CN113716950B - Low-temperature sintered flexible magnetic sheet and preparation method thereof - Google Patents
Low-temperature sintered flexible magnetic sheet and preparation method thereof Download PDFInfo
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- CN113716950B CN113716950B CN202111279412.XA CN202111279412A CN113716950B CN 113716950 B CN113716950 B CN 113716950B CN 202111279412 A CN202111279412 A CN 202111279412A CN 113716950 B CN113716950 B CN 113716950B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 239000006247 magnetic powder Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000011521 glass Substances 0.000 claims abstract description 20
- 239000007888 film coating Substances 0.000 claims abstract description 19
- 238000009501 film coating Methods 0.000 claims abstract description 19
- 238000004537 pulping Methods 0.000 claims abstract description 11
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000000498 ball milling Methods 0.000 claims description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- 238000005266 casting Methods 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- 239000008096 xylene Substances 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000010345 tape casting Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 17
- 235000019485 Safflower oil Nutrition 0.000 description 16
- 235000005713 safflower oil Nutrition 0.000 description 16
- 239000003813 safflower oil Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 12
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
- 230000035699 permeability Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009766 low-temperature sintering Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 1
- 229910001053 Nickel-zinc ferrite Inorganic materials 0.000 description 1
- 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 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
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- 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
- C04B35/265—Compositions containing one or more ferrites of the group comprising manganese or zinc and one or more ferrites of the group comprising nickel, copper or cobalt
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- 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
- H01F1/342—Oxides
- H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
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Abstract
The invention provides a low-temperature sintered flexible magnetic sheet and a preparation method thereof, which mainly obtains nano-scale ferrite magnetic powder by a high-energy ball mill, and mixes glass powder in the nano-scale ferrite magnetic powder, and finally, the nano-scale ferrite magnetic powder is sintered at a lower temperature to obtain a product with a compact structure. The uniformity of the grain diameter of the used powder is high, and the consistency of the electromagnetic performance of the sample is also high. And the sintering at low temperature not only avoids the problem of adhesion of the upper and lower layers of the magnetic sheets during sintering, but also has the effects of reducing energy consumption and production cost. The method mainly comprises the steps of raw material mixing, 2) presintering, 3) high-energy ball milling, 4) pulping, 5) tape casting, 6) sintering and 7) film coating and splitting. Finally, the magnetic sheet with low loss, high Bs and strong toughness is obtained.
Description
Technical Field
The invention relates to the technical field of magnetic materials, in particular to a soft magnetic flexible material and a preparation process thereof.
Background
With the rise of wireless charging technology in recent years, magnetic shielding materials in wireless charging equipment are receiving increasingly wide attention. The magnetic shielding material can enhance the coil induction magnetic field in a wireless charging system, improve the coil coupling coefficient and further improve the charging efficiency; meanwhile, the attenuation interference of the metal conductor to the magnetic field of the coil is shielded, the battery is prevented from heating due to eddy current loss, and the EMC function of the wireless charging system and the terminal equipment is realized. The wireless charging magnetic shielding materials which are widely applied at present comprise four types of manganese zinc ferrite thin magnetic sheets, nickel zinc ferrite thin magnetic sheets, amorphous alloys and nanocrystalline alloy thin magnetic sheets. The amorphous and nanocrystalline have obvious advantages in the aspects of performances such as saturation magnetic induction intensity and magnetic permeability and can be simultaneously soft and ultrathin, but the costs of the amorphous and nanocrystalline are high, so that the amorphous and nanocrystalline are very necessary to perform corresponding performance improvement on a low-cost ferrite soft magnetic sheet, and especially are developed towards the directions of flexibility, high frequency, high Bs and high stability so as to improve the charging power and stability of wireless charging.
The production efficiency of products is generally improved by adopting a stacking sintering process in the production process of magnetic sheets, however, in the process of crystal grain growth during sintering, the upper layer and the lower layer of the magnetic sheets can be adhered due to higher sintering temperature, the toughness of the magnetic sheets is reduced, the problem of adhesion can be solved by reducing the sintering temperature, the reaction can be insufficient, the density of the products is not enough, and the performance of the magnetic sheets is reduced, so that a method for preparing the high-performance ferrite soft magnetic sheets by adopting a low-temperature sintering process is urgently needed to be researched and developed, the production efficiency can be improved, the cost can be reduced, the high-performance magnetic sheets are more favorably obtained, and the requirement of wireless charging application is met.
