阅读说明：本技术 磁珠用增强型材料、其制备方法与叠层片式磁珠的制备方法 (Enhanced material for magnetic beads, preparation method of enhanced material and preparation method of laminated magnetic beads ) 是由 温术来 于树永 赵寰宇 范佳斌 卢江 于 2020-06-19 设计创作，主要内容包括：本发明提供了一种磁珠用增强型材料,由基料和添加料组成,所述基料为核壳结构的FeCoNiCrAl@SiO<Sub>2</Sub>高熵合金；所述添加料由ZrO<Sub>2</Sub>、SiO<Sub>2</Sub>、Al<Sub>2</Sub>O<Sub>3</Sub>、TiO<Sub>2</Sub>、B<Sub>2</Sub>O<Sub>3</Sub>和云母KAl<Sub>2</Sub>(AlSi<Sub>3</Sub>O<Sub>10</Sub>)(OH)<Sub>2</Sub>组成。本申请还提供了磁珠用增强型材料的制备方法。进一步的,本申请还提供了一种叠层片式磁珠的制备方法。本申请以FeCoNiCrAl@SiO<Sub>2</Sub>壳核结构的高熵合金作为基料,而添加料中含有一定比例的ZrO<Sub>2</Sub>粉体,在煅烧过程中SiO<Sub>2</Sub>与ZrO<Sub>2</Sub>原位形成锆英石ZrSiO<Sub>4</Sub>,以此来增加基料之间、基料与添加料之间的结合强度,最终提高了叠层片式磁珠的性能。(The invention provides an enhanced material for magnetic beads, which consists of a base material and an additive, wherein the base material is FeCoNiCrAl @ SiO with a core-shell structure 2 High entropy alloy; the additive consists of ZrO 2 、SiO 2 、Al 2 O 3 、TiO 2 、B 2 O 3 And mica KAl 2 (AlSi 3 O 10 )(OH) 2 And (4) forming. The application also provides a preparation method of the enhanced material for the magnetic beads. Further, the application also provides a preparation method of the laminated magnetic bead. FeCoNiCrAl @ SiO 2 The high-entropy alloy with a shell-core structure is used as a base material, and the addition material contains ZrO with a certain proportion 2 Powder of SiO during calcination 2 And ZrO 2 In-situ formation of zircon ZrSiO 4 Therefore, the bonding strength between the base materials and the additive is increased, and the performance of the laminated magnetic bead is finally improved.)

1. The reinforced material for the magnetic beads comprises a base material and an additive, wherein the base material is FeCoNiCrAl @ SiO with a core-shell structure₂High entropy alloy;

the additive consists of ZrO₂、SiO₂、Al₂O₃、TiO₂、B₂O₃And mica KAl₂(AlSi₃O₁₀)(OH)₂And (4) forming.

2. The reinforced material for a magnetic bead according to claim 1, wherein the ZrO based on the total mass of the binder₂0.1 to 3 wt% of SiO₂0.1-0.5 wt% of Al₂O₃0.3-3 wt% of TiO₂In an amount of 0.3 to 1.5 wt%, B₂O₃0.5 to 2 wt% of mica KAl₂(AlSi₃O₁₀)(OH)₂The content of (B) is 0.1-0.5 wt%.

3. Enhanced material for magnetic beads according to claim 1, characterized in that the FeCoNiCrAl @ SiO is₂The preparation method of the high-entropy alloy comprises the following specific steps:

mixing iron powder, cobalt powder, nickel powder, chromium powder and aluminum powder according to equal atomic ratio to obtain mixed powder;

ball-milling the mixed powder to obtain FeCoNiCrAl powder;

mixing FeCoNiCrAl powder, ethanol and ammonia water, mixing with ethyl orthosilicate, and reacting to obtain FeCoNiCrAl @ SiO₂High entropy alloy.

4. The reinforced material for magnetic beads according to claim 3, wherein the particle sizes of the iron powder, the cobalt powder, the nickel powder, the chromium powder and the aluminum powder are all 1 to 10 μm.

