CN117867417A

CN117867417A - Cobalt-based amorphous soft magnetic alloy material, and preparation method and application thereof

Info

Publication number: CN117867417A
Application number: CN202410124915.7A
Authority: CN
Inventors: 黎嘉威; 庄妍; 潘丽宁; 牟春阳; 贺爱娜; 董亚强; 满其奎; 沈保根
Original assignee: Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2024-01-29
Filing date: 2024-01-29
Publication date: 2024-04-12

Abstract

The invention relates to the technical field of amorphous soft magnetic material preparation, and discloses a cobalt-based amorphous soft magnetic alloy material, and a preparation method and application thereof. The cobalt-based amorphous soft magnetic alloy material of the invention has the specific chemical composition of Co _a Fe _b Mo _c Si _d B _e C _f M _g Wherein a, b, c, d, e, f, g represents the atomic percent of the corresponding components: wherein a is more than or equal to 50 and less than or equal to 70,2, b is more than or equal to 8, c is more than or equal to 0.5 and less than or equal to 5, d is more than or equal to 10 and less than or equal to 20, e is more than or equal to 10 and less than or equal to 20, f is more than or equal to 0.01 and less than or equal to 0.5, g is more than or equal to 0.1 and less than or equal to 5, and a+b+c+d+e+f+g=100. The M represents at least one of the elements V, cr, mn, nb. The cobalt-based amorphous soft magnetic alloy material provided by the invention has low saturation magnetic induction intensity and low correctionThe soft magnetic performance such as the coercivity, the high rectangular ratio and the like are excellent, the corrosion resistance is good, and the preparation is easy; the magnetic probe prepared from the alloy material shows extremely high precision in sensor test, and has important significance in promoting the development of small-sized high-precision fluxgate current sensors.

Description

Cobalt-based amorphous soft magnetic alloy material, and preparation method and application thereof

Technical Field

The invention relates to the technical field of amorphous soft magnetic material preparation, in particular to a cobalt-based amorphous soft magnetic alloy material, and a preparation method and application thereof.

Background

The current sensor is a necessary measuring device for detecting the current magnitude and direction in a conductor as a necessary tool for current measurement, and plays an important role in the fields of smart grids of automatic equipment, new energy automobiles and the like. The fluxgate works through the nonlinear characteristic of the magnetic permeability of the soft magnetic material when the soft magnetic material is saturated under the excitation action, and the magnetic permeability is directly determined by the material. The higher the permeability of the material, the higher the sensitivity of the fluxgate sensor, so the choice of magnetic material is critical. With the continuous progress in the fields of 5G, new energy sources and the like, current sensors are developed towards miniaturization, integration, intellectualization and the like, so that soft magnetic materials are required to have low saturation induction, low coercive force, high rectangular ratio and high magnetic permeability.

Soft magnetic materials suitable for fluxgate sensors mainly include Fe-Ni- (Mo) permalloy, iron-based nanocrystalline alloys, and cobalt-based amorphous alloys, which all have high magnetic permeability (μ) and low coercivity (H) _c ). However, the Fe-Ni- (Mo) permalloy with high magnetic conductivity has small rectangular ratio and poor high-frequency magnetic property, and the Fe-Ni- (Mo) permalloy with high rectangular ratio has poor soft magnetic property, so that the application of the Fe-Ni- (Mo) permalloy in a current sensor is limited.

The iron-based nanocrystalline alloy represented by Fe-Si-B-Nb-Cu (Finemet) has the advantages of high saturation induction intensity, high magnetic permeability, low cost and the like, and is often applied to a current sensor in the form of a toroidal core, but is difficult to saturate, has large brittleness, does not contain corrosion-resistant elements, and is difficult to achieve miniaturization, high frequency and reliability. The cobalt-based amorphous alloy has lower saturation magnetic induction intensity and loss, and higher magnetic permeability at high frequency, so that the cobalt-based amorphous alloy is easier to saturate, has high rectangular ratio and has good high-frequency magnetic characteristics. And the addition of the corrosion-resistant element enables the alloy to be prepared and heat treated under the atmospheric or low vacuum condition, thereby greatly reducing the production cost and improving the service stability of the device under severe environment. Therefore, the cobalt-based amorphous soft magnetic alloy material is more suitable for high-precision small-sized fluxgate current sensors.

With the wide application of high-precision magnetic sensors, many students at home and abroad have developed research work on cobalt-based amorphous soft magnetic alloy materials. The German VAC company adds a small amount of Mo element on the basis of CoFeSiB, so that the alloy has better production manufacturability, but the heat treatment process is complex and the giant magneto-impedance effect is to be optimized.

Domestic scholars try to add Cr, nb, mn and other elements on the basis of CoFeSiB so as to improve the amorphous forming capability and soft magnetic performance of the alloy material at the same time, but the performance is still not ideal, and the problems such as complex process, large saturated magnetic induction intensity, low magnetic permeability, high cost and the like exist.

The Chinese patent document with publication number 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, wherein a is 0.6-0.8; x is 5-10. The amorphous alloy has good mechanical property and yield strength, the plasticity can reach 11.5%, and the plasticity of the existing cobalt-based amorphous alloy is about 2-8%. However, the material has high saturation induction intensity, is difficult to saturate, and is not suitable for a high-precision small-sized current sensor.

The Chinese patent document with publication number CN113462993A discloses a Co ₆₈ Fe _6.5 Si _12.5 B ₁₀ Nb _x Ni _3-x The cobalt-based amorphous alloy ribbon is prepared by adding Ni and Nb elements into the traditional cobalt-based amorphous CoFeSiB, so that the soft magnetic performance of the amorphous alloy is improved, and a more obvious skin effect is obtained. However, the magnetostriction coefficient is not zero, the thermal stability is to be optimized, and the addition of noble metal elements increases the preparation cost.

The Chinese patent document with publication number CN110993239A discloses Fe _a Co _b Si _c B _d Cu _e The iron-cobalt-based amorphous soft magnetic alloy material has excellent soft magnetic performance and better amorphous forming capability, and in the embodiment 1, the magnetic permeability of the material after stress relief annealing of a magnetic field is 13200 at the highest, but the coercive force of the material is 1.4A/m at the lowest, and the magnetic field heat treatment process is complex and still needs to be optimized.

