阅读说明：本技术 一种新型纳米结晶磁性材料的制备方法 (Preparation method of novel nanocrystalline magnetic material ) 是由 徐灿华 于 2019-11-11 设计创作，主要内容包括：本发明涉及磁性材料的制备方法,公开了一种新型纳米结晶磁性材料的制备方法。其原料按照如下百分比组成：Pd 0.3～0.6％,Ni 0.8～1.2％,In 0.2～0.6％,Ga 0.05～-0.08％,Ge 0.2～0.5％,Be 0.03～0.06％,Ce 0.01～0.05％,Au 0.003～0.006％,Si 2～5％,B 1～3％,Fe余量,原料的质量百分比之和等于100％,熔炼成合金带,侵入试剂熔盐保持一定时间即成。(The invention relates to a preparation method of a magnetic material, and discloses a preparation method of a novel nanocrystalline magnetic material. The raw materials of the material comprise the following components in percentage by weight: 0.3-0.6% of Pd, 0.8-1.2% of Ni, 0.2-0.6% of In, 0.05-0.08% of Ga, 0.2-0.5% of Ge, 0.03-0.06% of Be, 0.01-0.05% of Ce, 0.003-0.006% of Au, 2-5% of Si, 1-3% of B and the balance of Fe, wherein the sum of the mass percentages of the raw materials is equal to 100%, smelting the raw materials into an alloy belt, and immersing the alloy belt In reagent molten salt for a certain time.)

1. A preparation method of a novel nanocrystalline magnetic material is characterized in that the raw materials comprise the following components in percentage by weight:

and Fe and the balance, wherein the sum of the mass percentages of the raw materials is equal to 100%, smelting the raw materials into an alloy strip, and then soaking the alloy strip into reagent molten salt for a certain time to obtain the alloy strip.

2. The method for preparing a novel nanocrystalline magnetic material according to claim 1, characterized In that the purities of Pd, Ni, In, Ga, Ge, Be, Ce, Au and Fe In the raw materials are all more than 99.9%, B is added In the form of ferroboron, wherein the percentage by weight of B is 24%.

3. The method for preparing a novel nanocrystalline magnetic material according to claim 1, characterized in that the raw materials in the above ratio are put into a vacuum induction furnace to be smelted into liquid at a temperature of 1480-1500 ℃, and then cooled to be made into a block-shaped alloy blank.

4. The method for preparing a novel nanocrystalline magnetic material according to claim 3, characterized in that an alloy blank prepared from the raw material is put into a melting tube type crucible in a vacuum induction forming furnace for remelting, the melting temperature is 1500-1520 ℃, and the alloy is melted into an alloy in a solution state.

5. The method for preparing a novel nanocrystalline magnetic material according to claim 4, wherein in the whole process of alloy smelting in the vacuum induction forming furnace, the upper part of the smelting tube type crucible is connected with a nitrogen system through a valve, and the pressure of the nitrogen system is 1.5-1.8 atmospheres.

6. The method for preparing a novel nanocrystalline magnetic material according to claim 4, wherein a through hole is formed in the bottom of the melting tube type crucible, the diameter of the through hole is 1-1.5 mm, the inner diameter is 12-14 mm, and the height is 250-280 mm.

7. The method of claim 4, wherein the bottom of the melting tube crucible is placed 2-4 mm above the rim of the forming furnace runner, and after the alloy is melted, a valve at the upper part of the melting tube crucible is opened, and the liquid alloy is sprayed from the through hole at the bottom of the crucible to the rim of the rotating forming furnace runner under the pressure of nitrogen to form a continuous alloy strip.

8. A method for preparing a novel nanocrystalline magnetic material according to any one of claims 1 to 7, characterized in that the linear speed of rotation of the forming furnace wheel is 24 to 26m/s, and the resulting alloy ribbon has a thickness of 200 to 350 μm and a width of 3 to 5 mm.

9. A method for preparing a novel nanocrystalline magnetic material according to any one of claims 1 to 7, wherein the alloy strip is kept at a constant temperature for 20min when the temperature of the alloy strip is lowered to 650 to 750 ℃, the alloy strip is immersed in a reagent molten salt, a direct current power supply is connected, pulse power supply is adopted, and the average current density is controlled to be 60mA/cm₂The alloy belt moves at a constant speed in the molten salt, the advancing speed is 0.03-0.096/min, and the residence time of each point of the alloy belt in the molten salt is 30-35 min.

