Iron-based amorphous nanocrystalline soft magnetic alloy material and preparation method thereof

Abstract

The invention discloses an iron-based amorphous nanocrystalline magnetically soft alloy material and a preparation method thereof, and relates to the field of iron-based amorphous nanocrystalline magnetically soft alloy materials, and the iron-based amorphous nanocrystalline magnetically soft alloy material is prepared by weighing and proportioning Fe, Si, B, Cr and alpha-Fe phases and amorphous phases according to a chemical component formula. The amorphous nanocrystalline soft magnetic alloy provided by the invention has a gradient structure, the structure of the amorphous nanocrystalline soft magnetic alloy is converted from a complete amorphous state to a complex phase structure in which an alpha-Fe phase is distributed in an amorphous phase from a copper roller surface to a free surface, and the size and the volume fraction of the alpha-Fe phase are gradually increased, so that the alloy has excellent soft magnetic performance and smaller brittleness due to the special structure; the surface quality is good and void-free, and the bending toughness is excellent; the method is very beneficial to practical application; the material has high saturation magnetization and low coercive force; the soft magnetic performance is excellent.

Description

Technical Field

[0001] The present invention relates to the field of iron-based amorphous and nanocrystalline soft magnetic alloy materials, and particularly to an iron-based amorphous and nanocrystalline soft magnetic alloy material and a preparation method thereof. Background Art

[0002] Iron-based amorphous and nanocrystalline soft magnetic alloy materials are advanced soft magnetic materials combining amorphous and nanocrystalline structures, with characteristics such as high saturation magnetic induction intensity, low coercivity, and low high-frequency loss.

[0003] In the prior art, the single-roll melt spinning method is generally used to prepare amorphous ribbons to ensure the formation of the initial amorphous structure of the material.

[0004] However, the soft magnetic properties and brittleness of iron-based amorphous and nanocrystalline soft magnetic alloy materials in the prior art still need to be improved.

[0005] Therefore, it is necessary to propose an iron-based amorphous and nanocrystalline soft magnetic alloy material and a preparation method thereof to solve the above problems. Summary of the Invention

[0006] The purpose of the present invention is to provide an iron-based amorphous and nanocrystalline soft magnetic alloy material and a preparation method thereof to solve the problems raised in the above background art.

[0007] To achieve the above purpose, the present invention provides the following technical solution: An iron-based amorphous and nanocrystalline soft magnetic alloy material, comprising:

[0008] Fe, Si, B, Cr, and the α-Fe phase and the amorphous phase are weighed and proportioned according to the chemical composition formula.

[0009] Preferably, the mass percentage purity of Fe, Si, B, Cr, and the α-Fe phase and the amorphous phase is 99.7%.

[0010] Preferably, the chemical composition formula ratio of Fe, Si, B, Cr, and the α-Fe phase and the amorphous phase is: 80.2 - 81.9, 4 - 7, 5 - 8, 1.2 - 2.0, 1 - 3, 1 - 3.

[0011] The present invention also discloses a preparation method of an iron-based amorphous and nanocrystalline soft magnetic alloy material for preparing the iron-based amorphous and nanocrystalline soft magnetic alloy material, comprising the following steps:

[0012] S101: Weigh and proportion Fe, Si, B, Cr, the α-Fe phase and the amorphous phase with a mass percentage purity of not less than 99.7% according to the chemical composition formula: Fe: 80.2 - 81.9, B: 5 - 8, stable phase α-Fe: 1 - 3, amorphous phase α-Fe: 1 - 3, Si: 4 - 7, and Cr: 1.2 - 2.0;

[0013] S102: Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.2 - 1.8 Pa, introduce nitrogen to 0.08 - 0.15 MPa, keep the melting temperature at 1300 - 1500 °C, hold for 5 - 30 min after uniform melting, and when the vacuum degree in the furnace reaches 5×10 -3 pa, remelt 3 - 8 times, and stir magnetically for 5 - 8 min each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material;

[0014] S103: Crush the master alloy material, place it in a high - vacuum single - roll spin - quenching furnace, evacuate to less than 0.6 - 1.2 Pa, introduce nitrogen and adjust the injection pressure difference to 0.06 - 0.09 MPa. After completely melting the master alloy material, spray it onto the surface of a rotating copper roll to spin - quench the master alloy material, and the obtained master alloy material has a thickness of 15 - 35 μm and a width of 1.2 - 2.1 mm.

