-shell structure distributed in the copper matrix. On the one hand, they can act as a dispersion strengthening phase to improve the strength and hardness of the material. On the other hand, the design of the core-shell structure enables a good interface between the particles and the copper matrix, which can effectively hinder dislocation movement and thus enhance the wear resistance of the material. At the same time, such composite nanoparticles can also improve the thermal conductivity of the material, helping to transfer heat faster and ensure the cooling effect.

[0020] (3) Gradient cooling heat treatment process: Different cooling rates are used in the three stages of solution treatment, aging and stress relief to regulate the microstructure transformation and performance of the material. The rapid heating and water quenching operation in the solution treatment stage allows the strengthening phase to be fully dissolved into the matrix, laying a good foundation for the subsequent aging treatment. The moderate cooling and heat preservation in the aging treatment stage promotes the precipitation of fine and dispersed strengthening phases, significantly improving the strength and hardness of the material. The slow cooling and heat preservation in the stress relief stage can effectively eliminate the residual stress inside the material, avoid cracks and deformation caused by stress concentration, and improve the dimensional stability and reliability of the material. This gradient cooling heat treatment process effectively refines the grains and gives full play to the synergistic effect of the process and nanoparticles, so that the copper roller material has better comprehensive performance, can better adapt to the complex working conditions in the production process of iron-based amorphous strip, and further improve production efficiency and product quality.

[0021] (4) In summary, the present invention can effectively improve the comprehensive performance of the copper roller by optimizing the composition of the copper roller material and adopting a unique gradient heat treatment process. This allows the copper roller to maintain good cooling effect, wear resistance, and thermal conductivity during long-term continuous production, thereby ensuring the stability of the quality and production efficiency of the iron-based amorphous strip. At the same time, for iron-based amorphous strips with different specifications and performance requirements, the copper roller material dimensional parameters can be flexibly adjusted according to actual conditions to achieve the best production effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Schematic diagram and photo of the tensile test specimen; Figure 2 Schematic diagram of the wear scar profile of the specimen in the wear test; Figure 3 Figure 1 is the metallographic structure diagram of Example 1 of the present invention and C17200 beryllium copper as-cast; Figure 4 This is a projection electron microscope image of the ZrO2-WC@Al2O3 core-shell particles of the present invention. DETAILED DESCRIPTION

[0023] The technical solution of the present invention will be further described below with reference to specific embodiments, but is not limited thereto.

[0024] Example 1 A copper roller material for an iron-based amorphous strip comprises the following elements by weight: 0.02% Si, 0.02% W, 0.05% Zr, 0.05% Al, 0.02% Mg, 0.04% ZrO2-WC@Al2O3 core-shell particles, and the balance being copper (Cu), with a total weight percentage of 100%.

[0025] The preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows: (1) Preparation of the core layer: zirconium oxychloride ZrOCl2·8H2O was dissolved in deionized water to prepare a 0.5 mol / L solution. The pH of the system was adjusted to 9-10 with ammonia water. The solution was hydrothermally reacted at 75-80℃ for 6 h. The Zr(OH)4 colloid was centrifuged and calcined at 550-600℃ for 2 h to obtain monoclinic ZrO2 particles. The monoclinic ZrO2 particles were then mixed with ammonium metatungstate at a molar ratio of 1:1.2. Polyvinylpyrrolidone (5 wt% by weight of the mixture) was added and ball milled for 12 h. The mixture was calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles. (2) Shell Preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, and aluminum isopropoxide was added. The mixture was refluxed at 85-90°C for 3 h, with the Al / Zr molar ratio in the system controlled to be 0.5:1. After centrifugal drying, the mixture was calcined at 750°C under argon for 1 h to form a γ-Al2O3 coating layer, ultimately obtaining ZrO2-WC@Al2O3 core-shell particles. Transmission electron microscopy (Talos F200i high-resolution transmission electron microscope field emission electron microscope) was used to observe the particles, revealing a distinct core-shell structure.

[0026] The polyvinylpyrrolidone was PVP-K30.

[0027] The solid-liquid ratio of ZrO2-WC composite nanoparticles and ethanol is 10g:30mL.

