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CN115995339A - Iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability and preparation method - Google Patents

Iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability and preparation method Download PDF

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CN115995339A
CN115995339A CN202310089729.XA CN202310089729A CN115995339A CN 115995339 A CN115995339 A CN 115995339A CN 202310089729 A CN202310089729 A CN 202310089729A CN 115995339 A CN115995339 A CN 115995339A
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equal
tensile stress
less
magnetic field
iron
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朱政权
孙保安
苏枫超
李伟峰
刘果明
周靖
李雪松
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Friendship Nano Crystal Technology Co ltd
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Friendship Nano Crystal Technology Co ltd
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Abstract

The invention provides an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability and a preparation method thereof, and relates to the technical field of amorphous nanocrystalline magnetic core preparation. The method provided by the invention can be used for preparing the nanocrystalline magnetic core with low coercive force and low constant magnetic permeability, and the magnetic permeability attenuation is not more than 10% in the frequency range of 10kHz-1 MHz. Compared with the magnetic field annealing, the method shortens the heat treatment time within 5min, and shortens the process of industrial production; the low heat treatment temperature is favorable for environmental protection and energy saving to a certain extent, so the cost is lower, and the method has better application prospect.

Description

Iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability and preparation method
Technical Field
The invention relates to the technical field of amorphous nanocrystalline magnetic core preparation, in particular to an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability and a preparation method thereof.
Background
The magnetic core with constant magnetic conductivity has wide application prospect in low-power small devices with stable transmission, such as high-precision current transformers, linear chokes and the like.
Ferrite powder soft magnetic materials have extremely stable low and constant permeability over a wide frequency range, even though the attenuation of permeability is low in the MHz range; however, the weak magnetic exchange coupling of the ferrite results in a ferrite having only a low saturation induction (B s ) High coercivity (H) c ) And poor temperature stability, which limits its range of applications.
Chinese patent CN104376950a discloses an iron-based constant magnetic conduction nanocrystalline magnetic core and its preparation method, the alloy molecular formula is Fe a Cu b Nb c Si d B e M f X g Wherein M is at least one of the elements V, ti, mn, cr, mo and X is at least one of the elements C, ge, P and impurities. The patent obtains low constant magnetic permeability and large anisotropic field through isothermal constant stress annealing, has better DC resistance, however B s The low value of about 1.2T and a coercivity greater than 10A/m makes the core severely lossy when operating in a high frequency environment.
Disclosure of Invention
The invention aims to provide an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability, which comprises the following steps:
carrying out induction smelting on the raw materials of the iron-based nanocrystalline magnetic core to obtain a master alloy ingot;
heating the master alloy ingot to be molten, spraying the obtained alloy liquid onto the surface of a metal roller for quenching to obtain an amorphous thin strip;
simultaneously applying tensile stress and a magnetic field along the strip direction of the amorphous thin strip to perform tensile stress-magnetic field composite annealing to obtain an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability; the temperature of the tensile stress-magnetic field composite annealing is T x1 ±8℃,T x1 A first crystallization temperature for the amorphous ribbon; the tensile stress of the tensile stress-magnetic field composite annealing is 20-50 MPa;
the molecular formula of the iron-based nanocrystalline magnetic core is Fe a Si b B c Cu d Nb e Wherein a, b, c, d and e are atomic percent, b is more than or equal to 7 and less than or equal to 18; c is more than or equal to 5 and less than or equal to 13; d is more than or equal to 0.5 and less than or equal to 1.5; e is more than or equal to 0.5 and less than or equal to 4; the balance being a.
Preferably, the time of the tensile stress-magnetic field composite annealing is 10-300 s.
Preferably, the tensile stress of the tensile stress-magnetic field composite annealing is 25-45 MPa.
Preferably, the external magnetic field strength of the tensile stress-magnetic field composite annealing is below 800Gs.
Preferably, the external magnetic field strength of the tensile stress-magnetic field composite annealing is 800Gs.
