CN102360670A - Composite material with ferrite magnetic layer and amorphous soft magnetic core as well as preparation method thereof - Google Patents

Abstract

The invention provides a ferrite magnetic layer amorphous soft magnetic core composite material and a preparation method thereof. The composite wire has good functionality. The preparation method has simple process, low production cost and is suitable for industrialized production. The weight percent content of each component in the nanoparticle ferrite magnetic layer amorphous soft magnetic core composite material is: 3-6% Si, 0.5-1% Zr, 0.1-0.3% Y, 0.1-0.2% Ce, 0.6-0.9% Ni, 2-5% B, and the rest is Fe.

Description

A ferrite magnetic layer amorphous soft magnetic core composite material and preparation method thereof

Technical field:

The invention belongs to the field of electronic composite materials, and relates to a nanoparticle ferrite magnetic layer amorphous soft magnetic core information composite material and a preparation method thereof.

Background technique:

Application No. CN200910096349.9 discloses an iron-based amorphous alloy magnetic material and a preparation method thereof. The chemical molecular formula of the alloy material is: (Fe _100-a Co _a ) _x -Dy _y -B _z -Si _w , where x, y, z, and w are atomic percentages: 60≤x≤75, 5≤y ≤25, 20≤z≤25, 0≤w≤10, 0≤a≤10, and x+y+z+w=100. The preparation process of the alloy is as follows: industrially pure metal raw materials and FeB alloy are mixed according to the alloy formula, and the master alloy is formed by vacuum induction melting, and then the amorphous thin strip is obtained by the single-roller stripping method. The line speed of the copper roller is 25-40m/s, the air pressure in the cavity is 0.05MPa, and the injection pressure difference is 0.05-0.10MPa. The raw material purity of the constituent elements Fe, Co, Dy or Si of the iron-based amorphous alloy magnetic material is 99.5%-99.9%. The iron-based amorphous alloy magnetic material has a wide supercooled liquid phase region from 41K to 60K. The amorphous alloy-based magnetic material has a high saturation magnetization M _s =83.73emu/g-108.24emu/g, and a low coercive force H _ci =0.51Oe-0.30Oe.

The problem is that the line speed of the copper roller is 25-40m/s, which requires a lot of energy and is uneconomical. In addition, it also shows that the alloy has a small amorphous forming ability, and the physical properties of the alloy magnetic material are limited.

Invention content:

The purpose of the present invention is to provide a ferrite magnetic layer amorphous soft magnetic core composite material for the above technical defects, and the composite wire has good functionality.

Another object of the present invention is to provide a method for preparing a ferrite magnetic layer amorphous soft magnetic core composite material. The preparation method has simple process, low production cost and is suitable for industrial production.

The purpose of the present invention is achieved through the following technical solutions:

A ferrite magnetic layer amorphous soft magnetic core composite material is characterized in that: the weight percentage of each component is: 3-6% Si, 0.5-1% Zr, 0.1-0.3% Y, 0.1-0.2% %Ce, 0.6-0.9% Ni, 2-5% B, and the rest is Fe.

The method for preparing the ferrite magnetic layer amorphous soft magnetic core wire composite material is characterized in that the preparation steps are as follows:

Amorphous soft magnetic core: according to the above-mentioned amorphous soft magnetic core alloy ingredients, the purity of the raw materials Si, Zr, Y, Ce, Ni, B, Fe are all greater than 99.9%, put the raw materials into the vacuum induction furnace for melting, melting The temperature is 1610-1630°C to obtain the master alloy, and then put it into the remelting tubular crucible in the vacuum induction quenching furnace for remelting. The remelting temperature is 1590-1600°C. At 2-4mm below the rim of the furnace runner, put the above-mentioned master alloy in a remelting tubular crucible and melt it. After the alloy is melted, it overflows from the top of the crucible under the action of argon and contacts the edge of the rotating runner to form a diameter of 100mm. - 110 micron amorphous soft magnetic core alloy wire; the rotational speed of the wheel rim is 20-24m/s;

