Fe-based nanocrystalline alloy material and preparation method and application thereof

Abstract

The invention relates to a Fe-based nanocrystalline alloy material and a preparation method and application thereof, and belongs to the technical field of nanocrystalline alloy materials. The invention provides a Fe-based nanocrystalline alloy material, the atomic percentage expression of the Fe-based nanocrystalline alloy material is FexGdyBz, x is the atomic content corresponding to the Fe element, and x is greater than or equal to 82 and less than or equal to 87; y is the atom content corresponding to the Gd element, and 0.5 < = y < = 3; z is the atom content corresponding to the element B, and z is greater than or equal to 12 and less than or equal to 16; x + y + z is equal to 100. After the Gd element is added, the coercive force of the Fe-based nanocrystalline alloy material can be further reduced, the saturation magnetization of the Fe-based nanocrystalline alloy material is improved, and the Fe-based nanocrystalline alloy material with excellent soft magnetic performance and high iron content is obtained. It is found that the contents of Fe, Gd and B elements have a certain relation, and under the specific contents, the soft magnetic performance of the Fe-based nanocrystalline alloy material can be improved.

Description

Technical Field

[0001] This invention relates to the field of nanocrystalline alloy materials technology, and in particular to an Fe-based nanocrystalline alloy material, its preparation method, and its application. Background Technology

[0002] Fe-based nanocrystalline alloys are a class of soft magnetic materials with excellent soft magnetic properties, including high saturation flux density (Bs), permeability (μ), resistivity (ρ), low high-frequency core loss (W), near-zero magnetostriction, and low coercivity (Hc). Their overall performance far surpasses that of silicon steel, ferrites, and permalloys. Therefore, Fe-based nanocrystalline alloys have found wide application as attractive core materials in high-frequency transformers, switch-mode power supplies, and motor stators / rotors.

[0003] In the 1990s, Yoshizawa et al. in Japan developed the first Fe-based nanocrystalline alloy, which they named Finemt alloy, with Fe as its main component. 73.5 Si 13.5 B9Cu1Nb3 exhibits significantly improved overall magnetic properties compared to its original amorphous state. However, the saturation magnetic induction (Bs) of typical finemet-type nanocrystalline alloys is far lower than that of silicon steel, which is detrimental to the miniaturization of power electronic devices and equipment. Japanese researchers, including Suzuki, successfully developed the Nanoperm alloy, with the composition Fe-MB (M = Zr, Nb, Hf). The Nanoperm alloy further improves Bs and reduces noise when used as a magnetic core. However, the Nanoperm alloy contains easily oxidizable elements such as Zr and Hf, requiring a high vacuum level during preparation, and its raw material costs are high, making it unsuitable for large-scale use. Based on the Nanoperm alloy, Willard prepared a Hitperm-type nanocrystalline alloy by partially replacing Fe with Co, with the composition (Fe, Co)-(Nb, Zr, Hf)-B-Cu, thereby increasing the alloy's Bs and significantly raising its Curie temperature. However, the cost of raw materials containing Co is relatively high, and Hitperm alloys also contain easily oxidized and expensive elements such as Zr and Hf, which are not conducive to commercial use and competition.

[0004] Currently, there are two main methods for preparing Fe-based nanocrystalline alloys: (1) obtaining amorphous precursor alloys through rapid quenching, vapor deposition, etc., followed by annealing and crystallization treatment to precipitate fine-sized and dispersed nanoparticles on the amorphous matrix; (2) directly obtaining nanocrystals through rapid quenching of metal melts. This method has strict requirements on the cleanliness and cooling rate of the melt, and must ensure that there are no impurities in the melt that generate heterogeneous nucleation. It can save the preparation process of nanocrystals, saving time and cost, and is therefore favored by the academic community. Component diversity is one of the important ways to improve the soft magnetic properties of Fe-based nanocrystalline alloys. By improving the composition of Fe-based nanocrystalline alloys, it is expected that excellent soft magnetic materials can be obtained while simplifying the preparation process, thus promoting the development and application of Fe-based nanocrystalline alloys. Therefore, it is necessary to further improve the composition of Fe-based nanocrystalline alloys to further enhance their soft magnetic properties. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide an Fe-based nanocrystalline alloy material, its preparation method, and its application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides an Fe-based nanocrystalline alloy material, wherein the atomic percentage expression of the Fe-based nanocrystalline alloy material is: Fe x Gd y B z Where x is the atomic content of Fe, 82≤x≤87; y is the atomic content of Gd, 0.5≤y≤3; z is the atomic content of B, 12≤z≤16; and x+y+z=100.

