A high T c Magnetic FeCo-based multi-component single-phase alloys and their preparation methods

Abstract

The application discloses a high-T c The application discloses a magnetic FeCo-based multi-element single-phase alloy and a preparation method thereof. The preparation method comprises the following steps: preparing a metal ion mixed solution by taking Fe ions and Co ions as the basis and adding at least one ion of Al, Cu, Zn, Cr and Mn while adding a chelating agent; spraying and drying the metal ion mixed solution by using a spraying and drying device to obtain a powder precursor; annealing the powder precursor in air to remove the chelating agent and obtain a metal oxide sample; and reducing the metal oxide sample in a hot atmosphere to obtain the FeCo-based multi-element single-phase alloy. The application has the advantages of simple process, large product yield, single-phase structure, high Curie temperature, good magnetic performance and mechanical performance, and wide application prospect in the electromagnetic field.

Description

Technical Field

[0001] This invention belongs to the field of magnetic materials technology, specifically relating to a high-T c Magnetic FeCo-based multi-component single-phase alloys and their preparation methods. Background Technology

[0002] Magnetic FeCo-based multi-element alloys are alloys composed of iron (Fe), cobalt (Co), and other metallic elements, possessing excellent magnetic properties, high-temperature stability, and good mechanical properties. Iron and cobalt are common transition metals with good electrical and magnetic properties, providing a stable magnetic basis in the alloy. FeCo alloys typically exhibit excellent magnetic properties such as high permeability, low hysteresis, and high saturation magnetic induction, making them widely used in the electromagnetic field, commonly in the manufacture of sensors, transformers, and motors. Simultaneously, FeCo-based alloys can also be used in magnetic recording materials, electromagnetic wave absorbing materials, and other fields.

[0003] FeCo alloys have a high Curie temperature (T). c The Curie temperature is the critical temperature at which a material loses its magnetism; for magnetic materials, this is a very important parameter. Due to the high TCr of FeCo alloys... c Its characteristic is that it can maintain stable magnetic properties even at high temperatures. This characteristic makes FeCo-based alloys a promising candidate for applications in electromagnetic devices that require high-temperature resistance. Whether in extremely high-temperature industrial environments or in high-tech fields such as aerospace, FeCo-based alloys can leverage their unique advantages to provide stable magnetic performance support for related equipment.

[0004] In practical applications, to further optimize the performance of FeCo alloys, it is often necessary to incorporate other metals to form multi-component solid solution alloys. However, the doping of other metals usually leads to phase separation, which not only affects the magnetic properties of the alloy but also has an adverse effect on its mechanical properties. Current preparation processes often result in the precipitation of heterogeneous alloy phases, which is detrimental to the material's mechanical properties. Therefore, overcoming the phase separation problem and preparing alloys with high TT is a crucial challenge. c Magnetic FeCo-based multi-element single-phase alloys have become a focus of current research. Researchers are working to develop advanced production processes to ensure that phase separation does not occur when other metals are incorporated, by precisely controlling the composition and phase structure of the alloy.

[0005] For example, Chinese patent application CN107419155A discloses a Fe-Co-based single-phase solid solution Fe-Co-Cu ternary alloy and its preparation method. This method utilizes a solidification forming apparatus to prepare the Fe-Co-based single-phase solid solution Fe-Co-Cu ternary alloy by designing a reasonable alloy component ratio, the pressure of the two vacuum chambers, and the linear velocity of the Cu roller surface. However, this method requires a specialized solidification forming apparatus, which may increase equipment costs. Especially for large-scale production, it also requires precise control of multiple parameters, resulting in a certain degree of process complexity.

[0006] In addition, Chinese patent application CN115896516A discloses a micro / nano magnetic high-entropy alloy microwave absorbing material and its preparation method. It uses Fe, Co, Ni, Cr, and Cu to mechanically alloy and form a stable single-phase magnetic high-entropy alloy. The powder particle size is refined by low-temperature ball milling with liquid nitrogen at room temperature to enhance the microwave absorption performance. However, this method requires a large amount of liquid nitrogen for low-temperature ball milling, increasing the economic burden. Furthermore, the ball milling process is prone to powder oxidation and agglomeration, which may increase the difficulty and cost of preparation.