5. The method for preparing the enhanced material for magnetic beads of claim 1, comprising the following steps:

A) ZrO 2 is mixed with₂Powder material, SiO₂Powder material, Al₂O₃Powder material, TiO₂Powder material, B₂O₃Powder and mica KAl₂(AlSi₃O₁₀)(OH)₂Ball milling and mixing the powder to obtain an additive;

B) FeCoNiCrAl @ SiO with core-shell structure₂High entropy alloy and said additive mixAnd synthesizing to obtain the enhanced material for the magnetic beads.

6. The production method according to claim 5, wherein the ZrO₂Powder material, SiO₂Powder material, Al₂O₃Powder material, TiO₂Powder material, B₂O₃Powder and mica KAl₂(AlSi₃O₁₀)(OH)₂The particle size of the powder is 1-20 mu m.

7. The preparation method of claim 5, wherein the ball-milling has a ball-to-material ratio of (10-20): 1, the rotating speed is 100 to 300 r/min.

8. A preparation method of laminated magnetic beads comprises the following steps:

preparing the magnetic beads into a film by using an enhanced material, and performing screen printing to obtain a laminated structure material;

and calcining the laminated structure material at high temperature to obtain the laminated sheet type magnetic bead.

9. The production method according to claim 8, wherein the film is produced by a casting process.

Technical Field

The invention relates to the technical field of magnetic bead materials, in particular to an enhanced material for magnetic beads, a preparation method of the enhanced material and a preparation method of laminated magnetic beads.

Background

The magnetic bead is used as an element with wide application, has the function of absorbing high-frequency harmonic waves in a circuit, and the preparation material of the magnetic bead is required to have the performances of high magnetic conductivity, high impedance and the like.

The high-entropy alloy FeCoNiCrAl powder has good magnetic property and high impedance characteristic, and has potential application prospect in the field of magnetic bead preparation. However, the high-entropy alloy FeCoNiCrAl powder is used as an alloy material, and has the problem of low bonding strength between the powder and additives.

Disclosure of Invention

The invention aims to provide a reinforced material for magnetic beads, which can be used for preparing laminated magnetic beads.

In view of the above, the present application provides a reinforced material for magnetic beads, which comprises a base material and an additive material, wherein the base material is FeCoNiCrAl @ SiO with a core-shell structure₂High entropy alloy;

the additive consists of ZrO₂、SiO₂、Al₂O₃、TiO₂、B₂O₃And mica KAl₂(AlSi₃O₁₀)(OH)₂And (4) forming.

Preferably, the ZrO based on the total mass of the binder₂0.1 to 3 wt% of SiO₂0.1-0.5 wt% of Al₂O₃0.3-3 wt% of TiO₂The content of (B) is 0.3-1.5 wt%,B₂O₃0.5 to 2 wt% of mica KAl₂(AlSi₃O₁₀)(OH)₂The content of (B) is 0.1-0.5 wt%.

Preferably, the FeCoNiCrAl @ SiO₂The preparation method of the high-entropy alloy comprises the following specific steps:

mixing iron powder, cobalt powder, nickel powder, chromium powder and aluminum powder according to equal atomic ratio to obtain mixed powder;

ball-milling the mixed powder to obtain FeCoNiCrAl powder;

mixing FeCoNiCrAl powder, ethanol and ammonia water, mixing with ethyl orthosilicate, and reacting to obtain FeCoNiCrAl @ SiO₂High entropy alloy.

Preferably, the particle sizes of the iron powder, the cobalt powder, the nickel powder, the chromium powder and the aluminum powder are all 1-10 μm.

