CN111138182A - Method for preparing manganese-zinc ferrite with high magnetic conductivity - Google Patents

Method for preparing manganese-zinc ferrite with high magnetic conductivity Download PDF

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CN111138182A
CN111138182A CN201911415747.2A CN201911415747A CN111138182A CN 111138182 A CN111138182 A CN 111138182A CN 201911415747 A CN201911415747 A CN 201911415747A CN 111138182 A CN111138182 A CN 111138182A
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manganese
zinc ferrite
sintering
ferrite
high magnetic
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瞿德林
沈建元
王久如
王晓祥
李丛俊
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Zhongde Electronics Co ltd
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Zhongde Electronics Co ltd
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Abstract

The invention provides a method for preparing high-permeability manganese-zinc ferrite, which comprises the following steps: weighing manganese chloride, zinc sulfate, cobalt chloride and ferric trichloride, adding into deionized water to prepare a mixed solution, adding a mixed alkali solution into the mixed solution, heating for reaction, filtering, washing, drying, grinding and presintering to obtain the compound Mn-Mn alloy with a chemical formulaxZnyCo1‑x‑yFe2O4The cobalt-doped manganese-zinc ferrite; mixing cobalt doped manganese zinc ferrite with CaCO3、Nb2O5、TiO2、ZrO2、Bi2O3Mixing, ball milling, granulating, forming, sintering, heating to 1250-. The invention adopts a chemical coprecipitation methodThe manganese-zinc ferrite is effectively doped, so that the magnetic conductivity of the manganese-zinc ferrite is greatly enhanced.

Description

Method for preparing manganese-zinc ferrite with high magnetic conductivity
Technical Field
The invention relates to the technical field of ferrite, in particular to a method for preparing high-permeability manganese-zinc ferrite.
Background
The Mn-Zn ferrite is a typical soft magnetic material and is widely applied to various recording magnetic heads of multipath communication, switching power supplies, transformer magnetic cores, filters, recording and video recording, information storage systems, medical diagnosis, military and civil anti-electromagnetic interference materials and the like. Its basic requirements are high magnetic permeability, high saturation magnetic induction, low loss, low coercive force and high stability.
At present, the manganese zinc ferrite industry in China has a larger gap compared with the foreign industry, and the research for improving the performance of the manganese zinc ferrite is very important and urgent.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for preparing high-permeability manganese-zinc ferrite, which is used for effectively doping the manganese-zinc ferrite by a chemical coprecipitation method, so that the magnetic conductivity of the manganese-zinc ferrite is greatly enhanced.
The invention is realized by the following technical scheme:
a method for preparing high-permeability manganese-zinc ferrite comprises the following steps:
s1, based on MnxZnyCo1-x-yFe2O4The preparation method comprises the steps of weighing manganese chloride, zinc sulfate, cobalt chloride and ferric trichloride according to the stoichiometric proportion, adding deionized water to prepare a mixed solution, adding a mixed alkali solution into the mixed solution under the condition of stirring, heating for reaction, filtering, washing, drying, grinding and presintering to obtain the compound Mn with the chemical formulaxZnyCo1-x-yFe2O4The cobalt-doped manganese-zinc ferrite;
s2, mixing the cobalt-doped manganese-zinc ferrite obtained in S1 with CaCO3、Nb2O5、TiO2、ZrO2、Bi2O3Mixing, ball milling, granulating, molding, sintering at 800 ℃ for 1-2h, heating to 1150 ℃ for 1-2h, heating to 1350 ℃ for 2-4h, and cooling in furnace to obtain the high-permeability manganeseZinc ferrite.
Preferably, in S1, 0.4. ltoreq. y < x. ltoreq.0.5.
Preferably, in S1, the mixed alkali solution is a mixed solution of ammonia water, 1, 3-propane diamine and triethanolamine in a volume ratio of 3-5:1-2:2-3, wherein the concentration of the ammonia water is 25-30 wt%.
