阅读说明：本技术 一种镍锌铁氧体材料及制备方法和应用 (Nickel-zinc ferrite material and preparation method and application thereof ) 是由 朱晓丽 陈军林 蒋玉梅 于 2021-09-15 设计创作，主要内容包括：本发明提供了一种镍锌铁氧体材料及制备方法和应用,所述镍锌铁氧体材料包括主成分和添加剂,主成分包括Fe-(2)O-(3)、NiO、ZnO和CuO,添加剂包括Co-(2)O-(3)、Nb-(2)O-(5)和Bi-(2)O-(3),所述添加剂包括Co-(2)O-(3)、Nb-(2)O-(5)和Bi-(2)O-(3),所述主成分中,Fe-(2)O-(3)的含量为47.8～49.8mol％,NiO含量为13.5～15mol％,ZnO含量为29～31mol％,CuO的含量为5～7mol％,Co-(2)O-(3)含量为0.15～0.3wt％,Nb-(2)O-(5)含量为0.04～0.075wt％,Bi-(2)O-(3)含量为0.05～0.15wt％,本发明通过严格控制各组分的比例可以获得高Bs高Q值低比温度系数的镍锌铁氧体材料。(The invention provides a nickel-zinc ferrite material and a preparation method and application thereof, wherein the nickel-zinc ferrite material comprises a main component and an additive, and the main component comprises Fe 2 O 3 NiO, ZnO and CuO, and the additive comprises Co 2 O 3 、Nb 2 O 5 And Bi 2 O 3 Said additive comprising Co 2 O 3 、Nb 2 O 5 And Bi 2 O 3 In the main component, Fe 2 O 3 47.8-49.8 mol%, NiO content 13.5-15 mol%, ZnO content 29-31 mol%, CuO content 5-7 mol%, Co 2 O 3 0.15 to 0.3 wt% of Nb 2 O 5 0.04 to 0.075 wt% of Bi 2 O 3 The content is 0.05-0.15 wt%, and the invention is tightThe proportion of each component is controlled by grids, so that the nickel-zinc ferrite material with high Bs, high Q value and low temperature coefficient can be obtained.)

1. A nickel zinc ferrite material, characterized in that the nickel zinc ferrite material comprises a main component and an additive, wherein the main component comprises Fe₂O₃NiO, ZnO and CuO, the additive comprising Co₂O₃、Nb₂O₅And Bi₂O₃The Fe is calculated by taking the molar weight of the main component as 100 percent₂O₃47.8-49.8 mol%, 13.5-15 mol% of NiO, 29-31 mol% of ZnO, 5-7 mol% of CuO, and the mass of the main component is 100%, the Co is Co₂O₃0.15 to 0.3 wt% of Nb₂O₅0.04 to 0.075 wt.% of the Bi₂O₃The mass of (B) is 0.05-0.15 wt%.

2. The nickel-zinc-ferrite material according to claim 1, wherein said Fe is contained in an amount of 100% by mole of said main component₂O₃The molar percentage of the component (a) is 48-49.3 mol%;

preferably, the molar percentage of NiO is 14-15 mol%;

preferably, the mol percentage of the ZnO is 30-31 mol%;

preferably, the mol percentage of the CuO is 5.6-6.5 mol%.

3. The nickel zinc ferrite material of claim 1 or 2 wherein the additive further comprises CaCO₃、ZrO₂Or V₂Any one or a combination of at least two of O;

preferably, based on the principal component100 percent of CaCO₃The mass of (A) is 0-0.07 wt%;

preferably, the ZrO₂The mass of (A) is 0-0.08 wt%;

preferably, said V₂O₅The mass of (B) is 0 to 0.06 wt%.

