CN117945742A - Manganese zinc ferrite material and preparation method thereof - Google Patents
Manganese zinc ferrite material and preparation method thereof Download PDFInfo
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- CN117945742A CN117945742A CN202211274376.2A CN202211274376A CN117945742A CN 117945742 A CN117945742 A CN 117945742A CN 202211274376 A CN202211274376 A CN 202211274376A CN 117945742 A CN117945742 A CN 117945742A
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- 239000000463 material Substances 0.000 title claims abstract description 110
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 58
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 11
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 41
- 239000001301 oxygen Substances 0.000 claims description 41
- 229910052760 oxygen Inorganic materials 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000005496 tempering Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 34
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 230000001276 controlling effect Effects 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000011701 zinc Substances 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012496 blank sample Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
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Abstract
The invention provides a manganese zinc ferrite material and a preparation method thereof. The manganese-zinc ferrite material comprises main components of Fe 2O3 51.30-51.78 mol%, znO 11.42-11.64 mol%, mnO 36.58-37.27 mol% and CoO 0.02-0.1 mol%; and an auxiliary component CaCO3：200～2000ppm,Bi2O3：200～2000ppm,MoO：200～2000ppm,NbO：200～2000ppm,ZrO：200～2000ppm. which has a high curie temperature of greater than 230 ℃, bs (25 ℃) of greater than 530mT, and magnetic permeability in a temperature range of 0 to 230 ℃ enables high magnetic permeability and low temperature coefficient. The manganese-zinc ferrite material provided by the invention can realize stable operation under wider and more extreme environmental conditions, and greatly widens the application of the manganese-zinc ferrite in the field of electronic devices.
Description
Technical Field
The invention relates to the technical field of ferrite materials, in particular to a manganese zinc ferrite material and a preparation method thereof.
Background
At present, the high-permeability Mn-Zn ferrite is widely applied in the fields of electronic signal transmission, electromagnetic interference resistant technology, environmental protection, energy conservation and the like. When the Mn-Zn ferrite is applied to electronic products, the comprehensive properties of the Mn-Zn ferrite are often required to be improved, such as: can ensure stable high permeability in a wider temperature range. Generally, the working temperature is about-40-90 ℃, but for military electronic products and environment-extreme civil electronic products, higher temperatures are often required, sometimes up to 0-230 ℃, i.e. the electronic products are required to be in a stable high permeability state in the temperature range. The range of mass production temperatures that can be achieved at present has not been reported. Therefore, the manganese-zinc ferrite material with high Bs, high magnetic permeability, high Curie temperature and low temperature coefficient characteristics needs to be developed to realize the application range in the field of electronic signals.
The current Mn-Zn ferrite technology is developed in the field of Mn-Zn ferrite materials with wide temperature range and high magnetic permeability, and is mainly aimed at effectively controlling the range limitation of the main component formula, the component types and the addition amount of additives, the molding density, the sintering process and other parameters aiming at different performances, and the prior invention patent is mentioned.
For example, CN101863657B discloses an mn—zn ferrite having a magnetic permeability of 5000 or more in a temperature range of-60 to 130 ℃, in which the main component iron oxide is in a range of 51 to 56mol% and zinc oxide is in a range of 16 to 26mol%, but the temperature coefficient of magnetic permeability is relatively high in its temperature range and the curie temperature is low.
In CN101560091a, an Mn-Zn ferrite material having a low temperature coefficient of permeability in the temperature range of-25 to 150 ℃ is disclosed, and in the main component of the material, iron oxide is in the range of 52.5 to 55mol% and zinc oxide is in the range of 10 to 18mol%, but in this patent, there is no description about how to achieve high permeability in the temperature ranges of-40 to-25 ℃ and 150 to 230 ℃.
In CN103588471B, a Mn-Zn ferrite material with magnetic permeability over 5000 at-55-125 deg.C is disclosed, whose main components are iron oxide 54-55 mol% and zinc oxide 14-15.9 mol%.
In CN104961450A, a Mn-Zn ferrite material with magnetic permeability over 2900 at-40-85 deg.C is disclosed, whose main component is iron oxide in 47.5-54.5 mol% and zinc oxide in 15-24 mol%, and its magnetic permeability is far lower than 5000.
