A wide-temperature high-magnetic-inductance manganese-zinc ferrite material, a preparation method and application thereof

Abstract

The application relates to the technical field of manganese-zinc ferrite material, in particular to a wide-temperature high-permeability manganese-zinc ferrite material and a preparation method and application thereof. The application discloses a wide-temperature high-permeability manganese-zinc ferrite material, which comprises main components and additives, and the main components comprise the following raw materials in terms of molar percentage: Fe2O3: 53.17-53.4%, ZnO: 18.55-19.4%, and MnO: 27.43-28.1%. The application is prepared to obtain a manganese-zinc ferrite material with mu i =10000 (1+ / -20%), Curie temperature T c >=160 DEG C, mu i_min >=8500 in the range of 20 DEG C-120 DEG C, solves the problems of the current T c >=160 DEG C mu i =10000 manganese-zinc ferrite material mu i -T curve valley point is large, the temperature stability is relatively poor, and the competitive advantage of the manganese-zinc ferrite material in a harsh use environment such as automobile electronics is improved.

Description

Technical Field

[0001] This invention relates to the field of manganese-zinc ferrite materials technology, specifically to a wide-temperature, high-permeability manganese-zinc ferrite material, its preparation method, and its applications. Background Technology

[0002] Currently, the production and development of electronic products are moving towards miniaturization and weight reduction. However, miniaturization and weight reduction inevitably lead to severe electromagnetic interference (EMI) problems and difficulties in heat dissipation. Common-mode filters and other devices are typically used to improve EMI, and high-permeability manganese-zinc ferrite materials are the core materials for common-mode filters. This necessitates that high-permeability ferrite materials possess even higher permeability and better temperature stability. Developing high-Curie-temperature, high-permeability manganese-zinc ferrite materials is therefore crucial.

[0003] Various grades of high-permeability manganese-zinc ferrite materials have been developed both domestically and internationally. These include materials such as R15K, TSR10, TSR13, A101, and A102 developed by companies like Hengdian Dongci, Tiantong, and Yuefeng (Taiwan), and materials such as 3E10, 3E6, 3E13, and T38 developed by companies like Ferroxcube and TDK. However, these mainstream ferrite materials, with permeability around 10,000, have a Curie temperature of <140℃, making them unsuitable for demanding applications at higher temperatures.

[0004] Currently, the main problems with high-permeability manganese-zinc ferrite with a permeability of around 10,000 are: ①μ i Materials with smaller T curve valleys have smaller T c 160℃ (basic); 2T c Materials with a temperature ≥160℃ μ i The -T curve has a large valley point, indicating relatively poor material temperature stability. Develop a μ... i =10000(1±20%), Curie temperature T c μ ≥160℃, in the range of 20℃~120℃ i_min High temperature stability and high magnetic permeability manganese-zinc ferrite materials with a temperature range of ≥8500°C can obtain a wider market prospect.

[0005] In addition, patent CN115650719A demonstrates a permeability μ. i A manganese-zinc ferrite material with approximately 10,000 (1 ± 25%) and a Curie temperature > 160 °C, but the material's μ i μ in the 20℃~120℃ segment of the -T curve i_min <8500, insufficient temperature stability.

[0006] Therefore, this application proposes a wide-temperature, high-permeability manganese-zinc ferrite material, its preparation method, and its application. SUMMARY

[0007] The application provides a wide-temperature high-permeability manganese-zinc ferrite material and a preparation method and application thereof. i =10000(1±20%), a Curie temperature T c ≥160℃, a μ i_min ≥8500 high-temperature stability high-permeability manganese-zinc ferrite material, which can solve the problems of the current T c ≥160℃ μ i =10000 manganese-zinc ferrite material μ i -T curve valley point is large, the temperature stability is relatively poor, and the competitive advantage of the manganese-zinc ferrite material in a harsh use environment such as automobile electronics is improved.

[0008] The purpose of the application is achieved by the following technical solutions.

[0009] The first purpose of the application is to provide a wide-temperature high-permeability manganese-zinc ferrite material, which comprises main components and additives.

[0010] Fe2O3 53.17-53.4%

[0011] ZnO 18.55-19.4%

[0012] MnO 27.43-28.1%

[0013] The additive comprises the following raw materials in terms of weight percentage of the additive in the main components.

[0014]

[0015] Further, the main components comprise the following raw materials in terms of mole percentage.

[0016] Fe2O3 53.21%

[0017] ZnO 18.75%

[0018] MnO 28.04%.

