A copper roll material for iron-based amorphous ribbon and a gradient heat treatment process

Abstract

The application discloses a copper roller material for iron-based amorphous strip and a gradient heat treatment process, and belongs to the technical field of amorphous alloy material preparation. The material contains the following elements in percentage 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 of Cu, with the total amount being 100%. The application 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, so that the copper roller can still maintain good cooling effect, wear resistance and heat conductivity in a long-time continuous production process, thereby guaranteeing the stability of the quality and production efficiency of the iron-based amorphous strip. Therefore, the quality and production efficiency of the iron-based amorphous strip are improved.

Description

Technical Field

[0001] This invention belongs to the field of amorphous alloy material preparation technology, specifically relating to a copper roller material for iron-based amorphous strips and a gradient heat treatment process. Background Technology

[0002] Amorphous alloys, also known as metallic glasses, emerged in the 1970s. They are produced by rapidly cooling molten steel into a single, micrometer-thick strip. The resulting solid alloy (strip) has a different atomic arrangement than the regularly arranged crystalline structure of cold-rolled silicon steel. This irregular atomic arrangement gives it a narrow Blass-H loop, resulting in high magnetic permeability and low losses. Furthermore, the irregular atomic arrangement restricts electron movement, leading to higher resistivity than crystalline alloys, which also helps reduce eddy current losses. Transformer cores made from amorphous alloys exhibit lower no-load losses compared to traditional transformers using silicon steel sheets, resulting in significant energy savings and environmental benefits. When amorphous alloy transformer cores are used in oil-immersed transformers, they can significantly reduce emissions of various harmful gases. Therefore, an increasing number of manufacturers are using amorphous alloys as the raw material for transformer cores.

[0003] Iron-based amorphous alloys have attracted much attention from researchers due to their excellent soft magnetic properties and corrosion resistance. Currently, the main method for producing iron-based amorphous ribbons is the single-roll rapid quenching method. This method involves spraying molten alloy onto the surface of a high-speed rotating copper roller, where the rapid cooling of the roller causes the alloy to solidify quickly, forming an amorphous ribbon. For example, Chinese patent application CN201410469941.X pertains to a method for preparing iron-based amorphous alloys. This method is low-cost and simple to implement, and can significantly improve amorphous formation capability without reducing saturation magnetization. This invention uses single-roll rapid quenching or copper mold casting to prepare strip and bulk iron-based amorphous alloy samples, respectively. Specifically, under argon protection, trace elements are added to the iron-based amorphous alloy, melted in a reactor according to a stoichiometric ratio, and rapidly cooled and solidified. The added element is copper, accounting for 0.1% to 1.0% of the total atomic percentage of the iron-based amorphous alloy. This yields an iron-based amorphous alloy with both high saturation magnetization and strong amorphous formation capability.

[0004] In this process, the cooling copper roller is a key component in the industrial production equipment for amorphous ribbons, and its cooling effect directly affects the changes in the amorphous grain structure and magnetic properties. The copper roller must not only provide sufficient cooling speed to ensure the formation of amorphous ribbons, but also possess good wear resistance and thermal conductivity to ensure the quality of the ribbons and production efficiency. However, existing copper roller materials still have some shortcomings in performance, such as limited cooling speed and poor wear resistance, which to some extent affect the quality and production efficiency of iron-based amorphous ribbons.

[0005] Therefore, developing a high-performance copper roller material for iron-based amorphous ribbons and its corresponding processing technology is of great practical significance. Summary of the Invention

[0006] This invention addresses the problems in existing technologies by providing a copper roller material for iron-based amorphous ribbons and a gradient heat treatment process, thus overcoming the shortcomings of existing copper roller materials in terms of cooling rate and wear resistance. The copper roller material for iron-based amorphous ribbons of this invention, through a reasonable element ratio and a unique preparation process, endows the copper roller with superior performance, better meeting the needs of amorphous ribbon production. The gradient heat treatment process further optimizes the microstructure and properties of the copper roller material, significantly improving the cooling effect, wear resistance, and thermal conductivity, thereby enhancing the quality and production efficiency of iron-based amorphous ribbons.

[0007] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention is as follows:

[0008] A copper roller material for iron-based amorphous ribbon contains the following elements by weight percentage: 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%, with the balance being copper (Cu), totaling 100%.

[0009] Preferably, the copper roller material for iron-based amorphous ribbon 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%, with the balance being copper Cu, and the total amount is 100%.

[0010] Preferably, the preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows:

[0011] (1) Core layer preparation: 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 system was hydrothermally reacted at 75-80℃ for 6 h. After centrifugation, Zr(OH)4 colloid was obtained. It was then 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. 5 wt% of polyvinylpyrrolidone was added to the mixture, and the mixture was ball-milled for 12 h. The mixture was then calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles.