The soft magnetic properties of CoFeSiB series alloys are improved to different degrees through component optimization in the patent, but the materials cannot simultaneously have the comprehensive properties of low saturation magnetic induction intensity, low coercive force, high initial magnetic permeability and the like, and the cobalt-based amorphous soft magnetic materials which can be suitable for current sensors are difficult to prepare. Therefore, the cobalt-based amorphous soft magnetic alloy material with low saturation magnetic induction, low coercivity and high initial permeability is developed, and has important significance for promoting the development of fluxgate current sensors and the popularization and application of the cobalt-based amorphous soft magnetic alloy material.

Disclosure of Invention

Aiming at the problem that the cobalt-based amorphous soft magnetic alloy material is difficult to have low saturation magnetic induction intensity, low coercive force and high initial magnetic permeability, the cobalt-based amorphous soft magnetic alloy material provided by the invention has the comprehensive properties of saturation magnetic induction intensity (Bs) below 0.5T, coercive force below 1A/m and high initial magnetic permeability by utilizing the synergistic effect of different elements.

In order to achieve the above purpose, the invention adopts the following technical scheme:

a cobalt-based amorphous soft magnetic alloy material, the cobalt-based amorphous soft magnetic alloy material composition having the following expression: co (Co) _a Fe _b Mo _c Si _d B _e C _f M _g Wherein a is,b. c, d, e, f, g the atomic percentages of the corresponding components are respectively represented, wherein a is more than or equal to 50 and less than or equal to 70,2 and less than or equal to 8, c is more than or equal to 0.5 and less than or equal to 5, d is more than or equal to 10 and less than or equal to 20, e is more than or equal to 10 and less than or equal to 20, f is more than or equal to 0.01 and less than or equal to 0.5, g is more than or equal to 0.1 and less than or equal to 5, and a+b+c+d+e+f+g=100; m is at least one of V, cr, mn, nb.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percentage of Co of 60.ltoreq.a.ltoreq.70.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of Fe of 3.ltoreq.b.ltoreq.5.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of Mo of 0.5.ltoreq.c.ltoreq.3.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of Si of 14.ltoreq.d.ltoreq.17.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of B of 10.ltoreq.e.ltoreq.15.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of C of 0.01.ltoreq.f.ltoreq.0.3.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of M of 0.1.ltoreq.g.ltoreq.3.5.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of M of 0.5.ltoreq.g.ltoreq.3, preferably 0.5.ltoreq.g.ltoreq.2.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has a total atomic percent of Co and Fe of 65.ltoreq.a+b.ltoreq.75.

In some embodiments, M is Cr and/or Mn.

In some embodiments, M is Cr.

In some embodiments, the Fe, co, mo, B, si, C and M starting materials are both above 99wt.% pure.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has a saturation induction of 0.5T or less and a coercivity of 1A/m or less.

The invention also provides a preparation method of the cobalt-based amorphous soft magnetic alloy material, which comprises the following steps:

step 1, weighing raw materials of each element according to alloy composition, and smelting the raw materials into a master alloy ingot;

step 2, preparing the master alloy ingot into an amorphous soft magnetic alloy strip or wire;

and step 3, annealing and heat-treating the amorphous soft magnetic alloy strip or wire to obtain the cobalt-based amorphous soft magnetic alloy material.

In some embodiments, preparing the amorphous soft magnetic alloy ribbon or wire in step 2 comprises at least one of a single roll rapid quenching process, a twin roll rapid quenching process, an internal round water spinning process, a glass cladding spinning process; preferably, the amorphous soft magnetic alloy strip or wire prepared in the step 2 is prepared by a single-roller rapid quenching method or an internal circular water spinning method.

In some embodiments, when the method for preparing the amorphous soft magnetic alloy strip or wire in the step 2 is a single-roll rapid quenching method, the process parameters of the single-roll rapid quenching method are as follows: the spraying pressure is 0.01-0.03MPa, and the rotating speed of the copper rod is 3000-5000r/min.

In some embodiments, when the method for preparing the amorphous soft magnetic alloy strip or wire in the step 2 is an internal circular water spinning method, the technological parameters of the internal circular water spinning method are as follows: the spraying pressure is 0.3-0.5MPa, and the rotating speed of the copper rod is 1000-1400r/min.

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

In some embodiments, the annealing heat treatment in step 3 is carried out under vacuum at a constant temperature of 400-560 ℃ for 10-60min. The vacuum condition refers to the vacuum degree in the equipment of 5.0X10 ^-3 Pa or less;

in some embodiments, the material is annealed and then water quenched to room temperature.

The invention also provides a magnetic probe which comprises the cobalt-based amorphous soft magnetic alloy material.

The invention also provides the application of the magnetic probe in preparing sensors, electronic inductance devices or current transformers, and the like, such as fluxgate current sensors, and the accuracy of the magnetic probe is tested by adopting a TK1000.200A type direct current sensor detection device, so that the obtained sensor has very high accuracy.

Compared with the prior art, the invention has the following beneficial effects:

(1) The cobalt-based amorphous soft magnetic alloy material with the specific composition has the advantages of low saturation magnetic induction intensity, low coercive force, high initial magnetic conductivity, high rectangular ratio and the like, and has excellent soft magnetic performance, high amorphous forming capability can be maintained under the condition that no P element is added, and the comprehensive performance is excellent.

(2) The cobalt-based amorphous soft magnetic alloy material also has the advantages of good corrosion resistance, long service time and high service stability, can be applied to various severe environments, and has wider adaptability.

(3) The cobalt-based amorphous soft magnetic alloy material disclosed by the invention does not contain rare earth metal elements and volatile elements, and is lower in cost and more stable in performance.

(4) The cobalt-based amorphous soft magnetic alloy material does not contain harmful substances such as cadmium, lead, mercury and the like, avoids negative effects on human health, and is more environment-friendly.

(5) The cobalt-based amorphous soft magnetic alloy material disclosed by the invention is simple in preparation process, and the material subjected to simple constant-temperature annealing heat treatment has more excellent comprehensive soft magnetic performance, does not need complicated steps such as magnetic field annealing and the like, and is beneficial to industrialized popularization and application.

(6) The magnetic probe prepared from the alloy material is applied to the fields of sensors, electronic inductance devices or current transformers, and the like, greatly improves the precision, and has important significance in promoting the development of small-sized high-precision fluxgate current sensors and other devices.

Drawings

Fig. 1 is an XRD diffraction pattern of the cobalt-based amorphous alloy material in examples 1, 2, 3 and comparative examples 1, 2.

