CN113998999B - Manufacturing method of wide-temperature low-loss high-Bs manganese-zinc ferrite material - Google Patents
Manufacturing method of wide-temperature low-loss high-Bs manganese-zinc ferrite material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 18
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 21
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 18
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims description 71
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 229910000859 α-Fe Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims description 12
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- 238000002156 mixing Methods 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 11
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- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of manganese-zinc ferrite materials, and discloses a method for manufacturing a wide-temperature low-loss high-Bs manganese-zinc ferrite material, wherein the material manufactured by the method comprises main components and auxiliary components, wherein the main components are as follows: fe2O3、ZnO、Mn3O4The auxiliary components comprise: co2O3、CaCO3、Nb2O5、ZrO2、Li2CO3And CCTO. The invention adopts a mode of twice presintering to crush the presintering material after the once presintering, solves the problem of large difference of magnetic force and activity of the presintering material caused by insufficient presintering of inner and outer layers of powder particles or particle agglomeration, and adds CaCO when sanding after the once presintering3And the other auxiliary components are added during ball milling after the secondary presintering, so that the finally prepared manganese-zinc ferrite material has the characteristics of uniform grain size distribution, high density, low power loss, high magnetic permeability and high Bs within the temperature range of 25-140 ℃.
Description
Technical Field
The invention belongs to the field of preparation technology and application of high-performance power ferrite soft magnetic materials, and relates to a manufacturing method of a wide-temperature low-loss high-Bs manganese-zinc ferrite material. The high Bs material manufactured by the manufacturing method has low power loss under a wide temperature condition (25-140 ℃), and the power loss-temperature curve is stable within a temperature range of 25-140 ℃.
Background
In the field of new energy automobiles and charging thereof, the manganese-zinc power ferrite material can be applied to a transformer part in a charging pile, the power of the charging pile is generally high, instantaneous large current can be generated during working, an internal core magnetic device can be heated to about 120 ℃ due to heating, so that the manganese-zinc power ferrite material is required to have low power consumption at the working temperature of 100-140 ℃, in addition, the manganese-zinc power ferrite material is required to still maintain low power in a standby state at about 25 ℃ so as to improve the overall utilization rate, and therefore the manganese-zinc power ferrite material is required to have the characteristics of wide temperature and low loss at 25-140 ℃; and because the charging power is larger, a ferrite magnetic core with high saturation magnetic flux density is needed to improve the power density, the size of the charger is greatly reduced, and the charging efficiency is improved.
Therefore, in order to meet the development requirements of various new energy industries, many developers have studied manganese-zinc ferrite materials with wide temperature range, low loss and high Bs, and the patent with publication number CN112456996A discloses a manganese-zinc ferrite material with high Bs, wide temperature range and low loss power, and a preparation method and application thereof, wherein the manganese-zinc ferrite material comprises a main component of Fe respectively in terms of mole ratio of oxides2O3：55.0～57.0mol％、Mn3O4: 33.5-35.0 mol% and the balance of ZnO; the trace additive is CaO: 400 to 800ppm of Co2O3: 2700-3700 ppm, NiO: 6000 to 8000 ppm. Although the power loss of the material is low and gentle within 25-100 ℃, the high-temperature loss of 120 ℃ and above is not mentioned, and the Bs under the condition of 100 ℃ is only 420mT, the Bs is lower, and the application range is limited.
The patent with publication number CN107459344A discloses a Mn-Zn ferrite material with wide temperature range, low loss and high Bs and a manufacturing method thereof, and the prepared material has a second peak temperature near 100 ℃ by improving the material components and the mixture ratio, thereby effectively reducing the loss of the working temperature. However, at higher temperatures, the deterioration of the losses associated with high Bs is still not addressed.
The patent with publication number CN111517776A discloses a preparation method of a manganese-zinc soft magnetic ferrite material, the prepared material has good wide temperature property, lower power loss and excellent saturation magnetic flux density, but in the preparation method, the preparation of briquettes is needed before secondary pre-sintering, however, in large-scale production, the preparation of large briquettes consumes a large amount of manpower and material resources; and the doping system uses rare earth elements and graphene components, so the price is high, and the production cost is increased.