[0015] Preferably, after obtaining the master alloy material:

[0016] Use an X - ray diffractometer and a transmission electron microscope to analyze the structure of the alloy;

[0017] Use a vibrating sample magnetometer and a DC hysteresis loop tester to measure the magnetic properties of the alloy;

[0018] Use an alloy brittleness device to determine the relative fracture strain of the alloy.

[0019] Preferably, the relative fracture strain of the master alloy material is 3.5 - 4.8%.

[0020] The technical effects and advantages of the present invention:

[0021] 1. The amorphous - nanocrystalline soft - magnetic alloy provided by the present invention has a gradient structure. From the copper - roll surface to the free surface, its structure changes from a completely amorphous state to a composite structure with α - Fe phase distributed in the amorphous phase, and the size and volume fraction of the α - Fe phase gradually increase. This special structure makes the alloy have excellent soft - magnetic properties and low brittleness; it has good surface quality without voids and excellent bending toughness; it is very helpful for practical applications; it has a high saturation magnetization intensity and a low coercivity; and its soft - magnetic properties are excellent.

[0022] 2. The preparation method of the amorphous - nanocrystalline soft - magnetic alloy provided by the present invention is simple. The master alloy can be directly made into the amorphous - nanocrystalline soft - magnetic alloy with the above - mentioned structure by the liquid - state rapid - cooling method without heat treatment, which can significantly improve production efficiency and reduce process costs, and is of great significance for the development and industrialization of nanocrystalline alloys. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a process chart of the preparation method of the iron - based amorphous - nanocrystalline soft - magnetic alloy material of the present invention. Detailed implementation mode

[0024] The present invention provides a kind of iron-based amorphous nanocrystalline soft magnetic alloy material as shown in Figure 1 and its preparation method.

[0025] Example 1:

[0026] (1) Weigh and mix Fe, Si, B, Cr, α-Fe phase and amorphous phase with a mass percentage purity of not less than 99.7% according to the chemical composition formula: Fe: 81.4, B: 7, stable phase α-Fe: 3, amorphous phase α-Fe: 3, Si: 4 and Cr: 1.6;

[0027] (2) Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.5 Pa, introduce nitrogen to 0.08 - 0.1 MPa, the melting temperature is 1300 - 1500 °C, keep warm for 5 - 10 min after melting evenly, the vacuum degree in the furnace reaches 5×10-3 Pa, melt repeatedly for 3 - 8 times, and stir magnetically for 5 - 8 min each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material;

[0028] (3) Crush the master alloy material, place it in a high-vacuum single-roll spinning quenching furnace, evacuate to less than 0.8 Pa, introduce nitrogen and adjust the injection pressure difference to 0.08 MPa, completely melt the master alloy material and then spray it onto the surface of the rotating copper roll to spin-quench the master alloy material, and the obtained master alloy material has a thickness of about 30 μm and a width of about 2.0 mm;

[0029] (4) Use an X-ray diffractometer and a transmission electron microscope to analyze the structure of the alloy; use a vibrating sample magnetometer and a DC hysteresis loop tester to measure the magnetic properties of the alloy; use an alloy brittleness device to determine the relative fracture strain (ab) of the alloy;

[0030] Among them, the smaller ab is, the smaller the strain generated before the alloy fractures and the greater the brittleness. After measurement and calculation, the ab of the master alloy material is 4.8%.

[0031] Example 2:

[0032] (1) Weigh and mix Fe, Si, B, Cr, α-Fe phase and amorphous phase with a mass percentage purity of not less than 99.7% according to the chemical composition formula: Fe: 80.2, B: 6, stable phase α-Fe: 3, amorphous phase α-Fe: 3, Si: 6 and Cr: 1.8;

[0033] (2) Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.4 Pa, introduce nitrogen to 0.05 - 0.1 MPa, the melting temperature is 1300 - 1500 °C, keep warm for 10 - 20 min after melting evenly, the vacuum degree in the furnace reaches 5×10 -3 pa, melt it repeatedly for 3 to 8 times, with magnetic stirring for 5 to 8 minutes each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material;

