CN118271075A - Direct current superposition resistant wide-temperature low-loss MnZn ferrite and preparation method and application thereof - Google Patents
Direct current superposition resistant wide-temperature low-loss MnZn ferrite and preparation method and application thereof Download PDFInfo
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- CN118271075A CN118271075A CN202410369234.7A CN202410369234A CN118271075A CN 118271075 A CN118271075 A CN 118271075A CN 202410369234 A CN202410369234 A CN 202410369234A CN 118271075 A CN118271075 A CN 118271075A
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- ball milling
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- direct current
- mnzn ferrite
- loss
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 122
- 238000000498 ball milling Methods 0.000 claims abstract description 121
- 239000000843 powder Substances 0.000 claims abstract description 97
- 239000000654 additive Substances 0.000 claims abstract description 73
- 230000000996 additive effect Effects 0.000 claims abstract description 71
- 238000001035 drying Methods 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 229910002367 SrTiO Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 9
- 238000004364 calculation method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 43
- 230000008569 process Effects 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 20
- 230000036961 partial effect Effects 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 17
- 238000003825 pressing Methods 0.000 claims description 15
- 230000002829 reductive effect Effects 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000011858 nanopowder Substances 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011268 mixed slurry Substances 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000010963 304 stainless steel Substances 0.000 claims description 3
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 16
- 230000005415 magnetization Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- 239000000306 component Substances 0.000 description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 13
- 238000011049 filling Methods 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000011162 core material Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910005979 Ge2O3 Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
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Abstract
A direct current superposition resistant wide-temperature low-loss MnZn ferrite and a preparation method and application thereof comprise the following steps: according to 52.3 to 53.3mol percent of Fe 2O3, 35.2 to 36.2mol percent of MnO,0.12 to 0.18mol percent of TiO 2 and the balance of ZnO, the weight of the raw materials required by calculation is obtained to obtain a MnZn ferrite main material; mixing CaCO 3 in 0.12-0.16 wt%, siO 2 in 0.02-0.04 wt%, V 2O5 in 0.03-0.04 wt%, co 2O3 in 0.12-0.18 wt% and SrTiO 3 nanometer powder in 0.1-0.3 wt% to obtain additive; placing the main material into a ball mill for ball milling and mixing for one time, and then drying and presintering; and (3) putting the presintered powder and the additive into a ball mill for secondary ball milling, then drying, granulating, forming into annular green blanks, and sintering the annular green blanks to obtain the ferrite. The MnZn ferrite material with high direct current superposition resistance and low loss can be prepared, the magnetization magnetic permeability is 2933, H μ70, namely, the direct current superposition magnetic field value corresponding to the magnetic permeability reduction of 70% is 200A/m, and the loss in the range of 25-100 ℃ is lower than 330kW/m 3 under 100kHz 200 mT.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a direct current superposition resistant wide-temperature low-loss MnZn ferrite, a preparation method and application thereof.
Background
The high-speed development of the power electronic technology enables magnetic components such as filters, transformers, power inductors and the like to be widely applied. MnZn ferrite has high resistivity, high initial permeability and low loss, and ferrite cores made therefrom are the core components of these magnetic elements. The performance of MnZn ferrite is closely related to the overall performance of the device, especially the loss of the core has a decisive influence on the efficiency and stability of the device. The properties of MnZn ferrite are closely related to the exterior. On the one hand, the MnZn ferrite core is often impacted by an external magnetic field, for example, electromagnetic fields radiated by other electromagnetic elements during operation can reduce the magnetic permeability of materials, and further reduce the inductance value of devices; on the other hand, the loss of the core varies with the temperature of the external environment. In general, as the temperature increases, the loss-temperature characteristic curve of the MnZn ferrite presents a "concave" curve, and when the loss curve reaches the lowest value, the corresponding temperature is the most suitable working temperature of the material, at this time, the material loss is the lowest, and the efficiency of the magnetic element is the highest. When the ambient temperature deviates from this temperature, the loss of material increases and the efficiency of the magnetic element decreases, thereby decreasing the energy conversion efficiency of the switching power supply. This loss characteristic of MnZn ferrite severely constrains its versatility of application in different temperature ranges. In the process of designing a device, mnZn ferrite materials with corresponding loss-temperature characteristics can be selected only for different working temperatures of the device. This not only makes MnZn ferrite materials of a wide variety and increases production costs, but also increases core loss once the operating temperature of the ferrite core deviates from its optimum operating temperature range, and decreases device efficiency, even with the vicious circle of "loss increase-temperature increase-loss further increase". With the development of integration of electronic devices, the working environment of the MnZn ferrite core is also more and more severe, and how to keep the excellent performance of the core in complex electromagnetic and temperature environments, and the application range of the MnZn ferrite is widened is a difficult problem to be solved in the electronic information industry.
In the patent 'a preparation method of a medium-broadband wide-temperature low-loss MnZn ferrite material' (CN 112573912A), caCO 3、SiO2、Nb2O5、ZrO2、Co2O3 is adopted as an additive, and the main components are in mole percent: 52.5 to 53.5mol percent of Fe 2O3, 8.8 to 9.8mol percent of ZnO and the balance of MnO; the additive comprises the following auxiliary components in percentage by weight: caCO 3 is 0.04-0.06%, nb 2O5 is 0.02-0.03%, co 2O3 is 0.35-0.45%, zrO 2 is 0.01-0.03%, siO 2 is 30-120 ppm, the grain size of sintered ferrite is regulated, the grain refinement is realized, and meanwhile, the loss caused by the dispersibility of the grain size of ferrite is reduced, but the scheme aims at a wide frequency range (100-500 kHz), the loss at the medium frequency is still very high, the loss at 25-100 ℃ exceeds 560kW/m 3 under the condition of 500kHz 100mT, and the patent does not regulate the direct current superposition characteristic. Therefore, the invention can further reduce the loss at the intermediate frequency and improve the direct current superposition resistance of the material.
