FeBC series amorphous alloy with high soft magnetic performance and preparation method and application of FeBC series amorphous alloy

Abstract

The invention belongs to the field of materials, and particularly relates to a FeBC series amorphous alloy with high soft magnetic performance and a preparation method and application thereof, the expression is FeaBbCcXd, X in the expression is one of Ge, C, Si and Sn, and a, b, c and d are atomic percent contents of corresponding components and meet the following conditions that the sum of a, b, c and d is 100, 81 < = a < = 85, 8 < = b < = 10, 5 < = c < = 7 and 1.5 < = d < = 2.5. Compared with the prior art, the alloy has good alloy soft magnetic performance and mechanical performance, the amorphous forming ability is high, the preparation process is simple, no additional heat treatment technology is needed, and industrial production is better facilitated.

Description

Technical Field

[0001] The invention belongs to the technical field of materials, and in particular relates to a FeBC-based amorphous alloy with high soft magnetic properties, and a preparation method and application thereof. Background Art

[0002] Compared with traditional silicon steel, iron-based amorphous alloys have lower coercivity and core loss. Therefore, iron-based amorphous strips are widely used in magnetic devices such as transformers, motors and sensors. However, compared with traditional soft magnetic materials, iron-based amorphous strips have relatively low saturation magnetization. For example, 1K101 (Fe 78 SiC 13 ) The saturation magnetization of amorphous strip is 1.56 T, which is much lower than the saturation magnetization of silicon steel (2.01 T), limiting its commercial application and further development.

[0003] In order to improve the saturation magnetization of iron-based amorphous alloy strips, the most common method is to heat-treat the iron-based amorphous strips to obtain nanocrystals. For example, Chinese patent CN110093565B discloses a heat treatment method to obtain an iron-based nanocrystalline alloy strip with a saturation magnetization of 1.73-1.81 T. However, the heat treatment process of crystallization annealing is not easy to control. When the temperature is too low, nanocrystals will not be generated. When the temperature is too high, large-sized grains are easily formed, causing the soft magnetic properties to deteriorate rapidly. At the same time, the redundant heat treatment process will also increase its production cost.

[0004] In addition, due to the low elastic modulus and hardness of iron-based amorphous alloys, their mechanical properties are relatively poor. Therefore, it is necessary to design an iron-based amorphous alloy with high saturation magnetization and explore a method to improve its mechanical properties to expand its application scenarios. Summary of the invention

[0005] In order to solve the above-mentioned deficiencies in the art, a FeBC-based amorphous alloy material with excellent soft magnetic properties (high saturation magnetization and low coercive force) was invented without using a subsequent heat treatment process.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a FeBC-based amorphous alloy with high soft magnetic properties, characterized in that the expression of the FeBC-based amorphous alloy is Fe a B b C c X d, in which X is one of Ge, C, Si, and Sn, a, b, c, and d are the atomic percentage contents of the corresponding components, and the following conditions are satisfied: the sum of a, b, c, and d is 100, and 81≤a≤85, 8≤b≤10, 5≤c≤7, and 1.5≤d≤2.5.

[0008] As a preferred technical solution of the present invention, a is 83, b is 9, c is 6, and d is 2, that is, the expression of the FeBC-based amorphous alloy is Fe 83 B9C6X2, wherein X is one of Ge, C, Si, and Sn.

[0009] As a preferred technical solution of the present invention, the saturation magnetization intensity of the FeBC-based amorphous alloy is greater than 1.70T.

[0010] As a preferred technical solution of the present invention, the coercive force of the FeBC-based amorphous alloy is 9 to 13 A / m.

[0011] As a preferred technical solution of the present invention, the Young's modulus of the FeBC-based amorphous alloy is 130-155 GPa, and the hardness is 10-11 GPa.

[0012] On the other hand, the present invention provides a method for preparing the above-mentioned FeBC-based amorphous alloy strip with high soft magnetic properties, comprising the following steps:

[0013] (1) converting the atomic percentage of the FeBC-based amorphous alloy into mass percentage and weighing the raw materials according to the mass percentage for batching, wherein the purity of the raw materials should be higher than 99%;

[0014] (2) using a vacuum arc furnace to heat the ingredients to about 1500 degrees Celsius under vacuum or inert atmosphere protection to melt them and repeatedly smelt them by cooling with cooling water to obtain Fe a B b C c X d of master alloy ingot;

[0015] (3) The master alloy ingot is placed in a quartz tube with a nozzle at the bottom, and heated and melted under an induction coil, so that the rotation speed of the copper roller is maintained at 4000 r / min, the linear speed is 45 m / s, and the pressure difference is 0.13 MPa. When the master alloy ingot is melted into liquid, it is sprayed onto the copper roller of a vacuum belt spinning machine to obtain a FeBC-based amorphous alloy strip with a width of 1 to 3 mm and a thickness of 20 to 30 μm.