The patent with the publication number of CN111039667A provides a wide-temperature low-loss ferrite and a preparation method thereof, relating to the technical field of ferrite processing. The wide-temperature low-loss ferrite is composed of a first mixture and a second mixture, and the prepared ferrite has low power loss value at various temperatures by adopting a cooling treatment and a secondary sintering process, but the saturation magnetic flux density at the high temperature of 100 ℃ is still lower than 422 mT, so that the application range of the material is limited; in the manufacturing process of the material, the first mixture and the second mixture need to be manufactured independently and involve a strong acid corrosion step, so that certain operation difficulty exists in actual production.
Therefore, a high saturation magnetic flux density (Bs) and a high initial permeability (. mu.) were developedi) And the manganese zinc ferrite material with lower power loss characteristic in a wide temperature range and the manufacturing method thereof have important significance.
Disclosure of Invention
In order to solve the problems, the invention provides a method for manufacturing a manganese-zinc ferrite material with low cost, wide temperature range, low loss and high Bs, which can adapt to mass production, by optimizing the process flow and improving the formula.
The technical scheme adopted by the invention is as follows:
the wide-temperature low-loss high-Bs manganese-zinc ferrite material comprises main components and auxiliary components, wherein the main components comprise the following components: 53.8-55.2mol% Fe2O39.8-13mol% of ZnO, and the balance of Mn3O4The auxiliary components comprise: 0.3-0.6wt% of Co2O3(ii) a 0.05-0.1wt% of CaCO3(ii) a 0.015-0.035wt% Nb2O5(ii) a 0.015-0.035wt% ZrO2(ii) a 0.15-0.25wt% Li2CO3(ii) a 0.01-0.03wt% of CCTO; the above auxiliary component is relative to Fe2O3、Mn3O4The total amount of ZnO is calculated by weight percentage, wherein CaCO3The auxiliary components are added during sanding, and the other auxiliary components are added during ball milling, so that a better effect can be obtained by matching with a secondary pre-sintering process. The preparation method comprises the following specific steps:
the method comprises the following steps: the main component Fe2O3、Mn3O4Adding deionized water according to the ratio of 1:1 into ZnO according to the metering of the raw materials of the components, adding a proper amount of dispersing agent, mixing for 20-30min, taking out slurry, drying to obtain uniform mixed powder, pre-burning at the temperature of 700-800 ℃, controlling the oxygen content to be 5-20vol% by controlling the ratio of air and nitrogen for 2-3 h, and cooling along with a furnace;
step two: adding auxiliary components into the pre-sintered material obtained by the primary pre-sintering, adding deionized water according to the proportion of 1:1, sanding and drying, wherein the added auxiliary components are 0.05-0.1wt% of CaCO3And the sanding time is 60-100 min, and the particle size D90 after sanding is controlled: 3.0 to 3.3 μm;
step three: crushing the mixture prepared in the step two, screening the mixture by a 28-mesh screen, performing secondary pre-sintering, selecting the pre-sintering temperature to be 850-950 ℃, controlling the oxygen content to be 5-20vol% by controlling the ratio of air and nitrogen, controlling the time to be 2-3 h, and cooling along with a furnace;
step four: adding auxiliary components into the powder subjected to secondary presintering, performing ball milling, drying, wherein the ball milling time is 40-60 min, and controlling the particle size D90 after ball milling: 2.5-2.7 μm;
step five: crushing the dried powder, sieving the crushed powder by a 40-mesh sieve, adding 15% PVA (polyvinyl alcohol) for granulation, sieving, removing uneven granules of granulation, drying the granulated powder at 120-140 ℃ for 10-20min to obtain powder with good fluidity and filling property, and performing bidirectional pressing to obtain a green ring with the diameter of 25 x 15 x 8mm under the pressure of 300-350 MPa;
step six: and sintering the green ring pressed in the fifth step in a bell jar furnace, wherein the sintering heat preservation temperature is 1280-1320 ℃, the heat preservation time is 4-8h, the oxygen content is 3.5-4.6vol%, and finally the manganese zinc ferrite sample ring is obtained.
Preferably, the content of the auxiliary component can be 0.05-0.07wt% of CaCO3(ii) a 0.35-0.5wt% Co2O3(ii) a 0.02-0.03wt% of Nb2O5(ii) a 0.015-0.025wt% ZrO2(ii) a 0.2-0.25wt% Li2CO3(ii) a 0.015-0.025wt% of CCTO.
