A 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloys and their preparation methods

Abstract

This invention provides a 3D printing Ni 57‑x Co 23 Fe 15 Al5Ta x This invention relates to high-entropy soft magnetic alloys and their preparation methods, falling within the technical field of high-entropy soft magnetic alloy materials and their preparation. The 3D-printed Ni... 57‑ x Co 23 Fe 15 Al5Ta x The high-entropy soft magnetic alloy composition, by atomic percentage, is: Ta 1-3%, Al 5%, Fe 15%, Co 23%, Ni 54-56%. The preparation method includes raw material weighing and vacuum melting, cutting and cleaning, tape spinning, ball milling into powder, and 3D printing to obtain Ni. 57‑x Co 23 Fe 15 Al5Ta x The high-entropy soft magnetic alloy product synergistically improves mechanical properties and corrosion resistance. The method of this invention is simple to implement, easy to operate, and allows for convenient modification of the device structure. It is low-cost, highly efficient, and conducive to large-scale industrial production and widespread application.

Description

Technical Field

[0001] This invention relates to the technical field of high-entropy soft magnetic alloy materials and their preparation, particularly to a 3D-printed Ni... 57- x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloys and their preparation methods are disclosed, which is a method for the synergistic forming of high-entropy soft magnetic alloy components based on strip spinning pre-alloying and additive manufacturing. Background Technology

[0002] Soft magnetic materials are magnetic materials that can be magnetized to saturation under a weak magnetic field and demagnetized and have their polarity reversed under a magnetic field of opposite polarity. This excellent magnetization-demagnetization reversible property makes them irreplaceable in the fields of electronics and power industries (such as high-frequency transformers, reactors, and inductors) and signal communication (such as filters, sensors, and magnetic coupling devices). In recent years, higher requirements have been placed on the saturation magnetization (Bs), coercivity (Hc), permeability (μ), and thermal stability of soft magnetic materials, propelling the research and development of new soft magnetic materials into a critical breakthrough period.

[0003] High-entropy alloys, a novel alloy system composed of five or more metallic elements in equimolar or near-equimolar ratios, exhibit excellent mechanical properties, corrosion resistance, and thermal stability due to their high mixing entropy, lattice distortion, and hysteretic diffusion effects. In recent years, the application of high-entropy alloys in the soft magnetic field has gradually attracted attention, as their multi-principal element characteristics provide a new path for the synergistic optimization of magnetic and mechanical properties. For example, FeCoNi-based high-entropy alloys can form an FCC / BCC two-phase structure by adjusting the content of elements such as Al and Ti, achieving a balance between saturation magnetization (Bs) and coercivity (Hc). However, traditional high-entropy alloy preparation processes (such as arc melting) easily lead to component segregation, coarse grains, and the precipitation of non-magnetic phases, significantly reducing soft magnetic properties. Furthermore, the high melting point and high viscosity of high-entropy alloys increase the difficulty of melt homogenization, further limiting their application in extreme environments such as high frequency and high temperature.

[0004] Currently, there are many problems in the preparation methods of high-entropy soft magnetic alloys, such as: difficulty in controlling compositional uniformity, leading to unstable magnetic properties; complex and costly processes, limiting large-scale production; and the tendency of some methods to introduce impurities or form non-ideal phase structures during preparation, affecting the overall performance of the material. In addition, traditional preparation methods have limited ability to control the microstructure of the alloy, making it difficult to meet the requirements of low loss and high permeability in high-frequency applications.

[0005] Chinese patent CN109930085A discloses a high-temperature and corrosion-resistant high-entropy amorphous soft magnetic alloy and its preparation method. It is evident that iron, cobalt, and nickel are in an equiatomic mass ratio, followed by silicon, then boron, and finally chromium, molybdenum, niobium, or vanadium. The preparation method involves first obtaining a master alloy ingot through vacuum arc melting, then melting it with an induction coil, and finally spraying it onto a copper roller surface for rapid cooling. Clearly, the composition is complex, and the preparation method is limited by the inherent technical constraints of the strip spinning method. The resulting product is only strip-shaped and has a single form, which to some extent limits its application in scenarios requiring complex shapes.

[0006] Chinese patent CN117626091A discloses a soft magnetic high-entropy alloy with high thermal stability and its preparation method. It uses iron and cobalt as the main components of the high-entropy alloy, nickel and aluminum as minor components, and silicon as a supplement. The preparation method involves high-temperature heat treatment and water quenching of the alloy ingot. The preparation method is limited by vacuum arc melting, which carries the risk of segregation. Furthermore, no high-temperature mechanical data is provided, so it is impossible to confirm its mechanical reliability during long-term service in a high-temperature environment.

[0007] Chinese patent CN118726794A discloses a soft magnetic high-entropy alloy with high corrosion resistance and high strength and toughness and its preparation method. The alloy composition has many choices. The preparation method involves wire cutting, mechanical polishing and high-temperature homogenization treatment of the suction-cast alloy ingot, oil quenching, cold rolling, recrystallization and oil quenching, and high-temperature aging and oil quenching. The composition design range of this patent is wide and the verification is insufficient. The addition of Cr element can easily cause an imbalance between magnetic properties and corrosion resistance. The preparation process is lengthy and complicated and can only achieve single-form thin sheet. Moreover, the overall soft magnetic and mechanical performance is weak.

[0008] Chinese patent CN117684066A discloses a two-phase soft magnetic high-entropy alloy and its preparation method. The alloy is composed of four elements: Fe, Co, Cr, and V. The preparation method involves homogenization treatment of the smelted and cast alloy ingot, controlled cold rolling, and two-stage isothermal treatment. Therefore, the preparation process of this patent is cumbersome, and the large amount of cold rolling deformation easily leads to material damage. It can only achieve single-form forming of 2-3mm thick plates, with moderate plasticity; its magnetic properties are significantly weak, and its coercivity is relatively high. Summary of the Invention

[0009] The main objective of this invention is to solve the problems of Ni in the prior art. 57-x Co 23 Fe 15 Al5Ta xThe high-entropy soft magnetic alloy faces several technical challenges. These include: the inability to precisely control element content to achieve synergistic optimization of magnetic and mechanical properties; the failure of compositional ratios to effectively suppress the precipitation of non-magnetic phases while simultaneously meeting the combined requirements of high saturation magnetization, low coercivity, and corrosion resistance; and limitations in preparation methods such as traditional smelting processes leading to compositional segregation and coarse grains; the inability of single processes to achieve cross-scale forming from two-dimensional thin sheets to three-dimensional complex structures; insufficient compositional uniformity and flowability during powder preparation, making it difficult to adapt to additive manufacturing feed requirements; and poor microstructure control. These issues limit the improvement of soft magnetic and mechanical properties. Therefore, a 3D printing method for Ni alloys is proposed to address these problems. 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloys and their preparation methods.

[0010] A 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloy, the 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x The composition of high-entropy soft magnetic alloys by atomic percentage is: Ta 1-3%, Al 5%, Fe 15%, Co 23%, Ni 54-56%.

[0011] Optionally, the 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloys have a uniform equiaxed crystal structure with an average grain size of 30-40 μm.

[0012] Optionally, the 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x The high-entropy soft magnetic alloy has a tensile strength of 600-1000MPa, a yield strength of 250-750MPa, a yield ratio of 0.4-0.7, an elongation of 20-70%, and a strength-ductility product of 0.01-0.05GPa.

[0013] Optionally, the 3D printed Ni 57-x Co 23 Fe 15 Al5Ta xThe saturation magnetization of high-entropy soft magnetic alloys is 100-150 emu / g, the coercivity is 2-6 Oe, the corrosion potential is -200~90 mV, and the corrosion current density is 4×10⁻⁶ mV. -6 -8×10 -6 A / cm 2 .

[0014] A method based on the aforementioned 3D printing Ni 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys, including 3D-printed Ni 57-x Co 23 Fe 15 Al5Ta x The preparation method of high-entropy soft magnetic alloys includes the following steps:

[0015] S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 57-x Co 23 Fe 15 Al5Ta x The atomic percentage of the high-entropy soft magnetic alloy is used to determine the proportion and weighing of raw materials. Then, vacuum arc melting is performed, and after cooling, the ingot is flipped. After multiple meltings, the high-entropy soft magnetic alloy ingot is obtained by suction casting.