4. A method for preparing a nickel zinc ferrite material as claimed in any one of claims 1 to 3, characterized in that said method comprises the steps of:

(1) uniformly mixing a main component material, an additive material and a solvent, grinding the mixture for one time to obtain a primary mixture, drying the mixture, and then pre-burning the mixture to obtain a pre-burned material;

(2) and (2) mixing the pre-sintered material obtained in the step (1) with a solvent, then carrying out secondary grinding treatment to obtain a secondary mixture, and carrying out granulation, molding and sintering treatment to obtain the nickel-zinc ferrite material.

5. The method according to claim 4, wherein the primary grinding treatment in step (1) comprises ball milling;

preferably, the ball milling time is 1-3 h;

preferably, the mass ratio of the raw materials, the grinding balls and the water during ball milling is 1 (4.5-6) to 0.6-1.2;

preferably, the temperature of the pre-sintering treatment is 750-950 ℃;

preferably, the pre-sintering treatment time is 2-6 h.

6. The method according to claim 4 or 5, wherein the secondary grinding treatment in step (2) comprises sanding;

preferably, the sanding time is 1-3 h;

preferably, the mass ratio of the pre-sintering material to the grinding ball to the water during sanding is 1 (4-7) to 1.0-1.2;

preferably, the average particle size of the powder after sanding is 0.8-1.5 μm.

7. The method according to any one of claims 4 to 6, wherein the granulating in the step (2) comprises mixing the secondary abrasive, the polyvinyl alcohol solution and the antifoaming agent, rapidly stirring, and spraying to obtain a granulated powder;

preferably, the concentration of the polyvinyl alcohol solution is 5-15 wt%;

preferably, the antifoaming agent comprises n-octanol;

preferably, the concentration of the n-octanol is 0.05-0.2 wt%;

preferably, the mass ratio of the secondary grinding material to the polyvinyl alcohol solution is 1 (0.08-0.1);

preferably, the time of the rapid stirring is 2-5 h.

8. The production method according to any one of claims 4 to 7, wherein the molding in the step (2) includes pressing the granulated powder and zinc stearate after mixing them into a green body;

preferably, the mass ratio of the granulated powder to the zinc stearate is 1 (0.001-0.004);

preferably, the pressing pressure is 3-12 MPa.

9. The production method according to any one of claims 4 to 8, wherein the sintering treatment in the step (2) includes one-step temperature-raising sintering, two-step temperature-raising sintering, one-step temperature-lowering, two-step temperature-lowering, and three-step temperature-lowering;

preferably, the one-step heating sintering comprises heating from room temperature to 950-1000 ℃ within 5-8 h and keeping the temperature for 1-2 h;

preferably, the two-step heating sintering comprises continuously heating the green body to 1100-1160 ℃ within 0.5-2 h and preserving the temperature for 3-6 h;

preferably, the oxygen content of the two-step temperature rise sintering is 0.01-0.05%.

Preferably, the one-step cooling comprises cooling to 400-600 ℃ within 2-4 h;

preferably, the secondary cooling comprises continuously cooling to 100-200 ℃ within 1-3 h;

preferably, the three-step temperature reduction comprises the step of continuously and naturally reducing the temperature to the room temperature within 0.5-1 h.

10. Use of a nickel zinc ferrite material as claimed in any one of claims 1 to 3 for microwave communication and/or as a magnetic material.

Technical Field

The invention belongs to the technical field of soft magnetic ferrite, and relates to a nickel-zinc ferrite material, and a preparation method and application thereof.

Background

The ferrite magnetic material mainly comprises spinel-type, garnet-type and magnetoplumbite-type polycrystalline and single crystal ferrite materials, has high resistivity, small loss, good dielectric property and frequency characteristic, is an important magnetic functional material, and has wide application in the fields of modern communication, military, electronics, information, chemical industry, biology, medicine and the like.

In recent years, with the wide application of ferrite in various industries such as communication, IT industry, automobile industry, aerospace field, warships and national defense weapon equipment systems, and the like, in outdoor facilities of modern communication equipment, equipment such as satellites and the like, the currently adopted NiZn soft magnetic ferrite material has the magnetic permeability of 500-700, but the Curie temperature is only 120 ℃ and the Bs is below 360mT, so that the defects of low inductance after current superposition, low energy conversion efficiency, high loss and the like occur in the use process of products made of the NiZn material.

