CN118084475A - Low-temperature sintered ultralow-permeability NiCuZn material and preparation method thereof - Google Patents
Low-temperature sintered ultralow-permeability NiCuZn material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 49
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 230000035699 permeability Effects 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 47
- 239000002270 dispersing agent Substances 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 32
- 238000007873 sieving Methods 0.000 claims description 29
- 238000005245 sintering Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000853 adhesive Substances 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 239000007921 spray Substances 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 239000013530 defoamer Substances 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 6
- 238000009766 low-temperature sintering Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 abstract description 46
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 30
- 238000013461 design Methods 0.000 abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- 239000002518 antifoaming agent Substances 0.000 description 33
- 230000005381 magnetic domain Effects 0.000 description 14
- -1 amine salt Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000748 compression moulding Methods 0.000 description 10
- 229920005646 polycarboxylate Polymers 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 9
- 230000007547 defect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 238000001514 detection method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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Abstract
The application relates to the technical field of soft magnetic ferrite materials, and discloses a low-temperature sintered ultralow-permeability NiCuZn material and a preparation method thereof. The low-temperature sintered ultralow-permeability NiCuZn material comprises a main component and an additive; the main components comprise the following raw materials in percentage by mole: fe 2O3 40.0.0-48.0%, znO1-10%, niO35-45%, and CuO in balance; the additive comprises the following raw materials in percentage by mass based on the weight of the main components: 0.5-1.5% SiO 21.0-5.0%、CaCO31.5-7.5%、WO3 and 0.1-0.5% Bi 2O3. The NiCuZn ferrite material prepared by unique components, proportion design and additive selection has excellent current saturation performance, ultralow magnetic permeability, excellent mechanical strength and high-frequency impedance performance, and simultaneously has a higher Q value in high frequency, thereby effectively reducing magnetic loss.
Description
Technical Field
The application relates to the technical field of soft magnetic ferrite materials, in particular to a low-temperature sintered ultralow-permeability NiCuZn material and a preparation method thereof.
Background
Ferrite is a ferromagnetic ceramic material and is widely applied to the fields of electronics, communication, energy sources, environmental protection and the like. Among ferrite materials, niCuZn ferrite is regarded as an important soft magnetic material due to its excellent magnetic properties and good sintering properties.
However, conventional NiCuZn ferrite materials generally need to be sintered at a higher temperature during the preparation process, which not only increases the production cost, but also may cause a change in the crystal structure inside the material, affecting the magnetic properties thereof. In addition, the magnetic permeability of the NiCuZn ferrite material prepared at present is generally higher, and meanwhile, the magnetic loss is higher, the mechanical strength is lower, and the requirement of the material with low magnetic permeability in certain specific applications cannot be met.
For example, in certain magnetic field measurement or magnetically induced sensor applications, it is desirable to use low permeability materials to reduce the effects of magnetic interference, improving measurement accuracy and stability; in the field of electromagnetic interference suppression, the problem of electromagnetic interference in electronic equipment and systems is increasingly serious, and low-permeability materials can be used for electromagnetic shielding and interference suppression, so that the influence of electromagnetic radiation and interference is effectively reduced; in the field of energy conversion, in the energy conversion technologies such as magnetic power generation and magnetohydrodynamic power generation, a low-permeability material is required to reduce magnetic loss and improve energy conversion efficiency; in biomedical fields, in biomedical technologies such as nuclear magnetic resonance imaging and magnetic separation, a low magnetic permeability material is required to reduce the influence on living bodies and improve the imaging quality and separation effect.
Thus, there is an urgent need to prepare a NiCuZn ferrite material with ultra-low permeability and high mechanical strength to meet the needs in specific applications.
Disclosure of Invention
In order to solve at least one technical problem, a NiCuZn ferrite material with ultralow magnetic permeability and high mechanical strength is developed, and the application provides a low-temperature sintered ultralow magnetic permeability NiCuZn material and a preparation method thereof.
On one hand, the low-temperature sintered ultralow-permeability NiCuZn material provided by the application comprises a main component and an additive; wherein the main components comprise the following raw materials in mole percent: fe 2O3 40.0.0-48.0 mol%, znO 1-10mol%, niO35-45mol% and CuO for the rest; the additive comprises the following raw materials in percentage by mass based on the weight of the main components: 0.5-1.5wt% of SiO 2 1.0-5.0wt％、CaCO3 1.5-7.5wt％、WO3 and 0.1-0.5wt% of Bi 2O3.
