Iron-manganese-zinc ferrite material, preparation method and application thereof

Abstract

The application provides an iron-manganese-zinc ferrite material, a preparation method and application thereof. The iron-manganese-zinc ferrite material comprises main components and auxiliary components. The main components comprise Fe2O3 with a mass fraction of 68-71 wt%, ZnO with a mass fraction of 11-15 wt%, and the balance of Mn3O4, with the mass of the main components being 100%. The auxiliary components comprise any one or a combination of at least two of CaCO3, Bi2O3, TiO2 or MoO3. The iron-manganese-zinc ferrite material provided by the application has low stress sensitivity, high initial magnetic permeability and wide frequency and high impedance, so that the magnetic core made of the iron-manganese-zinc ferrite material has a smaller inductance drop ratio under the same stress.

Description

Technical Field

[0001] This invention belongs to the field of ferrite material technology, and relates to an iron-manganese-zinc ferrite material, and more particularly to an iron-manganese-zinc ferrite material, its preparation method and application. Background Technology

[0002] In recent years, as humanity has gradually entered the electronic information age, electronic products have become indispensable for work, leisure, entertainment, learning, and video conferencing. While bringing convenience, electronic products also cause environmental pollution, namely electromagnetic interference. High-permeability manganese-zinc ferrite is widely used in signal transmission and electromagnetic interference suppression technologies. High-permeability manganese-zinc ferrite materials have gained popularity due to their high permeability, low price, and miniaturization. However, because the resistivity of high-permeability manganese-zinc ferrite materials is relatively low, it is difficult to meet voltage withstand requirements, necessitating coating treatment, as well as assembly and winding by downstream customers. These subsequent operations on the core will generate stress on the core, leading to a decrease in its inductance.

[0003] CN101870578A discloses a high-permeability (μi) wide-temperature manganese-zinc ferrite material. By limiting the iron oxide content to 53–58 mol%, the zinc oxide content to 20–28 mol%, and the remainder to manganese oxide, a high permeability (μi) of 12000 with a wide temperature range is achieved. However, the high-permeability (μi) wide-temperature manganese-zinc ferrite material disclosed in this patent exhibits excessively high stress sensitivity.

[0004] CN103011791A discloses a high-permeability manganese-zinc ferrite material. By limiting the content of iron oxide to 51-54 mol%, the content of zinc oxide to 23-27 mol%, and the remainder to manganese oxide, the high permeability of the manganese-zinc ferrite material is achieved. However, this high-permeability manganese-zinc ferrite material has excessively high stress sensitivity.

[0005] CN105541316A discloses a manganese-zinc ferrite material for EMI suppression and its preparation method. By limiting the content of iron oxide to 50.5–52.5 mol%, the content of zinc oxide to 18.5–20.5 mol%, and the remainder being manganese oxide, a manganese-zinc ferrite material with a magnetic permeability >12000 for EMI suppression was prepared. However, this manganese-zinc ferrite material for EMI suppression exhibits excessively high stress sensitivity.

[0006] Currently available iron-manganese-zinc ferrite materials all have certain drawbacks, including the inability to simultaneously possess low stress sensitivity, high permeability, and wide-bandwidth high impedance. Therefore, developing and designing a novel iron-manganese-zinc ferrite material and its preparation method is of paramount importance. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide an iron-manganese-zinc ferrite material, its preparation method, and its application. The iron-manganese-zinc ferrite material provided by the present invention has low stress sensitivity, high initial permeability, and wide-band high impedance, thereby making the magnetic core made of the iron-manganese-zinc ferrite material have a smaller inductance drop ratio under the same stress.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides an iron-manganese-zinc ferrite material, the iron-manganese-zinc ferrite material comprising a main component and an auxiliary component;

[0010] The main component comprises 68-71 wt% Fe2O3, 11-15 wt% ZnO, and the balance is Mn3O4, based on the mass percentage of the main component.

[0011] The auxiliary components include any one or a combination of at least two of CaCO3, Bi2O3, TiO2, or MoO3.

[0012] In this invention, the main component is defined as 100% by mass. The main component includes Fe2O3 with a mass fraction of 68 to 71 wt%, for example, 68 wt%, 68.5 wt%, 69 wt%, 69.5 wt%, 70 wt%, 70.5 wt%, or 71 wt%, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0013] In this invention, the main component is defined as 100% by mass. The main component includes ZnO with a mass fraction of 11 to 15 wt%, for example, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, or 15 wt%, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0014] The auxiliary components described in this invention include any one or a combination of at least two of CaCO3, Bi2O3, TiO2 or MoO3. Typical but non-limiting combinations include combinations of CaCO3 and Bi2O3, combinations of Bi2O3 and TiO2, combinations of TiO2 and MoO3, or combinations of CaCO3, Bi2O3 and TiO2.

[0015] The iron-manganese-zinc ferrite material provided by the present invention has low stress sensitivity, high initial permeability and wide-band high impedance, thereby making the magnetic core made of the iron-manganese-zinc ferrite material have a smaller inductance drop rate under the same stress.

[0016] Preferably, based on the mass of the main component as the total mass, the auxiliary components include CaCO3 with a mass fraction of 200-2000 ppm, Bi2O3 with a mass fraction of 200-2000 ppm, TiO2 with a mass fraction of 200-2000 ppm, and MoO3 with a mass fraction of 200-2000 ppm.