[0012] (2) Shell preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, aluminum isopropoxide was added, and the mixture was refluxed at 85-90℃ for 3h. The Al / Zr molar ratio in the system was controlled to be 0.5:1. After centrifugation and drying, the mixture was calcined at 750℃ under argon protection for 1h to form a γ-Al2O3 coating layer, and finally ZrO2-WC@Al2O3 core-shell particles were obtained.

[0013] More preferably, polyvinylpyrrolidone is PVP-K30.

[0014] More preferably, the solid-liquid ratio of ZrO2-WC composite nanoparticles to ethanol is 10g:30-50mL.

[0015] 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.

[0016] A copper roller material for iron-based amorphous ribbon includes smelting, casting, forging, and heat treatment steps, specifically:

[0017] (1) Smelting: Pure copper, Si, W, Zr, Al and Mg raw materials are smelted in a vacuum induction furnace under argon protection, with oxygen content controlled at ≤50ppm, temperature controlled at 1150-1200℃, and holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles are prepared, and the core-shell particles are added to the system and ultrasonically dispersed for 10-15min;

[0018] (2) Casting: The molten alloy is poured into a metal mold preheated to 300-350℃, and the cooling rate is ≥50℃ / min;

[0019] (3) Forging: Heat the ingot obtained in step (2) to 850-880℃, hold for 1-2 hours, and perform multi-directional forging. The final forging temperature is ≥650℃.

[0020] (4) Heat treatment:

[0021] a. Solution treatment stage: Heat to 980-1000℃ at 8-10℃ / min and hold for 1.5-2 hours; after holding, quench with water to ensure that the strengthening phase is fully dissolved;

[0022] b. Aging treatment stage: Cool down to 450-480℃ at 5-8℃ / min and keep warm for 3-4 hours;

[0023] c. Stress relief stage: Slowly cool to 200-220℃ at 1-2℃ / min, hold for 1 hour, and air cool to room temperature to obtain a copper roller material with a uniform fine-grained structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling rollers of iron-based amorphous strips.

[0024] Even better, the heat treatment process is protected by argon gas throughout.

[0025] More preferably, the copper roller sleeve is an annular alloy with a thickness of 20-26 mm.

[0026] Currently, the preparation of amorphous ribbon is mainly carried out using the single-roller method. The basic process involves melting the master alloy in a vacuum induction furnace, then spraying the molten alloy onto the surface of a high-speed rotating copper roller. The rapid cooling of the copper roller causes the alloy to solidify quickly, forming the amorphous ribbon. However, in actual production, as continuous production time increases, the surface of the copper roller gradually experiences wear and thermal fatigue, which leads to a decrease in cooling efficiency and affects production efficiency.

[0027] Meanwhile, the different qualities of copper rollers result in different cooling rates, which in turn affect the atomic arrangement of amorphous alloys, thus directly impacting their performance and consequently the quality of amorphous strips. Therefore, improving the quality of copper rollers is crucial for both increasing production efficiency and product quality.

[0028] Beneficial effects:

[0029] (1) Optimize the elemental composition; adding elements such as Si, W, Zr, Al, and Mg significantly improves the performance of copper rollers. Si can improve the strength and hardness of copper alloys; W helps to enhance the wear resistance and high-temperature stability of materials; Zr can refine grains and improve the strength and toughness of materials; Al can improve the corrosion resistance of materials; and Mg helps to improve the fluidity and casting performance of alloys.

[0030] (2) Addition of nanoparticles: ZrO2-WC@Al2O3 core-shell particles were prepared, forming a uniform core-shell structure distributed in the copper matrix. On the one hand, it can act as a dispersed reinforcing phase, improving the strength and hardness of the material; on the other hand, the core-shell structure design allows for good interfacial bonding between the particles and the copper matrix, effectively hindering dislocation movement and thus enhancing the wear resistance of the material. Simultaneously, such composite nanoparticles can also improve the thermal conductivity of the material, helping to transfer heat more quickly and ensuring a better cooling effect.

[0031] (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 properties of the material. The rapid heating and water quenching in the solution treatment stage allow the reinforcing phase to fully dissolve into the matrix, laying a good foundation for the subsequent aging treatment. The moderate cooling and holding in the aging treatment stage promotes the precipitation of fine and dispersed reinforcing phases, significantly improving the strength and hardness of the material. The slow cooling and holding in the stress relief stage can effectively eliminate 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, fully utilizes the synergistic effect of the process and nanoparticles, and enables the copper roller material to have better comprehensive performance, better adapt to the complex working conditions in the production process of iron-based amorphous ribbon, and further improve production efficiency and product quality.