CN104529423A discloses a low-temperature coefficient anti-stress nickel-zinc soft magnetic ferrite material, which comprises main components of ferric oxide, zinc oxide, nickel protoxide and copper oxide and auxiliary components of nano SiO₂Nano Bi₂O₃、Co₃O₄、TiO₂And 0.10-0.45 w of talcum powder, the invention provides a preparation method of the nickel-zinc ferrite with a high specific temperature coefficient of magnetic conductivity, but the magnetic conductivity mu i of the ferrite reaches 600, the requirement of high magnetic conductivity is met, and the ferrite does not have high Q value performance.

CN109369168A discloses a ferrite composition containing Fe as the main component₂O₃40.0 to 49.8 mol% of iron oxide in terms of CuO, 5.0 to 14.0 mol% of copper oxide in terms of CuO, 0 to 32.0 mol% of zinc oxide in terms of ZnO, and the balance of nickel oxide, wherein the amount of ZrO contained is 100 wt% based on the main component₂0.5 to 4.0 wt% of tin oxide in terms of Bi₂O₃0.10 to 1.00 wt% converted bismuth oxide, Co₃O₄Cobalt oxide in a reduced amount of 0.21 to.00 wt% is used as a subcomponent, and the magnetic permeability of the material of the present invention is about 500, and the material can achieve a high magnetic permeability. However, the ferrite has low saturation induction, residual induction and remanence, and high coercive force and dielectric loss.

CN109485399A discloses a NiCuZn ferrite magnetic sheet for NFC and wireless charging, and discloses a magnetic sheet made of 48-49 mol% Fe₂O₃、8～12mol％CuO、15～18mol％NiO, the balance ZnO, and 0.1 to 1 wt% of Bi₂O₃、0.01～0.1wt％Co₂O₃、0.05～0.3wt％ZrO₂The ferrite magnetic sheet has excellent characteristics of high saturation magnetic induction, high residual magnetic ratio, low coercive force, low dielectric loss, low ferromagnetic resonance line width and the like, but is mainly used for NFC and wireless charging, but the material has a low specific permeability and a high temperature coefficient, and the inductance of the product can change under high and low temperature conditions.

The above scheme has the problems of low Q value, low saturation magnetic induction, residual magnetic induction and residual magnetism ratio, high coercive force and dielectric loss and high low specific permeability temperature coefficient, so that the development of a ferrite material with high Q value, high saturation magnetic induction, residual magnetic induction and residual magnetism ratio, low coercive force and dielectric loss and low specific permeability temperature coefficient is necessary.

Disclosure of Invention

The invention aims to provide a nickel-zinc ferrite material, a preparation method and application thereof₂O₃NiO, ZnO and CuO, the additive comprising Co₂O₃、Nb₂O₅And Bi₂O₃The nickel zinc ferrite material with high Bs, high Q value and low temperature coefficient can be obtained by strictly controlling the proportion of each component.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a nickel zinc ferrite material comprising a main component and an additive, the main component comprising Fe₂O₃NiO, ZnO and CuO, the additive comprising Co₂O₃、Nb₂O₅And Bi₂O₃The Fe is calculated by taking the molar weight of the main component as 100 percent₂O₃The molar percentage of (a) is 47.8 to 49.8 mol% (e.g., 47.8 mol%, 47.9 mol%, 48 mol%, 48.3 mol%, 48.5 mol%, 48.8 mol%, 49 mol%, 49.5 mol%, or 49.8 m)ol%, etc.), the molar percentage of the NiO is 13.5-15 mol% (for example: 13.5 mol%, 13.8 mol%, 14 mol%, 14.5 mol%, 15 mol%, etc.), and the molar percentage of ZnO is 29 to 31 mol% (for example: 29 mol%, 29.5 mol%, 30 mol%, 30.5 mol%, 31 mol%, or the like), and the molar percentage content of the CuO is 5 to 7 mol% (for example: 5 mol%, 5.5 mol%, 6 mol%, 6.5 mol%, 7 mol%, or the like) of the main component, the Co being present in an amount of 100% by mass of the main component₂O₃0.15 to 0.3 wt% (e.g., 0.15 wt%, 0.18 wt%, 0.2 wt%, 0.25 wt%, or 0.3 wt%), and Nb₂O₅0.04 to 0.075 wt% (e.g., 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, or 0.075 wt%), and Bi₂O₃0.05 to 0.15 wt%, for example: 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.12 wt%, or 0.15 wt%, etc.

