阅读说明：本技术 一种低温烧结锰锌软磁铁氧体材料的制备方法 (Preparation method of low-temperature sintered manganese-zinc soft magnetic ferrite material ) 是由 瞿德林 王久如 李丛俊 于 2020-11-27 设计创作，主要内容包括：本发明公开了一种低温烧结锰锌软磁铁氧体材料的制备方法,包括以下步骤：按配方称取主料,与水混合后,经过一次球磨,烘干,保温预烧得到预烧料；再称取适量CaCO-3、CoO、SiO-2、V-2O-5、Bi-2O-3添加剂,与上述预烧料混合后,加入2-膦酸丁烷-1,2,4-三羧酸和水,进行二次球磨,得到混合料；将上述混合料与聚乙烯醇粘结剂混合后,先加热保温处理,然后喷雾造粒、压制成型,得到坯料,再经过低温烧结得到锰锌软磁铁氧体材料。本发明通过对锰锌软磁铁氧体配方以及低温烧结工艺的优化,可以在降低烧结温度、减少能耗的同时,使制备的锰锌软磁铁氧体材料具有高饱和磁感应强度、低损耗的优点,软磁性能优良。(The invention discloses a preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material, which comprises the following steps: weighing the main materials according to the formula, mixing the main materials with water, performing primary ball milling, drying, and performing heat preservation and presintering to obtain a pre-sintered material; then weighing appropriate amount of CaCO 3 、CoO、SiO 2 、V 2 O 5 、Bi 2 O 3 An additive, which is mixed with the pre-sintering material, and then added with 2-phosphonic butane-1, 2, 4-tricarboxylic acid and water for secondary ball milling to obtain a mixture; and mixing the mixture with a polyvinyl alcohol binder, heating and preserving heat, then carrying out spray granulation and compression molding to obtain a blank, and sintering at a low temperature to obtain the manganese-zinc soft magnetic ferrite material. The invention can reduce the sintering temperature and the sintering process by optimizing the formula of the manganese-zinc soft magnetic ferrite and the low-temperature sintering processThe prepared manganese-zinc soft magnetic ferrite material has the advantages of high saturation magnetic induction intensity, low loss and excellent soft magnetic performance while the energy consumption is low.)

1. A preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material is characterized by comprising the following steps:

s1, weighing the main materials according to the following molar percentage: 52.5-54.0 mol% Fe₂O₃38.5-40.5 mol% MnO and the balance of ZnO;

s2, mixing the main material with water, and performing primary ball milling, drying, heat preservation and presintering to obtain a presintering material;

s3, weighing CaCO 0.05-0.08% of the mass of the pre-sintered material₃0.03-0.05% of CoO, 0.01-0.02% of SiO₂0.01-0.02% of V₂O₅0.005-0.01% of Bi₂O₃Mixing the mixture with the pre-sintered material, adding 2-phosphonic butane-1, 2, 4-tricarboxylic acid and water, and performing secondary ball milling to obtain a mixture;

s4, mixing the mixture with a polyvinyl alcohol aqueous solution, performing heat preservation treatment at the temperature of 140 ℃ and 180 ℃, and then granulating and pressing to form a blank;

and S5, heating the blank to 1050-.

2. The method of preparing a low temperature sintered manganese-zinc soft magnetic ferrite material according to claim 1, wherein the mass of 2-phosphonobutane-1, 2, 4-tricarboxylic acid is 0.25-0.3% of the mass of the pre-sintering material.

3. The method for preparing a low-temperature sintered manganese-zinc soft magnetic ferrite material according to claim 1 or 2, wherein the mass of the polyvinyl alcohol is 0.7-0.75% of the mass of the pre-sintering material.

4. The method for preparing a low-temperature sintered manganese-zinc soft magnetic ferrite material according to any one of claims 1 to 3, wherein in the step S5, the blank is heated to 240 ℃ at a heating rate of 2 to 2.5 ℃/min, then heated to 480 ℃ at 440-.