As can be seen, no report is currently made on Mn-Zn ferrite materials with magnetic permeability reaching over 5000 in the temperature range of-55-230 ℃. Therefore, there is a need to prepare a manganese-zinc-ferrite material with high Bs, high permeability, high curie temperature, low temperature coefficient characteristics.
Disclosure of Invention
The invention mainly aims to provide a manganese-zinc ferrite material and a preparation method thereof, which are used for solving the problem that the manganese-zinc ferrite material in the prior art is difficult to realize the characteristics of high Bs, high magnetic permeability, high Curie temperature and low temperature coefficient at the same time.
In order to achieve the above object, according to one aspect of the present invention, there is provided a manganese-zinc-ferrite material characterized in that the manganese-zinc-ferrite material includes a main component and an auxiliary component; wherein the main component comprises Fe 2O3: 51.30 to 51.78mol percent, znO:11.42 to 11.64mol percent, mnO:36.58 to 37.27mol%, coO:0.02 to 0.1mol%; the content of each component of the auxiliary components is based on the total weight of the main components CaCO3：200～2000ppm,Bi2O3：200～2000ppm,MoO：200～2000ppm,NbO：200～2000ppm,ZrO：200～2000ppm.
Further, the main component comprises Fe 2O3: 51.02 to 51.63mol percent, znO:11.30 to 11.60mol percent, coO:0.02 to 0.1mol percent, and the balance of MnO; preferably, the content of each component of the auxiliary component is based on the total weight of the main component CaCO3：200～1000ppm,Bi2O3：200～1000ppm,MoO：200～800ppm,NbO：200～2000ppm,ZrO：200～2000ppm.
According to another aspect of the present invention, there is provided a method for preparing a manganese zinc ferrite material, characterized in that the method comprises the steps of: (1) presintering: weighing the raw materials of each component of the main component respectively, performing wet ball milling and drying on the raw materials, and presintering to obtain a presintering material; (2) mixing: carrying out wet ball milling on the pre-sintered material and the raw materials of each component of the auxiliary component to obtain mixed slurry; (3) tempering: drying the mixed slurry, and tempering to obtain a tempered material; (4) granulating: drying the tempering material to obtain a drying material, mixing the drying material with a binder, grinding and granulating to obtain granules; (5) pressing: pressing and molding the granules to obtain a molded body; (6) sintering: sintering the molded body to obtain the Mn-Zn ferrite material.
Further, the temperature in the sintering process is 1250-1300 ℃, and the sintering time is 5-7 h; preferably, the oxygen content in the sintering atmosphere in the sintering process is 3-5 vol%, and the rest atmosphere except oxygen in the sintering atmosphere is inert gas.
Further, before the sintering process, the preparation method further comprises a heating process, wherein the heating process comprises the following steps: under the sintering atmosphere with the oxygen content of 19-21 vol%, firstly heating the molded body to 600-800 ℃ and preserving heat for 2-3 h; and then heating to 1100-1300 ℃ within 6-10 h, and preserving heat for 5-8 h.
Further, after the sintering process, the preparation method further comprises a cooling process, wherein the cooling process is performed under the balance of oxygen partial pressure.
Further, the presintering process is performed under an air atmosphere; the presintering temperature is 650-800 ℃ and the presintering time is 2-3 h.
Further, the tempering temperature is 650-800 ℃.
Further, the wet ball milling time is 70-90 min.
Further, the particle size of the pellets is 1.0 to 1.05. Mu.m.
Further, the binder accounts for 10 to 12 weight percent of the baking material; the binder comprises one or more of PVA, glue and epoxy resin.
By applying the technical scheme of the invention, the manganese-zinc ferrite material is prepared. The material has a high Curie temperature of greater than 230 ℃, a Bs (25 ℃) of greater than 530mT, and magnetic permeability in a temperature range of-55 to 230 ℃ can realize high magnetic permeability and low temperature coefficient. The manganese-zinc ferrite material provided by the invention can realize stable operation under wider and more extreme environmental conditions, and greatly widens the application of the manganese-zinc ferrite in the field of electronic devices.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
In order to solve the technical problems as described above, according to an aspect of the present invention, there is provided a manganese zinc ferrite material including a main component and an auxiliary component; wherein the main component comprises Fe 2O3: 51.30 to 51.78mol percent, znO:11.42 to 11.64mol percent, mnO:36.58 to 37.27mol%, coO:0.02 to 0.1mol%; the manganese zinc ferrite material is prepared by applying the technical scheme of the invention with the content of each component of the auxiliary components being CaCO3：200～2000ppm,Bi2O3：200～2000ppm,MoO：200～2000ppm,NbO：200～2000ppm,ZrO：200～2000ppm. based on the total weight of the main component. The material has a high Curie temperature of greater than 230 ℃, a Bs (25 ℃) of greater than 530mT, and permeability in the temperature range of 0-230 ℃ can realize high permeability and low temperature coefficient. The manganese-zinc ferrite material provided by the invention can realize stable operation under wider and more extreme environmental conditions, and greatly widens the application of the manganese-zinc ferrite in the field of electronic devices.