[0028] The final ZrO2-WC@Al2O3 core-shell particles have a particle size of no more than 100 nm and an average particle size of about 50 nm.

[0029] A copper roller material for iron-based amorphous strip includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Pure copper, Si, W, Zr, Al, and Mg raw materials were melted in a vacuum induction furnace under argon protection, with the oxygen content controlled to ≤50 ppm, the temperature controlled to 1150-1200°C, and the holding time ≥1 h; ZrO2-WC@Al2O3 core-shell particles were prepared, the core-shell particles were added to the system, and ultrasonic dispersion was performed for 10 min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 1 hour, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat to 980-1000℃ at 8-10℃ / min and keep warm for 1.5h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 5-8℃ / min and keep warm for 3h; c. Stress relief stage: Slowly cool to 200-220°C at a rate of 1-2°C / min, hold for 1 hour, and air-cool to room temperature to obtain a copper roller material with uniform fine grain structure. Based on actual use requirements, the alloy can be processed into copper roller sleeves for cooling iron-based amorphous strip. Argon protection is used throughout the heat treatment process.

[0030] Example 2 A copper roller material for an iron-based amorphous strip comprises the following elements by weight: 0.05% Si, 0.04% W, 0.06% Zr, 0.07% Al, 0.03% Mg, 0.1% ZrO2-WC@Al2O3 core-shell particles, and the balance being copper (Cu), with a total weight percentage of 100%.

[0031] The preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows: (1) Preparation of the core layer: zirconium oxychloride ZrOCl2·8H2O was dissolved in deionized water to prepare a 0.5 mol / L solution. The pH of the system was adjusted to 9-10 with ammonia water. The solution was hydrothermally reacted at 75-80℃ for 6 h. The Zr(OH)4 colloid was centrifuged and calcined at 550-600℃ for 2 h to obtain monoclinic ZrO2 particles. The monoclinic ZrO2 particles were then mixed with ammonium metatungstate at a molar ratio of 1:1.2. Polyvinylpyrrolidone (5 wt% by weight of the mixture) was added and ball milled for 12 h. The mixture was calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles. (2) Shell preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, and aluminum isopropoxide was added. The mixture was refluxed at 85-90 °C for 3 h, and the Al / Zr molar ratio in the system was controlled to be 0.5:1. After centrifugal drying, the mixture was calcined at 750 °C under argon protection for 1 h to form a γ-Al2O3 coating layer, and finally ZrO2-WC@Al2O3 core-shell particles were obtained.

[0032] The polyvinylpyrrolidone was PVP-K30.

[0033] The solid-liquid ratio of ZrO2-WC composite nanoparticles and ethanol is 10g:50mL.

[0034] The final ZrO2-WC@Al2O3 core-shell particles have a particle size of no more than 100 nm and an average particle size of about 50 nm.

[0035] A copper roller material for iron-based amorphous strip includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Pure copper, Si, W, Zr, Al, and Mg raw materials were melted in a vacuum induction furnace under argon protection, with the oxygen content controlled to ≤50 ppm, the temperature controlled to 1150-1200°C, and the holding time ≥1 h; ZrO2-WC@Al2O3 core-shell particles were prepared, the core-shell particles were added to the system, and ultrasonic dispersion was performed for 10 min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 1.5 hours, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat to 980-1000℃ at 8-10℃ / min and keep warm for 1.5h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 5-8℃ / min and keep warm for 4h; c. Stress relief stage: Slowly cool to 200-220°C at a rate of 1-2°C / min, hold for 1 hour, and air-cool to room temperature to obtain a copper roller material with uniform fine grain structure. Based on actual use requirements, the alloy can be processed into copper roller sleeves for cooling iron-based amorphous strip. Argon protection is used throughout the heat treatment process.

[0036] Example 3 A copper roller material for an iron-based amorphous strip comprises the following elements by weight: 0.10% Si, 0.05% W, 0.08% Zr, 0.1% Al, 0.04% Mg, 0.13% ZrO2-WC@Al2O3 core-shell particles, and the balance being copper (Cu), with a total weight percentage of 100%.