[0032] (4) In summary, by optimizing the composition of the copper roller material and employing a unique gradient heat treatment process, this invention can effectively improve the overall performance of the copper roller, enabling it 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 ribbon. Furthermore, for iron-based amorphous ribbons with different specifications and performance requirements, the dimensional parameters of the copper roller material can be flexibly adjusted according to the actual situation to achieve the best production results. Attached Figure Description

[0033] Figure 1 Here are schematic diagrams and photographs of the specimen used in this tensile test;

[0034] Figure 2 This is a schematic diagram of the wear track contours of the specimen during the wear test;

[0035] Figure 3 The metallographic diagrams are of the as-cast state of Example 1 of the present invention and C17200 beryllium copper.

[0036] Figure 4 This is a transmission electron microscope (TEM) image of the ZrO2-WC@Al2O3 core-shell particles of this invention. Detailed Implementation

[0037] The technical solution of the present invention will be further described below with reference to specific embodiments, but it is not limited thereto.

[0038] Example 1

[0039] A copper roller material for iron-based amorphous ribbon contains the following elements by weight percentage: Si 0.02%, W 0.02%, Zr 0.05%, Al 0.05%, Mg 0.02%, ZrO2-WC@Al2O3 core-shell particles 0.04%, with the balance being copper Cu, and the total amount is 100%.

[0040] The preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows:

[0041] (1) Core layer preparation: 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 system was hydrothermally reacted at 75-80℃ for 6 h. After centrifugation, Zr(OH)4 colloid was obtained. It was then 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. 5 wt% of polyvinylpyrrolidone was added to the mixture, and the mixture was ball-milled for 12 h. The mixture was then calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles.

[0042] (2) Shell preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, aluminum isopropoxide was added, and the mixture was refluxed at 85-90℃ for 3 h. The Al / Zr molar ratio in the system was controlled to be 0.5:1. After centrifugation and drying, the mixture was calcined at 750℃ under argon protection for 1 h to form a γ-Al2O3 coating layer, thus obtaining ZrO2-WC@Al2O3 core-shell particles. The particles were observed using a transmission electron microscope (Talos F200i high-resolution transmission electron microscope / field emission electron microscope), and a clear core-shell structure could be observed.

[0043] Polyvinylpyrrolidone is PVP-K30.

[0044] The solid-liquid ratio of ZrO2-WC composite nanoparticles to ethanol is 10g:30mL.

[0045] 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.

[0046] A copper roller material for iron-based amorphous ribbon includes smelting, casting, forging, and heat treatment steps, specifically:

[0047] (1) Smelting: Pure copper, Si, W, Zr, Al and Mg raw materials are smelted in a vacuum induction furnace under argon protection, with oxygen content controlled at ≤50ppm, temperature controlled at 1150-1200℃, and holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles are prepared, and the core-shell particles are added to the system and ultrasonically dispersed for 10min;

[0048] (2) Casting: The molten alloy is poured into a metal mold preheated to 300-350℃, and the cooling rate is ≥50℃ / min;

[0049] (3) Forging: Heat the ingot obtained in step (2) to 850-880℃, hold for 1 hour, and perform multi-directional forging. The final forging temperature is ≥650℃.

[0050] (4) Heat treatment:

[0051] a. Solution treatment stage: Heat to 980-1000℃ at 8-10℃ / min and hold for 1.5h; after holding, quench with water to ensure that the strengthening phase is fully dissolved;

[0052] b. Aging treatment stage: Cool down to 450-480℃ at 5-8℃ / min and keep warm for 3 hours;

[0053] c. Stress relief stage: Slowly cool to 200-220℃ at 1-2℃ / min, hold for 1 hour, and air cool to room temperature to obtain a copper roller material with a uniform fine-grained structure. Depending on actual application requirements, the alloy can be processed into copper roller sleeves for cooling rollers used in iron-based amorphous ribbons. The entire heat treatment process is protected by argon gas.

[0054] Example 2

[0055] A copper roller material for iron-based amorphous ribbon contains the following elements by weight percentage: Si 0.05%, W 0.04%, Zr 0.06%, Al 0.07%, Mg 0.03%, ZrO2-WC@Al2O3 core-shell particles 0.1%, with the balance being copper Cu, and the total weight is 100%.

[0056] The preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows:

[0057] (1) Core layer preparation: 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 system was hydrothermally reacted at 75-80℃ for 6 h. After centrifugation, Zr(OH)4 colloid was obtained. It was then 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. 5 wt% of polyvinylpyrrolidone was added to the mixture, and the mixture was ball-milled for 12 h. The mixture was then calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles.

[0058] (2) Shell preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, aluminum isopropoxide was added, and the mixture was refluxed at 85-90℃ for 3h. The Al / Zr molar ratio in the system was controlled to be 0.5:1. After centrifugation and drying, the mixture was calcined at 750℃ under argon protection for 1h to form a γ-Al2O3 coating layer, and finally ZrO2-WC@Al2O3 core-shell particles were obtained.

[0059] Polyvinylpyrrolidone is PVP-K30.

[0060] The solid-liquid ratio of ZrO2-WC composite nanoparticles to ethanol is 10g:50mL.