[0016] S2, Cutting + Cleaning: Cut the high-entropy soft magnetic alloy ingot of S1 into blocks using a wire cutting machine, polish them with sandpaper, and then put them into a beaker containing anhydrous ethanol for ultrasonic cleaning. Place the cleaned block high-entropy soft magnetic alloy ingot sample into a quartz tube and load it into a single-roller belt winch.

[0017] S3, Strip spinning: The diameter of the copper roller, surface roughness Ra, and rotation speed of the single-roller strip spinning machine in S2 are set and run according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and sprayed onto the surface of the copper roller through a round hole nozzle to obtain a micron-sized high-entropy soft magnetic alloy thin strip.

[0018] S4. Ball milling into powder: Place the micron-sized high-entropy soft magnetic alloy strip of S3 into a ball mill jar, seal the ball mill jar in an argon atmosphere glove box, and then place it into a planetary ball mill. Set the ball milling parameters and run the mill to obtain high-entropy soft magnetic alloy powder.

[0019] S5, 3D printing: Place the high-entropy soft magnetic alloy powder from S4 into the powder feeder, set the printing power, printing speed and powder feeding rate, and then print to obtain the high-entropy soft magnetic alloy product.

[0020] Optionally, in S1, the metals are placed into a vacuum melting furnace according to their atomic ratios, and after three gas washing processes, the furnace is finally evacuated to a vacuum level of 2 × 10⁻⁶. -3 -9×10 -3 Pa, then argon gas is introduced as a protective gas; the current is adjusted to 150-300A by controlling the knob during the melting process, and at least 6 meltings are performed; the dimensions of the high-entropy soft magnetic alloy ingot are 12×12×70-10×21×70mm.

[0021] Optionally, the feature is that the S2 wire cutting machine cuts the blocks into sizes of 7×7×7-10×10×10mm, and the sandpaper used for sanding has a grit of 240, 400, and 800; the ultrasonic cleaning has an ultrasonic frequency of 28-48KHz and a cleaning time of 3-5min.

[0022] Optionally, in S3, the diameter of the copper roller is set to 350-400mm, the surface roughness Ra is 0.5-0.8μm, and the rotation speed of the copper roller is 10-15m / s; the diameter of the round nozzle is 2-5mm, the pressure is 0.1-0.5MPa, and the spray angle is 60-90°; the thickness of the micron-level high-entropy soft magnetic alloy strip is 80-100μm.

[0023] Optionally, in S4, the grinding balls occupy two-thirds of the volume of the grinding jar, and the diameter of the grinding balls is 2-5 mm; the grinding balls are placed in first, followed by the micron-sized high-entropy soft magnetic alloy thin strip in S3; the grinding parameters are set as follows: grinding speed is 400-500 r / min, grinding time is 50-85 h; the average particle size of the high-entropy soft magnetic alloy powder is 60-70 μm.

[0024] Optionally, the S5 printer has a printing power of 800-1000W, a printing speed of 6-12mm / s, a printing layer thickness of 0.5-0.6mm, a substrate material of 45 steel, an alternating S-shaped printing path, and a powder feed rate of 4-12g / min. The high-entropy soft magnetic alloy products come in shapes including cuboids and rings, with a volume of 8-16cm³. 3 .

[0025] Technical principle of the invention:

[0026] The technical principle of this invention is based on the intrinsic effects of high-entropy alloys, namely "high mixing entropy, lattice distortion, and hysteretic diffusion," and is achieved through precise design of Ni... 57-x Co 23 Fe 15 Al5Ta xBy adjusting the atomic percentage ratio, high saturation magnetization is ensured through the magnetic moment coupling of Fe and Co, magnetocrystalline anisotropy is optimized by adjusting the lattice of Ni, and grain refinement and suppression of non-magnetic phase precipitation by Al and Ta through lattice distortion, a synergistic effect of magnetic properties, mechanical properties and thermal stability is achieved. At the same time, through the coupling of multiple processes such as "arc melting-spinning-high-energy ball milling-additive manufacturing", a closed loop of "composition optimization-micro-control-structural forming" is formed, which ultimately improves the saturation magnetization, corrosion resistance, mechanical properties and forming freedom of the alloy.

[0027] The above technical solution has at least the following advantages compared with the existing technology:

[0028] The above-described solution, proposed in this invention, is a method for 3D printing Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloys and their preparation methods can solve the problems of Ni in existing technologies. 57-x Co 23 Fe 15 Al5Ta x The high-entropy soft magnetic alloy faces several technical challenges, including the failure to precisely control element content to achieve synergistic optimization of magnetic and mechanical properties; the inability of the composition ratio to effectively suppress the precipitation of non-magnetic phases and the difficulty in simultaneously meeting the comprehensive requirements of high saturation magnetization, low coercivity, and corrosion resistance; and the limitations of traditional smelting processes in preparation, which can easily lead to compositional segregation and coarse grains. Furthermore, single processes cannot achieve cross-scale forming from two-dimensional thin sheets to three-dimensional complex structures, and the powder preparation process suffers from insufficient compositional uniformity and flowability, making it difficult to adapt to additive manufacturing feed requirements. Finally, the poor microstructure control capability further limits the improvement of soft magnetic and mechanical properties.

[0029] This invention achieves an ultra-high-speed cooling process by employing an advanced belt-spinning process. This rapid solidification method significantly suppresses the component segregation problem commonly encountered in traditional material preparation processes, effectively avoids the formation of coarse grains, and thus greatly improves the uniformity of the material's microstructure, laying a solid foundation for subsequent material performance optimization.

[0030] This invention further refines the thin strip formed after spinning into micron-level powder through a ball milling alloying process. This not only enhances the soft magnetic properties of the material but also improves its magnetic permeability and saturation magnetization. At the same time, it provides a guarantee of high-uniformity and high-quality raw materials for subsequent additive manufacturing processes, ensuring the performance consistency and reliability of the final product.

[0031] This invention enables the precise molding of complex structures through the application of 3D printing, overcoming the limitations of traditional manufacturing processes in molding structures, expanding the design freedom of high-entropy soft magnetic alloys, and providing a new technical path and broad development prospects for their engineering applications in fields such as motors and sensors.

[0032] Ni obtained by additive manufacturing by the method of the present invention 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic materials and Ni obtained by casting 57- x Co 23 Fe 15 Al5Ta x Compared with high-entropy soft magnetic materials, the tensile strength is increased by about 4.96%, the strain is increased by about 60.70%, the corrosion current is reduced by about 43.67%, and the saturation magnetization is increased by about 12.5%.

[0033] In summary, the method of the present invention is superior to existing Ni 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys involves raw material weighing and vacuum melting, cutting and cleaning, tape spinning, ball milling into powder, and 3D printing to obtain Ni. 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloy products synergistically improve mechanical properties and corrosion resistance; therefore, the method is simple to process, easy to operate, and the device structure can be easily improved. It is low in cost and high in efficiency, which is conducive to large-scale industrial production and application. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x Ni in high-entropy soft magnetic alloys by vacuum arc melting 56 Co 23 Fe 15 Actual image of Al5Ta1 ingot;

[0036] Figure 2 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x Ni in high-entropy soft magnetic alloys by vacuum arc melting 56 Co 23 Fe 15 Physical image of Al5Ta1 strip;

[0037] Figure 3 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x Ni in high-entropy soft magnetic alloys by vacuum arc melting 56 Co 23 Fe 15 A schematic diagram of the ball milling process of Al5Ta1, wherein (a) is a schematic diagram of the initial stage of ball milling, (b) is a schematic diagram of the ball milling process, and (c) is a schematic diagram of the ball milling completion stage.

