阅读说明：本技术 一种高磁导率锰锌铁氧体磁性材料及其制备方法 (High-permeability manganese-zinc ferrite magnetic material and preparation method thereof ) 是由 谭孝强 陈明 于 2020-12-29 设计创作，主要内容包括：本发明属于锰锌铁氧体磁性材料技术领域,具体涉及一种高磁导率锰锌铁氧体磁性材料及其制备方法。该材料包括主料组分和添加组分,主料组分包括下述质量百分比的成分：60-68％Fe-2O-3、23-30％MnO、5-9％ZnO,添加组分的各成分按主料组分总质量的百分数计,包括：0.020-0.035％CaCO-3、0.005-0.015％SiO-2、0.01-0.02％Bi-2O-3、0.01-0.02％MoO-3、0.02-0.03％P-2O-5。本发明通过一次砂磨、一次喷雾造粒、预烧、二次砂磨、二次喷雾造粒、压型和烧结后得到锰锌铁样体材料,提高了材料的磁导率,并改善了材料的综合性能。(The invention belongs to the technical field of manganese-zinc ferrite magnetic materials, and particularly relates to a manganese-zinc ferrite magnetic material with high magnetic permeability and a preparation method thereof. The material comprises main material components and additive components, wherein the main material components comprise the following components in percentage by mass: 60-68% Fe 2 O 3 23-30% of MnO and 5-9% of ZnO, wherein the additive components comprise the following components in percentage by mass of the total mass of the main material components: 0.020-0.035% CaCO 3 、0.005‑0.015％SiO 2 、0.01‑0.02％Bi 2 O 3 、0.01‑0.02％MoO 3 、0.02‑0.03％P 2 O 5 . The manganese-zinc-iron sample material is obtained by primary sanding, primary spray granulation, pre-sintering, secondary sanding, secondary spray granulation, compression molding and sintering, the magnetic conductivity of the material is improved, and the method is changed into the methodThe comprehensive performance of the material is improved.)

1. The manganese-zinc ferrite magnetic material with high magnetic conductivity is characterized by comprising main material components and additive components, wherein the main material components comprise the following components in percentage by mass: 60-68% Fe₂O₃23-30% of MnO and 5-9% of ZnO, wherein the additive components comprise the following components in percentage by mass of the total mass of the main material components: 0.020-0.035% CaCO₃、0.005-0.015％SiO₂、0.01-0.02％Bi₂O₃、0.01-0.02％MoO₃、0.02-0.03％P₂O₅。

2. The manganese-zinc-ferrite magnetic material with high magnetic permeability as claimed in claim 1, wherein the main material component comprises the following components by mass percent: 66% Fe₂O₃27% MnO and 7% ZnO, wherein the components of the additive component comprise the following components in percentage by total mass of the main material component: 0.025% CaCO₃、0.008％SiO₂、0.015％Bi₂O₃、0.012％MoO₃、0.023％P₂O₅。

3. The method of claim 1, wherein the method comprises the steps of:

(1) mixing the main ingredients to obtain a mixed material, and performing primary spray granulation after primary sanding on the mixed material;

(2) presintering after primary spray granulation, and adding an additive component into the presintering material;

(3) after pre-sintering, sequentially carrying out secondary sanding and secondary spray granulation;

(4) and carrying out profiling and sintering processes after secondary spray granulation to obtain the manganese-zinc-iron sample material.

4. The method of claim 3, wherein in step (1), the average particle size of the primary-sanded particles is 1.2-2.2 μm.

5. The method for preparing a manganese zinc ferrite magnetic material with high magnetic permeability according to claim 3, wherein in the step (2), the pre-sintering step: and (3) placing the pre-sintering material in a high-temperature electric furnace for pre-sintering, adopting a programmed heating process to raise the temperature to 600-700 ℃ at the speed of 10 ℃/min, preserving the heat for 1-2h, and then lowering the temperature in the sintering furnace to room temperature at the cooling speed of 5 ℃/min to finish the pre-sintering.

6. The method of claim 3, wherein in step (3), the average particle size of the particles after secondary sanding is 0.5-0.7 μm.

