Nickel magnesium zinc copper iron oxide and its manufacturing method and application

Abstract

The present invention provides nickel magnesium zinc copper iron oxide and its manufacturing method and application. The nickel magnesium zinc copper iron oxide includes a main component and auxiliary additives. The main component includes, by mass fraction, 66.95% to 71.8% Fe2O3, 15.6% to 19.7% ZnO, 2.1% to 4.2% NiO, 2.1% to 5.0% MnO, 2.0% to 4.9% CuO, and 1.82% to 2.98% MgO. The auxiliary additives include CaCO3, Bi2O3, MgO, and ZnO. O The nickel magnesium zinc copper iron oxide contains O3 and Co2O3. A method for producing nickel magnesium zinc copper iron oxide includes the steps of: weighing out a main component and wet-grinding to obtain a first mixture; drying the first mixture and then pre-calcining to obtain a pre-calcined product; weighing out auxiliary additives and wet-grinding the pre-calcined product and drying to obtain a second mixture; and crushing, molding, and sintering the second mixture to obtain nickel magnesium zinc copper iron oxide. The nickel magnesium zinc copper iron oxide can be used in magnetic devices.

Description

[Technical Field]

[0001] <Cross-reference to related patent applications> This application claims priority from a Chinese patent application filed on December 13, 2022, bearing application number 202211594105.5 and entitled "Nickel magnesium zinc copper iron oxide and its manufacturing method and application," the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to the technical field of soft magnetic iron oxide, and in particular to nickel magnesium zinc copper iron oxide and its manufacturing method and application. [Background technology]

[0003] Soft magnetic iron oxide materials, primarily including spinel, garnet, and magnetoplumbite-type polycrystalline and single-crystalline iron oxide materials, are important magnetic functional materials due to their high resistivity, low loss, and excellent dielectric and frequency characteristics. These materials are widely used in many fields, including modern medicine, communications, military, smart electronics, information, solar power generation, energy storage, and automotive electronics. Among spinel-type soft magnetic iron oxide materials, nickel zinc iron oxide, in particular, has a wide bandwidth and high magnetic permeability, making it a soft magnetic iron oxide material widely used in the high frequency range of 1 MHz to 100 MHz. Summary of the Invention [Problem to be solved by the invention]

[0004] However, in related art, nickel-zinc-iron oxide materials with broadband high magnetic permeability typically contain more than 15 mol% NiO, which increases the price of nickel raw materials on the market, resulting in high production costs and reduced competitiveness for nickel-zinc-iron oxides made from nickel-zinc materials. Furthermore, while nickel-zinc-iron oxide materials have the advantage of broadband high magnetic permeability, when the magnetic permeability exceeds 900 H / m, the Curie temperature of nickel-zinc-iron oxide materials typically does not reach 110°C. Therefore, during use, conventional nickel-zinc-iron oxide materials cannot meet the high Curie temperature requirements in fields such as automotive electronics, network communications, and aerospace. Furthermore, conventional nickel-zinc-iron oxide materials have difficulty simultaneously achieving high Curie temperature and high impedance while maintaining broadband high magnetic permeability. [Means for solving the problem]

[0005] To solve the above problems, the present invention provides nickel magnesium zinc copper iron oxide and its manufacturing method and application. Nickel magnesium zinc copper iron oxide maintains high magnetic permeability over a wide bandwidth, has a high Curie temperature and high impedance, and has low production costs, which can meet the market needs of magnetic devices.

[0006] The nickel magnesium zinc copper iron oxide contains a main component and auxiliary additives. The main component contains, by mass fraction, 66.95% to 71.8% Fe2O3, 15.6% to 19.7% ZnO, 2.1% to 4.2% NiO, 2.1% to 5.0% MnO, 2.0% to 4.9% CuO, and 1.82% to 2.98% MgO. The auxiliary additives include CaCO3, Bi2O3, MgO, and ZnO. O The mass of the CaCO3 is 0.1% to 0.3% of the mass of the main component, the mass of the Bi2O3 is 0.1% to 0.4% of the mass of the main component, and the mass of the M O The nickel magnesium zinc copper iron oxide is characterized in that the mass of O3 is 0.01% to 0.39% of the mass of the main component, and the mass of Co2O3 is 0.01% to 0.29% of the mass of the main component.

[0007] In one embodiment, the main components include 68.2 wt% to 70.9 wt% Fe2O3, 16.1 wt% to 19.1 wt% ZnO, 2.2 wt% to 3.5 wt% NiO, 2.7 wt% to 5.0 wt% MnO, 3.5 wt% to 4.9 wt% CuO, and 1.95 wt% to 2.35 wt% MgO.

[0008] In one embodiment, the mass of the CaCO3 is 0.15 to 0.3% of the mass of the main component. In one embodiment, the mass of the Bi2O3 is 0.1% to 0.3% of the mass of the main component. In one embodiment, the M O The mass of O3 is 0.05% to 0.3% of the mass of the main components. In one embodiment, the mass of Co2O3 is 0.01% to 0.2% of the mass of the main components.