[0038] Figure 4 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x Ni in high-entropy soft magnetic alloys 56 Co 23 Fe 15 A picture of a ball mill of Al5Ta1;

[0039] Figure 5 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x Ni in high-entropy soft magnetic alloys 56 Co 23 Fe 15 SEM image of Al5Ta1 powder after ball milling;

[0040] Figure 6 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x Ni in high-entropy soft magnetic alloys 56 Co 23 Fe 15 Grain size distribution of Al5Ta1 powder after ball milling;

[0041] Figure 7 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x Schematic diagram of 3D printing in the preparation method of high-entropy soft magnetic alloys;

[0042] Figure 8 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x 3D printing of Ni in the preparation method of high-entropy soft magnetic alloy 56 Co 23 Fe 15 Physical image of Al5Ta1 high-entropy soft magnetic alloy;

[0043] Figure 9(a) is a metallographic image of the high-entropy soft magnetic alloy prepared in Example 1 of the present invention;

[0044] Figure 9(b) is a metallographic image of the high-entropy soft magnetic alloy prepared by melting and solidification in Comparative Example 1 of the present invention;

[0045] Figure 10 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x 3D printing of Ni in the preparation method of high-entropy soft magnetic alloy 56 Co 23 Fe 15 Hysteresis loop diagram of Al5Ta1 high-entropy soft magnetic alloy;

[0046] Figure 11 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x 3D printing of Ni in the preparation method of high-entropy soft magnetic alloy 56 Co 23 Fe 15 A magnified view of the hysteresis loop of Al5Ta1 high-entropy soft magnetic alloy.

[0047] Figure 12 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x 3D printing of Ni in the preparation method of high-entropy soft magnetic alloy 56 Co 23 Fe 15Stress-strain curve of Al5Ta1 high-entropy soft magnetic alloy;

[0048] Figure 13 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x 3D printing of Ni in the preparation method of high-entropy soft magnetic alloy 56 Co 23 Fe 15 Polarization curve of Al5Ta1 high-entropy soft magnetic alloy;

[0049] Figure 14 This is a 3D printing Ni according to Embodiment 1 of the present invention. 57-x Co 23 Fe 15 Al5Ta x 3D printing of Ni in the preparation method of high-entropy soft magnetic alloy 56 Co 23 Fe 15 XRD diffraction pattern of Al5Ta1 high-entropy soft magnetic alloy. Detailed Implementation

[0050] The technical solution of the present invention will now be described with reference to the accompanying drawings.

[0051] In embodiments of the present invention, words such as "exemplarily," "for example," etc., are used to indicate that something is an example, illustration, or description. Any embodiment or design described as "exemplary" in the present invention should not be construed as being more preferred or advantageous than other embodiments or designs. Specifically, the use of the word "exemplary" is intended to present the concept in a concrete manner. Furthermore, in embodiments of the present invention, the meaning expressed by "and / or" can be both, or either one.

[0052] In the embodiments of the present invention, the terms "image" and "picture" may sometimes be used interchangeably. It should be noted that when the distinction is not emphasized, their intended meanings are consistent.

[0053] In this embodiment of the invention, sometimes a subscript such as W1 may be written in a non-subscript form such as W1. When the difference is not emphasized, the meaning they express is the same.

[0054] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.

[0055] A 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloy, the 3D printed Ni57-x Co 23 Fe 15 Al5Ta x The composition of high-entropy soft magnetic alloys by atomic percentage is: Ta 1-3%, Al 5%, Fe 15%, Co 23%, Ni 54-56%.

[0056] Specifically, the 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloys have a uniform equiaxed crystal structure with an average grain size of 30-40 μm.

[0057] Specifically, the 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x The high-entropy soft magnetic alloy has a tensile strength of 600-1000MPa, a yield strength of 250-750MPa, a yield ratio of 0.4-0.7, an elongation of 20-70%, and a strength-ductility product of 0.01-0.05GPa.

[0058] Specifically, the 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x The saturation magnetization of high-entropy soft magnetic alloys is 100-150 emu / g, the coercivity is 2-6 Oe, the corrosion potential is -200~90 mV, and the corrosion current density is 4×10⁻⁶ mV. -6 -8×10 -6 A / cm 2 .

[0059] A method based on the aforementioned 3D printing Ni 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys, including 3D-printed Ni 57-x Co 23 Fe 15 Al5Ta x The preparation method of high-entropy soft magnetic alloys includes the following steps:

[0060] S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 57-x Co 23 Fe 15 Al5Ta xThe atomic percentage of the high-entropy soft magnetic alloy is used to determine the proportion and weighing of raw materials. Then, vacuum arc melting is performed, and after cooling, the ingot is flipped. After multiple meltings, the high-entropy soft magnetic alloy ingot is obtained by suction casting.

[0061] S2, Cutting + Cleaning: Cut the high-entropy soft magnetic alloy ingot of S1 into blocks using a wire cutting machine, polish them with sandpaper, and then put them into a beaker containing anhydrous ethanol for ultrasonic cleaning. Place the cleaned block high-entropy soft magnetic alloy ingot sample into a quartz tube and load it into a single-roller belt winch.

[0062] S3, Strip spinning: The diameter of the copper roller, surface roughness Ra, and rotation speed of the single-roller strip spinning machine in S2 are set and run according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and sprayed onto the surface of the copper roller through a round hole nozzle to obtain a micron-sized high-entropy soft magnetic alloy thin strip.

[0063] S4. Ball milling into powder: Place the micron-sized high-entropy soft magnetic alloy strip of S3 into a ball mill jar, seal the ball mill jar in an argon atmosphere glove box, and then place it into a planetary ball mill. Set the ball milling parameters and run the mill to obtain high-entropy soft magnetic alloy powder.

[0064] S5, 3D printing: Place the high-entropy soft magnetic alloy powder from S4 into the powder feeder, set the printing power, printing speed and powder feeding rate, and then print to obtain the high-entropy soft magnetic alloy product.

[0065] Specifically, in S1, the metals are placed into a vacuum melting furnace according to their atomic ratios. After three rounds of gas washing, the furnace is finally evacuated to a vacuum level of 2 × 10⁻⁶. -3 -9×10 -3 Pa, then argon gas is introduced as a protective gas; the current is adjusted to 150-300A by controlling the knob during the melting process, and at least 6 meltings are performed; the dimensions of the high-entropy soft magnetic alloy ingot are 12×12×70-10×21×70mm.

[0066] Specifically, the S2 wire cutting machine cuts blocks to a size of 7×7×7-10×10×10mm, and the sandpaper used for sanding is 240 grit, 400 grit, and 800 grit; the ultrasonic cleaning uses an ultrasonic frequency of 28-48KHz and a cleaning time of 3-5min.

[0067] Specifically, in S3, the diameter of the copper roller is set to 350-400mm, the surface roughness Ra is 0.5-0.8μm, and the rotation speed of the copper roller is 10-15m / s; the diameter of the round nozzle is 2-5mm, the pressure is 0.1-0.5MPa, and the spray angle is 60-90°; the thickness of the micron-level high-entropy soft magnetic alloy strip is 80-100μm.

[0068] Specifically, in S4, the grinding balls occupy two-thirds of the volume of the grinding jar, and the diameter of the grinding balls is 2-5 mm; the grinding balls are placed in first, followed by the micron-sized high-entropy soft magnetic alloy thin strip from S3; the grinding parameters are set as follows: grinding speed is 400-500 r / min, grinding time is 50-85 h; the average particle size of the high-entropy soft magnetic alloy powder is 60-70 μm.

[0069] Specifically, the S5 features a printing power of 800-1000W, a printing speed of 6-12mm / s, a layer thickness of 0.5-0.6mm, a 45 steel substrate, an alternating S-shaped printing path, and a powder feed rate of 4-12g / min. The high-entropy soft magnetic alloy products come in rectangular and toroidal shapes, with a volume of 8-16cm³. 3 .