[0037] The preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows: (1) Preparation of the core layer: zirconium oxychloride ZrOCl2·8H2O was dissolved in deionized water to prepare a 0.5 mol / L solution. The pH of the system was adjusted to 9-10 with ammonia water. The solution was hydrothermally reacted at 75-80℃ for 6 h. The Zr(OH)4 colloid was centrifuged and calcined at 550-600℃ for 2 h to obtain monoclinic ZrO2 particles. The monoclinic ZrO2 particles were then mixed with ammonium metatungstate at a molar ratio of 1:1.2. Polyvinylpyrrolidone (5 wt% by weight of the mixture) was added and ball milled for 12 h. The mixture was calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles. (2) Shell preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, and aluminum isopropoxide was added. The mixture was refluxed at 85-90 °C for 3 h, and the Al / Zr molar ratio in the system was controlled to be 0.5:1. After centrifugal drying, the mixture was calcined at 750 °C under argon protection for 1 h to form a γ-Al2O3 coating layer, and finally ZrO2-WC@Al2O3 core-shell particles were obtained.

[0038] The polyvinylpyrrolidone was PVP-K30.

[0039] The solid-liquid ratio of ZrO2-WC composite nanoparticles and ethanol is 10g:50mL.

[0040] The final ZrO2-WC@Al2O3 core-shell particles have a particle size of no more than 100 nm and an average particle size of about 50 nm.

[0041] A copper roller material for iron-based amorphous strip includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Pure copper, Si, W, Zr, Al, and Mg raw materials were melted in a vacuum induction furnace under argon protection, with the oxygen content controlled to ≤50 ppm, the temperature controlled to 1150-1200°C, and the holding time ≥1 h; ZrO2-WC@Al2O3 core-shell particles were prepared, and the core-shell particles were added to the system and ultrasonically dispersed for 15 min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 2 hours, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat up to 980-1000℃ at 8-10℃ / min and keep warm for 2h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 5-8℃ / min and keep warm for 4h; c. Stress relief stage: Slowly cool to 200-220°C at a rate of 1-2°C / min, hold for 1 hour, and air-cool to room temperature to obtain a copper roller material with uniform fine grain structure. Based on actual use requirements, the alloy can be processed into copper roller sleeves for cooling iron-based amorphous strip. Argon protection is used throughout the heat treatment process.

[0042] Comparative Example 1 In this comparative example, except that ZrO2-WC@Al2O3 core-shell particles are not added, the rest of the raw materials and process steps are the same as those in Example 1. A copper roller material for an iron-based amorphous strip comprises the following elements by weight: 0.02% Si, 0.02% W, 0.05% Zr, 0.05% Al, 0.02% Mg, and the balance being copper (Cu), with a total weight percentage of 100%.

[0043] A copper roller material for iron-based amorphous strip includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Melt pure copper, Si, W, Zr, Al, and Mg raw materials in a vacuum induction furnace under argon protection, control the oxygen content to ≤50ppm, control the temperature to 1150-1200℃, and keep the temperature for ≥1h; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 1 hour, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat to 980-1000℃ at 8-10℃ / min and keep warm for 1.5h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 5-8℃ / min and keep warm for 3h; c. Stress relief stage: Slowly cool to 200-220°C at a rate of 1-2°C / min, hold for 1 hour, and air-cool to room temperature to obtain a copper roller material with uniform fine grain structure. Based on actual use requirements, the alloy can be processed into copper roller sleeves for cooling iron-based amorphous strip. Argon protection is used throughout the heat treatment process.

[0044] Comparative Example 2 In this comparative example, except for changing the composition of the added metal composite particles, the rest of the raw materials and process steps are the same as in Example 1. A copper roller material for an iron-based amorphous strip comprises the following elements by weight: 0.02% Si, 0.02% W, 0.05% Zr, 0.05% Al, 0.02% Mg, 0.04% ZrO2-WC particles, and the balance being copper (Cu), with a total weight percentage of 100%.