[0016] As a preferred technical solution of the present invention, in the batching step, B is added in the form of Fe-B alloy.

[0017] In a third aspect, the present invention provides the application of the above-mentioned FeBC-based amorphous alloy strip with high soft magnetic properties in the field of magnetic devices.

[0018] By adopting the above technical solution, the beneficial effects of the present invention are:

[0019] (1) The FeBC alloy strip provided by the present invention has excellent soft magnetic properties, a saturation magnetization of 1.71 to 1.76 T, and a coercive force of 9 to 13 A / m.

[0020] (2) The FeBC alloy strip provided by the present invention has excellent mechanical properties, a Young's modulus of 130 to 155 GPa, and a hardness of 10 to 11 GPa.

[0021] (3) The present invention has found a way to simultaneously improve the soft magnetic properties and mechanical properties of the alloy, namely, doping the alloy with 2 at.% of Group IV elements, especially Ge.

[0022] (4) The iron-based amorphous alloy strip provided by the present invention has strong amorphous forming ability, does not contain precious metals and high melting point metal elements, has low raw material cost, and has a simple preparation process without additional heat treatment process, which is more conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0024] Figure 1 The Cu target K-ray XRD diagram of the master alloy ingots obtained in Example 1, Example 2, Example 3, and Example 4 of the present invention.

[0025] Figure 2 TEM image and selected area electron diffraction pattern of the master alloy ingot prepared in Example 3 of the present invention.

[0026] Figure 3 The Cu target K-ray XRD diagrams of the alloy strips prepared in Examples 1, 2, 3 and 4 of the present invention.

[0027] Figure 4 VSM hysteresis loops of the alloy strips obtained in Examples 1, 2, 3 and 4 of the present invention.

[0028] Figure 5 These are the nanoindentation curves obtained in Example 1, Example 2, Example 3, and Example 4 of the present invention. DETAILED DESCRIPTION

[0029] It should be noted that the following detailed descriptions are all illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0030] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0031] In the following examples, the melting furnace type is a vacuum arc melting furnace (Ebmund Büehler, MAM-1). The copper roller belt spinning machine type is a vacuum belt spinning machine (SKY, SD500). The X-ray diffractometer type is XRD (Bruker D8 Advance). The transmission electron microscope type is TEM (FEITalos F200). Magnetic test: vibrating sample magnetometer (VSM, JDAW-2000D) and DC BH hysteresis loop instrument (MATS-2010SD). Nanoindentation test: Bruker nanoindentation instrument (Hysitron TI980).

[0032] The present invention will be further explained below in conjunction with the accompanying drawings and embodiments.

[0033] Example 1

[0034] The alloy's molecular formula is Fe 83 B9C8, preparation steps are as follows:

[0035] Step 1: 5 g of raw materials Fe, B, and C with a purity greater than 99 wt.% are prepared according to the molecular formula of this embodiment, wherein B is added in the form of Fe-B alloy. The main purpose of adding the Fe-B alloy is to make it easier for the B element to melt into the master alloy ingot, and to avoid melting in the form of boron monomer, which will cause arc heating of the boron monomer and easily cause boron splashing, making the composition of the alloy inaccurate and increasing the risk of splashing.

[0036] Step 2: Heat the ingredients to about 1500 degrees Celsius in a vacuum arc furnace under vacuum or argon atmosphere protection to melt them and repeatedly smelt them by cooling with cooling water to obtain Fe 83 Master alloy ingot of B9C8.

[0037] Step 3: Fill the quartz tube with a nozzle at the bottom and the chamber of the belt spinning machine with argon gas, and keep the pressure difference at 0.13MPa. Place the master alloy ingot in the quartz tube, adjust the speed of the copper roller of the belt spinning machine to 45m / s, and maintain the speed of the copper roller at 4000r / min. When the master alloy ingot is melted into liquid, spray it onto the copper roller of the vacuum belt spinning machine to obtain Fe with a width of 1-3mm and a thickness of 20-30μm. 83 B9C8 is an amorphous alloy strip.