[0009] The method for producing the nickel magnesium zinc copper iron oxide includes the steps of: weighing out main components in a predetermined ratio and wet-grinding them to obtain a first mixture; drying the first mixture and then pre-calcining it to obtain a pre-calcined product; weighing out auxiliary additives in a predetermined ratio and wet-grinding them with the pre-calcined product and drying them to obtain a second mixture; and pulverizing, molding, and sintering the second mixture to obtain the nickel magnesium zinc copper iron oxide.

[0010] In one embodiment, in the step of measuring the main component in a predetermined ratio and performing wet grinding to obtain a first mixture, the weight ratio of the main component, the grinding balls and the solvent is 1:(4.5-6):(0.6-1.2).

[0011] In one embodiment, in the step of measuring the auxiliary additives in a predetermined ratio and wet-grinding the pre-calcined material, the weight ratio of the total of the auxiliary additives and the pre-calcined material to the grinding balls and the solvent is 1:(4-7):(1-1.2).

[0012] In one embodiment, the particle size of the second mixture is 0.5 μm to 1.6 μm.

[0013] In one embodiment, the sintering is performed by increasing the temperature stepwise.

[0014] In one embodiment, the molding pressure is 3 MPa to 10 MPa.

[0015] In one embodiment, the nickel magnesium zinc copper iron oxide is applied to a magnetic device.

[0016] The details of one or more embodiments of the invention are set forth in the drawings and description below. Other features, objects, and advantages of the invention will become apparent from the description, drawings, and claims. DETAILED DESCRIPTION OF THE INVENTION

[0017] The following clearly and completely describes the technical solutions of the embodiments of the present invention in combination with the drawings of the embodiments of the present invention, but it is obvious that the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts fall within the protection scope of the present invention.

[0018] To facilitate understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be embodied in many different forms and is not limited to the embodiments and examples described herein. Rather, the purpose of providing these embodiments and examples is to provide a deeper and more complete understanding of the disclosed subject matter of the present invention.

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are intended to describe specific embodiments and examples, and are not intended to limit the scope of the present invention.

[0020] The present invention provides a nickel magnesium zinc copper iron oxide. The nickel magnesium zinc copper iron oxide contains a main component and auxiliary additives. The main component includes, by mass fraction, 66.95% to 71.8% Fe2O3, 15.6% to 19.7% ZnO, 2.1% to 4.2% NiO, 2.1% to 5.0% MnO, 2.0% to 4.9% CuO, and 1.82% to 2.98% MgO.

[0021] The auxiliary additives are CaCO3, Bi2O3, M O The mass of CaCO3 is 0.1% to 0.3% of the mass of the main components, the mass of Bi2O3 is 0.1% to 0.4% of the mass of the main components, and M O The mass of O3 is 0.01% to 0.39% of the mass of the main components, and the mass of Co2O3 is 0.01% to 0.29% of the mass of the main components.

[0022] In the nickel magnesium zinc copper iron oxide of the present invention, the content of NiO is reduced, and specific contents of Fe2O3, ZnO, MgO, MnO, CuO and specific ratios of CaCO3, Bi2O3, M O The cooperative blending of O3 and Co2O3 as auxiliary additives improves the microstructure of nickel magnesium zinc copper iron oxide, densifies the nickel magnesium zinc copper iron oxide, maintains the spinel lattice structure, and avoids distortion of the crystal lattice. As a result, nickel magnesium zinc copper iron oxide can maintain high permeability over a wide frequency range of 1KHz to 1000KHz, has a high Curie temperature of above 160°C, and high impedance, while significantly reducing production costs.

[0023] To further adjust the magnetic permeability and Curie temperature, even a small excess of Fe2O3 can cooperate with NiO, MgO, MnO, and CuO to jointly suppress the volatilization of Zn in ZnO. In some embodiments, the main components include 68.2 wt% to 70.9 wt% Fe2O3, 16.1 wt% to 19.1 wt% ZnO, 2.2 wt% to 3.5 wt% NiO, 2.7 wt% to 5.0 wt% MnO, 3.5 wt% to 4.9 wt% CuO, and 1.95 wt% to 2.35 wt% MgO.

[0024] CaCO3, Bi2O3, M O The combination of O3 and Co2O3 as auxiliary additives can stably improve the electromagnetic properties of nickel magnesium zinc copper iron oxide by coordinating with the main components Fe2O3, ZnO, MgO, MnO and CuO.

[0025] CaCO3, Bi2O3, M O By adjusting the compounding ratio of O3 and Co2O3 more precisely, nickel magnesium zinc copper iron oxide with better performance can be obtained.

[0026] Specifically, by fine-tuning the blending ratio of CaCO3, the solid-state reaction can be improved, promoting further densification of the nickel magnesium zinc copper iron oxide, improving the density of the nickel magnesium zinc copper iron oxide, and cooperatively adjusting the particle size of the nickel magnesium zinc copper iron oxide, thereby improving the performance of the nickel magnesium zinc copper iron oxide. In some examples, the mass of CaCO3 is 0.15% to 0.3% of the mass of the main components.