[0017] In this invention, the mass of the main component is taken as the total mass. The auxiliary component includes CaCO3 with a mass fraction of 200 to 2000 ppm, for example, it can be 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, 1500 ppm, 1600 ppm, 1700 ppm, 1800 ppm, 1900 ppm or 2000 ppm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0018] In this invention, the mass of the main component is used as the total mass. The auxiliary component includes Bi2O3 with a mass fraction of 200 to 2000 ppm, for example, it can be 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, 1500 ppm, 1600 ppm, 1700 ppm, 1800 ppm, 1900 ppm or 2000 ppm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0019] In this invention, the mass of the main component is used as the total mass. The auxiliary component includes TiO2 with a mass fraction of 200 to 2000 ppm, for example, it can be 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, 1500 ppm, 1600 ppm, 1700 ppm, 1800 ppm, 1900 ppm or 2000 ppm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0020] In this invention, the mass of the main component is used as the total mass. The auxiliary component includes MoO3 with a mass fraction of 200 to 2000 ppm, for example, it can be 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 1100 ppm, 1200 ppm, 1300 ppm, 1400 ppm, 1500 ppm, 1600 ppm, 1700 ppm, 1800 ppm, 1900 ppm or 2000 ppm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0021] Preferably, the main component comprises 69-70 wt% Fe2O3, 12.5-13.5 wt% ZnO, and the balance being Mn3O4, based on the mass percentage of the main component.

[0022] In this invention, the main component is defined as 100% by mass. The main component includes 69-70 wt% Fe2O3, for example, 69 wt%, 69.1 wt%, 69.2 wt%, 69.3 wt%, 69.4 wt%, 69.5 wt%, 69.6 wt%, 69.7 wt%, 69.8 wt%, 69.9 wt%, or 70 wt%, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0023] In this invention, the main component is defined as 100% by mass. The main component includes ZnO with a mass fraction of 12.5 to 13.5 wt%, for example, it can be 12.5 wt%, 12.6 wt%, 12.7 wt%, 12.8 wt%, 12.9 wt%, 13 wt%, 13.1 wt%, 13.2 wt%, 13.3 wt%, 13.4 wt%, or 13.5 wt%, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0024] Preferably, based on the mass of the main component as the total mass, the auxiliary components include CaCO3 with a mass fraction of 200-1000 ppm, Bi2O3 with a mass fraction of 200-1000 ppm, TiO2 with a mass fraction of 200-1000 ppm, and MoO3 with a mass fraction of 200-1000 ppm.

[0025] In this invention, the mass of the main component is used as the total mass. The auxiliary component includes CaCO3 with a mass fraction of 200 to 1000 ppm, for example, it can be 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm or 1000 ppm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0026] In this invention, the mass of the main component is used as the total mass. The auxiliary component includes Bi2O3 with a mass fraction of 200 to 1000 ppm, for example, it can be 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm or 1000 ppm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0027] In this invention, the mass of the main component is used as the total mass. The auxiliary component includes TiO2 with a mass fraction of 200 to 1000 ppm, for example, it can be 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm or 1000 ppm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0028] In this invention, the mass of the main component is used as the total mass. The auxiliary component includes MoO3 with a mass fraction of 200 to 1000 ppm, for example, it can be 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm or 1000 ppm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0029] In a second aspect, the present invention provides a method for preparing the iron-manganese-zinc ferrite material described in the first aspect, the method comprising:

[0030] (1) After mixing the main components and solvent to obtain a slurry, the slurry is pre-calcined to obtain a pre-calcined material. The main components include Fe2O3, ZnO and Mn3O4.

[0031] (2) Mix the pre-burned material obtained in step (1) with the auxiliary components to obtain a mixture;

[0032] (3) The mixture obtained in step (2) is sintered in a protective atmosphere to obtain iron-manganese-zinc ferrite material.

[0033] Preferably, the mixing method in step (1) includes a first ball milling, the ball milling time being 20 to 80 minutes, for example, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, 75 minutes or 80 minutes, but not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0034] Preferably, during the first ball milling process, the mass ratio of the main component, the grinding balls, and the solvent is (0.5-1.5):(3.5-4.5):(0.5-1.5).

[0035] The mass ratio of the main component to the grinding ball described in this invention is 0.5:3.5, 0.6:3.5, 0.9:3.5, 1.1:3.5, 1.3:3.5, 1.5:3.5, 0.5:4, 0.6:4, 0.9:4, 1.1:4, 1.3:4, 1.5:4, 0.5:4.5, 0.6:4.5, 1.1:4.5, or 1.3:4.5, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0036] The mass ratio of grinding balls to solvent in this invention is 3.5:0.5, 3.5:0.6, 3.5:0.9, 3.5:1.1, 3.5:1.3, 3.5:1.5, 4:0.5, 4:0.6, 4:0.9, 4:1.1, 4:1.3, 4:1.5, 4.5:0.5, 4.5:0.6, 4.5:1.1, or 4.5:1.3, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0037] Preferably, the solvent in step (1) includes water.

[0038] Preferably, the pre-calcination temperature in step (1) is 980-1035°C, the pre-calcination is carried out in a rotary kiln, and the slurry enters the rotary kiln at a rate of 400-500 kg / h.