The patent 'a low-loss MnZn power ferrite and a preparation method thereof' (CN 113956031A) discloses a MnZn ferrite material which consists of a main component and auxiliary materials, wherein the main component comprises 52.38-52.49 mol% of Fe 2O3, 8.69-8.78 mol% of ZnO and the balance of MnO; the inclusion of 0.07～0.08wt％CaCO3、0.0035～0.04wt％Nb2O5、0.46～0.47wt％Co2O3、0.15～0.2wt％SnO2, reduces losses over a wide frequency range of 100-300kHz, but no exploration is made for the dc superposition characteristics of the material.
The patent 'high-bandwidth, low-temperature and low-loss MnZn ferrite material and a preparation method thereof' (CN 110517840A) discloses a MnZn ferrite material, which consists of a main component and an auxiliary component, wherein the main component comprises 71-77.4 mol% of Fe 2O3 and 2-13.8 mol% of ZnO, 0.001-1 mol% of Ni 2O3 and the balance of Mn 3O4; the auxiliary component comprises CaCO3：200～2000ppm、Nb2O5：0～500ppm、V2O5：0～500ppm、SnO2：0～1000ppm、TiO2：0～2000ppm、ZrO2：0～200ppm、Ta2O5：0～200ppm、GeO2：0～1000ppm、Co3O4：0～3000ppm、Bi2O3：0～1000ppm、SiO2：0～200ppm, of the prepared material, which has the characteristic of keeping lower loss in the range of medium and high frequency (500 kHz-5 MHz) and wide temperature (-30-140 ℃), and enlarges the temperature use range.
In summary, the materials disclosed in the above patent are only aimed at the loss in the mid-frequency range, and the direct current superposition characteristics of the materials are considered. Aiming at the problem, the invention can reduce the high-temperature loss of the material and simultaneously consider the direct current superposition characteristic of the material.
Patent 'Wide Wen Naichao heavy current MnZn ferrite material and preparation method thereof' (CN 113292331A) discloses a MnZn ferrite material, the main components are: fe 2O3: 51.80 to 54.00mol percent, znO: 15.00-18.00 mol%, mnO:29.50 to 32.00mol%; the auxiliary components ：Nb2O5：100～500ppm,ZrO2：200～600ppm,TiO2：100～500ppm,CaCO3：300～800ppm,SiO2：10～80ppm,Co2O3：2000～5000ppm,V2O5：100～500ppm. are that the superposition characteristics of-40 ℃ and 85 ℃ and the magnetic permeability and the incremental magnetic permeability of the material are comprehensively controlled by adjusting and controlling the content of Fe 2O3 and the content of additives Co 2O3 and V 2O5, the prepared material has good direct current superposition characteristics within-40 ℃ to 85 ℃, but the temperature characteristics of loss are not considered, and the 100kHz 200mT loss within-40 ℃ to 85 ℃ is more than 400kW/m 3.
The patent MnZn ferrite material with high direct current superposition characteristics and a preparation method thereof (CN 105174932A) disclose the MnZn ferrite material with high direct current superposition characteristics, which is characterized in that the material comprises main materials and doping agents, wherein the main materials comprise 53.0-55.0 mol% of Fe 2O3, 38.0-40.0 mol% of MnO, 0-1.5 mol% of NiO and the balance of ZnO, the weight of the main materials is calculated as the basis, and the doping agents comprise the following components in terms of oxide: the MnZn ferrite with high temperature, low loss and high direct current superposition characteristics is obtained by 0.02 to 0.20wt% nanometer CaCO3、0.001～0.10wt％V2O5、0.001～0.06wt％Bi2O3、0.01～0.40wt％Co2O3、0.01～0.09wt％ZrO2、0.01～0.20wt％Ge2O3,. The invention regulates the direct current superposition characteristic of magnetic permeability to a certain extent, but the magnetic permeability is reduced to 85% of the initial value in a 250mA direct current magnetic field, and the invention aims at the loss at low frequency of 100kHz and does not explore the loss condition in the range of 500kHz of intermediate frequency. Similarly, patent publication 10033613.6a and 10518405.6 disclose similar high temperature low loss materials with good dc superposition characteristics, but are directed to high Wen Sunhao at low frequencies and do not explore the loss temperature characteristics at medium frequencies.
The material disclosed by the patent combines the direct current superposition resistance and the loss of the material to a certain extent, but aims at the loss under low frequency, and does not explore the loss condition under the medium frequency condition. In order to reduce the volume of the power supply, the operating frequency of the core material is continuously increased from a low frequency (100 kHz) to an intermediate frequency (500 kHz). Based on the method, the MnZn ferrite material with direct current superposition resistance and low medium frequency loss is prepared by inhibiting the loss at the medium frequency on the premise of considering the direct current superposition characteristic of the material.
