A cobalt-based amorphous soft magnetic alloy material, a preparation method and application thereof

Abstract

The application relates to the technical field of amorphous soft magnetic material preparation, and discloses a cobalt-based amorphous soft magnetic alloy material, a preparation method thereof and application. a Fe b Mo c Si d B e C f M g In the formula, a, b, c, d, e, f and g respectively represent the atomic percentage content of corresponding components; wherein 50<=a<=70, 2<=b<=8, 0.5<=c<=5, 10<=d<=20, 10<=e<=20, 0.01<=f<=0.5, 0.1<=g<=5, and a+b+c+d+e+f+g=100; and M represents at least one of elements V, Cr, Mn and Nb. The cobalt-based amorphous soft magnetic alloy material provided by the application has low saturation magnetic induction intensity, low coercive force, high rectangular ratio and other superior soft magnetic properties, is good in corrosion resistance and easy to prepare; and a magnetic probe prepared from the alloy material has high precision in sensor testing, and has important significance for promoting the development of small high-precision magnetic flux gate current sensors.

Description

Technical Field

[0001] This invention relates to the field of amorphous soft magnetic material preparation technology, specifically to a cobalt-based amorphous soft magnetic alloy material, its preparation method, and its application. Background Technology

[0002] Current sensors, as essential tools for current measurement, are necessary measuring devices for detecting the magnitude and direction of current in conductors, playing a crucial role in fields such as automated equipment, smart grids, and new energy vehicles. Fluxgates operate by utilizing the nonlinear characteristics of the permeability of soft magnetic materials when saturated under excitation, and permeability is directly determined by the material. The higher the permeability of the material, the higher the sensitivity of the fluxgate sensor; therefore, the selection of magnetic materials is crucial. With the continuous advancement of 5G, new energy, and other fields, current sensors are developing towards miniaturization, integration, and intelligence, thus requiring soft magnetic materials with low saturation magnetic induction, low coercivity, high aspect ratio, and high permeability.

[0003] Soft magnetic materials suitable for fluxgate sensors mainly include Fe-Ni-(Mo)permalloy, iron-based nanocrystalline alloys, and cobalt-based amorphous alloys. These soft magnetic materials all possess high permeability (μ) and low coercivity (H). c However, specifically, Fe-Ni-(Mo)permalloy with high magnetic permeability has a small rectangularity and poor high-frequency magnetic properties, while Fe-Ni-(Mo)permalloy with high rectangularity has very poor soft magnetic properties, which limits its application in current sensors.

[0004] Iron-based nanocrystalline alloys, represented by Fe-Si-B-Nb-Cu (Finemet), possess advantages such as high saturation magnetic induction, high permeability, and low cost. They are often used in current sensors in the form of toroidal iron cores. However, due to their difficulty in saturation, high brittleness, and lack of corrosion-resistant elements, they struggle to simultaneously achieve miniaturization, high frequency operation, and reliability. Cobalt-based amorphous alloys, on the other hand, exhibit lower saturation magnetic induction and losses, and higher permeability at high frequencies, resulting in easier saturation, higher rectangularity, and better high-frequency magnetic properties. Furthermore, the addition of corrosion-resistant elements allows the alloys to be prepared and heat-treated under atmospheric or low-vacuum conditions, significantly reducing production costs and improving the stability of devices in harsh environments. Therefore, cobalt-based amorphous soft magnetic alloys are more suitable for high-precision, miniature fluxgate current sensors.

[0005] With the widespread application of high-precision magnetic sensors, many scholars at home and abroad have carried out research on cobalt-based amorphous soft magnetic alloy materials. VAC GmbH in Germany added a small amount of Mo to CoFeSiB, which improved the alloy's processability; however, its heat treatment process is complex and the giant magnetoresistance effect needs further optimization.

[0006] Domestic scholars have attempted to add elements such as Cr, Nb, and Mn to CoFeSiB to simultaneously improve the amorphous forming ability and soft magnetic properties of the alloy material, but the performance is still not ideal, with problems such as complex processes, high saturation magnetic induction, low magnetic permeability, and high cost.

[0007] Chinese patent document CN114875343A discloses a [(Co 0.65 Fe 0.35 ) 0.54 Mn 0.32 Sn 0.09 Nd 0.05 ] 100-x (Zn a Ca 1-a ) x A cobalt-based amorphous alloy system, where a is 0.6-0.8 and x is 5-10. This amorphous alloy has good mechanical properties and yield strength, with a plasticity of up to 11.5%, while the plasticity of existing cobalt-based amorphous alloys is about 2-8%. However, this material has an excessively high saturation magnetic induction intensity, making it difficult to saturate and unsuitable for use in high-precision small current sensors.

[0008] Chinese patent document CN113462993A discloses a Co 68 Fe 6.5 Si 12.5 B 10 Nb x Ni 3-x Cobalt-based amorphous alloy ribbons, which incorporate Ni and Nb elements into traditional cobalt-based amorphous CoFeSiB, can enhance the soft magnetic properties of the amorphous alloy and achieve a more pronounced skin effect. However, its magnetostriction coefficient is not zero, its thermal stability needs optimization, and the addition of precious metal elements increases the preparation cost.

[0009] Chinese patent document CN110993239A discloses a Fe a Co b Si c B d Cu e Iron-cobalt based amorphous soft magnetic alloy. This alloy material has excellent soft magnetic properties and good amorphous forming ability. In Example 1, the material has the highest permeability of 13200 after magnetic field stress relief annealing, but its coercivity is the lowest of 1.4 A / m. Moreover, the magnetic field heat treatment process is complicated and still needs to be optimized.

[0010] The aforementioned patents have improved the soft magnetic properties of CoFeSiB series alloys to varying degrees through composition optimization. However, these materials cannot simultaneously possess the comprehensive properties of low saturation magnetic induction, low coercivity, and high initial permeability, making it difficult to fabricate cobalt-based amorphous soft magnetic materials suitable for current sensors. Therefore, developing a cobalt-based amorphous soft magnetic alloy material that combines low saturation magnetic induction, low coercivity, and high initial permeability is of great significance for promoting the development of fluxgate current sensors and the widespread application of cobalt-based amorphous soft magnetic alloy materials. Summary of the Invention

[0011] This invention addresses the problem that cobalt-based amorphous soft magnetic alloys struggle to simultaneously possess low saturation magnetic induction, low coercivity, and high initial permeability. It provides a cobalt-based amorphous soft magnetic alloy material that, through the synergistic effect between different elements, achieves comprehensive performance with a saturation magnetic induction (Bs) below 0.5T, a coercivity below 1A / m, and high initial permeability.

[0012] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0013] A cobalt-based amorphous soft magnetic alloy material, wherein the composition of the cobalt-based amorphous soft magnetic alloy material has the following expression: Co a Fe b Mo c Si d B e C f M g In the formula, a, b, c, d, e, f, and g represent the atomic percentage content of the corresponding components, where 50≤a≤70, 2≤b≤8, 0.5≤c≤5, 10≤d≤20, 10≤e≤20, 0.01≤f≤0.5, 0.1≤g≤5, and a+b+c+d+e+f+g=100; M is at least one of V, Cr, Mn, and Nb.

[0014] In some embodiments, the atomic percentage of Co in the cobalt-based amorphous soft magnetic alloy material is 60 ≤ a ≤ 70.

[0015] In some embodiments, the atomic percentage of Fe in the cobalt-based amorphous soft magnetic alloy material is 3 ≤ b ≤ 5.