Preferably, the Fe a Si b B c Cu d Nb e In the formula, 73 is less than or equal to a and less than or equal to 76, 20 is less than or equal to b+c is less than or equal to 25,1 is less than or equal to d is less than or equal to 1.5, and 1 is less than or equal to e is less than or equal to 3.
Preferably, the Fe a Si b B c Cu d Nb e Is Fe 73.5 Si 15.5 B 7 Cu 1 Nb 3
Preferably, the average grain size of the iron-based nanocrystalline core is 13.02-17.75 nm.
The invention provides the iron-based nanocrystalline magnetic core prepared by the preparation method of the scheme, and the coercive force H c 2.6 to 4.0A/m; relative to the initial magnetic permeability mu i 800-1000.
Preferably, the permeability decay rate is not more than 10% in the frequency range of 10kHz to 1 MHz.
The invention provides a preparation method of an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability, which comprises the following steps: carrying out induction smelting on the raw materials of the iron-based nanocrystalline magnetic core to obtain a master alloy ingot; heating the master alloy ingot to be molten, spraying the obtained alloy liquid onto the surface of a metal roller for quenching to obtain an amorphous thin strip; simultaneously applying tensile stress and a magnetic field along the strip direction of the amorphous thin strip to perform tensile stress-magnetic field composite annealing to obtain an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability; the temperature of the tensile stress-magnetic field composite annealing is T x1 ±8℃,T x1 A first crystallization temperature for the amorphous ribbon; the tensile stress of the tensile stress-magnetic field composite annealing is 20-50 MPa; the molecular formula of the iron-based nanocrystalline magnetic core is Fe a Si b B c Cu d Nb e Wherein a, b, c, d and e are atomic percent, b is more than or equal to 7 and less than or equal to 18; c is more than or equal to 5 and less than or equal to 13; d is more than or equal to 0.5 and less than or equal to 1.5; e is more than or equal to 0.5 and less than or equal to 4; the balance being a. The content of nonmetallic elements Si and B in the iron-based nanocrystalline magnetic core provides better amorphous forming capability for the material, the appropriate amount of Cu element improves the nucleation density of alpha-Fe nanocrystalline grains, and the appropriate amount of Nb can inhibit the growth of the alpha-Fe nanocrystalline grains, thereby being beneficial to the amorphous nanocrystalline dual-phase structure with fine performance and reducing the coercive force of the material. The invention adopts the tensile stress-magnetic field composite annealing to fully release the internal stress of the strip, and can further reduce the magnetic conductivity and coercive force of the iron-based nanocrystalline magnetic core.
The method provided by the invention can be used for preparing the nanocrystalline magnetic core with low coercive force and low constant magnetic permeability, and the magnetic permeability attenuation is not more than 10% in the frequency range of 10kHz-1 MHz.
Furthermore, compared with magnetic field annealing, the annealing time of the invention can be shortened to be within 5 minutes, and the process of industrial production is shortened; the low heat treatment temperature is favorable for environmental protection and energy saving to a certain extent, so the cost is low and the application prospect is good.
Drawings
FIG. 1 is a schematic structural diagram of a tensile stress-magnetic field composite heat treatment furnace used in the invention, wherein 1 is a general control system, 2 is a belt releasing side transmission shaft system, 3 is a heating pipeline, 4 is a belt collecting side transmission shaft system, and 5 is an electromagnet;
FIG. 2 is a plot of coercivity versus applied tensile stress value in an anneal for a magnetic core;
FIG. 3 shows the microstructure (left) and grain size distribution (right) of the nanocrystalline core obtained at an annealing temperature of 490℃and a tensile stress of 29 MPa.
Detailed Description
The invention provides a preparation method of an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability, which comprises the following steps:
carrying out induction smelting on the raw materials of the iron-based nanocrystalline magnetic core to obtain a master alloy ingot;
heating the master alloy ingot to be molten, spraying the obtained alloy liquid onto the surface of a metal roller for quenching to obtain an amorphous thin strip;
simultaneously applying tensile stress and a magnetic field along the strip direction of the amorphous thin strip to perform tensile stress-magnetic field composite annealing to obtain an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability; the temperature of the tensile stress-magnetic field composite annealing is T x1 ±8℃,T x1 A first crystallization temperature for the amorphous ribbon; the tensile stress of the tensile stress-magnetic field composite annealing is 20-50 MPa;