Disclosure of Invention
The invention aims to provide a direct current superposition resistant wide-temperature low-loss MnZn ferrite, a preparation method and application thereof, so as to solve the problem of loss at low frequency.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
In a first aspect, the invention provides a method for preparing a direct current superposition resistant wide-temperature low-loss MnZn ferrite, which comprises the following steps:
According to 52.3 to 53.3mol percent of Fe 2O3, 35.2 to 36.2mol percent of MnO,0.12 to 0.18mol percent of TiO 2 and the balance of ZnO, the weight of the raw materials required by calculation is obtained to obtain a MnZn ferrite main material;
Mixing CaCO 3 in 0.12-0.16 wt%, siO 2 in 0.02-0.04 wt%, V 2O5 in 0.03-0.04 wt%, co 2O3 in 0.12-0.18 wt% and SrTiO 3 nanometer powder in 0.1-0.3 wt% to obtain additive;
placing the main material into a ball mill for ball milling and mixing for one time, and then drying and presintering;
And (3) putting the presintered powder and the additive into a ball mill for secondary ball milling, then drying, granulating, forming into annular green blanks, and sintering the annular green blanks to obtain the ferrite.
Optionally, during one-time ball milling, the main material is put into a ball mill for ball milling and mixing, the ball milling time is 2-4 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, the mixed slurry is put into an oven for drying for 24 hours, and the slurry is sieved by a 40-mesh sieve after being dried; during secondary ball milling, the ball milling time is 4.5-5.5 h, and the rotating speed is 241 rpm; srTiO 3 contained in the additive is nano powder, and the particle size is 30-100 nm.
Optionally, the primary material after one ball milling is dried and then put into a muffle furnace for presintering, the temperature is 900-910 ℃, the heat preservation time is 2.0-2.5 h, and the atmosphere is air.
Optionally, during granulation, the powder after secondary ball milling is dried, and then 12.5 to 16.5 weight percent of PVA glue is added to mix the powder with the glue
Optionally, during molding, filling the granulated powder into a mold, and pressing into annular green blanks by a hydraulic press, wherein the pressure is 6-7 MPa, and the pressure maintaining time is 10-15 s;
Optionally, during sintering, placing the green body into an atmosphere tube furnace, sintering at 1310-1330 ℃, keeping the temperature for 5 hours, keeping the oxygen partial pressure at the temperature keeping stage between 2.4 and 2.7 percent, and then gradually cooling to room temperature; the cooling stage is divided into 3 stages: the first stage is to keep the temperature at 1150 ℃ and reduce the oxygen partial pressure to 0.8%; the second stage is 1150-950 deg.c, oxygen partial pressure reduced to 0.08%; the third stage is 950-50 deg.c and oxygen pressure drop to 0.01%.
Optionally, a hand rubbing method is adopted in the Step4 granulation process, and after powder is mixed with PVA glue, the powder is rubbed by hand for 20-30 min until the powder is changed from a loose state to a quicksand state; in the molding process, zinc stearate accounting for 2-3wt% is added into the powder before pressing, and the powder is mixed for 5min by using a stirrer so as to facilitate demoulding of a green body; in the molding process, the pressure is applied in the sequence of rising to 3-4 MPa and keeping for 5s, so that the gas in the powder is fully discharged, and then rising to 6-7 MPa and keeping for 10-15 s.
Optionally, in the primary ball milling and secondary ball milling processes, the adopted ball milling medium is deionized water and stainless steel balls, and the powder is: deionized water: the weight ratio of the steel balls is 1:1.6:3, a step of; the steel balls are made of 304 stainless steel, and are formed by mixing four stainless steel balls with different specifications according to a specific weight ratio, wherein the weight ratio is phi 1.5mm: Φ3.0mm: phi 5.0mm: Φ8.5mm=1: 3:3:4, a step of;
In a second aspect, the invention provides a direct current superposition-resistant wide-temperature low-loss MnZn ferrite, which is prepared by a preparation method of the direct current superposition-resistant wide-temperature low-loss MnZn ferrite.
In a third aspect, the invention provides an application of a direct current superposition-resistant wide-temperature low-loss MnZn ferrite, and the direct current superposition-resistant wide-temperature low-loss MnZn ferrite is applied to electronic elements.
Compared with the prior art, the invention has the following technical effects:
The invention provides a direct current superposition resistant low-loss MnZn ferrite material and a preparation method thereof. Firstly, the main material is composed of MnZnFeTi quaternary system, ti 4+ is directly introduced into the main formula of MnZn ferrite, compared with the traditional method of adding TiO 2 in the secondary ball milling process, ti4 < + > can well enter the crystal lattice of the MnZn ferrite and form an ion pair with Fe 2+, the grain resistivity is improved, the eddy current loss is suppressed, the magnetocrystalline anisotropy constant can be regulated, and the direct current superposition resistance of the MnZn ferrite is improved. And secondly, nanometer SrTiO 3 particles with high resistivity are introduced into the additive, so that a grain boundary with high resistivity can be constructed, and the eddy current loss is further reduced. Finally, in the preparation method, steel balls with specific proportions are used in the ball milling process, so that the ball milling efficiency can be increased and the introduced impurities can be reduced; the two-step pressing method is adopted in the forming process, so that gas in the powder can be effectively discharged, and densification of the green body is facilitated.
The invention provides a MnZn power ferrite material which is resistant to direct current superposition and low in loss. The main materials are Fe 2O3、MnO、TiO2 and ZnO, wherein the introduction of Ti 4+ can increase the content of Fe 2+ with positive magnetocrystalline anisotropy, so that the direct current superposition resistance of the material is effectively improved, meanwhile, ti 4+ can bind Fe 2+, the electron transition process between the Ti and Fe 3+ is avoided, and the resistivity of crystal grains is improved.