In manganese zinc ferrite materials, the permeability increases with increasing zinc oxide content and the resistance decreases. Thus, in a certain range, the increase of the zinc oxide content is beneficial to improving the magnetic permeability of the manganese zinc ferrite, but excessive zinc oxide can reduce the Curie temperature and the temperature stability of the material, so that the material cannot be used in a wide temperature range. It is therefore critical to select the composition ratio of the principal components depending on the working environment and use. In the present invention, the content of zinc oxide is 11.42 to 11.64mol%.
In the manganese zinc ferrite material, coO is added as a main component, the anisotropy constant (K 1) is larger than 0, the value of K 1 is suddenly reduced along with the rise of temperature, and the manganese zinc ferrite material is matched and adjusted with other main components to enable K 1 to move to low temperature, the curve is smoother at 0-230 ℃, and the magnetic permeability mu i (0-230 ℃) is 5000-5500.
Meanwhile, the auxiliary components doped in the technical scheme provided by the invention can also have the beneficial effects of improving the magnetic conductivity of the material and keeping a lower temperature coefficient. And the main components and the auxiliary components also play a synergistic interaction role, so that the temperature characteristic of the material is improved.
In summary, the main component, the auxiliary component and the range values thereof provided in the technical scheme of the invention just enable the Curie temperature of the manganese-zinc ferrite material provided by the invention to be more than 230 ℃, the manganese-zinc ferrite material can be applied at 0-230 ℃, and the manganese-zinc ferrite material has good performances of magnetic permeability, saturated magnetic flux, temperature coefficient and the like in the range.
In order to further increase the curie temperature and temperature stability of the manganese-zinc-ferrite material, in a preferred embodiment, the main component of the manganese-zinc-ferrite material includes Fe 2O3: 51.02 to 51.63mol percent, znO:11.30 to 1160mol percent, coO:0.02 to 0.1mol percent, and the balance of MnO; preferably, the content of each component of the auxiliary component is based on the total weight of the main component CaCO3：200～1000ppm,Bi2O3：200～1000ppm,MoO：200～800ppm,NbO：200～2000ppm,ZrO：200～2000ppm.
According to another aspect of the present invention, there is provided a method for preparing the above manganese zinc ferrite material, comprising the steps of: (1) presintering: respectively weighing the raw materials of each component of the main component, performing wet ball milling, drying and presintering to obtain a presintering material; (2) mixing: carrying out wet ball milling on the pre-sintered material and the raw materials of each component of the auxiliary component to obtain mixed slurry; (3) tempering: drying the mixed slurry, and tempering to obtain a tempered material; (4) granulating: drying the tempering material to obtain a drying material, mixing the drying material with a binder, grinding and granulating to obtain granules; (5) pressing: pressing and molding the granules to obtain a molded body; (6) sintering: sintering the molded body to obtain the Mn-Zn ferrite material. By applying the technical scheme of the invention, the manganese-zinc ferrite material is prepared. The material has a high Curie temperature of greater than 230 ℃, a Bs (25 ℃) of greater than 530mT, and permeability in the temperature range of 0-230 ℃ can realize high permeability and low temperature coefficient. The manganese-zinc ferrite material provided by the invention can realize stable operation under wider and more extreme environmental conditions, and greatly widens the application of the manganese-zinc ferrite in the field of electronic devices.