[0019] Further, the additive comprises the following raw materials in terms of weight percentage of the additive in the main components.

[0020]

[0021] Further, the manganese-zinc ferrite material has a μ i =10000(1±20%), a Curie temperature T c≥ 160℃, μ in 20℃~120℃ segment i_min ≥ 8500.

[0022] The second object of the present application provides a preparation method of a wide-temperature high-permeability manganese-zinc ferrite material, comprising the following steps:

[0023] According to the composition of main components and additives, prepare corresponding raw materials; mix each raw material of the main components, and pre-sinter; after the pre-sintering is completed, add each raw material of the additives, mix thoroughly, and then spray granulation; after pressing and sintering, the manganese-zinc ferrite material is obtained.

[0024] Further, mix each raw material of the main components, pre-sinter, and sinter in an air atmosphere in a high-temperature furnace, with a sintering temperature of 750~850℃ and a holding time of 100~150 minutes.

[0025] Further, after the pre-sintering is completed, wet crush each raw material of the additives to obtain a slurry, and then spray granulate the slurry.

[0026] Further, granulate the slurry by using a spraying device, control the water content at 0.02~0.05wt%, and select 60~220 mesh particles for standby use.

[0027] Further, press and form the particles obtained by spray granulation into corresponding blanks, and control the density of the blanks at 3.0~3.15g / cm 3 .

[0028] Further, place the press-formed ring blanks in a pressure furnace, use a vacuum sintering method in the heating segment of 800~1200℃, and control the relative pressure in the furnace to be less than -0.07MPa; set the final sintering temperature at 1370℃~1400℃, control the pressure in the furnace at 100±10MPa at the final sintering temperature, and hold for 4.0~6.0 hours

[0029] The third object of the present application provides an application of a wide-temperature high-permeability manganese-zinc ferrite material, which applies the manganese-zinc ferrite material prepared by the above-mentioned preparation method to the preparation of a common-mode filter.

[0030] The beneficial effects of the present application are:

[0031] In the present application, the main components are doped with appropriate amounts of Ti, Ca, Bi and Cu, and Ti and Cu elements are synchronously added to flatten the μ i -T curve valley point, improve the temperature stability of the manganese-zinc ferrite material, and doping with trace Bi improves the magnet density and improves the μ i , and the Ca element appropriately improves the Curie temperature T c Therefore, the obtained manganese-zinc ferrite material meets the requirements of μ i= 10000 (1 ± 20%), Curie temperature T c ≥ 160°C, μ in the range of 20°C to 120°C i_min ≥ 8500, which can improve the competitive advantage of the manganese-zinc ferrite material in harsh use environments such as automotive electronics. BRIEF DESCRIPTION OF DRAWINGS

[0032] The application is further illustrated below in conjunction with the accompanying drawings and examples.

[0033] Figure 1 The μi-T curve of the manganese-zinc ferrite material prepared for Examples 1-4;

[0034] Figure 2 The μi-T curve of the manganese-zinc ferrite material prepared for Comparative Examples 1-4;

[0035] Figure 3 The μi-T curve of the manganese-zinc ferrite material prepared for Examples 5-8;

[0036] Figure 4 The μi-T curve of the manganese-zinc ferrite material prepared for Examples 5-7. DETAILED DESCRIPTION

[0037] In order to facilitate the understanding of those skilled in the art, the application is further illustrated below in conjunction with the examples, and the content mentioned in the embodiments is not a limitation of the application.

[0038] As used herein, "and / or" includes the term "and" and the term "or", all combinations of one or more associated listed items. The term used herein is only used to describe specific embodiments, and is not intended to limit the application. As used herein, the singular forms "one", "a", "an" and "the" are also intended to include the plural forms, unless the context clearly indicates otherwise. It is further understood that "comprising" is used in this specification to specify the stated features, integers, steps, operations, elements, and / or components, but does not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or combinations thereof.