According to the invention, steel balls with a specific proportion are used as ball milling media in the ball milling process, so that powder can be quickly and uniformly mixed, and pre-sintered powder is ground into particles smaller than 1 micrometer, thereby being beneficial to uniform growth of crystal grains. And in the molding process, a step-by-step pressurizing method is adopted to fully release air in the powder material, so that a compact green body is obtained, and air holes generated in the sintering process are reduced. The additive nanometer SrTiO 3 particles can be enriched in the grain boundary of the MnZn ferrite to construct a high-resistance grain boundary layer, so that the resistivity of the MnZn ferrite is further improved.
Through the scheme, the MnZn ferrite material with high direct current superposition resistance and low loss can be prepared, the magnetization magnetic permeability is 2933, H μ70, namely, the direct current superposition magnetic field value corresponding to the magnetic permeability reduction of 70% is 200A/m, and the loss in the range of 25-100 ℃ is lower than 330kW/m 3 under 100kHz 200 mT.
Drawings
FIG. 1 shows the change of MnZn ferrite permeability with the DC superimposed magnetic field.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s).
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be a mass unit which is known in the chemical industry field such as mu g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
At 100khz 200mt, the loss of MnZn consists of hysteresis loss and eddy current loss, where the eddy current loss is closely related to the resistivity of the material. Studies have shown that Ti 4+ ions can form ion pairs with Fe 2+ ions in MnZn ferrite, which will bind Fe 2+ ions, thereby reducing the electron transition process between Fe 2+ ions and Fe 2+ ions, and improving the material resistivity. Meanwhile, fe 2+ ions have positive magnetocrystalline anisotropy, so that the magnetocrystalline anisotropy constant of the MnZn ferrite can be influenced, and the direct current superposition characteristic of magnetic conductivity can be further adjusted. In general, ti 4+ is introduced by adding an additive TiO 2 in the secondary ball milling process, but Ti 4+ introduced by the method is difficult to completely enter a crystal lattice, and the rest part is enriched in a crystal boundary to form a hetero-phase, so that the electromagnetic performance of the MnZn ferrite is deteriorated. On the one hand, ti 4+ is directly introduced into a main formula of the MnZn ferrite to promote the MnZn ferrite to enter a crystal lattice of the MnZn ferrite, so that the grain resistivity is improved, and meanwhile, the magnetocrystalline anisotropy constant is regulated, and the direct current superposition resistance of the MnZn ferrite is improved; on the other hand, nanometer SrTiO 3 particles with high resistivity are introduced into the additive to construct grain boundaries with high resistivity, so that eddy current loss is reduced. Based on the thought, the magnetocrystalline anisotropy and the grain/grain boundary conductivity of the MnZn ferrite are regulated and controlled simultaneously, so that the MnZn ferrite with direct current superposition resistance and low loss can be prepared
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
In a first aspect, the application provides a MnZn power ferrite material which is resistant to direct current superposition and low in loss, and the composition of the MnZn power ferrite material comprises a main material and an additive.
In the scheme, the main material is 52.3 to 53.3mol percent of Fe 2O3, 35.2 to 36.2mol percent of MnO,0.12 to 0.18mol percent of TiO 2 and the balance of ZnO; the additive is CaCO 3 accounting for 0.12-0.16 wt% of the weight of the main material, siO 2 accounting for 0.02-0.04 wt% of the weight of the main material, V 2O5 accounting for 0.03-0.04 wt% of the weight of the main material, co 2O3 accounting for 0.12-0.18 wt% of the weight of the main material and SrTiO 3 accounting for 0.1-0.3 wt% of the weight of the main material.
In a second aspect, the application provides a preparation method of a MnZn power ferrite material with direct current superposition resistance and low loss, which comprises the following preparation processes:
Step 1 is configured with a MnZn ferrite main material. According to 52.3 to 53.3mol percent of Fe 2O3, 35.2 to 36.2mol percent of MnO,0.12 to 0.18mol percent of TiO 2 and the balance of ZnO, the weight of the required raw materials is calculated, and the raw materials are accurately weighed by using an analytical balance.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 2-4 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900-910 ℃ for 2.0-2.5 h under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the presintered powder, and weighing the required additive according to the weight of the presintered powder, wherein the additive comprises 0.12-0.16 wt% of CaCO 3, 0.02-0.04 wt% of SiO 2, 0.03-0.04 wt% of V 2O5, 0.12-0.18 wt% of Co 2O3 and 0.1-0.3 wt% of SrTiO 3 nano powder;
Step 5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 4.5 to 5.5 hours at the rotating speed of 241 rpm;
step 6 granulating. Drying the powder after secondary ball milling, adding 12.5-16.5 wt% of PVA glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6-7 MPa, and the pressure maintaining time is 10-15 s;
Step 8 sintering. Sintering the green embryo in an atmosphere tube furnace at 1310-1330 deg.c for 5 hr with oxygen partial pressure of 2.4-2.7% and cooling to room temperature gradually.
Using an LCR digital bridge (TH 2828) and a direct current power supply (PLR 36-20) to test the magnetic conductivity of the annular sample, wherein the number of winding turns is 10, and the test condition is 1kHz 1A/m 25 ℃; the loss P cv of the annular sample in the range of 25-100 ℃ was measured using a BH analyzer (IWATSU SY-8218), with 5 turns of wire winding, under 100kHz 200mT conditions.