By adopting the technical scheme, the NiCuZn ferrite material prepared by unique components, proportion design and additive selection has good sintering property, excellent current saturation property, ultralow magnetic conductivity and excellent mechanical strength, and simultaneously has a higher Q value in high frequency, so that the magnetic loss is effectively reduced, and the prepared NiCuZn ferrite material has uniform appearance and color;
the application adopts Fe 2O3 with specific proportion, which is beneficial to controlling the magnetic property of the material; znO with a specific proportion can promote the formation of oxygen defects in the material, and the oxygen defects can serve as pinning centers for the movement of magnetic domain walls to block the rotation of magnetic domains, so that the magnetic permeability is reduced; the NiO with a specific proportion has stronger magnetism, the magnetic domain structure and the magnetic property of the material can be obviously influenced, and excessive magnetic domains are generated in the material by controlling the content of the NiO to block the rotation of the magnetic domains, so that the magnetic permeability is reduced;
The application adopts the additive SiO 2 with specific proportion to improve the insulation performance and mechanical strength of the material, and simultaneously, siO 2 can also co-act with other additives to further optimize the magnetic performance of the material; the interaction of CaCO 3、WO3、Bi2O3 with a specific proportion and the main component is adopted to influence the magnetic property and sintering property of the material, and the microstructure and magnetic domain structure of the material can be improved, so that the magnetic property and current saturation capacity are improved.
Optionally, the additive comprises the following raw materials in percentage by mass: caCO 3 -7.5wt% and WO 3 0.5.5-1.5 wt%.
Preferably, the additive comprises the following raw materials in percentage by mass: caCO 3 4.5.5 wt% and WO 3 wt%.
By adopting the technical scheme, the application adopts the specific CaCO 3 and WO 3 to act together, so that the formation of lattice defects in the material is promoted, and the defects can pin the movement of magnetic domains, thereby further reducing the magnetic permeability.
Preferably, the additive comprises the following raw materials in percentage by mass: siO 2 3wt％、WO3% by weight and Bi 2O3 0.3.3% by weight.
Preferably, the additive comprises the following raw materials in percentage by mass: siO 2 3wt％、CaCO3 4.5.5 wt% and Bi 2O3 0.3.3 wt%.
Preferably, the additive comprises the following raw materials in percentage by mass: siO 2 3wt％、CaCO3 4.5wt％、WO3% by weight and Bi 2O3 0.3.3% by weight.
By adopting the technical scheme, the specific additive system is adopted, and the prepared NiCuZn ferrite material has more excellent comprehensive performance.
Optionally, the main components comprise the following raw materials in mole percent: fe 2O3 42.2.2-45.6 mol%, znO 3.5-6.3mol%, niO 38.4-40.5mol% and CuO for the rest.
Preferably, the main component comprises the following raw materials in mole percent: fe 2O3 43.5.5 mol%, znO 4.1mol%, niO 39.2mol% and the balance CuO.
By adopting the technical scheme, the NiCuZn ferrite material prepared by adopting the main component raw materials with better proportion has better comprehensive performance.
Optionally, the additive further comprises one or both of Y 2O3 0.1-0.6wt% and Ga 2O3 1.0-2.2 wt%.
Preferably, the additive further comprises Y 2O3 0.1.1-0.6 wt% and Ga 2O3 1.0.0-2.2 wt%.
Preferably, the additive further comprises Y 2O3 0.4.4 wt% and Ga 2O3 1.8.8 wt%.
By adopting the technical scheme, the specific dosage of Y 2O3 and Ga 2O3 are added into the additive, so that the crystallinity of ferrite can be effectively improved, impurities and defects are reduced, the magnetic performance is improved, and the mechanical strength and the high-frequency impedance characteristic are improved.
