High-Bs iron-based soft magnetic amorphous alloy prepared based on industrial raw materials and preparation method of high-Bs iron-based soft magnetic amorphous alloy

Abstract

The invention discloses a high-Bs iron-based soft magnetic amorphous alloy prepared based on industrial raw materials and a preparation method of the high-Bs iron-based soft magnetic amorphous alloy, and belongs to the field of metal materials. The chemical formula of the iron-based soft magnetic amorphous alloy is FeaBbSicMf, a, b, c and f are atomic percentages of corresponding elements respectively, a is larger than or equal to 80 and smaller than or equal to 85, b is larger than or equal to 10 and smaller than or equal to 16, c is larger than or equal to 2 and smaller than or equal to 3, f is larger than or equal to 0.001 and smaller than or equal to 1, a + b + c + f = 100, and M is a microelement and is one or a composition of Co, Zn, Mn, N, Cu, Al, Ti and S. According to the iron-based amorphous alloy, an industrial-grade high-Bs-value amorphous strip can be prepared through a single-roller quenching method, and the purposes of large-scale production and batch application can be achieved.

Description

Technical Field

[0001] This application relates to the technical field of amorphous alloy composites, and particularly to a high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials and a preparation method thereof. Background Art

[0002] Iron-based amorphous alloys are prepared by rapid cooling technology, and their atomic arrangement is in a glassy state structure with short-range order and long-range disorder. This unique microstructure results in a significant reduction in the number of structural defects such as grain boundaries and dislocations, thereby reducing the domain wall pinning effect, making amorphous alloy soft magnetic materials have excellent properties such as high saturation magnetic induction intensity, low coercivity, and low loss. They are known as new green energy-saving materials in the 21st century and are currently widely used in the information communication and power electronics industries, promoting the development of electronic products towards high efficiency, miniaturization, and high power density, providing important support and guarantee for the development of China's power electronics industry. Currently, the development of the amorphous alloy soft magnetic material industry presents the following major characteristics.

[0003] The output growth rate of amorphous ribbon is fast. According to statistical data, in 2021, the output of iron-based amorphous ribbon in China was 68,000 tons, a year-on-year increase of 28.3%; in 2022, the output of iron-based amorphous ribbon in China was 91,000 tons, a year-on-year increase of 33.8%. In 2023, the output of iron-based amorphous ribbon in China was 117,000 tons, a year-on-year increase of 28.6%. This is mainly due to the following aspects: First, the downstream industries such as new energy have developed rapidly; second, the upgrading of amorphous products has accelerated. For example, Zhongyue Amorphous has developed iron-based amorphous alloy ribbons with advantages such as a width of 232 mm, high saturation magnetic induction intensity, high stacking factor, high density, and low coercivity; third, the export has increased. In 2023, nearly 50% of the amorphous ribbons in China were exported overseas.

[0004] The demand for "multi-form" amorphous materials is increasing, mainly manifested as the growing market demand mainly for ribbons, supplemented by powders and wires. In terms of ribbons, the demand for amorphous ribbons is currently stable and has formed a scale in fields such as distribution transformers and new energy vehicles. In terms of powders, amorphous alloy powders are often used in inductive magnetic components and are currently exploring application potential in fields such as coatings, 3D printing, and catalysis, with broad prospects. In terms of wires and bulk materials, amorphous wires are mainly used for high-sensitivity and high-precision weak magnetic and micro-stress detection, and amorphous bulk structural components are mainly used in fields such as consumer electronics, medical, and aerospace.

[0005] The competition is fierce, and only the fittest survive. In the case of insufficient talent, equipment, technology, and applied research among some domestic enterprises, they blindly invest in order to seize the opportunity, resulting in a large gap in the stability, consistency, and reliability of some amorphous products compared with enterprises with technological accumulation. Generally speaking, the large-scale production of amorphous materials has become a development trend, and the ability to stably produce high-quality industrial-grade amorphous ribbons has become the core requirement for enterprises to have sustainable competitiveness.