[0016] In some embodiments, the atomic percentage of Mo in the cobalt-based amorphous soft magnetic alloy material is 0.5 ≤ c ≤ 3.

[0017] In some embodiments, the atomic percentage of Si in the cobalt-based amorphous soft magnetic alloy material is 14 ≤ d ≤ 17.

[0018] In some embodiments, the atomic percentage of B in the cobalt-based amorphous soft magnetic alloy material is 10 ≤ e ≤ 15.

[0019] In some embodiments, the atomic percentage of C in the cobalt-based amorphous soft magnetic alloy material is 0.01 ≤ f ≤ 0.3.

[0020] In some embodiments, the atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is 0.1 ≤ g ≤ 3.5.

[0021] In some embodiments, the atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is 0.5 ≤ g ≤ 3, preferably 0.5 ≤ g ≤ 2.

[0022] In some embodiments, the total atomic percentage of Co and Fe in the cobalt-based amorphous soft magnetic alloy material is 65 ≤ a + b ≤ 75.

[0023] In some implementations, M is Cr and / or Mn.

[0024] In some implementations, M is Cr.

[0025] In some embodiments, the purity of the Fe, Co, Mo, B, Si, C and M raw materials is all above 99 wt.%.

[0026] In some embodiments, the saturation magnetic induction of the cobalt-based amorphous soft magnetic alloy material is below 0.5T, and the coercivity is below 1A / m.

[0027] This invention also provides a method for preparing the cobalt-based amorphous soft magnetic alloy material, comprising the following steps:

[0028] Step 1: Weigh out each element raw material according to the alloy composition and then melt it into a master alloy ingot;

[0029] Step 2: The master alloy ingot is processed into amorphous soft magnetic alloy strips or wires;

[0030] Step 3: Annealing heat treatment of amorphous soft magnetic alloy strips or wires to obtain the cobalt-based amorphous soft magnetic alloy material.

[0031] In some embodiments, the preparation of amorphous soft magnetic alloy strips or wires in step 2 includes at least one of single-roll rapid quenching, double-roll rapid quenching, inner-circle water spinning, and glass-coated spinning; preferably, the preparation of amorphous soft magnetic alloy strips or wires in step 2 is by single-roll rapid quenching or inner-circle water spinning.

[0032] In some embodiments, when the method for preparing amorphous soft magnetic alloy strips or wires in step 2 is the single-roller rapid quenching method, the process parameters of the single-roller rapid quenching method are: spray pressure of 0.01-0.03MPa and copper roller rotation speed of 3000-5000r / min.

[0033] In some embodiments, when the method for preparing amorphous soft magnetic alloy strips or wires in step 2 is the inner-circle water spinning method, the process parameters of the inner-circle water spinning method are: spray pressure of 0.3-0.5MPa and copper roller rotation speed of 1000-1400r / min.

[0034] In some implementations, in step 2, the strip width is 1-1.3 mm and the thickness is 18-25 μm; the wire diameter is 80-120 μm.

[0035] In some embodiments, the annealing heat treatment in step 3 is carried out under vacuum conditions at a constant temperature of 400-560°C for 10-60 minutes. The vacuum conditions refer to a vacuum level of 5.0 × 10⁻⁶ within the equipment. -3 When Pa is below;

[0036] In some embodiments, the material is removed after annealing heat treatment and then water-quenched to room temperature.

[0037] The present invention also provides a magnetic probe comprising the aforementioned cobalt-based amorphous soft magnetic alloy material.

[0038] The present invention also provides that the magnetic probe is used to prepare sensors, electronic inductive devices or current transformers, such as fluxgate current sensors, and its accuracy is tested using a TK1000·200A type DC current sensor detection device, and the obtained sensor has very high accuracy.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] (1) The cobalt-based amorphous soft magnetic alloy material with the specific composition of the present invention has the advantages of low saturation magnetic induction, low coercivity, high initial permeability and high rectangularity ratio, and excellent soft magnetic properties. It can still maintain a high amorphous forming ability without the addition of P element, and has excellent comprehensive performance.

[0041] (2) The cobalt-based amorphous soft magnetic alloy material of the present invention also has good corrosion resistance, long service time, high service stability, and can be applied to a variety of harsh environments, with wider adaptability.

[0042] (3) The cobalt-based amorphous soft magnetic alloy material of the present invention does not contain rare earth metal elements or volatile elements, and has lower cost and more stable performance.

[0043] (4) The cobalt-based amorphous soft magnetic alloy material of the present invention does not contain harmful substances such as cadmium, lead, and mercury, thus avoiding negative impacts on human health and being more environmentally friendly.

[0044] (5) The cobalt-based amorphous soft magnetic alloy material of the present invention has a simple preparation process. The material after simple isothermal annealing heat treatment has better comprehensive soft magnetic properties. It does not require cumbersome steps such as magnetic field annealing, which is conducive to industrial promotion and application.

[0045] (6) The magnetic probe made of the alloy material of the present invention is applied in the fields of sensors, electronic inductors or current transformers, and its accuracy is greatly improved. It is of great significance for promoting the development of small high-precision fluxgate current sensors and other equipment. Attached Figure Description

[0046] Figure 1 The XRD diffraction patterns are those of the cobalt-based amorphous alloy materials in Examples 1, 2, 3 and Comparative Examples 1 and 2.

[0047] Figure 2 The figures show the coercivity variation curves of cobalt-based amorphous alloy materials in Examples 1, 2, 3 and Comparative Example 3 at different annealing temperatures.

[0048] Figure 3 The curves showing the coercivity and initial permeability changes of the cobalt-based amorphous alloy materials in Examples 1, 2, 3 and Comparative Examples 1 and 2 are shown.

[0049] Figure 4 The curves showing the saturation magnetic induction intensity changes of the cobalt-based amorphous alloy materials prepared in Examples 1, 2, 3 and Comparative Examples 1 and 2 are shown.

[0050] Figure 5 Electrochemical curves of the cobalt-based amorphous alloy materials prepared in Examples 1, 2, 3 and Comparative Example 3. Detailed Implementation

[0051] Before further describing specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terminology used in the embodiments of the present invention is for describing specific embodiments and not for limiting the scope of protection of the present invention. Test methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the respective manufacturers.

[0052] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, apparatus, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, apparatus, and materials similar to or equivalent to those described, apparatus, and materials in the embodiments of this invention may be used to implement the present invention.

[0053] This invention provides the following specific embodiments and all possible combinations thereof. For the purpose of brevity, this application only describes a few representative components to represent all possible combinations of the described technical solutions.

[0054] Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in this application's specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0055] As used herein, the terms "and / or," "or / and," and "and / or" encompass any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that, in this application, the technical solution undoubtedly includes solutions connected by "logical AND," and also undoubtedly includes solutions connected by "logical OR."

[0056] For example, "A and / or B" includes three parallel solutions: A, B, and A+B. Another example is the technical solution "A, and / or, B, and / or, C, and / or, D," which includes any one of A, B, C, and D (i.e., all connected by "logical OR"), any and all combinations of A, B, C, and D, including combinations of any two or three of A, B, C, and D, and combinations of all four of A, B, C, and D (i.e., all connected by "logical AND").

[0057] The terms “containing,” “comprising,” and “including” as used in this invention are synonyms and are inclusive or open-ended, and do not exclude additional, uncited members, elements, or method steps.