[0027] Bi2O3 and M with low melting point properties O O3 can form a liquid phase during the production of nickel magnesium zinc copper iron oxide, which helps to promote the solid-state reaction. In the main component with a slight excess of Fe2O3, M OBy fine-tuning the proportion of O3, the crystal growth of nickel magnesium zinc copper iron oxide can be further promoted, the initial permeability can be improved, and the amount of Bi2O3 added can be reduced. In some embodiments, the mass of Bi2O3 is 0.1% to 0.3% of the mass of the main components, and / or M O The mass of O3 is 0.05% to 0.3% of the mass of the main components.

[0028] Co2O3 can substitute for the main component and dissolve in the spinel lattice. By adjusting the proportion of Co2O3, the microstructure of the nickel magnesium zinc copper iron oxide can be further improved, the cutoff frequency can be increased, and at the same time, the electrical resistivity can be increased, the loss can be reduced, the high frequency impedance performance can be improved, and the magnetic permeability can be maintained. In some embodiments, the mass of Co2O3 is 0.01% to 0.2% of the mass of the main component.

[0029] In some embodiments, the nickel magnesium zinc copper iron oxide has a major component of 68.2 wt% to 70.9 wt% Fe2O3, 16.1 wt% to 19.1 wt% ZnO, 2.2 wt% to 3.5 wt% NiO, 2.7 wt% to 5.0 wt% MnO, 3.5 wt% to 4.9 wt% CuO, and 1.95 wt% to 2.35 wt% MgO. The auxiliary additives include CaCO3, Bi2O3, MgO, and the like. O The mass of CaCO3 is 0.15-0.3% of the mass of the main component, the mass of Bi2O3 is 0.1%-0.3% of the mass of the main component, and M O The mass of O3 is 0.05% to 0.3% of the mass of the main components, and the mass of Co2O3 is 0.01% to 0.2% of the mass of the main components.

[0030] The present invention provides a method for producing nickel magnesium zinc copper iron oxide, which comprises the following steps:

[0031] S1: Weigh out the main components in a predetermined ratio and perform wet grinding to obtain a first mixture.

[0032] S2: After drying the first mixture, pre-calcination is carried out to obtain a pre-calcined product.

[0033] S3, weigh out the auxiliary additives in a predetermined ratio, and then pre-calcinate and wet grind, and after drying, obtain a second mixture.

[0034] S4, the second mixture is crushed, molded, and sintered to obtain nickel magnesium zinc copper iron oxide.

[0035] In step S1, the water content of the first mixture is adjusted to uniformly mix the first mixture, and the permeability of the first mixture is improved to thereby improve the efficiency of sintering of nickel magnesium zinc copper iron oxide. In this step, the main components are weighed in a predetermined ratio and wet-grinded, where the weight ratio of the main components, grinding balls, and solvent is 1:(4.5-6):(0.6-1.2). In some embodiments, the solvent is water.

[0036] Furthermore, in order to mix the main component and the solvent uniformly, in some embodiments, the wet polishing treatment time is 1 to 3 hours.

[0037] In step S2, drying can reduce the influence of the solvent in the first mixture on the sintering process, and the pre-calcination process can improve the texture of the nickel magnesium zinc copper iron oxide, ensuring the stability of the volume and the accuracy of the shape and size of the nickel magnesium zinc copper iron oxide, thereby improving the performance of the nickel magnesium zinc copper iron oxide.

[0038] Specifically, the pre-baking temperature is 920°C to 1000°C, and the pre-baking time is 6 hours to 10 hours.

[0039] In step S3, auxiliary additives are weighed out in a predetermined ratio to provide the second mixture with an appropriate particle size distribution, good flowability, and a predetermined bulk density to facilitate subsequent milling and shaping, and to produce a high-quality nickel magnesium zinc copper iron oxide. In the step of wet-grinding with the pre-calcined material, the weight ratio of the auxiliary additives to the pre-calcined material, the grinding balls, and the solvent is 1:(4-7):(1-1.2). In some embodiments, the wet-grinding treatment time is 2-6 hours.

[0040] Furthermore, in consideration of the efficiency of the subsequent grinding, in some embodiments, the particle size of the second mixture is 0.5 μm to 1.6 μm.

[0041] In step S4, the second mixture is pulverized to produce granulated powder with uniform particle size and good activity, which can be uniformly distributed during the molding process and ensure the consistency and compactness of the density of the compact.

[0042] In order to further ensure the compressibility of the molding process and the strength of the molded body, spray milling is employed as the milling method in some embodiments.

