CN114031388B - Mn-Zn ferrite material and preparation method thereof - Google Patents

Mn-Zn ferrite material and preparation method thereof Download PDF

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CN114031388B
CN114031388B CN202111393852.8A CN202111393852A CN114031388B CN 114031388 B CN114031388 B CN 114031388B CN 202111393852 A CN202111393852 A CN 202111393852A CN 114031388 B CN114031388 B CN 114031388B
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ferrite
temperature
sintering
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CN114031388A (en
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徐士亮
韩卫东
宋兴连
解丽丽
周艳辉
廖文举
朱孔磊
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Shandong Chunguang Magnetoelectric Technology Co ltd
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Abstract

The invention discloses a method for utilizing industrial MnO 2 Compared with the traditional method of preparing high-performance high-frequency low-power-consumption MnZn ferrite material by using Mn as a raw material 3 O 4 The process for preparing MnZn ferrite by using the raw material has the advantages of low cost, high quality, production efficiency and qualification rate, and obvious microstructure and performance advantages, and uses industrial iron oxide red (Fe) 2 O 3 ) Pyrolusite or electrolytic MnO 2 Industrial ZnO is used as a raw material to prepare the high-frequency low-power soft magnetic Mn-Zn ferrite material.

Description

Mn-Zn ferrite material and preparation method thereof
Technical Field
The invention relates to the technical field of magnetic materials, in particular to a Mn-Zn ferrite material and a preparation method thereof.
Background
MnZn ferrite is a widely used material in the electronic industry, and is widely used as various electronic and electrical equipment such as filters, transformers and the like. In recent years, the application of MnZn ferrite is advancing toward high-Bs high-frequency miniaturization, and high-Bs high-frequency low-power MnZn ferrite materials have become the focus of research by various MnZn ferrite manufacturers. The key point of the preparation of the high-Bs high-frequency low-power-consumption MnZn ferrite material is to ensure that the material has a microstructure with small crystal grains, few pores and a compact structure. With Mn 3 O 4 The high-frequency low-power MnZn ferrite prepared by the raw material has the problems of uneven grain size, more pores, low density and low saturation magnetic flux density Bs. The main reason is the raw material Mn 3 O 4 In the pre-sintering stage, the raw material Fe is mixed with 2 O 3 Ferrite reaction occurs:
3Fe 2 O 3 +Mn 3 O 4 →3MnFe 2 O 4 +1/2O 2
the ferrite is made of MnFe in the secondary sintering process 2 O 4 The growth of crystal nucleus causes abnormal growth of some crystal grains, resulting in uneven crystal grain size, more pores and low density. And with MnO 2 The raw materials do not react with Fe in the pre-sintering process 2 O 3 Reaction, thus with MnO 2 The high-frequency low-power consumption soft magnetic ferrite material prepared from the raw materials has the advantages of fine and uniform crystal grains, few pores and high density and saturation magnetic flux density Bs.
Further, with Mn 3 O 4 The MnZn ferrite material prepared by the raw material is pre-sintered to form MnFe in the temperature range of 500-700 ℃ in the sintering process 2 O 4 Oxidation reactions can occur, causing shrinkage cracking of the blank.
2MnFe 2 O 4 +1/2O 2 →Mn 2 O 3 +2Fe 2 O 3
In order to avoid such problems, it is necessary to increase the temperature at a very slow rate in the temperature increase stage to avoid MnFe 2 O 4 The blank cracking caused by oxidation.
The conventional MnZn ferrite material generally uses Fe 2 O 3 、Mn 3 O 4 And ZnO is used as a main raw material, and the ZnO is mixed according to a certain proportion and then is subjected to presintering, sanding, granulation and sintering. Wherein Fe 2 O 3 The iron oxide red is mainly a byproduct of steel-making production, and because acid pickling is needed in the preparation process of the iron oxide red, a lot of impurities such as chloride ions, sulfate ions and the like are inevitably contained in the raw material iron oxide red, and the impurities need to be removed under the conditions of high temperature, high oxygen and slow temperature rise in the pre-sintering or secondary sintering process, otherwise, great harm is brought to the production of the ferrite magnetic core.