Patent No. CN109231978B discloses a sintering method using low temperature and low pressure, but the simple low temperature sintering inevitably results in the decrease of magnetic permeability, and the invention reduces the temperature and particle size, thereby ensuring the magnetic permeability to be unchanged. In the patent with the publication number of CN108911732B, the Bs reaches 400mT (25 ℃) while the high magnetic conductivity and the low loss are considered at the same time by adjusting the formula, but the performance technical parameters are still lower than that of the invention because the invention is further optimized in process. Patent publication No. CN110156449B discloses a method for improving the reliability of ferrite materials, but does not involve low temperature sintering, and does not require the power loss performance of the materials.
Disclosure of Invention
The invention provides a low-temperature sintered flexible magnetic sheet and a preparation method thereof, which mainly obtains nano-scale ferrite powder through high-energy ball milling, and mixes a glass powder cosolvent in auxiliary components, so that a product with a compact structure can still be obtained through sintering at a lower temperature. The invention mainly comprises the following steps:
1) mixing raw materials: sanding the high-purity oxide raw material for preparing ferrite, uniformly mixing and drying;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, and sintering the burning pot into a ferrite phase, wherein the pre-burning temperature is 750-950 ℃;
3) high-energy ball milling: doping auxiliary components into the pre-sintered powder, and ball-milling the powder to nano-scale ferrite magnetic powder in a high-energy ball mill;
4) pulping: adding the nanoscale ferrite magnetic powder, an organic solvent and a dispersing agent into a ball milling tank, mixing uniformly, adding a binder and a plasticizer, and performing secondary ball milling to obtain uniform powder;
5) casting: screening the prepared slurry, removing bubbles, and casting into a green belt with the thickness of 0.03-0.5 mm;
6) and (3) sintering: cutting the green body into required size, laminating the green body to the thickness of 0.03-3 mm, and sintering the green body at the temperature of 800-1300 ℃;
7) film coating and splitting: and (5) laminating and splitting the cooked slices by using an automatic laminating and splitting machine.
The technical scheme for solving the technical problem further comprises the following steps:
the high-purity oxide raw material in the step 1) mainly comprises three substances of zinc oxide, iron oxide and nickel oxide or three substances of zinc oxide, iron oxide and manganese oxide, and the preferable component proportion is Fe2O360-70 wt%, ZnO 5-20 wt%, and the balance of MnO or NiO;
the particle size of the nano-scale ferrite magnetic powder in the step 3) is 10-1000 nm;
the auxiliary component doped in the step 3) is glass powder and one or more of Ca, Nb, V, Co, Ti, Zr and Cu element oxides;
the glass powder is formed by combining at least 3 of B, Si, Bi, Zn, Li, Al and Mg oxides;
the preferable content of the auxiliary components is as follows: 10000ppm of glass powder 100-;
the organic solvent in the step 4) comprises one or more of methyl ethyl ketone, toluene, xylene, ethanol, acetone, butanone and cycloethanone.
The invention reduces the grain diameter of ferrite powder to nanometer level by high energy ball milling method, so as to improve the activity of powder particles and reduce the activation energy required by grain growth, thereby ensuring high magnetic conductivity. On the basis, the glass powder is doped to generate a liquid phase during low-temperature sintering so as to accelerate the ion diffusion speed and achieve good densification effect, and meanwhile, the disordered structure substance without a fixed melting point prevents secondary crystallization caused by generation of a large amount of liquid phase at the same time during sintering to a certain extent, so that the problem of performance deterioration possibly caused by addition of a single oxide cosolvent is avoided; and the different softening temperature ranges of different types of glass powder also determine different degrees of reducing the sintering temperature. The invention not only solves the technical problem of adhesion of upper and lower magnetic sheets in the magnetic sheet stacking and sintering process while ensuring the high Q value and Bs performance of the magnetic sheet, so as to improve the production efficiency, but also further reduces the production cost through the low-temperature sintering process.