FIG. 2 is a graph showing the coercivity change curves of cobalt-based amorphous alloy materials of examples 1, 2, and 3 and comparative example 3 at different annealing temperatures.

Fig. 3 is a graph showing the coercive force and initial permeability change curves of the cobalt-based amorphous alloy materials in examples 1, 2, and 3 and comparative examples 1 and 2.

Fig. 4 is a graph showing the saturation induction intensity change curves of the cobalt-based amorphous alloy materials prepared in examples 1, 2, and 3 and comparative examples 1 and 2.

Fig. 5 is an electrochemical curve of the cobalt-based amorphous alloy materials prepared in examples 1, 2, 3 and comparative example 3.

Detailed Description

Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.

Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention may be used to practice the present invention according to the knowledge of one skilled in the art and the description of the present invention.

The invention provides the following specific embodiments and all possible combinations between them. For the sake of brevity, only a few representative elements have been written in this application to represent all of the possible combinations of the described embodiments.

Unless defined otherwise, all technical and scientific terms used in the specification of 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 the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application.

The term "and/or," "and/or," as used herein, includes any one of two or more of the listed items in relation to each other, as well as any and all combinations of the listed items in relation to each other, including any two of the listed items in relation to each other, any more of the listed items in relation to each other, or all combinations of the listed items in relation to each other. It should be noted that, when at least three items are connected by a combination of at least two conjunctions selected from "and/or", "or/and", "and/or", it should be understood that, in this application, the technical solutions certainly include technical solutions that all use "logical and" connection, and also certainly include technical solutions that all use "logical or" connection.

For example, "a and/or B" includes three parallel schemes A, B and a+b. For another example, the technical schemes of "a, and/or B, and/or C, and/or D" include any one of A, B, C, D (i.e., the technical scheme of "logical or" connection), and also include any and all combinations of A, B, C, D, i.e., any two or three of A, B, C, D, and also include four combinations of A, B, C, D (i.e., the technical scheme of "logical and" connection).

The terms "comprising," "including," and "comprising," as used herein, are synonymous, inclusive or open-ended, and do not exclude additional, unrecited members, elements, or method steps.

In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.

In the present invention, "preferred", "better", "preferred" are merely embodiments or examples which are better described, and it should be understood that they do not limit the scope of the present invention. If there are multiple "preferences" in a solution, if there is no particular description and there is no conflict or constraint, then each "preference" is independent of the others.

In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.

In order to obtain the cobalt-based amorphous soft magnetic alloy material with low saturation magnetic induction, low coercive force and high initial magnetic permeability, a small amount of transition metal elements are added to improve the amorphous forming capability and corrosion resistance of the alloy, and the comprehensive soft magnetic performance of the alloy material is improved through isothermal annealing heat treatment.

The invention provides a cobalt-based amorphous soft magnetic alloy material, which comprises the following components in percentage by weight: co (Co) _a Fe _b Mo _c Si _d B _e C _f M _g Wherein a, b, c, d, e, f, g represents the atomic percentage of the corresponding components, wherein a is more than or equal to 50 and less than or equal to 70,2 and less than or equal to 8, c is more than or equal to 0.5 and less than or equal to 5, d is more than or equal to 10 and less than or equal to 20, e is more than or equal to 10 and less than or equal to 20, f is more than or equal to 0.01 and less than or equal to 0.5, g is more than or equal to 0.1 and less than or equal to 5, and a+b+c+d+e+f+g=100; m is one of V, cr, mn, nb.

The invention takes CoFeSiB material as research basis, improves the soft magnetic property of the material by using a small amount of Mo, and adds a small amount of transition metal to improve the corrosion resistance and physical property of the material, but reduces the permeability of the material part due to the addition of the transition metal and reduces the amorphous forming capability. The inventor finds that the amorphous soft magnetic alloy with the composition can have low saturation magnetic induction intensity, low coercive force and high initial magnetic permeability, and also has excellent corrosion resistance and oxidation resistance, and the comprehensive performance reaches the global center level.

Amorphous soft magnetic alloy refers to an alloy in which atoms are arranged in a non-long order and have excellent soft magnetic characteristics, and cobalt-based amorphous soft magnetic alloy refers to a cobalt-based alloy having an amorphous structure and excellent soft magnetic properties, and generally co—ni-B system and co—fe-B system. The Co-Fe-B system is specially designed in the invention, the main component is CoFeSiB, and the Co content is highest.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percentage of Co of 60.ltoreq.a.ltoreq.70. Such as the values 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 therebetween; in some embodiments, preferably, 62.ltoreq.a.ltoreq.67.5; further preferably, 63.ltoreq.a.ltoreq.67; still more preferably, 64.ltoreq.a.ltoreq.66.5; the cobalt-based amorphous alloy has lower saturation magnetic induction intensity and loss, and higher magnetic permeability at high frequency, so that the cobalt-based amorphous alloy is easier to saturate, has high rectangular ratio and has good high-frequency magnetic characteristics.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of Fe of 3.ltoreq.b.ltoreq.5. Such as a value of 3.25, 3.5, 3.75, 4, 4.25, 4.5, 4.75, or any value therebetween; in some embodiments, preferably, 3.5.ltoreq.b.ltoreq.4.5; further preferably, b is 3.ltoreq.b.ltoreq.4; the proper iron content can reduce the coercive force of the amorphous alloy, and improve the magnetic permeability and the saturation induction intensity, thereby improving the soft magnetic performance.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of Mo of 0.5.ltoreq.c.ltoreq.3. Such as values of 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 therebetween; in some embodiments, preferably, 1.5.ltoreq.c.ltoreq.2.5; further preferably, c is 1.ltoreq.c.ltoreq.2; the addition of Mo can reduce the saturation magnetic induction intensity of the material to a certain extent, reduce the vacuum degree requirement of the sprayed strip or wire and the oxidation phenomenon caused by the vacuum degree in the heat treatment process, but the addition of noble metals also increases the cost of raw materials.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of Si of 14.ltoreq.d.ltoreq.17. Such as the values 14.25, 14.5, 14.75, 15, 15.25, 15.5, 15.75, 16, 16.25, 16.5, 16.75, or any value therebetween; in some embodiments, preferably, 14.5.ltoreq.d.ltoreq.16.5; further preferably, d is 15.ltoreq.d.ltoreq.16; the Si element can lower the melting point of the amorphous alloy, thereby more easily forming an amorphous structure during rapid cooling or rapid solidification. In addition, the Si element can change the viscosity of the alloy, further promote amorphous formation and improve the amorphous forming capability of the alloy.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of B of 10.ltoreq.e.ltoreq.15. Such as the values 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or any value therebetween; in some embodiments, preferably, 10.ltoreq.d.ltoreq.14; more preferably, d is 10.ltoreq.d.ltoreq.13.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of C of 0.01.ltoreq.f.ltoreq.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 therebetween; in some embodiments, preferably, 0.05.ltoreq.f.ltoreq.0.2; further preferably, f is more than or equal to 0.05 and less than or equal to 0.15; more preferably, f is more than or equal to 0.05 and less than or equal to 0.1; the addition of C can improve the soft magnetic performance to a certain extent, and the oxidation resistance and corrosion resistance of the material can be prevented from being influenced in the range.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an atomic percent of M of 0.1.ltoreq.g.ltoreq.3.5. Such as 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 therebetween; in the invention, a small amount of transition metal is used for improving the corrosion resistance of the material so as to adapt to more application environments, and in some embodiments, the atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is more than or equal to 0.5 and less than or equal to 3, and preferably more than or equal to 0.5 and less than or equal to 2. The soft magnetic property of the material is better in the range, and the amorphous forming capability of the whole material is strong. Further preferably 0.55.ltoreq.g.ltoreq.1.5. The amorphous forming ability, corrosion resistance and oxidation resistance in this range are all excellent. Too much may result in a decrease in amorphous properties of the material and loss of permeability.