Specific:
The invention provides a direct current superposition resistant MnZn power ferrite material with low loss, which consists of components and additives, wherein the main component comprises 52.30-53.30 mol% of Fe 2O3, 35.20-36.20 mol% of MnO, 0.20-0.40 mol% of TiO 2 and the balance of ZnO; the additive comprises CaCO 3 accounting for 0.12-0.16 wt% of the weight of the main material, siO 2 accounting for 0.02-0.04 wt% of the weight of the main material, V 2O5 accounting for 0.03-0.04 wt% of the weight of the main material, co 2O3 accounting for 0.12-0.18 wt% of the weight of the main material and SrTiO 3 accounting for 0.1-0.3 wt% of the weight of the main material.
Besides Fe 2O3, mnO and ZnO, tiO 2 is also added into the main material to form a MnZnFeTi quaternary system;
SrTiO 3 contained in the additive is nano powder, and the particle size is 30-100 nm;
The method comprises the following steps:
Step 1 is configured with a MnZn ferrite main material. According to 52.3 to 53.3mol percent of Fe 2O3, 35.2 to 36.2mol percent of MnO,0.12 to 0.18mol percent of TiO 2 and the balance of ZnO, the weight of the required raw materials is calculated, and the raw materials are accurately weighed by using an analytical balance.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 2-4 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900-910 ℃ for 2.0-2.5 h under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the presintered powder, and weighing the required additive according to the weight of the presintered powder, wherein the additive comprises 0.12-0.16 wt% of CaCO 3, 0.02-0.04 wt% of SiO 2, 0.03-0.04 wt% of V 2O5, 0.12-0.18 wt% of Co 2O3 and 0.1-0.3 wt% of SrTiO 3 nano powder;
Step 5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 4.5 to 5.5 hours at the rotating speed of 241 rpm;
step 6 granulating. Drying the powder after secondary ball milling, adding 12.5-16.5 wt% of PVA glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6-7 MPa, and the pressure maintaining time is 10-15 s;
step 8 sintering. Placing the green body into an atmosphere tube furnace, sintering at 1310-1330 ℃ for 5h, wherein the oxygen partial pressure in the heat preservation stage is 2.4-2.7%, and then gradually cooling to room temperature;
in the process of Step1 primary ball milling and Step3 secondary ball milling, the adopted ball milling medium is deionized water and stainless steel balls, and the powder is prepared from the following materials: deionized water: the weight ratio of the steel balls is 1:1.6:3, a step of;
In the process of the primary ball milling of Step1 and the secondary ball milling of Step3, the steel balls are made of 304 stainless steel, and are formed by mixing four stainless steel balls with different specifications according to a specific weight ratio, wherein the weight ratio is phi 1.5mm: Φ3.0mm: phi 5.0mm: Φ8.5mm=1: 3:3:4, a step of;
The Step4 granulation process adopts a manual rubbing method, and after powder is mixed with PVA glue, the powder is rubbed by hand for 20-30 min until the powder is changed from a loose state to a quicksand state;
in the Step5 forming process, 2-3wt% of zinc stearate is added into the powder before pressing, and the powder is mixed for 5min by using a stirrer so as to facilitate demoulding of a green body;
In the Step5 forming process, the pressure is firstly increased to 3-4 MPa and kept for 5s, so that the gas in the powder is fully discharged, and then is slowly increased to 6-7 MPa and kept for 10-15 s;
In the Step6 sintering process, the cooling stage is divided into 3 stages: the first stage is to keep the temperature at 1150 ℃ and reduce the oxygen partial pressure to 0.8%; the second stage is 1150-950 deg.c, oxygen partial pressure reduced to 0.08%; the third stage is 950-50 deg.c and oxygen pressure drop to 0.01%.