[0038] The master alloy ingots and amorphous alloy strips prepared above were tested:

[0039] X-ray diffractometer test of master alloy ingot: The master alloy ingot prepared in step 2 is tested by diffractometer. The XRD spectrum is as follows: Figure 1 As shown in (a), it can be seen that the master alloy ingot is mainly composed of two phases: α-Fe and Fe3C.

[0040] Amorphous alloy strip X-ray diffractometer test: XRD spectrum is as follows Figure 3 As shown in , it can be seen that unlike the parent alloy ingot, the quenched alloy strip presents a broad low-intensity diffuse scattering peak at 2θ≤44°, without the presence of an obvious sharp high-intensity crystal peak, indicating that the alloy strip has an amorphous structure.

[0041] Vibrating sample magnetometer test of amorphous alloy strip: The saturation magnetization intensity B of the alloy strip is tested using a vibrating sample magnetometer. s , the results are as follows Figure 4 As shown in . It can be seen that the saturation magnetization intensity B of the alloy s It is 1.713T.

[0042] Amorphous alloy strip DC BH hysteresis loop test: DC BH hysteresis loop tester is used to test the coercive force H of alloy strip. c , we know that the coercivity H of the alloy c It is 12.97A / m.

[0043] Indentation test of amorphous alloy strip: The hardness H and Young's modulus E of the alloy strip are tested using Bruker nanoindentation instrument Y , the results are as follows Figure 5 As shown. It can be seen that the hardness H and Young's modulus E of the alloy Y They are 10.63 and 133.6 Gpa respectively.

[0044] Example 2

[0045] The alloy's molecular formula is Fe 83 B9C6Si2, the preparation method is the same as that in Example 1.

[0046] X-ray diffractometer test of master alloy ingot: The structure of the master alloy ingot is tested by diffractometer, and the XRD spectrum is as follows: Figure 1 As shown in (b), it can be seen that the master alloy ingot is mainly composed of three phases: α-Fe, Fe3C and B(Fe,Si)3. Compared with Example 1, the (200) diffraction peak intensity of the α-Fe phase at 65° is significantly increased, indicating that the trace doping of Si element makes it easier for the α-Fe phase to precipitate and grow in the alloy ingot.

[0047] Amorphous alloy strip X-ray diffractometer test: XRD spectrum is as follows Figure 3 As shown in , a nanocrystalline crystallization peak corresponding to α-Fe appears in the middle of the diffuse scattering peak, which is a typical nanocrystalline structure, indicating that trace doping of Si element will reduce its amorphous forming ability.

[0048] Vibrating sample magnetometer test of amorphous alloy strip: The saturation magnetization intensity B of the alloy strip is tested using a vibrating sample magnetometer. s , the results are as follows Figure 4 As shown in . It can be seen that the saturation magnetization intensity B of the alloy s It is 1.733T. Compared with Example 1, the saturation magnetization intensity of the alloy strip is improved.

[0049] Amorphous alloy strip DC BH hysteresis loop test: DC BH hysteresis loop tester is used to test the coercive force H of alloy strip. c , we know that the coercivity H of the alloy c It is 12.26 A / m, and the coercive force of the alloy strip is close to that of Example 1.

[0050] Indentation test of amorphous alloy strip: The hardness H and Young's modulus E of the alloy strip are tested using Bruker nanoindentation instrument Y , the results are as follows Figure 5 As shown. It can be seen that the hardness H and Young's modulus E of the alloy Y The hardness of the alloy strip is close to that of Example 1, and the Young's modulus is improved, indicating that the micro-doping of Si element can appropriately improve the mechanical properties of the alloy strip. Compared with Example 1, the saturation magnetization and Young's modulus of Example 2 are improved, but this also comes at the cost of reduced amorphous forming ability, which may be difficult to prepare in the actual production process.

[0051] Example 3

[0052] The alloy's molecular formula is Fe 83 B9C6Ge2, the preparation method is the same as that in Example 1.

[0053] X-ray diffractometer test of master alloy ingot: The structure of the master alloy ingot is tested by diffractometer, and the XRD spectrum is as follows: Figure 1 As shown in (c), it can be seen that the master alloy ingot is mainly composed of two phases, α-Fe and Fe3C. Compared with Examples 1 and 2, the (200) diffraction peak intensity of the α-Fe phase at 65° is reduced, indicating that the trace doping of Ge element makes it difficult for the α-Fe phase to grow in the alloy ingot.

[0054] The morphology and structure of the master alloy ingot prepared in step 2 were tested by transmission electron microscopy. Figure 2 As shown. 83 The B9C6Ge2 master alloy ingot is mainly composed of a gray elongated plate-like α-Fe phase with a width of about 400 nm and a relatively narrower black plate-like Fe3C phase. The Ge element is easily dispersed in the master alloy ingot without precipitating a corresponding crystal phase.