[0039] In this invention, the pre-firing temperature in step (1) is 980 to 1035°C, for example, it can be 980°C, 985°C, 990°C, 995°C, 1000°C, 1005°C, 1010°C, 1015°C, 1020°C, 1025°C, 1030°C or 1035°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0040] In this invention, the slurry enters the rotary kiln at a rate of 400–500 kg / h, for example, 400 kg / h, 410 kg / h, 420 kg / h, 430 kg / h, 440 kg / h, 450 kg / h, 460 kg / h, 470 kg / h, 480 kg / h, 490 kg / h, or 500 kg / h, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0041] Preferably, the mixing in step (2) further includes mixing the dispersant and the binder.

[0042] Preferably, the mixing method in step (2) includes a second ball milling, the time of which is 120 to 150 minutes, for example, 120 minutes, 125 minutes, 130 minutes, 135 minutes, 140 minutes, 145 minutes or 150 minutes, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0043] Preferably, during the second ball milling process, the mass ratio of pre-burned material, dispersant, binder to grinding balls is (0.5-1.5):(0.005-0.015):(0.05-0.15):(3-5).

[0044] In the second ball milling process of this invention, the mass ratio of pre-calcined material to dispersant is (0.5-1.5):(0.005-0.015), for example, it can be 0.5:0.005, 0.7:0.005, 0.9:0.005, 1.1:0.005, 1.3:0.005, 1.5:0.005, 0.5:0.007, 0.9:0.007, 1.1: The values ​​are 0.007, 1.3:0.007, 1.5:0.007, 0.5:0.009, 0.7:0.009, 1.1:0.009, 1.3:0.009, 0.5:0.015, 0.7:0.015, 1.1:0.015, or 1.3:0.015, but are not limited to the listed values; other unlisted values ​​within this range also apply.

[0045] In the second ball milling process of this invention, the mass ratio of pre-calcined material to binder is (0.5-1.5):(0.05-0.15), for example, it can be 0.5:0.05, 0.7:0.05, 0.9:0.05, 1.1:0.05, 1.3:0.05, 1.5:0.05, 0.5:0.07, 0.9:0.07, 1.1:0.07, 1.3:0.07, 1.5:0.07, 0.5:0.09, 0.7:0.09, 1.1:0.09, 1.3:0.09, 0.5:0.15, 0.7:0.15, 1.1:0.15 or 1.3:0.15, but it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0046] In the second ball milling process of this invention, the mass ratio of pre-burned material to grinding balls is (0.5-1.5):(3-5), for example, it can be 0.5:3, 0.7:3, 0.8:3, 1.1:3, 1.3:3, 1.5:3, 0.5:4, 0.7:4, 0.8:4, 1.1:4, 1.3:4, 1.5:4, 0.5:5, 0.7:5, 0.8:5, 1.1:5, 1.3:5 or 1.5:5, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0047] Preferably, the dispersant comprises citric acid.

[0048] Preferably, the adhesive comprises PVA.

[0049] Preferably, spray granulation is further included between step (2) and step (3).

[0050] Preferably, the spray granulation step (3) is further divided into preforming step.

[0051] Preferably, the oxygen content in the protective atmosphere described in step (3) is 0–21 vol%, for example, it can be 0 vol%, 1 vol%, 3 vol%, 5 vol%, 7 vol%, 9 vol%, 11 vol%, 13 vol%, 15 vol%, 17 vol%, 19 vol%, or 21 vol%, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable, preferably 0–10 vol%.

[0052] Preferably, the sintering temperature in step (3) is 1200-1400℃ and the time is 4-10h.

[0053] In this invention, the sintering temperature in step (3) is 1200 to 1400°C, for example, it can be 1200°C, 1210°C, 1220°C, 1230°C, 1240°C, 1250°C, 1260°C, 1270°C, 1280°C, 1290°C, 1300°C, 1310°C, 1320°C, 1330°C, 1340°C, 1350°C, 1360°C, 1370°C, 1380°C, 1390°C or 1400°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0054] In this invention, the sintering time in step (3) is 4 to 10 hours, for example, it can be 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0055] Preferably, the sintering in step (3) is carried out in three stages; the temperature of the first stage is 1350-1400℃ and the time is 7-9h; the temperature of the second stage is 1350-1400℃ and the time is 0.5-1.5h; the temperature of the third stage is 1300-1350℃ and the time is 0.5-1.5h.

[0056] In this invention, the temperature of the first segment is 1350 to 1400°C, for example, it can be 1350°C, 1360°C, 1370°C, 1380°C, 1390°C or 1400°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0057] In this invention, the time for the first segment is 7 to 9 hours, for example, it can be 7 hours, 7.2 hours, 7.4 hours, 7.6 hours, 7.8 hours, 8 hours, 8.2 hours, 8.4 hours, 8.6 hours, 8.8 hours or 9 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0058] In this invention, the temperature of the second segment is 1350 to 1400°C, for example, it can be 1350°C, 1360°C, 1370°C, 1380°C, 1390°C or 1400°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0059] In this invention, the second segment time is 0.5 to 1.5 hours, for example, it can be 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hour, 1.1 hours, 1.2 hours, 1.35 hours, 1.4 hours or 1.5 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0060] In this invention, the temperature of the third segment is 1300 to 1350°C, for example, it can be 1300°C, 1310°C, 1320°C, 1330°C, 1340°C or 1350°C, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0061] In this invention, the time of the third segment is 0.5 to 1.5 hours, for example, it can be 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hour, 1.1 hours, 1.2 hours, 1.35 hours, 1.4 hours or 1.5 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0062] Preferably, step (3) further includes cooling after sintering, wherein the cooling is carried out under equilibrium oxygen partial pressure.