In the ferrite preparation process, the ferrite raw material is generally mixed by a wet method, added with PVA for granulation, and then put into a rotary kiln or a roller kiln for presintering after granulation. In the rotary kiln, due to the irregular shape of particles and the adhesion effect on powder after multiple sintering of the furnace wall, different batches of charging materials even the same furnace head material and the furnace tail material have certain difference, so that the microstructure uniformity is reduced due to the activity difference of the powder during final sintering. The roller kiln is adopted for presintering, and due to the volume effect of the presintering carrier, the presintering degree of the powder at the center of the presintering powder and the powder at the periphery close to the box wall are different. The invention adopts twice presintering process to sand the primary presintering material powder, so as to crush the structure, eliminate the problem of large difference of magnetic force and activity of the presintering material caused by insufficient presintering of the inner layer and the outer layer of the powder particles or particle agglomeration, create a foundation with uniform components and activity for the secondary presintering, reserve the powder after the secondary presintering, and obtain a relatively narrower particle size distribution range after ball milling and crushing, promote the homogenization of the sintered tissue, obtain a better microstructure, improve the initial permeability and reduce the hysteresis loss.
The crushing mode after the secondary presintering does not adopt the sanding but adopts the ball-milling, because obtain a relatively even particle size distribution scope after the sanding, if adopt the sanding again this moment, strong stirring crushing effect can make D50 appear agglomerating, influence active homogeneity, still can lead to the particle diameter too thin the phenomenon of crystallization appears, so with the sanding with the method of ball-milling combined use more reliable stable.
The invention adds CaCO as an auxiliary component during sanding after primary presintering3The principle of action is Ca2+The high-resistance grain-oriented electrical steel has larger radius, can not enter a spinel structure, can be uniformly segregated in a grain boundary after being dispersed by sanding, and forms a high-resistance layer during presintering, the formation of the high-resistance layer not only improves the resistivity, but also plays a role in filling gaps among particles, improves the compactness, and compared with a method for improving the compactness by preparing briquettes, the method simplifies the process steps, improves the presintering effect and further reduces the production cost.
The dielectric material of Copper Calcium Titanate (CCTO) is added into the auxiliary components, so that the actual dielectric constant and microstructure of the manganese zinc ferrite can be improved, the resistivity is improved, and the hysteresis loss and the eddy current loss are further reduced. Co3+And Li+The composite addition of (A) will replace Fe on B position3+And Mn3+Substituted Fe3+Into the A position, thus increasing Fe3+-O-Fe3+Of Fe in manganese-zinc ferrite3+-O-Fe3+The exchange of A-B is enhanced, so that the Curie temperature is increased and the Bs at high temperature is increased.
Compared with the prior art, the invention has the following beneficial effects:
(1) the material disclosed by the invention has high Bs, and simultaneously has the characteristic of lower power loss under a wide temperature condition (25-140 ℃), and the power keeps a loss-temperature curve stable and smooth in the whole application temperature range of 25-140 ℃. The material of the invention achieves the following performance parameters:
μi（25℃）=3000±25%（10kHz,5mV）；
Bs(100℃)≥460mT；
Pcv(25℃)≤345kW/m3，Pcv(100℃)≤290kW/m3；
Pcv(140℃)≤350kW/m3。
(2) the invention adopts the process of twice presintering, the primary presintering powder is ground and crushed, and the secondary presintering is followed by ball milling and crushing, so that the particle size distribution is uniform, the homogenization of the sintered tissue is promoted, a better microstructure is obtained, the initial permeability is improved, and the hysteresis loss is reduced.
(3) The invention adds CaCO as an auxiliary component during one-time presintering3The method is not only beneficial to improving the resistivity, but also has the function of filling gaps among particles, improves the compactness, improves the pre-sintering effect, simplifies the process steps and further reduces the production cost.
(4) In the invention, the dielectric material Copper Calcium Titanate (CCTO) as an auxiliary component is added during secondary pre-sintering, so that the actual dielectric constant and microstructure of the manganese-zinc ferrite can be improved, the loss is reduced, and the Curie temperature and the high temperature Bs (saturation temperature) are improved.