The invention has the beneficial effects that:
1. under the condition of reducing the sintering temperature of 100 ℃, the real part of the magnetic permeability of the manganese-zinc product is basically unchanged, but the Q value is improved from 147 to 426, and is improved by 189%, and the Bs is improved from 462 to 498, and is improved by 7.8%; under the condition of reducing the sintering temperature of 150 ℃, the magnetic permeability is slightly reduced by 1.6 percent, but the Q value is improved from 147 to 309 and 110 percent, and the Bs is improved from 462 to 485 and is improved by 5.0 percent. Under the condition of reducing the sintering temperature of 100 ℃, the magnetic permeability of the nickel-zinc product is basically unchanged, the Q value is improved from 35 to 58 and is improved by 66 percent, and the Bs is improved from 388 to 405 and is improved by 4.4 percent.
2. The sintering temperature is reduced while the high performance of the magnetic sheet is ensured, the technical problem of adhesion of upper and lower magnetic sheets in the magnetic sheet stacking and sintering process is solved, the production efficiency and the performance of the magnetic sheet are improved, and the production cost is also reduced.
Detailed Description
The embodiment is a preferred embodiment of the present invention, and all other embodiments obtained by other technicians without creative efforts belong to the protection scope of the present invention.
Example 1
This example prepares low temperature sintered flexible magnetic sheets as follows:
1) mixing raw materials: raw materials are mixed according to the proportion of Fe2O369.5 wt%, ZnO 7.00wt% and MnO balance, sanding, mixing, and drying;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, heating to 850 ℃ at a heating rate of 5 ℃/min, and preserving heat for two hours for pre-burning;
3) high-energy ball milling: after the pre-sintered powder is vibrated and ground, the auxiliary component CaCO is added3:500ppm、Nb2O5:200、CuO: 1000 ppm、Co2O3： 3000ppm、B2O3-ZnO-Li21000ppm of O-series glass, and then ball-milling for 2h in a high-energy ball mill to obtain nano-scale magnetic powder with D50 of 150-450 nm and D90 of 250-450 nm;
4) pulping: adding the nano-scale magnetic powder prepared in the step 3), xylene, ethanol and safflower oil into a ball milling tank according to a certain proportion, mixing for 12 hours, adding a certain amount of DBP and PVB, and carrying out secondary ball milling for 6 hours to prepare slurry with proper viscosity for tape casting. Wherein the ferrite magnetic powder: xylene: ethanol: safflower oil: DBP: the mass ratio of PVB is 70 wt%: 10 wt%: 12 wt%: 1 wt%: 3 wt%: 4 wt%;
5) casting: screening the prepared slurry, stirring in vacuum, removing bubbles, and casting into a green belt with the thickness of 0.1 mm;
6) and (3) sintering: the green bodies were cut to 100 x 100mm size and 10 layers stacked and then fired to sinter the green sheets at 1100 ℃ for 2 hours. The temperature rise speed of the 25-800 ℃ glue discharging stage is 1.2 ℃/min, the temperature rise speed of 800 plus 1100 ℃ is 2.4 ℃/min, the temperature reduction speed is 2 ℃/min, and the heat preservation oxygen content is 4 vol%;
7) film coating and splitting: and (5) coating and splitting the sintered cooked piece by using an automatic film coating and splitting machine, and performing performance test.