[0007] This invention adds Gd to the Fe-B alloy system to obtain Fe-based nanocrystalline alloy materials with high iron content and excellent soft magnetic properties.

[0008] Furthermore, in the Fe-based nanocrystalline alloy material, 85.5 ≤ x ≤ 86.3.

[0009] Furthermore, in the Fe-based nanocrystalline alloy material, 0.72 ≤ y ≤ 1.52.

[0010] Furthermore, in the Fe-based nanocrystalline alloy material, 12.5 ≤ z ≤ 13.5.

[0011] Furthermore, in the Fe-based nanocrystalline alloy material, x = 87.02 - y. At this point, z = 12.98.

[0012] Preferably, the atomic percentage expression of the Fe-based nanocrystalline alloy material is Fe 86.30 Gd0.72 B 12.98 Its coercivity is 30.29 A / m and its saturation magnetization is 1.64 T.

[0013] Preferably, the atomic percentage expression of the Fe-based nanocrystalline alloy material is Fe 85.90 Gd 1.12 B 12.98 Its coercivity is 21.25 A / m and its saturation magnetization is 1.58 T.

[0014] Preferably, the atomic percentage expression of the Fe-based nanocrystalline alloy material is Fe 85.50 Gd 1.52 B 12.98 Its coercivity is 18.68 A / m and its saturation magnetization is 1.55 T.

[0015] Furthermore, the thickness of the Fe-based nanocrystalline alloy material is 18–22 μm.

[0016] Furthermore, the thickness of the Fe-based nanocrystalline alloy material is 20 μm.

[0017] Secondly, the present invention provides a method for preparing the Fe-based nanocrystalline alloy material, comprising the following steps: S1: According to the stoichiometric ratio of the Fe-based nanocrystalline alloy material, the elemental raw materials are placed in the order of lower melting point to lower melting point and higher melting point to higher melting point. After vacuuming, inert gas is introduced and electric arc melting is carried out to form an alloy ingot. S2: The alloy ingot from step S1 is placed in the quartz tube of a high-vacuum single-roller quenching system. After evacuation, an inert gas is introduced to melt the alloy ingot from step S1 into alloy droplets, which are then dropped onto a copper roller and cooled to form the Fe-based nanocrystalline alloy material.

[0018] Further, in step S1 or S2, the inert gas is selected from at least one of argon, nitrogen, and helium.

[0019] Furthermore, in step S1 or S2, the inert gas is selected from argon.

[0020] Furthermore, in step S1 or S2, the purity of the inert gas introduced is 99.95–99.99 wt%.

[0021] Furthermore, in step S1 or S2, the purity of the inert gas introduced is 99.99 wt%.

[0022] Further, in step S1 or S2, a vacuum is drawn until the pressure is 3.5 × 10⁻⁶. -3 ~5×10 -3 Pa.

[0023] Furthermore, in step S1 or S2, a vacuum is drawn until the pressure reaches 3.5 × 10⁻⁶. -3 Pa.

[0024] Further, in step S1, an inert gas is introduced until the pressure is -0.08 to 0.03 MPa.

[0025] Furthermore, in step S1, an inert gas is introduced until the pressure is -0.08 MPa.

[0026] Furthermore, in step S1, the elemental raw materials are ultrasonically cleaned in petroleum ether and anhydrous ethanol in sequence before use.

[0027] Furthermore, in step S1, the smelting current is 200-500A.