[0007] Therefore, in order to overcome the problems existing in the current preparation process, and to further develop a simple and efficient method for preparing high-T... c The production process of magnetic FeCo-based multi-component single-phase alloys has significant practical implications. It not only helps improve the magnetic and mechanical properties of the alloys but also reduces production costs and increases production efficiency, thereby promoting further development in the field of magnetic materials. Summary of the Invention

[0008] In view of the above, the object of the present invention is to provide a high T c Magnetic FeCo-based multi-component single-phase alloys and their preparation methods, which can maintain a relatively high Curie temperature (T c At the same time, other target metal elements are dissolved in the alloy to form a single-phase multi-element alloy, which can take into account both excellent magnetic and mechanical properties. The preparation process is simple, the product yield is large, and it is suitable for large-area preparation. It has broad application prospects in the electromagnetic field.

[0009] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0010] The present invention provides a high T c A method for preparing magnetic FeCo-based multi-component single-phase alloys includes the following steps:

[0011] A mixed solution of metal ions was prepared by using Fe and Co ions as the base and incorporating at least one ion from Al, Cu, Zn, Cr and Mn, while adding a chelating agent.

[0012] A powder precursor was obtained by spray drying a mixed solution of metal ions using a spray drying device.

[0013] The powder precursor was annealed in air to remove the chelating agent, thus obtaining a metal oxide sample.

[0014] FeCo-based multi-component single-phase alloys were obtained by reducing metal oxide samples in a hot atmosphere.

[0015] Preferably, in the metal ion mixed solution, the total concentration of metal ions is maintained at 0.05–1.5 mol / L, the concentration of chelating agent is 10–100 mmol / L, and the metal ion mixed solution is ultrasonically stirred until homogeneous.

[0016] Preferably, in the metal ion mixed solution, the molar ratio of Fe ions to Co ions is 1:1. This ratio results in a higher Curie temperature for the FeCo alloy, ensuring the alloy's magnetic properties and high-temperature stability.

[0017] Preferably, the chelating agent is polyvinylpyrrolidone, sucrose, or ethylenediaminetetraacetic acid.

[0018] Preferably, the spray temperature of the spray drying device is 150–180°C, the vacuum pump is set to 100%, and the feed rate is 0.1–20 ml / min. Spray drying ensures that the powder precursor has a uniform elemental distribution, guaranteeing consistent properties in the prepared alloy.

[0019] Preferably, the annealing conditions are controlled by holding the obtained powder precursor at 500–700°C for 1–24 h, with a heating rate of 1–10°C / min. The annealing process effectively removes chelating agents and maintains the purity of the metal oxide.

[0020] Preferably, the annealing process is carried out using a muffle furnace.

[0021] Preferably, the reduction conditions are controlled by holding the metal oxide sample at 600–1000°C for 1–10 h in an argon-hydrogen atmosphere, where the hydrogen gas fraction is 5–99.99%, and the heating rate is 1–5°C / min. The metal oxide sample undergoes a reduction reaction, ultimately yielding an FeCo-based multi-component single-phase alloy.

[0022] Preferably, the apparatus for the reduction process is a tube furnace.

[0023] To achieve the above-mentioned objectives, embodiments of the present invention also provide a high-T c Magnetic FeCo-based multi-component single-phase alloys were prepared using the above-described method to obtain high-T alloys. c Magnetic FeCo-based multi-component single-phase alloy.

[0024] Compared with the prior art, the beneficial effects of the present invention include at least the following:

[0025] (1) This invention uses FeCo ions as the base and adds other specific metal ions (including at least one ion selected from Al, Cu, Zn, Cr and Mn) to obtain a mixed metal ion solution. By reasonably controlling the Fe and Co content, the alloy material is guaranteed to have high T. c Stable magnetic properties.

[0026] (2) This invention obtains FeCo-based multi-element alloys through spray drying, annealing, and reduction processes. The preparation process is simple, the product yield is large, and the prepared FeCo-based multi-element alloys have a single-phase structure, that is, different elements can be completely dissolved into the FeCo phase. They can be multi-element doped and still maintain a relatively high T. c .

[0027] (3) The FeCo-based multi-component single-phase alloy prepared by this invention not only maintains the original high T c It possesses magnetic properties and, due to its single-phase structure, improves the mechanical properties of alloy materials, making it a promising candidate for a wide range of applications in the electromagnetic field, particularly excelling in applications requiring high-temperature and high-strength materials. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the 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.