For the reasons stated above, mn is used 3 O 4 The problems of easy cracking of a blank, insufficient impurity removal, long sintering time, low production efficiency and the like exist in the sintering process of the MnZn ferrite material, the quality and the qualification rate of the product are seriously influenced, and the production cost of an enterprise is indirectly improved. Relative to Mn 3 O 4 ，MnO 2 Has the following application characteristics:
(1)MnO 2 belongs to high valence oxide, is unstable, and is firstly changed into Mn at 500-600 ℃ in the heating process 2 O 3 And then changed to Mn at 900-1000 deg.C 3 O 4 . The MnZn ferrite needs to be pre-sintered in the production process, and the pre-sintering temperature is 800-1000 ℃. MnO 2 Since it does not become Mn until 900 deg.C 3 O 4 And thus do not react with Fe 2 O 3 The direct reaction is adopted, the blank pressed by the powder is not easy to crack during secondary sintering, the temperature can be rapidly raised in the temperature raising stage, and the production qualification rate and the production efficiency are greatly improved.
(2)MnO 2 During the high temperature addition, mn is first changed 2 O 3 And then changed into Mn 3 O 4 ，
2MnO 2 →Mn 2 O 3 +1/2O 2
3Mn 2 O 3 →2Mn 3 O 4 +1/2O 2
The two reactions release oxygen, and the oxygen release can promote the oxidation and volatilization of chloride ions and sulfate ions, so that the harm caused by the impurity atoms is reduced, the temperature rise time can be shortened, and the production efficiency and the qualification rate of the MnZn ferrite are effectively improved. Therefore, the invention provides a method for utilizing industrial MnO 2 Mn-Zn ferrite material prepared by using the raw material and a preparation method thereof.
Disclosure of Invention
In view of the above, the present invention is directed to providing a method for utilizing industrial MnO 2 Compared with the traditional method of using Mn as a raw material to prepare a high-performance high-frequency low-power-consumption MnZn ferrite material 3 O 4 The method for preparing the MnZn ferrite by using the raw materials has the advantages of low cost, high quality, high production efficiency and qualification rate and obvious microstructure and performance advantages.
In order to achieve the purpose, the invention adopts the following technical scheme:
an Mn-Zn ferrite material comprising a main component and an auxiliary component, the main component comprising Fe 2 O 3 、MnO 2 And ZnO; the auxiliary components comprise CaO and SiO 2 、Nb 2 O 5 、Co 2 O 3 、TiO 2 And SnO 2 。
Preferably, the mole percentage of each component in the main component is as follows: fe 2 O 3 50-57%, znO4-12%, and MnO as the rest 2 。
Preferably, the content of each component in the auxiliary components is as follows according to the weight of the main component: caO0.03-0.2%, siO 2 0.01-0.03％、Nb 2 O 5 0.01-0.06％、Co 2 O 3 0.05-0.3％、TiO 2 0.05-0.2% and SnO 2 0.05-0.3％。
The preparation method of the Mn-Zn ferrite material comprises the following steps:
(1) Accurately weighing iron oxide red and MnO according to the formula 2 And ZnO, putting into a sand mill, adding water, mixing, and drying at 200 ℃ for 2h to obtain a dried material;
(2) Putting the dried material into a muffle furnace for presintering at the presintering temperature of 800-950 ℃ for 1-4h to obtain a presintering material;
(3) After the pre-sintered material is cooled, weighing each component in the auxiliary components according to the total weight of the main components, mixing with the pre-sintered material, adding water for sanding for 1-5 hours to obtain a sand abrasive, wherein D50 of the sand abrasive is 0.8-1.2 mu m;
(4) Adding polyvinyl alcohol accounting for 0.1-0.5% of the weight of the pre-sintered material into the sand grinding material, and performing spray granulation;
(5) And (3) granulating, performing compression molding to obtain a Mn-Zn ferrite blank, and sintering the pressed Mn-Zn ferrite blank in an atmosphere protection bell jar furnace to obtain the Mn-Zn ferrite material.
Preferably, the amount of water added in step (1) is the same as the total weight of the main components.