Preferably, in S1, a mixed alkali solution is added to the mixed solution, and the solution is adjusted to pH 8 to 9.
Preferably, in S1, the heating reaction is carried out at 40-50 deg.C for 0.5-1 h.
Preferably, in S1, the pre-sintering temperature is 850-950 ℃, and the pre-sintering time is 1-2 h.
Preferably, in S2, CaCO is used as the reference based on the mass of the cobalt-doped manganese-zinc ferrite3In an amount of 0.1 to 0.2 wt%, Nb2O5In an amount of 0.05 to 0.1 wt%, TiO2Is added in an amount of 0.1 to 0.2 wt%, ZrO2In an amount of 0.01 to 0.08 wt%, Bi2O3The amount of (B) is 0.01-0.1 wt%.
Preferably, in S2, the ball milling is wet ball milling, the ball milling time is 2-4h, and the average particle size of the ball milled particles is 0.4-0.8 μm.
Preferably, in S2, the granulation mode is spray granulation, and the reagent used for granulation is polyvinyl alcohol solution with the concentration of 8-10 wt%.
Preferably, in S2, the temperature is raised to 600-800 ℃ at a temperature raising rate of 2-3 ℃ for min during sintering.
In the method for preparing the manganese-zinc ferrite with high magnetic permeability, the manganese-zinc ferrite prepared by the wet method is not only simple in process compared with the manganese-zinc ferrite prepared by the dry method, but also can be used for obtaining the cobalt-doped micron-sized manganese-zinc ferrite, and has the advantages of high initial magnetic permeability, small crystal grain size and good uniformity. Furthermore, the cobalt-doped manganese-zinc ferrite is subjected to composite doping of other oxides, so that the magnetic conductivity of the manganese-zinc ferrite is further improved.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A method for preparing high-permeability manganese-zinc ferrite comprises the following steps:
(1) according to Mn0.48Zn0.5Co0.02Fe2O4Weighing manganese chloride, zinc sulfate, cobalt chloride and ferric trichloride according to the stoichiometric proportion, adding deionized water to prepare a mixed solution, adding a mixed alkali solution into the mixed solution under the stirring condition, wherein the mixed alkali solution is a mixed solution of ammonia water, 1, 3-propane diamine and triethanolamine in a volume ratio of 4:1.5:2.5, the concentration of the ammonia water is 28 wt%, adjusting the solution to pH 9, heating and reacting at 45 ℃ for 0.8h, filtering, washing with water, drying, grinding, presintering at 900 ℃ for 1.5h to obtain the manganese chloride with the chemical formula of Mn0.48Zn0.5Co0.02Fe2O4The cobalt-doped manganese-zinc ferrite;
(2) mixing the cobalt-doped manganese-zinc ferrite obtained in the step (1) with CaCO3、Nb2O5、TiO2、ZrO2、Bi2O3Mixing, based on the mass of the cobalt-doped manganese-zinc ferrite, CaCO3Is added in an amount of 0.15 wt%, Nb2O5Is added in an amount of 0.08 wt%, TiO2Is added in an amount of 0.15 wt%, ZrO2Is added in an amount of 0.05 wt%, Bi2O3The addition amount of the manganese-zinc ferrite is 0.05 wt%, the ball milling is carried out for 6h until the average grain diameter of the grains is 0.9 mu m, 9 wt% polyvinyl alcohol solution is added after drying for spray granulation, the addition amount of the polyvinyl alcohol solution is 12% of the weight of the dried material, the compression molding and sintering are carried out, the temperature is increased to 700 ℃ at the temperature rising rate of 2.5 ℃ for min, the heat preservation sintering is carried out for 1.5h under the condition of 700 ℃, the temperature is increased to 1100 ℃ again, the heat preservation sintering is carried out for 1.5h, the temperature is increased to 1300 ℃ finally, the heat preservation sintering is carried out for 3h, and the manganese-zinc ferrite with high magnetic conductivity is obtained after furnace cooling.