As described above, in the manganese zinc ferrite material provided by the invention, coO is added as a main component, so that in the preparation method of the invention, the CoO component is subjected to multiple processes of ball milling, presintering, tempering and sintering. The process treatment can lead the Co 2+ to be uniformly distributed, thereby leading the manganese zinc ferrite material obtained by the preparation method of the invention to have excellent performances of high initial permeability, low temperature coefficient, wide temperature range and the like. In particular, although the prior art has reported that the ferrite is improved in the comprehensive performance by pre-sintering the main component, for example, in CN114195500a, the powder obtained by ball milling after pre-sintering is subjected to a secondary tempering process, but in the patent, co 2O3 is present as an auxiliary component, so Co 2O3 is not pre-sintered as an auxiliary material. In contrast, in the technical scheme of the invention, the addition amount of CoO is more, and the CoO is innovatively used as a main component to be presintered with Fe 2O3, znO and MnO, so that the element distribution is more uniform, the K 1 can be better regulated to move to low temperature as the main component with other components, the magnetic permeability mu i (0-230 ℃) is between 5000 and 5500, the excellent temperature coefficient is realized, and unexpected beneficial technical effects are obtained.
In order to further improve the temperature characteristics of the manganese zinc ferrite material, in a preferred embodiment, the sintering process is carried out at a temperature of 1250-1300 ℃ for a sintering time of 5-7 h; preferably, the oxygen content in the sintering atmosphere in the sintering process is 3-5 vol%, and the rest atmosphere except oxygen in the sintering atmosphere is inert gas. In actual operation, the inert gas may be nitrogen, argon, or the like, which does not react with the manganese zinc ferrite. The lower sintering temperature is preferred to enable the grains in the ferrite to achieve high densification and more uniform ion distribution, thereby obtaining the manganese-zinc ferrite material with high curie temperature, high Bs and initial permeability.
For the purpose of further improving the temperature characteristics of the manganese zinc ferrite material, in a preferred embodiment, the preparation method further comprises, prior to the sintering process, a temperature increasing process comprising: under the sintering atmosphere with the oxygen content of 19-21 vol%, firstly heating the molded body to 600-700 ℃ and preserving heat for 2-3 h; and then heating to 1100-1300 ℃ within 6-10 h, and preserving heat for 5-8 h. Through the optimized multiple heating and heat preservation processes, low-temperature gradient sintering is realized, and lattice defects can be better improved, so that the material with better comprehensive magnetic properties is prepared.
In practice, preferably, the preparation method further comprises a cooling process, which is carried out under an equilibrium oxygen partial pressure, after the sintering process.
In order to further improve the magnetic properties of the manganese zinc ferrite material, in a preferred embodiment, the pre-firing process is performed under an air atmosphere; the presintering temperature is 650-800 ℃ and the presintering time is 2-3 h.
In order to further increase the stability of the structure within the material and to make the distribution of the components within the material more uniform, in a preferred embodiment the tempering temperature is between 650 and 800 ℃.
The process conditions for wet ball milling may be conventional in the art, but for the purpose of further thoroughly mixing the components, it is preferable that the time for wet ball milling is 70 to 90 minutes.
In order to further ensure uniform mixing of the components and uniform distribution of the ions, the particle size of the pellets is preferably 1.0 to 1.05. Mu.m.
In order to enable better mixing of the tempering material, in a preferred embodiment the binder comprises 10 to 12wt% of the drying material; the binder comprises one or more of PVA, glue and epoxy resin.
In actual operation, the pressing of the pellets is preferably carried out in a press. The size of the pressed shaped body is preferably H25X 15X 8.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
The design formula is Fe 2O3: 51.63mol%, mnO 36.3mol%, znO 11.60mol%, coO: precisely weighing 0.47mol% of four main component components, putting the four main component components into a ball mill for ball milling, mixing until the four main component components are uniform, putting the four main component components into an oven for drying, presintering the four main component components for 3 hours at 700 ℃ to obtain a presintering material, and adding auxiliary components (based on the total amount of the main components) into the presintering material: bi 2O3:400ppm、CaCO3: 400ppm, moO:200ppm, nbO:200ppm, zrO:200ppm is ball-milled in a ball mill for 70min, and then dried and tempered at 750 ℃. Then 10wt% PVA is added to granulate to obtain ferrite particles, and the ferrite particles are sieved. Ferrite particles were pressed by a press to form a blank of size h25×15×8, placed in a condition of N 2 controlling the oxygen content to 21vol% and sintered at 600 ℃ for 2 hours, placed in a condition of N 2 controlling the oxygen content to 21vol% and sintered at 1100 ℃ for 8 hours, then sintered at 1290 ℃ for 7 hours under N 2 controlling the oxygen content to 4vol%, and cooled under the equilibrium oxygen partial pressure to obtain a powder core for testing.