[0058] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0059] In this invention, terms such as "preferred," "better," "more suitable," and "ideal" merely describe implementation methods or embodiments that yield better results and should be understood not to limit the scope of protection of this invention. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.

[0060] In this invention, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this invention.

[0061] To obtain cobalt-based amorphous soft magnetic alloys with low saturation magnetic induction, low coercivity, and high initial permeability, a small amount of transition metal elements is added to enhance the amorphous forming ability and corrosion resistance of the alloy. Isothermal annealing heat treatment is then used to improve the overall soft magnetic properties of the alloy.

[0062] This invention provides a cobalt-based amorphous soft magnetic alloy material, the composition of which has the following expression: Co a Fe b Mo c Si d B e C f M g In the formula, a, b, c, d, e, f, and g represent the atomic percentage content of the corresponding components, where 50≤a≤70, 2≤b≤8, 0.5≤c≤5, 10≤d≤20, 10≤e≤20, 0.01≤f≤0.5, 0.1≤g≤5, and a+b+c+d+e+f+g=100; M is one of V, Cr, Mn, and Nb.

[0063] This invention is based on CoFeSiB material. A small amount of Mo is used to improve the soft magnetic properties of the material, and a small amount of transition metal is added to improve the corrosion resistance and physical properties. However, the addition of transition metal can lead to a decrease in the permeability and amorphous formation ability of the material. This invention adds a very small amount of non-metallic C to adjust the soft magnetic properties of the material, but this may also lead to a decrease in oxidation resistance and corrosion resistance. Different elements have different effects on different properties of the material, and they also influence each other. The inventors have found that the amorphous soft magnetic alloy with the above composition can simultaneously possess low saturation magnetic induction, low coercivity, and high initial permeability, while also exhibiting excellent corrosion resistance and oxidation resistance, achieving a comprehensive performance level that is among the world's top.

[0064] Amorphous soft magnetic alloys refer to alloys with atoms arranged in a non-long-range order and possessing excellent soft magnetic properties. Cobalt-based amorphous soft magnetic alloys refer to cobalt-based alloys with an amorphous structure and excellent soft magnetic properties, typically including Co-Ni-B and Co-Fe-B systems. This invention specifically refers to the Co-Fe-B system, whose main component is CoFeSiB, with Co being the most abundant element.

[0065] In some embodiments, the atomic percentage of Co in the cobalt-based amorphous soft magnetic alloy material is 60 ≤ a ≤ 70. Values ​​such as 60.5, 61, 61.5, 62, 62.5, 63, 63.5, 64, 64.5, 65, 65.5, 66, 66.5, 67, 67.5, 68, 68.57, 69, 69.5, or any value between them are preferred in some embodiments; more preferably, 62 ≤ a ≤ 67.5; further preferably, 63 ≤ a ≤ 67; even more preferably, 64 ≤ a ≤ 66.5. The cobalt-based amorphous alloy has lower saturation magnetic induction and loss, and higher permeability at high frequencies, thus it is easier to saturate, has a high rectangularity ratio, and good high-frequency magnetic properties.

[0066] In some embodiments, the atomic percentage of Fe in the cobalt-based amorphous soft magnetic alloy material is 3 ≤ b ≤ 5. Values ​​such as 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, or any value between them are preferred in some embodiments; more preferably, 3.5 ≤ b ≤ 4.5; and even more preferably, 3 ≤ b ≤ 4. An appropriate iron content can reduce the coercivity of the amorphous alloy, increase its permeability and saturation magnetic induction, thereby improving its soft magnetic properties.

[0067] In some embodiments, the atomic percentage of Mo in the cobalt-based amorphous soft magnetic alloy material is 0.5 ≤ c ≤ 3. Values ​​such as 0.6, 0.7, 0.9, 1.0, 1.2, 1.25, 1.4, 1.5, 1.6, 1.75, 1.8, 2, 2.2, 2.4, 2.5, 2.6, 2.8, or any value between them are preferred in some embodiments; more preferably, 1.5 ≤ c ≤ 2.5; and even more preferably, 1 ≤ c ≤ 2. The addition of Mo can reduce the saturation magnetic induction intensity of the material to a certain extent, reducing the vacuum requirements for sprayed strips or wires and the oxidation phenomenon caused by vacuum during heat treatment. However, the addition of this precious metal also increases the cost of raw materials.

[0068] In some embodiments, the atomic percentage of Si in the cobalt-based amorphous soft magnetic alloy material is 14 ≤ d ≤ 17. Values ​​such as 14.25, 14.5, 14.75, 15, 15.25, 15.5, 15.75, 16, 16.25, 16.5, 16.75, or any value between them are preferred in some embodiments; more preferably, 14.5 ≤ d ≤ 16.5; even more preferably, 15 ≤ d ≤ 16. Si can lower the melting point of the amorphous alloy, thus making it easier to form an amorphous structure during rapid cooling or rapid solidification. Furthermore, Si can change the viscosity of the alloy, further promoting amorphous formation and improving the alloy's amorphous forming ability.

[0069] In some embodiments, the atomic percentage of B in the cobalt-based amorphous soft magnetic alloy material is 10 ≤ e ≤ 15. Values ​​such as 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or any value between them are preferred in some embodiments; more preferably, 10 ≤ d ≤ 14; and even more preferably, 10 ≤ d ≤ 13.

[0070] In some embodiments, the atomic percentage of C in the cobalt-based amorphous soft magnetic alloy material is 0.01 ≤ f ≤ 0.3, such as 0.015, 0.03, 0.04, 0.05, 0.06, 0.07, 0.075, 0.08, 0.1, 0.0125, 0.15, 0.0175, 0.2, 0.25, 0.275, or any value between them; in some embodiments, preferably, 0.05 ≤ f ≤ 0.2; more preferably, 0.05 ≤ f ≤ 0.15; even more preferably, 0.05 ≤ f ≤ 0.1; the addition of C can improve the soft magnetic properties to a certain extent, and within this range, it is better to avoid affecting the oxidation resistance and corrosion resistance of the material.

[0071] In some embodiments, the atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is 0.1 ≤ g ≤ 3.5. For example, 0.2, 0.3, 0.4, 0.45, 0.5, 0.6, 0.75, 1, 1.25, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, or any value between them. In this invention, a small amount of transition metal is used to improve the material's corrosion resistance to adapt to more types of application environments. In some embodiments, the atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is 0.5 ≤ g ≤ 3, preferably 0.5 ≤ g ≤ 2. Within this range, the material exhibits good soft magnetic properties and strong overall amorphous forming ability. Further preferably, it is 0.55 ≤ g ≤ 1.5. Within this range, the amorphous forming ability, corrosion resistance, and oxidation resistance are all well-developed. Excessive M may lead to a decrease in the amorphous properties of the material and a loss of magnetic permeability.

[0072] In some embodiments, the total atomic percentage of Co and Fe in the cobalt-based amorphous soft magnetic alloy material is 65 ≤ a + b ≤ 75.

[0073] In some embodiments, M is Cr and / or Mn. Compared to other elements, the addition of Cr and / or Mn gives the alloy material superior amorphous forming ability, zero magnetostriction coefficient, excellent soft magnetic properties at high temperatures, and improved corrosion resistance. Furthermore, when the Mn concentration is low, the substitution of some Fe atoms by Mn atoms to form an MnFe alloy helps reduce the drag of magnetic domain walls, thereby reducing coercivity.

[0074] In some embodiments, the purity of the Fe, Co, Mo, B, Si, C, and M raw materials is all above 99 wt.%. Preferably, the purity of all raw materials is above 99.5 wt.%.

