阅读说明：本技术 一种超细晶耐高温高频锰锌铁氧体制备方法 (Preparation method of superfine-crystal high-temperature-resistant high-frequency manganese-zinc ferrite ) 是由 唐少春 赵宇飞 于 2021-09-29 设计创作，主要内容包括：本发明公开了一种超细晶耐高温高频锰锌铁氧体制备方法,主要步骤为：以Fe-(2)O-(3)、MnO-(2)、ZnO为主要原料,SnO-(2)为辅助原料进行配料,一次球磨,预烧,掺杂CaCO3、V-(2)O-(5)、TiO-(2)、Co-(2)O-(3),二次球磨,添加PVA进行造粒,室温预加压成型,高温形变,高温加压成型,烧结,急冷降温,得到锰锌铁氧体。本发明以SnO-(2)为辅助原料,Sn能够进入锰锌铁氧体晶格内部,阻碍电子在高温和高频下的跃迁,降低损耗；采用CaCO-(3)、V-(2)O-(5)、TiO-(2)、Co-(2)O-(3)进行掺杂,杂质元素富集在晶界中,增大晶界电阻率,降低损耗；采用高温压缩形变,提供形变储存能,增多晶粒形成位置,进而细化晶粒,降低损耗；采用急冷降温,降低降温过程中的元素扩散,增强铁氧体的高温特性。所得锰锌铁氧体具有超细晶、饱和磁感应强度高、耐高温、高频损耗低的优点。(The invention discloses a preparation method of ultrafine-grained high-temperature-resistant high-frequency manganese-zinc ferrite, which mainly comprises the following steps: with Fe 2 O 3 、MnO 2 ZnO as main material, SnO 2 Mixing the raw materials, ball milling, pre-sintering, doping CaCO3 and V 2 O 5 、TiO 2 、Co 2 O 3 And performing secondary ball milling, adding PVA (polyvinyl alcohol) for granulation, performing room-temperature pre-pressing molding, performing high-temperature deformation, performing high-temperature pressing molding, sintering, and performing quenching and cooling to obtain the manganese-zinc ferrite. In the invention, SnO 2 As an auxiliary raw material, Sn can enter the interior of manganese-zinc ferrite crystal lattices, so that transition of electrons at high temperature and high frequency is blocked, and loss is reduced; using CaCO 3 、V 2 O 5 、TiO 2 、Co 2 O 3 Doping is carried out, impurity elements are enriched in grain boundaries, the resistivity of the grain boundaries is increased, and loss is reduced; high-temperature compression deformation is adopted to provide deformation storage energy, the forming positions of crystal grains are increased, the crystal grains are refined, and loss is reduced; and the rapid cooling is adopted, so that the element diffusion in the cooling process is reduced, and the high-temperature characteristic of the ferrite is enhanced. The obtained manganese-zinc ferrite has the advantages of ultrafine crystal, high saturation magnetic induction intensity, high temperature resistance and low high-frequency loss.)

1. A preparation method of superfine crystal high-temperature and high-frequency manganese-zinc ferrite is characterized by comprising the following steps: the method comprises the following steps:

A. with Fe₂O₃、MnO₂ZnO as main material, SnO₂Preparing auxiliary raw materials;

B. b, performing primary ball milling on the raw materials obtained in the step A, wherein the rotating speed is 220-250 r/min, and the ball milling time is 2-3 h;

C. b, pre-sintering the raw materials obtained in the step B, wherein the pre-sintering temperature is 850-950 ℃, and the heat preservation time is 2-3 h;

D. c, doping the raw material obtained in the step C, wherein the doping element is CaCO₃、V₂O₅、TiO₂、Co₂O₃；

E. D, performing secondary ball milling on the raw materials obtained in the step D, wherein the rotating speed is 220-250 r/min, and the ball milling time is 3-5 h;

F. adding 10-15% of PVA into the raw material obtained in the step E for granulation;

G. c, pre-pressing the raw materials obtained in the step F at room temperature to form, wherein the applied pressure is 3-4 MPa;

H. carrying out high-temperature deformation on the raw material obtained in the step G, wherein the temperature is 1000-1100 ℃;

I. carrying out high-temperature pressure forming on the raw material obtained in the step H, wherein the temperature is 1000-1100 ℃, and the applied pressure is 6-7 MPa;

J. sintering the raw materials obtained in the step I at a high temperature, wherein the sintering temperature is 1140-1160 ℃, the heat preservation time is 6 hours, and the oxygen partial pressure is 5%;

K. and D, carrying out quenching and cooling on the raw material obtained in the step J to obtain the manganese-zinc ferrite.

