CN116179923A - A kind of high saturation magnetization soft magnetic multi-principal alloy with high Curie temperature and its preparation method and application - Google Patents

Abstract

The invention provides a soft magnetic multi-principal element alloy with high saturation magnetization intensity and high Curie temperature, and a preparation method and application thereof, belonging to the technical field of novel functional metal materials. The invention provides a high saturation magnetization soft magnetic multi-principal element alloy with high Curie temperature, which comprises an A element and an X element, wherein the A element comprises a and/or b, and the X element comprises two or more of Al, si, ti, V, cr, mo, pt, ni, cu, sc, nb, Y and Ge. The high saturation magnetization soft magnetic multi-principal element alloy is a high-entropy alloy, atoms of different elements have stronger ionic bonding, the crystal structure of the alloy is more stable, the atom and phase transition mobility of the alloy are reduced at high temperature, the high saturation magnetization soft magnetic multi-principal element alloy has more excellent thermal stability and high-temperature mechanical property, and the alloy is more suitable for being used as a high-temperature soft magnetic functional material, and has good room temperature plasticity due to the high entropy effect caused by the multi-principal elements.

Description

A soft magnetic multi-principal alloy with high saturation magnetization and high Curie temperature and its Preparation method and application

technical field

The invention relates to the technical field of new functional metal materials, in particular to a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature and a preparation method and application thereof.

Background technique

With the development of the electronic power industry, people have put forward higher requirements for soft magnetic materials in response to the needs of energy saving and emission reduction, not only requiring materials to have magnetic properties such as high resistivity, high magnetic permeability, low coercive force and low loss. , It also requires the material to have mechanical properties such as high strength and high hardness. At present, intermetallic compounds are a class of materials with great potential. They are not only used as structural materials because of their good oxidation resistance and high room temperature processing performance, but also have good magnetic properties, such as ferrite soft magnetic Material. However, the strong order in intermetallic compounds makes it brittle at room temperature, which greatly limits its application, and the low saturation magnetization and low Curie temperature of ferrite soft magnetic materials also limit the Application of intercompounds in magnetic materials. Amorphous materials have unique advantages such as high magnetic permeability and low coercive force, high system free energy, and strong chemical corrosion resistance, but poor mechanical properties of amorphous materials and the inability to achieve large-scale materials also limit their application.

There is a "cocktail" effect in multi-principal alloys, and its performance comes from the overall contribution of the alloy constituent phases, and is affected by phase shape, phase distribution, and phase boundaries. Each solid solution phase is a multi-component solid solution, so the properties of the alloy are not only determined by the basic properties of each element, but also affected by the common properties and lattice distortion caused by the mixing of multiple components. These factors affect not only the mechanical properties of the alloy but also the functional properties of the alloy. Therefore, multi-principal alloys will also be well developed in the fields of magnetic, thermoelectric, superconducting and other functional materials. However, the low Curie temperature and low high-temperature magnetization of current multi-principal alloys limit their engineering applications.

Contents of the invention

In view of this, the object of the present invention is to provide a high saturation magnetization soft magnetic multi-principal alloy with high Curie temperature, its preparation method and application. The high-performance soft magnetic metal material of the invention not only has relatively high Curie temperature and high saturation magnetization strength, but also has stable magnetization performance at high temperature.

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

The invention provides a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature, which includes A element and X element, the A element includes a and/or b, and the a includes Co, Fe and Ni One or more of, said b includes Gd and/or Dy, and said X element includes two of Al, Si, Ti, V, Cr, Mo, Pt, Ni, Cu, Sc, Nb, Y and Ge one or more species.

Preferably, the high saturation magnetization soft magnetic multi-principal alloy is Co3 (AlSiTi).

Preferably, the high saturation magnetization soft magnetic multi-principal alloy is FeCoNiAlCu.

The present invention also provides a method for preparing a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature described in the above technical solution, comprising the following steps:

Melting the raw materials to obtain a molten material;

Ingot metallurgy is carried out on the molten material to obtain the soft magnetic multi-principal element alloy with high saturation magnetization and high Curie temperature.

The present invention also provides a method for preparing a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature described in the above technical solution, comprising the following steps:

The raw material is subjected to ultra-high pressure solidification to obtain the soft magnetic multi-principal alloy with high saturation magnetization and high Curie temperature.

The present invention also provides a method for preparing a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature described in the above technical solution, comprising the following steps:

The raw materials are directional solidified to obtain the soft magnetic multi-principal alloy with high saturation magnetization and high Curie temperature.