[0039] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. It is further understood that terms such as those defined in a commonly used dictionary, are interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and are not interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0040] The exemplary applications described herein can appropriately lack any one or more of the element limitations not specifically disclosed herein. Thus, the terms "comprising," "including," "containing," etc. shall be read expansively and without limitation. Additionally, the terms "comprising," "having," "including," and the like can be used interchangeably with respect to the terms "consisting of." The terms "consisting of" and "consisting essentially of" are used interchangeably. The use of the terms "comprise," "comprising," "comprises," "include," "including," "includes," "have," "has," "having," or variants thereof are not limited to the items recited. Rather, they are meant to encompass those items as well as other items. Additionally, the term "about" is used in the context of the present application to mean approximately, in the sense of having the same function or result. Therefore, even though the application has been described in detail by reference to specific embodiments, it is the applicant's intention that changes and modifications can be made by those skilled in the art that do not depart from the spirit of the application in its broader aspect and, therefore, the appropriate scope of the application is to be determined not by the Abstract, but by the appended claims which follow.

[0041] The raw materials or reagents used in the examples and comparative examples of the present application are purchased from mainstream manufacturers in the market. If the manufacturer is not specified or the concentration is not specified, it is an analytical pure raw material or reagent that can be obtained conventionally, and there is no particular limitation as long as it can play the expected role. The stirring or mixing related instruments and equipment used in the examples are purchased from major manufacturers in the market, and there is no particular limitation as long as they can play the expected role. If the specific technology or condition is not specified in the examples, it is carried out according to the technology or condition described in the literature in the art or according to the product instruction.

[0042] The inventors found that the current T c μ≥160℃ i =10000 Mn-Zn ferrite material, there is a problem of large valley point of T i curve and relatively poor temperature stability. Therefore, the present application provides a wide temperature high permeability Mn-Zn ferrite material.

[0043] A wide temperature high permeability Mn-Zn ferrite material, comprising main components and additives, the main components, in terms of mole percentage, comprising the following raw materials:

[0044] Fe2O3 53.17-53.4%

[0045] ZnO 18.55-19.4%

[0046] MnO 27.43-28.1%

[0047] The additives, in terms of weight percentage of the main components, comprise the following raw materials:

[0048] TiO2 0.1-0.3%

[0049] Bi2O3 0.01-0.03%

[0050] CuO 0.02-0.06%

[0051] CaO 0.01-0.03%.

[0052] Specifically, for example, in the main ingredients, by molar percentage, including the following raw materials:

[0053] Fe2O3: 53.17%, ZnO: 18.73%, MnO: 28.1%; or for example, in the main ingredients, by molar percentage, including the following raw materials: Fe2O3: 53.21%, ZnO: 18.75%, MnO: 28.04%; or for example, in the main ingredients, by molar percentage, including the following raw materials: Fe2O3: 53.4%, ZnO: 19.17%, MnO: 27.43%.

[0054] Specifically, for example, in the additives, by weight percentage of the additives in the main ingredients, the additives include the following raw materials: TiO2: 0.3%, Bi2O3: 0.03%, CuO: 0.06%, CaO: 0.03%. For example, in the additives, by weight percentage of the additives in the main ingredients, the additives include the following raw materials: TiO2: 0.1%, Bi2O3: 0.01%, CuO: 0.02%, CaO: 0.01%. Or for example, by weight percentage of the additives in the main ingredients, the additives include the following raw materials: TiO2: 0.2%, Bi2O3: 0.02%, CuO: 0.04%, CaO: 0.02%. In the main ingredients, the manganese zinc ferrite material is prepared by doping appropriate amounts of Ti, Ca, Bi and Cu, and Ti and Cu elements are added synchronously to flatten μ i The valley point of the T curve improves the temperature stability of the material, and a small amount of Bi doping improves the magnet density and improves μ i The Ca element appropriately improves the Curie temperature T c .

[0055] In some embodiments, a method for preparing a wide-temperature high-permeability manganese zinc ferrite material includes the following steps:

[0056] According to the composition of the main ingredients and the additives, prepare the corresponding raw materials; mix the raw materials of the main ingredients, and pre-burn; after the pre-burning is completed, add the raw materials of the additives, mix thoroughly, and then spray granulation; after pressing and sintering, the manganese zinc ferrite material is obtained. The specific steps are as follows:

[0057] (1)Preparation: the main component raw materials are selected from Fe2O3, ZnO, MnO oxides, the content of Fe2O3 is 53.17mol%~53.4mol%, the content of ZnO is 18.55mol%~19.4mol%, and the content of MnO is 27.43mol%~28.1mol%, the required raw material mass is calculated according to the total set mass, the purity of the raw material, and each raw material is weighed for standby, and each raw material is fully mixed by using a strong mixer for 40 minutes;

[0058] (2) Pre-sintering: the mixed raw materials are sintered in a high-temperature furnace in an air atmosphere, the sintering temperature is 750~850℃, and the temperature is kept for 100~150 minutes;