[0075] The cobalt-based amorphous soft magnetic alloy material of this invention has the advantages of low saturation magnetic induction, low coercivity, high initial permeability and high rectangularity ratio, and has excellent soft magnetic properties.

[0076] In some embodiments, the cobalt-based amorphous soft magnetic alloy material has a saturation magnetic flux density below 0.5 T and can simultaneously achieve a coercivity below 1 A / m. Preferably, the saturation magnetic flux density is below 0.48 T, 0.45 T, or 0.4 T; and the coercivity is below 0.9 A / m, 0.95 A / m, 0.85 A / m, 0.8 A / m, or 0.78 A / m.

[0077] In some embodiments, the initial permeability of the cobalt-based amorphous soft magnetic alloy material is above 25,000, preferably above 25,500, above 26,000, above 26,500, above 27,000, above 27,500, or above 27,600.

[0078] In some embodiments, the cobalt-based amorphous soft magnetic alloy material further has an initial magnetic permeability of 25,000-30,000, a saturation magnetic induction of 0.1-0.5T, and a coercivity of 0.3-1A / m.

[0079] In some embodiments, the cobalt-based amorphous soft magnetic alloy material further has an initial magnetic permeability of 27,000-30,000, a saturation magnetic induction of 0.2-0.5T, and a coercivity of 0.4-1A / m.

[0080] This invention also provides a method for preparing the cobalt-based amorphous soft magnetic alloy material, comprising the following steps:

[0081] Step 1: Weigh out each element raw material according to the alloy composition and then melt it into a master alloy ingot;

[0082] Step 2: The master alloy ingot is processed into amorphous soft magnetic alloy strips or wires;

[0083] Step 3: Annealing heat treatment of amorphous soft magnetic alloy strips or wires to obtain the cobalt-based amorphous soft magnetic alloy material.

[0084] The amorphous soft magnetic alloy material in this invention can be obtained by simple melting, preparation of strips or wires, and then isothermal annealing. It does not require complex and cumbersome processes, and the annealing does not require the addition of a magnetic field, which is conducive to the rapid advancement of industrial production and application.

[0085] In some implementations, in step 1, the amount of each element is calculated based on the alloy composition before weighing, with the error range being within 0.0005g when weighing, in order to avoid operational errors affecting the material properties.

[0086] In some embodiments, step 1, when melting the master alloy ingot, includes the following steps: placing the weighed alloy raw material in a melting device and melting it under an inert atmosphere; holding it at a temperature for 5-20 minutes after melting, and then pouring the molten alloy ingot into a prepared copper mold and cooling it for more than 30 minutes to obtain the master alloy ingot.

[0087] The melting method for the aforementioned pure metals is arbitrary; for example, it may involve melting the metal by high-frequency heating after evacuating a chamber. Furthermore, the master alloy and the final soft magnetic alloy typically have the same composition.

[0088] In some embodiments, the raw materials are heated to melt them, resulting in molten metal (metal melt). There are no particular limitations on the temperature of the molten metal, as long as it is sufficient to melt all the raw materials, for example, 1300–1500°C.

[0089] Preferably, the smelting process is carried out 1-3 times to ensure that the components in each alloy ingot are evenly distributed.

[0090] In some embodiments, the preparation of amorphous soft magnetic alloy strips or wires in step 2 includes, but is not limited to, at least one of the following: single-roll rapid quenching method, double-roll rapid quenching method, inner-circle water spinning method, and glass-coated spinning method; single-roll spinning method can also be used.

[0091] Preferably, the amorphous soft magnetic alloy strip or wire prepared in step 2 is prepared by single-roll rapid quenching or inner-circle water spinning.

[0092] In this invention, the "single-roller rapid quenching method" refers to melting an ingot and pouring it onto the surface of a rotating water-cooled copper roller, which is then rapidly cooled to obtain a thin strip in an amorphous to microcrystalline state. The preparation process involves using a high-speed rotating roller to rapidly cool the molten liquid column into a thin strip.

[0093] In some embodiments, when the method for preparing amorphous soft magnetic alloy strips or wires in step 2 is a single-roll rapid quenching method, the process parameters of the single-roll rapid quenching method are: spray pressure of 0.01-0.03 MPa and copper roller rotation speed of 3000-5000 r / min. In some embodiments, the preferred process parameters of the single-roll rapid quenching method are: spray pressure of 0.01-0.03 MPa and copper roller rotation speed of 3500-4500 r / min.

[0094] Preferably, the process parameters for the single-roller rapid quenching method are: spray pressure of 0.02 MPa and copper roller rotation speed of 4000 r / min.

[0095] In some embodiments, the preparation of amorphous soft magnetic alloy strips or wires by the single-roll rapid quenching method specifically includes the following steps: after crushing the master alloy ingot, it is placed in a quartz tube with a nozzle at the bottom, the nozzle diameter being 0.7-0.8 mm; the quartz tube is placed in a strip spinning machine to melt the alloy ingot therein for a second time, and a continuous alloy amorphous strip is prepared by the single-roll rapid quenching method.

[0096] Furthermore, the preparation of amorphous soft magnetic alloy strips or wires by the single-roller rapid quenching method specifically includes the following steps: After crushing the master alloy ingot, it is loaded into a quartz tube with a nozzle at the bottom having a diameter of 0.75-0.8 mm. The upper and lower positions of the quartz tube are adjusted to control the distance between the tube opening and the roller surface to be 0.1-0.4 mm. The vacuum is evacuated to below 0.02 Pa, and the pressure difference between the inside and outside of the quartz tube is adjusted to 0.01-0.03 MPa. The single-roller rapid quenching strip spinning process is adopted, and the strip is spun at a speed of 30-50 m / s under an argon protective atmosphere, i.e., the copper roller speed is set to 3000-5000 r / min. The heating current is turned on, and when the solenoid heats and melts the master alloy ingot until it is completely melted and a white light shaking phenomenon is observed, the heating current is turned off and the spray button is pressed at the same time to obtain a continuous amorphous alloy strip.

[0097] In this invention, the "inner circular water spinning method" involves heating metals, metal-non-metal mixtures, and metal alloys to a molten state, and then uniformly spraying the molten metal into cooling water through a high-speed rotating inner circular water basin to form amorphous filaments.

[0098] In some embodiments, when the method for preparing amorphous soft magnetic alloy strips or wires in step 2 is the inner-circle water spinning method, the process parameters of the inner-circle water spinning method are: spray pressure of 0.3-0.5MPa and copper roller rotation speed of 1000-1400r / min.

[0099] In some embodiments, the preparation of amorphous soft magnetic alloy strips or wires by the inner-circle hydrospinning method specifically includes the following steps: after crushing the master alloy ingot, it is placed into a quartz tube with a hole at the bottom, the hole diameter being 5-10 μm larger than that of the wire. The copper roller is turned on (rotation speed of 1000-1400 r / min) and water is added to form a water film, with a water-spinning thickness of 15-20 mm.

[0100] Next, the quartz tube is placed in a high-frequency induction coil for secondary melting of the alloy ingot. An inner-circle water spinning method is used, pressurizing the top of the quartz tube to allow the alloy jet to enter the water film at a pressure of 0.3-0.5 MPa, forming amorphous alloy wires before breaking into droplets. Preferably, the jetting pressure is 0.45 MPa, and the copper roller rotation speed is 1200 r / min when using the inner-circle water spinning method.

