CN110803920A - Preparation method of high-frequency low-power-consumption NiZn soft magnetic ferrite material - Google Patents

Preparation method of high-frequency low-power-consumption NiZn soft magnetic ferrite material Download PDF

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CN110803920A
CN110803920A CN201910859510.7A CN201910859510A CN110803920A CN 110803920 A CN110803920 A CN 110803920A CN 201910859510 A CN201910859510 A CN 201910859510A CN 110803920 A CN110803920 A CN 110803920A
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powder
soft magnetic
sintering
magnetic ferrite
primary
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陈军林
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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Abstract

The invention relates to the technical field of magnetic materials, and discloses a preparation method of a high-frequency low-power-consumption NiZn soft magnetic ferrite material. The method comprises the following steps: 1) primary burdening: respectively weighing compounds containing Fe, Ni, Zn and Cu elements as main components; 2) performing primary ball milling; 3) primary sintering: pre-burning in air atmosphere; 4) secondary burdening: respectively weighing compounds containing Co, Nb, Ti, V, Bi, Ca and Si elements as auxiliary components, and adding the compounds containing Cu elements or the compounds containing Cu elements and the auxiliary components into the primary sintering powder; 5) performing secondary ball milling; 6) granulating; 7) pressing and forming; 8) and (3) secondary sintering: and sintering the green body in the air atmosphere, and cooling to obtain the material. The NiZn soft magnetic ferrite material obtained by the invention obviously reduces the power loss of the soft magnetic ferrite material at 5-10MHz by adding elements such as Cu, Co, Nb, Ti and the like.

Description

Preparation method of high-frequency low-power-consumption NiZn soft magnetic ferrite material
Technical Field
The invention relates to the technical field of magnetic materials, in particular to a preparation method of a high-frequency low-power-consumption NiZn soft magnetic ferrite material.
Background
The power ferrite is widely applied to power transformers in the fields of electronics and communication, and the transformers are further miniaturized particularly in a high-power transformer module, and the key point is to reduce the size of a switching power supply, while the key point is to use a low-loss material.
The power ferrite material appears as a first generation product from the 70 s in the 20 th century, and the working frequency is 20 KHz; in the 80 s, second-generation products appear, and the working frequency of the second-generation products reaches 100-500 KHz, such as PC30 and PC40 of TDK company; in the 90 s, third-generation products appear, and the working frequency reaches 0.5-1 MHz, such as PC50 of TDK company. As the IT industry develops towards high frequency, products with working frequency of 1-3 MHz are correspondingly produced, and 3F4, 3F45 and 3F5 of FERROCUBE company are representative of the products. At present, manufacturers at home and abroad produce MnZn power ferrite in a large quantity by second generation products and third generation products, and the fourth generation products have smaller market share. The MnZn power ferrite produced abroad is concentrated on top-grade products of third generation and fourth generation products, similar to PC44 and PC50 of TDK company and 3F4, 3F45 and 3F5 of FERROCUBE, and the like, and is gradually expanded by receiving the influence of miniaturization of devices under the application condition of the current market. Enterprises such as Taida and Huashi propose that the design frequency of the transformer reaches 1-3 MHz high frequency within several years, and the transformer can be developed to higher frequency (more than or equal to 3MHz) in the future. However, the loss of the existing manganese-zinc ferrite is high when the frequency is 3-5 MHz, and the loss of the ferrite when the frequency is 5-10MHz is also mentioned, which seriously restricts the development of the switching power supply to the high frequency direction. For example, chinese patent publication No. CN102491739 discloses a lead-free NiZn soft magnetic ferrite material and a patent of the invention of the preparation method thereof, the preparation method comprises the following steps: the material is prepared by the steps of material proportioning, ball milling in sequence, material presintering, secondary ball milling, press forming, high-temperature sintering and stress relief treatment, and the problem of environmental pollution is solved because the material formula does not contain heavy metal Pb, but the material has serious loss when the frequency reaches 7.6 MHz.