According to the invention, the specific component proportion of the main component and the additive in the nickel-zinc ferrite material is optimized and adjusted, and the problem of large inductance change of the material at-40-125 ℃ is solved by accurately controlling the proportion and the content of each component, so that the output stability of the inductor under the extremely low temperature/high temperature condition is improved.

Preferably, the Fe is present in an amount of 100 mol% based on the molar amount of the main component₂O₃The molar percentage of (b) is 48-49.3 mol%, for example: 48 mol%, 48.3 mol%, 48.5 mol%, 48.8 mol%, 49 mol%, 49.3 mol%, or the like.

Preferably, the molar percentage of the NiO is 14-15 mol%, for example: 14 mol%, 14.2 mol%, 14.5 mol%, 14.8 mol%, 15 mol%, or the like.

Preferably, the molar percentage of the ZnO is 30 to 31 mol%, for example: 30 mol%, 30.2 mol%, 30.5 mol%, 30.8 mol%, 31 mol%, or the like.

Preferably, the molar percentage content of the CuO is 5.6 to 6.5 mol%, for example: 5.6 mol%, 5.8 mol%, 6 mol%, 6.3 mol%, 6.5 mol%, or the like.

Preferably, the additive further comprises CaCO₃、ZrO₂Or V₂Any one of O orA combination of at least two.

Preferably, the CaCO is 100% by mass of the main component₃0 to 0.07 wt%, for example: 0 wt%, 0.01 wt%, 0.02 wt%, 0.04 wt%, 0.05 wt%, or 0.07 wt%, etc.

Preferably, the ZrO₂0 to 0.08 wt%, for example: 0 wt%, 0.01 wt%, 0.02 wt%, 0.04 wt%, 0.05 wt%, or 0.08 wt%, etc.

Preferably, said V₂O₅0 to 0.06 wt%, for example: 0 wt%, 0.01 wt%, 0.02 wt%, 0.04 wt%, 0.05 wt%, or 0.06 wt%, etc.

In a second aspect, the present invention provides a method for preparing a nickel-zinc-ferrite material according to the first aspect, the method comprising the steps of:

(1) uniformly mixing a main component material, an additive material and a solvent, grinding the mixture for one time to obtain a primary mixture, drying the mixture, and then pre-burning the mixture to obtain a pre-burned material;

(2) and (2) mixing the pre-sintered material obtained in the step (1) with a solvent, then carrying out secondary grinding treatment to obtain a secondary mixture, and carrying out granulation, molding and sintering treatment to obtain the nickel-zinc ferrite material.

Preferably, the primary grinding treatment in step (1) comprises ball milling.

Preferably, the time of ball milling is 1-3 h, such as: 1h, 1.2h, 1.5h, 2h, 2.5h or 3h and the like.

Preferably, the mass ratio of the raw materials, the grinding balls and the water during ball milling is 1 (4.5-6) to (0.6-1.2), such as: 1:4.5:0.6, 1:4.8:0.8, 1:5:0.8, 1:4.9:1 or 1:6:1.2, etc.

Preferably, the temperature of the pre-sintering treatment is 750-950 ℃, for example: 750 deg.C, 800 deg.C, 850 deg.C, 900 deg.C or 950 deg.C.