the molecular formula of the iron-based nanocrystalline magnetic core is Fe a Si b B c Cu d Nb e Wherein a, b, c, d and e are atomic percent, b is more than or equal to 7 and less than or equal to 18; c is more than or equal to 5 and less than or equal to 13; d is more than or equal to 0.5 and less than or equal to 1.5; e is more than or equal to 0.5 and less than or equal to 4; the balance being a.
The invention carries out induction smelting on the raw materials of the iron-based nanocrystalline magnetic core to obtain a master alloy ingot.
In the present invention, the induction smelting is preferably performed under nitrogen protection, and the induction smelting is preferably multiple induction smelting. After each smelting, the invention preferably also comprises deslagging.
After a master alloy ingot is obtained, the master alloy ingot is heated to be molten, and the obtained alloy liquid is sprayed on the surface of a metal roller for quenching, so that an amorphous ribbon is obtained.
In the present invention, the metal roll is preferably a copper roll, and the rotational speed of the metal roll is preferably 30 to 40m/s. The thickness of the amorphous ribbon is not particularly limited in the present invention, and may be any thickness known in the art, such as 17 μm or 20 μm. In the present invention, the width of the amorphous ribbon is preferably 10mm. The invention preferably provides for the amorphous ribbon to be subjected to a subsequent step in the form of a roll.
According to the invention, tensile stress and a magnetic field are applied simultaneously along the strip direction of the amorphous thin strip for carrying out tensile stress-magnetic field composite annealing, so that the iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability is obtained.
In the present invention, the tensile stress-magnetic field composite annealing is preferably performed in a tensile stress-magnetic field composite heat treatment furnace. In order to facilitate a better understanding of the technical solution of the present application, a description will now be given with reference to fig. 1. FIG. 1 is a schematic structural view of a tensile stress-magnetic field composite heat treatment furnace.
The invention firstly fixes the coiled amorphous thin belt in the belt-releasing-side conveying shaft system 2, and sequentially bypasses each sub-transmission shaft to ensure the uniformity of the stress of the belt in the stretching process and prevent the belt from breaking; after the fixation is completed, the strip passes through the heating pipeline 3 and the electromagnet 5 and is sent to the belt collecting side transmission system 4, and then the amorphous thin belt bypasses each sub-transmission shaft according to the symmetrical sequence in the belt releasing side transmission shaft system 1 and is fixed; then, the general control system 1 is programmed to adjust the annealing time, the heating pipeline temperature and the intensity of the external magnetic field, the equipment is started to perform tensile stress-magnetic field composite annealing (i.e. the annealing is performed by simultaneously applying tensile stress along the strip direction and magnetic field parallel to the strip direction), and finally, the annealed strip is wound into a magnetic core with a specified size by using the manual winding equipment.
In the invention, the temperature of the tensile stress-magnetic field composite annealing is T x1 Preferably T at + -8deg.C x1 ±5℃,T x1 A first crystallization temperature for the amorphous ribbon; the time is preferably 10 to 300 seconds, more preferably 30 to 280 seconds, still more preferably 50 to 230 seconds, most preferably100-200 s. The invention controls the annealing temperature and time in the range, has low effective annealing time, saves energy and protects environment, and fully ensures that the nanocrystalline in the amorphous is evenly separated out.
In the present invention, the tensile stress of the tensile stress-magnetic field composite annealing is 20 to 50MPa, preferably 25 to 45MPa, and more preferably 28 to 40MPa. The tensile stress in the range plays a role in promoting the growth of alpha-Fe nanocrystalline, balances the saturated magnetostriction of the amorphous matrix and nanocrystalline phases, and reduces the coercive force of the magnetic core.
In the present invention, the external magnetic field strength of the tensile stress-magnetic field composite annealing is preferably 800Gs or less, more preferably 800Gs. The invention controls the magnetic field intensity in the above range, and can ensure that the effect of improving the performance is good.
In the invention, the molecular formula of the iron-based nanocrystalline magnetic core is Fe a Si b B c Cu d Nb e Wherein a, b, c, d and e are atomic percent, b is more than or equal to 7 and less than or equal to 18; c is more than or equal to 5 and less than or equal to 13; d is more than or equal to 0.5 and less than or equal to 1.5; e is more than or equal to 0.5 and less than or equal to 4; the rest is a; preferably, 73.ltoreq.a.ltoreq.76, 20.ltoreq.b+c.ltoreq.25, 1.ltoreq.d.ltoreq.1.5, 1.ltoreq.e.ltoreq.3. In an embodiment of the present invention, the Fe a Si b B c Cu d Nb e Is Fe 73.5 Si 15.5 B 7 Cu 1 Nb 3 . The proper amount of nonmetallic elements Si and B provide better amorphous forming capability for the magnetic core, the proper amount of Cu element improves the nucleation density of alpha-Fe nanocrystalline grains, and the proper amount of Nb can inhibit the growth of the alpha-Fe nanocrystalline grains, thereby being beneficial to the amorphous nanocrystalline dual-phase structure with fine performance and reducing the coercive force of the material.