Disclosure of Invention
The invention provides a preparation method of a high-frequency low-power-consumption NiZn soft magnetic ferrite material, aiming at overcoming the problem that the loss of the NiZn soft magnetic ferrite material in the prior art is serious under the high-frequency condition. According to the NiZn soft magnetic ferrite material obtained by the invention, the power loss of the soft magnetic ferrite material at 5-10MHz is obviously reduced by adding elements such as Cu, Co, Nb and Ti.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: respectively weighing compounds containing Fe, Ni, Zn and Cu elements as main components for later use;
2) primary ball milling: uniformly mixing the compounds containing Fe, Ni and Zn elements in the step 1), crushing, and performing ball milling to obtain primary ball milling powder;
3) primary sintering: placing the primary ball-milling powder in an air atmosphere for presintering, and cooling to obtain primary sintering powder;
4) secondary burdening: respectively weighing compounds containing Co, Nb, Ti, V, Bi, Ca and Si elements as auxiliary components, and adding the compound containing the Cu element in the step 1) or the compound containing the Cu element in the step 1) and the auxiliary components into the primary sintered powder to obtain secondary mixed powder;
5) secondary ball milling: uniformly mixing the secondary ingredient powder, and then carrying out ball milling to obtain secondary ball milling powder;
6) and (3) granulation: adding a polyvinyl alcohol solution into the secondary ball-milled powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding a polyvinyl alcohol solution into the granular material, and pressing into a green body;
8) and (3) secondary sintering: and sintering the green blank in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
For the selection of the main components, in order to obtain wider use frequency, the magnetic permeability is required to be not obviously reduced under the use frequency of 10MHz, and the Curie temperature is higher, so that a main formula with lower Zn content, lower magnetic permeability and higher saturation magnetic induction intensity is selected according to the Snoek limit.
For high-frequency NiZn ferrite materials widely applied to various components and parts, the high-frequency NiZn ferrite materials are generally expected to have very low power loss under higher use frequency and in a wider temperature range, the invention adds Cu, Co, Nb, Ti, V, Bi, Ca and Si elements in secondary ingredients, substitutes the interaction mechanism between ions through the combination of different additive ions, and reasonably controls the sintering process, and the obtained product NiZn ferrite material is characterized in that: the saturation magnetic flux density is higher than 460mT at 25 ℃, the initial magnetic permeability is higher than 150, the power loss is lower than 300Kw/m3 under the test conditions of 10mT, 100 ℃ and 10MHz, the power loss is lower than 130Kw/m3 under the test conditions of 5mT, 100 ℃ and 10MHz, the loss does not exceed 30% along with the temperature change within the range of 20-120 ℃, and the Curie temperature of the material is higher than 260 ℃. According to the NiZn soft magnetic ferrite material obtained by the invention, the power loss of the soft magnetic ferrite material at 5-10MHz is obviously reduced by adding elements such as Cu, Co, Nb and Ti
Preferably, in the step 1), the main components are oxides containing Fe, Ni, Zn, and Cu elements, respectively.
Preferably, the main component comprises the following components in percentage by mass:
Fe2O345-55mol% of CuO, 2-12mol% of ZnO, 5-35mol% of NiO and the balance of NiO.
Preferably, the compound containing Co, Nb, Ti, V, Bi, Ca, and Si elements in step 4) is an oxide, a carbonate, or a silicate.
Preferably, the accessory component is a compound containing Co, Nb, Ti, V, Bi, Ca and Si elements, and is an oxide; the addition amount of the accessory component is 0-1.5 wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 500~12000ppm ，Nb2O5: 50~2000ppm，TiO2: 0~5000ppm；V2O5: 0~2000ppm，Bi2O3：0~2000ppm，CaO: 0~3000ppm，SiO2: 0~2000ppm。
Co2O3as an additive, although the magnetic permeability of the material is reduced, the material can induce local uniaxial anisotropy in the material, block domain wall movement, remarkably improve the cut-off frequency of the material, reduce the power loss caused by domain wall resonance and eddy current loss of the material at high frequency, and simultaneously, the magnetic spectrum of the material shows obvious resonance type, thereby being beneficial to the use of the material at higher frequency. But the addition of excessive amounts leads to temperatures at which the permeability is significantly reduced and at the same time the power loss is causedThe stability is reduced.