[0070] Example 1

[0071] This embodiment describes a 3D printed Ni 56 Co 23 Fe 15 Al5Ta1 high-entropy soft magnetic alloy, the 3D printed Ni 56 Co 23 Fe 15 The preparation method of Al5Ta1 high-entropy soft magnetic alloy includes the following steps:

[0072] S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 56 Co 23 Fe 15 The atomic percentages of Al5Ta1 high-entropy soft magnetic alloy were used to determine the proportions and weights of the raw materials. Then, each metal was placed into a vacuum melting furnace according to its atomic ratio. After three gas washing processes, the furnace was finally evacuated to a vacuum level of 2 × 10⁻⁶. -3 Pa, then argon gas is introduced as a protective gas; the melting process is controlled by adjusting the current to 230A via a knob, and vacuum arc melting is performed at least 6 times. After cooling, the ingot is flipped, and after multiple meltings, it is obtained by suction casting to obtain a high-entropy soft magnetic alloy ingot with dimensions of 10×21×70mm. Figure 1 As shown;

[0073] S2. Cutting and Cleaning: The high-entropy soft magnetic alloy ingot of S1 is cut into blocks using a wire EDM machine. The size of the blocks cut by the wire EDM machine is 10×10×10mm. After being sanded with sandpaper, the blocks are placed in beakers containing anhydrous ethanol. The sandpaper grits are 240 grit, 400 grit, and 800 grit. Ultrasonic cleaning is performed at a frequency of 40KHz for 3 minutes. The cleaned block samples of high-entropy soft magnetic alloy ingots are placed in quartz tubes and loaded into a single-roller belt winch.

[0074] S3. Strip Spinning: The copper roller diameter, surface roughness Ra, and rotation speed of the single-roller strip spinner in S2 are set and operated according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The copper roller diameter is set to 350 mm, the surface roughness Ra to 0.6 μm, and the rotation speed to 10 m / s. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and pressure-sprayed onto the surface of the copper roller through a circular nozzle with a diameter of 4 mm, a pressure of 0.3 MPa, and a spray angle of 90°. A high-entropy soft magnetic alloy thin strip is obtained, such as... Figure 2 As shown, the strip has a smooth and flat surface, a thickness of 100μm, and a width of 3mm;

[0075] S4. Ball milling into powder: such as Figure 4 As shown, the S3 micron-sized high-entropy soft magnetic alloy strip was placed in a ball mill jar, with the grinding balls occupying two-thirds of the jar's volume. The grinding balls had a diameter of 5 mm. The grinding balls were placed in first, followed by the S3 micron-sized high-entropy soft magnetic alloy strip. The ball mill jar was sealed in an argon-atmospheric glove box and then placed in a planetary ball mill. The ball milling parameters were set and run. The set ball milling parameters were: ball milling speed of 450 r / min and ball milling time of 50 h.

[0076] The process of ball milling strip powder production is as follows Figure 3 As shown, the process is divided into three key stages: (a) the initial stage of ball milling, in which the ball mill jar is filled with alloy ribbons and grinding balls, and the material is initially dispersed in ribbon and spherical shapes; (b) the ball milling stage, in which the grinding balls impact, crush and shear the alloy ribbons at high speed, and the ribbons gradually break down and form alloy powder particles; (c) the ball milling completion stage, in which the alloy ribbons are completely transformed into alloy powder, and the powder particles are mixed and distributed with the grinding balls in the ball mill jar.

[0077] Ball milling yielded high-entropy soft magnetic alloy powder, the powder morphology of which is as follows: Figure 5 As shown, the particles are mainly spherical or near-spherical, with some particles exhibiting slightly irregular shapes and relatively rough surfaces; the powder size distribution is as follows. Figure 6 As shown, the particle diameter is between 40-110 μm, with an average particle size of 65 μm;

[0078] S5 3D Printing: Place the high-entropy soft magnetic alloy powder from S4 into the powder feeder. First, set the printing power, printing speed, and powder feed rate. The printing laser power is 800W, the printing speed is 12mm / s, the printing layer thickness is 0.5mm, the substrate material is 45 steel, the printing path uses an alternating S-shaped pattern, and the powder feed rate is 5g / min. Then proceed with printing. A schematic diagram is shown below. Figure 7 As shown. High-entropy soft magnetic alloy products are obtained, such as... Figure 8As shown, the alloy exhibits good formability, with no macroscopic cracks or collapse defects on the surface. The high-entropy soft magnetic alloy product is a cuboid with a volume of 8 cm³. 3 .

[0079] The 3D printed Ni prepared in this embodiment 56 Co 23 Fe 15 Al5Ta1 high-entropy soft magnetic alloy has a uniform equiaxed crystal structure with an average grain size of 35μm; its tensile strength is 639.9MPa, yield strength is 325.92MPa, yield ratio is 0.35, elongation is 64.9%, and strength-ductility product is 0.042GPa.

[0080] The 3D printed Ni prepared in this embodiment 56 Co 23 Fe 15 The Al5Ta1 high-entropy soft magnetic alloy has a saturation magnetization of 119.40 emu / g, a coercivity of 3.99 Oe, a corrosion potential of -156 mV, and a corrosion current density of 7.593 × 10⁻⁶. -6 A / cm 2 .

[0081] 3D printing Ni 56 Co 23 Fe 15 The microstructure of Al5Ta1 is shown in Figure 9(a): the microstructure exhibits a uniform, fine granular structure with small grain size and relatively uniform distribution. Figure 9(b) shows the as-cast Ni. 56 Co 23 Fe 15 Microstructure of Al5Ta1: The structure is a typical dendritic structure with interlocking dendrite arms forming an irregular network. Comparing Figure 9(a) and Figure 9(b), it can be seen that additive manufacturing can significantly change the microstructure of the material, resulting in smaller and more uniform grain size.

[0082] 3D printing Ni 56 Co 23 Fe 15 The stress-strain curve of Al5Ta1 high-entropy soft magnetic alloy is shown below. Figure 12 As shown in the figure. It can be seen from the figure that the deposited Ni... 56 Co 23 Fe 15 The tensile strength and yield strength of Al5Ta1 are 639.72 MPa and 325.92 MPa, respectively, with a strain of 69.89%. In the as-cast state, the tensile strength and yield strength are 609.49 MPa and 395.32 MPa, respectively, with a strain of 40.38%. Compared to the as-cast state, the tensile strength of the deposited state increases by approximately 4.96%, and the strain increases by approximately 60.70%.

[0083] 3D printing Ni 56 Co 23 Fe 15 The hysteresis loop and a magnified view of the Al5Ta1 high-entropy soft magnetic alloy are shown below. Figure 10 , Figure 11 As shown in the figure. The figure shows the deposited Ni after 3D printing. 56 Co 23 Fe 15 The saturation magnetization of Al5Ta1 is 119.40 emu / g, and the coercivity is 3.99 Oe. As-cast Ni... 56 Co 23 Fe 15 The saturation magnetization of Al5Ta1 is 106.14 emu / g, and the coercivity is 2.52 Oe. Compared with the as-cast state, the saturation magnetization of the deposited state increased by 12.5%, while the coercivity decreased slightly.

[0084] 3D printing Ni 56 Co 23 Fe 15 The polarization curve of Al5Ta1 high-entropy soft magnetic alloy is as follows: Figure 13 As shown. For Ni 56 Co 23 Fe 15 The Al5Ta1 material in both its deposited and as-cast states has similar corrosion potentials (deposited state -156mV, as-cast state -158mV), and its spontaneous corrosion tendency is basically the same at the thermodynamic level; however, there are significant differences in its kinetic corrosion performance: the corrosion current in the deposited state is 7.593 × 10⁻⁶ mV. -6 A / cm 2 The as-cast corrosion current reached 1.348 × 10⁻⁶. -5 A (approximately 1.77 times that of the deposited state), indicating that the deposited state has a lower corrosion rate and better corrosion resistance.

[0085] 3D printing Ni 56 Co 23 Fe 15 The XRD diffraction pattern of Al5Ta1 high-entropy soft magnetic alloy is as follows: Figure 14 As shown, the diffraction peaks in both states correspond to the (111), (200), and (220) crystal planes, which are typical characteristics of face-centered cubic (FCC) structures. This indicates that the phase structures of the deposited and cast states are completely identical, both being a single FCC phase with no impurities precipitated. The diffraction peak intensity of the deposited state is significantly higher than that of the cast state, indicating that the FCC phase in the deposited material has higher crystallinity and a more obvious preferred orientation of crystal planes.