[0061] 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.

[0062] A copper roller material for iron-based amorphous ribbon includes smelting, casting, forging, and heat treatment steps, specifically:

[0063] (1) Smelting: Pure copper, Si, W, Zr, Al and Mg raw materials are smelted in a vacuum induction furnace under argon protection, with oxygen content controlled at ≤50ppm, temperature controlled at 1150-1200℃, and holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles are prepared, and the core-shell particles are added to the system and ultrasonically dispersed for 10min;

[0064] (2) Casting: The molten alloy is poured into a metal mold preheated to 300-350℃, and the cooling rate is ≥50℃ / min;

[0065] (3) Forging: Heat the ingot obtained in step (2) to 850-880℃, hold for 1.5h, and perform multi-directional forging. The final forging temperature is ≥650℃.

[0066] (4) Heat treatment:

[0067] a. Solution treatment stage: Heat to 980-1000℃ at 8-10℃ / min and hold for 1.5h; after holding, quench with water to ensure that the strengthening phase is fully dissolved;

[0068] b. Aging treatment stage: Cool down to 450-480℃ at 5-8℃ / min and keep warm for 4 hours;

[0069] c. Stress relief stage: Slowly cool to 200-220℃ at 1-2℃ / min, hold for 1 hour, and air cool to room temperature to obtain a copper roller material with a uniform fine-grained structure. Depending on actual application requirements, the alloy can be processed into copper roller sleeves for cooling rollers used in iron-based amorphous ribbons. The entire heat treatment process is protected by argon gas.

[0070] Example 3

[0071] A copper roller material for iron-based amorphous ribbon 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%, with the balance being copper Cu, and the total weight is 100%.

[0072] The preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows:

[0073] (1) Core layer preparation: 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 system was hydrothermally reacted at 75-80℃ for 6 h. After centrifugation, Zr(OH)4 colloid was obtained. It was then 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. 5 wt% of polyvinylpyrrolidone was added to the mixture, and the mixture was ball-milled for 12 h. The mixture was then calcined at 1150-1200℃ for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles.

[0074] (2) Shell preparation: ZrO2-WC composite nanoparticles were dispersed in ethanol, aluminum isopropoxide was added, and the mixture was refluxed at 85-90℃ for 3h. The Al / Zr molar ratio in the system was controlled to be 0.5:1. After centrifugation and drying, the mixture was calcined at 750℃ under argon protection for 1h to form a γ-Al2O3 coating layer, and finally ZrO2-WC@Al2O3 core-shell particles were obtained.

[0075] Polyvinylpyrrolidone is PVP-K30.

[0076] The solid-liquid ratio of ZrO2-WC composite nanoparticles to ethanol is 10g:50mL.

[0077] 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.

[0078] A copper roller material for iron-based amorphous ribbon includes smelting, casting, forging, and heat treatment steps, specifically:

[0079] (1) Smelting: Pure copper, Si, W, Zr, Al and Mg raw materials are smelted in a vacuum induction furnace under argon protection, with oxygen content controlled at ≤50ppm, temperature controlled at 1150-1200℃, and holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles are prepared, and the core-shell particles are added to the system and ultrasonically dispersed for 15min;

[0080] (2) Casting: The molten alloy is poured into a metal mold preheated to 300-350℃, and the cooling rate is ≥50℃ / min;

[0081] (3) Forging: Heat the ingot obtained in step (2) to 850-880℃, hold for 2 hours, and perform multi-directional forging. The final forging temperature is ≥650℃.

[0082] (4) Heat treatment:

[0083] a. Solution treatment stage: Heat to 980-1000℃ at 8-10℃ / min and hold for 2 hours; after holding, quench with water to ensure that the strengthening phase is fully dissolved;

[0084] b. Aging treatment stage: Cool down to 450-480℃ at 5-8℃ / min and keep warm for 4 hours;

[0085] c. Stress relief stage: Slowly cool to 200-220℃ at 1-2℃ / min, hold for 1 hour, and air cool to room temperature to obtain a copper roller material with a uniform fine-grained structure. Depending on actual application requirements, the alloy can be processed into copper roller sleeves for cooling rollers used in iron-based amorphous ribbons. The entire heat treatment process is protected by argon gas.

[0086] Comparative Example 1

[0087] In this comparative example, except for the absence of ZrO2-WC@Al2O3 core-shell particles, the raw materials and process steps are the same as in Example 1. That is:

[0088] A copper roller material for iron-based amorphous ribbon contains the following elements by weight percentage: Si 0.02%, W 0.02%, Zr 0.05%, Al 0.05%, Mg 0.02%, with the balance being copper Cu, and the total amount is 100%.