[0059] (3) Adding additives and grinding: 0.1~0.3wt% of TiO2, 0.01~0.03wt% of Bi2O3, 0.02~0.06wt% of CuO and 0.01~0.03wt% of CaO additives of electronic pure grade are added to the prepared pre-sintered material, and then wet crushing is performed by using a sand mill, pure water is used in the grinding process, and the average particle size of the slurry is controlled to be 1.0μm~1.5μm;

[0060] (4) Spray granulation: the slurry prepared in step (3) is granulated by using a spray device, the water content is controlled to be 0.02~0.05wt%, and after adding an appropriate amount of dry lubricant for granulation, 60mesh~220mesh particles are selected for standby;

[0061] (5) Pressing forming: the granular material of step (4) is pressed into a corresponding ring blank by using a full-automatic dry powder press, and the ring blank forming density is controlled to be 3.0~3.15g / cm 3 ;

[0062] (6) Bell furnace sintering: the ring blank formed in step (5) is placed in a pressure furnace, the temperature rising section is 800~1200℃, the vacuum sintering method is used, the relative pressure in the furnace is controlled to be less than-0.07MPa, the final sintering temperature is set to be 1370℃~1400℃, the pressure in the furnace is controlled to be 100±10MPa during the final sintering temperature, and the temperature is kept for 4.0~6.0 hours, and the balanced oxygen partial pressure atmosphere is used from the time when the final sintering temperature is reached to the end of sintering.

[0063] The technical solutions of the present application are illustrated by the following detailed examples:

[0064] Examples 1-4 and Comparative Examples 1-4 are manganese-zinc ferrite materials prepared by adding the additives shown in Table 1 to the main components shown in Table 1. The additives are TiO2, Bi2O3, CuO, and CaO. The amounts of the additives are 0.1% for TiO2, 0.01% for Bi2O3, 0.02% for CuO, and 0.001% for CaO. The main components are shown in Table 1. The manganese-zinc ferrite materials are prepared by wet milling using pure water as the grinding aid, and the average particle size of the slurry is controlled to be 1.0-1.5 μm.

[0065] Examples 5-8 are manganese-zinc ferrite materials prepared by adding the additives shown in Table 2 to the main components shown in Table 1. The additives are TiO2, Bi2O3, CuO, and CaO. The amounts of the additives are 0.1% for TiO2, 0.01% for Bi2O3, 0.02% for CuO, and 0.001% for CaO. The main components are shown in Table 1. The manganese-zinc ferrite materials are prepared by wet milling using pure water as the grinding aid, and the average particle size of the slurry is controlled to be 1.0-1.5 μm.

[0066] Comparative Examples 5-7 are manganese-zinc ferrite materials prepared by adding the additives shown in Table 2 to the main components shown in Table 1. The additives are TiO2, Bi2O3, CuO, and CaO. The amounts of the additives are 0.1% for TiO2, 0.01% for Bi2O3, 0.02% for CuO, and 0.001% for CaO. The main components are shown in Table 1. The manganese-zinc ferrite materials are prepared by wet milling using pure water as the grinding aid, and the average particle size of the slurry is controlled to be 1.0-1.5 μm.

[0067] Table 1

[0068]

[0069] Table 2

[0070]

[0071] As shown in Table 1, in Examples 1-4, the manganese-zinc ferrite materials, which have only the main components, exhibit μ i of 10082-11107, Tc of 160-170°C, and μ i_min of 9116-10078.

[0072] In Comparative Example 1 or Comparative Example 2, the amount of ZnO is increased, and the manganese-zinc ferrite material exhibits a significantly increased μ i , an increased T c , and an increased μ i_min . In Comparative Example 3 or Comparative Example 4, the amount of MnO is increased, and the manganese-zinc ferrite material exhibits a significantly decreased μ i , an increased T c , and a decreased μ i_min .

[0073] In Examples 5-8, the manganese-zinc ferrite materials are prepared by adding the additives shown in Table 2 to the main components shown in Table 1. The additives are TiO2, Bi2O3, CuO, and CaO. The amounts of the additives are 0.1% for TiO2, 0.01% for Bi2O3, 0.02% for CuO, and 0.001% for CaO. The main components are shown in Table 1. The manganese-zinc ferrite materials are prepared by wet milling using pure water as the grinding aid, and the average particle size of the slurry is controlled to be 1.0-1.5 μm. i are stable at 10145-10457, and μ i_minIn 9287-9500, the requirement of ≥8500 is met. It can be seen that by doping 0.1-0.3wt% of TiO2, 0.01-0.03wt% of Bi2O3, 0.02-0.06wt% of CuO and 0.01-0.03wt% of CaO, the valley point of the μi-T curve can be simultaneously flattened and the temperature stability of the material can be improved.