[0034] (3) Crush the master alloy material, place it in a high-vacuum single-roll spin quenching furnace, evacuate to less than 0.9 Pa, introduce nitrogen and adjust the injection pressure difference to 0.06 MPa. After melting the master alloy material, spray it onto the surface of the rotating copper roll to spin quench the master alloy material, and the obtained alloy has a thickness of about 35 μm and a width of about 1.5 mm;

[0035] (4) Use an X-ray diffractometer and a transmission electron microscope to analyze the structure of the alloy; use a vibrating sample magnetometer and a DC hysteresis loop instrument to measure the magnetic properties of the alloy; use an alloy brittleness device to determine the relative fracture strain (ab) of the alloy;

[0036] Among them, the smaller the ab, the smaller the strain generated before the alloy fractures and the greater the brittleness. After measurement and calculation, the ab of the master alloy material is 4.2%.

[0037] Example 3:

[0038] (1) Weigh and mix Fe, Si, B, Cr, α-Fe phase and amorphous phase with a mass percentage purity of not less than 99.7% according to the chemical composition formula: Fe: 81, B: 8, stable phase α-Fe: 1, amorphous phase α-Fe: 1, Si: 7 and Cr: 2.0;

[0039] (2) Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.3 Pa, introduce nitrogen to 0.08 MPa, the melting temperature is 1300 - 1500 °C, keep it warm for 5 minutes after melting evenly, and the vacuum degree in the furnace reaches 5×10 -3 pa, melt it repeatedly for 3 to 8 times, with magnetic stirring for 5 to 8 minutes each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material;

[0040] (3) Crush the master alloy material, place it in a high-vacuum single-roll spin quenching furnace, evacuate to less than 1.2 Pa, introduce nitrogen and adjust the injection pressure difference to 0.09 MPa. After melting the master alloy material, spray it onto the surface of the rotating copper roll to spin quench the master alloy material, and the obtained alloy has a thickness of about 15 μm and a width of about 1.2 mm;

[0041] (4) Use an X-ray diffractometer and a transmission electron microscope to analyze the structure of the alloy; use a vibrating sample magnetometer and a DC hysteresis loop instrument to measure the magnetic properties of the alloy; use an alloy brittleness device to determine the relative fracture strain (ab) of the alloy;

[0042] Among them, the smaller the ab, the smaller the strain generated before the alloy fractures and the greater the brittleness. After measurement and calculation, the ab of the master alloy material is 4.0%.

[0043] Example 4:

[0044] (1) Weigh and mix Fe, Si, B, Cr and FeC with a mass percentage purity of not less than 99.7% according to the chemical composition formula of Fe: 81.5, B: 6, stable phase α-Fe: 2, amorphous phase α-Fe: 2, Si: 4 and Cr: 1.6;

[0045] (2) Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.5 Pa, introduce nitrogen to 0.08 - 0.1 MPa, the melting temperature is 1300 - 1500 °C, keep warm for 5 - 10 min after uniform melting, the vacuum degree in the furnace reaches 5×10 - 3 Pa, melt repeatedly for 3 - 8 times, and stir magnetically for 5 - 8 min each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material;

[0046] (3) Crush the master alloy material and place it in a high-vacuum single-roll spinning quenching furnace, evacuate to less than 0.8 Pa, introduce nitrogen and adjust the injection pressure difference to 0.08 MPa, completely melt the master alloy material and then spray it onto the surface of the rotating copper roll to spin-quench the master alloy material, and the obtained master alloy material has a thickness of about 30 μm and a width of about 2.0 mm;

[0047] (4) Use an X-ray diffractometer and a transmission electron microscope to analyze the structure of the alloy; use a vibrating sample magnetometer and a DC hysteresis loop meter to measure the magnetic properties of the alloy; use an alloy brittleness device to determine the relative fracture strain (ab) of the alloy;

[0048] Among them, the smaller ab is, the smaller the strain generated before the alloy fractures and the greater the brittleness. After measurement and calculation, the ab of the master alloy material is 3.8%.