[0089] A copper roller material for iron-based amorphous ribbon includes smelting, casting, forging, and heat treatment steps, specifically:

[0090] (1) Smelting: Pure copper, Si, W, Zr, Al and Mg raw materials are smelted in a vacuum induction furnace under argon protection, with oxygen content controlled at ≤50ppm, temperature controlled at 1150-1200℃, and holding time ≥1h;

[0091] (2) Casting: The molten alloy is poured into a metal mold preheated to 300-350℃, and the cooling rate is ≥50℃ / min;

[0092] (3) Forging: Heat the ingot obtained in step (2) to 850-880℃, hold for 1 hour, and perform multi-directional forging. The final forging temperature is ≥650℃.

[0093] (4) Heat treatment:

[0094] a. Solution treatment stage: Heat to 980-1000℃ at 8-10℃ / min and hold for 1.5h; after holding, quench with water to ensure that the strengthening phase is fully dissolved;

[0095] b. Aging treatment stage: Cool down to 450-480℃ at 5-8℃ / min and keep warm for 3 hours;

[0096] c. Stress relief stage: Slowly cool to 200-220℃ at 1-2℃ / min, hold for 1 hour, and air cool to room temperature to obtain a copper roller material with a uniform fine-grained structure. Depending on actual application requirements, the alloy can be processed into copper roller sleeves for cooling rollers used in iron-based amorphous ribbons. The entire heat treatment process is protected by argon gas.

[0097] Comparative Example 2

[0098] In this comparative example, except for the change in the composition of the added metal composite particles, the raw materials and process steps are the same as in Example 1. That is:

[0099] A copper roller material for iron-based amorphous ribbon contains the following elements by weight percentage: Si 0.02%, W 0.02%, Zr 0.05%, Al 0.05%, Mg 0.02%, ZrO2-WC particles 0.04%, with the balance being copper Cu, and the total amount is 100%.

[0100] The preparation method of the ZrO2-WC particles is as follows:

[0101] (1) Dissolve zirconium oxychloride ZrOCl2·8H2O in deionized water to prepare a 0.5 mol / L solution. Adjust the pH of the system to 9-10 with ammonia water. Perform hydrothermal reaction at 75-80℃ for 6 h. Centrifuge to obtain Zr(OH)4 colloid. Calcinate it at 550-600℃ for 2 h to obtain monoclinic ZrO2 particles. Mix the monoclinic ZrO2 particles with ammonium metatungstate at a molar ratio of 1:1.2. Add 5 wt% polyvinylpyrrolidone to the mixture and ball mill for 12 h. Calcinate at 1150-1200℃ for 2 h under argon protection. After appropriate ball milling, obtain ZrO2-WC particles with an average particle size of 50 nm.

[0102] Comparative Example 3

[0103] In this comparative example, except for the direct addition of nano-Al2O3 with the same particle size, the raw materials and process steps are the same as in Example 1. That is:

[0104] A copper roller material for iron-based amorphous ribbon contains the following elements by weight percentage: Si 0.02%, W 0.02%, Zr 0.05%, Al 0.05%, Mg 0.02%, nano Al2O3 0.04%, with the balance being copper Cu, and the total weight is 100%.

[0105] The average particle size of nano Al2O3 is about 50nm, and commercially available finished products can be used.

[0106] Comparative Example 4

[0107] In this comparative example, except for the heat treatment stage which uses a unique high-speed cooling rate of 8-10℃ / min, the raw materials and process steps are the same as in Example 1. That is:

[0108] A copper roller material for iron-based amorphous ribbon includes smelting, casting, forging, and heat treatment steps, specifically:

[0109] (1) Smelting: Pure copper, Si, W, Zr, Al and Mg raw materials are smelted in a vacuum induction furnace under argon protection, with oxygen content controlled at ≤50ppm, temperature controlled at 1150-1200℃, and holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles are prepared, and the core-shell particles are added to the system and ultrasonically dispersed for 10min;

[0110] (2) Casting: The molten alloy is poured into a metal mold preheated to 300-350℃, and the cooling rate is ≥50℃ / min;

[0111] (3) Forging: Heat the ingot obtained in step (2) to 850-880℃, hold for 1 hour, and perform multi-directional forging. The final forging temperature is ≥650℃.

[0112] (4) Heat treatment:

[0113] a. Solution treatment stage: Heat to 980-1000℃ at 8-10℃ / min and hold for 1.5h; after holding, quench with water to ensure that the strengthening phase is fully dissolved;

[0114] b. Aging treatment stage: Cool down to 450-480℃ at 8-10℃ / min and keep warm for 3 hours;

[0115] c. Stress relief stage: Slowly cool to 200-220℃ at 8-10℃ / min, hold for 1 hour, and air cool to room temperature to obtain a copper roller material with a uniform fine-grained structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling rollers of iron-based amorphous strips.