Example 2
This example prepares low temperature sintered flexible magnetic sheets as follows:
1) mixing raw materials: raw materials are mixed according to the proportion of Fe2O369.5 wt%, ZnO 7.00wt% and MnO for the rest, sand grinding, mixing, oven drying；
2) Pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, heating to 850 ℃ at the heating rate of 5 ℃/Min, and preserving heat for two hours for pre-burning;
3) high-energy ball milling: after the pre-sintered powder is vibrated and ground, the auxiliary component CaCO is added3:500ppm、Nb2O5:200、CuO: 1000 ppm、Co2O3： 3000ppm、Bi2O3-B2O3-SiO2The glass is 500ppm, and then the nano-scale magnetic powder with D50 of 150-450 nm and D90 of 250-450nm is obtained by ball milling for 2h in a high-energy ball mill;
4) pulping: adding the nano-scale magnetic powder prepared in the step 3), xylene, ethanol and safflower oil into a ball milling tank according to a certain proportion, mixing for 12 hours, adding a certain amount of DBP and PVB, and carrying out secondary ball milling for 6 hours to prepare slurry with proper viscosity for tape casting. Wherein, the ferrite magnetic powder: xylene: ethanol: safflower oil: DBP: the mass ratio of PVB is 70 wt%: 10 wt%: 12 wt%: 1 wt%: 3 wt%: 4 wt%;
5) casting: screening the prepared slurry, stirring in vacuum, removing bubbles, and casting into a green belt with the thickness of 0.1 mm;
6) and (3) sintering: the green bodies were cut to 100 x 100mm size and 10 layers stacked and then fired to sinter the green sheets at 1050 ℃ for 2 hours. The temperature rise speed in the glue discharging stage at 25-800 ℃ is 1.2 ℃/min, the temperature rise speed at 800-. The heat preservation oxygen content is 4 vol%;
7) film coating and splitting: and (5) coating and splitting the sintered cooked piece by using an automatic film coating and splitting machine, and performing performance test.
Example 3
This example prepares low temperature sintered flexible magnetic sheets as follows:
1) mixing raw materials: raw materials are mixed according to the proportion of Fe2O369.5 wt%, ZnO 7.00wt% and MnO in balance, sanding, mixing, and drying;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, heating to 850 ℃ at the heating rate of 5 ℃/Min, and preserving heat for two hours for pre-burning;
3) high-energy ball milling: after the pre-sintered powder is vibrated and ground, the auxiliary component CaCO is added3:500ppm、Nb2O5:200、CuO: 1000 ppm、Co2O3： 3000ppm、Bi2O3-B2O3-SiO2The glass is 500ppm, and then the nano-scale magnetic powder with D50 of 400-700 nm and D90 of 500-700nm is obtained by ball milling for 1h in a high-energy ball mill;
4) pulping: adding the nano-scale magnetic powder prepared in the step 3), xylene, ethanol and safflower oil into a ball milling tank according to a certain proportion, mixing for 12 hours, adding a certain amount of DBP and PVB, and carrying out secondary ball milling for 6 hours to prepare slurry with proper viscosity for tape casting. Wherein the ferrite magnetic powder: xylene: ethanol: safflower oil: DBP: the mass ratio of PVB is 70 wt%: 10 wt%: 12 wt%: 1 wt%: 3 wt%: 4 wt%;
5) casting: screening the prepared slurry, stirring in vacuum, removing bubbles, and casting into a green belt with the thickness of 0.1 mm;
6) and (3) sintering: the green bodies were cut to 100 x 100mm size and 10 layers stacked and then fired to sinter the green sheets at 1100 ℃ for 2 hours. The temperature rise speed of the 25-800 ℃ glue discharging stage is 1.2 ℃/min, the temperature rise speed of 800 plus 1100 ℃ is 2.4 ℃/min, the temperature reduction speed is 2 ℃/min, and the heat preservation oxygen content is 4 vol%;
7) film coating and splitting: and (5) coating and splitting the sintered cooked piece by using an automatic film coating and splitting machine, and performing performance test.
Example 4
This example prepares low temperature sintered flexible magnetic sheets as follows:
1) mixing raw materials: raw materials are mixed according to the proportion of Fe2O365.5 wt%, 18wt% of ZnO and the balance of NiO, sanding, uniformly mixing and drying;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, heating to 850 ℃ at the heating rate of 5 ℃/Min, and preserving heat for two hours for pre-burning;
3) high-energy ball milling: after the pre-sintered powder is vibrated and ground, the auxiliary component Co is added2O3：10000ppm、Cu：50000ppm、B2O3-ZnO-Li2O-based glass 1000ppm, and then ball milling for 2h in a high-energy ball mill to obtain nano-scale magnetic powder with D50 of 150-450 nm and D90 of 250-450 nm;
4) pulping: adding the nano-scale magnetic powder prepared in the step 3), xylene, ethanol and safflower oil into a ball milling tank according to a certain proportion, mixing for 12 hours, adding a certain amount of DBP and PVB, and carrying out secondary ball milling for 6 hours to prepare slurry with proper viscosity for tape casting. Wherein the ferrite magnetic powder: xylene: ethanol: safflower oil: DBP: the mass ratio of PVB is 70 wt%: 10 wt%: 12 wt%: 1 wt%: 3 wt%: 4 wt%;
5) casting: screening the prepared slurry, stirring in vacuum, removing bubbles, and casting into a green belt with the thickness of 0.1 mm;
6) and (3) sintering: the green bodies were cut to 100 x 100mm size and 10 layers stacked and then sintered to a green sheet by holding at 850 ℃ for 2 hours. Sintering at the temperature rising speed of 1.2 ℃/min, at the temperature rising speed of 2.4 ℃/min and at the temperature falling speed of 2 ℃/min at the temperature of 700-700 ℃ and 850 ℃ in the air atmosphere;
7) film coating and splitting: and (5) coating and splitting the sintered cooked piece by using an automatic film coating and splitting machine, and performing performance test.