[0049] Example 5:

[0050] (1) Weigh and mix Fe, Si, B, Cr and FeC with a mass percentage purity of not less than 99.7% according to the chemical composition formula of Fe: 81.4, B: 6, stable phase α-Fe: 2.5, amorphous phase α-Fe: 2.5, Si: 4 and Cr: 1.6;

[0051] (2) Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.2 Pa, introduce nitrogen to 0.08 - 0.1 MPa, the melting temperature is 1300 - 1500 °C, keep warm for 10 - 12 min after uniform melting, the vacuum degree in the furnace reaches 5×10 - 3 Pa, melt repeatedly for 3 - 8 times, and stir magnetically for 5 - 8 min each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material;

[0052] (3) Crush the master alloy material, place it into a high-vacuum single-roll spin quenching furnace, evacuate to less than 0.9 Pa, introduce nitrogen and adjust the injection pressure difference to 0.08 MPa. After completely melting the master alloy material, spray it onto the surface of a rotating copper roll to spin quench the master alloy material. The obtained master alloy material has a thickness of about 28 μm and a width of about 1.7 mm.

[0053] (4) Use an X-ray diffractometer and a transmission electron microscope to analyze the structure of the alloy; use a vibrating sample magnetometer and a DC hysteresis loop meter to measure the magnetic properties of the alloy; use an alloy brittleness device to determine the relative fracture strain (ab) of the alloy.

[0054] Among them, the smaller the ab, the smaller the strain generated before the alloy fractures, and the greater the brittleness. After measurement and calculation, the ab of the master alloy material is 3.6%.

[0055] Example 6:

[0056] (1) Weigh and mix Fe, Si, B, Cr and FeC with a mass percentage purity of not less than 99.7% according to the chemical composition formula of Fe: 81.5, B: 7, stable phase α-Fe: 3.5, amorphous phase α-Fe: 2.5, Si: 6 and Cr: 1.2.

[0057] (2) Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.8 Pa, introduce nitrogen to 0.05 - 0.12 MPa, the melting temperature is 1300 - 1500 °C, keep warm for 15 - 30 min after melting evenly, and the vacuum degree in the furnace reaches 5×10 - 3 pa, melt repeatedly for 3 - 8 times, and stir magnetically for 5 - 8 min each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material.

[0058] (3) Crush the master alloy material, place it into a high-vacuum single-roll spin quenching furnace, evacuate to less than 0.6 Pa, introduce nitrogen and adjust the injection pressure difference to 0.09 MPa. After completely melting the master alloy material, spray it onto the surface of a rotating copper roll to spin quench the master alloy material. The obtained master alloy material has a thickness of about 32 μm and a width of about 2.1 mm.

[0059] (4) Use an X-ray diffractometer and a transmission electron microscope to analyze the structure of the alloy; use a vibrating sample magnetometer and a DC hysteresis loop meter to measure the magnetic properties of the alloy; use an alloy brittleness device to determine the relative fracture strain (ab) of the alloy.

[0060] Among them, the smaller the ab, the smaller the strain generated before the alloy fractures, and the greater the brittleness. After measurement and calculation, the ab of the master alloy material is 3.5%.

[0061] Example 7:

[0062] (1) Weigh and proportion Fe, Si, B, Cr, and FeC with a mass percentage purity of not less than 99.7% according to the chemical composition formula of Fe: 81.9, B: 5, stable phase α-Fe: 2.3, amorphous phase α-Fe: 2.5, Si: 7, and Cr: 1.6.

[0063] (2) Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.2 Pa, introduce nitrogen to 0.08 - 0.15 MPa, the melting temperature is 1300 - 1500 °C, keep warm for 5 - 10 min after melting evenly, and the vacuum degree in the furnace reaches 5×10 - 3 Pa, melt repeatedly for 3 - 8 times, and stir magnetically for 5 - 8 min each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material.

[0064] (3) Crush the master alloy material, place it in a high-vacuum single-roll spinning quenching furnace, evacuate to less than 0.8 Pa, introduce nitrogen and adjust the injection pressure difference to 0.08 MPa, completely melt the master alloy material and then spray it onto the surface of the rotating copper roll to spin-quench the master alloy material, and the obtained master alloy material has a thickness of about 30 μm and a width of about 2.0 mm.

[0065] (4) Use an X-ray diffractometer and a transmission electron microscope to analyze the structure of the alloy; use a vibrating sample magnetometer and a DC hysteresis loop instrument to measure the magnetic properties of the alloy; use an alloy brittleness device to determine the relative fracture strain (ab) of the alloy.

[0066] Among them, the smaller the ab, the smaller the strain generated before the alloy fractures and the greater the brittleness. After measurement and calculation, the ab of the master alloy material is 3.5%.