10. The method for preparing a novel nanocrystalline magnetic material according to claim 9, characterized in that the prepared alloy strip is placed in a liquid nitrogen atmosphere for low temperature treatment at-100 ℃ to-130 ℃ and is kept warm for 10 to 15 min; then standing for 1-2 h at room temperature; and then placing the mixture in a furnace at the temperature of 200-250 ℃, preserving heat for 2-4 hours, and then cooling to room temperature.

The technical field is as follows:

the invention relates to the technical field of magnetic material formulas and preparation processes, in particular to a preparation method of a novel nano-crystalline magnetic material.

Background art:

the yield of the permanent magnet and soft magnet ferrites in China accounts for 68-72% of the global yield since 2011, the market supply of the magnetic product raw materials in China is sufficient, and the magnetic material is supported by a huge application market and is a genuine large country for producing and manufacturing the magnetic materials.

From the production aspect, the global production of magnetic materials is mainly focused on Japan and China at present, from the technical and productivity aspects, Japan is a magnetic material technology capturer, and the productivity of the magnetic materials in China is the top world, and about 68-75% of the world magnets are produced every year. But most of them are hard magnetic material products using rare earth ore.

In terms of product competition, the international market is leading in japan, the united states and a part of european countries. The countries start early in the production of magnetic materials, the development capability of new products is strong, the technical content is high, the competition of high-grade ferrite magnetic materials in the international market is mainly concentrated in the countries, and a large number of enterprises participate in the international market competition of high-grade magnetic materials in China. With the continuous development of new application markets, such as new markets in the development of automotive electronics, LEDTV, LED lighting, EMC, 4C (computer, communication, radio and television, content service) fusion, 4G and 5G communication, smart grid, Internet of things, new energy automobiles and the like, more new development opportunities are provided for the development of the Chinese magnetic material industry, and the utilization of a large amount of rare earth ores can be saved.

The invention content is as follows:

in view of the above problems, the present invention provides a method for preparing a novel nanocrystalline magnetic material, which is characterized in that the raw materials comprise, by weight:

and Fe and the balance, wherein the sum of the mass percentages of the raw materials is equal to 100%, smelting the raw materials into an alloy strip, and then soaking the alloy strip into reagent molten salt for a certain time to obtain the alloy strip.

Furthermore, the purities of Pd, Ni, In, Ga, Ge, Be, Ce, Au and Fe In the raw materials are all more than 99.9%, B is added In the form of ferroboron, wherein the weight percentage of B is 24%.

Further, the raw materials in the proportion are put into a vacuum induction furnace to be smelted into liquid at the temperature of 1480-1500 ℃, and then the liquid is cooled to be made into a blocky alloy blank.

Further, the alloy blank prepared from the raw materials is put into a smelting tube type crucible in a vacuum induction forming furnace for smelting again, the smelting temperature is 1500-1520 ℃, and the alloy is smelted into an alloy in a solution state.

Furthermore, in the whole process of smelting the alloy in the vacuum induction forming furnace, the upper part of the smelting tube type crucible is connected with a nitrogen system through a valve, and the pressure of the nitrogen system is 1.5-1.8 atmospheric pressures.

Furthermore, the bottom of the smelting tube type crucible is provided with a through hole, the aperture is 1-1.5 mm, the inner diameter is 12-14 mm, and the height is 250-280 mm.

Furthermore, the bottom of the smelting tube type crucible is arranged 2-4 mm above the rim of the rotating wheel of the forming furnace, after the alloy is melted, a valve at the upper part of the smelting tube type crucible is opened, and the liquid alloy is sprayed to the rim of the rotating wheel of the forming furnace from the through hole at the bottom of the crucible under the pressure of nitrogen, so that a continuous alloy strip is formed.

Furthermore, the rotating linear speed of the rotating wheel of the forming furnace is 24-26 m/s, the thickness of the obtained alloy strip is 200-350 μm, and the width of the obtained alloy strip is 3-5 mm.

Further, when the temperature of the alloy belt is reduced to 650-750 ℃, keeping the temperature for 20min, immersing the alloy belt into the reagent molten salt, switching on a direct-current power supply, adopting pulse power supply, controlling the average current density to be 60mA/cm2, enabling the alloy belt to move at a constant speed in the molten salt, enabling the moving speed to be 0.03-0.096/min, and ensuring that the residence time of each point of the alloy belt in the molten salt is 30-35 min.

Further, the prepared alloy belt is placed in liquid nitrogen atmosphere for low-temperature treatment, the temperature is-100 ℃ to-130 ℃, and the temperature is kept for 10-15 min; then standing for 1-2 h at room temperature; and then placing the mixture in a furnace at the temperature of 200-250 ℃, preserving heat for 2-4 hours, and then cooling to room temperature.