On the other hand, the application provides a preparation method of the low-temperature sintered ultralow-permeability NiCuZn material, which comprises the following steps:
S1, mixing and stirring main components and additives, ball milling, spraying and granulating, and then presintering to prepare a presintering material;
S2, mixing and stirring the presintered material, the adhesive, deionized water, the defoamer and the dispersing agent, and then performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixture;
S3, spraying and granulating the mixture to obtain granules;
s4, placing the granular materials into a die for compression molding to prepare a blank;
S5, sintering the blank to prepare the low-temperature sintered ultralow-permeability NiCuZn material.
By adopting the technical scheme, the preparation method of the ultralow-permeability NiCuZn material by low-temperature sintering is simple and efficient to operate, is environment-friendly and can be used for industrial production; meanwhile, the prepared NiCuZn material has excellent comprehensive performance.
Optionally, in the step S1, the presintering temperature is 850-950 ℃, and the heat preservation time is 150-200min.
Optionally, in S2, the average particle size D50 of the mixture is 0.4-0.8 μm.
Preferably, in S2, the average particle diameter D50 of the mixture is 0.4-0.6 μm.
Optionally, in the step S3, the binder is selected from polyvinyl alcohol solution, and the weight of the polyvinyl alcohol is 0.8-1.5wt% of the weight of the mixture.
Optionally, in the step S5, the sintering temperature is 1000-1150 ℃ and the heat preservation time is 150-200min.
Preferably, in S5, the sintering temperature is 1050-1100 ℃.
In summary, the present invention includes at least one of the following beneficial technical effects:
1. The NiCuZn ferrite material prepared by unique components, proportion design and additive selection has good sintering property, excellent current saturation property, ultralow magnetic conductivity and excellent mechanical strength, and simultaneously has higher Q value in high frequency, thereby effectively reducing magnetic loss;
2. The application adopts Fe 2O3 with specific proportion, which is beneficial to controlling the magnetic property of the material; znO with a specific proportion can promote the formation of oxygen defects in the material, and the oxygen defects can serve as pinning centers for the movement of magnetic domain walls to block the rotation of magnetic domains, so that the magnetic permeability is reduced; the NiO with a specific proportion has stronger magnetism, the magnetic domain structure and the magnetic property of the material can be obviously influenced, and excessive magnetic domains are generated in the material by controlling the content of the NiO to block the rotation of the magnetic domains, so that the magnetic permeability is reduced;
3. The application adopts the additive SiO 2 with specific proportion to improve the insulation performance and mechanical strength of the material, and simultaneously, siO 2 can also co-act with other additives to further optimize the magnetic performance of the material; the interaction of CaCO 3、WO3、Bi2O3 with a specific proportion and the main component is adopted to influence the magnetic property and sintering property of the material, so that the microstructure and magnetic domain structure of the material can be improved, and the magnetic property and current saturation capacity are improved;
4. the preparation method of the low-temperature sintered ultralow-permeability NiCuZn material is simple and efficient to operate, is environment-friendly, and can be used for industrial production.
Drawings
FIG. 1 is a graph showing the frequency-impedance characteristics of the NiCuZn material prepared in example 4;
FIG. 2 is an external view of NiCuZn material prepared in example 24.
Detailed Description
The application is described in further detail below with reference to the drawings and examples.
The application designs a low-temperature sintered ultralow-permeability NiCuZn material, which comprises a main component and an additive; wherein the main components comprise the following raw materials in mole percent: fe 2O3 40.0.0-48.0 mol%, znO 1-10mol%, niO 35-45mol% and CuO for the rest; the additive comprises the following raw materials in percentage by mass based on the weight of the main components: 0.5-1.5wt% of SiO 2 1.0-5.0wt％、CaCO3 1.5-7.5wt％、WO3 and 0.1-0.5wt% of Bi 2O3.