Preferably, the Mn-Zn ferrite ingot in the step (5) has a density of 2.8 to 3.0kg/cm 3 。
Preferably, the sintering process of the sintering in the step (5) is as follows:
(1) raising the temperature to 200 ℃ at the speed of 2-5 ℃/min in the air, and then raising the temperature to 300 ℃ at the speed of 0.5-1 ℃/min;
PVA added in the granulation process can be decomposed and volatilized at 200-300 ℃, and if the temperature is raised too fast in the stage, the PVA is volatilized violently, so that blanks are easy to crack, the temperature needs to be raised slowly at 200-300 ℃, and the PVA is ensured to have sufficient time to volatilize;
(2) continuously heating to 1100-1250 deg.C at a speed of 5-10 deg.C/min, reducing oxygen content in sintering atmosphere to 0.5-5.0%, and maintaining for 150-300min;
due to the use of MnO 2 Substitute for Mn 3 O 4 Not forming MnFe after pre-sintering 2 O 4 So that MnFe does not exist in the temperature rising section 2 O 4 And the blank is cracked due to oxidation. Simultaneous MnO 2 Release of O by decomposition reaction 2 And the volatilization of chlorine radical and sulfate radical impurities in the blank is promoted, so that the harm caused by acid radical ions is avoided. Therefore, the temperature of the temperature rising section can be rapidly raised, and the production efficiency is effectively improved. For MnZn ferrite material with high Bs, high frequency and low power consumption, the microstructure crystal grains must be small, the air holes are few, the density is high, so the sintering temperature cannot be too high, and the sintering temperature is moderate between 1100 ℃ and 1250 ℃. The reduction of the oxygen content of the sintering atmosphere is favorable for promoting the elimination of pores and the microcosmic densification of the material, the oxygen content of the sintering heat-preservation atmosphere is reduced to 0.5-5.0 percent, the heat preservation time of 150-300min can be matched, the magnetic permeability of the material can be controlled to be 1000-1500, and the density is controlled to be 4.8-4.9g/cm 3 The power consumption characteristic of the material 500K-3M is better;
(3) after the heat preservation is finished, the temperature is reduced to 1000 ℃ at the speed of 0.3-1.5 ℃/min, the oxygen content is controlled to be 0.5-1.0% at 1100 ℃, 0.1-0.3% at 1050 ℃ and 0.02-0.05% at 1000 ℃;
and in the MnZn ferrite sintering heat preservation stage, impurities such as doped Ca, si and the like are dissolved in MnZn spinel in a solid solution mode, in the cooling stage, the impurities move and segregate to grain boundaries, and after cooling is finished, an insulating layer with high resistivity is formed on the grain boundaries, so that the grain boundary resistivity is improved, and the high-frequency power consumption characteristic of the material is reduced. By slowly cooling at the temperature of heat preservation-cooling of 1000 ℃, impurities such as Ca, si and the like can be guaranteed to have sufficient time to move and segregate towards the grain boundary, so that the thickness of the grain boundary layer of the material is increased, and the high-frequency power consumption characteristic of the material is improved. The oxygen content of the sintering atmosphere is reduced at 1050 ℃ and 1000 ℃ mainly to avoid the oxidation of MnFe2O4 and Fe3O4 formed in the heat preservation stage so as to deteriorate the performance of the material;
(4) finally, cooling to 200 ℃ at a cooling speed of 3-10 ℃/min, and controlling the oxygen content to be less than 50ppm;
the purpose of reducing the temperature of the low-oxygen atmosphere in the stage is to protect MnFe formed in the heat preservation stage 2 O 4 And Fe 3 O 4 And the material performance is prevented from being damaged.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1)MnO 2 the pre-sintering stage does not react with Fe 2 O 3 Ferrite reaction is carried out, and MnFe does not exist in the secondary sintering stage 2 O 4 The problem of blank cracking is caused, so that the temperature rise sintering can be carried out at a higher speed, the sintering time is shortened, and the production efficiency is improved;
(2)MnO 2 oxygen is released by decomposition in the temperature rise stage, so that acid radicals and other impurities in the blank are oxidized and removed, and the quality and the qualification rate of a fired product are improved;
(3)MnO 2 the pre-sintering stage does not react with the raw material Fe 2 O 3 The ferrite reaction is carried out, so that crystal nuclei required by the growth of the secondary sintered ferrite can not be formed, the uniform growth of secondary sintered crystal grains is facilitated, and a microstructure with uniform crystal grain size and few pores is formed, thereby improving the high-frequency power consumption characteristic of the material.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The Mn — Zn ferrite material provided by the present embodiment includes a main component and an auxiliary component,the mol percentage of each component in the main component is Fe 2 O 3 57%, znO12%, and the balance MnO 2 (ii) a The contents of the components in the auxiliary components are as follows according to the weight of the main components: caO0.2%, siO 2 0.03％、Nb 2 O 5 0.06％、Co 2 O 3 0.3％、TiO 2 0.2% and SnO 2 0.3％。
In this example, an Mn-Zn ferrite material was prepared as follows:
(1) Accurately weighing iron oxide red (Fe) 2 O 3 )、MnO 2 And ZnO, putting into a sand mill, adding water, mixing, and drying to obtain a dried material;
(2) Putting the dried material into a muffle furnace for presintering at 950 ℃ for 1h to obtain a presintering material;
(3) After the pre-sintered material is cooled, weighing each component in the auxiliary components according to the total weight of the main components, mixing the components with the pre-sintered material, adding water for sanding for 5 hours to obtain a sand abrasive, wherein D50 of the sand abrasive is 1.2 mu m;
(4) Adding polyvinyl alcohol accounting for 0.5 percent of the weight of the pre-sintered material into the sand grinding material, and performing spray granulation;
(5) And (2) after granulation, performing compression molding to obtain a Mn-Zn ferrite blank, and sintering the pressed Mn-Zn ferrite blank in an atmosphere protection bell jar furnace, wherein the sintering process comprises the following steps:
(1) raising the temperature to 200 ℃ at a speed of 2 ℃/min in the air, and then raising the temperature to 300 ℃ at a speed of 0.5 ℃/min;
(2) continuously heating to 1100 deg.C at a speed of 5 deg.C/min, reducing oxygen content in sintering atmosphere to 2.5%, and maintaining for 150min;
(3) after the heat preservation is finished, the temperature is reduced to 1000 ℃ at the speed of 0.3 ℃/min, the oxygen content is controlled to be 0.5% at 1100 ℃, 0.1% at 1050 ℃ and 0.02% at 1000 ℃;
(4) finally, the temperature is reduced to 200 ℃ at the speed of 10 ℃/min, and the oxygen content is controlled to be less than 50ppm.