Drawings
FIG. 1 is a graph comparing μ i of examples of the present invention and comparative examples;
FIG. 2 is a comparison of Pcv (100 ℃) of examples of the present invention and comparative examples;
FIG. 3 is a comparison of Pcv (140 ℃ C.) of examples of the present invention and comparative examples;
FIG. 4 is a metallographic microstructure diagram according to example 1 of the present invention;
FIG. 5 is a metallographic microstructure diagram of comparative example 6 of the present invention;
FIG. 6 is a metallographic microstructure diagram of comparative example 9 of the present invention;
FIG. 7 is a metallographic microstructure diagram of comparative example 10 of the present invention;
FIG. 8 is a metallographic microstructure diagram of comparative example 11 of the present invention;
FIG. 9 is a graph showing power loss vs. temperature curves (25 ℃ C. to 140 ℃ C.) at 100kHz and 200mT for example 1 and comparative example 8.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
It should be noted that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 5 and comparative example 6 manganese-zinc power ferrite materials were prepared in the following manner.
Using commercially available purity as Fe2O3(purity is more than or equal to 99.3 percent) and Mn3O4(Mn content is more than or equal to 71 percent) and ZnO (purity is more than or equal to 99.7 percent) according to the main formula of Fe2O3: 54.08 mol%, ZnO 10.74 mol%, Mn3O4The balance being. The preparation method comprises the following specific steps:
the method comprises the following steps: placing the prepared raw materials in a sand mill, adding deionized water according to the mass ratio of 1:1, adding a proper amount of dispersing agent, mixing for 20min, taking out slurry, drying, pre-sintering the dried powder in a rotary kiln for one time, wherein the pre-sintering atmosphere is air and the time is 2h, the pre-sintering temperature is shown in table 1, and the oxygen content of the pre-sintering atmosphere is 20 vol%;
step two: and (3) doping auxiliary components into the primary pre-sintered material: CaCO3: 500 ppm; sanding is carried out, deionized water is added according to the proportion of 1:1, the sanding time is as shown in Table 1, and the sanding grain size D90 is controlled: 3.0-3.3 mu m, putting the ground slurry into an oven, and completely removing water;
step three: crushing the dried powder, screening the crushed powder by a 28-mesh screen, putting the crushed powder into a rotary kiln for secondary pre-sintering, wherein the pre-sintering temperature is shown in table 1;
step four: adding an auxiliary component Nb into the secondary pre-sintered material2O5：250ppm；Co2O3：4000ppm；ZrO2：250ppm；Li2CO3:2000 ppm; CCTO: 200ppm, ball milling is carried out for the ball milling time according to the table 1, and the ball milling particle size D90 is controlled: 2.5-2.7 μm;
step five: crushing the dried powder, sieving with a 40-mesh sieve, adding 15% PVA for granulation, drying at 130 deg.C for 12min, and bidirectionally pressing into green compact ring with inner diameter of 15mm, outer diameter of 25mm and height of 8mm by press machine, and density of 3.1g/cm3Left and right;
step six: and finally, sintering the green ring at the sintering temperature of 1300 ℃, preserving the heat for 6 hours, cooling the green ring to 120 ℃ in a balanced atmosphere at the oxygen partial pressure of 3.8vol%, and discharging the green ring from the furnace, wherein the balanced oxygen partial pressure is adopted in the temperature reduction process.
Comparative example 7a manganese-zinc power ferrite material was prepared as follows.
Using commercially available purity as Fe2O3(purity is more than or equal to 99.3 percent) and Mn3O4(Mn content is more than or equal to 71 percent) and ZnO (purity is more than or equal to 99.7 percent) according to the main formula of Fe2O3: 54.08 mol%, ZnO 10.74 mol%, Mn3O4The balance being. The preparation method comprises the following specific steps:
the method comprises the following steps: placing the prepared raw materials in a sand mill, adding deionized water according to the mass ratio of 1:1, adding a proper amount of dispersing agent, mixing for 20min, taking out slurry, drying, pre-sintering the dried powder in a rotary kiln for one time, wherein the pre-sintering atmosphere is air and the time is 2h, the pre-sintering temperature is shown in table 1, and the oxygen content of the pre-sintering atmosphere is 20 vol%;
step two: and (3) doping auxiliary components into the primary pre-sintered material: CaCO3: 500 ppm; sanding is carried out, deionized water is added according to the proportion of 1:1, the sanding time is as shown in Table 1, and the sanding grain size D90 is controlled: 3.0-3.3 mu m, putting the ground slurry into an oven, and completely removing water;
step three: crushing the dried powder, screening the crushed powder by a 28-mesh screen, putting the crushed powder into a rotary kiln for secondary pre-sintering, wherein the pre-sintering temperature is shown in table 1;
step four: adding an auxiliary component Nb into the secondary pre-sintered material2O5：250ppm；Co2O3：4000ppm；ZrO2：250ppm；Li2CO3:2000 ppm; performing ball milling, wherein the ball milling time is as shown in table 1, and the ball milling particle size D90 is controlled: 2.5-2.7 μm;
step five: crushing the dried powder, sieving with a 40-mesh sieve, adding 15% PVA for granulation, drying at 130 deg.C for 12min, and bidirectionally pressing into green compact ring with inner diameter of 15mm, outer diameter of 25mm and height of 8mm by press machine, and density of 3.1g/cm3Left and right;
step six: and finally, sintering the green ring at the sintering temperature of 1300 ℃, preserving the heat for 6 hours, cooling the green ring to 120 ℃ in a balanced atmosphere at the oxygen partial pressure of 3.8vol%, and discharging the green ring from the furnace, wherein the balanced oxygen partial pressure is adopted in the temperature reduction process.