2. The preparation method of the ultrafine grained high temperature and high frequency resistant manganese zinc ferrite according to claim 1, characterized in that: the ingredient content is Fe₂O₃53-56mol% of MnO₂33-36mol% of ZnO, 8-12mol% of SnO₂The content is 0.001 to 0.005 wt%.

3. The preparation method of the ultrafine grained high temperature and high frequency resistant manganese zinc ferrite according to claim 1, characterized in that: the content of the doping element is CaCO₃0.01 to 0.1wt% of V₂O₅0.001 to 0.01wt% of TiO₂0.1-0.2 wt% of Co₂O₃The content is 0.2-0.4 wt%.

4. The preparation method of the ultrafine grained high temperature and high frequency resistant manganese zinc ferrite according to claim 1, characterized in that: the high-temperature deformation is multiple transverse and longitudinal compression deformation, and the compression ratio of each deformation is 5-15%.

5. The preparation method of the ultrafine grained high temperature and high frequency resistant manganese zinc ferrite according to claim 4, characterized in that: the multiple transverse and longitudinal compression deformation processes are transverse deformation and then longitudinal deformation, and the deformation times are 4-10 times respectively in the transverse direction and the longitudinal direction.

6. The preparation method of the ultrafine grained high temperature and high frequency resistant manganese zinc ferrite according to claim 1, characterized in that: the cooling rate of the rapid cooling is 50-100 ℃/s.

Technical Field

The invention relates to the field of preparation of high-frequency manganese-zinc ferrite.

Background

In the 5G era, electronic devices are continuously developing towards high frequency, and the high frequency characteristics of soft magnetic ferrite represented by manganese-zinc ferrite and the high frequency low loss characteristics at high temperature generated by device heating are important. In addition, the increase of the working frequency is beneficial to reducing the volume and the weight of the magnetic core, and is beneficial to the miniaturization and the light weight of the device.

At present, the preparation of the high-frequency manganese-zinc ferrite applied to 2-4 MHz becomes a technical difficulty. The manganese-zinc ferrite prepared by the existing preparation process has the defects of large high-frequency loss, poor high-temperature characteristics and the like.

Disclosure of Invention

The invention overcomes the defects and provides a preparation method of ultrafine-grained high-temperature-resistant high-frequency manganese-zinc ferrite, which is characterized by comprising the following steps:

A. with Fe₂O₃、MnO₂ZnO as main material, SnO₂Preparing auxiliary raw materials;

B. b, performing primary ball milling on the raw materials obtained in the step A, wherein the rotating speed is 220-250 r/min, and the ball milling time is 2-3 h;

C. b, pre-sintering the raw materials obtained in the step B, wherein the pre-sintering temperature is 850-950 ℃, and the heat preservation time is 2-3 h;

D. c, doping the raw material obtained in the step C, wherein the doping element is CaCO₃、V₂O₅、TiO₂、Co₂O₃；

E. D, performing secondary ball milling on the raw materials obtained in the step D, wherein the rotating speed is 220-250 r/min, and the ball milling time is 3-5 h;

F. adding 10-15% of PVA into the raw material obtained in the step E for granulation;

G. c, pre-pressing the raw materials obtained in the step F at room temperature to form, wherein the applied pressure is 3-4 MPa;

H. carrying out high-temperature deformation on the raw material obtained in the step G, wherein the temperature is 1000-1100 ℃;

I. carrying out high-temperature pressure forming on the raw material obtained in the step H, wherein the temperature is 1000-1100 ℃, and the applied pressure is 6-7 MPa;

J. sintering the raw materials obtained in the step I at a high temperature, wherein the sintering temperature is 1140-1160 ℃, the heat preservation time is 6 hours, and the oxygen partial pressure is 5%;

K. and D, carrying out quenching and cooling on the raw material obtained in the step J to obtain the manganese-zinc ferrite.

The preparation method of the ultrafine-grained high-temperature-resistant high-frequency manganese-zinc ferrite is further improved,the ingredient content is Fe₂O₃53-56mol% of MnO₂33-36mol% of ZnO, 8-12mol% of SnO₂The content is 0.001 to 0.005 wt%.

The preparation method of the ultrafine-grained high-temperature-resistant high-frequency manganese-zinc ferrite is further improved in that the content of the doping element is CaCO₃0.01 to 0.1wt% of V₂O₅0.001 to 0.01wt% of TiO₂0.1-0.2 wt% of Co₂O₃The content is 0.2-0.4 wt%.

The preparation method of the ultrafine-grained high-temperature-resistant high-frequency manganese-zinc ferrite is further improved in that the high-temperature deformation is multiple transverse and longitudinal compression deformation, and the compression ratio of each deformation is 5-15%.