7. The method for preparing a manganese zinc ferrite magnetic material with high magnetic permeability according to claim 3, wherein in the step (3), PVA liquid is added into the slurry after secondary sanding for component correction, and secondary spray granulation is performed after stirring for 1.5h, wherein the concentration of the PVA liquid is 10-12%, and the addition amount is 7-9% of the total mass of the main material components.

8. The method for preparing a manganese zinc ferrite magnetic material with high magnetic permeability according to claim 3, wherein in the step (4), the sintering process comprises the following steps: and (3) feeding the material subjected to secondary spray granulation into a sintering furnace for sintering, adopting a program to heat up at the oxygen partial pressure of 6-10%, increasing the temperature to 550-152 ℃ at the speed of 10 ℃/min and preserving the heat for 0.5-1h, then increasing the temperature to 1100-1300 ℃ at the speed of 12 ℃/min and preserving the heat for 2-3h, finally cooling to 550-650 ℃ at the speed of 8 ℃/min and preserving the heat for 1-2h, and finally cooling the temperature in the sintering furnace to room temperature at the cooling speed of 5 ℃/min to finish the sintering process.

Technical Field

The invention belongs to the technical field of manganese-zinc ferrite magnetic materials, and particularly relates to a manganese-zinc ferrite magnetic material with high magnetic permeability and a preparation method thereof.

Background

The manganese-zinc ferrite is Mn_0.5Zn_0.5Fe₂O₄The soft magnetic ferrite with the spinel structure is used as a very important basic functional material in the electronic industry and the information industry, has the magnetic properties of high saturation magnetic induction intensity, high initial permeability, low loss, low coercive force and the like, and has the advantages of clean energy, LED illumination, aerospace, hybrid power, electric vehicles and other fieldsHas important application and is inseparable from the production and life of people. Nowadays, electronic devices and the like are developing towards miniaturization, and in order to adapt to the development trend, higher requirements on the magnetic properties of manganese-zinc ferrite magnetic materials are provided in the industry.

At present, the method generally adopted in the industry for improving the magnetic conductivity of the manganese-zinc ferrite magnetic material is to improve the ZnO content in the manganese-zinc ferrite magnetic material, but when the ZnO content is improved, Fe₂O₃The content of (b) becomes relatively low, resulting in a decrease in curie temperature and saturation magnetic flux density, and the wide temperature characteristics are also poor, and the fluctuation in magnetic permeability of the manganese-zinc ferrite material is large when the temperature change of the surrounding environment is large. Therefore, there is a need to develop a manganese-zinc-ferrite magnetic material having a high magnetic permeability without degrading its overall performance.

Disclosure of Invention

In order to solve the problem that the comprehensive performance of the existing manganese-zinc-iron ferrite material cannot be ensured while the magnetic conductivity is improved, the invention provides a manganese-zinc-iron ferrite magnetic material with high magnetic conductivity, which improves the magnetic conductivity of the material and improves the comprehensive performance of the material.

The manganese-zinc ferrite magnetic material with high magnetic conductivity provided by the invention comprises main material components and additive components, wherein the main material components comprise the following components in percentage by mass: 60-68% Fe₂O₃23-30% of MnO and 5-9% of ZnO, wherein the additive components comprise the following components in percentage by mass of the total mass of the main material components: 0.020-0.035% CaCO₃、0.005-0.015％SiO₂、0.01-0.02％Bi₂O₃、0.01-0.02％MoO₃、0.02-0.03％P₂O₅。

Further, the main material components comprise the following components in percentage by mass: 66% Fe₂O₃27% MnO and 7% ZnO, wherein the components of the additive component comprise the following components in percentage by total mass of the main material component: 0.025% CaCO₃、0.008％SiO₂、0.015％Bi₂O₃、0.012％MoO₃、0.023％P₂O₅。

The preparation method of the manganese-zinc ferrite magnetic material with high magnetic permeability comprises the following steps:

(1) mixing the main ingredients to obtain a mixed material, and performing primary spray granulation after primary sanding on the mixed material;

(2) presintering after primary spray granulation, and adding an additive component into the presintering material;

(3) after pre-sintering, sequentially carrying out secondary sanding and secondary spray granulation;

(4) and carrying out profiling and sintering processes after secondary spray granulation to obtain the manganese-zinc-iron sample material.