Coating preparation: Add orthosilicate ethyl ester, γ-methacryloxypropyltrimethoxysilane and ethanol in proportion to a three-necked flask equipped with a stirrer, and the molar ratio is 3:2:2; Add acetic acid dropwise, the amount added is 5g/100mL, after reacting at room temperature for 3h, add methyl methacrylate and initiator azobisisobutyronitrile, the amount added is 10g/100mL and 5g/100mL respectively, then stir at room temperature for 20min Obtaining the sol for use; then mixing commercially available manganese-zinc ferrite powder with a particle size of 50-100nm and the sol to obtain a coating, the weight ratio of the manganese-zinc ferrite powder and the sol is 6:0.4-0.6;

Coating: Then apply the coating to the above-mentioned amorphous soft magnetic core alloy wire, the coating thickness is 3-5 microns; bake and solidify for 15 minutes to obtain soft magnetic alloy powder coating amorphous soft magnetic core magnetic sensitive composite wire material , the baking temperature is 130°C.

Compared with the prior art, the present invention has the following beneficial effects:

The amorphous soft magnetic core material of the present invention adopts Si, Zr, Y, B and Fe in combination to ensure that the iron-based alloy is easily amorphized. The combined use of Y and Ce can strengthen the alloy and ensure that the alloy core material has sufficient strength. Among them, the combination of elements Ni and Y can inhibit the crystallization of the alloy. Among them, V can improve the toughness of the alloy.

The manganese-zinc ferrite powder in the coating is coupled with the amorphous soft magnetic core material, which greatly increases the saturation magnetization of the soft magnetic alloy material, and at the same time obtains a lower coercive force.

The properties of the alloy of the present invention are shown in Table 1.

The invention adjusts the coupling effect between the nano-manganese-zinc ferrite powder in the coating and the internal amorphous soft magnetic core material by adopting the coating method, which can greatly increase the saturation magnetization of the soft magnetic alloy while maintaining a low correction Tenacious. The invention adopts iron as the matrix without using cobalt, and greatly reduces the cost of the material under the condition of ensuring the high performance of the material. Materials can be processed in batches with short production cycles. The preparation process of the composite material is simple and convenient, the produced composite material has certain good properties, and is very convenient for industrialized production.

Description of drawings:

Figure 1 is the organizational diagram of the internal amorphous core material.

It can be seen from Figure 1 that the structure of the material is dense and uniform.

Detailed ways

Embodiment one:

Ingredients: The weight percentage of each component is: 3% Si, 0.5% Zr, 0.1% Y, 0.1% Ce, 0.6% Ni, 2% B, and the rest is Fe. The coating thickness is about 3 microns. The purity of the raw materials Si, Zr, Y, Ce, Ni, B, and Fe is greater than 99.9%. The raw materials are melted in a vacuum induction furnace at a melting temperature of 1610-1630°C to obtain a master alloy, and then put into a vacuum induction quenching Remelting is carried out in the remelting tubular crucible in the furnace. The remelting temperature is 1590-1600°C. Melting in the remelting tubular crucible, the molten alloy overflows from the top of the crucible under the action of argon and contacts the edge of the rotating runner to form an amorphous soft magnetic core alloy wire with a diameter of 100-110 microns; the rotation of the rim of the runner The line speed is 20~24m/s;

Coating preparation: Add orthosilicate ethyl ester, γ-methacryloxypropyltrimethoxysilane and ethanol in proportion to a three-necked flask equipped with a stirrer, and the molar ratio is 3:2:2; Add acetic acid dropwise, the amount added is 5g/100mL, after reacting at room temperature for 3h, add methyl methacrylate and initiator azobisisobutyronitrile, the amount added is 10g/100mL and 5g/100mL respectively, then stir at room temperature for 20min Obtaining the sol for use; then mixing commercially available manganese-zinc ferrite powder with a particle size of 50-100nm and the sol to obtain a coating, the weight ratio of the manganese-zinc ferrite powder and the sol is 6:0.4-0.6;

Coating: Then apply the coating to the above-mentioned amorphous soft magnetic core alloy wire, the coating thickness is 3 microns; after 15 minutes of baking and solidification, the soft magnetic alloy powder coating amorphous soft magnetic core magnetic sensitive composite wire material is obtained, and baked The baking temperature is 130°C.