Example 2
A method for preparing high-permeability manganese-zinc ferrite comprises the following steps:
(1) according to Mn0.4Zn0.48Co0.02Fe2O4Weighing manganese chloride, zinc sulfate, cobalt chloride and ferric trichloride according to the stoichiometric proportion, adding deionized water to prepare a mixed solution, adding a mixed alkali solution into the mixed solution under the stirring condition, wherein the mixed alkali solution is a mixed solution of ammonia water, 1, 3-propane diamine and triethanolamine in a volume ratio of 3:2:2, the concentration of the ammonia water is 25 wt%, adjusting the solution until the pH value is 9, heating and reacting for 1h at 40 ℃, filtering, washing with water, drying, grinding, presintering for 2h at 850 ℃ to obtain the manganese chloride with the chemical formula of Mn0.4Zn0.48Co0.02Fe2O4The cobalt-doped manganese-zinc ferrite;
(2) mixing the cobalt-doped manganese-zinc ferrite obtained in the step (1) with CaCO3、Nb2O5、TiO2、ZrO2、Bi2O3Mixing, based on the mass of the cobalt-doped manganese-zinc ferrite, CaCO3Is added in an amount of 0.2 wt%, Nb2O5Is added in an amount of 0.05 wt%, TiO2Is added in an amount of 0.2 wt%, ZrO2Is added in an amount of 0.01 wt%, Bi2O3The addition amount of the composite material is 0.1 wt%, ball milling is carried out for 4h until the average grain diameter of the grains is 1.0 mu m, polyvinyl alcohol solution with the concentration of 8 wt% is added after drying for spray granulation, the addition amount of the polyvinyl alcohol solution is 13% of the weight of the dried material, pressing and forming are carried out, sintering is carried out, the temperature is increased to 600 ℃ at the temperature increasing rate of 3 ℃ for min, heat preservation and sintering are carried out for 2h under the condition of 600 ℃, the temperature is increased to 1150 ℃ for heat preservation and sintering for 1h, the temperature is increased to 1350 ℃, heat preservation and sintering are carried out for 2h, furnace cooling is carried out, and the manganese zinc ferrite with high magnetic conductivity is obtained.
Example 3
A method for preparing high-permeability manganese-zinc ferrite comprises the following steps:
(1) according to Mn0.4Zn0.5Co0.01Fe2O4The method comprises the steps of weighing manganese chloride, zinc sulfate, cobalt chloride and ferric trichloride according to the stoichiometric proportion, adding deionized water to prepare a mixed solution, adding a mixed alkali solution into the mixed solution under the condition of stirring, and dissolving the mixed alkali solution in the mixed alkali solutionThe solution is a mixed solution of ammonia water, 1, 3-propane diamine and triethanolamine with the volume ratio of 5:1:3, wherein the concentration of the ammonia water is 30 wt%, the solution is adjusted to pH 8, the solution is heated and reacted for 0.5h at 50 ℃, filtered, washed by water, dried, ground and presintered for 1h at 950 ℃ to obtain the compound with the chemical formula of Mn0.4Zn0.5Co0.01Fe2O4The cobalt-doped manganese-zinc ferrite;
(2) mixing the cobalt-doped manganese-zinc ferrite obtained in the step (1) with CaCO3、Nb2O5、TiO2、ZrO2、Bi2O3Mixing, based on the mass of the cobalt-doped manganese-zinc ferrite, CaCO3Is added in an amount of 0.1 wt%, Nb2O5Is added in an amount of 0.1 wt%, TiO2Is added in an amount of 0.1 wt%, ZrO2Is added in an amount of 0.08 wt%, Bi2O3The addition amount of the manganese zinc ferrite is 0.01 wt%, the ball milling is carried out for 8 hours until the average grain diameter of the grains is 0.8 mu m, the polyvinyl alcohol solution with the concentration of 10 wt% is added after drying for spray granulation, the addition amount of the polyvinyl alcohol solution is 14% of the weight of the dried material, the compression molding and sintering are carried out, the temperature is increased to 800 ℃ at the temperature increasing rate of 2 ℃ for \\ min, the heat preservation sintering is carried out for 1 hour at the temperature of 800 ℃, the temperature is increased to 1000 ℃ for the heat preservation sintering for 2 hours, the temperature is increased to 1250 ℃, the heat preservation sintering is carried out for 4 hours, and the manganese zinc ferrite with high magnetic conductivity is obtained after furnace cooling.