Adding Nb2O5The grain is refined, the grain boundary resistivity is improved by increasing the grain boundary, and the eddy current loss under high frequency, high magnetic flux density and high temperature is reduced, so that the power consumption of the material is obviously reduced.
TiO2The sintering temperature can be reduced without promoting the growth of crystal grains, and the hysteresis loss and residual loss of the material can be reduced.
Ca and Si are common additives for preparing NiZn ferrite in industry, CaO and SiO2The magnetic material does not enter the magnetic main phase basically and acts on a grain boundary part mainly, so that the grain boundary resistivity is increased, the resistivity of the whole material is increased, and the eddy current loss of the material can be obviously reduced. However, Ca and Si ions are easily distributed at the trigeminal grain boundary between grains, which is not favorable for increasing the overall resistivity, so that some cations with other valence states such as V need to be added5+Or other ions cause certain lattice distortion, thereby promoting the generation of ion vacancy in the material crystal grain, so that Ca and Si ions can move to the grain boundary between two crystal grains more easily, but not to the trigeminal grain boundary between three crystal grains, which is a synergistic effect among the ions.
V2O5And Bi2O3Are common sintering aids, but the sintering mechanisms of the sintering aids are not completely the same, so the addition amounts of the sintering aids are different, and Bi is2O3The main sintering aid mechanism is that because the oxide is low-melting point oxide, the mass transfer process among crystal grains in the sintering process can be promoted by forming liquid phase sintering, the sintering is promoted, the sintering temperature is reduced, the ionic radius of trivalent Bi ions is much larger than the radius of other metal ions in the material, so the trivalent Bi ions basically do not enter the inside of the crystal grains, main phase components are not influenced but are enriched in the crystal boundary, a high resistance layer is formed, and the power loss is reduced; and V2O5Is also a low melting point compound, but the ion radius of the pentavalent V ion is close to or even lower than that of the metal ion in the material, so that the pentavalent V ion can enter the inside of the crystal grain in the sintering process, and because the pentavalent V ion has higher valence state, some ion vacancies can be generated for maintaining charge balance, and the ion vacancies can promote the pure process in the crystal grain, except forThe method is beneficial to reducing the sintering temperature and also beneficial to Ca and Si ions distributed in the crystal grains to move to the crystal boundary between the two crystal grains more easily, and the power loss is obviously reduced. Therefore, V is comprehensively considered based on the mass transfer process inside and outside the crystal grains, the formation of a crystal boundary high-resistance layer, the reduction of sintering temperature and the like2O5And Bi2O3The CuO is matched with CuO to use, the advantages of each element are fully utilized, but if some elements are added excessively, the material is sintered too fast, and grains grow abnormally and are uneven, so that the CuO is not beneficial to use under high frequency.
Preferably, when the compound containing V, Bi elements is V2O5And Bi2O3When, V2O5And Bi2O3The total addition amount of (b) is 80-b ppm of the main component weight, and when the molar ratio of CuO in the main component is a mol%, b =3900-200 a.
Preferably, the primary sintering temperature is 900-1060 ℃, and the sintering time is 4-6 h; the secondary sintering temperature is 900-1180 ℃, and the sintering time is 6-10 hours.
Preferably, the particle size of the secondary ball-milling powder obtained by the secondary ball-milling is 0.8-1.8 μm.
Preferably, the addition amount of the polyvinyl alcohol solution in the granulating step is 5-20 wt% of the secondary ball-milling powder; the addition amount of the polyvinyl alcohol solution in the step of pressing and forming is 0.1-2 wt% of the particle material, and the density of the green blank obtained by pressing is more than or equal to 3.1g/cm3。
The NiZn soft magnetic ferrite material is prepared by the preparation method of the high-frequency low-power NiZn soft magnetic ferrite material.