[0063] As a preferred embodiment of the preparation method of the present invention, the preparation method includes:

[0064] (1) The main components and water are mixed by ball milling for 20-80 minutes to obtain a slurry. During the ball milling process, the mass ratio of the main components, grinding balls and solvent is (0.5-1.5):(3.5-4.5):(0.5-1.5). Then, the slurry is pre-calcined in a rotary kiln at a temperature of 980-1035℃. The slurry enters the rotary kiln at a rate of 400-500 kg / h to obtain a pre-calcined material. The main components include Fe2O3, ZnO and Mn3O4.

[0065] (2) The pre-calcined material obtained in step (1) is mixed with auxiliary components, dispersant and binder by ball milling. During the ball milling process, the mass ratio of pre-calcined material, dispersant, binder and milling balls is (0.5~1.5):(0.005~0.015):(0.05~0.15):(3~5) to obtain a mixture;

[0066] (3) The mixture obtained in step (2) is spray-granulated and pressed into a preform to obtain a preform. The preform is then sintered in three stages. The temperature of the first stage is 1350-1400℃ and the time is 7-9h. The temperature of the second stage is 1350-1400℃ and the time is 0.5-1.5h. The temperature of the third stage is 1200-1350℃ and the time is 0.5-1.5h. The preform is then cooled under balanced oxygen partial pressure to obtain an iron-manganese-zinc ferrite material.

[0067] Thirdly, the present invention provides an application of the iron-manganese-zinc ferrite material described in the first aspect, wherein the iron-manganese-zinc ferrite material is used for signal transmission or electromagnetic interference suppression.

[0068] Compared with the prior art, the present invention has the following beneficial effects:

[0069] The iron-manganese-zinc ferrite material provided by the present invention has low stress sensitivity, high initial permeability and wide-band high impedance, thereby making the magnetic core made of the iron-manganese-zinc ferrite material have a smaller inductance drop rate under the same stress. Detailed Implementation

[0070] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0071] Example 1

[0072] This embodiment provides an iron-manganese-zinc ferrite material, which includes a main component and an auxiliary component;

[0073] The main component comprises 69.08 wt% Fe2O3, 12.23 wt% ZnO, and the balance is Mn3O4, based on the mass percentage of the main component.

[0074] Based on the mass of the main components, the auxiliary components include CaCO3 with a mass fraction of 400 ppm, Bi2O3 with a mass fraction of 500 ppm, TiO2 with a mass fraction of 300 ppm, and MoO3 with a mass fraction of 200 ppm.

[0075] The preparation method of the iron-manganese-zinc ferrite material is as follows:

[0076] (1) The main components and water are mixed by ball milling for 30 minutes to obtain a slurry. During the ball milling process, the mass ratio of the main components, grinding balls and water is 1:4:1. Then, the slurry is pre-calcined in a rotary kiln at a temperature of 1020℃. The slurry enters the rotary kiln at a rate of 450 kg / h to obtain the pre-calcined material. The main components include Fe2O3, ZnO and Mn3O4.

[0077] (2) The pre-burned material obtained in step (1) is mixed with auxiliary components, citric acid and PVA by ball milling. During the ball milling process, the mass ratio of pre-burned material, citric acid, PVA and milling balls is 1:0.01:0.1:4 to obtain a mixture. The auxiliary components include CaCO3, Bi2O3, TiO2 and MoO3.

[0078] (3) The mixture obtained in step (2) is spray-granulated and pressed into a preform to obtain a preform. The preform is sintered at 1385°C for 8 hours in a nitrogen atmosphere with an oxygen content of 21 vol%, then sintered at 1385°C for 1 hour in a nitrogen atmosphere with an oxygen content of 8 vol%, then sintered at 1260°C for 1 hour in a nitrogen atmosphere with an oxygen content of 6 vol%, and then cooled under a balanced oxygen partial pressure. The cooling is carried out in a nitrogen atmosphere with an oxygen content of 0 vol%, to obtain an iron-manganese-zinc ferrite material.

[0079] Example 2

[0080] This embodiment provides an iron-manganese-zinc ferrite material, which includes a main component and an auxiliary component;

[0081] The main component comprises 69.24 wt% Fe2O3, 12.41 wt% ZnO, and the balance is Mn3O4, based on the mass percentage of the main component.

[0082] Based on the mass of the main components, the auxiliary components include CaCO3 with a mass fraction of 400 ppm, Bi2O3 with a mass fraction of 500 ppm, TiO2 with a mass fraction of 300 ppm, and MoO3 with a mass fraction of 200 ppm.