Example 4
A method for preparing high-permeability manganese-zinc ferrite comprises the following steps:
(1) according to Mn0.43Zn0.49Co0.08Fe2O4Weighing manganese chloride, zinc sulfate, cobalt chloride and ferric trichloride according to the stoichiometric proportion, adding deionized water to prepare a mixed solution, adding a mixed alkali solution into the mixed solution under the stirring condition, wherein the mixed alkali solution is a mixed solution of ammonia water, 1, 3-propane diamine and triethanolamine in a volume ratio of 4:1:3, the concentration of the ammonia water is 30 wt%, adjusting the solution to pH 8, heating and reacting at 50 ℃ for 0.5h, filtering, washing with water, drying, grinding, presintering at 900 ℃ for 2h to obtain Mn with the chemical formula0.43Zn0.49Co0.08Fe2O4The cobalt-doped manganese-zinc ferrite;
(2) mixing the cobalt-doped manganese-zinc ferrite obtained in the step (1) with CaCO3、Nb2O5、TiO2、ZrO2、Bi2O3Mixing, based on the mass of the cobalt-doped manganese-zinc ferrite, CaCO3Is added in an amount of 0.16 wt%, Nb2O5Is added in an amount of 0.07 wt%, TiO2Is added in an amount of 0.15 wt%, ZrO2Is added in an amount of 0.05 wt%, Bi2O3The addition amount of the manganese-zinc ferrite is 0.06 wt%, the ball milling is carried out for 5h until the average grain diameter of the grains is 1.0 mu m, the polyvinyl alcohol solution with the concentration of 9 wt% is added after drying for spray granulation, the addition amount of the polyvinyl alcohol solution is 15% of the weight of the dried material, the compression molding and sintering are carried out, the temperature is increased to 700 ℃ at the temperature increasing rate of 3 ℃ for min, the heat preservation sintering is carried out for 1.5h under the condition of 700 ℃, the temperature is increased to 1050 ℃ for heat preservation sintering for 2h, the temperature is increased to 1300 ℃, the heat preservation sintering is carried out for 3h, and the manganese-zinc ferrite with high magnetic conductivity is obtained after furnace cooling.
Comparative example 1
A method for preparing manganese-zinc ferrite comprises the following steps:
(1) according to Fe2O3Respectively weighing Fe with the mol ratio of ZnO to MnO of 50:25:242O3Grinding ZnO and MnO, and pre-sintering at 900 ℃ for 1.5h to obtain a pre-sintered material;
(2) mixing the pre-sintered material obtained in the step (1) with CoO and CaCO3、Nb2O5、TiO2、ZrO2、Bi2O3Mixing, based on the mass of the pre-sintering material, the adding amount of CoO is 0.64 wt%, CaCO3Is added in an amount of 0.15 wt%, Nb2O5Is added in an amount of 0.08 wt%, TiO2Is added in an amount of 0.15 wt%, ZrO2Is added in an amount of 0.05 wt%, Bi2O3The addition amount of the polyvinyl alcohol is 0.05 wt%, the ball milling is carried out for 6h until the average grain diameter of the particles is 0.9 mu m, the polyvinyl alcohol solution with the concentration of 9 wt% is added after drying for spray granulation, the addition amount of the polyvinyl alcohol solution is 12% of the weight of the dried material, the mixture is pressed, formed and sintered at the temperature of 2.5 ℃ for minAnd raising the temperature to 700 ℃ at a temperature rate, carrying out heat preservation sintering for 1.5h under the condition of 700 ℃, raising the temperature to 1100 ℃, carrying out heat preservation sintering for 1.5h, finally raising the temperature to 1300 ℃, carrying out heat preservation sintering for 3h, and carrying out furnace cooling to obtain the magnetic permeability manganese-zinc ferrite.