[0055] Amorphous alloy strip X-ray diffractometer test: XRD spectrum is as follows Figure 3 As shown in , the quenched alloy ribbon presents a broad low-intensity diffuse scattering peak at 2θ≈44°, without the presence of an obvious sharp high-intensity crystal peak, indicating that the alloy ribbon is an amorphous structure. 83 B9C6Ge2 alloy strip has good amorphous glass forming ability.

[0056] Vibrating sample magnetometer test of amorphous alloy strip: The saturation magnetization intensity B of the alloy strip is tested using a vibrating sample magnetometer. s , the results are as follows Figure 4 As shown in . It can be seen that the saturation magnetization intensity B of the alloy s It is 1.754T. Compared with Example 2, the saturation magnetization intensity of the alloy strip is further improved.

[0057] Amorphous alloy strip DC BH hysteresis loop test: DC BH hysteresis loop tester is used to test the coercive force H of alloy strip. c , we know that the coercivity H of the alloy c The coercive force of the alloy strip is 12.82 A / m, which is close to that of Example 1 and Example 2.

[0058] Indentation test of amorphous alloy strip: The hardness H and Young's modulus E of the alloy strip are tested using Bruker nanoindentation instrument Y , the results are as follows Figure 5 As shown. It can be seen that the hardness H and Young's modulus E of the alloy YThe hardness of the alloy strip is close to that of Example 1 and Example 2, and the Young's modulus is further improved, indicating that the trace doping of Ge element will further improve the mechanical properties of the alloy strip. Compared with Example 2, the saturation magnetization and Young's modulus of Example 3 are further improved, and it has good amorphous forming ability, maintains low coercive force and high hardness, and is easy to be prepared and used in the actual production process.

[0059] Example 4

[0060] The alloy's molecular formula is Fe 83 B9C6Sn2, the preparation method is the same as that in Example 1.

[0061] X-ray diffractometer test of master alloy ingot: The structure of the master alloy ingot is tested by diffractometer, and the XRD spectrum is as follows: Figure 1 As shown in (d), it can be seen that the master alloy ingot is mainly composed of α-Fe and Fe 23 Compared with Example 3, the (200) diffraction peak of the α-Fe phase at 65° maintains a lower intensity, indicating that the α-Fe phase is not easy to grow in the alloy ingot.

[0062] Amorphous alloy strip X-ray diffractometer test: XRD spectrum is as follows Figure 3 As shown in , the quenched alloy ribbon presents a broad low-intensity diffuse scattering peak at 2θ≈44°, without the presence of an obvious sharp high-intensity crystal peak, indicating that the alloy ribbon is an amorphous structure. 83 B9C6Sn2 alloy strip also has good amorphous forming ability.

[0063] Vibrating sample magnetometer test of amorphous alloy strip: The saturation magnetization intensity B of the alloy strip is tested using a vibrating sample magnetometer. s , the results are as follows Figure 4 As shown in . It can be seen that the saturation magnetization intensity B of the alloy s It is 1.713T, which is equal to the saturation magnetization intensity of Example 1.

[0064] Amorphous alloy strip DC BH hysteresis loop test: DC BH hysteresis loop tester is used to test the coercive force H of alloy strip. c , we know that the coercivity H of the alloy c The coercive force of the alloy strip is 9.32 A / m. The coercive force of the alloy strip is lower than those of Example 1, Example 2 and Example 3.

[0065] Indentation test of amorphous alloy strip: The hardness H and Young's modulus E of the alloy strip are tested using Bruker nanoindentation instrument Y , the results are as follows Figure 5As shown. It can be seen that the hardness H and Young's modulus E of the alloy Y The hardness of the alloy strip is close to that of Example 1, Example 2, and Example 3, and the Young's modulus is relatively high, indicating that the trace doping of Sn element will also appropriately improve the mechanical properties of the alloy strip. Compared with Example 1, Example 2 and Example 3, Example 4 has the lowest coercive force, better amorphous forming ability and mechanical properties.