[0067] In the present invention, an X-ray diffraction and a transmission electron microscope are used to analyze the structure of the alloy, and it can be known that the obtained alloy is an amorphous nanocrystalline structure with a gradient structure. After analysis, its average size and volume fraction can be obtained.

[0068] Use a vibrating sample magnetometer and a DC hysteresis loop instrument to measure the magnetic properties of the alloy, and measure its Bs and Hc.

[0069] Use a brittleness device to determine the relative fracture strain (ab) of the alloy.

[0070] The amorphous and nanocrystalline soft magnetic alloy provided by the present invention has a gradient structure. From the copper roller surface to the free surface, its structure changes from a completely amorphous state to a duplex structure in which α-Fe phases are distributed in the amorphous phase, and the size and volume fraction of the α-Fe phases gradually increase. This special structure enables the alloy to have excellent soft magnetic properties and low brittleness; it has good surface quality without voids and excellent bending toughness; it is very helpful for practical applications; it has a high saturation magnetization intensity and a low coercive force; and it has excellent soft magnetic properties.

[0071] The preparation method of the amorphous and nanocrystalline soft magnetic alloy provided by the present invention is simple. The master alloy can be directly made into the amorphous and nanocrystalline soft magnetic alloy with the above structure by the liquid quenching method without heat treatment, which can significantly improve the production efficiency and reduce the process cost, and is of great significance to the development and industrialization of nanocrystalline alloys.

Claims

1. A kind of iron-based amorphous and nanocrystalline soft magnetic alloy material, characterized in that, Including: Fe, Si, B, Cr, α-Fe phase and amorphous phase are weighed and proportioned according to the chemical composition formula.

2. The iron-based amorphous and nanocrystalline soft magnetic alloy material according to claim 1, wherein: The mass percentage purity of the Fe, Si, B, Cr, α-Fe phase and amorphous phase is 99.7%.

3. The iron-based amorphous and nanocrystalline soft magnetic alloy material according to claim 1, wherein: The chemical composition formula ratio of the Fe, Si, B, Cr, α-Fe phase and amorphous phase is: 80.2 - 81.9, 4 - 7, 5 - 8, 1.2 - 2.0, 1 - 3, 1 - 3.

4. A preparation method of an iron-based amorphous and nanocrystalline soft magnetic alloy material, characterized in that: For preparing the iron-based amorphous nanocrystalline soft magnetic alloy material described in any one of claims 1 - 3, the following steps are included: S101: Weigh and proportion Fe, Si, B, Cr, α-Fe phase and amorphous phase with a mass percentage purity of not less than 99.7% according to the chemical composition formula: Fe: 80.2 - 81.9, B: 5 - 8, stable phase α-Fe: 1 - 3, amorphous phase α-Fe: 1 - 3, Si: 4 - 7, and Cr: 1.2 - 2.

0. S102: Put the prepared alloy raw materials into a melting furnace, evacuate to less than 1.2 - 1.8 Pa, introduce nitrogen to 0.08 - 0.15 MPa, the melting temperature is 1300 - 1500 °C, keep warm for 5 - 30 min after uniform melting, and the vacuum degree in the furnace reaches 5×10 -3 Pa, melt repeatedly for 3 - 8 times, stir magnetically for 5 - 8 min each time to ensure the chemical uniformity of the alloy ingot and form the master alloy material; S103: Crush the master alloy material, place it into a high-vacuum single-roll spin quenching furnace, evacuate to less than 0.6 - 1.2 Pa, introduce nitrogen and adjust the injection pressure difference to 0.06 - 0.09 MPa. After completely melting the master alloy material, spray it onto the surface of a rotating copper roll to spin quench the master alloy material, and the obtained master alloy material has a thickness of 15 - 35 μm and a width of 1.2 - 2.1 mm.

5. The preparation method of an iron-based amorphous and nanocrystalline soft magnetic alloy material according to claim 4, characterized in that: After obtaining the master alloy material: Use an X-ray diffractometer and a transmission electron microscope to analyze the structure of the alloy; Use a vibrating sample magnetometer and a DC hysteresis loop tester to measure the magnetic properties of the alloy; Use an alloy brittleness device to determine the relative fracture strain of the alloy.

6. The preparation method of an iron-based amorphous and nanocrystalline soft magnetic alloy material according to claim 5, characterized in that: The relative fracture strain of the master alloy material is 3.5 - 4.8%.

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