Therefore, the invention has the following beneficial effects: (1) according to the NiZn soft magnetic ferrite material, the power loss of the soft magnetic ferrite material at 5-10MHz is obviously reduced by adding elements such as Cu, Co, Nb and Ti; (2) co2O3As an additive, although the magnetic permeability of the material is reduced, the additive can induce local uniaxial anisotropy in the material, inhibit domain wall movement, remarkably improve the cut-off frequency of the material and reduce power loss caused by domain wall resonance and eddy current loss of the material at high frequencyMeanwhile, the magnetic spectrum of the material shows an obvious resonance type, which is beneficial to the use of the material under higher frequency. However, excessive addition results in a significant decrease in permeability and a decrease in temperature stability which leads to power loss; (3) v is based on comprehensive consideration of the mass transfer process inside and outside the crystal grains, the formation of a crystal boundary high-resistance layer, the reduction of sintering temperature and the like2O5And Bi2O3The CuO is matched with CuO to use, the advantages of each element are fully utilized, but if some elements are added excessively, the material is sintered too fast, and grains grow abnormally and are uneven, so that the CuO is not beneficial to use under high frequency.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the main components selected are as follows: fe2O3: 48.6 mol%, ZnO: 24 mol%, CuO: 7 mol%, NiO: the rest is reserved;
2) primary ball milling: mixing Fe in the step 1)2O3Uniformly mixing ZnO and NiO, crushing, and ball-milling for 2h to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milled powder in a sintering furnace in air atmosphere at 950 ℃ for presintering for 4h, and cooling to obtain primary sintered powder;
4) secondary burdening: adding the CuO obtained in the step 1) into the primary sintering powder to obtain secondary batching powder;
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 2wt% of the granular material, and pressing into the granular material with the density of 3.1g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 6h at 1100 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
The performance test of the NiZn soft magnetic ferrite material prepared by the method is as follows:
the saturation magnetic flux density is 465mT at 25 ℃, the initial magnetic conductivity is 150, the power loss is 150KW/m3 under the test conditions of 10mT, 100 ℃ and 5MHz, the power loss is 280kW/m3 under the test conditions of 10mT, 100 ℃ and 10MHz, the change of the loss along with the temperature is not more than 30% within the range of 20-120 ℃, and the Curie temperature of the material is 265 ℃.
Example 2
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the main components selected are as follows: fe2O3: 48.6 mol%, ZnO: 20 mol%, CuO: 7 mol%, NiO: the rest is reserved;
2) primary ball milling: mixing Fe in the step 1)2O3Uniformly mixing ZnO and NiO, crushing, and ball-milling for 2h to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milled powder in a sintering furnace in air atmosphere at 950 ℃ for presintering for 4h, and cooling to obtain primary sintered powder;
4) secondary burdening: adding the CuO and the accessory ingredients in the step 1) into the primary sintering powder to obtain secondary batching powder; wherein the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si elements; the addition amount of the accessory component is 1.28wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 8000ppm ，Nb2O5: 800ppm，TiO2: 2000ppm，V2O5: 500ppm，Bi2O3：1000ppm，CaO:500ppm；
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 2wt% of the granular material, and pressing into the granular material with the density of 3.2g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 6h at 1100 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
The performance test of the NiZn soft magnetic ferrite material prepared by the method is as follows:
the saturation magnetic flux density is 460mT at 25 ℃, the initial magnetic conductivity is 135, the power loss is 128Kw/m3 under the test conditions of 10mT, 100 ℃ and 5MHz, the power loss is 262kW/m3 under the test conditions of 10mT, 100 ℃ and 10MHz, the loss is not more than 30 percent along with the change of the temperature within the range of 20-120 ℃, and the Curie temperature of the material is 280 ℃.