[0116] Comparative Example 5

[0117] In this comparative example, except for the heat treatment stage, which uses a unique medium-speed cooling rate of 5-8℃ / min, the raw materials and process steps are the same as in Example 1. That is:

[0118] A copper roller material for iron-based amorphous ribbon includes smelting, casting, forging, and heat treatment steps, specifically:

[0119] (1) Smelting: Pure copper, Si, W, Zr, Al and Mg raw materials are smelted in a vacuum induction furnace under argon protection, with oxygen content controlled at ≤50ppm, temperature controlled at 1150-1200℃, and holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles are prepared, and the core-shell particles are added to the system and ultrasonically dispersed for 10min;

[0120] (2) Casting: The molten alloy is poured into a metal mold preheated to 300-350℃, and the cooling rate is ≥50℃ / min;

[0121] (3) Forging: Heat the ingot obtained in step (2) to 850-880℃, hold for 1 hour, and perform multi-directional forging. The final forging temperature is ≥650℃.

[0122] (4) Heat treatment:

[0123] a. Solution treatment stage: Heat to 980-1000℃ at 5-8℃ / min and hold for 1.5h; after holding, quench with water to ensure that the strengthening phase is fully dissolved;

[0124] b. Aging treatment stage: Cool down to 450-480℃ at 5-8℃ / min and keep warm for 3 hours;

[0125] c. Stress relief stage: Slowly cool to 200-220℃ at 5-8℃ / min, hold for 1 hour, and air cool to room temperature to obtain a copper roller material with a uniform fine-grained structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling rollers of iron-based amorphous strips.

[0126] Comparative Example 6

[0127] In this comparative example, except for the use of a single slow cooling rate of 1-2℃ / min during the heat treatment stage, the raw materials and process steps are the same as in Example 1. That is:

[0128] A copper roller material for iron-based amorphous ribbon includes smelting, casting, forging, and heat treatment steps, specifically:

[0129] (1) Smelting: Pure copper, Si, W, Zr, Al and Mg raw materials are smelted in a vacuum induction furnace under argon protection, with oxygen content controlled at ≤50ppm, temperature controlled at 1150-1200℃, and holding time ≥1h; ZrO2-WC@Al2O3 core-shell particles are prepared, and the core-shell particles are added to the system and ultrasonically dispersed for 10min;

[0130] (2) Casting: The molten alloy is poured into a metal mold preheated to 300-350℃, and the cooling rate is ≥50℃ / min;

[0131] (3) Forging: Heat the ingot obtained in step (2) to 850-880℃, hold for 1 hour, and perform multi-directional forging. The final forging temperature is ≥650℃.

[0132] (4) Heat treatment:

[0133] a. Solution treatment stage: Heat to 980-1000℃ at a rate of 1-2℃ / min and hold for 1.5h; after holding, quench with water to ensure that the strengthening phase is fully dissolved;

[0134] b. Aging treatment stage: Cool down to 450-480℃ at a rate of 1-2℃ / min and hold for 3 hours;

[0135] c. Stress relief stage: Slowly cool to 200-220℃ at 1-2℃ / min, hold for 1 hour, and air cool to room temperature to obtain a copper roller material with a uniform fine-grained structure. According to actual use requirements, the alloy can be processed into a copper roller sleeve for cooling rollers of iron-based amorphous strips.

[0136] Comparative Example 7

[0137] The model number is C17200 beryllium copper, a commercially available alloy copper.

[0138] Performance testing

[0139] Copper materials were prepared according to the examples and comparative methods, and their performance was tested. Ten samples were prepared for each experimental group, and the average value of all test results was taken. 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: Test method at room temperature".

[0140] For the smelted ingots, samples were first cut parallel to the bottom surface at a distance of 10 mm from the bottom using a metallographic cutting machine. The samples were then finely polished with 400-3000# sandpaper and polished with 0.1W diamond polishing paste. After cleaning and drying with anhydrous ethanol, the samples were etched with a FeCl3 hydrochloric acid ethanol solution (1.4g FeCl3 + 2ml concentrated HCl + 48ml anhydrous ethanol) for approximately 6-7 seconds. Macroscopic solidification structure observation and photography were performed using a scanning machine. As-cast microstructure photographs were taken using an XJP-6A inverted optical microscope at a position half the radius of the sample cross-section. The secondary dendrite arm spacing (SDAS) of the alloy was measured using the truncation method and S-Viewer metallographic analysis software. Metallographic structure observation: The secondary dendrite arm spacing (SDAS) of the alloy was measured using the truncation method and S-Viewer metallographic analysis software.

[0141] Hardness test:

[0142] The Vickers hardness of the samples was tested using an HVS-1000 digital display microhardness tester.

[0143] Mechanical property testing:

[0144] TSE 105D Microcomputer-Controlled Electronic Universal Testing Machine, Sample Preparation: Alloy samples are prepared by wire cutting, with dimensions as shown... Figure 1As shown. Tensile tests were conducted at room temperature at a tensile rate of 1 mm / min.