Comparative example 8 a manganese-zinc power ferrite material was prepared as follows.
Using commercially available purity as Fe2O3(purity is more than or equal to 99.3 percent) and Mn3O4(Mn content is more than or equal to 71 percent) and ZnO (purity is more than or equal to 99.7 percent) according to the main formula of Fe2O3: 54.08 mol%, ZnO 10.74 mol%, Mn3O4The balance being. The preparation method comprises the following specific steps:
the method comprises the following steps: placing the prepared raw materials in a sand mill, adding deionized water according to the mass ratio of 1:1, adding a proper amount of dispersing agent, mixing for 20min, taking out slurry, drying, pre-sintering the dried powder in a rotary kiln for one time, wherein the pre-sintering atmosphere is air and the time is 2h, the pre-sintering temperature is shown in table 1, and the oxygen content of the pre-sintering atmosphere is 20 vol%;
step two: and (3) doping auxiliary components into the primary pre-sintered material: CaCO3: 500 ppm; sanding is carried out, deionized water is added according to the proportion of 1:1, the sanding time is as shown in Table 1, and the sanding grain size D90 is controlled: 3.0-3.3 mu m, putting the ground slurry into an oven, and completely removing water;
step three: crushing the dried powder, screening the crushed powder by a 28-mesh screen, putting the crushed powder into a rotary kiln for secondary pre-sintering, wherein the pre-sintering temperature is shown in table 1;
step four: adding an auxiliary component Nb into the secondary pre-sintered material2O5：250ppm；Co2O3：4000ppm；ZrO2：250ppm；Li2CO3:2000 ppm; CCTO: 500ppm, ball milling is carried out for the ball milling time according to the table 1, and the ball milling particle size D90 is controlled: 2.5-2.7 μm;
step five: crushing the dried powder, sieving with a 40-mesh sieve, adding 15% PVA for granulation, drying at 130 deg.C for 12min, and bidirectionally pressing into green compact ring with inner diameter of 15mm, outer diameter of 25mm and height of 8mm by press machine, and density of 3.1g/cm3Left and right;
step six: and finally, sintering the green ring at the sintering temperature of 1300 ℃, preserving the heat for 6 hours, cooling the green ring to 120 ℃ in a balanced atmosphere at the oxygen partial pressure of 3.8vol%, and discharging the green ring from the furnace, wherein the balanced oxygen partial pressure is adopted in the temperature reduction process.
Comparative example 9 a manganese-zinc power ferrite material was prepared as follows.