[0101] In some embodiments, in step 2, the strip width is 1-1.3 mm and the thickness is 18-25 μm; the wire diameter is 80-120 μm.

[0102] In some implementations, the strip width in step 2 is 1.1 mm, 1.15 mm, 1.2 mm, 1.25 mm, or any value between them, and the thickness is 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, or any value between them.

[0103] In some embodiments, the annealing heat treatment in step 3 is performed under vacuum conditions at a constant temperature of 440-560°C for 10-60 minutes. The isothermal treatment can be performed within a temperature range of 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, or any value between these ranges. The treatment time can be 10 minutes, 12 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or any value between these ranges.

[0104] Preferably, the processing time is 10-30 minutes, and more preferably 10-20 minutes. In this invention, the amorphous alloy material can achieve excellent soft magnetic properties after a short annealing heat treatment, with a short process time and lower industrialization costs.

[0105] DSC testing of the cobalt-based amorphous alloy material of the present invention shows a crystallization temperature of approximately 560-580°C, and in some embodiments, the crystallization temperature is approximately 565-575°C. The annealing heat treatment temperature should be within this range. In some embodiments, it is preferably isothermal treatment at 400-560°C; more preferably 440-560°C; even more preferably 480-560°C; and even more preferably 480-540°C. Too low a temperature makes it difficult to achieve amorphous structure rearrangement, while too high a temperature causes the alloy material to melt.

[0106] The annealing heat treatment in this invention is isothermal annealing heat treatment, that is, the program of the tubular heat treatment furnace is set according to the predetermined temperature. After the temperature inside the furnace reaches the preset temperature and the vacuum degree of the quartz tube drops below the target value, the quartz tube containing alloy strip or wire is quickly pushed into the middle part of the tubular heat treatment furnace, and the holding time is calculated at the same time.

[0107] In some embodiments, the material is annealed and then water-quenched to room temperature. Rapid cooling ensures that the amorphous structure inside the material is not altered; that is, the high-temperature alloy is rapidly cooled into water, causing it to reach a supercooled state instantaneously, thereby forming an amorphous alloy. When the alloy cools fast enough, a supercooled liquid is formed. The molecules or atoms in the supercooled liquid are arranged randomly, and there is no fixed crystal lattice structure. In this case, if the supercooled liquid is subjected to appropriate perturbation, such as mechanical vibration or thermal fluctuation, structural relaxation may occur, forming an amorphous alloy. During water quenching, the liquid alloy in the supercooled state is easily perturbed, leading to the formation of an amorphous structure.

[0108] The present invention also provides a magnetic probe comprising the aforementioned cobalt-based amorphous soft magnetic alloy material.

[0109] This invention also provides the magnetic probe for use in the fabrication of sensors, electronic inductive devices, or current transformers. For example, it can be applied to the fabrication of fluxgate current sensors, and its accuracy is tested using a TK1000·200A type DC current sensor detection device. The magnetic probe prepared with the alloy material described in this invention exhibits extremely high accuracy in sensor testing, which is of great significance for promoting the development of small, high-precision fluxgate current sensors.

[0110] All raw materials used in the following specific implementation methods were purchased from the market.

[0111] Example 1

[0112] In this embodiment, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co 66 Fe4) 68.9 Mo2Si 16 B 12 C 0.1 The specific preparation method of Cr1 alloy material is as follows:

[0113] Step 1: Combine raw materials Co, Fe, Mo, Si, B, C, and Cr with a purity greater than 99.5% according to the compositional formula (Co... 66 Fe4) 68.9 Mo2Si 16 B 12 C 0.1 Cr1 is used for batching, and the weighing error is controlled within 0.0005g;

[0114] Step 2: Place the proportioned raw materials into an alumina crucible in a clean induction melting furnace, evacuate to below -0.002 Pa, and perform induction melting under an argon atmosphere. After melting, hold at the temperature for more than 10 minutes, then pour the molten alloy ingot into a copper mold and cool it in the furnace for 25 minutes to obtain a homogeneous master alloy ingot.

[0115] Step 3: After crushing the master alloy ingot obtained in Step 2, load it into a quartz tube with a nozzle of about 0.8mm at the bottom. Adjust the vertical position of the quartz tube to control the distance between the tube opening and the roller surface to about 0.25mm. Evacuate to less than 0.02Pa, adjust the pressure difference between the inside and outside of the quartz tube to 0.02MPa, and use a single-roller rapid quenching strip spinning process. Spin the strip at a speed of 40m / s under an argon protective atmosphere, i.e., set the copper roller speed to 4000r / min. Turn on the heating current, and wait until the solenoid heats and melts the master alloy ingot until it is completely melted and a white light shaking phenomenon is observed. Then turn off the heating current and press the spray button at the same time to obtain a continuous amorphous alloy strip; the strip width is 1.26mm and the thickness is 23μm.

[0116] Step 4: Cut the amorphous alloy strip prepared in Step 3 into strips approximately 75 mm long, wrap them in tin foil, and place them into the quartz tube of a tubular annealing furnace. First, evacuate to a low vacuum of 5 Pa, then evacuate to a high vacuum of 5.0 × 10⁻⁶ Pa. -3 Pa; Set the heating program of the heat treatment furnace in advance. After the temperature inside the furnace reaches the preset temperature (540℃) and remains stable, push the quartz tube into the tube furnace and start calculating the holding time at the same time; after holding for 10 minutes, take out the quartz tube and quench it in water to room temperature to obtain the heat-treated cobalt-based amorphous soft magnetic alloy material.

[0117] Example 2

[0118] In this embodiment, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co 66 Fe4) 67.9 Mo2Si 16 B 12 C 0.1 The specific preparation method of Cr2 alloy material is as follows:

[0119] Step 1: Prepare raw materials Co, Fe, Mo, Si, B, C, and Cr with a purity greater than 99.5% according to the material's molecular formula, and control the weighing error within 0.0005g;

[0120] Step 2: Place the proportioned raw materials into an alumina crucible in a clean induction melting furnace, evacuate to below -0.002 Pa, and perform induction melting under an argon atmosphere. After melting, hold at the temperature for more than 10 minutes, then pour the molten alloy ingot into a copper mold and cool it in the furnace for 25 minutes to obtain a homogeneous master alloy ingot.

[0121] Step 3: After crushing the master alloy ingot obtained in Step 2, load it into a quartz tube with a nozzle of about 0.8mm at the bottom. Adjust the upper and lower positions of the quartz tube to control the distance between the tube opening and the roller surface to about 0.25mm. Evacuate to less than 0.02Pa, adjust the pressure difference between the inside and outside of the quartz tube to 0.02MPa, and use a single-roller rapid quenching strip spinning process. Spin the strip at a speed of 40m / s under an argon protective atmosphere, i.e., set the copper roller speed to 4000r / min. Turn on the heating current, and wait until the solenoid heats and melts the master alloy ingot until it is completely melted and a white light shaking phenomenon is observed. Then turn off the heating current and press the spray button at the same time to obtain a continuous amorphous alloy strip; the strip width is 1.28mm and the thickness is 24μm.

[0122] Step 4: Cut the amorphous alloy strip prepared in Step 3 into strips approximately 75 mm long, wrap them in tin foil, and place them into the quartz tube of a tubular annealing furnace. First, evacuate to a low vacuum of 5 Pa, then evacuate to a high vacuum of 5.0 × 10⁻⁶ Pa. -3 Pa; Set the heating program of the heat treatment furnace in advance. After the temperature inside the furnace reaches the preset temperature (540℃) and remains stable, push the quartz tube into the tube furnace and start calculating the holding time at the same time; after holding for 10 minutes, take out the quartz tube and quench it in water to room temperature to obtain the heat-treated cobalt-based amorphous soft magnetic alloy material.