[0028] Furthermore, in step S1, the melting current is 450A.

[0029] Further, in step S1, the raw materials are smelted until all the elemental raw materials have melted to form an alloy ingot, cooled, the alloy ingot is flipped over, smelted again and magnetically stirred.

[0030] Furthermore, in step S1, the electric arc melting is repeated 5 to 10 times.

[0031] Furthermore, in step S1, the electric arc melting is repeated 6 times.

[0032] Furthermore, in step S2, the rotational speed of the copper roller is 3200–3400 r / min.

[0033] Furthermore, in step S2, the rotational speed of the copper roller is 3300 r / min.

[0034] Further, in step S2, an inert gas is introduced until the pressure is 350-400 mbar.

[0035] Furthermore, in step S2, an inert gas is introduced until the pressure reaches 400 mbar.

[0036] Furthermore, in step S2, the alloy ingot is first melted under a current of 200-300A, and then completely melted under a current of 400-500A.

[0037] Furthermore, in step S2, the alloy ingot is first melted under a current of 300A, and then completely melted under a current of 450A.

[0038] Thirdly, the present invention provides the application of the Fe-based nanocrystalline alloy material in the preparation of magnetic materials, such as transformers and sensors.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention adds other elements to the Fe-B nanocrystalline alloy system to prepare Fe-based nanocrystalline alloy materials. It was found that the addition of Gd element can further reduce the coercivity of Fe-based nanocrystalline alloy materials and increase their saturation magnetization, thus obtaining Fe-based nanocrystalline alloy materials with high iron content and excellent soft magnetic properties.

[0040] 2. This invention discovers that the contents of Fe, Gd and B elements in the prepared Fe-based nanocrystalline alloy material are related. If the contents of each element are too high or too low, a high-iron-content Fe-based nanocrystalline alloy material with excellent soft magnetic properties cannot be obtained. Only at specific contents can the soft magnetic properties of the Fe-based nanocrystalline alloy material be improved. Attached Figure Description

[0041] Figure 1 For the embodiments 1 to 3 of the present invention (Fe) 86.30 Gd 0.72 B 12.98 Fe 85.90 Gd 1.12 B 12.98 Fe 85.50 Gd 1.52 B 12.98 ) and Comparative Example 2 (Fe 85.10 Gd 1.92 B 12.98 X-ray diffraction images of Fe-based nanocrystalline alloy materials prepared by [the study / process]. Figure 2 Examples 1-3 of the present invention (Fe) 86.30 Gd 0.72 B 12.98 Fe 85.90 Gd 1.12 B 12.98 Fe 85.50 Gd 1.52 B 12.98 ) and Comparative Example 2 (Fe 85.10 Gd 1.92 B 12.98 The saturation magnetization curve of the Fe-based nanocrystalline alloy material prepared by [the study / process]. Figure 3 Comparative Examples 1-4 of this invention (Fe) 87 B 13 Fe 85.10 Gd 1.92 B 12.98 Fe 83 Gd2B 15 Fe 83 Dy2B 15The saturation magnetization curve of the Fe-based nanocrystalline alloy material prepared by [the experiment]. Detailed Implementation

[0042] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments. Unless otherwise specified, other materials and reagents used in the embodiments are commercially available.

[0043] Example 1 1. A high-iron-content Fe-based nanocrystalline alloy material with excellent soft magnetic properties, containing Fe, Gd, and B elements, with the atomic percentage expression being Fe 86.30 Gd 0.72 B 12.98 The thickness is 20μm.

[0044] 2. The atomic percentage expression is Fe 86.30 Gd 0.72 B 12.98 Preparation method of Fe-based nanocrystalline alloy materials.

[0045] Step (1): Using Fe, Gd, and B elements with a purity of not less than 99.9% as raw materials, according to the atomic percentage expression, Fe 86.30 Gd 0.72 B 12.98 The elemental ratios (atomic ratios) were determined by weighing Fe, Gd, and B elements, with Fe 95 g, Gd 2.23 g, and B 2.77 g. The raw materials of each element were then ultrasonically cleaned in petroleum ether and anhydrous ethanol in sequence to obtain the cleaned raw materials of each element.