Further, in the step (1), the average particle diameter of the particles after primary sanding is 1.2-2.2 μm.

Further, in the step (2), the burn-in step: and (3) placing the pre-sintering material in a high-temperature electric furnace for pre-sintering, adopting a programmed heating process to raise the temperature to 600-700 ℃ at the speed of 10 ℃/min, preserving the heat for 1-2h, and then lowering the temperature in the sintering furnace to room temperature at the cooling speed of 5 ℃/min to finish the pre-sintering. With the rise of the presintering temperature, the saturation magnetization of the powder is gradually increased, the coercive force and the relative residual magnetization are firstly increased and then decreased, the invention adopts the temperature programming, the temperature of 600-700 ℃ is set as the optimal temperature, and the saturation magnetization of the powder is ensured.

Further, in the step (3), the average particle diameter of the particles after secondary sanding is 0.5-0.7 μm.

Further, in the step (3), after secondary sanding, PVA liquid is added into the slurry for component correction, and secondary spray granulation is performed after stirring for 1.5h, wherein the concentration of the PVA liquid is 10-12%, and the addition amount is 7-9% of the total mass of the main material components.

Further, in the step (4), the sintering process: and (3) feeding the material subjected to secondary spray granulation into a sintering furnace for sintering, adopting a program to heat up at the oxygen partial pressure of 6-10%, increasing the temperature to 550-152 ℃ at the speed of 10 ℃/min and preserving the heat for 0.5-1h, then increasing the temperature to 1100-1300 ℃ at the speed of 12 ℃/min and preserving the heat for 2-3h, finally cooling to 550-650 ℃ at the speed of 8 ℃/min and preserving the heat for 1-2h, and finally cooling the temperature in the sintering furnace to room temperature at the cooling speed of 5 ℃/min to finish the sintering process. The grain size can be increased by properly increasing the temperature rise speed, so that the initial permeability is improved, and the power consumption is reduced, but if the temperature rise speed is too high, the pores are increased, the uniformity of the grains is poor, the power consumption is increased, and the temperature rise speed of 10 ℃/min and 12 ℃/min is the optimal temperature rise speed.

The invention has the beneficial effects that:

the manganese zinc ferrite magnetic material with high magnetic conductivity provided by the invention is simultaneously added with a plurality of elements for composite doping, and the proper proportion is selected, so that the magnetic conductivity of the material is improved, and the comprehensive performance of the material is improved. With addition of CaCO₃And SiO₂The calcium silicate can be formed by the composite doping of the two, the thickness of a crystal boundary can be improved, the resistivity of the material is obviously improved, and the eddy current loss is reduced; adding MoO₃Not only can generate liquid phase sintering to promote the grain growth, but also can inhibit the generation of overlarge grains, promote the uniform growth of the grains, improve the initial permeability, and MoO₃When the content of (A) is too high, pores are increased, and the growth of crystal grains is hindered, and the invention selects the optimal MoO through experiments₃Adding amount; bi₂O₃Can form a liquid phase to promote solid phase reaction and grain growth, but an excessive amount of Bi₂O₃The grains can grow abnormally and influence the performance of Bs, and the optimal MoO is selected through experiments₃Adding amount; p₂O₅The porosity can be reduced, the density can be increased, and the magnetic conductivity, the resistivity, the Curie temperature and other properties of the manganese-zinc ferrite magnetic material can be further improved.