Embodiment two:

Ingredients: The weight percentage of each component is: 6% Si, 1% Zr, 0.3% Y, 0.2% Ce, 0.9% Ni, 5% B, and the rest is Fe. The coating thickness is about 5 microns.

The purity of the raw materials Si, Zr, Y, Ce, Ni, B, and Fe is greater than 99.9%. The raw materials are melted in a vacuum induction furnace at a melting temperature of 1610-1630°C to obtain a master alloy, and then put into a vacuum induction quenching Remelting is carried out in the remelting tubular crucible in the furnace. The remelting temperature is 1590-1600°C. Melting in the remelting tubular crucible, the molten alloy overflows from the top of the crucible under the action of argon and contacts the edge of the rotating runner to form an amorphous soft magnetic core alloy wire with a diameter of 100-110 microns; the rotation of the rim of the runner The line speed is 22m/s;

Coating preparation: Add orthosilicate ethyl ester, γ-methacryloxypropyltrimethoxysilane and ethanol in proportion to a three-necked flask equipped with a stirrer, and the molar ratio is 3:2:2; Add acetic acid dropwise, the amount added is 5g/100mL, after reacting at room temperature for 3h, add methyl methacrylate and initiator azobisisobutyronitrile, the amount added is 10g/100mL and 5g/100mL respectively, then stir at room temperature for 20min The sol is obtained for use; then commercially available particle size of 50-100nm manganese zinc ferrite powder and the sol are mixed to obtain a coating, and the weight ratio of the manganese zinc ferrite powder and the sol is 6:0.5;

Coating: Then apply the coating to the above-mentioned amorphous soft magnetic core alloy wire, the coating thickness is 5 microns; after 15 minutes of baking and solidification, the soft magnetic alloy powder coating amorphous soft magnetic core magnetic sensitive composite wire material is obtained, and baked The baking temperature is 130°C.

Embodiment three:

Ingredients: The weight percentage of each component is: 4% Si, 0.7% Zr, 0.2% Y, 0.2% Ce, 0.7% Ni, 3% B, and the rest is Fe. The coating thickness is about 4 microns.

The purity of the raw materials Si, Zr, Y, Ce, Ni, B, Fe is greater than 99.9%. The raw materials are melted in a vacuum induction furnace at a melting temperature of 1610°C to obtain a master alloy, which is then placed in a vacuum induction quenching furnace The remelting tube crucible is remelted, and the remelting temperature is 1590°C. The top of the remelting tube crucible is placed 2-4mm below the rim of the runner of the quenching furnace, and the above master alloy is placed in the remelting tube Melting in the crucible, the molten alloy overflows from the top of the crucible under the action of argon and contacts the edge of the rotating runner to form an amorphous soft magnetic core alloy wire with a diameter of 100-110 microns; the rotation speed of the rim of the runner is 20 ~24m/s;

Coating preparation: Add orthosilicate ethyl ester, γ-methacryloxypropyltrimethoxysilane and ethanol in proportion to a three-necked flask equipped with a stirrer, and the molar ratio is 3:2:2; Add acetic acid dropwise, the amount added is 5g/100mL, after reacting at room temperature for 3h, add methyl methacrylate and initiator azobisisobutyronitrile, the amount added is 10g/100mL and 5g/100mL respectively, then stir at room temperature for 20min The sol is obtained for use; then commercially available particle size of 50-100nm manganese zinc ferrite powder and the sol are mixed to obtain a coating, and the weight ratio of the manganese zinc ferrite powder and the sol is 6:0.5;

Coating: Then apply the coating to the above-mentioned amorphous soft magnetic core alloy wire, the coating thickness is 4 microns; after 15 minutes of baking and solidification, the soft magnetic alloy powder coating amorphous soft magnetic core magnetic sensitive composite wire material is obtained, and baked The baking temperature is 130°C.