In some embodiments, M is Cr and/or Mn. Compared with other elements, the addition of Cr and/or Mn enables the alloy material to have more excellent amorphous forming capability, zero magnetostriction coefficient, excellent soft magnetic performance at high temperature and improved corrosion resistance. Further, when the Mn concentration is low, since Mn atoms replace part of Fe atoms, a MnFe alloy is formed, which helps to reduce the resistance of the magnetic domain wall, thereby reducing the coercive force.

In some embodiments, the Fe, co, mo, B, si, C and M starting materials are both above 99wt.% pure. Preferably, the purity of all the starting materials is above 99.5 wt.%.

The cobalt-based amorphous soft magnetic alloy material has the advantages of low saturation magnetic induction intensity, low coercive force, high initial magnetic conductivity, high rectangular ratio and the like, and has excellent soft magnetic performance.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has a saturation induction of less than 0.5T and can achieve a coercivity of less than 1A/m at the same time. Preferably, for example, the saturation induction is below 0.48T, below 0.45T and below 0.4T; the coercive force is 0.9A/m or less, 0.95A/m or less, 0.8 5A/m or less, 0.8A/m or less, and 0.78A/m or less.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an initial magnetic permeability of 25000 or more, preferably 25500 or more, 26000 or more, 26500 or more, 27000 or more, 27500 or more, 27600 or more.

In some embodiments, further, the cobalt-based amorphous soft magnetic alloy material has an initial magnetic permeability of 25000 to 30000, a saturation induction of 0.1 to 0.5T, and a coercivity of 0.3 to 1A/m.

In some embodiments, the cobalt-based amorphous soft magnetic alloy material has an initial magnetic permeability of 27000 to 30000, a saturation induction of 0.2 to 0.5T, and a coercivity of 0.4 to 1A/m.

The amorphous soft magnetic alloy material can be obtained by adopting simple smelting, preparing strips or wires and then carrying out constant-temperature thermal annealing treatment, does not need complex and complicated technical processes, does not need to add a magnetic field during annealing, and is beneficial to rapidly promoting industrial production and application.

In some embodiments, in step 1, the amount of each element is calculated according to the alloy composition, and then the element is weighed, wherein the error range of the weighing is within 0.0005 g; to avoid operating errors affecting material properties.

In some embodiments, step 1, when melting a master alloy ingot, comprises the steps of: placing the weighed alloy raw materials into a smelting device, and smelting in an inert atmosphere; preserving heat for 5-20 minutes after melting, and then pouring the melted alloy ingot into a placed copper mold to be cooled for more than 30 minutes to obtain a master alloy ingot;

the method of melting the pure metal is arbitrary, and there is a method of melting the pure metal by, for example, vacuum-pumping in a chamber and then heating at high frequency. In addition, the master alloy and the resulting soft magnetic alloy typically become the same composition.

In some embodiments, the raw material is heated and melted to obtain a molten metal (molten metal). The temperature of the molten metal is not particularly limited, and may be, for example, 1300 to 1500 ℃ in terms of melting all the raw materials.

Preferably, the smelting process is performed 1-3 times to ensure a uniform distribution of the components in each alloy ingot.

In some embodiments, preparing the amorphous soft magnetic alloy ribbon or wire in step 2 includes, but is not limited to, at least one of a single roll rapid quench process, a twin roll rapid quench process, an internal round water spinning process, a glass cladding spinning process, and the like; can also adopt a single-roller melt-spinning method,

Preferably, the amorphous soft magnetic alloy strip or wire prepared in the step 2 is prepared by a single-roller rapid quenching method or an internal circular water spinning method.

The single-roller quick quenching method is to melt cast ingot and cast the cast ingot onto the surface of a rotating water-cooled copper roller, and the cast ingot is quickly cooled to obtain amorphous to microcrystalline thin strips.

In some embodiments, when the method for preparing the amorphous soft magnetic alloy strip or wire in the step 2 is a single-roll rapid quenching method, the process parameters of the single-roll rapid quenching method are as follows: the spraying pressure is 0.01-0.03MPa, and the rotating speed of the copper rod is 3000-5000r/min. In some embodiments, the process parameters of the preferred single roll rapid quench process are: the spraying pressure is 0.01-0.03MPa, and the rotating speed of the copper rod is 3500-4500r/min.

Preferably, the single-roller rapid quenching method comprises the following technological parameters: the spraying pressure is 0.02MPa, and the rotating speed of the copper rod is 4000r/min.

In some embodiments, the single roll rapid quenching method for preparing amorphous soft magnetic alloy strips or wires specifically comprises the steps of: crushing a master alloy ingot, and then placing the crushed master alloy ingot into a quartz tube with a nozzle at the bottom, wherein the aperture of the nozzle is 0.7-0.8 mm; and putting the quartz tube into a melt-spinning machine to melt alloy ingots in the quartz tube for the second time, and preparing a continuous alloy amorphous strip by adopting a single-roller rapid quenching method.