And (3) performance testing: the manganese-zinc-ferrite material finished products obtained in the above examples 1 to 4 and comparative example 1 were subjected to electrical property tests, and the results are shown in the following table:
Figure BDA0002351149440000061
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 as the technical scope of the present invention, and equivalents and modifications thereof should be included in the technical scope of the present invention.

Claims (10)

1. A method for preparing high-permeability manganese-zinc ferrite is characterized by comprising the following steps:
s1, based on MnxZnyCo1-x-yFe2O4The preparation method comprises the steps of weighing manganese chloride, zinc sulfate, cobalt chloride and ferric trichloride according to the stoichiometric proportion, adding deionized water to prepare a mixed solution, adding a mixed alkali solution into the mixed solution under the condition of stirring, heating for reaction, filtering, washing, drying, grinding and presintering to obtain the compound Mn with the chemical formulaxZnyCo1-x-yFe2O4The cobalt-doped manganese-zinc ferrite;
s2, mixing the cobalt-doped manganese-zinc ferrite obtained in S1 with CaCO3、Nb2O5、TiO2、ZrO2、Bi2O3Mixing, ball milling, granulating, molding, sintering, heat-preserving and sintering for 1-2h under the conditions of 600-800 ℃, heating to 1000-1150 ℃, heat-preserving and sintering for 1-2h, finally heating to 1250-1350 ℃, heat-preserving and sintering for 2-4h, and cooling along with a furnace to obtain the manganese-zinc ferrite with high magnetic permeability.
2. The method of claim 1, wherein in S1, y is 0.4 ≦ y < x is 0.5.
3. The method for preparing manganese zinc ferrite with high magnetic permeability according to claim 1 or 2, wherein in S1, the mixed alkali solution is a mixed solution of ammonia water, 1, 3-propane diamine and triethanolamine in a volume ratio of 3-5:1-2:2-3, wherein the concentration of ammonia water is 25-30 wt%.
4. The method of any one of claims 1 to 3, wherein the mixed solution is added with a mixed alkali solution and the solution is adjusted to pH 8-9 in S1.
5. The method for preparing a manganese zinc ferrite with high magnetic permeability according to any one of claims 1 to 4, wherein the heating reaction in S1 is carried out at a temperature of 40 to 50 ℃ for 0.5 to 1 hour.
6. The method for preparing Mn-Zn ferrite with high magnetic permeability according to any one of claims 1 to 5, wherein the pre-sintering temperature in S1 is 850-950 ℃ and the pre-sintering time is 1-2 h.
7. The method for preparing Mn-Zn ferrite with high magnetic permeability according to any one of claims 1 to 6, wherein in S2, CaCO is used as the reference based on the mass of the Co-doped Mn-Zn ferrite3In an amount of 0.1 to 0.2 wt%, Nb2O5In an amount of 0.05 to 0.1 wt%, TiO2Is added in an amount of 0.1 to 0.2 wt%, ZrO2In an amount of 0.01 to 0.08 wt%, Bi2O3The amount of (B) is 0.01-0.1 wt%.
8. The method for preparing a manganese zinc ferrite with high magnetic permeability according to any one of claims 1 to 7, wherein in S2, the ball milling is wet ball milling, the ball milling time is 2 to 4 hours, and the average particle size of the ball milled particles is 0.4 to 0.8 μm.
9. The method of preparing a manganese zinc ferrite with high magnetic permeability according to any one of claims 1 to 8, wherein in S2, the granulation is performed by spray granulation, and the reagent used for granulation is a polyvinyl alcohol solution with a concentration of 8 to 10 wt%.
10. The method for preparing Mn-Zn ferrite with high magnetic permeability according to any one of claims 1 to 9, wherein in S2, the temperature is raised to 600-800 ℃ at a temperature rise rate of 2-3 ℃ min during sintering.
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