[0083] The preparation method of the iron-manganese-zinc ferrite material is as follows:

[0084] (1) The main components and water are mixed by ball milling for 30 minutes to obtain a slurry. During the ball milling process, the mass ratio of the main components, grinding balls and solvent is 1:4:1. Then, the slurry is pre-calcined in a rotary kiln at a temperature of 1020℃. The slurry enters the rotary kiln at a rate of 450 kg / h to obtain the pre-calcined material. The main components include Fe2O3, ZnO and Mn3O4.

[0085] (2) The pre-burned material obtained in step (1) is mixed with auxiliary components, citric acid and PVA by ball milling. During the ball milling process, the mass ratio of pre-burned material, citric acid, PVA and milling balls is 1:0.01:0.1:4 to obtain a mixture. The auxiliary components include CaCO3, Bi2O3, TiO2 and MoO3.

[0086] (3) The mixture obtained in step (2) is spray-granulated and pressed into a preform to obtain a preform. The preform is sintered at 1385°C for 8 hours in a protective atmosphere with an oxygen content of 21 vol%, then sintered at 1385°C for 1 hour in a nitrogen atmosphere with an oxygen content of 8 vol%, then sintered at 1260°C for 1 hour in a nitrogen atmosphere with an oxygen content of 6 vol%, and then cooled under a balanced oxygen partial pressure. The cooling is carried out in a nitrogen atmosphere with an oxygen content of 0 vol%, to obtain an iron-manganese-zinc ferrite material.

[0087] Example 3

[0088] This embodiment provides an iron-manganese-zinc ferrite material, which includes a main component and an auxiliary component;

[0089] The main component comprises 69.4 wt% Fe2O3, 12.6 wt% ZnO, and the balance is Mn3O4, based on the mass percentage of the main component.

[0090] Based on the mass of the main components, the auxiliary components include CaCO3 with a mass fraction of 400 ppm, Bi2O3 with a mass fraction of 500 ppm, TiO2 with a mass fraction of 300 ppm, and MoO3 with a mass fraction of 200 ppm.

[0091] The preparation method of the iron-manganese-zinc ferrite material is as follows:

[0092] (1) The main components and water are mixed by ball milling for 30 minutes to obtain a slurry. During the ball milling process, the mass ratio of the main components, grinding balls and solvent is 1:4:1. Then, the slurry is pre-calcined in a rotary kiln at a temperature of 1020℃. The slurry enters the rotary kiln at a rate of 450 kg / h to obtain the pre-calcined material. The main components include Fe2O3, ZnO and Mn3O4.

[0093] (2) The pre-burned material obtained in step (1) is mixed with auxiliary components, citric acid and PVA by ball milling. During the ball milling process, the mass ratio of pre-burned material, citric acid, PVA and milling balls is 1:0.01:0.1:4 to obtain a mixture. The auxiliary components include CaCO3, Bi2O3, TiO2 and MoO3.

[0094] (3) The mixture obtained in step (2) is spray-granulated and pressed into a preform to obtain a preform. The preform is sintered at 1385°C for 8 hours in a nitrogen atmosphere with an oxygen content of 21 vol%, then sintered at 1385°C for 1 hour in a nitrogen atmosphere with an oxygen content of 8 vol%, then sintered at 1260°C for 1 hour in a nitrogen atmosphere with an oxygen content of 6 vol%, and then cooled under a balanced oxygen partial pressure. The cooling is carried out in a nitrogen atmosphere with an oxygen content of 0 vol%, to obtain an iron-manganese-zinc ferrite material.

[0095] Example 4

[0096] This embodiment provides an iron-manganese-zinc ferrite material, which includes a main component and an auxiliary component;

[0097] The main component comprises 69.56 wt% Fe2O3, 12.78 wt% ZnO, and the balance is Mn3O4, based on the mass percentage of the main component.

[0098] Based on the mass of the main components, the auxiliary components include CaCO3 with a mass fraction of 400 ppm, Bi2O3 with a mass fraction of 500 ppm, TiO2 with a mass fraction of 300 ppm, and MoO3 with a mass fraction of 200 ppm.

[0099] The preparation method of the iron-manganese-zinc ferrite material is as follows:

[0100] (1) The main components and water are mixed by ball milling for 30 minutes to obtain a slurry. During the ball milling process, the mass ratio of the main components, grinding balls and solvent is 1:4:1. Then, the slurry is pre-calcined in a rotary kiln at a temperature of 1020℃. The slurry enters the rotary kiln at a rate of 450 kg / h to obtain the pre-calcined material. The main components include Fe2O3, ZnO and Mn3O4.

[0101] (2) The pre-burned material obtained in step (1) is mixed with auxiliary components, citric acid and PVA by ball milling. During the ball milling process, the mass ratio of pre-burned material, citric acid, PVA and milling balls is 1:0.01:0.1:4 to obtain a mixture. The auxiliary components include CaCO3, Bi2O3, TiO2 and MoO3.

[0102] (3) The mixture obtained in step (2) is spray-granulated and pressed into a preform to obtain a preform. The preform is sintered at 1385°C for 8 hours in a nitrogen atmosphere with an oxygen content of 21 vol%, then sintered at 1385°C for 1 hour in a nitrogen atmosphere with an oxygen content of 8 vol%, then sintered at 1260°C for 1 hour in a nitrogen atmosphere with an oxygen content of 6 vol%, and then cooled under a balanced oxygen partial pressure. The cooling is carried out in a nitrogen atmosphere with an oxygen content of 0 vol%, to obtain an iron-manganese-zinc ferrite material.