[0145] Thermal conductivity: The thermal conductivity of the material was tested using a laser thermal conductivity meter manufactured by Xi'an Xiaxi Electronic Technology Co., Ltd. First, the material was cut into circular pieces 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 onto the top and bottom surfaces of the samples to reduce laser reflection and enhance laser pulse energy absorption. To improve measurement accuracy and reduce errors, the sample surface was flat and parallel, with an error within 0.5% of the thickness. The sample surface was polished to avoid defects. The thermal conductivity of duplicate samples from the same experimental group was tested, and the results were averaged.

[0146] 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.

[0147] The friction and wear test lasted for 2 minutes, with a friction reciprocating length of 5 mm. The instantaneous friction coefficient diagram after the test can be obtained from the testing software. The wear track profile cross-section can be measured using a wear track probe, such as... Figure 2 As shown, the depth, width, and wear volume of the wear track can be obtained from the cross-sectional view. The wear rate of the sample can also be calculated using the formula: In the formula, K is the wear rate (unit: mm). 2 / N); V is the wear volume (unit: mm). 3 v' represents the friction velocity (mm / min); t represents the friction duration (min); and W represents the applied load (N). After the wear experiment, the surface morphology was observed using a scanning electron microscope.

[0148] Table 1 Performance Test Results

[0149]

[0150] As can be seen from the data in the table, the copper roller material prepared in the embodiments of the present invention exhibits excellent performance in terms of tensile strength, hardness, thermal conductivity, and wear resistance. The tensile strength of Examples 1-3 is between 480-545 MPa. In terms of hardness, the hardness of the examples reaches 320-366 HV, which is significantly higher than that of the comparative examples. Regarding thermal conductivity, the values ​​of the examples are 395-410 W / m·K, indicating that the material of the embodiments of the present invention has better thermal conductivity and can conduct heat more efficiently. In terms of wear resistance, the wear rate of the examples is as low as 0.06%-0.12%, which means that the copper roller material prepared in the present invention is more wear-resistant and has a longer service life during friction. In contrast, the comparative examples 1-3, which changed the way nanoparticles were added, showed different results. Comparative example 1, without nanoparticle reinforcement, experienced increased wear; comparative example 2, without the Al2O3 shell, showed decreased interfacial bonding ability; and comparative example 3, with only Al2O3 added, showed weakened thermal conductivity. It is evident that the use of ZrO2-WC@Al2O3 core-shell particles in the present invention can effectively improve the comprehensive performance of the copper roller material. Comparative Examples 4-6, which altered the heat treatment process, exhibited different characteristics. Comparative Example 4, with its high-speed cooling throughout, may have residual stress leading to microcracks; Comparative Example 5, with its medium-speed cooling throughout, may have resulted in coarsening of the precipitated phase size; and Comparative Example 6, with its slow cooling throughout, may have led to excessive grain growth. This resulted in a weakening of the overall performance of Comparative Examples 4-6. Therefore, in summary, by adding ZrO2-WC@Al2O3 core-shell particles and employing a specific heat treatment process, the overall performance of copper roller materials for iron-based amorphous ribbons can be significantly improved, meeting practical application requirements. The microstructure samples of the embodiments of this invention and C17200 beryllium copper ingots also show that the embodiments of this invention exhibit refined dendrites and reduced secondary dendrite arm spacing.

[0151] Further, using the materials from the examples and comparative examples as copper sleeves for cooling rollers to prepare iron-based amorphous ribbons, with a copper sleeve thickness of 26 mm, the preparation method is as follows:

[0152] Raw material composition: By mass percentage, the raw materials include: B 2.35wt%, Si 4.82wt%, Al and Ti content both <50ppm, the balance being iron, containing unavoidable trace impurity elements, with the total amount of impurity elements ≤0.5%.

[0153] Manufacturing method:

[0154] (1) Smelting: The raw materials are proportioned according to the percentage and put into the medium frequency furnace for smelting. The final composition of the molten steel is controlled at B 2.35wt%, Si 4.80wt%, Al and Ti content <50ppm, the balance is iron, and it contains unavoidable trace impurity elements with a total impurity element content ≤0.5%. During smelting, protective gas is used to protect the molten steel. The heating temperature of the smelting furnace is 1350℃. After the molten steel is completely melted, it continues to be smelted for 7min under the action of electromagnetic stirring.

[0155] (3) Heat preservation treatment: Vacuum the intermediate heat preservation bag, fill it with protective gas, heat the intermediate bag to 1350°C, pour the molten alloy in step (2) into the intermediate heat preservation bag, keep the temperature constant for 12 minutes, and keep the alloy liquid constant to 1350°C.

[0156] (4) Spraying: The alloy liquid after heat preservation in step (3) is injected into the spraying package and sprayed onto the cooling copper roller through the nozzle of the spraying package under protective gas to form an iron-based amorphous strip.