Using commercially available purity as Fe2O3(purity is more than or equal to 99.3 percent) and Mn3O4(Mn content is more than or equal to 71 percent) and ZnO (purity is more than or equal to 99.7 percent) according to the main formula of Fe2O3: 54.08 mol%, ZnO 10.74 mol%, Mn3O4The balance being. The preparation method comprises the following specific steps:
the method comprises the following steps: placing the prepared raw materials in a sand mill, adding deionized water according to a ratio of 1:1, adding a proper amount of dispersing agent, mixing for 20min, taking out slurry, drying, pre-sintering the dried powder in a rotary kiln for one time, wherein the pre-sintering atmosphere is air and the time is 2h, the pre-sintering temperature is shown in table 1, and the oxygen content of the pre-sintering atmosphere is 20 vol%;
step two: add the sand milling after 1:1 proportion adds deionized water with a presintering material, the sand milling time is shown according to table 1, control sand milling particle size D90: 3.0-3.3 mu m, putting the ground slurry into an oven, and completely removing water;
step three: crushing the dried powder, screening the crushed powder by a 28-mesh screen, putting the crushed powder into a rotary kiln for secondary pre-sintering, wherein the pre-sintering temperature is shown in table 1;
step four: adding auxiliary component CaCO into secondary pre-sintering material3：500ppm；Nb2O5：250ppm；Co2O3：4000ppm；ZrO2：250ppm；Li2CO32000 ppm; CCTO: 200ppm, ball milling is carried out for the ball milling time according to the table 1, and the ball milling particle size D90 is controlled: 2.5-2.7 μm;
step five: crushing the dried powder, sieving with a 40-mesh sieve, adding 15% PVA for granulation, drying at 130 deg.C for 12min, pressing into blank ring with inner diameter of 15mm, outer diameter of 25mm and height of 8mm by two-way pressing with a press, and density of 3.1g/cm3Left and right;
step six: and finally, sintering the green ring at the sintering temperature of 1300 ℃, preserving the heat for 6 hours, cooling the green ring to 120 ℃ in a balanced atmosphere at the oxygen partial pressure of 3.8vol%, and discharging the green ring from the furnace, wherein the balanced oxygen partial pressure is adopted in the temperature reduction process.
Comparative example 10 a manganese-zinc power ferrite material was prepared as follows.
Using commercially available purity as Fe2O3(purity is more than or equal to 99.3 percent) and Mn3O4(Mn content is more than or equal to 71 percent) and ZnO (purity is more than or equal to 99.7 percent) according to the main formula of Fe2O3: 54.08 mol%, ZnO 10.74 mol%, Mn3O4The balance being. The preparation method comprises the following specific steps:
the method comprises the following steps: placing the prepared raw materials in a sand mill, adding deionized water according to a ratio of 1:1, adding a proper amount of dispersing agent, mixing for 20min, taking out slurry, drying, pre-sintering the dried powder in a rotary kiln for one time, wherein the pre-sintering atmosphere is air and the time is 2h, the pre-sintering temperature is shown in table 1, and the oxygen content of the pre-sintering atmosphere is 20 vol%;
step two: and (3) doping auxiliary components into the primary pre-sintered material: CaCO3: 500 ppm; sanding is carried out, deionized water is added according to the proportion of 1:1, the sanding time is as shown in Table 1, and the sanding grain size D90 is controlled: 3.0-3.3 mu m, putting the ground slurry into an oven, and completely removing water;
step three: crushing the dried powder, screening the crushed powder by a 28-mesh screen, putting the crushed powder into a rotary kiln for secondary pre-sintering, wherein the pre-sintering temperature is shown in table 1;
step four: adding an auxiliary component Nb into the secondary pre-sintered material2O5：250ppm；Co2O3：4000ppm；ZrO2：250ppm；Li2CO32000 ppm; CCTO: 200ppm, carry out the secondary sanding, the sanding time is shown according to table 1, control sanding particle size D90: 2.5-2.7 μm;
step five: crushing the dried powder, sieving with a 40-mesh sieve, adding 15% PVA for granulation, drying at 130 deg.C for 12min, pressing into blank ring with inner diameter of 15mm, outer diameter of 25mm and height of 8mm by two-way pressing with a press, and density of 3.1g/cm3Left and right;
step six: and finally, sintering the green ring at the sintering temperature of 1300 ℃, preserving the heat for 6 hours, cooling the green ring to 120 ℃ in a balanced atmosphere at the oxygen partial pressure of 3.8vol%, and discharging the green ring from the furnace, wherein the balanced oxygen partial pressure is adopted in the temperature reduction process.
Comparative example 11, a manganese-zinc power ferrite material was prepared according to a conventional method.