[0103] Example 5

[0104] This embodiment provides an iron-manganese-zinc ferrite material, which is the same as that in Example 1 except that the mass fraction of CaCO3 in the auxiliary component is 100 ppm.

[0105] Example 6

[0106] This embodiment provides an iron-manganese-zinc ferrite material, which is the same as that in Example 1 except that the mass fraction of CaCO3 in the auxiliary component is 2500ppm.

[0107] Example 7

[0108] This embodiment provides an iron-manganese-zinc ferrite material, which is the same as that in Example 1 except that the mass fraction of Bi2O3 in the auxiliary component is 2500ppm.

[0109] Example 8

[0110] This embodiment provides an iron-manganese-zinc ferrite material, which is the same as that in Example 1 except that the mass fraction of TiO2 in the auxiliary component is 100 ppm.

[0111] Example 9

[0112] This embodiment provides an iron-manganese-zinc ferrite material, which is the same as that in Example 1 except that the mass fraction of TiO2 in the auxiliary component is 2500 ppm.

[0113] Example 10

[0114] This embodiment provides an iron-manganese-zinc ferrite material, which is the same as that in Example 1 except that the mass fraction of MoO3 in the auxiliary component is 2500 ppm.

[0115] Example 11

[0116] This embodiment provides an iron-manganese-zinc ferrite material. Except for replacing "sintering the obtained preform at 1385°C for 8 hours in a nitrogen atmosphere with an oxygen content of 21 vol%, then sintering at 1385°C for 1 hour in a nitrogen atmosphere with an oxygen content of 8 vol%, and then sintering at 1260°C for 1 hour in a nitrogen atmosphere with an oxygen content of 6 vol%" in step (3) with "sintering the obtained preform at 1385°C for 10 hours in a nitrogen atmosphere with an oxygen content of 21 vol%", the rest is the same as in Example 1.

[0117] Example 12

[0118] This embodiment provides an iron-manganese-zinc ferrite material. Except for replacing "sintering the obtained preform at 1385°C for 8 hours in a nitrogen atmosphere with an oxygen content of 21 vol%" in step (3) with "sintering the obtained preform at 1500°C for 8 hours in a nitrogen atmosphere with an oxygen content of 21 vol%", the rest is the same as in embodiment 1.

[0119] Example 13

[0120] This embodiment provides an iron-manganese-zinc ferrite material. Except for replacing "sintering at 1260°C for 1 hour in a nitrogen atmosphere with an oxygen content of 6 vol%" in step (3) with "sintering at 1100°C for 1 hour in a nitrogen atmosphere with an oxygen content of 6 vol%", the rest is the same as in embodiment 1.

[0121] Comparative Example 1

[0122] This comparative example provides an iron-manganese-zinc ferrite material, except that the mass fraction of Fe2O3 in the main component is 65wt%, and the mass fraction of Mn3O4 is increased accordingly, and the rest is the same as in Example 1.

[0123] Comparative Example 2

[0124] This comparative example provides an iron-manganese-zinc ferrite material, which is the same as in Example 1 except that the mass fraction of Fe2O3 in the main component is 73wt% and the mass fraction of Mn3O4 is reduced accordingly.

[0125] Comparative Example 3

[0126] This comparative example provides an iron-manganese-zinc ferrite material, which is the same as in Example 1 except that the mass fraction of ZnO in the main component is 9 wt% and the mass fraction of Mn3O4 is increased accordingly.

[0127] Comparative Example 4

[0128] This comparative example provides an iron-manganese-zinc ferrite material, which is the same as in Example 1 except that the mass fraction of ZnO in the main component is 17wt% and the mass fraction of Mn3O4 is reduced accordingly.

[0129] Comparative Example 5

[0130] This comparative example provides an iron-manganese-zinc ferrite material, which is the same as that in Example 1 except that the auxiliary components in the iron-manganese-zinc ferrite material are omitted.

[0131] The iron-manganese-zinc ferrite materials in the above embodiments and comparative examples were subjected to stress sensitivity tests, initial permeability tests, and broadband impedance tests, respectively.

[0132] The stress sensitivity test method is the hydraulic method, and the permeability at 10 MPa is compared with the permeability at 0 MPa as shown in Table 1.

[0133] The method for testing the initial permeability is as follows: the wire is wound for 10Ts, the inductance is tested, and then the initial permeability μi at 0.25V, 25℃ and 10KHz is obtained according to the calculation formula of inductance and permeability, as shown in Table 1.

[0134] The method for broadband impedance testing is as follows: the wire is wound for 1 Ts, and the impedance Z at a frequency of 1 MHz is obtained by using an impedance analyzer, as shown in Table 1.

[0135] Table 1

[0136]

[0137] From Table 1, we can obtain:

[0138] (1) The iron-manganese-zinc ferrite materials prepared in Examples 1 to 4 have high permeability, indicating that the obtained iron-manganese-zinc ferrite materials have low stress sensitivity. At the same time, the obtained iron-manganese-zinc ferrite materials also have high initial permeability and wideband high impedance.