[0086] Example 2

[0087] This embodiment describes a 3D printed Ni 55 Co23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy, the 3D printed Ni 55 Co 23 Fe 15 The preparation method of Al5Ta2 high-entropy soft magnetic alloy includes the following steps:

[0088] S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 55 Co 23 Fe 15 The atomic percentages of Al5Ta2 high-entropy soft magnetic alloy were used to determine the proportions and weights of the raw materials. Then, each metal was placed into a vacuum melting furnace according to its atomic ratio. After three gas washing processes, the furnace was finally evacuated to a vacuum level of 2×10⁻⁶. -3 Pa, then argon gas is introduced as a protective gas; the current is adjusted to 230A by controlling the knob during the melting process, and the vacuum arc melting is carried out at least 6 times. After cooling, the ingot is flipped. After multiple meltings, a high-entropy soft magnetic alloy ingot with dimensions of 10×21×70mm is obtained by suction casting.

[0089] S2. Cutting and Cleaning: The high-entropy soft magnetic alloy ingot of S1 is cut into blocks using a wire EDM machine. The size of the blocks cut by the wire EDM machine is 10×10×10mm. After being sanded with sandpaper, the blocks are placed in beakers containing anhydrous ethanol. The sandpaper grits are 240 grit, 400 grit, and 800 grit. Ultrasonic cleaning is performed at a frequency of 40KHz for 3 minutes. The cleaned block samples of high-entropy soft magnetic alloy ingots are placed in quartz tubes and loaded into a single-roller belt winch.

[0090] S3. Strip spinning: The diameter, surface roughness Ra, and rotation speed of the copper roller in the single-roller strip spinning machine of S2 are set and operated according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The copper roller diameter is set to 350 mm, the surface roughness Ra is 0.6 μm, and the copper roller rotation speed is 10 m / s. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and pressure-sprayed onto the surface of the copper roller through a round-hole nozzle with a diameter of 4 mm, a pressure of 0.3 MPa, and a spray angle of 90°. A micron-sized high-entropy soft magnetic alloy thin strip with a thickness of 100 μm is obtained.

[0091] S4. Ball milling to powder: Place the micron-sized high-entropy soft magnetic alloy ribbon of S3 into a ball mill jar, with the grinding balls occupying two-thirds of the jar's volume. The grinding balls have a diameter of 5 mm. Place the grinding balls first, then the micron-sized high-entropy soft magnetic alloy ribbon of S3. Seal the ball mill jar in an argon-atmospheric glove box, then place it in a planetary ball mill. Set the ball milling parameters and run the mill. The set ball milling parameters are: ball milling speed 450 r / min, ball milling time 50 h. Ball milling yields high-entropy soft magnetic alloy powder with an average particle size of 65 μm.

[0092] S5 3D Printing: High-entropy soft magnetic alloy powder from S4 is placed in the powder feeder. The printing power, printing speed, and powder feed rate are set as follows: laser power 800W, printing speed 12mm / s, layer thickness 0.5mm, substrate material 45 steel, printing path using an alternating S-shaped pattern, and powder feed rate 5g / min. Printing is then performed to obtain the high-entropy soft magnetic alloy product. The high-entropy soft magnetic alloy product is a cuboid with a volume of 8cm³. 3 .

[0093] The 3D printed Ni prepared in this embodiment 55 Co 23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy has a uniform equiaxed crystal structure with an average grain size of 33μm; its tensile strength is 863.86MPa, yield strength is 436.67MPa, yield ratio is 0.51, elongation is 47.17%, and strength-ductility product is 0.041GPa.

[0094] The 3D printed Ni prepared in this embodiment 55 Co 23 Fe 15 The Al5Ta2 high-entropy soft magnetic alloy has a saturation magnetization of 122.84 emu / g, a coercivity of 5.22 Oe, a corrosion potential of -105 mV, and a corrosion current density of 4.515 × 10⁻⁶. -6 A / cm 2 .

[0095] Comparative Example 1

[0096] Preparation of cast Ni 56 Co 23 Fe 15 Al5Ta1: Its chemical composition by atomic percentage is: Ta 1%, Al 5%, Fe 15%, Co 23%, Ni 56%. The metals are placed in a vacuum melting furnace and evacuated to a vacuum of 2 × 10⁻⁶. -3 The process involves three gas purgings, followed by the introduction of argon as a protective gas. Arc ignition is initiated in a vacuum environment, and the current is adjusted using a control knob until the material is completely melted. After cooling, the ingot is flipped and melted again. This process is repeated at least six times to ensure the ingot's uniformity. After melting, the ingot is vacuum-cast into 10×21×70mm samples, which are then cut, polished, and subjected to performance testing and microstructure analysis.

[0097] The 3D printed Ni prepared in this comparative example 56 Co 23 Fe 15Al5Ta1 high-entropy soft magnetic alloy has a dendritic structure with an average grain size of 92 μm; its tensile strength is 609.39 MPa, yield strength is 329.10 MPa, yield ratio is 0.54, elongation is 40.38%, and strength-ductility product is 0.025 GPa.

[0098] The as-cast Ni prepared in this comparative example 56 Co 23 Fe 15 The Al5Ta1 high-entropy soft magnetic alloy has a saturation magnetization of 106.14 emu / g, a coercivity of 2.52 Oe, a corrosion potential of -158 mV, and a corrosion current density of 1.348 × 10⁻⁶. -5 A / cm 2 .

[0099] Comparative Example 2

[0100] Preparation of cast Ni 55 Co 23 Fe 15 Al₅Ta₂: Its chemical composition by atomic percentage is: Ni 55%, Fe 15%, Co 23%, Al 5%, and Ta 2%. The metals are placed in a vacuum melting furnace and evacuated to a vacuum of 2 × 10⁻⁶. -3 The process involves three gas purgings, followed by the introduction of argon as a protective gas. Arc ignition is initiated in a vacuum environment, and the current is adjusted using a control knob until the material is completely melted. After cooling, the ingot is flipped and melted again. This process is repeated at least six times to ensure the ingot's uniformity. After melting, the ingot is vacuum-cast into 10×21×70mm samples, which are then cut, polished, and subjected to performance testing and microstructure analysis.

[0101] The as-cast Ni prepared in this comparative example 55 Co 23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy has a dendritic structure with an average grain size of 90μm; its tensile strength is 816.62MPa, yield strength is 472.54MPa, yield ratio is 0.58, elongation is 34.76%, and strength-ductility product is 0.028GPa.

[0102] The as-cast Ni prepared in this comparative example 55 Co 23 Fe 15 The Al5Ta2 high-entropy soft magnetic alloy has a saturation magnetization of 111.25 emu / g, a coercivity of 3.68 Oe, a corrosion potential of -110 mV, and a corrosion current density of 2.485 × 10⁻⁶. -6 A / cm 2 .

[0103] Comparing Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 1 with Example 2, it can be seen that, compared with the simple vacuum melting and casting process, the high-entropy soft magnetic alloy prepared by 3D printing has a more uniform microstructure, significantly refined grains, and achieves a synergistic improvement in mechanical properties, with a better yield strength ratio (the lower the yield strength ratio, the better the plasticity of the material, the greater the safety margin from yield to fracture, and the better the overall mechanical properties of the material). The saturation magnetization and corrosion resistance are significantly improved, and although the coercivity increases slightly, it still maintains the soft magnetic properties. While keeping the proportions of Co, Fe, and Al unchanged, increasing the proportion of Ta atoms from 1% to 2% can further refine the grains of the 3D printed alloy, significantly improving tensile strength and corrosion resistance.