Preferably, the time of the pre-burning treatment is 2-6 h, for example: 2h, 3h, 4h, 5h or 6h and the like.

Preferably, the secondary grinding treatment in step (2) comprises sanding.

Preferably, the sanding time is 1-3 h, for example: 1h, 1.2h, 1.5h, 2h, 2.5h or 3h and the like.

Preferably, the mass ratio of the pre-sintering material to the grinding balls to the water during sanding is 1 (4-7) to (1.0-1.2), such as: 1:4:1, 1:5:1.1, 1:6:1.1 or 1:7:1.2, etc.

Preferably, the average particle diameter of the powder after sanding is 0.8-1.5 μm, for example: 0.8 μm, 1 μm, 1.2 μm, 1.3 μm, or 1.μm 8.

Preferably, the granulation in the step (2) comprises mixing the secondary grinding material, the polyvinyl alcohol solution and the defoaming agent, rapidly stirring, and spraying to obtain the granulated powder.

Preferably, the concentration of the polyvinyl alcohol solution is 5-15 wt%, for example: 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, or the like.

Preferably, the antifoaming agent comprises n-octanol.

Preferably, the concentration of n-octanol is 0.05 to 0.2 wt%, for example: 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.15 wt%, or 0.2 wt%, etc.

Preferably, the mass ratio of the secondary grinding material to the polyvinyl alcohol solution is 1 (0.08-0.1), such as: 1:0.08, 1:0.09 or 1:0.1, etc.

Preferably, the time of the rapid stirring is 2-5 h, for example: 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h and the like.

Preferably, the molding in the step (2) comprises mixing the granulated powder and zinc stearate and pressing into a green body.

Preferably, the mass ratio of the granulated powder to the zinc stearate is 1 (0.001-0.004), such as: 1:0.001, 1:0.002, 1:0.003 or 1:0.004, etc.

Preferably, the pressure of the pressing is 3-12 Mpa, such as: 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 MPa.

Preferably, the sintering treatment in the step (2) comprises one-step heating sintering, two-step heating sintering, one-step cooling, two-step cooling and three-step cooling.

Preferably, the one-step temperature-rising sintering comprises raising the temperature from room temperature to 950-1000 ℃ (such as 950 ℃, 955 ℃, 960 ℃, 980 ℃ or 1000 ℃ and the like) within 5-8 h (such as 5h, 6h, 7h or 8h and the like), and preserving the temperature for 1-2 h, such as: 1h, 1.2h, 1.5h, 1.8h or 2h and the like.

Preferably, the two-step temperature rise sintering comprises the steps of continuously raising the temperature of the green body to 1100-1160 ℃ (for example, 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃ or 1160 ℃ and the like) within 0.5-2 h (for example, 0.5h, 0.8h, 1h, 1.5h or 2 and the like) and preserving the temperature for 3-6 h, for example: 3h, 3.5h, 4h, 5h or 6h and the like.

Preferably, the oxygen content of the two-step temperature-rising sintering is 0.01-0.05%, for example: 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, etc.

Preferably, the one-step temperature reduction comprises temperature reduction to 400-600 ℃ within 2-4 h (for example: 2h, 2.2h, 2.5h, 3h, 3.5h or 4h, etc.), for example: 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, etc.

Preferably, the two-step temperature reduction comprises the step of continuously reducing the temperature to 100-200 ℃ within 1-3 h (for example: 1h, 1.2h, 1.5h, 2h, 2.5h or 3h, etc.), for example: 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃ or the like.

Preferably, the three-step cooling comprises the step of continuously cooling to the room temperature within 0.5-1 h (for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h and the like).

In a third aspect, the present invention provides a use of a nickel zinc ferrite material as described in the first aspect for microwave communication and/or as a magnetic material.

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

(1) according to the invention, the specific component proportion of the main component and the additive in the nickel-zinc ferrite material is optimized and adjusted, and the problem of large inductance change of the material at-40-125 ℃ is solved by accurately controlling the proportion and the content of each component, so that the output stability of the inductor under the extremely low temperature/high temperature condition is improved.