The preparation method of the ultrafine-grained high-temperature-resistant high-frequency manganese-zinc ferrite is further improved in that the multiple transverse and longitudinal compression deformation processes are transverse deformation and then longitudinal deformation is carried out alternately, and the deformation times are 4-10 times respectively in the transverse direction and the longitudinal direction.

The preparation method of the ultrafine-grained high-temperature-resistant high-frequency manganese-zinc ferrite is further improved in that the cooling rate of rapid cooling is 50-100 ℃/s.

In the invention, SnO₂As an auxiliary raw material, Sn can enter the interior of manganese-zinc ferrite crystal lattices, so that transition of electrons at high temperature and high frequency is blocked, and loss is reduced; using CaCO₃、V₂O₅、TiO₂、Co₂O₃Doping is carried out, impurity elements are enriched in grain boundaries, the resistivity of the grain boundaries is increased, and loss is reduced; high-temperature compression deformation is adopted to provide deformation storage energy, and the forming positions of crystal grains are increased, so that the crystal grains are refined, the crystal boundary is increased, and the loss is reduced; and the rapid cooling is adopted, so that the element diffusion in the cooling process is reduced, and the high-temperature characteristic of the ferrite is enhanced. The manganese-zinc ferrite prepared by the invention has the advantages of ultra-fine grain structure, small high-frequency loss and good high-temperature characteristic, is beneficial to improving the working frequency, reducing the volume and the weight of a magnetic core and meeting the requirements of miniaturization and light weight of devices.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.

Example 1:

with Fe₂O₃、MnO₂ZnO as main material, SnO₂Compounding as an auxiliary raw material, Fe₂O₃Content 53mol%, MnO₂36mol% of ZnO, 11mol% of ZnO, SnO₂The content is 0.001 wt%; performing primary ball milling after the material mixing is finished, wherein the rotating speed is 220 r/min, and the ball milling time is 2 h; presintering the raw materials subjected to primary ball milling at the presintering temperature of 850 ℃ for 2 hours; after completion, doping with CaCO₃Content 0.01wt%, V₂O₅0.01wt% of TiO₂0.1wt% of Co₂O₃The content is 0.2 wt%; performing secondary ball milling on the obtained raw materials, wherein the rotating speed is 220 r/min, and the ball milling time is 3 h; after the secondary ball milling is finished, adding 10PVA for granulation; then carrying out room temperature pre-pressing molding, wherein the applied pressure is 3 MPa; then, carrying out high-temperature deformation alternately in the transverse direction and the longitudinal direction, wherein the temperature is 1000 ℃, the deformation compression rate is 5%, and the deformation times are 10 times respectively in the transverse direction and the longitudinal direction; then, high-temperature pressure molding is carried out, the temperature is 1000 ℃, and the applied pressure is 6 MPa; then, high-temperature sintering is carried out, the sintering temperature is 1160 ℃, the heat preservation time is 6 hours, and the oxygen partial pressure is 5%; and carrying out quenching and cooling after the reaction is finished, wherein the cooling rate is 50 ℃/s, and obtaining the manganese-zinc ferrite.

Example 2:

with Fe₂O₃、MnO₂ZnO as main material, SnO₂Compounding as an auxiliary raw material, Fe₂O₃Content 56mol%, MnO₂36mol% of ZnO, 8mol% of ZnO, SnO₂The content is 0.005 wt%; performing primary ball milling after the material mixing is finished, wherein the rotating speed is 250 revolutions per minute, and the ball milling time is 3 hours; pre-sintering the raw materials subjected to the primary ball milling at the pre-sintering temperature of 950 ℃ for 3 hours; after completion, doping with CaCO₃Content 0.1wt%, V₂O₅0.001wt% of TiO₂0.2wt% of Co₂O₃The content is 0.4 wt%; performing secondary ball milling on the obtained raw materials, wherein the rotating speed is 250 revolutions per minute, and the ball milling time is 5 hours; finish the secondary ball millingAfter the formation, 15% PVA is added for granulation; then carrying out room temperature pre-pressing molding, wherein the applied pressure is 4 MPa; then, carrying out high-temperature deformation alternately in the transverse direction and the longitudinal direction, wherein the temperature is 1100 ℃, the deformation compression rate is 15 percent, and the deformation times are 4 times respectively in the transverse direction and the longitudinal direction; then, high-temperature pressure molding is carried out, the temperature is 1100 ℃, and the applied pressure is 7 MPa; then, high-temperature sintering is carried out, wherein the sintering temperature is 1140 ℃, the heat preservation time is 6 hours, and the oxygen partial pressure is 5%; and carrying out quenching and cooling after the reaction is finished, wherein the cooling rate is 100 ℃/s, and obtaining the manganese-zinc ferrite.