Using commercially available purity as Fe2O3(purity is more than or equal to 99.3 percent) and Mn3O4(Mn content is more than or equal to 71 percent) and ZnO (purity is more than or equal to 99.7 percent) according to the main formula of Fe2O3: 54.08 mol%, ZnO 10.74 mol%, Mn3O4The balance being. The preparation method comprises the following specific steps:
the method comprises the following steps: placing the prepared raw materials in a sand mill, adding deionized water according to a ratio of 1:1, adding a proper amount of dispersant, sanding for 20min, taking out slurry, drying, presintering the dried powder in a rotary kiln at a presintering temperature of 900 ℃ and an oxygen content of 20vol% in the presintering atmosphere for 2 h;
step two: and (3) doping auxiliary components into the pre-sintered material: CaCO3：500ppm；Nb2O5：250ppm；Co2O3：4000ppm；ZrO2：250ppm；Li2CO32000 ppm; CCTO: 200ppm, sanding, adding deionized water according to a ratio of 1:1, wherein the sanding time is 100min, and controlling the secondary sanding particle size D90: 2.5-2.7 mu m, putting the ground slurry into an oven, and completely removing water;
step three: crushing the dried powder, sieving with a 40-mesh sieve, adding 15% PVA for granulation, drying at 130 deg.C for 12min, pressing into blank ring with inner diameter of 15mm, outer diameter of 25mm and height of 8mm by two-way pressing with a press, and density of 3.1g/cm3Left and right;
step four: and finally, sintering the green ring at the sintering temperature of 1300 ℃, preserving the heat for 6 hours, cooling the green ring to 120 ℃ in a balanced atmosphere at the oxygen partial pressure of 3.8vol%, and discharging the green ring from the furnace, wherein the balanced oxygen partial pressure is adopted in the temperature reduction process.
TABLE 1
Note: the scheme numbered with a symbol is a comparative example. In table 1, the numbers 1 to 5 are inventive examples, and 6 to 11 are comparative examples.
The sample ring prepared through the above steps was subjected to a test of power consumption Pcv and saturation magnetic flux density Bs in SY8218 apparatus of Kawasaki corporation, Japan. The test conditions were respectively: testing the Pcv under the conditions of 100kHz and 200 mT; the properties of the test at 1kHz, 1194A/m are reported in Table 2, and FIG. 1, FIG. 2, FIG. 3 are graphs comparing examples of the invention with comparative examples μ i, 100 ℃ Pcv, 140 ℃ Pcv, respectively.
TABLE 2
As can be seen from the data in Table 2: embodiment 1 ~ 5, adopt suitable temperature of presintering, the crushing mode that sanding and ball-milling combined together, the material performance who makes: μ i (25 ℃) =3000 ± 25% (10 kHz,5 mV); bs (100 ℃) is more than or equal to 460 mT; pcv (25 ℃) is less than or equal to 345kW/m3，Pcv(100℃)≤290kW/m3；Pcv(140℃)≤350kW/m3(ii) a Compared with the comparative example, the material has higher Bs, lower loss in the range of 25-140 ℃, better temperature stability, uniform grain size of the microstructure (shown in figure 4) and small porosity.
In comparative example 6, the pre-sintering temperature was out of the range defined in the present invention, and too high a pre-sintering temperature decreased the reactivity of the powder, and after sintering, the crystal grains did not grow completely, many pores were formed (as shown in FIG. 5), and the high temperature loss was increased.
In comparative example 7, the dielectric material CCTO was not added to the auxiliary component, and the obtained material had low resistivity and increased power loss.
In comparative example 8, the additive amount of the auxiliary component CCTO was 500ppm, and the amount of CCTO in excess of the range defined in the present invention resulted in a decrease in initial permeability and Bs, and an irregular change in resistivity and an increase in loss.
Comparative example 9 auxiliary component CaCO3The particles are not added before the secondary pre-sintering, gaps (shown in figure 6) are filled among the particles, the pre-sintering degree of the inner layer and the outer layer is not uniform, the pre-sintering effect is poor, and the sintered structure is not uniform.
In comparative example 10, the secondary pre-firing and then pulverizing method was performed by sand milling, which resulted in agglomeration of particles, and in the subsequent sintering, the activity was not uniform, the crystal grain size was not uniform, the number of pores was large (as shown in fig. 7), and the loss was deteriorated.
In comparative example 11, the uniformity of the composition and activity of the powder was inferior to that of the secondary pre-firing process, and the obtained microstructure was inferior (as shown in fig. 8), and the loss was increased, using the conventional production method.