[0123] Example 3

[0124] In this embodiment, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co 66 Fe4) 66.9 Mo2Si 16 B 12 C 0.1 Cr3, the specific preparation method is as follows:

[0125] Step 1: Prepare raw materials Co, Fe, Mo, Si, B, C, and Cr with a purity greater than 99.5% according to the material's molecular formula, and control the weighing error within 0.0005g;

[0126] Step 2: Place the proportioned raw materials into an alumina crucible in a clean induction melting furnace, evacuate to below -0.002 Pa, and perform induction melting under an argon atmosphere. After melting, hold at the temperature for more than 10 minutes, then pour the molten alloy ingot into a copper mold and cool it in the furnace for 25 minutes to obtain a homogeneous master alloy ingot.

[0127] Step 3: After crushing the master alloy ingot obtained in Step 2, put it into a quartz tube with a nozzle of about 0.8mm at the bottom. Adjust the upper and lower positions of the quartz tube to control the distance between the tube opening and the roller surface to about 0.25mm. Evacuate to less than 0.02Pa, adjust the pressure difference between the inside and outside of the quartz tube to 0.02MPa, and use a single-roller fast quenching strip spinning process. Spin the strip at a speed of 40m / s under an argon protective atmosphere, i.e., set the copper roller speed to 4000r / min. Turn on the heating current, and wait until the solenoid heats and melts the master alloy ingot until it is completely melted and a white light shaking phenomenon is observed. Then turn off the heating current and press the spray button at the same time to obtain a continuous amorphous alloy strip with a width of 1.19mm and a thickness of 23μm.

[0128] Step 4: Cut the amorphous alloy strip prepared in Step 3 into strips approximately 75 mm long, wrap them in tin foil, and place them into the quartz tube of a tubular annealing furnace. First, evacuate to a low vacuum of 5 Pa, then evacuate to a high vacuum of 5.0 × 10⁻⁶ Pa. -3 Pa; Set the heating program of the heat treatment furnace in advance. After the temperature inside the furnace reaches the preset temperature (540℃) and remains stable, push the quartz tube into the tube furnace and start calculating the holding time at the same time; after holding for 10 minutes, take out the quartz tube and quench it in water to room temperature to obtain the heat-treated cobalt-based amorphous soft magnetic alloy material.

[0129] Example 4

[0130] In this embodiment, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co 66 Fe4) 67.9 Mo2Si 16 B 12 C 0.1 The specific preparation method of Cr1Mn1 alloy material is as follows:

[0131] Step 1: Prepare raw materials Co, Fe, Mo, Si, B, C, Cr, and Mn with a purity greater than 99.5% according to the material's molecular formula, and control the weighing error within 0.0005g;

[0132] Step 2: Place the proportioned raw materials into an alumina crucible in a clean induction melting furnace, evacuate to below -0.002 Pa, and perform induction melting under an argon atmosphere. After melting, hold at the temperature for more than 10 minutes, then pour the molten alloy ingot into a copper mold and cool it in the furnace for 25 minutes to obtain a homogeneous master alloy ingot.

[0133] Step 3: After crushing the master alloy ingot obtained in Step 2, load it into a quartz tube with a nozzle of about 0.8mm at the bottom. Adjust the upper and lower positions of the quartz tube to control the distance between the tube opening and the roller surface to about 0.25mm. Evacuate to less than 0.02Pa, adjust the pressure difference between the inside and outside of the quartz tube to 0.02MPa, and use a single-roller rapid quenching spinning process. Spin the strip at a speed of 40m / s under an argon protective atmosphere, i.e., set the copper roller speed to 4000r / min. Turn on the heating current, and wait until the solenoid heats and melts the master alloy ingot until it is completely melted and a white light shaking phenomenon is observed. Then turn off the heating current and press the spray button at the same time to obtain a continuous amorphous alloy strip with a width of 1.25mm and a thickness of 25μm.

[0134] Step 4: Cut the amorphous alloy strip prepared in Step 3 into strips approximately 75 mm long, wrap them in tin foil, and place them into the quartz tube of a tubular annealing furnace. First, evacuate to a low vacuum of 5 Pa, then evacuate to a high vacuum of 5.0 × 10⁻⁶ Pa. -3 Pa; Set the heating program of the heat treatment furnace in advance. After the temperature inside the furnace reaches the preset temperature (540℃) and remains stable, push the quartz tube into the tube furnace and start calculating the holding time at the same time; after holding for 10 minutes, take out the quartz tube and quench it in water to room temperature to obtain the heat-treated cobalt-based amorphous soft magnetic alloy material.

[0135] Comparative Example 1

[0136] In this comparative example, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co 66 Fe4) 68.9 Mo2Si 16 B 12 C 0.1 The specific preparation method of this alloy material is as follows: Cr

[0137] Step 1: Prepare raw materials Co, Fe, Mo, Si, B, C, and Cr with a purity greater than 99.5% according to their molecular formulas, and control the weighing error within 0.0005g.

[0138] Step 2: Place the proportioned raw materials into an alumina crucible in a clean induction melting furnace, evacuate to below -0.002 Pa, and perform induction melting under an argon atmosphere. After melting, hold at the temperature for more than 10 minutes, then pour the molten alloy ingot into a copper mold and cool it in the furnace for 25 minutes to obtain a homogeneous master alloy ingot.

[0139] Step 3: After crushing the master alloy ingot obtained in Step 2, load it into a quartz tube with a nozzle of about 0.8mm at the bottom. Adjust the upper and lower positions of the quartz tube to control the distance between the tube opening and the roller surface to about 0.25mm. Evacuate to less than 0.02Pa, adjust the pressure difference between the inside and outside of the quartz tube to 0.02MPa, and use a single-roller rapid quenching spinning process. Spin the strip at a speed of 40m / s under an argon protective atmosphere, i.e., set the copper roller speed to 4000r / min. Turn on the heating current, and wait until the solenoid heats and melts the master alloy ingot until it is completely melted and a white light shaking phenomenon is observed. Then turn off the heating current and press the spray button at the same time to obtain a continuous amorphous alloy strip with a width of 1.27mm and a thickness of 22μm.

[0140] Comparative Example 2

[0141] The molecular formula (Co) was prepared according to the method in Example 1. 68.15 Fe 4.35 ) 71.5 Si 12.5 B 15 The specific preparation method of the Cr1 cobalt-based amorphous soft magnetic alloy material is as follows:

[0142] Step 1: Prepare raw materials Co, Fe, Si, B and Cr with a purity greater than 99.5% according to the material molecular formula, and control the weighing error within 0.0005g;

[0143] Step 2: Place the proportioned raw materials into an alumina crucible in a clean induction melting furnace, evacuate to below -0.002 Pa, and perform induction melting under an argon atmosphere. After melting, hold at the temperature for more than 10 minutes, then pour the molten alloy ingot into a copper mold and cool it in the furnace for 25 minutes to obtain a homogeneous master alloy ingot.