Comparative example 1
The comparative example a low temperature sintered flexible magnetic sheet was prepared as follows:
1) mixing raw materials: raw materials are mixed according to the proportion of Fe2O369.5 wt%, ZnO 7.00wt% and MnO in balance, sanding, mixing, and drying;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, heating to 850 ℃ at the heating rate of 5 ℃/Min, and preserving heat for two hours for pre-burning;
3) ball milling: after the pre-sintered powder is vibrated and ground, the auxiliary component CaCO is added3:500ppm、Nb2O5:200、CuO: 1000 ppm、Co2O3： 3000ppm、B2O3-ZnO-Li21000ppm of O-series glass, and then ball-milling the O-series glass in a ball mill for 1 hour to obtain micron-sized magnetic powder with D50 of 0.8 to 1.2 mu m and D90 of 1.5 to 3.0 mu m;
4) pulping: adding the nano-scale magnetic powder prepared in the step 3), xylene, ethanol and safflower oil into a ball milling tank according to a certain proportion, mixing for 12 hours, adding a certain amount of DBP and PVB, and carrying out secondary ball milling for 6 hours to prepare slurry with proper viscosity for tape casting. Wherein the ferrite magnetic powder: xylene: ethanol: safflower oil: DBP: the mass ratio of PVB is 70 wt%: 10 wt%: 12 wt%: 1 wt%: 3 wt%: 4 wt%;
5) casting: screening the prepared slurry, stirring in vacuum, removing bubbles, and casting into a green belt with the thickness of 0.1 mm;
6) and (3) sintering: the green bodies were cut to 100 x 100mm size and 10 layers stacked and then fired to sinter the green sheets at 1150 ℃ for 2 hours. The temperature rising speed of the glue discharging stage at 25-800 ℃ is 1.2 ℃/min, the temperature rising speed at 800-. The heat preservation oxygen content is 4 vol%;
7) film coating and splitting: and (5) coating and splitting the sintered cooked piece by using an automatic film coating and splitting machine, and performing performance test.
Comparative example 2
The comparative example a low temperature sintered flexible magnetic sheet was prepared as follows:
1) mixing raw materials: raw materials are mixed according to the proportion of Fe2O369.5 wt%, ZnO 7.00wt% and MnO in balance, sanding, mixing, and drying;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, heating to 850 ℃ at the heating rate of 5 ℃/Min, and preserving heat for two hours for pre-burning;
3) ball milling: after the pre-sintered powder is vibrated and ground, the auxiliary component CaCO is added3:500ppm、Nb2O5:200、CuO: 1000 ppm、Co2O3: 3000ppm, then ball milling for 2h in a high-energy ball mill to obtain nano-scale magnetic powder with D50 of 150 and 250 and D90 of 250 and 450 nm;
4) pulping: adding the nano-scale magnetic powder prepared in the step 3), xylene, ethanol and safflower oil into a ball milling tank according to a certain proportion, mixing for 12 hours, adding a certain amount of DBP and PVB, and carrying out secondary ball milling for 6 hours to prepare slurry with proper viscosity for tape casting. Wherein the ferrite magnetic powder: xylene: ethanol: safflower oil: DBP: the mass ratio of PVB is 70 wt%: 10 wt%: 12 wt%: 1 wt%: 3 wt%: 4 wt%;
5) casting: screening the prepared slurry, stirring in vacuum, removing bubbles, and casting into a green belt with the thickness of 0.1 mm;
6) and (3) sintering: the green bodies were cut to 100 x 100mm size and 10 layers stacked and then fired to sinter the green sheets at 1150 ℃ for 2 hours. The temperature rise speed of the glue discharging stage at 25-800 ℃ is 1.2 ℃/min, the temperature rise speed at 800-1150 ℃ is 2.4 ℃/min, the temperature reduction speed is 2 ℃/min, and the heat preservation oxygen content is 4 vol%;
7) film coating and splitting: and (5) coating and splitting the sintered cooked piece by using an automatic film coating and splitting machine, and performing performance test.