The power consumption parameters measured in the embodiment 1 and the comparative example 8 are selected to draw a power consumption-temperature curve, and as shown in fig. 9, compared with an ideal value, the technical scheme of the invention has a more obvious effect of improving the performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (8)
1. A manufacturing method of a wide-temperature low-loss high-Bs manganese-zinc ferrite material is characterized by comprising the following steps of:
the method comprises the following steps: the material is measured and proportioned according to the main component proportion: 53.8-55.2mol% Fe2O39.8 to 13mol percent of ZnO and the balance of Mn3O4Then adding deionized water for mixing, drying to obtain uniform mixed powder, and pre-burning for the first time at the temperature of 700-800 ℃;
step two: adding auxiliary component CaCO into the powder obtained by primary presintering30.05 to 0.1 weight percent, and then drying after sanding;
step three: performing secondary pre-sintering on the mixture prepared in the second step, wherein the temperature of the secondary pre-sintering is 850-950 ℃;
step four: adding the powder subjected to the secondary pre-sintering into the rest auxiliary components, namely 0.3-0.6wt% of Co2O30.015-0.035 wt.% Nb2O50.015 to 0.035 wt.% ZrO20.15-0.25wt% Li2CO3And CCTO with the weight percentage of 0.01-0.03, performing ball milling, drying, wherein the ball milling time is 40-60 min, and controlling the particle size after ball milling to be D90: 2.5-2.7 μm;
step five: granulating the dried powder to obtain powder with good fluidity and filling property, and pressing into a green ring;
step six: sintering the green compact ring pressed in the fifth step to obtain a manganese-zinc ferrite-like ring;
the Mn-Zn ferrite material with wide temperature range, low loss and high Bs prepared by the preparation method has the mu i of 3000 +/-25% under the conditions of 10kHz,5mV and 25 ℃, the Bs of not less than 460mT under the conditions of 1kHz, 1194A/m and 100 ℃, and the Pcv of not more than 345kW/m under the conditions of 100kHz, 200mT and 25 DEG C3The flow rate of the gas at 100kHz,200mT, the Pcv under the condition of 100 ℃ is not higher than 290kW/m3Pcv under the conditions of 100kHz, 200mT and 140 ℃ is not higher than 350kW/m3。
2. The method for preparing a Mn-Zn ferrite material with wide temperature range, low loss and high Bs according to claim 1, wherein in the first step, deionized water is added into the main components according to the mass ratio of 1:1, and the mixture is mixed for 20-30 min.
3. The method as claimed in claim 1, wherein in the first step, the temperature of one pre-sintering is selected from 700 to 800 ℃, the oxygen content is controlled to be 5 to 20vol% by controlling the air and nitrogen mixture ratio, and the pre-sintering time is 2 to 3 hours.
4. The method as claimed in claim 1, wherein the second step is carried out by adding 0.05-0.07wt% CaCO as an auxiliary component3Sanding time is 60~100min, particle size D90 after the control sanding: 3.0 to 3.3 μm.
5. The method for preparing a Mn-Zn ferrite material with wide temperature range, low loss and high Bs according to claim 1, wherein in the third step, the temperature of the second pre-sintering is selected to be 850-950 ℃, the oxygen content is controlled to be 5-20vol% by controlling the ratio of air and nitrogen, and the pre-sintering time is 2-3 h.
6. The method as claimed in claim 1, wherein the supplementary material in the fourth step is Co in an amount of 0.35-0.5wt%2O3(ii) a 0.02-0.03wt% of Nb2O5(ii) a 0.015-0.025wt% ZrO2(ii) a 0.2-0.25wt% Li2CO3(ii) a 0.015-0.025wt% of CCTO.
7. The manufacturing method of the wide-temperature low-loss high-Bs manganese-zinc ferrite material according to claim 1, wherein in the fifth step, 15% of PVA is added into the dried powder for granulation, the granulated powder is dried at 120-140 ℃ for 10-20min to obtain powder with good fluidity and filling property, and the powder is pressed into a green ring under 300-350 MPa.
8. The method as claimed in claim 1, wherein in step six, the sintering temperature is 1280-1320 ℃, the holding time is 4-8h, and the oxygen content is 3.5-4.6 vol%.
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| CN113998999B (en) * | 2022-01-04 | 2022-04-01 | 天通控股股份有限公司 | Manufacturing method of wide-temperature low-loss high-Bs manganese-zinc ferrite material |
| CN114195500B (en) * | 2022-02-18 | 2022-07-12 | 天通控股股份有限公司 | Wide-temperature high-frequency high-magnetic-flux-density manganese-zinc soft magnetic ferrite for charging pile and preparation method thereof |
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| CN115650718A (en) * | 2022-11-18 | 2023-01-31 | 浙江工业大学 | Manganese-zinc ferrite material with ultra-wide temperature, low power consumption and magnetic conductivity and temperature stability and preparation method thereof |
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| CN113998999A (en) | 2022-02-01 |
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