[0066] Similarly, the inventors designed the following embodiments to compare the soft magnetic properties and mechanical properties, and the results are shown in the following table:

[0067] Example Chemical formula <![CDATA[B s (T)]]> <![CDATA[H c (A / m)]]> H(Gpa) <![CDATA[E Y (Gpa)]]> 1 <h2 style=";text-align:left;direction:ltr"><![CDATA[Fe <h2 style=";text-align:left;direction:ltr"> 83 <h2 style=";text-align:left;direction:ltr"> B9C8]]><h2 style=";text-align:left;direction:ltr"> 1.713 12.97 10.63 133.6 2 <h2 style=";text-align:left;direction:ltr"><![CDATA[Fe <h2 style=";text-align:left;direction:ltr"> 83 <h2 style=";text-align:left;direction:ltr"> B9C6Si2<h2 style=";text-align:left;direction:ltr"> 1.733 12.26 10.20 142.2 3 <![CDATA[Fe 83 B9C6Ge2]]> 1.754 12.82 10.65 151.5 4 <![CDATA[Fe 83 B9C6Sn2]]> 1.713 9.32 10.33 151.0 5 <![CDATA[Fe 83 B 9.5 C 7.5 ]]> 1.712 12.96 10.61 133.3 6 <![CDATA[Fe 83 B 8.5 C 8.5 ]]> 1.713 12.98 10.65 133.7 7 <![CDATA[Fe 83 B9C 6.5 And 1.5 ]]> 1.729 12.04 10.15 140.9 8 <![CDATA[Fe 83 B9C 5.5 And 2.5 ]]> 1.747 12.48 10.26 143.8 9 <![CDATA[Fe 83 B9C 6.5 Ge 1.5 ]]> 1.732 13.04 10.62 133.3 10 <![CDATA[Fe 83 B9C 5.5 Ge 2.5 ]]> 1.735 13.11 10.66 133.7 11 <![CDATA[Fe 83 B9C 6.5 Sn 1.5 ]]> 1.712 9.17 10.24 133.2 12 <![CDATA[Fe 83 B9C 5.5 Sn 2.5 ]]> 1.715 9.42 10.37 133.9

[0068] Among them, B s is the saturation magnetization, H c is the coercive force, H is the hardness, E is Y is Young's modulus.

[0069] In summary, the lower saturation magnetization of amorphous alloys is the biggest obstacle to their application. Compared with other alloy strips, Example 4 has better amorphous forming ability, the highest saturation magnetization and Young's modulus, so this alloy strip has broad application prospects.

[0070] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A FeBC-based amorphous alloy with high soft magnetic properties, characterized in that: The expression of the FeBC-based amorphous alloy is Fe a B b C c X d , in which X is one of Ge, C, Si, and Sn, a, b, c, and d are the atomic percentage contents of the corresponding components, and the following conditions are satisfied: the sum of a, b, c, and d is 100, and 81≤a≤85, 8≤b≤10, 5≤c≤7, and 1.5≤d≤2.

5.

2. The alloy according to claim 1, characterized in that a is 83, b is 9, c is 6, and d is 2, that is, the expression of the FeBC-based amorphous alloy is Fe 83 B9C6X2, wherein X is one of Ge, C, Si, and Sn.

3. The alloy according to claim 2, characterized in that The saturation magnetization of the FeBC-based amorphous alloy is greater than 1.70T.

4. The alloy according to claim 2, characterized in that The coercive force of the FeBC-based amorphous alloy is 9 to 13 A / m.

5. The alloy according to claim 2, characterized in that The Young's modulus of the FeBC-based amorphous alloy is 130-155 GPa, and the hardness is 10-11 GPa.

6. A method for preparing a FeBC-based amorphous alloy strip with high soft magnetic properties, characterized in that: The steps include: (1) converting the atomic percentage of the FeBC-based amorphous alloy into mass percentage and weighing the raw materials according to the mass percentage for batching, wherein the purity of the raw materials should be higher than 99%; (2) using a vacuum arc furnace to heat the ingredients to about 1500 degrees Celsius under vacuum or inert atmosphere protection to melt them and repeatedly smelt them by cooling with cooling water to obtain Fe a B b C c X d of master alloy ingot; (3) The master alloy ingot is placed in a quartz tube with a nozzle at the bottom, and heated and melted under an induction coil, so that the rotation speed of the copper roller is maintained at 4000 r / min, the linear speed is 45 m / s, and the pressure difference is 0.13 MPa. When the master alloy ingot is melted into liquid, it is sprayed onto the copper roller of a vacuum belt spinning machine to obtain a FeBC-based amorphous alloy strip with a width of 1 to 3 mm and a thickness of 20 to 30 μm.

7. The method according to claim 6, characterized in that In the batching step, B is added in the form of Fe-B alloy.

8. Application of the FeBC-based amorphous alloy with high soft magnetic properties as claimed in any one of claims 1 to 7 in the field of magnetic devices.

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