In the invention, the average grain size of the iron-based nanocrystalline magnetic core is preferably 13.02-17.75 nm; the iron-based nanocrystalline magnetic core is preferably of an annular structure without air gaps.
The invention provides the iron-based nanocrystalline magnetic core prepared by the preparation method of the scheme, and the coercive force H c 2.6 to 4.0A/m; relative to the initial magnetic permeability mu i 800-1000. Saturation induction intensity B s Preferably 1.25T, in the frequency range of 10kHz to 1MHzThe permeability decay rate in is preferably not more than 10%.
The iron-based nanocrystalline core with low coercivity and low permeability and the method of manufacturing the same according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Examples and comparative examples
By Fe 73.5 Si 15.5 B 7 Cu 1 Nb 3 The amorphous alloy is used for preparing a nanocrystalline magnetic core, and the specific steps are as follows:
(1) The raw materials of each group are weighed and mixed according to the proportion, and the high-purity master alloy ingot is obtained by using an induction arc furnace to carry out vacuum smelting for a plurality of times.
(2) Melting the master alloy ingot obtained in the step (1) to obtain alloy liquid, and spraying the alloy liquid onto the surface of a copper roller (the rotating speed is 35 m/s) to obtain an iron-based amorphous alloy ribbon (T) x1 490 deg.c) was cut with a fixed-width roll to obtain an amorphous ribbon 10mm wide and 17 μm thick.
(3) Carrying out tensile stress-magnetic field composite annealing on the amorphous strip obtained in the step (2) by using a tensile stress-magnetic field composite heat treatment furnace (shown in figure 1), firstly fixing the coiled amorphous strip in a strip releasing side conveying shaft system 2, and sequentially bypassing the amorphous strip around each sub-transmission shaft so as to ensure the stress uniformity of the amorphous strip in the stretching process and prevent the amorphous strip from being broken; after the fixation is completed, the amorphous thin belt passes through the heating pipeline 3 and the electromagnet 5 and is sent to the belt collecting side transmission system 4, and then the amorphous thin belt bypasses each sub-transmission shaft according to the symmetrical sequence in the belt releasing side transmission shaft system 1 and is fixed; then, the total control system 1 is programmed to adjust the annealing time, the heating pipeline temperature and the intensity of the externally applied magnetic field, the equipment is started to anneal, and finally, the annealed strip is coiled into a magnetic core with a specified size by using a manual coiling equipment.
And applying tensile stress and an external magnetic field along the stretching direction of the belt shaft in the whole annealing process, wherein the temperature control precision is not more than +/-1 ℃, the control precision of the tensile stress is not more than +/-1 MPa, the magnetic field strength is 800Gs, and the annealing temperature, time and tensile stress are specifically shown in Table 1. The thickness of the annealed strip is not greatly reduced.
(4) The annealed nanocrystalline strip is wound into a magnetic core with the specification of 24mm multiplied by 20mm multiplied by 10mm according to the size.
Table 1 annealing conditions and soft magnetic properties of the cores of examples and comparative examples
Numbering device Temperature/. Degree.C Time/s σ/MPa H c /Am -1 μ i μ e Attenuation rate (10 KHz-1 MHz)
Comparative example 1 480 270 0 7.51 1149 5.23%
Comparative example 2 480 270 29 7.47 1122 3.88%
Comparative example 3 480 270 59 7.45 1148 5.59%
Comparative example 4 480 270 88 7.46 1195 5.11%
Comparative example 5 490 270 0 4.56 902 4.71%
Example 1 490 270 24 3.57 930 4.21%
Example 2 490 270 29 2.67 986 5.15%
Example 3 490 270 35 2.80 994 5.59%
Example 4 490 270 41 3.07 902 6.02%
Comparative example 6 490 270 59 4.86 950 5.30%
Comparative example 7 490 270 88 6.92 917 6.33%
Comparative example 8 500 270 29 2.80 1369 8.99%
As is clear from Table 1, the magnetic core prepared by the tensile stress-magnetic field composite annealing has low initial permeability and low coercive force, and the permeability attenuation rate in the frequency range of 10kHz-1MHz is not more than 10%, and the magnetic performance is excellent.