5. The method for preparing a low-temperature sintered manganese-zinc soft magnetic ferrite material according to any one of claims 1 to 4, wherein the time for the heat-preservation sintering in step S5 is 4 to 6 hours.

6. The method for preparing a low temperature sintered manganese-zinc soft magnetic ferrite material according to any one of claims 1 to 5, wherein the time of the heat preservation treatment in step S4 is 2 to 4 hours.

7. The method for preparing a low-temperature sintered manganese-zinc soft magnetic ferrite material according to any one of claims 1 to 6, wherein in the step S2, the temperature for the heat preservation and pre-sintering is 800-950 ℃ for 1.5-3 h.

8. The method for preparing a low-temperature sintered manganese-zinc soft magnetic ferrite material according to any one of claims 1 to 7, wherein the mass concentration of the polyvinyl alcohol aqueous solution is 8 to 10%.

Technical Field

The invention relates to the technical field of soft magnetic ferrite materials, in particular to a preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material.

Background

The soft magnetic ferrite material is a magnetic material with small coercive force and easy magnetization, and is used for manufacturing important electronic components such as transformers, filters, inductors and the like in electricians and electronic equipment. The Mn-Zn soft magnetic ferrite material is one of the most applied soft magnetic ferrite materials, has the characteristics of high initial permeability, low power loss and the like, is favorable for reducing energy loss, and is widely applied to the fields of communication, automobiles, illumination, household appliances and the like. At present, the sintering temperature of the manganese-zinc soft magnetic ferrite is usually 1300-. Moreover, with the continuous development of the technology, electronic components gradually tend to be miniaturized, and higher requirements are put forward on the performance of the manganese-zinc soft magnetic ferrite material. Therefore, the preparation of the manganese-zinc soft magnetic ferrite material with high saturation magnetic induction and low loss has important significance under the low-temperature sintering process.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides a preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material.

The invention provides a preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material, which comprises the following steps:

s1, weighing the main materials according to the following molar percentage: 52.5-54.0 mol% Fe₂O₃38.5-40.5 mol% MnO and the balance of ZnO;

s2, mixing the main material with water, and performing primary ball milling, drying, heat preservation and presintering to obtain a presintering material;

s3, weighing CaCO 0.05-0.08% of the mass of the pre-sintered material₃0.03-0.05% of CoO, 0.01-0.02% of SiO₂0.01-0.02% of V₂O₅0.005-0.01% of Bi₂O₃Mixing the mixture with the pre-sintered material, adding 2-phosphonic butane-1, 2, 4-tricarboxylic acid and water, and performing secondary ball milling to obtain a mixture;

s4, mixing the mixture with a polyvinyl alcohol aqueous solution, performing heat preservation treatment at the temperature of 140 ℃ and 180 ℃, and then granulating and pressing to form a blank;

and S5, heating the blank to 1050-.

Preferably, the mass of the 2-phosphonobutane-1, 2, 4-tricarboxylic acid is 0.25-0.3% of the mass of the pre-sintering material.

Preferably, the mass of the polyvinyl alcohol is 0.7-0.75% of the mass of the pre-sintering material.

Preferably, in the step S5, the blank is first heated to 240 ℃ at a heating rate of 2-2.5 ℃/min, then heated to 480 ℃ at 440-.

Preferably, in the step S5, the time for the heat preservation sintering is 4-6 h.

Preferably, in the step S4, the time of the heat preservation process is 2-4 h.

Preferably, in the step S2, the temperature for the heat preservation and pre-sintering is 800-950 ℃, and the time is 1.5-3 h.

Preferably, the mass concentration of the polyvinyl alcohol aqueous solution is 8-10%.