The application discloses a preparation method of a low-temperature sintered ultralow-permeability NiCuZn material, which comprises the following steps:
S1, mixing and stirring main components and additives, ball milling, spraying and granulating, and then presintering to prepare a presintering material;
S2, mixing and stirring the presintered material, the adhesive, deionized water, the defoamer and the dispersing agent, and then performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixture;
S3, carrying out spray granulation on the mixture to obtain granule materials;
s4, placing the granular materials into a die to be pressed and molded to prepare a blank;
S5, sintering the blank to prepare the low-temperature sintered ultralow-permeability NiCuZn material.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The raw materials of the application are as follows, and all the raw materials of the application are from commercial sources unless specified otherwise:
fe 2O3: purity 99%;
ZnO: purity 99%;
NiO: purity 98.5-99%;
CuO: purity 99.9%;
SiO 2: purity 99.9%;
CaCO 3: purity 99%;
WO 3: purity 99.9%;
Bi 2O3: purity 99.9%;
Y 2O3: purity 99.9%;
Ga 2O3: purity 99%;
polyvinyl alcohol: purity 99.99%;
defoaming agent: BYK-024 organosilicon defoamer;
Polycarboxylate amine salt dispersant 5029: fangda Dong chemical Co., ltd.
Detection item and detection method saturation current: when current passes through the ferrite magnetic ring, a magnetic saturation phenomenon of a magnetic body is generated, and inductance is reduced, wherein the characteristic is called direct current superposition characteristic, the number of windings is 10 when the sample of the embodiment is tested, the HP4284A-LCR tester is used for continuously passing through direct current to the sample, so that inductance is reduced, and a current value corresponding to the reduction of the inductance to 30% is defined as saturation current;
Initial permeability: using an E4991B impedance analyzer to test a sample, setting a frequency of 4MHz, inputting parameters of the outer diameter, the inner diameter and the height of the sample, and then reading panel data to obtain an initial permeability value of the sample;
Q value at 20 MHz: uniformly winding 20 circles of insulated copper wires on the surface of a sintered magnet ring sample, and testing the Q value of the sintered magnet ring sample at 20MHz by using Agilent (Agilent technology) equipment E4991 +16192;
Hardness: detecting according to the standard of the apparent hardness and microhardness of GB/T9097-2016 sintered metal materials;
Impedance: the impedance of the sample was tested using an E4991B impedance analyzer.
Examples 1 to 15
The specific raw material weights for the NiCuZn materials of examples 1-15 are shown in Table 1.
TABLE 1
Wherein the balance of the main component is CuO.
Example 1
The preparation method of the low-temperature sintered ultralow-permeability NiCuZn material comprises the following steps:
S1, respectively mixing, ball milling and spray granulating the main components and the additives, and then presintering at 850 ℃ for 200min to prepare a presintering material 1 and a presintering material 2;
S2, mixing and stirring the presintering material 1 and the presintering material 2, and then performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixture with the average particle size D50 of 0.6 mu m; wherein the weight ratio of raw materials, deionized water and steel balls in the two ball milling processes is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour
S3, mixing and stirring the mixture, an adhesive, a defoaming agent and a dispersing agent to obtain slurry, and performing spray granulation to obtain particles with the water content of 0.2wt%, wherein the adding amount of the defoaming agent is 2mL/kg, and the adding amount of the dispersing agent is 1mL/kg;
S4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
s5, sintering the blank at 1050 ℃ for 200min to obtain the low-temperature sintered ultralow-permeability NiCuZn material;
In S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 0.8wt% of the weight of the mixture.
Example 2
The preparation method of the low-temperature sintered ultralow-permeability NiCuZn material comprises the following steps:
S1, respectively mixing, ball milling and spray granulating the main components and the additives, and then presintering at 880 ℃ for 170min to prepare a presintering material 1 and a presintering material 2;
s2, mixing and stirring the presintering material 1 and the presintering material 2, and then performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixture with the average particle size D50 of 0.5 mu m; wherein the weight ratio of raw materials, deionized water and steel balls in the two ball milling processes is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour;
S3, mixing and stirring the mixture adhesive, the defoamer and the dispersant to obtain slurry, and performing spray granulation to obtain particles with the water content of 0.2 wt%; wherein, the adding amount of the defoaming agent is 2mL/kg, and the adding amount of the dispersing agent is 1mL/kg;
S4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
S5, sintering the blank at 1070 ℃ for 180min to obtain the low-temperature sintered ultralow-permeability NiCuZn material; in S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 1wt% of the weight of the mixture.