[0144] Step 3: After crushing the master alloy ingot obtained in Step 2, load it into a quartz tube with a nozzle of about 0.8mm at the bottom. Adjust the upper and lower positions of the quartz tube to control the distance between the tube opening and the roller surface to about 0.25mm. Evacuate to less than 0.02Pa, adjust the pressure difference between the inside and outside of the quartz tube to 0.02MPa, and use a single-roller rapid quenching strip spinning process. Spin the strip at a speed of 40m / s under an argon protective atmosphere, i.e., set the copper roller speed to 4000r / min. Turn on the heating current, and wait until the solenoid heats and melts the master alloy ingot until it is completely melted and a white light shaking phenomenon is observed. Then turn off the heating current and press the spray button at the same time to obtain a continuous amorphous alloy strip with a width of 1.30mm and a thickness of 25μm.

[0145] Step 4: Cut the amorphous alloy strip prepared in Step 3 into strips approximately 75 mm long, wrap them in tin foil, and place them into the quartz tube of a tubular annealing furnace. First, evacuate to a low vacuum of 5 Pa, then evacuate to a high vacuum of 5.0 × 10⁻⁶ Pa. -3Pa; Set the heating program of the heat treatment furnace in advance. After the temperature inside the furnace reaches the preset temperature (540℃) and remains stable, push the quartz tube into the tube furnace and start calculating the holding time at the same time; after holding for 10 minutes, take out the quartz tube and quench it in water to room temperature to obtain the heat-treated cobalt-based amorphous soft magnetic alloy material.

[0146] Comparative Example 3

[0147] The molecular formula Co was prepared according to the method in Example 1. 66 Fe4Mo2Si 16 B 12 The specific preparation method of the cobalt-based amorphous soft magnetic alloy material is as follows:

[0148] Step 1: Prepare raw materials Co, Fe, Mo, Si and B with a purity greater than 99.5% according to the material molecular formula, and control the weighing error within 0.0005g;

[0149] Step 2: Place the proportioned raw materials into an alumina crucible in a clean induction melting furnace, evacuate to below -0.002 Pa, and perform induction melting under an argon atmosphere. After melting, hold at the temperature for more than 10 minutes, then pour the molten alloy ingot into a copper mold and cool it in the furnace for 25 minutes to obtain a homogeneous master alloy ingot.

[0150] Step 3: After crushing the master alloy ingot obtained in Step 2, load it into a quartz tube with a nozzle of about 0.8mm at the bottom. Adjust the upper and lower positions of the quartz tube to control the distance between the tube opening and the roller surface to about 0.25mm. Evacuate to less than 0.02Pa, adjust the pressure difference between the inside and outside of the quartz tube to 0.02MPa, and use a single-roller rapid quenching strip spinning process. Spin the strip at a speed of 40m / s under an argon protective atmosphere, i.e., set the copper roller speed to 4000r / min. Turn on the heating current, and wait until the solenoid heats and melts the master alloy ingot until it is completely melted and a white light shaking phenomenon is observed. Then turn off the heating current and press the spray button at the same time to obtain a continuous amorphous alloy strip; the strip width is 1.26mm and the thickness is 24μm.

[0151] Step 4: Cut the amorphous alloy strip prepared in Step 3 into strips approximately 75 mm long, wrap them in tin foil, and place them into the quartz tube of a tubular annealing furnace. First, evacuate to a low vacuum of 5 Pa, then evacuate to a high vacuum of 5.0 × 10⁻⁶ Pa. -3 Pa; Set the heating program of the heat treatment furnace in advance. After the temperature inside the furnace reaches the preset temperature (540℃) and remains stable, push the quartz tube into the tube furnace and start calculating the holding time at the same time; after holding for 10 minutes, take out the quartz tube and quench it in water to room temperature to obtain the heat-treated cobalt-based amorphous soft magnetic alloy material.

[0152] Examples 4-6 and 1-3: Adjustment of annealing heat treatment process

[0153] Amorphous soft magnetic alloy strips were prepared according to steps 1-3 in Examples 1-3, and the temperatures of direct water quenching to room temperature and annealing heat treatment were adjusted to 400℃, 440℃, 480℃, 520℃ and 560℃ in each example and step 4. The properties of the obtained materials were tested and studied to understand the effect of annealing temperature on the material properties.

[0154] Adjustment of annealing heat treatment process in Comparative Example 4 and Comparative Example 3

[0155] Amorphous soft magnetic alloy strips were prepared according to steps 1-3 in Comparative Example 3. Step 4 in each example was adjusted to direct water quenching to room temperature and annealing heat treatment temperatures of 400℃, 440℃, 480℃, 520℃, and 560℃. The properties of the obtained materials were tested and studied to understand the influence of annealing temperature on the material properties.

[0156] Performance testing

[0157] Figure 1 The XRD patterns obtained by structural characterization of the alloy strips prepared in Examples 1, 2, and 3, and Comparative Examples 1 and 2, are shown using a D8 DISCOVER high-power rotating target polycrystalline X-ray diffractometer. The patterns show that all alloy materials exhibit only one broadened diffuse diffraction peak at 45 degrees, a typical amorphous diffuse scattering peak, indicating that the obtained alloy materials have a completely amorphous structure and possess excellent amorphous forming ability.

[0158] Figure 2 The figures show the coercivity and performance tests of the alloy materials in Examples 1, 2, 3, and Comparative Example 3 after annealing at different temperatures. The coercivity of the alloy materials annealed at 440℃-560℃ was all below 1 A / m, with even better results at 480-560℃. The material obtained by isothermal annealing at 540℃ achieved the lowest coercivity, all significantly better than direct quenching. The addition of elements C and M resulted in lower coercivity in the alloy materials.

[0159] Depend on Figure 2 It was found that the alloy sample reached its optimal coercivity at a heat treatment temperature of 540℃. Therefore, the initial magnetic permeability of the sample at this temperature was tested. The initial magnetic permeability testing equipment was a BH instrument (EXPH-100). Figure 3 The figure shows the coercivity and initial permeability variation curves of different samples after heat treatment at 540℃. It can be seen from the figure that the coercivity of the embodiment is significantly lower than that of the comparative example, while maintaining a higher initial permeability.

[0160] The differences between Example 1 and Comparative Example 1 show that isothermal annealing heat treatment can effectively reduce the coercivity of the alloy while increasing its initial permeability. The examples demonstrate that the addition of element M to the alloy system results in superior soft magnetic properties. Examples 1-3 show that increasing element M improves the initial permeability of the alloy to some extent, but excessive amounts should be avoided as they can degrade the magnetic properties.

[0161] Figure 4 The images shown are obtained by testing the saturation magnetic induction intensity of the alloy materials prepared in Examples 1, 2, and 3, and Comparative Examples 1 and 2 using a vibrating sample magnetometer (VSM, LakeShore: 7410). As can be seen from the images, the saturation magnetic induction intensity of the alloy materials in the examples is significantly lower than that in the comparative examples, and is below 0.5T, while maintaining a high aspect ratio. This indicates that the alloy composition in this invention can effectively improve the soft magnetic properties of the alloy material, and the low saturation magnetic induction intensity makes the material suitable for detecting weak currents, thus improving the sensitivity of current sensors.

[0162] The soft magnetic properties test results of the amorphous alloy materials prepared in the examples and comparative examples are summarized in Table 1-2.