Example 2
The design formula is Fe 2O3: 51.44mol%, mnO 36.60mol%, znO 11.49mol%, coO: precisely weighing four main components of 0.47mol%, ball milling by a ball mill, uniformly mixing, putting into a baking oven for baking, presintering for 3 hours at 800 ℃ to obtain a presintering material, and adding auxiliary components (based on the total amount of the main components) into the presintering material: caCO 3：400ppm、Bi2O3:400 ppm, moO:200ppm, nbO:300ppm, zrO:200ppm is ball-milled in a ball mill for 80min, and then dried for 800 ℃ tempering process. Then 10wt% PVA is added to granulate to obtain ferrite particles, and the ferrite particles are sieved. Ferrite particles were pressed by a press to form a blank of size h25×15×8, placed in a condition of controlling the oxygen content to 21vol% by N 2 and sintered at 650 ℃ for 3 hours, under controlling the oxygen content to 21vol% by N 2 and sintered at 1120 ℃ for 5 hours, then under controlling the oxygen content to 3vol% by N 2 and sintered at 1290 ℃ for 5 hours, cooled under the equilibrium oxygen partial pressure, and tested to obtain a powder core.
Example 3
The design formula is Fe 2O3:51.24 mol%, mnO 36.81mol%, znO 11.49mol%, coO: precisely weighing four main components of 0.55mol%, ball milling and mixing uniformly by a ball mill, putting into an oven for drying, presintering for 2 hours at 800 ℃ to obtain a presintering material, and adding auxiliary components (based on the total amount of the main components) into the presintering material: caCO 3：200ppm、Bi2O3:600 ppm, moO:200ppm, nbO:200ppm, zrO:250ppm is ball-milled in a ball mill for 100min, ball-milled in the ball mill for 80min, and then dried and tempered at 850 ℃. Then 10wt% PVA is added to granulate to obtain ferrite particles, and the ferrite particles are sieved. Ferrite particles were pressed by a press to form a blank of size h25×15×8, placed in a condition of N 2 controlling the oxygen content to 21vol% and sintered at 700 ℃ for 2 hours, placed in a condition of N 2 controlling the oxygen content to 21vol% and sintered at 1100 ℃ for 8 hours, then sintered at 1280 ℃ for 7 hours under N 2 controlling the oxygen content to 5vol%, and cooled under the equilibrium oxygen partial pressure to obtain a powder core for testing.
Example 4
The design formula is Fe 2O3:51.03 mol%, mnO 36.81mol%, znO 11.40mol%, coO: precisely weighing four main components of 0.47mol%, ball milling and mixing uniformly by a ball mill, putting into an oven for drying, presintering for 3 hours at 650 ℃ to obtain a presintering material, and adding auxiliary components (the auxiliary components are calculated according to the total amount of the main components) into the presintering material: caCO 3：600ppm、Bi2O3:600 ppm, moO:200ppm, nbO:250ppm, zrO: ball milling 250ppm in ball mill for 90min, stoving and tempering at 750 deg.c. Then 10wt% PVA is added to granulate to obtain ferrite particles, and the ferrite particles are sieved. Ferrite particles were pressed by a press to form a blank of size h25×15×8, placed in a condition of N 2 controlling the oxygen content to 21vol% and sintered at 700 ℃ for 2 hours, placed in a condition of N 2 controlling the oxygen content to 21vol% and sintered at 1100 ℃ for 8 hours, then sintered at 1300 ℃ for 5 hours under N 2 controlling the oxygen content to 5vol%, and cooled under the equilibrium oxygen partial pressure to obtain a powder core for testing.