[0006] In recent years, with the large-scale application of third-generation semiconductors in power electronic devices, electronic equipment has been developing towards the direction of miniaturization, high efficiency, and high power density. Soft magnetic devices have a wide range of applications in many fields due to their excellent magnetic properties, mechanical properties, corrosion resistance, etc. In the field of power electronics, amorphous ribbons can be used as ideal materials for manufacturing high-efficiency transformers. Amorphous alloy transformers can significantly reduce no-load losses, improve energy efficiency, and reduce carbon emissions, meeting the global trend of green energy and sustainable development. In the field of new energy vehicles, amorphous materials can be used to manufacture the stator cores of drive motors for new energy vehicles, which can improve the efficiency and power density of the motors, reduce energy consumption, and extend the vehicle's cruising range. Their excellent magnetic properties enable the motors to convert electrical energy more efficiently while achieving lightweight design. In the field of aerospace, amorphous materials, with their high saturation magnetic induction intensity and low coercivity, are often used to manufacture small, lightweight, and high-performance magnetic components, such as magnetic components in aerospace communication systems, navigation systems, and flight control systems.

[0007] However, at present, amorphous ribbons with extremely high saturation magnetic induction intensity (1.6T - 2.0T) are often prepared in small quantities in the laboratory and do not have the production conditions for industrial pilot production, and there is still a considerable distance from the large-scale production of hundreds of kilograms of ribbons. For the patents that have been applied for currently, it is often difficult for industrial-grade wide-width ribbons that can be used for industrial production to have a high saturation magnetic induction intensity. For example, in the patent with the publication number CN 102509603 A, for the Fe-Si-B-Cr-M series amorphous alloy composition, the saturation magnetic induction intensity after annealing is only 1.5 - 1.55T. Therefore, developing a high-Bs wide-width industrial ribbon that can be used for industrial production is an urgent problem to be solved. Summary of the Invention

[0008] In order to solve the problems existing in the prior art, the first object of the present application is to provide a high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials.

[0009] The present application adopts the following technical solution: A high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials, and the chemical formula of the iron-based soft magnetic amorphous alloy is: Fe a B b Si c M f, where a, b, c, and f are the atomic percentages of the corresponding elements respectively, 80 ≤ a ≤ 85, 10 ≤ b ≤ 16, 2 ≤ c ≤ 3, 0.001 ≤ f ≤ 1, and a + b + c + f = 100. M is a trace element, which is one or more combinations of Co, Zn, Mn, N, Cu, Al, Ti, and S.

[0010] In this application, one or several elements are selected from three types of elements, namely ferromagnetic elements, metalloid elements, and transition metal elements, to design a new composition of the iron-based amorphous alloy composite material. The iron-based amorphous alloy composite material is based on the Fe element first, which is the main element to increase the Bs value of the amorphous ribbon. Elements such as B and Si are selected from the metalloid elements. The addition of the B element can not only significantly improve the amorphous formation ability of the amorphous alloy but also reduce the crystallization temperature of the alloy and promote the formation of the amorphous state. The addition of the Si element can improve the corrosion resistance of the alloy, enabling the material to maintain stable performance under complex conditions. The addition of the Cu element in the transition metal elements can induce the precipitation of nanocrystalline phases such as the α-Fe phase in the amorphous matrix. These nanocrystalline phases can significantly improve the mobility of magnetic domain walls, thereby increasing the saturation magnetic induction intensity. The addition of Cu can also weaken the binding force between atoms, reduce the energy barrier of crystallization, and promote the precipitation of the crystalline phase. Compared with Ag and Au elements, the Cu element is more economical and easier to conduct a large number of experiments for research. There is a strong chemical interaction between Al and other elements (such as Fe, B, etc.), and a negative mixing enthalpy is presented, which helps to improve the amorphous formation ability. The Mn element can refine the microstructure of the amorphous alloy, increase the degree of atom discretization, and thus improve the amorphous formation ability. The Ti element can form strong chemical bonds with Fe atoms, enhance the binding force between atoms, and thus improve the strength and hardness of the iron-based amorphous alloy.