Example 3
The preparation method of the low-temperature sintered ultralow-permeability NiCuZn material comprises the following steps:
S1, respectively mixing, ball milling and drying the main components and the additives, and then presintering at 910 ℃ for 160min to prepare a presintering material 1 and a presintering material 2;
S2, mixing and stirring the presintering material 1 and the presintering material 2, and then performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixture with the average particle size D50 of 0.4 mu m; wherein the weight ratio of raw materials, deionized water and steel balls in the two ball milling processes is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour;
S3, mixing and stirring the mixture adhesive, the defoamer and the dispersant to obtain slurry, and performing spray granulation to obtain particles with the water content of 0.2 wt%; wherein, the adding amount of the defoaming agent is 2mL/kg, and the adding amount of the dispersing agent is 1mL/kg;
S4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
s5, sintering the blank at 1090 ℃ for 160min to obtain the low-temperature sintered ultralow-permeability NiCuZn material;
In S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 1.5wt% of the weight of the mixture.
Example 4
The preparation method of the low-temperature sintered ultralow-permeability NiCuZn material comprises the following steps:
S1, respectively mixing, ball milling and spray granulating the main components and the additives, and then presintering at 950 ℃ for 150min to prepare a presintering material 1 and a presintering material 2;
S2, mixing and stirring the presintering material 1 and the presintering material 2, and then performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixture with the average particle size D50 of 0.8 mu m; wherein the weight ratio of raw materials, deionized water and steel balls in the two ball milling processes is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour;
s3, mixing and stirring the mixture adhesive, the defoamer and the dispersant to obtain slurry, and performing spray granulation to obtain particles with the water content of 0.2 wt%; wherein, the adding amount of the defoaming agent is 2mLkg, and the adding amount of the dispersing agent is 1mL/kg;
S4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
S5, sintering the blank at 1100 ℃ for 150min to obtain the low-temperature sintered ultralow-permeability NiCuZn material;
in S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 0.1.3wt% of the weight of the mixture.
Examples 5 to 7
The preparation method of the low-temperature sintered ultralow-permeability NiCuZn material of examples 5-7 is identical to that of example 1.
Examples 8 to 15
The preparation method of the low-temperature sintered ultralow-permeability NiCuZn material of examples 8-15 is identical to that of example 2.
Example 16
The procedure of example 14 was followed except that the D50 of the mixture in S2 was 0.8. Mu.m, and the composition and preparation were the same as in example 14.
Example 17
Based on example 14, the other components and preparation methods were identical to those of example 14, except that the sintering temperature in S5 was 1000 ℃.
Example 18
Based on example 14, the other components and preparation methods were the same as in example 14 except that the sintering temperature in S5 was 1150 ℃.
Example 19
The preparation was identical to that of example 14, except that the additive comprises 0.1% by weight of Y 2O3, based on example 14; the preparation method of the NiCuZn material with ultralow magnetic conductivity by low-temperature sintering comprises the following steps:
S1, respectively mixing, ball milling and spray granulating the main components and the additives, and then presintering at 880 ℃ for 170min to prepare a presintering material 1 and a presintering material 2;
s2, mixing and stirring the presintering material 1 and the presintering material 2, and then performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixture with the average particle size D50 of 0.5 mu m; wherein the weight ratio of raw materials, deionized water and steel balls in the two ball milling processes is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour;
S3, mixing and stirring the mixture adhesive, the defoamer and the dispersant to obtain slurry, and performing spray granulation to obtain particles with the water content of 0.2 wt%; wherein, the adding amount of the defoaming agent is 2mL/kg, and the adding amount of the dispersing agent is 1mL/kg;
S4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
S5, sintering the blank at 1070 ℃ for 180min to obtain the low-temperature sintered ultralow-permeability NiCuZn material;
In S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 1wt% of the weight of the mixture.