[0139] (2) By comparing Example 1 with Examples 5 and 6, it can be seen that the mass fraction of CaCO3 in the auxiliary components of the present invention will affect the performance of the iron-manganese-zinc ferrite material. When the mass fraction of CaCO3 is low, the impedance R of the iron-manganese-zinc ferrite material will decrease because the resistivity will decrease due to the low calcium carbonate content. When the mass fraction of CaCO3 is high, the permeability ratio of the iron-manganese-zinc ferrite material will remain unchanged and the initial permeability μi will decrease.

[0140] (3) By comparing Examples 1 and 7, it can be seen that the mass fraction of Bi2O3 in the auxiliary components of the present invention will affect the performance of the iron-manganese-zinc ferrite material. When the mass fraction of Bi2O3 is too high, it will lead to an increase in the permeability ratio, a decrease in the initial permeability μi, and a decrease in the impedance R of the iron-manganese-zinc ferrite material. This is because the low content of Bi2O3 results in a larger grain size.

[0141] (4) By comparing Example 1 with Examples 8 and 9, it can be seen that the mass fraction of TiO2 in the auxiliary components of the present invention will affect the performance of the iron-manganese-zinc ferrite material. When the mass fraction of TiO2 is low, the permeability ratio of the iron-manganese-zinc ferrite material will remain unchanged, the initial permeability μi will decrease, and the impedance R will remain unchanged. This is because the change of TiO2 will change the position of the two peaks. When the mass fraction of TiO2 is high, the permeability ratio of the iron-manganese-zinc ferrite material will remain unchanged, the initial permeability μi will decrease, and the impedance R will remain unchanged. This is because the change of TiO2 will change the position of the two peaks.

[0142] (5) By comparing Examples 1 and 10, it can be seen that the mass fraction of MoO3 in the auxiliary components of the present invention will affect the performance of the iron-manganese-zinc ferrite material. When the mass fraction of MoO3 is too high, the magnetic permeability ratio of the iron-manganese-zinc ferrite material will increase, the initial magnetic permeability μi will decrease, and the impedance R will decrease. This is because the low content of MoO3 makes the grain size larger.

[0143] (6) By comparing Example 1 and Example 11, it can be seen that the sintering in step (3) of the present invention is carried out in three stages, which will affect the performance of the iron-manganese-zinc ferrite material. When the three-stage sintering is replaced by one-stage sintering, the magnetic permeability ratio of the iron-manganese-zinc ferrite material will increase or decrease, the initial magnetic permeability μi will decrease, and the impedance R will decrease or increase. This is because the grain size has been changed.

[0144] (7) By comparing Example 1 with Examples 12 and 13, it can be seen that the sintering temperature described in step (3) of the present invention will affect the performance of the iron-manganese-zinc ferrite material. When the sintering temperature is too low, the initial permeability μi of the iron-manganese-zinc ferrite material will decrease. When the sintering temperature is too high, the permeability ratio of the iron-manganese-zinc ferrite material will increase, the initial permeability μi will decrease, and the impedance R will decrease. This is because the grain size increases and more zinc oxide volatilizes.

[0145] (8) By comparing Example 1 with Comparative Examples 1 and 2, it can be seen that the mass fraction of Fe2O3 in the main component of the present invention will affect the performance of the iron-manganese-zinc ferrite material. When the mass fraction of Fe2O3 in the main component is low, the permeability ratio of the iron-manganese-zinc ferrite material will remain unchanged, the initial permeability μi will decrease, and the impedance R will remain unchanged. This is because the two peaks will shift. When the mass fraction of Fe2O3 in the main component is high, the permeability ratio of the iron-manganese-zinc ferrite material will remain unchanged, the initial permeability μi will decrease, and the impedance R will remain unchanged. This is because the two peaks will shift.

[0146] (9) By comparing Example 1 with Comparative Examples 3 and 4, it can be seen that the mass fraction of ZnO in the main component of the present invention will affect the performance of the iron-manganese-zinc ferrite material. When the mass fraction of ZnO in the main component is low, the permeability ratio of the iron-manganese-zinc ferrite material will remain unchanged, the initial permeability μi will decrease, and the impedance R will remain unchanged. This is because the two peaks will shift. When the mass fraction of ZnO in the main component is high, the permeability ratio of the iron-manganese-zinc ferrite material will remain unchanged, the initial permeability μi will decrease, and the impedance R will remain unchanged. This is because the two peaks will shift.

[0147] (9) By comparing Example 1 and Comparative Example 5, it can be seen that the auxiliary components in the iron-manganese-zinc ferrite material of the present invention will affect the performance of the iron-manganese-zinc ferrite material. When the auxiliary components are omitted, the magnetic permeability ratio of the iron-manganese-zinc ferrite material remains unchanged, the initial magnetic permeability μi decreases, and the impedance R remains unchanged. This is due to abnormal grain growth.

[0148] In summary, the iron-manganese-zinc ferrite material provided by the present invention has low stress sensitivity, high initial permeability and wide-band high impedance, thereby making the magnetic core made of the iron-manganese-zinc ferrite material have a smaller inductance drop rate under the same stress.