[0045] The preparation method of the ZrO2-WC particles is as follows: (1) Zirconium oxychloride ZrOCl2·8H2O was dissolved in deionized water to prepare a 0.5 mol / L solution. The pH of the system was adjusted to 9-10 with ammonia water. The solution was hydrothermally reacted at 75-80℃ for 6 h. The Zr(OH)4 colloid was centrifuged and calcined at 550-600℃ for 2 h to obtain monoclinic ZrO2 particles. The monoclinic ZrO2 particles were then mixed with ammonium metatungstate at a molar ratio of 1:1.2. Polyvinylpyrrolidone (5 wt% by weight of the mixture) was added and ball milled for 12 h. The solution was calcined at 1150-1200℃ for 2 h under argon protection. After moderate ball milling, ZrO2-WC particles with an average particle size of 50 nm were obtained.

[0046] Comparative Example 3 In this comparative example, except for the direct addition of nano-Al2O3 with the same particle size, the rest of the raw materials and process steps are the same as those in Example 1. A copper roller material for an iron-based amorphous strip comprises the following elements by weight: 0.02% Si, 0.02% W, 0.05% Zr, 0.05% Al, 0.02% Mg, 0.04% nano-Al2O3, and the balance being copper (Cu), with a total weight percentage of 100%.

[0047] The average particle size of nano-Al2O3 is about 50nm, and commercially available products can be used.

[0048] Comparative Example 4 In this comparative example, except that a high-speed cooling rate of 8-10°C / min was used in the heat treatment stage, the rest of the raw materials and process steps were the same as those in Example 1. A copper roller material for iron-based amorphous strip includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Pure copper, Si, W, Zr, Al, and Mg raw materials were melted in a vacuum induction furnace under argon protection, with the oxygen content controlled to ≤50 ppm, the temperature controlled to 1150-1200°C, and the holding time ≥1 h; ZrO2-WC@Al2O3 core-shell particles were prepared, the core-shell particles were added to the system, and ultrasonic dispersion was performed for 10 min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 1 hour, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat to 980-1000℃ at 8-10℃ / min and keep warm for 1.5h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 8-10℃ / min and keep warm for 3h; c. Stress relief stage: slowly cool to 200-220℃ at 8-10℃ / min, keep warm for 1h, and air cool to room temperature to obtain a copper roller material with uniform fine grain structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling the iron-based amorphous strip.

[0049] Comparative Example 5 In this comparative example, except that a single medium-speed cooling rate of 5-8°C / min was used in the heat treatment stage, the rest of the raw materials and process steps were the same as those in Example 1. A copper roller material for iron-based amorphous strip includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Pure copper, Si, W, Zr, Al, and Mg raw materials were melted in a vacuum induction furnace under argon protection, with the oxygen content controlled to ≤50 ppm, the temperature controlled to 1150-1200°C, and the holding time ≥1 h; ZrO2-WC@Al2O3 core-shell particles were prepared, the core-shell particles were added to the system, and ultrasonic dispersion was performed for 10 min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 1 hour, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat to 980-1000℃ at 5-8℃ / min and keep warm for 1.5h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 5-8℃ / min and keep warm for 3h; c. Stress relief stage: slowly cool to 200-220℃ at 5-8℃ / min, keep warm for 1h, and air cool to room temperature to obtain a copper roller material with uniform fine grain structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling the iron-based amorphous strip.

[0050] Comparative Example 6 In this comparative example, except that a slow cooling rate of 1-2°C / min was used in the heat treatment stage, the rest of the raw materials and process steps were the same as those in Example 1. A copper roller material for iron-based amorphous strip includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Pure copper, Si, W, Zr, Al, and Mg raw materials were melted in a vacuum induction furnace under argon protection, with the oxygen content controlled to ≤50 ppm, the temperature controlled to 1150-1200°C, and the holding time ≥1 h; ZrO2-WC@Al2O3 core-shell particles were prepared, the core-shell particles were added to the system, and ultrasonic dispersion was performed for 10 min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 1 hour, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat to 980-1000℃ at 1-2℃ / min and keep warm for 1.5h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 1-2℃ / min and keep warm for 3h; c. Stress relief stage: slowly cool to 200-220℃ at 1-2℃ / min, keep warm for 1h, and air cool to room temperature to obtain a copper roller material with uniform fine grain structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling the iron-based amorphous strip.