Examples
Table 1 examples 1 to 6 main materials, additive components and holding temperatures
Example 1
A preparation method of a direct current superposition resistant low-loss MnZn power ferrite material comprises the following preparation steps:
step 1 is configured with a MnZn ferrite main material. The required raw material weights were calculated as 52.3mol% Fe 2O3,36.2mol％MnO,0.12mol％TiO2, 11.38mol% ZnO and accurately weighed using an analytical balance.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 3 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900 ℃ for 2 hours under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the pre-sintered powder, and weighing the required additive according to the weight of the pre-sintered powder, wherein the additive comprises 0.12wt% of CaCO 3, 0.03wt% of SiO 2, 0.03wt% of V 2O5, 0.15wt% of C o2O3 and 0.1wt% of SrTiO 3 nano powder;
Step5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 5 hours at the rotating speed of 241 rpm;
Step 6 granulating. Drying the powder after secondary ball milling, adding 14.5wt% of PVA (polyvinyl alcohol) glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6MPa, and the pressure maintaining time is 10s;
Step 8 sintering. Placing the green body into an atmosphere tube furnace, sintering at 1310 ℃, keeping the temperature for 5 hours, keeping the oxygen partial pressure at the temperature keeping stage at 2.5%, and then gradually cooling to room temperature;
Example 2
A preparation method of a direct current superposition resistant low-loss MnZn power ferrite material comprises the following preparation steps:
step 1 is configured with a MnZn ferrite main material. The required raw material weight was calculated from 52.4mol% Fe 2O3,36.1mol％MnO,0.13mol％TiO2, 11.37mol% ZnO and accurately weighed.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 3 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900 ℃ for 2 hours under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the pre-sintered powder, and weighing the required additive according to the weight of the pre-sintered powder, wherein the additive comprises 0.12wt% of CaCO 3, 0.03wt% of SiO 2, 0.03wt% of V 2O5, 0.15wt% of Co 2O3 and 0.1wt% of SrTiO 3 nano powder;
Step5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 5 hours at the rotating speed of 241 rpm;
Step 6 granulating. Drying the powder after secondary ball milling, adding 14.5wt% of PVA (polyvinyl alcohol) glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6MPa, and the pressure maintaining time is 10s;
Step 8 sintering. Placing the green body into an atmosphere tube furnace, sintering at 1310 ℃, keeping the temperature for 5 hours, keeping the oxygen partial pressure at the temperature keeping stage at 2.5%, and then gradually cooling to room temperature;
Example 3
A preparation method of a direct current superposition resistant low-loss MnZn power ferrite material comprises the following preparation steps:
Step 1 is configured with a MnZn ferrite main material. The required raw material weight was calculated from 52.6mol% Fe 2O3,35.9mol％MnO,0.14mol％TiO2, 11.36mol% ZnO and accurately weighed.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 3 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900 ℃ for 2 hours under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the pre-sintered powder, and weighing the required additive according to the weight of the pre-sintered powder, wherein the additive comprises 0.12wt% of CaCO 3, 0.03wt% of SiO 2, 0.03wt% of V 2O5, 0.15wt% of C o2O3 and 0.2wt% of SrTiO 3 nano powder;
Step5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 5 hours at the rotating speed of 241 rpm;
Step 6 granulating. Drying the powder after secondary ball milling, adding 14.5wt% of PVA (polyvinyl alcohol) glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6MPa, and the pressure maintaining time is 10s;
Step 8 sintering. Placing the green body into an atmosphere tube furnace, sintering at 1320 ℃, keeping the temperature for 5 hours, keeping the oxygen partial pressure at the temperature keeping stage at 2.5%, and then gradually cooling to room temperature;
Example 4
A preparation method of a direct current superposition resistant low-loss MnZn power ferrite material comprises the following preparation steps:
step 1 is configured with a MnZn ferrite main material. The required raw material weight was calculated from 52.8mol% Fe 2O3,35.7mol％MnO,0.15mol％TiO2, 11.35mol% ZnO and accurately weighed.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 3 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900 ℃ for 2 hours under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the pre-sintered powder, and weighing the required additive according to the weight of the pre-sintered powder, wherein the additive comprises 0.12wt% of CaCO 3, 0.03wt% of SiO 2, 0.03wt% of V 2O5, 0.15wt% of C o2O3 and 0.2wt% of SrTiO 3 nano powder;
Step5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 5 hours at the rotating speed of 241 rpm;
Step 6 granulating. Drying the powder after secondary ball milling, adding 14.5wt% of PVA (polyvinyl alcohol) glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6MPa, and the pressure maintaining time is 10s;
Step 8 sintering. Placing the green body into an atmosphere tube furnace, sintering at 1320 ℃, keeping the temperature for 5 hours, keeping the oxygen partial pressure at the temperature keeping stage at 2.5%, and then gradually cooling to room temperature;
Example 5
A preparation method of a direct current superposition resistant low-loss MnZn power ferrite material comprises the following preparation steps:
Step 1 is configured with a MnZn ferrite main material. The required raw material weight was calculated from 53.0mol% Fe 2O3,35.5mol％MnO,0.16mol％TiO2, 11.34mol% ZnO and accurately weighed.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 3 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900 ℃ for 2 hours under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the pre-sintered powder, and weighing the required additive according to the weight of the pre-sintered powder, wherein the additive comprises 0.12wt% of CaCO 3, 0.03wt% of SiO 2, 0.03wt% of V 2O5, 0.15wt% of Co 2O3 and 0.2wt% of SrTiO 3 nano powder;
Step5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 5 hours at the rotating speed of 241 rpm;
Step 6 granulating. Drying the powder after secondary ball milling, adding 14.5wt% of PVA (polyvinyl alcohol) glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6MPa, and the pressure maintaining time is 10s;
Step 8 sintering. Placing the green body into an atmosphere tube furnace, sintering at 1320 ℃, keeping the temperature for 5 hours, keeping the oxygen partial pressure at the temperature keeping stage at 2.5%, and then gradually cooling to room temperature;
Example 6
A preparation method of a direct current superposition resistant low-loss MnZn power ferrite material comprises the following preparation steps:
Step 1 is configured with a MnZn ferrite main material. The required raw material weight was calculated from 53.3mol% Fe 2O3,35.2mol％MnO,0.18mol％TiO2, 11.32mol% ZnO and accurately weighed.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 3 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900 ℃ for 2 hours under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the pre-sintered powder, and weighing the required additive according to the weight of the pre-sintered powder, wherein the additive comprises 0.12wt% of CaCO 3, 0.03wt% of SiO 2, 0.03wt% of V 2O5, 0.15wt% of Co 2O3 and 0.3wt% of SrTiO 3 nano powder;
Step5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 5 hours at the rotating speed of 241 rpm;
Step 6 granulating. Drying the powder after secondary ball milling, adding 14.5wt% of PVA (polyvinyl alcohol) glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6MPa, and the pressure maintaining time is 10s;
step 8 sintering. Placing the green body into an atmosphere tube furnace, sintering at 1330 ℃, keeping the temperature for 5 hours, keeping the oxygen partial pressure at the heat-preserving stage to be 2.5%, and then gradually cooling to room temperature;
Comparative example
Table 2 main materials and additive components of comparative examples 1 and 2 and holding temperatures
Comparative example 1
A preparation method of a MnZn power ferrite material comprises the following preparation steps:
Step 1 is configured with a MnZn ferrite main material. The required raw material weight was calculated from 52.3mol% Fe 2O3,36.2mol％MnO,0.05mol％TiO2, 11.45mol% ZnO and accurately weighed.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 3 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900 ℃ for 2 hours under the atmosphere of air;
Step 4, preparing an additive. Adding an additive into the pre-sintered powder, and weighing the required additive according to the weight of the pre-sintered powder, wherein the additive comprises 0.12wt% of CaCO 3, 0.03wt% of SiO 2, 0.03wt% of V 2O5, 0.15wt% of C o2O3 and 0.0wt% of SrTiO 3 nano powder;
Step5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 5 hours at the rotating speed of 241 rpm;
Step 6 granulating. Drying the powder after secondary ball milling, adding 14.5wt% of PVA (polyvinyl alcohol) glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6MPa, and the pressure maintaining time is 10s;
Step 8 sintering. Placing the green body into an atmosphere tube furnace, sintering at 1310 ℃, keeping the temperature for 5 hours, keeping the oxygen partial pressure at the temperature keeping stage at 2.5%, and then gradually cooling to room temperature;
comparative example 2
A preparation method of a MnZn power ferrite material comprises the following preparation steps:
Step 1 is configured with a MnZn ferrite main material. The required raw material weight was calculated from 53.3mol% Fe 2O3,35.2mol％MnO,0.25mol％TiO2, 11.25mol% ZnO and accurately weighed.
Step 2, ball milling for the first time: putting the main material into a ball mill for ball milling and mixing, wherein the ball milling time is 3 hours, the ball milling medium is zirconium balls with the diameter of 3mm, the ball milling rotating speed is 241 r/min, and the mixed slurry is put into an oven for drying for 24 hours and then is sieved by a 40-mesh sieve;
Step 3 presintering. Drying the primary ball-milled main material, and placing the dried main material into a muffle furnace for presintering at 900 ℃ for 2.0h under the atmosphere of air;
step 4, preparing an additive. Adding an additive into the pre-sintered powder, and weighing the required additive according to the weight of the pre-sintered powder, wherein the additive comprises 0.12wt% of CaCO 3, 0.03wt% of SiO 2, 0.03wt% of V 2O5, 0.15wt% of C o2O3 and 0.5wt% of SrTiO 3 nano powder;
Step5, ball milling is carried out twice. The presintered powder and the additive are simultaneously put into a ball mill for ball milling for 5 hours at the rotating speed of 241 rpm;
Step 6 granulating. Drying the powder after secondary ball milling, adding 14.5wt% of PVA (polyvinyl alcohol) glue, and mixing the powder with the glue;
Step 7, molding. Filling the granulated powder into a mould, and pressing into annular green blanks by using a hydraulic press, wherein the pressure is 6MPa, and the pressure maintaining time is 10s;
Step 8 sintering. The green body is put into an atmosphere tube furnace, sintered at 1330 ℃ for 5 hours, the oxygen partial pressure in the heat preservation stage is 2.5%, and then gradually cooled to room temperature.
TABLE 3 Table 3
As can be seen from Table 3 and the performance parameters of examples 1 to 6 in FIG. 1, the MnZn ferrite prepared by adjusting the Ti substitution amount in the main formula and the doping amount of the nanometer SrTiO 3 in the additive and combining the adjustment of the sintering temperature has high magnetic initial permeability and saturated magnetic induction intensity, excellent direct current superposition resistance and low magnetic core loss.
In comparative examples 1 and 2, after the Ti substitution amount was increased with the same SrTiO 3 doping amount, the initial permeability was slightly decreased due to the increase of Fe 2+ content, H μ70 was slightly increased, and the saturation induction was slightly increased due to the increase of Fe content, and the loss was lower than 360kW/m 3 in the range of 25-100 ℃.
Compared with examples 1 and 2, examples 3,4 and 5 simultaneously improve the doping amount and the Ti substitution amount of SrTiO 3, on one hand, the grain resistance is improved by the constraint effect of Ti ions on Fe 2+ ions; on the other hand, the SrTiO 3 is used for constructing a high-resistance grain boundary, so that the resistivity of the MnZn ferrite is improved, and the loss in the range of 25-100 ℃ is further reduced. Meanwhile, the increase of Ti ions means that Fe 2+ ions with positive magnetocrystalline anisotropy are increased, so that H μ70 is increased, and the direct current superposition resistance of the material is further improved. Since high melting point SrTiO 3 inhibits MnZn ferrite grain growth, the sintering temperature is also raised to 1320 ℃ to ensure sufficient MnZn ferrite grain growth.
Example 6 further increased the doping amount of SrTiO 3 and the Ti substitution amount compared to examples 3, 4, 5. Although H μ70 increases, the initial permeability also decreases to 3014 and the loss at 25-100 ℃ is not significantly reduced.
Compared with examples 1-6, the substitution amount of Ti in comparative example 1 is small, srTiO 3 is not doped, and although the initial magnetic permeability and the saturation magnetic induction intensity are maximum, H μ70 is only 67A/m, which shows that the direct current superposition resistance is poor and the loss in the range of 25-100 ℃ is large.