[0043] Specifically, the spray milling manufacturing procedure involves mixing the adhesive, antifoaming agent, and second mixture for 1 to 3 hours, followed by spray milling to produce a granulated powder. The adhesive is 5% to 15% by mass of the second mixture, and the antifoaming agent is 0.03% to 0.3% by mass of the second mixture. In some embodiments, the adhesive is a polyvinyl alcohol solution having a concentration of 8% to 10%. In some embodiments, the antifoaming agent is nonanol.

[0044] To facilitate demolding of the compact, in some embodiments, a lubricant is added to the granulated powder, which is then mixed and compressed into a compact. The mass of the lubricant is 0.01% to 0.1% of the mass of the granulated powder, and in some embodiments, the lubricant is zinc stearate.

[0045] In one embodiment, the molding pressure is between 3 MPa and 10 MPa.

[0046] Sintering can be performed by increasing the temperature all at once, or by increasing the temperature stepwise. In some embodiments, sintering is performed by increasing the temperature stepwise. In some embodiments, sintering by increasing the temperature stepwise includes a first temperature increase, a second temperature increase, a temperature holding stage, a temperature reduction stage, and a cooling stage. The first temperature increase is from 800°C to 1000°C, and the time is from 5 to 10 hours. The second temperature increase is from 1180°C to 1220°C, and the time is from 1.5 to 3 hours. In the temperature holding stage, the second temperature increase is maintained for 3 to 6 hours. The temperature in the temperature reduction stage is from 130°C to 200°C, and the time is from 7 to 10 hours. In the cooling stage, the sintered molded body is cooled to room temperature.

[0047] The present invention further provides an application of nickel magnesium zinc copper iron oxide to magnetic devices.

[0048] Nickel magnesium zinc copper iron oxide can be applied to magnetic devices to meet the performance requirements of nickel magnesium zinc copper iron oxide, such as wideband high impedance and high Curie temperature, in modern fields such as medicine, automotive, solar power generation, communications, and aerospace, thereby improving market demand for nickel magnesium zinc copper iron oxide in application fields such as inductor filters, optical energy storage transformers, medical devices, etc. In addition, nickel magnesium zinc copper iron oxide can significantly reduce production costs, further improving the market competitiveness of nickel magnesium zinc copper iron oxide magnetic devices.

[0049] Hereinafter, nickel magnesium zinc copper iron oxide and its manufacturing method and application will be further described through specific examples.

[0050] Example 1 68.6 wt% Fe2O3, 18.65 wt% ZnO, 3.4 wt% NiO, 2.7 wt% MnO, 4.6 wt% CuO, and 2.05 wt% MgO were weighed and mixed with the main components, grinding balls, and water in a weight ratio of 1:4.5:0.8, followed by wet grinding for 1 hour to obtain a first mixture.

[0051] After drying the first mixture, it is pre-fired at 950°C for 6 hours and kept at that temperature for 4 hours to obtain a pre-fired product.

[0052] CaCO3, Bi2O3, M O O3 and Co2O3 were weighed as auxiliary additives, the mass of CaCO3 was 0.15% of the mass of the main component, the mass of Bi2O3 was 0.3% of the mass of the main component, and M O The mass of O3 is 0.08% of the mass of the main component, and the mass of Co2O3 is 0.05% of the mass of the main component. The pre-calcined material containing auxiliary additives, grinding balls, and water are mixed in a weight ratio of 1:4:1, and then wet-grinded for 3 hours. After drying, a second mixture with an average particle size of 1.2 μm is obtained.

[0053] A polyvinyl alcohol solution (5 wt%) and nonanol were added to the second mixture and stirred rapidly for two hours to obtain a granulated powder. The mass of the polyvinyl alcohol solution was 5% of the mass of the second mixture, and the mass of nonanol was 0.1% of the mass of the second mixture. Zinc stearate was added to the granulated powder, and after uniform stirring, a compact was formed at a compaction pressure of 5 MPa. The amount of zinc stearate added was 0.1% of the mass of the granulated powder. The compact was placed in a pushed slab kiln and subjected to stepwise heating and sintering. Specifically, the compact was first heated from room temperature to 900°C over eight hours, then further heated to 1205°C over two hours and held at that temperature for three hours. The compact was then cooled to 150°C over ten hours and finally cooled to room temperature to obtain a cyclic nickel magnesium zinc copper iron oxide with an outer diameter of 25 mm, an inner diameter of 15 mm, and a height of 7 mm.

[0054] <Example 2> 70.1 wt% Fe2O3, 16.65 wt% ZnO, 2.8 wt% NiO, 3.5 wt% MnO, 4.6 wt% CuO, and 2.35 wt% MgO were weighed and mixed with the main components, grinding balls, and water in a weight ratio of 1:5:1.2, followed by wet grinding for 1 hour to obtain a first mixture.

[0055] After drying the first mixture, it is pre-fired at 980°C for 8 hours and kept at that temperature for 4 hours to obtain a pre-fired product.