[0157] (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 by a cross-field magnetic field; the annealed and crystallized strip is then passed through an alloy rolling mill, and then die-cut and packaged to obtain the final product.

[0158] The obtained strips were tested. Magnetic properties were performed according to GB / T 19346.3-2021. A Lake Shore 7407 VSM vibrating sample magnetometer (VSM) was used to test the saturation magnetic induction (Bs) of the sample, with a test magnetic field strength of 800 kA / m. The coercivity (Hc) of the strip samples was measured using a BH hysteresis loop analyzer (MATS-2010SD) manufactured by Hunan Lianzhong Technology Co., Ltd., with a maximum test magnetic field strength of 800 A / m. The stacking factor was tested according to GB / T 19346.2-2017. The test results are shown in Table 2.

[0159] Table 2 Performance test results of iron-based amorphous ribbon

[0160]

[0161] As can be seen from the data in Table 2, the improved quality of the copper roller sleeve, along with its improved cooling rate and uniformity, leads to improved uniformity and flatness of the amorphous ribbon, which is macroscopically manifested as an improvement in the stacking coefficient and overall magnetic properties.

[0162] It should be noted that the above embodiments are merely some preferred embodiments of the present invention, and not all embodiments. Obviously, based on the above embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

Claims

1. A copper roll material for an iron-based amorphous ribbon, characterized by, comprises the following elements by weight percentage: 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 of Cu, with the total amount being 100%; the preparation method of the ZrO2-WC@Al2O3 core-shell particles is as follows: (1) Core layer preparation: dissolve zirconium oxychloride ZrOCl2·8H2O in deionized water to prepare a 0.5 mol / L solution, adjust the pH of the system to 9-10 using ammonia water, and perform hydrothermal reaction at 75-80°C for 6 h. Centrifugation obtains Zr(OH)4 colloid, which is calcined at 550-600°C for 2 h to obtain monoclinic ZrO2 particles. Then, the monoclinic ZrO2 particles are mixed with ammonium metatungstate at a molar ratio of 1:1.2, and 5wt% of polyvinylpyrrolidone is added to the mixture. Ball milling is performed for 12 h. Calcination is performed at 1150-1200°C for 2 h under argon protection to obtain ZrO2-WC composite nanoparticles; (2) Shell layer preparation: disperse the ZrO2-WC composite nanoparticles in ethanol, add aluminum isopropylate, and perform reflux reaction at 85-90°C for 3 h. The molar ratio of Al / Zr in the system is controlled to be 0.5:

1. After centrifugal drying, calcination is performed at 750°C under argon protection for 1 h to form a γ-Al2O3 coating layer. Finally, ZrO2-WC@Al2O3 core-shell particles are obtained.

2. The copper roll material for Fe-based amorphous ribbon according to claim 1, characterized by comprises 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 of copper Cu, with the total amount being 100%.

3. The copper roll material for Fe-based amorphous ribbon according to claim 1, wherein The polyvinylpyrrolidone is PVP-K30.

4. The copper roll material for Fe-based amorphous ribbon according to claim 3, characterized by The copper roll sleeve is a ring-shaped alloy with a thickness of 20-26 mm.

5. The copper roll material for Fe-based amorphous ribbon according to claim 1, wherein In step (2), the solid-liquid ratio of ZrO2-WC composite nanoparticles to ethanol is 10g:30-50mL.

6. A method of producing a copper roll material for an Fe-based amorphous ribbon according to any one of claims 1 to 2, characterized by, The steps include melting, casting, forging, and heat treatment, specifically as follows: (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 be ≤50ppm, control the temperature to be 1150-1200°C, and control the holding time to be ≥1h. Prepare ZrO2-WC@Al2O3 core-shell particles, and add the core-shell particles to the system and ultrasonic dispersion for 10-15min; (2) Casting: pour the molten alloy into a metal mold preheated to 300-350°C, and control the cooling rate to be ≥50°C / min; (3) Forging: heat the cast ingot obtained in step (2) to 850-880°C, and hold for 1-2h. Perform multi-directional forging, and control the final forging temperature to be ≥650°C; (4) Heat treatment: a. Solution treatment stage: increase the temperature to 980-1000°C at a rate of 8-10°C / min, and hold for 1.5-2h. After the holding is completed, water quenching is performed to fully solid-solve the strengthening phase; b. Aging treatment stage: decrease the temperature to 450-480°C at a rate of 5-8°C / min, and hold for 3-4h; c. Stress relief stage: slow cooling at 1-2 ℃ / min to 200-220 ℃, holding for 1 h, air cooling to room temperature, obtaining copper roller material with uniform fine grain structure, according to actual use requirements, the alloy is processed into copper roller sleeve for cooling roller for cooling of amorphous strip, which can be used directly.

7. The method for preparing copper roller material for iron-based amorphous ribbon according to claim 6, characterized in that, In the heat treatment, the whole process is protected by argon.

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