Further, the method for preparing the amorphous soft magnetic alloy strip or wire by the single-roller rapid quenching method specifically comprises the following steps: crushing a master alloy ingot, then placing the crushed master alloy ingot into a quartz tube with a nozzle with the aperture of 0.75-0.8mm reserved at the bottom, and adjusting the upper and lower positions of the quartz tube to control the distance between the nozzle and the roll surface to be 0.1-0.4mm; vacuumizing to below 0.02Pa, regulating the pressure difference between the inside and the outside of the quartz tube to be 0.01-0.03MPa, adopting a single-roller rapid quenching and melt-spinning process, and melt-spinning at a speed of 30-50m/s under the protection of argon, namely setting the rotating speed of a copper rod to be 3000-5000r/min, switching on heating current, and when a solenoid heats and melts a master alloy ingot to be completely melted and a white light-emitting shaking phenomenon is observed, closing the heating current and simultaneously pressing a spray button to obtain a continuous amorphous alloy strip;

the inner circle water spinning method is that after metal, metal and nonmetal mixture and metal alloy are heated to a molten state, the molten metal is evenly sprayed into cooled water through an inner circle water basin rotating at a high speed to form amorphous wires;

In some embodiments, the method for preparing the amorphous soft magnetic alloy strip or wire by the internal circular water spinning method specifically comprises the following steps: the master alloy ingot is crushed and then put into a quartz tube with holes at the bottom, and the aperture is 5-10 mu m thicker than the wire. The copper roller (the rotating speed is 1000-1400 r/min) is started, water is added to form a water film, and the thickness of the water mill is 15-20mm.

Then, the quartz tube is put into a high-frequency induction coil to perform secondary smelting on the alloy ingot. The inner circle water spinning method is adopted to pressurize the top of the quartz tube to enable the alloy jet flow to enter a water film, the pressure is 0.3-0.5MPa, and amorphous alloy wires are formed before the alloy jet flow is broken into liquid drops. Preferably, the spraying pressure is 0.45MPa, and the rotating speed of the copper rod is 1200r/min when the internal circle water spinning method is adopted.

In some embodiments, the width of the web in step 2 is 1.1mm, 1.15mm, 1.2mm, 1.25mm, or any value therebetween, and the thickness is 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, or any value therebetween.

In some embodiments, the annealing heat treatment in step 3 is maintained at a constant temperature of 440-560 ℃ under vacuum for 10-60min. Such as 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, or any value therebetween. The treatment time can be 10min, 12min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, or any value therebetween.

Preferably, the treatment time is 10 to 30min, more preferably 10 to 20min. The amorphous alloy material can achieve excellent soft magnetic performance after annealing heat treatment in a short time, the process flow time is short, and the industrialized popularization cost is lower.

DSC tests of the cobalt-based amorphous alloy material of the present invention show that the crystallization temperature is about 560-580 ℃, and in some embodiments, the crystallization temperature of the material is about 565-575 ℃. The temperature of the annealing heat treatment should be within this temperature range, and in some embodiments is preferably constant temperature treatment at 400-560 ℃; further preferably 440 to 560 ℃, further preferably at 480 to 540 ℃. It is difficult to achieve rearrangement of amorphous structure at too low a temperature, and too high a temperature causes melting of the alloy material.

The annealing heat treatment is isothermal annealing heat treatment, namely, a program of a tubular heat treatment furnace is set according to a preset temperature, and after the temperature in the furnace reaches the preset temperature and the vacuum degree of a quartz tube is reduced below a target value, the quartz tube filled with alloy strips or wires is rapidly pushed into the middle part of the tubular heat treatment furnace, and meanwhile, the heat preservation time is calculated;

in some embodiments, the material is annealed and then water quenched to room temperature. The amorphous alloy is cooled quickly to ensure that the amorphous structure inside the material is not changed, namely, the alloy with high temperature is cooled quickly into water, so that the alloy reaches a supercooled state instantly, and the amorphous alloy is formed. Supercooled liquids are formed when the alloy cools fast enough. The molecular or atomic arrangement in supercooled liquids is disordered and there is no fixed lattice structure. In this case, if the supercooled liquid is subjected to an appropriate disturbance such as mechanical vibration or thermal fluctuation, structural relaxation may occur to form an amorphous alloy. In the water quenching process, the liquid alloy is easy to be disturbed to form an amorphous structure in a supercooled state.

The invention also provides the magnetic probe which is used for preparing a sensor, an electronic inductance device or a current transformer. If the method is applied to preparing a fluxgate current sensor, the precision of the fluxgate current sensor is tested by adopting a TK1000.200A type direct current sensor detection device. The magnetic probe prepared from the alloy material shows extremely high precision in sensor test, and has important significance in promoting the development of small-sized high-precision fluxgate current sensors.

The raw materials used in the following embodiments are all commercially available.

Example 1

In this embodiment, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co ₆₆ Fe ₄ ) _68.9 Mo ₂ Si ₁₆ B ₁₂ C _0.1 Cr ₁ The specific preparation method of the alloy material comprises the following steps:

step 1: the raw material Co, fe, mo, si, B, C, cr with the purity of more than 99.5 percent is prepared according to the composition relation (Co ₆₆ Fe ₄ ) _68.9 Mo ₂ Si ₁₆ B ₁₂ C _0.1 Cr ₁ Batching, wherein the weighing error is controlled within 0.0005 g;

step 2: and (3) placing the proportioned raw materials into an alumina crucible in a cleaned induction smelting furnace, vacuumizing to be lower than-0.002 Pa, and carrying out induction smelting in an argon atmosphere. After melting, preserving heat for more than 10 minutes, then pouring the melted alloy ingot into a copper mold, and cooling for 25 minutes along with a furnace to obtain a mother alloy ingot with uniform components;

Step 3: crushing the master alloy ingot obtained in the step 2, and then placing the crushed master alloy ingot into a quartz tube with a nozzle of about 0.8mm left at the bottom, and adjusting the upper and lower positions of the quartz tube to control the distance between the nozzle and the roll surface to be about 0.25 mm; vacuumizing to less than 0.02Pa, regulating the pressure difference between the inside and the outside of the quartz tube to be 0.02MPa, adopting a single-roller rapid quenching and melt-spinning process, and melt-spinning at a speed of 40m/s under the protection of argon, namely setting the rotating speed of a copper rod to be 4000r/min, switching on heating current, and when a solenoid heats and melts a master alloy ingot to be completely melted and a white light-emitting shaking phenomenon is observed, switching off the heating current and simultaneously pressing a spray button to obtain a continuous amorphous alloy strip; the width of the strip was 1.26mm and the thickness was 23. Mu.m.