The present invention also provides a method for preparing a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature described in the above technical solution, comprising the following steps:

Powdering the raw materials to obtain a powder;

The powder is processed by powder metallurgy to obtain the soft magnetic multi-principal alloy with high saturation magnetization and high Curie temperature.

Preferably, the powder metallurgy method includes hot isostatic pressing, high temperature and high pressure sintering or additive manufacturing, the temperature of the high temperature and high pressure sintering is above 1000°C, the pressure is above 50MPa, and the time is 5-20min.

Preferably, the pressure of the hot isostatic pressing is above 120 MPa, the time is 2-6 hours, and the temperature is 500-950°C.

The present invention also provides the high saturation magnetization soft magnetic multi-principal alloy with high Curie temperature described in the above technical solution or the high saturation magnetization soft magnetic multi-principal alloy with high Curie temperature prepared by the preparation method described in the above technical solution. The main alloy.

The invention provides a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature, which includes A element and X element, the A element includes a and/or b, and the a includes Co, Fe and Ni One or more of, said b includes Gd and/or Dy, and said X element includes two of Al, Si, Ti, V, Cr, Mo, Pt, Ni, Cu, Sc, Nb, Y and Ge one or more species.

The high saturation magnetization soft magnetic multi-principal alloy of the present invention has a single crystal structure or a double crystal structure. The single crystal structure includes a B2 structure and an FCC structure, and the double crystal structure is a B2+L12 structure. The present invention combines traditional soft magnetic alloys According to the characteristics of multi-principal high-entropy alloys, a variety of elements that constitute the same crystal structure are added in close to equimolar ratios, thereby forming a class of multi-principal soft materials that have both a highly ordered crystal structure and a single phase of high-entropy alloys. Magnetic metal material, because the multi-principal soft magnetic metal material obtained in the present invention is still a high-entropy alloy, the atoms of different elements have strong ionic bonds, and the crystal structure of the alloy is more stable, making its atoms and phase transitions Mobility decreases at high temperatures. Compared with traditional soft magnetic metal materials, it has better thermal stability and high-temperature mechanical properties, and is more suitable for high-temperature soft magnetic functional materials. Due to the high entropy brought by its multi-principal elements Effect, has good room temperature plasticity, for example, compared with soft magnetic amorphous alloy, the service temperature of multi-principal soft magnetic metal materials can reach 500 ° C, the room temperature tensile strength can reach 800 MPa, and the plasticity can reach more than 30%. The above-mentioned characteristics of multi-principal soft magnetic metal materials make them have broad application prospects in aviation, aerospace, military, civil and other fields, and have important commercial value.

The present invention also provides a preparation method of the soft magnetic multi-principal alloy with high saturation magnetization and high saturation magnetization described in the above technical proposal. The preparation method of the present invention makes the composition of the alloy more uniform.

Description of drawings

Fig. 1 is the M-H curve of the Co3 (AlSiTi) multi-principal element soft magnetic metal material low temperature that embodiment 1 obtains;

Fig. 2 is the M-H curve of the Co3 (AlSiTi) multi-principal soft magnetic metallic material high temperature that embodiment 1 obtains;

Fig. 3 is the M-H curve of the FeCoNiAlCu multi-principal element soft magnetic metallic material that embodiment 2 obtains;

Fig. 4 is the relationship curve of saturation magnetization and coercive force with temperature of the FeCoNiAlCu multi-principal soft magnetic metal material obtained in Example 2.

Detailed ways

The invention provides a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature, which includes A element and X element, the A element includes a and/or b, and the a includes Co, Fe and Ni One or more of, said b includes Gd and/or Dy, and said X element includes two of Al, Si, Ti, V, Cr, Mo, Pt, Ni, Cu, Sc, Nb, Y and Ge one or more species.

In the present invention, the high saturation magnetization soft magnetic multi-principal alloy is preferably Co3(AlSiTi) or FeCoNiAlCu.

In the present invention, the high saturation magnetization soft magnetic multi-principal alloy has a single crystal structure or a double crystal structure, and the phase composition of the single crystal structure is preferably B2 or FCC structure phase; the phase composition of the double crystal structure Preferably it is a B2+L12 structural phase.

In the present invention, when the valence electron concentration of the added element is ≥8 or <6.87, it is a single crystal structure, and when the valence electron concentration of the added element is 6.87-8, it is a double crystal structure.