Example 20
The preparation was identical to that of example 14, except that the additive comprises 1.0 wt.% Ga 2O3, based on example 14; the preparation method of the NiCuZn material with ultralow magnetic conductivity by low-temperature sintering comprises the following steps:
S1, respectively mixing, ball milling and drying the main components and the additives, ball milling and spray granulating, and then presintering at 880 ℃ for 170min to prepare a presintering material 1 and a presintering material 2;
S2, after mixing and stirring the presintering material 1 and the presintering material 2, carrying out primary ball milling and sieving and secondary ball milling and sieving treatment, and carrying out ball milling and sieving treatment to prepare a mixture with the average particle diameter D50 of 0.5 mu m; wherein the weight ratio of raw materials, deionized water and steel balls in the two ball milling processes is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour;
s3, mixing and stirring the mixture, an adhesive, a defoaming agent and a dispersing agent to obtain slurry, and performing spray granulation to obtain particles with the water content of 0.2 wt%; wherein, the adding amount of the defoaming agent is 2mL/kg, and the adding amount of the dispersing agent is 1mL/kg;
S4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
S5, sintering the blank at 1070 ℃ for 180min to obtain the low-temperature sintered ultralow-permeability NiCuZn material;
In S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 1wt% of the weight of the mixture.
Examples 21 to 23
The preparation was identical to that of example 14, except that the additives included Y 2O3 and Ga 2O3, based on example 14; the preparation method of the NiCuZn material with ultralow magnetic conductivity by low-temperature sintering comprises the following steps:
S1, respectively mixing, ball milling and drying the main components and the additives, ball milling and spray granulating, and then presintering at 880 ℃ for 170min to prepare a presintering material 1 and a presintering material 2;
S2, after mixing and stirring the presintering material 1 and the presintering material 2, carrying out primary ball milling and sieving and secondary ball milling and sieving treatment, and carrying out ball milling and sieving treatment to prepare a mixture with the average particle diameter D50 of 0.5 mu m; wherein the weight ratio of raw materials, deionized water and steel balls in the two ball milling processes is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour;
s3, mixing and stirring the mixture, an adhesive, a defoaming agent and a dispersing agent to obtain slurry, and performing spray granulation to obtain particles with the water content of 0.2 wt%; wherein, the adding amount of the defoaming agent is 2mL/kg, and the adding amount of the dispersing agent is 1mL/kg;
S4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
S5, sintering the blank at 1070 ℃ for 180min to obtain the low-temperature sintered ultralow-permeability NiCuZn material;
In S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 1wt% of the weight of the mixture.
Example 21
Y 2O3 0.1.1 wt% and Ga 2O3 1.0.0 wt%.
Example 22
Y 2O3 0.4.4 wt% and Ga 2O3 1.8.8 wt%.
Example 23
Y 2O3 0.6.6 wt% and Ga 2O3 2.2.2 wt%.
Example 24
Based on example 22, the preparation methods were the same as in example 22 except that S1 and S2 were different;
the preparation method of the low-temperature sintered ultralow-permeability NiCuZn material comprises the following steps:
S1, mixing and stirring main components and additives, performing ball milling and spray granulation, and performing presintering treatment, wherein the presintering temperature is 880 ℃, and the heat preservation time is 170min, so as to prepare a presintering material;
s2, performing primary ball milling and sieving and secondary ball milling and sieving treatment on the presintered material, and performing ball milling and sieving treatment on the presintered material to prepare a mixture with the average particle size D50 of 0.5 mu m; wherein the weight ratio of raw materials, deionized water and steel balls in the two ball milling processes is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour;
s3, mixing and stirring the mixture, an adhesive, a defoaming agent and a dispersing agent to obtain slurry, and performing spray granulation to obtain particles with the water content of 0.2 wt%; wherein, the adding amount of the defoaming agent is 2mL/kg, and the adding amount of the dispersing agent is 1mL/kg;
S4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
S5, sintering the blank at 1070 ℃ for 180min to obtain the low-temperature sintered ultralow-permeability NiCuZn material;
In S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 1wt% of the weight of the mixture.