According to the preparation method of the manganese zinc ferrite magnetic material with high magnetic conductivity, provided by the invention, twice sanding and twice spray granulation are adopted, so that slurry is mixed more uniformly and sufficiently, the full completion of solid phase reaction in the pre-sintering process is facilitated, the time of twice sanding and twice spray granulation is reduced, the energy consumption is reduced, and the preparation method is simple and practical to operate and has good applicability.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The manganese-zinc ferrite magnetic material with high magnetic permeability provided by the embodiment comprises main material components and additive components, wherein the main material components comprise the following components in percentage by mass: 64% Fe₂O₃27% MnO and 9% ZnO, wherein the additive components comprise the following components in percentage by mass of the total mass of the main material components: 0.02% CaCO₃、0.005％SiO₂、0.01％Bi₂O₃、0.01％MoO₃、0.02％P₂O₅。

The preparation method of the manganese-zinc ferrite magnetic material with high magnetic permeability comprises the following steps:

(1) mixing the main ingredients to obtain a mixed material, and performing primary spray granulation on the mixed material after primary sanding, wherein the average particle size of particles after primary sanding is 1.5 mu m;

(2) presintering after primary spray granulation, adding an additive component into the presintering material, putting the presintering material into a high-temperature electric furnace for presintering, raising the temperature to 600 ℃ at the speed of 10 ℃/min by adopting a program, preserving the temperature for 1.5h, and then reducing the temperature in a sintering furnace to room temperature at the temperature reduction speed of 5 ℃/min to finish the presintering;

(3) pre-burning, performing secondary sanding, wherein the average particle size of particles after secondary sanding is 0.6 mu m, adding PVA liquid into the slurry after secondary sanding for component correction, stirring for 1.5h, and performing secondary spray granulation, wherein the concentration of the PVA liquid is 10%, the addition amount is 7% of the total mass of the main material components, and performing secondary spray granulation after PVA component correction;

(4) carrying out compression molding and sintering processes after secondary spray granulation, wherein the sintering process comprises the following steps: and (3) feeding the material subjected to secondary spray granulation into a sintering furnace for sintering, heating to 550 ℃ at the speed of 10 ℃/min by adopting a program under the oxygen partial pressure of 6%, preserving heat for 1h, then heating to 1100 ℃ at the speed of 12 ℃/min, preserving heat for 2.5h, finally cooling to 550 ℃ at the speed of 8 ℃/min, preserving heat for 1.5h, and finally cooling the temperature in the sintering furnace to room temperature at the cooling speed of 5 ℃/min to finish the sintering process to obtain the ferromanganese-zinc sample material.

Example 2

The manganese-zinc ferrite magnetic material with high magnetic permeability provided by the embodiment comprises main material components and additive components, wherein the main material components comprise the following components in percentage by mass: 68% Fe₂O₃27% MnO and 5% ZnO, wherein the additive components comprise the following components in percentage by mass of the total mass of the main material components: 0.035% CaCO₃、0.015％SiO₂、0.02％Bi₂O₃、0.02％MoO₃、0.03％P₂O₅。

The preparation method of the manganese-zinc ferrite magnetic material with high magnetic permeability comprises the following steps:

(1) mixing the main ingredients to obtain a mixed material, and performing primary spray granulation on the mixed material after primary sanding, wherein the average particle size of particles after primary sanding is 1.7 mu m;

(2) presintering after primary spray granulation, adding an additive component into the presintering material, putting the presintering material into a high-temperature electric furnace for presintering, raising the temperature to 680 ℃ at the speed of 10 ℃/min by adopting a program, preserving the temperature for 1.2h, and then reducing the temperature in a sintering furnace to room temperature at the temperature reduction speed of 5 ℃/min to finish the presintering;

(3) pre-burning, performing secondary sanding, wherein the average particle size of particles after secondary sanding is 0.6 mu m, adding PVA liquid into the slurry after secondary sanding for component correction, stirring for 1.5h, and performing secondary spray granulation, wherein the concentration of the PVA liquid is 10%, the addition amount is 9% of the total mass of the main material components, and performing secondary spray granulation after PVA component correction;

(4) carrying out compression molding and sintering processes after secondary spray granulation, wherein the sintering process comprises the following steps: and (3) feeding the material subjected to secondary spray granulation into a sintering furnace for sintering, heating to 600 ℃ at the speed of 10 ℃/min by adopting a program under the oxygen partial pressure of 10 percent, preserving heat for 0.5h, then heating to 1250 ℃ at the speed of 12 ℃/min, preserving heat for 2.5h, finally cooling to 620 ℃ at the speed of 8 ℃/min, preserving heat for 1.5h, and finally cooling the temperature in the sintering furnace to room temperature at the cooling speed of 5 ℃/min to finish the sintering process to obtain the ferromanganese-zinc sample material.