[0029] Figure 1 This is a high-T provided by an embodiment of the present invention. c A schematic diagram of the preparation method of magnetic FeCo-based multi-component single-phase alloy;

[0030] Figure 2 This is the XRD pattern of the FeCo-based ternary single-phase alloy prepared in Example 1 of this invention;

[0031] Figure 3 This is the Curie temperature diagram of the FeCo-based ternary single-phase alloy prepared in Example 1 of this invention, measured by thermogravimetric analysis.

[0032] Figure 4 This is a SEM image of the FeCo-based quaternary single-phase alloy prepared in Example 2 of this invention;

[0033] Figure 5 This is the XRD pattern of the FeCo-based quaternary single-phase alloy prepared in Example 2 of this invention. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of protection of this invention.

[0035] The inventive concept of this invention is as follows: Addressing the problems of existing FeCo multi-element alloy preparation processes often resulting in the precipitation of dissimilar alloying phases that negatively impact the material's mechanical properties, and the complexity and high cost of existing preparation processes, this invention provides a high-T... c A magnetic FeCo-based multi-component single-phase alloy and its preparation method are disclosed. First, a mixed solution containing Fe, Co, and other specific metal ions is prepared. Then, the homogeneous metal ion mixture containing multiple metal ions and a chelating agent is atomized and dried using a spray drying method to obtain spherical powder. The chelating agent is then removed by air annealing, and finally, the powder is reduced in a hot atmosphere to obtain the FeCo-based multi-component single-phase alloy. This preparation method yields a high production volume, maintains a high Curie temperature while possessing a single-phase structure, and achieves a balance between magnetic and mechanical properties.

[0036] Figure 1 This is a high-T provided by an embodiment of the present invention. c A schematic flowchart illustrating the preparation method of magnetic FeCo-based multi-component single-phase alloys. Figure 1 As shown, the embodiment provides a high T c A method for preparing magnetic FeCo-based multi-component single-phase alloys includes the following steps:

[0037] S1 is a solution of mixed metal ions, based on Fe and Co ions and doped with at least one of Al, Cu, Zn, Cr and Mn, with the addition of a chelating agent.

[0038] Specifically, Fe ions, Co ions, and other specific metal ions (at least one of Al, Cu, Zn, Cr, and Mn) are dissolved in an aqueous solution with polyvinylpyrrolidone (PVP), sucrose, or ethylenediaminetetraacetic acid to obtain a mixed metal ion solution. The total concentration of metal ions is maintained at 0.05–1.5 mol / L, the concentration of PVP, sucrose, or ethylenediaminetetraacetic acid is 10–100 mmol / L, and the molar ratio of Fe ions to Co ions is 1:1. The mixed metal ion solution is then ultrasonically stirred until homogeneous.

[0039] S2, a powder precursor is obtained by spray drying a mixed solution of metal ions using a spray drying device.

[0040] Specifically, a metal ion mixed solution is spray-dried using a spray drying device to obtain a powder precursor. The spray temperature is set to 150–180°C, the vacuum pump is adjusted to 100%, and the feed rate is 0.1–20 ml / min.

[0041] S3, the powder precursor is annealed in air to remove the chelating agent and obtain a metal oxide sample.

[0042] Specifically, the obtained powder precursor is placed in a muffle furnace and kept at 500–700°C in air for 1–24 h with a heating rate of 1–10°C / min to obtain a metal oxide sample.

[0043] S4, reducing the metal oxide sample in a hot atmosphere to obtain FeCo-based multi-component single-phase alloy.

[0044] Specifically, the metal oxide sample was placed in a tube furnace and held at 600–1000 °C for 1–10 h in an argon-hydrogen (5–99.99% H2) atmosphere, with the heating rate controlled at 1–5 °C / min, to obtain the final FeCo-based multi-element single-phase alloy.

[0045] The preparation method provided in this invention first involves spray drying a homogeneous metal ion mixture solution containing multiple metal ions and a chelating agent to obtain a spherical powder precursor. Then, the powder precursor is annealed in air to remove the chelating agent, yielding a metal oxide sample. Finally, the metal oxide sample is reduced in a hot atmosphere to prepare the FeCo-based multi-component alloy. This preparation method yields a large product volume, and the obtained FeCo-based multi-component alloy exhibits a single-phase structure and a high Curie temperature.