[0046] Step (2): Place the elemental raw materials cleaned in step (1) into a copper crucible in the order of lowest melting point to highest melting point, and evacuate the furnace until the pressure inside the furnace reaches 3.5 × 10⁻⁶. -3 Pa, then high-purity argon gas with a purity of 99.99 wt% is introduced as a protective gas until the pressure inside the furnace reaches -0.08 MPa, and then electric arc melting is carried out with a melting current of 450 A. After all the alloy is melted to form an alloy ingot, it is cooled, the alloy ingot is flipped, and melted again with magnetic stirring. The above method is repeated 6 times to obtain the alloy ingot.

[0047] Step (3): The alloy ingot prepared in step (2) is placed in the quartz tube of a high-vacuum single-roller quenching system. After evacuation, high-purity argon gas with a purity of 99.99 wt% is introduced until the pressure reaches 400 mbar. The alloy ingot is first melted under a current of 300 A, and then completely melted under a current of 450 A to obtain alloy droplets. The alloy droplets are dropped onto a copper roller rotating rapidly at 3300 r / min and cooled to form an alloy with the atomic percentage expression Fe. 86.30Gd 0.72 B 12.98 Fe-based nanocrystalline alloy materials.

[0048] 3. X-ray diffraction analysis like Figure 1 As shown, Fe 86.30 Gd 0.72 B 12.98 Fe-based nanocrystalline structure.

[0049] Example 2 1. A high-iron-content Fe-based nanocrystalline alloy material with excellent soft magnetic properties, containing Fe, Gd, and B elements, with the atomic percentage expression being Fe 85.90 Gd 1.12 B 12.98 The thickness is 20μm.

[0050] 2. The atomic percentage expression is Fe 85.90 Gd 1.12 B 12.98 Preparation method of Fe-based nanocrystalline alloy materials.

[0051] The preparation method differs from Example 1 in that the atomic percentage expression for the Fe-based nanocrystalline alloy material is: Fe 85.90 Gd 1.12 B 12.98 The composition was 93.81 g of Fe, 3.44 g of Gd, and 2.74 g of B, with the others being the same.

[0052] 3. X-ray diffraction analysis like Figure 1 As shown, Fe 85.90 Gd 1.12 B 12.98 Fe-based nanocrystalline structure.

[0053] Example 3 1. A high-iron-content Fe-based nanocrystalline alloy material with excellent soft magnetic properties, containing Fe, Gd, and B elements, with the atomic percentage expression being Fe 85.50 Gd 1.52 B 12.98 The thickness is 20μm.

[0054] 2. The atomic percentage expression is Fe 85.50 Gd 1.52 B 12.98 Preparation method of Fe-based nanocrystalline alloy materials.

[0055] The preparation method differs from Example 1 in that the atomic percentage expression for the Fe-based nanocrystalline alloy material is: Fe 85.50 Gd1.52 B 12.98 The composition was 92.64 g of Fe, 4.64 g of Gd, and 2.72 g of B, with the others being the same.

[0056] 3. X-ray diffraction analysis like Figure 1 As shown, Fe 85.50 Gd 1.52 B 12.98 Fe-based nanocrystalline structure.

[0057] Comparative Example 1 1. A high-iron-content Fe-based nanocrystalline alloy material, containing Fe and B elements, with the atomic percentage expression being Fe 87 B 13 The thickness is 20μm.

[0058] 2. The atomic percentage expression is Fe 87 B 13 Preparation method of Fe-based nanocrystalline alloy materials.

[0059] The preparation method differs from Example 1 in that the atomic percentage expression for the Fe-based nanocrystalline alloy material is: Fe 87 B 13 The composition was 97.19 g of Fe, 2.81 g of B, and the rest were the same.

[0060] Comparative Example 2 1. A high-iron-content Fe-based nanocrystalline alloy material, containing Fe, Gd, and B elements, with the atomic percentage expression being: Fe 85.10 Gd 1.92 B 12.98 The thickness is 20μm.