Example 25
Based on example 24, the preparation methods were the same as in example 24 except that S2 and S3 were different;
the preparation method of the low-temperature sintered ultralow-permeability NiCuZn material comprises the following steps:
S1, mixing and stirring main components and additives, performing ball milling and spray granulation, and performing presintering treatment, wherein the presintering temperature is 880 ℃, and the heat preservation time is 170min, so as to prepare a presintering material;
S2, mixing and stirring the presintered material, the adhesive, the deionized water, the defoaming agent and the dispersing agent to obtain slurry, and performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixed material with the average particle size D50 of 0.5 mu m, wherein the weight ratio of the raw materials to the deionized water to the steel balls in the secondary ball milling process is 2:1:6, the primary ball milling time is 3 hours, and the secondary ball milling time is 1 hour; the adding amount of the defoaming agent is 2mL/kg, and the adding amount of the dispersing agent is 1mL/kg;
s3, taking the mixture, and carrying out spray granulation to obtain granules with the water content of 0.2 wt%; s4, placing the granules into a die for compression molding to prepare a blank, wherein the specification of the blank is phi 25 multiplied by phi 15 multiplied by 7.5mm;
S5, sintering the blank at 1070 ℃ for 180min to obtain the low-temperature sintered ultralow-permeability NiCuZn material;
In S3, the defoaming agent is BYK-024 organic silicon defoaming agent; the dispersant is polycarboxylate amine salt dispersant 5029; the adhesive is a polyvinyl alcohol solution with the concentration of 10 weight percent; the weight of the polyvinyl alcohol is 1wt% of the weight of the mixture.
Comparative examples 1 to 6
Comparative example 1
The composition and preparation were the same as in example 2 except that the main component had a Fe 2O3 mol% and CuO mol% of 23.1 mol% based on example 2.
Comparative example 2
The composition and preparation were the same as in example 2 except that the main component had a Fe 2O3 mol% and CuO mol% of 50.1 mol% based on example 2.
Comparative example 3
The composition and preparation were the same as in example 2, except that the mol% of ZnO in the main component was 12% and the mol% of CuO was 7.4% based on example 2.
Comparative example 4
The composition and preparation were the same as in example 2 except that the mol% of ZnO in the main component was 0.5% and the mol% of CuO was 18.9% based on example 2.
Comparative example 5
The composition and preparation were the same as in example 2, except that the molar percentage of NiO in the main component was 30% and the molar percentage of CuO was 24.3%, based on example 2.
Comparative example 6
The composition and preparation were the same as in example 2, except that the molar percentage of NiO in the main component was 48% and the molar percentage of CuO was 6.3%, based on example 2.
The NiCuZn materials prepared in examples 1 to 21 and comparative examples 1 to 6 were subjected to performance test, and the test results are shown in Table 2.
TABLE 2
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As can be seen from examples 1-4, comparative examples 1-6 and Table 2, the NiCuZn ferrite material prepared by adopting specific components and proportion design and selection of additives has excellent current saturation performance, ultralow magnetic permeability, high Q value and excellent hardness and high-frequency impedance; meanwhile, as can be seen from fig. 1, the NiCuZn ferrite material prepared in example 4 of the present application has excellent high frequency impedance characteristics, and the impedance is 1682 Ω at 1000 MHz;
As can be seen from examples 5-7, 1 and Table 2, the NiCuZn ferrite material prepared by adopting both SiO 2 and Bi 2O3 as the additive of the application has more excellent comprehensive properties than the NiCuZn ferrite material prepared by singly adding SiO 2 or Bi 2O3; from examples 8-10, 2 and Table 2, it is clear that the additives of the present application can co-act with CaCO 3、WO3 to promote the formation of lattice defects in the material, which can pin the movement of magnetic domains to further reduce magnetic permeability;
As can be seen from examples 11-13, 9 and Table 2, the additive of the application adopts SiO 2、CaCO3、WO3 and Bi 2O3 with specific contents, which is more beneficial to reducing magnetic permeability and improving current saturation performance, and the prepared NiCuZn ferrite material has more excellent comprehensive performance;
as can be seen from examples 13-15 and Table 2, the NiCuZn ferrite material prepared by adopting the main components with better proportion has better comprehensive performance;
As is clear from examples 16 and 14 and table 2, although the saturation current is better and the magnetic permeability is lower when the D50 of the mixture in S2 is higher than the value range, the mechanical properties of the prepared NiCuZn ferrite material are poor, the brittleness is large, the contact area between particles is reduced, and the sintering is not facilitated;
As is clear from examples 17 to 18, 14 and Table 2, when the sintering temperature in S5 is too high or too low, the saturation performance and permeability of the prepared NiCuZn ferrite material are good, but the lattice structure inside the material is unstable, and the mechanical strength is further reduced; as can be seen from examples 19 to 23, 14 and table 2, the addition of Y 2O3 and Ga 2O3 to the additive of the present application can effectively improve the crystallinity of ferrite, reduce impurities and defects, improve magnetic properties, and improve mechanical strength;
As can be seen from examples 22, 24, 25 and table 2, in the present application, in S1, after mixing and stirring the main component and the additive, ball milling, spray granulation and pre-sintering are performed, so that the prepared pre-sintering material has higher dispersibility, which is more beneficial to improving the comprehensive performance of the ferrite material; in the grinding stage in S2, adding the adhesive, deionized water, the defoamer and the dispersant to perform ball milling and sieving and secondary ball milling and sieving treatment together, so that the dispersion uniformity of the mixture is further promoted, and the prepared ferrite material has excellent comprehensive performance; meanwhile, as can be seen from fig. 2, the NiCuZn ferrite material prepared by the application has a black and uniform appearance and color;
As is clear from comparative examples 1 to 6, example 2 and Table 2, the NiCuZn ferrite material prepared by adopting the specific mole percentages of Fe 2O3, niO and ZnO has excellent current saturation performance and ultralow magnetic permeability.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes according to the principles of the present application should be covered by the scope of the present application.