[0163] Table 1: Soft magnetic properties and sensor test results of amorphous alloy materials prepared in the examples and comparative examples

[0164]

[0165] Table 2: Coercivity properties of amorphous alloy materials prepared by annealing at different temperatures in Examples 1-3 and Comparative Example 3

[0166]

[0167]

[0168] Figure 5The image shows the potential polarization curves obtained from corrosion resistance tests of the alloy materials prepared in Examples 1, 2, 3, and Comparative Example 3 using a Chenhua CHI660E electrochemical workstation. A three-electrode system was used: a saturated calomel electrode as the reference electrode, a platinum electrode as the auxiliary electrode, and a 3.5 wt.% NaCl solution (pH = 7) as the electrolyte. In designing the experiment, we tried to make the experimental conditions as close to actual conditions as possible. Therefore, during the test, both sides of the alloy strip were immersed in the electrolyte solution as working surfaces. This design better simulates actual conditions, resulting in more accurate test results. Before the formal test, the surface of the alloy samples was first polished to remove the oxide film. Furthermore, to prevent discharge at the sharp corners of the samples, the sharp corners were wrapped with paraffin wax to ensure the smooth progress of the experiment.

[0169] The polarization curve tests show that, compared to the comparative example, the corrosion potential (Ecorr) of the alloy material in the embodiment shifts in the positive direction, with a lower corrosion current density and a higher corrosion potential, indicating a reduced corrosion rate and the appearance of a clear passivation region. These results demonstrate that the incorporation of element M in this invention endows the alloy material with excellent corrosion resistance, and the passivation film of the alloy with the passivation region can further inhibit corrosion. This excellent corrosion resistance makes the alloy material more stable during preparation and service, while also reducing the requirements for vacuum levels and lowering production costs.

[0170] Application examples

[0171] Magnetic probes were fabricated using cobalt-based amorphous soft magnetic alloy materials from Examples 1-4 and Comparative Examples 1-3. The specific process involved placing the alloy material on a frame, winding it with two turns of 0.1 mm diameter enameled wire, and welding it to the connectors at both ends to obtain the magnetic probe. This magnetic probe was applied to a fluxgate current sensor, and its accuracy was tested using a TK1000·200A DC current sensor detection device. Each sample was tested at least three times to prevent experimental errors. The test results are listed in Table 1.

[0172] The test results show that the sensor prepared using the magnetic probe of this invention has better accuracy. The embodiment is not only superior to the comparative example, but also superior to the sensor products of LEM (based on its product catalog data of 0.8%). In this invention, the soft magnetic alloy material not only optimizes the soft magnetic properties, but also broadens its application in current sensors, resulting in a significant improvement in accuracy. This is of great significance in the research on the correlation between soft magnetic alloy materials and current sensors.

[0173] The embodiments described above provide a detailed explanation of the technical solution of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, additions, or similar 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 cobalt-based amorphous soft magnetic alloy material, characterized in that, The composition of the cobalt-based amorphous soft magnetic alloy material has the following expression: Co a Fe b Mo c Si d B e C f M g In the formula, a, b, c, d, e, f, and g represent the atomic percentage content of the corresponding components, where 50≤a≤70, 2≤b≤8, 0.5≤c≤5, 10≤d≤20, 10≤e≤20, 0.01≤f≤0.5, 0.1≤g≤5, and a+b+c+d+e+f+g = 100; M is at least one of Cr and Mn. The preparation method of the cobalt-based amorphous soft magnetic alloy material includes the following steps: Step 1: Weigh out each element raw material according to the alloy composition and then melt it into a master alloy ingot; Step 2: The master alloy ingot is processed into amorphous soft magnetic alloy strips or wires; Step 3: Annealing heat treatment of amorphous soft magnetic alloy strips or wires to obtain the cobalt-based amorphous soft magnetic alloy material; In step 3, the annealing heat treatment is carried out under vacuum conditions at a constant temperature of 400-560 ℃ for 10-60 min.

2. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The atomic percentage of Co in the cobalt-based amorphous soft magnetic alloy material is 60 ≤ a ≤ 70.

3. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The atomic percentage of Fe in the cobalt-based amorphous soft magnetic alloy material is 3 ≤ b ≤ 5.

4. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The atomic percentage of Mo in the cobalt-based amorphous soft magnetic alloy material is 0.5 ≤ c ≤ 3.

5. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The atomic percentage of Si in the cobalt-based amorphous soft magnetic alloy material is 14 ≤ d ≤ 17.

6. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The atomic percentage of B in the cobalt-based amorphous soft magnetic alloy material is 10 ≤ e ≤ 15.

7. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The atomic percentage of C in the cobalt-based amorphous soft magnetic alloy material is 0.01 ≤ f ≤ 0.

3.

8. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is 0.1 ≤ g ≤ 3.

5.

9. The cobalt-based amorphous soft magnetic alloy material according to claim 1 or 8, characterized in that, The atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is 0.5 ≤ g ≤ 3.

10. The cobalt-based amorphous soft magnetic alloy material according to claim 1 or 8, characterized in that, The atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is 0.5 ≤ g ≤ 2.

11. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The total atomic percentage of Co and Fe in the cobalt-based amorphous soft magnetic alloy material is 65 ≤ a + b ≤ 75.

12. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The purity of the Fe, Co, Mo, B, Si, C and M raw materials is all above 99 wt.%.

13. The cobalt-based amorphous soft magnetic alloy material according to claim 1, characterized in that, The saturation magnetic induction intensity of the cobalt-based amorphous soft magnetic alloy material is below 0.5 T, and the coercivity is below 1 A / m.

14. The method for preparing cobalt-based amorphous soft magnetic alloy material according to any one of claims 1-13, characterized in that, Including the following steps: Step 1: Weigh out each element raw material according to the alloy composition and then melt it into a master alloy ingot; Step 2: The master alloy ingot is processed into amorphous soft magnetic alloy strips or wires; Step 3: Annealing heat treatment of amorphous soft magnetic alloy strips or wires to obtain the cobalt-based amorphous soft magnetic alloy material.

15. The method for preparing cobalt-based amorphous soft magnetic alloy material according to claim 14, characterized in that, Step 2 involves preparing amorphous soft magnetic alloy strips or wires using at least one of the following methods: single-roll rapid quenching, double-roll rapid quenching, inner-circle water spinning, and glass-coated spinning.

16. The method for preparing cobalt-based amorphous soft magnetic alloy material according to claim 14, characterized in that, In step 2, the amorphous soft magnetic alloy strip or wire is prepared by single-roll rapid quenching or inner-circle water spinning.

17. The method for preparing cobalt-based amorphous soft magnetic alloy material according to claim 14 or 15, characterized in that, When the method for preparing amorphous soft magnetic alloy strips or wires in step 2 is single-roll rapid quenching, the process parameters of single-roll rapid quenching are: spray pressure of 0.01-0.03 MPa and copper roller rotation speed of 3000-5000 r / min.

18. The method for preparing cobalt-based amorphous soft magnetic alloy material according to claim 14 or 15, characterized in that, When the method for preparing amorphous soft magnetic alloy strips or wires in step 2 is the inner circular water spinning method, the process parameters of the inner circular water spinning method are: spray pressure of 0.3-0.5 MPa and copper roller rotation speed of 1000-1400 r / min.

19. The method for preparing cobalt-based amorphous soft magnetic alloy material according to claim 14, characterized in that, In step 2, the strip width is 1-1.3 mm and the thickness is 18-25 μm; the wire diameter is 80-120 μm.

20. A magnetic probe, characterized in that, Includes the cobalt-based amorphous soft magnetic alloy material as described in any one of claims 1-13.

21. The magnetic probe according to claim 20 is used to manufacture sensors, electronic inductive devices, or current transformers.

Images