[0061] 2. The atomic percentage expression is Fe 85.10 Gd 1.92 B 12.98 Preparation method of Fe-based nanocrystalline alloy materials.

[0062] The preparation method differs from Example 1 in that the atomic percentage expression for the Fe-based nanocrystalline alloy material is: Fe 85.10 Gd 1.92 B 12.98 The composition was 91.49 g of Fe, 5.81 g of Gd, and 2.7 g of B, with the others being the same.

[0063] 3. X-ray diffraction analysis like Figure 1 As shown, Fe 85.10 Gd 1.92 B 12.98Fe-based nanocrystalline structure.

[0064] Comparative Example 3 1. A high-iron-content Fe-based nanocrystalline alloy material, containing Fe, Gd, and B elements, with the atomic percentage expression being: Fe 83 Gd2B 15 The thickness is 20μm.

[0065] 2. The atomic percentage expression is Fe 83 Gd2B 15 Preparation method of Fe-based nanocrystalline alloy materials.

[0066] The preparation method differs from Example 1 in that the atomic percentage expression for the Fe-based nanocrystalline alloy material is: Fe 83 Gd2B 15 The composition was 90.68 g of Fe, 6.15 g of Gd, and 3.17 g of B, with the others being the same.

[0067] Comparative Example 4 1. A high-iron-content Fe-based nanocrystalline alloy material, containing Fe, Dy, and B elements, with the atomic percentage expression being Fe 83 Dy2B 15 The thickness is 20μm.

[0068] 2. The atomic percentage expression is Fe 83 Dy2B 15 Preparation method of Fe-based nanocrystalline alloy materials.

[0069] The preparation method differs from Example 1 in that the atomic percentage expression for the Fe-based nanocrystalline alloy material is: Fe 83 Dy2B 15 The composition was 90.49 g of Fe, 6.34 g of Dy, and 3.17 g of B, with the others being the same.

[0070] Performance testing The Fe-based nanocrystalline alloy materials prepared in Examples 1-3 and Comparative Examples 1-4 were used as test samples. A vibrating sample magnetometer (VSM) was used for testing. By vibrating the sample in the coil, an alternating signal was induced in the detection coil. The alternating voltage was proportional to the magnetic moment of the sample. The measured hysteresis loop was analyzed and calculated to obtain the coercivity and saturation magnetization of the test sample.

[0071] In Example 1, the atomic percentage expression is Fe. 86.30 Gd 0.72 B 12.98 The Fe-based nanocrystalline alloy material has a saturation magnetization (Ms) of 1.64 T and a coercivity (Hc) of 30.29 A / m.

[0072] Example 2: Atomic percentage expression for Fe 85.90 Gd 1.12 B 12.98 The Fe-based nanocrystalline alloy material has a saturation magnetization (Ms) of 1.58 T and a coercivity (Hc) of 21.25 A / m.

[0073] Example 3: Atomic percentage expression for Fe 85.50 Gd 1.52 B 12.98 The Fe-based nanocrystalline alloy material has a saturation magnetization (Ms) of 1.55T and a coercivity (Hc) of 18.68A / m.

[0074] Comparative Example 1: Atomic percentage expression for Fe 87 B 13 The Fe-based nanocrystalline alloy material has a saturation magnetization (Ms) of 1.55T and a coercivity (Hc) of 32.17A / m.

[0075] Comparative Example 2: Atomic percentage expression for Fe 85.10 Gd 1.92 B 12.98 The Fe-based nanocrystalline alloy material has a saturation magnetization (Ms) of 1.50 T and a coercivity (Hc) of 14.06 A / m.

[0076] Comparative Example 3: Atomic Percentage Expression for Fe 83 Gd2B 15 The Fe-based nanocrystalline alloy material has a saturation magnetization (Ms) of 1.51 T and a coercivity (Hc) of 28.37 A / m.