Example 3
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the main components selected are as follows: fe2O3: 48.6 mol%, ZnO: 26 mol%, CuO: 10 mol%, NiO: the rest is reserved;
2) primary ball milling: mixing Fe in the step 1)2O3ZnO and NiO are evenly mixedCrushing and ball-milling for 2 hours to obtain primary ball-milling powder;
3) primary sintering: placing the primary ball-milled powder in a sintering furnace in air atmosphere at 950 ℃ for presintering for 2.5h, and cooling to obtain primary sintered powder;
4) secondary burdening: adding the CuO and the accessory ingredients in the step 1) into the primary sintering powder to obtain secondary batching powder; wherein the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si elements; the addition amount of the accessory component is 0.79wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 1000ppm ，Nb2O5: 800ppm，TiO2: 2000ppm，V2O5: 1000ppm，Bi2O3：800ppm，CaO:1000ppm，SiO2：500ppm；
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 2wt% of the granular material, and pressing into the granular material with the density of 3.5g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 6h at 1060 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
The performance test of the NiZn soft magnetic ferrite material prepared by the method is as follows:
the saturation magnetic flux density is 450mT at 25 ℃, the initial magnetic conductivity is 180, the power loss is 228Kw/m3 under the test conditions of 10mT, 100 ℃ and 5MHz, the power loss is 436Kw/m3 under the test conditions of 10mT, 100 ℃ and 10MHz, the change of the loss along with the temperature is not more than 30% within the range of 20-120 ℃, and the Curie temperature of the material is 240 ℃.
Example 4
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the main components selected are as follows: fe2O3: 48.6 mol%, ZnO: 25 mol%, CuO: 15 mol%, NiO: the rest is reserved;
2) primary ball milling: mixing Fe in the step 1)2O3Uniformly mixing ZnO and NiO, crushing, and ball-milling for 2h to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milling powder in a sintering furnace in air atmosphere at 930 ℃ for presintering for 4h, and cooling to obtain primary sintering powder;
4) secondary burdening: adding the CuO and the accessory ingredients in the step 1) into the primary sintering powder to obtain secondary batching powder; wherein the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si elements; the addition amount of the accessory component is 0.88wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 4000ppm ，Nb2O5: 800ppm，TiO2: 2000ppm，V2O5: 50ppm，Bi2O3：50ppm，CaO:1600ppm，SiO2：300ppm；
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 2wt% of the granular material, and pressing to obtain a compactThe degree is 3.5g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 2.5h at 930 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
The performance test of the NiZn soft magnetic ferrite material prepared by the method is as follows:
the saturation magnetic flux density is 430mT at 25 ℃, the initial magnetic permeability is 205, the power loss is 110Kw/m3 under the test conditions of 10mT, 100 ℃ and 5MHz, the power loss is 216Kw/m3 under the test conditions of 10mT, 100 ℃ and 10MHz, the change of the loss along with the temperature is not more than 30% within the range of 20-120 ℃, and the Curie temperature of the material is 230 ℃.
Example 5
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the selected main component is Fe2O355mol percent of CuO, 12mol percent of ZnO, 35mol percent of NiO and the balance of NiO for standby;
2) primary ball milling: mixing Fe in the step 1)2O3Uniformly mixing ZnO and NiO, crushing, and ball-milling for 2h to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milling powder in a sintering furnace in an air atmosphere at 1060 ℃ for pre-sintering for 6 hours, and cooling to obtain primary sintering powder;
4) secondary burdening: adding the CuO and the accessory ingredients in the step 1) into the primary sintering powder to obtain secondary batching powder; wherein the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si elements; the addition amount of the accessory component is 1.5wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 12000ppm ，Nb2O5: 2000ppm，TiO2: 1000ppm；
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 20wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 2wt% of the granular material, and pressing into the granular material with the density of 3.5g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) sintering the green body in a sintering furnace at 1180 ℃ in air atmosphere for 2.5h, and cooling to obtain the NiZn soft magnetic ferrite material.