Example 2
The Mn-Zn ferrite material provided by the present embodiment comprises a main component and an auxiliary component, the main componentThe mol percentage of each component in the composition is Fe 2 O 3 50%, znO4%, and the balance MnO 2 (ii) a The contents of the components in the auxiliary components are as follows according to the weight of the main components: caO0.03%, siO 2 0.01％、Nb 2 O 5 0.01％、Co 2 O 3 0.05％、TiO 2 0.052% and SnO 2 0.05％。
In this example, an Mn-Zn ferrite material was prepared as follows:
(1) Accurately weighing iron oxide red (Fe) 2 O 3 )、MnO 2 And ZnO, putting into a sand mill, adding water, mixing, and drying to obtain a dried material;
(2) Putting the dried material into a muffle furnace for presintering at 800 ℃ for 4 hours to obtain a presintering material;
(3) After the pre-sintered material is cooled, weighing each component in the auxiliary components according to the total weight of the main components, mixing with the pre-sintered material, adding water for sanding for 1h to obtain a sand abrasive, wherein the D50 of the sand abrasive is 0.8 mu m;
(4) Adding polyvinyl alcohol accounting for 0.5 percent of the weight of the pre-sintered material into the sand grinding material, and performing spray granulation;
(5) And (2) after granulation, performing compression molding to obtain a Mn-Zn ferrite blank, and sintering the pressed Mn-Zn ferrite blank in an atmosphere protection bell jar furnace, wherein the sintering process comprises the following steps:
(1) raising the temperature to 200 ℃ at a temperature raising speed of 5 ℃/min in the air, and then raising the temperature to 300 ℃ at a speed of 1 ℃/min;
(2) continuously heating to 1100-1250 deg.C at a speed of 10 deg.C/min, reducing oxygen content in sintering atmosphere to 5.0%, and maintaining for 150-300min;
(3) after the heat preservation is finished, the temperature is reduced to 1000 ℃ at the speed of 1.5 ℃/min, the oxygen content is controlled to be 1.0% at 1100 ℃, 0.3% at 1050 ℃ and 0.05% at 1000 ℃;
(4) finally, the temperature is reduced to 200 ℃ at the speed of 3 ℃/min, and the oxygen content is controlled to be less than 50ppm.