[0104] Example 3

[0105] This embodiment describes a 3D printed Ni 54 Co 23 Fe 15 Al5Ta3 high-entropy soft magnetic alloy, the 3D printed Ni 54 Co 23 Fe 15 The preparation method of Al5Ta3 high-entropy soft magnetic alloy includes the following steps:

[0106] S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 54 Co 23 Fe 15 The atomic percentages of Al5Ta3 high-entropy soft magnetic alloy were used to determine the proportions and weights of the raw materials. Then, the metals were placed into a vacuum melting furnace according to their atomic ratios. After three gas washing processes, the furnace was finally evacuated to a vacuum level of 2 × 10⁻⁶. -3 Pa, then argon gas is introduced as a protective gas; the current is adjusted to 230A by controlling the knob during the melting process, and the vacuum arc melting is carried out at least 6 times. After cooling, the ingot is flipped. After multiple meltings, a high-entropy soft magnetic alloy ingot with dimensions of 10×21×70mm is obtained by suction casting.

[0107] S2. Cutting and Cleaning: The high-entropy soft magnetic alloy ingot of S1 is cut into blocks using a wire EDM machine. The size of the blocks cut by the wire EDM machine is 10×10×10mm. After being sanded with sandpaper, the blocks are placed in beakers containing anhydrous ethanol. The sandpaper grits are 240 grit, 400 grit, and 800 grit. Ultrasonic cleaning is performed at a frequency of 40KHz for 3 minutes. The cleaned block samples of high-entropy soft magnetic alloy ingots are placed in quartz tubes and loaded into a single-roller belt winch.

[0108] S3. Strip spinning: The diameter, surface roughness Ra, and rotation speed of the copper roller in the single-roller strip spinning machine of S2 are set and operated according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The copper roller diameter is set to 350 mm, the surface roughness Ra is 0.6 μm, and the copper roller rotation speed is 10 m / s. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and pressure-sprayed onto the surface of the copper roller through a round-hole nozzle with a diameter of 4 mm, a pressure of 0.3 MPa, and a spray angle of 90°. A micron-sized high-entropy soft magnetic alloy thin strip with a thickness of 100 μm is obtained.

[0109] S4. Ball milling: Place the micron-sized high-entropy soft magnetic alloy ribbon from S3 into a ball mill jar, with grinding balls occupying two-thirds of the jar's volume. The grinding balls have a diameter of 5 mm. Place the grinding balls first, then the micron-sized high-entropy soft magnetic alloy ribbon from S3. Seal the ball mill jar in an argon-atmosphere glove box, then place it in a planetary ball mill. Set the ball milling parameters and run the mill. The set parameters are: ball milling speed 400 r / min, ball milling time 85 h. Ball milling yields high-entropy soft magnetic alloy powder with an average particle size of 65 μm.

[0110] S5 3D Printing: High-entropy soft magnetic alloy powder from S4 is placed in the powder feeder. The printing power, printing speed, and powder feed rate are set as follows: printing power 800W, printing speed 12mm / s, layer thickness 0.5mm, substrate material 45 steel, printing path using an alternating S-shaped pattern, and powder feed rate 5g / min. Printing is then performed to obtain the high-entropy soft magnetic alloy product. The high-entropy soft magnetic alloy product is a cuboid with a volume of 8cm³. 3 .

[0111] The 3D printed Ni prepared in this embodiment 54 Co 23 Fe 15 Al5Ta3 high-entropy soft magnetic alloy has a uniform equiaxed crystal structure with an average grain size of 32μm; its tensile strength is 957.24MPa, yield strength is 657.24MPa, yield ratio is 0.69, elongation is 20.68%, and strength-ductility product is 0.042GPa.

[0112] The 3D printed Ni prepared in this embodiment 54 Co 23 Fe 15 The Al5Ta3 high-entropy soft magnetic alloy has a saturation magnetization of 107.51 emu / g, a coercivity of 4.92 Oe, a corrosion potential of -143 mV, and a corrosion current density of 6.475 × 10⁻⁶. -6 A / cm 2 .

[0113] Example 4

[0114] This embodiment describes a 3D printed Ni 55 Co 23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy, the 3D printed Ni 55 Co 23 Fe 15 The preparation method of Al5Ta2 high-entropy soft magnetic alloy includes the following steps:

[0115] S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 55 Co 23 Fe 15 The atomic percentages of Al5Ta2 high-entropy soft magnetic alloy were used to determine the proportions and weights of the raw materials. Then, each metal was placed into a vacuum melting furnace according to its atomic ratio. After three gas washing processes, the furnace was finally evacuated to a vacuum level of 2×10⁻⁶. -3 Pa, then argon gas is introduced as a protective gas; the current is adjusted to 150-300A by controlling the knob during the melting process, and vacuum arc melting is carried out at least 6 times. After cooling, the ingot is flipped. After multiple meltings, a high-entropy soft magnetic alloy ingot with dimensions of 10×21×70mm is obtained by suction casting.

[0116] S2. Cutting and Cleaning: The high-entropy soft magnetic alloy ingot of S1 is cut into blocks using a wire EDM machine. The size of the blocks cut by the wire EDM machine is 10×10×10mm. After sanding with sandpaper, the blocks are placed in beakers containing anhydrous ethanol. The sandpaper grits are 240 grit, 400 grit, and 800 grit. Ultrasonic cleaning is performed at a frequency of 48KHz for 3 minutes. The cleaned block samples of high-entropy soft magnetic alloy ingots are placed in quartz tubes and loaded into a single-roller belt winch.

[0117] S3. Strip spinning: The diameter, surface roughness Ra, and rotation speed of the copper roller in the single-roller strip spinning machine of S2 are set and operated according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The copper roller diameter is set to 350 mm, the surface roughness Ra is 0.6 μm, and the copper roller rotation speed is 10 m / s. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and pressure-sprayed onto the surface of the copper roller through a round-hole nozzle with a diameter of 4 mm, a pressure of 0.3 MPa, and a spray angle of 90°. A micron-sized high-entropy soft magnetic alloy thin strip with a thickness of 100 μm is obtained.

[0118] S4. Ball milling to powder: Place the micron-sized high-entropy soft magnetic alloy ribbon of S3 into a ball mill jar, with the grinding balls occupying two-thirds of the jar's volume. The grinding balls have a diameter of 5 mm. First, place the grinding balls, then the micron-sized high-entropy soft magnetic alloy ribbon of S3 into the jar. Seal the ball mill jar in an argon-atmospheric glove box, then place it in a planetary ball mill. Set the ball milling parameters and run the mill. The set ball milling parameters are: ball milling speed 400 r / min, ball milling time 50 h. Ball milling yields high-entropy soft magnetic alloy powder with an average particle size of 65 μm.

[0119] S5 3D Printing: High-entropy soft magnetic alloy powder from S4 is placed in the powder feeder. The printing power, printing speed, and powder feed rate are set as follows: printing power 900W, printing speed 12mm / s, layer thickness 0.5mm, substrate material 45 steel, printing path using an alternating S-shaped pattern, and powder feed rate 5g / min. Printing is then performed to obtain the high-entropy soft magnetic alloy product. The high-entropy soft magnetic alloy product is a cuboid with a volume of 8cm³. 3 .

[0120] The 3D printed Ni prepared in this embodiment 55 Co 23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy has a uniform equiaxed crystal structure with an average grain size of 60μm; its tensile strength is 902.51MPa, yield strength is 467.87MPa, yield ratio is 0.52, elongation is 32.75%, and strength-ductility product is 0.030GPa.

[0121] The 3D printed Ni prepared in this embodiment 55 Co 23 Fe 15 The Al5Ta2 high-entropy soft magnetic alloy has a saturation magnetization of 122.05 emu / g, a coercivity of 5.20 Oe, a corrosion potential of -97.50 mV, and a corrosion current density of 3.75 × 10⁻⁶. -6 A / cm 2 .

[0122] Example 5

[0123] This embodiment describes a 3D printed Ni 55 Co 23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy, the 3D printed Ni 55 Co 23 Fe 15 The preparation method of Al5Ta2 high-entropy soft magnetic alloy includes the following steps:

[0124] S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 55 Co23 Fe 15 The atomic percentages of Al5Ta2 high-entropy soft magnetic alloy were used to determine the proportions and weights of the raw materials. Then, each metal was placed into a vacuum melting furnace according to its atomic ratio. After three gas washing processes, the furnace was finally evacuated to a vacuum level of 2×10⁻⁶. -3 Pa, then argon gas is introduced as a protective gas; the current is adjusted to 230A by controlling the knob during the melting process, and the vacuum arc melting is carried out at least 6 times. After cooling, the ingot is flipped. After multiple meltings, a high-entropy soft magnetic alloy ingot with dimensions of 10×21×70mm is obtained by suction casting.