Example 6
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the selected main component is Fe2O345mol percent of CuO, 2mol percent of ZnO, 5mol percent of NiO and the balance for standby;
2) primary ball milling: mixing Fe in the step 1)2O3Uniformly mixing ZnO and NiO, crushing, and ball-milling for 2h to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milling powder in a sintering furnace in an air atmosphere at 900 ℃ for pre-sintering for 6 hours, and cooling to obtain primary sintering powder;
4) secondary burdening: adding the CuO and the accessory ingredients in the step 1) into the primary sintering powder to obtain secondary batching powder; wherein the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si elements; the addition amount of the accessory component is 1.355wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 500ppm ，Nb2O5: 50ppm，TiO2: 5000，V2O5: 1000ppm，Bi2O3： 2000ppm，CaO:3000ppm，SiO2: 2000ppm；
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 0.1wt% of the granular material, and pressing into the granular material with the density of 3.5g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 10h at 900 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
Example 7
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the selected main component is Fe2O345mol percent of CuO, 2mol percent of ZnO, 5mol percent of NiO and the balance for standby;
2) primary ball milling: mixing Fe in the step 1)2O3Uniformly mixing ZnO and NiO, crushing, and ball-milling for 2h to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milling powder in a sintering furnace in an air atmosphere at 900 ℃ for pre-sintering for 6 hours, and cooling to obtain primary sintering powder;
4) secondary burdening: adding the CuO and the accessory ingredients in the step 1) into the primary sintering powder to obtain secondary batching powder; wherein the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si elements; the addition amount of the accessory component is 0.855wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 500ppm ，Nb2O5: 50ppm， V2O5: 2000ppm，Bi2O3：1000ppm，CaO: 3000ppm，SiO2:2000ppm；
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 0.1wt% of the granular material, and pressing into the granular material with the density of 3.5g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 10h at 900 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
Example 8
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the selected main component is Fe2O345mol percent of CuO, 2mol percent of ZnO, 5mol percent of NiO and the balance for standby;
2) primary ball milling: mixing Fe in the step 1)2O3Uniformly mixing ZnO and NiO, crushing, and ball-milling for 2h to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milling powder in a sintering furnace in an air atmosphere at 900 ℃ for pre-sintering for 6 hours, and cooling to obtain primary sintering powder;
4) secondary burdening: adding the CuO and the accessory ingredients in the step 1) into the primary sintering powder to obtain secondary batching powder; wherein the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si elements; the addition amount of the accessory component is 0.635wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 500ppm ，Nb2O5: 50ppm， V2O5: 40ppm，Bi2O3：40ppm，CaO: 3000ppm，SiO22000 ppm; 5) Secondary ball milling: mixing the secondary ingredient powderUniformly mixing the materials, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, drying, and performing grinding dispersion to obtain secondary ball milling powder, wherein the particle size of the powder particles is in normal distribution;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 0.1wt% of the granular material, and pressing into the granular material with the density of 3.5g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 10h at 900 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
Comparative example 1
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the main components selected are as follows: fe2O3: 48.6 mol%, ZnO: 24 mol%, CuO: 7 mol%, NiO: the rest is reserved;
2) primary ball milling: uniformly mixing the main components in the step 1), crushing, and carrying out ball milling for 2 hours to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milled powder in a sintering furnace in air atmosphere at 950 ℃ for presintering for 4h, and cooling to obtain primary sintered powder;
4) secondary burdening: adding the same amount of CuO in the step 1) into the primary sintered powder to obtain secondary mixed powder;
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 2wt% of the granular material, and pressing into the granular material with the density of 3.1g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 6h at 1100 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
The performance test of the NiZn soft magnetic ferrite material prepared by the method is as follows:
the saturation magnetic flux density is 430mT at 25 ℃, the initial magnetic permeability is 140, the power loss is 330Kw/m3 under the test conditions of 10mT, 100 ℃ and 5MHz, the power loss is 620Kw/m3 under the test conditions of 10mT, 100 ℃ and 10MHz, and the Curie temperature of the material is 265 ℃.