The present invention also provides a method for preparing a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature described in the above technical solution, comprising the following steps:

Melting the raw materials to obtain a molten material;

Ingot metallurgy is performed on the molten material to obtain the soft magnetic multi-principal alloy with high saturation magnetization and high Curie temperature.

In the present invention, the melting is preferably performed using an electric arc furnace or an induction melting furnace.

In the present invention, the ingot metallurgy is preferably carried out in a mold.

The present invention also provides a method for preparing a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature described in the above technical solution, comprising the following steps:

The raw material is subjected to ultra-high pressure solidification to obtain the soft magnetic multi-principal alloy with high saturation magnetization and high Curie temperature.

In the present invention, the ultra-high pressure solidification is preferably performed using ultra-high pressure six-sided roof or ultra-high pressure solidification equipment.

In the present invention, the pressure of the ultra-high pressure solidification is preferably 1-5 GPa.

The present invention also provides a method for preparing a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature described in the above technical solution, comprising the following steps:

The raw materials are directional solidified to obtain the soft magnetic multi-principal alloy with high saturation magnetization and high Curie temperature.

In the present invention, the drawing speed of the directional solidification is preferably 15-100 μm/s.

The present invention also provides a method for preparing a high saturation magnetization soft magnetic multi-principal alloy with a high Curie temperature described in the above technical solution, comprising the following steps:

Powdering the raw materials to obtain a powder;

The powder is processed by powder metallurgy to obtain the soft magnetic multi-principal alloy with high saturation magnetization and high Curie temperature.

In the present invention, the powder metallurgy method preferably includes hot isostatic pressing, high temperature and high pressure sintering or additive manufacturing, the temperature of the high temperature and high pressure sintering is preferably above 1000°C, the pressure is preferably above 50MPa, and the time is preferably 5-20min .

In the present invention, the pressure of the hot isostatic pressing is preferably above 120 MPa, the time is preferably 2-6 hours, and the temperature is preferably 500-950°C.

The present invention also provides the high saturation magnetization soft magnetic multi-principal alloy with high Curie temperature described in the above technical solution or the high saturation magnetization soft magnetic multi-principal alloy with high Curie temperature prepared by the preparation method described in the above technical solution. The main alloy.

The present invention has no special limitation on the specific manner of the application, and the methods well known to those skilled in the art can be adopted.

In order to further illustrate the present invention, the high saturation magnetization soft magnetic multi-principal alloy with high Curie temperature provided by the present invention and its preparation method and application are described in detail below in conjunction with examples, but they cannot be interpreted as limitations on the protection scope of the present invention limited.

Example 1

A multi-principal soft magnetic metal material is Co3 (AlSiTi) multi-principal soft magnetic metal material, the crystal structure is FCC structure phase, and the molar ratio of Al, Si and Ti elements is the same.

Preparation method: ingredients are prepared according to the above ratio, the raw materials of Co element, Al element, Si element and Ti element are all simple substances (purity>99.5wt.%), and then the ingredients are put into a non-consumable vacuum electric arc furnace, non-consumable The vacuum electric arc furnace is evacuated and flushed with high-purity argon for more than three times, and the raw materials are smelted under the protection of inert gas. The smelting is repeated 6 times, and the smelting billet needs to be turned over 180° for each smelting before smelting; The final ingot is taken out from the furnace after cooling, and the obtained material is Co3 (AlSiTi) multi-principal soft magnetic metal material. The composition of the alloy prepared by this method is more uniform, and the structure control is easy to realize.

Fig. 1 is the M-H curve of the Co3 (AlSiTi) multi-principal soft magnetic metal material low temperature that embodiment 1 obtains, and Fig. 2 is the M-H curve of the Co3 (AlSiTi) multi-principal soft magnetic metal material high temperature that embodiment 1 obtains, The illustration in Fig. 2 is the variation curve of saturation magnetization of Co3 (AlSiTi) multi-principal soft magnetic metal material with temperature. It can be seen from Fig. 1-2 that the obtained Co3 (AlSiTi) multi-principal soft magnetic metal material shows excellent low and high temperature magnetic properties. Under low temperature conditions, the soft magnetic properties of the material are the best, and the saturation magnetization reaches above 130emu/g. When the temperature rises to 900K, its saturation magnetization still reaches above 70emu/g, and its coercive force is about 80Oe, which is in line with the characteristics of soft magnetic materials.