Embodiment four: (the proportioning of ingredients is not within the scope of the case design example)

Ingredients: The weight percentage of each component is: 2% Si, 0.3% Zr, 0.08% Y, 0.06% Ce, 0.5% Ni, 1% B, and the rest is Fe. The coating thickness is 2 microns.

The purity of the raw materials Si, Zr, Y, Ce, Ni, B, Fe is greater than 99.9%. The raw materials are melted in a vacuum induction furnace at a melting temperature of 1620°C to obtain a master alloy, which is then put into a vacuum induction quenching furnace The remelting tube crucible is used for remelting. The remelting temperature is 1600°C. Melting in the crucible, the molten alloy overflows from the top of the crucible under the action of argon and contacts the edge of the rotating runner to form an amorphous soft magnetic core alloy wire with a diameter of 100-110 microns; the rotational speed of the rim of the runner is 24m /s;

Coating preparation: Add orthosilicate ethyl ester, γ-methacryloxypropyltrimethoxysilane and ethanol in proportion to a three-necked flask equipped with a stirrer, and the molar ratio is 3:2:2; Add acetic acid dropwise, the amount added is 5g/100mL, after reacting at room temperature for 3h, add methyl methacrylate and initiator azobisisobutyronitrile, the amount added is 10g/100mL and 5g/100mL respectively, then stir at room temperature for 20min Obtaining the sol for use; then mixing commercially available manganese-zinc ferrite powder with a particle size of 50-100nm and the sol to obtain a coating, the weight ratio of the manganese-zinc ferrite powder and the sol is 6:0.6;

Coating: Then apply the coating to the above-mentioned amorphous soft magnetic core alloy wire, the coating thickness is 2 microns; after 15 minutes of baking and solidification, the soft magnetic alloy powder coated amorphous soft magnetic core magnetic sensitive composite wire material is obtained, and baked The baking temperature is 130°C.

Embodiment five: (the proportioning of ingredients is not an example within the scope of the design of this case)

Ingredients: The weight percentage of each component is: 7% Si, 2% Zr, 0.5% Y, 0.3% Ce, 1% Ni, 6% B, and the rest is Fe. The coating thickness was 6 microns. The purity of the raw materials Si, Zr, Y, Ce, Ni, B, Fe is greater than 99.9%. The raw materials are melted in a vacuum induction furnace at a melting temperature of 1620°C to obtain a master alloy, which is then put into a vacuum induction quenching furnace Remelting in the remelting tubular crucible, the remelting temperature is 1595°C. Melting in the crucible, the molten alloy overflows from the top of the crucible under the action of argon and contacts the edge of the rotating runner to form an amorphous soft magnetic core alloy wire with a diameter of 100-110 microns; the rotational speed of the rim of the runner is 22m /s;

Coating preparation: Add orthosilicate ethyl ester, γ-methacryloxypropyltrimethoxysilane and ethanol in proportion to a three-necked flask equipped with a stirrer, and the molar ratio is 3:2:2; Add acetic acid dropwise, the amount added is 5g/100mL, after reacting at room temperature for 3h, add methyl methacrylate and initiator azobisisobutyronitrile, the amount added is 10g/100mL and 5g/100mL respectively, then stir at room temperature for 20min The sol is obtained for use; then the commercially available particle size of 50-100nm manganese-zinc ferrite powder and the sol are mixed to obtain a coating, and the weight ratio of the manganese-zinc ferrite powder and the sol is 6:0.4;

Coating: Then apply the coating to the above-mentioned amorphous soft magnetic core alloy wire, the coating thickness is 6 microns; after 15 minutes of baking and solidification, the soft magnetic alloy powder coating amorphous soft magnetic core magnetic sensitive composite wire material is obtained, and baked The baking temperature is 130°C.