[0011] Preferably, 5 ≤ b / c ≤ 8.

[0012] Preferably, b / c = 5 and b + c = 17.

[0013] The second object of this application is to provide a preparation method of a high-Bs iron-based soft magnetic amorphous alloy prepared based on industrial raw materials, including the following steps: (1) Weighing: Weigh the raw materials according to the predetermined ratio to ensure that the raw materials are completely dry; (2) Loading: First, load part of the pure iron to the bottom of the furnace cavity of the melting furnace, then place part of the nodular cast iron above the pure iron, then add ferrosilicon and silicon, and finally add the trace element. Finally, place the remaining pure iron in the surrounding gaps; (3) Melting: Melt the raw materials in the melting furnace to melt them into molten steel; (4) Secondary melting: Add the remaining raw materials to the melting furnace for melting, and perform slag removal after melting; (5) Insulation: After the raw materials are completely melted, insulation is carried out, and slag removal is carried out again during the insulation period; (6) Sampling: The molten steel is taken out with a mold and cooled at room temperature to form a solid master alloy, and then a spectrum test is performed. If the spectrum test results show that the content of each component element is basically consistent with the content of the added element, the smelting is successful. If the spectrum test results show inconsistency, return to step (4), add the corresponding element raw materials to the smelting furnace for smelting, and then keep warm and take samples for spectrum measurement according to steps (5) and (6) until the content is basically consistent with the added element content; (7) Deslagging: After the elements of the solid master alloy are basically consistent with the added elements, deslagging is performed again after standing; (8) Steel pouring: After slag removal, let it stand and then pour the steel ingot; (9) Spraying: The steel ingot is placed in a crucible and heated, and then sprayed through the nozzle of the spraying equipment. During the spraying process, amorphous strip is prepared by a single-roll extreme cooling method.

[0014] Preferably, the smelting temperature in step (3) is 1400°C to 1580°C.

[0015] Preferably, in step (4), slag removal is performed after the smelting temperature reaches 1580°C.

[0016] Preferably, the insulation temperature in step (5) is between 1550°C and 1580°C.

[0017] Preferably, in step (7), the slag is removed again after standing for 15 minutes.

[0018] Preferably, in step (8), after standing, the temperature of the molten steel is cooled to 1250° C. before pouring the steel ingot.

[0019] Preferably, the nozzle in step (9) is preheated to 900°C, and then the steel ingot is heated to 1370°C before spraying.

[0020] Through secondary smelting and multiple slag removal, high Bs soft magnetic amorphous alloys can be prepared more efficiently, which has greatly promoted and facilitated the industrialization and industrialization of amorphous materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings of the embodiments will be briefly introduced below. Obviously, the drawings in the following description only relate to some embodiments of the present application, rather than limiting the present application.

[0022] Figure 1 It is a flow chart of the preparation method of the iron-based soft magnetic amorphous alloy of the present application. DETAILED DESCRIPTION

[0023] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the following will further elaborate on this application in conjunction with the accompanying drawings. The components of the embodiments of this application described and illustrated herein can generally be arranged and designed in various different configurations. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.

[0024] It should be noted that like reference numerals and letters denote like items in the following drawings. Therefore, once an item is defined in one drawing, it does not need to be further defined and explained in subsequent drawings.

[0025] Unless otherwise defined, the technical terms or scientific terms used in this patent document should have the ordinary meaning understood by those of ordinary skill in the art to which this application pertains. The terms "first", "second", and similar terms used in the patent specification and claims of this application do not denote any order, quantity, or importance, but are merely used to distinguish different components. Similarly, terms such as "a", "an", or "the" do not denote a quantity limitation, but rather indicate the presence of at least one. The terms "comprising" or "including" and similar terms mean that the elements or items appearing before "comprising" or "including" encompass the elements or items listed after "comprising" or "including" and their equivalents, and do not exclude other elements or items. Terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are only used to represent relative positional relationships. When the absolute position of the object being described changes, the relative positional relationship may also change accordingly. These are only for the convenience of describing this application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation of this application.