Step 4: cutting the amorphous alloy strip prepared in the step 3 into strips with the length of about 75mm, wrapping the strips with tinfoil paper, then placing the strips into a quartz tube of a tube annealing furnace, firstly pumping low vacuum to 5Pa, and then pumping high vacuum to 5.0X10 ^-3 Pa; setting a heating program of a heat treatment furnace in advance, pushing a quartz tube into the tube furnace after the temperature in the furnace reaches a preset temperature (540 ℃) and is kept stable, and simultaneously starting to calculate the heat preservation time; and (3) after preserving heat for 10 minutes, taking out the quartz tube, and carrying out water quenching to room temperature to obtain the cobalt-based amorphous soft magnetic alloy material after heat treatment.

Example 2

In this embodiment, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co ₆₆ Fe ₄ ) _67.9 Mo ₂ Si ₁₆ B ₁₂ C _0.1 Cr ₂ The specific preparation method of the alloy material comprises the following steps:

step 1: proportioning raw materials Co, fe, mo, si, B, C, cr with purity of more than 99.5% according to a molecular formula of the materials, and controlling weighing error within 0.0005 g;

step 3: crushing the master alloy ingot obtained in the step 2, and then placing the crushed master alloy ingot into a quartz tube with a nozzle of about 0.8mm left at the bottom, and adjusting the upper and lower positions of the quartz tube to control the distance between the nozzle and the roll surface to be about 0.25 mm; vacuumizing to less than 0.02Pa, regulating the pressure difference between the inside and the outside of the quartz tube to be 0.02MPa, adopting a single-roller rapid quenching and melt-spinning process, and melt-spinning at a speed of 40m/s under the protection of argon, namely setting the rotating speed of a copper rod to be 4000r/min, switching on heating current, and when a solenoid heats and melts a master alloy ingot to be completely melted and a white light-emitting shaking phenomenon is observed, switching off the heating current and simultaneously pressing a spray button to obtain a continuous amorphous alloy strip; the width of the strip was 1.28mm and the thickness was 24. Mu.m.

Example 3

In this embodiment, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co ₆₆ Fe ₄ ) _66.9 Mo ₂ Si ₁₆ B ₁₂ C _0.1 Cr ₃ The preparation method comprises the following steps:

step 3: crushing the master alloy ingot obtained in the step 2, and then placing the crushed master alloy ingot into a quartz tube with a nozzle of about 0.8mm left at the bottom, and adjusting the upper and lower positions of the quartz tube to control the distance between the nozzle and the roll surface to be about 0.25 mm; vacuumizing to less than 0.02Pa, regulating the pressure difference between the inside and the outside of the quartz tube to be 0.02MPa, adopting a single-roller rapid quenching and melt-spinning process, and melt-spinning at a speed of 40m/s under the protection of argon, namely setting the rotating speed of a copper rod to be 4000r/min, switching on heating current, and when a solenoid heats and melts a master alloy ingot to be completely melted and a white light-emitting shaking phenomenon is observed, switching off the heating current and simultaneously pressing a spray button to obtain a continuous amorphous alloy strip; the width is 1.19mm and the thickness is 23 μm.

Example 4

In this embodiment, the molecular formula of the cobalt-based amorphous soft magnetic alloy material is (Co ₆₆ Fe ₄ ) _67.9 Mo ₂ Si ₁₆ B ₁₂ C _0.1 Cr ₁ Mn ₁ The specific preparation method of the alloy material comprises the following steps:

step 1: proportioning raw materials Co, fe, mo, si, B, C, cr, mn with purity of more than 99.5% according to a molecular formula of the materials, and controlling weighing error within 0.0005 g;

Step 3: crushing the master alloy ingot obtained in the step 2, and then placing the crushed master alloy ingot into a quartz tube with a nozzle of about 0.8mm left at the bottom, and adjusting the upper and lower positions of the quartz tube to control the distance between the nozzle and the roll surface to be about 0.25 mm; vacuumizing to less than 0.02Pa, regulating the pressure difference between the inside and the outside of the quartz tube to be 0.02MPa, adopting a single-roller rapid quenching and melt-spinning process, and melt-spinning at a speed of 40m/s under the protection of argon, namely setting the rotating speed of a copper rod to be 4000r/min, switching on heating current, and when a solenoid heats and melts a master alloy ingot to be completely melted and a white light-emitting shaking phenomenon is observed, switching off the heating current and simultaneously pressing a spray button to obtain a continuous amorphous alloy strip; the width is 1.25mm and the thickness is 25 μm.

Comparative example 1

In this comparative example, the molecular formula of the cobalt-based amorphous soft magnetic alloy material was (Co ₆₆ Fe ₄ ) _68.9 Mo ₂ Si ₁₆ B ₁₂ C _0.1 The specific preparation method of the Cr alloy material comprises the following steps:

step 1: proportioning raw materials Co, fe, mo, si, B, C, cr with purity more than 99.5% according to a material molecular formula, wherein the weighing error is controlled within 0.0005 g;

step 3: crushing the master alloy ingot obtained in the step 2, and then placing the crushed master alloy ingot into a quartz tube with a nozzle of about 0.8mm left at the bottom, and adjusting the upper and lower positions of the quartz tube to control the distance between the nozzle and the roll surface to be about 0.25 mm; vacuumizing to less than 0.02Pa, regulating the pressure difference between the inside and the outside of the quartz tube to be 0.02MPa, adopting a single-roller rapid quenching and melt-spinning process, and melt-spinning at a speed of 40m/s under the protection of argon, namely setting the rotating speed of a copper rod to be 4000r/min, switching on heating current, and when a solenoid heats and melts a master alloy ingot to be completely melted and a white light-emitting shaking phenomenon is observed, switching off the heating current and simultaneously pressing a spray button to obtain a continuous amorphous alloy strip; the width was 1.27mm and the thickness was 22. Mu.m.