[0051] Comparative Example 7 The model is C17200 beryllium copper, a commercially available copper alloy.

[0052] Performance Testing Copper materials were prepared according to the methods in the Examples and Comparative Examples, and their performance was tested. Ten samples were prepared for each experimental group, and all test results were averaged. Relevant performance tests can be performed with reference to GB / T 4340.1-2009, "Metallic Materials—Vickers Hardness Test—Part 1: Test Method," and GB / T 228.1-2021, "Metallic Materials—Tensile Test—Part 1: Room Temperature Test Method."

[0053] From the melted ingots, specimens were first cut parallel to the bottom surface 10 mm from the bottom using a metallographic cutting machine. The specimens were then finely polished with 400-3000# sandpaper and polished with 0.1W diamond polishing paste. After rinsing with anhydrous ethanol and drying, the specimens were etched with a FeCl₃ hydrochloric acid-ethanol solution (1.4 g FeCl₃ + 2 ml concentrated HCl + 48 ml anhydrous ethanol) for approximately 6-7 seconds. Macroscopic solidification microstructure observations were performed using a scanner. Microstructure photographs of the as-cast specimens were taken at the half-radius of the cross-section using an XJP-6A inverted optical microscope. The secondary dendrite arm spacing (SDAS) of the alloy was measured using the line section method and S-Viewer metallographic analysis software.

[0054] Hardness test: The Vickers hardness of the samples was tested using an HVS-1000 digital microhardness tester.

[0055] Mechanical properties test: TSE 105D microcomputer controlled electronic universal testing machine, sample preparation: alloy samples are prepared by wire cutting, the size is as follows Figure 1 The tensile test was carried out at room temperature with a tensile rate of 1 mm / min.

[0056] Thermal conductivity: The thermal conductivity of the material was tested using a laser thermal conductivity meter produced by Xi'an Xiaxi Electronic Technology Co., Ltd. First, the material was cut into discs with a diameter of 12.7 mm and a thickness of 1.5 mm using wire cutting. Before testing, a layer of graphite was sprayed on the upper and lower surfaces of the sample to reduce the reflection of the laser on the sample surface and enhance the absorption of the laser pulse energy by the sample surface. In order to improve the accuracy of the measurement and reduce the error in the measurement process, the surface flatness of the sample should be measured to be flat and parallel, with an error within 0.5% of the thickness. The surface of the sample was polished to avoid defects. The thermal conductivity of repeated samples in the same experimental group was tested, and the results were averaged.

[0057] Wear resistance: The equipment used was an HSR-2M high-speed reciprocating friction and wear testing machine. Friction pair: φ3 mm ceramic balls. Friction speed: 4000 mm / min. Test temperature: room temperature. Load: 10 N.

[0058] The friction and wear test lasts for 2 minutes, with a reciprocating friction length of 5 mm. After the experiment, the instantaneous friction coefficient diagram can be obtained by the test software. The wear scar profile cross-section diagram can be measured by the wear scar probe, such as Figure 2 As shown, the depth, width and wear volume of the wear scar can be obtained from the cross-sectional diagram, and the wear rate of the sample can be calculated by the formula: , where K is the wear rate (unit: mm 2 / N); V is the wear volume (unit: mm 3 ); v' is the friction velocity (mm / min); t is the friction duration (min); and W is the applied load (N). After the wear experiment, the surface morphology was observed using a scanning electron microscope.