[0056] CaCO3, Bi2O3, M O O3 and Co2O3 were weighed as auxiliary additives, the mass of CaCO3 was 0.15% of the mass of the main component, the mass of Bi2O3 was 0.15% of the mass of the main component, and M O The mass of O3 is 0.1% of the mass of the main component, and the mass of Co2O3 is 0.05% of the mass of the main component. The pre-calcined material containing auxiliary additives, grinding balls, and water are mixed in a weight ratio of 1:5:1.2, and then wet-grinded for 4 hours. After drying, a second mixture with an average particle size of 1.1 μm is obtained.

[0057] A polyvinyl alcohol solution (10 wt%) and nonanol were added to the second mixture and stirred rapidly for three hours to obtain a granulated powder. The mass of the polyvinyl alcohol solution was 10% of the mass of the second mixture, and the mass of nonanol was 0.1% of the mass of the second mixture. Zinc stearate was added to the granulated powder, and after uniform stirring, a compact was formed at a molding pressure of 5 MPa. The amount of zinc stearate added was 0.1% of the mass of the granulated powder. The compact was placed in a slat furnace and subjected to stepwise heating and sintering. Specifically, the compact was first heated from room temperature to 950°C over six hours, then further heated to 1205°C over two hours and held at that temperature for three hours. The compact was then cooled to 150°C within ten hours and finally cooled to room temperature to obtain a cyclic nickel magnesium zinc copper iron oxide with an outer diameter of 25 mm, an inner diameter of 15 mm, and a height of 7 mm.

[0058] Example 3 69.5 wt% Fe2O3, 16.1 wt% ZnO, 2.2 wt% NiO, 4.6 wt% MnO, 4.75 wt% CuO, and 2.85 wt% MgO were weighed and mixed with the main components, grinding balls, and water in a weight ratio of 1:5:1.2, followed by wet grinding for 1 hour to obtain a first mixture.

[0059] After drying the first mixture, it is pre-fired at 980°C for 8 hours and kept at that temperature for 4 hours to obtain a pre-fired product.

[0060] CaCO3, Bi2O3, M O O3 and Co2O3 were weighed as auxiliary additives, the mass of CaCO3 was 0.2% of the mass of the main component, the mass of Bi2O3 was 0.15% of the mass of the main component, and M O The mass of O3 is 0.15% of the mass of the main component, and the mass of Co2O3 is 0.1% of the mass of the main component. The pre-calcined material containing auxiliary additives, grinding balls, and water are mixed in a weight ratio of 1:5:1.2, and then wet-grinded for 5 hours. After drying, a second mixture with an average particle size of 1.2 μm is obtained.

[0061] A polyvinyl alcohol solution (7 wt%) and nonanol were added to the second mixture and stirred rapidly for three hours to obtain a granulated powder. The mass of the polyvinyl alcohol solution was 10% of the mass of the second mixture, and the mass of nonanol was 0.12% of the mass of the second mixture. Zinc stearate was added to the granulated powder, and after uniform stirring, a compact was formed at a molding pressure of 5.5 MPa. The amount of zinc stearate added was 0.2% of the mass of the granulated powder. The compact was placed in a slat furnace and subjected to stepwise heating and sintering. Specifically, the compact was first heated from room temperature to 920°C over nine hours, then further heated to 1190°C over three hours and held at that temperature for two hours. The compact was then cooled to 150°C over ten hours and finally cooled to room temperature to obtain a cyclic nickel magnesium zinc copper iron oxide with an outer diameter of 25 mm, an inner diameter of 15 mm, and a height of 7 mm.

[0062] Example 4 68.6 wt% Fe2O3, 17.65 wt% ZnO, 3.1 wt% NiO, 3.7 wt% MnO, 4.6 wt% CuO, and 2.35 wt% MgO were weighed and mixed with the main components, grinding balls, and water in a weight ratio of 1:5:1.2, followed by wet grinding for 1 hour to obtain a first mixture.

[0063] After drying the first mixture, it is pre-fired at 980°C for 8 hours and kept at that temperature for 4 hours to obtain a pre-fired product.

[0064] CaCO3, Bi2O3, M O O3 and Co2O3 were weighed as auxiliary additives, the mass of CaCO3 was 0.15% of the mass of the main component, the mass of Bi2O3 was 0.1% of the mass of the main component, and M O The mass of O3 is 0.2% of the mass of the main component, and the mass of Co2O3 is 0.2% of the mass of the main component. The pre-calcined material containing auxiliary additives, grinding balls, and water are mixed in a weight ratio of 1:5:1.2, and then wet-grinded for 4 hours. After drying, a second mixture with an average particle size of 1.1 μm is obtained.

[0065] A polyvinyl alcohol solution (10 wt%) and nonanol were added to the second mixture and stirred rapidly for three hours to obtain a granulated powder. The mass of the polyvinyl alcohol solution was 10% of the mass of the second mixture, and the mass of nonanol was 0.1% of the mass of the second mixture. Zinc stearate was added to the granulated powder, and after uniform stirring, a compact was formed at a molding pressure of 5 MPa. The amount of zinc stearate added was 0.1% of the mass of the granulated powder. The compact was placed in a slat furnace and subjected to stepwise heating and sintering. Specifically, the compact was first heated from room temperature to 950°C over six hours, then further heated to 1195°C over two hours and held at that temperature for three hours. The compact was then cooled to 150°C within ten hours and finally cooled to room temperature to obtain a cyclic nickel magnesium zinc copper iron oxide with an outer diameter of 25 mm, an inner diameter of 15 mm, and a height of 7 mm.