Example 5
The design formula is Fe 2O3: 51.58mol%, mnO 36.35mol%, znO 11.52mol%, coO: precisely weighing four main components of 0.55mol%, ball milling and mixing uniformly by a ball mill, putting into an oven for drying, presintering for 3 hours at 650 ℃ to obtain a presintering material, and adding auxiliary components (the auxiliary components are calculated according to the total amount of the main components) into the presintering material: caCO 3：400ppm、Bi2O3, 800ppm, moO:300ppm, nbO:400ppm, zrO:400ppm was ball milled in a ball mill for 90min, then dried and tempered at 850 ℃. Then 12wt% of PVA is added to granulate to obtain ferrite particles, and the ferrite particles are sieved. Ferrite particles were pressed by a press to form a blank of size h25×15×8, placed in a condition of N 2 controlling the oxygen content to 19vol% and sintered at 700 ℃ for 2 hours, placed in a condition of N 2 controlling the oxygen content to 21vol% and sintered at 1120 ℃ for 6 hours, then sintered at 1260 ℃ for 7 hours under N 2 controlling the oxygen content to 5vol%, and cooled under the equilibrium oxygen partial pressure to obtain a powder core for testing.
Comparative example 1
Three main components with the design formula of 49.7mol% of Fe 2O3, 38.9mol% of MnO and 11.4mol% of ZnO are precisely weighed, ball-milled and uniformly mixed by a ball mill, put into an oven for drying, presintered for 3 hours at 800 ℃ to obtain a presintered material, and auxiliary components (based on the total amount of the main components) are added into the presintered material: caCO 3：400ppm、Bi2O3:400 ppm, coO:2000ppm, moO:200ppm was ball-milled in a ball mill for 80min, and then 10wt% PVA was added to granulate to obtain ferrite particles, which were then sieved. Pressing ferrite powder into a blank sample of H25×15X8 by a press, sintering at 1100 ℃ for 6 hours under the condition that the oxygen content is controlled to be 21vol% by N 2, then sintering at 1330 ℃ for 2 hours under the condition that the oxygen content is controlled to be 5vol% by N 2, and performing a cooling stage under the condition of balanced oxygen partial pressure to obtain the magnetic core for testing.
Comparative example 2
Three main components of which the design formulas are 53.0mol percent of Fe 2O3, 35.4mol percent of MnO and 11.6mol percent of ZnO are precisely weighed, ball-milled and uniformly mixed by a ball mill, presintered for 3 hours at 750 ℃ to obtain a presintered material, and auxiliary components (based on the total amount of the main components) are added into the presintered material: caCO 3：400ppm、Bi2O3:400 ppm, coO:1000ppm, moO:200ppm is ball-milled in a ball mill for 70min, and then ferrite particles are obtained through spray granulation and are sieved. Pressing ferrite powder into a blank sample of H25×15X8 by a press, sintering at 1100 ℃ for 6 hours under the condition that the oxygen content is controlled to be 21vol% by N 2, then sintering at 1300 ℃ for 2 hours under the condition that the oxygen content is controlled to be 5vol% by N 2, and performing a cooling stage under the condition of balanced oxygen partial pressure to obtain the magnetic core test.
Comparative example 3
Three main components with the design proportions of 52.0mol% of Fe 2O3, 36.3mol% of MnO and 11.7mol% of ZnO are precisely weighed, ball-milled and uniformly mixed by a ball mill, put into an oven for drying, presintered for 3 hours at 700 ℃ to obtain a presintered material, and auxiliary components (based on the total amount of the main components) are added into the presintered material: caCO 3：400ppm、Bi2O3:400 ppm, moO:200ppm is ball-milled in a ball mill for 100min, and then ferrite particles are obtained through spray granulation and are sieved. Pressing ferrite powder into a blank sample of H25×15X8 by a press, sintering at 1110 ℃ for 6 hours under the condition that the oxygen content is controlled to be 21vol% by N 2, then sintering at 1310 ℃ for 2 hours under the condition that the oxygen content is controlled to be 5vol% by N 2, and performing a cooling stage under the condition of balanced oxygen partial pressure to obtain the magnetic core for testing.
The performance indexes of the Mn-Zn ferrite material prepared by the method are shown in Table 1 and Table 2
TABLE 1
TABLE 2
According to the embodiment, the main component in the range of the invention, coO is taken as the main component, the magnetic permeability reaches the target value, the temperature coefficient is extremely low, and the target requirement is met.