[0077] Comparative Example 4: Atomic Percentage Expression for Fe 83 Dy2B 15 The Fe-based nanocrystalline alloy material has a saturation magnetization (Ms) of 1.53 T and a coercivity (Hc) of 24.81 A / m.

[0078] As can be seen from the above results, compared with Comparative Example 1, the addition of Gd element to Fe-B alloy significantly changed the soft magnetic properties of Fe-based nanocrystalline alloy material, significantly increased the saturation magnetization and significantly reduced the coercivity, thereby improving the soft magnetic properties of the alloy sample. This indicates that the soft magnetic properties of Examples 1-3 are superior to those of Comparative Example 1.

[0079] Comparative Example 2 further increased the Gd content, and after reducing the Fe content, the coercivity decreased, and the saturation magnetization also decreased.

[0080] Compared with Comparative Example 2 and Examples 1-3, Comparative Example 3 further increased the Gd content and reduced the Fe content. The coercivity was higher than that of Comparative Example 2, but the saturation magnetization was still low.

[0081] In Comparative Example 4, after replacing Gd with Dy, the coercivity was slightly lower than in Comparative Example 3, but the saturation magnetization was still not high.

[0082] like Figure 2 As shown, based on the above analysis, the magnetization of the Fe-based nanocrystalline alloy materials in Examples 1-3 increases sharply with the increase of the magnetic field under low magnetic field and then gradually reaches saturation, exhibiting typical soft magnetic properties, which are better than those of Comparative Example 2.

[0083] like Figure 3 As shown, based on the above analysis, the Fe-based nanocrystalline alloy materials prepared in Comparative Examples 1 to 4 cannot achieve good soft magnetic properties.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An Fe-based nanocrystalline alloy material, characterized by, The Fe-based nanocrystalline alloy material has an atomic percentage expression of Fe x Gd y B z wherein x is an atomic content corresponding to the Fe element, 82≤x≤87; y is an atomic content corresponding to the Gd element, 0.5≤y≤3; z is an atomic content corresponding to the B element, 12≤z≤16; and x+y+z=100.

2. The Fe-based nanocrystalline alloy material of claim 1, wherein, In the Fe-based nanocrystalline alloy material, 85.5≤x≤86.

3.

3. The Fe-based nanocrystalline alloy material of claim 1, wherein, In the Fe-based nanocrystalline alloy material, 0.72≤y≤1.

52.

4. The Fe-based nanocrystalline alloy material of claim 1, wherein, In the Fe-based nanocrystalline alloy material, 12.5≤z≤13.

5.

5. The Fe-based nanocrystalline alloy material of claim 1, wherein, In the Fe-based nanocrystalline alloy material, x=87.02-y.

6. The method of producing the Fe-based nanocrystalline alloy material according to any one of claims 1 to 5, characterized by, The method comprises the following steps: S1: placing the elemental substance raw materials according to the order of low melting point to high melting point in stoichiometric ratio in the Fe-based nanocrystalline alloy material, introducing inert gas after vacuumizing, and performing arc melting to form an alloy ingot; S2: placing the alloy ingot of step S1 in a quartz tube of a high-vacuum single-roller spinning-chilling system, introducing inert gas after vacuumizing, melting the alloy ingot of step S1 into alloy droplets, and dropping the alloy droplets on a copper roller to be cooled and formed into the Fe-based nanocrystalline alloy material.

7. The method for preparing the Fe-based nanocrystalline alloy material as described in claim 6, characterized in that, In step S1 or S2, the inert gas is at least one selected from argon, nitrogen and helium.

8. The method for preparing the Fe-based nanocrystalline alloy material as described in claim 6, characterized in that, In step S1 or S2, the pressure is reduced to 3.5 x 10 -3 ~ 5 x 10 -3 Pa.

9. The method for preparing the Fe-based nanocrystalline alloy material as described in claim 6, characterized in that, In step S1, the arc melting is repeated 5-10 times.

10. Use of the Fe-based nanocrystalline alloy material according to any one of claims 1-5 in preparing a magnetic material.

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