The application also provides a preparation method of the enhanced material for the magnetic beads, which comprises the following steps:

A) ZrO 2 is mixed with₂Powder material, SiO₂Powder material, Al₂O₃Powder material, TiO₂Powder material, B₂O₃Powder and mica KAl₂(AlSi₃O₁₀)(OH)₂Ball milling and mixing the powder to obtain an additive;

B) FeCoNiCrAl @ SiO with core-shell structure₂And mixing the high-entropy alloy with the additive to obtain the enhanced material for the magnetic beads.

Preferably, the ZrO₂Powder material, SiO₂Powder material, Al₂O₃Powder material, TiO₂Powder material, B₂O₃Powder and mica KAl₂(AlSi₃O₁₀)(OH)₂The particle size of the powder is 1-20 mu m.

Preferably, the ball-milling ball-material ratio is (10-20): 1, the rotating speed is 100 to 300 r/min.

The application also provides a preparation method of the laminated magnetic bead, which comprises the following steps:

preparing the magnetic beads into a film by using an enhanced material, and performing screen printing to obtain a laminated structure material;

and calcining the laminated structure material at high temperature to obtain the laminated sheet type magnetic bead.

Preferably, the film is prepared by a casting process.

The application provides an enhanced material for magnetic beads, which consists of a base material and an additive, wherein the base material is FeCoNiCrAl @ SiO with a core-shell structure₂High entropy alloy; the additive consists of ZrO₂、SiO₂、Al₂O₃、TiO₂、B₂O₃And mica KAl₂(AlSi₃O₁₀)(OH)₂And (4) forming. The application provides a shell layer SiO on high entropy alloy surface in enhancement mode material for magnetic bead₂SiO in layers and additives₂With ZrO in the additive₂In-situ generation of ZrSiO₄The bonding strength between the base material and the additive material can be improved, so that the magnetic material can be used for laminated magnetic beads, and the magnetic performance and the high-impedance characteristic of the laminated magnetic beads are obviously improved.

Drawings

FIG. 1 is a graph of impedance values of the laminated magnetic bead prepared in example 1 in the frequency domain of 2-18 GHz;

FIG. 2 is a graph showing the attenuation constant of the laminated magnetic bead prepared in example 1 in the frequency domain of 2-18 GHz.

Detailed Description

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.

The magnetic bead material needs to satisfy two key performance indexes, namely high resistivity and good magnetism. The high-entropy alloy has good magnetic property as an advanced material with potential application prospect, the resistivity of the high-entropy alloy is much higher than that of typical magnetic metal materials such as Fe, Co, Ni and the like, the high-entropy alloy is mainly applied to the field of structural mechanics at present, and has not been reported in the field of components and parts, particularly the application of magnetic beads, and the high-entropy alloy is an alloy material and is mixed with a base materialThe bonding strength is not high, thereby limiting the application of the high-entropy alloy in the aspect of magnetic beads. Therefore, the application provides an enhancement mode material for magnetic bead, it is through introducing the high entropy alloy of nucleocapsid structure to mix it with the addition material, realized the improvement of base material high entropy alloy and addition material direct bond strength at last, make the high entropy alloy can be applied to the magnetic bead material and have better effect. Specifically, the application provides an enhancement mode material for magnetic beads, which consists of a base material and an additive, wherein the base material is FeCoNiCrAl @ SiO of a core-shell structure₂High entropy alloy;

the additive consists of ZrO₂、SiO₂、Al₂O₃、TiO₂、B₂O₃And mica KAl₂(AlSi₃O₁₀)(OH)₂And (4) forming.

In the enhancement type material for the magnetic beads, provided by the application, the base material is FeCoNiCrAl @ SiO with a core-shell structure₂High entropy alloys, i.e. FeCoNiCrAl as a core, SiO₂As a shell layer; the silicon dioxide is used as the shell material, and besides the high resistivity of the silicon dioxide, the silicon dioxide can react with the additive, so that the bonding strength between the high-entropy alloy particles is effectively enhanced through the generation of the product.