Comparative example 2

The molecular formula (Co) was prepared by the method of reference example 1 _68.15 Fe _4.35 ) _71.5 Si _12.5 B ₁₅ Cr ₁ The specific preparation method of the cobalt-based amorphous soft magnetic alloy material is as follows:

step 1: proportioning raw materials Co, fe, si, B, cr with purity of more than 99.5% according to a molecular formula of the materials, and controlling weighing error within 0.0005 g;

step 3: crushing the master alloy ingot obtained in the step 2, and then placing the crushed master alloy ingot into a quartz tube with a nozzle of about 0.8mm left at the bottom, and adjusting the upper and lower positions of the quartz tube to control the distance between the nozzle and the roll surface to be about 0.25 mm; vacuumizing to less than 0.02Pa, regulating the pressure difference between the inside and the outside of the quartz tube to be 0.02MPa, adopting a single-roller rapid quenching and melt-spinning process, and melt-spinning at a speed of 40m/s under the protection of argon, namely setting the rotating speed of a copper rod to be 4000r/min, switching on heating current, and when a solenoid heats and melts a master alloy ingot to be completely melted and a white light-emitting shaking phenomenon is observed, switching off the heating current and simultaneously pressing a spray button to obtain a continuous amorphous alloy strip; the width is 1.30mm and the thickness is 25 μm.

Comparative example 3

Preparation of Co according to the method of example 1 ₆₆ Fe ₄ Mo ₂ Si ₁₆ B ₁₂ The specific preparation method of the cobalt-based amorphous soft magnetic alloy material is as follows:

step 1: proportioning raw materials Co, fe, mo, si, B with purity of more than 99.5% according to a molecular formula of the materials, and controlling weighing error within 0.0005 g;

Step 3: crushing the master alloy ingot obtained in the step 2, and then placing the crushed master alloy ingot into a quartz tube with a nozzle of about 0.8mm left at the bottom, and adjusting the upper and lower positions of the quartz tube to control the distance between the nozzle and the roll surface to be about 0.25 mm; vacuumizing to less than 0.02Pa, regulating the pressure difference between the inside and the outside of the quartz tube to be 0.02MPa, adopting a single-roller rapid quenching and melt-spinning process, and melt-spinning at a speed of 40m/s under the protection of argon, namely setting the rotating speed of a copper rod to be 4000r/min, switching on heating current, and when a solenoid heats and melts a master alloy ingot to be completely melted and a white light-emitting shaking phenomenon is observed, switching off the heating current and simultaneously pressing a spray button to obtain a continuous amorphous alloy strip; the width of the strip was 1.26mm and the thickness was 24. Mu.m.

Examples 4-6 examples 1-3 annealing Heat treatment Process adjustment

Amorphous soft magnetic alloy strips are prepared according to steps 1-3 in examples 1-3, and the effects of annealing temperature on material properties are known by adjusting the temperature of the direct water quenching to room temperature and the annealing heat treatment temperature to 400 ℃, 440 ℃, 480 ℃, 520 ℃, 560 ℃ and performing test study on the properties of the obtained materials in each of examples and step 4.

Comparative example 4 comparative example 3 annealing heat treatment process adjustment

Amorphous soft magnetic alloy strips were prepared according to steps 1-3 of comparative example 3, and each of examples and step 4 was adjusted to be directly water quenched to room temperature and annealing heat treatment temperature of 400 ℃, 440 ℃, 480 ℃, 520 ℃, 560 ℃ and the properties of the obtained material were tested and studied to understand the effect of annealing temperature on the properties of the material.

Performance testing

FIG. 1 shows XRD patterns obtained by structural characterization of the alloy strips prepared in examples 1, 2 and 3 and comparative examples 1 and 2 using a D8 DISCOVER high power rotary target polycrystalline X-ray diffractometer. As can be seen from the graph, all alloy materials only have a widened dispersion diffraction peak at 45 degrees, which is a typical amorphous diffuse scattering peak, and the obtained alloy materials are of a completely amorphous structure and have excellent amorphous forming capability.

FIG. 2 shows coercivity and performance tests of the alloy materials of examples 1, 2, 3 and comparative example 3 after annealing at different temperatures. The coercivity of the alloy material obtained by annealing at 440-560 ℃ is lower than 1A/m, the effect is more excellent at 480-560 ℃, and the material obtained by constant-temperature annealing at 540 ℃ reaches the lowest coercivity and is far better than direct quenching cooling. The addition of elements C and M enables the alloy material to have lower coercivity.

As can be seen from fig. 2, the alloy sample reached the optimal coercivity at the 540 ℃ heat treatment temperature, and thus the initial permeability test was performed on the sample at that temperature. The initial permeability test equipment is a B-H meter (EXPH-100), and FIG. 3 shows the coercivity and initial permeability change curves of different samples under the heat treatment of 540 ℃. As can be seen from the figure, the coercivity of the examples is significantly lower than the comparative examples while maintaining a higher initial permeability.

From the difference between example 1 and comparative example 1, it can be seen that the isothermal annealing heat treatment can effectively reduce the coercive force of the alloy while improving the initial permeability. The embodiment can reduce the coercive force and keep higher initial magnetic permeability at the same time, which shows that the addition of the element M in the alloy system ensures that the alloy material obtains more excellent soft magnetic performance. Examples 1-3 show that the increase in element M results in a certain increase in the initial permeability of the alloy material, but that it is not desirable to overdose it, otherwise the magnetic properties would deteriorate. .

FIG. 4 shows images of the alloy materials prepared in examples 1, 2, 3 and comparative examples 1, 2 as measured by saturation induction using a vibrating sample magnetometer (VSM, vibrating Sample Magnetometer, lake Shore: 7410). As can be seen from the graph, the saturation induction of the alloy material of the example is significantly lower than that of the comparative example and lower than 0.5T, while maintaining a high rectangular ratio. The alloy composition can effectively improve the soft magnetic performance of the alloy material, and the low saturation induction intensity enables the material to be suitable for the field of weak current detection, and improves the sensitivity of a current sensor.

The results of the soft magnetic property test of the amorphous alloy materials prepared in examples and comparative examples are summarized in tables 1 to 2.