Comparative example 2
The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material comprises the following steps:
1) primary burdening: the main components selected are as follows: fe2O3: 48.6 mol%, ZnO: 25 mol%, CuO: 15 mol%, NiO: the rest is reserved;
2) primary ball milling: mixing Fe in the step 1)2O3Uniformly mixing ZnO and NiO, crushing, and ball-milling for 2h to obtain primary ball-milled powder;
3) primary sintering: placing the primary ball-milling powder in a sintering furnace in air atmosphere at 930 ℃ for presintering for 4h, and cooling to obtain primary sintering powder;
4) secondary burdening: adding the CuO and the accessory ingredients in the step 1) into the primary sintering powder to obtain secondary batching powder; wherein the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si elements; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 4000ppm ，Nb2O5: 800ppm，TiO2: 2000ppm，V2O5: 3000ppm，Bi2O3：3000ppm，CaO:1600ppm，SiO2：300ppm；
5) secondary ball milling: uniformly mixing the secondary ingredient powder, adding deionized water accounting for 8% of the mass of the secondary ingredient powder, performing ball milling for 6 hours to obtain powder particles with the particle size of 0.8-1.8 mu m, wherein the particle size of the powder particles is in normal distribution, drying, and performing grinding dispersion to obtain secondary ball-milled powder;
6) and (3) granulation: adding a polyvinyl alcohol aqueous solution with the mass concentration of 10% into the secondary ball-milling powder, wherein the addition amount of the polyvinyl alcohol aqueous solution is 5wt% of the secondary ball-milling powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding 10% polyvinyl alcohol solution into the granular material, wherein the addition amount of the polyvinyl alcohol solution is 2wt% of the granular material, and pressing into the granular material with the density of 3.5g/cm3Performing embryo production;
8) and (3) secondary sintering: and (3) placing the green body in a sintering furnace, sintering for 2.5h at 930 ℃ in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
The performance test of the NiZn soft magnetic ferrite material prepared by the method is as follows:
the saturation magnetic flux density is 420mT at 25 ℃, the initial magnetic conductivity is 140, the power loss is 230Kw/m3 under the test conditions of 10mT, 100 ℃ and 5MHz, the power loss is 380Kw/m3 under the test conditions of 10mT, 100 ℃ and 10MHz, the maximum change of the loss along with the temperature is 70% within the range of 20-120 ℃, and the Curie temperature of the material is 240 ℃.
By comparing example 1 with comparative example 1, it can be found that the power loss of the material can be significantly changed by adjusting the order of addition of the main components of CuO. The main reason is that when primary sintering is carried out, because the CuO is contained as the sintering aid in the comparative example 1, the powder material is reacted too fully after presintering for 4 hours at 950 ℃, so that the spinel structure proportion in the powder material is too large, the hardness is higher, the powder material is difficult to break during secondary ball milling, the activity of the powder material in the subsequent sintering process is lower, and the performance of the final product is deteriorated.
By comparing example 4 and comparative example 2, it can be seen that in both cases the same high CuO content is used, but V2O5And Bi2O3Is not consistent, comparative example 4 is due to the addition of an excess of V2O5And Bi2O3In the sintering process, the crystal grain grows too fast, the magnetic conductivity is obviously increased, but in the aspect of power loss of key performance indexes, the loss is greatly increased, and the requirement of low loss cannot be met. In example 4, V is the subcomponent2O5And Bi2O3The addition amount of the composite material is more reasonable, and the obtained composite material has more excellent comprehensive performance.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A preparation method of a high-frequency low-power NiZn soft magnetic ferrite material is characterized by comprising the following steps:
1) primary burdening: respectively weighing compounds containing Fe, Ni, Zn and Cu elements as main components for later use;
2) primary ball milling: uniformly mixing the compounds containing Fe, Ni and Zn elements in the step 1), crushing, and performing ball milling to obtain primary ball milling powder;
3) primary sintering: placing the primary ball-milling powder in an air atmosphere for presintering, and cooling to obtain primary sintering powder;
4) secondary burdening: respectively weighing compounds containing Co, Nb, Ti, V, Bi, Ca and Si elements as auxiliary components, and adding the compound containing the Cu element in the step 1) or the compound containing the Cu element in the step 1) and the auxiliary components into the primary sintered powder to obtain secondary mixed powder;
5) secondary ball milling: uniformly mixing the secondary ingredient powder, and then carrying out ball milling to obtain secondary ball milling powder;
6) and (3) granulation: adding a polyvinyl alcohol solution into the secondary ball-milled powder, prepressing, grinding and sieving to obtain a granular material;
7) and (3) pressing and forming: adding a polyvinyl alcohol solution into the granular material, and pressing into a green body;
8) and (3) secondary sintering: and sintering the green blank in the air atmosphere, and cooling to obtain the NiZn soft magnetic ferrite material.