The additive of the reinforced material for magnetic beads is selected mainly by improving the bonding strength with the base material by using a reaction product between the additives. The alumina, titanium oxide and boron oxide in the additive can react chemically, and the generated product plays the role of a binder; the alumina, the titanium oxide and the boron oxide can also generate chemical action with the silicon dioxide shell, and the bonding strength is improved similar to that of the zirconia; the silicon dioxide in the additive is used for avoiding the deterioration of the final reaction effect caused by the insufficient amount of the shell silicon dioxide, and is properly added into the additive; mica KAl₂(AlSi₃O₁₀)(OH)₂The performance is stable, the main function is to dilute the additives, slow down the reaction rate between the additives and the silica shell, and in addition, the mica can increase the resistivity.

Based on the total mass of the binder, the ZrO₂In an amount of0.1～3wt％，SiO₂0.1-0.5 wt% of Al₂O₃0.3-3 wt% of TiO₂In an amount of 0.3 to 1.5 wt%, B₂O₃0.5 to 2 wt% of mica KAl₂(AlSi₃O₁₀)(OH)₂The content of (A) is 0.1-0.5 wt%; more specifically, the ZrO₂0.5-2 wt% of SiO₂0.2-0.4 wt% of Al₂O₃0.8-2 wt% of TiO₂In an amount of 1.0 to 1.5 wt%, B₂O₃1 to 1.8 wt% of mica KAl₂(AlSi₃O₁₀)(OH)₂The content of (B) is 0.2-0.4 wt%. The amount of the above additives should not be too large, otherwise the main effect of the base material is reduced.

In the present application, the FeCoNiCrAl @ SiO₂The preparation method of the high-entropy alloy comprises the following specific steps:

mixing iron powder, cobalt powder, nickel powder, chromium powder and aluminum powder according to equal atomic ratio to obtain mixed powder;

ball-milling the mixed powder to obtain FeCoNiCrAl;

mixing FeCoNiCrAl, ethanol and ammonia water, then mixing with ethyl orthosilicate, and reacting to obtain FeCoNiCrAl @ SiO₂High entropy alloy.

In the above FeCoNiCrAl @ SiO₂In the process of preparing the high-entropy alloy, firstly, mixing iron powder, cobalt powder, nickel powder, chromium powder and aluminum powder according to equal atomic proportion, preferably cleaning the powder in 0.1% hydrochloric acid for 3-5 min to remove surface oxide skin, then sequentially cleaning with deionized water and absolute ethyl alcohol, drying in vacuum, and mixing to obtain mixed powder. The particle sizes of the iron powder, the cobalt powder, the nickel powder, the chromium powder and the aluminum powder are respectively 1-10 mu m.

According to the invention, the mixed powder is subjected to ball milling, the ball-to-material ratio of the ball milling is 10-20: 1, the rotating speed is 100-300 r/min, and the ball milling time is 30-50 h, so that the high-entropy alloy powder FeCoNiCrAl is obtained.

According to the method, a reaction solution is prepared, namely, absolute ethyl alcohol, deionized water and ammonia water are mixed, the high-entropy alloy powder is added into the mixed solution, ethyl orthosilicate is added, and reaction is carried out to obtain the base material. In the mixed solution, the volume percentage of the ammonia water is 1-5%, and in a specific embodiment, the volume percentage of the ammonia water is 1%; the ethyl orthosilicate is added in the form of an ethanol solution of ethyl orthosilicate, the volume percentage of the ethyl orthosilicate in the ethanol solution of the ethyl orthosilicate is 5-10%, and in a specific embodiment, the volume percentage of the ethyl orthosilicate is 5%. The factors are beneficial to ensuring that the silicon dioxide is uniformly and tightly coated on the surface of the high-entropy alloy particles.

In the process of preparing the base material, a silicon dioxide shell layer is deposited on the surface of the high-entropy alloy by a chemical reaction method, and the silicon dioxide is uniformly and tightly coated around the high-entropy alloy particles by controlling the chemical reaction rate.