Example 3:

with Fe₂O₃、MnO₂ZnO as main material, SnO₂Compounding as an auxiliary raw material, Fe₂O₃Content 55mol%, MnO₂33mol% of ZnO, 12mol% of ZnO, SnO₂The content is 0.003 wt%; performing primary ball milling after the material preparation is finished, wherein the rotating speed is 230 r/min, and the ball milling time is 2.5 h; pre-sintering the raw materials subjected to the primary ball milling at the pre-sintering temperature of 900 ℃ for 2.5 hours; after completion, doping with CaCO₃Content 0.05wt%, V₂O₅0.005wt% of TiO₂0.15wt% of Co₂O₃The content is 0.3 wt%; performing secondary ball milling on the obtained raw materials, wherein the rotating speed is 230 r/min, and the ball milling time is 4 h; after the secondary ball milling is finished, adding 12% PVA for granulation; then carrying out room temperature pre-pressing molding, wherein the applied pressure is 3.5 MPa; then, transverse and longitudinal alternate high-temperature deformation is carried out, wherein the temperature is 1050 ℃, the deformation compression ratio is 10%, and the deformation times are 8 times respectively in the transverse direction and the longitudinal direction; then, high-temperature pressure molding is carried out, the temperature is 1050 ℃, and the applied pressure is 6.5 MPa; then high-temperature sintering is carried out, the sintering temperature is 1150 ℃, the heat preservation time is 6 hours, and the oxygen partial pressure is 5 percent; and carrying out quenching and cooling after the reaction is finished, wherein the cooling rate is 80 ℃/s, and obtaining the manganese-zinc ferrite.

Example 4:

with Fe₂O₃、MnO₂ZnO as main material, SnO₂Compounding as an auxiliary raw material, Fe₂O₃Content 54mol%, MnO₂35mol% of ZnO, 11mol% of ZnO, SnO₂The content is 0.03 wt%; ball milling is carried out once after the material preparation is finished, and the rotating speed250 revolutions per minute and 3 hours of ball milling time; pre-sintering the raw materials subjected to the primary ball milling at the pre-sintering temperature of 950 ℃ for 3 hours; after completion, doping with CaCO₃Content 0.1wt%, V₂O₅0.004wt% of TiO₂0.2wt% of Co₂O₃The content is 0.2 wt%; performing secondary ball milling on the obtained raw materials, wherein the rotating speed is 250 revolutions per minute, and the ball milling time is 5 hours; after the secondary ball milling is finished, adding 15% PVA for granulation; then carrying out room temperature pre-pressing molding, wherein the applied pressure is 4 MPa; then, carrying out high-temperature deformation alternately in the transverse direction and the longitudinal direction, wherein the temperature is 1100 ℃, the deformation compression rate is 15 percent, and the deformation times are 10 times respectively in the transverse direction and the longitudinal direction; then, high-temperature pressure molding is carried out, the temperature is 1100 ℃, and the applied pressure is 6 MPa; then, high-temperature sintering is carried out, the sintering temperature is 1160 ℃, the heat preservation time is 6 hours, and the oxygen partial pressure is 5%; and carrying out quenching and cooling after the reaction is finished, wherein the cooling rate is 100 ℃/s, and obtaining the manganese-zinc ferrite.

Comparative example (prior art):

with Fe₂O₃、MnO₂ZnO as raw material, Fe₂O₃Content 55mol%, MnO₂After the ingredients with the content of 35mol% and the ZnO content of 10mol% are finished, carrying out primary ball milling at the rotation speed of 250 revolutions per minute for 3 hours; pre-sintering the raw materials subjected to the primary ball milling at the pre-sintering temperature of 950 ℃ for 3 hours; after completion, doping with CaCO₃、SiO₂、Nb₂O₅、ZrO₂、SnO₂、TiO₂、V₂O₅、P₂O₅、Ni₂O₃、Co₂O₃、MoO₃、Ta₂O₅、Bi₂O₃Three or more of (1); performing secondary ball milling on the obtained raw materials, wherein the rotating speed is 250 revolutions per minute, and the ball milling time is 5 hours; after the secondary ball milling is finished, adding 15% PVA for granulation; then pressurizing and forming, wherein the applied pressure is 6 MPa; then high-temperature sintering is carried out, the sintering temperature is 1150 ℃, the heat preservation time is 6 hours, and the oxygen partial pressure is 5 percent; and cooling the mixture after the reaction is finished, wherein the cooling rate is 300 ℃/h, and the manganese-zinc ferrite is obtained.

The manganese-zinc ferrite of the invention has ultra-fine grains, high temperature characteristic and high frequency characteristic, and the performance test is as follows:

finally, it should be noted that although the above embodiments have been described herein, the scope of the present invention is not limited thereby. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein or by using equivalent structures or equivalent processes performed in the present specification, and are included in the scope of the present invention.