2. The method for preparing a high-frequency low-power NiZn soft magnetic ferrite material as claimed in claim 1, wherein the main components in step 1) are oxides respectively containing Fe, Ni, Zn and Cu elements.
3. The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material according to claim 1 or 2, wherein the main components comprise the following components in percentage by mass:
Fe2O345-55mol percent of CuO, 2-12mol percent of ZnO, 5-35mol percent of NiO and the balance of NiO.
4. The method for preparing a high-frequency low-power NiZn soft magnetic ferrite material according to claim 1, wherein the compound containing Co, Nb, Ti, V, Bi, Ca and Si in the step 4) is an oxide, a carbonate or a silicate.
5. The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material according to claim 1 or 4, characterized in that the accessory components are oxides containing Co, Nb, Ti, V, Bi, Ca and Si; the addition amount of the accessory component is 0-1.5 wt% of the main component; the additive amount of each component in the accessory components accounts for the mass fraction of the main component as follows:
Co2O3: 500~12000ppm ，Nb2O5: 50~2000ppm，TiO2: 0~5000ppm；V2O5: 0~2000ppm，Bi2O3：0~2000ppm，CaO: 0~3000ppm，SiO2: 0~2000ppm。
6. the method for preparing a high-frequency low-power NiZn soft magnetic ferrite material as claimed in claim 1, wherein when a compound of element V, Bi is V2O5And Bi2O3When, V2O5And Bi2O3The total addition amount of (b) is 80-bppm based on the weight of the main component, and when the molar ratio of CuO in the main component is a mol%, b =3900-200 a.
7. The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material as claimed in claim 1, wherein the primary sintering temperature is 900-1060 ℃, and the sintering time is 2.5-6 h; the secondary sintering temperature is 900-1180 ℃, and the sintering time is 2.5-10 h.
8. The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material according to claim 1, wherein the grain size of secondary ball-milled powder obtained by secondary ball milling is 0.8-1.8 μm.
9. The preparation method of the high-frequency low-power NiZn soft magnetic ferrite material according to claim 1, wherein the addition amount of the polyvinyl alcohol solution in the granulation step is 5-20 wt% of the secondary ball-milled powder; the addition amount of the polyvinyl alcohol solution in the step of pressing and forming is 0.1-2 wt% of the particle material, and the density of the green blank obtained by pressing is more than or equal to 3.1g/cm3。
10. The NiZn soft magnetic ferrite material prepared by the preparation method of the high-frequency low-power NiZn soft magnetic ferrite material as claimed in claim 1.
CN201910859510.7A 2019-09-11 2019-09-11 Preparation method of high-frequency low-power-consumption NiZn soft magnetic ferrite material Pending CN110803920A (en)

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CN114560690A (en) * 2022-03-28 2022-05-31 电子科技大学 Densification technology of high-coercivity M-type barium ferrite for self-biased circulator
CN114853461A (en) * 2022-06-20 2022-08-05 西安锐磁电子科技有限公司 Wide-temperature-range low-loss NiZn soft magnetic ferrite material and preparation method thereof
CN115894005A (en) * 2022-11-17 2023-04-04 横店集团东磁股份有限公司 Nickel-zinc ferrite material and preparation method and application thereof
CN116490467A (en) * 2020-10-20 2023-07-25 株式会社东金 MnZn ferrite

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CN116490467A (en) * 2020-10-20 2023-07-25 株式会社东金 MnZn ferrite
CN114560690A (en) * 2022-03-28 2022-05-31 电子科技大学 Densification technology of high-coercivity M-type barium ferrite for self-biased circulator
CN114853461A (en) * 2022-06-20 2022-08-05 西安锐磁电子科技有限公司 Wide-temperature-range low-loss NiZn soft magnetic ferrite material and preparation method thereof
CN115894005A (en) * 2022-11-17 2023-04-04 横店集团东磁股份有限公司 Nickel-zinc ferrite material and preparation method and application thereof
CN115894005B (en) * 2022-11-17 2023-09-08 横店集团东磁股份有限公司 Nickel-zinc ferrite material and preparation method and application thereof

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Application publication date: 20200218