Example 3

The manganese-zinc ferrite magnetic material with high magnetic permeability provided by the embodiment comprises main material components and additive components, wherein the main material components comprise the following components in percentage by mass: 66% Fe₂O₃27% MnO and 7% ZnO, wherein the additive components comprise the following components in percentage by mass of the total mass of the main material components: 0.025% CaCO₃、0.008％SiO₂、0.015％Bi₂O₃、0.012％MoO₃、0.023％P₂O₅。

The preparation method of the manganese-zinc ferrite magnetic material with high magnetic permeability comprises the following steps:

(1) mixing the main ingredients to obtain a mixed material, and performing primary spray granulation on the mixed material after primary sanding, wherein the average particle size of particles after primary sanding is 1.8 mu m;

(2) presintering after primary spray granulation, adding an additive component into the presintering material, putting the presintering material into a high-temperature electric furnace for presintering, raising the temperature to 650 ℃ at the speed of 10 ℃/min by adopting a program, preserving the temperature for 1.5h, and then reducing the temperature in a sintering furnace to room temperature at the temperature reduction speed of 5 ℃/min to finish the presintering;

(3) pre-burning, performing secondary sanding, wherein the average particle size of particles after secondary sanding is 0.6 mu m, adding PVA liquid into the slurry after secondary sanding for component correction, stirring for 1.5h, and performing secondary spray granulation, wherein the concentration of the PVA liquid is 10%, the addition amount is 8% of the total mass of the main material components, and performing secondary spray granulation after PVA component correction;

(4) carrying out compression molding and sintering processes after secondary spray granulation, wherein the sintering process comprises the following steps: and (3) feeding the material subjected to secondary spray granulation into a sintering furnace for sintering, heating to 580 ℃ at the speed of 10 ℃/min by adopting a program under the oxygen partial pressure of 6-10%, preserving heat for 1h, heating to 1200 ℃ at the speed of 12 ℃/min, preserving heat for 2.5h, cooling to 600 ℃ at the speed of 8 ℃/min, preserving heat for 1.5h, and cooling the temperature in the sintering furnace to room temperature at the cooling speed of 5 ℃/min to finish the sintering process to obtain the ferromanganese-zinc sample material.

Comparative example 1

The manganese zinc ferrite magnetic material with high magnetic permeability provided by the comparative example does not add CaCO in the added components₃And SiO₂The other components and the preparation method are the same as those in example 3.

Comparative example 2

The manganese-zinc ferrite magnetic material with high magnetic permeability provided by the comparative example does not add Bi in the added components₂O₃The other components and the preparation method are the same as those in example 3.

Comparative example 3

The manganese zinc ferrite magnetic material with high magnetic permeability provided by the comparative example does not add MoO in the added components₃The other components and the preparation method are the same as those in example 3.

Comparative example 4

The manganese zinc ferrite magnetic material with high magnetic permeability provided by the comparative example does not add P in the additive components₂O₅The other components and the preparation method thereof were the same as in example 3.

The manganese-zinc-ferrite magnetic materials prepared in the above examples 1 to 3 and comparative examples 1 to 4 were subjected to performance tests, and the results of the tests are shown in table 1.

TABLE 1-Performance test results of manganese Zinc ferrite magnetic materials

As can be seen from table 1, compared with comparative examples 1 to 4, the manganese zinc ferrite magnetic materials of examples 1 to 3 have excellent and stable magnetic properties such as high magnetic permeability, wide temperature, high Bs, strong coercive force, etc., which indicates that several elements doped compositely according to the mixture ratio of the invention can improve the magnetic permeability of the materials and can improve the comprehensive properties of the materials.

Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.