(2) The initial permeability mu i of the nickel-zinc ferrite material can reach more than 421, the Q value can reach more than 45, alpha mu r can reach less than 24.9 ppm/DEG C, Bs can reach more than 318.6mT at 25 ℃, Bs can reach more than 226mT at 100 ℃, the initial permeability mu i of the nickel-zinc ferrite material can reach 520, the Q value can reach 155, alpha mu r can reach 11.15 ppm/DEG C, Bs can reach 456mT at 25 ℃, and Bs can reach 356mT at 100 ℃ by adjusting the contents of the main components and the additives.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. 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.

The compositions of the nickel zinc ferrite materials prepared in examples 1 to 10 of the present invention and comparative examples 1 to 7 are shown in Table 1:

TABLE 1

Example 1

The present embodiment provides a nickel zinc ferrite material, the composition of which is shown in table 1, and the nickel zinc ferrite material is prepared by the following method:

(1) uniformly mixing a main component material and an additive material according to the mass ratio of the raw materials to grinding balls to water of 1:4.9:1, carrying out ball milling for 2 hours to obtain a primary mixture, drying the mixture, and presintering the mixture at 850 ℃ for 4 hours to obtain a presintering material;

(2) mixing the pre-sintering material obtained in the step (1) according to the mass ratio of the pre-sintering material to the grinding ball to the water of 1:7:1.2, sanding to obtain a two-step mixture with the average particle size of 1.2 mu m, adding a polyvinyl alcohol solution with the concentration of 5 wt% and n-octyl alcohol with the weight of 8% of the secondary sand abrasive, quickly stirring for 2h to obtain granulation powder, adding zinc stearate with the weight of 0.15% of the granulation powder into the granulation powder, uniformly stirring, pressing into a blank under the forming pressure of 5MPa, heating the blank from room temperature to 960 ℃ within 6h, keeping the temperature for 1.2h, continuously heating the blank to 1120 ℃ within 1.5h, keeping the temperature for 5h, cooling the blank to 300 ℃ within 2.5h, continuously cooling the blank to 150 ℃ within 0.5h, and naturally and quickly cooling the blank to room temperature within 1h to obtain the nickel-zinc ferrite material.

Example 2

The present embodiment provides a nickel zinc ferrite material, the composition of which is shown in table 1, and the nickel zinc ferrite material is prepared by the following method:

(1) uniformly mixing a main component material and an additive material according to the mass ratio of the raw materials to the grinding balls to the water of 1:4.8:0.8, performing ball milling for 2 hours to obtain a primary mixture, drying the mixture, and then pre-sintering at 800 ℃ for 4 hours to obtain a pre-sintered material;

(2) mixing the pre-sintering material obtained in the step (1) according to the mass ratio of the pre-sintering material to grinding balls to water of 1:5:1.5, sanding to obtain a two-step mixture with the average particle size of 1 mu m, adding a polyvinyl alcohol solution with the concentration of 5 wt% and n-octyl alcohol with the weight of 8% of the secondary sand grinding material, quickly stirring for 2h to obtain granulation powder, adding zinc stearate with the weight of 0.15% of the granulation powder into the granulation powder, uniformly stirring, pressing into a blank under the forming pressure of 5MPa, heating the blank to 960 ℃ from room temperature within 6h, keeping the temperature for 1.2h, continuously heating the blank to 1120 ℃ within 1.5h, keeping the temperature for 5h, cooling the blank to 300 ℃ within 2.5h, continuously cooling the blank to 150 ℃ within 0.5h, and naturally and quickly cooling the blank to room temperature within 1h to obtain the nickel-zinc ferrite material.

Example 3

This example is different from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of NiO is 47.8 mol%, the molar percentage of NiO is 15 mol%, the molar percentage of ZnO is 30.9 mol%, and the molar percentage of CuO is 6.3 mol%.