Combining the performance parameters of each product in the table below:

Table 1 Performance parameters of each product

Alloy No. Element Saturation magnetization M _s / emu/g Coercivity _Hci /e contrast material Materials obtained from CN200910096349.9 application 83.73～108.24 0.51O ～0.30O product one The product that embodiment one makes 108 0.31 product two The product that embodiment two makes 110 0.28 product three The product that embodiment three makes 112 0.28 product four The product that embodiment four makes 98 0.34 product five The product that embodiment five makes 102 0.30

It can be seen from the above table that the saturation magnetization and the coercive force of the product 1, product 2 and product 3 prepared by the present invention are all improved. The performance of product 5 and product 6 shows that the component composition of the composite material is not within the designed composition range, the saturation magnetization of the material will decrease, and the coercive force will increase. The reason is that the composition of the components is insufficient, and the effect of the alloying elements is not enough; if the composition of the components is too large, unnecessary compounds will be formed, which will reduce the magnetic properties of the material.

Claims (4)

1. A ferrite magnetic layer amorphous soft magnetic core composite material is characterized in that: the weight percentage of its components is: 3～6%Si, 0.5-1%Zr, 0.1～0.3%Y, 0.1% ~0.2% Ce, 0.6-0.9% Ni, 2-5% B, and the rest is Fe. 2. The ferrite magnetic layer amorphous soft magnetic core composite material according to claim 1, characterized in that: the surface coating thickness of the composite material is 3-5 microns. 3. ferrite magnetic layer amorphous soft magnetic core composite material according to claim 1 or 2, is characterized in that: The preparation method of the coating is as follows: In a three-necked flask equipped with a stirrer, tetraethyl orthosilicate, γ-methacryloxypropyl trimethoxysilane and ethanol are added in proportion, and its molar ratio is 3: 2:2; under vigorous stirring, add acetic acid dropwise, the addition amount is 5g/100mL, after reacting at room temperature for 3h, add methyl methacrylate and initiator azobisisobutyronitrile, the addition amount is 10g/100mL and 5g/ 100mL, then stirred at room temperature for 20min to obtain a sol for use; then mix manganese zinc ferrite powder with a particle size of 50-100nm and the sol to obtain a coating, and the weight ratio of the manganese zinc ferrite powder to the sol is 6:0.4-0.6. 4. A method for preparing a ferrite magnetic layer amorphous soft magnetic core wire composite material, characterized in that: the preparation steps are as follows: Amorphous soft magnetic core: according to weight percentage: 3-6% Si, 0.5-1% Zr, 0.1-0.3% Y, 0.1-0.2% Ce, 0.6-0.9% Ni, 2-5% B, the rest Dosing for the alloy composition of Fe; the purity of the raw materials Si, Zr, Y, Ce, Ni, B, and Fe are all greater than 99.9%, put the raw materials into a vacuum induction furnace for melting, and the melting temperature is 1610-1630°C to obtain the master alloy , and then put it into the remelting tubular crucible in the vacuum induction quenching furnace for remelting. The remelting temperature is 1590-1600°C. Place the above-mentioned master alloy in a remelting tubular crucible and melt it. After the alloy is melted, it overflows from the top of the crucible under the action of argon and contacts the edge of the rotating runner to form an amorphous soft magnetic core alloy with a diameter of 100-110 microns. wire; the rotational speed of the wheel rim is 20-24m/s; Coating preparation: Add orthosilicate ethyl ester, γ-methacryloxypropyltrimethoxysilane and ethanol in proportion to a three-necked flask equipped with a stirrer, and the molar ratio is 3:2:2; Add acetic acid dropwise, the amount added is 5g/100mL, after reacting at room temperature for 3h, add methyl methacrylate and initiator azobisisobutyronitrile, the amount added is 10g/100mL and 5g/100mL respectively, then stir at room temperature for 20min The sol is obtained for use; then the manganese zinc ferrite powder and the sol with a particle size of 50-100nm are mixed to obtain a coating, and the weight ratio of the manganese zinc ferrite powder and the sol is 6:0.4-0.6; Coating: Then apply the coating to the above-mentioned amorphous soft magnetic core alloy wire, the coating thickness is 3-5 microns; bake and solidify for 15 minutes to obtain soft magnetic alloy powder coating amorphous soft magnetic core magnetic sensitive composite wire material , the baking temperature is 130°C.

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