[0066] <Comparative Example 1> The difference between Comparative Example 1 and Example 1 is that no auxiliary additives were added, and the pre-fired material was dry ground to an average particle size of 1.1 μm, and then crushed, molded, and sintered.

[0067] <Comparative Example 2> The difference between Comparative Example 2 and Example 2 is that the mass of Co2O3 in the auxiliary additives is 0.4% of the mass of the main components.

[0068] <Comparative Example 3> The difference between Comparative Example 3 and Example 3 is that M O The mass of O3 is 0.4% of the mass of the main component.

[0069] <Comparative Example 4> The difference between Comparative Example 4 and Example 4 is that the mass of CaCO3 in the auxiliary additives is 0.4% of the mass of the main component.

[0070] <Comparison 5> The difference between Comparative Example 5 and Example 4 is that Co2O3 is not included in the auxiliary additives.

[0071] <Comparative Example 6> The difference between Comparative Example 6 and Example 4 is that M O The difference is that O3 is not included.

[0072] <Comparative Example 7> The difference between Comparative Example 7 and Example 4 is that CaCO3 is not included in the auxiliary additives.

[0073] <Comparative Example 8> The difference between Comparative Example 8 and Example 4 is that the main components are Fe2O3 64.91 wt%, ZnO 19.37 wt%, NiO 3.1 wt%, MnO 4.2 wt%, CuO 6.37 wt%, and MgO 2.05 wt%.

[0074] <Comparative Example 9> The difference between Comparative Example 9 and Example 4 is that the main components contained 20 wt % ZnO and 70.95 wt % Fe2O3.

[0075] <Comparative Example 10> The difference between Comparative Example 10 and Example 4 is that the main components contained 1.2 wt% of MnO and 71.1 wt% of Fe2O3.

[0076] <Comparative Example 11> The difference between Comparative Example 11 and Example 4 is that the main components are Fe2O3 70.6 wt%, ZnO 17.65 wt%, NiO 3.45 wt%, MnO 3.7 wt%, and CuO 4.6 wt%.

[0077] The performance of the magnetic bodies manufactured in Examples 1 to 4 and Comparative Examples 1 to 11 was tested, and the results are shown in Table 1.

[0078] Under the conditions of T=25℃ and u=0.25v, the Curie temperature (Tc) and initial permeability (μi) under frequency conditions of 1KHz, 100KHz, 200KHz, and 1000KHz are measured using Aglient E4980A and a high / low temperature control oven. The surface resistance is tested using SM-8220 measurement equipment. The impedance is tested under frequency conditions of 1MHz, 25MHz, 100MHz, and 200MHz using HP4291B.

[0079] JPEG2025530274000001.jpg148170

[0080] From Table 1, in the nickel magnesium zinc copper iron oxide, the content of NiO is reduced, and specific contents of Fe2O3, ZnO, MgO, MnO, CuO and specific ratios of CaCO3, Bi2O3, M O By synergistically blending O3 and Co2O3 as auxiliary additives, nickel magnesium zinc copper iron oxide maintains a wide band high permeability from 1KHz to 1000KHz, and has a high Curie temperature of 160°C or more and a magnetic field strength of 10 5 It can be seen that the electrical resistivity is over Ω·m (DC 500V, spacing 10mm).

[0081] In Comparative Example 1, the main components are concentrated without the addition of auxiliary additives, so the Curie temperature is lowered to 120°C. In Comparative Example 2, the amount of Co2O3 used exceeds 0.29%, so lattice distortion occurs and the initial permeability is reduced. In Comparative Example 3, M O The amount of O3 used exceeds 0.39%, which causes discontinuous growth of partial crystal grains, increases stress at the crystal interface, and increases porosity, resulting in decreased density, permeability, and Curie temperature. In Comparative Example 4, the amount of CaCO3 used exceeds 0.3%, which significantly reduces magnetic performance. In Comparative Example 5, no Co2O3 is used, which increases loss, reduces electrical resistivity, and reduces high-frequency impedance performance. In Comparative Example 6, M O Since O3 is not used, the initial permeability is reduced. Since CaCO3 is not used in Comparative Example 7, the density is reduced and the magnetic performance is significantly reduced. Since the Fe2O3 content is less than 68.2 wt% and the CuO content is more than 4.9 wt%, the amount of zinc volatilization increases, causing a "dezincification" phenomenon, which reduces the electrical resistivity and permeability. Since the ZnO content is more than 19.7 wt% in Comparative Example 9, the Curie temperature is reduced. Since the MnO content is less than 2.1 wt% in Comparative Example 10, the permeability and Curie temperature are reduced. Since MgO is not used in Comparative Example 11, the permeability is reduced.