Example 4

This example is different from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of NiO is 49.8 mol%, the molar percentage of NiO is 14.2 mol%, the molar percentage of ZnO is 30 mol%, and the molar percentage of CuO is 6 mol%.

Example 5

This example is different from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of NiO is 49.5 mol%, the molar percentage of NiO is 13.5 mol%, the molar percentage of ZnO is 30.7 mol%, and the molar percentage of CuO is 6.3 mol%.

Example 6

This example is different from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of the NiO is 49 mol%, the molar percentage of the NiO is 15 mol%, the molar percentage of the ZnO is 30 mol%, and the molar percentage of the CuO is 6 mol%.

Example 7

This example is different from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of NiO is 49.6 mol%, the molar percentage of NiO is 15 mol%, the molar percentage of ZnO is 29 mol%, and the molar percentage of CuO is 6.4 mol%.

Example 8

This example is different from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of the NiO is 49 mol%, the molar percentage of the NiO is 14 mol%, the molar percentage of the ZnO is 31 mol%, and the molar percentage of the CuO is 6 mol%.

Example 9

This example is different from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of NiO is 49.7 mol%, the molar percentage of NiO is 14.8 mol%, the molar percentage of ZnO is 30.5 mol%, and the molar percentage of CuO is 5 mol%.

Example 10

This example is different from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of NiO is 48.8 mol%, the molar percentage of NiO is 14.3 mol%, the molar percentage of ZnO is 30 mol%, and the molar percentage of CuO is 7 mol%.

Comparative example 1

This comparative example differs from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of NiO is 52.4 mol%, the molar percentage of NiO is 33.2 mol%, the molar percentage of ZnO is 11.5 mol%, and the molar percentage of CuO is 2.9 mol%.

Comparative example 2

This comparative example differs from example 1 only in that Fe is contained in the main component₂O₃The molar percentage of the NiO is 45 mol%, the molar percentage of the NiO is 14.5 mol%, the molar percentage of the ZnO is 30.5 mol%, and the molar percentage of the CuO is 10 mol%.

Comparative example 3

This comparative example differs from example 1 only in that Co₂O₃Was 0.12 wt%, and the other conditions and parameters were exactly the same as in example 1.

Comparative example 4

This comparative example differs from example 1 only in that Co₂O₃Was 0.35 wt%, and the other conditions and parameters were exactly the same as in example 1.

Comparative example 5

This comparative example differs from example 1 only in that Nb₂O₅Was 0.02 wt%, and the other conditions and parameters were exactly the same as those in example 1.

Comparative example 6

This comparative example differs from example 1 only in that Nb₂O₅Was 0.08 wt%, and the other conditions and parameters were exactly the same as those in example 1.

Comparative example 7

This comparative example differs from example 1 only in that Bi₂O₃Was 0.03 wt%, and the other conditions and parameters were exactly the same as those in example 1.

Comparative example 8

This comparative example differs from example 1 only in that Bi₂O₃Is 0.18 wt%, and the other conditions and parameters are exactly the same as those in example 1.

And (3) performance testing:

samples of the NiZn ferrite materials prepared in the above examples 1 to 10 and comparative examples 1 to 8 were subjected to inductance and Q value tests using an Aglient E4991A tester. The test conditions were respectively: measuring inductance at 25 deg.C and 125 deg.C under the condition of f 1MHzu 0.25v, and converting into magnetic permeability μ i; testing the Curie temperature Tc and the magnetic permeability mui of each temperature by using an Aglient E4991A and a high-low temperature controllable oven, and calculating a specific temperature coefficient alpha mur by using a formula according to data; the magnetic flux density Bs was measured by SY8232 instrument of kawasaki corporation, and the measurement results are shown in table 2:

TABLE 2

As can be seen from Table 2, in examples 1 to 10, the initial permeability μ i of the nickel-zinc ferrite material of the present invention can be more than 421, the Q value can be more than 45, α μ r can be less than 24.9 ppm/DEG C, Bs at 25 ℃ can be more than 318.6mT, and Bs at 100 ℃ can be more than 226mT, by adjusting the contents of the main components and the additives, the initial permeability μ i of the nickel-zinc ferrite material can be 520, the Q value can be 155, α μ r can be 11.15 ppm/DEG C, Bs at 25 ℃ can be 456mT, and Bs at 100 ℃ can be 356 mT.