The application also provides a preparation method of the enhanced material for the magnetic beads, which comprises the following steps:

A) ZrO 2 is mixed with₂Powder material, SiO₂Powder material, Al₂O₃Powder material, TiO₂Powder material, B₂O₃Powder and mica KAl₂(AlSi₃O₁₀)(OH)₂Ball milling and mixing the powder to obtain an additive;

B) FeCoNiCrAl @ SiO with core-shell structure₂And mixing the high-entropy alloy with the additive to obtain the enhanced material for the magnetic beads.

In the reinforced material for magnetic beads, the ZrO₂Powder material, SiO₂Powder material, Al₂O₃Powder material, TiO₂Powder material, B₂O₃Powder and mica KAl₂(AlSi₃O₁₀)(OH)₂The particle size of the powder is 1-20 mu m. In the ball milling process, the ball-to-material ratio of the ball milling is (10-20): 1, the rotating speed is 100 to 300 r/min.

The above-mentioned base materials and additives have been described in detail, and are not repeated herein.

The application also provides a preparation method of the laminated magnetic bead, which comprises the following steps:

preparing the magnetic beads into a film by using an enhanced material, and performing screen printing to obtain a laminated structure material;

and calcining the laminated structure material at high temperature to obtain the laminated sheet type magnetic bead.

In the above-mentioned preparation method, the preparation into a thin film, screen printing and high-temperature calcination are well-known technical means to those skilled in the art, and the present application is not particularly limited.

Although the resistivity of the high-entropy alloy is higher than that of a typical magnetic metal material, compared with the existing mainstream preparation material ferrite of the magnetic bead, the resistivity of the high-entropy alloy has the defect of being lower; the design of the shell-core structure is also crucial: a silicon dioxide shell layer is deposited on the surface of the high-entropy alloy by a chemical reaction method, silicon dioxide is uniformly and tightly coated around high-entropy alloy particles by controlling the chemical reaction rate, a zircon layer can be uniformly formed on the surface of the high-entropy alloy after the base material is mixed with the additive and calcined, and the bonding strength between powder is improved by tight mechanical bonding between the high-entropy alloy and the zircon. Therefore, the design of the core-shell structure plays an important role in improving the bonding strength between the powders, and the simple mixing of the powders in the conventional magnetic bead preparation method obviously cannot achieve the effect of the core-shell structure.

The magnetic bead material related to the application is finally calcined at high temperature to form a block material for use, so that the improvement of the bonding strength has a significant meaning for improving the use performance of the block material, for example, the magnetic bead needs to meet performance indexes of vibration resistance, impact resistance, thermal shock resistance and the like in the application process. The choice of silica is therefore, in addition to its high resistance, also strongly related to the choice of the additive, since there is a further chemical reaction between the two.

The application adopts high-entropy alloy FeCoNiCrAl @ SiO₂Provides an enhanced material for magnetic beads as a basic material and a preparation method thereof, and mainly forms a layer of SiO uniformly on the surface of high-entropy alloy FeCoNiCrAl₂The shell forms FeCoNiCrAl @ SiO₂The shell-core structure is used as a base material, and the additive contains ZrO in a certain proportion₂Powder of SiO during calcination₂And ZrO₂In-situ formation of zircon ZrSiO₄So as to increase the bonding strength between the base materials and the additives; and due to SiO₂Is uniformly formed on the surface of the high-entropy alloy powder, so that SiO is relatively high₂The effect of directly mixing the additive and sintering the mixture is good.

In addition, the main raw material high-entropy alloy in the base material is prepared by a ball milling method, is mainly in a lamellar shape, has shape anisotropy in the aspect of magnetic property and is prepared according to a Snoek limit formulaWherein H_kIt is known that a magnetic material having a strong shape anisotropy more easily obtains a good high-frequency magnetic permeability due to the anisotropic field, and thus magnetic beads made of a lamellar high-entropy alloy have excellent magnetic properties.

For further understanding of the present invention, the reinforced material for magnetic beads and the preparation method thereof provided by the present invention are described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.