[0125] S2. Cutting and Cleaning: The high-entropy soft magnetic alloy ingot of S1 is cut into blocks using a wire EDM machine. The size of the blocks cut by the wire EDM machine is 10×10×10mm. After being sanded with sandpaper, the blocks are placed in beakers containing anhydrous ethanol. The sandpaper grits are 240 grit, 400 grit, and 800 grit. Ultrasonic cleaning is performed at a frequency of 40KHz for 3 minutes. The cleaned block samples of high-entropy soft magnetic alloy ingots are placed in quartz tubes and loaded into a single-roller belt winch.

[0126] S3. Strip spinning: The diameter, surface roughness Ra, and rotation speed of the copper roller in the single-roller strip spinning machine of S2 are set and operated according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The copper roller diameter is set to 350 mm, the surface roughness Ra is 0.6 μm, and the copper roller rotation speed is 10 m / s. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and pressure-sprayed onto the surface of the copper roller through a round-hole nozzle. The diameter of the round-hole nozzle is 4 mm, the pressure is 0.3 MPa, and the spray angle is 90°. A micron-sized high-entropy soft magnetic alloy thin strip with a thickness of 100 μm is obtained.

[0127] S4. Ball milling to powder: Place the micron-sized high-entropy soft magnetic alloy ribbon of S3 into a ball mill jar, with the grinding balls occupying two-thirds of the jar's volume. The grinding balls have a diameter of 5 mm. First, place the grinding balls, then the micron-sized high-entropy soft magnetic alloy ribbon of S3 into the jar. Seal the ball mill jar in an argon-atmospheric glove box, then place it in a planetary ball mill. Set the ball milling parameters and run the mill. The set ball milling parameters are: ball milling speed 400 r / min, ball milling time 50 h. Ball milling yields high-entropy soft magnetic alloy powder with an average particle size of 65 μm.

[0128] S5 3D Printing: High-entropy soft magnetic alloy powder from S4 is placed in the powder feeder. The printing power, printing speed, and powder feed rate are set as follows: printing power 800W, printing speed 6mm / s, layer thickness 0.5mm, substrate material 45 steel, printing path using an alternating S-shaped pattern, and powder feed rate 5g / min. Printing is then performed to obtain the high-entropy soft magnetic alloy product. The high-entropy soft magnetic alloy product is a cuboid with a volume of 8cm³. 3 .

[0129] The 3D printed Ni prepared in this embodiment 55 Co 23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy has a uniform equiaxed crystal structure with an average grain size of 61 μm; its tensile strength is 930.17 MPa, yield strength is 490.52 MPa, yield ratio is 0.53, elongation is 31.53%, and strength-ductility product is 0.029 GPa.

[0130] The 3D printed Ni prepared in this embodiment 55 Co 23 Fe 15 The Al5Ta2 high-entropy soft magnetic alloy has a saturation magnetization of 121.34 emu / g, a coercivity of 5.75 Oe, a corrosion potential of -92.56 mV, and a corrosion current density of 3.15 × 10⁻⁶. -6 A / cm 2 .

[0131] Example 6

[0132] This embodiment describes a 3D printed Ni 55 Co 23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy, the 3D printed Ni 55 Co 23 Fe 15 The preparation method of Al5Ta2 high-entropy soft magnetic alloy includes the following steps:

[0133] S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 55 Co 23 Fe 15 The atomic percentages of Al5Ta2 high-entropy soft magnetic alloy were used to determine the proportions and weights of the raw materials. Then, each metal was placed into a vacuum melting furnace according to its atomic ratio. After three gas washing processes, the furnace was finally evacuated to a vacuum level of 2×10⁻⁶. -3 Pa, then argon gas is introduced as a protective gas; the current is adjusted to 230A by controlling the knob during the melting process, and the vacuum arc melting is carried out at least 6 times. After cooling, the ingot is flipped. After multiple meltings, a high-entropy soft magnetic alloy ingot with dimensions of 10×21×70mm is obtained by suction casting.

[0134] S2. Cutting and Cleaning: The high-entropy soft magnetic alloy ingot of S1 is cut into blocks using a wire EDM machine. The size of the blocks cut by the wire EDM machine is 10×10×10mm. After being sanded with sandpaper, the blocks are placed in beakers containing anhydrous ethanol. The sandpaper grits are 240 grit, 400 grit, and 800 grit. Ultrasonic cleaning is performed at a frequency of 40KHz for 3 minutes. The cleaned block samples of high-entropy soft magnetic alloy ingots are placed in quartz tubes and loaded into a single-roller belt winch.

[0135] S3. Strip spinning: The diameter, surface roughness Ra, and rotation speed of the copper roller in the single-roller strip spinning machine of S2 are set and operated according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The copper roller diameter is set to 350 mm, the surface roughness Ra is 0.6 μm, and the copper roller rotation speed is 10 / s. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and pressure-sprayed onto the surface of the copper roller through a round-hole nozzle with a diameter of 4 mm, a pressure of 0.3 MPa, and a spray angle of 90°. A micron-sized high-entropy soft magnetic alloy thin strip with a thickness of 100 μm is obtained.

[0136] S4. Ball milling to powder: Place the micron-sized high-entropy soft magnetic alloy ribbon of S3 into a ball mill jar, with the grinding balls occupying two-thirds of the jar's volume. The grinding balls have a diameter of 5 mm. First, place the grinding balls, then the micron-sized high-entropy soft magnetic alloy ribbon of S3 into the jar. Seal the ball mill jar in an argon-atmospheric glove box, then place it in a planetary ball mill. Set the ball milling parameters and run the mill. The set ball milling parameters are: ball milling speed 400 r / min, ball milling time 50 h. Ball milling yields high-entropy soft magnetic alloy powder with an average particle size of 65 μm.

[0137] S5 3D Printing: High-entropy soft magnetic alloy powder from S4 is placed in the powder feeder. The printing power, printing speed, and powder feed rate are set as follows: printing power 800W, printing speed 12mm / s, layer thickness 0.5mm, substrate material 45 steel, printing path using an alternating S-shaped pattern, and powder feed rate 7g / min. Printing is then performed to obtain the high-entropy soft magnetic alloy product. The high-entropy soft magnetic alloy product is a cuboid with a volume of 8cm³. 3 .

[0138] The 3D printed Ni prepared in this embodiment 55 Co 23 Fe 15 Al5Ta2 high-entropy soft magnetic alloy has a uniform equiaxed crystal structure with an average grain size of 70μm; its tensile strength is 887.37MPa, yield strength is 475.63MPa, yield ratio is 0.54, elongation is 34.32%, and strength-ductility product is 0.030GPa.

[0139] The 3D printed Ni prepared in this embodiment55 Co 23 Fe 15 The Al5Ta2 high-entropy soft magnetic alloy has a saturation magnetization of 123.24 emu / g, a coercivity of 5.02 Oe, a corrosion potential of -101.38 mV, and a corrosion current density of 4.15 × 10⁻⁶. -6 A / cm 2 .

[0140] The above-described solution, proposed in this invention, is a method for 3D printing Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloys and their preparation methods can solve the problems of Ni in existing technologies. 57-x Co 23 Fe 15 Al5Ta x The high-entropy soft magnetic alloy faces several technical challenges, including the failure to precisely control element content to achieve synergistic optimization of magnetic and mechanical properties; the inability of the composition ratio to effectively suppress the precipitation of non-magnetic phases and the difficulty in simultaneously meeting the comprehensive requirements of high saturation magnetization, low coercivity, and corrosion resistance; and the limitations of traditional smelting processes in preparation, which can easily lead to compositional segregation and coarse grains. Furthermore, single processes cannot achieve cross-scale forming from two-dimensional thin sheets to three-dimensional complex structures, and the powder preparation process suffers from insufficient compositional uniformity and flowability, making it difficult to adapt to additive manufacturing feed requirements. Finally, the poor microstructure control capability further limits the improvement of soft magnetic and mechanical properties.