[0026] In the description of this application, it should be noted that unless otherwise clearly specified and limited, the terms "installed", "connected", and "coupled" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0027] The following will elaborate on some embodiments of this application in conjunction with the accompanying drawings. Without conflict, the features in the following embodiments can be combined with each other.

[0028] This application relates to a high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials, and its chemical formula is: Fea B b Si c M f , where a, b, c, and f are the atomic percentages of the corresponding elements respectively, 80 ≤ a ≤ 85, 10 ≤ b ≤ 16, 2 ≤ c ≤ 3, 0.001 ≤ f ≤ 1, and a + b + c + f = 100. M is a trace element, which is one or more combinations of Co, Zn, Mn, N, Cu, Al, Ti, and S.

[0029] In this application, one or several elements are selected from three types of elements: ferromagnetic elements, metalloid elements, and transition metal elements to design a new composition of the iron-based amorphous alloy composite material. The iron-based amorphous alloy composite material is first based on the Fe element, which is the main element to increase the Bs value of the amorphous ribbon; elements such as B and Si are selected from the metalloid elements. The addition of the B element can not only significantly improve the amorphous formation ability of the amorphous alloy, but also reduce the crystallization temperature of the alloy and promote the formation of the amorphous state. The addition of the Si element can improve the corrosion resistance of the alloy, so that the material can maintain stable performance under complex conditions; the addition of the Cu element in the transition metal elements can induce the precipitation of nanocrystalline phases such as the α-Fe phase in the amorphous matrix. These nanocrystalline phases can significantly improve the mobility of magnetic domain walls, thereby increasing the saturation magnetic induction intensity; the addition of Cu can also weaken the binding force between atoms, reduce the energy barrier of crystallization, and promote the precipitation of the crystalline phase. Compared with Ag and Au elements, the Cu element is more economical and easier to conduct a large number of experiments for research; there is a strong chemical interaction between Al and other elements (such as Fe, B, etc.), and a negative mixing enthalpy is presented, which helps to improve the amorphous formation ability; the Mn element can refine the microstructure of the amorphous alloy, increase the degree of atomic discretization, and thus improve the amorphous formation ability; the Ti element can form strong chemical bonds with Fe atoms, enhance the binding force between atoms, and thus improve the strength and hardness of the iron-based amorphous alloy.