[0082] <Example 5> The difference between Example 5 and Example 2 is that the main components are Fe2O3 66.96 wt%, ZnO 19.7 wt%, NiO 4.12 wt%, MnO 4.3 wt%, CuO 3.1 wt%, and MgO 1.82 wt%.

[0083] Example 6 The difference between Example 6 and Example 2 is that the main components are Fe2O3 71.8 wt%, ZnO 15.6 wt%, NiO 3.5 wt%, MnO 4.12 wt%, CuO 2 wt%, and MgO 2.98 wt%.

[0084] Example 7 The difference between Example 7 and Example 2 is that the main components are Fe2O3 70.9 wt%, ZnO 17.95 wt%, NiO 2.1 wt%, MnO 2.1 wt%, CuO 4.9 wt%, and MgO 2.05 wt%.

[0085] Example 8 The difference between Example 8 and Example 2 is that the main components are Fe2O3 68.2 wt%, ZnO 19.1 wt%, NiO 3.25 wt%, MnO 4 wt%, CuO 3.5 wt%, and MgO 1.95 wt%.

[0086] The performance of the magnetic bodies produced in Examples 5 to 8 was measured, and the results are shown in Table 2.

[0087] JPEG2025530274000002.jpg68170

[0088] Comparing Comparative Example 2 with Examples 5 to 8, it can be seen that the performance of the nickel magnesium zinc copper iron oxide is improved when the main components include 68.2 wt% to 70.9 wt% Fe2O3, 16.1 wt% to 19.1 wt% ZnO, 2.2 wt% to 3.5 wt% NiO, 2.7 wt% to 5.0 wt% MnO, 3.5 wt% to 4.9 wt% CuO, and 1.95 wt% to 2.35 wt% MgO.

[0089] Example 9 The difference between Example 9 and Example 2 is that the mass of CaCO3 in the auxiliary additives is 0.1% of the mass of the main component, the mass of Bi2O3 is 0.4% of the mass of the main component, and M O The mass of O3 is 0.05% of the mass of the main components, and the mass of Co2O3 is 0.29% of the mass of the main components.

[0090] Example 10 The difference between Example 10 and Example 2 is that the mass of CaCO3 in the auxiliary additives is 0.1% of the mass of the main component, the mass of Bi2O3 is 0.1% of the mass of the main component, and M OThe mass of O3 is 0.39% of the mass of the main components, and the mass of Co2O3 is 0.01% of the mass of the main components.

[0091] Example 11 The difference between Example 11 and Example 2 is that the mass of CaCO3 in the auxiliary additives is 0.3% of the mass of the main component, the mass of Bi2O3 is 0.25% of the mass of the main component, and M O The mass of O3 is 0.01% of the mass of the main components, and the mass of Co2O3 is 0.15% of the mass of the main components.

[0092] Example 12 The difference between Example 12 and Example 2 is that the mass of CaCO3 in the auxiliary additives is 0.1% of the mass of the main component, the mass of Bi2O3 is 0.2% of the mass of the main component, and M O The mass of O3 is 0.3% of the mass of the main components, and the mass of Co2O3 is 0.01% of the mass of the main components.

[0093] The performance of the magnetic bodies produced in Examples 9 to 12 was measured, and the results are shown in Table 3.

[0094] JPEG2025530274000003.jpg68170

[0095] Comparing Example 2 with Examples 9 to 12, the auxiliary additives CaCO3, Bi2O3, M O O3 and Co2O3, in which the mass of CaCO3 is 0.15% to 0.3% of the mass of the main component, the mass of Bi2O3 is 0.1% to 0.3% of the mass of the main component, and M O It can be seen that when the mass of O3 is 0.05% to 0.3% of the mass of the main components and the mass of Co2O3 is 0.01% to 0.2% of the mass of the main components, the performance of the nickel magnesium zinc copper iron oxide is improved.

[0096] Furthermore, when Examples 1, 2, and 4 are comprehensively compared with Examples 5 to 12, the nickel magnesium zinc copper iron oxide contains 68.2 wt% to 70.9 wt% of Fe2O3, 16.1 wt% to 19.1 wt% of ZnO, 2.2 wt% to 3.5 wt% of NiO, 2.7 wt% to 5.0 wt% of MnO, 3.5 wt% to 4.9 wt% of CuO, and 1.95 wt% to 2.35 wt% of MgO as the main components, and the auxiliary additives are CaCO3, Bi2O3, MgO, and Bi2O3. O O3 and Co2O3, in which the mass of CaCO3 is 0.15% to 0.3% of the mass of the main component, the mass of Bi2O3 is 0.1% to 0.3% of the mass of the main component, and M O It can be seen that when the mass of O3 is 0.05% to 0.3% of the mass of the main components and the mass of Co2O3 is 0.01% to 0.2% of the mass of the main components, the performance of the nickel magnesium zinc copper iron oxide is improved.