[0046] Example 1

[0047] High T c The preparation method of magnetic FeCo-based ternary single-phase alloys comprises the following steps:

[0048] (1) Take 9.09g Fe(NO3)3, 6.55g Co(NO3)2, 1.88g Al(NO3)3 and 17.11g sucrose and dissolve them in 500ml of aqueous solution. Then, sonicate the solution for 1h to obtain a homogeneous metal ion mixed solution.

[0049] (2) Place the metal ion mixed solution obtained in step (1) on the spray drying device, insert the liquid inlet tube into the bottom of the solution, turn on the air compressor and vacuum pump, set the spray temperature to 160℃, adjust the air pump to 100%, and the feed rate to 1ml / min. When the temperature rises to the set temperature, start feeding. Finally, obtain a powdery and fluffy substance in the sample collection bottle as a powder precursor.

[0050] (3) The powder precursor obtained in step (2) was placed in a muffle furnace and kept at 550°C for 10 hours with a heating rate of 2°C / min.

[0051] (4) Place the product obtained in step (3) in a tubular furnace and heat it at 650°C for 5 hours in an argon-hydrogen (10% H2) atmosphere with a heating rate of 5°C / min. Once the furnace temperature has cooled to room temperature, Fe can be obtained. 0.45 Co 0.45 Al 0.1 Ternary alloy.

[0052] Fe prepared according to Example 1 0.45 Co 0.45 Al 0.1 XRD patterns of ternary alloys are as follows: Figure 2 As shown, the obtained Fe 0.45 Co 0.45 Al 0.1 Ternary alloys are single-phase materials. Their Curie temperatures are determined using thermogravimetric analysis (TGA), such as... Figure 3 As shown, the obtained Fe 0.45 Co 0.45 Al 0.1 Ternary single-phase alloys still exhibit a high Curie temperature (Ti). c ).

[0053] Example 2

[0054] High T c The preparation method of magnetic FeCo-based quaternary single-phase alloys comprises the following steps:

[0055] (1) Dissolve 8.89g Fe(NO3)3, 6.40g Co(NO3)2, 0.56g Al(NO3)3, 1.80g Cr(NO3)3 and 17.11g sucrose in 500ml of aqueous solution, and then sonicate the solution for 1h to obtain a homogeneous metal ion mixed solution.

[0056] (2) Place the metal ion mixed solution obtained in step (1) on the spray drying device, insert the liquid inlet tube into the bottom of the solution, turn on the air compressor and vacuum pump, set the spray temperature to 160℃, adjust the air pump to 100%, and the feed rate to 1ml / min. When the temperature rises to the set temperature, start feeding. Finally, obtain a powdery and fluffy substance in the sample collection bottle as a powder precursor.

[0057] (3) The powder precursor obtained in step (2) was placed in a muffle furnace and kept at 600℃ for 10h with a heating rate of 2℃ / min.

[0058] (4) Place the product obtained in step (3) in a tubular furnace and heat it at 700°C for 5 hours in an argon-hydrogen (80% H2) atmosphere with a heating rate of 5°C / min. Once the furnace temperature has cooled to room temperature, Fe can be obtained. 0.44 Co 0.44 Al 0.03Cr 0.09 Quaternary alloy.

[0059] Fe prepared by Example 2 0.44 Co 0.44 Al 0.03 Cr 0.09 SEM images of quaternary alloys are shown below. Figure 4 As shown, it exhibits a uniform microstructure. Its XRD pattern is as follows. Figure 5 As shown, the obtained Fe 0.44 Co 0.44 Al 0.03 Cr 0.09 Quaternary alloys are single-phase materials.

[0060] Example 3

[0061] High T c The preparation method of magnetic FeCo-based quaternary single-phase alloys comprises the following steps:

[0062] (1) Dissolve 364.91 mg FeCl3, 321.21 mg CoCl2, 44.62 mg Zn(NO3)2, 23.94 mg CuSO4 and 0.5 g PVP in 10 ml of aqueous solution, and then sonicate the solution for 1 h to obtain a homogeneous metal ion mixed solution.