As can be seen from a comparison of example 1 with examples 3-10, the proportions of the components in the main component, the Fe, which affects the properties of the resulting nickel-zinc-ferrite material₂O₃The mol percentage of the NiO is controlled to be 48-49.3 mol%, the mol percentage of the NiO is controlled to be 14-15 mol%, the mol percentage of the ZnO is controlled to be 30-31 mol%, and the mol percentage of the CuO is controlled to be 5.6-6.5 mol%, so that the nickel-zinc ferrite material with excellent performance can be prepared.

As can be seen from comparison of example 1 with comparative examples 1 to 2, the present invention strictly controls the molar ratio of each material in the main component to Fe₂O₃47.8-49.8 mol%, the molar percentage of NiO is 13.5-15 mol%, the molar percentage of ZnO is 29-31 mol%, the molar percentage of CuO is 5-7 mol%, and if the molar percentage of CuO is not less than 4 mol%, the molar percentage of NiO is not less than 13.5-15 mol%, and if the molar percentage of ZnO is not less than 29 mol%, the molar percentage of ZnO is not more than 31 mol%, the molar percentage of CuO is not less than 5 mol%, and if the molar percentage of CuO is not less than 7 mol%, the molar percentage of NiO is not less than 4 mol%, and if the NiO is not less than 4 mol%, the NiO is not more than 4 mol%, and if the NiO is not more than 4 mol%, the NiO is not more than 15 mol%, the NiO is not more than 29Beyond the above range, the performance of the material is drastically reduced, and the performance in various aspects is remarkably reduced.

From example 1 and comparative examples 3 to 8, a comparison is made of Co in the additive₂O₃、Nb₂O₅And Bi₂O₃The content of (A) significantly affects the properties of the ferrite material obtained, and the Co is added to the ferrite material in an amount of 100% by mass of the main component₂O₃The mass of Nb is controlled to 0.15 to 0.3 wt%, and the Nb is added₂O₅The quality of (B) is controlled to be 0.04-0.075 wt%, and the Bi is added₂O₃The quality of the Co-based ferrite material is controlled to be 0.05-0.15 wt%, so that a nickel-zinc ferrite material with excellent performance can be prepared, and if the Co-based ferrite material is Co₂O₃、Nb₂O₅And Bi₂O₃If the content of (b) is outside the above range, various properties of the resulting material may be significantly deteriorated.

Anisotropy constant K of spinel ferrite in general₁Is negative and Co₂O₃Anisotropy constant K₁＞0，Co²⁺After addition, Co²⁺Contributing K₁The value decreases sharply with increasing temperature, so that it is possible for K to be present in a temperature range below the Curie temperature₁The second peak of the μ i-T curve is generated at the offset point of 0, thereby reducing the specific temperature coefficient α μ r, and the inventors have studied and found that: the CoO auxiliary component is added, the mass percentage is controlled to be 0.15-0.3 wt%, the specific temperature coefficient alpha mu r can be effectively reduced, and meanwhile Co²⁺Has the effect of improving the Q value.

Additive Nb₂O₅Mainly plays a role in refining crystal grains, prevents the abnormal growth of the crystal grains and ensures the uniformity of the crystal grain size.

Additive Bi₂O₃The melting point of the nickel-zinc ferrite is lower, so that liquid phase sintering is generated in the sintering process of the nickel-zinc ferrite, and the sintering temperature can be effectively reduced. But Bi₂O₃Excessive addition can cause abnormal growth of grains, resulting in poor material properties.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.