[0030] Please refer to Figure 1 as shown, the preparation method of the high-Bs iron-based soft magnetic amorphous alloy includes the following steps: (1) Weighing: Weigh the raw materials according to the predetermined ratio to ensure that the raw materials are completely dry; (2) Loading: First, load part of the pure iron to the bottom of the furnace cavity of the melting furnace, then place part of the nodular cast iron above the pure iron, then add ferroboron and silicon, and finally add the trace element. Finally, place the remaining pure iron in the surrounding gaps; (3) Melting: The raw materials in the melting furnace are melted to form molten steel. In this embodiment, heating is carried out at a power of 132 KW for 30 minutes. At this time, the temperature of the melting furnace is about 1400 °C, and some raw materials begin to melt. Continue heating to about 1580 °C. At this time, the raw materials in the melting furnace are completely melted. If there is a large amount of slag during the melting process, covering the surface of the molten steel in the furnace, slagging is carried out once. If there is less slag, slagging is not necessary; (4) Secondary melting: Add the remaining raw materials to the melting furnace for melting, and carry out slagging after melting. In secondary melting, in order to improve efficiency, the remaining raw materials are generally added all at once, unless the melting furnace is relatively small and the surface of the molten steel will be completely covered after adding the remaining raw materials, then they will be added in batches and melted separately after each addition, and slagging will be carried out separately after melting; among them, the added raw materials cannot cover the surface of the molten steel, that is, after adding the raw materials, it is based on the standard that the flowing molten steel can be seen. The purpose is to prevent crusting. The purpose of secondary melting is, firstly, to reduce the volume of the melting furnace and reduce costs, and secondly, to make the raw materials mix more evenly. The melting temperature of secondary melting is still between 1400 °C and 1580 °C to completely melt the raw materials. Slagging is carried out only after the temperature rises to 1580 °C; (5) Heat preservation: After the raw materials are completely melted, heat preservation is carried out. Slagging is carried out again during heat preservation. During heat preservation, the temperature of the molten steel is measured with a temperature measuring gun every five minutes to ensure that the temperature always remains between 1550 °C and 1580 °C; (6) Sampling: Take out the molten steel with a mold, cool it to form a solid master alloy at room temperature, and then conduct a spectral test. If the spectral test results show that the content of each component element is consistent with the added element content, the melting is successful. If the spectral test results show inconsistency, return to step (4), add the corresponding elemental raw materials to the melting furnace for melting, and then carry out heat preservation and sampling for spectral measurement according to steps (5) and (6) until it is consistent with the added element content; (7) Slagging: After the elements of the solid master alloy are consistent with the added element content, slagging is carried out again after standing for 15 minutes; (8) Pouring steel: After slagging, let it stand again. After the molten steel cools to 1250 °C, pour the ingot; (9) Spray strip: Load the ingot into the crucible for heating. Before starting the spray strip, first check the surfaces of each cooling roller to ensure that each roller surface has high smoothness, no sand holes, no scratches, no potholes, and no residual adhesive materials. Then, install nozzles of different models according to the different target thicknesses and widths of the strip, and preheat the nozzles. In this embodiment, the nozzles are preheated to 900 °C. Subsequently, start heating the ingot to about 1370 °C, and ensure that the rotational speed of the copper roller is 40 m / s. The spray strip equipment starts to spray the strip. When the strip can be stably prepared, insert the plug rod so that the uniform amorphous strip can be stably wound on the copper roller. The target amorphous strip is prepared by the spray strip equipment and the single-roller extreme cooling method.

[0031] Finally, according to the needs of subsequent experiments and applications, the prepared wide-width industrial strip can be roll-sheared and wound into rolls, stored in test bags and then vacuum-preserved to prevent performance deterioration caused by oxidation.

[0032] Using the above preparation method to prepare the iron-based soft magnetic amorphous alloy, after a large number of experiments by the applicant, it is found that the iron-based amorphous soft magnetic alloy strip with a weight of 150 - 250 kg, a width of 40 - 50 mm, and a thickness controllable within 20 μm and suitable for industrial raw materials can be successfully prepared in a single preparation. The applicant selects some as-cast amorphous strips prepared by this preparation method for performance characterization, and the results are shown in Table 1.

[0033] Table 1: Performance characterization of as-cast amorphous strips

[0034] Note: The subscript "bal." represents the balance. The saturation magnetic induction intensity of the iron-based soft magnetic amorphous alloy in this application is above 1.6 T, which has been significantly improved compared with the existing saturation magnetic induction intensity of 1.5 T - 1.55 T.

[0035] It can be clearly seen from Table 1 that after controlling the atomic content ratio of B and Si elements at 15:3 (i.e., b / c = 5), the saturation magnetic induction intensity of the amorphous strip changes little compared with when B:Si is 16:2 (i.e., b / c = 8), but the coercivity decreases. After the content of ferromagnetic elements (Fe element) is slightly increased, the saturation magnetic induction intensity of the as-cast strip does not increase significantly and is basically stable in the range of 1.6 T - 1.65 T. At the same time, the industrial production cost is reduced to less than 10,000 yuan per ton. It can also be known from Table 1 that when the atomic content ratio of B and Si elements is 5 and the sum of the atomic contents of B and Si elements accounts for 17% of the total atomic content (i.e., b + c = 17), the comprehensive performance of the prepared wide-width amorphous strip is the best, not only with good soft magnetic properties but also with considerable economic benefits.