Comparative example 3
The comparative example a low temperature sintered flexible magnetic sheet was prepared as follows:
1) mixing raw materials: raw materials are mixed according to the proportion of Fe2O369.5 wt%, ZnO 7.00wt% and MnO in balance, sanding, mixing, and drying;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, heating to 850 ℃ at the heating rate of 5 ℃/Min, and preserving heat for two hours for pre-burning;
3) ball milling: after the pre-sintered powder is vibrated and ground, the auxiliary component CaCO is added3:500ppm、Nb2O5:200、CuO: 1000 ppm、Co2O3: 3000ppm, then ball milling for 1h in a ball mill to obtain micron-sized magnetic powder with D50 of 0.8-1.2 μm and D90 of 1.5-3.0 μm;
4) pulping: adding the micron-sized magnetic powder prepared in the step 3), xylene, ethanol and safflower oil into a ball milling tank according to a certain proportion, mixing for 12 hours, adding a certain amount of DBP and PVB, and performing secondary ball milling for 6 hours to prepare slurry with proper viscosity and suitable tape casting. Wherein the ferrite magnetic powder: xylene: ethanol: safflower oil: DBP: the mass ratio of PVB is 70 wt%: 10 wt%: 12 wt%: 1 wt%: 3 wt%: 4 wt%;
5) casting: screening the prepared slurry, stirring in vacuum, removing bubbles, and casting into a green belt with the thickness of 0.1 mm;
6) and (3) sintering: the green bodies were cut to 100 x 100mm size and 10 layers stacked and then sintered to a green sheet by holding at 1200 ℃ for 2 hours. The temperature rise speed of the glue discharging stage at 25-800 ℃ is 1.2 ℃/min, the temperature rise speed at 800-;
7) film coating and splitting: and (5) coating and splitting the sintered cooked piece by using an automatic film coating and splitting machine, and performing performance test.
Comparative example 4
The comparative example a low temperature sintered flexible magnetic sheet was prepared as follows:
1) mixing raw materials: raw materials are mixed according to the proportion of Fe2O365.5 wt%, 18wt% of ZnO and the balance of NiO, sanding, uniformly mixing and drying;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, heating to 850 ℃ at the heating rate of 5 ℃/Min, and preserving heat for two hours for pre-burning;
3) ball milling: after the pre-sintered powder is vibrated and ground, the auxiliary component Co is added2O3: 10000ppm, Cu: 50000ppm, then ball milling in a ball mill for 1h to obtain micron-sized magnetic powder with D50 of 0.8-1.2 μm and D90 of 1.5-3.0 μm;
4) pulping: adding the micron-sized magnetic powder prepared in the step 3), xylene, ethanol and safflower oil into a ball milling tank according to a certain proportion, mixing for 12 hours, adding a certain amount of DBP and PVB, and performing secondary ball milling for 6 hours to prepare slurry with proper viscosity and suitable tape casting. Wherein the ferrite magnetic powder: xylene: ethanol: safflower oil: DBP: the mass ratio of PVB is 70 wt%: 10 wt%: 12 wt%: 1 wt%: 3 wt%: 4 wt%;
5) casting: screening the prepared slurry, stirring in vacuum, removing bubbles, and casting into a green belt with the thickness of 0.1 mm;
6) and (3) sintering: the green bodies were cut to 100 x 100mm size and 10 layers stacked and then sintered to a green sheet by holding at 950 ℃ for 2 hours. Sintering at the temperature rising speed of 1.2 ℃/min, at the temperature rising speed of 2.4 ℃/min and at the temperature lowering speed of 2 ℃/min in the glue discharging stage at the temperature of 25-700 ℃, at the temperature rising speed of 890 ℃ and at the temperature lowering speed of 2 ℃/min in the air atmosphere;
7) film coating and splitting: and (5) coating and splitting the sintered cooked piece by using an automatic film coating and splitting machine, and performing performance test.