[0097] The nickel magnesium zinc copper iron oxide of the present invention has a reduced NiO content and at the same time contains specific contents of Fe2O3, ZnO, MgO, MnO, CuO and specific ratios of CaCO3, Bi2O3, M O The co-additives O3 and Co2O3 are used to improve the microstructure of nickel magnesium zinc copper iron oxide, increasing its density while maintaining the spinel structure and avoiding distortion of the crystal lattice. As a result, nickel magnesium zinc copper iron oxide maintains high permeability over a wide frequency range of 1KHz to 1000KHz, has a high Curie temperature of over 160°C, high impedance, and significantly reduces manufacturing costs.

[0098] Therefore, nickel magnesium zinc copper iron oxide can meet the performance requirements of nickel magnesium zinc copper iron oxide, such as wideband high impedance and high Curie temperature, in modern medical, automotive, photovoltaic power generation, network communication, aerospace and other fields, which not only increases the market demand for nickel magnesium zinc copper iron oxide in application fields such as inductor filters, optical energy storage transformers and medical equipment, but also further improves the market competitiveness of nickel magnesium zinc copper iron oxide.

[0099] The technical features of the above embodiments can be combined in any combination, and for the sake of brevity, not all combinations of the technical features of the above embodiments are described. However, as long as the combinations of these technical features are not contradictory, they are deemed to be included in the scope described herein.

[0100] The above examples are specifically and in detail described, showing only some embodiments of the present invention, but are not intended to limit the scope of the invention patent. It should be noted that those skilled in the art can make some variations and modifications without departing from the spirit and scope of the present invention, and all of them fall within the scope of protection of the present invention. Therefore, the scope of patent protection of the present invention should be defined by the appended claims.

Claims

1. In nickel magnesium zinc copper iron oxide containing main component and auxiliary additives, The main component is 66.95% to 71.8% Fe by mass fraction. ２ O ３ , 15.6% to 19.7% ZnO, 2.1% to 4.2% NiO, 2.1% to 5.0% MnO, 2.0% to 4.9% CuO, and 1.82% to 2.98% MgO; The auxiliary additive is CaCO ３ , Bi ２ O ３ , M Ｏ O ３ and Co ２ O ３ The CaCO ３ The mass of the Bi is 0.1% to 0.3% of the mass of the main component. ２ O ３ The mass of the main component is 0.1% to 0.4% of the mass of the main component, and the mass of the M Ｏ O ３ The mass of the Co is 0.01% to 0.39% of the mass of the main component. ２ O ３ The nickel magnesium zinc copper iron oxide is characterized in that the mass of the main component is 0.01% to 0.29%.

2. The main component is 68.2 wt% to 70.9 wt% Fe ２ O ３ 2.7wt%-5.0wt% MnO, 3.5wt%-4.9wt% CuO, and 1.95wt%-2.35wt% MgO.

3. CaCO ３ is between 0.15 and 0.3% by weight of the main component, and / or The Bi ２ O ３ is between 0.1% and 0.3% by weight of the main component, and / or Said M Ｏ O ３ is between 0.05% and 0.3% by weight of the main component, and / or The Co ２ O ３ The nickel magnesium zinc copper iron oxide according to claim 1 or 2, characterized in that the mass of the main component is 0.01% to 0.2%.

4. Weighing out the main components in a predetermined ratio and wet grinding to obtain a first mixture; drying the first mixture and then pre-calcining it to obtain a pre-calcined product; Weighing auxiliary additives in a predetermined ratio, wet grinding with the pre-calcined material, and drying to obtain a second mixture; and a step of crushing, molding, and sintering the second mixture to obtain nickel magnesium zinc copper iron oxide.

5. 5. The method for producing nickel magnesium zinc copper iron oxide according to claim 4, wherein in the step of measuring the main components in a predetermined ratio and performing wet grinding to obtain a first mixture, the weight ratio of the main components, grinding balls and solvent is 1:(4.5-6):(0.6-1.2).

6. 5. The method for producing nickel magnesium zinc copper iron oxide according to claim 4, wherein in the step of weighing the auxiliary additives at a predetermined ratio and wet-grinding the pre-calcined material, the weight ratio of the total of the auxiliary additives and the pre-calcined material to the grinding balls and the solvent is 1:(4-7):(1-1.2).

7. 5. The method for producing nickel magnesium zinc copper iron oxide according to claim 4, wherein the particle size of the second mixture is 0.5 μm to 1.6 μm.

8. 5. The method for producing nickel magnesium zinc copper iron oxide according to claim 4, wherein the sintering is performed by increasing the temperature stepwise.

9. 5. The method for producing nickel magnesium zinc copper iron oxide according to claim 4, wherein the molding pressure is 3 MPa to 10 MPa.

10. The nickel magnesium zinc copper iron oxide according to any one of claims 1 to 3 is applied to a magnetic device.

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