[0059] Table 1 Performance test results The data in the table show that the copper roller materials prepared in the examples of the present invention exhibit excellent tensile strength, hardness, thermal conductivity, and wear resistance. The tensile strength of Examples 1-3 ranged from 480 to 545 MPa. In terms of hardness, the examples achieved a hardness of 320 to 366 HV, significantly higher than the comparative examples. The thermal conductivity of the examples ranged from 395 to 410 W / m·K, indicating that the materials in the examples of the present invention exhibited improved thermal conductivity and were able to conduct heat more efficiently. In terms of wear resistance, the wear rates of the examples were as low as 0.06% to 0.12%, indicating that the copper roller materials prepared in the present invention were more wear-resistant during friction and had a longer service life. In contrast, in Comparative Examples 1-3, which varied the nanoparticle addition method, the wear of Comparative Example 1, which lacked nanoparticle reinforcement, was increased, while the interfacial bonding ability of Comparative Example 2, which lacked an Al2O3 shell, was reduced. Furthermore, the thermal conductivity of Comparative Example 3, which incorporated only Al2O3, was weakened. This demonstrates that the use of the ZrO2-WC@Al2O3 core-shell particles of the present invention can effectively improve the overall performance of the copper roller material. However, in comparison examples 4-6, which have changed the heat treatment process, the comparison example 4 with high-speed cooling throughout the whole process may have residual stress causing microcracks, the comparison example 5 with medium-speed cooling throughout the whole process may cause the size of the precipitated phase to coarsen, and the comparison example 6 with slow cooling throughout the whole process may cause excessive grain growth, thereby weakening the comprehensive performance of comparison examples 4-6. Therefore, in summary, by adding ZrO2-WC@Al2O3 core-shell particles and adopting a specific heat treatment process, the comprehensive performance of the copper roller material for iron-based amorphous strip can be significantly improved to meet actual use requirements. It can also be seen from the implementation of the present invention and the microstructure samples of the C17200 beryllium copper ingot that the dendrites in the embodiment of the present invention are refined and the secondary dendrite arm spacing is reduced.

[0060] Further, the materials of the embodiment and the comparative example were used as the copper sleeve of the cooling roller to prepare an iron-based amorphous strip. The thickness of the copper roller sleeve was 26 mm. The preparation method was as follows: Raw material composition: In terms of mass percentage, the raw materials include: B2.35wt%, Si4.82wt%, Al and Ti contents are both less than 50ppm, the balance is iron, and contains inevitable trace impurity elements, the total amount of impurity elements is ≤0.5%.

[0061] Manufacturing method: (1) Melting: The raw materials are mixed according to the percentage and placed in a medium frequency furnace for smelting, so that the final composition of the molten steel is controlled to be B2.35wt%, Si4.80wt%, Al and Ti contents are both less than 50ppm, the balance is iron, and contains inevitable trace impurity elements, the total amount of impurity elements is ≤0.5%; during smelting, the steel liquid is protected by a protective gas; the heating temperature of the smelting furnace is 1350℃; the completely melted steel liquid is further smelted for 7 minutes under the action of electromagnetic stirring; (3) Insulation treatment: the intermediate insulation bag is evacuated and filled with protective gas, and the intermediate bag is heated to 1350°C. The molten alloy in step (2) is poured into the intermediate insulation bag and kept at a constant temperature for 12 minutes to keep the alloy liquid at a constant temperature of 1350°C. (4) Spraying: The alloy liquid after heat preservation in step (3) is injected into the spraying bag, and sprayed onto the cooling copper roller through the nozzle of the spraying bag under protective gas to form an iron-based amorphous strip; (5) Annealing treatment: The amorphous alloy continuous strip is placed in a vacuum annealing tunnel furnace and subjected to annealing and crystallization treatment at 400°C in a horizontal and vertical staggered magnetic field; the annealed and crystallized strip is passed through an alloy rolling machine, and then die-cut and packaged to obtain the final product.

[0062] The resulting strips were tested for magnetic properties according to GB / T 19346.3-2021. The saturation magnetic induction (Bs) of the samples was measured using a Lake Shore 7407 VSM vibrating sample magnetometer (VSM) at a magnetic field strength of 800 kA / m. The coercivity (Hc) of the strips was measured using a BH hysteresis loop analyzer (MATS-2010SD) manufactured by Hunan Lianzhong Technology Co., Ltd. at a maximum magnetic field strength of 800 A / m. The lamination coefficient was measured according to GB / T 19346.2-2017. The test results are shown in Table 2. Table 2 Performance test results of iron-based amorphous strip From the data in Table 2, it can be seen that the quality of the copper roller sleeve is improved, and its cooling rate and uniformity are improved, thereby achieving an improvement in the uniformity of the amorphous strip and an improvement in the flatness. The macroscopic manifestation is an improvement in the stacking coefficient and the comprehensive magnetic properties.