Through tests, the test performance of the examples and the comparative examples is shown in table 1, and compared with comparative example 3, comparative example 1 can reduce the sintering temperature by doping the glass powder, and comparative example 2 can reduce the sintering temperature by reducing the particle size of the magnetic powder. Comparing example 1 and example 2 with comparative example 3, respectively, it can be found that different glass frits have different temperature-lowering effects, and therefore, the selection of the glass frits is very important to the material properties. In examples 1, 2, 3 and 4, the glass powder was doped while reducing the particle size of the magnetic powder, and the performance of the material in examples was higher by comparison with the comparative example.
Example 4 and comparative example 4 demonstrate that the invention is equally applicable in nickel zinc materials. The invention reduces the sintering temperature and improves the Q value and Bs, thereby not only overcoming the technical problem of adhesion during the sintering of the magnetic sheet and reducing the loss, but also enhancing the density of the magnetic sheet, which means the enhancement of the toughness, and having important significance for the production optimization of the flexible magnetic sheet.
TABLE 1
Claims (5)
1. A low-temperature sintered flexible magnetic sheet is characterized in that the preparation method comprises the following steps:
1) mixing raw materials: sanding the oxide raw material for preparing the ferrite, uniformly mixing and drying, wherein the oxide raw material is three substances of zinc oxide, iron oxide and nickel oxide or three substances of zinc oxide, iron oxide and manganese oxide, and the proportion is Fe2O360-70 wt%, ZnO 5-20 wt%, and the balance of MnO or NiO;
2) pre-burning: putting the dried powder into a burning pot, putting the burning pot into a pre-burning furnace, and sintering into a ferrite phase;
3) high-energy ball milling: after doping auxiliary components into the pre-sintered powder, ball-milling the powder in a high-energy ball mill to obtain nano-scale ferrite magnetic powder with the particle size of 10-1000 nm, wherein the doped auxiliary components comprise glass powder and one or more oxides containing Ca, Nb, V, Co, Ti, Zr and Cu elements, and the content of the auxiliary components is as follows: 10000ppm of glass powder, 100-800ppm of Ca, 100-400 ppm of Nb, 100-400 ppm of V, 1000-4000 ppm of Co, 1000-4000 ppm of Ti, 100-600 ppm of Zr and 100-70000 ppm of Cu, wherein the glass powder is formed by combining at least 3 of B, Si, Bi, Zn, Li, Al and Mg oxides;
4) pulping: adding the nanoscale ferrite magnetic powder, an organic solvent and a dispersing agent into a ball milling tank, mixing uniformly, adding a binder and a plasticizer, and carrying out secondary ball milling until the mixture is uniform;
5) casting: screening the prepared slurry, removing bubbles, and casting to form a green belt;
6) and (3) sintering: cutting the green body into required size, laminating, and sintering at 800-1300 deg.C to obtain the final product;
7) film coating and splitting: and (5) laminating and splitting the cooked slices by using an automatic laminating and splitting machine.
2. A low temperature sintered flexible magnetic sheet according to claim 1, wherein said pre-firing temperature in step 2) is 750 to 950 ℃.
3. A low-temperature-sintered flexible magnetic sheet according to claim 1, wherein said organic solvent in step 4) comprises one or more of methyl ethyl ketone, toluene, xylene, ethanol, acetone, methyl ethyl ketone and cycloethanone.
4. A low-temperature-sintered flexible magnetic sheet as claimed in claim 1, wherein in the step 5), said cast green sheet has a thickness of 0.03 to 0.5 mm.
5. A low-temperature-sintered flexible magnetic sheet according to claim 1, wherein in the step 6), the thickness of said laminate is 0.03 to 3 mm.
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