Description of the drawings:

FIG. 1 is a linear plot of the saturation magnetic flux density coercivity;

FIG. 2 is a graph showing the change in coercive force versus Cu concentration;

fig. 3 is a comparison of the metallographic structure of the ratios of the four components.

The specific implementation mode is as follows:

the method comprises the steps of putting raw materials weighed according to a proportion into a vacuum induction furnace for smelting, wherein the smelting temperature is 1480-1500 ℃, fully smelting to obtain an alloy solution, and cooling to obtain a blocky alloy blank. Then, putting the mixture into a smelting tube type crucible in a vacuum induction forming furnace for smelting again, wherein the smelting temperature is 1500-1520 ℃.

After the alloy is completely smelted into a liquid state, a valve at the upper part of the smelting tube type crucible is opened, the liquid alloy is sprayed to the rotating wheel rim of the forming furnace from a through hole at the bottom of the crucible under the pressure of nitrogen to form a continuous alloy strip, and meanwhile, the alloy strip is immersed into the analytically pure reagent molten salt.

The analytically pure reagent molten salt is connected with a direct current power supply, pulse power supply is adopted, and the average current density is controlled to be 60mA/cm 2; the alloy belt moves at a constant speed in the molten salt, and the advancing speed is 0.03-0.096/min; keeping the residence time of each point of the alloy strip in the molten salt to be 30-35 minutes; after the alloy strip is extracted from the molten salt, the alloy strip is wound into a coil by a strip winding machine, and the material preparation is finished;

and then placing the alloy strip in a liquid nitrogen atmosphere for low-temperature treatment, standing at room temperature, heating, preserving heat and cooling to room temperature.

Further, the bottom of the smelting tube type crucible is provided with a through hole, the upper part of the smelting tube type crucible is connected with a nitrogen system through a valve, and the pressure of the nitrogen system is 1.5-1.8 atmospheric pressures; the bottom of the smelting tube type crucible is arranged 2-4 mm above the rim of the runner of the forming furnace; the inner diameter of the smelting tube type crucible is 12-14 mm, the height of the smelting tube type crucible is 250-280 mm, and the aperture of a through hole at the bottom of the smelting tube type crucible is 1-1.5 mm.

Further, the rotating linear speed of the rotating wheel is 24-26 m/s; the thickness of the obtained alloy strip is 200-350 mu m, and the width is 3-5 mm.

Furthermore, AgCl, CaCl2, NaCl, NaF and SiO2 reagents used were all analytically pure.

Further, the low-temperature treatment temperature is-100 ℃ to-130 ℃, and the heat preservation time is 15-0 min; then standing for 1-2 hours at room temperature; and then, preserving the heat for 2 to 4 hours at the temperature of between 200 and 250 ℃, and then cooling the mixture to room temperature along with the furnace.

The invention has the beneficial effects that:

in the invention, the Ge and the second transition system Pd can effectively inhibit the growth of crystal grains, are beneficial to obtaining a finer and uniform crystal grain structure and can improve the thermal stability of the magnet.

The In, Ga, Au and B In the raw material components act together to improve the amorphous forming capability; si, Be and Ce can prevent the crystal grains from growing up in the heat treatment, and the crystal grains are refined, so that the resistivity is improved, and the loss is reduced.

The Ni of the first transition system inhibits the growth of grains at the grain intersection and refines the grains, thereby inhibiting the enhancement of stray fields around the grains and further improving the magnetic performance of the material.

The alloy material adopts a mode of combining rapid cooling, heat treatment and alloying in solidification, so that the phase size in the alloy is effectively reduced, the uniform distribution of chemical components in the material is ensured, the magnetic property of the alloy is ensured, the internal stress caused by rapid cooling is greatly reduced through gradient treatment, and the mechanical property of the alloy is also ensured.

The product obtained by the invention has the performance superior to other soft magnetic materials, heavy rare earth elements are not used in the preparation, the used rare earth elements are trace, and the cost of other raw materials is lower.

The alloy is rapidly cooled in the preparation process, so that the uniformity of the components, the structure and the performance of the alloy is ensured, and the quality of the alloy is ensured.

The alloy has simple preparation process and simple process, and the produced alloy has good performance and is very convenient for industrial production.

The material prepared by the invention can be widely applied and can be used for manufacturing magnetic material devices in the fields of information, communication and the like.