FIG. 2 shows the coercivity H of a magnetic core c (A/m) a trend curve of the magnitude of tensile stress sigma (MPa) applied during annealing. As can be seen from fig. 2, the precipitation and growth of the nanocrystals are less at the annealing temperature of 480 ℃, and the adjustment effect of the tensile stress on the nanocrystals is very small. At this time, the coercive force of the magnetic core is maintained at about 7.5A/m, and the whole process can be regarded as stress relief annealing. The annealing temperature is increased to 490 ℃, enough energy is obtained for the nanocrystalline to start growing, and the adjusting effect of tensile stress on the coercive force of the magnetic core can be obviously seen. The adjusting effect reaches the best comprehensive performance at 490 ℃ and 29MPa, at this time H c =2.67A/m. However, when the annealing temperature was further increased to 500 ℃, since a fine nanocrystalline structure was already formed inside the material when no tensile stress was applied, the tensile stress applied caused the nanocrystalline size to rapidly grow, but rather caused deterioration of magnetic properties, and thus, comparative example 8 had both an increased magnetic core coercive force and an initial permeability, and magnetic properties were lowered, as compared with example 2.
Further, as can be seen from fig. 2 and table 1, when the tensile stress is too large, the grain size inside the material is rapidly increased, the magnetocrystalline anisotropy is increased, and the soft magnetic properties are deteriorated, and thus the coercive force of comparative examples 6 and 7 is increased as compared with comparative examples 5 and 1 to 4.
FIG. 3 shows a microstructure (left) and a grain size distribution (right) of a nanocrystalline core obtained at an annealing temperature of 490℃and a tensile stress of 29 MPa. It can be seen that the α -Fe nanocrystals were uniformly distributed in the amorphous matrix, and the selected area electron diffraction pattern showed three diffraction rings of standard (110) (200) (211), with an average grain size of 13.02 μm.
To sum up, fe 73.5 Si 15.5 B 7 Cu 1 Nb 3 Conditions for the core to obtain low coercivity and low constant permeability: at T x1 Annealing at + -8deg.C for 270s while applying a certain tensile stress and magnetic field. The magnetic core has low processing cost and short annealing time, and simultaneously has coercivity as low as 2.6A/m and adjustable relative constant permeability (10 kHz-1 MHz) between 800 and 1000.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The preparation method of the iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability is characterized by comprising the following steps of:
carrying out induction smelting on the raw materials of the iron-based nanocrystalline magnetic core to obtain a master alloy ingot;
heating the master alloy ingot to be molten, spraying the obtained alloy liquid onto the surface of a metal roller for quenching to obtain an amorphous thin strip;
simultaneously applying tensile stress and a magnetic field along the strip direction of the amorphous thin strip to perform tensile stress-magnetic field composite annealing to obtain an iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability; the temperature of the tensile stress-magnetic field composite annealing is T x1 ±8℃,T x1 A first crystallization temperature for the amorphous ribbon; the tensile stress of the tensile stress-magnetic field composite annealing is 20-50 MPa;
the molecular formula of the iron-based nanocrystalline magnetic core is Fe a Si b B c Cu d Nb e Wherein a, b, c, d and e are atomic percent, b is more than or equal to 7 and less than or equal to 18; c is more than or equal to 5 and less than or equal to 13; d is more than or equal to 0.5 and less than or equal to 1.5;0E is more than or equal to 5 and less than or equal to 4; the balance being a.
2. The method according to claim 1, wherein the time of the tensile stress-magnetic field composite annealing is 10 to 300 seconds.
3. The method according to claim 1, wherein the tensile stress of the tensile stress-magnetic field composite annealing is 25 to 45MPa.
4. The method according to claim 1, wherein the external magnetic field strength of the tensile stress-magnetic field composite annealing is 800Gs or less.
5. The method according to claim 4, wherein the tensile stress-magnetic field composite annealed external magnetic field strength is 800Gs.
6. The method according to claim 1, wherein the Fe a Si b B c Cu d Nb e In the formula, 73 is less than or equal to a and less than or equal to 76, 20 is less than or equal to b+c is less than or equal to 25,1 is less than or equal to d is less than or equal to 1.5, and 1 is less than or equal to e is less than or equal to 3.
7. The method according to claim 6, wherein the Fe a Si b B c Cu d Nb e Is Fe 73.5 Si 15.5 B 7 Cu 1 Nb 3
8. The method of claim 1, wherein the iron-based nanocrystalline core has an average grain size of 13.02 to 17.75nm.
9. The iron-based nanocrystalline core produced by the production method according to any one of claims 1 to 8, having a coercivity H c 2.6 to 4.0A/m; relative to the initial magnetic permeability mu i 800-1000.
10. The iron-based nanocrystalline core according to claim 9, wherein a permeability decay rate in a frequency range of 10kHz to 1MHz is not more than 10%.
CN202310089729.XA 2023-02-08 2023-02-08 Iron-based nanocrystalline magnetic core with low coercivity and low magnetic permeability and preparation method Pending CN115995339A (en)