[0141] This invention achieves an ultra-high-speed cooling process by employing an advanced belt-spinning process. This rapid solidification method significantly suppresses the component segregation problem commonly encountered in traditional material preparation processes, effectively avoids the formation of coarse grains, and thus greatly improves the uniformity of the material's microstructure, laying a solid foundation for subsequent material performance optimization.

[0142] This invention further refines the thin strip formed after spinning into micron-level powder through a ball milling alloying process. This not only enhances the soft magnetic properties of the material but also improves its magnetic permeability and saturation magnetization. At the same time, it provides a guarantee of high-uniformity and high-quality raw materials for subsequent additive manufacturing processes, ensuring the performance consistency and reliability of the final product.

[0143] This invention enables the precise molding of complex structures through the application of 3D printing, overcoming the limitations of traditional manufacturing processes in molding structures, expanding the design freedom of high-entropy soft magnetic alloys, and providing a new technical path and broad development prospects for their engineering applications in fields such as motors and sensors.

[0144] Ni obtained by additive manufacturing by the method of the present invention 57-x Co23 Fe 15 Al5Ta x High-entropy soft magnetic materials and Ni obtained by casting 57- x Co 23 Fe 15 Al5Ta x Compared with high-entropy soft magnetic materials, the tensile strength is increased by about 4.96%, the strain is increased by about 60.70%, the corrosion current is reduced by about 43.67%, and the saturation magnetization is increased by about 12.5%.

[0145] In summary, the method of the present invention is superior to existing Ni 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys involves raw material weighing and vacuum melting, cutting and cleaning, tape spinning, ball milling into powder, and 3D printing to obtain Ni. 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloy products synergistically improve mechanical properties and corrosion resistance; therefore, the method is simple to process, easy to operate, and the device structure can be easily improved. It is low in cost and high in efficiency, which is conducive to large-scale industrial production and application.

[0146] It should be understood that the term "and / or" in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. Additionally, the character " / " in this article generally indicates an "or" relationship between the preceding and following related objects, but it can also represent an "and / or" relationship. Please refer to the context for a more accurate understanding.

[0147] In this invention, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of a single item or a plurality of items. For example, at least one of a, b, or c can represent: a, b, c, ab, ac, bc, or abc, where a, b, and c can be a single item or multiple items.

[0148] It should be understood that, in various embodiments of the present invention, the order of the above-mentioned process numbers does not imply the order of execution. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.

[0149] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for 3D printing Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloy, characterized in that, The 3D printed Ni 57- x Co 23 Fe 15 Al5Ta x The high-entropy soft magnetic alloy composition is, in atomic percentage: Ta 1-3%, Al 5%, Fe 15%, Co 23%, Ni 54-56%.

2. The 3D printed Ni according to claim 1 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloy, characterized in that, The 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloys have a uniform equiaxed crystal structure with an average grain size of 30-40 μm.

3. The 3D printed Ni according to claim 1 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloy, characterized in that, The 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x The high-entropy soft magnetic alloy has a tensile strength of 600-1000MPa, a yield strength of 250-750MPa, a yield ratio of 0.4-0.7, an elongation of 20-70%, and a strength-ductility product of 0.01-0.05GPa.

4. The 3D printed Ni according to claim 1 57-x Co 23 Fe 15 Al5Ta x High-entropy soft magnetic alloy, characterized in that, The 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x The saturation magnetization of high-entropy soft magnetic alloys is 100-150 emu / g, the coercivity is 2-6 Oe, the corrosion potential is -200~90 mV, and the corrosion current density is 4×10⁻⁶ mV. -6 -8×10 -6 A / cm 2 .

5. A method for 3D printing Ni based on claim 1 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys, characterized in that, The 3D printed Ni 57-x Co 23 Fe 15 Al5Ta x The preparation method of high-entropy soft magnetic alloys includes the following steps: S1. Raw material weighing + vacuum melting: Following the instructions for 3D printing Ni... 57-x Co 23 Fe 15 Al5Ta x The atomic percentage of the high-entropy soft magnetic alloy is used to determine the proportion and weighing of raw materials. Then, vacuum arc melting is performed, and after cooling, the ingot is flipped. After multiple meltings, the high-entropy soft magnetic alloy ingot is obtained by suction casting. S2, Cutting + Cleaning: Cut the high-entropy soft magnetic alloy ingot of S1 into blocks using a wire cutting machine, polish them with sandpaper, and then put them into a beaker containing anhydrous ethanol for ultrasonic cleaning. Place the cleaned block high-entropy soft magnetic alloy ingot sample into a quartz tube and load it into a single-roller belt winch. S3, Strip spinning: The diameter of the copper roller, surface roughness Ra, and rotation speed of the single-roller strip spinning machine in S2 are set and run according to the size of the blocky high-entropy soft magnetic alloy ingot sample placed in the quartz tube. The blocky high-entropy soft magnetic alloy ingot sample in the quartz tube is melted and sprayed onto the surface of the copper roller through a round nozzle under pressure to obtain a micron-sized high-entropy soft magnetic alloy thin strip. S4. Ball milling into powder: Place the micron-sized high-entropy soft magnetic alloy strip of S3 into a ball mill jar, seal the ball mill jar in an argon atmosphere glove box, and then place it into a planetary ball mill. Set the ball milling parameters and run the mill to obtain high-entropy soft magnetic alloy powder. S5, 3D printing: Place the high-entropy soft magnetic alloy powder from S4 into the powder feeder, set the printing power, printing speed and powder feeding rate, and then print to obtain the high-entropy soft magnetic alloy product.

6. The 3D printed Ni according to claim 5 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys, characterized in that, In S1, the metals are placed into a vacuum melting furnace according to their atomic ratios. After three rounds of gas washing, the furnace is finally evacuated to a vacuum level of 2 × 10⁻⁶. -3 -9×10 -3 Pa, then argon gas is introduced as a protective gas; the current is adjusted to 150-300A by controlling the knob during the melting process, and at least 6 meltings are performed; the dimensions of the high-entropy soft magnetic alloy ingot are 12×12×70-10×21×70mm.

7. The 3D printed Ni according to claim 5 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys, characterized in that, The S2 wire EDM machine cuts blocks to sizes ranging from 7×7×7 to 10×10×10mm. The sandpaper used for sanding is 240, 400, and 800 grit. The ultrasonic cleaning process uses an ultrasonic frequency of 28-48KHz and a cleaning time of 3-5 minutes.

8. The 3D printed Ni according to claim 5 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys, characterized in that, In S3, the diameter of the copper roller is set to 350-400mm, the surface roughness Ra is 0.5-0.8μm, and the rotation speed of the copper roller is 10-15m / s; the diameter of the round nozzle is 2-5mm, the pressure is 0.1-0.5MPa, and the spray angle is 60-90°; the thickness of the micron-level high-entropy soft magnetic alloy strip is 80-100μm.

9. The 3D printed Ni according to claim 5 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys, characterized in that, In S4, the grinding balls occupy two-thirds of the volume of the grinding jar, and the diameter of the grinding balls is 2-5 mm. The grinding balls are placed in first, followed by the micron-sized high-entropy soft magnetic alloy thin strip from S3. The grinding parameters are set as follows: grinding speed is 400-500 r / min, grinding time is 50-85 h, and the average particle size of the high-entropy soft magnetic alloy powder is 60-70 μm.

10. The 3D printed Ni according to claim 5 57-x Co 23 Fe 15 Al5Ta x A method for preparing high-entropy soft magnetic alloys, characterized in that, The S5 printer has a printing power of 800-1000W, a printing speed of 6-12mm / s, a layer thickness of 0.5-0.6mm, uses 45 steel as the substrate, employs an alternating S-shaped printing path, and has a powder feed rate of 4-12g / min. High-entropy soft magnetic alloy products are available in cuboid and toroidal shapes, with a volume of 8-16cm³. 3 .

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