[0074] Comparative Examples 5-7: Manganese-zinc ferrite materials were prepared by adding the corresponding additives; in Comparative Example 5, the content of TiO2 was high (CaO was not added), TiO2 was 0.32%, Bi2O3 was 0.04%, CuO was 0.01%, μ i was significantly reduced to 7803, μ i_min was reduced to 7750; therefore, increasing Zn in the main components can greatly improve μ i , and T c was reduced.

[0075] Comparative Example 6: The weight of each raw material in the additives was less, TiO2 was 0.05%, Bi2O3 was 0.04%, CuO was 0.07%, CaO was 0.04%, μ i was significantly reduced to 9045, μ i_min was reduced to 7601.

[0076] Comparative Example 7: Bi2O3 was not added, TiO2 was 0.1%, CuO was 0.07%, CaO was 0.04%, μ i was significantly reduced to 8755, μ i_min was reduced to 7641.

[0077] The above examples are the preferred implementation of the present application, in addition to this, the present application can be implemented in other ways, without departing from the concept of the present application, any obvious substitution is within the protection scope of the present application.

Claims

1. A wide-temperature, high-permeability manganese-zinc ferrite material, comprising main components and additives, characterized in that, The main components, in molar percentage, include the following raw materials: Fe2O3 53.17~53.32% ZnO 18.58~19.4% MnO 27.43~28.1%; The additives, based on their weight percentage relative to the main components, include the following raw materials: TiO2 0.1-0.3% Bi2O3 0.01~0.03% CuO 0.02–0.06% CaO 0.01–0.03%.

2. The wide-temperature, high-permeability manganese-zinc ferrite material according to claim 1, characterized in that, The main components, in molar percentage, include the following raw materials: Fe2O3 53.21% ZnO 18.75% MnO 28.04%.

3. The wide-temperature, high-permeability manganese-zinc ferrite material according to claim 1, characterized in that, The additives, based on their weight percentage relative to the main components, include the following raw materials: TiO2 0.2% Bi2O3 0.02% CuO 0.04% CaO 0.02%.

4. The wide-temperature, high-permeability manganese-zinc ferrite material according to claim 1, characterized in that, The manganese zinc ferrite material μ i =10000(1±20%), Curie temperature T c μ ≥160℃, in the range of 20℃~120℃ i_min ≥8500.

5. A method for preparing a wide-temperature, high-permeability manganese-zinc ferrite material according to any one of claims 1-4, characterized in that, Includes the following steps: Prepare the corresponding raw materials according to the composition of the main components and additives; mix the raw materials of the main components and pre-fire them; after pre-fire, add the raw materials of the additives, mix them thoroughly, and then spray granulate them; after pressing and sintering, manganese zinc ferrite material is obtained.

6. The preparation method according to claim 5, characterized in that, The main components are mixed and pre-fired, then sintered in an air atmosphere in a high-temperature furnace at a temperature of 750–850°C for 100–150 minutes.

7. The preparation method according to claim 5, characterized in that, After pre-calcination, the raw materials with added additives are wet-milled to obtain a slurry, which is then spray-granulated.

8. The preparation method according to claim 7, characterized in that, The slurry is granulated using a spray gun, with the water content controlled at 0.02–0.05 wt%, and 60–220 mesh particles are selected for later use.

9. The preparation method according to claim 5, characterized in that, The granules obtained by spray granulation are pressed into corresponding blanks, with the density of the blanks controlled between 3.0 and 3.15 g / cm³. 3 .

10. The preparation method according to claim 9, characterized in that, The pressed ring blank is placed in a pressure furnace, and vacuum sintering is used in the heating section of 800-1200℃; the final firing temperature is set to 1370-1400℃, and the holding time is 4.0-6.0 hours.

11. An application of a wide-temperature, high-permeability manganese-zinc ferrite material, characterized in that, The manganese-zinc ferrite material according to any one of claims 1-4 or the manganese-zinc ferrite material prepared by the preparation method according to any one of claims 5-10 is applied to the preparation of common-mode filters.

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