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Cited By (1)

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CN117095933A (en) * 2023-08-10 2023-11-21 深圳市驭能科技有限公司 Amorphous nanocrystalline strip magnetic core and preparation method and application thereof

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CN215975969U (en) * 2021-09-23 2022-03-08 长兴俊隆机电科技有限公司 Continuous amorphous and nanocrystalline alloy strip tension annealing furnace
CN114807758A (en) * 2022-04-25 2022-07-29 江苏亿仕源新材料科技有限公司 Low-coercivity iron-based nanocrystalline alloy and preparation method thereof
CN115206659A (en) * 2022-05-10 2022-10-18 金玻新材料技术有限公司 Preparation method and preparation device of partially crystallized soft magnetic alloy belt and iron core

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JP2021046592A (en) * 2019-09-19 2021-03-25 日本製鉄株式会社 Grain-oriented electromagnetic steel sheet
CN113851302A (en) * 2021-09-23 2021-12-28 东莞理工学院 Differential mode-common mode integrated magnetic core structure and manufacturing method and application thereof
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117095933A (en) * 2023-08-10 2023-11-21 深圳市驭能科技有限公司 Amorphous nanocrystalline strip magnetic core and preparation method and application thereof

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Inventor after: Zhu Zhengquan

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Inventor after: Liu Guoming

Inventor before: Zhu Zhengquan

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Inventor before: Li Weifeng

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Application publication date: 20230421