In comparative example 2, the substitution amount of Ti was greatly increased compared with examples 1 to 6, and although H μ70 was increased to 142A/m and the dc superposition resistance was improved, the binding effect of Ti ions was limited, and excessive Fe 2+ caused the decrease in grain resistivity and the loss to be drastically increased. Even if the doping amount of SrTiO 3 is increased synchronously, the resistivity of MnZn ferrite cannot be restrained from being reduced, but the initial permeability and the saturation induction intensity are reduced due to the introduction of excessive nonmagnetic phases.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (10)
1. The preparation method of the direct current superposition resistant wide-temperature low-loss MnZn ferrite is characterized by comprising the following steps of:
According to 52.3 to 53.3mol percent of Fe 2O3, 35.2 to 36.2mol percent of MnO,0.12 to 0.18mol percent of TiO 2 and the balance of ZnO, the weight of the raw materials required by calculation is obtained to obtain a MnZn ferrite main material;
Mixing CaCO 3 in 0.12-0.16 wt%, siO 2 in 0.02-0.04 wt%, V 2O5 in 0.03-0.04 wt%, co 2O3 in 0.12-0.18 wt% and SrTiO 3 nanometer powder in 0.1-0.3 wt% to obtain additive;
placing the main material into a ball mill for ball milling and mixing for one time, and then drying and presintering;
And (3) putting the presintered powder and the additive into a ball mill for secondary ball milling, then drying, granulating, forming into annular green blanks, and sintering the annular green blanks to obtain the ferrite.
2. The method for preparing the direct current superposition resistant wide-temperature low-loss MnZn ferrite according to claim 1, wherein during one ball milling, main materials are put into a ball mill for ball milling and mixing, the ball milling time is 2-4 h, ball milling media are zirconium balls with phi 3mm, the ball milling rotating speed is 241 r/min, the mixed slurry is put into an oven for drying for 24h, and the dried slurry is sieved by a 40-mesh sieve; during secondary ball milling, the ball milling time is 4.5-5.5 h, and the rotating speed is 241 rpm; srTiO 3 contained in the additive is nano powder, and the particle size is 30-100 nm.
3. The method for preparing the direct current superposition resistant wide-temperature low-loss MnZn ferrite according to claim 1, wherein the main material after primary ball milling is dried and then put into a muffle furnace for presintering, the temperature is 900-910 ℃, the heat preservation time is 2.0-2.5 h, and the atmosphere is air.
4. The method for preparing direct current superposition resistant wide temperature range low loss MnZn ferrite according to claim 1, wherein, during granulation, the powder after secondary ball milling is dried, and then 12.5-16.5 wt% of PVA glue is added to mix the powder with the glue.
5. The method for preparing the MnZn ferrite with direct current superposition resistance and wide temperature range and low loss according to claim 1, wherein during molding, the granulated powder is filled into a mold, and is pressed into annular green blanks by a hydraulic press, the pressure is 6-7 MPa, and the dwell time is 10-15 s.
6. The method for preparing the direct current superposition resistant wide-temperature low-loss MnZn ferrite according to claim 1, which is characterized in that, during sintering, the green body is put into an atmosphere tube furnace, sintering is carried out at 1310-1330 ℃, the heat preservation time is 5h, the oxygen partial pressure in the heat preservation stage is 2.4-2.7%, and then the temperature is gradually reduced to room temperature; the cooling stage is divided into 3 stages: the first stage is to keep the temperature at 1150 ℃ and reduce the oxygen partial pressure to 0.8%; the second stage is 1150-950 deg.c, oxygen partial pressure reduced to 0.08%; the third stage is 950-50 deg.c and oxygen pressure drop to 0.01%.
7. The method for preparing the direct current superposition resistant wide-temperature low-loss MnZn ferrite according to claim 1, wherein a hand rubbing method is adopted in the Step4 granulation process, and after powder and PVA glue are mixed, the powder is rubbed by hand for 20-30 min until the powder is changed from a loose state to a quicksand state; in the molding process, zinc stearate accounting for 2-3wt% is added into the powder before pressing, and the powder is mixed for 5min by using a stirrer so as to facilitate demoulding of a green body; in the molding process, the pressure is applied in the sequence of rising to 3-4 MPa and keeping for 5s, so that the gas in the powder is fully discharged, and then rising to 6-7 MPa and keeping for 10-15 s.
8. The method for preparing the direct current superposition resistant wide-temperature low-loss MnZn ferrite according to claim 1, wherein in the primary ball milling and the secondary ball milling processes, adopted ball milling media are deionized water and stainless steel balls, and powder: deionized water: the weight ratio of the steel balls is 1:1.6:3, a step of; the steel balls are made of 304 stainless steel, and are formed by mixing four stainless steel balls with different specifications according to a specific weight ratio, wherein the weight ratio is phi 1.5mm: Φ3.0mm: phi 5.0mm: Φ8.5mm=1: 3:3:4.
9. The direct current superposition-resistant wide-temperature low-loss MnZn ferrite is characterized by being prepared by the preparation method of the direct current superposition-resistant wide-temperature low-loss MnZn ferrite according to any one of claims 1 to 8.
10. The use of a direct current stack resistant and wide temperature range low loss MnZn ferrite as defined in claim 9, wherein the direct current stack resistant and wide temperature range low loss MnZn ferrite is used in electronic components.
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