As can be seen from comparative examples 1 to 3, the manganese zinc ferrite having main components and auxiliary components added in amounts outside the technical range of the present invention and CoO as only the auxiliary components without pre-sintering has a relatively high temperature coefficient of permeability in the range of 0 to 230 ℃ and a large change in permeability with temperature, so that it is difficult to ensure the normal operation of the electronic device in the temperature range.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
By applying the technical scheme of the invention, the manganese-zinc ferrite material is prepared. The material has a high Curie temperature of greater than 230 ℃, a Bs (25 ℃) of greater than 530mT, and permeability in the temperature range of 0-230 ℃ can realize high permeability and low temperature coefficient. The manganese-zinc ferrite material provided by the invention can realize stable operation under wider and more extreme environmental conditions, and greatly widens the application of the manganese-zinc ferrite in the field of electronic devices.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A manganese-zinc-ferrite material, characterized in that the manganese-zinc-ferrite material comprises a main component and an auxiliary component;
Wherein the main component comprises Fe 2O3: 51.30 to 51.78mol percent, znO:11.42 to 11.64mol percent, mnO:36.58 to 37.27mol%, coO:0.02 to 0.1mol%;
The content of each component of the auxiliary component is based on the total weight of the main component CaCO3：200～2000ppm,Bi2O3：200～2000ppm,MoO：200～2000ppm,NbO：200～2000ppm,ZrO：200～2000ppm.
2. The manganese-zinc-ferrite material according to claim 1, wherein the main component comprises Fe 2O3: 51.02 to 51.63mol percent, znO:11.30 to 11.60mol percent, coO:0.02 to 0.1mol percent, and the balance of MnO;
Preferably, the content of each component of the auxiliary component is based on the total weight of the main component CaCO3：200～1000ppm,Bi2O3：200～1000ppm,MoO：200～800ppm,NbO：200～2000ppm,ZrO：200～2000ppm.
3. The method of preparing a manganese zinc ferrite material according to claim 1 or 2, characterized in that the method comprises the steps of:
S1, presintering: weighing the raw materials of each component of the main component respectively, performing wet ball milling and drying on the raw materials, and presintering to obtain a presintering material;
S2, mixing: carrying out wet ball milling on the pre-sintered material and the raw materials of each component of the auxiliary components to obtain mixed slurry;
S3, tempering: drying the mixed slurry, and tempering to obtain a tempered material;
S4, granulating: drying the tempering material to obtain a drying material, mixing the drying material with a binder, grinding and granulating to obtain granules;
s5, pressing: pressing and molding the granules to obtain a molded body;
s6, sintering: and sintering the molded body to obtain the manganese-zinc ferrite material.
4. The method for preparing a manganese-zinc-ferrite material according to claim 3, wherein the sintering process is carried out at a temperature of 1250-1300 ℃ for a sintering time of 5-7 hours;
Preferably, the oxygen content in the sintering atmosphere in the sintering process is 3-5 vol%, and the rest atmosphere except oxygen in the sintering atmosphere is inert gas.
5. The method of preparing a manganese zinc ferrite material according to claim 3 or 4, further comprising a temperature increasing process prior to the sintering process, the temperature increasing process comprising: under the sintering atmosphere with the oxygen content of 19-21 vol%, firstly heating the molded body to 600-800 ℃ and preserving heat for 2-3 h; and then heating to 1100-1300 ℃ within 6-10 h, and preserving heat for 5-8 h.
6. The method of manufacturing a manganese zinc ferrite material according to any one of claims 3 to 5, further comprising a cooling process after the sintering process, the cooling process being performed at an equilibrium oxygen partial pressure.
7. The method of manufacturing a manganese-zinc-ferrite material according to any one of claims 3 to 6, wherein the pre-firing process is performed under an air atmosphere; the presintering temperature is 650-800 ℃ and the presintering time is 2-3 h.
8. The method of producing a manganese-zinc-ferrite material according to any one of claims 3 to 7, wherein the tempering temperature is 650 to 800 ℃.
9. The method of preparing a manganese zinc ferrite material according to any one of claims 3 to 8, wherein the wet ball milling time is 70 to 90min.
10. The method of producing a manganese-zinc-ferrite material according to any one of claims 3 to 9, characterized in that the particle size of the pellets is 1.0 to 1.05 μm.
11. The method of producing a manganese-zinc-ferrite material according to any one of claims 3 to 10, wherein the binder accounts for 10 to 12wt% of the baking material; the binder comprises one or more of PVA, glue and epoxy resin.
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| JP2010173888A (en) * | 2009-01-29 | 2010-08-12 | Tdk Corp | METHOD FOR PRODUCING MnZn FERRITE |
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