Table 1: soft magnetic properties and sensor test results of amorphous alloy materials prepared in examples and comparative examples

Table 2: examples 1-3 and comparative example 3 coercivity properties of amorphous alloy materials prepared by annealing at different temperatures

FIG. 5 shows potential polarization curves of corrosion resistance tests of the alloy materials prepared in examples 1, 2, 3 and comparative example 3 using Chenhua CHI660E electrochemical workstation. The experiment used a three electrode system, the reference electrode was a saturated calomel electrode, the auxiliary electrode was a platinum electrode, and the electrolyte solution was 3.5wt.% NaCl solution (ph=7). In the experimental design, we brought the experimental conditions as close to the actual conditions as possible. Thus, during the test, both sides of the alloy strip were immersed in the electrolyte solution as working surfaces. The design can better simulate the actual situation, so that the test result obtained by us is more accurate. Before the official test, we first need to polish the surface of the alloy sample to remove the oxide film on the surface. In addition, in order to prevent the discharge at the sharp corner of the sample, we wrapped the sharp corner with paraffin to ensure the smooth performance of the experiment.

As can be seen from the results of the polarization curve test, compared with the comparative example, the corrosion potential (Ecorr) of the alloy material of the example was shifted in the positive direction, the corrosion current density was smaller, the corrosion potential was higher, indicating that the corrosion rate was decreased, and a significant passivation zone occurred. The above results show that the alloy material has good corrosion resistance due to the doping of the element M, and the passivation film of the alloy with the passivation section can further prevent corrosion. The good corrosion resistance ensures that the alloy material is more stable in the preparation and service processes, simultaneously reduces the requirement on vacuum degree and reduces the production cost.

Application example

Magnetic probes were prepared using cobalt-based amorphous soft magnetic alloy materials of examples 1-4 and comparative examples 1-3. The specific process is that the alloy material is placed on the framework, and the two windings inside and outside the enameled wire with the diameter of 0.1mm are adopted and welded on the joints at the two ends, so as to obtain the magnetic probe. The magnetic probe is applied to a fluxgate current sensor, and an accuracy test is carried out by adopting a TK1000.200A type direct current sensor detection device. Each sample was tested repeatedly three more times to prevent experimental error and the test results are listed in table 1.

As can be seen from the test results, the sensor prepared by the magnetic probe has better precision, and the embodiment is not only superior to the comparative example, but also superior to LEM company sensor products (based on 0.8% of the product volume data). The soft magnetic alloy material provided by the invention has the advantages that the soft magnetic property is optimized, the application of the soft magnetic alloy material in a current sensor is widened, the precision is greatly improved, and the soft magnetic alloy material is significant in the research on the relevance between the soft magnetic alloy material and the current sensor.

While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.

Claims

1. The cobalt-based amorphous soft magnetic alloy material is characterized by comprising the following components in percentage by weight: co (Co) _a Fe _b Mo _c Si _d B _e C _f M _g Wherein a, b, cD, e, f, g represent the atomic percentages of the corresponding components, wherein a is more than or equal to 50 and less than or equal to 70,2 and less than or equal to 8, c is more than or equal to 0.5 and less than or equal to 5, d is more than or equal to 10 and less than or equal to 20, e is more than or equal to 10 and less than or equal to 20, f is more than or equal to 0.01 and less than or equal to 0.5, g is more than or equal to 0.1 and less than or equal to 5, and a+b+c+d+e+f+g=100; m is at least one of V, cr, mn, nb.

2. The cobalt-based amorphous soft magnetic alloy material according to claim 1, wherein the cobalt-based amorphous soft magnetic alloy material has an atomic percentage of Co of 60-70.

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

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

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

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

7. The cobalt-based amorphous soft magnetic alloy material according to claim 1, wherein the atomic percentage of C in the cobalt-based amorphous soft magnetic alloy material is 0.01.ltoreq.f.ltoreq.0.3.

8. The cobalt-based amorphous soft magnetic alloy material according to claim 1, wherein the atomic percentage of M in the cobalt-based amorphous soft magnetic alloy material is 0.1-3.5.

9. 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 0.5-3, preferably 0.5-2.

10. The cobalt-based amorphous soft magnetic alloy material according to claim 1, wherein the total content of Co and Fe in atomic percent in the cobalt-based amorphous soft magnetic alloy material is 65-75.

11. Cobalt-based amorphous soft magnetic alloy material according to claim 1, wherein M is Cr and/or Mn.

12. The cobalt-based amorphous soft magnetic alloy material according to claim 1 or 11, wherein M is Cr.

13. The cobalt-based amorphous soft magnetic alloy material according to claim 1, wherein the purity of both the Fe, co, mo, B, si, C and M raw materials is 99wt.% or more.

14. The cobalt-based amorphous soft magnetic alloy material according to claim 1, wherein the cobalt-based amorphous soft magnetic alloy material has a saturation induction of 0.5T or less and a coercive force of 1A/m or less.

15. The method for producing a cobalt-based amorphous soft magnetic alloy material according to any one of claims 1 to 14, comprising the steps of:

16. The method of preparing a cobalt-based amorphous soft magnetic alloy material according to claim 15, wherein the preparing an amorphous soft magnetic alloy strip or wire in step 2 comprises at least one of a single-roll rapid quenching method, a twin-roll rapid quenching method, an internal round water spinning method, and a glass cladding spinning method; preferably, the amorphous soft magnetic alloy strip or wire prepared in the step 2 is prepared by a single-roller rapid quenching method or an internal circular water spinning method.

17. The method for preparing a cobalt-based amorphous soft magnetic alloy material according to claim 15 or 16, wherein when the method for preparing the amorphous soft magnetic alloy strip or wire in the step 2 is a single-roll rapid quenching method, the technological parameters of the single-roll rapid quenching method are as follows: the spraying pressure is 0.01-0.03MPa, and the rotating speed of the copper rod is 3000-5000r/min.

18. The method for preparing cobalt-based amorphous soft magnetic alloy material according to claim 15 or 16, wherein when the method for preparing amorphous soft magnetic alloy strip or wire in step 2 is an internal circular water spinning method, the process parameters of the internal circular water spinning method are as follows: the spraying pressure is 0.3-0.5MPa, and the rotating speed of the copper rod is 1000-1400r/min.

19. The method for producing cobalt-based amorphous soft magnetic alloy material according to claim 15, wherein the width of the strip in step 2 is 1-1.3mm and the thickness is 18-25 μm; the diameter of the wire is 80-120 mu m.

20. The method for preparing a cobalt-based amorphous soft magnetic alloy material according to claim 15, wherein the annealing heat treatment in step 3 is performed under vacuum at 400-560 ℃ for 10-60min.

21. A magnetic probe comprising the cobalt-based amorphous soft magnetic alloy material of any one of claims 1 to 14.

22. The magnetic probe of claim 21 for use in preparing a sensor, an electronic inductance device or a current transformer.