[0149] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. An iron-manganese-zinc ferrite material, characterized by, The iron-manganese-zinc ferrite material includes a main component and an auxiliary component; The main component, by mass percentage, comprises 68-69.56 wt% Fe2O3, 12.23-12.78 wt% ZnO, and the balance is Mn3O4. The auxiliary components are a combination of CaCO3, Bi2O3, TiO2 and MoO3; Based on the mass of the main components as the total mass, the auxiliary components include CaCO3 with a mass fraction of 200-2000 ppm, Bi2O3 with a mass fraction of 200-2000 ppm, TiO2 with a mass fraction of 200-2000 ppm, and MoO3 with a mass fraction of 200-2000 ppm. The preparation method of the iron-manganese-zinc ferrite material includes: (1) After mixing the main components and solvent to obtain a slurry, the slurry is pre-calcined to obtain a pre-calcined material, wherein the main components include Fe2O3, ZnO and Mn3O4; (2) The pre-burned material obtained in step (1) is mixed with the auxiliary components to obtain a mixture; (3) The mixture obtained in step (2) is sintered in a protective atmosphere to obtain an iron-manganese-zinc ferrite material; The sintering process described in step (3) is carried out in three stages.

2. The ferrimagnesian zinc ferrite material according to claim 1, characterized in that, Based on the mass of the main components as the total mass, the auxiliary components include CaCO3 with a mass fraction of 200-1000 ppm, Bi2O3 with a mass fraction of 200-1000 ppm, TiO2 with a mass fraction of 200-1000 ppm, and MoO3 with a mass fraction of 200-1000 ppm.

3. The ferrimagnesian zinc ferrite material according to claim 1, characterized in that, The mixing method in step (1) includes a first ball milling, the ball milling time being 20~80 min.

4. The ferrimagnesian zinc ferrite material according to claim 3, characterized in that, During the first ball milling process, the mass ratio of the main component, the grinding balls, and the solvent is (0.5~1.5):(3.5~4.5):(0.5~1.5).

5. The ferrimanganese zinc ferrite material of claim 1, wherein, The pre-calcination temperature in step (1) is 980~1035℃, and the pre-calcination is carried out in a rotary kiln. The slurry enters the rotary kiln at a rate of 400~500kg / h.

6. The ferrimanganese zinc ferrite material of claim 1, wherein, The mixing in step (2) also includes mixing the dispersant and the binder.

7. The iron-manganese-zinc ferrite material according to claim 6, characterized in that, The mixing method in step (2) includes a second ball milling, the time of which is 120-150 min.

8. The ferrimagnesian zinc ferrite material according to claim 7, characterized in that, In the second ball milling process, the mass ratio of pre-burned material, dispersant, binder to grinding balls is (0.5~1.5):(0.005~0.015):(0.05~0.15):(3~5).

9. The ferrimanganese zinc ferrite material of claim 1, wherein, Spray granulation is also included between steps (2) and (3).

10. The ferrimagnesian zinc ferrite material according to claim 9, characterized in that, The process between spray granulation and step (3) also includes pressing.

11. The ferrimagnesian zinc ferrite material of claim 1, wherein, The oxygen content in the protective atmosphere described in step (3) is 0~21 vol%.

12. The ferrimagnesian zinc ferrite material of claim 1, wherein, The oxygen content in the protective atmosphere described in step (3) is 0~10 vol%.

13. The ferrimanganese zinc ferrite material of claim 1, wherein, The sintering temperature in step (3) is 1200~1400℃ and the time is 4~10h.

14. The ferrimanganese zinc ferrite material of claim 1, wherein, In the sintering process in step (3) which is carried out in three stages, the temperature of the first stage is 1350~1400℃ and the time is 7~9h; the temperature of the second stage is 1350~1400℃ and the time is 0.5-1.5h; and the temperature of the third stage is 1200~1350℃ and the time is 0.5-1.5h.

15. The ferrimagnesian zinc ferrite material of claim 1, wherein, Step (3) includes cooling after sintering, which is carried out under equilibrium oxygen partial pressure.

16. The ferrimagnesian zinc ferrite material of claim 1, wherein, The preparation method includes: (1) The main components and water are mixed by ball milling for 20-80 minutes to obtain a slurry. During the ball milling process, the mass ratio of the main components, grinding balls and solvent is (0.5-1.5):(3.5-4.5):(0.5-1.5). Then, the slurry is pre-calcined in a rotary kiln at a temperature of 980-1035℃. The slurry enters the rotary kiln at a rate of 400-500 kg / h to obtain the pre-calcined material. The main components include Fe2O3, ZnO and Mn3O4. (2) The pre-burned material obtained in step (1) is mixed with auxiliary components, dispersant and binder by ball milling. During the ball milling process, the mass ratio of pre-burned material, dispersant, binder and milling balls is (0.5~1.5):(0.005~0.015):(0.05~0.15):(3~5) to obtain a mixture; (3) The mixture obtained in step (2) is spray-granulated and pressed into a preform to obtain a preform. The preform is then sintered in three stages. The temperature of the first stage is 1350~1400℃ and the time is 7~9h. The temperature of the second stage is 1350~1400℃ and the time is 0.5-1.5h. The temperature of the third stage is 1200~1350℃ and the time is 0.5-1.5h. The preform is then cooled under balanced oxygen partial pressure to obtain an iron-manganese-zinc ferrite material.

17. An application of the iron-manganese-zinc ferrite material according to claim 1 or 2, characterized in that, The iron-manganese-zinc ferrite material is used for signal transmission or electromagnetic interference suppression.

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