[0063] It should be noted that the above embodiments are only some of the preferred embodiments of the present invention, and not all of them. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work should fall within the scope of protection of the present invention.

Claims

1. A copper roller material for iron-based amorphous strip, characterized in that: The material comprises the following elements by weight: Si 0.02%-0.10%, W 0.02%-0.05%, Zr 0.05%-0.08%, Al 0.05%-0.1%, Mg 0.02%-0.04%, ZrO2-WC@Al2O3 core-shell particles 0.04%-0.13%, and the balance is Cu, with a total amount of 100%.

2. The copper roller material for iron-based amorphous strip according to claim 1, characterized in that: The composition comprises the following elements by weight: Si 0.10%, W 0.05%, Zr 0.08%, Al 0.1%, Mg 0.04%, ZrO2-WC@Al2O3 core-shell particles 0.13%, and the balance is copper Cu, with a total amount of 100%.

3. The copper roller material for iron-based amorphous strip according to claim 1, characterized in that: The preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows: (1) Preparation of the core layer: zirconium oxychloride ZrOCl2·8H2O was dissolved in deionized water to prepare a 0.5 mol / L solution. The pH of the system was adjusted to 9-10 with ammonia water. The solution was hydrothermally reacted at 75-80℃ for 6 h. The Zr(OH)4 colloid was centrifuged and calcined at 550-600℃ for 2 h to obtain monoclinic ZrO2 particles. The monoclinic ZrO2 particles were then mixed with ammonium metatungstate at a molar ratio of 1:1.

2. Polyvinylpyrrolidone (5 wt% by weight of the mixture) was added and ball milled for 12 h. The solution was then calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles. (2) Shell preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, and aluminum isopropoxide was added. The mixture was refluxed at 85-90 °C for 3 h, and the Al / Zr molar ratio in the system was controlled to be 0.5:

1. After centrifugal drying, the mixture was calcined at 750 °C under argon protection for 1 h to form a γ-Al2O3 coating layer, and finally ZrO2-WC@Al2O3 core-shell particles were obtained.

4. The copper roller material for iron-based amorphous strip according to claim 3, characterized in that: The polyvinylpyrrolidone was PVP-K30.

5. The copper roller material for iron-based amorphous strip according to claim 3, characterized in that: In step (2), the solid-liquid ratio of ZrO2-WC composite nanoparticles to ethanol is 10 g:30-50 mL.

6. A copper roller material for iron-based amorphous strip according to any one of claims 1 to 3, characterized in that: It includes smelting, casting, forging and heat treatment steps, specifically: (1) Melting: Pure copper, Si, W, Zr, Al, and Mg raw materials were melted in a vacuum induction furnace under argon protection, with the oxygen content controlled to ≤50ppm, the temperature controlled to 1150-1200°C, and the holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles were prepared, the core-shell particles were added to the system, and ultrasonic dispersion was performed for 10-15min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, with a cooling rate of ≥50°C / min; (3) Forging: heating the ingot obtained in step (2) to 850-880°C, keeping it warm for 1-2 hours, and performing multi-directional forging, with the final forging temperature being ≥650°C; (4) Heat treatment: a. Solution treatment stage: heat to 980-1000℃ at 8-10℃ / min and keep warm for 1.5-2h; quench with water after the end of the heat preservation to fully dissolve the strengthening phase; b. Aging treatment stage: cool down to 450-480℃ at 5-8℃ / min and keep warm for 3-4h; c. Stress relief stage: slowly cool to 200-220℃ at 1-2℃ / min, keep warm for 1h, and air cool to room temperature to obtain a copper roller material with uniform fine grain structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling the iron-based amorphous strip.

7. The copper roller material for iron-based amorphous strip according to claim 4, characterized in that: The heat treatment process is protected by argon throughout.

8. The copper roller material for iron-based amorphous strip according to claim 4, characterized in that: The copper roller sleeve is a ring-shaped alloy with a thickness of 20-26 mm.

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