Claims (10)
1. The low-temperature sintered ultralow-permeability NiCuZn material is characterized by comprising a main component and an additive; wherein the main components comprise the following raw materials in mole percent: fe 2O3 40.0.0-48.0 mol%, znO 1-10mol%, niO 35-45mol% and CuO for the rest; the additive comprises the following raw materials in percentage by mass based on the weight of the main components: 0.5-1.5wt% of SiO 21.0-5.0wt%、CaCO3 1.5-7.5wt%、WO3 and 0.1-0.5wt% of Bi 2O3.
2. The low-temperature sintered ultralow permeability NiCuZn material according to claim 1, wherein said additive comprises the following raw materials in mass percent: caCO 3 -7.5wt% and WO 3 0.5.5-1.5 wt%.
3. The low-temperature sintered ultralow permeability NiCuZn material according to claim 1, wherein said additive comprises the following raw materials in mass percent: siO 2 3wt%、CaCO3 4.5wt%、WO3% by weight and Bi 2O3 0.3.3% by weight.
4. The low temperature sintered ultralow permeability NiCuZn material according to claim 1, wherein said main component comprises the following raw materials in mole percent: fe 2O3 42.2.2-45.6 mol%, znO 3.5-6.3mol%, niO 38.4-40.5mol% and CuO for the rest.
5. A low temperature sintered ultralow permeability NiCuZn material according to claim 1, wherein said additive further comprises one or both of Y 2O3 0.1-0.6wt% and Ga 2O3 1.0-2.2 wt%.
6. A method for preparing the low-temperature sintered ultralow permeability NiCuZn material as defined in any one of claims 1 to 5, comprising the steps of:
S1, mixing and stirring main components and additives, ball milling, spraying and granulating, and then presintering to prepare a presintering material;
S2, mixing and stirring the presintered material, the adhesive, deionized water, the defoamer and the dispersing agent, and then performing primary ball milling and sieving and secondary ball milling and sieving treatment to prepare a mixture;
S3, carrying out spray granulation on the mixture to obtain granule materials;
s4, placing the granular materials into a die to be pressed and molded to prepare a blank;
s5, sintering the blank to obtain the low-temperature sintered ultralow-permeability NiCuZn material.
7. The method for preparing the ultralow permeability NiCuZn material by low temperature sintering according to claim 6, wherein in the step S1, the presintering temperature is 850-950 ℃, and the heat preservation time is 150-200min.
8. The method for preparing a low temperature sintered ultralow permeability NiCuZn material according to claim 6, wherein in S2, the average particle diameter D50 of the mixture is 0.4 to 0.8 μm.
9. The method for preparing a low temperature sintered ultralow permeability NiCuZn material according to claim 6, wherein in S3, the binder is selected from polyvinyl alcohol solution, and the weight of the polyvinyl alcohol is 0.8-1.5wt% of the weight of the mixture.
10. The method for preparing a low temperature sintered ultralow permeability NiCuZn material according to claim 6, wherein in S5, the sintering temperature is 1000-1150 ℃ and the heat preservation time is 150-200min.
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