The invention has the following beneficial effects:

according to the invention, the appropriate additive is added into the material, so that the sintering temperature can be reduced, and the manganese-zinc soft magnetic ferrite material is prepared under the low-temperature sintering process, but the reduction of the sintering temperature can also bring about the problems of insufficient grain growth, large pores, reduced sintering density and the like, so that the soft magnetic performance of the material is reduced, and the improvement of the saturation magnetic induction intensity of the material and the reduction of loss are not facilitated; according to the invention, a proper amount of 2-phosphonic butane-1, 2, 4-tricarboxylic acid is added as a dispersing agent in the ball milling process of the pre-sintering material and the additive, compared with the conventional dispersing agent, the 2-phosphonic butane-1, 2, 4-tricarboxylic acid can be more effectively adsorbed on the surface of the powder, and the repulsive force between the powder is increased, so that a better dispersing effect is achieved, the agglomeration degree of the pre-sintering material powder is reduced, the particle size is reduced, the solid phase reaction activity is enhanced, the porosity is reduced, the sintering density is improved, and the saturation magnetic induction intensity of the material and the loss are favorably improved; and after the polyvinyl alcohol binder is added, proper heating and heat preservation treatment is carried out, carboxyl in 2-phosphonic acid butane-1, 2, 4-tricarboxylic acid and hydroxyl in polyvinyl alcohol are subjected to proper esterification and crosslinking, so that the binding effect of the binder is improved, the using amount of the binder is reduced, the porosity is reduced, the sintering density is improved, the saturation magnetic induction intensity of the material is improved, and the loss is reduced. By optimizing the formula of the manganese-zinc soft magnetic ferrite and the low-temperature sintering process, the invention can reduce the sintering temperature and the energy consumption, and simultaneously ensure that the prepared manganese-zinc soft magnetic ferrite material has the advantages of high saturation magnetic induction intensity, low loss and excellent soft magnetic performance.

Detailed Description

The technical solution of the present invention will be described in detail below with reference to specific examples.

Example 1

A preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material comprises the following steps:

s1, weighing the main materials according to the following molar percentage: 52.5 mol% Fe₂O₃38.5 mol% MnO and the balance of ZnO;

s2, mixing the main material with water, performing primary ball milling, drying, and pre-burning at 800 ℃ for 3 hours to obtain a pre-burnt material;

s3, weighing CaCO accounting for 0.05 percent of the mass of the pre-sintered material₃0.03% of CoO, 0.01% of SiO₂0.01% of V₂O₅0.005% of Bi₂O₃After being mixed with the pre-sintering material, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and water are added for secondary ball milling to obtain a mixture, wherein the mass of the 2-phosphonic butane-1, 2, 4-tricarboxylic acid is 0.25 percent of that of the pre-sintering material;

s4, mixing the mixture with a polyvinyl alcohol aqueous solution with the mass concentration of 8%, carrying out heat preservation treatment for 4 hours at 140 ℃, and then granulating, pressing and forming to obtain a blank, wherein the mass of the polyvinyl alcohol is 0.7% of that of the pre-sintered material;

and S5, heating the blank to 220 ℃ at a heating rate of 2 ℃/min, heating to 440 ℃ at a heating rate of 1 ℃/min, heating to 850 ℃ at a heating rate of 2.5 ℃/min, heating to 1050 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation sintering for 6h to obtain the manganese-zinc soft magnetic ferrite material.

Example 2

A preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material comprises the following steps:

s1, weighing the main materials according to the following molar percentage: 54.0 mol% Fe₂O₃40.5 mol% MnO and the balance of ZnO;

s2, mixing the main material with water, performing primary ball milling, drying, and pre-burning at 950 ℃ for 1.5 hours to obtain a pre-burnt material;

s3, weighing CaCO accounting for 0.08 percent of the mass of the pre-sintered material₃0.05% of CoO, 0.02% of SiO₂0.02% of V₂O₅0.01% of Bi₂O₃After being mixed with the pre-sintering material, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and water are added for secondary ball milling to obtain a mixture, wherein the mass of the 2-phosphonic butane-1, 2, 4-tricarboxylic acid is 0.3 percent of that of the pre-sintering material;

s4, mixing the mixture with a polyvinyl alcohol aqueous solution with the mass concentration of 10%, carrying out heat preservation treatment for 2 hours at 180 ℃, and then granulating, pressing and forming to obtain a blank, wherein the mass of the polyvinyl alcohol is 0.75% of that of the pre-sintered material;

s5, heating the blank to 240 ℃ at a heating rate of 2.5 ℃/min, heating to 480 ℃ at a heating rate of 1.5 ℃/min, heating to 880 ℃ at a heating rate of 3 ℃/min, heating to 1150 ℃ at a heating rate of 1.5 ℃/min, and carrying out heat preservation and sintering for 4 hours to obtain the manganese-zinc soft magnetic ferrite material.