[0036] In summary, reasonably controlling the atomic content ratio of elements B and Si can, to a certain extent, optimize the soft magnetic properties (saturation magnetic induction intensity, coercivity) of as-cast industrialized strip, while effectively controlling the economic cost of preparing large quantities of amorphous strip. Comprehensive optimization is carried out from multiple aspects such as preparation difficulty, strip properties, and economic cost, making great contributions to promoting the industrial development of iron-based amorphous soft magnetic alloys.

[0037] As described above, the above is only the specific implementation manner of this application, but the protection scope of this application is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed in this application should be covered within the protection scope of this application. Therefore, the protection scope of this application shall be subject to the protection scope of the claims.

Claims

1. A high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials, characterized in that, The chemical formula of the iron-based soft magnetic amorphous alloy is: Fe a B b Si c M f , where a, b, c, and f are the atomic percentages of the corresponding elements respectively, 80 ≤ a ≤ 85, 10 ≤ b ≤ 16, 2 ≤ c ≤ 3, 0.001 ≤ f ≤ 1, and a + b + c + f = 100. M is a trace element, which is one or a combination of Co, Zn, Mn, N, Cu, Al, Ti, and S.

2. The high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials according to claim 1, wherein: 5≤b / c≤8.

3. The high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials according to claim 2, wherein: b / c=5, and b+c=17.

4. A preparation method of a high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials, characterized in that, The following steps are involved: (1) Weighing: Weigh the raw materials according to the predetermined ratio to ensure that the raw materials are completely dry; (2) Loading: First, load part of the pure iron to the bottom of the furnace chamber of the smelting furnace, then place part of the ductile iron on top of the pure iron, then add ferroboron and silicon, and finally add trace elements, and finally place the remaining pure iron in the gaps around it; (3) Melting: Melting the raw materials in the melting furnace to melt the raw materials into molten steel; (4) Secondary smelting: Add the remaining raw materials into the smelting furnace for melting, and then slag is removed after melting; (5) Insulation: After the raw materials are completely melted, insulation is carried out, and slag removal is carried out again during the insulation period; (6) Sampling: The molten steel is taken out with a mold and cooled at room temperature to form a solid master alloy, and then a spectrum test is performed. If the spectrum test results show that the content of each component element is basically consistent with the content of the added element, the smelting is successful. If the spectrum test results show inconsistency, return to step (4), add the corresponding element raw materials to the smelting furnace for smelting, and then keep warm and take samples for spectrum measurement according to steps (5) and (6) until the content is basically consistent with the added element content. (7) Deslagging: After the elements of the solid master alloy are basically consistent with the added elements, deslagging is performed again after standing; (8) Steel pouring: After slag removal, let it stand and then pour the steel ingot; (9) Spraying: The steel ingot is placed in a crucible and heated, and then sprayed through the nozzle of the spraying equipment. During the spraying process, amorphous strip is prepared by a single-roll extreme cooling method.

5. The preparation method of the high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials according to claim 4, characterized in that, The smelting temperature in step (3) is 1400°C to 1580°C.

6. The preparation method of the high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials according to claim 4, characterized in that, In the step (4), slag removal is performed after the smelting temperature reaches 1580°C.

7. The preparation method of the high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials as described in claim 4, characterized in that, The insulation temperature in step (5) is between 1550°C and 1580°C.

8. The preparation method of the high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials according to claim 4, characterized in that, In the step (7), the slag is removed again after standing for 15 minutes.

9. The preparation method of the high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials as described in claim 4, characterized in that, After standing in step (8), the molten steel is cooled to 1250°C before pouring the steel ingot.

10. The preparation method of the high-Bs iron-based soft magnetic amorphous alloy prepared from industrial raw materials according to claim 4, characterized in that, The nozzle in step (9) is first preheated to 900°C, and then the steel ingot is heated to 1370°C before the spraying begins.

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