Example 3
The Mn-Zn ferrite material provided by the present embodiment comprises a main component and an auxiliary component, the main componentThe mol percentage of each component in the composition is Fe 2 O 3: 52mol% ZnO, 6mol% ZnO, and the balance MnO 2 (ii) a The contents of the components in the auxiliary components are as follows according to the weight of the main components: 0.08 percent of CaO and SiO 2: 0.015％、Nb 2 O 5: 0.02％、Co 2 O 3 0.1％、TiO 2 0.08% and SnO 2 0.08％。
This example prepares an Mn-Zn ferrite material as follows:
(1) Accurately weighing iron oxide red (Fe) 2 O 3 )、MnO 2 And ZnO, putting into a sand mill, adding water, mixing, and drying to obtain a dried material;
(2) Putting the dried material into a muffle furnace for presintering at 800 ℃ for 4 hours to obtain a presintering material;
(3) After the pre-sintered material is cooled, weighing each component in the auxiliary components according to the total weight of the main components, mixing with the pre-sintered material, adding water for sanding for 1h to obtain a sand abrasive, wherein the D50 of the sand abrasive is 0.8 mu m;
(4) Adding polyvinyl alcohol accounting for 0.5 percent of the weight of the pre-sintered material into the sand grinding material, and performing spray granulation;
(5) And (2) after granulation, performing compression molding to obtain an Mn-Zn ferrite blank, and sintering the pressed Mn-Zn ferrite blank in an atmosphere protection bell jar furnace, wherein the sintering process comprises the following steps:
(1) raising the temperature to 200 ℃ at a speed of 3 ℃/min in the air, and then raising the temperature to 300 ℃ at a speed of 1 ℃/min;
(2) continuously heating to 1250 ℃ at the speed of 10 ℃/min, reducing the oxygen content of the sintering atmosphere to 5.0 percent, and preserving the heat for 200min;
(3) after the heat preservation is finished, the temperature is reduced to 1000 ℃ at the speed of 1.5 ℃/min, the oxygen content is controlled to be 1.0% at 1100 ℃, 0.3% at 1050 ℃ and 0.02% at 1000 ℃;
(4) finally, the temperature is reduced to 200 ℃ at the speed of 10 ℃/min, and the oxygen content is controlled to be less than 50ppm.
Performance testing
The specific properties of the Mn-Zn ferrite-like ring prepared in example 3, as measured by initial permeability of 1000-1500 and sintered density of 4.7-4.9kg/cm3, are shown in Table 1:
TABLE 1
Figure BDA0003369723160000081
Figure BDA0003369723160000091
As can be seen from the above table, the present invention uses MnO 2 Substitute for Mn 3 O 4 The Mn-Zn ferrite material with high Bs, high frequency and low power consumption is prepared.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (3)

1. An Mn-Zn ferrite material characterized by comprising a main component and an auxiliary component, the main component comprising Fe 2 O 3 、MnO 2 And ZnO; the auxiliary components comprise CaO and SiO 2 、Nb 2 O 5 、Co 2 O 3 、TiO 2 And SnO 2 ；
The main components comprise the following components in percentage by mol: fe 2 O 3 50-57mol%, znO4-12mol%, and the balance MnO 2 ；
The contents of the components in the auxiliary components are as follows according to the weight of the main components: caO0.03-0.2%, siO 2 0.01-0.03％、Nb 2 O 5 0.01-0.06％、Co 2 O 3 0.05-0.3％、TiO 2 0.05-0.2% and SnO 2 0.05-0.3％；
The Mn-Zn ferrite material is prepared by the following method:
(1) Accurately weighing iron oxide red and MnO according to the formula 2 Mixing with ZnO, adding water, and drying at 200 deg.C for 2 hr to obtain dried material;
(2) Pre-burning the dried material at 800-950 ℃ for 1-4h to obtain a pre-burned material;
(3) After the pre-sintered material is cooled, weighing each component in the auxiliary components according to the total weight of the main components, mixing the components with the pre-sintered material, and then adding water for sanding for 1-5 hours to obtain a sand abrasive;
(4) Adding polyvinyl alcohol accounting for 0.1-0.5% of the weight of the pre-sintered material into the sand grinding material, and performing spray granulation;
(5) After granulation, pressing and forming to obtain a Mn-Zn ferrite blank, and sintering the pressed Mn-Zn ferrite blank in an atmosphere protection bell jar furnace to obtain the Mn-Zn ferrite material;
the sintering process of the sintering in the step (5) comprises the following steps:
(1) raising the temperature to 200 ℃ at the speed of 2-5 ℃/min in the air, and then raising the temperature to 300 ℃ at the speed of 0.5-1 ℃/min;
(2) continuously heating to 1100-1250 deg.C at a speed of 5-10 deg.C/min, reducing oxygen content in sintering atmosphere to 0.5-5.0%, and maintaining for 150-300min;
(3) after the heat preservation is finished, the temperature is reduced to 1000 ℃ at the speed of 0.3-1.5 ℃/min, the oxygen content is controlled to be 0.5-1.0% at 1100 ℃, 0.1-0.3% at 1050 ℃ and 0.02-0.05% at 1000 ℃;
(4) finally, the temperature is reduced to 200 ℃ at the speed of 3-10 ℃/min, and the oxygen content is controlled to be less than 50ppm.
2. An Mn-Zn ferrite material as claimed in claim 1, wherein the water is added in the same amount as the total weight of the main components in step (1).
3. A Mn-Zn ferrite material as claimed in claim 2, wherein the density of the Mn-Zn ferrite ingot in the step (5) is 2.8 to 3.0kg/cm 3 。
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