[0063] (2) Place the metal ion mixed solution obtained in step (1) on the spray drying device, insert the liquid inlet tube into the bottom of the solution, turn on the air compressor and vacuum pump, set the spray temperature to 180℃, adjust the air pump to 100%, and the feed rate to 0.5ml / min. When the temperature rises to the set temperature, start feeding. Finally, obtain a powdery and fluffy substance in the sample collection bottle as a powder precursor.

[0064] (3) The powder precursor obtained in step (2) was placed in a muffle furnace and kept at 700℃ for 4 hours with a heating rate of 2℃ / min.

[0065] (4) Place the product obtained in step (3) in a tubular furnace and heat it at 700°C for 4 hours in an argon-hydrogen (50% H2) atmosphere with a heating rate of 5°C / min. Once the furnace temperature has cooled to room temperature, Fe can be obtained. 0.45 Co 0.45 Zn 0.05 Cu 0.05 Quaternary single-phase alloy.

[0066] It should be noted that, in addition to the above-mentioned Examples 1, 2 and 3, for other examples, the type, quantity and proportion of the added metal salt can be controlled to change in step (1), the chelating agents "sucrose" and "PVP" can be changed to other substances and the amount can also be changed, the volume of the aqueous solution can be changed; the spray temperature and feed rate set in step (2) can be changed; the heating temperature, holding time and heating rate in step (3) can be changed; the hydrogen content, temperature, holding time and heating rate in the reaction atmosphere in step (4) can be changed; the rest is the same as in Examples 1, 2 or 3.

[0067] In summary, the embodiments of the present invention provide a high T c A method for preparing magnetic FeCo-based multi-element single-phase alloys involves first preparing a mixed solution of Fe, Co, and other specific metal ions doped with these elements. Then, the solute in the mixed solution is sprayed into spherical particles using a spray dryer. The resulting material is then subjected to heat treatment annealing, and finally reduced to a metallic alloy under a hot atmosphere. This method can produce FeCo-based multi-element single-phase alloys doped with some dissimilar metal elements. These alloys can maintain the original FeCo phase structure to preserve a high Curie temperature, while allowing for the solidification of target metal elements according to application requirements. Simultaneously, they retain good magnetic and mechanical properties, showing broad application prospects in the electromagnetic field.

[0068] The specific embodiments described above illustrate the technical solution and beneficial effects of the present invention in detail. It should be understood that the above description is only the most preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, additions, and equivalent substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-T c A method for preparing magnetic FeCo-based multi-component single-phase alloys, characterized in that, Includes the following steps: Based on Fe and Co ions, and incorporating at least one ion selected from Al, Cu, Zn, Cr, and Mn, a chelating agent is added to obtain a mixed metal ion solution. The chelating agent is polyvinylpyrrolidone, sucrose, or ethylenediaminetetraacetic acid. In the mixed metal ion solution, the molar ratio of Fe ions to Co ions is 1:1, the total concentration of metal ions is maintained at 0.05~1.5 mol / L, and the concentration of the chelating agent is 10~100 mmol / L. A metal ion mixed solution was spray-dried using a spray drying device to obtain a powder precursor. The spray temperature of the spray drying device was set to 150~180 ℃, the vacuum pump was set to 100%, and the feed rate was 0.1~20 ml / min. The powder precursor was annealed in air to remove the chelating agent to obtain a metal oxide sample. The annealing conditions were controlled by holding the obtained powder precursor at 500~700 ℃ for 1~24 h with a heating rate of 1~10 ℃ / min. FeCo-based multi-component single-phase alloys were obtained by reducing metal oxide samples in a hot atmosphere. The reduction conditions were controlled by holding the metal oxide samples at 600-1000 °C for 1-10 h in an argon-hydrogen atmosphere, with a hydrogen gas integral of 5-99.99% and a heating rate of 1-5 °C / min.

2. The high-T according to claim 1 c A method for preparing magnetic FeCo-based multi-component single-phase alloys, characterized in that, The annealing process is carried out using a muffle furnace.

3. The high-T according to claim 1 c A method for preparing magnetic FeCo-based multi-component single-phase alloys, characterized in that, The reduction process is carried out using a tube furnace.

4. A high-T c Magnetic FeCo-based multi-component single-phase alloy, characterized in that, High T was prepared by the preparation method according to any one of claims 1-3. c Magnetic FeCo-based multi-component single-phase alloy.

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