Example 2

A multi-principal soft magnetic metal material is FeCoNiAlCu multi-principal soft magnetic metal material, the crystal structure is B2 structural phase, and the molar ratio among the elements is the same.

Preparation method: batching is carried out according to the above ratio, and the raw materials of Co element, Al element, Cu element, Fe element and Ni element are all simple substances (purity>99.5wt.%), and then the batching is put into a non-consumable vacuum electric arc furnace, The non-consumable vacuum electric arc furnace is evacuated and flushed with high-purity argon for more than three times, and the raw materials are smelted under the protection of inert gas, and the smelting is repeated 6 times. The smelting billet needs to be turned over 180° for each smelting and then smelting; After smelting 6 times, the ingot is cooled and taken out of the furnace. The obtained material is FeCoNiAlCu multi-principal soft magnetic metal material. The composition of the alloy prepared by this method is more uniform, which can effectively avoid composition segregation caused by multi-element addition. question.

Fig. 3 is the M-H curve of the FeCoNiAlCu multi-principal soft magnetic metallic material that embodiment 2 obtains, and Fig. 4 is the relational curve of saturation magnetization and coercivity and temperature of the FeCoNiAlCu multi-principal soft magnetic metallic material that embodiment 2 obtains, It can be seen from Figures 3 to 4 that the obtained FeCoNiAlCu multi-principal soft magnetic metal material exhibits excellent magnetic properties, and the comprehensive performance at around 150K is the best. The material shows a ferromagnetic state curve, and the saturation magnetization of the material is 72emu /g, the coercive force is 70Oe, in line with the characteristics of soft magnetic materials.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any form. It should be pointed out that those skilled in the art can make some improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims (10)

1. A high saturation magnetization soft magnetic multi-principal element alloy having a high curie temperature, characterized by comprising an a element and an X element, the a element comprising a and/or b, the a comprising one or more of Co, fe and Ni, the b comprising Gd and/or Dy, the X element comprising two or more of Al, si, ti, V, cr, mo, pt, ni, cu, sc, nb, Y and Ge.

2. The high saturation magnetization soft magnetic multi-principal component alloy according to claim 1, wherein the high saturation magnetization soft magnetic multi-principal component alloy is Co3 (AlSiTi).

3. The high saturation magnetization soft magnetic multi-principal component alloy according to claim 1, wherein the high saturation magnetization soft magnetic multi-principal component alloy is FeCoNiAlCu.

4. A method for producing a high saturation magnetization soft magnetic multi-principal component alloy having a high curie temperature according to any one of claims 1 to 3, comprising the steps of:

melting the raw materials to obtain a molten material;

and carrying out ingot metallurgy on the melting material to obtain the soft magnetic multi-principal element alloy with high saturation magnetization intensity and high Curie temperature.

5. A method for producing a high saturation magnetization soft magnetic multi-principal component alloy having a high curie temperature according to any one of claims 1 to 3, comprising the steps of:

and (3) carrying out ultrahigh pressure solidification on the raw materials to obtain the soft magnetic multi-principal component alloy with high saturation magnetization and high Curie temperature.

6. A method for producing a high saturation magnetization soft magnetic multi-principal component alloy having a high curie temperature according to any one of claims 1 to 3, comprising the steps of:

and (3) directionally solidifying the raw materials to obtain the soft magnetic multi-principal element alloy with high saturation magnetization and high Curie temperature.

7. A method for producing a high saturation magnetization soft magnetic multi-principal component alloy having a high curie temperature according to any one of claims 1 to 3, comprising the steps of:

powdering the raw materials to obtain powder;

and treating the powder by a powder metallurgy method to obtain the soft magnetic multi-principal element alloy with high saturation magnetization and high Curie temperature.

8. The method according to claim 7, wherein the powder metallurgy method comprises hot isostatic pressing, high-temperature high-pressure sintering or additive manufacturing, wherein the high-temperature high-pressure sintering is performed at a temperature of 1000 ℃ or higher, the pressure is 50MPa or higher, and the time is 5 to 20min.

9. The method according to claim 8, wherein the hot isostatic pressing is performed under a pressure of 120MPa or more for 2 to 6 hours at a temperature of 500 to 950 ℃.

10. Use of a high saturation magnetization soft magnetic multi-element alloy having a high curie temperature according to any one of claims 1 to 3 or a high saturation magnetization soft magnetic multi-element alloy having a high curie temperature according to any one of claims 4 to 9 in the fields of electric power industry and electronic equipment.

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