Example 3

A preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material comprises the following steps:

s1, weighing the main materials according to the following molar percentage: 53 mol% Fe₂O₃39.5 mol% MnO, and the balance ZnO;

s2, mixing the main material with water, performing primary ball milling, drying, and pre-burning at 850 ℃ for 2 hours to obtain a pre-burnt material;

s3, weighing CaCO accounting for 0.06 percent of the mass of the pre-sintered material₃0.04% ofCoO, 0.015% SiO₂0.015% of V₂O₅0.008% of Bi₂O₃After being mixed with the pre-sintering material, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and water are added for secondary ball milling to obtain a mixture, wherein the mass of the 2-phosphonic butane-1, 2, 4-tricarboxylic acid is 0.28 percent of that of the pre-sintering material;

s4, mixing the mixture with a polyvinyl alcohol aqueous solution with the mass concentration of 9%, carrying out heat preservation treatment for 3 hours at 160 ℃, and then granulating, pressing and forming to obtain a blank, wherein the mass of the polyvinyl alcohol is 0.72% of that of the pre-sintered material;

s5, heating the blank to 235 ℃ at a heating rate of 2.5 ℃/min, heating to 460 ℃ at a heating rate of 1 ℃/min, heating to 860 ℃ at a heating rate of 2.5 ℃/min, heating to 1100 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation sintering for 5h to obtain the manganese-zinc soft magnetic ferrite material.

Comparative example 1

A preparation method of a low-temperature sintered manganese-zinc soft magnetic ferrite material comprises the following steps:

s1, weighing the main materials according to the following molar percentage: 53 mol% Fe₂O₃39.5 mol% MnO, and the balance ZnO;

s2, mixing the main material with water, performing primary ball milling, drying, and pre-burning at 850 ℃ for 2 hours to obtain a pre-burnt material;

s3, weighing CaCO accounting for 0.06 percent of the mass of the pre-sintered material₃0.04% of CoO, 0.015% of SiO₂0.015% of V₂O₅0.008% of Bi₂O₃Mixing the ammonium citrate with the pre-sintering material, adding ammonium citrate and water, and performing secondary ball milling to obtain a mixture, wherein the mass of the ammonium citrate is 0.4% of that of the pre-sintering material;

s4, mixing the mixture with a polyvinyl alcohol aqueous solution with the mass concentration of 9%, granulating, and performing compression molding to obtain a blank, wherein the mass of the polyvinyl alcohol is 0.9% of that of the pre-sintered material;

s5, heating the blank to 200 ℃ at a heating rate of 2.5 ℃/min, heating to 400 ℃ at a heating rate of 1 ℃/min, heating to 860 ℃ at a heating rate of 2.5 ℃/min, heating to 1100 ℃ at a heating rate of 1 ℃/min, and carrying out heat preservation sintering for 5h to obtain the manganese-zinc soft magnetic ferrite material.

The performance of the manganese-zinc soft magnetic ferrite materials prepared in examples 1 to 3 and comparative example 1 was tested by using a magnetic measuring instrument, and the test sample was ring-shaped, and had an outer diameter of 30mm, an inner diameter of 15mm and a height of 5 mm. The test results are shown in table 1:

TABLE 1 ferrite Material Performance test results

Test items	Example 1	Example 2	Example 3	Comparative example 1
					Bs(mT)	432	435	441	405
tgδ/μi(×10-6)	1.45	1.48	1.39	1.77

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.